CN107400411B

CN107400411B - High-speed printing water-based gravure ink for non-absorbent substrate

Info

Publication number: CN107400411B
Application number: CN201710653356.9A
Authority: CN
Inventors: 杨换丽; 侯琛; 冯文照; 麦允程
Original assignee: Yips Ink Zhongshan Co ltd
Current assignee: Yips Ink Zhongshan Co ltd
Priority date: 2017-08-02
Filing date: 2017-08-02
Publication date: 2020-08-21
Anticipated expiration: 2037-08-02
Also published as: CN107400411A

Abstract

The invention provides a high-speed printing water-based gravure ink for a non-absorbent substrate, which comprises the following components A and B in parts by weight, wherein the component A comprises the following components: 2-8 parts of water-based acrylic resin, 0.1-0.5 part of pH regulator, 0.1-0.5 part of kaolin, 35-45 parts of rutile titanium dioxide, 2-6 parts of ethanol and 5-15 parts of water; wherein the B component comprises: 20-40 parts of waterborne polyurethane resin, 0.1-0.5 part of rheological additive, 0.1-0.5 part of defoaming agent, 1-4 parts of ethanol and 5-10 parts of water. The invention solves the problem of high-speed printing of the water-based ink for non-absorbent substrates, realizes high-speed printing at a printing speed of 250m/min or more on the premise of not modifying equipment, improves the production efficiency, belongs to green printing, has low energy consumption and is more environment-friendly. The ink disclosed by the invention is simple in formula, convenient and fast to operate, low in production cost and suitable for large-scale production and application.

Description

High-speed printing water-based gravure ink for non-absorbent substrate

Technical Field

The invention relates to the technical field of ink, in particular to high-speed printing water-based gravure ink for non-absorbent substrates.

Background

The water-based ink is more and more concerned by people as a novel low-volatility, green, economical and environment-friendly ink. The research of domestic waterborne polyurethane starts in the 70 th 20 th century, and the development is slow, especially in recent years, due to the requirements of environmental protection and food and drug packaging safety, higher requirements are put on printing ink and adhesive for plastic flexible packaging, and the change is gradually towards solvent-free type, and the waterborne polyurethane ink is a hot point of research for meeting the requirements and the change.

However, most of the so-called 'water-based ink' in the domestic market is water-based ink, most of the so-called 'water-based ink' is applied to printing paper concave absorbent substrates, and the printing speed is far from the requirement of high-speed printing; the successful implementation of high-speed printing of water-based ink on non-absorbent substrates has not been seen at present. Therefore, the implementation of high-speed printing water-based gravure ink becomes a necessary way for solving the current water-based ink.

In the prior art, the printing volatilization drying of the printing water-based gravure ink for non-absorbent substrates is mainly based on the volatilization of water, so the comprehensive printing application evaluation needs to be specifically evaluated according to the oven and exhaust states of an actual printing machine, and the printability of a high-shrinkage film needs to be particularly concerned in the printing process.

The prior ink of the system has the following problems: 1. the requirement of the system ink on the drying oven and the air exhaust of a printing machine table is slightly higher. The printing water-based gravure ink body for the non-absorbent substrate contains about 35% of water, and in addition, the addition of water in a diluted solvent in the printing process, the drying speed of the ink in a printing machine completely depends on the volatilization speed of the water, but the natural volatilization speed of the water is far slower than that of an organic solvent, so that the ideal printing effect can be achieved by adjusting the temperature of an oven of the printing machine to be 10-15 ℃; in addition, a large number of printing tests show that the ventilation of the printing machine is properly increased, and volatile water in the printing ink can be effectively taken away from the machine table, so that the printing ink is ensured to be thoroughly dried and formed into a film. Therefore, in this respect, it is necessary to increase the oven temperature and the ventilation rate appropriately to match the printing with the aqueous ink to achieve a desired printing effect. 2. Evaluation of printability of the ink of this system to print a high shrink film. The aqueous gravure ink printing process for non-absorbent substrates requires a moderate increase in oven temperature depending on the on-site press conditions and printing speed requirements, but some highly shrinkable films (e.g., PVDC) may stretch above 40 ℃, resulting in misregistration; BOPP films also stretch at temperatures greater than 85 ℃ resulting in overprint misalignment. Therefore, in the field printing process of the system ink, the field oven temperature of the film which is easy to stretch at high temperature is set according to the printing film, so that the overprint deviation caused by the stretching of the film is avoided. Therefore, it is difficult to achieve both of the printing quality and the printing speed.

Disclosure of Invention

The development of high-speed printing water-based gravure ink for non-absorbent substrates aims to solve the problem of high-speed printing of the current water-based ink on the non-absorbent substrates. At present, most of water-based ink in the market is water-based ink, is not real water-based ink, is mostly used for printing application of paper concave substrates of absorbent substrates, and cannot achieve high-speed printing application. The method solves the problem of high-speed printing of the water-based ink on a non-absorbent substrate, reduces the application of an organic solvent in the ink, and promotes the printing industry to advance to green environmental protection; and secondly, the implementation of the water-based ink fundamentally ensures the safety of food packaging.

Aiming at the problems in the prior art, the invention provides a high-speed printing water-based gravure ink for non-absorbent substrates.

A high-speed printing water-based gravure ink for non-absorbent substrates comprises the following components A and B in parts by weight,

wherein the A component comprises:

wherein the B component comprises:

preferably, wherein the a component comprises: 5 parts of water-based acrylic resin, 0.3 part of pH regulator, 0.3 part of kaolin, 40 parts of rutile titanium dioxide, 4 parts of ethanol and 10 parts of water; wherein the B component comprises: 30 parts of waterborne polyurethane resin, 0.2 part of rheological additive, 0.2 part of defoaming agent, 2 parts of ethanol and 8 parts of water.

Wherein the water-based acrylic resin is anionic water-based acrylic resin.

The aqueous acrylic resin and the aqueous polyurethane resin are liquid or emulsion.

Further, a monomer of the water-based acrylic resin is prepared by selecting methacrylic acid and maleic anhydride and carrying out neutralization reaction with organic amine, reacting 30-50 parts of methacrylic acid and/or maleic anhydride with 1-5 parts of initiator azodiisobutyl ester at 60-80 ℃ for 3-5 hours, adding 5-10 parts of one or more of dimethylethanolamine, diethanolamine and glycol amine, stirring for 5-8 hours under heat preservation, and then neutralizing with one or more of N, N-dimethylethanolamine, ethylenediamine, diethylamine and triethylamine; further preferably, the organic amine is one or more of monoethylamine, diethylamine, triethylamine, diisopropylethylamine and diethylenetriamine. The water-based acrylic resin has good compatibility and printability, good wetting dispersibility, low odor residue, good hydrophilicity and good alcohol solubility, and can be mixed and dissolved with an alcohol solution with the content of 10-100%.

Further, 5-10 parts of a redissolving hydrophilic auxiliary agent is added in the process of the neutralization reaction. The redissolved hydrophilic auxiliary agent is one or more of propylene glycol and ether thereof, n-butyl alcohol and isopropanol.

Further, the aqueous polyurethane resin is prepared by reacting diisocyanate, polyol and a hydrophilic chain extender under the catalysis to obtain a prepolymer with self-emulsifying property, wherein the reaction temperature is preferably 65-95 ℃, and the reaction time is 1-4 hours. The reaction can be carried out in the presence or absence of a solvent, and the solvent is preferably acetone, ethyl acetate or dimethylformamide. The molecular weight of the prepolymer obtained is preferably 5000-. The polyol is polyester polyol and/or polyether polyol; the polyester polyol can be obtained by carrying out dehydration polymerization reaction on dibasic acid and dihydric alcohol, wherein the dibasic acid is one or more of ethanediol, malonic acid, succinic acid, maleic acid and fumaric acid, and the dihydric alcohol is one or more of ethanediol, propanediol, butanediol, neopentyl glycol, isoprene glycol and 2, 3-dimethyl-1, 3-butanediol. The water-based polyurethane resin can generate a crosslinking reaction with active groups participating in the reaction, and the crosslinking reaction is generated during the film forming process, so that the crosslinking density is increased. In addition, the water-soluble polyvinyl alcohol has good miscibility with water and alcohol.

The diisocyanate may be 1, 6-hexamethylene diisocyanate, 2, 4-trimethylhexamethylene diisocyanate, 2, 6-diisocyanatohexanoic acid, methylcyclohexyl diisocyanate, 4' -diphenylmethane diisocyanate or toluene diisocyanate.

The waterborne polyurethane resin meets the following index requirements:

in addition, the waterborne polyurethane resin has the characteristics of good film forming property, composite strength, universality, high solid content and the like, and endows the system with excellent printability, plate re-solubility and ink post-processing application performance. And the water-based ink has good water solubility and strong water resistance after drying, and solves the problem of systematic contradiction of the ink in the industry all the time.

Further, the hydrophilic chain extender is a tertiary amine compound, a compound containing carboxyl or a diamine compound containing polyoxyethylene ether chain segments. The tertiary amine compound is preferably N-methyldiethanolamine or N-methyldiethyltriamine. The compound containing carboxyl is preferably polycaprolactone diol containing carboxyl obtained by reacting diaminocaproic acid, dithioalanine, 3, 5-diaminocarbonic acid, 2, 6-dihydroxy benzoic acid, 2-dihydroxy propionic acid or 2, 2-dihydroxy propionic acid with caprolactone.

Further, the pH regulator is an alcamines organic matter. The pH regulator can effectively regulate the pH value of a system, endows the system with good pH stability, has no adverse reaction with resin, has an auxiliary dissolving effect on the contrary, and can endow the ink with excellent water dilutability and good printing adaptability.

Further, the alcohol amine organic matter is one or more of monoethanolamine, diethanolamine, triethanolamine, dimethylethanolamine, ethylene glycol amine and propylene glycol amine.

Further, the rheological additive is polyether polyol and/or polyether polyurethane. The rheological additive has high-efficiency rheological efficiency, is effectively combined with ink main body resin and the like to generate ideal rheological property, sag resistance and sedimentation resistance, can be added at any stage of the production process, is not influenced by the pH value of an ink system, and cannot generate any adverse effect.

The polyether polyol is preferably one or a mixture of more than two of polyethylene glycol, polypropylene glycol and polytetramethylene glycol. The polyether polyol can be prepared by the addition reaction of low-molecular-weight dihydric alcohol and cycloalkane, and can also be prepared by ring-opening polymerization of cycloalkane. The polyether polyurethane may be prepared by reacting polyethylene glycol, polyoxypropylene diol, polyoxypropylene triol and isocyanate.

Further, the defoaming agent is modified polyol and/or high molecular weight alcohol substances. More preferably, the modified polyol is prepared by stirring and dispersing 50 parts of alkynediol, 40 parts of alcohol-water mixture and 10 parts of organic amine compound at the temperature of 50-80 ℃ for 10-30 minutes; the alkynediol is one or more of 1, 4-butynediol, 2, 5-dimethyl-3-hexynediol, 2-methyl-3-butynediol and dimethyl hexynediol; the proportion of alcohol in the alcohol-water mixture is 40-70%, wherein the alcohol is one or more of ethanol, isopropanol and isobutanol; the organic amine compound is one or more of monoethanolamine, diethanolamine, triethanolamine, dimethylethanolamine, glycol amine and glycol amine; the high molecular weight alcohol substance is one or more of tridecanol, tetradecanol, pentadecanol and hexadecanol.

The defoaming agent has good compatibility with other materials of the system, can provide a long-term defoaming effect, and does not cause poor printing problems such as fish eyes, pinholes and the like.

The invention innovates a solvent system, adopts environment-friendly water and a small amount of alcohol solvent as diluting solvents, and leads the environment of a printing workshop to be more environment-friendly.

Fineness: mixing the raw materials of the component A, putting the mixture into a plastic tank, adding a proper amount of glass beads (the mass of the glass beads is 70 percent of the mass of the raw materials), sealing, placing the mixture into a red devil rocking machine for sanding for 2 hours, and sampling and detecting the fineness of the mixture after sanding, wherein the standard is less than or equal to 20 mu m. And mixing the raw materials of the component B, placing the mixture in a devil's-red ghost swinging machine, swinging and dispersing for 10 minutes, sampling and rechecking the fineness, and filtering by adopting a 150-mesh filter screen after the fineness reaches the standard.

The ink testing items and methods are as follows:

production process parameters

Production facility and detection tool:

(1) production equipment: a blade type dispersion machine (highest speed: 1200 r/min), a cylinder type sand mill (discharge capacity 50L), a 1 ton capacity storage tank, a filter press packaging machine, a 150-mesh filter screen and a 15-micron filter bag.

(2) A detection tool: gas phase color/mass spectrometer, fineness plate, corona pen, viscosity cup, color difference instrument, KPP proof press, proportion cup, thermometer, pH meter, NanoZS90 potential particle size analyzer, Kinexus high-grade rotational rheometer, and high-temperature sterilization pot.

The production process flow comprises the following steps:

stock preparation → high-speed pre-dispersion → pigment grinding → late-stage adjustment → quality detection (QC) → assay (environmental protection) → filtration packaging.

The aqueous acrylic resin, the pH regulator, the kaolin, the ethanol and the water are added while dispersing by using a dispersing machine (at a low speed of 300 revolutions per minute), and after the addition, the speed of the dispersing machine is increased to 800 revolutions per minute for 5 minutes. Regulating the rotating speed of the dispersing agent to 500 revolutions per minute, adding rutile titanium dioxide, accelerating the speed of a dispersion machine to 1000 revolutions per minute, dispersing at a high speed for 30 minutes, then grinding, and entering a sanding section.

Controlling a sand grinding process: the temperature of the sand mill is 45-55 ℃, the flow rate is 600kg/h, and the fineness is less than or equal to 20 mu m; 3 machine-coupled grinding/1 pass mode is adopted. And after the sanding working section is finished, the sanding equipment and the dispersing equipment are cleaned by water and ethanol.

After sanding, starting a dispersion machine (300 revolutions per minute), sequentially adding the waterborne polyurethane resin, the rheological additive, the defoaming agent, the ethanol and the water, and after finishing, increasing the speed of the dispersing agent to 1000 revolutions per minute and dispersing at a high speed for 15 minutes.

The process notes are as follows:

firstly, the temperature has great influence on the color and the transparency, and the grinding temperature must be controlled within a standard range.

Secondly, the flow adjustment exceeds the standard, and the grinding temperature change and the grinding efficiency are caused.

Thirdly, because the specific gravity of the titanium dioxide is large, the titanium dioxide needs to be dispersed and put into the reactor at the same time; if stop the dispenser and drop into titanium white powder, titanium white powder easily deposits the dispersion inhomogeneous, and causes stifled sanding equipment and causes the shut down problem.

QC quality detection project:

routine detection: hue, viscosity, fineness, (BOPP, PET, NY) adhesion, surface tension, initial drying, pH value, water resistance, rheological property, electric potential, composite strength, and cooking property.

Testing and detecting: a-type heavy metal environmental protection index, plasticizer index and halogen-free index.

And thirdly, testing indexes qualified through QC, and filtering (filter pressing) and packaging.

The printing parameters and performance indexes of the high-speed printing water-based gravure ink for the non-absorbent substrate are as follows:

the printing speed is up to 250m/min and above.

② ink printing dilution ratio 1: 1.1 (ethanol: water: 7:3-0:10), 13 sec/TOYO 3^#。

And the ink has good solvent release, low solvent residue, strong ink covering power, good leveling property, good shallow net transfer property, clear image and text and strong printing adaptability.

And fourthly, the ink has good printability to substrates such as PET, BOPP, NY and the like, and is a universal composite ink.

Adopting a solvent-free (280 plus 300 m/min; glue amount of 1.3-1.6g) and water glue (150 m/min; glue amount of 1.5-2.0g) composite process without white spots and foaming phenomena.

From workshop production to actual printing application, the series of printing inks can well meet the application requirements of various composite structures of PET, BOPP and NY substrates, and meet the requirements of mass production application.

The high-speed printing water-based gravure ink for the non-absorbent substrate is proved to have good printing adaptability on the non-absorbent substrate through deep study and comparison tests, and the printing speed can reach 250m/min or even higher; as an ink product, the system completely uses water to dilute, dissolve and print, has the characteristic of excellent scraping performance, and completely meets the post-processing application performance of customers; the system appears in a new product form, gradually replaces the whole food packaging ink in a transition mode, promotes transformation and upgrade of the printing and packaging industry, and fundamentally ensures the food packaging safety.

The invention solves the following technical problems:

1. high speed printing on non-absorbent substrates

The technical indexes and the application characteristics of the resin are set completely according to the field application requirements by independently developing and designing the water-based polyurethane resin of the system, the application space of the water-based ink is expanded, the high-speed printing of the water-based ink on a non-absorbent substrate is realized, and the printing effect is superior to that of the traditional solvent-based ink.

2. Excellent performance of extremely low odor

The method is applied to the food packaging industry, and the low-odor residue of printing ink printing is also an important index requirement. The aqueous ink system has only water and alcohol as solvents, so the odor of the dried prints is lower than that of traditional solvent-based inks. Extensive customer application experience shows that customers have great acceptance of the odor of current water-based inks.

3. Excellent shallow web transition characteristics and print relief

In consideration of the defects that the traditional solvent type ink is easy to dry and excessively print in a shallow net mode, the water-based ink is endowed with special dynamic surface tension embodiment through special treatment on resin when the formula characteristics are set, the defects that the traditional solvent type ink is excessively in a shallow net mode are overcome, the outstanding characteristics of excessively in the shallow net mode are shown, in the same comparison of printing samples, the printing effect of the water-based ink is far better than that of the traditional solvent type ink, and the stereoscopic impression of a printed product is obviously better than that of the traditional solvent type ink.

The invention has the beneficial effects that:

(1) the invention solves the problem of high-speed printing of the water-based ink for non-absorbent substrates, and the printing speed can reach 250m/min or more on the premise of not modifying equipment, thereby realizing high-speed printing and improving the production efficiency;

(2) the ink disclosed by the invention can be completely suitable for traditional printing equipment, mechanical equipment is not required to be modified, and the ink can be directly butted with the traditional solvent-based ink equipment;

(3) the invention reduces the use of organic solvent, realizes green printing, has low energy consumption and is more environment-friendly;

(4) the ink disclosed by the invention has wide applicability and completely meets the subsequent processing requirements of BOPP, NY, PET and PVDC printing machines;

(5) the printing ink does not contain volatile harmful substances in the production and application processes, and is beneficial to protecting the health of human bodies;

(6) the ink disclosed by the invention is safe and environment-friendly, and provides a powerful guarantee for food packaging safety;

(7) compared with the existing solvent-based ink product, the ink provided by the invention has the advantages that the printing applicability is enhanced, the printing efficiency is high, and the printing fault is not easy to generate;

(8) the ink has enhanced surface characteristics, and is suitable for green compounding processes (solvent-free compounding and water-gel compounding);

(9) the ink has high composite strength, and is suitable for conventional (non-steamed and non-boiled) BOPP, (steamed) PET and NY food composite packaging;

(10) the residual amount of the solvent after the ink is compounded is very low, and the ink conforms to the national standard GB/T10004-2008 environmental protection regulation;

(11) the ink disclosed by the invention is strong in formula simplification, convenient to operate, low in production cost and suitable for large-scale production and application.

Detailed Description

For better explanation of the present invention, the following specific examples are further illustrated, but the present invention is not limited to the specific examples.

Example 1

wherein the A component comprises:

wherein the B component comprises:

example 2

wherein the A component comprises:

wherein the B component comprises:

example 3

wherein the A component comprises:

wherein the B component comprises:

through actual production inspection, the examples 1-3 can successfully realize high-speed printing on non-absorbent substrates, the printing speed is up to more than 250m/min, downstream customers do not need to change printing equipment, the thorough drying of the ink layer is ensured while high-speed printing is carried out, no adverse effect is caused on subsequent composite application, the special application requirements of high-temperature cooking and water cooking of the customers are met, the problem of high-speed printing of the conventional water-based ink on the non-absorbent substrates is fundamentally solved, no printing defect exists, the color layering sense and the three-dimensional sense are superior to those of the conventional solvent-based ink, and the quality detection of the ink meets various index requirements.

The above description is only exemplary of the present invention and is not intended to limit the scope of the present invention, which is defined by the claims appended hereto, as well as the appended claims.

Claims

1. A high-speed printing water-based gravure ink for non-absorbent substrates is characterized by comprising the following components A and B in parts by weight,

wherein the A component comprises:

wherein the B component comprises:

wherein the aqueous acrylic resin is an anionic aqueous acrylic resin;

the waterborne polyurethane resin is prepared by reacting diisocyanate, polyol and a hydrophilic chain extender, wherein the polyol is polyester polyol and/or polyether polyol; the polyester polyol is obtained by dehydrating and polymerizing dibasic acid and dihydric alcohol, wherein the dibasic acid is one or more of ethanediol, malonic acid, succinic acid, maleic acid and fumaric acid, and the dihydric alcohol is one or more of ethanediol, propanediol, butanediol, neopentyl glycol, isoprene glycol and 2, 3-dimethyl-1, 3-butanediol; the hydrophilic chain extender is a tertiary amine compound, a compound containing carboxyl or a diamine compound containing polyoxyethylene ether chain segments.

2. The high-speed printing water-based gravure ink for non-absorbent substrates as claimed in claim 1, wherein the monomers of the water-based acrylic resin are methacrylic acid and maleic anhydride, and are prepared by neutralization reaction with organic amine, wherein the organic amine is one or more of monoethylamine, diethylamine, triethylamine, diisopropylethylamine, and diethylenetriamine.

3. High speed printing water based intaglio ink for non-absorbent substrates according to claim 2 characterized by the fact that a redissolving hydrophilic adjuvant is added during said neutralization reaction.

4. The high-speed printing water-based intaglio ink for non-absorbent substrates according to claim 1 characterized in that said pH adjusting agent is an organic substance of the alcamines type.

5. The high-speed printing water-based gravure ink for non-absorbent substrates according to claim 4, wherein said alcohol amine organic substance is one or more of monoethanolamine, diethanolamine, triethanolamine, dimethylethanolamine, ethyleneglycol amine, propyleneglycolamine.

6. High speed printing water based intaglio ink for non-absorbent substrates according to claim 1 characterized in that said rheological aid is a polyether polyol and/or polyether polyurethane.

7. The high-speed printing water-based gravure ink for non-absorbent substrates as claimed in claim 1, wherein said antifoaming agent is a high molecular weight alcohol and/or a modified polyol.

8. The high-speed printing water-based intaglio ink for non-absorbent substrates according to claim 7 characterized in that said high molecular weight alcohols are one or more of tridecanol, tetradecanol, pentadecanol, hexadecanol; the modified polyol is prepared by stirring and dispersing 50 parts of alkynediol, 40 parts of an alcohol-water mixture and 10 parts of an organic amine compound at the temperature of 50-80 ℃ for 10-30 minutes; the alkynediol is one or more of 1, 4-butynediol, 2, 5-dimethyl-3-hexynediol and 2-methyl-3-butynediol; the proportion of the alcohol in the alcohol-water mixture is 40-70%, and the alcohol in the alcohol-water mixture is one or more of ethanol, isopropanol and isobutanol; the organic amine compound is one or more of monoethanolamine, diethanolamine, triethanolamine, dimethylethanolamine, glycol amine and glycol amine.