JPS59121044A - Photosolubilizable composition - Google Patents

Abstract

PURPOSE:To improve the developability of a photosolubilizable composition used in the manufacture of a photomask without reducing the sensitivity by adding an amphoteric surfactant and an org. surfactant contg. boron to the composition contg. an o-quinone diazide compound and an alkali-soluble resin as essential components. CONSTITUTION:An amphoteric surfactant and an org. surfactant contg. boron are added to a photosolubilizable composition contg. an o-quinone diazide compound and an alkali-soluble resin as essential components. An o-naphthoquinone diazide compound is preferably used as the o-quinone diazide compound, and novolak resin, phenolformaldehyde resin or the like is used as the alkali-soluble resin. The preferred amount of the o-quinone diazide compound in the composition is 20-40wt%. An imidazoline deriv., a betaine type compound or an alkylaminocarboxylic acid type compound is used as the amphoteric surfactant, and a compound represented by the structural formula (where R1 is H or COR2, and R2 is 1-25C alkyl or optionally substituted phenyl) is used as the org. surfactant contg. boron.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a photo-solubilizable composition suitable for the production of lithographic printing plates, IC circuits and photomasks. More specifically, the present invention relates to a photo-solubilized composition comprising an O-quinonediazide compound, an alkali-soluble resin, and at least one selected from the group consisting of an amphoteric surfactant and an organic boron surfactant.

Conventionally, photo-solubilized compositions comprising an 0-quinonediazide compound and an alkali-soluble resin have very excellent performance and have been widely used industrially in the production of lithographic printing plates and as photoresists. However, coating films using this photo-solubilized composition have narrow tolerance under development conditions (development tolerance), and therefore it is difficult to control the alkaline concentration of the developer, the temperature of the developer, and the development time. . Various attempts have been made to address these shortcomings. For example, JP-A Shoj J-41,2
In order to improve the strength of the coating film, the use of fillers such as Merck powder, glass powder, viscous powder, starch, wheat flour, corn flour, and Teflon powder is proposed in the publication. However, these general fillers described in Japanese Patent Application Laid-Open No. 13-13-t/λ are not effective in widening the development tolerance, and most of them are not suitable for use as lithographic printing plates. However, it has the disadvantage of making it difficult for printing ink to adhere to the image area.

In addition, when the ratio of the 0-quinonediazide compound in the photo-solubilized composition is increased, the development tolerance becomes wider and the development processing ability increases, but the accompanying low sensitivity poses a problem in practical use.

On the other hand, as described in U.S. Pat. Therefore, by increasing the amount of the 0-quinonediazide compound and adding a cyclic acid anhydride, the development tolerance can be increased without changing the sensitivity.

However, this method has its limitations; if the amount of 0-quinonediazide compound is increased to obtain sufficient development tolerance, the amount of cyclic acid anhydride must be extremely increased to prevent a decrease in sensitivity. This, in turn, led to the disadvantage of weakening the physical strength of the coating film.

Further, for the purpose of coloring images, the inclusion of a pigment in a photo-solubilized composition consisting of an 0-quinonediazide compound and an alkali-soluble resin is described in US Pat. No. 4! //, t121
This is a well-known technology that is described in the specification of the No. By incorporating pigments, image coloring properties can be improved, but if the amount of pigments added is increased until the physical strength of the coating film is increased by the pigments, there is a drawback that sensitivity decreases extremely. TO-Ittori issue publication and Tokukaisho! 3
-, S'/co is a photosensitive lithographic printing plate with photo-erasable print-out properties (ability to obtain a visible image without developing immediately after light) as described in the publication. etc. had the disadvantage that the printed image was difficult to see due to the color of the pigment.

An object of the present invention is to provide a photosolubilizing composition that has wide development latitude without reducing sensitivity.

As a result of various studies, the present inventors have found that a photo-solubilized composition containing an 0-quinonediazide compound and an alkali-soluble resin as essential components contains amphoteric surfactants and organoboron-based surfactants. It has been found that the above object can be achieved by adding at least one of the following to the photosolubilizing composition.

The 0-quinonediazide compound used in the present invention has at least one 0-quinonediazide group, and its solubility changes upon irradiation with actinic rays.

Regarding such 0-quinonediazide compounds, see "Light-Sensitive Systems" by J. Koser.
hn Wilay & 5ons, Tnc,) No. 332
-312 pages, and these can be used in the present invention.

Particularly preferred 0-quinonediazide compounds are 0-su7toquinonediazide compounds, such as U.S. Pat.
44. //, r issue, same issue, 2,7t7゜022, same issue, 77 issue, ri 7 issue, same issue λ.

rzy, ii, No. 2, same No. 2. ri07. tlrj issue, issue 3.0≠t, published by iio, closed 3,04tt, issue 1/1, issue 3. oat, IIS No. 3.0414.1
No. 11, No. 3.0 dub, //ri No. 3.0 gt,
No. 120, No. 3.0 da 4,721, No. 3.04t
No. 6,122, No. 3, 0≠j, No. 121, No. j
, OAI, ≠ 30th, 3rd issue, ioa, tori issue,
3rd, 10th, Ill! R No. 8 Do No. 3. t3j, 70
It is described in many publications, including the P issue ＼ same issue J and A μ 7 ゜ 4t 73, and many other publications.These can be used suitably. Among these, in particular, 0-naphthoquinonediazide sulfonic acid ester or 0-naphthoquinonediazidecarboxylic acid ester of an aromatic hydroxy compound, and 0-naphthoquinonediazide sulfonic acid azide or 0-naphthoquinonediazide carboxylic acid ester of an aromatic amino compound. Acid amides are preferred, particularly those prepared by esterifying a condensate of pyrogallol and acetone with 0-naphthoquinonediazide sulfonic acid, as described in U.S. Pat. No. 3.43j, No. 702;
θ, 2t, iii ester reaction of a polyester having a hydroxyl group at the terminal with 0-s7toquinonediazide sulfonic acid or 0-naphthoquinonediazidecarboxylic acid, US Patent No.
13, 0-naphthoquinonediazide sulfonic acid or 0-naphthoquinonediazidecarboxylic acid to a homopolymer of p-hydroxystyrene or a copolymer of this with other copolymerizable monomers as described in No. 3T1 specification. Those obtained by ester reaction are very good.

Suitable alkali-soluble resins for use in the present invention include novolac resins, specifically phenol formaldehyde resins, cresol formaldehyde resins, p
Examples include tert-butylphenol-4-formaldehyde resin, phenol-modified xylene resin, and phenol-modified xylene mesitylene resin. Its unique alkali-soluble resins include:
Included are polyhydroxystyrene, polyhalogenated hydroxystyrene, copolymers of (meth)acrylic acid and other vinyl compounds (eg, methyl methacrylate), and the like.

The amount of the 0-quinonediazide compound in the pre-solubilized composition consisting of the 0-quinonediazide compound and the alkali-soluble resin is 1o-soz′i:h, more preferably 1.20-
≠O heavy tchi. The amount of alkali-soluble resin blended is 0 to 40 times, preferably 10 to 60 times.

Examples of the amphoteric surfactant used in the present invention include imidacillin conductors, betaine type compounds, and alkylaminocarboxylic acid type compounds, such as those having the following structure.

3 R: Alkyl group with carbon X number V to λ0 R2: CH3, (CI-T2CH20), HI3:
CH3, (CH2CH,,0), Hp+q=,2~
70, n: / ~ / AR: Alkyl group with carbon number ≠ ~ λO R6: CH2CH20H CI (2CH20CH2COONa CH2CH20(CH2)3S03NaCH2CH20
(HCH2CH2N in CH2CH20H (CH2COO
Na)2n=/~/0, 1. =j N/ 07- R,: H, CH2C00NIL R8: Alkyl group with carbon number l-coO R9: H, Na n=1~! These amphoteric surfactants are already well-known compounds and can also be obtained as commercial products.

Examples of the organic boron surfactant include those having the following structure.

-ter- 1- As the alkyl group for R2tR7, for example, CH3C
H3CH2-1CH3(CT-I2)21CH3(CI
■2) 8-70- CH3(CH2) B t CH3(CH2) 1(
p CH3(CH2) 12 +CH3(CH2)14
．． CH3 (CH2)1. , CH3(CH2)18
゜CH3 (CH2) 20・CH3 (CH2) 22・
A straight chain or branched alkyl group having carbon number/-j- such as CH3(CH2) 2° is preferred. In addition, the above R2, R7,
Examples of the substituted 7-enyl group for R8 include the following.

Methods for synthesizing these organic shelf compounds are described in Toho Chemical Industries' product catalog under the trade name Emalbon. Moreover, these Ichiki shelf compounds are published in Tokuko Sho 4t, 2-2.
1104t No. 3, same town μJ-/4tJ22, same town +
J-/! No. 310 publications, U.S. Patent No. 2.22
It is also written in AkiraS such as // issue, 2λλ3 tag number 2, etc.

The amount of the surfactant used in the present invention is 0.0000000000 with respect to the photosoluble composition consisting of 0-quinonediazide and an alkali-soluble resin. /-20 weights is appropriate. 0.1
If the amount added is less than 11% by weight, the effect will be insufficient, and if the amount added is more than 20% by weight, sensitivity will decrease.

The composition of the present invention may contain a cyclic acid anhydride to increase sensitivity, a printout agent to obtain a visible image immediately after exposure, a dye as an image coloring agent, and other fillers. As a cyclic acid anhydride, US Patent No.≠//jtl
Jt specification, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride,
! , 4-endoxy-Δ4-tetrahydrophthalic anhydride, tetrachlorophthalic anhydride, maleic anhydride, chloromaleic anhydride, α-phenylmaleic anhydride, succinic anhydride, pyromellitic acid, and the like. These cyclic acid anhydrides from 7 in the entire composition! ! The sensitivity can be increased up to about 3 times by including the seed amount. Typical print-out agents for obtaining a visible image immediately after exposure include a combination of a photosensitive compound that releases an acid upon exposure and an organic dye that can form a salt. Specifically, Tokukai Akira! 0
The combination of 0-naphthoquinonediazide-7-sulfonic acid halide and salt-forming organic dye described in JP-A-36.702, JP-A-33-TI, JP-A-2R, and JP-A-33-3T2.23. Publication, JP-A-Sho Jll-7g 721
The combination of a trihalomethyl compound and a salt-forming organic dye described in the above publication can be mentioned. In addition to the above-mentioned salt-forming organic dyes, other dyes can also be used as image coloring agents. Suitable dyes including salt-forming organic dyes include oil-soluble dyes and basic dyes. Specifically, Oil Yellow #10/, Oil Yellow @/30. Oil pink #j/J, oil green BG, oil blue BO8, oil blue #tO3,
Oil black BY1 oil black BS, oil black T-joj (manufactured by Orient Chemical Industry Co., Ltd.), crystal violet, methyl violet, rhodamine B1 malachite green, methylene boo/4-lue, etc. can be used.

The composition of the present invention is applied onto a support after being dissolved in a solvent that dissolves each of the above components. The solvent used here is
Ethylene dichloride, cyclohexanone, methyl ethyl ketone, ethylene glycol monomethyl ether, ethylene glycol, monoethyl ether, λ-methoxyethyl acetate, toluene, ethyl acetate, etc.
These solvents may be used alone or in combination. And the concentration (solid content) in the above components is 2~! O% by weight. In addition, the amount of application is generally O1j ~! as solid content! ,
097m is preferred. As the coating amount decreases, the photosensitivity increases, but the physical properties of the photosensitive film deteriorate.

When producing a lithographic printing plate using the photosolubilizing composition of the present invention, the support may be an aluminum plate treated to make it hydrophilic, such as a silicate-treated aluminum plate, an anodized aluminum plate, a grained aluminum plate, or a silicate aluminum plate. Electrodeposited aluminum plate, other zinc plate,
Stainless steel plates, chromium-treated steel plates, hydrophilized plastic films and paper can be used.

Examples of developing solutions 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, tribasic ammonium phosphate, diphosphoric acid, Aqueous solutions of inorganic alkaline agents such as ammonium acid, sodium polysilicate, sodium bicarbonate, aqueous ammonia, etc. are suitable, and their concentrations are 0. It is added in an amount of /~10% by weight, preferably 0.2~1% by weight.

Moreover, a surfactant and an organic solvent such as alcohol can be added to the alkaline aqueous solution as required.

Next, the present invention will be explained in more detail with reference to Examples. In addition, in the following example. All Q-cents are weight percent unless otherwise specified.

Example 1 A 2S aluminum plate with a thickness of 0.11 mm was degreased by immersing it in an aqueous solution of tertiary sodium phosphate kept at 10°C for 3 minutes, and then grained with a nylon brush. Desmut treatment was performed with an aqueous solution of water. This aluminum plate was treated with a 70° C. sodium silicate/j% aqueous solution for 1 minute to produce an aluminum plate (I).

Apply the following photosensitive liquid to the aluminum plate (I) with ioo
Drying was performed for a few minutes at oC.

Photosensitive liquid: 7-toquinone-71.2-diazide-! - Esterified product of sulfonyl chloride and pyrogallol-acetone resin Olli V (U.S. Patent No. J, l
, No. 31,70, Example 1) Cresol formaldehyde resin 1. ri fP-nonylphenol formaldehyde resin 0.0J? Amphoteric surfactants Table 1: Tetrahydrophthalic anhydride 0. λ--(p-butoxyphenyl)-S, t-bis77-(trichloromethyl)-S-) riazine θ, 02su7toquinone-/, cordiazido≠-sulfonic acid chloride 0.02f Oil Blue 8
603 0.01? (manufactured by Orient Chemical Industry Co., Ltd.) Crystal Bai, Olette 0. O1f methyl ethyl ketone jrf ethylene glycol monomethyl ether/J'v The coated weight after drying was about 2.617 m 2 .

The photosensitive lithographic printing plates were each exposed to a 30 ampere carbon arc lamp at 70 m (from a distance of 2 m, S 10
The sensitivity was measured by developing with a 26% aqueous solution (l(72,7)) of sodium silicate with a molar ratio of 2/N a 20 of 7 da for 40 seconds at xzoC.The appropriate exposure time at this time was The point where the 5th step is completely white in the gray scale of the difference o and iz (the point where the photosensitive layer is completely dissolved) was determined.The development tolerance was determined by the density difference of 0.7j at 2j'c with the same developer. In the gray scale, white areas are indicated by development -/I- time in which the number of stages changes by one step.

In this way, the development tolerance could be expanded without impairing the appropriate exposure time (sensitivity).

Example 2 A CoS aluminum plate with a thickness of O and 1/-mm is rθ0C
It was degreased by immersing it in a 10% aqueous solution of tribasic sodium phosphate maintained at a temperature of went. This aluminum plate was heated at a current density of 2 A/dt in 20 sulfuric acid.
r? Anodized the aluminum plate (1
1) was produced.

Apply the following photosensitive liquid to this aluminum plate ('H) and
It was dried at 00°C for 2 minutes.

Photosensitive liquid: Instead of the amphoteric surfactant in Example 1, the organic boron surfactant EMULBON S-20 (
Uses 0.0 to 1 of glycerol polyto laurate (trade name, manufactured by Toho Chemical Industry ■).

Appropriate exposure time and development tolerance were determined in the same manner as in Example 1. The appropriate exposure time was ioo seconds, and the development tolerance was 5 minutes. For comparison, when Emalpon S-10 was not added, the appropriate exposure time was ioo seconds and the development tolerance was 3 minutes. In this way, by adding Emalbon S-20, it was possible to improve the development acceptability without impairing the appropriate exposure time (sensitivity).

Applicant: Fuji Photo Film Co., Ltd.

Claims (1)

[Claims] The inclusion of at least one member selected from the group consisting of monoampholytic surfactants and organoboron surfactants in a photo-solubilized composition containing an 0-quinonediazide compound and an alkali-soluble resin as essential components is considered a gluteal sign. A photo-solubilized composition.