JPH0612448B2 - Photosensitive composition and photosensitive lithographic printing plate - Google Patents

Description

The present invention relates to a photosensitive lithographic printing plate and a photosensitive composition used for the printing plate.

BACKGROUND OF THE INVENTION Orthoquinonediazide compounds have been conventionally known as photosensitive substances for photosensitive compositions used for photosensitive lithographic printing plates. The composition has been widely used as a lithographic printing plate and a photoresist for photoetching. Examples of such orthoquinonediazide compounds include, for example, JP-A-47-5303, JP-A-48-63802, JP-A-48-63803, and JP-A-49-3870.
1, No. 56-1044, No. 56-1045, Japanese Patent Publication No. 41-11222,
43-28403, 45-9610, 49-17481 publications,
U.S. Patent Nos. 2,797,213, 3,046,120, 3,188,21
No. 0, 3,454,400, 3,544,323, 3,573,917,
No. 3,674,495, No. 3,785,825, British Patent No. 1,277,
No. 602, No. 1,251,345, No. 1,267,005, No. 1,32
Examples thereof include those described in each specification such as 9,888, 1,330,932, and German Patent No. 854,890.

The above-mentioned orthoquinonediazide compounds are used because they are decomposed by irradiation with an actinic ray and are solubilized in a developer for a photosensitive lithographic printing plate, but they all have a drawback of low sensitivity.

As a method of increasing the sensitivity of a photosensitive substance used in a photosensitive composition, there is a method of causing a second step reaction by an acid generated by photolysis, and as a result, solubilizes a portion exposed by actinic rays. That is, a positive-working photosensitive material is used. Specifically, it is a photosensitive composition comprising a combination of a compound capable of generating an acid by photolysis and a compound capable of being decomposed by the acid, and examples of the compound capable of being decomposed by the acid include, for example, JP-A-48 Or O, N-acetal compound described in JP-A-89003, a compound having an orthocarboxylic acid ester group and / or a carboxylic acid amide acetal group described in JP-A-51-120714, JP-A-53-133429. There are polymers having an acetal group or a ketal group in the main chain described in JP-A No. 1993-187, or a polymer having an orthocarboxylic acid ester group in the main chain described in JP-A-56-17345.

However, in these compounds, even in the case of a photosensitive substance showing higher sensitivity than the above-mentioned orthoquinonediazide compound, in the case of an acetal or O, N-acetal compound, and a polymer having an acetal group or a ketal group in its main chain. In that case, there was a drawback that the sensitivity was not sufficient and they were not suitable for actual use.

Further, in the case of a polymer having an orthocarboxylic acid ester group in the main chain, when used as a photosensitive lithographic printing plate, there is a drawback that the development tolerance of the photosensitive lithographic printing plate during development is narrow and it becomes a practical problem. It was Therefore, as a photosensitive composition used for the photosensitive layer of a photosensitive lithographic printing plate, a high-performance photosensitive composition having improved overall performance has been demanded.

As a result of earnest research, the researchers of the present invention can obtain a photosensitive composition having high sensitivity and wide development latitude by using a compound which can be decomposed by an acid and has at least one of the following structural units. The present invention has been completed by discovering that a photosensitive lithographic printing plate using this as a photosensitive layer can be sufficiently put to practical use.

(Where X and Y are -O- or And X and Y may be the same or different. ) [Object of the Invention] An object of the present invention is to provide a novel photosensitive composition having high sensitivity and broad development acceptability. Another object of the present invention is to provide a photosensitive lithographic printing plate having a photosensitive layer with a photosensitive composition having high sensitivity and wide development tolerance.

[Constitution of the Invention] The above object of the present invention is to provide a photosensitive composition which is a compound capable of generating an acid upon irradiation with actinic rays, and a compound having at least one of the following structural units capable of being decomposed by an acid, and further a support. This is accomplished by a photosensitive lithographic printing plate having thereon a photosensitive layer formed from the above photosensitive composition.

(Where X and Y are -O- or And X and Y may be the same or different. [Specific Configuration of the Invention] The photosensitive composition of the present invention contains a compound capable of generating an acid upon irradiation with actinic rays and a compound capable of being decomposed by the acid.

The acid-decomposable compound is specifically a compound containing at least one structural unit represented by the following general formula [I] that can be decomposed by an acid.

General formula [I] [In the formula, X and Y are R ₃ O, R ₄ O, and R, respectively.
₅ (R ₆ ) N, R ₇ (R ₈ ) N, And R _{1 to} R ₁₀ may be the same or different,
Substituted or unsubstituted alkyl group, substituted or unsubstituted aryl group, substituted or unsubstituted alkenyl group, substituted or unsubstituted alkylene group, substituted or unsubstituted arylene group, substituted or unsubstituted alkenylene group, or substituted Alternatively, it represents an unsubstituted alkylene group. Further, each of the above groups may be an ether group, an amino group, a carbonyl group (aldehyde group,
A ketone group, a carboxylic acid ester group, a carbonic acid ester group).

R ₅ , R ₆ and R ₇ , R ₈ may form a ring with each other. The above R ₁ O-, R ₂ O-, X and Y may be the same or different, and at least two of them are bonded to each other to form an aliphatic ring or an aromatic ring. You may form the part.

At least one structural unit represented by the general formula [I] is used.
As a specific compound contained therein, a compound containing at least one structural unit (unit) of an orthocarbonate represented by the following general formula [II] can be mentioned.

General formula [II] (In the formula, R _{1 to} R ₄ are the same as those described above for the general formula [I].
It is the same as _{1 to} R ₄ . As the compound containing at least one orthocarbonate unit represented by the general formula [II], for example, a compound having at least one phenolic OH group and / or at least one alcoholic OH group (hereinafter referred to as O
At least one of (H group-containing compound) and tetraalkoxymethane can be synthesized by a transesterification reaction in one step or in two or more steps.

Regarding the above-mentioned transesterification reaction, for example, Svensk K
A method similar to or similar to the method described in em.Tidskr.65, 10 (1953) can be used.

Examples of the OH group-containing compound include monovalent alcohols, divalent alcohols, trivalent alcohols, tetravalent or higher alcohols, monovalent phenol-based compounds, divalent phenol-based compounds, and trivalent phenol-based compounds. Examples of the compound include a tetravalent or higher-valent phenolic compound, and a compound having a phenolic OH group and an alcoholic OH group at the same time.

Examples of the monohydric alcohol include n-propyl alcohol, n-butyl alcohol, n-pentyl alcohol, n-hexyl alcohol, n-heptyl alcohol, n-octyl alcohol, n-decyl alcohol, n-dodecyl alcohol. , N-tetradecyl alcohol, n-hexadecyl alcohol, n-octadecyl alcohol, isopropyl alcohol, isobutyl alcohol, sec-butyl alcohol, tert-butyl alcohol, isopentyl alcohol, active amyl alcohol, tert-pentyl alcohol, cyclopentanol ,
Cyclohexanol, allyl alcohol, crotyl alcohol, methyl vinyl carbinol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether,
Aliphatic alcohols such as diethylene glycol monoethyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, benzyl alcohol, α-phenylethyl alcohol, β-
Phenylethyl alcohol, diphenylcarbinol,
Examples thereof include aromatic alcohols such as triphenylcarbinol and cinnamyl alcohol.

Examples of the dihydric alcohol include pentane-1,5-diol and n-hexane- described in JP-A-53-133429.
1,6-diol, 2-ethyl-hexane-1,6-diol, 2,3-dimethyl-hexane-1,6-diol, heptane-1,7-diol, cyclohexane-
1,4-diol, nonane-1,7-diol, nonane-1,9-diol, 3,6-dimethyl-nonane-1,
9-diol, decane-1,10-diol, dodecane-1,12-diol, 1,4-bis- (hydroxymethyl) -cyclohexane, 2-ethyl-1,4-bis-
(Hydroxymethyl), cyclohexane, 2-methyl-
Cyclohexane-1,4-diethanol, 2-methyl-
Cyclohexane-1,4-dipropanol, thio-dipropylene glycol, 3-methyl-pentane-1,5-
Diol, dibutylene-glycol, oxypivalic acid-neopentyl glycol ester, 4,8-bis-
(Hydroxymethyl) -tricyclodecane, n-butene- (2) -1,4-diol, n-but-2-yne-
1,4-diol, n-hex-3-yne-2,5-diol, 1,4-bis- (2-hydroxyethoxy)-
Butyne- (2), p-xylylene glycol, 2,5-
Dimethyl-hex-3-yne-2,5-diol, bis- (2-hydroxyethyl) -sulfide, 2,2
Aliphatic alcohols such as 4,4-tetramethylcyclobutane-1,3-diol, di-, tri-, tetra-, penta- and hexaethylene glycol, di- and tripropylene glycol and polyethylene glycols with an average molecular weight of 200, 300, 400 and 600 And aromatic alcohols such as p-xylylene glycol and 2-methyl-2-phenyl-1,3-propanediol.

Examples of the trihydric alcohol include glycerol, butane-1,2,4-triol described in JP-A-56-17345,
2-hydroxymethyl-butane-1,4-diol, pentane-1,2,5-triol, 2-hydroxymethyl-pentane-1,5-diol, hexane-1,2,
5-triol, 2-hydroxymethyl-hexane-
1,6-diol, hexane-1,2,6-triol, 4-ethyl-hexane-1,4,5-triol,
Hebutane-1,4,5-triol, 1- (1,2-dihydroxyethyl) -4-hydroxymethyl-benzene, 2,4,6-triethyl-5-propyl-heptane-1,3,7-triol, 1- (2,3-dihydroxy-propoxy) -4-hydroxymethyl-benzene,
1- (2,3-dihydroxypropyl) -4-hydroxymethyl-benzene, oct-3-nin-1,7,8-
Triol, octane-1,2,8-triol, octane-1,3,8-triol, nonane-1,4,5-
Triol, 3- (1-hydroxy-1-methyl-ethyl) -5-oxa-octane-2,8-diol, 2,
6,8-Trimethyl-3-hydroxymethyl-nonane-
6,7-diol, 2-hydroxymethyl-3-oxa-heptane-1,7-diol and hexadecane-1,
Aliphatic or aromatic alcohols such as 2,16-triol can be mentioned.

Examples of tetrahydric or higher alcohols include aliphatic alcohols such as pentaerythritol, threitol, pentitol, sorbitol and polyvinyl alcohol. Aromatic alcohol may also be used.

Examples of monovalent phenol compounds include phenol, o-cresol, m-cresol, p-cresol, 3,5-xylenol, carvacrol, thymol, α-naphthol and β-naphthol.

The divalent phenolic compound includes catechol, resorcin, hydroquinone, 2,2-bis (4-hydroxyphenyl) butane, bis (p-hydroxyphenyl) methane, 2,2-bis (4-hydroxyphenyl) propyne, 2,3-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene and the like can be mentioned.

Examples of trivalent phenol compounds include pyrogallol and phloroglucin.

The tetravalent or higher phenolic compounds include 1, 4, 9,
Examples thereof include 10-tetrahydroxyanthracene.

As a compound having both phenolic OH and alcoholic OH at the same time, 2- (bis (4-hydroxyphenyl))
Methyl) benzyl alcohol and the like can be mentioned.

Further, in some of these OH group-containing compounds, at least one OH group may be esterified with an acetyl group or the like.

As the tetraalkoxymethane, for example, tetramethoxymethane or tetraethoxymethane is generally used.

Tetraethoxymethane can be obtained, for example, from Organic Synthesis, Collect, Volum IV (Organic Synthenes, Co
ll. Vol. IV) 457 (1963), it can be synthesized with chloropicrin and sodium ethoxide. Other tetraalkoxymethanes can be synthesized by the same method. Also, Journal of Organic Chemistry (J. Org. Chem.,) 36, 1176 (197).
Method similar to that described in 1) or Journal of Organic Chemistry (J.Org.Chem.,) 3
It can also be synthesized by a method similar to the method described in 7,4198 (1972).

The compound of the present invention includes, for example, the tetraalkoxymethane and the OH group-containing compound at 60 to 170 ° C. without using a solvent.
Can be obtained by reacting at a temperature of, preferably at a temperature of 80 to 150 ° C. The liberated lower alcohol is optionally distilled off. At this time, the reaction is preferably carried out in the presence of an acidic catalyst such as p-toluenesulfonic acid or sulfuric acid. In some cases, the reaction may be performed under reduced pressure. Further, a solvent inert under the above reaction conditions, for example, benzene, toluene, xylene, dioxane, chlorinated hydrocarbon and the like can be used as a reaction solvent. The liberated lower alcohol is optionally distilled off together with part of the solvent.

The amount ratio in the reaction between the tetraalkoxymethane and the OH group-containing compound is such that the total amount of OH groups is 4 mol per 1 mol of tetraalkoxymethane, but in some cases, a different amount ratio may be used. .

When two kinds of OH group-containing compounds are used, a total of three tetraalkoxymethanes and two kinds of OH group-containing compounds may be reacted at the same time. In some cases, first, tetraalkoxymethane and one OH group-containing compound are contained. The compound may be reacted and then the product and the other OH group containing compound. The reaction can be similarly performed when three or more kinds of OH group-containing compounds are used.

It can also be synthesized by a method similar to or similar to the method described in Chem. Ber. 544 (1961). For example, obtained by the method of the literature Examples thereof include a method of reacting diphenyloxydichloromethane with the above-mentioned OH group-containing compound.

The product obtained by the above method is the compound of the present invention, and the orthocarbonic acid ester represented by the above general formula [II]
A compound containing at least one unit. As an example thereof, a compound containing one of the following orthocarbonic acid ester group units, a compound containing two or more or a mixture thereof can be mentioned.

The above R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ each represent an alkyl group, an aryl group, an aralkyl group, an alkenyl group or the like. These alkyl group, aryl group, aralkyl group and alkenyl group include those having a substituent. In addition, at least two of R _{11 to} R ₁₄ may be bonded to each other to form a ring.

Further, the bond part is a substituted or unsubstituted alkylene group, arylene group, alalkylene group, alkenylene group [these groups may be an ether group, amino group, carbonyl group (aldehyde group, ketone group, carboxylic acid ester group ,
It may contain a carbonic acid ester group). ], Etc., and may be further bonded to the one having the same or other orthocarbonate unit described above.

Further, as the compound having at least one orthocarbonate unit, the one having an orthocarbonate unit in the region of 1 to 300 in the molecule is suitable.

It is preferably one having a region of 1 to 100.

Specific examples of the compound of the present invention having at least one orthocarbonic acid ester unit are shown below.

Exemplified compound No. 1 No.2 No.3 No.4 No.5 No.6 (CH ₃ O) ₄ C and HOCH ₂ CH (OH) reaction products of C ₃ H ₆ CH ₂ OH No.7 _{No.8 (C 2 H 5 O)} 4 and _{HOCH 2 CH (OH) C 3} H 6 CH 2 OH and the reaction product No.9 (C ₄ H ₉ O) of ₄ C and (HOCH _{2) 4} C and Reaction product No. 10 (C ₂ H ₅ O) ₄ C with HOCH ₂ CH (OH) CH (OH) CH ₂ OH reaction product No. 11 (C ₃ H ₇ O) ₄ C with HOCH ₂ CH (OH) C ₃ H ₆ CH ₂ OH Reaction product No. 12 No.13 No.14 No.15 No.16 No.17 No. 18 No. 19 No.20 No.21 No.22 No.23 No. 24 No.25 No.26 No. 27 No. 28 No. 29 No.30 No.31 No. 32 No.33 No.34 As another specific compound containing at least one structural unit represented by the general formula [I], a compound represented by the following general formula [II
Examples thereof include compounds containing at least one structural unit represented by [I].

General formula [III] (In the formula, R ₁ , R ₂ , and R _{5 to} R ₈ are the same as R ₁ , R ₂ , and R _{5 to} R ₈ described above for the general formula [I].) Shown in the general formula [III]. The compound containing at least one structural unit can be obtained, for example, by reacting diaryloxydichloromethane with an amine compound. The diaryloxydichloromethane in this case is, for example, the chemical compound described above for the synthesis of the general formula [II].
It can be synthesized by a method similar to or similar to the method described in Chem.Ber. 544 (1961).

Examples of the amine compound include methylamine,
Ethylamine, propylamine, isopropylamine,
Butylamine, amylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, undecylamine, dodecylamine, tridecylamine, detradecylamine, pentadecylamine, cetylamine, dimethylamine, diethylamine, dipropylamine, diisopropylamine , Dibutylamine, diamylamine, cyclopropylamine, cyclobutylamine, cyclopentylamine, cyclohexylamine,
Allylamine, diallylamine, piperidine, ethylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane , Aliphatic amines such as piperazine and aniline, methylaniline, ethylaniline, o-toluidine, m-
Toluidine, p-toluidine, benzylamine, dibenzylamine, diphenylamine, α-naphthylamine,
Examples include aromatic amines such as β-naphthylamine, p-phenylenediamine, and 2-aminopyrimidine.

Furthermore, β-propiolactam, α-pyrrolidone, β-pyrrolidone, α-piperidone, β-piperidone, γ-piperidone, propionanilide, propionamide, succinimide, phthalimide, phthalamide, diaminoacridone, urea and the like can also be mentioned. .

Examples of specific compounds are shown below.

No.35 No. 36 No. 37 No. 38 No. 39 No.40 No.41 p is a positive integer, preferably an integer of 1 to 500.

As another specific compound containing at least one structural unit represented by the general formula [I], the following general formula [IV]
A compound containing at least one structural unit represented by

General formula [IV] _{(Wherein, R 1, R 2, R} 9, R 10 are the same as _{R 1, R 2, R 9} , R 10 described above with respect to general formula [I].) Represented by the general formula [IV] The compound containing at least one structural unit represented by the formula can be obtained by, for example, reacting diaryloxydichloromethane with a compound containing a carboxyl group in the same manner as in the synthesis of the compound containing at least one structural unit represented by the general formula [III]. it can.

The carboxyl group-containing compound, for example, formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, linolenic acid , Cyclohexanecarboxylic acid, phenylacetic acid, benzoic acid, o-toluic acid, m-toluic acid, p-toluic acid, o-chlorobenzoic acid, m-chlorobenzoic acid, p-
Chlorobenzoic acid, o-bromobenzoic acid, m-bromobenzoic acid, p-bromobenzoic acid, o-nitrobenzoic acid, m-
Nitrobenzoic acid, p-nitrobenzoic acid, phthalic acid, isophthalic acid, terephthalic acid, o-methoxybenzoic acid, m-
Methoxybenzoic acid, p-methoxybenzoic acid (anisic acid), oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, speric acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, tricarballylic acid ,
Examples thereof include trimesic acid and benzylidene malonic acid.

Examples of specific compounds are shown below.

Exemplified compound No. 42 No.43 No.44 No. 45 q is a positive integer, preferably an integer of 1 to 500.

Examples of the other specific compound containing at least one structural unit represented by the general formula [I] include the compounds shown below.

No.46 No.47 No. 48 No. 49 No.50 x is a positive integer, preferably an integer of 1 to 500.

Further, the compounds of the present invention are further represented by the above general formulas [II], [II
Examples thereof include compounds having two or more types of structural units represented by [I] or [IV] in one molecule.

The content of the compound of the present invention is preferably 5 to 70% by weight, and particularly preferably 10 to 50% by weight, based on the total solid content of the photosensitive composition of the present invention.

The compounds of the present invention may be used alone or in combination of two or more. When the compound of the present invention is obtained as a mixture of several compounds, the compound may be used as it is or may be separated and produced.

It is essential that the photosensitive composition of the present invention further contains a compound capable of generating an acid upon irradiation with actinic rays (hereinafter referred to as the acid generating compound of the present invention).

Examples of the acid generating compound of the present invention include various known compounds and mixtures. For example, diazonium salt, phosphonium salt, sulfonium salt, and iodonium BF _4.
⁻ , PF ₆ ⁻ , SbF ₆ ⁻ , SiF ₆ ⁻ , ClO ₄ ^−.
Salts such as, organic halogen compounds, orthoquinone-diazide sulfonyl chlorides, and organometallic / organohalogen compounds are also actinic ray-sensitive components that form or separate acids upon irradiation with actinic rays, and as acid generating compounds of the present invention, Can be used. All organohalogen compounds which are in principle known as free-radical-forming photoinitiators are compounds which form hydrohalic acid and can be used as acid-generating compounds according to the invention.

Examples of the compound forming a hydrohalic acid are U.S. Pat.Nos. 3,515,552, 3,536,489 and 3,773.
The compounds described in JP-A-9,778 and West German Patent Publication No. 2,243,621 can be mentioned, and compounds capable of generating an acid by photolysis as described in West German Patent Publication No. 2,610,842 can also be used.

Further, 2 described in JP-A-54-74728, JP-A-55-24113, JP-A-55-77742, JP-A-60-3626 and JP-A-60-138539. -Halomethyl-1,
A 3,4-oxadiazole-based compound or the like can also be used.

Specific examples of the acid-generating compound of the present invention include those disclosed in JP-A-56-173.
The following can be cited as described in Japanese Patent No. 45.

4- (di-n-propylamino) -benzenediazonium tetrafluoroborate, 4-p-tolyl-mercapto-2,5-diethoxy-benzenediazonium hexafluorophosphate and tetrafluoroborate, diphenylamine-4-diazonium sulfate , 4-
Methyl-6-trichloromethyl-2-pyrone, 4-
(3,4,5-Trimethoxy-styryl) -6-trichloromethyl-2-pyrone, 4- (4-methoxy-styryl) -6- (3,3,3-trichloro-propenyl)-
2-pyrone, 2-trichloromethyl-benzimidazole, 2-tribromomethyl-quinolone, 2,4-dimethyl-1-tribromoacetyl-benzene, 3-nitro-
1-tribromoacetyl-benzene, 4-dibromoacetyl-benzoate, 1,4-bis-dibromomethyl-benzene, tris-dibromomethyl-s-triazine, 2-
(6-Methoxy-naphth-2-yl)-, 2- (naphth-1-yl)-, 2- (naphth-2-yl)-, 2-
(4-Ethoxyethyl-naphth-1-yl)-, 2-
(Benzopyrani-3-yl)-, 2- (4-methoxy-
Anthrac-1-yl)-and 2- (phenanth-9-
Yl) -4,6-bis-trichloromethyl-s-triazine, and o-naphthoquinonediazide-4-sulfonic acid halogenide described in JP-A No. 50-36209 can also be used.

In addition to the compound having a halomethyl group in combination with a suitable dye, o-naphthoquinonediazide-
When a 4-sulfonic acid halogenide or an o-naphthenone diazide type compound described in JP-A-55-6244 or JP-A-59-218442 is used in combination, an unexposed portion and an exposed portion are exposed. In the meantime, a clear visible contrast with good stability over time can be obtained.

The acid-generating compound of the present invention can be varied over a wide range depending on its chemical properties and the composition or physical properties of the photosensitive composition of the present invention. A range of 0.1 to about 10% by weight is suitable, preferably a range of 0.2 to 5% by weight.

In the photosensitive composition of the present invention, in addition to the acid generating compound of the present invention and the compound of the present invention, a water-soluble resin, an alkali-soluble resin or an organic solvent-soluble resin may be mixed and used. preferable. Of these, alkali-soluble resins are particularly preferable, and suitable alkali-soluble resins include novolak resins composed of formaldehyde and at least one of phenol, o-cresol, m-cresol, and p-cresol.

Specifically, for example, m-cresol / p-cresol /
Examples thereof include formaldehyde / novolak resin or phenol / m-cresol / p-cresol / formaldehyde / novolac resin.

The above novolak resins may be used alone or in combination of two or more.

The molecular weight of the novolac resin is (polystyrene standard measurement), the number average molecular weight Mn is 3.00 × 10 ^{2 to} 7.50 × 10 ³ ,
A weight average molecular weight Mw of 1.00 × 10 ^{3 to} 3.00 × 10 ⁴ is suitable, and Mn of 5.00 × 10 ^{2 to} 4.00 × 10 is preferable.
³ , Mw is 3.00 × 10 ^{3 to} 2.00 × 10 ⁴ .

The molecular weight of the novolak resin is measured by GPC (gel permeation chromatography method). The number average molecular weight Mn and the weight average molecular weight Mw are calculated by Morio Tsuge, Tatsuya Miyabayashi, and Masayuki Tanaka, “Journal of the Chemical Society of Japan,” pages 800-8.
According to the method described on page 05 (1972), the peaks in the oligomer region are averaged (the peaks and valleys are connected to each other).

The content of these novolac resins contained in the photosensitive composition of the present invention is preferably 30 to 95% by weight, more preferably 50 to 90% by weight.

In the photosensitive composition of the present invention, in addition to the respective materials such as the acid generating compound of the present invention, the compound of the present invention, and a soluble resin,
If necessary, dyes such as dyes and pigments, plasticizers and the like can be added, and further, if necessary according to the purpose of use, a sensitizer (acid generation efficiency of the acid generating compound of the present invention described above. Can also be added.

Examples of pigments such as dyes and pigments used in the photosensitive composition of the present invention include Victoria Pure Bull-BOH [Hodogaya Kagaku], Oil Blue # 603 [Orient Chemistry], Patent Pure Blue [Sumitomo Mikuni Kagaku], Crystal Violet, Brilliant Green, Ethyl Violet, Methyl Green, Erythrosin B, Basic Fuchsin, Malachite Green, Oil Red,
m-cresol purple, rhodamine B, auramine,
4-p-diethylaminophenyliminonaphthoquinone,
Cyano-p-diethylaminophenylacetanilide,
Examples thereof include triphenylmethane type, diphenylmethane type, oxazine type, xanthene type, iminonaphthoquinone type, azomethine type and anthraquinone type.

Further, as the plasticizer, for example, phthalic acid esters, triphenyl phosphates, maleic acid esters, surfactants as coatability improvers, for example, fluorine-based surfactants, nonionic activity represented by ethyl cellulose polyalkylene ether, etc. Examples thereof include agents.

Furthermore, a lipophilic resin can be added to the photosensitive composition of the present invention in order to improve the oil sensitivity of the photosensitive composition.

Examples of the lipophilic resin (hereinafter referred to as an oil sensitizer) include phenols substituted with an alkyl group having 3 to 15 carbon atoms as described in JP-A No. 50-12806. A condensate of aldehyde with aldehyde, specifically, t-butylphenol formaldehyde resin or the like can be added. It is also possible to add a photosensitive resin obtained by condensing a novel oily substituted phenol-formaldehyde resin and a sulfonic acid chloride of o-quinonediazide.
These oil sensitizers are preferably contained in the photosensitive composition of the present invention in an amount of 0.1 to 5% by weight.

In the photosensitive composition of the present invention, the components described above are dissolved in the following solvents, and these are coated and dried on the surface of a suitable support to form a photosensitive layer, thereby providing the photosensitive composition of the present invention. A photosensitive lithographic printing plate (hereinafter referred to as the photosensitive lithographic printing plate of the present invention) can be formed from the photosensitive composition.

Examples of the solvent that can be used when dissolving each component of the photosensitive composition of the present invention include methyl cellosolve, methyl cellosolve acetate, ethyl cellosolve, cellosolves such as ethyl cellosolve acetate, 1,2-propanediol monomethyl ether or the like. Examples thereof include acetate, 1,2-propanediol monoethyl ether or its acetate, dimethylformamide, dimethylsulfoxide, dioxane, acetone, cyclohexanone, trichloroethylene, methylethylketone and the like. These solvents may be used alone or in admixture of two or more.

Further, the method described in JP-A-60-208750, that is, the photosensitive composition is dissolved in an organic solvent, the organic solvent solution is emulsified and dispersed in water, and then the organic solvent is substantially removed, followed by photosensitive coating. A method for producing a liquid can also be used.

As the coating method, conventionally known methods such as spin coating, wire bar coating, dip coating, air knife coating, roll coating, blade coating and curtain coating can be used. The coating amount varies depending on the application, but for example, in the case of a photosensitive lithographic printing plate, the solid content is preferably 0.5 to 5.0 g / m ² .

The support provided with the photosensitive layer using the photosensitive composition of the present invention is a metal plate of aluminum, zinc, steel, copper or the like, and plated or vapor-deposited with chromium, zinc, copper, nickel, aluminum, iron or the like. Examples thereof include a metal plate, paper, a plastic film and a glass plate, a paper coated with a resin, a paper covered with a metal foil such as aluminum, and a plastic film subjected to hydrophilic treatment. Of these, the aluminum plate is preferable. As the support of the photosensitive lithographic printing plate of the present invention, it is more preferable to use an aluminum plate that has been subjected to surface treatment such as graining treatment, anodizing treatment and, if necessary, sealing treatment.

A known method can be applied to these treatments.

Examples of the graining treatment method include a mechanical method and an electrolytic etching method. Examples of mechanical methods include a ball polishing method, a brush polishing method, a liquid honing polishing method, and a buff polishing method. The above-mentioned various methods can be used alone or in combination depending on the composition of the aluminum material.

For electrolytic etching, phosphoric acid, sulfuric acid, hydrochloric acid,
It is carried out using a bath containing an inorganic acid such as nitric acid alone or a mixture of two or more kinds. After the graining treatment, if necessary, desmut treatment is performed with an aqueous solution of alkali or acid to neutralize and wash with water.

The anodizing treatment is performed by using a solution containing one or more kinds of sulfuric acid, chromic acid, oxalic acid, phosphoric acid, malonic acid, etc. as an electrolytic solution and electrolyzing with an aluminum plate as an anode. The amount of the anodic oxide coating formed is suitably 1 to 50 mg / dm ² , preferably 10 to 40 mg / dm ² , and particularly preferably 25 to 40 mg / dm ² . The amount of anodized film is
For example, an aluminum plate is treated with a phosphoric acid chromic acid solution (phosphoric acid 8
5% liquid: 35 ml, chromium oxide (VI): 20 g is dissolved in 1 of water) to dissolve the oxide film, and the weight change before and after film dissolution of the plate is measured.

Specific examples of the sealing treatment include boiling water treatment, steam treatment, sodium silicate treatment, and dichromate aqueous solution treatment. In addition to this, the aluminum plate support may be subjected to an undercoating treatment with an aqueous solution of a water-soluble polymer compound or a metal salt such as fluorinated zirconic acid.

In addition, generally, when a film original is contact-printed on a photosensitive lithographic printing plate, the baking frame is evacuated. A method for improving this vacuum adhesion is also a photosensitive lithographic printing plate using the photosensitive composition of the present invention. Can be applied to. As a method of improving vacuum adhesion, a method of mechanically making unevenness on the surface of the photosensitive layer is used. A method of spraying a solid powder on the surface of the photosensitive layer. JPA
A method of providing a matte layer on the surface of a photosensitive layer as described in JP-A-50-125805. And a method of heat-fusing a solid powder on the surface of the photosensitive layer as described in JP-A-55-12974.

The photosensitive lithographic printing plate of the present invention can be exposed and printed by the same method as conventionally used. As the exposure means, for example, through a transparent positive film, it is exposed by a light source such as an ultra-high pressure mercury lamp, a metal halide lamp, a xenon lamp, a tungsten lamp or the like, or it is scanned and exposed by a laser beam, and then developed by a developing solution, and only an unexposed portion is exposed. Remain on the surface of the support to form a positive-positive relief image.

As the developing solution used for developing the photosensitive lithographic printing plate of the present invention, an aqueous alkaline developing solution is suitable. The above-mentioned aqueous alkaline developer (hereinafter referred to as the developer of the present invention) is, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium metasilicate, potassium metasilicate, dibasic sodium phosphate, or third. Examples thereof include aqueous solutions of alkali metal salts such as sodium phosphate. The concentration of the above-mentioned alkali metal salt is preferably used in the range of 0.05 to 20% by weight, more preferably 0.1 to 10% by weight.

If necessary, an organic solvent such as an anionic surfactant, an amphoteric surfactant or alcohol can be added to the developer of the present invention.

As the organic solvent, ethylene glycol monophenyl ether, benzyl alcohol, n-propyl alcohol,
1,2-propanediol monomethyl ether and the like are useful. The content of the organic solvent in the developer is preferably 0.5 to 15% by weight, and more preferably 1 to 5% by weight.

Specific Examples of the Invention Hereinafter, the photosensitive composition of the present invention and the photosensitive lithographic printing plate of the present invention will be described with reference to Examples, but the present invention is not limited thereto.

Synthesis Example 1 (Synthesis of Exemplified Compound No. 1) Tetramethoxymethane (manufactured by Tokyo Chemical Industry Co., Ltd., Tokyo Chemical Standard No. 1) 13.6 g (0.1 mol), triethylene glycol (manufactured by Kanto Chemical Co., Inc., Kanto Chemical Standard First grade) 30.0 g
(0.2 mol) and 20 mg of p-toluenesulfonic acid are gradually heated to 90 ° C. with stirring. After stirring at 90 ° C for 3 hours, the mixture is gradually heated and heated to 150 ° C over 3 hours. During this period, methanol produced by the reaction is distilled off. After cooling, the reaction product contains tetrahydrofuran 12
0 ml was added, 50 mg of anhydrous potassium carbonate was further added, and the mixture was stirred and then filtered. The solvent was distilled off from the filtrate under reduced pressure to obtain 32.6 g of a colorless transparent viscous liquid product.

The molecular weight is G.I. P. C. The measurement was performed using (gel permeation chromatography). The GPC measurement conditions are as follows. Equipment: Hitachi 635 type, Separation column: Showa Denko KK's Shodex A802, A803 and A804 are directly connected, activity: room temperature, solvent: tetrahydrofuran, flow rate: 1.5 ml / min, calibration using polystyrene as standard Lines were made. The number average molecular weight Mn and the weight average molecular weight Mw are calculated by Morio Tsuge, Tatsuya Miyabayashi, and Masayuki Tanaka “Chemical Society of Japan” 80
The method described on pages 0 to 805 (1972) was used to average the peaks in the oligomer region (connect the centers of peaks and valleys of the peaks), and the weight average molecular weight Mw was 5,000.
0, the number average molecular weight was Mn = 950, and the dispersity was Mw / Mn = 5.3.

Synthesis Example 2 (Synthesis of Exemplified Compound No. 6) 17.8 g of 1,2,6-hexanetriol (manufactured by Wako Pure Chemical Industries, Ltd.) instead of triethylene glycol in the synthesis of Exemplified Compound No. 1 of Example 1 Synthesis and post-treatment were performed in the same manner except that (0.133 mol) was used.

20.0 g of a colorless transparent viscous liquid product was obtained.

G. P. When the molecular weight was measured in the same manner with C,
Weight average molecular weight Mw = 50,000, number average molecular weight Mn = 1,50
The degree of dispersion was Mw / Mn = 33.3.

Synthesis Example 3 (Synthesis of Exemplified Compound No. 27) Bisphenol A (Tokyo Chemical Industry Co., Ltd., Tokyo Chemical Standard First Grade) 11.4 g (0.05 mol), triamine 15 ml in 100 ml of dichloromethane under ice cooling while stirring. A solution of 13.5 g (0.05 mol) of dichlorodiphenoxymethane (synthesized by the method described in Chem. Ber. 544 (1961)) in 35 ml of dichloromethane was gradually added to the above. Then, stirring was continued at room temperature for 20 hours. The reaction mixture was washed with brine, then dried over sodium sulfate and the solvent removed under reduced pressure. As a result, 13 g of a white solid product was obtained.

G. P. When the molecular weight was measured in the same manner with C,
Weight average molecular weight Mw = 12,000, number average molecular weight Mn = 6,50
The degree of dispersion was Mw / Mn = 1.8.

Synthesis Example 4 (Synthesis of Exemplified Compound No. 28) Synthesis Example 3 was carried out by using 7.5 g (0.05 mol) of triethylene glycol instead of bisphenol A in Synthesis Example 3.
Reaction and post-treatment were performed in the same manner as in.

9 g of a colorless transparent viscous liquid product was obtained.

G. P. When the molecular weight was measured in the same manner with C,
Weight average molecular weight Mw = 4,000, number average molecular weight Mn = 1,40
The degree of dispersion was Mw / Mn = 2.9.

Synthesis Example 5 (Synthesis of Exemplified Compound No. 29) Instead of bisphenol A in Synthesis Example 3, 3.5 g (0.025 mol) of p-xylylene glycol and 4.9 g (0.025 mol) of tetraethylene glycol were used.
Reaction and post-treatment were performed in the same manner as in.

10 g of a light brown viscous liquid product was obtained.

G. P. When the molecular weight was measured in the same manner with C,
Weight average molecular weight Mw = 1,800, number average molecular weight Mn = 1,00
The degree of dispersion was Mw / Mn = 1.8.

Synthesis Example 6 (Synthesis of Exemplified Compound No. 30) Triethylene glycol 3.8 g (0.025 mol), 1,6-
Hexanediol 3.0g (0.025mol), Pyridine 12g
While stirring in 100 ml of benzene under ice cooling, a solution of 13.5 g (0.05 mol) of dichlorodiphenoxymethane in 35 ml of benzene was gradually added thereto. Then, stirring was continued at room temperature for 20 hours. The reaction mixture was washed with brine, then dried over sodium sulfate and the solvent removed under reduced pressure. As a result, 8 g of a colorless transparent viscous liquid product was obtained.

G. P. When the molecular weight was measured in the same manner with C,
Weight average molecular weight Mw = 5,000, number average molecular weight Mn = 2,000
The degree of dispersion was Mw / Mn = 2.5.

Synthesis Example 7 (Synthesis of Exemplified Compound No. 36) Piperazine 8.6 g (0.1 mol), triethylamine 30 ml
In 200 ml of dichloromethane under ice cooling, a solution of 26.9 g (0.1 mol) of dichlorodiphenoxymethane in 70 ml of dichloromethane was gradually added thereto while stirring. Then, stirring was continued under water cooling for 3 hours.

The solid formed in the reaction mixture was filtered off, and the filtrate was washed with aqueous potassium carbonate solution and then brine. Subsequent drying over sodium sulfate and removal of the solvent under reduced pressure gave 9 g of a brown solid product.

G. P. When the molecular weight was measured in the same manner with C,
Weight average molecular weight Mw = 1,800, number average molecular weight Mn = 900,
The dispersity Mw / Mn was 2.0.

Synthesis Example 8 (Synthesis of Exemplified Compound No. 43) Instead of bisphenol A in Synthesis Example 3, 8.3 g (0.05 mol) of terephthalic acid was used, and a reaction and a post-treatment were performed in the same manner as in Synthesis Example 3.

8 g of a white solid product was obtained.

G. P. When the molecular weight was measured in the same manner with C,
Weight average molecular weight Mw = 2,300, number average molecular weight Mn = 1,20
The degree of dispersion was Mw / Mn = 1.9.

Example 1 [Preparation of photosensitive lithographic printing plate sample 1] 0.24 mm thick aluminum plate (material 1050, temper H16)
Was degreased in 5% caustic soda aqueous solution at 60 ° C. for 1 minute, and then in a 0.5 mol / liter hydrochloric acid aqueous solution at a temperature of 25
The electrolytic etching treatment was performed under conditions of a temperature of 60 ° C., a current density of 60 A / dm ² , and a treatment time of 30 seconds. Then, after desmutting at 60 ° C. for 10 seconds in a 5% aqueous solution of caustic soda, temperature in a 20% sulfuric acid solution; temperature: 20 ° C., current density;
Anodizing treatment was performed under the conditions of 3 A / dm ² , treatment time; 1 minute. Further, hot water sealing treatment was performed with hot water at 30 ° C. for 20 seconds to prepare an aluminum plate as a support for a lithographic printing plate material.

Next, a photosensitive composition coating solution having the following composition was applied to this aluminum plate using a spin coater and dried at 90 ° C. for 4 minutes to obtain a positive photosensitive lithographic printing plate sample 1.

(Photosensitive composition coating liquid composition) Compound obtained by synthesizing Exemplified Compound No. 1 (Synthesis Example 1) 2.14 g Copolycondensation resin of phenol, m-cresol, p-cresol and formaldehyde (phenol, m-cresol) , And p-cresol at a molar ratio of 2.0: 4.
8: 3.2, weight average molecular weight Mw = 10,000, dispersity Mw / M
n = 6.7, Mn; number average molecular weight) 5.74 g Victoria Pureable-BOH (Hodogaya Chemical Co., Ltd.)
0.05 g 2-trichloromethyl-5- [β- (2-benzophthal) vinyl] 1,3,4-oxadiazol (JP-A-60)
Exemplified Compound (1) described in JP-A-138539 0.27 g Ethyl Cellosolve 100 ml The coating weight after drying was about 20 mg / dm ² . The molecular weight and dispersity of the copolycondensation resin of phenol, m-cresol and formaldehyde were measured by GPC in the same manner as above.

The photosensitive lithographic printing plate sample 1 thus obtained was subjected to a sensitivity measurement step tablet (Eastman Kodak No.
2, gray scale of 21 steps with 0.15 density difference each)
And a 2 Kw metal halide lamp (Idlefin 2000, manufactured by Iwasaki Electric Co., Ltd.) as a light source were exposed under a condition of 8.0 mW / cm for 10 seconds to prepare a sample. Next, this sample SDR-1 (Konishi Rokusha Kogyo Co., Ltd.) was developed with a developer diluted 8 times with water at 25 ° C. for 40 seconds.

When the sensitivity was measured with the gray scale of the step tablet, the fifth step was completely developed (clear).

Example 2 A photosensitive lithographic printing plate was prepared in the same manner as in Example 1, except that Exemplified Compound No. 6 obtained in Synthesis Example 2 was used instead of Exemplified Compound No. 1 in the preparation of the photosensitive lithographic printing plate sample 1. Printing plate sample 2 was prepared, exposed and developed in the same manner as in Example 1, and the sensitivity was determined. As a result, the fifth stage was completely developed (clear) on the gray scale of the step tablet.

Comparative Example 1 Instead of Exemplified Compound No. 1 in the photosensitive composition coating solution of Example 1, polyacetal (a benzaldehyde was prepared by the method described in JP-A-53-133429) on the aluminum support prepared in Example 1. A photosensitive lithographic printing plate sample 3 was obtained in the same manner as in Example 1 except that (condensed with triethylene glycol) was used.

The coating weight after drying was about 20 mg / dm ² . Next, using this photosensitive lithographic printing plate sample 3, exposure and development were carried out in the same manner as in Example 1, and the sensitivity was determined. As a result, the second half stage was completely developed in the gray scale of the step tablet (clear). It was).

Example 3 Development acceptability was examined using the photosensitive lithographic printing plate samples 1 and 2 obtained in Examples 1 and 2.

As a method for examining the development acceptability, a developer having a diluted alkali concentration and a developer having a concentrated alkali concentration are prepared, and the photosensitive lithographic printing plate sample 1 is prepared.
Using a sample in which a positive original film was in close contact with and exposed for 10 seconds, the developability (underdevelopment) with respect to a developer having a reduced development ability and the developability (overdevelopment) with a developer having an excessive development ability (overdevelopment) Sex) was examined. The above developability is DP-4 (manufactured by Fuji Photo Film Co., Ltd.)
The dilution ratio was changed, development was carried out at 25 ° C. for 45 seconds, and it was judged by the solubility of the non-image area and the erosion of the image area. The results are shown in Table 1.

The better the underdeveloping property is, the more the photosensitive layer in the non-image area is dissolved with a more diluted developing solution, and the better the overdeveloping property is, as the developing solution with a higher alkali concentration causes less erosion in the image area. become. Good development tolerance means that both underdeveloping property and overdeveloping property are good.

Comparative Example 2 Photosensitive lithographic printing was performed in the same manner as Comparative Example 1 except that the following comparative compound was used in place of the polyacetal in the photosensitive composition coating liquid of Comparative Example 1 on the aluminum support prepared in Comparative Example 1. Plate sample 4 was obtained. The development acceptability of the sample 4 was examined in the same manner as in Example 3. The results are shown in Table 1.

[Comparative Compound] Polymer orthocarboxylic acid ester (condensed with 1,2,6-hexanetriol and trimethyl orthoformate by the method described in JP-A-56-17345; M
w = 2,500, Mw / Mn = 2.4) The coating weight after drying is about 2
It was 0 mg / dm ² .

From the above results, the photosensitive lithographic printing plate of the present invention having the photosensitive composition of the present invention on the support is seen in the comparison between Samples 1 and 2 of Examples 1 and 2 and Sample 3 of Comparative Example 1. As described above, the photosensitive lithographic printing plate samples 1 and 2 of the present invention are the same as the sample 4 of the comparative example 2 from the results of Table 1 as well as having high sensitivity and being sufficiently developed for practical use. As can be seen in the comparison, since it is possible to perform development that is sufficiently suitable for practical use in a wide range of dilution rates of the developing solution used,
It can be seen that development acceptability is extremely good.

Overall, it is clear that the photosensitive lithographic printing plate of the present invention is a photosensitive lithographic printing plate with improved overall performance.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Nobumasa Inventor Nobumasa No. 1 Sakura-cho, Hino City, Tokyo Konishi Roku Photo Industrial Co., Ltd. (72) Inventor Yoshihiro Maeda 1000 No. Kamoshida-cho, Midori-ku, Yokohama-shi, Kanagawa Sanryo Kasei Kogyo Co., Ltd. (72) Inventor Toshiyuki Urano 1000 Kamoshida-cho, Midori-ku, Yokohama, Kanagawa Sanryo Kasei Industry Co., Ltd.

Claims (2)

[Claims] 1. A photosensitive composition comprising a compound capable of generating an acid upon irradiation with an actinic ray, and a compound having at least one of the following structural units decomposable by an acid. (Where X and Y are -O- or And X and Y may be the same or different. ) 2. A photosensitive composition formed from a photosensitive composition containing, on a support, a compound capable of generating an acid upon irradiation with actinic rays, and a compound having at least one of the following structural units decomposable by the acid. A photosensitive lithographic printing plate having a photosensitive layer. (Where X and Y are -O or And X and Y may be the same or different. )