JPH10158564A - Aqueous printing ink composition and production of printed matter by using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an aqueous printing ink composition excellent in leveling properties, etc., when being printed on a paper or a plastic film by including a pigment and an aqueous binder resin vanish as main components, and further a small amount of water-soluble or water-dispersable alkylene oxide adduct of water-dispersable dimethylpolysiloxane. SOLUTION: The objective aqueous printing ink composition excellent in repeatability of fine lines and half-tone dots is obtained by including a pigment and an aqueous binder resin vanish as main components, and further 0.005-5wt.% water-soluble or water-dispersable alkylene oxide adduct of water-dispersable dimethylpolysiloxane of the formula (m) is >=0; (n) is >=1; X is the formula R<1> -(O-R<2> -)p -O-R<3> [(p) is >=1; R<1> is a radically polymerizable hydroxy compound residue used for introducing OH to a siloxane chain; R<2> is ethylene or propylene with the proviso that one thereof is ethylene; R<3> is H or an alkyl having C number within the range capable of keeping the compound of the formula water- soluble or water-dispersable]; groups of (m) and (n) are random- or block-form}.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to an aqueous printing ink composition. More specifically, the present invention relates to an aqueous printing ink composition having good leveling properties and excellent fine line reproducibility and halftone dot reproducibility when printed on paper or a plastic film.

[0002]

2. Description of the Related Art In recent years, environmental problems, resource saving, occupational safety,
From the standpoint of disaster prevention and the like, there is a demand for aqueous printing inks that use as little organic solvents as possible.

[0003] The same applies to inks for printing on paper or plastic films used for packaging containers of foods and electric appliances, etc., but in general, water-based inks are inferior in leveling property as compared with organic solvent-based inks. Therefore, there is a tendency that it is difficult to obtain a cosmetic print.

[0004] In order to improve the leveling property of the ink, a method of adding a necessary minimum amount of an organic solvent and a method of adding a surfactant have been attempted. But,
Although these all improve the leveling property, they cause factors such as thickening of a halftone dot (defective halftone dot reproducibility) and blurring of a thin line (defective thin line reproducibility).

[0005] In order to obtain a cosmetic print, all of these properties must be good. However, since the leveling property of the printing ink and the dot reproducibility and the fine line reproducibility are contradictory, both of them are required. It is very difficult to obtain aqueous printing inks that satisfy higher levels of performance.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above problems and to provide a printing ink composition which has good leveling properties even though it is an aqueous ink, and which is excellent in fine line reproducibility and halftone dot reproducibility. Is to do.

[0007]

Means for Solving the Problems The present invention provides (1) a pigment,
In an aqueous printing ink composition containing an aqueous binder resin varnish as a main component, a water-soluble or water-dispersible dimethylpolysiloxane alkylene oxide adduct represented by the following general formula (1) is further added in an amount of 0.1% to the ink composition.
The present invention relates to an aqueous printing ink composition containing 005 to 5% by weight.

[0008]

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In the general formula (1), m is 0 or an integer of 1 or more, n is an integer of 1 or more, and n Xs are each independently a general formula (2):

[0010]

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Wherein p is an integer of 1 or more, R ¹ is a residue of a radically polymerizable hydroxy compound used for introducing a hydroxyl group into a siloxane chain, and p R ² are each independently ethylene. Or a propylene group, at least one of which is an ethylene group, and R ³ is a hydrogen atom or a carbon number within a range in which the compound represented by the general formula (1) can maintain water solubility or water dispersibility. Which is an alkyl group).

In general formula (1), formula (3):

[0013]

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And a group represented by the formula (4):

[0015]

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The groups represented by the formula (wherein X is the same as described above) may be arranged at random or may be arranged in blocks.

The present invention further provides (2) the aqueous solution according to (1), wherein the water-soluble or water-dispersible dimethylpolysiloxane alkylene oxide adduct is contained in an ink composition in an amount of 0.05 to 2% by weight. The present invention relates to a printing ink composition.

The present invention further provides (3) at least one kind of the binder resin varnish selected from the group consisting of a polyurethane resin, an acrylic resin, a styrene-maleic acid resin, and an ethylene-acrylic acid resin. The aqueous printing ink composition according to the above (1) or (2), which is an aqueous binder resin varnish obtained by dissolving or dispersing in water in the presence of an emulsifier and / or a basic compound.

The present invention further provides (4) the above (1) to
The aqueous printing ink composition according to any of (3),
The present invention relates to a method for producing a printed material, which comprises printing on paper or a plastic film by flexographic or gravure printing.

[0020]

DESCRIPTION OF THE PREFERRED EMBODIMENTS In a printing method using a plate, a printed pattern such as a character or a pattern is constituted by a set of small dots of ink. When the ink is transferred from the plate to the adherend, the area of the halftone dot does not increase or decrease as it is, and there is no color unevenness within the halftone dot by leveling, and the original printed image can be reproduced for the first time. .

However, the conventional method of improving the leveling property of the aqueous ink by adding an organic solvent or a surfactant is based on the effect of lowering the surface tension of the ink. After transferring to the adherend, the net weight is reduced by its own weight. The periphery of the point spreads, and the dot itself or a thin line causes thickening.

Further, in the case of fibrous paper or the like, the ink penetrates between the fibers, so that the thickness of the halftone dots and the like are further promoted.

On the other hand, the present inventors have made it possible to improve the leveling property by adding a specific amount of the above-mentioned specific dimethylpolysiloxane alkylene oxide adduct to the aqueous printing ink composition, although the reason is not clear. Nevertheless, the present inventors have found a peculiar performance of providing a printed material having excellent dot reproducibility and fine line reproducibility, and completed the present invention.

Hereinafter, the present invention will be described in more detail.

The aqueous printing ink composition of the present invention comprises a pigment,
It contains, as an essential component, a water-soluble or water-dispersible dimethylpolysiloxane alkylene oxide adduct represented by the general formula (1) in addition to the aqueous binder resin varnish.

As the pigment used in the present invention, an inorganic or organic coloring pigment or extender which can be generally used in an aqueous ink can be used.

Examples of the inorganic pigment include titanium oxide, red iron oxide, antimony red, cadmium red,
Examples of organic pigments such as cadmium yellow, cobalt blue, navy blue, ultramarine, carbon black, and graphite include soluble azo pigments, insoluble azo pigments, azo lake pigments, condensed azo pigments, copper phthalocyanine pigments, condensed polycyclic pigments, and the like. .

Examples of the extender include calcium carbonate, kaolin, clay, barium sulfate, aluminum hydroxide, and talc. These pigments generally have a content of 1 to 50 in the aqueous ink composition. % By weight.

Next, the aqueous binder resin varnish used in the present invention comprises a known polyurethane resin, acrylic resin, styrene-maleic acid resin, and ethylene-acrylic acid resin used in the ink composition. An aqueous binder resin varnish obtained by making at least one selected from the group aqueous can be used.

<Aqueous Polyurethane Resin Varnish> The polyurethane resin used as the aqueous binder resin in the present invention includes:
It is obtained by reacting an organic diisocyanate compound with a high molecular weight diol compound to synthesize a urethane prepolymer, and then reacting with a chain extender and a reaction terminator. To make it aqueous, in the presence of an emulsifier and / or a basic compound.

Examples of the organic diisocyanate compound include an aliphatic diisocyanate compound represented by hexamethylene diisocyanate, an alicyclic diisocyanate compound represented by isophorone diisocyanate, α,
aromatic and alicyclic diisocyanate compounds represented by α, α ′, α′-tetramethylxylylene diisocyanate;
Aromatic diisocyanate compounds represented by tolylene diisocyanate and the like are mentioned, and among them, alicyclic and aromatic alicyclic diisocyanate compounds are preferable.

Examples of the high molecular diol compound include a polycondensate obtained by polycondensing a low molecular diol compound having about 2 to 8 carbon atoms such as glycols and a dibasic acid, or a cyclic ester compound such as a lactone. Polyester diols obtained by a ring reaction, or polyether diols obtained by polymerizing or copolymerizing ethylene oxide, propylene oxide, etc., and further obtained by reacting the low molecular weight diol compound with a carbonate component or phosgene Examples thereof include polycarbonate diols and polybutadiene glycols.

In order to introduce a carboxyl group into a molecule for the purpose of making the polyurethane resin aqueous, a polymer diol compound having a free carboxyl group can be used. A polymer diol compound obtained by reacting a tetrabasic acid anhydride such as melitic acid or by ring-opening polymerization of a lactone using dimethylolpropionic acid or the like as an initiator can be used.

These high molecular weight diol compounds have a molecular weight (number average molecular weight, hereinafter the same) of 500 to 400.
0 can be suitably used. In addition, polyester diols and polycarbonate diols can be suitably used from the viewpoint of adhesiveness to a plastic film and suitability for lamination.

Examples of the chain extender include the above-mentioned low molecular weight diol compounds and diamine compounds, and those which can be used in combination therewith are aliphatic polyols having 3 or more hydroxyl groups, alicyclic polyols, amino Aliphatic polyamines having three or more groups can be mentioned.

Further, in order to introduce a free carboxyl group into the molecule of the polyurethane resin, a chain extender having a free carboxyl group, and for the purpose of imparting higher adhesiveness to a plastic film,
A chain extender having a hydrazine residue in the molecule, such as polyaminohydrazide, can be used.

Examples of the reaction terminator include alkyl monoamines, alkanolamines, and monoalcohols.

Further, in order to introduce a hydrazine residue into the polyurethane molecule, the above-mentioned polyaminohydrazide can be preferably used, and hydrazine, alkylenedihydrazine, or a dihydrazide compound of a saturated dibasic acid can also be used.

Using each of these reaction components, a polyurethane resin can be produced by a known production method, and a method of using a known emulsifier or a method of introducing a carboxyl group into a molecule to neutralize with a basic compound. It can be made aqueous.

The molecular weight of the polyurethane resin preferably used in the present invention is from 5,000 to 200,000, more preferably from 10,000 to 100,000.

When the molecular weight of the polyurethane resin is less than the above range, the obtained resin film has poor elasticity and becomes brittle, while when the molecular weight exceeds the above range, dispersion or dissolution stability in water tends to decrease. .

When the polyurethane resin of the present invention is made aqueous by introducing a carboxyl group into the molecule and neutralizing it with a basic compound, the acid value of the polyurethane resin is 5
The range of ~ 100 is preferred. If the acid value is smaller than the above range, it is difficult to make the aqueous solution aqueous, whereas if the acid value is larger than the above range, the water resistance and the drying property are undesirably reduced.

The ink composition using an aqueous polyurethane resin varnish as a binder is suitably used particularly for a plastic film.

<Aqueous Acrylic Resin Varnish> The acrylic resin used as the aqueous binder resin varnish in the present invention is a copolymer obtained by copolymerizing a styrene monomer, a maleic acid monomer and the like with an acrylic monomer as an essential component. It is a polymer resin, and can be made water-soluble in the presence of an emulsifier and / or a basic compound by introducing a free carboxyl group into the molecule, if necessary.

The acrylic monomers include (meth) acrylic acid and alkyl esters having 1 to 18 carbon atoms, alkyl amides having 1 to 18 carbon atoms, and hydroxyalkyl esters having 2 to 4 carbon atoms. Can be mentioned.

Here, (meth) acrylic acid means acrylic acid or methacrylic acid.

Styrene-based monomers include styrene and derivatives thereof, and maleic-based monomers include maleic anhydride and maleic acid.
8 alkyl esters, alkyl amides having 1 to 18 carbon atoms, hydroxyalkyl esters having 2 to 4 carbon atoms, and the like.

Further, the acrylic resin used in the present invention may be a resin produced by further using a known monomer other than the above-mentioned components generally used as a reaction component of an aqueous acrylic resin. Absent.

An acrylic resin can be produced by a known production method using each of these reaction components, a method using a known emulsifier and / or a protective colloid of a polymer,
It can be made aqueous by a method of introducing a carboxyl group into the molecule and neutralizing with a basic compound.

A carboxyl group is introduced into the molecule,
When the acrylic resin of the present invention is made aqueous by neutralization with a basic compound, the acid value of the acrylic resin is 10
A range of -350 is preferred. When the acid value is smaller than the above range, it is difficult to make the aqueous solution aqueous. On the other hand, when the acid value is larger than the above range, the water resistance and the drying property are undesirably reduced.

The ink composition using a water-based acrylic resin varnish as a binder is suitably used particularly for paper and some plastic films.

<Aqueous styrene-maleic acid resin varnish> The styrene-maleic acid resin used as the aqueous binder resin varnish of the present invention can be obtained by copolymerizing the styrene monomer and the maleic acid monomer,
If necessary, a free carboxyl group can be introduced into the molecule to make it aqueous.

A styrene-maleic resin or a styrene-maleic acid resin can be produced by a known production method using each of these reaction components.
The aqueous solution can be made aqueous by a method using a known emulsifier and / or a protective colloid of a polymer, or a method of introducing a carboxyl group into the molecule and neutralizing the molecule with a basic compound.

When the styrene-maleic acid resin of the present invention is converted to an aqueous solution by introducing a carboxyl group into the molecule and neutralizing the resin with a basic compound, the acid value of the styrene-maleic acid resin is 10 A range of -350 is preferred.
When the acid value is smaller than the above range, it is difficult to make the aqueous solution aqueous. On the other hand, when the acid value is larger than the above range, the water resistance and the drying property are undesirably reduced.

The ink composition using an aqueous styrene-maleic acid resin varnish as a binder is suitably used particularly for paper.

<Aqueous ethylene-acrylic acid resin varnish> The ethylene-acrylic acid copolymer used as the aqueous binder resin varnish of the present invention is ethylene 60-90.
% By weight, 10 to 30% by weight of acrylic acid or methacrylic acid, 0 to 30 other copolymerizable vinyl group-containing compounds
A copolymer obtained by copolymerization at a composition of weight% is suitable, and can be dispersed in water to form an aqueous varnish in the presence of a basic compound and, if necessary, an emulsifier.

Here, as other copolymerizable vinyl group-containing compounds, the above-mentioned alkyl esters of acrylic acid or methacrylic acid, alkylamides, styrene monomers, vinyl chloride, vinyl acetate, and the like can be used.

Here, the reason why the content of (meth) acrylic acid is preferably 10 to 30% by weight is that when the content of (meth) acrylic acid is less than 10% by weight, the water content of the copolymer relative to water is low. This is because the emulsifying ability is reduced and the use is limited, while if it exceeds 30% by weight, the drying property is reduced.

The ethylene-acrylic acid copolymer used in the present invention preferably has a melt index of 100.
~ 2000g / 10min, more preferably 300 ~ 1000
g / 10 minutes. If the melt index of the copolymer is smaller than the above range, the dispersion stability of the resin in water is reduced, while if it exceeds the range, the resin becomes too flexible, and the printing surface and film of the resulting aqueous ink are obtained. Blocking is likely to occur between

Using each of these reaction components, an ethylene-acrylic acid resin can be produced by a known production method, and can be made aqueous by a method using a known basic compound and, if necessary, a known emulsifier. .

The ethylene-acrylic acid resin is commercially available as a solid resin and an aqueous resin varnish. For example, as a pellet-shaped solid resin, an ethylene-acrylic acid copolymer A-200W (manufactured by Mitsubishi Chemical Corporation) ), As a resin varnish dispersed in water in the presence of a basic compound, Seixen AC (manufactured by Sumitomo Seika Co., Ltd.) is available.

The ink composition using the aqueous ethylene-acrylic acid resin varnish as a binder is suitably used for paper and plastic film.

The use ratio (as solid content) of the above aqueous binder resin varnish is about 1 to 40% by weight in the aqueous ink composition of the present invention.

In the present invention, an aqueous binder resin varnish obtained by making various other resins aqueous, such as a cellulose resin, a polyester resin, a polyamide resin and a hard resin, is added as another auxiliary aqueous binder resin. Can't do anything.

The present invention is further characterized by containing a water-soluble or water-dispersible dimethylpolysiloxane alkylene oxide adduct represented by the following general formula (1).

[0066]

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In the general formula (1), m is 0 or an integer of 1 or more, n is an integer of 1 or more, and n Xs are each independently of the general formula (2):

[0068]

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(In the formula, p is an integer of 1 or more, R ¹ is a residue of a radical polymerizable hydroxy compound used for introducing a hydroxyl group into a siloxane chain, and p R ² are each independently ethylene. Or a propylene group, at least one of which is an ethylene group, and R ³ is a hydrogen atom or a carbon number within a range in which the compound represented by the general formula (1) can maintain water solubility or water dispersibility. Which is an alkyl group).

In the general formula (1), the formula (3):

[0071]

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And a group represented by the formula (4):

[0073]

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The groups represented by the formula (wherein, X is the same as described above) may be arranged at random or may be arranged in blocks.

In the general formula (2), examples of the radical polymerizable hydroxy compound which provides a residue of the radical polymerizable hydroxy compound used for introducing a hydroxyl group into the siloxane chain represented by R ¹ include, for example, allyl alcohol And so on. The alkyl group having a carbon number within the range in which the compound represented by the general formula (1) represented by R ³ can maintain water solubility or water dispersibility varies depending on the type of R ² and the value of p. Has 1 carbon atom
3 to 3 lower alkyl groups are preferred.

As the dimethylpolysiloxane alkylene oxide adduct having the above-mentioned specified structure, those having a range that can be dispersed or dissolved in water can be used.
ILWET L-77, L-720, L-7001, L
-7002, L-7602, L-7604, Y-700
6, FZ-2104, FZ-2120 (all manufactured by Nippon Unicar Co., Ltd.), BYK348 (BYK Chemi)
cal company) is commercially available.

In the compound of the general formula (1), m
A compound having a small sum of + n has a high hydrophilicity and a good solubility in water can be obtained, but a dot or a thin line is apt to be thickened.

On the other hand, a compound having a large sum of m + n has high hydrophobicity and tends to have poor dispersibility in water.
Repelling and pinholes are likely to occur. In that case,
A method of dispersing in water using an emulsifier or the like can also be used.

From these points, in the present invention, m + n
Is preferably about 3 to 200.

Further, the compound of the general formula (1) has at least one structural unit represented by-(OC ₂ H ₄ )-in the molecule.
And optionally a structural unit represented by-(OC ₃ H ₆ )-.

As the total number of the structural units-(OC ₂ H ₄ )-increases, the phase shifts from hydrophobic to hydrophilic.
If it exceeds 0, thickening of halftone dots and thin lines is likely to occur.

Therefore, when the total number of m + n is not very large (for example, m + n = 1 to 50), the structural unit-(OC ₂ ) is added so that the compound as a whole does not become too hydrophilic.
It is preferable that the total number of H ₄ )-be about 3 to 50.

The structural unit-(OC ₃ H ₆ )-is 10 units of the structural unit-(OC ₂ H ₄ )-from the viewpoint of water solubility and water dispersibility.
It is preferred to be at most mol%.

In the aqueous printing ink composition of the present invention,
The amount of the water-soluble or water-dispersible dimethylpolysiloxane alkylene oxide adduct represented by the general formula (1) is 0.005 to 5% by weight, preferably 0.05 to 2% by weight in the ink composition. More preferably, it is 0.1 to 1% by weight.

When the amount of the compound represented by the general formula (1) is less than the above range, the effect of the present invention cannot be obtained. On the other hand, when the amount is too large, poor dot reproducibility occurs. Is not preferred.

The aqueous ink composition of the present invention may further contain various additives such as a water-miscible solvent such as methanol, ethanol, propanol, methoxypropanol and N-methylpyrrolidone, a pigment dispersant, an antiblocking agent, an antifoaming agent and a crosslinking agent. Adding additives is optional.

As a method for producing an aqueous printing ink composition using these various materials, a pigment, an aqueous binder resin varnish and, if necessary, a pigment dispersing resin or a pigment dispersing agent are mixed, kneaded, and further mixed. The method of adding and mixing the compound of the general formula (1) and the remainder of the predetermined material is general.

As the aqueous binder resin varnish, those having a carboxyl group in the molecule, neutralized with a basic compound and dissolved in water are advantageous in order to improve the pigment dispersibility.

The printing ink composition obtained as described above is prepared by using paper or a plastic film as an adherend.
Printing can be performed by flexographic or gravure printing.

Examples of paper usable as an adherend include jute paper, kraft paper, a water-repellent liner, and various types of coated paper. Examples of plastic films include various plastic films such as polyolefin, polyester, and nylon. Surface treatments such as corona discharge treatment are more preferable.

The printed matter obtained by the present invention has very clear fine lines and fine characters, and has excellent color reproducibility.

[0092]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the present invention is limited thereto.
Unless otherwise specified, “parts” and “%” represent “parts by weight” and “% by weight”, respectively.

<Production of Aqueous Acrylic Resin Varnish> Production Example 1 Ethyl acetate (600 parts) was charged into a four-necked flask equipped with a thermometer, a stirrer, a condenser, and a dropping funnel.
After heating to 78 ° C., a mixture of 38.4 parts of acrylic acid, 180 parts of butyl acrylate, 181.6 parts of methyl methacrylate, and 4 parts of ditertiary butyl peroxide as a polymerization initiator was introduced over 3 hours while introducing nitrogen gas. It was dropped. After completion of the dropwise addition, polymerization was carried out at reflux temperature for 3 hours to complete the reaction, and ethyl acetate was distilled off to obtain an acrylic copolymer 1 having an acid value of 75.

A container equipped with a stirrer was charged with 300 parts of the crushed acrylic copolymer 1 and 700 parts of aqueous ammonia containing 1.2 equivalents of ammonia with respect to the neutralized amount, and stirred at 80 ° C. The aqueous acrylic resin varnish having a solid content of 30% was heated and dissolved. 1 was obtained.

Production Example 2 In the same manner as in Production Example 1, 25.6 parts of acrylic acid, 180 parts of butyl acrylate, and 80 parts of methyl methacrylate
, 114.4 parts of styrene and 4 parts of ditertiary butyl peroxide as a polymerization initiator were reacted,
After the acrylic copolymer 2 having an acid value of 50 was obtained, the acrylic copolymer 2 was further heated and dissolved in aqueous ammonia in the same manner as in Production Example 1 to obtain an aqueous acrylic resin varnish No. 3 having a solid content of 30%. 2 was obtained.

Production Example 3 In a four-necked flask equipped with a thermometer, an emulsifier, a nitrogen gas inlet tube, and a dropping funnel, 690 parts of water and 10 parts of polyoxyethylene nonylphenyl ether (25 moles of ethylene oxide added) were added. It heated to 80 degreeC, mixing and stirring and mixing.

A mixture of 160 parts of methyl methacrylate, 160 parts of styrene, 80 parts of butyl acrylate and 8 parts of ammonium persulfate was added dropwise over 3 hours, reacted, and further reacted for 2 hours to obtain an aqueous solution having a solid content of 40%. Acrylic resin varnish No. 3 was obtained.

<Production of Aqueous Styrene-Maleic Resin Varnish> Production Example 4 A four-necked flask equipped with a thermometer, a stirrer, a condenser, and a dropping funnel was charged with 600 parts of ethyl acetate.
After heating to 78 ° C., while introducing nitrogen gas, 150.8 parts of styrene, 249.2 parts of monobutyl maleate, and ditertiary butyl peroxide 4 as a polymerization initiator were added.
Parts of the mixture were added dropwise over 3 hours. After completion of the dropwise addition, polymerization was carried out at reflux temperature for 3 hours to complete the reaction, and ethyl acetate was distilled off to obtain a styrene-maleic acid copolymer 1 having an acid value of 209.

In a container equipped with a stirrer, 300 parts of the crushed styrene-maleic acid copolymer 1 and 700 parts of aqueous ammonia containing 1.2 equivalents of ammonia with respect to the neutralized amount were charged and stirred. While heating and dissolving at 80 ° C.
0% aqueous styrene-maleic acid resin varnish 1
I got

<Production of Aqueous Polyurethane Resin Varnish> Production Example 5 300 parts of polyneopentyl glycol adipate diol having a molecular weight of 1,000 were placed in a four-necked flask equipped with a thermometer, a stirrer, a condenser, and a nitrogen inlet tube, and isophorone. 133.2 parts of diisocyanate was charged and reacted at 100 to 105 ° C. for 4 hours with stirring while introducing nitrogen gas.
Next, 24.1 parts of dimethylolpropionic acid was charged and reacted at 100 to 110 ° C. for 2 hours.

Thereafter, the mixture is cooled to 100 ° C.
And 20.2 parts of triethylamine to prepare an aqueous solution, and the reaction was terminated with 12.1 parts of monoethanolamine. The aqueous polyurethane resin varnish No. 1 having a solid content of 30%, an acid value of 24 for the resin, and a molecular weight of 5,000 for the resin. 1 was obtained.

Production Example 6 In the same apparatus as in Production Example 5, 300 parts of a polycarbonate diol having a molecular weight of 12,000, and α, α, α ′,
α'-tetramethylxylylene diisocyanate
7 parts were charged, and 100 parts were stirred while introducing nitrogen gas.
Reaction at -105 ° C for 4 hours, then the reaction product of trimellitic anhydride and trimethylolpropane in a 1: 1 molar ratio. One part was added and reacted at 100 to 110 ° C for 2 hours.

Thereafter, the mixture was cooled to 100 ° C., charged with 997 parts of water and 14 parts of triethylamine to make it aqueous, and further quenched with 13.3 parts of dihydrazine adipate to give a solid content of 30%, an acid value of 31 for the resin, Molecular weight of 6
2,000 aqueous polyurethane resin varnish No. 2 was obtained.

<Production of Aqueous Printing Inks> Examples 1 to 15 and Comparative Examples 1 to 9 First, according to the formulations in Tables 1 and 2, a pigment and the aqueous binder resin varnish obtained above (Examples 10, 11 and Comparative Examples 6, a commercially available aqueous ethylene-acrylic acid resin varnish is used), and the mixture is kneaded with a Red Devil type paint conditioner for 30 minutes, and further, a predetermined material is mixed and stirred, and Examples 1 to 15 and The aqueous printing ink compositions of Comparative Examples 1 to 9 were obtained.

The pigment used is Lionol Blue FG-.
7330 (manufactured by Toyo Ink Mfg. Co., Ltd.), aqueous ethylene-
Examples of the acrylic acid resin varnish include Seixen AC (Sumitomo Seika Co., Ltd., acrylic acid content 20%, melt index 300 g / 10 minutes, solid content 30%), and dimethylpolysiloxane alkylene oxide adduct B
YK348 (manufactured by BYK Chemical) was used.

<Evaluation of aqueous printing ink> Examples 1 to 10
In the case of the inks of Comparative Examples 1 to 6, paper was used as an adherend, and in the case of the inks of Examples 11 to 15 and Comparative Examples 7 to 9, a plastic film was used as an adherend. went. The results are shown in Tables 1 and 2.

The evaluation method and evaluation criteria are as follows.

Using a gravure proofing machine, a plate depth of 32 μm
m, a gravure plate with a cell diameter of 130 μm and a length of 50 m
m, 0.7mm-thick fine line pattern on coated paper and OP
Printing was performed on a P film (biaxially oriented polypropylene film).

Leveling Ability Evaluation Method Halftone dots of the gravure printed matter were enlarged and observed, and the leveling property of the printed matter was visually evaluated. Evaluation Criteria The leveling property was judged to be better if there was no difference in color density between the central part and the peripheral part of the halftone dot, and ranking was performed as follows. A: Almost no difference in density. B: Slight difference in density. C: A crescent-shaped mottled pattern is observed in the halftone dots.

Evaluation Method of Halftone Reproducibility The halftone dot reproducibility was evaluated based on the halftone dot diameter of the printed material obtained by the gravure printing. Evaluation criteria A: The halftone dot diameter of the printed matter is less than 137 μm (105% of the plate cell diameter). B: The dot diameter of the printed matter is 137 μm or more and 156 μm
(Less than 120% of plate cell diameter). C: Printed matter having a dot size of 156 μm or more.

Evaluation Method of Fine Line Reproducibility The fine line reproducibility was evaluated from the width of the fine line of the printed matter obtained by the gravure printing. Evaluation criteria A: The width of the fine line of the printed matter is less than 0.74 mm (105% of the width of the design of the plate). B: The width of the fine line of the printed matter is 0.74 mm or more and 0.84 m
m (120% of the width of the plate design). C: The fine line width of the printed matter is 0.84 mm or more.

[0112]

[Table 1]

[0113]

[Table 2]

[0114]

As described above, as specifically shown in the embodiments,
The aqueous printing ink composition of the present invention has a good leveling property when printed on paper or a plastic film, and gives a printed matter having excellent dot reproducibility and fine line reproducibility.

Claims (4)

[Claims] 1. An aqueous printing ink composition comprising a pigment and an aqueous binder resin varnish as main components, further comprising a water-soluble or water-dispersible dimethylpolysiloxane alkylene oxide adduct represented by the following general formula (1):
An aqueous printing ink composition comprising 0.005 to 5% by weight of the ink composition. Embedded image In the general formula (1), m is 0 or an integer of 1 or more, n is an integer of 1 or more, and n Xs are each independently a general formula (2): (In the formula, p is an integer of 1 or more, R ¹ is a residue of a radically polymerizable hydroxy compound used for introducing a hydroxyl group into a siloxane chain, and p R ² are each independently an ethylene group or a propylene group. At least one of which is an ethylene group, and R ³ is a hydrogen atom or an alkyl group having a carbon number within a range in which the compound represented by the general formula (1) can maintain water solubility or water dispersibility. Is a group represented by In the general formula (1), the formula (3): And a group represented by the formula (4): (In the formula, X is the same as described above), the groups represented by the above may be randomly arranged, or each may be arranged in a block shape. 2. The aqueous printing ink composition according to claim 1, wherein the water-soluble or water-dispersible dimethylpolysiloxane alkylene oxide adduct is contained in the ink composition at 0.05 to 2% by weight. 3. An emulsifier and / or a basic compound, wherein the binder resin varnish comprises at least one selected from the group consisting of a polyurethane resin, an acrylic resin, a styrene-maleic acid resin, and an ethylene-acrylic acid resin. The aqueous printing ink composition according to claim 1 or 2, which is an aqueous binder resin varnish obtained by dissolving or dispersing in water in the presence of (a). 4. A method for producing printed matter, comprising printing the aqueous printing ink composition according to claim 1 on paper or a plastic film by flexo or gravure printing.