JPH10237117A - Photopolymerizable composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a phtopolymerizable composition, having high sensitivity to visible light and excellent in solubility in coating solvents, by making the composition include a combination of a titanocene compound with a coumarone derivative having a specific structure as a photopolymrization initiating system therein. SOLUTION: This composition is obtained by including (A) a compound having an ethylenic double bond capable of carrying out the addition polymerization [e.g. (meth)acrylic acid] and (B) a photoplymerization initiation system composed of a combination of (i) a titanocene compound functioning as a sensitizer [e.g. di-cyclopentadienyl-Ti-bis-2,6-difluoro-3-(pyrr-1-yl)-phenyl-1-yl] with (ii) a coumarone derivative, capable of generating active radicals by irradiation of light in the coexistence of the sensitizer and represented by formula I [R<1> and R<2> are each H, a (substituted)alkyl, etc.; R<3> and R<4> are each H or a 1-10C alkyl; R<5> is H, a 1-10C alkyl, etc.; R<6> and R<7> are each a group, etc., represented by formula II (R<9> and R<10> are each cyano, etc.); R<8> is H or a 1-10C alkyl] (e.g. a compound represented by formula III). The composition can be used together with an activator such as a Michler's ketone capable of generating radical other than the titanocene compound.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a photopolymerizable composition. In particular, the present invention relates to a photopolymerizable composition having extremely high sensitivity to light in the visible region.

[0002]

2. Description of the Related Art Conventionally, many image forming methods using a photopolymerization system are known. For example, a photopolymerizable composition comprising an addition-polymerizable compound containing an ethylenic double bond, a photopolymerization initiator, and an organic polymer binder used as desired is prepared, and the photopolymerizable composition is supported. Create a light-sensitive material with a layer of photopolymerizable composition applied to the body, image-expose the desired image, polymerize and cure the exposed part, and dissolve and remove the unexposed part to form a cured relief image Wherein the photosensitive material described above is provided with a layer of the photopolymerizable composition between two supports, at least one of which is transparent,
A method of forming an image by exposing the support after imagewise exposing from the transparent support side to cause a change in adhesive strength due to light, and other methods utilizing a change in toner adhesion due to light of the photopolymerizable composition layer. There are image creation methods and the like. As the photopolymerization initiator of the photopolymerizable composition applied to these methods, conventionally, benzoyl, benzoin alkyl ether,
Benzyl ketal, benzophenone, anthraquinone,
Benzyl or Michler's ketone has been used. However, these photoinitiators have 400 nm
Compared with the photopolymerization initiation ability for light in the ultraviolet region below, the photopolymerizable composition using these photopolymerization initiators is limited in its application range because it is extremely low for light in the visible light region of 400 nm or more. Was.

In recent years, with the development of image forming technology, there has been a strong demand for a photopolymerizable composition having high adaptability to light rays in the visible region. These are photosensitive materials suitable for, for example, non-contact type projection exposure plate making and laser plate making with a visible light laser. Several proposals have been made for a photopolymerizable composition containing a photopolymerization initiation system capable of responding to light in the visible light region. For example, a system of hexaarylbiimidazole and a radical generator and a dye (JP-B-45-37377), and a system of hexaarylbiimidazole and (p-dialkylaminobenzylidene) ketone (JP-A-47-2528, JP-A-47-2528) JP-A-54-155292), a system of a cyclic cis-α-dicarbonyl compound and a dye (JP-A-48-84183).
JP-A-52-112681, a system of a substituted triazine and a merocyanine dye (JP-A-54-151024), a system of a ketocoumarin and an activator (JP-A-52-112681, and JP-A-58-1).
5503, JP-A-60-88005), a system of a substituted triazine and a sensitizer (JP-A-58-29803,
JP-A-58-40302), biimidazole,
Styrene derivative, thiol-based system (JP-A-59-5640)
No. 3), a system of an organic peroxide and a dye (Japanese Unexamined Patent Publication No.
No. 40203, JP-A-59-189340).

Examples of the use of titanocene in a photopolymerization initiation system are disclosed in JP-A-59-152396 and JP-A-6-152396.
1-1151197, JP-A-63-10602, JP-A-63-41484, JP-A-2-291, JP-A-3-291
-12403, JP-A-3-20293 and JP-A-3-20293
27393, JP-A-3-52050, and
A system combining a titanocene with a xanthene dye and an addition-polymerizable ethylenic double bond-containing compound having an amino group or a urethane group (JP-A-4-221958 and JP-A-4-219756); A system of titanocene and 3-ketocoumarin dye having excellent sensitivity to emitted light of about 488 nm (JP-A-63
No. 221110), a system of titanocene and a coumarin dye having a heterocyclic group at the 3-position (JP-A-6-289335).
Pyran dyes and diarylhalonium salts, halomethyl-s-triazines, bisimidazole derivatives, halogen compounds or organic peroxides used in photopolymerization compositions for holography. (Japanese Patent Laid-Open No. 6-3296)
No. 54) and a system comprising a coumarin derivative and halomethyl-s-triazine (US Pat. No. 4,810,618).

[0005]

However, although the above photopolymerization system is certainly sensitive to light rays in the visible region, it is difficult to perform laser plate making using a small air-cooled argon ion laser or semiconductor laser. The sensitivity is insufficient, and a photopolymerization system with higher sensitivity has been desired. Therefore, an object of the present invention is to provide a photopolymerizable composition that is more sensitive to long-wavelength light such as visible light, and further has a sensitivity to light around 488 nm, which is the oscillation wavelength of an argon ion laser. It is an object of the present invention to provide a photopolymerizable composition which is extremely excellent in solubility and excellent in solubility in a coating solvent.

[0006]

The photopolymerizable composition according to the present invention essentially comprises a compound having at least one ethylenic double bond capable of addition polymerization and a photopolymerization initiation system. It is characterized in that the polymerization initiation system is a combination of a coumarone derivative of the general formula (1) acting as a sensitizer and a titanocene compound capable of generating an active radical upon receiving light irradiation in the presence of the sensitizer. It is assumed that.

[0007]

Embedded image

Wherein R ¹ and R ² are each independently:
A hydrogen atom or an alkyl group having 1 to 16 carbon atoms which may be substituted (substituents are a fluorine atom, a chlorine atom, a bromine atom, a hydroxyl group, an alkoxy group having 1 to 15 carbon atoms,
To 16 acyloxy group, an aryloxy group having 6 to 12 carbon atoms, indicates chosen) from alkoxycarbonyl acyl group hydroxycarbonyl acyl group and 4 to 10 carbon atoms having 3 to 10 carbon atoms, R ³ and R ⁴ ,
Each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, wherein R ¹ and R ³ and / or R ² and R ⁴ are bonded to each other directly or via an oxygen atom or a sulfur atom to form a substituent; The ring which may have may be formed. R ⁵
Is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or 3 carbon atoms
To 17 to 17 heterocyclic groups. At least one of R ⁶ and R ⁷ is a group represented by the following general formula (2), and the other is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or a group represented by the general formula (2).

[0009]

Embedded image

(Wherein at least one of R ⁹ and R ¹⁰ is a cyano group, and the other is a cyano group, an alkoxycarbonyl group having 2 to 10 carbon atoms, an acyl group having 2 to 10 carbon atoms, or A good phenylcarbonyl group or a naphthylcarbonyl group (substituents are a fluorine atom, a chlorine atom,
Selected from a bromine atom, a hydroxyl group, an alkoxy group having 1 to 15 carbon atoms and an acyloxy group having 2 to 16 carbon atoms)). R ⁸ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. ]

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. In the photopolymerizable composition of the present invention, the addition-polymerizable compound having at least one ethylenic double bond (hereinafter abbreviated as “ethylenic compound”) contained as the first essential component is a photopolymerizable compound. When the composition is irradiated with actinic rays, it is a compound having an ethylenic double bond that undergoes addition polymerization and cures by the action of a photopolymerization initiation system, which is a second essential component. It is a monomer having a heavy bond or a polymer having an ethylenic double bond in a side chain or a main chain. In the present invention, the meaning of the monomer is a concept corresponding to a so-called polymer substance, and therefore includes not only monomers in a narrow sense but also dimers, trimers, and oligomers. is there.

Examples of the monomer having an ethylenic double bond include unsaturated carboxylic acids and alkyl esters thereof, esters of aliphatic polyhydroxy compounds with unsaturated carboxylic acids, and aromatic polyhydroxy compounds with unsaturated carboxylic acids. And an ester obtained by an esterification reaction of an unsaturated carboxylic acid with a polyvalent carboxylic acid and a polyvalent hydroxy compound such as the above-mentioned aliphatic polyhydroxy compound and aromatic polyhydroxy compound. Examples of the unsaturated carboxylic acid and its alkyl ester include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid and alkyl esters having 1 to 5 carbon atoms of these carboxylic acids, and methyl of acrylic acid or methacrylic acid, Ethyl, propyl, butyl ester and the like can be mentioned.

Examples of the ester of the aliphatic polyhydroxy compound and the unsaturated carboxylic acid include ethylene glycol diacrylate, triethylene glycol diacrylate,
Acrylics such as trimethylolpropane triacrylate, trimethylolethane triacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and glycerol acrylate Acid esters, methacrylates in which the acrylic acid portion of these esters is replaced with methacrylic acid, itaconates in which itaconic acid is similarly replaced, crotonates in which crotonic acid is replaced, and maleates in which maleic acid is replaced.

Examples of the ester of the aromatic polyhydroxy compound and the unsaturated carboxylic acid include hydroquinone diacrylate, hydroquinone dimethacrylate, resorcin diacrylate, resorcin dimethacrylate, and pyrogallol triacrylate. The ester obtained by the esterification reaction of the unsaturated carboxylic acid with the polyvalent carboxylic acid and the polyvalent hydroxy compound is not necessarily a single ester, but typical examples include acrylic acid, phthalic acid and ethylene glycol. Condensate, condensate 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, and the like.

Other examples of the ethylenic compound used in the present invention include acrylamides such as ethylene bisacrylamide; allyl esters such as diallyl phthalate; and vinyl esters such as divinyl phthalate. Examples of the polymer having an ethylenic double bond in the main chain include, for example, a polyester obtained by a polycondensation reaction of an unsaturated divalent carboxylic acid and a hydroxy compound, and a polycondensation reaction of an unsaturated divalent carboxylic acid and a diamine. And the like. Polymers having an ethylenic double bond in the side chain are divalent carboxylic acids having a double bond in the side chain, for example, condensation polymers of dihydroxy or diamine compounds with itaconic acid, propylidene succinic acid, ethylidene malonic acid, etc. There is. Further, a polymer having a functional group having a reactive activity such as a hydroxy group or a methyl halide group in a side chain, for example, polyvinyl alcohol, poly (2-hydroxyethyl methacrylate), polyepichlorohydrin, etc., and acrylic acid, methacrylic acid, crotonic acid, etc. A polymer obtained by a polymer reaction with an unsaturated carboxylic acid of formula (I) can also be suitably used.

Of the above-mentioned ethylenic compounds, acrylate or methacrylate 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 photopolymerizable composition of the present invention is composed of a combination of two components, and the first component is a sensitizer represented by the above-mentioned general formula (1). This sensitizer is K
irpichenok, MA; etc. Khim. Ge
terotsiki Soedin, (1988)
(6) The compound can be synthesized according to the method described in 751 to 6. The reaction proceeds, for example, as follows.

[0017]

Embedded image

In the general formula (1), R¹And R^Two
Are each independently a hydrogen atom or may be substituted
An alkyl group having 1 to 16 carbon atoms (substituent is a fluorine atom,
Chlorine atom, bromine atom, hydroxyl group, alcohol having 1 to 15 carbon atoms
Xyl group, acyloxy group having 2 to 16 carbon atoms, 6 to 6 carbon atoms
12 aryloxy groups, hydroxy having 3 to 10 carbon atoms
Carbonyl acyloxy group and alcohol having 4 to 10 carbon atoms
Selected from a xycarbonylacyloxy group)
Has a carbon number of 1 to 8 which may be substituted
Alkyl groups are preferred, and the substituents include a hydroxyl group and a chlorine atom.
Atom, bromine atom, acyloxy group having 2 to 5 carbon atoms, carbon number
3 to 6 hydroxycarbonylacyloxy groups or carbon
Alkoxycarbonylacyloxy groups of formulas 4 to 7 are preferred
New R^ThreeAnd R^FourAre each independently a hydrogen atom or carbon
Represents an alkyl group having a prime number of 1 to 10, preferably a hydrogen atom
No. Also, R¹And R^Three, And R^TwoAnd R^FourAre directly
Is linked via an oxygen or sulfur atom to form a ring
May be¹And R ^Three, And R^TwoAnd R^FourBy
Ring structure formed by piperidine ring or benzene
Alicyclic amine rings such as julolidine rings containing
No. A substituent may be bonded to these rings, and
A hydroxyl group, a halogen atom, an alkyl having 1 to 8 carbon atoms
Group, an alkoxy group having 1 to 5 carbon atoms, an acyl group having 2 to 5 carbon atoms
A ruoxy group is preferred. R^FiveIs a hydrogen atom, having 1 to 1 carbon atoms
Represents an alkyl group of 0 or a heterocyclic group having 3 to 17 carbon atoms
Is a nitrogen-containing aromatic condensed ring system having 3 to 11 carbon atoms.
Group heterocyclic group is preferable, benzothiazolyl group, benzo
Xazolyl or benzimidazolyl is particularly preferred.
No. Also, R⁶And R⁷At least one of the general formula
A group represented by the formula (2), and⁹
And R^TenAt least one of

[0019]

Embedded image

Is a cyano group. When either R ⁹ or R ¹⁰ represents a group other than a cyano group, it has 2 to 2 carbon atoms.
It is preferably an alkoxycarbonyl group having 5 or an acyl group having 2 to 5 carbon atoms. It is particularly preferred that R ⁹ and R ¹⁰ are both cyano groups or one is a cyano group and the other is an ethoxycarbonyl group. When R ⁶ and R ⁷ are different in the general formula (1), and when R ⁹ and R ¹⁰ are different in the general formula (2), the sensitizer has a geometric isomer. The sensitizer usually obtained is a mixture of such geometric isomers. Preferred specific examples of the sensitizer used in the present invention are shown in Table 1 below. In Table 1, R ⁶ and R ⁷ are indicated as being different from each other, but are actually a mixture of geometric isomers. When R ⁹ and R ¹⁰ are different, they are also a mixture of geometric isomers.

[0021]

[Table 1]

[0022]

[Table 2]

[0023]

[Table 3]

[0024]

[Table 4]

[0025]

[Table 5]

The second component constituting the photopolymerizable composition according to the present invention is a titanocene compound capable of generating an active radical when irradiated with light in the presence of the sensitizer. The titanocene compound is not particularly limited, but examples thereof include JP-A-59-152396 and JP-A-61-151.
197 and JP-A-6-41170 can be appropriately selected and used from various titanocene compounds. Some examples are di-cyclopentadienyl-Ti-di-chloride, di-cyclopentadienyl-Ti-bis-phenyl, di-cyclopentadienyl-Ti-bis-2,3,4,4. 5,6-pentafluorophenyl-1-yl, dicyclopentadienyl-Ti-
Bis-2,3,5,6-tetrafluorophenyl-1-
Yl, di-cyclopentadienyl-Ti-bis-2,
4,6-trifluorophenyl-1-yl, di-cyclopentadienyl-Ti-bis-2,6-di-fluorophenyl-1-yl, di-cyclopentadienyl-Ti-
Bis-2,4-di-fluorophenyl-1-yl, di-
Methylcyclopentadienyl-Ti-bis-2,3,
4,5,6-pentafluorophenyl-1-yl, di-methylcyclopentadienyl-Ti-bis-2,3,5
6-tetrafluorophenyl-1-yl, di-methylcyclopentadienyl-Ti-bis-2,6-difluorophenyl-1-yl, di-cyclopentadienyl-Ti-
Bis-2,6-difluoro-3- (pyr-1-yl)-
Phenyl-1-yl, bis [cyclopentadienyl] bis [6-chloro-2-i-butylthio-4- (3-methylbut-1-oxy) pyrimidinyl] titanium, bis [cyclopentadienyl] bis [2 , 4-bis (1,1-dimethylpropoxy) pyrimidyl] titanium and the like.

An activator capable of generating a radical other than the titanocene compound can also be used in combination.
No. 56403, s-triazine compounds, JP-A-58-29803, thiol compounds, and amine compounds, and the like. Particularly preferred additives are N-phenylglycine and dialkylamine derivative compounds. And specifically, Michler's ketone,
Examples include compounds having a dialkylaminophenyl group. Examples of the compound having a dialkylaminophenyl group include compounds represented by the following general formulas (3) to (5).

[0028]

Embedded image

In the general formulas (3) to (5), R ^{11 to} R ^11
21 represents an alkyl group which may have a substituent selected from a halogen atom, an aryl group, an acyl group, a carboxyl group and an alkoxy group, and R ¹¹ , R ¹² and R ¹⁴
~ R ²¹ is preferably a lower alkyl group, especially 1 to 1 carbon atoms.
4 represents an alkyl group. R ¹³ usually represents an alkyl group having 1 to 20 carbon atoms which may have a substituent described above. Each of these may be linear or have a branched structure.

Some examples of the compounds represented by formulas (3) to (5) include, for example, ethyl p-dimethylaminobenzoate, ethyl p-diethylaminobenzoate, and isopropyl p-dimethylaminobenzoate. Dialkylaminobenzoic acid alkyl esters such as esters, p-dimethylaminobenzoic acid-n-butyl ester, p-dimethylaminobenzoic acid-n-octyl ester or p-di-n-butylaminobenzoic acid ethyl ester; 4,4 Bisaminobenzophenones such as' -bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone or 4,4'-bis (diisopropylamino) benzophenone; 4,4'-bis (dimethylamino) benzyl or , 4'-bis (diethylamino) ben Bis-aminobenzyl such Le like. Of these, compounds represented by the general formula (3) or (4), particularly alkyl dialkylaminobenzoate, are preferred.

The amount of the sensitizer and the compound capable of generating active radicals constituting the photopolymerization initiation system used in the photopolymerizable composition of the present invention is based on 100 parts by weight of the ethylenic compound. Preferably 0.05 to 20 parts by weight, more preferably 0.2 to 10 parts by weight, the compound capable of generating an active radical is generally 0.1 to 30 parts by weight, preferably 0.5 to 20 parts by weight. , More preferably 0.5 to 10 parts by weight.

The photopolymerizable composition of the present invention may contain, in addition to the above components, an organic polymer substance as a binder for modifying the composition and improving the physical properties after photocuring. preferable. The type may be appropriately selected according to the purpose of improving the compatibility, the film forming property, the developing property, the adhesive property, and the like. For example,
For improving aqueous developability, acrylic acid copolymer, methacrylic acid copolymer, itaconic acid copolymer, partially esterified maleic acid copolymer, modified acid cellulose having a carboxyl group in the side chain, polyethylene oxide, polyvinyl Pyrrolidone and the like are used.

To improve the film strength and adhesiveness, polyether of epichlorohydrin and bisphenol A; soluble nylon; polyalkyl methacrylate or polyalkyl acrylate such as polymethyl methacrylate; alkyl methacrylate and acrylonitrile, acrylic Copolymers of acid, methacrylic acid, vinyl chloride, vinylidene chloride, styrene, etc .; copolymers of acrylonitrile and vinyl chloride, vinylidene chloride; copolymers of vinylidene chloride, chlorinated polyolefin, vinyl chloride and vinyl acetate; Polyvinyl acetate; copolymer of acrylonitrile and styrene; copolymer of acrylonitrile and butadiene, styrene; polyvinyl alkyl ether; polyvinyl alkyl ketone; polystyrene; polyamide; polyurethane; polyethylene terephthalate Sofutareto; it can be used acetone cellulose and polyvinyl butyral. These binders are generally contained in a weight ratio of not more than 500%, preferably not more than 200% with respect to the ethylenic compound.

The photopolymerizable composition of the present invention may further contain, if necessary, a thermal polymerization inhibitor, a coloring agent, a plasticizer, a storage stabilizer, a surface protective agent, a leveling agent, a coating aid and other additives. be able to. Examples of the thermal polymerization inhibitor include hydroquinone, p-methoxyphenol, pyrogallol, catechol, 2,6-t-butyl-p-cresol, β-naphthol, and the like, and coloring agents such as phthalocyanine pigments, azo pigments, There are pigments such as carbon black and titanium oxide, ethyl violet, crystal violet, azo dyes, anthraquinone dyes, and cyanine dyes. When the binder is used, the amount of the thermal polymerization inhibitor and the coloring agent is 0.01 to 3% based on the total weight of the ethylenic compound and the binder, and the amount of the coloring agent is 0.1%. 1-20% by weight is preferred.

As the plasticizer, for example, dioctyl phthalate, didodecyl phthalate, triethylene glycol dicaprylate, dimethyl glycol phthalate, tricresyl phosphate, dioctyl adipate, dibutyl sebacate, triacetyl glycerin and the like are used. When an agent is used, it is preferably added in an amount of 10% by weight or less based on the total weight of the ethylenic compound and the binder.

When using the photopolymerizable composition of the present invention,
Usually, a light-sensitive material is prepared by dissolving in a suitable solvent to form a solution, coating this on a support and drying. As the solvent,
For example, 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 and the like are used, and if desired, two or more kinds can be used in combination.

The support for preparing a photosensitive material using the photopolymerizable composition of the present invention may be a conventional one. For example, aluminum, magnesium, copper, zinc, chromium,
Sheets of metals such as nickel and iron or alloys containing these as main components; papers such as fine paper, art paper, release paper; glass;
Inorganic sheets such as ceramics; polymer sheets such as polyethylene terephthalate, polyethylene, polymethyl methacrylate, polyvinyl chloride, vinyl chloride-vinylidene chloride copolymer, polystyrene, 6-nylon, cellulose triacetate, and cellulose acetate butyrate are used.

The light-sensitive material prepared using the photopolymerizable composition of the present invention may further contain a known technique for preventing adverse effects such as a decrease in sensitivity and a deterioration in storage stability due to oxygen, for example, a method for forming a photosensitive layer on a photosensitive layer. And a cover layer made of a wax-like substance having low oxygen permeability, a water-soluble polymer, or the like. The exposure light source applicable to the photopolymerizable composition of the present invention is not particularly limited, and includes a carbon arc, a high-pressure mercury lamp, a xenon lamp, a metal halide lamp, a fluorescent lamp, a tungsten lamp, a helium cadmium laser, an argon ion laser, and YA.
A general-purpose light source including visible light of 400 nm or more, such as a G laser, can be used.

[0039]

EXAMPLES Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples unless it exceeds the gist thereof. Examples 1 to 6 and Comparative Examples 1 to 5 On a grained and anodized aluminum sheet, a photosensitive composition coating solution having the following composition was applied using a wheeler to a dry film thickness of 2 μm. A photosensitive material sample was prepared by applying an aqueous solution of polyvinyl alcohol on the surface so that the dry film thickness was 3 μm.

[Coating solution of photosensitive composition] Methyl methacrylate / methacrylic acid / methyl acrylate copolymer 50 parts (weight average molecular weight 45,000, copolymerization ratio 80/7/13) trimethylolpropane triacrylate 50 parts Methyl cellosolve 500 parts Propylene glycol monomethyl ether acetate 500 parts Sensitizer; compound shown in Table 2 Compounding amount shown in Table 2 Active radical generator; compound shown in Table 2 Compounding amount shown in Table 2 The following items were evaluated for this photosensitive material sample. Table 2 shows the results.

(Sensitivity) A xenon lamp (UI-501C, manufactured by Ushio Electric Co., Ltd.) was used as a photosensitive material sample, and the wavelength was plotted on the abscissa and the light intensity was logarithmically ordinate on the ordinate using a spectral sensitivity measuring device manufactured by Narumi. Irradiated for 10 seconds. The exposed sample was developed with an aqueous solution containing 1% by weight of sodium carbonate and 0.5% by weight of an anionic surfactant (Perex NBL manufactured by Kao Corporation), and a photocured image was formed based on the height of the cured image obtained at 488 nm. The minimum required exposure was calculated and used as the sensitivity of the photosensitive material sample.

[Solubility of Sensitizer] Photosensitive Composition Coating Solution 2
When 0 ml is placed in a 30 ml sample bottle and stirred at 300 revolutions per minute with a 5 mm long Teflon stirrer tip, the sensitizer depends on the time until the sensitizer in the photosensitive composition coating solution is completely dissolved. Was evaluated for solubility. A: Dissolved in less than 5 minutes. B: Dissolved in 5 minutes or more and less than 10 minutes. C: Dissolved in 10 minutes or more and less than 20 minutes. D: It took more than 20 minutes to dissolve.

[0043]

[Table 6]

[0044]

[Table 7] * 1: The amount in parentheses indicates the amount (parts by weight) in the photosensitive composition coating solution.

In Table 2, among the abbreviations in the column of the sensitizer, S-
1, S-2, S-4 and S-5 respectively represent the compounds described in Table 1. Further, T-1 and T-2 represent the following compounds.

[0046]

Embedded image

In Table 2, the abbreviations in the column of the active radical generator (B-1, C-1, C-2, D-1, D-2, D-3)
Represents the following compounds, respectively.

[0048]

Embedded image

[0049]

The photopolymerizable composition of the present invention has a very high sensitivity to visible light, enables a plate making operation which is extremely advantageous in terms of cost and time, and also provides a sensitizer. Since it is excellent in solubility in a coating solvent, it is possible to shorten the liquid preparation time and realize high productivity. Thus, the compositions are useful in a wide range of applications, such as lithographic, intaglio,
It can be used for the production of printing plates such as letterpress, photoresist for dry wiring and IC, image formation such as relief image and image duplication, photo-curable ink, paint, adhesive etc. Extremely useful.

Claims (2)

[Claims] 1. A photopolymerizable composition comprising a compound having at least one ethylenic double bond capable of addition polymerization and a photopolymerization initiation system, wherein the photopolymerization initiation system comprises a titanocene compound and the following general formula (1) A photopolymerizable composition containing the coumarone derivative represented by the formula (1). Embedded image [Wherein, R ¹ and R ² each independently represent a hydrogen atom or an optionally substituted alkyl group having 1 to 16 carbon atoms (substituents are a fluorine atom, a chlorine atom, a bromine atom, a hydroxyl group, Selected from an alkoxy group having 1 to 15 carbon atoms, an acyloxy group having 2 to 16 carbon atoms, an aryloxy group having 6 to 12 carbon atoms, a hydroxycarbonylacyloxy group having 3 to 10 carbon atoms, and an alkoxycarbonylacyloxy group having 4 to 10 carbon atoms. R ³ and R ⁴ are each independently
A hydrogen atom or an alkyl group having 1 to 10 carbon atoms,
¹ and R ³ and / or R ² and R ⁴ may be bonded to each other directly or via an oxygen atom or a sulfur atom to form a ring which may have a substituent. R ⁵ represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or a heterocyclic group having 3 to 17 carbon atoms. At least one of R ⁶ and R ⁷ is a group represented by the following general formula (2), and the other is a hydrogen atom or a group having 1 carbon atom.
To 10 or an alkyl group represented by the general formula (2). Embedded image (In the formula, at least one of R ⁹ and R ¹⁰ is a cyano group, and the other is a cyano group, an alkoxycarbonyl group having 2 to 10 carbon atoms, an acyl group having 2 to 10 carbon atoms, or phenylcarbonyl which may be substituted. Or a naphthylcarbonyl group (substituents are a fluorine atom, a chlorine atom, a bromine atom, a hydroxyl group, an alkoxy group having 1 to 15 carbon atoms and a
6). R ⁸ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. ] 2. The photopolymerizable composition according to claim 1, wherein the photopolymerizable composition further contains at least one compound represented by the following general formula (3) or (4). . Embedded image [In the formula, R ^{11 to} R ¹⁷ each represent an alkyl group which may be substituted (the substituent is selected from a halogen atom, an aryl group, an acyl group, a carboxyl group, and an alkoxy group). ]