JP2643564B2 - Photoinitiator composition - Google Patents

Description

The present invention relates to a novel photoinitiator composition for photopolymerizing a polymerizable unsaturated compound and a cyclic compound. The present invention relates to a high-sensitivity photoinitiator composition which is sensitive to light having a wavelength of 600 nm to 720 nm at a low light intensity.

(Prior art) It is well known that monomers, oligomers and polymers containing an ethylenically unsaturated bond or a reactively active cyclic moiety in the molecule undergo photopolymerization in the presence of a photoinitiator.
Widely used for printing plate making, printed circuit boards, inks, paints, varnishes, photoresists, etc. In addition, attention has been paid to an image forming material using a laser beam and a photosensitive material instead of a silver salt.

With regard to the photosensitive material used as such a material, increasing the photosensitive speed as much as possible is important for its performance and much research has been conducted. However, most of the research so far has been concerned with photoinitiator compositions that are active in ultraviolet light or light having a wavelength shorter than 600 nm, and the photosensitive properties for light having a longer wavelength (600 nm or more) are not the same as conventional ones. Because of its sufficient size, it has the disadvantage that light sources such as He-Ne laser (oscillation wavelength 633 nm), Kr ⁺ laser (oscillation wavelength 647 nm), and semiconductor laser cannot be used because it is compact and has a stable light source. I have. In recent years, a semiconductor laser having an oscillation wavelength shorter than the wavelength (670 nm or less) has also been developed, and a high sensitivity that is sensitive to light of a longer wavelength (600 nm or more) than the conventional one with a small amount of light. The development of a light-sensitive material is desired.

On the other hand, a photocurable composition comprising methylene blue, p-toluenesulfonic acid, and barium acrylate exhibiting high photosensitivity to a He-Ne laser has been proposed [[Photographic and Scientific. Engineering (Photogr.Sci.Eng.) ", Volume 12,
177 (1968)], which has the disadvantage that it is hydrophilic and is not suitable for lipophilic resin compositions. Further, as a lipophilic photocurable resin composition having photosensitivity to a long wavelength light source such as a He-Ne laser, a Kr ⁺ laser, and a semiconductor laser, porphyrins, azaporphyrins, phthalocyanines or metal complexes thereof. And a diaryl iodonium salt as a photopolymerization initiator (JP-A-60-78442). However, the porphyrins have low photosensitivity to long-wavelength light of 600 nm or more. In addition, azaporphyrins have low sensitizing efficiency, and phthalocyanines have low solubility in various organic solvents. A photocurable resin composition comprising a combination of a tetrabenzoporphyrin and an electron-accepting radical generator has also been proposed (JP-A-63-243102). However, there is a problem that the synthesis method in has not been established yet.

(Problems to be Solved by the Invention) The present invention overcomes the drawbacks of such conventional photoinitiator compositions and photopolymerizable compositions, and provides excellent sensitivity to light having a wavelength of 600 nm to 720 nm. The purpose of the present invention is to provide a highly sensitive photoinitiator composition having a property.

(Means for Solving the Problems) In view of the above points, the present inventors have conducted intensive studies to achieve the above object, and as a result, have found that a porphyrazine-based compound having a specific structure is at least one kind and at least one kind. It has been found that the above object can be achieved by combining the above-described radical generator, and the present invention has been completed based on this finding.

That is, the first invention is based on the following general formula (I): [In the formula (I), rings A ^{1 to} A ⁴ are each independently Wherein all of the rings A ^{1 to} A ⁴ are simultaneously Will not be.

R ^{1 to} R ¹² each independently represent a hydrogen atom, a halogen atom and an organic residue other than a hydrogen atom and a halogen atom, R ¹ and R ² , R ³ and R ⁴ , R ⁴ and R ⁵ , R ⁶ and R ^7, R ⁹ and R ^10, R
An annular structure in which ¹⁰ and R ¹¹ and R ¹¹ and R ¹² are integrated may be used.

M represents two hydrogen atoms or atoms having a valence of 2 or more which may have a substituent.

Y and Z each independently represent a halogen atom, an oxygen atom and an organic residue other than a halogen atom and an oxygen atom, and among these, the atom in the organic residue directly bonded to M is an oxygen atom, Limited to nitrogen, carbon or sulfur atoms.

l and m each independently represent an integer of 0 or 1. ] A photoinitiator composition comprising a combination of at least one porphyrazine-based compound represented by the formula and (ii) at least one or more electron-accepting radical generators.

According to a second aspect of the present invention, the electron acceptor radical generator is an onium salt compound, a 1,3,5-triazine derivative substituted by at least one mono-, di- or trihalomethyl group, an iron allene compound, and an organic peroxide. At least one electron-accepting radical generator selected from the group consisting of

 Hereinafter, the present invention will be described in detail.

Explaining the substituent in the general formula (I), R ¹
To R ¹² are each independently a hydrogen atom, a halogen atom,
And an organic residue other than a hydrogen atom and a halogen atom. Among them, the halogen atom is a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like, and the hydrogen atom and the organic residue other than the halogen atom are:
An alkyl group which may have a substituent, an aryl group which may have a substituent, a vinyl group which may have a substituent, a nitro group, a hydroxyl group, an alkoxy group which may have a substituent, Aryloxy group which may have a group, acyloxy group which may have a substituent, acyl group which may have a substituent, carboxylic acid group, carboxylate group, carbamoyl group, mercapto group, substituent Alkylthio group which may have, an arylthio group which may have a substituent, a substituted sulfinyl group, a substituted sulfonyl group, a sulfonic acid group, a sulfonic acid ester group, a thiocarboxylic acid group, a dithiocarboxylic acid group, a thiocarbamoyl group, A cyano group, an amino group which may have a substituent,
Substituted azo group, phosphino group which may have a substituent,
A phosphono group which may have a substituent, a substituted silyl group,
Examples thereof include a substituted siloxy group and a heterocyclic group which may have a substituent, but are not limited to these substituents.

Further, when the above organic residue is described in detail,
Examples of the alkyl group which may have a substituent include a methyl group, an ethyl group, an n-butyl group, a tert-butyl group, an octyl group, a stearyl group, a cyclohexyl group, a mentyl group,
Bornyl group, allyl group, benzyl group, trifluoromethyl group, trichloromethyl group, methoxymethyl group, carboxymethyl group, hydroxymethyl group and the like, and the aryl group which may have a substituent include a phenyl group, a tolyl group, A vinyl group, a butenyl group, a 2-bromoethenyl group, a naphthyl group, a cumenyl group, a trichlorophenyl group, a hydroxyphenyl group, a mesityl group, a carboxoxyphenyl group, or the like; A carboxyethenyl group or the like, and an optionally substituted alkoxy group includes a methoxy group, an ethoxy group, a tert-butoxy group, a benzyloxy group, a 2-hydroxyethoxy group, etc. Aryloxy group which may be phenoxy group, 2,4,6-trimethylphenoxy group 4-bromophenoxy group, naphthyloxy group and the like, and the acyloxy group which may have a substituent include an acetoxy group, a benzoyloxy group, a formyloxy group, an acryloyloxy group and a methacryloyloxy group. Examples of the acyl group which may have a group include a formyl group, an acetyl group, a butyroyl group, a lauroyl group, an acryloyl group, a methacryloyl group, an oleoyl group, a benzoyl group, and a cinnamoyl group. A methoxycarbonyl group, an ethoxycarbonyl group, a phenoxycarbonyl group, and the like; and an alkylthio group which may have a substituent include a methylthio group, an ethylthio group, a hydroxymethylthio group, and an arylthio group which may have a substituent. Is a phenylthio group, 4 Methoxyphenyl thio group, a naphthylthio group, and examples of the substituted sulfinyl group, methylsulfinyl group, phenylsulfinyl group, a hydride carboxymethyl ethylsulfinyl group,
Examples of the substituted sulfonyl group include a methylsulfonyl group, a benzenesulfonyl group, a tosyl group, and a sulfamoyl group.Examples of the sulfonic acid ester group include a methoxysulfonyl group, an ethoxysulfonyl group, and a phenoxysulfonyl group. Examples of the amino group which may be an amino group, a methylamino group, a dimethylamino group, an anilino group, a toluidino group, and the like, and the substituted azo group include a phenylazo group, a naphthylazo group, and the like.
Examples of the phosphino group which may have a substituent include a dimethylphosphino group and a diphenylphosphino group.
Examples of the phosphono group which may have a substituent include a phosphono group, a dimethylphosphono group, a diphenylphosphono group, and the like.As the substituted silyl group, a trimethylsilyl group, a triethylsilyl group, and the like.As the substituted siloxy group, ,
Heterocyclic groups which may be substituted, such as trimethylsiloxy and triethylsiloxy, include furyl, thienyl, pyridyl, pyrrolyl, piperidino, morpholino, methylquinolyl, and phenylthiazolyl. Groups, chlorobenzothiazolyl group, methyloxazolyl group, methylimidazolyl group and the like, but are not limited to these substituents.

In the general formula (I), R ¹ and R ² , R ³ and R ⁴ , and R ⁴ and
R ⁵ , R ⁶ and R ⁷ , R ⁹ and R ¹⁰ , R ¹⁰ and R ¹¹ , R ¹¹ and R ¹² may each be a united cyclic structure, for example, trimethylene group, tetramethylene group, etc. Other than an alkylene group, an ethylenedioxy group, an ethylenediamino group, And the like, but is not limited to these substituents.

Further, in the general formula (I), M represents two hydrogen atoms or divalent or higher valent atoms which may have a substituent, and Zn, Pd, Cd, Mg, Al, Ti, Ge, Sn, V , Si and the like.

Y and Z each independently represent a halogen atom, an oxygen atom and an organic residue other than a halogen atom and an oxygen atom. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Yes, and as an organic residue other than a halogen atom and an oxygen atom,
Alkyl group which may have a substituent, aryl group which may have a substituent, hydroxyl group, alkoxy group which may have a substituent, aryloxy group which may have a substituent, carboxylic acid group A carboxylate group, a carbamoyl group, a mercapto group, an alkylthio group which may have a substituent, an arylthio group which may have a substituent, a substituted sulfonyl group, a sulfonic acid group, a sulfonic acid ester group, a sulfamoyl group, An amino group which may have a substituent, a heterocyclic group which may have a substituent, -OSO
₂ R ¹³ groups, -O-PR ¹⁴ R ¹⁵ groups, -O (P = O) R ¹⁶ R ¹⁷ groups (however, R ¹³
To R ¹⁷ are an alkyl group which may have a substituent, an aryl group which may have a substituent, a hydroxyl group, an alkoxy group which may have a substituent, and an aryloxy group which may have a substituent And heterocyclic groups which may have a substituent), but are not limited to these substituents. However, among these, the atoms in the organic residue directly bonded to M are limited to an oxygen atom, a nitrogen atom, a carbon atom or a sulfur atom.

Compounds which are preferably used as an electron-accepting radical generator, which is the other component of the photoinitiator composition, are described below. First, the radical generator is represented by the general formula (II) among the onium salt compounds: (Wherein, R ¹⁸ and R ¹⁹ are a hydrogen atom, a halogen atom, a lower alkyl group, a methoxy group, a nitro group or a cyano group, respectively, X ⁻ is a halogen ion, BF ₄ ⁻ , PF ₆ ⁻ , AsF ₆ ⁻ , ClO
₄ ^-, SbPF ₆ ^- are shown) diaryliodonium salt [represented by the general formula (II) "Macromolecules scan (Macromolecules)" 10
Volume, 1307 (1977)], General formula (III) (Wherein R ²⁰ and R ²¹ are an alkyl group, and R ¹⁸ and X ⁻ have the same meanings as described above), [Journal of Polymer Science (J. Polym. Sci. .) "Volume 17, page 2877 (19
79)], general formula (IV) (Wherein R ²² and R ²³ are an alkyl group or an aryl group, respectively, and R ¹⁸ and X ⁻ have the same meanings as described above) (European Patent No. 44274), Equation (V) (Wherein R ¹⁸ , R ²² , R ²³ and X ⁻ have the same meaning as described above) (European Patent No. 44274), a general formula (VI) (Wherein R ²⁴ , R ²⁵ and R ²⁶ each represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an aryl group,
Represents an aryl group, a nitro group or an amino group, Q represents oxygen, represents sulfur or selenium, X ^- is pyrylium salt represented by having) as defined above, thiapyrylium salt or Serena pyrylium (JP 59- No. 45303).

In addition to the above, general formula (VII) (Wherein R ²⁷ , R ²⁸ and R ²⁹ represent a methyl group or a trihalomethyl group, respectively) (JP-A-60-60104); ) (R ³⁰ is an alkyl group in the formula, X ^- is sulfate, nitrate, acetate _{^{ion, BF 4 -, PF 6 -}} , AsF 6 -, ClO 4 -, SbPF 6 - are shown) iron arene compound represented by the [European Patent No.
No. 109,851, EP 126,712, "Journal of Imaging Science (J.IMAG.S
CI, Vol. 30, p. 174 (1986)], and organic peroxides having at least one oxygen-oxygen bond in the molecule (JP-A-59-140203).

Examples of the diaryliodonium salt represented by the general formula (II) include iodonium such as diphenyliodonium, phenyl (p-anisyl) iodonium, bis (m-nitrophenyl) iodonium, and bis (p-tert-butylphenyl) iodonium. Chloride, bromide, borofluoride, hexafluorophosphate,
Examples of the phenacylsulfonium salt represented by the general formula (III) such as hexafluoroarsenate salt include chlorides, bromides, borofluorides such as dimethylphenacylsulfonium, phenacyltetramethylenesulfonium, and P-chlorophenacylsulfonium. Salts, hexafluorophosphate salts, hexafluoroarsenate salts and the like, as phenacylsulfoxonium salts represented by the general formula (IV), for example, chlorides such as dimethylphenacylsulfoxonium and diphenylphenacylsulfoxonium; Bromide, borofluoride, hexafluorophosphate salt, hexafluoroarsenate salt, etc.
Examples of the phenacylsulfoxonium salt represented by the general formula (V) include chlorides such as dimethylphenoxysulfoxonium and diphenylphenoxysulfoxonium, bromides, borofluorides, hexafluorophosphate salts, hexafluoroarsenate salts and the like. Is a pyrylium salt represented by the general formula (VI), a thiapyrylium salt,
Examples of selenapyrylium salts include 2,4,6-triphenylpyrylium, 2,4,6-tris (trichloromethyl) pyrylium, 2,4,6-tri-tert-butylthiapyrylium,
4,6-tris (tribromomethyl) thiapyrylium, 2,
Chloride such as 4,6-tris (trichloromethyl) selenapyrylium, bromide, borofluoride, hexafluorophosphate salt, hexafluoroarsenate salt, etc.
As the 1,3,5-triazine compound represented by the general formula (VII), 2,4,6-tris (trichloromethyl) -1,3,5-
Triazine, 2,4,6-tris (tribromomethyl) -1,
3,5-triazine, 2-phenyl-4,6-bis (trichloromethyl) -1,3,5-triazine and the like are represented by the general formula (VIII)
Examples of the iron allene compound represented by are (η ⁶ -benzene) (η ⁵ -pentadienyl) iron and (η ⁶ -cumene)
(Eta ⁵ - methyl cyclopentadienyl) iron, (eta ⁶ - naphthalene) (eta ⁵ - ethyl cyclopentadienyl) chloride, such as iron,
Bromides, borofluorides, hexafluorophosphate salts, hexafluoroarsenate salts and the like, and organic peroxides such as methyl ethyl ketone peroxide and 1,1-bis (tert-butylperoxy) -3,3,5-trimethylcyclohexane , Cumene hydroperoxide, benzoyl peroxide and the like.

The porphyrazine-based compound represented by the above general formula (I) used in the present invention generally has the following general formula (IX) to
The nitriles represented by (XII) (the desired product cannot be obtained by using (XII) alone) and various metal salts (in the case of non-metallic porphyrazine, not used or alkali metal salts are used) are preferred. Can be prepared by heating in an organic solvent [Journal of General Chemistry in USSR (J. Gen. Che.
m.USSR) ", vol. 39, p. 2477 (1969), JP-A-64
-34791].

Various porphyrazine compounds can also be obtained by mixing and reacting nitriles having different substituents represented by the above general formulas (IX) to (XII). The porphyrazine-based compound of the general formula (I) can also be produced from isoindolinediimine derivatives represented by the following general formulas (VIII) to (XIV) [“Journal of Heterocyclic Chemistry ( J.HETERO
CYCL.CHEM) ", Volume 7, page 1403 (1970), Journal of the Chemical Society of Japan, page 219 (1990)].

Representative examples (compounds (a) to (i)) of the porphyrazine-based compound represented by the general formula () used in the present invention are shown below.

In the above compounds (a) to (i), t-Bu is a tert-butyl group, Me is a methyl group, Ph is a phenyl group, Pr is an n-propyl group, and ^nC ₉ H ₁₉ represents an n-nonyl group.

The photoinitiator composition of the present invention contains at least one porphyrazine-based compound as described above and at least one or more of the above-described radical generators as an active ingredient, and the mixing ratio of both is by weight. (Porphyrazine-based compound): (Radical generator) is 1 to 99:99 to 1, more preferably 25 to 75:75 to 25.

The photoinitiator composition of the present invention is capable of photopolymerizing almost all polymerizable unsaturated compounds with long-wavelength light of 600 nm or more in a very short time. Examples of these unsaturated compounds include acrylic acid, methacrylic acid, itaconic acid, maleic acid and its esters and anhydrides, acrylamide, styrene, acrylonitrile, N-vinylpyrrolidone, vinyl acetate, various unsaturated polyesters, and unsaturated polyesters. Examples include compounds such as polyethers and unsaturated polyurethanes.

The photoinitiator composition of the present invention is added to one or a mixture of two or more of these unsaturated compounds, and if necessary, ordinary dyes, pigments, additives, inhibitors and the like and an appropriate diluting solvent are added. It is a photopolymerizable composition.

The addition amount of the photoinitiator composition is 0.1 to 30 parts by weight, preferably 0.5 to 20 parts by weight based on 100 parts by weight of the unsaturated compound.

As the appropriate diluting solvent, any solvent can be used as long as it dissolves the photoinitiator composition of the present invention and the unsaturated compound to be used.For example, water, methanol, ethanol, propanol, acetone, methyl ethyl ketone,
Examples include methyl cellosolve, ethyl cellosolve, benzene, toluene, xylene, tetrahydrofuran, dioxane, ethyl acetate, dichloromethane, chloroform, trichloroethylene, dimethylformamide, dimethylsulfoxide, pyridine and the like.

(Synthesis Examples) Synthesis examples of compounds (a) to (i) will be described before the Examples, but the present invention is not limited to these Examples.

Synthesis Example 1: Synthesis of compound (a) 2-tert-butyl-5,6-dicyanopyrazine 5.00 g
And 0.955 g of anhydrous zinc chloride were dissolved in 30 ml of quinoline, heated and stirred at 180 ° C. for 4 hours in a nitrogen atmosphere, allowed to cool, diluted with 100 ml of water, filtered, extracted with chloroform, chloroform / methanol Recrystallized at 1.14 g of compound (a)
I got

Synthesis Example 2: Synthesis of compound (b) To 25.00 g of the above compound, 150 ml of 2- (dimethylamino) ethanol was added, and the mixture was heated and refluxed for 8 hours while stirring under a nitrogen atmosphere, allowed to cool, and diluted with 300 ml of water. The mixture was filtered, extracted with chloroform, and recrystallized from chloroform / methanol to obtain 3.0 g of compound (b).

Synthesis Example 3: Synthesis of compound (c) 32 g of 2,3-dicyano-5,6-ethylenedioxypyridine
And 7.8 g of anhydrous cadmium chloride and 20 g of 1,8-diazabicyclo [5.4.0] undec-7-ene (DBU) were dissolved in 150 ml of n-amyl alcohol, heated under reflux in a nitrogen atmosphere for 4 hours, allowed to cool, and reacted. The liquid was diluted with 300 ml of water, separated by filtration, extracted with chloroform, and recrystallized with methanol to obtain 9.67 g of compound (c).

Synthesis Example 4: Synthesis of compound (d) 13.3 g of 4,5-dicyano-2-phenoxypyridine and
3.14 g of 2,6-dimethyl-3,4-dicyanopyridine, 4.58 g of magnesium diethoxide, 100 ml of n-amyl alcohol
And heated under reflux for 9 hours under a nitrogen atmosphere, allowed to cool, diluted with 300 ml of water, filtered, and extracted with chloroform.
It was separated and purified by column chromatography (silica gel / chloroform), and recrystallized from chloroform / methanol to obtain 3.44 g of compound (d).

Synthesis Example 5: Synthesis of compound (e) 17.3 g of 2,3-dibromo-5,6-dicyanopyrazine and
5.08 g of 1,2-dicyano-4-nonylbenzene, 4.49 g of palladium acetate, and 10 g of DBU were dissolved in 100 ml of n-amyl alcohol, heated under reflux in a nitrogen atmosphere for 12 hours, allowed to cool, and then cooled with water.
The mixture was diluted with 300 ml, filtered, extracted with chloroform, separated and purified by column chromatography (silica gel / chloroform), and recrystallized with chloroform / methanol to obtain 3.62 g of compound (e).

Synthesis Example 6: Synthesis of compound (f) 14.3 g of the compound shown above and 2,3-dicyanopyridine
2.58 g, vanadium trichloride 3.15 g, DBU7.0 g quinoline 100
The reaction solution was dissolved under reflux in a nitrogen atmosphere for 11 hours, allowed to cool, diluted with 300 ml of methanol, filtered, extracted with chloroform, separated by column chromatography (silica gel / chloroform), purified and purified. The crystals were recrystallized from / methanol to obtain 2.80 g of compound (f).

Synthesis Example 7: Synthesis of compound (g) 14.28 g of 2,3-dicyano-5,6-dipropoxypyrazine and 3.5 g of 4,5-dicyano-2-methylthiopyridine, 5.34 g of aluminum chloride, and 8 g of DBU are dissolved in 100 ml of quinoline. After heating and refluxing for 8 hours under a nitrogen atmosphere, the reaction solution was allowed to cool, diluted with 300 ml of methanol, filtered, and extracted with chloroform.
It was separated and purified by column chromatography (silica gel / chloroform), and recrystallized from chloroform / methanol to obtain 2.64 g of compound (g).

Synthesis Example 8: Synthesis of compound (h) 5.13 g of 4,5-dicyanonicotinic acid and 1.71 g of 2-carboxyl-5,6-dicyanopyridine, 7.59 of lead acetate trihydrate
g, 3 g of 1,4-diazabicyclo [2.2.2] octane was dissolved in 100 ml of nitrobenzene, heated under reflux in a nitrogen atmosphere for 15 hours, allowed to cool, diluted with 100 ml of hexane, filtered, extracted with methanol, Separation and purification by reverse phase column chromatography (octadecyl chemically modified silica gel / ethanol), recrystallization from methanol and 1.2 g of compound (h)
I got

Synthesis Example 9: Synthesis of compound (i) 15.5 g of 2,3-dicyano-4-dimethylaminopyridine and 1,2-dicyano-3,4,5,6-tetraiodobenzene 1
8.95 g, sodium acetate 12 g and n-amyl alcohol 200 m
The mixture was dissolved in l, heated under reflux in a nitrogen atmosphere for 15 hours, allowed to cool, the reaction solution was diluted with 500 ml of water, and filtered to obtain 3.69 g of compound (i).

(Examples) Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. The middle part in the examples is part by weight.

Examples 1 to 9 The molar ratio of chloromethylstyrene to methyl methacrylate
The copolymer having a ratio of 1: 1 and potassium acrylate are reacted in 40 ml of dimethylformamide at 40 ° C. for 12 hours under oxygen gas bubbling using tetrabutylammonium chloride and potassium carbonate as a phase transfer catalyst. ,
A polymer having an acryloyl group in a side chain was obtained. The obtained polymer was dissolved in dioxane to prepare a solution having a concentration of 5% by weight, and thereafter used as a resin for evaluating sensitivity characteristics.

To 2 g of a dioxane solution of the above polymer, 50 parts by weight of pentaerythritol triacrylate based on the polymer, and 10 parts of each of the porphyrazine compounds and diphenyliodonium tetrafluoroborate shown in Table 1 were added.
The photosensitive solution prepared by adding a part by weight was applied on a glass plate to a thickness of about 2 μm using a spin coater, and further coated with a 10% aqueous solution of polyvinyl alcohol as an oxygen inhibition layer. with a beam diameter of mm
Exposure was performed with a 0.14 mW / cm ² He-Ne laser beam of 633 nm for various irradiation times, developed with water and toluene, and an exposure amount that gave a cured spot diameter equivalent to the laser beam diameter was used as the sensitivity. The results are shown in Table 1. The porphyrazine compounds in the table are the compounds (a) to (i) shown above.
And the same substance.

Examples 10 to 16 In the polymer solution prepared in the same manner as in Examples 1 to 9,
Porphyrazine derivative represented by compound (a) and second
10 parts by weight of each of the radical generators shown in the table were added to the polymer to prepare a photosensitive solution, which was evaluated in the same manner as in Examples 1 to 9. The results are shown in Table 2.

(Effect of the Invention) The photoinitiator composition of the present invention comprises a carbon arc,
Xenon lamps, metal halide lamps, fluorescent lamps,
Tungsten lamps can be used, and 60
High sensitivity to light with wavelengths from 0 nm to 720 nm (0.1 mJ /
cm ² to several mJ / cm ² ), a gas laser such as a He-Ne or Kr ⁺ laser or a semiconductor laser can be used. In addition, since it does not show reciprocity failure behavior even in high-speed scanning exposure by laser beam scanning, it can be applied to image forming materials by laser beam scanning, such as direct printing plates, photoresist for printed wiring boards, non-silver salt image forming materials, etc. In addition, Lippmann-type holograms that require high sensitivity for the formation of subtle interference fringes, and hologram recording materials for relief-type hologram recording in rainbow holograms, for which it was difficult to increase the area, are widely used. Applicable to

Claims (2)

(57) [Claims] 1. Photoinitiation characterized by combining (a) at least one porphyrazine-based compound represented by the following general formula (I) and (b) at least one or more electron-accepting radical generators. Composition. General formula (I) (In the formula (I), rings A ^{1 to} A ⁴ are each independently Wherein all of the rings A ^{1 to} A ⁴ are simultaneously Will not be. R ^{1 to} R ¹² each independently represent a hydrogen atom, a halogen atom and an organic residue other than a hydrogen atom and a halogen atom, R ¹ and R ² , R ³ and R ⁴ , R ⁴ and R ⁵ , R ⁶ and R ^7, R ⁹ and R ^10, R ¹⁰
And R ¹¹ , and a ring structure in which R ¹¹ and R ¹² are integrated. M represents two hydrogen atoms or atoms having a valence of 2 or more which may have a substituent. Y and Z each independently represent a halogen atom, an oxygen atom and an organic residue other than a halogen atom and an oxygen atom, and among these, the atom in the organic residue directly bonded to M is an oxygen atom, Limited to nitrogen, carbon or sulfur atoms. l and m each independently represent an integer of 0 or 1. ) 2. The method according to claim 1, wherein the radical generator is at least one selected from onium salt compounds, 1,3,5-triazine derivatives substituted by at least one mono-, di- or trihalomethyl group, iron allene compounds and organic peroxides. 2. The photoinitiator composition according to claim 1, which is one kind of electron accepting radical generator.