CN108753013A - A kind of antifouling anti-graffiti auxiliary agent of water solubility and its application - Google Patents
A kind of antifouling anti-graffiti auxiliary agent of water solubility and its application Download PDFInfo
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- CN108753013A CN108753013A CN201810384122.3A CN201810384122A CN108753013A CN 108753013 A CN108753013 A CN 108753013A CN 201810384122 A CN201810384122 A CN 201810384122A CN 108753013 A CN108753013 A CN 108753013A
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- auxiliary agent
- water solubility
- antifouling anti
- graffiti
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- 0 CCCCC(C*)(CCC[C@@](CC)(CClIC(*)*=C)C[Cl+]C*)CC(C1)C1[C@](CC)C=C Chemical compound CCCCC(C*)(CCC[C@@](CC)(CClIC(*)*=C)C[Cl+]C*)CC(C1)C1[C@](CC)C=C 0.000 description 3
- YDAHJNIANAOZEG-UHFFFAOYSA-N CCC(C)(N(C)C)OC Chemical compound CCC(C)(N(C)C)OC YDAHJNIANAOZEG-UHFFFAOYSA-N 0.000 description 1
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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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Abstract
The invention discloses a kind of antifouling anti-graffiti auxiliary agent of water solubility and its applications, the auxiliary agent introduces the groups such as polysiloxanes segment, the organic segment of water solubility, photocuring active group and-CO-NH- containing tertiary amino on the basis of perfluoropolyether segment, improve intermiscibility, the adhesive force of auxiliary agent and aqueous UV paint films, and perfluoropolyether segment relocation site can be made more thorough, so that paint film has good antifouling property and wear-resisting property;Using:Its application in antifouling anti-graffiti water-based ultraviolet (UV) curable coating.
Description
Technical field
The invention belongs to polymeric material fields, more particularly to water-soluble and suitable for water-based ultraviolet (UV) curable coating
Auxiliary agent, and in particular to a kind of antifouling anti-graffiti auxiliary agent of water solubility and its application.
Background technology
Water-based ultraviolet (UV) curable coating has curing rate fast, saves the energy, and environmental pollution is small, and cured product performance is good,
The advantages that being suitable for high-speed automated production is the main substitute of traditional coating (especially solvent based coating), increasingly by
To the attention of coating circle.However, containing a large amount of carbonyl, amino isopolarity function since waterborne UV coating is formed by paint film
Group, leads to the anti-scribble poor performance of the anti-pollution of paint film.Improve antifouling, the anti-sticking and anti-graffiti property of existing waterborne UV coating coating surface
Can, it is always the hot and difficult issue of coating research, the 3C for being particularly applied to the surfaces such as computer, communication and consumer electronics is applied
The rigidity-increasing dope of material and the optics film surface such as display and touch screen is also useful for the anti-graffiti painting of prevention city psoriasis
The low surface energy coatings such as material.Technically, the hydrophobic oleophobic function of material surface is realized, there are mainly two types of approach, when
Low-surface energy substance, mainly Organic fluoride and organosilicon are added in material surface;Second is that building coarse structure in material surface.In the least
It is undoubtedly that a kind of efficient anti-pollution auxiliary agent is added in research in existing formulation for coating material, without changing the other of original coating
Performance is a kind of quick, efficient and practical method.
Perfluoropolyether (PFPE) is a kind of fluorine of safety and environmental protection without containing environment cumulative bad chemical compositions such as PFOA, PFCS
Source.It is poor with other hydrocarbon component intermiscibilities in coating, floats on the surface of paint film in film forming procedure in meeting, and then reduce paint film
Surface energy finally realizes the functions such as grease proofing, waterproof and dustproof.It is poly- that Chinese invention patent CN106220839A discloses a kind of perfluor
Anti-graffiti auxiliary agent of ether and preparation method thereof, structural formula is as follows:
Wherein, n is natural number and 2≤n≤30;X is R1N(R2)-or-HN-R2, R1、R2Respectively containing polyurethane structural
Substituent group, and alcoholic extract hydroxyl group is contained in the end of X.However this compound is difficult to apply mainly containing groups such as polyurethane structurals
In UV photocureable coating, the poor compatibility in UV photocureable coating, it is difficult to play its antifouling anti-graffiti function.
For another example patent of invention CN2005800145739 discloses a kind of perfluoropolyether-modified acrylic acid with antifouling effect
Ester, however after the compound of this patent disclosure is applied to coating, coating is in occurring UV Light Curings, the oxygen meeting in air
Oxygen inhibition effect is generated to solidification, while the adhesive force and compatibility of this compound and paint film are all poor, and then can be in product
Perfluoropolyether occurs during use and is constantly detached from coating surface, the durability for eventually leading to paint film anti-pollution function is deteriorated, because
Although this its realize certain antifouling wearability, effect is still undesirable, and the compound can not be dissolved in aqueous UV
Coating, that is, may not apply to the antifouling antigraffiti properties of waterborne UV coating improves.
Invention content
It is antifouling anti-graffiti the technical problem to be solved by the present invention is to overcome the deficiencies of the prior art and provide a kind of water solubility
Auxiliary agent, it is suitable for water-based ultraviolet (UV) curable coating, and can realize antifouling antigraffiti effect steady in a long-term, and wearability is good.
The present invention also provides a kind of antifouling anti-graffiti water-based ultraviolet (UV) curable coating.
In order to solve the above technical problems, a kind of technical solution that the present invention uses is as follows:
A kind of antifouling anti-graffiti auxiliary agent of water solubility, the antifouling anti-graffiti auxiliary agent of water solubility have the following structure general formula:
Wherein, RfFor perfluoro polyether acyl group;
X1For the organic group containing secondary amino group, RfIt is connected with the nitrogen-atoms of the secondary amino group;
X2For the water-soluble organic group containing tertiary amino;
RAFor the organic group containing photocuring active group He-CO-NH-, the RABy its contain described in-CO-
Carbon atom on NH- and the X2In the tertiary amino nitrogen-atoms be connected;
RCFor-CnH2n-1, n is positive integer;
A, b, c are separately selected from the integer more than or equal to 1.
Some preferred aspects according to the present invention, the RfFor one or more groups in group as follows
It closes:
Wherein, 50 >=d >=2;
Wherein, 50 >=e >=2;
Wherein, 50 >=f >=2,50 >=g >=2;
Wherein, 50 >=h >=2,50 >=i >=2.
Some preferred aspects according to the present invention, the X1For-R1- NH-, wherein R1For C1-20Alkylidene group.
It is highly preferred that R1For C1-10Alkylidene group.Some specific aspects according to the present invention, R1Can be-CH2-、-
CH2CH2-、-CH2CH2CH2-、-CH2CH2CH2CH2-、 -CH2CH2CH2CH2CH2-、-CH2CH2CH2CH2CH2CH2-、-CH(CH3)
CH2-、-C(CH3) 2CH2-。
Some preferred aspects according to the present invention, the X2ForWherein, R2For C1-20Alkylene
Base group.It is highly preferred that R2For C1-10Alkylidene group.Some specific aspects according to the present invention, R2Can be-CH2-、-
CH2CH2-、-CH2CH2CH2-、-CH2CH2CH2CH2-、 -CH2CH2CH2CH2CH2-、-CH2CH2CH2CH2CH2CH2-、-CH(CH3)
CH2-、-C(CH3) 2CH2-。
Some preferred aspects according to the present invention, the photocuring active group are unsubstituted acrylate-functional groups
And/or C1-10Alkyl-substituted acrylate-functional groups.The structural formula of acrylate-functional groups is CH2=CHCOO, alkyl take
The acrylate-functional groups in generation can be CH2=C (CH3)COO、CH2=C (CH2CH3)COO、CH2=C (CH2CH2CH3)COO、
CH2=C (CH2CH2CH2CH3) COO etc..
More according to the present invention specific and preferred aspect, the photocuring active group have at least three and are located at
The RAThe end of structure.
Some preferred aspects according to the present invention ,-CO-NH- have multiple.Be conducive to introduce other groups or
Suitably form longer segment.
Some preferred aspects according to the present invention, the RAFor-CO-NH-R3-NH-COO-R4, wherein the R3ForR4For-(CH2) j-C(CH2OOC-
CH=CH2)3, or,
-(CH2)k-C(CH2OOC-CH=CH2)2-CH2-O-CH2-C(CH2OOC-CH=CH2)3, wherein j, k are independently
Ground is selected from positive integer;It is highly preferred that j, k separately integer in 1-100.
R5、R6It is separately-NH-CO-O-R7- O-CO-NH-, R7To be selected from C1-10Alkylidene ,-(CmH2mO)r1-
CmH2m-、-(CpH2pO)r2-(CsH2sO)r3-CmH2mIn one or more combinations, m, p, s, r1, r2 and r3 are separately
Selected from positive integer, p and s is different.Specifically, m, p, s, r1, r2 and r3 separately integer in 1-50.According to this
Some specific aspects of invention, C1-10Alkylidene can be-CH2-、-CH2CH2-、-CH2CH2CH2-、-CH2CH2CH2CH2-、
-CH2CH2CH2CH2CH2-、-CH2CH2CH2CH2CH2CH2-、-CH(CH3)CH2-、-C(CH3) 2CH2-.It is according to the present invention another
A little specific aspects, m, p, s, r1, r2 and r3 separately integer in 1-20.
In the present invention,It indicates that other groups can be connected at shown position.
Some preferred aspects according to the present invention, the RCFor C1-10Alkyl.Some specific aspects according to the present invention,
RCCan be-CH3、-CH2CH3、-CH2CH2CH3、-CH2CH2CH2CH3、 -CH2CH2CH2CH2CH3、-
CH2CH2CH2CH2CH2CH3、-CH(CH3)CH3Or-C (CH3) 2CH3。
Some preferred aspects according to the present invention, a, b are separately selected from 1,2,3,4,5,6,7,8,9,10.
Some preferred aspects according to the present invention, c are the integer in 3-30.It is highly preferred that c is in 3-20
Integer.Some specific aspects according to the present invention, c are the integer in 3-15.
More according to the present invention specific and preferred aspect, the antifouling anti-graffiti auxiliary agent of water solubility are selected from following knot
One kind in structure formula:
Wherein, 50 >=d >=2, a, b, c and t1 are separately positive integer;
Wherein, 50 >=d >=2, a, b, c and t2 are separately positive integer;
Wherein, 50 >=d >=2, a, b, c and t3 are separately positive integer;
Wherein, 50 >=d >=2, a, b, c, t4 and t5 are separately positive integer;
Wherein, 50 >=d >=2, a, b, c, t6 and t7 are separately positive integer.
Some specific aspects according to the present invention, t1, t2, t3, t4, t5, t6 and t7 are separately in 1-50
Integer.
Another technical solution provided by the invention:A kind of antifouling anti-graffiti water-based ultraviolet (UV) curable coating, raw material contain
State the antifouling anti-graffiti auxiliary agent of water solubility.
In the present invention, in parts by weight, the composition of raw materials of the antifouling anti-graffiti water-based ultraviolet (UV) curable coating includes:
Wherein, the UV reactive compounds can choose aqueous polyurethane acrylate, waterborne epoxy acrylate, water
One or more combinations in property polyester acrylate, 2 functional group propenoic acid ester monomers, 3 degree of functionality acrylate monomers etc..
The PH conditioning agents can be chosen in triethylamine, ammonium hydroxide, diethanol amine, triethanolamine, methylethanolamine etc.
One or more combinations.
The photoinitiator can choose Irgacure500, Irgacure819, Irgacure2959,
One or more combinations in Irgacure754 and Irgacure819DW etc..
In the present invention, raw material described in whole can not have by commercially available and/or take known means and be prepared
When being illustrated, it is satisfied by the requirement of standard chemical products.
Due to the implementation of above-mentioned technical proposal, the present invention has the following advantages that compared with prior art:
The materials compatibility of the antifouling anti-graffiti auxiliary agent of water solubility provided by the invention and water-based ultraviolet (UV) curable coating is good, is painting
Migration in film is strong, can make the perfluoropolyether group contained in auxiliary agent during coating forms a film quickly and thoroughly
It migrates to the surface of paint film and reaches excellent antifouling anti-graffiti and other effects, while can also realize with the adhesive force of paint film more
By force, it will not fall off during the use of product, and then ensure that steady in a long-term antifouling anti-graffiti and other effects and wear-resisting of paint film
Property is more preferable.
Description of the drawings
Fig. 1 is the nuclear-magnetism H of the PFPE-1 of embodiment 11NMR analysis of spectra.
Specific implementation mode
The preparation method of the antifouling anti-graffiti auxiliary agent of water solubility provided by the invention, the preparation method include the following steps:
1) silane coupling agent 1 containing primary amino group and the silane coupling agent containing secondary amino group 2 are mixed, hydrolysis occurs
And condensation reaction, head product is obtained, then by gained head product and siloxanes ring body, organosilicon end capping in the presence of the first catalyst
Polycondensation reaction occurs for agent, generates amido silicon oil product 1;
2) so that amido silicon oil product 1 prepared by step 1) is carried out amidation process with per-fluoro polyether compound, generate product
2;
3) in the presence of the second catalyst, in the presence of polymerization inhibitor, make isocyanate compound and hydroxyl third in a solvent
Enoic acid ester compounds react, and generate product 3;
4) product 3 prepared by step 3) is added in the product 2 prepared to step 2), it is antifouling to generate the water solubility for reaction
Anti-graffiti auxiliary agent.
The preparation method is simple, easy to operate, and reaction condition is mild, safe preparation process, environmental protection.
Specific and preferred aspect, the silane coupling agent 1 containing primary amino group more according to the present invention can choose γ-
Aminopropyltriethoxy dimethoxysilane, γ-aminopropyltriethoxy diethoxy silane, γ-aminopropyl ethyldimethoxysilane and
One or more combinations in γ-aminopropyl ethyl diethoxy silane.
Specific and preferred aspect, the silane coupling agent 2 containing secondary amino group more according to the present invention can choose γ-
Piperazinopropyl methyl dimethoxysilane, γ-piperazinopropyl methyldiethoxysilane, γ-piperazinopropyl ethyl two
Methoxy silane, γ-piperazinopropyl ethyl diethoxy silane, N- (normal-butyl)-γ-aminopropyltriethoxy dimethoxy silicon
One kind in alkane, 3- piperazinopropyls methyl dimethoxysilane and N- (normal-butyl)-γ-aminopropyltriethoxy diethoxy silanes
Or a variety of combination.
Preferably, in step 1), the hydrolysis and condensation reaction is made to be carried out in desalted water.
Preferably, first catalyst is basic catalyst, and the basic catalyst is selected from potassium hydroxide, hydroxide
One or more combinations in the catalyst such as sodium and tetramethylammonium hydroxide.
Preferably, the siloxanes ring body is selected from octamethylcy-clotetrasiloxane, hexamethyl cyclotrisiloxane and decamethyl
One or more combinations in cyclopentasiloxane.
Preferably, the organosilicon end capping agent is selected from hexamethyldisiloxane, octamethyltrisiloxane and decamethyl four
One or more combinations in siloxanes.
Preferably, in step 1), the hydrolysis and condensation reaction carry out at 10 DEG C~200 DEG C, the reaction time 1
~12 hours.It is highly preferred that in step 1), the hydrolysis and condensation reaction carry out at 10 DEG C~100 DEG C, the reaction time
It is 2~8 hours.
Preferably, in step 1), the polycondensation reaction carries out at 10 DEG C~200 DEG C, and the reaction time is 1~12 hour.
It is highly preferred that in step 1), the polycondensation reaction carries out at 80 DEG C~200 DEG C, and the reaction time is 2~8 hours.
Preferably, make the amidation process of step 2) in the presence of protective gas (such as can be nitrogen etc.) into
Row.
Preferably, the general structure of the per-fluoro polyether compound is RfOR8, wherein R8For the alkyl of C1-10.According to this
Some specific aspects of invention, R8Can be-CH3、-CH2CH3、-CH2CH2CH3、 -CH2CH2CH2CH3、-
CH2CH2CH2CH2CH3、-CH2CH2CH2CH2CH2CH3、-CH(CH3) CH3Or-C (CH3)2CH3。
Preferably, in step 2), the amidation process is made to be carried out at 50 DEG C~200 DEG C, the reaction time is 1~12 small
When.It is highly preferred that in step 2), the amidation process is made to be carried out at 50 DEG C~150 DEG C, the reaction time is 3~12 hours.
It is further preferred that in step 2), the amidation process is made to be carried out at 50 DEG C~120 DEG C, the reaction time is 3~10 small
When.
Preferably, second catalyst can be to choose triethylamine, butyl tetra titanate, dibutyltindilaurylmercaptide cinnamic acid
One or more combinations in ester, stannous octoate, two (dodecyl sulphur) dibutyl tins and dibutyltin diacetate.
Preferably, the polymerization inhibitor is selected from hydroquinone, 1,4-benzoquinone, methylnaphthohydroquinone, p-hydroxyanisole, 2- tertiary butyls
Hydroquinone and 2, one or more combinations in 5- di-tert-butyl hydroquinones.
Preferably, in step 3), the solvent is selected from ethyl acetate, ethyl ester propyl, butyl acetate, pentyl acetate, fourth
One or more combinations in ketone, methyl butyl ketone and methyl iso-butyl ketone (MIBK).
Preferably, the isocyanate compound is selected from isophorone diisocyanate and its tripolymer, and toluene two is different
Cyanate and its dimer, tripolymer, hexamethylene diisocyanate and its dimer, tripolymer, dicyclohexyl methyl hydride two are different
One or more combinations in cyanate.Can also be above-mentioned isocyanates reacts with hydrophilic both-end hydroxy compounds
Product, wherein the hydrophilic both-end hydroxy compounds be selected from polytetrahydrofuran ether glycol, polyethylene glycol, polypropylene glycol,
One or more combinations in polyethylene glycol propylene glycol copolymers.When the isocyanate compound is above-mentioned isocyanic acid
When the reaction product of ester and hydrophilic both-end hydroxy compounds, the specific implementation mode of step 3) is:First make above-mentioned isocyanic acid
Ester and hydrophilic both-end hydroxy compounds reacted in the presence of the second catalyst generate NCO sealing ends performed polymer product (for
Description is convenient, referred to as step a), adds polymerization inhibitor and hydroxy acrylic acid ester compounds, reaction (for convenience of description, referred to as step
B), it generates and contains NCO and the product of acrylate-functional groups 3.
Preferably, the hydroxy acrylic acid ester compounds are selected from pentaerythritol triacrylate and/or dipentaerythritol
Tetraacrylate.
Preferably, in step 3), the reaction is made to be carried out at 20~150 DEG C, the reaction time is 1~12 hour.
Preferably, in step 3), when the isocyanate compound is above-mentioned isocyanates and hydrophilic both-end hydroxyl
When the reaction product of compound, step a is made to be carried out at 60~150 DEG C.
Preferably, in step 3), when the isocyanate compound is above-mentioned isocyanates and hydrophilic both-end hydroxyl
When the reaction product of compound, step b is made to be carried out at 20~80 DEG C.
Preferably, in step 4), the reaction is made to be carried out at 0 DEG C~80 DEG C, the reaction time is 2~12 hours.
Some specific aspects according to the present invention, the embodiment of step 4) are:In the product 2 prepared to step 2) slowly
Product 3 prepared by step 3) is instilled, reaction.
Said program is described further below in conjunction with specific embodiment;It should be understood that these embodiments are for illustrating
The basic principles, principal features and advantages of the present invention, and the present invention is not by the scope limitation of following embodiment;It is used in embodiment
Implementation condition further adjustment can be done according to specific requirement, the implementation condition being not specified is usually the item in routine experiment
Part.
In following unless otherwise specified, all raw materials are prepared both from commercially available or conventional method by this field
It forms.
Embodiment 1
The present embodiment provides a kind of antifouling anti-graffiti auxiliary agent 1# samples (PFPE-1) of water solubility, the structural formula of PFPE-1 is as follows
It is shown:
Wherein, a=1, b=1, c=8, d=11, PEG represent peg molecule segment.
Preparation method is as follows:
γ-aminopropyltriethoxy dimethoxysilane (5.25g), 3- piperazinopropyl methyl are added in the three-necked flask of 1L
Dimethoxysilane (5.8g) and desalted water 10g, stir hydrolysis 5 hours under the conditions of 50 DEG C, slowly open negative pressure and take off
Water obtains dry silane low-boiling-point substance;Add potassium hydroxide powder (0.01g), octamethylcy-clotetrasiloxane (15g) and hexamethyl
Disiloxane (4.05g), is to slowly warm up to 130 DEG C, and it is 4 hours to be stirred to react the time, most afterwards through vacuum removal low-boiling-point substance technique,
Obtain dry amido silicon oil;Perfluoropolyether methanol ester (50g, the following institute of structural formula is added in above-mentioned product under nitrogen protection
Show, wherein RfHexafluoropropylene oxide polymerized unit is chosen, Taicang Zhonghua Environmental Protection Medical Co., Ltd. provides), it is to slowly warm up to 80
DEG C, the reaction time is 8 hours, obtains perfluoropolyether-modified amido silicon oil.
In the three-necked flask of 1L be added dibutyltindilaurylmercaptide cinnamic acid tin (2g), isophorone diisocyanate (11g),
(25g, molecular weight are 1000g/mol to polyethylene glycol, and polymerized unit is CH2CH2O) and butyl acetate (100g), under nitrogen protection
80 DEG C are to slowly warm up to, it is 2 hours to be stirred to react, and obtains isocyanate prepolymer;Reaction system is cooled to 50 DEG C, and inhibition is added
Agent p-hydroxyanisole (0.25g) is slowly added to pentaerythritol triacrylate (7.75g), reaction time 4 under agitation
Hour, the acrylate compounds containing NCO are obtained, then add solvent acetic acid butyl ester (188g);Controlling reaction temperature is 10
DEG C, above-mentioned product is slowly dropped into perfluoropolyether-modified amido silicon oil under agitation, the reaction time is 4 hours, sampling
It carries out the peaks infrared spectrum analysis NCO to disappear, water-soluble antifouling anti-graffiti auxiliary agent PFPE- is made to reaction product removed under reduced pressure solvent
1。
Involved raw material perfluoropolyether methanol ester R in preparation methodfOCH3Middle RfStructure be:
Wherein, d=11;
Nuclear-magnetism H is carried out to product PFPE-1 compounds1NMR is analyzed, the H of PFPE-11NMR analysis results as shown in Figure 1, by
Known to Fig. 1:Mixed and disorderly chemical shift peak within the scope of 0ppm~0.2ppm belongs to silicon onychostroma in dimethyl silicone polymer side group
The absorption peak of son;It is sub- that mixed and disorderly chemical shift peak within the scope of 1.0ppm~2.0ppm belongs to silicon in dimethyl silicone polymer side group
Proton uptake peak on methyl and isophorone Molecular Ring;Chemical shift peak near 3.5ppm belongs to polyethylene glycol intermediate chain
Methylene in section;Other mixed and disorderly chemical shift peaks within the scope of 2.0ppm~4.5ppm belong to piperazine and isophorone point
The methylene being connected with urea groups (or amide groups and urethane bond) in subring, the also absorption of the methylene on pentaerythrite
Peak;Occurs in acrylate structural chemical shift of proton peak in double bond in the range of 5.5~6.5ppm, it was demonstrated that there is acrylic acid
Ester functional group has been successfully introduced on PFPE strands.
Embodiment 2
The present embodiment provides a kind of antifouling anti-graffiti auxiliary agent 2# samples (PFPE-2) of water solubility.
According to the step and technique shown in embodiment 1, isophorone diisocyanate quality is changed to 22g, polyethylene glycol
Quality is changed to 50g, and solvent acetic acid butyl ester additional amount is changed to 300g, and pentaerythritol triacrylate quality is changed to 15.5g,
3- piperazinopropyl methyl dimethoxysilane quality is changed to 11.6g, remaining condition and quality are same as Example 1, system
Standby water-soluble antifouling anti-graffiti auxiliary agent 2# samples (PFPE-2).
Embodiment 3
The present embodiment provides a kind of antifouling anti-graffiti auxiliary agent 3# samples (PFPE-3) of water solubility.
According to the step and technique shown in embodiment 1, isophorone diisocyanate quality is changed to 22g, polyethylene glycol
Molecular weight is changed to 2000g/mol, and polyethylene glycol quality is changed to 100g, and solvent acetic acid butyl ester additional amount is changed to 425g, season
Penta tetrol triacrylate quality is changed to 15.5g, and 3- piperazinopropyl methyl dimethoxysilane quality is changed to 11.6g,
Remaining condition and quality are same as Example 1, prepare water-soluble antifouling anti-graffiti auxiliary agent 3# samples (PFPE-3).
Comparative example 1
The present embodiment provides a kind of preparation methods of the antifouling anti-graffiti auxiliary agent 4# samples (PFPE-4) of water solubility, specifically such as
Under:
Perfluoropolyether methanol ester (100g, specification are identical as example 1) and ethylaminoethanol are added in the three-necked flask of 1L
(10g, specification are identical as example 1) is to slowly warm up to 80 DEG C, and the reaction time is 8 hours, and sampling infrared analysis measures the red of ester bond
Outer absorption peak (1792cm-1) disappear, amido bond absorption peak (1712cm-1) occur;Reaction product crude product is stirred with absolute methanol
Mix cleaning, stratification takes lower liquid, repetition 3 times, the de- low boiling drying of decompression, acquisition perfluoropolyether acylamino- second at 80 DEG C
Alcohol sterling.
In the three-necked flask of 1L be added dibutyltindilaurylmercaptide cinnamic acid tin (5g), isophorone diisocyanate (11g),
(200g, molecular weight are 4000g/mol to polyethylene glycol, and polymerized unit is CH2CH2O) and butyl acetate (800g), in nitrogen protection
Under be to slowly warm up to 80 DEG C, it is 2 hours to be stirred to react, obtain isocyanate prepolymer;Reaction system is cooled to 50 DEG C, and resistance is added
Poly- agent p-hydroxyanisole (0.50g), is slowly added to pentaerythritol triacrylate (15.50g) under agitation, when reaction
Between 4 hours, obtain the acrylate compounds containing NCO, then add solvent acetic acid butyl ester (188g);Controlling reaction temperature is 10
DEG C, above-mentioned product is slowly dropped into perfluoropolyether acylamino- ethyl alcohol purified product under agitation, the reaction time is 4 small
When, sampling carries out infrared spectrum analysis NCO peaks and disappears, and being made water-soluble to reaction product removed under reduced pressure solvent antifouling anti-graffiti helps
Agent PFPE-4.
Wherein, a=11, q=45.
The preparation of coating
It is compounded according to (each component additive amount is in parts by weight) is formulated shown in table 1, high speed dispersion 20 minutes, system
It is standby go out UV coating, then coating is sprayed on makrolon (PC) plastic paint test board, the first levelling 5min at room temperature of paint film,
It is placed in again in 50 DEG C of baking ovens and toasts 30min, be finally placed in RW-UVA201-20 type UV photo solidification machines and cured, solidified bars
Part is light source power 2kw, 2.5 ms/min of delivery rate.In table, UV2282 represents UV-curable waterborne dispersions of polyurethanes2282 Cohans of UV are created company and are provided, and HDDA represents 1,6- hexanediyl esters, and (lark prestige company carries
For), Irgacure2959 represents the offer of trigger for optical solidification BASF;
The performance test of paint film
Anti- scribble property evaluation:It scribbles and is dried at room temperature for 4 hours in coating surface using capable oiliness black marking pen
Afterwards, the spot of coating surface is wiped with dry paper handkerchief, whether there are spots for observation coating surface.Classification mark is carried out according to following standard
Show:
1 grade:Expression can be easy to wipe spot, and without any residual inside paint film;
2 grades:Expression can wipe spot, but relatively elaborate, and without any residual inside paint film;
3 grades:Expression can wipe spot, but have the ink marks of infiltration inside paint film;
4 grades:Expression cannot wipe spot.
Contact angle test method:Test piece without any abrasion is placed in contact angle instrument (model:DSA30, German Ke Lvshi
Co., Ltd provides) on, using deionized water and dodecane as tested media, test droplets volume is 4 μ L, record 3 dropping liquids drop
Contact angle values, and take the arithmetic mean of instantaneous value of 3 test datas.
Rub durability evaluation:Test piece is fixed on wear-resistant tester to (ESIDA-NM-002, the easy generation in Shenzhen reach instrument
Equipment Co., Ltd provides), bundle polypropylene non-woven fabric (model on contact head friction probe:B95, the auspicious industrial material of Jiangxi sky
Expect Co., Ltd);Probe top applies 500g test loads, test trip 20mm, 10 beats/min of sample speed;Wear testing into
Row after twenty minutes, stops experiment, and the contact angle on surface is lost.
It is anti-scribble property, contact angle, rub durability test result referring to table 1.
Table 1 is the formula and the performance test results of coating
It is compared by coating sample S1, S2, S3, S4, S5, S6 and blank sample coating S7, it can be seen that in aqueous painting
PFPE is introduced in material formula can be obviously improved antigraffiti properties, and the paint film for being not introduced into PFPE does not have a pollution resistance, and oleic acid can be
Coating surface is sprawled completely, and permanent pen prepared Chinese ink can pollute paint film and cannot wipe;Compared with S6, S1, S2, S3, S4
With the contact angle with higher water and oleic acid after the abrasion of the coating surface of S5, this is because water paint S1, S2, S3, S4 and
Multiple acrylate UV photocurings active function groups and polysiloxanes segment are introduced in S5, are had more with water paint ontology
High intermiscibility and adhesive force makes water paint have higher wear-resisting property, and keeps perfluoropolyether segment relocation site more thorough,
Greatly improve antifouling antigraffiti properties;It is found simultaneously by the comparison of water paint sample S1, S4 and S5, in paint film
The increase of the anti-scribble auxiliary agent content of PFPE base anti-pollutions contributes to the promotion of antifouling property, but increase rate with content variation not
Obviously, it was demonstrated that pollution resistance improves not after the content of the anti-scribble auxiliary agent of PFPE bases anti-pollution in aqueous coating formulation reaches a certain level
Obviously.Experimental result explanation:It is provided by the present invention to have both that the water-soluble and active water solubility of UV photocurings is antifouling anti-graffiti to be helped
Agent can have good intermiscibility, adhesive force with aqueous UV paint films, perfluoropolyether segment relocation site can be made more thorough, therefore add
Its paint film has good antifouling property and wear-resisting property.
The present invention is described in detail above, its object is to allow the personage for being familiar with this field technology that can understand this
The content of invention is simultaneously implemented, and it is not intended to limit the scope of the present invention, and the present invention is not limited to above-mentioned implementations
, equivalent change or modification made by all Spirit Essences according to the present invention should be covered by the protection scope of the present invention.
Claims (10)
1. a kind of antifouling anti-graffiti auxiliary agent of water solubility, which is characterized in that the antifouling anti-graffiti auxiliary agent of water solubility has following knot
Structure general formula:
Wherein, RfFor perfluoro polyether acyl group;
X1For the organic group containing secondary amino group, RfIt is connected with the nitrogen-atoms of the secondary amino group;
X2For the water-soluble organic group containing tertiary amino;
RAFor the organic group containing photocuring active group He-CO-NH-, the RABy its contain described on-CO-NH-
Carbon atom and the X2In the tertiary amino nitrogen-atoms be connected;
RCFor-CnH2n-1, n is positive integer;
A, b, c are separately selected from the integer more than or equal to 1.
2. the antifouling anti-graffiti auxiliary agent of water solubility according to claim 1, which is characterized in that the RfIt is as follows to be selected from
One or more combinations in group:
Wherein, 50 >=d >=2;
Wherein, 50 >=e >=2;
Wherein, 50 >=f >=2,50 >=g >=2;
Wherein, 50 >=h >=2,50 >=i >=2.
3. the antifouling anti-graffiti auxiliary agent of water solubility according to claim 1, which is characterized in that the X1For-R1- NH-,
In, R1For C1-20Alkylidene group.
4. the antifouling anti-graffiti auxiliary agent of water solubility according to claim 1, which is characterized in that the X2ForWherein, R2For C1-20Alkylidene group.
5. the antifouling anti-graffiti auxiliary agent of water solubility according to claim 1, which is characterized in that the photocuring active group is
Unsubstituted acrylate-functional groups and/or C1-10Alkyl-substituted acrylate-functional groups.
6. water-soluble antifouling anti-graffiti auxiliary agent according to claim 1 or 5, which is characterized in that the photocuring active group
Group is at least three and is located at the RAThe end of structure;And/or-the CO-NH- is with multiple.
7. the antifouling anti-graffiti auxiliary agent of water solubility according to claim 1, which is characterized in that the RAFor-CO-NH-R3-NH-
COO-R4, wherein the R3For
R4For-(CH2)j-C(CH2OOC-CH=CH2)3, or,
-(CH2)k-C(CH2OOC-CH=CH2)2-CH2-O-CH2-C(CH2OOC-CH=CH2)3, wherein j, k are separately selected
From positive integer;
R5、R6It is separately-NH-CO-O-R7- O-CO-NH-, R7To be selected from C1-10Alkylidene ,-(CmH2mO)r1-
CmH2m-、-(CpH2pO)r2-(CsH2sO)r3-CmH2mIn one or more combinations, m, p, s, r1, r2 and r3 are separately
Selected from positive integer, p and s is different.
8. the antifouling anti-graffiti auxiliary agent of water solubility according to claim 1, which is characterized in that the RCFor C1-10Alkyl;
And/or separately the integer in 1-10, c are the integer in 3-30 by a, b.
9. the antifouling anti-graffiti auxiliary agent of water solubility according to claim 1, which is characterized in that the water solubility is antifouling anti-graffiti
Auxiliary agent is one kind in following structural formula:
Wherein, 50 >=d >=2, a, b, c and t1 are separately positive integer;
Wherein, 50 >=d >=2, a, b, c and t2 are separately positive integer;
Wherein, 50 >=d >=2, a, b, c and t3 are separately positive integer;
Wherein, 50 >=d >=2, a, b, c, t4 and t5 are separately positive integer;
Wherein, 50 >=d >=2, a, b, c, t6 and t7 are separately positive integer.
10. a kind of antifouling anti-graffiti water-based ultraviolet (UV) curable coating, which is characterized in that its raw material contains any in claim 1-9
The antifouling anti-graffiti auxiliary agent of water solubility described in item claim.
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