JP2019218517A - Brilliant chromatic ink composition for lithographic printing and method for manufacturing printed matter - Google Patents

Abstract

To provide a brilliant chromatic ink composition for lithographic printing that has high printability and can produce a chromatic printed matter having high glossiness, specularity and color development.SOLUTION: The brilliant chromatic ink composition for lithographic printing is an ink composition for lithographic printing which includes an aluminum pigment, a chromatic coloring agent, a binder resin and a solvent. The binder resin includes at least one kind of resin selected from an alkyd resin and a petroleum resin and the aluminum pigment includes a flat aluminum pigment having an average thickness of 15 to 100 nm in an amount of 3 to 20 wt% based on the total amount of the ink composition.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a brilliant colored ink composition for lithographic printing and a method for producing a printed matter.

2. Description of the Related Art In recent years, printed materials provided with a metallic luster (brightness, glossiness) such as gold, silver, or bronze for the purpose of improving the design properties of printed materials have been increasing as market needs.

Conventionally, these printed materials are created by a printing method such as gravure, silk screen, flexo, or the like. However, the above-described printing method is not suitable for small-quantity and various kinds of printed matter because it takes time and effort to exchange plate materials due to a change in a picture pattern, and also has a problem in terms of printing speed.

On the other hand, when creating a printed matter with a metallic luster using lithographic printing, which has a high printing speed, up to now, paper on which a metal layer has been deposited in advance, or post-processing such as foil stamping or in-line wheeler is used. Needed. However, the method of producing printed matter by paper or post-processing requires a special device to be installed in the printing machine, selecting a base material to use a special paste,
The burden on versatility of base materials, production and cost was great, such as difficulty in forming delicate patterns and small characters. In particular, the post-processing method described above involves applying a foil to a size larger than a required pattern and cutting out only the required pattern. This is wasteful when used for a small pattern.

In order to solve the above-mentioned problems, glittering inks for lithographic printing for imparting metallic luster have been studied and developed.However, conventional products are used for printed materials created by printing methods such as the above gravure, silk screen and flexo. In comparison, the glossiness was significantly inferior.

The reason for this is that it is necessary to select a material for the brilliant ink for lithographic printing in consideration of not only the gloss but also the inking property and emulsification suitability specific to the lithographic printing method. For example, even if an arbitrary aluminum pigment is used, printability and glossiness are not exhibited unless the binder resin used in combination is appropriate.

Another reason is that a paper substrate is used in lithographic printing. Generally, a paper substrate is rough and opaque, unlike a film substrate used in a printing method such as gravure, silk screen, or flexo. The glossiness of the printed material changes due to the influence of the roughness of the substrate surface, and the characteristics of the film substrate cannot be used (for example, the printed material can be visually recognized from the substrate side). However, in order to obtain a printed matter having a mirror surface, it is required that the surface of the printed matter be as smooth as that of the printed matter on the film substrate.

The above problem becomes more remarkable when obtaining a colored print having metallic luster. Specifically, in order to obtain a colored printed matter having metallic luster, when producing a brilliant colored ink for lithographic printing containing a colorant, in addition to glossiness and printability, coloring properties are also required. In addition, the difficulty in selecting the material is increased as compared with the case where no coloring agent is contained. Further, in a printed material using a brilliant colored ink for lithographic printing containing a colorant, incident light may be irregularly reflected or the surface smoothness may be deteriorated by the colorant in the print layer.

As an example of a brilliant colored ink capable of obtaining a colored print having metallic luster, which has been studied so far, Patent Literature 1 discloses a lithographic printing paste ink using an aluminum pigment. In Patent Literature 1, gold (metallic yellow) brilliant ink is manufactured using gold-colored metal powder, but the evaluation of printability has not been sufficiently performed, and the printability has also been poor. There is no description about a method for obtaining an excellent brilliant ink for lithographic printing and further obtaining a printed matter having high gloss, mirror surface and coloring.

Further, as disclosed in Patent Documents 2 and 3, although there are other disclosures regarding a brilliant colored ink containing a colorant, none of the disclosures is for lithographic printing. As described above, the lithographic printing method has many unique problems, and it is difficult to divert the techniques according to Patent Documents 2 and 3 to lithographic printing as it is.

On the other hand, in order to obtain a colored printed matter having a metallic luster, a printed layer made of a brilliant ink (hereinafter also referred to as a “brilliant layer”) and a printed layer made of a colored ink (hereinafter also referred to as a “colored ink layer”) are formed on a substrate. ) Is superimposed and printed. However, in this case, since the incident light is irregularly reflected by the components such as the colorant contained in the colored ink layer, the glossiness of the printed matter is lower than in the case of the glittering layer alone. In addition, since printing is performed using two types of inks, there is a load in terms of production and cost, such as a need to increase the size of the printing apparatus.

For example, Patent Literature 4 discloses a colored printed matter having metallic luster produced by printing pearl ink by flexographic printing and then printing the colored ink by a lithographic printing method.
However, as described in Patent Document 4, since the surface of the printing layer made of the pearl ink is uneven, diffused reflection of light results in a printed matter having poor glossiness. Further, as described above, since the pearl ink specifically disclosed in Patent Document 4 is not for lithographic printing, there is no description about a method of using a brilliant ink in a lithographic printing method and further improving its printability. In addition, as described above, the glossiness of the pearl ink may not be sufficiently exhibited.

As described above, high suitability for printing, high glossiness, and a colored print having specularity and coloring can be obtained.Study on the brilliant colored ink for lithographic printing has not been conducted so far. is there.

JP-T-2007-513206 JP-A-59-74174 JP 2017-171712 A JP 2004-202749 A

The present invention has been made in order to solve the above problems, the purpose of which is high printability,
Another object of the present invention is to provide a brilliant colored ink composition for lithographic printing, from which a colored print having high gloss, specularity and coloring can be obtained.

As a result of intensive studies by the present inventors, while using an alkyd resin and / or a petroleum resin as a binder resin, a flat aluminum pigment having an average thickness of 15 to 100 nm,
It has been found that the above object can be achieved by using a colorant in combination, and the present invention has been completed.

That is, the present invention is an ink composition for lithographic printing containing an aluminum pigment, a colored colorant, a binder resin, and a solvent,
The binder resin contains at least one resin selected from alkyd resins and petroleum resins,
The present invention relates to a brilliant colored ink composition for lithographic printing, wherein the aluminum pigment contains a flat aluminum pigment having an average thickness of 15 to 100 nm in an amount of 3 to 20% by weight based on the total amount of the ink composition.

Furthermore, the present invention relates to the above brilliant colored ink composition for lithographic printing, wherein the flat aluminum pigment has an average particle diameter of 2 to 25 μm.

Further, in the present invention, the alkyd resin has a weight average molecular weight of 1,000 to 120,000,
The present invention relates to the brilliant colored ink composition for lithographic printing, wherein the petroleum resin has a weight average molecular weight of 500 to 5,000.

Further, the present invention relates to the above brilliant colored ink composition for lithographic printing, wherein the binder resin contains the alkyd resin in an amount of 30 to 90% by weight based on the total amount of the ink composition.

Furthermore, the present invention relates to the above brilliant colored ink composition for lithographic printing, wherein the binder resin contains the alkyd resin in an amount of 50 to 100% by weight based on the total amount of the binder resin contained in the ink composition.

Furthermore, the present invention relates to the above brilliant colored ink composition for lithographic printing, wherein the binder resin further contains a rosin-modified phenol resin.

Furthermore, the present invention relates to the above brilliant colored ink composition for lithographic printing, wherein the solvent contains at least one selected from vegetable oils, polymerized vegetable oils, fatty acid esters, and non-aromatic petroleum solvents.

Further, the present invention includes a step of printing using the brilliant colored ink composition for lithographic printing,
The present invention relates to a method for manufacturing printed matter.

Further, the present invention relates to the above-mentioned method for producing a printed matter, further comprising a step of subjecting the printed matter to heat and pressure.

Furthermore, the present invention relates to a printed matter obtained by printing the above-described brilliant colored ink composition for lithographic printing on a substrate.

According to the present invention, it has become possible to provide a brilliant colored ink composition for lithographic printing, in which a colored printed matter having high printability and high glossiness, specularity and color development is obtained.

FIG. 1 is a scanning electron micrograph (× 30,000) of the aluminum pigment 4 used in the examples. FIG. 2 is a scanning electron micrograph (5,000 times) of the aluminum pigment 4 used in the examples.

Hereinafter, the glittering colored ink composition for lithographic printing of the present invention will be described in detail. In the following, the term “brilliant colored ink composition for lithographic printing” is simply referred to as “ink composition” or “ink”.
There is a case.

The ink composition of the present invention contains a flat aluminum pigment having an average thickness of 15 to 100 nm as the aluminum pigment. The average thickness is preferably 15 to 80 nm.
And particularly preferably 15 to 50 nm. When the average thickness is 15 nm or more, the adhesion to the paper base material is improved, and the blocking, the rear body residue and the like are prevented, and the ink composition has excellent printability. In addition, the printed matter becomes less susceptible to the influence of the underlayer, for example, the irregularities due to the paper fibers, is not whitened, has an improved glossiness, and has a mirror-like shine. On the other hand, when the average thickness is 100 nm or less, when the aluminum pigment is oriented on the substrate,
By the step of the overlapping portion is sufficiently small, the aluminum pigment is uniformly oriented,
A remarkable effect of improving glossiness can be obtained, and a printed matter having a mirror-like shine can be obtained. Furthermore, if it is a flat aluminum pigment having the above thickness, it can be uniformly oriented on the paper without being hindered by the coloring agent, so that the smoothness of the printed matter surface is prevented from deteriorating, and the coloring property and the mirror surface of the printed matter are prevented. It is possible to balance with sex.

The average particle diameter of the flat aluminum pigment is preferably 2 to 25 μm, more preferably 3 to 20 μm, and still more preferably 4 to 15 μm. Average particle size is 2
When the particle size is at least μm, no graininess will be produced when the particles are oriented on the substrate, so that irregular reflection of light can be prevented and the glossiness can be improved. On the other hand, when the thickness is 25 μm or less, the overlap of the aluminum pigments becomes preferable, and the glossiness is also improved by preventing irregular reflection of light. In addition, it is possible to uniformly hide the base material of the image area, and it is possible to prevent incomplete attachment. Furthermore, if the flat aluminum pigment has the above average particle diameter, it is less susceptible to the irregular reflection of incident light due to the colored colorant after the formation of the printing layer, so that the color development and mirror finish of the printed matter can be further improved. Some improvement can be realized.

The average thickness and the average particle diameter of the flat aluminum pigment can be measured by a scanning electron microscope. Specifically, the average thickness is a scanning electron micrograph (FIG. 1 is 30,000-fold magnification. A plurality of photographs may be used as necessary.) , Magnification, acceleration voltage, measurement distance, etc. may be changed in a range where the thickness can be measured by an image.) From the above, 100 portions where the thickness of the pigment can be confirmed are extracted, and the thickness of the pigment is measured. Can be obtained by averaging The thickness of the pigment is measured by selecting a pigment that can be measured from a direction parallel to the plane direction of the pigment (perpendicular to the thickness direction of the pigment).

The average particle diameter is a scanning electron micrograph (magnification: 5,000 times; FIG. 2 is a magnification of 5,000. A plurality of photographs may be used, if necessary.) The voltage, the measurement distance, and the like may be changed in a range where the particle diameter can be measured by an image.) From the image, 100 particles whose particle diameter can be confirmed are extracted, and the particle diameter of the pigment (a circle corresponding to the area of the measured particle) is extracted. Can be determined by measuring the average diameter of the sample and averaging the measured values.

There are a plurality of manufacturing methods for the aluminum pigment, and in the present invention, any of the manufacturing methods can be used. For example, the pulverization method melts an aluminum lump (ingot),
This is a method in which flakes or solids are taken out, subjected to surface treatment if necessary, and then milled in a solvent to shape the particle size, thickness and surface state. In the present invention, as the flat aluminum pigment, a form (aluminum paste) as taken out of a mill (dispersed in a solvent) may be used.

In addition, in the vapor deposition method, a flat aluminum pigment is collected by uniformly coating a release layer on a film, further spreading an aluminum layer thereon, and then dissolving the release layer. And, for the obtained aluminum pigment, by agitation treatment, ultrasonic treatment, spray treatment, etc.
This is a technique for adjusting the shape.

In the present invention, if the average thickness is 15 to 100 nm, more preferably the average particle diameter is 2 to
If it is within the range of 25 μm, a flat aluminum pigment manufactured by any of the above manufacturing methods may be used, but a flat aluminum pigment manufactured by a vapor deposition method has a uniform thickness of the pigment. It is preferably selected because it is easy to form a uniform thin film on the surface of the printed matter when printed, and is excellent in glossiness and printability of the printed matter.

Further, aluminum pigments are classified according to the dispersion state in the printing layer, and leafing types and non-leafing types are known. These can be controlled by, for example, the surface treatment of an aluminum pigment.
A leafing type is obtained by performing the treatment described in JP-A No. 4 and surface treatment with a higher fatty acid such as stearic acid. Leafing type aluminum pigments are protruded on the surface of the printing layer and are arranged in parallel, and easily exhibit glossiness. On the other hand, non-leafing type aluminum pigments are likely to be uniformly dispersed in the print layer.

In the present invention, either type can be used as the flat aluminum pigment. However, the leafing type is preferable because the glossiness is quickly expressed and the glossiness is high.

As a commercially available aluminum pigment, "METALURE (Eckert)"
R) series, "PLATINVARIO series" manufactured by ECKERT, "Metasheen (R) series" manufactured by BASF, and the like. In the present invention, any of those that satisfy the above conditions can be suitably used.

The content of the flat aluminum pigment is 3 to 20% by weight, preferably 3 to 15% by weight, more preferably 4 to 10% by weight based on the total amount of the ink composition. When the content of the flat aluminum pigment is 3% by weight or more, the amount becomes sufficient to uniformly cover the base material in the image area,
Image defects such as missing colors are eliminated. Further, since the image is not affected by the background, an image having excellent gloss can be obtained without whiteness. On the other hand, when the content is 20% by weight or less, the flat aluminum pigments do not excessively overlap with each other on the substrate after printing, and a uniform printed surface that does not easily cause irregular reflection is obtained. As a result, the glossiness is improved, A printed matter having a mirror-like shine is obtained.

The ink composition of the present invention contains a colored colorant, and known dyes and pigments can be optionally used. In the present invention, “colored” represents colors other than colorless and white.

Dyes that can be used in the ink composition of the present invention include azo dyes, metal complex salt azo dyes, pyrazolone azo dyes, anthraquinone dyes, phthalocyanine dyes, carbonium dyes, quinone imine dyes, methine dyes, cyanine dyes, and the like.

On the other hand, in the present invention, it is preferable to use a pigment as a colored colorant in terms of light resistance of the printed matter, matching with other materials, and the like. As an ink pigment, general inorganic pigments and organic pigments can be used. Specifically, examples of the inorganic pigment include graphite, zinc yellow, navy blue, cadmium red, red iron oxide, ultramarine, carbon black, graphite and the like. Soluble azo pigments such as C-based (β-naphthol), 2B-based and 6B-based (β-oxynaphthoic) organic pigments; β-naphthol, β-oxynaphthoic anilide, monoazo yellow, disazo yellow, pyrazolone Insoluble azo pigments such as phthalocyanine acetoacetate; condensed azo pigments such as acetoacetic acid arylide; copper phthalocyanine pigments (α blue, β blue, γ blue), halogenated copper phthalocyanine pigments, metal-free phthalocyanine pigments; perylene pigments, quinacridone pigments,
Thioindigo pigments, dioxazine pigments, isoindolinone pigments, and quinophthalone pigments can be mentioned. As described below, the alkyd resin or petroleum resin having an aromatic ring in the structure, which is preferably used in the present invention, has a glossiness, a specularity, by adsorbing on a colored coloring agent.
It is considered that this contributes to the realization of coloring properties. Therefore, it is preferable to use a pigment having an aromatic ring in the structure as the above-mentioned pigment from the viewpoint of enhancing the adsorption.

The amount of the colorant in the present invention is preferably from 0.3 to 15% by weight, more preferably from 0.4 to 12% by weight, based on the total amount of the ink composition, from the viewpoint of ensuring the color developability of the printed matter. It is particularly preferably 0.5 to 8% by weight.

In addition, from the viewpoint of obtaining a printed material having both glossiness and color developing property, the compounding amount of the colored colorant is preferably 2 to 150 parts by weight with respect to 100 parts by weight of the flat aluminum pigment, It is more preferably from 4 to 120 parts by weight, particularly preferably from 5 to 70 parts by weight.

In the present invention, in addition to the pigments described above, colorless pigments such as barium sulfate, calcium carbonate, silicon oxide, titanium oxide, zinc white, alumina white, bentonite, clay, talc, kaolinite (kaolin) and white pigments May be used in combination.

The ink composition of the present invention contains, as a binder resin, at least one resin selected from alkyd resins and petroleum resins. Using these resins as binder resin, and
By using in combination with the flat aluminum pigment and the colorant described above, it is possible to obtain a printed matter having a higher glossiness and color developing property than before and a mirror surface while maintaining lithographic printing suitability. Although the reason is not clear, for example, the following reason can be considered. That is, the alkyd resin and the petroleum resin preferably contain an aromatic ring in the structure, and the aromatic ring is adsorbed on the surface of the flat aluminum pigment or the colored coloring agent, thereby preventing aggregation of each other, and even in the ink composition. It is believed that the pigment is uniformly dispersed. Thereby, it is considered that the flat aluminum pigment is present without unevenness in the printed layer after printing, and excellent gloss, specularity, and color development are exhibited by uniform orientation. Further, it is considered that the viscoelasticity of the ink composition becomes suitable for lithographic printing by being uniformly dispersed, and that trouble during printing can be suppressed. Further, it is considered that the alkyd resin and the petroleum resin preferably have little steric hindrance in molecular structure and do not hinder the orientation of the flat aluminum pigment. In addition, alkyd resins and petroleum resins can impart to the ink composition emulsification suitability, roller transferability, and viscoelasticity suitable for lithographic printing.

As the alkyd resin that can be suitably used in the ink composition of the present invention, for example, a polymer containing an aromatic ring obtained by using a dibasic acid such as phthalic anhydride and a polyhydric alcohol, and a petroleum resin include For example, a polymer obtained by polymerizing a cyclic hydrocarbon such as a cyclic hydrocarbon having 5 carbon atoms and a cyclic hydrocarbon having 9 carbon atoms is exemplified.

The acid value of the alkyd resin is preferably 25 mgKOH / g or less,
More preferably, it is OH / g or less. When the acid value is 25 mgKOH / g or less, there is a tendency that stain during printing due to emulsification is easily prevented. The lower limit is not particularly limited, but is, for example, 5 mgKOH / g or more, preferably 7 mgKOH / g or more.

When an alkyd resin is used in the ink composition of the present invention, its weight average molecular weight is 1,000.
It is preferably from 0 to 120,000, more preferably from 1,000 to 30,000, and still more preferably from 1,000 to 10,000. When the weight average molecular weight is 1,000 or more, an appropriate viscosity can be imparted to the ink composition. When the ink composition has an appropriate viscosity, stains are less likely to occur at the time of printing, so that the addition of a thickener for imparting viscosity can be suppressed. Generally, excessive addition of a thickener tends to cause refraction between incident light and reflected light on the printing paper surface, causing a reduction in gloss. In the present invention, when the weight average molecular weight is 1,000 or more, a decrease in gloss can be effectively suppressed. Further, when the weight average molecular weight is 120,000 or less, the obstruction of the orientation of the flat aluminum pigment can be prevented, a mirror-like shine is developed, and the roughness of the printed surface is easily prevented.

On the other hand, when a petroleum resin is used in the ink composition of the present invention, the weight average molecular weight is preferably from 500 to 5,000, more preferably from 800 to 3,000 for the same reason as in the case of the alkyd resin. And more preferably 800 to 2,000.

The weight average molecular weight can be measured by a known method, for example, a gel permeation chromatography (GPC) method.

In the present invention, the above two types of resins may be used alone or in combination,
It is more preferable to include at least an alkyd resin from the viewpoints of dispersion stability of the flat aluminum pigment and the colored colorant and ease of orientation. In that case, the addition amount of the alkyd resin is
It is preferably from 30 to 90% by weight, more preferably from 40 to 85% by weight of the total amount of the ink composition.
%, Particularly preferably 50 to 80% by weight. When the addition amount is 30% by weight or more, the addition amount of a material that inhibits the orientation of the flat aluminum pigment is suppressed, and a decrease in glossiness can be prevented. When the content is 90% by weight or less, softening and over-emulsification of the ink composition will not occur, and an ink composition having improved printability as well as improved glossiness can be obtained.

When an alkyd resin is contained, the ratio of the content to the total resin in the ink composition is 5%.
It is preferably from 0 to 100% by weight. When the content is 50% by weight or more, the ratio of a resin having a relatively complicated resin structure such as a petroleum resin and a rosin-modified phenol resin can be reduced, and the orientation of the flat aluminum pigment can be made more preferable. As a result, it is possible to improve glossiness and specularity.

In the ink composition of the present invention, a rosin-modified phenol resin can be used in combination, if necessary. At that time, the weight average molecular weight of the rosin-modified phenol resin is from 5,000 to 200,000.
It is preferably 0. When it is 5,000 or more, the effect of imparting viscoelasticity is large, and image defects can be prevented. When it is 200,000 or less, an image having higher glossiness and specularity can be obtained without hindering the orientation of the flat aluminum pigment.

As the solvent used in the ink composition of the present invention, conventionally known solvents can be arbitrarily used. From the viewpoint of making the compatibility with the binder resin, and the viscoelasticity and drying properties of the ink composition suitable, at least one selected from vegetable oils, polymerized vegetable oils, fatty acid esters, and non-aromatic petroleum solvents. It is preferred to include. These solvents may be used alone or in combination of two or more.

In addition, "vegetable oil" represents triglyceride which is an esterification reaction product of glycerin and a fatty acid, and monoglyceride and diglyceride generated by a transesterification reaction. The fatty acid may be a saturated fatty acid or an unsaturated fatty acid.

Representative examples of "vegetable oil" include hemp seed oil, linseed oil, eno oil, euca deer oil, olive oil, cacao oil, kapok oil, kaya oil, mustard oil, kyonin oil, kiri oil, kukui oil,
Walnut oil, poppy oil, sesame oil, safflower oil, radish seed oil, soybean oil, soybean oil, camellia oil, corn oil, rapeseed oil, niger oil, nuka oil, palm oil, castor oil, sunflower oil, grape seed oil Gentian oil, pine seed oil, cottonseed oil, coconut oil, peanut oil, dehydrated castor oil and the like. Particularly, soybean oil, coconut oil, linseed oil, rapeseed oil, and tung oil are preferable.

"Polymerized vegetable oil" means, for example, heating and stirring one or more of the vegetable oils listed above,
Obtained by polymerization. The vegetable oil may be heated and stirred while blowing oxygen. The polymerization reaction may be thermal polymerization, and oxidation polymerization is not essential. As the vegetable oil used for producing the polymerized vegetable oil, soybean oil, coconut oil, linseed oil, rapeseed oil, and tung oil are particularly preferable.

Examples of "fatty acid esters" include vegetable oils produced from one or more of the vegetable oils listed above, such as soybean oil, cottonseed oil, linseed oil, safflower oil, tall oil, dehydrated castor oil, canola oil, rapeseed oil, and the like. Esters are mentioned.

Other examples include fatty acid monoalkyl ester compounds. Among them, the fatty acid constituting the monoester is preferably a saturated or unsaturated fatty acid having 16 to 20 carbon atoms,
Stearic acid, isostearic acid, hydroxystearic acid, oleic acid, linoleic acid,
Linolenic acid, eleostearic acid and the like can be exemplified. The alcohol-derived alkyl group constituting the fatty acid monoalkyl ester compound preferably has 1 to 10 carbon atoms, and includes a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, An example thereof is an ethylhexyl group. Alcohols having these alkyl groups are
They can be used alone or in combination of two or more.

The alcohol constituting the “fatty acid ester” is preferably a monohydric alcohol.

The "non-aromatic petroleum solvent" includes paraffinic, naphthenic, and mixed solvents thereof. As examples of commercially available non-aromatic petroleum solvents, JXTG Energy Co., Ltd. “
AF Solvent No. 5, "AF Solvent No. 6,""AF Solvent No. 7," and the like.
The content of the mixed aromatic hydrocarbon is 1% by weight based on the total amount of the non-aromatic petroleum solvent.
The following is preferred.

When a non-aromatic petroleum solvent is used, its aniline point is preferably from 60 to 130 ° C. When the aniline point is 130 ° C. or lower, the binder resin in the ink composition has excellent solubility and the fluidity of the ink composition can be sufficiently ensured, so that a printed matter having improved leveling and excellent gloss can be obtained. On the other hand, when the temperature is 60 ° C. or higher, the releasability of the solvent from the printing layer during drying is improved, and an ink composition having more excellent drying properties is obtained.

Further, ethers can be used in combination in the ink composition of the present invention. Representative examples include di-n-octyl ether, dinonyl ether, diheptyl ether, dihexyl ether, didecyl ether, nonylhexyl ether, nonylheptyl ether, nonyloctyl ether, and the like.

Further, a metal dryer can be added to the ink composition of the present invention as needed. Examples of the metal dryer include manganese, cobalt, nickel, and zinc complexes.

Furthermore, a thickener can be added to the ink composition of the present invention as needed. Examples of the thickener include carboxylic acid copolymers, gel fatty acid glycerides described in JP-A-2013-213112, and long-chain hydrocarbon copolymers composed of at least one of isobutene and normal butene. No.

Further, the ink composition of the present invention may contain a gelling agent, a pigment dispersant, a drying inhibitor, an antioxidant, a friction resistance improver, a set-off inhibitor, a nonionic surfactant, a polyhydric alcohol, if necessary. Such additives as can be added as appropriate. The ink composition of the present invention has a viscosity of 10.0 to 60.
It is preferably 0 Pa · s.

The ink composition of the present invention is printed on a base material described later using a known lithographic printing method, which is printed by a printing mechanism utilizing repulsion of water and oil. Incidentally, as the printing press used in the lithographic printing, any of an offset rotary printing press and an offset sheet-fed printing press may be used, but from the viewpoint of the orientation of the flat aluminum pigment and the drying property of the ink, It is preferable to select an offset sheet-fed printing press.

In addition, as a method of drying the ink composition, any of a heat set type, an oxidation polymerization type, and a permeation drying type may be selected, but in the case of the present invention, the flat aluminum pigment is gradually leafed over time. From the viewpoint of obtaining a printed matter excellent in glossiness, it can be suitably used especially in lithographic printing having an oxidation polymerization type drying method.

Furthermore, by heating and pressurizing the printed matter obtained above with an endless press machine, a flat press machine, or the like, it is possible to homogenize the flat aluminum pigment randomly oriented on the paper surface, and to obtain a glossiness. Significant improvements can be realized. The heating and pressurizing conditions are preferably from 40 to 130 ° C. and from 10 to 500 kgf / cm ² , since the above-mentioned effects can be more suitably exhibited. There is no particular limitation on the drive speed and time for applying the heating and pressurizing treatment. For example, in the case of an endless press machine, it is in the range of 1 to 40 m / min, and in the case of a flat press machine, it is in the range of 1 to 30 seconds. Preferably, a treatment is performed.

The substrate on which the ink composition of the present invention is printed may be any substrate, such as coated paper, lightly coated paper, or uncoated paper, as long as it is a substrate such as paper printed by a lithographic printing method. Coated paper having a smooth paper surface is preferred because glossiness can be developed.

The ink composition of the present invention can be preferably used for printed materials such as magazines, books, and posters. ADVANTAGE OF THE INVENTION According to the ink composition of this invention, the glossiness is higher than before, maintaining the lithographic printing aptitude, and the printed matter which achieved both glossiness and color development can be obtained.

Next, the present invention will be described based on examples. However, the scope of the present invention is not limited to the following examples. In the following examples, “parts” and “%” mean “parts by weight” and “% by weight”, respectively, unless otherwise specified.

<Measurement conditions of particle size and thickness of aluminum pigment>
The particle size and thickness of the aluminum pigment are determined by a scanning electron microscope “JSM-” manufactured by JEOL Ltd.
6390 LA ", and measured by the method described above.
The measurement conditions and the like are as follows.
Acceleration voltage: 10 kV
Measuring distance: 10mm
Photographing magnification: The photograph was taken at a particle size of 5,000 times and a thickness of 30,000 times.
Measurement angle: Particle size is for aluminum pigment photographed from the direction perpendicular to the plane direction
Measured, and the thickness is measured on the aluminum pigment taken from the direction parallel to the surface direction.
Was measured.
Measurement number: 100 particles of aluminum pigment were measured for particle diameter and thickness, respectively.
Was.

<Measurement conditions of weight average molecular weight>
The weight average molecular weight is determined by gel permeation chromatography "HLC" manufactured by Tosoh Corporation.
-8020 ". A calibration curve was created using a standard polystyrene sample. Tetrahydrofuran was used as the eluent, and three TSKgel SuperHM-M (manufactured by Tosoh Corporation) were used as the column. The measurement was performed at a flow rate of 0.6 ml / min, an injection volume of 10 μl, and a column temperature of 40 ° C.

<Viscosity measurement conditions>
Resins and ink viscosities are measured by Thermo Electron Corporation.
"HAAKE Rheostress600" manufactured at 25 ° C, share rate 117 /
The measurement was performed under the condition of s.

<Measurement conditions of acid value>
The acid value was measured according to JIS K0070. Specifically, 1 g of the resin was dissolved in 20 ml of a mixed solvent of xylene and ethanol at a weight ratio of 2: 1. Then 3
A 3% by weight phenolphthalein solution was added, and neutralization titration was performed with a 0.1 mol / l aqueous solution of potassium hydroxide.

<Gloss measurement conditions>
Using a digital gloss meter “GM-26D” manufactured by Murakami Color Research Laboratory, 20 ° gloss was measured under the following conditions.
Measurement area: about 3 × 3mm
Measurement window area: diameter 10mm
Light source lamp: Halogen lamp (12V, 50W)
If necessary, for example, when the measured value is out of the allowable measurement range, the measured value was corrected according to the method described in the manual attached to the digital photometer to obtain the glossiness.

<Production example of alkyd resin 1>
300 parts of soybean white squeezed oil and 50 parts of phthalic anhydride are added to the container, and the mixture is stirred at 280 ° C. for 2 hours.
30 parts of pentaerythritol and 100 parts of xylene were added and stirred at 200 ° C. for 3 hours. Thereafter, the temperature was raised to 250 ° C., and the mixture was further stirred for 3 hours to obtain a weight average molecular weight of 5,000,
An alkyd resin 1 having an acid value of 14.0 and a viscosity of 10.7 Pa · s was obtained.

<Production example of alkyd resin 2>
After adding 220 parts of soybean squeezed oil and 80 parts of phthalic anhydride to the container, stirring at 280 ° C. for 2 hours,
30 parts of pentaerythritol, 0.02 part of paratoluenesulfonic acid, and xylene 100
And stirred at 200 ° C. for 3 hours. Thereafter, the temperature was raised to 250 ° C., and the mixture was further stirred for 7 hours to obtain an alkyd resin 2 having a weight average molecular weight of 100,000, an acid value of 19.4 and a viscosity of 669.0 Pa · s.

<Production example of alkyd resin 3>
200 parts of soybean white squeezed oil and 100 parts of phthalic anhydride are added to a container, and after stirring at 280 ° C. for 2 hours, 30 parts of pentaerythritol, 0.02 part of paratoluenesulfonic acid, and 10 parts of xylene 10
0 parts was added and the mixture was stirred at 200 ° C. for 3 hours. Thereafter, the temperature was raised to 250 ° C., and the mixture was further stirred for 10 hours to obtain an alkyd resin 3 having a weight average molecular weight of 150,000, an acid value of 9.6, and a viscosity of 820.0 Pa · s.

<Production example of alkyd resin 4>
400 parts of soybean white squeezed oil and 20 parts of phthalic anhydride are added to the container, and the mixture is stirred at 280 ° C. for 2 hours.
30 parts of pentaerythritol and 100 parts of xylene were added and stirred at 200 ° C. for 3 hours. Thereafter, the temperature was raised to 250 ° C., and the mixture was further stirred for 30 minutes to obtain an alkyd resin 4 having a weight average molecular weight of 700, an acid value of 8.8, and a viscosity of 6.0 Pa · s.

<Production example of petroleum resin varnish 1>
40 parts of a petroleum resin (Nissekineopolymer 120, manufactured by JXTG Energy Co., Ltd., weight average molecular weight 1500) and 60 parts of soybean oil are added to the container, the temperature is raised to 140 ° C., the mixture is stirred at the same temperature for 30 minutes, and then cooled. Petroleum resin varnish 1 was obtained.

<Production example of petroleum resin varnish 2>
20 parts of petroleum resin (Nisequineopolymer 160, weight average molecular weight 3500, manufactured by JXTG Energy Co., Ltd.), petroleum resin (Nisequineopolymer 130, manufactured by JXTG Energy Co., Ltd.)
, Weight average molecular weight 1800) and 60 parts of soybean oil were added to a container, heated to 160 ° C., stirred at the same temperature for 60 minutes, and allowed to cool to obtain a petroleum resin varnish 2.

<Production example of rosin-modified phenolic resin varnish 1>
Weight average molecular weight 130,00 synthesized by the production method described in JP-A-09-249726.
0, 38 parts of a rosin-modified phenol resin having an acid value of 24.3, 30 parts of soybean oil, and 31 parts of a non-aromatic solvent AF Solvent No. 5 (manufactured by JXTG Energy Co., Ltd., aniline point: 88.2 degrees) Was added to the container, and the temperature was raised to 180 ° C. After stirring at the same temperature for 30 minutes, the mixture was allowed to cool, and 1.0 part of ethyl acetoacetate aluminum diisopropoxide (ALCH, manufactured by Kawaken Fine Chemical Co., Ltd.) was added as a gelling agent. A modified phenol resin varnish 1 was obtained.

<Production example of rosin-modified phenol resin varnish 2>
A weight average molecular weight of 10,000 synthesized by the production method described in JP-A-2016-155907.
0, 44 parts of a rosin-modified phenol resin having an acid value of 23.6, 29 parts of soybean oil, and 26 parts of a non-aromatic solvent AF Solvent No. 5 (manufactured by JXTG Energy Co., Ltd., aniline point: 88.2 degrees) Was added to the container, and the temperature was raised to 190 ° C. After stirring at the same temperature for 30 minutes, the mixture was allowed to cool, and 1.0 part of ethyl acetoacetate aluminum diisopropoxide (ALCH, manufactured by Kawaken Fine Chemical Co., Ltd.) was added as a gelling agent. A modified phenol resin varnish 2 was obtained.

<Ink production example>
Aluminum pigments and coloring pigments described in Table 1 (LIONOL BLU manufactured by Toyo Ink Co., Ltd.)
E FG7330), an alkyd resin, a petroleum resin varnish, and a rosin-modified phenol resin varnish were charged into a container at a mixing ratio shown in Tables 2 and 3 while mixing and stirring with a mixer, and the temperature was raised to 80 ° C. with stirring. did. After stirring for 120 minutes, the mixture was cooled to 30 ° C., and 2.0 parts of a metal dryer (MK dryer manufactured by Toyo Ink Co., Ltd.) and isotridecanol as an emulsification inhibitor were described in Tables 2 and 3. And the mixture was stirred with a mixer. Thereafter, the viscosity was adjusted to 15.0 to 25.0 Pa · s using a thickener (Polybutene HV-1900, manufactured by JXTG Energy Co., Ltd.), polymerized vegetable oil, and drill oil, and Examples 1 to 37 and Comparative Examples 1 to 12 inks were obtained.

<Content of evaluation>
Each of the inks of Examples 1 to 37 and Comparative Examples 1 to 12 was printed with a pattern containing a solid color and halftone dots (10% in 1 to 100%) under the following printing conditions, and the following was confirmed. And evaluated.
・ Glossiness (glossiness and roughness on the printed surface)
・ Coloring properties ・ Stain resistance ・ Filling properties of paper (piling and white spots)

<Print conditions>
Printing machine: LITHRONE26 (Komori Corporation)
Paper: Mirror Coat Platinum (127.9 g / m ² ) (Oji Paper Co., Ltd.)
Fountain solution: Akwa Unity C 2.0% tap water diluent (Toyo Ink Co., Ltd.)
Printing speed: 6000 sheets / hour: SUPERIA XP-F (Fuji Film Co., Ltd.)
Number of copies: 3000 sheets Solid area Immediately after printing Density: 0.45 ± 0.03

<Glossiness evaluation method>
The glossiness of the solid portion of the obtained printed matter was measured by the above method, and the roughness of the printed surface was visually confirmed to evaluate the glossiness. The evaluation criteria are as follows, ◎, ○
, △ were set to the practical range.
◎: Gloss value of 200 or more and no roughness on the surface of the printed matter ○: Gloss value of 200 or more, but slight roughness was observed on the surface of the printed matter △: Gloss value of 150 or more and less than 200 ×: Some roughness was observed on the surface of the printed matter ×: Gloss value was less than 150 and / or the roughness of the surface of the printed matter was severe

<Evaluation method of color development>
The solid portion of the obtained printed matter was visually evaluated for coloring (coloring). The evaluation criteria were as follows, and ○ and △ were within the practicable range.
：: Printed matter having a colored feeling (indigo color) was observed, and indigo color development was confirmed. Δ: Colored feeling was not so much felt, and only a pale indigo color was formed. X: Colored feeling was felt. It was not colored and only developed silver

<Evaluation method for stain resistance>
Under the above printing conditions, the water amount value of the dampening solution is reduced by 1 from 20 for every 200 copies,
The stain resistance was evaluated by visually confirming the amount of water when stains were observed on the printed matter.
The evaluation criteria were as follows, and ◎, △, and と し た were within the practicable range.
◎: No stain was generated even when the water value was 10 ○: Dirt was generated when the water value was 10 to 12 △: Dirt was generated when the water value was 13 to 15 ×: Dirt was generated even when the water value was 16 or more did

<Evaluation method of inking property>
Printing was performed under the above printing conditions, and the inking property was evaluated by confirming the presence or absence of pilling and white spots. The evaluation criteria were as follows, and ◎, △, and と し た were within the practicable range.
◎: Good inking ability without piling or white spots ○: Some piling was observed, but the inking property was within the allowable range △: Some white spotting was observed, but Poorness was within the allowable range ×: Piling and white spots were conspicuous, and poor inking property

From the results described in Tables 2 and 3, it is a lithographic printing ink composition containing an aluminum pigment, a colored colorant, a binder resin, and a solvent, wherein the binder resin is selected from alkyd resins and petroleum resins. Comprising at least one resin, wherein the aluminum pigment is
The brilliant colored ink composition for lithographic printing, comprising a flat aluminum pigment having an average thickness of 15 to 100 nm in an amount of 3 to 20% by weight based on the total amount of the ink composition, is one of gloss, color developing properties and lithographic printing suitability. Was also a good result.

Claims (10)

An aluminum pigment, a colored colorant, a binder resin, and a lithographic printing ink composition containing a solvent,
The binder resin contains at least one resin selected from alkyd resins and petroleum resins,
The brilliant colored ink composition for lithographic printing, wherein the aluminum pigment contains a flat aluminum pigment having an average thickness of 15 to 100 nm in an amount of 3 to 20% by weight based on the total amount of the ink composition. The brilliant colored ink composition for lithographic printing according to claim 1, wherein the average particle diameter of the flat aluminum pigment is 2 to 25 µm. The alkyd resin has a weight average molecular weight of 1,000 to 120,000,
The glittering colored ink composition for lithographic printing according to claim 1 or 2, wherein the petroleum resin has a weight average molecular weight of 500 to 5,000. The brilliant colored ink composition for lithographic printing according to any one of claims 1 to 3, wherein the binder resin contains the alkyd resin in an amount of 30 to 90% by weight based on the total amount of the ink composition. The glittering colored ink composition for lithographic printing according to any one of claims 1 to 4, wherein the binder resin contains the alkyd resin in an amount of 50 to 100% by weight based on the total amount of the binder resin contained in the ink composition. The glittering colored ink composition for lithographic printing according to any one of claims 1 to 5, wherein the binder resin further contains a rosin-modified phenol resin. The glittering colored ink composition for lithographic printing according to any one of claims 1 to 6, wherein the solvent includes at least one selected from vegetable oils, polymerized vegetable oils, fatty acid esters, and non-aromatic petroleum solvents. A method for producing a printed matter, comprising a step of printing using the glittering colored ink composition for lithographic printing according to claim 1.   9. The method for producing a printed matter according to claim 8, further comprising a step of subjecting the printed matter to a heat and pressure treatment. A printed matter obtained by printing the glittering colored ink composition for lithographic printing according to any one of claims 1 to 7 on a substrate.