WO2020133616A1 - 水性防雾树脂和水性防雾涂料组合物及其制备方法 - Google Patents

水性防雾树脂和水性防雾涂料组合物及其制备方法 Download PDF

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Publication number
WO2020133616A1
WO2020133616A1 PCT/CN2019/072789 CN2019072789W WO2020133616A1 WO 2020133616 A1 WO2020133616 A1 WO 2020133616A1 CN 2019072789 W CN2019072789 W CN 2019072789W WO 2020133616 A1 WO2020133616 A1 WO 2020133616A1
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Prior art keywords
compound
water
fog
diisocyanate
based anti
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PCT/CN2019/072789
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English (en)
French (fr)
Inventor
缪培凯
凌云剑
王卫国
杨波
吕国强
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湖南松井新材料股份有限公司
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Application filed by 湖南松井新材料股份有限公司 filed Critical 湖南松井新材料股份有限公司
Priority to US16/614,608 priority Critical patent/US11332639B2/en
Priority to JP2019565799A priority patent/JP6934538B2/ja
Priority to EP19783966.5A priority patent/EP3699217A4/en
Publication of WO2020133616A1 publication Critical patent/WO2020133616A1/zh

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    • C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
    • C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
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Definitions

  • the invention relates to the technical field of water-based coatings, in particular, to a water-based anti-fog resin and a preparation method thereof.
  • the present invention also relates to a water-based anti-fog coating composition including the above-mentioned water-based anti-fog resin and a preparation method thereof.
  • the invention provides a water-based anti-fog resin, a preparation method thereof and an anti-fog coating composition having the water-based anti-fog resin, to solve the technical problem that an organic solvent needs to be added in the preparation of the existing polymer coating and is not an aqueous coating.
  • an aqueous anti-fog resin having the following structural formula:
  • m, s, n, p, q, a, b, and c represent the degree of polymerization of each monomer, and the value of the degree of polymerization of each monomer is limited to the number average molecular weight of the water-based anti-fog resin of 5000 to 100,000.
  • m, s, n, p, q, a, b, c are all positive integers,
  • R 1 and the isocyanate group form a diisocyanate compound
  • R 1 is the parent structure of the diisocyanate compound
  • R 2 is a compound containing both hydroxyl (OH) and carboxyl (COOH),
  • R 3 , R 4 , R 5 and R 6 are each selected from one of H and CH 3 ,
  • R 7 is one of -O - N + H(C 2 H 5 OH) 3 , -O - N + H(C 2 H 5 ) 3 , -O - K + or -O - Na + .
  • the diisocyanate compound is one of toluene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate or dicyclohexylmethane diisocyanate.
  • R 2 is lactic acid or dimethylolpropionic acid.
  • R 1 is the parent structure of isophorone diisocyanate
  • R 2 is dimethylolpropionic acid
  • R 3 , R 4 and R 6 are CH 3
  • R 5 is H
  • R 7 is -O - N + H(C 2 H 5 OH) 3 .
  • the number average molecular weight of the water-based anti-fog resin is 50000-100000.
  • the compound 1 and the compound 2 are reacted at 60 to 90°C for 0.5 to 4 hours, and then a basic compound is added, and the reaction is performed at 60 to 90°C for 0.1 to 0.5 hours.
  • the basic compound and some sulfonic acid groups and carboxyl groups The reaction forms a salt to obtain an aqueous anti-fog resin, and the basic compound is triethanolamine, triethylamine, potassium hydroxide or sodium hydroxide.
  • the diisocyanate compound is toluene diisocyanate or diphenylmethane diisocyanate or hexamethylene diisocyanate or isophorone diisocyanate or dicyclohexylmethane diisocyanate, and the R 2 compound containing hydroxyl and carboxyl groups is lactic acid Or dimethylolpropionic acid;
  • step (1) the molar ratio of the R 2 compound containing hydroxyl groups and carboxyl groups and the diisocyanate compound containing R 1 is 1:2 to 2.5, and the mass of the catalyst is the R 2 compound containing hydroxyl groups and carboxyl groups and containing The total mass of the diisocyanate compound of R 1 is 0.2 to 1%.
  • step (2) isooctyl acrylate, methacrylamide or acrylamide, methyl methacrylate or methyl acrylate, acrylic acid or methacrylic acid, 2-acrylamide-2-methylpropanesulfonic acid
  • the molar ratio of N,N-dimethylacrylamide, hydroxyethyl methacrylate or hydroxyethyl acrylate is 1:0.1 ⁇ 0.4:0.8 ⁇ 1:0.1 ⁇ 0.4:0.4 ⁇ 0.8:0.1 ⁇ 0.4:0.6 ⁇ 1.2
  • the amount of azobisisobutyronitrile is 0.1-0.5% of the total mass of the remaining reaction raw materials.
  • step (3) the molar ratio of compound 2 to compound 1 is 1:0.2 to 0.8, and the molar ratio of basic compound to compound 2 is 1:0.5 to 1.2.
  • a water-based anti-fog coating composition comprising the above-mentioned water-based anti-fog resin or the water-based anti-fog resin prepared by the above-mentioned preparation method 30 to 60 parts and a cross-linking agent 5 to 20 Parts, 5-10 parts of surfactant, 0.1-1 part of leveling agent, 20-60 parts of diluent, the above contents are all parts by weight.
  • the cross-linking agent is an aqueous polycarbodiimide
  • the leveling agent is a polyether-modified silicone containing acrylic functional groups
  • the diluent is deionized water or distilled water.
  • a method for preparing the above coating composition comprising the following steps: mixing the water-based anti-fog resin, crosslinking agent, surfactant, leveling agent, and diluent according to the above weight parts Evenly, the water-based anti-fog coating composition is obtained.
  • the coating composition adopts a thermal curing method: the baking temperature is 60-120°C, and the baking time is 5-30 minutes.
  • the water-based anti-fog resin of the present invention introduces molecular segments and functional groups with good hydrophilicity and hygroscopicity: N,N-dimethylacrylamide has excellent hygroscopicity and antistatic properties, hydroxyethyl methacrylate or Hydroxyethyl acrylate provides hydrophilic hydroxy functional groups, methacrylic acid or acrylic acid and lactic acid or dimethylolpropionic acid provides hydrophilic carboxyl functional groups, 2-acrylamide-2-methylpropanesulfonic acid provides hydrophilicity , Methacrylamide or acrylamide has high water absorption characteristics, methyl methacrylate or methyl acrylate provides rigidity, isooctyl acrylate provides flexibility.
  • the water-based anti-fog resin can be given excellent anti-fog performance, coating film strength and transparent leveling appearance, and the water contact angle of the cured coating can reach 1-10°.
  • the water-based anti-fog resin of the present invention contains a carboxyl COOH, which can undergo a chemical cross-linking reaction with polycarbodiimide to enhance the strength and performance of the cured paint film, and at the same time, polycarbodiimide can help improve the adhesion to the coating material Stability function.
  • the cured coating of the coating composition of the present invention has good anti-fog performance, abrasion resistance, water resistance, chemical resistance, stain resistance, and ultraviolet resistance, and excellent adhesion to the substrate; at the same time, the coating is strong and has excellent
  • the film-forming strength and Quluo resistance can be used for anti-fog treatment on the surface of mobile phone windows, PC or PMMA transparent materials, automobile glass and bathroom mirrors, and has good long-term stability.
  • One aspect of the present invention provides a water-based anti-fog resin having the following structural formula:
  • m, s, n, p, q, a, b, and c represent the degree of polymerization of each monomer, and the value of the degree of polymerization of each monomer is limited to the number average molecular weight of the water-based anti-fog resin of 5000 to 100,000.
  • m, s, n, p, q, a, b, and c are all positive integers.
  • R 1 and the isocyanate group form a diisocyanate compound.
  • R 1 is the parent structure of the diisocyanate compound.
  • the diisocyanate compound can be toluene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, isophor One of ketone diisocyanate or dicyclohexylmethane diisocyanate.
  • R 2 is a compound containing both a hydroxyl group (OH) and a carboxyl group (COOH), and can be selected from one of hydroxyl group-containing lactic acid and dimethylolpropionic acid.
  • R 3 , R 4 , R 5 and R 6 are each selected from one of H and CH 3 .
  • R 7 is one of -O - N + H(C 2 H 5 OH) 3 , -O - N + H(C 2 H 5 ) 3 , -O - K + or -O - Na + .
  • the water-based anti-fog resin is formed by polymerizing multiple compound monomers.
  • R 1 is the parent structure of the diisocyanate compound, that is, the structural unit of the diisocyanate compound, and the isocyanate group forms a diisocyanate compound on the parent structure represented by R 1 .
  • two isocyanate groups of the diisocyanate compound participate in the reaction to form
  • the specific structure is shown in the structural formula of water-based anti-fog resin.
  • Some of the above diisocyanate compounds contain multiple isomers, and R 1 is the parent structure corresponding to the corresponding structure.
  • Toluene diisocyanate includes Two isomers, the corresponding R 1 is
  • R 2 is a structural unit of a hydroxyl-containing compound, and the hydroxyl-containing compound includes lactic acid and dimethylolpropionic acid.
  • the terminal hydroxyl group of the hydroxyl-containing compound removes H to obtain an R 2 group.
  • the water-based anti-fog resin of the present invention introduces molecular segments and functional groups with good hydrophilicity and hygroscopicity: N,N-dimethylacrylamide has excellent hygroscopicity and antistatic properties, hydroxyethyl methacrylate or Hydroxyethyl acrylate provides hydrophilic hydroxy functional groups, methacrylic acid or acrylic acid and lactic acid or provides hydrophilic carboxyl functional groups, 2-acrylamide-2-methylpropanesulfonic acid provides hydrophilic, methacrylamide or Acrylamide has high water absorption properties, methyl methacrylate or methyl acrylate provides rigidity, and isooctyl acrylate provides flexibility.
  • the water-based anti-fog resin can be given excellent anti-fog performance and coating film strength, and the water contact angle of the cured coating can reach 1-10°.
  • a part of the sulfonic acid group and carboxylic acid group are neutralized to form a salt by the basic compound, and the water-based anti-fog resin is made water-soluble, and can be dissolved/dispersed in distilled water or deionized water.
  • R 1 is the parent structure of isophorone diisocyanate
  • R 2 is dimethylolpropionic acid
  • R 3 , R 4 and R 6 are CH 3
  • R 5 is H
  • R 7 is -O - N + H(C 2 H 5 OH) 3 .
  • the water-based anti-fog resin of this structure has a small water contact angle, better anti-fog effect and more excellent performance.
  • the number average molecular weight of the water-based anti-fog resin is 50,000 to 100,000.
  • the number-average molecular weight water-based anti-fog resin is easy to form a film, and the anti-fog effect is further improved.
  • Another aspect of the present invention provides a method for preparing the aforementioned water-based anti-fog resin, including the following steps:
  • the compound 1 and the compound 2 are reacted at 60 to 90°C for 0.5 to 4 hours, and then a basic compound is added, and the reaction is performed at 60 to 90°C for 0.1 to 0.5 hours.
  • the basic compound and some sulfonic acid groups and carboxyl groups The reaction forms a salt to obtain an aqueous anti-fog resin.
  • the basic compound is triethanolamine or triethylamine, potassium hydroxide or sodium hydroxide.
  • step (1) using dibutyltin dilaurate or p-toluenesulfonic acid as a catalyst, the R 2 compound containing hydroxyl and carboxyl groups and the monomer of the R 1 containing diisocyanate compound are reacted at 40 to 60° C. for 0.5 to In 2 hours, compound 1 was obtained.
  • the reaction equation of step (1) is as follows:
  • the diisocyanate compound is toluene diisocyanate or diphenylmethane diisocyanate or hexamethylene diisocyanate or isophorone diisocyanate or dicyclohexylmethane diisocyanate, and the hydroxyl-containing R 2 compound is Lactic acid or dimethylolpropionic acid, but not limited to this.
  • the final synthetic resin of the present invention contains carboxyl COOH, which can undergo a chemical crosslinking reaction with polycarbodiimide to enhance the strength and performance of the cured paint film, and at the same time, polycarbodiimide can help improve the stability of adhesion to the coating material Function.
  • step (2) isooctyl acrylate monomer, methacrylamide or acrylamide, methyl methacrylate or methyl acrylate, acrylic acid or methacrylic acid, 2-acrylamide- 2-Methylpropanesulfonic acid, N,N-dimethylacrylamide, hydroxyethyl methacrylate or hydroxyethyl acrylate, azobisisobutyronitrile monomer, and use nitrogen replacement to remove the air in the reaction bottle, Under a nitrogen atmosphere, the temperature was raised to 60 to 90°C, and the reaction was condensed and refluxed for 4 to 8 hours to obtain Compound 2.
  • step (3) the above-mentioned compound 2 and compound 1 are reacted at 60-90°C for 0.5-4 hours; then a basic compound is added and reacted at 60-90°C for 0.1-0.5 hours to finally obtain an aqueous anti-fog resin.
  • the degree of polymerization of hydroxyethyl methacrylate or hydroxyethyl acrylate is s+(ns).
  • the structure where the polymer is s has reacted with compound 1
  • the reacted polymer is described by the structure of ns.
  • the reaction equation of step (3) is as follows:
  • the reaction temperature and time are lower than the set value, the degree of progress of the reaction in each step is low, and the corresponding product has a low degree of polymerization, resulting in a low molecular weight of the water-based anti-fog resin synthesized, and the resin is difficult to form a film ,
  • the anti-fog effect is poor; if the reaction temperature and time are higher than the set value, it will consume energy and time, and the water-based anti-fog resin has the risk of bursting gel.
  • step (1) the molar ratio of the R 2 compound containing hydroxyl and carboxyl groups and the diisocyanate compound containing R 1 is 1:2 to 2.5.
  • the mass of the catalyst is 0.2 to 1% of the total mass of the R 2 compound containing hydroxyl and carboxyl groups and the diisocyanate compound containing R 1 .
  • step (2) isooctyl acrylate, methacrylamide or acrylamide, methyl methacrylate or methyl acrylate, acrylic acid or methacrylic acid, 2-acrylamide-2-methylpropanesulfonic acid
  • the molar ratio of N,N-dimethylacrylamide, hydroxyethyl methacrylate or hydroxyethyl acrylate is 1:0.1 ⁇ 0.4:0.8 ⁇ 1:0.1 ⁇ 0.4:0.4 ⁇ 0.8:0.1 ⁇ 0.4:0.6 ⁇ 1.2, if the molar ratio is not within this range, the content of isocyanate groups in compound 1 is low or high, and the low value may easily lead to inadequate reaction of the hydroxyl groups in compound 1 and compound 2 and lower the molecular weight of the water-based anti-fog resin; If it is too high, the isocyanate groups in the water-based anti-fog resin are likely to remain too much, which affects the storage stability of the resin and is easy to gel.
  • the amount of azobisisobutyronitrile is 0.1-0.5% of the total mass of the above monomers. That is, the amount of azobisisobutyronitrile is isooctyl acrylate, methacrylamide or acrylamide, methyl methacrylate or methyl acrylate, acrylic acid or methacrylic acid, 2-acrylamide-2-methylpropanesulfonic acid , N,N-dimethylacrylamide, hydroxyethyl methacrylate or hydroxyethyl acrylate 0.1 to 0.5% of the total mass.
  • step (3) the molar ratio of compound 2 to compound 1 is 1:0.2 to 0.8, and the molar ratio of basic compound to compound 2 is 1:0.5 to 1.2. If the molar ratio is not within this range, it is difficult to control the molecular weight of the water-based anti-fog resin within the set range, and the film-forming properties and anti-fog effect of the resin will deteriorate.
  • step (1) the R 2 compound containing a hydroxyl group and a carboxyl group and the diisocyanate compound containing R 1 are reacted at 60° C. for 2 hours. Under this condition, the reaction conditions are mild, and the yield of the reaction is higher.
  • reaction temperature in step (2) is 90°C, and the reaction time is 8 hours. Under this condition, the reaction conditions are mild, and the yield of the reaction is higher.
  • step (3) compound 2 and compound 1 are reacted at 90°C for 4 hours, triethanolamine is added and reacted at 90°C for 0.5 hour, and the molar ratio of the amount of triethanolamine added to compound 2 is 1:1.2. Under this condition, the reaction conditions are mild, and the yield of the reaction is higher.
  • a water-based anti-fog coating composition comprising the above-mentioned water-based anti-fog resin or the water-based anti-fog resin prepared by the above-mentioned preparation method 30 to 60 parts and the cross-linking agent 5 to 20 parts , 5-10 parts of surfactant, 0.1-1 part of leveling agent, 20-60 parts of diluent, the above contents are all parts by weight.
  • the cross-linking agent is water-based polycarbodiimide (for example, water-based polycarbodiimide UN-557 of Shanghai Union Chemical Co., Ltd.), which can be combined with the carboxylic acid structural unit (COOH) in the water-based anti-fog resin.
  • a chemical cross-linking reaction to form a film can improve the wear resistance, water resistance, chemical resistance, stain resistance, and ultraviolet resistance of the coating, and improve the adhesion to the special substrate; at the same time, the coating can be stronger, thereby improving the Film strength and resistance to Quluo;
  • the surfactant is at least one of water-soluble sodium lauryl sulfate and dioctyl sodium sulfosuccinate.
  • the leveling agent is a polyether-modified silicone containing acrylic functional groups (for example, BYK475 of BYK in Germany) to promote mirror leveling of the paint film; the solvent is deionized water or distilled water to adjust the construction viscosity.
  • the preparation method of the above coating composition includes the following steps: mixing the water-based anti-fog resin, crosslinking agent, leveling agent, and diluent according to the above-mentioned parts by weight to obtain the water-based anti-fog coating composition.
  • the coating composition adopts a thermal curing method: a baking temperature of 60 to 120°C and a baking time of 5 to 30 minutes.
  • the synthetic resin of the present invention is a thermosetting resin, so a thermosetting method is used.
  • dibutyltin dilaurate as a catalyst, dimethylolpropionic acid and toluene diisocyanate monomer were reacted at 40°C for 0.5 hour to obtain compound 1.
  • the molar ratio of dimethylol propionic acid and toluene diisocyanate monomer is 1:2; the amount of catalyst is 0.2% of the total mass of the above two raw materials.
  • isooctyl acrylate, methacrylamide, methyl methacrylate, methacrylic acid, 2-acrylamide-2-methylpropanesulfonic acid, N,N-dimethylacrylamide, hydroxyethyl acrylate The molar ratio is 1:0.1:0.8:0.4:0.4:1.2.
  • the amount of azobisisobutyronitrile is 0.1% of the total mass of the above monomers.
  • lactic acid and isophorone diisocyanate monomer were reacted at 60°C for 2 hours to obtain compound 1.
  • the molar ratio of lactic acid and isophorone diisocyanate monomer is 1:2.5; the amount of catalyst is 0.5% of the total mass of the above two raw materials.
  • the molar ratio of isooctyl acrylate, acrylamide, methyl acrylate, methacrylic acid, 2-acrylamide-2-methylpropanesulfonic acid, N,N-dimethylacrylamide, hydroxyethyl methacrylate It is 1:0.4:1:0.4:0.8:0.4:1.2.
  • the amount of azobisisobutyronitrile is 0.5% of the total mass of the above monomers.
  • isooctyl acrylate, methacrylamide, methyl methacrylate, methacrylic acid, 2-acrylamide-2-methylpropanesulfonic acid, N,N-dimethylacrylamide, hydroxyethyl acrylate The molar ratio is 1:0.2:0.9:0.2:0.6:0.3:0.8.
  • the amount of azobisisobutyronitrile is 0.2% of the total mass of the above monomers.
  • isooctyl acrylate, methacrylamide, methyl methacrylate, methacrylic acid, 2-acrylamide-2-methylpropanesulfonic acid, N,N-dimethylacrylamide, hydroxyethyl acrylate The molar ratio is 1:0.3:0.9:0.2:0.6:0.2:0.9.
  • the amount of azobisisobutyronitrile is 0.3% of the total mass of the above monomers.
  • dimethylol propionic acid and toluene diisocyanate monomer were reacted at 50°C for 0.3 hours to obtain compound 1.
  • the molar ratio of dimethylol propionic acid and toluene diisocyanate monomer is 1:1.5; the amount of catalyst is 0.1% of the total mass of the above two raw materials.
  • isooctyl acrylate, methacrylamide, methyl methacrylate, methacrylic acid, 2-acrylamide-2-methylpropanesulfonic acid, N,N-dimethylacrylamide, hydroxyethyl acrylate The molar ratio is 1:0.05:0.2:0.1:0.2:0.1:0.3.
  • the amount of azobisisobutyronitrile is 0.1% of the total mass of the above monomers.
  • dibutyltin dilaurate as a catalyst, dimethylolpropionic acid and toluene diisocyanate monomer were reacted at 35°C for 0.5 hour to obtain compound 1.
  • the molar ratio of dimethylol propionic acid and toluene diisocyanate monomer is 1:2; the amount of catalyst is 0.2% of the total mass of the above two raw materials.
  • isooctyl acrylate, methacrylamide, methyl methacrylate, methacrylic acid, 2-acrylamide-2-methylpropanesulfonic acid, N,N-dimethylacrylamide, hydroxyethyl acrylate The molar ratio is 1:0.1:0.8:0.4:0.4:1.2.
  • the amount of azobisisobutyronitrile is 0.1% of the total mass of the above monomers.
  • Table 1 The content of each component in the water-based anti-fog coating composition in Examples 5 to 8 and Comparative Examples 1 to 2
  • the coating compositions of the above Examples 5 to 8 were coated on the surface of the transparent PC material, and a baking temperature of 70° C. and a baking time of 20 minutes were used to obtain an anti-fog coating.
  • the coatings obtained after the coating of the above Examples 5 to 8 were tested for adhesion, abrasion resistance, hardness, water contact angle and anti-fog properties. The test method is as follows:
  • the adhesion is tested according to GB9286-1998 standard.
  • the RCA abrasion resistance test method is the conventional RCA abrasion resistance test method, using Norman RCA abrasion resistance tester, with a paint film load of 175 g.
  • Pencil hardness test according to GB/T 6739-2006 standard test, load 1000g; adhesion test according to GB 9286-1998 standard test.
  • Water contact angle test is tested according to GB/T 23764-2009 standard.
  • the anti-fog performance test is evaluated by two methods: cold fog and hot fog: the cold fog test method is to store the glass product with the cured coating at -15 °C for 30 minutes, and then take it out at room temperature of 50% humidity Observe the transparency of the coated product.
  • the hot mist test method is that the coated surface of the product is placed in saturated water vapor at 80°C for 60 minutes and then taken out, and the transparency of the coated product is observed under the room temperature condition of 50% humidity. Transparency levels are expressed in order from 1 to 5, with 5 being completely transparent and 1 being cloudy and opaque.
  • the coating compositions formed by the coating compositions of Examples 5 to 8 are applied to transparent PC, all of which show good surface properties; the anti-fogging performance of the coating composition of Example 6 is particularly remarkable, and at the same time has good The adhesion and wear resistance and hardness.
  • the number-average molecular weights of the prepared water-based anti-fog resins in comparative examples 1 and 2 are 3000 and 2000, respectively, both of which are less than the values required by the present invention, the anti-fog properties of the cured coatings of their coating compositions are all Significantly reduced, and the wear resistance and hardness of the coating are significantly reduced.

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Abstract

一种水性防雾树脂及其制备方法，该水性防雾树脂的制备方法包括：在催化剂的存在下使含羟基和羧基的R 2化合物与含R 1的二异氰酸酯类化合物反应得到化合物1；将丙烯酸异辛酯、甲基丙烯酰胺或丙烯酰胺、甲基丙烯酸甲酯或丙烯酸甲酯、丙烯酸或甲基丙烯酸、2-丙烯酰胺-2-甲基丙磺酸、N,N-二甲基丙烯酰胺、甲基丙烯酸羟乙酯或丙烯酸羟乙酯、偶氮二异丁腈反应得到化合物 2；将化合物1和化合物2在60～90℃条件下反应0.5～4小时，再加入碱性化合物，在60～90℃反应0.1～0.5小时。一种水性防雾涂料组合物，包括该水性防雾树脂30～60份、交联剂5～20份、表面活性剂5～10份、流平剂0.1～1份、稀释剂20～60份，以上含量均为重量份。

Description

水性防雾树脂和水性防雾涂料组合物及其制备方法 技术领域
本发明涉及水性涂料技术领域，特别地，涉及一种水性防雾树脂及其制备方法。此外，本发明还涉及一种包括上述水性防雾树脂的水性防雾涂料组合物及其制备方法。
背景技术
在日常生活中，由于塑胶或玻璃两侧存在明显的温差和湿度差。温度较高一侧的空气中，汽化液体遇到塑胶或玻璃等材料时会凝结在其表面形成流动性较差的小液滴，使塑胶或玻璃表面产生雾气。这些小液滴可使光线产生不规则的散射、反射和衍射，影响了塑胶或玻璃等透明材料对光线的透射能力而变得模糊。
为了减少上述现象的发生，现有技术中存在多种针对塑胶或玻璃表面进行防雾改进的方法。例如(1)表面活性剂直接渗入法；(2)表面活性剂直接涂覆法；(3)高分子材料涂覆法。第1)～2)种方法所形成的防雾涂层稳定性较差，防雾效果难以持久，需经常重复多次在塑胶或玻璃表面进行活性剂处理。方法3)的防雾效果好，且防雾涂层耐磨，防雾效果持久。但是现有的高分子涂料制备过程中需加入多种有机溶剂，其环境友好性有所欠缺，而且不是水性涂料。
发明内容
本发明提供了一种水性防雾树脂及其制备方法及具有该水性防雾树脂的防雾涂料组合物，以解决现有的高分子涂料制备需加入有机溶剂、且不是水性涂料的技术问题。
根据本发明的一个方面，提供一种水性防雾树脂，具有以下结构式：
Figure PCTCN2019072789-appb-000001
其中，m、s、n、p、q、a、b、c分别代表各单体的聚合度，各单体的聚合度取值以水性防雾树脂的数均分子量为5000～100000为限，m、s、n、p、q、a、b、c均为正整数，
R 1和异氰酸酯基团形成二异氰酸酯类化合物，R 1为二异氰酸酯类化合物的母体结构，
R 2为同时含羟基(OH)和羧基(COOH)的化合物，
R 3、R 4、R 5、R 6分别选自为H和CH 3中的一种，
R 7为-O -N +H(C 2H 5OH) 3、-O -N +H(C 2H 5) 3、-O -K +或-O -Na +中的一种。
进一步地，二异氰酸酯类化合物为甲苯二异氰酸酯、二苯基甲烷二异氰酸酯、六亚甲基二异氰酸酯、异佛尔酮二异氰酸酯或二环己基甲烷二异氰酸酯中的一种。
进一步地，R 2为乳酸或二羟甲基丙酸。
进一步地，R 1为异佛尔酮二异氰酸酯的母体结构，R 2为二羟甲基丙酸，R 3、R 4、R 6为CH 3，R 5为H，R 7为-O -N +H(C 2H 5OH) 3。
进一步地，水性防雾树脂的数均分子量为50000-100000。
根据本发明的另一方面，还提供了上述的水性防雾树脂的制备方法，包括以下步骤：
(1)以二月桂酸二丁基锡或对甲苯磺酸为催化剂，含羟基和羧基的R 2化合物与含R 1的二异氰酸酯类化合物在40～60℃下反应0.5～2小时，得到化合物1；
(2)在氮气保护下，将丙烯酸异辛酯、甲基丙烯酰胺或丙烯酰胺、甲基丙烯酸甲酯或丙烯酸甲酯、丙烯酸或甲基丙烯酸、2-丙烯酰胺-2-甲基丙磺酸、N,N-二甲基丙烯酰胺、甲基丙烯酸羟乙酯或丙烯酸羟乙酯、偶氮二异丁腈在60～90℃反应4～8小时，得到化合物2；
(3)将化合物1和化合物2在60～90℃条件下反应0.5～4小时，再加入碱性化合物，在60～90℃反应0.1～0.5小时，碱性化合物与部分磺酸基团和羧基反应成盐，得到水性防雾树脂，碱性化合物为三乙醇胺、三乙胺、氢氧化钾或氢氧化钠。
进一步地，二异氰酸酯类化合物为甲苯二异氰酸酯或二苯基甲烷二异氰酸酯或六亚甲基二异氰酸酯或异佛尔酮二异氰酸酯或二环己基甲烷二异氰酸酯，含羟基和羧基的R 2化合物为乳酸或二羟甲基丙酸；
进一步地，步骤(1)中，含羟基和羧基的R 2化合物、含R 1的二异氰酸酯类化合物的摩尔比为1:2～2.5，催化剂的质量为含羟基和羧基的R 2化合物和含R 1的二异氰酸酯类化合物总质量的0.2～1％。
进一步地，步骤(2)中，丙烯酸异辛酯、甲基丙烯酰胺或丙烯酰胺、甲基丙烯酸甲酯或丙烯酸甲酯、丙烯酸或甲基丙烯酸、2-丙烯酰胺-2-甲基丙磺酸、N,N-二甲基丙烯酰胺、甲基丙烯酸羟乙酯或丙烯酸羟乙酯的摩尔比为1:0.1～0.4:0.8～1:0.1～0.4:0.4～0.8:0.1～0.4:0.6～1.2，偶氮二异丁腈用量为其余反应原料总质量的0.1～0.5％。
进一步地，步骤(3)中，化合物2和化合物1的摩尔比为1:0.2～0.8，碱性化合物与化合物2的摩尔比为1：0.5～1.2。
根据本发明的另一方面，还提供了一种水性防雾涂料组合物，包括上述的水性防雾树脂 或由上述制备方法制得的水性防雾树脂30～60份、交联剂5～20份、表面活性剂5～10份、流平剂0.1～1份、稀释剂20～60份，以上含量均为重量份。
进一步地，所述交联剂为水性聚碳化二亚胺；所述流平剂为含丙烯酸官能团的聚醚改性有机硅；所述稀释剂为去离子水或蒸馏水。
根据本发明的另一方面，还提供了上述涂料组合物的制备方法，包括以下步骤：将所述水性防雾树脂、交联剂、表面活性剂、流平剂、稀释剂按照上述重量份混合均匀，即得所述水性防雾涂料组合物。该涂料组合物采用热固化方法：烘烤温度60-120℃、烘烤时间5-30分钟。
本发明具有以下有益效果：
本发明的水性防雾树脂中引入了具有良好亲水、吸湿性的分子链段和官能团：N,N-二甲基丙烯酰胺具有优异的吸湿性和防静电性、甲基丙烯酸羟乙酯或丙烯酸羟乙酯提供亲水性的羟基官能团、甲基丙烯酸或丙烯酸和乳酸或二羟甲基丙酸提供亲水性的羧基官能团、2-丙烯酰胺-2-甲基丙磺酸提供亲水性、甲基丙烯酰胺或丙烯酰胺具有高吸水特性，甲基丙烯酸甲酯或丙烯酸甲酯提供刚性、丙烯酸异辛脂提供柔韧性。因此，由于大量亲水、吸水性官能团的存在，可赋予水性防雾树脂优异的防雾性能、涂膜强度及透明流平外观，固化涂层的水接触角可达1～10°。本发明的水性防雾树脂含有羧基COOH，其可与聚碳化二亚胺发生化学交联反应而增强固化漆膜的强度和性能，同时聚碳化二亚胺具有可辅助提高对于涂覆素材附着力稳定性的功能。本发明的涂料组合物的固化涂层，具有良好的防雾性能、耐磨、耐水、耐化学品、耐污、耐紫外光性能，对底材的附着力优良；同时涂层坚固，具有优异的成膜强度及耐曲娆性能，可用于手机视窗、PC或PMMA透明材料、汽车玻璃和浴室镜子等表面做防雾处理，长期使用稳定性好。
除了上面所描述的目的、特征和优点之外，本发明还有其它的目的、特征和优点。下面将对本发明作进一步详细的说明。
具体实施方式
以下对本发明的实施例进行详细说明，但是本发明可以由下述所限定和覆盖的多种不同方式实施。
本发明一方面提供了一种水性防雾树脂，具有以下结构式：
Figure PCTCN2019072789-appb-000002
其中，m、s、n、p、q、a、b、c分别代表各单体的聚合度，各单体的聚合度取值以水性防雾树脂的数均分子量为5000～100000为限，m、s、n、p、q、a、b和c均为正整数。
R 1和异氰酸酯基团形成二异氰酸酯类化合物，R 1为二异氰酸酯类化合物的母体结构，二异氰酸酯类化合物可以为甲苯二异氰酸酯、二苯基甲烷二异氰酸酯、六亚甲基二异氰酸酯、异佛尔酮二异氰酸酯或二环己基甲烷二异氰酸酯中的一种。
R 2为同时含羟基(OH)和羧基(COOH)的化合物，可以选自含羟基的乳酸、二羟甲基丙酸中的一种。
R 3、R 4、R 5、R 6分别选自为H和CH 3中的一种。
R 7为-O -N +H(C 2H 5OH) 3、-O -N +H(C 2H 5) 3、-O -K +或-O -Na +中的一种。
水性防雾树脂由多个化合物单体聚合而成。R 1为二异氰酸酯类化合物的母体结构，即二异氰酸酯类化合物的结构单元，异氰酸酯基团在R 1表示的母体结构上形成二异氰酸酯类化合物。具体在水性防雾树脂中，二异氰酸酯类化合物的两个异氰酸酯基团均参与反应，形成
Figure PCTCN2019072789-appb-000003
的结构，具体如水性防雾树脂结构式中所示。上述二异氰酸酯类化合物中某些物质包含多种同分异构体，R 1为相应结构对应的母体结构。以R 1为甲苯二异氰酸酯的母体结构为例进行说明。甲苯二异氰酸酯包括
Figure PCTCN2019072789-appb-000004
两种异构体，相应的R 1为
Figure PCTCN2019072789-appb-000005
R 2为含羟基化合物的结构单元，含羟基化合物包括乳酸、二羟甲基丙酸。含羟基化合物的末端羟基除去H得到R 2基团。
本发明的水性防雾树脂中引入了具有良好亲水、吸湿性的分子链段和官能团：N,N-二甲基丙烯酰胺具有优异的吸湿性和防静电性、甲基丙烯酸羟乙酯或丙烯酸羟乙酯提供亲水性的 羟基官能团、甲基丙烯酸或丙烯酸和乳酸或提供亲水性的羧基官能团、2-丙烯酰胺-2-甲基丙磺酸提供亲水性、甲基丙烯酰胺或丙烯酰胺具有高吸水特性，甲基丙烯酸甲酯或丙烯酸甲酯提供刚性、丙烯酸异辛脂提供柔韧性。因此，由于大量亲水、吸水性官能团的存在，可赋予水性防雾树脂优异的防雾性能和涂膜强度，固化涂层的水接触角可达1～10°。另外，一部分磺酸基团和羧酸基团通过碱性化合物中和成盐，实现水性防雾树脂的水性化，可溶解/分散于蒸馏水或去离子水中。
进一步地，R 1为异佛尔酮二异氰酸酯的母体结构，R 2为二羟甲基丙酸，R 3、R 4、R 6为CH 3，R 5为H，R 7为-O -N +H(C 2H 5OH) 3。该结构的水性防雾树脂的水接触角小，防雾效果更好，性能更为优异。
进一步地，水性防雾树脂的数均分子量为50000～100000。该数均分子量的水性防雾树脂易于成膜，防雾效果得到进一步提升。
本发明另一方面提供上述水性防雾树脂的制备方法，包括以下步骤：
(1)以二月桂酸二丁基锡或对甲苯磺酸为催化剂，含羟基和羧基的R 2化合物与含R 1的二异氰酸酯类化合物在40～60℃下反应0.5～2小时，得到化合物1；
(2)在氮气保护下，将丙烯酸异辛酯、甲基丙烯酰胺或丙烯酰胺、甲基丙烯酸甲酯或丙烯酸甲酯、丙烯酸或甲基丙烯酸、2-丙烯酰胺-2-甲基丙磺酸、N,N-二甲基丙烯酰胺、甲基丙烯酸羟乙酯或丙烯酸羟乙酯、偶氮二异丁腈在60～90℃反应4～8小时，得到化合物2；
(3)将化合物1和化合物2在60～90℃条件下反应0.5～4小时，再加入碱性化合物，在60～90℃反应0.1～0.5小时，碱性化合物与部分磺酸基团和羧基反应成盐，得到水性防雾树脂，碱性化合物为三乙醇胺或三乙胺、氢氧化钾或氢氧化钠。
步骤(1)中，以二月桂酸二丁基锡或对甲苯磺酸为催化剂，将含羟基和羧基的R 2化合物与含R 1的二异氰酸酯类化合物的单体在40～60℃下反应0.5～2小时，得到化合物1。步骤(1)的反应方程式如下：
Figure PCTCN2019072789-appb-000006
步骤(1)中，二异氰酸酯类化合物为甲苯二异氰酸酯或二苯基甲烷二异氰酸酯或六亚甲基二异氰酸酯或异佛尔酮二异氰酸酯或二环己基甲烷二异氰酸酯，含羟基的R 2化合物为乳酸或二羟甲基丙酸，但并不限于此。本发明最终合成树脂含有羧基COOH，其可与聚碳化二亚胺发生化学交联反应而增强固化漆膜的强度和性能，同时聚碳化二亚胺具有可辅助提高对于涂覆素材附着力稳定性的功能。
步骤(2)中，可依次在四口烧瓶中加入丙烯酸异辛酯单体、甲基丙烯酰胺或丙烯酰胺、甲基丙烯酸甲酯或丙烯酸甲酯、丙烯酸或甲基丙烯酸、2-丙烯酰胺-2-甲基丙磺酸、N,N-二甲基丙烯酰胺、甲基丙烯酸羟乙酯或丙烯酸羟乙酯、偶氮二异丁腈单体，并采用氮气置换排除 反应瓶中的空气，在氮气保护的条件下，升温至60～90℃，冷凝回流反应4～8小时，得到化合物2。甲基丙烯酰胺或丙烯酰胺、甲基丙烯酸甲酯或丙烯酸甲酯、丙烯酸或甲基丙烯酸、甲基丙烯酸羟乙酯或丙烯酸羟乙酯中的“或”表示二选一，步骤(2)中的反应方程式如下：
Figure PCTCN2019072789-appb-000007
步骤(3)中，将上述化合物2与化合物1在60～90℃条件下反应0.5～4小时；再加入碱性化合物，在60～90℃反应0.1～0.5小时，最终得到水性防雾树脂。其中，甲基丙烯酸羟乙酯或丙烯酸羟乙酯的聚合度为s+(n-s)，为便于理解其反应，将其分为两个部分即聚合物为s的结构已与化合物1反应，以及未反应的聚合物为n-s的结构进行描述。步骤(3)的反应方程如下：
Figure PCTCN2019072789-appb-000008
在上述步骤中，如反应温度和时间低于设定值，则各步骤中反应进行程度较低，相应的产物聚合度较低，导致所合成水性防雾树脂的分子量偏低，树脂难以成膜，防雾效果差；如反应温度和时间高于设定值，则耗费能源及时间，且水性防雾树脂有爆聚凝胶风险。
进一步地，步骤(1)中，含羟基和羧基的R 2化合物、含R 1的二异氰酸酯类化合物的摩尔比为1:2～2.5。催化剂的质量为含羟基和羧基的R 2化合物和含R 1的二异氰酸酯类化合物总质量的0.2～1％。
进一步地，步骤(2)中，丙烯酸异辛酯、甲基丙烯酰胺或丙烯酰胺、甲基丙烯酸甲酯或 丙烯酸甲酯、丙烯酸或甲基丙烯酸、2-丙烯酰胺-2-甲基丙磺酸、N,N-二甲基丙烯酰胺、甲基丙烯酸羟乙酯或丙烯酸羟乙酯的摩尔比为1:0.1～0.4:0.8～1:0.1～0.4:0.4～0.8:0.1～0.4:0.6～1.2，如摩尔比未在该范围，则化合物1中异氰酸酯基团含量偏低或偏高，偏低易导致化合物1与化合物2中的羟基反应不充分，使水性防雾树脂的分子量偏低；偏高则使水性防雾树脂中异氰酸酯基团易残留过多，影响树脂的存储稳定性，易胶化。偶氮二异丁腈用量为上述单体总质量的0.1～0.5％。即偶氮二异丁腈用量为丙烯酸异辛酯、甲基丙烯酰胺或丙烯酰胺、甲基丙烯酸甲酯或丙烯酸甲酯、丙烯酸或甲基丙烯酸、2-丙烯酰胺-2-甲基丙磺酸、N,N-二甲基丙烯酰胺、甲基丙烯酸羟乙酯或丙烯酸羟乙酯总质量的0.1～0.5％。
进一步地，步骤(3)中，化合物2和化合物1的摩尔比为1:0.2～0.8，碱性化合物与化合物2的摩尔比为1：0.5～1.2。如摩尔比未在该范围，则水性防雾树脂的分子量难以控制在设定范围值，使树脂的成膜性及防雾效果变差。
进一步地，步骤(1)中，含羟基和羧基的R 2化合物与含R 1的二异氰酸酯类化合物在60℃下反应2小时。在该条件下，反应条件温和，反应的产率更高。
进一步地，步骤(2)中的反应温度为90℃，反应时间为8小时。在该条件下，反应条件温和，反应的产率更高。
进一步地，步骤(3)中，化合物2与化合物1在90℃条件下反应4小时，加入三乙醇胺在90℃反应0.5小时，三乙醇胺的加入量与化合物2的摩尔比为1：1.2。在该条件下，反应条件温和，反应的产率更高。
根据本发明的另一方面，还提供了一种水性防雾涂料组合物，包括上述水性防雾树脂或由上述制备方法制得的水性防雾树脂30～60份、交联剂5～20份、表面活性剂5～10份、流平剂0.1～1份、稀释剂20～60份，以上含量均为重量份。
进一步地，所述交联剂为水性聚碳化二亚胺(例如上海尤恩化工有限公司的水性聚碳化二亚胺UN-557)，其可与水性防雾树脂中羧酸结构单元(COOH)发生化学交联反应成膜，可提高涂层的耐磨、耐水、耐化学品、耐污、耐紫外光性能，提高对于特殊底材的附着力；同时可使涂层更加坚固，从而提高成膜强度及耐曲娆性能；
所述表面活性剂至少为水溶性的十二烷基硫酸钠和磺基琥珀酸钠二辛酯中的一种。
所述流平剂为含丙烯酸官能团的聚醚改性有机硅(例如德国BYK公司的BYK475)，促进漆膜镜面流平；所述溶剂为去离子水或蒸馏水，调节施工粘度。
上述涂料组合物的制备方法，包括以下步骤：将所述水性防雾树脂、交联剂、流平剂、稀释剂按照上述重量份混合均匀，即得所述水性防雾涂料组合物。该涂料组合物采用热固化方法：烘烤温度60～120℃、烘烤时间5～30分钟。本发明所合成树脂为热固型树脂，因此采用热固化方法。
水性防雾树脂制备实施例：
实施例1
(1)以二月桂酸二丁基锡为催化剂，将二羟甲基丙酸与甲苯二异氰酸酯单体在40℃下反应0.5小时，得到化合物1。其中，二羟甲基丙酸和甲苯二异氰酸酯单体的摩尔比为1:2；催化剂用量为上述两种原料质量总和的0.2％。
(2)依次在四口烧瓶中加入丙烯酸异辛酯、甲基丙烯酰胺、甲基丙烯酸甲酯、甲基丙烯酸、2-丙烯酰胺-2-甲基丙磺酸、N,N-二甲基丙烯酰胺、丙烯酸羟乙酯、偶氮二异丁腈，并采用氮气置换排除反应瓶中的空气，在氮气保护下，升温至60℃，冷凝回流反应4小时，得到化合物2。其中，丙烯酸异辛酯、甲基丙烯酰胺、甲基丙烯酸甲酯、甲基丙烯酸、2-丙烯酰胺-2-甲基丙磺酸、N,N-二甲基丙烯酰胺、丙烯酸羟乙酯的摩尔比为1:0.1:0.8:0.4:0.4:0.4:1.2。偶氮二异丁腈用量为上述单体总质量的0.1％。
(3)将上述化合物2与化合物1以摩尔比1:0.2在60℃条件下反应0.5小时；再加入三乙醇胺，其与化合物2的摩尔比为1:0.5，在60℃反应0.1小时，最终得到水性防雾树脂1，其数均分子量为5000。
实施例2
(1)以二月桂酸二丁基锡为催化剂，将乳酸与异佛尔酮二异氰酸酯单体在60℃下反应2小时，得到化合物1。其中，乳酸和异佛尔酮二异氰酸酯单体的摩尔比为1:2.5；催化剂用量为上述两种原料质量总和的0.5％。
(2)依次在四口烧瓶中加入丙烯酸异辛酯、丙烯酰胺、丙烯酸甲酯、甲基丙烯酸、2-丙烯酰胺-2-甲基丙磺酸、N,N-二甲基丙烯酰胺、甲基丙烯酸羟乙酯、偶氮二异丁腈，并采用氮气置换排除反应瓶中的空气，在氮气保护下，升温至90℃，冷凝回流反应8小时，得到化合物2。其中，丙烯酸异辛酯、丙烯酰胺、丙烯酸甲酯、甲基丙烯酸、2-丙烯酰胺-2-甲基丙磺酸、N,N-二甲基丙烯酰胺、甲基丙烯酸羟乙酯的摩尔比为1:0.4:1:0.4:0.8:0.4:1.2。偶氮二异丁腈用量为上述单体总质量的0.5％。
(3)将上述化合物2与化合物1以摩尔比1:0.8在90℃条件下反应4小时；再加入三乙醇胺，其与化合物2的摩尔比为1:1.2，在90℃反应0.5小时，最终得到水性防雾树脂2，其数均分子量为100000。
实施例3
(1)以对甲苯磺酸为催化剂，将二羟甲基丙酸与六亚甲基二异氰酸酯单体在50℃下反应1小时，得到化合物1。其中，二羟甲基丙酸和六亚甲基二异氰酸酯单体的摩尔比为1:2.2；催化剂用量为上述两种原料质量总和的1％。
(2)依次在四口烧瓶中加入丙烯酸异辛酯、甲基丙烯酰胺、甲基丙烯酸甲酯、甲基丙烯酸、2-丙烯酰胺-2-甲基丙磺酸、N,N-二甲基丙烯酰胺、丙烯酸羟乙酯、偶氮二异丁腈，并采用氮气置换排除反应瓶中的空气，在氮气保护下，升温至70℃，冷凝回流反应5小时，得到化合物2。其中，丙烯酸异辛酯、甲基丙烯酰胺、甲基丙烯酸甲酯、甲基丙烯酸、2-丙烯酰胺-2-甲基丙磺酸、N,N-二甲基丙烯酰胺、丙烯酸羟乙酯的摩尔比为1:0.2:0.9:0.2:0.6:0.3:0.8。偶氮二异丁腈用量为上述单体总质量的0.2％。
(3)将上述化合物2与化合物1以摩尔比1:0.6在80℃条件下反应1小时；再加入三乙胺，其与化合物2的摩尔比为1:1，在70℃反应0.2小时，最终得到水性防雾树脂3，其数均分子量为60000。
实施例4
(1)以二月桂酸二丁基锡为催化剂，将二羟甲基丙酸与二苯基甲烷二异氰酸酯单体在50℃下反应1.5小时，得到化合物1。其中，二羟甲基丙酸、异佛尔酮二异氰酸酯单体的摩尔比为1:2.2；催化剂用量为上述两种原料质量总和的0.4％。
(2)依次在四口烧瓶中加入丙烯酸异辛酯、甲基丙烯酰胺、甲基丙烯酸甲酯、甲基丙烯酸、2-丙烯酰胺-2-甲基丙磺酸、N,N-二甲基丙烯酰胺、丙烯酸羟乙酯、偶氮二异丁腈，并采用氮气置换排除反应瓶中的空气，在氮气保护下，升温至70℃，冷凝回流反应6小时，得到化合物2。其中，丙烯酸异辛酯、甲基丙烯酰胺、甲基丙烯酸甲酯、甲基丙烯酸、2-丙烯酰胺-2-甲基丙磺酸、N,N-二甲基丙烯酰胺、丙烯酸羟乙酯的摩尔比为1:0.3:0.9:0.2:0.6:0.2:0.9。偶氮二异丁腈用量为上述单体总质量的0.3％。
(3)将上述化合物2与化合物1以摩尔比1:0.6在80℃条件下反应2小时；再加入氢氧化钾，其与化合物2的摩尔比为1:0.6，在60℃反应0.2小时，最终得到水性防雾树脂4，其数均分子量为30000。
对比例1
(1)以二月桂酸二丁基锡为催化剂，将二羟甲基丙酸与甲苯二异氰酸酯单体在50℃下反应0.3小时，得到化合物1。其中，二羟甲基丙酸和甲苯二异氰酸酯单体的摩尔比为1:1.5；催化剂用量为上述两种原料质量总和的0.1％。
(2)依次在四口烧瓶中加入丙烯酸异辛酯、甲基丙烯酰胺、甲基丙烯酸甲酯、甲基丙烯酸、2-丙烯酰胺-2-甲基丙磺酸、N,N-二甲基丙烯酰胺、丙烯酸羟乙酯、偶氮二异丁腈，并采用氮气置换排除反应瓶中的空气，在氮气保护下，升温至80℃，冷凝回流反应4小时，得到化合物2。其中，丙烯酸异辛酯、甲基丙烯酰胺、甲基丙烯酸甲酯、甲基丙烯酸、2-丙烯酰胺-2-甲基丙磺酸、N,N-二甲基丙烯酰胺、丙烯酸羟乙酯的摩尔比为1:0.05:0.2:0.1:0.2:0.1:0.3。偶氮二异丁腈用量为上述单体总质量的0.1％。
(3)将上述化合物2与化合物1以摩尔比1:0.2在60℃条件下反应0.5小时；再加入三乙醇胺，其与化合物2的摩尔比为1:0.2，在60℃反应0.1小时，最终得到水性防雾树脂5，其数均分子量为3000。
对比例2
(1)以二月桂酸二丁基锡为催化剂，将二羟甲基丙酸与甲苯二异氰酸酯单体在35℃下反应0.5小时，得到化合物1。其中，二羟甲基丙酸和甲苯二异氰酸酯单体的摩尔比为1:2；催化剂用量为上述两种原料质量总和的0.2％。
(2)依次在四口烧瓶中加入丙烯酸异辛酯、甲基丙烯酰胺、甲基丙烯酸甲酯、甲基丙烯 酸、2-丙烯酰胺-2-甲基丙磺酸、N,N-二甲基丙烯酰胺、丙烯酸羟乙酯、偶氮二异丁腈，并采用氮气置换排除反应瓶中的空气，在氮气保护下，升温至50℃，冷凝回流反应4小时，得到化合物2。其中，丙烯酸异辛酯、甲基丙烯酰胺、甲基丙烯酸甲酯、甲基丙烯酸、2-丙烯酰胺-2-甲基丙磺酸、N,N-二甲基丙烯酰胺、丙烯酸羟乙酯的摩尔比为1:0.1:0.8:0.4:0.4:0.4:1.2。偶氮二异丁腈用量为上述单体总质量的0.1％。
(3)将上述化合物2与化合物1以摩尔比1:0.2在50℃条件下反应0.5小时；再加入三乙醇胺，其与化合物2的摩尔比为1:0.5，在50℃反应0.1小时，最终得到水性防雾树脂6，其数均分子量为2000。
水性防雾涂料组合物实施例：
以下水性防雾涂料组合物实施例5～8和对比例1～2中各组分的含量，如表1中所示；其中，涂料组合物的含量分别为重量份。
表1实施例5～8中水性防雾涂料组合物和对比例1～2中各组分含量
Figure PCTCN2019072789-appb-000009
将上述实施例5～8的涂料组合物涂覆在透明PC素材表面，采用烘烤温度70℃和烘烤时间20分钟得到防雾涂层。对上述实施例5～8涂覆后得到的涂层进行附着力、耐磨性能、硬度、水接触角和防雾性能测试。测试方法如下：
附着力按照GB9286-1998标准测试。
RCA耐磨测试方法为常规RCA耐磨测试方法，采用Norman RCA耐磨测试仪，漆膜负重175 g。
铅笔硬度测试按GB/T 6739-2006标准测试，负重1000g；附着力测试按GB 9286-1998标准测试。
水接触角测试按GB/T 23764-2009标准测试。
防雾性能测试采用冷雾和热雾两种方法进行评估：冷雾测试法为将含固化涂层的玻璃产品静置于-15℃下保存30分钟后取出，在50％湿度的室温条件下观察涂层产品的透明情况。热雾测试法为产品涂层面静置于80℃的饱和水蒸气中60分钟后取出，在50％湿度的室温条件下观察涂层产品的透明情况。透明度等级依次采用1至5表示，其中5代表完全透明，1代表浑浊不透明。
实施例5～8和对比例1～2涂覆在透明PC上后得到的涂层，性能测试结果如表2所示。
表2实施例5～8和对比例1～2涂覆后得到的涂层性能测试结果
性能 实施例5 实施例6 实施例7 实施例8 对比例1 对比例2
对PC的附着力 5B 5B 5B 5B 5B 5B
RCA耐磨 400次 500次 400次 400次 300次 200次
铅笔硬度 HB H F HB 1B 2B
水接触角 10° 1° 5° 7° 25° 30°
防雾性能(冷雾) 4 5 5 4 3 2
防雾性能(热雾) 4 5 5 4 3 2
由表2可知，实施例5～8的涂料组合物涂覆到透明PC上形成的涂层，均表现出良好的表面性能；实施例6的涂料组合物防雾性能尤其显著，并同时具有良好的附着力和耐磨性能及硬度。对比例中，对比例1～2中由于所制备水性防雾树脂的数均分子量分别为3000和2000，均小于本发明所要求值，而使它们的涂料组合物固化涂层的防雾性能均显著降低，且涂层的耐磨和硬度均显著降低。
以上所述仅为本发明的优选实施例而已，并不用于限制本发明，对于本领域的技术人员来说，本发明可以有各种更改和变化。凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。

Claims (12)

  1. 一种水性防雾树脂，其特征在于，具有以下结构式：
    Figure PCTCN2019072789-appb-100001
    其中，m、s、n、p、q、a、b、c分别代表各单体的聚合度，各单体的聚合度取值以水性防雾树脂的数均分子量为5000～100000为限，m、s、n、p、q、a、b、c均为正整数，
    R 1和异氰酸酯基团形成二异氰酸酯类化合物，R 1为二异氰酸酯类化合物的母体结构，
    R 2为同时含羟基(OH)和羧基(COOH)的化合物，
    R 3、R 4、R 5、R 6分别选自为H和CH 3中的一种，
    R 7为-O -N +H(C 2H 5OH) 3、-O -N +H(C 2H 5) 3、-O -K +或-O -Na +中的一种。
  2. 根据权利要求1所述的一种水性防雾树脂，其特征在于，
    所述二异氰酸酯类化合物为甲苯二异氰酸酯、二苯基甲烷二异氰酸酯、六亚甲基二异氰酸酯、异佛尔酮二异氰酸酯或二环己基甲烷二异氰酸酯中的一种，所述R 2为乳酸或二羟甲基丙酸。
  3. 根据权利要求2所述的一种水性防雾树脂，其特征在于，
    所述R 1为异佛尔酮二异氰酸酯的母体结构，所述R 2为二羟甲基丙酸，R 3、R 4、R 6为CH 3，R 5为H，R 7为-O -N +H(C 2H 5OH) 3。
  4. 根据权利要求1所述的一种水性防雾树脂，其特征在于，
    所述水性防雾树脂的数均分子量为50000-100000。
  5. 一种如权利要求1所述的水性防雾树脂的制备方法，其特征在于，包括以下步骤：
    (1)以二月桂酸二丁基锡或对甲苯磺酸为催化剂，含羟基和羧基的R 2化合物与含R 1的二异氰酸酯类化合物在40～60℃下反应0.5～2小时，得到化合物1；
    (2)在氮气保护下，将丙烯酸异辛酯、甲基丙烯酰胺或丙烯酰胺、甲基丙烯酸甲酯或丙烯酸甲酯、丙烯酸或甲基丙烯酸、2-丙烯酰胺-2-甲基丙磺酸、N,N-二甲基丙烯酰胺、甲基丙烯酸羟乙酯或丙烯酸羟乙酯、偶氮二异丁腈在60～90℃反应4～8小时，得到化合物 2；
    (3)将所述化合物1和所述化合物2在60～90℃条件下反应0.5～4小时，再加入碱性化合物，在60～90℃反应0.1～0.5小时，碱性化合物与部分磺酸基团和羧基反应成盐，得到水性防雾树脂，所述碱性化合物为三乙醇胺、三乙胺、氢氧化钾或氢氧化钠。
  6. 根据权利要求5所述的一种水性防雾树脂的制备方法，其特征在于，
    所述二异氰酸酯类化合物为甲苯二异氰酸酯或二苯基甲烷二异氰酸酯或六亚甲基二异氰酸酯或异佛尔酮二异氰酸酯或二环己基甲烷二异氰酸酯，所述含羟基和羧基的R 2化合物为乳酸或二羟甲基丙酸。
  7. 根据权利要求5所述的一种水性防雾树脂的制备方法，其特征在于，
    所述步骤(1)中，所述含羟基和羧基的R 2化合物、含R 1的二异氰酸酯类化合物的摩尔比为1:2～2.5，所述催化剂的质量为含羟基和羧基的R 2化合物和含R 1的二异氰酸酯类化合物总质量的0.2～1％。
  8. 根据权利要求5所述的一种水性防雾树脂的制备方法，其特征在于，
    所述步骤(2)中，所述丙烯酸异辛酯、甲基丙烯酰胺或丙烯酰胺、甲基丙烯酸甲酯或丙烯酸甲酯、丙烯酸或甲基丙烯酸、2-丙烯酰胺-2-甲基丙磺酸、N,N-二甲基丙烯酰胺、甲基丙烯酸羟乙酯或丙烯酸羟乙酯的摩尔比为1:0.1～0.4:0.8～1:0.1～0.4:0.4～0.8:0.1～0.4:0.6～1.2，所述偶氮二异丁腈用量为其余反应原料总质量的0.1～0.5％。
  9. 根据权利要求5所述的一种水性防雾树脂的制备方法，其特征在于，
    所述步骤(3)中，所述化合物2和所述化合物1的摩尔比为1:0.2～0.8，所述碱性化合物与所述化合物2的摩尔比为1：0.5～1.2。
  10. 一种水性防雾涂料组合物，其特征在于，
    包括权利要求1所述的水性防雾树脂30～60份、交联剂5～20份、表面活性剂5～10份、流平剂0.1～1份、稀释剂20～60份，以上含量均为重量份。
  11. 根据权利要求10所述的水性防雾涂料组合物，其特征在于，
    所述交联剂为水性聚碳化二亚胺；所述流平剂为含丙烯酸官能团的聚醚改性有机硅；所述稀释剂为去离子水或蒸馏水。
  12. 一种如权利要求10所述的水性防雾涂料组合物的制备方法，其特征在于，
    将所述水性防雾树脂30～60份、交联剂5～20份、表面活性剂5～10份、流平剂0.1～1份、稀释剂20～60份混合均匀，即得所述水性防雾涂料组合物，以上含量均为重量份。
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