WO2010133095A1 - Release agent and applications thereof - Google Patents

Release agent and applications thereof Download PDF

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Publication number
WO2010133095A1
WO2010133095A1 PCT/CN2010/000772 CN2010000772W WO2010133095A1 WO 2010133095 A1 WO2010133095 A1 WO 2010133095A1 CN 2010000772 W CN2010000772 W CN 2010000772W WO 2010133095 A1 WO2010133095 A1 WO 2010133095A1
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WO
WIPO (PCT)
Prior art keywords
release agent
ether
particles
polyoxyethylene
agent according
Prior art date
Application number
PCT/CN2010/000772
Other languages
French (fr)
Chinese (zh)
Inventor
徐健岩
刑文涛
李志明
张勇
Original Assignee
汉高（中国）投资有限公司
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Publication date
Application filed by 汉高（中国）投资有限公司 filed Critical 汉高（中国）投资有限公司
Publication of WO2010133095A1 publication Critical patent/WO2010133095A1/en

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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
    • B29C33/56—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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/12—Polysiloxanes containing silicon bound to hydrogen

Definitions

  • the present invention relates to a release agent and its use.
  • Patent JP2003231150 describes a method for preparing a matt resin by injecting molten resin into a mold having a concave and convex surface to form a matt resin by cooling and solidifying.
  • Patent US 4,954,297 describes a matt resin prepared by heating a pressure-molded resin on a rough cast surface to prepare fine grooves.
  • patent JP58029622 (A) introduces a small amount of talc and barium sulfate powder in a polyacrylic resin, and is in the range of 200-300. Kneading extrusion molding to prepare a matt polyacrylic resin.
  • Patent CN1468900A describes an improved method of a polyvinyl chloride nitrile rubber cable material, in which a crosslinked polyvinyl chloride resin and a polyvinyl chloride are used as a base material to provide a matting effect and a matt effect.
  • a crosslinked polyvinyl chloride resin and a polyvinyl chloride are used as a base material to provide a matting effect and a matt effect.
  • Another method is to use a sanding process after the rubber molding to make the appearance of the rubber matt, but the subsequent process of this method is very complicated.
  • Patent WO2009017675A2 describes a release agent which contains siloxane, aqueous matt particles, a curing agent, and a substance having both hydrophobic and hydrophilic properties, and optionally contains a carrier in the release agent.
  • the release agent can impart a matt effect to the molding material, and can achieve multiple matte demolding, but in the use thereof, a coating of 2-3 kinds of emulsions is sequentially sprayed on the mold to realize a matt function, and each molded product The difference in gloss is large. Complex construction techniques and fluctuations in the gloss of each molded article limit the application of the release agent. Summary of the invention
  • the technical problem to be solved by the invention is to overcome the defects of the existing matte agent with complex matt effect and the difference in gloss of the product, and provide a simple construction, good release property and matt effect, and can be realized.
  • Semi-permanent demoulding, and the release of the product after repeated demolding can maintain a substantially constant gloss, without affecting product performance, storage stability of the release agent.
  • the release agent of the present invention can be cured in a wide curing temperature range, and is suitable for a variety of articles of different materials. At the same time, the demoulding can be completed on a variety of molds, and the application range is wide.
  • the release agent of the present invention comprises: a polysiloxane compound having three or more silicon hydrogen bonds, matt particles, an emulsifier, and water.
  • the polysiloxane compound having three or more silicon hydrogen bonds may have a reactive silicon hydrogen bond at its polymer chain end and/or side chain, and may be combined with a curing agent or an unsaturated polymer.
  • the reaction forms a relatively high-hardness crosslinked polymer, which is cured to form a hard film, thereby fixing the matt particles on the film without being transferred to the molded article, thereby achieving multiple matte demolding.
  • the emulsion prepared by the silicone-hydrogen-bonded polysiloxane compound can be stably present for a long period of time, so that the mold release agent of the present invention is a long-term stable water-based emulsion.
  • the polysiloxane compound having three or more silicon hydrogen bonds may be any polysiloxane compound having a silicon-hydrogen bond number of 3 or more, preferably having three or more silicon hydrogen bonds.
  • One or more of the following polymers (1) a homopolymer formed from a structural unit as shown in Formula I; (2) a random formed from structural units as shown in Formula I and Formula II , alternating, block and graft copolymers, the copolymer being a linear or cyclic copolymer; and (3) cross-linking copolymerization of one or more of the polymers of (1) and (2) above Things.
  • the terminal group of the linear or crosslinked polymer may be a conventional terminal group, preferably one or more of hydrogen, a hydroxyl group, an alkoxy group of Crdo, and a hydrocarbon group of d-o. Substituted silicon fluorenyl.
  • ⁇ is an alkoxy group of -do or a hydrocarbyl group of d-do, preferably independently of a fluorenyloxy group of ( ⁇ - ⁇ or a hydrocarbyl group of ( ⁇ - ⁇ ; and independently a hydroxy group of a hydroxyl group, dC ⁇ )
  • the hydrocarbyl group of the group or d-do is preferably independently a hydroxyl group, an alkoxy group of Ci-C 6 or a hydrocarbon group of ( ⁇ - ⁇ ), but the 1 2 and 13 are not simultaneously a hydroxyl group.
  • the content of the polysiloxane compound having three or more silicon hydrogen bonds is preferably from 1 to 65%, more preferably from 3 to 50%, based on the total mass of the release agent.
  • the polysiloxane composition having three or more silicon hydrogen bonds has a viscosity of from 5 to 10,000 cst, preferably from 5 to 5,000 cSt, more preferably from 5 to 1000 cst; and the above viscosities are measured at 25 ° C Got it.
  • the hydrogen content of the silicon-hydrogen bond of the polysiloxane compound having three or more silicon hydrogen bonds is preferably from 0.10 to 1.63%, more preferably from 0.50 to 1.63%; and the percentage is percentage by mass.
  • the matte particles are inorganic particles and/or organic particles capable of imparting a matt effect to a release agent, and various conventional matte particles may be used, preferably silica particles or metal oxides.
  • One or more of the particles, the inorganic salt particles and the polymer particles; the metal oxide particles are preferably one or more of titanium dioxide particles, aluminum oxide particles, zinc oxide particles, and silver oxide particles.
  • the inorganic salt particles are preferably calcium carbonate particles and/or barium sulfate particles.
  • the polymer particles are preferably one or more of polyethylene particles, polyvinyl chloride particles, polypropylene particles, polystyrene particles, and polytetrafluoroethylene particles.
  • the matte particles may be one or more of the following: ACEMATT® HK125, ACEMATT® HK400, ACEMATT® HK440, ACEMATT® H 450, ACEMATT® HK460, ACEMATT® OK412, ACEMATT from Degussa, Germany.
  • the particle size of the matt particles is preferably 0.2-15.0 ⁇ , more preferably 0.5-10.0 ⁇ .
  • the content of the matte particles is preferably 0.50.0%, more preferably 0.5-30.0%, of the total mass of the release agent.
  • the emulsifier in the present invention may be various emulsifiers in the prior art, which can stabilize a component such as a polysiloxane compound having three or more silicon hydrogen bonds in the release agent, and a component such as a matte particle, preferably.
  • It is a nonionic surfactant.
  • the nonionic surfactant preferably has an HLB value of from 3 to 50. More preferably, the nonionic surfactant is a polyoxyethylene type nonionic surfactant, a polyol type nonionic surfactant, an alkyl alcohol amide type nonionic surfactant, and a silicone type nonionic surfactant. One or more of them.
  • the numbers in the above brackets indicate the degree of polymerization of the polymer.
  • the number of carbon atoms before the mercapto alcohol polyoxyethylene ether is a limitation on the number of carbon atoms in the mercapto alcohol, such as C 12 alkyl alcohol polyoxyethylene (7) ether represents dodecyl alcohol polyoxyethylene (7) ether .
  • the content of the emulsifier is preferably from 0.2 to 25.0%, more preferably from 0.25 to 20.00%, based on the total mass of the release agent.
  • the water content is preferably from 20 to 98%, more preferably from 30 to 94%, based on the total mass of the release agent.
  • the release agent of the present invention may further contain other additives conventional in the art as long as it does not exert a significant negative effect on the release agent of the present invention.
  • the other additives preferably further comprise one or more of the following: an organosilicon compound, an emulsifying aid and a catalyst; the organosilicon compound contains a silyl group and/or can be hydrolyzed to form a silyl group. Group of organosilicon compounds.
  • the organosilicon compound can enhance the adhesion of the release agent to the mold.
  • the content of the organosilicon compound is preferably less than or equal to 50% of the total mass of the release agent, more preferably 30% or less.
  • the organosilicon compound is selected from one or more of the following:
  • Y, Y 2 and Y 3 are independently -H, -OH, -R 8 , -NR 9 Rio -RiiX, -R I2 SH, -R 13 OH, ⁇ _ _ o
  • R4 is ( ⁇ -(: 16 hydrocarbon group
  • R 5 is ( ⁇ -(:
  • Re and 1 7 are the same or different, independent of ( ⁇ ⁇ hydrocarbon group, but the total number of carbon atoms in R 6 and R 7 is less than or equal to 15;
  • R 1 9 and R 1Q are the same or different, independently hydrogen or C, -C 16 hydrocarbon group, but the total number of carbon atoms in R 9 and R 1 () is less than or equal to 16;
  • R 8 , R u , R l2 , R 13 and R" are independently a hydrocarbon group of ( ⁇ -(: ⁇ ;
  • R l5 is a hydrocarbon group of dC 14 ;
  • R l6 and R 17 are the same or different, independently hydrogen or ( ⁇ - (hydrocarbyl group of 13 , but not hydrogen at all, and the total number of carbon atoms in R 16 and R 17 is less than or equal to 13;
  • R l8 to R 2 o are the same or different and are independently a hydrocarbon group of CM, but the total number of carbon atoms in 1 18 , R 19 and R 20 is less than or equal to 16.
  • III (b), III (c) and III (d) More preferably, in III (b), III (c) and III (d),
  • Y, ⁇ 2, and ⁇ 3 are independently OH, -R 8 , -NH 2 , -R,, X -R 12 SH, ⁇ _ _ o
  • R 5 or -0-N CR 6 R 7 , Y, Y 2 and Y 3 are independently OH or -R 8 ; wherein R 4 to R 2 () are as defined above.
  • R 21 and R 22 are independently a hydroxyl group or a hydrocarbon group of ( ⁇ - ⁇ 1 () , R 21 and R 22 are not simultaneously a hydroxyl group, and m is an integer of from 3 to 10;
  • R 23 to R 3C are independently a hydroxyl group, an alkoxy group of - o or a. a hydrocarbon group, preferably a hydrocarbon group of ( ⁇ - ⁇ ); and R 26 and R 27 are not simultaneously a hydroxyl group, and R 23 , R 24 and R 25 are not simultaneously a hydroxyl group, R 28 , R 29 and R 3 are not simultaneously a hydroxyl group; q is an integer from 0 to 1000; the number of hydroxyl groups and/or decyloxy groups in the linear compound of the siloxane compound of the formula V is 2.
  • the above hydrocarbon group is preferably an alkyl group.
  • the organosilicon compound is one or more of the following: ⁇ -chloropropyltriethoxysilane, chloropropylmethyldiethoxysilane, bromopropylmethyldiethyl Oxysilane, tetraethoxysilane, tetra-n-butoxysilane, methyldiethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxy Silane, dimethyldiethoxysilane, propyltrimethoxysilane, allyltriethoxysilane, methylethyldimethoxysilane, phenyltriethoxysilane, benzene Tris-propoxysilane, phenyl triisopropoxysilane, phenyl tri-n-butoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, methylphenyl
  • the emulsification aid may be various types of emulsification aids which are conventionally used in the art and which do not significantly adversely affect the release agent of the present invention, and are used for increasing the hydrophilicity of the polymer and the release agent. Consistency and stability, etc.
  • the content of the emulsification aid is preferably less than or equal to 8% of the total mass of the release agent, more preferably less than or equal to 5%.
  • the emulsifying aid is one or more of a hydrophilic auxiliary agent, a thickener, a stabilizer, and a pH adjusting agent.
  • the hydrophilic auxiliary agent is preferably a water-soluble polymer compound, preferably one or more of polyvinylpyrrolidone, polyethylene glycol, polyvinyl alcohol and polyvinyl methyl ether.
  • the thickener is a thickener conventionally used in the art, preferably an aqueous thickener, more preferably a hydroxyalkyl cellulose, a cellulose ether and a polyacrylate emulsion thickener. One or more.
  • the stabilizer comprises a heat stabilizer or a freeze-thaw stabilizer.
  • the pH modifier is a ruthenium modifier conventionally used in the art, preferably one or more of an acid, a base and a salt having a molecular weight of less than or equal to 10,000; more preferably acetic acid, ammonia water, carbonic acid One or more of ammonium, sodium carbonate, and ammonium chloride.
  • the catalyst is capable of promoting between silicon hydrogen groups, silicon hydrogen groups and silicon oxygen
  • the alkyl group, and the catalyst for reacting the silicon hydride group with the silanol group include an amine catalyst and/or an organometallic catalyst.
  • the amine catalyst is preferably selected from one or more of the following: triethylenediamine, bis(dimethylaminoethyl ether), dimethylcyclohexylamine, N-methyldicyclohexyl Amine, pentamethyldiethylenetriamine, pentamethyldipropylenetriamine, tetramethylethylenediamine, tetramethylpropanediamine, tetramethylhexamethylenediamine, N-methylmorpholine, N-ethylmorpholine, 2,2-bismorpholinyl diethyl ether, cocomorpholine, N-methylimidazole, 1,2-dimethylimidazole, 1,4-dimethylpiperazine, N , N-dimethylbenzylamine, tris(dimethylaminopropyl)amine, triethylamine, hydrazine, hydrazine-dimethyl(hexadecanoyl)amine and tetramethyliminodipropyl
  • the organometallic catalyst is preferably selected from one or more of the following: dibutyltin dilaurate, stannous octoate, di(dodecylsulfide) dibutyltin, dibutyltin diacetate, potassium isooctylate , potassium acetate, potassium oleate, lead isooctanoate, zinc isooctanoate, phenylmercuric acetate, tetrabutyl titanate and tetraisopropyl titanate.
  • the content of the catalyst is preferably from 0.1 to 10.0%, more preferably from 0.1 to 8.0%, based on the total mass of the release agent.
  • the release agent of the present invention preferably has a pH of from 3 to 7, more preferably from 4 to 7.
  • the solid content of the release agent of the present invention can be adjusted by adding water.
  • the mold release agent preferably has a solid content of from 0.1 to 80.0%, more preferably from 1 to 75%.
  • the solid content is preferably 40%; in the absence of the thickener, the solid content is preferably 40-75%.
  • the solids content is from 2 to 40% when the release agent is contained in the release agent; and the solid content is from 40 to 75% when the thickener is not contained.
  • the release agent of this preferred embodiment has a long shelf life and can be stably placed at room temperature for more than one month. The percentage stated is the mass percentage.
  • the release agent of the present invention may be in the form of one component in which all the components are mixed together, or may be in a multicomponent form in which the components are separately mixed in several groups, as needed.
  • the releasing agent contains a catalyst
  • the releasing agent of the present invention preferably contains two components in which the catalyst does not coexist in the same component with the polysiloxane compound having three or more silicon hydrogen bonds.
  • the release agent contains a mixture of hydrazine and a mixture, wherein the release agent
  • the compound A contains a polysiloxane compound having three or more silicon hydrogen bonds, an emulsifier and water; the mixture B contains a catalyst and water; and the matte particles are independently present in the mixture A and/or the mixture B.
  • the mixture A further contains an organosilicon compound and/or an emulsification aid; the mixture B further contains an emulsifier and/or an emulsification aid.
  • polysiloxane means a polymer in which a main chain is composed of a repeating unit silicon-oxygen (Si-O) bond in which an organic group is directly bonded to a silicon atom.
  • the term “matte particles” means solid particles which impart a matt effect to an article.
  • the term “matt” means that the molded rubber article has a gloss of less than 5.0 (including 5.0 and an incident angle of 60).
  • the term "semi-permanent demolding" means that the release agent is sprayed once, and the release of the mold can be achieved more than five times, and the gloss of each molded product is constant.
  • the term "constant gloss of each molded article” means that the gloss of the molded article after molding is ⁇ 0.1 °.
  • the preparation method of the release agent of the present invention can be carried out by referring to a conventional method for preparing a release agent in the prior art, preferably according to the method of the patent CN 101230138A.
  • the present invention also provides the use of the release agent described in the preparation of a matt rubber article, a matt plastic article or a matt composite article.
  • the release agent of the invention has simple construction, good release property and matt effect, and forms a hard film when solidified, thereby fixing the matt particles on the film without being transferred to the molded article, This achieves semi-permanent demolding, and the gloss of the obtained product can be kept substantially constant after multiple demolding, and the gloss error is ⁇ 0.1°, which does not affect the product performance.
  • the release agent of the present invention has good stability and can be stored for more than one week at room temperature; when the polysiloxane compound having three or more silicon hydrogen bonds in the release agent does not coexist in the same mixture, the present invention
  • the release agent can be stored for more than one month, even for more than three months.
  • the release agent of the invention can be cured at different temperatures, so it can be applied to high curing temperature. Articles of the product can also be used for articles with low curing temperatures.
  • the release agent of the present invention can be used in almost all existing molds. Especially for metal molds, the silicon hydrogen bonds in the release agent can form chemical crosslinks and physical crosslinks with the hydroxyl groups on the surface of the metal mold, so that the release agent of the present invention has better adhesion to the metal mold.
  • the viscosity of the polymer was measured by a rotary viscometer of NDJ-1A from China Shende Technology Development Co., Ltd. at 25 °C ⁇ 1 °C.
  • the molecular weight of the polymer and its distribution were determined by Waters Breeze 1515 High Performance Gel Permeation Chromatography from Waters, USA.
  • the solid content of the emulsion was measured by Mettler-Toledo HB43-S Halogen Moisture Analyzer at 125 °C after cross-linking.
  • the surface energy of the film was determined by OCA-15 of Dataphysics, Germany.
  • Methylhydrogenated silicone oil Syl-off® 7048 Dow Corning, USA, containing 1.58- 1.60% hydrogen, 30cst viscosity;
  • Methyl-containing silicone oil Syl-Off®7672 Dow Corning, USA, containing 0.90% hydrogen and 70cst viscosity;
  • Methyl-containing silicone oil Syl-Off®7678 Dow Corning, USA, containing 1.05% hydrogen, viscosity 29cst;
  • Methyl Hydrogenated Silicone Oil Dow Corning® 1107 Dow Corning, USA, containing 1.60% hydrogen, Viscosity is 30cst;
  • Methyl hydrogenated silicone oil ORG202: Shanghai Langyu Industrial Co., Ltd., containing 1.58-1.63% hydrogen, viscosity 15-40cst;
  • VISC ALEX® AT88 Swiss Ciba.
  • the components in Table 1 were placed in a high-speed dispersion vessel at room temperature, and stirred at 1,500 rpm for 20 minutes to make them uniformly mixed. Then, at a speed of 1500 rpm, 31.6 g of deionized water was added dropwise at a constant rate over 30 minutes; after the completion of the dropwise addition, stirring was continued at 200 rpm for 30 minutes.
  • the release agent has a solid content of 50%, is stored at room temperature for 1 month, and can be diluted with water when used.
  • the release agent prepared in Example 1 was sprayed on a metal mold and cured at 160 Torr for 10 minutes. The film, by using this release agent to release the EPDM rubber, gives a gloss of 0.7.
  • the rubber product can be demolded more than 20 times in one spray, and the rubber gloss of each mold is constant.
  • the release thermoplastic polyurethane material can obtain a product with a gloss of 2.7°; the release polybenzoxazine material can obtain a product with a gloss of 2.3°, and can be demolded more than 5 times in one spray, and each molded product The gloss is constant.
  • the components in Table 2 were placed in a high-speed dispersion vessel at room temperature, and stirred at 1,500 rpm for 20 minutes to uniformly mix. Then, at a speed of 1500 rpm, 3 1.6 g of deionized water was added dropwise at a constant rate over 30 minutes; after the completion of the dropwise addition, stirring was continued at 200 rpm for 30 minutes.
  • the release agent has a solid content of 55%, is stored at room temperature for 2 months, and can be diluted with water when used.
  • the release agent prepared in Example 2 was sprayed on a metal mold, and the film was cured at 160 ° C for 10 minutes, and the release agent was used to release the EPDM rubber to obtain a gloss of 1.0 °. Rubber products can be demolded more than 20 times in one spray, and the rubber gloss of each mold is constant.
  • the components in Table 3 were placed in a high-speed dispersion vessel at room temperature, and stirred at 1,500 rpm for 20 minutes to uniformly mix. Then, at 1500 rpm, 30.4 g of deionized water was added dropwise at a constant rate over 30 minutes; after the completion of the dropwise addition, stirring was continued at 200 rpm for 30 minutes.
  • the release agent has a solid content of 50%, is stored at room temperature for 1 month, and can be diluted with water when used.
  • the release agent prepared in Example 3 was sprayed on a metal mold to form a film at 160 ° C for 10 minutes, and the release agent was used to release the EPDM rubber to obtain a gloss of 2.7.
  • the rubber product can be demolded more than 20 times in one spray, and the rubber gloss of each mold is constant.
  • the components in Table 4 were placed in a high-speed dispersion vessel at room temperature, and stirred at 1,500 rpm for 20 minutes to uniformly mix. Then, at 1500 rpm, 31.6 g of deionized water was added dropwise at a constant rate over 30 minutes; after the completion of the dropwise addition, stirring was continued at 200 rpm for 30 minutes.
  • the release agent has a solid content of 48%, is stored at room temperature for 2 months, and can be diluted with water when used.
  • the release agent prepared in Example 4 was sprayed on a metal mold, and the film was cured at 160 ° C for 10 minutes to form a film. Using the release agent to release the EPDM rubber, a rubber product having a gloss of 2.0° was obtained. , can be demolded more than 20 times in one spray, and the rubber gloss of each mold is constant.
  • the components in Table 5 were placed in a high-speed dispersion vessel at room temperature, and stirred at 1,500 rpm for 20 minutes to uniformly mix. Then, at a speed of 1500 rpm, 31.6 g of deionized water was added dropwise at a constant rate over 30 minutes; after the completion of the dropwise addition, stirring was continued at 200 rpm for 30 minutes.
  • the release agent has a solid content of 59%, is stored at room temperature for 2 months, and can be diluted with water when used.
  • the release agent prepared in Example 5 was sprayed on a metal mold to form a film at 160 Torr for 10 minutes, and the release agent was used to release the EPDM rubber to obtain a gloss of 0.9.
  • the rubber product can be demolded more than 20 times in one spray, and the rubber gloss of each mold is constant.
  • the components in Table 6 were placed in a high-speed dispersion vessel at room temperature, and stirred at 1,500 rpm for 20 minutes to uniformly mix. Then, at a speed of 1500 rpm, 31.6 g of deionized water was added dropwise at a constant rate over 30 minutes; after the completion of the dropwise addition, stirring was continued at 200 rpm for 30 minutes.
  • the release agent has a solid content of 62%, is stored at room temperature for 2 months, and can be diluted with water when used.
  • the release agent prepared in Example 6 was sprayed on a metal mold, and the film was cured at 160 ° C for 10 minutes to form a film. Using the release agent to release the EPDM rubber, a rubber product having a gloss of 0.9° was obtained. , can be demolded more than 20 times in one spray, and the rubber gloss of each mold is constant.
  • the components in Table 7 were placed in a high-speed dispersion vessel at room temperature, and stirred at 1,500 rpm for 20 minutes to uniformly mix. Then, at a speed of 1500 rpm, 31.6 g of deionized water was added dropwise at a constant rate over 30 minutes; after the completion of the dropwise addition, stirring was continued at 200 rpm for 30 minutes.
  • the release agent has a solid content of 64%, is stored at room temperature for 2 months, and can be diluted with water when used.
  • the release agent prepared in Example 7 was sprayed on a metal mold and cured to form a film at 160 Torr for 10 minutes. The film has a lower surface energy. By using this release agent to release the EPDM rubber, a gloss of 5 can be obtained.
  • the rubber product can be demolded more than 20 times in one spray, and the rubber gloss of each mold is constant.
  • the components in Table 8 were placed in a high-speed dispersion vessel at room temperature, and stirred at 1,500 rpm for 20 minutes to uniformly mix. Then, at a speed of 1500 rpm, 3 1.6 g of deionized water was added dropwise at a constant rate over 30 minutes; after the completion of the dropwise addition, stirring was continued at 200 rpm for 30 minutes.
  • the release agent has a solid content of 63%, is stored at room temperature for 2 months, and can be diluted with water when used.
  • the release agent prepared in Example 8 was sprayed on a metal mold and cured at 160 ° C for 10 minutes. Membrane, by using this release agent to release EPDM rubber, a rubber product having a gloss of 1.8° can be obtained, and the spray can be released more than 20 times in one spray, and the rubber gloss of each mold is constant.
  • the components in Table 9 were placed in a high-speed dispersion vessel at room temperature, and stirred at 1,500 rpm for 20 minutes to uniformly mix. Then, at 1500 rpm, 93.0 g of deionized water was added dropwise at a constant rate over 30 minutes; after the completion of the dropwise addition, stirring was continued at 200 rpm for 30 minutes.
  • the release agent has a solid content of 5.8%, is stored at room temperature for 3 months, and can be diluted with water when used.
  • the release agent prepared in Example 9 was sprayed on a metal mold, and the film was cured at 160 Torr for 10 minutes to form a film, and the release agent was used to release the EPDM rubber to obtain a matt rubber product having a gloss of 0.7°. , can be demolded more than 20 times in one spray, and the rubber gloss of each mold is constant.
  • Mixture A and mixture B are uniformly mixed at a mass ratio of 1:1, and then sprayed on a metal mold at 60 ° C for 30 minutes to form a film, and the release agent is used to release EPDM rubber to obtain a gloss of 0.7 °.
  • Light rubber products can be demolded more than 20 times in one spray, and the rubber gloss of each mold is constant.

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
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  • Medicinal Chemistry (AREA)
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  • Compositions Of Macromolecular Compounds (AREA)
  • Moulds For Moulding Plastics Or The Like (AREA)

Abstract

A release agent comprising polysiloxane compound having three or more silicon-hydrogen bonds, matt particles, emulsifier and water is disclosed. Applications of the release agent in production of matt rubber products, matt plastic products, or matt composite products are also provided. The release agent can be widely applied to almost all existing molds, and good adhesion is especially obtained in case of metal mold.

Description

一种脱模剂及其应用  Release agent and application thereof
技术领域 Technical field
本发明涉及一种脱模剂及其应用。  The present invention relates to a release agent and its use.
背景技术 Background technique
随着人们对光污染认识的提高， 亚光制品越来越受青睐。 通常对于 有亚光要求的制品， 例如橡胶、 塑料、 复合材料等， 现有的技术中常用 的一种办法是利用模具来实现亚光， 即将模具做成凹凸不平的表面， 然 后压模成型。 专利 JP2003231150 ( A ) 介绍了一种将熔融的树脂注入表面 凸凹不平的模具中冷却凝固成型制备亚光树脂的方法。 专利 US4954297 ( A ) 介绍了一种在粗糙铸造表面上加热加压成型树脂， 制备有微细凹槽 的亚光树脂。 但是凸凹不平的模具表面积增加， 不利于脱模剂的涂布和 模具的清洗， 造成制品脱模困难， 破坏制品表面形貌。 另一种办法是在 制品中加入亚光助剂， 以实现橡胶亚光效果， 例如专利 JP58029622 ( A ) 介绍了一种在聚丙烯酸树脂中加入少量滑石粉和硫酸钡粉末， 并在 200-300°C捏合挤出成型， 制备亚光聚丙烯酸树脂。专利 CN1468900A介绍 了一种聚氯乙烯丁腈橡胶电缆料的改进方法， 其中提到交联聚氯乙烯树 脂与聚氯乙烯同作基料， 可起到消光作用， 产生亚光效果。 但助剂的加 入会降低橡胶本身的一些性能。 另一种办法是橡胶成型后另行采用砂磨 工艺使橡胶外观呈亚光状态， 但这种办法后续工艺非常复杂。  As people's awareness of light pollution increases, matt products are increasingly favored. Typically for products having matt requirements, such as rubber, plastics, composites, etc., one approach commonly used in the prior art is to use a mold to achieve matt, i.e., to make the mold a rugged surface, and then to form a mold. Patent JP2003231150 (A) describes a method for preparing a matt resin by injecting molten resin into a mold having a concave and convex surface to form a matt resin by cooling and solidifying. Patent US 4,954,297 (A) describes a matt resin prepared by heating a pressure-molded resin on a rough cast surface to prepare fine grooves. However, the surface area of the uneven mold increases, which is not conducive to the application of the release agent and the cleaning of the mold, which makes the release of the product difficult, and damages the surface topography of the product. Another method is to add a matt additive to the product to achieve a rubber matt effect. For example, patent JP58029622 (A) introduces a small amount of talc and barium sulfate powder in a polyacrylic resin, and is in the range of 200-300. Kneading extrusion molding to prepare a matt polyacrylic resin. Patent CN1468900A describes an improved method of a polyvinyl chloride nitrile rubber cable material, in which a crosslinked polyvinyl chloride resin and a polyvinyl chloride are used as a base material to provide a matting effect and a matt effect. However, the addition of additives will reduce some of the properties of the rubber itself. Another method is to use a sanding process after the rubber molding to make the appearance of the rubber matt, but the subsequent process of this method is very complicated.
因此， 既有脱模性能又有亚光效果的脱模剂越来越受欢迎。 专利 WO2009017675A2 介绍了一种脱模剂， 其配方中含有硅氧垸、 水性亚光粒 子、 固化剂、 以及同时具有疏水和亲水特性的物质， 此外脱模剂中可选择的 含有载体。 该脱模剂可以赋予成型物质亚光效果， 且可实现多次亚光脱模， 但其使用时在模具上要依次喷涂 2-3种乳液的涂层以实现亚光功能， 且每模 制品之间的光泽度相差较大。复杂的施工工艺及每模制品光泽度的波动限制 了该脱模剂的应用。 发明内容 Therefore, release agents having both release properties and matt effects are becoming more and more popular. Patent WO2009017675A2 describes a release agent which contains siloxane, aqueous matt particles, a curing agent, and a substance having both hydrophobic and hydrophilic properties, and optionally contains a carrier in the release agent. The release agent can impart a matt effect to the molding material, and can achieve multiple matte demolding, but in the use thereof, a coating of 2-3 kinds of emulsions is sequentially sprayed on the mold to realize a matt function, and each molded product The difference in gloss is large. Complex construction techniques and fluctuations in the gloss of each molded article limit the application of the release agent. Summary of the invention
本发明所要解决的技术问题是克服了现有的具有亚光效果的脱模剂 施工复杂、 制品光泽度相差大的缺陷， 提供了一种施工简单， 脱模性和亚 光效果倶佳， 可实现半永久型脱模， 且多次脱模后所得制品光泽度能保持基 本恒定， 不影响制品性能， 存放稳定性高的脱模剂。 且本发明的脱模剂能 在较宽固化温度范围内固化， 适用于多种不同材质的制品。 同时能在多 种模具上完成脱模， 应用范围广。  The technical problem to be solved by the invention is to overcome the defects of the existing matte agent with complex matt effect and the difference in gloss of the product, and provide a simple construction, good release property and matt effect, and can be realized. Semi-permanent demoulding, and the release of the product after repeated demolding can maintain a substantially constant gloss, without affecting product performance, storage stability of the release agent. Moreover, the release agent of the present invention can be cured in a wide curing temperature range, and is suitable for a variety of articles of different materials. At the same time, the demoulding can be completed on a variety of molds, and the application range is wide.
本发明的脱模剂包含： 具有三个以上硅氢键的聚硅氧垸化合物、亚光 粒子、 乳化剂和水。  The release agent of the present invention comprises: a polysiloxane compound having three or more silicon hydrogen bonds, matt particles, an emulsifier, and water.
本发明中， 所述的具有三个以上硅氢键的聚硅氧烷化合物由于在其聚 合链端和 /或侧链带有具有反应活性的硅氢键， 可与固化剂或不饱和聚合 物反应形成较高硬度的交联聚合物， 即可固化形成较硬的膜， 从而将亚 光粒子固定在膜上， 而不被转移到成型品上， 由此实现多次亚光脱模。 此外， 具有硅氢键的聚硅氧垸化合物制备的乳液可以长期稳定存在， 使 得本发明的脱模剂为长期稳定的水基乳液。  In the present invention, the polysiloxane compound having three or more silicon hydrogen bonds may have a reactive silicon hydrogen bond at its polymer chain end and/or side chain, and may be combined with a curing agent or an unsaturated polymer. The reaction forms a relatively high-hardness crosslinked polymer, which is cured to form a hard film, thereby fixing the matt particles on the film without being transferred to the molded article, thereby achieving multiple matte demolding. Further, the emulsion prepared by the silicone-hydrogen-bonded polysiloxane compound can be stably present for a long period of time, so that the mold release agent of the present invention is a long-term stable water-based emulsion.
所述的具有三个以上硅氢键的聚硅氧垸化合物可以为任何现有的所 含硅氢键数量大于或等于 3 的聚硅氧烷化合物， 较佳地为具有三个以上 硅氢键的下述聚合物中的一种或多种： （ 1 )由如式 I所示的结构单元形成 的均聚物； （2 ) 由如式 I和式 II所示的结构单元形成的无规、 交替、 嵌 段和接枝共聚物， 该共聚物为线性或环状共聚物； 和 （3 ) 由上述 （1 ) 和 （2 ) 的聚合物中的一种或多种形成的交联共聚物。 上述聚合物中， 线 性或交联聚合物的封端基可为常规的封端基，较佳的为由氢、羟基、 Crdo 的烷氧基和 d- o的烃基中的一种或多种取代的硅垸基。  The polysiloxane compound having three or more silicon hydrogen bonds may be any polysiloxane compound having a silicon-hydrogen bond number of 3 or more, preferably having three or more silicon hydrogen bonds. One or more of the following polymers: (1) a homopolymer formed from a structural unit as shown in Formula I; (2) a random formed from structural units as shown in Formula I and Formula II , alternating, block and graft copolymers, the copolymer being a linear or cyclic copolymer; and (3) cross-linking copolymerization of one or more of the polymers of (1) and (2) above Things. In the above polymer, the terminal group of the linear or crosslinked polymer may be a conventional terminal group, preferably one or more of hydrogen, a hydroxyl group, an alkoxy group of Crdo, and a hydrocarbon group of d-o. Substituted silicon fluorenyl.
Figure imgf000003_0001
其中， ^为 -do的烷氧基或 d-do的烃基， 较佳地独立的为（^-^的 垸氧基或 (^-^的烃基； 和 独立的为羟基、 d-C^的垸氧基或 d-do 的烃基， 较佳地独立的为羟基、 Ci-C6的烷氧基或 (^-^的烃基， 但 1 2和 1 3不同时为羟基。
Figure imgf000003_0001
Wherein ^ is an alkoxy group of -do or a hydrocarbyl group of d-do, preferably independently of a fluorenyloxy group of (^-^ or a hydrocarbyl group of (^-^; and independently a hydroxy group of a hydroxyl group, dC^) The hydrocarbyl group of the group or d-do is preferably independently a hydroxyl group, an alkoxy group of Ci-C 6 or a hydrocarbon group of (^-^), but the 1 2 and 13 are not simultaneously a hydroxyl group.
所述的具有三个以上硅氢键的聚硅氧烷化合物的含量较佳的为脱模 剂总质量的 1-65%， 更佳的为 3-50%。 所述的具有三个以上硅氢键的聚硅 氧垸化合物的粘度为的 5-10000cst， 较佳的为 5-5000cst， 更佳的为 5-1000cst; 上述粘度皆为在 25°C下测得。所述的具有三个以上硅氢键的聚 硅氧烷化合物的硅氢键上的氢含量较佳的为 0.10-1.63%， 更佳的为 0.50-1.63%； 百分比为质量百分比。  The content of the polysiloxane compound having three or more silicon hydrogen bonds is preferably from 1 to 65%, more preferably from 3 to 50%, based on the total mass of the release agent. The polysiloxane composition having three or more silicon hydrogen bonds has a viscosity of from 5 to 10,000 cst, preferably from 5 to 5,000 cSt, more preferably from 5 to 1000 cst; and the above viscosities are measured at 25 ° C Got it. The hydrogen content of the silicon-hydrogen bond of the polysiloxane compound having three or more silicon hydrogen bonds is preferably from 0.10 to 1.63%, more preferably from 0.50 to 1.63%; and the percentage is percentage by mass.
本发明中， 所述的亚光粒子为能赋予脱模剂亚光效果的无机粒子和 / 或有机粒子， 可采用现有的各种亚光粒子， 较佳的为二氧化硅粒子、 金 属氧化物粒子、 无机盐粒子和聚合物粒子中的一种或多种； 所述的金属 氧化物粒子较佳的为二氧化钛粒子、 氧化铝粒子、 氧化锌粒子和氧化银 粒子中的一种或多种。 所述的无机盐粒子较佳的为碳酸钙粒子和 /或硫酸 钡粒子。 所述的聚合物粒子较佳的为聚乙烯粒子、 聚氯乙烯粒子、 聚丙 烯粒子、 聚苯乙烯粒子和聚四氟乙烯粒子中的一种或多种。 所述的亚光 粒子非限定的可以为下列中的一种或多种： 德国 Degussa 公司的 ACEMATT®HK125 、 ACEMATT®HK400 、 ACEMATT®HK440 、 ACEMATT®H 450 、 ACEMATT®HK460 、 ACEMATT®OK412 、 ACEMATT®OK500 、 ACEMATT®OK412LC 、 ACEMATT®OK607 、 ACEMATT®TS 100 、 ACEMATT®3300 、 Aeroxide®TiO2T805 和 Aeroxide®AluC805；美国 Grace公司的 SYLOBLOC®K200、 SYLOID®C803、 SYLOID®ED2、 SYLOID®Sy7000、 SYLOID®C805、 SYLOID®C305、 SYLOID®C807、 SYLOID®C809和 SYLOID®ED5 ; 美国 Cabot 公司生产 的气相法纳米二氧化硅 CAB-O-SIL®M-5和 CAB-0-SIL®H-5 ;美国 3M公 司生产的 Dyneon TF-9207 等。 所述的亚光粒子的粒径较佳的为 0.2-15.0μιτι, 更佳的为 0.5-10.0μηι。 所述亚光粒子的含量较佳的为脱模剂 总质量的 0. 50.0%, 更佳的为 0.5-30.0%。 In the present invention, the matte particles are inorganic particles and/or organic particles capable of imparting a matt effect to a release agent, and various conventional matte particles may be used, preferably silica particles or metal oxides. One or more of the particles, the inorganic salt particles and the polymer particles; the metal oxide particles are preferably one or more of titanium dioxide particles, aluminum oxide particles, zinc oxide particles, and silver oxide particles. . The inorganic salt particles are preferably calcium carbonate particles and/or barium sulfate particles. The polymer particles are preferably one or more of polyethylene particles, polyvinyl chloride particles, polypropylene particles, polystyrene particles, and polytetrafluoroethylene particles. The matte particles may be one or more of the following: ACEMATT® HK125, ACEMATT® HK400, ACEMATT® HK440, ACEMATT® H 450, ACEMATT® HK460, ACEMATT® OK412, ACEMATT from Degussa, Germany. ® OK500, ACEMATT® OK412LC, ACEMATT® OK607, ACEMATT® TS 100, ACEMATT® 3300, Aeroxide® TiO 2 T805 and Aeroxide® AluC805; SYLOBLOC® K200, SYLOID® C803, SYLOID® ED2, SYLOID® Sy7000 from Grace, USA SYLOID®C805, SYLOID®C305, SYLOID®C807, SYLOID®C809 and SYLOID®ED5; Gasoline Nanosilica CAB-O-SIL®M-5 and CAB-0-SIL®H-5 from Cabot, USA ; Dyneon TF-9207 produced by 3M Company of the United States. The particle size of the matt particles is preferably 0.2-15.0 μιτι, more preferably 0.5-10.0 μηι. The content of the matte particles is preferably 0.50.0%, more preferably 0.5-30.0%, of the total mass of the release agent.
本发明中的乳化剂可为现有的各种乳化剂， 其可对脱模剂中的具有 三个以上硅氢键的聚硅氧垸化合物和亚光粒子等成分起稳定作用， 较佳 的为非离子表面活性剂。 所述的非离子表面活性剂的 HLB 值较佳的为 3-50。 所述的非离子表面活性剂更佳的为聚氧乙烯型非离子表面活性剂、 多元醇型非离子表面活性剂、 烷基醇酰胺型非离子表面活性剂和有机硅 型非离子表面活性剂中的一种或多种。 更佳的， 所述的乳化剂选自下列 中的一种或多种： 聚氧化乙烯 （4) 壬基酚醚硫酸铵 （HLB=44)、 月桂醇 聚氧化乙烯（2)醚（HLB=9.5)、 月桂醇聚氧化乙烯（7)醚（HLB=11.0)、 月桂醇聚氧化乙烯 （12) 醚 （HLB=14.8)、 月桂醇聚氧化乙烯 （15) 醚 The emulsifier in the present invention may be various emulsifiers in the prior art, which can stabilize a component such as a polysiloxane compound having three or more silicon hydrogen bonds in the release agent, and a component such as a matte particle, preferably. It is a nonionic surfactant. The nonionic surfactant preferably has an HLB value of from 3 to 50. More preferably, the nonionic surfactant is a polyoxyethylene type nonionic surfactant, a polyol type nonionic surfactant, an alkyl alcohol amide type nonionic surfactant, and a silicone type nonionic surfactant. One or more of them. More preferably, the emulsifier is selected from one or more of the following: polyoxyethylene (4) nonylphenol ether ammonium sulfate (HLB=44), lauryl alcohol polyoxyethylene (2) ether (HLB= 9.5), lauryl alcohol polyoxyethylene (7) ether (HLB = 11.0), lauryl alcohol polyoxyethylene (12) ether (HLB = 14.8), lauryl alcohol polyoxyethylene (15) ether
(HLB=15.5)、 月桂醇聚氧化乙烯 (23) 醚 （HLB=16.9)、 C9-Cn垸基醇 聚氧化乙烯 (6) 醚 (例如 Neodol91-6， HLB=12.5)、 C12-C14垸基醇聚氧 化乙烯 (7)醚（例如 Imbentin- AG/124/070, Marlipal, HLB=12.0)、 C12-C15 烷基醇聚氧化乙烯 （12) 醚 （例如 Alkasurf LA-12， Tergitol 25-L-12, HLB=14.4)、 十三垸基醇聚氧化乙烯 （6) 醚 （HLB=11.4)、 十三烷基醇 聚氧化乙烯 （ 10) 醚 （HLB=13.8)、 十三垸基醇聚氧化乙烯 （ 15) 醚(HLB=15.5), lauryl alcohol polyoxyethylene (23) ether (HLB=16.9), C 9 -C n mercapto alcohol polyoxyethylene (6) ether (eg Neodol 91-6, HLB=12.5), C 12 - C 14 mercapto alcohol polyoxyethylene (7) ether (eg Imbenin-AG/124/070, Marlipal, HLB=12.0), C 12 -C 15 alkyl alcohol polyoxyethylene (12) ether (eg Alkasurf LA-12 , Tergitol 25-L-12, HLB=14.4), Tridecyl alcohol polyoxyethylene (6) ether (HLB=11.4), tridecyl alcohol polyoxyethylene (10) ether (HLB=13.8), ten Tridecyl alcohol polyoxyethylene (15) ether
(HLB=15.5)、 鲸蜡基醇聚氧化乙烯 （15) 醚 （HLB=15.5)、 鲸蜡基醇聚 氧化乙烯（20)醚（HLB=17.0)、鲸蜡基醇聚氧化乙烯（30)醚（HLB=19.5)、 异鲸蜡基醇聚氧化乙烯（20)醚（HLB=15.7)、十六烷基醇聚氧化乙烯（12) 醚、 十八垸基醇聚氧化乙烯 (12) 醚 （例如 IncropolCS-12，HLB=12.0)、 十六垸基醇聚氧化乙烯 （30) 醚、 十八烷基醇聚氧化乙烯 （30) 醚 （例 如 Incropol CS-30, HLB=16.7)、硬脂基醇聚氧化乙烯（20)醚（HLB=15.3)、 硬脂基醇聚氧化乙烯 （40) 醚 （ HLB=17.4)、 油醇聚氧化乙烯 （20) 醚(HLB=15.5), cetyl alcohol polyoxyethylene (15) ether (HLB=15.5), cetyl alcohol polyoxyethylene (20) ether (HLB=17.0), cetyl alcohol polyethylene oxide (30) Ether (HLB=19.5), isocetyl alcohol polyoxyethylene (20) ether (HLB=15.7), cetyl alcohol polyoxyethylene (12) ether, octadecyl alcohol polyoxyethylene (12) ether (eg Incropol CS-12, HLB = 12.0), hexadecanol polyoxyethylene (30) ether, octadecyl alcohol polyoxyethylene (30) ether (eg Incropol CS-30, HLB = 16.7), hard fat Alcohol polyoxyethylene (20) ether (HLB = 15.3), stearyl alcohol polyoxyethylene (40) ether (HLB = 17.4), oleyl alcohol polyoxyethylene (20) ether
(HLB=15.5)、 壬基酚聚氧化乙烯 （9) 醚 （HLB=13.5)、 壬基酚聚氧化 乙烯 （10) 醚 （HLB=14.0)、 壬基酚聚氧化乙烯 （12) 醚 （HLB=14.6)、 壬基酚聚氧化乙烯 （30) 醚 （HLB=17.5)、 壬基酚聚氧化乙烯 （40) 醚 (HLB=18.0)、 壬基酚聚氧化乙烯 （70) 醚 （HLB=18.7)、 壬基酚聚氧化 乙烯 (·5) 醚 （HLB=10.0)、 壬基酚聚氧化乙烯 （8) 醚 （HLB=12.4)、 壬 基酚聚氧化乙烯 （ 100) 醚 （HLB=19.1)、 椰油胺聚氧化乙烯 （ 15) 醚 (HLB=15.7)、 乙二胺聚氧化乙烯-聚氧化丙烯-聚氧化乙烯嵌段聚醚 (HLB=12-18 )、 二月桂酸聚乙二醇 （8) 酉旨 （HLB=10.8)、 二月桂酸聚 乙二醇 （20) 酯 （HLB=10.8)、 硬脂酸聚乙二醇 （40) 酯 （HLB=16.9)、 硬脂酸聚乙二醇 （100) 酯 （HLB=18.5)、 聚氧化乙烯 (20) 甘油单硬脂酸 酯 （HLB=13.1)、 聚氧化乙烯 (5)失水山梨醇单油酸酯 （HLB=10.0)、 聚氧 乙烯山梨醇酐三油酸酯 （HLB=11.0) 和聚醚改性聚硅氧烷。 上述括号中 的数字表示聚合物的聚合度。 垸基醇聚氧化乙烯醚前的碳原子数是对垸 基醇中碳原子数的限定， 如 C12烷基醇聚氧化乙烯 （7) 醚表示十二烷基 醇聚氧化乙烯 （7) 醚。 所述的乳化剂的含量较佳的为脱模剂总质量的 0.2-25.0%, 更佳的为 0.25-20.00%。 (HLB=15.5), nonylphenol polyoxyethylene (9) ether (HLB=13.5), nonylphenol polyoxyethylene (10) ether (HLB=14.0), nonylphenol polyoxyethylene (12) ether (HLB =14.6), Nonylphenol polyoxyethylene (30) ether (HLB=17.5), nonylphenol polyoxyethylene (40) ether (HLB=18.0), nonylphenol polyoxyethylene (70) ether (HLB=18.7), sulfhydryl Phenol polyoxyethylene (·5) ether (HLB=10.0), nonylphenol polyoxyethylene (8) ether (HLB=12.4), nonylphenol polyoxyethylene (100) ether (HLB=19.1), cocoamine Polyethylene oxide (15) ether (HLB=15.7), ethylenediamine polyoxyethylene-polyoxypropylene-polyoxyethylene block polyether (HLB=12-18), dilaurate polyethylene glycol (8) 酉(HLB=10.8), polyethylene glycol (20) dilaurate (HLB=10.8), polyethylene glycol (40) stearate (HLB=16.9), stearic acid polyethylene glycol (100 Ester (HLB=18.5), polyoxyethylene (20) glyceryl monostearate (HLB=13.1), polyethylene oxide (5) sorbitan monooleate (HLB=10.0), polyoxyethylene sorbitol Alcoholic anhydride trioleate (HLB = 11.0) and polyether modified polysiloxane. The numbers in the above brackets indicate the degree of polymerization of the polymer. The number of carbon atoms before the mercapto alcohol polyoxyethylene ether is a limitation on the number of carbon atoms in the mercapto alcohol, such as C 12 alkyl alcohol polyoxyethylene (7) ether represents dodecyl alcohol polyoxyethylene (7) ether . The content of the emulsifier is preferably from 0.2 to 25.0%, more preferably from 0.25 to 20.00%, based on the total mass of the release agent.
本发明中， 所述的水的含量较佳的为脱模剂总质量的 20-98%， 更佳 的为 30-94%。  In the present invention, the water content is preferably from 20 to 98%, more preferably from 30 to 94%, based on the total mass of the release agent.
本发明的脱模剂还可含有本领域常规的其他添加剂， 只要其对本发 明的脱模剂不起到明显负效果。 所述的其他添加剂较佳地还含有下列中 的一种或多种： 有机硅化合物、 乳化助剂和催化剂； 所述的有机硅化合 物为含有硅羟基基团和 /或可水解形成硅羟基基团的有机硅化合物。  The release agent of the present invention may further contain other additives conventional in the art as long as it does not exert a significant negative effect on the release agent of the present invention. The other additives preferably further comprise one or more of the following: an organosilicon compound, an emulsifying aid and a catalyst; the organosilicon compound contains a silyl group and/or can be hydrolyzed to form a silyl group. Group of organosilicon compounds.
本发明中， 所述的有机硅化合物， 能利于增强脱模剂与模具的粘结 性。 所述的有机硅化合物的含量较佳的为小于或等于脱模剂总质量的 50%, 更佳的为小于或等于 30%。  In the present invention, the organosilicon compound can enhance the adhesion of the release agent to the mold. The content of the organosilicon compound is preferably less than or equal to 50% of the total mass of the release agent, more preferably 30% or less.
较佳的， 所述的有机硅化合物选自下述中的一种或多种：  Preferably, the organosilicon compound is selected from one or more of the following:
(1) 式 III (a)、 式 III (b)、 式 III (c) 和式 III (d) 所示的硅烷化合 物；
Figure imgf000007_0001
(1) a silane compound of the formula III (a), the formula III (b), the formula III (c) and the formula III (d);
Figure imgf000007_0001
式 III (a) 式 III (b) 式 III (c) 式 III (d) 其中， W为 -OR4、 一 O—
Figure imgf000007_0002
； Formula III (a) Formula III (b) Formula III (c) Formula III (d) wherein W is -OR4, an O-
Figure imgf000007_0002
;
Y,、 Y2和 Y3独立的为 -H、 -OH、 -R8、 -NR9Rio -RiiX、 -RI2SH、 -R13OH、 ― ― _ o Y, Y 2 and Y 3 are independently -H, -OH, -R 8 , -NR 9 Rio -RiiX, -R I2 SH, -R 13 OH, ― _ _ o
-R,4NH CwC— R 5_ 、 -R16OOCR17C = CH2或 — R18O— P-OR20 ； -R, 4 NH C w C- R 5_ , -R 16 OOCR 17 C = CH 2 or - R 18 O- P-OR 20 ;
ORi9  ORi9
R4为 (^-(：16的烃基; R4 is (^-(: 16 hydrocarbon group;
R5为（^-(：|5的烃基； R 5 is (^-(: |5 hydrocarbon group;
Re和 17相同或不相同， 独立的为（^ ^的烃基， 但 R6和 R7中碳 原子总数小于或等于 15; Re and 1 7 are the same or different, independent of (^ ^ hydrocarbon group, but the total number of carbon atoms in R 6 and R 7 is less than or equal to 15;
19和 R1Q相同或不相同， 独立的为氢或 C,-C16的烃基， 但 R9和 R1() 中碳原子总数小于或等于 16; 1 9 and R 1Q are the same or different, independently hydrogen or C, -C 16 hydrocarbon group, but the total number of carbon atoms in R 9 and R 1 () is less than or equal to 16;
R8、 Ru、 Rl2、 R13和 R"独立的为（^-(：^的烃基； R 8 , R u , R l2 , R 13 and R" are independently a hydrocarbon group of (^-(:^;
Rl5为 d-C14的烃基； R l5 is a hydrocarbon group of dC 14 ;
Rl6和 R17相同或不相同， 独立的为氢或（^-( 13的烃基， 但不同时 为氢， 且 R16和 R17中碳原子总数小于或等于 13; R l6 and R 17 are the same or different, independently hydrogen or (^- (hydrocarbyl group of 13 , but not hydrogen at all, and the total number of carbon atoms in R 16 and R 17 is less than or equal to 13;
Rl8〜R2o相同或不相同， 独立的为 CM的烃基， 但118、 R19和 R20 中碳原子总数小于或等于 16。 R l8 to R 2 o are the same or different and are independently a hydrocarbon group of CM, but the total number of carbon atoms in 1 18 , R 19 and R 20 is less than or equal to 16.
更佳的， 在 III (b)、 式 III (c) 和式 III (d) 中，  More preferably, in III (b), III (c) and III (d),
当 W为 -OR4时， Y,、 Υ2和 Υ3独立的为 OH、 -R8、 -NH2、 -R,,X -R12SH、 ― ― _ o When W is -OR4, Y, Υ 2, and Υ 3 are independently OH, -R 8 , -NH 2 , -R,, X -R 12 SH, ― _ _ o
-R13OH、 -R14NH、 C\^C— Rl5—、 -R16OOCR17C=CH2或一 R18。一 -OR20 ; -R 13 OH, -R 14 NH, C \^ C - Rl5 -, -R 16 OOCR 17 C=CH 2 or a R 18 . One-OR 20 ;
o OR19 o OR 19
当 W为―。 _R5或 -0-N=CR6R7时， Y,、 Y2和 Y3独立的为 OH或 -R8; 其中， R4〜R2()如前述。 When W is "." When R 5 or -0-N=CR 6 R 7 , Y, Y 2 and Y 3 are independently OH or -R 8 ; wherein R 4 to R 2 () are as defined above.
(2) 式 IV所示的硅氧垸环状化合物；
Figure imgf000008_0001
式 IV 其中， R21和 R22独立的为羟基或（^-< 1()的烃基， R21和 R22不同时为羟基， m为 3-10的整数； (2) a siloxane ring compound represented by Formula IV;
Figure imgf000008_0001
Wherein R 21 and R 22 are independently a hydroxyl group or a hydrocarbon group of (^-< 1 () , R 21 and R 22 are not simultaneously a hydroxyl group, and m is an integer of from 3 to 10;
以及 （3 ) 式 V所示的硅氧垸线性化合物；  And (3) a siloxane linear compound represented by Formula V;
Figure imgf000008_0002
Figure imgf000008_0002
式 V 其中， R23〜R3C独立地为羟基、 - o的烷氧基或 。的烃基， 优 选为（^-^的烃基； 且 R26和 R27不同时为羟基， R23、 R24和 R25不同时为 羟基， R28、 R29和 R3。不同时为羟基； q为 0- 1000的整数； 式 V的硅氧院 线性化合物中羟基和 /或垸氧基的个数 2。 Wherein R 23 to R 3C are independently a hydroxyl group, an alkoxy group of - o or a. a hydrocarbon group, preferably a hydrocarbon group of (^-^); and R 26 and R 27 are not simultaneously a hydroxyl group, and R 23 , R 24 and R 25 are not simultaneously a hydroxyl group, R 28 , R 29 and R 3 are not simultaneously a hydroxyl group; q is an integer from 0 to 1000; the number of hydroxyl groups and/or decyloxy groups in the linear compound of the siloxane compound of the formula V is 2.
上述烃基优选为烷基。  The above hydrocarbon group is preferably an alkyl group.
较佳地， 所述的有机硅化合物为下列中的一种或多种： γ-氯丙基三乙 氧基硅烷、 氯丙基甲基二乙氧基硅垸、 溴丙基甲基二乙氧基硅垸、 四乙 氧基硅垸、 四正丁氧基硅烷、 甲基二乙氧基硅垸、 甲基三甲氧基硅垸、 甲基三乙氧基硅垸、 乙基三乙氧基硅烷、 二甲基二乙氧基硅烷、 丙基三 甲氧基硅垸、 烯丙基三乙氧基硅垸、 甲基乙基二甲氧基硅垸、 苯基三乙 氧基硅烷、 苯基三丙氧基硅烷、 苯基三异丙氧基硅垸、 苯基三正丁氧基 硅烷、 二苯基二甲氧基硅垸、 二苯基二乙氧基硅烷、 甲基苯基二甲氧基 硅烷、 甲基苯基二乙氧基硅烷、 乙基苯基二乙氧基硅垸、 二乙磷酸酯乙 基三乙氧基硅烷、 乙烯基三乙氧基硅烷、 乙烯基三 （β -甲氧基乙氧基） 硅烷、 γ-氨丙基三乙氧基硅烷、 γ- (β-氨乙基) -氨丙基甲基二甲氧基硅烷、 γ-(β-氨乙基) -氨丙基三甲氧基硅垸、 γ- ( β-羟乙基氨乙基） -氨丙基甲基二 甲氧基硅烷、 Ν,Ν-二乙基个胺丙基三甲氧基硅垸、 Ν-甲基 -3-氨丙基三甲 氧基硅垸、 3-环己基-氨丙基甲基二甲氧基硅烷、 γ-缩水甘油醚氧基丙基 三甲氧基硅垸、 γ-¾水甘油醚氧基丙基三乙氧基硅垸、 γ-缩水甘油醚氧基 丙基甲基二乙氧基硅垸、 γ-甲基丙烯酰氧基丙基三甲氧基硅烷、 γ-甲基丙 烯酰氧基甲基二甲氧基硅垸、 3-脲基丙基三甲氧基硅烷 、 γ-巯丙基三乙 氧基硅垸、 γ-巯丙基三甲氧基硅烷、 苯胺甲基三乙氧基硅垸、 羟乙基二甲 基苯基硅垸、 二羟丙基二甲基硅垸、 四乙酰氧基硅垸、 甲基三乙酰氧基 硅垸、 甲基三丙酰氧基硅垸、 三苯基乙酰氧基硅垸、 乙烯基三丁酮肟基 硅烷、 甲基三丙酮肟基硅垸和氯丙基三丁酮肟基硅垸、 十甲基环五硅氧 烷、 羟基聚二甲基硅氧烷、 三乙氧基硅垸化聚二甲基硅氧垸、 乙烯基二 甲氧基硅烷化聚二甲基硅氧垸、 甲基乙基甲氧基硅垸化聚二甲基硅氧垸 和乙烯基二甲氧基硅烷化聚甲基苯基硅氧烷等。 Preferably, the organosilicon compound is one or more of the following: γ-chloropropyltriethoxysilane, chloropropylmethyldiethoxysilane, bromopropylmethyldiethyl Oxysilane, tetraethoxysilane, tetra-n-butoxysilane, methyldiethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxy Silane, dimethyldiethoxysilane, propyltrimethoxysilane, allyltriethoxysilane, methylethyldimethoxysilane, phenyltriethoxysilane, benzene Tris-propoxysilane, phenyl triisopropoxysilane, phenyl tri-n-butoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, methylphenyl Methoxysilane, methylphenyldiethoxysilane, ethylphenyldiethoxysilane, diethylphosphoric acid ethyltriethoxysilane, vinyltriethoxysilane, vinyl tri --methoxyethoxy)silane, γ-aminopropyltriethoxysilane, γ-(β-aminoethyl)-aminopropylmethyldimethoxysilane, Γ-(β-aminoethyl)-aminopropyltrimethoxysilane, γ-(β-hydroxyethylaminoethyl)-aminopropylmethyldimethoxysilane, hydrazine, hydrazine-diethyl Aminopropyltrimethoxysilane, Ν-methyl-3-aminopropyltrimethoxysilane, 3-cyclohexyl-aminopropylmethyldimethoxysilane, γ-glycidyloxypropane Trimethoxysilane, γ-3⁄4 glyceryloxypropyltriethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-methacryloyloxy Propyltrimethoxysilane, γ-methacryloyloxymethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-巯Propyltrimethoxysilane, aniline methyltriethoxysilane, hydroxyethyldimethylphenylsilica, dihydroxypropyldimethylsilyl, tetraacetoxysilane, methyltriacetoxy Silicon germanium, methyl tripropionyloxy silicon germanium, triphenylacetoxy silicon germanium, vinyl tributyl ketone sulfonium silane, methyl triacetone fluorenyl silicon germanium and chloropropyl tributol ketone silicon Bismuth, decamethylcyclopentasiloxane, hydroxypolydimethylsiloxane Triethoxy silicon germanium polydimethyl siloxane, vinyl dimethoxy silylated polydimethyl siloxane, methyl ethyl methoxy silicon germanium polydimethyl siloxane and ethylene Dimethoxysilylated polymethylphenylsiloxane and the like.
本发明中， 所述的乳化助剂可为本领域常规使用的不显著地对本发 明脱模剂带来不利影响的各类乳化助剂， 其用于增加聚合物的亲水性、 脱模剂的稠度和稳定性等。 所述的乳化助剂的含量较佳的为小于或等于 脱模剂总质量的 8%， 更佳的为小于或等于 5%。 所述的乳化助剂为亲水 性助剂、 增稠剂、 稳定剂和 ρΗ调节剂等中的一种或多种。  In the present invention, the emulsification aid may be various types of emulsification aids which are conventionally used in the art and which do not significantly adversely affect the release agent of the present invention, and are used for increasing the hydrophilicity of the polymer and the release agent. Consistency and stability, etc. The content of the emulsification aid is preferably less than or equal to 8% of the total mass of the release agent, more preferably less than or equal to 5%. The emulsifying aid is one or more of a hydrophilic auxiliary agent, a thickener, a stabilizer, and a pH adjusting agent.
其中， 所述的亲水性助剂优选水溶性高分子化合物， 较佳的为聚乙 烯基吡咯垸酮、 聚乙二醇、 聚乙烯醇和聚乙烯基甲基醚中的一种或多种。  Among them, the hydrophilic auxiliary agent is preferably a water-soluble polymer compound, preferably one or more of polyvinylpyrrolidone, polyethylene glycol, polyvinyl alcohol and polyvinyl methyl ether.
其中， 所述的增稠剂为本领域常规使用的增稠剂， 较佳的为水性增 稠剂， 更佳的为羟烃基纤维素、 纤维素醚和聚丙烯酸酯乳液类增稠剂等 中的一种或多种。  Wherein, the thickener is a thickener conventionally used in the art, preferably an aqueous thickener, more preferably a hydroxyalkyl cellulose, a cellulose ether and a polyacrylate emulsion thickener. One or more.
其中， 所述的稳定剂包括热稳定剂或冻融稳定剂。  Wherein, the stabilizer comprises a heat stabilizer or a freeze-thaw stabilizer.
其中， 所述的 ρΗ调节剂为本领域常规使用的 ρΗ调节剂， 较佳的为 分子量小于或等于 10000的酸、 碱和盐中的一种或多种； 更佳的为乙酸、 氨水、 碳酸铵、 碳酸钠和氯化铵中的一种或多种。  Wherein, the pH modifier is a ruthenium modifier conventionally used in the art, preferably one or more of an acid, a base and a salt having a molecular weight of less than or equal to 10,000; more preferably acetic acid, ammonia water, carbonic acid One or more of ammonium, sodium carbonate, and ammonium chloride.
本发明中， 所述的催化剂为能促进硅氢基团之间， 硅氢基团与硅氧 烷基团， 以及硅氢基团与硅羟基基团发生反应的催化剂， 包括胺类催化 剂和 /或有机金属类催化剂。 In the present invention, the catalyst is capable of promoting between silicon hydrogen groups, silicon hydrogen groups and silicon oxygen The alkyl group, and the catalyst for reacting the silicon hydride group with the silanol group, include an amine catalyst and/or an organometallic catalyst.
所述的胺类催化剂较佳地选自下列中的一种或多种： 三亚乙基二胺、 双 （二甲氨基乙基醚）、 二甲基环己胺、 N-甲基二环己胺、 五甲基二亚乙 基三胺、 五甲基二亚丙基三胺、 四甲基乙二胺、 四甲基丙二胺、 四甲基 己二胺、 N-甲基吗啉、 N-乙基吗啉、 2， 2-双吗啉基二乙基醚、 可可吗啉、 N-甲基咪唑、 1， 2-二甲基咪唑、 1， 4-二甲基哌嗪、 N， N-二甲基苄胺、 三 （二甲氨丙基） 胺、 三乙胺、 Ν,Ν-二甲基 （十六垸基） 胺和四甲基亚 胺基二丙基胺。  The amine catalyst is preferably selected from one or more of the following: triethylenediamine, bis(dimethylaminoethyl ether), dimethylcyclohexylamine, N-methyldicyclohexyl Amine, pentamethyldiethylenetriamine, pentamethyldipropylenetriamine, tetramethylethylenediamine, tetramethylpropanediamine, tetramethylhexamethylenediamine, N-methylmorpholine, N-ethylmorpholine, 2,2-bismorpholinyl diethyl ether, cocomorpholine, N-methylimidazole, 1,2-dimethylimidazole, 1,4-dimethylpiperazine, N , N-dimethylbenzylamine, tris(dimethylaminopropyl)amine, triethylamine, hydrazine, hydrazine-dimethyl(hexadecanoyl)amine and tetramethyliminodipropylamine.
所述的有机金属类催化剂较佳地选自下列中的一种或多种： 二月桂 酸二丁基锡、 辛酸亚锡、 二 （十二烷基硫） 二丁基锡、 二醋酸二丁基锡、 异辛酸钾、 醋酸钾、 油酸钾、 异辛酸铅、 异辛酸锌、 醋酸苯汞、 钛酸四 丁酯和钛酸四异丙酯。 所述的催化剂的含量较佳的为脱模剂总质量的 0.1 - 10.0%, 更佳的为 0.1-8.0%。  The organometallic catalyst is preferably selected from one or more of the following: dibutyltin dilaurate, stannous octoate, di(dodecylsulfide) dibutyltin, dibutyltin diacetate, potassium isooctylate , potassium acetate, potassium oleate, lead isooctanoate, zinc isooctanoate, phenylmercuric acetate, tetrabutyl titanate and tetraisopropyl titanate. The content of the catalyst is preferably from 0.1 to 10.0%, more preferably from 0.1 to 8.0%, based on the total mass of the release agent.
本发明的脱模剂的 ρΗ值优选为 3-7， 更优选 4-7。  The release agent of the present invention preferably has a pH of from 3 to 7, more preferably from 4 to 7.
本发明的脱模剂的固含量可通过加水进行调节。 脱模剂的固含量较 佳的为 0.1-80.0%， 更佳的为 1-75%。 当脱模剂中含有增稠剂时， 固含量较 佳的为卜 40%; 在不含增稠剂时， 固含量较佳的为 40-75%。 在本发明一较 佳的实施例中， 当脱模剂中含有增稠剂时固含量为 2-40%; 当不含增稠剂 时固含量为 40-75%。 该较佳实施例的脱模剂具有较长的保存时间， 可在 室温下稳定放置一个月以上。 所述的百分比为质量百分比。  The solid content of the release agent of the present invention can be adjusted by adding water. The mold release agent preferably has a solid content of from 0.1 to 80.0%, more preferably from 1 to 75%. When the releasing agent contains a thickener, the solid content is preferably 40%; in the absence of the thickener, the solid content is preferably 40-75%. In a preferred embodiment of the invention, the solids content is from 2 to 40% when the release agent is contained in the release agent; and the solid content is from 40 to 75% when the thickener is not contained. The release agent of this preferred embodiment has a long shelf life and can be stably placed at room temperature for more than one month. The percentage stated is the mass percentage.
根据需要， 本发明的脱模剂可以为所有成分一起混合的一组分形式， 也可为将各成分分成若干组分别混合的多组分形式。 当脱模剂中含有催 化剂时， 本发明的脱模剂较佳地含有 2 个组分， 其中催化剂与具有三个 以上硅氢键的聚硅氧垸化合物不共存于同一组分中。  The release agent of the present invention may be in the form of one component in which all the components are mixed together, or may be in a multicomponent form in which the components are separately mixed in several groups, as needed. When the releasing agent contains a catalyst, the releasing agent of the present invention preferably contains two components in which the catalyst does not coexist in the same component with the polysiloxane compound having three or more silicon hydrogen bonds.
本发明一较佳实例中， 该脱模剂含有混合物 Α和混合物 Β， 其中混 合物 A 中含有具有三个以上硅氢键的聚硅氧烷化合物、 乳化剂和水； 混 合物 B中含有催化剂和水； 亚光粒子独立的存在于混合物 A和 /或混合物 B 中。 在本发明一更佳实施例中， 所述的混合物 A 中还含有有机硅化合 物和 /或乳化助剂； 混合物 B中还含有乳化剂和 /或乳化助剂。 In a preferred embodiment of the present invention, the release agent contains a mixture of hydrazine and a mixture, wherein the release agent The compound A contains a polysiloxane compound having three or more silicon hydrogen bonds, an emulsifier and water; the mixture B contains a catalyst and water; and the matte particles are independently present in the mixture A and/or the mixture B. In a further preferred embodiment of the invention, the mixture A further contains an organosilicon compound and/or an emulsification aid; the mixture B further contains an emulsifier and/or an emulsification aid.
本发明中， 术语 "聚硅氧烷" 是指主链由重复单元硅-氧 (Si— O)键构 成， 其中硅原子上直接连结有机基团的聚合物。  In the present invention, the term "polysiloxane" means a polymer in which a main chain is composed of a repeating unit silicon-oxygen (Si-O) bond in which an organic group is directly bonded to a silicon atom.
本发明中， 术语 "亚光粒子" 是指赋予制品亚光效果的固体颗粒。 本发明中， 术语 "亚光"是指成型后的橡胶制品光泽度小于 5.0° (包括 5.0°， 入射角为 60°)。  In the present invention, the term "matte particles" means solid particles which impart a matt effect to an article. In the present invention, the term "matt" means that the molded rubber article has a gloss of less than 5.0 (including 5.0 and an incident angle of 60).
本发明中， 术语 "半永久型脱模" 是指喷涂一次脱模剂， 可实现 5 次以上的脱模， 且每一模成型的制品光泽度恒定。  In the present invention, the term "semi-permanent demolding" means that the release agent is sprayed once, and the release of the mold can be achieved more than five times, and the gloss of each molded product is constant.
本发明中， 术语 "每一模成型的制品光泽度恒定" 是指成型后的制 品光泽度的误差为 ± 0.1°。  In the present invention, the term "constant gloss of each molded article" means that the gloss of the molded article after molding is ± 0.1 °.
本发明的脱模剂的制备方法可参照现有技术中常规的制备脱模剂的 方法进行， 较佳地根据专利 CN 101230138A的方法进行制备。  The preparation method of the release agent of the present invention can be carried out by referring to a conventional method for preparing a release agent in the prior art, preferably according to the method of the patent CN 101230138A.
本发明还提供了所述的脱模剂在制备亚光型橡胶制品、 亚光型塑料 制品或亚光型复合材料制品中的应用。  The present invention also provides the use of the release agent described in the preparation of a matt rubber article, a matt plastic article or a matt composite article.
本发明的各优选条件可任意组合， 即得本发明的各优选实施例。 本发明的积极进步效果在于：  The preferred conditions of the invention may be combined arbitrarily to obtain preferred embodiments of the invention. The positive effects of the present invention are:
1、 本发明的脱模剂施工简单， 脱模性和亚光效果俱佳， 固化时可形 成较硬的膜， 从而将亚光粒子固定在膜上， 而不被转移到成型制品上， 由此实现半永久型脱模， 且多次脱模后所得制品光泽度能保持基本恒定， 光 泽度的误差为 ± 0. 1 °， 不影响制品性能。  1. The release agent of the invention has simple construction, good release property and matt effect, and forms a hard film when solidified, thereby fixing the matt particles on the film without being transferred to the molded article, This achieves semi-permanent demolding, and the gloss of the obtained product can be kept substantially constant after multiple demolding, and the gloss error is ±0.1°, which does not affect the product performance.
2、 本发明的脱模剂稳定性好， 室温下可存储 1周以上; 当脱模剂中 具有三个以上硅氢键的聚硅氧垸化合物与催化剂不共存于同一混合物中 时， 本发明的脱模剂可存储一个月以上， 甚至达到 3个月以上。  2. The release agent of the present invention has good stability and can be stored for more than one week at room temperature; when the polysiloxane compound having three or more silicon hydrogen bonds in the release agent does not coexist in the same mixture, the present invention The release agent can be stored for more than one month, even for more than three months.
3、 本发明的脱模剂能在不同温度下固化， 因此既能适用于高固化温 度的制品也能用于低固化温度的制品。 3. The release agent of the invention can be cured at different temperatures, so it can be applied to high curing temperature. Articles of the product can also be used for articles with low curing temperatures.
4、本发明的脱模剂能用于几乎所有现有的模具。尤其对于金属模具， 脱模剂中的硅氢键可与金属模具表面上的羟基形成化学交联和物理交 联， 使得本发明的脱模剂与金属模具具有更好的粘结性。  4. The release agent of the present invention can be used in almost all existing molds. Especially for metal molds, the silicon hydrogen bonds in the release agent can form chemical crosslinks and physical crosslinks with the hydroxyl groups on the surface of the metal mold, so that the release agent of the present invention has better adhesion to the metal mold.
具体实施方式 detailed description
下面用实施例来进一步说明本发明， 但本发明并不受其限制。  The invention is further illustrated by the following examples, but the invention is not limited thereto.
除非另有指明， 以下各实施例中制备脱模剂的各步骤都在常压下进 行， 温度为常温。  Unless otherwise specified, the steps of preparing the release agent in the following examples were carried out under normal pressure at a normal temperature.
本发明制得的脱模剂的性能表征如下：  The performance of the release agent prepared by the present invention is characterized as follows:
聚合物粘度由中国申德技术发展有限公司的 NDJ- 1A 的旋转粘度仪 在 25 °C±1 °C测定。  The viscosity of the polymer was measured by a rotary viscometer of NDJ-1A from China Shende Technology Development Co., Ltd. at 25 °C ± 1 °C.
聚合物分子量及其分布由美国 Waters公司的 Waters Breeze 1515高效 凝胶渗透色谱仪测定。  The molecular weight of the polymer and its distribution were determined by Waters Breeze 1515 High Performance Gel Permeation Chromatography from Waters, USA.
乳液的固含量采用梅特勒-托利多 HB43-S 卤素水分测定仪在 125 °C 交联后膜的表面能由德国 Dataphysics公司的 OCA-15测定。  The solid content of the emulsion was measured by Mettler-Toledo HB43-S Halogen Moisture Analyzer at 125 °C after cross-linking. The surface energy of the film was determined by OCA-15 of Dataphysics, Germany.
橡胶制品的光泽度由 Rhopoint Instumentation 公司的 NOVO-GLOSS The gloss of rubber products by NOVO-GLOSS of Rhopoint Instumentation
60°统计型光泽仪测得。 Measured by a 60° statistical gloss meter.
实施例中使用的具有三个以上硅氢键的聚硅氧垸化合物的详细信息 为：  The details of the polysiloxane compound having three or more silicon hydrogen bonds used in the examples are:
甲基含氢硅油 Syl-off® 7048: 美国道康宁公司， 含氢量 1.58- 1.60%， 粘度为 30cst;  Methylhydrogenated silicone oil Syl-off® 7048: Dow Corning, USA, containing 1.58- 1.60% hydrogen, 30cst viscosity;
甲基含氢硅油 Syl-Off®7672 : 美国道康宁公司， 含氢量 0.90%， 粘度 为 70cst;  Methyl-containing silicone oil Syl-Off®7672: Dow Corning, USA, containing 0.90% hydrogen and 70cst viscosity;
甲基含氢硅油 Syl-Off®7678: 美国道康宁公司， 含氢量 1.05%， 粘度 为 29cst; Methyl-containing silicone oil Syl-Off®7678 : Dow Corning, USA, containing 1.05% hydrogen, viscosity 29cst;
甲基含氢硅油 Dowcorning®1107 : 美国道康宁公司， 含氢量 1.60%， 粘度为 30cst; Methyl Hydrogenated Silicone Oil Dow Corning® 1107: Dow Corning, USA, containing 1.60% hydrogen, Viscosity is 30cst;
甲基含氢硅油 ORG202 :上海朗裕实业有限公司，含氢量 1.58-1.63%， 粘度为 15-40cst;  Methyl hydrogenated silicone oil ORG202: Shanghai Langyu Industrial Co., Ltd., containing 1.58-1.63% hydrogen, viscosity 15-40cst;
实施例中使用的亚光粒子的详细信息为：  The details of the matt particles used in the examples are:
SYOID® C803 , 美国格雷斯 （Grace ) 公司， 粒径 3.0-4.0μιη;  SYOID® C803, Grace, USA, particle size 3.0-4.0μιη;
SYOID® C805 , 美国格雷斯 （Grace ) 公司， 粒径 4.6-5.4μΐΏ ;  SYOID® C805, Grace, USA, particle size 4.6-5.4μΐΏ;
SYOID® ED2， 美国格雷斯 ( Grace ) 公司， 粒径 3.0-4.0μΐΏ ;  SYOID® ED2, Grace, USA, particle size 3.0-4.0μΐΏ;
SYOID®Sy7000， 美国格雷斯 （Grace ) 公司， 粒径 4.6-5.4μιη;  SYOID®Sy7000, Grace, USA, particle size 4.6-5.4μιη;
SYOID® C305 , 美国格雷斯 ( Grace ) 公司， 粒径 4.6-5.4μιη;  SYOID® C305, Grace, USA, particle size 4.6-5.4μιη;
CAB-0-SIL®H-5， 美国卡博特 （Cabot) 公司， 粒径 0.2-0.3μηι; ACEMATT®HK125， 德国 Degussa公司， 粒径 10.5μιη。 实施例中使用有机硅化合物的详细信息为：  CAB-0-SIL®H-5, Cabot, USA, particle size 0.2-0.3μηι; ACEMATT®HK125, Germany Degussa, particle size 10.5μιη. The details of the organosilicon compounds used in the examples are:
羟基封端的聚二甲基硅氧烷 Dowcorning®l-3563 Fluid: 美国道康宁 公司， 粘度 55-90cst;  Hydroxyl terminated polydimethylsiloxane Dowcorning® l-3563 Fluid: Dow Corning, USA, viscosity 55-90cst;
羟基封端的聚二甲基硅氧烷 Dowcorning®4-2737: 美国道康宁公司， 粘度 42cst; Hydroxy-terminated polydimethylsiloxane Dow Corning® 4-2737 : Dow Corning, USA, viscosity 42 cst;
乙烯基二甲氧基封端的聚二甲基硅氧垸： 德国汉高公司， 粘度 （参 见专利 US5300608 )。 实施例中使用增稠剂的详细信息为：  Vinyl dimethoxy-terminated polydimethylsiloxane: German Henkel, viscosity (see US 5300608). The details of the use of thickeners in the examples are:
VISC ALEX® AT88 : 瑞士汽巴公司。 实施例 1  VISC ALEX® AT88: Swiss Ciba. Example 1
室温下， 将表 1 中的各成分加入高速分散釜中， 以 1500rpm的转速 搅拌 20分钟， 使其混合均匀。 再在 1500rpm转速下， 于 30分钟内匀速 滴加 31.6克去离子水； 滴完后， 于 200rpm转速下继续搅拌 30分钟， 即 得。 该脱模剂固含量为 50%， 室温储存 1个月， 使用时可加水稀释。 将 实施例 1制备的脱模剂喷涂在金属模具上， 可在 160Ό下 10分钟固化成 膜， 利用此脱模剂脱模三元乙丙橡胶， 可得到光泽度为 0.7。的橡胶制品， 一次喷涂可脱模 20次以上， 且每一模的橡胶光泽度恒定。 脱模热塑性聚 氨酯材料， 可得到光泽度为 2.7°的制品； 脱模聚苯并噁嗪材料， 可得到光 泽度为 2.3°的制品， 一次喷涂可脱模 5次以上， 且每一模的制品光泽度 恒定。 The components in Table 1 were placed in a high-speed dispersion vessel at room temperature, and stirred at 1,500 rpm for 20 minutes to make them uniformly mixed. Then, at a speed of 1500 rpm, 31.6 g of deionized water was added dropwise at a constant rate over 30 minutes; after the completion of the dropwise addition, stirring was continued at 200 rpm for 30 minutes. The release agent has a solid content of 50%, is stored at room temperature for 1 month, and can be diluted with water when used. The release agent prepared in Example 1 was sprayed on a metal mold and cured at 160 Torr for 10 minutes. The film, by using this release agent to release the EPDM rubber, gives a gloss of 0.7. The rubber product can be demolded more than 20 times in one spray, and the rubber gloss of each mold is constant. The release thermoplastic polyurethane material can obtain a product with a gloss of 2.7°; the release polybenzoxazine material can obtain a product with a gloss of 2.3°, and can be demolded more than 5 times in one spray, and each molded product The gloss is constant.
表 1 Table 1
Figure imgf000014_0001
实施例 2
Figure imgf000014_0001
Example 2
室温下， 将表 2 中的各成分加入高速分散釜中， 以 1500rpm的转速 搅拌 20分钟， 使其混合均匀。 再在 1500rpm转速下， 于 30分钟内匀速 滴加 3 1.6克去离子水； 滴完后， 于 200rpm转速下继续搅拌 30分钟， 即 得。 该脱模剂固含量为 55%， 室温储存 2个月， 使用时可加水稀释。 将 实施例 2制备的脱模剂喷涂在金属模具上， 可在 160°C下 10分钟固化成 膜， 利用此脱模剂脱模三元乙丙橡胶， 可得到光泽度为 1 .0°的橡胶制品， 一次喷涂可脱模 20次以上， 且每一模的橡胶光泽度恒定。  The components in Table 2 were placed in a high-speed dispersion vessel at room temperature, and stirred at 1,500 rpm for 20 minutes to uniformly mix. Then, at a speed of 1500 rpm, 3 1.6 g of deionized water was added dropwise at a constant rate over 30 minutes; after the completion of the dropwise addition, stirring was continued at 200 rpm for 30 minutes. The release agent has a solid content of 55%, is stored at room temperature for 2 months, and can be diluted with water when used. The release agent prepared in Example 2 was sprayed on a metal mold, and the film was cured at 160 ° C for 10 minutes, and the release agent was used to release the EPDM rubber to obtain a gloss of 1.0 °. Rubber products can be demolded more than 20 times in one spray, and the rubber gloss of each mold is constant.
表 2 Table 2
Figure imgf000014_0002
实施例 3
Figure imgf000014_0002
Example 3
室温下， 将表 3中的各成分加入高速分散釜中， 以 1500rpm的转速 搅拌 20分钟， 使其混合均匀。 再在 1500rpm转速下， 于 30分钟内匀速 滴加 30.4克去离子水； 滴完后， 于 200rpm转速下继续搅拌 30分钟， 即 得。 该脱模剂固含量为 50%， 室温储存 1 个月， 使用时可加水稀释。 将 实施例 3制备的脱模剂喷涂在金属模具上， 可在 160°C下 10分钟固化成 膜， 利用此脱模剂脱模三元乙丙橡胶， 可得到光泽度为 2.7。的橡胶制品， 一次喷涂可脱模 20次以上， 且每一模的橡胶光泽度恒定。 The components in Table 3 were placed in a high-speed dispersion vessel at room temperature, and stirred at 1,500 rpm for 20 minutes to uniformly mix. Then, at 1500 rpm, 30.4 g of deionized water was added dropwise at a constant rate over 30 minutes; after the completion of the dropwise addition, stirring was continued at 200 rpm for 30 minutes. The release agent has a solid content of 50%, is stored at room temperature for 1 month, and can be diluted with water when used. The release agent prepared in Example 3 was sprayed on a metal mold to form a film at 160 ° C for 10 minutes, and the release agent was used to release the EPDM rubber to obtain a gloss of 2.7. The rubber product can be demolded more than 20 times in one spray, and the rubber gloss of each mold is constant.
Figure imgf000015_0001
Figure imgf000015_0001
Figure imgf000015_0002
实施例 4
Figure imgf000015_0002
Example 4
室温下， 将表 4中的各成分加入高速分散釜中， 以 1 500rpm的转速 搅拌 20分钟， 使其混合均匀。 再在 1500rpm转速下， 于 30分钟内匀速 滴加 31 .6克去离子水； 滴完后， 于 200rpm转速下继续搅拌 30分钟， 即 得。 该脱模剂固含量为 48%， 室温储存 2个月， 使用时可加水稀释。 将 实施例 4制备的脱模剂喷涂在金属模具上， 可在 160°C下 10分钟固化成 膜， 利用此脱模剂脱模三元乙丙橡胶， 可得到光泽度为 2.0°的橡胶制品， 一次喷涂可脱模 20次以上， 且每一模的橡胶光泽度恒定。  The components in Table 4 were placed in a high-speed dispersion vessel at room temperature, and stirred at 1,500 rpm for 20 minutes to uniformly mix. Then, at 1500 rpm, 31.6 g of deionized water was added dropwise at a constant rate over 30 minutes; after the completion of the dropwise addition, stirring was continued at 200 rpm for 30 minutes. The release agent has a solid content of 48%, is stored at room temperature for 2 months, and can be diluted with water when used. The release agent prepared in Example 4 was sprayed on a metal mold, and the film was cured at 160 ° C for 10 minutes to form a film. Using the release agent to release the EPDM rubber, a rubber product having a gloss of 2.0° was obtained. , can be demolded more than 20 times in one spray, and the rubber gloss of each mold is constant.
表 4  Table 4
实施 具有硅氢键的聚 亚光粒子  Implementing poly Matte particles with silicon hydrogen bonds
乳化剂 ( g )  Emulsifier ( g )
例 硅氧垸 （g ) ( g )  Example siloxane (g) ( g )
月桂醇聚 月桂醇聚 聚山梨醇  Lauryl alcohol polylauric alcohol poly polysorbitol
4 Dowcorning®! 107 SYOID® C803 氧化乙烯 氧化乙烯 酯 -85  4 Dowcorning®! 107 SYOID® C803 Ethylene Oxide Ethylene Oxide Ester -85
醚 -4 醚 -23 30.0 4.0 3.0 9.0 5.4 实施例 5 Ether-4 ether-23 30.0 4.0 3.0 9.0 5.4 Example 5
室温下， 将表 5中的各成分加入高速分散釜中， 以 1500rpm的转速 搅拌 20分钟， 使其混合均匀。 再在 1500rpm转速下， 于 30分钟内匀速 滴加 31.6克去离子水； 滴完后， 于 200rpm转速下继续搅拌 30分钟， 即 得。 该脱模剂固含量为 59%， 室温储存 2个月， 使用时可加水稀释。 将 实施例 5制备的脱模剂喷涂在金属模具上， 可在 160Ό下 10分钟固化成 膜， 利用此脱模剂脱模三元乙丙橡胶， 可得到光泽度为 0.9。的橡胶制品， 一次喷涂可脱模 20次以上， 且每一模的橡胶光泽度恒定。 The components in Table 5 were placed in a high-speed dispersion vessel at room temperature, and stirred at 1,500 rpm for 20 minutes to uniformly mix. Then, at a speed of 1500 rpm, 31.6 g of deionized water was added dropwise at a constant rate over 30 minutes; after the completion of the dropwise addition, stirring was continued at 200 rpm for 30 minutes. The release agent has a solid content of 59%, is stored at room temperature for 2 months, and can be diluted with water when used. The release agent prepared in Example 5 was sprayed on a metal mold to form a film at 160 Torr for 10 minutes, and the release agent was used to release the EPDM rubber to obtain a gloss of 0.9. The rubber product can be demolded more than 20 times in one spray, and the rubber gloss of each mold is constant.
Figure imgf000016_0001
Figure imgf000016_0001
Figure imgf000016_0002
实施例 6
Figure imgf000016_0002
Example 6
室温下， 将表 6中的各成分加入高速分散釜中， 以 1500rpm的转速 搅拌 20分钟， 使其混合均匀。 再在 1500rpm转速下， 于 30分钟内匀速 滴加 31.6克去离子水； 滴完后， 于 200rpm转速下继续搅拌 30分钟， 即 得。 该脱模剂固含量为 62%， 室温储存 2个月， 使用时可加水稀释。 将 实施例 6制备的脱模剂喷涂在金属模具上， 可在 160°C下 10分钟固化成 膜， 利用此脱模剂脱模三元乙丙橡胶， 可得到光泽度为 0.9°的橡胶制品， 一次喷涂可脱模 20次以上， 且每一模的橡胶光泽度恒定。  The components in Table 6 were placed in a high-speed dispersion vessel at room temperature, and stirred at 1,500 rpm for 20 minutes to uniformly mix. Then, at a speed of 1500 rpm, 31.6 g of deionized water was added dropwise at a constant rate over 30 minutes; after the completion of the dropwise addition, stirring was continued at 200 rpm for 30 minutes. The release agent has a solid content of 62%, is stored at room temperature for 2 months, and can be diluted with water when used. The release agent prepared in Example 6 was sprayed on a metal mold, and the film was cured at 160 ° C for 10 minutes to form a film. Using the release agent to release the EPDM rubber, a rubber product having a gloss of 0.9° was obtained. , can be demolded more than 20 times in one spray, and the rubber gloss of each mold is constant.
表 6  Table 6
具有硅氢  Hydrogenated silicon
实施 亚光粒子 有机硅化合物 键的聚硅 乳化剂 ( g )  Implementation of matt particles Silicone compound bond polysilicon emulsifier ( g )
例 ( g ) ( g)  Example ( g ) ( g)
氧垸 ( g ) 月桂醇 Oxygen oxime ( g ) Lauryl alcohol
月桂醇聚  Lauryl alcohol
SYOID Cabot 聚山梨 Dowcorning® SYOID Cabot Poly Pear Dowcorning®
ORG202 氧化乙烯 ORG202 ethylene oxide
®C803 ®H-5 醇酯 -85 4-2737 ®C803 ® H-5 Alcohol Ester -85 4-2737
6 乙烯醚 6 vinyl ether
醚 -23  Ether -23
-4  -4
30.0 3.0 1 .2 3.0 9.0 5.4 15.0  30.0 3.0 1 .2 3.0 9.0 5.4 15.0
实施例 7 . Example 7 .
室温下， 将表 7 中的各成分加入高速分散釜中， 以 1500rpm 的转速 搅拌 20分钟， 使其混合均匀。 再在 1500rpm转速下， 于 30分钟内匀速 滴加 3 1 .6克去离子水； 滴完后， 于 200rpm转速下继续搅拌 30分钟， 即 得。 该脱模剂固含量为 64%， 室温储存 2个月， 使用时可加水稀释。 将 实施例 7制备的脱模剂喷涂在金属模具上， 可在 160Ό下 10分钟固化成 膜。 该膜有较低的表面能。 利用此脱模剂脱模三元乙丙橡胶， 可得到光 泽度为 5。的橡胶制品， 一次喷涂可脱模 20次以上， 且每一模的橡胶光泽 度恒定。  The components in Table 7 were placed in a high-speed dispersion vessel at room temperature, and stirred at 1,500 rpm for 20 minutes to uniformly mix. Then, at a speed of 1500 rpm, 31.6 g of deionized water was added dropwise at a constant rate over 30 minutes; after the completion of the dropwise addition, stirring was continued at 200 rpm for 30 minutes. The release agent has a solid content of 64%, is stored at room temperature for 2 months, and can be diluted with water when used. The release agent prepared in Example 7 was sprayed on a metal mold and cured to form a film at 160 Torr for 10 minutes. The film has a lower surface energy. By using this release agent to release the EPDM rubber, a gloss of 5 can be obtained. The rubber product can be demolded more than 20 times in one spray, and the rubber gloss of each mold is constant.
表 7  Table 7
Figure imgf000017_0001
实施例 8
Figure imgf000017_0001
Example 8
室温下， 将表 8中的各成分加入高速分散釜中， 以 1500rpm的转速 搅拌 20分钟， 使其混合均匀。 再在 1500rpm转速下， 于 30分钟内匀速 滴加 3 1.6克去离子水； 滴完后， 于 200rpm转速下继续搅拌 30分钟， 即 得。 该脱模剂固含量为 63%， 室温储存 2个月， 使用时可加水稀释。 将 实施例 8制备的脱模剂喷涂在金属模具上， 可在 160°C下 10分钟固化成 膜， 利用此脱模剂脱模三元乙丙橡胶， 可得到光泽度为 1.8°的橡胶制品， 一次喷涂可脱模 20次以上， 且每一模的橡胶光泽度恒定。 The components in Table 8 were placed in a high-speed dispersion vessel at room temperature, and stirred at 1,500 rpm for 20 minutes to uniformly mix. Then, at a speed of 1500 rpm, 3 1.6 g of deionized water was added dropwise at a constant rate over 30 minutes; after the completion of the dropwise addition, stirring was continued at 200 rpm for 30 minutes. The release agent has a solid content of 63%, is stored at room temperature for 2 months, and can be diluted with water when used. The release agent prepared in Example 8 was sprayed on a metal mold and cured at 160 ° C for 10 minutes. Membrane, by using this release agent to release EPDM rubber, a rubber product having a gloss of 1.8° can be obtained, and the spray can be released more than 20 times in one spray, and the rubber gloss of each mold is constant.
表 8  Table 8
Figure imgf000018_0001
实施例 9
Figure imgf000018_0001
Example 9
室温下， 将表 9中的各成分加入高速分散釜中， 以 1500rpm的转速 搅拌 20分钟， 使其混合均匀。 再在 1500rpm转速下， 于 30分钟内匀速 滴加 93.0克去离子水； 滴完后， 于 200rpm转速下继续搅拌 30分钟， 即 得。 该脱模剂固含量为 5.8%， 室温储存 3个月， 使用时可加水稀释。 将 实施例 9制备的脱模剂喷涂在金属模具上， 可在 160Ό下 10分钟固化成 膜，利用此脱模剂脱模三元乙丙橡胶， 可得到光泽度为 0.7°的亚光橡胶制 品， 一次喷涂可脱模 20次以上， 且每一模的橡胶光泽度恒定。  The components in Table 9 were placed in a high-speed dispersion vessel at room temperature, and stirred at 1,500 rpm for 20 minutes to uniformly mix. Then, at 1500 rpm, 93.0 g of deionized water was added dropwise at a constant rate over 30 minutes; after the completion of the dropwise addition, stirring was continued at 200 rpm for 30 minutes. The release agent has a solid content of 5.8%, is stored at room temperature for 3 months, and can be diluted with water when used. The release agent prepared in Example 9 was sprayed on a metal mold, and the film was cured at 160 Torr for 10 minutes to form a film, and the release agent was used to release the EPDM rubber to obtain a matt rubber product having a gloss of 0.7°. , can be demolded more than 20 times in one spray, and the rubber gloss of each mold is constant.
表 9  Table 9
Figure imgf000018_0002
实施例 10
Figure imgf000018_0002
Example 10
制备混合物 A:  Preparation of the mixture A:
在高速分散釜中， 加入 3.0克甲基含氢硅油、 0.3克聚山梨醇酯 -85、 0.9 克月桂醇聚醚 -4、 0.54 克月桂醇聚醚 -23， 室温下 1500rpm 转速搅拌 20分钟混合均匀。 在 1500rpm转速下， 30分钟内匀速滴加 95.86克水； 滴完后， 200rpm转速下继续搅拌 30分钟， 即可得到混合物八。 In a high-speed dispersion kettle, 3.0 g of methyl hydrogen silicone oil, 0.3 g of polysorbate-85, 0.9 g of laureth-4, 0.54 g of laureth-23, and mix well at room temperature for 1500 rpm for 20 minutes. At 1500 rpm, 95.86 g of water was added dropwise at a constant rate over 30 minutes; after the completion of the dropwise addition, stirring was continued for 30 minutes at 200 rpm to obtain a mixture of eight.
制备混合物 B:  Preparation of mixture B:
在高速分散釜中， 加入 0.6克二氧化硅、 0.1克辛酸亚锡、 0.5克增稠 剂 （VISCALEX®AT88 )。 在 1500rpm转速下， 10分钟内匀速滴加 98.9 克水； 滴完后， 200rpm转速下继续搅拌 10分钟， 即可得到混合物 B。  In a high-speed dispersion vessel, 0.6 g of silica, 0.1 g of stannous octoate, and 0.5 g of a thickener (VISCALEX® AT88) were added. At 1500 rpm, 98.9 g of water was added dropwise at a constant rate over 10 minutes; after the completion of the dropwise addition, stirring was continued for 10 minutes at 200 rpm to obtain a mixture B.
混合物 A和混合物 B按质量比 1 : 1的比例混合均匀， 然后喷涂在金 属模具上 60°C固化 30分钟成膜， 利用此脱模剂脱模 EPDM橡胶， 可得 到光泽度为 0.7°的亚光橡胶制品， 一次喷涂可脱模 20次以上， 且每一模 的橡胶光泽度恒定。  Mixture A and mixture B are uniformly mixed at a mass ratio of 1:1, and then sprayed on a metal mold at 60 ° C for 30 minutes to form a film, and the release agent is used to release EPDM rubber to obtain a gloss of 0.7 °. Light rubber products can be demolded more than 20 times in one spray, and the rubber gloss of each mold is constant.

Claims

权利要求 Rights request
1、 一种脱模剂， 其含有： 具有三个以上硅氢键的聚硅氧垸化合物、 亚光粒子、 乳化剂和水。 A mold release agent comprising: a polysiloxane compound having three or more silicon hydrogen bonds, a matting particle, an emulsifier, and water.
2、 如权利要求 1所述的脱模剂， 其特征在于： 所述的具有三个以上硅 氢键的聚硅氧烷化合物为具有三个以上硅氢键的下述聚合物中的一种或 多种： （1) 由如式 I所示的结构单元形成的均聚物； （2) 由如式 I和式 II 所示的结构单元形成的无规、 交替、 嵌段和接枝共聚物， 该共聚物为线 性或环状共聚物； 以及 （3) 由上述 （1) 和 （2) 的聚合物中的一种或多 种形成的交联共聚物；  The release agent according to claim 1, wherein the polysiloxane compound having three or more silicon hydrogen bonds is one of the following polymers having three or more silicon hydrogen bonds; Or a plurality of: (1) a homopolymer formed from a structural unit as shown in Formula I; (2) a random, alternating, block and graft copolymer formed from structural units as shown in Formula I and Formula II And the copolymer is a linear or cyclic copolymer; and (3) a crosslinked copolymer formed from one or more of the polymers of the above (1) and (2);
Figure imgf000020_0001
Figure imgf000020_0001
其中， R,为 -do的垸氧基或 -do的烃基， 较佳地为 -C6的垸 氧基或 -C6的烃基； R2和 13独立的为羟基、 - o的垸氧基或 -Co 的烃基， 较佳地独立的为羟基、 CrC6的垸氧基或 -C6的'烃基； 但 R2和 13不同时为羟基。 Wherein, R, is a hydrocarbyl group or embankment of -do -do, and preferably a group having 6 or -C embankment -C 6 hydrocarbon; R 2, and 1 3 is independently hydroxy, - o is oxygen embankment The hydrocarbon group of the group or -Co is preferably independently a hydroxyl group, a decyloxy group of C r C 6 or a 'hydrocarbyl group of -C6; however, R 2 and 13 are not simultaneously a hydroxyl group.
3、 如权利要求 1所述的脱模剂， 其特征在于： 所述的具有三个以上硅 氢键的聚硅氧烷化合物为线性或交联聚合物时， 其封端基为由氢、 羟基、 C,-C10的垸氧基和 do的烃基中的一种或多种取代的硅烷基。 3. The release agent according to claim 1, wherein: when the polysiloxane compound having three or more silicon hydrogen bonds is a linear or crosslinked polymer, the terminal group is hydrogen, One or more substituted silane groups of a hydroxyl group of a hydroxyl group, C, -C 10 and a hydrocarbon group of do.
4、 如权利要求 1所述的脱模剂， 其特征在于： 所述的具有三个以上硅 氢键的聚硅氧垸化合物的粘度为 5-10000cst;较佳的为 5-5000cst;粘度在 25°C下测得。 The mold release agent according to claim 1, wherein the polysiloxane composition having three or more silicon hydrogen bonds has a viscosity of from 5 to 10,000 cst ; preferably from 5 to 5,000 cSt; Measured at 25 ° C.
5、 如权利要求 1所述的脱模剂， 其特征在于： 所述的具有三个以上硅 氢键的聚硅氧垸化合物的硅氢键上的氢含量为 0.10-1.63%; 更佳的为 0.50-1.63%： 百分比为质量百分比。 The mold release agent according to claim 1, wherein the polysiloxane composition having three or more silicon-hydrogen bonds has a hydrogen content on a silicon hydrogen bond of 0.10-1.63%; more preferably 0.50-1.63%: The percentage is the mass percentage.
6、 如权利要求 1所述的脱模剂， 其特征在于： 所述的具有三个以上硅 氢键的聚硅氧烷化合物的含量为脱模剂总质量的 1 -65% ; 更佳的为 3-50%。 6. The release agent according to claim 1, wherein the content of the polysiloxane compound having three or more silicon hydrogen bonds is from 1 to 65% of the total mass of the release agent; more preferably It is 3-50%.
7、 如权利要求 1所述的脱模剂， 其特征在于： 所述的亚光粒子为无机 粒子和 /或有机粒子；亚光粒子的粒径为 0.2- 15.0μηι，更佳的为 0.5- 10.0μτη。  The release agent according to claim 1, wherein the matte particles are inorganic particles and/or organic particles; and the matte particles have a particle diameter of 0.2 to 15.0 μm, more preferably 0.5- 10.0μτη.
8、 如权利要求 1所述的脱模剂， 其特征在于： 所述的亚光粒子为二 氧化硅粒子、 金属氧化物粒子、 无机盐粒子和聚合物粒子中的一种或多 种； 所述的金属氧化物粒子较佳的为二氧化钛粒子、 氧化铝粒子、 氧化 锌粒子和氧化银粒子中的一种或多种； 所述的无机盐粒子较佳的为碳酸 钙粒子和 /或硫酸钡粒子； 所述的聚合物粒子较佳的为聚乙烯粒子、 聚氯 乙烯粒子、 聚丙烯粒子、 聚苯乙烯粒子和聚四氟乙烯粒子中的一种或多 种。  The mold release agent according to claim 1, wherein the matte particles are one or more of silica particles, metal oxide particles, inorganic salt particles, and polymer particles; The metal oxide particles are preferably one or more of titanium dioxide particles, aluminum oxide particles, zinc oxide particles, and silver oxide particles; and the inorganic salt particles are preferably calcium carbonate particles and/or barium sulfate. The polymer particles are preferably one or more of polyethylene particles, polyvinyl chloride particles, polypropylene particles, polystyrene particles, and polytetrafluoroethylene particles.
9、 如权利要求 1所述的脱模剂， 其特征在于： 所述的亚光粒子的含 量为脱模剂总质量的 0.1 -50.0%, 更佳的为 0.5-30.0%。  The release agent according to claim 1, wherein the matte particles are contained in an amount of from 0.1 to 50.0%, more preferably from 0.5 to 30.0%, based on the total mass of the release agent.
10、 如权利要求 1 所述的脱模剂， 其特征在于： 所述的乳化剂为非 离子表面活性剂。  The release agent according to claim 1, wherein the emulsifier is a nonionic surfactant.
1 1、 如权利要求 10所述的脱模剂， 其特征在于： 所述的非离子表面 活性剂的 HLB值为 3-50。  The release agent according to claim 10, wherein the nonionic surfactant has an HLB value of from 3 to 50.
12、 如权利要求 10所述的脱模剂， 其特征在于： 所述的非离子表面 活性剂为聚氧乙烯型非离子表面活性剂、 多元醇型非离子表面活性剂、 烷基醇酰胺型非离子表面活性剂和有机硅型非离子表面活性剂中的一种 或多种。  The mold release agent according to claim 10, wherein the nonionic surfactant is a polyoxyethylene type nonionic surfactant, a polyol type nonionic surfactant, or an alkyl alcohol amide type. One or more of a nonionic surfactant and a silicone type nonionic surfactant.
13、 如权利要求 1 所述的脱模剂， 其特征在于： 所述的乳化剂为下 列中的一种或多种： 聚氧化乙烯 （4 ) 壬基酚醚硫酸铵、 月桂醇聚氧化乙 烯 （2 ) 醚、 月桂醇聚氧化乙烯 （7 ) 醚、 月桂醇聚氧化乙烯 （12 ) 醚、 月桂醇聚氧化乙烯 （15 ) 醚、 月桂醇聚氧化乙烯 （23 ) 醚、 C9-C H烷基醇 聚氧化乙烯 （6 ) 醚、 C12-C14烷基醇聚氧化乙烯 （7 ) 醚、 Cl 2-C,5垸基醇 聚氧化乙烯 （12 ) 醚、 十三烷基醇聚氧化乙烯 （6 ) 醚、 十三烷基醇聚氧 化乙烯 （10) 醚、 十三垸基醇聚氧化乙烯 （15) 醚、 鲸蜡基醇聚氧化乙 烯 （15) 醚、 鲸蜡基醇聚氧化乙烯 （20) 醚、 鲸蜡基醇聚氧化乙烯 （30) 醚、 异鲸蜡基醇聚氧化乙烯 （20) 醚、 十六烷基醇聚氧化乙烯 （12) 醚、 十八垸基醇聚氧化乙烯 （12) 醚、 十六垸基醇聚氧化乙烯 （30) 醚、 十 八垸基醇聚氧化乙烯 （30) 醚、 硬脂基醇聚氧化乙烯 （20) 醚、 硬脂基 醇聚氧化乙烯 （40) 醚、 油醇聚氧化乙烯 （20) 醚、 壬基酚聚氧化乙烯 (9) 醚、 壬基酚聚氧化乙烯 （10) 醚、 壬基酚聚氧化乙烯 （12) 醚、 壬 基酚聚氧化乙烯 （30) 醚、 壬基酚聚氧化乙烯 （40) 醚、 壬基酚聚氧化 乙烯 （70) 醚、 壬基酚聚氧化乙烯 （5) 醚、 壬基酚聚氧化乙烯 （8) 醚、 壬基酚聚氧化乙烯 （100) 醚、 椰油胺聚氧化乙烯 （15) 醚、 乙二胺聚氧 化乙烯-聚氧化丙烯-聚氧化乙烯嵌段聚醚、 二月桂酸聚乙二醇 （8) 酉旨、 二月桂酸聚乙二醇 （20) 酯、 硬脂酸聚乙二醇 （40) 酯、 硬脂酸聚乙二 醇 （100) 酯、 聚氧化乙烯 (20) 甘油单硬脂酸酯、 聚氧化乙烯 (5)失水山梨 醇单油酸酯、 聚氧乙烯山梨醇酐三油酸酯和聚醚改性聚硅氧烷。 13. The release agent according to claim 1, wherein: the emulsifier is one or more of the following: polyoxyethylene (4) nonylphenol ether ammonium sulfate, lauryl alcohol polyoxyethylene (2) Ether, lauryl alcohol polyoxyethylene (7) ether, lauryl alcohol polyoxyethylene (12) ether, lauryl alcohol polyoxyethylene (15) ether, lauryl alcohol polyoxyethylene (23) ether, C 9 -CH alkane Alcohol polyoxyethylene (6) ether, C 12 -C 14 alkyl alcohol polyoxyethylene (7 ) ether, C 2 -C, 5 mercapto alcohol polyoxyethylene (12 ) ether, tridecyl alcohol Ethylene oxide (6) ether, tridecyl alcohol polyoxygen Ethylene (10) ether, tridecyl alcohol polyoxyethylene (15) ether, cetyl alcohol polyoxyethylene (15) ether, cetyl alcohol polyoxyethylene (20) ether, cetyl alcohol polyoxidation Ethylene (30) ether, iso cetyl alcohol polyoxyethylene (20) ether, cetyl alcohol polyoxyethylene (12) ether, octadecyl alcohol polyoxyethylene (12) ether, hexadecanol Polyethylene oxide (30) ether, octadecyl alcohol polyoxyethylene (30) ether, stearyl alcohol polyoxyethylene (20) ether, stearyl alcohol polyoxyethylene (40) ether, oleyl alcohol polyoxyethylene (20) Ether, nonylphenol polyoxyethylene (9) ether, nonylphenol polyoxyethylene (10) ether, nonylphenol polyoxyethylene (12) ether, nonylphenol polyoxyethylene (30) ether, hydrazine Polyphenol (40) ether, nonylphenol polyoxyethylene (70) ether, nonylphenol polyoxyethylene (5) ether, nonylphenol polyoxyethylene (8) ether, nonylphenol polyethylene oxide ( 100) Ether, cocamine polyoxyethylene (15) ether, ethylenediamine polyoxyethylene-polyoxypropylene-polyoxyethylene block polyether, polyethylene glycol dilaurate (8) 酉, PEG (20) ester of lauric acid, polyethylene glycol (40) ester of stearic acid, polyethylene glycol (100) ester of stearic acid, polyoxyethylene (20) glycerol Stearate, polyethylene oxide (5) sorbitan monooleate, polyoxyethylene sorbitan trioleate and polyether modified polysiloxane.
14、 如权利要求 1 所述的脱模剂， 其特征在于： 所述的乳化剂的含 量为脱模剂总质量的 0.2-25.0%, 更佳的为 0.25-20.00%。  The release agent according to claim 1, wherein the emulsifier is contained in an amount of from 0.2 to 25.0%, more preferably from 0.25 to 20.00%, based on the total mass of the release agent.
15、 如权利要求 1 所述的脱模剂， 其特征在于： 所述的水的含量为 脱模剂总质量的 20-98%， 更佳的为 30-94%。  The release agent according to claim 1, wherein the water is contained in an amount of from 20 to 98%, more preferably from 30 to 94%, based on the total mass of the release agent.
16、 如权利要求 1 所述的脱模剂， 其特征在于： 所述的脱模剂还含 有下列中的一种或多种： 有机硅化合物、 乳化助剂和催化剂； 所述的有 机硅化合物为含有硅羟基基团和 /或可水解形成硅羟基基团的有机硅化合 物。  16. The release agent according to claim 1, wherein: said release agent further comprises one or more of the following: an organosilicon compound, an emulsification aid, and a catalyst; said organosilicon compound It is an organosilicon compound containing a silyl group and/or hydrolyzable to form a silyl group.
17、 如权利要求 16所述的脱模剂， 其特征在于： 所述的脱模剂含有 混合物 A和混合物 B， 其中混合物 A中含有具有三个以上硅氢键的聚硅 氧垸化合物、 乳化剂和水； 混合物 B 中含有催化剂和水； 亚光粒子独立 的存在混合物 A和 /或混合物 B中。  The mold release agent according to claim 16, wherein: said release agent contains a mixture A and a mixture B, wherein the mixture A contains a polysiloxane compound having three or more silicon hydrogen bonds, and is emulsified. And water; mixture B contains a catalyst and water; the matt particles are independently present in mixture A and/or mixture B.
18、 如权利要求 17所述的脱模剂， 其特征在于： 所述的混合物 A中 还含有有机硅化合物和 /或乳化助剂；所述的混合物 B中还含有乳化剂和 / 或乳化助剂。 18. The release agent according to claim 17, wherein: the mixture A further contains an organosilicon compound and/or an emulsification aid; and the mixture B further contains an emulsifier and/or an emulsification aid. Agent.
19、 如权利要求 16所述的脱模剂， 其特征在于： 所述的有机硅化合 物的含量为小于或等于脱模剂总质量的 50%， 更佳的为小于或等于 30%; 所述的乳化助剂的含量为小于或等于脱模剂总质量的 8%， 更佳的为小于 或等于 5%; 所述的催化剂的含量为脱模剂总质量的 0.1-10.0%， 更佳的 为 0.1-8.0°/。； 上述含量均不包括 0%。 The release agent according to claim 16, wherein: the content of the organosilicon compound is less than or equal to 50% of the total mass of the release agent, more preferably less than or equal to 30%; The content of the emulsifying aid is less than or equal to 8% of the total mass of the releasing agent, more preferably less than or equal to 5%; the content of the catalyst is 0.1-10.0% of the total mass of the releasing agent, more preferably It is 0.1-8.0 ° /. The above contents do not include 0%.
20、 如权利要求 16所述的脱模剂， 其特征在于：  20. The release agent of claim 16 wherein:
所述的有机硅化合物为下列中的一种或多种：  The organosilicon compound is one or more of the following:
( 1) 式 III (a)、 式 III (b)和式 III (c)和式 III (d)所示的硅垸化合 物；  (1) a silicon germanium compound of the formula III (a), the formula III (b) and the formula III (c) and the formula III (d);
Figure imgf000023_0001
Figure imgf000023_0001
式 III (a) 式 III (b) 式 III (c) 式 III (d)  Formula III (a) Formula III (b) Formula III (c) Formula III (d)
o II  o II
W为 -0 、 — O-C-R 5 或 -0-N=CR6R  W is -0, — O-C-R 5 or -0-N=CR6R
Y, Y2和 Y3独立的为 -H、 -OH、 -R8、 -NR9RI0、 -RUX, -R12SH> Y, Y 2 and Y 3 are independently -H, -OH, -R 8 , -NR 9 R I0 , -R U X, -R 12 SH>
0  0
-Rl3OH、 - R14NH、 V 15 、 - Rl6OOC Rl7C = CH2或— R18O— fi-。R20 ； 为 C,-C，6的烃基； QR19 R5为（^( ^的烃基； -R l3 OH, - R 14 NH, V 15 , - R l6 OOC R l7 C = CH 2 or - R 18 O- fi-. R 20 ; is a hydrocarbon group of C, -C, 6 ; QR19 R 5 is a hydrocarbon group of (^(^;
R6和 R7相同或不相同， 独立的为（^ ^的烃基， 但 R6和 R7中碳 原子总数小于或等于 15; R 6 and R 7 are the same or different, independently a hydrocarbon group of (^, but the total number of carbon atoms in R 6 and R 7 is less than or equal to 15;
19和 R1Q相同或不相同，独立的为氢或 (^-€16的烃基，但 R9和 R10 中碳原子总数小于或等于 16; 1 9 and R 1Q are the same or different, independently hydrogen or (-- 16 hydrocarbon groups, but the total number of carbon atoms in R 9 and R 10 is less than or equal to 16;
R8、 R,,, Rl2、 Rl3和 R14独立的为 （^-( 16的烃基； R 8 , R,,, R l2 , R l3 and R 14 are independently (^-( 16 hydrocarbon group;
R15为 d-C14的烃基； R 15 is a hydrocarbon group of dC 14 ;
Rl6和 Rn相同或不相同， 独立的为氢或 C C13的烃基， 但不同时 为氢， 且 R16和 R,7中碳原子总数小于或等于 13; RI8〜R2Q相同或不相同， 独立的为 C^-C 的烃基， 但 R18、 R19和 R2o中碳原子总数小于或等于 16; R l6 and Rn are the same or different, independently hydrogen or CC 13 hydrocarbon group, but not hydrogen at all, and the total number of carbon atoms in R 16 and R, 7 is less than or equal to 13; R I8 R R 2Q are the same or different, independently a C ^ - C hydrocarbon group, but the total number of carbon atoms in R 18 , R 19 and R 2 o is less than or equal to 16;
(2) 式 IV所示的硅氧垸环状化合物；  (2) a siloxane ring compound represented by Formula IV;
Figure imgf000024_0001
式 IV 其中， R2I和 R22独立的为羟基或 Crd。的烃基， R2I和 R22不同时为羟基， m为 3-10的整数；
Figure imgf000024_0001
Wherein R 2I and R 22 are independently a hydroxyl group or a Crd. a hydrocarbon group, R 2I and R 22 are not simultaneously a hydroxyl group, and m is an integer of from 3 to 10;
以及 （3) 式 V所示的硅氧垸线性化合物；  And (3) a siloxane linear compound represented by Formula V;
Figure imgf000024_0002
Figure imgf000024_0002
式 V 其中， R23〜R3。独立的为羟基、 d-do的垸氧基或 d-C^的烃基， 较佳地 为 Cr 的烃基； 且 R26和 R27不同时为羟基， R23、 R24和 R25不同时为羟 基， R28、 R29和 R3C不同时为羟基； q为 0-1000的整数； 式 V所示的硅氧 烷线性化合物中羟基和 /或垸氧基的个数 2; Wherein R 23 to R 3 are . Independent of a hydroxyl group, a d-do decyloxy group or a dC^ hydrocarbon group, preferably a hydrocarbyl group of Cr; and R 26 and R 27 are not simultaneously a hydroxyl group, and R 23 , R 24 and R 25 are not simultaneously a hydroxyl group, R 28 , R 29 and R 3C are not simultaneously a hydroxyl group; q is an integer of 0-1000; the number of hydroxyl groups and/or alkoxy groups in the siloxane linear compound represented by formula V is 2;
所述的乳化助剂为亲水性助剂、 增稠剂、 稳定剂和 pH调节剂中的一 种或多种；  The emulsification aid is one or more of a hydrophilic auxiliary agent, a thickener, a stabilizer and a pH adjuster;
所述的催化剂为胺类催化剂和 /或有机金属类催化剂。  The catalyst is an amine catalyst and/or an organometallic catalyst.
21、 如权利要求 20 所述的脱模剂， 其特征在于： 式 III (b)、 式 ΙΠ (c) 和式 III (d) 所示的有机硅化合物中，  The mold release agent according to claim 20, wherein: in the organosilicon compound represented by the formula III (b), the formula ΙΠ (c) and the formula III (d),
当 W为 -OR4时， Y,、丫2和丫3独立的为 OH、 -R8、 -NH2、 -R,,X -R12SH、 When W is -OR4, Y, 丫2, and 丫3 are independently OH, -R 8 , -NH 2 , -R,, X -R 12 SH,
o  o
-Rl3OH、 -R14NH、 c c— Ris- R16OOC R17C = CH2或一 R18O— ^— OR20 o -R l3 OH, -R 14 NH, cc- R is- R 16 OOC R 17 C = CH 2 or a R 18 O— ^— OR 20 o
OR19 O OR19 O
当 W为一0 -c— R5或 -0-N=CR6R7时， Y,、 Y2和 Y3独立的为 OH或 -R8 ; 其中， R4〜R2«)同权利要求 20所述； When W is 0- c- R 5 or -0-N=CR 6 R 7 , Y, Y 2 and Y 3 are independently OH or -R 8 ; wherein R 4 R R 2 «) are as claimed 20 stated;
所述的亲水性助剂为水溶性高分子化合物， 更佳的为聚乙烯基吡咯 烷酮、 聚乙二醇、 聚乙烯醇和聚乙烯基甲基醚中的一种或多种；  The hydrophilic auxiliary agent is a water-soluble polymer compound, more preferably one or more of polyvinylpyrrolidone, polyethylene glycol, polyvinyl alcohol and polyvinyl methyl ether;
所述的增稠剂为水性增稠剂， 更佳的为羟烃基纤维素、 纤维素醚和 聚丙烯酸酯乳液类增稠剂中的一种或多种；  The thickener is an aqueous thickener, more preferably one or more of a hydroxyalkyl cellulose, a cellulose ether and a polyacrylate emulsion thickener;
所述的稳定剂为热稳定剂或冻融稳定剂；  The stabilizer is a heat stabilizer or a freeze-thaw stabilizer;
所述的 pH调节剂为数均分子量小于或等于 10000的酸、碱和盐中的 一种或多种， 更佳的为乙酸、 氨水、 碳酸铵、 碳酸钠和氯化铵中的一种 或多种；  The pH adjusting agent is one or more of an acid, a base and a salt having a number average molecular weight of less than or equal to 10,000, more preferably one or more of acetic acid, ammonia water, ammonium carbonate, sodium carbonate and ammonium chloride. Species
所述的胺类催化剂选自下列中的一种或多种： 三亚乙基二胺、 双（二 甲氨基乙基醚）、 二甲基环己胺、 N-甲基二环己胺、 五甲基二亚乙基三胺、 五甲基二亚丙基三胺、 四甲基乙二胺、 四甲基丙二胺、 四甲基己二胺、 N-甲基吗啉、 N-乙基吗啉、 2， 2-双吗啉基二乙基醚、 可可吗啉、 N-甲基 咪唑、 1， 2-二甲基咪唑、 1， 4-二甲基哌嗪、 N， N-二甲基苄胺、 三 （二 甲氨丙基） 胺、 三乙胺、 Ν,Ν-二甲基 （十六垸基） 胺和四甲基亚胺基二 丙基胺；  The amine catalyst is selected from one or more of the following: triethylenediamine, bis(dimethylaminoethyl ether), dimethylcyclohexylamine, N-methyldicyclohexylamine, five Methyldiethylenetriamine, pentamethyldipropylenetriamine, tetramethylethylenediamine, tetramethylpropanediamine, tetramethylhexamethylenediamine, N-methylmorpholine, N-B Mymorpholine, 2,2-bismorpholinyl diethyl ether, cocomorpholine, N-methylimidazole, 1,2-dimethylimidazole, 1,4-dimethylpiperazine, N, N- Dimethylbenzylamine, tris(dimethylaminopropyl)amine, triethylamine, hydrazine, hydrazine-dimethyl(hexadecanoyl)amine and tetramethyliminodipropylamine;
所述的有机金属类催化剂选自下列中的一种或多种： 二月桂酸二丁 基锡、 辛酸亚锡、 二 （十二烷基硫） 二丁基锡、 二醋酸二丁基锡、 异辛 酸钾、 醋酸钾、 油酸钾、 异辛酸铅、 异辛酸锌、 醋酸苯汞、 钛酸四丁酯 和钛酸四异丙酯。  The organometallic catalyst is selected from one or more of the following: dibutyltin dilaurate, stannous octoate, di(dodecylsulfate) dibutyltin, dibutyltin diacetate, potassium isooctoate, potassium acetate , potassium oleate, lead isooctanoate, zinc isooctanoate, phenylmercuric acetate, tetrabutyl titanate and tetraisopropyl titanate.
22、 如权利要求 16所述的脱模剂， 其特征在于： 所述的有机硅化合 物为下列中的一种或多种： γ-氯丙基三乙氧基硅烷、 氯丙基甲基二乙氧基 硅垸、 溴丙基甲基二乙氧基硅垸、 四乙氧基硅垸、 四正丁氧基硅垸、 甲 基二乙氧基硅烷、 甲基三甲氧基硅烷、 甲基三乙氧基硅垸、 乙基三乙氧 基硅烷、 二甲基二乙氧基硅垸、 丙基三甲氧基硅烷、 烯丙基三乙氧基硅 烷、 甲基乙基二甲氧基硅烷、 苯基三乙氧基硅烷、 苯基三丙氧基硅垸、 苯基三异丙氧基硅垸、 苯基三正丁氧基硅垸、 二苯基二甲氧基硅垸、 二 苯基二乙氧基硅烷、 甲基苯基二甲氧基硅垸、 甲基苯基二乙氧基硅烷、 乙基苯基二乙氧基硅烷、 二乙磷酸酯乙基三乙氧基硅烷、 乙烯基三乙氧 基硅烷、 乙烯基三 （β -甲氧基乙氧基） 硅垸、 γ-氨丙基三乙氧基硅烷、 γ- (β-氨乙基)-氨丙基甲基二甲氧基硅烷、 γ-(β-氨乙基) -氨丙基三甲氧基硅 垸、 γ- ( β-羟乙基氨乙基） -氨丙基甲基二甲氧基硅烷、 Ν,Ν-二乙基 -γ-胺 丙基三甲氧基硅烷、 Ν-甲基 -3-氨丙基三甲氧基硅烷、 3-环己基-氨丙基甲 基二甲氧基硅烷、 γ-缩水甘油醚氧基丙基三甲氧基硅垸、 γ-缩水甘油醚氧 基丙基三乙氧基硅垸、 γ-缩水甘油醚氧基丙基甲基二乙氧基硅烷、 γ-甲基 丙烯酰氧基丙基三甲氧基硅烷、 γ-甲基丙烯酰氧基甲基二甲氧基硅垸、 3- 脲基丙基三甲氧基硅垸、 γ-巯丙基三乙氧基硅烷、 γ-巯丙基三甲氧基硅垸、 苯胺甲基三乙氧基硅垸、 羟乙基二甲基苯基硅垸、 二羟丙基二甲基硅烷、 四乙酰氧基硅垸、 甲基三乙酰氧基硅垸、 甲基三丙酰氧基硅垸、 三苯基 乙酰氧基硅垸、 乙烯基三丁酮肟基硅垸、 甲基三丙酮肟基硅垸、 氯丙基 三丁酮肟基硅垸、 十甲基环五硅氧烷、 羟基聚二甲基硅氧垸、 三乙氧基 硅垸化聚二甲基硅氧烷、 乙烯基二甲氧基硅烷化聚二甲基硅氧烷、 甲基 乙基甲氧基硅烷化聚二甲基硅氧垸和乙烯基二甲氧基硅烷化聚甲基苯基 硅氧烷。 The mold release agent according to claim 16, wherein the organosilicon compound is one or more of the following: γ-chloropropyltriethoxysilane, chloropropylmethyldi Ethoxysilane, bromopropylmethyldiethoxysilane, tetraethoxysilane, tetra-n-butoxysilane, methyldiethoxysilane, methyltrimethoxysilane, methyl Triethoxysilane, ethyltriethoxysilane, dimethyldiethoxysilane, propyltrimethoxysilane, allyltriethoxysilane, methylethyldimethoxysilane Phenyltriethoxysilane, phenyltripropoxysilane, Phenyltriisopropoxysilane, phenyltri-n-butoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, methylphenyldimethoxysilane, Methylphenyldiethoxysilane, ethylphenyldiethoxysilane, diethylphosphoric acid ethyltriethoxysilane, vinyltriethoxysilane, vinyltris(β-methoxyB) Oxylate) silicon germanium, γ-aminopropyltriethoxysilane, γ-(β-aminoethyl)-aminopropylmethyldimethoxysilane, γ-(β-aminoethyl)-aminopropyl Trimethoxysilane, γ-(β-hydroxyethylaminoethyl)-aminopropylmethyldimethoxysilane, hydrazine, hydrazine-diethyl-γ-aminopropyltrimethoxysilane, hydrazine -methyl-3-aminopropyltrimethoxysilane, 3-cyclohexyl-aminopropylmethyldimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidyl ether Oxypropylpropyltriethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloyloxy Methyldimethoxysilane, 3-ureidopropyltrimethoxysilane , γ-mercaptopropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, aniline methyltriethoxysilane, hydroxyethyldimethylphenylsilane, dihydroxypropyldimethyl Silane, tetraacetoxysilane, methyltriacetoxysilane, methyltripropionyloxysilane, triphenylacetoxysilane, vinyltributyl sulfonium silicon, methyl Triacetone decyl silicon germanium, chloropropyl tributyl ketone decyl silicon germanium, decamethylcyclopentasiloxane, hydroxy polydimethylsiloxane, triethoxysilyl polydimethylsiloxane , vinyl dimethoxy silylated polydimethylsiloxane, methyl ethyl methoxy silylated polydimethyl siloxane and vinyl dimethoxy silylated polymethyl phenyl siloxane .
23、 如权利要求 1〜22中任一项所述的脱模剂， 其特征在于： 所述的 脱模剂的 ρΗ为 3-7。  The release agent according to any one of claims 1 to 22, wherein the release agent has a pH of 3-7.
24、 如权利要求 1〜23中任一项所述的脱模剂， 其特征在于： 当脱模 剂中不含增稠剂时， 脱模剂的固含量为 40-75%; 当含有增稠剂时， 脱模 剂的固含量为 1-40%; 百分比为质量百分比。  The release agent according to any one of claims 1 to 23, wherein: when the release agent does not contain a thickener, the solid content of the release agent is 40-75%; In the case of a thickener, the solid content of the release agent is 1 to 40%; the percentage is a mass percentage.
25、 如权利要求 1〜24 中任一项所述的脱模剂在制备亚光型橡胶制 品、 亚光型塑料制品或亚光型复合材料制品中的应用。  The use of the release agent according to any one of claims 1 to 24 for the preparation of a matt type rubber article, a matt type plastic article or a matt composite article.
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1539762A (en) * 1975-03-07 1979-01-31 Toray Silicone Co Parting composition for tyre mouldings
EP0491598A2 (en) * 1990-12-17 1992-06-24 Shin-Etsu Chemical Co., Ltd. Curable organopolysiloxane composition having constant mould-release properties
US20090030150A1 (en) * 2007-07-26 2009-01-29 Henkel Corporation Mold Release Agents Employing Polyvinyl Alcohol

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1539762A (en) * 1975-03-07 1979-01-31 Toray Silicone Co Parting composition for tyre mouldings
EP0491598A2 (en) * 1990-12-17 1992-06-24 Shin-Etsu Chemical Co., Ltd. Curable organopolysiloxane composition having constant mould-release properties
US20090030150A1 (en) * 2007-07-26 2009-01-29 Henkel Corporation Mold Release Agents Employing Polyvinyl Alcohol

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103706756A (en) * 2012-09-29 2014-04-09 天能电池(芜湖)有限公司 Film-spraying agent for pouring grid of lead-acid storage battery, and preparation method thereof
WO2021231719A1 (en) * 2020-05-14 2021-11-18 Quaker Chemical Corporation Water-soluble silicone-based release agent
CN112812688A (en) * 2020-12-30 2021-05-18 南京科悦新材料有限公司 Method for preparing release agent material for transfer of adhesive
CN114232381A (en) * 2021-12-22 2022-03-25 东莞市伟邦新材料科技有限公司 Anti-sticking agent for gum dipping process and preparation method thereof

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