JPS603626A - Photosensitive composition - Google Patents

Abstract

PURPOSE:To obtain a photosensitive compsn. hardly remaining on nonimage areas after development and suitable for use in a lithographic plate, etc. by incorporating a specified oxazole compd. and a compd. causing interreaction with the photo-decomposed product of said compd. CONSTITUTION:An intended photosensitive compsn. is obtained by incorporating (A) an oxazole compd., such as ones of formulae II and III, represented by general formula I in which X is H, alkyl, or aryl; Y is F, Cl, or Br; n is 1-3; m is 1 or 2; and l is 0 or 1: and (B) a compd. causing interreaction with the photo-decomposed product of said compd. (A). Said component (B) is exemplified by an additionally polymerizable ethylenically unsatd. monomer, and a compd., such as diphenylamine, colorable, decolorable, or discolorable with an acid. The compd. of formula II typical of the component (A) can be easily synthesized with the starting materials of p-methoxycinnamic acid and p-nitrophenol.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to photosensitive compositions containing novel photo-generated free radical compounds. More specifically, 2-1-lomethyl-l, 3. This invention relates to a photosensitive composition containing a ≠-oxadiazole compound.

Compounds that decompose to produce free radicals on exposure to light (
Free radical generators) are well known in the field of graphic arts. They are photoinitiators 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. Such free radical generators are used to make a variety of photosensitive materials useful in printing, duplication, copying and other imaging systems.

Organohalogen compounds photolyze to give chlorine free h(, bromine free radicals... halogen free radicals +1). These halogen free radicals are good hydrogen abstracting agents, and in the presence of hydrogen donors produce acids.Those PPE6/~37
It is written in 0.

Due to the action of this type of light, compounds that generate R1 radicals include carbon tetrabromide, iodoform,
Typical examples include tribromoacetophenone,
It has been widely used. However, since these free radical generating agents sublimate or have a bad odor, if they are used in a photosensitive material with a photosensitive layer provided on a support, the photosensitive layer may be damaged during manufacture, use, or storage of the photosensitive material. The effect is reduced by volatilization from fc.

It became a sanitary problem. Furthermore, these free radical generating agents have problems in compatibility with other elements contained in the photosensitive layer. Furthermore, they can be used, for example, during the production of printing plates (
Because the sensitivity of photolysis to commonly used light sources (metal halide lamps, etc.) is low, it was necessary to add large amounts to exhibit sufficient effects. When added in a large amount to a photosensitive layer, it has usually had a large adverse effect on the mechanical properties, phenomenon, etc. of the photosensitive layer.

To solve this problem, JP-A-4T-747, JP-A-1.1, and JP-A-36-777-2 disclose compounds that generate halogen free radicals, such as λ-88tmethyl-1vinyl, respectively. /, 3, Hiro-4 xadiazol compound,')! J Halomethyl! -Arry Lou/, 3
．． Photosensitive compositions using 41-oxadiazole compounds have been proposed. Such compounds have excellent stability over time and are highly sensitive to photolysis against commonly used ultraviolet light sources. However, when used as a component of the photosensitive composition of a lithographic printing plate, a portion of the photosensitive composition tends to remain in the non-imprinted area after development (particularly when absorbent cotton,
When developing by soaking a developing solution into a sponge or the like and rubbing it, the photosensitive composition may remain partially in the non-image areas, becoming uneven and damaging the appearance, and when used as a lithographic printing plate. is often less likely to leave photosensitive compositions,
When used in planographic printing plates, ij1! has a photosensitive composition that does not easily cause scumming. It is to provide. Another object of the present invention is to provide a photosensitive composition that is stable over time (i.e., maintains the same performance as immediately after production even after being stored for a long time). be. Still another object of the present invention is to provide a light source for commonly used ultraviolet light.
An object of the present invention is to provide a photosensitive resist-forming composition exhibiting high sensitivity. Still another object of the present invention is to provide a photosensitive layer with excellent physical properties and developability. Further objects of the invention will become apparent from the following description.

In order to achieve the above object, the present inventors have made the present invention as a result of repeated research, which includes (a)
This is a photosensitive composition containing an oxadiazole compound represented by the following general formula (I) and (b) a compound that interacts with a photodecomposition product of the oxadiazole compound.

) (Here, X is a hydrogen atom, an alkyl group, or an aryl group,
Y is a fluorine atom, a chlorine atom, or a bromine atom, and n is /~3
m is an integer from / to ko, l is O or / and does not represent an integer. ) In the above general formula (I), X is a hydrogen atom, the number of carbon atoms/~
Among the alkyl groups and aryl groups mentioned above, particularly preferred alkyl groups are methyl and propyl groups, and examples of the aryl groups include phenyl groups.

As mentioned above, Tokukaisho! ≠-74t721 Public: 1 En and Tokukai Sho! ; J-777 Kou No. 2, λ-halomethyl, 1-vinyl-/, 3. '+-Oxadiazole compound, 2-tri/10 methyl-! -Arry Lou/, 3. Although Hiro-oxadiazole compounds are disclosed, the compound represented by the above general formula (I) used in the present invention is characterized in that it contains a phenolic OH group, which makes it difficult to use after development. An effect is achieved in which the photosensitive composition does not remain in the non-image area of the image.

The compound represented by the general formula (1) is, for example,
3-. 2≠//3 Publication, U.S. Patent No. 2.23, l
The ether bond moiety of the compound of the following general formula m or It is synthesized by (* means dealkylenation).

N- to λ General formula (where, The dealkylation (or dealkylenation reaction) of the ether bond moiety of the compounds of
nic 5yntheses+CoCo11ectvo
lu V, II / 2-II / tl-(/ri7
3), by M. Gerecke et al., Helv
eticaChimica Acta+ jri, J, j
The method described in j/, -, 2jj7 (/ri76), E, H
, Vickery et al., Journal of Or
Ganic Chemistry.

The method described in Guru Hiromu, II Hiro≠μ～Hiro≠Hirot (/ri7ri), or the method described in M. Node et al., Jo□urnal o
fOrganic Chemistry,'A-j,
It can be carried out according to the method described in Ko 27j-'il' 277 (/10).

Hereinafter, specific compounds represented by the general formula (I) used in the present invention will be illustrated, and some synthesis examples will be shown.

/I6/ /162 H 63 (Jtl /f64t //6t /167 \ H Synthesis example 1 2-trichloromethyl-j~(p-hydroxystyryl)-/, 3.'t-oxadiaso°-/shik1 hydrating compound 16/) Synthesis/7. Ii of p-methoxycinnamic acid and 13゜95J of p-
Nitrophenol 6 r Oml's thionyl and j
The mixture was heated under reflux for 1 hour in aqueous benzene. After distilling the j+3 residue of thionyl chloride and benzene, the solid obtained was washed with water and then dried. 1) -Methoxytetrazoic acid p'-nitrophenyl ester was obtained substantially according to theory.

p-Methoxy 41 dinic acid p'-nitrophenyl ester I
1. O9 was added to a solution of 0% hydrazine hydrate, tt, ag and 7 mL of methanol, and the mixture was heated for 30 minutes. L was refluxed. After cooling the reaction solution, add triethylamine t.

3 g was added and pressurized to 4'00 ml of water. Colorless p-titoxycarnamic acid hydrazide 7 and hydrazide precipitated.

The mixture was added to a solution of -2g of p-methoxybenzoic acid hydrazide, 0.2I of hexachloroacetone and 100% acetonitrile, and heated under reflux for 1.20 minutes.

When the reaction layer is cooled, a colorless foil of N-p-methoxycinnamoyl-N'-trichloroacetylhydrazide 30,
1 g was precipitated.

N-p-methoxycinnamoyl-N'-trichloroacetyl hydrazide and oxychloride were heated to reflux for 15 liters for 3 hours, then divided into 〇〇g of ice water. The resulting precipitate was recrystallized from methanol and coated with chloride. O)' Chiru! -(p-methoxystyryl)-/, 3. Guoxadiazole λ. I got it.

1 disaster methylene, 2 o mi! Anhydrous aluminum chloride/6.9 was added to the solution, and while stirring at room temperature, 2-
Trichloromethyl-1-(p-methoxystyryl)-/
, 3. Hiro - Oxadiazole/Hiro! J is methylene chloride
A solution dissolved in ome was added dropwise. After the dropwise addition, the mixture was stirred at room temperature for 7 hours to continue the reaction.

After washing the reaction solution with ice-cold water, methylene chloride was distilled off under reduced pressure. The remaining solid after erasure was recrystallized from a mixed solvent of fNli M ethyl and n-hexane to give 2-trichloromethyl-j~(p-hydroxystyryl)/,
3. 'l--Oxadiazole (X point/79-/Ir0
0C) 9.1. g'Il-obtained.

Synthesis Example 2 1-Trichloromethyl-3-(3',t'~dihydroxystyryl)-/, 3. 'Synthesis of I-oxadiazole (exemplified compound/16J) 3, Hiro-methylenedioxycinnamic acid, 2. a, 17°p-
Nitrophenol, 3 gY) Luene 601n
After adding 33.1 g of thionyl chloride to the mixture, the mixture was heated under reflux for 2 hours. After distilling off excess thionyl chloride and toluene, 3. ≠2 g of ≠-methylenedioxycinnamic acid 'A'-nitrophenyl ester was obtained.

3, ≠-methylenedioki/1 kepi r ≠'-nitrophenyl ester 3/, 3g and KO% hydrazine hydrate l
Add 1 g to methyl alcohol/23 md,
The mixture was heated to reflux for an hour. After cooling, the reaction mixture is mixed with water 7θθd
K was added, and the resulting precipitate was separated in a furnace to give 3,≠-methylenedioxybenzoic acid hydrazide.

I got 7g.

3. Hiro-methylenedioxycinnamic acid hydrazide 77.6g
Hexachloroacetone 26.39 to acetonitrile 1
The mixture was heated under reflux for 30 minutes. By cooling the reaction solution, N-(3,a-methylenedioxy/
Nonamoyl) -N'-1! J chloroacetyl hydrazide r1.29 was obtained.

N-(j,!-methylenedioxycinnamoyl)N/
) Lichloroacetyl hydrazide〇,.

Add phosphorus oxychloride/zoml to g, heat under reflux for 3 hours, then pour the reaction solution into ice water, filter the resulting precipitate,
Recrystallized from methanol to give -trichloromethyl-j
(3/, Hiro'-methylenedioxystyryl)-/, 3
．． ta-oxadiazole/l,/9 was obtained.

Methylene chloride, anhydrous aluminum chloride in 20ml//g
Add ethanedithiol while cooling on ice! ml and add λ-trichloromethyl-(j/, t, t
/-methylenedioxystyryl)-/.

3. 6.7 I of Hiro-oxadiazole was added.

After the reaction solution was returned to room temperature, the reaction was continued for an additional 3 hours. After washing the reaction solution with ice-cooled water, methylene chloride was distilled off under reduced pressure, and the residue was recrystallized from a mixed solvent of ethyl acetate and n-hexane to give 2-trichloromethyl-'j-(
j', l-dihydrochinstyryl) -/ , 3, ≠
-Oxadiazole (1・″1.J! point/i3~/I!
0C) 3°7pY was obtained.

Synthesis Example 3 Cochloromethyl-j-(p-hydroxystyryl)-
/, 3.41-oxadiazole (Exemplary compound/167
) Synthesis of the intermediate p-methoxymalt hydrazide obtained in Synthesis Example 1, and monochloroacetic anhydride/.

7g and acetic acid/! rul mixture for 30 minutes at room temperature! il
l! :: ≧ Stirred. The precipitate obtained by removing the water was recrystallized from a mixed solvent of methanol and water to obtain N'-p-methoxycinnamoyl, IN'-chloroacetyl hydranide o, rg.

N-p-, J), Ya, /, 7yo E-N・-ri. . 1
Acetyl hydrazide o, rg and phosphorus oxychloride 1Orr
After heating under reflux for 7 hours, the reaction solution was poured into ice water; the precipitate that leaked out was recrystallized from ethanol to give cochloromethyl-j-(p-methoxystyryl)-/.

3. Hiro-oxadiazole was obtained.

Add 10 g of anhydrous boron tribromide to 20 ml of methylene chloride, cool to 70 CvC, and add 2-chloromethyl-!;-(p-methoxystyryl)-/, 3.I with stirring.
5 g of I-oxadiazole was added to 110 vtl of methylene chloride.
was added dropwise. After the dropwise addition, the reaction was continued at -200C for 2 hours and at room temperature for 3 hours. After washing with ice-cold water, methylene chloride was distilled off under reduced pressure, and the residue was recrystallized from a mixed solvent of ethyl acetate and n-hexane. -(p-hydroxystyryl)
-/, 3゜Hiro-oxadiazole (melting point /74'~/7
j-'C) 3.39 was obtained.

Synthesis Example 4 Synthesis of λ-° trichloromethyl-3-(3', Hiro'-dihydroxyphenyl) -/, J, ≠-oxadiazole (exemplified compound A6/j) 3, methylta methoxybenzoate, ♂g (0,03
mol) and Irjt% hydrazide hydrate 7/jml were rapidly flowed for 2-s for 3 hours without stirring. The reaction solution was cooled, and the resulting crystals were separated in a furnace and washed with water to obtain 3゜Hiro-dimethoxybenzoic acid hydrazide. The yield was quantitative.

3 obtained above, ≠l dimethoxybenzoic acid hydrazide 3
．． ri g (o, oλ moles) otrichlor: (tonic anhydride 6
．． 2 g (0.0 λ mol) of the solution was added under concealed stirring, and stirring was continued for 30 minutes. Then, phosphorus oxychloride izg (o, i mol) was added, and the mixture was refluxed with stirring for 3 hours. After cooling this reaction solution, it was poured into 300 g of crushed ice. The generated precipitate is P
After collecting, washing with water and drying, it was recrystallized from ethyl acetate to obtain λ-trichloromethyl-1-(J',≠'-dimethoxyphenyl)-/, J, Hiro-oxadiazole r, og.

Add 10〃 of anhydrous boron tribromide and jml of ethanethiol to xornl of methylene chloride, and while cooling to θ0C, prepare λ-trichloromethyl-5 (3/, tl/l dithoxyphenyl)-/, 3.1-L. Oxadiazole j
A solution prepared by dissolving 20 g of methylene chloride was added dropwise. After dropping, the reaction was continued for 2 hours at -200℃ and 3 hours at room temperature. After washing with ice-cold water, methylene chloride was distilled off under reduced pressure, and the residue was recrystallized from ethyl acetate. and coat trichloromethyl-3 (3/, 4t
3.7 g of 1-dihydroxyphenyl)-/3.41-oxadiazole (melting point/Taco-19g 0C) was obtained.

Synthesis Example 5 λ-Trichloromethyl-3-(p-hydroxyphenyl)'p3r4'-oxadiazole (Exemplary Compound/16
Synthesis of //) 8. The above compound was obtained by the same method as in Synthesis Example 4 using methyl p-methoxybenzoate as a raw material.

Melting point/Hiro 7~/Hiro 0C Synthesis Example 6 -2-Tribromomethyl! -(p-hydroxystyryl)-/, 3,4t-oxadiazole (exemplary compound/
Synthesis of Synthesis Example 16) The intermediate p-methoxybenzoic acid hydrazide 73I obtained in Synthesis Example 1 was dissolved in dioxane/l0mlK and then mixed with tribromoacetic acid bromide with stirring.

2g was added dropwise during io sorting. After stirring this reaction solution at room temperature for a long time, the resulting precipitate was filtered out. Water in p liquid? :200
After adding m1, it is cooled and N-p-methoxycinnamoyl-
N/), Libromore hair tilhydrazide♂. A crystal of ♂y was obtained.

This crystal 3゜g and phosphorus oxychloride 2θ1nl f; 3
(After heating under reflux for / hour, the reaction solution was poured into ice water, and the resulting precipitate was recrystallized from ethyl acetate to give 2-tribromomethyl-!-(p-methoxystyryl)-/.

3. 2.0 g of Hiro-oxadiazole was obtained.

Methylene chloride 2 omlvc anhydrous aluminum chloride λ.

θI was added, and while stirring with a iron at room temperature, 2-tribromomethyl-! -(p~methoxystyryl)-/,! ,l
A heart fluid prepared by dissolving I-oxazole/6j9 in methylene chloride Q- was added dropwise. After the dropwise addition, the mixture was further stirred at room temperature for 7 hours to continue the reaction. After pouring the reaction solution into ice water, washing with water was repeated (repeatedly). Methylene chloride was distilled off under reduced pressure at 1.
The solid fl is recrystallized from ethyl iliate,
2-Tribromomethyl-! -(p~hydroxystyryl)-/, 3. ≠-Oxazole (work point 17ri~/g/
0C)/, /I were obtained.

The compound represented by the general formula (I) has a wavelength of about 230 nm to about ! When irradiated with actinic radiation within the range of 0.00 nm, it generates free radicals very efficiently.
(a) A compound that generates free radicals when irradiated with actinic rays (free radical generating agent) and (b) A compound that interacts with the photodecomposition product of the free radical generating agent as essential components. Photosensitive compositions, e.g., photosensitive materials used for making printing plates such as lithography, letterpress, intaglio, etc., photoresist materials and other photographic elements used for producing 1' photosensitive compositions and exposure only. Therefore, when the compound represented by the above general formula (I) is used as the free radical generator of a photosensitive composition that immediately provides a visible contrast between the unexposed area and the unexposed area, a highly sensitive photosensitive composition can be obtained. It will be done.

Component (I) above may be an addition polymerizable ethylenically unsaturated monomer or an oligomer, such as c-o
- At least one acid cleavable group such as a c bond
It includes a variety of compounds, such as compounds that have their own properties, and compounds that develop, discolor, or change color with acids (hereinafter referred to as color-changing agents).

The compound represented by the general formula (1) in the present invention is:
A photosensitive resist-forming composition for producing lithographic printing plates, IC circuits, photomasks, etc. has the ability to immediately provide visible contrast between the unexposed area (hereinafter referred to as printout) without being developed by exposure to light. This is sometimes useful when the photosensitive resist 4111 composition having such printout ability can obtain a visible image only by exposure under a yellow safety light during the exposure operation. For example, in the process of exposing many printing plates at the same time, it is possible to know whether a plate given to the platemaker has been exposed or not, eg when work is interrupted.

At the same time, for example, when making a lithographic printing plate, the so-called printing plate 1
When a large plate is exposed to light many times, as in Akatsuki, the operator can immediately tell which part is the exposure method.

The composition used to impart such printout ability (hereinafter referred to as printout composition) changes color due to the free 11fffl group generating agent and the free radicals generated from the free radical generating agent. According to the present invention, a compound represented by the general formula (I) is 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 a photodecomposition product of a free radical generator (a compound represented by the general formula T);
There is a problem with things that originally have a unique color becoming discolored or bleached.

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, p-toluidine, Hiromu.

Hiro'-biphenyldiamine, 0-chloroaniline, o-
Bromoaniline, Hiro-chloro〇-phenylenediamine, o-bromo-N,N-diethylaniline, 'l'
p 3) Riphenylguanidine, naphthylamine,
Diaminodiphenylmethane, aniline, J, t-dichloroaniline, N-methyldiphenylamine, o-toluidine, I) + ])'-detramethyldiaminodiphenylmethane N, N'-dimethyl-p-phenylenediamine, /, 2 -dianilinoethylene, I)yl”+1
) “-hexamethyltriaminotriphenylmethane, 1
) II)'-tetramethyldiaminodiphenylmethane, I) ILI'-tetramethyldiaminodiphenylmethylimine, ppp'pp"-triamino-0-methyltriphenylmethane, p'+1)" F riaminotri 1 phenyl Carbinol, I) + 1)'-tetramethylaminodiphenyl-Hiro-anilinonaphthylmethane, p
, p', p"-triaminotriphenylmethane, rijl
)'91)“-hexapropyltriaminotriphenylmethane.

In addition, examples of color-changing agents that 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 xanthine-based agents. , anthraquinone-based, iminonaphthoquinone-based, azomethine-based dyes, and the like are effectively used.

Examples of these are: Brilliant green, eosin, ethyl violet, erythrosin B1 methyl green, crystal violet, pacific tuxin, phenolphthalein, /, 3-diphenyl triazine, alizarin red S1 thymolphthalein, methyl violet, 2B, quinalzine red, rose bengal , methanyl yellow, thymol sulfophthalein, xylenol blue, methyl orange,
Orange ■, diphenylthiocarbazone, λ, 7-dichlorofluorescein, paramethyl red, Congo red, benzopurpurin + B, α-naphthyl red, Nile blue 2f3. Nile Blue A1 Phenacetalin, Methyl Violet, Malachite Green, /ξMiratsukufun Oil Blue 1 #403 [manufactured by Orient Chemical Industry ■], Oil Pink #3/, 2. (Orient Chemical Industry t
, +*sr, Oil Red tB (Orient Chemical Industry ■
], Oil Blue Let #30g [Orient Chemical Industry (110-11'! J1 Oil Red OG [Orient Chemical Industry (opened)], Oil Red RR [Orient Chemical Industry (Pray! t'! J, Oil Green #, !r0
2 [Manufactured by Orient Chemical Industry Yifin], Spiron Red BEH Special [Hodo G Chemical Industry ('M:) 4iJ
,] ,] m-cresol ξ-pur, ri''/Zol Red, rhodamine B, rhodamine, 4G, fast acid violet it, sulforhodamine B1 auramine, Hiro-p-diethylaminophenylimino naphthoquinone, cocarboxy7anilino≠-p- Diethyla ξnophenylimino naphthoquinone, λ-carbostearylaminophenyl p-dihydroxyethylaminophenyl nonaphthoquinone, p-methoxybenzoyl-p
'-Diethylamino-07-methylphenyliminoacetanilide, cyanop-diethylaminophenyliminoacetanilide, /-phenyl-3-methyl-
p-diethylaminophenyl ibanoterpyrazolone,
/-β-naphthyl-≠-p-diethylminophenylimino! -Pyrazolone.

In the printout composition according to the invention, the general formula (
The compound represented by I) is stable over time, but among those used as color changing agents, leucotriphenylmethane dyes are generally easily oxidized.

Therefore, when using these dyes, it is effective to include some kind of stabilizer. Stabilizers for this purpose include US Pat. θgλ,! 7! Amines, zinc oxide, phenols described in No. dAal, 3.0≠2. Sulfur compounds described in JLT No. AID document, 3. θguco, ri/
Alkali metal iodides, organic acids, 30g, 20g, described in the specification No. 6 [organic acid anhydrides,
Antimony, arsenic, as described in 3377147,
Triaryl compounds of bismuth and phosphorus are effective.

The ratio of the color change agent as described above and the compound represented by the general formula (1) is approximately 090/1 part of the color change agent to approximately 700 parts of the compound represented by the general formula (1). parts by weight, more preferably 0. /-10 parts by weight, most preferably 0. ! The compound of general formula (I) may be used in a mixture of 21 or more.

On the other hand, the photosensitive resist-forming composition, which is the object to which the printout ability is imparted by the printout composition of the present invention, can be used for various printing plates such as anti-printing plates, IC circuits, photo resists, etc., as described above. This includes items such as heels that are used to create masks, etc. Below, we will explain some typical items.

(1) Composition consisting of diazo resin p-diazodiphenylamine and paraformal feF"
yo” ad &ei, □o, 72.4kej! IWl!,
It may be a 7,1-isomer or a water-insoluble one, but preferably one that is water-insoluble and has an i+iIu property in a normal organic solvent is used. Particularly preferred diazo compounds include salts of a combination of p-diazophenylamine and formaldehyde or acetaldehyde, such as phenol salts, fluorocaprates, and triisopropylnaphthalenesulfonic acid, Hiroshi.

≠-biphenyldisulfonic acid, ternitroortho-toluenesulfone IL -t-sulfosalicylic acid, λ, j-
Dimethylbenzenesulfonic acid, λ-nitrobenzenesulfonic acid, 3-chlorobenzenesulfonic acid, 3-f-romobenzenesulfonic acid, cochloro-nitrobenzenesulfonic acid, 2-fluorocara-lylnaphthalenesulfonic acid, l-naphthol-! -Sulfonic acid,! -Methoxygoo hydroxy! -Benzoyl- A compound having two or more diazo groups in one molecule, such as salts of sulfonic acids such as benzenesulfonic acid and para-toluenesulfonic acid. Other desirable diazo resins include λ,j-dimethoxy Hirop-to! containing the above-mentioned salts. J. Lumerca - 7 tons A combination of benzenediazonium and formaldehyde, 2. It includes a combination of j-dimethoxy-≠-morpholinobenzenediazonium and formaldehyde or acetaldehyde.

Also, British Patent No. 1, 3/2. Ri2! The diazo resin described in No. 7) is also preferred.

The diazo resin can be used alone as a photoresist for making a resist, but is preferably used in conjunction with a binder.

Various polymeric compounds can be used as such binders, but those containing groups such as hydroxy, amino, carboxylic acid, amide, sulfonamide, active methylene, thioalcohol, and epoxy are preferred. Such preferred binders include those described in British Patent Nos. 1 and 3 O. Irsheratsk, British Patent No. 1. gtθ
, 27f and U.S. Patent No. u,/, 23. ．． 271.
Polymers containing one hydroxyethyl acrylate unit or hydroxyethyl methacrylate unit as a main repeating unit as described in each specification of US Pat. phenolic resins and polyvinyl acetal resins such as polyvinyl formal resins, polyvinyl butyral resins, U.S. Pat. No. 3. lt
Linear polyurethane resin described in the specification of No. 027, phthalate of polyvinyl alcohol) Polymers containing more amino groups, celluloses such as cellulose acetate, cellulose alkyl ether, and cellulose acetate phthalate are included.

The content of the binder is suitably such that the weight of the binder is ≠θ to ≠j in the photosensitive resist-forming composition. If the amount of binder is large (i.e., if the amount of diazo resin is small), the photosensitivity will naturally increase, but the stability over time will decrease.The optimal amount of binder is about 70 to 20% Ii: I am in charge.

Compositions comprising diazo resins are further described in U.S. Pat.
Additives such as phosphoric acid, dyes and pigments that are not color change agents, as described in the specification of No. 23T, can be added.

(2) Compositions comprising o-quinonediazide compounds Particularly preferred O-quinonediazide compounds are O-naphthoquinonediazide compounds, such as U.S. Pat. No. 2,7J4.1
No. 11, No. J, 7 t 7 +02 No. 2, No. 2
, No. 772.27, same, Calendar No.

1rjY, //, No. 2, No. 2, 2. ri07. tt evening issue,
Same No. 3,041t, No. 110, Same No. 3. θ≠4. /l1
No. 3. O1l/,, No. 113, No. 3.0'/-
No. 6,111, same No. J, Ou Ap/79
No. 3.04 LA, No. 120, @J, 0 Hiroshi 4. /λ1 No. 3.0 Hiro & , No. 122, MJ
, 0≠Otsu, No. 123, No. 3. θl/, ≠3θ No. J, No. 102.10, No. 3, 10t, No. G+1, No. 3. t3j, No. 707, same No. 3, 6g 7゜,,,
one. □、1□2゜. Ah, yay. -I"ll?□'I
IIJLCi%', 1, and these can be suitably used. Among these, in particular, 0-naphthoquinonediazide sulfonic acid ester or 0-naphthoquinonediazidecarboxylic acid ester of aromatic hydroxy 11 compound, and 0-naphthoquinonediazide sulfonic acid amide or 0-naphthoquinonediazidecarboxylic acid amide of aromatic amine compound. is preferred, especially U.S. Pat. No. 3.
t3j, a condensate of pyrogallol and acetone described in No. 707, subjected to an ester reaction with 0-naphthoquinonediazide sulfonic acid, US Patent No. 1I, 02
The polyester Ko-naphthoquinonediazide sulfonic acid having a hydroxyl group at the terminal described in the specification of No. 111, or the product obtained by ester reaction of 0-naphthoquinonediazidecarboxylic acid, British Patent No. 1≠9≠ ,
O-naphthoquinonediazide sulfonic acid or O-naphthoquinonediazidecarboxylic acid is added to a homopolymer of p-hydroxystyrene or a copolymer of this with other copolymerizable monomers as described in No. 0113-A. Ester-reacted product, U.S. Patent No. 3,7j,
The copolymer of p-aminostyrene and other copolymerizable monomers described in the specification of No. 7//, which is obtained by amide reaction with 1co-naphthoquinonediazide sulfonic acid or 0-naphthoquinonediazidecarboxylic acid, is Very good.

These 0-quinonediazide compounds can be used alone, but it is preferable to use them in combination with alkali-soluble cotton fat. Suitable alkali-soluble resins include novolak-type phenols, specifically phenol formaldehyde, IL o-cresol formaldehyde, and 1n-cresol formaldehyde resins. etc. are included. Furthermore, Tokukai F
K3! ;0-/2! ;As stated in Za01 publication, the above-mentioned phenol 4 ('J Ili\) and t
It is even more preferable to use a condensate of formaldehyde and phenol or cresol in which If' has been replaced with an alkyl group having 3 to 3 carbon atoms in the -7' tylphenol formaldehyde resin. The alkali-soluble resin has a content of from about SO to about 13 t, more preferably t, based on the total weight of the photosensitive resist-forming composition.
It is contained in an amount of 0% by weight.

A photosensitive composition comprising an 0-quinonediazide compound includes
If necessary, pigments, dyes, plasticizers, etc. that are not color change agents can be further included.

Suitable photosensitive azide compounds are aromatic azide compounds in which the azide group is bonded to an aromatic ring directly or via a carbonyl group or a sulfonyl group.

In these, the azide group is decomposed by light to produce nitrene, which undergoes various reactions and becomes insolubilized. Preferred aromatic azide compounds include compounds containing 7 or more groups such as azidophenyl, azidostyryl, azidobenzal, azidobenzoyl and azidocinnamoyl, such as p,l-diazidochalcone, ≠-azidohiro/ (< 2-azidobenzoylethoxy) chalcone, N,N-bis-p-azidobenzal-p-phenylenediamine, /, 2,4-tri(≠'-
azidobenzoxy)hexane, λ-azido 3-chlorobenzoquinone, λ, ≠-diazido-hiro'-ethoxyazobenzene, 2,6-di(hiro'-azidobenzal)-gumethylcyclohexanone, ≠, hiro'-diazidobenzophenone , λ, j-diazido 3. t-dichlorobenzoquinone, U, t-bis(≠-azidostyryl)-l.

3.4t-oxadiazole, '(Hiro-azidocinnamoyl)thiophene, λ, j-di(11/--azidobenzal)cyclohexanone, ≠, ψ'-diazidodiphenylmethane, /-(<2-azidophenyl) -Yo-Freelu Cohenter λ, <A-diene-l-on, /-(≠
-azidophenyl) -1-(Hiro-methoxyphenyl)
-Penta-1, Koichi dien-3-one, /-(!-azidophenyl)-J-(/-naphthyl)70 is norl-one, /-(≠-azidophenyl)-3-(4/-- dimenalaminophenyl)-pronoξy-/-oy, /-(
≠-Acidophenyl)-Yo-Phenyl-/, Riichi is Phtadien-3-one,' (Hiro-Acidophenyl)
-3-(≠-nitrophenyl)-λ-furoben-/-one, /-(≠-acidophenyl)-3-(2-furyl)
=2-propene-7-one, 1.2,1s-)(≠/
, ycytobenzoxy)hexane, λ, t-bis-(≠
-azidobenzylidine-p-t--1+'thyl)cyclohexanone, p,1-diazidodibenzalacetone, ≠
, μ′-Diazidostilbene! , 2'-disulfone L
m-andbenzalacetophenone-cosulfonic acid,
Hiro, ≠′-diazidostilbene-α-carboxylic acid, di(+-′azido-1′-hydroxybenzal)acetone-cosulfonic acid, Hiro-acitobenzalacetophenone-λ-sulfonic acid, 2-azido)” -/, Hiro-dibenzenesulfonylamitnaphtha V7.'/-, 'l/-diandose stilbene-2°2/-disulfonic acid anilide, and the like.

In addition to these low-molecular-weight aromatic azide compounds, there are also Tokko Akihiro≠-TAO-Hiro No. 7 and I1. Goo 3/r37, same≠
! -Tat/No. 3, same gu! −, 2 Hiro No. 73, same≠j−,
No. 237/3, Japanese Unexamined Patent Publication No. 237/3.

No. 2, same! tO-411302, same j (V-411-
The azide group-containing polymers described in Japanese Patent Applications No. 303 and JJ-/2-1R-Hiro No. 303 are also suitable.

These photosensitive azide compounds are preferably used together with a polymer compound as a binder.

Preferred binders include alkali-based binders, such as natural binders such as Sierran and rosin.7.
R-fat, for example, phenol formaldehyde resin Nl1
1-Cresol-formaldehyde resins, non-porous phenolic resins such as polyacrylic acid, polymethacrylic acid, methacrylic acid-styrene copolymers, methacrylic acid-methyl acrylate copolymers, styrene-maleic anhydride copolymers, etc. f<,! A homopolymer of a carboxylic acid or a copolymer of this with a monomer that can be combined with it, a partially or completely saponified product of polyvinyl acetate, such as acetaltehyde, benzaldehyde, hydroxybenzaltehyde, carboxybenzaldehyde, etc. Examples include resins partially acetalized with aldehydes, polyhydroxystyrene, etc. Furthermore, organic solvent-soluble resins such as cellulose methyl ether, cellulose alkyl ethers such as cellulose ethyl ether, and the like can also be used as binders.

The binder is preferably contained in an amount ranging from about 10% to about 70% by weight based on the total weight of the composition comprising the photosensitive azide compound.

The composition comprising the photosensitive azide compound may further contain dyes and pigments that are not discolorants, such as heptatarates, phosphates, aliphatic carboxylates, glycols, sulfonamides, and other plasticizers, such as Michler's ketone, terfluorenone. , /-dito, lopyrene, 72g-dinitropyrene, 2-chloro-/, 2-benzanthraquinone, copromo-/ , 2-benzanthraquinone,
Pyrene-/.

Additives such as sensitizers such as t-quinone, cochlorine, male-phthaloylnaphthalene, and cyanoacridine may be added. 0 1 Polyester containing -CH-CH-C- as a photosensitive group in the polymer main chain or side chain (page 9), Poly1 Polyester containing photosensitive polymers as main component such as amides, polycarbonates (for example, in the US) Patent No. 3゜030.20
1, 3.707.373 and 3. Hiro 33.
Compounds such as those described in each Memorandum I of '237); photosensitive polyesters derived from (,2-probelidene) malonic acid compounds such as cinnamylidene malonic acid and difunctional glycols; The main component (for example, photosensitivity as described in the specifications of U.S.!1. polymers); cinnamate esters of hydroxyl-containing polymers such as polyvinyl alcohol, starch, cellulose, and the like (e.g., U.S. Pat.
Riotsu No. 6, No. 2, 7! , No. 2.372, ``Photosensitive polymers such as those described in ``K iiL '61;c'' 1], and the like. These compositions may also contain sensitizers, stabilizers, plasticizers, pigments and dyes other than color change agents, and the like.

Composition This composition preferably consists of (a) a vinyl monomer having a small amount (both having two terminal vinyl groups), (b) a photoinitiator, and (c) a polymeric compound as a binder.

As the vinyl monomer of component (a), Japanese Patent Publication No. 3J-5
o73, special public show 3! -7 Hiro 7/9, special public show 4'4'
-, 21727, etc., the polyol acrylic acid ti is a methacrylic ester, that is, diethylene glycol di(meth)acrylate, triethylene glycol/(meth)acrylate, pentaerythritol tri(meth)acrylate, Methylolpropane tri(meth)acrylate, etc., or bis(meth)acrylamides such as methylenebis(meth)acrylamide, ethylenebis(meth)acrylamide, or unsaturated monomers containing urethane groups, such as di(,2/ -methacryloquine ethyl) -λ.

Examples include reaction products of photo diol mono(meth)acrylates and diisocyanates such as ≠-tolylene diurethane and di(2'-acryloxyethyl) trimethylene diurethane.

As the photopolymerization initiator of component (b), the above-mentioned one-part formula (I
) can be used, but other (+, 'f
:j':fJ can also be used. For example, "Light Sensitive Systems" by J. Coser, Part J:
The carbonyl compound 'I11i' as described in t.
゛Organic sulfur compounds, peroxides, redox compounds, azo and diazo compounds,...rogen compounds, light 1.1! There are natural pigments, etc. More specifically, the UK! 1 te permissible/
.

Gu! the law of nature,! It is disclosed in No. 63 Specification:

On the other hand, as the binder for component (C), any known polymer can be used. Details of specific binders can be found in U.S. Patent Maki, 072. ．． f, described in specification No. 27. Furthermore, UK '1. 'i' first ゜hiroj! i
', 363, are particularly preferred binders.

Component a) and component (C) are contained in combination in a weight ratio of /: t to t. In addition, the component (bl is the component (aJ
It is contained in a range of 0.005 to 10% by weight based on .

The photopolymerizable composition may further contain a dye or pigment that is not a thermal polymerization inhibitor, a plasticizer, or a color change agent.

When such a photosensitive resist-forming composition contains the printout composition, the printout composition is added in an amount of about 0.1 weight per 100 parts of the photosensitive resist-forming acid inhibitor. It can be contained in a range of from 1 part to about 30 parts by weight, more preferably from 1 to 30 parts by weight.

Solvents used when applying the photosensitive resist-forming composition imparted with printout capability include ethylene dichloride, nclohexanone, methyl ethyl ketone, 2-methoxyethyl acetate, monochlorobenzene, toluene, and ethyl acetate. These can be used alone or in combination.

It is advantageously used as a photosensitive layer provided with such printout ability. In this case, the support may be, for example, aluminum (including aluminum alloys), zinc, iron, copper, etc., or plastics on which such metals are laminated or vapor-deposited; Most preferred are aluminum plates.In the case of supports with a surface of metal, especially aluminum, graining, sodium silicate, potassium fluorozirconate,
It is preferable that the surface be subjected to a surface treatment such as immersion treatment in an aqueous solution such as ``'j t'ju salt'' or anodization treatment.

Also, U.S. Patent No. λ, 7/Hiro, ott specification jjj r,
As described in U.S. Pat. ivl, ttti issue details 'f4' lc note r! U'
5. ,,A7.9=tsu4□□wi,gaj,
J: jl L % Later, in an aqueous solution of alkali metal silicate? After processing two bonds, the next one is also preferably 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 sulfamino acid, or a salt thereof, either alone or in combination. Among these, it is particularly preferably carried out by passing an electric current through an aluminum plate as an anode in an aqueous solution of phosphoric acid, sulfuric acid, or a mixture thereof. Also, U.S. Patent No. 3. Silicate electrodeposition as described in JT, TT No. 2 is also effective. Furthermore, as described in British Patent No. 1°, 201,22≠ Specification J1, an aluminum plate is also produced by electrolyzing the aluminum plate in a hydrochloric acid electrolyte with alternating current, and then oxidizing it in a sulfuric acid solution. preferable. In addition, it is preferable to provide an undercoat layer of cellulose resin containing a water-soluble salt of a metal such as lead 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 O,
1 to about 7 i/m2, preferably o, s-+so/m2.

The thus obtained PS plate is subjected to image 7 and madder light, and then subjected to processing including development by a conventional method to form image 1. For example, in the case of JAM of a PS plate having a photosensitive layer made of a photosensitive composition containing a printout composition in the composition (1) made of a diazo resin, after image exposure, the unexposed portions of the photosensitive layer are developed. A lithographic printing plate is obtained. In addition, in the case of a PS plate having a photosensitive layer made of a ΔP-1 photosensitive composition containing a printout composition in the above-mentioned 5111 composition (2), after image peeling, an alkaline aqueous solution is used. By developing, the exposed part is removed,
The lithographic printing plate leaks 7i'j. No matter what kind of photosensitivity the PS plate has, no special measures are required due to the printout ability imparted by the present invention, and conventionally known PS plates suitable for each Il+;': photosensitive composition are used. Developing solution can be used for development.

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

Furthermore, the above-mentioned seven-part composition can also be used for producing a film for a photomask. Suitable supports include a polyethylene terephthalate film on which aluminum or aluminum alloy Yachrome is vapor-deposited, and a polyethylene terephthalate film on which a colored layer is provided.

Additionally, the composition described above can be used as a photoresist. In this case, a copper plate, a copper plated plate, a stainless steel plate, a glass plate or the like can be used as the support.

In a photoresist-forming composition in which the free radical generator according to the invention comprises a photoresist-forming compound,
It is surprising that when exposed to light, the coexisting color change agent decomposes and changes color efficiently (immediately). As a result, a sharp border is obtained between the exposed and unexposed areas, and the contrast is improved. It can be recognized as a visible image.

Furthermore, since a wide range of color changing agents can be used, [f! An appropriate color change agent can be selected when various additives are added.

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

Furthermore, the free radical generating agent according to the present invention exhibits a very rapid reaction (and is not significantly inhibited by the coexisting photosensitive resist-forming compound), so that it is effective even when added in a small amount.

Furthermore, since the free radical generating agent according to the present invention does not significantly inhibit the photodecomposition of photosensitive layer resist-forming compositions, such as the above-mentioned compositions (1) and (2), (photosensitivity)). Further, since the free radical generating agent according to the present invention is effective when added in a small amount, it does not deteriorate the physical properties of the resist image obtained after imagewise exposure and development of the photosensitive diheto-1 forming composition. Another example is the developability of a printing plate obtained when the photosensitive resist-forming composition imparted with printout ability according to the present invention is used as a photosensitive layer of a photosensitive lithographic printing plate.

Properties such as oil sensitivity, printing stains, and printing durability are the same as when no free radical generator is added.

Hereinafter, the present invention will be explained in more detail with reference to Examples. Note that r%J indicates weight % unless otherwise specified.

Example 1 The following photosensitive solution was applied to an aluminum plate with a thickness of 0.2 mm, whose surface was grained and then anodized, and heated at 1000C for 2 hours.
Let dry for a minute.

Esterification reaction product of naphthoquinone-(/2.2)-diazide-(2)-t-sulfonyl chloride and Talezol novolac 1 fat 0.7 tag Talezol novolac resin 2.10jJ Tetrahydrophthalic anhydride 0. /A-9 free radical generator (listed in Table 1) 0.037J crystal violet o,
oig oil sol-@403 0. θ/So (manufactured by Orient Chemical Industry Co., Ltd.) ethylene dichloride /IjJ comethoxyethyl acetate) /2ji The coating amount after drying was 2.1 g7 m2. Each of these photosensitive lithographic printing plates was exposed for ti, o seconds using a 2 KW metal halide lamp through a positive transparent original from a distance of 7 m.

Exposed part and un””F? The optical bankruptcy of the photosensitive layer in the optical part was measured using a Macbeth reflection densitometer.

The image obtained by exposure is 1.・Optical of exposure part 0゛, 4
The larger the difference (△D) between the degree and that of the unexposed area, the jjl
i': Looks clear. Also, in gray scale (the optical density difference between two adjacent stages is 0./3; the optical γ↓ degree of the first stage is O
9/ and 1.2/ steps. ) and then exposed to light using the same method as above, and then exposed to a sodium metasilicate aqueous solution [, 2 minutes at 0C/minute] to check the resist sensitivity. Sensitivity is indicated by the number of solid steps (the higher the number, the higher the sensitivity).

Also, after exposing in the same way as above through a positive transparent original image,
≠ Rub it with a sponge soaked in sodium metasilicate solution! Then, the unevenness in the non-image area (sengen unevenness) was investigated. For the 18th item, choose one with almost no unevenness.
Items that appear uneven are marked with an x. As is clear from the first situation, according to the present invention, it is possible to provide a dawning image (printout) without lowering the sensitivity of the resist, and without causing unevenness in the non-image area at EJi 9.
: I was able to do it in a benevolent way.

/ Example 2 In the same manner as in Example 1, the following photosensitive liquid was applied to an aluminum plate and dried.

Copolymer of methyl methacrylate and methacrylic acid (copolymerization molar ratio - ta:/) o, Otsuko I Trimethylolpropane triacrylate 0.3♂9 2-benzoylmethylene-3-methyl-β-naphthothiazoline o, o2I! i+ Free radical generating agent (exemplified compound/16/) 0,04'
jp Leuco Crystal Violet 0.00gg Methyl Ethyl Ketone /j ji After drying, the coating weight was 5g7m. When this photosensitive lithographic printing plate 1HilJ plate was exposed through a transparent uA negative in the same manner as in Example 1, ? The illuminated portion of the NN was colored purple, and a printout image (printout) with a high contrast was obtained.

Then 1.2g of caustic sorg, 3g of isopropyl alcohol
A lithographic printing plate was obtained by removing the unexposed areas with a developer consisting of 00d1 water and 00m2. When using a photosensitive solution in which the free radical generator (exemplary compound A/) is excluded from the above photosensitive solution, the printed image is He didn't appear.

Example 3 The following photosensitive liquid was applied to the uncoated aluminum plate used in Example 1 using a Whaler. Inui 1: Sugi'i tOOo
C for 2 minutes.

p-Toluenesulfonate of compound B of p-diazodiphenylamine and paraformaldehyde o, ;t g polyvinyl formal 0.7 J-, free radical generator (exemplary compound A62) 0.02 crystal violet o
, o, x,! 7λ-methoxyethanol, 2
0,! /methanol j'd 3 The dry coating amount was /, Og/+n2. When this non-optical lithographic printing plate was exposed for 30 seconds from a distance of 70 cm using a 30 amp carbon arc lamp, a clear printed image with rich contrast was obtained in which the exposed areas were discolored. .

In addition, in the above photosensitive solution, a free-forming agent (exemplified compound/162
) When using a photosensitive solution other than those mentioned above, a clear printout pattern could not be obtained.

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

Polyester synthesized by condensation of ethyl p-phenylene diacrylate and equimolar amounts of /,≠-bis-β-hydroxyethoxycyclohexane (molecules are approximately g, ooo) o, t g λ-benzoylmethylene-3-methyl -β-Naphthothiazoline 0, 039 Free radical generating agent (exemplary compound //6A) 0.00gg Leuco Crystal Piolet) 0.00♂I Monochlorobenzene I Ethylene dichloride Otsu, 9 Coated stitch after drying /, 397m When this photosensitive lithographic printing plate was exposed through a transparent negative in the same manner as in Example 1, a printed image rich in contrast was obtained. The surface was developed by wiping the surface to obtain a '17-plate printing plate.The above photosensitive solution was prepared by excluding free t'ift and group-forming compound 3111 (exemplified compound/r6.). Compared to this +1.4 go, the printed image is clearly clearer than JXi.
The sensitivity of the resists was about the same.

Developer composition in Silk - Butyrolactone 1000 he Glycerol 100mI! Methyl abinitate / Orrt

Claims (1)

Claims: A photosensitive composition comprising (a) an oxadiazole compound represented by the following general formula (I) and (b) a compound that interacts with a photodecomposition product of the oxadiazole compound. λ (where X is a hydrogen atom, an alkyl group or an IJ-al group, Y is a fluorine atom, a chlorine atom or a bromine atom, and n is
m represents an integer of / to 2; l represents 0 or /; )