CN113549368A - High-stability printing ink and preparation method thereof - Google Patents
High-stability printing ink and preparation method thereof Download PDFInfo
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- CN113549368A CN113549368A CN202110947366.XA CN202110947366A CN113549368A CN 113549368 A CN113549368 A CN 113549368A CN 202110947366 A CN202110947366 A CN 202110947366A CN 113549368 A CN113549368 A CN 113549368A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/101—Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
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- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
Abstract
The application relates to the technical field of printing ink, and particularly discloses high-stability printing ink and a preparation method thereof. The high-stability printing ink comprises the following components in parts by weight: 40-60 parts of urethane acrylate, 15-25 parts of color paste, 10-15 parts of reactive diluent, 2-5 parts of photoinitiator and 0.5-2 parts of auxiliary agent. The preparation method comprises the following steps: adding the polyurethane acrylate into a stirring kettle according to a formula, sequentially adding the reactive diluent, the color paste, the auxiliary agent and the photoinitiator under the condition of keeping out of the sun, adding the next raw material after adding the raw materials each time, and stirring uniformly to obtain the high-stability printing ink after all the raw materials are added. This application adopts polyurethane acrylate as the binder, has excellent wearability, pliability and adhesive force, and pigment adopts the mill base form to add in this application, and has better compatibility between the matrix resin, and stability is high, helps improving the degree of consistency of colour, and mill base exhibition look is good in polyurethane acrylate, is favorable to obtaining good printing effect.
Description
Technical Field
The application relates to the technical field of gloss oil, in particular to high-stability printing ink and a preparation method thereof.
Background
The ink is a uniform mixture composed of color bodies (such as pigments, dyes and the like), connecting materials, filling materials, additives and the like; printing can be carried out, and drying is carried out on the printed body; is a colored pasty adhesive with certain fluidity. Thus, color (hue), body (rheology such as thickness, fluidity, etc.) and drying properties are the three most important properties of the ink. They are of various types, have different physical properties, and are thick and sticky; while some are quite rare. Some vegetable oil is used as a connecting material; some use resin and solvent or water as connecting material. These are determined by the object to be printed (substrate), the printing method, the type of printing plate, the drying method, and the like.
Chinese patent document CN 107286746A discloses a high-adhesion water-based ink applied to PVC printing, which comprises the following components in parts by mass: 38-46 parts of waterborne polyurethane-acrylic resin emulsion, 35-45 parts of deionized water, 7-17 parts of pigment, 1-2 parts of ammonia water, 1-2 parts of defoaming agent and 2-3 parts of auxiliary agent; the aqueous polyurethane-acrylic resin emulsion is prepared by emulsion polymerization of polyurethane emulsion and acrylic monomer, and a silane coupling agent, sodium m-carboxybenzenesulfonate and graphene are added as emulsion polymerization auxiliaries in the polymerization process. The pigment is organic pigment and inorganic pigment, and the problem of uneven pigment dispersion easily exists when the powder pigment is directly added into an ink system, so that the printing effect is influenced.
In view of the above, it is necessary to change the pigment adding method to improve the dispersion effect of the pigment in the ink system, and further to improve the color uniformity and obtain good printing effect.
Disclosure of Invention
In order to solve the problems, the application provides a high-stability printing ink and a preparation method thereof, the high-stability printing ink adopts polyurethane acrylate as a connecting material, and multiple hydrogen bonds can be formed among polyurethane acrylate polymer molecular chains, so that a polyurethane film has excellent mechanical wear resistance and flexibility, and has better adhesive force for a substrate, especially a substrate difficult to bond.
In a first aspect, the present application provides a high stability printing ink, which adopts the following technical scheme:
a high-stability printing ink comprises the following components in parts by weight:
preferably, the color paste comprises the following components in parts by weight:
preferably, the silane coupling agent is one or two of nanda-42 and an antibacterial coupling agent.
Preferably, the structural formula of the antibacterial coupling agent is:
the antibacterial coupling agent is prepared by the following method:
dissolving 2- (4-aminophenyl) phenol and chloropropyltriethoxysilane in a molar ratio of 1:1 in excessive ethanol, heating to 150 ℃ under stirring for reacting for 6-8h, and distilling out ethanol and unreacted raw materials under reduced pressure, wherein the reaction equation is as follows:
preferably, the pigment is one or more of carbon black, titanium dioxide, iron oxide red, phthalocyanine blue and lead chrome yellow.
Preferably, the cosolvent is ethanol.
Preferably, the reactive diluent is one or more of hydroxyethyl methacrylate, tripropylene glycol diacrylate, 1, 6-hexanediol diacrylate and trimethylolpropane triacrylate.
Preferably, the photoinitiator is one or more of isopropyl thioxanthone, 2-hydroxy-2-methyl-1-phenyl acetone and 1-hydroxycyclohexyl benzophenone.
Preferably, the preparation method of the color paste comprises the following steps: according to the formula, the polyurethane acrylate and the cosolvent are added into a stirring kettle to be uniformly mixed, then the silane coupling agent is added to be stirred for 5-10min, then the wetting dispersant, the defoaming agent and the pigment are sequentially added, the mixture is stirred for 5min at the stirring speed of 800 plus materials and 1500r/min, and then the mixture is ground by a ball mill until the fineness reaches below 20 mu m.
In a second aspect, the present application provides a method for preparing a high-stability printing ink, which adopts the following technical scheme:
a preparation method of high-stability printing ink comprises the following steps: adding the polyurethane acrylate into a stirring kettle according to a formula, sequentially adding the reactive diluent, the color paste, the auxiliary agent and the photoinitiator under the condition of keeping out of the sun, adding the next raw material after adding the raw materials each time, and stirring uniformly to obtain the high-stability printing ink after all the raw materials are added.
In summary, the present application has the following beneficial effects:
(1) this application adopts urethane acrylate as the binder, can form multiple hydrogen bond between urethane acrylate high polymer molecular chain, make the polyurethane film have excellent mechanical wear resistance and pliability, and to the substrate, especially the substrate that is difficult to bond, better adhesive force has, in addition, pigment in this application adopts the form of mill base to add, and have better compatibility between the urethane acrylate matrix resin, stability is high, help improving the degree of consistency of colour, and mill base has good exhibition look nature in urethane acrylate, be favorable to obtaining good printing effect.
(2) The color paste in the application pre-disperses the pigment in the polyurethane acrylate and adds the silane coupling agent, the addition of the silane coupling agent is favorable for the uniform dispersion of the pigment in the color paste, the polyurethane acrylate in the color paste can improve the compatibility of the color paste in the printing ink, the dispersion uniformity of the pigment is further improved, and the more excellent printing effect is realized.
(3) The silane coupling agent in the color paste adopts one or two of Nadama-42 and an antibacterial coupling agent, the structures of the two contain benzene rings, so that larger steric hindrance can be generated, the distance between adjacent pigment particles can be increased, the dispersion uniformity can be improved, and chain segments of other substances can penetrate through the benzene rings due to the existence of the benzene rings to form a complex penetrating network, the benzene rings can be firmly anchored in a system after curing to form a strong fixing effect, so that the problem of ink pulverization can be effectively solved;
(4) the antibacterial coupling agent added in the color paste has the structure of the antibacterial agent 2-hydroxybiphenyl, can play a certain antibacterial role, and can be used for printed matters with certain antibacterial requirements.
Detailed Description
The present application will be described in further detail with reference to examples.
The preparation method of the color paste comprises the following steps: according to the formula, the polyurethane acrylate and the cosolvent are added into a stirring kettle to be uniformly mixed, then the silane coupling agent is added to be stirred for 5-10min, then the wetting dispersant, the defoaming agent and the pigment are sequentially added, the mixture is stirred for 5min at the stirring speed of 800 plus materials and 1500r/min, and then the mixture is ground by a ball mill until the fineness reaches below 20 mu m.
Color pastes with different component contents are prepared according to the preparation method, and the formula of each color paste is as follows:
color paste 1
20 parts of urethane acrylate, 20 parts of titanium dioxide, 426 parts of silane coupling agent, 1 part of wetting dispersant, 0.1 part of defoaming agent and 6 parts of ethanol.
Color paste 2
40 parts of urethane acrylate, 35 parts of titanium dioxide, 4215 parts of silane coupling agent, 1.5 parts of wetting dispersant, 0.5 part of defoaming agent and 10 parts of ethanol.
Color paste 3
30 parts of urethane acrylate, 30 parts of titanium dioxide, 30 parts of silane coupling agent Nadama-4210 parts, 1 part of wetting dispersant, 0.3 part of defoaming agent and 8 parts of ethanol.
Color paste 4
30 parts of urethane acrylate, 30 parts of titanium dioxide, 10 parts of antibacterial coupling agent, 1 part of wetting dispersant, 0.3 part of defoaming agent and 8 parts of ethanol.
Color paste 5
30 parts of urethane acrylate, 30 parts of titanium dioxide, 425 parts of silane coupling agent, 5 parts of antibacterial coupling agent, 1 part of wetting dispersant, 0.3 part of defoaming agent and 8 parts of ethanol.
Color paste 6
30 parts of urethane acrylate, 30 parts of titanium dioxide, 79210 parts of silane coupling agent KH 79210 parts of wetting dispersant, 0.3 part of defoaming agent and 8 parts of ethanol.
Color paste 7
30 parts of urethane acrylate, 30 parts of titanium dioxide, 427 parts of silane coupling agent Nada-427 parts, 1 part of wetting dispersant, 0.3 part of defoaming agent, 8 parts of ethanol and 3 parts of 2-hydroxybiphenyl.
Color paste 8
40 parts of urethane acrylate, 30 parts of titanium dioxide, 1 part of wetting dispersant, 0.3 part of defoaming agent and 8 parts of ethanol.
The preparation method of the high-stability printing ink comprises the following steps: adding the polyurethane acrylate into a stirring kettle according to a formula, sequentially adding the reactive diluent, the color paste, the auxiliary agent and the photoinitiator under the condition of keeping out of the sun, adding the next raw material after adding the raw materials each time, and stirring uniformly to obtain the high-stability printing ink after all the raw materials are added.
Inks with different component contents were prepared according to the above preparation method, and the formulation of each ink was as follows:
example 1
40 parts of urethane acrylate, 115 parts of color paste, 6 parts of hydroxyethyl methacrylate, 5 parts of tripropylene glycol diacrylate, 1 part of isopropyl thioxanthone, 1 part of 2-hydroxy-2-methyl-1-phenyl acetone, 0.3 part of defoaming agent and 0.3 part of leveling agent.
Example 2
60 parts of urethane acrylate, 225 parts of color paste, 6 parts of hydroxyethyl methacrylate, 9 parts of trimethylolpropane triacrylate, 5 parts of 1-hydroxycyclohexyl benzophenone, 0.8 part of defoaming agent and 1 part of leveling agent.
Example 3
50 parts of urethane acrylate, 320 parts of color paste, 6 parts of hydroxyethyl methacrylate, 7 parts of 1, 6-hexanediol diacrylate, 1 part of isopropyl thioxanthone, 2 parts of 2-hydroxy-2-methyl-1-phenyl acetone, 0.5 part of defoaming agent and 0.5 part of leveling agent.
Example 4
50 parts of urethane acrylate, 420 parts of color paste, 6 parts of hydroxyethyl methacrylate, 7 parts of 1, 6-hexanediol diacrylate, 1 part of isopropyl thioxanthone, 2 parts of 2-hydroxy-2-methyl-1-phenyl acetone, 0.5 part of defoaming agent and 0.5 part of leveling agent.
Example 5
50 parts of urethane acrylate, 520 parts of color paste, 6 parts of hydroxyethyl methacrylate, 7 parts of 1, 6-hexanediol diacrylate, 1 part of isopropyl thioxanthone, 2 parts of 2-hydroxy-2-methyl-1-phenyl acetone, 0.5 part of defoaming agent and 0.5 part of leveling agent.
Comparative example 1
50 parts of urethane acrylate, 620 parts of color paste, 6 parts of hydroxyethyl methacrylate, 7 parts of 1, 6-hexanediol diacrylate, 1 part of isopropyl thioxanthone, 2 parts of 2-hydroxy-2-methyl-1-phenyl acetone, 0.5 part of defoaming agent and 0.5 part of leveling agent.
Comparative example 2
50 parts of urethane acrylate, 720 parts of color paste, 6 parts of hydroxyethyl methacrylate, 7 parts of 1, 6-hexanediol diacrylate, 1 part of isopropyl thioxanthone, 2 parts of 2-hydroxy-2-methyl-1-phenyl acetone, 0.5 part of defoaming agent and 0.5 part of leveling agent.
Comparative example 3
50 parts of urethane acrylate, 820 parts of color paste, 6 parts of hydroxyethyl methacrylate, 7 parts of 1, 6-hexanediol diacrylate, 1 part of isopropyl thioxanthone, 2 parts of 2-hydroxy-2-methyl-1-phenyl acetone, 0.5 part of defoaming agent and 0.5 part of leveling agent.
The inks prepared in examples 1 to 5 and comparative examples 1 to 3 were coated on the surface of a PET substrate using a 0 # wire rod, and various performance tests were performed after UV curing, and the test results are shown in table 1.
TABLE 1
Wherein, the adhesive force is taken as an evaluation standard according to GB/T9286-98.
The water resistance test method comprises the following steps: samples prepared in examples 1-5 and comparative examples 1-3 are respectively taken and placed in deionized water at 24 ℃ for constant-temperature soaking for 72 hours, and the samples are taken out for observing the conditions of the samples.
The test method of the wear resistance comprises the following steps: a sample plate with the specification of 10cm multiplied by 10cm is manufactured and placed on a Taber 5135 rotary abrasion-resistant testing machine for testing, and the testing conditions are as follows: the load is 500g, a CS-10F grinding wheel is used for rotating 100 times, the gloss before and after the comparison test is carried out, and the gloss retention rate is more than or equal to 80 percent, so that the product is qualified.
The test method of ethanol resistance comprises the following steps: and wrapping a 400g weight with cotton cloth, dipping absolute ethyl alcohol with the purity of 99.8%, wiping the printed ink pattern back and forth 100 times (one back and forth is one time), and observing the ink falling condition on the surface of the sample after wiping.
The method for testing the ethanol resistance after 100h of aging resistance comprises the following steps: the samples prepared in examples 1 to 5 and comparative examples 1 to 3 were taken, respectively, subjected to accelerated aging for 100 hours using an accelerated aging tester, and then subjected to ethanol resistance test according to the above-described method.
Combining color pastes 1-8, examples 1-5, comparative examples 1-3, and Table 1, it can be seen that examples 1-5 are excellent in performance, except that examples 1-3 do not contain an antimicrobial component and do not have an antimicrobial property. Example 4 the antibacterial coupling agent is used to obtain a better antibacterial effect, and a good antibacterial rate can be maintained after 90 days. In example 5, nanda-42 and the antibacterial coupling agent are compounded and used practically, and all performances are good, but the antibacterial performance is reduced to some extent due to the reduction of the content of the antibacterial coupling agent. Compared with the example 3, the silane coupling agent Nanda-42 in the color paste is replaced by KH792, the wear resistance is reduced to some extent due to the lack of a benzene ring structure, the ethanol resistance is slightly reduced, a complex penetrating network cannot be formed with a system due to the lack of the benzene ring structure, and the ethanol resistance after 100h of aging resistance is obviously reduced. Compared with the example 4, the antibacterial agent 2-hydroxybiphenyl is independently added in combination with Nanda-42, so that the antibacterial rate is relatively low, and the antibacterial rate is obviously reduced after 90 days, probably because the 2-hydroxybiphenyl has the same benzene ring structure, but the compatibility of the 2-hydroxybiphenyl independently added in color paste is poor, the 2-hydroxybiphenyl has no good linking effect with organic resin and inorganic pigment, the dispersion is uneven, the antibacterial effect is relatively poor, and the 2-hydroxybiphenyl is easy to separate out after a long time, so that the antibacterial effect is seriously reduced. Compared with the example 3, the pigment of the comparative example 3 has uneven dispersion, poor luster, poor water resistance, abrasion resistance, ethanol resistance and the like because the silane coupling agent is not added in the color paste.
The ink obtained in the case of only using the silane coupling agent Nanda-42 in the formulation (as in examples 1 to 3) has no antibacterial property and can be used in the field having no special requirement for antibacterial property; the ink obtained in the case of using part of Nanda-42 and part of the antibacterial coupling agent in the formula (as in example 5) can be applied to the fields with certain requirements on antibacterial property but low requirements; the ink obtained in the case where all of the antimicrobial coupling agents are used in the formulation (as in example 4) can be applied to fields where the requirement for antimicrobial properties is high.
The present embodiment is only for explaining the present application and is not limited to the present application, and those skilled in the art can make modifications of the present embodiment without inventive contribution as required after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present application.
Claims (10)
1. A high stability printing ink is characterized in that: the paint comprises the following components in parts by weight:
2. the high stability printing ink of claim 1, wherein: the color paste comprises the following components in parts by weight:
3. the high stability printing ink of claim 2, wherein: the silane coupling agent is one or two of south Dai-42 and an antibacterial coupling agent.
4. A high stability printing ink according to claim 3, characterized in that: the structural formula of the antibacterial coupling agent is as follows:
5. the high stability printing ink of claim 2, wherein: the pigment is one or more of carbon black, titanium dioxide, iron oxide red, phthalocyanine blue and lead chrome yellow.
6. The high stability printing ink of claim 2, wherein: the cosolvent is ethanol.
7. The high stability printing ink of claim 1, wherein: the active diluent is one or more of hydroxyethyl methacrylate, tripropylene glycol diacrylate, 1, 6-hexanediol diacrylate and trimethylolpropane triacrylate.
8. The high stability printing ink of claim 1, wherein: the photoinitiator is one or more of isopropyl thioxanthone, 2-hydroxy-2-methyl-1-phenyl acetone and 1-hydroxycyclohexyl benzophenone.
9. The high stability printing ink of claim 1, wherein: the preparation method of the color paste comprises the following steps: according to the formula, the polyurethane acrylate and the cosolvent are added into a stirring kettle to be uniformly mixed, then the silane coupling agent is added to be stirred for 5-10min, then the wetting dispersant, the defoaming agent and the pigment are sequentially added, the mixture is stirred for 5min at the stirring speed of 800 plus materials and 1500r/min, and then the mixture is ground by a ball mill until the fineness reaches below 20 mu m.
10. A method for preparing a high stability printing ink according to any of claims 1 to 9, characterized in that: the method comprises the following steps: adding the polyurethane acrylate into a stirring kettle according to a formula, sequentially adding the reactive diluent, the color paste, the auxiliary agent and the photoinitiator under the condition of keeping out of the sun, adding the next raw material after adding the raw materials each time, and stirring uniformly to obtain the high-stability printing ink after all the raw materials are added.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114231081A (en) * | 2022-01-19 | 2022-03-25 | 深圳市丽冠卓宏科技有限公司 | Ultra-high aging-resistant UV (ultraviolet) ink and preparation method thereof |
| CN114806267A (en) * | 2022-04-12 | 2022-07-29 | 江西优科工业材料有限公司 | Radiation-curable high-stability antibacterial ink |
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| CN103224731A (en) * | 2012-10-24 | 2013-07-31 | 北京印刷学院 | Pinkish red UV ink-jet ink for high-speed ink-jet printing and preparation method thereof |
| CN109354925A (en) * | 2018-10-31 | 2019-02-19 | 传美讯电子科技（珠海）有限公司 | A kind of LED-UV ink-jet ink and preparation method thereof |
| CN109749484A (en) * | 2017-11-03 | 2019-05-14 | 北京化工大学 | A kind of preparation method and aluminium pigment of the based aluminum pigment of antimicrobial form |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102417760A (en) * | 2011-11-21 | 2012-04-18 | 东莞劲胜精密组件股份有限公司 | Radiation-curable ink-jet ink and preparation method thereof |
| CN103224731A (en) * | 2012-10-24 | 2013-07-31 | 北京印刷学院 | Pinkish red UV ink-jet ink for high-speed ink-jet printing and preparation method thereof |
| CN109749484A (en) * | 2017-11-03 | 2019-05-14 | 北京化工大学 | A kind of preparation method and aluminium pigment of the based aluminum pigment of antimicrobial form |
| CN109354925A (en) * | 2018-10-31 | 2019-02-19 | 传美讯电子科技（珠海）有限公司 | A kind of LED-UV ink-jet ink and preparation method thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114231081A (en) * | 2022-01-19 | 2022-03-25 | 深圳市丽冠卓宏科技有限公司 | Ultra-high aging-resistant UV (ultraviolet) ink and preparation method thereof |
| CN114806267A (en) * | 2022-04-12 | 2022-07-29 | 江西优科工业材料有限公司 | Radiation-curable high-stability antibacterial ink |
| CN114806267B (en) * | 2022-04-12 | 2024-05-03 | 江西优科工业材料有限公司 | Radiation-curable high-stability antibacterial ink |
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