JP2022157067A - High solid ink composition for organic solvent-based gravure printing and gravure printing method - Google Patents

Abstract

To provide a high solid ink composition for organic solvent-based gravure printing which is reduced in odor, has good temporal stability, and has good printing density, printability and laminate suitability even when used for gravure printing using a shallowed printing plate, and a gravure printing method using the ink composition.SOLUTION: A high solid ink composition for organic solvent-based gravure printing contains a pigment, a binder resin and an organic solvent, where the pigment is an organic pigment and/or an inorganic pigment, the binder resin contains a specific polyurethane polyurea resin, and the pigment in the high solid ink composition for organic solvent-based gravure printing has a specific ratio.SELECTED DRAWING: None

Description

TECHNICAL FIELD The present invention relates to an organic solvent-based high solids ink composition for gravure printing and a gravure printing method.

Recently, dealing with environmental problems has become a business theme that should be addressed by all industries as a social responsibility, and of course the same applies to the field of plastic film printing.
However, printing on plastic films generally uses inks containing a large amount of organic solvents due to printability restrictions, which imposes a large burden on the environment. Therefore, manufacturers of inks and printed matter are working to solve environmental problems by reducing the amount of organic solvent emissions and developing simple treatment methods.

As one of such efforts, ink manufacturers are trying to reduce organic solvents contained in inks that have a higher environmental impact. For example, the content of organic solvents such as aromatics and ketones, which have a high environmental impact, has been reduced in conventional inks. Furthermore, in recent years, not only the types and composition ratios of organic solvents to be replaced, but also the overall materials used in ink such as binder resins and additives have been reviewed. As a result, ester-alcohol inks containing little or no aromatic or ketone solvents have been put to practical use.

On the other hand, as a solution to the environmental problems described above, printing companies are trying to minimize the emission of organic solvents in ink into the atmosphere during printing. As an example, by making the gravure printing plate depth (cell depth) shallower (shallower plate), it is possible to reduce the amount of ink used during printing and reduce the amount of organic solvents volatilizing into the atmosphere. Attempts have been made (see, for example, Patent Document 1).
However, as the gravure printing plate becomes shallower, the cell volume decreases and the transfer amount of the ink composition during printing decreases. Therefore, although the amount of the organic solvent in the ink composition can be suppressed, there is a problem that sufficient printing (color) density cannot be obtained if the amount of coloring agent in the ink film is also small due to the small amount of ink transfer. Therefore, in order to form a thin film and a coating with a high pigment concentration at the time of printing, an ink composition with a high pigment concentration is usually used for printing.

However, increasing the pigment concentration of the ink composition is a factor of increasing the viscosity of the ink, which relatively tends to lead to a reduction in plate fogging and doctor burnout.
In order to prevent such an ink composition from becoming highly viscous, a method of reducing the amount of other solids is known, but such a method leads to a decrease in the amount of the binder resin in the ink composition. Become. As a result, the ratio of the binder resin to the pigment is lowered, and the cohesion of the ink film is also lowered.
In order to solve this problem, the present applicant has developed organic solvent-based gravure printing high-performance resins using low-viscosity polyurethane polyurea resins having primary amino groups and/or secondary amino groups at their ends as binder resins. A solid ink composition has been proposed (see, for example, Patent Document 3). However, in order to obtain a low-viscosity polyurethane-polyurea resin, it is necessary to lower the molecular weight of the polyurethane-polyurea resin. When a polyurethane polyurea resin is prepared by a conventional method, a large amount of free amine is generated, and a high solid ink composition for organic solvent-based gravure printing using this has a problem of generating odor. In addition, the organic solvent-based high-solid ink composition for gravure printing tends to deteriorate in stability over time.

International Publication No. 2007/088733 JP 2013-231122 A International Publication No. 2017/098660

In the printing method for making the gravure printing plate shallower, it is necessary to increase the pigment concentration in the ink composition. There was a problem that the viscosity became high and the printed matter easily became dirty.
On the other hand, if the amount of the binder resin is reduced in order to lower the viscosity, the cohesive force of the ink film is lowered, resulting in a problem that the friction resistance and lamination suitability are lowered. Therefore, the polyurethane-polyurea resin used as the binder resin is a low-molecular-weight polyurethane-polyurea resin. However, this low-molecular-weight polyurethane-polyurea resin generates a large amount of free amine, and a high-solid ink composition for organic solvent-based gravure printing using this resin has problems such as generation of odor and deterioration of stability over time. had
Therefore, the problem to be solved by the present invention is that it has little odor, good stability over time, and good printing density and printability even when gravure printing is performed using a lightened printing plate. and to obtain a high-solids ink composition for organic solvent-based gravure printing having lamination suitability, and a gravure printing method using the high-solids ink composition for organic-solvent-based gravure printing.

The present inventors have found that the above problems can be solved by adopting an organic solvent-based high solids ink composition for gravure printing containing a specific polyurethane polyurea resin.
That is, the present invention is as follows.
1. A high solid ink composition for organic solvent-based gravure printing containing a pigment, a binder resin and an organic solvent,
The pigment is an organic pigment and / or an inorganic pigment,
The binder resin contains the following (A) and / or (B) polyurethane polyurea resin,
A high-solid ink composition for organic solvent-based gravure printing, wherein the pigment and the binder resin satisfy the following conditions 1 to 3.
(A) one or more polyurethane polyurea resins having a weight average molecular weight of 20,000 to 50,000 selected from the following (A-1) and (A-2): (A-1) reacting a diol compound and a diisocyanate compound; Polyurethane polyurea resin obtained by subjecting the resulting urethane prepolymer and a compound in which the amino group of the polyamine compound is ketiminized with a ketone compound to chain extension and reaction termination in an organic solvent (A-2) Diol compound and diisocyanate A urethane prepolymer obtained by reacting a compound is reacted with a reaction terminator in an organic solvent, and then chain elongation and reaction termination are performed with a compound in which the amino group of the polyamine compound is ketiminated with a ketone compound. Obtained polyurethane polyurea resin (B) one or more polyurethane polyurea resins having a weight average molecular weight of 20,000 to 50,000 selected from the following (B-1) and (B-2) (B-1) diol compound and diisocyanate To a urethane prepolymer solution of a urethane prepolymer obtained by reacting a compound and an organic solvent, a compound in which the amino group of a polyamine compound is ketiminized by a ketone compound is added and mixed with stirring. Polyurethane polyurea resin obtained by elongation and reaction termination (B-2) A reaction terminator is added to a urethane prepolymer solution of a urethane prepolymer obtained by reacting a diol compound and a diisocyanate compound with an organic solvent to react, Next, a polyurethane polyurea resin obtained by adding a compound in which the amino group of the polyamine compound is ketiminized with a ketone compound and stirring and mixing, and then adding water, followed by chain elongation and reaction termination (Condition 1)
When the pigment is an organic pigment, the content of the organic pigment in the organic solvent-based high solid ink composition for gravure printing is 5 to 20% by mass (Condition 2)
When the pigment is an inorganic pigment, the content of the inorganic pigment in the organic solvent-based high solid ink composition for gravure printing is 30 to 70% by mass (Condition 3)
When the pigment contains both an organic pigment and an inorganic pigment, the content of the organic pigment in the organic solvent-based high solid ink composition for gravure printing is 5 to 20% by mass, and the mass ratio of the inorganic pigment to the organic pigment is {Inorganic pigment (mass)/Organic pigment (mass)} is 0<Inorganic pigment (mass)/Organic pigment (mass)<7.0.
2. The polyurethane polyurea resin includes a polyurethane polyurea resin having a primary amino group at the terminal, a polyurethane polyurea resin having a primary amino group and a secondary amino group at the terminal, and a primary amino group at the terminal being ketimine. 2. The organic solvent-based high-solid ink composition for gravure printing according to 1, which is at least one selected from polyurethane polyurea resins having a group having a modified group.
3. 3. The organic solvent-based high solid ink composition for gravure printing according to 1 or 2, which contains a vinyl chloride/vinyl acetate copolymer and/or a vinyl chloride/acrylic copolymer as a binder resin.
4. At least one selected from rosin and its derivatives, chlorinated polypropylene, dammar resin as an adhesion improver, and silica particles, polyethylene wax, fatty acid amide, cellulose acetate propionate resin, cellulose acetate butyrate resin, and nitrocellulose as an antiblocking agent. 4. The organic solvent-based high-solid ink composition for gravure printing according to any one of 1 to 3, which contains 1 type.
5. 5. The organic solvent-based high-solid ink composition for gravure printing according to any one of 1 to 4, wherein the organic solvent is a mixed solvent of an ester-based organic solvent and an alcohol-based organic solvent.
6. At the time of gravure printing, an organic solvent-based high-solid ink composition for gravure printing is diluted by adding an organic solvent, and the organic solvent is a mixed solvent of an ester-based organic solvent and an alcohol-based organic solvent,
The ratio of the ester-based solvent and the alcohol-based organic solvent used in the organic solvent-based high-solid ink composition for gravure printing is ester-based organic solvent/alcohol-based organic solvent=50/50 to 95/5. 3. The organic solvent-based high solid ink composition for gravure printing according to .
7. 7. The high solids ink composition for organic solvent gravure printing according to 5 or 6, which contains 5% by mass or more of propyl acetate as an ester solvent in the high solids ink composition for organic solvent gravure printing.
8. A gravure printing method using the organic solvent-based high solids ink composition for gravure printing according to any one of 1 to 7,
preparing a high solids ink composition for organic solvent gravure printing by adding an organic solvent to the high solids ink composition for organic solvent gravure printing and diluting it;
A gravure printing method, wherein printing is performed by a gravure printing method using the high-solid ink composition for organic solvent-based gravure printing and using a shallow gravure plate.

According to the present invention, the organic solvent-based high-solids ink composition for gravure printing has good stability over time, and even when gravure printing is performed using a shallow printing plate, the printed matter does not have an odor. With a small amount, the effect of having good print density, printability, and lamination suitability can be exhibited.

The organic solvent-based high-solid ink composition for gravure printing of the present invention is described below.

<Pigment>
As the pigment, various inorganic pigments and organic pigments generally used in printing inks can be used.
Examples of the inorganic pigments include colored pigments such as titanium oxide, red iron oxide, antimony red, cadmium yellow, cobalt blue, Prussian blue, ultramarine blue, carbon black, graphite, silica, calcium carbonate, kaolin, clay, barium sulfate, and aluminum hydroxide. , extender pigments such as talc, aluminum paste containing aluminum particles surface-treated with acrylic resin, and pearl pigments such as mica whose surface is coated with titanium oxide, tin oxide and zirconium oxide.
Examples of the organic pigment include soluble azo pigments, insoluble azo pigments, azo lake pigments, condensed azo pigments, copper phthalocyanine pigments, and condensed polycyclic pigments.

The content of the pigment in the organic solvent-based high solid ink composition for gravure printing of the present invention is 5 to 20% by mass, preferably 6 to 15% by mass when the pigment is an organic pigment, and the pigment is an inorganic pigment. is 30 to 70% by mass, preferably 35 to 60% by mass.
Further, when both an organic pigment and an inorganic pigment are used as pigments, the content of the organic pigment in the organic solvent-based high solid ink composition for gravure printing is 5 to 20% by mass, and the ratio of the inorganic pigment to the organic pigment is A weight ratio {inorganic pigment (mass)/organic pigment (mass)} is preferably such that 0<inorganic pigment (mass)/organic pigment (mass)<7.0. And an organic pigment and an inorganic pigment can also be used together.
When the content of each of the organic pigment and the inorganic pigment in the organic solvent-based high solid ink composition for gravure printing of the present invention is less than the above range, the coloring power of the ink composition is lowered and the ink composition is used for gravure printing. It tends to be difficult to deal with shallow editions. On the other hand, when the amount is more than the above range, the viscosity becomes high, and there is a problem that the printed material tends to be stained during gravure printing.

<Binder resin>
The binder resin in the present invention contains the following (A) and/or (B) polyurethane polyurea resin.
(A) one or more polyurethane polyurea resins having a weight average molecular weight of 20,000 to 50,000 selected from the following (A-1) and (A-2): (A-1) reacting a diol compound and a diisocyanate compound; Polyurethane polyurea resin obtained by subjecting the resulting urethane prepolymer and a compound in which the amino group of the polyamine compound is ketiminized with a ketone compound to chain extension and reaction termination in an organic solvent (A-2) Diol compound and diisocyanate A urethane prepolymer obtained by reacting a compound is reacted with a reaction terminator in an organic solvent, and then chain elongation and reaction termination are performed with a compound in which the amino group of the polyamine compound is ketiminated with a ketone compound. Obtained polyurethane polyurea resin (B) one or more polyurethane polyurea resins having a weight average molecular weight of 20,000 to 50,000 selected from the following (B-1) and (B-2) (B-1) diol compound and diisocyanate To a urethane prepolymer solution of a urethane prepolymer obtained by reacting a compound and an organic solvent, a compound in which the amino group of a polyamine compound is ketiminized by a ketone compound is added and mixed with stirring. Polyurethane polyurea resin obtained by elongation and reaction termination (B-2) A reaction terminator is added to a urethane prepolymer solution of a urethane prepolymer obtained by reacting a diol compound and a diisocyanate compound with an organic solvent to react, Next, a polyurethane polyurea resin obtained by adding a compound in which the amino group of the polyamine compound is ketiminated with a ketone compound, stirring and mixing, and then adding water, followed by chain elongation and reaction termination. , a polyurethane polyurea resin having a primary amino group at the terminal, a polyurethane polyurea resin having a primary amino group and a secondary amino group at the terminal, and a primary amino group at the terminal being ketiminated It is preferably one or more selected from polyurethane polyurea resins having groups.

(Polyurethane polyurea resin of (A))
The polyurethane-polyurea resin (A) is one or more polyurethane-polyurea resins selected from (A-1) and (A-2), which are described below.
(A-1) is a urethane prepolymer obtained by reacting a diol compound and a diisocyanate compound, a compound in which the amino group of the polyamine compound is ketiminized with a ketone compound, chain extension and reaction termination in an organic solvent. It is a polyurethane polyurea resin obtained by performing.
(A-2) is obtained by reacting a urethane prepolymer obtained by reacting a diol compound and a diisocyanate compound with a reaction terminator in an organic solvent, and then ketiminating the amino group of the polyamine compound with a ketone compound. It is a polyurethane polyurea resin obtained by chain extension and reaction termination with a compound.
One or more polyurethane polyurea resins selected from (A-1) and (A-2) each have a weight average molecular weight of 20,000 to 50,000. Both are preferably 25,000 or more, and preferably 45,000 or less. If the weight-average molecular weight is less than 20,000, storage stability tends to decrease.
In addition, the weight average molecular weight of the present invention can be measured by a gel permeation chromatography (GPC) method. As an example, using Water2690 (manufactured by Waters) as a GPC apparatus, PLgel, 5μ, MIXED-D (manufactured by Polymer Laboratories) as a column, tetrahydrofuran as a developing solvent, column temperature 25 ° C., flow rate 1 ml / min, RI Chromatography is performed under the conditions of a detector, a sample injection concentration of 10 mg/ml, and an injection amount of 100 microliters, and the polystyrene equivalent weight average molecular weight can be determined.
Both (A-1) and (A-2) are preferably polyurethane polyurea resins having a terminal group in which a primary amino group is ketiminated. The polyurethane resin having a group in which a primary amino group is ketiminated at the terminal has a very high pigment dispersing effect compared to binder resins used in general ink compositions, and the pigment concentration in the ink composition is very high. is increased, the film cohesion of the ink composition is not lowered. Therefore, the high solids ink composition for organic solvent-based gravure printing containing the polyurethane resin having a group in which the primary amino group is ketiminated at the terminal is prepared using a shallow printing plate. Even if it is gravure printed, it has good print density, printability, and lamination suitability.

Diol compound As the diol compound used in (A-1) and (A-2) above, a polymer diol compound and a biopolyester diol compound can be used.
Examples of polymeric diol compounds include one or more of dibasic acids such as adipic acid, sebacic acid and phthalic anhydride, and ethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol, 3 -Polyester diols obtained by condensation reaction with one or more glycols such as methyl-1,5-pentanediol, polyester diol compounds such as polycaprolactone diols, polyethylene glycol, polypropylene glycol, etc. polyether diol compounds such as polyalkylene glycols of bisphenol A, ethylene oxide of bisphenol A, alkylene oxide adducts of propylene oxide, and the like. These polymer diol compounds can be used singly or in combination of two or more. Among them, 3-methyl-1,5-pentylene adipate diol having a number average molecular weight of 1,000 to 8,000 obtained by condensation reaction of adipic acid and 3-methyl-1,5-pentanediol is preferable, and moreover the number average molecular weight is 3-Methyl-1,5-pentylene adipate diol of 1000-4000 is preferred.

• Bio-polyester diol compound Bio-polyester polyol is used as the polyester polyol compound in consideration of the environment.
The biopolyester diol compound is preferably a biopolyester polyol compound obtained by reacting a short-chain diol component having 2 to 4 carbon atoms with a carboxylic acid component. At least one of the short-chain diol component and the carboxylic acid component is derived from plants. More preferably both are of plant origin.

The plant-derived short-chain diol component having 2 to 4 carbon atoms is not particularly limited. By way of example, the short chain diol component may be 1,3-propanediol, 1,4-butanediol, ethylene glycol, etc., obtained from plant sources by the following method. These may be used in combination.

1,3-Propanediol can be produced from glycerol via 3-hydroxypropylaldehyde (HPA) by a fermentation process in which plant sources (such as corn) are broken down to yield glucose. Compared to 1,3-propanediol compounds produced by EO production, 1,3-propanediol compounds produced by bio-methods such as the above fermentation method do not produce useful by-products such as lactic acid from the standpoint of safety. It is possible to obtain and keep the manufacturing cost low. 1,4-Butanediol can be produced by hydrogenating succinic acid obtained by producing and fermenting glycol from plant resources. Ethylene glycol can also be produced from bioethanol obtained by conventional methods via ethylene.

The plant-derived carboxylic acid component is not particularly limited. Examples of carboxylic acid components are sebacic acid, succinic acid, lactic acid, glutaric acid, dimer acid, and the like. These may be used in combination.
Among these, the carboxylic acid component preferably contains at least one selected from the group consisting of sebacic acid, succinic acid and dimer acid. Also, 0.05 to 0.5 parts by mass of malic acid may be contained with respect to 100 parts by mass of sebacic acid.

The biomass urethane prepolymer obtained from these plant-derived components preferably contains 10% by mass or more, more preferably 40% by mass or more, in terms of solid content in the total urethane prepolymer from an environmental point of view. .

Furthermore, in addition to the above polymer diol compounds, alkanediols such as 1,4-pentanediol, 2,5-hexanediol and 3-methyl-1,5-pentanediol, ethylene glycol, propylene glycol, 1,4- Low-molecular-weight diol compounds such as butanediol and 1,3-butanediol can be used singly or in combination of two or more.

Diisocyanate compound As the diisocyanate compound used in (A-1) and (A-2) above, an organic diisocyanate can be used.
Examples of organic diisocyanate compounds include 1,3- and/or 1,4-phenylene diisocyanate, 4,4-diisocyanatobiphenyl, 3,3-dimethyl-4,4-diisocyanatobiphenyl, tolylene diisocyanate, and the like. aromatic diisocyanate compounds, dicyclohexylmethane 4,4′-diisocyanate, 1,4-cyclohexane diisocyanate, cyclohexylene diisocyanate, dicyclohexylmethane-4,4-diisocyanate (hydrogenated MDI), methylcyclohexylene diisocyanate (hydrogenated TDI), Alicyclic diisocyanate compounds such as isophorone diisocyanate, hexamethylene diisocyanate (HDI), ethylene diisocyanate, tetramethylene diisocyanate, dodecamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, aliphatic diisocyanate compounds such as m- and/or p-xylylene diisocyanate (XDI), α, α, α', α'-tetramethyl xylylene diisocyanate and other araliphatic diisocyanate compounds, and these organic diisocyanate compounds may be used alone or in combination of two or more. Can be mixed and used. Among them, alicyclic diisocyanates, aliphatic diisocyanates and araliphatic diisocyanates are more preferred.

<Organic solvent>
The organic solvent used for obtaining the polyurethane polyurea resin (A-1) or (A-2) in the present invention is not particularly limited, but from the viewpoint of consideration for the environment, an aromatic hydrocarbon organic solvent is used. It is preferable not to contain. Examples of such solvents include alcohol-based organic solvents such as methanol, ethanol, n-propanol, isopropanol and butanol; ketone-based organic solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone; methyl acetate, ethyl acetate, propyl acetate and butyl acetate. n-hexane, n-heptane, n-octane and other aliphatic hydrocarbon organic solvents; cyclohexane, methylcyclohexane, ethylcyclohexane, cycloheptane, cyclooctane and other alicyclic hydrocarbon organic solvents Examples include solvents. At least one of the solvents may be used, and two or more of them may be used in combination in consideration of the solubility and drying properties of the binder resin.
However, from the viewpoint of consideration for the environment, it is preferable to suppress the use of ketone-based organic solvents among the above solvents. As a more preferable solvent, a mixed solvent of an ester solvent and an alcohol solvent is preferable. Furthermore, a solvent obtained by mixing isopropyl alcohol is preferable. Among them, a solvent obtained by mixing a mixed ester solvent and isopropyl alcohol at a ratio of 1 to 5:1 is more preferable.

- A compound in which the amino group of a polyamine compound is ketiminated with a ketone compound (polyamine compound)
As the polyamine compound used to obtain the polyurethane-polyurea resin (A-1) or (A-2) in the present invention, known polyamine compounds used in polyurethane-polyurea resins as binders for ink compositions can be used. For example, among polyamine compounds, aliphatic diamines such as ethylenediamine, propylenediamine, tetramethylenediamine, and hexamethylenediamine; alicyclic diamines such as isophoronediamine and 4,4′-dicyclohexylmethanediamine; aromatic diamines such as amines, araliphatic diamines such as xylenediamine, N-(2-hydroxyethyl)ethylenediamine (aminoethylethanolamine), N-(2-hydroxyethyl)propylenediamine, N,N'- Examples include diamines having a hydroxyl group such as di(2-hydroxyethyl)ethylenediamine, diol compounds such as ethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol, diethylene glycol and triethylene glycol.
Furthermore, polyamine compounds such as diethylenetriamine and triethylenetetramine can be used in combination as long as the polyurethane-polyurea resin does not gel.

(Compound in which the amino group of a polyamine compound is ketiminated with a ketone compound)
A polyamine compound obtained by converting a polyamine compound into a ketimine with an excess amount of a ketone compound in advance can be used. In particular, it is preferable to employ isophoronediamine and/or N-(2-hydroxyethyl)ethylenediamine as the polyamine compound.
A polyamine compound ketiminized with a ketone compound has a structure in which the oxygen atom of the ketone compound is substituted by the nitrogen atom of the amino group of the polyamine compound. Acetone, diethyl ketone, methyl ethyl ketone, and diacetone alcohol are preferable as the ketone compound to be used.
A compound in which the amino group of a polyamine compound is ketiminized by a ketone compound functions as chain elongation and reaction termination.
It is preferable not to use a solvent other than the ketone compound in this ketiminization reaction. An organic solvent other than the ketone compound may be blended as long as it does not impair the subsequent chain extension reaction and the effect that the polyurethane-polyurea resin has no odor.

Reaction terminator Examples of the reaction terminator used in obtaining the polyurethane polyurea resin (A-2) in the present invention include alkanolamines such as monoethanolamine and diethanolamine, and monoamines such as n-propylamine and n-butylamine. Known reaction terminating agents such as compounds, dialkylamines such as di-n-butylamine, and monoalcohol compounds such as ethanol can be used. Also in (A-1), the above reaction terminator that can be used in (A-2) can also be used as described below.

(Method for producing (A-1) polyurethane polyurea resin, (A-2) polyurethane polyurea resin))
The polyurethane-polyurea resin (A-1) is obtained by dissolving a urethane prepolymer obtained by reacting a diol compound and a diisocyanate compound in an organic solvent to form a urethane prepolymer solution, and then converting the amino groups of the polyamine compound into ketimines with a ketone compound. A polyurethane polyurea resin can be obtained by adding the above compound and performing chain elongation and reaction termination. In addition, after forming a urethane prepolymer solution, a compound in which the amino group of the polyamine compound is ketiminated with a ketone compound and a reaction terminator are added to carry out chain extension and reaction termination to obtain a polyurethane polyurea resin.
The polyurethane polyurea resin (A-2) is prepared by dissolving a urethane prepolymer obtained by reacting a diol compound and a diisocyanate compound in an organic solvent to form a urethane prepolymer solution, and then adding a reaction terminator to react with the urethane polymer. Next, a compound in which the amino group of the polyamine compound is ketiminized with a ketone compound is added, followed by chain elongation and reaction termination to obtain a polyurethane polyurea resin.

When the diisocyanate compound and the diol compound are reacted, the ratio of their use is such that the equivalent ratio of isocyanate group/hydroxyl group (isocyanate index) is usually 1.2 to 3.0, more preferably 1.3:1 to 2. .0. If the isocyanate index is less than 1.2, it tends to be a flexible polyurethane polyurea resin, and the blocking resistance etc. may be low when the ink composition is printed. It may be necessary to use them together.

A catalyst can be used during the reaction between the diisocyanate compound and the diol compound. Among them, it is preferable to use organometallic compounds, and examples of such organometallic compounds include titanium compounds such as dibutyl titanium dichloride, tetrabutyl titanate, and butoxy titanium trichloride, dibutyl tin sulfide, tributyl tin sulfide, and tributyl tin oxide. , dibutyltin dichloride, dibutyltin oxide, dibutyltin dibromide, dibutyltin dimaleate, dibutyltin dilaurate, dibutyltin diacetate, dioctyltin dilaurate, tributyltin acetate, tributyltin chloride, triethyltin ethoxide, tributyltin ethoxide, dioctyltin oxide , tributyltin trichloroacetate, and tin compounds such as tin 2-ethylhexanoate; lead compounds such as lead oleate, lead 2-ethylhexanoate, lead benzoate, and lead naphthenate; and iron 2-ethylhexanoate. , iron acetylacetonate, cobalt benzoate, cobalt 2-ethylhexanoate, zinc naphthenate, zinc 2-ethylhexanoate, zirconium naphthenate and the like. Among these, titanium compounds such as tetrabutyl titanate are preferred. Tertiary amine compounds can also be used, such as triethylamine, triethylenediamine, 1,4-diazabicyclo(2,2,2)octane, and 1,8-diazabicyclo(5,4,0)-undecene-7 (DBU). can be used.

(Polyurethane polyurea resin of (B))
The polyurethane-polyurea resin (B) is one or more polyurethane-polyurea resins selected from (B-1) and (B-2), which are described below.
(B-1) is a urethane prepolymer solution of a urethane prepolymer obtained by reacting a diol compound and a diisocyanate compound with an organic solvent, and a compound in which the amino group of the polyamine compound is ketiminated with a ketone compound is added and stirred. It is a polyurethane polyurea resin obtained by mixing, adding water, followed by chain extension and reaction termination.
(B-2) is obtained by reacting a urethane prepolymer obtained by reacting a diol compound with a diisocyanate compound and a urethane prepolymer solution in an organic solvent, adding a reaction terminator to the reaction, and then reacting the amino group of the polyamine compound with a ketone compound. is a polyurethane polyurea resin obtained by adding a ketiminized compound by stirring and mixing, further adding water, followed by chain elongation and reaction termination.
One or more polyurethane polyurea resins selected from (B-1) and (B-2) each have a weight average molecular weight of 20,000 to 50,000. Both are preferably 25,000 or more, and preferably 45,000 or less.
Both (B-1) and (B-2) are preferably polyurethane polyurea resins having groups in which primary amino groups are ketiminated at the ends. The polyurethane resin having a group in which a primary amino group is ketiminated at the terminal has a very high pigment dispersing effect compared to binder resins used in general ink compositions, and the pigment concentration in the ink composition is very high. is increased, the film cohesion of the ink composition is not lowered. Therefore, the high-solids ink composition for organic solvent-based gravure printing containing the polyurethane polyurea resin having a group in which the primary amino group is ketiminated at the end uses a shallow printing plate. Even if it is gravure-printed, it has good print density, printability, and lamination suitability. The amine value of the polyurethane polyurea resin is preferably 1 to 10 mgKOH/g. If the amine value is less than 1 mgKOH/g, for example, when laminated, the adhesiveness to the film may decrease, and further, the suitability for lamination may decrease. Blocking property may decrease.
In the present invention, the amine value means the amine value per 1 g of solid content, and is measured using a 0.1N aqueous solution of hydrochloric acid using a potentiometric titration method (e.g., COMTITE (AUTO TITRATOR COM-900, BURET B-900, TITSTATIONK -900), manufactured by Hiranuma Sangyo Co., Ltd.) and converted to the equivalent of potassium hydroxide.

The diol compound, the diisocyanate compound, the organic solvent, the reaction terminator, the compound in which the amino group of the polyamine compound is ketiminated with a ketone compound, and the catalyst used in the reaction between the diisocyanate compound and the diol compound are polyurethane polyurea resins (A). can be used.

(water)
The amount of water used is preferably within a range in which the polyurethane-polyurea resin obtained by the method for producing a polyurethane-polyurea resin solution does not precipitate. Specifically, it is preferably 0.2 to 5.0% by mass, more preferably 0.4 to 1.5% by mass, based on the solid content of the polyurethane-polyurea resin solution.

(Method for producing (B-1) polyurethane polyurea resin, (B-2) polyurethane polyurea resin))
The polyurethane polyurea resin (B-1) is obtained by dissolving a urethane prepolymer obtained by reacting a diol compound and a diisocyanate compound in an organic solvent to form a urethane prepolymer solution, and then adding an amino group of a polyamine compound to the urethane prepolymer solution. A polyurethane polyurea resin can be obtained by adding a compound ketiminized by a ketone compound, stirring and mixing, and then adding water, followed by chain elongation and reaction termination to obtain a polyurethane polyurea resin. After preparing the urethane prepolymer solution, a compound in which the amino group of the polyamine compound is ketiminated with a ketone compound and a reaction terminator are added and mixed with stirring to carry out chain extension and/or reaction termination to obtain a polyurethane polyurea resin. can also
The polyurethane polyurea resin (B-2) is obtained by dissolving a urethane prepolymer obtained by reacting a diol compound and a diisocyanate compound in an organic solvent to form a urethane prepolymer solution, and then adding a reaction terminator to the urethane prepolymer solution to form a urethane resin. A polyurethane polyurea resin is obtained by reacting with a polymer, then adding a compound in which the amino group of the polyamine compound is ketiminized with a ketone compound, stirring and mixing, further adding water, and then carrying out chain extension and reaction termination. can be done.

When the diisocyanate compound and the diol compound are reacted, the ratio of their use is such that the equivalent ratio of isocyanate group to hydroxyl group (isocyanate index) is usually 1.2:1 to 3.0:1, more preferably 1.2:1. It is in the range of 3:1 to 2.0:1. If the isocyanate index is less than 1.2, it tends to be a flexible polyurethane polyurea resin, and the blocking resistance etc. may be low when the ink composition is printed. It may be necessary to use them together.

<Organic solvent>
For the organic solvent-based high solids ink composition for gravure printing of the present invention, the organic solvents described in the binder resin can be used.
Furthermore, 0.1 to 20% by mass of a glycol ether organic solvent can be contained in 100% by mass of the organic solvent in order to improve the wetting and spreading properties. Specific examples of glycol ether-based organic solvents include ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol monoisopropyl ether, diethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, and ethylene glycol. Examples include monoisobutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, propylene glycol mono-n-propyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether and the like.

<Other compounds>
The organic solvent-based high-solid ink composition for gravure printing of the present invention contains vinyl chloride/vinyl acetate copolymers, vinyl chloride/acrylic copolymers, etc. as binder resins, rosin and its derivatives as adhesion improvers, Chlorinated polypropylene, dammar resin, anti-blocking agents such as silica particles, polyethylene wax, fatty acid amide, cellulose acetate propionate resin, cellulose acetate butyrate resin, nitrocellulose, etc., pigment dispersants and dispersing aids, organic solvents, water , an antistatic agent, and a silane coupling agent.

(Vinyl chloride/vinyl acetate copolymer as binder resin)
As the binder resin, a vinyl chloride/vinyl acetate copolymer can be used in combination with the polyurethane-polyurea resin in order to improve adhesion depending on the pigment to be blended.
As the vinyl chloride/vinyl acetate copolymer, vinyl chloride monomer and vinyl acetate monomer, which are conventionally used in gravure ink compositions, are essential components, and if necessary, vinyl propionate, vinyl monochloroacetate, Versatic Fatty acid vinyl monomers such as vinyl acid vinyl, vinyl laurate, vinyl stearate, and vinyl benzoate, and monomers having functional groups such as hydroxyl groups, which are produced by conventionally known methods, can be used.
Among them, the vinyl chloride/vinyl acetate copolymer has a hydroxyl group in the organic solvent system of the environmentally friendly ink composition, preferably vinyl chloride/acetic acid having a hydroxyl group value of 50 to 200 mgKOH/g. A vinyl copolymer is preferred. Such a vinyl chloride/vinyl acetate copolymer having a hydroxyl group can be obtained by saponifying a part of the acetate moiety and introducing a (meth)acrylic monomer having a hydroxyl group.
In the case of a vinyl chloride/vinyl acetate copolymer having a hydroxyl group obtained by saponifying a part of the acetate moiety, a structural unit based on the reaction site of vinyl chloride in the molecule (formula 1 below), acetic acid The physical properties and dissolution behavior of the resin are determined by the ratio of the structural unit based on the reactive site of vinyl (formula 2 below) and the structural unit based on saponification of the reactive site of vinyl acetate (formula 3 below). That is, the structural units based on the reactive sites of vinyl chloride impart toughness and hardness to the resin film, the structural units based on the reactive sites of vinyl acetate provide adhesiveness and flexibility, and the reactive sites of vinyl acetate are saponified. The structural unit based on imparts good solubility in organic solvent systems to the environmentally friendly ink composition.
Formula 1 -CH2-CHCl-
Formula 2 -CH2-CH(OCOCH ₃ )-
Formula 3 -CH2-CH(OH)-
Such vinyl chloride/vinyl acetate copolymers may be commercially available, for example, Solbin A, AL, TA5R, TA2, TA3, TAO, TAOL, C, CH, CN, CNL etc. can be mentioned.
The vinyl chloride/vinyl acetate copolymer used in the ink composition containing the polyurethane-polyurea resin obtained by the present invention has various properties in the molecule from the viewpoint of solubility in organic solvents and printability, which will be described later. It preferably has a functional group.
Further, when an environmentally friendly solvent is used as the organic solvent, the vinyl chloride/vinyl acetate copolymer preferably has 50 to 200 hydroxyl groups. Commercially available vinyl chloride/vinyl acetate copolymers such as Solbin A, AL, TA5R, TA2, TA3, TAO and TAOL manufactured by Nissin Chemical Industry Co., Ltd. are preferably used.

(Vinyl chloride/acrylic copolymer as binder resin)
As the binder resin, a vinyl chloride/acrylic copolymer can be used in combination with the polyurethane-polyurea resin in order to improve adhesion depending on the pigment to be blended.
The vinyl chloride/vinyl acetate copolymer is mainly composed of a copolymer of vinyl chloride and an acrylic monomer. The form of the copolymer is not particularly limited. For example, the acrylic monomer may be incorporated into the main chain of polyvinyl chloride in a block or random manner, or may be graft-copolymerized with the side chain of polyvinyl chloride. .
As the acrylic monomer, a (meth)acrylic acid ester, an acrylic monomer having a hydroxyl group, or the like can be used. Examples of (meth)acrylic acid esters include (meth)acrylic acid alkyl esters, and the alkyl group may be linear, branched, or cyclic, but linear alkyl groups are preferred. For example, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, cyclohexyl (meth)acrylate , 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, decyl (meth)acrylate, dodecyl (meth)acrylate, tetradecyl (meth)acrylate, hexadecyl (meth)acrylate, (meth)acrylic acid octadecyl and the like.
Examples of acrylic monomers having a hydroxyl group include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, Hydroxyalkyl (meth)acrylates such as 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, and 8-hydroxyoctyl (meth)acrylate; , polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, glycol mono(meth)acrylate such as 1,4-cyclohexanedimethanol mono(meth)acrylate, caprolactone-modified (meth)acrylate, hydroxyethylacrylamide, etc. mentioned.
Moreover, an acrylic monomer having a functional group other than a hydroxyl group can also be used as the acrylic monomer. Examples of functional groups other than hydroxyl groups include carboxyl groups, amide bond groups, amino groups, and alkylene oxide groups.
The vinyl chloride/acrylic copolymer resin preferably has a weight average molecular weight of 10,000 to 70,000.
Further, from the viewpoint of solubility in an environmentally friendly solvent as the organic solvent and adhesiveness to a substrate, the vinyl chloride/acrylic copolymer preferably has 50 to 200 hydroxyl groups.

When vinyl chloride/vinyl acetate copolymer or vinyl chloride/acrylic copolymer is contained as a binder resin, polyurethane polyurea resin and (vinyl chloride/vinyl acetate copolymer and/or vinyl chloride/acrylic copolymer combined) can be contained in a polyurethane polyurea resin/(vinyl chloride/vinyl acetate copolymer and/or vinyl chloride/acrylic copolymer)=100/0 to 45/55 (mass ratio). More preferably, this mass ratio may be 95/5 to 70/30. By containing the polyurethane polyurea resin and the vinyl chloride/vinyl acetate copolymer and/or the vinyl chloride/acrylic copolymer in such a ratio, the organic solvent-based high solid ink for gravure printing obtained by the present invention. The composition will have better printability and adhesion to films. Furthermore, when lamination is performed, it will have better lamination aptitude.
When the polyurethane polyurea resin/(vinyl chloride/vinyl acetate copolymer and/or vinyl chloride/acrylic copolymer) is less than 45/55, (vinyl chloride/vinyl acetate copolymer and/or vinyl chloride/ (acrylic copolymer) increases, the printed material formed using the organic solvent-based high solids ink composition for gravure printing obtained by the present invention becomes hard, and the adhesiveness to the film may become insufficient. have a nature.

(Rosin and its derivative as an adhesion improver)
Rosins include gum rosin, tall oil rosin, wood rosin and the like. Generally, rosin is an amber colored, amorphous resin obtained from pine trees, which is a mixture of abietic acid, neoabietic acid, parastric acid, pimaric acid, isopimaric acid, sandaracopimaric acid, Each component of dehydroabietic acid may be isolated and used, and these are also defined as rosin in the present invention.
Rosin derivatives are compounds obtained by modifying the above rosin, and are specifically listed below.
(1) Hydrogenated rosin: Rosin with improved weather resistance by adding hydrogen to conjugated double bonds (hydrogenation).
(2) Disproportionated rosin: Disproportionation is the reaction of two molecules of rosin to form two molecules of abietic acid with conjugated double bonds, one of which constitutes an aromatic and the other a single double It is the modification that becomes the binding molecule. Weather resistance is generally inferior to hydrogenated rosin, but better than untreated rosin.
(3) Rosin-modified phenolic resin: A rosin-modified phenolic resin is often used as a main binder in ink compositions for offset printing. A rosin-modified phenolic resin can be obtained by a known production method.
(4) Rosin ester: An ester resin derived from rosin, which has long been used as a tackifier for adhesives.
(5) Rosin-modified maleic acid resin: A resin obtained by subjecting rosin to an addition reaction with maleic anhydride, and optionally grafting a hydroxyl group-containing compound such as glycerin with an acid anhydride group through esterification.
(6) Polymerized rosin: a derivative containing dimerized resin acids derived from the natural resin rosin.
In addition, known rosin and rosin derivatives can also be used, and these can be used alone or in combination.
Furthermore, the acid value of rosin and rosin derivatives is preferably 120 mgKOH/g or more. When the acid value is 120 mgKOH/g or more, the lamination strength is improved. More preferably, the acid value is 160 mgKOH/g or more. The total amount of rosin and rosin derivative used is 3.0% by mass or less, preferably 0.1% to 3.0% by mass, in terms of solid content mass% of the organic solvent-based high solid ink composition for gravure printing of the present invention. It is 0% by mass.

(Chlorinated polypropylene as adhesion improver)
As chlorinated polypropylene, those having a degree of chlorination of 20 to 50 can be used. Chlorinated polypropylene having a degree of chlorination of less than 20 tends to have reduced compatibility with organic solvents. On the other hand, when the degree of chlorination exceeds 50, the chlorinated polypropylene tends to have reduced adhesion to films. Incidentally, the degree of chlorination is defined by mass % of chlorine atoms in the chlorinated polypropylene resin. Also, the chlorinated polypropylene is preferably modified or unmodified chlorinated polypropylene having a weight average molecular weight of 5,000 to 200,000. If the weight-average molecular weight is less than 5000, the chlorinated polypropylene tends to have poor adhesiveness. On the other hand, when the weight average molecular weight exceeds 200,000, the chlorinated polypropylene tends to be less soluble in organic solvents. The amount of chlorinated polypropylene used is 3.0% by mass or less, preferably 0.1% to 3.0% by mass, in solid content mass% of the organic solvent-based high-solid ink composition for gravure printing of the present invention. %.

(Dammar resin as adhesion improver)
Dammar resin is also described as dammar or dammer, and is a type of natural resin derived from plants. Specifically, it is a kind of natural resin obtained from Dipterocarpaceae or Bursiaceae plants that grow in Southeast Asia such as Malaysia and Indonesia. When used, it is dissolved in a suitable organic solvent to form a varnish. Since the dammar resin does not contain chlorine, chlorine can be eliminated or reduced compared to the case of using a chlorinated polyolefin resin in the ink composition. Further, the amount of dammar resin used is 3.0% by mass or less, preferably 0.1% to 3.0% by mass, in solid content mass% of the organic solvent-based high-solid ink composition for gravure printing of the present invention. is.

(Silica particles as antiblocking agent)
Examples of silica include naturally occurring silica, synthetic silica, crystalline silica, amorphous silica, hydrophobic silica, and hydrophilic silica. Silica particles preferably have an average particle size in the range of 1 to 5 μm (the average particle size of silica particles means the particle size at an integrated value of 50% (D50) in the particle size distribution, and is obtained by the Coulter counter method. can be done). The silica particles may be hydrophilic silica having a hydrophilic functional group on the surface, or hydrophobic silica obtained by modifying the hydrophilic functional group with an alkylsilane or the like to make it hydrophobic, but hydrophilic particles are preferred. An ink composition containing hydrophilic silica particles promotes wetting and spreading of the ink composition during overprinting, and also has the effect of improving the overprinting effect (hereinafter sometimes referred to as "trapping property"). The amount of silica particles used is 3.0% by mass or less, preferably 0.1 to 3.0% by mass, more preferably 0.2 to 1%, in the organic solvent-based high solids ink composition for gravure printing of the present invention. 0.5 mass %. If the content is more than 3.0% by mass, gloss tends to decrease.

(Polyethylene wax as antiblocking agent)
The polyethylene wax used has an average particle size in the range of 1.0 to 20 μm (the average particle size is #1: the particle size measured by Microtrac UPA manufactured by Honeywell). If the particle size of the polyethylene wax is smaller than 1.0 μm, the slipping property and blocking property during the production of the laminate are lowered, and if the particle size is larger than 20 μm, the trapping property is lowered. Moreover, the content of the polyethylene wax is preferably in the range of 0.1 to 1.5% by mass in the organic solvent-based high solid ink composition for gravure printing of the present invention. If the content is less than 0.1% by mass, the desired effect cannot be obtained, and if the content is more than 1.5% by mass, gloss tends to decrease.

(Fatty acid amide as antiblocking agent)
The fatty acid amide is not particularly limited as long as it has a fatty acid residue and an amide group.
Examples of fatty acid amides include monoamides, substituted amides, bisamides, methylolamides, esteramides, and the like, and are at least one selected from the group consisting of monoamides, substituted amides, and bisamides to improve blocking resistance. is preferred. The amount of fatty acid amide to be used is 1% by mass or less, preferably in the range of 0.01 to 1% by mass, in the organic solvent-based high-solids ink composition for gravure printing of the present invention.
- Monoamide: Monoamide is represented by the following general formula (1).
General formula (1) R1-CONH ₂
(Wherein, R1 represents a residue obtained by removing COOH from a fatty acid.)
Specific examples of monoamides include lauric acid amide, palmitic acid amide, stearic acid amide, behenic acid amide, hydroxystearic acid amide, oleic acid amide, and erucic acid amide.
• Substituted amide: A substituted amide is represented by the following general formula (2).
General formula (2) R2-CONH-R3
(Wherein, R2 and R3 represent residues obtained by removing COOH from a fatty acid, and may be the same or different.)
Specific examples of substituted amides include N-oleyl palmitic acid amide, N-stearyl stearic acid amide, N-stearyl oleic acid amide, N-oleyl stearic acid amide, N-stearyl erucic acid amide and the like.
- Bisamide: Bisamide is represented by the following general formula (3) or general formula (4).
General formula (3) R4-CONH-R5-HNCO-R6
General formula (4) R7-NHCO-R8-CONH-R9
(Wherein, R4, R6, R7, and R9 represent residues obtained by removing COOH from a fatty acid and may be the same or different, and R5 and R8 represent an alkylene group or an arylene group having 1 to 10 carbon atoms. )
Specific examples of bisamides include methylenebisstearic acid amide, ethylenebiscapric acid amide, ethylenebislauric acid amide, ethylenebisstearic acid amide, ethylenebishydroxystearic acid amide, ethylenebisbehenic acid amide, and hexamethylenebisstearic acid amide. , hexamethylenebisbehenamide, hexamethylenehydroxystearateamide, ethylenebisoleamide, ethylenebiserucamide, hexamethylenebisoleamide, N,N'-distearyladipamide, N,N'- distearylsebacic acid amide, N,N'-dioleyladipic acid amide, N,N'-dioleylsebacic acid amide and the like.
- Methylolamide: Methylolamide is represented by the following general formula (5).
General formula (5) R10-CONHCH ₂ OH
(Wherein, R10 represents a residue obtained by removing COOH from a fatty acid.)
Specific examples of methylolamide include methylol palmitic acid amide, methylol stearic acid amide, methylol behenic acid amide, methylol hydroxystearic acid amide, methylol oleic acid amide, methylol erucic acid amide and the like.
- Esteramide: Esteramide is represented by the following general formula (6).
General formula (6) R11-CONH-R12-OCO-R13
(Wherein, R11 and R13 represent a residue obtained by removing COOH from a fatty acid and may be the same or different, and R12 represents an alkylene group having 1 to 10 carbon atoms or an arylene group.)
Specific examples of esteramides include stearamidoethyl stearate and oleylamidoethyl ureate.
The melting point of the fatty acid amide is preferably 50°C to 150°C.
Further, the fatty acid constituting the fatty acid amide is preferably a saturated fatty acid having 12 to 22 carbon atoms and/or an unsaturated fatty acid having 16 to 25 carbon atoms, and a saturated fatty acid having 16 to 18 carbon atoms and/or a saturated fatty acid having 18 to 22 carbon atoms. unsaturated fatty acids are more preferred. Particularly preferred saturated fatty acids are lauric acid, palmitic acid, stearic acid, behenic acid and hydroxystearic acid, and particularly preferred unsaturated fatty acids are oleic acid and erucic acid.

(Cellulose Acetate Propionate Resin as Antiblocking Agent)
As the cellulose acetate propionate resin, cellulose acetate propionate resins conventionally used in gravure ink compositions and the like can be used.
Cellulose acetate propionate resin is obtained by hydrolyzing after tri-esterifying cellulose with acetic acid and propionic acid. In general, resins containing 0.6 to 2.5% by mass of acetyl groups, 42 to 46% by mass of propionate groups, and 1.8 to 5% by mass of hydroxyl groups are commercially available. The amount of the cellulose acetate propionate resin used is preferably 3.0% by mass or less in the organic solvent-based high solids ink composition for gravure printing of the present invention.

(Cellulose Acetate Butyrate Resin as Antiblocking Agent)
As the cellulose acetate butyrate resin, cellulose acetate butyrate resins conventionally used in gravure ink compositions and the like can be used.
Cellulose acetate butyrate resin is obtained by hydrolysis after triesterification with acetic acid and butyric acid. In general, resins containing 2 to 30% by mass of acetylation, 17 to 53% by mass of butyrylation, and 1 to 5% of hydroxyl groups are commercially available. The amount of the cellulose acetate butyrate resin used is preferably in the range of 0.1 to 3.0% by mass in the organic solvent-based high solids ink composition for gravure printing of the present invention.

(Nitrate cotton as anti-blocking agent)
As the nitrocellulose, nitrocellulose that has been conventionally used in gravure ink compositions and the like can be used. The nitrocellulose is obtained by reacting natural cellulose with nitric acid to replace three hydroxyl groups in the 6-membered ring of the anhydride glucopyranose group in the natural cellulose with nitric acid groups. As the nitrocellulose used in the present invention, those having a nitrogen content of 10 to 13% and an average degree of polymerization of 35 to 90 are preferably used. Specific examples include SS1/2, SS1/4, SS1/8, TR1/16, NC RS-2, (KCNC, manufactured by KOREA CNC LTD) and the like. The amount of nitrocellulose used is preferably in the range of 2.0% by mass or less in the organic solvent-based high-solid ink composition for gravure printing obtained by the production method of the present invention.

(Pigment dispersant)
As the pigment dispersant, a polyester-based pigment dispersant that can be used in ink compositions such as gravure ink compositions generally containing an organic solvent can be used. Specifically, Ajisper PB821, PB822, PB824, PB881 (manufactured by Ajinomoto Fine-Techno Co., Ltd.), Solsperse 24000, 56000 (manufactured by Nippon Lubrizol Co., Ltd.) and the like can be mentioned. can be preferably used.
The content of the pigment dispersant is generally preferably 1 to 200 parts by mass, more preferably 1 to 60 parts by mass, based on 100 parts by mass of all pigments.

(water)
Polyurethane polyurea resin solutions contain water, and water is contained in organic solvent-based gravure printing high-solid ink compositions in order to alleviate printing defects due to static electricity, prevent plate fogging, and improve cell reproducibility. The amount is preferably 10% by weight or less, more preferably in the range of 0.1 to 5.0% by weight.

<Method for producing organic solvent-based high solid ink composition for gravure printing>
As a method for producing the organic solvent-based high solids ink composition for gravure printing of the present invention using each constituent material, a known method can be used. Specifically, for example, a mixture of a polyurethane polyurea resin solution, a pigment, and, if necessary, a binder resin, an organic solvent, a pigment dispersant, etc., is kneaded using a high-speed mixer, ball mill, sand mill, attritor, or the like, and then kneaded. , an adhesion improver, an antiblocking agent, an organic solvent, an antistatic agent, water and the rest of the materials are added and mixed.

<Method for producing laminated printed matter using the organic solvent-based high-solids ink composition for gravure printing obtained by the production method of the present invention>
A method for obtaining a laminate printed matter using the organic solvent-based high-solids ink composition for gravure printing obtained by the production method of the invention will be described.
Methods for obtaining laminated prints include at least the following printing methods. For example, an ink composition for gravure printing is printed at least one time or more on a known resin film serving as a base material for lamination by a gravure printing method. Next, another ink composition for gravure printing is printed by a gravure printing method on any part of the surface side of the ink composition for gravure printing (after the final lamination, the lower layer side when viewed from the surface layer) formed by these printings. and dry with a dryer.
A laminated printed matter for packaging bags can be obtained by laminating a resin film or the like by various methods on the side of the layer of the organic solvent gravure high solid ink composition of the printed matter obtained by the above method. can. The lamination process includes the extrusion lamination method, in which an anchor coating agent is applied to the surface of the printed matter and then laminated with a molten polymer, and the dry lamination method, in which an adhesive is applied to the surface of the printed matter and then a film-like polymer is laminated. A lamination method can be used.

In the above extrusion lamination method, the surface of the printed material including the layer of the organic solvent-based high-solid ink composition for gravure printing is coated with an anchor coating agent such as titanium, urethane, imine, or polybutadiene, if necessary. After that, a known extrusion lamination machine is used to laminate a molten polymer. Further, a molten resin can be used as an intermediate layer to laminate other materials in a sandwich form.
Conventionally used resins such as low-density polyethylene, ethylene-vinyl acetate copolymer, and polypropylene can be used as the molten polymer used in the extrusion lamination method. Among them, low-density polyethylene, which is easily oxidized to generate carbonyl groups when melted, enhances the effect of the present invention.

In the above dry lamination method, after applying a urethane-based or isocyanate-based adhesive to the surface of a layer made of an organic solvent-based gravure printing high-solid ink composition, a film-like polymer is formed by a known dry lamination machine. It is a method of bonding. Polyethylene, non-stretched polypropylene, and the like can be used as the resin for the film used in the dry lamination method.
In order to obtain a packaging material that is particularly used for retort applications, it is also possible to laminate by sandwiching an aluminum foil between the substrate and the resin film to be laminated. Such a laminated product can also be used for boiling and retorting after making a bag and filling it with contents.
Examples of the resin film used at this time include stretched and non-stretched polyolefins such as polyethylene and polypropylene, polyester, nylon, cellophane, and vinylon. Further, for these resin films, it is also possible to use a film obtained by processing a resin film in advance, such as coating and kneading an antifogging agent, surface coating and kneading a matting agent.

EXAMPLES The present invention will be described in more detail below with reference to Examples, but the present invention is not limited only to these Examples. Unless otherwise specified, "%" means "% by mass" and "parts" means "parts by mass". In addition, the number of the amount of each material in the table is also "mass part". The unit of acid value is mgKOH/g.

<Method for producing ketimine solution 1>
51 parts of isophoronediamine, 31.2 parts of N-(2-hydroxyethyl)ethylenediamine, and 174 parts of acetone were mixed and stirred at room temperature for 1 hour to obtain a ketimine solution 1.

<Method for producing ketimine solution 2>
51 parts of isophoronediamine, 31.2 parts of N-(2-hydroxyethyl)ethylenediamine, and 258 parts of diethylketone were mixed and stirred at room temperature for 1 hour to obtain a ketimine solution 3.

Polyurethane resin varnish is described as PU.
<Method for producing PU-1 (ketimine conversion with acetone)>
400 parts of 3-methyl-1,5-pentylene adipate diol having a number average molecular weight of 4000, 33.3 parts of isophorone diisocyanate and 0 of tetrabutyl titanate were added to a four-necked flask equipped with a stirrer, a condenser tube and a nitrogen gas inlet tube. 0.04 part was charged and reacted at 90 to 100° C. for 6 hours while nitrogen gas was introduced.
Next, after adding 812 parts of propyl acetate and 203 parts of isopropyl alcohol, the mixture was cooled to near room temperature, 32.29 parts of ketimine solution 1 was added, and the mixture was stirred for 50 minutes. 30%) was obtained.

<Method for producing PU-2 (ketimine conversion with diethyl ketone)>
400 parts of 3-methyl-1,5-pentylene adipate diol having a number average molecular weight of 4000, 33.3 parts of isophorone diisocyanate and 0 of tetrabutyl titanate were added to a four-necked flask equipped with a stirrer, a condenser tube and a nitrogen gas inlet tube. 0.04 part was charged and reacted at 90 to 100° C. for 6 hours while nitrogen gas was introduced.
Next, after adding 803 parts of propyl acetate and 201 parts of isopropyl alcohol, the mixture was cooled to near room temperature, 42.88 parts of ketimine solution 2 was added, and the mixture was stirred for 50 minutes. 30%) was obtained.

<Method for producing PU-3 (ketimine conversion with acetone)>
400 parts of 3-methyl-1,5-pentylene adipate diol having a number average molecular weight of 4000, 33.3 parts of isophorone diisocyanate and 0 of tetrabutyl titanate were added to a four-necked flask equipped with a stirrer, a condenser tube and a nitrogen gas inlet tube. 0.04 part was charged and reacted at 90 to 100° C. for 6 hours while nitrogen gas was introduced.
Next, after adding 810 parts of propyl acetate and 202 parts of isopropyl alcohol, the mixture was cooled to near room temperature, 30.78 parts of ketimine solution 1 was added, and the mixture was stirred for 50 minutes. 30%) was obtained.

<Method for producing PU-4 (ketimine conversion with acetone)>
400 parts of 3-methyl-1,5-pentylene adipate diol having a number average molecular weight of 4000, 33.3 parts of isophorone diisocyanate and 0 of tetrabutyl titanate were added to a four-necked flask equipped with a stirrer, a condenser tube and a nitrogen gas inlet tube. 0.04 part was charged and reacted at 90 to 100° C. for 6 hours while nitrogen gas was introduced.
After adding 810 parts of propyl acetate and 202 parts of isopropyl alcohol, cool to near room temperature, add 36.56 parts of ketimine solution 1 and stir for 50 minutes to obtain a weight average molecular weight of 25,000 PU-4 (solid content: 30%). Obtained.

<Method for producing PU-5 (monoethanolamine, ketimine with acetone)>
400 parts of 3-methyl-1,5-pentylene adipate diol having a number average molecular weight of 4000, 33.3 parts of isophorone diisocyanate and 0 of tetrabutyl titanate were added to a four-necked flask equipped with a stirrer, a condenser tube and a nitrogen gas inlet tube. 0.04 part was charged and reacted at 90 to 100° C. for 6 hours while nitrogen gas was introduced.
After adding 810 parts of propyl acetate and 202 parts of isopropyl alcohol, the mixture was cooled to near room temperature, 0.6 parts of monoethanolamine was added, and after stirring for 15 minutes, 32.39 parts of ketimine solution 1 was further added and stirred for 50 minutes. , and a weight average molecular weight of 25,000 PU-5 (solid content 30%).

<Method for producing PU-6 (biomass, monoethanolamine, ketimine with acetone)>
Sebacic acid (derived from castor oil) / succinic acid (derived from plant) having a number average molecular weight of 4000 = 70/30 (mass ratio) and 1,3- 400 parts of a polyester diol having an average molecular weight of 4000 obtained from propanediol (derived from a plant), 33.3 parts of isophorone diisocyanate and 0.04 part of tetrabutyl titanate were charged and reacted at 90 to 100° C. for 6 hours while introducing nitrogen gas. rice field.
After adding 810 parts of propyl acetate and 202 parts of isopropyl alcohol, the mixture was cooled to near room temperature, 0.6 parts of monoethanolamine was added, and after stirring for 15 minutes, 32.39 parts of ketimine solution 1 was further added and stirred for 50 minutes. , and a weight average molecular weight of 25,000 PU-6 (solid content 30%).

<Method for producing PU-7 (ketimine with water and acetone)>
400 parts of 3-methyl-1,5-pentylene adipate diol having a number average molecular weight of 4000, 33.3 parts of isophorone diisocyanate and 0 of tetrabutyl titanate were added to a four-necked flask equipped with a stirrer, a condenser tube and a nitrogen gas inlet tube. 0.04 part was charged and reacted at 90 to 100° C. for 6 hours while nitrogen gas was introduced.
Next, after adding 812 parts of propyl acetate and 203 parts of isopropyl alcohol, the mixture was cooled to near room temperature, 32.29 parts of ketimine solution 1 was added and stirred for 20 minutes, and 3 parts of water was further added and stirred for 15 minutes. PU-7 (30% solids content) having an average molecular weight of 35,000 and an amine value of 6.5 was obtained.

<Method for producing PU-8 (ketiminization with water and diethyl ketone)>
400 parts of 3-methyl-1,5-pentylene adipate diol having a number average molecular weight of 4000, 33.3 parts of isophorone diisocyanate and 0 of tetrabutyl titanate were added to a four-necked flask equipped with a stirrer, a condenser tube and a nitrogen gas inlet tube. 0.04 part was charged and reacted at 90 to 100° C. for 6 hours while nitrogen gas was introduced.
Next, after adding 803 parts of propyl acetate and 201 parts of isopropyl alcohol, the mixture was cooled to near room temperature, 42.88 parts of ketimine solution 2 was added and stirred for 20 minutes, and 3 parts of water was added and stirred for 15 minutes. PU-8 (30% solids) having an average molecular weight of 35,000 and an amine value of 6.5 was obtained.

<Method for producing PU-9 (ketimine with water and acetone)>
400 parts of 3-methyl-1,5-pentylene adipate diol having a number average molecular weight of 4000, 33.3 parts of isophorone diisocyanate and 0 of tetrabutyl titanate were added to a four-necked flask equipped with a stirrer, a condenser tube and a nitrogen gas inlet tube. 0.04 part was charged and reacted at 90 to 100° C. for 6 hours while nitrogen gas was introduced.
Next, after adding 810 parts of propyl acetate and 202 parts of isopropyl alcohol, the mixture was cooled to near room temperature, 30.78 parts of ketimine solution 1 was added and stirred for 20 minutes, and 3 parts of water was added and stirred for 15 minutes. PU-9 (solid content 30%) having an average molecular weight of 40,000 and an amine value of 5.57 was obtained.

<Method for producing PU-10 (ketimine with water and acetone)>
400 parts of 3-methyl-1,5-pentylene adipate diol having a number average molecular weight of 4000, 33.3 parts of isophorone diisocyanate and 0 of tetrabutyl titanate were added to a four-necked flask equipped with a stirrer, a condenser tube and a nitrogen gas inlet tube. 0.04 part was charged and reacted at 90 to 100° C. for 6 hours while nitrogen gas was introduced.
After adding 810 parts of propyl acetate and 202 parts of isopropyl alcohol, cool to near room temperature, add 36.56 parts of ketimine solution 1, stir for 20 minutes, add 3 parts of water, stir for 15 minutes, and stir for 50 minutes. to obtain PU-10 (solid content: 30%) having a weight average molecular weight of 25,000 and an amine value of 8.95.

<Method for producing PU-11 (water, monoethanolamine, ketimine with acetone)>
400 parts of 3-methyl-1,5-pentylene adipate diol having a number average molecular weight of 4000, 33.3 parts of isophorone diisocyanate and 0 of tetrabutyl titanate were added to a four-necked flask equipped with a stirrer, a condenser tube and a nitrogen gas inlet tube. 0.04 part was charged and reacted at 90 to 100° C. for 6 hours while nitrogen gas was introduced.
After adding 810 parts of propyl acetate and 201 parts of isopropyl alcohol, the mixture was cooled to near room temperature, 0.6 parts of monoethanolamine was added, and after stirring for 15 minutes, 32.3 parts of ketimine solution 1 was further added and stirred for 20 minutes. Further, 3 parts of water was added and stirred for 15 minutes to obtain PU-11 (solid content: 30%) having a weight average molecular weight of 25,000 and an amine value of 7.74.

<Method for producing PU-12 (water, biomass, monoethanolamine, ketimine with acetone)>
Sebacic acid (derived from castor oil) / succinic acid (derived from plant) having a number average molecular weight of 4000 = 70/30 (mass ratio) and 1,3- A polyester diol having an average molecular weight of 4000 obtained from propanediol (derived from a plant), 33.3 parts of isophorone diisocyanate and 0.04 part of tetrabutyl titanate were charged and reacted at 90 to 100° C. for 6 hours while introducing nitrogen gas.
After adding 810 parts of propyl acetate and 201 parts of isopropyl alcohol, the mixture was cooled to near room temperature, 0.6 parts of monoethanolamine was added, and after stirring for 15 minutes, 32.35 parts of ketimine solution 1 was further added and stirred for 20 minutes. Further, 3 parts of water was added and stirred for 15 minutes to obtain PU-12 (solid content: 30%) having a weight average molecular weight of 45,000 and an amine value of 7.74.

<Method for producing PU-13 (without ketiminization)>
400 parts of 3-methyl-1,5-pentylene adipate diol having a number average molecular weight of 4000, 33.3 parts of isophorone diisocyanate and 0 of tetrabutyl titanate were added to a four-necked flask equipped with a stirrer, a condenser tube and a nitrogen gas inlet tube. 0.04 part was charged and reacted at 90 to 100° C. for 6 hours while nitrogen gas was introduced.
Next, after adding 813.5 parts of propyl acetate and 202.8 parts of isopropyl alcohol, the mixture was cooled to near room temperature, added with 4.3 parts by mass of monoethanolamine and stirred for 20 minutes, followed by 1.26 parts of isophoronediamine and N. 0.77 part of -(2-hydroxyethyl)ethylenediamine was added and mixed with stirring for 20 minutes to obtain PU-13 (solid content: 30%) having a weight average molecular weight of 25,000 and an amine value of 0.

<Method for producing PU-14 (chain elongation followed by ketiminization with acetone)>
400 parts of 3-methyl-1,5-pentylene adipate diol having a number average molecular weight of 4000, 33.3 parts of isophorone diisocyanate and 0 of tetrabutyl titanate were added to a four-necked flask equipped with a stirrer, a condenser tube and a nitrogen gas inlet tube. 0.04 part was charged and reacted at 90 to 100° C. for 6 hours while nitrogen gas was introduced.
Next, after adding 803 parts of propyl acetate and 201 parts of isopropyl alcohol, the mixture was cooled to near room temperature, and 6.43 parts of isophoronediamine and 3.93 parts of N-(2-hydroxyethyl)ethylenediamine were added and mixed with stirring for 20 minutes. After elongation and termination of the reaction, 21.93 parts of acetone was added and stirred for 60 minutes to obtain PU-14 (solid content: 30%) with a weight average molecular weight of 35,000.

(vinyl chloride-vinyl acetate resin)
Solbin TA-3, manufactured by Nissin Chemical Industry Co., Ltd.

(pigment)
Titanium oxide: R-960, manufactured by DuPont Phthalocyanine Blue: C.I. I. PB15:4

(Adhesion improver)
<Rosin and its derivatives>
Polymerized rosin (acid value 160 mgKOH/g)

<Chlorinated polypropylene>
40 parts by mass of chlorinated polypropylene (solid content: 50%) having a chlorination degree of 40% and a number average molecular weight of 100,000 and 60 parts by mass of methylcyclohexane were mixed and stirred to obtain a chlorinated polypropylene varnish 1 with a solid content of 20%.

<Dammar resin>
50 parts of commercially available natural dammar resin (solid) was dissolved in 50 parts of methylcyclohexane to obtain a dammar resin solution having a solid content of 50%.

<Silica particles>
Average particle size: 4.5 μm

<Polyethylene wax>
Average particle size: 2.11 μm

<Fatty acid amide>
Ethylene bis stearamide

<Production Examples of Ink Compositions of Examples and Comparative Examples>
Pigments, polyurethane polyurea resin varnishes (PU-1 to PU-14), silica and solvents were kneaded using a paint conditioner manufactured by Red Devil to obtain ink compositions of Examples and Comparative Examples shown in Table 1. .

<Stability of ink composition over time>
The ink compositions of Examples and Comparative Examples obtained above were sampled in glass bottles, and the change in viscosity value before and after aging at 40°C for 14 days (the viscosity at a liquid temperature of 25°C was The viscosity stability over time was evaluated from the ink viscosity measurement data at 30 rpm using a No. 2 rotor manufactured by Keiki Co., Ltd. The results are shown in Table 1.
Good: The viscosity ratio after aging/before aging was less than 1.5.
x: The viscosity ratio after aging/before aging was 1.5 or more.

<Print>
100 parts by mass of each of the ink compositions of Examples and Comparative Examples was diluted with a mixed solvent (ethyl acetate/propyl acetate/isopropyl alcohol = 50/25/25, mass ratio), and the viscosity was adjusted to Zahn Cup No. 3 manufactured by Rigo Co., Ltd. was adjusted to 15 seconds. Using a gravure printing machine, each diluted ink composition was printed on the treated surface of various films under the following conditions and dried to obtain prints. Moreover, the amine odor was evaluated using the obtained printed matter. A specific evaluation method is shown below.
(Printing method/Printing conditions)
Room environment during printing: temperature 25°C, humidity 50%
Coating machine: gravure printing machine
Coating speed: 150m/min
Printing plate: Direct 175 line 28 μm solid plate Drying temperature: 55°C

(Various films)
OPP: Biaxially oriented polypropylene film treated with corona discharge, P-2161 manufactured by Toyobo Co., Ltd., thickness 25 μm
PET (film): polyethylene terephthalate film with corona discharge treatment on one side, manufactured by Toyobo Co., Ltd., E-5102, thickness 12 μm
NY: Nylon film, manufactured by Toyobo Co., Ltd., N-1102, thickness 15 μm

(Ketimine odor and amine odor in printed matter)
The nose was applied to the printed surface of each printed matter obtained, and the odor was evaluated by a sensory test. Table 1 shows the results.
A: No ketimine odor or amine odor is observed.
B: Ketimine odor and amine odor are slightly recognized.
C: Ketimine odor and amine odor are recognized.

(Blocking resistance)
The printed surface of each film printed one day after printing with each test ink was put together with the untreated surface of each film, and a load of 400 g/cm ² was applied and allowed to stand at 40°C for 12 hours, and then each film was peeled off. Blocking resistance was evaluated from the state of time.
A: There is no resistance when the film is peeled off, and the ink does not peel off from the printed surface.
B: There is resistance when the film is peeled off, but the ink does not peel off from the printed surface.
C: There is resistance when the film is peeled off, and the ink is peeled off from the printed surface.

(guide roll taken)
The slidability was evaluated by guide roll removal.
After printing, a test was conducted to determine whether ink adhered to the guide roll (guide roll removal) by the following method, and printability was evaluated. In addition, since the ink that has once adhered to the guide roll transfers to the printing surface again and causes staining, if "guide roll removal" occurs, it adversely affects the ability to obtain a decorative printed matter.
The presence or absence of dropout of the ink film on the printed matter by the guide roll of the gravure printing machine was visually evaluated.
A: None B: Some C: Yes

(Adhesiveness)
After rubbing the printed surface of each printed matter immediately after printing with the abdomen of the thumb twice, a cellophane tape was attached, and the adhesiveness was evaluated from the ratio of the area where the ink film was peeled off from the adherend when the tape was peeled off. did.
A: Not peeled off at all.
B: The peeled area is less than 20%.
C: The peeled area is 20% or more.

(Retort resistance)
A urethane-based adhesive (Takelac A-616/Takenate A-65, manufactured by Mitsui Chemicals Polyurethane Co., Ltd.) was added to each printed matter printed on NY and PET one day after printing so that the solid content was 2.0 g/m ² . was applied, a non-stretched polypropylene film (RXC-3, thickness 60 μm, manufactured by Tohcello Co., Ltd.) was laminated with a dry laminator, and left at 40° C. for 3 days to obtain a dry laminate. A mixture of 90% by mass of water and 10% by mass of salad oil is packed into a bag from this dry laminate, sealed, and then immersed in pressurized hot water at 135°C for 30 minutes. The retort resistance was evaluated from The evaluation criteria were the same as the boiling suitability.
A: No lamination is observed at all.
B: A pinhole-like or partially thin and short lamination float is observed.
C: Long stripe-like lamination lift is observed on the entire surface.
-: The retort suitability test was not performed because the film itself used for printing did not have retort suitability.

According to the results of each example according to the present invention, the printed matter did not have an amine odor or ketimine odor, the ink composition had excellent stability over time, and the guide roll was not stained. Furthermore, it was excellent in blocking resistance, adhesiveness and retort resistance to various films.
On the other hand, according to Comparative Examples 1 and 3, in which polyurethane polyurea resins not converted to ketimine were used, the prints had amine and ketimine odors, and the ink compositions were inferior in stability over time. Furthermore, the adhesion to various films and retort resistance were not particularly excellent.
Furthermore, according to Comparative Examples 2 and 4, in which polyurethane polyurea resins ketiminated with acetone after chain elongation were used, prints had amine and ketimine odors, and the ink compositions were inferior in stability over time.

Claims (8)

A high solid ink composition for organic solvent-based gravure printing containing a pigment, a binder resin and an organic solvent,
The pigment is an organic pigment and / or an inorganic pigment,
The binder resin contains the following (A) and / or (B) polyurethane polyurea resin,
A high-solid ink composition for organic solvent-based gravure printing, wherein the pigment and the binder resin satisfy the following conditions 1 to 3.
(A) one or more polyurethane polyurea resins having a weight average molecular weight of 20,000 to 50,000 selected from the following (A-1) and (A-2): (A-1) reacting a diol compound and a diisocyanate compound; Polyurethane polyurea resin obtained by subjecting the resulting urethane prepolymer and a compound in which the amino group of the polyamine compound is ketiminized with a ketone compound to chain extension and reaction termination in an organic solvent (A-2) Diol compound and diisocyanate A urethane prepolymer obtained by reacting a compound is reacted with a reaction terminator in an organic solvent, and then chain elongation and reaction termination are performed with a compound in which the amino group of the polyamine compound is ketiminated with a ketone compound. Obtained polyurethane polyurea resin (B) one or more polyurethane polyurea resins having a weight average molecular weight of 20,000 to 50,000 selected from the following (B-1) and (B-2) (B-1) diol compound and diisocyanate To a urethane prepolymer solution of a urethane prepolymer obtained by reacting a compound and an organic solvent, a compound in which the amino group of a polyamine compound is ketiminized by a ketone compound is added and mixed with stirring. Polyurethane polyurea resin obtained by elongation and reaction termination (B-2) A reaction terminator is added to a urethane prepolymer solution of a urethane prepolymer obtained by reacting a diol compound and a diisocyanate compound with an organic solvent to react, Next, a polyurethane polyurea resin obtained by adding a compound in which the amino group of the polyamine compound is ketiminized with a ketone compound and stirring and mixing, and then adding water, followed by chain elongation and reaction termination (Condition 1)
When the pigment is an organic pigment, the content of the organic pigment in the organic solvent-based high solid ink composition for gravure printing is 5 to 20% by mass (Condition 2)
When the pigment is an inorganic pigment, the content of the inorganic pigment in the organic solvent-based high solid ink composition for gravure printing is 30 to 70% by mass (Condition 3)
When the pigment contains both an organic pigment and an inorganic pigment, the content of the organic pigment in the organic solvent-based high solid ink composition for gravure printing is 5 to 20% by mass, and the mass ratio of the inorganic pigment to the organic pigment is {Inorganic pigment (mass)/Organic pigment (mass)} is 0<Inorganic pigment (mass)/Organic pigment (mass)<7.0. The polyurethane polyurea resin includes a polyurethane polyurea resin having a primary amino group at the terminal, a polyurethane polyurea resin having a primary amino group and a secondary amino group at the terminal, and a primary amino group at the terminal being ketimine. 2. The organic solvent-based high-solids ink composition for gravure printing according to claim 1, which is at least one selected from polyurethane polyurea resins having a modified group. 3. The organic solvent-based high-solid ink composition for gravure printing according to claim 1, which contains a vinyl chloride/vinyl acetate copolymer and/or a vinyl chloride/acrylic copolymer as a binder resin. At least one selected from rosin and its derivatives, chlorinated polypropylene, dammar resin as an adhesion improver, and silica particles, polyethylene wax, fatty acid amide, cellulose acetate propionate resin, cellulose acetate butyrate resin, and nitrocellulose as an antiblocking agent. 4. The organic solvent-based high-solid ink composition for gravure printing according to any one of claims 1 to 3, which contains one. The organic solvent-based high-solid ink composition for gravure printing according to any one of claims 1 to 4, wherein the organic solvent is a mixed solvent of an ester-based organic solvent and an alcohol-based organic solvent. At the time of gravure printing, an organic solvent-based high-solid ink composition for gravure printing is diluted by adding an organic solvent, and the organic solvent is a mixed solvent of an ester-based organic solvent and an alcohol-based organic solvent,
The proportion of the ester-based solvent and the alcohol-based organic solvent used in the organic solvent-based high-solid ink composition for gravure printing is ester-based organic solvent/alcohol-based organic solvent=50/50 to 95/5. Item 6. The organic solvent-based high-solid ink composition for gravure printing according to item 5. 7. The high solids ink composition for organic solvent gravure printing according to claim 5 or 6, which contains 5% by mass or more of propyl acetate as the ester solvent. A gravure printing method using the organic solvent-based high solids ink composition for gravure printing according to any one of claims 1 to 7,
preparing a high solids ink composition for organic solvent gravure printing by adding an organic solvent to the high solids ink composition for organic solvent gravure printing and diluting it;
A gravure printing method, wherein printing is performed by a gravure printing method using the high-solid ink composition for organic solvent-based gravure printing and using a shallow gravure plate.