CN107353688A - A kind of photocureable coating anti-soil auxiliary agent and its application - Google Patents
A kind of photocureable coating anti-soil auxiliary agent and its application Download PDFInfo
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- CN107353688A CN107353688A CN201710563517.5A CN201710563517A CN107353688A CN 107353688 A CN107353688 A CN 107353688A CN 201710563517 A CN201710563517 A CN 201710563517A CN 107353688 A CN107353688 A CN 107353688A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1606—Antifouling paints; Underwater paints characterised by the anti-fouling agent
- C09D5/1637—Macromolecular compounds
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- 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/91—Polymers modified by chemical after-treatment
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- 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
- C08G77/38—Polysiloxanes modified by chemical after-treatment
- C08G77/382—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon
- C08G77/388—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon containing nitrogen
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- 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
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/002—Dendritic macromolecules
- C08G83/005—Hyperbranched macromolecules
- C08G83/006—After treatment of hyperbranched macromolecules
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/0427—Coating with only one layer of a composition containing a polymer binder
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1687—Use of special additives
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2333/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
- C08J2333/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C08J2333/10—Homopolymers or copolymers of methacrylic acid esters
- C08J2333/12—Homopolymers or copolymers of methyl methacrylate
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2475/04—Polyurethanes
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Abstract
The invention discloses a kind of photocureable coating anti-soil auxiliary agent and its application；The auxiliary agent is specially the fluorine silicon light-cured type hyper-branched polyester containing acrylate and maleate structure of following structure：Under ultraviolet light, acrylate and maleate double bond in the auxiliary agent structure can crosslink with the acrylate in coating and the double bond of acrylate monomer is solidified to form the excellent coating of hydrophobic oleophobic performance, so as to have excellent antifouling effect.
Description
Technical field
The invention belongs to UV-curing chemoprevention dirt field of material technology, and in particular to a kind of photocureable coating anti-soil auxiliary agent
And its application；More particularly, it is to be related to the fluorine silicon light-cured type hyper-branched polyester containing acrylate and maleate structure
Preparation method and its application as anti-soil auxiliary agent in ultraviolet-curing paint.
Background technology
Ultraviolet-curing paint (UV coating) because its efficiently, energy-saving and environmental protection, economic dispatch advantage, and its film have it is excellent
The features such as different resistance to marring, chemical resistance, high glossiness, it is widely used to mobile phone, tablet personal computer, optical lens, machine
The plastic basis material surface stiffened of the electronic products such as control panel, GPS panels, and improve the hardness of the plastic basis material, transparency, wear-resisting
The performances such as consumption, shock resistance.But during the use of these electronic products, its screen surface easily fingerprints, skin oil
Fat, ink marks, etc. spot, and spot is difficult to remove, and so as to reduce surface transparency, have impact on practicality and attractive in appearance.Especially
In recent years, the popularization based on 3C Products such as touch-screen type mobile phone, computer, TVs, the hardness except requiring coating are transparent, wear-resisting
It is even more that higher requirement is proposed to the antifouling property of coating outside consumption.
With the rise and development of fluorine chemistry, people gradually recognize the property of fluorochemical/resin.Fluorine element
With highest electronegativity, it is most short with the C-F keys bond distance of carbon atom formation and polarizability is low, therefore in fluoropolymer chain
Fluorine atom is mutually exclusive, is densely wrapped on the outside of main chain and forms fine and close helical form screen layer.In addition, the bond energy of C-F keys
Higher, general ultraviolet irradiation is difficult to make C-F keys be broken and destroy resin structure.Exactly this special design feature assigns
The excellent property such as fluorine resin low surface tension, water-oil resistance, chemical stability and weatherability.However, containing fluorination
There is the shortcomings that cost is high in compound, therefore using cheap, and the relatively low organo-silicon compound of surface energy with containing fluorination
Compound is cooperateed with to reach reduction surface tension, hydrophobic oleophobic effect is improved, so as to realize that the method for functions is to cause people
Common concern.
Chinese patent CN103665022A discloses a kind of anti-soil auxiliary agent of novel perfluoropolyether alkoxysilane, but the auxiliary agent
Synthesis uses two-step synthesis method, and the first step uses flammable solvent ether, with expensive PFPE acyl fluorides and allyl amine
Reaction obtains pi-allyl Perfluoropolyether amide, and generated time is longer, also needs removing solvent just to carry out second step reaction.The
The reaction of two steps needs more expensive platinum catalyst, using above-mentioned product pi-allyl using the larger low boiling point solvent dichloromethane of toxicity
Perfluoropolyether amide reacts with trimethoxy silane, reaction time length, but also need to carry out removing solvent.But while by so
Complicated building-up process, the expensive final product of gained are the chemical combination with perfluoropolyether group and trimethoxy silane
Thing, it does not have photocurable group, therefore photo-crosslinking can not occur with the resin in photocureable coating system and monomer.
In addition because the product has trimethoxy silane structure, hydrolabil, facile hydrolysis, therefore problems of stability in storage be present.
On the other hand, the patent does not provide the using effect that synthetic product is used in anti-pollution paint yet.
Chinese patent CN104755514A discloses one kind and can be used for antifouling coating composition, and it gathers comprising fluorine highly -branched
Compound and siloxane oligomer.But fluorine-containing hyper branched polymer and siloxane oligomer are both needed to be manufactured separately, and the former also needs
Carry out desolventizing and vacuum drying step, complex operation.The preparation of siloxane oligomer is to pass through methacryloxypropyl
Preparation is hydrolyzed in triethoxysilane in ethanol solution under acid condition, although preparation technology is simple, be difficult to obtain
The oligomer of estimated molecular weight, if misoperation, crosslinking can be produced.In addition, the fluorine-containing hyper branched polymer that the invention is mentioned
Simply side chain contains the random bipolymer of more officials of double bond, and its fluorinated volume is relatively low, because its fluorine raw material simply contains 6
2- (perfluoro hexyl) ethyl propylene acid esters of fluorine atom, fluorine-containing groupses are shorter, therefore hydrophobic oleophobic effect is low, and the polymer
The structural regularity of dissaving polymer is not had, therefore viscosity is higher, can cause the phase with other components in coating system
Capacitive is poor and influences film effect.
The content of the invention
Overspend it is an object of the invention to provide a kind of containing acrylate and the fluorine silicon light-cured type of maleate structure
Change the defects of polyester anti-soil dirt auxiliary agent is to overcome prior art, effectively improve the hydrophobic of transparent plastic substrate surface light solidifying coating
Oleophobic performance, to reach excellent antifouling effect.
The purpose of the present invention is achieved through the following technical solutions：
The present invention relates to a kind of auxiliary agent being used in photocureable coating, the auxiliary agent is to contain acrylate and maleate
The fluorine silicon light-cured type hyper-branched polyester of structure；Its structure is as follows：
；Wherein R1, R3Represent alkyl of the carbon number as 2-5, R2, R4Represent alkylidene of the carbon number as 2-5；M=35
~80；N=2,3,4 ..., wherein n=3 composition accounts for more than 60%.More preferably n is any several, the wherein n=3 in 2~10
Composition account for more than 60%.
Under ultraviolet light and in the presence of light trigger, the fluorine of the invention containing acrylate and maleate structure
Silicon light-cured type hyper-branched polyester can occur polymerisation with the acrylic resin in ultraviolet-curing paint and monomer and be crosslinked
Solidification, forms super-hydrophobic oleophobic film on plastic basis material surface.
Preferably, the fluorine silicon light-cured type hyper-branched polyester containing acrylate and maleate structure is to pass through bag
Include what the methods of following steps was prepared：
S1, under nitrogen protection, using toluene as solvent, using dibutyl tin laurate as catalyst, MEHQ
For polymerization inhibitor, diisocyanate is with crylic acid hydroxy ester with the rate of charge of mol ratio 1: 1, and at 70~75 DEG C, reaction 3~4 is small
When, it is isocyanate groups to obtain one end, and one end is the compound of acrylic double bond；
S2, the double carbon hydroxyl modification silicon for adding into step S1 reaction solution identical with crylic acid hydroxy ester molal quantity
Oil, reacted 3~4 hours at 75~80 DEG C and obtain the modified silicon oil that one end is hydroxyl, one end is acrylic double bond；
S3, toluene, perfluoroalkyl ethanol, maleic anhydride, catalyst pyrovinic acid are added into step S2 reaction solution,
React that to obtain within 7~8 hours having one end be unsaturated carboxyl, one end is changing for acrylate unsaturated double-bond at 95~100 DEG C
The mixture of the maleic mono-ester of property silicone oil and perfluoroalkyl；
S4, hyperbranched poly ester polyol, MEHQ, pyrovinic acid and first are added into step S3 reaction solution
Benzene, back flow reaction 7~8 hours at 115~120 DEG C, obtain the fluorine silicon photocuring containing acrylate and maleate structure
The toluene solution of type hyper-branched polyester.
In the present invention, useTo replace the structure of hyperbranched poly ester polyol.
Preferably, the crylic acid hydroxy ester described in step S1 is hydroxy-ethyl acrylate, hydroxypropyl acrylate, acrylic acid hydroxyl fourth
One kind in ester.Preferably hydroxy-ethyl acrylate.
Preferably, the diisocyanate described in step S1 is hexamethylene diisocyanate, IPDI
In one kind.Preferably hexamethylene diisocyanate.
Preferably, (i.e. with two hydroxyls, and hydroxyl is not directly to connect to double carbon hydroxyl modification silicone oil described in step S2
Onto silicon atom, but it is connected to by alkylidene on silicon atom) for two end carbon hydroxyl modification silicone oil, (i.e. two hydroxyls are distinguished
Positioned at the both ends of silicone oil structure, be connected to by alkylidene on silicon atom), (two hydroxyls are located at the double carbon hydroxy silicon oils in single end
Single-ended, alternatively referred to as single glycol modified silicone oil in end of silicone oil structure) in one kind.The double carbon hydroxyl silicon in more preferably single end
Oil.
Preferably, the mole of the double carbon hydroxy silicon oils in single end is 3000~6000.
Preferably, the perfluoroalkyl ethanol in step S3 is the mixing of the perfluoroalkyl ethanol (TEOH-N) of different fluorinated volumes
Thing, its molecular formula are as follows：
F(CF2CF2)nCH2CH2OH, n=2,3,4 ...；Wherein n=3 composition accounts for more than 60%.Contain 13 fluorine atoms
Perfluoroalkyl ethanol be main component.
Preferably, the addition of perfluoroalkyl ethanol is the addition based on crylic acid hydroxy ester in step S1 in step S3
The ratio between amount, the two molal quantity are 9: 1~1: 9.Preferably 8: 2~2: 8.Most preferably 7: 3~5: 5.The actual representative of the ratio contains
Fluorine part and the ratio of siliceous part.
Preferably, the molal quantity of maleic anhydride is that the molal quantity of double carbon hydroxy silicon oils rubs with perfluoroalkyl ethanol in step S3
That number sum.
Preferably, in step S4 the hydroxyl moles of hyperbranched poly ester polyol be double carbon hydroxy silicon oils molal quantity with it is complete
Fluoroalkyl ethanol molal quantity sum, the i.e. molal quantity equal to maleic anhydride.
The fluorine silicon light-cured type hyper-branched polyester of acrylate and maleate structure in the present invention, its architectural feature exist
In：Fluorine-containing and siliceous part is located at the end of hyper-branched polyester, similar to the claw distal portion of octopus, and fluorine silicon segment
Surface energy is low, so fluorine silicon segment is very easy to move to the surface of coating, the low-down surface of surface energy is formed, so having
Excellent hydrophobic oleophobic and antifouling effect.Because dissaving structure, contain acrylate and the horse that can much carry out photocuring
Carry out acid esters unsaturated double-bond, can be sent out with the acrylic resin in photocureable coating and acrylate monomer under illumination condition
The third contact of a total solar or lunar eclipse is crosslinked.So the fluorine silicon segment of these hydrophobic oleophobics is securely fixed on coating, so that coating has persistently
Antifouling effect.
Compared with prior art, the fluorine silicon light containing acrylate and maleate structure of design synthesis is consolidated in the present invention
Change type hyper-branched polyester has dissaving structure, so degree of functionality is high.And the light-cured type hyper-branched polyester has many tables
The low fluorine silicon segment of face energy, their badge fish claws are equally located at end.This structure makes acrylate and maleate structure
Fluorine silicon light-cured type hyper-branched polyester when being applied in photocureable coating, can be fast with acrylate and acrylate monomer
Fast crosslinking curing forms the network of densification, and fluorine silicon segment dense distribution is in coating surface, so as to effectively improve dredging for coating
Water oleophobic performance and reach the effect of anti-soil.Because the fluorine silicon light-cured type hyperbranched poly of the acrylate and maleate structure
Ester forms cross-linked network with the resin in coating system and monomer after photocuring, therefore, even if fluorine silicon segment part is distributed in
Coating surface, it will not be also removed because of external force friction or solvent wiping, lose antifouling property.
In addition, the raw material for preparing the acrylate and the fluorine silicon light-cured type hyper-branched polyester of maleate structure are cheap
It is easy to get, it is simple using the synthesis technique of one kettle way, technique, it is easy to accomplish industrialized production.In addition, it is not necessary that extra removing is molten
The aftertreatment technologys such as agent, directly it can be used in the form of a solution as anti-soil auxiliary agent.
Brief description of the drawings
The detailed description made by reading with reference to the following drawings to non-limiting example, further feature of the invention,
Objects and advantages will become more apparent upon：
Fig. 1 is the red of the fluorine silicon light-cured type hyper-branched polyester containing acrylate and maleate structure of embodiment 1
External spectrum analysis chart.
Embodiment
The fluorine silicon light-cured type for describing acrylate of the present invention and maleate structure in detail with embodiment below is hyperbranched
The preparation method of polyester and its application as anti-soil auxiliary agent in ultraviolet-curing paint.But it should be noted that the present invention
Embodiment be not limited to following examples, other are any without departing from the principle of the invention and the lower any forms carried out of design
Modification, change, replacement or simplification, all the present invention protection among.
The preparation method of acrylate and the fluorine silicon light-cured type hyper-branched polyester of maleate structure：
A perfluoroalkyl ethanol (TEOH-N) sold using Fuxin Heng Tong fluorine chemistry Co., Ltd.Wherein each component contains
Amount is as follows：
Embodiment 1
Into 250 milliliters of four-hole bottles equipped with magnetic agitation, coil condenser, thermometer and water knockout drum, in nitrogen
Under protection, add 3.36 grams of hexamethylene diisocyanates (0.02mol), hydroxy-ethyl acrylate 2.32 grams (0.02mol), 10 grams
Toluene and 0.028 gram of MEHQ, 0.01 gram of dibutyl tin laurate, at 70 DEG C, react 3 hours.Then add
60.0 grams of single-ended double carbon hydroxy silicon oils (molecular weight 3000,0.02mol), 0.028 gram of MEHQ, 0.067 gram of two bay
Sour dibutyl tin, reacted 3 hours at 80 DEG C.Then 40 grams of toluene of addition, 6.54 grams of maleic anhydrides (0.0667mol), 24.16
Gram perfluoroalkyl ethanol (hydroxyl value 108.4mgKOH/g, 0.0466mol), 0.32 gram of pyrovinic acid, 0.028 gram of para hydroxybenzene first
Ether, reacted 7 hours at 95 DEG C.Then add 6.61 grams of hyperbranched poly ester polyols (hydroxyl value 565.9mgKOH/g,
0.0667mol-OH), 0.057 gram of MEHQ, 0.32 gram of pyrovinic acid and 20 grams of toluene, are warming up to 115 DEG C next time
Stream reaction 7 hours.After reaction terminates reaction, a small amount of insoluble matter is filtered to remove while hot, appropriate ethyl acetate is added and is diluted to 20%
Solid content.
To products therefrom, after removing solvent, after 40 degree are dried in vacuo 12 hours, gained sample carries out infrared spectrum analysis
(Fig. 1).It is the stretching vibration absworption peak for coming from C=O in hyper-branched polyester and acrylate, maleate at 1720cm-1；
1630cm-1 is the stretching vibration absworption peak for coming from C=C in acrylate and maleic acid diester；1521cm-1 is from amino
The combination absworption peak of N-H flexural vibrations and C-N stretching vibrations in formic acid ester structure；1410cm-1 be come from acrylate=
C-H in-plane bending vibration absworption peaks；1251cm-1 and 795cm-1 is the vibration absorption peak for coming from Si-C structures；1198cm-1
For the stretching vibration absworption peak from C-F keys；1146cm-1 is the vibration absorption peak of the C-O-C in ester；1016cm-1 is next
From in the vibration absorption peak of Si-O-Si structures.Therefore infrared spectrum analysis learns that product is acrylate and maleate structure
Fluorine silicon light-cured type hyper-branched polyester.
Embodiment 2
Into 250 milliliters of four-hole bottles equipped with magnetic agitation, coil condenser, thermometer and water knockout drum, in nitrogen
Under protection, 2.52 grams of hexamethylene diisocyanates (0.015mol), hydroxy-ethyl acrylate 1.74 grams of (0.015mol), 10 are added
Gram toluene and 0.021 gram of MEHQ, 0.01 gram of dibutyl tin laurate, at 70 DEG C, react 3 hours.Then plus
Enter 75.0 grams of single-ended double carbon hydroxy silicon oils (molecular weight 5000,0.015mol), 0.021 gram of MEHQ, 0.08 gram of February
Dilaurylate, reacted 3 hours at 80 DEG C.Then 40 grams of toluene of addition, 4.90 grams of maleic anhydrides (0.05mol), 18.11
Gram perfluoroalkyl ethanol (hydroxyl value 108.4mgKOH/g, 0.035mol), 0.24 gram of pyrovinic acid, 0.021 gram of para hydroxybenzene first
Ether, reacted 7 hours at 95 DEG C.Then add 4.96 grams of hyperbranched poly ester polyols (hydroxyl value 565.9mgKOH/g,
0.05mol-OH), 0.043 gram of MEHQ, 0.24 gram of pyrovinic acid and 20 grams of toluene, are warming up at 115 DEG C and flow back
Reaction 7 hours.After reaction terminates reaction, a small amount of insoluble matter is filtered to remove while hot, and adding appropriate ethyl acetate, to be diluted to 20% solid
Content.
Embodiment 3
Into 250 milliliters of four-hole bottles equipped with magnetic agitation, coil condenser, thermometer and water knockout drum, in nitrogen
Under protection, 2.18 grams of hexamethylene diisocyanates (0.013mol), hydroxy-ethyl acrylate 1.51 grams of (0.013mol), 10 are added
Gram toluene and 0.018 gram of MEHQ, 0.005 gram of dibutyl tin laurate, at 70 DEG C, react 3 hours.Then plus
Enter 78.0 grams of single-ended double carbon hydroxy silicon oils (molecular weight 6000,0.013mol), 0.018 gram of MEHQ, 0.082 gram of February
Dilaurylate, reacted 3 hours at 80 DEG C.Then 40 grams of toluene, 4.25 grams of maleic anhydrides (0.0433mol) are added,
15.70 grams of perfluoroalkyl ethanols (hydroxyl value 108.4mgKOH/g, 0.0303mol), 0.21 gram of pyrovinic acid, 0.018 gram to hydroxyl
Base methyl phenyl ethers anisole, reacted 7 hours at 95 DEG C.Then add 4.30 grams of hyperbranched poly ester polyols (hydroxyl value 565.9mgKOH/g,
0.0433mol-OH), 0.037 gram of MEHQ, 0.21 gram of pyrovinic acid and 20 grams of toluene, are warming up to 115 DEG C next time
Stream reaction 7 hours.After reaction terminates reaction, a small amount of insoluble matter is filtered to remove while hot, appropriate ethyl acetate is added and is diluted to 20%
Solid content.
Embodiment 4
Into 250 milliliters of four-hole bottles equipped with magnetic agitation, coil condenser, thermometer and water knockout drum, in nitrogen
Under protection, 3.87 grams of hexamethylene diisocyanates (0.023mol), hydroxy-ethyl acrylate 2.67 grams of (0.023mol), 10 are added
Gram toluene and 0.033 gram of MEHQ, 0.006 gram of dibutyl tin laurate, at 70 DEG C, react 3 hours.Then plus
Enter 69.0 grams of single-ended double carbon hydroxy silicon oils (molecular weight 3000,0.023mol), 0.033 gram of MEHQ, 0.076 gram of February
Dilaurylate, reacted 3 hours at 80 DEG C.Then 40 grams of toluene, 5.70 grams of maleic anhydrides (0.0575mol) are added,
17.86 grams of perfluoroalkyl ethanols (hydroxyl value 108.4mgKOH/g, 0.0345mol), 0.28 gram of pyrovinic acid, 0.033 gram to hydroxyl
Base methyl phenyl ethers anisole, reacted 7 hours at 95 DEG C.Then add 3.47 grams of hyperbranched poly ester polyols (hydroxyl value 565.9mgKOH/g,
0.0575mol-OH), 0.04 gram of MEHQ, 0.17 gram of pyrovinic acid and 20 grams of toluene, are warming up to 115 DEG C next time
Stream reaction 7 hours.After reaction terminates reaction, a small amount of insoluble matter is filtered to remove while hot, appropriate ethyl acetate is added and is diluted to 20%
Solid content.
Embodiment 5
Into 250 milliliters of four-hole bottles equipped with magnetic agitation, coil condenser, thermometer and water knockout drum, in nitrogen
Under protection, 2.69 grams of hexamethylene diisocyanates (0.016mol), hydroxy-ethyl acrylate 1.86 grams of (0.016mol), 10 are added
Gram toluene and 0.023 gram of MEHQ, 0.005 gram of dibutyl tin laurate, at 70 DEG C, react 3 hours.Then plus
Enter 80.0 grams of single-ended double carbon hydroxy silicon oils (molecular weight 5000,0.016mol), 0.023 gram of MEHQ, 0.085 gram of February
Dilaurylate, reacted 3 hours at 80 DEG C.Then 40 grams of toluene of addition, 3.92 grams of maleic anhydrides (0.04mol), 12.42
Gram perfluoroalkyl ethanol (hydroxyl value 108.4mgKOH/g, 0.024mol), 0.19 gram of pyrovinic acid, 0.023 gram of para hydroxybenzene first
Ether, reacted 7 hours at 95 DEG C.Then add 3.97 grams of hyperbranched poly ester polyols (hydroxyl value 565.9mgKOH/g,
0.04mol-OH), 0.045 gram of MEHQ, 0.19 gram of pyrovinic acid and 20 grams of toluene, are warming up at 115 DEG C and flow back
Reaction 7 hours.After reaction terminates reaction, a small amount of insoluble matter is filtered to remove while hot, and adding appropriate ethyl acetate, to be diluted to 20% solid
Content.
Embodiment 6
Into 250 milliliters of four-hole bottles equipped with magnetic agitation, coil condenser, thermometer and water knockout drum, in nitrogen
Under protection, 2.52 grams of hexamethylene diisocyanates (0.015mol), hydroxy-ethyl acrylate 1.74 grams of (0.015mol), 10 are added
Gram toluene and 0.021 gram of MEHQ, 0.005 gram of dibutyl tin laurate, at 70 DEG C, react 3 hours.Then plus
Enter 90.0 grams of single-ended double carbon hydroxy silicon oils (molecular weight 6000,0.015mol), 0.021 gram of MEHQ, 0.094 gram of February
Dilaurylate, reacted 3 hours at 80 DEG C.Then 40 grams of toluene, 3.60 grams of maleic anhydrides (0.0375mol) are added,
11.64 grams of perfluoroalkyl ethanols (hydroxyl value 108.4mgKOH/g, 0.0225mol), 0.18 gram of pyrovinic acid, 0.033 gram to hydroxyl
Base methyl phenyl ethers anisole, reacted 7 hours at 95 DEG C.Then add 3.72 hyperbranched poly ester polyols (hydroxyl value 565.9mgKOH/g,
0.0375mol-OH), 0.04 gram of MEHQ, 0.18 gram of pyrovinic acid and 20 grams of toluene, are warming up to 115 DEG C next time
Stream reaction 7 hours.After reaction terminates reaction, a small amount of insoluble matter is filtered to remove while hot, appropriate ethyl acetate is added and is diluted to 20%
Solid content.
Embodiment 7
Into 250 milliliters of four-hole bottles equipped with magnetic agitation, coil condenser, thermometer and water knockout drum, in nitrogen
Under protection, 4.21 grams of hexamethylene diisocyanates (0.025mol), hydroxy-ethyl acrylate 2.91 grams of (0.025mol), 10 are added
Gram toluene and 0.036 gram of MEHQ, 0.007 gram of dibutyl tin laurate, at 70 DEG C, react 3 hours.Then plus
Enter 75.0 grams of single-ended double carbon hydroxy silicon oils (molecular weight 3000,0.025mol), 0.036 gram of MEHQ, 0.082 gram of February
Dilaurylate, reacted 3 hours at 80 DEG C.Then 40 grams of toluene of addition, 4.90 grams of maleic anhydrides (0.05mol), 12.94
Gram perfluoroalkyl ethanol (hydroxyl value 108.4mgKOH/g, 0.025mol), 0.24 gram of pyrovinic acid, 0.033 gram of para hydroxybenzene first
Ether, reacted 7 hours at 95 DEG C.Then add 4.96 grams of hyperbranched poly ester polyols (hydroxyl value 565.9mgKOH/g,
0.05mol-OH), 0.07 gram of MEHQ, 0.24 gram of pyrovinic acid and 20 grams of toluene, are warming up at 115 DEG C and flow back
Reaction 7 hours.After reaction terminates reaction, a small amount of insoluble matter is filtered to remove while hot, and adding appropriate ethyl acetate, to be diluted to 20% solid
Content.
Embodiment 8
Into 250 milliliters of four-hole bottles equipped with magnetic agitation, coil condenser, thermometer and water knockout drum, in nitrogen
Under protection, 2.86 grams of hexamethylene diisocyanates (0.017mol), hydroxy-ethyl acrylate 1.97 grams of (0.017mol), 10 are added
Gram toluene and 0.024 gram of MEHQ, 0.005 gram of dibutyl tin laurate, at 70 DEG C, react 3 hours.Then plus
Enter 85.0 grams of single-ended double carbon hydroxy silicon oils (molecular weight 5000,0.017mol), 0.023 gram of MEHQ, 0.085 gram of February
Dilaurylate, reacted 3 hours at 80 DEG C.Then 40 grams of toluene of addition, 3.33 grams of maleic anhydrides (0.034mol), 8.80
Gram perfluoroalkyl ethanol (hydroxyl value 108.4mgKOH/g, 0.017mol), 0.16 gram of pyrovinic acid, 0.024 gram of para hydroxybenzene first
Ether, reacted 7 hours at 95 DEG C.Then add 3.37 grams of hyperbranched poly ester polyols (hydroxyl value 565.9mgKOH/g,
0.034mol-OH), 0.048 gram of MEHQ, 0.16 gram of pyrovinic acid and 20 grams of toluene, are warming up to 115 DEG C next time
Stream reaction 7 hours.After reaction terminates reaction, a small amount of insoluble matter is filtered to remove while hot, appropriate ethyl acetate is added and is diluted to 20%
Solid content.
Embodiment 9
Into 250 milliliters of four-hole bottles equipped with magnetic agitation, coil condenser, thermometer and water knockout drum, in nitrogen
Under protection, 2.52 grams of hexamethylene diisocyanates (0.015mol), hydroxy-ethyl acrylate 1.74 grams of (0.015mol), 10 are added
Gram toluene and 0.021 gram of MEHQ, 0.005 gram of dibutyl tin laurate, at 70 DEG C, react 3 hours.Then plus
Enter 90.0 grams of single-ended double carbon hydroxy silicon oils (molecular weight 6000,0.015mol), 0.021 gram of MEHQ, 0.094 gram of February
Dilaurylate, reacted 3 hours at 80 DEG C.Then 40 grams of toluene of addition, 2.94 grams of maleic anhydrides (0.03mol), 7.76
Gram perfluoroalkyl ethanol (hydroxyl value 108.4mgKOH/g, 0.015mol), 0.144 gram of pyrovinic acid, 0.021 gram of para hydroxybenzene first
Ether, reacted 7 hours at 95 DEG C.Then 2.97 hyperbranched poly ester polyols (hydroxyl value 565.9mgKOH/g, 0.03mol- are added
OH), 0.04 gram of MEHQ, 0.144 gram of pyrovinic acid and 20 grams of toluene, it is small to be warming up to back flow reaction 7 at 115 DEG C
When.After reaction terminates reaction, a small amount of insoluble matter is filtered to remove while hot, appropriate ethyl acetate is added and is diluted to 20% solid content.
Comparative example 1
Into 250 milliliters of four-hole bottles equipped with magnetic agitation, coil condenser, thermometer and water knockout drum, in nitrogen
Under protection, 40 grams of toluene, 14.71 grams of maleic anhydrides (0.15mol) are added, (hydroxyl value is for 77.63 grams of perfluoroalkyl ethanols
108.4mgKOH/g, 0.15mol), 0.72 gram of pyrovinic acid, 0.064 gram of MEHQ, reacted 7 hours at 95 DEG C.So
14.87 grams of hyperbranched poly ester polyols (hydroxyl value 565.9mgKOH/g, 0.15mol-OH), 0.21 gram of para hydroxybenzene first are added afterwards
Ether, 0.72 gram of pyrovinic acid and 30 grams of toluene, are warming up to back flow reaction 7 hours at 115 DEG C.After reaction terminates reaction, while hot
A small amount of insoluble matter is filtered to remove, appropriate ethyl acetate is added and is diluted to 20% solid content.
Comparative example 2
Into 250 milliliters of four-hole bottles equipped with magnetic agitation, coil condenser, thermometer and water knockout drum, in nitrogen
Under protection, add 5.05 grams of hexamethylene diisocyanates (0.03mol), hydroxy-ethyl acrylate 3.48 grams (0.03mol), 10 grams
Toluene and 0.043 gram of MEHQ, 0.008 gram of dibutyl tin laurate, at 70 DEG C, react 3 hours.Then add
90 grams of single-ended double carbon hydroxy silicon oils (molecular weight 3000,0.025mol), 0.099 gram of MEHQ, 0.043 gram of tin dilaurate
Dibutyl tin, reacted 3 hours at 80 DEG C.Then 40 grams of toluene, 2.94 grams of maleic anhydrides (0.03mol), 0.144 gram of first are added
Base sulfonic acid, 0.043 gram of MEHQ, reacted 7 hours at 95 DEG C.Then 2.97 grams of hyperbranched poly ester polyols are added
(hydroxyl value 565.9mgKOH/g, 0.03mol-OH), 0.085 gram of MEHQ, 0.144 gram of pyrovinic acid and 20 grams
Toluene, it is warming up to back flow reaction 7 hours at 115 DEG C.After reaction terminates reaction, a small amount of insoluble matter is filtered to remove while hot, is added suitable
Amount ethyl acetate is diluted to 20% solid content.
Comparative example 3
Into 250 milliliters of four-hole bottles equipped with magnetic agitation, coil condenser, thermometer and water knockout drum, in nitrogen
Under protection, 3.87 grams of hexamethylene diisocyanates (0.023mol), hydroxy-ethyl acrylate 2.67 grams of (0.023mol), 10 are added
Gram toluene and 0.033 gram of MEHQ, 0.006 gram of dibutyl tin laurate, at 70 DEG C, react 3 hours.Then plus
Enter 69.0 grams of double end carbon hydroxyl modification silicone oil (molecular weight 3000,0.023mol), 0.033 gram of MEHQ, 0.076 gram
Dibutyl tin laurate, reacted 3 hours at 80 DEG C.Then 40 grams of toluene, 5.70 grams of maleic anhydrides are added
(0.0575mol), 17.86 grams of perfluoroalkyl ethanols (hydroxyl value 108.4mgKOH/g, 0.0345mol), 0.28 gram of pyrovinic acid,
0.033 gram of MEHQ, reacted 7 hours at 95 DEG C.Then adding 3.47 grams of hyperbranched poly ester polyols, (hydroxyl value is
565.9mgKOH/g, 0.0575mol-OH), 0.04 gram of MEHQ, 0.17 gram of pyrovinic acid and 20 grams of toluene, rise
Temperature was to back flow reaction at 115 DEG C 7 hours.After reaction terminates reaction, a small amount of insoluble matter is filtered to remove while hot, adds appropriate acetic acid second
Ester is diluted to 20% solid content.
Comparative example 4
Into 250 milliliters of four-hole bottles equipped with magnetic agitation, coil condenser, thermometer and water knockout drum, in nitrogen
Under protection, 5.56 grams of hexamethylene diisocyanates (0.033mol), hydroxy-ethyl acrylate 3.83 grams of (0.033mol), 10 are added
Gram toluene and 0.047 gram of MEHQ, 0.005 gram of dibutyl tin laurate, at 70 DEG C, react 3 hours.Then plus
Enter 66.0 grams of single-ended double carbon hydroxy silicon oils (molecular weight 2000,0.033mol), 0.075 gram of MEHQ, 0.047 gram of February
Dilaurylate, reacted 3 hours at 80 DEG C.Then 40 grams of toluene, 6.47 grams of maleic anhydrides (0.066mol) are added,
17.08 grams of perfluoroalkyl ethanols (hydroxyl value 108.4mgKOH/g, 0.033mol), 0.32 gram of pyrovinic acid, 0.047 gram to hydroxyl
Methyl phenyl ethers anisole, reacted 7 hours at 95 DEG C.Then add 6.54 grams of hyperbranched poly ester polyols (hydroxyl value 565.9mgKOH/g,
0.066mol-OH), 0.047 gram of MEHQ, 0.32 gram of pyrovinic acid and 20 grams of toluene, are warming up to 115 DEG C next time
Stream reaction 7 hours.After reaction terminates reaction, a small amount of insoluble matter is filtered to remove while hot, appropriate ethyl acetate is added and is diluted to 20%
Solid content.
Comparative example 5
Into 250 milliliters of four-hole bottles equipped with magnetic agitation, coil condenser, thermometer and water knockout drum, in nitrogen
Under protection, add 1.26 grams of hexamethylene diisocyanates (0.0075mol), hydroxy-ethyl acrylate 0.87 gram (0.033mol),
10 grams of toluene and 0.011 gram of MEHQ, 0.001 gram of dibutyl tin laurate, at 70 DEG C, react 3 hours.Then
Add 90.0 grams of single-ended double carbon hydroxy silicon oils (molecular weight 12000,0.0075mol), 0.011 gram of MEHQ, 0.092 gram
Dibutyl tin laurate, reacted 3 hours at 80 DEG C.Then 40 grams of toluene, 2.45 grams of maleic anhydrides (0.025mol) are added,
9.06 grams of perfluoroalkyl ethanols (hydroxyl value 108.4mgKOH/g, 0.0175mol), 0.12 gram of pyrovinic acid, 0.011 gram to hydroxyl
Methyl phenyl ethers anisole, reacted 7 hours at 95 DEG C.Then add 2.48 grams of hyperbranched poly ester polyols (hydroxyl value 565.9mgKOH/g,
0.025mol-OH), 0.021 gram of MEHQ, 0.12 gram of pyrovinic acid and 20 grams of toluene, are warming up to 115 DEG C next time
Stream reaction 7 hours.After reaction terminates reaction, a small amount of insoluble matter is filtered to remove while hot, appropriate ethyl acetate is added and is diluted to 20%
Solid content.
Application in photocureable coating
The anti-soil that embodiment and comparative example synthesis are separately added into the UV photocuring stiffened coating being formulated table 1 Suo Shi helps
Agent, addition be coating weight 1% (because anti-soil auxiliary agent solid content is 20%, be actually added into auxiliary agent as 0.2%), in PMMA and
Showering is carried out on PET sheet, is toasted under 45 degree celsius temperatures 3~5 minutes, is obtained sheet material after then carrying out UV photocurings, solidify energy
Measure as 600mJ/cm2, coating test result such as table 2：
Table 1, UV photocuring stiffened formulation for coating material
Performance test：
1. anti-soil type is evaluated：Water contact angle and oil pen
1.1. initial water contact：Measured by DSA25 type Standard contacts angle measuring instrument (Kr ü ss, Germany), diverse location is surveyed
Three times, results averaged.
1.2. oil resistivity pen wipes number：Oil pen is drawn into horizontal line in coating same position, is wiped with non-dust cloth, entered repeatedly
Row test, pen trace wipe complete number.
2. anti-fingerprint performance test：Fingerprint is pressed on coating, wiped with non-dust cloth, observes fingerprint residues situation；Wherein,
Zero represent fingerprint easily wipe and wipe after fingerprint noresidue, wiping still has antifouling effect more than 50 times, and × expression fingerprint can be with
Wipe but fingerprint is difficult to clean, antifouling effect is bad.
Water contact angle after 3. durability anti-soil-steel wool wipes：
Using 0000# steel wool, under 1000 gram forces, the water contact angle after wiping 100 times is (by DSA25 type Standard contacts
Angle measuring instrument (Kr ü ss, Germany) is measured, and diverse location is surveyed three times, results averaged.).
The application of table 2, anti-soil auxiliary agent in photocuring stiffened coating
Remarks：The adjuvant used auxiliary agent corresponded in synthetic example of formulation Example, is helped as used in formulation Example 1
Agent is the auxiliary agent synthesized in embodiment 1.It is formulated the adjuvant used auxiliary agent in corresponding synthesis comparative example of comparing embodiment.
The anti-soil that the addition in ultraviolet light curing hardening coating is 0.2% can be seen that by the embodiment 1-9 of table 2
Auxiliary agent, in PET and PMMA substrate surfaces, the initial water contact through photocuring rear substrate face coat is 110 degree or so for showering；
Anti-fingerprint excellent performance.Oil resistivity number is more than 120 times.0000# steel wool, under the load of 1000 gram forces, wipe 100
Also at 105 degree or so, this shows that coating has and continues antifouling property water contact angle after secondary.
And there is a big difference compared with embodiment for the combination property of comparative example.Comparative example 1 is the horse without organosilicon structures
Carry out the fluorine-containing light-cured type hyper-branched polyester of acrylate structure, although after it has higher water contact angle at initial stage and steel wool friction
Water contact angle, but its oil resistivity number is low, anti-fingerprint poor performance.Comparative example 2 for without fluorine structure acrylate and
The siliceous light-cured type hyper-branched polyester of maleate structure, although it has higher oil resistivity number, its at initial stage water
Contact angle is relatively low, is below 95 degree, fingerprint resistance can be also excessively poor.The molecular weight that comparative example 3 uses is double for 3000 silicone oil
End carbon hydroxyl modification silicone oil, because this structure so that the silicone portion being introduced into super esterified polyester is connect with block fashion
Onto the corresponding arm of hyper-branched polyester, this structure causes silicone portion, after photocuring, because unsaturated double-bond crosslinking is solid
Change and be fixed on coat inside, thus be not easy to move on coating surface.And single end that the embodiment 4 compareed therewith uses is double
Carbon hydroxy silicon oil is connected in a manner of grafting on the corresponding arm of hyper-branched polyester, even if after photocuring, unsaturated double-bond
Crosslinking curing, it is not easy to be fixed on coat inside, and is prone to migrate into coating surface, therefore has good pollution resistance
Energy.Comparative example 4 is low with the antifouling property of comparative example 5, respectively due to too low and too high using the molecular weight of single-ended double carbon hydroxy silicon oils
Caused, the reason for causing fluorine-containing and siliceous part too high respectively, causes.
In addition, the auxiliary agent can be also used in addition to available for polymethyl methacrylate (PMMA) and polyester (PET)
In a variety of transparent plastic substrate top layer films such as PC, PVC, to meet the needs of different.The acrylate and maleate structure
Fluorine silicon light-cured type hyper-branched polyester synthesis technique is simple, raw material are cheap and easily-available, there is good application value.
The specific embodiment of the present invention is described above.It is to be appreciated that the invention is not limited in above-mentioned
Particular implementation, those skilled in the art can make various deformations or amendments within the scope of the claims, this not shadow
Ring the substantive content of the present invention.
Claims (8)
1. a kind of auxiliary agent being used in photocureable coating, it is characterised in that the auxiliary agent is to contain acrylate and maleate
The fluorine silicon light-cured type hyper-branched polyester of structure；Its structure is as follows：
；Wherein, R1, R3Represent alkyl of the carbon number as 2-5, R2, R4Represent alkylidene of the carbon number as 2-5；M=35~80；n
=2,3,4 ..., wherein n=3 composition accounts for more than 60%.
2. the auxiliary agent according to claim 1 being used in photocureable coating, it is characterised in that it is described containing acrylate and
The fluorine silicon light-cured type hyper-branched polyester of maleate structure be prepared by a method comprising the following steps obtained by：
S1, under nitrogen protection, using toluene as solvent, using dibutyl tin laurate as catalyst, MEHQ is resistance
Poly- agent, diisocyanate, with the rate of charge of mol ratio 1: 1, at 70~75 DEG C, react 3~4 hours, obtained with crylic acid hydroxy ester
It is isocyanate groups to one end, one end is the compound of acrylic double bond；
S2, the double carbon hydroxyl modification silicone oil for adding into step S1 reaction solution identical with crylic acid hydroxy ester molal quantity,
Reacted 3~4 hours at 75~80 DEG C and obtain the modified silicon oil that one end is hydroxyl, one end is acrylic double bond；
S3, toluene, perfluoroalkyl ethanol, maleic anhydride, catalyst pyrovinic acid are added into step S2 reaction solution, 95~
Reacted at 100 DEG C and obtain within 7~8 hours that there is the modified silicon that one end is unsaturated carboxyl, one end is acrylate unsaturated double-bond
The mixture of the maleic mono-ester of oil and perfluoroalkyl；
S4, hyperbranched poly ester polyol, MEHQ, pyrovinic acid and toluene are added into step S3 reaction solution,
Back flow reaction 7~8 hours at 115~120 DEG C, obtain containing acrylate and the fluorine silicon light-cured type of maleate structure over-expense
Change the toluene solution of polyester.
3. the auxiliary agent according to claim 2 being used in photocureable coating, it is characterised in that the crylic acid hydroxy ester is
One kind in hydroxy-ethyl acrylate, hydroxypropyl acrylate, hy-droxybutyl.
4. the auxiliary agent according to claim 2 being used in photocureable coating, it is characterised in that the diisocyanate is six
One kind in methylene diisocyanate, IPDI.
5. the auxiliary agent according to claim 2 being used in photocureable coating, it is characterised in that double carbon hydroxy silicon oils are two ends
Hold one kind in the double carbon hydroxy silicon oils of carbon hydroxyl modification silicone oil, single end.
6. the auxiliary agent according to claim 2 being used in photocureable coating, it is characterised in that the perfluoroalkyl ethanol is
The mixture of the perfluoroalkyl ethanol (TEOH-N) of different fluorinated volumes, its molecular formula are as follows：
F(CF2CF2)nCH2CH2OH, n=2,3,4 ...；Wherein n=3 composition accounts for more than 60%.
7. the auxiliary agent according to claim 2 being used in photocureable coating, it is characterised in that in step S3, the perfluor
The addition of alkyl alcohol is that the ratio between the addition, the two molal quantity based on crylic acid hydroxy ester in step S1 is 9: 1~1: 9.
8. a kind of consolidate preparing anti-soil light according to the auxiliary agent according to any one of claims 1 to 7 being used in photocureable coating
Change the purposes in coating, it is characterised in that the auxiliary agent is anti-soil auxiliary agent.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109722089A (en) * | 2018-12-21 | 2019-05-07 | 上海乘鹰新材料有限公司 | Ultraviolet-curing paint anti-pollution auxiliary agent |
| CN109722088A (en) * | 2018-12-19 | 2019-05-07 | 上海乘鹰新材料有限公司 | A kind of photocureable coating anti-pollution auxiliary agent and its application |
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| JP2006200083A (en) * | 2005-01-21 | 2006-08-03 | Kenji Saito | Water repellant composition for fiber, method for water repellence-treating fibrous product and silk fibrous product |
| CN101367922A (en) * | 2008-09-12 | 2009-02-18 | 中国科学技术大学 | Fluorine-containing hyperbranched polyester acrylic ester and method of preparing the same |
| CN104558580A (en) * | 2014-12-26 | 2015-04-29 | 上海维凯光电新材料有限公司 | Fluorine-containing hyperbranched polyester maleic acid ester, preparation and application thereof and coating composition comprising fluorine-containing hyperbranched polyester maleic acid ester |
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|---|---|---|---|---|
| JP2006200083A (en) * | 2005-01-21 | 2006-08-03 | Kenji Saito | Water repellant composition for fiber, method for water repellence-treating fibrous product and silk fibrous product |
| CN101367922A (en) * | 2008-09-12 | 2009-02-18 | 中国科学技术大学 | Fluorine-containing hyperbranched polyester acrylic ester and method of preparing the same |
| CN104558580A (en) * | 2014-12-26 | 2015-04-29 | 上海维凯光电新材料有限公司 | Fluorine-containing hyperbranched polyester maleic acid ester, preparation and application thereof and coating composition comprising fluorine-containing hyperbranched polyester maleic acid ester |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109722088A (en) * | 2018-12-19 | 2019-05-07 | 上海乘鹰新材料有限公司 | A kind of photocureable coating anti-pollution auxiliary agent and its application |
| CN109722088B (en) * | 2018-12-19 | 2020-10-16 | 上海乘鹰新材料有限公司 | Anti-fouling auxiliary agent for photocureable coating and application thereof |
| CN109722089A (en) * | 2018-12-21 | 2019-05-07 | 上海乘鹰新材料有限公司 | Ultraviolet-curing paint anti-pollution auxiliary agent |
| CN109722089B (en) * | 2018-12-21 | 2020-10-16 | 上海乘鹰新材料有限公司 | Anti-fouling auxiliary agent for ultraviolet curing coating |
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