JPS60138545A - Photosensitive composition - Google Patents

Abstract

PURPOSE:To prevent generation of scumming, etc. by compounding sulfonate or sulfinate or alkyl sulfate with a photosensitive compsn. consisting of an o- naphthoquinone diazide compd., free group forming compd. and discoloring agent. CONSTITUTION:A photosensitive compsn. is incorporated therein with (A) an o-naphthoquinone diazide compd., (B) a compd. forming a free group when irradiated with active light (e.g.; 2-trihalomethyl-5-vinyl-1,3,4-oxadiazole compd.), (C) a discoloring agent which changes the color tone by making the interaction with the photodecomposition product of the component B (e.g.; crystal violet) and (D) 0.05-5wt%, by the weight of the entire compsn., sulfonate (e.g.; sodium p-toluenesulfonate) or sulfinate (e.g.; sodium p-toluenesulfinate) or alkyl sulfate (e.g.; sodium lauryl sulfate), by which the intended photosensitive compsn. is obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a photosensitive composition suitable for manufacturing lithographic printing plates, letterpress printing plates, IC circuits, and photomasks.

More specifically, the present invention relates to a photosensitive composition containing an 0-naphthoquinonediazide compound and capable of producing a visible image immediately after exposure.

[Prior art]

It is known to use an ester compound of O-naphthoquinoynoazide sulfonic acid or an amidated metal material as a photosensitive composition. Due to their very excellent performance, these compounds can be used in lithographic printing plates, especially j'!, which are prepared by pre-layering a photosensitive composition vE on a support. 7r ii) 'J It is widely used industrially as a photoresist for producing sensitized plates (usually referred to as 85 plates), letterpress printing plates, IC circuits, photomasks, or printed wiring. However, photosensitive compositions using these 0-naphthoquinone diazide compounds have the following drawbacks.

In other words, the photosensitive 0-naphthoquinonezoazide, which has a yellow color, fades when exposed to light and becomes a colorless or pale yellow photodegradable component, but under the yellow safety light in exposed confectionery, the exposed and unexposed areas are separated after exposure. cannot distinguish between parts. For this reason,
For example, in the process of exposing many printing plates at the same time, when work is interrupted, it is difficult or impossible to know whether a plate given to the platemaker has been overexposed. Similarly, for example, when making a lithographic printing plate, Jjr =
i'f print printing is like a law for one large plate.
If exposure is applied even once per minute, the operator cannot confirm which part is exposed. This often leads to erroneous operations, which is one of the causes of a significant reduction in work efficiency.

In order to improve these drawbacks, the following techniques are known for forming a four-wave visible image on a photosensitive composition.

1] For example, US TF! J Patent No. 206 Otsu No. 9/3 and rtbigss No. uAa %+', which use various reducible salts mixed with diazo compounds, and those shown in Japanese Patent Publication No. 10-2203. One that obtains a visible image from a photosensitive diazo compound and an acid-base indicator, which is disclosed in Japanese Patent Publication No. 19-3-OlI1, and one that consists of a photosensitive positive-acting diazo resin and a merocyanine dye; In the printing original plate previously photosensitized with O-naphthoquinone diazide as shown in BH4tO-2709.3, puλS-mu5 is added in the photosensitive layer.
JP-A-Sho! contains homogeneous granular organic colorants that change the color tone. ;0-3 A The 0-naphthoquinonediazide sulfone disclosed in the 2θ publication is used in photosensitive copying j- containing an ester or amide, when the photosensitive copying layer has a total content of ()-naphthoquinonediazide compound. 0-naphthoquinone diazide goose sulfone halognide 10 to 75 9-cents by weight, and an M-like compound having salt-forming ability as a dye in the range of 1 cent by weight, JP-A Esterification adduct of phenol substituted with an electron-absorbing direct substituent group and 0-naphthoquinone noanodo-goose sulfo/acid and photodecomposition of the 0-naphthoquinonediazide compound shown in Kogugu No. 1987-6 Examples include those containing organic dyes that change the color tone by interacting with objects. However, even with these improved images, the contrast of the visible 1III image obtained by exposure is small, and the contrast further deteriorates due to changes in the photosensitive composition over time, making it difficult to withstand practical use. It wasn't.

On the other hand, JP-A-5G17DA-72G and JP-A-Sho!
;! ; -Romethyloxadiazole compound shown in Publication No.-7774t2 or JP-A-Sho! ;! ;-3=
Halomethyl S-)ryanone compounds shown in Publications No. 070 and JP-A No. 070 and JP-A No. 3 Otsunoza No. 7; The photosensitive composition containing the above-mentioned photosensitive composition has become popular in recent years because it immediately produces a clear visible image after being exposed to light and has excellent stability over time.

However, by adding these halomethyl oxazazole compounds and halomethyl S-)lyasin compounds to the photosensitive composition, compared to the case where no additives are used,
A portion of the photosensitive composition tended to remain in the non-image area after development. In particular, when developing a lithographic printing plate by impregnating a developing solution with absorbent cotton, sponzo, etc. and rubbing the printing plate, a photosensitive <11 compound may remain partially in the non-image area, resulting in so-called uneven hand appearance, which may deteriorate the appearance. Soneru was often the cause of scumming, not Kakashi.

[Purpose of the invention]

Accordingly, an object of the present invention is to provide a photosensitive composition that can provide a clear LIJ image immediately upon exposure. Another object of the present invention is to provide a photosensitive composition in which the photosensitive composition remains in the non-image area after development and is less prone to scumming when used as a printing plate.

[Structure of the invention]

The inventors of the present invention have conducted extensive research to achieve the above object, and as a result, have completed the present invention. Restoration: a group-forming compound, (C) a color change agent that changes its color by interacting with the photodecomposition product of (b), and (d) for the entire composition. This is a photosensitive composition containing 0.005 to 3% by weight of a sulfonate, a sulfinate, or an alkyl sulfate.

The present invention will be explained in detail below.

Examples of the 0-naphthoquinone diazide compound used in the present invention include the following: The most preferred ester is

Other suitable 0-naphthoquinone diazide compounds include rice l-! ! I Patent No. 30 Ko 6/Tsu O and No. 3
/gg210 specification, described in the middle of the day/.

Non-naphthoquinone-nonoazido-5-sulfone The ester of chloride and phenol-formaldehyde resin is heated overnight. Other useful 0-naphthoquinonediazide compounds are known and reported in numerous patents, such as JP-A No. 7-3303 and JP-A No. 7-3303, Shoda G-6
3za02, Akihiro g-1, 3g03, Akihiro g-9
1. ! ;7! ; issue, Show 19-3g70/ issue, Show 1
Ig-/33! ;'No. 1, Akira Machikoda/-//No. 2 here,
Dosho 9. T-wa No. 670, same bean paste 9-/74tg/
Publication No. 2,797.2/3, U.S. Permit No. 3. t3g, No. 400, No. 3! i Guda, No. 3.23, No. 3.373.9/7, No. J, 67 Hiro,'
1.93, 3rd and 7th s, gaS, UK LI81
First permission. J J Z Aθko issue, same g/, , 2
,! -/, 34 & issue, same issue/, Kootsu'7.00!
; No. 1.3.2? , Zaza No. 5, Same No./, 33
0.932 issue, l'(7Special 1fmg! It, g90 issue, etc.) can be mentioned.

Occupies in the photosensitive composition of the present invention. - The naphthoquinonediazide compound has 10-tθM or less, preferably 2o-tθM or less.

Irradiation of actinic rays used in the present invention
Examples of the compound that generates the group include %Kaisho Sanhiro-74t7.
Written in the 2g issue l7i1! Not trihalomethyl-S-vinyl-/, 3.4t-oxasoazole compound vIJ, which has been described in Japanese Patent Application Laid-open No. 777-777, , 3. Oxazoazole compound *a is preferable. In addition, λ, Dervis(trihalomethyl)-6-pinylu-s-trianonated-8-section proboscis described in JP-A No. 35-32θ70 Noaryruda, 6-bis(trihalomethyl)-S-triazone compounds 'a', etc., which have been described above, can also be suitably used. Seven types of these free radical generating agents may be used, or a mixture of ams or more may be used.

The amount of the compound that generates free radicals upon irradiation with actinic rays in the photosensitive composition of "non-exploding ψ" is a/~20% by weight, preferably 05 to 5% by weight.

The color changing agent used in the present invention changes the color tone by interacting with the photodecomposition product of the compound that generates free radicals upon irradiation with actinic rays, from originally colorless to colored. There are two types: those that change their state, and those that originally have a unique color but change or bleach their color.

Typical color changing agents belonging to the 14fJ type include arylamines.

Arylamines missing in this date 9 include primary,
In addition to simple leuco-amino acids such as secondary aromatic amines, so-called leuco dyes are included, and examples of these dyes include the following.

Nophenylamine, dibenzylaniline, triphenylamine, diethylaniline, diphenyl-p-phenylenediamine, 1)-) Luisonda Hiroshi l-biphenyldiamine, 0-chloroaniline 0-bromoaniline, terchloro-〇-phenylenediamine, 0 -Promo N, N
-trimethylaniline, /, 2,3-triphenylguanidine, naphthylamine, diaminodiphenylmethane,
Aniline, 2. S-dichloroaniline, N-methyldiphenylamine, O-)Lewisson, pl l''7tramethylsoaminodiphenylmethane, N,N-dimethyl-p
-phenylenediamine, /, 2-dianilinoethylene,
p, p', p"-hexamethyltriaminotriphenylmethane, p, p'-tetramethyldiaminotriphenylmethane, pz p'-tetramethyldiaminonophenylmethylimine, g'sp yl) triamino-0-methyl Triphenylmethane, p, p', p"-triaminotriphenylcarbinol, p, p'-tetramethelaminosobuenylruderanilinonaphthylmethane, pt
F"1p" - triaminotriphenylmethane, p, p
',p''-hexanolopyltriaminotriphenylmethane.

It also has a unique color and nucleus. - Photodecomposition products of naphthoquinone diazide compounds. Examples of discolorants that change or decolorize the photolysis product include diphenylmethane, triphenylmethane-based thiazine, oxacin-based, xanthine-based, anth-quinone-based, and iminonaphthoquinone. Various dyes such as azomethine-based dyes and azomethine-based dyes can be effectively used.

Examples of these include: Brilliant Green, Eosin, Ethyl Violet, Erythrosin B1 Methyl Green, Crystal Violet, Pesic 7 Cusin, Phenolphthalein, /, 3-Diphenyl Triazine, Alizoline Red S1 Thymolphthalein, Methyl Violet 2B1 Quinaldine Red, Rose Bengal, Methanil Yellow , thymol sulfophthalein, xylenol blue, methyl orange, orange ■, diphenylthiocarbazone, co, 7-nochlorofluorescein, noya methyl red, Congo red, penzolpurinda B1 α-naphthyl red, Nile blue 2B, Nile Blue A1 Fena Shitalin, Methyl Violet, Malachite Green, Baratuxin, Oil Blue φ6θ3 [Orient Chemical Industry Co., Ltd.], Oil Pin Funa 3/2 [Orient Chemical Industry Co., Ltd.]
Incorrect], Oil Red SB [Orient Chemical Industry Co., Ltd.]
], Oil Scarlet Toner 30gC Orient Kagaku Kogyo ml) ML Oillet "OG" [Orient Kagaku Kogyo (
Manufactured by:], Ooil Red RR Orient Chemical Industry Co., Ltd.), Oil Green ◆502 [Orient Chemical Industry Co., Ltd. J), Subiron Red BEH Special [Hodogaya Chemical Industry Co., Ltd.], m- Cresol bar full, cresol red, rhodamine B, rhodamine AG,
Fast Acid 'Violet R, Sulforhodamine B1 Auramine, 'l 9-Diethylaminophenylimino naphthoquinone, Dical is xyanilino-t-p
-diethylaminophenylimino naphthoquinone, nocarpostearylamino-9-p-nohydroxyethyl amino-phenylimino naphthoquinone, p-methocykpe/silu p'-noethylamino-o'-methylphenyliminoacetanilide, cyano-p noethylaminophenylimino acetanyl 1',/-phenyl-3
-methyluda-ρ-diethylaminophenylimino-5
-pyrazolone, l-β-naphthyluda-p-noethylaminophenylimino-3-pinzolone.

The above-mentioned color-changing agent changes color by irradiation with the above-mentioned actinic rays.
About a for the compound/intussusception producing 1i1 & , 4
It is used in a yoke of oizd part, more preferably θ/~10 ply part.

Sulfonic acid salt or sulfinic acid J modified according to the present invention:
The iL or alkyl sulfate is preferably a single metal salt such as sodium or potassium. These salts can be used by adding sulfonic acid, sulfinic acid, or alkyl iAi i& and a base such as sodium hydroxide or potassium hydroxide separately to the coating solution, in addition to adding the photosensitive composition directly to the photosensitive composition. It is also possible to add the salt of the present invention and use it by forming it during the 7 night of application.

Specific examples of the sulfonate salt, sulfine salt, or alkyl sulfate that can be used in the present invention include sodium p-toluenesulfonate, potassium p-1'toluenesulfonate, sodium mesitylenesulfonate, and ethane sulfonate. Sodium sulfonate, sodium benzene sulfonate,
Sodium p-toluenesulfinate, potassium p-1'toluenesulfinate, sodium p-chlorobenzenesulfone, /-sodium naphthalenesulfone, /
- Potassium 7talenesulfonate, Sodium naphthalenesulfonate, Sodium isoglobylnaphthalenesulfone, Sodium t-butylnaphthalenesulfonate, Sodium salt of sulfonated argylinophenyl oxide, Sodium salt of fused aryl sulfonate, (n: /~io) anionic surfactant, ko.

Sodium 6-di-t-butylnaphthalene sulfonate,
-,6-not-t-butylnaphthalene*7tm')
f thorium, diphenyl-q-sulfone v sodium,
Diphenyl ether-17-sulfone 1 wave sodium,
Examples include sodium nophenylamine-y-sulfonate, sodium ρ-vinylbenzenesulfonate, sodium lauryl sulfate, sodium polyoxyethylene alkyl ether sulfate, sodium polyoxyethylene alkylphenol ether sulfate, and the like.

Such salts are used in combination of 7 types or 2411m or more, and θθ, ! for the entire photosensitive composition. T-,! -% by weight
, more preferably in the range of θ to 2 pages.

If the amount of salt added in the present invention is too small, the young fruits of the present invention cannot be produced, and on the other hand, if the amount of salt added is too large, the visible image after exposure may become difficult to see, and the image area may be damaged during development. It's getting easier.

It is preferable to include an alkali-soluble resin in the composition of the present invention. By including the alkali-soluble resin, the 51 [51] of the photosensitive film can be improved. Suitable alkali-soluble resins include 2-type phenolic resins, specifically phenol formaldehyde'l
Id fat, op resol formaldehyde 411'l
resin, m-cresol formal r heptad resin, etc. Other phenol-modified xylene resins, polyhydroxystyrene, polyhalogenated hydroxystyrene, etc.
Known alkali-soluble resins can be included.

Such alkali-soluble resins are used in amounts of up to 9 QM in the total composition.

A cyclic acid anhydride for increasing sensitivity and a dye for coloring images can be added to the composition of the present invention. As a cyclic acid anhydride, rice 1 = ljl, please note // 3.
Phthalic anhydride, as stated in No. 72g specifications,
Tetrahydrophthalic anhydride, hexahydrophthalic anhydride, 3.1-monoendogycin Δ4-tetrahydrophthalic anhydride, tetrachloromaleic anhydride, maleic anhydride, chlor 1QIIihydromaleic acid, α-phenylmaleic anhydride modified, succinic anhydride, pyro Examples include mellitic acid. The amount of these cyclic acid anhydrides in/from 1 syt q in the total composition
By including b, the sensitivity can be increased up to three times.

In addition to the above-mentioned color change agents, other dyes can also be used as image colorants. Suitable dyes including the color change agents mentioned above include oil bath dyes and basic dyes.

Specifically, Victoria Vinia Blue BOH (manufactured by Hodogaya Chemical Industry Co., Ltd.), Oil Bin Funa 3/Co, Oil Green BG, Oil Blue 8051 Oil Pruner 6o3
,oil! Rack BY, Oil Black BS, Oil Black T-! ;0! ; (manufactured by Orient Chemical Industry Co., Ltd.), Crystal Violet (Cl Da 2!;!;
! ), methyl violet) (Cl Hiro, 2s3.t
), Rhodamine B (CIV5/70B), Malachite Gly-y (C14I-Coθ00), Methylene Blue (
CI,! -Koi! f> etc. can be opened.

Such dyes are used in an amount of .theta./.about.5 by weight in the total composition.

The composition of the present invention may contain additives for improving the ink receptivity of the image area when used in lithographic printing plates, such as the p-1-butylphenol formaldehyde resin described in JP-A-Sho-i2sgob. Alternatively, p-n-octylphenol formaldehyde resin may be added. In addition, a surfactant such as a nonionic fluorine surfactant may be added to the composition of the present invention to improve coating properties.

In addition, the composition of the present invention contains talc powder, glass powder, clay, starch,
Known matting agents such as wheat flour, corn flour, I-lyethylene powder, polynolopyrene powder, and crosslinked bi=/L polymer powder can also be included. When a matting agent is included, the properties of the vacuum layer will be the same as above, and the film strength will also be improved.

The composition of the present invention is applied onto a support after being dissolved or dispersed in the above-mentioned propellant. The solvents used here include ethylene fucuroid, cyclohexanone, methyl ethyl ketone, ethylene glycol monomethyl ether,
Examples include ethylene glycol monoethyl ether, noromethoxyethyl acetate, ethyl acetate, water, etc., and these solvents are used alone or in combination. And above [
+The solid content in the self-component is -~Sθ%.

In addition, the coating amount is generally θ, S −3, θ as solid content.
1/ln is preferred. As the coating amount decreases, the photosensitivity improves, but the physical properties of the photosensitive film deteriorate.

In order to produce a lithographic printing plate using the photosensitive composition of the present invention, known supports include hydrophilized aluminum plates, such as silicate-treated aluminum plates, anodized aluminum plates, electrolytic grains, brush grains, etc. Aluminum plates grained using the method described above, silicate electrodeposited aluminum plates, lead plates, stainless steel plates, chromium-treated steel plates, hydrophilized Norastic film, paper, and composite supports of aluminum and paper. I can lift my body up. In particular, in the present invention, an aluminum plate that has been grained and then anodized is preferably used.

Examples of developing solutions for the photosensitive composition of the present invention include sodium silicate, potassium silicate, sodium hydroxide, potassium hydroxide, lithium hydroxide, tertiary phosphorous sodium,
Aqueous solutions of inorganic alkaline agents such as sodium diphosphate, ammonium diphosphate, ammonium diphosphate, sodium metasilicate, sodium bicarbonate, aqueous ammonia, etc. are suitable; Shigetoshi Chi,
Preferably, θ is added so that it becomes t-4 multiplier/)
.

Furthermore, a surfactant, a 4-i solvent such as alcohol, etc. can be added to the alkaline aqueous solution, if necessary.

〔Example〕

Next, the present invention will be further explained in detail with reference to Examples. It should be noted that all percentages in the following examples are by volume unless otherwise specified.

Example 1 A 027 mm thick aluminum plate was degreased by immersing it in a tertiary sodium phosphate/θ water bath maintained at gθ°C for 3 minutes, and then grained with a nylon brush. Etching was performed for about 70 seconds using solution M, and desmutting was performed using a 3% aqueous solution of sodium hydrogen sulfate. This aluminum plate was subjected to anode captivity at a current density of λA/d in 20 inch TJ & I waves to produce an aluminum plate (1).

Apply the following photosensitive liquid to this aluminum plate (1).
The plate was dried at 00° C. for 2 minutes to produce a photosensitive planographic printing plate.

u/,, 2-naphthoquinone-nodiazide-5-sulfonyl chloride docresol-formal esterified with human resin θ90110 cresol-formaldehyde tl fat lq 902-trichloromethyl-! ;
-(p-methoxystyryl)-/, 3. U-Oxadiazole (Example of JP-A-5-711.7)
) θθ3I O Crystal Violet θθ2SIO Sulfonate or sulfinate salt in the present invention (those listed in Table 47) A photosensitive liquid from which sulfonates or sulfinates have been removed, and 11 trichloromethyl! ;-(p-methoxystyryl)-/, 3.4-
A photosensitive liquid without oxadiazole was also applied in the same manner to prepare a photosensitive lithographic printing plate.

The coating weight after drying was 317 Y/m2 in each case.

Each of these photosensitive planographic printing plates was passed through a positive transparent original image from a distance of 7 m using a 2 kW metal halide driver.
The light was exposed for θ seconds. The optical density of the exposed area and the photosensitive layer of Miji Koto was measured using a Macbeth reflectance meter. The results are shown in Table 7. The image obtained with each lotus light appears sharper as the difference (ΔD) between the optical clarity of the unexposed area and that of the exposed area is larger.

In addition, after exposing the above and colleagues through a 4F transparent image, I rubbed it with a stain coated with 4g% Metakeikyo Sodium Mizunuma solution and developed it, resulting in uneven development in non-image areas (hand development unevenness).
I looked into it. In Table 7, cases where almost no unevenness occurs are marked with an ○, and cases where unevenness occurs are marked with an x. After exposure in the same manner as above through a positive transparent original, it was added to a 1% sodium metasilicate aqueous solution at 25°C for 3 minutes.
I investigated the back of the image area when it was developed by immersion in a river. No./
If the degree of damage is small, mark it with ○, and if the degree of damage is large, mark it with ×1-
I8 The intermediate value is indicated by Δ.

*) 2-trichloromethyl-5-(p-methoxystyryl)-/, 3. 'A photosensitive composition that also excludes I-oxadiazole.

From Table 1, it can be seen that the photosensitive composition vIJ of the present invention gives a clear visible image upon exposure and is excellent in appearance with little unevenness.

EXAMPLE The following photosensitive liquid was applied to the aluminum plate (I) used in Example/in the same manner as in Example/, to prepare a photosensitive lithographic printing plate.

l, an esterified product of eunaphthoquinone-eusoazido-5-sulfonyl chloride and pyrogallol-acetone (produced by the method described in U.S. Pat. No. 363!; ) θ73 & cresol formaldehyde resin 2. ,/! ; 1,4t-bis(trichloromethyl)-b-p-methoxystyryl-s-trianone (Japanese Patent Application Laid-Open No. 1999-1993-362G1, published by Ztl/ij) θθgy oil pruner 603 [ Orient Toilet Take [Ei Co., Ltd.]t),
03. ! Ethylene glycol monomethyl ether /θ
g Methyl ethyl ketone Ko θ y Water 2y All of the 11th row of dry line dust is Yu! ;9/m.

Each of these photosensitive lithographic printing plates was exposed to light in the same manner as in Example 1, and the a degree travel (ΔD) of the exposed and unexposed areas and the actual hl! Similarly to Example 1, the ease of occurrence of unevenness in the appearance of the printed matter was evaluated, and then printed using a printing press, and the occurrence of scumming was examined. The results will be summarized in the second section.

It is clear from Table 2 that the photosensitive composition of the present invention is an excellent composition.

Claims (1)

[Claims] (a) 0-su7toquinonediazide compound, (b) a compound that generates a free radical upon irradiation with actinic rays, (C) the above (
b) a color change agent that changes its color tone by interacting with the photolysis products of
1. A photosensitive composition comprising an o, t-si amount of a sulfonate, a sulfinate, or an alkyl sulfate.