JPS61143748A - Photosensitive composition - Google Patents

Abstract

PURPOSE:To reduce tendency of a photosensitive compsn. to remain on nonimage parts and to prevent scumming in the case of using if for a lithographic plate by incorporating a specified compd. CONSTITUTION:The compd. is used as a free radical generating agent, it is 2-halomethyl-1,3,4-oxadiazole having a benzofuryl group, preferably, having one or 2 OH groups, at the 5-position directly or through a vinyl group, and it is soluble in water in a pH of >=9. A compd. causing interreaction with the photodecomposition product of said agent, such as a discoloring agent and an o-naphthoquinone diazide compd. is, preferably, incorporated together with it. When such a free radical generating agent is irradiated with light in a photosensitive resist forming compsn., it immediately discolor the coexisting discoloring agent and forms a visible image high in contrast. The photodecomposition reaction of said agent is rapid and not interrupted with the resist forming compsn., and it does not deteriorate the photosensitivity of the resist, and its stability with the lapse of time is good, and it has good storage stability when it is used for PS plates, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to photosensitive compositions containing novel photoactive radical generating compounds. For more details, see co-halomethyl/,! , relates to a photosensitive composition containing a Hiro-oxadiazole compound.

Compounds that silolyze to produce free radicals on exposure to light (
free radical generators) are well known in the graphic arts field. They are photopolymerization initiators in photopolymerizable compositions,
It is widely used as a photoactive agent in free radical photographic compositions and as a photoinitiator for reactions catalyzed by photogenerated acids. Printing, duplication, copying using such free radical generators 2
A variety of photosensitive materials are made that are useful in and other imaging systems.

Organic halogen compounds are photolyzed to form chlorine free radicals, J4.
Provides free radicals such as free radicals. These halogen radicals are good hydrogen abstractors and produce acids in the presence of hydrogen donors. El, pp. 1-370.

[Prior art]

Conventionally, carbon tetrabromide, iodoform, tribromoacetophenone, and the like are representative compounds that generate halogen free radicals by the action of light, and have been widely used. However, these free radical generators have sublimation properties or have a bad odor, so if they are used in a photosensitive material with a photosensitive layer provided on a support, they may cause damage during production, convenience, or storage of the photosensitive material. It volatilized from the photosensitive layer, reducing its effectiveness and posing a sanitary problem. Furthermore, these free radical generating agents have problems in compatibility with other elements contained in the photosensitive layer. Furthermore, they have low photodegradation sensitivity to the light sources (metal halide lamps, etc.) commonly used in the production of printing plates, so it was necessary to collect them in large quantities in order to show sufficient effectiveness. . When added in large amounts to the photosensitive layer, it has generally had a large adverse effect on the mechanical properties, developability, etc. of the photosensitive layer.

In response to this problem, JP-A No. 74 cm 7 Hiroshi 72 and JP-A-Sho! J-77714λ publication lists n,2-halomethyl- as a compound that generates halogen free radicals.
j-vinyl-/, j, 44-4xadiazolyl compound, cotrihalomethyl-j-aryl-7,3,
Photosensitive compositions using Hiro-oxadiazole compounds have been proposed. Furthermore, JP-A No. 71-71 discloses, as a compound generating a halogen free radical, 1-halomethyl-7,J,ttL, which is characterized by having a benzofuryl group at the 5-position either directly or via a vinyl group. -Oxadiazole compounds were proposed.

Especially Akira Tokukai! The oxadiazole compound disclosed in the T17RTI publication has excellent properties such as extremely high photodecomposition sensitivity to commonly used ultraviolet-rich light sources and excellent stability over time. However, when used as a component of a photosensitive composition in a lithographic printing plate, a portion of the photosensitive composition tends to remain in the non-image areas after development. In the case of development by rubbing, the photosensitive composition remained partially in the non-image areas, which not only caused unevenness and spoiled the appearance, but also often caused scumming when used as a lithographic printing plate.

[Purpose of the invention]

Accordingly, an object of the present invention is to provide a photosensitive composition that leaves a residual photosensitive composition in non-image areas after development and is less likely to cause scumming when used in a lithographic printing plate. Another object of the present invention is to provide a photosensitive composition with excellent stability over time (that is, the property of maintaining performance equivalent to that immediately after production even after long-term storage). Still another object of the present invention is to provide a photosensitive resist-forming composition a:J that exhibits high sensitivity to commonly used ultraviolet light sources.
The goal is to provide the following. Still another object of the present invention is to provide a photosensitive layer with excellent physical properties 2 and developability. Further objects of the invention will become apparent from the following description.

[Summary of the invention]

In order to achieve the above object, the Ministry of the Invention, etc. has completed the present invention as a result of various studies. co-halomethyl/ having a benzofuryl group directly or via a vinyl group; 3. A luminous composition containing a Hiro-oxadiazole free radical generator is used.

Here, the above "soluble" refers to dissolving at a concentration of 0.00λwt% or more, and alkaline water refers to hydroxide (hydroxide), silicic acid (hydroxide), etc. that does not contain organic solvents).
Indicates an aqueous solution of Jium.

As mentioned above, Tokukai Shojter/G! r7g≠ The publication states that co-lomemethyl-1,3 is characterized by having a benzofuryl group at the 5-position either directly or via a vinyl group.
, Hiro-Oxadiazole type free radical generating agent is disclosed, but this compound is insoluble even in alkaline water having a pH higher than or equal to, and in this point, it is substantially different from the present invention. That is, the main feature of the present invention is that it contains a free radical generating agent that is soluble in an aqueous alkali solution of E) H or higher,
This is probably why the photosensitive composition remains in the non-image area after development, making it extremely difficult for scumming to occur when used in planographic printing plates, for example, and the effect is not remarkable. be.

The free radical generating agent in the present invention preferably has a carboxylic acid group or a hydroxyl group in the benzofuryl group, and among these, those having a hydroxyl group are particularly preferred. The general formula of the preferred free radical generator of the present invention is shown below [! ] can be shown.

General formula CI) Here, X is all chlorine atoms or bromine atoms, Y is a hydrogen atom, a halogen atom, an alkyl group or an aryl group 'kA represents a benzofuryl group substituted with 1 to 1 hydroxyl group, is an integer, n is O or l.

The benzofuryl group substituted with 7 to 2 hydroxyl groups represented by A may be a cobenzofuryl group or a 3-benzofuryl group, and in addition to the hydroxyl group, the benzofuryl group may include an alkyl group, an alkoxy group, It may be substituted with groups or atoms such as cyano, nitro, phenoxy, phenyl and halogen atoms. Here, the alkyl group,
The alkoxy group preferably has 1 to 2 carbon atoms.

Examples of particularly preferred compounds in the present invention are shown below.

[Exemplary compounds]

0H The compound represented by the general formula [l] is, for example,
It is synthesized by dealkylating (or dealkylenating) the ether bond moiety of a compound represented by the following general formula [■] or (III), which is synthesized according to the synthesis method described in the tttryru publication. Ru.

General formula (n) General formula CII [) Goro crystal (here, X, YSmS n are synonymous with general formula CI). R represents a lower alkyl group or a benzyl group, l
is/or λ) The dealkylation (or dealkylenation) reaction of the ether moiety can be carried out using, for example, Organic 5ynthesi
s.

Co11ect Volume■, No. tLt/u ~
The method described in l'/page 44 (l. 73), M, Ge
Helvetica Chimi by Recke et al.
ca Acta, Volume J2, Volume 1! ! /~Ko! The method described on page j7 (l. 76), E. H. Vickery
et al., Journal of Organic C
hemistry, the method described in Volume 9, Volume 9, μ'IL4'Hiro - Hirohiro, μ6 pages (l. 7), M, Nod
E et al., Journal of OrganicC
Hemistry Chapter V! Volume, No. (, L27j, 142
This can be carried out according to the method described on page 77 (/10).

The photosensitive composition containing the free radical generating agent of the present invention contains at least one addition-polymerizable ethylenically unsaturated monomer or oligomer, for example, an acid-cleavable group such as a C-Q-C bond. It includes compounds that interact with photodecomposition products of free radical generating agents, such as compounds that develop, decolor, or change color with acids (hereinafter referred to as color change agents).

The free radical generating agent in the present invention can be added to a photosensitive cysost-forming composition for manufacturing lithographic printing plates, IC circuits, photomasks, etc., to immediately create a visible contrast between the unexposed area and the unexposed area without being developed upon exposure. This is particularly useful when providing the ability to print out (hereinafter referred to as printout ability). With a photosensitive resist composition having such printout ability, a visible image can be obtained only by exposure under a yellow safety light during exposure work. It becomes possible to know whether or not the plate given to the plate maker has been exposed, such as when the printing is interrupted. At the same time, for example, when a single large plate is exposed to light many times, as is the case with so-called plate printing when making lithographic printing plates, the operator must immediately check which part is the exposure source. I can do it.

The composition used to provide such printout ability (hereinafter referred to as print-act composition) contains a free radical generating agent and a discoloration that changes color due to the free radicals generated from the free radical generating agent. The free radical generating agent of the present invention is effectively used as the free radical generating agent.

In the present invention, as a color change agent, one that changes from an originally colorless state to a colored state due to the action of the photodegradation product of the free radical generating agent of the present invention, and one that changes color from an originally colorless state to a colored state, and a color change agent that changes color from an originally colorless state to a colored state due to the action of the photodecomposition product of the free radical generating agent of the present invention. There are two types: one that bleaches color and one that bleaches color.

Typical color changing agents used in the former type include arylamines. Arylamines suitable for this purpose include simple arylamines such as primary and secondary aromatic amines, as well as so-called leuco dyes, examples of which are as follows.

Diphenylamine, dibenzylaniline, triphenylamine, diethylaniline, diphenyl-p-phenylenediamine, T)) Luidine, Hiroshi.

≠′-biphenyldiamine, 0-chloroaniline, ゛O
-Bromoaniline, Hiro-chloro-0-phenylenediamine, 0-bromo-N,N-dimethylaniline 7, /
2, J-) I7 Phenylguanidine, naphthylamine, diaminodiphenylmethane, aniline, co,! −
Dichloroaniline, N-methyldiphenylamine, 0-
Toluidine, Ri+! ” -tetramethyldiaminodiphenyl meta y, N, N-dimethyl-p-7 22 diamine, l, codeianilinoethylene, p, p', p
”-hexamethyltriaminotriphaermethane, p,
p'-tetramethyldiaminotriphenylmethane, pr
p'-tetramethyldiaminodiphenylmethylimine,
1) TI)'lp"-triamino-0-methyltriphenylmethane, p, p', p"-triaminotriphenylcarbinol, p, p'-tetramethylaminodiphenyl-μm anilinonaphthylmethane, p, p′,
p"-triaminotriphenylmethane, p, p'rp"
-hexapropyltriaminotriphenylmethane.

In addition, examples of color-changing agents that originally have a unique color and whose color changes or decolors due to photodecomposition products of free-radical generating agents include diphenylmethane, triphenylmethane, thiazine, oxazine, and oxazine. Various dyes such as ten-based, anthraquinone-based, iminonaphthoquinone-based, and azomethine-based dyes are effectively used.

Examples of these are: Bu IJ I
J Ant Green, Eosin, Ethyl Violet, Erythrosin B1 Methyl Green, Crystal Violet, Pesic Tsuksin, Phenolphthalein, 1.
3-diphenyltriazine, Alizarin Red S, Thymol Phthalein/, Methyl Violet JB, Quinaldine Red, Rose Bengal, Methanil Yellow, Thymol Sulfophthalein, Xylenol Blue, Methyl Orange, Orange■, Diphenylthiocal/Z Syn, 2.7
-Dichlorofluorescein, paramethyl red, Congo red, benzo blue ring B1α-naphthyl red, Nile blue JB, Nile blue A1 phenacetaline, methyl violet, malachite green, rose 7 cucin, oil blue #603 [Orient Chemical Industry ■Drain], Oil pink #3/ko [manufactured by Orient Chemical Industry ■]
, Oil Red jB (manufactured by Orient Chemical Industry ■), Oil Blue Let #3ot [manufactured by Orient Chemical Industry @],
Oil Red OG (manufactured by Orient Chemical Industry ■), Oil Red RRC (manufactured by Orient Chemical Industry ■), Oil Green 910 (manufactured by Orient Chemical Industry ■), Spiron Red BEH Special (manufactured by Hodogaya Chemical Industry ■), m-cresol purple, Cresol red, Rhodamine B10
- Damin 4G.

First Acid Violet R1 Sulphorodamiy
13. Auramine, ψ-p-diethylaminophenyliminonaphthoquinone, λ-calfoquinanilinohiro-p-
Diethylaminophenylimino naphthoquinone, cocarbostearylaminog-p-dihydroxyethyl-
Amino-phenylimino naphthoquinone, p-methoxybenzoyl-p'-diethylamine-〇'-methylphenyliminoacetanilide, cyano-p-diethylaminophenyliminoacetanilide, 1-7enyl-3-methyl-hiro-p-diethylaminophenylimino- -pyrazolone, 1-β-f7fk-4'-p-diethylaminophenylimino-yo-pyrazolone.

In printout compositions according to the invention, the free radical generators of the invention are stable over time, but among those used as color changing agents, leucotriphenylmethane dyes are generally susceptible to oxidation. Therefore, when using these dyes, it is effective to include some kind of stabilizer. A US patent for a stabilizer for this purpose! , 0μ2. ! Amines, zinc oxide, and phenols described in Specification No. 73, 3,0 Hiroshi λ,! lt specification' (Sulfur compounds described in FIC, 3
゜0μm, alkali metal iodides described in the specification of No. 111, organic version, organic anhydrides described in the specification of 1 Kamo JC #20It, antimony, arsenic, bismuth, phosphorus described in the specification of No. 3377/67. Triaryl compounds are effective.

The ratio of the above-mentioned color change agent and the free radical generating agent in the present invention is about 700 parts by weight, more preferably 0.00 to 700 parts by weight of the free radical generating agent in the present invention per 1 part by weight of the color change agent. /~io parts by weight, most preferably O0! ~j
Used within the range of heavy ligatures. Further, they may be used in combination with the free radical generating agent in the present invention.

On the other hand, the photosensitive resist-forming composition, which is the object to which printout ability is imparted by the printout composition according to the present invention, can be used to prepare various printing plates such as lithographic printing plates, ICO paths, photomasks, etc. be redeemed for the purpose of Includes oaks. The representative ones include (1
) a composition made of a diazo resin, (2) a composition made of an 0-quinonediazide compound, (3) a composition made of a photosensitive azide compound, (4) a composition containing -CH-CH in the main chain or side chain of the polymer.
Composition consisting of a polymer compound containing a -Co- group, (5)
A photopolymerizable composition comprising an addition-polymerizable unsaturated compound and a photopolymerization initiator is included, and details of these compositions are described in U.S. Pat. ! It is described in column r, line 11 to column ii, line 31 of the specification of No. 2.

When such a photosensitive resist-forming composition contains the printout composition, the printout composition is added in an amount of about 0.1 parts by weight to ioo parts by weight of the photosensitive resist-forming composition. It can be contained in an amount of about 710 parts by weight, more preferably in a range of 7 to 40 parts by weight.

Solvents used when coating the photosensitive resist-forming composition imparted with printout ability in this way include ethylene dichloride, cyclohexanone, methyl ethyl ketone, λ-metho? Diethyl acetate, monochlorobenzene, toluene, ethyl acetate, etc.
These may be used alone or in combination of λ or more.

It is advantageously used as a photosensitive layer provided with such printout ability. In this case, the support is
For example, aluminum (also includes aluminum alloys).
, metal plates such as zinc, iron, copper, etc., plastics laminated or vapor-deposited with such metals, and most preferably aluminum plates. In the case of supports with a surface of metal, especially aluminum, graining treatment,
It is preferable that the surface be treated by immersion in an aqueous solution of sodium silicate, potassium fluorozirconate, g% acid salt, or the like, or by anodizing with lubricious Fi.

Further, as described in British Patent No. 11/119, an aluminum plate which has been grained and then immersed in an aqueous sodium silicate solution or anodized in acid, US Patent No. 3, /I/.

An aluminum plate which has been anodized and then immersed in an aqueous solution of an alkaline earth silicate as described in ≠No. 67 is also suitably used. The above-mentioned anodizing treatment can be carried out using, for example, an aqueous or non-aqueous solution of an inorganic acid such as phosphoric acid, chromic acid, sulfuric acid, or boric acid, or an organic acid such as oxalic acid or sulfamic acid, or a salt thereof, either alone or in combination. Among these, the method is particularly preferably carried out by applying electric current to an aluminum plate as an anode in an aqueous solution of phosphoric acid, sulfuric acid, or a mixture thereof. Also, US Patent No. 3.6! Electrodeposition of silicate as described in R.R., No. 662 is also effective.

Furthermore, British Patent No. 1. Also preferred is an aluminum plate obtained by electrolyzing an aluminum plate in an alternating current electrolyte in a hydrochloric acid electrolyte and then anodizing it in a sulfuric acid electrolyte, as described in Koor, Co. No. 24L. Further, it is preferable to provide an undercoat layer of a cellulose resin containing a water-soluble salt of a metal such as zinc on the aluminum plate anodized in the above process in order to prevent scum during printing.

The amount of photosensitive layer provided on such a support is approximately O0
l ~ about 79/m2, preferably O0! ~Hiroshi? /
m range.

The thus obtained PS plate is subjected to image exposure, and then an image is formed by processing including development using a conventional method.

For example, in the case of a PS plate having a photosensitive layer made of a photosensitive composition in which the above-mentioned composition (1) made of diazo resin contains a printout composition, after image exposure, the unexposed portions of the photosensitive layer cannot be developed. A lithographic printing plate is obtained by removing the scratches. In the case of a PS plate having a photosensitive layer made of a photosensitive composition containing a printout composition in the composition (2) above, after image exposure, the exposed portion is removed by developing with an aqueous alkaline solution. A lithographic printing plate is obtained. No matter what type of photosensitive layer the PS plate has, no special measures are required due to the present invention (improving printout ability), and conventionally known developers suitable for each photosensitive composition can be used. can be developed.

The photosensitive resist-forming composition imparted with the above-mentioned printout ability can be used for producing printing proof plates, films for overhead projectors, films for original drawings, and lumens. Suitable supports include transparent films such as polyethylene terephthalate film and cellulose triacetate film, and these plastic films whose surfaces have been chemically or physically matted.

Moreover, the above-mentioned composition can also be used for manufacturing a film for a photomask. Suitable supports include aluminum, an aluminum alloy, a polyethylene terephthalate film on which chromium is vapor-deposited, and a polyethylene terephthalate film provided with a colored rattan.

Furthermore, the composition described above can be used as a photoresist. In this case, a color change agent that decomposes and coexists when exposed to light in a photosensitive resist-forming composition containing various cyst-forming compounds such as a copper plate, a steel plated plate, a stainless steel plate, a glass plate, etc. It is surprising that the color can be changed efficiently and instantly. As a result, a clear boundary is obtained between the exposed and unexposed areas, which can be recognized as a visible image with rich contrast.

Further, since a wide range of color change agents can be used in one process, an appropriate color change agent can be selected when various color additives are added to improve the performance of the photosensitive composition.

Additionally, the free radical generators used in the present invention remain stable over time, thereby improving the shelf life of these articles, for example when used in PS plates.

Furthermore, the photodecomposition reaction of the free radical generating agent in the second aspect of the present invention is very fast and is not inhibited by the coexisting photosensitive resist-forming compound, so that even a small amount added can be effective.

Furthermore, since the free radical generating agent in the present invention does not significantly inhibit the photodecomposition of the photosensitive resist-forming composition, for example, the above-mentioned compositions (1) and (2), the photosensitivity (resist (photosensitivity) does not decrease significantly. Furthermore, since the free radical generating agent according to the present invention is effective when added in a small amount, the photosensitive resist-forming composition can be obtained after image exposure and development, and the physical characteristics of the cyst image do not deteriorate. Even if the photosensitive resist-forming composition imparted with printout ability according to the present invention is used as the photosensitive layer of a photosensitive lithographic printing plate, the developability, oil sensitivity, printing stain, and printing durability of the printing plate obtained are as follows: Various physical properties such as properties are the same as when no free radical generator is added.

′ [Example] The present invention will be explained in more detail below with reference to Examples. Note that "%" indicates weight unless otherwise specified.

Example 1 The following photosensitive solution was applied to an aluminum plate with a thickness Q of 2 μmm, the surface of which had been grained and then anodized, and the photosensitive solution was
Dry for a minute.

Esterification reaction of naphthoquinone-(/,co)-diazide-+21-7-sulfonyl chloride and Talezol novolak resin xenobiotics 0.7! F Cresol novolac resin C, ioy Tetrahydro anhydrous 7
Taric acid 0. /If free radical generator (listed in Table 1) o, o#y crystal violet
o, oty Oil Blue 0603 (manufactured by Orient Chemical Industry Co., Ltd.) Even, ρl ethylene dichloride / If comethoxyethyl acetate lλ2 The coating solution after drying is: / ? /
It was 7FL 2. Each of these photosensitive lithographic printing plates was exposed to light for .mu.O seconds using a KW metal halide lamp through a positive transparent light from a distance of . The optical density of the exposed and unexposed areas of the photosensitive layer was measured using a Macbeth reflection densitometer.

The image obtained by exposure appears sharper as the difference (ΔD) between the optical a degree of the exposed area and that of the unexposed area is larger. i gray scale (after exposing two adjacent stages under similar conditions, Gc sodium thimeta silicate aqueous solution @C
I immersed it in water for 1 minute and checked the resist sensitivity't--good. Sensitivity was indicated by the number of solid steps (the higher the number of steps, the higher the sensitivity).

Also, after exposing in the same way as above through a positive transparent cost price,
The image was developed by rubbing with a sponge impregnated with a Hirochi sodium metasilicate aqueous solution, and unevenness in the non-image area (hand development unevenness) f: was investigated. Table 1 shows those with almost no unevenness in hand: 1-0.
．． Items with uneven hand appearance are marked with an x.

On the other hand, in order to examine the ease with which dirt (scumming) appears,
These photosensitive lithographic printing plates were treated with a tired developer, and the presence or absence of stains was examined using a printing press. The results are shown in Table 19.

As is clear from Table 1, according to the present invention, it was possible to provide a printout image, without lowering the sensitivity of the resist, and without causing unevenness in non-image areas during development. .

In addition, with the known free radical generating agent cited as a comparative example, stains occur in the exhausted developer and fc (experiment/1tL7, grave), whereas with the free radical generating agent of the present invention, stains do not occur,
It can be seen that the present invention is extremely superior.

Example 2 The following photosensitive solution was applied to an aluminum plate and dried in the same manner as in Example 1.

Copolymer of methyl methacrylate and methacrylic acid (copolymerization molar ratio = 2:/) 0. Trimethylolpropane triacrylate 0. Jrf Kobe/
Zoylmethylene-3-methyl-β-naphthothiazoline
0. 0 λ? Free radical generator [Exemplary compound (1)]
o, o<<y leuco crystal violet o,
ooze methyl ethyl ketone is
The coating amount after drying was λ, j 9 / 7rL2. When this photosensitive lithographic printing sheet metal was exposed to light through a transparent negative in the same manner as in Example 1, the exposed portions were colored purple and a printed image (printout) with rich contrast was obtained.

Then caustic no-dye I, iy, isopropyl alcohol J
A lithographic printing plate was obtained by removing the unexposed areas with a developer consisting of OOml and water ooILt. (2) When a photosensitive solution was used in which the free radical generator (exemplified compound (1)) was excluded from the above photosensitive solution, almost no printed image appeared even when exposed in the same manner.

Example 3 The following photosensitive solution was applied to the photorecoated aluminum plate used in Example 1 using a Whaler. Drying was carried out for 100 minutes.

p-)Luenesulfo/acid acid of condensate of p-diazodiphenylamine and paraformaldehyde 0.2 ? Polyvinyl formal 0, 7'? Free radical generator [Exemplary compound (2)) 0, 0 t Crystal Violet 0.021 Comethoxyethanol λQ2 Methanol
Yo ? Dry applied ligature /, 0? / Rarely happened in WL2. When this photosensitive lithographic printing plate was exposed to light for 3Q seconds from a distance of 70 mm using the i/kW metalnoride plate, a clear printed image with rich contrast was obtained in which the exposed areas were discolored.

In addition, in the photosensitive solution, a free radical generating agent (exemplary compound f2)
When the photosensitive liquids except for No. 31 were used, clear printout images could not be obtained.

Example 4' In the same manner as in Example 1, the following photosensitive solution was applied to an aluminum plate and dried.

Polyester synthesized by condensation of p-7 22-ethyl diacrylate and equimolar amount of l,1-bis-1β-hydroxyethoxy7-cyclohexane (molecular weight approximately r, ooo > o, r t cobenzoylmethylene-3- Methyl-β-naphthothiazoline 0.OJf free radical generator (exemplified compound α4)) o, oory leuco crystal violet o, oozt monochlorobenzene 2 ethylene dichloride 6 ? The amount of application after drying is /,z?
/m. When this photosensitive lithographic printing plate was exposed through a transparency in the same manner as in Example 1, a printed image rich in contrast was obtained. The surface was then developed by wiping with a developer having the composition shown below to obtain a lithographic printing plate. In addition, in the above photosensitive solution, a free radical generating agent [exemplified compound α
Compared to the case of using a photosensitive liquid without the chlorine, the printout image was clearly clearer, and the sensitivity of the resist was almost the same.

Developer composition

Claims (1)

[Claims] 1. A 2-halomethyl-1,3,4-oxadiazole free radical generating agent having a benzofuryl group at the 5-position directly or via a vinyl group, which is soluble in alkaline water with a pH of 9 or more. A photosensitive composition containing. 2. Claim 1, wherein the benzofuryl group of the oxadiazole has 1 to 2 hydroxyl groups.
The photosensitive composition described in . 1-2 at the 5th position of the 3,1,3,4-oxadiazole nucleus
A benzofuryl group having hydroxyl groups interacts with the 2-halomethyl-1,3,4-oxadiazole free radical generator bound directly or via a vinyl group and the photodecomposition product of the free radical generator. A photosensitive composition containing a compound. 1-2 at the 5th position of the 4,1,3,4-oxadiazole nucleus
A 2-halomethyl-1,3,4-oxadiazonyl free radical generator to which a benzofuryl group having hydroxyl groups is bonded directly or via a vinyl group, a compound that interacts with a photolysis product of the free radical generator, and A photosensitive composition containing an o-naphthoquinone diazide compound.