CN105482766A - Polyurethane acrylate UV-curing material and preparation method thereof - Google Patents

Abstract

The invention discloses a polyurethane acrylate UV-curing material which comprises the following components in parts by weight: 30-70% of polyurethane acrylate low polymer, 20-55% of reactive diluent, 1-10% of photoinitiator, 0.1-3% of dodecafluoroheptyl methacrylate, 0.1-3% of plasticizer, 0.1-3% of silane coupling agent and 0.1-3% of leveling agent. The polyurethane acrylate low polymer is prepared by the following steps: mixing a hexamethylene diisocyanate tripolymer, hydroxy acrylate, a catalyst and a polymerization inhibitor, and reacting at 60-80 DEG C until the NCO value is less than or equal to 10%. Compared with the existing polyurethane acrylate UV-curing material, the material disclosed by the invention has the advantages of no pollution, low volatility, high curing rate, high glossiness, high hardness and high shear strength. The preparation method is simple, is low in cost and does not need to add any solvent. The polyurethane acrylate UV-curing material can be used as a paint and adhesive.

Description

Polyurethane acrylate type UV curing material and preparation method thereof

technical field

The invention belongs to the field of organic coatings and adhesives, and in particular relates to a polyurethane acrylate type UV curing material that can be used as coatings or adhesives and a preparation method thereof.

Background technique

Today, with the increasingly stringent requirements of environmental protection laws and regulations, the awareness of environmental protection in countries around the world is also increasing, and countries are accelerating the research and development of new varieties of coatings with high performance, low cost and low pollution. Polyurethane acrylate UV-curable coatings have the characteristics of high efficiency, wide adaptability, economy, energy saving and environmental friendliness. They have superior comprehensive performance and belong to the global high-end technology industry products. The core competitiveness of domestic related products, therefore, has important economic significance and social value.

Contents of the invention

The technical problem to be solved by the present invention is to overcome the existing defects and provide a polyurethane acrylate type UV curing material and a preparation method thereof. The material can be used as a coating or as an adhesive.

In order to solve the problems of the technologies described above, the present invention provides the following technical solutions:

Urethane acrylate type UV curing material, by weight, includes the following components: urethane acrylate oligomer 30-70%, reactive diluent 20-55%, photoinitiator 1-10%, dodecafluoromethacrylate Heptyl ester 0.1-3%, plasticizer 0.1-3%, silane coupling agent 0.1-3%, leveling agent 0.1-3%,

Wherein, the urethane acrylate oligomer is obtained by the following method: mixing hexamethylene diisocyanate trimer, acrylate hydroxyl ester, catalyst and polymerization inhibitor, and reacting at 60-80°C until the NCO value is ≤10wt %.

Further, the active diluent is dipropylene glycol diacrylate, tripropylene glycol diacrylate, 1,6-hexanediol diacrylate, pentaerythritol triacrylate, trimethylolpropane triacrylate, pentaerythritol tetraacrylate at least one of esters.

Further, the photoinitiator is 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-1-propanone, 2,4,6-trimethylbenzoyl-di Phenylphosphine oxide, 2-methyl-2-(4-morpholinyl)-1-[4-(methylthio)phenyl]-1-propanone, 2,4,6-trimethylbenzoyl At least one of ethyl phenylphosphonate.

Further, the plasticizer is at least one of diethyl phthalate, dibutyl phthalate, dioctyl phthalate, tributyl phosphate, triphenyl phosphate, tricresyl phosphate kind.

Further, the silane coupling agent is at least one of vinyltriethoxysilane, γ-(methacryloyloxy)propyltrimethoxysilane, γ-glycidyl etheroxypropyltrimethoxysilane .

Further, the molar ratio of the hexamethylene diisocyanate trimer to the hydroxy acrylate is 1:3˜1:4.

Further, the hydroxy acrylate is hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate or hydroxybutyl acrylate.

Further, the catalyst is at least one of stannous octoate, dibutyltin dilaurate, triethylenediamine, dibutyltin diacetate, dibutyltin maleate, zinc octoate, preferably, the The dosage is 0.02-0.20% of the total mass of hexamethylene diisocyanate trimer and hydroxy acrylate.

Further, the polymerization inhibitor is at least one of hydroquinone, p-methoxyphenol, o-methylhydroquinone, p-benzoquinone, and phenothiazine. Preferably, the amount of the polymerization inhibitor It is 0.02-0.20% of the total mass of hexamethylene diisocyanate trimer and hydroxy acrylate.

The leveling agent can be any commercially available silicone or acrylic leveling agent suitable for oil-soluble systems.

The preparation method of above-mentioned polyurethane acrylate type UV curable material, comprises the steps:

(1) Mix hexamethylene diisocyanate trimer, hydroxy acrylate, catalyst and polymerization inhibitor, react at 60-80°C until the NCO value is ≤10%, and cool to obtain a polyurethane acrylate oligomer;

(2) Mix polyurethane acrylate oligomer, dodecafluoroheptyl methacrylate, reactive diluent, photoinitiator, plasticizer, silane coupling agent and leveling agent evenly.

Compared with the existing polyurethane acrylate UV curing material, the polyurethane acrylate UV curing material of the present invention has the advantages of no pollution, low volatilization, fast curing rate, high gloss, high hardness and high shear strength. The preparation method is simple, the cost is low, and no solvent needs to be added.

Description of drawings

The accompanying drawings are used to provide a further understanding of the present invention, and constitute a part of the description, and are used together with the embodiments of the present invention to explain the present invention, and do not constitute a limitation to the present invention. In the attached picture:

Fig. 1 is the infrared spectrogram of polyurethane acrylate oligomer.

detailed description

The preferred embodiments of the present invention will be described below in conjunction with the accompanying drawings. It should be understood that the preferred embodiments described here are only used to illustrate and explain the present invention, and are not intended to limit the present invention.

Example 1

Proportion: The molar ratio of hexamethylene diisocyanate trimer to hydroxy acrylate is 1:3, and the catalyst and polymerization inhibitor are both 0.10% of the total mass of hexamethylene diisocyanate trimer and hydroxy acrylate. In a clean and dry reactor with a nitrogen inlet, a stirrer, a thermometer and a reflux condenser, first add hexamethylene diisocyanate trimer and catalyst (stannous octoate) according to the proportion, stir, and protect in a nitrogen atmosphere Lower the temperature to 40-60°C, then add hydroxyethyl acrylate (HEA) and polymerization inhibitor (hydroquinone) dropwise, and the dropping time is about 0.5-1.5h. After dropping, keep the temperature for 10-60min, then continue to heat up to 60-80°C, keep the temperature for about 3-5h, until the NCO value (that is, the content of isocyanate groups in the sample, measured by acetone-di-n-butylamine titration method)≤ 10wt%, stop heating, stir and cool, and discharge to obtain polyurethane acrylate oligomer.

The infrared spectrum of urethane acrylate oligomers is shown in Figure 1. The stretching vibration absorption peak of the NH bond appears at 3369.3 cm ⁻¹ , and the stretching vibration absorption peak of the urethane bond -C=O appears at 1725.9 cm ⁻¹ , indicating the formation of There is no characteristic absorption peak around ^{2275cm −1} , indicating that the reaction of -NCO is almost complete, and the = _{CH 2} ^scissor vibration and =CH The characteristic absorption peak of the out-of-plane bending vibration indicates that the carbon-carbon double bond in HEA has been successfully connected to the end of the polyurethane molecule.

Weigh urethane acrylate oligomer, dodecafluoroheptyl methacrylate, reactive diluent, photoinitiator, plasticizer, silane coupling agent and leveling agent, mix, and in the dark condition, ultrasonic 0.5- About 2.0 hours, mix well to get polyurethane acrylate type UV curing material.

The role of dodecafluoroheptyl methacrylate is to increase the reactivity, enhance the water resistance, oil resistance, and stain resistance of the product, and improve the adhesion, surface hardness and gloss of the product.

Urethane acrylate oligomer is the main component of urethane acrylate UV-curable materials. It plays a major role in determining the light-curing rate, hardness, flexibility, shear strength and other properties of the material. The effect of its content on the properties of UV-curable materials Such as Table 1 and Table 2:

Table 1 Effect of urethane acrylate oligomer content on properties of UV-curable coatings

Table 2 Effect of urethane acrylate oligomer content on properties of UV-curable adhesives

Table note: dodecafluoroheptyl methacrylate 1.0wt%, plasticizer (diethyl phthalate) 1.0wt%, silane coupling agent (vinyltriethoxysilane) 1.0wt%, leveling agent (Yick Chemicals, YCK-1470) 1.0wt%, the mass ratio of reactive diluent to photoinitiator is 24:5, wherein the reactive diluent is pentaerythritol triacrylate and tripropylene glycol diacrylate (mass ratio 2:1), the photoinitiator is a mixture of 1-hydroxycyclohexyl phenyl ketone and 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (mass ratio 1.5:1) .

Performance test process: Apply polyurethane acrylate UV-curable material on the base material that has been decontaminated, degreased and dried beforehand, place it flat in the dark for 10 minutes, and then cure it under the irradiation of ultraviolet light.

Shear strength 1 is the shear strength after curing for 24 hours, and shear strength 2 is the shear strength after curing for 24 hours + soaking for 24 hours.

From the test results in Table 1 and Table 2, it can be found that the mass difference between before and after curing is not more than 5% (ie low VOC), the gloss used as a coating is not lower than 70, the hardness is not lower than 4H, and the shear strength used as an adhesive is not less than 5MPa, the shear strength is not less than 4.5MPa after soaking for 24 hours.

Example 2

Proportion: The molar ratio of hexamethylene diisocyanate trimer to hydroxy acrylate is 1:4, and the catalyst and polymerization inhibitor are both 0.20% of the total mass of hexamethylene diisocyanate trimer and hydroxy acrylate. In a clean and dry reactor with a nitrogen inlet, a stirrer, a thermometer and a reflux condenser, first add hexamethylene diisocyanate trimer and catalyst (dibutyltin dilaurate) according to the proportion, stir, and Under the protection of atmosphere, raise the temperature to 40-60°C, then add hydroxypropyl acrylate and polymerization inhibitor (p-methoxyphenol) dropwise, and the dropping time is about 0.5-1.5h. After dropping, keep the temperature for 10-60 minutes, then continue to heat up to 60-80°C, keep the temperature for about 3-5 hours, until the NCO value is ≤10wt%, stop heating, stir and cool, and discharge to obtain polyurethane acrylate oligomer.

According to urethane acrylate oligomer 61wt%, reactive diluent (trimethylolpropane triacrylate) 20wt%, photoinitiator (2,4,6-trimethylbenzoylphenylphosphonic acid ethyl ester) 10wt %, dodecafluoroheptyl methacrylate 3wt%, plasticizer (tributyl phosphate) 2wt%, silane coupling agent (γ-glycidyl etheroxypropyltrimethoxysilane, KH560) 3wt%, leveling (Deqian, 835) 1wt%, weighed polyurethane acrylate oligomer, dodecafluoroheptyl methacrylate, reactive diluent, photoinitiator, plasticizer, silane coupling agent and leveling agent, mixed , under the condition of avoiding light, ultrasonically for about 0.5-2.0h, and mix well to obtain polyurethane acrylate type UV curable material.

Example 3

Proportion: The molar ratio of hexamethylene diisocyanate trimer to hydroxy acrylate is 1:3.5, and the catalyst and inhibitor are both 0.02% of the total mass of hexamethylene diisocyanate trimer and hydroxy acrylate. In a clean and dry reactor with nitrogen inlet, stirrer, thermometer and reflux condenser, first add hexamethylene diisocyanate trimer and catalyst (zinc octoate) according to the proportion, stir, and under the protection of nitrogen atmosphere Raise the temperature to 40-60°C, then add hydroxybutyl acrylate and polymerization inhibitor (p-benzoquinone) dropwise, and the dropping time is about 0.5-1.5h. After dropping, keep the temperature for 10-60 minutes, then continue to heat up to 60-80°C, keep the temperature for about 3-5 hours, until the NCO value is ≤10wt%, stop heating, stir and cool, and discharge to obtain polyurethane acrylate oligomer.

According to urethane acrylate oligomer 58.6wt%, reactive diluent (pentaerythritol tetraacrylate) 40wt%, photoinitiator (2-hydroxy-2-methyl-1-phenyl-1-propanone) 1wt%, methyl Dodecafluoroheptyl acrylate 0.1wt%, plasticizer (dioctyl phthalate) 0.1wt%, silane coupling agent (γ-(methacryloyloxy)propyltrimethoxysilane, KH570) 0.1 wt%, leveling agent (byk, byk-331) 0.1wt%, weigh urethane acrylate oligomer, dodecafluoroheptyl methacrylate, reactive diluent, photoinitiator, plasticizer, silane The joint agent and the leveling agent are mixed, and under the condition of avoiding light, the ultrasonic wave is about 0.5-2.0h, and the mixture is uniform to obtain the polyurethane acrylate type UV curing material.

Finally, it should be noted that: the above is only a preferred embodiment of the present invention, and is not intended to limit the present invention. Although the present invention has been described in detail with reference to the foregoing embodiments, for those skilled in the art, it still The technical solutions recorded in the foregoing embodiments may be modified, or some technical features thereof may be equivalently replaced. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principles of the present invention shall be included within the protection scope of the present invention.

Claims (10)

1. Polyurethane acrylate type UV curing material, by weight, includes the following components: 30-70% polyurethane acrylate oligomer, 20-55% reactive diluent, 1-10% photoinitiator, 10% methacrylic acid Difluoroheptyl ester 0.1-3%, plasticizer 0.1-3%, silane coupling agent 0.1-3%, leveling agent 0.1-3%, Wherein, the urethane acrylate oligomer is obtained by the following method: mixing hexamethylene diisocyanate trimer, acrylate hydroxyl ester, catalyst and polymerization inhibitor, and reacting at 60-80°C until the NCO value is ≤10wt %. 2. polyurethane acrylate type UV curing material according to claim 1, is characterized in that, described reactive diluent is dipropylene glycol diacrylate, tripropylene glycol diacrylate, 1,6-hexanediol diacrylate At least one of ester, pentaerythritol triacrylate, trimethylolpropane triacrylate, pentaerythritol tetraacrylate. 3. polyurethane acrylate type UV curing material according to claim 1, is characterized in that, described photoinitiator is 1-hydroxycyclohexyl phenyl ketone, 2-hydroxyl-2-methyl-1-phenyl -1-acetone, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, 2-methyl-2-(4-morpholinyl)-1-[4-(methylthio)benzene At least one of -1-propanone, 2,4,6-trimethylbenzoylphenylphosphonic acid ethyl ester. 4. polyurethane acrylate type UV curing material according to claim 1, is characterized in that, described plasticizer is diethyl phthalate, dibutyl phthalate, dioctyl phthalate , at least one of tributyl phosphate, triphenyl phosphate, and tricresyl phosphate. 5. polyurethane acrylate type UV curing material according to claim 1, is characterized in that, described silane coupling agent is vinyltriethoxysilane, gamma-(methacryloyl oxygen) propyltrimethoxy At least one of silane and γ-glycidyloxypropyltrimethoxysilane. 6 . The polyurethane acrylate type UV curing material according to claim 1 , wherein the molar ratio of the hexamethylene diisocyanate trimer to hydroxy acrylate is 1:3˜1:4. 7. The polyurethane acrylate type UV curing material according to claim 1 or 6, wherein the hydroxy acrylate is hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, hydroxy methacrylate Propyl or Hydroxybutyl Acrylate. 8. The polyurethane acrylate type UV curing material according to claim 1 or 6, wherein the catalyst is stannous octoate, dibutyltin dilaurate, triethylenediamine, dibutyltin diacetate, cis-butyl At least one of dibutyltin olefinic acid and zinc octoate, preferably, the amount of the catalyst is 0.02-0.20% of the total mass of hexamethylene diisocyanate trimer and hydroxy acrylate; the polymerization inhibitor is At least one of hydroquinone, p-methoxyphenol, o-methylhydroquinone, p-benzoquinone, and phenothiazine. Preferably, the amount of the polymerization inhibitor is hexamethylene diisocyanate tris 0.02-0.20% of the total mass of polymer and hydroxy acrylate. 9. The application of the polyurethane acrylate type UV curing material described in any one of claims 1-8 as a coating or an adhesive. 10. the preparation method of the described polyurethane acrylate type UV curable material of claim 1, is characterized in that, comprises the steps: (1) Mix hexamethylene diisocyanate trimer, hydroxy acrylate, catalyst and polymerization inhibitor, react at 60-80°C until the NCO value is ≤10%, and cool to obtain a polyurethane acrylate oligomer; (2) Mix polyurethane acrylate oligomer, dodecafluoroheptyl methacrylate, reactive diluent, photoinitiator, plasticizer, silane coupling agent and leveling agent evenly.