WO2017035693A1

WO2017035693A1 - Plastic aqueous gravure ink and preparation method therefor

Info

Publication number: WO2017035693A1
Application number: PCT/CN2015/088369
Authority: WO
Inventors: 刘志忠
Original assignee: 刘志忠
Priority date: 2015-08-28
Filing date: 2015-08-28
Publication date: 2017-03-09
Also published as: CN106459628A

Abstract

Provided is a plastic aqueous gravure ink, which consists of the following components, by weight percent: 25%-35% of an amino resin, 3%-8% of an aliphatic aqueous polyurethane resin, 30%-40% of a solvent, 8%-12% of an auxiliary, 8%-12% of a pigment and 8%-12% of a diluent. Also provided is a preparation method for the ink, which comprises: first dissolving the amino resin with the solvent under a condition of a thermostatic water bath of 80°C-100°C, so as to formulate same into an aqueous solution; then sequentially adding the aliphatic aqueous polyurethane resin, a catalyst and a surfactant, and reacting same for 1.5-2.5 h under a condition of a temperature of 20°C-25°C, then adding a defoamer and a levelling agent, and then continuous stirring same for 10-20 min; and adding a pigment at a temperature of 20°C-25°C and continuous stirring same for 15-25 min, then adding a diluent and a preservative and stirring same for 5-10 min.

Description

Plastic water-based gravure ink and preparation method thereof

Technical field

The invention belongs to the technical field of water-based gravure inks, and in particular relates to a plastic water-based gravure ink and a preparation method thereof.

Background technique

As a kind of environmentally friendly, non-toxic and energy-saving, solvent-free plastic water-based gravure ink, it has no pungent odor, and it can get clear and refreshing graphic effects with the same traditional printing method. For a long time, traditional plastic gravure inks are basically solvent-based inks, which are composed of benzene, formaldehyde, xylene, butyl acetate and other compounds. They are volatile, flammable, explosive, toxic, and highly irritating. Even today, when the environmental protection is improved, the ink used is only a solvent such as benzene or methanol. Still retaining esters and alcohol solvents, although there are improvements in environmental protection, there are still great hidden dangers in terms of flammability and explosiveness.

technical problem

The use of existing plastic water-based gravure inks has a specific specificity and can only be used on a certain variety. For example, an aliphatic modified polyvinyl alcohol as an ink prepared from an aqueous ink binder, an aromatic waterborne polyurethane modified polyvinyl alcohol as an ink prepared from an aqueous ink binder, an aqueous ink prepared by using polyvinyl alcohol alone as a binder, and a separate polyurethane as an ink The ink prepared by the binder, the ink prepared by using acrylic acid alone as a binder, and the ink prepared by using benzene, toluene and xylene as solvents, have low adhesion to pigments and other fine particles, and have a large amount of volatile substances. The printed product is water resistant, weather resistant, and has poor stability and is limited in application.

Technical solution

In order to solve the problem that the existing plastic water-based gravure ink can only be printed on a single product and the quality of the printed product is poor, the present invention proposes a plastic water-based gravure ink, which uses a thermosetting amino resin as a binder, and simultaneously modified The agent aliphatic aqueous polyurethane resin synergistically can be applied to a plurality of products, thereby changing the problem that the printed image is rough, the wrinkle appears, the overprinting is poor, and the application range is limited.

The technical solution of the present invention is implemented as follows:

A plastic water-based gravure ink consisting of the following components in terms of weight percentage: 25-35% amino resin, 3-8% aliphatic aqueous polyurethane resin, 30-40% solvent, 8-12% auxiliary, 8- 12% pigment, 8-12% diluent.

Further, the amino resin is one or more selected from the group consisting of a urea resin, a melamine formaldehyde resin, and a polyamide polyamine epichlorohydrin.

Further, the solvent is water, and the diluent is a mixture of deionized water and ethanol in a volume ratio of 8:2.

Further, the auxiliary agent is a mixture of a dispersing agent, a catalyst, a surfactant, an antifoaming agent, a preservative, and a leveling agent; the dispersing agent, a catalyst, a surfactant, an antifoaming agent, a preservative, and a leveling agent; The weight ratio of the agent is 2.5:2.5:1.5:1.5: 0.2: 1.8.

Further, the dispersing agent is diisopropanolamine or monoethanolamine; the antifoaming agent is SPA102 or SPA202; the catalyst is sorbitan trioleate, sorbitan monododecanoate or palm sorbitan The surfactant is OP-10 or Tween 60; the preservative is imidazolidinyl urea or dehydroacetic acid; and the leveling agent is ethylene glycol or propylene glycol.

Further, the pigment is selected from the group consisting of light fast yellow, permanent red, indigo blue, indigo green, permanent orange, light fast purple, carbon black, and titanium white powder.

Further, the plastic water-based gravure ink has a pH of 8.5 to 9.5.

Another object of the present invention is to provide a method for preparing a plastic aqueous gravure ink comprising the following specific steps:

1) Weigh 25-35% amino resin, 3-8% aliphatic water-based polyurethane resin, 30-40% solvent, 8-12% auxiliary agent, 8-12% pigment, 8-12% thinner according to the weight percentage The auxiliary agent is a mixture of a dispersant, a catalyst, a surfactant, an antifoaming agent, a preservative, and a leveling agent;

2) using the solvent weighed in step 1), dissolving the amino resin in a constant temperature water bath at 80 ° C - 100 ° C to prepare an aqueous solution of the amino resin;

3) Pour the prepared aqueous solution of the amino resin into the reaction vessel, sequentially add the aliphatic aqueous polyurethane resin, the catalyst and the surfactant, and react at a temperature of 20-25 ° C for 1.5-2.5 hours, and then add defoaming. And leveling agent, continue to stir for 10-20 minutes;

4) At a temperature of 20-25 ° C, add the pigment and continue to stir for 15-25 minutes, then add the diluent and preservative to stir for 5-10 minutes, the receipt is obtained.

Further, the dispersing agent is diisopropanolamine or monoethanolamine; the antifoaming agent is SPA102 or SPA202; the catalyst is sorbitan trioleate, sorbitan monododecanoate or palm sorbitan The surfactant is OP-10 or Tween 60; the preservative is imidazolidinyl urea or dehydroacetic acid; the leveling agent is ethylene glycol or propylene glycol; the dispersant, catalyst, surface active The weight ratio of the agent, antifoaming agent, preservative and leveling agent is 2.5:2.5:1.5:1.5: 0.2: 1.8.

Further, the step 1) the amino resin content is 30%, the aliphatic aqueous polyurethane resin content is 6%, the solvent content is 34%, the auxiliary content is 10%, the pigment content is 10%, and the diluent content is 10%; The step 2) reaction temperature is 95 ° C; the step 3) reaction temperature is 23 ° C, the reaction time is 2.2 hours, the stirring time is 15 minutes; the step 4) reaction temperature is 23 ° C, the dye mixing time is 13 minutes , stirring time is 8 minutes.

Beneficial effect

1. The binder of the invention is an amino resin, the amino resin is a few water-soluble low molecular resins, and the binder is used as a binder without solvent evaporation; the modifier is an aliphatic waterborne polyurethane resin for modifying the amino resin, and the water is used. The advantages of polyurethane improve the drying speed of amino resin, enhance adhesion, improve the high temperature-solid ratio of amino resin, and reduce drying time. Waterborne polyurethane itself is a kind of polymer material, which uses water as a medium, has the advantages of flame retardant, no pollution to the environment, and convenient processing.

2, the surfactant is OP-10 or Tween 60, mainly to increase the softness of plastic water-based gravure ink. The catalyst is sorbitan trioleate, sorbitan monosuccinate or palm sorbitan, which mainly increases the softness in the aqueous plastic gravure ink. The defoaming agent is used to suppress the foam generated when the ink is produced and the ink is reflowed at a high speed of the printing machine, thereby improving the stability of the ink. Preservatives are used to inhibit and kill microbes. In the process of ink printing, it is possible to use raw water in the field, and there are many microorganisms in raw water. The leveling agent is used to improve the printing of the ink onto the substrate to moisten the substrate, to improve the appearance of blooming, and the appearance of uneven color. The role of the diluent is to increase printing speed, dryness, color stability, and viscosity control during printing.

3. The water-resistance, acid-base resistance, solvent resistance and rubbing resistance of the plastic water-based gravure ink of the invention are obviously improved compared with other similar inks, and can be applied to high-quality printing. The plastic water-based gravure ink of the invention can be applied to a plurality of products, such as PE, PET, POPP and PVC products.

4. Most of the traditional water-based gravure inks have a pH below 8.0, and it is considered that the pH value is lower than 8.0, which is advantageous for increasing the printing speed. However, in the actual gravure printing process, the problem of blocking the printing plate often occurs. If only the pH of the aqueous gravure ink on the market is adjusted to 8.0 or higher, the problem of poor stability and poor gravure effect may occur. In order to solve this problem, we improved the binder by using amino resin and aliphatic waterborne polyurethane resin as raw materials, and adjusting the pH value to 8.5-9.5 by dispersing agent. It was surprisingly found that the water-based gravure ink not only did not appear. The problem of blocking the printing plate is very stable, that is, the three characteristics of ink transferability, wettability and resolubility. In the actual printing process, the production efficiency is high, the color is bright and the reduction is good.

Embodiments of the invention

Example 1

1) Weigh 25kg urea-formaldehyde resin, 3kg aliphatic water-based polyurethane resin, 40kg water, 8kg auxiliary, 12kg light fast yellow, 12kg thinner, auxiliary agent is 2kg diisopropanolamine, 2kg sorbitan trioleate, 1.2kg Tween 60, 1.2kg SPA102, 0.16kg imidazolidinyl urea and 1.44kg ethylene glycol a mixture; the diluent is a mixture of deionized water and ethanol in a volume ratio of 8:2;

2) using the water weighed in step 1), dissolving the urea-formaldehyde resin in a constant temperature water bath at 80 ° C to prepare an aqueous solution of urea-formaldehyde resin;

3) Pour the prepared aqueous solution of the urea-formaldehyde resin into the reaction vessel, and sequentially add the aliphatic aqueous polyurethane resin, the sorbitan trioleate and the Tween 60, and react at a temperature of 20 ° C for 2.5 hours, and then add SPA102 and ethylene glycol, stirring for another 10 minutes;

4) At a temperature of 25 ° C, add the light fast yellow and continue to stir for 25 minutes, then add the diluent and the imidazolidinyl urea for 5 minutes, and obtain the plastic water-based gravure ink.

Example 2

1) Weigh 30kg of melamine formaldehyde resin, 5kg of aliphatic water-based polyurethane resin, 35kg of water, 12kg auxiliary, 8kg indigo blue, 10kg thinner, the auxiliary agent is 3kg monoethanolamine, 3kg sorbitan monosuccinate, 1.8kg OP-10, 1.8kg SPA202, 0.24kg dehydroacetic acid and 2.16kg propylene glycol a mixture; the diluent is a mixture of deionized water and ethanol in a volume ratio of 8:2;

2) using the water weighed in step 1), Dissolving a melamine formaldehyde resin in an isothermal water bath at 90 ° C to prepare an aqueous solution of a melamine formaldehyde resin;

3) Pour the prepared aqueous solution of the melamine formaldehyde resin into the reaction vessel, and sequentially add the aliphatic aqueous polyurethane resin, sorbitan monosuccinate and OP-10, and react at a temperature of 25 ° C for 1.5 hours. Then add SPA202 and propylene glycol, and continue to stir for 20 minutes;

4) At a temperature of 20 ° C, add indigo blue and continue to stir for 25 minutes, then add the diluent and dehydroacetic acid for 10 minutes, and obtain the plastic water-based gravure ink.

Example 3

1) 35kg polyamide polyamine epichlorohydrin, 8kg aliphatic aqueous polyurethane resin, 30kg water, 10kg auxiliary, 9kg carbon black, 8kg diluent, the auxiliary agent is 2.5kg monoethanolamine, 2.5kg palm sorbitan, a mixture of 1.5 kg OP-10, 1.5 kg SPA 202, 0.2 kg dehydroacetic acid and 1.8 kg ethylene glycol; the diluent is a mixture of deionized water and ethanol in a volume ratio of 8:2;

2) using the water weighed in step 1), dissolving the aqueous solution of polyamide polyamine epichlorohydrin in a constant temperature water bath at 100 ° C;

3) Pour the prepared aqueous solution of the polyamide polyamine epichlorohydrin into the reaction vessel, and sequentially add the aliphatic aqueous polyurethane resin, palm sorbitan and OP-10, and react at a temperature of 22 ° C for 2 hours. Then add SPA202 and ethylene glycol, and continue to stir for 15 minutes;

4) At a temperature of 22 ° C, carbon black was added and stirring was continued for 20 minutes, and then a diluent and a dehydroacetic acid were added for stirring for 8 minutes, and a plastic water-based gravure ink was obtained.

Example 4

1) 30kg polyamide polyamine epichlorohydrin, 6kg aliphatic water-based polyurethane resin, 34kg water, 10kg auxiliary, 10kg permanent orange, 10kg diluent, the auxiliary agent is 2.5kg diisopropanolamine, 2.5kg a mixture of sorbitan trioleate, 1.5 kg Tween 60, 1.5 kg SPA 102, 0.2 kg imidazolidinyl urea and 1.8 kg propylene glycol; the diluent is a mixture of deionized water and ethanol in a volume ratio of 8:2;

2) using the water weighed in step 1), Dissolving polyamide polyamine epichlorohydrin in a constant temperature water bath at 95 ° C to prepare an aqueous solution of polyamide polyamine epichlorohydrin;

3) Pour the prepared aqueous solution of polyamide polyamine epichlorohydrin into the reaction vessel, and sequentially add aliphatic aqueous polyurethane resin, sorbitan trioleate and Tween 60 at a temperature of 23 ° C. The reaction was carried out for 2.2 hours, then SPA102 and propylene glycol were added, and stirring was continued for 15 minutes;

4) At a temperature of 23 ° C, the addition of Yonggu orange was continued for 13 minutes, and then the diluent and the imidazolidinyl urea were added for 8 minutes, and the plastic water-based gravure ink was obtained.

The plastic water-based gravure inks prepared in Examples 1-4 were subjected to the following experiments:

1. pH test results: The pH of Example 1 was 8.5, the pH of Example 2 was 9.0, the pH of Example 3 was 9.2, and the pH of Example 4 was 9.5.

2, viscosity test results: Example 1 Cai En 2 # cup 25 ° C 45 seconds, Example 2 Cai En 2 # cup 25 ° C 50 seconds, Example 3 Cai En 2# Cup 25 ° C for 50 seconds, Example 4 Caien 2 # cup 25 ° C for 60 seconds.

3. Water resistance test: 100 g of purified water was placed in a beaker, and 10×10 mm of ink printed with PVC substrate was taken at room temperature for 25 hours to dry in water for 24 hours at room temperature. Examples 1-4 were not fade.

4, alkali resistance: using a beaker to prepare 1% sodium hydroxide 100 g aqueous solution, in the environment of 25 ° C, take 10X10mm ink printed with POPP substrate finished at room temperature, dry for 24h, soak in sodium hydroxide solution For 2 hours, none of Examples 1-4 did not fade.

5. Acid resistance: 100 g of 1% hydrochloric acid aqueous solution was prepared in a beaker, and 10×10 mm of ink-printed PET substrate printed on the substrate was placed in an aqueous solution of hydrochloric acid at room temperature, and Examples 1-4 were used. Does not fade.

6. Solvent resistance: Take a 10×10 mm ink-printed PE substrate print at a room temperature of 25 ° C in a beaker, and dry at room temperature for 24 hours in a hexane for 2 hours. Example 1 -4 does not fade.

7. Stability: 6h freezing and heating test on water-based gravure ink to observe whether the ink has gelation or anti-coarse phenomenon. The results showed that none of Examples 1-4 had a gelation condition and an anti-coarse phenomenon.

The above is only the preferred embodiment of the present invention, and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc., which are included in the spirit and scope of the present invention, should be included in the present invention. Within the scope of protection.

Claims

A plastic water-based gravure ink characterized by being composed of the following components in a weight percentage: 25-35% amino resin, 3-8% aliphatic aqueous polyurethane resin, 30-40% solvent, 8-12% auxiliary Agent, 8-12% pigment, 8-12% diluent.
The plastic water-based gravure ink according to claim 1, wherein the amino resin is one or more selected from the group consisting of a urea resin, a melamine resin, and a polyamide polyamine epichlorohydrin.
The plastic water-based gravure ink according to claim 2, wherein the solvent is water, and the diluent is a mixture of deionized water and ethanol in a volume ratio of 8:2.
The plastic water-based gravure ink according to claim 2, wherein the auxiliary agent is a mixture of a dispersant, a catalyst, a surfactant, an antifoaming agent, a preservative, and a leveling agent; the dispersing agent, The weight ratio of catalyst, surfactant, antifoaming agent, preservative and leveling agent is 2.5:2.5:1.5:1.5: 0.2: 1.8.
The plastic water-based gravure ink according to claim 4, wherein the dispersing agent is diisopropanolamine or monoethanolamine; the antifoaming agent is SPA102 or SPA202; and the catalyst is sorbitan trioleate. An acid ester, sorbitan monosuccinate or palm sorbitan; the surfactant is OP-10 or Tween 60; the preservative is imidazolidinyl urea or dehydroacetic acid; the leveling agent is Ethylene glycol or propylene glycol.
The plastic water-based gravure ink according to any one of claims 1 to 5, wherein the plastic water-based gravure ink has a pH of 8.5 to 9.5.
The method for preparing a plastic water-based gravure ink according to claim 1, comprising the following specific steps:

1) Weigh 25-35% amino resin, 3-8% aliphatic water-based polyurethane resin, 30-40% solvent, 8-12% auxiliary agent, 8-12% pigment, 8-12% thinner according to the weight percentage The auxiliary agent is a mixture of a dispersant, a catalyst, a surfactant, an antifoaming agent, a preservative, and a leveling agent;

2) using the solvent weighed in step 1), Dissolving an amino resin in an isothermal water bath at 80 ° C - 100 ° C to prepare an aqueous solution of an amino resin;

3) Pour the prepared aqueous solution of the amino resin into the reaction vessel, sequentially add the aliphatic aqueous polyurethane resin, the catalyst and the surfactant, and react at a temperature of 20-25 ° C for 1.5-2.5 hours, and then add defoaming. And leveling agent, continue to stir for 10-20 minutes;

4) At a temperature of 20-25 ° C, add the pigment and continue to stir for 15-25 minutes, then add the diluent and preservative to stir for 5-10 minutes, the receipt is obtained.
The method for preparing a plastic water-based gravure ink according to claim 7, wherein the amino resin is one or more selected from the group consisting of urea formaldehyde resin, melamine formaldehyde resin and polyamide polyamine epichlorohydrin; The solvent was water and the diluent was a mixture of deionized water and ethanol in a volume ratio of 8:2.
The method for preparing a plastic water-based gravure ink according to claim 7, wherein the dispersing agent is diisopropanolamine or monoethanolamine; the antifoaming agent is SPA102 or SPA202; and the catalyst is sorbitol. An anhydride trioleate, sorbitan monosuccinate or palm sorbitan; the surfactant is OP-10 or Tween 60; the preservative is imidazolidinyl urea or dehydroacetic acid; the stream The flat agent is ethylene glycol or propylene glycol; the weight ratio of the dispersant, catalyst, surfactant, antifoaming agent, preservative and leveling agent is 2.5:2.5:1.5:1.5: 0.2: 1.8.
The method for preparing a plastic water-based gravure ink according to claim 7, wherein the step 1) the amino resin content is 30%, the aliphatic water-based polyurethane resin content is 6%, and the solvent content is 34%. The content is 10%, the pigment content is 10% and the diluent content is 10%; the step 2) the reaction temperature is 95 ° C; the step 3) the reaction temperature is 23 ° C, the reaction time is 2.2 hours, and the stirring time is 15 minutes; The reaction temperature of the step 4) was 23 ° C, the dye mixing time was 13 minutes, and the stirring time was 8 minutes.