WO2003044101A1

WO2003044101A1 - Non-water-rub-offset gravure printing ink composition

Info

Publication number: WO2003044101A1
Application number: PCT/CN2002/000832
Authority: WO
Inventors: Peng Fan; Wei Zhang; Chunhua Zhou
Original assignee: Fan, Guanbao
Priority date: 2001-11-21
Filing date: 2002-11-21
Publication date: 2003-05-30
Also published as: AU2002349741A1

Abstract

The invention provides a non-water-rub-offset gravure printing ink composition having good printability. Polymeric binders and adjuncts used in this composition are also provided, including modified phenolic resin binders, oil soluble phenolic resin binders, water soluble modified alkyd resin binders, modified alkyd resin binders unsaturated polyester resin binders, polyurethane resin binders, rosins and derivatives thereof, polyol ester resin binders, epoxy resin binders, mixed waxs, high boiling point solvents, etc. The ink composition of the invention features by the stability of performance on the gravure printer, good printability, the ability of effectively reducing the contents of sodium hydroxide and alizarin oil in water-rub liquid, tolerant requirements on printing conditions, low environmental hazards, etc.

Description

Water-erasable engraving gravure printing ink composition Technical field

The present invention relates to the field of printing inks, and in particular, to a gravure printing ink composition that is engraved with water and does not smudge.

Background technique

Engraving gravure printing ink composition is mainly used for trademark printing of bank currency, securities, various certificates and famous products. Previously, pigments (organic and inorganic pigments), polymer binders (vegetable oil modified alkyd resin binders, polyurethane resin binders, rosin and Its derivative polyol ester resin adhesive, rosin modified phenolic resin adhesive, oil-soluble pure phenolic resin adhesive, epoxy resin adhesive, mixture, etc.), auxiliary (anionic surfactant, non-ionic Surfactants, waxes, desiccants, solvents, etc.). When adjusting the viscosity of the engraving gravure printing ink composition that is not stained with water, or in the composition of the above-mentioned polymer binder and adjuvant, or in the process of preparing these polymer binders and adjuvants , Using # 200 solvent oil and / or 210 mineral oil and / or aromatic-free mineral oil (boiling range 170 ~ 190Ό) and / or diethylene glycol monoethyl ether and / or diethylene glycol monomethyl ether and other low boiling points Or a solvent with a narrow boiling range. After these polymer binders and auxiliaries are used in water-gravity engraving gravure printing ink compositions, these solvents have a lower boiling point or a narrower boiling range. When the ink composition is printed, the ink composition increases. It is sticky, not easy to clean, and easy to produce printing ink, such as flying ink and dirty printing. In addition, water rubbing does not stain the engraving gravure printing ink composition, which requires relatively high printing conditions, such as ink fountain temperature, printing plate temperature, color film roller temperature, color collecting roller temperature, and erasing liquid temperature. The range is narrow. Therefore, it causes a lot of inconvenience to printing. At the same time, due to the volatilization of the solvent, a certain degree of pollution is brought to the environment during or after printing.

Prior to the present invention, a rosin-modified diphenol-based propane-methyl casein resin was used as a modified phenolic casein resin used as an intaglio engraving gravure printing ink composition which was not stained with water. In vegetable oils, mixed into polymer binders. However, during the preparation process, the resin was opaque after dissolving in vegetable oil at low temperature. Only when the temperature is gradually increased above 220 ° C will it become transparent. This fully shows that these modified phenolic resins have poor oil solubility. Thanks to these modified phenolics Poor oil solubility of the resin results in poor storage stability of the polymer binder and poor storage stability of the ink composition. In the printing process, the ink composition has poor transferability, the solvent is volatile, the plate-wiping effect is not ideal (easy to hang on the printing plate), flying ink is easy to occur, and the printability is poor.

Prior to the present invention, rosin-modified phenolic resin and rosin-modified phenolic resin adhesive, vegetable oil-modified alkyd resin adhesive, polyurethane resin adhesive, Resin and polymer adhesives, such as epoxy resin adhesives, incense and its derivative polyol ester resins, and rosin and its derivative polyol ester resin adhesives, do not contain ether groups in their molecular structure, or The number of ether groups is negligible. In order to reduce environmental pollution, reduce the content of sodium hydroxide and Taikoo oil in the water wiping solution, and meet the requirements of the water-wiping non-staining engraving gravure printing, the present inventors conducted intensive research, and as a result, completed the present invention.

Summary of the Invention

The purpose of the present invention is to provide a water-wiping non-staining engraving gravure printing ink composition having good printability. Another object of the present invention is to reduce the content of sodium hydroxide and Taikoo oil in a water-wiping liquid, reduce environmental pollution, and Printing provides more relaxed printing conditions.

The water-erasable sculpted gravure printing ink composition of the present invention is composed of) pigment, (B) polymer binder, (C) auxiliary agent, etc., wherein (A) pigment accounts for the total composition of the composition 5-55%, (B) polymer binder accounts for 10-60% of the total composition of the composition, and (C) adjuvant accounts for 5-40% of the total composition of the composition.

The water-erasable engraving gravure printing ink composition of the present invention is in the composition or preparation process of the composition, or in the composition or preparation process of the polymer binder and auxiliary agent for the composition Adding vegetable oil and / or varnish and / or high boiling point solvent to adjust the viscosity of the composition, or adjusting the viscosity of the polymer binder for the composition, or adjusting the viscosity or state of the auxiliary agent for the composition.

The water-erasable engraving gravure printing ink composition of the present invention, wherein in the preparation process of the polymer binder for the composition, process control and / or chemical reaction is used to make the composition use the polymer binder After the viscosity reaches a certain level, set aside.

The polymer binder used in the water-erasable non-staining engraving gravure printing ink composition is selected from the group consisting of high acid value modified phenolic resin adhesive, oil-soluble pure phenolic resin adhesive, and modified alkyd resin adhesive. Mixture, water-soluble modified alkyd resin adhesive, polyurethane resin adhesive, unsaturated And one or more of polyester resin adhesive, epoxy resin adhesive, high acid value rosin and its derivative polyol ester resin adhesive; or solid resin, vegetable oil, varnish, Two or more of water-soluble polymer binders, polymer binders, surfactants, solvents, other additives for engraving gravure printing ink compositions, etc., which are not rubbed with water, can be arranged in any ratio and in any order A combination of polymer binder mixtures obtained by kneading or mixing.

The water-erasable sculpted gravure printing ink composition of the present invention, wherein the high-acid-value modified phenolic resin in the high-acid-value modified phenol resin binder is composed of (A) phenol, (B) aldehyde, (C) Condensation catalyst, (D) modifier, (E) polyol, (F) neutralizer (neutralizer is limited to the preparation of water-soluble modified phenol, fat and / or water-soluble modified phenol resin) when using agents) and the like, wherein (a) and hope (B) an aldehyde condensate accounts for ^1-70 percent of the total resin composition, preferably ^{^{5 - 6 5%, (C}} ) condensing agent accounted ^ ft) phenol 0.1-3.5% by weight, preferably 0.2-3%. (D) modifier accounts for 1-95%, preferably 2-75% of the total composition of the resin, (E) polyol accounts for 0-40%, preferably 0-35%, of the total composition of the resin; (F) neutralization The agent accounts for 0-40% of the total composition of the resin, preferably 0-35%. The molar ratio of (A) a phenol and (B) an aldehyde of 1: ^0.6 - In the range of ^2.5.

The water-erasable sculpted gravure printing ink composition of the present invention, wherein the oil-soluble pure phenol resin in the oil-soluble pure phenol resin binder is composed of (A) phenol, (B) aldehyde, and (C) condensation Catalyst and other components, wherein the molar ratio of (A) phenol to (B) aldehyde is 1: 1.5-4, preferably 1: 1.5-3; (C) the condensation catalyst accounts for 0.1-2% by weight of (A) phenol, preferably 0.2 -1.5%.

The water-erasable sculpted gravure printing ink composition of the present invention, wherein the water-soluble modified alkyd resin binder is composed of (A) modifier, (B) polyol, (C) transesterification catalyst Or esterification catalyst, (D) organic acid, (E) esterification catalyst, (F) sulfonating agent, (G) neutralizing agent, etc., where) the modifier accounts for 1 to ^{9 of the} total composition of the adhesive 0%, preferably ² 0- ^85%, (B) a polyhydric alcohol accounts for 1-49% of the total binder composition, preferably 2-40%, (C) an esterification catalyst or transesterification catalyst accounting for the total binder The composition is from 0 to 1%, preferably from 0 to 0.8%, (D) the organic acid accounts for 1-50%, preferably 2-45% of the total composition of the adhesive, and (E) the esterification catalyst accounts for the total composition of the adhesive 0-1%, preferably 0-0.8%, (F) the sulfonating agent is excessive, and (G) the neutralizing agent is an appropriate amount.

The water-erasable non-staining engraving gravure printing ink composition of the present invention, wherein the modified alkyd resin binder is composed of (A) a modifier, (B) a polyol, (C) a transesterification catalyst or an ester (D) organic acid, (E) esterification catalyst, etc., where (A) modifier accounts for the viscosity 1-90% of the total composition of the mixture, preferably 20-85%, (B) the polyol constitutes the total composition of the adhesive

1-49%, preferably 2-40%, (C) transesterification catalyst or esterification catalyst accounts for 0-1% of the total composition of the adhesive, preferably 0-0.8%, (D) organic acid accounts for the adhesive 1-50% of the total composition, preferably

2 to 40%, (E) The esterification catalyst accounts for Q-1% of the total composition of the binder, preferably 0-0.8%.

The water-erasable engraving gravure printing ink composition of the present invention, wherein the polyurethane resin binder is composed of (A) polyol, (B) organic acid, (C) catalyst, (D) organic isocyanate, ( E) composition such as capping agent, wherein (A) polyhydric alcohol accounts for 1-50% of the total composition of the adhesive, preferably 2-45%, (B) organic acid accounts for 1-90% of the total composition of the adhesive Preferably, 10-80%, (C) the catalyst accounts for 0-1% of the total composition of the adhesive, preferably 0-0.8%, (D) organic isocyanate accounts for 1-50% of the total composition of the adhesive, preferably 1 -45%, (E) the end-capping group accounts for the total composition of the adhesive

0-15%.

The water-erasable sculpted gravure printing ink composition of the present invention, wherein the polyurethane resin binder is composed of (A) vegetable oil or vegetable oleic acid, (B) polyol, (C) transesterification catalyst or esterification catalyst , (D) organic isocyanate, (E) organic acid, (F) catalyst, (G) blocking agent, etc., where (A) vegetable oil or vegetable oleic acid accounts for 1-90% of the total composition of the adhesive, (B ) Polyol accounts for 1-49% of the total composition of the adhesive, (C) transesterification catalyst or esterification catalyst accounts for 0-1% of the total composition of the adhesive, (D) Organic isocyanate accounts for the total amount of the adhesive consist of

1-50%, (E) organic acid accounts for 1-50% of the total composition of the adhesive, (F) catalyst accounts for 0-1% of the total composition of the adhesive, (G) end-capping agent accounts for the bonding The total composition of the agent is 0-15%.

The water-erasable non-staining engraving gravure printing ink composition of the present invention, wherein the unsaturated polyester resin binder is composed of) a polyol, (B) an organic acid, (C) a catalyst, and (D) an antioxidant. etc., wherein (a) a polyol representing ²⁵ _ ^80% of the total composition of the adhesive, preferably ^{^{25 - 7 4%, (B}} ) an organic binder accounts for 20-75% of the total composition, preferably 26 -7 ^5%, (C) of the catalyst of 0-2.5% of the total binder composition, preferably 0-1%, (D) an antioxidant accounts for 0-2.5% of the total binder composition, preferably 0_1% .

The water-erasable engraving gravure printing ink composition of the present invention, wherein the epoxy resin adhesive is composed of (A) epoxy resin, (B) organic acid, (C) polyol, (D) (A) epoxy resin accounts for 1-50% of the total adhesive composition, preferably 5-48%, (B) organic acid accounts for 1-50% of the total adhesive composition, preferably 5-48%, (C) Polyol accounts for the adhesive The total composition is 0-50%, preferably 0-48%, and the (D) neutralizing agent accounts for 0-40% of the total composition of the adhesive (the neutralizing agent is limited to use when preparing a water-soluble epoxy resin adhesive).

Detailed description

Next, the 7j indelible engraving gravure printing ink composition of the present invention will be described. The above-mentioned water-erasable non-smudged engraved gravure printing ink composition is prepared by a conventional three-roll ink machine.

The non-basic pigments (organic pigments and inorganic pigments) used in the water-erasable non-stained engraving gravure printing ink composition are various organic pigments conventionally permitted to be used in the water-erasable non-stained engraving gravure printing ink composition And inorganic pigments.

The (A) phenol used in the oil-soluble pure phenolic resin used in the high-acid-value modified phenolic resin binder or the oil-soluble pure phenolic resin binder used as the high-acid-value modified phenolic resin adhesive is selected from phenol, O-methylphenol, m-methylphenol, p-fluorenylphenol, 2,4-difluorenylphenol, 2,5-dimethylphenol, 2,6-difluorenylphenol, 3,5-difluorenylphenol , 2,3-dimethylphenol, 3,4-dimethylphenol, dipanylpropane, p-tert-butylphenol, p-isoamylphenol, p-octylphenol, p-nonylphenol, p-phenylene and Its derivatives are one or more of phenol, p-cyclohexylphenol and other para-substituted phenols.

The (B) aldehyde used in the high acid value modified phenolic resin and oil-soluble pure phenol resin in the present invention is selected from aldehydes having a molecular weight of less than 500, such as an aqueous formaldehyde solution, solid polyacetaldehyde, acetaldehyde, and propanal , One or more of butanal, heptaldehyde, furfural, glutaraldehyde, glyoxylic acid, etc. and one or more of other aldehydes.

The (C) condensation catalyst used in the high acid value modified phenolic resin in the present invention is selected from the group consisting of urotropine, low molecular primary amines (such as ethylamine), low molecular secondary amines (such as dibutylamine), and hydrogen. One or more of basic salts of sodium oxide, calcium hydroxide, barium hydroxide, potassium hydroxide, lithium hydroxide, ammonia, zinc or magnesium, and one or more of other organic and inorganic bases. As the amount of the (C) condensation catalyst, it is from 0.1 to 3 · 5% by weight of the (A) phenol, preferably from 0.2 to 2%.

The (C) reducing agent used in the oil-soluble pure phenolic resin in the present invention is one or more selected from the group consisting of formic acid, acetic acid, oxalic acid, lactic acid, hydrochloric acid, nitric acid, phosphoric acid, sulfuric acid, and p-toluenesulfonic acid. And other organic or inorganic acids. As the amount of (C) condensation catalyst, it is G. 1-2% by weight of (A) phenol, preferably 0.2 to 1.5%. In the composition of the high acid value modified phenol casein resin, it is 1-70% of the total composition of the high acid value modified phenol resin as a condensate (content 100%) of (A) phenol and (B) aldehyde, preferably 5-65%. The molar ratio of phenol to aldehyde is in the range of 1: 0.6-2.5, and preferably 1: 1-2.

The (D) modifier used in the high acid value modified phenolic resin in the present invention is selected from one or more of rosin and its derivatives, tung oil, tung oleic acid, chemical substances having conjugated double bonds, and others One or more of the chemicals that can react with phenolic resin. The amount of the (D) modifier is 1-95%, preferably 2-75%, of the total composition of the high acid value modified phenolic resin.

The (E) polyol used in the high acid value modified phenol casein resin in the present invention is selected from ethylene glycol, neopentyl glycol, propylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, Tripropylene glycol, tetrapropylene glycol, glycerol, trimethylolpropane, pentaerythritol, dimer pentaerythritol, polyether diol, polyether triol, polyether tetraol, polyether pentanol, xylose Alcohol, sorbitol, mannitol, polyethylene glycol with an average molecular weight of 200-9500, polypropylene glycol with an average molecular weight of 400-7000, polymer polyols, one or more of polyester polyols, and other polyols One or more of them. (E) The amount of the polyhydric alcohol accounts for 0-40%, preferably 0-35%, of the total composition of the high acid value modified phenolic casein resin.

In the molecular structure of the high acid value modified phenolic casein resin, the introduction of a polyhydric alcohol with an ether group is helpful to improve the printing performance of the high acid value modified phenolic casein resin. As the ether group, 0-40% is preferable, and 0-35% is preferable.

During the preparation of the high acid value modified phenolic resin, an appropriate amount of vegetable oil or vegetable oleic acid is added, and the reaction is carried out by the vegetable oil or vegetable oleic acid, the aldehyde condensate, the modifier, and the unsaturated organic acid to improve the performance of the modified phenolic resin. The acid value is then neutralized with a neutralizing agent to obtain a water-soluble modified phenol resin binder.

The (F) neutralizer used in the high acid value modified phenolic casein resin of the present invention is selected from the group consisting of sodium hydroxide, potassium hydroxide, calcium hydroxide, ammonium bicarbonate, urotropine, urea, ammonia, and ammonia water. , One or more of monoethanolamine, diethanolamine, and triethanolamine, and one or more of other organic bases, inorganic bases, organic amines or inorganic ammonium salts that easily release ammonia gas when heated. The amount of (F) neutralizing agent accounts for 0-40%, preferably 0-35%, of the total composition of the high acid value modified phenolic resin.

The above-mentioned high acid value modified phenolic resin adhesive can be used alone or mixed with a plurality of polymer adhesives, the amount of which accounts for the total composition of the gravure printing ink composition 1-60% _{o The} above-mentioned oil-soluble pure phenolic resin adhesive is used in an amount of 0-30% of the total composition of the engraving gravure printing ink composition which is not stained with water. As specific examples, the products of Beijing Wanyang Anti-Counterfeiting Technology Co., Ltd. can be listed: high acid value such as WY-206, WY-216; ^ modified phenol casein resin, WY-111 oil-soluble pure phenolic resin; WY-2061, ¥ Υ-2064, WY-2065, WY-2066, WY-2161, WY-2162, WY-2163 High acid value rosin modified phenolic resin adhesive, WY-1111 oil-soluble pure phenolic resin adhesive, etc.

The modifier used as a water-soluble modified alkyd resin adhesive or modified alkyd resin adhesive is selected from vegetable oils or vegetable oleic acids, rosin and its derivatives, styrene, butadiene, organic isocyanates, One of acrylic acid and its derivatives, epoxy resin, epoxy resin modified vegetable oil, maleic acid and its gf or fumaric acid modified vegetable oil, phenol casein resin, rosin modified phenolic resin, amino resin One or more of one or more and other chemicals capable of reacting with the alkyd resin. The amount of the modifier (A) accounts for 1-90%, preferably 20-85% of the total composition of the water-soluble modified alkyd resin adhesive or the modified alkyd resin adhesive.

The vegetable oil or vegetable oleic acid used as the (A) modifier is selected from linseed oil, tung oil, dehydrated castor oil, castor oil, perilla oil, catal oil, ITICICA oil, soybean oil, sunflower oil, grape seed oil, vegetable oleic acid, One or more of tower oil fatty acids and one or more of other vegetable oils and / or vegetable oleic acids.

The epoxy resin modified vegetable oil used as the (A) modifier is an epoxy resin modified with maleic acid and its anhydride, or trans maleic acid, or rosin and its derivatives, or other resins. Vegetable oleic acid-derived products, such as Beijing Wanyang Anti-Counterfeiting Technology Co., Ltd. products: WY-2041 epoxy resin and maleic anhydride modified linoleic acid varnish for gravure inks.

The maleic acid and its anhydride or fumaric acid modified vegetable oil used as the (A) modifier is a product obtained from maleic acid and its anhydride or fumaric acid modified vegetable oil, such as Beijing Products of Wanyang Anti-counterfeiting Technology Co., Ltd .: WY- ² 051 maleic acid modified for engraving gravure ink, 1. Tung oil for ink.

The aldehyde resin used as the (A) modifier is the above-mentioned phenol and aldehyde. The phenol resin obtained under alkali catalysis.

The rosin-modified phenolic casein resin used as the (A) modifier is the same as the above-mentioned modified formaldehyde resin. The base resin used as the (A) modifier is an alkyl-etherified melamine-formaldehyde resin, such as hexamethyloxymelamine-formaldehyde resin and the like.

The (B) polyol used in the water-soluble modified alkyd resin adhesive or modified alkyd resin adhesive in the present invention is selected from ethylene glycol, neopentyl glycol, propylene glycol, diethylene glycol, and triethylene glycol. Alcohol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, glycerol, trimethylolpropane, pentaerythritol, dimer pentaerythritol, polyether diol, polyether triol, polyether tetra Alcohols, polyether pentanols, xylitol, sorbitol, mannitol, polyethylene glycol with an average molecular weight of 200-9500, polypropylene glycol with an average molecular weight of 400-7000, polymer polyols, polyester polyols One or more of them and one or more of other polyols. The amount of (B) polyol used is 1-49%, preferably 2-40 ° / of the total composition of the water-soluble modified alkyd resin adhesive or modified alkyd resin adhesive. .

The (C) transesterification catalyst or esterification catalyst used in the water-soluble modified alkyd resin binder or modified alkyd resin binder in the present invention is selected from the group consisting of sodium hydroxide, potassium hydroxide, and lithium hydroxide And one or more of other inorganic bases, or one or more selected from the group consisting of sulfuric acid, oxide, magnesium oxide, and other esterification catalysts. 8%。 (C) The amount of transesterification catalyst or esterification catalyst accounts for 0-1%, preferably 0-0. 8% of the total composition of the water-soluble modified alkyd resin binder or modified alkyd resin binder.

The (D) organic acid used in the water-soluble modified alkyd resin adhesive or modified alkyd resin adhesive in the present invention is selected from benzoic acid, acrylic acid, p-tert-butylbenzoic acid, rosin, and adipic acid , Sebacic acid, phthalic acid and its anhydride, isophthalic acid, terephthalic acid, methine tetrahydrophthalic acid and its anhydride, tetrahydrophthalic acid and its anhydride, chlorine Bridge anhydride, tetrachlorophthalic anhydride, hydrogenated phthalic anhydride, pyromellitic acid and its anhydride, pyromellitic acid, trimellitic acid and its liver, succinic acid, maleic acid and its anhydride, fumaric acid, One or more of itaconic acid, rotonic acid, chloromaleic acid, tower oil fatty acid, vegetable oleic acid, and one or more other organic acids. The amount of (D) the organic acid accounts for 1-50%, preferably 2-45%, of the total composition of the water-soluble modified alkyd resin adhesive or modified alkyd resin adhesive.

The (E) esterification catalyst used in the water-soluble modified alkyd resin binder or modified alkyd resin binder in the present invention is selected from one or more of sulfuric acid, zinc oxide, magnesium oxide, and others One or more of the esterification catalysts. The amount of (E) esterification catalyst accounts for water-soluble modification 8%。 Alkyd resin adhesive or modified alkyd resin adhesive composition of 0-1%, preferably 0-0. 8%. The (F) sulfonating agent used in the water-soluble modified alkyd resin adhesive in the present invention is selected from the group consisting of one or more of ^ acid, oleum, and other sulfonates with a content of 85% or more One or more of the agents. When preparing a water-soluble modified alkyd resin adhesive, sulfonation with concentrated oleic acid or oleum is used, and the amount of (F) sulfonating agent is excessive.

The (G) neutralizer used in the water-soluble modified alkyd resin adhesive in the present invention is selected from the group consisting of sodium hydroxide, potassium hydroxide, calcium hydroxide, ammonium bicarbonate, urotropine, urea, and ammonia. , One or more of ammonia, monoethanolamine, diethanolamine, and triethanolamine, and one or more of other organic minus, inorganic base, organic amine or inorganic ammonium salt that easily release ammonia gas when heated.

After the water-soluble modified alkyd resin binder is sulfonated, the amount of (G) neutralizing agent is measured by pH when neutralized with organic base, ammonia, organic amine or inorganic ammonium salt which can easily release ammonia when heated. The results are determined; after neutralization with an inorganic base such as sodium hydroxide, potassium hydroxide, hydroxide, etc., the water must be removed.

In the molecular structure of the modified alkyd resin adhesive, the introduction of polyalcohols with ^ & is helpful to improve the printing performance of the modified alkyd resin adhesive. As an ether group, it should preferably contain 0-40%. Preferably 0-35% _{0 The} above-mentioned modified alkyd resin adhesive can be used alone or mixed with a plurality of polymer adhesives, and the amount accounts for 0- 50 ° /. . As a specific example, the products of Beijing Wanyang Anti-Counterfeiting Technology Co., Ltd. can be listed: ¥ Y-2801, WY-2803 modified alkyd resin adhesive.

The amount of water-soluble modified alkyd resin adhesive is 0-20% of the total composition of the engraving gravure printing ink composition. It has the advantages of surfactants, and at the same time participates in the oxidative polymerization and drying of engraving gravure printing inks that are not stained by water. In a humid climate, the drying effect of the water-soluble modified alkyd resin adhesive is significantly better than that of the ammonium alkylaryl sulfonate. The water wiping effect after adding the water-soluble modified alkyd resin adhesive is the same as the water wiping effect when the ammonium alkylaryl sulfonate is added. The alkali-resistance (2% sodium hydroxide) of the printed products added with the water-soluble modified alkyd resin adhesive is improved compared with the printed products added with the alkylaryl ammonium sulfonate. The above-mentioned water-soluble modified alkyd resin adhesive is usually mixed with other polymer adhesives for use. As a specific example, the products of Beijing Wanyang Anti-counterfeiting Technology Co., Ltd. can be listed: WY-2802 water-soluble modified alkyd resin adhesive. The (A) polyol or (B) polyol used in the polyurethane resin adhesive in the present invention is selected from the group consisting of ethylene glycol, neopentyl glycol, propylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, and one shrinkage. Dipropylene glycol, tripropylene glycol, tetrapropylene glycol, glycerol, trimethylolpropane, pentaerythritol, dimer pentaerythritol, polyether diol, polyether triol, polyether tetraol, polyether pentaol , Xylitol, sorbitol, mannitol, polyethylene glycol with an average molecular weight of 200-9500, polypropylene glycol with an average molecular weight of 400-7000, polymer polyols, polyester polyols, and one or more of them, and One or more of the other polyols. The amount of the polyhydric alcohol or (B) polyhydric alcohol accounts for 1-50%, preferably 2-45% of the total composition of the polyurethane resin adhesive.

The (B) organic acid or (E) organic acid used in the polyurethane resin adhesive in the present invention is selected from the group consisting of benzoic acid, acrylic acid, p-tert-butylbenzoic acid, rosin, adipic acid, sebacic acid, and phthalic acid. Formic acid and its anhydride, isophthalic acid, terephthalic acid, bridged methine tetrahydrophthalic acid and its anhydride, tetrahydrophthalic acid and its anhydride, chloro bridge anhydride, tetrachlorobenzene hydrazone, Hydrogenated phthalic anhydride, pyromellitic acid and its anhydride, trimellitic acid, trimellitic acid and its anhydride, succinic acid, maleic acid and its anhydride, fumaric acid, itaconic acid, spinaconic acid, One or more of chloromaleic acid, tower oil fatty acid, vegetable oleic acid, and other organic acids. The amount of the (B) organic acid or (E) organic acid accounts for 1-90%, preferably 10-80%, of the total composition of the polyurethane resin adhesive.

During the preparation of the polyurethane resin adhesive, the esterification reaction between the polyol and the organic acid includes the transesterification reaction between the vegetable oil and the polyol. In formula calculation, glycerin in vegetable oil is counted into the amount of polyol; vegetable oleic acid in vegetable oil is counted into the amount of organic acid.

The (C) catalyst or (F) catalyst used in the polyurethane resin adhesive in the present invention is selected from the group consisting of dibutyltin dilaurate, cobalt naphthenate, cobalt octoate, potassium oleate, triethylamine, and stannous octoate. One or more of one or more of other catalysts that facilitate the reaction of organic isocyanates. 8%。 The amount of (C) catalyst or (F) catalyst is 0-1%, preferably 0-0. 8% of the total composition of the polyurethane resin binder.

The (D) organic isocyanate used in the polyurethane resin adhesive in the present invention is one or more selected from the group consisting of TDI, MDI, PAPI, HDI, XDI, HMDI, IPDI, TMDI, HTDI and other organic isocyanate group-containing One or more of the prepolymers. The amount of (D) organic isocyanate accounts for 1-50%, preferably 1-45%, of the total composition of the polyurethane resin adhesive.

(E) end-capping agent or (G) end-capping agent used in the polyurethane resin adhesive in the present invention, One or more selected from methanol, ethanol, n-propanol, n-butanol, and one or more of other primary or secondary alcohols. The amount of (E) end-capping agent or (G) end-capping agent accounts for 0-15% of the total composition of the polyurethane resin adhesive.

In the molecular structure of the polyurethane resin adhesive, the introduction of a polyol with an ether group is helpful to improve the stenciling performance of the polyurethane resin adhesive. As the ether group, it should preferably contain 0-40%, preferably 0-35%. The above-mentioned polyurethane resin adhesive can be used alone or mixed with a plurality of polymer adhesives, and the amount of the polyurethane resin adhesive accounts for 0-50% of the total composition of the engraving gravure printing ink composition. As specific examples, the products of Beijing Wanyang Anti-Counterfeiting Technology Co., Ltd. can be listed: WY-2901, WY- ² 902 polyurethane resin adhesive.

The (A) polyol used in the unsaturated polyester resin adhesive in the present invention is selected from ethylene glycol, neopentyl glycol, propylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, Tripropylene glycol, tetrapropylene glycol, glycerol, trimethylolpropane, pentaerythritol, dimer pentaerythritol, polyether diol, polyether triol, polyether tetraol, polyether pentanol, xylose Alcohol, sorbitol, mannitol, polyethylene glycol with an average molecular weight of 200-9500, polypropylene glycol with an average molecular weight of 400-7000, polymer polyol, one or more of polyester polyols and other polyols One or more of them. As U), the amount of the polyol accounts for 25-80%, preferably 25-74% of the total composition of the unsaturated polyester resin adhesive.

The (B) organic acid used in the unsaturated polyester resin adhesive in the present invention is selected from the group consisting of benzoic acid, acrylic acid, p-tert-butylbenzoic acid, rosin, adipic acid, sebacic acid, phthalic acid, and Its anhydride, isophthalic acid, terephthalic acid, bridged methine tetrahydrophthalic acid and its anhydride, tetrahydrophthalic acid and its anhydride, chlorobridged anhydride, tetrachlorophthalic anhydride, hydrogenated phthalic anhydride, Pyromellitic acid and its anhydride, trimesic acid, trimellitic acid and its anhydride, succinic acid, maleic acid and its liver, fumaric acid, itaconic acid, rotaconic acid, chlorocis One or more of butenedioic acid, tower oil fatty acid, vegetable oleic acid, and one or more of other organic acids. The amount of (B) organic acid accounts for 20-75%, preferably 26-75% of the total composition of the unsaturated polyester resin binder.

The (C) esterification catalyst used in the unsaturated polyester resin binder in the present invention is selected from one or more of sulfuric acid, zinc oxide, magnesium oxide, and one or more of other esterification catalysts. The amount of (C) the esterification catalyst accounts for 0-2.5%, preferably 0-1% of the total composition of the unsaturated polyester resin binder. The (D) antioxidant used in the unsaturated polyester resin adhesive in the present invention is one or more selected from the group consisting of hydroquinone, antioxidant 264, butanone oxime, and one of other antioxidants. Or more. The amount of the (D) antioxidant is 0-2.5%, preferably 0-1%, of the total composition of the unsaturated polyester resin adhesive.

1-4 Pa. S The molecular weight of the unsaturated polyester resin binder is controlled by its viscosity. When the unsaturated polyester resin is used as a varnish, the viscosity is controlled at less than 6 Pa. S / 40 C, preferably 0. 1-4 Pa. S / 40 is appropriate. When unsaturated polyester resin is used as a polymer binder, the viscosity should be controlled at 4-200 Pa. S / 40 ° C.

In the molecular structure of unsaturated polyester resin adhesives, the introduction of polyols with ether groups can help to improve the printing performance of unsaturated polyester resin adhesives. As ether groups, it should contain 0-70%, It is preferably 0-60%; the organic acid introduced should contain a certain amount of vegetable oleic acid; the amount of unsaturated double bonds introduced; The amount and the ink film properties of the engraving gravure printing ink are determined. The aforementioned unsaturated polyester resin adhesive can be used alone or mixed with multiple polymer adhesives, and the amount of the unsaturated polyester resin adhesive accounts for 0-50% of the total composition of the engraved gravure printing ink composition. As specific examples, the products of Beijing Wanyang Anti-counterfeiting Technology Co., Ltd. can be listed: WY-5001 water-soluble unsaturated polyester resin toner, WY-5002 unsaturated polyester resin adhesive.

The (A) epoxy resin used in the epoxy resin adhesive in the present invention is selected from A-95, B-63, E_03, E-06, E-12, E-14, E-20, E- 31, E-35, E-42, E-44, E_51, F-44, F-46, ET-40, EG-02 and one or more of other epoxy resins . The amount of (A) epoxy resin accounts for 1-50%, preferably 5-48% of the total composition of the epoxy resin adhesive.

The (B) organic acid used in the epoxy resin adhesive in the present invention is selected from benzoic acid, acrylic acid, p-tert-butylbenzoic acid, rosin, adipic acid, sebacic acid, phthalic acid and its anhydride. , Isophthalic acid, terephthalic acid, methine tetrahydrophthalic acid and its anhydride, tetrahydrophthalic acid and its anhydride, chlorobridged anhydride, tetrachlorophthalic anhydride, hydrogenated phthalic anhydride, pyromellitic acid Acids and their anhydrides, trimesic acid, trimellitic acid and its anhydride, succinic acid, maleic acid and its anhydride, fumaric acid, itaconic acid, rotaconic acid, chloromaleic acid One or more of acids, tower oil fatty acids, vegetable oleic acid, and one or more of other organic acids. The amount of (B) organic acid used is 1-50%, preferably 5-48%, of the total composition of the epoxy resin adhesive. The (C) polyol used in the epoxy resin adhesive in the present invention is selected from ethylene glycol, neopentyl glycol, propylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, diethylene glycol Triglyceride, Triglyceride, Glycerol, Trimethylolpropane, Pentaerythritol, Dimer Pentaerythritol, Polyether Glycol, Polyether Triol, Polyether Tetraol, Polyether Pentaol, Xylitol , Sorbitol, mannitol, polyethylene glycol with an average molecular weight of 200-9500, polypropylene glycol with an average molecular weight of 400-7000, polymer polyols, one or more of polyester polyols and other polyols One or more. The amount of the (C) polyol is 0-50%, preferably 0-48%, of the total composition of the epoxy resin adhesive.

The (D) neutralizing agent used in preparing the water-soluble epoxy resin adhesive in the present invention is selected from the group consisting of sodium hydroxide, potassium hydroxide, calcium hydroxide, ammonium bicarbonate, urotropine, urea, and liquid. One or more of ammonia, ammonia, monoethanolamine, diethanolamine, and triethanolamine, and one or more of other organic bases, organic amines or inorganic ammonium salts that are free of ammonia gas when heated. Neutralize with organic base, ammonia, organic amine or inorganic ammonium salt which can easily release ammonia gas when heated. (D) The amount of neutralizing agent is determined by measuring the value of ra. Use inorganic base, such as sodium hydroxide, hydroxide After neutralizing potassium, hydroxide, etc., the water must be removed, and the amount of (D) neutralizing agent is determined by the pH measurement result.

In the molecular structure of an epoxy adhesive, introduction of polyols with ½, help to improve the performance of epoxy resin adhesive Wiping as tt, preferably contain 0-40%, preferably ^0-35% ; The introduced organic acid should contain a certain amount of vegetable oleic acid. The above-mentioned epoxy resin adhesive can be used alone or mixed with a plurality of polymer adhesives, and the amount of the epoxy resin adhesive accounts for 0-50% of the total composition of the engraving gravure printing ink composition. As specific examples, the products of Beijing Wanyang Anti-Counterfeiting Technology Co., Ltd. can be listed: WY-3001, WY-300 ² epoxy resin adhesive.

As the high acid value rosin and its derivative polyol ester resin adhesive, one or more kinds of high acid value rosin and its derivative polyol ester resin adhesive can be selected. The high acid value rosin and its derivative polyol ester resin used as the high acid value rosin and its derivative polyol ester resin adhesive can be selected from the group consisting of high acid value rosin and its derivative polyol ester resin composition. The alcohols are ethylene glycol, neopentyl glycol, propylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, glycerol, trihydroxymethylpropane, pentaerythritol, Dimer pentaerythritol, polyether diol, polyether triol, polyether tetraol, polyether pentaol, One or more of xylitol, sorbitol, mannitol, polyethylene glycol with an average molecular weight of 200-9500, polypropylene glycol with an average molecular weight of 400-7000, polymer polyol, polyester polyol One or more of high acid value rosin and its derivative polyol ester resin and other high acid value rosin and its derivative polyol ester resin obtained after reacting with rosin and its derivative.

As a rosin and its derivative polyol ester resin binder, maleic acid and its anhydride or fumaric acid, vegetable oil and / Or vegetable oleic acid, after rosin and its derivatives are modified with maleic acid and its anhydride or fumaric acid, rosin is modified by neutralizer, maleic acid or fumaric acid and its derivatives Compounds, vegetable oils and / or vegetable oleic acids, polyols, etc., to obtain water-soluble rosin and its derivative polyol ester resin binder, wherein the neutralizing agent is selected from sodium hydroxide, potassium hydroxide, calcium hydroxide, One or more of ammonium bicarbonate, urotropine, urea, liquid ammonia, ammonia, monoethanolamine, diethanolamine, triethanolamine, and other organic bases, inorganic bases, organic amines or inorganic ammonium that can easily emit ammonia when heated One or more of the salts. Use ^ ammonia, organic amine or inorganic ammonium salt which can easily release ammonia gas when heated, and the amount of neutralizing agent is determined by measuring the pH value; use inorganic bases, such as sodium hydroxide, potassium hydroxide, hydroxide After the calcium and the like are neutralized, the water must be removed, and the amount of the neutralizing agent is determined by the measurement result of the pH value.

The molecular structure of the high acid value rosin and its derivative polyol ester resin preferably contains 0 to 40%, preferably 0 to 35%, of ether groups. The above-mentioned high acid value rosin and its derivative polyol ester resin adhesive can be used alone or mixed with multiple polymer adhesives. -50%. Such as Beijing Wanyang Anti-counterfeiting Technology Co., Ltd. Products: WY-2301, WY-2302 dimerized rosin polyol ester resin adhesive.

The water-cleaning and non-staining engraving gravure printing ink composition of the present invention, the auxiliary agent is selected from the group consisting of a desiccant, a retarder, a release agent, a wax, a surfactant, a vegetable oil, a varnish, and a high boiling point solvent. One or more.

As the desiccant, it is selected from the metal salts of organic acids, such as: cobalt, manganese, cerium, vanadium, lanthanum, iron, lithium, lead, zirconium, aluminum, calcium, saturated naphthenic acid, caprylic acid, and capric acid. The amount of one or more of salt and manganese borate accounts for 0-6% of the total composition of the engraving gravure printing ink composition which is not rubbed with water. Such as the products of Beijing Wanyang Anti-counterfeiting Technology Co., Ltd .: Compound desiccant (mixture of cobalt, manganese and zirconium). As a slow-drying agent, one or more selected from the group consisting of BHT, hydroquinone, p-tert-butylphenol, butanone oxime, and butyraldehyde oxime, the amount of which accounts for the total composition of the engraving gravure printing ink composition 0-6%.

As a debonding agent, one or more selected from 8043 debonding agent (product of Tianjin Ink Co., Ltd.) and other debonding agents, the amount of which accounts for 0-6% of the total composition of the gravure printing ink composition .

As the wax, it is selected from carnauba wax, candelilla wax, spanish wax, small crown coconut wax, Japanese wax, fir wax, palm wax, beeswax, insect wax, wool wax, paraffin wax, microcrystalline wax, montan wax , Mineral wax, stearic acid and its derivatives or their esterified products with alcohol, stearyl alcohol, polyethylene wax, oxidized polyethylene wax, chlorinated wax, high molecular aliphatic amide, aluminum stearate, petrolatum One or more of them. These waxes can be used alone or in combination. The combination of two or more waxes is also called mixed wax. The amount of wax used is 1-15% of the total composition of the engraving gravure printing ink composition which is not stained with water. Such as Beijing Wanyang anti-counterfeiting technology ^ 7 Gen products: WY-1201 mixed wax.

As a surfactant, it is selected from various anionic surfactants (such as pit-based aryl sulfonate, Taikoo oil, etc.), and various non-ionic surfactants (such as alkylbenzene polyoxyethylene ether, polypropylene glycol). Etc.) and one or more of other surfactants. When the above-mentioned surfactant is used in the process of gravure engraving gravure printing without water rubbing, it must also meet the requirements of the post-treatment process of engraving gravure printing. The amount of the surfactant accounts for 0-15% of the total composition of the engraving gravure printing ink composition which cannot be soiled by water. Such as Beijing Wanyang anti-counterfeiting technology limited liability company's products: WY-100 alkyl aryl sulfonate ammonium, WY-100-1 alkyd resin ammonium sulfonate and so on.

As the vegetable oil, one or more selected from the group consisting of linseed oil, tung oil, dehydrated castor oil, castor oil, perilla oil, catal oil, OITICICA oil, soybean oil, sunflower oil, grape seed oil, vegetable oleic acid, and tower oil fatty acid, and One or more of other vegetable oils or vegetable oleic acids. In the composition of the engraving gravure printing ink composition that is not wiped with dirt, as the amount of vegetable oil, when adjusting the viscosity of the composition, it is preferably 0-30% of the total composition, preferably 0-25%; adjustment When the viscosity of the polymer binder for the composition is preferably 0-50% of the total polymer binder for the composition, preferably 0-45%; adjusting the viscosity or state of the auxiliary agent for the composition In this case, it is preferably 0-50% of the total amount of the adjuvant for the composition, and preferably 0-45%. As the varnish, it is selected from polymer varnishes (such as:

# 4 adjusting oil, # 6 adjusting oil, cooked tung oil, etc.), low viscosity modified alkyd resin modified oil, low viscosity modified phenolic resin modified oil, low viscosity pure phenolic resin modified oil, styrene Or maleic acid and its anhydride or fumaric acid and other modified vegetable oils and / or oleic acid-based varnishes, one or more of low molecular unsaturated polyester resin varnishes and other One or more of the inks. The viscosity of the varnish is less than 6 Pa. S / 40 ° C, preferably 0. 4 Pa. S / 40 ° C. In the composition of the engraving gravure printing ink composition which is not rubbed with water, as the amount of the adjusting oil, when adjusting the viscosity of the composition, it is preferably 0-30% of the total composition, preferably 0-25% When adjusting the viscosity of the polymer binder for the composition, it is preferably 0-50% of the total polymer binder for the composition, preferably 0-45%; adjusting the viscosity of the auxiliary agent for the composition In the state or state, it is preferably 0-50% of the total amount of the adjuvant for the composition, and preferably 0-45%. Such as Beijing Wanyang Anti-counterfeiting Technology Co., Ltd. products: WY-204 # 6 ink oil, WY-205 cooked tung oil, WY-2705 low viscosity vegetable oil modified alkyd resin ink, WY-1385 low viscosity rosin modified phenolic Resin varnish, WY-2165 low viscosity rosin modified phenolic resin varnish, Y-3600 low viscosity unsaturated polyester resin varnish.

As a high boiling point solvent, it can be selected from non-toxic or low-toxic solvents with a boiling point higher than 2101C, liquid solvents at room temperature and non-toxic or low-toxic solvents with a boiling point higher than 210 ° C. The single component is solid at room temperature, and other substances After mixing, one or more of a mixture of solvents that are liquid at room temperature; or one or more of solvents approved for food and / or food packaging materials with a boiling point above 210; or Selected from high boiling point kerosene, diethyl maleate, dibutyl maleate, diisooctyl maleate, dibutyl tartrate, triethyl citrate, tributyl citrate, acetyl tributyl citrate Ester, acetyl triisooctyl citrate, dibutyl phosphite, phenyl di ( ² -ethylhexyl) phosphite, diphenyl phosphate 2-ethylhexyl phosphate, tri ( ² -chloroethyl) phosphate ) Esters, tris (2,3-dibromopropyl) phosphate, bis ( ² -ethylhexyl) phosphate, triethyl phosphate, tributyl phosphate, tributyl borate, triisooctyl borate, boric acid Tripentyl ester, dibutyl sebacate, phenethyl acetate, benzyl acetate, menthol acetate Tricyclodecenyl acetate, oxalan acetate, glyceryl triacetate, benzyl propionate, geranyl propionate, tricyclodecenyl propionate, oxalan propionate, phenethyl butyrate, isoamyl Phenylethyl ester, allyl heptanoate, ethyl nonanoate, ethyl decanoate, ethyl hexanoate, 2-ethylhexyl acrylate, ² -hydroxyethyl methacrylate, methacrylic acid-2 -Hydroxyl Propyl acrylate, ethyl undecylenate, ethyl linoleate, butyl oleate, tetrahydrofuran oleate, dibutyl oxalate, dibutyl malonate, diethyl n-butylmalonate, Diethyl ethoxymethylenemalonate, diethyl phenylethylmalonate, diisooctyl adipate, diisooctyl nylon acid, diisooctyl sebacate, sebacic acid Dioctyl octyl ester, diethyl sebacate, dimethyl phthalate, diethyl phthalate, dibutyl phthalate, diisobutyl phthalate, phthalate Dicyclohexyl ester, diheptyl phthalate, diisooctyl phthalate, di-n-octyl phthalate, di-sec-octyl phthalate, sec-octyl phthalate.Iso Octyl ester, Diisodecyl phthalate, Butyl tetradecyl phthalate, Octyl tridecyl phthalate, Benzyl phthalate, Phthalidene Acid dimethoxyethyl, butyl phthalate. Butyl ½ methyl ester, di (2-ethyl) phthalate, hexyl phthalate, undecyl phthalate, diphthalate Isononyl ester, phthalate Diallyl formate, di (tridecyl) phthalate, di C7-C9 alcohol phthalate (average molecular weight 380-390), dimethyl terephthalate, diterephthalate Isooctyl, diisooctyl isophthalate, tripropylene glycol monomethyl ether, polypropylene glycol (molecular weight 400-1200 and molecular weight> 2000), ethyldiethanolamine, thiodiglycol, methyl salicylate, phenyl Cellosolve acetate, carbitol acetate, butyl carbitol acetate, decanol, undecanol, dodecanol, benzyl alcohol, rosin alcohol, terpineol, 1. 3-propanediol, 1 3-butanediol, 1.5-pentanediol, 2-ethyl-1,3-hexanediol, glycerol monobutyrate, hexyl ether, pentylphenyl ether, dibenzyl ether, ethylene glycol Dibutyl ether, diethylene glycol dibutyl ether, oleic acid, triisooctyl trimellitate, tetra (2-ethylhexyl) pyromellitic acid, phenyl alkyl sulfonate (average molecular weight 368-390) ), Epoxy tetrahydrophthalate diisooctyl ester, benzyl benzoate, benzyl butyrate, benzyl propionate, butyl phenylacetate, amyl acetate, citral, citronellol, acetic acid Mao , Citronellate gallate, sage aldehyde, dimethyl benzyl acetate, ethyl laurate, ethyl caprate, ethyl laurate, strawberry aldehyde, ethyl nonanoate, ethyl phenylacetate, water Ethyl salicylate, amyl salicylate, isoamyl salicylate, eugenol, geraniol, geranyl formate, geranyl acetate, geranyl propionate, geranyl butyrate, hexamethylene Lactone, hexyl hexanoate, hexyl 2-fluorenylbutyrate, hydroxycitronellal, methylionone, ethylionone, isoamyl hexanoate, isoamyl phenylacetate, isoeugenol, aryl acetate Camphor ester, linalyl propionate, menthol acetate, anisaldehyde, p-methylacetophenone, isoeugenol methyl ether, methyl octynecarboxylate, methyl ² -octynoate, threonyl acetate, formazan Nonyl acetaldehyde, nerol, nerol, neryl acetate, cucumol, coconut aldehyde, Jasmonate, nonanoic acid, nonyl acetate, phenethyl acetate, phenethyl alcohol, phenethyl butyrate, phenethyl isovalerate, phenylacetic acid, phenylpropanol, phenylpropionaldehyde, rose alcohol, terpine acetate, Myraldehyde, Undecylaldehyde, 10-Undecenal, Ethyl Myristate, Glycol Monoacetate, Diethylene Glycol Diacetate, Glycerol Monoacetate, Glycerol Diacetate, Glycerin Triacetate, glyceryl monobutyrate, benzyl rosinate, ethyl rosinate, ethyl cinnamate, isoamyl benzoate, butyl benzoate, propyl benzoate, ethyl benzoate, stearin Amyl ester, butyl stearate, ethylene glycol-phenyl ether, ethylene glycol-benzyl ether, diethylene glycol-butyl ether, triethylene glycol, triethylene glycol, dipropylene glycol-butyl ether , Tripropylene glycol monobutyl ether, polyethylene glycol (average molecular weight is less than 630), dipropylene glycol, C5-C9 fatty acid glycol ester, C5-C9 fatty acid diethylene glycol ester, C5-C9 fatty acid pentaerythritol ester Or more. In the composition of the water-erasable engraving gravure printing ink composition, when the amount of the high boiling point solvent is used, when adjusting the viscosity of the composition, it is preferably 0-30% of the total composition, preferably 0-25% . When adjusting the viscosity of the polymer binder for the composition, it is preferably 0-50%, and preferably 0-45%. When adjusting the viscosity or state of the auxiliary agent for the composition, it is preferably 0-50%, and preferably 0-45%.

In the following, the water-erasable sculpted gravure printing ink composition of the present invention is further described by way of example, but the present invention is not limited by these specific examples.

Example 1. Synthesis of high acid value rosin modified phenolic resin

In a 5L four-neck round bottom flask equipped with a stirrer, thermometer, reflux condenser, and nitrogen introduction tube, add 405 g of T tt tert-butylphenol, 331 g of liquid formaldehyde, 15 g of ammonia, 2207 g of rosin, and 90-110r; After 4 hours, the temperature was raised to 130, 66 g of maleic anhydride was added, and the temperature was further increased to 190-210. C, react for 2 hours, add 5g of glycerin, pass nitrogen, and raise the temperature to 250 ° F, and react until the acid value is 140-150mgKOH / g to obtain high acid value rosin modified phenol resin.

The high acid value rosin modified phenolic casein resin has a softening point of 120Ό, an acid value of 144 mgKOH / g, and a number average molecular weight of 6,200.

Example 1-1. Water soluble rosin modified phenolic resin

On the basis of Example 1, polyglycerol and / or triethylene glycol and / or tetraethylene glycol were used instead of glycerol, and the amount of polyether diol and / or triethylene glycol and / or tetraethylene glycol was added, so that Example 1 The acid value was reduced from 140-150 mgKOH / g to 70-80 mgKOH / g to obtain a water-soluble rosin-modified phenolic resin.

Example 1-2. Water-soluble rosin modified phenolic resin adhesive In the preparation of Example 1, linseed oil and / or tung oil in the amount of rosin-modified phenolic resin was added, and the linoleum and / or tung oil, phenolic condensate, rosin, and maleic anhydride were added at 190-200 ° C. After the reaction, monoethanolamine was added for neutralization, and the viscosity was adjusted with diethylene glycol butyl ether to obtain a water-soluble rosin-modified phenol resin binder.

Example 1-3. Water soluble rosin modified phenolic resin adhesive

In the preparation of Example 1, linseed oil and / or tung oil in the amount of rosin-modified phenolic resin was added at 190-200 * from linseed oil and / or tung oil, phenolic condensate, rosin, and maleic acid liver. After the reaction, polyether triol and / or triethylene glycol or tetraethylene glycol are added for the esterification reaction, and the amount of the polyhydric alcohol is added to calculate the equivalent, that is, the number of equivalents of the polyol and the number of equivalents of the organic acid are 1: 1 05-1. 3, preferably 1: 1. 05- 1.1 is suitable. The viscosity was adjusted with diethylene glycol butyl ether to obtain a water-soluble rosin-modified phenol resin binder.

Example 2: Synthesis of high acid value modified phenolic resin adhesive

In a 5 L four-neck round bottom flask equipped with a stirrer, a thermometer and a nitrogen introduction tube, 2000 g of tung oil was added, and the temperature was raised while nitrogen was passed on the surface. When the temperature is raised to be higher than the softening point of 30- 50Ό resin, phenolic resin was added 2000g _o pieces at a process temperature above the resin softening point of 30- 50Ό, the viscosity of the polymer binder of the insulation of 50-70Pa. S / 40O, reduce the temperature to 150 ° C, and adjust the viscosity of the polymer adhesive to 4-7 Pa with cooked tung oil. (If necessary, dibutyl phthalate can be used to adjust the viscosity of the polymer adhesive. Ensure that the acid value of the polymer binder is 55-65 mgKOH / g), and discharge it to obtain a modified phenolic resin binder.

The viscosity of the polymer binder is 5-7 Pa. S / 40 ° C, the acid value is 55-65 mgKOH / g, the appearance is clear and transparent, and there are no mechanical impurities.

Example 2-1 Synthesis of high viscosity and high acid value modified phenolic resin adhesive

During the operation of Example 2, at a process temperature 30-50 ° C higher than the softening point of the resin, the temperature was maintained until the viscosity of the polymer binder reached 50-70Pa. S / 40O (or higher viscosity), After the temperature was lowered to 150 ° C, the material was discharged to obtain a high-viscosity and high-acid-value modified phenolic resin adhesive.

Example 3. Synthesis of linseed oil modified alkyd resin adhesive

In a 3L four-neck round bottom flask equipped with a stirrer, thermometer, reflux condenser, oil-water separator, and nitrogen introduction tube, add linseed oil 75, glycerol 96g, pentaerythritol 80.4g, lithium hydroxide 0.3g, temperature increase, while the surface nitrogen, alcoholysis reaction 2 ⁵ 0 ° C (or Say fat exchange reaction). After the alcoholysis is qualified (add 5 ML95% ethanol to 1ML resin, and it is transparent after being shaken to be qualified), cool down to 190-200 ° C, stop nitrogen, add 327g isophthalic acid, 0.45g oxidation group isobutyl ketone 100g, an esterification reaction at ²² 0_ ² 30 ° C. During the esterification reaction, if the temperature is higher than 230 ° C, methyl isobutyl ketone can be added appropriately to keep the reflux normal. After the acid value drops below 30 mgKOH / g, the temperature is reduced to 150-160 ° C, and all methyl isobutyl ketone is removed therefrom. According to the viscosity (the viscosity at this time is generally 20-40 Pa. S / 40 ° C), adjust the viscosity of the polymer adhesive to 4-7 Pa. S / 40 "C with # 6 ink, and then discharge To obtain a linseed oil modified alkyd resin binder.

Example 3-1. High viscosity linseed oil modified alkyd resin adhesive

During the operation of Example 3, when the viscosity of the polymer binder reached 20-40 Pa. S / 40X (or higher viscosity), after the temperature was lowered to 150 ° C, the material was discharged to obtain a high-viscosity linseed oil modified alkyd resin. Adhesive.

Example 4. Synthesis of water-soluble linseed oil modified alkyd resin adhesive

In a 1 L four-neck round bottom flask equipped with a stirrer, a thermometer, a reflux condenser, an oil-water separator, and a nitrogen introduction tube, 24.6 g of linseed oil, 29.7 g of glycerol, 25, 5 g of pentaerythritol, and 0.3 g of lithium hydroxide were added. , The temperature is raised, while the surface is nitrogen, and an alcoholysis reaction (or a lipid exchange reaction) is performed at 250 ° C. 45g ， After the alcoholysis is qualified (5 ML95% ethanol is added to 1ML resin, and it is transparent after being shaken to be qualified), the temperature is lowered to 190-200r; the nitrogen is stopped, and 156.5 g of isophthalic acid is added, and 0.45 g of zinc oxide is added. 100 g of methyl isobutyl ketone was subjected to an esterification reaction at 220-230 F. During the esterification reaction, if the temperature is higher than 230 ° F, methyl isobutyl fluorenone can be appropriately added to keep the reflux normal. After 1.5 hours at reflux, 47.7 g of triethylene glycol was added, and the esterification was continued. After the acid value was reduced to 30-40 mgKOH / g, the temperature was lowered to 150-1 ⁶ 0Ό, and methyl isobutyl ketone ^ was removed therefrom. except. According to the viscosity, the viscosity of the polymer binder was adjusted to 4-7 Pa. S / 40 "C with soybean oil, and the material was discharged to obtain a water-soluble linseed oil modified alkyd resin binder.

Example 5 Synthesis of polyurethane resin adhesive

In 1L four-necked round flask equipped with a stirrer, thermometer, reflux condenser, water separator and a nitrogen inlet tube was charged with linseed oil ^{2 .8g,} pentaerythritol 51. 93g, lithium hydroxide 0. 04g, heating, while the surface nitrogen, a solution of an alcohol (aliphatic or exchange) reaction is 2 ⁵ 0T. After the alcoholysis is qualified (add 5 ML9 ⁵ % ethanol to 1ML resin, and it will be transparent after shaking), Reduce the temperature to 190-200 ° C, stop nitrogen, add 35. 25g of phthalic anhydride, 35ml of xylene at 220-230. (Esterification reaction is performed. During the esterification reaction, if the temperature is higher than 230 ° C, xylene can be added appropriately to keep the reflux normal. After the acid value drops below 5 mgKOH / g, the temperature is lowered to 150-160 ° C, remove all of the xylene therein. Then, add 100 g of dibutyl phthalate, reduce the temperature to 50 "C, add 0.05 g of dibutyltin dilaurate, 54.66 g of TDI dropwise, and The temperature will rise naturally, react at 80-85 ° C for 3 hours, add 1.1 ml of methanol, and then react for 1 hour. Start measuring the viscosity, and adjust the polymer binder with dibutyl phthalate according to the viscosity. Viscosity to 4- 7 Pa. S / 40 C, the material was discharged to obtain a polyurethane resin adhesive.

Example 5-1 water-soluble polyurethane resin adhesive

Based on Example 5, after adding dibutyl phthalate, more TDI 30g and TDI 30g equivalents of polyether diol or polyether triol were added. Alkyd resin, polyether diol or polyether After the ether triol and TDI react, a water-soluble polyurethane resin binder is obtained.

Example 6.Synthesis of high acid value epoxy resin adhesive

In a 3 L four-neck round bottom flask equipped with a stirrer, a thermometer, and a nitrogen introduction tube, 946 g of tungoleic acid was added, and the temperature was raised while nitrogen was passed on the surface. When the temperature rises to 200, add 241g of fragmented dimerized rosin, 459g of 634 epoxy resin, and heat it at 180-200Ό until the acid value of the epoxy resin adhesive reaches 60-65 mgKOH / g, and the viscosity reaches 50- At 70Pa. S / 40 * C, reduce the temperature to 150. Use dibutyl phthalate to adjust the viscosity of the polymer adhesive to 4-7 Pa. S / ⁴⁰ 0 "C, and discharge it to obtain a high acid value epoxy. Resin adhesive.

Example 6-1 Water-soluble epoxy resin adhesive

On the basis of Example 6, 90 g of maleic anhydride was added, and after the reaction, an appropriate amount of monoethanolamine was added to neutralize to obtain a water-soluble epoxy resin adhesive.

Example 6-2 water-soluble epoxy resin adhesive

In Example 6-1, 1.84 equivalents of polyether diol and / or polyether triol and / or triethylene glycol or tetraethylene glycol were added. After the reaction, a water-soluble epoxy resin adhesive was obtained. .

Example 7. Synthesis of water-soluble modified alkyd resin adhesive

In ² L four-necked round flask equipped with a stirrer, thermometer, reflux condenser, water separator and a nitrogen inlet tube was charged with linseed oil ^2. 80g, pentaerythritol 51. 93g, lithium hydroxide 0. 04g, heating, and nitrogen surface, alcoholysis reaction 2 ⁵ 0 ° C. Qualified for alcoholysis (in 1ML resin was added with 5 ML95% ethanol, and it became transparent after being shaken to be qualified), then the temperature was reduced to 190-200 ° C, nitrogen was stopped, 25. 00 g of phenyl liver was added, and 35 ml of xylene was esterified at 220- 230 ° C reaction. In the course of the esterification reaction, if the temperature is higher than 230 ° C, dibenzobenzene can be added appropriately to keep the reflux normal. After the acid value drops below 3 mgK0H / g, the temperature is lowered to 150-160 C, and all the xylene therein is removed. Then, the temperature is lowered to 30-35 ° C, and 98% concentrated gram acid is added dropwise. When the 98% concentrated ^^ acid is added dropwise, the temperature will naturally rise. After reacting for 4 hours at 30-35, 98% concentrated dropwise is added. In the process of sulfuric acid, take samples every 10 minutes after two hours, and measure the sulfonation end point of the alkyd resin (take 3 drops of resin, add 10ML distilled water, shake well, clear and transparent as the end point). After the sulfonation reaches the end point, immediately Add 2 times the amount of water in the material, stir well, and then stand still to separate the layers. Discard the lower aqueous solution, and perform the same three times of water washing. Then, add 60 g of dibutyl phthalate, at 50-55, neutralize with ammonia to pH = 4-5 as the end point. After discharging, a water-soluble modified alkyd resin adhesive was obtained.

Material name Example 8 Example 9 Example 10 Example 11 Example 12 Example 13 Example 14 Example 15 p-octylphenol 30. 02 35. 17-14. 58-p-nonylphenol ―-30. 84 15. 57 ― 27. 37-p-tert-butylphenol ―---8.78-14. 4 Carboxaldehyde 37% ― t-mono---11. 0 Polycarbaldehyde 6.55 7.68 o 7. 72 7. 57 7. 65 7. 75 7 40-urotropine 0.43 0.70 0.44 0.43 0. 43 0.65 0. 62 0.20 rosin 58.74 51.57 57.76 57.76 56.63 57, 19 62. 52 59.68 72.4 maleic anhydride 4.27 5, 58 4.62 4.53 4. 57 5.42 4.93 2. 0 Softening point 155.0 0 147. 0 147. 0 156. 0 108. Acid value mgKOH / g 128.4 147.8 125.9 109.6 130. 0 146. 0 148. Engraving gravure ink

Basic performance: t

o o

Water cleaning effect ○ ◎ O 〇O 〇 o 〇〇 Oil solubility ◎ ◎ O 〇 ◎ 〇〇〇 Non-staining performance o 〇〇〇o 〇 ◎ 〇 Abrasion resistance of printed products ◎ ◎ ◎ ◎ ◎ ◎ ◎ printed products Alkali resistance □ □ □ o □ □ □ Δ Print resistance to wrinkle 〇〇〇〇〇〇 ο 〇 Printing wastewater treatment o O 〇o 〇ο ο 〇

Table 2

Material name Example 16 Example 17 Example 18 Example 19 Example 20 Example 21 Example 22 Example 23 p-tert-butylphenol 16. 44 19. 75-14. 57 58. 1 3 ― 21 · 67 A pair of octylphenol---- ---12. 76 p-nonylphenol-5. 77-----Phenol 5. 18-------Bisphenol A--10. 09---Monocarboxaldehyde 37%--14 87-21 · 84 12. 86 Paraformaldehyde 6. 90 6. 32-------Ammonia-0, 50 0 · 35---0 · 44 0. 2 Urotropine 0.49 ― 0 25----Hydrochloric acid-Mono--0.33---Rosin 65. 76 62. 66 72. 57 58. 27--24. 06 14. 17 Maleic anhydride 5. 23 10. 03 2 12 6. 99-―--Pentaerythritol Mono--3. 96----Magnesium Oxide---0.065-------Ethyl Cellulose--Mono -------4. 34 Tungonic Acid-- ---1 30. 50 tung oil-----9.91-

# 6 调油油 ―--One--8. 00

E-12 Epoxy resin-----60. 00--Linoleic acid-----26. 60--Phthalic acid di------7.93 17. 17 Butyl ester

Softening point 140 · 5 135 160 113-―-Acid value m _g K0H / g 152 144 140 107 90 5. 00 78. 76 Viscosity Pa. S / 40 "C-----2. 70 5. 50 4. 00 Engraving Gravure Oil

Basic ink performance

Test:

Water cleaning effect □ ◎ △ △ Δ O 〇 Oil solubility 〇厶〇〇〇 ◎ ◎ Non-staining performance 〇〇〇〇〇〇〇 o Prints abrasion resistance 〇〇〇〇〇〇 ◎ ◎ Prints Alkali resistance □ □ □ 〇〇〇 □ o Printed products are resistant to wrinkling 〇〇〇〇〇〇〇 ◎ ◎ ◎ Printing sewage treatment 〇〇〇〇〇〇〇oo table 3

Table 4

Material name Example 32 Example 33 Example 34 Example 35 Example 36 Example 37 Linoleic acid ― 40. 27-― 52. 41 Tungoleic acid ―--― 35. 13 Maleic anhydride ― 40. 73 37. 93 3, 83 11. 75 Phthalic anhydride ― 12.73 Mono-dipic acid ― 13. 48 ― Monoethylene glycol ― ― 11.15 Diethylene glycol monobutyl ether ― Moderate amount-One shrink Diethylene glycol ― 14. 69 ― diethylene glycol triethylene glycol ― 21. 71 － 20. 38 ― —— dimer pentaerythritol ― 10. 90 ― mono-glycerol ― 31. 10 28. 96 ―-poly Propylene glycol ― ― ― 23. 98 Epoxy resin ― 20. 55 Monoisopropanolamine — ― 7. 86 ― Hydroquinone ― 0. 15 0. 13 ― Rosin ― ― ― 1

Dioctyl phthalate 20. 00 Appropriate amount --- Appropriate amount of polyethylene wax 10. 00-One-One-Paraffin 80. 00----One acid value mgKOH / g--One-30 Viscosity Pa. S / 40 ― 2. 0 2. 5 2. 0 3. 5 7. 0 Basic engraving four printing ink

Performance test:

Water cleaning effect Δ ◎ O ◎ ◎ 0 Oil solubility ◎ ◎ Δ Δ o ◎ Non-staining performance ◎ O O o

Abrasion resistance of printed products ◎ O o

Alkali resistance of printed products o ◎ ◎ ◎ □ Crease resistance of printed products ◎ ◎ ◎

Printing wastewater treatment O Material name Example 38 Example 39 Example 40 Example 41 Example 42 Example 43 Phenolic resin adhesive ① 27.0 0 ― ― ― Monophenol resin adhesive ② ― 27.0-― Monophenol resin adhesive ③ ― ― 27.4 ― ―-Phenolic resin adhesive ④ ― ― 27. 0 ——-Butyl resin adhesive ⑤ 8. 6 7. 8 7. 0 6. 8 6. 8 6. 2 Phenolic resin resin Adhesive ⑥ ― ― ― 27. 0 23. 9 Alkyd resin adhesive ① 9. 4 9. 9 9. 5 9. 6 9. 4 9. 0 Alkyd resin adhesive ② ― ― One ― A 6.0 surfactant 3. 6 3. 6 3. 4 3. 6 3. 8-mixed wax 6. 6 6. 6 6. 6 6. 7 6. 9 6. 6 Calcium carbonate 30. 5 31. 3 31. 5 31. 3 31. 3 32. 5 Organic yellow pigments 1. 3 1. 3 1. 3 1. 3 1. 3 1. 3 Organic blue Pigment 8. 7 8. 7 8. 7 8. 7 8. 7 8. 7 Desiccant (added later) 2. 2 2. 0 2. 0 2. 0 2. 0 2. 0 Dibutyl phthalate Esters 1. 5 2. 1 2. 6 3. 0 2. 8 3. 8 (added later)

Basic characteristics of engraving gravure ink

Can test:

Water cleaning effect 〇〇 ◎ 〇〇 ◎ Non-staining performance 〇〇〇〇〇〇 Printing resistance to alkali □ □ □ □ □ O Printing sewage treatment 〇〇〇〇〇〇〇〇 Table 6

Material name Example 44 Example 45 Example 46 Example 47 Example 48 49 Alkyd resin adhesive ① 5. 0 ― ― 5. 0 5. 0 5. 0 Alkyd resin adhesive ② ― 5. 0 ― ―-― Alcohol Acid resin adhesive ③ ― ― 5. 0 ― ― ― Polyurethane resin adhesive ① 5. 5 5. 5 6. 0 ― ― urethane resin adhesive ② ― ― 6. 5 ― 6. 5 Unsaturated Polyester resin bonding ― One ― 7. 0 One dose ①

Unsaturated polyester resin bonding ― One ― 1. 8 1. 6 agent ② (added later)

Phenolic resin adhesive ⑥ 26. 5 26. 7 26. 5 27. 0 26. 5 27. 0 Phenolic resin adhesive ⑤ 7. 2 7. 0 7. 6 6. 8 7. 0 6. 8 Surface activity Agent 3. 1 3. 6 2. 5 3. 1 2. 8 3. 1 Mixed wax 6. 5 6. 3 6. 5 6. 6 6. 6 6. 6 Calcium carbonate 31.0 0 31. 4 31.3 31. 5 31. 3 31. 4 Organic yellow pigments 1. 3 "1. 3 1. 3 1. 3 1. 3 1. 3 Organic blue pigments 8. 7 8. 7 8. 7 8. 7 8. 7 8 . 7 Desiccant (added later) 2. 1 2. 0 2. 2 2. 1 2. 0 2. 0 Dibutyl phthalate (late 3. 1 2. 5 2. 4 1. 4 ― 1 Plus)

Basic characteristics of engraving gravure ink

Can test:

Water cleaning effect ○ ◎ ◎ 〇〇Stainless performance 〇〇〇〇〇 Alkali resistance of printed products □ □ □ □ □ Printing wastewater treatment 〇〇 OO OO Table 7

The above ink composition test indicators:

Viscosity: 4- 6Pa. S / 40 * C (HAAKE), fineness: less than 15 μ straight scrape, viscosity increase: 0, Drying speed: 15-18 minutes / 80 ° C; During the preparation process, the viscosity and dryness can be appropriately adjusted so that the index of the ink composition reaches the requirements.

The unconventional chemical materials used in Example 1-37 are as follows:

Phenolic resin ①: WY-206 high acid value rosin modified phenolic resin, softening point 125-135 ° C, acid value 140-150mgKOH / g, product of Beijing Wanyang Anti-counterfeiting Technology Co., Ltd .; phenolic resin ②: fY-216 high Acid value rosin modified phenol casein resin, softening point 143 ° C, acid value 145mgKOH / g, products of Beijing Wanyang Anti-counterfeiting Technology Co., Ltd .; phenol, lipid ③: WY-111 oil-soluble pure phenolic resin, softening point 113Ό, acid The value is 90mgKOH / g, Beijing Wanyang Anti-counterfeiting Technology Co., Ltd. product; Tungolinic acid: Beijing Wanyang Anti-counterfeiting Technology Co., Ltd. self-produced raw materials; # 6 adjusting ink: WY- 204 # 6 adjusting ink, Beijing Wanyang Anti-counterfeiting Products of Technology Co., Ltd .; Cooked tung oil: WY-205 cooked tung oil, Beijing Wanyang anti-counterfeiting technology ^ "Limited liability company product"; Polyethylene wax: LPE-3 polyethylene wax, Beijing Chemical University Fine Chemical Plant product; Paraffin wax: 58- 60Ό paraffin wax, product of Beijing Yanshan Petrochemical Company; epoxy resin: E-20; polypropylene glycol: average molecular weight 400; linoleic acid: self-produced product of Beijing Wanyang Anti-counterfeiting Technology Co., Ltd .;

Examples 8-19 are high acid value rosin modified phenolic resins, and Example 20 is an oil-soluble pure phenolic resin. Refer to the device and method of Example 1 and use the raw materials listed in the table above. According to different raw materials and varieties, the process control is omitted. There are different. Examples 2 and 29 are polymer adhesives. The devices and methods of Examples 1-7 can be used. The raw materials described in the table above are used. The process control is slightly different according to different raw materials and varieties. On the basis of Example 22, an appropriate amount of maleic acid and its liver or fumaric acid was added, reacted with vegetable oleic acid, and then neutralized with monoethanolamine to obtain a water-soluble modified phenolic resin adhesive; After adding an appropriate amount of maleic acid and its anhydride or fumaric acid, after reacting with vegetable oleic acid, diethylene glycol and / or triethylene glycol and / or tetraethylene glycol and / or dipropylene glycol and / or diethylene glycol are used. Tripropylene glycol and / or tetrapropylene glycol and / or polyether triol and / or polyether tetraol and / or polyether pentanol and / or polyethylene glycol with an average molecular weight of 200-9500 and / or One or more of 400-7000 polypropylene glycols are subjected to an esterification reaction to obtain a water-soluble modified phenolic resin binder, and at the same time, improve the physical and chemical fastness of the printed product. Examples 30-32 are dirtied water adjuvant engraving gravure ink composition in water is not rub smear variety intaglio ink composition adjuvants multi Gen 4, Examples ^30-32 only represent it. For Example 30, the apparatus and method of Example 3 can be referred to, and the raw materials described in the above table can be used to obtain a water-soluble unsaturated polyester resin. Ink or adhesive. For Example 31, referring to the apparatus and method of Example 7, using the raw materials described in the table above, ammonium alkylarylsulfonate can be obtained, which is an anionic surfactant. Example 32 is obtained by mixing and dissolving the raw materials described in the above table to obtain a mixed wax. Examples 33-36 are varnishes used in water-impartible engraving gravure printing ink compositions. There are many types of varnishes in 7j-impartible engraving gravure printing ink compositions. Examples 33-36 are just representative. Example 37 is a polymer binder for engraving gravure printing ink compositions which does not smudge with water.

The unconventional chemical materials used in Examples 38-55 are as follows:

Phenolic casein adhesive ①: WY-2061 high acid value rosin modified phenolic resin adhesive, viscosity 4-6Pa. S / 40 "C, acid value 55-65mgKOH / g, Beijing Wanyang anti-counterfeiting technology ^" Limit Responsible company products; Phenolic resin adhesive ②: WY-2064 high acid value rosin modified phenolic resin adhesive, viscosity 4-7Pa. S / 40 C, acid value 55-65mgKOH / g, Beijing Wanyang anti-counterfeiting technology ^ "Limited liability company products; Phenolic resin adhesives ③: WY-2065 high acid value rosin modified phenol casein adhesive, viscosity 4-6Pa. S / 40X, acid value 70-80mgKOH / g, Beijing Wanyang Anti-Counterfeiting Technical ^ Gen products from Responsible Company; Phenolic resin adhesive ④: WY-2066 high acid value rosin modified phenolic resin adhesive, viscosity 4-6Pa. S / 40 ° C, acid value 65-75mgKOH / g, Beijing Wan Foreign anti-counterfeiting technology ^ W limited liability company products; Phenolic resin adhesive ⑤: WY-1111 oil-soluble pure phenol casein adhesive, viscosity 9-10 Pa. S / 40 ° C, Beijing Wanyang Anti-counterfeiting Technology W limited liability company Product; Phenolic resin adhesive ⑥: WY-2161 high acid value rosin modified phenolic resin adhesive, viscosity 4-6Pa. S / 40 "Ό, acid value 55-65mgK0H / g, Beijing Wanyang anti-counterfeiting technology Products of the limited liability company; Alkyd resin adhesive ①: WY-2801 linseed oil modified alkyd resin adhesive, viscosity 4-6Pa. S / 40 * C, acid value less than 30mgKOH / g, Beijing Wanyang anti-counterfeiting technology Products of the limited liability company; Alkyd resin adhesive ②: WY-2802 water-soluble linseed oil modified alkyd resin adhesive, viscosity 4-6 Pa. S / 40 ° C, acid value less than 30mgKOH / g, Beijing Wan Products of Western Anti-counterfeiting Technology Co., Ltd .; Alkyd resin adhesives ③: WY-2803 water-soluble linseed oil modified alkyd resin adhesives, viscosity 4-6 Pa. S / 40 C, acid value less than 30mgKOH / g, Products of Beijing Wanyang Anti-counterfeiting Technology Co., Ltd .; Polyurethane resin adhesive①: WY-2901 polyurethane resin adhesive, viscosity 4-6 Pa. S / 40, acid value less than 15mgK0H / g, Beijing Wanyang Anti-counterfeiting Technology Co., Ltd. Company products; polyurethane resin adhesive ②: WY-2902 water-soluble polyurethane resin adhesive, viscosity 4-6Pa. S / 40 ° C, acid value less than 15mgK0H / g, Beijing Wanyang Anti-counterfeiting Technology Co., Ltd. product; no Saturated polyester resin bonding Agent ①: WY-5001 linoleic acid modified unsaturated polyester resin adhesive, viscosity 4-6 Pa. S / 40. C, acid value 70-80mgKOH / g, product of Beijing Wanyang Anti-counterfeiting Technology Co., Ltd .; unsaturated polyester resin adhesive ②: WY-5002 linoleic acid modified unsaturated polyester resin adhesive, viscosity 0. 5-4. OPa. S / 40 ° C, acid value 300-360mgKOH / g, product of Beijing Wanyang Anti-counterfeiting Technology Co., Ltd .; epoxy resin adhesive ①: WY-3001 epoxy resin adhesive, viscosity 4 -7Pa. S / 40, acid value 50-60mgKOH / g, products of Beijing Wanyang Anti-counterfeiting Technology Co., Ltd .; epoxy resin adhesive ②: W- 3002 water-soluble epoxy resin adhesive, viscosity 4-7Pa. S / 40O, acid value 55-65mgKOH / g, product of Beijing Wanyang Anti-counterfeiting Technology Co., Ltd .; scent and its derivative polyol ester resin adhesive ①: WY-2301 maleic acid modified rosin pentaerythritol ester resin Adhesive, viscosity 4-7Pa. S / 40O, acid value 55-65mgK0H / g, Beijing Wanyang anti-counterfeiting technology is a product of Pugu Responsible Company; rosin and its derivative polyol ester resin adhesive ②: WY- 2302 maleic acid-modified rosin ester resin binder polyether triol, viscosity ^{^{4 -. 7 Pa s / 40O}} , acid value 55-65mgKOH / g, Beijing Wanyang Products of Counterfeit Technology Co., Ltd .; Surfactants: WY-100 Ammonium Alkylbenzene Sulfonate, Beijing Wanyang Anti-Counterfeiting Technology Co., Ltd .; Mixed Wax: WY-1201 Mixed Wax, Beijing Wanyang Anti-Counterfeiting Technology ^ W Co., Ltd. Products; Calcium carbonate: Light calcium carbonate; Organic yellow pigment: benzidine yellow; Organic blue pigment: Phthalocyanine; Desiccant: Composite desiccant (combination of cobalt, manganese, zirconium), Beijing Wanyang Anti-counterfeiting Technology Co., Ltd. Company products; # 6 ink varnish: WY- 204 # 6 ink varnish, a product of Beijing Wanyang Anti-counterfeiting Technology Co., Ltd .; The basic performance evaluation test of the engraving gravure printing ink composition that is not wiped by dirt is as follows: Cleaning effect test:

A cleaning solution # 1 - 1% sulfonated castor oil; 1% NaOH; 2 # ^98% aqueous cleaning solution --- sulphonated castor oil 0.5%; sodium hydroxide, ^0.5%; water ^99% Polymer adhesive cleaning effect test: Test site temperature: 23-27 Ό, relative humidity 65-70%, cleaning liquid temperature 43-47 ° C. The polymer binder was made into a mixed polymer binder (without pigment), spread on a glass plate, and dripped a drop of # 1 cleaning solution or # ² cleaning solution, and observed the time when milky white appeared, in seconds. The evaluation results are expressed as 0 within 1 second as good; 0 as good within 2 seconds; medium as mouth within 3 seconds; and Δ as difference if above 3 seconds. The test of polymer adhesive's water cleaning effect is based on # 1 cleaning solution; the purpose is to reduce the content of sodium hydroxide and Taikoo oil in the water wiping liquid, that is, to aid the test of water-soluble polymer adhesive, using # 2 cleaning solution As the basis. Oil solubility test: The modified phenolic resin and oil-soluble pure phenol resin were dissolved in vegetable oil at a temperature of 5 ° C higher than the resin's softening point, and stirred for 10 minutes to observe the transparency of the polymer binder. The evaluation results were clear Transparency is indicated by excellent; Basic transparency is indicated by O; More transparent is indicated by mouth; Opaque is indicated by △.

Print abrasion resistance test: Printed product is the test sample, qualitative filter paper is a standard sample, and the printed product abrasion resistance test is performed on a Figuera abrasion tester. The temperature of the test place is 23-27 ° C and the relative humidity is 65-70%. The evaluation results are indicated by the qualitative filter paper standard after being rubbed, and no staining is preferred. The qualitative filter paper standard sample is slightly dirty after being rubbed (floating color). It is indicated by O for good quality. After the qualitative filter paper standard sample is rubbed, if there is dirt (not floating color, but with a slight ink stain), it is indicated by the mouth. The difference is represented by 厶.

Non-staining performance test: The non-staining performance test is based on the water-cleaning effect test of the polymer binder. The normal use of water-stained non-staining engraving gravure printing ink composition is used as a standard sample, and one of the polymers is replaced. After the adhesive or adjuvant is used, it is a test sample. Under the same printing conditions and the same amount of piled paper, a non-smudged performance test is performed. The evaluation result is indicated by no stain at all. There is almost no dirt on the back of the printed product, but only some parts-a deep pattern is slightly stained, but no obvious contour of the pattern is formed. It is good for O; it is less dirty (deep version on the back of the printed product) Grain spots are slightly stained, but no obvious contour of the pattern is formed), which is indicated by mouth; stains of dirt (dark patterns on the back of the printed product have obvious contours of the pattern) are indicated by Δ.

Alkali resistance test of printed products: The printed products are immersed in 2% sodium hydroxide aqueous solution, and left to stand at 25 ° C for 30 minutes. The evaluation result is that no change in the ink is better than 0; there is a slight change in the ink and the ink is Less than 5% of the sodium hydroxide soaked is indicated by good O; the ink has changed, and less than 20% of the ink soaked by sodium hydroxide is indicated by the mouth; the ink is changed, and the ink is soaked by sodium hydroxide The difference exceeding 20% is indicated by △.

Print wrinkle resistance test: The printed product is cut into a test specimen of 60 mm and 60 mm, and the print wrinkle resistance test is performed on an IGT wrinkle resistance tester. The temperature of the test place is 23-27 ° C, and the relative humidity is 65-70%. The evaluation result is that the ink has no change after the print is wrinkled. It is indicated by ◎. After the print is wrinkled, there is a slight ink loss. 5%) is good for O; printed ink is wrinkled, and ink is lost (less than 20%) is medium, □ is used for printing; Over 20%) is the difference expressed by Δ.

Printing wastewater treatment test: Printing wastewater treatment is to add emulsifier to the emulsified printing wastewater to make the emulsified printing wastewater (its composition is roughly a variety of organic pigments, a variety of inorganic materials, a variety of resins, Water in various vegetable oils, various ink adjuvants, various surfactants, various solvents, organic acids, inorganic acids, inorganic bases, water, etc.) is separated from other components. Water can be reused. The water-wiping non-staining engraving gravure printing ink composition, the polymer binder and auxiliary agent used, various surfactants, various solvents, etc., can all meet the requirements for printing wastewater treatment. In addition, the printing wastewater treatment effect can meet environmental protection requirements.

As described above, according to the present invention, it is possible to provide a water-erasable non-staining engraving gravure printing ink composition having good printability. The composition can effectively reduce the content of sodium hydroxide and Taikoo oil in water wipes (sodium hydroxide content is reduced from 1% to 0.5%, and the value of Taikoo oil is reduced from 1% to 0.5%), reducing the environment Pollution, the temperature of the ink fountain of the printing press (from 25-30Ό to uncontrolled), the temperature of the color film stick (from 25-30Ό to uncontrolled), the temperature of the color stick (from 35-38Ό to uncontrolled) The control range is greatly relaxed, and this condition is also applicable to light-varying ink (0VI), which provides looser printing conditions for printing.

Claims

Rights request

1. Water engraving does not stain the engraving gravure printing ink composition, which is composed of (A) pigment,

(B) polymer binder, (C) adjuvant, etc., characterized in that (A) pigment accounts for 5-55% of the total composition of the composition, (B) polymer binder accounts for the total of the composition 10-60% of the composition;

(C) Adjuvant accounts for 5-40% of the total composition of the composition, and (B) the polymer binder is selected from the group consisting of high acid value modified phenolic casein binder, oil-soluble pure phenolic casein resin Adhesives, modified alkyd resin adhesives, water-soluble modified alkyd resin adhesives, polyurethane resin adhesives, unsaturated polyester resin adhesives, epoxy resin adhesives, rosin and its derivatives One or more of the polyhydric alcohol ester resin binders; or solid resins, vegetable oils, varnishes, water-soluble polymer binders, polymer binders, surfactants, high-boiling solvents, A polymer binder mixture obtained by kneading or mixing two or more of other auxiliaries such as other adjuvants for engraving gravure printing ink composition with water rubbing without mixing.

2. The water-erasable non-staining engraving gravure printing ink composition according to claim 1, wherein the (B) polymer binder of the high acid value modified phenolic resin binder, High acid value modified phenolic resin, modified alkyd resin adhesive, 7J soluble modified alkyd resin adhesive, polyurethane resin adhesive, epoxy resin adhesive, rosin and its derivative polyol ester resin The molecular structure of the binder, rosin and its derivative polyol ester resin contains 0-40% ether groups; the molecular structure of the unsaturated polyester resin binder contains 0-70% ether groups.

3. The water-erasable non-staining engraving gravure printing ink composition according to claim 1, wherein the high acid value modified phenolic resin in the high acid value modified phenol casein binder is composed of (A) Composition of phenol, (B) aldehyde, (C) condensation catalyst, (D) modifier, (E) polyol, (F) neutralizer, etc., characterized by (A) phenol and (B) aldehyde condensation It accounts for 1-70% of the total composition of the resin.

(C) condensation catalyst accounts) 0.1-3.50% by weight of phenol, (D) modifying agent comprises from 1-95% of the total resin composition, (E) polyhydric alcohol accounts for ^0-40% of the total resin composition, ( F) neutralizing agent (neutralizing agent is limited to the preparation of water-soluble modified phenolic resin and / or water-soluble modified phenolic resin binder) accounts for 0-40% of the total composition of the resin, (A) 酴 and ( B) in a molar ratio of aldehyde: the range of 0.6 to ^2.5.

4. The water-erasable sculpted gravure printing ink composition according to claim 1, wherein the oil-soluble pure phenolic resin in the oil-soluble pure phenolic resin binder is composed of (A) phenol, (B) aldehyde, (C) condensation catalyst, etc., characterized in that the molar ratio of (A) phenol to (B) aldehyde is 1: 1.5-4, and (C) the condensation catalyst accounts for 0.1- 2%.

The water-erasable non-staining engraving gravure printing ink composition according to claim 1, wherein the water-soluble modified alkyd resin adhesive is composed of (A) a modifier, (B) a polyol, (C) a transesterification catalyst or an esterification catalyst, (D) an organic acid, (E) an esterification catalyst, (F) a sulfonating agent, (G) a neutralizing agent, etc., which is characterized by (A) a modifier It accounts for 1-90% of the total composition of the adhesive. (B) Polyol accounts for 1-49% of the total composition of the adhesive, (C) Transesterification catalyst or esterification catalyst accounts for 0 of the total composition of the adhesive -1%, (D) organic acid accounts for 1-50% of the total composition of the adhesive, (E) esterification catalyst accounts for 0-1% of the total composition of the adhesive, (F) the sulfonating agent is an excess,

(G) The neutralizing agent is an appropriate amount.

The water-erasable non-staining engraving gravure printing ink composition according to claim 1, wherein the modified alkyd resin binder is composed of (A) modifier, (B) polyol, (C ) A transesterification catalyst or an esterification catalyst, (D) an organic acid, (E) an esterification catalyst, etc., characterized in that (A) the modifier accounts for 1-90% of the total composition of the adhesive, (B) Polyol accounts for 1-49% of the total composition of the adhesive, (C) transesterification catalyst or esterification catalyst accounts for

0-1%, (D) organic acid accounts for 1-50% of the total composition of the adhesive, and (E) esterification catalyst accounts for 0-1% of the total composition of the adhesive.

The water-erasable non-staining engraving gravure printing ink composition according to claim 1, wherein the polyurethane resin binder is composed of (A) a polyol, (B) an organic acid, (C) a catalyst,

(D) composition of organic isocyanate, (E) blocking agent, etc., characterized in that (A) polyol accounts for 1-50% of the total composition of the adhesive, and (B) organic acid accounts for 1-90%, (C) catalyst 0-1% of the total composition of the binder, (D) organic isocyanate

1-50%, (E) the end-capping agent accounts for 0-15% of the total composition of the adhesive.

8. The water-smear-proof stain-gravure engraving gravure printing ink composition according to claim 1, wherein the polyurethane resin binder is composed of (A) vegetable oil or vegetable oleic acid, (B) polyol,

(C) a transesterification catalyst or an esterification catalyst, (D) an organic isocyanate, (E) an organic acid, (F) a catalyst, (G) a blocking agent, etc., characterized in that (A) vegetable oil or vegetable oleic acid accounts for the 1-90% of the total composition of the adhesive, (B) 1-49% of the total composition of the adhesive, (C) transesterification catalyst or esterification catalyst of 0-1 of the total composition of the adhesive %, (D) Organic isocyanate 1-50% of the total composition of the adhesive, (E) Organic acid 1-50% of the total composition of the adhesive, (F) Catalyst 0-1% of the total composition of the adhesive, (G The capping agent accounts for the total composition of the adhesive

0-15%.

The water-erasable non-staining engraving gravure printing ink composition according to claim 1, wherein the unsaturated polyester resin binder is composed of (A) a polyol, (B) an organic acid, and (C) Catalyst, (D) antioxidant, etc., characterized in that (A) polyhydric alcohol accounts for 25-80% of the total composition of the adhesive, and (B) organic acid accounts for 20-75% of the total composition of the adhesive (C) Catalyst accounts for 0-2.5% of the total composition of the adhesive, and (D) Antioxidant accounts for 0-2.5% of the total composition of the adhesive.

10. The water-erasable non-staining engraving gravure printing ink composition according to claim 1, wherein the epoxy resin adhesive is composed of (A) epoxy resin, (B) organic acid, and (C) multiple alcohol,

(D) a composition such as a neutralizer, characterized in that (A) epoxy resin accounts for

1-50%, (B) organic acid accounts for 1-50% of the total composition of the adhesive, (C) polyol accounts for 0-50% of the total composition of the adhesive, (D) neutralizer (neutralization The agent is limited to the preparation of water-soluble epoxy resin adhesive) accounting for 0-40% of the total composition of the adhesive.

The water-erasable non-staining engraving gravure printing ink composition according to claim 1, characterized in that, in the composition or the preparation process of the composition, or in the polymer binder and auxiliary used in the composition In the composition of the agent or in the preparation process, vegetable oil and / or varnish and / or high boiling point solvent are added to adjust the viscosity of the composition, or to adjust the viscosity of the polymer binder used in the composition, or to adjust the composition. The viscosity or state of the adjuvant used, where the high-boiling solvent refers to a non-toxic or low-toxic solvent with a boiling point higher than 210 ° C and / or allowed for use in food or food packaging and / or allowed for contact with food packaging Solvent.

12. The polymer binder or auxiliary agent for 7j non-smudgeable engraving gravure printing ink is characterized in that the composition of the polymer binder or auxiliary agent for non-smudgeable engraving gravure printing ink contains: Vegetable oils and / or varnishes and / or non-toxic or low-toxic solvents with a boiling point higher than 2101: and / or solvents allowed for food or food packaging and / or solvents allowed for food contact.