JP2003063126A - Ink jet printing - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for manufacturing an ink jet printed matter having a favorite design and an excellent weather resistance. SOLUTION: The method for manufacturing the ink jet printed matter comprises the steps of forming a printing layer (I) by an ink jet method using a water base ink composition containing a pigment dispersive resin of, (A) a polymerizable unsaturated monomer containing at least one type of ionic functional group selected from the group consisting of a tertiary amino group, a quaternary ammonium salt and a sulfonic acid group, (B) a nonionic polymerizable unsaturated monomer having a polyoxyalkylene chain, and (C) a copolymer of other ethylenically unsaturated monomer, a pigment and an aqueous medium; and then forming a clear coating layer (II) thereon by using a clear paint.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to ink jet printing, and more particularly, it is an ink jet printed product having a desired design and excellent weather resistance, which is suitable for outdoor applications such as building walls, outdoor signs, road signs, and car bodies. The present invention relates to a method for producing the same, and an inkjet printed material obtained by the method.

[0002]

2. Description of the Related Art Conventionally, ink jet printers have been widely used as computer printing devices. This inkjet printer ejects inks of three primary colors of red, blue, and yellow and four colors of black from nozzles according to the color tone of each pixel of image data stored in a storage device of a computer, and prints them on a printing paper. By attaching them in dots and overlapping them on printing paper,
The image data is drawn on the printing paper by reproducing the color tone of the pixel and further driving the nozzle in the left-right direction and driving the printing paper in the vertical direction.

In recent years, objects to be drawn by the ink jet method have spread not only to printed paper but also to building wall surfaces, outdoor signboards, road signs, car bodies, etc., and the ink jet inks used have water resistance and weather resistance. However, improvement in light resistance is required.

For this reason, the coloring material of the ink jet ink is being changed from a dye to a pigment, but the aqueous pigment ink is still insufficient in the print density of the printed image, and the dispersion stability of the pigment is insufficient. However, when used as an inkjet ink, there is a problem of clogging at the head, and improvement of the wettability of the pigment and the dispersion stability of the pigment is demanded.

On the other hand, as a method for imparting functions such as weather resistance, scratch resistance, and acid resistance to an ink jet type printed matter, a method of laminating and adhering a plastic film containing an ultraviolet absorber or the like to the printing layer is adopted. Has been done. However, this method has a problem that a great number of man-hours are required for laminating and that the above function is not sufficiently imparted.

[0006]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that a printing layer is formed on a substrate surface by an inkjet method using a specific water-based ink composition. After the formation of the ink, a clear coating layer is formed thereon by using a clear coating, whereby the water-based ink composition is excellent in wettability and dispersibility even at a high pigment concentration, and is excellent in color development and finished appearance. It has been found that a printed matter which can form a layer and is excellent in weather resistance, scratch resistance, acid resistance and the like can be obtained, and has completed the present invention.

Thus, the present invention provides (A) on the surface of the substrate.
A polymerizable unsaturated monomer containing at least one ionic functional group selected from the group consisting of a tertiary amino group, a quaternary ammonium salt group and a sulfonic acid group, (B) a nonionic polymerizable compound having a polyoxyalkylene chain. A printing layer (I) is formed by an inkjet method using an aqueous ink composition containing a pigment-dispersing resin which is a copolymer of an unsaturated monomer and (C) another ethylenically unsaturated monomer, a pigment and an aqueous medium. After that, a clear coat layer (II) is formed thereon by using a clear paint to provide a method for producing an inkjet printed product.

The present invention also provides an ink jet print obtained by the above method.

The method for producing the ink jet printed material of the present invention will be described in more detail below.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION Substrate: The substrate on which a printed matter can be formed according to the present invention is not particularly limited, and examples thereof include materials such as paper, wood, metal and plastics. And base materials such as mortar and slate, and those obtained by subjecting these base materials to surface treatment and / or coating film formation. Further, these base materials may be provided in the form of a pressure-sensitive adhesive sheet by providing an adhesive layer on the surface opposite to the surface on which the print layer is formed, if necessary.

Formation of Printing Layer (I): According to the present invention, the printing layer (I) is formed on the surface of the substrate as described above by the ink jet method using the aqueous ink composition.

In the present invention, the printing layer (I) is, in particular, (A) a tertiary amino group, a quaternary ammonium salt group and a sulfonic acid from the viewpoint of the wettability and dispersion stability of the pigment, and further the color developability. Of a polymerizable unsaturated monomer containing at least one ionic functional group selected from the group, (B) a nonionic polymerizable unsaturated monomer having a polyoxyalkylene chain, and (C) another ethylenically unsaturated monomer It is formed by using an aqueous ink composition containing a resin for dispersing a pigment which is a copolymer, a pigment and an aqueous medium.

The aqueous ink composition will be described in more detail below.

The pigment-dispersing resin contained in the aqueous ink composition which is preferably used for forming the pigment-dispersing resin printing layer (I) is an ionic functional group-containing polymerizable unsaturated monomer (described below). A),
It is a copolymer of a nonionic polymerizable unsaturated monomer (B) and another ethylenically unsaturated monomer (C).

A polymerizable unsaturated resin containing an ionic functional group
Nomer (A): The monomer (A) is a monomer component for introducing a specific ionic functional group into the pigment dispersion resin, and is selected from the group consisting of a tertiary amino group, a quaternary ammonium group and a sulfonic acid group. A polymerizable unsaturated monomer containing at least one selected ionic functional group is used.

Specific examples of the monomer (A) include N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, N, N-dialkylaminoalkyl (meth) acrylates such as N, N-di-t-butylaminoethyl (meth) acrylate and N, N-dimethylaminobutyl (meth) acrylate; N, N-dimethylaminoethyl (meth ) Tertiary amino group-containing polymerizable unsaturated such as N, N-dialkylaminoalkyl (meth) acrylamide such as acrylamide, N, N-diethylaminoethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide Monomer, 2- (methacryloyloxy) ethyl Methyl ammonium chloride, 2- (methacryloyloxy) ethyl trimethyl ammonium bromide, 2- (methacryloyloxy)
(Meth) acryloyloxyalkyltrialkylammonium salts such as ethyltrimethylammonium dimethylphosphate; (meth) acryloylaminoalkyltrialkylammonium salts such as methacryloylaminopropyltrimethylammonium chloride and methacryloylaminopropyltrimethylammonium bromide; tetrabutylammonium (meth) Tetraalkyl (meth) acrylates such as acrylates; Quaternary ammonium base-containing polymerizable unsaturated monomers such as trialkylbenzylammonium (meth) acrylates such as trimethylbenzylammonium (meth) acrylate, 2-acrylamido-2-methylpropanesulfone (Meth) acrylamide-alkanesulfonic acid such as acid; 2-sulfoethyl (Meth) sulfonic acid group-containing polymerizable unsaturated monomers such as sulfoalkyl (meth) acrylates such as acrylate. These monomers can be used alone or in combination of two or more. Among these monomers, as the polymerizable unsaturated monomer (A), particularly N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, 2- (methacryloyloxy) ethyltrimethyl Ammonium chloride and 2
-Acrylamido-2-methylpropanesulfonic acid is preferred.

Further, the above-mentioned polymerizable unsaturated monomer containing a quaternary ammonium base is used in combination with a polymerizable unsaturated monomer containing a tertiary amino group, and particularly 2- (methacryloyloxy) ethyltrimethylammonium chloride is added to N, N.
When used in combination with dimethylaminoethyl (meth) acrylate and / or N, N-diethylaminoethyl (meth) acrylate, the range of pigments to which the resin for pigment dispersion of the present invention can be applied can be expanded.

When used in combination, the proportion of the quaternary ammonium salt group-containing polymerizable unsaturated monomer (a) and the tertiary amino group-containing polymerizable unsaturated monomer (b) is usually (a) /
The weight ratio of (b) is 10/1 to 1/20, especially 5/1 to 1
The range of / 10 is preferable.

Tertiary amino groups and / or quaternary groups introduced into the resin when a tertiary amino group-containing polymerizable unsaturated monomer and / or a quaternary ammonium salt group-containing polymerizable unsaturated monomer is used as the monomer (A). The ammonium base works particularly effectively on the dispersibility of acidic pigments and neutral pigments, while the sulfonic acid group introduced into the resin when a sulfonic acid group-containing polymerizable unsaturated monomer is used as the monomer (A) is particularly effective. Effectively affects the dispersibility of the basic pigment.

Nonionic having polyoxyalkylene chain
Polymerizable unsaturated monomer (B): The monomer (B) is a monomer component that imparts hydrophilicity to the formed copolymer, and has a polyoxyalkylene chain and a polymerizable unsaturated group in one molecule. It is a monomer. Examples of the polyoxyalkylene chain include a polyoxyethylene chain, a polyoxypropylene chain, and a block chain of polyoxyethylene and polyoxypropylene.

The polyoxyalkylene chain has a molecular weight of 200-3.
It is preferred to have a molecular weight in the range 000, especially in the range 300 to 2,500.

A typical example of the monomer (B) is, for example, the following formula (1)

[0023]

[Chemical 1]

In the formula, R ₁ represents a hydrogen atom or a methyl group, R ₂ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, m is an integer of 4 to 60, preferably 6 to 50,
n is an integer of 2 to 3, preferably 2, wherein m oxyalkylene units (CnH ₂ nO) may be the same or different from each other. it can.

Specific examples of such a monomer (B) include, for example, tetraethylene glycol (meth) acrylate, methoxytetraethylene glycol (meth) acrylate, ethoxytetraethylene glycol (meth) acrylate, n-butoxytetraethylene glycol. (Meth) acrylate, tetrapropylene glycol (meth) acrylate, methoxytetrapyroprene glycol (meth) acrylate, ethoxytetrapropylene glycol (meth) acrylate, n-butoxytetrapropylene glycol (meth) acrylate, polyethylene glycol (meth) acrylate, Polypropylene glycol (meth) acrylate, methoxy polyethylene glycol (meth) acrylate, ethoxy polyethylene glycol Meth) acrylate, and the like. Among these, polyethylene glycol (meth) acrylate and polypropylene glycol (meth) acrylate are particularly preferable.

These can be used alone or in combination of two or more.

Other ethylenically unsaturated monomers
(C): The other ethylenically unsaturated monomer (C) is
A polymerizable unsaturated monomer other than the monomer (A) and the monomer (B), which is copolymerizable with the monomer (A) and the monomer (B) described above, and has properties desired for a pigment dispersion resin. It is appropriately selected and used accordingly.

Specific examples of such a monomer (C) include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth). Acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, C ₁ -C ₂₄ linear or cyclic alkyl (meth) acrylate monomers such as isobornyl (meth) acrylate and tridecyl (meth) acrylate; 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, Hydroxyl group-containing polymerizable unsaturated monomers such as hydroxybutyl (meth) acrylate (typically hydroxyalkyl (meth) acrylate monomers); carboxyl group-containing polymerizable unsaturated monomers such as methacrylic acid and acrylic acid; acrylamide, methacrylamide; Oxetane ring-containing (meth) acrylates such as 3-ethyl-3- (meth) acryloyloxymethyloxetane, 3-methyl-3- (meth) acryloyloxymethyloxetane, 3-butyl-3- (meth) acryloyloxymethyloxetane Aromatic vinyl compounds such as styrene, α-methylstyrene and vinyltoluene; (meth) acrylonitrile and vinyl acetate. These polymerizable unsaturated monomers may be used alone or in combination of two or more.

Ease of wetting of a water-based ink composition onto a printed surface using the above-mentioned monomer (A), the copolymer formed from the monomer (B) and the monomer (C) as a resin for dispersing pigment. From the standpoint of ease of ink sticking and reactivity with the curing agent component, it is desirable that the monomer (C) contains a hydroxyl group-containing polymerizable unsaturated monomer as at least a part of the component.

Specific examples of the hydroxyl group-containing polymerizable unsaturated monomer include 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, 2,3-dihydroxybutyl (meth) acrylate and 4-hydroxybutyl. Monoester products of polyhydric alcohols and (meth) acrylic acid, such as (meth) acrylate and polyethylene glycol mono (meth) acrylate; ε-caprorapton is added to the monoester products of the above polyhydric alcohols and (meth) acrylic acid. Examples thereof include compounds obtained by ring-opening polymerization. Among them, 4-hydroxybutyl (meth) acrylate, polyethylene glycol mono (meth) acrylate [other than the above-mentioned monomer (B)], and a monoesterified product of a polyhydric alcohol and (meth) acrylic acid with ε-caprorapton. A compound obtained by ring-opening polymerization is preferable in terms of reactivity. The above-exemplified compounds can be used alone or in combination of two or more kinds. The hydroxyl group-containing polymerizable unsaturated monomer is used in an amount of 3 to 30% by weight, preferably 5 to 25% by weight, based on the total amount of the monomers (A), (B) and (C).

In order to ensure water dispersibility of the resin,
In addition to the hydrophilic monomer (B), a carboxyl group-containing polymerizable unsaturated monomer can be used as at least a part of the other ethylenically unsaturated monomer (C), if necessary. The pigment-dispersing resin obtained using the carboxylic group-containing polymerizable unsaturated monomer is preferably not used in combination with a basic neutralizing agent.

Further, for the purpose of improving the weather resistance of the formed printing layer (I), at least a part of the above-mentioned monomer (C) may be used, as the case may be, as will be described below. And / or UV-stable polymerizable unsaturated monomers (D) can be used.

UV absorbing polymerizable unsaturated monomer and /
Alternatively, the UV stable polymerizable unsaturated monomer (D) is used to improve the weather resistance of the copolymer formed by imparting UV absorption and / or UV stability to the copolymer. It is a monomer component of.

Examples of the UV absorbing polymerizable unsaturated monomer used for such a purpose include hydroxybenzophenones such as 2,4-diidoxybenzophenone and 2,2 ', 4-trihydroxybenzophenone and glycidyl ( Addition reaction product with (meth) acrylate,
For example, 2-hydroxy-4- (3-methacryloyloxy-2-hydroxypropoxy) benzophenone, 2
-Hydroxy-4- (3-acryloyloxy-2-hydroxypropoxy) benzophenone, 2,2'-dihydroxy-4- (3-methacryloyloxy-2-hydroxypropoxy) benzophenone, 2,2'-dihydroxy-4- ( 3-acryloxy-2-hydroxypropoxy) benzophenone and the like; or 2- (2′-hydroxy-5′-methacryloyloxyethylphenyl) -2H-benzotriazole and the like. Among these, particularly those having a (2′-hydroxyphenyl) -benzotriazole structure and a (meth) acryloyl group, specifically, 2- (2′-hydroxy-5′-methacryloyloxyethylphenyl) exemplified above. ) -2
H-benzotriazole is preferred.

Examples of the UV stable polymerizable unsaturated monomer include 4- (meth) acryloyloxy-
1,2,2,6,6-pentamethylpiperidine, 4-
(Meth) acryloyloxy-2,2,6,6-tetramethylpiperidine, 4-cyano-4- (meth) acryloylamino-2,2,6,6-tetramethylpiperidine, 1- (meth) acryloyl-4 -(Meth) acryloylamino-2,2,6,6-tetramethylpiperidine, 1- (meth) acryloyl-4-cyano-4- (meth) acryloylamino-2,2,6,6-tetramethylpiperidine, 4-crotonoyloxy-2,2,6
6-tetramethylpiperidine, 4-crotonoylamino-2,2,6,6-tetramethylpiperidine, 1-crotonoyl-4-crotonoyloxy-2,2,6,6-
Tetramethylpiperidine and the like can be mentioned. Of these, 4- (meth) acryloyloxy-1,2,
2,6,6-Pentamethylpiperidine is preferred.

The ultraviolet absorbing polymerizable unsaturated monomer and the ultraviolet stable polymerizable unsaturated monomer are appropriately selected depending on the pigment to be dispersed, and either one or both can be used in combination.

The pigment-dispersing resin includes a polymerizable unsaturated monomer (A) containing an ionic functional group as described above, a nonionic polymerizable unsaturated monomer (B) and other ethylenically unsaturated monomer (C). ). The ratio of the monomers (A), (B) and (C)) used in the copolymerization is not strictly limited,
Although it can be changed depending on the desired physical properties of the copolymer to be formed, it is generally within the following range based on the total amount of the monomers (A), (B) and (C). it can. Monomer (A): 0.5-40% by weight, preferably 1-
35% by weight, more preferably 1.5 to 30% by weight, monomer (B): 5 to 40% by weight, preferably 7 to 35
% By weight, more preferably 10 to 25% by weight, monomer (C): 20 to 94.5% by weight, preferably 3
0 to 92% by weight, more preferably 45 to 88.5% by weight.

In particular, when the ultraviolet absorbing polymerizable unsaturated monomer and / or the ultraviolet stable polymerizable unsaturated monomer (D) is used as a part of the monomer (C), the monomers (A) and (B) are used. The proportions of C, (C) and (D) used can generally be within the following ranges based on the total amount of these four monomer components. Monomer (A): 0.5 to 30% by weight, preferably 1 to
20% by weight, more preferably 1.5 to 15% by weight, monomer (B): 5 to 40% by weight, preferably 10 to 3%
0% by weight, more preferably 15 to 25% by weight, monomer (C): 25 to 94.4% by weight, preferably 4
7-88.5% by weight, more preferably 57.5-8
2.5% by weight, monomer (D): 0.1 to 5% by weight, preferably 0.5
.About.3% by weight, more preferably 1 to 2.5% by weight.

The copolymerization of the monomers (A), (B) and (C) can be carried out by a method known per se, for example, a solution polymerization method in an organic solvent or an emulsion polymerization method in water. However, the solution polymerization method is preferable. As the copolymerization method by the solution polymerization method, for example, a mixture of the monomers (A), (B) and (C) and a radical polymerization initiator is dissolved or dispersed in an organic solvent,
Usually, a method of heating at a temperature of about 80 ° C. to about 200 ° C. with stirring for about 1 to 10 hours to polymerize can be mentioned.

The organic solvent that can be used in the copolymerization is
For example, hydrocarbon solvents such as heptane, toluene, xylene, octane, mineral spirits; ester solvents such as ethyl acetate, n-butyl acetate, isobutyl acetate, ethylene glycol monomethyl ether acetate, diethylene glycol monobutyl ether acetate; methyl ethyl ketone, methyl isobutyl Ketone, diisobutyl ketone, cyclohexanone and other ketone solvents; methanol, ethanol, isopropanol, n-butanol, sec-butanol, isobutanol and other alcohol solvents; n-butyl ether, dioxane, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether. Aromatic solvents such as; Sarosol 310, Swazol 1000, Swazol 1500, etc. made by Cosmo Oil Co., Ltd. Oil-based solvents and the like. These organic solvents can be used alone or in combination of two or more. At the time of the polymerization reaction, the above organic solvent can be used usually in a ratio of 400 parts by weight or less based on 100 parts by weight of the total amount of the monomer components.

Examples of the radical polymerization initiator include ketone peroxides such as cyclohexanone peroxide, 3,3,5-trimethylcyclohexanone peroxide, and methylcyclohexanone peroxide; 1,1-bis (tert-butylperoxy). ) -3,
3,5-trimethylcyclohexane, 1,1-bis (te
rt-butylperoxy) cyclohexane, n-butyl-
Peroxyketals such as 4,4-bis (tert-butylperoxy) valerate; hydroperoxides such as cumene hydroperoxide and 2,5-dimethylhexane-2,5-dihydroperoxide; 1,3 −
Dialkyl peroxides such as bis (tert-butylperoxy-m-isopropyl) benzene, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane, diisopropylbenzene peroxide, and tert-butylcumyl peroxide. Kinds; decanoyl peroxide,
Diacyl peroxides such as lauroyl peroxide, benzoyl peroxide and 2,4-dichlorobenzoyl peroxide; peroxycarbonates such as bis (tert-butylcyclohexyl) peroxydicarbonate; tert-butylperoxybenzoate
Organic peroxide-based polymerization initiators such as peroxyesters such as 2,5-dimethyl-2,5-di (benzoylperoxy) hexane; 2,2′-azobisisobutyronitrile, 1,1- Examples thereof include azo-based polymerization initiators such as azobis (cyclohexane-1-carbonitrile), azocumene 2,2′-azobismethylvaleronitrile, and 4,4′-azobis (4-cyanovaleric acid). The amount of these radical polymerization initiators used is not particularly limited, but is usually in the range of 0.1 to 15 parts by weight, particularly 0.3 to 10 parts by weight, based on 100 parts by weight of the total of the polymerizable monomers. Is desirable.

In the above polymerization reaction, the method of adding the monomer component and the polymerization initiator is not particularly limited,
The polymerization initiator can be divided and added in several divided portions from the initial polymerization to the latter half of the polymerization rather than being charged at the beginning of the polymerization all at once. It is suitable from the viewpoint.

The molecular weight of the copolymer thus obtained is not particularly limited, but in view of water dispersion stability, pigment dispersibility, viscosity, VOC, resin color number (coloring degree) and the like. Usually, the weight average molecular weight is 500 to 100,000.
0, especially 1,000 to 70,000, more particularly 3,0
It is preferably in the range of 00 to 50,000.

The pigment-dispersing resin made of the copolymer produced as described above is used for preparing an aqueous pigment dispersion, so that it is possible to achieve both wettability with the pigment and stabilization of dispersion of the pigment. It is necessary to be. The monomer (A) component that constitutes the pigment-dispersing resin of the present invention can improve the adsorption of the pigment-dispersing resin to the pigment, and improves both the wettability to the pigment and the dispersion stability of the resin. Can work in an advantageous way. The monomer (B) component constituting the pigment-dispersing resin of the present invention contributes to the improvement of the solubility of the pigment-dispersing resin in the continuous phase (aqueous medium), and particularly the dispersion stability of the pigment-dispersing resin. It can work for improvement.
Furthermore, 3 as at least a part of the monomer (A)
By copolymerizing with a polymerizable unsaturated monomer containing a primary amino group, it is possible to obtain a pigment-dispersing resin in which the dispersibility of a black (carbon black) pigment, which is a particularly difficult-to-disperse pigment, is remarkably improved.

The aqueous ink composition used for forming the printing layer (I) is a pigment dispersion resin produced as described above (hereinafter referred to as a pigment dispersion resin (a)).
In addition, the pigment, the aqueous medium, and, if necessary, other pigment dispersion resin (hereinafter, referred to as pigment dispersion resin (b)), dispersion aid, basic neutralizing agent, other additives, for example, , Water-soluble resins, thickeners, flow regulators, film-forming aids, surfactants, pH regulators, fungicides, antioxidants, UV absorbers, UV stabilizers, chelating agents and other additives, Furthermore, it can be prepared by blending dyes.

Examples of the pigments include bright pigments such as aluminum powder, copper powder, nickel powder, stainless powder, chromium powder, mica-like iron oxide, titanium oxide-coated mica powder, iron oxide-coated mica powder, and bright graphite. ; Pink EB,
Organic red pigments such as azo and quinacridone pigments, organic blue pigments such as cyanine blue and cyanine green, organic yellow pigments such as benzimidazolone pigments, isoindoline pigments and quinophthalone pigments; titanium white, titanium yellow, red iron oxide, Inorganic coloring pigments such as carbon black, yellow lead, iron oxide, and various baked pigments can be used. Further, an extender pigment may be included. These pigments may be subjected to surface treatment known per se, for example, acid / base treatment, coupling agent treatment, plasma treatment, oxidation / reduction treatment and the like.

Of these, as specific examples of pigments used in ink jet inks, for example, Ra
ven7000, Raven5750, Raven52
50, Raven5000 ULTRAII, Raven
3500, Raven2000, Raven1500,
Raven1250, Raven1200, Raven
1190 ULTRAII, Raven 1170, Rav
en1255, Raven1080, Raven106
0 (above, Columbian Carbon Co., Ltd.), Regal
400R, Regal330R, Regal660R,
Mogul L, Black Pearls L, Mon
arch 700, Monarch 800, Monar
ch 880, Monarch 900, Monarch
1000, Monarch 1100, Monarch
1300, Monarch 1400 (above, manufactured by Cabot), Color Black FW1, Color
Black FW2, Color Black FW2
V, Color Black18, Color Blac
k FW200, Color Black S150, C
color Black S160, Color Blac
kS170, Printex35, PrintexU,
PrintexV, Printex140U, Prince
tex140V, Special Black6, Sp
ecological Black 5, Special Black
k 4A, Special Black 4 (all manufactured by Degussa), No. 25, No. 33, No. 40, No. 4
7, No. 52, No. 900, No. 2300, MCF
Black pigments such as -88, MA600, MA7, MA8, MA100 (all manufactured by Mitsubishi Chemical Corporation); CI Pigment
Blue-1, CI Pigment Blue-2,
CI Pigment Blue-3, CI Pigm
ent Blue-15, CI Pigment Blu
e-15: 1, CI Pigment Blue-1
5: 3, CI Pigment Blue-15: 3
4, CI Pigment Blue-16, CIIP
Pigment Blue-22, CI Pigment
Cyan Pigment such as Blue-60; CI Pigme
nt Red-5, CI Pigment Red-7,
CI Pigment Red-12, CI Pigm
ent Red-48, CI Pigment Red-
48: 1, CI Pigment Red-57, C.I.
I. Pigment Red-112, C. I. Pigme
nt Red-122, CI Pigment Red-
123, CI Pigment Red-146, C.I.
I. Pigment Red-168, C. I. Pigme
nt Red-184, CI Pigment Red-
Magenta color pigments such as 202; CI Pigment Y
hello-1, CI Pigment Yellow
-2, CI Pigment Yellow-3, C.I.
I. Pigment Yellow-12, C. I. Pig
ment Yellow-13, CI Pigment
Yellow-14, CI Pigment Yell
ow-16, CI Pigment Yellow-1
7, CI Pigment Yellow-73, C.I.
I. Pigment Yellow-74, C. I. Pig
ment Yellow-75, CI Pigment
Yellow-83, CI Pigment Yell
ow-93, CI Pigment Yellow-9
5, CI Pigment Yellow-97, C.I.
I. Pigment Yellow-98, C. I. Pig
ment Yellow-114, CI Pigmen
t Yellow-128, CI Pigment Y
hello-129, CI Pigment Yell
ow-151, CI Pigment Yellow-
Examples thereof include yellow pigments such as 154, but these are merely examples and the present invention is not limited thereto.

The blending ratio of these pigments is not particularly limited, but usually, the pigment dispersing resin (a) 100 is used.
10 to 3,000 parts by weight, especially 15 to
It is preferably 2,000 parts by weight, more preferably 15 to 1500 parts by weight, from the viewpoints of pigment dispersibility, dispersion stability, and coloring power of the resulting pigment dispersion.

Examples of the aqueous medium include water, and a water-organic solvent mixed solution prepared by dissolving an organic solvent such as a water-soluble organic solvent in water. Examples of the organic solvent used here include water-soluble organic solvents such as methyl alcohol, ethyl alcohol, isopropyl alcohol, propyl propylene glycol, butyl cellosolve, propylene glycol monomethyl ether, and 3-methyl-3-methoxybutanol; xylene, toluene, cyclohexanone. , Sparingly soluble or insoluble organic solvents such as hexane and pentane. The organic solvent may be used alone or in combination of two or more. A small amount of water-insoluble organic solvent can also be used together with the water-soluble organic solvent.
The mixing ratio of water and the organic solvent is not particularly limited,
The content of the organic solvent is 50% by weight or less of the mixed solution, especially 3
It is preferably 5% by weight or less. The mixing ratio of the aqueous medium is not particularly limited, but is usually 50 to 5,000 parts by weight per 100 parts by weight of the resin (a) for dispersing pigment.
Particularly 100 to 3,000 parts by weight, more particularly 100 to
It is preferably in the range of 2,000 parts by weight from the viewpoint of viscosity at the time of dispersing the pigment, pigment dispersibility, dispersion stability and production efficiency.

Other pigment-dispersing resins (b) used as required include, for example, carboxyl group-containing polymerizable unsaturated monomers such as (meth) acrylic acid and 2-hydroxyethyl (meth) acrylate. Examples thereof include an acrylic resin obtained by copolymerizing a hydroxyl group-containing polymerizable unsaturated monomer and another polymerizable unsaturated monomer in the presence of a radical polymerization initiator. The acrylic resin has a weight average molecular weight of about 2,000 to 150,
000, especially 5,000 to 100,000, and an acid value of 5
Those having a range of 150, particularly 15 to 100, a hydroxyl value of 10 to 160, and particularly 30 to 120 are preferable. Also,
As other pigment dispersion resins, for example, ethylene glycol, butylene glycol, 1,6-hexanediol,
Polyester obtained by condensation reaction of polyhydric alcohols such as trimethylolpropane and pentaerythritol with polyhydric carboxylic acid components such as adipic acid, isophthalic acid, terephthalic acid, phthalic anhydride, hexahydrophthalic anhydride and trimellitic anhydride Resins are also included. The polyester resin has a weight average molecular weight of about 1,0.
00-100,000, especially 1,500-70,000
0, acid value 5 to 150, especially 15 to 100, hydroxyl value 1
Those in the range of 0 to 160, especially 30 to 120 are preferable.

In the step of preparing an aqueous ink composition, the pigment and the pigment-dispersing resin (a) are usually dispersed in an aqueous medium and then diluted with another pigment-dispersing resin (b) to prepare an ink. Time stability and long-term storage stability can be obtained.

The ratio (solid content) of the pigment-dispersing resin (a) to the other pigment-dispersing resin (b) is usually 1 (resin (a)).
It is suitable that the amount of the resin (b) is 5 to 300 parts by weight, especially 20 to 150 parts by weight, per 100 parts by weight.

Examples of the dispersion aid used as necessary include Disperb manufactured by BYK-Chemie.
yk184, 190, etc.
Examples of other additives include antifoaming agents, preservatives, rust preventives, and plasticizers. In consideration of the dispersibility of the pigment, the stability of the paste, the letdown stability, and the coating film performance, these compounding amounts are all 100% for the pigment dispersion resin.
The amount is preferably 50 parts or less per part by weight.

Specific examples of the above defoaming agent include "BY.
K-019 "," BYK-021 "," BYK-02 "
3 "," BYK-024 "," BYK-025 "," B "
YK-028 "(all manufactured by BYK-Chemie,
Water-based silicone defoamer), "BYK-011" (BYK
-Chemie, silicon-free polymer-based defoaming agent) and the like.

The basic neutralizing agent neutralizes the pigment-dispersing resin (a) and the other pigment-dispersing resin (b), if they have a carboxyl group, to obtain these pigment-dispersing resins. It is used for water-solubilization or water-dispersion, and specific examples thereof include inorganic bases such as ammonium hydroxide, sodium hydroxide and potassium hydroxide; aminomethyl propanol, aminoethyl propanol and dimethyl. Examples include amines such as ethanolamine, triethylamine, diethylethanolamine, dimethylaminopropanol, aminomethylpropanol and the like. The amount of the basic neutralizing agent to be added is an amount necessary for making the pigment-dispersing resin water-soluble or water-dispersing, and the neutralization equivalent of the carboxyl group in the pigment-dispersing resin is usually 0.3 to 1 It is preferable that the ratio is within the range of 0.5, particularly 0.4 to 1.3.

When the pigment is dispersed using the pigment dispersing resin (a), it is desirable not to use a basic neutralizing agent. If used, the basic neutralizing agent may be adsorbed before the pigment-dispersing resin (a) is adsorbed on the pigment, which may impair the dispersibility. On the other hand, when the pigment is dispersed with the pigment-dispersing resin (a) and then diluted with another pigment-dispersing resin (b), it is desirable to neutralize with the basic neutralizing agent.

As described above, the water-based ink composition may further contain a water-soluble resin, a thickener, a flow regulator, a film-forming aid, a surfactant, a pH regulator, an antifungal agent, if necessary. Additives such as antioxidants, ultraviolet absorbers, ultraviolet stabilizers, chelating agents, and dyes may be added.

As the water-soluble resin, from the viewpoint of controlling ink characteristics, for example, polyethyleneimine, polyamines,
Polyvinylpyrrolidone, cellulose derivatives, polysaccharides, acrylic emulsions, polyurethane emulsions and the like can be used. Further, a curing agent may be contained as a resin component, and examples thereof include an amino resin and an optionally blocked polyisocyanate compound.

As the amino resin used as a curing agent, a melamine resin is generally used. Among them, at least a part of the methylol group of the methylolated melamine resin or the methylolated melamine resin is a monohydric alcohol having 1 to 4 carbon atoms. A melamine resin obtained by etherification is preferable, and a water-soluble or water-dispersible resin is particularly preferable, but a water-insoluble resin can also be used.

Commercial products of the above melamine resins include, for example, U-Van 20SE-60 and U-Van 225 (above,
Butyl etherified melamine resins such as Mitsui Chemicals, Inc., trade name), Super Beckamine G840, Super Beckamine G821 (all are products of Dainippon Ink and Chemicals, Inc., trade names); Sumimar M-100, Sumimar M -40S, Sumimar M-55 (all are products of Sumitomo Chemical Co., Ltd., trade names), Cymel 303, Cymel 3
25, Cymel 327, Cymel 350, Cymel 37
Methyl etherification of 0 (above, all manufactured by Mitsui Cytec Co., Ltd.), Nikarac MS17, Nicalaque MS15 (above all manufactured by Sanwa Chemical Co., Ltd.), Regimin 741 (manufactured by Monsanto Co., Ltd.) Melamine resin; Cymel 235, Cymel 202, Cymel 23
8, Cymel 254, Cymel 272, Cymel 113
Mixed etherified melamine resin of 0 (above, all manufactured by Mitsui Cytec, trade name), Sumimar M66B (manufactured by Sumitomo Chemical Co., Ltd., trade name), etc .; Cymel XV805 (manufactured by Mitsui Cytec Co., Ltd. Name), Nikalac MS95 (manufactured by Sanwa Chemical Co., Ltd.), and the like, and mixed etherified melamine resin of methylation and n-butylation.

The above-mentioned optionally blocked polyisocyanate compound which can be used as a curing agent includes both a polyisocyanate compound having a free isocyanate group and a polyisocyanate compound having an isocyanate group blocked. As the polyisocyanate compound having a free isocyanate group, for example,
Aliphatic diisocyanates such as hexamethylene diisocyanate and trimethylhexamethylene diisocyanate; cycloaliphatic diisocyanates such as hydrogenated xylylene diisocyanate and isophorone diisocyanate; aromatic diisocyanates such as tolylene diisocyanate and 4,4'-diphenylmethane diisocyanate; tri Phenylmethane-4,4 ', 4 "-triisocyanate, 1,3,5-triisocyanatobenzene,
Organic polyisocyanate compounds such as 2,4,6-triisocyanatotoluene, 4,4'-dimethyldiphenylmethane-2,2 ', 5,5'-tetraisocyanate, and other polyisocyanate compounds having three or more isocyanate groups. Isocyanate itself, or an adduct of each of these organic polyisocyanates with a polyhydric alcohol, a low molecular weight polyester resin, water, or the like, or a cyclized polymer of each of the above organic polyisocyanates, and an isocyanate
A biuret body etc. can be mentioned.

Commercially available products of polyisocyanate compounds having free isocyanate groups include, for example, Burnock D-750, Burnock D-800, Burnock D.
N-950, Burnock DN-970, Burnock DN
-15-455 (all manufactured by Dainippon Ink and Chemicals, Inc.), Death Module L, Death Module N, Death Module HL, Death Module N3390 (all manufactured by Sumitomo Bayer Urethane Co., Ltd., trade name), Takenate D -102, Takenate D-202, Takenate D-1
10, Takenate D-123N (above, all manufactured by Takeda Pharmaceutical Co., Ltd., trade name), Coronate EH, Coronate L, Coronate HL, Coronate 203 (above, all manufactured by Nippon Polyurethane Industry Co., Ltd., trade name), Duranate 24A- 90CX (manufactured by Asahi Kasei Kogyo KK, trade name) and the like.

As the polyisocyanate compound in which the isocyanate group is blocked, the isocyanate group of the above-mentioned polyisocyanate compound having a free isocyanate group can be prepared from oxime, phenol, alcohol, lactam, malonic acid diester, acetoacetic acid ester or mercaptan. Examples thereof include those blocked with a known blocking agent. Examples of these typical commercial products are:
Barnock D-550 (manufactured by Dainippon Ink and Chemicals, Inc., trade name), Takenate B-815-N (manufactured by Takeda Pharmaceutical Co., Ltd., trade name), Aditol VXL-80 (Germany,
Hoechst, trade name), Coronate 2507 (Nippon Polyurethane Industry Co., trade name), Desmodur N35
00 (manufactured by Sumitomo Bayer Urethane Co., Ltd.) and the like. A curing catalyst may be contained when these curing agents are used.

Examples of the ultraviolet absorber include benzophenone-based, benzotriazole-based, cyanoacrylate-based, salicylate-based, oxalic acid anilide-based compounds and the like, and examples of the ultraviolet stabilizer include hindered amine-based compounds. You can

The water-based ink composition contains the above-mentioned components, for example, paint shaker, scan disk,
It can be prepared by uniformly mixing and dispersing using a disperser such as LMZ mill or DCP pearl mill.

The aqueous ink composition thus prepared is
The average particle size of dispersed particles contained therein is 1 to 300 n.
m, particularly preferably in the range of 1 to 200 nm, and the viscosity of the ink liquid is 1.0 to 10 mPa ·
s, particularly preferably in the range of 1.5 to 7 mPa · s.

According to the present invention, the printing layer (I) can be formed by the ink jet drawing method using the water-based ink composition as described above. Inkjet drawing may be performed by any conventionally known method such as a piezo inkjet method or a thermal inkjet method. In addition to a normal inkjet drawing device, a drawing device equipped with a heater or the like for controlling ink drying, or an intermediate transfer mechanism is installed,
It is also possible to form the printing layer (I) using a recording device that prints a recording material on an intermediate body and then transfers the recording material onto a recording medium such as paper, an automatic drawing device that draws directly on a wall surface, an outdoor signboard, an automobile body, or the like. it can.

The printing layer (I) is usually composed of the basic primary colors of red, blue, yellow, and
It can be formed by drawing a desired pattern, character or the like by using a head having dedicated nozzles of four colors of black.

The printing layer (I) formed is usually about 0.01 to about 10 μm in dry film thickness, especially about 0.01 to about 5 μm.
It can be a thin film layer within the range of m.

The formed printing layer (I) is, if necessary, air-dried, touch-dried by hot air spraying, semi-cured or heat-cured, and a clear coat layer (II) is formed thereon by using a clear coating. Be punished. Formation of clear coat layer (II): The clear coating applied on the printing layer (I) is for protecting the printing layer (I), and if the clear coating has good weather resistance,
Organic solvent-based paints, water-based paints, powder paints, etc. can be used without limitation. Examples of the base resin component used in the coating material include various resins such as acrylic resin-based, polyester resin-based, alkyd resin-based, silicone resin-based, and fluororesin-based resins. If necessary, a polyisocyanate compound, A crosslinking agent such as an amino resin, an epoxy group-containing compound and a carboxyl group-containing compound can also be used in combination. These coating materials may be either a room temperature curing type or a thermosetting type, and may be a type that is cured by an actinic ray such as an ultraviolet ray or an electron beam. Among them, a urethane-curable clear coating material containing a combination of a polyacrylic polyol or polyester polyol and a polyisocyanate compound that may be blocked as a resin component, and an ultraviolet-curable acrylic resin based on an ultraviolet-curable acrylic resin. The clear paint of is preferable. Further, it is desirable that the clear coating material contains an ultraviolet absorber and / or an ultraviolet stabilizer from the viewpoint of weather resistance. As the ultraviolet absorber and the ultraviolet stabilizer, those listed in the description of the aqueous ink composition can be used, and their compounding amount is
Usually, it is 0.1 with respect to 100 parts by weight of resin solids in the paint.
It can be in the range of up to 5 parts by weight.

The above clear paint can be applied by a method known per se, for example, an air spray, an airless spray, an electrostatic rotary atomization type coating method and the like. The thickness of the clear coat layer (II) is usually about 10 to about 50 μm, preferably about 20 to about 45 μm as a dry film thickness.
It can be within the range of m.

[0072]

EXAMPLES The present invention will be described more specifically below with reference to production examples, examples and comparative examples. Unless otherwise specified, "part" and "%" mean "part by weight" and "% by weight", respectively.

Production of Resin (a) for Pigment Dispersion Production Example 1 Ethylene glycol monobutyl ether 3 was placed in an ordinary acrylic resin reaction tank equipped with a stirrer, a thermometer and a reflux condenser.
8 parts and 12 parts of isobutyl alcohol were charged, heated and stirred and maintained at 110 ° C. In this, 50 parts of methyl methacrylate, 20 parts of n-butyl acrylate, 5 parts of 2-acrylamido-2-methyl sulfonic acid, 5 parts of 2-hydroxyethyl acrylate, and "NF bisomer S20.
W "(manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., trade name, 50% water-diluted product of methoxypolyethylene glycol monomethacrylate, molecular weight about 2080) 40 parts, mixture consisting of 1 part azobisisobutyronitrile and 20 parts isobutyl alcohol Was added dropwise over 3 hours. After completion of the dropping, the mixture was aged at 110 ° C. for 30 minutes, and then an additional catalyst mixed solution containing 10 parts of ethylene glycol monobutyl ether and 0.5 part of azobisisobutyronitrile was added dropwise over 1 hour. Then, age it at 110 ° C for 1 hour and then cool it to a solid content of 50%.
To obtain a resin (a-1) solution for dispersing pigment.

Production Examples 2 to 4 In the above Production Example 1, the same operation as in Production Example 1 was carried out except that the composition shown in Table 1 below was used, and each pigment dispersion resin solution (a-2) having a solid content of 50%. ~ (A-4) were obtained. The resin acid value and the like of these pigment dispersion resins are shown in Table 1 below. still,
In Table 1, the amount of "NF Byomer S20W" indicates the solid content.

[0075]

[Table 1]

Synthesis of Pigment Dispersion Resin (b) Synthesis Example 1 40 parts of ethylene glycol monobutyl ether in an acrylic resin reaction tank equipped with a stirrer, thermometer, reflux condenser, etc.
Charge 30 parts of isobutyl alcohol, heat and stir to 1
After reaching 00 ° C., a mixture of the following monomers and the like was added dropwise over 3 hours.

Methyl methacrylate 34 parts n-Butyl acrylate 30 parts 2-Ethylhexyl methacrylate 20 parts 2-Hydroxyethyl acrylate 10 parts Acrylic acid 6 parts 2,2'-Azobisisobutyronitrile 1 part Isobutyl alcohol 10 parts After the dropping is completed, the temperature is kept at 100 ° C. for another 30 minutes, and then 2,
An additional catalyst solution, which is a mixture of 0.5 parts of 2'-azobisisobutyronitrile and 10 parts of ethylene glycol monobutyl ether, was added dropwise over 1 hour. Further 100 ℃
After continuing stirring for 1 hour, the mixture was cooled to obtain an acrylic resin solution (b-1) having a solid content concentration of 50%. The obtained resin is
Acid value 47 mgKOH / g, hydroxyl value 48 mgKOH / g
And a weight average molecular weight of 40,000.

Synthesis Example 2 In a reaction vessel equipped with a stirrer, a thermometer, a rectification column, a nitrogen introducing tube, a reflux condenser, etc., 317.8 parts of isophthalic acid, 196.5 parts of hexahydrophthalic acid, 372. 6
Part, neopentyl glycol 268 part, 1,6-hexanediol 217.8 part, trimethylolpropane 26
Charge 3.5 parts, heat and stir under nitrogen gas introduction, and
After reaching 60 ° C, the temperature was raised to 235 ° C over 3 hours. Thereafter, the temperature was maintained at the same temperature for 1.5 hours, the rectification column was switched to a reflux condenser, 100 parts of toluene was introduced, and the reaction was continued under reflux. After reacting at the same temperature for 6 hours, toluene was removed under reduced pressure, cooled to 170 ° C., and 122.5 parts of trimellitic anhydride was added. 3 at 170 ℃
After holding for 0 minutes, 322 parts of butyl cellosolve was added and then cooled to 80 ° C. Next, after adding 4 parts of N, N-dimethylaminoethanol and keeping it at 80 ° C. for 30 minutes as it is, cooling to 50 ° C. and adding 2600 parts of deionized water and stirring for 30 minutes, a polyester resin solution having a solid content concentration of 50% (B-2) was obtained. The obtained resin had an acid value of 56 mgKOH / g, a hydroxyl value of 90 mgKOH / g and a weight average molecular weight of 25,000.

Synthetic Example of Acrylic Emulsion Synthetic Example 3 400 parts of deionized water and "Newcol 562S" were placed in an acrylic resin reaction tank equipped with a stirrer, a thermometer, a reflux condenser and the like.
F "(trade name, surfactant manufactured by Nippon Emulsifier Co., Ltd.) 2.
After adding 4 parts and heating and stirring to reach 82 ° C., the mixture for preparing a pre-emulsion was charged. The mixture for preparing the pre-emulsion was mixed with 6 parts of styrene, 8.5 parts of n-butyl acrylate, 0.5 part of allyl methacrylate, 0.175 parts of "Newcol 562SF" and 7.5 parts of deionized water, and mixed with a disper. About 1000 rpm It was stirred for 10 minutes.

Charge the pre-emulsion preparation mixture 2
After 0 minutes, 15 parts of deionized water and potassium persulfate were added.
54 parts were added. After 10 minutes, 114 parts of styrene and 16 parts of n-butyl acrylate were kept at 82 ° C.
1.5 parts, 9.5 parts allyl methacrylate, 3.325 parts "Newcol 562SF" and deionized water 142.
Mix 5 parts and disperse about 1000 rpm. In 1
The mixture was stirred for 0 minutes, and the first monomer mixture obtained by adding 15 parts of deionized water and 0.54 part of potassium persulfate was added dropwise over 3 hours. After dropping, hold at 82 ° C for 30 minutes,
Then 50 parts of styrene, 23 of n-butyl acrylate
Parts, 10 parts of 2-hydroxyethyl acrylate, 5 parts of methacrylic acid, 1.6 parts of "Newcol 562SF" and 60 parts of deionized water, and mixed with a disper for about 1000
r.p.m. The mixture was stirred for 10 minutes at 10 minutes, and a second monomer mixture obtained by adding 15 parts of deionized water and 0.54 part of potassium persulfate was added dropwise over 1.5 hours. After completion of dropping, 8
The mixture was kept at 2 ° C for 30 minutes, cooled, and when it reached 75 ° C, a mixture of 7 parts of N, N-dimethylaminoethanol and 280 parts of deionized water was added dropwise over 15 minutes. Then, the mixture was kept at 75 ° C. for 15 minutes and cooled to synthesize an acrylic emulsion having a solid content concentration of 30%.

Preparation of Aqueous Ink Preparation Examples 1 to 6 Acrylic resin solution (b-1) 50 obtained in Synthesis Example 1 above
Part, polyester resin solution (b-2) 4 obtained in Synthesis Example 2
2.8 parts, acrylic emulsion obtained in Synthesis Example 3 66.
6 parts, "Cymel 325" (manufactured by Mitsui Cytec Co., Ltd., trade name, methyl etherified melamine resin solution having a solid content of about 80%), and "Primal ASE-60" (manufactured by Nippon Acrylic Chemical Co., Ltd., trade name, 1 part of 28% water dilution of thickener), 0.8 part of dimethylethanolamine, 167 parts of deionized water and 2-ethylhexyl alcohol 2
Add 1.8 parts to the container and stir with a disper to obtain a solid content of 25
% Mixed resin solution was obtained.

Pigment dispersion resin solutions (a-2) to (a-4) having a solid content of 50% obtained in the above Production Examples 1 to 4, pigment "B"
YK-028 "(manufactured by BYK-Chemie, trade name,
Silicone antifoaming agent), isopropanol, glycerin and deionized water are added in a volume of 2 according to the composition shown in Table 2 below.
The mixture was placed in a 25 cc wide-mouthed glass bottle, glass beads having a diameter of about 1.3 mmφ were added as a dispersion media, the mixture was sealed, and each aqueous pigment dispersion obtained by dispersing for 4 hours with a paint shaker and the mixed resin prepared as described above. Using the solution, add to the container with the composition shown in the same table and stir with a disper,
Each aqueous ink was obtained.

Preparation Examples 7 to 10 Commercially available ink-jet pigment aqueous inks a to d and the mixed resin solution prepared as described above were added to a container with the composition shown in Table 3 below, followed by stirring with a disper, and comparison. Example aqueous inks ~ 10 were obtained.

Table 2 and Table 3 (Note 1) and each of the commercially available water-based inks a to d are as follows.

(Note 1) RT355D: Organic red pigment manufactured by Ciba Specialty Chemicals, trade name "cinquasia magenta RT355D".

A: "HP Design Jet pigment ink system UV magenta CI894A", manufactured by Hewlett Packard, magenta ink for inkjet b: "μ-Crysta MC5CL01 magenta color", manufactured by Epson, c: "HP Design Jet" Pigment ink system
UV yellow CI895A ", manufactured by Hewlett Packard, yellow ink for inkjet d:" μ-Crysta MC5CL01 yellow color ", manufactured by Epson, inkjet ink

[0087]

[Table 2]

[0088]

[Table 3]

Examples 1 to 6 and Comparative Examples 1 to 4 Inkjet drawing apparatus "BJ" was prepared by using each of the above water-based inks to 10 on the polyester film surface as shown in Table 4.
Printing was performed using "F660V" (manufactured by Canon Inc.) to form a printing layer. After being dried at room temperature for 10 minutes, a two-pack type acrylic urethane organic solvent type clear paint "Retan PG2K clear" (manufactured by Kansai Paint Co., including an ultraviolet absorber) is dried on the printed layer to a thickness of 30 to 40 μm. Air spray coating to achieve
Each inkjet print was obtained by drying for one minute.

A durability test was carried out and evaluated for each ink jet printed material by the following method. The results are also shown in Table 4. (* 1) Durability test : Each inkjet print was immersed in deionized water at room temperature for 24 hours, and the degree of bleeding on the printed surface was visually evaluated. Good condition without bleeding. The state where the image on the printed surface was broken due to bleeding was defined as x.

[0091]

[Table 4]

Examples 7 to 18 and Comparative Examples 5 to 10 On a cold rolled dull steel sheet having a thickness of 0.8 mm which has been subjected to zinc phosphate chemical conversion treatment, an epoxy resin-based cationic electrodeposition coating is applied to give a dry film thickness of about 20 μm. Electrodeposition coating and baking were performed so that the resulting electrodeposition coating film was coated with an automotive polyester resin-based intermediate coating paint so that the dry film thickness was about 20 μm and baked. The coated plate was subjected to water polishing with # 400 sandpaper, drained and dried, and degreased with petroleum benzine. Then, on the degreasing plate, using each of the above water-based inks to 10 as shown in Table 5,
Inkjet type automatic coating machine "Michelangelo V7" (manufactured by LAC Inc.)
Paint and print at 0%, let stand for 5 minutes at room temperature to dry, and then bake for 10 minutes at 80 ° C in an electric hot air dryer to form a printed layer, and volatilize most of the volatile components, and then indoor And left to cool, and then the clear coatings (II-1) to (II-4) shown in Table 5 were applied thereto to obtain a dry film thickness of 40 μm.
Each of the ink jet prints was obtained by air-spray coating so as to obtain the following and baked at 140 ° C. or 80 ° C. for 30 minutes in an electric hot air dryer depending on the paint used.

These were subjected to a 600-hour and 2000-hour test with a xenon weatherometer, and the ΔE of the coated plate after the test was measured by a "color view spectrocolorimeter" (BYK-Che.
The color was measured by Mie Inc.) and the weather resistance was evaluated. The results are also shown in Table 5. The smaller the ΔE value, the better the weather resistance.

In Table 5, each clear coating material is as follows. (II-1): Acrylic resin organic solvent type thermosetting clear coating "KINO1200T" (manufactured by Kansai Paint Co., including UV absorber) (II-2): Acrylic resin organic solvent type clear coating "Aclick 2026" (Kansai Paint Co., Ltd., including UV absorber) (II-3): Acrylic melamine resin-based organic solvent type thermosetting clear paint "Magiclon TC-71" (Kansai Paint Co., Ltd. including UV absorber) ( II-4): Two-component acrylic urethane-based organic solvent type clear paint "Retan PG2K clear" (manufactured by Kansai Paint Co., including UV absorber)

[0095]

[Table 5]

[0096]

EFFECTS OF THE INVENTION According to the present invention, a coloring layer is formed by forming a printing layer on a substrate surface by an ink jet method using a specific aqueous ink composition and further forming a clear coat layer by using a clear coating. In addition to forming a printed layer having an excellent finished appearance, further providing a clear layer makes it possible to obtain an ink-jet printed material having excellent weather resistance and the like. The inkjet printed material is particularly suitable for outdoor applications such as building wall surfaces, outdoor signboards, road signs, and vehicle bodies.

Front page continuation (51) Int.Cl. ⁷ identification code FI theme code (reference) B41J 3/04 101Y (72) Inventor Akihiko Yamauchi 4-17-1, Higashi-Hachiman, Hiratsuka-shi, Kanagawa Kansai Paint Co., Ltd. ( 72) Inventor Isao Kammori 4-17-1, Higashi-Hachiman, Hiratsuka-shi, Kanagawa Kansai Paint Co., Ltd. F-term (reference) 2C056 EA04 EE17 FC01 HA44 2H086 BA01 BA05 BA38 BA53 BA55 BA59 4J039 AD20 BE01 BE12 BE22 CA06 EA15 EA16 EA17 EA19 EA34 EA36 EA40 EA44 EA48 GA24

Claims (5)

[Claims] 1. A polymerizable unsaturated monomer containing at least one ionic functional group selected from the group consisting of (A) tertiary amino group, quaternary ammonium salt group and sulfonic acid group, and (B) polyoxyalkylene. Inkjet method using a water-based ink composition containing a pigment dispersion resin, which is a copolymer of a nonionic polymerizable unsaturated monomer having a chain and (C) another ethylenically unsaturated monomer, a pigment, and an aqueous medium A method for producing an ink-jet printed product, comprising forming a print layer (I) by the method described above, and then forming a clear coat layer (II) thereon using a clear coating material. 2. The pigment-dispersing resin uses a UV-absorbing polymerizable unsaturated monomer and / or a UV-stable polymerizable unsaturated monomer (D) as at least a part of the other ethylenically unsaturated monomer (C). The method according to claim 1, which is formed by the following method. 3. The method according to claim 1, wherein the print layer (I) is formed by an inkjet drawing method using a head having dedicated nozzles for each of the four color water-based ink compositions of red, blue, yellow and black. . 4. The method according to claim 1, wherein the clear coating contains an ultraviolet absorber and / or an ultraviolet stabilizer. 5. An inkjet printed material produced by the method according to any one of claims 1 to 4.