JPS60241049A - Photosensitive composition - Google Patents

Abstract

PURPOSE:To immediately change the color of a color-changeable agent by exposure to light, to form shape border lines between the exposed areas and the unexposed areas, and to obtain a visible image rich in contrast by incorporating a specified oxadiazole compd. as a free radical producing agent. CONSTITUTION:The compd. to be contained as the free radical producing agent is 2-halomethyl-5-substd.-1,3,4-oxadiazole represented by the formula in which (A) is an aromatic residue, Y is Cl or Br, and n is 1-3. Such a free radical producing agent, when added to compsns. contg. compds. capable of forming various photosensitive resists, is decomposed by exposure to light, and effectively and immediately changes the color of the coexisting color-changeable agent, resulting in forming sharp border lines between the exposed and unexposed areas, and obtaining an image rich in contrast. This free radical producting agent is especially useful when it is used for the photopolymn. initiator of a photopolymerizable compsn., and for obtaining ability of forming a visible image only by exposure without development on the photosensitive resist forming compsn. for manufacture of a lithographic plate, an IC circuit, and a photomask.

Description

DETAILED DESCRIPTION OF THE INVENTION "Industrial Application Field" The present invention relates to a photosensitive composition containing a novel compound that generates free radicals when exposed to light. More specifically, the novel λ-no-lomethyl-j-substituted-/, J
, relates to a photosensitive composition containing a 44-oxadiazole compound.

“Conventional technology” Compounds that decompose and generate free radicals when exposed to light (
free radical generators) are well known in the field of graphic arts. 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. 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 halogen radicals such as chlorine and bromine radicals; these halogen radicals are good hydrogen abstracting agents and yield acids in the presence of hydrogen donors. For their application to photopolymerization processes and free radical photography processes, see J. Kosar, Lig.
ht 5ensj tiveSystemsJ J,W
ily & 5ons (New York 63)
/10~/Ir/pages and 3t/~370 pages.

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 the disadvantage that they are only decomposed by light in a very limited wavelength range.

In other words, it was sensitive to the ultraviolet region, which is shorter than the dominant wavelength of commonly used light sources. Therefore, these compounds lack the ability to effectively utilize light in the near-ultraviolet to visible range emitted by a light source, and therefore have poor free radical-generating ability.

In order to improve this drawback, it has been proposed to widen the sensitive wavelength range by mixing a certain kind of sensitizer. For example, U.S. Pat. /
2/, sensitizers such as merocyanine dyes, styryl bases and cyanine bases as described in A33. It is true that the addition of these sensitizers has expanded the sensitivity wavelength range of carbon tetrabromide and iodoform to visible light, but this is still not satisfactory. This is because it is necessary to select a sensitizer that has good compatibility with the free radical generator or other elements in the photosensitive composition. This is because it was difficult to choose.

In order to improve this drawback, a halogen free radical generator has been proposed whose photosensitive wavelength range is from near ultraviolet to visible light. For example, U.S. Patent No. 3. 311. l17. No. 3, 2
No. 17.037 and No. 44. There is a group of halomethyl-S-) riazine compounds described in No. 323, No. 323. Although these compound groups have a photosensitive wavelength range from near ultraviolet to visible light, the irradiated light is not used effectively and the sensitivity of photolysis is relatively low. In addition, those with high sensitivity include JP-A Shoj≠-7 Gu 7-Hiro and JP-A Shojtjt-777112.
There is an oxadiazole compound described in the above issue, but its aging properties are not sufficient.

"Problems to be Solved by the Invention" An excellent photosensitive composition that is a free radical generating agent whose photosensitive wavelength range is from near ultraviolet to visible region, has high photosensitivity, and has no compound with excellent aging properties. was not obtained.

"Means for Solving the Problems" As a result of various studies, the present inventors have found that the above-mentioned problems have been solved by the novel J-/.romethyl-j-[conversion-
The problem was solved by a photosensitive composition containing a 3,4'-oxadiazole compound as a free radical generator. The compound of the present invention also had good compatibility with other components in the composition.

CI) where A represents a substituted or unsubstituted aromatic residue, Y
represents a chlorine atom or a bromine atom, and n represents an integer of / to 3.

The present invention will be explained in more detail.

In the general formula (1), the aromatic residue of A includes an aryl group and a heteroaromatic residue, and is preferably a monocyclic or bicyclic residue, such as a f-J'-enyl group, l-naphthyl group, etc. group, conaphthyl group, λ-furyl group, λ-chenyl group, cortiazole group, cortiazole group, 2-imidazole group, cohiridyl group, cortiazole group, λ-benzochenyl group, cobenzoxazole group, cobenzothiazole group, λ-penzimidazose group, benzotriazole group, λ-indolyl group,
-monoquinolyl group and the like. Preferably it is a monocyclic aryl group.

Examples of substituted aromatic residues for A include aromatic residues such as those mentioned above, alkyl groups having 1-2 carbon atoms such as methyl groups and ethyl groups, and 1-2 carbon atoms such as methoxy groups and ethoxy groups. - Includes those substituted with two alkoxy groups, such as halogen atoms such as chlorine atoms, hydroxy groups, nitro groups, phenyl groups, carboxy groups, cyano groups, etc. Specifically, p-chlorophenyl groups, -2- Chlorophenyl group, cubromophenyl group, ≠-nitrophenyl group, 3-nitrophenyl group, Hiro-phenylphenyl group, p-methylphenyl group, cortiazole group, 6-μ-ethylphenyl group, l-methoxyphenyl group, Komethoxyphenyl group, μ-ethoxyphenyl group, Coca/I/hokidiphenyl group, Hiro-cyanophenyl M, 3.
'l-methylenedioxyphenyl group, j-phenoxyphenyl group, ≠-a7toxyphenyl group, cu-hydroxyphenyl group, 3-hydroxyphenyl & p-methyl-
l-naphthyl group, l-chloro-/-naphthyl group, j-nitro l-naphthyl group, t-chloro-2-naphthyl group,
Gopromo 2-naphthyl group, j-nitroconaphthyl group, 6-methyl-2-benzofuryl group, t-methyl-
Examples include λ-benzoxazole group, 6-methyl-λ-benzothiazole group, and t-chlorocobenzotheazole group. Preferably it is a monocyclic aromatic residue.

The co-halomethyl-j-substituted mono/, J, 4cm-long xadiazole compound represented by the general formula (I) used in the present invention is synthesized by the following method. Namely, D. H. Wadsworth et al., Journal
l of Organic Chemistry.

30 volume, 110-ttj pages (tqts) VC method, written by Hiroji Matsui et al., Industrial Chemistry Magazine, 73 volume, lr7-l tag pages (lr7θ) method, J.

W. Wilson et al., Journal
of Organic Chemistry X/1
vol. 4-705 (l. j3), or R. C. Fuson et al.
he American Chemical 5ocie
ty,, A2 volume, /1rO-//lrJ page (/91
General formula (II) synthesized according to the method described in 10)
) using a known method as a raw material, for example, U.S. Patent No. G, 232.107. No. specification,
By proceeding the reaction according to the method described in U.S. Pat. ) co-halomethyl-j-substituted-/,
3. II-oxadiazose compound.

Compounds having the structure shown below are particularly advantageous as release generators for use in the present invention.

ya/ bend coater flat 3 10- AA boiled α 10 A/1 CH3 73- 1 l ko - -/! - The free radical generator of the present invention is used as a photoinitiator in photopolymerizable compositions and in photosensitive resist-forming compositions for the production of lithographic printing plates, IC circuits, and photomasks, which are developed by exposure to light. This is particularly useful in providing the ability to provide a visible image without the need for any damage.

When the free radical generator of the present invention is used in a photopolymerizable composition, the photopolymerizable composition comprises a polymerizable compound having an ethylenically unsaturated bond, a photoinitiator, and, if necessary, a binder. and, if necessary, a sensitizer, and is particularly useful for photosensitive layers of photosensitive printing plates, photoresists, etc.

The polymerizable compound having an ethylenically unsaturated bond in the photopolymerizable composition of the present invention is a compound having at least one ethylenically unsaturated bond in its chemical structure, and is a monomer, a prepolymer, i.e. It has chemical forms such as λ-mer, trimer and other oligomers, mixtures thereof, and copolymers thereof. Examples thereof include unsaturated carboxylic acids and their salts, esters with aliphatic polyhydric alcohol compounds, amides with aliphatic polyhydric amine compounds, and the like.

Specific examples of unsaturated carboxylic acids include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, incrotonic acid,
These include maleic acid.

Salts of unsaturated carboxylic acids include sodium and potassium salts of the aforementioned acids.

Specific examples of esters of aliphatic polyhydric alcohol compounds and unsaturated carboxylic acids include acrylic esters such as ethylene glycol diacrylate, triethylene glycol diacrylate'f, l, 3-butanediol diacrylate, and tetramethylene. Glyco diacrylate, zolopylene glycol diacrylate, trimethylolpropane triacrylate, trimethylolethane triacrylate), 4'-cyclohexanediol diacrylate, tetraethylene glycol diacrylate, pentaerythritol diacrylate, penta Examples include erythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol triacrylate, dipentaerythritol tetraacrylate, sorbitol triacrylate, sorbitol triacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, and polyester acrylate oligomer. Examples of methacrylic acid esters include tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, ethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, pentaerythritol dimethacrylate, and pentaerythritol dimethacrylate. Erythritol trimethacrylate, dipentaerythritol dimethacrylate, sorbitol trimethacrylate, sorbitol tetramethacrylate, bis-(p-(3-methacryloxy-monohydroxypropoxy)phenyl)dimethylmethane,
Bis-(p-(acryloxyethoxy)phenyl)dimethylmethane, etc.Itaconic acid ester ν includes:
Ethylene l 7-glycol shiitaconate, propylene glycol shiitaconate, 1,3-butanediol shiitaconate, /, +-butanediol shiitaconate, tetramethylene glycol shiitaconate, pentaerythritol shiitaconate, sorbitol Examples include tetrataconate. Examples of crotonic acid esters include ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, bentaerythritol dicrotonate, and sorbitol tetracrotonate. Examples of incrotonic acid esters include ethylene glycol diincrotonate, pentaerythritol diincrotonate, and sorbitol diincrotonate. Examples of maleic esters include ethylene glycol simarate, triethylene glycol simarate, pentaerythritol simarate, and sorbitol tetramaleate. Furthermore, mixtures of the aforementioned esters may also be mentioned.

Specific examples of amides of aliphatic polyvalent amine compounds and unsaturated carboxylic acids include methylenebis-acrylamide, methylenebis-methacrylamide, /, J
-hexamethylene bis-acrylamide, 4-hexamethylene bis-methacrylamide, diethylene triamine tris-acrylamide, xylylene bis-acrylamide, xylylene bis-methacrylamide, and the like.

As another example, a polyisocyanate compound having two or more isocyanate groups in one molecule, which is described in Japanese Patent Publication No. 4TT-PI'YOR, contains a hydroxyl group represented by the following general formula (1). Examples include vinyl urethane compounds containing two or more polymerizable vinyl groups in one molecule to which a vinyl hexamer is added.

Of(=C(R)C00Cf(2C1((R/)O)l
(III) (However, 几 and R' are H or C
Indicates H3. ) When the free radical generating agent of the present invention is used as a photopolymerization initiator in a photopolymerizable composition, the photopolymerizable composition can contain a binder if necessary.

As the binder in the photopolymerizable composition of the present invention, the compatibility with the polymerizable ethylenically unsaturated compound and the photopolymerization initiator is determined in the manufacturing process of the photosensitive material including preparation of the coating solution, coating, and drying of the composition. The photosensitive layer or resist layer should be of good quality to the extent that no demixing occurs, and the photosensitive layer or resist layer should be capable of being developed after image exposure, whether by solution development or peeling development. It is required to have properties such as the ability to form a film, and is usually appropriately selected from linear organic polymers. Specific examples of binders include chlorinated polyethylene, chlorinated polypropylene, polyacrylic acid alkyl esters (alkyl groups include methyl group, ethyl group, n-butyl group, 1so-butyl group, n-hexyl group, coechahexyl group, etc.), acrylic acid alkyl ester (the alkyl group is the same as above) and acrylonitrile, [
Copolymers with at least one monomer such as vinyl chloride, vinylidene chloride, styrene, butadiene, polyvinyl chloride, copolymers of vinyl chloride and acrylonitrile, polyvinylidene chloride, copolymers of vinylidene chloride and acrylonitrile, polyvinyl chloride, copolymers of vinylidene chloride and acrylonitrile, Vinyl acetate, polyvinyl alcohol, polyacrylonitrile, copolymers of acrylonitrile and styrene, copolymers of acrylonitrile with butadiene and styrene, polymethacrylic acid alkyl esters (alkyl groups include methyl, ethyl, n-
Propyl group, n-butyl group, is.

-butyl L (n-hexyl group, cyclohexyl group, coethylhexyl group, etc.), methacrylic acid alkyl ester (the alkyl group is the same as above) and at least one of the seven polymers such as acrylonitrile, vinyl chloride, vinylidene chloride, styrene, butadiene, etc. copolymer, polystyrene,
Examples include poly-α-methylstyrene, polyamide (bu-nylon, J, A-nylon, etc.), methylcellulose, ethylcellulose, acetylcellulose, polyvinyl formal, polyvinyl butyral, and the like.

Furthermore, if a water- or potassium-water soluble organic polymer-cono-polymer is used, water or alkaline water development becomes possible. Examples of such high molecular weight polymers include addition polymers having carboxylic acid in their side chains, such as methacrylic acid copolymers (
For example, copolymers of methyl methacrylate and methacrylic acid, copolymers of ethyl methacrylate and methacrylic acid, copolymers of butyl methacrylate and methacrylic acid, copolymers of ethyl acrylate and methacrylic acid, copolymers of methacrylic acid and styrene and methacrylic acid, etc.)
, acrylic acid copolymers (such as copolymers of ethyl acrylate and acrylic acid, copolymers of butyl acrylate and acrylic acid, copolymers of ethyl acrylate and styrene and acrylic acid), and even itacon. Examples include acid copolymers, crotonic acid copolymers, and partially esterified maleic acid copolymers, as well as acidic cellulose derivatives having carboxylic acids in their side chains.

These high molecular weight polymers may be used alone as a binder, but two or more types must be compatible with each other to the extent that demixing does not occur during the manufacturing process from preparation of the coating solution to application and drying. Good high molecular weight polymers can be mixed in suitable ratios and used as binders.

The molecular weight of the high molecular weight polymer used as a binder can vary widely depending on the type of polymer, but generally ranges from 3,000 to 3,000.
0,000,000, more preferably in the range of 70,000 to 1,000,000. When the photopolymerizable composition of the present invention further contains a sensitizer, it is represented by general formula (1). A sensitizer that increases the rate of photopolymerization when used in combination with a photopolymerization initiator is used.

Specific examples of such sensitizers include benzoin, benzoin methyl ether, benzoin ethyl ether, terfluonone, λ-chlorotorfluorenone, -monomethylterfluorenone, teranthrone, copromoteranthrone, coethyluteranthrone, ?
, IO-anthraquinone, coech router.

IO-anthraquinone, λ-1-butyl? I Examples include -methylstyryl ketone, benzophenone, p-(dimethylamino)benzophenone (or Michler's ketone), p-(diethylamino)benzophenone, benzanthrone, and the like. Among these compounds, it is particularly preferable to use Michler's ketone.

Furthermore, during the production or storage of the composition of the present invention, it is desirable to add a thermal polymerization inhibitor to prevent unnecessary thermal polymerization of the polymerizable compound having an ethylenically unsaturated bond. Suitable thermal polymerization inhibitors include hydroquinone, p-methoxyphenol, di-t-7'thyl-p-
Cresol, hyrogallol, t-7' tilcatechol,
Examples include benzoquinone, cuprous chloride, phenothiazine, floranil, naphthylamine, β-naphthol, nitrobenzene, and dinitrobenzene.

In some cases, dyes or pigments may be used for coloring, such as methylene blue, crystal violet, rhodamine B1 fuchsin, auramine, azo dyes, anthraquinone dyes, titanium oxide, carbon black, iron oxide, phthalocyanine pigments, azo pigments, etc. may be added.

Furthermore, a plasticizer can be added to the photopolymerizable composition of the present invention, if necessary. Examples of plasticizers include phthalate esters such as dimethyl phthalate, diethyl phthalate, dibutyl phthalate, dihexyl phthalate, dicyclohexyl phthalate, ditridecyl phthalate, dimethyl glycol phthalate, ethyl phthalyl ethyl glycolate, and butylphthalate. Glycol esters such as rubutyl glycolate, phosphate esters such as tricresyl phosphate and triphenyl phosphate, diimbutyl adipate, dioctyl adipate,
Examples include aliphatic dibasic acid esters such as dibutyl sepacate and dibutyl maleate.

The photopolymerizable composition of the present invention is used by dissolving the aforementioned various constituent components 23- in a solvent and coating it on a suitable support by a known method. Next, preferred ratios of the various constituent components in this case are expressed in parts by weight relative to ioo parts by weight of the polymerizable compound having an ethylenically unsaturated bond.

26- ・−＼ tλ20′/? ? ? / / θ　00o　o　.

When the free radical generating agent of the present invention is used in a photosensitive resist-forming composition, the photosensitive resist composition can be used for many printings at the same time, since a visible image can be obtained only by exposure under a yellow safety light during the exposure operation. In the process of exposing the plate,
For example, when work is interrupted, it becomes possible for a plate maker to know whether a given plate has been exposed or not.

Similarly, for example, when making a lithographic printing plate, when a large plate is exposed to light many times, as is the case with so-called plate printing, the operator must immediately know which areas have been sawn. I can confirm it.

A photosensitive resist-forming composition that gives a visible image immediately upon exposure, in which the free radical generating agent of the present invention can be advantageously used, contains as essential components a photosensitive resist-forming compound, a free radical generating agent, a color change agent, and optionally one or more. Or, it usually consists of a plurality of plasticizers, binders, dyes that are not color change agents, pigments, antifoggants, sensitizers for photosensitive resist-forming compounds, etc.

A photosensitive resist-forming compound is a compound whose physical properties such as solubility, tackiness, and adhesion to a substrate change upon exposure to light, such as a photosensitive diazo compound, a photosensitive azide compound, and an ethylenically unsaturated compound. It includes compounds that have a bond, and compounds that undergo a reaction catalyzed by a photogenerated acid.

Suitable photosensitive diazo compounds include salts of p-diazodiphenylamine, such as phenol salts, fluorocaprates, and triisopropylnaphthalenesulfonic acid, 1. t'-bisphenyldisulfone H1z-nitroortho-toluenesulfonic acid, j-sulfosalicylic acid, co,! -dimethylbenzenesulfonic acid, λ-nitrobenzenesulfonic acid, 3-chlorobenzenesulfonic acid, 3-bromobenzenesulfonic acid, cochlorobenzenesulfonic acid, sufluorocapryanaphthalenesulfone lJ, /-naphthol-j-sulfonic acid , comethoxy≠-hydroxy-j-benzoylbenzenesulfone MEtE (compounds having two or more diazo groups in one molecule, such as a condensate of a salt of a sulfonic acid such as radluenesulfonic acid and formaldehyde) are preferred. Other preferred cotard diazo compounds include a condensate of u,j-dimethoxy-4'-p-)lylmercabutobenzenediazonium and formaldehyde, and a condensate of 2,3-dimethoxy-gmorpholinobenzenediazonium and formaldehyde or acetaldehyde, including the above-mentioned salts. There is a condensate of

Additionally, other useful diazo compounds are described in U.S. Pat.
Data, No. 373.

The diazo group of these is decomposed by irradiation with actinic light and becomes insoluble.

On the other hand, photosensitive diazo compounds that become alkali-soluble upon irradiation with actinic light can also be used. These are compounds having at least one 0-quinonediazide group in the molecule, particularly preferred are sulfonic acid esters or sulfonic acid amides of 0-quinonediazide.

Many such compounds are already known.

For example, US Patent No. 3011t/10, US Patent No. 30411
///No. 301/-4//j, No. 304It
//Y No. '304AA/20, same No. 30443
0-61ko No. 1, same No. 30111s/22, same No. 3/30
No. 0 No. 7, No. 3/300111, No. 3/fr2t
No. o, No. 3/r4c3/θ, No. 313oopr, No. 3io2roy, No. 3141913, No. 3111171700, No. 31590? ? Examples include those described in each specification such as No.

Suitable photosensitive azide compounds include 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 becomes insolubilized through various reactions of nitrene. Preferred aromatic azide compounds include compounds containing one or more groups such as azidophenyl, azidostyryl, azidobenzal, azidobenzoyl and azidocinnamoyl, such as p , p /-diazidochalcone, gouazido-p / (p -azidobenzoxyethoxy)chalcone, N,N-bis-p-azide, benzal-p-phenylenediamine, /,u,G-tri(ri'-azidobenzoxy)hexane, noazido-3-chlorobenzoquinone, λ,4! -diazidog'-ethoxyazobenzene, 2. t-di(p/-azidobenzal)-l-methylcyclohexano/, μ, μ'-diazidobenzophenone, co,! -Diazido J, 4-dichlorobenzoquinone, λ,! -bis(cuazidostyryl)-7゜3, goooxadiazole, -'(''-azidocinnamoyl)thiophene, J,s-,)(u'-azidobenzal)cyclohexanone, μ, ri'-diazidophenyl methane,
l-(guazidophenyl)-j-furyl-λ-venter 21≠-dien-/-one, 1-(4t-azidophenyl)-j-(coumethoxyphenyl)-venter 1.
Hiro-dien-3-one, /-(4(-azidophenyl)
-3-(l-naphthyl)zoloben-7-one, no(guazidophenyl)-J-(F-dimethylaminophenyl)-propan-7-one, l-(≠-7di)"phenyl-j- Phenyl-7,p--<phtadien-3-one, /-(guazidophenyl)-J-(!-nitrophenyl)-λ-propen-7-one, /-(44-azidophenyl)-3- (--furyl)-coproben-7-
on,/.

λ, tri(p/-azidobenzoxy)hexane,
λ, t-bis(guazidobenzylidine-p-1-butya)/chlorhexanone, j, ≠'-diazidodibenzalacetone, ri, ≠'-diazidostilbene, 2. ．． 2
'-Disulfonic acid, μ'-azidobenzalacetophenone-2-sulfonic acid, ≠, μ'-diazidostilbene-α-carboxylic acid, di(p-azido-λ'-hydroxybenzal)acetone-nosulfonic acid ,≠-azidobenzathyacetophenone-cosulfonic acid, noazide-1
, the gauge is sulfonic acid aminonaphthalene, ≠14
Examples include ``-diazide-stilbene-λ, 2'-disulfonic acid anilide, and the like.

In addition to these low molecular weight aromatic azide compounds, there are
7/3, the azide group-containing polymer 33-- is also suitable.

Suitable compounds having ethylenically unsaturated bonds include polymers that can be crosslinked by photodimerization of ethylene bonds and polymerizable compounds that are photopolymerized to give inactive polymers in the presence of a photoinitiator.

For example, polymers that have ethylenically unsaturated bonds and become insolubilized by photodimerization include polyesters, polyamides, and polycarbonates containing -Cf (=CH-C- groups. Examples of such polymers include, for example, U.S. Pat. 3.030.201 and 3.707.373, such as photosensitive polymers containing photosensitive groups in the polymer backbone, e.g. consisting of p-phenylene diacrylic acid and diol. Photosensitive polyester, US Patent No. 2. rt, r'y
Photosensitive polymers such as those described in the specifications of No. R and No. J, /73.717, such as mono-prohelitenmalone M compounds such as cinnamylidenemalonic acid and cofunctional glycols. A photosensitive polyester derived from U.S. Pat. No. 2,490. ri AJ No. 2.732
．． 372 and 2,732.3o1, such as cinnamate esters of hydroxyl group-containing polymers such as polyvinyl alcohol, starch, cellulose and their analogs. It is.

Furthermore, examples of polymerizable compounds that can be photopolymerized to give an inactive polymer include those shown as components of the photopolymerizable composition.

Color-changing agents used to produce photosensitive resist-forming compositions that can produce visible images only by exposure to light include those that are originally colorless due to the action of photodecomposition products of free radical generators. There are two types: those that change to a colored state and those that originally have a unique color but change color or bleach.

Typical examples of color changing agents belonging to 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, ≠.

j'-biphenyldiamine, 0-chloroaniline, 0-
Bromoaniline, t-chloro-O-phenylenediamine, 0-bromo-N,N-dimethylaniline, /, 2.
3-1 rifhenylguanidine, naphthylamine, diaminodipheni with methane, aniline, J, j-dichloroaniline, N-methyldiphenylamine, 0-) luidine,
p, p'-tetramethyldiaminodiphenylmethane, N
, N-dimethyl-p-phenylenediamine, /, ,2-
Dianilinoethylene, p+p'+p"-hexamethyltriaminotriphenylmethane, p,p'-tetramethylaminodiphenyl-tetramethyldiaminodiphenylmethylimine, p*
p'of) // ) riamino-〇-methyltriphenylmethane, p, p/, p"-triaminotriphenylcarbinol, p, p'-tetramethylaminodiphenyl-
≠-anilinonaphthylmethane, p, p/, p
// ) lyaminotriphenylmethane, p, p', p
“-Methane to hexazolopyltriaminotripheni.

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-based thiazine, oxazine-based, xanthine-based, and anthracite-based agents. Quinones,
Various dyes such as iminonaphthoquinone type and azomethine type are effectively used.

Examples of these are: Brilliant green, eosin, ethylene (iolet, erythrosin B1 methyl green, crystal violet,
Peisic tuxin, phenoltucrein, 1.3-
Diphenyltriazine, Alizarin Red S1 Thymolphthalein, Methyl Violet 2B, Quinaldine Red, Rose Bengal, Methanil Yellow, Thymol Sulfof-37 = Thalein, Xylenol Blue, Methyl Orange, Orange ■, Diphenylthiocarbazone, Co, 7 Dichlorofluorescein, ) g-methyl red, Congo red, benzobrulin 4AB, α-naphthyl red, Nile blue JB, Nile blue A1 phenacetaline, methyl violet, malachite green, baratuxin,
Oil Blue #403 [manufactured by Orient Chemical Industry ■], Oil Pink #3/J [manufactured by Orient Chemical Industry ■], Oil Red jB (manufactured by Orient Chemical Industry ■), Oil Scarlet g30tC-manufactured by Orient Chemical Industry ■], Oil Red OG (manufactured by Orient Chemical Industry ■), Oil Red RR [manufactured by Orient Chemical Industry ■], Oil Green J
$t (7J (manufactured by Orient Chemical Industry ■), Subiron Red BEH Special [manufactured by Hojitani Chemical Industry ■], m-cresol chimi-pull, cresol red, rhodamine B1
Rhodamine AG.

Fast acid violet R1 sulforhodamine B1 auramine, μmp-diethylaminophenylimino naphthoquinone, cocarboxia 31-nilino II-p-diethylaminophenylimino naphthoquinone, cocarbostearylamino μmp-dihydroxyethyl-amino-phenylimino naphthoquinone, p- Methoxybenzoyl-p'-diethylamine-0'-methylphenyliminoacetanilide, cyano-p-diethylaminophenyliminoacetanilide,
l-phenyl-J-mef-II-p-diethylaminophenylimino-j-pyrazolone, l-β-naphthyl-q-p-diethylaminophenylimino-! -Pyrazolone.

In the photosensitive composition of the present invention, the photoactive agent 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. As a stabilizer for this purpose, US Pat.
．． The amines, zinc oxide, and phenols described in Ou2,675, 3. Sulfur compounds described in Ou 2.11A specification, Ou 3.0 Hiroko, alkali metal iodides and organic acids described in Ou 111 specification, organic acid anhydrides described in Ou 30r2ort specification, Ou 3377/ The triaryl compounds of antimony, arsenic, bismuth, and phosphorus described in No. 67 are effective.

The photosensitive composition of the present invention is used by dissolving the above-mentioned various components in a solvent and coating the solution on a suitable support by a known method. Next, preferred ratios and particularly preferred ratios of the various constituent components in this case are expressed in parts by weight relative to parts by weight of each ioθ of the photosensitive resist-forming compound.

Solvents used when coating the photosensitive composition of the present invention include ethylene dichloride, cyclohexanone, methyl ethyl ketone, cellosolve in methiacetate, monochlorobenzene, toluene, and ethyl acetate.

These solvents may be used alone or in combination.

When manufacturing a photosensitive lithographic printing plate, the coating amount is generally θ, /-/θ, 09/m in terms of solid content, and is particularly preferably 0.9/m. ! -, t, θ7/m2.

The photosensitive composition of the present invention is suitable as a photosensitive layer of a photosensitive lithographic printing plate. Suitable supports for photosensitive lithographic printing plates include hydrophilized aluminum plates, such as silicate-treated aluminum plates, anodized aluminum plates, grained aluminum plates, and silicate electrodeposited aluminum plates; Examples include plates, stainless steel plates, chrome-treated copper plates, and hydrophilized plastic films and paper.

In addition, when the photosensitive composition of the present invention is used to produce printing proof plates, films for overhead projectors, and films for second original drawings, suitable supports include polyethylene terephthalate film, cellulose triacetate film, etc. Examples include transparent films such as these, and those obtained by chemically or physically matting the surface of these plastic films.

When the photosensitive composition of the present invention is used for producing a film for a photomask, suitable supports include aluminum,
Examples include a polyethylene terephthalate film on which aluminum alloy or chromium is vapor-deposited, and a polyethylene terephthalate film on which a colored layer is provided.

Further, when the composition of the present invention is used as a photoresist, various materials such as a copper plate, a copper plated plate, a stainless steel plate, a glass plate, etc. can be used as a support.

When the free radical generating agent according to the present invention is exposed to light in a photosensitive resist-forming composition containing various photosensitive resist-forming compounds, it decomposes and efficiently and instantly discolors the coexisting color-changing agent. That is surprising. 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.

Furthermore, the free radical generating agent according to the present invention does not significantly inhibit the photodecomposition of the photosensitive resist-forming compound, and therefore does not significantly reduce the photosensitivity of the photosensitive resist-forming composition (the photosensitivity of the resist). Furthermore, since the free radical generating agent according to the present invention is effective when added in a small amount, physical characteristics of the resist image obtained after imagewise exposure and development of the photosensitive resist-forming composition are observed.
Does not deteriorate. For example, when the photosensitive resist-forming composition of the present invention is used as the photosensitive layer of a photosensitive lithographic printing plate, the characteristics such as developability, oil sensitivity, printing stains, and printing durability are affected by free radicals. Equivalent to when no generating agent was added.

The free radical generating agents of the present invention are also good hydrogen abstracting agents, producing acids in the presence of hydrogen donors. Therefore, by coexisting with a compound that can be decomposed by an acid, a photodegradable photosensitive composition can be obtained.

Examples of compounds that decompose with acids include U.S. Pat.
10/, No. 323, Ibid., Ko4A7. t// issue, same≠,
It is described in the specifications of 2gf, No. 937, μIλso, λj7, and No. 311.712.

Synthesis examples of the free radical generating agent used in the present invention and Examples of the present invention will be described below, but the present invention is not limited thereto.

Synthesis example: Cotetrichloromethyl-3-(p-styrylphenyl)
-/, 3, 1/, -Oxadiazole (synthesized p-aminobenzoic compound from a hardware store) Add 7f to 100ml of concentrated hydrochloric acid, add 100ml of water, and add sodium nitrite while cooling on ice. 23. A solution of jf dissolved in water jOgl was added dropwise.Furthermore, cinnamic acids re and r were added to this reaction solution.
After dropping a solution of y dissolved in acetone 2 j O,1, 70 ? of sodium acetate was added while cooling on ice. ,
A solution of cupric chloride ij, sy dissolved in #j g/water was added. The mixture was stirred on ice-cooled F for 2 hours and then at room temperature for 2 hours to react, and then left in the apparatus overnight to complete the reaction. After acetone was distilled off under reduced pressure, the mixture was cooled with water and the resulting precipitate was collected. By recrystallizing from acetic acid and further from ethanol, stilbene-gucarboxylic acid was obtained.

Stilbene-gucarboxylic acid-4Z,09, p-nitrophenol lt,'yy, f-ol chloride 3/.

02 and toluene 200111 were heated under reflux for 2 hours. After distilling off excess thionyl chloride, the reaction solution was cooled, and the precipitated stilbene-l-carboxylic acid p-nitrophenyl ester was collected in F*.

Stilbene-carboxylic acid p-nitrophenyl ester/2. Of and rOqA hydrazine hydrate, Of was added to 10@l methanol and heated under reflux for 30 minutes.

After cooling, the reaction solution is hydroxylated) IJumt2 is added to 301 ml of water.
A solution dissolved in 1 was added to obtain stilbene-l-carboxylic acid hydrazide.

Stilbene-Hiro-carboxylic acid hydrazide lj.

≠1 was added to a solution of hexachloroacetone 2/2f and acetonitrile/j O@l, and heated under reflux for 30 minutes. The reaction solution was cooled, the precipitate was evaporated, and N-(p
-Styrylbenzoyl)-N'-)lichloroacetyl hydrazide was obtained.

N-(p-styrylbenzoyl)-N'-)lichloroacetylhydrazide/2.09 and phosphorus oxychloride 10@l
After heating under reflux for 2 hours, the reaction solution was poured into 5 oz of ice water.
The resulting precipitate was recrystallized from acetonitrile to give 2-trichloromethyl-j-(p-styrylphenyl)-/, 3°goxadiazot-5zr, jf (melting point lμ2-3°
C) was obtained.

Example 1 After graining with a nylon brush, the following photosensitive solution was applied to a silicate-treated aluminum plate using a rotary coating machine.
O00C was dried for 13 minutes to form a photosensitive layer to produce a photosensitive plate.

The photosensitive liquids were prepared using the compound represented by the general formula (1) of the present invention and using a known compound for comparison. The compounds are shown in Table 1.

[Photosensitive liquid] Methyl methacrylate-methacrylic acid (molar ratio 1j//r) copolymer (in MBK, intrinsic viscosity at 300C O0 /1,1.) t, lf Trimethylolpropane triacrylate 3tf General formula (1 ) compounds (listed in Table 7) Cogtriphenyl phosphate lθV Ethyl cellosolve 430@1 Methylene chloride 330@1 For exposure, a step wedge (density step 0, / jO Concentration step number θ~is step)
was placed and irradiated with a metal halide lamp (Oljkw), and after exposure, development was performed using a developer having the following formulation.

[Developer]

Trisodium phosphate 21f/ Sodium phosphate sy Butyl cellosol 709 Activator 2xt Water /1 After the uncured portion was removed, the highest number of corresponding step wedges of the remaining image was shown in Table 1 as the sensitivity of the sample. . The higher the number of stages, the higher the sensitivity. Furthermore, Table 1 shows the sensitivity in the absence of the addition of a free radical generator of the general formula CI) as an experiment.

Table 1≠2- As shown in Table 1, when the free radical generator of the general formula CI) is used as a photopolymerization initiator, it exhibits extremely high sensitivity and the desired effect of the present invention is sufficiently achieved. Admitted.

Example 2 The following photosensitive liquid was applied to the aluminum plate obtained in Example 1,
A photosensitive printing plate was obtained.

Pentaerythritol tetraacrylate Hiroy Compound of general formula (1) (exemplary compound Ar), 2y Benzyl methacrylate-methacrylic acid (molar ratio 73/27) copolymer 409 Methyl ethyl ketone μ00 @1 Methyl cellosolve acetate 3oOyslThis photosensitive printing plate Jet printer (kW ultra-high pressure mercury lamp,
After imagewise exposure with a (Oak Manufacturing Co., Ltd.), the unexposed areas were removed and a clear image was obtained by developing with a developer having the composition shown below.

SO- Anhydrous sodium carbonate i0y Butyl cellosolve j1 Water /1 In addition, an unexposed printing plate was subjected to a forced aging test (ps0c7s%
Even after exposure and development after coating (FL, H0s0s), a clear image was obtained that was exactly the same as the printing plate immediately after coating.

Example 3 The following photosensitive liquid was applied to the aluminum plate obtained in Example/,
A photosensitive printing plate was obtained.

trimethylolzoro/e-trimethacrylate) 0.309 triethylene glycol diacrylate) 0. Off Methyl methacrylate-ethyl acrylate-methacrylic acid (molar ratio ro7io7io) Copolymer θ, t'2f Compound of general formula (() (Exemplary Compound Shop//) 0.02V Leuco Crystal Violet Q, 00 When the photosensitive lithographic printing plate containing 10 methyl ethyl ketone was imagewise exposed, a printed image with rich contrast was obtained.

Then caustic soda/M, isopropyl alcohol 30θ
A lithographic printing plate was obtained by removing the unexposed areas with a developer consisting of 11,000 @l of water.

Example 4 The following photosensitive liquid was applied to a 0.11 mm thick aluminum plate with a grained surface using a Whaler.

A photosensitive lithographic printing plate was prepared by drying at 0C for 2 minutes.

Naphthoquinone-(/,λ)-diazide(2)-j-sulfonylchloroIJ)'',!: esterified product with hyrogallolacet/resin o,'ysy cresol novolak resin 2,/f tetrahydrophthalic anhydride 0. /1?Crystal/(Iolet 0
．． 029 Free radical generator (listed in Table 2) 0.03? Ethylene dichloride /If Methyl cellosolve i2y The coating amount after drying was f/m'2.

After each of these photosensitive lithographic printing plates was exposed to a 30 amp carbon arc lamp from a distance of 70 cIR, DP
-/(Product name: Fuji Photo Film Co., Ltd., positive type P
To
The film was developed for seconds and the sensitivity was measured.

The appropriate exposure time at this time was determined to be a point at which the 5th step is completely clear in the gray scale with optical density differences o and ij.

In addition, the optical densities of the exposed and unexposed areas of the photosensitive layer over time were measured using a macroscopic reflection densitometer.

Furthermore, after forcing these photosensitive planographic printing plates to age,
The above measurements were repeated. Conditions for forced aging are temperature≠j'C,
The humidity was 7j% for 7 days.

53- The image obtained by exposure appears sharper as the difference (ΔD) between the density of the exposed area and that of the unexposed area is larger. These results are shown in Table 2.

-! - From Table 2, the free radical generator A/ of the present invention has a longer aging property than the conventional one, '(1)-chlorostyryl)-quattrichloromethyl-/, J, 4Z-oxadiazole. Are better. In addition, 11 μm bis(trichloromethyl)-a-p-methoxystyryl-8-triazine is as good as the free radical generator A/ of the present invention in terms of aging properties, but is slightly inferior in printout performance and resist sensitivity. It is also inferior in that it reduces

Example 5 The following photosensitive liquid was applied to the aluminum plate obtained in Example G to obtain a photosensitive printing plate.

Esterification reaction product of naphthoquinone-(/,co)-diazide-(2)-r-sulfonyl chloride and cresol novolac resin 0.7jf Cresol novolac resin λ, ioy Tetrahydrophthalic anhydride o, 1jy General formula (1) Free radical generator A7 0.02V Crystal Violet 0. O1f/oilbu n, -
1JA 03 0.0/ fl (Orient Chemical Industry Co., Ltd.) % formula % Application type i after drying is 2. It was 2/m2.

By imagewise exposing this photosensitive lithographic printing plate, it was possible to obtain a clear printed image without developing it. The exposed areas faded, while the unexposed areas remained at their original density, making it possible to recognize the details of the image even under safety lights.

Example 6 The following photosensitive liquid was applied to the aluminum plate obtained in Example 1 to obtain a photosensitive printing plate.

p-)luenesulfonate, a condensate of p-diazodiphenylamine and paraformaldehyde 0.21 Polyvinyl formal 0.7jf Free radical generator / 0.0 t N,N-dimethylaniline 0.029 Methyl cellosolve The dry coating amount of methanol jv was /,097 m2. When this photosensitive lithographic printing plate was image-exposed, the exposed areas developed a purple color, while the unexposed areas remained their original yellow color, making it possible to obtain printed images that were recognizable in detail even under safety lights. Ta.

Example 7 The following photosensitive liquid was applied to the aluminum plate obtained in Example 1 to obtain a photosensitive printing plate.

p-phenylene diacrylic acid Equimolar 7. Hiroshi Bis(β-hydrogyceto) xy) with cyclohexane Polyvarnish synthesized by condensation Chill O1!1 Cobenzoylmethylene-3 zr- -Methyl-β-naphthothia Pudding 0.037 Free radical generator A/0,00rfl leuco crystal violets to . , θ ozy Monochlorobenzene 2 Ethylene dichloride t2 The coating weight after drying was 297 m2.

When this photosensitive lithographic printing plate was exposed to light, the exposed areas developed a purple color, while the unexposed areas remained their original yellow color, making it possible to obtain printed images that were recognizable in detail even under safety lights. Ta.

Patent applicant: Fuji Photo Film Co., Ltd.

Claims (1)

[Claims] Co-halomethyl-j-substituted-/ represented by the following general formula (1), 3. A photosensitive composition containing a II-oxadiazole compound as a free radical generator. Here, A represents a substituted or unsubstituted aromatic residue, and Y
represents a chlorine atom or a bromine atom, and n represents an integer of 1 to 3.