CN101892115A - Release agent and application thereof - Google Patents

Release agent and application thereof Download PDF

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Publication number
CN101892115A
CN101892115A CN2009100517727A CN200910051772A CN101892115A CN 101892115 A CN101892115 A CN 101892115A CN 2009100517727 A CN2009100517727 A CN 2009100517727A CN 200910051772 A CN200910051772 A CN 200910051772A CN 101892115 A CN101892115 A CN 101892115A
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ether
releasing agent
polyoxyethylene
silane
alkyl
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Inventor
徐健岩
张宜荣
张勇
邢文涛
李志明
陆征
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Henkel China Investment Co Ltd
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Henkel China Investment Co Ltd
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Priority to CN2009100517727A priority Critical patent/CN101892115A/en
Priority to PCT/CN2010/000772 priority patent/WO2010133095A1/en
Publication of CN101892115A publication Critical patent/CN101892115A/en
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C33/00—Moulds or cores; Details thereof or accessories therefor
    • B29C33/56—Coatings, e.g. enameled or galvanised; Releasing, lubricating or separating agents
    • B29C33/60—Releasing, lubricating or separating agents
    • B29C33/62—Releasing, lubricating or separating agents based on polymers or oligomers
    • 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

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Moulds For Moulding Plastics Or The Like (AREA)

Abstract

The invention discloses a release agent. The release agent comprises polysiloxane compound of which the molecule has more than three silicon-hydrogen (Si-H) bonds, semigloss particles, an emulsifying agent and water. The invention also provides the application of the release agent in the preparation of semigloss type rubber products, semigloss type plastic products or semigloss type composite material products. The release agent of the invention has simple construction, high release property and a good semigloss effect, and can form a harder film after being cured, so that the semigloss particles are fixed on the film without being transferred to the molded products, and semi-permanent demoulding is realized; the obtained products after multiple demoulding still have basically constant glossiness and high storage stability without being influenced on the product property. The release agent of the invention is almost suitable for all moulds, particularly has higher caking property with metal moulds and has a wide application range.

Description

A kind of releasing agent and application thereof
Technical field
The present invention relates to a kind of releasing agent and application thereof.
Background technology
Along with the raising of people to light pollution understanding, inferior finished product is more and more favored.Usually for the goods that inferior light requirement is arranged, for example rubber, plastics, matrix material etc., a kind of way commonly used in the existing technology is to utilize mould to realize inferior light, is about to mould and makes rough surface, moulded section then.Patent JP2003231150 (A) has introduced and a kind of the fused resin has been injected the method that the moulding of surperficial scraggly mould cooled and solidified prepares inferior photopolymer resin.Patent US4954297 (A) introduced a kind of on coarse casting surface the heating and pressurizing moulding resin, preparation has the inferior photopolymer resin of fine groove.Increase but scraggly die surface is long-pending, be unfavorable for the coating of releasing agent and the cleaning of mould, cause goods demoulding difficulty, destroy the product surface pattern.Another kind of way is to add inferior light auxiliary agent in goods, to realize the rubber matt effect, for example patent JP58029622 (A) has introduced a kind of a small amount of talcum powder and barium sulfate powder of adding in polyacrylic resin, and mediates extrusion moulding at 200-300 ℃, prepares inferior light polyacrylic resin.Patent CNl468900A has introduced improving one's methods of a kind of polychloroethylene acrylonitrile butadiene CABLE MATERIALS, wherein mentions crosslinked pvc resin and polyvinyl chloride with making base-material, can play photoextinction, produces matt effect.But some performances that add affiliation reduction rubber itself of auxiliary agent.Another kind of way is to adopt sand milling technology to make the rubber outward appearance be inferior light state behind the rubber-moulding separately, but this way subsequent technique is very complicated.
Therefore, it is more and more welcome that existing demolding performace has the releasing agent of matt effect again.Patent WO2009017675A2 has introduced a kind of releasing agent, the material that contains siloxanes, the inferior light particle of water-based, solidifying agent in its prescription and have hydrophobic and water-wet behavior simultaneously, the selectable carrier that contains in this external release agent.This releasing agent can be given the formed substance matt effect, and can realize repeatedly the inferior light demoulding, but its coating that will spray 2-3 kind emulsion when using on mould successively to be realizing inferior light function, and the glossiness between every moulded product differs bigger.The complicated construction technology and the fluctuation of every moulded product glossiness have limited the application of this releasing agent.
Summary of the invention
Technical problem to be solved by this invention is to have overcome the existing defective that the releasing agent construction is complicated, the goods glossiness differs greatly with matt effect, provide a kind of construction simple, release property and matt effect are all good, can realize the semi-permanent mould demoulding, and repeatedly the resulting product glossiness can keep substantially constant after the demoulding, do not influence product properties, the releasing agent that shelf stability is high.And releasing agent of the present invention can solidify in broad solidification value scope, is applicable to the goods of multiple unlike material.Simultaneously can on multiple kinds of molds, finish the demoulding, applied range.
Releasing agent of the present invention comprises: have the polysiloxane compound of three above si-h bonds, inferior light particle, emulsifying agent and water.
Among the present invention, described have the polysiloxane compound of three above si-h bonds owing to have the si-h bond with reactive behavior at its polymerization end of the chain and/or side chain, can form the cross-linked polymer of higher hardness with solidifying agent or unsaturated polymer reaction, can solidify to form harder film, thereby inferior light particle is fixed on the film, and be not transferred on the moulding product, realize the repeatedly inferior light demoulding thus.In addition, the emulsion with polysiloxane compound preparation of si-h bond can steady in a long-termly exist, and makes releasing agent of the present invention be water-base emulsion steady in a long-term.
Described polysiloxane compound with three above si-h bonds can for any existing contained si-h bond quantity more than or equal to 3 polysiloxane compound, preferably be in the following polymkeric substance with three above si-h bonds one or more: (1) is by the homopolymer that forms suc as formula the structural unit shown in the I; (2) by form suc as formula the structural unit shown in I and the formula II random, alternately, block and graft copolymer, this multipolymer is linearity or cyclocopolymer; (3) by one or more cross-linking copolymers that form in the polymkeric substance of above-mentioned (1) and (2).In the above-mentioned polymkeric substance, the END CAPPED GROUP of linearity or cross-linked polymer can be conventional END CAPPED GROUP, and preferable is by hydrogen, hydroxyl, C 1-C 10Alkoxyl group and C 1-C 10Alkyl in the silylation of one or more replacements.
Figure B2009100517727D0000031
Formula I formula II
Wherein, R 1Be C 1-C 10Alkoxyl group or C 1-C 10Alkyl, preferably independently be C 1-C 6Alkoxyl group or C 1-C 6Alkyl; R 2And R 3Independently be hydroxyl, C 1-C 10Alkoxyl group or C 1-C 10Alkyl, preferably independently be hydroxyl, C 1-C 6Alkoxyl group or C 1-C 6Alkyl, but R 2And R 3Be not hydroxyl simultaneously.
The content of described polysiloxane compound with three above si-h bonds is preferable is the 1-65% of releasing agent total mass, and that better is 3-50%.The 5-10000cst that described viscosity with polysiloxane compound of three above si-h bonds is, that preferable is 5-5000cst, that better is 5-1000cst; Above-mentioned viscosity is all under 25 ℃ and records.Hydrogen richness on the si-h bond of described polysiloxane compound with three above si-h bonds is preferable is 0.10-1.63%, and that better is 0.50-1.63%; Per-cent is mass percent.
Among the present invention, described inferior light particle is for giving the inorganic particulate and/or the organic filler of releasing agent matt effect, can adopt existing various inferior light particle, one or more that preferable is in silicon dioxide granule, metal oxide particle, inorganic salt particle and the polymer particle; Described metal oxide particle is preferable is in TiO 2 particles, aluminium oxide particles, zinc oxide particle and the silver suboxide particle one or more.What described inorganic salt particle was preferable is calcium carbonate particles and/or barium sulfate particle.Described polymer particle is preferable is in polyethylene particles, particulate polyvinyl chloride, polypropylene particles, polystyrene particle and the polytetrafluoroethylparticle particle one or more.Described inferior light particle is infinite can be in following one or more: German Degussa company
Figure B2009100517727D0000032
Figure B2009100517727D0000033
With
Figure B2009100517727D0000034
U.S. Grace company
Figure B2009100517727D0000035
Figure B2009100517727D0000041
Figure B2009100517727D0000042
With
Figure B2009100517727D0000043
The fumed nano silicon-dioxide that U.S. Cabot company produces
Figure B2009100517727D0000044
With
Figure B2009100517727D0000045
The Dyneon TF-9207 that Minnesota Mining and Manufacturing Company produces etc.That the particle diameter of described inferior light particle is preferable is 0.2-15.0 μ m, and that better is 0.5-10.0 μ m.That the content of described inferior light particle is preferable is the 0.1-50.0% of releasing agent total mass, and that better is 0.5-30.0%.
Emulsifying agent among the present invention can be existing various emulsifying agent, and it can play stabilization to compositions such as polysiloxane compound with three above si-h bonds in the releasing agent and inferior light particles, and preferable is nonionogenic tenside.That the HLB value of described nonionogenic tenside is preferable is 3-50.Described nonionogenic tenside is better is in polyoxyethylene-type nonionogenic tenside, polyol-based non-ionic surfactant, alkylol amide type nonionogenic tenside and the organosilicon type nonionogenic tenside one or more.Better, described emulsifying agent is selected from one or more in following: polyoxyethylene (4) nonyl phenol 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), lauryl alcohol polyoxyethylene (23) ether (HLB=16.9), C 9-C 11Alkyl alcohol polyoxyethylene (6) ether (Neodol 91-6 for example, HLB=12.5), C 12-C 14Alkyl alcohol polyoxyethylene (7) ether (Imbentin-AG/124/070 for example, Marlipal, HLB=12.0), C 12-C 15Alkyl alcohol polyoxyethylene (12) ether (Alkasurf LA-12 for example, Tergitol 25-L-12, HLB=14.4), tridecyl alcohol polyoxyethylene (6) ether (HLB=11.4), tridecyl alcohol polyoxyethylene (10) ether (HLB=13.8), tridecyl alcohol polyoxyethylene (15) ether (HLB=15.5), hexadecyl alcohol polyoxyethylene (15) ether (HLB=15.5), hexadecyl alcohol polyoxyethylene (20) ether (HLB=17.0), hexadecyl alcohol polyoxyethylene (30) ether (HLB=19.5), different hexadecyl alcohol polyoxyethylene (20) ether (HLB=15.7), hexadecyl alcohol polyoxyethylene (12) ether, stearyl alcohol polyoxyethylene (12) ether (Incropol CS-12 for example, HLB=12.0), hexadecyl alcohol polyoxyethylene (30) ether, stearyl alcohol polyoxyethylene (30) ether (Incropol CS-30 for example, HLB=16.7), stearyl alcohol polyoxyethylene (20) ether (HLB=15.3), stearyl alcohol polyoxyethylene (40) ether (HLB=17.4), oleyl alcohol polyoxyethylene (20) ether (HLB=15.5), polyoxyethylene nonyl phenyl ethene (9) ether (HLB=13.5), polyoxyethylene nonyl phenyl ethene (10) ether (HLB=14.0), polyoxyethylene nonyl phenyl ethene (12) ether (HLB=14.6), polyoxyethylene nonyl phenyl ethene (30) ether (HLB=17.5), polyoxyethylene nonyl phenyl ethene (40) ether (HLB=18.0), polyoxyethylene nonyl phenyl ethene (70) ether (HLB=18.7), polyoxyethylene nonyl phenyl ethene (5) ether (HLB=10.0), polyoxyethylene nonyl phenyl ethene (8) ether (HLB=12.4), polyoxyethylene nonyl phenyl ethene (100) ether (HLB=19.1), coco amine polyoxyethylene (15) ether (HLB=15.7), ethylenediamine polyoxyethylene-polyoxytrimethylene-polyoxyethylene block polyether (HLB=12-18), two lauric acid polyoxyethylene glycol (8) esters (HLB=10.8), two lauric acid polyoxyethylene glycol (20) esters (HLB=10.8), stearic acid polyoxyethylene glycol (40) ester (HLB=16.9), stearic acid polyoxyethylene glycol (100) ester (HLB=18.5), polyoxyethylene (20) Zerol (HLB=13.1), polyoxyethylene (5) sorbitan monooleate (HLB=10.0), polyoxyethylene sorbitol acid anhydride trioleate (HLB=11.0) and polyether-modified polysiloxane.The polymerization degree of the numeral polymkeric substance in the above-mentioned bracket.Carbonatoms before the alkyl alcohol polyoxyethylene ether is the qualification to carbonatoms in the alkyl alcohol, as C 12Alkyl alcohol polyoxyethylene (7) ether is represented dodecyl alcohol polyoxyethylene (7) ether.That the content of described emulsifying agent is preferable is the 0.2-25.0% of releasing agent total mass, and that better is 0.25-20.00%.
Among the present invention, that the content of described water is preferable is the 20-98% of releasing agent total mass, and that better is 30-94%.
Releasing agent of the present invention also can contain other additives of this area routine, as long as it does not play obvious negative effects to releasing agent of the present invention.Described other additives preferably also contain one or more in following: silicoorganic compound, emulsion adjuvant and catalyzer; Described silicoorganic compound are the silicoorganic compound that contain silicon oh group and/or hydrolyzable formation silicon oh group.
Among the present invention, described silicoorganic compound can be beneficial to the cohesiveness that strengthens releasing agent and mould.The content of described silicoorganic compound preferable for being less than or equal to 50% of releasing agent total mass, better for being less than or equal to 30%.
Preferable, described silicoorganic compound are selected from one or more in following:
(1) silane compound shown in formula III (a), formula III (b), formula III (c) and the formula III (d);
Figure B2009100517727D0000061
Formula III (a) formula III (b) formula III (c) formula III (d)
Wherein, W is-OR 4, Or-O-N=CR 6R 7
Y 1, Y 2And Y 3Independently be-H ,-OH ,-R 8,-NR 9R 10,-R 11X ,-R 12SH ,-R 13OH ,-R 14NH, -R 16OOCR 17C=CH 2Or
Figure B2009100517727D0000064
R 4Be C 1-C 16Alkyl;
R 5Be C 1-C 15Alkyl;
R 6And R 7Identical or inequality, independently be C 1-C 15Alkyl, but R 6And R 7Middle the total number of carbon atoms is less than or equal to 15;
R 9And R 10Identical or inequality, independently be hydrogen or C 1-C 16Alkyl, but R 9And R 10Middle the total number of carbon atoms is less than or equal to 16;
R 8, R 11, R 12, R 13And R 14Independently be C 1-C 16Alkyl;
R 15Be C 1-C 14Alkyl;
R 16And R 17Identical or inequality, independently be hydrogen or C 1-C 13Alkyl, but be not hydrogen simultaneously, and R 16And R 17Middle the total number of carbon atoms is less than or equal to 13;
R 18～R 20Identical or inequality, independently be C 1-C 14Alkyl, but R 18, R 19And R 20Middle the total number of carbon atoms is less than or equal to 16.
Better, in III (b), formula III (c) and formula III (d),
When W is-OR 4The time, Y 1, Y 2And Y 3Independently be OH ,-R 8,-NH 2,-R 11X ,-R 12SH ,-R 13OH ,-R 14NH,
Figure B2009100517727D0000065
-R 16OOCR 17C=CH 2Or
Figure B2009100517727D0000066
When W is
Figure B2009100517727D0000071
Or-O-N=CR 6R 7The time, Y 1, Y 2And Y 3Independently be OH or-R 8
Wherein, R 4～R 20As described above.
(2) the siloxanes ring compound shown in the formula IV;
Figure B2009100517727D0000072
Formula IV
Wherein, R 21And R 22Independently be hydroxyl or C 1-C 10Alkyl, R 21And R 22Be not hydroxyl simultaneously, m is the integer of 3-10;
And the siloxanes ol cpds shown in (3) formula V;
Figure B2009100517727D0000073
Formula V
Wherein, R 23～R 30Be hydroxyl, C independently 1-C 10Alkoxyl group or C 1-C 10Alkyl, be preferably C 1-C 8Alkyl; And R 26And R 27Be not hydroxyl simultaneously, R 23, R 24And R 25Be not hydroxyl simultaneously, R 28, R 29And R 30Be not hydroxyl simultaneously; Q is the integer of 0-1000; Number 〉=2 of hydroxyl and/or alkoxyl group in the siloxanes ol cpds of formula V.
Above-mentioned alkyl is preferably alkyl.
Preferably, described silicoorganic compound are one or more in following: γ-chloropropyl triethoxysilane, the chloropropyl methyldiethoxysilane, the bromopropyl methyldiethoxysilane, tetraethoxysilane, four n-butoxy silane, methyldiethoxysilane, methyltrimethoxy silane, Union carbide A-162, ethyl triethoxysilane, dimethyldiethoxysilane, propyl trimethoxy silicane, allyltriethoxysilane, methylethyl dimethoxy silane, phenyl triethoxysilane, phenyl tripropoxy silane, phenyl three isopropoxy silane, phenyl three n-butoxy silane, dimethoxydiphenylsilane, the phenylbenzene diethoxy silane, aminomethyl phenyl dimethoxy silane, the aminomethyl phenyl diethoxy silane, the ethylphenyl diethoxy silane, diethyl phosphoric acid ester ethyl triethoxysilane, vinyltriethoxysilane, vinyl three ('beta '-methoxy oxyethyl group) silane, γ-An Bingjisanyiyangjiguiwan, γ-(β-aminoethyl)-aminopropyl methyl dimethoxysilane, γ-(β-aminoethyl)-aminopropyl trimethoxysilane, γ-(beta-hydroxyethyl aminoethyl)-aminopropyl methyl dimethoxysilane, N, N-diethyl-γ-amine propyl trimethoxy silicane, N-methyl-3-aminopropyl trimethoxysilane, 3-cyclohexyl-aminopropyl methyl dimethoxysilane, γ-glycidyl ether oxygen base propyl trimethoxy silicane, γ-glycidyl ether oxygen base propyl-triethoxysilicane, γ-glycidyl ether oxygen base propyl group methyldiethoxysilane, γ-methacryloxypropyl trimethoxy silane, γ-methacryloxy methyl dimethoxysilane, 3-urea groups propyl trimethoxy silicane, gamma-mercaptopropyltriethoxysilane, γ-mercaptopropyl trimethoxysilane, anilinomethyl triethoxysilane, the hydroxyethyl dimethyl phenyl silane, the dihydroxypropyl dimethylsilane, the tetrem acyloxy silane, methyl triacetoxysilane, methyl three propionyloxy silane, the triphenyl acetoxysilane, the vinyl tributanoximo silane, methyl tri acetylacetonate oximino silane and chloropropyl tributanoximo silane, decamethylcyclopentaandoxane, the hydroxyl polydimethylsiloxane, triethoxysilicane alkanisation polydimethylsiloxane, vinyl-dimethyl TMOS polydimethylsiloxane, methylethyl methoxy silane polydimethylsiloxane and vinyl-dimethyl TMOS PSI etc.
Among the present invention, described emulsion adjuvant can be the conventional all kinds of emulsion adjuvants that indistinctively releasing agent of the present invention brought disadvantageous effect that use in this area, and it is used to increase the denseness of wetting ability, releasing agent of polymkeric substance and stability etc.The content of described emulsion adjuvant preferable for being less than or equal to 8% of releasing agent total mass, better for being less than or equal to 5%.Described emulsion adjuvant is one or more in wetting ability auxiliary agent, thickening material, stablizer and the pH regulator agent etc.
Wherein, described wetting ability auxiliary agent preferably water solubleness high molecular compound, one or more that preferable is in Polyvinylpyrolidone (PVP), polyoxyethylene glycol, polyvinyl alcohol and the polyvinyl methyl ether.
Wherein, described thickening material is the conventional thickening material that uses in this area, and preferable is water-based thickener, one or more that better is in hydroxyalkyl cellulose, ether of cellulose and the polyacrylate dispersion class thickening material etc.
Wherein, described stablizer comprises thermo-stabilizer or freeze-thaw stabiliser.
Wherein, described pH regulator agent is the conventional pH regulator agent of using in this area, preferable is less than or equal in 10000 acid, alkali and the salt one or more for molecular weight; One or more that better is in acetate, ammoniacal liquor, volatile salt, yellow soda ash and the ammonium chloride.
Among the present invention, described catalyzer be for can promote between the silicon hydrogen group, and silicon hydrogen group and siloxane groups, and the catalyzer that reacts of silicon hydrogen group and silicon oh group comprise amines catalyst and/or organo-metallic class catalyzer.
Described amines catalyst preferably is selected from one or more in following: triethylenediamine, two (dimethylaminoethyl ethers), dimethylcyclohexylamine, N-methyl bicyclic hexylamine, five methyl diethylentriamine, the pentamethyl-dipropylenetriamine, Tetramethyl Ethylene Diamine, 4-methyl-diaminopropane, 4-methyl hexamethylene diamine, N-methylmorpholine, N-ethylmorpholine, 2, the 2-dual-morpholinyl diethyl ether, the cocoa morpholine, the N-Methylimidazole, 1, the 2-methylimidazole, 1, the 4-lupetazin, N, the N-dimethyl benzylamine, three (dimethylaminopropyl) amine, triethylamine, N, N-dimethyl (hexadecyl) amine and tetramethyl-imido grpup dipropylamine.
Described organo-metallic class catalyzer preferably is selected from one or more in following: dibutyl tin laurate, stannous octoate, two (dodecyl sulphur) dibutyl tin, dibutyltin diacetate, isocaprylic acid potassium, Potassium ethanoate, potassium oleate, isocaprylic acid lead, isocaprylic acid zinc, Phenylmercuric Acetate, tetrabutyl titanate and titanium isopropylate.That the content of described catalyzer is preferable is the 0.1-10.0% of releasing agent total mass, and that better is 0.1-8.0%.
The pH value of releasing agent of the present invention is preferably 3-7, more preferably 4-7.
The solid content of releasing agent of the present invention can be regulated by adding water.That the solid content of releasing agent is preferable is 0.1-80.0%, and that better is 1-75%.When containing thickening material in the releasing agent, that solid content is preferable is 1-40%; When not containing thickening material, that solid content is preferable is 40-75%.In the present invention's one preferred embodiment, solid content is 2-40% when containing thickening material in the releasing agent; Solid content is 40-75% when not containing thickening material.The releasing agent of this preferred embodiment has the long shelf time, can at room temperature stablize and place more than one month.Described per-cent is mass percent.
As required, the component form that releasing agent of the present invention can be mixed together for all the components also can be each composition is divided into the other blended polycomponent of fractions form.When containing catalyzer in the releasing agent, releasing agent of the present invention preferably contains 2 components, and wherein catalyzer does not coexist as in the same component with the polysiloxane compound with three above si-h bonds.
In the present invention's one preferred embodiments, this releasing agent contains mixture A and mixture B, wherein contains polysiloxane compound, emulsifying agent and the water with three above si-h bonds among the mixture A; Contain catalyzer and water among the mixture B; Inferior light particle independently is present among mixture A and/or the mixture B.In the present invention one better embodiment, also contain silicoorganic compound and/or emulsion adjuvant among the described mixture A; Also contain emulsifying agent and/or emulsion adjuvant among the mixture B.
Among the present invention, term " polysiloxane " is meant that main chain is made of repeating unit silicon-oxygen (Si-O) key, wherein directly links the polymkeric substance of organic group on the Siliciumatom.
Among the present invention, term " inferior light particle " is meant the solid particulate of giving the goods matt effect.
Among the present invention, term " inferior light " is meant that rubber item glossiness after the moulding is less than 5.0 ° (comprise 5.0 °, input angle is 60 °).
Among the present invention, term " the semi-permanent mould demoulding " is meant releasing agent of spraying, can realize the demoulding more than 5 times, and the goods glossiness of each mold forming is constant.
Among the present invention, term " the goods glossiness of each mold forming is constant " is meant that the error of the goods glossiness after the moulding is ± 0.1 °.
The preparation method of releasing agent of the present invention can carry out with reference to the method for preparing releasing agent conventional in the prior art, and preferably the method according to patent CN101230138A is prepared.
The present invention also provides the application of described releasing agent in preparation sub-smooth type rubber item, sub-smooth type plastics or sub-smooth type composite product.
But each optimum condition arbitrary combination of the present invention promptly gets each preferred embodiment of the present invention.
Positive progressive effect of the present invention is:
1, releasing agent construction of the present invention is simple, release property and matt effect are all good, can form harder film during curing, thereby inferior light particle is fixed on the film, and be not transferred on the moulded products, realize the semi-permanent mould demoulding thus, and repeatedly after the demoulding resulting product glossiness can keep substantially constant, the error of glossiness is ± 0.1 °, does not influence product properties.
2, releasing agent good stability of the present invention can be stored more than 1 week under the room temperature; When the polysiloxane compound that has three above si-h bonds in the releasing agent and catalyzer did not coexist as in the same mixture, releasing agent of the present invention can be stored more than one month, even reaches more than 3 months.
3, releasing agent of the present invention can solidify under differing temps, can be applicable to that therefore the goods of high solidification value also can be used for the goods of low solidification value.
4, releasing agent of the present invention can be used for nearly all existing mould.Especially for metal die, the si-h bond in the releasing agent can form chemically crosslinked and physical crosslinking with the lip-deep hydroxyl of metal die, makes releasing agent of the present invention and metal die have better cohesiveness.
Embodiment
Further specify the present invention with embodiment below, but the present invention is not limited.
Unless otherwise, below among each embodiment each step of preparation releasing agent all under normal pressure, carry out, temperature is a normal temperature.
The performance characterization of the releasing agent that the present invention makes is as follows:
Polymer viscosity by the rotary viscometer of the NDJ-1A of Chinese Shen De Technology Dev Company Ltd. 25 ℃ ℃ ± 1 ℃ mensuration.
Polymericular weight and distribution thereof are measured by the Waters Breeze 1515 efficient gel permeation chromatographs of U.S. Waters company.
The solid content of emulsion adopts plum Teller-Tuo benefit HB43-S halogen moisture content tester 125 ℃ of mensuration.
The surface energy of crosslinked caudacoria is measured by the OCA-15 of German Dataphysics company.
The glossiness of rubber item is recorded by NOVO-GLOSS60 ° of statistics type glossometer of Rhopoint Instumentation company.
The details of the polysiloxane compound with three above si-h bonds that uses among the embodiment are:
Methyl Hydrogen Polysiloxane Fluid
Figure B2009100517727D0000111
Dow corning company, hydrogen content 1.58-1.60%, viscosity is 30cst;
Methyl Hydrogen Polysiloxane Fluid Dow corning company, hydrogen content 0.90%, viscosity is 70cst;
Methyl Hydrogen Polysiloxane Fluid Dow corning company, hydrogen content 1.05%, viscosity is 29cst;
Methyl Hydrogen Polysiloxane Fluid
Figure B2009100517727D0000122
Dow corning company, hydrogen content 1.60%, viscosity is 30cst;
Methyl Hydrogen Polysiloxane Fluid ORG202: the bright abundant Industrial Co., Ltd. in Shanghai, hydrogen content 1.58-1.63%, viscosity is 15-40cst;
The details of the inferior light particle that uses among the embodiment are:
Figure B2009100517727D0000123
U.S. Gray Si (Grace) company, particle diameter 3.0-4.0 μ m;
Figure B2009100517727D0000124
U.S. Gray Si (Grace) company, particle diameter 4.6-5.4 μ m;
Figure B2009100517727D0000125
U.S. Gray Si (Grace) company, particle diameter 3.0-4.0 μ m;
Figure B2009100517727D0000126
U.S. Gray Si (Grace) company, particle diameter 4.6-5.4 μ m;
Figure B2009100517727D0000127
U.S. Gray Si (Grace) company, particle diameter 4.6-5.4 μ m;
Figure B2009100517727D0000128
U.S.'s Cabot (Cabot) company, particle diameter 0.2-0.3 μ m;
Germany Degussa company, particle diameter 10.5 μ m.
Use the details of silicoorganic compound to be among the embodiment:
Hydroxy-end capped polydimethylsiloxane
Figure B2009100517727D00001210
Fluid: Dow corning company, viscosity 55-90cst;
Hydroxy-end capped polydimethylsiloxane
Figure B2009100517727D00001211
Dow corning company, viscosity 42cst;
The end capped polydimethylsiloxane of vinyl-dimethyl oxygen base: Henkel KGaA company, viscosity (referring to patent US5300608).
Use the details of thickening material to be among the embodiment:
Switzerland vapour Bagong department.
Embodiment 1
Under the room temperature, each composition in the table 1 is added in high speed dispersion still, stirred 20 minutes, it is mixed with the rotating speed of 1500rpm.Under the 1500rpm rotating speed, in 30 minutes, at the uniform velocity drip 31.6 gram deionized waters again; After dripping off, continue down to stir 30 minutes in the 200rpm rotating speed, promptly.This releasing agent solid content is 50%, room temperature storage 1 month, but thin up during use.The releasing agent of embodiment 1 preparation is sprayed on the metal die, can utilize this releasing agent demoulding terpolymer EP rubber at 160 ℃ of following 10 minutes film-formings, can obtain glossiness and be 0.7 ° rubber item, but once spray the demoulding more than 20 times, and the rubber glossiness of each mould is constant.Demoulding thermoplastic polyurethane material can obtain glossiness and be 2.7 ° goods; Demoulding Polybenzoxazine material, can obtain glossiness is 2.3 ° goods, but once sprays the demoulding more than 5 times, and the goods glossiness of each mould is constant.
Table 1
Embodiment 2
Under the room temperature, each composition in the table 2 is added in high speed dispersion still, stirred 20 minutes, it is mixed with the rotating speed of 1500rpm.Under the 1500rpm rotating speed, in 30 minutes, at the uniform velocity drip 31.6 gram deionized waters again; After dripping off, continue down to stir 30 minutes in the 200rpm rotating speed, promptly.This releasing agent solid content is 55%, room temperature storage 2 months, but thin up during use.The releasing agent of embodiment 2 preparations is sprayed on the metal die, can utilize this releasing agent demoulding terpolymer EP rubber at 160 ℃ of following 10 minutes film-formings, can obtain glossiness and be 1.0 ° rubber item, but once spray the demoulding more than 20 times, and the rubber glossiness of each mould is constant.
Table 2
Figure B2009100517727D0000132
Embodiment 3
Under the room temperature, each composition in the table 3 is added in high speed dispersion still, stirred 20 minutes, it is mixed with the rotating speed of 1500rpm.Under the 1500rpm rotating speed, in 30 minutes, at the uniform velocity drip 30.4 gram deionized waters again; After dripping off, continue down to stir 30 minutes in the 200rpm rotating speed, promptly.This releasing agent solid content is 50%, room temperature storage 1 month, but thin up during use.The releasing agent of embodiment 3 preparations is sprayed on the metal die, can utilize this releasing agent demoulding terpolymer EP rubber at 160 ℃ of following 10 minutes film-formings, can obtain glossiness and be 2.7 ° rubber item, but once spray the demoulding more than 20 times, and the rubber glossiness of each mould is constant.
Table 3
Figure B2009100517727D0000142
Embodiment 4
Under the room temperature, each composition in the table 4 is added in high speed dispersion still, stirred 20 minutes, it is mixed with the rotating speed of 1500rpm.Under the 1500rpm rotating speed, in 30 minutes, at the uniform velocity drip 31.6 gram deionized waters again; After dripping off, continue down to stir 30 minutes in the 200rpm rotating speed, promptly.This releasing agent solid content is 48%, room temperature storage 2 months, but thin up during use.The releasing agent of embodiment 4 preparations is sprayed on the metal die, can utilize this releasing agent demoulding terpolymer EP rubber at 160 ℃ of following 10 minutes film-formings, can obtain glossiness and be 2.0 ° rubber item, but once spray the demoulding more than 20 times, and the rubber glossiness of each mould is constant.
Table 4
Figure B2009100517727D0000143
Figure B2009100517727D0000151
Embodiment 5
Under the room temperature, each composition in the table 5 is added in high speed dispersion still, stirred 20 minutes, it is mixed with the rotating speed of 1500rpm.Under the 1500rpm rotating speed, in 30 minutes, at the uniform velocity drip 31.6 gram deionized waters again; After dripping off, continue down to stir 30 minutes in the 200rpm rotating speed, promptly.This releasing agent solid content is 59%, room temperature storage 2 months, but thin up during use.The releasing agent of embodiment 5 preparations is sprayed on the metal die, can utilize this releasing agent demoulding terpolymer EP rubber at 160 ℃ of following 10 minutes film-formings, can obtain glossiness and be 0.9 ° rubber item, but once spray the demoulding more than 20 times, and the rubber glossiness of each mould is constant.
Table 5
Figure B2009100517727D0000152
Embodiment 6
Under the room temperature, each composition in the table 6 is added in high speed dispersion still, stirred 20 minutes, it is mixed with the rotating speed of 1500rpm.Under the 1500rpm rotating speed, in 30 minutes, at the uniform velocity drip 31.6 gram deionized waters again; After dripping off, continue down to stir 30 minutes in the 200rpm rotating speed, promptly.This releasing agent solid content is 62%, room temperature storage 2 months, but thin up during use.The releasing agent of embodiment 6 preparations is sprayed on the metal die, can utilize this releasing agent demoulding terpolymer EP rubber at 160 ℃ of following 10 minutes film-formings, can obtain glossiness and be 0.9 ° rubber item, but once spray the demoulding more than 20 times, and the rubber glossiness of each mould is constant.
Table 6
Figure B2009100517727D0000161
Embodiment 7
Under the room temperature, each composition in the table 7 is added in high speed dispersion still, stirred 20 minutes, it is mixed with the rotating speed of 1500rpm.Under the 1500rpm rotating speed, in 30 minutes, at the uniform velocity drip 31.6 gram deionized waters again; After dripping off, continue down to stir 30 minutes in the 200rpm rotating speed, promptly.This releasing agent solid content is 64%, room temperature storage 2 months, but thin up during use.The releasing agent of embodiment 7 preparations is sprayed on the metal die, can be at 160 ℃ of following 10 minutes film-formings.This film has lower surface energy.Utilize this releasing agent demoulding terpolymer EP rubber, can obtain glossiness is 5 ° rubber item, but once sprays the demoulding more than 20 times, and the rubber glossiness of each mould is constant.
Table 7
Figure B2009100517727D0000162
Embodiment 8
Under the room temperature, each composition in the table 8 is added in high speed dispersion still, stirred 20 minutes, it is mixed with the rotating speed of 1500rpm.Under the 1500rpm rotating speed, in 30 minutes, at the uniform velocity drip 31.6 gram deionized waters again; After dripping off, continue down to stir 30 minutes in the 200rpm rotating speed, promptly.This releasing agent solid content is 63%, room temperature storage 2 months, but thin up during use.The releasing agent of embodiment 8 preparations is sprayed on the metal die, can utilize this releasing agent demoulding terpolymer EP rubber at 160 ℃ of following 10 minutes film-formings, can obtain glossiness and be 1.8 ° rubber item, but once spray the demoulding more than 20 times, and the rubber glossiness of each mould is constant.
Table 8
Figure B2009100517727D0000171
Embodiment 9
Under the room temperature, each composition in the table 9 is added in high speed dispersion still, stirred 20 minutes, it is mixed with the rotating speed of 1500rpm.Under the 1500rpm rotating speed, in 30 minutes, at the uniform velocity drip 93.0 gram deionized waters again; After dripping off, continue down to stir 30 minutes in the 200rpm rotating speed, promptly.This releasing agent solid content is 5.8%, room temperature storage 3 months, but thin up during use.The releasing agent of embodiment 9 preparations is sprayed on the metal die, can utilize this releasing agent demoulding terpolymer EP rubber at 160 ℃ of following 10 minutes film-formings, can obtain glossiness and be 0.7 ° inferior light rubber item, but once spray the demoulding more than 20 times, and the rubber glossiness of each mould is constant.
Table 9
Figure B2009100517727D0000172
Embodiment 10
Preparation mixture A:
In the high speed dispersion still, add 3.0 gram Methyl Hydrogen Polysiloxane Fluids, 0.3 gram polysorbate-85,0.9 gram laureth-4,0.54 gram laureth-23, the 1500rpm rotating speed stirs and mixed in 20 minutes under the room temperature.Under the 1500rpm rotating speed, at the uniform velocity drip 95.86 gram water in 30 minutes; After dripping off, the 200rpm rotating speed continues down to stir 30 minutes, can obtain mixture A.
Preparation mixture B:
In the high speed dispersion still, add 0.6 gram silicon-dioxide, 0.1 gram stannous octoate, 0.5 gram thickening material
Figure B2009100517727D0000181
Under the 1500rpm rotating speed, at the uniform velocity drip 98.9 gram water in 10 minutes; After dripping off, the 200rpm rotating speed continues down to stir 10 minutes, can obtain mixture B.
It is even that mixture A and mixture B press 1: 1 mixed of mass ratio, be sprayed on 30 minutes film forming of 60 ℃ of curing on the metal die then, utilize this releasing agent demoulding EPDM rubber, can obtain glossiness and be 0.7 ° inferior light rubber item, but once spray the demoulding more than 20 times, and the rubber glossiness of each mould is constant.

Claims (25)

1. releasing agent, it contains: have the polysiloxane compound of three above si-h bonds, inferior light particle, emulsifying agent and water.
2. releasing agent as claimed in claim 1 is characterized in that: described polysiloxane compound with three above si-h bonds is to have in the following polymkeric substance of three above si-h bonds one or more: (1) is by the homopolymer that forms suc as formula the structural unit shown in the I; (2) by form suc as formula the structural unit shown in I and the formula II random, alternately, block and graft copolymer, this multipolymer is linearity or cyclocopolymer; And (3) are by one or more cross-linking copolymers that form in the polymkeric substance of above-mentioned (1) and (2);
Formula I formula II
Wherein, R 1Be C 1-C 10Alkoxyl group or C 1-C 10Alkyl, preferably be C 1-C 6Alkoxyl group or C 1-C 6Alkyl; R 2And R 3Independently be hydroxyl, C 1-C 10Alkoxyl group or C 1-C 10Alkyl, preferably independently be hydroxyl, C 1-C 6Alkoxyl group or C 1-C 6Alkyl; But R 2And R 3Be not hydroxyl simultaneously.
3. releasing agent as claimed in claim 1 is characterized in that: when described polysiloxane compound with three above si-h bonds was linearity or cross-linked polymer, its END CAPPED GROUP was by hydrogen, hydroxyl, C 1-C 10Alkoxyl group and C 1-C 10Alkyl in the silylation of one or more replacements.
4. releasing agent as claimed in claim 1 is characterized in that: described viscosity with polysiloxane compound of three above si-h bonds is 5-10000cst; That preferable is 5-5000cst; Viscosity records under 25 ℃.
5. releasing agent as claimed in claim 1 is characterized in that: the hydrogen richness on the si-h bond of described polysiloxane compound with three above si-h bonds is 0.10-1.63%; That better is 0.50-1.63%; Per-cent is mass percent.
6. releasing agent as claimed in claim 1 is characterized in that: described content with polysiloxane compound of three above si-h bonds is the 1-65% of releasing agent total mass; That better is 3-50%.
7. releasing agent as claimed in claim 1 is characterized in that: described inferior light particle is inorganic particulate and/or organic filler; The particle diameter of inferior light particle is 0.2-15.0 μ m, and that better is 0.5-10.0 μ m.
8. releasing agent as claimed in claim 1 is characterized in that: described inferior light particle is one or more in silicon dioxide granule, metal oxide particle, inorganic salt particle and the polymer particle; Described metal oxide particle is preferable is in TiO 2 particles, aluminium oxide particles, zinc oxide particle and the silver suboxide particle one or more; What described inorganic salt particle was preferable is calcium carbonate particles and/or barium sulfate particle; Described polymer particle is preferable is in polyethylene particles, particulate polyvinyl chloride, polypropylene particles, polystyrene particle and the polytetrafluoroethylparticle particle one or more.
9. releasing agent as claimed in claim 1 is characterized in that: the content of described inferior light particle is the 0.1-50.0% of releasing agent total mass, and that better is 0.5-30.0%.
10. releasing agent as claimed in claim 1 is characterized in that: described emulsifying agent is a nonionogenic tenside.
11. releasing agent as claimed in claim 10 is characterized in that: the HLB value of described nonionogenic tenside is 3-50.
12. releasing agent as claimed in claim 10 is characterized in that: described nonionogenic tenside is one or more in polyoxyethylene-type nonionogenic tenside, polyol-based non-ionic surfactant, alkylol amide type nonionogenic tenside and the organosilicon type nonionogenic tenside.
13. releasing agent as claimed in claim 1 is characterized in that: described emulsifying agent is one or more in following: polyoxyethylene (4) nonyl phenol 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-C 11Alkyl alcohol polyoxyethylene (6) ether, C 12-C 14Alkyl alcohol polyoxyethylene (7) ether, C 12-C 15Alkyl alcohol polyoxyethylene (12) ether, tridecyl alcohol polyoxyethylene (6) ether, tridecyl alcohol polyoxyethylene (10) ether, tridecyl alcohol polyoxyethylene (15) ether, hexadecyl alcohol polyoxyethylene (15) ether, hexadecyl alcohol polyoxyethylene (20) ether, hexadecyl alcohol polyoxyethylene (30) ether, different hexadecyl alcohol polyoxyethylene (20) ether, hexadecyl alcohol polyoxyethylene (12) ether, stearyl alcohol polyoxyethylene (12) ether, hexadecyl alcohol polyoxyethylene (30) ether, stearyl alcohol polyoxyethylene (30) ether, stearyl alcohol polyoxyethylene (20) ether, stearyl alcohol polyoxyethylene (40) ether, oleyl alcohol polyoxyethylene (20) ether, polyoxyethylene nonyl phenyl ethene (9) ether, polyoxyethylene nonyl phenyl ethene (10) ether, polyoxyethylene nonyl phenyl ethene (12) ether, polyoxyethylene nonyl phenyl ethene (30) ether, polyoxyethylene nonyl phenyl ethene (40) ether, polyoxyethylene nonyl phenyl ethene (70) ether, polyoxyethylene nonyl phenyl ethene (5) ether, polyoxyethylene nonyl phenyl ethene (8) ether, polyoxyethylene nonyl phenyl ethene (100) ether, coco amine polyoxyethylene (15) ether, ethylenediamine polyoxyethylene-polyoxytrimethylene-polyoxyethylene block polyether, two lauric acid polyoxyethylene glycol (8) esters, two lauric acid polyoxyethylene glycol (20) esters, stearic acid polyoxyethylene glycol (40) ester, stearic acid polyoxyethylene glycol (100) ester, polyoxyethylene (20) Zerol, polyoxyethylene (5) sorbitan monooleate, polyoxyethylene sorbitol acid anhydride trioleate and polyether-modified polysiloxane.
14. releasing agent as claimed in claim 1 is characterized in that: the content of described emulsifying agent is the 0.2-25.0% of releasing agent total mass, and that better is 0.25-20.00%.
15. releasing agent as claimed in claim 1 is characterized in that: the content of described water is the 20-98% of releasing agent total mass, and that better is 30-94%.
16. releasing agent as claimed in claim 1 is characterized in that: described releasing agent also contains one or more in following: silicoorganic compound, emulsion adjuvant and catalyzer; Described silicoorganic compound are the silicoorganic compound that contain silicon oh group and/or hydrolyzable formation silicon oh group.
17. releasing agent as claimed in claim 16 is characterized in that: described releasing agent contains mixture A and mixture B, wherein contains polysiloxane compound, emulsifying agent and the water with three above si-h bonds among the mixture A; Contain catalyzer and water among the mixture B; Inferior light particle independently exists among mixture A and/or the mixture B.
18. releasing agent as claimed in claim 17 is characterized in that: also contain silicoorganic compound and/or emulsion adjuvant among the described mixture A; Also contain emulsifying agent and/or emulsion adjuvant among the described mixture B.
19. releasing agent as claimed in claim 16 is characterized in that: the content of described silicoorganic compound is to be less than or equal to 50% of releasing agent total mass, and is better for being less than or equal to 30%; The content of described emulsion adjuvant is to be less than or equal to 8% of releasing agent total mass, and is better for being less than or equal to 5%; The content of described catalyzer is the 0.1-10.0% of releasing agent total mass, and that better is 0.1-8.0%; Above-mentioned content does not all comprise 0%.
20. releasing agent as claimed in claim 16 is characterized in that:
Described silicoorganic compound are one or more in following:
(1) silane compound shown in formula III (a), formula III (b) and formula III (c) and the formula III (d);
Figure F2009100517727C0000041
Formula III (a) formula III (b) formula III (c) formula III (d)
Wherein, W is-OR 4,
Figure F2009100517727C0000042
Or-O-N=CR 6R 7
Y 1, Y 2And Y 3Independently be-H ,-OH ,-R 8,-NR 9R 10,-R 11X ,-R 12SH ,-R 13OH ,-R 14NH,
Figure F2009100517727C0000043
-R 16OOC R 17C=CH 2Or
Figure F2009100517727C0000044
R 4Be C 1-C 16Alkyl;
R 5Be C 1-C 15Alkyl;
R 6And R 7Identical or inequality, independently be C 1-C 15Alkyl, but R 6And R 7Middle the total number of carbon atoms is less than or equal to 15;
R 9And R 10Identical or inequality, independently be hydrogen or C 1-C 16Alkyl, but R 9And R 10Middle the total number of carbon atoms is less than or equal to 16;
R 8, R 11, R 12, R 13And R 14Independently be C 1-C 16Alkyl;
R 15Be C 1-C 14Alkyl;
R 16And R 17Identical or inequality, independently be hydrogen or C 1-C 13Alkyl, but be not hydrogen simultaneously, and R 16And R 17Middle the total number of carbon atoms is less than or equal to 13;
R 18～R 20Identical or inequality, independently be C 1-C 14Alkyl, but R 18, R 19And R 20Middle the total number of carbon atoms is less than or equal to 16;
(2) the siloxanes ring compound shown in the formula IV;
Figure F2009100517727C0000051
Formula IV
Wherein, R 21And R 22Independently be hydroxyl or C 1-C 10Alkyl, R 21And R 22Be not hydroxyl simultaneously, m is the integer of 3-10;
And the siloxanes ol cpds shown in (3) formula V;
Figure F2009100517727C0000052
Formula V
Wherein, R 23～R 30Independently be hydroxyl, C 1-C 10Alkoxyl group or C 1-C 10Alkyl, preferably be C 1-C 8Alkyl; And R 26And R 27Be not hydroxyl simultaneously, R 23, R 24And R 25Be not hydroxyl simultaneously, R 28, R 29And R 30Be not hydroxyl simultaneously; Q is the integer of 0-1000; Number 〉=2 of hydroxyl and/or alkoxyl group in the siloxanes ol cpds shown in the formula V;
Described emulsion adjuvant is one or more in wetting ability auxiliary agent, thickening material, stablizer and the pH regulator agent;
Described catalyzer is amines catalyst and/or organo-metallic class catalyzer.
21. releasing agent as claimed in claim 20 is characterized in that: in the silicoorganic compound shown in formula III (b), formula III (c) and the formula III (d),
When W is-OR 4The time, Y 1, Y 2And Y 3Independently be OH ,-R 8,-NH 2,-R 11X ,-R 12SH ,-R 13OH ,-R 14NH,
Figure F2009100517727C0000053
-R 16OOCR 17C=CH 2Or
Figure F2009100517727C0000054
When W is
Figure F2009100517727C0000061
Or-O-N=CR 6R 7The time, Y 1, Y 2And Y 3Independently be OH or-R 8
Wherein, R 4～R 20Described with claim 20;
Described wetting ability auxiliary agent is a water-soluble high-molecular compound, one or more that better is in Polyvinylpyrolidone (PVP), polyoxyethylene glycol, polyvinyl alcohol and the polyvinyl methyl ether;
Described thickening material is a water-based thickener, one or more that better is in hydroxyalkyl cellulose, ether of cellulose and the polyacrylate dispersion class thickening material;
Described stablizer is thermo-stabilizer or freeze-thaw stabiliser;
Described pH regulator agent is that number-average molecular weight is less than or equal to one or more in 10000 acid, alkali and the salt, one or more that better is in acetate, ammoniacal liquor, volatile salt, yellow soda ash and the ammonium chloride;
Described amines catalyst is selected from one or more in following: triethylenediamine, two (dimethylaminoethyl ethers), dimethylcyclohexylamine, N-methyl bicyclic hexylamine, five methyl diethylentriamine, the pentamethyl-dipropylenetriamine, Tetramethyl Ethylene Diamine, 4-methyl-diaminopropane, 4-methyl hexamethylene diamine, N-methylmorpholine, N-ethylmorpholine, 2, the 2-dual-morpholinyl diethyl ether, the cocoa morpholine, the N-Methylimidazole, 1, the 2-methylimidazole, 1, the 4-lupetazin, N, the N-dimethyl benzylamine, three (dimethylaminopropyl) amine, triethylamine, N, N-dimethyl (hexadecyl) amine and tetramethyl-imido grpup dipropylamine;
Described organo-metallic class catalyzer is selected from one or more in following: dibutyl tin laurate, stannous octoate, two (dodecyl sulphur) dibutyl tin, dibutyltin diacetate, isocaprylic acid potassium, Potassium ethanoate, potassium oleate, isocaprylic acid lead, isocaprylic acid zinc, Phenylmercuric Acetate, tetrabutyl titanate and titanium isopropylate.
22. releasing agent as claimed in claim 16, it is characterized in that: described silicoorganic compound are one or more in following: γ-chloropropyl triethoxysilane, the chloropropyl methyldiethoxysilane, the bromopropyl methyldiethoxysilane, tetraethoxysilane, four n-butoxy silane, methyldiethoxysilane, methyltrimethoxy silane, Union carbide A-162, ethyl triethoxysilane, dimethyldiethoxysilane, propyl trimethoxy silicane, allyltriethoxysilane, methylethyl dimethoxy silane, phenyl triethoxysilane, phenyl tripropoxy silane, phenyl three isopropoxy silane, phenyl three n-butoxy silane, dimethoxydiphenylsilane, the phenylbenzene diethoxy silane, aminomethyl phenyl dimethoxy silane, the aminomethyl phenyl diethoxy silane, the ethylphenyl diethoxy silane, diethyl phosphoric acid ester ethyl triethoxysilane, vinyltriethoxysilane, vinyl three ('beta '-methoxy oxyethyl group) silane, γ-An Bingjisanyiyangjiguiwan, γ-(β-aminoethyl)-aminopropyl methyl dimethoxysilane, γ-(β-aminoethyl)-aminopropyl trimethoxysilane, γ-(beta-hydroxyethyl aminoethyl)-aminopropyl methyl dimethoxysilane, N, N-diethyl-γ-amine propyl trimethoxy silicane, N-methyl-3-aminopropyl trimethoxysilane, 3-cyclohexyl-aminopropyl methyl dimethoxysilane, γ-glycidyl ether oxygen base propyl trimethoxy silicane, γ-glycidyl ether oxygen base propyl-triethoxysilicane, γ-glycidyl ether oxygen base propyl group methyldiethoxysilane, γ-methacryloxypropyl trimethoxy silane, γ-methacryloxy methyl dimethoxysilane, 3-urea groups propyl trimethoxy silicane, gamma-mercaptopropyltriethoxysilane, γ-mercaptopropyl trimethoxysilane, anilinomethyl triethoxysilane, the hydroxyethyl dimethyl phenyl silane, the dihydroxypropyl dimethylsilane, the tetrem acyloxy silane, methyl triacetoxysilane, methyl three propionyloxy silane, the triphenyl acetoxysilane, the vinyl tributanoximo silane, methyl tri acetylacetonate oximino silane, the chloropropyl tributanoximo silane, decamethylcyclopentaandoxane, the hydroxyl polydimethylsiloxane, triethoxysilicane alkanisation polydimethylsiloxane, vinyl-dimethyl TMOS polydimethylsiloxane, methylethyl methoxy silane polydimethylsiloxane and vinyl-dimethyl TMOS PSI.
23. as each described releasing agent in the claim 1～22, it is characterized in that: the pH of described releasing agent is 3-7.
24. as each described releasing agent in the claim 1～23, it is characterized in that: when not containing thickening material in the releasing agent, the solid content of releasing agent is 40-75%; When containing thickening material, the solid content of releasing agent is 1-40%; Per-cent is mass percent.
25. as the application of each described releasing agent in the claim 1～24 in preparation sub-smooth type rubber item, sub-smooth type plastics or sub-smooth type composite product.
CN2009100517727A 2009-05-22 2009-05-22 Release agent and application thereof Pending CN101892115A (en)

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