High-wear-resistance UV resin with anti-fingerprint function and preparation method thereof
阅读说明：本技术 一种具有抗指纹功能的高耐磨uv树脂及其制备方法 (High-wear-resistance UV resin with anti-fingerprint function and preparation method thereof ) 是由 张航文 徐涛 陈坤 卢德圣 于 2021-03-01 设计创作，主要内容包括：本发明涉及一种具有抗指纹功能的高耐磨UV树脂及其制备方法,该树脂的原料包括如下组份：异氰酸酯混合物、一端含有羟基的全氟聚醚醇、单端碳羟基聚硅氧烷和双端碳羟基聚硅氧烷的混合物、不含氟和硅的线型聚酯二元醇、含有聚氨酯结构的羟基丙烯酸酯以及聚氨酯反应催化剂；本发明通过组份之间的反应将全氟聚醚和有机硅链段同时引入UV树脂聚合物分子链中,利用氟硅分子的协同效应来降低树脂表面的摩擦系数和表面能,从而使得制备的UV树脂具有良好的抗指纹耐磨性能；同时通过在UV树脂聚合物分子链中引入较高含量的氨基甲酸酯来提高分子链的氢键含量,进而提高了分子链的内聚能,进一步提高了UV树脂的耐磨性能。(The invention relates to a high-wear-resistance UV resin with an anti-fingerprint function and a preparation method thereof, wherein the resin comprises the following raw materials: isocyanate mixture, perfluoropolyether alcohol with hydroxyl at one end, mixture of single-end hydroxyl polysiloxane and double-end hydroxyl polysiloxane, linear polyester diol without fluorine and silicon, hydroxyl acrylate containing a polyurethane structure and a polyurethane reaction catalyst; according to the invention, through the reaction among the components, the perfluoropolyether and the organosilicon chain segment are simultaneously introduced into the polymer molecular chain of the UV resin, and the friction coefficient and the surface energy of the resin surface are reduced by utilizing the synergistic effect of the fluorine and silicon molecules, so that the prepared UV resin has good fingerprint-resistant and wear-resistant properties; meanwhile, the high-content carbamate is introduced into the polymer molecular chain of the UV resin to improve the hydrogen bond content of the molecular chain, so that the cohesive energy of the molecular chain is improved, and the wear resistance of the UV resin is further improved.)
1. The utility model provides a high wear-resisting UV resin with anti fingerprint function which characterized in that: the raw materials of the resin comprise the following components: isocyanate mixture, perfluoropolyether alcohol containing hydroxyl at one end, mixture containing single-end hydroxyl polysiloxane and double-end hydroxyl polysiloxane, linear polyester diol containing no fluorine and silicon, hydroxyl acrylate containing a polyurethane structure and a polyurethane reaction catalyst.
2. The high abrasion resistant UV resin with fingerprint resistance function according to claim 1, wherein: the sum of the mole numbers of the functional groups of the hydroxyl in the perfluoropolyether alcohol containing hydroxyl at one end, the mixture containing single-end carbon hydroxyl polysiloxane and double-end carbon hydroxyl polysiloxane, the linear polyester diol containing no fluorine and silicon and the hydroxyl acrylic acid containing a polyurethane structure is equal to the mole number of the functional groups of the isocyanate group in the isocyanate mixture.
3. The high abrasion resistant UV resin with fingerprint resistance function according to claim 1, wherein: the isocyanate mixture comprises:
an isocyanate compound having a functionality of 3 for the isocyanate group;
and an isocyanate compound having a functionality of 2 for the isocyanate group;
the sum of the number of moles of the perfluoropolyether alcohol having a hydroxyl group at one end and the number of moles of the monohydroxy polysiloxane at one end is equal to the number of moles of the isocyanate compound having a functionality of 3;
the number of moles of the isocyanate compound having a functionality of 2 in the isocyanate group is 2 times the number of moles of the double-terminal hydroxyl polysiloxane.
4. The high abrasion resistant UV resin with fingerprint resistance function according to claim 3, wherein:
the isocyanate compound with the isocyanate group having the functionality of 3 is selected from one or more of a trimer of toluene diisocyanate, a trimer of isophorone diisocyanate and a trimer of hexamethylene diisocyanate;
the isocyanate compound with the isocyanate group functionality of 2 is selected from one or more of 2, 4-toluene diisocyanate, 2, 6-toluene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, 1, 5-naphthalene diisocyanate and diphenylmethane diisocyanate.
5. The high abrasion resistant UV resin with fingerprint resistance function according to claim 1, wherein: the perfluoropolyether alcohol having a hydroxyl group at one end has a structure represented by the following formula (1), formula (2), formula (3), formula (4), formula (5) or formula (6):
CF3CF2CF2O(CF(CF3)CF2O)nCF(CF3)CH2OH （1）；
CF3CF2CF2O(CF(CF3)CF2O)nCF(CF3)CH2O(CH2CH2O)mH （2）;
CF3CF2CF2O(CF2CF2CF2O)nCF2CF2CH2OH （3）；
CF3CF2CF2O(CF2CF2CF2O)nCF2CF2CH2O(CH2CHO)mH （4）；
CF3CF2CF2O(CF(CF3)CF2O)nCF(CF3)CO-X1-OH （5）；
CF3CF2CF2O(CF2CF2CF2O)nCF2CF2CO-X1-OH （6）；
n in the formulas (1) to (6) is a natural number and satisfies 2. ltoreq. n.ltoreq.60; m is a natural number and satisfies that m is more than or equal to 1 and less than or equal to 10; x1Has the structural formula of-O-R1-OH or-NH-R-OH, R1Is a divalent alkyl group containing a saturated carbon-oxygen chain.
6. The high abrasion resistant UV resin with fingerprint resistance function according to claim 1, wherein: in the mixture containing single-terminal carbon hydroxyl polysiloxane and double-terminal carbon hydroxyl polysiloxane:
the chemical formula of the single-end carbon hydroxyl polysiloxane is shown as the following formula (7):
（7）；
a dicarbohydroxyl polysiloxane having the formula (8):
（8）；
wherein the content of the first and second substances,
in the above formulas (7) and (8):
R2and R3Is also a monovalent alkyl radical containing a saturated carbon-oxygen chain and having the formula CqH2q-1Wherein q is a natural number and satisfies 1. ltoreq. q.ltoreq.10;
X2has a structural formula of CH2(CH2)cCH2OCH2(CH2)dCH2；
a is a natural number and satisfies a condition that a is more than or equal to 2 and less than or equal to 100;
b is a natural number and satisfies that b is more than or equal to 2 and less than or equal to 100;
c is an integer and satisfies 0-10;
d is an integer and satisfies 0. ltoreq. d.ltoreq.10.
7. The high abrasion resistant UV resin with fingerprint resistance function according to claim 1, wherein: the linear polyester diol not containing fluorine and silicon is selected from one or more of aliphatic polyester diol, alicyclic polyester diol and aromatic polyester diol.
8. The high abrasion resistant UV resin with fingerprint resistance function according to claim 7, wherein: the aliphatic polyester diol is selected from one or more of polyethylene glycol adipate diol, polycarbonate diol and polypropylene glycol adipate diol;
the synthetic raw materials corresponding to the aliphatic ring in the alicyclic polyester diol structural unit are selected from one or more of cyclohexane dimethanol, cyclohexanediol, tricyclodecanedimethanol, dodecanediol and spiroglycol;
the synthetic raw materials corresponding to the aromatic ring in the aromatic polyester diol structural unit are selected from one or more of the combination of poly phthalic anhydride, methyl phthalic anhydride, phthalic acid, methyl phthalic acid, hydroquinone bis hydroxyethyl ether and resorcinol bis hydroxyethyl ether.
9. The high abrasion resistant UV resin with fingerprint resistance function according to claim 1, wherein: the functionality of the hydroxy acrylate containing a polyurethane structure is at least 5.
10. The high abrasion resistant UV resin with fingerprint resistance function according to claim 9, wherein: the hydroxyl acrylate containing a polyurethane structure is an equimolar ratio addition reaction product of a small molecular polyol compound and an acrylate compound containing an isocyanate group.
11. The high abrasion resistant UV resin with fingerprint resistance of claim 10, wherein: the small molecule polyol compound is selected from one or more of glycerol, butanetriol, hexanetriol, dipentaerythritol and tripentaerythritol.
12. The high abrasion resistant UV resin with fingerprint resistance of claim 10, wherein: the isocyanate group-containing acrylate compound has a functionality of 1.
13. A method for preparing the high abrasion resistant UV resin having anti-fingerprint function according to claim 1, wherein: the method comprises the following process steps:
step 1: diluting an isocyanate compound with isocyanate group functionality of 3 and a polyurethane reaction catalyst with a solvent, heating under the protection of dry nitrogen, slowly dropwise adding perfluoropolyether alcohol with one end containing hydroxyl under the stirring condition, and carrying out heat preservation reaction after the dropwise adding is finished to obtain a solution containing an intermediate product 1, wherein the solid content of a reaction system is 10-70%;
step 2: diluting an isocyanate compound with isocyanate group functionality of 3 and a polyurethane reaction catalyst with a solvent, heating under the protection of dry nitrogen, slowly dropwise adding single-end carbon hydroxyl polysiloxane under the stirring condition, and carrying out heat preservation reaction after the dripping is finished to prepare a solution containing an intermediate product 2, wherein the solid content of a reaction system is 10-70%;
and step 3: diluting an isocyanate compound with isocyanate group functionality of 2 and a polyurethane reaction catalyst with a solvent, heating under the protection of dry nitrogen, slowly dripping double-ended carbon hydroxyl polysiloxane under the condition of stirring, and carrying out heat preservation reaction after dripping is finished to prepare a solution containing an intermediate product 3, wherein the solid content of a reaction system is 10-70%;
and 4, step 4: uniformly mixing a solution containing an intermediate product 1, an intermediate product 2 and an intermediate product 3, heating under the protection of dry nitrogen, slowly dropwise adding linear polyester dihydric alcohol which does not contain fluorine and silicon under the stirring condition, and carrying out heat preservation reaction after the dropwise adding is finished to prepare a solution containing an intermediate product 4, wherein the solid content of a reaction system is 10-70%;
and 5: diluting a bifunctional isocyanate compound and a polyurethane reaction catalyst with a solvent, heating under the protection of dry nitrogen, slowly dropwise adding a monohydroxy acrylate compound under the stirring condition, and carrying out heat preservation reaction after the dropwise adding is finished to obtain a solution containing an intermediate product 5, wherein the solid content of a reaction system is 10-70%;
step 6: diluting a small molecular polyol compound and a polyurethane reaction catalyst with a solvent, heating under the protection of dry nitrogen, slowly dropwise adding hydroxyl acrylate containing a polyurethane structure under the stirring condition, and carrying out heat preservation reaction after the dropwise adding is finished to obtain a solution containing an intermediate product 6, wherein the solid content of a reaction system is 10-70%;
and 7: under the conditions of dry nitrogen protection and stirring, heating the solution containing the intermediate product 4, then slowly dropwise adding the solution containing the intermediate product 6 into the solution containing the intermediate product 4, and carrying out heat preservation reaction after the dropwise adding is finished to obtain the solution containing the UV resin product, wherein the solid content of the product is 10-70%.
14. The method of claim 13, wherein:
the stirring speed during material dropping in the reaction systems of the step 1, the step 2, the step 3 and the step 4 is all 100-500 rpm, the material dropping time is all 1h-5h, the temperature during the heat preservation reaction is all 10-100 ℃, and the reaction time is all 1h-5 h;
the stirring speed during material dropping in the reaction systems of the step 5, the step 6 and the step 7 is 100-500 rpm, the material dropping time is 1-5 h, the temperature during the heat preservation reaction is 10-80 ℃, and the reaction time is 1-5 h.
15. The method of claim 13, wherein:
the molar ratio of the isocyanate group to the hydroxyl group in the reaction systems of the step 1 and the step 2 is 3: 1;
the molar ratio of the isocyanate group to the hydroxyl group in the reaction systems of the step 3 and the step 5 is 2: 1.
16. The method of claim 13, wherein:
the mass addition amount of the polyurethane reaction catalyst in the reaction system of the step 1 is 0.01-0.5% of the total mass of the reaction solid components in the reaction system;
the mass addition amount of the polyurethane reaction catalyst in the reaction system of the step 2 is 0.01-0.5% of the total mass of the reaction solid components in the reaction system;
the mass addition amount of the polyurethane reaction catalyst in the reaction system of the step 3 is 0.01-0.5% of the total mass of the reaction solid components in the reaction system;
the mass addition amount of the polyurethane reaction catalyst in the reaction system of the step 5 is 0.01-0.5% of the total mass of the reaction solid components in the reaction system;
the mass addition amount of the polyurethane reaction catalyst in the reaction system of the step 6 is 0.01-0.5% of the total mass of the reaction solid components in the reaction system.
Technical Field
The invention relates to the technical field of high polymer materials, in particular to high-wear-resistance UV resin with an anti-fingerprint function, and further relates to a method for preparing the UV resin.
Background
With the rapid development of the 5G technology, the utilization rate of plastic materials in the surfaces of electronic communication equipment and the like is gradually improved, and the plastic materials have a tendency of replacing the existing glass, ceramics and metals. However, the plastic surface is not wear-resistant and is easy to be stained, and the wear-resistant and stain-resistant treatment is required in practical application.
The UV coating belongs to a purple-line curing coating, mainly comprises an oligomer, a reactive diluent, a photoinitiator, an auxiliary agent and the like, has higher hardness and good wear resistance, can improve the wear resistance when being coated on the surface of plastic, has the characteristics of low-temperature curing, energy conservation, no pollution, quick film forming, convenient construction and the like, and can effectively avoid the damage of high temperature in the production process to electronic product materials. The curing mechanism of the UV coating is mainly acrylate functional group free copolymerization reaction, a large number of polar functional groups exist on the surface of a cured paint film, although the paint film has higher hardness, the surface tension of the paint film surface is high, water and oil substances are easy to spread on the surface of the paint film, and therefore the surface of the UV coating is very weak to stain.
In recent years, researchers have proposed that an assistant with an anti-fingerprint function is added into the existing UV coating to solve the problem that the surface of a paint film is not resistant to stains, for example, a Chinese patent with application number CN200580014573.9 discloses a perfluoropolyether modified acrylate with an anti-stain effect, and the anti-stain property of the paint film can be improved by adding the perfluoropolyether modified acrylate into the UV coating, but the compound has poor compatibility with common UV resin, so that the wear resistance of the final paint film is poor.
Another US patent with US15029867 discloses an anti-fingerprint additive for UV coatings which gives the paint film a high anti-fingerprint and abrasion resistance, however, the compound can still only be used as a functional additive and cannot be used as the main UV resin in the formulation of UV coatings, so that the paint film finally shows an unsatisfactory abrasion resistance and cannot meet the requirement of high abrasion resistance.
Therefore, there is a need to provide a new technical solution to overcome the above-mentioned drawbacks.
Disclosure of Invention
The invention aims to provide a high-wear-resistance UV resin with an anti-fingerprint function and a preparation method thereof, which can effectively solve the technical problems.
In order to achieve the purpose of the invention, the following technical scheme is adopted:
a high wear-resistant UV resin with an anti-fingerprint function comprises the following raw materials: isocyanate mixture, perfluoropolyether alcohol containing hydroxyl at one end, mixture containing single-end hydroxyl polysiloxane and double-end hydroxyl polysiloxane, linear polyester diol containing no fluorine and silicon, hydroxyl acrylate containing a polyurethane structure and a polyurethane reaction catalyst.
Preferably, the sum of the number of moles of the hydroxyl functional groups in the perfluoropolyether alcohol having a hydroxyl group at one end, the mixture of the single-terminal hydroxyl polysiloxane and the double-terminal hydroxyl polysiloxane, the linear polyester diol containing no fluorine and silicon, and the hydroxy acrylic acid containing a polyurethane structure is equal to the number of moles of the isocyanate functional groups in the isocyanate mixture.
Preferably, the isocyanate mixture comprises:
an isocyanate compound having a functionality of 3 for the isocyanate group;
and an isocyanate compound having a functionality of 2 for the isocyanate group;
the sum of the number of moles of the perfluoropolyether alcohol having a hydroxyl group at one end and the number of moles of the monohydroxy polysiloxane at one end is equal to the number of moles of the isocyanate compound having a functionality of 3;
the number of moles of the isocyanate compound having a functionality of 2 in the isocyanate group is 2 times the number of moles of the double-terminal hydroxyl polysiloxane.
Preferably, the isocyanate compound having a functionality of 3 in the isocyanate group is selected from one or more of a trimer of toluene diisocyanate, a trimer of isophorone diisocyanate and a trimer of hexamethylene diisocyanate;
the isocyanate compound with the isocyanate group functionality of 2 is selected from one or more of 2, 4-toluene diisocyanate, 2, 6-toluene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, 1, 5-naphthalene diisocyanate and diphenylmethane diisocyanate.
Preferably, the perfluoropolyether alcohol having a hydroxyl group at one end has a structure represented by the following formula (1) or formula (2) or formula (3) or formula (4) or formula (5) or formula (6):
CF3CF2CF2O(CF(CF3)CF2O)nCF(CF3)CH2OH （1）；
CF3CF2CF2O(CF(CF3)CF2O)nCF(CF3)CH2O(CH2CH2O)mH （2）;
CF3CF2CF2O(CF2CF2CF2O)nCF2CF2CH2OH （3）；
CF3CF2CF2O(CF2CF2CF2O)nCF2CF2CH2O(CH2CHO)mH （4）；
CF3CF2CF2O(CF(CF3)CF2O)nCF(CF3)CO-X1-OH （5）；
CF3CF2CF2O(CF2CF2CF2O)nCF2CF2CO-X1-OH （6）；
n in the formulas (1) to (6) is a natural number and satisfies 2. ltoreq. n.ltoreq.60; m is a natural number and satisfies that m is more than or equal to 1 and less than or equal to 10; x1Has the structural formula of-O-R1-OH or-NH-R-OH, R1Is a divalent alkyl group containing a saturated carbon-oxygen chain.
Preferably, in the mixture containing single-terminal carbon hydroxyl polysiloxane and double-terminal carbon hydroxyl polysiloxane:
the chemical formula of the single-end carbon hydroxyl polysiloxane is shown as the following formula (7):
（7）；
a dicarbohydroxyl polysiloxane having the formula (8):
（8）；
wherein the content of the first and second substances,
in the above formulas (7) and (8):
R2and R3Is also a monovalent alkyl radical containing a saturated carbon-oxygen chain and having the formula CqH2q-1Wherein q is a natural number and satisfies 1. ltoreq. q.ltoreq.10;
X2has a structural formula of CH2(CH2)cCH2OCH2(CH2)dCH2；
a is a natural number and satisfies a condition that a is more than or equal to 2 and less than or equal to 100;
b is a natural number and satisfies that b is more than or equal to 2 and less than or equal to 100;
c is an integer and satisfies 0-10;
d is an integer and satisfies 0. ltoreq. d.ltoreq.10.
Preferably, the linear polyester diol containing no fluorine and silicon is selected from one or more of aliphatic polyester diol, alicyclic polyester diol and aromatic polyester diol.
Preferably, the aliphatic polyester diol is selected from one or more of polyethylene adipate diol, polycarbonate diol and polypropylene adipate diol;
the synthetic raw materials corresponding to the aliphatic ring in the alicyclic polyester diol structural unit are selected from one or more of cyclohexane dimethanol, cyclohexanediol, tricyclodecanedimethanol, dodecanediol and spiroglycol;
the synthetic raw materials corresponding to the aromatic ring in the aromatic polyester diol structural unit are selected from one or more of the combination of poly phthalic anhydride, methyl phthalic anhydride, phthalic acid, methyl phthalic acid, hydroquinone bis hydroxyethyl ether and resorcinol bis hydroxyethyl ether.
Preferably, the functionality of the hydroxy acrylate containing a polyurethane structure is at least 5.
Preferably, the hydroxyl acrylate containing a polyurethane structure is an equimolar ratio addition reaction product of a small molecular polyol compound and an acrylate compound containing an isocyanate group.
Preferably, the small molecule polyol compound is selected from one or more of glycerol, butanetriol, hexanetriol, dipentaerythritol and tripentaerythritol.
Preferably, the functionality of the isocyanate group in the acrylate compound containing an isocyanate group is 1.
Preferably, the acrylate compound having an isocyanate group is selected from the group consisting of an equimolar adduct of isophorone diisocyanate and hydroxyethyl acrylate, an equimolar adduct of isophorone diisocyanate and hydroxyethyl methacrylate, an equimolar adduct of 2, 4-toluene diisocyanate and hydroxyethyl acrylate, an equimolar adduct of 2, 4-toluene diisocyanate and hydroxyethyl methacrylate, an equimolar adduct of isophorone diisocyanate and pentaerythritol triacrylate, a combination of one or more of equimolar adducts of 2, 4-toluene diisocyanate and pentaerythritol triacrylate, equimolar adducts of isophorone diisocyanate and dipentaerythritol pentaacrylate, equimolar adducts of 2, 4-toluene diisocyanate and dipentaerythritol pentaacrylate, isocyanate ethyl acrylate, and isocyanate ethyl methacrylate.
The invention also provides a method for preparing the high-wear-resistance UV resin with the fingerprint resistance function, which comprises the following process steps:
step 1: diluting an isocyanate compound with isocyanate group functionality of 3 and a polyurethane reaction catalyst with a solvent, heating under the protection of dry nitrogen, slowly dropwise adding perfluoropolyether alcohol with one end containing hydroxyl under the stirring condition, and carrying out heat preservation reaction after the dropwise adding is finished to obtain a solution containing an intermediate product 1, wherein the solid content of a reaction system is 10-70%;
step 2: diluting an isocyanate compound with isocyanate group functionality of 3 and a polyurethane reaction catalyst with a solvent, heating under the protection of dry nitrogen, slowly dropwise adding single-end carbon hydroxyl polysiloxane under the stirring condition, and carrying out heat preservation reaction after the dripping is finished to prepare a solution containing an intermediate product 2, wherein the solid content of a reaction system is 10-70%;
and step 3: diluting an isocyanate compound with isocyanate group functionality of 2 and a polyurethane reaction catalyst with a solvent, heating under the protection of dry nitrogen, slowly dripping double-ended carbon hydroxyl polysiloxane under the condition of stirring, and carrying out heat preservation reaction after dripping is finished to prepare a solution containing an intermediate product 3, wherein the solid content of a reaction system is 10-70%;
and 4, step 4: uniformly mixing a solution containing an intermediate product 1, an intermediate product 2 and an intermediate product 3, heating under the protection of dry nitrogen, slowly dropwise adding linear polyester dihydric alcohol which does not contain fluorine and silicon under the stirring condition, and carrying out heat preservation reaction after the dropwise adding is finished to prepare a solution containing an intermediate product 4, wherein the solid content of a reaction system is 10-70%;
and 5: diluting a bifunctional isocyanate compound and a polyurethane reaction catalyst with a solvent, heating under the protection of dry nitrogen, slowly dropwise adding a monohydroxy acrylate compound under the stirring condition, and carrying out heat preservation reaction after the dropwise adding is finished to obtain a solution containing an intermediate product 5, wherein the solid content of a reaction system is 10-70%;
step 6: diluting a small molecular polyol compound and a polyurethane reaction catalyst with a solvent, heating under the protection of dry nitrogen, slowly dropwise adding hydroxyl acrylate containing a polyurethane structure under the stirring condition, and carrying out heat preservation reaction after the dropwise adding is finished to obtain a solution containing an intermediate product 6, wherein the solid content of a reaction system is 10-70%;
and 7: under the conditions of dry nitrogen protection and stirring, heating the solution containing the intermediate product 4, then slowly dropwise adding the solution containing the intermediate product 6 into the solution containing the intermediate product 4, and carrying out heat preservation reaction after the dropwise adding is finished to obtain the solution containing the UV resin product, wherein the solid content of the product is 10-70%.
Preferably, the stirring speed during material dropping in the reaction systems of the step 1, the step 2, the step 3 and the step 4 is 100-;
the stirring speed during material dropping in the reaction systems of the step 5, the step 6 and the step 7 is 100-500 rpm, the material dropping time is 1-5 h, the temperature during the heat preservation reaction is 10-80 ℃, and the reaction time is 1-5 h.
Preferably, the molar ratio of the isocyanate group to the hydroxyl group in the reaction systems of the step 1 and the step 2 is 3: 1;
the molar ratio of the isocyanate group to the hydroxyl group in the reaction systems of the step 3 and the step 5 is 2: 1.
Preferably, the mass addition amount of the polyurethane reaction catalyst in the reaction system of the step 1 is 0.01-0.5% of the total mass of the reaction solid components in the reaction system;
the mass addition amount of the polyurethane reaction catalyst in the reaction system of the step 2 is 0.01-0.5% of the total mass of the reaction solid components in the reaction system;
the mass addition amount of the polyurethane reaction catalyst in the reaction system of the step 3 is 0.01-0.5% of the total mass of the reaction solid components in the reaction system;
the mass addition amount of the polyurethane reaction catalyst in the reaction system of the step 5 is 0.01-0.5% of the total mass of the reaction solid components in the reaction system;
the mass addition amount of the polyurethane reaction catalyst in the reaction system of the step 6 is 0.01-0.5% of the total mass of the reaction solid components in the reaction system.
Preferably, the difunctional isocyanate compound in the step 5 is selected from one or more of isophorone diisocyanate and 2, 4-toluene diisocyanate; the acrylate compound containing monohydroxy in the step 5 is one or more of hydroxyethyl acrylate, hydroxyethyl methacrylate, pentaerythritol triacrylate and dipentaerythritol pentaacrylate.
Preferably, the hydroxyl acrylate containing a polyurethane structure in the step 6 is selected from one or more of the group consisting of intermediate 5, isocyanate ethyl acrylate and isocyanate ethyl methacrylate.
Compared with the prior art, the invention has the following beneficial effects:
1. according to the invention, through the reaction among the components, the perfluoropolyether and the organosilicon chain segment are simultaneously introduced into the polymer molecular chain of the UV resin, and the friction coefficient and the surface energy of the resin surface are reduced by utilizing the synergistic effect of the fluorine and silicon molecules, so that the prepared UV resin has good fingerprint-resistant and wear-resistant properties; meanwhile, the high-content carbamate is introduced into the polymer molecular chain of the UV resin to improve the hydrogen bond content of the molecular chain, so that the cohesive energy of the molecular chain is improved, and the wear resistance of the UV resin is further improved.
2. The UV resin prepared by the invention has excellent intermiscibility with common UV resin, and can be used as main resin to be compounded with the common UV resin to prepare the UV coating with fingerprint resistance and high wear resistance; meanwhile, performance tests are carried out on the UV coating prepared from the UV resin disclosed by the invention, and the results show that the final paint film not only has very high fingerprint and wear resistance, but also the surface of the paint film still keeps a high water contact angle after the paint film is worn by steel wool, namely the surface of the paint film still has very high anti-fouling property after the paint film is worn by the steel wool.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the following will clearly and completely describe the technical solutions in the embodiments of the present invention, and it is obvious that the described embodiments are some embodiments of the present invention, but not all embodiments.
Firstly, resin preparation
Example 1
This example provides a high abrasion resistant UV resin 1# sample (UV-1) with anti-fingerprint function, which is prepared as follows:
(1) after 7.25 g of a trimer of isophorone diisocyanate (trade name T1890/100, supplied by winning company) and 0.15 g of dibutyltin dilaurate were diluted with 47.25 g of benzotrifluoride, the temperature was raised to 80 ℃ under the protection of dry nitrogen, and 40.00g of perfluoropolyether alcohol (trade name DOL-4000, molecular formula CF-4000, slowly added dropwise with stirring3CF2CF2O(CF(CF3)CF2O)nCF(CF3)CH2OH, the molecular weight is 4000, which is provided by Taicang chemical environmental protection chemical company), the stirring speed is 200 r/min, the dripping time is 1h, the reaction temperature is kept after the dripping is finished, and the reaction is continued for 2h to prepare a solution containing an intermediate product 1;
(2) after 7.25 g of trimer of isophorone diisocyanate (the trademark is T1890/100, provided by winning company) and 0.15 g of dibutyltin dilaurate are diluted by 17.25 g of benzotrifluoride, the temperature is raised to 80 ℃ under the protection of dry nitrogen, 10.00g of single-end hydroxy dimethyl silicone oil (the trademark is IOTA2050, the molecular weight is 1000, provided by Anhui Eyota Silicone oil Co., Ltd.) is slowly dripped under the stirring condition, the stirring speed is 200 r/min, the dripping time is 1h, the reaction temperature is kept after the dripping is finished, and the reaction is continued for 2h, so that a solution containing an intermediate product 2 is prepared;
(3) after 17.80 g of isophorone diisocyanate and 0.15 g of dibutyltin dilaurate are diluted by 47.80 g of benzotrifluoride, the temperature is raised to 80 ℃ under the protection of dry nitrogen, 40.00g of double-end hydroxyl dimethyl silicone oil (the trade name is Silok, the molecular weight is 1000, provided by Stocko high molecular polymer Co., Ltd., Guangzhou) is slowly dripped under the stirring condition, the stirring speed is 200 r/min, the dripping time is 1h, the dripping is finished, the reaction temperature is kept, and the reaction is continued for 2h, so that a solution containing an intermediate product 3 is prepared;
(4) uniformly mixing the solution containing the intermediate product 1, the intermediate product 2 and the intermediate product 3, heating to 50 ℃ under the protection of dry nitrogen, slowly dropwise adding a mixed solution of 160.00 g of polycarbonate diol (the brand is UH-CARB200, the molecular weight is 2000 and the molecular weight is provided by Japan and Japan) and 160.00 g of butanone under the stirring condition, stirring at the speed of 200 r/min for 1h, and keeping the reaction temperature and continuing to react for 2h after the dropwise adding is finished to obtain a solution containing an intermediate product 4;
(5) after 23.71 g of tripentaerythritol, 0.40 g of p-hydroxyanisole and 0.15 g of dibutyltin dilaurate are diluted by 55.00 g of butanone, the temperature is raised to 50 ℃ under the protection of dry nitrogen, 31.29g of isocyanate ethyl acrylate is slowly dripped under the stirring condition, the stirring speed is 200 r/min, the dripping time is 1h, the reaction temperature is kept after the dripping is finished, and the reaction is continued for 2h, so that a solution containing an intermediate product 6 is prepared;
(6) under the protection of dry nitrogen and stirring, heating the solution containing the intermediate product 4 to 50 ℃, slowly dropwise adding the solution containing the intermediate product 6, stirring at the speed of 200 revolutions per minute for 4 hours, keeping the reaction temperature after dropwise adding is finished, and continuously reacting for 4 hours to obtain the product UV-1 with the solid content of 50%.
Example 2
This example provides a high abrasion resistant UV resin 1# sample (UV-2) with anti-fingerprint function, which is prepared as follows:
following the procedure and procedure as shown in example 1, the tripentaerythritol was replaced by dipentaerythritol in step (5), the corresponding mass was replaced by 16.24g, the mass of ethyl isocyanate acrylate was replaced by 22.46g, and the mass of butanone in this step was replaced by 38.70g, all other conditions and masses being the same as in example 1, to give UV-2, a solid content of 50%.
Example 3
This example provides a high abrasion resistant UV resin 1# sample (UV-3) with anti-fingerprint function, which is prepared as follows:
according to the procedure and process shown in example 1, the mass of isophorone diisocyanate was changed to 8.90g, the mass of dihydroxy dimethylsilicone oil was changed to 20.00g, and the mass of trifluorotoluene in this step was changed to 28.90g in step (3); in step (5), tripentaerythritol is replaced by dipentaerythritol, the corresponding mass is replaced by 16.24g, the mass of ethyl isocyanate acrylate is replaced by 22.46g, and the mass of butanone in this step is replaced by 38.70 g; the remaining conditions and mass were the same as in example 1, giving the product UV-3, a solids content of 50%.
Preparation of coatings and paint films
Step 1: compounding UV coating according to a formula (the addition amount of each component is calculated by weight parts) shown in Table 1, and uniformly stirring and mixing at a high speed;
step 2: carrying out reaction and secondary filtration on the UV coating by using a PP (polypropylene) filter element with the diameter of 2 microns;
and step 3: scraping the filtered coating on an acrylic plastic plate by using a 20-micron wire rod, and baking for 5 minutes in a 55-DEG C blast drying oven;
and 4, step 4: placing the baked plastic plate on a crawler-type UV photocuring machine for photocuring operation, wherein a light source is a high-pressure mercury lamp, the wavelength is 365nm, and finally preparing the cured acrylic plate coated with the UV coating;
table 1 coating formulation table
In table 1, CN9013NS represents a multifunctional urethane acrylate produced by Sartomer corporation, which has a functionality of 9; SIO-P100 represents the nano-silica powder produced by Shanghai Zhengnano materials. KY1203 represents an anti-fingerprint functional auxiliary agent for UV coating produced by Japan shinier-shin-Etsu, and contains an acrylate functional group which can be cured by UV light.
Table 2 paint film performance test tables for paints 1 to 6
The paint film property test methods for paints 1 to 6 in table 2 are as follows:
1) hardness: the pencil hardness test method is adopted:
the test was carried out according to the method of GBT 6739-.
2) The adhesion test method comprises the following steps:
the test was performed according to GB _ T9286-1998 method.
3) Water contact angle test method:
test pieces prepared from coatings 1 to 6 were placed on a contact angle meter (model: DSA30, supplied by kluyvers ltd, germany) with deionized water and dodecane as test media and a test droplet volume of 4 μ L, and the contact angle values of 3 droplets were recorded and the arithmetic mean of the 3 test data was taken.
4) And (3) wear resistance test:
the test pieces prepared from the coatings 1 to 6 were fixed to an abrasion resistance tester (ESIDA-NM-002, available from Shimada instruments Co., Ltd., Shenzhen), and the contact area was 2X 2cm2Binding 0000# steel wool on the contact friction probe;
applying 1000g of test load above the probe, testing for 35-40 times/min at a speed of 3-4cm in stroke, performing reciprocating friction for 3000 times, and stopping the test after performing a wear test for 20 minutes;
observing the appearance of a paint film in the abrasion area, judging the paint film to be OK if the abrasion area is not scratched, and otherwise, judging the paint film to be Fail; the water contact angle of the paint film in the abraded area was also tested.
By comparing the performance test data of the paint film of the test piece prepared by the paint 1-6, the UV paint prepared by the UV resin has a higher water contact angle and higher steel wool resistance compared with the common UV paint; meanwhile, the surface of the paint film still keeps a higher water contact angle after being worn by steel wool, namely the surface of the paint film still has high anti-fouling property after being worn by the steel wool, so that the UV resin can enhance the anti-fouling and wear-resisting properties of the UV coating and can meet the production requirements of high-wear-resisting and stain-resisting products.
Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention.