JPH03209477A - Aluminate complex and photopolymerizable composition using this complex - Google Patents

Abstract

PURPOSE:To obtain the aluminate complex which is stable in air and has radical generatability by devising the substituent species of aluminum atoms and the cation species of the aluminate complex. CONSTITUTION:This aluminate complex comprises the generation of radicals by photoexcitation. Namely, the novel aluminate complex formed by devising the substituent species of the aluminum atoms and the cation species of the aluminate complex and the photopolymerizable compsn. contg. a polymerizable compd. having an ethylenic unsatd. bond in at least the molecule and the aluminate complex are used. The aluminate complex as a photopolymn. initiator having improved stability is obtd. in this way.

Description

DETAILED DESCRIPTION OF THE INVENTION "Field of Industrial Application" The present invention relates to a novel aluminate complex and a photopolymerizable composition using the aluminate complex. More specifically, novel aluminate complexes with radical generation ability and improved stability, and lithographic printing, resin letterpress printing, resists or photomasks for producing printed circuit boards, and sheets for monochrome or color transfer coloring using the same. Alternatively, the present invention relates to a highly sensitive and spectrally sensitized photopolymerizable composition that can be used for producing color-forming sheets and the like.

"Prior Art" Although there are few examples of research on aluminum compounds themselves that have the ability to generate radicals, there is a possibility that they can be used as radical generators. For example, an example in which an acrylonitrile complex of dichloroethylaluminum and butadiene were mixed and radical copolymerized (W, Kuran et al.
Die Makromolekulare Chem
ie174.73-80 (1973)), an example of detecting radicals by measuring the ESR spectrum of an oxidized alkyldiphenoxyaluminum compound (, Pa5yn
K iewicz et al, J, of O
rganometallic chemistry, 1
41° 149-156 (1977)), and it has been suggested that aluminum compounds have the ability to generate radicals.

Although there have been few examples of research on the radical-generating ability of aluminum ate complexes (aluminate complexes), it can be expected by analogy that the ate complexes have radical-generating ability. However, organoaluminum compounds
In general, there are problems such as poor stability in air and difficulty in handling during synthesis, and so far there have been few attempts to use it as a radical generator for any purpose.

On the other hand, a photopolymerizable composition basically contains a photopolymerization initiator and an addition-polymerizable compound containing two or more ethylenically unsaturated bonds in the molecule (hereinafter referred to as "polyfunctional monomer"), 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. Ideas and application examples are described in many of the books. For example, “Light Sensitive Systems” by J. A. Kosar.
G.W. Willey and Sons, New York (
J, Kosar rLight 5intensive
SystemsJJ, Wiley & 5ons, N
ew York) 1965, pp. 158-193, and "Imaging Systems" by K. I. Jacobson and R. E. Jacobson, J.W. Willey and Sons, New York (K, 1. Jacobs
“Imagi” by R.E. Jacobson, R.E.
ng SystemsJ J, 11ey & 5o
ns, New York) 181-22 in 1976
Details on page 2 etc.

Furthermore, in recent years, as an image forming method using a photopolymerizable composition, an image forming system using photosensitive microcapsules in which a photopolymerizable composition is encapsulated in microcapsules has been proposed. For example, JP-A-57-124343, JP-A No. 57-1
No. 79836 and No. 57-197538 disclose that a color-forming sheet coated with microcapsules containing a photopolymerizable composition consisting of a vinyl compound and a photopolymerization initiator and a dye is overlapped with an image-receiving sheet after exposure, and pressure is applied to the entire surface. A method of forming a dye image is disclosed.

Furthermore, in recent years, consideration has been given to the application of these photopolymerizable compositions to full-color photosensitive materials that are spectrally sensitized to the visible light region.

For example, Journal of the Photographic Society of Japan, Vol. 49, No. 3, p. 230 (1986
) and Functional Materials, September 1983 issue, pages 48-60, describe spectral sensitization methods for photopolymerizable compositions. Further, JP-A-59-189340 describes a method of spectrally sensitizing an organic peroxide initiator with an organic dye. Further, European Patent No. 223587A1 discloses an organic boron anion salt of an organic cationic dye as a new photopolymerization initiator.

In particular, this method of using an organic boron compound anion salt of an organic cationic dye compound as a photosensitive initiator has the advantage that the cationic color compound can be selected from a wide range and a photopolymerizable composition sensitive to any wavelength can be designed. This is a useful method.

``Problems to be Solved by the Invention'' However, boron compounds are generally expensive, and organoaluminum compounds generally have poor stability in air, which limits their industrial use.

The present inventors have conducted extensive research in order to impart stability to aluminum ate complexes, and as a result, by devising the type of substituents on the aluminum atom and the cation type of the aluminate complex, it has been found that it is stable in the air, We also succeeded in developing an aluminate complex that has the ability to generate radicals.

That is, the object of the present invention is to provide an aluminate complex as a photopolymerization initiator, which is sensitive to light sources of visible light or higher, is highly sensitive, is derived from inexpensive starting materials, and has improved stability. An object of the present invention is to provide a photopolymerizable composition using. More specifically, we offer high-sensitivity and visible light-sensitive lithographic printing plates, resin letterpress plates, resists and photomasks for making printed circuit boards,
The object of the present invention is to provide an inexpensive photopolymerizable composition that can be advantageously used for forming black and white or color images.

"Means for Solving the Problem" As a result of intensive research, the present inventors discovered a compound using cheaper aluminum as a starting material. That is, the object of the present invention is to provide a novel aluminate complex in which the substituent type of the aluminum atom and the cation type of the aluminate complex are devised, and at least (a) a polymerizable compound having an ethylenically unsaturated bond in the molecule. and (b) a photopolymerizable composition characterized by containing the above aluminate complex.

The present invention will be explained in detail below.

The aluminate complex referred to in the present invention refers to all compounds consisting of an anion species having an aluminum atom having four substituents as a central metal and a cation species that is ionically bonded. This includes lithium aluminum hydride and its derivatives, which are commonly used as reducing agents.

Among the aluminate complexes according to the present invention, the following general formula (I
) is preferred.

Here, D+ represents a cationic compound; R1, R2, R
3 and R4 may be the same or different, and are an alkyl group or a substituted alkyl group, an aryl group, a substituted aryl group, an aralkyl group, a substituted aralkyl group, an alkaryl group, a substituted alkaryl group, which may have an unsaturated bond. , alkenyl group, substituted alkenyl group, alkynyl group, substituted alkynyl group, alicyclic group, aryloxy group, substituted aryloxy group, arylthio group, substituted arylthio group, arylamino group, substituted arylamino group, arylseleno group, substituted A group selected from the group consisting of an arylseleno group, a cycloalkyl group, a substituted cycloalkyl group, a heterocyclic group, and a substituted heterocyclic group; R1, R2, R3 and R4 are two or more of the groups bonded together. It may be a cyclic structure.

Among these compounds, R1, R2, R3 and R4,
Compounds in which at least one is a group represented by general formula (U), general formula (m), or general formula (IV) are preferred because they have good stability.

General formula (II) General formula (m)-X-R
5-N-R6 7 General formula (IV) -N=R8 Here, X represents an oxygen atom, a sulfur atom, or a selenium atom; R5, R6, and R7 may be the same or different, and each , a substituted alkyl group, an aryl group, a substituted aryl group, an aralkyl group, a substituted aralkyl group, a heterocyclic group, and a substituted polycyclic group; R6 and R7 are bonded to each other to form a cyclic structure. You may do so.

R8 represents an aliphatic group, an aromatic group or a heterocyclic group, which may further have a substituent.

In the aluminate complex according to the present invention, at least one of the four substituents on the aluminum atom is preferably a substituted hydroxy group, a substituted mercapto group, a substituted seleno group, or a substituted amino group. Particularly preferred is an aryloxy group.

In the above formula, R1, R2, R3 and R4 are represented by the above general formula (I[
) to (TV), an alkyl group which may contain an unsaturated bond having 1 to 20 carbon atoms as a substituent,
Aryl group having 6 to 20 carbon atoms, 7 to 20 carbon atoms
An aralkyl group is preferred. R1, R2, R3 and R
When 4 represents an alkyl group, they may be bonded to each other to form a ring containing a heteroatom.

As R1, R2, R3 and R4, in particular, an alkyl group having 1 to 10 carbon atoms and optionally containing an unsaturated bond;
Aryl group having 6 to 10 carbon atoms, 7 to 10 carbon atoms
An aralkyl group is preferred.

Among the substituents represented by R5 in the above formula, an aryl group is preferred. The term aryl group here means an aromatic ring which may contain a heteroatom, with a benzene ring being particularly preferred.

In order to impart stability, the aryl group is preferably substituted at the 2-position (relative to X in the above formula), and the nucleus may be further substituted. In this case, substituents include an alkyl group having 1 to 20 carbon atoms which may contain an unsaturated bond, an aryl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and 6 carbon atoms. -20 aryloxy groups, halogen atoms, alkoxycarbonyl groups having 2 to 20 carbon atoms, and the like are preferred. In particular, an alkyl group having 1 to 10 carbon atoms is preferred, and one in which the α-position from the benzene ring is a tertiary carbon is preferred. Further, it may be bonded to R1, R2, R3, R4, etc. as a linking group.

Among the substituents represented by X in the above formula, an oxygen atom is preferred.

Among the substituents represented by R6 and R7 in the above formula, the number of carbon atoms is 1
An alkyl group which may contain up to 20 unsaturated bonds and an aryl group having 6 to 20 carbon atoms are preferred. R1, R2
, R3 and R4 represent an alkyl group, they may be bonded to each other to form a ring containing a heteroatom.

In the above formula, the cationic compound represented by D+ means any compound that is positively charged. Preferred inorganic compounds include metal ions belonging to group 1.2 of the periodic table, such as sodium, potassium, and magnesium, and preferred organic compounds include those having heteroatoms such as oxygen, sulfur, and nitrogen atoms. In particular, quaternary ammonium cations or organic cationic dyes are preferred.

When D+ represents a quaternary ammonium cation, it is represented by the following general formula (V).

In the above formula, R9, RIOl, R11 and R12 may be the same or different and represent a hydrogen atom, an alkyl group, or an aryl group. These groups may have a substituent.

Among the substituents represented by R9, RIOlRll and R12, an alkyl group having 1 to 20 carbon atoms which may contain an unsaturated bond and an aryl group having 6 to 20 carbon atoms are preferred. When R1, R2, R3 and R4 represent an alkyl group, they may be bonded to each other to form a ring containing a heteroatom. Particularly preferred are alkyl groups having 1 to 10 carbon atoms and aryl groups having 6 to 10 carbon atoms.

Specific examples of quaternary ammonium salts include tetramethylammonium cation, tetraethylammonium cation, tetrabutylammonium cation, phenyltrimethylammonium cation, benzyltrimethylammonium cation, dodecyltrimethylammonium cation, dimethylethylhexylammonium cation, and the like.

When D+ represents an organic cationic dye, examples of the organic cationic dye include cationic methine dyes,
Polymethine dyes: preferably cyanine dyes, hemicyanine dyes, styryl dyes, azamethine dyes; more preferably among these dyes having at least one indolenine skeleton or benzselenazole skeleton. Carbonium dye: preferably a triarylmethane dye. Pyrylium compound: preferably biryllium dye or thiapyrylium dye. Quinoneimine dye: preferably azine dye,
Thiazine dye, oxazine dye. Xanthene dye: preferably rhodamine dye. Acridine dye. Azulenium pigment. It is possible to use one or a combination of dyes selected from the following.

In the present invention, the above-mentioned organic cationic dyes that are commercially available or known in the industry can be used. Examples of these dyes include, for example, the section on basic dyes in the dye handbook edited by the Organic Chemistry Society, and the book "Theory of Photographic Processes" by T. H. James, published by Macmillan Publishing Co., Ltd.
The Theory of the Photo-g
rapic ProcessJ Macmill
an Publishing Co.

, Inc.) 1977, pp. 194-290, and ``
Chemistry of Functional Pigments J (CMC Publishing, 1981), pages 1-32, pages 189-206, and pages 401-413, JP-A-59-189340, European Patent No. 22
No. 3587A1 etc. can be referred to.

Among the above dyes, particularly useful in the present invention are cyanine dyes and xanthene dyes. Specific examples of cyanine dyes useful in the present invention include dyes represented by the following general formula (■).

General formula (VI) - where ZL Z2 is a heterocyclic nucleus commonly used in cyanine dyes, preferably a thiazole nucleus, thiazoline nucleus, benzothiazole nucleus, naphthothiazole nucleus, oxazole nucleus, oxazoline nucleus, benzoxazole nucleus, naphthoxazole Necessary to complete the nucleus, tetrazole nucleus, pyridine nucleus, quinoline nucleus, imidacilline nucleus, imidazole nucleus, benzimidazole nucleus, naphthoimidazole nucleus, selenazoline nucleus, selenazole nucleus, benzoselenazole nucleus, naphthoselenazole nucleus, or indolenine nucleus, etc. represents a group of atoms. These nuclei include an alkyl group having 1 to 4 carbon atoms, a halogen atom, an aryl group having 6 to 12 carbon atoms, a hydroxyl group, an alkoxy group having 1 to 4 carbon atoms, a carboxyl group,
alkoxycarbonyl group, alkylsulfamoyl group,
Alkylcarbamoyl group, acetyl group, acetoxy group,
It may be substituted with a cyano group, trichloromethyl group, trifluoromethyl group, nitro group, etc.

Ll, R2 or R3 represents a methine group or a substituted methine group. As the substituted methine group, an alkyl group having 1 to 4 carbon atoms,
an aryl group or substituted aryl group having 6 to 12 carbon atoms,
A methine group substituted with an alkoxy group having 1 to 4 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, or the like is preferred.

Ll and R13, and L3 and R14 may be alkylene bridged to form a ring. The ring is preferably a 5- or 6-membered ring.

ml represents an integer of 1 to 4. As ml is 2-4 [
L2=L3] has a repeating unit, L2 of a certain unit and L2 of an adjacent unit may be bonded to each other to form a ring.

R13 and R14 are alkyl groups (preferably carbon atoms 1 to 8
) or a substituted alkyl group. Substituents include alkyl groups having 1 to 8 carbon atoms, halogen atoms, and 6 to 1 carbon atoms.
2 aryl group, aralkyl group having 7 to 12 carbon atoms, hydroxyl group, carboxyl group, sulfo group, 1 to 4 carbon atoms
Examples include alkoxy groups. Preferably, the alkylene moiety is C1-C5. For example, β-sulfoethyl, γ-sulfobrovir, γ-sulfobutyl, δ-sulfobutyl, 2-[2-(3-sulfopropoxy)ethoxyconityl, 2-hydroxysulfopropyl, 2-chlorosulfopropyl, 2-methoxyethyl, 2- hydroxyethyl, carboxymethyl, 2-carboxyethyl,
2.2.3.3-tetrafluoropropyl, 3,3.3
-) Lifluoroethyl, allyl group, and other substituted alkyl groups commonly used as the N-substituent of cyanine dyes.

A- represents an anion moiety of the aluminum compound of the structural formula (I).

Specific examples of xanthene dyes useful in the present invention include dyes represented by the following general formula (■).

General formula (■) R21, R22, R23, and R24 each independently represent a hydrogen atom, an alkyl group, or an aryl group, particularly an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an aryl group having 1 to 10 carbon atoms. -8 alkoxy groups, C7-12 aralkyl groups, etc. are preferred.

These may have a substituent, such as an alkyl group, a halogen atom, an aryl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, a carboxyl group, an acylcarbonyl group, an alkylsulfamoyl group, or an alkylcarbamoyl group. , acetyl group, acetoxy group, cyano group, trichloromethyl group, trifluoromethyl group,
A nitro group and the like are preferred.

A- represents an anion of the aluminum compound of the general formula (I), and Y represents a hydrogen atom, an alkyl group, an aryl group, or an alkali metal.

Preferred quaternary ammonium salt part (T-No) and organic cationic dye part (D-No) that can be used in the present invention
Examples of the organic aluminum compound anion part (A-No) are listed below.

Preferred compounds that can be used in the present invention include:
Examples include salts in which these organic cationic moieties and organoaluminum compound anion moieties are arbitrarily combined.

however, This is the effect of the present invention. The present invention is not limited to these compounds.

The aluminate complex represented by the general formula (I) may be prepared by uniformly mixing an organic cationic salt and an anionic salt of an organic aluminum compound in an organic solvent, and then using the mixture as it is, or by first taking it out and purifying it. You can stay a month later.

The organoaluminum compound of the present invention can be synthesized by various methods. For example, trialkylaluminium, which is known to be inexpensive, is reacted with a phenol compound to obtain dialkyl-phenoxyaluminum or monoalkyl-diphenoxyaluminum, and then alkyllithium is reacted, and the counter ion is changed to quaternary ammonium. can be exchanged and synthesized. Further, by using the quaternary ammonium salt of the organoaluminum anion and the halogen salt of the cationic dye, counterion exchange can be performed to obtain an organoaluminum compound anion' salt of the organic cationic dye compound.

References include lithium tetraphenylaluminate (G
, Wittet at, Ann, , 566, 113
(1950)], sodium tetraethyl aluminate (
E, B, Baker etat, J, Am, Chem.
, Soc, 75.5193 (1953).

For example, when synthesizing the compound represented by [(PhO)2R2All NR' 4, the method shown in the following three steps is preferred.

(Step 1) R3Al + 2XPhOH → (Phi)2 RAl + 2XRH (Step 2) (PhO)2RA1 + RLi → [(P h 0)2R2A l ] Li (Step 3
) [(PhO)2R2A lcoLi + HalNR
'4→[(Ph ○)2R2Al ko NR'4
+ LiHal (however, R, R' are alkyl groups,
ph represents a phenyl group, and Hal represents a halogen atom. ) The aluminate complex used in the present invention may be used in any manner for the purpose of being used as a radical generator.

The amount is %. If it is less than 0.01% by weight, the improvement in sensitivity will be weak, and if it exceeds 10% by weight, no improvement in sensitivity can be expected.

A thermal polymerization inhibitor may be further added to the composition of the present invention, mainly for the purpose of preventing polymerization of the photopolymerizable composition during storage. Specific examples of thermal polymerization inhibitors include p-methoxyphenol, hydroquinone, alkyl- or aryl-substituted hydroquinone, t-butylcatechol,
Pyrogallol, cuprous chloride, floranil, naphthylamine, β-naphthol, 2,6-di-t-butyl-p-
Examples include cresol, lysine, nitrobenzene, dinitrobenzene, p-)luidine, methylene blue organic steel, and methyl salicylate. These thermal polymerization inhibitors are used in an amount of 0.001 parts per 1001 parts of the ethylenically unsaturated compound.
It is preferably contained in a range of 5 parts by weight.

Furthermore, since the photopolymerizable composition of the present invention is highly sensitive and sensitive to visible light, it is particularly useful for image forming systems using microcapsules. It has a physical form. 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, isocrotonic acid,
Maleic acid, etc.

Examples of the salts of unsaturated carboxylic acids include sodium salts 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,
Penta, erythritol diacrylate Pentaerythritol triacrylate, bentaenothritol tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol triacrylate, dipentaerythritol tetraacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol Examples include hexaacrylate and polyester acrylate oligomer. Examples of methacrylic acid esters include tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, ethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, pentaerythritol dimethacrylate, and pentaerythritol. Trimethacrylate, dipentaerythritol dimethacrylate, sorbitol trimethacrylate, sorbitol tetramethacrylate, bis-[p-(3-methacryloxy-2-hydroxypropoxy)phenylkoshimethylmethane, bis-[p-(acryloxyethoxy)phenylkoshi Examples include methylmethane. Examples of itaconic acid esters include ethylene glycol shiitaconate, propylene glycol shiitaconate, 1,3-butanediol shiitaconate, 1,4-butanediol shiitaconate, tetramethylene glycol shiitaconate, and pentaerythritol shiitaconate. , sorbitol tetrataconate, etc. Examples of crotonic acid esters include ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate, and sorbitol tetracrotonate. Isocrotonic acid esters include ethylene glycol diisocrotonate, pentaerythritol diisocrotonate, sorbitol tetraisocrotonate, and the like. Examples of maleic esters include ethylene glycol simarate, triethylene glycol simarate, pentaerythritol simarate, and sorbitol tetramaleate.

Furthermore, mixtures of the aforementioned esters may also be mentioned.

Specific examples of amides of aliphatic polyvalent amine compounds and unsaturated carboxylic acids include methylenebis-acrylamide, methylenebis-methacrylamide, 1,6-hexamethylenebis-acrylamide, and 1.6-hexamethylenebis-methacryl. amide, diethylenetriamine trisacrylamide, xylylene bisacrylamide, xylylene bismethacrylamide, etc.

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

The content of aluminate complex is 0 relative to the polymerizable compound.
．． The content is from 0.01 to 50% by weight, preferably from 0.2 to 40% by weight, and more preferably from 5 to 20% by weight. o
If the amount of oiI is less than % by weight, the sensitivity will be insufficient, and if it exceeds 50% by weight, no increase in sensitivity can be expected.

The novel photopolymerizable composition containing the above-mentioned polymerizable compound having an ethylenically unsaturated bond and an aluminate complex can be used for various purposes.

For example, a layer containing this photopolymerizable composition and a binder polymer is provided on a support in US Pat.
No. 652, No. 4431723, No. 4550073,
With reference to JP-A Nos. 61-285444 and 61-213213, JP-A No. 62-67529 and U.S. Patent No. 4604 were used as resist materials for printing plates and printed circuit boards.
340 etc. as a color blue material, JP-A-60
It can be applied to many fields according to methods known in the industry, such as optical recording thermal development type recording materials, etc. with reference to No. 11952 and JP-A-61-123838.

Although the photopolymerizable composition of the present invention has high sensitivity and sensitivity to visible light, it may also contain a reducing agent, such as an oxygen scavenger, as an auxiliary agent to further promote polymerization.
ger) and a chain transfer agent of an active hydrogen donor, and other compounds that promote polymerization in a chain transfer manner can also be used in combination. Oxygen scavengers that have been found to be useful include phosphines, phosphonates, phosphites,
tin salts and other compounds that are easily oxidized by oxygen. Examples include N-phenylglycine, trimethylbarbital acid, N,N-dimethyl-2,6-diitubrobylaniline, N,N,N-2,4,6-pentamethylaniline. Further, for example, U.S. Pat. No. 4,414,312
For example, thiols such as those described in US Pat. No. 3,558,322 and JP-A-64-17048, etc.

Furthermore, when the organoaluminum compound anion salt of the organic cationic dye compound of the present invention is used in combination with other photopolymerization initiators, an improvement in sensitivity is observed, and preferred specific examples include the following compounds. Aromatic ketones: for example, benzophenone, 4,4'-bis(dimethylamino)
Benzophenone, 4-methoxy-4'-dimethylaminobenzophenone, 4,4'-dimethoxybenzophenone, 4-dimethylaminobenzophenone, 4-dimethylaminoacetophenone, Hensyl, anthraquinone, 2
-tert-butylanthraquinone, 2-methylanthraquinone, xanthone, thioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthone, fluorenone, acridone; and benzoin and benzoin ethers: for example benzoin methyl ether,
Benzoin ethyl ether, benzoin isopropyl ether, benzoin phenyl ether; and 2,
4. 5-) Realyl imidazole dimer: e.g. 2
-(o-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(0-chlorophenyl)-4,5-
Di(m-methoxyphenyl)imidazole dimer, 2-
(0-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(o-methoxyphenyl)-4,5
-diphenylimidazole dimer, 2-(p-methoxyphenyl)-4,5-diphenylimidazole dimer;
and polyhalogen compounds such as carbon tetrabromide, phenyl tribromomethyl sulfone, phenyl trichloromethyl ketone and Compounds described in each specification, S-) riazine derivatives having a trihalogen-substituted methyl group described in JP-A-58-29803: For example, 2. 4.
6-tris(trichloromethyl)-S-) riazine, 2
-methoxy-4,6-bis(trichloromethyl)-5-
Compounds such as triazine, 2-amino-4,6-bis(trichloromethyl)-5-)riazine, 2-(P-methoxystyryl)-4,6-bis(trichloromethyl>-s-triazine; and e.g. Japanese Patent Publication No. 59-189
Organic peroxides described in No. 340: for example, methyl ethyl ketone peroxide, cyclohexanone peroxide,
3゜3.5-) Limethylcyclohexanone peroxide, benzoyl peroxide, ditertiarybutyl diperoxyisophthalate, 2,5-dimethyl-2,
5-di(benzoylperoxy)hexane, tert-butylperoxybenzoate, α,α′-his(tert-butylperoxyisopropyl)benzene,
Dicumyl peroxide, 3. 3', 4. 4'
Compounds such as -tetra-(tert-butylperoxycarbonyl)benzophenone. and azinium salt compounds as described, for example, in US Pat. No. 4,743,530; and organoboron compounds as described in, for example, EP 0223587: for example, the tetramethylammonium salt of triphenylbutylborate, the tetrabutylammonium salt of triphenylbutylborate. , Tori (P-
Photopolymerization initiators well known in the art such as tetramethylammonium salts of methoxyphenylbutyl catal; other diaryliodonium salts and iron arene complexes can be usefully used.

The content of the photopolymerization initiator for improving sensitivity is preferably 0.01 to 20% by weight, and more preferably 0.01 to 20% by weight, based on the total weight of the photopolymerizable composition. The content is 2 to 15% by weight, and the most preferred content is 5 to 10% by weight. If it is less than 0.01% by weight, the improvement in sensitivity will be weak, and if it exceeds 10% by weight, no improvement in sensitivity can be expected.

A thermal polymerization inhibitor may be further added to the composition of the present invention, mainly for the purpose of preventing polymerization of the photopolymerizable composition during storage. Specific examples of thermal polymerization inhibitors include p-methoxyphenol, hydroquinone, alkyl- or aryl-substituted hydroquinone, t-butylcatechol,
Pyrogallol, cuprous chloride, floranil, naphthylamine, β-naphthol, 2,6-di-t-butyl-p-
Examples include cresol, pyridine, nitrobenzene, dinitrobenzene, p-)luidine, methylene blue organic steel, methyl salicylate, and the like. These thermal polymerization inhibitors are 0.001 parts by weight per 100 parts by weight of the ethylenically unsaturated compound.
It is preferably contained in a range of 5 parts by weight.

Furthermore, the photopolymerizable composition of the present invention is highly sensitive and sensitive to visible light, and is therefore particularly useful for image forming systems using microcapsules.

For use in an image forming system using microcapsules, for example, Japanese Patent Laid-Open Nos. 57-197538 and 61-
No. 130945, No. 58-88739, No. 58-88
No. 740, European Patent No. 223587A1, etc. can be referred to. In this image forming method, for example, microcapsules containing a photopolymerizable composition comprising an ethylenic vinyl compound and a photopolymerization initiator and a dye precursor are coated on a support, and this photosensitive sheet is imagewise exposed to expose the exposed areas. After curing the microcapsules, a developer sheet is placed over the entire surface and pressure is applied to destroy the microcapsules in the unexposed area, and transfer the color image forming substance (e.g. dye precursor) to the image receiving element (e.g. developer layer). ) to develop color. 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 color image forming substance (dye, dye breaker, or pigment), etc. can be added.

Hereinafter, a method for producing a photosensitive material using the photopolymerizable composition of the present invention will be described.

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

The polymerizable compound of the photopolymerizable composition of the present invention can be emulsified and contained in the photosensitive layer as droplets, or the droplets can be surrounded by microcapsule walls. At this time, it is preferable that the organic aluminum compound anion salt of the organic cationic dye compound is also contained in the droplets.

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 using these, a color image can be formed by destroying the portions (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 publicly 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 the Japan Pigment Technology Association, published in 1978). are available. 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. 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 develop color upon heating, pressurization, 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 that uses azo coupling reactions of diazosulfonates, naphthols, anilines, active methylenes, etc.; reactions of hexamethylenetetramine with ferric ions and gallic acid, and reactions of phenolphthalein-combrexonic acid with alkaline earth. Chelate formation reactions such as reactions with similar metal ions; reactions between ferric stearate and pyrogallol, and reactions between silver behenate and 4-
Redox reactions such as methoxy-1-naphthol reactions can be used.

Further, as another example of a system in which color is generated by a reaction between two components, a case where 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/g color agent system is (1
) triarylmethane type, (2) diphenylmethane type,
(3) xanthene compounds, (4) thiazine compounds, and (5) spiropyran compounds, and specific examples include those described in JP-A-55-27253. Among these, (1) triarylmethane-based coloring agents and (3) xanthene-based coloring agents are preferred because they cause less fog and provide high coloring density.

Specific examples include crystal violet lactone, 3
-diethylamino-6-chloro-7-(β-ethoxyethylamino)fluoran, 3-diethylamino-6-methyl-7-anilinofluorane, 3-triethylamino-6-methyl-7-anilinofluorane, 3 -cyclohexylmethylamino-6-methyl-7-anilinofluorane, 3-diethylamino-7-〇-chloroanilinofluorane, etc., and these 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'-isopropylidene-diphenol (bisphenol A)/p-te
rt-butylphenol, 2,4-dinitrophenol, 3,4-dichlorophenol, 4,4'-methylene-
bis(2,6-di-tert-butylphenol),
p-phenylphenol, 1,l-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)-2-ethylhexane, 2,2-bis(4-hydroxyphenyl)butane, 2, 2'-methylenebis(4-tert-butylphenol), 2,2'
-Methylenebis(α-phenyl-p-cresol)thiodiphenol, 4,41-thiobis(6-tert-butyl-m-cresol), sulfonyldiphenol, as well as p-tert-butylphenol-formalin condensate, p- Examples include phenylphenol-formalin condensates.

Examples of organic acids or metal salts thereof include phthalic acid, phthalic anhydride, maleic acid, benzoic acid, gallic acid, 〇-toluic acid, p-toluic acid, salicylic acid, 3-tert-butylsalicylic acid, 3,5-di-tert -butylsalicylic acid, 6-α-methylbenzylsalicylic acid, 3.5-
(α-methylbenzyl)salicylic acid, 3-tert-octylsalicylic acid and its zinc, lead, aluminum salts,
Magnesium salts or nickel salts are useful. In particular, salicylic acid derivatives and their zinc salts or aluminum salts are excellent in terms of color developing ability, fastness of colored images, storage stability of recording sheets, and the like.

Examples of oxybenzoic acid esters include ethyl p-oxybenzoate, butyl p-oxybenzoate, heptyl p-oxybenzoate, pencil p-oxybenzoate, and the like.

In addition, an oil-absorbing white pigment can be used in combination to diffuse and fix the capsule contents.

These color developers can be added as a eutectic with a thermofusible substance with a low melting point, or a low melting point compound can be added to the surface of the color developer particles in order to melt at a desired temperature and cause a color reaction. 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 stearamide, erucic acid amide, valmitic acid amide, ethylene bisstearamide or higher fatty acid esters, phenyl benzoate derivatives, aromatic ether derivatives, Alternatively, there are urea derivatives, but the invention is not limited to these.

Examples of other color formers/developers include phenolphthalein, fluorescein, 2'4', 5'
, 7'-tetrabromo3.4.5.6-titrachlorofluorescein, tetrabromophenol blue
4.5.6.7-titrabromophenolphthalein,
Examples include eosin, alarin cresolette, and 2-naphtholphenolphthalein.

Color developers include inorganic and organic ammonium salts, organic amines, amides, urea and thiourea and their derivatives, thiazoles, virols, pyrimidines, piperazines, guanidines, indoles, imidazoles, imidacillins, and triazoles. Examples include nitrogen-containing compounds such as morpholines, piperidines, amidines, formacins, and pyridines. Specific examples of these include ammonium acetate, tricyclohexylamine, tribenzylamine, octadecylbenzylamine, stearylamine, allyl urea, thiourea, methylthiourea, allylthiourea, ethylenethiourea, 2-benzylimidazole, 4-phenylimidazole. ,2-phenyl-4
-Methyl-imidazole, 2-undecyl-imidacillin, 2.4.5-trifuryl-2-imidacillin, 1.
2-diphenyl-4,4-dimethyl-2-imidacillin, 2-feco-2-imidacillin, 1,2.3-1 rifhenylguanidine, 1,2-ditolylguanidine, l
, 2-dicyclohexylguanidine, 1,2-dicyclohexyl-3-phenylguanidine, l,2゜3-tricyclohexylguanidine, guanidine trichloroacetate, N,N'-dibenzylpiperazine, 4,4' -dithiomorpholine, morpholinium trichloroacetate, 2-
These include amino-benzothiazole and 2-benzoylhydrazino-benzothiazole.

In the present invention, the color image forming substance is a polymerizable compound 100
0.5 to 20 parts by weight, particularly preferably 2 parts by weight
~7! Used in terms of parts. 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 the photopolymerizable composition of the present invention is to be microencapsulated, it can be produced by a method known in the art.

For example, US Patent Nos. 2,800,457 and 2,800,045
No. 8, a method utilizing coacervation of a hydrophilic wall-forming material, U.S. Pat. No. 3,287,154;
Interfacial polymerization methods as seen in British Patent No. 990443, Japanese Patent Publication No. 38-19574, Japanese Patent Publication No. 42-446, and Japanese Patent Publication No. 42-771, US Patent Nos. 3418250 and 366
0304, methods using isocyanate polyol wall materials as found in U.S. Pat. No. 3,796,669, U.S. Pat. No. 3,914,511
U.S. Pat. No. 4,001,140, U.S. Pat. No. 4,087,376, U.S. Pat.
89802, a method using wall forming materials such as urea-formaldehyde and urea formaldehyde resorcinol, and a method using wall forming materials such as melamine-formaldehyde resin and hydroxypropyl cellulose, as shown in U.S. Patent No. 4,025,455, and Japanese Patent Publication No. 36 -91
No. 68, JP-A No. 51-9079, the in situ method by polymerization of monomers, British Patent Nos. 952,807 and 965,074, the electrolytic dispersion cooling method, U.S. Pat. No. 3,111,407, British Patent No. 93
There is a spray drying method as seen in No. 0422.

Although not limited thereto, it is preferable to emulsify the core material and then form a polymer membrane as the microcapsule wall.

The microcapsule wall of the present invention is particularly effective when using a microencapsulation method by polymerizing a glue actant from inside an oil droplet. That is, it is possible to obtain capsules, which are desirable as a recording material and have a uniform particle size and excellent storage stability, within a short time.

For example, when polyurethane is used as the capsule wall material, a polyvalent isocyanate and a second substance that reacts with it to form the capsule wall (e.g., polyol, polyamine) are mixed into the oily liquid to be encapsulated, emulsified and dispersed in water, and then By increasing the temperature, a polymer formation reaction occurs at the oil droplet interface, forming a 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. 49-241
No. 59, JP-A No. 48-80191, JP-A No. 48-8408
No. 6, and they can also be used.

Examples of polyvalent isocyanates include m-phenylene diisocyanate, p-phenylene diisocyanate,
2.6-) lylene diisocyanate, 2.4-) lylene diisocyanate, naphthalene-1,4-diisocyanate, diphenylmethane-4,4'-diisocyanate, 3,3'-dimethoxy-4,4'-biphenyl-diisocyanate, 3 ,3'-dimethyldiphenylmethane-
4,4'-diisocyanate, xylylene-1,4-diisocyanate, 4,4'-diphenylpropane diisocyanate, trimethylene diisocyanate, hexamethylene diisocyanate, propylene-1,2-diisocyanate, butylene-1,2-diisocyanate, cyclohexylene - diisocyanates such as 1,2-diisocyanate and cyclohexylene-1,4-diisocyanate; triisocyanates such as 4.4',4''-)liphenylmethane triisocyanate and toluene-2,4,6-1 diisocyanate; 4. Tetraisocyanates such as 4゛-dimethyldiphenylmethane-2,2', 5゜5'-tetraisocyanate, adducts of hexamethylene diisocyanate and trimethylolpropane, 2
．． 4-) There are isocyanate butyl polymers such as adducts of lylene diisocyanate and trimethylolpropane, adducts of xylylene diisocyanate and trimethylolpropane, and adducts of tolylene diisocyanate and hexanetriol.

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

Examples of polyamines include ethylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, p-phenylenediamine, m-phenylenediamine, piperazine, 2-methylpiperazine, 2,5-dimethylpiperazine, and 2-hydroxytrimethylene. Examples include diamine, diethylenetriamine, triethylenetriamine, triethylenetetramine, diethylaminopropylamine, tetraethylenepentamine, and amine adducts of epoxy compounds. The polyamine is preferably used in a proportion of hydroxyl groups of 0.02 to 2 moles per mole of isocyanate groups. 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 anionic polymers, nonionic polymers, and amphoteric polymers.

As the anionic polymer, both natural and synthetic polymers can be used, and ffl-COO-1-SO2
- groups, etc. can be mentioned. Specific anionic natural polymers include gum arabic, alginic acid, pectin, etc., and semi-synthetic products include carboxymethyl cellulose, phthalated gelatin, sulfated starch, sulfated cellulose, lignin sulfonic acid, etc.

In addition, synthetic products include maleic anhydride-based (including hydrolyzed) copolymers, acrylic acid-based (including methacrylic acid-based) monopolymers and copolymers, and vinylbenzenesulfonic acid-based polymers and copolymers. , carboxy-modified polyvinyl alcohol, etc.

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 a 0.01 to 101% by weight aqueous solution. The particle size of microcapsules is 20μm
Adjusted below.

The size of the capsules used in the present invention is 80 μm or less, and preferably 20 μm or less from the viewpoint of storage stability and handling properties. Also, if the capsule is too small, there may be holes in the matrix or! There is a possibility that it will be erased during i & li, but this depends on the nature of the substrate or support, so it cannot be generalized, but it is 0.
．． Preferably, the diameter is 1 μm or more [8] The capsule used in the present invention does not substantially change when the pressure is less than about 10 kg/cm 2 , and preferably breaks when a pressure greater than this is applied. The magnitude of the pressure at which this destruction occurs can be changed depending on the application and is not limited to a specific value, but it is approximately 5
It is preferable to destroy it at a pressure of about 00 kg/cm2 or less. 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 the capsule. 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 the capsule by a known method such as the method described in No. 7. 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 the solvent used in the capsule is preferably 1 to 500 parts by weight per 100 parts by weight of the polymerizable compound.

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, naphthenic oils, alkylated biphenyls, alkylated terphenyls, chlorinated paraffins, alkylated naphthalenes and 1-phenyl-1-xylylethanes, 1 -Diarylethanes such as phenyl-1-p-ethyl phenylethane, 1,1'-ditolylethane, and the like.

Phthalic acid alkyl esters (dibutyl phthalate, dioctyl phthalate, etc.), phosphoric acid esters (diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, dioctyl butyl phosphate), citric acid esters (e.g. acetyl tributyl citrate)
, benzoic acid esters (octyl benzoate), alkylamides (e.g. diethyl laurylamide), fatty acid esters (e.g. dibutoxyethyl succinate, dioctyl acelate), trimesic acid esters (e.g. tributyl trimesate), ethyl acetate, acetic acid. Examples include lower alkyl acetates such as butyl, ethyl propionate, secondary butyl alcohol, methyl isobutyl ketone, β-ethoxyethyl 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/or fixing the color image-forming substance released from the photosensitive microcapsules. The photosensitive microcapsules and the image receiving element may be in the same layer on the same support, or in separate layers on the same support, or the layer containing the photosensitive microcapsules may be on the support. They may be on separate supports, such as a combination of a photosensitive sheet with a layer containing an image-receiving element and an image-receiving sheet with 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 combine 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 gelatin, gelatin derivatives, cellulose derivatives, starch,
Other synthetic polymers include natural polymers such as polysaccharides such as gum arabic and synthetic polymers such as water-soluble polyvinyl compounds such as polyvinylpyrrolidone, acrylamide polymers, etc. Dispersed vinyl compounds in the form of latex There is.

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

To apply each coating solution for the photosensitive material and image-receiving material of the present invention, use a blade coater, rod coater, knife coater, roll doctor coater, comma coater, reverse roll coater, transfer roll coater, gravure coater, kiss roll coater, curtain coater.
An extrusion coater or the like can be used.

The application method is Re5earch Disclose.
re, Vol, 200° December 1980, l te
m 2003B X V section can be referred to.

The appropriate thickness of the layer is from 0.1μ to 50μ.

Recording materials using the photopolymerizable composition of the present invention can be used for various purposes. For example, the recording material of the present invention can be used for applications such as copiers, fax machines, printer labels, color proofs, overhead projector second original drawings, and the like. Suitable supports for the photosensitive material and image receiving material of the present invention include paper, coachite paper, laminated paper, synthetic paper, polyethylene terephthalate film, cellulose triacetate film, polyethylene film, polystyrene film, polycarbonate film, etc. Examples include transparent films, plates of metal such as aluminum, zinc, and copper, and those obtained by subjecting the surface of the above-mentioned support to various treatments such as surface treatment, undercoating, and metal vapor deposition treatment.

As a support, Re5earch Disclosure
e, Vol, 200. December 1980, Item 2
0036 The support described in section X■ may also be referred to. Further, these supports can be provided with layers depending on the purpose, such as an antihalation layer on the surface and a slip layer, an anti-stack layer, an anti-curl layer, an adhesive layer, etc. on the back side, if necessary.

In addition, light-sensitive materials and image-receiving materials may contain antifoggants, optical brighteners, anti-fading agents, anti-halation and irradiation dyes, pigments (including white pigments such as titanium oxide), and material colors as necessary. It may also contain colorants for conditioning or coloring, thermal polymerization inhibitors, surfactants, dispersed vinyl compounds, and the like.

Various exposure means can be used for the photopolymerizable composition of the present invention. It goes without saying that commonly used light sources such as sunlight, tungsten lamps, mercury lamps, halogen lamps such as iodine lamps, xenon lamps, CRT light sources, plasma light sources, fluorescent tubes, light emitting diodes, etc. can be used as the light source. In addition, light sources suitable for high-intensity, short-time recording, such as strobes, flashes, lasers, and LC
It is also possible to use an exposure means that combines a micro-shutter array using D (liquid crystal), PLZT (lead titanium zirconate doped with lanthanum), etc., and a linear light source or a planar light source.

As an image recording method, various exposure methods can be used, such as close exposure of an original such as a lithographic film, enlarged exposure of a slide or liquid crystal image, and reflection exposure using reflected light from the original.

When performing multicolor recording, image recording may be performed multiple times using light of different wavelengths. Light of different wavelengths can be obtained by changing the light source or changing the optical filter.

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

The present invention will be explained in more detail by examples below.
The present invention is not limited to these "Examples" Example 1 A solution of 9.5 g of 2,6-di-7-butylphenol in 10 ml of dehydrated toluene was added to a solution of 80 ml of dehydrated toluene containing 4.4 g of tri-n-butylaluminum. The solution was heated at room temperature for about 15 minutes.
After the mixture was added dropwise over several minutes, the mixture was slowly heated over about 1 hour until the toluene refluxed, and the mixture was stirred for 1 hour while the toluene was refluxed. The solvent of the reaction solution was distilled off, and then unreacted 2,6-di-t-butylphenol was removed by vacuum distillation. The thus obtained mixture of bis(2,6-di-t-butylphenoxy)-n-butylaluminum and tri-n-butylaluminum weighed 8.8 g.

100 ml of dehydrated toluene was added to this mixture, and under water cooling,
11 ml of n-hexane solution containing 1.15 g of n-butyllithium was slowly added dropwise so as to keep the internal temperature below 5°C, and the mixture was stirred at 0°C for 1 hour and at room temperature for 1 hour. After distilling off the solvent, 1 ml of dehydrated n-hexane was added to obtain a hexane-insoluble lithium salt. This was recrystallized from n-hexane-toluene to give bis(2,6-di-t-butylphenoxy)
-5.5 g of lithium di-n-butylaluminate was obtained.

The above lithium salt was dissolved in 50 ml of dehydrated dichloromethane and 12.0 ml of tetra-n-butylammonium chloride was added.
A solution of 8 g in 10 ml of dichloromethane was added at room temperature, and the mixture was stirred at the same temperature for 1 hour. The generated dichloromethane-insoluble lithium chloride was filtered off, and the filtrate was concentrated to obtain 7.1 g of an aluminate complex consisting of compounds (A-1) and (T-2).

The structure of compound (A-1) was confirmed by NMR.

0.08 g of the aluminate complex, 2 dichloromethane
g1 trimethylolpropane triacrylate) 7g,
A sample was prepared by dropping one drop of a solution containing 0.07 g of the salt of the above dye compound (D-7) onto a polyethylene terephthalate film with a thickness of 100 μm, and then covering it with another polyethylene terephthalate film. . When this sample was sandwiched between vacuum baking frames and exposed for 0.1 count under vacuum using a jet light (manufactured by Oak Co., Ltd., IKW), this sample was photocured and clearly gave a polymerized product.

Example 2 Photopolymerizable composition solutions S-1 to S-4 shown in Table 1 were prepared.

The obtained photopolymerizable composition solutions S-1 to S-4 were each used at 10%
A sample was prepared by placing one drop on a 0 μm polyethylene terephthalate film and covering it with another polyethylene terephthalate film.

This sample was placed in a vacuum baking frame and heated to zero with a jet light (manufactured by Oak Co., Ltd., IKW) under vacuum. When exposed for one count, samples S-3 and S-4 were photocured.

It can be seen that the organoaluminum compound anion salt of the organic cationic dye compound of the present invention has the ability to initiate photopolymerization. In addition, a mixture of the iodonium salt of an organic cationic dye compound and the tetrabutylammonium salt of an organoaluminum compound anion also forms an organoaluminum compound anion complex of the organic cationic dye compound in solution, so photopolymerization equivalent to the complex occurs. It is found that it has the ability to initiate.

Table - Prescription monomer (M) of photopolymerizable composition solution: Salt of trimethylolpropane triacrylate dye compound (D-7): Photopolymerization initiator (A-1) + (T-1): Photopolymerization Initiator (A-1) + (D-7) 2 Examples 3 to 4 Using the photopolymerization initiator solutions B-1 to B-2 shown in Table 2, the following photopolymerizable combination C- 1 to C-2 were adjusted.

[Photopolymerizable composition] Pentaerythritol tetraacrylate benzyl methacrylate/methacrylic acid (molar ratio 73/27 copolymer) acetone methyl ethyl ketone propylene brecol monomethyl ether acetate photopolymerization initiator solution (shown in Table 2) 1° 0゜g g g 0g g! g Table 2: Photopolymerization initiator solution Salt of dye compound (D-8): The obtained photopolymerizable combinations C-1 to C-2 were coated on a 100 μm polyethylene terephthalate film to a thickness of 2 μm. Then, dry at a temperature of 100°C for 2 minutes, then apply the following overcoat layer to a thickness of 1 μm, and dry at a temperature of 100°C.
After drying for 2 minutes, photosensitive sheets 1 and 2 were obtained.

[Coating liquid water required for overcoat 9
8 g Polyvinyl alcohol 1.7 g Hydroxypropyl 1.7 g Methyl cellulose Polyvinyl pyrrolidone 8.7 g Exposure was carried out using a vacuum printing frame device, and a step wedge (density step 0.15, number of density steps 0 to 15 steps) was placed on the photosensitive sheets 1 to 2. Light was irradiated from an ultra-high pressure mercury lamp using a jet light (manufactured by Oak Co., Ltd.) through Fuji Step Guide P (manufactured by Fuji Photo Film ■).After exposure, development was performed using a developer having the following formulation.

[Developer solution: Anhydrous soda soda 10g Butyl cellosolve 5g Water
After 1 g of development, the steps of the wedge with the lower exposure amount were eluted and the polyethylene terephthalate surface was exposed, 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 3.

Table 3: Evaluation results Table 3 shows that the photopolymerizable composition of the present invention has high sensitivity.

Example 5 Perscript Red I-6-8 (as a color former) was added to the photopolymerization initiator solutions F-1-F-2 shown in Table 4.
A solution prepared by dissolving 8.4 g of Ciba Geigy II) in 35 g of trimethylolpropane triacrylate was mixed with each other. 18. This mixed solution was adjusted to pH 7.0.
6% isobutylene/maleic anhydride copolymer aqueous solution 1
It was added to a mixed solution of 9 g of gum arabic, 18 g of a 9.1% aqueous gum arabic solution, and 28 g of water, and the pH was adjusted to 3.5. 6 of this liquid
The mixture was heated to 0°C, and 4.6 g of urea and 0.56 g of resorcin were added and emulsified and dispersed. Then, 30% formalin 13
gti: Added and stirred for 1 hour. 9 g of 5% ammonium sulfate was added to this reaction solution, and the reaction was further continued for 1 hour until the pH
was adjusted to 7°0 to obtain microcapsule liquids E-1 and E-2 with a particle size of 3.5 μm.

Table 4: Photopolymerization initiator solution [g Preparation of optical sheet and image-receiving sheet] 5 g of each of the thus obtained capsule solutions E-1 to E-2, 53 g of a 15% polyvinyl alcohol aqueous solution, and 3.0 g of distilled water.
47 g and 0.57 g of starch were added to prepare a coating liquid. Apply this to art paper using a coating rod IO,
The photosensitive sheets 3 to 5 were obtained by drying at 50° C. for 15 minutes.

On the other hand, 48% SBR latex 0.6 in 21.8g water
g, 10% etherified starch aqueous solution 4g, zinc carbonate 2
．． 1g, 50% sodium silicate aqueous solution 1.3g, sodium hexametaphosphate 0.1g.

13 g of acid clay was added and stirred with a homogenizer for 15 minutes.

This was applied to art paper using the coating rod 18 and dried at 100° C. for 2 minutes to obtain an image receiving sheet.

[Image Reproduction and Results] Image reproduction was performed as follows. Jet light (made of oak ■) is applied to the original line drawing on the photosensitive sheet mentioned above.
Light was irradiated from an ultra-high pressure mercury lamp using a step wedge (density step 0.15, number of density steps 0 to 15, Fuji Step Guide P (manufactured by Fuji Photo Film ■). After exposure, these exposed photosensitive sheets The coated surfaces of the image-receiving sheets were placed one on top of the other and passed through a pressure roller with a linear pressure of 100 kg/cm.The capsules in the unexposed areas were destroyed, and the capsule core material was transferred to the image-receiving sheet. The exposed area gave a clear black image with a density of 1.0.The density of the area corresponding to the exposed area changes depending on the exposure amount, but the sensitivity (corresponding to foot sensitivity) is determined by the minimum number of exposure steps that results in a density of 0.1 or less. ), that is, the larger the number of exposure steps, the higher the sensitivity.The results are shown in Table 5.

Table 5: Evaluation Results Table 5 shows that the photopolymerizable composition of the present invention has high sensitivity.

Claims (9)

[Claims] (1) An aluminate complex characterized by generating radicals upon photoexcitation. (2) In claim (1), the aluminate complex is
An aluminate complex characterized by being represented by the following general formula (I). General formula (I) ▲ Numerical formulas, chemical formulas, tables, etc. ▼ [Here, D+ represents a cationic compound; R1, R2, R
3 and R4 may be the same or different, and are an alkyl group or a substituted alkyl group, an aryl group, a substituted aryl group, an aralkyl group, a substituted aralkyl group, an alkaryl group, a substituted alkaryl group, which may have an unsaturated bond. , alkenyl group, substituted alkenyl group, alkynyl group, substituted alkynyl group, alicyclic group, aryloxy group, substituted aryloxy group, arylthio group, substituted arylthio group, arylamino group, substituted arylamino group, arylseleno group, substituted A group selected from the group consisting of an arylseleno group, a cycloalkyl group, a substituted cycloalkyl group, a heterocyclic group, and a substituted heterocyclic group; R1, R2, R3 and R4 are two or more of the groups bonded together. It may be a cyclic structure. ] (3) In claim (2), at least one of R1, R2, R3, and R4 is a group represented by general formula (II), general formula (III), or general formula (IV). Characteristic aluminate complex. General formula (II) -X-R5 General formula (III) -N-R6 General formula (IV) -N=R8 Here, X represents an oxygen atom, sulfur atom or selenium atom; R5, R6 and R7 are the same a group selected from the group consisting of a hydrogen atom, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, an aralkyl group, a substituted aralkyl group, a heterocyclic group, and a substituted heterocyclic group; R6 and R7 may be bonded to each other to form a cyclic structure. R8 represents an aliphatic group, an aromatic group or a heterocyclic group, which may further have a substituent. (4) Claims (1) to (3), wherein the cationic compound is a quaternary ammonium salt;
Aluminate complex. (5) The aluminate complex according to any of claims (1) to (3), wherein the cationic compound is a cationic dye. (6) In claims (1) to (3), the cationic dye is selected from the group consisting of cationic methine dyes, polymethine dyes, carbonium dyes, pyrylium compounds, quinoneimine dyes, xanthene dyes, acridine dyes, and azulenium dyes. An aluminate complex characterized by being a colored pigment. (7) A photopolymerizable composition containing at least a polymerizable compound having an ethylenically unsaturated bond and an aluminate complex that generates radicals when exposed to light. (8) In claim (7), the aluminate complex is
A photopolymerizable composition characterized by being represented by the above general formula (I). (9) The photopolymerizable composition according to claim (7), characterized in that a polymerizable compound having at least an ethylenically unsaturated bond is encapsulated in microcapsules.