JP2660108B2 - Photoinitiator composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel photoinitiator composition for photopolymerizing a polymerizable unsaturated compound, and more particularly, to a low light quantity for light having a wavelength of from 600 nm to 720 nm. And a high-sensitivity photo-peroxide-forming radical generator sensitive to the above.

[0002]

2. Description of the Related Art It is well known that monomers, oligomers and polymers containing an ethylenically unsaturated bond in a molecule undergo photopolymerization in the presence of a photoinitiator. , Paints, varnishes, photoresists, etc. Attention has also been focused on image forming materials using laser light, such as hologram recording and non-silver-salt type photosensitive materials that replace silver salts.

In photosensitive materials used as such materials, increasing the photosensitive speed as much as possible is important for its performance, and much research has been conducted.

However, much of the work to date has been directed to photoinitiator compositions that are active in ultraviolet light or light at wavelengths shorter than 600 nm, and have been studied for longer wavelengths (600 nm).
The above-described light sensitivity characteristics of conventional light sources were insufficient, so that He is advantageous in that it is small and the light source is stable.
There is a drawback that a light source such as a -Ne laser (oscillation wavelength 633 nm), a Kr ⁺ laser (oscillation wavelength 647 nm), and a semiconductor laser cannot be used.

In recent years, shorter wavelengths (670 n
m), a high-power (several tens of mW or more) semiconductor laser having an oscillation wavelength has been developed. The development of photosensitive materials is desired.

On the other hand, there has been proposed a photocurable composition comprising methylene blue, p-toluenesulfonic acid and barium acrylate exhibiting high photosensitivity to a He-Ne laser [see "Photographic and Science". Tifik Engineering (Photogr.Sci.En
g.), Vol. 12, p. 177 (1968)], which has the disadvantage that it is hydrophilic and 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 There has been proposed a composition using a combination of the metal complex and a diaryliodonium salt as a photopolymerization initiator (Japanese Patent Application Laid-open No. Sho.
0-78442), and 600 porphyrins
The problem remains that photosensitivity to long-wavelength light of nm or more is low, 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).
), There is a problem that the synthesis method of tetrabenzoporphyrins on an industrial scale has not been established yet.

On the other hand, Japanese Patent Publication No. Sho 58-42459 proposes a method for producing a printing plate using a photosensitive composition comprising a photo-oxidizable composition and a photo-oxidizable sensitizer.

[0010]

However, in order to enhance the sensitivity characteristics of the photosensitive composition using these photopolymerization initiators in the above-mentioned attempts, oxygen which suppresses the photopolymerization reaction is cut off at the time of light irradiation. It is necessary to use a dry film or an oxygen-inhibiting layer, for example, a polyvinyl alcohol film, on the photosensitive layer, which is difficult to handle and economic.

In the latter photosensitive composition comprising a photo-oxidizable composition and a photo-oxidizable sensitizer, the solubility of the photo-oxidizable sensitizer in various solvents and the photo-oxidizable composition It is not always satisfactory in any or all of the ability to generate peroxide or the wavelength matching property with the laser light source, so that the sensitivity characteristics are insufficient, and those that can withstand laser high-speed scanning exposure. Did not.

The present invention overcomes the disadvantages of the conventional photoinitiator compositions and photopolymerizable compositions and has a 600 nm
The object of the present invention is to provide a highly sensitive photoperoxide-forming photoinitiator composition having excellent photosensitivity to light having a wavelength of up to 720 nm.

[0013]

Means for Solving the Problems The present inventors have made intensive studies in order to achieve the above object in consideration of the above points, and
It has been found that the object can be achieved by combining a porphyrazine-based compound (A) having a specific structure, at least one or more photo-oxidizable compounds (B), and at least one or more redox catalysts (C). The present invention has been completed based on this finding.

That is, the first invention comprises at least one of the following general formulas (I) and (I)

[0015]

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(In the formula (I), rings A ^{1 to} A ⁴ are each independently

[0017]

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Wherein all of the rings A ^{1 to} A ⁴ are simultaneously

[0019]

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Does not occur.

R ^{1 to} R ¹² each independently represent a hydrogen 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 ¹⁰ represent a halogen atom and an organic residue other than a hydrogen atom and a halogen atom. ¹¹ , R ¹¹ and R
¹² may have an annular structure integrally formed.

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, or an organic residue other than a halogen atom and an oxygen atom. Of these, the atoms in the organic residue directly bonded to M are: Limited to oxygen, nitrogen, carbon or sulfur atoms.

L and m are each independently 0 or 1
Represents an integer. ), At least one or more photo-oxidizable compounds (B), and at least one or more redox catalysts (C)
A photoinitiator composition comprising a photoperoxide-forming radical generator comprising:

The second invention relates to the above photooxidizable compound (B)
Is an olefin compound having at least one or more methyl groups on a double bond carbon, which can react with singlet oxygen to form a photoperoxide.

The third invention relates to the redox catalyst (C)
Is a metal salt or complex that can exist in more than one valence state.

Hereinafter, the present invention will be described in detail.

The substituents in the general formula (I) will be described. 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. Among them, a halogen atom is a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like, and an organic residue other than a hydrogen atom and a halogen atom is 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, an aryloxy group which may have a substituent, and a substituent An acyloxy group which may have a substituent, an acyl group which may have a substituent, a carboxylic acid group, a carboxylate group, a carbamoyl group, a mercapto group, an alkylthio group which may have a substituent, Arylthio group, substituted sulfinyl group, substituted sulfonyl group, sulfonic acid group, sulfonic ester group, thiocarboxylic acid group, dithiocal Acid group, thiocarbamoyl group, cyano group, amino group optionally having a substituent, substituted azo group, phosphino group optionally having a substituent, phosphono group optionally having a substituent, substituted silyl Groups, substituted siloxy groups, heterocyclic groups which may have a substituent, and the like, but are not limited to these substituents.

Further, the above organic residue will be 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 and a stearyl group. , Cyclohexyl group, menthyl group, bornyl group, allyl group, benzyl group, trifluoromethyl group, trichloromethyl group, methoxymethyl group, carboxymethyl group, hydroxymethyl group and the like,

Examples of the aryl group which may have a substituent include a phenyl group, a tolyl group, a naphthyl group, a cumenyl group, a trichlorophenyl group, a hydroxyphenyl group, a mesityl group and a carboxyphenyl group.

Examples of the optionally substituted vinyl group include a vinyl group, a butenyl group, a 2-bromoethenyl group and a 2-carboxyethenyl group.

Examples of the optionally substituted alkoxy group include a methoxy group, an ethoxy group, a tert-butoxy group,
Benzyloxy group, 2-hydroxyethoxy group and the like,

The aryloxy group which may have a substituent includes a phenoxy group, a 2,4,6-trimethylphenoxy group, a 4-bromophenoxy group, a naphthyloxy group and the like.

The acyloxy group which may have a substituent includes 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 substituent 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.

Examples of the carboxylate group include a methoxycarbonyl group, an ethoxycarbonyl group and a phenoxycarbonyl group.

Examples of the alkylthio group which may have a substituent include a methylthio group, an ethylthio group and a hydroxymethylthio group.

The arylthio group which may have a substituent includes a phenylthio group, a 4-methoxyphenylthio group, a naphthylthio group and the like.

Examples of the substituted sulfinyl group include a methylsulfinyl group, a phenylsulfinyl group and a hydroxyethylsulfinyl 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 have a substituent include an amino group, a methylamino group, a dimethylamino group, an anilino group and a toluidino group.

Examples of the substituted azo group include a phenylazo group and a naphthylazo group.

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 and a diphenylphosphono group.

Examples of the substituted silyl group include a trimethylsilyl group and a triethylsilyl group.

Examples of the substituted siloxy group include a trimethylsiloxy group and a triethylsiloxy group.

The heterocyclic group which may have a substituent includes a furyl group, a thienyl group, a pyridyl group, a pyrrolyl group,
Examples thereof include a piperidino group, a morpholino group, a methylquinolyl group, a phenylthiazolyl group, a chlorobenzothiazolyl group, a methyloxazolyl group, and a methylimidazolyl group, but are not limited to these substituents.

In the general formula (I), 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 R ¹¹ and R ¹² may each be a united cyclic structure, for example, an alkylene group such as a trimethylene group, a tetramethylene group, an ethylenedioxy group,
Other than ethylenediamino group, etc.

[0050]

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The substituents are not limited to these.

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

Further, Y and Z each independently represent a halogen atom, an oxygen atom and an organic residue other than the halogen atom and the oxygen atom. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Atom, etc.

As the organic residue other than the halogen atom and the oxygen atom, an 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, carboxylate group, carbamoyl group, 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, have a substituent heterocyclic group, -OSO ₂ R ¹³ group, -0-PR ¹⁴ R ¹⁵ group,
—0 (P ＝ O) R ¹⁶ R ¹⁷ group (where 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 optionally substituted alkoxy group, an optionally substituted aryloxy group, and an optionally substituted heterocyclic group), but are not limited to these substituents.

However, the atoms in the organic residue directly bonded to M are limited to oxygen, nitrogen, carbon and sulfur atoms. Among the photo peroxide-forming radical generators, the photo-oxidizable compound (B) is represented by the formula (II)

Formula (II)

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(In the formula, R ¹⁸ represents a hydrogen atom or a halogen atom such as chlorine or bromine, and R ¹⁹ represents a methyl group or a trifluoromethyl group.)

A dimethylcyclohexene compound represented by the formula (JP-B-58-42459) or a compound represented by the formula (II)
I)

Formula (III)

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(Wherein R ¹⁸ and R ¹⁹ have the same meanings as in formula (II)) or a compound of formula (IV)

Formula (IV)

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(Wherein R ¹⁸ and R ¹⁹ have the same meanings as in formula (III)) represented by formula (V):

Equation (V)

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(Wherein R ¹⁸ and R ¹⁹ have the same meanings as in formula (III)), and the like.

These compounds have at least one methyl group on carbon forming a double bond, and this methyl group reacts with singlet oxygen to form a peroxide.

Among the photo peroxide-forming radical generators,
(C) The redox catalyst is preferably a metal salt or complex that can exist in two or more valence states, for example, vanadium oxyacetylacetone, vanadium oxysulfate, vanadium oxynaphthenate, oxytetraphenylporphyrinatovanadyl, oxyocta. Oxyvanadium salts or complexes such as ethylporphyrinatovanadyl, oxytetra-t-butylphthalocyanine vanadyl,

Cobalt acetylacetonate, cobaltous acetylacetonate, cobaltous naphthenate,
Cobaltous naphthenate, cobaltous stearate,
Cobalt salts or complexes of cobalt stearate, cobalt acetate, tetraphenylporphyrinatocobalt, octaethylporphyrinatocobalt, tetra-t-butylphthalocyanine cobalt,

Manganese stearate, manganese stearate, manganese acetylacetonate,
Manganese acetylacetonate, manganese acetate, manganese naphthenate, manganese tetraphenylporphyrinato,
Manganese salts or complexes such as octaethylporphyrinatomanganese, tetra-t-butylphthalocyanine manganese,

Iron (III) acetylacetonate, iron (I
II) Benzoylacetonato, tetraphenylporphyrinatoiron (III) chloride, octaethylporphyrinatoiron (III) chloride, tetra-t-butylphthalocyanine iron (III) chloride, iron naphthenate (I)
II) iron salts or complexes such as ferrocene, cyclopentadienyl-cumene iron hexafluorophosphate, iron (II) O-phenanthroline,

Titanium salts or complexes of titanylacetylacetonato, titanocene, dicyclopentadienyltitanium (II) dichloride, oxytitanium acetylacetonato and the like can be mentioned.

The porphyrazine compound represented by the above general formula (I) used in the present invention is generally represented by the following formula (V)
The nitriles represented by I) to (IX) (the desired product cannot be obtained by using only (IX) alone) and various metal salts (in the case of non-metallic porphyrazine, it is not used or an alkali metal salt is used) Is preferably heated in an organic solvent [see Journal of General Chemistry in USSR
(J. Gen. Chem. USSR) ", vol. 39, p. 2477 (1969), JP-A-64-34791].

Formula (VI)

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Formula (VII)

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Formula (VIII)

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Formula (IX)

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Various porphyrazine compounds can also be obtained by mixing and reacting nitriles having different substituents represented by the above formulas (VI) to (IX).

The porphyrazine compounds of the general formula (I) can be obtained from the isoindolinediimine derivatives represented by the following formulas (X) to (XIII) (the desired product cannot be obtained by using only (XIII) alone). [Journal of heterocyclic chemistry (J. Heterocycl. Chem)], Vol. 7, No. 1403
Page (1970), Journal of the Chemical Society of Japan, page 219 (1990)].

Formulas (X) to (XIII)

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Representative examples of the porphyrazine compounds represented by the general formula (I) used in the present invention (compounds (a) to
(I)) is shown below.

Compound (a)

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Compound (b)

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Compound (c)

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Compound (d)

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Compound (e)

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Compound (f)

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Compound (g)

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Compound (h)

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Compound (i)

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

The photoinitiator composition of the present invention comprises at least one porphyrazine-based compound (A) represented by the general formula (I), at least one or more photo-oxidizable compounds (B), and at least one or more Redox catalyst (C)
And a photoperoxide-forming radical generator consisting of: (porphyrazine-based compound (A)) :( photo-oxidizable compound (B)) ) Is from 10 to 90:90 to 10, more preferably from 25 to 75:75 to 25, and the redox catalyst (C) is 0.01% by weight with respect to the photo-oxidizable compound (B). ~ 90%, more preferably 0.1 ~ 20
% Is desirably added.

In the photoinitiator composition of the present invention, almost all polymerizable unsaturated compounds can be photopolymerized in a very short time by long-wavelength light of 600 nm or more. 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, oligomers, polymers and the like and an appropriate diluting solvent are added. To obtain 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, per 100 parts by weight of the unsaturated compound.

As a suitable diluting solvent, any solvent which dissolves or disperses the photoinitiator composition of the present invention and the unsaturated compound to be used can be used.
Water, methanol, ethanol, propanol, acetone, methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, benzene, toluene, xylene, tetrahydrofuran, dioxane, ethyl acetate, dichloromethane,
Chloroform, trichloroethylene, dimethylformamide, dimethylsulfoxide, pyridine and the like can be mentioned.

[0095]

Next, the present invention will be described in more detail by way of examples, but the present invention is not limited to these examples. The middle part in the examples is part by weight. The examples of the synthesis of the compounds (a) to (i) will be described first.

Synthesis Example 1 Synthesis of Compound (a) 5.00 g of 2-tert-butyl-5,6-dicyanopyrazine and 0.955 g of anhydrous zinc chloride were dissolved in 30 ml of quinoline, and the mixture was dissolved in a nitrogen atmosphere.
Heat and stir at 180 ° C for 4 hours.
, Filtered off, extracted with chloroform, and recrystallized with chloroform / methanol to obtain 1.14 g of compound (a).

Synthesis Example 2: Synthesis of compound (b) 2- (dimethylamino) was added to 25.00 g of the following compound (j).
Add 150 ml of ethanol and stir under nitrogen atmosphere.
After heating under reflux, the reaction solution was allowed to cool, diluted with 300 ml of water, filtered, extracted with chloroform, and recrystallized with chloroform / methanol to obtain 30.0 g of compound (b).

Compound (j)

Embedded image Synthesis Example 3: Synthesis of compound (c) 2,3-dicyano-5,6-ethylenedioxypyridine 32 g and anhydrous cadmium chloride 7.84 g, 1,8-diazabicyclo [5.4.0]
20 g of undec-7-ene (DBU) was dissolved in 150 ml of n-amyl alcohol, and heated under reflux in a nitrogen atmosphere for 4 hours.
The reaction solution was allowed to cool, diluted with water (300 ml), filtered, extracted with chloroform, and recrystallized from methanol to give 9.67 g of compound (c).
I got

Synthesis Example 4: Synthesis of compound (d) 13.3 g of 4,5-dicyano-2-phenoxypyridine and 2,6-
3.14 g of dimethyl-3,4-dicyanopyridine and 4.58 g of magnesium diethoxide were dissolved in 100 ml of n-amyl alcohol, heated and refluxed for 9 hours under a nitrogen atmosphere, allowed to cool, diluted with 300 ml of water, and filtered. Separately, the mixture was extracted with chloroform, 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 1,2-
5.08 g of dicyano-4-nonylbenzene, palladium acetate 4.
49 g 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, diluted with 300 ml of water, filtered off, extracted with chloroform, and extracted by column chromatography (silica gel). / Chloroform) and recrystallized from chloroform / methanol to obtain 3.62 g of compound (e).

Synthesis Example 6: Synthesis of compound (f) 14.3 g of the compound (k) shown below, 2.58 g of 2,3-dicyanopyridine, 3.15 g of vanadium trichloride and 7.0 g of DBU were dissolved in 100 ml of quinoline, and a nitrogen atmosphere was used. After heating under reflux for 11 hours, the reaction solution was allowed to cool, diluted with 300 ml of methanol, filtered and filtered.
Extraction with chloroform, separation and purification by column chromatography (silica gel / chloroform), and recrystallization with chloroform / methanol gave 2.80 g of compound (f).

Compound (k)

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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 were dissolved in 100 ml of quinoline, heated under reflux in a nitrogen atmosphere for 8 hours, allowed to cool, diluted with 300 ml of methanol and filtered. The mixture was extracted with chloroform, separated and purified by column chromatography (silica gel / chloroform), and recrystallized from chloroform / methanol to obtain 2.64 g of a compound (g).

Synthesis Example 8 Synthesis of Compound (h) 5.13 g of 4,5-dicyanonicotinic acid and 2-carboxyl-
5,6-dicyanopyridine 1.71 g, lead acetate trihydrate 7.59
g, 1,4-diazabicyclo [2.2.2] octane (3 g) dissolved in nitrobenzene (100 ml), heated to reflux for 15 hours under a nitrogen atmosphere, allowed to cool, diluted with 100 ml of hexane, filtered, and filtered. Extraction, separation and purification by reversed-phase column chromatography (octadecyl chemically modified silica gel / ethanol), recrystallization from methanol to give compound (h) 11.7
g was obtained.

Synthesis Example 9 Synthesis of Compound (i) 15.5 g of 2,3-dicyano-4-dimethylaminopyridine and
1,2-dicyano-3,4,5,6-tetrafluorobenzene 12.61
g, 12 g of sodium acetate in 200 ml of n-amyl alcohol
After heating under reflux in a nitrogen atmosphere for 12 hours, the reaction solution was allowed to cool, diluted with 400 ml of water, and separated by filtration to obtain 2.31 g of compound (i).

A copolymer having chloromethylstyrene and methyl methacrylate in a molar ratio of 1: 1 and potassium acrylate were mixed in 40 ml of dimethylformamide with tetrabutylammonium chloride and potassium carbonate as a phase transfer catalyst. Under oxygen gas bubbling, 40
The reaction was carried out at 12 ° C. for 12 hours to obtain a polymer having an acryloyl group in a side chain. 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.

Examples 1 to 9 In this example, the following bisphenol derivative of dimethylcyclohexene (XIV) is used as a photo-oxidizable compound.

Bisphenol derivative (XIV)

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In 2 g of a dioxane solution of the above polymer, 50 parts by weight of pentaerythritol triacrylate based on the polymer, 10 parts by weight of a porphyrazine compound shown in Table 1, and a dimethylcyclohexene derivative (XIV)
Was added on a glass plate to a thickness of about 2 μm using a spin coater, and a photosensitive solution prepared by adding 10 parts by weight of oxyvanadium acetylacetonate and 0.1 part by weight of oxyvanadium acetylacetonate was applied to a photosensitive plate. Exposure with a He-Ne laser (633 nm light) for different irradiation times and 1 mmHg
After performing the heat treatment at 60 ° C. for 3 minutes under the above vacuum,
Table 1 shows, as sensitivity, the amount of exposure which gave development with toluene and gave a cured spot diameter equivalent to the laser beam diameter. The porphyrazine compounds in the table are the same as the compounds (a) to (i) shown above.

Examples 10 to 12 In the compositions of Examples 1 to 9, the porphyrazine-based compound (a) shown in Example 1 was used as a dye instead of (XIV) as a photo-oxidizable compound. XV)
Table 2 shows the sensitivity characteristics when the olefin derivatives of (XVII) to (XVII) were used.

[0111]

[Table 1]

[0112]

[Table 2]

Formula (XV)

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Formula (XVI)

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Formula (XVII)

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[0116]

The photoinitiator composition of the present invention comprises a carbon arc, a xenon lamp, a metal halide lamp,
A fluorescent lamp, a tungsten lamp, or the like can be used, and a high sensitivity (0.1 mJ / cm ² to several mJ / c) to light having a wavelength of 600 nm to 720 nm can be used.
m ² ), a gas laser such as a He—Ne or Kr ⁺ laser or a semiconductor laser can be used.

Also, since reciprocity failure behavior is not exhibited even in high-speed scanning exposure by laser beam scanning, image forming materials by laser beam scanning, such as direct printing plates, photoresists for printed wiring boards, non-silver salt image forming materials, etc. Lip hologram, which is required to have high sensitivity to form subtle interference fringes, and hologram recording material for relief hologram recording in rainbow holograms, for which it was difficult to increase the area. It can be applied to a wide range of fields.

 ──────────────────────────────────────────────────続 き Continuation of front page (56) References JP-A-2-135351 (JP, A) JP-A-2-972 (JP, A) JP-A-61-278506 (JP, A) JP-A-60-1985 78442 (JP, A) JP-A-50-83103 (JP, A) JP-A-4-113361 (JP, A)

Claims (3)

(57) [Claims] 1. At least one kind of the following general formula (I)
A porphyrazine-based compound represented by the formula (A), at least one or more photo-oxidizable compounds (B), and at least one or more redox catalysts (C). A photoinitiator composition comprising: General formula (I) (In the formula (I), the 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, or an organic residue other than a hydrogen atom and a halogen atom, and 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, R
An annular structure in which ¹¹ and R ¹² are each 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
Independently represent a halogen atom, an oxygen atom, and an organic residue other than a halogen atom and an oxygen atom. Of these, the atoms in the organic residue directly bonded to M are an oxygen atom, a nitrogen atom, Limited to carbon or sulfur atoms. l and m each independently represent an integer of 0 or 1. ) 2. An olefin compound having at least one methyl group on a double bond carbon, wherein the photooxidizable compound (B) is capable of reacting with singlet oxygen to form a photoperoxide. The photoinitiator composition according to claim 1, wherein: 3. The photoinitiator composition according to claim 1, wherein the redox catalyst (C) is a metal salt or complex capable of existing in two or more valence states.