JPS5924842A - Image forming material - Google Patents

Abstract

PURPOSE:To obtain the entitled material having good coating stability during preparing an image forming material, not causing discoloration and increase of viscosity, and further, background fog, and capable of forming a sharp image, by using a metallic complex compd. as a substance becoming metallic development nuclei when reduced. CONSTITUTION:An image forming layer is formed on the surface of a substrate, such as polyester film or triacetate film. This layer consists of a hydrophilic binder layer, such as gelatin or PVA, contg. a metallic complex compd. such as bis(ethylenediamine) palladium (II) salt or tetrachlorodiamine platinum (IV) salt, becoming metallic development nuclei when reduced, and a development inhibitor, such as p-N,N-diethylaminobenzenediazonium chloride zinc chloride composite salt. As a result, the obtained image forming material has good coating stability and not changing viscosity of the coating during the formation of the image forming material, and since said metallic complex compd. hardly reacts with the development inhibitor, the binder, and other components in the coating, and causes no fog, a sharp image can be obtained.

Description

[Detailed description of the invention]

The present invention relates to an imaging material of the type that obtains a visible image by physical development. Physical development refers to a process in which metal development nuclei forming a latent image are treated with a developer 11 containing reducible metal ions and a reducing agent to provide a visible image consisting of grown metal particles. In recent years, the non-silver salt photosensitive material Oni I has been reconsidered due to the limited resources of silver salt and the rise and fluctuation of prices, but there are still very few examples of non-silver salt photosensitive materials. For example, F Utilizing the reaction to form topo Fe2+, Fe2-' reduces the metal/f-on and uses it as a "metal development nucleus." How to perform physical development? Chisel, quinone force 1, hydrogen donor and metal capable of nucleation A method of forming metal development nuclei from a metal compound using the reducing power of hydroquinones generated by exposure to light, and performing physical development to precipitate copper (Proceedings of the 1981 IW Photographic Society Annual Conference) ), etc. However, all of these are used only for pudding) M plates. An image-forming feed comprising a hydrophilic binder layer containing a metal compound serving as a development nucleus and a compound having a diazo group or an azide group is disclosed (Japanese Patent Application No. 182,661/1989). , in such ryōroku-forming materials, when physical development is performed using the product of the reduction of metal compounds such as gold, platinum, palladium uno, 6no, !, iron, copper, etc. as development nuclei, it is possible that the materials themselves undergo photodecomposition. When a compound having a diazo group or an azide group is used, development is automatically suppressed by these compounds.By performing pattern exposure, reduction and physical development using this image forming material, transmission optical lubrication can be achieved. A black image with a resolution of 4.0 or higher can be formed if necessary, and since each component is a dissolved system, the resolution is high and it is possible to reduce the power, etc. Because of these advantages, the image-forming material can be used as a substitute for lithographic film or as a screen material.While it has various advantages,
This image forming feed 4 [-, Jf; In addition, since the compound having a diazo group or azide group, which is a development inhibitor, reacts with the precipitated metal, the physical properties of the compound in image forming material H (11.1) (iQ suppressing effect decreases, Ji-kabu!J (fog)'?+
There are inconveniences that arise. The inventors of the present invention have conducted various studies in view of the conventional shortcomings mentioned above. By using e:li compounds of these metals, the reaction with the polar groups of the binder and other components in the paint is suppressed, and the above-mentioned drawbacks can be eliminated. The present invention was developed based on the discovery that an image forming layer is formed on the surface of a substrate,
The gist of the image forming layer is an image forming material consisting of a single layer of a hydrophilic binder containing a metal complex compound which is reduced to form a metal complex and a development inhibitor. The present invention will be explained in detail below. The image-forming feed of the present invention includes one in which an image-forming layer 3 is whitened on the soil of the substrate 2, as shown in FIG. As the substrate 2, any solid material such as glass, wood, paper, metal 51.1, plastic, film, woven fabric, non-woven fabric can be used, among which polyethylene film, polyethylene film, polyvinyl chloride film, Poly-filled vinylidene film, polyvinyl alcohol copolymer film, polynalene terephthalate film, polycarbonate soil no 1, nylon film, polyimide film, ethylene vinylidene film, ethylene vinyl alcohol copolymer film, a.
Plastic films such as f-onomer, cellulose diarbidate, cellulose triacetate, polysulfone film, and polyimide film are preferably used, particularly polyester film, triacetate filano, and the like. If necessary, these substrates 2 are pretreated to improve adhesion, such as corona discharge treatment or brimer treatment, and then an image forming layer 3 is provided thereon. The image forming layer 3 is formed by dissolving a metal complex compound which is reduced and becomes a metal development nucleus and a development inhibitor in a hydrophilic (ing) layer. Examples of the binder include -V latin, casein, etc. , natural polymers such as glue, arabicol\, hiratsuki, carboquine, methylcellulose, egg white albumin〉',
It? Polyvinyl alcohol (nB)/polyvinyl acetate, including carboxylic acid-modified polyvinyl alcohol), polyacrylic acid, polyacrylamide, polyvinylpyrrolidone (1.), polyethylene oxide, maleic anhydride copolymerization (, etc. are used, but as long as it is water-soluble or hydrophilic 1α11 old-1″,
The degree of hydrophilicity ++L required for the inder is also determined by the hole forming layer 3.
Contact with physical developer! I (Physical curse 13 when painting)
! The temperature is +y degrees at which the liquid penetrates into the image forming layer 3 and physical development becomes possible. Complex compounds of the four groups (such as palladium, gold, silver, platinum, copper, etc.) are used as the reduced metal phenomenon nucleus and the complex compounds of the four metal groups, such as palladium, gold, silver, platinum and copper. It is possible to use a pair [7-electron donor and a compound known as a naro ligand, such as the following as a tJQ compound]; bis(ethylenediamine)paradiuno^ (If) 4Xh, dichloroethylenediamine palladium tIll, 70 (ethylenediamine) platinum + If) yen;, detrachlorodiammine platinum (Seki 5 Kyo, Tsukuro L1 bis(ethylenediamine) platinum (IV3 t=, tetraethylammoni shim) j (11+ salt, bis (ethylenediamine) II
(If) tU. (As a ligand that forms a metal complex compound, 2
The cyclic structure is formed by coordinating with force or more (1) using a so-called chelating agent, and (1) the formation is performed using a chelating agent. The filter is made of metal and is suitable for filters with high chemical stability. Chelate 11. Examples of the agent include primary, secondary or tertiary amines, cuximes, imines, and tritones.4. More specifically, the following table of contents can be mentioned: dimethylglymexime, dithizone, mexine, acetylacetone, glycine, ethylenediaminetetraacetic acid, nitrilotriacetic acid, and uramyl diacetic acid. Those using the above chelating agents include bis(2,goubipyridine)palladium(It) salt, bis(acetylacet)palladium(11), bis(N,
N-diethylni! , solenediamine) vil (If
) JllK, Bis(2゜2'-BibilyC-sin) fi
I! (Ill tJ, i, bis(1,10-phenanthroline) 6-(It) salt, bis(dimethyl'glyoximate)copper (Ill, bis(acetylacetonato)copper (11), bis(acetylacetonate) -1.) Platinum (11 etc. is preferred. As the development inhibitor, a compound having a diazo group or -azido group is used, and as the compound having a diazo group, a zinc chloride double salt or a fluoride salt having a diazo group, or IJi
Diazo resins, which are condensation compounds obtained from these compounds such as paraformaldehyde, are preferably used. More specifically, +1-N. N-diethylaminobenzenediazonium zinc chloride double salt, p-N-ethyl-N-β-hydroxyethyldiptogycybenzenediazonium zinc chloride double salt, 4-benzoylamino-2,5-jethoxybenzenediazonium zinc chloride 1u salt, 4-(4'-methoxybenzoylamino)
-2,5-sheduginbenvindiazonium cyclized zinc j
Jjim, 4-(p-)ruil merkab)
)-2,5-L/meth)・Kidbenzenediazonium zinc chloride salt, 4-diazo-4'-methquine diphenylamine chloride) 11j lead 11-1, 4-diazo-3-methquine-diphenylamine VK lhia 6i 111i
Shiogi, (li+, <Kel1l-like jurisdiction
. r91°,) It; /, (rl' t-71 conversion'
F 'l'; as J) t, p-azidoacetophenone, 4,4'-thia, NdobuJrucon, 2,6-bis=(・1'-ash>doben'al'l)-acetone,
2, 6-bis-(4'-azidopendel)-cyclohextanone, 2. (5-bis-(11'-azidobenzal)-4-methylcyclohexylinone, 2゜6~bis-
(4'-A2-dostyryl)-Alζton, Azitobelay zero can be used. Or a Schiff'zo group or azide X
Compounds other than those mentioned above may be used as long as they have the following diazo group or azide group, and it is also possible to use two or more compounds that form a diazo group or an azide group. The inclusion of the metal complex compound and development inhibitor described above in the image forming layer 3 is as follows.
(1 part (1 part ゛[gold 1116'i'
．． 1 to 100 parts by weight, especially 1 to 120 parts by weight, and 1 to 100 parts by weight, especially 2 Q =,
5 Q anterior segment, ζ). Gold complex compound is 01 heavy iI
If part t is less than 1, the concentration will not be sufficient, and 1001!
If T, l', 1 part is ρ, then it is not ll! The strength of the image area is /IX and J'<7. In addition, if the development inhibitor is less than 1 part 1''1TTl', the effect of suppressing the development of L'1',l is small, so soil blurring is likely to occur, and 1007[
If the number exceeds 1111 parts, the processing time for one image becomes longer in order to increase the density by one. i+! u I, 'St formation layer 3 or more

[7] The metal complex compound and the development inhibitor are mixed with an aqueous solution of the binder so that the content is within the range of 10 to 1000 c.
, p. It can be formed on the surface of the substrate 2 by a known coating method using a coating liquid of about 71-cm, and usually has a thickness of 1 = 307)+
++. In addition to the aqueous phase, water, lower alniol, and ketones can be used as solvents. Ether q with water rIC compatible solvents and 71i4, ff solvents are also used. In addition, among the metal complex compounds used in this book and 11 gates, the complex compounds of the above-mentioned chelating agent and noble metal are generally poorly soluble in water, and such complex compounds are simply added to the binder aqueous solution. When used in combination, the image forming material obtained has low resolution and the transmission optical density of the image is also low, so it is necessary to add a complex compound in a large amount to increase the transmission optical aIW of the image. The disadvantage of using complex compounds with such a force q・1l solubility is l
・After dissolving the IF-soluble complex compound in a water-miscible organic solvent, it is mixed with an aqueous binder solution and d+! In addition to the above, specific organic solvents include celonulp acetate, methyl cellosol tate, methyl cellosolve nitrile, Tlrl'', pyridine, methyl ethyl ketone, and isophorone. Among the inhibitors mentioned above, fluoroborate salts of diazonium compounds and azide compounds are urea-soluble, so
As with the above complex compound, it is best to dissolve it in the same water-miscible organic solvent as above and then mix it with the aqueous binder solution.The particle size of the development inhibitor should be made smaller to further promote dissolution! 1f is desirable. Since the image forming layer 33 is subjected to a physical development treatment or a water washing treatment, a hardening treatment is preferably performed after its formation in order to prevent the dissolution of the binder or the elution of the contained components. The compound is mixed in the coating for forming the image forming layer 3 at a ratio of 1 to 50 parts per 100 parts of the bar fender. This is done by applying one stitch to the "forming layer": Al compounds such as light bread, ammonium light bread, etc.・0.!l'J Tunformaldehyde, glyoxal, glutaraldehyde, 2-methylglutaraldel:
l', Riku? /Aldehydes such as naldehyde; 0-benzoquinone, p-benzoquinone, nclohexane-1.
2-i dione, Schiff [gopentane-1,2-dione, ε
diketones such as acetyl, 2°3-pentane C2one, 2,5-hexenedione, 2°5-hexenedione;
Evogind such as triglyndylisonanurate; tetraphthaloyl chloride, 4,41-difunylmethanedisulfonyl chloride, 4,4t-dichloro-6-hydroxy-8-triazine, and the general formula % formula % of phosphorus compounds or carposis represented by 2) [mido; styrene/'7leic acid copolymer, vinylpyrrolidone/maleic acid copolymer, vinyl methyl ether/maleic acid]
F acid copolymer, ethylene-(Ene/maleic acid copolymer)
j combination, methacrylic acid/methacrylonitrile copolymer,
Polytutacrylamide, methacrylic acid ester copolymerization 1
・1, etc. (1) l lipid top. Carboxylic acids include glutaric acid, r-succinic acid, human carboxylic acids such as malic acid, lactic acid, citric acid, aspartic acid, gelcholic acid, tartaric acid, organic carboxylic acids such as 2, dimethylol urea, and 1-limethylol melamine. Dimethylolization of etc. 41
You can also use restraints 2). A typical embodiment of the present invention has been described above with reference to FIG. 1, but further modifications may be made. First, the +l+i image forming layer 3 of the image forming material of the present invention
A protective layer 4 may be provided on the surface as shown in FIG. The protective layers 4 and 7 are first formed using a hydrophilic 4II binder similar to that used in forming the image forming layer 3. Alternatively, it may be one in which an inorganic filler is added to the backside of the combinable binder. Further, a charging agent 1υ and i is added to this protective layer 4, and the bands tlf, l! It may also have the role of stopping 7j. Ho, 4
5. The layer 4 may be hardened if necessary. 1: By providing the eel retaining layer 4, the components constituting the I sono 111 picture forming layer 171 can be eluted (7) l')j
In addition, since the peak is made of metal, it is possible to prevent capri due to the anti-f1·1 of light during close exposure and to prevent the emission of knee-ton rings by 1vj. Secondly, a band 'tti, lυ111' layer 5 may be provided on the back surface of the base body 2, and a band? As layer 5, the above-mentioned hydrophilic binder, an appropriate parent/11 binder, and an anti-corrosion agent were added to the layer 5.
．． 111111. It is best to apply and form using a paint made of . Thirdly, as shown in No. 41 C1, the substrate 2 and the image forming layer 3 are
A primer layer 6 may be provided using an appropriate material and method between the primer layer 6 and the primer layer 6. For example, as the primer layer 7, chloroprene rubber and polyisocyanate are mixed in a ratio of 25:1 to polyester filtrate 1-. It can be provided by diluting with a mixed solvent of 1ViEK:) luene = 1:1, coating it to a thickness of 17 nn, and drying. To form 1llllllll using 1.
It's cold. In addition, vehicles for brimer coating 1 include phenolic resin, resolunol resin, urea resin, ethylene urea resin, melamine 1.111)7, evogishi resin, unsaturated polyester filtrate, etc.
<1 fat 1. H! (for acid-resistant vinyl wood) 1. Polycarboy・
- resin, polymethacrylic acid mep resin, polyacetal it'l + fat 1. Jτ styrene resin, ethylene itself 1
vinyl acid, J(il + fi body, thermoplastic such as polyvinyl butyral resin) (I1(☆1 fat, natural rubber, S13
14. Rubber adhesives such as acrylonitrile butadiene rubber, chloroprene rubber, polyisoprene/isobutylene rubber, etc. can be selected. When using the above-mentioned resins, heat treatment is required.
In addition, thermal radiation f'Ji property (151 resin also has glass transition during adhesion)
: 11 It is important to heat the adhesive to a temperature higher than 11, which may lead to thermal deterioration of the photosensitive component, so rubber-based adhesives with a glass transition point that is lower than room temperature are preferred. The method for forming an image on the image forming material of the present invention will be explained in II! For example, as shown in FIG. A compound having a diazo group or an azide group is decomposed to a degree according to cli.Any light source can be used as long as it can resolve one angle of light (jij is the above-mentioned diazo group or azide compound) into 4J-. Next, the image forming layer 3 having a latent image in which the compound having a diazo group or an azide group is decomposed in a pattern is brought into contact with an aqueous reducing agent by blue or coating to form the image forming layer 3. Metal development nuclei are generated almost uniformly in the agent. Zan, trimethylamine borazane, other borazane derivatives, borane derivatives such as borane, diborane, methyldiborane, hydrazine, etc. can be used. Particularly preferably, acidic 8 g 1 tin solution of chloride, stannous sulfate solution ( Weias solution) or a commercially available senticizer solution for electroless plating is used, but generally any strong reducing agent can be used.
! Generally speaking, the reducing agent is 01 to 50'i
Iiii 7r, containing /g of warmth? ilj meltitk
Using 7F'+' 17nf l or e'il A for 10 seconds to 40 (+ seconds) A physical developer is immersed in or brought into contact with the circular image M3 having a latent image formed by a selected surface of the compound jMl, and the metal inside is reduced to the development 71 centering around the metal development nuclei in the polar light area. ) and then deposited to form an 11-view image 3134 as shown in FIG. As a physical developer, a water r+'x solution containing water 1f+' and a reducing agent is added as necessary. It is used as a reducible small metal salt (!, 1911, for example nickel,
cobalt, iron and chromium □, 1i·v+ group b metals,
Copper tanning: Ib, water-soluble salts of group metals are used alone or in mixtures. As suitable water-soluble single-layer reducing heavy metal salts, for example, the following can be used. Cobaltous chloride, cobaltous iodide, ferrous bromide,
Heavy metal halides such as ferrous chloride, nichrome bromide, nichrome iodide, cupric chloride; nickel sulfate, ferrous sulfate, cobaltous sulfate, ferric sulfate rubber, cupric sulfate, etc. Heavy metal sulfates; heavy metal nitrates such as nickel nitrate, ferrous nitrate, cobaltous nitrate, dichromium nitrate, and dichromic nitrate; For example, 10 to 1 O(19/
It is included in the proportion of l. Reduction hl+ −: 1. , °C), such as hypophosphorous acid, sodium hypophosphorous acid, sodium borohydride, hydrazine, formalin, diethylamine borane,
Dimethylamine borane, trimethylamine borane, borane, diborane, methyldiborane, diborazane, borazine, borazine, t-butylamine borazane, pyridine borane, 2,6-ruticine borane, ethylenediamine bokun, hydrazine diborane, dimethylstibine borare, phenylphosphine borane , dimethylarsineborane, phenylarsinephorane, dimethylstivineborane, diethylstivineborane, etc. can be used. These reducing agents are contained in a physical state (for example, 0.1 to
5 Q 9/l is used. The physical developer contains organic carboxylic acids as a complexing agent in order to prevent the heavy metal ions produced by dissolving the reducible metallic salt described in i'*iJ from precipitating as hydroxides. In order to improve storage stability, operability, etc., physical developing solutions often contain l, J, buffering agents, etc.
Anti-Ill All, surfactants, etc. are always 11: I'C
i; j, added a). As described above, in the present invention, a monometal complex compound is used as a substance that is reduced and becomes a metal development nucleus.
Good coating/10 stability when creating image forming materials, i:
ff is the stability of the paint (r is the stability, /r is the viscosity of the paint)
Also, metal complex compounds are development inhibitors,
It is possible to provide an image-forming material that does not easily react with other components in the paint and other components in the paint (and produces clear images because it does not cause fogging). Below are some examples that more specifically illustrate the present invention. Example 1 A photosensitive solution having the following composition was mixed and prepared, and applied onto undercoated polyester Filno (manufactured by Toshi, Lumirror Q-82) using a wire bar plate 36, and dried to create a photosensitive solution. did. Exposure was carried out by applying a single ray of ultra-high pressure mercury lamp at 1 m and 11° to 1 μm 111". Next, the sample was placed in a 40°C reduction bath (Oku! 11r made by Mulberry, Shiba Nickel) for 10 seconds. Clean, E Ni'c (7)
i&, 20'C physical developer (manufactured by Okuno Pharmaceutical, i"M
By immersing it in P chemical nickel for 60 seconds, the transmission optical a L (j-4,. The viscosity of the photosensitive material 71 used above is RN'd.
Immediately after Ij'u] 20 c, p, s, and even after 24 hours had passed, it was 150 c, p, s, and it was difficult to apply. The variation C1 of Example 1 could not be overcome either.
$7: Instead of body, P(l C12 hydrochloric acid (l [water soluble 11'j-(1, (1(] 011.11.Ill,)
Step 1h was carried out in exactly the same manner as in Example 1. The viscosity immediately after adjusting the exposure temperature is 330 C.
, ++, S, and 8- is 8j1 after adjustment! f-interval,”
, in L, the viscosity after (i 90 e, Il, s,
Therefore, it was necessary to dilute it during application. or,
After 8 hours, the color of the photosensitive solution changed! ill's 111
11- (The color has changed from the bottom to reddish brown, and the number of HL is 97 due to this change) 1- Created using liquid 1. Fog will occur if the track order is not formed using a light-sensitive material, and the i4 color of the base part optical d“
, 1 (Suga 025.
A similar result M was obtained in the same manner as in Example 1, except that the preparation was 98% or higher. However, in the end, the Pd-BDTA inscription was also changed.
C12Jg l'lif acid i'1 If it is an aqueous solution, the preparation j
l1% #a After o minutes, 1゛C1, (♂``11
1 was seen. Examples Photosensitive solutions having the following composition were prepared. The viscosity of the photosensitive solution immediately after adjustment was 95 c, p, s, and υ. When 118 yen of each J6 was created and an image was formed, the processing time for developing hemorrhoids was the same. can be,
The same thing happened when the transmitted light of the image was measured at room temperature.No fogging occurred either.

[Brief explanation of the drawing]

Figure 1~aa 4 Figure + Book B I'll (7) (
+l+i image formation ii'' (1, 111i, 5th figure showing 4 examples, 5th ゛, 1st non and 5th figure are images formed using paulownia wood of the present invention (lii image I f 2 formation zu each) , l J1% is a neo-1zer plane view. 1...Direct image forming abrasive material 2...Base; 3... ++!lI image forming layer 4...
...Transparent synthetic resin layer 5 ...Charged. 1 (, lj stop layer 6...
...Brima 1 layer 7...1fFl over-manuscript! Applicant: Tai L] Hon Printing Co., Ltd.: 1111 Patent Attorneys: Nishi γ7 Beauty: 1, 2, 8, 4, δ, 0

Claims (1)

[Claims] (1) An image-forming feed consisting of a single layer of a hydrophilic binder containing a metal complex compound and a development inhibitor, in which an image-forming layer is formed on the surface of a substrate, and the image-forming layer is reduced to become metal development nuclei.