JPH0327105B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an image forming material capable of producing a positive relief image of arbitrary density and tone, and an image forming method thereof. Reversal films, overlay-type pre-press color proofs that require a color tone very close to that of printing ink, and those that allow the same image-forming material to be used for close reversal and proofing work, as well as character proofing films and plates. The present invention relates to image forming materials and image forming methods used in printing materials such as base photographic paper, light-shielding mask films, and second original drawing films in the field of design and drafting.

Conventionally, methods for obtaining positive relief images using ultraviolet light as a light source include (1) an image forming material in which a photosensitive layer consisting of a 1,2-quinonediazide compound and an alkali-soluble resin binder such as novolac resin is formed on a support; A method in which the exposed areas are developed using an alkaline aqueous solution.

(2) Using an image forming material in which a photosensitive layer consisting of a reaction product of p-diazodiphenylamine and phosphotungstic acid and a vinylidene chloride-acrylonitrile copolymer binder is formed on a support, the exposed areas are A method of developing with a water-alcohol solution.

(3) A method in which an image-forming material is prepared by forming a photosensitive layer comprising a water-soluble diazonium salt and a water-soluble resin binder on a support, and the exposed areas are treated with an alkali and then developed by washing away with water.

etc. are known.

However, such conventional methods have the following problems.

In other words, in method (1), the binder resin is difficult to dye, and it is difficult to combine it with an efficient and stable coloring mechanism.Additionally, adding a large amount of coloring agent to the photosensitive layer lowers the sensitivity, resulting in high-density images. is not obtained. Furthermore, the formed image has low solvent resistance to commercially available film cleaners and the like, and since the binder resin is dissolved in the alkaline aqueous solution together with the decomposed sensitizer in the non-image area, the alkaline aqueous solution is quickly exhausted.

In method (2), by further providing a colorant layer on the photosensitive layer formed on the transparent support, it is possible to obtain a high density image without reducing the sensitivity. This has to be done from the body side, and a decrease in resolution due to the thickness of the base material cannot be avoided. Furthermore, although high-density images can be obtained by staining with method (3), images with arbitrary tones cannot be obtained due to the coloring reaction during alkali treatment.
The photosensitive layer has no water resistance, the photosensitive layer has strong tack,
It has disadvantages such as low storage stability.

The inventors of the present invention have been earnestly conducting research on new photosensitive materials that solve the above-mentioned conventional difficulties, and discovered that a water-soluble polymeric compound, diacetone acrylamide-acrylamide copolymer, and a water-insoluble 1,2-quinonediazide compound have been developed. A positive relief image is formed by coating a photosensitive layer on a support, exposing it to pattern light through a positive original, immersing it in an alkaline aqueous solution, washing away the exposed non-image area, and drying it. We have discovered a phenomenon in which a highly colored positive relief image can be obtained by dyeing this with an aqueous dye solution.

The mechanism of this image formation is to form a photosensitive layer on a support using, for example, diacetone acrylamide-acrylamide copolymer as a binder and containing a water-insoluble 1,2-quinonediazide compound.
Pattern exposure through a positive manuscript, 1,2-
Although the decomposed product of the quinonediazide compound is eluted from the photosensitive layer, the binder is hardly eluted, and the 1,2-quinonediazide compound in the unexposed area is not eluted at all. Next, by washing with water, 1,2-
The binder in the area where the quinonediazide compound has eluted is removed by washing with water, but the area where the 1,2-quinonediazide compound remains is water resistant and is therefore not removed by washing with water, forming a positive relief image.

Furthermore, this positive relief image can also be highly concentratedly stained using a staining solution.

Based on the above knowledge, the present invention has general performance that (1) has image reproduction characteristics that can sharply reproduce 175 lines, 3 to 97% halftone image, and high resolution; (2)
Optical density 3.00 by staining with staining solution
(3) By selecting the coloring agent added to the photosensitive layer or the dye in the dyeing solution, images with arbitrary tone and density can be obtained; (4) Low influence by temperature and humidity. , has excellent storage stability, (5) the photosensitive layer is water resistant and does not tack, (6) the formed image has excellent solvent resistance to commercially available film cleaners, etc., (7) an alkaline aqueous solution contains 1, Since the photodegradable product of the 2-quinonediazide compound elutes and the photosensitive layer binder hardly elutes,
The object of the present invention is to provide an image forming material capable of forming a positive relief image and an image forming method using the same, which have practical performance such as less fatigue of alkaline aqueous solution and (8) high workability because it can be processed in a bright room.

The present invention will be explained in more detail below.

In the image-forming material of the present invention, a photosensitive layer is formed on a support that has been subjected to primer treatment if necessary.
Supports used in the present invention include plastic films such as polyethylene terephthalate, polypropylene, polyethylene, polyvinyl chloride, polystyrene, polycarbonate, and triacetate, glass plates, and paper made waterproof by laminating polyethylene or polypropylene on both sides. Can be mentioned. In addition, sand matte film is produced by the sandplast method on one or both sides to allow writing with pencil, ink, ballpoint pen, etc., and chemical matte film has a coated surface made by blending additives such as dyes, pigments, and fillers in the binder. It is also possible to use film, plastic film that has been made suitable for drafting, such as etched matte film that has been etched with alkali, and opalescent film that has been kneaded with white pigment.

The photosensitive layer may be applied directly to the support, but
To improve adhesion, corona discharge treatment,
It is desirable to apply a primer treatment agent or to perform an adhesive treatment using a combination of these agents. As the primer treatment agent, phenol resin, polyester resin, urethane resin, vinylidene chloride-vinyl acetate copolymer, vinylidene chloride-acrylonitrile copolymer, etc., and mixtures thereof are used, and a treated film of 0.1 to 2.0μ is formed on the support. Apply thickness. In particular, when using sand matte film or chemical matte film as a support, the above-mentioned primer treatment is used to strengthen the adhesion between the matte layer and the photosensitive layer and to prevent adsorption of colorants, dyes, etc. used in the photosensitive layer. It is preferable to apply a coating agent.

The photosensitive layer of the present invention includes a copolymer of diacetone acrylamide and acrylamide and/or a copolymer of diacetone acrylamide and acrylamide and one or more other components as a binder, and a water-insoluble 1,2-quinone diazide as a sensitizer. It consists of a compound, and if necessary, a coloring agent is added.

The above diacetone acrylamide-acrylamide copolymer is diacetone acrylamide 20~
It is used as a copolymer with 50 mol% of acrylamide and 50 to 80 mol% of acrylamide. However, if the amount of diacetone acrylamide exceeds this copolymerization ratio, the dyeability of the formed image will decrease and the removability of non-image areas will decrease. On the other hand, if it decreases, the coating film becomes more soluble in alkaline aqueous solution, and it becomes difficult to adjust the coating solution for the photosensitive layer due to the decrease in compatibility with the water-insoluble 1,2-quinonediazide compound. There are other problems. In addition, the above-mentioned binder is used to improve the storage stability of the photosensitive layer, the water resistance of images, the dyeability of images, the washability of non-image areas, the adhesion with supports, and the stability and reproducibility of copolymerization reactions during synthesis. Copolymers consisting of diacetone acrylamide, acrylamide, and one or more other components are also used for the purpose of improving
Diacetone acrylamide 20-50 mol%, acrylamide 50-80 mol%, one or more other components 15
It can be used as a copolymer of components of up to mol %, more preferably up to 10 mol %.

The other one or more components mentioned above include methyl methacrylate, hydroxyethyl methacrylate,
Hydroxypropyl methacrylate, t-butyl methacrylate, styrene, α-methylstyrene, chloromethylstyrene, methacrylic acid, 2-
Acrylamido-2-methylpropanesulfonic acid, acrylonitrile, and the like are effective.

Further, as the binder, a copolymer of diacetone acrylamide and acrylamide, and a copolymer of diacetone acrylamide, acrylamide, and one or more other components may be mixed.

Furthermore, for example, polyvinyl alcohol,
It is also possible to use a mixture of a small amount of a water-soluble polymer compound such as polyacrylamide or polyvinylpyrrolidone, or an alkali-soluble polymer compound such as a phenol novolak resin or styrene-maleic anhydride.

The water-insoluble 1,2-quinonediazide compound may be one of the known 1,2-quinonediazide compounds, and any one can be used as long as it is compatible with the binder. i.e. 1, 2-
Naphthoquinonediazide = (2)-4-sulfonyl chloride, 1,2-naphthoquinonediazide (2)-5-
Examples include sulfonyl chlorides and condensates of these with alkali-soluble phenol novolac resins. Also, “Light−
Sensitive Systems” 339-352, (1965), John
Wiley & Sons (New York) and WSDeForest
“Photo-reist”50, (1975) Mc GrawHiLL,
Inc. (New York), water-insoluble 1,2-quinonediazide compounds and the like can also be used.
The amount of 1,2-quinone azide compound added varies depending on the type, but if it is too large, sensitivity may decrease,
If the dye density is too low, the water resistance will decrease and good images will not be obtained. It is desirable that there be.

A colorant can be added to the photosensitive layer used in the present invention, but if the amount of colorant added is too large, the sensitivity will decrease, so the amount added must be selected within a range that does not significantly increase the optical density. There is. As the coloring agent, used are coloring pigments and dyes that have good miscibility with the binder and the water-insoluble 1,2-quinonediazide compound and do not adversely affect photosensitivity, developability, storage stability, etc. For example, color pigments such as Permanent Yellow HR, Permanent Yellow DHG, and Permanent Carmine.
Examples include FB, permanent carmine FBB, phthalocyanine blue, carbon black, etc., and mixtures thereof, and for any of them, sufficient consideration must be given to particle size, dispersion state, etc. so as not to deteriorate the quality of the formed image. The dyes are Direct First Yellow GC, Rose Bengal, Rhodamine B,
Water-soluble dyes such as Congo Red, Dimethylene Blue, Soluble Blue, Direct Sky Blue 5B and mixtures thereof, Oil Yellow 5G,
Oil Yellow 3G, Oil Red G, Oil Red ERR, Oil Red 5B, Oil Black
Oil-soluble dyes such as HB, Savon Fastread BB, Savon First Blue HFL, etc. and mixtures thereof can be used.

In addition to the above-mentioned components, the photosensitive layer of the present invention may contain a stabilizer to prevent dark reactions, a leveling agent, an antifoaming agent, etc. to improve coating properties when forming the photosensitive layer. Can be added.

There is no particular restriction on the coating thickness of the photosensitive layer of the present invention, but for reasons such as resolution and image reproducibility, it is preferably as thin as possible and preferably 5 μm or less.

The primer treatment agent and photosensitive layer may be coated by any conventionally known method such as roll coating, reverse roll coating, dip coating, wire bar coating, etc., and can be applied uniformly without pinholes or uneven coating. There are no particular limitations as long as a coating film can be obtained.

The image forming material of the present invention uses ultraviolet rays as a light source, and after exposure through a document, an image is formed by immersing the material in an alkaline solution and removing the exposed non-image areas by washing with water.

The ultraviolet light source used in the present invention may be one having a spectral energy distribution that effectively decomposes the water-insoluble 1,2-quinonediazide compound, such as various mercury lamps, carbon arc lamps, xenon lamps, metal halide lamps, Ultraviolet fluorescent lamps, etc. can be used.

The alkaline aqueous solution used in the present invention includes sodium hydroxide, potassium hydroxide, sodium carbonate,
An aqueous solution of sodium silicate, sodium metasilicate, etc. is used, and the immersion time of the exposed image-forming material at room temperature is sufficient to be 90 seconds or less.

In the present invention, the binder in the non-image area is removed by washing with water, using room temperature water jetted from a nozzle pressurized to 2 kg/cm ² or less, or by lightly rubbing with a sponge in room temperature water.

The image-forming material of the present invention forms a positive relief image through the above steps, but if no colorant is added to the photosensitive layer, or if a higher density image is to be obtained, the image-forming material may be immersed in an aqueous dye solution. It is possible to dye. Dyes used for dyeing include Primula Yellow 2R, Paper Yellow 2G, Primula Orange FP, Direct Roselyn Red B, and Direct Fast Red.
Direct dyes such as FA, Direct Brown MA, Direct Brown 3G, Direct Fast Black B, Direct Dup Black XA, Chuganol Blue G, Chuganol Milling Green 8GH, Chuganol Milling Red
Acidic dyes such as 3G and Acidol Brown M-BL can be used, and if necessary, alcohol-based dyes,
The dyeability can be improved by adding ether-based, glycol-based, or other water-compatible organic solvents and various surfactants, and by increasing the temperature of the dyeing solution. Furthermore, after dyeing, it is also possible to use a nonionic surfactant as a cleaning agent and an aqueous solution of potassium alum, tannic acid, glacial acetic acid, etc. as a hardening mordant.

Examples are shown below to further clarify the present invention, but the present invention is not limited thereto.
In addition, each transmission density and reflection density are provided by Dainippon Screen Manufacturing.
The values are based on DM-500 and DM-400 manufactured by Co., Ltd.

Example 1 Liquid A (photosensitive layer coating liquid) Diacetone acrylamide 70 parts by weight - Acrylamide copolymer 15% solution of water/ethylene glycol monomethyl ether = 9/1 Copolymerization ratio 40:60 Viscosity 2000 cps at 25°C 1, 2-Naphthoquinonediazide (2)-5-
3 parts by weight Sulfonyl chloride Ethylene glycol monoethyl ether
60 parts by weight Methanol 140 parts by weight Apply liquid A using a wire bar to the mat surface of a polyethylene terephthalate film with a thickness of 80 μm that has been subjected to sand mat processing using the sandblasting method, and dry for 1 minute in a blow dryer at 80°C to form a photosensitive layer. A positive original was brought into close contact with the photosensitive layer of the image forming material having an average film thickness of 3.0 μm and exposed for 20 seconds from a distance of 1 m using a 2 KW ultra-high pressure mercury lamp.

The image-forming material thus exposed is immersed in a 10% sodium hydroxide aqueous solution for 30 seconds, and then the exposed non-image area is removed by lightly rubbing the photosensitive layer with a sponge soaked in water under running water, resulting in a positive relief image. was gotten.

Solution B (staining solution) Direct Fast Black B 3 parts by weight Ethylene glycol 20 parts by weight Water 80 parts by weight The obtained image was then immersed in Solution B at 30°C for 2 minutes, resulting in a good positive color with an optical density of 2.50. A relief image was obtained.

The image forming material and image forming method obtained in this example could be widely and effectively used in fields such as surveying, mapping, and design drawing as a second original drawing film suitable for drafting and its processing method.

Example 2 Liquid C (primer treatment agent) Vinylidene chloride - 10 parts by weight Acrylonitrile copolymer Methyl ethyl ketone 100 parts by weight Trichloroacetic acid 2 parts by weight Liquid D (photosensitive layer coating liquid) Diacetone acrylamide 70 parts by weight - Acrylamide - Hydroxypropyl Methacrylate copolymer 15% solution of water/ethylene glycol monomethyl ether = 9/1 Copolymerization ratio 38:57:5 Viscosity 1600 cps at 25°C 1,2 naphthoquinone diazide (2)-4-
3.5 parts by weight Condensate of sulfonyl chloride and alkali-soluble phenol novolak resin 5 parts by weight of pigment dispersion (20% carbon black) Fluorine surfactant 0.2 parts by weight Ethylene glycol monoethyl ether
220 parts by weight Isopropyl alcohol 10 parts by weight However, the pigment dispersion liquid was obtained by dispersing in an ink mixer for 3 hours with the following composition.

Pigment 60 parts by weight Polyethylene glycol alkyl phenyl
1 part by weight Ether-based nonionic activator ethylene glycol monoethyl ether
59 parts by weight Water 180 parts by weight 80μ thick synthetic paper (Yupo manufactured by Oji Yuka Synthetic Paper Co., Ltd.)
Liquid C was applied to one side of FPG (80μ) using a roll coater and dried at 100°C for 1 minute to provide a primer treatment with a dry film thickness of 1.5μ. Next, apply Solution D on the primer-treated surface using a wire bar to a dry film thickness of 2.5 μm, and then dry it for 2 minutes in a blow dryer at 80°C to form a colored photosensitive layer with a reflection density of 1.50. An imaging material was obtained.

Next, a positive original was brought into close contact with the photosensitive layer of this image forming material and exposed for 150 seconds from a distance of 1 m using a 2 KW ultra-high pressure mercury lamp.

After immersing the thus exposed image forming material in a 5% aqueous sodium metasilicate solution for 30 seconds,
The non-image area was washed away with water using a room temperature water shower sprayed from a nozzle under a pressure of 1.5 kg/cm ² , and a good positive relief image colored with a reflection image density of 1.50 was obtained.

The image forming material and the image forming method obtained in this example were able to sharply reproduce halftone images of 3 to 97% of 175 lines, so they were used as proofing materials in the printing and plate making field, and as silver halide photographic paper used in the preparation of block plates. It could be used effectively for a wide range of purposes, including as a substitute.

Example 3 Liquid E (photosensitive layer coating liquid) Diacetone acrylamide - 70 parts by weight Acrylamide-styrene copolymer 15% solution of ethylene glycol monomethyl ether/isopropyl alcohol = 8/2 Copolymerization ratio 38:60:2 Viscosity 25 2200 cps at °C 1,2-naphthoquinone azide (2)-5- 3 parts by weight Condensate of sulfonyl chloride and alkali-soluble phenol novolak resin 4 parts by weight of pigment dispersion (20% carbon black) Fluorine surfactant 0.2 Part by weight Ethylene glycol monoethyl ether
240 parts by weight Liquid F (photosensitive layer coating liquid) Only the pigment dispersion is made into a 20% permanent yellow dispersion using liquid E. Liquid G (photosensitive layer coating liquid) Only the pigment dispersion is made into a 20% permanent carmine FB dispersion using liquid E. Solution H solution (photosensitive layer coating solution) Only the pigment dispersion in E solution was made into a 20% phthalocyanine blue dispersion.However, the pigment dispersion of E solution, F solution, G solution, and H solution is the same as Example 2. Prepared in the same manner.

The C solution (primer treatment agent) used in Example 2 was applied to one side of a 100μ thick polyethylene terephthalate film using a roll coater, and the film was coated at 100℃ for 1 hour.
After drying for minutes, a primer treatment was performed to give a dry film thickness of 2.0 μm.

Next, apply liquid E on the primer treated surface to a dry film thickness.
After coating with a wire bar to a thickness of 3μ, 80℃
The image forming material was dried for 2 minutes in a blow dryer to obtain a black colored image forming material.

Next, solutions F, G, and H were applied to polyethylene terephthalate film that had been primed in the same manner as solution E, and the films were colored yellow, magenta, and cyan, respectively.
An image-forming material of

Next, a black plate of color-separated halftone positive film was brought into close contact with the photosensitive layer of film-1, and from a distance of 1 m,
After exposure for 120 seconds with a 2KW ultra-high pressure mercury lamp,
% sodium metasilicate aqueous solution for 30 seconds,
The non-image area was washed away with room temperature water jetted from a nozzle pressurized to 1.5 kg/cm ² to obtain a positive relief image colored black.

Next, the yellow version of the color-separated halftone positive film, the magenta version for the film, and the cyan version for the film were used in the same way as the film, with only the exposure times changed to 60 seconds, 40 seconds, and 60 seconds, respectively. Positive relief images colored yellow, magenta, and cyan were obtained. The transmission density of each image was 0.75, 0.63, 0.75, and 0.80. When these four kinds of colored positive relief images are formed on the films and observed on a white paper, each image is combined and a color image that closely resembles the final printed matter is obtained, which can be used as an excellent overlay type pre-press color proof for the printing process. It could be used effectively for proofreading work.

Next, the films with each colored image were soaked in solution B (staining solution) used in Example 1 at 40°C for 2 minutes.
When immersed in the liquid, each image was colored into a black image with a density of 3.0 or more, and the density of the non-image area was 0.08 or less.

Furthermore, when these were used as manuscripts and each color separation plate was printed on a commercially available PS plate, four-color printing was performed using an offset printing proofing machine, and the finish was good.

The image-forming material and image-forming method obtained in this example can be widely and effectively used in the printing and plate-making field as a pre-press color proof, a contact reversal film, and as a device that can perform these operations with the same image-forming material. did it.

As is clear from the above examples, the present invention provides an image forming material and an image forming method thereof that can be widely and effectively used in the printing plate making field, reproduction field, etc., but also in Examples 1 to 3. The exemplified image-forming materials of the present invention have a heat resistance test of 50°C and a temperature of 90°C.
%RH and 30℃ humidity resistance test, there was no change in sensitivity, image reproducibility, developability, stainability, etc. after 30 days, and it has excellent storage stability. The photosensitive layer is water resistant, does not touch with fingers, and can be worked in a bright room, so it has excellent workability. The formed image also has properties such as solvent resistance against commercially available film cleaners mainly containing 1,1,1-trichloroethane.

Claims (1)

[Scope of Claims] 1. A copolymer of diacetone acrylamide and acrylamide and/or a copolymer of diacetone acrylamide and acrylamide and one or more other components, a water-insoluble 1,2-quinonediazide compound, and further necessary 1. An image forming material comprising a photosensitive layer formed on a support, to which a colorant is added according to the conditions. 2. The image forming material according to claim 1, wherein the components of the copolymer of diacetone acrylamide and acrylamide are 20 to 50 mol% of diacetone acrylamide and 50 to 80 mol% of acrylamide. 3 The components of the copolymer consisting of the above diacetone acrylamide and one or more other components are 20 to 50 mol% of diacetone acrylamide, acrylamide
The image-forming material according to claim 1, wherein the content of one or more other components is 50 to 80 mol % and 15 mol % or less. 4 A copolymer of diacetone acrylamide and acrylamide and/or a copolymer of diacetone acrylamide and acrylamide and one or more other components, a water-insoluble 1,2-quinonediazide compound, and a colorant if necessary. A process of forming a positive relief image by exposing the image forming material on which the photosensitive layer formed by adding the above-mentioned photosensitive layer is formed on the support (A) to pattern light through a positive original, immersing it in an alkaline aqueous solution, and removing the exposed non-image area by washing with water. (B) In the process of dyeing the positive relief image obtained in step (A) with an aqueous dye solution to form an image with a higher optical density than that obtained in step (A), a coloring agent is added to the photosensitive layer. A colored positive relief image is formed by the steps (A) or (A) and (B) if the colorant is added, or by the steps (A) and (B) if the colorant is not added to the photosensitive layer. An image forming method characterized by: