阅读说明：本技术 一种uv固化水性树脂及其制备方法 (UV (ultraviolet) curing water-based resin and preparation method thereof ) 是由 徐涛 龙绪俭 熊东路 肖增钧 易松 杨轩 鲁晓东 李斌仁 于 2020-06-04 设计创作，主要内容包括：本发明提供一种UV固化水性树脂及其制备方法。该UV固化水性树脂为由聚氨酯改性丙烯酸酯和胺烷基磺酸盐反应生成的聚氨酯改性丙烯酸酯UV树脂,具有软硬可调性,可通过改变合成聚氨酯改性丙烯酸酯所用原料中的二元醇的分子量来调控固化膜的硬度及柔韧性；兼具聚氨酯和丙烯酸酯的特征,其固化膜具有较高的硬度和良好的附着力、柔韧性,外观光滑,漆膜饱满；可通过控制亲水基团的含量来平衡树脂的乳化性能和固化膜的耐水性能。以该UV固化水性树脂作为UV固化水性涂料主要组分时,可通过水替代活性稀释剂来调节涂料的流动性,对环境友好,还改善了膜固化收缩现象,具有可薄涂、施工设备易清洗等优点。其制备方法简单、对设备要求低,易于实现产业化。(The invention provides a UV-curable water-based resin and a preparation method thereof. The UV-cured waterborne resin is polyurethane modified acrylate UV resin generated by the reaction of polyurethane modified acrylate and amine alkyl sulfonate, has hardness adjustability, and can adjust and control the hardness and flexibility of a cured film by changing the molecular weight of dihydric alcohol in raw materials for synthesizing the polyurethane modified acrylate; the curing agent has the characteristics of polyurethane and acrylate, and a curing film of the curing agent has high hardness, good adhesive force and flexibility, smooth appearance and full paint film; the emulsifying property of the resin and the water resistance of the cured film can be balanced by controlling the content of the hydrophilic group. When the UV-curable water-based resin is used as the main component of the UV-curable water-based paint, the fluidity of the paint can be adjusted by replacing an active diluent with water, the UV-curable water-based resin is environment-friendly, the film curing shrinkage phenomenon is improved, and the UV-curable water-based resin has the advantages of thin coating, easy cleaning of construction equipment and the like. The preparation method is simple, has low requirements on equipment, and is easy to realize industrialization.)

1. The UV-curable water-based resin is characterized by being prepared by reacting A and B, wherein A is polyurethane modified acrylate, and B is amine alkyl sulfonate.

2. The UV-curable aqueous resin according to claim 1, wherein A has the formula:

wherein R isR₁Is composed of

R₀Is H or Me, R₄Is H or Me, R₇Is H or Me, R₈Is H or Me; n ranges from 2 to 20, n₁The value range of (1) to (30), the value range of m is from 2 to (20), m₁The value range of (a) is 1-30, and the value range of p is 1-30.

3. The UV-curable aqueous resin according to claim 1 or 2, wherein B is selected from the group consisting ofAnd/orThe components of the composition are as follows,

wherein, the value range of x is 2-20, and Y⁺Is Na⁺And/or K⁺And/or NH₄ ⁺，Z⁺Is Na⁺And/or K⁺And/or NH₄ ⁺。

4. The UV-curable aqueous resin according to claim 3, wherein the reaction is a Michael addition reaction, and the molar ratio of A to B is 1: (0.5-2.0) carrying out the reaction.

5. A preparation method of UV curing water-based resin is characterized by preparing A and B as required, adding A into a reaction bottle, adding a solvent to dissolve A, heating to 40-50 ℃, slowly dripping B into the reaction bottle, after finishing dripping, carrying out heat preservation reaction until the reaction is finished, and carrying out post-treatment to obtain the UV curing water-based resin, wherein A is polyurethane modified acrylate, and B is amine alkyl sulfonate.

6. The method for producing a UV-curable aqueous resin according to claim 5, wherein the solvent is added in an amount of 0.5 to 2 times by volume based on the volume of the A; the solvent is prepared by mixing water and an organic solvent according to a volume ratio of 1: and (1-4) are mixed according to the proportion.

7. The method for preparing a UV-curable aqueous resin according to claim 6, wherein the solvent is one of an ethanol/water mixed solvent, an acetone/water mixed solvent, and an N-methylpyrrolidone/water mixed solvent.

8. The method for preparing the UV-curable aqueous resin according to claim 7, wherein the reaction time of the incubation reaction is 24 to 48 hours.

9. The method for producing a UV-curable aqueous resin according to any one of claims 5 to 8, wherein the post-treatment is: removing the organic solvent by distillation under reduced pressure; the pressure of the reduced pressure distillation is-0.09 MPa to-0.1 MPa, and the temperature is 40-150 ℃.

10. The method for producing a UV-curable aqueous resin according to claim 9, wherein the primary amine value in the reaction system is detected, and when the primary amine value is less than 4mg KOH/g and tends to be stable, the reaction is judged to be completed.

Technical Field

The invention relates to the technical field of water-based paint, in particular to UV (ultraviolet) curing water-based resin and a preparation method thereof.

Background

The UV curing coating has the advantages of environmental protection, high efficiency and the like, and the formed curing film has excellent comprehensive performance and is widely applied to coating of wooden products, plastic products and metal products. The UV-curable water-based resin is a key component in the UV-curable water-based paint, and the molecular structure, molecular weight, functionality and the like of the UV-curable water-based resin determine the performance of a cured film. The polyurethane modified acrylate UV resin has good flexibility, adhesive force, wear resistance, weather resistance and the like, the hardness can be regulated and controlled through a molecular structure, the viscosity is usually high, and an active diluent is required to be added in a coating formula. The traditional UV curing coating needs to be added with an acrylate reactive diluent, and the reactive diluent has certain sensitization, possibly causes certain harm to human bodies and can cause a curing film to shrink to a certain extent.

Disclosure of Invention

The technical problem to be solved by the invention is as follows: the novel UV-curing water-based resin is obtained by modifying the existing polyurethane modified acrylate, so that the novel UV-curing water-based resin does not need to be added with an acrylate reactive diluent during application.

In order to solve the technical problems, the invention adopts the technical scheme that:

the UV-curable water-based resin is prepared by reacting A and B, wherein A is polyurethane modified acrylate, and B is amine alkyl sulfonate.

Further, the structural formula of A is as follows:

wherein R is

R₁Is composed of

R₂Is composed of

R₃Is composed ofR₅Is composed ofR₆Is composed ofR₀Is H or Me, R₄Is H or Me, R₇Is H or Me, R₈Is H or Me; n ranges from 2 to 20, n₁The value range of (1) to (30), the value range of m is from 2 to (20), m₁The value range of (a) is 1-30, and the value range of p is 1-30.

Further, said B is composed of

And/orThe components of the composition are as follows,

wherein, the value range of x is 2-20, and Y⁺Is Na⁺And/or K⁺And/or NH₄ ⁺，Z⁺Is Na⁺And/or K⁺And/or NH₄ ⁺。

Further, the reaction is a Michael addition reaction, and the molar weight ratio of the A to the B is 1: (0.5-2.0) carrying out the reaction.

A preparation method of UV-cured water-based resin comprises the steps of preparing A and B as required, adding A into a reaction bottle, adding a solvent to dissolve A, heating to 40-50 ℃, slowly dropwise adding B into the reaction bottle, keeping the temperature after dropwise adding is finished, reacting until the reaction is finished, and carrying out post-treatment to obtain the UV-cured water-based resin, wherein A is polyurethane modified acrylate, and B is amine alkyl sulfonate.

Further, the volume of the added solvent is 0.5-2 times of the volume of the A; the solvent is prepared by mixing water and an organic solvent according to a volume ratio of 1: and (1-4) are mixed according to the proportion.

Further, the solvent is one of ethanol/water mixed solvent, acetone/water mixed solvent and N-methylpyrrolidone/water mixed solvent.

Further, the reaction time of the heat preservation reaction is 24-48 h.

Further, the post-processing is as follows: removing the organic solvent by distillation under reduced pressure; the pressure of the reduced pressure distillation is-0.09 MPa to-0.1 MPa, and the temperature is 40-150 ℃.

Further, detecting the primary amine value in the reaction system, and judging that the reaction is finished when the primary amine value is less than 4mg KOH/g and tends to be stable.

The invention has the beneficial effects that:

1. the UV-cured water-based resin is polyurethane modified acrylate UV resin, has hardness adjustability, and can adjust and control the hardness and flexibility of a cured film by changing the molecular weight of dihydric alcohol in raw materials for synthesizing the polyurethane modified acrylate.

2. The UV-cured water-based resin has the characteristics of polyurethane and acrylate, and a cured film of the UV-cured water-based resin has high hardness, good adhesive force and flexibility, smooth appearance and full paint film.

3. The UV-curable aqueous resin of the present invention can balance the emulsification properties of the resin and the water resistance of the cured film by controlling the content of hydrophilic groups.

4. The preparation method of the UV-curable water-based resin provided by the invention is simple, has low requirements on equipment, and is easy to realize industrialization.

5. The UV-curable water-based resin provided by the invention is used as a UV-curable water-based paint, the fluidity of the paint can be adjusted by replacing an active diluent with water, and the UV-curable water-based resin is environment-friendly and can improve the film curing shrinkage phenomenon. In addition, the UV-curable water-based paint also has the advantages of thin coating, easy cleaning of construction equipment and the like.

Detailed Description

The most key concept of the invention is as follows: hydrophilic groups are introduced into the molecular structure to enable the molecular structure to have certain hydrophilicity, the UV-cured waterborne polyurethane modified acrylate resin is prepared, and water is used for replacing an acrylate reactive diluent for dilution when the UV-cured waterborne polyurethane modified acrylate resin is applied.

In order to further discuss the feasibility of the inventive concept, the detailed description of the technical content, the constructional features, the objects and the effects achieved according to the invention is given in detail.