JPS61233736A - Photopolymerizable composition - Google Patents

Abstract

PURPOSE:To obtain a photopolymerizable compsn. high in sensitivity to rays of light in the visible wavelength region by using a compsn. composed essentially of a photopolymerization initiator compsn. contg. a compd. having at least one azulenium salt ring and a photopolymerizable photosensitive component. CONSTITUTION:The photopolymerizable compsn. is composed essentially of the photopolymerization initiator compsn. contg. the azulenium photosensitive compd. representable by formulae [I]-[III) having at least one azulenium salt ring and a photopolymerizable component. The photopolymerization initiator compsn. is added in an amt. of 0.1-100, preferably, 0.5-50pts.wt. per 100pts.wt. of the photopolymerizable photosensitive component, thus permitting the obtained photopolymerizable compsn. to complete polymerization reaction in a short time by irradiating actinic rays ranging from UV to the visible light.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a photopolymerizable photosensitive resin composition having a photoinitiator composition, and more particularly, it is sensitive to ultraviolet light and visible light at low light doses and can be used for laser applications. The present invention relates to a highly sensitive photopolymerizable composition.

It is well known that monomers, dimers, trimers, oligomers, and polymers containing unsaturated bonds in their molecules are photopolymerized in the presence of a photoinitiator. Furthermore, this phenomenon is widely used in photopolymerizable photopolymers and photoresists used in manufacturing printing plates, printed circuit boards, ICs, and the like.

Various substances have been reported and actually used as photopolymerization initiators used in these photosensitive resins. For example, benzoin compounds such as benzoin, benzoin methyl nityl, benzoin ethyl ether, etc., and carbonyl compounds such as benzyl, benzophenone,
Azo compounds such as acetophuninone and Michael's ketone, azobisisobutyronitrile, azodibenzoyl, etc.
Also, as a sulfur compound, dipenzothiazolyl sulfide,
Examples of halogen compounds include tetraethylthiuram disulfide, il) lipromphenylsulfone tetrabromide, and benzanthraquinone and pyrylium salts.

However, these photopolymerization initiators are not yet fully satisfactory, and when combined with various unsaturated compounds, they cannot necessarily be said to have good sensitivity as a photopolymer.

In addition, in recent years, methods of forming images using lasers have been studied, and technologies such as laser direct engraving, laser facsimile, and holography for printing plate production are already at the stage of practical use, and their application in many other fields is being considered in the future. , and expected.

The laser photosensitive materials used in this case include silver salt photosensitive materials, electrophotographic photosensitive materials, photochromic materials, and photopolymers, but among these, photopolymers have extremely low sensitivity compared to silver salt photosensitive materials and electrophotographic materials. Furthermore, its sensitivity wavelength range is from ultraviolet to visible light. For example, the sensitivity of silver halide film (Cogris Orthofilm 2556 Type 3) is 48.
The amount of energy required for 8 nm monochromatic light is 0.0205
mJ/c+++2, but ti7000 with 7 otobolimer (Kodak Bolimachi Chrysoplate LN-L)
mJ/6n” is also required, wavelength 351/364
Even if nanometer ultraviolet rays are used, an energy of 100 mJ/era is required.

As described above, the conventional 7 otobolimer was unsatisfactory in both sensitivity and sensitive wavelength range, and was particularly unsuitable as a photosensitive material for visible light lasers.

Accordingly, an object of the present invention is to provide a photopolymerizable composition that solves the above-mentioned problems and is highly sensitive even in the visible light region.

These objects of the present invention are achieved by a photoinitiator composition containing an azulenium salt compound having at least one azulenium salt core and a photopolymerizable composition containing a photopolymerizable photosensitive component as a main component. In particular, the azulenium salt compound described above has the following general formula [:I), [:U) or [■]
can be represented by

[ID R1 In the general formula, R1 to R7 represent a hydrogen atom, a chlorine atom (chlorine atom, bromine atom, iodine atom), or a monovalent organic residue. Monovalent organic residues can be selected from a wide variety, but especially alkyl groups (methyl,
Ethyl, n-propyl, isopropyl, n-butyl, t
-butyl, n-i/L/, n-hexyl, n-octyl, 2-ethylhexyl, t-octyl, etc.), alkoxy groups (methoxy, ethoxy, propoxy, butoxy, etc.), substituted or unsubstituted aryl groups (phenyl, tolyl, xylyl, ethylphenyl, methoxyphenyl,
ethoxyphenyl, po phenyl, nitrophenyl, dimethylaminophenyl, α-naphthyl, β-naphthyl, etc.), substituted or unsubstituted aralkyl groups (benzyl, 2-phenylethyl, 2-phenyl-1-methylethyl, bromopenzyl, 2-bromophenylethyl, methylbenzyl, methoxybenzyl, nitrobenzyl), acyl groups (acetyl, globionyl, styryl, valeryl, benzoyl, triooyl, naphthoyl, phthaloyl, furoyl, etc.), substituted or unsubstituted amino groups (
amines, dimethylamino, diethylamino, dipropylamino, acetylamino, benzoylamino, etc.), substituted or unsubstituted styryl groups (styryl, dimethylaminostyryl, diethylaminostyryl, dipropylaminostyryl, methoxystyryl, ethoxystyryl, methylstyryl, etc.) , a nitro group, a hydroxy group, a carboxyl group, a cyano group, or a substituted or unsubstituted arylazo group (phenylazo, α-naphthylazo, β-naphthylazo, dimethylaminostyrylazo, chlorophenylazo, nitrophenylazo, methoxystyrylazo, tolylazo, etc.) can be mentioned.

Also, a fused ring substituted or unsubstituted with at least one combination of R1 and R,, R, and R3, R, 3 and R,, R, 4 and R5, R5 and R6, and R6 and R7. may be formed. The fused ring is 5 or 6 members.

or a 7-membered condensed ring, including aromatic rings (benzene, naphthalene, chlorobenzene, bromobenzene, methylbenzene, ethylbenzene, methoxybenzene, ethoxybenzene, etc.), heterocycles (7-ring ring, benzofuran ring,
Pyrrole ring, thiophene ring, pyridine ring, quinoline ring,
thiazole rings, etc.) aliphatic rings (dimethylene, trimethylene, tetonamethylene, etc.).

ze represents an anion residue.

A represents a divalent organic residue bound by a double bond. A specific example of the present invention including such a person is represented by the following general formula (
1) to αυ can be mentioned. However, Qo in the formula indicates the following azulenium salt removal, and the right side excluding Qe in the formula indicates A3.

(2) Azulenium salt extraction (Q) LS General formula In the formula, 几1 to Ry #: have the same definitions as defined above.

R1 where R7 has the same definition as defined above.

In the formula, R'1 to FLl are hydrogen atoms, halogen atoms (
chlorine atom, bromine atom, iodine atom) or a monovalent organic residue. Monovalent organic residues can be selected from a wide variety of groups, but in particular alkyl groups (methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, n-amyl, n-hexyl, n-octyl, 2-ethylhexyl, t-octyl, etc.), alkoxy groups (methoxy, ethoxy, propoxy, butoxy, etc.), substituted or unsubstituted aryl groups (phenyl, tolyl, xylyl, ethylphenyl, methoxyphenyl, ethoxyphenyl) , chloropher, nitrophenyl, dimethylaminophenyl, α-naphthyl, β-su7thyl), substituted or unsubstituted aralkyl groups (benzyl, 2-phenylethyl, 2-phenyl-1-)thylethyl, bromo , benzyl, 2-7' romophenylethyl, methylbenzyl, methoxybenzyl, nitrobenzyl), acyl group (acetyl, flopionyl, styryl, valeryl, benzoyl, triooyl, naphthoyl, 7taloyl, 70yl, etc.), substituted or Unsubstituted amine groups (amino, dimethylamino, diethylamino, dipropylamino, acetylamino, benzoylamino, etc.), substituted or unsubstituted styryl groups (styryl, dimethylaminostyryl, etc.)
diethylaminostyryl, diethylaminostyryl, methoxystyryl, ethoxystyryl, methylstyryl, etc.), nitro group, hydroxy group, carboxyl group, cyano group, or substituted or unsubstituted arylazo group (phenylazo, α-naphthylazo, β-naphthylazo, dimethylamino 7-ethyl azo, chlorotetraphenylazo, nitro-7-ethylazo, methoxyphenylazo, tolylazo, etc.).

Also, R'1 and R'2. R′2 and t・k3 and R;
R- and R'.

At least one combination of R- and R'6 and R- and R'7 may form a substituted or unsubstituted fused ring. Examples of fused rings include 5-, 6-, or 7-membered fused rings, aromatic rings (benzene, naphthalene, chlorobenzene, bromobenzene, methylbenzene, ethylbenzene, methoxybenzene, ethoxybenzene, etc.)
), heterocycles (furan ring, benzofuran ring, pyrrole ring,
Examples include thiophene ring, pyridine ring, quinoline ring, thiazole ring, etc.) and aliphatic rings (dimethylene, trimethylene, tetonamethylene, etc.).

Further, the azulenium salt removal indicated by ζ and the azulene salt removal on the right side of the formula (C) may be symmetrical or asymmetrical. Zoke has the same definition as defined above. R8, hydrogen atom, nitro group, cyan group,
Alkyl groups (methyl, ethyl, propyl, butyl, etc.)
Also, H7+7-l group (phenyl, tolyl, xylyl, etc.)
, and n represents 0, 1 or 2.

& where R1-R7 and Zo have the same definitions as defined above.

In the formula, R1 to R7a R- to R'7 and Zo have the same definitions as defined above.

(6)　　　　　　　　　　　　　　　　　　　　,--X--,.

In the formula, X is pyridine, thiazole, benzothiazole,
Represents a nonmetallic gold group necessary to complete a nitrogen-containing heterocycle such as naphthothiazole, oxazole, benzoxazole, naphthoxazole, imidazole, benzimidazole, naphthoimidazole, 2-quinoline, 4-quinoline, isoquinoline, or indole; Heterocycles include halogen atoms (chlorine atoms, bromine atoms, iodine atoms)
, an alkyl group (methyl, ethyl, propyl, butyl, etc.), an aryl group (phenyl, tolyl, xylyl, etc.), or the like. R9 alkyl group (
methyl, ethyl, propyl, butyl, etc.), substituted alkyl groups (2-hydroxyethyl, 2-methoxyfer, 2
-ethoxyethyl, 3-hydroxypropyl, 3-methoxypropyl, 3-methoxypropyl, 3-chloropropyl, 3-bromopropyl, 3-carboxypropyl, etc.), cyclic alkyl groups (cyclohexyl, cyclopropyl), allyl, aralkyl Groups (benzyl, 2=phenylethyl, 3-phenylpropyl, 4-phenylbutyl,
α-naphthylmethyl, β-su7thylmethyl), substituted aralkyl groups (methylbenzyl, ethylbenzyl, dimethylbenzyl, trimethylbenzyl, chlorobenzyl, bromohensyl, etc.), aryl groups (phenyl, tolyl, xylyl, α-naphthyl, β- naphthyl) or a substituted aryl group (chlorophenyl, dichlorophenyl, trichlorophenyl, ethylphenyl, methoxyphenyl, dimethoxyphenyl, aminophenyl, nitrophenyl, hydroxyphenyl, etc.). m represents 0 or 1 and has the same definition as defined above.

(7) Q0=CH-Rt.

In the formula, Rlo is a substituted or unsubstituted aryl group (7enyl, tolyl, xylyl, biphenyl, α-su7tyl, β-
Naphthyl, anthralyl, pyrenyl, methoxyphenyl, dimethoxyphenyl, trimethoxyphenyl, ethoxyphenyl, jetoxyphenyl, chlorophenyl, dichlorophenyl, trichlorophenyl, bromophenyl, cyanophenyl, tribromophenyl, ethylphenyl, diethylphenyl, nitrophenyl, amino Phenyl, dimethylaminophenyl, diethylaminophenyl, dibenzylaminophenyl, dipropylaminophenyl, morpholinophenyl, piperidinylphenyl, piperazinophenyl, diphenylaminophenyl, acetylaminophenyl, benzoylaminophenyl, acetylphenyl, benzoylphenyl, cyanophenyl, etc.)
and Ze has the same definition as defined above.

1°) 9■=CH-Rol Ze In the formula, a monovalent heterocyclic group derived from a heterocycle such as R11#'i7 run, thiophene, benzofuran, thionaphthene, dibenzofuran, carbazole, phenothiazine, phenoxazine, pyridine, etc. The expression Zo has the same definition as defined above.

cf'= CH-CH=C-R1゜In the formula, R12 is a hydrogen atom, an alkyl group (methyl, ethyl, propyl, butyl, etc.) or a substituted or unsubstituted aryl group (phenyl, tolyl, xylyl, biphenyl,
Ethylphenyl, chlorophenyl, methoxyphenyl,
ethoxyphenyl, nitrophenyl, aminophenyl,
Dimethylaminophenyl, diethylaminophenyl, acetylaminophenyl, α-su7tyl, β-naphthyl,
anthralyl, pyrenyl, etc.). RIO and ZO have the same definitions as defined above.

e In the formula, R11 and ze have the same definitions as defined above.

iD In the formula, X2 represents an atomic group necessary to complete biran, thiapyran, selenabiran, pe/zobilane, benzothiapyran, benzoselenaviran, naphthopyran, naphthothiapyran, or naphthoselenapyran/, which may be substituted. l
is O or 1. Y represents a sulfur atom, an oxygen atom or a selenium atom. R13 and R14 are hydrogen atoms (
methyl, ethyl, propyl, butyl, etc.), alkoxy groups (methoxy, ethoxy, propoxy, butoxy, etc.)
, substituted or unsubstituted aryl groups (phenyl, tolyl, xylyl, chlorophenyl, biphenyl, methoxyphenyl, etc.), substituted or unsubstituted styryl groups (styryl, p-methylstyryl, o-chlorostyryl, p-
methoxystyryl, etc.), substituted or unsubstituted 4-phenyl 1,3-butadienyl group (4-phenyl 1,3-
7'tadienyl, 4-(p-methylphenyl)-1,3
-butadiyl, etc.) or substituted or unsubstituted heterocyclic groups (quinolyl, pyridyl, carbazolyl, furyl, etc.)
represents. ze a=one residue.

In addition, the anion residue in the formula ze, verchlorate, fluorotetraborate, sulfoacetate, iodide, chloride, bromide, P-toluenesulfonate, alkylsulfonate, alkyldisulfonate, benzenedisulfonate, halosulfonate, picrate, tetra Represents anion residues such as cyanoethylene anion and tetracyanoquinodimethane anion.

Specific examples of the azulenium salt compounds used in the present invention are listed below.

Example (1) of the compound represented by the general formula (1).

H3CHa CH32BF4eO(3 2BP,e C104e CH.

28F 4” Ie Example of the compound represented by the above general formula (6)CI!04e C10♀Example of the compound represented by the above general formula Cczo4゜(6o) CH3 BF4゜Represented by the above general formula Examples of compounds with the general formula αυ
Example of a compound represented by CI! 0? Compounds represented by general formulas (1) and (2) are manufactured by Angewandte chemistry.
e) Volume 78, 420, P, 937 (1966) K
As described, it can be easily obtained by reacting an azulene compound with squaric acid or croconic acid in a suitable solvent. Among the compounds represented by the general formula (3), the compound where n=Q has been published in the Journal of the Chemical Society.
the chemical 5ociety).

P, 5Q1 (1960) by heating a 1-7 year old lumi-azulene compound and an azulene compound in a suitable solvent in the presence of a strong acid, or by heating the 1-7 year old Lumi-Azulene compound and the azulene compound described in Journal of the Chemica/I/ -Society (Jou)
rnal of the chemical society
ty), P, 1724-P, 1730 (19
By mixing a 1-ethoxymethylene azulenium salt compound and an azulene compound in a suitable solvent as described in 1961), or by mixing a 1-ethoxymethylene azulenium salt compound and an azulene compound in a suitable solvent, as described in
chemical 5ociety), P.

359 (1961), by heating 2-hydroxymethylenecyclohexanone and an azulene compound in a suitable solvent in the presence of a strong acid. General formula (
3), the compounds with n = 1 and n = 2 are
urnal of chemical 5oci
ety), P, 3591-P, 3592 (1
It can be obtained by mixing an azulene compound and malondialdehydes or glutacondialdehydes in a suitable solvent in the presence of a strong acid, as described in 1996).

The compound represented by general formula (4) has been published in the Journal of the Chemical Society.
the chemical 8ociety),
It can be easily obtained by heating an azulene compound and glyoxal in a suitable solvent in the presence of a strong acid as described in J.P., 358 B (1961).

The compound represented by general formula (5) has been published in the Journal of the Chemical Society (Journa 1o
f the chemical 5ociety),
It can be obtained by heating a 1,3-cyphorazulene compound and an azulene compound in a suitable solvent in the presence of a strong acid as described in J.P., 504 (1960).

The compound represented by general formula (6) has been published in Journal Op, The Chemical Society (Journa 1o
f the chemical 5ociety)
P, 163-P, 167 (1961), heating a 1-7 ormylazulene compound and a heterocyclic quaternary ammonium salt compound having an active methyl group in a suitable solvent. You can get it easily.

Compounds represented by general formulas (7), (8), (9) and aυ were published in the Journal of the Chemical
Society (Journal of the ch
chemical 5ociety).

P, 1110-P, 1117 (1958), Journal of the Chemical Society
al of the chemical 5ociet
y), p. 494-P. 501 (1960) and Journal of the Chemical Society (Jo
urnalof the chemical 5oci
ety), P, 3579-P.

3593 (1961) by mixing an azulene compound and a corresponding aldehyde compound in a suitable solvent in the presence of a strong acid.

The compound represented by the general formula aυ can be obtained by reacting a 1-7 year old lumi-azulene compound with a compound represented by the general formula a in a solvent.

General formula α2 ,,-X,-.

R13R14 where X, , Y, R13, R14, Zo and j have the same definitions as defined above.

Reaction solvents used include alcohols such as ethanol, butanol, and benzyl alcohol, nitriles such as acetonitrile and propionitrile, organic carboxylic acids such as acetic acid, acid anhydrides such as acetic anhydride, dioxane, and tetrahydro-7rane. Alicyclic ethers, etc. are used. Furthermore, aromatic hydrocarbons such as benzene can be mixed with butanol, benzyl alcohol, and the like. The temperature during the reaction can be selected from the range of room temperature to boiling point.

Synthesis examples of representative compounds of the present invention will be shown below.

Synthesis Example 1 (Compound/I63) 3.4-dihydroxy-3 in a 200 m/Mitsuro flask
-cyclobutene-1,2-dione 1.2f (0,010
5 mol) and 80 ml of n-butanol were added, and the mixture was heated to Loo'c without stirring to dissolve it.

Next, 3 ml of quinoline, 4.46 f (0,0225 mol) of 1,4-dimethyl-7-itubrobil azulene, and 30 ml of benzene were sequentially added into the flask to start the reaction. The reaction was carried out at 95-110°C with benzene 4
5m1! , n-butanol aomz was added in portions while water was azeotropically distilled off for 5 hours.

After cooling the reaction solution, it was filtered with suction, and 59 m of n-butanol was added.
l, 100 ml of methanol! A crude pigment was obtained.

Further, the mixture was boiled and filtered twice with 100 m/g of tetrahydrofuran to obtain compound/I63 3,7. Yield 74.7% Melting point = 237-239°C (capillary method) Elemental analysis:
Molecular formula C34H3402 Calculated value (%) Analysis value (
%) C: 86.02 85.91H: 7
．． 23 7.34 Solution absorption spectrum: λmax ” 770 nm in chloroform Synthesis Example 2 (Compound 414) A solution consisting of 0.64f azulene, 7.5ml of ethyl orthoformate! and 15ml of ethanol was stirred at room temperature, and the solution A solution consisting of 1.25 rrR of 7ON perchloric acid and 7.5 m of ethanol was added to the solution. Immediately, the precipitation of black needle-shaped crystals was observed. After stirring this solution for 40 minutes at room temperature, it was suctioned. Compound 412 was obtained by filtration. After washing and filtration twice with 20 ml of ethanol, it was poured into 30 ml of water, stirred for 30 minutes, and then filtered. Next, it was washed again with 20 ml of ethanol and dried. 95 .34 Synthesis Example 3
(Compound layer 15) Azulene 1. Of, 3-ethoxymethylene guaia azulenium verchlorate 2.77? and methanol 47
The solution consisting of m1 was stirred and refluxed for 5 minutes, and the reaction solution was left overnight. The precipitate was filtered, washed with 20 m/m of methanol, and dried to obtain 2.35 t of crude product. (Gross revenue 69
%), the crude product 2, Of was recrystallized from acetone trile to obtain 1.3F compound 413.

Melting point: 194-196°C (capillary method) Solution absorption spectrum: λmax ” 648 nm Elemental analysis: Molecular formula Cx5HzsC104 calculated value (%) Analysis value (9 g) C71,4671,24 H5,785,81 C18,118,17 Synthesis example 4 (Compound layer 24) 1.4-dimethyl-7-itsuprobil azulene 2.4f
, 4ON glyoxal aqueous solution 3. Of.

Acetonitrile 50ml! and 7ON perchloric acid 3,0
ml of liquid was heated and stirred at 75 to 80°C for 4 minutes,
It was left to cool. The next day, treat the precipitate with F and add 15 m of acetonitrile.
Washed and filtered with / and dried to obtain compound 421 at 1.53 f
Obtained. (Yield! 40.8X) Melting point: 260℃ or higher (
Capillary method) Solution absorption spectrum: λmax in acenitrile = 534 nm Elemental analysis: Molecular formula C3, H3, CI! 203
Calculated value (X) Analytical value (%) C62,0361,97 H5,875,96 Cl 11.44 11.78 Synthesis example 5 (Compound/4630) 1.
4f and 184-dimethyl-7-itsuprobil azulene 3
．． Of was added, and the mixture was stirred and heated to 105°C. To this liquid was added 3.4 m of 70X perchloric acid, heated at the same temperature for 5 minutes, and then left overnight. The precipitate was filtered, washed and filtered with 10ml of glacial acetic acid, washed twice with 50ml of water, filtered, and dried to obtain 2.4f of crude dye.

(Rough collection vehicle 65N) Crude product 2. Of was recrystallized from acetonitrile to obtain 1.2 f of Compound A26.

Melting point: 260°C or higher (capillary method) Solution absorption spectrum: λmax = 660 nm in glacial acetic acid Elemental analysis: Molecular formula C42H42C120s Calculated value (%) Analysis value (X) C67,6467,76 H5,695,78 Cl 9°51 9 .31 Synthesis Example 6
(Compound layer 38) 1-7 ormylu-5-isopropyl-3,8-dimethylazulene 0.60f, 4-methyl-1-ethylquinolinium iodide 0.79f, piperidine 1.8m
/And 22ml of ethanol! The solution was heated and stirred, reacted for 10 minutes at a solution temperature of 75 to 80°C, and then left overnight. The precipitated crystals were filtered and diluted with 10 m/2 of ethanol.
After repeated washing and filtration, the mixture was dried to obtain a compound layer 34 of sO, 72t.

(Yield 55X) Melting point = 243~5℃ (Capillary method) Solution absorption spectrum: λmax" 644 nm in dichloromethane Elemental analysis: Molecular formula C,, H2゜IN calculation value (
%) Analysis value (%) C66,2666,34 H5,975,81 N 2.76 2.711 2
5.01 25.14 Synthesis Example 7 (Compound/16
44) P-dimethylaminobenzaldehyde 5.96t, 70
X perchloric acid 10rrl/and tetrahydro 7 run 400m
1, 1,4-dimethyl-7-iprobil azulene 7,92 f and tetrahydrofuran 400 m/
A solution consisting of the above was added dropwise at room temperature, stirred for 2 hours, and then allowed to stand overnight. The precipitate was filtered and diluted with tetrahydrofuran Loom.
Washing and filtration was performed three times at /. Next, 200m of water! 'de 2
Wash and filtrate twice, further wash and filtrate with 100 m/l of tetrahydrofuran, and then dry to remove compound/l639 at 10.40 m/l.
Obtained. (Yield 60.6%) Melting point: 160.5-162°C (capillary method) Solution absorption spectrum: λmax 640 nm in acetone Elemental analysis Binary Molecular formula C, 4H, 8C/NO.

Calculated value (X) Analyzed value (X) C67,0467,17 H6,586,68 N 3.26 3.19Cl
8.25 8.16 Synthesis Example 8 (Compound 57) P-dimethylaminobenzaldehyde 1.5 (1,7O
N perchloric acid 5, Oml! A solution consisting of 1.28 f of azulene and 150 m of acetic acid was added dropwise to the solution consisting of 1.28 f of azulene and 150 nR of acetic acid at room temperature, and the mixture was stirred for 1 hour.

The precipitate was filtered, washed with 100ml of acetic acid, and then washed with 250ml of water.
/, stirred for 30 minutes, and then filtered.

Next, wash and filter with 200 m of water 7 times, then dry.
2.41F of compound 450 was obtained. (Yield 67, ON
') Melting point: 260℃ or higher (capillary method) Solution absorption spectrum: λmax 634℃m in acetonitrile Elemental analysis: Molecular formula Ct*HtsC/No4 Calculated value (X) Analysis value (X) C63,4264,58 H5,055,32 N 3.89 4.04C19,8
59,64 Synthesis Example 9 (Compound 462) Tetrahydrofuran 160ml! N-ethyl-3-
Formylcarbazole 2.26 f and guaiazulene (
Aldrich Chemical Company 201, Zoo-4)2.
After adding and dissolving Of, add 70X perchloric acid 5 at room temperature.
．． 0 m/ was added and heated, and the mixture was reacted for 10 minutes at a liquid temperature of 60°C to 65°C.

Thereafter, it was cooled, left to stand for days and nights, and the precipitate formed was taken from house to house, washed and filtered four times with 40 ml of tetrahydrofuran, and dried to obtain a crude product of 3.37 F (
A crude mass e 6.2 N) was obtained. Next, this crude product 0.9F was mixed with a mixed solvent of methyl ethyl ketone and acetonitrile (methyl ethyl ketone: acetonitrile = 8:5).
Recrystallization was performed to obtain a purified compound layer 54 with a concentration of 0.429.

Melting point = 206℃ ~ 208℃ (capillary method) Solution absorption spectrum (in dichloromethane): λmax "'
612℃m Elemental analysis: Molecular formula C3, H3, CI! No.

Calculated value (%) Analysis value (X) C71,4872,04 H6,016,14 N 2.78 2.80Cl
7-03 7.01 Infrared absorption spectrum: Characteristics shown in Figure 1 Synthesis Example 10 (Compound A72) Acetic acid 50ml! p-dimethylaminocinnamic aldehyde in 1.77? and 2.02 g of guaiazulene (manufactured by Aldrich Chemical Company: 01,100-4) were added and dissolved, and then heated to 103°C. Then, after adding 10 m/7ON perchloric acid, the mixture was heated at 103°C to 106°C for 20 minutes.
The mixture was stirred while heating for a minute and then cooled. This reaction solution was left to stand overnight, the precipitate formed was separated in a furnace, and this was soml
! of acetic acid three times. Next, 250m1! 2 with water
After repeated washing and filtration, 250ml! After repeated washing and filtration twice with ethyl alcohol,
After drying, compound 463 was obtained with a weight of 1.889 (40,9 N).

Solution absorption spectrum (in dichloromethane): λmax
” 728 nm Elemental analysis: Molecular formula C26H3°C/NO4 Calculated value (X) Analysis value (%) C68,4868,57 H6,646,73 N 3.07 3.14G
Cl 7.77 7.64
Infrared absorption spectrum: Characteristic synthesis example 11 shown in Figure 2 (
Compound/1679) Guaiazulene 3. Of, phenylprobalagylaldehyde (manufactured by Aldrich Chemical Company:
P3,100-0)2. Of and acetonitrile 20m
A liquid consisting of / was added dropwise at room temperature and stirred for 2 hours. Filter the precipitate and add 20ml of acetonitrile! The mixture was washed twice, filtered, and dried.

Yield: 3.73f (Collection: 60.ON) Melting point: 199~
200°C (capillary method) solution absorption spectrum: λmax 501 nm Elemental analysis: Molecular formula CztH2sCI! 04 Calculated value (%) Analysis value (X) C70,1570,06 H5,655,74 CI! 8.63 8.68 The photoinitiator composition of the present invention preferably contains an organic peroxide as a photoinitiator, and this organic peroxide has at least one oxygen-oxygen bond in its molecule. This includes almost all organic compounds that have more than one. For example, methyl ethyl ketone peroxide, cyclohexanone peroxide, 3,3.5-trimethylcyclohexanone peroxide, methylcyclohexanone peroxide, acetylacetone peroxide, 1,1-bis(
tert-butylperoxy)-3,3,5-trimethylcyclohexane, 1゜1-bis(tert-butylperoxy)cyclohexane, n-butyl-4,4
-bis(tert-butylperoxy)parer),
2.2-bis(tert-butylperoxy)butane, tert-butyl hydroperoxide, cumene hydroperoxide, diisopropylbenpine hydroperoxide, para-menthane hydroperoxide, 2,5-dimethylhexane-2,- Civid rober oxide, 1,1,3.3-tetramethylbutyl hydroperoxide, ditertiary butyl peroxide, tertiary butyl tamyl peroxide,
Dicumyl peroxide, α,α-bis(tert-butylperoxyisopropyl)benzene, 2,5-dimethyl-2,5-di(tert-butylperoxy)
Hexane, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexyne-3, acetyl peroxide, imbutyryl peroxide, octanoyl peroxide, decanoyl peroxide, lauroyl peroxide, 3.5 .5-trimethylhexanoyl peroxide, succinic peroxide, benzoyl peroxide,
2.4-dichlorobenzoyl peroxide, meta-toluoyl peroxide, diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, di-n-propyl peroxydicarbonate, di-2-ethoxyethyl peroxydicarbonate, dimethoxy isoprobil baroxycarbonate,
Di(3-methyl-3-methoxybutyl) peroxydicarbonate, tert-butyl peroxyacetate, tert-butyl peroxyisobutyrate, tert-butyl peroxypivalate, tert-butyl peroxyneodecanoate, tertiary butyl peroxyoctanoate, tertiary butyl peroxy-3,5,5-trimethylhexanoate, tertiary butyl peroxylaurate, tertiary butyl peroxybenzoate, ditertiary isoperoxy isophthalate, 2 .5-dimethyl-2,5-
Examples include di(benzoylperoxy)hexane, tert-butyl peroxymaleic acid, tert-butyl peroxyisopropyl carbonate, and the like.

In addition, the above-mentioned known photopolymerization initiators may be mixed into the photoinitiator composition comprising the azulenium salt compound and the organic peroxide.

The photopolymerizable photosensitive component used in the present invention can include all unsaturated compounds, and examples of these unsaturated compounds include hexamers having a polymerizable ethylenically unsaturated bond;
There are oligomers and polymers, such as acrylic acid,
Unsaturated acids such as methacrylic acid, itaconic acid, maleic acid and its anhydride, 7-talic acid and its anhydride, 7-malic acid,
Methyl acrylate, ethyl (meth)acrylate,
Butyl (meth)acrylate, glycidyl (meth)acrylate, hydroxyethyl (meth)acrylate, dimethyl maleate, diethyl maleate, dimethyl fumarate,
Unsaturated acid esters such as pentaerythritol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate,
and styrene, acrylamide, acrylonitrile, N
Examples include -vinyl bisodone, vinyl acetate, and various unsaturated polyesters, unsaturated polyethers, unsaturated polyurethanes, and epoxy (meth)acrylate compounds.

A photoinitiator composition comprising an azulenium salt compound of the general formula [:I]["lI] or (I[[]) of the present invention is added to one or a mixture of two or more photopolymerizable photosensitive components as described above. Alternatively, a photoinitiator composition consisting of the azulenium salt compound and the organic peroxide is added, and if necessary, ordinary dyes, pigments, additives, inhibitors, binders, etc. and a suitable diluting solvent are added. In addition, it is used as a photopolymerizable composition.

In particular, as the binder, any polymer capable of forming a coating film can be used, and examples thereof include poly-N-vinylpyrrolidone, polymethyl methacrylate, polystyrene, polyvinyl acetate, and copolymers thereof.

The amount of the photoinitiator composition added is 0.1 to 100 parts by weight, preferably 0.5 to 100 parts by weight, per 100 parts by weight of the photopolymerizable photosensitive component.
It is 50 parts by weight. When the photoinitiator composition contains the azulenium salt compound and organic peroxide as active ingredients, the weight ratio of the azulenium salt compound:organic peroxide is 0.1:99.9 or more. The ratio is 100:0, preferably 3-95:97-5.

Further, as a suitable diluting solvent, any solvent that dissolves the photopolymerizable composition of the present invention can be used, for example,
Water, methanol, ethanol, propatool, butanol, acetone, methyl ethyl ketone, methyl isobutyl lactone, methyl cellosolve, ethyl cellosolve, benzene, toluene, xylene, ethyl acetate, butyl acetate, tetrahydrofuran, dioxane, dichloromethane, chloroform, carbon tetrachloride, Examples include trichlorethylene, dimethylformamide, dimethyl sulfoxide, etc.

The photopolymerizable composition thus obtained can undergo a polymerization reaction in a short time by irradiating it with active light in a wide range from ultraviolet to visible light. Ultra-high pressure as a beam of light,
High pressure, medium pressure, low pressure.

Mercury lamps, chemical lamps, carbon arc lamps, xenon lamps, metal halide lamps, various visible and ultraviolet laser lamps, fluorescent lamps, tungsten lamps, sunlight, etc. can be used.

The photopolymerizable composition of the present invention can generally be used in photopolymerization reactions, as well as photocurable paints and printing inks.

It can be applied to many fields such as adhesives, printing plate production, and photoresists for producing printed circuit boards, ICs, etc.
and its effects are very good. In particular, the photopolymerizable composition of the present invention has surprisingly good effects when applied to photosensitive materials for visible light lasers such as Ar lasers due to its high sensitivity and wide spectral sensitivity characteristics up to the visible light region. It will be done.

Hereinafter, the present invention will be explained in more detail with reference to Examples. Note that parts in the examples are parts by weight. These examples are provided for illustrative purposes and are not intended to limit the invention in any way.

Examples 1 to 16 100 parts of pentaerythritol triacrylate was used as a photopolymerizable photosensitive material, 100 parts of poly-N-vinylpyrrolidone was used as a binder, and 16 kinds of 7 as shown in Table 1 below were used as a photoinitiator composition. Dulenium salt compound 5
1000 parts of methyl cellulol were added thereto, and these were further mixed uniformly with 1000 parts of methyl cellulol to prepare a photosensitive liquid.

These photosensitive solutions were applied onto an anodized aluminum plate using a spinner coating method so that the dry film thickness was 1 μm.

11A Optical test B 25 W (D Ar v-The (
488 part m) single line with a beam diameter of 1.25 m
The amount of energy required to expose the photosensitive film using m and until the coating film is completely photocured (m J /CIl+")
) Sensitivity was measured.

Comparative Examples 1 to 3 The photosensitivity was exactly the same as in the examples when conventionally known photoinitiators listed in Table 1 below were used instead of the photoinitiator compositions used in Examples 1 to 16. A test was conducted to measure the sensitivity.

The results of Examples 1 to 16 and Comparative Examples 1 to 3 are shown in Table 1.

Table-1 Photosensitivity test results-21,2-benzaanthraquinone 6000-3
Thioacridone 730-4 benzophenone *1)1) *50000
It represents a material that was not cured even after exposure of mJ/am2.

Examples 17 to 25 Examples 1 to 50 except that the photoinitiator composition was added in the ratio of 3 parts of the azulenium salt compound and 3 parts of the organic peroxide listed in Table 2 below. A photosensitive solution was prepared in exactly the same manner as above, and a photosensitivity test was conducted to measure the sensitivity.

Table-2 Photosensitivity test results 17 (3) BPO2) 0.131
8 (3) FBIP3) 0.
0919 (3) POZ4)
0.3220 (44) BPOO,
1521 (44) FBIP 0.13
22 (83) BPOO,1223(
83) PBIF 0.0725
(83) POZ O, 182)
Benzoyl peroxide 3) Shit-tert-butyl diperoxyisophthalate 4) 2,5-dimethyl-2,5-di(benzoylperoxy)hexane Examples 26-31 Poly-N- as binder in Examples 17-25
Instead of vinylpyrrolidone, polymethyl methacrylate (
PMMA), polystyrene (ps), polyvinyl acetate (
Photosensitive solutions were prepared in exactly the same manner as in Examples 17 to 25, except that PVAc) was used, and a photosensitivity test was conducted. The results are shown in Table-3.

Claims (3)

[Claims] (1) A photopolymerizable composition comprising as main components a photoinitiator composition containing a compound having at least one azulenium salt core and a photopolymerizable photosensitive component. (2) The photopolymerizable composition according to claim 1, wherein the compound having at least one azulenium salt nucleus is a compound represented by the following general formula [I], [II] or [III]. General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [II] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [III] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (However, general formula [I], In [II] and [III], R_1, R_2, R_3, R_4, R_5, R_6 and R_7 represent a hydrogen atom, a halogen atom, or a monovalent organic residue, or R_1 and R_2, R_2 and R_3,
At least one combination of R_3 and R_4, R_4 and R_5, R_5 and R_6, and R_6 and R_7 may form a substituted or unsubstituted fused ring. Z^■
represents an anionic residue. ) (3) The photopolymerizable composition according to claim 1, wherein the photoinitiator composition contains an organic peroxide.