JPS60149045A - Mask image forming material - Google Patents

Abstract

PURPOSE:To enable formation of a transmittable original without receiving damage at all from a light source having high intensity by forming a transparent base and a mask layer thereon so as to have respectively specific total ray transmittances and forming a photoresist layer on said mask layer. CONSTITUTION:A white mask layer having <=70% total ray transmittance at 600-1,200nm wavelength region is provided on a transparent base having >=80% total ray transmittance to visible light and near IR rays and further a photoresist layer is provided on the mask layer. A polyester film, triacetate film, glass plate or the like is used for the base. The mask layer is constituted preferably of a white pigment and film formable polymer. The white pigment is incorporated at 5-500wt% by the weight of the film formable polymer. The photoresist layer consists of a photosensitive and film formable material and has the nature that either of only the exposed part or the non-exposed part can remain on the white mask layer and that the residual part is insoluble with an etching soln. The transmittable original of which the image is not damaged even if the original is exposed by a powerful light source is obtd. by the above- mentioned constitution.

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. , such as xenon lamps, halogen lamps, tungsten lamps, etc., which are particularly light resistant to intense xenon flash lamp light, and heat sensitive I [!
Mask useful for forming a transparent original using the ll image forming method @
Relating to imaging materials.

As an image forming method, as described in Example 6 of Published Publication No. 11i454-1087.0, heat-sensitive bacterial molecules and particles dispersed in the heat-sensitive polymer absorb light and generate heat. A method is known in which a heat-sensitive recording layer made of material particles to be converted, such as carbon black, is provided on a support, a transparent original is stacked on top of the other, and a recorded image is formed by exposing and developing the original from the original side using a high-intensity xenon flash source. There is.

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 is much easier to operate than polymer-based photosensitive materials. However, in this method, exposure involves visible light and near-infrared light #11 as described in Example 6 of the aforementioned Japanese Patent Publication No. 54-10870.
The original conditions of irradiation energy of 1.8 J/crl and g-light time of 1/10110 seconds are all required, and the light YM is extremely strong compared to the conventional photosensitive forest materials mentioned above. Furthermore, when the heat-sensitive recording layer and the transparent original are overlapped and exposed from the original barrel side, the original is exposed to this strong light source, so the original used in this exposure method is repeatedly shielded from visible light and near-infrared light. It must have sufficient lightfastness to allow the film to be exposed to light and must not be damaged by exposure to light.

However, in the above exposure method, when using a transparent original composed of line drawings or halftone dot images, if the transparent original is, for example, a silver halide lithium film made of blackened silver distributed imagewise in a ceratin binder, However, when exposed to light, the blackened silver in the image absorbs light and generates heat, causing thermal damage to the serine binder and causing damage or disappearance of the image.

It is an object of the present invention to provide a method for forming a thermal image, in which the image is not damaged even when exposed to an extremely powerful light source such as the above-mentioned tube-enhanced xenon flash lamp light;
An object of the present invention is to provide a mask imaging material useful for forming a mask.

As a result of intensive studies to achieve the above objective, the inventors of the present invention found that
80% total light encounter rate for visible light and near-infrared light
White color and wavelength range 600 to 1
A mask image-forming forest material comprising a mask layer having a total light encounter rate of 70% or less at 200 nm and a photoresist layer provided on the mask layer is highly K 9 such as the S1 intensity xenon flash beam light described above. The present invention was completed based on the knowledge that a transparent original for a thermal image forming method can be provided which is not damaged by a high-temperature light source.

That is, the gist of the present invention is to provide a transparent support that is white and has a total light transmittance of 70% or less in an influence area of 600 to 200 nm on a transparent support that has a total light transmittance of 80% or more for the PJ viewing direction and near infrared rays. The mask image forming material has a mask layer, and further has a photoresist layer on the mask layer.

The present invention will be explained in detail below.

The support in the image-forming forest material of the present invention is a transparent chisel material that has excellent dimensional stability and has a total transmittance of 80% or more for visible light and near-infrared light, and is unique to this support. , plastic films such as Holies Null film, triacetate film, polycarbonate film, polyimide film, polysulfone film, polystyrene film, polypropylene film, +M4 resin board such as acrylic resin board, polycarbonate resin board, polyester resin board, glass board, etc. The above-mentioned support may be made of aluminum, copper, bismuth, chromium, brass, indium oxide, etc., or may contain dyes and pigments, as long as the total light transmittance for visible light and near-infrared light does not become less than 80%. However, 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 or an electric discharge treatment may be applied to the support, if necessary. You can leave it there.

According to the present invention, on the above-mentioned support, it is white and has a total light transmittance of 70% in the wavelength range of 600 to 1200 nm.
The mask layer required below is provided. Mask 1- is preferably composed of a white pigment and a film-forming polymer. As white pigments, babata m1ntJl, dtita7
(TiO2), m'jl=lead carbonate (2PbCO8
-Pb(,0H)t), LitoponejZn8 and B a
Composite M material I consisting of S 04 can be prepared, and its content is 5 to 5% of the film-forming polymer so that the total light encounter rate in the mask layer's influence range of 000 to 1200 nm is 70% or less. 500 turtles 1m% preferably 3
0 to 300, please call the Sumire staff.

Film-forming polymers include water, alkaline water injection solution, acidic water bath solution, neutral salt water solution, hydrocarbon-based halogenated hydrogenated yarn commonly called Minamisonuma agent, alcohol-based, ether-based, and acetal yarn. , ketone series, ester series, polyhydric alcohols and their derivatives, fatty acids and liquid organic compounds such as phenol threads, nitrogen compound threads, etc., such as hexane, toluene, xylene, carbon tetrachloride, trichloroethane, methanol, ethanol, and alcohols. propatool, tetrahydrofuran, methyl ethyl ketone, ethyl acetate,
Methyl cellosolve, ether, etc. singly or in mixtures can be used for electromolecularization @ monodemeri, tatoe is ceratin, methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, calhoki, cinyl methyl cellulose, polyvinyl alcohol, polyacrylic disodium, Water-bathable resin such as polyethylene oxide; cellulose acetate, cellulose dissolved in propionic acid, l:lll1:
11m of cellulose steel such as hacellulose; polyvinyl acetate, polyvinyl formal, polyvinyl butyral, vinyl chloride-vinyl acetate copolymer, vinyl chloride-vinyl acetate-vinyl alcohol copolymer, vinyl chloride-vinyl butyrate-maleic acid copolymer Copolymer, vinylidene chloride-vinyl chloride copolymer, vinylidene chloride-acryloni copolymer, ethylene-vinyl acetate copolymer, methacrylic acrylate ester copolymer, styrene-maleic anhydride copolymer partial ester Acrylamide-diacetone acrylamide copolymer, methacrylate dimethylaminoether-methyl methacrylate copolymer, methyl meccrylate-2-hydroxyethyl methacrylate copolymer, methyl vinyl ether-maleic anhydride copolymer,
Vinyl resins such as vinyl vitritone-vinyl acetate co-contaminated @r body; phenolic resins such as resol type phenol resin, novolac type phenolic resin; nylon resin; saturated polyester resin, etc. It should be noted that the thickness of the film formed on the support by the molecularized material containing the white pigment is preferably 0.5 to 20 .mu.m, more preferably 2 to 8 .mu.m.

A photoresist layer is disposed over 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 is developed by exposure to ultraviolet rays, visible light, etc. in water, alkaline water bath, acidic water bath, neutral salt water bath, or disintegrating solvent. The compatibility, wetness, etc. change with respect to the room, and only either the exposed part or the non-exposed part can remain on the white mask layer, and the remaining part is the white mask layer. Water, alkaline bath liquid, acidic bath liquid,
Various conventionally known photoresists described below can be used as long as they have the property of not bathing in etching solutions such as organic F6 agents.

(1) A photosensitive resin made by combining a 1,2-naphthoquinone diazide group and an alkali-based resin, for example, as described in Takahiro Tsunoda's "Sensitive Photosensitive Resin," published by the Printing Society of Japan in 1981, pp. 78-79. 2.3.4-)lyoxypenzophenone-3,4-bis[naphthoquinone-
1,2-diazide-5-sulfo/acid) niestermetacresol formaldehyde l11 fat (novolac type) mixture, 2-[naphthoquinone-1,2-diazide-5-sulfonyloki7-oxynaphthalene and shellac or a mixture of styrene-maleic anhydride copolymer, naphthoquinone-1,2-diazide-5-sulfanilide and 4-aminostyrene (5t 11L combination)
Naphthoquinone-1,2-diazide-5
- A mixture of sulfone rice novolac ester and phenol-formaldehyde resin (novolac type) is available.
-5 Hipley's AZ series, Kodak in the US
Company's KAP (type 3), Fuji Rakuhin Kogyo Company's F
Examples include PPR1 Photosol from Tokyo Ohka Kogyo Co., Ltd.

(2), diazo resin and water-soluble t'4: photosensitive resin that is a combination of resin or alkali-soluble resin, photosensitive resin that is a combination of diazo resin and water-soluble resin or alkali-soluble resin, P-diazodiphenylamine Diazo resin represented by paraformaldehyde compound, gelatin, polyvinyl alcohol, polyvinylpyrrolidone, hydroxyethyl cellulose, methyl vinyl ether-maleic anhydride copolymer, acrylamide
Photosensitive I@blood, which is a combination of all water-bathable resins such as Shea-1T acrylamide copolymer, or methacrylic l! #2 A photosensitive resin in combination with an alkali-soluble resin such as hydroxyethyl-acrylonitrile-methacrylic methyl-methacrylic acid copolymer is prepared.

(3) Photosensitive resin having an azide group as a photosensitive group Photosensitive resin having an azide group as a photosensitive group is a combination of natural rubber, synthetic rubber, cyclized rubber where a part of the rubber molecule is tl-cyclized, and an azide compound. Commuazide-based sensitivity 11 made by mixing Shikagame 9,
P-phenylene bisazide, P-azidobenzophenone, 4.4'-
Diazidobenzophenone, 4.4'-Diazidodiphenylmethane, 4.4'-Diazidostilbene, 4.4'-
Examples of the above azide compounds include diazidochalcone, 2,6-di(4'-azidobenzalnocyclohexane, 2,6-di(4'-azidobenzal)-4-methylcyclohexane).Commercially available rubbers -Azide photosensitive liquids are available in the United States such as AK's KTF solution, Tokyo Ohka Kogyo's gpt'it, OMI-L, and Fuji Rakuhin Kogyo's 1! ' SIL, Tissue Resist S1 manufactured by Kaihon Kagaku Kogyo Co., Ltd., and KY Resist manufactured by Yamatoya Shokai.

In addition, photosensitive resins incorporating an azide group into the molecule include polyazidovinyl benzoate, polyazidophthalic vinyl, polyazidostyrene, polyvinylazidobenzal, which are described in the above-mentioned "Photosensitive Resins", pages 104 to 105. Acetal, polyvinylazidonaphthyl acecool, azidopenzaldehyde-phenol 8411M, azidodiphenylamine formalin condensation polymer, etc. can be used.

Furthermore, photosensitive adhesives obtained by mixing the azide photosensitizer and polymer described in Enki 1"#Photosensitive Research, pages 107 to 108, such as 4,4'-diazidostilbene-
2,2'-disulfone anilide, 4-7 di)"-1-
Examples include photosensitive resins prepared by mixing phenylaminobenzene-2-sulfonic acid anilide or 4-4'-diazide chalcone with a novolac type phenolic resin.

(4) Photosensitive resin having a cinnamoyl group or cinnamylidene crystal as a photosensitive group Polyvinyl cinnamate is used as a photosensitive resin having a cinnamoyl group as a photosensitive group, and commercially available polyvinyl cinnamate photosensitive liquids are K01) A: KPR from K Company, TPI from Tokyo Ohka Kogyo Co., Ltd. (8PR from Sanpo Chemical Co., Ltd.). Militane acetate and its derivatives were opened, for example,
ii polyvinyl cinnamate-cinnamylidene acetate according to Nos. 56 to 57 of the above IXfr photosensitive resin,
polyvinyl penzoate cinnamyrite acetate,
Examples include polyvinylcarboethoxymethyl carbamate-cinnamylidene acetate, polypynylacetate-cinnamylidene acetate, and the like. In addition, polychloroethyl acrylic acid is reacted with potassium cinnamate,
Acrylic cinnamoyl type boria such as glycidyl methacrylate copolymer with all cinnamic acid added thereto can also be used.

(5) Photosensitive resin having an acryloyl group as a photosensitive group 10 to 40% by weight of monomer having an acryloyl group in total, 1 to 20% by weight of a photopolymerization initiator, dissolved or swollen in a developer, and capable of forming a 01-functional reflection. The polymer is lO~SON@%,
and other additives such as sensitizers and thermal polymerization inhibitors.
A photosensitive resin having a weight of 1 ljt% or less is dissolved.

The above monomer having an acryloyl group is
iJ-functional unsaturated acrylates, specifically polyester acrylates such as 1,6-hexanediol diacrylate, polyethylene glycol 200 diacrylate, diethylene glycol diacrylate, neopentyl glycol diacrylate, Ethylene glycol diacrylate, hydroxypivalic acid ester neopentyl glycol diacrylate, bis(acryloxyethoxy J bisphenol A1 bis(acryloxyboriethoxy 7), bisphenol A,)limethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol Hexaacrylate is preferable, and other examples include phenoxyethyl acrylate, stearyl acrylate, lauryl acrylate,
Methoxyethyl acrylate, N1N dimenalaminoethyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-methoxyethoxyethyl acrylate), 2-ethoxyethoxyethyl acrylate, 2-hydroxyethyl acryloyl phosphate, atrahydro Minor n-order acrylates such as furfuryl acrylate can also be used in combination with all the above-mentioned polyfunctional n-order acrylates.

Photopolymerization initiators include acetophenone, P-dimethylacetophenone, pentuphenone, PP-dichlorobenzophenone, Michler's ketone (4-4'-hisdimethylaminobenzophenone, benzyl, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether). , pentuin n-propyl ether, benzoin butyl needle, benzoin n
-butyl ether, 2-chlorothioxanthone, 2-methylthioxanthone, azobisisobutylnitrile, benzoin peroxide, 2.4.5-triphenylimidazole diplex, etc. can be used.

Film-forming polymers that can be dissolved or swelled in a developing solution include polyvinyl alcohol, polyacrylic acid, acrylamide-diacetone acrylamide copolymer, etc. when the developing solution consists of water alone. In the case of alkaline water, acrylic acid-methacrylic acid ester combination, styrene-maleic anhydride combination K
Il 1 minute esterified product, novolac type phenol Il@
Oil, nylon resin, etc. can be used. 1, the developer is
For example, in the case of an 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 gold having a photopolymerizable unsaturated group in the main chain, chain end, or side chain may be used in the above-mentioned composition as required.

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

Implementation 911゜Crow beads 801kA8fr-te were dispersed in the above composition for 6 hours using a paint shaker, and then mixed with m cloth. & I got it.

This coating has a wavelength range of 600 to 120 at a thickness of 1()0μ.
It was coated using a wire bar on a corona discharge treated polyethylene terephthalate film having a total light transmittance of 85% or more and less than 90% at 0 nm.
It was dried with hot air at .degree. C. for 2 minutes to form a white mask 11 having a dry coating thickness of about 3.0 .mu.m.

The total light transmittance of this white mask layer was measured from the base film side: 48% at 600 nm, 54% at 800 nm, 60% at 11000 nm, 1200 nm
nm VC was 66% C Next, on this white mask layer, a photoresist coated with the following KJl composition was applied using a wire bar, and dried with warm air at 90°C for 1 minute and 30 seconds to form a dry coating film. 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 as described above, and a photoresist layer having a film thickness of about 2.0 μm was formed. The exposure time was 20 seconds with exposure time of 20 seconds at exposure fi 200'''J/cd1 using a 2 kW GET light manufactured by Oak Seisakusho ■.

Next, the exposed area of the mask image forming material of the present invention was immersed in a 1st volume NaOH aqueous solution at 20°C for 90 seconds, and then rubbed and developed in tap water with absorbent cotton to remove the exposed area and form a clear, slightly yellowish white color. A negative image was obtained.

After draining and drying, the exposure amount is 200''iJ/c+ using the above light source.
Upon re-exposure at +1, most of the yellowish coloration disappeared, and a negative white mask image was obtained.

This negative white mask image 1 water * u gI # xenon flash lamp light source (manufactured by Riso Kagaku Kogyo Kuri ■, used Riso Xenofax n1x-180J +, Sumire Sumoto 3.
When the support was repeatedly exposed 100 times at 9J/Cr/ls exposure time of 1/1000 seconds, no damage was observed in this negative white mask image.

On the other hand, when a black negative image obtained by applying :fi to a silver halide lithium film containing ceratin as a binder was exposed in the same manner, it was found that the black silver image area was absorbed by Gysenon Fufutschlumb jl in the single exposure source. Heat was generated and caused heat loss to the gelatin binder, resulting in the use of negative images of 1+ degrees.

When the above-described white mask image repeatedly exposed 100 times was used as a negative transmission original for 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 a natural pre-density density. Clear black positive I [! 111 was formed, and one area of the white mask image of the present invention was useful as a transmission original.

Heat-sensitive recording material described in Example 1 of Application No. 58-205683 The above composition was dispersed using glass beads to prepare a coating solution.

This coating solution was coated and dried on a polyethylene terephthalate film with a thickness of 100μ, and the dry coating film was approximately 2.0 #
/(d) A heat-sensitive recording material was prepared.

Example 2゜In place of the photoresist in Example 1, a photosensitive liquid having the following composition was used and applied onto the same white mask layer as in Example 1,
It was dried with warm air at 90° C. for 1 minute and 30 seconds to form a photoresist layer with a dry film thickness of about 1.0 μm.

A positive original was placed on the mask image formation material of the present invention having a photoresist layer on the white mask layer formed as described above, and an exposure wrinkle was 100 mJ/cLIt.

Exposure was performed from the original side with an exposure time of 10 seconds. Next, the present invention mask II! of this exposure source! ll Image formation charge at 20'C
Rinse with running tap water for 10 seconds, then immerse in a 4% aqueous solution of sodium alkylnaphthalene sulfonate (manufactured by Kao Seiroku ■, Perex N) 3 Paste 9 for 60 seconds at 30°C, and then soak in tap water with absorbent cotton. When developed, the unexposed areas were removed and a clear white negative image was obtained.

Similar to the negative white Ukii water used in Example 1, the Igative white image showed poor lightfastness to high-intensity xenon flash light.

Further, when this adhesive tape 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 blur density, and the present invention The white image was useful as a transparency manuscript.

Claims (1)

[Claims] Total light transmittance for visible light and near-infrared light is 80%
White and wavelength range 600~
A mask image forming material comprising a mask layer having a total light transmittance of 70% or less at 12,000 m, and further comprising a photoresist J- on the mask layer.