JPH086245A - Photopolymerizable composition - Google Patents

Abstract

(57) [Summary] [Structure] A photopolymerizable composition comprising at least an addition-polymerizable compound and a photopolymerization initiation system, wherein the addition-polymerizable compound contains at least one ethylenically unsaturated double bond. And a sensitizer having a skeleton of a specific pyrromethene dye having an acyl group in a side chain, which has a photopolymerization initiation system,
It is characterized by containing a compound capable of generating an active radical upon irradiation with light under coexistence with the sensitizer. [Effect] The photopolymerizable composition of the present invention has extremely excellent sensitivity to visible light, particularly long-wavelength light.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a photopolymerizable composition. In particular, it 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 the photopolymerizable composition is provided between two supports in which at least one of the above-mentioned photosensitive materials is transparent, and the transparent support side is imagewise exposed to cause a change in adhesive strength by 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 have a photopolymerization initiation ability of 4 nm or less in the ultraviolet region of 400 nm or less.
It is significantly lower for light in the visible region above 00 nm and thus has limited the range of applications of photopolymerizable compositions containing them.

In recent years, with the development of image forming technology, there has been a strong demand for a photopolymer having a high adaptability to light rays in the visible region. For example, it is a light-sensitive 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 oscillation beam of visible light of an argon ion laser is considered to be one of the most promising techniques in the future.

Several proposals have hitherto been made for a photopolymerizable composition containing a photopolymerization initiation system which is sensitive to light rays in the visible light region. For example, a system of hexaarylbiimidazole, a radical generator and a dye (Japanese Patent Publication No.
5-37377), a system of hexaarylbiimidazole and (p-dialkylaminobenzylidene) ketone (JP-A-47-2528, JP-A-54-155292).
Each of the above publications), a system of a cyclic cis-α-dicarbonyl compound and a dye (JP-A-48-84183), a system of a substituted triazine and a merocyanine dye (JP-A-54-151024).
No.), a system of ketocoumarin and an activator (JP-A-52-1).
12681, JP-A-58-15503, JP-A-60
-88005), a system of substituted triazine and a sensitizer (JP-A-58-29803, JP-A-58-40302).
Each of the above publications), biimidazole, a styrene derivative, a thiol system (JP-A-59-56403), an organic peroxide-dye system (JP-A-59-140203, JP-A-59-140203).
As an example of using titanocene in a photopolymerization initiation system, JP-A-59-152396.
No. 61-151197, 63-106.
02, JP-A-63-41484, JP-A-2-291.
Japanese Patent Laid-Open No. 3-12403, Japanese Patent Laid-Open No. 3-20293
JP-A-3-27393, JP-A-3-52050 and JP-A-3-52050, and a system in which a titanocene and a xanthene dye and an addition-polymerizable ethylenic saturated double bond-containing compound having an amino group or a urethane group are combined (Japanese Patent Application Laid-Open No. Hei-HEI (Kokai)). 4-221
958 and JP-A-4-219756) A system of a titanocene and a 3-ketocoumarin dye having excellent sensitivity in the vicinity of an argon ion laser of 488 nm (JP-A-63-2211).
No. 10) and the like.

Further, Japanese Patent Application No. 5-83587 discloses a YAG laser 53 in which a titanocene and a pyrromethene dye are combined.
It has been reported that it has excellent sensitivity near 0 nm and an argon ion laser near 488 nm. However, the dye described in the report is certainly the YAG laser of 530 nm.
Although it shows high photosensitivity to YAG laser 530n, the sensitivity around 488 nm of argon ion laser is high.
It was slightly inferior to the sensitivity near m.

[0006]

DISCLOSURE OF THE INVENTION The present invention provides a photopolymerizable composition which is very excellent in sensitivity near 488 nm by using a specific pyrromethene dye having an acyl group in its side chain as a sensitizer. It makes it possible.

[0007]

Means for Solving the Problems As a result of intensive investigations by the present inventors to overcome such difficulties and obtain an excellent photopolymerizable composition, the present inventors have found that at least a compound capable of addition polymerization and a photopolymerization initiation system are included. In the photopolymerizable composition, wherein the addition-polymerizable compound has one or more ethylenically unsaturated double bonds, the photopolymerization initiation system has a specific group having an acyl group in a side chain. It was found that by containing a sensitizer having a pyrromethene dye skeleton and a compound capable of generating an active radical upon irradiation with light in the coexistence with the sensitizer, high sensitivity and high practicality can be obtained, and the present invention Arrived

That is, an object of the present invention is to provide a photopolymerizable composition which is more sensitive to long-wavelength light such as visible light. 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, an object of the present invention is a photopolymerizable composition containing at least an addition-polymerizable compound and a photopolymerization initiation system, wherein the addition-polymerizable compound has at least one ethylenically unsaturated double bond. And a photopolymerizable composition having a photopolymerization initiation system containing at least an addition-polymerizable compound and a photopolymerization initiation system, the addition-polymerizable compound contains at least an ethylenically unsaturated double bond. And the photopolymerization initiation system has (a) a sensitizer represented by the following general formula [I]:

[0009]

[Chemical 4]

[Wherein, X ¹ and X ² each represent a halogen atom, an alkyl group, an aryl group, a substituted or unsubstituted hydrocarbon ring group or a substituted or unsubstituted heterocyclic group, and R ^{1 to} R ⁴ are Hydrogen atom, halogen atom,
Alkyl group, acyl group, alkoxycarbonyl group, aryl group, allyl group, aralkyl group, substituted or unsubstituted hydrocarbon ring group, substituted or unsubstituted heterocyclic group or-
Represents SO ₃ -R ⁶ , wherein R ⁶ is a hydrogen atom, an alkyl group,
Aryl group, aralkyl group, alkali metal atom or 4
Represents a ^primary ammonium, and Y ¹ and Y ² are each represented by the following general formula [II], a hydrogen atom, a halogen atom, an alkyl group, an acyl group, an alkoxycarbonyl group, an aryl group,
Allyl group, aralkyl group, substituted or unsubstituted hydrocarbon ring group, substituted or unsubstituted heterocyclic group or -SO _3-
Represents R ^7, R ⁷ represents a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, and an alkali metal atom or a quaternary ammonium, at least one of Y ¹ and Y ² represent the following general formula [II],

[0011]

Embedded image —CO— (CR ⁸ = CR ⁹ ) _n —R ¹⁰ [II]

(In the formula, n is an integer of 0 to 3, R ⁸ and R ⁹ represent a hydrogen atom, an alkyl group, an aryl group and an aralkyl group, respectively, and R ¹⁰ is an alkyl group, an aryl group, an aralkyl group, Represents a substituted or unsubstituted hydrocarbon ring group or a substituted or unsubstituted heterocyclic group) R ⁵ represents a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, an allyl group, a substituted or unsubstituted hydrocarbon ring group or a substituted group Alternatively, it represents an unsubstituted heterocyclic group. 〕as well as,
(B) A photopolymerizable composition characterized by containing a compound capable of generating an active radical upon irradiation with light in the presence of 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 a photopolymerization initiation system that is a 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, and therefore, in addition to the narrowly defined monomer, a dimer,
It also includes trimers and oligomers.

Examples of the monomer having an ethylenically unsaturated bond include unsaturated carboxylic acid, ester of aliphatic polyhydroxy compound and unsaturated carboxylic acid; ester of aromatic polyhydroxy compound and unsaturated carboxylic acid; 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, trimethylolethane triacrylate. Acrylic esters such as pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, glycerol acrylate, etc. Methacrylic acid ester replaced, Itaconic acid ester similarly replaced with itaconate Crotonate is maleic acid ester, and was replaced with crotonic acid ester or maleate was replaced.

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 or 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, adipic 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 divalent carboxylic 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 condensation polymer of a dicarboxylic acid having an unsaturated bond in the side chain, such as itaconic acid, propylidene succinic acid, ethylidene malonic acid, etc. and a dihydroxy or diamine compound. . 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, methacrylic acid, crotonic acid, etc. Polymers obtained by the macromolecular reaction with the unsaturated carboxylic acid can also be suitably used.

Of the above-mentioned ethylenic compounds, acrylic acid ester or methacrylic acid ester monomers are particularly preferably used. Next, the photopolymerization initiation system which is the second essential component of the photopolymerization 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, and the first component thereof is the sensitizer represented by the above general formula [I] represented as (a) in the present invention. .

These sensitizers include, but are not limited to, US Pat. No. 4,774,339, J. H. Boye
ret. al, Heteroatom Chemis
try, Vol. 1,5,389 (1990), Lie
bigs Ann Chem. 718, 208-223
The sensitizer of the present invention having an acyl group is synthesized by the method described in (1968) and the like.

In the general formula [I], X ¹ and X ² each represent a halogen atom, an alkyl group, an aryl group, a substituted or unsubstituted hydrocarbon ring group or a substituted or unsubstituted heterocyclic group, and R ¹ to R ⁴ is a hydrogen atom,
Represents a halogen atom, an alkyl group, an acyl group, an alkoxycarbonyl group, an aryl group, an allyl group, an aralkyl group, a substituted or unsubstituted hydrocarbon ring group, a substituted or unsubstituted heterocyclic group or -SO ₃ -R ⁶ , R ⁶ represents a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, an alkali metal atom or a quaternary ammonium, and Y ¹ and Y ² are each represented by the following general formula [II], a hydrogen atom, a halogen atom, an alkyl group or an acyl group. , An alkoxycarbonyl group, an aryl group, an allyl group, an aralkyl group, a substituted or unsubstituted hydrocarbon ring group, a substituted or unsubstituted heterocyclic group or —SO ₃ —R ⁷ , and R ⁷ is a hydrogen atom or an alkyl group. , an aryl group, an aralkyl group, and an alkali metal atom or a quaternary ammonium, at least one of Y ¹ and Y ² is represented by the following general formula It represents the II],

[0021]

Embedded image --CO-(CR ⁸ = CR ⁹ ) _n --R ¹⁰ [II]

(In the formula, n is an integer of 0 to 3, R ⁸ and R ⁹ represent a hydrogen atom, an alkyl group, an aryl group and an aralkyl group, respectively, and R ¹⁰ is an alkyl group, an aryl group, an aralkyl group, Represents a substituted or unsubstituted hydrocarbon ring group or a substituted or unsubstituted heterocyclic group) R ⁵ represents a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, an allyl group, a substituted or unsubstituted hydrocarbon ring group or a substituted group Alternatively, it represents an unsubstituted heterocyclic group.

When X ¹ and X ² , R ^{1 to} R ¹⁰ and Y ¹ and Y ² represent an alkyl group, it preferably has 1 to 6 carbon atoms, particularly preferably 1 to 3 carbon atoms, It may be linear or may have a side chain. R ¹ ~
When R ¹⁰ and Y ¹ and Y ² represent an aralkyl group or an aryl group, and X ¹ and X ² represent an aryl group,
It preferably has 6 to 20 carbon atoms, and has 6 to 1 carbon atoms.
5 is particularly preferable. When R ^{1 to} R ⁴ and Y ¹ and Y ² each represent an acyl group or an alkoxycarbonyl group, the carbon number of the carbon chain thereof is particularly preferably 1 to 3, respectively. X ¹ and X ² , R ^{1 to} R ^{4 and} Y
^{When 1} and Y ² represent a halogen atom, they are generally a fluorine atom, a bromine atom or a chlorine atom, and when R ⁶ and R ⁷ represent an alkali metal atom, they generally represent
It is a lithium atom, a sodium atom, or a potassium atom.

X¹And X², R¹~ R^TenAnd Y¹Oh
And Y²Is a substituted or unsubstituted hydrocarbon ring group
When the hydrocarbon ring is mononuclear or dinuclear,
The substituent should be an alkyl group having 1 to 3 carbon atoms.
And are particularly preferable, and X ¹And X², R¹~ R^Ten
And Y¹And Y²Is a substituted or unsubstituted heterocyclic group
When represented, as a hetero atom contained in the heterocyclic group
Is generally a nitrogen atom, oxygen atom or sulfur atom.
And are preferred. Also, R¹~ R^FiveAnd Y¹And Y²
When represents an allyl group, it must have 2 to 10 carbon atoms.
preferable.

In particular, at least one of Y ¹ and Y ² .
In the case of the general formula [III], the sensitivity near 480 nm and the sensitivity near 530 nm are extremely high and suitable. Typical examples of the sensitizer represented by the general formula [I] are shown below. The general formula [I] used in the present invention is as follows.
The sensitizer represented by is not limited to these specific examples. In the following examples, unless otherwise stated, R
^{1 to} R ⁴ represent a methyl group, and X ¹ and X ² represent a fluorine atom.

[0026]

[Table 1]

[0027]

[Table 2]

[0028]

[Table 3]

[0029]

[Table 4]

In the present invention, at least one sensitizer as described above is selected and used. The second component constituting the photoinitiator system of the present invention, when represented by (b) in the present invention, is irradiated with light in the presence of the sensitizer,
It is a compound that can generate active radicals.

As the compound capable of generating the active radical, a titanocene compound is preferable, and the titanocene compound is not particularly limited, but for example, JP-A-59-1523.
96, JP-A-61-151197, JP-A-6-41
It can be appropriately selected and used from various titanocene compounds described in JP-A No. 170. More specifically, di-cyclopentadienyl-Ti-di-chloride, di-cyclopentadienyl-Ti-bis-phenyl, di-cyclopentadienyl-Ti-bis-2,3.
4,5,6-Pentafluorophenyl-1-yl, dicyclopentadienyl-Ti-bis-2,3,5,6-tetrafluorophen-1-yl, di-cyclopentadienyl-Ti-bis -2,4,6-trifluorophenyl-1
1-yl, di-cyclopentadienyl-Ti-bis-2,
6-di-fluorophen-1-yl, di-cyclopentadienyl-Ti-bis-2,4-di-fluorophenyl-
1-yl, di-methylcyclopentadienyl-Ti-bis-2,3,4,5,6-pentafluorophenyl-1-
Di-methylcyclopentadienyl-Ti-bis-
2,3,5,6-tetrafluorophen-1-yl, di-methylcyclopentadienyl-Ti-bis-2,6-
Difluorophen-1-yl, di-cyclopentadienyl-Ti-bis-2,6-difluoro-3- (pyr-1
-Yl) -phen-1-yl (hereinafter referred to as B-1),
Bis [cyclopentadienyl] bis [6-chloro-2-
i-Butylthio-4- (3-methylbut-1-oxy)
Pyrimidinyl] titanium, bis [cyclopentadienyl]
Examples include bis [2,4-bis (1,1-dimethylpropoxy) pyrimidyl] titanium.

Examples of activators capable of generating radicals other than titanocene compounds include s-triazine compounds described in JP-A-59-56403 and JP-A-58-29.
Examples thereof include a thiol compound described in JP-A No. 803 or an amine compound, and particularly preferable additives include dialkylamine derivative compounds, and specific examples thereof include Michler's ketone and ethyl p-diethylaminobenzoate.

The suitable amounts of the sensitizer and the compound capable of generating an active radical which constitute the photopolymerization initiation system used in the photopolymerizable composition of the present invention described above are not particularly limited, but the ethylenic compound 100 is used. With respect to parts by weight, the sensitizer is preferably 0.05 to 20 parts by weight, more preferably 0.
2 to 10 parts by weight, generally 0.1 to 30 parts by weight, preferably 0.5 to 20 parts by weight of the compound capable of generating an active radical.
By weight, more preferably 0.5 to 10 parts by weight.

In the photopolymerizable composition of the present invention, in addition to the above-mentioned core constituents, it is preferable to further add an organic polymer substance as a binder for the purpose of modifying the composition and improving 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; polyalkylmethacrylate such as polymethylmethacrylate or polyalkylalkylacrylate; alkylmethacrylate 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; Acrylonitrile-butadiene-styrene copolymer; Polyvinyl alkyl ether; Polyvinyl alkyl ketone; Polystyrene; Polyamide; Polyurethane; Polyethylene terephthalate Phthalate; acetyl cellulose and polyvinyl butyral, and the like. The weight ratio of these binders to the ethylenic compound is preferably 500% or less, more preferably 200% or less.
It can be added and mixed in the range of not more than%.

If necessary, the photopolymerizable composition of the present invention may further contain a thermal polymerization inhibitor, a colorant, a plasticizer, a storage stabilizer, a surface protective agent, a smoothing agent, a coating aid and other additives. it can. Examples of the thermal polymerization inhibitor include hydroquinone,
p-methoxyphenol, pyrogallol, catechol,
There are 2,6-di-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, and azo. There are series dyes, anthraquinone series dyes, and cyanine series 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. -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 of the total weight of the ethylenic compound and the binder can be added.

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 dissolving it in a suitable solvent to form a solution, which is coated 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, trichloroethane, dimethylformamide, methyl cellosolve, ethyl cellosolve, tetrahydrofuran,
Bentoxone, propylene glycol monomethyl ether, etc. are available, and one or more of them can be used in combination.

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, a sheet of metal such as aluminum, magnesium, copper, zinc, chromium, nickel, iron or an alloy containing them as a main component; high-quality paper, art paper,
Papers such as release paper; inorganic sheets such as glass and ceramics; polyethylene terephthalate, polyethylene, polymethylmethacrylate, polyvinyl chloride, vinyl chloride-
Polymer sheets such as vinylidene chloride copolymer, polystyrene, 6-nylon, cellulose triacetate, and cellulose acetate butyrate are available.

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,
It is also possible to provide a coating layer made of a water-soluble polymer or the like.
The exposure light source applicable to the composition of the present invention is not particularly limited, but carbon arc, high pressure mercury lamp, xenon lamp, metal halide lamp, fluorescent lamp, tungsten lamp, helium cadmium laser, argon ion laser, YAG laser, etc. A general-purpose light source including a light ray can be used more suitably.

[0041]

EXAMPLES The present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples unless it exceeds the gist. Synthesis Example of [I-7] The sensitizer [I-1] (0.01 mol) and p-dimethylaminocinnaraldehyde (0.01 mol) were dissolved in 20 ml of t-butyl alcohol, and potassium t-butoxide was added. (3
g) and after stirring for 12 hours at 25 ° C.,
After adding 200 ml of water to this reaction solution and allowing it to stand overnight,
The precipitate was filtered and extracted.

This precipitate was recrystallized from ethanol,
I-7 was obtained. Examples 1 to 17 and Comparative Examples 1 to 3 On a grained and anodized aluminum sheet, using a whirler, a photosensitive composition coating solution having the following composition was applied to a dry film thickness of 2 μm, and further, 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 xenon lamp; UI-501C manufactured by USHIO INC. Was used as a sample of this photosensitive material, and the abscissa axis represents wavelength and the ordinate axis represents logarithmically weak light intensity by a spectral sensitivity measuring device manufactured by Narumi. 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 exposure amount required for photocured image formation was calculated from the height of the cured image obtained at 488 nm, and the exposure was calculated. The sensitivity of the composition was used. The results are shown in Table-1.

[0044]

[Table 5] [Photosensitive composition coating liquid] Methyl methacrylate / methacrylic acid / methyl acrylate copolymer 60 parts (weight average molecular weight 45,000, copolymerization ratio 80/10/10) trimethylolpropane triacrylate 40 Parts Methyl cellosolve 800 parts Tetrahydrofuran 50 parts Sensitizer (listed in Table-1) Compound capable of generating active radicals (listed in Table-1)

[0045]

[Table 6]

[0046]

[Table 7]

[0047]

[Table 8]

[0048]

[Table 9] In Table-1, [S-1], [S-2] and [S-3] are respectively [S-1] Eosin Yellowish.

[0049]

[Chemical 7]

Represents Further, for Examples 3, 10 and 11, when the minimum exposure amount required for photo-curing image formation was calculated even at 530 nm, the sensitivity (m
Jcm ^-2 ) is 0.60, 0.16, and 0.16, respectively.
Met.

[0051]

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, production of printing plates such as planographic printing, intaglio printing, relief printing, printed wiring and I printing.
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.

Claims (4)

[Claims] 1. A photopolymerizable composition containing at least an addition-polymerizable compound and a photopolymerization initiation system, wherein the addition-polymerizable compound has at least one ethylenically unsaturated double bond, and The photopolymerization initiation system is (a) a sensitizer represented by the following general formula [I]: [Wherein, X ¹ and X ² each represent a halogen atom, an alkyl group, an aryl group, a substituted or unsubstituted hydrocarbon ring group or a substituted or unsubstituted heterocyclic group, and R ¹ to
R ⁴ is a hydrogen atom, a halogen atom, an alkyl group,
Acyl group, alkoxycarbonyl group, aryl group, allyl group, aralkyl group, substituted or unsubstituted hydrocarbon ring group, substituted or unsubstituted heterocyclic group or -SO ₃ -R
Represents ^6, R ⁶ is a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, an alkali metal atom or represents a quaternary ammonium, respectively Y ¹ and Y ² are the following general formula [II], hydrogen atom, a halogen atom, an alkyl Group, acyl group, alkoxycarbonyl group, aryl group, allyl group,
An aralkyl group, a substituted or unsubstituted hydrocarbon ring group, a substituted or unsubstituted heterocyclic group or -SO ₃ -R ⁷ , wherein R ⁷ is a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, an alkali metal atom or It represents a quaternary ammonium, and at least one of Y ¹ and Y ² represents the following general formula [II]: embedded image —CO— (CR ⁸ = CR ⁹ ) _n —R ¹⁰ [II] (Formula 2 In the formula, n is an integer of 0 to 3, R ⁸ and R ⁹ each represent a hydrogen atom, an alkyl group, an aryl group or an aralkyl group, and R ¹⁰ represents an alkyl group, an aryl group, an aralkyl group, a substituted or unsubstituted group. hydrocarbon ring represents a group or a substituted or unsubstituted heterocyclic group) R ⁵ is a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, an allyl group, a substituted or unsubstituted hydrocarbon ring group or a substituted or unsubstituted heterocyclic It represents a group. 〕as well as,
(B) A photopolymerizable composition containing a compound capable of generating an active radical upon irradiation with light in the presence of the sensitizer. 2. In the general formula [I], Y ¹ and Y
^2. The photopolymerizable composition according to claim 1, wherein at least one of ² is the general formula [III]. [Chemical 3] 3. The photopolymerizable composition according to claim 1, wherein the compound capable of generating an active radical is a titanocene compound. 4. The photopolymerizable composition according to claim 1, wherein the compound capable of generating an active radical is a titanocene compound and a dialkylamine derivative compound.