JPH0128369B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention involves adding a dye, o-quinonediazide-4-sulfonic acid halide, and a compound containing a halogen to a photosensitive composition consisting of an o-quinonediazide compound and a phenolic resin, which dissociates an acid when irradiated with active light. The present invention relates to a photosensitive composition from which a visible image can be obtained without immediate development. A photo-solubilized composition comprising an o-quinone diazide compound and a novolac resin has extremely excellent performance and has been widely used industrially for the production of lithographic printing plates and as a photoresist. However, when this photo-solubilized composition is exposed to light, the o-quinonediazide compound, which is itself colored yellow, photodecomposes and becomes colorless, and although it is possible to obtain a visible image with low contrast, the actual It had the disadvantage that a visible image could not be recognized under yellow safety lights during exposure work. This point can be improved by adding a PH indicator, a print-out agent such as a leuco dye or a spiropyran compound to the photo-solubilized composition, and a visible image that can be clearly recognized even under a yellow safety light can be obtained. is possible. However, Tokukai Akira
As described in Publication No. 52-80022, in a photo-solubilized composition containing a cyclic acid anhydride to improve sensitivity and developability, adding a PH indicator, leuco dye, or spiropyran compound to the photo-solubilizing composition improves the effect. It has been found that it has the disadvantage that it disappears and a visible image cannot be obtained by exposure. On the other hand, JP-A-50-36209 discloses that o-naphthoquinonediazide-4-sulfonic acid halide and an organic dye having salt-forming ability are added to a photo-solubilized composition consisting of an o-quinonediazide compound and a novolac resin. A printing method is described in which a visible image is obtained immediately after exposure. However, systems containing o-naphthoquinonediazide-4-sulfonic acid halide had problems in that the image density decreased over time and the printout contrast decreased. In order to increase the contrast of the baked-out o-
Systems to which a large amount of naphthoquinonediazide-4-sulfonic acid halide is added have problems in that the image density decreases significantly over time, and the sensitivity also decreases significantly. In order to improve this drawback, JP-A-53-8128 proposes adding 2-8% by weight of o-naphthoquinonediazide-4-sulfonic acid halide to the total content of the o-quinonediazide compound. However, in this case, since the amount of o-naphthoquinonediazide-4-sulfonic acid halide added is small, the contrast in printing out is insufficient, and in particular, the contrast deteriorates over time. Furthermore, JP-A No. 53-36223 proposes the addition of trihalomethyl-2-pyrone and trihalomethyltriazine, which have better contrast in printing out than o-naphthoquinonediazide-4-sulfonic acid halide. When added to the photosensitive layer, excellent contrast in printout can be obtained, but this has the disadvantage of causing a decrease in the sensitivity of the photosensitive layer itself. Moreover, excellent printout properties are observed immediately after exposure, but
This product also had the disadvantage that if it was left as it was, the contrast in the printout would be lost. SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a photosensitive composition which improves the above-mentioned drawbacks, has a high contrast when printed out, is stable over time, and exhibits little decrease in sensitivity. As a result of various studies, the present inventors have found that (1) an organic dye capable of forming a salt is added to a photosensitive composition comprising an o-naphthoquinonediazide compound and a phenolic resin in an amount of 0.3 to 5% by weight of the total composition ( 2) 0.2 to 7% by weight of o-naphthoquinonediazide-4-sulfonic acid halide in the total composition and (3) General formula ()
By adding 0.2 to 7% by weight of a compound containing a halogen that dissociates acid when irradiated with actinic rays to the total composition, the contrast of printing out is large upon exposure, stable over time, and relatively It has been found that a photosensitive composition with less decrease in sensitivity can be obtained. [In the formula, Ra is a trihaloalkyl group or trihaloalkenyl group having 1 to 3 carbon atoms,
is N, S, Se, or C, Y is O, N, S, Se
or C and Z has a chromophore group, and X and Y
Indicates a group consisting of a group of nonmetallic atoms necessary to cyclize. ] The o-quinonediazide compound used in the present invention is a compound having at least one o-quinonediazide group, and its alkali solubility is increased by active irradiation, and compounds with extremely various structures can be used. Regarding such o-quinonediazide compounds, see "Light-Sensitive Systems" by J. Koser, John Wiley & Sons,
Inc.) pages 339-352, which can be used in the present invention. In particular, sulfonic acid esters or sulfonamides of o-quinonediazide reacted with various aromatic polyhydroxy compounds or amines are suitable. Among the o-quinonediazide compounds used in the present invention, esters of benzoquinone (1,2)-diazide sulfonic acid chloride and polyhydroxyphenyl or naphthoquinones as described in Japanese Patent Publication No. 43-28403 Most preferred is an ester of -(1,2)-diazide sulfonic acid chloride and pyrogallol-acetone resin. Other suitable o-quinonediazide compounds include benzoquinone-(1,2)-diazide sulfonic acid chloride or naphthoquinone-(1,2) described in U.S. Pat. Nos. 3,046,120 and 3,188,210. -An ester of diazide sulfonic acid chloride and phenol-formaldehyde resin. Other useful o-quinonediazide compounds are known and reported in numerous patents.
For example, JP-A-47-5303, JP-A-48-63802,
No. 63803, No. 96573, No. 96573, No. 49.
No. 38701, No. 13354, Special Publication No. 11222, No. 11222,
US Patent No. 45-9610, US Patent No. 17481, US Patent No. 2797213, US Patent No. 3454400, US Patent No. 3544323,
Same No. 3573917, Same No. 3674495, Same No. 3785825,
British Patent No. 1227602, British Patent No. 1251345, British Patent No.
Examples include those described in specifications such as German Patent No. 1267005, German Patent No. 1329888, German Patent No. 1330932, and German Patent No. 854890. The phenolic resin used in the present invention refers to a novolac resin and a polyvinyl compound having a phenolic hydroxyl group, and the novolac resin is one obtained by condensing phenols and formaldehyde in the presence of an acidic catalyst. Also includes those modified with xylene or mesitylene. Such novolak resins include phenol-
Representative examples include formaldehyde resin, cresol-formaldehyde resin, p-tert-butylphenol-formaldehyde resin, and phenol-modified xylene resin. Examples of the polyvinyl compound having a phenolic hydroxyl group include polyhydroxystyrene polymers and copolymers thereof, and halogenated polyhydroxystyrene polymers and copolymers. The amount of o-quinonediazide compound in the total composition is
It is 10 to 50% by weight, more preferably 20 to 40% by weight. The amount of phenolic resin blended is 45 to 79% by weight, preferably 50 to 70% by weight of the total composition.
It is. Examples of the o-naphthoquinonediazide-4-sulfonic acid halide used in the present invention include o-naphthoquinonediazide-4-sulfonic acid chloride and o-naphthoquinonediazide-4-sulfonic acid fluoride. A compound having a halogen and having the following general formula () and dissociating an acid when irradiated with actinic rays used in the present invention: [In the formula, Ra is a trihaloalkyl group or trihaloalkenyl group having 1 to 3 carbon atoms,
is N, S, Se or C, Y is O, N, S, Se or C, and Z is a group having a chromophore group and consisting of a group of nonmetallic atoms necessary to cyclize X and Y. shows. ] includes compounds represented by the following general formulas (), (), or (). [In the formula, A represents H or CH ₃ , and B represents an optionally substituted aryl group or heterocyclic group. n is 0, 1 or 2. ] More specifically, compounds having the structures shown in Table 1 can be mentioned as compounds of the general formula (). As a compound of general formula (), JP-A-53-
The trihalomethyl-2-pyrone compound described in Japanese Patent No. 36223 can be mentioned. As a compound of general formula (), JABonham
Examples include vinyl-halomethyl-S-triazine compounds and allyl-halomethyl-S-triazine compounds described in US Pat. No. 3,954,475 and US Pat. No. 3,987,037. Specifically, 2-(p
-methoxystyryl)-4,6-bis(trichloromethyl)-S-triazine, 2-(p-methylstyryl)-4,6-bis(trichloromethyl)
-S-triazine, 2-(p-dimethylaminostyryl)-4,6-bis(trichloromethyl)-
S-triazine, 2-styryl-4,6-bis(trichloromethyl)-S-triazine, 2-
(p-methoxyphenyl)-4,6-bis(trichloromethyl)-S-triazine, 2-phenyl-4,6-bis(trichloromethyl)-S-triazine, 2-(p-tolyl)-4, 6-bis(trichloromethyl)-S-triazine or the general formula () where Ra is a trichloromethyl group and B is a trichloromethyl group.

Examples include compounds where n=0 in the formula. The amount of o-quinonediazide-4-sulfonic acid halide in the total composition is from 0.2 to 7% by weight, more preferably from 0.3 to 2% by weight. The amount of the compound of general formula () is also 0.2 to 7% by weight, more preferably 0.3 to 2% by weight. The total amount of o-quinonediazide-4-sulfonic acid halide and the compound of general formula () is 0.5 to 8% by weight, more preferably 0.7 to 3% by weight. o-quinonediazide-4-sulfonic acid halide and general formula ()
If the total amount of the compounds is less than 0.5% by weight, the contrast in printing will be insufficient, which is undesirable. If the total amount is 8% by weight or more, the contrast in print-out will be large, but the sensitivity will be significantly lowered, which is undesirable. When o-quinonediazide-4-sulfonic acid halide is added alone in a small amount of 0.2 to 7% by weight as described above, the contrast in printout is insufficient and the contrast deteriorates significantly over time. Furthermore, if the compound of general formula () is used alone for a long time (about one week) after exposure, the contrast of the printout will decrease. Moreover, the compound of general formula () lowers the sensitivity of the photosensitive material more than o-quinonediazide-4-sulfonic acid halide when added in an increased amount, so it is preferable to add as little amount as possible. By using a combination of o-quinonediazide-4-sulfonic acid halide and the compound of the general formula () as in the present invention, the printout contrast is excellent, and in particular, there is little decrease in the printout contrast over time, and in addition, exposure It is possible to obtain a photosensitive composition that exhibits little decrease in contrast and relatively little decrease in sensitivity due to subsequent natural standing. Organic dyes capable of forming salts used in the present invention include basic triphenylmethane dyes such as crystal violet, crystal violet base, methyl violet, malachite green, fuchsin, and parafuchsin, and oil blue #603 [Orient Chemical [manufactured by Kogyo Co., Ltd.], Oil Pink #312 [manufactured by Orient Chemical Industry Co., Ltd.], Oil Red
5B [manufactured by Orient Chemical Industry Co., Ltd.], Oil Scarlet #308 [manufactured by Orient Chemical Industry Co., Ltd.], Oil Red OG [manufactured by Orient Chemical Industry Co., Ltd.], Oil Red RR [manufactured by Orient Chemical Industry Co., Ltd.], Oil Green #502 [manufactured by Orient Chemical Industry Co., Ltd.], Spiron Red BEH Special [manufactured by Hodogaya Chemical Industry Co., Ltd.]
oil-soluble dyes such as m-cresol purple, cresol red, acidic triphenylmethane dyes such as thymol blue, or basic xanthene dyes such as rhodamine B, rhodamine 6G, fast acid violet R, sulfurhodamine B, etc. can be given. These dyes can be used alone or in combination. The composition of the present invention is applied onto a support after being dissolved in a solvent that dissolves each of the above components. Examples of the solvent used here include ethylene dichloride, cyclohexanone, methyl ethyl ketone, methyl cellosolve acetate, toluene, and ethyl acetate, and these solvents may be used alone or in combination. The concentration of solid content in the coating solution is 2-
50% by weight is suitable. In addition, in the case of photosensitive planographic printing plates, the coating amount is generally
A suitable amount is 0.5-3.0g/ ^m2 . As the coating amount decreases, the photosensitivity increases, but the physical properties of the photosensitive film, such as mechanical strength, chemical strength, development tolerance, and oil sensitivity, decrease. Supports suitable for use when producing lithographic printing plates using the compositions of the invention include hydrophilized aluminum plates, such as silicate-treated aluminum plates, anodized aluminum plates, grained aluminum plates, etc. There are aluminum plates with electrodeposited silicate, zinc plates, stainless steel plates, chrome-treated copper plates, hydrophilized plastic films, and paper. Supports suitable for producing printing proof plates, films for overhead bloggers, and films for second originals include transparent films such as polyethylene terephthalate film and cellulose triacetate film, and the surface of these plastic films can be chemically or physically modified. I can give you something that has become matte. Supports suitable for producing photomask films include aluminum,
Examples include polyethylene terephthalate film deposited with aluminum alloy or chromium, and polyethylene terephthalate film with a yellow layer. Further, as a photoresist, the photo-solubilizing composition of the present invention can be applied on various supports such as a copper plate, a copper plated plate, a stainless steel plate, a glass plate, etc. and used. Examples of the developer for the photosensitive composition of the present invention include sodium silicate, potassium silicate, sodium hydroxide, potassium hydroxide, lithium hydroxide,
Tribasic sodium phosphate, dibasic sodium phosphate,
Tertiary ammonium phosphate, dibasic ammonium phosphate, sodium metasilicate, sodium bicarbonate,
An aqueous solution of an inorganic alkaline agent such as aqueous ammonia or an organic alkaline agent such as monoethanolamine or diethanolamine is suitable, and the concentration thereof is 0.1 to 10% by weight, preferably 0.5 to 5% by weight.
% by weight. Moreover, a surfactant and an organic solvent such as alcohol can be added to the alkaline aqueous solution as necessary. Sensitivity can be increased by adding an acid anhydride compound described in JP-A-52-80022 to the composition of the present invention. In addition, fillers, other non-interacting dyes, pigments, etc. can be added to the composition of the present invention. Adding a filler not only makes it possible to further improve the physical properties of the coating film, but also makes it possible to make the surface of the photosensitive layer matte, which improves vacuum adhesion during image printing. Blur can be prevented.
Such fillers include talcum powder, glass powder, clay, starch, wheat flour, corn flour, Teflon powder, and the like. Next, the present invention will be explained in more detail by giving examples. In addition, all "%" in the following examples are weight % unless otherwise specified. Example 1 A 2S aluminum plate with a thickness of 0.15 mm was degreased by immersing it in a 10% aqueous solution of tertiary sodium phosphate kept at 80°C for 3 minutes, grained with a nylon brush, and then soaked in a 3% aqueous solution of sodium hydrogen sulfate. Desmat processing was performed. This aluminum plate was treated with a 1.5% sodium silicate aqueous solution at 70° C. for 1 minute to produce an aluminum plate ( ). The following photosensitive solution was applied to this aluminum plate (2) and dried at 100°C for 2 minutes. Naphthoquinone-(1,2)-diazide-(2)-5
-Esterified product of sulfonic acid chloride and pyrogallol-acetone resin (U.S. Patent No.
3635709 Example 1)
0.75g Cresol novolac resin 2.10g Tetrahydrophthalic anhydride 0.15g Oil Blue #603 (manufactured by Orient Chemical Industry Co., Ltd.) 0.01g Crystal Violet 0.01g o-Naphthoquinonediazide-4-sulfonic acid chloride 0.02g Compounds in Table 1 No. 10 0.02g Ethylene dichloride 16g 2-methoxyethyl acetate 12g The coating amount after drying was 2.4 to 2.5/m ² . After exposing this photosensitive lithographic printing plate to a 30 ampere carbon arc lamp from a distance of 70 cm, DP-1 (product name:
The sensitivity was measured by developing with a 6-fold diluted solution of sodium silicate aqueous solution (manufactured by Fuji Photo Film Co., Ltd.) at 25°C for 60 seconds. At this time, the appropriate exposure time was determined to be a point at which the 5th step is completely clear in a gray scale with a density difference of 0.15. Further, the density of the photosensitive layer in the exposed and unexposed areas over time was measured using a Macbeth reflection densitometer. The wet thermostat conditions in Table 2 (temperature 45°C, humidity 75%, 5 days) are considered to correspond to about 1 year and 6 months over natural aging. Table 2 shows naphthoquinone - (1,2) diazide -
(2) Changes in sensitivity and printout contrast over time of a mixed system with a compound of -4-sulfonic acid chloride No. 10 are shown in comparison with each system alone.

[Table] Table 2 shows that when using o-naphthoquinonediazide-4-sulfonic acid chloride alone, when the plate was kept in a wet thermostat (45°C/75% for 7 days), the contrast of the printout decreased significantly. When used alone, if left indoors for 7 days after exposure, the contrast of the printout decreases significantly, but when the two are used in combination, the contrast of the printout remains relatively stable even when the plate is left in a wet thermostat for 7 days. It can be seen that the contrast of the printout does not deteriorate significantly even after being left for 7 days.
Moreover, while compound No. 10 causes a significant decrease in sensitivity when used alone, no significant decrease in sensitivity is observed when using the mixed system. Example 2 A 2S aluminum plate with a thickness of 0.24 mm was degreased by immersing it in a 10% aqueous solution of tertiary sodium phosphate kept at 80°C for 3 minutes, grained with a nylon brush, and then etched with sodium aluminate for about 10 seconds. do,
Desmut treatment was performed with a 3% aqueous solution of sodium hydrogen sulfate. This aluminum plate was anodized in 20% sulfuric acid at a current density of 2 A/dm ² for 2 minutes to produce an aluminum plate ( ). The following photosensitive solution was applied to this aluminum plate (2) and dried at 100°C for 2 minutes. Naphthoquinone-(1,2)-diazide-(2)-5
-Esterified product of sulfonic acid chloride and pyrogallol-acetone resin 0.85g Cresol novolac resin 2.10g Hexahydrophthalic anhydride 0.15g o-naphthoquinonediazide-4-sulfonic acid chloride 0.02g 2-(p-methoxystyryl)-4, 6-bis(trichloromethyl)-S-triazine 0.01g Oil Blue #603 0.04g (manufactured by Orient Chemical Industry Co., Ltd.) Ethylene chloride 16g 2-methoxyethyl acetate 12g The coating weight after drying is 2.5g/ ^m2 . Ta. This photosensitive lithographic printing plate has a high contrast when printed out when exposed to light, and there is little decrease in contrast even if the plate is left in a room for 7 days after exposure. It was not recognized. In Examples 3 to 5, printed images with high contrast were obtained without development by exposing the photosensitive lithographic printing plates obtained in the same manner as in Example 2, so only the photosensitive solution formulations will be described. Example 3 Photosensitive liquid: Naphthoquinone-(1,2)-diazide-(2)-
5-Sulfonic acid chloride and pyrogallol-
Esterified product with acetone resin 0.85g Cresol novolak resin 2.05g pt-butylphenol resin 0.05g Methyltetrahydrophthalic anhydride 0.15g o-naphthoquinonediazide-4-sulfonic acid chloride 0.02g No.9 in Table 1 Compound 0.02g Crystal violet 0.02g Methyl ethyl ketone 8g 2-methoxyethyl acetate 18g Example 4 Photosensitive solution: Naphthoquinone-(1,2)diazide-(2)-5
- Esterified product of sulfonic acid chloride and poly-p-hydroxystyrene (molecular weight 7000) 0.70g Cresol novolak resin 2.25g pt-butylphenol resin 0.05g Tetrahydrophthalic anhydride 0.15g o-naphthoquinonediazide-4-sulfone Acid chloride 0.02g 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-S-triazine
0.01g Oil Blue #603 0.01g (manufactured by Orient Chemical Industry Co., Ltd.) Crystal Violet 0.01g Tetrahydrofuran 16g 2-methoxyethyl acetate 12g Example 5 Photosensitive solution: Naphthoquinone-(1,2)-diazide-(2)-
5-sulfonic acid chloride and pyrogallol
Esterified product with acetone resin 0.92g Cresol novolak resin 2.03g pt-butylphenol resin 0.05g o-naphthoquinonediazide-4-sulfonic acid chloride 0.03g Compound No. 7 in Table 1 0.02g Oil Blue #603 0.015g (manufactured by Orient Chemical Industry Co., Ltd.) Crystal Violet 0.015g Methyl ethyl ketone 19g 2-methoxyethyl acetate 29g Examples 6 to 9 and Comparative Examples 3 to 13 A 2S aluminum plate with a thickness of 0.15 mm was kept at 80°C. It was degreased by immersion in a 10% aqueous solution of sodium triphosphate for 3 minutes, grained with a nylon brush, and then desmatted with a 3% aqueous solution of sodium hydrogen sulfate. This aluminum plate was treated with a 1.5% sodium silicate aqueous solution at 70° C. for 1 minute to produce an aluminum plate ( ). Apply photosensitive liquid to this aluminum plate ()
Drying was carried out at 100°C for 2 minutes. Naphthoquinone-(1,2)-diazide-(2)-5
- Esterified product of sulfonic acid chloride and pyrogallol acetone resin (US Patent No. 3635709)
0.75g Cresol novolak resin 2.10g Tetrahydrophthalic anhydride 0.15g Oil Blue #603 (manufactured by Orient Chemical Industry Co., Ltd.) 0.01g Crystal Violet 0.01g Printing agent Table 3 Ethylene dichloride 16g 2-methoxyethyl acetate 12g The coating amount after drying was 2.4 to 2.5/m ² . This photosensitive lithographic printing plate was image-exposed from a distance of 1 m using a 3KW methyl halide lamp, and then diluted with a 6-fold dilution of DP-1 (product name: Fuji Photo Film Co., Ltd., sodium silicate aqueous solution) at 25°C for 60°C. The film was developed for seconds and the sensitivity was measured. At this time, the appropriate exposure time was determined to be a point at which the 5th step is completely clear in a gray scale with a density difference of 0.15. Further, the density of the photosensitive layer in the exposed and unexposed areas over time was measured using a Masbeth reflection densitometer. The wet thermometer conditions in Table 3 (temperature 45°C, humidity 75%, 5 days) are considered to correspond to approximately 1 year and 6 months over natural aging. Changes in sensitivity and printout contrast over time are shown in comparison with each individual system. Processing ability and development latitude were also evaluated as follows. Processing capacity: Using the developer described above, a photosensitive lithographic printing plate on which only gray scale was printed was processed at a rate ^of 0.5 m ² / hour by developing at 25°C for 60 seconds. Processed up to /.
Sampling is performed every 0.25 m ² / between 2 and 3 m ² /, and the RP-
After applying 1 (erasing liquid manufactured by Fuji Photo Film Co., Ltd.), 10
After being left for a minute and removed with water, GU-2 (gum manufactured by Fuji Photo Film Co., Ltd.) was applied and printing was performed. The processing capacity is shown in Table 3 based on the following criteria. Note that fringe stains are stains caused by components of the photosensitive layer remaining in non-image areas being spread by the erasing liquid and gathering around the erasing liquid. If fringe stains do not occur, it indicates that the developer has developing ability. 〇: Fringe stains occur from 2.75 m ² / △: Fringe stains occur from 2.5 m ² / ×: Fringe stains occur from 2.25 m ² / Development latitude: Image-exposed photosensitive printing plate is exposed to white light. The number of solid gray scales when exposed under the same conditions under a lamp and developed with the above developer at 25℃ for 3 minutes, and when developed with the same developer for 1 minute at 25℃ without exposure to white light. Based on the difference in the number of solid gray scales, the following criteria were used to display the images. The smaller the difference, the stronger it is against exposure to white light. ○: 2 stages or less Δ: 2 to 3 stages ×: 3 stages or more The structural formulas of Compound No. 18 and Compound No. 19 are as follows. Compound No. A represents o-naphthoquinonediazide-4-sulfonic acid chloride.

【table】

[Table] The following can be seen from the results shown in Table 3. In Comparative Example 3, in which o-naphthoquinonediazide-4-sulfonic acid chloride was used in an amount of 13.3% based on the o-naphthoquinonediazide sulfonic acid ester, when left indoors for 5 days, good baking was achieved and contrast was provided, but WetThermo 7 After aging for several days, the print-out contrast deteriorates significantly, and the sensitivity and development latitude are poor. Furthermore, reducing the amount of o-naphthoquinonediazide-4-sulfonic acid chloride improves the sensitivity and development latitude, but further degrades printout contrast, resulting in poor printout contrast even after 5 days of indoor aging. (Comparative Example 4 and Comparative Example 9). On the other hand, o-naphthoquinone diazide-4-
When sulfonic acid chloride and Compound No. 18, No. 19, No. 10, or No. 3 corresponding to component (3) of the present invention are used in combination, the printout contrast is good regardless of aging. , sensitivity, throughput, and development latitude are also good (Examples 6 to 9). On the other hand, in Comparative Examples 5 to 8 in which Compound No. 18, No. 19, No. 10, or No. 3 was used and o-naphthoquinonediazide-4-sulfonic acid chloride was not used in combination, the contrast of the printout was similar to that immediately after exposure. Although the image quality is good, it deteriorates significantly within 7 days after exposure, and the sensitivity and processing ability are low. In addition, compounds No. 18, No. 19,
By reducing the amount of No. 10 or No. 3 used, sensitivity and processing power will be improved, but the contrast of the printout will be lower even immediately after exposure, and the decrease in contrast over time after exposure will be improved. Not done. From the above, the photosensitive composition according to the present invention has a high contrast when printed out, and the high contrast performance is maintained even when exposed after a long period of time and even after a long period of time. It is clear that the film has excellent properties such as good sensitivity, processing ability, and development latitude.

Claims (1)

[Scope of Claims] 1. (1) An organic dye capable of forming a salt in a photosensitive composition comprising an o-quinonediazide compound selected from o-quinonediazide sulfonic acid ester or o-quinonediazide sulfonic acid amide and a phenolic resin. 0.3 to 5% by weight of the total composition, (2) o-naphthoquinonediazide-4-sulfonic acid halide 0.2 to 7% by weight of the total composition, and (3) the following general formula ()
1. A photosensitive composition characterized in that a compound having a halogen and dissociating an acid when irradiated with actinic rays is added in an amount of 0.2 to 7% by weight based on the total composition. [In the formula, Ra is a trihaloalkyl group or trihaloalkenyl group having 1 to 3 carbon atoms,
is N, S, Se, or C, Y is O, N, S, Se
or C and Z has a chromophore group, and X and Y
Indicates a group consisting of a group of nonmetallic atoms necessary to cyclize. 2. The photosensitive composition according to claim 1, wherein the general formula () is represented by the following general formula (), (), or (). [In the formula, A represents H or CH ₃ , and B represents an optionally substituted aryl group or heterocyclic group. Ra is
Same meaning as for general formula (). n is 0, 1 or 2. 3. The photosensitive composition according to claim 1, wherein component (1) is triphenylmethane, azine or anthraquinone dye. 4. The photosensitive composition according to claim 1, wherein the phenolic resin is a cresol formaldehyde condensation resin. 5. The photosensitive composition according to claim 1, wherein the o-quinonediazide compound is o-naphthoquinonediazide-5-sulfonic acid ester.