A plastic matte UV-curing coating and preparation method thereof

Abstract

The present invention relates to the field of ultraviolet curing coatings, and in particular to a plastic matte ultraviolet curing coating and a preparation method thereof, which is composed of the following components in parts by weight: 30-40 parts of acrylic resin, 15-30 parts of bifunctional monomers, 30-45 parts of trifunctional monomers, 5-10 parts of modifiers, 1-5 parts of active amines, 3-6 parts of initiators, and 1-3 parts of auxiliary agents; the structural formula of the modifier is as follows: The coating prepared by the present invention has good mechanical properties after ultraviolet curing and has strong adhesion to a plastic substrate.

Description

Technical Field

[0001] The present invention relates to the field of ultraviolet curing coatings, in particular to a plastic matte ultraviolet curing coating and a preparation method thereof. Background Art

[0002] Compared with traditional coatings, UV-curing coatings do not contain any organic solvents or volatile components, have a solid content of nearly 100%, and cause less pollution to the environment. At the same time, they have the characteristics of low curing energy consumption, high film-forming efficiency, good chemical stability, and wide applicability. They are widely used in the surface treatment of plastic structural parts such as home appliances, automobiles, mobile phones, PCs, medical equipment, and lighting appliances. They are a high-efficiency, energy-saving, and environmentally friendly modern coating.

[0003] However, UV-curing coatings have insufficient wettability and weak penetration on plastic substrates, which affects adhesion and limits their application to a certain extent. Summary of the Invention

[0004] Purpose of the invention: In order to solve the above technical problems, the present invention provides a plastic matte UV-curing coating and a preparation method thereof.

[0005] The technical solutions adopted are as follows:

[0006] A plastic matte UV-curing coating, comprising the following components in parts by weight: 30-40 parts of acrylic resin, 15-30 parts of bifunctional monomer, 30-45 parts of trifunctional monomer, 5-10 parts of modifier, 1-5 parts of active amine, 3-6 parts of initiator, and 1-3 parts of auxiliary agent;

[0007] The acrylic resin is composed of aromatic polyurethane modified acrylate, epoxy modified acrylate and polyester modified acrylate;

[0008] The mass ratio of the aromatic polyurethane modified acrylate, epoxy modified acrylate and polyester modified acrylate is 1-3:1-3:1-3;

[0009] The structural formula of the modifier is as follows:

[0010] .

[0011] Furthermore, the preparation method of the modifier is as follows:

[0012] ;

[0013] S1: 4,4',4''-methylenetriphenol undergoes esterification reaction with 2,2-dimethylolpropionic acid to obtain an intermediate product;

[0014] ;

[0015] S2: The intermediate product undergoes a condensation reaction with epichlorohydrin to obtain the modifier.

[0016] Furthermore, the bifunctional monomer is one or a combination of two or more of ethylene glycol dimethacrylate, ethylene glycol dimethacrylate, triethylene glycol methacrylate, tripropylene glycol methacrylate, tetraethylene glycol methacrylate, polyethylene glycol dimethacrylate, 1,4-butanediol dimethacrylate, neopentyl glycol dimethacrylate, propoxylated neopentyl glycol diacrylate, 1,6-ethylene glycol dimethyl diacrylate, phthalic acid dimethacrylate, phthalic acid monoethylene glycol dimethacrylate, ethoxylated bisphenol A dimethacrylate, and hydroxypivalic acid neopentyl glycol monoester dimethacrylate.

[0017] Furthermore, the trifunctional monomer is one or a combination of two or more of trimethylolpropane trimethacrylate, ethoxylated trimethylolpropane triacrylate, propoxylated trimethylolpropane triacrylate, glycerol trihydroxypropyl ether triacrylate, and pentaerythritol triacrylate.

[0018] Furthermore, the active amine consists of triethanolamine and isophoronediamine.

[0019] Furthermore, the mass ratio of triethanolamine to isophoronediamine is 1-5:1-5.

[0020] Furthermore, the initiator is one or a combination of two or more of 1-hydroxycyclohexyl benzophenone, p-phenyl benzophenone, 2-hydroxy-2-methyl-1-phenyl-1-propanone, 2-hydroxy-4-(2-hydroxyethoxy)-2-methylpropiophenone, 2-benzyl-2-methylamino-1-(4-morpholinophenyl)-1-butanone, 2-(4-methylbenzyl)-2-methylamino-1-(4-morpholinophenyl)-1-butanone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, ethyl 2,4,6-trimethylbenzoylphenylphosphonate, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, 4,4'-bis(diethylamino)benzophenone, and isopropylthioxanthone.

[0021] Furthermore, the auxiliary agent includes one or a combination of two or more of a dispersant, a leveling agent, a defoaming agent, and a matting powder.

[0022] The present invention also provides a method for preparing a matte plastic UV-curable coating:

[0023] Under light-proof conditions, first mix the acrylic resin, bifunctional monomer, trifunctional monomer, and modifier evenly, then add the active amine, initiator, and auxiliary agent and stir thoroughly.

[0024] Beneficial effects of the present invention:

[0025] The present invention provides a plastic matte UV curing coating. The aromatic polyurethane modified acrylate has good flexibility, strong adhesion and strength after film formation, and good weather resistance and chemical resistance. The epoxy modified acrylate can make the coating cure quickly after addition, improve the glossiness and wear resistance after film formation, and the polyester modified acrylate has low viscosity, high wettability, good leveling and fast curing speed. After addition, it can improve the adhesion of the coating. The three are combined to jointly improve the mechanical properties of the light curing coating after film formation and the adhesion to the plastic substrate. The modifier has an aromatic structure and multiple epoxy groups. The epoxy group can The active amine composed of triethanolamine and isophoronediamine can inhibit the oxygen inhibition effect of UV-curing coatings and catalyze the crosslinking of epoxy groups, thereby improving the density of the coating film. The coating prepared by the present invention has good mechanical properties and strong adhesion to the plastic substrate after UV curing. DETAILED DESCRIPTION

[0026] Unless otherwise specified, the following examples and comparative examples were conducted in parallel, using the same processing steps and parameters.

[0027] Aromatic polyurethane modified acrylate: Model R2205, purchased from Green Union (Jining) Chemical Technology Co., Ltd.

[0028] Epoxy modified acrylate: model UV-51600, purchased from Jining Fangyu Chemical Co., Ltd.

[0029] Polyester modified acrylate: model R3201, purchased from Green Union (Jining) Chemical Technology Co., Ltd.

[0030] Ethylene glycol dimethacrylate: purchased from Jiangsu Bosite Chemical Technology Co., Ltd.

[0031] Trimethylolpropane trimethacrylate: purchased from Jiangsu Bosite Chemical Technology Co., Ltd.

[0032] Modifier: homemade;

[0033] Triethanolamine: Merck;

[0034] Isophorone diamine: Merck;

[0035] 1-Hydroxycyclohexylbenzophenone: purchased from Wuhan Kemik Biopharmaceutical Technology Co., Ltd.

[0036] BYK-110 dispersant: purchased from Shanghai Kaiyin Chemical Co., Ltd.

[0037] BYK-380 leveling agent: purchased from Shanghai Kaiyin Chemical Co., Ltd.

[0038] BYK-1790 defoamer: purchased from Shanghai Kaiyin Chemical Co., Ltd.

[0039] RAD-2105 matte powder: Shenzhen Jitian Chemical Co., Ltd.

[0040] Example 1:

[0041] A plastic matte UV-curing coating, comprising the following components in parts by weight:

[0042] 12 parts of aromatic polyurethane modified acrylate, 12 parts of epoxy modified acrylate, 12 parts of polyester modified acrylate, 20 parts of ethylene glycol dimethacrylate, 35 parts of trimethylolpropane trimethacrylate, 8 parts of modifier, 2 parts of triethanolamine, 1 part of isophorone diamine, 4 parts of 1-hydroxycyclohexyl benzophenone, 0.5 parts of BYK-110 dispersant, 0.2 parts of BYK-380 leveling agent, 0.2 parts of BYK-1790 defoamer, 1 part of RAD-2105 matting powder;

[0043] The structural formula of the modifier is as follows:

[0044] .

[0045] The preparation method of the modifier is as follows:

[0046] ;

[0047] S1: Under nitrogen protection, add 4,4',4''-methylenetriphenol (0.1 mol), 2,2-dihydroxymethylpropionic acid (0.3 mol), and p-toluenesulfonic acid (1 g) as a catalyst to a flask. Stir and heat to 140°C for 5 h. During the reaction, separate the generated water with a water separator. After the reaction, stop the nitrogen flow and connect a vacuum pump to distill under reduced pressure until no water is distilled out. Cool to room temperature, dissolve with an appropriate amount of acetone, recrystallize in toluene, and filter. The obtained product is the intermediate product.

[0048] ;

[0049] S2: Under nitrogen protection, the intermediate product (0.01 mol) and epichlorohydrin (0.1 mol) were added to a flask, stirred and heated to 110 ° C, and then 4.5 g of sodium hydroxide was added. After the reaction was continued for 1 h, the reaction solution was cooled to room temperature and 100 ml of dichloromethane and 100 ml of deionized water were added. After sufficient stirring, the dichloromethane phase was separated and washed with 100 ml of 20 wt% sodium hydroxide solution. The dichloromethane phase was separated and dried with anhydrous sodium sulfate and concentrated under reduced pressure to obtain the modifier. ESI-MS (m / z) (M + ): Theoretical value 977.07, measured value 977.21.

[0050] Preparation method of the above-mentioned plastic matte UV-curing coating:

[0051] Under light-proof conditions, first mix the aromatic polyurethane modified acrylate, epoxy modified acrylate, polyester modified acrylate, ethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, and modifier, and stir at 200r / min for 30 minutes to mix evenly. Then add triethanolamine, isophoronediamine, 1-hydroxycyclohexyl benzophenone, BYK-110 dispersant, BYK-380 leveling agent, BYK-1790 defoamer, and RAD-2105 matting powder, and finally stir at 50°C for 10 minutes.

[0052] Example 2:

[0053] A plastic matte UV-curing coating, comprising the following components in parts by weight:

[0054] 12 parts of aromatic polyurethane modified acrylate, 10 parts of epoxy modified acrylate, 10 parts of polyester modified acrylate, 30 parts of ethylene glycol dimethacrylate, 45 parts of trimethylolpropane trimethacrylate, 10 parts of modifier, 2 parts of triethanolamine, 1 part of isophorone diamine, 5 parts of 1-hydroxycyclohexyl benzophenone, 0.5 parts of BYK-110 dispersant, 0.2 parts of BYK-380 leveling agent, 0.2 parts of BYK-1790 defoamer, 1 part of RAD-2105 matting powder;

[0055] The structural formula and preparation method of the modifier are the same as those in Example 1;

[0056] Preparation method of the above-mentioned plastic matte UV-curing coating:

[0057] Under light-proof conditions, first mix the aromatic polyurethane modified acrylate, epoxy modified acrylate, polyester modified acrylate, ethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, and modifier, and stir at 200r / min for 30 minutes to mix evenly. Then add triethanolamine, isophoronediamine, 1-hydroxycyclohexyl benzophenone, BYK-110 dispersant, BYK-380 leveling agent, BYK-1790 defoamer, and RAD-2105 matting powder, and finally stir at 50°C for 10 minutes.

[0058] Example 3:

[0059] A plastic matte UV-curing coating, comprising the following components in parts by weight:

[0060] 10 parts of aromatic polyurethane modified acrylate, 12 parts of epoxy modified acrylate, 12 parts of polyester modified acrylate, 15 parts of ethylene glycol dimethacrylate, 30 parts of trimethylolpropane trimethacrylate, 5 parts of modifier, 2 parts of triethanolamine, 1 part of isophorone diamine, 3 parts of 1-hydroxycyclohexyl benzophenone, 0.5 parts of BYK-110 dispersant, 0.2 parts of BYK-380 leveling agent, 0.2 parts of BYK-1790 defoamer, 1 part of RAD-2105 matting powder;

[0061] The structural formula and preparation method of the modifier are the same as those in Example 1;

[0062] Preparation method of the above-mentioned plastic matte UV-curing coating:

[0063] Under light-proof conditions, first mix the aromatic polyurethane modified acrylate, epoxy modified acrylate, polyester modified acrylate, ethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, and modifier, and stir at 200r / min for 30 minutes to mix evenly. Then add triethanolamine, isophoronediamine, 1-hydroxycyclohexyl benzophenone, BYK-110 dispersant, BYK-380 leveling agent, BYK-1790 defoamer, and RAD-2105 matting powder, and finally stir at 50°C for 10 minutes.

[0064] Comparative Example 1:

[0065] The method is basically the same as Example 1, except that aromatic polyurethane modified acrylate of the same mass is used to replace the combination of aromatic polyurethane modified acrylate, epoxy modified acrylate and polyester modified acrylate.

[0066] Comparative Example 2:

[0067] The method is basically the same as Example 1, except that epoxy-modified acrylate of the same mass is used to replace the combination of aromatic polyurethane-modified acrylate, epoxy-modified acrylate, and polyester-modified acrylate.

[0068] Comparative Example 3:

[0069] The method is basically the same as Example 1, except that polyester-modified acrylate of the same mass is used to replace the combination of aromatic polyurethane-modified acrylate, epoxy-modified acrylate, and polyester-modified acrylate.

[0070] Comparative Example 4:

[0071] The process is basically the same as Example 1, except that no modifier is added.

[0072] Comparative Example 5:

[0073] The process is substantially the same as Example 1, except that no triethanolamine is added.

[0074] Comparative Example 6:

[0075] The process is basically the same as Example 1, except that isophorone diamine is not added.

[0076] Performance testing:

[0077] The PVC plastic plate was wiped with deionized water and dried for use. The coatings in Examples 1-3 and Comparative Examples 1-6 were evenly applied thereon using a wire rod coater to obtain a smooth and flat coating film with a thickness of 8 μm. The PVC plastic plate was irradiated under a 5000 W, 300 nm UV lamp for 5 seconds. The performance of the cured coating was tested. The test results are shown in Table 1 below.

[0078] Adhesion test was conducted with reference to GB / T 9286-1998 "Scratch test for paint and varnish films";

[0079] Refer to GB / T 6739-2006 "Paints and varnishes - Determination of film hardness - Pencil method" for pencil hardness test;

[0080] The scratch resistance test was carried out with reference to GB / T 31591-2015 “Determination of scratch resistance of paints and varnishes”;

[0081]

[0082] As can be seen from Table 1 above, the coating prepared by the present invention has good mechanical properties and strong adhesion to the plastic substrate after UV curing.

[0083] By comparing Example 1 with Comparative Examples 1-3, it can be seen that the film-forming effect of the combination of aromatic polyurethane modified acrylate, epoxy modified acrylate, and polyester modified acrylate is better than that of a single film-forming effect;

[0084] By comparing Example 1 with Comparative Example 4, it can be seen that the addition of the modifier can greatly improve the mechanical properties of the coating film formed after the coating is cured and the adhesion to the plastic substrate;

[0085] By comparing Example 1 with Comparative Examples 5-6, it can be seen that the combination of triethanolamine and isophoronediamine has a greater improvement in the mechanical properties of the coating film formed after the coating is cured.

[0086] The above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit the same. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned embodiments, or make equivalent replacements for some of the technical features therein. However, these modifications or replacements do not deviate the essence of the corresponding technical solutions from the spirit and scope of the technical solutions of the various embodiments of the present invention.

Claims

1. A plastic matte UV-curing coating, characterized in that: The invention is composed of the following components in parts by weight: 30-40 parts of acrylic resin, 15-30 parts of bifunctional monomer, 30-45 parts of trifunctional monomer, 5-10 parts of modifier, 1-5 parts of active amine, 3-6 parts of initiator and 1-3 parts of auxiliary agent; The acrylic resin is composed of aromatic polyurethane modified acrylate, epoxy modified acrylate and polyester modified acrylate; The mass ratio of the aromatic polyurethane modified acrylate, epoxy modified acrylate and polyester modified acrylate is 1-3:1-3:1-3; The structural formula of the modifier is as follows: ； The auxiliary agent includes one or a combination of two or more of a dispersant, a leveling agent, a defoamer and a matting powder.

2. The plastic matte UV-curing coating according to claim 1, characterized in that: The preparation method of the modifier is as follows: ； S1: 4,4',4''-methylenetriphenol and 2,2-dihydroxymethylpropionic acid undergo esterification to obtain an intermediate product; ； S2: The intermediate product undergoes a condensation reaction with epichlorohydrin to obtain the modifier.

3. The plastic matte UV-curing coating according to claim 1, characterized in that: The trifunctional monomer is one or a combination of two or more of trimethylolpropane trimethacrylate, ethoxylated trimethylolpropane triacrylate, propoxylated trimethylolpropane triacrylate, glycerol trihydroxypropyl ether triacrylate, and pentaerythritol triacrylate.

4. The plastic matte UV-curing coating according to claim 1, characterized in that: The active amine consists of triethanolamine and isophoronediamine.

5. The plastic matte UV-curing coating according to claim 4, characterized in that: The mass ratio of triethanolamine to isophoronediamine is 1-5:1-5.

6. The plastic matte UV-curing coating according to claim 1, characterized in that: The initiator is one or a combination of two or more of 1-hydroxycyclohexyl benzophenone, p-phenyl benzophenone, 2-hydroxy-2-methyl-1-phenyl-1-propanone, 2-hydroxy-4-(2-hydroxyethoxy)-2-methylpropiophenone, 2-benzyl-2-methylamino-1-(4-morpholinophenyl)-1-butanone, 2-(4-methylbenzyl)-2-methylamino-1-(4-morpholinophenyl)-1-butanone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, ethyl 2,4,6-trimethylbenzoylphenylphosphonate, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, 4,4'-bis(diethylamino)benzophenone, and isopropylthioxanthone.

7. A method for preparing a plastic matte UV-curable coating as claimed in any one of claims 1 to 6, characterized in that: Under light-proof conditions, firstly mix the acrylic resin, bifunctional monomer, trifunctional monomer and modifier evenly, then add the active amine, initiator and auxiliary agent and stir thoroughly.

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