A rubbing-resistant uv-coated gloss varnish, and a preparation method and application thereof

Abstract

The present application relates to a kind of rub-resistant UV coating varnish and its preparation method and application, belong to ink technical field.The rub-resistant UV coating varnish of the present application includes the following component by weight fraction: polymeric oligomer 30~40 parts, active diluent 40~50 parts, active amine assistant initiator 5~15 parts, photoinitiator 5~10 parts and additive 1~5 parts;The polymeric oligomer is mainly composed of epoxy soybean oil acrylate and acrylic ester modified rosin with mass ratio ≤0.5, and the active diluent is mainly composed of ethoxylated trimethylolpropane triacrylate and acryloyl morpholine with mass ratio ≤4.The rub-resistant UV coating varnish of the present application has good adhesion, coating-4 cup viscosity and drying property, can give the excellent rub-resistant performance and high gloss of cigarette packet grade and food grade printed matter coating.

Description

Technical Field

[0001] This invention relates to the field of ink technology, and in particular to a rub-resistant UV coating varnish, its preparation method, and its application. Background Technology

[0002] With the rapid development of offset printing in the packaging technology field, various types of paper packaging have emerged. Besides paper boxes for cigarettes, alcohol, children's toys, cosmetics, and gifts, food packaging, represented by chocolates, lollipops, and vacuum packaging, is also rapidly developing. At the same time, because foods like chocolates and lollipops involve a lot of handling during packaging or consumption, the printed materials used in these food packaging need to have excellent abrasion resistance to prevent the printing material from peeling off during packaging or consumption, thus affecting the packaging appearance or food quality.

[0003] Currently, printed materials such as chocolates, lollipops, and vacuum food packaging mostly use gold or silver cardboard or substrates such as aluminized layers, aluminum foil, or oxide vapor-deposited films for printing. Compared with ordinary white cardboard or coated paper, these substrates have lower surface tension and stronger tensile properties, which results in poor adhesion of varnish or ink printed on their surface. Moreover, because they involve rubbing and deformation in different directions during packaging or consumption, the rubbing stability of the printed materials is poor. Summary of the Invention

[0004] The purpose of this invention is to overcome the shortcomings of the prior art and provide a rub-resistant UV coating varnish, its preparation method, and its application.

[0005] To achieve the above objectives, the technical solution adopted by the present invention is as follows:

[0006] In a first aspect, the present invention provides a rub-resistant UV coating varnish, which comprises the following components by weight:

[0007] 30-40 parts of polymerizable oligomer, 40-50 parts of reactive diluent, 5-15 parts of reactive amine co-initiator, 5-10 parts of photoinitiator, and 1-5 parts of additives;

[0008] The polymeric oligomer is mainly composed of epoxidized soybean oil acrylate and acrylate-modified rosin, wherein the mass ratio of epoxidized soybean oil acrylate to acrylate-modified rosin is ≤0.5.

[0009] The active diluent is mainly composed of ethoxylated trimethylolpropane triacrylate and acrylmorpholine, and the mass ratio of ethoxylated trimethylolpropane triacrylate to acrylmorpholine is ≤4.

[0010] This invention combines epoxidized soybean oil acrylate with acrylate-modified rosin in a specific mass ratio to form a polymeric oligomer, and then combines it with an active diluent mainly composed of ethoxylated trimethylolpropane triacrylate and acryloylmorpholine in a specific mass ratio. This not only gives the rub-resistant UV coating varnish low viscosity, good wetting and adhesion to enhance its bonding performance with different substrates, but also enables it to cure rapidly to form a polymer network structure with both good hardness and flexibility, thereby giving the printed layer excellent rub resistance.

[0011] Optionally, by weight, the polymerizable oligomer can be 31, 33, 35, 37, or 39 parts; the reactive diluent can be 41, 43, 45, 47, or 49 parts; the reactive amine co-initiator can be 6, 8, 10, 12, or 14 parts; the photoinitiator can be 5.5, 6.5, 7.5, 8.5, or 9.5 parts; and the additive can be 1.5, 2.5, 3.5, or 4.5 parts.

[0012] In addition, the mass ratio of epoxidized soybean oil acrylate to acrylate-modified rosin in the above-mentioned polymeric oligomers can be 0.1, 0.2, 0.3, 0.4 or 0.5, and the mass ratio of ethoxylated trimethylolpropane triacrylate to acryloylmorpholine in the reactive dilution can be 0.5, 1, 1.5, 2, 2.5, 3, 3.5, 4 or 4.5.

[0013] As a preferred embodiment of the rub-resistant UV coating varnish of the present invention, the polymeric oligomer is mainly composed of epoxidized soybean oil acrylate and acrylate-modified rosin in a mass ratio of 1:(2-3); optionally, the mass ratio of epoxidized soybean oil acrylate to acrylate-modified rosin can be 1:2.1, 1:2.3, 1:2.5, 1:2.7 or 1:2.9.

[0014] In a preferred embodiment of the rub-resistant UV coating varnish of the present invention, the reactive diluent is mainly composed of ethoxylated trimethylolpropane triacrylate and acrylmorpholine in a mass ratio of 4:(1-2); optionally, the mass ratio of ethoxylated trimethylolpropane triacrylate to acrylmorpholine can be 4:1.1, 4:1.3, 4:1.5, 4:1.7 or 4:1.9.

[0015] As a preferred embodiment of the rub-resistant UV coating varnish of the present invention, the epoxidized soybean oil acrylate has a viscosity of 10,000 to 30,000 Pa·s at 30°C and an acid value of less than or equal to 15 mg KOH / g.

[0016] The epoxidized soybean oil acrylate with the above viscosity and acid value can better balance the polymerization rate and degradation performance of the rub-resistant UV coating varnish, and enhance the adhesion performance of the coating formed therefrom, so as to significantly improve the rub resistance.

[0017] Furthermore, the epoxidized soybean oil acrylate used in this invention is a transparent liquid with a functionality of 3 and a refractive index of 1.453±0.1. The viscosity of the epoxidized soybean oil acrylate can be measured using GB / T 10247-2008, and the acid value can be measured using GB / T 18609-2011.

[0018] As a preferred embodiment of the rub-resistant UV coating varnish of the present invention, the acrylate-modified rosin has an acid value of 200-250 mgKOH / g and a softening point of 100-150℃.

[0019] The acrylate-modified rosin with the above-mentioned acid value and softening point not only enables the coating formed by curing the rub-resistant UV coating varnish to have good adhesion, but also better balances the hardness and flexibility of the coating to achieve better rub resistance.

[0020] Furthermore, the acrylate-modified rosin used in this invention is a pale yellow transparent solid with a functionality of 3 and a color (Fe-Co) of 1 to 2. The acid value of the acrylate-modified rosin can be measured using GB / T 18609-2011, and the softening point can be measured using GB / T 12007.6-1989.

[0021] As a preferred embodiment of the rub-resistant UV coating varnish of the present invention, at least one of the following (I) to (III) is used;

[0022] (I) The active amine co-initiator is ethylenediamine and / or propylenediamine;

[0023] (II) The photoinitiator is at least one of 3-methyl-4-phenylbenzophenone, 1-(biphenyl-4-yl)-2-methyl-2-morpholinylpropane-1-one, and phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide;

[0024] (III) The additive is at least one of defoamer, leveling agent and polymerization inhibitor.

[0025] Optionally, the defoamer may be at least one of silicone defoamer, alcohol defoamer, and mineral oil defoamer; the leveling agent may be at least one of silicone leveling agent, polyurethane leveling agent, and acrylic polymer leveling agent; and the polymerization inhibitor may be at least one of polyphenol polymerization inhibitor, aromatic amine polymerization inhibitor, and p-hydroxyanisole.

[0026] Secondly, the present invention provides a method for preparing the above-mentioned rub-resistant UV coating varnish, which includes the following steps: mixing polymeric oligomers, reactive diluents, reactive amine co-initiators, photoinitiators and additives evenly to obtain rub-resistant UV coating varnish.

[0027] Preferably, the above preparation method includes the following steps: first, the polymeric oligomer, reactive diluent, reactive amine co-initiator and photoinitiator are stirred at 1000-1500 r / min until the fineness of the mixture reaches below 5 μm; then, the additives are added and mixed evenly at 500-1000 r / min to obtain the rub-resistant UV coating varnish.

[0028] Thirdly, the present invention provides the application of the above-mentioned rub-resistant UV coating varnish in the preparation of UV printing inks or printing layers of packaging materials.

[0029] Fourthly, the present invention provides a UV printing ink comprising pigment and the above-mentioned rub-resistant UV coating varnish.

[0030] Fifthly, the present invention provides a packaging film material comprising a base film and a printing layer attached to the base film, wherein the printing layer is prepared from the aforementioned UV printing ink.

[0031] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0032] This invention combines epoxidized soybean oil acrylate with acrylate-modified rosin in a specific mass ratio to form a polymeric oligomer, and then combines it with an active diluent mainly composed of ethoxylated trimethylolpropane triacrylate and acrylamide morpholine in a specific mass ratio. This results in a rub-resistant UV coating varnish with good adhesion, a Teack cup 4 viscosity, and good drying properties, which can impart excellent rub resistance and high gloss to cigarette packaging and food-grade printed coatings. Detailed Implementation

[0033] To better illustrate the purpose, technical solution, and advantages of the present invention, the present invention will be further described below in conjunction with specific embodiments.

[0034] Unless otherwise specified, all other materials, reagents, etc. used in the examples and comparative examples are commercially available.

[0035] 1. Raw materials and reagents

[0036] Epoxidized soybean oil acrylate 1: B-106, Jining Hongming Chemical Reagent Co., Ltd.

[0037] Epoxidized soybean oil acrylate 2:MDH, Hubei Maidehao Chemical Co., Ltd.;

[0038] Acrylate-modified rosin 1: 83137-13-7, Nantong Runfeng Petrochemical Co., Ltd.;

[0039] Acrylate-modified rosin 2: AMR-110, Shanghai Yunsen Industrial Co., Ltd.;

[0040] Ethoxylated trimethylolpropane triacrylate: L-61015, Guangdong Lankelu New Materials Co., Ltd.;

[0041] Acryloylmorpholine: 5117-12-4, Wuhan Jixin Yibang Biotechnology Co., Ltd.;

[0042] Polyurethane acrylate: T20D, Yuming (Shanghai) Chemical Co., Ltd.;

[0043] Polyester acrylate: EBECRYL 852, Zhanxin Resin (China) Co., Ltd.;

[0044] Tripropylene glycol diacrylate: TPGDA, Guangdong Lankelu New Materials Co., Ltd.;

[0045] Triethylene glycol dimethacrylate: TEGDMA, Jining Tangyi Chemical Co., Ltd.;

[0046] Trimethylolpropane triacrylate monomer: TMPTA, Hubei Jianchu Biomedical Co., Ltd.;

[0047] Modified epoxy acrylate: UV-51600, Jining Fangyu Chemical Co., Ltd.

[0048] 2. Preparation method of rub-resistant UV coating varnish

[0049] The polymeric oligomer, reactive diluent, reactive amine co-initiator and photoinitiator are mixed and stirred at 1200 r / min until the fineness of the mixture reaches below 5 μm. Then, the additives are added and stirred evenly at 700 r / min to obtain the rub-resistant UV coating varnish.

[0050] The material formulations of the rub-resistant UV coating varnishes in Examples 1 to 10 are shown in Table 1. Photoinitiator 1 is 3-methyl-4-phenylbenzophenone, photoinitiator 2 is 1-(biphenyl-4-yl)-2-methyl-2-morpholinylpropane-1-one, and photoinitiator 3 is phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide.

[0051] Table 1. Material formulations of rub-resistant UV coating varnishes in Examples 1-10

[0052]

[0053] The material formulations of the rub-resistant UV coating varnishes in Comparative Examples 1 to 7 are shown in Table 2. Among them, photoinitiator 1 is 3-methyl-4-phenylbenzophenone, photoinitiator 2 is 1-(biphenyl-4-yl)-2-methyl-2-morpholinylpropane-1-one, photoinitiator 3 is phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, and photoinitiator 4 is 1-hydroxy-cyclohexyl-phenyl ketone.

[0054] Table 2. Material formulations of rub-resistant UV coating varnishes in Comparative Examples 1-7

[0055]

[0056] 3. Performance Testing

[0057] (1) Coating gloss: The gloss was measured at an incident angle of 60° as specified in GB / T 9754-2007.

[0058] (2) Dryness: Determined according to QB / T 2826-2017.

[0059] (2) Fineness: The fineness of ink particles was determined according to Method 2 of QB / T 2624-2012.

[0060] (4) Fore-4 cup viscosity: determined according to GB / T 1723-1993.

[0061] (5) Adhesion: The adhesion was determined according to GB / T 9286-1998.

[0062] (6) Kneading resistance: Tested according to GB / T 41347-2022, using mode B - long stroke kneading 900 times.

[0063] The rub-resistant UV coating varnishes in each embodiment and comparative example were tested according to the above performance test method, and the test results are shown in Table 3.

[0064] Table 3 shows the performance of the rub-resistant UV coating varnishes in each embodiment and comparative example.

[0065]

[0066] As shown in Table 3, the gloss of the rub-resistant UV coating varnishes in Examples 1 to 10 is greater than or equal to 107, the adhesion grade is 0, and the difference in the number of pinholes before and after the rubbing test is less than or equal to 10. This indicates that the rub-resistant UV coating varnish of the present invention not only has high gloss, good adhesion performance, and excellent rub resistance, but also maintains good fineness, Forte 4 cup viscosity, and drying properties.

[0067] As can be seen from Comparative Example 1, when epoxy soybean oil acrylate is replaced with polyurethane acrylate and combined with acrylic-modified rosin as a polymerizable oligomer, it is difficult to effectively improve the adhesion and abrasion resistance of the rub-resistant UV coating varnish. According to Comparative Examples 2 and 3, it can be found that the reactive diluent formed by combining tripropylene glycol diacrylate or triethylene glycol dimethacrylate with acryloylmorpholine not only fails to effectively improve the adhesion and abrasion resistance of the rub-resistant UV coating varnish, but also leads to a decrease in gloss.

[0068] As shown in Comparative Examples 4 and 5, when there is an excessive amount of epoxidized soybean oil acrylate in the polymeric oligomer, or an excessive amount of ethoxylated trimethylolpropane triacrylate in the reactive diluent, it is difficult to effectively improve the adhesion and abrasion resistance of the rub-resistant UV coating varnish. Meanwhile, as shown in Comparative Example 6, when the content of each component in the rub-resistant UV coating varnish is not within a suitable range, although the abrasion resistance is improved to some extent, the improvement effect is limited. Furthermore, as shown in Comparative Example 7, the rub-resistant UV coating varnish of the present invention, compared with existing similar UV coating varnishes, not only improves gloss and enhances adhesion, but also significantly improves abrasion resistance.

[0069] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit the scope of protection of the present invention. Although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art should understand that modifications or equivalent substitutions can be made to the technical solutions of the present invention without departing from the essence and scope of the technical solutions of the present invention.

Claims

1. A rub-resistant UV coating varnish, characterized in that, By weight, it includes the following components: 30-40 parts of polymeric oligomer, 40-50 parts of reactive diluent, 5-15 parts of reactive amine co-initiator, 5-10 parts of photoinitiator, and 1-5 parts of additives; The polymeric oligomer is composed of epoxidized soybean oil acrylate and acrylate-modified rosin, wherein the mass ratio of epoxidized soybean oil acrylate to acrylate-modified rosin is 1:(2~3). The active diluent is composed of ethoxylated trimethylolpropane triacrylate and acrylmorpholine, wherein the mass ratio of ethoxylated trimethylolpropane triacrylate to acrylmorpholine is 4:(1~2). The epoxidized soybean oil acrylate has a viscosity of 10,000~30,000 Pa·s at 30°C and an acid value ≤15 mgKOH / g. The acrylate-modified rosin has an acid value of 200-250 mgKOH / g and a softening point of 100-150 ℃.

2. The rub-resistant UV coating varnish as described in claim 1, characterized in that, The rub-resistant UV coating varnish satisfies at least one of the following conditions (I) to (III); (I) The active amine co-initiator is ethylenediamine and / or propylenediamine; (II) The photoinitiator is at least one of 3-methyl-4-phenylbenzophenone, 1-(biphenyl-4-yl)-2-methyl-2-morpholinylpropane-1-one, and phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide; (III) The additive is at least one of defoamer, leveling agent and polymerization inhibitor.

3. The method for preparing the rub-resistant UV coating varnish according to claim 1 or 2, characterized in that, Includes the following steps: The polymeric oligomer, reactive diluent, reactive amine co-initiator, photoinitiator and additives are mixed evenly to obtain a rub-resistant UV coating varnish.

4. The application of the rub-resistant UV coating varnish according to claim 1 or 2 in the preparation of UV printing inks or printing layers of packaging materials.

5. A UV printing ink comprising pigment and the rub-resistant UV coating varnish as described in claim 1 or 2.

6. A packaging film material, comprising a base film and a printed layer attached to the base film, characterized in that, The printed layer is prepared from the UV printing ink of claim 5.

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