JPS63149638A - Photosensitive composition and photosensitive lithographic printing plate - Google Patents

Abstract

PURPOSE:To stabilize sensitivity after exposing of a printing plate and to enhance the reproducibility of small dots by incorporating a compd. which captures the acid generated by active rays and forms amine when irradiated with said ray into a titled compsn. CONSTITUTION:The compd. (A) which generates the acid when irradiated with the active rays, the compd. (B) which has >=1 bonds to be decoposed by said acid, and the compd. (C) which captures the acid and forms the amine compd. when irradiated with the active rays are incorporated into the titled compsn. A 2-halomethyl-1,3,4-oxadiazole compd. is usable for the component A and the compd. expressed by the formula (where Mw=810, Mw/Mn=1.6) for the component B. Acetoanilide, etc., are usable for the component C. A novolak resin, etc., are usable as a high mol.wt. binder and if necessary, a dye, plasticizer, sensitizer, etc., may be added thereto.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a photosensitive lithographic printing plate and a photosensitive composition used in the printing plate.

[Background of the Invention] As a positive photosensitive composition, a first reaction in which an acid is generated by irradiation with actinic rays, a second reaction with the generated acid,
That is, various types of photosensitive adhesives are known that utilize the principle that exposed areas become soluble in a developer through an acid decomposition reaction. The acid-decomposed compound used in the second reaction is
8-890034, No. 51-120714, No. 53
-133429, 55-12995, 55-1
Mei 1 [1il] No. 26236, No. 56-17345, etc.
Compounds having a C-0-C bond described in JP-A-60-37549 and JP-A-60-121446, etc. Japanese Patent Publication No. 60-3625, No. 60-10
Examples include compounds described in specifications such as No. 247.

All of these photosensitive compositions had different sensitivities depending on whether they were developed immediately after exposure or developed some time after exposure, that is, the stability of sensitivity after exposure was low. In order to improve the stability of sensitivity after exposure, a technique for adding a compound that generates radical inhibiting species upon irradiation with light is disclosed in JP-A-61-167945, but the stability of sensitivity is still insufficient. No, further improvements were desired.

[Objective of the Invention 1 Therefore, the object of the present invention is to provide a photosensitive lithographic printing plate which has high sensitivity stability after exposure and excellent reproducibility of small halftone dots, and a photosensitive composition used therein. Our goal is to provide the following.

Another object of the present invention is to provide a photosensitive planographic printing plate whose sensitivity stabilizing effect does not decrease even after long-term storage of the photosensitive planographic printing plate, and a photosensitive composition used therein. .

[Structure of the Invention] The object of the present invention is to provide a compound that can generate an acid when irradiated with actinic rays, a compound that has at least one bond that can be decomposed by the acid, and a compound that can capture the acid and generate an acid when irradiated with actinic rays. This was achieved using a photosensitive lithographic printing plate having a photosensitive composition containing a compound that produces an amine compound, and a photosensitive layer formed from the photosensitive composition on a support.

[Specific Structure of the Invention] A compound that generates an acid upon irradiation with actinic rays (hereinafter referred to as the acid-generating compound of the present invention) will be described.

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-
Salts such as 1PFs-1Sb F625iFs-1CIO+-, organohalogen compounds, orthoquinone-diazide sulfonyl chloride, and organometallic/organohalogen compounds are also sensitive to actinic radiation, forming or separating acids upon irradiation with actinic radiation. It is a component and can be used as an acid generating compound of the present invention. All organic halogen compounds, which are known in principle as free-radical-forming photoinitiators, are compounds which form hydrohalic acids and can be used as acid-generating compounds according to the invention.

Examples of compounds forming the aforementioned hydrohalic acids are U.S. Pat. No. 3,515,552, U.S. Pat.
89 and 3.779.778 and West German Patent Application No. 2,243,621;
．． Compounds that generate acids upon photolysis as described in US Pat. No. 6,100,842 can also be used.

Furthermore, JP-A-54-74728, JP-A-55-
24113, JP 55-77742, JP 60-3626, JP 60-138539
Specifically, the 2-halomethyl-1,3,4-oxadiazole compounds described in the above publication include 2-trichloromethyl-5-[β(2-benzofuryl)vinyl] 1.3.4
-Oxadiazoles can be used.

Specific examples of the acid generating compound of the present invention include JP-A-56-
Examples include those described in Japanese Patent No. 17345.

Further, 0-naphthoquinonediazide-4-sulfonic acid halide described in JP-A-50-36209 can also be used.

The acid-generating compound of the present invention can vary widely depending on its chemical properties and the composition or physical properties of the photosensitive composition of the present invention, but is approximately A range of 0.1 to about 20% by weight is suitable, preferably a range of 0.2 to 10% by weight.

A compound having at least one bond that can be decomposed by the acid generated by the acid-generating compound of the present invention (hereinafter referred to as the acid-decomposable compound of the present invention) will be described.

Specifically, the acid-decomposed compound of the present invention includes JP-A No. 4
No. 8-89003, No. 51-120714, No. 53-
No. 133429, No. 55-12995, No. 55-1
Compounds having a C-〇-C bond described in the specifications of No. 26236 and No. 56-17345, JP-A-60
Compounds having a 5i-0-C bond described in the specifications of JP-A-37549 and JP-A Nos. 60-121446, and compounds described in the specifications of JP-A-60-3625 and JP-A-60-10247. Other acid-degradable compounds. Furthermore, the S mentioned in the memo of Japanese Patent Application No. 16687/1987
Compound having i-N bond, Patent Application No. 61-94603
Carbonic ester described in the specification of No. 1, patent application No. 1983
Ortho carbonate esters described in the specification of O-25j744, orthotitanate esters described in the specification of Japanese Patent Application No. 125473/1982, Japanese Patent Application No. 1983
Orthosilicate esters described in Mei 1illi of Japanese Patent Application No. 125474, acetals and ketals described in Mei 1B of Japanese Patent Application No. 155481/1981;
Examples include compounds having a C-8 bond described in the specification of Japanese Patent Application No. 87769/1982.

゛Among these acid-decomposed compounds, in the present invention, JP-A-48-89003, JP-A-51-120714, JP-A-5
No. 3-133429, No. 55-12995, No. 55
-126236, 56-17345 and Japanese Patent Applications 60-251744 and 61-155481 are preferred; More preferred are the compounds described in Japanese Patent Application No. 60-251744 and Japanese Patent Application No. 61-155481.

Further, specific exemplary compounds and synthesis methods of the acid-decomposed compound of the present invention are described in each of the above-mentioned specifications.

゛The content of the acid-decomposed compound of the present invention is preferably 5 to 70% by weight based on the total solid content of the photosensitive composition of the present invention,
Particularly preferred is 10 to 50% by weight.

Further, the acid decomposition compound of the present invention may be used alone, or two
A mixture of more than one species may be used.

Examples of synthesis of the acid-decomposed compound of the present invention are shown below.

Synthesis Example 1> 1.1-Dimethoxycyclohexane (manufactured by Tokyo Kasei Kogyo Co., Ltd.) 72.1 g (0.5 mol), triethylene glycol (manufactured by Kanto Kagaku ■) 75.1 (1 (0.5 mol) and 1 g of p-toluenesulfone R80Il was reacted at 100°C for 1 hour with stirring, then the temperature was gradually raised to 150°C, and the reaction was further carried out at 150°C for 4rR.

Methanol produced by the reaction was distilled off during this time. After cooling, 500 iQ of tetrahydrofuran and 2.5 g of anhydrous potassium carbonate were added, stirred, and filtered. The solvent was distilled off from the filtrate under reduced pressure, and low-boiling components were further distilled off at 150° C. under high vacuum to obtain a viscous oily product D-1.

D-1; Mw = 980. Mw /Mu = 2.3 Synthesis Example 2> Benzaldehyde (manufactured by Kanto Kagaku ■) 53.1 g (0.5
mole), triethylene glycol 75.1+1 (0,5
t-/Iz) (D Hensen 500x (1m liquid G, :I
i[2.5 fJ was added and reacted under reflux for 200 hours.

The reaction water produced by the reaction was separated as an azeotrope.

After the reaction is complete, add 25% of anhydrous potassium carbonate (+) and add 25% of anhydrous potassium carbonate
Stir for an hour and then filter. Benzene was distilled off from the filtrate under reduced pressure, and low-boiling components were further distilled off under a high vacuum of about 150'C1 to obtain a viscous oily product D-2.

D-2; Mvi = 810. Mw /Mn = 1.6 Synthesis Example 3> 53.1 g of methyl orthoformate and 55.8Q of 1,2,6-hexandriol were reacted in the same manner as in Synthesis Example 1 to produce a polymer orthocarboxylic acid ester having the following structural unit. D
I got -3.

D-3; Mw =1700. Mw /Mn = 2.1 Synthesis Example 4> Thioglycerol 10.9g (0.1 mol), methyl orthoformate 10.6Q (0.1 mol) and p-toluenesulfonic acid 0.16111 (as an acid catalyst) 0,00
1 mol) was gradually heated while stirring for 5 hours, and the temperature was raised to 130° C. while distilling off methanol as a by-product. The amount of methanol distilled off was 8.6 g.

Thereafter, the reaction was stopped by cooling, and anhydrous potassium carbonate 1.
1 g was added and filtered to obtain a colorless and transparent viscous liquid.

This liquid was then heated under vacuum (about 1 nmt-1 g) for about 8
After drying at 0° C. for 10 hours, about 16 g of orthothioformic acid ester D-4 having the following structural unit was obtained.

D-4: Synthesis Example 5> To a mixture of 34.5 g of p-xylylene glycol, 48.6 g of tetraethylene glycol, 87 g of pyridine, and 600 d of ethyl acetate, 64.5 g of dichlorodimethylsilane was added.
A solution of Q in ethyl acetate 1501 (i) was added dropwise at room temperature with stirring, and stirring was continued at 50"C for 3 hours.

The produced pyridine hydrochloride was separated by filtration and washed with a 5% aqueous NaHCO3 solution and then with saturated brine. After drying the solution over anhydrous sodium sulfate, the solvent was distilled off under reduced pressure to obtain a product, silyl ether polymer D-5.

Mw = 16.00 (+, Mw / Mn =
1, 7 Synthesis Example 6> Ol 1 to methyl carbonate 68.1o, 1,2,6-hexane-1-liol 89o and p-toluenesulfonic acid 0
．． Gradually heat 1 g to 90° C. with stirring.

After stirring at 90°C for 3 hours cJ, the mixture is further gradually heated and the temperature is raised to 150°C over 3 hours. During this time, methanol produced by the reaction is distilled off. After cooling, 501 p of tetrahydrofuran was added to the reaction product, followed by 3 g of anhydrous potassium carbonate, stirred, and then filtered. The solvent was distilled off from the filtrate under reduced pressure to obtain a polymer orthocarbonate D-6 having the following structural unit.

D-6; Mw = 48,000. M11/Mn = 33〈
Synthesis Example 7> 1.1-dimethoxycyclopentane 13.0C1 (0,
5 mol), triethylene glycol monomethyl ether 164.2 (J (1.0 mol)) and 1 g of p-toluenesulfonic acid 80II were reacted at 100°C for 1 hour with stirring, then the temperature was gradually raised to 150°C, and further The reaction was carried out at 150°C for 4 hours.

Methanol produced by the reaction was distilled off during this time. After cooling, tetrahydrofuran 500112 and 2.5 g of anhydrous potassium carbonate were added, stirred, and filtered. The solvent was distilled off from the filtrate under reduced pressure, and low-boiling components were further distilled off at 150° C. under high vacuum to obtain a viscous oily product D-7.

D-7; <Synthesis VA8> 1.1-dimethoxycyclohexane and phenyllerosolve were reacted in the same manner as in Synthesis Example 7 to produce a viscous oily product D-
8 is 19.

D-8: A compound that can capture an acid and generates an amine compound upon irradiation with actinic rays (hereinafter referred to as the photoamine generator of the present invention) will be described.

The photoamine generator of the present invention has the property of being able to capture the acid generated from the acid-generating compound of the present invention, and specifically has the general formula Ar -NHCOR [where Ar is an aryl group (for example, a phenyl group)]. , naphthyl group), R represents an alkyl group (e.g. methyl group, ethyl group, propyl group, i-propyl group, butyl group, (-butyl group, hexyl group). Examples include dihydride, propionanilide, and the like.

The amount added is equivalent to i/10 of the acid generating compound of the present invention.
0 to 10 times, preferably 1/20 to equivalent,
A suitable amount is 01% to 10% by weight based on the total weight of the solid content of the photosensitive composition of the present invention.

The photoamine generator of the present invention can be easily synthesized by, for example, a dehydrohalogenation reaction between a corresponding amine and a carboxylic acid halide, or a dehydration condensation reaction between a corresponding amine and a carboxylic acid. Methods similar to or similar to these are described, for example, in Jikken Kagaku Koza, Vol. 19, p. 483 onwards. It can also be easily obtained using commercially available reagents.

In the present invention, in addition to the acid-generating compound of the present invention, the acid-decomposing compound of the present invention, and the photoamine generator of the present invention, a high molecular weight binder may be used. Examples of the polymeric binder include novolac resins, polymers having hydroxystyrene units, and polymers having structural units represented by the general formula [E].

Examples of the novolak resin include phenol formaldehyde resin, cresol formaldehyde resin,
Phenol-cresol-formaldehyde copolycondensate resin as described in JP-A-55-57841; p-1! as described in JP-A-55-127553; Examples include copolycondensate resins of phenol and phenol or cresol and formaldehyde.

Examples of polymers having hydroxystyrene units include polyhuman O-oxystyrene and hydroxystyrene copolymers described in Japanese Patent Publication No. 52-41050.

A polymer having a structural unit represented by the general formula [I] refers to a homopolymer having a repeating structure of only the structural unit,
(, s is a copolymer in which the structural unit is combined with one or more structural units having a structure in which the unsaturated double bond of another vinyl monomer is cleaved).

General formula [I] CoNR4→X+-Y-OH In general formula [I], R1 and R2 each represent a hydrogen atom, an alkyl group such as a methyl group or an ethyl group, or a carbon M group, and preferably a hydrogen atom. . , R3
represents a hydrogen atom, a halogen atom such as an MA atom or a bromine atom, or an alkyl group such as a methyl group or an ethyl group, preferably a hydrogen atom or a methyl group. R4 represents a hydrogen atom, an alkyl group such as a methyl group or an ethyl group, a phenyl group or a naphthyl group.

Y represents a phenylene group or a naphthylene group, including those with substituents, and the substituents include alkyl groups such as methyl and ethyl groups, halogen atoms such as chlorine and bromine, carboxylic acid groups, methoxy and ethoxy groups. Examples include alkoxy groups, hydroxyl groups, sulfonic acid groups, cyano groups, nitro groups, acyl groups, etc., but preferably those that have no substituent or are substituted with a methyl group.

X is a divalent i that connects a nitrogen atom and an aromatic carbon atom
In the group, n represents an integer of 0 to 5, preferably when n is O.

A polymer having a structural unit represented by general formula [I] is
More specifically, it can be represented by, for example, a) to 11).

a) In a) to h), R1-R5 are each a hydrogen atom,
It represents an alkyl group or a halogen atom, and X represents an alkyl group or a halogen atom. Moreover, m, n, i, and S represent the mole % of each structural unit.

Further, a novolak resin, a polymer having a hydroxystyrene unit, and a polymer having a structural unit represented by the general formula [I] can be used in combination.

The photosensitive composition of the present invention may further contain pigments such as dyes and pigments, plasticizers, etc., as necessary. Furthermore, if necessary depending on the purpose of use, a sensitizer (as described above) may be added to the photosensitive composition of the present invention. Compound that increases the acid generation efficiency of the acid generation compound of the present invention)
etc. can also be added.

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 a liposensitizing agent) include phenols substituted with an alkyl group having 3 to 15 carbon atoms, as described in JP-A-50-125806. and aldehyde condensates, specifically [
- Butylphenol formaldehyde resin etc. can be added. Further, a photosensitive resin obtained by condensing a lipophilic substituted phenol formaldehyde resin with a sulfonic acid oxyhydride of O-quinonediazide can also be added. These oil-sensitizing agents are used in the photosensitive composition of the present invention.
．． It is preferably contained in an amount of 1 to 5% by weight.

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 coating 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 acetate, ethyl cellosolve, and ethyl cellosolve acetate, 1,2-propanediol monomethyl ether, and its like. Examples include acetate, 1,2-propanediol monoethyl ether or its acetate, dimethylformamide, dimethyl sulfoxide, dioxane, acetone, cyclohexanone, trichloroethylene, methyl ethyl ketone, and the like.

Alternatively, the method described in JP-A No. 60-208750, that is, the photosensitive composition is dissolved in an organic solvent, the organic solvent solution is emulsified and dispersed in water, and the V4-containing solvent is substantially removed.
Methods for producing photosensitive coating solutions can also be used.

As the coating method, a conventionally known method can be used.

The support provided with the photosensitive layer using the photosensitive composition of the present invention may be a metal plate made of aluminum, zinc, steel, copper, etc., or a support plate plated or vapor-deposited with chromium, zinc, copper, nickel, aluminum, iron, etc. Examples include metal plates, paper, plastic films, glass plates, paper coated with resin, paper covered with metal foil such as aluminum, and plastic films treated to make them hydrophilic. Among these, preferred is an aluminum plate treated to make it hydrophilic. As the support for the photosensitive lithographic printing plate of the present invention, it is more preferable to use an aluminum plate that has been subjected to surface treatments such as grain treatment, anodization treatment, and if necessary, pore sealing treatment.

In the present invention, the active light rays may be any light rays sufficient to cause the acid-generating compound of the photosensitive composition of the present invention to form an acid. A conventional exposure and printing apparatus can be used, and for example, an apparatus that uses a light source such as an ultra-high-pressure mercury lamp, a metal halide lamp, a xenon lamp, or a tungsten lamp, or an apparatus that performs scanning exposure using a laser beam may be used as appropriate. . The exposure amount is 0.1
It can be appropriately selected within the range of mJ to 2000 mJ.

The photosensitive lithographic printing plate of the present invention is exposed and baked using the above-mentioned exposure baking apparatus, and then developed with a developer, so that only the unexposed areas remain on the surface of the support, forming a positive-positive type relief image.

Aqueous alkaline developers can be suitably used for developing the photosensitive lithographic printing plate of the present invention, such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate,
Examples include aqueous solutions of alkali metal salts such as sodium metasilicate, potassium metasilicate, sodium diphosphate, and sodium triphosphate.

[Effect of the invention 1] The present invention provides a photosensitive material that has high sensitivity stability after exposure, excellent reproducibility of small dots, and does not lose its sensitivity stabilizing effect even after long-term storage of a photosensitive lithographic printing plate. A photolithographic printing plate and a photosensitive composition used therein were obtained.

[Examples] Specific examples of the present invention will be shown below, but the embodiments of the present invention are not limited thereto.

[Preparation of photosensitive lithographic printing plate sample] An aluminum plate (material 1050, tempered H16) with a thickness of 0.24 mm was heated at 60°C in a 5% aqueous solution of caustic soda.
- After degreasing for 1 minute, in a 0.5 mol 12 hydrochloric acid aqueous solution, temperature = 25°C, current density: 60A/d1B2
The electrolytic etching treatment was performed for a treatment time of 30 seconds. Then, in a 5% caustic soda aqueous solution at 60°C, 10
After performing a desmut treatment for seconds, in a 20% sulfuric acid solution, temperature: 20''C1 current density = 3A/dt', treatment time:
Anodic oxidation treatment was performed for 1 minute. Furthermore, 30℃
A hot water sealing treatment was performed using hot water 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 a positive photosensitive lithographic printing plate sample.

Example 1 Photosensitive liquid (I) - Acid decomposed compound 2.14 (tonovolac resin Copolycondensation resin of phenol, m-cresol, p-cresol and formaldehyde (molar ratio of each of phenol, 1-cresol and p-cresol) is 2.0:
4.8: 3.2, Mw = 10,0001Mw /
Mn = 6.7) 5.74 a.2-trichloromethyl-5-[β-(2-benzofuryl)vinyl 11°3.4-oxadiazole (exemplified compound described in JP-A-60-138539) (1) ) 0.27 g・Victoria Pure Blue BOHO, 05 (1 (manufactured by Odogaya Chemical Co., Ltd.)・Photoamine generator of the present invention Table 1 ・Methyl cellosolve 10 (hQ) Photosensitive planar plate thus obtained A step tablet for sensitivity measurement (NO12 manufactured by Eastman Kodak, 21 gray scale levels with a density difference of 0.15) was placed in close contact with the printing plate material, and a 2KW ultra-high pressure mercury lamp was used as the light source from a distance of 50cm for 30 seconds. exposed.

Next, for the samples that had been exposed for 1 minute and 120 minutes, 5DR-1 (manufactured by Konishiroku Photo Industry ■) was added with water for 80 minutes.
After developing for 40 seconds at 25°C with a twice diluted developer,
Clear sensitivity was evaluated. The results are shown in Table 1.

Furthermore, in order to examine the raw storage stability, the temperature was 40℃ and the humidity was 80%.
The clear sensitivity of the photosensitive lithographic printing plates degraded under forced degradation conditions for 3 days was similarly evaluated. The results are shown in Table 1.

Table 1 As is clear from Table 1, in Comparative Examples 1 to 7 in which no photoamine generator was added, the number of clear stages varied greatly over time and the sensitivity was not stable. Furthermore, in Comparative Examples 8 and 9 in which a compound other than the photoamine generator of the present invention was added, the sensitivity was similarly unstable. On the other hand, in Examples 1 to 11 of the present invention, sensitivity stability is high and stability is well maintained even after forced deterioration.

Example 12 A printing test was conducted using the lithographic printing plates obtained in Examples 1 to 11 and Comparative Examples 1 to 9. However, in addition to 1 minute and 2 hours, the elapsed time from exposure to development is 4 hours, 6 hours, and 10 hours.
I also talked about things that I had time for.

In the lithographic printing plates using the photosensitive compositions having the compositions of Comparative Examples 1 to 9, so-called "skipping small dots" occurred in the printed matter when developed 6 hours and 10 hours after exposure. On the other hand, with the compositions of Examples 1 to 11, printed matter with good dot reproducibility was obtained regardless of the elapsed time from exposure to development and even after forced deterioration.

Actual M Example 13 In Examples 1 to 11, Comparative Examples 1 to 9, and Example 12, the photosensitive liquid (I) novolac resin 5.74 (J [
The same novolak resin 2.870, 2.87 g of a polymer having a structural unit represented by the following general formula [I]] were used in the same manner, except that the difference in the number of clear steps, the difference in the number of clear steps after forced deterioration, and the small point were A reproducibility test was conducted.

As with the results of Examples 1 to 11, Comparative Examples 1 to 9, and Example 12, the results showed that the present invention had high stability after exposure and excellent spot reproducibility.

Mn: number average molecular weight

Claims (2)

[Claims] (1) Contains a compound that can generate an acid when irradiated with actinic rays, a compound that has at least one bond that can be decomposed by the acid, and a compound that can capture the acid and generates an amine compound when irradiated with actinic rays. A photosensitive composition characterized by: (2) In a photosensitive lithographic printing plate having a photosensitive layer formed from a photosensitive composition on a support, the photosensitive composition is a compound capable of generating an acid upon irradiation with actinic rays, and is decomposed by the acid. A compound having at least one bond capable of
and a photosensitive lithographic printing plate, comprising a compound capable of capturing the acid and producing an amine compound upon irradiation with actinic rays.