JPS61169835A - Photosolubilizable composition - Google Patents

Abstract

PURPOSE:To obtain superior photosensitivity, wide development latitude, and good printing resistance by using a compsn. composed of a specified compd. producing a free halogen radical upon irradiation of actinic rays, a compd. having a silyl ether, and an alkali-soluble resin. CONSTITUTION:The compsn. is composed of 0.01-1wt% 2-trihalomethyl-5- substd.-1,3,4-oxadiazole compd., 10-40wt% compd. having at least one silyl ether group decomposable with acid in the molecule represented by the formula shown on the right, and 60-90wt% alkali-soluble resin, thus permitting the obtained positive type photosensitive material to be high in photosensitivity, wide in development latitude, superior in storage stability, storable for a long term, superior in printing resistance, simple and easy in manufacture, and usable for a lithographic plate, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to a photo-solubilizable composition suitable for the production of lithographic printing plates. For more details, see (a) Courtolino-lomethyl, which generates halogen free radicals by irradiation with actinic rays! -Substituted mono/, 3,4t-oxadiazole compound, Φ) At least a silyl ether group that can be decomposed by an acid in the molecule
The present invention relates to a photo-solubilized composition comprising a compound having the same properties and (C) an alkali-soluble resin.

(Prior Art) Orthoquinonediazide compounds are conventionally known as photosensitive substances that act on so-called positive chips and are solubilized by actinic rays, and have been widely used in lithographic printing plates, photoresists, and the like. Examples of such orthoquinone diazide compounds include, for example, US Patent J, 744. //r issue,
It is described in numerous publications, including the specifications of the same No. 2.7d and No. 0ta.

These orthoquinonediazide compounds decompose when exposed to active light! These methods take advantage of the fact that they produce a ring-membered carboxylic acid and are soluble in alkali, but all of them have the drawback of insufficient photosensitivity. This is because, in the case of orthoquinonediazide compounds, the quantum yield essentially does not exceed .

Various attempts have been made to increase the photosensitivity of photosensitive compositions containing orthoquinonediazide compounds, but all of them have only increased the sensitivity by two to three times. For example, as an example of such an attempt,
t/-7224t, No. 2, Tokukai Sho! Co410/Co! No. 307.173, U.S. Patent No. 307.173.

Also, recently, several proposals have been made regarding photosensitive compositions that act on positive chips without using an orthoquinone diazide compound. As for seven of them, for example,
Examples include polymer compounds containing orthonitrocarbinol ester groups described in the specification of No. 25-6. However, in this case too, the photosensitivity cannot be said to be sufficient for the same reason as in the case of orthoquinone diazide. In addition, as a method of increasing photosensitivity using a photosensitive system activated by contact action, there is a known method in which the acid generated by photolysis causes the second reaction, thereby solubilizing the exposed area. The principle of is applied.

Examples of this include, for example, a combination of a compound that generates an acid upon photolysis and an acetal or an O,N-acetal compound (JP-A No. 19003), or a combination with an orthoester or an amide acetal compound (JP-A No. 19003). Kaisho!/
-/co07/41), combination with a polymer having an acetal or ketal group in the main chain (JP-A-Sho, tj-/3!
4t Kota), a combination with an enol ether compound (JP-A No. 72 Tata J), a combination with an N-acylimino carbonate compound (JP-A No. 1-726234), and a combination with an orthoester group in the main chain. (JP-A-Sho, !+4-/734tj). In principle, these have a quantum yield exceeding /, so they may exhibit high photosensitivity. Since the rate of the second reaction by the acid produced in is slow, it does not exhibit sufficient photosensitivity for actual use. In addition, orthoester or amide acetal compounds, enol ether compounds, and N-acylimino carbonate compounds certainly exhibit high photosensitivity, but their stability over time is poor and they cannot be stored for long periods of time. do not have. Polymers having orthoester groups in their main chains also have high sensitivity, but have the disadvantage of narrow development tolerance during development.

(Object of the Invention) An object of the present invention is to provide a photo-solubilizable composition that solves these problems and has printing durability. That is, the object is to provide a photo-solubilized composition that has high photosensitivity, wide development latitude during development, excellent stability over time, can be stored for a long period of time, and has printing durability.

Yet another object of the present invention is to provide a photosolubilizable product that is simple to produce and easily obtainable.

(Structure of the Invention) As a result of intensive studies to achieve the above object, the present inventors have found that the above object can be achieved by using the photo-solubilized composition described below, and have arrived at the present invention.

That is, the present invention provides (a) Co-trihalomethyl which generates halogen free radicals by irradiation with actinic rays! -Replacement-/,!
, +1-oxadiazole compound 0.07-7% by weight,
φ) A compound having at least/one acid-decomposable silyl ether group represented by the following general formula (1) in the molecule/0-10% by weight, and (C) an alkali-soluble resin from 40 to 0% by weight The present invention provides a highly sensitive photo-solubilized composition with high printing durability.

The silyl ether group-containing compound used on the second side (in the present invention) is a compound having at least seven silyl ether groups that can be decomposed by an acid and is represented by the following general formula (1).

Specifically, Tokugan Shojl-/4tbuOri! No. Tokugansho! ?
-230377, special request! Day issue (Showa! February 2016/Da date patent application (A)) and patent application Showa! Tar
No. (Patent Application (A) dated February 46, 1920).These are silyl ether compounds described in each specification.

Among these, the silyl ether compounds containing a hydrophilic group described in Japanese Patent Application No. Shojl"-Jjθ327 are particularly useful. Specific examples of the hydrophilic group include those shown below.

(-(cH2), 09, Ship In formula 09, l represents an integer of /~da, m and n are integers of 7 or more, preferably integers of 1 to 100, more preferably /~2
Indicates an integer of 0. R represents an alkyl group or a phenyl group which may have a substituent.

A particularly preferred hydrophilic group is +cH2CH2-0÷.

Specific examples of the compound in Φ) of the present invention include those shown below.

In the specific examples, X%y indicates a molar ratio, where x=θ to 3 mol% and y=7 to 100 mol%. n represents an integer of 7 or more.

The amount of the silyl ether group-containing compound added in the entire composition is 1
0-10% by weight. If the weight is less than 10%, no image will be formed. Moreover, if it is more than 4 tO weight, it becomes unstable over time and is not preferable. A more preferable addition amount is 76 to 30% by weight.

Coat trihalomethane which generates norogen free radicals by irradiation with actinic rays used in the present invention! -Replacement-/,!
, 41-oxadiazole compound is disclosed in JP-A-Sho! j-
7774tco, Tokukai Sho! Tar/4t17r4 issue or special request Shoj'? -341010 Compounds of the following general formula (I) whose descriptions are reproduced in each specification can be mentioned.

Here, X represents a chlorine atom or a bromine atom, and A represents a phenyl group, a naphthyl group, a norogen atom, an alkyl group,
Y represents a hydrogen atom, a cyano group, an alkyl group, or an aryl group, such as a phenylene group substituted with an alkoxy group, a nitro group, a cyano group, or a methylenedioxy group, or an unsubstituted aromatic residue. ).

The amount of the compound of general formula (II) that generates acid upon irradiation with actinic rays is 0.07 to 1% by weight. If the amount added is less than 0.07% by weight, the amount of acid generated is too small, resulting in a poor feeling. In addition, when 1 weight or more of the additive is added, if the printing plate is left in a bright room during printing after development, acid will be generated in the image area and the printing durability will be significantly reduced. A suitable addition amount is 0. /~O9! Weight -.

Suitable alkali-soluble resins used in the present invention include novolak resins such as phenol formaldehyde resin, cresol formaldehyde resin, p-ter-7' methylphenol formaldehyde resin, phenol-modified xylene resin, and phenol-modified xylene mesitylene resin;
Pyrogallol/acetone condensates, polyhydroxystyrene polymers and copolymers, polyhalogenated hydroxystyrene polymers and copolymers, copolymers of (meth)acrylic acid and other vinyl compounds (e.g. methyl methacrylate) Examples include crotonic acid copolymers, maleic acid copolymers and their partially esterified products, and itaconic acid copolymers. These alkali-soluble resins may be used alone or in a mixture of λ or more.

The amount of alkali-soluble resin added in the entire composition is 40 to 0.
The weight of the cake is preferably 70-13'.

The photosoluble composition of the present invention may further contain a dye (
For example, C,1, Solvent Orange 6, C,I, Solvent Red/4t3, C,1, Norvent Red/4t
! ,c,1. Solvent Blue 36, c, 1. anthraquinone dyes such as Solvent Blue/- and monoazo metal complex dyes), pigments (e.g. C, 1, Pigment Blue ♂, c, 1. Pigment Blue/j), fillers (
For example, silica powder, polyethylene powder, fluorinated polyethylene powder, calcium carbonate powder, barium sulfate powder, etc.)
, plasticizers, cyclic acid anhydrides that increase sensitivity (e.g. phthalic anhydride, tetrahydrophthalic anhydride, maleic anhydride, succinic anhydride, etc.), and compounds that increase the acid generation efficiency of the compounds capable of generating the acids (so-called Sensitizers) etc. can be included.

The photosoluble composition of the present invention is dissolved in a solvent that dissolves each of the above components and applied onto a support. Solvents used here include ethylene dichloride, cyclohexanone, methyl ethyl ketone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, comethoxyethyl acetate, toluene, and ethyl acetate, and these solvents can be used alone or in combination. do.

And the concentration in the above ingredients (total solid content including additives) is:
Ko~! O weight -. Among these, composition (a) of the present invention
+ (b) + The preferred concentration (solid content) of (C) is O1/~2j% by weight. In addition, the coating amount is generally O1 as a solid content for a photosensitive planographic printing plate! ~3゜0g7
m2 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 photosoluble composition of the present invention, the support may be a hydrophilized aluminum plate, such as a silicate-treated aluminum plate, an anodized aluminum plate, a grained aluminum plate, or a silicate electrode. There is a coated aluminum plate, as well as a zinc plate,
Examples include stainless steel plates, chromium-treated steel plates, and hydrophilic plastic films and paper.

Examples of active light sources used in the present invention include mercury lamps, metal halide lamps, xenon lamps, chemical lamps, and carbon arc lamps. Scanning exposure with a high-density energy beam (laser beam or electron beam) can also be used in the present invention. Such laser beams include helium neon lasers, argon lasers, krypton ion lasers, and helium neon lasers.
Examples include cadmium lasers.

Examples of developing solutions for the photosoluble 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, dibasic diphosphate, Aqueous solutions of inorganic alkaline agents such as ammonium acid, sodium metasilicate, sodium bicarbonate, aqueous ammonia, etc. are suitable, and their concentrations are 0. / ~ / θ Shigekei,
Preferably 0. T~! It is added so that the weight becomes -.

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

Hereinafter, the present invention will be explained in more detail with reference to Synthesis Examples and Examples, but the content of the present invention is not limited thereto.

Synthesis example / /, /-octanediol 7.32g (θ, 0jO/m
ole), tetraethylene glycolta.

1g (0.01θOmole), pyridine/7°4t
g (O,, 2 Omole), dehydrated distilled toluene r
om1 mixture, dichlorodimethylsilane/2. Rig
(0,100 mole) run, 20rrt
/ solution was added from the dropping funnel over 30 minutes while stirring and cooling on ice. After the addition, stirring was continued for 1 hour at to0c. The produced white salt (pyridine hydrochloride) was filtered off, and the toluene solution was concentrated under reduced pressure. After that, under vacuum (approx./m
mHg), and was dried for 70 hours while heating at about ro0c. A colorless transparent liquid, yield 20.7g 6NMH, confirmed that the structure was a compound. Furthermore vP
O(vapour pressure Qsmom
When the number average molecular weight was measured using Mn
=/? /θ.

Synthesis example / in /, ? - p-xylylene glycol J instead of octanediol and tetraethylene glycol, 63 g (θ, o4t00mole)
, polyethylene glycol Luna 300 (manufactured by Kanto Kagaku ■, average molecular weight 3oo) irg (o.

Using θgθmole), the reaction and post-treatment were performed in the same manner as in Synthesis Example. Colorless transparent viscous liquid, yield 26°/g, N
The structure was confirmed to be compound example &- by MR, and the number average molecular weight was measured by vPO, and it was found that Mn=/
It was 730.

Example/ A JS aluminum plate with a thickness of θ, 2 am was immersed in a 10% aqueous solution of tertiary sodium phosphate kept at ♂00C for 3 minutes to degrease it, grained with a nylon brush, and then soaked in sodium aluminate for about 70 seconds. It was etched and desmutted with a 3-chloride aqueous solution of sodium hydrogen sulfate. This aluminum plate was heated at a current density of λA/d m in sulfuric acid.
In step 2, anodic oxidation was performed for 2 minutes to produce an aluminum plate.

Next, the photosensitive liquid [A] of the present invention in which the type and amount of the acid generator was changed
)-/~[A]-4 and [A]-7~[A
]-9 was prepared, and this photosensitive solution was applied onto an anodized aluminum plate and dried at 100°C for 2 minutes to form each photosensitive lithographic printing plate (A]-/~[A]- The amount of coating at this time was all dry weight, Og/
It was m2.

Further, the type and amount of the acid generator used in the photosensitive liquids (A)-/ to [A)-ta are shown in Table 1.

Photosensitive liquid CA) Photosensitive lithographic printing plate (A) -/~ [A) - ta, density difference θ,
/! A gray scale was placed in close contact with the sample, and exposure was performed from a distance of 70 cm using a 10 ampere high pressure mercury lamp.

After 30 minutes of exposure, the photosensitive lithographic printing plate (A) -/~CAl-ta was immersed and developed in a 10-fold diluted aqueous solution of 0P-3 (product name: manufactured by Fuji Photo Film ■) at 5z0c for 60 seconds to obtain a density difference of O1/ ! The exposure time that would make the first row completely clear on the gray scale was determined. In addition, half of each developed printing plate was left in a bright room for 2 hours and exposed to light, and the other half was covered with black polyethylene and not exposed to light, and its printing durability was examined using a Heidel printing machine. The results are shown in Table/.

From Table 7, the acid generator is coat-rehalomethyl! -Replacement 1/
, J, As the amount of the 4t-oxadiazole compound added increases, the sensitivity increases, but if the printing plate is exposed to light in a bright room after development, the printing durability deteriorates. (All-g
When the amount added is about 0.002% by weight, the deterioration rate is slight, but when the amount added exceeds 7% by weight, as in Comparative Example [A]-7, the printing durability is extremely deteriorated.

Also, in the case of the same acid generator, the present invention's Coat Reha methyl! -Substituted-/, J, Trihalomethyl compounds of 8-) riazine other than 4t-oxadiazole compounds have a large deterioration in printing durability due to exposure to light.

This is presumably because the trihalomethyl compound of 3-triazine generates a large amount of acid.

Example 2 A photosensitive lithographic printing plate [B] was prepared in the same manner as in Example 1, except that the compound in Synthesis Example 1 was used in place of the compound in Synthesis Example 1 in [A]-1. By the method shown in Example/, the concentration difference θ, /! In grayscale! The exposure time for completely clearing the rows was determined to be about 2 seconds. After leaving this printing plate in a bright room, I printed it with a Heidel printing machine and it turned out to be 11! I was able to print a million copies.

Patent applicant: Fuji Photo Film Co., Ltd.

Claims (1)

Scope of Claims: (a) 0.01 to 1% by weight of a 4-trihalomethyl-5-substituted-1,3,4-oxadiazole compound that generates halogen free radicals upon irradiation with actinic rays; (b) ) 10 to 40% by weight of a compound having at least one acid-decomposable silyl ether group represented by the following general formula (I) in the molecule; and (c) 60 to 90% by weight of an alkali-soluble resin. Solubilizing composition. ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I)