JPS6380254A - Photosensitive composition - Google Patents

Abstract

PURPOSE:To obtain a photosensitive composition capable of forming a lithographic plate wide in the range of proper development conditions and high in printing resistance by incorporating a polyurethane resin having o- quinonediazide groups. CONSTITUTION:The polyurethane resin to be used has the o-quinonediazide groups on the main chain, preferably, having a fundamental skeleton obtained by reacting a diisocyanate compound represented by formula (I) with a diol compound having the quinonediazide groups represented by formula (II) or (III). In formulae (I)-(III), R1 is a divalent aliphatic or aromatic group; R2 is H, alkyl, aryloxy, or the like; each of R3-R5 is a divalent aliphatic or aromatic group; Ar is a tetravalent aromatic group; X is O or N-R6; R6 is alkyl or aryl; and D is o-quinonediazide.

Description

DETAILED DESCRIPTION OF THE INVENTION "Industrial Application Field" The present invention relates to photosensitive compositions, particularly 0-
The present invention relates to a photosensitive composition containing a quinonediazide compound as a photosensitive component and suitable for use in lithographic printing plates. In addition, in this specification, the 〇-quinonediazide compound is
1.2-benzoquinone-2-diazide compound and 1.2
-A general term for aromatic 0-quinonediazide compounds such as naphthoquinone-2-diazide compounds.

"Prior Art" It is known that when an 0-quinonediazide compound is irradiated with actinic rays, it decomposes to produce a five-membered ring carboxylic acid, which becomes soluble in alkaline water. Therefore, photosensitive compositions containing an 0-quinonediazide compound have been widely used in lithographic printing plates, photoresists, and the like as photosensitive compositions for producing positive-type images.

These diazo compounds are generally applied to lithographic printing plates, etc. in the form of sulfonic acid esters obtained by chemical condensation of an 0-quinonediazide compound having a halogenosulfonyl group such as sulfonyl chloride and a mono- or polyhydroxyphenyl compound. .

Examples of low molecular weight 0-quinonediazide compounds include t
l;! '2.2'-dihydroxydiphenyl, 2.3
-dihydroxynaphthalene and p-t-butylphene/
-ol 0-quinonediazide sulfonic acid ester, etc.

On the other hand, as a high molecular weight O-quinonediazide compound,
For example, the phenol-formaldehyde resins described in U.S. Pat. No. 3,046,120 or
-0-Naphthoquinonediazide sulfonic acid ester of cresol-formaldehyde resin, or JP-A-1988-
No. 1045, JP-A-56-1044, JP-A-43-28403 and JP-A-49-24361
There are 0-quinonediazide sulfonic acid esters of condensates of polyhydric phenols and aldehydes or ketones, which are disclosed in Japanese Patent Publication No. 2003-100003. However, when these 0-quinonediazide compounds are used alone as a photosensitive composition, various drawbacks arise. That is, when used alone, it generally has poor film-forming properties and crystals precipitate, and the mechanical strength or chemical resistance of the image is low, making it difficult to withstand multiple printings or chemical etching. Have difficulty. In order to solve these drawbacks, alkali-soluble resins such as novolac-type phenol resins have generally been used together with O-quinonediazide compounds. However, due to the nature of the novolac type phenolic resin, it still has poor film-forming properties, low mechanical strength or chemical resistance of images, and is difficult to withstand printing on a large number of sheets. Furthermore, there is a problem that the range of appropriate developing conditions is narrow.

"Problems to be Solved by the Invention" The purpose of the present invention is to overcome the above-mentioned problems and to provide a photosensitive composition that provides a lithographic printing plate with a wide range of appropriate development conditions (and a high printing durability). It is.

"An unsuccessful means to solve the problem" As a result of intensive study to achieve the above objectives, the inventors of the present invention discovered that these objectives could be achieved by using a new photosensitive resin. invention has been achieved.

That is, the present invention provides a photosensitive composition containing a polyurethane resin having an 0-quinonediazide group,
It provides:

The polyurethane resin suitably used in the present invention is mainly a polyurethane resin containing a group having an 0-quinonediazide group in the main chain, and preferably has the following general formula (
A diisocyanate compound represented by I) and a diisocyanate compound represented by the general formula (
Polyurethane resins whose basic skeleton is a reaction product of a diol compound having an O-quinonediazide group represented by II) or (III) are included.

0CN-R, -NC○ (I) ■ ■ SO□ In the formula, R1 represents a divalent aliphatic or aromatic hydrocarbon which may have a substituent. If necessary, other functional groups 111 that do not react with the incyanate group in R1, such as esters,
It may have a urethane, amide, or ureido group.

R2 is a hydrogen atom, alkyl which may have a substituent,
It represents an aralkyl, aryl, alkoxy, or aryloxy group, preferably a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an aryl group having 6 to 15 carbon atoms. R3, R6,
R5 may be the same or different, and may be a single bond,
Indicates a divalent aliphatic or aromatic hydrocarbon that may have a substituent. Preferably, it is an alkylene group having 1 to 20 carbon atoms, an arylene group having 6 to 15 carbon atoms, and more preferably an alkylene group having 1 to 8 carbon atoms. Also, if necessary 1
．． R: l, R4, Rs other functional groups that do not react with the incyanate group, such as ester, urethane, amide,
It may have a ureido or ether group. Note that R2-
Two or three rings among 1R3, R1, and Rs may be formed.

Ar represents a tetravalent aromatic hydrocarbon which may have a substituent, preferably an aromatic group having 6 to 15 carbon atoms.

X represents 0 or N-R5.

R6 represents a hydrogen atom or an alkynopearyl group which may have a substituent, preferably a hydrogen atom or an alkynopearyl group having 1 to 1 carbon atoms.
8 alkyl represents an aryl group having 6 to 15 carbon atoms.

Note that R6 may form a ring together with one or two of R2, R3, R4, and Rs.

D represents an 0-quinonediazide group which may have a substituent. It preferably represents an 0-naphthoquinone diazide group linked at the 4- or 5-position.

Specifically, the diisocyanate compound represented by the general formula (I) includes those shown below.

That is, 2.4-) lylene diisocyanate, a dimer of 2,4-tolylene diisocyanate, 2.6-) lylene diisocyanate, p-xylylene diisocyanate, m
-xylylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 1°5-naphthylene diisocyanate, 3,3'-dimethylbiphenyl-4,4'-
Aromatic diisocyanate compounds such as diisocyanate; aliphatic diisocyanate compounds such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, dimer acid diisocyanate, etc.: isophorone diisocyanate, 4.4
'-Methylenebis(cyclohexyl isocyanate)
, alicyclic diisocyanate compounds such as methylcyclohexane-2,4 (or 2,6) diisocyanate, 1,3-(incyanatomethyl)cyclohexane; 1,
Examples include diisocyanate compounds which are reaction products of diols and diisocyanates, such as adducts of 1 mol of 3-butylene glycol and 2 mols of tolylene diisocyanate.

Further, the diol compound having an 0-quinonediazide group represented by the general formula (n) or (III) is preferably an ester of an 0-quinonediazide compound having a halogenosulfonyl group and a trihydroxy compound, or a monoamino dihydroxy compound. amide, and specifically includes those shown below.

That is, 2,6-bis(hydroxymethyl)-4-methylphenyl71.2-naphthoquinone-2-diazide-5-
Sulfonate, 3.5-dihydroxyphenyl/1.2
-naphthoquinone-2-diazide-5-sulfonate, 2
．． 2-bis(hydroxymethyl)propyl/1,2-naphthoquinone-2-diazide-5-sulfonate, N-(
1,1-bis(hydroxymethyl)propyl)-1,2
-naphthoquinone-2-diazide-5-sulfonamide,
Examples include N-(3,5-dihydroxyphenyl)-1,2-naphthoquinone-2-diazide-5-sulfonamide.

The polyurethane resin of the present invention is a diisocyanate compound represented by general formula (I) and general formula (n) or (I
It may be formed from two or more diol compounds having an 0-quinonediazide group represented by II).

Furthermore, diol compounds which may have other substituents may be used in combination to the extent that the range of appropriate development conditions is not narrowed.

Specifically, such diol compounds include those shown below.

So, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, polypropylene glycol, polyethylene glycol, polypropylene glycol, neopentyl glycol, 1,3-butylene glycol, 1,
6-hexanediol, 2-butene-1,4-dionope2.4-)dimethyl-1,3-bentanediol,
1.4-bis-β-hydroxyethoxycyclohexane, cyclohexane dimetatool, tricyclodecane dimetatool, hydrogenated bisphenol A1 hydrogenated bisphenol F1 ethylene oxide adduct of bisphenol A, propylene oxide adduct of bisphenol A, Ethylene oxide adduct of bisphenol F, propylene oxide adduct of bisphenol F, ethylene oxide adduct of hydrogenated bisphenol, propylene oxide adduct of hydrogenated bisphenol A, hydroquinone dihydroxyethyl ether, p-xylylene glycol, dihydroxyethyl sulfone , bis-(2-hydroxyethyl')-2,4-tolylene dicarbamate, 2.4
-) IJ Renbisu(2-hydroxyethylcarbamide), bis-(2-hydroxyethyl)-m-xylylenecarbamate, bis-(2-hydroxyethyl)terephthalate, 3.5-dihydroxybenzoic acid, 2.2-bis (Hydroxymethyl)propionic acid, 2,2-bis(
2-hydroxyethyl)propionic acid, 2,2-bis(
3-hydroxypropyl) propionic acid, bis(hydroxymethyl') vinegar L bis(4-hydroxyphenyl)
Examples include acetic acid, 4,4-bis(4-hydroxyphenyl)pentanoic acid, and tartaric acid.

The polyurethane resin of the present invention is synthesized by heating the above diisocyanate compound and diol compound in an aprotic solvent, adding a known catalyst having an activity corresponding to the reactivity of each compound.

The molar ratio of the diisocyanate and diol compound used is preferably 0.8:1 to 1.2:1, and if incyanate groups remain at the end of the polymer, the final It is synthesized in such a way that no isocyanate groups remain.

The molecular weight of the polyurethane resin of the present invention is preferably 1,000 or more on weight average, more preferably 5. OO
It is in the range of 0 to 100,000.

In the present invention, the amount of polyurethane resin in the photosensitive composition is 2 to 80% by weight, more preferably 20 to 4% by weight.
It is 0% by weight.

In the photosensitive composition of the present invention, the polyurethane resin having an 0-quinonediazide group according to the present invention can be used alone as a photosensitive component, but it may also be used together with a known 0-naphthoquinonediazide compound.

As known 0-naphthoquinonediazide compounds, those which are esters of 1,2-naphthoquinone-2-diazide-5-sulfonyl chloride and pyrogallol-acetone resin described in Japanese Patent Publication No. 43-28403 are most preferred. . Other suitable known orthoquinone diazide compounds include U.S. Pat.
There are esters of 1,2-naphthoquinone-2-diazido-5-sulfonyl chloride and phenol-formaldehyde resins described in No. 3 and No. 3, 188.210. As a known 0-naphthoquinonediazide compound that can be used in the pond water invention, JP-A-47-
No. 5303, 48-63802, 4'8-6, same town
No. 3803, No. 48-96575 of the same town, No. 49-38 of the same town
No. 701, No. 48-13354 of the same town, Special Public Interest Publication No. 41-11 of the 1970s
No. 222, No. 45-9610 of the same town, No. 49-1748 of the same town
Publications such as U.S. Patent No. 1, U.S. Pat. issue,
No. 3.785.825, British Patent No. 1, 227.6
No. 02, No. 1.251.345, No. 1.267,
No. 005, No. 1.329.888, No. 1.330
．． Examples include those described in various specifications such as No. 932 and German Patent No. 854.890.

The amount of the 0-quinonediazide compound in the photosensitive composition of the present invention is 5 to 80% by weight, more preferably 20 to 40% by weight, in total of the known compound and the polyurethane resin having an 0-quinonediazide group.

The composition of the present invention may contain known alkali-soluble polymer compounds such as phenol formaldehyde resin, cresol formaldehyde resin, phenol-modified xylene resin, polyhydroxystyrene, and polyhalogenated hydroxystyrene. Such alkali-soluble polymer compound is used in an amount of 70% by weight or less of the total composition.

The composition of the present invention may contain a cyclic acid anhydride to increase sensitivity, a printout agent to obtain a visible image immediately after exposure, a dye as an image coloring agent, and other fillers. As a cyclic acid anhydride, US Pat. No. 4.115.
Fucric anhydride, as described in No. 128;
Tetrahydrophthalic anhydride, hexahydrophthalic anhydride, 3.6-nindooxy-Δ4-tetrahydrophthalic anhydride, tetrachlorophthalic anhydride, maleic anhydride, chloromaleic anhydride, α-phenylmaleic anhydride, succinic anhydride, pyromellitic acid etc. By containing these cyclic acid anhydrides in an amount of 1 to 15% by weight based on the total composition, the sensitivity can be increased up to about 3 times. Typical print-out agents for obtaining a visible image immediately after exposure include a combination of a photosensitive compound that releases an acid upon exposure and an organic dye that can form a salt. Specifically, JP-A-50-36209, JP-A-53-81
The combination of 0-naphthoquinonediazide-4-sulfonic acid halide and a salt-forming organic dye described in JP-A No. 28, JP-A-53-36223, JP-A-Sho 54-74
The combination of a trihalomethyl compound and a salt-forming organic dye described in Japanese Patent No. 728 can be mentioned. In addition to the above-mentioned salt-forming organic dyes, other dyes can also be used as image coloring agents. Suitable dyes include oil-soluble dyes and basic dyes, including salt-forming organic dyes. Specifically, oil yellow #101, oil yellow #130, oil pink #312, oil green BG, oil blue BoS1 oil blue #603
, Oil Black BY1 Oil Black BS, Oil Black T-505 (manufactured by Orient Chemical Industry Co., Ltd.) Crystal Violet (CI42555), Methyl Violet (CI42535), Rhodamine B (C
I45170B), malachite green (CI4200
0), methylene blue (CI52015), etc.

The composition of the present invention is applied onto a support after being dissolved in a solvent that dissolves each of the above components. The solvent used here is
Examples include ethylene dichloride, cyclohexanone, methyl ethyl ketone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, toluene, and ethyl acetate, and these solvents may be used alone or in combination. The concentration (solid content) of the above components is 2 to 50% by weight.

Additionally, the amount of waste varies depending on the application, but for example, for photosensitive planographic printing plates, the solid content is generally 0.5 to 0.5.
3.0 g/m' is preferred. As the coating amount decreases, the photosensitivity increases, but the physical properties of the photosensitive film deteriorate.

When producing a lithographic printing plate using the photosensitive composition of the present invention, the support may be a hydrophilized aluminum plate, such as a silicate-treated aluminum plate, an anodized aluminum plate, a grained aluminum plate, or a silicate electrode. There is a coated aluminum plate, and there are also surface lead plates, stainless steel plates, chrome-treated steel plates, hydrophilized plastic films and paper.

Examples of developing solutions for the photosensitive composition of the present invention include sodium silicate, potassium silicate, sodium hydroxide, potassium hydroxide, lithium hydroxide, tribasic sodium phosphate, dibasic sodium phosphate, tribasic ammonium phosphate, dibasic diphosphate, Aqueous solutions of inorganic alkaline agents such as ammonium chloride, sodium metasilicate, sodium bicarbonate, aqueous ammonia, etc. are suitable, with concentrations of O, ranging from 1 to 10% by weight, preferably from 0.5 to 5% by weight. It is added as follows.

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

The photosensitive composition of the present invention coated on a support can form a line image,
By exposing to light through a transparent original having a halftone image or the like, and then developing with an aqueous developer, a positive relief image is given to the original.

Light sources used for exposure include carbon arc lamps, mercury lamps, xenon lamps, tungsten lamps, and metal halide lamps.

The photosensitive composition of the present invention has excellent solubility in organic coating solvents when coated on a support, and also has appropriate development conditions when developing unexposed areas with an alkaline developer after coating, drying, and image exposure. The range is wide. Furthermore, the obtained relief image has good abrasion resistance, oil sensitivity, and adhesion to a support, and when used as a printing plate, a large number of good prints can be obtained.

"Examples" The present invention will be explained in more detail with reference to synthesis examples and examples, but the content of the present invention is not limited thereto.

Synthesis Example 1 64.5 g (0.24 mol') of 1.2-naphthoquinone-2-diazide-5-sulfonyl chloride was placed in a 1J 3-day round bottom flask equipped with a pH meter, a dropping funnel, and a stirrer. 6-bis(hi)″roxymethyl)-p-
Cresol 40.4g (0.24mol), acetonitrile 440mj! and water 176rnl! was added and stirred at room temperature to disperse the solid. A mixture of 36.4 g (0.36 mol) of triethylamine and 80 g of acetonitrile was added dropwise to this mixture using a dropping funnel. At this time, the pH of the reaction mixture was adjusted to be 5 to 6. A mixture of triethylamine and acetonitrile was added dropwise until the pll of the reaction mixture remained unchanged at around 6. After the reaction is complete, the precipitate is filtered, washed with water, and dried.
32 g of 2,6-bis(hydroxymethyl)-4-methylphenyl 1,2-naphthoquinone-2-diazide-5-
Sulfonate was obtained. Furthermore, 500mj equipped with a condenser and a stirrer! 03 days 2゜6- in a round bottom flask
Bis(hydroxymethyl)-4-methylphenyl 1.2
-naphthoquinone-2-diazide-5-sulfonate 14
．． 0 g (0,035 mol) and 5.9 g (0,035 mol) of hexamethylene diisocyanate and 400 mj of dioxane! dissolved in. 0.25 g of di-n-butyltin dilaurate was added as a catalyst, and the mixture was heated to 50° C. for 3 hours with stirring. Thereafter, the reaction solution was poured into water 21 with stirring to precipitate a yellow polymer. By filtering and drying this polymer, 16
Polymer (a) of g was obtained.

The molecular weight was measured by gel permeation chromatography (OFC) and found to be 12.000 in weight average (polystyrene standard).

Synthesis Examples 2 to 5 Hereinafter, in the same manner as in Synthesis Example 1, diol compounds having an 0-quinonediazide group shown in Table 1 were synthesized, and subsequently reacted with diisocyanate compounds shown in the same table to form the corresponding polyurethane resin (b). ~(e) was synthesized.

All molecular weights are weight averages (polystyrene equivalent)
It was 5,000 to 30,000.

Examples 1 to 3 An aluminum plate with a thickness of 0.30 and a nylon brush with a thickness of 40
The surface was gritted using a water suspension of 0 mesh pumice stone, and then thoroughly washed with water.

After etching by immersing it in 10% sodium hydroxide at 70° C. for 60 seconds, it was washed with running water, neutralized with 20% HN◯3, and washed with water. This was subjected to electrolytic surface roughening treatment in a 1% nitric acid aqueous solution under the condition of 12.7 V using a sinusoidal alternating waveform current at an anode special electricity amount of 160 clones/dm'. When the surface roughness was measured, it was found to be 0.
It was 6 μ (expressed as Ra). Continued 30% H2
After immersion in SO, aqueous solution and desmutting at 55 °C for 2 minutes, 20% HSO, current density 2 A in aqueous solution.
/d m' to a thickness of 2.7 g/m'.

The photosensitive liquids (I) to (In) shown below were applied to the aluminum plate thus obtained using a wheeler, and
Dry for 2 minutes at °C. Coating weight after drying is 2.5 g
/ m'.

(Photosensitive solution) Next, as a comparative example, a condensation product of phenol-formaldehyde resin and 1,2-naphthoquinone-2-diazide-5-sulfonyl chloride was used instead of the polyurethane resin of the present invention in the above photosensitive solution. A photosensitive liquid (TV) was similarly applied and dried. Coating weight after drying is 2.5g/m
'Met.

In order to check the development tolerance, a gray scale with a density difference of 0.15 was brought into close contact with the photosensitive layer of each of the photosensitive planographic printing plates (I) to (rV) obtained using the photosensitive solutions (I) to (■). Exposure was carried out with a 30 amp carbon arc lamp from a distance of 70 cm. Continue, D
It was immersed and developed in an 8-fold diluted aqueous solution of P-4 (trade name: manufactured by Fuji Photo Film Ql) at 25° C. for 30 seconds and 5 minutes. 30 seconds and 5 on a gray scale with a density difference of 0.15
Table 2 shows the difference in the number of steps required to obtain a completely solid image during minute development.

As can be seen from Table 2, all of the photosensitive lithographic printing plates (I) to (III) using the photosensitive composition of the present invention had small changes in the number of grayscale stages in the vector area and had greatly excellent development tolerance. It was something.

Furthermore, each of the above photosensitive lithographic printing plates (I) to (IV) was imagewise exposed at a distance of 70 cm using a 30 ampere carbon arc lamp, and then exposed at 60° C. at 25° C. using the same developer.
Second immersion development. Next, the lithographic printing plates (I) to (TV) were printed on high-quality paper using a commercially available ink using an offset printing machine. The final number of printed sheets of the lithographic printing plates (I) to (IV) was examined and was as shown in Table 3.

As can be seen from Table 3, all of the photosensitive lithographic printing plates (I) to (I[I) using the photosensitive compositions of the present invention had excellent printing durability.

Procedural Amendment Commissioner of the Patent Office Black 1) Akio Yu 1, Indication of the case 1985 Patent Patent No. 225182
No. 2, Title of the invention Photosensitive composition 3, Person making the amendment.

Relationship to the case Applicant name (520) Fuji Photo Film Co., Ltd. 4, agent 5, ? Ii Date of original order Provision 6, Subject of amendment Detailed description of the invention in the specification column (1) Page 20, line 8 of the specification (D"Enyl/1 , 2-naphthoquinone-''.

(2) "Enyl 1,2-naphthoquinone-" in lines 11-12 of the same page of the same book is corrected to "enyl/1,2-naphthoquinone-".

(3) “Chromatography” in the second line of page 21 of the same book is changed to “
Chromatography” is corrected.

Claims (1)

[Claims] A photosensitive composition containing a polyurethane resin having an 0-quinonediazide group.