JPS5879246A - Formation of metallic image and reducing method for metallic image - Google Patents

Abstract

PURPOSE:To considerably shorten the time required to develop a metallic image forming material by using an alkaline soln. contg. iron ions or copper ions as a developer. CONSTITUTION:A metallic image forming material is obtd. b8 laminating a metallic thin layer soluble in an alkaline aqueous soln. such as an Al film having about 50-3,000Angstrom thickness and a photosensitive resin layer such as a layer of naphthoquinone-1,2-diazido-5-sulfonic ester of novolak resin having about 0.5- 10mum thcikness on a support such as a polyethylene terephthalate film in order. The material is imagewise exposed and developed with an alkaline aqueous soln. of about 9-14pH contg. about 1-600ppm iron ions or copper ions. By using said developer, the metallic thin layer can be developed rapidly at about 20-50 deg.C in about 20-90sec.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for forming a metallic image and a method for reducing force.

Conventionally, ultra-high contrast lithium film has been used as a double-sided forming material suitable for halftone images and line drawings, but since the development fIII of this lithography film is due to contagious development, the image during the development process expands with the development time. Growing up and now *? It is impossible to stop the process instantly, and the development continues to progress, albeit slightly, immediately after the development process is finished. Therefore the obtained i
There was a problem in that fringes appeared around ii*, making it impossible to obtain an image of ideal quality. In order to eliminate the drawbacks of the above-mentioned lithium film, a thin metal layer mainly made of aluminum is provided on the support, and a photosensitive resin layer is provided on the thin metal layer. iiiig
I! A formable material is exposed using a dot original, and this is 3j
1gI! Then, depending on the characteristics of the photosensitive resin, an image with almost completely reversed brightness or the same image as the original can be obtained, and can be used as an original to be printed on a printing plate.

However, since it takes time to transport the known metal image-forming material from the warehouse, the overall development time is long, and the processing time of the rolled metal-based image-forming material in an automatic processor increases, and as the development time increases, the overall development time becomes longer. Therefore, there are problems such as the processing tank of the automatic processor must be made large in size and expensive.90 The present invention was made in view of the above circumstances, and it When developing a metal-based image-forming material that has a metal-based thin layer soluble in an alkaline aqueous solution and a photosensitive resin layer, or when erasing a metal-based image obtained by development processing, a metal-based thin layer is used. This makes it possible to atomize the layer with an alkali containing iron ions 1 and/or steel ions ν. That is, the present invention forms a metal image by exposing and developing a metal image-forming material with actinic rays, which has at least a thin metal layer soluble in an alkaline aqueous solution and a photosensitive resin layer on a support. In the method of
A metal image-forming method having one feature, and a metal image-forming material having at least a metal thin layer soluble in an alkaline aqueous solution and a photosensitive resin layer on a support are imagewise exposed to actinic rays. After that, according to the method of reducing the strength of the metal-based image obtained by development, the metal-based thin layer is reduced in strength with an alkaline aqueous solution containing iron ions and/or steel ions. The present invention will be described in more detail below.

The support constituting the metal image-forming material in this invention may be a commonly used transparent support such as polyester, polydeoxylene, polyethylene, polyvinyl chloride, polyvinylidene monochloride, polycarbonate, acetic acid cellulose, etc. A thin metal layer soluble in an alkaline aqueous solution on the support is preferably a polyethylene terephthalate film from the viewpoint of strength, transparency, dimensional stability, etc. 1 = Consists of metals such as umium, zinc, lead, tin, aluminum, rumanium, alloys of the above metals, and metal compounds such as nitrides, holides, carbides, sulfides, and salts, and the above-mentioned Preferably, the metal is aluminum or an arionium iron alloy, and the metal compound is preferably aluminum oxide.

The metal thin layer is formed on the support by a conventional method such as vacuum evaporation, sputtering, high frequency ion silating, plating, etc., and the thickness of the metal thin layer is 50 to 30 mm.
0OA% Particularly preferably in the range of Zoo to 1000% 0 A thin metal layer soluble in an acidic aqueous solution and a photosensitive resin layer are provided on the support when developing the friend metal image-forming material. When a thin metal layer is developed with an acidic aqueous solution containing iron ions and/or copper ions, the development time is hardly shortened compared to when developed with an acidic aqueous solution that does not contain mosquito ions.

The photosensitive resin formed on the metal thin layer in the present invention is soluble in various solvents, such as a photosensitive resin having a shear group, an azide group, a cinnamoyl group, or an acrylic group.・As the photosensitive resin having the above-mentioned shear group, naphthoquinone-1,2-diazyl-5-sulfonic acid ester of resin, sulfonated phenol 1111-N,N-zomethyla-denophenyl=r-
Examples of the reaction products with sia-tonium salts include photosensitive resins having azide groups, such as partially saponified resins, 3-(4
-azidophenoxy) ethanol styrene maleate ester is exemplified, and as a photosensitive resin containing a cinnamyl group, styrene-anhydride! An example is an esterified resin of a leic acid copolymer and an ethylene oxide adduct of cinnamic acid.

Also, the above Acrylicity! Photosensitive resins having groups include polymeric substances, photopolymerizable unsaturated compounds, photopolymerizable It is a mixture of initiators, free radical generators, heat stabilizers, sensitizers, etc. Examples of polymeric substances having more than one of the above groups include methyl methacrylate/methacrylic acid copolymer, styrene/methacrylic acid copolymer, etc. -1J acid copolymer, and methacrylic acid-methacrylic acid/methacrylic acid/2-ethylhexyl acrylate copolymer. Other polymeric substances include sulfonic acid group-containing monoester or f-ryad, 2-methyl-! -(N
, N-zomethylaζ)) methyl-1,3-propanediol/terrestallic acid copolymer, bis-aminozolobyl/adipic acid/o-casic lactam copolymer, etc., and copolymerizable Examples of unsaturated compounds include monomers such as alkyl acrylates, lates, 2-hydroxy acrylates, annoalkyl acrylates, polytetraalkoxy acrylates, glycidyl acrylates, halogenated alkyl acrylates, and polyfunctional acrylates. Polymer compounds containing ethylenically unsaturated groups in the body and side chains, such as partial esterification products of styrene/i-leic anhydride copolymers with aryl alcohols, glycidyl methacrylate adducts of methacrylic acid methacrylate/methacrylic acid copolymers The photopolymerization initiator is exemplified by alkyl ether, pen ψ phenone, yodozozusuke) ν, anthraquinone and its derivatives, triallyl If, lunimer, etc., and free radical generators. Examples of the heat stabilizers include r-anophenylketone compounds, diallene dyes, cyclic diketone compounds, thioketone compounds, mercaptan compounds, etc., and heat stabilizers include hyde gastric quinone monomethyl ether, phenothiazine, etc. Examples of the sensitizers include color patches such as xantholyte, acridice, cyanide, pitchlin, and coumarin.

Furthermore, the above-mentioned photosensitive resin may be added with actinic ray absorbers such as inorganic materials such as carbon black, iron oxide, and titanium oxide, as well as organic pigments and dyes to form a colored metal image. When the photosensitive resin layer contains an actinic ray absorbing agent such as carbon black, the active ray m intensity of the photosensitive resin layer is 1. O ~ 4.0, preferably S ~ 3.5.
In order to form the above-mentioned colored metal ims, it is best to blend carbon black.0 The above-mentioned active light 11iI degree melts, ultraviolet light with a wavelength of 350 to 400 nm St active light me, spectrophotometer needle CB stand 32G The spectral transmittance is measured using a spectral transmittance model (type 1), and the value is the light amount ratio of the incident light and the transmitted light at the maximum spectral transmittance expressed in logarithm.

It is preferable that the thickness of the photosensitive resin layer is 0.5 to 10 microns.

Between the metal thin layer and the photosensitive resin layer, adhesive resin and active light! ! An active light 1IIa collection layer composed of an absorber and/or a colorant may be provided to increase the light-shielding property.

Rough metal 11gI! Formable materials include an adhesive layer between each layer and a cover film on the photosensitive resin layer, as necessary.
A sleeping layer or the like may be provided.

The above-mentioned metal Si* forming material is subjected to imagewise exposure with active light from various light sources such as a mercury lamp, an arc lamp, a metal halogen lamp, a xenon lamp, etc., and then is subjected to an am treatment using the 01A method. is a thin metallic layer with iron ions and/or
Alternatively, development is performed with an alkaline earth metal containing copper ions, but in this case, the photosensitive resin layer and the metal thin layer are developed in the same alkaline aqueous solution, and the photosensitive resin layer is developed in an organic solvent or an acidic aqueous solution. Or two-component II, which develops with an alkaline aqueous solution and develops the metal thin layer with an alkaline aqueous solution.
You can do any of the fun methods. However, in either method, the alkaline aqueous solution for developing the thin metal layer 1 contains iron ions and /l or steel ions, and compared to development using an alkaline aqueous solution that does not contain these ions. , development time is significantly shortened. Iron ions in the developer are produced by Copper Ion Co., Ltd. Compounds added to the iron developer IIw, which act effectively regardless of their valence, include ferrous chloride, ferrous chloride, ferric chloride, ferric phosphate,
Examples include anhydrous or hydrated iron oxides such as ferric iron, #IA cupric oxide, and ferric chloride, and ferrous oxide, but chlorides with good scale properties are preferred. If the concentration of iron ions and /l or copper ions in the developer is too low, the development time will not be shortened much, and the concentration of iron ions and /l or copper ions in the developer will not be much shortened.
s PPM or higher is good. However, if a large amount of the above-mentioned compound is added to the developer solution, precipitation occurs and the development time becomes longer. Therefore, the iron ions and /l or copper ions in the current *W are 600 PPM or less, preferably 4QQPPM or less.

In the two-component development method, if the photosensitive resin layer is insoluble in an alkaline earth metal-containing aqueous solution, the photosensitive resin layer is developed with an acidic aqueous solution or an organic solvent, and then the alkaline earth metal It is desirable to develop with a metal-containing aqueous solution.

The alkaline aqueous solution used in the one-component development method includes aqueous solutions of hydroxides and carbonate of alkali metals, such as lithium, sodium, potassium, rubidium, and cesium, containing iron ions and/or copper ions. Particularly preferred are aqueous solutions of sodium hydroxide, sodium carbonate, potassium hydroxide, potassium carbonate, and the like. The - of the above-mentioned developer is set depending on the type, composition and development speed of the photosensitive resin layer, but is usually in the range of 9 to 14, preferably Fill-13J. Furthermore, thermal bridging salts exhibiting alkalinity such as trisodium phosphate and sodium aluminium monoxide, and oxidizing agents such as sodium chlorite, potassium brobate, and sodium folate can be added. Two-component development method Development gI when developing a photosensitive resin layer with an alkaline aqueous solution! As the solution, an alkaline aqueous solution for the above-mentioned 11K imaging method or alkaline water that does not contain iron ions and/or copper ions and gold is used. [[For alcohols such as methyl alcohol, ethyl alcohol, and alcohol, ketones such as methyl ethyl ketone, acetone, and diethyl ketone, esters such as ethyl acetate, butyl acetate, and amyl acetate, trichloroethane, ethylene chloride, Examples include halodanized hydrocarbons such as tetrahydrofuran, and ethers such as tetrahydrofuran and dioxane. In addition, when the photosensitive resin layer is ampered with an acidic aqueous solution, the developing solution is an aqueous solution with or without acid, such as hydrochloric acid, acetic acid, formic acid, Sierra Leone, etc., with a rit value of -1 to 5, preferably rit to 3. To develop the photosensitive resin layer as described above and then to etch the thin metal layer, the developer tube of the one-component development method described above can be used.In addition, in the two-component development method.

If the photosensitive resin layer is insoluble in an aqueous solution containing an alkaline earth metal, the etching solution for the metal thin layer after developing the photosensitive resin layer may be magnesium or calcium containing iron ions and/or copper ions. , PH1j of this developer.

It is set depending on the type of metal thin layer, the shape of etching, and the development speed, but it is usually 10-14, and preferably 11-14. To this developing solution, an inorganic salt of an alkaline earth metal such as alkaline earth calcium or an oxidizing agent such as hypotonic calcium or magnesium may be added to form a thin layer of metal. Development gII#'i, temperature 20-50℃, preferably 30-40υ, development time 2
0 to 90 seconds, preferably 20 to 70 seconds. There is no problem even if the processing conditions for this metal thin layer are slightly or slightly excessive, but if the processing conditions are insufficient, fine image areas may be
In order to facilitate contact with each of the above layers, an organic solvent or a surfactant may be mixed with the developer for the photosensitive resin layer and metal thin layer, which may cause problems. Such organic solvents include:
Alcohols such as methyl alcohol, ethyl alcohol, benzyl alcohol, ethylene glycol, ethyl cellosolve, ethyl cellosolve, monomethylamine, dimethylamine, trimethylamine, monoethylamine,
Dimethylamine, triethylone, monoethanolamine, diethanolamine, triethanolamine, etc., and ketones such as atomylamine, methyl ethyl ketone, etc. are mentioned, and these organic solvents °0 mixing amount egA
IIs graviton or less for st, preferably tisxt-
Examples of the following surfactants include ionic and nonionic commercial products, 3M Company II), etc.
This mixing amount is less than 5% by weight based on the developer, preferably #
If the method of the present invention having the above configuration is applied, the developing time of the metal thin layer can be greatly shortened with simple operations, and the overall developing time can be significantly shortened. .

f&, When the force is reduced according to the method of the present invention, the force can be reduced satisfactorily in a short time. Examples of the present invention will be described below.

Example! (1) Creation of metallic image-forming material A 100-micron-thick biaxially oriented polyethylene film (7#L/-) was used as a support, and its surface was washed (dry) and then coated with a resistance heating vacuum evaporator. Aluminum with a thickness of 500x and 700'11 was deposited under a vacuum of about Ig-' Torr.The aluminum deposited layer had many pinholes of 20 to 501 chrome, and its optical density was They were 2.70 and 3.81, respectively.The above optical density was measured using a densitometer DM-25 manufactured by Dainippon Screen Co., Ltd.
6, wavelength range 280~7QQn
The composition of the resin solution of the photosensitive resin layer provided on the aluminum ζ vapor deposited layer is as follows: As shown in the table.

Table 1 In Table 1, the polymeric substance is methyl methacrylate/methacrylic acid/acrylic @-2-ethylhexyl copolymer (C mol-W45:25:30), and the numbers in the table indicate parts by weight. Dispersion of Naori-bon black is carried out using a Pedernl tube.
Coated to a solid content thickness of 3 microns using a Perscoat, dried to form a photosensitive resin layer tube, and then coated with polyvinyl alcohol C 105 using a reverse coater on top of the tube.
Iyshisha 11) 7 o weight 11, /'fr7BA14
G (II-manufactured by Kogyo Seiyaku Co., Ltd.) 3 parts by weight, ethylene glycol
6. A protective layer composition solution containing 7 parts by weight of monodecyl ether and 920 parts by weight of water was applied to a solid content of 2Z thick and dried to form a protective layer tube.
The above sample 1, in which ffi-forming material was prepared, has a black surface and a metallic luster of aluminum on the back surface, and the front and back surfaces are clearly distinguishable, and there are no pinholes in the aluminium-deposited layer. Black photosensitive resin layer (optical density 2.70
), and furthermore, the optical density of sample 1 is 4 or more and has high luminescence.・Sample 2F
i. The photosensitive resin layer was almost colorless and transparent, and both the front and back surfaces had a metallic luster of aluminum, and the pinholes in the aluminum vapor-deposited layer were not completely hidden.

(b) Exposure and development Sample 1 and sample! O gold metal-based image-forming material, 2
1 step step guide, 5~ess halftone rtso//i
n) Using a test negative film with thin lines, letters, and 1 independent point, sample 1 time for 15 seconds using an ultra-high pressure mercury lamp (sKW70aa). After each exposure for tf1 second, the film-retaining layer was removed by washing with water. This exposed material was mixed with sodium hydroxide 21/1. Sodium chlorite 3? /l, trisodium phosphate 5? /l, a developer (38° C.) consisting of 0.1 tel of the surfactant listed in Table 1 above and 0.7 tel of cupric chloride. After immersion in K, the sample was washed with water and subjected to partial development II. 3 Eh.

Comparative Example 1 The metallic image-forming materials of Sample 1 and Sample 2 in Example 1 were successfully developed in 32 seconds for Sample 1 and 49 seconds for Sample 2 without leaving any deposited aluminum. When the sample IF168 was developed in the same manner as in Example 1 using a developing solution containing no cupric chloride, the sample IF168
sample 2tf required 99 seconds.

Example 2 The metallic image-forming materials of Sample 1 and Sample 2 in Example 1 were mixed with the developer of Example 1 which did not contain cupric chloride (
Sample 1 was immersed for 7 seconds and sample 2 was immersed for 19 seconds in 30℃), washed with water to remove the unexposed portion of the photosensitive resin layer, and then subjected to a first incubation process.Next, 1.5 tel of calcium hydroxide and 0 tel of aluminum chloride were added. .1 tel.

Nokuin Emu-140 (manufactured by Dai-Kogyo Seiyaku Co., Ltd.) 2 ml,
Triethanolamine lf/l, ferric chloride 0. 'l?
Sample 1 was developed in 51 seconds and sample 2 in 74 seconds. It was developed well.

The black metal image formed material of sample 1 after the above development treatment is only a black photosensitive resin when viewed from the front side, and no metallic luster of aluminum is seen at all, and when viewed from the back side, only Al 1 = cum metallic luster is observed. However, no coloring of the black photosensitive resin was observed, and the respective sizes of the photosensitive resin layer and the aluminum vapor deposited layer were gold (vh9). Furthermore, there are a lot of pinholes in the bottom part of the film after K11e, and the optical density decreases, and the gamma value of the optical density of Step Guy is xol
I&'s ultra-high contrast 1 was showing 0 Another sample after the development process! After dyeing the OO color metal image formed object with an aqueous solution that absorbs methylene blue, the front and back sides of the object are dyed.
tApparently, the sizes of the photosensitive resin layer and the aluminum vapor deposited layer are exactly the same. The unexposed areas of the photosensitive resin layer were removed, and then Example! When etching the alonium layer by immersing it in a ferric chloride-free ferric chloride-free ferric chloride solution, it took 2 seconds for Sample 1 and 3 minutes and 17 seconds for Sample 1.Example 3 Example 1 Anhydrous! Styrenic acid styrene resin C trade name: Phytron 820. Mitsubishi Montsan) Co., Ltd. 11) t.

parts by weight, actinic ray a absorber (2,2'-4,4'tetrahydroxybenone phenone) 3 parts by weight, material C product winter channel black, Mitsubishi Chemical Industries, Ltd. 11) 1 part by weight, dye C product Name Nige Shishi Pace LL% BARF Co. @) 0.1
An actinic ray absorbing layer composition liquid consisting of 1 part by weight and 2 parts by weight of methyl seron red tool was applied to a solids thickness of 3 densities using a stomach router, and dried. The active ray concentration was 1.7 and 0. This actinic ray absorption layer cane! II Example 1 45 parts by weight of the polymeric substance shown in Table 1, 36 parts by weight of trimethy4-ruzo-tetrapane triacrylate, 8 parts by weight of trialycyi 5-dylamide, and 2-mercazotopene ψ-idenda were added to a door. A photosensitive resin composition liquid consisting of 3 parts by weight, 0.032 parts by weight of high PO quinone monomethyl ether, and 368 parts by weight of methanol was applied to a solids thickness of 11 chrome using Roll Sea 4, and the underarm photosensitive area was dried with On the resin layer, the same protective layer composition solution as in Example! Vmm type and thickness 2z thick was applied and dried to produce a metal surface 11 forming material.This gold layer IIR
*Using the same test negative film as in Example 1 as the formable material, ultra-high pressure water chain lamp C3 armor, 100aa>K, therefore 1
After exposure for 11 seconds, the protective layer was removed by washing with water.The exposed material was then removed in the same manner as in the previous example to remove the photosensitive resin layer and actinic ray absorbing layer. D K11ll ferric (0,4f) substitute for ferric chloride in the second liquid II
/4) When etching the alumonium vapor-deposited layer with a working liquid having the same composition except for the addition of tm, it remained for 49 seconds.Comparative Example 3 Similarly, 211! As shown in the current line, it takes 2 minutes and 11 seconds to etch the aluminum vapor deposited layer.
, immersed in the 1st present II cabinet of Example 2 for 211 seconds, washed with water, and then soaked in the 1st present II cabinet of Example 2. It was immersed in the current cabinet for 49 seconds and washed with water to reduce the force. As a result, the halftone area of 50- is 40
It is reduced to 91 dots and has a good dot shape.

Comparative Example 4 When the net 4 portion of the black metal image of Sample 1 was reduced in force with the second developer of Comparative Example 2 in the same manner as in Example 4, the immersion time of the second developing solution was 49 seconds. However, the size of the evaporated alonium layer was much larger than that of the photosensitive resin layer, and etching of the evaporated alonium layer was insufficient. Even more!
When immersed in 1ull solution for 2 minutes and 4 seconds in total, the size of the photosensitive resin layer and the aluminum vapor deposited layer matched, and the size of the 50-
The halftone dot density was reduced to 4091 halftone dots.

Comparative Example 5 The metallic pattern-forming material of Sample 1 in Example IK was subjected to a first development gII to remove the photosensitive resin layer in the same manner as in Example 2, and then treated with phosphoric acid r8all)ss.

t, nitric acid r611s)%15j', water 500f carana:
When the aluminum vapor deposited layer was etched using the second developer (38°C), it took 1 second to remove the photosensitive resin layer in the same manner. When the aluminum vapor deposited layer was etched by immersing it in aqueous solution 11 with the addition of iron fO, 43f, the etching time was 2 minutes and 29 seconds, and the etching time was not shortened. The photosensitive resin layer was then removed, and the aluminum vapor deposited layer was etched with an aqueous solution (38°C) consisting of 12 parts by weight of ferric chloride and 1 part by weight of citric acid. Example S The metal-based paint-forming materials of Sample 1 and Sample 2 in Example IK were added to the current solution of Example 1 at 0.5 f/ferric chloride.
I was added, and am was carried out in the same manner as in Example 1. Sample 1 achieved good m in 2I seconds and sample snow in 45 seconds.
I was able to do it.

Patent applicant: Toyobo Co., Ltd. Toppan Printing Co., Ltd. Continuation of page 1 0 shots clear by Takao Taguchi 942-174 Naganumaharacho, Chiba 0 applicants Toppan Printing Co., Ltd. 1-5-1 Taito, Taito-ku, Tokyo issue

Claims (1)

[Claims] (1) In a method of forming a metal surface on a support using a metal soluble in an alkaline aqueous solution, a thin metal layer containing iron ions and /17'E containing steel ions is provided. (2)
2. The gold-1 film forming method according to claim 1, wherein the photosensitive resin layer contains an active light absorber and/or a colorant. (3) Claim 1, wherein an active light I/s absorption layer and/or a colored layer are provided between the metal thin layer soluble in an alkaline aqueous solution and the photosensitive resin layer. Money H"?'
va *Formation method・t(4) Am light is irradiated with actinic rays onto a metal-forming material provided with at least a thin alkaline water 111f[K-soluble metal layer and a photosensitive resin layer on a support. After applying
In a method for reducing the strength of a metal-based image obtained by development, the metal-based thin layer contains iron ions and/or (5) the metal-based thin layer of the metal-based image contains iron ions and/or copper ions. 5. The method for reducing the force of a metal yoke according to claim 4, wherein the method is performed using an alkaline aqueous solution. (6) Actinic ray absorber and /1 (7) in the photosensitive resin layer
An actinic ray absorbing layer and/or an active light absorbing layer is provided between the metal thin layer soluble in an alkaline aqueous solution and the photosensitive resin layer.