JPH03263405A - Photopolymerizable composition - Google Patents

Abstract

PURPOSE:To obtain the new title composition having high sensitivity and photosensitive properties to laser light source and useful for photomask, etc., by blending an ethylenic unsaturated bond-containing polymerizable compound with a new compound as a photosensitive initiator. CONSTITUTION:The aimed composition containing (A) a polymerizable compound (e.g. acrylylic acid) having an ethylenic unsaturated bond and (B) an organic boron compound anion salt of organocationic dye compound expressed by formula I [D<+> is formula II (R<11> and R<12> are alkyl; L<1> to L<3> are methine, n is 0-4; A<1> to A<4> and B<1> to B<4> are H or electron attracting group, provided that at least one among A<1> to A<4> and B<1> to B<4> is electron attracting group; Y<1> and Y<2> are atomic groups capable of taking a cyclic structure together with carbon atom located at 3 position of indolenin nuclei; R<1> to R<4> are alkyl or aryl].

Description

DETAILED DESCRIPTION OF THE INVENTION "Industrial Application Field" The present invention relates to a photopolymerizable composition containing a novel photopolymerization initiator. More specifically, it is a high-sensitivity product that can be used for applications such as i4 plate printing, resin letterpress, printing board production l/cyst or photomask, monochrome or color transfer coloring sheet or coloring sheet production, etc. The present invention relates to a photopolymerizable composition that is spectrally sensitized.

"Prior Art" A photopolymerizable composition basically consists of a photopolymerization initiator and an addition-polymerizable compound containing two or more ethylenically unsaturated bonds in the molecule (hereinafter referred to as "polyfunctional monomer"). including;
When exposed to light, it hardens, changing its tackiness or becoming insoluble in solvents. Taking advantage of these properties, it is widely used in photography, printing, metal surface processing, ink, etc. The concept and application examples are described in many publications. For example, J.
Written by Cote [Light System Systems]
THE WILLY AND THEN'S NEURO-RI (
J, Kosar “Light 5-ensitive
Systems JJ, Wiley & 5ons,
New Yoyk) 1965, pp. 158-193° - Coma Ai, Jacobun, Boul Φ - - Ja; -ri(
K+I+Jacohson, El, ,'E+Jae
l'Irnaging 5ystenn by obson
s-i J.

Wiley &; 5ons, New York
) 1976, pages 181-222, etc. for details.

Furthermore, in recent years, as an image forming method using a photopolymerizable composition, an image forming system using a photosensitive microcapsule in which a photopolymerizable composition is encapsulated in microcapsules has been proposed. For example, Shima-kai No. 157-124343, JP-A-57-179836, and JP-A-57-1.97538 disclose microcapsules containing a photopolymerizable composition consisting of a vinyl compound and a photopolymerization initiator and a dye. A method of forming a dye image is disclosed by stacking a coated color-forming sheet on an image-receiving sheet after exposure and applying pressure to the entire sheet.

In addition, in recent years, the application of these photopolymerizable compositions to color photosensitive materials has been studied in an attempt to form digital images by spectral sensitization up to 7 visual ranges and using a laser as a light source. There is C.

For example, Journal of the Photographic Society of Japan, Vol. 49, 3. No. 230 pages (198
6) and "Functional Materials, September 1983, 4," pages 48 to 60, describe a method for spectral sensitization of photopolymerizable compositions for use in laser recording. “Stop.

JP-A-59-189340 describes a method of spectral sensitization using an organic peroxide initiator and an all-organic dye.

Further, Tsuba Patent No. 223.587A1 discloses an organic boron anion salt of an organic cationic dye as a new photopolymerization initiator.

In particular, the method of using the organic boron compound anion salt of the organic cationic dye compound as a photosensitive Shi-1 initiator is as follows:
This method is useful in that it allows a wide selection of cationic color-forming compounds and allows designing a photopolymerization initiator composition that is sensitive to any wavelength.

``Problem to be Solved by the Invention-1'' However, although these methods yielded photopolymerization initiator compositions that were sensitive to visible light, satisfactory photosensitivity could not be obtained.

``Object of the Invention'' One object of the present invention is to provide a novel photopolymerization initiator composition that is highly sensitive and sensitive to light sources of visible light or higher. More specifically, a resist for making lithographic printing plates, resin letterpress plates, and printed circuit boards that is highly sensitive and sensitive to visible light or higher light sources, such as laser light sources, using a novel organic boron compound anion salt of an organic cationic dye. Another object of the present invention is to provide a photopolymerization initiator composition that can be advantageously used in photomasks. Another object of the present invention is to provide a photopolymerization initiator composition for microcapsules that has high sensitivity and is sensitive to a light source of visible light or higher, which can be advantageously used for black-and-white or color image formation.

"Means for Solving the Problem" As a result of research by Eisho, the present inventors discovered that (a) a polymerizable compound having an ethylenically unsaturated bond in one molecule and (b) an organic cation represented by the following general formula (1). The inventors have discovered that the above object can be achieved by using a photopolymerizable composition containing an organic boron anion salt compound of a cationic dye and gold, the organic cationic dye compound being represented by the following general formula (If). .

General formula (1) Here, D represents a cationic color scheme represented by general formula (It); R4, B2, R3 and R4 may be the same or different, and include an alkyl group, a substituted alkyl group, an aryl group, Substituted aryl group, aralkyl group, substituted aralkyl group,
alkaryl group, substituted alkaryl group, alknyl group,
Substituted alkynyl group, alkynyl group, substituted alkynyl group,
A group selected from an alicyclic group, a heterocyclic group, and a substituted heterocyclic group; R1, R2, R3, and R4 are the 2
It may be a cyclic structure in which more than one group is bonded.

General Formula (It) In the formula, Bli and B12 each represent an alkyl group, and Ll, B2, Jaku and B3 all represent a methine group. n represents an integer from θ to 4, and AI, A2, A3, A4,
B1, B2, B3 and B4 each represent a hydrogen atom or an electron-withdrawing group (Hammett's 〉0). However, A1
, A2, A3, A4, B1, B2, B3, B4, at least one represents an electron-absorbing group.

Examples of the alkyl group represented by R11 and R+12 include alkyl groups having 1 to 18 carbon atoms (unsubstituted alkyl groups (e.g., methyl, ethyl, propyl, isopropyl,
Butyl, inbutyl, hexyl, octyl, dodecyl,
octadecyl), substituted alkyl groups such as aralkyl groups (side-light benzyl, 2-phenylethyl), hydroxyalkyl groups C examples, tjf, 2-hydroxyethyl, 3
-hydroxypropyl), carboxyalkyl groupull
, 2-carboxyethyl, 3-carboxypropyl, 4
-carboxybutyl, carboxymethyl), alkoxyalkyl groups (e.g. 2-methoxyethyl, 2-(2-
methoxyethoxy)ethyl), sulfoalkyl groups [e.g., 2-sulfoethyl, 3-sulfopropyl, 3-sulfobutyl, 4-sulfobutyl, 2-[3-sulfopropoxy]ethyl, 2-hydroxy-3-sulfopropyl,
3-sulfopropoxyethoxyethyl), sul7atoalkyl groups (e.g. 3-sul7atobrovir, 4-sul7atoptyl), heterocyclic-substituted alkyl groups (e.g. evaz-(
pyrrolidin-2-one-1-yl)ethyl, tetrahydrofurfuryl), 2-acetoxyethyl, carbomethoxymethyl, 2-methanesulfonylaminoethyl)allyl group).

Ll, B2. The methine group represented by Lll may be substituted, and examples of the substituent include an alkyl group (
methyl, ethyl), aryl groups (e.g. phenyl), aralkyl groups (e.g. benzyl) or halogen atoms (e.g. chlorine, bromine), alkoxy groups (e.g. methoxy, ethoxy), and substitution of methine chains. The groups may form a 4 I/s L 6 negative ring.

Further, B11 or B12 may form a 4- to 6-membered ring together with Ll, B2, or B3.

Examples of electron-withdrawing groups represented by A%A%A, A%B%B, and B%B include halogen atoms (
fluorine atom, chlorine atom, bromine atom, iodine atom), nitro group, carbamoyl group 11thl'carbamoyl group, N-ethylcarbamoyl group, N-propylcarbamoyl group, N
-hexylcarb7yl group), alkoxycarbonyl group (e.g. methoxycarbonyl group, ethoxycarbonyl group, 2-ethylhexyloxycarbonyl group, octyloxycarbonyl group), sulfamoyl group [e.g. sulfamoyl group, N-butylsulfamoyl group] ) and cyano bases.

Yl and Y2 together with the bromine atom at the 3-position of the (3H)indole nucleus represent a 4- to 7-membered ring (e.g., cyclobutane, cyclopentane, cyclo\xane, cycloheptane, tetravitrobilane, N~Methylpiperidine, etc.) 'fc formation' kH, T ability j' atomic group n...represented.

Organoboron compounds represented by general formula (1), U.S. Pat. Nos. 3,567,453 and 4,307,182
No. 1, 4,343. g No. 91・, 4, 44.7,
No. 521, No. 4,45 O, No. 227, JP-A-62-1
Various compounds can be used with reference to No. 50242, No. 143044, etc., but the most preferred compounds are 1==R2=R, 3: phenyl, p-methoxyphenyl, p--butoxyphenyl, It is a compound of p-dimethylaminoneenyl or p-chlorophenyl, methyl, ethyl, propyl, butyl, n-hexyl or n-hebutyl.

As the compound of general formula (1), it is also possible to use an anion salt of an organic boron compound of an organic cation dye synthesized based on the above-mentioned patents. Any salts such as chloro salts, iodo salts, etc. and any salts of organic boron compounds such as butragtylammonium salts may be optionally added.

Specific organic compounds and side tones of organic boron compound anion salts of divalent dye compounds are listed below. However, the effects of the present invention are limited to the following compounds.

H3 Hx 04m9-B(-Q)s ■ 5H11 CsH+1 C4H9-stone-Q)5 7H15 C7H+s 10°3-4 The polymerizable compound having an ethylenically unsaturated bond in the composition of the present invention is defined by its chemical structure. at least 1 in
compounds with ethylenically unsaturated bonds in chemical forms such as monomers, prepolymers, i.e. dimers, trimers and other oligomers, mixtures thereof and copolymers thereof. It is. 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 triacrylate, 1.3=butanediol diacrylate, tetramethylene glycol diacrylate,
Propylene glycol diacrylate, trimethylolpropane triacrylate, trimethylolethane triacrylate, 1,4-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, Examples include polyester acrylate oligomers. Examples of methacrylic acid esters include tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, trimethylpropane trimethacrylate, trimethylolethane trimethacrylate, ethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate,
dipentaerythritol dimethacrylate, sorbitol trimethacrylate, nrubitol tetramethacrylate, bis-[:p-(3-methacryloxy-2-hydroxypropoxy)phenylfudimethylmethane, bis-1:p-(acryloxyethoxy)phenyl Examples include Fujimethylmethane. The itaconic acid esters include ethylene glycol shiitaconate, brobylene glycol diitaconate), 1,3-butanediol diitaconate), 1,4-butanediol shiitaconate, tetramethylene glycol shiitaconate, and pentaerythritol. Examples include shitaconate and sorbitol tetrataconate. Examples of crotonic acid esters include ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate, and sorbitol tetracrotonate. As the incrotonic acid ester, ethylene glycol diisochloro 1
7- -18 = tonate, pentaerythritol diisocrotonate, sorbitol tetrine crotonate, etc. Examples of maleic esters include ethylene glycol simarate, triethyl 1/glycol dimalate, pentaerythritol simarate, and sorbitol detramarate. 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, methylene bis-methacrylamide, 1,6-heximethylene bis-acrylamide, and the like.

Examples include 6-hexamethylene bis-methacrylamide, diethylene triamine tris-acrylamide, xylylene bis-acrylamide, and xylylene bis-methacrylamide.

As another example, the following general formula (
There are beer urethane compounds containing two or more polymerizable vinyl groups in one molecule to which a vinyl monomer containing a hydroxyl group as shown in III) is added.

CHz-C(R')COOC112Ci(('B')D
H(I[) (where R/ and R″ are H or Cl
ll5 is shown. ) Also, a polymer compound having a vinyl group or vinylidene group, for example, a polymer compound having a hydroxyl group, amine group, epoxy group, halogen atom, or sulfonyloxy group in the side chain, and acrylic acid, methacrylic acid, or these Condensation with a derivative of can also be used in the present invention.

Furthermore, compounds containing vinyl groups in the molecules of color image-forming substances, such as dyes or leuco dyes, can also be utilized as polymerizable compounds.

The organic boron compound as the organic cationic dye compound is preferably added in an amount of 0.01 to 50 M to the polymerizable compound.

The novel photopolymerizable composition containing the above-mentioned polymerizable compound having an ethylenically unsaturated bond and the compound having an organic boron compound anion salt of a hair root turnip dye compound can be used for various purposes. can do.

For example, a layer comprising the photopolymerizable composition and a binder polymer may be deposited on a support in accordance with U.S. Pat.
No. 2, No. 4,587,199, No. 4,629゜680
No. 4,415.652, No. 4,431.7
No. 23, No. 4,550,073 1 Japanese Government) J Special Edition 6
1-285,444, 61-213213, etc., Japanese Patent Publication No. 62-67529, U.S. Patent No. 4,
It can be applied to many fields (C) according to methods known in the industry, such as color proof materials with reference to No. 604,340.

Further, since the photopolymerizable composition of the present invention is highly sensitive and sensitive to visible light, it can be particularly advantageously used for image forming systems using microcapsules.

Used in image forming systems using microcapsules
For example, JP-A No. 57-1.97538 and JP-A No. 6
No. 1-130945, No. 5g-88739, No. 58~
88740, European Patent No. 223.587A1, etc. can be referred to. This image forming method is, for example, %ethyl
A photopolymerization initiator composition consisting of a non-polymerized vinyl compound and a photoinitiator and microcapsules containing a dye precursor are coated on a support, and the photosensitive sheet 1-image-wise is photoneutralized.
After curing the microcapsules in the exposed area, the colorant sheet is stacked and pressurized over the entire surface to destroy the microcapsules in the unexposed area, and transfer the color image forming substance (e.g. dye pre-color) to the image receiving element (e.g. color developer). This is a method in which the color is transferred to the dye layer) and developed. The present invention will be explained below by taking an example of an image forming system using these microcapsules.

Various additives can be added to the photopolymerizable composition of the present invention depending on the purpose. For example, a thermal polymerization inhibitor, a polymerization accelerator, a color image forming substance (dye, dye precursor, or pigment), etc. can be added.

Photosensitive material 1-1 using the photopolymerizable composition of the present invention will be described below. 22- The method for producing the material will be described below.

Various methods can be used to manufacture photosensitive materials, but the general manufacturing method is to prepare a coating solution by dissolving, emulsifying, or dispersing the components of the photosensitive layer in an appropriate solvent, and then coating. This process consists of applying the liquid to a support as described above and drying it to obtain a photosensitive material.

Generally, each of the above-mentioned coating liquids is prepared by preparing a liquid composition containing each component and then mixing the respective liquid compositions. The above liquid composition may be prepared for each valley component, or may be prepared to contain a plurality of components. The constituent components of the photosensitive layer in part - can also be added during or after the preparation of the liquid composition or coating solution. Furthermore, as described below, an oil-based (or aqueous) composition containing one or more components,
Furthermore, a method of preparing a secondary composition by emulsifying it in an aqueous (or oil-based) solvent can also be used.

The polymerizable compound of the photopolymerizable composition of the present invention can be added to the photosensitive layer in the form of droplets, or the droplets can be surrounded by a microcapsule wall. At this time, it is preferable that the organic boron compound anion salt of the organic cationic dye compound is also contained in the droplets.

The composition of the present invention may further contain a thermal polymerization inhibitor mainly for the purpose of preventing polymerization of the photopolymerizable composition during storage. Specific examples of thermal polymerization inhibitors include:

Side light, p-methoxyphenol, hydroquinone, alkyl- or aryl-substituted hydroquinone, t-butylcatechol, pyrogallol, cupric oxide, floranil, naphthylamine, β-naphthol, 2,6-di-t
Examples include -butyl-p-cresol, pyridine, nitrobenzene, dinitrobenzene, I)-)luidine, methylene blue organic copper, and methyl salicylate. These thermal polymerization inhibitors are preferably contained in an amount of 0.001 to 5 parts by weight per 100 parts by weight of the ethylenically unsaturated compound.

The composition of the present invention further contains -8H in the molecule as a polymerization accelerator.
It is also possible to use reducing agents, such as compounds that act as oxygen scavengers and chain transfer agents for active water volume donors, in combination with compounds having . Oxygen scavengers that have been found to be useful include phosphines, phosphonates, phosphites,
Tin salts and other monomer compounds that are easily oxidized by oxygen. Useful chain transfer agents are N-phenylglycine,
Trimethylbarbic acid, 2-mercaptobenzoxazole.

2-Mercaptobenzthiazole, N,N-dimethyl-
2,6-diituprobylaniline, N, -2,4゜6-
pentamethylaniline and other compounds with hydrogen that can be easily extracted by radicals.

The composition of the present invention may contain a color image-forming substance, and after removing the unpolymerized portion, the polymerized portion may be colored, or the unpolymerized portion may be transferred to an image-receiving element to form a color image.

There are a variety of color image-forming materials that can be used in the present invention. For example, dyes and pigments are examples of substances that are themselves colored. When these are used, a color image can be formed by destroying the portion (C microcapsules) in which no polymer is formed and transferring them to an image-receiving material using an appropriate method. In addition to commercially available dyes and pigments, there are also known dyes and pigments described in various documents (for example, "Dye Handbook" edited by the Organic Synthetic Chemistry Association, published in 1972; "Latest Pigment Handbook" edited by Japan Pigment Technology Association, published in 1978). I can use things. These dyes or pigments are used after being dissolved or dispersed.

On the other hand, uncolored color image-forming substances include those that are colorless or pale in themselves but develop color when subjected to some kind of energy such as heating, pressure, or light irradiation; It is classified as one that develops color when it comes into contact with another component. Known examples of the former include thermochromic compounds, piezochromic compounds, photochromic compounds, and leuco compounds such as triarylmethane dyes, quinone dyes, indigoid dyes, and azine dyes. All of these exhibit 1:1 color development upon heating, pressure, light irradiation, or air oxidation.

Examples of the latter include various systems that develop color through acid-base reactions, redox reactions, coupling reactions, chelate-forming reactions, etc. between two or more components. For example, a coloring system consisting of a coloring agent with a partial structure such as lactone, lactam, or spiropyran used in pressure-sensitive paper, and an acidic substance (coloring agent) such as acid clay or phenols: aromatic diazonium salts, diazotates, A system using azo coupling reaction of diazosulfonates, naphthols, anilines, active methylenes, etc.; reaction of hexamethylenetetramine with ferric ion and gallic acid, and phenolphthalein-combrexonic acid. A chelate-forming reaction such as a reaction between ferric stearate and an alkaline earth metal ion, and a redox reaction such as a reaction between ferric stearate and pyrogallol or a reaction between silver behenate and 4-methoxy-1-naphthol can be used.

Furthermore, as another example of a system in which color is generated by a reaction between two components, a case in which this reaction proceeds by heating is known. In this case, it is necessary to heat the mixture at the same time that the two components are mixed by breaking the microcapsules during pressurization, or immediately after pressurization.

The color former in the color former/color developer system is (1
Specific examples include 1) realy lumethane-based compounds, (2) diphenylmethane-based compounds, (3) xanthine threads, (4) thiazine-based compounds, and (5) spiropyran-based compounds.

Among them, (1) triarylmethane type, (
3) The coloring agent for xanthine threads is preferably one that causes less fog and provides high coloring density. Specific examples include crystal violet lactone, 3-diethylamino-6
-chloro7-(β-ethoxyethylamino)fluorane, 3-diethylamino-6-methyl-7-anilinofluorane, 3-triethylamino-6-methyl-7-anilinofluorane, 3-cyclohexylmethylamino-
Examples include 6-methyl-7-anilinofluorane and 3-diethylamino-7-chloroanilinofluorane, which may be used alone or in combination.

As the color developer, phenolic compounds, organic acids or metal salts thereof, oxybenzoic acid esters, acid clay, etc. are used.

Examples of phenolic compounds include 4,4'-isobrohylidene diphenol (bisphenol A), p-1e
rt-butylphenol, 2,4-dinitrophenol, 3,4-dichlorophenol, 4,4'-methylene-bis(2,6-tert-butylphenol),
p-phenylphenol, 1.1-bis(4-hydroxyphenyl)cyclohegizan, l11-bis(4-hydroxyphenyl)-2-x tylhexane, 2.2-bis(4-hydroxyphenyl)butane, 2.2' -methylenebis(4-tert-butylphenol L2,2'
-methylenebis(a-phenyl-p-cresol)thiodiphenol, 4,4'-thiobis(6-term-butyl-m-cresol), sulfonyldiphenol, p-tcrt-butylphenol-formalin condensate, p -Fue; lephenol-formalin m compound fx
There is.

Examples of organic acids or their metal salts include phthalic acid, anhydride 7
Talic acid, maleic acid, benzoic acid, gallic acid, 0-toluic acid, p-toluic acid, salicylic acid, 3 tert-
butylsalicylic acid, 3,5-di-ter1-butylsalicylic acid, 5-α-methylbenzylsalicylic acid, 3.5
-(α-methylbenzyl)salicylic acid, 3-tert.
-Octylsalicylic acid and its zinc, lead, aluminum, magnesium salts, nickel salts, etc. are useful. In particular, salicylic acid derivatives and their salivary lead salts or aluminum salts are excellent in terms of developing ability 5, fastness of color images, storage stability of recording sheets, and the like.

Examples of the oxybenzoic acid varnish sol include ethyl p-oxybenzoate, butyl p-oxybenzoate, heptyl p-oxybenzoate, benzyl p-oxybenzoate, and the like.

In addition, all oil-absorbing white pigments are used in combination, and 29-1 in the capsule is 30- It is also possible to diffuse and fix colored objects.

These color developers are added as a eutectic with a thermofusible substance of a low melting point in order to melt at a desired temperature and cause a color reaction, or a low melting point compound is added to the surface of the color developer particles. It is preferable to add it in a fused state.

Specific examples of low melting point compounds include waxes such as higher fatty acid amides such as stearic acid amide, erucic acid amide, valmitic acid amide, ethylene bisstearamide or higher fatty acid esters, benzoyl phenyl derivatives, and aromatic ether derivatives. , or urea derivatives, but are not limited thereto.

Examples of other color formers/developers include phenolphthalein, fluorescein, and 2'.

4/, 5/, 7'-tetrabromo-3,4,5,6-titrachlorofluorescein, tetrabromophenol blue, 4,5,6.7-tetrabromophenolphthalein, eosin, ararin cresol red , 2-7-tholephenolphthalein, and the like.

Color developers include inorganic and organic ammonium salts, organic amines, amides, urea and thiourea and their derivatives, 17zoles, virols, biridines, piperazines, guanidines, indoles, imidazoles, Examples include nitrogen-containing compounds such as imidacillins, triazoles, morpholines, piperidines, amidines, formacins, and pyridines. Specific examples of these include ammonium acetate, tricyclohexylamine, )lihenzylamine, octadecylbenzylamine, stearylamine, allyl urea, thiourea, methylthiourea, allylthiourea, and ethylenethiourea.

2-benzylimidazole, 4-phenylimidazole, 2-phenyl-4-methyl-imidazole, 2-undecyl-imidacillin, 2,4.5-trifuryl-2-
Imidacillin% 1.2-di7-di-4,4-dimethyl-2-imidacillin, 2-phenyl-2-imidazoli/, 1,2.3-triphenylguanidine, 1.2-ditolylguanidine, lI2- Dicyclohexylguanidine, 1,2-dicyclohexyl-3-phenylguanidine, 1.2.3-tricyclohexylguanidine, guanidine trichloroacetate, N,N'-dibenzylpiperazine.

4.4'-dithiomorpholine, morpholinium trichloroacetate, 2-amino-benzothiazole, and 2-benzoylhydrazino-benzothiazole.

The color image forming material of the present invention is used in an amount of 0.5 to 20 parts by weight, particularly preferably 2 to 7 parts by weight, based on 100 parts by weight of the polymerizable compound. The color developer is used in a proportion of about 0.3 to 80 parts by weight per 1 part by weight of the color former.

When microcapsulating the photopolymerizable composition of the present invention, it can be produced by methods known in the industry. For example, methods utilizing coacervation of hydrophilic wall-forming materials as seen in US Pat. No. 2,800,457 and US Pat. No. 2,800,458, US Pat.
No. 43, Special Publication No. 38-19574, 446-1973
No. 42-771, the interfacial polymerization method,
Methods based on polymer precipitation described in U.S. Pat. No. 3,418,250 and U.S. Pat. No. 3,660,304; U.S. Pat.
No. 9, U.S. Pat. No. 3,914,511; U.S. Pat.
Methods using urea-formaldehyde-based or urea-formaldehyde resorcinol-based wall forming materials as seen in US Pat. No. 4,087,376 and US Pat. The in 5 ftu method by polymerization of monomers, which is found in Japanese Patent Publication No. 36-9168 and Japanese Patent Application Laid-Open No. 51-9079, British Patent No. 95280
7, No. 965,074, and the spray drying method as shown in US Pat. No. 311.1407 and British Patent No. 930,422. Although not limited thereto, it is preferable to emulsify the core material and then form a polymer film as the wall of the micro-33-34 capsule.

The microcapsule wall of the present invention is particularly effective when the microcapsule method by polymerizing the adhesive actant from inside the oil droplet is used. That is, within a short period of time, the particle size becomes uniform.

Capsules with a sharp neck can be obtained as recording materials with excellent life-saving properties.

For example, when polyurethane is used as a capsule wall material, a polyvalent isocyanate and a second substance (e.g. polyol, polyamine) that reacts with it to form the capsule wall are used.
is mixed into the oil-based liquid to be encapsulated, emulsified and dispersed in water, and then the temperature is completely raised to cause a reaction to form light molecules at the oil droplet interface.

Forms the microcapsule wall. At this time, a co-solvent with a low boiling point and strong dissolving power can be used in the oily liquid.

In this case, regarding the polyvalent isocyanate to be used and the polyol and polyamine to be reacted with it, US Pat.
No. 268, Special Publication No. 48-40347, No. 49-24
No. 159! Ichigokai No. 48-80191, 4th-84
It was opened in issue 086 and can also be used for convenience.

Examples of polyisocyanates include nl-phenylene diisocyanate, p-phenylene/cyisocyanate, and 2.6-ylene diisocyanate.

2.4-Tolylene diisocyanate, naphthalene 1.4
-diincyanate, diphenylmethane-4゜4'-diisocyanate, 3.3'-dimethoxy-4゜4x-vinoenyl diisocyanate, 3.3'-dimethoxy-diphenylmethane-4,J'-diisocyanate, xylylene-1 , 4-diisocyanate, 4゜4'-dinenylpropane diisocyanate),) I7 methylene diisocyanate, hegisamethylene diisocyanate;'y-t, propylene-1,2-diisocyanate, butylene-1,2
-Diisocyanate, cyclomethane-1,2-
Diisocyanate, diisocyanate such as cyclohexylene-1,4-diisocyanate, 4.4',! ”
-) Triisocyanates such as 2,4,6-inocyanate, toluene-2,4,6-inocyanate, 4,4'-dimethyldiphenylmethane-
Tetraisocyanates such as 2,2', 5.5'-tetrine cyanate, adducts of hexamethylene diisocyanate and trimethylolpropane, 2.4-) adducts of lylene diisocyanate and trimethylolbrono, xylylene diisocyanate There are isocyanate prepolymers such as adducts of tolylene diisocyanate and trimethylolpropane, and adducts of tolylene diisocyanate and Santriol.

Examples of polyols include aliphatic and aromatic polyhydric alcohols, hydroxy polyesters, and hydroxy polyalkylene ethers.

The following polyols described in @Kai No. 60-49991 can also be used: ethylene glycol, 1°3-propanediol, and 1,4-butanediol.

1.5-bentanediol, 1.6-hexanediol, 1.7-hebutanediol, 1.8-octanediol
・L, propylene glycol, 2.3-dihydroxybutane, 1,2-dihydroxybutane, 1.3-dihydroxybutane, 2.2-henmethyl-1,3-propanediol, 2.4-bentanediol, 2.5 -Hekylene diol, 3-methyl-1,5-1:tanthane diol, 1,4-cyclohexane dimetatool, dihydro-4-dicyclohexane, diethyl lenco-A/%
1,2.6-)! J hydroxyhexane, 2-non-21-nylbrobylene glycol, L, 1.1-) IJ mef*-
Aromatic compounds such as 1 propane, hexane) + J-ol, hentaerythritol, bentaerythritol ethylene oxide adduct, glycerin ethylene oxide adduct, glycerin, 1,4-di(2-hydroxyethoxy)benzene, resorcinol dihydro diethyl ether, etc. Condensation product of polyhydric alcohol and alkylene oxide, p-xylylene glycol, m-xylylene glycol, a, a'-dihydro, p-diisopropylbense/, 4,4'-dihydroxy-diphenylmethane,
2-εp, p'-dihydroxydiphenylmethyl)＼
Examples include adducts of ethyl alcohol, bisphenol A and ethylene oxide, and bisphenol A and propylene oxide adducts. Polyol has a ratio of hydroxyl groups to 1 mole of incyanate groups of 0.0.
It is preferable to use 2 to 2 mol.

Examples of polyamines include ethylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, p-phenylenediamine, m-phenylenediamine, piperazine, 2-methylbiperazine, 2,5-dimefkpiperazine, and 2-hydroxytrimethylenediamine. , diethylenetriamine, triethylenetriamine, triethylenetetramine, diethylaminoprobylamine, tetraethylenepentamine,
Examples include amine adducts of epoxy compounds.

Polyvalent isocyanates can also react with water to form polymeric substances.

When making microcapsules, water-soluble polymers can be used, and the water-soluble polymers may be any of water-soluble 7-ionic polymers, nonionic polymers, and amphoteric polymers.

Both natural and synthetic anionic molecules can be used, such as -coo-so;
Examples include those having groups such as tl, ru. Specific anionic natural polymers include gum arabic, alginic acid, and pectin, while semi-synthetic products include carboxymethyl cellulose, phthalated gelatin, sulfated starch, sulfated cellulose, and lignin sulfo/acid.

Synthetic products include maleic anhydride-based (including hydrolyzed) copolymers, acrylic acid-based (including methacrylic acid-based) polymers and copolymers, vinylbenzenesulfonic acid-based polymers and copolymers, Examples include carboxy-modified polyvinyl alcohol.

Examples of nonionic polymers include polyvinyl alcohol, hydroxyethyl cellulose, and methyl cellulose.

Examples of amphoteric compounds include gelatin.

These water-soluble polymers are used as an aqueous solution of 0.01 to 10 wt1. The particle size of the microcapsules is adjusted to 20μ or less.

The size of the capsule used in the present invention is 80μ or less,
In particular, it is preferably 20 μm or less from the viewpoint of storage stability and handling properties. Furthermore, if the capsule is too small, there is a risk that it will disappear into the pores or fibers of the substrate, but this depends on the properties of the substrate or support and cannot be definitively determined, but it is preferably 0.1 μm or more.

The capsule used in the present invention does not substantially change at pressures below about 1011/cd, and preferably breaks when a pressure greater than this is applied, but the magnitude of the pressure at which this breakage occurs depends on the application. Although it can be changed and is not limited to a specific value, approximately 5
00 Kf/a! It is preferable that the rupture occurs at a pressure of less than a certain degree. These pressure characteristics can be controlled by the particle size of the capsule, the thickness of the capsule wall, and the type of wall material used.

A solvent can be used in conjunction with the encapsulation of the polymerizable compound and color image forming substance according to the present invention. A solvent can also be used when introducing a reducing agent, color developer, etc. into necessary elements. For example, a solution dissolved in water or a hydrophilic organic solvent can be coated directly on the support together with a binder if necessary;
It can be introduced into necessary elements by known methods such as the method described in No. 27. By using a solvent in the microcapsules, it is also possible to control the degree of destruction of the capsules upon pressurization and the amount of transfer of the color image-forming substance within the capsules to the image receiving element. The amount of solvent used in the capsule is 1 to 50 parts by weight per 100 parts by weight of the polymerizable compound.
A ratio of 0 parts to 0 parts is preferred.

Natural oil or synthetic oil can be used in combination as the solvent used in the present invention.

Examples of these solvents include, for example, cottonseed oil, kerosene, aliphatic ketones, aliphatic esters, paraffins, aliphatic ketones, alkylated biphenyls, alkylated terphenyls, chlorinated paraffins, alkylated nanthalenes, and 1-phenyl- Diarylethanes such as 1-xylylethane, 1-phenyl-1-p-ethylphenylethane, 1,1'-ditolylethane and the like.

41-42 Fucuric acid alkyl esters (dibutyl phthalate, dioctyl 7-talate, etc.), phosphoric acid esters (diphenylphos 7-ace), )! j phenyl phosphate, tricresyl phosphate, dioctyl butyl phosphate)
, citric acid esters (e.g. acetyl tributyl citrate), benzoic acid, rx? ru (octyl tetraate), 7
lower alkyl acetates such as ruamide (eg diethyl laurylamide), fatty acid esters (eg dibutoxyethyl succinate, dioctyl acetate), trimesic acid esters (eg tributyl trimesate), ethyl acetate, butyl acetate.

Examples include ethyl propionate, secondary butyl alcohol, methyl imbutyl alcohol, β-ethoxylated acetate, methyl cellosolve acetate, and cyclohexanone.

The image-receiving element used with the photosensitive element using the composition of the present invention is an element for developing and possibly immobilizing the color image-forming material released from the photosensitive microcapsules.

The photosensitive microcapsules and the image receiving element may be in the same layer on the same support, or may be in separate layers on the same support. The photosensitive sheet may be on separate supports, such as a combination of a photosensitive sheet having a layer containing an image receiving element and an image receiving sheet having a layer containing an image receiving element on the support.

Furthermore, the image receiving element of the present invention may contain a mordant such as an anionic polymer or a cationic polymer, or may contain a combination of these anionic polymers and cationic polymers, if necessary.

The binders used in the photosensitive material and image-receiving material of the present invention may be contained alone or in combination. Hydrophilic binders are typically transparent or translucent, such as proteins such as zegitin, zegitin derivatives, cellulose derivatives, starch,
It includes natural materials such as polyaxes such as gum abyss, and synthetic polymeric materials such as water-soluble polyvinyl compounds such as polyvinylpyrrolidone and acrylamide polymers. Other synthetic polymeric materials include dispersed vinyl compounds in the form of latex.

Moreover, a binder of a vinyl addition polymer soluble in an organic solvent can also be used.

The supports used in the light-sensitive material and image-receiving material in the present invention are those that can withstand processing pressure or processing temperature. Common supports include glass, paper,
Not only are wood-free papers, coated papers, art papers, synthetic papers, metals and their analogs used, but also cellulose acetate films, cellulose ester films, polyvinyl acetal films, polystyrene films, polycarbonate films, polyethylene terephthalate films and related materials. Contains film or resin materials. Paper supports laminated with polymers such as polyethylene can also be used. American special pestle 363
The polynisdel films described in No. 4089 and No. 3725070 are preferably used. Ru.

The photosensitive material of the present invention may optionally include a protective layer, an antistatic layer,
Auxiliary layers such as an anti-curl layer, a peeling layer, and a matting agent layer can be provided. In particular, the protective layer preferably contains an organic or inorganic matting agent for the purpose of preventing adhesion.

In addition, photosensitive materials and image-receiving materials may contain C-capri anti-capri agents, fluorescent whitening agents, anti-fading agents, no-ration and irradiation-preventing dyes, and pigments (including white pigments such as acid ratio titanium). , pigments that adjust or color materials, thermal polymerization inhibitors, and surfactants.

It may also contain a dispersed vinyl compound and the like.

In the present invention, various exposure means can be used. In general, commonly used light sources such as sunlight, strobes, flashes, tungsten lamps, mercury lamps, halogen lamps such as mercury lamps, xenon lamps, laser beams, and CRT light sources, plasma light sources, fluorescent tubes,
You can use light emitting diodes etc. as a light source 6!
! A combination of a micro-shutter' array using CD (liquid crystal), PLZT (lanthanum-doped lead titanium zirconate), etc., and a linear or planar light source 4;5 6-Exposure means combined It can also be used.

In the present invention, the layer containing photosensitive microcapsules can be heated before and/or during and/or after exposure to increase sensitivity.

In the present invention, the image is developed on the exposure method element by washing out the unexposed, non-insolubilized areas with a solvent, by thermal transfer of the unexposed, non-hardened areas, or by other methods known to those skilled in the art. You can also do that. In the case of the method of washing with a solvent, an organic solvent can be used, but an alkaline aqueous solution can also be used as the developing solvent.

Suitable developer solutions include solutions of alkali carbonates such as sodium carbonate; solutions of alkali hydroxides such as sodium hydroxide; mixtures thereof; lower alcohols such as ethanol, propatool, etc. and alanolamines such as ethanolamine, propatoolamine. %2
-Aqueous solutions with diethylaminoethanol, etc.; and similar solutions.

The presence of a surfactant in the developer solution aids in clean development of the element. The alkaline strength of the developer solution depends on the particular composition used. The developer can also contain dyes, pigments, and the like. The developed image is then rinsed with distilled water;
It can also be dried and optionally post-baked.

"Example" Example 1 Using photopolymerization initiator solutions A-1 to A2 shown in Table 1,
Photopolymerizable compositions B-1 and B-2 shown below were prepared.

Pentaerythritol tetraacrylate 1.0t
Acetone methyl ethyl ketone propylene glycol monomethyl ether acetate photopolymerization initiator solution (shown in Table 1) f 0f f t Table 1 *** Additive (al * Photopolymerization initiator (a) Hs H3 ** Photopolymerization initiator ( b) The obtained photopolymerizable compositions B-1 and B-2 were coated on a 100μ polyethylene terephthalate film to a film thickness of 2μ, dried at a temperature of 100°C for 2 minutes, and then the following overcoat layer was applied to a 1μ thick film. The photosensitive sheets 1 and 2 were obtained by applying a film to a thickness and drying at a temperature of 100° C. for 2 minutes.

[Coating liquid required for overcoat]

Water 98f Polyvinyl alcohol 1.7F Hydroxypropyl methylcellulose 1.71 Polyvinylpyrrolidone 8.7f For exposure, use a vacuum printing frame device and apply a step wedge (density step 0.15, 'a degree step number θ) onto the photosensitive sheets 1 and 2. ~15 steps, Fuji Step Guide P (manufactured by Fuji Photo Film Co., Ltd.)'ft:
Through the Φsenon lamp (manufactured by Ushio@)'t-use light? I-irradiated. After exposure 49-50- Developed using a developer having the following formulation.

[Developer]

Anhydrous carbonated soda 10F butyl cellosolve 5 and water
After developing No. 1, the steps of the wedge with the lower exposure amount were eluted and the polyethylene terephthalate surface appeared, so the highest number of steps corresponding to the step wedge was determined as the number of steps of the photosensitive material. The higher the number of stages, the higher the sensitivity.

The results are shown in Table 2.

Table 2 As can be seen from Table 2, when a compound having an electron-withdrawing Ct group is used in the indolenine nucleus of the present invention, Ct
This brings about a remarkable effect of improving photosensitivity compared to the case where a compound without groups is used.

In the photosensitive sheet 1 of the comparative example, since the photosensitive layer was not cured, the image flowed and the number of stages could not be determined.

Example 2 Photopolymerization initiator solutions C-1 to C-2 shown in Table 3 consisting of organic cationic dye/organoboron anion salt and other additives
Polyisocyanate [Sumidur N-75 (manufactured by Sumitomo Chemical ■):) 3.39 was added to the solution, and Perser#pt Red (-6 to B(
A solution prepared by dissolving 12f (manufactured by Ciba Geigy) in 50f (trimethylolpropane triacrylate) is mixed. 4. Add this mixed solution to 154 tons of water and use sodium polystyrene sulfonate (Parsa TL502, manufactured by National Starch).
After dissolving 3f and then further dissolving pectin 5.1f into this.

It was added to an aqueous solution adjusted to pX[-6.0 and emulsified and dispersed.

44 ml of water in this dispersion? , melamine 3.9F, and 37 thiformin 6°52 were reacted in advance at 60°C for 30 minutes, and a reaction solution was added thereto, and after mixing, the pH was adjusted to 6.0. Thereafter, the temperature was raised to 65°C, and the reaction was carried out with stirring for 3 hours. 7.7ft of urea was added to this reaction solution, and then the pH was adjusted with NaOH solution.
-jjH was adjusted to 9.5 to obtain microcapsule liquids D-1 to D-2 with a particle size of 3.5p.

Table 3 The same photopolymerization initiators (a) and (b) as in Table 1 were used.

＊＊＊＊Additive (g)) [Preparation of photosensitive sheet and image-receiving sheet] Capsule liquids D-1 to D-2, 5f respectively obtained in this way
15% polyvinyl alcohol aqueous solution 1,532, distilled water 3.47? , 0.57 ft of starch was added to prepare a coating solution. This was applied to art paper using Coach in Blonde 10, dried at 50°C for 15 minutes, and photosensitive sheet 3
-4 was obtained.

On the other hand, 21.8 tons of water contains 48% SDR latex 0
．． 6f, 10% etherified starch aqueous solution 4f% zinc carbonate 2.1? , 1.3 tons of sodium silicate aqueous solution, 0°1f of sodium hexametaphosphate, 131'i of acid clay
The mixture was added and stirred for 15 minutes using a homogenizer.

This was applied to art paper using Coach-in-Blonde 18 and dried at 100° C. for 2 minutes to obtain an image-receiving sheet.

[Image playback and results]

Image reproduction was performed as follows. Light was irradiated onto the above-mentioned photosensitive sheet through a step wedge (Fuji Step Guide P (manufactured by Fuji Photo Film)) that had a density difference of 2 around the entire circumference of the xenon lamp (manufactured by Ushio).After exposure 53-4 The exposed sensitive photosensitive sheet and the image-receiving sheet were stacked so that their coated surfaces faced each other and passed through a pressure roller with a linear pressure of 100 Kf/an.The capsules in the unexposed areas were destroyed and the image-receiving sheet The transferred part gave a clear image with a density of 1.0.The density of the part corresponding to the exposed part changes depending on the exposure amount, but the minimum number of exposure steps to achieve a density of 0°1 or less was set. In other words, the higher the number of exposure steps, the higher the sensitivity.The results are shown in Table 4.

Table 4 It turns out that

Example 3 In place of the photopolymerization initiator (b), a compound having electron-withdrawing Ctg@ in the indolenine nucleus of the present invention was used as shown in Table 4. Samples were prepared in the same manner as in Example 1, except that when a compound without a Ct group was used, a compound having a higher W and degree was used. When these samples were tested in the same manner as in Example 1, they all had higher sensitivity than Comparative Example 1.
Time and city using photopolymerization initiators etc.! showed equivalent sensitivity.

Claims (1)

[Claims] (1) Contains a polymerizable compound having an ethylenically unsaturated bond and an organic boron compound anion salt of an organic cationic dye compound represented by the following general formula (I), wherein the organic cationic dye compound is A photopolymerizable composition represented by formula (II). General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ Here, D^+ represents the cationic dye of general formula (II); R
^1, R^2, R^3 and R^4 may be the same or different, and are an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, an aralkyl group, a substituted aralkyl group,
alkaryl group, substituted alkaryl group, alkenyl group,
Substituted alkenyl group, alkynyl group, substituted alkynyl group,
A group selected from an alicyclic group, a heterocyclic group, and a substituted heterocyclic group; R^1, R^2, R^3 and R^4 are a cyclic structure in which two or more of these groups are bonded. It's okay to be hot. General formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ Here, R^1^1 and R^1^2 each represent an alkyl group, and L^1, L^2 and L^3 are methine groups. represents. n represents an integer from 0 to 4, A^1, A^2
, A^3, A^4, B^1, B^2, B^3 and B^
4 is a hydrogen atom or an electron-withdrawing group (>
0). However, A^1, A^2, A^3, A^4
, B^1, B^2, B^3, and at least one of B^4
One represents an electron-absorbing group. Y^1 and Y^2 represent an atomic group that enables a cyclic structure to be formed together with the carbon atom at the 3-position of the indolenine nucleus.