JPH11279471A - Water-based printing ink composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject ink composition with excellent adhesiveness, laminating suitability and storage stability. SOLUTION: This ink composition essentially comprises a water-based polyurethane resin varnish and a colorant; wherein the varnish is such that a polyurethane resin having carboxy-bearing side chain, acid value of 10-100, and a number-average molecular weight of >=200 attributable to the polyol compound A described below, lies dissolved or dispersed in the presence of a basic substance. By the way, the polyurethane resin is obtained by the following procedure: a carboxy-contg. high-molecular weight polyol compound A consisting mainly of a carboxy-contg. high-molecular weight diol compound and prepared by reaction of a compound bearing one carboxylic anhydride group with a high-molecular weight polyol 500-10,000 in number-average molecular weight having three or more hydroxyl groups in the molecule, is reacted with an organic diisocyanate compound, a chain extender, and, as necessary, a reaction terminator.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an aqueous printing ink composition, and more particularly, to an aqueous printing ink composition having excellent adhesiveness and laminating suitability for various plastic films or various laminate packaging materials. About things.

[0002]

2. Description of the Related Art In recent years, with the diversification of packaging containers and the enhancement of the functionality of synthetic resin products such as synthetic leather, coating materials used for these materials have sufficient adhesiveness to adherends, strong resistance,
In addition, suitability for post-processing is required.

[0003] For example, printing inks used for various laminate packaging materials are required to have adhesiveness to various packaging materials, printing suitability, laminating suitability, and the like.

Here, there are generally the following two methods for laminating. After printing ink using various plastic films as a printing base material, apply an anchor coat agent to the printing surface as needed, then press the molten plastic and laminate it into a film shape by extrusion lamination, and adhere to the printing surface This is a dry laminating method in which an agent is applied, and a plastic film, a metal foil and the like are further laminated thereon and laminated.

[0005] Therefore, the printing ink used in the printed material to be laminated must not only adhere well to the printing substrate but also have excellent lamination strength with the film to be laminated.

Conventionally, a solvent-type printing ink using a polyurethane resin as a binder has been used as the printing ink. However, higher adhesiveness, lamination strength, boil resistance, and retort resistance are required. There is a problem that it cannot be applied to applications used under severe conditions.

Further, recently, from the viewpoints of environmental problems, resource saving, occupational safety, fire, and the like, there has been an increasing demand for aqueous-type printing inks in which the use of organic solvents is minimized.

Particularly, in a laminated packaging bag, the ink film is embedded between the film to be printed and the laminated film, so that a harmful organic solvent is likely to remain and adversely affect the contents. There is a strong demand for this aqueous solution.

In order to make the printing ink water-based, it is necessary to make the binder resin water-based. As a method for this, generally, the binder resin used in the solvent-based ink is dissolved in water in the presence of a surfactant. Emulsified (emulsion type), or an acid group introduced into the binder resin molecule and dissolved (water-soluble type) or dispersed (self-emulsifying type) in water in the presence of a basic compound. .

The polyurethane resin used for the printing ink for lamination can be made water-soluble by the above-mentioned method.
Ink fluidity and resolubility become poor. Therefore, a water-soluble or self-emulsifying type polyurethane resin is often used.

Here, the following method is disclosed as a method for introducing an acid group into a molecule for the purpose of making a polyurethane resin water-soluble.

A method in which a diol monocarboxylic acid such as dimethylolpropionic acid is used in addition to a polymer diol compound (Japanese Patent Application Laid-Open No. 4-178418, etc.) Tetracarboxylic dianhydride represented by pyromellitic anhydride Using condensates of diols and diol compounds (JP-A-6-184485, etc.)

However, in the case of an ink using a polyurethane resin obtained by the method described above, if a necessary amount of carboxyl group is introduced into a molecule to obtain resolubility, which is the basic performance of a gravure ink, the molecule itself becomes hard. In addition, there is a problem that the adhesiveness of the ink tends to decrease, and it is difficult to obtain an aqueous printing ink having both resolubility and adhesiveness.

According to the above method, the structure of the skeleton having a carboxyl group constituting a part of the main chain of the polyurethane resin by the reaction of the tetracarboxylic dianhydride and the diol compound is changed to the tetracarboxylic dianhydride and the diol compound. Molecular cleavage occurs due to hydrolysis of the ester bond with
There is a problem that the adhesion, lamination strength, and re-dissolvability of the aqueous ink over time decrease.

Therefore, in the aqueous printing ink for lamination using the above-mentioned aqueous polyurethane resin as a main binder, sufficient performance has not been obtained from the viewpoint of adhesion, laminating suitability and storage stability at present. is there.

[0016]

SUMMARY OF THE INVENTION The present invention has been made to solve these problems, and an object of the present invention is to provide an aqueous printing ink composition having excellent adhesion, laminability, and storage stability. is there.

[0017]

Means for Solving the Problems The present inventors have conducted various studies to solve the above problems, and as a result, as a high molecular weight polyol compound for obtaining a polyurethane resin, a high molecular weight polyol having 3 or more hydroxyl groups has been used. Using a carboxyl group-containing high molecular weight polyol compound (A) having a carboxyl group-containing side chain obtained by reacting a compound having one carboxylic acid anhydride group in the molecule with a polyurethane resin, It has been found that these problems can be solved by introducing a side chain having a carboxyl group having a number average molecular weight of 200 or more resulting from the above, and the present invention has been completed.

That is, the present invention provides (1) reacting a compound having one carboxylic acid anhydride group in a molecule with a high molecular weight polyol having a number average molecular weight of 500 to 10,000 having three or more hydroxyl groups in the molecule. Reaction of a carboxyl group-containing high molecular weight polyol compound (A) containing a carboxyl group-containing high molecular weight diol compound as a main component, an organic diisocyanate compound, a chain extender, and, if necessary, a reaction terminator. Having a side chain having a carboxyl group having a number average molecular weight of 200 or more and resulting from the polyol compound (A), and having an acid value of 10 to 10.
The present invention relates to an aqueous printing ink composition mainly composed of an aqueous polyurethane resin varnish and a colorant in a state in which a polyurethane resin is dissolved or dispersed in the presence of a basic substance.

The present invention also relates to (2) a carboxyl group-containing high molecular weight polyol compound (A) according to the above (1).
Has a number average molecular weight of 500 to 3 having three hydroxyl groups in the molecule.
A carboxyl group having a carboxyl group-containing high molecular weight diol compound obtained by reacting a compound having one carboxylic acid anhydride group in the molecule with 10,000 polyester triols so that the number of remaining hydroxyl groups becomes two. The present invention relates to an aqueous printing ink composition, which is a high-molecular-weight polyol compound (A).

The present invention also provides (3) the compound having one carboxylic acid anhydride group in the molecule according to the above item (1) or (2), wherein the compound having one carboxylic acid anhydride group in the molecule has one carboxyl group which does not form an anhydride ring.
The present invention relates to an aqueous printing ink composition comprising a compound having one carboxylic acid anhydride group.

Further, the present invention provides (4) the above (1) to
(3) The aqueous printing ink composition, wherein the compound having one carboxylic anhydride group in the molecule according to any one of (3) is trimellitic anhydride.

Further, the present invention provides (5) the above (1) to
(4) A water-based printing ink composition, characterized in that the terminal of the main chain of the polyurethane resin described in any one of (4) is a hydrazine residue.

Further, the present invention provides (6) the above (1) to
The basic substance according to any one of the above (5) has a boiling point of 120
The present invention relates to an aqueous printing ink composition characterized by being a non-volatile amine at a temperature of at least ℃.

[0024]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, as a high molecular weight polyol compound for obtaining a polyurethane resin, a compound having one carboxylic acid anhydride group in a molecule is reacted with a high molecular weight polyol having 3 or more hydroxyl groups. A carboxyl group-containing high molecular weight polyol compound (A) having a carboxyl group-containing side chain obtained by the above method is used, and a polyurethane resin is provided with a carboxyl group having a number average molecular weight of 200 or more due to the polyol compound (A). By introducing a side chain having the same, an aqueous printing ink composition having excellent storage stability, adhesiveness, suitability for lamination, and the like can be obtained.

The side chain having a carboxyl group having a number average molecular weight of 200 or more in the polyurethane resin due to the carboxyl group-containing high molecular weight polyol compound (A) will be described with reference to the drawings.

The carboxyl group-containing high molecular weight polyol compound (A) is obtained, for example, by reacting a high molecular weight triol having three hydroxyl groups with a compound having one carboxylic acid anhydride group in the molecule. When the high molecular weight diol compound (a-1) is contained, the diol compound (a-1) is schematically shown in FIG. In FIG. 1, the diol compound (a-1) is incorporated into the main chain of the polyurethane resin by two hydroxyl groups.
In the case of this diol compound (a-1), the chain b-1 branched from the main chain whose both ends are hydroxyl groups is the side chain in the present invention. The main chain differs depending on which hydroxyl group of the high molecular weight triol reacts with the carboxylic acid anhydride group of the compound having one carboxylic acid anhydride group in the molecule, and the side chain also differs accordingly. (The same applies to the following examples).

The carboxyl group-containing high molecular weight polyol compound (A) is obtained, for example, by reacting a high molecular weight tetraol having 4 hydroxyl groups with a compound having one carboxylic acid anhydride group in the molecule. When the carboxyl group-containing high molecular weight diol compound (a-2) is used, the diol compound (a-2) is schematically shown in FIG. In FIG. 2, the diol compound (a-2) is 2
Two hydroxyl groups will be incorporated into the main chain of the polyurethane resin. In the case of this diol compound (a-2), chains b-2 and b having both terminals branched from a main chain having a hydroxyl group.
-3 is a side chain.

When a compound having one carboxylic acid anhydride group in the molecule is reacted with the above-mentioned high molecular weight tetraol, the compound shown in FIG.
In some cases, a small amount of the triol compound (a-3) is formed as shown in (1). In the case of this triol compound (a-3), it is considered that all three hydroxyl groups are incorporated in the main chain of the polyurethane resin, and the closest main chain (OH (1) The chain b-4 branched from the main chain between OH (1) and OH (2) or the main chain between OH (1) and OH (3)) is defined as a side chain. Such handling can be applied to polyol compounds of triol or more.

The compound of the present invention is obtained by reacting a compound having one carboxylic acid anhydride group in the molecule with the high molecular weight polyol having a number average molecular weight of 500 to 10,000 having three or more hydroxyl groups in the molecule. A carboxyl group-containing high molecular weight diol compound as a main component, a carboxyl group-containing high molecular weight polyol compound (A), an organic diisocyanate compound, a chain extender, and if necessary, a reaction terminator. A polyurethane resin having a side chain having a carboxyl group having a number average molecular weight of 200 or more due to the polyol compound (A) and having an acid value of 10 to 100 is dissolved or dispersed in the presence of a basic substance. The aqueous printing ink composition mainly composed of the aqueous polyurethane resin varnish and the colorant in the state described above will be described in detail.

As the carboxyl group-containing high molecular weight polyol compound (A) of the present invention, a high molecular weight polyol having 3 or more hydroxyl groups, preferably having a number average molecular weight of 500 to 1 is preferred.
A carboxyl obtained by reacting a compound having one carboxylic acid anhydride group in the molecule at a ratio of 2 remaining hydroxyl groups to a high molecular weight polyol of 000, especially 1,000 to 6,000. A carboxyl group-containing high molecular weight polyol compound (A) containing a group-containing high molecular weight diol compound as a main component can be used.

As the high molecular weight polyol having three or more hydroxyl groups used for obtaining the carboxyl group-containing high molecular weight polyol compound (A) of the present invention, for example, the following high molecular weight polyols can be used.

(1) Polyhydric alcohols having 3 or more hydroxyl groups such as glycerin, trimethylolethane, trimethylolpropane and pentaerythritol, or saccharides such as sorbitol and sucrose are used as polyfunctionalizing agents. These include one such as ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran and the like.
Polyether polyol obtained by addition polymerization of a kind or two or more kinds (2) ε-caprolactone, δ-
Polyester polyol obtained by addition polymerization of one or more cyclic ester compounds such as valerolactone and β-methyl-δ-valerolactone (3) 1,3-propanediol in the presence of the polyfunctionalizing agent, One kind of low molecular weight diol compounds such as 1,4-butanediol, 1,6-hexanediol, 1,2-propanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, diethylene glycol and triethylene glycol Or a polyester polyol obtained by condensation polymerization of two or more kinds with one or more kinds of dibasic acid components such as adipic acid, phthalic acid, and isophthalic acid. (4) In the presence of the above-mentioned polyfunctionalizing agent, Low molecular weight diol compound and a carbonate component such as cyclic carbonate, dialkyl carbonate or phosgene. Polycarbonate polyols obtained by condensation polymerization

Among these high molecular weight polyols having an average of 3 or more hydroxyl groups, the polyester polyol (3) can be suitably used from the viewpoint of obtaining a wide lamination suitability for various films.

The compound having one carboxylic anhydride group in the molecule for obtaining the carboxyl group-containing high molecular weight polyol compound (A) of the present invention includes succinic anhydride, maleic anhydride, glutaric anhydride, phthalic anhydride, and the like. And trimellitic anhydride.

Among these, from the viewpoint of achieving both film properties such as adhesion and lamination suitability of the aqueous printing ink composition and resolubility, the aqueous printing ink composition has one carboxyl group which does not form an anhydride ring, and contains carboxylic acid. Trimellitic anhydride having one anhydride group can be suitably used.

The carboxyl group-containing high-molecular-weight polyol compound (A) of the present invention is incorporated into the above-mentioned molecule so that the number of remaining hydroxyl groups is two with respect to the high-molecular-weight polyol having an average of three or more hydroxyl groups. It is obtained by reacting a compound having one carboxylic anhydride group.

In the present invention, in addition to the above-mentioned carboxyl group-containing high molecular weight polyol compound (A), other high molecular weight diols not containing a carboxyl group may be used, if necessary, in such a range that the desired performance is not reduced. Such high molecular weight diols may have a number average molecular weight in the range of 500 to 10,000, and include polyether diols, polyester diols, polycarbonate diols conventionally used generally for the synthesis of polyurethane resins. Polyacetal diol, polyacrylate diol, polyester polyamide diol, polythioether diol, polybutadiene diol and the like can be used.

Examples of the polyether diol include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, trimethylene glycol, 1,4-butanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 1,6 −
Examples thereof include those obtained by addition-polymerizing ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran, or the like using one or more compounds having two active hydrogen atoms, such as hexanediol and bisphenol A, as initiators.

Examples of the polyester diol include ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, pentane Diol,
One or more of various saturated or unsaturated known glycol components such as 3-methyl-1,5-pentanediol, 1,6-hexanediol, and dipropylene glycol, and adipic acid, maleic acid, and fumaric acid Dibasic acids such as phthalic anhydride, isophthalic acid, terephthalic acid, succinic acid, oxalic acid, malonic acid, glutaric acid, azelaic acid, sebacic acid, suberic acid, and the corresponding acids such as acid anhydrides and dimer acids Polyester diols obtained by dehydrating and condensing one or more of the components, propiolactone, butyrolactone, ε-caprolactone, δ
-Valerolactone, cyclic ester compounds such as β-methyl-δ-valerolactone are used to prepare ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, trimethylene glycol, 4-butanediol, neopentyl glycol, 1,6-hexanediol. And polyester diols obtained by ring-opening polymerization with one or more compounds having two active hydrogen atoms such as bisphenol A and the like.

Examples of the polycarbonate diol include 1,
Compounds obtained by reacting glycols such as 4-butanediol, 1,6-hexanediol, diethylene glycol and the like with diphenyl carbonate and phosgene can be used.

The number average molecular weight of the high molecular weight diol having no carboxyl group which can be used in combination with the high molecular weight polyol compound having a carboxyl group (A) is 500 for the purpose of optimizing the film strength and cohesion of the obtained polyurethane resin. 〜１０10,000, preferably 1.00
Those having 0 to 6,000 can be suitably used.

In addition, a high molecular weight polyol containing no trifunctional or higher carboxyl group can be used in the range where the polyurethane resin does not gel or the aqueous solution does not become difficult. Specific examples include the above-mentioned high molecular weight polyols having 3 or more hydroxyl groups used for obtaining the carboxyl group-containing high molecular weight polyol compound (A).

In addition to the carboxyl group-containing high molecular weight polyol compound (A) of the present invention and the carboxyl group-free high molecular weight diol or polyol which can be used in combination,
By using a low molecular weight diol or polyol in combination and setting the number average molecular weight in the above range, a polyurethane resin capable of imparting good performance can be obtained.

Specifically, ethylene glycol, propylene glycol, 1,4-butanediol, 1,3-butanediol, 1,6-hexanediol, 1,8-octamethylenediol, neopentyl glycol,
9-nonanediol, bishydroxymethylcyclohexane, alkyl dialkanolamine, 1,4-pentanediol, 2,5-hexanediol, 3-methyl-
1,5-pentanediol, 2,2,4-trimethyl-
Examples thereof include low molecular weight diols having a number average molecular weight of less than 500, such as 1,6-hexanediol and the like, and low molar adducts of these alkylene oxides and low molecular weight adducts of bisphenol A.

Examples of the organic diisocyanate compound used for obtaining the polyurethane resin of the present invention include aromatic diisocyanate compounds such as tolylene diisocyanate and diphenylmethane diisocyanate, alicyclic diisocyanates such as 1,4-cyclohexane diisocyanate and isophorone diisocyanate, and hexadecane. Aliphatic diisocyanates such as methylene diisocyanate, 2,2,4- or 2,4,4-trimethylhexamethylene diisocyanate, and araliphatic diisocyanates such as α, α, α, α-tetramethylxylylene diisocyanate and xylylene diisocyanate Can be used.

Examples of the chain extender used to obtain the polyurethane resin of the present invention include ethylenediamine, propylenediamine, hexamethylenediamine, isophoronediamine, 4,4'-dicyclohexylmethanediamine, xylylenediamine, tolylenediamine and polydiamine. Oxyethylene diaminopropyl ether, methyliminobisethylamine, methyliminobispropylamine, ethyliminobisisopropylamine, N- (2-hydroxyethyl) ethylenediamine, N- (2-hydroxyethyl) propylenediamine, N, N'-di (2-hydroxyethyl) ethylenediamine, N- (2-hydroxypropyl) ethylenediamine, dimerdiamine obtained by converting a carboxyl group of dimer acid into an amino group, diaminopropionic acid, gluta , Asparagine, lysine, diamino compounds such as diaminobenzoic acid, oxalic acid dihydrazide, malonic acid dihydrazide, succinic acid dihydrazide, glutaric acid dihydrazide, adipic acid dihydrazide, sebacic acid dihydrazide, maleic acid dihydrazide, fumaric acid dihydrazide, itaconic dihydrazide Phthalic dihydrazide, carbonic dihydrazide, carbodihydrazide,
Dihydrazide compounds such as thiocarbodihydrazide, ethylene glycol, diethylene glycol, triethylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, pentanediol, 3-methyl-1 Glycol components such as 1,5-pentanediol, 1,6-hexanediol and dipropylene glycol can be used.

Further, a chain extender having three or more functional groups can be used in combination as long as the polyurethane resin does not gel or the aqueous solution does not become difficult.

Specifically, polyols such as glycerin, trimethylolethane, trimethylolpropane and pentaerythritol, and polyamines such as diethylenetriamine, triethylenetetramine and hexamethylenepentamine can be used.

As a reaction terminator optionally used for obtaining the polyurethane resin of the present invention, alkanolamines, hydrazine, dihydrazide compounds, alcohols and the like can be used. Further, bifunctional or more functional amines or the like can be used in a range in which the polyurethane resin does not gel or in a range in which aqueous conversion is not difficult.

Among them, in order to effectively utilize the interaction with the carbonyl group on the surface of the base plastic film for the purpose of obtaining suitability for lamination to various plastic films, the molecular terminal of the main chain of the polyurethane resin has a hydrazine residue. A compound having a hydrazine residue and / or hydrazine can be suitably used as a reaction terminator.

The polyurethane resin of the present invention has a number average molecular weight of 200 or more, preferably 300 to 300, from the viewpoint of obtaining suitability for lamination, good printing effect when formed into ink, printability, and resolubility. 25
And preferably has a side chain having a carboxyl group at the end, and has an acid value in the range of 10 to 100. The ratio needs to be determined.

If the acid value is less than 10, the printing effect, printing suitability and re-dissolvability of the ink are reduced because the water-soluble ability of the polyurethane resin is too low. On the other hand, if the acid value exceeds 100, the water-soluble ability is sufficient, but the film becomes too hard,
In addition, the feature of good lamination suitability, which is the object of the present invention, is impaired because the amount of the polar functional group is too large.

The basic substance for neutralizing the polyurethane resin of the present invention to obtain an aqueous polyurethane resin varnish includes volatile basic substances such as ammonia and triethylamine, and inorganic alkali compounds such as sodium hydroxide and potassium hydroxide. And non-volatile amines such as triethylenediamine, diethanolamine, triethanolamine, diethylenetriamine and diazabicyclooctene.

When used in a laminated container for food packaging, the volatile basic substance migrates to the contents through the sealant base material and emits an odor, which is not preferable. It is preferred to use a neutral amine. In addition, lamination suitability,
It is more preferable to use a non-volatile amine having a boiling point of 120 ° C. or more from the viewpoint of not lowering the water resistance. Among them, triethylenediamine is preferable from the viewpoint of lamination suitability and water resistance.

In order to make the urethane resin of the present invention aqueous, it is preferable not to use an emulsifier. However, as long as the performance is not reduced, a small amount of an emulsifier may be used in combination for the purpose of improving mechanical stability and the like. It is possible.

Examples of the emulsifier include an alkylphenyl ether type such as polyoxyethylene nonylphenyl ether, an alkyl ether type such as polyoxyethylene lauryl ether, an alkyl ester type such as polyoxyethylene laurate, and polyoxyethylene styrenated phenyl ether. Alkanols such as alkylphenyl condensate ether type, sorbitan derivatives such as polyoxyethylene sorbitol tetraoleate, alkylamine type such as polyoxyethylene lauryl amino ether, monool type lauryl diethanolamide such as polyoxyalkylene alkyl ether Nonionic emulsifiers such as amides, fatty acid salts such as sodium oleate, alkyl sulfates, alkyl benzene sulfonates, alkyl sulfosuccinates, Lid Reference sulfone salts, polyoxyethylene alkyl sulfates, alkane sulfonates sodium salt, is an anionic emulsifier such as phosphate ester may be used.

The polyurethane resin used in the present invention can be produced by a conventionally known general method. For example, an organic diisocyanate, a carboxyl group-containing high molecular weight polyol compound (A) and a high molecular weight diol or polyol which can be used in combination, if necessary, are prepared in an equivalent ratio NCO / O
The reaction is performed at a ratio of H = 1.3 to 2.5, preferably 1.5 to 2.0 to obtain a prepolymer. Next, a chain extender and, if necessary, a solvent, a catalyst and the like are added and reacted,
Further, a reaction terminator is reacted to complete the reaction.

Instead of using a reaction terminator, the reaction can also be produced by a method of terminating the reaction using an excess chain extender, or a method of simultaneously adding a chain extender and a reaction terminator.

In synthesizing the prepolymer, an organic solvent inert to NCO and hydrophilic, for example, 1-methyl-2-pidridone, acetone or the like can be used if necessary.

Further, for making the polyurethane resin water-soluble, a method of completing the reaction by adding an alkaline aqueous solution containing a basic compound after forming the prepolymer and then adding a chain extender and a reaction terminator, or After the reaction is completed in a solvent, an alkaline aqueous solution is added, and then, if necessary, the solvent can be removed.

The aqueous printing ink composition of the present invention is mainly composed of the above-mentioned aqueous polyurethane resin (one or all of which has been neutralized with a basic substance to be aqueous) and a colorant.

The amount of the polyurethane resin used in the aqueous printing ink composition of the present invention is 5 to 30% by weight, preferably 10 to 25% by weight.

For the purpose of improving the ink performance, other aqueous resins such as polyurethane resins, acrylic resins, polyester resins, styrene-maleic acid resins other than the present invention, as long as the effects of the present invention are not reduced. An ethylene-acrylic acid resin or the like can be used in combination.

Next, as the coloring agent used in the present invention,
Inorganic materials conventionally used in aqueous printing inks,
Organic pigments or extenders can be used.

The inorganic pigments usable herein include titanium oxide, red iron oxide, antimony red, cadmium red, cadmium yellow, cobalt blue, ultramarine, navy blue, carbon black, graphite and the like. Organic pigments include soluble azo pigments and insoluble Examples include azo pigments, azo lake pigments, condensed azo pigments, copper phthalocyanine pigments, condensed polycyclic pigments, and the like.

Further usable extenders include calcium carbonate, kaolin, clay, barium sulfate, aluminum hydroxide, talc and the like.

The usual use amount of these coloring agents is 1 to 50% by weight in the aqueous printing ink composition.

Further, depending on the necessity of drying properties and other ink properties, a water-miscible solvent such as a lower alcohol such as methanol, ethanol, isopropanol or methoxypropanol or a lower alkoxypropanol; Various additives such as a compound, a fluorine compound, an antifoaming agent, a crosslinking agent, and an antistatic agent can be contained.

As a method for producing an aqueous printing ink composition using the above materials, first, a pigment and an aqueous binder resin are stirred and mixed, and then kneaded in a usual dispersing apparatus.
Further, it can be produced by adding and mixing predetermined components.

The method for printing the aqueous printing ink composition of the present invention on various plastic films and the like is as follows. First, as the plastic film used as the substrate in the present invention, polyolefin, polyester, nylon,
Films such as polystyrene and those obtained by applying various surface coating agents such as vinylidene chloride resin to these films can be used. The aqueous printing ink composition of the present invention can be printed by a flexographic or gravure printing method using a known flexographic printing machine or gravure printing machine.

Further, as a method of laminating the printed matter obtained by the above method, the extrusion lamination method and the dry lamination method described in the prior art can be used.

Here, the extrusion lamination method uses a titanium-based, isocyanate-based,
After applying an anchor coating agent such as imine-based or polybutadiene-based, it is a method of laminating a molten polymer by a conventionally known extrusion laminating machine, and furthermore, a molten resin is used as an intermediate layer to form a sandwich with other materials. They can also be stacked. As the molten resin used in the extrusion lamination method, conventionally used resins such as low-density polyethylene, ethylene-vinyl acetate copolymer, and polypropylene can be used.

In the dry lamination method, a water-based, solvent-based or solvent-free adhesive composition such as a urethane-based or isocyanate-based adhesive is applied to the surface of a printed material, and then a conventionally known dry laminating machine is used. Is a method of laminating a film-like polymer. From the viewpoint of safety and health, environmental protection, and the like, it is preferable to use a water-based or solvent-free adhesive composition in order to obtain a completely water-based laminated product. In addition, as the film-like polymer used in the dry lamination method, polyethylene, unstretched polypropylene, etc. can be used. Lamination can be performed by sandwiching foil.

[0074]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples and the like.

<Production of Aqueous Polyurethane Resin Varnish> Aqueous polyurethane resin varnish 1 Adipine using trimethylolpropane as a trifunctionalizing agent in a four-necked flask equipped with a stirrer, a cooling tube, a nitrogen gas inlet tube and a dropping funnel. Acid and 3-methyl-1,
300 parts of triol having a number average molecular weight of 3,000 obtained by condensation polymerization of 5-pentanediol and 19.2 parts of trimellitic anhydride were charged and reacted at a reaction temperature of 110 to 130 ° C. for 1 hour. After cooling to 40 ° C., 35.5 parts of isophorone diisocyanate and 41 parts of N-methyl-2-pyrrolidone were charged and reacted at 50 to 60 ° C. for 4 hours.
After adding 04 parts, 83 parts of isopropanol and 22.4 parts of triethylenediamine as a basic substance and stirring uniformly, 6.13 parts of isophoronediamine as a chain extender was added and stirred for 5 minutes, and then water was added as a reaction terminator. 2.4 parts of hydrazine was added, and the mixture was stirred for 20 minutes to obtain an aqueous polyurethane resin varnish 1 having a solid content of 32% and an acid value of 31 (a side chain (hereinafter simply referred to as a carboxyl group-containing high molecular weight diol compound of a polyurethane resin). Theoretical number average molecular weight of 1192).

Here, the theoretical number average molecular weight of the side chain was determined as follows. It is assumed that the triol has a polyester chain uniformly attached to the three OH groups of the trifunctionalizing agent (trimethylolpropane). Therefore, the number average molecular weight of each of the three polyester chains is 1,000. One of the polyester chains has trimellitic anhydride (molecular weight 192) attached to the end of the polyester chain, so that the theoretical number average molecular weight of the side chain is 1192.

Aqueous polyurethane resin varnish 2 In the production of aqueous polyurethane resin varnish 1, 20.2 parts of triethylamine was used as a neutralizing agent instead of 22.4 parts of triethylenediamine, and the solid content concentration was 30%.
An aqueous polyurethane resin varnish 2 having an acid value of 31 was obtained (theoretical number average molecular weight of the side chain of the polyurethane resin was 1192).

Aqueous Polyurethane Resin Varnish 3 In the production of aqueous polyurethane resin varnish 1, 39.1 parts of tetramethylxylylene diisocyanate were used instead of 35.5 parts of isophorone diisocyanate, and an aqueous solution having a solid content of 32% and an acid value of 30 was used. Polyurethane resin varnish 3 was obtained (theoretical number average molecular weight of side chain of polyurethane resin 1192).

Aqueous Polyurethane Resin Varnish 4 In the production of the aqueous polyurethane resin varnish 1, as chain extender, 6.13 parts of isophoronediamine were replaced by N
-(2-hydroxyethyl) -ethylenediamine 3.7
Using 5 parts, an aqueous polyurethane resin varnish 4 having a solid content of 32% and an acid value of 31 was obtained (theoretical number average molecular weight of the side chain of the polyurethane resin was 1192).

Aqueous polyurethane resin varnish 5 In the production of aqueous polyurethane resin varnish 1, phthalic anhydride 1 was used instead of 19.2 parts of trimellitic anhydride.
Using 4.8 parts, the addition amount of the basic substance triethylenediamine was changed to 11.2 parts, and the solid content concentration was 31%.
An aqueous polyurethane resin varnish 5 having an acid value of 16 was obtained (theoretical number average molecular weight of the side chain of the polyurethane resin was 1148).

Aqueous Polyurethane Resin Varnish 6 An adipic acid and 3-methyl-1,5-pentanediol using trimethylolpropane as a trifunctionalizing agent were added to the same apparatus as used in the production of the aqueous polyurethane resin varnish 1. 300 parts of triol having a number average molecular weight of 3,000 obtained by condensation and 19.2 parts of trimellitic anhydride were charged and reacted at a reaction temperature of 110 to 130 ° C. for 1 hour. Then, after cooling, 5 parts of neopentyl glycol was added, and the mixture was stirred uniformly. After cooling to 40 ° C, 52.6 parts of isophorone diisocyanate and 44 parts of N-methyl-2-pyrrolidone were charged and reacted at 50 to 60 ° C for 4 hours. . 75 more water
After adding 3 parts, 89 parts of isopropanol and 22.4 parts of triethylenediamine as a basic substance and stirring uniformly, 9.09 parts of isophoronediamine as a chain extender was added and stirred for 5 minutes, and then water was added as a reaction terminator. 3.57 parts of hydrazine was added, and the mixture was stirred for 20 minutes.
An aqueous polyurethane resin varnish 6 having an acid value of 29 was obtained (theoretical number average molecular weight of the side chain of the polyurethane resin was 1192).

Aqueous Polyurethane Resin Varnish 7 An adipic acid and 3-methyl-1,5-pentanediol using trimethylolpropane as a trifunctionalizing agent were added to the same apparatus as used in the production of the aqueous polyurethane resin varnish 1. 150 parts of triol having a number average molecular weight of 1000 obtained by condensation and 28.8 parts of trimellitic anhydride were charged and reacted at a reaction temperature of 110 to 130 ° C. for 1 hour. 4
After cooling to 0 ° C, 150 parts of (poly 3-methyl-1,5-pentane adipate) diol having a number average molecular weight of 5000,
63.9 parts of isophorone diisocyanate, N-methyl-
46 parts of 2 pyrrolidone were charged and reacted at 50 to 60 ° C. for 4 hours, and then 781 parts of water, 92 parts of isopropanol,
After adding 33.6 parts of triethylenediamine as a basic substance and stirring uniformly, 11.1 parts of isophoronediamine as a chain extender was added and stirred for 5 minutes, and then 4.33 parts of hydrazine hydrate was added as a reaction terminator. Stir for 20 minutes,
An aqueous polyurethane resin varnish 7 having a solid content of 33% and an acid value of 41 was obtained (the theoretical number average molecular weight of the side chain of the polyurethane resin was 525).

Aqueous Polyurethane Resin Varnish 8 An apparatus similar to that used for the production of the aqueous polyurethane resin varnish 1 was charged with (poly-3-methyl-methyl) having a number average molecular weight of 1500.
300 parts of 1,5-pentane adipate) diol and 21.8 parts of pyromellitic anhydride were charged, and the reaction temperature was 90 to 1
The reaction was performed at 00 ° C. for 2 hours. After cooling to 50 ° C., 35.5 parts of isophorone diisocyanate, N-methylpyrrolidone 4
2 parts were charged and reacted at 50 to 60 ° C. for 4 hours. Then, 708 parts of water, 83 parts of isopropanol and 22.4 parts of triethylenediamine were added, and the mixture was stirred uniformly. Then, 6.13 parts of isophoronediamine was added as a chain extender. After stirring for 5 minutes, hydrazine hydrate was added as a reaction terminator and 2.4 parts were added, followed by stirring for 20 minutes to obtain a polyurethane resin varnish 8 having a solid content of 32% and an acid value of 31.

Aqueous polyurethane resin varnish 9 In the same apparatus as used for the production of aqueous polyurethane resin varnish 1, 240 parts of (poly-3-methyl-1,5-pentane adipate) diol having a number average molecular weight of 4000, dimethylolpropionic acid 24.1 parts, 85.2 parts of isophorone diisocyanate and 42 parts of N-methylpyrrolidone were charged and reacted at a reaction temperature of 90 ° C. for 8 hours. After cooling to 60 ° C., 716 parts of water, 84 parts of isopropanol, and 20.2 parts of triethylenediamine were added, and the mixture was stirred uniformly. Then, 14.7 parts of isophoronediamine was added as a chain extender, and stirred for 5 minutes. 5.77 parts of hydrazine was added and stirred for 20 minutes to obtain a polyurethane resin varnish 9 having a solid concentration of 32% and an acid value of 27.

Aqueous Polyurethane Resin Varnish 10 Condensation polymerization of adipic acid and 3-methyl-1,5-pentanediol using trimethylolpropane as a trifunctionalizing agent in the same apparatus as used in the production of aqueous polyurethane resin varnish 1. Then, 150 parts of triol having a number average molecular weight of 3000 and 7.41 parts of phthalic anhydride obtained were charged and reacted at a reaction temperature of 110 to 130 ° C. for 1 hour. After cooling to 40 ° C, (poly 3-methyl-1,
5-pentane adipate) diol 150 parts, isophorone diisocyanate 44.4 parts, N-methyl-2-pyrrolidone 42 parts were charged and reacted at 50 to 60 ° C. for 4 hours,
Then, 714 parts of water, 84 parts of isopropanol, and 5.61 parts of triethylenediamine as a basic substance were added, and the mixture was stirred uniformly, followed by isophoronediamine as a chain extender.
66 parts were added and stirred for 5 minutes. Then, 3.01 parts of hydrazine hydrate as a reaction terminator was added and stirred for 20 minutes to obtain an aqueous polyurethane resin varnish 10 having a solid content of 31% and an acid value of 8 (a polyurethane resin varnish). Side chain theoretical average molecular weight 114
8).

Aqueous polyurethane resin varnish 11 In the same apparatus as in the case of producing aqueous polyurethane resin varnish 1, trimethylolpropane was used as a trifunctionalizing agent.
-120 parts of triol having a number average molecular weight of 400 obtained by addition polymerization of caprolactone, and trimellitic anhydride 5
7.6 parts were charged and reacted at a reaction temperature of 110 to 130 ° C. for 1 hour. After cooling to 50 ° C., 106.6 parts of isophorone diisocyanate and 33 parts of N-methyl-2-pyrrolidone were charged and reacted at 50 to 60 ° C. for 4 hours.
3 parts, 66 parts of isopropanol and 63.3 parts of triethylenediamine as a basic substance were added and stirred uniformly, then 18.4 parts of isophoronediamine was added as a chain extender, stirred for 5 minutes, and then added with water as a reaction terminator. 7.21 parts of hydrazine was added and stirred for 20 minutes to obtain a solid content of 36%.
An aqueous polyurethane resin varnish 11 having an acid value of 109 was obtained (the theoretical number average molecular weight of the side chain of the polyurethane resin was 32).
5).

[Aqueous Printing Ink Composition for Laminating] Examples 1 to 8 and Comparative Examples 1 to 4 Using aqueous polyurethane resin varnishes 1 to 11,
According to the composition shown in Table 2, an aqueous printing ink composition for lamination was produced.

That is, the pigment and the polyurethane resin are stirred for 30 minutes with a Red Devil-type disperser, and when water, isopropyl alcohol and the combined resin are added, the water, isopropyl alcohol and the combined resin are added, and the mixture is further added for 15 minutes. Stirring was performed.

Here, titanium oxide (Taipu R-960, manufactured by DuPont) was used as a pigment, and Seixen AC (manufactured by Sumitomo Seika Co., Ltd.) was used as an ethylene-acrylic acid resin.

[Evaluation Test] The resolubility, adhesiveness, and extrusion lamination strength of the obtained aqueous printing ink composition for lamination were evaluated by the following methods. The results are shown in Tables 1 and 2.

The inks immediately after production were set to the a state, and the inks aged at 40 ° C. for one month were set to the b state. Changes in the respective properties due to long-term storage of the ink were also observed.

(1) Resolubility Test Method After operating for 10 seconds using the aqueous printing ink composition for lamination with a gravure calibrator, the operation was stopped and left as it was for 60 seconds. Subsequently, a corona-treated stretched polypropylene film (manufactured by Toyobo Co., Ltd., P-2161, thickness 25)
μm, hereinafter referred to as a processed OPP film), and the resolubility of the ink was determined from the number of pitches until a normal printed matter was obtained.

Evaluation Criteria A: Return to normal within 10 pitches B: Return to normal at 11 to 30 pitches C: Return to normal at 31 to 50 pitches D: Do not return to normal at 50 pitches

(2) Adhesiveness test method Each of the aqueous printing ink compositions for lamination was treated with a gravure proofing machine using an OPP film or a corona-treated stretched PET film (manufactured by Toyobo Co., Ltd., E-5102, thickness 15 μm).
m, hereinafter referred to as a treated PET film) by printing with a heliocrysograph 200 lines / inch plate, affixing scotch tape to the printing surface, and when peeling it off, the adhesiveness is determined from the degree to which the printed film is peeled off from the film. evaluated.

Evaluation Criteria A: The print film does not peel off from the film at all. B: The print film has an area ratio of less than 20% that peels off from the film. C: The print film has an area ratio of 20% or more and less than 50%. Is peeled off from the film D: 50% or more of the printed film is peeled off from the film

(3) Extrusion Lamination Strength Test Method After printing each aqueous printing ink composition for lamination on a treated OPP film and a treated PET film with a helioxograph 200 lines / inch plate using a gravure proofing machine, an anchor coating agent [ For processed OPP film, imine series (manufactured by Toyo Morton Co., Ltd., EL-420), processed PET
An isocyanate (EL-443A / C, manufactured by Toyo Morton Co., Ltd.) is applied to the film, and molten polyethylene is laminated to a thickness of 45 μm by an extrusion laminator to obtain a laminated product. Was. After aging these laminated products at 40 ° C. for 3 days, 15 m
It was cut to a width of m and the T-peel strength was measured using a peel tester manufactured by Yasuda Seiki Co., Ltd.

Evaluation method The actual measured value of the peel strength (g / 15 mm) was described.

[0098]

[Table 1]

[0099]

[Table 2]

[0100]

As specifically described above with reference to the examples, the use of the carboxyl group-containing high molecular weight polyol compound (A) specified in the present invention as a high molecular weight polyol for obtaining a polyurethane resin. Thus, an aqueous printing ink composition having excellent storage stability, adhesiveness, suitability for lamination, and the like can be obtained.

[Brief description of the drawings]

FIG. 1 is a schematic view showing one example of a structure of a carboxyl group-containing high molecular weight polyol compound (A) for obtaining a polyurethane resin used in the present invention.

FIG. 2 is a schematic view showing another example of the structure of the carboxyl group-containing high molecular weight polyol compound (A) for obtaining the polyurethane resin used in the present invention.

FIG. 3 is a schematic view showing still another example of the structure of the carboxyl group-containing high molecular weight polyol compound (A) for obtaining the polyurethane resin used in the present invention.

[Explanation of symbols]

 b-1, b-2, b-3, b-4 side chain

Claims (6)

[Claims] 1. A high molecular weight polyol having three or more hydroxyl groups in the molecule and having a number average molecular weight of 500 to 10,000,
A carboxyl group-containing high molecular weight polyol compound (A) having a carboxyl group-containing high molecular weight diol compound as a main component, obtained by reacting a compound having one carboxylic acid anhydride group in the molecule, an organic diisocyanate compound, and a chain elongation. A side chain having a carboxyl group having a number average molecular weight of 200 or more derived from the polyol compound (A), which is obtained by reacting an agent and, if necessary, a reaction terminator, and having an acid value of 10 to 10. An aqueous printing ink composition mainly comprising an aqueous polyurethane resin varnish and a colorant in which 100 polyurethane resins are dissolved or dispersed in the presence of a basic substance. 2. A carboxyl group-containing high-molecular-weight polyol compound (A) according to claim 1, which has a number average molecular weight of 500 to 10,000 having three hydroxyl groups in the molecule and a carboxylic anhydride in the molecule. A carboxyl group-containing high molecular weight polyol compound (A) having a carboxyl group-containing high molecular weight diol compound obtained by reacting a compound having one group so that the number of remaining hydroxyl groups becomes two; Aqueous printing ink composition. 3. The compound according to claim 1, wherein the compound having one carboxylic acid anhydride group in the molecule has one carboxyl group not forming an anhydride ring and one carboxylic acid anhydride group. A water-based printing ink composition comprising: 4. The aqueous printing ink composition according to claim 1, wherein the compound having one carboxylic acid anhydride group in a molecule thereof is trimellitic anhydride. 5. An aqueous printing ink composition, wherein the terminal of the main chain of the polyurethane resin according to claim 1 is a hydrazine residue. 6. An aqueous printing ink composition, wherein the basic substance according to claim 1 is a nonvolatile amine having a boiling point of 120 ° C. or higher.