JPH05210240A - Photopolymerizable composition - Google Patents

Abstract

PURPOSE:To provide a high sensitivity to visible ray and more particularly long-wavelength ray by incorporating a specific sensitizer and activators which can generate active radicals at the time of photoirradiation in the co-presence with the sensitizer to the photopolymn. initiator. CONSTITUTION:The photopolymn. initiator of the photopolymerizable compsn. contg. an addition polymerizable compd. having at least one piece of ethylenic unsatd. double bonds and a photopolymn. initiator contains the sensitizer expressed by formula I or II and at least one kind of the activators which can generate the active radicals at the time of the photoirradiation in the co- presence with the sensitizer. In the formula I, R<1> to R<3> denote a hydrogen atom, alkyl group, etc.; R<1> and R<2> may form a ring structure by bonding to each other; R<4>, R<5> respectively denote a hydrogen atom, halogen atom, etc.; R<4>, R<5> are not simultaneously the hydrogen atom; n denotes 0 or 1. In the formula II, R<6> to R<8> denote a hydrogen atom, alkyl group, etc.; R<6> and R<7> may form a ring structure by bonding to each other; R<9> to R<11> respectively denote an alkoxy group; m denotes 0 or 1.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a photopolymerizable composition. In particular, the present invention relates to a photopolymerizable composition having extremely high sensitivity to light rays in the visible region.

[0002]

2. Description of the Related Art Conventionally, many image forming methods utilizing a photopolymerization system are known. For example, a photopolymerizable composition comprising a compound containing an addition-polymerizable ethylenic double bond, a photopolymerization initiator, and an organic polymer binder optionally used is prepared, and the photopolymerizable composition is supported. A photosensitive material having a layer of a photopolymerizable composition applied on the body is prepared, and a desired image is imagewise exposed to polymerize and cure the exposed portion, and the unexposed portion is dissolved and removed to form a cured relief image. And a layer of a photopolymerizable composition is provided between two supports in which at least one of the above-mentioned light-sensitive materials is transparent, and the transparent support side is imagewise exposed to cause a change in adhesive strength due to light. After that, there is a method of forming an image by peeling the support, and an image forming method utilizing the change of toner adhesion of the photopolymerizable composition layer due to light.

Conventionally, benzoyl, benzoin alkyl ether, benzyl ketal, benzophenone, anthraquinone, benzyl, Michler's ketone, etc. have been used as the photopolymerization initiator of the photopolymerizable composition applied to these methods. However, these photopolymerization initiators are remarkably low in light in the visible light region of 400 nm or more as compared with the photopolymerization initiating ability for the light in the ultraviolet region of 400 nm or less, and therefore, the application of the photopolymerizable composition containing them is significantly reduced. The range has been limited.

In recent years, with the development of image forming technology, there has been a strong demand for photopolymers having a high sensitivity to light rays in the visible region. For example, it is a photosensitive material suitable for non-contact type projection exposure plate making, laser plate making by visible light laser, and the like. Among these techniques, the plate making method using an 488 nm oscillation beam of an argon ion laser is considered to be one of the most promising techniques in the future.

[0005]

Several proposals have hitherto been made for a photopolymerizable photosensitive material containing a photopolymerization initiation system capable of being sensitive to light rays in the visible light region. For example,
System of hexaarylbiimidazole and radical generator and dye (JP-B-45-37737), system of hexaarylbiimidazole and (p-dialkylaminobenzylidene) ketone (JP-A-47-2528, JP-A-47-2528) 54-155292), a system of a cyclic cis-α-dicarbonyl compound and a dye (JP-A-48-84183), a system of substituted triazine and a merocyanine dye (JP-A-54-151024), ketocoumarin and activity. System of agents (JP-A-52-112681, JP-A-58-58)
15503, JP-A-60-88005),
Systems of substituted triazines and sensitizers (JP-A-58-29803)
No. 40302), biimidazole, styrene derivative, thiol system (JP-A-59-56403), organic peroxide and dye system (JP-A-59-140).
No. 203, No. 189340) and the like.

[0006]

However, although these prior arts are certainly effective for visible light, they have the drawback that they are not very sensitive and still inadequate from a practical point of view. It was

[0007]

Means for Solving the Problems The inventors of the present invention have made earnest studies to overcome such difficulties and obtain an excellent photopolymerizable composition. As a result, at least an addition-polymerizable ethylenic double bond is at least one. In a photopolymerizable composition comprising a compound having an individual compound and a photopolymerization initiation system, a sensitizer having a tetrahydroquinoline skeleton and a 1-indanone skeleton in which the photopolymerization initiation system has a specific skeleton and coexistence of the sensitizer Therefore, they have found that the sensitivity and the practicality are enhanced by containing at least one activator capable of generating an active radical upon irradiation with light, and thus arrived at the present invention.

That is, it is an object of the present invention to provide a photopolymerizable composition which is more sensitive to visible light, especially to long wavelength light such as 488 nm. Another object of the present invention is to provide a photopolymerizable composition which enables a higher speed plate making work by using a laser having a lower output, for example, an air-cooled argon laser in the case of laser plate making with an argon ion laser. Especially.

Another object of the present invention is to provide a photopolymerizable composition which enables a plate making operation which is extremely advantageous in terms of cost and time. Thus, at least an object of the present invention is to provide a photopolymerizable composition containing an addition-polymerizable compound having at least one ethylenically unsaturated double bond and a photopolymerization initiation system, wherein the photopolymerization initiation system is (a) ) A sensitizer represented by the following general formula [I] or [II]

[0010]

[Chemical 3]

(Wherein R ¹ represents a hydrogen atom or an alkyl group, R ² and R ³ each represent a hydrogen atom, an alkyl group, an alkoxy group or an alkylthio group, or R 2
¹ and R ² may be bonded to each other to form a ring structure, and R ⁴ and R ⁵ each represent a hydrogen atom, a halogen atom or an alkyl group, but R ⁴ and R ⁵ simultaneously represent a hydrogen atom. Don't l represents 0 or 1. )

[0012]

[Chemical 4]

(In the formula, R ⁶ represents a hydrogen atom or an alkyl group, R ⁷ and R ⁸ represent a hydrogen atom, an alkyl group, an alkoxy group or an alkylthio group, or R ⁶ and R ⁷ are bonded to each other. May form a ring structure,
R ^{9 to} R ¹¹ each represent an alkoxy group, and m represents 0 or 1. (B) It is easily achieved by a photopolymerizable composition characterized in that it contains at least one activator capable of generating an active radical upon irradiation with light in the coexistence with the sensitizer.

The present invention will be described in detail below. The addition-polymerizable compound having at least one ethylenically unsaturated double bond (hereinafter abbreviated as “ethylenic compound”) contained as the first essential component in the photopolymerizable composition of the present invention means photopolymerization. When the photosensitive composition is irradiated with actinic rays, it is a compound having an ethylenically unsaturated double bond that undergoes addition polymerization by the action of the photopolymerization initiation system that is the second essential component and is cured, for example, It is a monomer having the above double bond, or a polymer having an ethylenically unsaturated double bond in the side chain or main chain. Incidentally, the meaning of the monomer in the present invention is a concept facing a so-called polymer substance, therefore, in addition to the monomer in a narrow sense, a dimer,
It also includes trimers and oligomers.

Examples of the monomer having an ethylenically unsaturated bond include unsaturated carboxylic acids, esters of aliphatic polyhydroxy compounds with unsaturated carboxylic acids; esters of aromatic polyhydroxy compounds with unsaturated carboxylic acids; Examples thereof include esters obtained by an esterification reaction of a saturated carboxylic acid with a polyvalent carboxylic acid and the above-mentioned aliphatic polyhydroxy compound, polyvalent hydroxy compound such as aromatic polyhydroxy compound, and the like.

The ester of the aliphatic polyhydroxy compound and the unsaturated carboxylic acid is not limited, but specific examples thereof include ethylene glycol diacrylate, triethylene glycol diacrylate, trimethylolpropane triacrylate, and trimethylolethane triacrylate. , Pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate,
Acrylic esters such as glycerol acrylyl, methacrylic acid esters obtained by replacing acrylates of these exemplified compounds with methacrylates, itaconic acid esters similarly replaced with itaconate, crotonic acid esters replaced with crotonate or maleic acid esters replaced with maleate, etc. is there.

Examples of the ester of an aromatic polyhydroxy compound and an unsaturated carboxylic acid include hydroquinone diacrylate, hydroquinone dimethacrylate, resorcin diacrylate, resorcin dimethacrylate and pyrogallol triacrylate. The ester obtained by the esterification reaction of an unsaturated carboxylic acid with a polyvalent carboxylic acid and a polyvalent hydroxy compound is not necessarily a single substance, but representative specific examples include acrylic acid, phthalic acid and ethylene glycol. Examples thereof include condensates, condensates of acrylic acid, maleic acid and diethylene glycol, condensates of methacrylic acid, terephthalic acid and pentaerythritol, condensates of acrylic acid, adibic acid, butanediol and glycerin.

Other examples of the ethylenic compound used in the present invention include acrylamides such as ethylenebisacrylamide; allyl esters such as diallyl phthalate;
Vinyl group-containing compounds such as divinyl phthalate are useful. The polymer having an ethylenically unsaturated bond in the main chain described above is, for example, a polyester obtained by a polycondensation reaction of an unsaturated dicarboxylic acid and a dihydroxy compound,
There are polyamides and the like obtained by polycondensation reaction of unsaturated divalent carboxylic acid and diamine.

The polymer having an ethylenically unsaturated bond in the side chain is a polycondensation product of a divalent carboxylic acid having an unsaturated bond in the side chain such as itaconic acid, propylidene succinic acid, ethylidene malonic acid and the like with a dihydroxy or diamine compound. There is coalescence. Further, a polymer having a functional group having a reactive activity such as a hydroxy group or a methyl halide group in its side chain, for example, polyvinyl alcohol, poly (2-hydroxyethyl methacrylate), polyepichlorohydrin, etc. and acrylic acid,
Polymers obtained by polymer reaction with unsaturated carboxylic acids such as methacrylic acid and crotonic acid can also be suitably used.

Of the above-mentioned ethylenic compounds, acrylic acid ester or methacrylic acid ester monomers can be particularly preferably used. Next, the photopolymerization initiation system which is the second essential component of the photopolymerizable composition of the present invention will be described. The photopolymerization initiation system of the present invention is composed of a combination of two kinds of components, the first component of which is represented by (a) in the present invention and represented by the structural formula [I] or [II] above. Is a compound represented by.

It has been found that all of these sensitizers have a tetrahydroquinoline structure in the molecule, which significantly increases the sensitivity to visible light. This effect is particularly remarkable with respect to the compounds represented by the above-mentioned two general formulas, and by replacing the N, N-dialkylbenzene structure in the molecule with a derivative having a tetrahydroquinoline structure, as will be described later in Examples and Comparative Examples, 4
A significant increase in sensitivity was observed for the 88 nm light.
The usefulness of this effect indicates that it can be applied to an air-cooled argon laser having a low output in the image forming method by the argon ion laser scanning.

In the formulas [I] and [II] of the sensitizer,
When R ^{1 to} R ¹¹ each represent an alkyl group, and when R ² , R ³ , R ⁷ and R ⁸ each represent an alkoxy group or an alkylthio group, it preferably has 1 to 10 carbon atoms. It is particularly preferably 1 to 5 and may be linear or may have a side chain. R ⁴ , R ⁵
When each represents a halogen atom, it is generally preferred that it is a bromine atom or a chlorine atom.

The following is represented by the general formula [I] or [II].
Of tetrahydroquinoline sensitizers
For example, the tetrahydroquinoline type used in the present invention
The sensitizer is not limited to these specific examples. Na
Unless otherwise stated in the following examples, l = m = 0, R
¹~ R⁸Are each a hydrogen atom. Also, R
¹And R²Or R ⁶And R⁷Forms the following ring structure
If

[0024]

[Chemical 5]

R ¹ -R ² or R ⁶ -R ⁷ ; represented by julolidine ring. Compound Example [I-1] R ¹ -R ² ; julolidine ring, R ⁴ ; bromine atom, R ⁵ ; methyl group [I-2] R ¹ -R ² ; julolidine ring, R ⁴ ; methyl group, R ⁵ ; Bromine atom [I-3] R ¹ -R ² ; julolidine ring, R ³ ; ethoxy group, R ⁴ ; bromine atom, R ⁵ ; methyl group [I-4] R ¹ -R ² ; julolidine ring, R ³ ; Ethoxy group, R ⁴ ; methyl group, R ⁵ ; bromine atom [I-5] R ¹ -R ² ; julolidine ring, R ³ ; methyl group, R ⁴ ; bromine atom, R ⁵ ; methyl group [I-6] R ¹ -R ² ; julolidine ring, R ³ ; methyl group, R ⁴ ; methyl group, R ⁵ ; bromine atom [I-7] R ¹ ; methyl group, R ⁴ ; bromine atom, R ⁵ ;
Methyl group [I-8] R ¹ ; Methyl group, R ⁴ ; Methyl group, R ⁵ ;
Bromine atom [I-9] l = 1, R ¹ -R ² ; julolidine ring, R
⁴ ; bromine atom, R ⁵ ; methyl group [I-10] l = 1, R ¹ -R ² ; julolidine ring,
R ⁴ ; methyl group, R ⁵ ; bromine atom [I-11] l = 1, R ⁴ ; bromine atom, R ⁵ ; methyl group [I-12] l = 1, R ⁴ ; methyl group, R ⁵ ; bromine Atom [I-13]

[0026]

[Chemical 6]

[I-14] R ¹ -R ² ; julolidine ring, R ⁴ ; chlorine atom [I-15] R ¹ -R ² ; julolidine ring, R ⁴ ; bromine atom [II-1] R ⁶ -R ⁷ ; julolidine ring, R ^{9 to} R
^11; methoxy ^{[II-2] R 6 -R} 7; julolidine ring, R ^8; ethoxy, R ⁹ to R ^11; methoxy [II-3] R ^6; methyl, R ⁹ to R ^11; methoxy Group [II-4] R ⁶ ; ethyl group, R ^{9 to} R ¹¹ ; methoxy group [II-5] m = 0, R ⁶ -R ⁷ ; julolidine ring,
R ^{9 to} R ¹¹ ; Methoxy group Particularly preferred are [I-1], [I-2],
[I-3], [I-4], [II-1], [II-2]
The compound shown by each formula of is mentioned.

The sensitizers of the present invention exemplified above are not limited, but for example, corresponding indanone derivatives and tetrahydroquinoline-derived aldehydes under acid or base catalysis as exemplified in Synthesis Examples 1 and 2 later. It can be synthesized by dehydration condensation. The sensitizer used in the photopolymerizable composition of the present invention can be preferably used alone or in combination of two or more kinds.

The second component constituting the photoinitiating system of the present invention is an activator capable of generating active radicals when irradiated with light in the coexistence with the above-mentioned sensitizer represented by (b) in the present invention. Is. As the activator, any activator can be used as long as it has a property of generating an active radical by causing some action with the photoexcited sensitizer. Preferred activators include, for example, hexaarylbiimidazole, halogenated hydrocarbon derivatives, organic thiol compounds, diaryliodonium salts and the like. In particular, the combined use of hexaarylbiimidazole and an organic thiol compound significantly increases the sensitivity.

Specific examples of hexaarylbiimidazole include 2,2'-bis (o-chlorophenyl)-
4,4 ', 5,5'-tetraphenylbiimidazole,
2,2'-bis (o-chlorophenyl) -4,4 ',
5,5′-tetra (p-carboethoxyphenyl) biimidazole, 2,2′-bis (o-chlorophenyl)-
4,4 ', 5,5'-Tetra (p-bromophenyl) biimidazole, 2,2'-bis (o-chlorophenyl)
-4,4 ', 5,5'-tetra (o, p-dichlorophenyl) biimidazole, 2,2'-bis (o-bromophenyl) -4,4', 5,5'-tetraphenylbiimidazole, 2,2'-bis (o, p-dichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (o-chlorophenyl) -4,
4 ', 5,5'-tetra (m-methoxyphenyl) biimidazole, 2,2'-bis (o, o'-dichlorophenyl) -4,4', 5,5'-tetraphenylbiimidazole, 2, 2'-bis (o-nitrophenyl) -4,
4 ', 5,5'-tetraphenylbiimidazole, 2,
2'-bis (o-methylphenyl) -4,4 ', 5
5'-tetraphenyl biimidazole etc. are mentioned.

As the halogenated hydrocarbon derivative,
For example, 2,4,6-tris (trichloromethyl) -S
-Triazine, 2,4,6-tris (tribromomethyl) -S-triazine, 2-methyl-4,6-di (trichloromethyl) -S-triazine, 2- (p-methoxyphenyl) -4,6 -Di (trichloromethyl) -S-triazine, 2,2,2-trichloromethylacetophenone, tribromomethylphenyl sulfone, 2-trichloromethyl-5- (p-methoxystyryl) -1,3,4
-Oxadiazole etc. are mentioned.

Examples of the organic thiol compound include 2
-Mercaptobenzthiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2
-Mercapto-4 (3H) -quinazolinone, β-mercaptonaphthalene and the like can be mentioned. Examples of the diaryliodonium salt include diphenyliodonium hexafluorophosphate, diphenyliodonium tosylate, diphenyliodonium fluoroborate, diphenyliodonium hexafluoroarsenate, diphenyliodonium chloride, ditolyliodonium hexafluorophosphate, phenyl (p-anisyl) iodonium hexafluoro. Examples thereof include phosphate and bis (m-nitrophenyl) iodonium hexafluorophosphate.

Other than the above, the activator in the present invention is known, for example, ketoxime esters such as 3-benzoyloxyiminobutan-2-one, 3,3 ′,
4,4'-Tetra (t-butylperoxycarbonyl)
Organic peroxides such as benzophenone, N-phenylglycine, dimedone and the like can also be used. The activator used in the photopolymerizable composition of the present invention can be preferably used alone or in combination of two or more kinds.

The suitable amount of the sensitizer and activator constituting the photopolymerization initiation system used in the photopolymerizable composition of the present invention described above is not particularly limited, but the ethylenic compound 1 is used.
The sensitizer is preferably 0.05 to 20 parts by weight with respect to 00 parts by weight.
Parts by weight, more preferably 0.2 to 10 parts by weight, activator preferably 0.5 to 100 parts by weight, more preferably 1 to
It is suitable to use 50 parts by weight.

In the photopolymerizable composition of the present invention, in addition to the above-mentioned constituents, it is preferable to further add an organic polymer substance as a binder in order to modify the composition and improve the physical properties after photocuring. .. The binder may be appropriately selected depending on the improvement purpose such as compatibility, film forming property, developability, and adhesiveness. Specifically, for example, to improve the water-based developability, acrylic acid copolymer, methacrylic acid copolymer, itaconic acid copolymer, partially esterified maleic acid copolymer, acidic cellulose modified product having a carboxyl group in the side chain, Examples include polyethylene oxide and polyvinylpyrrolidone.

To improve the film strength and adhesiveness, a polyether of epichlorohydrin and bisphenol A; soluble nylon; alkyl polymethacrylate such as polymethylmethacrylate or alkyl polyacrylate; alkyl methacrylate and acrylonitrile, acrylic acid , Copolymers with methacrylic acid, vinyl chloride, vinylidene chloride, styrene, etc .; copolymers of acrylonitrile with vinyl chloride, vinylidene chloride; vinylidene chloride, chlorinated polyolefins, copolymers of vinyl chloride with vinyl acetate; poly Vinyl acetate; Acrylonitrile / styrene copolymer; Acrylonitol / butadiene / styrene copolymer; Polyvinyl alkyl ether; Polyvinyl alkyl ketone;
Polystyrene; polyamide; polyurethane; polyethylene terephthalate isophthalate; acetyl cellulose, polyvinyl butyral and the like.
These binders can be added and mixed in a weight ratio of preferably 500% or less, more preferably 200% or less, relative to the ethylenic compound.

The photopolymerizable composition of the present invention may further contain a thermal polymerization inhibitor, a colorant, a plasticizer, a surface protective agent, a smoothing agent, if necessary.
Coating aids and other additives can be added. Examples of the thermal polymerization inhibitor include hydroquinone, p-methoxyphenol, pyrogallol, catechol, 2,6-di-
There are t-butyl-p-cresol, β-naphthol, and the like. Examples of the colorant include phthalocyanine pigments, azo pigments, carbon black, pigments such as titanium oxide, ethyl violet, crystal violet, azo dyes, anthraquinone dyes. , There are cyanine dyes. When the binder is used, the thermal polymerization inhibitor and the colorant are added in an amount of 0.01% to 3% of the thermal polymerization inhibitor and 0.1% of the colorant with respect to the total weight of the ethylenic compound and the binder.
1% to 20% is preferable.

Examples of the plasticizer include dioctyl phthalate, didodecyl phthalate, triethylene glycol dicaprylate, dimethyl glycol phthalate, tricresyl phosphate, dioctyl adipate, dibutyl sebacate, triacetyl glycerin, and the like. When used, 10% or less can be added to the total weight of the ethylenic compound and the binder.

When using the photopolymerizable composition of the present invention,
The light-sensitive material can be prepared by forming the light-sensitive material without a solvent or by dissolving it in a suitable solvent to form a solution, which is applied on a support and dried. Examples of the solvent include methyl ethyl ketone, cyclohexanone, butyl acetate, amyl acetate, ethyl propionate, toluene, xylene, monochlorobenzene, carbon tetrachloride, trichloroethylene,
There are trichloroethane, dimethylformamide, methyl cellosolve, ethyl cellosolve, tetrahydrofuran, bentoxone and the like, and one kind or a combination of two or more kinds can be used.

The support applied when preparing a light-sensitive material using the photopolymerizable composition of the present invention may be any of those usually used. For example, sheets of metals such as aluminum, magnesium, copper, zinc, chromium, nickel and iron or alloys containing them as a main component; fine paper, art paper,
Papers such as release paper; inorganic sheets such as glass and ceramics; polyethylene terephthalate, polyethylene, polymethylmethacrylate, vinyl chloride, vinyl chloride-vinylidene chloride copolymer, polystyrene, 6-nylon, cellulose triacetate, cellulose acetate butyrate, etc. Polymer sheets, etc.

Further, the photopolymerizable composition of the present invention is further provided with a known technique for preventing adverse effects such as sensitivity deterioration and storage stability deterioration due to oxygen, for example, providing a peelable transparent cover sheet on the photosensitive layer. Wax-like substance with low oxygen permeability,
An undercoat layer made of a water-soluble polymer or the like can be provided.
The exposure light source that can be applied to the composition of the present invention is not particularly limited, but includes carbon arc, high pressure mercury lamp, xenon lamp, metal halide lamp, fluorescent lamp, tungsten lamp, helium cadmium laser, argon ion laser, etc. A general-purpose light source can be used more suitably.

[0042]

EXAMPLES The present invention will be described in more detail with reference to Synthesis Examples, Examples, and Comparative Examples, but the present invention is not limited to these Examples unless the gist thereof is exceeded.

Synthesis Example 1 (Preparation of sensitizer [I-1]) Julolidine-9-carbaldehyde, 4.1 g, 7-bromo, prepared from julolidine as a starting material and using dimethylformamide and phosphorus oxychloride according to a conventional method. -4-Methyl-1-indanone 4.3 g, potassium hydroxide 0.5 g
Was reacted in an ethanol solvent under a nitrogen atmosphere at 80 ° C. for 10 hours. The reaction product was a silica gel column (Wako Gel C-20) using a mixed solvent of ethyl acetate and hexane (1: 9).
0, separated and purified by Wako Pure Chemical Industries, Ltd. [I-
1] 1 g was obtained. [I-1] was identified by thin layer chromatography, nuclear magnetic resonance spectrum, and infrared absorption spectrum.

Synthesis Example 2 (Preparation of sensitizer [II-1]) 3,4,5-trimethoxyphenylpropionic acid 10 g
Was reacted in 100 g of polyphosphoric acid at 70 ° C. for 5 hours,
5 g of 6,7-trimethoxy-1-indanone was obtained.
4 g of 5,6,7-trimethoxy-1-indanone, 4 g of julolidine-9-carbaldehyde and 0.5 g of potassium hydroxide were reacted in an ethanol solvent in a nitrogen atmosphere at 80 ° C. for 2 hours. The reaction solution at 80 ° C. was suction filtered, then washed with water and washed with methanol to obtain 4 g of [II-1] crystals. [II-1] was identified by thin layer chromatography, nuclear magnetic resonance spectrum, and infrared absorption spectrum.

Examples 1 to 23 and Comparative Examples 1 to 14 Using a whirler, a photosensitive composition coating solution having the following composition was coated on a grained and anodized aluminum sheet to a dry film thickness of 2 μm. Then, a polyvinyl alcohol aqueous solution was applied on the surface so that the dry film thickness was 3 μm to prepare a photosensitive material sample. Next, a step tablet (manufactured by Kodak Co., Ltd.) in which the amount of light is attenuated by 1 / √2 each time it is increased by one step is brought into close contact with this photosensitive material sample, and 1 m to 1 kW xenon lamp (OSB manufactured by Ushio Inc.) -1001A / 2) The light of 480 to 490 nm obtained through a glass filter (Y-47 and KL-49 manufactured by Toshiba Glass Co., Ltd.) was irradiated for 10 seconds. The exposed sample was developed with an aqueous solution containing 2% by weight of butyl cellosolve and 1% by weight of sodium silicate, and the minimum amount of exposure required for image formation was calculated from the number of step steps of the obtained step-cured image, and the exposure was calculated. The sensitivity of the composition was used.
The results are shown in Table 2.

[0046]

[Photosensitive composition coating liquid] Methyl methacrylate / methacrylic acid copolymer 50 parts (weight average molecular weight 45,000, copolymerization ratio 85/15) Trimethylolpropane triacrylate 50 parts Victoria Pure Blue BOH 0 1 part Methylsecosolve 800 parts Tetrahydrofuran 50 parts Sensitizer (listed in Table 2) Activator (listed in Table 2)

[0047]

[Table 2]

[0048]

[Table 3]

[0049]

[Table 4]

In Table 2, the sensitizers [S-1] to [S-5] are respectively

[Chemical 7]

Represents In addition, in Table 2, the activator [B-
1] to [B-7] are respectively

[0052]

[Chemical formula 8] [B-1]

[B-2]

[Chemical 9]

[B-3] 2,4,6-Trichloromethyl-S-triazine [B-4] Diphenyliodonium hexafluorophosphate [B-5] 2-mercaptobenzthiazole [B-6] 2-mercaptobenzoxazole [B-7] Represents 2-mercaptobenzimidazole.

[0055]

The photopolymerizable composition of the present invention is
In particular, it is extremely sensitive to long-wavelength light. Therefore, the composition is useful in a wide range of application fields, for example, for producing a printing plate such as a flat plate, an intaglio, a relief plate, a printed wiring and
Photoresist for making C, dry film, image formation such as relief image and image duplication, photocurable ink,
Since it can be used for paints, adhesives, etc., it is extremely useful industrially.

[Procedure amendment]

[Submission date] April 15, 1992

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be amended] Claims

[Correction method] Change

[Correction content]

[Claims]

[Chemical 1](In the formula, R¹Represents a hydrogen atom or an alkyl group, R
²And R³Are a hydrogen atom, an alkyl group, and an alcohol
Represents an oxy group or an alkylthio group, or R¹And R²But
Each may be bonded to each other to form a ring structure,
R^FourAnd R^FiveAre hydrogen atom, halogen atom and
Represents an alkyl group, but R^FourAnd R ^FiveIs hydrogen at the same time
It does not become an atom.nRepresents 0 or 1. )

[Chemical 2] (In the formula, R ⁶ represents a hydrogen atom or an alkyl group,
⁷ and R ⁸ each represent a hydrogen atom, an alkyl group, an alkoxy group or an alkylthio group, or R ⁶ and R ⁷ may be bonded to each other to form a ring structure,
R ^{9 to} R ¹¹ each represent an alkoxy group, and m represents 0 or 1. (B) A photopolymerizable composition comprising at least one activator capable of generating an active radical upon irradiation with light in the presence of the sensitizer.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0007

[Correction method] Change

[Correction content]

The inventors of the present invention have made earnest studies to overcome such difficulties and obtain an excellent photopolymerizable composition, and as a result, a photopolymerization system containing at least an addition-polymerizable compound and a photopolymerization initiation system has been obtained.
In the polymerizable composition, the addition-polymerizable compound is ethylene.
A sensitizer having at least one lenically unsaturated double bond, and the photopolymerization initiation system having a tetrahydroquinoline skeleton having a specific skeleton and a 1-indanone skeleton, and in the coexistence of the sensitizer. The present inventors have found that the presence of at least one activator capable of generating active radicals upon irradiation with light results in high sensitivity and high practicality, and has reached the present invention.

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0009

[Correction method] Change

[Correction content]

Another object of the present invention is to provide a photopolymerizable composition which enables a plate making operation which is extremely advantageous in terms of cost and time. Therefore, the object of the present invention is to
At least a compound capable of addition polymerization and a photopolymerization initiation system
A photopolymerizable composition containing
Having at least one ethylenically unsaturated double bond
And the photopolymerization initiation system is (a) a sensitizer represented by the following general formula [I] or [II]

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0010

[Correction method] Change

[Correction content]

[0010]

[Chemical 3]

[Procedure Amendment 5]

[Document name to be amended] Statement

[Correction target item name] 0011

[Correction method] Change

[Correction content]

(Where R¹Is a hydrogen atom or an alkyl group
And R²And R³Are hydrogen atom and alk
Represents an alkyl group, an alkoxy group or an alkylthio group,
R¹And R²Are linked to each other to form a ring structure
You may stay, R^FourAnd R^FiveAre hydrogen atom and halo
Represents a gen atom or an alkyl group, but R^FourAnd R ^Five
Cannot be hydrogen atoms at the same time.nRepresents 0 or 1
You )

[Procedure correction 6]

[Document name to be amended] Statement

[Name of item to be corrected] 0023

[Correction method] Change

[Correction content]

Typical examples of the tetrahydroquinoline sensitizer represented by the general formula [I] or [II] are shown below, but the tetrahydroquinoline sensitizer used in the present invention is not limited to these specific examples. is not. Unless otherwise stated in the following examples, n = m = 0, R
Each of ^{1 to} R ⁸ represents a hydrogen atom. or,
When R ¹ and R ² or R ⁶ and R ⁷ form the following ring structure

[Procedure Amendment 7]

[Document name to be amended] Statement

[Name of item to be corrected] 0025

[Correction method] Change

[Correction content]

R ¹ -R ² or R ⁶ -R ⁷ ; represented by julolidine ring. Compound Example [I-1] R ¹ -R ² ; julolidine ring, R ⁴ ; bromine atom, R ⁵ ; methyl group [I-2] R ¹ -R ² ; julolidine ring, R ⁴ ; methyl group, R ⁵ ; Bromine atom [I-3] R ¹ -R ² ; julolidine ring, R ³ ; ethoxy group, R ⁴ ; bromine atom, R ⁵ ; methyl group [I-4] R ¹ -R ² ; julolidine ring, R ³ ; Ethoxy group, R ⁴ ; methyl group, R ⁵ ; bromine atom [I-5] R ¹ -R ² ; julolidine ring, R ³ ; methyl group, R ⁴ ; bromine atom, R ⁵ ; methyl group [I-6] R ¹ -R ² ; julolidine ring, R ³ ; methyl group, R ⁴ ; methyl group, R ⁵ ; bromine atom [I-7] R ¹ ; methyl group, R ⁴ ; bromine atom, R ⁵ ;
Methyl group [I-8] R ¹ ; Methyl group, R ⁴ ; Methyl group, R ⁵ ;
Bromine atom [I-9] n = 1, R ¹ -R ² ; julolidine ring, R
⁴ ; bromine atom, R ⁵ ; methyl group [I-10] n = 1, R ¹ -R ² ; julolidine ring, R
⁴ ; methyl group, R ⁵ ; bromine atom [I-11] n = 1 and R ⁴ ; bromine atom, R ⁵ ; methyl group [I-12] n = 1 and R ⁴ ; methyl group, R ⁵ ; bromine atom [I-13]

[Procedure Amendment 8]

[Document name to be amended] Statement

[Name of item to be corrected] 0027

[Correction method] Change

[Correction content]

[I-14] R ¹ -R ² ; julolidine ring, R ⁴ ; chlorine atom [I-15] R ¹ -R ² ; julolidine ring, R ⁴ ; bromine atom [II-1] R ⁶ -R ⁷ ; julolidine ring, R ^{9 to} R
^11; methoxy ^{[II-2] R 6 -R} 7; julolidine ring, R ^8; ethoxy, R ⁹ to R ^11; methoxy [II-3] R ^6; methyl, R ⁹ to R ^11; methoxy Group [II-4] R ⁶ ; ethyl group, R ^{9 to} R ¹¹ ; methoxy group [II-5] m = 1 , R ⁶ -R ⁷ ; julolidine ring,
R ^{9 to} R ¹¹ ; Methoxy group Particularly preferred are [I-1], [I-2],
[I-3], [I-4], [II-1], [II-2]
The compound shown by each formula of is mentioned.

[Procedure Amendment 9]

[Document name to be amended] Statement

[Correction target item name] 0049

[Correction method] Change

[Correction content]

[0049]

[Table 4]

[Procedure Amendment 10]

[Document name to be amended] Statement

[Correction target item name] 0050

[Correction method] Change

[Correction content]

In Table 2, the sensitizers [S-1] to [S-5] are respectively

[Chemical 7]

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI Technical display location G03F 7/029 7/031 H01L 21/027 H05K 3/06 H 6921-4E

Claims (1)

[Claims] 1. A photopolymerizable composition comprising at least an addition-polymerizable compound having at least one ethylenically unsaturated double bond and a photopolymerization initiation system, wherein the photopolymerization initiation system is (a) Sensitizer represented by [I] or [II] (In the formula, R ¹ represents a hydrogen atom or an alkyl group, and R ²
And R ³ each represent a hydrogen atom, an alkyl group, an alkoxy group or an alkylthio group, or R ¹ and R ² may be bonded to each other to form a ring structure, and R ⁴
And R ⁵ each represent a hydrogen atom, a halogen atom or an alkyl group, but R ⁴ and R ⁵ do not become hydrogen atoms at the same time. l represents 0 or 1. ) [Chemical 2] (In the formula, R ⁶ represents a hydrogen atom or an alkyl group, and R ⁷
And R ⁸ each represents a hydrogen atom, an alkyl group, an alkoxy group or an alkylthio group, or R ⁶ and R ⁷ may be bonded to each other to form a ring structure, and R ⁹
To R ¹¹ each represent an alkoxy group, and m represents 0 or 1. (B) A photopolymerizable composition comprising at least one activator capable of generating an active radical upon irradiation with light in the presence of the sensitizer.