JPH11242325A - Photosensitive composition and lithographic printing plate formed by using same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the positive photosensitive composition having development characteristics high in contrast and superior in development latitude by incorporating a photosensitive compound obtained by linking plural atomic groups having urethane bonds or urethane bonds to each other through atomic groups having biuret bonds. SOLUTION: The photosensitive composition contains the photosensitive compound obtained by linking plural atomic groups having urethane bonds or urethane bonds to each other through atomic groups having biuret bonds and this photosensitive contains a condensation product of o- naphthoquinonediazido-sulfonyl chloride with B(-R-NH-CO-NH-X-Y-OH)n ; the adduct of a compound of a formula: B(-R-NCO)n to a compound of formula: H2 -N-X-Y-OH in which B is an atomic group having a biuret bond; R is an optionally substituted hydrocarbon group; (n) is >=2; X is a simple bond or a divalent bonding group; and Y is an optionally substituted aliphatic or aromatic hydrocarbon group.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a lithographic printing plate, an IC,
The present invention relates to a positive photosensitive composition suitable for manufacturing circuits and photomasks. More specifically, the present invention relates to a positive photosensitive lithographic printing plate having a high developing characteristic and excellent development latitude, and a photosensitive composition.

[0002]

2. Description of the Related Art JP-A-4-345164 discloses, for example, a photosensitive composition characterized by containing an ο-naphthoquinonediazide compound containing a structural unit having a specific atomic group as shown below. It describes a positive photosensitive composition in which it is provided on an aluminum support.

[0003]

Embedded image [R is a polyester or polyether residue having a molecular weight of 100 to 1,000, X is a divalent organic group, Y is a hydrogen atom, a hydroxyl group, a carboxyl group, an alkyl group or a halogen, Ph is a phenylene group, Z is a hydrogen atom, ο A naphthoquinonediazidosulfonyl group, n represents 2 or 3; ]

However, any of the photosensitive compositions containing a photosensitive compound having an atomic group having a specific structure described in the above-mentioned publication has insufficient developing latitude,
There is a drawback that hard development characteristics cannot be obtained.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a positive photosensitive composition having a high contrast and excellent development latitude, and a positive photosensitive composition having good solvent resistance as well as development characteristics. To provide a lithographic printing plate.

[0006]

Means for Solving the Problems The present inventors synthesized various photosensitive compounds having an atomic group having a specific structure, prepared a photosensitive composition, and evaluated the physical properties. As a result, it was found that a urea bond or a urethane bond was formed. The atomic group possessed is biuret (biuret)
t) The photosensitive compound linked by two or more via an atomic group having a bond is harder and has a lower development latitude than the photosensitive composition containing the photosensitive compound having an atomic group having the specific structure. It has been found that the photosensitive lithographic printing plate having a photosensitive layer comprising the composition exhibits excellent solvent resistance, and has completed the present invention.

That is, the present invention comprises a photosensitive compound characterized in that two or more atomic groups having a urea bond or a urethane bond are connected via an atomic group having a biuret bond. Provided is a photosensitive lithographic printing plate having a photosensitive composition and a photosensitive layer comprising the composition.

Further, the present invention relates to the above-mentioned photosensitive compound
-A photosensitive composition characterized by being a naphthoquinonediazide compound, further comprising: an o-naphthoquinonediazidesulfonic acid ester of an adduct of a biuret-type polyisocyanate and an aminophenol. Including the photosensitive composition.

Further, the photosensitive compound is a condensate of an adduct (III) of the compounds of the general formulas (I) and (II) with o-naphthoquinonediazidosulfonyl chloride. including.

[0010]

Embedded image B (—R—NCO) n (I)

[0011]

Embedded image H ₂ N—X—Y—OH (II)

[0012]

Embedded image B (—R—NH—CO—NH—X—Y—OH) n (III) wherein B is an atomic group having a biuret bond, and R is a hydrocarbon optionally having a substituent. A group, n is 2 or more, X is a single bond or a divalent linking group, and Y represents an aliphatic or aromatic hydrocarbon group which may have a substituent. "

[0013] The present invention also relates to the above-mentioned photosensitive composition, which comprises a positive photosensitive composition containing an alkali-soluble resin as a binder resin. Or a positive photosensitive composition which is a vinyl polymer resin.

The present invention further includes a positive photosensitive composition wherein the novolak resin is a meta-cresol novolak resin.

The present invention also includes a positive photosensitive composition in which the vinyl polymer resin contains at least one structural unit selected from the group consisting of the general formulas (IVa) to (IVe).

[0016]

Embedded image Wherein R ¹ and R ² each represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a carboxyl group, or a salt thereof, and R ³ represents a hydrogen atom, a halogen atom,
Represents an alkyl group or an aryl group, W represents an -O- or -NH- bond, X represents a divalent linking group, and Y represents a divalent aromatic group which may have a substituent. "

Further, the present invention includes a positive photosensitive lithographic printing plate comprising the above-described photosensitive composition provided on a metal support.

[0018]

BEST MODE FOR CARRYING OUT THE INVENTION In the following, the number of atomic groups having a urea bond or a urethane bond used in the photosensitive composition of the present invention and the method for producing the same is two via an atomic group having a biuret bond. The photosensitive compound and other components that are linked as described above, the method for preparing the positive photosensitive composition used in the present invention, and the method for producing the positive lithographic printing plate of the present invention will be described in detail. .

The photosensitive compound according to the present invention, characterized in that two or more atomic groups having a urea bond or a urethane bond are linked via an atomic group having a biuret bond, for example, o- Unexposed portions of an o-naphthoquinonediazide compound such as naphthoquinonediazide-5-sulfonic acid ester and o-naphthoquinonediazide-4-sulfonic acid ester and an acid-decomposable dissolution inhibiting compound in a three-component chemically amplified photosensitive composition. Any compound having an action of suppressing dissolution may be used and can be suitably used in the present invention. Among them, the ο-naphthoquinonediazide compound can be listed as a particularly suitable system because of its easy synthesis, and the system will be described below as an example.

The effect of the photosensitive compound of the present invention becomes stronger as the number of atomic groups having a urea bond or a urethane bond in the molecule increases. Therefore, two or more atomic groups having a urea bond or a urethane bond in the molecule are used. Preferably, it is present, more preferably 2 to 10. Further, when these atomic groups having a urea bond or a urethane bond in the molecule are connected to an atomic group having a biuret bond, the developing characteristics become hard and the developing latitude and the like are also suitable.

Such a photosensitive compound used in the present invention can be synthesized by various methods. In the case of an o-naphthoquinonediazide compound, for example, it can be easily synthesized by the following method. An adduct (III) of a compound having two or more isocyanate groups and urethane bonds of the general formula (I) and having a hydrocarbon skeleton and a compound having an amino group and a hydroxyl group of the general formula (II) is synthesized. By carrying out the condensation reaction of o-naphthoquinonediazidosulfonyl chloride with a basic compound, a photosensitive compound suitably used in the present invention can be easily synthesized.

[0022]

Embedded image B (—R—NCO) n (I)

[0023]

Embedded image H ₂ N—X—Y—OH (II)

[0024]

Embedded image B (—R—NH—CO—NH—X—Y—OH) n (III) “where B is an atomic group having a biuret bond, and R is a hydrocarbon that may have a substituent. A group, n is 2 or more, X is a single bond or a divalent linking group, and Y represents an aliphatic or aromatic hydrocarbon group which may have a substituent. "

Here, as a specific example of the isocyanate compound of the general formula (I), a biuret-type polyisocyanate can be mentioned as a typical example. Biuret-type polyisocyanates are described in the literature (Mitsuo Kase, Mitsuru Otsubo, DIC Technical Review, No. 3, pp. 55-63, 1997).
As described in (1), general formula (I) is considered to represent the structure having the highest existence probability because it contains isomers having different repeat numbers.

Examples of commercially available products of the biuret-type polyisocyanate compound include, but are not limited to, Sumidur N-75, Sumidur N3200, Sumidur N3200-90MX,
Biuret-type polyisocyanates such as Sumidur N3200-90E (all manufactured by Sumitomo Bayer Urethane Co., Ltd.) can be mentioned.

Specific examples of the amine compound of the general formula (II) include m-aminophenol, p-aminophenol, o-aminophenol, 2-amino-4-methylphenol, and 3-amino-2-methylphenol. Phenol, 4
-Amino-3-methylphenol, 5-amino-2-methylphenol, 2-amino-5-methylphenol,
Aminoresorcinol, 5-aminosalicylic acid, 2-aminophenol-4-sulfonamide, 2-amino-4-
Examples include aminophenols such as chlorophenol, and amino group-containing alcohols such as 3-amino-1-propanol, 3-aminobenzyl alcohol, 4-amino-1-butanol, and 2- (4-aminophenyl) ethanol. I can do it.

Specific examples of the general formula (III) include the adducts of the biuret-type polyisocyanate compound and aminophenols listed in the above specific examples.

By the condensation reaction of the compound of the general formula (III) with o-naphthoquinonediazidosulfonic acid chloride,
When synthesizing the o-naphthoquinonediazide compound, 0.01 to 0.01% of o-naphthoquinonediazidesulfonic acid chloride is added to the hydroxyl group of the compound of the general formula (III).
It is preferable to react 1.2 equivalents,
More preferably, the reaction is carried out in an equivalent amount. As the o-naphthoquinonediazidesulfonic acid chloride, various isomers can be used, and o-naphthoquinonediazide-4-sulfonic acid chloride and o-naphthoquinonediazide-5-sulfonic acid chloride are particularly preferable. Further, in the case of an o-naphthoquinonediazide compound obtained by a condensation reaction with o-naphthoquinonediazide-4-sulfonic acid chloride, a photosensitive composition having a wide development latitude and high sensitivity can be obtained. It is also easy.

Further, in the positive photosensitive composition of the present invention, alkali-soluble resins having various structures can be used as a binder resin, so that the developing characteristics and the like can be further improved. This alkali-soluble binder resin is preferably insoluble in water, and more preferably has an acidic group for development with an aqueous alkaline developer. Acidic groups such as a phenolic hydroxyl group, a carboxylic acid group, a sulfonic acid group, an imide group, a sulfonamide group, an N-sulfonamide group, an N-sulfonylurethane group and an active methylene group can be cited as examples of suitable acidic groups. .

Examples of the alkali-soluble binder resin which can be suitably used in the positive photosensitive composition of the present invention include phenol-formaldehyde resin, m-cresol-formaldehyde resin, p-cresol-formaldehyde resin, m- / p- Mixed cresol-formaldehyde resin, phenol / cresol (m-, p-, or m-
Novolak resin or resol resin such as formaldehyde resin, phenol-formaldehyde resin, resorcinol-formaldehyde resin, t-butylphenol-formaldehyde resin, N- (4-hydroxyphenyl) methacrylic Amide, monomethacryloylhydroquinone, o-hydroxystyrene, p-hydroxystyrene, p-isopropenylphenol, m-isopropenylphenol, acrylic acid, methacrylic acid, N- (4-sulfamoylphenyl) methacrylamide, N-phenyl Resin containing at least one kind of sulfonyl methacrylamide, N-phenylsulfonyl maleimide, etc .;
Active methylene group-containing resins described in JP-A-127237 and JP-A-8-339080.
Nos. 4,028,098; 6,086,098; and 4,887,098. Vinyl polymer resins such as binder resins described in JP-A-63-24047, carboxyl group-containing polyurethane resins described in JP-A-63-124047, and JP-A-63-261350.
Polyurethane resins having an N-sulfonylamide group, an N-sulfonyluureido group, and an N-aminosulfonylamide group described in JP-A No. 2-77748, polyurethane resins such as an active imide group-containing polyurethane resin described in JP-A-2-77748, Examples thereof include polyamides such as hydroxypolyamide described in 1-6947, and polyesters such as polyester resin having a phenolic hydroxyl group described in JP-A-6-236029.

The photosensitive layer containing these alkali-soluble resins may contain fine particles as described in JP-A-9-90610. In some cases, printing durability, development latitude, and the like are further improved.

These alkali-soluble resins can be used alone or as a mixture of a plurality of them. The addition amount of the alkali-soluble resin in the photosensitive composition,
It is preferably 3 to 90 with respect to the total solid content in the photosensitive composition.
% Range. These alkali-soluble resins have a number average molecular weight of 200 to 400,000 and a weight average molecular weight of 3
It is preferably from 00 to 800,000.

When a novolak resin is used among the above alkali-soluble resins, a photosensitive composition having particularly good developing characteristics can be obtained. As a feature of the use of the novolak resin, the development latitude is widened, and the sensitivity is hardly affected by the change in the activity of the developer. Novolak resins particularly preferably used in the present invention include m- / p-mixed cresol-formaldehyde resins and phenol-formaldehyde resins.

The photosensitive composition using m-cresol-formaldehyde resin as the binder resin tends to have high sensitivity, but the conventional ο-naphthoquinonediazide compound is soft and the use conditions are limited. . However, by using the photosensitive compound of the present invention, there is also a feature that development characteristics such as high contrast are improved.

On the other hand, a photosensitive composition using the above-mentioned alkali-soluble resin other than the novolak resin as a binder resin generally has a tendency that the developing characteristics such as high contrast and development latitude tend to decrease. By using the compound, the development characteristics are significantly improved. Therefore, even with the alkali-soluble resin, which can be used in combination with a novolak resin in the past, by using the photosensitive compound of the present invention, it is possible to use without using a novolak resin. Was.

As an example of the alkali-soluble binder resin other than the novolak resin which can be particularly preferably used in the present invention, a vinyl polymer resin can be mentioned.
Vinyl polymer binder resins are often used industrially in the photosensitive layer of lithographic printing plates for UV ink printing due to their strong solvent resistance, and have significant significance in improving their development characteristics.

Examples of such vinyl polymer binder resins include resins containing at least one structural unit selected from the group consisting of the general formulas (IVa) to (IVe).

[0039]

Embedded image

Wherein R ¹ and R ² are each a hydrogen atom,
A halogen atom, an alkyl group, an aryl group, or a carboxyl group, or a salt thereof, R ³ represents a hydrogen atom, a halogen atom, an alkyl group, or an aryl group;
X represents an O- or -NH- bond, X represents a divalent linking group, and Y represents a divalent aromatic group which may have a substituent. "

The resins containing the structures of the above general formulas (IVa) to (IVe) can be synthesized by various methods. For example, JP-A-2-866 and JP-A-8-1991 are known.
It can be synthesized by the method described in No. 2, etc.

Further, the vinyl polymer resin containing the structural units represented by the general formulas (IVa) to (IVe) preferably used in the present invention has the general formulas (IVa) to (IVe) per 100 parts by weight of the resin. The structural unit shown is 5-80
When used in a photosensitive lithographic printing plate as a binder resin, the solvent resistance, abrasion resistance,
Demonstrates even better performance in developing characteristics.

Further, in the photosensitive composition of the present invention, when a vinyl polymer resin having a structure represented by any of the general formulas (IVa) to (IVe) and a known novolak resin are used in combination as a binder resin, the developing characteristics are further improved. The resulting photosensitive composition can be obtained. Preferably, 5 to 50 parts by weight of a photosensitive compound is used per 100 parts by weight of a binder resin composed of a vinyl polymerizable resin and a novolak resin, and 3 to 98 parts by weight of a vinyl polymerizable resin is used per 100 parts by weight of the binder resin. By using the compound, particularly good developing characteristics can be obtained.

In the photosensitive composition of the present invention, a known positive-working photosensitive compound other than the above-described photosensitive compound of the present invention can be used in combination. A typical example is ο-
Although there is a naphthoquinonediazide compound, specifically, an ester of 1,2-naphthoquinonediazidesulfonic acid chloride and a pyrogallol-acetone resin described in JP-B-43-28403 is preferable.
Other suitable orthoquinonediazide compounds include:
U.S. Pat. Nos. 3,046,120 and 3,18
There is an ester of 1,2-naphthoquinonediazidesulfonic acid chloride and a phenol-formaldehyde resin described in US Pat. No. 8,210. Other useful o-naphthoquinonediazide compounds are described and known in numerous patents. For example, JP-A-47-
No. 5303, No. 48-63802, No. 48-63
Nos. 803, 48-96575 and 49-387
No. 01, No. 48-13354, and JP-B-37-180
No. 15, No. 41-11222, No. 45-9610
And those described in the respective specifications such as JP-A-49-17481. Particularly preferred o-naphthoquinonediazide compounds in the present invention are compounds obtained by reacting a polyhydroxy compound with 1,2-naphthoquinonediazidesulfonic acid chloride.
Specific examples of such compounds are described in JP-A-51-13940.
No. 2, No. 58-150948, No. 58-203434
No., 59-165053, 60-12445
No. 60-134235, No. 60-16343
No. 61-118744, No. 62-10645,
No. 62-10646, No. 62-153950, No. 6
Examples described in the specification such as 2-178562 can be given. When synthesizing these o-naphthoquinonediazide compounds, it is preferable to react 0.2 to 1.2 equivalents of 1,2-naphthoquinonediazidesulfonic acid chloride with respect to the hydroxyl group of the polyhydroxy compound, More preferably, 1.0 equivalent is reacted.

The resulting o-naphthoquinonediazide compound is a mixture of various 1,2-naphthoquinonediazidesulfonic acid ester groups having different positions and amounts of introduction, and all the hydroxyl groups are 1,2-naphthoquinonediazidesulfonic acid. The proportion of the compound converted by the ester in the mixture (the content of the completely esterified compound) is preferably 5 mol% or more, more preferably 20 to 100 mol%.

Further, examples of the positive photosensitive compound which can be used in combination other than the o-naphthoquinonediazide compound include, for example,
JP-B-56-2696, JP-A-48-89003,
JP-A-51-120714, JP-A-53-13342
9, JP-A-55-12995, JP-A-55-126
236, JP-A-56-17345, JP-A-60-1
0247, JP-A-60-37549, JP-A-60-375
No. 121446, JP-A-61-278847, JP-A-5-158230, JP-A-6-83047, JP-A-6-324495 and the like can be mentioned.

The positive photosensitive composition of the present invention can be used as a positive lithographic printing plate by coating it on an aluminum support.

In the case of a positive planographic printing plate, various additives can be added according to the purpose. For example, a surfactant for improving coating properties, a plasticizer for improving physical properties of a coating film, a sensitizing agent having a hydrophobic group for increasing ink inking property of an image area, and for increasing sensitivity. Further, a cyclic acid anhydride or a polyhydroxyphenyl compound, a printing-out agent for obtaining a visible image immediately after exposure, and a dye or other filler as an image coloring agent can be added.

As the surfactant, JP-A-62-366
No. 57, JP-A-62-226143, and the like. Examples of the plasticizer include diethyl phthalate, dibutyl phthalate, dioctyl phthalate, tributyl phosphate, trioctyl phosphate, tricresyl phosphate, tri (2-chloroethyl) phosphate, and tributyl citrate.

Examples of the sensitizer include novolak resins having a hydrophobic group such as p-octylphenol novolak and pt-butylphenol novolak. As cyclic acid anhydrides, US Pat.
As described in US Pat. No. 5,128, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, 3,6-endooxy- 無水 4-tetrahydrophthalic anhydride, tetrachlorophthalic anhydride, maleic anhydride Acid, chloromaleic anhydride, α-phenylmaleic anhydride, succinic anhydride, pyromellitic anhydride and the like. Examples of the polyhydroxyphenyl compound include pyrogallol, gallic acid, 2,3,4-trihydroxyacetophenone,
2,3,4-trihydroxybenzophenone and the like. By including these cyclic acid anhydrides or polyhydroxyphenyl compounds in an amount of 1 to 15% by weight in the total photosensitive composition, the sensitivity can be increased up to about three times.

As a printing-out agent for obtaining a visible image immediately after exposure, for example, a combination of a photosensitive compound which releases an acid upon exposure and an organic dye which can form a salt can be mentioned. More specifically, ο described in JP-A-50-36209 and JP-A-53-8128.
A combination of a naphthoquinonediazide-4-sulfonic acid halide with a salt-forming organic dye or JP-A-53-36223;
Nos. 54-74728, 60-3626, 6
1-1143748, 61-151644, 63
Combinations of a trihalomethyl compound and a salt-forming organic dye described in JP-A-58440 can be exemplified.

Other dyes besides the above-mentioned salt-forming organic dyes can be used as image coloring agents. Suitable dyes including salt-forming organic dyes include oil-soluble dyes and basic dyes. Specifically, Oil Yellow #
101, oil yellow # 130, oil pink # 31
2. Oil green BG, oil blue BOS, oil blue # 603, oil black BY, oil black BS, oil black T-505 (all manufactured by Orient Chemical Co., Ltd.), Victoria Pure Blue, crystal violet (CI42555), methyl Violet (CI42535), Rhodamine B (CI4517)
OB), malachite green (CI42000), methylene blue (CI52015) and the like.

The amount of these various additives varies depending on the purpose, but generally, the amount of the solid content of the photosensitive composition is from 0 to 0%.
A range of 30% by weight is preferred.

The above-mentioned photosensitive composition can be dissolved in various solvents as necessary and applied on a support. As the solvent, for example, a halogen-based solvent such as methylene chloride, chloroform, dichloroethane, trichloroethane, trichloroethylene, monochlorobenzene, dichlorobenzene, and carbon tetrachloride: an aliphatic or alicyclic ring such as hexane, heptane, cyclohexane, benzene, toluene, and xylene Aromatic or aromatic hydrocarbon solvents: ether solvents such as tetrahydrofuran, dioxane and diethyl ether: ester solvents such as methyl acetate, butyl acetate, ethyl acetate, butyl acetate, methyl cellosolve acetate, ethyl cellosolve acetate: acetone, methyl ethyl ketone, Ketone solvents such as methyl isobutyl ketone and cyclohexanone, methanol, ethanol, butanol, benzyl alcohol, diacetone alcohol, methyl cellosol , Ethyl cellosolve, such as alcohol solvents cyclohexanol: acetonitrile, N, N-
Nitrogen-containing solvents such as dimethylformamide, N, N-dimethylacetamide and N-methylpyrrolidone: dimethylsulfoxide and the like.
It is also possible to use a mixture of species or more.
Further, a mixed solvent with water may be used.

The photosensitive composition thus produced can be used, for example, by dip coating, curtain coating, roll coating,
It is applied to the support by a well-known application method such as spray application, wheeler application, spinner application, air knife application, doctor knife application and the like.

As the support, for example, aluminum,
Metal plate of zinc, copper, stainless steel, iron, etc .: Plastic film of polyethylene terephthalate, polycarbonate, polyvinyl acetal, polyethylene, etc .: Vapor deposition and lamination of a metal layer on paper or plastic film with synthetic resin melt coated or synthetic resin solution coated Composite materials provided by such techniques as above: and other various materials used as a support for a printing plate.

In the case of a support having a metal surface, particularly an aluminum surface, it is preferable that a surface treatment such as graining treatment, anodic oxidation treatment, and hydrophilization treatment is performed. Examples of the graining treatment include mechanical surface roughening, chemical surface roughening, and electrochemical surface roughening, and these may be combined. In the electrochemical surface roughening, a particularly suitable grain shape is easily obtained, and hydrochloric acid or nitric acid is often used as an electrolytic solution. In the anodic oxidation treatment, a strong oxide film is formed on the aluminum surface in an electrolytic solution such as sulfuric acid. Water-soluble polymers, silicates, hot water, etc. are used to improve the hydrophilicity of the non-image area, improve the adhesion between the photosensitive layer of the image area and the aluminum plate, and prevent staining (residual dye) after development. Surface treatment (sealing treatment) is performed.

After coating the photosensitive composition on the surface-treated aluminum plate, it is dried by a known method to obtain a photosensitive lithographic printing plate provided with a photosensitive layer on a support. The coating amount of the photosensitive composition is usually about 0.5 to 5 g / dry weight.
m2.

The photosensitive lithographic printing plate thus obtained can be used by a known method. For example, a positive type film is brought into close contact with this photosensitive lithographic printing plate, exposed with an ultra-high pressure mercury lamp, a metal halide lamp, etc., and developed with an aqueous alkali solution such as sodium metasilicate, potassium metasilicate, sodium phosphate, caustic soda, and the like. Used as When the film is adhered, it is also preferable to attach or disperse fine particles on the surface of the photosensitive layer or inside the photosensitive layer in order to improve the adhesion.

[0060]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples unless it exceeds the gist.

(Synthesis Example 1) 4-aminophenol (8.
58 g) with N, N-dimethylacetamide (200 g)
The mixture was added to the solvent and stirred, and Sumidur N-75S (20.00 g, manufactured by Sumitomo Bayer Urethane), which is a biuret-type polyisocyanate, was slowly added dropwise. 40 ℃
After stirring for 6 hours, it was confirmed by IR spectrum that the absorption of the isocyanate group had disappeared. 1,2-Naphthoquinonediazide-5-sulfonyl chloride (21.12 g) was added to and dissolved in the reaction mixture, and triethylamine (8.7 g) was added dropwise. After stirring for 5 hours, the reaction mixture was poured into water, and the formed precipitate was filtered to obtain a yellow powdery solid.

(Synthesis Example 2) 2-aminophenol-4-
Sulfonamide (20.63 g) was added to an N, N-dimethylacetamide (200 g) solvent and stirred, and Sumidur N3200, a biuret-type polyisocyanate, was added.
(20.00 g, manufactured by Sumitomo Bayer Urethane) was slowly dropped. This was stirred at 40 ° C. or lower for 6 hours, and it was confirmed by IR spectrum that the absorption of isocyanate groups had disappeared. To this reaction mixture, 1,2-naphthoquinonediazide-4-sulfonyl chloride (29.45 g) was added and dissolved, and triethylamine (13.0 g) was added dropwise.
After stirring for 5 hours, the reaction mixture was poured into water, and the formed precipitate was filtered to obtain a brown powdery solid.

(Comparative Synthesis Example 1) To a solution of tolylene diisocyanate (38.3 g) dissolved in acetone (50 g) was added tetraethylene glycol (23.3 g), acetone (50 g), and dibutyltin dilaurate (0.3 g).
g) was added dropwise, and the mixture was stirred for 2 hours. Furthermore, p
Aminophenol (22.0 g) in acetone (100
g) The solution was added and stirred at 60 ° C. for 3 hours. After cooling to room temperature, 1,2-naphthoquinonediazide-5-sulfonyl chloride (51.0 g) was added, and triethylamine (2
1.1 g) in acetone (100 g) was slowly added dropwise. After stirring for 4 hours, the reaction mixture was poured into a 1% aqueous hydrochloric acid solution, and the formed precipitate was filtered, washed with water and dried.
345164 photosensitive resin was obtained.

Next, for Examples 1 and 2 and Comparative Example 1, photosensitive solutions (photosensitive compositions) having the composition ratios shown in Table 1 below, and for Examples 3 and 4 and Comparative Example 2, compositions having the composition ratios shown in Table 2 below were obtained. Photosensitive liquids (photosensitive compositions) were prepared.

[0065]

[Table 1]

Note 1: The weight average molecular weight was 4,000. Note 2: Basic oil-soluble dye manufactured by Hodogaya Chemical Industry Co., Ltd. Note 3: Fluorinated surfactant manufactured by Dainippon Ink and Chemicals, Inc.

[0067]

[Table 2]

Note 4: Synthesized by the method described in Japanese Patent Application No. 8-19912. 2- (N '-(4-hydroxyphenylureido) ethyl methacrylate (72 g), N-phenylmaleimide (14 g), methacrylamide (14
g) was polymerized in N, N-dimethylacetamide (350 g) solvent (80 ° C., 5 hours, using AIBN). The reaction mixture was poured into water, and the resulting precipitate was filtered and dried to obtain an acrylic binder resin.

Note 5: The weight average molecular weight was 4,000. Note 6: Basic oil-soluble dye manufactured by Hodogaya Chemical Industry Co., Ltd. Note 7: Fluorosurfactant manufactured by Dainippon Ink and Chemicals, Inc.

(Examples 1 to 10) An aluminum plate having a thickness of 0.24 mm was degreased with an aqueous solution of sodium hydroxide, and subjected to electrolytic polishing in a 20% hydrochloric acid bath to obtain a center line average roughness (Ra). A grain of 0.65 μm was obtained. Then 20
In a sulfuric acid bath at a current density of 2 A / dm ² to form an oxide film of 2.8 g / m ² , washed with water and dried,
An aluminum support was obtained. The photosensitive solution (photosensitive composition) having the above composition was applied on the thus obtained aluminum support using a roll coater and dried at 130 ° C. for 1 minute to obtain a photosensitive lithographic printing plate. The dry coating amount was 2.0 g / m ² .

Comparative Example 1 The same method as in Examples 1 and 2 was used except that the photosensitive compound synthesized in Comparative Synthesis Example 1 was used in place of the photosensitive compound in Synthesis Examples 1 and 2 in the composition shown in Table 1. Produced a lithographic printing plate.

(Comparative Example 2) The same method as in Examples 3 and 4 was used except that the photosensitive compounds synthesized in Comparative Synthesis Example 1 were used in place of the photosensitive compounds in Synthesis Examples 1 and 2 in the composition shown in Table 2. Produced a lithographic printing plate.

A gray scale (optical density difference: 0.15) was brought into close contact with each of the resulting photosensitive lithographic printing plates in vacuum, and exposed from a distance of 1 m with a 3 kW metal halide lamp. This is an automatic processor PD-9 manufactured by Dainippon Screen Mfg. Co., Ltd.
Using No. 12, a developing solution PD-1 manufactured by Polychrome Japan Co., Ltd. sold by Dainippon Ink and Chemicals, Inc. was diluted with water at a predetermined ratio and developed at 30 ° C. for 12 seconds.

(Evaluation of High Contrast Property) The high contrast property is (solid number of steps) −
The length of the halftone portion was determined from (the number of clear steps). Here, the solid stage number indicates a portion where the photosensitive layer was not eroded by the developing solution, and the clear stage number indicates a portion where the photosensitive layer was completely dissolved in the developing solution. Therefore, it can be said that the smaller the number, the higher the contrast. The developer was used by diluting PD-1 nine times with water.

(Evaluation of Development Latitude) The development latitude was evaluated from the change in the number of clear stages by changing the dilution ratio of the developer. The developer used at this time was PD-1
One-fold dilution (A) and 15-fold dilution (B)
It was used. Therefore, the smaller the difference (AB) between the number of clear stages evaluated in (A) and (B) is, the smaller the effect of the developer concentration is, and it can be said that the development latitude is wide.

The development characteristics of the lithographic printing plate were evaluated as described above, and the results are shown in Tables 3 and 4.

[0077]

[Table 3]

* In the column of development latitude, column A shows the number of clear steps when PD-1 was developed with a developer diluted 6-fold with water. Column B shows the number of clear stages when PD-1 was developed with a developer diluted 15-fold with water. The difference (AB) indicates the difference in the number of clear stages.

[0079]

[Table 4]

* In the column of development latitude, column A shows the number of clear stages when PD-1 was developed with a developer diluted 6-fold with water. Column B shows the number of clear stages when PD-1 was developed with a developer diluted 15-fold with water. The difference (AB) indicates the difference in the number of clear stages.

As a result of the above evaluation, it was found that in the system using the novolak resin as the binder resin (Table 3), the use of the photosensitive compound of the present invention improved the high contrast and the development latitude. In Examples 1 and 2, the value of (the number of solid steps)-(the number of clear steps) is smaller than that of Comparative Example 1, and it can be seen that the contrast is high. Also,
Also in the development latitude, in Examples 1 and 2, the change in the number of clear stages due to the change in the concentration of the developer is smaller than that in Comparative Example 1, and it can be seen that the development latitude is wider.

On the other hand, it was found that even in a system using an acrylic resin as a binder resin (Table 4), the use of the photosensitive compound of the present invention tends to improve the high contrast and the development latitude. In Examples 3 and 4, the value of (the number of solid steps)-(the number of clear steps) is smaller than that of Comparative Example 2, and it can be seen that the contrast is high. Also in Examples 3 and 4, the change in the number of clear stages due to the change in the concentration of the developing solution was smaller than that in Comparative Example 2, and the developing latitude was wider. Further, the printing plates obtained in Examples 3 and 4 were excellent in printing durability and solvent resistance.

Therefore, even if the kind of the binder resin is changed, the effect of the photosensitive agent of the present invention appears, and the development of the acrylic binder resin or the like in which the developing characteristics are deteriorated with the conventional photosensitive agent (Comparative Example 2). It has been found that the characteristics can be improved.

[0084]

The coating film obtained from the photosensitive resin composition of the present invention has good development characteristics, and is excellent in high contrast and development latitude.

Claims (10)

[Claims] 1. A photosensitive composition comprising a photosensitive compound in which two or more atomic groups having a urea bond or a urethane bond are linked via an atomic group having a biuret bond. . 2. The photosensitive composition according to claim 1, wherein the photosensitive compound is an o-naphthoquinonediazide compound. 3. The compound of the formula (I)
And o-naphthoquinonediazidosulfonic acid ester of an adduct (III) of the compound of the formula (II).
4. The photosensitive composition according to item 1. B (-R-NCO) n (I) H ₂ NXY-OH (II) B (-R-NH-CO-NH-XY- OH) n (III) "where B is an atomic group having a biuret bond, R is a hydrocarbon group which may have a substituent, n is 2 or more, X is a single bond or a divalent linking group, Y is Represents an aliphatic or aromatic hydrocarbon group which may have a substituent. " 4. The photosensitive composition according to claim 1, wherein the photosensitive compound is a condensate of an adduct of a biuret-type polyisocyanate and an aminophenol and o-naphthoquinonediazidosulfonyl chloride. 5. The positive photosensitive composition according to claim 1, comprising an alkali-soluble resin as a binder resin. 6. The positive photosensitive composition according to claim 5, wherein the alkali-soluble resin is a novolak resin. 7. The positive photosensitive composition according to claim 6, wherein the novolak resin is a meta-cresol novolak resin. 8. The positive photosensitive composition according to claim 5, wherein the alkali-soluble resin is a vinyl polymer resin. 9. The method according to claim 1, wherein the vinyl polymer resin is of the general formula (I)
9. The positive photosensitive composition according to claim 8, wherein the composition contains at least one structural unit selected from the group consisting of Va) to (IVe). Embedded image Wherein R ¹ and R ² each represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a carboxyl group, or a salt thereof, and R ³ represents a hydrogen atom, a halogen atom,
Represents an alkyl group or an aryl group, W represents an -O- or -NH- bond, X represents a divalent linking group, and Y represents a divalent aromatic group which may have a substituent. " 10. A positive photosensitive lithographic printing plate comprising the photosensitive composition according to claim 1 provided on a metal support.