JPS62280841A - New photosensitive composition having orthotitanate as structural unit and photosensitive lithographic plate - Google Patents

Abstract

PURPOSE:To obtain the new photosensitive composition having processing chemicals resistance against the processing chemicals used after developing, by incorporating a compd. capable of producing an acid by radiating an active ray, and a compd. having a specific structure unit capable of decomposing by the acid to the photosensitive composition. CONSTITUTION:The titled composition contains the compd. capable of producing the acid by radiating the active ray, and the compd. which has at least one of the structural units shown by the formula and is capable of decomposing by the acid. The compd. capable of decomposing by the acid is composed of concretely the compd. contg. at least one of the orthotitanate unit and for example, is synthesized by reacting at least one of the compd. having at least one of a phenolic hydroxyl group and/or at least one of an alcoholic hydroxyl group and/or at least one of a carboxyl group and TiCl4 or Ti(OR6)4, etc., in one step or more than two steps reaction. The compd. capable of producing the acid principally includes all orgnohalo compd. which is well- known as a photo-initiator capable of forming a free radical and capable of forming hydrohalogenic acids may be used as said compd. capable of producing the acid.

Description

Detailed Description of the Invention 3. Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a photosensitive composition and a photosensitive lithographic printing plate obtained therefrom.

[Background of the Invention] Orthoquinonediazide compounds are conventionally known as photosensitive substances in photosensitive compositions used in photosensitive lithographic printing plates. The composition has been widely used for lithographic printing plates, photoresists for photoetching, and the like. Examples of such orthoquinone diazide compounds include, for example, JP-A No. 47-5303, JP-A No. 48-63802, JP-A No. 48-48-
No. 63803, No. 49-38701, No. 56-104
No. 4, No. 56-1045, Special Publication No. 41-11222, No. 43-28403, No. 45-9610, No. 49
-17481, U.S. Patent No. 2.797.21
No. 3, No. 3.048.120, No. 3,188,2
No. 10, No. 3,454,400, No. 3.544,
No. 323, No. 3.573.917, No. 3.674
．． No. 495, No. 3,785,825, British Patent No. 1
, 277.602, 1,251,345, L 267,005, 1.329,888, 1.330.932, German Patent No. 854, 13
Examples include those described in various publications such as No. 90.

The above-mentioned orthoquinone diazide compounds are decomposed by irradiation with actinic rays and are made to be solubilized in a phenomenon liquid for photosensitive planographic printing plates, but all of them have the drawback of low sensitivity.

As a method of increasing the sensitivity of photosensitive substances used in photosensitive compositions, there is a method in which a second reaction is caused by the acid generated by photolysis, and as a result, the area exposed to actinic light is solubilized. A type of photosensitive substance that acts positively is used. Specifically, it is a photosensitive composition consisting of a combination of a compound that generates an acid by photolysis and a compound that can be decomposed by the acid, and can be decomposed by ITi acids (for example, 'vf Acetal or O,N described in Publication No. 48-89003
-Acetal compound, described in JP-A-51-120714.

Compound having orthocarboxylic acid ester group and/or carboxylic acid amide acetal group, JP-A-53-1334
Polymers having an acetal group or ketal group in the main chain described in 29M Publication vii, or JP-A-56-1734
Polymers having an orthocarboxylic acid ester group in the main chain as described in Japanese Patent Publication No. 60-37549 and JP-A-60-37549;
There are polymers having a silyl ether group in the main chain described in Japanese Patent No. 121446.

However, even if these compounds are photosensitive materials that exhibit higher sensitivity than the above-mentioned orthoquinone diazide compounds, they may be acetal or O,N-acetal compounds, or polymers having an acetal or ketal group in the main chain. In both cases, the sensitivity was insufficient, making them unsuitable for actual use.

In addition, in the case of a polymer having an orthocarboxylic acid ester group or a palmyl ether group in the main chain, when used as a photosensitive lithographic printing plate, ink may be applied to the image area with a developing ink after the photosensitive lithographic printing plate is developed. In the printing process as well as when the plate surface is wiped with a cleaner used in the printing process, the halftone dots in the highlight areas of the image tend to disappear, which poses a practical problem.

Furthermore, when printing is performed using this photosensitive lithographic printing plate, there is a drawback that it has low stiffness resistance and is unsuitable for printing with a large number of prints.

Therefore, there has been a demand for a high-performance photosensitive composition with improved battery performance as a photosensitive composition for use in the photosensitive layer of a photosensitive lithographic printing plate.

As a result of intensive research, the researchers of the present invention have found that by containing a compound that can be decomposed by an acid and has at least one of the following groove units, it is possible to improve the process used in the current process, printing process, etc. Resistant to chemicals! p! It is possible to obtain a photosensitive composition with chemical properties, and a photosensitive lithographic printing plate using this composition in the photosensitive layer is fully put to practical use, and is a photosensitive lithographic printing plate with processing chemical resistance and Ff4 stiffness. This is what led to the present invention.

CObject of the Invention] The first object of the present invention is to use ff1I! used after development. l!
An object of the present invention is to provide a novel photosensitive composition that is resistant to processing chemicals for i-products.

Further, the second object of the present invention is to improve treatment chemical resistance.
Another object of the present invention is to provide a photosensitive lithographic printing plate having a photosensitive layer having printing durability.

[Structure of the Invention] The above object of the present invention is achieved by using a photosensitive composition that has an acid upon irradiation with actinic rays and a photosensitive lithographic printing plate that has a photosensitive layer formed from the photosensitive composition. .

[Specific Structure 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 having the above structural unit that can be decomposed by an acid.

Examples of the above acid-decomposable compounds include compounds having a structural unit represented by the following general formula [I] that is acid-decomposable.

General Formula [I] In the formula, R1-R4 may be the same or different, and each represents R5 or -0-Rs.

At least two of R+ to R+ may be bonded to each other to form a ring.

R5 is a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkylene group, a substituted or unsubstituted arylene group, a substituted or unsubstituted fulkenylene group, or a substituted or unsubstituted aralkylene group.

Examples of the compound containing at least 51 orthotitanate units represented by the general formula [I] include at least one phenolic ○H group and/or at least one alcoholic OH group and/or at least one Coo ) (at least one compound having a group (hereinafter referred to as an OH group-containing compound) and Ti Ctl + ,
Ti (OR6)4 or Ti (OR6)m Cpn
(m and n are integers of 1 or more, m + n = 4, R6
is the same school as R5. ) and one-step or two-step or more reaction (compounds that can be synthesized from two steps) can be mentioned.

The reaction of Ti C14 with an OHM-containing compound, Ti
Regarding the transesterification reaction between (OR6)4 and an OH group-containing compound and the reaction between Ti (OR6)m C1 and an OH group-containing compound, see, for example, Industrial Chemistry Journal, 12, 556 (1962), Annuel C.
Paris (8nn, Chin, (Paris))
6.

661 (1961), Boulletin Société Simy France (13ull, 3oc, Chil+1
．． France) 3.

537 (1961), Industrial Chemistry Magazine Hiruyu, 77
(1959), Australian Journal of
Applied Science (Australian J,
Appl, Sci.) 10, 458 (19
59), Journal of American Chemical
Sosatei LJ, Am, CherA, Soc.
) 77, 4408<1955), C v-t) I,
T-of Indian Chemical Society (J.

tndian, Chem, Soc
, > 3 1 , 68:l! , (1955
).

Journal of Organic Chemistry LJ,
○rg, Chem, ) Engineering 4, 655 (19
49), Industrial Chemistry Magazine Hiru 4, 1182 (1961
) etc. can be used in the same way or similar to the method of 2 and 0.

As the OH group-containing compound, for example, 1[1ffi
alcohols, 24 alcohols, trivalent anoricols, 411+ and higher alcohols, 11iIIi phenolic compounds, divalent phenolic compounds, trivalent phenolic compounds, 4 and higher phenolic compounds, 1 carboxylic acid, 2 carboxylic acid, 3 west carboxylic acid, 4
Carboxylic acids higher than phenolic, some I/X are phenolic ○H
Examples thereof include compounds having at least two of a group, a flucolic OH group, and a COO+ group at the same time.

Examples of the above alcohol include n-propyl alcohol, n-butyl alcohol, n-pentyl alcohol, rhohexyl alcohol, n-hebutyl alcohol, n-octyl alcohol, 0-7yl alcohol, n- -dodecyl alcohol, 1)-tetradecyl alcohol, n-hexadecyl alcohol, n-occudecyl alcohol, isopropyl alcohol, isobutyl alcohol, 5ec-butyl alcohol, tert-butyl alcohol, isopentyl alcohol, activated amyl alcohol, tert -pentyl alcohol, cyclopentanol, cyclopentanol, allyl afrecol,
Crotyl alcohol rubinol, ethylene glycol 7-methyl ether,
Aliphatic alcohols such as ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, benzyl alcohol, α-phenylethyl alcohol, β-phenylethyl alcohol, diphenyl carbyl. Examples include aroma-releasing alcohols such as Norrule and cinnamyl alcohol.

For dihydric alcohols, for example, JP-A-53-13342
Pentane-1,5-diol, n-hexane-1,6-diol, 2-ethyl-hexane-1 described in Publication No. 9
, 6-diol, 2,3-dimethyl-hexane-1,6
-diol, heptane-17-diol, cyclohexane-1,4-diol, nonane-1,7-diol,
Nonane-1,9-diol, 3,6-dimethyl-nonane-1,9-diol, decane-1,1o-diol, dodecane-1,12-diol, 1,4-bis-(hydroxymethyl)-cyclohexane, 2-ethyl-1,4-
Bis-(hydroxymethyl), cyclohexane, 2-methyl-cyclohexane-1,4-jetanol, 2-methyl-cyclohexane-1,4-dibrobanol, thio-dipropylene glycol, 3-methyl-pentane-1
, 5-diol, dibutylene-glycol, oxypivalic acid-neobentyl glycol ester, 4,8-bis-(hydroxymethyl)-to-1,1cyclodecane, n
-butene-(2)-1,4-diol, n-butene-2-
yne-1,4-diol, n-hex-3-yne-2,
5-diol, 1,4-bis-(2-human Ooxyethoxy)-butyne-(2), p-xylylene glycol, 2
, 5-dimethyl-hex-3-yne-2,5-diol, bis-(2-hydroxyethyl)-sulfide, 2
゜2.4.4-teramethylcyclobutane-1,3-
Diols, di-, tri-, tetra-, penta- and hexaethylene glycols, di- and tripropylene glycols and average molecular m 200.300.400 and 60
Examples thereof include aliphatic alcohols such as polyethylene glycol (1), aromatic alcohols such as p-xylylene glycol, and 2-methyl-2-phenyl-1,3-propanediol.

For trihydric alcohols, for example, JP-A-56-17345
Glycerol, butane-1,2,4-triol, 2-hydroxymethyl-butane-1,4-diol, pentane-1,2,5-triol, 2-hydroxymethyl-pentane-1゜5- as described in the publication diol, hexane
1,2,5-triol, 2-didroxymethyl-hexane-1,6-diol, hexane-1,2,6-triol, 4-ethyl-hexane-1,4,5-triol, heptane-1,4 ,5-triol,1-(1゜2
-dihydroxyethyl)-4-hydroxymethyl-benzene, 2,4,6-1-riethyl-5-propyl-hebutane-1,3,7-triol, 1(2,3-dihydroxy-propoxy)-4-hydroxy Methyl-benzene, 1-<2.3-dihydroxypropyl)-4-hydroxymethyl-benzene, off-thi-3-2-1.7.8
-1-diol, octane-1,2,8-triol,
Octane-1,3,8-1-diol, nonane-1゜4
．． 5-1-diol, 3-(1-hydroxy-1-methyl-ethyl)-5-ogisaoctane-2°8-diol, 2.6.8-1-limethyl-3-hydroxymethyl-nonane-6 , 7-diol, 2-hydroxymethyl-
Examples include aliphatic or aromatic alcohols such as 3-oxahebutane-17-diol and hexadecane-1,2,16-triol.

Examples of alcohols of 41i16 or higher include pentaerythritol, threitol, pentitol, sorbitol,
Mention may be made of aliphatic alcohols such as polyvinyl alcohol. It may also be an aromatic alcohol.

1 (Examples of phenolic compounds of iIFl include phenol, 0-cresol, m-cresol, p-talesol, 3.5-xylenol, carvacrol, thymol, α-naphthol, β-naphthol, etc.) It will be done.

Divalent phenolic compounds include catechol, resorcinol, hydroquinone, 2.2-bis(4-hydroxyphenyl)butane, bis(p-hydroxyphenyl)methane, 2.2-bis(4-hydroxyphenyl)propyne,
Examples include 2,3-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, and 2,6-dihydroxynaphthalene.

Examples of trivalent phenolic compounds include pyrogallol and phloroglucin.

As a phenolic compound having a valence of 4 or more, 1°4.9.
Examples include 10-tetrahydroxyanthracene.

(Group-containing compounds include, 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, linuric acid,
Cyclohexanecarboxylic acid, phenylacetic acid, benzoic acid,
o-toluic acid, m-t-toluic acid, p-toluic acid,
0-Chlorobenzoic acid, monozoic acid, m-chlorobenzoic acid, p-chlorobenzoic acid, 0-bromobenzoic acid, m-bromobenzoic acid, p-bromobenzoic acid, 0-nitrobenzoic acid, m-nitrobenzoic acid , p-nitrobenzoic acid, phthalic acid, isophthalic acid, terephthalic acid, 0-methoxybenzoic acid, m-methoxybenzoic acid, p-methoxybenzoic acid (anis 1S, oxalic acid, malonic acid, succinic acid, glutaric acid, Examples include adipic acid, pimelic acid, superric acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, tricarballylic acid, trimesic acid, and benzylidenemalonic acid.

Examples of the compound having both a phenolic OH group and a COOH group include p-hydroxyamino-6.1 acid.

Furthermore, examples of the compound having both phenolic OH and alcoholic OH include 2-(bis(4-hydroxyphenyl)methyl)benzyl alcohol.

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

The compound having at least one orthotitanate unit of the present invention is suitably one having nine orthotitanate units in the range of 1 to 500 in its molecule.

Preferably it is in the range of 1 to 200.

Examples of specific reaction products of the present invention and compounds having structural units are shown below, but the present invention is not limited thereto.

The following is a blank space for military-like reactions.
-CH20hH reaction product 2, Ti(OC-H
s), and F(O-(-CH,, CH2O%H)
Reaction product CH.

3, T i (OC, Hs) t and HO-(
-CHCH, ○+rl-i reaction product 4, Ti
(OC+ Hs ) + and HO+CH1hOH
- reaction product 5.7i(OC,)(,), and HO
-fcH, reaction product 6 with hOH, Ti(○C+H
sL and HOCH2C)1(OH)C,)(,0
Hkinl'i#d=lLIa thing? , Ti(○C,H,
Reaction products between L and (CH,C00CH2), C8, T i (OC* H*) 4 and (
CHsCOOCH2), reaction product with C9, T
i(○C,H,), and HOCH2CH(○)(
)CH(OH)C)(, reaction product t with CH, product HO-fCH, CH20h H,!: ) reaction product 1
1, Ti(OCzHs)+, Ti(OC,Hy)4
and HO÷ CH2C1(20hH reaction product 12, Ti(OC2Hs), and HO-(-C
H2CH20hH.

Reaction with HOCH2CH(CH)C,H,OH Yamu 1
6.TiCj! 4 and HO+cHzCHzOhH, product 17. TiC&', and CH
, OH, HocH, cH(oH)c, H, reaction product with oH 18, TlC0C4Hq)C1s and Ct
[Reaction oxide] with HsOHlHOfCHiOH,
White ○C, H.

Shih Ko　　　　　　　OC,H.

C48S 26・　6CH-6H2)- ■ ■ Oc　＊　　)l　s 31° CH.

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

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

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

The acid generating compound of the present invention includes various known compounds and mixtures. For example, diazonium salts, phosphonium salts, sulfonium salts, and iodonium BF4
-1PFs-1Sb Fs-1SiFs-1, CIO+
Salts such as -, organohalogen compounds, or-1-quinone-diazide sulfonyl chloride, and organometallic/organohalogen compounds are also actinic radiation-sensitive components that form or separate acids upon irradiation with actinic radiation, and are active radiation-sensitive components of the present invention. Can be used as an acid generating compound. All organohalogen compounds, which in principle are known as free-radical-forming photoinitiators,
A compound that forms halogenated water Ha, and can be used as an acid generating compound in the present invention.

Examples of compounds forming the aforementioned hydrohalic acids are U.S. Pat.
1189 and 3.779.778 and West German Patent Application No. 2,213,624; It is also possible to use the compounds described which do not generate acid upon photolysis.

Furthermore, JP-A-54-74728, JP-A-55-
24113, JP 55-77742, JP 60-3626, JP 60-138539
Substantively, the 2-halomethyl-1,3,4-oxadiazole compounds described in the above publication include 2-trichloromethyl-5-[β-(2-benzofuryl>vinyl]1.3
4-oxadiazole can be used.

Specific examples of the acid-generating compounds of the present invention include
The following can be mentioned as described in Publication No. 6-17345.

4-(di-n-propylamine)-benzenediazonium tetrafluorobole 1-. 4- D-tolyl-
Mercapto-2,5-die 1hexybenzenediazonium hexafluorophosphate and Te1-rafluor”
ruborate, diphenylamine-4-diazonium sulfate, 4-methyl-6-dolychloromethyl-2-pyrone, 4-(3,4°5-trimethoxy-styryl)-
6-dolychloromethyl-2-pyrone, 4-(4-methoxy-styryl)-6-(3,3,3-trichloro-propenyl)-2-pyrone, 2-1-lichloromethyl-penzimidazole, 2 -tribromomethyl-quinolone,
2,4-dimethyl-1-tribromoacetyl-benzene, 3-ditro-1-tribromoaretyl-benzene, 4
-dibromoacetyl-benzoic, 1,4-bis-dibromomethyl-benzene, 1-lis-dibromomethyl-S-
Triazine, 2-(6-methoxy-naphthi-2-yl)
-12-(naphthi-1-yl)-12-(naphthi-2-
yl)-,2-(4-ethoxyethyl-naphth-1-yl)-12-benzobilani-3-yl)-12-(4
-Methoxy-anthracy-1-yl)- and 2-(phenanthyl-9-yl)-4,6-sutrichloromethyl-S-triazine, and also JP-A-50-36209
〇-naphthoquinone diazido 4 described in the publication No.
- Sulfonic acid halogenides can be used.

In addition, in addition to the above-mentioned halomethyl group-containing compound in combination with a suitable dye, 0-naphthoquinonediazide-
4-sulfonic acid halide or "ff" 5S-6
When used in combination with the 0-naphthoenonediazide compounds described in JP-A No. 244 and JP-A-59-21L142, a clear visible line with good stability over time is created between the unexposed area and the exposed area. A contrast l- is obtained.

The acid-generating compound of the present invention can be varied widely depending on its chemical properties and the composition or physical properties of the photosensitive composition of the present invention. The range of about 0.1 to about 10% by weight is suitable, preferably 02 to 02-b. In addition, it is preferable to use a mixture of a water-soluble resin, an alkali-soluble resin, or a paid solvent-soluble resin. Among these, alkali-soluble resins are particularly preferred. Preferred 45 alkali-soluble resins include phenol, 0-cresol, m-
Examples include novolac resins made of formaldehyde and at least one of cresol and p-cresol.

Specifically, examples thereof include m-cresol, p-cresol, formaldehyde, and novolak resins, and phenol, m-cresol, p-cresol, formaldehyde, and novolak resins.

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

The molecular weight of the novolak resin is (borisdylene standard LJ1
11 constant) number average molecular weight Mn is 3.00 x 102 to 7.5
0 x 103. lfi average molecule 1M'N is 1.0
0 x 103 to 3.00 x 10+ is suitable, preferably i, t to + n is 5.00 x 102 to 4.
00 x 103, Mw is 3.00 x 103~2.
00 x 1Q4.

The molecular [■η] determination of the novolac resin is carried out by GPC (gel permeation chromatography). Calculation of the number average molecule jun and Ta 1 average molecule iMW is described in Morio Ishibani, Toya Miyabayashi, and Masayuki Tanaka °'Chemical Society of Japan Bi'8
By the method described on pages 00 to 805 (1972),
11 by averaging the peaks of the oligomer region ID (connecting the center of the peak and the center of the valley).

The content of these novolak resins in the photosensitive composition of the present invention is preferably 30-95% a%, more preferably 50-90fflff1%.

In addition to the above-mentioned materials such as the acid-generating compound of the present invention, the compound of the present invention, and the soluble resin, the photosensitive composition of the present invention may further contain pigments such as dyes and pigments, plasticizers, etc. In addition, if necessary depending on the purpose of use, a sensitizer (a compound that increases the A!i generation efficiency of the acid-generating compound of the present invention) or the like may be added.

Examples of the dye used in the photosensitive composition of the present invention, such as Junri, include Victoria Pure Blue BOH [
Hoduguya Chemical], Oil Blue #603 [Orient Chemical Co., Patent Pure Blue [manufactured by Sumitomo Mikuni Chemical], Crystal Violet, Brilliant Green, Ethyl Violet 1~, Methyl Green, Erythrosin B, Paysic Tsuksin, Malachite green, oil red, m-cresol purple, rhodamine B, auramine, 4-p-diethylamine phenyliminonaphthoquinone, cyano-p-diethylaminophenyl acetanilide, etc. i~riphenylmethane type, diphenylmethane type, oxazine type, Examples include xanthine type, iminonaphthoquinone type, azomethine type, and anthraquinone type.

Examples of plasticizers include phthalate esters, triphenyl phosphates, maleic esters, and surfactants such as nonionic surfactants such as fluorine surfactants and ethyl cellulose polyalkylene ethers. Agents, etc. can be mentioned.

Furthermore, 11:14 fat of mountain mass can be added to the photosensitive composition of the present invention in order to improve the fat sensitivity of the photosensitive composition.

The lipophilic body (hereinafter referred to as a liposensitizing agent) is, for example, a phenol substituted with an alkyl group having 3 to 15 carbon atoms, as described in JP-A-50-125806. Condensates of t and aldehydes, specifically t
- Butylphenol formaldehyde resin etc. can be added. It is also possible to add a photosensitive resin formed by condensing a lipophilic substituted phenol-formaldehyde sphere with a sulfonic acid 0-lide of 0-quinonediazide. These oil-sensitizing agents are used in the photosensitive composition of the present invention.
It is preferable that the content is 1 to 5%.

In the photosensitive composition of the present invention, a photosensitive layer is provided by dissolving each of the above-mentioned components in the following solvents and drying them on the surface of a suitable support. A photosensitive planographic printing plate (hereinafter referred to as the photosensitive planographic printing plate of the present invention) can be formed using the photosensitive composition.

Solvents that can be used to dissolve each component of the photosensitive composition of the present invention include cellosolves such as methyl cellosolve, methyl cellosolve acedate, ethyl cellosolve, and ethyl cellosolve acetate.

Examples include 1,2-propanediol monomethyl ether or its acetate, 1,2-propanediol monoethyl ether or its acetate, dimethylformamide, dimethyl sulfoxide, dioxane, acetone, cyclohexanone, l-lichloroethylene, and methyl ethyl ketone. These solvents may be used alone or in combination of two or more.

Alternatively, the method described in JP-A No. 60-208750, that is, the photosensitive composition is dissolved in a fabric solvent, the rich solvent solution is emulsified and dispersed in water, the fabric solvent is substantially removed, and the photosensitive composition is A method for producing a liquid coating solution 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, for photosensitive planographic printing plates, the solid content is 0.5 to 5.0 g/f.
is preferred.

The support on which the photosensitive layer using the photosensitive composition of the present invention is provided may be a metal plate made of aluminum, zinc, steel, copper, etc., or plated or vapor-deposited with chromium, zinc, copper, nickel, aluminum, iron, etc. Paper, plastic film and glass plates, paper coated with resin, paper covered with a metal box such as aluminum, and plastic film made of hydrocarbons are preferred. It is an aluminum plate. As the support for the 11th edition of the photosensitive composition of the present invention, it is more preferable to use an aluminum plate that has been subjected to surface treatments such as graining, anodizing, and, if necessary, sealing.

Known methods can be applied to these treatments.

Examples of methods for graining include a mechanical method and an electrolytic etching method.

Examples of mechanical methods include ball polishing, brush polishing, liquid honing, and puff polishing. The various methods described above can be used alone or in combination depending on the composition of the aluminum material.

For etching by electrolysis, use phosphoric acid, sulfuric acid, hydrochloric acid,
This is carried out using a bath containing one or a mixture of two or more inorganic acids such as nitric acid. After graining, if necessary, desmutting is performed using an aqueous alkali or acid solution to neutralize the material, followed by washing with water.

The anodic oxidation treatment is performed by electrolyzing using an aluminum plate as an anode using a solution containing one or more of sulfuric acid, chromic acid, oxalic acid, phosphoric acid, malonic acid, etc. as an electrolytic solution. The anodized ridges formed are 1 to 50 mo/df.
is suitable, preferably 10 to 40 mg/df, and most preferably 25 to 4 QIll+J/df.

The amount of anodic oxide coating can be determined by, for example, treating an aluminum plate with a phosphoric acid chromic acid solution (5% i: 35nf, i
The chromium (VI) Mide (prepared by dissolving 20q in 12 parts of water) is immersed in the plate to dissolve the oxide film, and it is determined by determining the weight change after dissolving the film on the plate.

Sealing treatment includes boiling water treatment, steam treatment, and sodium silicate9
8. Examples include treatment with dichromate aqueous solution, etc. In addition, the aluminum plate support may be subjected to subbing treatment using an aqueous solution of a water-soluble polymer compound or a metal salt such as fluorinated zirconate.

In addition, in general, when contact baking a film original onto a photosensitive lithographic printing plate, the baking frame is vacuumed, and a method for improving this vacuum adhesion is also photosensitive lithographic printing using the photosensitive composition of the present invention. Can be applied to any version. Methods for improving vacuum adhesion include a method of mechanically creating unevenness on the surface of the photosensitive layer, a method of rubbing solid powder on the surface of the photosensitive layer, and a method as described in JP-A-50-125805@. A method of forming a pine layer on the surface of a photosensitive layer, and a method of
Examples include a method of heat-sealing a solid powder onto the surface of a photosensitive layer, as described in Publication No. 5-12974@.

The photosensitive lithographic printing plate of the present invention can be exposed and baked in the same manner as conventionally used ones. As an exposure means, for example, a transparent positive film is exposed to light using a light source such as an ultra-high pressure mercury lamp, metal halide lamp, xenon lamp, or tungsten lamp, or scanning exposure is performed using a laser beam, and then the film is developed with a developer, and only the unexposed areas are exposed. remains on the surface of the support, creating a positive relief image.

As the developer used for the development of the photosensitive lithographic printing plate of the present invention, an aqueous alkaline developer is suitable. The aqueous alkaline developer (hereinafter referred to as the developer of the present invention) includes, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium metasilicate, potassium metasilicate, sodium diphosphate, and tertiary phosphate. Examples include aqueous solutions of alkali metal salts such as sodium chloride. The concentration of the alkali metal salt is preferably in the range of 0.05 to 20% by weight, more preferably 01 to 10% by weight.

Anionic surfactants, amphoteric surfactants, and organic solvents such as alcohols can be added to the developer of the present invention, if necessary.

Examples of organic solvents include 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 05 to 15%, and more preferably 1 to 5%.

The phenomenon ink used in the step of applying ink to the image area of the photosensitive lithographic printing plate of the present invention is made of resin, top husk, organic solvent, water-soluble polymer, KN, surfactant, etc.

In the photosensitive planographic printing plate of the present invention, the oil sensitivity of the fine halftone dots in the image area is sufficiently reinforced by the ink build-up using the development ink.

Further, as Plate 1 to cleaner for wiping and cleaning the plate surface in the printing process performed using the photosensitive lithographic printing plate of the present invention, those consisting of a paid solvent, mineral acid, surfactant, etc. are used.

In the photosensitive lithographic printing plate of the present invention, after development, if necessary, the plate-made image area may be inked with the development ink. This is a process in which the oil sensitivity of the image area is reinforced and the receptivity to printing ink during printing is improved.

In the photosensitive planographic printing plate of the present invention, a clear image area is formed on the plate surface without the fine halftone dots in the image area being dissolved and removed.

In the photosensitive lithographic printing plate of the present invention, the image area has good resistance to processing chemicals. Since a strong image area is formed even by the wiping operation to clean the plate surface, it is possible to print over a length of 111 mm, and a lithographic printing plate with improved rigidity can be produced.

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

Synthesis Example 1 (Synthesis of Specific Reaction Product 1) Ethyl orthotitanate (Tokyo Kasei Kou 2 (manufactured by Il), 22, h (0,
1 mol), triethylene glycol (Kanto Chemical ■1)
+5. OQ (0.1 mol) is stirred and reacted for 8 hours at room temperature in a moisture-free atmosphere.

During this time, ethanol produced by the reaction is distilled off. 27 g of a colorless and transparent liquid product was obtained.

The molecular weight is G, P, C, (gel permeation chroma 1
-graph). The GPCi1111 conditions are as follows. Equipment: Newly manufactured by Hitachi 635
Model, separation column: ShodeX△802 manufactured by Showa Denko Kogyo Co., Ltd.
, A303 and 804 are connected directly, temperature;
Room temperature, solvent: tetrahydrofuran, flow rate: 1.5 cm/m
In, a detection line was prepared using polystyrene as a standard.

Calculation of number average molecular weight Mn and weight average molecular weight ff1MW was carried out by Morio Tsuge, Tatsuya Miyabayashi, and Masayuki Tanaka, ``Journal of the Chemical Society of Japan.''
When the method described on pages 800 to 805 (1972) was carried out by averaging the peaks of the oligomer region (connecting the centers of peaks and valleys), the weight 1 average molecule f
iMw = 1,200. Number average molecule ff1Mn=6
00, and the degree of dispersion MW/'Mn = 2.0.

Synthesis Example 2 (Synthesis of Exemplified Compound 2) n-butyl orthotitanate (Kanto Kagaku (prepared) 34, O
a (0.1 mol), triethylene glycol 22.
5Q (0.15 mol) was reacted in the same manner as in Synthesis Example 1, and the molecular weight was measured using G, P, and C in the same manner.The weight average molecule ffiMW = 1,600, the number average molecule llMn = 900, and the degree of dispersion. Mw/Mn=
It was 1.8.

Synthesis Example 3 (Synthesis of Exemplary Compound 7) Ethyl orthotitanate 22.80 (0.1 mol),
Pentaerythritol tetraacetate (manufactured by Tokyo Chemical Industry Co., Ltd.) 30.40 (0.1 mol) and D-toluenesulfonic acid 401+1 (] are gradually heated to 90° C. with stirring in a moisture-blocked atmosphere.

Thereafter, the mixture is allowed to react while being gradually cooled to room temperature. The mixture was further stirred and reacted at room temperature for 6 hours to obtain a colorless and transparent liquid product. When the molecular weight was measured in the same manner using G, P, and C, the weight average molecule MW = 2,000, the number average molecule iMn = 1,000, and the degree of dispersion Mv /Mn
= 2.0.

Synthesis Example 4 (Synthesis of Specific Reaction Product 10) Ethyl orthotitanate 22.8Q (0.1 mol), ρ-xylylene glycol 6.9 g (0.05 mol), tetraethylene glycol 9.7 g (0.05 mol) , 05 mol) was reacted in the same manner as in Synthesis Example 3 to obtain a colorless and transparent liquid product. G.
When the molecule ■ was measured in the same manner using P and C, the weight average molecule @Mw = 2,700, the number average molecule ffl
Mn = 1,000, dispersity ~1w, /~In =
It was 2.7.

Synthesis Example 5 (Synthesis of Specific Reaction Product 11) Ethyl orthotitanate 11.4g (0.05 mol), n-butyl orthotitanate 17.0 (1 (0.05 mol)), triethylene glycol 15. Synthesis example 1 of OQ (0.1 mol)
The reaction was carried out in the same manner as above to obtain a colorless and transparent liquid product.

When the molecular weight was measured in the same manner using G, P, and C,
The weight average molecular weight fVIW = 1,500, the number average molecular weight 1Mn = 900, and the degree of dispersion Mw/Mn = 1.7.

Synthesis Example 6 (Synthesis of Exemplified Compound 19) Di-O-di-butyl titanate (Industrial Chemistry Magazine 65
, 556 (1962), titanium tetrachloride was synthesized from n-butanol) 26.5
(1 (0.1 mol) benzene + 00.Ω solution is water-cooled,
While stirring, a solution of triethylamine 2+ and Og in benzene 50iβ is gradually added dropwise. After completion of the dropwise addition, a solution of triethylene glycol IS,OG (0.1 mol) in 100 volumes of benzene was gradually added dropwise. After the addition was completed, the mixture was stirred at room temperature for 3 hours, and then at 60°C for 30 minutes. After cooling, the precipitated white solid was separated, washed several times with benzene, and the solvent was distilled off under reduced pressure to obtain a product.

When the molecular weight was measured in the same manner using G, P, and C,
weight l average molecule ff1Mw -4,500, number average molecule f
fiMn = 1,700, dispersion degree MW/Mn =
It was 2.6.

Synthesis Example 7 (Synthesis of Exemplified Compound 21) Trichloromono-〇-butyl titanate) ~ Synthesized from loubyl orthotitanate and titanium tetrachloride by the method described in (Industrial Chemistry Magazine) Dan 5, 556 (1962) > 22 .80 (0.1 mol), 1,2.
.

6-Hexandriol (manufactured by Wako Pure Chemical Industries, Ltd.) 13.4
0 (Oi mol) was reacted in the same manner as in Synthesis Example 6 (however, 315Q was used as triethylamine) to obtain a product.

When the molecular weight was measured in the same manner using G, P, and C,
Weight average molecule IMw -6,000, number average molecule 11y
jn = 2,0001, dispersity Mw /Mn = 30.

Synthesis Example 8 (Synthesis of Exemplified Compound 23) Dichlorodilope til titanate 265s (01 mol), bisphenol A (Tokyo Kasei Kotakuhat 1) 22.8
(1 (0.1 mol)) was reacted with Synthesis Example 6 in a @-like manner to obtain a product. The molecular weight was determined in the same manner using G, P, and C, and the weight average molecular weight Mw = 7,500 , number average molecule 1i1yln -3,300, dispersity M W /
There was M n = 2.0 te.

Synthesis Example 9 (Synthesis of Specific Reaction Product 24) Dichlorodi-
Rope titanate 26.5 (1 (0,1 mol), Te1~laedylene glycol 9.7 (1 (O, OS mol)
and 6.9 g (0.05 mol) of p-xylylene glycol were reacted in the same manner as in Synthesis Example 6 to obtain a product. G.P.
When the molecular weight was measured in the same manner using C, the weight average molecule IiM'' = 5.200, the number average molecule IMn =
2,600, and the degree of dispersion MW/Mn was -2.0.

Example 1 [Preparation of photosensitive lithographic printing plate sample 1] An aluminum plate (material 1050, tempered H16) with a thickness of 0.241 m was degreased in a 5% aqueous solution of caustic soda at 60°C for 1 minute, and then Temperature: 25°C, current density: 60A/df, treatment time: 3 in a .5 mol 1 t hydrochloric acid aqueous solution
Electrolytic etching treatment was performed for 0 seconds. Then,
After desmutting in a 5% caustic soda aqueous solution at 60°C for 10 seconds, desmutting in a 20% sulfuric acid solution at a temperature of 20°C,
The anodic oxidation treatment was performed at a current density of 3 A/di2 and a treatment time of 1 minute. Furthermore, a hot water sealing treatment was performed with hot water at 30° C. for 20 seconds to produce 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 rotary coater and dried at 90'C for 4 minutes to obtain positive photosensitive lithographic printing plate sample 1.

(Composition of photosensitive composition coating liquid) Compound obtained by synthesis of specific reaction product 1 (Synthesis Example 1) 2.14 (copolycondensation resin of J.m-cresol, p-cresol, and formaldehyde (m- The molar ratio of each of cresol and p-cresol is 6:4.1 m average molecule, m M W -10,0
00, dispersity Mw /Mn -6,7, i'VIn: number average molecular weight) 5゜749・Victoria Guarable-BOH (Fukadogaya Chemical tilN)
0.05+ff・2-trichloromethyl-5-[β-(2-benzofuryl)vinyl] 1,
3.4-Oxadiazole [JP-A-60-138539
Exemplary compound (1) described in the publication No.
0.27a・Ethylceronlube
The application mold stop after drying of 1001R is approximately 20m! 1/
It was df.

The molecular weight and dispersity of the copolycondensation resin of m-cresol, p-cresol, and formaldehyde are measured by G,
The same procedure as above was carried out using P and C.

The thus obtained photosensitive lithographic printing plate was coated with a step tablet No. manufactured by Eastman Kodak Company, 2° density difference 0.
21 levels of gray scale (gray scale of 15 increments) and a patterned positive film were exposed from a distance of 8 Qcm using a 2KW metal halide lamp (Idol Fin 2000, manufactured by Iwasaki Electric Co., Ltd.) as a light source, and then sodium metasilicate. Development was carried out with an aqueous solution of the above step tablet to obtain a lithographic printing plate in which the fifth stage of the step tablet was completely developed.

Printing was performed using the lithographic printing plate thus obtained. Ultra Plate Cleaner (A, B) is used to clean the printing plate every time 2000 sheets are printed.

A total of 30,000 sheets were printed by wiping the printing plate with a cloth (manufactured by Chemical Co., Ltd.), and the halftone dots in the highlighted areas did not disappear and 611 clear marks were obtained. did it.

Example 2 A photosensitive composition coating solution was prepared in the same manner as in Example 1 using the compound obtained by the synthesis of Exemplified Compound 7 (Synthesis Example 3). In addition, a photosensitive lithographic printing plate was prepared and plate-made in the same manner as in Actual tM Example 1, and a developed lithographic printing plate was obtained.

The image area of the lithographic printing plate thus obtained was filled with ink (manufactured by Konishiroku Photo Industry Co., Ltd., 5PO-1) to reinforce the image area.

Ultra plate cleaners (A, B, C, manufactured by Chemical Co., Ltd.) used to clean printing plates every time 2000 sheets are printed.
When we printed a total of 40,000 sheets by wiping and cleaning the plate surface, we found that the halftone dots, etc. in the printed areas disappeared both when inking was applied and when cleaning was performed with a cleaner. It had good printing durability. As a result, clear printed matter could be obtained.

Example 3 A photosensitive composition coating solution was prepared in the same manner as in Example 1 using the compound obtained by the synthesis of Exemplified Compound 23 (Synthesis Example 8), and a photosensitive lithographic printing plate was prepared and plate-made. The developed planographic printing plate is one-curve.

Printing was carried out using the lithographic printing plate prepared in this manner.Ultrabrae! Cleaner (A, B) was used to clean the printing plate every time 2000 sheets were printed.

After printing a total of 30,000 sheets by wiping the printing plate with a cloth (manufactured by Chemical Co., Ltd.), we were able to obtain clear prints without any distortion of the halftone dots in the highlighted areas. Ta.

Example 4 A photosensitive composition coating solution was prepared in the same manner as in Example 1 using the compound obtained by the synthesis of Exemplified Compound 24 (Synthesis Example 9), and a photosensitive lithographic printing plate was prepared and plate-made. A developed lithographic printing plate was obtained.

Printing was performed using the lithographic printing plate thus obtained. Ultra Plate Cleaner (A, B) is used to clean the printing plate every time 2000 sheets are printed.

After printing a total of 30,000 sheets by wiping the printing plate with C.Chemical Co., Ltd. (WA), we were able to obtain clear prints without any loss of halftone dots in the highlighted areas. .

Comparative Example 1 A compound (comparative compound) H3 having the following structural unit as an acid-decomposed compound (by the method described in JP-A-60-37549,
A lithographic printing plate was prepared in the same manner as in Example 1, and 4,000 sheets were printed. When the plate surface was wiped with Ultra Plate Cleaner, the image area was eroded and no residue was found. I was unable to print it because it had become corrupted.

Comparative Example 2 A coating liquid was prepared using (comparative compound) and a lithographic printing plate was prepared in the same manner as in Example 1. After printing 6,000 sheets, when the plate surface was wiped with Ultra Plate Cleaner, the image area was removed. It was eroded and damaged and could not print well.

From the above results, the photosensitive lithographic printing plate of the present invention having the photosensitive composition of the present invention on a support has excellent durability as seen in the comparison with Examples 1 to 4 and Comparative Examples 1 and 2. It has processing chemical properties and is fully suitable for practical use. It can perform ink filling operations and plate surface cleaning operations, and has printing durability.
Good printing can be done for a long time.

In summary, the lithographic printing plate whose photosensitive awn is the photosensitive resin composition of the present invention is a photosensitive lithographic printing plate with improved performance such as i'1 treatment, quality, printing power, etc. it is obvious.

Claims (2)

[Claims] (1) A photosensitive composition characterized by containing a compound capable of generating an acid upon irradiation with actinic light, and a compound having at least one of the following structural units that can be decomposed by an acid. ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ (2) A photosensitive layer formed on a support from a photosensitive composition containing a compound capable of generating an acid upon irradiation with actinic rays and a compound having at least one of the following structural units that can be decomposed by an acid. A photosensitive lithographic printing plate characterized by having the following. ▲Contains mathematical formulas, chemical formulas, tables, etc.▼