JP2003305941A - Manufacturing method for ink jet printed matter - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a manufacturing method for ink jet printed matter excellent in design effect, aesthetic properties and visibility, suitable for an outdoor use such as the wall surface of a building, an outdoor signboard, a road mark, a car body or the like, enhanced in ink fixability (density) and having excellent weatherability, and ink jet printed matter obtained thereby. <P>SOLUTION: A coating film layer (I) is formed on the surface of a substrate using luminous pigment-containing coating or light-coherent pigment-containing coating and a printing layer (II) is subsequently formed thereon by an ink jet system using an aqueous ink composition and, further, a clear coat layer (III) using clear coating is formed thereon to manufacture the ink jet printed matter. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention has an excellent design (aesthetic appearance) and visibility, and has a favorite pattern suitable for outdoor applications such as building wall surfaces, outdoor signboards, road signs, and vehicle bodies, and ink Relates to a method for producing an inkjet printed product having improved fixing property (density) and excellent weather resistance, and an inkjet printed product obtained thereby.

[0002]

2. Description of the Related Art Inkjet printers have been widely used as computer printing devices. This ink jet printer ejects ink 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 computer's storage device to form dots on printing paper. The color tones of the pixels are reproduced by attaching them in a circular shape and overlapping them on the printing paper.Furthermore, by driving the nozzle in the left and right direction and driving the printing paper in the vertical direction, the image data is printed on the printing paper. Can draw.

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. In addition, improvement in light resistance has been demanded, and designability (aesthetic appearance) as printed matter for these outdoor applications has also been demanded.

For this reason, the coloring material for ink jet inks is being changed from dyes to pigments, but with aqueous pigment inks, the print density of printed images is still insufficient, and the dispersion stability of pigments is insufficient. 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 are demanded.

On the other hand, as a method for imparting functions such as weather resistance, scratch resistance, and acid resistance to an ink jet printed matter, a plastic film containing an ultraviolet absorber or the like is laminated and adhered to the printed layer. It was being appreciated. However, this method requires a great number of man-hours for the laminating process and is insufficient in imparting the above function.

[0006]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that after forming a coating layer using a phosphorescent pigment-containing paint or a light interference pigment-containing paint, By forming a print layer by an inkjet method using an aqueous ink composition on the above, by further forming a clear coat layer using a clear coating, not only a print layer excellent in design and finished appearance can be formed, By providing a clear layer, it was found that a printed matter excellent in weather resistance and the like can be obtained, and the present invention has been completed.

That is, according to the present invention, the coating layer (I) is formed on the surface of the base material by using the coating material containing the phosphorescent pigment or the coating material containing the light interference pigment, and then the aqueous ink composition is used on the coating layer (I). To form a printing layer (II), and a clear coating layer (II) is formed on the printing layer (II).
The present invention provides a method for producing an inkjet printed article, which comprises forming I), and an inkjet printed article obtained by this production method.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, the substrate surface is
It is not particularly limited, for example, paper, metal base material,
Examples thereof include substrates such as plastics substrates, substrates such as mortar and slate, and those obtained by subjecting these substrates to surface treatment and / or coating film formation. In addition, a pressure-sensitive adhesive sheet having an adhesive layer provided on the surface of the base material opposite to the surface on which the print layer is formed can be applied.

In the present invention, a coating layer (I) is formed on the surface of the above-mentioned substrate using a phosphorescent pigment-containing coating material or a light interference pigment-containing coating material. Before forming (I), a white base coating film layer (V) may be formed on the surface of the base material.

The white base coating layer (V) has an oil absorption of 1
0-400 ml / 100 g, preferably 150-350
A white paint containing ml / 100 g of silica fine particles and having a pigment volume concentration (hereinafter sometimes abbreviated as “PVC”) in the paint solid content of 5 to 90%, preferably 10 to 55%. It is desirable to be formed by using. Here, "oil absorption" is defined as JIS K5101 21 (1991).
It is a measured value according to the method described in. The "pigment volume concentration (PVC)" is the volume ratio of the pigment component in the total solid content of the resin component and the pigment component, and the "pigment component" is a chromatic or achromatic color pigment, metal flake, or the like. The above-mentioned bright pigments, extender pigments containing fine silica particles, and rust preventive pigments are collectively referred to.

The silica fine particles are usually 0.1
Those having an average particle diameter in the range of 10 to 10 μm, particularly 1 to 7 μm are suitable. The content of the silica fine particles is 3 to 4 based on the total weight of all pigment components in the white paint.
A suitable range is 0% by weight, preferably 3 to 30% by weight, and more preferably 5 to 25% by weight.

Further, if the PVC is less than 5%, the resulting coating film is remarkably inferior in concealing property, whereas if the PVC content is more than 90%, the viscosity of the coating composition becomes high and it becomes difficult to form a smooth coating film, which is not preferable.

As the white paint, any organic paint, water-based paint, powder paint or the like can be used without limitation as long as it contains a white pigment. Examples of the base resin component of the coating include various acrylic resin-based, polyester resin-based, alkyd resin-based, urethane resin, epoxy resin, etc., which may have functional groups such as hydroxyl group, carboxyl group, amino group, etc. Resins can be used, and these can be used in combination with a crosslinking agent such as a polyisocyanate compound or an amino resin which may be appropriately blocked. Further, the white paint may be a room temperature or thermosetting type, or may be a type which is cured by an actinic ray such as an ultraviolet ray or an electron beam. In particular, a coating material made of an acrylic resin of a urethane curing type or an ultraviolet curing type, which is made of a polyisocyanate compound which may be blocked with an acrylic polyol or a polyester polyol, is suitable.

The white pigment that can be added to the above paint is
Usually, titanium oxide, zinc white, and lead white can be used. Further, these may contain, if necessary, extender pigments such as barium sulfate, calcium carbonate, hydrous magnesium silicate, talc, mica, clay, and perlite, and aggregates within a range that does not affect whiteness. . The white pigment is suitable in the range of at least 55% by weight, preferably 70 to 95% by weight, based on the total weight of the pigment components to be added.

The white paint is, for example, air spray,
It can be applied by a method such as airless spraying or electrostatic rotary atomization coating method, and if necessary, can be touch-dried, semi-cured or heat-cured by air-drying, hot-air spraying or the like. The film thickness of the white base coating film layer (V) thus obtained is usually about 5 to 50 μm as a dry film thickness.

In the present invention, the coating layer (I) formed on the surface of the substrate or on the white base coating layer (V) is a phosphorescent pigment-containing coating material or a light interference pigment-containing coating material. Is formed using.

The phosphorescent pigment-containing paint can be used without limitation as long as it contains a phosphorescent pigment, such as an organic solvent type paint, an aqueous paint, and a powder paint. As the base resin component of the coating material, for example, an acrylic resin type, a polyester resin type, an alkyd resin type, which may optionally have a functional group such as a hydroxyl group, a carboxyl group and an amino group,
Various resins such as urethane resin and epoxy resin can be used, and these can be used in combination with a polyisocyanate compound which may be appropriately blocked, and a crosslinking agent such as amino resin. Further, the coating material may be a room temperature or thermosetting type, or may be a type which is cured by an actinic ray such as an ultraviolet ray or an electron beam.

As the phosphorescent pigment, ones known per se can be used. For example, calcium sulfide phosphor (host crystal is CaS, activator is Bi); zinc sulfide phosphor (host crystal is ZnS, The activator is Cu) (commercially available products include Nemoto Special Chemical Co., Ltd., "GSS", etc.); Strontium aluminate (matrix crystal is SrA
l2 O4, activator is rare earth element (commercially available, Nemoto Special Chemical Co., Ltd., "N night light" NEW
-G300M, NEW-BG300M, NEW-V30
0M, etc.); Phosphor having strontium aluminate or calcium aluminate as a host crystal and europium, desprosium or neodymium as an activator; CaSrS as a host crystal and Bi as an activator; ZnS as a host crystal
The activator is Cu, Co; the host crystal is CaS, and the activator is europium, Tm, and the like, which develop purple blue, blue green, and yellow green. Further, trade name of "R-Bright" B-10, B-15, B manufactured by Lead Co.
-25, B-50 and the like can also be used as the luminous pigment.
All of these phosphorescent pigments are solid, can be easily mixed and dispersed with the resin composition, and have a particle size of 5 to 100 μm, particularly 1 to have a smooth coating surface.
It is preferable to grind so that the particle size becomes 0 to 30 μm. The ratio of the resin component and the phosphorescent pigment in the above phosphorescent pigment-containing paint is not particularly limited, but the resin component 100
10 to 500 parts by weight, particularly 100 to 400 parts by weight are suitable for the phosphorescent pigment per part by weight (solid content).

On the other hand, the light-interfering pigment-containing paint may be any organic solvent-based paint, water-based paint,
It can be used without limitation, such as powder paint. Examples of the base resin component of the coating include various acrylic resin-based, polyester resin-based, alkyd resin-based, urethane resin, epoxy resin, etc., which may have functional groups such as hydroxyl group, carboxyl group, amino group, etc. Resins can be used, and these can be used in combination with a crosslinking agent such as a polyisocyanate compound or an amino resin which may be appropriately blocked. Further, the coating material may be a room temperature or thermosetting type, or may be a type which is cured by actinic rays such as ultraviolet rays and electron beams. Examples of the light interference pigment include scaly mica and mica surface-coated with a metal oxide such as titanium oxide or iron oxide.
The shape of these light-interfering pigments is scaly, the size is 0.1 to 2 μm in thickness, and the longitudinal dimension is 2 to 40.
It is preferably μm. The ratio of the resin component and the light interference pigment in the above light interference pigment-containing coating material is not particularly limited, but per 100 parts by weight (solid content) of the resin component,
1 to 50 parts by weight, particularly 3 to 30 parts by weight is suitable for the light interference pigment.

The above-mentioned coating material containing a light-accumulating pigment or coating material containing a light-interfering pigment may contain an ink fixing resin, if necessary, from the viewpoint of the ink fixing property of the upper layer.

The ink fixing resin plays a role of quickly absorbing and fixing the ink, and the ink fixing resin is not particularly limited, and a conventionally known hydrophilic resin or ink that absorbs water of ink. It is possible to use an ink set resin or the like for fixing the ink. In particular, as the ink fixing resin, (a) at least one ionic functional group selected from a tertiary amino group, a quaternary ammonium salt group and a sulfonic acid group, which functions as both a hydrophilic resin and an ink setting agent. A polymerizable unsaturated monomer containing a group, (b)
A resin (A) obtained by copolymerizing a monomer mixture containing a nonionic polymerizable unsaturated monomer having a polyoxyalkylene chain and (c) another ethylenically unsaturated monomer in the presence of a radical polymerization initiator is preferable. Is.

Examples of the monomer (a) include N,
N-dimethylaminoethyl (meth) acrylate, N,
N-diethylaminoethyl (meth) acrylate, N,
N-dimethylaminopropyl (meth) acrylate,
Aminoalkyl (meth) acrylates containing tertiary amino groups such as N, N-di-t-butylaminoethyl (meth) acrylate, N, N-dimethylaminobutyl (meth) acrylate; N, N-dimethylamino Aminoalkyl (meth) acrylamide containing a tertiary amino group such as ethyl (meth) acrylamide, N, N-diethylaminoethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide; 2-
(Methacryloyloxy) ethyltrimethylammonium chloride, 2- (methacryloyloxy) ethyltrimethylammonium bromide, methacryloylaminopropyltrimethylammonium chloride, methacryloylaminopropyltrimethylammonium bromide, tetrabutylammonium (meth) acrylate, trimethylbenzylammonium (meth) acrylate, Quaternary ammonium base-containing monomers such as 2- (methacryloyloxy) ethyltrimethylammonium dimethylphosphate; (meth) acrylamide-such as 2-acrylamido-2-methylpropanesulfonic acid
Examples thereof include sulfonic acid group-containing polymerizable unsaturated monomers such as alkanesulfonic acid and sulfoalkyl (meth) acrylates such as 2-sulfoethyl (meth) acrylate. These compounds may be used alone or in combination of two or more. Among these, as the polymerizable unsaturated monomer (a), especially N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, 2- (methacryloyloxy) ethyltrimethylammonium chloride, Acrylamide-2-methylsulfonic acid and the like are suitable.

In the present specification, "(meth) acrylate" means "acrylate or methacrylate", and "(meth) acrylamide" means "acrylamide or methacrylamide".

The above-mentioned monomer (b) is a monomer having a polyoxyalkylene chain and a polymerizable unsaturated group. 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 20.
It is suitable to be in the range of 0 to 3,000, preferably 300 to 2,500. When the molecular weight is less than 200, the effect as a hydrophilic group cannot be sufficiently exerted, and the coating film performance (particularly water resistance) is adversely affected, which is not preferable. On the other hand, when the molecular weight is more than 3,000,
Since it solidifies at room temperature and the solubility deteriorates, it is difficult to handle and is not preferable.

As a typical example of the monomer (B), for example, the following formula (1) CH2 = C (R1) COO (CnH2n
O) m-R2 (1) (In the formula, R1 represents a hydrogen atom or CH3, R2 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and m represents an integer of 4 to 60, preferably 6 to 50. , N represents an integer of 1 to 3, preferably 2.), and these are one kind or 2
A combination of two or more species can be used.

Specific examples of the 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, methoxytetrapropylene 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, These can be used alone or in combination of two or more. Of these, polyethylene glycol (meth) acrylate and polypropylene glycol (meth) acrylate are particularly preferable.

The monomer (c) is a monomer copolymerizable with the monomer (a) and the monomer (b), and is the monomer (a) and the monomer (b).
It is a monomer other than. As a specific example, 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- Directly of C1-24 such as ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate and tridecyl (meth) acrylate. Chain or cyclic alkyl (meth) acrylate monomer; 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate and other hydroxyl group-containing polymerizable unsaturated Monomers; Carboxyl group-containing polymerizable unsaturated monomers such as methacrylic acid and acrylic acid; Acrylamide and methacrylamide; 3-Ethyl-
3- (meth) acryloyloxymethyl oxetane, 3
-Oxetane ring-containing (meth) acrylates such as methyl-3- (meth) acryloyloxymethyl oxetane and 3-butyl-3- (meth) acryloyloxymethyl oxetane; aromatic vinyls such as styrene, α-methylstyrene and vinyltoluene Compounds; (meth) acrylonitrile, vinyl acetate and the like can be mentioned. These polymerizable unsaturated monomers may be used alone or in combination of two or more.

The resin (A) includes the above-mentioned monomers (a) to (a).
It is obtained by copolymerizing (c). The composition of these monomer mixtures in the copolymerization is 1 to 40% by weight of the monomer (a), preferably 1 to 35% by weight, 5 to 40% by weight of the monomer (b), preferably 7.5 to 30%.
%, And 20 to 94% by weight of the monomer (c), preferably 35 to 91.5% by weight.

The copolymerization of the above monomers (a) to (c) is
It can be carried out by a method known per se, for example, a solution polymerization method in an organic solvent, an emulsion polymerization method in water, and the like, but the solution polymerization method is preferable.
As the copolymerization method by the solution polymerization method, for example, a mixture of the monomer component and the radical polymerization initiator is dissolved or dispersed in an organic solvent, and usually at a temperature of about 80 ° C. to 200 ° C. and usually for about 1 to 10 hours. A method of heating and polymerizing while stirring can be mentioned.

As the organic solvent which can be used at the time of copolymerization,
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. During the polymerization reaction, the organic solvent is usually added in an amount of 40 with respect to the total amount of the monomer components.
It is used in the range of 0 parts by weight or less.

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 (tert-butylperoxy) cyclohexane, n-butyl-4,4
-Peroxyketals such as bis (tert-butylperoxy) valerate; cumene hydroperoxide,
Hydroperoxides such as 2,5-dimethylhexane-2,5-dihydroperoxide; 1,3-bis (tert-butylperoxy-m-isopropyl) benzene, 2,5-dimethyl-2,5- Dialkyl peroxides such as di (tert-butylperoxy) hexane, diisopropylbenzene peroxide, tert-butylcumyl peroxide; decanoyl peroxide, lauroyl peroxide, benzoyl peroxide,
Diacyl peroxides such as 2,4-dichlorobenzoyl peroxide; Peroxycarbonates such as bis (tert-butylcyclohexyl) peroxydicarbonate; tert-butylperoxybenzoate, 2,5
-Organic peroxide type polymerization initiators such as peroxyesters such as dimethyl-2,5-di (benzoylperoxy) hexane and 2,2'-azobisisobutyronitrile,
Examples thereof include azo-based polymerization initiators such as 1,1-azobis (cyclohexane-1-carbonitrile), azocumene 2,2′-azobismethylvaleronitrile, and 4,4′-azobis (4-cyanovaleric acid). it can. The amount of these radical polymerization initiators used is not particularly limited, but is usually 0.1 to 15 parts by weight, particularly 0.3 to 10 parts by weight, based on 100 parts by weight of the total amount of the polymerizable monomers. It is desirable to be within the range of parts.

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 steps from the initial polymerization to the latter half of the polymerization rather than being charged at the beginning of the polymerization all at once, controlling the temperature in the polymerization reaction, suppressing the formation of a defective cross-linked product such as a gelled product, etc. It is preferable from the point of.

The molecular weight of the thus obtained copolymer is not particularly limited, but it is usually a weight from the viewpoint of water dispersion stability, viscosity, VOC, resin color number (coloring degree) and the like. The average molecular weight is preferably in the range of 500 to 100,000, particularly 1,000 to 50,000.

When the above resin (A) is contained as a resin for ink fixing in the above-mentioned paint containing a light-accumulating pigment or a paint containing a light-interfering pigment, 5 to 90% by weight based on the total solid content of the resin in the paint, It is desirable that the content is preferably 30 to 80% by weight.

If necessary, the above-mentioned phosphorescent pigment-containing paint or light interference pigment-containing paint may further include an organic solvent, a pigment dispersant, an anti-settling agent, a coloring pigment, a metallic pigment, an extender pigment, an ultraviolet absorber, and a light absorber. Stabilizers and the like can be appropriately added. As the extender pigment, silica fine particles exemplified in the above description of the white paint can be appropriately used.

The phosphorescent pigment-containing paint or the light interference pigment-containing paint is applied by a method such as air spray, airless spray, electrostatic rotary atomization coating method, etc., and if necessary, by air drying, hot air blowing, etc. It can be touch dried, semi-cured or heat cured.
The film thickness of the coating film layer (I) obtained is usually about 20 to 200 μm as a dry film thickness of a phosphorescent pigment-containing coating film and usually 5 to 80 μm as a light interference pigment-containing coating film. It is a degree.

The coating layer (I) may be a multi-layer coating film formed by sequentially coating the above-mentioned phosphorescent pigment-containing coating material and light interference pigment-containing coating material.

In the present invention, before forming the printing layer (II) on the surface of the coating layer (I) formed by the above-mentioned coating material containing the light-accumulating pigment or the coating material containing the light-interfering pigment, if necessary, an ink fixing agent layer ( IV) may be formed. The ink fixing agent layer (I)
Is a layer that plays a role of quickly absorbing and fixing ink, and is usually formed by using an ink fixing agent containing a hydrophilic resin that absorbs ink moisture or an ink setting agent that fixes the ink. Is.

As the above ink fixing agent, in particular, (a) 3 which functions as both a hydrophilic resin and an ink setting agent,
A polymerizable unsaturated monomer containing at least one ionic functional group selected from a primary amino group, a quaternary ammonium salt group and a sulfonic acid group, (b) a nonionic polymerizable unsaturated monomer having a polyoxyalkylene chain, And (c)
Copolymerized in the presence of a radical polymerization initiator a monomer mixture consisting of other ethylenically unsaturated monomers,
Those containing the resin (A) as described above are preferable.

The resin (A) made of the copolymer produced as described above is soluble in both hydrophilic solvent and hydrophobic solvent, and is made aqueous by using a basic neutralizing agent. It is also possible to mix with any organic solvent-based or water-based ink fixing agent. The monomer (A) constituting the resin (A) has an ionic functional group that can work favorably in terms of fixing the ink, and the hydrophilic monomer (B) has a function that favorably absorbs water in the ink. You can The resin (A) is
It is desirable that the total amount of resin solids in the ink fixing agent is 5% by weight or more, preferably 30 to 80% by weight.

If necessary, the ink fixing agent may be, for example, polyvinyl alcohol, polyethylene glycol,
Polyvinyl pyrrolidone, polyester resin, epoxy resin, acrylic resin, urethane resin and other resin components, amino resin, isocyanate compound and other crosslinking agents, pigments, organic solvents, thickeners, film-forming aids, UV absorbers, light Various additives such as stabilizers and leveling agents can be added.

As the above-mentioned pigment, it is desirable to add silica fine particles having an oil absorption of 10 to 400 ml / 100 g from the fixing surface of the ink. The silica fine particles can be appropriately used from the examples given in the above description of the white paint. The mixing ratio of the silica fine particles is not particularly limited, but is usually 0 with respect to 100 parts by weight of the resin (A).
It is desirable to be in the range of -80 parts by weight, particularly 10-40 parts by weight.

The above-mentioned ink fixing agent is applied by a method such as air spray, airless spray, electrostatic rotary atomization coating method, roll coater, gravure coater, etc., and if necessary, air-dried, touch-air dried by hot air spraying or the like. It can be semi-cured or heat-cured.
The thickness of the obtained ink fixing agent layer (I) is usually about 1 to 50 μm, preferably about 3 to 30 μm as a dry film thickness.

In the present invention, the printing layer (II) is provided on the surface of the coating layer (I) or the surface of the ink fixing agent layer (IV) formed by the above-mentioned paint containing a light-accumulating pigment or a paint containing a light interference pigment.
It is formed by an inkjet method using a water-based ink composition. As the water-based ink composition, conventionally known water-based dye inks and water-based pigment inks for inkjet can be used without particular limitation. However, regarding the water-based pigment ink, the wettability and dispersion stability of the pigment, and further the point of color developability In particular, (d) a polymerizable unsaturated monomer containing at least one ionic functional group selected from a tertiary amino group, a quaternary ammonium salt group and a sulfonic acid group, (e)
Pigmented resin (B) obtained by copolymerizing a monomer mixture containing a nonionic polymerizable unsaturated monomer having a polyoxyalkylene chain and (f) another ethylenically unsaturated monomer in the presence of a radical polymerization initiator. An aqueous ink composition which is contained as a dispersion resin and further contains a pigment and an aqueous medium is suitable.

The monomer (d) can be appropriately selected and used from the monomers (a) listed in the description of the ink fixing agent, and particularly N, N-dimethylaminoethyl (meth) acrylate. , N, N-diethylaminoethyl (meth) acrylate, 2- (methacryloyloxy) ethyltrimethylammonium chloride,
Acrylamide-2-methylsulfonic acid and the like are suitable. Furthermore, when N, N-dimethylaminoethyl (meth) acrylate and / or N, N-diethylaminoethyl (meth) acrylate is used in combination with 2- (methacryloyloxy) ethyltrimethylammonium chloride,
It is preferable because the range of applicable pigments is widened. 2- (methacryloyloxy) ethyltrimethylammonium chloride has a high pigment-dispersing effect even with a small amount, and therefore the ratio (weight) of the two is 5/1 to 1 (quaternary salt) / latter (tertiary).
It is about 1/10.

The monomer (d) has a tertiary amino group and /
In the case of a polymerizable unsaturated monomer containing a quaternary ammonium salt group, these groups particularly effectively act on the pigment dispersibility of an acidic pigment or a neutral pigment, and the monomer (d) is a sulfonic acid. In the case of the group-containing polymerizable unsaturated monomer, the sulfonic acid group particularly effectively acts on the pigment dispersibility of the basic pigment. The monomer (e) can be appropriately selected and used from the monomers (b) listed in the description of the ink fixing agent.

The above-mentioned monomer (f) can be appropriately selected and used from the monomers (c) listed in the above description of the ink fixing agent. Further, the monomer (f)
Is, if necessary, as at least part of its ingredients,
An ultraviolet absorbing polymerizable unsaturated monomer and / or an ultraviolet stable polymerizable unsaturated monomer may be used.

Examples of the ultraviolet absorbing polymerizable unsaturated monomer include 2,4-dihydroxybenzophenone,
Addition reaction product of hydroxybenzophenones such as 2,2 ′, 4-trihydroxybenzophenone and glycidyl (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-hydroxy Propoxy) benzophenone, 2,2'-dihydroxy-4- (3-acryloxy-2-hydroxypropoxy) benzophenone, etc .; or 2- (2'-hydroxy-5'-methacryloyloxyethylphenyl) -2H-benzotriazole, etc. Is mentioned. Of these, those having a (2'-hydroxyphenyl) -benzotriazole structure are particularly preferably used.

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

Further, the above-mentioned monomer (f) can be easily removed from the surface of the substrate, easily removed from the ink, and reacted with the cross-linking agent component in terms of adhesion and water resistance. It is desirable to contain a hydroxyl group-containing polymerizable unsaturated monomer as at least a part of the components.

Specific examples of the hydroxyl group-containing polymerizable unsaturated monomer include 2-hydroxyethyl (meth).
In addition to acrylates, polyhydric alcohols such as hydroxypropyl (meth) acrylate, 2,3-dihydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate and polyethylene glycol mono (meth) acrylate and acrylic acid or methacrylic acid Examples thereof include monoesters with acids; compounds obtained by ring-opening polymerization of ε-caprorapton with the above monoesters of polyhydric alcohols and acrylic acid or methacrylic acid.
Among them, 4-hydroxybutyl (meth) acrylate, polyethylene glycol mono (meth) acrylate
[Other than the above-mentioned monomer (e)], and a compound obtained by ring-opening polymerization of ε-caprorapton with a monoester product of a polyhydric alcohol and acrylic acid or methacrylic acid are preferable from the viewpoint of reactivity and the like. The exemplified compound is one kind,
Alternatively, two or more kinds can be used in combination. The copolymerization amount of the hydroxyl group-containing polymerizable unsaturated monomer is 3 to 30% by weight, preferably 5 to 25% by weight, based on the total amount of the monomers (d), (e) and (f). Is desirable.

Further, in order to secure the water dispersibility of the resin (B), a carboxyl group-containing polymerizable unsaturated monomer may be contained as at least a part of the above-mentioned monomer (f), if necessary. Even when the carboxyl group-containing polymerizable unsaturated monomer is contained, it is preferable from the viewpoint of pigment dispersibility that a basic neutralizing agent is not mixed.

The resin (B) contains the monomer (d),
It is obtained by copolymerizing (e) and (f).
The proportion of each of these monomers used in the copolymerization can be within the following range based on the total amount thereof. Monomer (d): 0.5 to 40% by weight, preferably 1 to 30% by weight, Monomer (e): 5 to 40% by weight, preferably 7 to 35% by weight, Monomer (f): 20 to 94.5 % By weight, preferably 35 to 92% by weight.

The polymerization method for obtaining the resin (B) is as follows:
The methods listed in the description of the resin (A) used for the ink fixing agent can be adopted.

The resin (B) thus obtained is not particularly limited in its molecular weight, but its water dispersion stability,
In terms of pigment dispersibility, viscosity, VOC, color number (coloring degree) of resin, etc., the weight average molecular weight is usually 500 to 100,0.
00, particularly preferably in the range of 1,000 to 50,000.

Since the resin (B) is used as a pigment-dispersing resin, it is necessary that the wettability with the pigment and the dispersion stabilization be compatible. The monomer (d) constituting the pigment-dispersed resin can improve the adsorption of the pigment-dispersed resin to the pigment, and works advantageously in terms of both the wettability to the pigment and the dispersion stability of the resin. You can Further, the monomer (e) that constitutes the pigment-dispersed resin can improve the solubility of the pigment-dispersed resin in the continuous phase (aqueous medium), and can particularly advantageously work to improve the dispersion stability of the pigment-dispersed resin. In particular, by copolymerizing the above-mentioned monomer (e), it is possible to remarkably improve the dispersion of a black (carbon black) pigment, which is a particularly difficult dispersion pigment.

The aqueous ink composition used in the present invention is
It contains the above resin (B), a pigment, an aqueous medium, and if necessary, a pigment dispersion resin other than the resin (B), a dispersion aid, a basic neutralizing agent, and other additives.

Examples of the above-mentioned 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; 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. Each of these pigments may be subjected to a known surface treatment such as acid / base treatment, coupling agent treatment, plasma treatment, oxidation / reduction treatment and the like.

Of these, specific examples of pigments used particularly in ink jet inks include, for example, Rave.
n7000, Raven5750, Raven525
0, Raven5000 ULTRAII, Raven3
500, Raven2000, Raven1500, R
aven1250, Raven1200, Raven1
190 ULTRAII, Raven1170, Rave
n1255, Raven1080, Raven1060
(Above, Columbian Carbon Co., Ltd.), Regal4
00R, Regal330R, Regal660R, M
ogul L, Black Pearls L, Mona
rch 700, Monarch 800, Monarc
h 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 include, but are not limited to, yellow pigments such as 154.

The mixing ratio of the pigment is not particularly limited, but usually 100 parts by weight of the pigment dispersion resin is used.
It is preferably in the range of 10 to 3,000 parts by weight, particularly 15 to 2,000 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. As an organic solvent,
For example, 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; sparingly soluble in xylene, toluene, cyclohexanone, hexane, pentane, or the like. Examples include insoluble organic solvents. The organic solvent may be used alone or in combination of two or more. As the organic solvent, those mainly containing a water-soluble organic solvent are suitable. The mixing ratio of water and the organic solvent is not particularly limited, but the content of the organic solvent is 5% of the mixed solution.
It is preferably 0% by weight or less, and particularly preferably 35% by weight or less. If it is out of this range, there is a possibility that a water-based ink cannot be substantially formed. The mixing ratio of the aqueous medium is not particularly limited, but is usually 50 to 5,000 parts by weight, particularly 100 to 100 parts by weight with respect to 100 parts by weight of the pigment dispersion resin or the dispersant.
It is preferably in the range of 3,000 parts by weight from the viewpoint of viscosity at the time of pigment dispersion, pigment dispersibility, dispersion stability, production efficiency and the like.

Examples of the pigment-dispersing resin other than the resin (B) which is used if necessary include, for example, a carboxyl group-containing polymerizable unsaturated monomer such as (meth) acrylic acid,
Examples thereof include acrylic resins obtained by copolymerizing a hydroxyl group-containing polymerizable unsaturated monomer such as 2-hydroxyethyl (meth) acrylate 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 15
50,000, especially 5,000 to 100,000, acid value 5 to 150, especially 15 to 100, hydroxyl value 10 to 16
Those in the range of 0, particularly 30 to 120 are preferable.
Further, as the pigment-dispersed resin other than the resin (B), for example, ethylene glycol, butylene glycol, 1,6
-Polyhydric alcohols such as hexanediol, trimethylolpropane, and pentaerythritol, adipic acid,
A polyester resin obtained by a condensation reaction with a polyvalent carboxylic acid component such as isophthalic acid, terephthalic acid, phthalic anhydride, hexahydrophthalic anhydride and trimellitic anhydride is also included. The polyester resin has a weight average molecular weight of about 1,000 to 100,000, particularly 1,500.
~ 70,000, acid value 5 ~ 150, especially 10 ~ 10
Those having a hydroxyl value of 0, a hydroxyl value of 10 to 160, and particularly 30 to 120 are preferable. In the step of obtaining the water-based ink composition, the pigment and the resin (B) are usually dispersed in an aqueous medium and then diluted with a pigment-dispersing resin other than the resin (B) to stabilize the enamel. And long-term storage stability are desirable.

Examples of the dispersion aid used as necessary include Disperby manufactured by BYK-Chemie.
Examples thereof include k184 and 190, and other additives include antifoaming agents, preservatives, rust preventives, plasticizers and the like. Considering the dispersibility of the pigment, the stability of the paste, the letdown stability, and the coating film performance, the amount of each of these components is preferably 50 parts or less with respect to 100 parts by weight of the pigment dispersion resin. As an antifoaming agent,
Specifically, "BYK-019", "BYK-02"
1 "," BYK-023 "," BYK-024 "," B
"YK-025", "BYK-028" (all are BYK
-Chemie, water-based silicone defoamer), "BY
K-011 "(manufactured by BYK-Chemie, a silicon-free polymer defoamer) and the like.

Further, the basic neutralizing agent, when the above-mentioned pigment-dispersing resin has a carboxyl group, functions to neutralize the carboxyl group and to make the pigment-dispersing resin water-soluble or water-dispersible. Examples include ammonium hydroxide, sodium hydroxide, inorganic bases such as potassium hydroxide, aminomethyl propanol, aminoethyl propanol,
Examples thereof include amines such as dimethylethanolamine, triethylamine, diethylethanolamine, dimethylaminopropanol and aminomethylpropanol. The amount of the basic neutralizing agent to be blended is such that it can be water-soluble or water-dispersible, and it is usually such that the neutralization equivalent of the carboxyl group in the pigment-dispersing resin is 0.3 to 1.5. Is preferred.

When the resin (B) is used as a pigment dispersion resin to disperse the pigment, it is desirable that no basic neutralizing agent be used. If it is used, the basic neutralizing agent is adsorbed before the resin (B) is adsorbed on the pigment, which hinders the dispersibility, which is not preferable. On the other hand, when the pigment is dispersed in the resin (B) and then diluted with a pigment dispersion resin other than this, it is desirable that the pigment is neutralized with the basic neutralizing agent.

The above water-based ink composition may further contain a water-soluble resin, a thickener, a flow control agent, a film-forming aid, if necessary.
Additives such as a surfactant, a pH adjuster, an antifungal agent, an antioxidant, an ultraviolet absorber, a light stabilizer, a chelating agent, and the like, and dyes can be added.

As the water-soluble resin, polyethyleneimine, polyamines, polyvinylpyrrolidone, cellulose attractant, polysaccharides, acrylic emulsion, polyurethane emulsion and the like can be added from the viewpoint of controlling ink characteristics. Further, a curing agent may be included as a resin component, and examples thereof include an amino resin and an optionally blocked polyisocyanate compound. These can be used alone or in combination of two or more. . The optionally blocked polyisocyanate compound includes both a blocked polyisocyanate compound in which an isocyanato group is blocked and an unblocked polyisocyanate compound. A curing catalyst may be contained when these curing agents are used.

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

In the above aqueous ink composition, the average particle size of the dispersed particles contained therein is suitably within the range of 1 to 300 nm, and the viscosity of the ink liquid is 1.0 to 10 mPa.s.
It is preferably within the range of s.

In the present invention, ink jet drawing can be carried out by the ink jet drawing method using the above water-based ink composition. Inkjet drawing methods include piezo inkjet method and thermal inkjet method.
Any known method may be used. In addition to ordinary inkjet drawing devices, drawing devices equipped with heaters for controlling ink drying,
Alternatively, a recording device that is equipped with an intermediate transfer mechanism and prints a recording material on the intermediate and then transfers it onto a recording medium such as paper, or an automatic drawing device that directly draws on a wall surface, an outdoor signboard, an automobile body, etc., is used. To form the printing layer (II).

The printing layer (II) 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 print layer (II) to be formed usually has a dry film thickness of 0.01 to 10 μm, preferably 0.01 to 1 μm.
It is a thin film layer.

In the present invention, after forming the printing layer (II) as described above, if necessary, it is touch-dried by air drying, hot air blowing, etc., semi-cured or heat-cured, and a clear coating layer is applied thereon with a clear coating layer. (III) is formed.

As the clear paint, any clear paint having good weather resistance such as organic solvent type paint, water-based paint, and powder paint can be used without limitation. As the base resin component used in the coating composition, various resins such as acrylic resin-based, polyester resin-based, alkyd resin-based, silicone resin-based, and fluororesin-based resins can be used. If necessary, polyisocyanate compound, amino resin, A crosslinking agent such as an epoxy group-containing compound or a carboxyl group-containing compound can also be used. These may be a room temperature or thermosetting type, or may be a type that is cured by an actinic ray such as an ultraviolet ray or an electron beam. Above all, a clear coating material such as a urethane-curable acrylic resin made of an acrylic or polyester polyol and a polyisocyanate compound, or an ultraviolet curable acrylic resin is preferable. From the viewpoint of weather resistance, the clear coating preferably contains an ultraviolet absorber and / or an ultraviolet stabilizer. As the ultraviolet absorber and the ultraviolet stabilizer, those listed in the description of the aqueous ink composition can be used. The blending amount of these is 0.1 with respect to 100 parts by weight of the resin solid content in the paint.
It is desirable to be about 5 parts by weight.

The clear paint can be applied by a method such as an air spray, an airless spray, an electrostatic rotary atomization type coating method and the like. The clear coat layer (III) usually has a dry film thickness of about 10 to 50 μm.

[0077]

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) Production Example 1 38 parts of ethylene glycol monobutyl ether and 12 parts of isobutyl alcohol were placed in a usual acrylic resin reaction tank equipped with a stirrer, a thermometer, and a reflux condenser, and heated and stirred. Hold 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%.
A resin (A-1) solution of was obtained.

Production Example 2 A resin solution (A-2) having a solid content of 50% was obtained by performing the same operation as in Production Example 1 except that the formulation shown in Table 1 below was used. The resin acid value of the resin (A) is shown in Table 1 below. In addition, in Table 1, "NF Byomer S20
The amount of "W" indicates the solid content.

[0080]

[Table 1]

Luminescent pigment-containing paint and light interference pigment-containing paint
Preparation of the material For 100 parts of the hydroxyl group-containing acrylic resin, the phosphorescent pigment "R-Bright B-15" (trade name, manufactured by Lead Co.)
300 parts by mixing and dispersing with an organic solvent, and then the resin (A-1) solution obtained above is added to 60% of the total resin solid content and mixed by stirring to obtain a luminous efficiency of 60% solid content. A pigment-containing paint (I-1) was prepared.

Similarly, to 100 parts of the hydroxy-containing acrylic resin, 20 parts of the light interference pigment "IRIODIN 103R" (manufactured by Merck & Co., Inc.) was added, and further the resin (A-1) was added.
The solution was added so as to be 60% of the total resin and stirred and mixed with an organic solvent to prepare a light interference pigment-containing coating material (I-2) having a solid content of 25%.

In the above paint (I-1), the resin (A
-1) A paint containing a phosphorescent pigment containing no solution (I-
3), similarly in the above paint (I-2), the resin (A-
1) A light-interfering coating material containing no solution was designated as (I-4).

Preparation of Ink Fixing Agent "Retane PG2K Aluminum Control Agent Clear"
(Kansai Paint Co., Ltd., 2 liquid type acrylic urethane type organic solvent type clear, resin solid content concentration 33.6%), the resin (A-1) solution obtained above to a resin solid content of 65 wt% Blended to make it even more "Carplex BS
-304N ”(Shionogi Pharmaceutical Co., Ltd., silica fine particles, oil absorption 171 ml / 100 g)
% Toluene dispersion was blended so as to be 20% by weight with respect to the blended solid content of the resin (A-1) to prepare an ink fixing agent (IV-1). Further, the ink fixing agent (IV-1)
In place of the resin (A-1) solution, the resin (A-2)
Ink fixing agent (IV-
2).

Production of Resin (B) for Dispersing Pigment Production Example 3 38 parts of ethylene glycol monobutyl ether and 12 parts of isobutyl alcohol were charged into a usual acrylic resin reaction tank equipped with a stirrer, a thermometer and a reflux condenser. The mixture was heated and stirred and kept at 110 ° C. In this, 48.5 parts of methyl methacrylate, 20 parts of n-butyl acrylate, 5 parts of methacryloyloxyethyl ammonium, 2-
(2'-hydroxy-5'-methacryloyloxyethylphenyl) -2H-benzotriazole 1.5 parts, 2-
Hydroxyethyl acrylate 5 parts, "NF Byomer S20W" (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., trade name, 50% water-diluted product of methoxy polyethylene glycol monomethacrylate, molecular weight about 2080) 40 parts, azobisisobutyronitrile 1 Part and 20 parts of isobutyl alcohol were added dropwise over 3 hours. 110 after the dropping
Aging for 30 minutes at 0 ° C, then 10 parts of ethylene glycol monobutyl ether and azobisisobutyronitrile 0.
An additional catalyst mixture consisting of 5 parts was added dropwise over 1 hour.
Then, the mixture was aged at 110 ° C for 1 hour and then cooled to obtain a solid content of 5
A 0% resin dispersion (B-1) solution for pigment dispersion was obtained.

Production Examples 4 and 5 In the above Production Example 3, the same operation as in Production Example 3 was carried out except that the composition shown in Table 2 below was used, and a resin solution (B-2) for pigment dispersion having a solid content of 50%. , (B-3) were obtained. The resin acid value and the like of these pigment dispersion resins are shown in Table 2 below. still,
In Table 2, the amount of "NF Byomer S20W" indicates the solid content.

[0087]

[Table 2]

Preparation of Aqueous Ink Resin solution for dispersing each pigment having a solid content of 50% obtained in Production Examples 3 to 5, pigment, "BYK-028" (BYK-Che).
Mie, trade name, silicone-based defoamer), isopropanol, glycerin and deionized water were used, and Table 3 below was used.
The mixture was placed in a wide-mouth glass bottle having a capacity of 225 cc with the composition shown in (1), glass beads having a diameter of about 1.3 mmφ were added as a dispersion media, and the mixture was sealed and dispersed with a paint shaker for 4 hours to obtain each aqueous ink.

Commercially available "BCI-31e" (manufactured by Canon Inc., ink for ink jet) blue, red, yellow,
Each black color ink was defined as a water-based ink.

[0090]

[Table 3]

Preparation of white base paint "Carplex BS-304N" (Shionogi Pharmaceutical Co., Ltd., silica fine particles, oil absorption 171 ml / 100 g) was used to prepare a toluene dispersion having a solid content of 25%.
Liquid type acrylic urethane type organic solvent type paint "Retan PG2
K White "(Kansai Paint Co., Ltd., pigment volume concentration 2
3.6%) so that the pigment volume concentration in the coating solid content was 35% to obtain a white base coating (V-1).

Preparation of Inkjet Printed Product Example 1 On the surface of a polyester film, the above white base paint (V-
1) is air-spray coated to a dry film thickness of 20 μm and dried for 20 minutes by air blowing at 60 ° C. to form a white base coating layer, and then the phosphorescent pigment-containing coating (I-1)
Is spray-coated to a dry film thickness of 50 μm and dried by air blowing at 60 ° C. for 20 minutes to form a phosphorescent pigment-containing coating layer, and an aqueous ink of each color is used thereon. Inkjet drawing device "BJF
660 V "(manufactured by Canon Inc.) was used for printing to form a printing layer. After drying at room temperature for 10 minutes, 2 on the printed layer
Liquid acrylic urethane type organic solvent type clear paint "Retan PG2K clear" (manufactured by Kansai Paint Co., including UV absorber) is air-spray coated to a dry film thickness of 30-40 µm and dried at 60 ° C for 20 minutes. Then, an ink jet printed matter was obtained.

Example 2 An ink jet printed material was obtained in the same manner as in Example 1 except that in place of ~ was used as the aqueous ink instead of ~.

Examples 3 and 4 In Examples 1 and 2, phosphorescent pigment-containing paint (I-1)
Inkjet printed materials were obtained in the same manner as in Examples 1 and 2 except that (I-3) was used instead of.

Comparative Examples 1 and 2 Ink jet prints were obtained in the same manner as in Examples 1 and 2 except that the coating layer containing the photoluminescent pigment was not formed.

Example 5 On the surface of a polyester film, the above white base paint (I-
1) is air-spray coated so that the dry film thickness is 20 μm, and dried for 20 minutes by air blowing at 60 ° C. to form a white base coating film layer, and then the light interference pigment-containing coating (I-
2) Air spray to a dry film thickness of 20 μm
It is coated and dried by air blowing at 60 ° C. for 20 minutes to form a coating layer containing a light interference pigment, and an ink fixing agent layer (IV-1) is air-dried thereon to a dry film thickness of 15 μm.
After spray coating and drying for 20 minutes at 60 ° C. with an air blow to form an ink fixing agent layer, and further on
Each of the aqueous inks of each color was used to perform printing with an inkjet drawing device "BJF660V" (manufactured by Canon Inc.) to form a printing layer. After drying at room temperature for 10 minutes, a two-component acrylic urethane-based organic solvent-based clear paint "Retan PG2K clear" (manufactured by Kansai Paint Co., Ltd.
(Including an ultraviolet absorber) was air-spray coated so that the dry film thickness was 30 to 40 μm, and dried at 60 ° C. for 20 minutes to obtain each inkjet printed material.

Example 6 An ink jet printed matter was obtained in the same manner as in Example 5, except that in place of was replaced with instead of as the aqueous ink.

Examples 7 and 8 In Examples 5 and 6, light interference pigment-containing paints (I-
Examples 5 and 6 except that (I-4) is used instead of 2)
In the same manner as above, each inkjet printed material was obtained.

Example 9 On the surface of a polyester film, the above white base paint (I-
1) is air-spray coated so that the dry film thickness is 20 μm, and dried for 20 minutes by air blowing at 60 ° C. to form a white base coating film layer, and then the phosphorescent pigment-containing coating material (I-1)
Is air-spray coated so that the dry film thickness is 50 μm, and dried by air blowing at 60 ° C. for 20 minutes to form a phosphorescent pigment-containing coating layer, and an ink fixing agent layer (IV
-2) is air-spray coated so that the dry film thickness is 15 μm, and dried for 20 minutes with an air blow at 60 ° C. to form an ink fixing agent layer, and on top of that an aqueous ink of each color is used. Inkjet drawing device "BJF
660 V "(manufactured by Canon Inc.) was used for printing to form a printing layer. After drying at room temperature for 10 minutes, 2 on the printed layer
Liquid acrylic urethane type organic solvent type clear paint "Retan PG2K clear" (manufactured by Kansai Paint Co., including UV absorber) is air-spray coated to a dry film thickness of 30-40 µm and dried at 60 ° C for 20 minutes. Then, each inkjet printed material was obtained.

Example 10 An ink jet printed matter was obtained in the same manner as in Example 9, except that in place of was replaced by instead of.

Examples 11 and 12 In Examples 9 and 10, the phosphorescent pigment-containing paint (I-
Examples 9 and 1 except that (I-3) is used instead of 1)
In the same manner as in No. 0, each inkjet printed material was obtained.

The ink jet printed materials obtained in each of the above Examples and Comparative Examples were subjected to printability and durability tests and evaluated as follows. Furthermore, the luminous properties and design properties at night were evaluated for those having the phosphorescent pigment-containing coating film, and the design properties were evaluated for those having the light interference pigment-containing coating film formed. The light emitting property and the design property were visually evaluated according to the criteria of ◯: good, Δ: somewhat inferior, and x: inferior. The results are shown in Table 4 for the water-based inks and in Table 5 for the water-based inks.

(* 1) Printability: The print state (dot shape) of each ink jet print before clear coating was observed with a microscope. The case where there is no ink bleeding and the printing density is high is indicated by ◯, and the case where ink bleeding occurs or the ink is not fixed is indicated by x. For blue, red, and yellow ink colors, the vividness of the printing surface is evaluated by the saturation value, while for black ink, the L * value of the lightness value is evaluated. (Manufactured by Minolta) was used. For blue, red, and yellow inks, the larger the value, the more vivid, and for black, the smaller the value, the higher the print density.

(* 2) Durability test: Water resistance was evaluated as a 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.

[0105]

[Table 4]

[0106]

[Table 5]

Example 13 On a 0.8 mm-thick cold rolled dull steel sheet which had been subjected to zinc phosphate chemical conversion treatment, an epoxy resin-based cationic electrodeposition coating was electrodeposited to a dry film thickness of about 20 μm and baked. On the electrodeposited coating film, an automotive polyester resin-based intermediate coating material was applied and baked so that the dry film thickness was about 20 μm. This coated plate is sanded with # 400 sandpaper, drained and dried,
Degreased with petroleum benzine. Then, the white base coating composition (V-1) was air-spray coated onto the degreasing plate so that the dry film thickness was 20 μm, and then air blown at 60 ° C.
After drying for 0 minutes to form a white base coating film layer, the phosphorescent pigment-containing coating material (I-1) was air-spray-coated so that the dry film thickness was 50 μm, and then air blown at 60 ° C.
After drying for a minute to form a luminous pigment-containing coating layer, the above aqueous inks are further used thereon, and an automatic coating machine "Michelangelo V7" by an inkjet method is used.
(Manufactured by LAC Co., Ltd.) at a booth humidity of 70% to form a printing layer by coating and printing, and after drying at room temperature for 10 minutes, a two-component acrylic urethane-based organic solvent type on the printing layer Clear paint "Retan PG2K clear" (Kansai Paint Co., Ltd., including UV absorber) with a dry film thickness of 30
Air-spray coating was performed so as to have a thickness of -40 μm, and the coating was dried at 60 ° C. for 20 minutes to obtain an inkjet print.

6 with a xenon weather meter
It was subjected to a 00-hour test, and ΔE of the coated plate after the test was measured with a "color view spectrocolorimeter" (manufactured by BYK-Chemie) to evaluate the weather resistance. As a result, for each color, the ΔE values are 1.5 for blue, 2.0 for red, and 3.0 for yellow.
It was found that each of them was as small as 0.2 and had good weather resistance.

[0109]

EFFECTS OF THE INVENTION According to the present invention, after forming a paint layer containing a light-absorbing pigment or a paint layer containing a light-interfering pigment, a printing layer is formed thereon by an inkjet method using a water-based ink composition, and a clear paint is further formed. By forming a clear coat layer using, the designability (aesthetic appearance), visibility,
Not only can a printed layer having excellent color developability and a finished appearance be formed, but by providing a clear layer, an ink jet printed article having excellent weather resistance can be obtained. Further, by providing a specific white base coat layer, an ink jet printed matter having excellent water resistance and durability can be obtained. In particular, an ink jet print containing a phosphorescent coating film can obtain an arbitrary pattern that emits light even at night. The inkjet printed material is particularly suitable for outdoor applications such as wall surfaces of buildings, outdoor signs, road signs, and vehicle bodies.

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Claims (12)

[Claims] 1. A coating layer (I) is formed on the surface of a base material by using a paint containing a phosphorescent pigment or a paint containing a light interference pigment, and then a printing layer is formed by an inkjet method using a water-based ink composition thereon. (II) is formed, and a clear coating layer (III) is further formed on it to form a clear coat layer (III). 2. The method for producing an inkjet printed product according to claim 1, wherein the paint containing a light-accumulating pigment or the paint containing a light interference pigment contains a resin for fixing an ink. 3. A polymerizable unsaturated monomer containing (a) at least one ionic functional group selected from a tertiary amino group, a quaternary ammonium salt group and a sulfonic acid group as an ink fixing resin, and (b). Contains a resin (A) obtained by copolymerizing a monomer mixture containing a nonionic polymerizable unsaturated monomer having a polyoxyalkylene chain and (c) another ethylenically unsaturated monomer in the presence of a radical polymerization initiator. The method for producing an inkjet printed material according to claim 2. 4. An ink fixing agent layer (IV) is formed on the surface of a coating layer (I) made of a coating material containing a light-accumulating pigment or a coating material containing a light interference pigment before forming a printing layer (II). Item 1
A method for producing the inkjet printed matter described. 5. The ink fixing agent comprises (a) a tertiary amino group, 4
Polymerizable unsaturated monomer containing at least one ionic functional group selected from primary ammonium base and sulfonic acid group, (b) nonionic polymerizable unsaturated monomer having polyoxyalkylene chain, and (c) other The method for producing an inkjet printed product according to claim 4, further comprising a resin (A) obtained by copolymerizing the monomer mixture of the ethylenically unsaturated monomer of 1) in the presence of a radical polymerization initiator. 6. The inkjet according to any one of claims 1 to 5, wherein the coating layer (I) is a multi-layer coating film obtained by sequentially coating a phosphorescent pigment-containing coating material and a light interference pigment-containing coating material. Method of manufacturing printed matter. 7. The method for producing an inkjet print according to claim 1, wherein the aqueous ink composition is a dye ink. 8. The method for producing an inkjet print according to claim 1, wherein the aqueous ink composition is a pigment ink. 9. An aqueous ink composition comprising (d) a polymerizable unsaturated monomer containing at least one ionic functional group selected from a tertiary amino group, a quaternary ammonium salt group and a sulfonic acid group, (e). Resin (B) obtained by copolymerizing a monomer mixture containing a nonionic polymerizable unsaturated monomer having a polyoxyalkylene chain and (f) another ethylenically unsaturated monomer in the presence of a radical polymerization initiator.
9. The method for producing an inkjet printed product according to claim 8, wherein the resin is used as a pigment dispersion resin. 10. The method for producing an inkjet print according to claim 1, wherein the clear paint contains an ultraviolet absorber and / or a light stabilizer. 11. A silica fine particle having an oil absorption of 10 to 400 ml / 100 g is contained on the surface of a base material before forming a coating layer (I) of a paint containing a phosphorescent pigment or a paint containing a light interference pigment, and The pigment volume concentration in the paint solid content is 5 to 90.
The method for producing an inkjet print according to any one of claims 1 to 10, wherein the white base coating film layer (V) is formed by using a white paint of 10%. 12. An inkjet printed material obtained by the manufacturing method according to claim 1.