JPH055005A - Photopolymerization initiator and photopolymerizable composition containing the same - Google Patents

Abstract

PURPOSE:To obtain the subject composition, containing an unsaturated monomer, a binder and a photopolymerization initiator composed of a specific squarylium derivative and a free radical former, capable of performing scanning and memorizing at a high speed with visible laser and useful for dry film resists, etc. CONSTITUTION:The objective photopolymerizable composition is obtained by dissolving an addition polymerizable compound (e.g. pentaerythritol triacrylate) having at least one ethylenically unsaturated double bond, a binder (e.g. polymethacrylic acid polymer) and a photopolymerization initiator composed of a squarylium derivative expressed by the formula (R1 is lower alkyl; R2 is H, alkyl, aryl or aralkyl; X is halogen) and a free radical former [e.g. 2,4,6- tris(trichloromethyl)-s-triazine] in a solvent such as ethyl cellosolve. Furthermore, the aforementioned composition is applied onto a substrate and dried to form a film, which can be overcoated with an aqueous solution of PVA, etc., and irradiated with light at about 630nm wavelength to afford a cured film.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a photopolymerization initiator and a photopolymerizable composition containing the same. Since the photopolymerizable composition has high sensitivity to visible light, particularly He-Ne laser having an oscillation wavelength in the wavelength range of 600 to 700 nm, light emitting diode, semiconductor laser, etc., high speed scanning recording by visible laser is performed. And is useful as a material for PS plates for laser direct plate making, dry film resists, digital proofs, holograms and the like.

[0002]

2. Description of the Related Art Squalylium derivatives have hitherto been used as charge generating agents for electrophotographic photoreceptors (for example, JP-A-52-5564).
No. 3, USP4353971, JP-A-60-224.
674, 60-243653), a dye for wet development by an electrophoretic method (USP4175956), a dye for a light-collecting resin plate (for example, JP-A-63-235370), L
B (Langmuir-Brodget) Membrane Material (Nikkei New Material)
s, October 26, 1987) etc. However, it is not known that the squarylium derivative is used as a photopolymerization initiator.

[0003]

INDUSTRIAL APPLICABILITY The present invention is excellent for visible light, particularly He-Ne lasers, light emitting diodes, semiconductor lasers, etc., which have a versatile low power and have an oscillation wavelength in the wavelength range of 600 to 700 nm. It is an object to provide a photopolymerization initiator having photosensitivity and a photopolymerizable composition containing the photopolymerization initiator.

[0004]

The present invention provides a compound of formula (I)

[0005]

[Chemical 3]

(In the formula, R ₁ represents lower alkyl,
₂ represents hydrogen, alkyl, aryl or aralkyl, and X represents hydrogen or halogen. ), A photopolymerization initiator comprising a squarylium derivative and a radical generator, the photopolymerization initiator, and an addition-polymerizable compound having at least one ethylenically unsaturated double bond (hereinafter referred to as an ethylenic compound) And a photopolymerizable composition containing a binder.

Examples of the lower alkyl of R ₁ in the formula (I) include C 1-5, for example, methyl, ethyl, propyl, isopropyl, butyl, pentyl and the like.
_In the definition of ₂ , alkyl has 1 to 20 carbon atoms, for example, methyl, ethyl, propyl, isopropyl, butyl, pentyl, hexyl, octyl, decyl, dodecyl, pentadecyl, octadecyl, eicosyl, and the like. Examples of the aralkyl include those having 6 to 10 carbon atoms such as phenyl and naphthyl, and examples of the aralkyl include those having 7 to 10 carbon atoms such as benzyl, phenylethyl and phenylpropyl. In the definition of X, examples of halogen include chlorine, bromine, fluorine and the like.

Examples of the squarylium derivative represented by the formula (I) include the compounds shown in Table 1.
The compound is a known compound (USP 417595).
6).

[0009]

[Table 1]

As the radical generator, s-triazine compounds substituted with at least one trihalomethyl group [2,4,6-tris (trichloromethyl) -s-triazine, 2- (4-methoxyphenyl)- 4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxy-1-naphthalenyl) -4,6-bis (trichloromethyl) -s-triazine, etc.], organic peroxides [3,
3 ', 4,4'-tetrakis (t-butyldioxycarbonyl) benzophenone (hereinafter referred to as BTTB)
Etc.], N-phenylglycines (N-phenylglycine, p-chloro-N-phenylglycine, m-methyl-
N-phenylglycine, etc.), aromatic sulfonyl halide compounds (benzenesulfonyl chloride, p-toluenesulfonyl chloride, etc.), imidazole dimers [2,2′-bis (o-chlorophenyl) -4,4 ′,
5,5'-tetraphenylbiimidazole and the like], iron arene complexes [eta ⁶ - benzene) (eta ⁵ - PF ₆ cyclopentadienyl) iron (II) ^- salt, etc.], titanocene (fluoroaryl titanocene etc. ), Diaryl iodonium salts, triaryl sulfonium salts, branched polyethyleneimines and the like. The amount of the radical generator used in the photopolymerization initiator of the present invention is 0.1 to 1 part by weight of the squarylium derivative (hereinafter, parts by weight will be referred to as parts).
It is 00 parts, preferably 1 to 50 parts. The photopolymerization initiator is used as a photopolymerization initiator of the photopolymerizable composition of the present invention described below.

Next, the photopolymerizable composition of the present invention will be described. The photopolymerizable composition is prepared by mixing an ethylenic compound, a binder, the above-mentioned photopolymerization initiator, and, if necessary, a usual additive (for example, a thermal polymerization inhibitor, a plasticizer, etc.). The ethylenic compound in the photopolymerizable composition means that when the photopolymerizable composition is exposed to actinic rays, it is cured by addition polymerization due to the action of the photodecomposition product of the photopolymerization initiator, and is substantially insolubilized. Is a monomer having an ethylenically unsaturated double bond or a polymer having an ethylenically unsaturated double bond in the main chain or side chain.

Examples of the monomer having an ethylenically unsaturated double bond include unsaturated carboxylic acids, esters of unsaturated carboxylic acids and aliphatic polyhydroxy compounds, unsaturated carboxylic acids and aromatic polyhydroxy compounds. And an ester obtained by an esterification reaction of an unsaturated carboxylic acid, a polycarboxylic acid and a polyhydroxy compound.

Examples of unsaturated carboxylic acids include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid and the like. Examples of the ester of an unsaturated carboxylic acid and an aliphatic polyhydroxy compound include ethylene glycol diacrylate, triethylene glycol diacrylate, trimethylol propane triacrylate, trimethylol ethane triacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate. Acrylic esters such as acrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, glycerol acrylate; triethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate , Pentaerythritol dimethacrylate , Methacrylic acid esters such as pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol dimethacrylate, dipentaerythritol trimethacrylate, dipentaerythritol tetramethacrylate; itaconic acid esters of aliphatic polyhydroxy compounds, crotonic acid Examples thereof include esters and maleic acid esters.

Examples of the ester of unsaturated carboxylic acid and aromatic polyhydroxy compound include hydroquinone diacrylate, hydroquinone dimethacrylate, resorcin diacrylate, resorcin dimethacrylate, and pyrogallol triacrylate. Examples of the ester obtained by the esterification reaction of an unsaturated carboxylic acid, a polyvalent carboxylic acid and a polyhydroxy compound include, for example, a condensate of acrylic acid, phthalic acid and ethylene glycol; a condensation of acrylic acid, maleic acid and diethylene glycol. Examples thereof include condensation products of methacrylic acid, terephthalic acid, and pentaerythritol; condensation products of acrylic acid, adipic acid, butanediol, and glycerin.

Other examples of the compound having an ethylenically unsaturated double bond used in the present invention include acrylamides such as ethylenebisacrylamide, allyl esters such as diallyl phthalate and prepolymers thereof, and vinyl groups such as divinylphthalate. Examples include contained compounds.
As the polymer having an ethylenically unsaturated double bond in the main chain, for example, polyester obtained by polycondensation reaction of unsaturated divalent carboxylic acid and dihydroxy compound, polycondensation reaction of unsaturated divalent carboxylic acid and diamine The polyamide and the like obtained by

Examples of the polymer having an ethylenically unsaturated double bond in the side chain include divalent carboxylic acids having an unsaturated bond in the side chain, such as itaconic acid, propylidene succinic acid and ethylidene malonic acid. Examples thereof include condensation polymers with dihydroxy or diamine compounds. Further, a polymer having a functional group such as a hydroxy group or a methyl halide group in its side chain, for example, polyvinyl alcohol, poly (2-hydroxyethyl methacrylate), an epoxy resin, a phenoxy resin, polyepichlorohydrin, etc., and acrylic acid, methacrylic acid, Polymers obtained by macromolecular reaction with unsaturated carboxylic acids such as crotonic acid can also be used.

As the binder, for example, polymethacrylic acid ester or a partial hydrolyzate thereof, polyacrylic acid ester or a partial hydrolyzate thereof, polystyrene, polyvinyl acetate or a partial hydrolyzate thereof, polyvinyl butyral, polychloroprene, poly Vinyl chloride,
Chlorinated polyethylene, chlorinated polypropylene, polyvinylpyrrolidone, polyethylene oxide, polymethacrylic acid or a methacrylic acid copolymer having a carboxyl group on the side chain, polyacrylic acid or an acrylic acid copolymer having a carboxyl group on the side chain, polyurethane, Polyamide, polycarbonate, acetyl cellulose, polyvinyl carbazole, other acrylic acid ester, methacrylic acid ester, (anhydrous) maleic acid, acrylonitrile, styrene, vinyl acetate, vinyl chloride, vinylidene chloride, butadiene, isoprene, chloroprene and other copolymers can give.

The amount of binder used is ethylenic compound 1
10 to 1000 parts with respect to 00 parts, preferably 60 to 2 parts
It is 00 copies. The amount of the squarylium derivative and the radical generator used in the photopolymerization initiator is the ethylenic compound 10
0.1 to 30 parts, preferably 0.5 to 0 parts, respectively
5 parts and 1 to 50 parts, preferably 2 to 30 parts.

Examples and comparative examples will be shown below.

[0020]

【Example】

Examples 1-7 and Comparative Examples 1-2 Pentaerythritol triacrylate 100 parts, polymethacrylic acid ester polymer (average molecular weight 150,000) 1
A photosensitive resin solution was obtained by dissolving 00 parts and a predetermined amount of the squarylium derivative and / or the radical generator shown in Table 2 in 900 ml of ethyl cellosolve. This photosensitive resin solution was applied to a grained and anodized aluminum plate using a rotary applicator so that the dry film thickness was 2 μm, and dried at 80 ° C. for 2 minutes. An aqueous solution of polyvinyl alcohol (Kuraray Poval 706) was applied onto this so that the dry film thickness would be 1.0 μm to form an overcoat layer. A step tablet with an optical density difference of 0.15 was placed on the obtained photosensitive sample, and a heat ray absorption filter HA-30 (manufactured by HOYA), a colored glass filter R-61, and an interference filter KL-63 from a 3 kw ultra-high pressure mercury lamp (all were used). Light (66 μJ / cm ² S) having a wavelength of about 630 nm obtained through Toshiba Glass Co., Ltd. was irradiated for 2 minutes. Then, after performing the phenomenon with PS plate developer DN3C (manufactured by Fuji Photo Film Co., Ltd.), ink is applied with PS plate developing ink PI-2 (manufactured by Fuji Photo Film Co., Ltd.), and it is necessary for curing from the number of curing stages where the ink adheres The amount of energy was calculated as the sensitivity. The results are shown in Table 2.

[0021]

[Table 2]

As is clear from the table, the photopolymerization initiator comprising the squarylium derivative and the radical generator is 630
It showed high sensitivity to light of wavelength around nm, but did not show sensitivity to light of the same wavelength only with squarylium derivative or radical generator.

Example 8 100 parts of pentaerythritol triacrylate, 100 parts of polyvinylpyrrolidone, 1.4 parts of compound 2 and s
14 parts of -Tri (1) was dissolved in 900 ml of ethyl cellosolve to obtain a photosensitive resin solution. This photosensitive resin solution was applied to a grained and anodized aluminum plate using a rotary applicator so that the dry film thickness was 2 μm, and dried at 80 ° C. for 2 minutes.

The resulting photosensitive sample had an optical density difference of 0.15.
Step tablet is piled up and heat ray absorption filter HA-30 (made by HOYA), colored glass filter R-61 and interference filter KL-63 from a 3kw ultra-high pressure mercury lamp.
630nm obtained through (all manufactured by Toshiba Glass Co., Ltd.)
Irradiation with light having a wavelength of before and after (66 μJ / cm ² S) was performed for 2 minutes under vacuum. After development with alcohol, dyeing was carried out from an aqueous solution of methyl blue, and the amount of energy required for curing was determined from the number of dyed curing stages. As a result, a very high sensitivity of 0.06 mJ / cm ² was exhibited.

Example 9 In Example 1, 0.6 part of Compound 1 and s-Tri were used.
(1) 1.6 parts of compound 1 and BTT instead of 3.7 parts
When the same procedure as in Example 1 was carried out except that 8.7 parts of B was used, the sensitivity was 0.07 mJ / cm ² .

Example 10 100 parts of pentaerythritol triacrylate, 100 parts of polymethacrylic acid ester polymer, compound 1 1.
9 and s-Tri (1) 7.4 parts with ethyl cellosolve 9
It was dissolved in 00 ml to obtain a photosensitive resin solution. This photosensitive resin solution was applied to a grained and anodized aluminum plate using a spin coater to a dry film thickness of 2.0 μm and dried at 80 ° C. for 2 minutes. Further, an aqueous solution of polyvinyl alcohol (Kuraray Poval 706) was applied on this so as to have a dry film thickness of 1.0 μm to form an overcoat layer. The obtained photosensitive sample was irradiated with a laser beam having a wavelength of 633 nm and a beam diameter of 0.8 mm using a He-Ne laser, and the irradiation energy required to obtain a cured diameter the same as the beam diameter was taken as the sensitivity. As a result, 0.5m
A sensitivity of J / cm ² was obtained.

Examples 11-14 In Example 1, 0.6 part of Compound 1 and s-Tri
(1) The sensitivity shown in Table 3 was obtained in the same manner as in Example 1 except that the squarylium derivative and the radical generator shown in Table 3 were used instead of 3.7 parts.

[0028]

[Table 3]

Example 15 In Example 7, 1.8 parts of compound 2 and s-Tri
(1) 1.4 parts of compound 2 and BTT instead of 8.8 parts
Same as Example 7 except that B8 part is used, and sensitivity is 0.29.
mJ / cm ² was obtained.

Example 16 A sensitivity of 0.78 mJ / cm ² was obtained in the same manner as in Example 15 except that 1.4 parts of compound 5 was used instead of 1.4 parts of compound 2 in Example 15.

Example 17 100 parts of styrene-isobutyl maleate copolymer, polyfunctional monomer M315 [manufactured by Toagosei Chemical Industry Co., Ltd.] 1
00 parts, Compound 1 0.76 parts and s-Tri (1) 7
A part was dissolved in 900 ml of methyl cellosolve to obtain a photosensitive resin solution. This photosensitive resin solution was applied onto a glass substrate so that the dry film thickness was 6 μm, and dried in an oven at 60 ° C. to obtain a photoreceptor.

Holographic recording was performed on the obtained photosensitive sample by exposure to 9 mJ / cm ² using a ^two- beam interference system using a He-Ne laser as a light source, and then 10 mJ / visible with visible light.
A full-area exposure of cm ² was performed. After completion of the exposure, the resultant was dipped in isopropanol for 90 seconds and then dipped in n-heptane for about 10 seconds to perform a development treatment, and dried to obtain a volume hologram. The maximum diffraction efficiency of the obtained volume hologram was about 85%.

Example 18 In Example 17, B was used instead of 7 parts of s-Tri (1).
A photoreceptor was obtained in the same manner as in Example 17, except that 7 parts of TTB was used. Hem of 5 mJ / cm ² was applied to the obtained photosensitive sample.
Holographic recording was performed by Denishk type exposure using a Ne laser as a light source. Thereafter, the same procedure as in Example 17 was performed to obtain a bright image of the subject.

Example 19 Polyvinylcarbazole 10 was used in place of 100 parts of styrene-isobutyl maleate copolymer in Example 17.
A photoreceptor was obtained in the same manner as in Example 17 except that 0 part was used. Holographic recording was performed on the obtained photosensitive sample by a Denishk type exposure using a He-Ne laser of 5 mJ / cm ² as a light source, and then the entire surface was exposed by visible light. Then, add 90% to a solution of toluene / xylene (1/1 v / v).
After soaking for 2 seconds, it was soaked in n-heptane for about 10 seconds to perform development processing, and a bright image of the subject was obtained.

[0035]

The photopolymerization initiator of the present invention has excellent photosensitivity.

Continuation of front page (51) Int.Cl. ⁵ Identification code Office reference number FI technical display area H01L 21/027

Claims (1)

What is claimed is: (Claim 1) Formula (I) (In the formula, R ₁ represents lower alkyl, R ₂ represents hydrogen, alkyl, aryl or aralkyl, and X represents hydrogen or halogen.) A photopolymerization initiator comprising a squarylium derivative and a radical generator. .. 2. An addition-polymerizable compound having at least one ethylenically unsaturated double bond, a binder and a compound represented by formula (I): (In the formula, R ₁ represents lower alkyl, R ₂ represents hydrogen, alkyl, aryl or aralkyl, and X represents hydrogen or halogen.) A photopolymerization initiator comprising a squarylium derivative and a radical generator. A photopolymerizable composition containing: