JPH07164727A - Laminated image body - Google Patents

Abstract

PURPOSE:To obtain a laminated image body having a excellent mar resistance by laminating an adhesive layer, a color image pattern layer, a transparent resin layer, and an antistatic hard coating layer made of a photopolymerizable resin composition having a specific composition successively on a substrate. CONSTITUTION:A laminated image body is formed by laminating an adhesive layer 2, a color image pattern layer 3, a transparent resin layer 4, and an antistatic hard coating layer 5 successively on a substrate 1. It is necessary that the antistatic hard coating layer 5 should be made of a photopolymerizable resin composition consisting of 100 pts.wt. (meth)acrylate compound having at least two (meth)acryloyl groups in a molecule, 0.1-10 pts.wt. photopolymerization initiator, and 20-1000 pts.wt. conductive metallic oxide powder having a particle diameter of 0.01-0.4mum. It is preferable that the color image pattern layer 3 is made of a photopolymerizable resin composition consisting of a linear copolymer, a photopolymerizable unsatd. compound, a photopolymerization initiator, and a coloring agent.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a laminated image body used for manufacturing a display panel or signboard having a predetermined colored image pattern formed on a substrate. The obtained display board is
It can be used for instrument panels of various devices and dials of vehicle speedometers.

[0002]

2. Description of the Related Art Conventionally, characters and numbers on a dial such as a meter are often formed on a substrate by printing, and screen printing is often used. However, in recent years, as the trend toward higher grades and diversification of products have advanced,
Adds a sense of quality to images such as these letters and numbers,
In order to improve decorativeness and visibility, studies are underway to make images multicolored.

However, in multicolor printing by screen printing, a plate is required for each color, which complicates the printing process and requires drying and curing of the ink for each printing of one color, thus increasing the working speed. There was a problem of being late.

Further, in the offset printing suitable for multicolor printing at high speed, it is difficult to thicken the coating film, so that there is a problem that a sufficient color density for use as a display panel cannot be obtained. .

Further, in the pattern formation by screen printing, since the ink used is a solvent type liquid, the solvent filled in the working environment becomes a source of offensive odor and it is necessary to always pay attention to the danger of explosion or fire. There was a problem.

Further, there is a problem in that the printing ink remains on the plate due to the evaporation of the solvent and causes clogging of the plate, and that it takes time to adjust the viscosity suitable for screen printing. Further, when a plate having a coarse mesh is used so that the printing ink does not become clogged in the plate, there is a problem that only a multicolor image having a low resolution can be obtained.

Therefore, in recent years, a photopolymerizable ink has been proposed for the purpose of eliminating the solvent and shortening the curing time.
However, in order to adjust the viscosity suitable for screen printing, it is necessary to add a reactive diluent such as a low molecular weight monomer to the photopolymerizable ink, which shows the same behavior as a solvent and does not react. Was volatilized with time from the coating film.

Further, the addition of such a reactive diluent reduces the molecular weight of the photopolymerizable ink as a whole,
There are drawbacks that the shrinkage during curing is large and the adhesiveness is deteriorated and the flexibility is lacking, and it cannot be said that it is sufficient from the practical point of view.

In order to solve these problems, a colored photopolymerizable composition containing a dye or a pigment is exposed, cured,
There is disclosed a method of developing an arbitrary image pattern on a substrate and laminating a transparent photopolymerizable composition layer on the upper surface of the substrate to form a display panel (JP-A-2-210220). However, this method has a problem that dust and dirt are likely to adhere to the surface of the image forming substrate, and the surface hardness is low and the scratch resistance is poor.

[0010]

SUMMARY OF THE INVENTION The present invention has been made in view of the above drawbacks, and an object thereof is to eliminate the need for using a solvent or a reactive diluent, to improve the working environment and to improve workability. It is an object of the present invention to provide a laminated image body which can be improved, is less likely to have dust and dirt on the surface of a colored image pattern, and is excellent in scratch resistance.

[0011]

The laminated image body of the present invention comprises:
An adhesive layer, a colored image pattern layer, a transparent resin layer and an antistatic hard coat layer are laminated in this order on a substrate.

Examples of the substrate used in the present invention include resin sheets such as polycarbonate, polyethylene terephthalate and acrylic resin; glass plates; ceramic plates; metal plates and the like.

The adhesive layer is preferably formed of a photopolymerizable resin composition (a) comprising an organic polymer, a photopolymerizable unsaturated compound and a photopolymerization initiator.

The above organic high molecular polymer preferably has an α, β-unsaturated ethylenic monomer as a constituent component,
Examples of the α, β-unsaturated ethylene-based monomer include styrene, o-methylstyrene, m-methylstyrene, p
-Methylstyrene, α-methylstyrene, p-ethylstyrene, 2,4-dimethylstyrene, pn-hexylstyrene, pn-octylstyrene, p-methoxystyrene, p-phenylstyrene, 3,4-dimethyl Styrenes such as chlorostyrene; Vinylnaphthalenes such as α-vinylnaphthalene; Ethylene, propylene, butylene or C _{5 to} C ₃₀ and higher α-olefins; Halogen such as vinyl chloride, vinyl bromide, vinyl fluoride Vinyl chlorides; vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate; methyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, (Meth) acrylate-n-octyl, (meth) acrylate lauryl, (meth) ac Le 2-ethylhexyl,
(Meth) acrylic acid esters such as 2-chloroethyl (meth) acrylate, methyl α-chloro (meth) acrylate, phenyl (meth) acrylate and dimethylaminoethyl (meth) acrylate; vinyl methyl ether, vinyl Vinyl ethers such as ethyl ether; vinyl ketones such as vinyl methyl ketone and vinyl ethyl ketone; N-vinyl compounds such as N-vinylpyrrole and N-vinylindole; (meth) acrylonitrile;
(Meth) acrylic acid amides may be mentioned, and one or more of these may be used.

The molecular weight of the above organic polymer is
When it becomes smaller, so-called cold flow is more likely to occur, and when it is rolled and stored, the photopolymerizable composition becomes wrinkled and unusable, and when it becomes larger, the solution viscosity during coating increases and coating unevenness occurs, so a weight average The molecular weight is preferably 20,000 to 1,000,000, more preferably 50,000 to 500,000.

Any method may be adopted as the method for producing the above-mentioned organic high-molecular polymer, and it can be easily obtained, for example, by radical polymerization in an organic solvent.

Examples of the photopolymerizable unsaturated compound include:
Monofunctional or polyfunctional monomers of (meth) acrylic acid derivatives are preferred. Examples of the monofunctional monomer include a methyl (meth) acrylate monomer, a benzyl (meth) acrylate monomer, and an urethane or polyester acrylate oligomer.

Examples of the polyfunctional (meth) acrylate monomer include, for example, triethylene glycol (meth).
Acrylate, tetraethylene glycol di (meth) acrylate, nonaethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, tetrapropylene glycol di (meth) acrylate, nonapropylene glycol di (Meth) acrylate, polypropylene glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate,
Dipentaerythritol penta (meth) acrylate,
Dipentaerythritol hexa (meth) acrylate,
Trimethylolpropane tri (meth) acrylate,
2,2-bis [4- (acryloxydiethoxy) phenyl] propane, 2,2-bis [4- (methacryloxydiethoxy) phenyl] propane, 3-phenoxy-2-
Examples thereof include propanoyl acrylate and 1,6-bis [3-acryloxy-2-hydroxypropyl] hexyl ether.

The above unsaturated compounds may be used alone or in combination of two or more kinds.

In the above photopolymerizable resin composition (a), when the amount of the unsaturated compound used is small, the surface hardness after exposure is insufficient, and when it is too large, the tackiness of the unexposed portion becomes strong and a good pattern is formed. Since it is difficult to obtain, the amount is preferably 10 to 250 parts by weight, more preferably 30 to 200 parts by weight, based on 100 parts by weight of the organic polymer.

Any photopolymerization initiator may be used as long as it has a property of activating the unsaturated compound by actinic rays such as ultraviolet rays and visible rays to initiate polymerization.

Among the above photopolymerization initiators, those which are activated by ultraviolet rays include, for example, sulfides such as sodium methyldithiocarbamate sulfide, tetramethylthiuram monosulfide, diphenylmonosulfide, dibenzothiazoylmonosulfide and disulfide. Thioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthone and other thioxanthone derivatives; hydrazone, azobisisobutyronitrile, benzenediazonium and other (di) azo compounds; benzoin, benzoin methyl ether, Benzoin ethyl ether, benzophenone, dimethylaminobenzophenone, Michler's ketone, benzyl anthraquinone, t-butyl anthraquinone, 2-methyl anthraquinone , 2-ethyl anthraquinone, 2
Aromatic carbonyl compounds such as aminoanthraquinone, 2-chloroanthraquinone, benzyldimethylketal, and methylphenylglyoxylate; 4- (2-hydroxyethoxy) phenyl (2-hydroxy-2-propyl) ketone [Darocur 2959 manufactured by Merck & Co., Inc. ]],
Acetophenone derivatives such as α-hydroxy-α, α'-dimethyl-acetophenone [“Darocur 1173” manufactured by Merck Ltd.], 2,2-diethoxyacetophenone and 2,2-dimethoxyacetophenone; methyl p-dimethylaminobenzoate, p -Ethyl dimethylaminobenzoate,
Dialkylaminobenzoic acid esters such as butyl p-dimethylaminobenzoate and isopropyl p-diethylaminobenzoate; peroxides such as benzoyl peroxide, di-t-butyl peroxide, dicumyl peroxide and cumene hydroperoxide; 9-phenylacridine, 9-p-methoxyphenylacridine, 9-
Acridine derivatives such as acetylaminoacridine and benzacridine; 9,10-dimethylbenzphenazine,
Phenazine derivatives such as 9-methylbenzphenazine and 10-methoxybenzphenazine; quinoxaline derivatives such as 6,4 ′, 4 ″ -trimethoxy-2,3-diphenylquinoxaline; 2,4,5-triphenylimidazoyl dimer A halogenated ketone; an acylated phosphorus compound such as acylphosphine oxide and acylphosphonate.

Further, those which are activated by visible light include, for example, 2-nitrofluorene, 2,4,6-triphenylpyrylyl boron tetrafluoride salt, 2,4,6-tris (trichloromethyl)- 1,3,5-triazine,
3,3′-carbonylbiscoumarin, thiomichler ketone and the like can be mentioned.

In the above photopolymerizable resin composition (a), if the amount of the photopolymerization initiator used is small, the curing time will be long, or the curing will be insufficient to form an image. Since the polymerizable resin composition (ii) becomes yellow or becomes brittle, 100 parts by weight of the organic high molecular polymer is
0.1 to 10 parts by weight is preferable.

In order to form the above adhesive layer, the photopolymerizable resin composition (a) may be diluted with a solvent, if necessary. Examples of such a solvent include n-hexane, n-heptane, cyclohexane, dichloroethane, dichloromethane, trichloroethane, chloroform, carbon tetrachloride,
Dibromoethane, dibromomethane, julorobenzene,
Examples thereof include bromobenzene, xylene, toluene, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, tetrahydrofuran, dioxane, ethyl acetate, butyl acetate and the like.

The thickness of the adhesive layer is not particularly limited, but if it is thin, it becomes difficult to handle, and if it is thick, a step is formed between the layers, so 0.5-20 μm is preferable.

For the adhesive layer, the photopolymerizable resin composition (a) is applied onto a support by a spray method, a roll coater method,
It can be obtained by applying after coating by a bar coat method, a doctor blade method or the like, and then drying.

As the above-mentioned support, those which are chemically and thermally stable are preferable. For example, polyesters such as polyethylene terephthalate; polyolefins such as polyethylene and polypropylene; polyhalogenated compounds such as polyvinyl chloride and polyvinylidene chloride. Vinyls; Polyamides;
A resin film such as polycarbonate can be used, and a biaxially stretched polyethylene terephthalate film is particularly preferable. Further, the support may be subjected to a release treatment with a silicone resin, a fluororesin, a fluorosurfactant or the like in order to improve the transferability of the adhesive layer.

The colored image pattern layer is preferably formed from a photopolymerizable resin composition (b) comprising a linear copolymer, a photopolymerizable unsaturated compound, a photopolymerization initiator and a colorant.

The above linear copolymer, which is soluble or swellable in an alkaline aqueous solution, contains an α, β-unsaturated ethylenic monomer containing a carboxyl group and an α, β-other than the above. Those having an unsaturated ethylenic monomer as a constituent are preferable.

The α, β-unsaturated ethylenic monomer containing a carboxyl group may be a monomer containing a carboxyl group and copolymerizable with the α, β-unsaturated ethylenic monomer. For example, unsaturated carboxylic acids such as (meth) acrylic acid, crotonic acid, maleic acid (including anhydride), fumaric acid and itaconic acid may be mentioned.

As the α, β-unsaturated ethylenic monomer other than the above, the α, β-unsaturated ethylenic monomer used in the photopolymerizable resin composition (a) is preferably used. It

When the amount of the portion corresponding to the α, β-unsaturated ethylenic monomer containing a carboxyl group in the constituents of the above linear copolymer becomes small, it becomes insoluble in the alkaline aqueous solution, and therefore, the alkaline aqueous solution. It becomes impossible to develop by the above method, and if it becomes too much, the compatibility with the coating solvent or other components is lowered and the resolution is also lowered. Therefore, the range of 10 to 40% by weight is preferable, and more preferably 15 to 35% by weight. is there.

Further, when the molecular weight of the linear copolymer is small, so-called cold flow is likely to occur, and when it is large, it is difficult to dissolve in an alkaline aqueous solution and it is difficult to develop, and the resolution is deteriorated. The average molecular weight is preferably in the range of 20,000 to 500,000, more preferably 50,000 to
It is 200,000.

As the method for producing the above-mentioned linear copolymer, any method may be adopted, and for example, it can be easily obtained by radical polymerization or the like in an organic solvent.

As the unsaturated compound, those used in the photopolymerizable resin composition (a) are preferably used. The amount of the unsaturated compound used is preferably 10 to 250 parts by weight with respect to 100 parts by weight of the linear copolymer.

As the photopolymerization initiator, those used for the photopolymerizable resin composition (a) are preferably used. The amount of the photopolymerization initiator used is preferably 0.1 to 10 parts by weight with respect to 100 parts by weight of the linear copolymer.

The colorant is a photopolymerizable resin composition (B).
It is used to color a predetermined color, conventionally known pigments and dyes can be used, at least yellow,
There are three types, magenta and cyan.

Examples of the yellow pigments include Hansa Yellow, Benzidine Yellow, Cadmium Yellow, Yellow Lead G, Zinc Chromate, Lemon Yellow, Strocian Yellow, Isoindolinone Yellow, Indian Yellow and the like. Two or more types are used.

Examples of the magenta pigments include rhodamine B lake, cadmium red, red iron oxide, chrome vermillion, pyrazolone red, resole red, red lead, watching red, and quinacridone red. Is used.

Examples of the cyan pigments include ultramarine blue, Prussian blue, cobalt blue, cerulean blue, manganese blue and phthalocyanine blue, and one or more of them may be used.

In the photopolymerizable resin composition (b), when the amount of the above-mentioned colorant used is small, the color density becomes low and sufficient coloring cannot be achieved, and when the amount is large, the colorant does not contribute to the curing of the obtained image. Therefore, the range of 0.1 to 300 parts by weight is preferable with respect to 100 parts by weight of the linear copolymer.

To form the colored image pattern layer,
At least three photopolymerizable resin compositions (b) of yellow, magenta, and cyan are coated on different supports and dried to form a photopolymerizable resin composition (b) layer. An image is prepared by separately preparing a halftone negative mask in which each color is separated into yellow, magenta and cyan, and the halftone negative mask is superimposed on the photopolymerizable resin composition (b) layer corresponding to each color and exposed, After curing, the unexposed portion is removed by development to form three types of image patterns of yellow, magenta and cyan. Then, above 3
A colored image pattern layer is obtained by sequentially transferring and laminating seed image patterns onto the adhesive layer by a thermal laminating method or the like.

As another method of forming a colored image pattern layer, a cyan-based photopolymerizable resin composition (b) layer is laminated on the adhesive layer by a thermal lamination method or the like, and then the resin composition is formed. A halftone negative mask color-separated into cyan is superposed on the object (b) layer, exposed and cured, and the unexposed portion is removed by development to form an image pattern corresponding to cyan. Next, by repeating similar operations in sequence, image patterns corresponding to magenta and yellow may be laminated in this order on the image pattern corresponding to cyan to form a colored image pattern layer.

The transparent resin layer is preferably formed of a photopolymerizable resin composition (C) comprising an organic high molecular polymer, a photopolymerizable unsaturated compound and a photopolymerization initiator.

As the above organic polymer, unsaturated compound and photopolymerization initiator, those used in the photopolymerizable resin composition (a) are preferably used.

For the transparent resin layer, the photopolymerizable resin composition (C) is coated on a support and dried to form a photopolymerizable resin composition (C) layer having a certain thickness, and then the colored image is formed. It can be obtained by transferring and laminating on the pattern layer by a thermal laminating method or the like.

The antistatic hard coat layer is composed of (meth)
It is formed from a photopolymerizable resin composition (d) comprising an acrylate compound (a), a photopolymerization initiator (b) and a conductive metal oxide powder (c).

The (meth) acrylate compound (a)
Has at least two (meth) acryloyl groups in the molecule, and the polyfunctional (meth) acrylate monomer used in the photopolymerizable resin composition (a) is preferably used.

As the photopolymerization initiator (b), those used in the photopolymerizable resin composition (a) are preferably used.

When the amount of the photopolymerization initiator (b) used in the photopolymerizable resin composition (d) is small, the curing time is long or the curing is insufficient. Since it turns yellow and becomes brittle, it is 0.1 to 1 with respect to 100 parts by weight of the (meth) acrylate compound (a).
Limited to 0 parts by weight.

Examples of the conductive metal oxide powder (c) include powders of SnO ₂ , In ₂ O ₃ , CdSnO ₄ , TiO and the like, and one or more of these may be used. In particular, a metal oxide containing tin oxide as a main component is preferable, and one containing tin oxide as a main component and 0.1 to 20% by weight of antimony is more preferable from the viewpoint of excellent transparency.

If the particle size of the above-mentioned conductive metal oxide powder (c) is small, it becomes difficult to handle, and if it is large, the transparency of the obtained coating film is deteriorated.
Limited to 4 μm.

In the photopolymerizable resin composition (d), when the amount of the conductive metal oxide powder (c) used is small, the conductivity cannot be obtained, and when it is large, the transparency and mechanical strength of the coating film are reduced. (Meth) acrylate compound (a) 100
It is limited to 20 to 1,000 parts by weight with respect to parts by weight.

In order to improve the dispersibility of the conductive metal oxide powder (c), the photopolymerizable resin composition (d) contains a silane coupling agent, a titanate coupling agent, a surfactant and olein. Organic acids such as acids, hydroxyl group-containing polymer compounds, and carboxyl group-containing polymer compounds may be added.

To disperse the above-mentioned conductive metal oxide powder (c) in the photopolymerizable resin composition (d), for example, a sand mill, a ball mill, an attritor, a high-speed rotary stirring device,
Three rolls etc. are used.

For the antistatic hard coat layer, the photopolymerizable resin composition (d) is applied on a support and dried to form a photopolymerizable resin composition (d) layer having a constant thickness. It can be obtained by transferring and stacking on the transparent resin layer by a thermal laminating method or the like.

Further, the photopolymerizable resin composition (a) to
In (c), if necessary, a plasticizer such as dioctyl phthalate, triethylene glycol diacetate, p-toluene sulfonamide, N-ethyltoluene sulfonamide; a thermal polymerization inhibitor such as hydroquinone or p-methoxyphenol; Stabilizers; UV absorbers; antioxidants and the like may be added.

[0059]

EXAMPLES The present invention will be described below based on examples. (Example 1) 1) Formation of an adhesive composition layer A photo-polymerizable resin composition (a) solution having the following composition was applied to a polyethylene terephthalate film support (thickness: 100 μm), the surface of which was treated with a silicone release agent. An adhesive composition layer having a film thickness after drying of 5 μm was formed by uniformly coating and drying the above. -Organic polymer 100 parts by weight (component: polymethyl methacrylate, Sumitomo Chemical Co., Ltd. "SUMIPEX L06" weight average molecular weight = 60,000) -Unsaturated compound 50 parts by weight (oligoester acrylate, Toagosei Co., Ltd. "M- 6100 ")-Unsaturated compound 50 parts by weight (oligoester acrylate," M-8030 "manufactured by Toagosei Co., Ltd.)-Photopolymerization initiator (component: acylphosphine oxide type) 4 parts by weight (" Lucirin TPO "manufactured by BASF) ) ・ Methyl ethyl ketone 330 parts by weight

2) Formation of a resin composition layer for a colored image pattern The following photopolymerizable resin composition (b) solution was applied onto a polyethylene terephthalate film support (thickness: 25 μm) the surface of which was treated with a silicone release agent. Then, it was uniformly applied and dried to form four types of resin composition layers for colored image patterns of yellow, magenta, cyan, and black having a film thickness after drying of 3 μm. -Linear copolymer 100 parts by weight (methyl methacrylate / methacrylic acid-n-butyl / methacrylic acid = 50/25/25 [weight ratio], weight average molecular weight = 150,000) -Unsaturated compound (trimethylolpropane tri) Acrylate) 100 parts by weight Photoinitiator (component: benzyl dimethyl ketal) 4 parts by weight ("Irgacure 651" manufactured by Ciba-Geigy) -Yellow pigment (Dainichi Seika's "FPF-27E Yellow") 10 parts by weight or 10 parts by weight of magenta pigment (“FPF-96Q red” manufactured by Dainichiseika Co., Ltd.) or 10 parts by weight of cyan pigment (“FPF-CP2 blue” manufactured by Dainichiseika Co., Ltd.) or • the above yellow, magenta and cyan pigments 3 Equal parts by weight of mixture Mixture (black) 10 parts by weight Methyl ethyl ketone 400 parts by weight

(3) Formation of transparent resin composition layer The following photopolymerizable composition (c) solution was applied onto a polyethylene terephthalate film having a thickness of 100 μm, and a transparent resin having a thickness of 20 μm after drying. A composition layer was formed. Organic polymer 100 parts by weight (component: polymethyl methacrylate, Asahi Kasei's "Delpet LP-1" weight average molecular weight = 110,000) -Unsaturated compound 60 parts by weight (component: trimethylol propane acrylate, Shin Nakamura Chemical company "A-TMPT")-Unsaturated compound 60 parts by weight (component: ethoxylated pentaerythritol tetraacrylate, Shin-Nakamura Chemical company "ATM-4E")-Photopolymerization initiator 4 parts by weight (component: acylphosphine Oxide type, "Lucirin TPO" manufactured by BASF) ・ Methyl ethyl ketone 330 parts by weight

(4) Formation of Resin Composition Layer for Antistatic Hard Coat The following photopolymerizable composition (d) solution was applied onto a polyethylene terephthalate film having a thickness of 25 μm to give a film thickness after drying. A 2 μm antistatic hard coat resin composition layer was formed. -Dipentaerythritol hexaacrylate 100 parts by weight ("DPHA" manufactured by Nippon Kayaku Co., Ltd.)-Conductive powder 300 parts by weight (component: tin oxide powder containing antimony oxide, manufactured by Mitsubishi Materials, primary particle size: 0.02 µm)- Dispersant 30 parts by weight (component: butyral resin, Sekisui Chemical Co., Ltd., residual hydroxyl group: 35%, degree of polymerization: 1700) Photopolymerization initiator 3 parts by weight (component: acylphosphine oxide type, BASF's "Lucirin TPO" ]) ・ Ethyl cellosolve 500 parts by weight

[Production of Laminated Image Body] A substrate having a thickness of 5
Using a polycarbonate sheet of 00 μm, as shown in FIG. 1, first, one sheet of the above-mentioned adhesive resin composition layer (1) was laminated on the sheet by a thermal lamination method, and then 300 mJ / cm ² by an ultra high pressure mercury lamp. The entire surface was irradiated with an ultraviolet ray having the strength of 3 to cure it, thereby forming an adhesive layer 2.

A black colored image pattern resin composition layer (2) was laminated on the adhesive layer 2 by a thermal laminating method, and then a halftone dot negative mask was overlaid on the resin composition layer (2). , 300mJ / cm with ultra high pressure mercury lamp
It was cured by irradiating it with ultraviolet rays having an intensity of ² . Next, the exposed surface of the resin composition layer (2) was developed with a 1% sodium carbonate aqueous solution at 30 ° C. to form an image pattern corresponding to black.

Further, by repeating the same operation using the halftone dot negative mask corresponding to cyan, magenta and yellow and the resin composition layer (2) for a colored image pattern, an image pattern corresponding to black is formed. cyan,
The colored image pattern layer 3 was formed by stacking image patterns corresponding to magenta and yellow.

One transparent resin composition layer (3) is laminated on the colored image pattern layer 3 by a thermal laminating method to form a transparent resin layer 4, and then the transparent resin layer 4 is further charged with the above-mentioned charged material. The antistatic hard coat resin composition layer (4) is laminated by a thermal lamination method, and the entire surface is irradiated with ultraviolet rays having an intensity of 1,000 mJ / cm ² by an ultra-high pressure mercury lamp to cure the resin composition. Coat layer 5
Was formed to obtain a laminated image body.

Example 2 An antistatic hard coat layer was added,
A laminated image body was obtained in the same manner as in Example 1 except that the following photopolymerizable composition (d) solution was used. -Pentaerythritol triacrylate 100 parts by weight (Osaka Organic Chemical Co., Ltd. "Viscoat # 300" -Conductive powder 300 parts by weight (component: antimony oxide-containing tin oxide powder, Mitsubishi Materials, primary particle size: 0.02 μm)- Dispersant 30 parts by weight (component: butyral resin, manufactured by Sekisui Chemical Co., residual hydroxyl degree: 35 mol%, degree of polymerization: 1700) ・ Photopolymerization initiator 3 parts by weight (component: acylphosphine oxide type, manufactured by BASF "Lucirin" TPO ")-Ethyl cellosolve 500 parts by weight

Example 3 An antistatic hard coat layer was added,
A laminated image body was obtained in the same manner as in Example 1 except that the following photopolymerizable composition (d) solution was used. Tetramethylol methane tetraacrylate 100 parts by weight (Shin-Nakamura Chemical Co., Ltd. "A-TMMT") Conductive powder 300 parts by weight (Component: antimony oxide-containing tin oxide powder, Mitsubishi Materials Co., primary particle size: 0.02 μm) Dispersant 30 parts by weight (component: butyral resin, manufactured by Sekisui Chemical Co., residual hydroxyl degree: 35 mol%, degree of polymerization: 1700) Photopolymerization initiator 3 parts by weight (component: acylphosphine oxide type, manufactured by BASF Lucillin TPO ") ・ Ethyl cellosolve 500 parts by weight

Example 4 An antistatic hard coat layer was added,
A laminated image body was obtained in the same manner as in Example 1 except that the following photopolymerizable composition (d) solution was used. 6 parts functional urethane acrylate 100 parts by weight (Kyoeisha Yushi Kagaku Co., Ltd. "UA-306T") Conductive powder 300 parts by weight (component: antimony oxide-containing tin oxide powder, Mitsubishi Materials Corporation, primary particle size: 0.02 μm) Dispersant 30 parts by weight (component: butyral resin, manufactured by Sekisui Chemical Co., residual hydroxyl degree: 35 mol%, degree of polymerization: 1700) ・ Photopolymerization initiator 3 parts by weight (component: acylphosphine oxide type, manufactured by BASF "Lucirin" TPO ")-Ethyl cellosolve 500 parts by weight

Comparative Example 1 A laminated image body was obtained in the same manner as in Example 1 except that the antistatic hard coat layer was not provided at all.

Comparative Example 2 A laminated image body was obtained in the same manner as in Example 1 except that the antistatic hard coat layer was formed from a photopolymerizable resin composition containing no conductive powder.

Evaluation of Laminated Image Body The laminated image bodies obtained in the above Examples and Comparative Examples were evaluated as follows, and the results are shown in Tables 1 and 2. Surface hardness After the laminated image body was prepared, it was measured using a pencil hardness meter in accordance with JIS K5400. Surface resistivity After the laminated image body was prepared, it was measured according to ASTM D257. Dust resistance After leaving the laminated image body for 1 week in the room, observe visually whether dust adheres to the surface. ○ If there is no dust on the surface, ○, if there is dust on the surface, ×
And

[0073]

[Table 1]

[0074]

[Table 2]

[0075]

The constitution of the laminated image body of the present invention is as described above, and since the antistatic hard coat layer is formed on the surface, antistatic performance is imparted and the surface hardness is significantly increased. As it improves, it is less likely to have dust and dirt on the surface and has excellent scratch resistance.

[Brief description of drawings]

FIG. 1 is a schematic sectional view showing a laminated image body of the present invention.

[Explanation of symbols]

 1 Substrate 2 Adhesive Layer 3 Colored Image Pattern Layer 4 Transparent Resin Layer 5 Antistatic Hard Coat Layer

Claims (1)

[Claims] 1. A laminated image in which a colored image pattern layer is laminated on a substrate via an adhesive layer, and a transparent resin layer and an antistatic hard coat layer are laminated in this order on the colored image pattern layer. Wherein the antistatic hard coat layer comprises (a) 100 parts by weight of a (meth) acrylate compound having at least two or more (meth) acryloyl groups in the molecule, and (b) a photopolymerization initiator of 0.1. A laminated image body comprising a photopolymerizable resin composition comprising 10 to 10 parts by weight and 20 to 1,000 parts by weight of a conductive metal oxide powder having a particle size of 0.01 to 0.4 μm.