JPS6049933A - Laminate for forming picture - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION [Technical Field] The present invention relates to an image-forming laminate that is provided with image print-out properties upon exposure, and more particularly relates to a peel-off or print-out property that allows a visible image to be obtained immediately after exposure. The present invention relates to an image forming laminate covered with a removable light-transmitting protective film.

[Conventional technology]

Many types of image forming materials are in practical use, such as lithographic printing plates, photoresists, and resin letterpress materials.

In such an image forming material, it is necessary to distinguish between exposed and unexposed areas after exposure under a safety light during exposure work. For example, in the exposure work of a lithographic printing plate, if the exposed portion cannot be identified in a multi-sided printing operation using a combiner or in a printing-out operation, erroneous operations such as multiple printing-out may occur, which significantly reduces the workability. In other imaging materials, it is necessary to be able to identify at least whether the material has been exposed or not.

Therefore, several attempts have been made in the past to form a visible image after exposure.

For example, as shown in Special Publication No. 40-2203,
Obtaining a visible image from a photosensitive diazo substance and an acid-base indicator, as shown in Japanese Patent Publication No. 40-21093,
- pH 2.5 in the photosensitive layer consisting of naphthoquinone siacite
~65 containing an organic coloring agent that changes its color tone, as shown in Japanese Patent Publication No. 57-6572, an organic dye that changes its color tone by interacting with the photodecomposition product of an O-naphthoquinonediaside compound. Examples include things that include.

However, even with these improvements.

The contrast of the visible image obtained by exposure is often not sufficient under yellow safety lights in actual work, and even when sufficient contrast is obtained, it is difficult to print out the image due to the presence of substances added to the photosensitive layer. However, sensitivity 1 had an adverse effect on image reproducibility, stability over time, and developability, and in some cases, after long-term storage, sufficient contrast performance was not achieved.

Also, lithographic printing plates that do not require dampening water and consist of a support, a photosensitive layer, and an ink-repellent silicone rubber layer, such as JP-A No. 48
-94504, JP-A-49-88607, JP-A-55-
No. 59466, JP-A No. 55-110249, JP-A-55-110249, /l'+ JP-A No. 56-80046, etc., do not give any consideration to the image printability.

[Purpose of the invention]

By eliminating these conventional drawbacks, a visible image with sufficient contrast can be obtained immediately after exposure.

And for this purpose, an image forming laminate that does not have any adverse effect on the image reproducibility or various originally required performances.

Among other things, the object is to provide a lithographic printing plate that does not require dampening water.

[Structure of the invention]

As a result of extensive research, the present inventors have developed a method of imparting print-out properties to a peelable or removable light-transmitting protective film that covers the main surface of an image-forming laminate.

It has been found that the above objectives are achieved.

The light-transmitting protective film of the present invention that has print-out property and is peelable or removable is one in which a thin film layer with print-out property constitutes an upper or lower layer portion of the protective film. The protective film is characterized in that the entire protective film has a print-out property.

The thin film layer having print-out property refers to the above-mentioned substance having image print-out property or a thin film formed from a material containing the same, and any known material can be used as long as it has film-forming properties. It is something that can be used. For example, U.S. Pat.
Mixtures of various reducible salts and diazo compounds as shown in No. 06691 3 and U.S. Pat. and an acid-base indicator, as shown in Japanese Patent Publication No. 49-3041; one consisting of a photosensitive positive-acting diazo resin and a merocyanine dye; as shown in Japanese Patent Publication No. 40-21093. , O-naphthoquinone diazide and pH 2.5
~65 containing an organic coloring agent that changes the color tone in homogeneous granular form, as shown in JP-A No. 50-36209.
+ O-Naphthoquinonediazide compound and 10 to 75% by weight of naphthoquinonediazide 4-sulfonic acid halide and an organic compound having salt-forming ability as a dye in the range of 1 to 50% by weight based on the total content thereof.

As shown in Japanese Patent Publication No. 57-6572.

Containing an organic dye that changes color tone through interaction with a naphthoquinone diazide compound and its photodecomposition product, JP-A-5
5. -48749 as shown.

Containing 0-naphthoquinonediazide sulfonic acid ester and specific triarylmethane dyes, Research Disclosure Na1 57 (May 1977) No. 5
As shown on pages 0 to 54, combinations of leuco dyes and organic azide compounds, as shown in JP-A-55-62070, containing dye precursors, specific triazines, and specific benzothiazoles. Examples include commercially available photosensitive liquids for Wipon plates (those with an image printout function).

The thickness of the thin film layer is not particularly limited as long as it does not interfere with image exposure of the image forming laminate, but it is usually 0.2 to 50 .mu.m, preferably 0.5 to 20 .mu.m.

However, the entire protective film still has bake-out properties.

For example, a photochromic protective film can be used.

The film or sheet used in the present invention, which holds the printable thin film layer on the upper or lower part to serve as a protective film, or the film or sheet that itself serves as a printoutable protective film, is usually easily produced. It is available in
It must have sufficient transparency to allow exposure light for image formation to pass through, and strength as a protective film, and must also be peelable or removable after exposure and before development. Is the moon that constitutes such a film or sheet a moon? ``Niuna Polyester'' from Lieterenteleftcrete.

BoIJ 7I celliolefin such as fluoropylene, polyethylene, polyvinyl chloride, polyvinylidene chloride, polyvinyl acetate, polystyrene, or a copolymer thereof, nitrocellulose, or a sheet having the above-mentioned properties Any polymer can be used as long as it can form a physical or film.

The thickness of such a film or sheet is selected within a range that does not impair image exposure, but is usually 0.5 to 100 μm.
, preferably 4 to 0 μm.

An image forming laminate suitable for use with the protective film of the present invention is a lithographic printing plate that does not require dampening water, and a particularly preferred one is a photosensitive layer on a support and an ink-repellent silicone rubber layer on the photosensitive layer. Laminated.

Alternatively, it consists of an ink-repellent silicone rubber layer on a support, and a photosensitive layer laminated thereon. For example, the method for manufacturing such a printing plate is as follows.

Special Publication Showa 46-16044. JP-A-48-94504, JP-A-50-5.9101. Unexamined Japanese Patent Publication No. 5O-i61ro 05.
JP-A-55-59466, JP-A-55-110249.
It is described in JP-A-56'-80 [No. 346, etc.].

Further, such a protective film may have either a smooth surface or a textured surface.

〔Effect of the invention〕

(1) Image printout properties can be imparted to the image forming laminate.

(2) The present invention, which allows the surface protective film to have some image printout properties, does not affect the image forming properties, which is the original role of the photosensitive layer, compared to the conventional method, which imparts image printout properties to the photosensitive layer. It must not cause any damage.

(3) The method of imparting printout properties to a photosensitive layer depends on the properties of the photosensitive layer itself, and must be adapted to each photosensitive layer used.9 According to the method of the present invention, the type of image forming laminate can be It can be used for almost anything you ask.

The present invention will be explained below with reference to Examples, but the present invention is not limited thereto.

Example 1 Phenol formaldehyde resol resin (Sumilight Resin PC-1.Sumitomo Durez←) was coated on a 0.24 mm thick aluminum plate manufactured by Sumitomo Light Metal @) to a thickness of 1μ (dry thickness) and heated at 200°C. - It was cured for 6 minutes and used as a support. The following photosensitive layer composition was spin-coated onto this support and cured by heating at 120° C. for 2 minutes to provide a 2 μm thick photosensitive layer.

(a) Phenol novolac resin 7-quinone, -
1,2-diazido-5-sulfonic acid partial ester 10 (] 1 part by weight b) 4,4'-diphenylmethane diisocyanate 30 parts by weight (c) Dibutyltin diacetate 0.2 part by weight (d)
A silicone rubber composition having the following composition was spin-coated onto this using 200 parts by weight of dioxane and cured under heat at 120°C and a dew point of 60°C for 2 minutes to form a 25μ thick silicone rubber layer.

(E,) 1 part of dimethylbolysilogysan 100M (molecular weight approximately 25,000. Both terminal hydroxyl groups) (b)
−+) , ;r, (2-phthanone oxime) sila 7
8 parts by weight (C) Dibutyltin diacetate 02 parts by weight (cl)
0.5 parts by weight of 3-aminopropyltrimethoxysilane (e) 1,800 parts by weight of Isopar E (manufactured by Exxon Chemical Co., Ltd.) A negative-working lithographic printing plate that does not require dampening water was prepared as described above, and furthermore, a @) polypropylene film''
Laminate the film with ``Torefan'' with a thickness of 8μ using a laminator.Furthermore, apply a negative-type photosensitive liquid ``Sanwa Ibon'' manufactured by Koyo Chemical Industry Co., Ltd. (RO) using a bar coater on floor 6 and dry it for 3 minutes at 35℃. 9 A protective film of the present invention was formed.

I-Gafilm was vacuum-adhered to the lithographic printing plate that did not require dampening water and was coated with such a protective film, and using a metal sheet lamp "Idol Fin" (manufactured by I-Graphic @),
When the image was exposed for 90 seconds at an illuminance of 11 mW/an2, the color of the 9 image exposed areas changed to blue-black.

Under yellow light, it was clearly distinguishable from the unexposed area (yellow). The protective film of this exposed plate material is removed.

As a known developer, ethanol/isopar 1r described in JP-A No. 146-146, ethanol/isopar 1r,
When developed with a mixed solution of Exxon Chemical (Pavement) (20/80 weight ratio), the silicone rubber layer in the exposed areas was removed and a printing plate with an image faithful to the negative film was obtained.

Example 2 Eboki 7/urea resin (KP color 87
04 Clear: Kansai Paint (I) Co., Ltd.) Coating liquid (solvent: ethyl cellosolve/ethyl cellosolve acetate-1/butyl cellosolve 40/40/20 ratio 1 weight ratio) was applied, and the coating solution was applied at 250°C and 60°C. A heat treatment was performed for seconds to form a cured resin coating film with a thickness of 5 μm.

Then, on top of this, a photosensitive solution of ethyl cellosolve solution consisting of 10% by weight solid components was applied with the following composition,
A photosensitive layer having a thickness of 4 μm was provided by drying in hot air at 80° C.

(a) Polyurethane resin “Pantex T-2501
” (manufactured by Inu Nippon Ink Chemical (Il!I)) 56 parts by weight (
b) Addition product of 4 moles of glycidyl methacrylate and 1 mole of xylylene diamine 40 parts by weight (c) 4 parts by weight of Michler's Keto 7 (d) Crystal iolet 04 weight M fjB
On this photosensitive layer, a solution of a silicone comb composition having the following composition in n-hexane was applied.

A silicone rubber layer having a thickness of 6 μm was provided by drying in hot air at 50° C.

(a) Poly/methylnoroxane 0 parts by weight (molecular weight approximately 80,000) (b) Methyltriacetoxane 5 parts by weight (C)
Dibutyltin diacetate 02 parts by weight The top layer of the printing plate thus prepared was laminated with a 10 micron thick polyethylene terephthalate film "Lumirror" (manufactured by Toshiki A) to form a positive working water-less lithographic plate of the present invention. Got the print version.

On top of this printing plate, a photosensitive liquid "Sanwaibo/" for Bojikub made by Koyo Kagaku Kogyo Co., Ltd. was applied using a whirlpool and dried, and a thin film layer with a thickness of 1 micron with image printing properties was provided on the top for protection. A film was formed.

A positive film was vacuum-adhered on top of this, and exposed for 120 seconds from a distance of 1 m using an ultra-high pressure mercury vapor lamp (manufactured by Oak Seisakusho (Ha)).
The exposed areas of the image developed a red color and were clearly distinguishable from the yellow unexposed areas under yellow light.

Then, after peeling off this protective layer film, a developer consisting of n-hexane/ethyl cellulose 7' = 98/2 (part i) was soaked into the developing pad.

The silicone rubber layer in the unexposed areas was peeled off by rubbing the printing plate, and development was performed. In this way, a printing plate with an image faithful to a positive film was obtained.

Patent applicant Higashi Shikikai Co., Ltd.

Claims (2)

[Claims] (1) An image-forming laminate whose main surface is covered with a light-transmissive protective film that is peelable or removable, characterized in that the protective film is coated with print-out properties. (2) The laminate according to claim 2, wherein the image forming laminate is a lithographic printing plate that does not require dampening water.