CN113999563B - Anti-yellowing UV-LED glass substrate white ink - Google Patents

Abstract

The invention provides anti-yellowing UV-LED glass substrate white ink which comprises the following components in percentage by mass: 8-12% of hyperbranched multifunctional polyester resin, 8-12% of epoxy acrylic resin, 6-10% of polyester acrylate prepolymer, 8-12% of UV (ultraviolet) light-cured resin, 8-12% of ethoxy ethyl acrylate, 8-12% of diethylene glycol diacrylate, 8-12% of photoinitiator, 1.5-2.5% of coupling agent, 25-35% of titanium dioxide, 0.5-0.9% of defoaming agent and 0.2-0.4% of flatting agent. The invention has the advantages of no yellowing of the ink layer in the drying process, good leveling degree, high surface gloss, high surface hardness, good adhesive force of the ink layer, excellent weather resistance and the like. In addition, the invention also has the characteristics of no solvent, energy saving and environmental protection.

Description

Anti-yellowing UV-LED glass substrate white ink

The application is a divisional application, the original application number is 2018103475299, the application date is 20180418, and the patent names of the invention are: a UV-LED glass substrate white ink and a preparation method thereof.

Technical Field

The invention relates to the field of white ink, in particular to anti-yellowing UV-LED glass substrate white ink.

Background

Along with the development of social economy, the requirements of people on energy conservation and environmental protection are higher and higher, the aesthetic appearance is improved at the same time, the visual effect and the requirements on environmental protection and energy conservation are more and more emphasized by people in the color crystal industry or the manufacture of mobile phone cover plates, and the color crystal cover plate can be used as one of the standards for measuring the quality.

Conventional glass inks are generally composed of resins, pigments, solvents, auxiliaries, fillers, etc. In the solvent and resin, Volatile Organic Compounds (VOC) are often contained, which are mostly toxic, while the solvent content in the solvent-based glass ink is generally more than 30% of the total amount of the ink, and a part of the solvent is added to adjust the viscosity when the solvent-based glass ink is used. Most of the organic solvent is released into the air without participating in the reaction during the printing construction, thereby causing pollution. Besides solvent volatilization, the ink layer can be dried only by high-temperature baking in the printing construction process, and a large amount of energy is consumed; meanwhile, since the raw material may contain amino resin, harmful substances such as formaldehyde are also released by the self-condensation reaction of the amino resin along with the extension of the baking time and the increase of the temperature. The solvent glass ink used in the current market has certain difficulty in manufacturing high-precision patterns because the solvent volatilizes to cause the collapse of printing dots in the construction and printing processes.

Ultraviolet (UV) curing glass ink is environment-friendly and energy-saving ink which is characterized by adopting a radiation curing technology, and compared with the traditional glass ink technology, the UV curing glass ink has the advantages of energy conservation, high efficiency, no pollution, small occupied equipment and the like. The radiation curing technology is applied to the industry of colored crystal glass, and is a brand-new green new technology. The UV curing technology is a photo-processing technology for rapidly polymerizing a prepolymer with active groups to form a film through the irradiation of ultraviolet light, and the essence of the reaction is the cross-linking reaction of a prepolymer resin and a monomer. With the development of economic society, people have higher and higher requirements on environmental protection and energy conservation, and the trend that radiation curing replaces the traditional thermal curing is necessary.

Although the radiation curing technology is already applied to the colored crystal glass industry and also applied to the glass cover plate industry nowadays with the popularization of smart phones, in the emission energy of a UV mercury lamp, about 45% of the emission energy is UV light, and the other about 55% of the emission energy is long-wave band light, and the long-wave band light carries a large amount of heat, so that the surface of an irradiated object is yellowed, especially when the colored crystal glass and the mobile phone cover plate glass are coated with white ink in a full-page mode, the yellowing of the glass is obvious, and the yellowing of the ink is obvious. At present, technical personnel in the industry try to apply a brand-new LED technology with low energy consumption and single waveband to the colored crystal glass industry and the mobile phone cover plate industry, but because the interface energy of a glass substrate is low, the surface is too smooth and hard, the ink layer shrinks greatly during curing, especially because the content of white titanium dioxide is too high, the content of resin is low, and then the crosslinking density of the ink layer is difficult to improve, the requirements of the drying speed, the adhesive force, the boiling resistance, the chemical resistance and the like of the LED white ink layer on the glass surface are difficult to meet, and the LED glass ink, especially the white ink, cannot be put on the market in time.

Disclosure of Invention

In order to overcome the defects of the prior art, the invention aims to provide the anti-yellowing UV-LED glass substrate white ink which is excellent in performance, good in whiteness, free from yellowing, energy-saving and environment-friendly.

The invention also aims to provide a preparation method of the anti-yellowing UV-LED glass substrate white ink, which can be used for high-speed and effective production.

The invention provides anti-yellowing UV-LED glass substrate white ink which comprises the following components in percentage by mass: 8-12% of hyperbranched multifunctional polyester resin, 8-12% of epoxy acrylic resin, 6-10% of polyester acrylate prepolymer, 8-12% of UV (ultraviolet) light-cured resin, 8-12% of ethoxy ethyl acrylate, 8-12% of diethylene glycol diacrylate, 8-12% of photoinitiator, 1.5-2.5% of coupling agent, 25-35% of titanium dioxide, 0.5-0.9% of defoaming agent and 0.2-0.4% of flatting agent; the photoinitiator comprises bis (2,4, 6-trimethylbenzoyl) -phenylphosphine oxide, 1-hydroxy-cyclohexyl-phenyl ketone, 2,4, 6-trimethylbenzoyl-diphenyl phosphine oxide and ketone hydrogen abstraction type photoinitiators, wherein the mass ratio of the photoinitiators is bis (2,4, 6-trimethylbenzoyl) -phenylphosphine oxide: 1-hydroxy-cyclohexyl-phenyl-methanone: 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide: the ketone hydrogen abstraction photoinitiator is 1:1:1: 1.5.

Further, the photoinitiator respectively accounts for the total mass of the ink in percentage by mass: 2% of bis (2,4, 6-trimethylbenzoyl) -phenylphosphine oxide, 2% of 1-hydroxy-cyclohexyl-phenyl ketone, 2% of 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide and 3% of ketone hydrogen abstraction type photoinitiator.

Furthermore, the hyperbranched multifunctional polyester resin is a hyperbranched tetrafunctional polyester resin with the brand new company model number IRR 859.

Further, the ketone hydrogen abstraction type photoinitiator is an LED liquid photoinitiator with the model number of GC-407 of Guangdong electronic materials company.

Further, the titanium dioxide is weather-resistant titanium dioxide of 2300 type by Huiyu chemical company.

Further, the coupling agent is methacryloxy functional silane. Methacryloxy functional silane coupling agent 6040 from dow corning is preferred.

Further, the defoaming agent is a polysiloxane mixture. Preferably 6800 adjuvant from hume (shanghai) chemical co.

Further, the leveling agent is polyether modified polysiloxane copolymer. BNK-LK610 acrylic levelling agents from Milliken & company are preferred.

The preparation method of the anti-yellowing UV-LED glass substrate white ink comprises the following steps:

s1, dispersing hyperbranched polyfunctional polyester resin, epoxy acrylic resin, polyester acrylate prepolymer, UV (ultraviolet) light curing resin, ethoxy ethyl acrylate, diethylene glycol diacrylate and photoinitiator by a high-speed stirrer until the mixture is heated and completely dissolved to prepare a semi-finished product A;

s2, adding titanium dioxide into the semi-finished product A, and fully stirring until the titanium dioxide is heated and dispersed to prepare a semi-finished product B;

s3, adding the leveling agent, the defoaming agent and the coupling agent into the semi-finished product B, and fully stirring to prepare a semi-finished product C;

s4, fully grinding the semi-finished product C on a three-roller machine until the semi-finished product C reaches a specified fineness to obtain a finished product, wherein the fineness is 1-5 micrometers;

and S5, canning the finished product by using a packaging method for preventing air from permeating.

The principle and the beneficial effects of the invention are as follows:

the hyperbranched multifunctional polyester resin, the epoxy acrylic resin, the polyester acrylate prepolymer and the UV light-cured resin are used as main resin to provide a framework on the surface of the ink layer, and have the advantages of high drying speed under an LED lamp tube, high surface hardness of the ink layer, good scratch resistance, good adhesive force and the like. The monofunctional monomer ethyl ethoxy acrylate is matched with the monomer diluent diethylene glycol diacrylate, and has the advantages of low shrinkage, low odor, high drying speed and the like.

The photoinitiator is prepared by combining bis (2,4, 6-trimethylbenzoyl) -phenyl phosphine oxide, 1-hydroxy-cyclohexyl-phenyl ketone, 2,4, 6-trimethylbenzoyl-diphenyl phosphine oxide and ketone hydrogen abstraction type photoinitiator according to the ratio of 1:1:1:1.5, wherein the ketone hydrogen abstraction type photoinitiator is an LED special initiator GC407 provided by Guangdong electronic materials company, the 1-hydroxy-cyclohexyl-phenyl ketone preferably selects Shenzhen 184S, 2,4, 6-trimethylbenzoyl-diphenyl phosphine oxide and the bis (2,4, 6-trimethylbenzoyl) -phenyl phosphine oxide respectively preferably selects TPO and 819 of Tianjin Jiu chemical company, and the raw materials are matched as the photoinitiator, so that the photoinitiator has the advantages of quick drying and no yellowing under LED light, in addition, the super-weather-resistant titanium pigment 2300 provided by the Huiyu chemical company has the advantages of high whiteness, good weather resistance, no yellowing and the like, and the yellowing resistance of the ink is further improved.

According to the invention, a methacryloxy functional group silane coupling agent is selected as an adhesion promoter, so that the adhesion problem is better solved. The leveling agent is polyether modified polysiloxane copolymer, preferably BNK-LK610 acrylic leveling agent of Milliken company, and has the advantages of good leveling, unstable foam, small influence on the surface energy of a substrate, and the like.

The invention has the advantages that: the anti-yellowing UV-LED glass substrate white ink provided by the invention has the advantages that an ink layer is not yellowed in a drying process, the leveling degree is good, the surface gloss is high, the surface hardness reaches 3H, the adhesive force of the ink layer is good, the ink layer does not fall off in a hundred-grid test, the ink layer does not fall off after being cooked for 2 hours in boiling water at the temperature of 100 ℃, and the weather resistance of the ink layer is excellent. The resin and the monomer used in the invention do not contain solvent, are very environment-friendly, are solvent-free ink, do not volatilize harmful substances in the transportation process and the construction and printing process, and do not release ozone like UV ink curing. The invention forms a compact curing ink layer through LED light source curing, can greatly reduce the emission of harmful gases of the base material, and is particularly environment-friendly. Meanwhile, the glass substrate irradiated by the LED light source used by the ink disclosed by the invention cannot be yellowed like the glass substrate irradiated by UV light.

Detailed Description

The invention will now be further described with reference to the following examples and corresponding performance tests:

the first embodiment is as follows:

the anti-yellowing UV-LED glass substrate white ink comprises the following components in percentage by mass: 10% of hyperbranched four-functional group polyester resin, 10% of epoxy acrylic resin, 8% of polyester acrylate prepolymer, 10% of UV (ultraviolet) light curing resin, 10% of ethyl ethoxy acrylate, 10% of diethylene glycol diacrylate, 9% of photoinitiator, 2% of coupling agent methacryloxy functional group silane, 30% of titanium dioxide, 0.7% of defoaming agent polysiloxane mixture and 0.3% of leveling agent polyether modified polysiloxane copolymer. The photoinitiator specifically comprises 2% of bis (2,4, 6-trimethylbenzoyl) -phenylphosphine oxide, 2% of 1-hydroxy-cyclohexyl-phenyl ketone, 2% of 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide and 3% of ketone hydrogen abstraction type photoinitiator.

Preferably, the hyperbranched tetra-functional polyester resin is polyester resin IRR859 from Zhanxin company. The epoxy acrylic resin is epoxy acrylic resin 601 of Baojun company. The polyester acrylate prepolymer is prepared from DM-272 resin of Songtai company. The UV light-cured resin is selected from UV light-cured resin WDS-4017 of Wuxi Weidos electronic materials Co. The ethoxy ethyl acrylate is a monofunctional monomer EOEOEA of Guangzhou Boxing company. The diethylene glycol diacrylate is DEGDA provided by Qianye company. The bis (2,4, 6-trimethylbenzoyl) -phenylphosphine oxide is 819 of Tianjin Jiu chemical company. 2% of the 1-hydroxy-cyclohexyl-phenyl methanone adopts Shenzhen 184S of chemical company. 2 percent of the 2,4, 6-trimethylbenzoyl-diphenyl phosphine oxide is TPO of Tianjin Jiu chemical company. The ketone hydrogen abstraction type photoinitiator is an LED special initiator GC407 provided by Guangdong electronic material company. The coupling agent is 6040 from Dow Corning company. The titanium dioxide is 2300 titanium dioxide of comet chemical company. The antifoaming agent is 6800 of the courtesy (Shanghai) chemical Co., Ltd. The leveling agent is BNK-LK610 of Milliken company.

The preparation method of the anti-yellowing UV-LED glass substrate white ink comprises the following steps:

s1, mixing hyperbranched multifunctional polyester resin, epoxy acrylic resin, polyester acrylate prepolymer, UV light curing resin, ethoxy ethyl acrylate, diethylene glycol diacrylate and photoinitiator: dispersing bis (2,4, 6-trimethylbenzoyl) -phenylphosphine oxide, 1-hydroxy-cyclohexyl-phenyl ketone, 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide and ketone hydrogen abstraction type photoinitiator by a high-speed stirrer until the photoinitiator is heated and completely dissolved to prepare a semi-finished product A;

s2, adding titanium dioxide into the semi-finished product A, and fully stirring until the titanium dioxide is heated and dispersed to prepare a semi-finished product B;

s3, adding the leveling agent, the defoaming agent and the coupling agent into the semi-finished product B, and fully stirring to prepare a semi-finished product C;

s4, fully grinding the semi-finished product C on a three-roller machine until the semi-finished product C reaches a specified fineness to obtain a finished product, wherein the fineness is 1-5 micrometers;

and S5, canning the finished product by using a packaging method for preventing air from permeating.

The finished product prepared from the anti-yellowing UV-LED glass substrate white ink according to the above proportion and the preparation method is subjected to performance test, and the results are shown in the following table 1:

TABLE 1

The test results show that the excellent properties of the product comprise:

1. the LED light source is adopted for curing, the efficiency is high, the energy consumption is low, the light curing time is about 5 seconds, the light curing energy is 3Kw, and a post-heating process is not needed; the baking time of the traditional solvent glass ink is generally 170 ℃ for 10min, and the energy of an adopted infrared drying tunnel is not lower than 70 KW. UV inks typically require 8-10 seconds and UV curing energy may require approximately 12 KW.

2. The cured ink layer is not yellowed, and the glass substrate is not yellowed after being irradiated by the LED light: the UV lamp tube is adopted for curing, a large amount of energy is not effectively converted into curing energy and is released in a heat mode, so that the ink layer is easy to yellow, the glass can also yellow, and the LED lamp light is adopted for curing, so that the energy conversion rate is high, the ink layer and the surface of the glass cannot generate high temperature and further cannot yellow easily, and the whiteness of the cured white ink is excellent, and the UV lamp tube is particularly suitable for the high-grade colored crystal glass industry and the mobile phone cover plate industry.

3. The cured film has the hardness of 3H, excellent wear resistance and adhesive force, and no falling off when the hundred-grid test is 100%;

4. excellent water resistance, and after the ink layer is completely cured, the adhesive force is not obviously influenced after the ink layer is soaked in water for 240 hours; the adhesive force is not obviously influenced after the mixture is cooked for 2 hours in boiling water of 100 ℃.

5. The silk screen printing ink does not contain volatile organic solvents, has no pungent smell, does not generate ozone, and does not block the screen during silk screen printing.

6. The surface leveling property of the ink layer is good, and the glossiness is high;

7. the odor is low, the irritation to the human body is small, no ozone is generated, a large amount of radiation substances are not generated, and the health of constructors is better ensured.

8. Acid and alkali resistance: 5% sodium hydroxide solution and 5% hydrochloric acid solution were dropped onto the ink layer prepared in the present invention, respectively, and no discoloration was observed after 8 hours.

9. Ink layer weatherability: the high-low temperature circulation (one circulation every two hours, the high temperature is 80 ℃, the low temperature is-30 ℃, and the total of 24 circulations) has no obvious color difference of the ink layer and no falling of the ink layer; no color change is caused after the ultraviolet (40w) is irradiated for 48 hours; after being irradiated by sunlight for 30 days, the ink layer still does not fade, and the bright color of the ink layer after long-time use is ensured.

10. Ink layer recoatability: there is no problem with adhesion when other colors of LED color inks or UV and conventional solvent inks are screen printed on the already cured LED white ink.

The anti-yellowing UV-LED glass substrate white ink has a profound leading effect in the application of the color crystal glass industry and the glass cover plate industry, overcomes the technical difficulty that the UV white ink is difficult to solve yellowing on the glass substrate, and successfully realizes the conversion of the glass ink from the traditional solvent baking ink to the high-efficiency UV ink and then to the LED ink which is more energy-saving and environment-friendly; the high-speed and effective production in the colored crystal glass industry and the mobile phone cover plate industry is realized, and the problems of wide occupied area, large occupied equipment, long construction time, high energy consumption, environmental pollution, high energy consumption and the like of the traditional solvent ink construction are solved; the problems that the traditional UV ink is difficult to solve that the glass is white and yellow and the glass itself can yellow under UV light are solved; the influence of the traditional solvent ink printing on environmental pollution and the health of workers is eliminated; the harmful effect that ozone breaks the atmosphere and the damage of UV radiation to the body of a constructor in the production process of the traditional UV printing ink are eliminated; the product quality is optimized, and the added value of the product is improved.

The above preferred embodiments should be considered as examples of the embodiments of the present application, and technical deductions, substitutions, improvements and the like similar to, similar to or based on the embodiments of the present application should be considered as the protection scope of the present patent.

Claims (6)

1. The anti-yellowing UV-LED glass substrate white ink is characterized by comprising the following components in percentage by mass: 10% of hyperbranched four-functional group polyester resin, 10% of epoxy acrylic resin, 8% of polyester acrylate prepolymer, 10% of UV (ultraviolet) light curing resin, 10% of ethoxy ethyl acrylate, 10% of diethylene glycol diacrylate, 9% of photoinitiator, 2% of coupling agent, 30% of titanium dioxide, 0.7% of defoaming agent and 0.3% of flatting agent;

the photoinitiator comprises bis (2,4, 6-trimethylbenzoyl) -phenylphosphine oxide, 1-hydroxy-cyclohexyl-phenyl ketone, 2,4, 6-trimethylbenzoyl-diphenyl phosphine oxide and ketone hydrogen abstraction type photoinitiators, wherein the mass ratio of the photoinitiators is bis (2,4, 6-trimethylbenzoyl) -phenylphosphine oxide: 1-hydroxy-cyclohexyl-phenyl-methanone: 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide: ketone hydrogen abstraction type photoinitiator is 1:1:1: 1.5;

the hyperbranched four-functional group polyester resin is selected from polyester resin IRR859 of Zhan new company, the epoxy acrylic resin is selected from epoxy acrylic resin 601 of Baojun company, the polyester acrylate prepolymer is selected from DM-272 resin of Songtai company, the UV light-cured resin is selected from UV light-cured resin WDS-4017 of Wuxi Weidos electronic materials Co., Ltd, the ethoxy ethyl acrylate is selected from monofunctional monomer EOEA of Guangzhou Boxing company, the diethylene glycol diacrylate is selected from DEGDA provided by Qianye company, the ketone hydrogen-abstraction type photoinitiator is an LED liquid photoinitiator of Guangdong electronic materials company with the model of GC-407, and the titanium dioxide is weather-resistant titanium dioxide of Huiyu chemical company with the model of 2300.

2. The anti-yellowing UV-LED glass substrate white ink according to claim 1, wherein: the photoinitiator respectively accounts for the total mass of the ink in percentage by mass: 2% of bis (2,4, 6-trimethylbenzoyl) -phenylphosphine oxide, 2% of 1-hydroxy-cyclohexyl-phenyl ketone, 2% of 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide and 3% of ketone hydrogen abstraction type photoinitiator.

3. The anti-yellowing UV-LED glass substrate white ink according to claim 1, wherein: the coupling agent is methacryloxy functional silane.

4. The anti-yellowing UV-LED glass substrate white ink according to claim 1, wherein: the defoaming agent is a polysiloxane mixture.

5. The anti-yellowing UV-LED glass substrate white ink according to claim 1, wherein: the leveling agent is polyether modified polysiloxane copolymer.

6. The anti-yellowing UV-LED glass substrate white ink according to claim 1, wherein: the preparation method of the anti-yellowing UV-LED glass substrate white ink comprises the following steps:

s1, dispersing hyperbranched polyfunctional polyester resin, epoxy acrylic resin, polyester acrylate prepolymer, UV (ultraviolet) light curing resin, ethoxy ethyl acrylate, diethylene glycol diacrylate and photoinitiator through a high-speed stirrer until the materials are heated and completely dissolved to prepare a semi-finished product A;

s2, adding titanium dioxide into the semi-finished product A, and fully stirring until the titanium dioxide is heated and dispersed to prepare a semi-finished product B;

s3, adding the leveling agent, the defoaming agent and the coupling agent into the semi-finished product B, and fully stirring to prepare a semi-finished product C;

s4, fully grinding the semi-finished product C on a three-roller machine until the semi-finished product C reaches a specified fineness to obtain a finished product, wherein the fineness is 1-5 micrometers;

and S5, canning the finished product by using a packaging method for preventing air from permeating.