JPS60239736A - Photosensitive composition - Google Patents

Abstract

PURPOSE:To elevate sensitivity of photodecomposition and to sufficiently enhance sensitivity of a photosensitive compsn. by incorporating an s-triazine compd. represented by formula I. CONSTITUTION:The photosensitive compsn. contains the photosensitive s-triazine compd. represented by formula I in which (A) is an optionally substd. aromatic residue; Y is Cl or Br; n is an integer of 1-3; and (A) is a group having an aryl or heterocyclic aromatic residue, preferably, mono- or bicyclic, such as phenyl, 1-naphthyl, 2-naphthyl, 2-furyl; 2-thienyl, 2-oxazole, 2-thiazole, 2-imidazole, 2- pyridyl, 2-benzofuryl, 2-benzothienyl, 2-quinoly, and far preferably, a monocyclic aryl group.

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 present invention relates to a photosensitive composition containing a novel photosensitive 8-) riazine compound.

“Conventional technology” Compounds that decompose and generate free radicals when exposed to light (
free radical generators) are well known in the graphic arts field. They are photopolymerization initiators in photopolymerizable compositions,
It is widely used as a photoactivator in free radical photographic compositions and as a photoinitiator for photogenerated acid-catalyzed reactions. Such free radical generators are used to make a variety of photosensitive materials useful in printing, duplication, copying and other imaging systems.

Organic halogen compounds photolyze to give halogen radicals such as chlorine radicals and bromine radicals. These halogen radicals are good hydrogen abstractors and produce acids in the presence of hydrogen donors. For their application to photopolymerization processes and free radical photography processes, see J. Kosar, “Li
ght Sensitive Systems JJ, Wi
ley & 5ons (New York/9tri/
10~/II 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 only separate light in a very limited wavelength range.

It was sensitive to ultraviolet wavelengths 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.
sensitizers such as merocyanine dyes, styryl bases and cyanine bases as described in US Pat. 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. rij44,117! No. 3, 21
There is a group of halomethyl-5-) lyazine compounds described in No. 7,037 and No. 323, No. 7,037. 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.

"Problems to be Solved by the Invention" Even with free radical generating agents whose photosensitive wavelength range is from near ultraviolet to visible light, the sensitivity to photodecomposition is still low and the sensitivity of photosensitive compositions is not sufficiently high.

"Means for Solving the Problems" As a result of extensive research, the present inventors found that the above problems were solved by a photosensitive composition containing a novel S-)IJ azine compound represented by the following general formula CI). did.

The compound of the present invention also had good compatibility with other components in the composition.

Here, A is an unsubstituted or substituted aromatic residue, Y
represents a chlorine atom or a bromine atom, and n represents an integer of 1 to 3.

The present invention will be explained in more detail.

In general formula CI), the aromatic residues include aryl groups and heteroaromatic residues, preferably monocyclic or bicyclic ones, such as phenyl group, l-naphthyl group, λ-naphthyl group. , cofuryl group, cochenyl group, cochiazole group, cochiazole group, 2-imidazole group, cochyridyl group, λ-benzo7lyl group, cobenzochenyl group, copenzoxazole group, λ-benzothiazole group, copen Examples include a zimidazole group, a benzotriazole group, a λ-indolyl group, and a coquinolyl group. Preferably it is a monocyclic aryl group.

The substituted aromatic residue for A is an alkyl group having 7 to 2 carbon atoms, such as a methyl group or an ethyl group, or an alkyl group having 7 to 2 carbon atoms, such as a methoxy group or an ethoxy group, in addition to the above-mentioned aromatic residues. Includes those substituted with ~2 alkoxy groups, such as halogen atoms such as chlorine atoms, nitro groups, phenyl groups, carboxy groups, hydroxy groups, cyano groups, etc. Specifically, ≠-chlorophenyl group, cochlorophenyl group , μm bromophenyl group, ≠-nitrophenyl group,
3-nitrophenyl group, ≠-phenylphenyl group, Hiro-
Methylphenyl group, comethylphenyl group, ≠-ethylphenyl group, ≠-methoxyphenyl group, λ-methoxyphenyl group, ≠-ethoxyphenyl group, cocarboxyphenyl group, ≠-cyanophenyl group, 3. Hiro-methylenedioxyphenyl group, ≠-phenoxyphenyl group, ≠-acetoxyphenyl group, ≠-hydroxyphenyl group, 2.
'l-dihydroxyphenyl group, ≠-methyl-l-naphthyl group, ≠-rio C1-/-f phthyl group, '-nitro=/-naphthyl group, t-chloro-2-naphthyl group, terflomo-2-naphthyl group group, j-nitro-1-naphthyl group, 6-methyl-2-benzofuryl group, t-methyl-λ~
Examples include a benzoxazole group, a t-methyl-λ-benzothiazole group, and a t-chloro-2=benzothiazole group. Preferably, it is a monocyclic substituted aromatic residue.

S − represented by the general formula (I) used in the present invention
) The IJ azine compound is synthesized by the following method. That is, R. Adam's et al. 1'-Orga
nic 5intheses J ('J, Wiley
& 5ons) Collective Volume
-2, t, the method described on page 23, or V, C
ovjell.

He1vetica Chimica Acta
K using an aromatic nitrile compound represented by the general formula (II) and haloacetonitrile synthesized according to the method described in

Written by Wakabayashi et al. (where A is synonymous with general formula CI) Bulletin of the Chemical
5ocietyof JapanX442, lid +2≠
It can be synthesized by cyclization according to the method described in .

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

A/ Ad m3 CH(J 2 Aμ j A ct3 A7 ya r Cα3 ya r cz CCl3 10 Boiled// A/, 2 ct3 Al2 A/ ≠ ll ct3 A/, 4 Al7 The free radical generating agent of the present invention Ability to provide a visible image without development by exposure when used as a photopolymerization initiator in a polymerizable composition and in a photosensitive resist-forming composition for producing lithographic printing plates, IC circuits, and photomasks. This is particularly useful when giving

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 the photosensitive layer of a photosensitive printing plate, 7-otonist, 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 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, J-butane diol diacrylate, and tetramethylene glycol diacrylate. acrylate, zolopylene glycol diacrylate, trimethylozoro/monotriacrylate, trimethylolethane triacrylate, /,≠-cyclohexanediol diacrylate, tetraethylene glycol diacrylate,
Pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol triacrylate, dipentaerythritol tetraacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, polyester There are acrylate oligomers, etc. Examples of methacrylate acid esters include tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, ethylene glycol dimethacrylate, l,3-butanediol dimethacrylate, and pentaerythritol. dimethacrylate, pentaerythritol trimethacrylate,
dipentaerythritol diacrylate, nrubitol trimethacrylate, sorbitol tetramethacrylate, bis-(p-(J-methacryloxy-cohydroxyzolopoxy)phenylcdimethylmethane, bis-(
Examples include p-, c-acryloxyethoxy) phenylcdimethylmethane. The itaconic acid esters include ethylene glycol shiitaconate, propylene glycol diitaconate), /, J-butanediol shiitaconate, l,≠-butanediol shiitaconate, tetramethylene glycol shiitaconate, pentaerythritol shiitaconate. nate, sorbitol tetrataconate”
etc. Examples of crotonic acid esters include ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, bentaerythritol dicrotonate, and sorbitol tetracrotonate. There are isocroton versions such as ethylene glycol diisocrotonate, bentaerythritol diynerotonate, and nrubitol diisocrotonate. Maleic acid esters include ethylene glycol simalate,
Examples include triethylene glycol simarate, pentaerythritol simarate, and tulpitot tetramalate.

Furthermore, mixtures of the aforementioned esters may also be mentioned.゛Specific examples of amides of aliphatic polyvalent amine compounds and unsaturated carboxylic acids include methylene/bis-acrylamide, methylenebis-methacrylamide, /, O-hexamethylenebis-acrylamide, /, 4-hexamethylenebis-acrylamide, -Methacrylamide, diethylenetriamine trisacrylamide, xylylene bisacrylamide, xylylene bismethacrylamide, etc.

Other examples include Tokko Sho≠? The following general formula (
CH=C(R)COOCH2CH(R')OH( III
) (However, R and R' represent H or CH3.) When the free radical generating agent of the present invention is used as a photopolymerization initiator in a photopolymerizable composition, the photopolymerizable composition may optionally contain A binder may be included.

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 photosensitive material manufacturing process leading to the preparation, coating, and drying of a coating solution of the phase composition. The photosensitive layer or resist layer should be able to be developed after image exposure, whether by solution development or peeling development, and be strong as a photosensitive layer or resist layer. Although it is required to have characteristics such as being able to form a film, it is usually selected as appropriate, such as a linear organic polymer. Specific examples of the binder include chlorinated polystyrene, chlorinated polypropylene, polyacrylic acid alkyl ester (alkyl groups include methyl group, ethyl group, n-butyl group, iso-7" f group, n-
hexyl group, 2-ethylhexyl group, etc.), copolymer of acrylic acid alkyl ester (alkyl group is same as above) and at least one monomer such as acrylonitrile, vinyl chloride, vinylidene chloride, styrene, butadiene, polyvinyl chloride, chloride Copolymers of vinyl and acrylonitrile, polyvinylidene chloride, copolymers of vinylidene chloride and acrylonitrile, polyvinyl acetate, polyvinyl alcohol, polyacrylonitrile, copolymers of acrylonitrile and styrene, copolymers of acrylonitrile with butadiene and styrene. Polymer, polymethacrylic acid alkyl ester (alkyl groups include methyl group, ethyl group, n-propyl group, n-butyl group, is.

-butyl group, n-hexyl group, cyclohexyl group, λ-
ethylhexyl group, etc.), a copolymer of a methacrylic acid alkyl ester (the alkyl group is the same as above) and at least one of heptamers such as acrylonitrile, vinyl chloride, vinylidene chloride, styrene, butadiene, polystyrene,
Poly-α-methylstyrene, polyamide (Otsu-nylon, A, j-nylon:/flto), methylcellulose,
Examples include ethyl cellulose, acetyl cellulose, polyvinyl formal, and polyvinyl butyral.

Furthermore, if a water or alkaline water soluble organic 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 methacrylic acid ether 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 (copolymers of ethyl acrylate and acrylic acid, copolymers of butyl acrylate and acrylic acid,
copolymers of ethyl acrylate with styrene and acrylic acid), itaconic acid copolymers, crotonic acid copolymers, partially esterified maleic acid copolymers, etc.; There are acidic cellulose derivatives with

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 5,000 to 5,000.
-2,000,000, more preferably in the range of 10,000 to 10,000,000.

When the photopolymerizable composition of the present invention further contains a sensitizer, a sensitizer that increases the photopolymerization rate when used in combination with the photopolymerization initiator represented by general formula (1) is selected. .

Specific examples of such sensitizers include benzoin, benzoin methyl ether, benzoin ethyl ether, terfluorenone, λ-chloro=2-fluorenone, λ-
Methylterafluorenone, teranthrone, λ-promoteranthrone, coethyluteranthrone, IO-anthraquinone, λ-ethylrutha.

IO-anthraquinone; ) Phenylstyryl ketone, p-(dimethylamine) phenyl p-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, preferred sensitizers in the present invention include compounds represented by the following general formula (■) described in Japanese Patent Publication No. Shoyo--≠grit.

1 In the formula, R is an alkyl group (e.g., methyl group, ethyl group, propyl group, etc.) or a substituted alkyl group (e.g.,
λ-hydroxyethyl group, comethoxyethyl group, carboxymethyl group, cocarboxyethyl group, etc.).

R2 is an alkyl group (for example, methyl group, ethyl group, etc.)
, or an aryl group (eg, phenyl group, p-hydroxyphenyl group, naphthyl group, chenyl group, etc.).

2 is a nonmetallic atomic group necessary to form the nitrogen-containing heterocyclic nucleus usually used in cyanine dyes, such as benzothiazoles (benzothiazole, j-chlorobenzothiazole, t-chlorobenzthiazole, etc.), naphthothiazole (α-naphthothiazole, β-naphthothiazole)
), benzoselenazole (benzoselenazole, !-chlorobenzoselenazole, t-methoxybenzosenazole, etc.), naphthoselenazole (α-naphthoselenazole, β-naphthoselenazole, etc.), benzoxazole (benzoxazole, j-methylbenzoxazole, j-phenylbenzoxazole, etc.), naphthoxazole (α-naphthoxazole, β-s7toxazole, etc.).

Specific examples of the compound represented by general formula (IV) include:
It has a chemical structure that is a combination of these Z, R, and R2, and many of them exist as known substances. Therefore, it is possible to appropriately select and use these known materials.

Furthermore, preferred sensitizers in the present invention include US Pat. The sensitizer described in No. trt, Example:
Bis(2-furoyl)methylenecou 3-methylbenzothiazoline, '(bis(2-thinoyl)methylenecou 3-
Examples include methylbenzothiazoline, 2-(bis(+2-furoyl)methylene-3-methylnat(/,2-d)thiazoline), and the like.

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-ti-p-cresol, hyrogallol, ti-chacatechol, benzoquinone, cuprous chloride, phenothiazine, floranil, naphthylamine, β-naphthol, and nitrobenzene. ,
Examples include dinitrobenzene.

In some cases, dyes or pigments 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. are used for coloring purposes. 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 dibutyl phthalate, diethyl phthalate, dibutyl phthalate, diethyl phthalate, dicyclohexyl phthalate, ditritecylphthalate, dimethyl glycol phthalate, ethyl phthalyl ethyl glycolate, butyl phthalyl butyl glycolate. Glycol esters such as chloride, phosphate esters such as tricresyl phosphate, triphenyl phosphate,
Examples include aliphatic dibasic acid esters such as diisobutyl adipate, dioctyl adipate, dibutyl sebacate, and dibutyl maleate.

The photopolymerizable composition of the present invention is used by dissolving the above-mentioned various components 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 based on 100 parts by weight of the polymerizable compound having an ethylenically unsaturated bond.

When the free radical generating agent of the present invention is used in a photosensitive resist-forming composition, the photosensitive resist composition is exposed to light under a yellow safety light during the exposure operation. For example, in the process of exposing many printing plates at the same time, a visible image is obtained only by
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 single large plate is exposed to light many times in the process of making a lithographic printing plate, the operator can immediately check which part has been exposed. be able to.

A photosensitive resist-forming composition which gives a visible image immediately upon exposure, in which the free permanent forming agent of the present invention can be advantageously used, contains as essential components a photosensitive resist-forming compound, a free radical generator, a color change agent and, optionally, a color change agent. It usually consists of one or more plasticizers, binders, non-color-changing dyes, pigments, antifoggants, sensitizers for photosensitive resist-forming compounds, and the like.

A photosensitive resist-forming compound is a compound that changes physical properties such as resistance to exposure to light, solubility, tackiness, and adhesion to a substrate. Includes compounds with saturated bonds and compounds that undergo photocatalyzed reactions.

Suitable photosensitive diazo compounds include salts of p-diazodiphenylamine, such as phenol salts, fluorocaprates, and triisopropylnaphthalenesulfonic acid, ≠
, H′-bisphenylcissulfonic acid, ! - ditroorthotoluenesulfonic acid, j-sulfosalicylic acid, 2. !
-dimethylbenzenesulfonic acid, λ-nitrobenzenesulfonic acid, 3-chlorobenzenesulfonic acid, 3-bromobenzenesulfonic acid, cochroro! -Nitrobenzenesulfonic acid, no-fluorocaprylnaphthalenesulfone L /-naphthol-j-sulfonic acid, comethoxy≠-hydroxy-! - Compounds having two or more diazo groups in one molecule, such as a condensate of formaldehyde and a salt of a sulfonic acid such as benzoylbenzenesulfonic acid and para-toluenesulfonic acid, are preferred. Other preferable diazo compounds include the above salts2. j? -dimethoxy-μmp-condensate of tolylmercazotobenzenediasonicum and formaldehyde, 2,3-dimethoxy-
Examples include condensates of l-morpholinobenzenediazonium and formaldehyde or acetaldehyde.

Additionally, other useful diazo compounds are described in U.S. Pat. t
≠includes compounds such as those described in No. 373.

These become insoluble due to decomposition of the cydiazo group by irradiation with actinic light.

On the other hand, photosensitive diazo compounds which 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, U.S. Patent No. 30≠tiio, U.S. Patent No. 30≠A//
/ No. 30 Hiroshi 4/16, No. 30≠1/, No. 30 6120, No. 30444/21, No. 30≠612λ, No. 3/300u7 , No. 31
No. 300uI, No. 311rJ'210, No. 311
No. 41310, same No. J/Jo OII r, same t7g
3io2ro No. 9, Jlti No. 1? 13, Jlti No. 31
Examples include those described in various specifications such as fij11'i00 and fij11'i022.

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. The azide group of these decomposes when exposed to light to produce nitrene, which becomes insolubilized through various reactions of nitrene. Preferred aromatic azide compounds include one or more groups such as azidophenyl, azidostyrylazidobenzal, azidobenzoyl and azidocinnamoyl;
For example, ≠ p/-diazide force, gouazide-u
'-(4cm azidobenzoylethoxy)chalcone, N
1N-bis-p-azide, benzal-p-phenylenediamine, /, J, 4-)su(benzoxy)
Hexane, λ-azido-3-chlorobenzoquinone, -
, Hiro-diazide-zhen'-ethoxyazobenzene, 2,6
-di(≠!-azidobenzal)-termethylcyclohexanone, ≠′-diazidobenzophenone, λ,! −
Diazido 3. t-dichlorobenzoquinone, λ, j-bis(4cm azidostyryl)-7゜3, oxadiazole, -1(≠-azidocinnamoyl)thiophene,
λ, j-di(4c/-azidobenzal)cyclohexanone, ≠, reference I-diazidophenylmethane, l-(4c
mazidophenyl)-yo-furyl-2-venter2. ≠
-dien-7-one, /-(4A-azidophenyl)-
j-(≠-methoxyphenyl)-venter 1. ≠-dien-3-one, /-(4C-azidophenyl)-3-(
l-su7thyl)zoloben-/-one, no(≠-azidophenyl)-J-(<4-dimethylaminophenyl)-
Propan-l-one, / (≠-acidophenyl-5-
Phenyl-/, 4t-pentadien-3-one, /-C
a-azidophenyl)-J-(≠-nitrophenyl)-
noproben-l-one, /-(≠-azidophenyl)
-3-(2-furyl)-norzoloben-l-one, l.

λ, tri(≠′-azidobenzoxy)hexane, co,6-bis(≠-azidobenzylidine-p-t-butyl)cyclohexanone, ≠,≠′-diazidodibenzalacetone, ri, z′- Diazidostilbene-X/-
Disulfonic acid, μ'-azidobenzalacetophenone-
Nosulfonic acid, μ, ≠′-diazidostilbene-α-
Carboxylic acid, cy(≠-azido λ'-hydroxybenzacy)acetone-nosulfonic acid, ψ-azidobenzalacetophenone-2-sulfonic acid, λ-azido7. ≠
-dibenzenesulfonylaminonaphthalene,.

Examples include ≠, ≠'-diazidose stilbene-2,2'-disulfonic acid anilide.

In addition to these low molecular weight aromatic azide compounds, there are also
113, same≠j-2μri/j, same≠j-2jt7/3,
The azide group-containing polymers described in the publications are 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 having ethylenically unsaturated bonds and becoming cine-solubilized by photodimerization include polyesters, polyamides, and polycarbonates containing -CH=CH-C- groups. Such polymers include, for example, U.S. Pat. No. 3,030.201.
Photosensitive polymers containing a photosensitive group in the polymer main chain, such as photosensitive polyesters consisting of p-phenylene diacrylic acid and diol, as described in the specifications of No. 3,707,373 and US Pat. Patent No. 2.9! A, 1
Photosensitive polymers, such as 2-probelidenmalonic acid compounds such as cinnamylidenemalonic acid, and cofunctional glinols, as described in the specifications of No. 7za and No. 73.71r7. A photosensitive polyester derived from U.S. Pat. tri 0. No. 46, No. 2, 73
2, J7J, and 2.732.3oi, such as polyvinyl alcohol, starch, cellulose, and cinnamic acid of hydroxyl group-containing polymers such as cellulose and the like. These include esters.

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, ≠.

μ/i phenyldiamine, 0-chloroaniline, O-bromoaniline, J-chloro-0-phenylenediamine,
o-i lomo N, N-dimethylaniline, /, 2.3-
) liphenylguanidine, naphthylamine, diaminodiphenylmethane, aniline, X, j-,) chloroaniline, N-methyldiphenylamine, o-toluidine, I
) l I) ``7'tramethyldiaminodipheni with methane, N,N-dimethyl-p-phenylenediamine, 1
．． 2-dianilinoethylene, p, p', p"-hexamethyltriaminotriphenylmethane, pII)'-tetramethyldiaminodiphenylmethane, p, p'-tetramethyldiaminodiphenylmethylimine, p, p'
, p“-triamino-0-methyltriphenylmethane,
prp'+p"-triaminotriphenylcarhinol, p, p'-tetramethylaminodiphenyl-≠-anilinonaphthylmethane, p, p', p"hetriaminotriphenylmethane, p, p', p" -hexapropyltriaminotriphenylmethane.

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

Examples of these are: Brilliant green, eosin, ethyl violet, erythrosin B1 methyl green, crystal violet, (
Ishitsuku fuchsin, phenolphthalein, l,3-diphenyltriazine, alizarin red S1 thymol butanein, methyl violet 2f3. Quinaldine Red, Rose Bengal, Methanil Yellow, Thymol Sulfophthalein, Xylenol Blue, Methyl Orange,
Orange ■, diphenylthiocarhason, 217-dichlorofluorescein, /1! Lamethyl Ret, Congo Red, Benzozolpurine 4 (B, α-Naphthyl Red, Nile Blue JB, Nile Blue A1 Phenacetaline, Methyl Violet, Malachite Green,) Laraxine Oil Blue #603 [Manufactured by Orient Chemical Industry ■] , Oil Pink #31-2 [manufactured by Orient Chemical Industry ■], Oil Red jB [manufactured by Orient Chemical Industry ■]
, Oil Blue Let #301 (manufactured by Orient Chemical Industry ■), Oil Red OG (manufactured by Orient Chemical Industry ■), Oil Red RR [manufactured by Orient Chemical Industry ■], Oil Green #jOλ [manufactured by Orient Chemical Industry ■] , Spiron Red BEH Special [manufactured by Hojidani Chemical Industry ■]
, m-cresol/nucle-sol, cresol red, rhodamine B, rhodamine AG.

Fast Acid Violet B1 Suphorodamine B1 Auramine, μ-p-diethylaminophenyliminona 7-toquinone, λ-carboxyanilino≠-p-diethylaminophenyliminonaphthoquinone, -1-carbostearylamino-μmp-dihydroxyethyl-amino- Phenylimino naphthoquinone, p-methoxybenzoyl-p'-diethylamine-07-methylphenylimituacetanilide, cyano-p-diethylaminophenyliminoacetanilide, l-phenyl-3-methylda-p-diethylaminophenylimino! -pyrazolone, l-β-naphthyl-≠-p-diethylaminophenylimino-j-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 patent
, 011, amines, zinc oxide, phenols described in J'7j specification, sulfur compounds described in J'7j specification 3.0≠2.114, 3.0≠2. ! Alkali metal iodide, organic acid, 30rdo described in the specification of No.lr
Organic acid anhydride described in rt specification, 3377/17
The triaryl compounds of antimony, arsenic, bismuth, and phosphorus described in the specification are effective.

The photosensitive composition of the present invention is used by dissolving the above-mentioned food constituents 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 each ioo part by weight of the photosensitive resist-forming compound.

o　O　also　os　.

Examples of solvents used when coating the photosensitive composition of the present invention include ethylene dichloride, cyclohexanone, methyl ethyl ketone, methyl cellosol acetate, monochlorobenzene, toluene, and ethyl acetate. - These solvents may be used alone or in mixtures.

When producing a photosensitive lithographic printing plate, the coating amount is generally suitably 0.1 to 10.097 m'' in terms of solid content, particularly preferably O1!~z, of/m.

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 hydrophilic aluminum plates, such as silicate-treated aluminum plates, anodized aluminum plates, grained aluminum plates, clay electrodeposited aluminum plates, and others. Examples include zinc plates, stainless steel plates, chromium-treated copper plates, and hydrophilized plastic films and paper.

In addition, when the photosensitive composition of the present invention is used to produce a printing proof plate, a film for an overherad projector, and a film for second original drawings, suitable supports for these include polyethylene terephthalate V-) film, triacetic acid film, etc. Examples include transparent films such as cellulose films, and plastic films whose surfaces have been chemically or physically matted.

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.

Furthermore, 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, since the free radical generating agent according to the present invention does not significantly inhibit the photodecomposition of the photosensitive resist-forming compound, it 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, it does not deteriorate the physical characteristics of the resist image obtained after imagewise exposure and development of the photosensitive resist-forming composition. 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 and generate acids in the presence of hydrogen donors. Therefore, by coexisting with a compound that is decomposed by acid, a photodegradable photosensitive composition can be obtained.

Examples of compounds that decompose with acids include U.S. Pat.
10/, No. 323, same φ, 2≠7. No. 611, same! ,
It is described in the specifications of No. 2411.937, No. 2411.937, No. 210.2≠7, No. 31/, and No. 7t2.

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 2 - Synthesis of (p-styrylphenyl)-4', g-bis(trichloromethyl)-8-triazine (Exemplary Compound A/) Terephthalaldehyde J/, It was dissolved in 200 parts methanol and added to it. A solution of sodium methoxide≠, 3f dissolved in methanol AO ml was added at room temperature.

To this reaction solution, add 30.71% of benzyltriphenylphosphonium chloride in methanol/! A solution dissolved in Oml was added dropwise at room temperature, and the reaction was further continued at room temperature for 2 hours.

The reaction solution was poured into a large amount of water, and the resulting precipitate was collected in a furnace.

Recrystallize from a mixed solvent of ethanol and water to obtain stilbene-≠
-Aldehydota,≠7 was obtained.

Stilbene-≠-aldehyde 20, J'ri was dissolved in ethanol 10.1 and hydroxylamine sulfate? A solution of RiV in 201 g of water was added. Furthermore, a solution of sodium hydroxide t,oy dissolved in 10@l of water was added to this reaction solution, and the reaction was allowed to proceed at room temperature for 3 hours. The resulting precipitate was collected in a furnace and washed with water to obtain stilbene-≠-aldoxime coO0≠1.This aldoxime λ0. ≠2 and acetic anhydride AOtsl were heated under reflux for 30 minutes and then poured into 300 ml of ice water to obtain the product sterilbe/zonitrile it,sy.

≠-styrylbenzonitrile, 29 and trichloroacetonitrile/3.09 in chloroform/! Boron fluoride ethyl ether complex/ml is added while cooling this solution to -j'C.
Furthermore, hydrogen chloride gas was introduced into the reaction system for 1 hour. After blowing in hydrogen chloride gas, the reaction was carried out at O0C for 2 hours and at room temperature for 3 hours.

After distilling off the solvent under reduced pressure, the residue was poured into 300 ml of ice water to obtain crude crystals. By recrystallizing the crude crystals from a mixed solvent of chloroform and hexane, 2-(p-styrylphenyl)-≠, 6-bis() IJ dichlorotyl)
-s-triazine s, sf was obtained (melting point/70.0~i
'yi, o 0c).

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.
It was dried at 0o 0c for 3 minutes to form a photosensitive layer and 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.

In the photosensitive liquid methyl methacrylate-methacrylic acid (molar ratio 1 s//s) copolymer CMEK, the intrinsic viscosity at 300C is 0. /it) iGcof Trimethylolpropane triacrylate 3rt Compound of general formula CI) (listed in Table 1) 22 Triphenylphosphate lOf Ethyl cellosolve tsogo Methylene chloride 33;0g11 Exposure was carried out using a vacuum printing frame apparatus, A step wedge (density step difference 0./j0 density step number O to is steps) was placed on the photosensitive plate, and a metal halide lamp (Oos kW ) was irradiated, and after exposure, development was performed using a developer having the following formulation.

Developer Trisodium Phosphate 252 Sodium Phosphate sr Butyl Cellosolve 70F Activator -2 ml Water/l Exposure time when exposed so that the density at the same number of step wedges in the image obtained by development is equal It is shown in Table 1. The shorter the exposure time, the higher the sensitivity.

As shown in Table 7, the compound represented by the general formula CI) according to the present invention has an existing trichloromethyl group.
It showed higher sensitivity than the triazine compounds (compounds with numbers 3 to 3), and the intended effects of the present invention were fully observed.

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

Pentaerythritol tetraacrylate ≠oy General formula C General formula C compound (Exemplary compound A) 2? Benzyl methacrylate-methacrylic acid (molar ratio 73/27) copolymer 609 Methyl ethyl ketone ≠00. l Methyl cellosolve acetate j 00 ml This photosensitive printing plate was image-exposed using a jet printer (2kW ultra-high pressure mercury lamp, manufactured by Oak Seisakusho), and then developed with a developer having the composition below to remove the unexposed areas and make the plate clear. A great image was obtained.

Anhydrous sodium carbonate 109 Butyl cellosolve! 2 Wednesday / 1 In addition, an unexposed printing plate was subjected to a forced aging test (≠50C714
Rin, H6! Even after exposure and development after 3 days), 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 1,
A photosensitive printing plate was obtained.

trimethylolpropane) IJ methacrylate) 0.309 triethylene glycol diacrylate), 0, Or? Methyl methacrylate-ethyl acrylate-methacrylic acid (molar ratio 1rO/10/lo) Copolymer o, tλ2 Compound of general formula CI) (exemplary compound At) 0.0co2 0icocrystalpiolet) 0.0019 Methyl ethyl ketone log When this photosensitive lithographic printing plate was imagewise exposed, a printed image with rich contrast was obtained.

Then caustic soda/, 2? , isozorobyl alcohol 3
oOm1. A lithographic printing plate was obtained by removing the unexposed areas using a developer of 00 ml of water.

Example 4 The following photosensitive solution was coated with whey 2- to an aluminum plate with a thickness of 0.16 mm with a grained surface, and heated at 1000C for 2-
A photosensitive lithographic printing plate was prepared by drying for a minute.

Naphthoquinone-(/,2)-diazide (2) Esterified product of -s-sulfonyl chloride and pyrogallol acetone resin 0.739 Cresol novolak resin λ,/f Tetrahydrophthalic anhydride 0. /jf Crystal Violet 0.02f Free radical generator (listed in Table 1) 0.029 Ethylene dichloride /1r2 Methyl Celloso Mb 129 These photosensitive printing plates were printed using the jet printer used in Example λ. The optical density of the exposed and unexposed areas of the photosensitive layer was measured using a Macbeth reflection density needle.

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.

Furthermore, after these photosensitive planographic printing FX were forced to age, the above measurements were repeated. The forced aging condition is temperature≠j'C
, humidity was 75% for 7 days.

These results are shown in Table 2.

As shown in Table 2, the free radical generating agent of the present invention had a large ΔD value and gave a clear image. In addition, when using the free radical generating agent of the present invention, '(1)-methoxystyryl)
-≠, when t-bis(trichloromethyl)-8-) riazine was used (comparative example), the value of ΔD was higher than that, demonstrating the high sensitivity of the free radical generator of the present invention. .

Furthermore, the development sensitivity of the exposed printing plate was measured using a 4-fold dilution of Dr-/ (product name: Fuji Photo Film Co., Ltd., developer for positive PS plates) at 2s 0c for 60 seconds. With the free radical generator of the invention (Table 2, Experiment S2) and without it (Table 2, Experiment A/
) was the same. This indicates that the free radical generating agent of the present invention does not reduce the resist sensitivity of photosensitive ψ.

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

Esterification reaction product of naphthoquinone-(/,2)-diazide-(2)-s-sulfonyl chloride and cresol novolac resin 0.73f Cresol novolac resin λ, IO? Tetrahydrophthalic anhydride o, 1zy free radical generating agent shown by general formula C7) o, oiy Crystal Piolet) 0.01f Oilb AI-#AO30,1) It (Orient Chemical Industry Co., Ltd.) % formula % After drying The coating weight was 2 f/m''.

By exposing this photosensitive lithographic printing plate to light, a clear printout image could be obtained without development. The exposed areas faded, while the unexposed areas remained at their original density, making it possible to see every detail in 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 of condensate of p-diazodiphenylamine and paraformaldehyde 0.21 Polyvinyl formal 0.719 Free radical generator A/ 0.02y N,N-dimethylaniline 0-029 Methyl cellosolve 20? The dry coating amount of methanol If was /,097 m''. When this photosensitive lithographic printing plate was imagewise exposed, the exposed areas developed a purple color, and the unexposed areas remained their original yellow color. We were able to obtain printed images that were recognizable in detail even under safety lights.

Example 7 The following photosensitive liquid was applied to the aluminum plate obtained in Example No. to obtain a photosensitive printing plate.

p-Phenicyl Acrylic Equimolar l and da of ethyl acid bis(β-hydroxyethyl) (Toxy)cyclohexane and Polyester synthesized by the condensation of Stell 0. ! f λ-benzoylmethylene-3 monomethyl-β-naphthothia Pudding 0.03? Free radical generator A7 0.001f leuco crystal pielets )o,oory Monochlorobenzene tag Ethylene dichloride t1 The coating weight after drying was 1.2 f/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, resulting in a printed image that could be recognized in detail even under safety lights. .

Claims (1)

[Scope of Claims] A photosensitive composition containing a photosensitive s-)riazine compound represented by the following general formula (T). Here, A is an unsubstituted or substituted aromatic residue, Y
represents a chlorine atom or a bromine atom, and n represents an integer of 1 to 3.