JPH07175220A - Photosensitive picture receptive sheet - Google Patents

Abstract

PURPOSE:To obtain an photosensitive picture receptive sheet excellent in transferability of picture pattern, without dust or dir being deposited on the surface and excellent in scratch resistance due to the improvement of surface hardness by forming an antistatic hard coat layer on one side of a substrate and a picture receptive layer on the other side. CONSTITUTION:An antistatic hard coat layer 71 is formed on one side of a substrate 11, and a picture receptive layer 72 is formed on the other side. The layer 71 is formed with the photopolymerizable resin composition consisting of the (meth)acrylates having at least two (meth)acryloyls in the molecule, a photopolymerization initiator and a conductive metal oxide powder, 0.1-10 pts.wt. of the initiator is used with 100 pts.wt. of the coplymer, and the grain diameter of the metal oxide powder is controlled to 0.01-0.4mum. Consequently, an antistatic performance is imparted, the surface hardness is drastically improved, dust and dirt hardly deposit on the surface, and the scratch resistance is improved.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive image receiving sheet used for obtaining a display panel or the like having a predetermined colored image pattern formed on a substrate. Such a display panel can be used, for example, as an instrument panel for various devices, a dial for a vehicle speedometer, a display panel on which a map or a landscape image is arranged, a display panel for advertisements, and the like.

[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 widely 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 is a problem of being late. Further, in offset printing suitable for multicolor printing, it is difficult to thicken the coating film, so that there is a problem that a sufficient color density for use as a display board cannot be obtained.

Further, in 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 is a problem.

Moreover, in the printing ink, the solid content remains on the plate due to the evaporation of the solvent, which may cause the plate to be clogged.
There is also a problem that it takes time to adjust the viscosity suitable for screen printing.

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. Is volatilized with time from the coating film.

Further, since the photopolymerizable ink is made to have a low molecular weight as a whole by the addition of such a reactive diluent,
Practicality was not sufficient because of the drawbacks of large shrinkage during curing, poor adhesiveness, and lack of flexibility.

In order to solve these problems, for example, JP-A-59-97140 discloses a method for forming a colored image using a colored photocurable composition.

In this manufacturing method, (1) a halftone dot photomask in which a desired image is color-separated in advance is prepared, and (2) a photocurable composition having a corresponding color through the photomask. The photocurable resin film obtained from (1) is irradiated with an actinic ray to be cured, (3) the uncured portion is removed by development to form a color-separated halftone image pattern, (4) obtained. The transferred dot-like image pattern is transferred and laminated for each color on the image receiving sheet having photopolymerization property, (5) the dot-like image pattern formed on the image receiving sheet is retransferred onto the substrate, It is a method of forming a predetermined colored image by photo-curing.

Here, by using a colorant such as yellow, magenta or cyan in combination as the colored photopolymerizable composition, it is possible to display an arbitrary color.

The image-receiving layer of the above-mentioned image-receiving sheet is formed from a photopolymerizable resin composition comprising a linear copolymer, a photopolymerizable unsaturated compound and a photopolymerization initiator,
Problems associated with screen printing and photopolymerizable inks are solved. However, it is easy for dust and dirt to adhere to the surface,
There is a problem that scratch resistance is poor due to low surface hardness.

[0012]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned drawbacks, and its object is to provide excellent transferability of an image pattern, to prevent dust and dirt from adhering to the surface, and to improve surface hardness. The improvement is to provide a photosensitive image-receiving sheet having excellent scratch resistance.

[0013]

In the photosensitive image receiving sheet of the present invention, an antistatic hard coat layer is formed on one side of a support and an image receiving layer is formed on the other side.

The support is not particularly limited, but for example, a resin film such as polyethylene terephthalate or biaxially oriented polypropylene is preferably used. This support may be previously subjected to primer treatment or corona treatment in order to improve the adhesion.

The antistatic hard coat layer comprises a (meth) acrylate compound (a) having at least two (meth) acryloyl groups in the molecule, a photopolymerization initiator (b) and a conductive metal oxide powder ( It is formed from the photopolymerizable resin composition (a) comprising c).

The (meth) acrylate compound (a)
Is a compound having at least two or more (meth) acryloyl groups in the molecule and having photopolymerization property.
Monofunctional and polyfunctional monomers of (meth) acrylic acid derivatives are preferably used.

Examples of the monofunctional monomer include
Examples thereof include a methyl (meth) acrylate monomer and a benzyl (meth) acrylate monomer.

Examples of the polyfunctional 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- (methacryloyl) Shijietokishi) phenyl] propane, 3-phenoxy-2-propanoyl acrylate,
1,6-bis [3-acryloxy-2-hydroxypropyl] hexyl ether, epichlorohydrin modified 1,
6-hexanediol diacrylate etc. are mentioned.

The photopolymerization initiator (b) may be any one having a property of activating the (meth) acrylate compound (a) by actinic rays such as ultraviolet rays and visible rays to initiate polymerization.

Among the above photopolymerization initiators (b), those which are activated by ultraviolet rays include, for example, sodium methyldithiocarbamate sulfide, tetramethylthiuram monosulfide, diphenylmonosulfide, dibenzothiazoyl monosulfide and disulfide. Sulfides such as; thioxanthone derivatives such as thioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, and 2,4-diethylthioxanthone; (di) azo compounds such as hydrazone, azobisisobutyronitrile, benzenediazonium; benzoin, benzoin Methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzophenone, dimethylaminobenzophenone, Michler's ketone, benzylanthraquinone, t-butyl Aromatic carbonyl compounds such as ntraquinone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-aminoanthraquinone, 2-chloroanthraquinone, benzyldimethylketal, methylphenylglyoxylate; methyl p-dimethylaminobenzoate, p-dimethylamino Dialkylaminobenzoic acid esters such as ethyl benzoate, butyl p-dimethylaminobenzoate and isopropyl p-diethylaminobenzoate;
Peroxides such as benzoyl peroxide, di-t-butyl peroxide, dicumyl peroxide, cumene hydroperoxide; 9-phenylacridine, 9
Acridine derivatives such as -p-methoxyphenylacridine, 9-acetylaminoacridine and benzacridine; phenazine derivatives such as 9,10-dimethylbenzphenazine, 9-methylbenzphenazine and 10-methoxybenzphenazine; 6,4 ', 4 "-Trimethoxy-
A quinoxaline derivative such as 2,3-diphenylquinoxaline; a 2,4,5-triphenylimidazoyl dimer; a halogenated ketone; an acylated phosphorus compound such as an acylphosphinoxide or an acylphosphonate.

As those which are activated by visible light, 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.

When the amount of the photopolymerization initiator (b) used in the above-mentioned photopolymerizable resin composition (a) is small, it takes a long exposure time or the curing after the exposure is insufficient, so that an image is formed. If the amount of the photopolymerizable resin composition cannot be increased, the cured photopolymerizable resin composition will turn yellow or become brittle.
It is limited to 0.1 to 10 parts by weight with respect to parts by weight.

A photopolymerization initiation aid may be added to the photopolymerization initiator (b) in order to accelerate the curing rate and reduce oxygen damage. As such a photopolymerization initiation assistant, for example, amine compounds such as triethanolamine and dialkylaminobenzoic acid esters are preferable.

Examples of the conductive metal oxide powder (c) include SnO ₂ , In ₂ O ₃ , ZnO, CdSnO ₄ , and S.
Powders of b ₂ O ₃ , Al ₂ O ₃ , TiO, etc. may be mentioned, and one or more of these may be used. In particular, as the conductive metal oxide powder (c), SnO _{2 having} excellent transparency is used.
Is preferable, and that containing 0.1 to 20% by weight of antimony in SnO ₂ is more preferable.

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

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

An organic solvent may be added to the photopolymerizable resin composition (a) in order to improve the dispersibility and coatability of the conductive metal oxide powder (c). The solvent is preferably colorless and transparent, for example, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone,
Methyl cellosolve, butyl acetate, isopropyl alcohol, acetone, anisole and the like can be mentioned, and one or more of these can be used.

Furthermore, in order to improve the dispersibility of the electroconductive metal oxide powder (c), the photopolymerizable resin composition (a) contains sodium phosphate, sodium sulfonate, sodium oleate and citric acid. A surfactant such as sodium; a silane compound such as an alkylsilane or an alkoxysilane; a titanate-based coupling agent such as an alkyl titanate or an acrylic titanate; a hydroxyl group-containing polymer compound or a carboxyl group-containing polymer compound may be added. Further, various additives such as a leveling agent, a surface modifier and a defoaming agent may be added.

In order to disperse the above-mentioned conductive metal oxide powder (c) in the photopolymerizable resin composition (a), for example, a sand mill, a ball mill, an attritor, a high-speed rotary stirring device, a three-roll mill or the like is used. To be

The image-receiving layer is an organic polymer copolymer,
It is preferably formed from a photopolymerizable resin composition (b) comprising a photopolymerizable unsaturated compound and a photopolymerization initiator.

As the above-mentioned organic polymer copolymer, those having a softening point of 150 ° C. or less are preferable. For example, polyolefin, a copolymer of polyolefin and α, β-unsaturated carboxylic acid, and metal ion of the copolymer. Crosslinked products, polyvinylidene chloride and its copolymers, polyacrylonitrile, poly-N-vinylcarbazole, polyvinyl alcohol, poly-N-vinylpyrrolidone, copolymer polyester, copolymer polyamide, copolymer polyurethane, ethylene-acetic acid Examples thereof include vinyl copolymers, styrene-butadiene copolymers, acrylonitrile-butadiene copolymers, styrene-isoprene copolymers, butyl rubber, acrylic polymers and the like.

Examples of the acrylic polymer include (co) polymers of an α, β-unsaturated ethylenic monomer containing a carboxyl group; Co) polymer; α, β containing a carboxyl group
A copolymer of an unsaturated ethylenic monomer and an α, β-unsaturated ethylenic monomer other than the above is preferable.

Examples of the α, β-unsaturated ethylenic monomer containing a carboxyl group include (meth) acrylic acid, crotonic acid, maleic acid (including anhydrides), fumaric acid and itaconic acid. Unsaturated carboxylic acids are mentioned.

Examples of α, β-unsaturated ethylenic monomers other than the above are, for example, styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, α-
Styrenes such as methylstyrene, p-ethylstyrene, 2,4-dimethylstyrene, pn-hexylstyrene, pn-octylstyrene, p-methoxystyrene, p-phenylstyrene, and 3,4-dimethylchlorostyrene. Vinylnaphthalenes such as α-vinylnaphthalene; ethylene, propylene, butylene or C _{5 to} C ₃₀
And higher α-olefins; vinyl halides such as vinyl chloride, vinyl bromide and vinyl fluoride; vinyl esters such as vinyl acetate, vinyl propionate and vinyl butyrate; methyl (meth) acrylate, (meth ) Propyl acrylate, (meth) acrylic acid-n-butyl, (meth) acrylic acid isobutyl, (meth) acrylic acid-n-
Octyl, lauryl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (meth) acrylic acid-2
-Chloroethyl, α-chloro (meth) acrylate, phenyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, dicyclopentaniel (meth) acrylate, isobornyl (meth) acrylate, (meth) acrylic (Meth) acrylic acid esters such as benzyl acid ester; vinyl ethers such as vinyl methyl ether and vinyl ethyl ether; vinyl ketones such as vinyl methyl ketone and vinyl ethyl ketone; N-vinyl such as N-vinylpyrrole and N-vinylindole Compound;
(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 high molecular weight 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.

The above acrylic polymer is polymerized by any conventionally known method, and examples thereof include radical polymerization in an organic solvent. The mixing ratio of the above monomers is
Appropriately determined according to required physical properties such as softening point, glass transition point, elastic modulus, flexibility

Examples of the photopolymerizable unsaturated compound include:
A monofunctional monomer or a polyfunctional monomer of a (meth) acrylic acid derivative is preferable, and the photopolymerizable resin composition (a) is used.
The monofunctional monomer and polyfunctional monomer used therein are preferably used.

In the photopolymerizable resin composition (b), when the amount of the unsaturated compound used is small, the surface hardness after exposure is insufficient, and when it is large, cold flow of the image-receiving layer is likely to occur. 10 to 200 parts by weight is preferable with respect to 100 parts by weight of the copolymer, and more preferably 30 to
It is 150 parts by weight.

As the photopolymerization initiator, the photopolymerization initiator used in the photopolymerizable resin composition (a) is preferably used.

In the above photopolymerizable resin composition (b), if the content of the photopolymerization initiator is too small, it takes a long time for the exposure, or the curing after the exposure is insufficient, so that an image cannot be formed. If the amount is too large, the cured photopolymerizable resin composition will turn yellow or become brittle, so 0.1 to 10 parts by weight is preferable with respect to 100 parts by weight of the organic polymer copolymer.

The photopolymerizable resin composition (b) has the same photopolymerization as that used in the photopolymerizable resin composition (a) in order to accelerate the curing rate and reduce oxygen damage. Initiation aids may be added.

In the photopolymerizable resin composition (b), a plasticizer such as dioctyl phthalate, triethylene glycol diacetate, p-toluene sulfonamide, N-ethyltoluene sulfonamide; hydroquinone, p
-Thermal polymerization inhibitors such as methoxyphenol; stabilizers; UV absorbers; antioxidants; methyl ethyl ketone (ME
A solvent such as K) or toluene may be added.

Next, the method for producing the photosensitive image-receiving sheet of the present invention will be described. First, a solvent-diluted solution of the photopolymerizable resin composition (a) is cast on one surface of a support so as to have a constant thickness and dried to form an antistatic hard coat layer. The thickness of the antistatic hard coat layer is preferably 1 to 200 μm, because if it is too thick, thermal strain will occur during manufacture and transparency will be impaired.

Then, a solvent diluted solution of the photopolymerizable resin composition (b) is cast on the other surface of the support so as to have a constant thickness and dried to form an image receiving layer.
A photosensitive image receiving sheet is obtained. If the thickness of the image receiving layer is too thin, the transferability of the colored halftone dot image pattern deteriorates, so the thickness is preferably 1 to 50 μm.

The method of using the above photosensitive image receiving sheet is as follows.
It is as follows. (1) First of all, the original image is yellow in advance by a color separation machine.
A yellow, magenta, cyan, and black halftone dot negative mask, which has been converted into halftone dots which have been separated into magenta, cyan, and black, and whose color shade has been converted into the size of halftone dots, is prepared.

(2) Four types of photocurable resin compositions colored yellow, magenta, cyan and black are coated on the respective supports to form photocurable resin layers, and the photocurable resin is formed. The layer is exposed and cured through a halftone negative mask corresponding to that color and the uncured portion is removed by development to form a halftone image pattern on each temporary support.

(3) The halftone dot image pattern is peeled from the temporary support, and the halftone dot image pattern colored in yellow, cyan, magenta and black is formed on the image receiving layer on the photosensitive image receiving sheet. By sequentially transferring, aligning, and laminating, a colored image composed of four types of dot image patterns can be formed on the support.

Examples of the photocurable resin composition include organic polymer copolymers, photopolymerizable unsaturated compounds,
What consists of a photoinitiator and a coloring agent is preferable.

The above organic polymer copolymer is an alkali-soluble α, β-unsaturated ethylenic monomer containing a carboxyl group, and an α, β-unsaturated ethylenic monomer other than those mentioned above. A copolymer containing and as a constituent is 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.

Examples of the α, β-unsaturated ethylenic monomers other than the above are, for example, styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, α-
Styrenes such as methylstyrene, p-ethylstyrene, 2,4-dimethylstyrene, pn-hexylstyrene, pn-octylstyrene, p-methoxystyrene, p-phenylstyrene, and 3,4-dimethylchlorostyrene. Vinylnaphthalenes such as α-vinylnaphthalene; ethylene, propylene, butylene or C _{5 to} C ₃₀
And higher α-olefins; vinyl halides such as vinyl chloride, vinyl bromide and vinyl fluoride; vinyl esters such as vinyl acetate, vinyl propionate and vinyl butyrate; methyl (meth) acrylate, (meth ) Propyl acrylate, n-butyl (meth) acrylate, (meth)
Isobutyl acrylate, n-octyl (meth) acrylate, lauryl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-chloroethyl (meth) acrylate, α-chloro (meth) acrylic acid methyl ester, (Meth) acrylic acid esters such as phenyl (meth) acrylate and dimethylaminoethyl (meth) acrylate; vinyl ethers such as vinyl methyl ether and vinyl ethyl ether; vinyl ketones such as vinyl methyl ketone and vinyl ethyl ketone; N -N-vinyl compounds such as vinylpyrrole and N-vinylindole; (meth) acrylonitrile; (meth) acrylic acid amides.

When the amount of the portion corresponding to the α, β-unsaturated ethylenic monomer containing a carboxyl group in the constituent components of the above organic polymer copolymer becomes small, it becomes insoluble in an alkaline aqueous solution. Since development with an aqueous solution becomes impossible, and when the amount becomes large, the compatibility with the coating solvent or other components decreases and the resolution also decreases, so the range of 10 to 40% by weight is preferable, and 15 to 35% by weight is more preferable. Is.

If the molecular weight of the above organic high molecular weight copolymer is small, so-called cold flow is likely to occur, and if it is large, it is difficult to dissolve in an alkaline aqueous solution and it is difficult to develop, and the resolution is lowered. The average molecular weight is preferably in the range of 20,000 to 500,000, more preferably 50,000 to 300,000.

The unsaturated compound is photopolymerizable, and the monofunctional and polyfunctional monomers used in the photopolymerizable resin composition (a) are preferably used.

When the amount of the unsaturated compound in the photocurable resin composition is small, the surface hardness after exposure is insufficient, and when it is large, cold flow is likely to occur. Therefore, 100 parts by weight of the organic polymer copolymer is used. On the other hand, it is preferably 10 to 200 parts by weight, more preferably 30 to 150 parts by weight.

The photopolymerization initiator is sensitized by an actinic ray, and a compound similar to the photopolymerization initiator (b) used in the photopolymerizable resin composition (a) is preferably used. .

When the amount of the photopolymerization initiator in the photocurable resin composition is small, the exposure time is long, or the image cannot be formed because the curing after the exposure is insufficient, and when the amount is large, it is cured. Since the photopolymerizable resin composition becomes yellow or becomes brittle, 100 parts by weight of the organic polymer copolymer is used.
0.1 to 20 parts by weight is preferable.

The above-mentioned colorants are used for coloring the photocurable resin composition, and include conventionally known pigments and dyes, and at least four types of yellow, magenta, cyan and black are used. used.

Examples of yellow pigments include Hansa Yellow, Benzidine Yellow, Cadmium Yellow, Yellow Lead G, Zinc Chromate, Lemon Yellow, Strocian Yellow and Indian Yellow.

Examples of magenta pigments include
Rhodamine B lake, cadmium red, red iron oxide, chrome vermillion, pyrazolone red, resole red, red lead, watching red and the like.

Examples of cyan pigments include ultramarine blue, Prussian blue, cobalt blue, cerulean blue, manganese blue, and phthalocyanine blue.

Examples of black pigments include
Examples include titanium black and carbon black.

The amount of the colorant in the photocurable resin composition is 100 parts by weight of the organic polymer copolymer.
A range of 0.1 to 300 parts by weight is preferable.

In the above photocurable resin composition, dioctyl phthalate, triethylene glycol diacetate,
Plasticizers such as p-toluenesulfonamide and N-ethyltoluenesulfonamide; thermal polymerization inhibitors such as hydroquinone and p-methoxyphenol; stabilizers; ultraviolet absorbers; antioxidants; solvents such as methyl ethyl ketone (MEK) and toluene. Etc. may be added.

As a method for forming a photocurable resin layer on a support from the above photocurable resin composition, for example, a dilute solution of the photocurable resin composition is used to form a resin film such as polyethylene terephthalate or biaxially oriented polypropylene. A method of casting on a support so as to have a constant thickness and then drying is mentioned. Further, this support may be previously subjected to a mold release treatment.

Examples of the solvent for diluting the photocurable resin composition include methyl ethyl ketone, ethyl acetate, methanol and the like.

The thickness of the photocurable resin layer is not particularly limited, but if it becomes thin, it becomes difficult to handle, and it becomes difficult to obtain a sufficient color density, and if it becomes thick, peeling between layers easily occurs. 0.5 to 20 μm is preferable.

It is also possible to change the gradation of the light and shade of the image pattern by setting the color density per sheet of the photo-curable resin layer to be low and adjusting the number of layers to be overlapped.

The support may be previously provided with a heat-fusible layer containing an alcohol-soluble polyamide as a main component.

The heat-fusible layer is preferably formed from a resin composition comprising an alcohol-soluble polyamide and a hydroxystyrene polymer, a rosin resin or a sulfonamide compound. In particular, it is more preferable to use a rosin resin or a sulfonamide compound.

As the alcohol-soluble polyamide, for example, the polyamide resin disclosed in JP-A-61-188537 can be used, and as commercially available products, "Amilan CM-4000" and "Amilan CM" manufactured by Toray Industries, Inc. -8000 "and the like.

As the above-mentioned hydroxystyrene polymer,
For example, those disclosed in JP-A-61-188537 can be used, and examples of commercially available products include "Resin M" manufactured by Maruzen Oil Co., Ltd.

If the amount of the above-mentioned hydroxystyrene polymer used is small, there is no effect of improving the heat fusion property, and if it is large, color cast occurs. Therefore, 5 to 20 parts by weight relative to 100 parts by weight of the alcohol-soluble polyamide is used. Is preferred.

The above-mentioned rosin resin is the remaining resin obtained by steam-distilling terpentine secreted from pine resin to remove volatile turpentine oil, which is obtained by purifying or modifying a mixture of abietic acid, dextropimaric acid and the like. However, polymerized rosin, disproportionated rosin, hydrogenated rosin, esters of these, and the like can also be used. In particular,
The rosin resin is preferably colorless and transparent with a Hazen display of 300 or less (Gardner display of 1 or less), an acid value of 10 to 250, and a softening point of 65 to 130 ° C. Examples include hydrogenated ultra-light color rosin "KR-610" manufactured by Arakawa Chemical Co., Ltd.

If the amount of the rosin resin used is small, there is no effect of improving the heat-sealing property, and if it is large, color cast occurs. Therefore, it is preferably 5 to 100 parts by weight with respect to 100 parts by weight of the alcohol-soluble polyamide. .

The above sulfonamide compounds include o
-Or p-toluenesulfonamide, N-ethyl-o-
Toluenesulfonamide, N-ethyl-p-toluenesulfonamide, N-methyl-o-toluenesulfonamide, N-methyl-p-toluenesulfonamide, N-methylbenzenesulfonamide, N-butylbenzenesulfonamide, N- Examples thereof include cyclohexyl-p-toluenesulfonamide, and one or more of these are used.

The amount of the above sulfonamide compound used is
When the amount is small, there is no effect of improving the heat fusion property, and when the amount is large, color cast occurs or bleeding occurs to cause tackiness on the surface.
The amount is preferably 1 to 30 parts by weight, more preferably 2 to 20 parts by weight, based on 0 parts by weight.

The resin composition used in the heat-fusible layer contains a thermal polymerization inhibitor such as hydroquinone and p-methoxyphenol, a stabilizer, an ultraviolet absorber, an antioxidant, a solvent such as methyl ethyl ketone and toluene. It may be added.

Examples of the solvent for diluting the resin composition used in the heat-fusible layer include methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, isobutanol, tert.
A lower aliphatic alcohol such as butanol; a mixed solvent of the lower aliphatic alcohol and an aromatic alcohol such as phenol or benzyl alcohol; a mixed solvent of the lower aliphatic alcohol and a cellosolve such as methyl cellosolve or ethyl cellosolve A mixed solvent of the above-mentioned lower aliphatic alcohol and ethylene glycol, propylene glycol, formic acid or water, and the like. However, when a mixed solvent is used, it is preferable that the lower aliphatic alcohol is contained in an amount of 50% by weight or more from the viewpoint of solution stability.

The thickness of the heat-fusible layer is not particularly limited, but if it is thin, handling becomes difficult and the heat-fusion force is insufficient, and if it is thick, misalignment may occur during image lamination. 1 to 20 μm is preferable.

A method for forming a colored halftone dot image pattern using the above-mentioned photocurable resin layer will be described below. First, as shown in FIG. 1, a black photo-curable resin layer 2 is formed on a temporary support 4 via a heat-fusible layer 3, and a protective layer 1 is further formed on the photo-curable resin layer 2. As shown in FIG. 2, the halftone dot negative mask 5 corresponding to black is superposed on the protective layer 1 by using the obtained photocurable film, and after exposure and curing through the halftone dot negative mask 5, The protective layer 1 is removed by development, and a halftone dot image pattern 6 corresponding to the halftone negative mask 5 is formed as shown in FIG.

By the same operation, a three-color photo-curable film in which halftone dot image patterns corresponding to halftone negative masks of yellow, magenta and cyan are formed on the temporary support is prepared.

The protective layer 1 may be formed of a resin film such as polyethylene terephthalate, biaxially oriented polypropylene, polyvinyl alcohol, polyvinylpyrrolidone, polyacrylic acid, polyacrylamide, or the above-mentioned alkali-soluble organic polymer copolymer. It may be formed by diluting the coalesced product with a solvent and applying and drying.

As the solvent, water, a mixed solvent of water and an aliphatic alcohol such as methanol, ethanol, n-propanol and isopropanol; a mixed solvent of water and an aromatic alcohol such as benzyl alcohol; water and methyl cellosolve, ethyl Mixed solvent with cellosolves such as cellosolve;
A mixed solvent of water and glycols such as ethylene glycol and propylene glycol can be used.

When the protective layer 1 is formed of a resin film, it is peeled off during development, and when the protective layer 1 is formed of an alkali-soluble organic polymer copolymer, it is dissolved in an alkaline aqueous solution during development. To remove.

In the above description, the halftone dot negative mask of four colors of yellow, magenta, cyan and black is used, but the number is not limited to four, and light of other colors (for example, white) may be used as required. A curable film may be used to form a halftone dot image pattern.

The light source for exposing the photocurable resin layer to light is not particularly limited, and a conventionally known light source can be used. For example, an ultrahigh pressure mercury lamp, a metal halide lamp or the like is preferably used.

The developing solution used for developing is not particularly limited, but may be, for example, 0.5.
An aqueous solution of sodium carbonate having a concentration of ˜5% by weight is preferably used. The developing device used for development is not particularly limited, and a known device can be used.

The method for transferring the colored halftone dot image pattern to the photosensitive image receiving sheet will be described below. First, as shown in FIG. 4, using a photosensitive image receiving sheet 7 having an antistatic hard coat layer 71 formed on one surface of a support 11 and an image receiving layer 72 formed on the other surface,
As shown in FIG. 5, the black halftone dot image pattern 6 of the photocurable film and the image receiving layer 72 of the photosensitive image receiving sheet 7 are superposed so as to face each other, and the laminator roller 12 is provided to the temporary support 4 side. From above, the temporary support 4 is peeled off while heating and pressurizing the halftone image pattern 6 and the image receiving layer 72. By the above operation, the black dot image pattern 6 is transferred and laminated on the image receiving layer 72 together with the heat fusion layer 3.

By the same operation as described above, as shown in FIG. 6, the cyan halftone dot image pattern 8 is transferred together with the heat adhesive layer 3 onto the heat adhesive layer 3 of the black halftone dot image pattern 6, Stack. By repeating the same operation as described above, the cyan halftone dot image pattern 8 is transferred onto the heat-sealing layer 3 and the magenta halftone dot image pattern 9 is transferred and laminated together with the heat-sealing layer 3, and then the heat-sealing layer 3 is melted. The yellow dot image pattern 10 is transferred and laminated together with the heat fusion layer 3 on the adhesion layer 3. By the above operation, as shown in FIG. 7, a colored image in which halftone dot image patterns of black, cyan, magenta and yellow are laminated on the image receiving layer 72 is obtained.

The temperature of the laminator roll is determined by the heat resistance of the substrate used, the softening temperature of the photocurable resin layer and the like, but is generally preferably 50 to 130 ° C. The pressure is preferably 0.5 to ¹⁰ kg / cm ² .

The colored image laminated on the image receiving layer 72 is irradiated with ultraviolet rays from the antistatic hard coat layer 71 side to cure the image receiving layer 72 and the colored image is formed on the support 11.
A display board can be obtained by adhering to the. In addition, after the colored image laminated on the image receiving layer 72 is transferred and laminated onto another substrate, ultraviolet rays are irradiated from the substrate side to cure the heat fusion layer, and the colored image is adhered to the substrate. ,
You may get a display board.

When the irradiation amount of the ultraviolet rays is small, the curing is insufficient and the surface hardness is insufficient, so that the obtained image is easily scratched, and when the irradiation amount is large, yellowing occurs.
It is preferably 4,000 mJ / cm ² .

The above-mentioned substrate is not particularly limited, and generally, a plastic plate such as an acrylic resin, a polycarbonate resin, a polyester resin, etc .; a glass plate; a ceramic plate; a metal plate, etc. It is preferably used and is selected in consideration of necessary properties such as flexibility, transparency and heat resistance. These substrates may be colored.
Further, a primer layer or an adhesive layer may be provided on these substrates in advance in order to improve the adhesion.

The present invention 2 will be described below. As shown in FIG. 8, the photosensitive image receiving sheet used in the present invention 2 has an antistatic hard coat layer 7 on one surface of a support 11.
1 is formed, and the image receiving layer 72 is formed on the antistatic hard coat layer 71, which is different from the present invention.

As the support, the same support as that used in the present invention is preferably used.

The antistatic hard coat layer is preferably formed from the same photopolymerizable resin composition (a) as in the present invention.

The image receiving layer is preferably formed from the same photopolymerizable resin composition (B) as in the present invention.

Using the photosensitive image-receiving sheet of the present invention 2 in the same manner as in the present invention, black, cyan,
A display board is obtained by forming a halftone dot image pattern of magenta and yellow and then laminating the halftone dot image pattern on the image receiving layer.

EXAMPLES The present invention will be described below based on examples. (Example 1) (1) Preparation of resin composition made by heat fusion-Alcohol-soluble polyamide ("CM-80 manufactured by Toray Industries, Inc."
00 ") 90 parts by weight-Stabilized ultra-light rosin (" KR-61 "manufactured by Arakawa Chemical Co.
0 ") 10 parts by weight The above components were dissolved in 900 parts by weight of methanol to prepare a heat-fusible resin composition solution.

(2) Preparation of photocurable resin composition 100 parts by weight of alkali-soluble organic polymer copolymer (methyl methacrylate / butyl methacrylate / 2-ethylhexyl acrylate / methacrylic acid = 31/31/13/25 ( Weight ratio), weight average molecular weight = 100,000) -67 parts by weight of unsaturated compound (component: trimethylolpropane triacrylate) -1.5 parts by weight of photopolymerization initiator (component: 2,4,6-trimethylbenzoyl) Diphenylphosphine oxide) ("Lucirin TPO" manufactured by BASF) -Yellow-based pigment ("FPF-27E Yellow" manufactured by Dainichiseika) 10 parts by weight or-Magenta-based pigment ("FPF-96Q red" manufactured by Dainichiseika) 10 10 parts by weight of cyan pigment (“FPF-CP2 blue” manufactured by Dainichi Seika) • Black pigment (Dainichi The reduction made "FPF-40S Black") 10 parts by weight The above components are dissolved in methyl ethyl ketone 400 parts by weight, yellow, magenta, cyan and black,
A solution of each of the four types of photocurable resin compositions that were colored was prepared.

(3) Preparation of resin composition for protective layer Polyvinyl alcohol 10 parts by weight (“GL-05” manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) The above components were dissolved in a mixed solvent consisting of 97 parts by weight of water and 3 parts by weight of methanol. A heat protection layer resin composition solution was prepared.

(4) Preparation of Photocurable Film Polyethylene terephthalate (hereinafter PE) having a thickness of 75 μm
A heat-fusible resin composition solution was cast on a temporary film support (T) and dried at 100 ° C. for 2 minutes, and then a heat-fusible layer having a thickness of 4 μm after drying was provided. Then, a photocurable resin composition solution was cast on the heat-fusible layer and dried at 90 ° C. for 2 minutes, and then colored with yellow, magenta, cyan and black each having a thickness of 4 μm after drying. Four types of photocurable films having the photocurable resin composition layer were obtained. Further, the protective layer resin composition solution was cast onto the photocurable resin composition layer of the photocurable film colored yellow, magenta, cyan and black, respectively, and 10
After drying at 5 ° C. for 2 minutes, a protective layer having a thickness of 1 μm after drying was provided.

(5) Preparation of Photopolymerizable Resin Composition (a): Conductive Metal Oxide Powder (Primary Particle Size: 0.02 μm) 300 Parts by Weight (Mitsubishi Materials' Antimony Oxide-Containing Tin Oxide Powder) Erythritol hexaacrylate 100 parts by weight ("DPHA" manufactured by Nippon Kayaku Co., Ltd.) ・ Dispersant 30 parts by weight (Sekisui Chemical Co., Ltd., butyral resin, residual hydroxyl group 35 mol%, degree of polymerization 1700) ・ Photopolymerization initiator (BASF) Manufactured by "Lucirin TPO") 3 parts by weight Each of the above components was dissolved in 500 parts by weight of methyl cellosolve to prepare a photopolymerizable resin composition (a) solution used for the antistatic hard coat layer.

(6) Preparation of Photopolymerizable Resin Composition (B) 65 parts by weight of organic polymer copolymer (methyl methacrylate / butyl methacrylate / 2-ethylhexyl acrylate / methacrylic acid = 31/31/13/25 (Weight ratio), weight average molecular weight = 100,000) ・ Unsaturated compound 10 parts by weight (Component: bifunctional urethane acrylate oligomer, "NK oligomer UA-4000" manufactured by Shin Nakamura Chemical Co., Ltd.) ・ Unsaturated compound 25 parts by weight (Ingredients: epichlorohydrin-modified 1,6-hexanediol diacrylate, Shin-Nakamura Chemical Co., Ltd. "Calayad R-167") Photoinitiator (BASF "Lucirin TPO") 1 part by weight 400 parts by weight of the above components To prepare a photopolymerizable resin composition (b) solution for use in the image receiving layer.

(7) Preparation of Photosensitive Image Receiving Sheet A photopolymerizable resin composition (a) solution was applied to one side of a transparent PET film support (“Tetron film HS series HPJ” manufactured by Teijin Ltd.) having a thickness of 75 μm. After spreading and drying at 115 ° C. for 2 minutes, an antistatic hard coat layer having a thickness after drying of 2 μm was formed. Then, the photopolymerizable resin composition (b) solution was cast on the other surface and dried at 115 ° C. for 2 minutes,
An image receiving layer having a thickness of 15 μm after drying was formed to obtain a photosensitive image receiving sheet.

(8) Formation of halftone dot image pattern On the protective layer of the black photocurable film obtained above, through a halftone negative mask corresponding to black, an ultrahigh pressure mercury lamp of 400 mJ / cm ² was used. Light irradiation was performed to cure the non-mask portion. Then, a 1% by weight sodium carbonate aqueous solution at 25 ° C. is sprayed at a pressure of ² kg / cm ² for 45 seconds to develop, and the unexposed portion is dissolved and removed to obtain a halftone dot image corresponding to a black halftone negative mask. A pattern was formed. Further, in the same manner, using the cyan, magenta, and yellow colored photocurable films obtained above, halftone dot image patterns corresponding to cyan, magenta, and yellow halftone negative masks were formed, respectively. .

(9) Formation of image First, a dot image pattern of a black photocurable film is superposed on the image receiving layer of the photosensitive image receiving sheet, and it is pressed with a laminator roll and heated (5 kg / c).
m ² , 120 ° C., 1.2 m / min), the temporary support is peeled off, and the halftone dot image pattern is transferred together with the heat-fusible layer,
Laminated. Then, the same operation was performed to transfer and laminate the halftone dot image pattern of the cyan photocurable film on the heat-fusible layer together with the heat-fusible layer. Further, by performing the same operation, by transferring and laminating the halftone dot image pattern of the magenta and cyan photocurable film together with the heat-fusible layer, black, cyan, and
The magenta and yellow halftone dot image patterns were laminated. Then, an ultraviolet ray of 1,000 mJ / cm ² was irradiated from the side of the photosensitive image receiving sheet with an ultra-high pressure mercury lamp to cure the image receiving layer and obtain a display board.

Example 2 An antistatic hard coat layer was added,
Using the photopolymerizable composition (a) solution below, a thickness of 25 μm
A display board was obtained in the same manner as in Example 1 except that the thickness was 2 μm after dried on a PET film of m. -Pentaerythritol triacrylate 100 parts by weight (Osaka Organic Chemical Co., Ltd. "Viscoat # 300" -Conductive tin oxide 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 (BASF's "Lucirin TPO") 3 parts by weight ・ Methyl Cellosolve 500 parts by weight

Example 3 An antistatic hard coat layer was added,
Using the following photopolymerizable composition (d) solution, the thickness is 25μ.
A display board was obtained in the same manner as in Example 1 except that the thickness was 2 μm after dried on a PET film of m. Tetramethylolmethane tetraacrylate 100 parts by weight (Shin-Nakamura Chemical Co., Ltd. "A-TMMT") Conductive metal oxide powder 300 parts by weight (Component: antimony oxide-containing tin oxide powder, Mitsubishi Materials, primary particle size: 0 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, BASF "Lucirin TPO" manufactured by the company) ・ Methyl cellosolve 500 parts by weight

Example 4 An antistatic hard coat layer was added,
Using the following photopolymerizable composition (d) solution, the thickness is 25μ.
A display board was obtained in the same manner as in Example 1 except that the thickness was 2 μm after dried on a PET film of m. 6-functional urethane acrylate 100 parts by weight ("UA-306T" manufactured by Kyoeisha Yushi Kagaku Co., Ltd.)-Conductive metal oxide powder 300 parts by weight (component: antimony oxide-containing tin oxide powder, manufactured by 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 (BASF's "Lucirin TPO") 3 parts by weight- Methyl cellosolve 500 parts by weight

Comparative Example 1 A display board 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 display board 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 metal oxide powder.

Example 5 A display board was obtained in the same manner as in Example 1 except that the method for producing the photosensitive image-receiving sheet was changed as follows. First, the thickness of the temporary support is 25μ
The photopolymerizable resin composition (b) prepared in Example 1 was applied to one surface of a transparent PET release film of m ("Tetron Film S-35" manufactured by Teijin Ltd.), and dried at 115 ° C for 2 minutes,
An image receiving layer having a thickness after drying of 15 μm was formed. Separately from the above, a transparent PET film support having a thickness of 75 μm (“Tetoron film HS series HPJ” manufactured by Teijin Ltd.)
The photopolymerizable resin composition (a) prepared in Example 1 was applied to one surface of the above, and dried at 115 ° C. for 2 minutes to form an antistatic hard coat layer having a thickness after drying of 2 μm. Then, an image receiving layer was laminated on the antistatic hard coat layer and laminated by lamination to prepare a photosensitive image receiving sheet.

Example 6 A display board was produced in the same manner as in Example 2 except that the photosensitive image-receiving sheet was produced in the same manner as in Example 5.

Example 7 A display board was produced in the same manner as in Example 3 except that the photosensitive image-receiving sheet was produced in the same manner as in Example 5.

Example 8 A display board was produced in the same manner as in Example 4 except that the photosensitive image-receiving sheet was produced in the same manner as in Example 5.

Comparative Example 3 A display board was obtained in the same manner as in Example 5, except that the antistatic hard coat layer was formed from a photopolymerizable resin composition containing no conductive metal oxide 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

[0119]

[Table 1]

[0120]

[Table 2]

[0121]

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 cross-sectional view showing a photocurable film used in the present invention.

FIG. 2 is a schematic cross-sectional view showing a situation in which a photocurable film used in the present invention is exposed through a halftone dot negative mask.

FIG. 3 is a schematic cross-sectional view showing a halftone dot image pattern obtained by exposing and developing the photocurable film used in the present invention.

FIG. 4 is a schematic sectional view showing a photosensitive receiving sheet used in the present invention.

FIG. 5 is a schematic cross-sectional view showing a state in which a halftone dot image pattern is transferred and laminated on an image receiving layer of a photosensitive receiving sheet.

FIG. 6 is a schematic cross-sectional view showing a state in which a halftone dot image pattern of another color is transferred and laminated on the halftone dot image pattern laminated on the image receiving layer of the photosensitive receiving sheet.

FIG. 7 is a schematic cross-sectional view showing a colored image in which four color dot image patterns are laminated on the image receiving layer of the photosensitive receiving sheet.

FIG. 8 is a schematic sectional view showing a photosensitive receiving sheet used in the present invention 2.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Protective layer 2 Photocurable resin layer 3 Heat-fusible layer 4 Temporary support 5 Halftone dot negative mask (black) 6 Halftone image pattern (black) 7 Photosensitive receiving sheet 71 Antistatic hard coat layer 72 Image receiving layer 8 Halftone Image Pattern (Cyan) 9 Halftone Image Pattern (Magenta) 10 Halftone Image Pattern (Yellow) 11 Support

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location G03F 7/004 513 7/105 504 7/34

Claims (2)

[Claims] 1. A photosensitive image receiving sheet having an antistatic hard coat layer provided on one surface of a support and an image receiving layer provided on the other surface, 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, (b) 0.1 to 10 parts by weight of a photopolymerization initiator, and a particle size of 0.01 to 0. 4 μm conductive metal oxide powder 20 to
A photosensitive image-receiving sheet comprising a photopolymerizable resin composition comprising 2,000 parts by weight. 2. A photosensitive image receiving sheet having an antistatic hard coat layer provided on one surface of a support, and an image receiving layer provided on the antistatic hard coat layer, wherein the antistatic hard coat layer is provided. Is formed from the photopolymerizable resin composition according to claim 1.