JPH0349423B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a mask image forming material comprising a white mask layer on a transparent support and a photoresist layer thereon, and a light source having high intensity radiation in a wavelength range of 600 nm to 1200 nm. The present invention relates to a mask image forming material which has light resistance particularly to high-intensity xenon flash lamp light such as a xenon lamp, a halogen lamp, a tungsten lamp, etc., and is useful for forming a transparent original in a thermal image forming method.

As an image forming method, as described in Example 6 of Japanese Patent Publication No. 54-10870, a heat-sensitive polymer and a material dispersed in the heat-sensitive polymer absorb light and convert it into heat. A method is known in which a heat-sensitive recording layer made of material particles such as carbon black is provided on a support, a transparent original is placed on top of the other, and a recorded image is formed by exposure and development from the original side with high-intensity xenon flash light.

This thermal image forming method enables operations such as handling, exposure, and development of image-forming materials without causing any exposure fog under daylight. It has superior ease of operation compared to other photosensitive materials. However, in this method, as described in Example 6 of the above-mentioned Japanese Patent Publication No. 54-10870, the conditions of irradiation energy of 1.8 J/cm ² and exposure time of 1/1000 seconds consisting of visible light and near-infrared light are required for exposure in this method. It is necessary to use a light source with extremely high intensity compared to the conventional photosensitive materials mentioned above. Furthermore, when the heat-sensitive recording layer and the transparent original are overlapped and exposed from the original side, the original is exposed to this high-intensity light source, so the original used in this exposure method must be repeatedly blocked from visible light and near-infrared rays. It must have sufficient lightfastness to allow for light exposure and must not be damaged by exposure to light.

By the way, conventional mask image forming materials include, for example, silver salt photosensitive materials such as silver halide lithographic film, and non-silver salt photosensitive materials such as diazo photosensitive materials with color tones such as black and sepia. The mask material is usually a photosensitive material sensitive to about 400 to 570 nm. Therefore, as mentioned above, when exposed to high-intensity xenon flash light with an output wavelength in the vicinity of 800 to 1000 nm, for example, the dye in the image absorbs the light and generates heat, which damages the binder and destroys the image. There was a problem that it was damaged or lost, and it was not usable.

SUMMARY OF THE INVENTION It is an object of the present invention to provide a transparent original for thermal imaging methods which does not damage the image even when exposed to extremely powerful light sources such as the high-intensity xenon flash lamp light described above. An object of the present invention is to provide a mask imaging material.

As a result of intensive studies to achieve the above-mentioned objective, the present inventors have developed a transparent support with a total light transmittance of 80% or more for visible light and near-infrared light, which is white and transmits total light in the wavelength range of 600 to 1200 nm. Rate is
70% or less and a photoresist layer on the mask layer, the masked imaging material has no damage to very high intensity light sources, such as the high intensity xenon flash lamp light mentioned above. The present invention was completed based on the knowledge that a transparent original for a thermal image forming method that does not undergo heat transfer can be provided.

That is, the thermal photographic mask image forming material of the present invention is formed by sequentially laminating a white mask layer and a photoresist layer on a substantially transparent support, and the total light transmittance of the white mask layer including the support is is the wavelength range
It is 70% or less at 600 to 1200 nm.

Here, the substantially transparent support refers to a wavelength range of 600 to 1200 nm used for exposure of thermographic materials.
Since it is necessary to have transparency in the visible light range for operations such as alignment, it is necessary to have a total light transmittance of at least 80% in the visible and near-infrared ranges.

Further, the reason why the mask layer is a white mask layer containing a white pigment is that the white pigment has durability against actinic light and has a high reflectance. As mentioned above, conventional mask materials in black or sepia colors are undesirable because they absorb actinic rays, generate heat, and are easily damaged. The total light transmittance of the mask layer including the support is in the wavelength range 600~
The reason why we set it to 70% or less at 1200 nm is that this wavelength range is normally used for exposure of thermographic materials, and in order to obtain performance as a transparent original, the difference from the total light transmittance of the support alone is required. is at least 10%
This is because it is necessary.

The present invention will be explained in detail below.

The support in the image forming material of the present invention is a transparent support with excellent dimensional stability and a total light transmittance of 80% or more for visible light and near-infrared light, and examples of the support include polyester film, Plastic films such as triacetate film, polycarbonate film, polyimide film, polysulfone film, polystyrene film, and polypropylene film, resin plates such as acrylic resin plates, polycarbonate resin plates, and polyester resin plates, glass plates, etc. can be used. The support is made of aluminum, copper, bismuth, chromium,
Brass, indium oxide, etc. are deposited,
It may be colored with dyes, pigments, etc. Also,
In order to improve the adhesion between the mask layer of the present invention and the support, a subbing layer may be provided on the support as necessary,
The support may be subjected to electrical discharge treatment.

According to the present invention, a mask layer that is white and has a total light transmittance of 70% or less in a wavelength range of 600 to 1200 nm is provided on the above-mentioned support. Preferably, the mask layer is composed of a white pigment and a film-forming polymer. White pigments include zinc oxide {ZnO}, titanium oxide {TiO ₂ }, basic lead carbonate {2PbCO ₃・Pb(OH) ₂ }, lithopone {ZnS and BaSO ₄
The content is 5 to 500% by weight based on the film-forming polymer so that the total light transmittance of the mask layer in the wavelength range of 600 to 1200 nm is 70% or less. %Preferably
It is 30-300% by weight.

Film-forming polymers include water, alkaline aqueous solutions, acidic aqueous solutions, neutral salt aqueous solutions, or hydrocarbon-based, halogenated hydrocarbon-based, alcohol-based, ether-based, acetal-based, ketone-based, and ester-based polymers. , polyhydric alcohols and their derivatives, fatty acids and phenols, nitrogen compounds, and other liquid organic compounds, such as hexane, toluene, xylene, carbon tetrachloride, trichloroethane, methanol, ethanol, isopropanol, tetrahydrofuran, methyl ethyl ketone, ethyl acetate, A polymeric compound that can be dissolved in methylcellosolve, ether, etc. alone or in a mixture, such as gelatin, methylcellulose, ethylcellulose, hydroxyethylcellulose, carboxymethylcellulose, polyvinyl alcohol, sodium polyacrylate,
Water-soluble resins such as polyethylene oxide. Cellulose resins such as cellulose acetate butyrate, cellulose acetate propionate, and cellulose acetate. Polyvinyl acetate, polyvinyl formal, polyvinyl butyral, vinyl chloride-vinyl acetate copolymer, vinyl chloride-vinyl acetate-vinyl alcohol copolymer,
vinyl chloride-vinyl acetate-maleic acid copolymer,
Vinylidene chloride-vinyl chloride copolymer, vinylidene chloride-acrylonitrile copolymer, ethylene-vinyl acetate copolymer, acrylic acid methacrylate copolymer, styrene-maleic anhydride copolymer partial ester, acrylamide-diacetone Acrylamide copolymer, dimethylaminoethyl methacrylate-methyl methacrylate copolymer,
Vinyl resins such as methyl methacrylate-2-hydroxyethyl methacrylate copolymer, methyl vinyl ether-maleic anhydride copolymer, and vinylpyridone-vinyl acetate copolymer. Phenol resins such as resol type phenolic resins and novolac type phenolic resins. Nylon resin. Examples include saturated polyester resin, and the thickness of the film formed on the support by the high molecular compound containing a white pigment dispersed therein is preferably 0.5 to 20 μm, more preferably 2 to 8 μm.

A photoresist layer is provided on top of the white mask layer of white pigment and film-forming polymer.
The photoresist layer in the present invention is made of a photosensitive film-forming substance, and becomes soluble in developing solutions such as water, alkaline aqueous solution, acidic aqueous solution, neutral salt aqueous solution, and organic solvent when exposed to ultraviolet light, visible light, etc. Ice, alkaline aqueous solution, acidic aqueous solution, organic solvent, etc. that change the swelling property and allow only either the exposed or non-exposed portion to remain on the white mask layer, and the remaining portion dissolves the white mask layer. Various conventionally known photoresists described below can be used as long as they have the property of being insoluble in the etching solution.

(1) Photoresist that combines 1,2-naphthoquinone diazide and alkali-soluble resin For example, "New Photosensitive Resin" by Takahiro Tsunoda, Showa
2, described on pages 78-79 published by the Printing Society Publishing Department in 1956.
3,4-trioxybenzophenone-3,4-
Bis[naphthoquinone-1,2-diazide-5-
Mixture of sulfonic acid] ester and metacresol formaldehyde resin (novolak type), 2-[naphthoquinone-1,2-diazide]
Mixture of 5-sulfonyloxy]-7-oxynaphthalene and sierac or styrene-maleic anhydride copolymer, naphthoquinone-1,2
- A mixture of diazide-5-sulfanilide and 4-aminostyrene (pentapolymer), a mixture of naphthoquinone-1,2-diazide-5-sulfonic acid novolac ester and phenol-formaldehyde resin (novolac type), etc. In addition, there are other commercial products available in the United States.
Azoplate-Shipley's AZ series, USA
Kodak's KAP (type 3), Fuji Pharmaceutical's
Examples include FPPR and Tokyo Ohka Kogyo Co., Ltd.'s Fotosol.

(2) Photoresist that combines diazo resin and water-soluble resin or alkali-soluble resin Photoresist that combines diazo resin and water-soluble resin or alkali-soluble resin includes:
Water-soluble diazo resins such as P-diazodiphenylamine paraformaldehyde condensate and gelatin, polyvinyl alcohol, polyvinylpyrrolidone, hydroxyethyl cellulose, methyl vinyl ether-maleic anhydride copolymer, acrylamide-diacetone acrylamide copolymer, etc. 2-hydroxyethyl methacrylate-acrylonitrile-methyl methacrylate-to a photoresist that is a combination of resins or an organic solvent-soluble version of the above diazo resin.
Examples include photoresists in combination with alkali-soluble resins such as methacrylic acid copolymers.

(3) Photoresists with azide groups as photosensitive groups Photosensitive resins with azide groups as photosensitive groups are made by mixing an azide compound with natural rubber, synthetic rubber, cyclized rubber that cyclizes a part of the rubber molecule, etc. There are rubber-azide photosensitive resins consisting of P-phenylene bisazide, P-azidobenzophenone, 4,4'-diazidobenzophenone, and 4,4'-diazidophenylmethane, 4,4'-diazidostilbene,
4,4'-Diazidochalcone, 2,6-di-
(4'-azidobenzal)cyclohexane, 2,
Examples of the above azide compounds include 6-di-(4'-azidobenzal)-4-methylcyclohexane. Commercially available rubber-azide photosensitive liquids include KTFR from KODAK in the US, EPPR and OMR from Tokyo Ohka Kogyo Co., Ltd., and Fuji Pharmaceutical Co., Ltd.
Examples include FSR, Okamoto Chemical Industry Co., Ltd.'s Teishu Resist S, and Yamatoya Shokai's KY Resist.

In addition, photosensitive resins incorporating an azide group into the molecule include polyazidovinyl benzoate, polyazidovinyl phthalate, polyazidostyrene, and polyvinylazidobenzal, which are described on pages 104 to 105 of the above-mentioned "New Photosensitive Resins". Examples include acetal, polyvinylazidonaphthyl acetal, azidobenzaldehyde-phenol resin, and azidodiphenylamine polymarin condensation polymer.

Furthermore, a photoresist obtained by mixing an azide photosensitive agent and a polymer described in the above-mentioned "New Photosensitive Resin" pages 107 to 108, such as 4,4'-diazidostilbene-2,2'-disulfonic acid anilide , 4-azido-1-phenylamidebenzene-2-sulfonic acid anilide, or 4-
Examples include photoresist layers made of a mixture of 4'-diazide chalcone and a novolak type phenolic resin.

(4) Photoresists with a cinnamoyl group or cinnamylidene group as a photosensitive group Examples of photoresists with a cinnamoyl group as a photosensitive group include polyvinyl cinnamate, and commercially available polyvinyl cinnamate photosensitive solutions are
KPR of KODAK, TPR of Tokyo Ohka Kogyo,
One example is Sanpo Chemical's SPR. Further, polyvinyl cinnamylidene acetate and its derivatives, which are obtained by esterifying PVA with cinnamylidene acetic acid instead of cinnamic acid, are mentioned, for example, polyvinyl cinnamylidene acetate and its derivatives are described in the above-mentioned "New Photosensitive Resins", pages 56-57. denacetate,
Examples include polyvinylzenzoate-cinnamylidene acetate, polyvinylcarbethoxymethyl carbamate-cinnamylidene acetate, polyvinyl acetate-cinnamylidene acetate, and the like. Other examples include acrylic cinnamoyl type polymers, such as those made by reacting polychloroethyl acrylic acid with potassium cinnamate, and those made by adding cinnamic acid to a glycidyl methacrylate copolymer.

(5) Photoresist with an acryloyl group as a photosensitive group 10 to 40% by weight of a monomer having an acryloyl group, 1 to 20% by weight of a photopolymerization initiator, and a film-forming polymer that can be dissolved or expanded in a developer.
Examples include photoresists in which 10 to 80% by weight and 10% by weight or less of other additives such as sensitizers and thermal polymerization inhibitors are dissolved.

The monomer having an acryloyl group is an unsaturated monomer capable of addition polymerization, and specifically,
Polyfunctional acrylates, such as 1,6-hexanediol acrylate, polyethylene glycol
200 diacrylate, diethylene glycol diacrylate, neopentyl glycol diacrylate, triethylene glycol diacrylate,
Hydroxypivalate ester neopentyl glycol diacrylate, bis(acryloxyethoxy)bisphenol A, bis(acryloxypolyethoxy)bisphenol A, trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol hexaacrylate, etc. Desirably, in addition, phenoxyethyl acrylate, stearyl acrylate, lauryl acrylate, methoxyethyl acrylate, N,N dimethylaminoethyl acrylate, 2-hydroxyethyl acrylate, 2-
Monofunctional acrylates such as hydroxypropyl acrylate, 2-methoxyethoxyethyl acrylate, 2-ethoxyethoxyethyl acrylate, 2-hydroxyethyl acryloyl phosphate, and tetrahydrofurfuryl acrylate can also be used in combination with the above-mentioned polyfunctional acrylates.

Photopolymerization initiators include acetophenone, P-dimethylacetophenone, benzophenone, PP-dichlorobenzophenone, Michler's ketone (4-
4′-bisdimethylaminobenzophenone), benzyl, benzoin, benzoin methyl ether,
Benzoin ethyl ether, benzoin isopropyl ether, benzoin n-propyl ether, benzoin isobutyl ether, benzoin n-butyl ether, 2-chlorothioxanthone, 2-methylthioxanthone, azobisisobutylnitrile, benzoin peroxide, 2,
4,5-triphenylimidazole dimer and the like can be used.

Film-forming polymers that can be dissolved or swelled in a developer include polyvinyl alcohol, polyacrylic acid, acrylamide-diacetone acrylamide copolymer, etc. when the developer consists of water alone, and when the developer consists of an alkaline aqueous solution. In this case, acrylic acid-methacrylic acid ester copolymer, partially esterified styrene-maleic anhydride copolymer, novolak type phenolic resin, nylon resin, etc. can be used. Moreover, when the developing solution consists of an acidic aqueous solution, dimethylaminoethyl methacrylate-methyl methacrylate copolymer or the like can be used. Michler's ketone, thiazine dye, etc. can be used as a sensitizer, and hydroquinone, etc. can be used as a thermal polymerization inhibitor. More desirably, a polymer or oligomer having a photopolymerizable unsaturated group in the main chain, chain end, or side chain may be used in the above-mentioned composition in a compatible manner, if necessary.

Hereinafter, the present invention will be specifically explained with reference to Examples.

Example 1 Titanium oxide (FR-22 manufactured by Furukawa Mining Co., Ltd.) 10 g Methyl methacrylate-2-hydroxyethyl methacrylate copolymer (methyl methacrylate 30 mol%, 2-hydroxyethyl methacrylate 40 mol%, methacrylate Copolymer containing 27 mol% nitrile and 3 mol% methacrylic acid) 5g Methyl cellosolve 60g Silicone surfactant (XB-2725, manufactured by Dow Corning) 0.1g Add 80g of glass beads to the above composition and paint A coating solution was obtained by dispersing for 6 hours using a sheaker. Apply this coating liquid to a thickness of 100μ in a wavelength range of 600~
The coating was applied using a wire bar onto a corona discharge treated polyethylene terephthalate film with a total light transmittance of 85% or more and less than 90% at 1200 nm, and dried with warm air at 90°C for 2 minutes to determine the dry coating film thickness. A white mask layer with a thickness of about 3.0μ was formed. The total light transmittance of this white mask layer was measured from the base film side: 48% at 600nm, 54% at 800nm, 60% at 1000nm, and 60% at 1200nm.
It was 66%. Next, on this white mask layer, a photosensitive solution with the following composition was applied using a wire bar, and dried with hot air at 90°C for 1 minute and 30 seconds to form a photoresist layer with a dry coating thickness of about 2.0μ. formed.

1-2-naphthoquinone diazide photosensitive liquid (Photosol manufactured by Tokyo Ohka Co., Ltd.) 10g Methyl ethyl ketone 20g A negative original was placed on the mask image forming material of the present invention having a photoresist layer on the white mask layer formed above, and an ultra-high pressure mercury lamp was used. Exposure amount 200 ^m with light source (Jet Light 2kW manufactured by Oak Seisakusho Co., Ltd.)
Exposure was performed from the original side at J/cm ² and an exposure time of 20 seconds.
Next, this exposed mask image forming material of the present invention was immersed in a 1% NaOH aqueous solution at 20°C for 90 seconds, and then
When developed by rubbing with absorbent cotton in tap water, the exposed areas were removed and a clear negative image with a slightly yellowish white color was obtained.

After draining and drying, the film was re-exposed using the above light source at an exposure dose of 200 ^mJ /cm ² , and the yellowish coloration was almost completely erased, yielding a negative white mask image.

This negative white mask image was exposed using a high-intensity xenon flash lamp light source (Riso-Xenofax FX-180, manufactured by Riso Kagaku Kogyo Co., Ltd.).
3.9J/cm ² , exposure time 1/1000 seconds from the support side
After repeated exposure 100 times, no damage was observed in this negative white mask image.

On the other hand, when a black negative image obtained by developing a silver halide lithium film using gelatin as a binder was exposed in the same way, the black silver image area absorbed xenon flash lamp light and heat was generated after one exposure. This caused thermal damage to the gelatin binder, making it impossible to use the negative image again.

When the above-mentioned negative white mask image repeatedly exposed 100 times was used as a negative transmission original of a heat-sensitive recording material described in Example 1 of Japanese Patent Application No. 58-205683, it was found that the heat-sensitive recording material had no background fog density. The white mask image of the present invention was useful as a transparent original.

Thermal recording material described in Example 1 of Japanese Patent Application No. 58-205683 Carbon black (average particle size 22 mμ) 4 g 10% ammoniacal aqueous solution of 2-hydroxyethyl methacrylate/methyl methacrylate/methacrylic acid copolymer 20 g Distilled water 36 g Surfactant: 0.1 g The above composition was dispersed using glass beads to prepare a coating liquid.

This coating solution was applied onto a polyethylene terephthalate film having a thickness of 100 μm and dried to prepare a heat-sensitive recording material having a dry coating weight of about 2.0 g/cm ² .

Example 2 A photosensitive solution having the following composition was used in place of the photoresist of Example 1, and was applied onto the same white mask layer as in Example 1, dried at a temperature of 90°C for 1 minute and 30 seconds,
A photoresist layer having a dry film thickness of about 1.0 μm was formed.

Acrylamide/diacetone acrylamide copolymer (copolymer consisting of 60 mol% acrylamide and 40 mol% diacetone acrylamide)
1g Distilled water 19g P-diazodiphenylamine/paraformaldehyde condensate 0.05g Silicone diameter surfactant (manufactured by Dow Corning)
XB-2725) 0.01g A positive original was placed on the mask image forming material of the present invention having a photoresist layer on the white mask layer formed as described above, and the exposure amount was 100 mJ/cm ² and the exposure time was 10 seconds from the original side. exposed. Next, this exposed mask image forming material of the present invention was washed with running tap water at 20°C for 10 seconds, and then soaked in a 4% aqueous solution of sodium alkylnaphthalene sulfonate (Perex NB Paste, manufactured by Kao Soap Co., Ltd.) for 30 minutes. After 60 seconds of immersion at ℃, the unexposed areas were removed and a clear white negative image was obtained by rubbing and developing with absorbent cotton in tap water.

Similar to the negative white image obtained in Example 1, this negative white image had light resistance to high-intensity xenon flash light.

Further, when this negative white image was used for a negative transmission original of the heat-sensitive recording material described in Example 1, the heat-sensitive recording material formed a clear black positive image with no background fog density, and the white color of the present invention The images were useful as transparencies.

By making the mask layer white, the mask image forming material of the present invention does not damage or erase the image even if it is repeatedly exposed to an extremely powerful light source, and improves the light resistance, which has not been good in the past, thereby making it suitable for thermal photography. The material could be used as a mask material.

Claims (1)

[Claims] 1 A white mask layer and a photoresist layer are sequentially laminated on a substantially transparent support, and the total light transmittance of the white mask layer including the support is 70% or less in the wavelength range of 600 to 1200 nm. A mask image forming material for a thermal photographic material, characterized in that: