JPH0743894A - Image forming material and image forming method - Google Patents

Abstract

PURPOSE:To make an image usable possible for a color proof and a printing plate and the like to be directly formed by a digital system by forming a specified composition on a support. CONSTITUTION:The image-forming material contains as a first essential component an o-quinonediazido compound and as a second essential component an additive having a chemical structure represented by formulae (1)-(7), selected from a cyanine type dye, an azulenium type dye, and a quinone type dye, a thiazine type dye, and the like having maximum absorption wavelength (lambdamax) in the wavelength region of 670-1250nm, and capable of forming an alkali- insoluble product by heat reaction with the photoreaction product of the o- quinonediazido compound in an amount of 0.03-0.7 pts.wt. of the quinonediazido compound. In formulae (1)-(7), each of R1 and R2 is, independently, H, alkyl, alkoxy, aralkyl, or aryl.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION An object of the present invention is to use an infrared laser such as a semiconductor laser and an image forming material which enables digital recording such as direct digital plate which is easy to print on a printing machine, and the use thereof. An object is to provide an image forming method.

[0002]

As is well known, when an o-quinonediazide compound is irradiated with an actinic ray, the diazo group in the compound is decomposed into a compound containing a carboxyl group and becomes alkali-soluble. Therefore, when a light-sensitive material containing an o-quinonediazide compound is imagewise exposed and then developed with an alkaline developer, the exposed portion is dissolved and removed in the developer, and the non-exposed portion remains on the light-sensitive material to form an image. A so-called positive working image forming material is obtained.

However, for example, JP-A-49-127
No. 615, No. -10802, No. 56-62.
No. 36, No. 56-36648, and Japanese Patent Publication No. 62-
No. 49613, No. 62-49614, etc., the o-quinone diazide compound is used as a photosensitive component, and further aliphatic amine, N-alcohol amine, aromatic ketone, quinone compound, imidazole compound The photosensitive material having a photosensitive layer composed of a composition containing an additive is capable of positive working to form a positive image by developing after imagewise exposure as described above. Alternatively, after imagewise exposure, heating is performed to provide uniform exposure, and development processing is performed, whereby negative working processing is possible.

By the way, these additives disclosed in the above specification do not substantially have large absorption in the visible region. If a dye or dye having an absorption in the visible region can be used as an additive for reversing negative working, after uniformly exposing it to the active light of an o-quinonediazide compound, patterning with a high-power argon laser etc. By irradiating and converting the light of the laser into heat to insolubilize the irradiated part, there is a possibility that various images including a printing plate can be directly formed by digital recording by the laser without using a mask.

Japanese Patent Publication No. 62-49615 discloses a technique based on such an idea. That is, o-
A quinonediazide compound as a photosensitive component, diphenylmethane dye, triphenylmethane dye, xanthene dye,
A photosensitive material is disclosed in which a support is provided with a photosensitive composition containing an additive for inverting a basic carbonyl dye selected from acridine dyes. This photosensitive material is exposed to the whole surface by using active light of an o-quinonediazide compound, and thereafter, a laser beam such as an argon laser is imagewise irradiated, and then the non-irradiated portion is dissolved and removed by an alkaline developer to perform negative working. An image is formed.

However, the system based on this technology has not yet appeared as a product in the world. The main reason for this is the use of large water-cooled lasers due to their low sensitivity, or the very slow scanning speed.

On the other hand, recent advances in semiconductor lasers that emit infrared laser light, such as miniaturization, higher output, and multi-beam laser technology incorporating several to several tens of these high-power lasers, are remarkable. There is something to watch. Due to these technological advances, the sensitivity of image forming materials is 100 mW.
If it is ~ 400 mW, it has become practical as a system.

The above Japanese Patent Publication No. 62-49615 discloses that
It is described that an infrared laser beam such as a YAG laser (oscillation wavelength 1.06 μm) can also be used, but a diphenylmethane dye or triphenylmethane which is an additive for reversal used in this photosensitive composition. A basic carbonium dye selected from dyes, xanthene dyes, and acridine dyes does not include a coloring material for light-to-heat conversion when an infrared laser is used. Therefore, it is necessary to add an additive for light-to-heat conversion in addition to the coloring material as an additive for reversal, and the amount of the additive contained in the system increases, so that the developability is impaired. However, there are drawbacks such as deterioration of image strength.

[0009]

SUMMARY OF THE INVENTION The main object of the present invention is to improve and further develop the technique disclosed in Japanese Patent Publication No. 62-49615. That is, it is possible to perform efficient light-to-heat conversion with respect to infrared laser light, and to directly or catalytically react with a photoreaction product of an o-quinonediazide compound by heating to efficiently generate an alkali insoluble substance. By finding a colorant additive that can be formed, an image forming material using a highly sensitive photosensitive composition containing the same is provided, and in response to an ever-increasing need, without a mask. An object of the present invention is to provide an image forming method which enables direct digital recording.

[0010]

The present inventors have analyzed the mechanism of reversal image formation using an o-quinonediazide compound,
It was estimated as follows.

[0011]

[Chemical 2]

As a result of intensive studies based on this, the object of the present invention is to include an o-quinonediazide compound as a first essential component, and as a second essential component, the following general formula (1) to A cyanine dye, an azurenium dye, a squalium dye, a croconium dye, a quinone dye, and a thiazine having the chemical structure represented by (7) and having a maximum absorption wavelength (λ _max ) in the range of 670 to 1250 nm. Selected from dyes or xanthene dyes,
0.03 to 0.7 part by weight of an additive that reacts with the photoreaction product of the o-quinonediazide by heating to form an alkali insoluble material, and is contained in an amount of 0.03 to 0.7 parts by weight. An image forming material having the composition provided on a support,

[0013]

[Chemical 3]

Here, R ₁ and R ₂ may be the same or different and each represents a hydrogen atom, an alkyl group, an alkoxy group, an aralkyl group or an aryl group.

Further, the above image-forming material is entirely exposed to the active light of an o-quinonediazide compound, and thereafter imagewise irradiated with an infrared laser beam, and then the alkaline developer is not irradiated with the infrared laser beam. It has been found that this can be achieved by an image forming method in which only the exposed area is dissolved and removed.

The support of the image forming material of the present invention includes:
There are planar and other shaped materials that do not undergo significant dimensional changes. Examples of flat materials include glass, silicon single crystal plate, silicon oxide, ceramics, paper, metal such as aluminum, magnesium, zinc, copper, iron, chromium, nickel, silver, gold, platinum, palladium, aluminum. Alloys containing main component, alloys containing zinc as main component, alloys containing magnesium as main component, copper-zinc alloy, iron-nickel-chromium alloy, alloys containing copper as main component, polymer,
For example, regenerated cellulose, cellulose nitrate, cellulose diacetate, cellulose triacetate, cellulose acetate butyrate, cellulose acetate propionate, polystyrene, polyethylene terephthalate, polyethylene isophthalate, polycarbonate of bisphenol A, polystyrene, polystyrene, Polypropylene, nylon (6-nylon, 6.6-nylon, 6 / 10-
Nylon, etc.), polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, vinyl chloride-acrylonitrile copolymer,
Examples thereof include vinyl chloride-vinylidene chloride copolymers, polyacrylonitrile, polymethyl acrylate, and polymethyl methacrylate.

Further, two or more thin plates of the above substances are firmly laminated, for example, cermet, iron-aluminum laminate, iron-copper-aluminum laminate, iron-chromium-copper laminate, and the surface is coated with polyethylene. Paper, paper coated with cellulose triacetate on the surface, aluminum plate with the surface anodized to form an aluminum oxide layer, synthetic paper or plastic with a hydrophilic layer on the surface, chromium oxide layer on the surface by a known method It is also possible to use a chrome plate on which is formed, a glass plate on which a tin oxide layer is provided, a silicon oxide plate on which an indium oxide layer is provided on the surface, and the like.

These supports may be appropriately selected from transparent or opaque ones depending on the purpose of the image forming material. Furthermore, even when it is transparent, it is not only colorless and transparent, but also "J. SMPTE", Vol. 67, p. 296 (1
958) etc., it is also possible to use those which are colored and transparent by adding a dye or a pigment. In the case of an opaque support, in addition to an originally opaque support such as paper or metal, a transparent material added with a dye or a pigment such as titanium oxide, the method described in JP-B-47-19068. It is also possible to use paper, plastic film or the like which has been made completely light-shielding by adding a plastic film and carbon black surface-treated with.

Furthermore, graining on the surface, electrolytic etching,
Supports with fine recesses formed by treatments such as anodic oxidation and chemical etching, or supports whose surface has been pretreated by corona discharge, ultraviolet irradiation, flame treatment, etc., glass fibers, carbon fibers, boron fibers, various metal fibers It is also possible to use a plastic support whose strength is increased by mixing a reinforcing agent such as metal whiskers.

If necessary, the surface of these supports may be provided with another coating layer, an antihalation layer, an ultraviolet ray absorbing layer, a visible ray absorbing layer or the like for strengthening the adhesion to the photosensitive resin composition layer. good.

Next, the photosensitive layer will be described. The photosensitive layer is composed of a photosensitive resin composition containing o-quinonediazide as a first component and an additive for vapor reversal as a second component. If necessary, it may further contain a binder polymer. The o-quinonediazide compound used in the present invention is a compound having at least one o-quinonediazide group in the molecule and increasing the solubility in an alkaline solution upon irradiation with an actinic ray, and compounds having various structures are known. For example, J. KOSAR "Light-S"
"Ensive System" (John Wil
ey & Sons Inc. 1965). Particularly, sulfonic acid esters of various hydroxy compounds and o-benzoquinone diazide or o-naphthoquinone diazide are preferable. Typical examples include 2,2'-dihydroxy-diphenyl-bis- [naphthoquinone-1,2-diazide-5-sulfonic acid ester], 2,2 ', 4,4'-tetrahydroxydiphenyl-tetra [Naphthoquinone-1,2-diazide-
5-sulfonic acid ester], 2,3,4-trioxybenzophenone-bis- [naphthoquinone-1,2-diazide-5-sulfonic acid ester], and the like.
The ester of naphthoquinone-1,2-diazide-5-sulfonic acid and polyhydroxybenzene obtained by polycondensation of acetone and pyrogallol described in JP-A-3-28403 can be advantageously used.

The photoreaction product of the o-quinonediazide compound, which is used as the second component of the present invention, absorbs infrared rays and converts light into heat, and acts as an additive for reversing the photosensitive layer. As a coloring material that acts as an additive capable of efficiently forming an alkali insoluble product by directly or catalytically reacting with heating, a cyanine dye (including cyanine, hemicyanine, streptocyanin) Azurenium-based dye, aquarium-based dye, croconium-based dye, naphthoquinone or anthraquinone-based dye, xanthene-based dye, oxazine or thiazine-based dye, including the structure of the general formula shown in (Chemical Formula 3), λ _max is 680 to 1250
Dyes in the nm range can be mentioned. Specifically, the following dyes can be mentioned.

[0023]

[Chemical 4]

[0024]

[Chemical 5]

Of these, dyes which undergo large photobleaching upon exposure to the entire surface are not preferable because the light-to-heat conversion efficiency deteriorates upon irradiation with an infrared laser.

The mixing ratio of the o-quinonediazide compound and the coloring material is preferably 0.01 to 1 part by weight, and more preferably 0.0 to 1 part by weight of the o-quinonediazide compound.
A range of 3 to 0.7 parts by weight is preferable.

Various additives may be added to the photosensitive composition used in the present invention in addition to the above-mentioned essential components.
Also, to enhance image strength or as a binder,
Known resins such as phenol resin and styrene / maleic acid copolymer resin can be added. These techniques are widely known to those skilled in the art.

To prepare an image forming material, a photosensitive resin composition having the above composition is provided on a support.
If necessary, the photosensitive resin composition is dissolved in a solvent. The solvent can be appropriately selected and used from known solvents that do not impair the photographic characteristics of the photosensitive composition. The photosensitive resin composition or the solution thereof can be provided on the support by appropriately selecting from known methods. A typical method is coating from a solution, which can be easily performed by those skilled in the art according to a known method.

The light-sensitive material formed as described above has an o
Actinic radiation of quinonediazide compounds (usually a wavelength of about 29
The entire surface is exposed by a usual method with 0-500 nm near-ultraviolet light and visible light. Sources of actinic rays include mercury lamps, xenon lamps, carbon arc lamps, tungsten lamps,
Fluorescent light, sunlight, etc. can be used.

Examples of infrared lasers for subsequent pattern exposure include semiconductor lasers, YAG lasers, carbon dioxide lasers and the like. From the viewpoint of image quality, short wavelength lasers are preferable, and semiconductor lasers are preferable from this point. A long-wave laser beam can also be used as a short-wave by a second harmonic generator.

The image forming material treated as described above is then subjected to a developing treatment. The developing solution used for the developing treatment can be selected from many known developing solutions conventionally used for developing a photosensitive layer containing an o-quinonediazide compound. That is, it is easily developed by immersing in an alkaline solution or washing with it. The preferred alkaline solution is an aqueous solution containing an inorganic compound such as sodium hydroxide, potassium hydroxide, sodium silicate, potassium silicate, trisodium phosphate, tripotassium phosphate, sodium carbonate, potassium carbonate, or ethanolamine, diethanolamine, triethanolamine, An aqueous solution containing an organic base such as tetramethylammonium hydroxide can be used. If necessary, an organic solvent, a surfactant and the like can be included.

The image obtained through the above-mentioned processing has many uses. For example, when a grained aluminum substrate is used as a support, a good printed matter can be obtained by applying it to a printing machine after development processing. Further, when a photosensitive layer containing the dye of the present invention is provided on a transparent plastic film such as a polyester film, it can be used for print proofing.

The developed image-forming material can be subjected to post-treatment depending on the purpose. For example, when the chromium vapor-deposited film provided on the glass substrate is used as the support, after the development treatment, the chromium vapor-deposited film is etched with a known etching solution containing a second cerium ion or the like using the photosensitive layer as an etching resist, and then, If the resist is removed, it can be used as a hard mask. Further, when a silicon substrate is used as a support, it can be used for an etching resist for a silicon oxide film and a lift-off process. Further, when a copper foil substrate for a printed wiring board is used, it can be used as an etching resist or a plating resist after the development treatment.

In the embodiment of the present invention in which an image is recorded using a laser, it can be used as a photomask, a laser recording of a computer output signal, and a facsimile terminal recording material.

In addition to these, it can be used in a video disc making process and the like, and the use of the image obtained by the method of the present invention is not limited to the above-mentioned examples.

Further, the image-forming material of the present invention can form a reversal image by heating the entire surface after image exposure and then developing with an alkaline developing solution. It is also possible to print with a conventional thermal printer and then remove the non-printed portion with an alkaline developer to form an image.

The present invention will be described in more detail based on the following examples, but the invention is not intended to be limited thereto.

[0038]

【Example】

Example 1 A polyethylene terephthalate film having a thickness of 100 μm was vacuum-deposited (thickness: 100 nm) so that the atomic ratio of aluminum was 98.5 and iron was 1.5 nm. 1 part by weight of 1,2-naphthoquinonediazide-5-sulfonic acid ester of polyhydroxybenzene obtained by polycondensation of acetone and pyrogallol described in Example 1 of Japanese Patent Laid-open Publication No. PR-50904, degree of polymerization 3-10) 2 parts by weight, 1,2-dichloromethane 20 parts by weight, methyl cellosolve acetate 20 parts by weight, and the compound example No. 1 described in the present specification. 1-No. Eight kinds of photosensitive solutions prepared by adding 0.2 parts by weight of each of the compounds of Example 8 and dissolving were applied by a spin coater so as to have a dry film thickness of 0.7 μm to prepare eight kinds of image forming materials.

A semiconductor laser (LN981500PR manufactured by Matsushita Electric Industrial Co., Ltd.) which emits an infrared beam of 830 nm is exposed to the surface of each of these eight kinds of image forming materials by a 2 kW ultra-high pressure mercury lamp for 30 seconds on the entire surface, and then output. 99.9 mW, scanning speed 4.0 m / sec, beam diameter 1
0 μm, scanning pitch 5.0 μm, strength of sensitive material surface 300 m
Recorded in W / cm ² .

After that, 4 g of sodium hydroxide, 10 g of sodium bromate and 10 g of trisodium phosphate were dissolved in 1 liter of water and immersed in a developing solution at 31 ° C. for 20 seconds. As a result, the photosensitive layer and the metal vapor deposition layer remained in the portion irradiated with the laser beam, but the metal vapor deposition layer eluted in the non-irradiated portion, and a good image was obtained. From this, the above No. 1 to
No. It was confirmed that the dye of 8 acts as an additive for reversal image formation.

Example 2 A 2S aluminum plate for lithographic plates which was grained by a mechanical method (99% aluminum, 0.6 magnesium)
%, Aluminum alloy plate consisting of 0.4% silicon) 40
1% in 2% by weight aqueous sodium hydroxide solution kept at ℃
The surface was etched by immersion for a minute. After washing with water, the surface of pure aluminum was exposed by immersing it in a sulfuric acid-chromic sulfuric acid mixed solution for about 1 minute, and then immersing in a 20% sulfuric acid solution kept at 30 ° C., with a DC voltage of 15 V and a current density of 3 A / dm ² . Anodization was performed for 2 minutes under the conditions. Then, a concentration of 2.0% by weight,
It was dipped in an aqueous solution of sodium molybdate at a temperature of 65 ° C. for 90 seconds and dried.

On the aluminum plate subjected to the above treatment,
No. 1 created in the first embodiment. The photosensitive solution containing the compound No. 1 was applied using a spin coater so that the dry film thickness was 1.0 μm. Thereafter, after exposing the entire surface and recording an image in the same manner as in Example 1, a positive film P manufactured by FUJIFILM Corporation was used.
By developing with the S plate developing solution (DP-1), an image was formed only on the portion irradiated with the semiconductor laser. After that, when printing was performed using an ordinary offset printing machine, the ink adhered favorably to the image, and a good printed matter corresponding to laser light irradiation was obtained.

[0043]

With the image forming material of the present invention, an image usable for a color proof, a printing plate or the like can be directly produced by a digital method.

Claims (2)

[Claims] 1. An image-forming material comprising a support and a composition containing at least the following (a) and (b). (A) an o-quinonediazide compound, (b) a cyanine dye having a chemical structure represented by the following general formulas (1) to (7) in the molecule, and a cyanine dye having a maximum absorption wavelength of 680 to 1250 nm, azurenium Addition for reacting with a photoreaction product of the o-quinonediazide compound by heating to form an alkali insoluble substance selected from the group consisting of dyes, squalium dyes, croconium dyes, quinone dyes, thiazine dyes or xanthene dyes 0.03 to 0.7 part by weight of the product with respect to the o-quinonediazide compound. [Chemical 1] Here, R ₁ and R ₂ may be the same or different and each represents a hydrogen atom, an alkyl group, an alkoxy group, an aralkyl group or an aryl group. 2. The image-forming material according to claim 1 is entirely exposed with an actinic ray of an o-quinnodiazide compound, is irradiated with an infrared laser beam, and is then irradiated with an alkaline developing solution. An image forming method characterized by removing the.