JPS58192032A - Formation of polymerized image - Google Patents

Abstract

PURPOSE:To strengthen a polymer image part and to form a scratch resistant image, by developing a silver halide sensor type polymerizable photosensitive material, and uniformly exposing it after forming an image. CONSTITUTION:A vinyl compd. is added to a silver halide emulsion layer and/or its adjacent layer to form a silver halide sensor type polymerizable photosensitive material, and it is developed to form an image, and the whole surface is exposed after image formation. The vinyl compd. is polymerized in the presence of the exposed silver halide, and this method has high sensitivity, raises strength of a polymer image part, and forms an image resistant to scratches.

Description

[Detailed description of the invention] The present invention relates to a method for forming images using polymers.

The present invention relates to a method of selectively producing a polymer compound in a portion corresponding to photographic 1% by the action of a silver halide photographic emulsion and a reducing agent.

A halogenated bride sensor type 1 polymerization reaction characterized by polymerizing an ethylenically unsaturated compound which undergoes addition polymerization at the same time as the reduction reaction of silver decagenide in the presence of a W-based halide complex. Regarding optical materials.

It has been proposed that all ethylenically unsaturated compounds be combined together to form a polymeric compound to form gI. It has also been proposed to use silver halide gold as a catalyst for il reaction of element 1 (UK Patent No. F4).
4,47/Specification, S.

Levinos et al. Photographic Inc.

Science and O Engineering (Photog
rapic 5science & Engineer
ing) Volume 6, No. λ here - λ 26 pages (/ri 62)). In this reaction, the next product produced by photolysis of silver halide is thought to act as a catalyst for the @ junction, and the degree of g is not as high as when reducing halide steel particles by ordinary methods. Not obtained. Also, after developing the exposed nine-halide emulsion grains with a conventional developer solution, the resulting nine*
It has also been proposed to use m* or unreacted halogenated at as a catalyst to conduct a polymerization of ethylenically unsaturated compounds to form a polymeric compound in the form of an entire image (Belgian patent No. 2 Ko 77). statement, etc.). This reaction is a manipulation of Genwei]! There is a drawback that the operation must be carried out separately. The exposed silver halide is treated with a reducing compound in the presence of a totally ethylenically unsaturated compound, and the oxidation product or its intermediate product produced in the process is treated with a reducing compound to cause polymerization of the ethylenically unsaturated compound. 111 Benzenoidization is carried out in such a way that two or more water groups or amine groups or amine groups substituted with alkyl or aryl are already present in the ortho or -R positions on the benzene base. It has been proposed to carry out such a reaction by using an alcoholic acid as a reducing agent (U.S. Patent No. 3.
Volume 0, page 127j (/rij7)). However, in this example of a reaction using a benzenoid compound, only a friend observed an increase in the optical temperature of silver halide by 1111 degrees, and there was no increase in viscosity or generation of reaction heat, which directly supports the growth of polymers. No separation of the mackerel or the produced polymer was performed.

Furthermore, other researchers have reported successful follow-up tests (S, Levinos and F).
, W, H, Muller Photographic Sci x y
Mueller, Photograp
hic 5science) & Engineering (En
gineering) Volume 2
)).

Then, in the presence of j-based silver halide, using resorcinol, naphthol, pyrazolone, hydrazine compound, and phenol compound as a polymerization initiator, the ethylenically unsaturated compound tm is synthesized. ? issue,
Same to-io≠rr issue, same Hiroj-JOJ Jr issue, same 44
No. 4-277JJ, PI≠7-11111, Doko 6-
6st/No., Kai-7-/Senbu Meng No. 7, Same≠7-/≠≦1
1, Dotai 7-/4444 de, Dotai @7-72431, Dotai 7-λ07 Hiro 1, Dotai 7-/Yuburi, Interchanger/! No. 70, Dokkei Ta Hiroshi No. 17≦2 and Dokou? -10
4F7 issue, special request 1974-23 R/RI issue, % request! ≦−λ
r/! ≠ (Silver halide sensor type polymerizable W & optical material).

However, although these inventions produce polymers of ethylenically unsaturated compounds, the strength of the polymers formed is still not sufficient.

It is an object of the present invention to provide an overall sensitive method for polymerizing ethylenically unsaturated compounds in the presence of exposed silver halide. Another object of the present invention is to provide an iwi-sensitive silver halide photosensitive material that can obtain a polymer gI gold that is positive with respect to the silver halide front. Another object of the present invention is to improve the strength of the body image, the sound strength, and the resistance to scratches! 11g11: To provide a method of forming.

The Ministry of the Invention et al. used a suitable polymerization initiator (reducing agent) to reduce silver halide in the presence of ethylenically unsaturated compounds, which caused polymerization of the ethylenically unsaturated compounds, resulting in When a silver halide emulsion is used as silver halide, the reaction takes place quickly when the silver halide microcrystals contain existing nuclei, and therefore the reaction takes place under appropriate reaction conditions. If you choose the reaction time, it becomes your own nuclear! A silver halide sensor type that can selectively cause a reaction only in areas where silver halide grains exist! Societal Materials Association, t
An image formed by developing, etching, peeling, and exposing the entire surface to light! It was found that the strength was significantly increased.

It is known that the photopolymerization system improves the image intensity after photopolymerization. It is used in large amounts as a photopolymerization inhibitor as a polymerization initiator (reducing agent). It was unexpected that after treatment with JJS rice containing a large amount of photopolymerization inhibitor, the image intensity would improve with full exposure.

In the present invention, a chemical lamp, high-pressure mercury lamp, ultra-high-pressure mercury lamp, carbon arc lamp, xenon lamp, etc. is used to irradiate the entire surface after the development process. Irradiate for O seconds.

The silver halide sensor type polymerizable photosensitive material α of the present invention may contain a non-gaseous ethylenically unsaturated compound (vinyl compound) in the halide emulsion layer and/or the adjacent layer. It is preferable to include it. Undercoat layer,
It doesn't matter if the protective layer or intermediate layer is removed.

The silver halide ii contained in the photosensitive material of the present invention is suitably 0,007 t/7 m<2 >and particularly preferably o, ort to /f. The total amount of binder gold in each layer is 7m.
Hit o, it or 30? are suitable, and o, ry and/or st are particularly preferred.

The vinyl compound is preferably used at a ratio of 30 to 30 times as much as the binder in the same layer. When adding a polymerization initiator to the sensitive material, which will be described later, the polymerization initiator is added to the processing solution in a convenient amount of 1/10 mol to 10 mol per 1 mol of silver halide contained in the same area. Although the optimum concentration differs somewhat depending on the compound used, the appropriate concentration is from 171,000 mol to j mol/l, particularly preferably from 1,710 mol to 1 mol.

When adding to the vinyl compound top treatment solution, 0.7 per /
mol to j mol is suitable, especially 0.3-E- to 3
Moles are preferred.

The photographic latent image described in the present invention is a disastrous change that occurs in a silver halide photographic emulsion due to the action of electromagnetic waves or particle beams and is normally invisible to the naked eye. It is a pole that becomes a statue. In an emulsion that produces a normal positive image, a latent image is generated due to @VC, where development nuclei are generated in the skin silver halide grains when irradiated with electromagnetic waves or particle beams. agI is produced as it disappears upon irradiation (Jam
e5) and/' 1 Fundamentals of Photographic Theory (F.
'undamantals of Photogr
aphicTheory )-@2@Morgam
& Morgan.

Co., Ltd., published in 1260, see chapters 3 and μ).

The silver halide photographic emulsion used in the present invention is a conventional halogenated iron emulsion which, by the action of electromagnetic waves or particle beams, generates a full-field nucleus in the irradiated area, that is, a negative image is generated by the action of the electromagnetic wave or particle beam. It can be used as a direct positive emulsion, and it can also be used as a so-called direct positive emulsion, in which a larger number of halogen particles exist in the other areas than in the areas irradiated with light.

In the present invention, silver halide photographic emulsions which yield 15jIINI are conveniently used, such as silver halide photographic emulsions used for conventional processing.

That is, silver chloride, silver bromide, silver chlorobromide, silver iodobromide, and silver chloroiodobromide 4 true emulsions can be conveniently used. The photographic emulsion commonly used in the present invention has chemical sensitization and optical sensitizing dyes that are superior to ordinary photographic emulsions. That is, as chemical sensitization, it is possible to perform sensitization by sensitization, noble metal sensitization, and reduction sensitization.
Photographique) li4λ version Photocinema Hall Montel Paris (Photocinema
Paul Montel Paris)/rit7
(See Year λμ7-30/jj). The Theory Op.
The Photographic Process
y of the PhotographicP
rocess) 1st edition Macmillan
See Chapter 1, published in 1977. In addition, for optical sensitization,
Optical sensitizing dyes used in the normal Yoshin method such as cyanine dyes and merocyanine dyes (for example, Makoto Kikuchi et al.
Volume 2, Published by Maruzen in 12 years, Volume 1, page 1) is valid. Furthermore, the emulsion used in the present invention may contain stabilizers such as those used in conventional photography.

The directly anointed silver halide odor-doping emulsion that can be conveniently used in the present invention can be exploited by solarization, the No. 1-shell effect, the Kleiden effect, and the Sabache effect. 1l12kJA with these effects are, for example, C and E.

The Theory of the Photographic Process by K.
of the Photographic Pr
ocess), Second II (MACMILL
It is described in Chapters 6 and 7 of the publication published by AN) Co., Ltd., 2010). Solaris (-John) is used to directly create a positive silver halide emulsion.K creates a type of halide fs emulsion that is easy to use for solarizing, and allows for sufficient ms without image exposure. All you have to do is expose the entire surface to light or apply a chemical to it. Examples of how to make such an emulsion can be found in, for example, the British Percentage Permit No. 1Q Co. 4 It-4 Specification and Equivalent Goo No. 2 Fu No. 30. This can be seen in detailed documents, etc.

The Burschel effect is caused by exposing the entire exposure tube to a long-wavelength halogen compound, which has the possibility of full KIA exposure due to chemicals, but in this case. Copper halide emulsions containing a large amount of silver chloride are advantageous, and desensitizing dyes such as pinacryptol yellow and phenosafranine fat may also be added to promote the Herschel effect. Direct positive I that fully utilizes the Barshell effect
For example, the method of manufacturing JL ceremonial medicine is as follows:
This can be seen in the specification of No. t, U.S.A.

In order to obtain direct sunlight using the Kleiden effect, it is necessary to expose the whole surface to light at a relatively low illuminance after giving a long exposure at a high illuminance, and it is necessary to expose the entire surface to light at a relatively low illumination. , 7IIJ of illuminance, the portions that did not receive the image light become developable.

The Sabache effect is produced by exposing a copper halide emulsion to light in an imagewise manner, and then immersing it in a current GII solution and then applying it to the entire surface in the next state, or by being subjected to the action of a chemical agent. This occurs depending on whether the process is developed without receiving FCS. The Kleiden effect and the Sabache effect are
Depending on the initial exposure, halogenation can occur easily and practically when using a halogenated complex emulsion in which there is a strong tendency for Kaede gI nuclei to form inside the grains, even on the surface of the grains. .

Examples of methods for manufacturing emulsions that tend to cause internal S development nuclear noise include rice! iii%FFth λ,! No. 12,210 qm, U.S. Patent No. 2,4!97,17 specification, English 1ii1%
Author: t, oit, otx44rEIJm, Germany!
First permission. It is described in Ko 57,7F/'ijj specification honor etc.

It is also possible to create positive l1jl using a core-shell emulsion. The method for producing core-shell emulsions is described in U.S. Patent Nos. 3 and 7.
4/, No. 276 Specification, U.S. Patent No. 3゜Co04.171
No. Specification - IK has been modified.

The above four true emulsions contain halogenated f1 in a solution of a polymeric substance.
Gelatin is widely used as the polymer material, but other water-absorbing colloids can also be used. For example, gelatin derivatives, graft polymers of gelatin and other polymers, albumin, casei/white matter: hydroxyethyl cellulose, i-carboxymethyl cellulose, cellulose derivatives such as cellulose sulfate linkages, IIWh conductors such as sodium alginate, starch derivatives, etc. ; Polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid (or poly(meth)acrylic acid ester-bonded with glycidyl (meth)acrylate), poly Multiple synthetic hydrophilic polymeric materials such as single or copolymers of acrylamide, polyvinylimidazole, polyvinylpyrazole, etc. can be used.

As the gelatin, in addition to lime-treated gelatin, acid-treated gelatin may be used, and gelatin hydrolysates and gelatin enzymatically decomposed products can also be used.

As gelatin derivatives, a wide variety of compounds such as acid halides, acid anhydrides, incyanates, bromoacetic acids, alkanesultones, vinyl sulfonamides, maleimide compounds, polyalkylene oxides, and epoxy compounds can be added to gelatin. The product obtained by the reaction is used. A specific example is the United States, which has a total of 2.4/44. Ri No. 21,
Same 3. /Jλ, riμj, same 3. IIt, IIIt issue,
3°31λ, No. 153, British Patent No. 161. Hiroshi / Sango,
Same/, OJI, /I issue, Same/, 00! , 71
No. 47, Special Public Sho Squirrel - 2tr Hiroshi! It is written in the number etc.

The gelatin graft polymer may include gelatin, acrylic acid, methacrylic acid, their esters, derivatives such as amides, acrylonitrile, styrene, etc., vinyl-based heptad polymers (homo) or co-mert polymers.
Crafted items can be used. Particularly preferred are graft polymers of gelatin and certain compatible polymers such as acrylic acid, methacrylic acid, acrylamide, methacrylamide, hydroxyalkyl methacrylates, etc. These examples are identical to US Pat. No. 747,4.2.

III, No. 747, Same, Pst, It No. 6, etc. 6 Representative synthetic hydrophilic polymer substances are
H1 patent issue 1ii (OL8), xiλ, 7or,
US Patent 3. ≦20, 7jtI No., IW, I3゜17
De, No. 201, and the one described in Special Publication No. 11-7-61.

The light-sensitive material of the present invention may contain an inorganic or organic hardening agent. In addition, various known surfactants may be included for various purposes such as coating aids, antistatic properties, improving slipperiness, emulsifying and dispersing, and preventing adhesion.

In the present invention, the vinyl compound (ethylenically unsaturated compound) is a liquid or solid compound or a mixture thereof that is liquid or solid at room temperature. use Such compounds include acrylide, acrylonitrile, N-hydroxymethylacrylamide, methacrylamide, Nt-
Butylacrylamide, methacrylic acid, acrylic acid,
Acrylic plate calcium, sodium acrylate-methacrylamide, methyl methacrylate, acrylic removed, ethyl acrylate, coacrylamide 1-methylpropa/sulfonic acid, vinylpyrrolidone, λ-vinylpyridine, l-vinylpyridine, comethyl- Hevinylimidazole, potassium vinylbenzenesulfonate,
Examples include vinyl carno τ sol. In the present invention, compounds having two or more vinyl [1%] are advantageous;
It is used in combination with a compound having a vinyl group 1r+ as described above, or alone as a compound having a plurality of vinyl groups 1r+. An example of such a compound is N.

N'-methylene bisacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, divinyl ether, divinylbenzene bisphenol-
Dimethacrylate, trimethylolbrono-dryacrylate, interaerythritol tetraacrylate, bisoxyethylated bisphenol-A-diacrylate, diintererythritol hexaacrylate or urethane group [containing unsaturated conjugates such as di(
J I-methacryloxyethyl)-λ.

≠-tolylene diurethane/diol mono(
Examples include reaction products of meth)acrylate and diisocyanate.

In the present invention, polymerization can be carried out easily using a water-soluble vinyl compound, or by adding a water-insoluble vinyl compound dissolved in an appropriate solvent as an emulsion. Emulsification can be carried out according to a conventional method in the presence of a surfactant and/or a polymer compound using a suitable stirring device.

In the present invention, the above vinyl compound can be added to the silver halide emulsion layer. The binder of the polymerizable layer contained in the vinyl material is a natural or synthetic polymer that is soluble or at least swellable in water or an alkaline aqueous solution. Examples of such natural polymers include gelatin, as well as binders in silver halogenide emulsions.
Examples of synthetic polymers include gelatin derivatives and gelatin graft polymers, starch, dextrin, polysaccharides, cellulose derivatives, diethylene, etc.
Acrylic acid or methacrylic acid alone or combined together, polymers containing free carboxyl groups such as copolymers of Malay/#R1 itaconic acid, vinyl ammonium, and sulfuric acid, and sulfonic acid groups such as sodium styrene sulfone copolymers. M-containing polymers, carboxylic anhydride group-containing M polymers such as maleic anhydride and itacone anhydride transparent copolymers, novolac resins such as phenol-formalin resins and cresol-formalin resins, polyhydroxystyrene, polyvinyl alcohol, and vinyl alcohol copolymers, etc. Hydroxy co-containing polymers of Examples include nylon, methoxymethylated nylon, and polyalkylene glycol.

The coloring material t-addition may be 0 to the above polymerizable layer.

Coloring materials include metal oxides such as acid 4t titanium, curved lead oxide, and iron oxide, pigments such as carbon black, phthalocyanine pigments, and azo pigments, xanthine dyes such as rhodakine, and triphenylmethane such as crystal violet. Dyes such as thiazine dyes such as methylene blue, azo dyes, and anthraquinone dyes are used. It can be added to dyes or pigments according to conventional methods such as dissolving, emulsifying, and dispersing.

A plasticizer may be added to the heavy layer. Examples of the plasticizer include dimethyl phthalate, diethyl phthalate, dibutyl phthalate, diisobutyl phthalate, dioctyl phthalate, octyl capryl phthalate, dicyclohexyl phthalate, ditridecyl phthalate, and butyl benzyl. Glycol esters such as phthalate, diindecyl phthalate, diaryl phthalate natonoheptalate ester, dimethyl glycol phthalate ethyl phthalylethyl glycol, methyl phthalylethyl glycol, butylphthalyl butyl glycol, triethylene glycol cycaprylate, Cresyl phosphate, triphenyl phosphate and other acid esters, diisobutyl adihart, dioctyl azide are one
Examples include aliphatic dibasic acid esters such as dimethyl sepacate, dibutyl sepacate, diisooctate, and tyl azelate, rienoic acid) IJ-1-tyl, glycerin triacetyl ester, and zotyl laurate.

A known surfactant may be added to the monochromatic coloring material layer for the purpose of improving coating properties.

TS image of the above silver halide sensor type 1 composite photosensitive material (
When carrying out the reduction reaction of silver halide and the polymerization reaction of vinylated adducts, the following polymerization initiators are used. The polymerization initiator may be contained in one film of the sensitive material or may be contained in the developing solution, but in order to achieve the object of the present invention, it is preferably contained in the developing solution. The method for preparing the material may be by immersing the black material in the liquid or by heating it only.

In the present invention, the following polymerization initiators are used. The polymerization initiator may be used alone or in combination with other glazes.

In the present invention, the polymerization initiators include resorcinol and its derivatives, naphthol and its derivatives, pyrazolone compounds, hydrazine compounds, catechol and its derivatives, p-phenylenediamine, m-phenylenediamine, alkylphenol, etc. You can use whatever you have. (% Kosho II-t
-///4I issue, 10-10μit issue, same t-3
No. 013, Dokei ≦-27723, N-7-yrzr
No. 1, e+-tzri No. 1, Open-7-74'447,
same! 7-iattr issue, 447-/#44ri issue, same<
47-/2tl1, same (47-20717/, same V
Tah/! No. 6, same getter/! No. 70, Taruhiro 17
6ri No. 6 and the same Vter 106ri No. 7].

It is also possible to use phenolic compounds represented by the following general formula.

General formula) In the formula, R1 represents an alkyl group or a substituted alkyl group,
R2 and R'2 each represent hydrogen, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, an aralkyl group, or a halogen atom, and R3 and R/3 each represent hydrogen, an alkyl group, a substituted alkyl group, an aryl group, Contains a substituted aryl group, aralkyl group, alkoxy group, thioalkyl group or haloken atom.

(II) (nl) CN) (JH (■n formula, 8 represents an oxygen atom or a sulfur atom,
Alkyl group, fil [M represents an alkyl group, aryl group, m-substituted aryl group or aralkyl group, R2 and R1'
2 each represents a hydrogen atom, an alkyl group, a substituted alkyl group, an alkoxy group, a thioalkyl group, an aryl group, a substituted aryl group, or a halogen atom; ,−
CH2-1 substituted aryl crystal or aralkyl group,
R2 and B/2 are each water X &amp; alkyl group, WIt
Substituted alkyl group, alkoxy group, thioalkyl group, aryl group, substituted aryl group or halogen atom? Clothes, k
L3 represents an aryl group, substituted lum or aralkyl group, X represents -CH2-1H3CH3-C-2, and n represents an integer 1 of /h·raμ.

[■] [-] In the formula, R1s R2, R3, and R4 each represent hydrogen, a rogone atom, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, an alkoxy group, a thioalkyl group, or a cyan group, and RIs R2, R3, )t4 represents a halogen atom.

Specific examples of phenolic compounds include the following.

([03)3u H3 C2H50 CH30 CH30 CH3 CH3 HOCH.

(n) C4Hg S CH30 CH30 H(, L; t13 H30 Hs0 C(JOH aa OHOH a α α a α 11 Br OH polymerization is promoted.

Sulfite ions may be added, for example, as compounds that already carry sulfite ions, such as alkali metal or ammonium sulfites or bisulfites, or as alkali metal or ammonium pyrobenzyl salts, or as sulfite ions. It may also be added as an additive, such as an adjunct between silicate and an aldehyde such as formaldehyde or glyoxal, which decomposes in the bath solution to generate sulfite ions. Excessive addition of sulfite ion Ii is caused by the reaction yarn itm being 0.002 mol or more depending on the phenol compound used, the seed koji and amount of vinyl monomer, and the pH of the system.
Particularly, o, oi moles or more are effective.

! li! Although the mechanism of action of sulfuric acid is not clear, it seems reasonable to think that it prevents the inhibitory effect of oxygen.

The 11-unit reaction can be accelerated by using a small amount of ordinary Yoshinkei GII drug or by pre-bathing with ordinary photographic dust and mulberry.

-NH2 or -N HR, where n is an integer 1r of μ or less, and R is a group selected from alkyl groups, hydroalkyl groups, alkoxyalkyl groups, and alkylsulfonamidoalkyl groups with a total carbon number of 1 or less, or Aryl base table. ), l-aryl-3-ocnovirazolidines, and/-aryl-3-iminopyrazolidines. Although these ordinary photographic developing agents do not have the effect of causing 1 polymerization by themselves, are they due to the mechanical effect of reducing agents that have the effect of initiating polymerization? By promoting the reaction, one reaction can be accelerated.

This reaction is generally carried out repeatedly under alkaline conditions, but the most appropriate pH varies depending on the A1 and A11 degrees of the halogenated plate, phenol compound, and medium polymer compound, and the reaction temperature.
At pHFJ of 1 or higher, the reaction is i' possible, and at pHFJ or higher, it is suitable for powder.

The reaction can be stopped by making the system acidic (e.g. pHs (below r)), cooling, dissolving the silver halide using a photographic fixer,
Alternatively, it can be easily stopped by adding a polymerization inhibitor to the system, but it can also be stopped by immersing the polymerizable layer in a treatment solution (along the etching line) that can be used to decompose the polymerization layer and eluting the uncoupled parts. can do.

Is there a photoinitiator in the polymerizable layer of the halogenated sensor type photosensitive material used in the present invention? Adding it is particularly preferable in view of the effects of the present invention.

Examples of photoinitiators for the photosensitive composition used in the present invention include conventionally well-known ones such as benzoin, benzoin methyl ether, benzoin ethyl ether, α-methylbenzoin, α-ethylbenzoin, benzyl, diacetyl, and copolymer. Naphthalene sulfonyl chloride, diphenyl disulfide, anthraquinone, benzophenone, di-tcrt-butyl peroxide, eosin, thionine, acetophenone, triphenylphosphine, λ-ethyl anthraquinone, coated t-butyl anthraquinone, β
-Methyl anthraquinone, AIBN, benzanthrone, benzoylacetone, benzoyl peroxide, tetramethylthiuram monosulfite, diphenyl disulfide and the like. These photoinitiators are conveniently used in an amount of o, ooi to 10 parts by weight per 100** parts of monopolytic hinyl monomer.

In the photosensitive material produced using the present invention, there is a monochromatic coloring material layer containing a vinyl compound and a coloring material, and a rogogenated photographic emulsion layer and other layers normally used in the photosensitive material. It can be applied to flexible supports such as plastic film, paper, and cloth, as well as rigid supports such as glass, ceramic, and gold maple. The flexible support 7 used in 1 is made of a semi-containing polymer such as cellulose nitrate, cellulose acetate, cellulose acetate, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, etc. films, baryta layers or a-olefin polymers (e.g. polyethylene, polypropylene, ethylene/
Paper coated with or laminated with butene. Is the support dye or pigment? It may be colored using.

It may be made black for the purpose of blocking light. The surface of these supports is coated with one coat to improve contact with the polymerizable layer and the like. The surface of the support is treated with corona discharge,
Ultraviolet irradiation and flame treatment may also be applied.

Suitable metals for forming the hydrophilic surface used in the present invention include metals such as aluminum (including aluminum alloys), curved lead, iron, copper, etc. It may be laminated or vapor deposited to form a composite support, or it may serve as a support itself.

Among the supports of cfL et al., aluminum plate,
Preferred is a composite sheet in which an aluminum sheet is bonded to a polyethylene prephthalate film as described in Japanese Patent No. 1-11327.

Since these supports have a hydrophilic property, they are subjected to surface treatment or treatment such as providing a water-seeing layer, if necessary. There are many types of hydrophilic treatment.

In the case of metal, especially aluminum, surface-bearing supports, surface treatments such as graining, silicate sorting, immersion in an aqueous solution of fluorozirconate, potassium phosphate, or other oxidation treatments can be used. It is preferable that this is done. Also, the US percentage; z, y/a, o6t4
Aluminum plate, grained and then immersed in a sodium silicate water bath, as described in the r3 specification, US%i! Fl-No. 3゜/l/, in specification No. 57!
An aluminum plate which has been subjected to positive and oxidation treatment as in iegrit, and then immersed in an aqueous solution of alkali gold silica is preferably used. The #A polar acid oxidation treatment described above, for example, inorganic acids such as fI4, chromic acid, sulfuric acid, boric acid, etc., or inorganic acids such as &, 'l, M acid, sulfamic acid, or aqueous dissolution of these acids, or An electric current is applied to an aluminum plate in an aqueous solution of phosphoric acid, Im-excludes or these admixtures, preferably in a non-aqueous solution of a number of single- or two-pole combinations. It is carried out by flowing. Also, the American sign F? Electrodeposition of silicate as described in No. J, Gtf, AA.lambda. specification also works. In the process described in the specification of the I, IOR, and λ Co., Ltd. to the United Kingdom, an aluminum plate was dissolved in an acid-resistant electrolytic solution with alternating current, and then soaked in a sulfuric acid electrolyte. Of these, an aluminum plate that has been anodized and oxidized in the above process is also preferably provided with an undercoat layer of cellulose thread resin containing a water-soluble salt of a metal such as curved lead. This is preferable in terms of preventing scum during printing.

In the VC of the present invention, any electromagnetic waves or particle beams to which ordinary photographic agents are sensitive can be used as the electron beam or particle beam that can be conveniently used to obtain a photographic image. M
llchi town holiday light, ultraviolet rays, 7.3μ up and down infrared rays, X
Particle beams such as rays, force/magnetic rays, electron beams, and Alfé rays can be applied. In particular, the ordinary mandencho, that is, tungsten'-
A variety of well-known devices such as fluorescent lamps, mercury lamps, xenon, arcna 1, charcoal arc lamps, xenon flash lamps, Haloken lamps, light emitting diodes, cathode ray tube flying spots, discharge tubes such as claw tubes, and laser sources such as argon lasers. It can be used in any light source.

Jikojikaku not only uses an exposure time of 10 seconds from 771,000 seconds, but also uses xenon flash lamps, cathode ray tubes, laser ft, etc.//1
0 ~/// You can use a 0 second photo-light session, or you can use a 50 second long I! You can also use the original. Depending on needs, the spectral composition of the light used for exposure can be adjusted using a color filter.

Sou Example L 110 benzyl methacrylate-methacrylic acid co-units (t
o:ao) o, zy, pentaerythritol tetraacrylate o, ty and p-methoxyphenol 0.0
/ was dissolved in methyl ethyl ketone / ≠ 21 ethylene glycol monomethyl ether acetate / 2 and cyclohexanone j2, and after adding Microlith Black CAI carbon) 0 ° tvl Michler's ketone o, ooty, it was dispersed with a small dispersion machine and applied as an undercoat. VC coating was performed on a polyethylene terephthalate film to obtain a heavy layer of film #coμ.

♂! It was prepared using silver halide t-ceratin consisting of a mol of silver chloride and a mol of a mol of silver bromide, and sulfur sensitized and gold sensitized in the usual manner. The average particle size of No. Rokenized button particles is 0.
．． ko Oμm'T: Yes. In addition to the merocyanine dye, which has a maximum photosensitivity, as a sensitizing dye, excess stabilizers and surfactants were added, and all the additives shown in Table 1 were added, and then gelatin was added as a sensitizing dye. Approximately o, rt per 100f! .

Hiroshi--Torylene diincyanate was added per 917 m2 of exposure, and the button of O, CoV and 0. A coating film sample was prepared by coating the If gelatin on top of the above TL sweetener.

This sample r was brought into close contact with the step wedge of the step o, is (△togE), and the white tungsten light of 200 lux (
The film was exposed to light for 1 second at 2160 K) and then immersed in the following 3J image solution under red safety light for 30 exposures at uO'C.

I immersed my current model in the following etching solution for 20 seconds.

Thoroughly wash with water and remove the non-rogenated emulsion layer and unexposed S(
One layer of unpolymerized portion) was eluted to obtain a black body with wheels.

After that, an ultra-high-pressure mercury lamp with a kilowatt capacity was used to irradiate ultraviolet light.
The whole surface was irradiated for 3 minutes from a distance of 4jffi using a llI meeting.

Example 2 Mechanically grained by the method of JP-A-1-33-11. 2s material aluminum@fl/LO0C was washed with an aqueous sodium hydroxide solution maintained at LO0C for 1 minute to corrode the -S on the surface. After washing with water, it was immersed in a sulfuric acid-chromic acid fIj solution for about 1 minute to expose the surface of the aluminum.

Immersed in CO04 sulfuric acid maintained at 300C, DC voltage t,
The bond was anodized for 2 minutes at a current density of 3 zV and 76 m'', then washed with water and dried.

Next, alcohol-soluble nylon (Higashi Amilan CM)
-1000)0. If, dipentaerythritol hexaacrylate o, rt, nitrocellulose θ, If,
It was dissolved in p-methoxyphenol 0°0/f, Michler's ketone O, 20% methanol, and cyclohexanone JF, and applied to the above aluminum plate. The dry film thickness was λμ.

Example 1 on top of the above one layer. The same effect was applied so that each m2 contained 0,0 of silver and 0.39 of gelatin, and #! Manufactured by Membrane Sample Manufacturing.

This sample'It Example 1. It was exposed, developed and etched in the same manner as above. Thoroughly wash with water, remove the oxidized steel emulsion layer and unexposed S (unpolymerized S) from the heavy St-bath, and combine with 1 Ikl.
I had a statue meeting. At this meeting, the area was irradiated in all directions for 3 minutes from a distance of ttcm using an ultraviolet irradiation field equipped with a zkW ultra-pressure mercury lamp.

When this treated sample was attached to a Tono Madaster TOOCD printing machine and printed using a commercially available dampening solution, more than 1 r of good prints were obtained.

Claims (1)

[Claims] ? Silver halide sensor type polymerizable photosensitive material and current processing i
i! A method for forming a polymerized image, which comprises forming an image and then exposing the entire surface to light.