JP2003105229A - Coloring pigment for printing ink, printing ink and pigment dispersion containing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a coloring pigment for a printing ink, being a coloring pigment for various printing inks such as a relief printing ink, an offset lithographic ink, a rotogravure ink, a screen ink, a flexographic ink, a water-color ink and inks for writing implements such as an aqueous ball-point pen and oleaginous ball-point pen, which is excellent in dispersibility and light resistance though it has a high tinting power and is a particulate. SOLUTION: The coloring pigment comprises a composite particle powder having an average particle diameter of 0.001-1.0 μm in which a particle surface of a white inorganic particle powder is coated with an adhesive agent, and further, an organic pigment or carbon black is together coated. A printing ink contains the coloring pigment.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention provides a coloring pigment for a printing ink, which has a high coloring power, is fine particles, and is excellent in dispersibility and light resistance.

Color pigments for printing inks according to the present invention are color pigments for various printing inks such as letterpress inks, offset inks, gravure inks, screen inks, flexo inks, water-based inks and inks for writing instruments such as water-based ballpoint pens and oil-based ballpoint pens. Can be used as

[0003]

As is well known, inorganic pigments and organic pigments are used as color pigments for printing inks such as letterpress inks, offset inks, gravure inks, screen inks, flexo inks, water-based inks and inks for writing instruments such as water-based ballpoint pens and oil-based ballpoint pens. Pigments are used depending on the application.

Inorganic pigments are generally high in hiding power and excellent in heat resistance and light resistance, but are known to be low in coloring power and difficult to obtain a clear hue. In addition, some inorganic pigments have a clear hue, but most of them contain harmful metals such as lead, mercury, cadmium, and chromium as constituent elements, so that hygiene, safety, and From the viewpoint of preventing environmental pollution, alternative pigments are required.

On the other hand, it is known that organic pigments generally have a clear hue and high coloring power, but have a small hiding power and poor light resistance and heat resistance.

The properties required of the color pigment for printing ink vary depending on the type of ink, purpose of use, etc., but in order to obtain a printed matter having a clear hue,
It is required that the color pigment has a clear hue.

Further, due to the speeding up of printing, an ink having a high density is required, and accordingly, a coloring pigment for a printing ink having a high coloring power is required.

Furthermore, the dispersibility of the coloring pigment for printing ink in the vehicle has a great influence on the productivity in the manufacturing process of the printing ink and the storage stability of the printing ink.
There is a demand for a coloring pigment for a printing ink which has excellent dispersibility and dispersion stability in a vehicle.

Further, since the printed matter may be exposed to direct sunlight and wind and rain outdoors, it is necessary to maintain a clear printed image for a long period of time, that is, to have excellent light resistance.

In order to obtain a colored pigment having excellent properties, a technique of combining an inorganic pigment and an organic pigment has been tried so far. For example, a method of coprecipitating yellow lead and phthalocyanine blue or an inorganic pigment. Of attaching an organic pigment to the particle surface of the above (Japanese Patent Laid-Open No. 4-132770),
JP-A-11-181329, etc.) and the like have been proposed.

[0011]

The coloring pigments for printing inks, which have high coloring power and are fine particles, but which are excellent in dispersibility and light resistance, are currently most demanded.
Not yet obtained.

That is, the above-mentioned method of coprecipitating yellow lead and phthalocyanine blue has toxicity because it uses yellow lead, and since it is produced by coprecipitation, the adhesion of phthalocyanine blue. It cannot be said that the strength is sufficient, and the printing ink obtained using this cannot be said to have sufficient storage stability.

Further, since the method described in Japanese Patent Application Laid-Open No. 4-132770 is a method of depositing an organic pigment in the presence of an inorganic pigment, it cannot be said that the adhesion strength of the organic pigment is sufficient. .

In the method described in JP-A No. 11-181329, the organopolysiloxane is dissolved in cyclic silicone, and an organic pigment is added to the resulting solution for atomization treatment, followed by high oil absorption. Impregnated with an inorganic pigment, then
This is a method of volatilizing the cyclic silicone, and it cannot be said that the adhesion strength of the organic pigment is sufficient.

In Japanese Patent Application Laid-Open No. 11-323174, the particle surface of black iron oxide particle powder or black iron oxide hydroxide particle powder is coated with an organosilane compound formed from alkoxysilane. Describes an iron-based black composite particle powder having carbon black fine particle powder attached thereto, which is a technique for fixing carbon black to black core particles.

[0016] Therefore, it is a technical object of the present invention to provide a coloring pigment for a printing ink, which has high coloring power and is fine particles, but which is excellent in dispersibility and light resistance.

[0017]

The above technical problems can be achieved by the present invention as follows.

That is, in the present invention, the surface of the particles of the white inorganic particle powder is coated with a sizing agent and the coating is coated with an organic pigment or carbon black. The composite has an average particle size of 0.001 to 10.0 μm. A color pigment for a printing ink, which is characterized by comprising particle powder (Invention 1).

Further, in the present invention, the particle surface of the white inorganic particle powder is coated with one or more kinds of sizing agents selected from organic silicon compounds and coupling agents, and the coating is coated with an organic pigment or carbon black. A colored pigment for printing ink, which is characterized in that it is composed of composite particle powder having an average particle diameter of 0.001 to 10.0 μm adhered (Invention 2).

Further, the present invention is characterized in that the amount of the organic pigment or carbon black attached is 1 to 500 parts by weight with respect to 100 parts by weight of the white inorganic particle powder, and the printing ink according to the present invention 1 or 2. A coloring pigment for use in the present invention (Invention 3).

Further, the present invention is a printing ink containing any one of the coloring pigments for printing ink according to any one of the first to the third inventions.

The present invention also provides a constituent base material 1 of the pigment dispersion.
A pigment dispersion containing 5 to 1,000 parts by weight of any one of the coloring pigments for printing inks of the invention 1 to invention 3 with respect to 00 parts by weight.

The structure of the present invention will be described in more detail as follows.

First, the color pigment for printing ink according to the present invention will be described.

In the coloring pigment for printing ink according to the present invention, the particle surface of the white inorganic particle powder, which is the core particle powder, has one or more kinds of paste selected from organic silicon compounds, coupling agents, oligomers and polymer compounds. Agent is coated with an organic pigment or carbon black (hereinafter,
It is called "organic pigment". ) Is attached to the composite particles having an average particle diameter of 0.001 to 10.0 μm.

The color pigment for printing ink according to the present invention may be provided with a plurality of colored adhesion layers made of organic pigment or the like on the surface of white inorganic particles which are core particles. For example, the particle surface of white inorganic particles is coated with a sizing agent, and a colored adhesion layer (hereinafter referred to as “first colored adhesion layer”) in which an organic pigment or the like is adhered to the coating is formed (hereinafter referred to as “first colored color layer”). The white inorganic particles on which the adhesive layer is formed are referred to as "intermediate pigments", and the surface of the first colored adhesive layer is coated with a sizing agent, and the organic pigment or the like is adhered to the coating. , "Second colored adhesion layer") is formed. If necessary, a colored adhesion layer may be further formed in the same manner. (Hereinafter, a color pigment having two or more colored adhesion layers is referred to as a "colored pigment having a plurality of colored adhesion layers".)

The white inorganic particles in the present invention include white pigments such as titanium dioxide and zinc oxide, pearl pigments such as titanium mica and muscovite, silica powder, white carbon, fine silica particles such as silicic acid and diatomaceous earth, clay, and the like. Examples include extender pigments such as calcium carbonate, barium sulfate, alumina white, white carbon, talc, transparent titanium oxide, and satin white.

The particle shape of the inorganic particles may be any of spherical, granular, polyhedral, acicular, spindle-shaped, rice granular, flake-shaped, scale-shaped and plate-shaped.

The particle size of the white inorganic particle powder is such that the average particle size is 0.0009 to 9.99 μm, preferably 0.0.
014 to 9.49 μm, more preferably 0.0019 to
It is 8.99 μm.

When the average particle diameter exceeds 9.99 μm, the coloring pigment obtained becomes coarse particles, so that the coloring power is lowered, and when it is less than 0.0009 μm, the intermolecular force due to the fineness of the particles is increased. Since the increase causes aggregation, it becomes difficult to uniformly coat the surface of the particles with a sizing agent and uniformly attach the particles with an organic pigment or the like.

The BET specific surface area value of the white inorganic particle powder is 0.5 m ² / g or more. BET specific surface area value is 0.5
When it is less than m ² / g, the white inorganic particles are particles and particles that are sintered between the particles, and the obtained color pigment becomes coarse particles and the coloring power is lowered. Considering the coloring power of the color pigment, the BET specific surface area value is preferably 1.0 m ² / g or more, more preferably 1.5 m ² / g or more. Considering the uniform coating treatment with the sizing agent and the uniform adhesion treatment with the organic pigment or the like on the particle surface of the white inorganic particle powder, the upper limit value is 500 m ² / g, preferably 400 m ² / g, and more preferably 300 m ² / g
Is.

The hue of the white inorganic particle powder has an L ^* value of 7
Those having a range of 0.00 or more and a C ^* value of 18.00 or less are preferable, and more preferably an L ^* value of 75.00 or more,
The C ^* value is 16.00 or less. When the L ^* value and the C ^* value are out of the above ranges, it is difficult to say that the hue is white, and it is difficult to obtain the colored pigment intended by the present invention.

The hiding power of the white pigment of the white inorganic particle powder in the present invention is 600 cm ² according to the evaluation method described later.
/ G or more is preferable. Further, the hiding power of the pearl pigment and the extender pigment among the white inorganic particle powders in the present invention is 600.
It is preferably less than cm ² / g.

With respect to the light resistance of the white inorganic particle powder, the lower limit of the ΔE ^* value exceeds 5.0 and the upper limit thereof is 12.0, preferably 11.0, and more preferably 1 by the evaluation method described later.
It is 0.0.

As the sizing agent in the present invention, any agent can be used as long as it can adhere an organic pigment or the like to the surface of the white inorganic particles, preferably an organosilicon such as alkoxysilane, polysiloxane or fluoroalkylsilane. One or more compounds, various coupling agents of silane type, titanate type, aluminate type and zirconate type, oligomers or polymer compounds. Considering the adhesion strength of the organic pigment and the like to the particle surface of the white inorganic particles, more preferably alkoxysilane, polysiloxane, organosilicon compounds such as fluoroalkylsilane, silane-based, titanate-based, aluminate-based and zirconate-based Various coupling agents.

Particularly when silica fine particles are used as the core particles, an organic silicon compound or a silane coupling agent is preferably used as the paste agent.

As the organosilicon compound in the present invention, an organosilane compound formed from an alkoxysilane represented by Chemical formula 1, a polysiloxane represented by Chemical formula 2, a modified polysiloxane represented by Chemical formula 3, and a terminal modified represented by Chemical formula 4. The polysiloxane and the fluoroalkylsilane represented by Chemical formula 5 or a mixture thereof can be used.

[0038]

[Chemical 1]

As the alkoxysilane, specifically,
Examples include methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, diphenyldiethoxysilane, dimethyldimethoxysilane, methyltrimethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, isobutyltrimethoxysilane, and decyltrimethoxysilane. To be

Considering the adhesion strength of the organic pigment or the like on the surface of the white inorganic particles, methyltriethoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane,
Organosilane compounds formed from isobutyltrimethoxysilane and phenyltriethoxysilane are more preferable, and most preferable are organosilane compounds formed from methyltriethoxysilane, methyltrimethoxysilane and phenyltriethoxysilane.

[0041]

[Chemical 2]

[0042]

[Chemical 3]

[0043]

[Chemical 4]

Considering the adhesion strength of the organic pigment or the like on the surface of the white inorganic particles, a polysiloxane having a methyl hydrogen siloxane unit, a polyether modified polysiloxane, and a terminal carboxylic acid modified polysiloxane whose terminal is modified with a carboxylic acid. Siloxane is preferred.

[0045]

[Chemical 5]

Specific examples of fluoroalkylsilanes include trifluoropropyltrimethoxysilane, tridecafluorooctyltrimethoxysilane, heptadecafluorodecyltrimethoxysilane, heptadecaflurodecylmethyldimethoxysilane, and trifluoropropylethoxy. Examples thereof include silane, tridecafluorooctyltriethoxysilane, and heptadecafluorodecyltriethoxysilane.

Considering the adhesion strength of the organic pigment or the like on the surface of the white inorganic particles, a fluorine-containing organosilane produced from trifluoropropyltrimethoxysilane, tridecafluorooctyltrimethoxysilane, or heptadecafluorodecyltrimethoxysilane. The compound is preferable, and a fluorine-containing organosilane compound produced from trifluoropropyltrimethoxysilane or tridecafluorooctyltrimethoxysilane is most preferable.

Among the coupling agents, the silane coupling agents include vinyltrimethoxysilane, vinyltriethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane,
γ-mercaptopropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, N-β (aminoethyl) -γ-aminopropyltrimethoxysilane,
γ-glycidoxypropylmethyldimethoxysilane, γ
-Chloropropyltrimethoxysilane and the like can be mentioned.

Examples of titanate coupling agents include isopropyl tristearoyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate,
Isopropyltri (N-aminoethyl / aminoethyl)
Titanate, tetraoctyl bis (ditridecyl phosphate) titanate, tetra (2-2-diallyloxymethyl-1-butyl) bis (ditridecyl) phosphate titanate, bis (dioctyl pyrophosphate)
Examples thereof include oxyacetate titanate and bis (dioctyl pyrophosphate) ethylene titanate.

As the aluminate-based coupling agent,
Acetoalkoxy aluminum diisopropylate, aluminum diisopropoxy monoethyl acetoacetate, aluminum trisethyl acetoacetate, aluminum tris acetylacetonate and the like can be mentioned.

As the zirconate type coupling agent,
Zirconium tetrakis acetyl acetonate, zirconium dibutoxy bis acetyl acetonate, zirconium tetrakis ethyl acetoacetate, zirconium tributoxy monoethyl acetoacetate, zirconium tributoxy acetyl acetonate, etc. are mentioned.

The oligomer has a molecular weight of 300 or more,
Those having a molecular weight of less than 10,000 are preferable, and those having a molecular weight of 10,000 or more and about 100,000 are preferable as the polymer compound. Considering the uniform coating treatment of the white inorganic particles, a liquid or an oligomer or a polymer compound soluble in water or various solvents is preferable.

The coating amount of the sizing agent is preferably 0.01 to 15.0% by weight, more preferably 0.02 to 12.5% by weight, most preferably 0.02 to 12.5% by weight in terms of C based on the sizing agent-coated white inorganic particle powder. Is 0.03 to 10.0% by weight.

When the amount is less than 0.01% by weight, it is difficult to attach 1 part by weight or more of the organic pigment or the like to 100 parts by weight of the white inorganic particle powder. If it exceeds 15.0% by weight, 1 to 500 parts by weight of an organic pigment or the like can be attached to 100 parts by weight of the white inorganic particle powder, so that it is meaningless to coat more than necessary.

Examples of the organic pigment and the like in the present invention include red organic pigments, blue organic pigments, yellow organic pigments, green organic pigments, orange organic pigments and brown organic pigments which are generally used as colorants for printing inks. Various organic pigments such as organic pigments, violet organic pigments and black organic pigments and carbon black can be used.

Examples of red organic pigments include quinacridone pigments such as quinacridone red, azo pigments such as permanent red, condensed azo pigments such as condensed azo red, vat dye pigments such as dianthraquinonyl red, and perylene red. Perylene pigments can be used. As the blue organic pigment, phthalocyanine-based pigments such as metal-free phthalocyanine blue, phthalocyanine blue, and fast sky blue, and alkali blue can be used. As the yellow organic pigment, a monoazo pigment such as Hansa Yellow, a disazo pigment such as benzidine yellow or permanent yellow, a condensed azo pigment such as condensed azo yellow or an isoindoline pigment such as isoindoline yellow can be used. As the green pigment, a phthalocyanine pigment such as phthalocyanine green can be used. As the black organic pigment, aniline black, perylene black or the like can be used.

As the carbon black in the present invention, fine particles of carbon black such as furnace black, channel black and acetylene black can be used.

The organic pigments may be mixed and used according to the required hue. Further, two or more kinds of colors of similar colors may be used depending on the required hue and characteristics.

In the color pigment having a plurality of colored adhesion layers, the organic pigment or the like adhered to the first colored adhesion layer and the organic pigment or the like adhered after the second colored coating layer may be the same or different in color. Any kind of organic pigments of different colors such as organic pigments of different types may be used. Further, by selecting, as an organic pigment or the like to be combined, one having a function such as light resistance, it becomes possible to obtain a color pigment for a printing ink having a plurality of functions.

The amount of the organic pigment attached is 1 to 500 parts by weight with respect to 100 parts by weight of the white inorganic particle powder.

If the amount is less than 1 part by weight or the amount is more than 500 parts by weight, it becomes difficult to obtain the color pigment of the present invention. It is preferably 30 to 400 parts by weight,
It is more preferably 50 to 300 parts by weight.

In the case of a colored pigment having a plurality of colored adhesion layers, the adhesion amount of the organic pigment or the like in each colored adhesion layer exceeds the upper limit value of the adhesion amount of the organic pigment or the like as a whole depending on the desired hue and characteristics. An appropriate amount may be applied within the range that does not exist.

The particle shape and particle size of the coloring pigment for printing ink according to the present invention largely depend on the particle shape and particle size of the white inorganic particles as core particles, and have a particle morphology similar to the core particles. .

That is, the color pigment for printing ink according to the present invention has an average particle size of 0.001 to 10.0 μm, preferably 0.0015 to 9.50 μm, and more preferably 0.
It is from 0020 to 9.00 μm.

When the average particle diameter of the color pigment for printing ink according to the present invention exceeds 10.0 μm, the particle size is too large and the coloring power is lowered. The average particle size is 0.
If it is less than 001 μm, aggregation tends to occur due to an increase in intermolecular force due to particle miniaturization, which makes it difficult to disperse it in the vehicle.

BE of the coloring pigment for printing ink according to the present invention
T specific surface area value is 1.0 to 500 m ^Two/ G and is preferred
1.5 to 400m^Two/ G, more preferably 2.0
~ 300m^Two/ G. BET specific surface area value is 1.0m
^TwoIf it is less than / g, the particles are coarse or
Particles are sintered between each other and particles, and coloring power
Is reduced. BET specific surface area value is 500m^TwoOver / g
In the case of
Decreases dispersibility in vehicle due to aggregation
To do.

The degree of desorption of the organic pigment and the like from the coloring pigment for printing ink according to the present invention is preferably 5 or 4 and more preferably 5 according to the evaluation method described later. When the degree of desorption of the organic pigment or the like is 3 or less, the desorbed organic pigment or the like may hinder the uniform dispersion in the vehicle, and also the hue of the white inorganic particle powder in the desorbed portion. Appear on the surface of the particles, and it is difficult to obtain a uniform hue.

The coloring power of the color pigment for printing ink according to the present invention is preferably 115% or more, more preferably 120% or more, according to the evaluation method described later.

The hiding power of the color pigment for a printing ink according to the present invention is as follows when a white pigment is used as the white inorganic particle powder.
Preferably at least 700 cm ² / g by the evaluation method described below, more preferably 750 cm ² / g or more. When an extender pigment or a pearl pigment is used as the white inorganic particle powder, it is preferably less than 700 cm ² / g, more preferably 650 cm ² / g or less, still more preferably 600 cm.
² / g or less, most preferably 580 cm ² / g or less.

The light resistance of the coloring pigment for printing ink according to the present invention is 5.0 or less, preferably 4.0 or less in ΔE ^* value in the evaluation method described later. Particularly, when titanium oxide, zinc oxide or the like having an ultraviolet protection effect is used as the core particles, the ΔE ^* value is preferably 4.0 or less, more preferably 3.0 or less.

The color pigment for a printing ink according to the present invention may, if necessary, have the surface of the white inorganic particle powder preliminarily applied to the surface thereof.
It may be coated with an intermediate coating composed of at least one selected from aluminum hydroxide, aluminum oxide, silicon hydroxide and silicon oxide. The desorption of the organic pigment and the like from the particle surface of the white inorganic particle powder can be further reduced, and the light resistance is improved.

The coating amount of the intermediate coating is calculated as Al in terms of Al with respect to the white inorganic particle powder coated with the intermediate coating.
₂ or the total of the amount converted to Al and the amount converted to SiO ₂ is 0.
01 to 20% by weight is preferable.

When the amount is less than 0.01% by weight, the effect of suppressing the detachment of the organic pigment and the like and the effect of improving the light resistance cannot be obtained. If the coating amount is 0.01 to 20% by weight, the effect of suppressing the detachment of the organic pigment and the like and the improvement of the light resistance can be sufficiently obtained.

The color pigment for a printing ink according to the present invention coated with the intermediate coating has a particle size, BET, which is almost the same as that of the color pigment for a printing ink according to the present invention not coated with the intermediate coating. Specific surface area value, hue (L ^* value, a
^* Value, b ^* value), coloring power and hiding power. Further, the degree of desorption and light resistance of the organic pigment and the like is improved by coating the intermediate coating, and the degree of desorption is preferably 5, and the light resistance is 4.0 or less, preferably 3 in ΔE ^* value. ．
It is 0 or less.

Next, the printing ink containing the coloring pigment for printing ink according to the present invention will be described.

The printing ink according to the present invention uses the coloring pigment for printing ink according to the present invention. The printing ink is not particularly limited, but examples thereof include letterpress ink, offset ink, gravure ink, screen ink, flexo ink, water-based ink and ink for writing instruments.

Among the printing inks according to the present invention, the constituent material and composition ratio of the letterpress printing ink are 5 to 40 parts by weight, preferably 8 to 35 parts by weight, more preferably 10 parts by weight of the color pigment.
To 30 parts by weight, the vehicle is 95 to 60 parts by weight, preferably 92 to 65 parts by weight, more preferably 90 to 70 parts by weight.
Parts by weight, and 0 to 20 parts by weight of other additives.

The vehicle of the letterpress printing ink is composed of resin, oil and solvent, and the resin includes rosin-modified phenol resin, alkyd resin, petroleum resin, gilsonite, rosin, hardened rosin, ester gum, oil-soluble phenol resin, rosin fumaric acid. , Highly oxidized maleic acid, highly oxidized fumaric acid, epoxy resin, etc., oils are vegetable oils, processed oils, mineral oils, solvents are high boiling petroleum solvents, glycols (ethylene glycol, propylene glycol, etc.), glycol derivatives. is there. If necessary, wax (polyethylene wax), compound, extender pigment, dryer, dispersant, thickener, gelling agent, thixotropy imparting agent, etc. may be used as other additives.

The letterpress printing ink containing the color pigment according to the present invention preferably has a storage stability of ΔE ^* value of 1.5 or less, more preferably 1.2 or less. When printed, in the composition described below, the light resistance of the coating film is ΔE ^* value of 5.0 or less, preferably 4.0 or less.

Among the printing inks according to the present invention, the constituent materials and composition ratios of the offset ink are such that the color pigment is 5 to 40.
Parts by weight, preferably 8-35 parts by weight, more preferably 1
0 to 30 parts by weight, the vehicle is 95 to 60 parts by weight,
Preferably 92-65 parts by weight, more preferably 90-7
0 parts by weight, and other additives are 0 to 20 parts by weight.

The vehicle of the offset ink is composed of resin, oil and solvent, and as the resin, rosin-modified phenol resin, alkyd resin, petroleum resin, gilsonite, rosin, ester gum, rosin ester, hydrocarbon solvent soluble maleic acid resin, Cyclized rubbers, epoxy resins and the like, oils such as vegetable oils, processed oils and mineral oils, and solvents such as high boiling point petroleum solvents, alcohols and soybean oils. If necessary, wax (polyethylene wax), compound, extender pigment, dryer, dispersant, thickener, gelling agent, thixotropy imparting agent, etc. may be used as other additives.

The offset ink containing the color pigment according to the present invention preferably has a glossiness of 70% or more, more preferably 75% or more, still more preferably 80% or more, and a storage stability of ΔE ^* value. It is preferably 1.5 or less, more preferably 1.2 or less. When printed, in the composition described below, the light resistance of the coating film is 5.0 in terms of ΔE ^* value.
The following is preferably 4.0 or less.

In the gravure ink constituting materials and composition ratio of the printing ink according to the present invention, the color pigment is 3 to 50 parts by weight, preferably 4 to 45 parts by weight, and more preferably 5 to 5.
40 parts by weight, vehicle is 97 to 50 parts by weight, preferably 96 to 45 parts by weight, more preferably 95 to 60 parts by weight, and other additives are 0 to 20 parts by weight, preferably 0 to 15 parts by weight. , And more preferably 0 to 10 parts by weight.

The vehicle of the gravure ink is composed of a resin and a solvent, and examples of the resin include petroleum resin, Gilsonite,
Rosin, hardened rosin, ester gum, rosin ester,
Maleic acid resin, cyclized rubber, nitrocellulose, acrylic resin, chlorinated rubber, polyamide resin, urethane resin, polyester resin, ethylene-vinyl acetate copolymer resin, vinyl chloride-vinyl acetate copolymer resin, etc., and the solvent is fat. Group hydrocarbons, aromatic hydrocarbons (toluene, xylene), esters (ethyl acetate), ketone solvents (methyl ethyl ketone), alcohols (isopropyl alcohol), glycol derivatives. If necessary, a plasticizer (dioctyl phthalate), a wax, a compound, an extender pigment, a drier, a dispersant, a thickener, a gelling agent, a thixotropy imparting agent and the like may be used as other additives.

The gravure ink containing the color pigment according to the present invention preferably has a glossiness of 70% or more, more preferably 75% or more, even more preferably 80% or more, and a storage stability of ΔE ^* value. It is preferably 1.5 or less, more preferably 1.2 or less. When printed, in the composition described below, the light resistance of the coating film is 5.0 in terms of ΔE ^* value.
The following is preferably 4.0 or less.

Among the printing inks according to the present invention, the constituent materials and composition ratios of the screen ink are such that the coloring pigment is 1 to 30.
Parts by weight, preferably 2 to 25 parts by weight, more preferably 3
To 20 parts by weight, extender pigment is 5 to 40 parts by weight, preferably 10 to 35 parts by weight, and vehicle is 94 to 30 parts by weight.
Parts by weight, preferably 93 to 40 parts by weight, more preferably 92 to 45 parts by weight, the drying oil is 0 to 40 parts by weight, preferably 0 to 35 parts by weight, and the other additives are 0 to 2 parts by weight.
It is 0 part by weight, preferably 0 to 15 parts by weight, more preferably 0 to 10 parts by weight.

The vehicle of the screen ink is composed of a resin and a solvent, and as the resin, an alkyd resin, a rosin-modified phenol resin, a ketone resin, a petroleum resin, a rosin ester, a maleic acid resin, a cyclized rubber, a cellulose derivative (nitrocellulose, ethyl cellulose). , Ethyl hydroxyethyl cellulose), acrylic resin, chlorinated rubber, polyamide resin, urethane resin, polyester resin, ethylene-vinyl acetate copolymer resin, vinyl chloride-vinyl acetate copolymer resin, epoxy resin, urea resin, melamine resin,
Polyvinyl chloride, polyester acrylate, urethane acrylate, epoxy acrylate, etc., and as the solvent, aliphatic hydrocarbon (mineral spirit), aromatic hydrocarbon, alcohol, glycol derivative, ester,
Examples include ketone solvents. If necessary, other additives such as plasticizers, compounds, dryers, dispersants, thickeners, gelling agents, thixotropy imparting agents, antioxidants, cross-linking agents, curing agents, defoamers, matting agents, and anti-UV agents. Alternatively, a surfactant or the like may be used.

The screen ink containing the color pigment according to the present invention has a glossiness of preferably 70% or more, more preferably 75% or more, even more preferably 80% or more, and storage stability in terms of ΔE ^* value. It is preferably 1.5 or less, more preferably 1.2 or less. When printed, in the composition described below, the light resistance of the coating film is 5.0 in terms of ΔE ^* value.
The following is preferably 4.0 or less.

In the printing ink according to the present invention, the constituent material and composition ratio of the water-based ink are 1 to 30 parts by weight, preferably 2 to 25 parts by weight, more preferably 3 to 2 parts by weight of the color pigment.
0 parts by weight, extender pigment is 0 to 40 parts by weight, preferably 0 to 30 parts by weight, and vehicle is 99 to 30 parts by weight, preferably 98 to 40 parts by weight, more preferably 97.
To 50 parts by weight, and 0 to 20 parts by weight of other additives,
It is preferably 0 to 15 parts by weight, more preferably 0 to 10 parts by weight.

The vehicle of the water-based ink comprises a water-based resin, a solvent and a water-solubilizing agent. As the water-based resin, there are water-soluble resins (starch, cellulose ester, cellulose ether, polyvinyl alcohol, polyvinyl methyl ether, polyacrylamide, polyethylene oxide, polyacryl). Acid salt), water-soluble resin (shellac, rosin / maleic acid resin, styrene / maleic acid resin, acrylic resin), aqueous dispersion resin (acrylic resin, vinyl acetate resin, styrene resin, vinyl chloride resin, synthetic rubber) Latex, polyurethane, polyester, alkyd resin, epoxy ester, rosin ester) and the like, and water as a solvent,
Alcohols, ester-based solvents, ketone-based solvents (methyl ethyl ketone), alcohols (isopropyl alcohol), glycol derivatives, and water-solubilizing agents include aqueous ammonia and water-soluble organic amines. If desired, other additives such as a plasticizer, wax, compound, anticorrosive, antifungal agent, antifoaming agent, drier, dispersant and the like may be used.

The water-based ink containing the color pigment according to the present invention preferably has a glossiness of 70% or more, more preferably 75% or more, even more preferably 80% or more, and a storage stability in ΔE ^* value. It is preferably 1.5 or less, more preferably 1.2 or less. When printed, in the composition described below, the light resistance of the coating film is 5.0 or less in ΔE ^* value,
It is preferably 4.0 or less.

Among the printing inks according to the present invention, the constituent materials and composition ratios of the ink for ballpoint pens are such that the color pigment is 5 to 5
0 parts by weight, preferably 5 to 45 parts by weight, more preferably 5 to 40 parts by weight, the solvent is 35 to 94 parts by weight, preferably 35 to 93 parts by weight, more preferably 35 to 92 parts by weight, 1 to 35 parts by weight of resin, preferably 2 to 3
0 parts by weight, more preferably 3 to 25 parts by weight, and other additives are 0 to 20 parts by weight, preferably 0 to 15 parts by weight, more preferably 0 to 10 parts by weight.

Among the inks for ballpoint pens, the solvents in the organic solvent type inks include glycol type solvents, fatty acids,
Glycol ether-based solvent, alcohol-based solvent, ester-based solvent, aliphatic hydrocarbon-based solvent, petroleum-based solvent, ketone-based solvent, etc., as the resin, vinyl resin, hydrocarbon resin, phenol resin, maleic acid resin, styrene/
Examples thereof include acrylic acid copolymer, methyl vinyl ether / maleic anhydride copolymer, and ketone resin. If necessary, other additives such as resins (viscosity modifiers), lubricants, antiseptics, antifungal agents, rust preventives, dispersants, and pH adjusters may be used.

The solvent for the water-based ink among the ballpoint pen inks is water, glycol-based solvent, fatty acid, glycol ether-based solvent, alcohol-based solvent, or the like.
As the resin, water-soluble resin (starch, cellulose ester, cellulose ether, polyvinyl alcohol, polyvinyl methyl ether, polyacrylamide, polyethylene oxide, polyacrylate), water-soluble resin (shellac, rosin maleic acid resin, styrene maleic acid resin, Acrylic resin), aqueous dispersion resin (acrylic resin,
Vinyl acetate resin, styrene resin, vinyl chloride resin, synthetic rubber latex, polyurethane, polyester, alkyd resin, epoxy ester, rosin ester) and the like. If necessary, other additives such as resin (viscosity modifier), lubricant, antiseptic, antifungal agent, rust inhibitor,
You may use a dispersing agent, a pH adjuster, etc.

The storage stability of the ballpoint pen ink containing the color pigment according to the present invention is preferably 1.5 or less, more preferably 1.2 or less in terms of ΔE ^* value. When printed, in the composition described below, the light resistance of the coating film is ΔE ^*.
The value is 5.0 or less, preferably 4.0 or less.

Next, a method for producing the color pigment for printing ink according to the present invention will be described.

The color pigment according to the present invention comprises mixing white inorganic particles and a sizing agent, coating the surface of the white inorganic particles with the sizing agent, and then coating the white inorganic particles with the sizing agent and the organic pigment. Can be obtained by mixing.

The white inorganic particle powder is coated on the particle surface with a sizing agent by mechanically mixing and stirring the white inorganic particle powder and a sizing agent or a solution of the sizing agent, or by mixing the white inorganic particle powder with a sizing agent solution or It suffices to mechanically mix and stir while spraying the sizing agent. Almost all of the added sizing agent is coated on the particle surface of the white inorganic particle powder.

When alkoxysilane or fluoroalkylsilane is used as the sizing agent, the coated alkoxysilane or fluoroalkylsilane is an organosilane produced from the alkoxysilane, a part of which is produced by the coating step. It may be coated as a fluorine-containing organosilane compound produced from a compound or a fluoroalkylsilane. Even in this case, it does not affect the subsequent adhesion of the organic pigment or the like.

In order to uniformly coat the surface of the white inorganic particles with the sizing agent, it is preferable that the agglomeration of the white inorganic particles is previously unraveled by using a pulverizer.

As a device for mixing and stirring the white inorganic particles and the sizing agent, and mixing and stirring the organic pigment and the white inorganic particles having the sizing agent coated on the surface of the particles, a shearing force is applied to the powder layer. A device that can be added is preferable, and it is preferable to use a device that can simultaneously perform shearing, spatula, and compression, such as a wheel-type kneader, a ball-type kneader, a blade-type kneader, and a roll-type kneader. The wheel type kneader can be used more effectively.

As the wheel type kneader, an edge runner (“Mix muller”, “Simpson mill”,
(Synonyms with "Sandmill"), Marutimaru, Stutzmill, wet pan mill, Connor mill, ring muller, etc., preferably edge runner, multi-maru, Stutzmill, wet pan mill, ring muller,
More preferably, it is an edge runner. As the ball type kneader, there is a vibration mill. Examples of the blade type kneader include a Henschel mixer, a planetary mixer, and a Nauta mixer. As the roll type kneader, there is an extruder.

The treatment conditions at the time of mixing and stirring the white inorganic particles and the sizing agent may be appropriately adjusted so that the sizing agent is coated on the surface of the white inorganic particles as uniformly as possible, and the line load is 19.6. ~ 1960 N / cm (2-200 Kg /
cm) is preferable, and more preferably 98-1470 N /
cm (10 to 150 Kg / cm), most preferably 14
7 to 980 N / cm (15 to 100 Kg / cm), the processing time is preferably 5 minutes to 24 hours, more preferably 10 minutes to 20 hours, and the stirring speed is 2 to 2
000 rpm is preferable, and more preferably 5 to 1000
rpm, most preferably 10-800 rpm.

The amount of the sizing agent added was 100% white inorganic powder particles.
0.15-45 parts by weight is preferable with respect to parts by weight. 0.
White inorganic particle powder 1 depending on the addition amount of 15 to 45 parts by weight
1 to 500 parts by weight of an organic pigment or the like can be attached to 100 parts by weight.

After the surface of the white inorganic particles is coated with the sizing agent, an organic pigment or the like is added and mixed and stirred to adhere the organic pigment or the like to the sizing agent coating. If necessary, drying or heat treatment may be further performed.

The organic pigment or the like is added little by little over a period of time, particularly 5 minutes to 24 hours, preferably 5 minutes to 20 hours, or white inorganic particle powder 1
It is preferable to add 5 to 25 parts by weight of the organic pigment and the like to 00 parts by weight in portions until the desired addition amount is achieved.

The treatment conditions at the time of mixing and stirring may be appropriately adjusted so that the organic pigment and the like are uniformly attached, and the linear load is 19.6 to 1960 N / cm (2 to 200 Kg / c).
m) is preferable, and more preferably 98-1470 N / c.
m (10 to 150 Kg / cm), most preferably 147
~ 980 N / cm (15-100 Kg / cm),
The treatment time is preferably 5 minutes to 24 hours, more preferably 10 minutes to 20 hours, and the stirring speed is 2 to 200.
0 rpm is preferred, more preferably 5-1000 rp
m, most preferably 10 to 800 rpm.

The amount of the organic pigment added is 1 to 500 parts by weight, preferably 30 to 400 parts by weight, and more preferably 50 to 300 parts by weight, based on 100 parts by weight of the white inorganic particle powder.
Parts by weight. If the addition amount of the organic pigment or the like is out of the above range, the intended color pigment for printing ink cannot be obtained.

The heating temperature for the drying or heat treatment is usually preferably 40 to 150 ° C, more preferably 6 ° C.
The heating time is 0 to 120 ° C., and the heating time is preferably 10 minutes to 12 hours, more preferably 30 minutes to 3 hours.

When an alkoxysilane and a fluoroalkylsilane are used as the sizing agent, the organosilane compound produced from the alkoxysilane or the fluorine-containing compound produced from the fluoroalkylsilane is finally obtained through these steps. It is coated with an organosilane compound.

In the color pigment for printing ink according to the present invention, the added organic pigment is finely and uniformly adhered to the particle surface of the white inorganic particles through the sizing agent through the treatment process. It is what forms a layer.

A color pigment for a printing ink having a plurality of colored adhesion layers is prepared by mixing white inorganic particle powder and a sizing agent, coating the surface of the white inorganic particle powder with a sizing agent, and then
White inorganic particle powder coated with a sizing agent is mixed with an organic pigment or the like to adhere the organic pigment or the like to the sizing agent coating to form a first colored adhesion layer (intermediate pigment). Then, the intermediate pigment on which the first colored adhesion layer is formed is mixed with a sizing agent, and further,
It can be obtained by mixing a sizing agent-coated intermediate pigment and an organic pigment or the like, and adhering the organic pigment or the like on the first colored adhesion layer via a sizing agent. The mixing treatment with the sizing agent and the mixing treatment with the organic pigment and the like in each of the above steps may be performed in the same manner as the above respective treatments. It should be noted that a coloring pigment for printing ink in which three or more colored adhesion layers are formed can be obtained by repeating coating with a sizing agent and adhesion of an organic pigment or the like as necessary.

The white inorganic particle powder is, if necessary, selected from aluminum hydroxide, aluminum oxide, silicon hydroxide and silicon oxide prior to mixing and stirring with the alkoxysilane or polysiloxane. You may coat with the intermediate coating material which consists of at least 1 type mentioned above.

The coating with the intermediate coating is carried out by adding an aluminum compound, a silicon compound or both compounds to an aqueous suspension obtained by dispersing white inorganic particle powder and mixing and stirring, or if necessary, PH after mixing and stirring
By adjusting the value, the particle surface of the white inorganic particle powder is coated with an intermediate coating consisting of at least one selected from aluminum hydroxide, aluminum oxide, silicon hydroxide and silicon oxide. And then
It is filtered, washed with water, dried and crushed. If necessary, deaeration / consolidation may be further performed.

As the aluminum compound, aluminum salts such as aluminum acetate, aluminum sulfate, aluminum chloride and aluminum nitrate, alkali aluminate salts such as sodium aluminate and the like can be used.

As the silicon compound, No. 3 water glass, sodium orthosilicate, sodium metasilicate or the like can be used.

Next, a method for producing printing ink will be described.

The printing ink according to the present invention may be produced by an appropriate manufacturing method depending on the type of printing ink used.
For example, in the case of producing a high-viscosity printing ink such as a letterpress ink or an offset ink, a resin, a drying oil, a solvent and / or other additives are mixed, heated and dissolved to prepare a vehicle, and then, Add the color pigment to the vehicle and mix using a mixer or kneader,
After kneading with a three-roll mill, etc., after kneading, it is diluted and adjusted to obtain a printing ink.

When producing a printing ink having a low viscosity such as a gravure ink or a flexo ink, a resin is dissolved in a solvent using a high speed stirrer to prepare a vehicle, and then the vehicle and the printing ink are used. It is mixed with a coloring pigment and kneaded, and then diluted and adjusted to obtain a printing ink.

In producing the printing ink, it is possible to easily disperse the coloring pigment for printing ink by using a pigment dispersion in which a high concentration of coloring pigment for printing ink is mixed in resin. The time for kneading can be shortened.

The pigment dispersion in the present invention means a pigment paste, a mill base, a colored chip, etc., and the coloring pigment according to the present invention is 5 to 1000 parts by weight, preferably 100 parts by weight of the pigment dispersion constituting base material. Contains 10 to 800 parts by weight.

As the base material for constituting the pigment dispersion, a resin, a solvent and / or an oil and fat, and if necessary, an antifoaming agent, an extender pigment, a drying accelerator, a surfactant, a curing accelerator, an auxiliary agent and the like are used. Be compounded.

As the resin, solvent and oil and fat used in the pigment dispersion of the present invention, the same resin, solvent and oil and fat as those for the printing ink can be used.

The composition of the resin in the pigment dispersion may be the same as the diluting resin used in the production of the printing ink, or may be different resins. May be determined in consideration of the compatibility between the resins.

The pigment dispersion in the present invention comprises the color pigment and the resin according to the present invention, and, if necessary, a solvent and / or oil and fat, and an additive, a butterfly mixer, a planetary mixer, a pony mixer, a dissolver, a tank mixer, High speed mixer, homo mixer, kneader,
It can be obtained by kneading and dispersing using a disperser such as a roll mill, a sand mill, an attritor and a ball mill.

In the case of colored chips, the color pigment and the resin according to the present invention are optionally mixed with a mixer such as a ribbon blender, a Nauter mixer, a Henschel mixer, a super mixer or the like, and then a known single-screw kneading extruder or It can be obtained by kneading with a twin-screw kneading extruder or the like and then cutting, or by kneading the above mixture with a Banbury mixer, a pressure kneader or the like, pulverizing or molding, and cutting. .

[0127]

BEST MODE FOR CARRYING OUT THE INVENTION A typical embodiment of the present invention is as follows.
It is as follows.

The average particle size of the particles was shown by the average value of the particle sizes of 350 particles shown in the electron micrographs.

The specific surface area value is shown by the value measured by the BET method.

The amount of Al and the amount of Si present on the particle surface of the white inorganic particle powder were measured by using a fluorescent X-ray analyzer 3063M type (manufactured by Rigaku Denki Kogyo Co., Ltd.).
It was measured in accordance with "General rules for X-ray fluorescence analysis" of JIS K0119.

The coating amount of the sizing agent coating the white inorganic particle powder and the coating amount of the organic pigment adhering to the white inorganic particle powder were determined by "Horiba Metal Carbon / Sulfur Analyzer EMIA-22".
It was determined by measuring the amount of carbon using "00 type" (manufactured by Horiba Ltd.).

The degree of detachment of the organic pigment and the like adhering to the white inorganic particles was evaluated by the following method in five levels. 5
Indicates that the amount of the organic pigment desorbed from the surface of the white inorganic particles is small.

2 g of measured particle powder and 20 ml of ethanol
Was placed in a 50 ml Erlenmeyer flask, ultrasonically dispersed for 60 minutes, and then centrifuged at a rotation speed of 10,000 rpm for 15 minutes to separate the particle powder to be measured and the solvent portion.
The measured particle powder thus obtained is dried at 80 ° C. for 1 hour, and the number of desorbed and reaggregated organic pigments and the like existing in the visual field shown in the electron micrograph (× 50,000) is visually observed. However, an electron micrograph (× 5) of the mixed pigment obtained by simply mixing the white inorganic particles and the organic pigment without using a sizing agent.
50,000) and evaluated in 5 steps.

1: White inorganic particles, an organic pigment, and the like are approximately the same as when they are simply mixed without using a sizing agent. 2: 30 or more and less than 50 per 100 white inorganic particles. 3: 10 or more and less than 30 per 100 white inorganic particles. 4: 5 to 10 per 100 white inorganic particles. 5: Less than 5 particles per 100 white inorganic particles.

The hue of the white inorganic particle powder, the organic pigment, and the color pigment for printing ink was 0.5 g of the sample and 0.5 of castor oil.
Knead ml with a Hoover-type Mahler to form a paste,
4.5g of clear lacquer was added to this paste and kneaded,
It is made into paint and 150μm (6m
il) using an applicator, a coated piece (coating thickness: about 30 μm) is prepared, and a standard white plate is used as a back for the coated piece, “Multi-source spectrophotometer MSC-IS-
2D "(manufactured by Suga Test Instruments Co., Ltd.)
The colorimetric index is shown by L ^* value, a ^* value and b ^* value in accordance with JIS Z 8729. It should be noted that the C ^* value represents the saturation and can be obtained according to the following mathematical expression 1.

[0136]

## EQU1 ## C ^* value = ((a ^* value) ² + (b value ^* ) ² ) ^1/2

The coloring power of the coloring pigment for printing ink is
Primary color enamel and developed color enamel manufactured according to the method described in
150 μm of each mel on cast coated paper
(6 mil) applicator applied and applied piece
Was prepared, and the coated piece was subjected to “multi-source spectrophotometer MS
C-IS-2D "(manufactured by Suga Test Instruments Co., Ltd.)
^*Measure the values and calculate the difference by ΔL^*Value.

Then, as a standard sample of the color pigment, a mixed pigment in which an organic pigment and the like and white inorganic particle powder are simply mixed in the same proportion as the color pigment is used, and the primary color enamel and the developed color enamel are prepared in the same manner as described above. A coated piece was prepared, the L ^* value of each coated piece was measured, and the difference was defined as the ΔLs ^* value.

[0139] Using the obtained DerutaLs ^* value of [Delta] L ^* value and the standard sample of colored pigment showed a value calculated according to the following equation 2 as a tinting strength (%).

[0140]

## EQU2 ## Coloring power (%) = 100 + {(ΔLs ^* −Δ
L ^* ) × 10}

Preparation of primary color enamel: 10 g of the above sample powder
And 16 g of amino alkyd resin and 6 g of thinner were mixed and added to a 140 ml glass bottle together with 90 g of 3 mmφ glass beads, and then 4 with a paint shaker.
After mixing and dispersing for 5 minutes, 50 g of amino alkyd resin was added, and further dispersed for 5 minutes with a paint shaker,
A primary color enamel was made.

Preparation of the spread color enamel: the above primary color enamel 1
2 g and 40 g of Amylak White (titanium dioxide-dispersed aminoalkyd resin) were blended and mixed and dispersed for 15 minutes with a paint shaker to prepare a spread enamel.

The hiding power of the white inorganic particle powder, the organic pigment and the like and the color pigment for printing ink is shown by the value obtained by the cryptometer method of JIS K 5101 8.2 using the primary color enamel obtained above. It was

The light resistance of the white inorganic particle powder, the organic pigment and the like and the coloring pigment for the printing ink is determined by comparing the primary color enamel prepared for measuring the coloring power with a transparent glass plate (0.8 m).
m (thickness) × 70 mm (width) × 150 mm (length)) with a thickness of 150 μm, and dried to form a coating film. Half of the obtained measurement application piece is covered with a metal foil, Irradiation intensity of ultraviolet rays is 100 m using "Eye Super UV Tester" (SUV-W13 (manufactured by Iwasaki Electric Co., Ltd.))
After continuous irradiation at W / cm ² for 6 hours, the hue (L ^* value, a ^* value, b ^* value) between the part not irradiated with ultraviolet rays and the part irradiated with ultraviolet rays was covered with a standard white by covering with a metal foil. The measurement was performed with the plate as a back, and the ΔE ^* value calculated according to the following equation 3 was used as a reference, based on the measured value of the portion not irradiated with ultraviolet rays.

[0145]

## EQU3 ## ΔE ^* value = ((ΔL ^* value) ² + (Δa ^* value) ²
+ (Δb ^* value) ² ) ^1/2 ΔL ^* value: Difference in L ^* value of sample to be compared with and without UV irradiation Δa ^* value: Difference in a ^* value of sample to be compared with and without UV irradiation Δb ^* value: Comparison Difference in b ^* value of the sample to be irradiated with and without UV irradiation

The hues of various printing inks using the coloring pigment for printing inks are the same as those of the respective printing inks prepared by the formulation described later on a transparent glass plate (0.8 mm (thickness) × 70 mm).
(Width) × 150 mm (length)) with a thickness of 150 μm, and dried to form a coating film.
"Multi-source spectrophotometer MSC-
"IS-2D" (manufactured by Suga Test Instruments Co., Ltd.) was used for measurement and indicated by L ^* value, a ^* value and b ^* value.

The glossiness of the coating film was shown by the glossiness when the incident angle was 60 ° using the "Glossmeter UGV-5D" (manufactured by Suga Test Instruments Co., Ltd.) for the coating piece for measurement. The higher the glossiness, the better the dispersibility of the printing ink containing the coloring pigment for printing ink.

The light resistance of the coating film using each printing ink was determined by covering one half of the measuring application piece prepared for measuring the hue of the above-mentioned printing ink with a metal foil, and measuring the "Eye Super UV Tester" (SUV). -W13 (manufactured by Iwasaki Electric Co., Ltd.) is used to irradiate ultraviolet rays with an intensity of 100 mW / cm ^2.
After continuously irradiating for 6 hours, the hue (L ^* value, a ^* value, b ^* value) of the part which was not irradiated with ultraviolet rays and the part which was irradiated with ultraviolet rays was measured by covering with a metal foil. It is shown by the ΔE ^* value calculated according to the above-mentioned Equation 3 on the basis of the measured value of the non-irradiated part.

The transparency of the coating films of various printing inks using color pigments is shown in the "self-recording photoelectric conversion" for the coating films obtained by applying the printing ink prepared by the method described below to a 100 μm thick clear base film. Spectrophotometer UV-210
0 ”(manufactured by Shimadzu Corp.) was used to show the linear absorption coefficient defined by the following equation 4 from the light transmittance.

[0150]

## EQU00004 ## Linear absorption coefficient (.mu.m.sup.- ¹ ) = ln (1 / t) / FT t: light transmittance at .lamda. = 900 nm (-) FT: thickness of coating film of film used for measurement (.mu.m)

The storage stability of the printing ink was measured by using each printing ink prepared by the formulation described later on a transparent glass plate (0.8
mm (thickness) x 70 mm (width) x 150 mm (length))
(JIS-G-3141) with a thickness of 150 μm,
L ^* value, a ^* value and b ^* value of the coating film produced by drying,
The L ^* value, a ^* value and b ^* value of a coating film produced by applying the printing ink obtained by allowing the printing ink in a closed container to stand at 60 ° C. for 1 week and drying it, The ΔE ^* value obtained by the measurement according to the following equation 5 was shown.

[0152]

## EQU5 ## ΔE ^* value = ((ΔL ^* ) ² + (Δa ^* ) ² +
(Δb ^* ) ² ) ^1/2 ΔL ^* value: difference in L ^* value before and after standing of the coating film to be compared Δa ^* value: difference in a ^* value before and after standing of coating film to be compared Δb ^* value: comparison Difference of b ^* value before and after leaving the coating film to stand

<Production of Coloring Pigment for Printing Ink> Silica particle powder (particle shape: spherical, average particle diameter 0.022 μm,
BET specific surface area value 193.8 m ² / g, L ^* value 92.
4, a ^* value of 0.2, b ^* value of 0.4, C ^* value of 0.4, hiding power of 10 cm ² / g, light resistance of 8.14, and 7.0 kg of methyl hydrogen polysiloxane (trade name: TSF4
84: GE Toshiba Silicone Co., Ltd.) 280 g was added to the silica particle powder while operating the edge runner, and 30 was applied at a linear load of 588 N / cm (60 Kg / cm).
Mixing and stirring were performed for a minute. The stirring speed at this time is 2
It was carried out at 2 rpm.

Next, organic pigment B-1 (type: phthalocyanine pigment, particle shape: granular, average particle diameter 0.06 μm)
m, BET specific surface area value 71.6 m ² / g, hiding power 240
cm ² / g, light resistance ΔE ^* value 10.84, L ^* value 17.
70, a ^* value 9.72, b ^* value-23.44) 7.0k
g is added over 30 minutes while operating the edge runner, and further mixed and stirred for 120 minutes with a linear load of 588 N / cm (60 Kg / cm) to attach the organic pigment B-1 to the methylhydrogenpolysiloxane coating. After letting
It was dried at 80 ° C. for 60 minutes using a dryer to obtain a color pigment for printing ink. The stirring speed at this time is 22
It was done at rpm.

The color pigment for printing inks obtained was granular particles having an average particle diameter of 0.026 μm. BET specific surface area value is 128.1 m ² / g, L ^* value of hue is 2
0.89, a ^* value is 9.41, b ^* value is -21.63, coloring power is 158%, hiding power is 550 cm ² / g,
Light resistance ΔE ^* value is 1.60, and the degree of desorption of organic pigment is 5
And the coating amount of methylhydrogenpolysiloxane was 1.08% by weight in terms of C. The amount of the organic pigment attached was 33.16% by weight in terms of C (corresponding to 100 parts by weight with respect to 100 parts by weight of the silica particle powder).

From the observation result of the electron micrograph of the obtained coloring pigment for printing ink, since almost no particles of the added organic pigment B-1 were observed, almost all the amount of the organic pigment B-1 was methyl hydrogen poly. It was found to be attached to the siloxane coating. Further, the organic pigment B-1 does not maintain the particle shape and particle size at the time of addition, and forms an adhesion layer on the particle surface of the core particles in a state of being much finer than the core particles. Admitted.

<Production of Offset Ink> 70.0 parts by weight of rosin-modified phenol resin, 20.0 parts by weight of linseed oil and 10.0 parts by weight of light oil were heated at 200 ° C. for 1 hour to prepare a varnish. 70.0 parts by weight of the varnish, 25.0 parts by weight of the color pigment for printing ink obtained above, 2.0 parts by weight of compound, 3.0 parts by weight of cobalt drier were kneaded using a three-roll mill, An offset ink was obtained.

[0158]   Coloring pigment for printing ink 25.0 parts by weight,   Rosin-modified phenolic resin 49.0 parts by weight,   14.0 parts by weight of linseed oil,   Petroleum solvent 7.0 parts by weight,   2.0 parts by weight of compound,   Dryer (cobalt dryer) 3.0 parts by weight.

The storage stability of the obtained offset ink was 0.97 in ΔE ^* value.

Next, the offset ink was applied to a transparent glass plate (0.8 mm (thickness) × 70 mm (width) × 150 mm).
(Length)), the gloss of the coating film obtained is 109
%, Hue L ^* value is 57.26, a ^* value is 4.72, b
^{The *} value was -22.58, the light resistance ΔE ^* value was 2.60, and the linear absorption coefficient was 0.0810 µm ^-1 .

<Production of Gravure Ink> Cured Rosin 2
0.0 parts by weight, petroleum resin 12.0 parts by weight and solvent 68.
0 parts by weight were mixed, and a varnish was prepared using a high speed stirrer. Next, 75.0 parts by weight of the varnish, 7.0 parts by weight of the coloring pigment for printing ink obtained above, and 15.0 of extender pigment.
Parts by weight and 3.0 parts by weight of the additive were mixed and kneaded using a sand mill to obtain a gravure ink.

[0162]   Coloring pigment for printing ink 7.0 parts by weight,   15.0 parts by weight of extender pigment (calcium carbonate),   15.0 parts by weight of cured rosin,   Petroleum resin 9.0 parts by weight,   51.0 parts by weight of solvent (toluene),   Additive (polyethylene wax) 3.0 parts by weight.

The storage stability of the obtained gravure ink is
The ΔE ^* value was 0.96.

Then, the gravure ink was mixed with transparent glass.
Plate (0.8 mm (thickness) x 70 mm (width) x 150 mm
(Length)), the glossiness of the coating film obtained is 112
%, Hue is L^*The value is 58.69, a^*The value is 4.98, b
^*Value is -23.16, light resistance ΔE ^*Value is 2.59
And the linear absorption coefficient is 0.0765 μm^-1Met.

<Production of Water-based Ink> Acrylic Resin 25.
0 part by weight was dissolved in 28% ammonia water 5.0 parts by weight, isopropyl alcohol 14.0 parts by weight and water 56.0 parts by weight to prepare an aqueous vehicle. Then, 28.0 parts by weight of the aqueous vehicle, 15.0 parts by weight of the color pigment for printing ink obtained above and 7.0 parts by weight of water are kneaded using a sand mill, and then 47.5 parts by weight of the aqueous vehicle. Parts, 2.0 parts by weight of additive and 0.5 parts by weight of antifoaming agent were additionally added to obtain an aqueous ink.

[0166]   Coloring pigment for printing ink 15.0 parts by weight,   28.0 parts by weight of aqueous vehicle,   7.0 parts by weight of water,   47.5 parts by weight of additional aqueous vehicle,   Additive (polyethylene wax) 2.0 parts by weight,   Defoamer 0.5 parts by weight.

The storage stability of the obtained water-based ink is ΔE.
^The value was 0.98.

Then, the water-based ink was applied to a transparent glass plate.
(0.8 mm (thickness) x 70 mm (width) x 150 mm (long
The gloss of the coating film obtained by coating
Phase is L ^*Value is 58.41, a^*The value is 4.92, b^*value
-23.22, light resistance ΔE^*The value is 2.53,
Collection coefficient is 0.0928 μm^-1Met.

[0169]

The most important point in the present invention is that the surface of the white inorganic particles is coated with a sizing agent, and a uniform adhesion layer is formed on the coating in a state where the organic pigment and the like are finely divided. It is a fact that the coloring pigment for printing ink has high coloring power and is excellent in dispersibility and light resistance even though it is fine particles.

The reason why the color pigment according to the present invention has excellent dispersibility is that the organic pigment which is detached from the particle surface of the extender pigment is firmly attached to the particle surface of the extender pigment. It is considered that this is because the amount of the pigment or carbon black is small, and therefore the dispersed organic pigment or carbon black does not hinder the dispersion in the system.

The reason why the color pigment for printing ink according to the present invention is excellent in light resistance is not clear yet, but
It is thought that it was due to the organic pigments, etc., which are significantly superior in light resistance compared to dyes, were attached to the particle surface of the core particles, which are relatively excellent in light resistance, through a paste agent excellent in light resistance. There is.

The printing ink obtained by using the color pigment for a printing ink according to the present invention is excellent in dispersibility and storage stability, and the printed image obtained by using the printing ink is excellent. Has light resistance.

The reason why the dispersibility of the printing ink according to the present invention is excellent is that the present inventor uses the coloring pigment for printing ink according to the present invention in which desorption of the organic pigment and the like from the surface of the core particles is suppressed. I think it was due to what happened.

The reason why the printing ink according to the present invention is excellent in storage stability is that the present inventors usually disperse the printing ink in the printing ink, and self-aggregate or crystal grow easily with time to precipitate. When the organic pigment or the like uses the color pigment for printing ink according to the present invention, the organic pigment or the like adheres to the surface of the core particles in a finely dispersed state, so that self-aggregation or crystal growth may occur. It is considered that the individual particles are present in the printing ink in a dispersed state.

The reason why the printed image obtained by using the printing ink according to the present invention has excellent light resistance is that the present inventor uses the above-mentioned printing ink according to the present invention as a coloring pigment for printing ink. We believe that this is due to the use of color pigments.

[0176]

EXAMPLES Next, examples and comparative examples will be shown.

Core particles 1 to 6: White inorganic particle powder having the characteristics shown in Table 1 was prepared as the core particle powder.

[0178]

[Table 1]

Core particle 7: Using 20 kg of the titanium oxide particle powder of the core particle 1 and 150 l of water, a slurry containing the titanium oxide particle powder was obtained. The pH value of the redispersion slurry containing the obtained titanium oxide particle powder was adjusted to 10.5 using an aqueous sodium hydroxide solution, and then water was added to the slurry to adjust the slurry concentration to 98 g / l. 150 l of this slurry was heated to 60 ° C., and 1.
5 mol of 0 mol / l sodium aluminate solution
(1.0% by weight in terms of Al based on titanium oxide particle powder)
(Corresponding to the above) was added and held for 30 minutes, and then the pH value was adjusted to 7.5 with acetic acid. After holding in this state for 30 minutes, the particles were filtered, washed with water, dried and pulverized to obtain titanium oxide particle powder having the particle surface coated with aluminum hydroxide.

Table 2 shows the production conditions at this time, and Table 3 shows various characteristics of the obtained surface-treated titanium oxide particle powder.

Core particles 8 to 12: The surface of the particles is coated in the same manner as the core particles 7 except that the white inorganic particle powders of the core particles 2 to 6 are used and the kind and amount of the surface coating are variously changed. A white inorganic particle powder coated with the product was obtained.

Table 2 shows the production conditions at this time, and Table 3 shows various characteristics of the obtained surface-treated white inorganic particle powder.

[0183]

[Table 2]

[0184]

[Table 3]

The type A of the coating material used in the surface treatment step is a hydroxide of aluminum, and S is an oxide of silicon.

Organic pigment and carbon black fine particle powder: An organic pigment and carbon black fine particle powder having various characteristics shown in Table 4 were prepared as the organic pigment and carbon black fine particle powder.

[0187]

[Table 4]

Examples 1 to 12 and Comparative Examples 1 to 3: Kind of additive in addition step in coating step with sizing agent, addition amount, line load and time of edge runner treatment, kind of organic pigment in adhering step of organic pigment, etc. A colored pigment was obtained in the same manner as in the embodiment of the present invention, except that the addition amount, the line load of the edge runner treatment and the time were variously changed.

Table 5 shows the production conditions at this time, and Table 6 shows various characteristics of the obtained color pigment for printing ink.

In Example 2, 50.0 parts by weight of the organic pigment R-1 and 30.0 parts by weight of the organic pigment Y-1 were mixed in advance with 100 parts by weight of the core particle powder by a Henschel mixer or the like. , 20.0 parts by weight of the mixed pigment
Added over 0 minutes. In Example 3, the core particle powder 100
To 1 part by weight, 15.0 parts by weight of the organic pigment B-1 was added in 10 batches. In Example 4, the core particle powder 1
100.0 parts by weight of the organic pigment C-1 was added to 100 parts by weight over 100 minutes. In Example 9, with respect to 100 parts by weight of the core particle powder, the organic pigment C-2 100.0
20 parts by weight were added in 5 parts by weight.

[0191]

[Table 5]

[0192]

[Table 6]

<Coloring Pigment for Printing Ink Having a Plurality of Colored Adhesive Layers> Example 13: Titanium oxide particle powder (particle shape: granular, average particle size 0.253 μm, BET specific surface area value 10.3 m)
² / g, L ^* value of 96.63, a ^* value of −0.58, b ^* value of −0.69, C ^* value of 0.90, hiding power of 1,560 cm ^2.
/ G, light resistance ΔE ^* value 6.15) 20 kg of pure water was stirred with a stirrer to loosen the aggregation,
Further, a "TK Pipeline Homo Mixer" (manufactured by Tokushu Kika Kogyo Co., Ltd.) was passed three times to obtain a slurry containing titanium oxide particle powder.

Next, a slurry containing this titanium oxide particle powder was applied to a horizontal sand grinder "Mighty Mill MH".
G-1.5L "(manufactured by Inoue Seisakusho Co., Ltd.) was passed five times at a shaft rotation speed of 2000 rpm to obtain a dispersion slurry containing titanium oxide particle powder.

325 mesh of the obtained dispersion slurry
The sieve residue at (opening 44 μm) was 0%. The dispersion slurry was filtered and washed with water to obtain a cake of titanium oxide particle powder. 1 cake of this titanium oxide particle powder
After drying at 20 ° C., 11.0 kg of the dry powder was put into an edge runner “MPUV-2 type” (product name, manufactured by Matsumoto Foundry Iron Works Co., Ltd.) and 294 N / cm (30 Kg / c).
m) was mixed and stirred for 30 minutes to lightly loosen the agglomeration of particles.

Next, methyltriethoxysilane (trade name: TSL8123: manufactured by GE Toshiba Silicone Co., Ltd.)
A methyltriethoxysilane solution obtained by mixing and diluting 220 g with 200 ml of ethanol was added to the titanium oxide particle powder while operating the edge runner, and 3
Mixing and stirring were performed for 20 minutes with a line load of 92 N / cm (40 Kg / cm). The stirring speed at this time is 22 rp
I went in m.

Next, organic pigment B-1 (kind: phthalocyanine pigment, particle shape: granular, average particle diameter 0.06 μm)
m, BET specific surface area value 71.6 m ² / g, hiding power 240
cm ² / g, L ^* value 17.70, a ^* value 9.72, b ^*
Value -23.44, light resistance ΔE ^* value 10.84) 2,20
0 g was added while operating the edge runner over 20 minutes, and further mixed and stirred for 60 minutes with a linear load of 392 N / cm (40 Kg / cm), and the organic pigment B-1 was coated on the methyltriethoxysilane coating. To obtain an intermediate pigment having adhered thereto. The stirring speed at this time was 22 rpm.

In order to confirm the coating amount of methyltriethoxysilane and the attached amount of organic pigment B-1, a part of the obtained intermediate pigment was taken and heated at 105 ° C. for 60 minutes using a dryer. Processed. The coating amount of methyltriethoxysilane is 0.130% by weight in terms of C, and the organic pigment B-1
The adhered amount of C was 11.04% by weight in terms of C (corresponding to 20 parts by weight with respect to 100 parts by weight of the titanium oxide particle powder). As a result of observing with an electron micrograph, almost no organic pigment B-1 was observed, and it was confirmed that almost the entire amount of the organic pigment B-1 was attached to the organosilane compound coating layer formed from methyltriethoxysilane. It was

Next, methyltriethoxysilane (trade name: TSL8123: manufactured by GE Toshiba Silicone Co., Ltd.)
220 g was added to the above intermediate pigment while operating the edge runner, and mixed and stirred for 30 minutes with a linear load of 588 N / cm (60 Kg / cm) to obtain an intermediate pigment having a surface coated with methyltriethoxysilane. Obtained. In addition,
The stirring speed at this time was 22 rpm.

Next, organic pigment B-2 (kind: phthalocyanine pigment, particle shape: granular, average particle diameter 0.08 μm)
m, BET specific surface area value 56.3 m ² / g, hiding power 272
cm ² / g, L ^* value 17.32, a ^* value-11.60,
b ^* value −26.53, light resistance ΔE ^* value 10.21) 55
00 g was added over 50 minutes while operating the edge runner, and further mixed and stirred for 120 minutes with a linear load of 588 N / cm (60 Kg / cm), and methyltriethoxysilane was added to the organic pigment B-1 adhesion layer. And organic pigment B-
After 2 was attached, heat treatment was carried out at 80 ° C. for 60 minutes using a dryer to obtain a color pigment for printing ink. The stirring speed at this time was 22 rpm.

As a result of electron micrograph observation, organic pigment B-
Since 2 was hardly observed, it was confirmed that almost the entire amount of the organic pigment B-2 was attached to the methyltriethoxysilane coating layer.

The production conditions at this time are shown in Tables 7 and 8, and various properties of the obtained color pigment for printing ink are shown in Table 11.

Examples 14 to 36, Comparative Examples 4 to 10: Type of core particles, type of sizing agent in the step of attaching the first colored adhesion layer, addition amount, line load and time of edge runner treatment, organic pigment, etc. Type, amount of addition, line load and time of edge runner treatment and type of paste in the second colored adhesion layer attachment process, amount of addition, line load and time of edge runner treatment, type of organic pigment, etc., amount of addition, edge Example 1 except that the line load and time of the runner treatment were variously changed.
A colored pigment was obtained in the same manner as in 3.

The manufacturing conditions at this time are shown in Tables 7 to 10.
Various properties of the obtained color pigment for printing ink are shown in Tables 11 to 13.

In Example 2, 50.0 parts by weight of the organic pigment R-1 and 30.0 parts by weight of the organic pigment Y-1 were mixed in advance with 100 parts by weight of the core particle powder by a Henschel mixer or the like. , 20.0 parts by weight of the mixed pigment
Added over 0 minutes. In Example 3, the core particle powder 100
To 1 part by weight, 15.0 parts by weight of the organic pigment B-1 was added in 10 batches. In Example 4, the core particle powder 1
100.0 parts by weight of the organic pigment C-1 was added to 100 parts by weight over 100 minutes. In Example 9, with respect to 100 parts by weight of the core particle powder, the organic pigment C-2 100.0
20 parts by weight were added in 5 parts by weight.

[0206]

[Table 7]

[0207]

[Table 8]

[0208]

[Table 9]

[0209]

[Table 10]

[0210]

[Table 11]

[0211]

[Table 12]

[0212]

[Table 13]

<Production of Offset Ink> Examples 37 to 52, Comparative Examples 11 to 30: Offset inks were obtained in the same manner as in the embodiment of the present invention, except that the type of the coloring pigment for printing ink was variously changed. It was

Various properties of the obtained offset ink and various properties of the coating film are shown in Tables 14 and 15.

[0215]

[Table 14]

[0216]

[Table 15]

<Production of Gravure Ink> Examples 53 to 68, Comparative Examples 31 to 50: Gravure inks were obtained in the same manner as in the embodiment of the present invention, except that the type of the coloring pigment for printing ink was variously changed. It was

Various properties of the obtained gravure ink are shown in Table 16.
And shown in Table 17.

[0219]

[Table 16]

[0220]

[Table 17]

<Production of Aqueous Inks> Examples 69 to 84, Comparative Examples 51 to 70: Aqueous inks were obtained in the same manner as the embodiment of the present invention except that the kind of the color pigment for printing ink was changed variously. It was

Various properties of the obtained water-based ink are shown in Tables 18 and 19.

[0223]

[Table 18]

[0224]

[Table 19]

<Production of Pigment Dispersion> Examples 85 to 92: Pigment dispersions were obtained by variously changing the types of color pigments for printing inks, the types of resins, the types of additives, the types of solvents, and the compounding amounts. .

Table 20 shows the manufacturing conditions at this time.

[0227]

[Table 20]

<Production of Printing Ink> Examples 93 to 100: types of pigment dispersion, types of resin,
Printing inks were obtained by variously changing the types of additives, the types of solvents, and the blending amounts.

Table 21 shows the manufacturing conditions at this time, and Table 22 shows various characteristics of the obtained printing ink.

[0230]

[Table 21]

[0231]

[Table 22]

[0232]

The coloring pigment for printing ink according to the present invention comprises:
It is suitable as a coloring pigment for printing inks because it has high coloring power, fine particles, and excellent dispersibility and light resistance.

Since the printing ink according to the present invention uses a coloring pigment having high coloring power and excellent dispersibility and light fastness, letterpress ink, offset ink, gravure ink, screen ink, flexo ink, water-based ink and It is suitable as a coloring pigment for various printing inks such as inks for writing instruments such as water-based ballpoint pens and oil-based ballpoint pens.

Continued front page    F-term (reference) 4J037 AA09 AA10 AA11 AA17 AA18                       AA22 AA25 AA26 AA27 CA02                       CB05 CB23 CB26 CB28 CC28                       DD01 DD05 DD07 DD10 EE02                       EE03 EE28 EE43 FF04 FF15                       FF22 FF23                 4J039 AE11 BA04 BA05 BA13 BA16                       BA21 BA22 BA23 BA30 BA32                       BA35 BC07 BC57 BE01 CA06                       CA07 EA35 EA44 EA45 GA01                       GA02 GA03 GA09 GA10 GA27

Claims (5)

[Claims] 1. An average particle size of 0.001 to 1 in which the surface of white inorganic particle powder is coated with a sizing agent and an organic pigment or carbon black is attached to the coating.
A coloring pigment for printing ink, which is composed of powder of composite particles of 0.0 μm. 2. The surface of the white inorganic particle powder is coated with one or more sizing agents selected from organic silicon compounds and coupling agents, and an organic pigment or carbon black is attached to the coating. A coloring pigment for a printing ink, which comprises a composite particle powder having an average particle diameter of 0.001 to 10.0 μm. 3. The coloring pigment for a printing ink according to claim 1, wherein the amount of the organic pigment or carbon black attached is 1 to 500 parts by weight with respect to 100 parts by weight of the white inorganic particle powder. . 4. A printing ink containing the coloring pigment for a printing ink according to claim 1. 5. The coloring pigment for printing ink according to claim 1, which is contained in an amount of 5 to 1,000 parts by weight based on 100 parts by weight of the constituent base material of the pigment dispersion. And a pigment dispersion.