JPH06295061A - Photopolymerizable composition - Google Patents

Abstract

PURPOSE:To provide a photopolymerizable compsn. having high sensitive for long wavelength rays by using an additionpolymerizable compd. having one ethylene-type unsatd. double bond and incorporating a specified sensitizer and one kind of titanocene compd. CONSTITUTION:The addition-polymerizable compd. has one ethylene-type unsatd. double bond. The photopolymn. initiating system contains a sensitizer expressed by formulae I-V and one kind of titanocene compd. which can produce active radictals. In formulae, R<1>-R<7>, R<12>-R<26> are hydrogen atoms, alkyl groups, alkoxy groups, alkylthion groups, phenyl groups, etc., Q, T, R<27>, R<28> are one- to five- nucleus aromatic heterocyclic residues and A, B, C are oneto three-nucleus residues, alpha, beta, lambda, theta, n are 0 or 1 zeta is 1 or 2, X is a specified group, Y is a bivalent atom or bivalent group, and k is 0-2.

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 optionally an organic polymer binder is prepared, and the photopolymerizable composition is supported. A photosensitive material having a layer of the photopolymerizable composition applied on the body is prepared, and the 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, a method of forming an image by peeling the support, a photosensitive material in which a microcapsule layer is provided by coating the support with microcapsules having a photopolymerizable composition and a color material such as a leuco dye in the contents Create The photosensitive material imagewise exposed to photocuring capsules exposed portion, the capsule in the unexposed portion was destroyed by pressure treatment, or heat treatment, and developed by contact with the color material developer,
There are a method for forming a colored image, and an image forming method utilizing a change in toner adhesion of the photopolymerizable composition layer due to light.

Conventionally, benzoyl, benzoylalkyl 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 significantly lower in light in the visible light region of 400 nm or more as compared with the photopolymerization initiating ability in the ultraviolet light region of 400 nm or less, and therefore the application of the photopolymerizable composition containing them is The range has been limited.

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 488 nm oscillation beam 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 photosensitive material containing a photopolymerization initiation system capable of being 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. 45-
37377), a system of hexaarylbiimidazole and (p-dialkylaminobenzylidene) ketone (JP-A-47-2528, JP-A-54-155292,
JP-A-56-166154), cyclic cis-α-
System of dicarbonyl compound and dye (JP-A-48-8418)
3), a system of substituted triazine and merocyanine dye (JP-A-54-151024), a system of ketocoumarin and an activator (JP-A-52-112681, JP-A-58).
-15503, JP-A-60-88005),
Systems of substituted triazines and sensitizers (JP-A-58-29803)
JP-A-58-40302), biimidazole, a styrene derivative, and a thiol system (JP-A-59-56).
403), a system of an organic peroxide and a dye (Japanese Patent Laid-Open No. 59-59).
-140203, JP-A-59-189340).

Examples of the use of titanocene in the photopolymerization initiation system are described in JP-A-59-152396, JP-A-61-151197, JP-A-63-10602, and JP-A-63-41484. , JP-A-2-291, JP-A-3-12403), systems of titanocene and 3-ketocoumarin dyes (JP-A-63-221110), and titanocene and xanthene dyes, and further amino or urethane groups. A system in which an addition-polymerizable compound containing an ethylenic saturated double bond is combined (JP-A-4-221958)
And Japanese Patent Laid-Open No. 4-219756).

[0007]

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 Further, a system of a sensitizing dye having a julolidine skeleton in the molecule and hexaarylbiimidazole is described in, for example, JP-A-2-69. Although these systems have high sensitivity to 488 nm argon ion laser light, the developability of non-image areas (unexposed areas) deteriorates due to storage over time, and a slight amount of the photosensitive layer remains on the non-image areas after development. Tend to do.

[0008]

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 inventors have found that addition polymerization having at least one ethylenic double bond is possible. Compound, at least one sensitizer having a specific tetrahydroquinoline skeleton in the molecule, and at least one titanocene compound as an activator capable of generating an active radical upon irradiation with light in the coexistence with the sensitizer As a result, they have found that the sensitivity is high and the practicality is high, and have reached 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 long wavelength light such as 488 nm. Further, an object of the present invention is to provide a photopolymerizable composition having excellent developability even after storage with time. 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. Therefore, the object of the present invention is to
In a photopolymerizable composition containing at least an addition-polymerizable compound and a photopolymerization initiation system, the addition-polymerizable compound has at least one ethylenically unsaturated double bond, and the photopolymerization initiation system is ( a) The following general formulas [I] to [V
I] at least one sensitizer represented by

[0011]

[Chemical 10]

(In the formula, R ¹ represents a hydrogen atom or an alkyl group, R ² and R ³ represent a hydrogen atom, an alkyl group, an alkoxy group or an alkylthio group, respectively,
R ¹ and R ² may be bonded to each other to form a ring structure, R ⁴ represents a hydrogen atom, an alkyl group, an alkoxy group or a phenyl group, and Q may have a substituent. Represents a mononuclear to pentanuclear fused polycyclic aromatic hydrocarbon residue or a mononuclear to pentanuclear aromatic heterocyclic residue which may have a substituent, and α and β represent 0 or 1 respectively . )

[0013]

[Chemical 11]

(In the formula, R ⁵ represents a hydrogen atom or an alkyl group, and R ⁶ and R ⁷ represent a hydrogen atom, an alkyl group, an alkoxy group or an alkylthio group, respectively,
R ⁵ and R ⁶ may be bonded to each other to form a ring structure, and A is optionally substituted 1 to 3
Represents a condensed polycyclic aromatic hydrocarbon residue of the nucleus or a mononuclear to heteronuclear aromatic heterocyclic residue which may have a substituent, and X is

[0015]

[Chemical 12]

(Wherein R ^{8 to} R ¹¹ each represent an alkyl group, an alkoxy group or a phenyl group, and δ is 1 to 1).
Represents an integer of 3, and ε represents an integer of 0 to 2. ), And γ represents 0 or 1. )

[0017]

[Chemical 13]

(In the formula, R ¹² represents a hydrogen atom or an alkyl group, and R ¹³ and R ¹⁴ each represent a hydrogen atom, an alkyl group, an alkoxy group or an alkylthio group,
R ¹² and R ¹³ may combine with each other to form a ring structure, and B may have a substituent from 1 nucleus to 3
Represents a condensed polycyclic aromatic hydrocarbon residue of a nucleus or a mononuclear to trinuclear aromatic heterocyclic residue which may have a substituent, Y represents a divalent atom or a divalent group, and ζ is Represents 1 or 2. )

[0019]

[Chemical 14]

(In the formula, R ¹⁵ represents a hydrogen atom or an alkyl group, R ¹⁶ represents a hydrogen atom, an alkyl group, an alkoxy group or an alkylthio group, or R ¹⁵ and R ¹⁶ are bonded to each other to form a ring structure. And T is a mononuclear to pentanuclear fused polycyclic aromatic hydrocarbon residue which may have a substituent or a mononuclear to pentanuclear which may have a substituent. Represents an aromatic heterocyclic residue, and θ and η each represent 0 or 1.)

[0021]

[Chemical 15]

(In the formula, R ¹⁷ represents a hydrogen atom or an alkyl group, R ¹⁸ and R ¹⁹ each represent a hydrogen atom, an alkyl group, an alkoxy group, or an alkylthio group, or R ¹⁷ and R ¹⁸ are the same as each other. R ²⁰ may represent a hydrogen atom, an alkyl group, an alkoxy group or a phenyl group, and R ²¹ represents a hydrogen atom, an acetyl group or

[0023]

[Chemical 16]

R ²² represents an alkyl group or an aralkyl group, and κ represents 0 to 2. D represents a mononuclear to trinuclear fused polycyclic aromatic hydrocarbon residue which may have a substituent or a mononuclear to trinuclear aromatic heterocyclic residue which may have a substituent. . )

[0025]

[Chemical 17]

(Wherein R ²³ represents a hydrogen atom or an alkyl group, R ²⁴ and R ²⁵ each represent a hydrogen atom, an alkyl group, an alkoxy group or an alkylthio group, or
R ²³ and R ²⁴ may be bonded to each other to form a ring structure, R ²⁶ represents a hydrogen atom, an alkyl group, an alkoxy group or a phenyl group, R ²⁷ and R ²⁸ each represent an alkyl group, An aralkyl group, an alkoxy group, an aryloxy group, a carboalkoxy group, a mononuclear to pentanuclear fused polycyclic aromatic hydrocarbon residue which may have a substituent, or an optionally substituted 1 Aromatic heterocyclic residue of 5 to nuclei or

[0027]

[Chemical 18]

And λ represents 0 or 1. And (b) a photopolymerizable composition characterized by containing at least one titanocene compound capable of generating an active radical upon irradiation with light in the coexistence with the ring-increasing agent.

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 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, and glycerol acrylate. 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 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.

Among 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 the above-mentioned general formulas [I] to [VI] represented as (a) in the present invention.
Is a compound represented by the structural formula:

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 for the compounds represented by the above general formulas [I] to [VI], and as described later in Examples and Comparative Examples, the intramolecular N, N-dialkylaniline structure is converted into a tetrahydroquinoline structure derivative. Substantial increase in sensitivity was observed for 488 nm rays. 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] to [VI] of the sensitizer, R¹
~ R²⁸Each represents an alkyl group, or R
²~ R^Four, R⁶~ R¹¹, R¹³, R¹⁴, R¹⁶, R¹⁸~
R²⁰, R ^{twenty four}~ R²⁸Is an alkoxy group or
When it represents a ruthio group, it preferably has 1 to 10 carbon atoms.
It is particularly preferable that it has 1 to 5 carbon atoms, and straight chain
Or may have a side chain. R^{twenty two}, R²⁷, R²⁸
When each represents an aralkyl group, it has 1 to 5 carbon atoms.
And the condensed polycyclic aromatic residue or aromatic heterocyclic residue is 1
It is preferably from nuclei to 3 nuclei. R²⁷, R²⁸Is aryl
When it represents an oxy group, it is a condensed polycyclic aromatic residue or aromatic group.
The aromatic heterocyclic residue is preferably mononuclear to trinuclear, and
When it represents a ruboalkoxy group, it has 1 to 5 carbon atoms.
Preferably.

In the formula [III], Y represents a divalent atom or a divalent group, but it is common to use an oxygen atom or a sulfur atom as the divalent atom, and especially as the divalent group, Although not limited, for example, an alkylene group, an alkyleneoxy group, or the like is used. When the alkylene group is used, it preferably has 1 to 5 carbon atoms and may have a straight chain or a side chain.

From the standpoint of suitability for spectral sensitivity with respect to the emission wavelength of 488 nm of an argon ion laser, when Q and T each represent a condensed polycyclic aromatic hydrocarbon residue or an aromatic heterocyclic residue, 1 to 5 nuclei. Is preferable, and when A, B and D each represent a condensed polycyclic aromatic hydrocarbon residue or an aromatic heterocyclic residue, it is preferably 1 to 3 nuclei. Further, the preferable substituents of Q, T, A, B and D are alkyl groups having 1 to 10 carbon atoms, particularly preferably 1 to 5 carbon atoms, alkoxy groups, or bromine atom or chlorine atom. .

Typical examples of the compounds represented by the general formulas [I] to [VI] are shown below, but the compounds used in the present invention are not limited to these specific examples as long as the gist thereof is not exceeded. In the example of the general formula [I], unless otherwise stated, α = 0, β = 0, R ⁴ represents a hydrogen atom, and R ^{1 to} R ³ are the following julolidine ring structures.

[0041]

[Chemical 19]

Shall be represented. [Compound example]

[0043]

[Table 1]

[0044]

[Table 2]

[0045]

[Table 3]

[0046]

[Table 4]

[0047]

[Table 5]

[0048]

[Table 6]

The synthesis method of the above-mentioned general formula [I] is selected depending on the case. For example, it can be synthesized by condensing the corresponding acetyl compound and dialkylaminobenzaldehyde or the like using a base or an acid as a catalyst. I can. Next, for the compound represented by the general formula [II],
Typical examples thereof will be given, but unless otherwise specified, γ = 0, x; methylene group, R ^{5 to} R ⁷ are the following julolidine structures.

[0050]

[Chemical 20]

In the following notation, A is assumed to have the carbon atom at the right end of the ring structure shared with the ring containing the ketone structure. [Compound example]

[0052]

[Table 7]

[0053]

[Table 8]

[0054]

[Table 9]

The synthesis method of the general formula [II] described above is selected depending on the case. For example, an aromatic hydrocarbon or aromatic hetero compound having a cyclic skeleton containing an active methine group adjacent to a corresponding carbonyl group. It can be synthesized by condensing a dialkylaminobenzaldehyde or the like with a base or an acid as a catalyst.

Typical examples of the compounds represented by the general formulas [III] to [V] are shown below, but the compounds used in the present invention are not limited to these specific examples unless the gist thereof is exceeded. Absent. [Compound example]

[0057]

[Table 10]

[0058]

[Table 11]

[0059]

[Table 12]

[0060]

[Table 13]

[0061]

[Table 14]

[0062]

[Table 15]

The synthesizing method of the above-mentioned general formulas [III] to [V] is selected depending on the case.
According to the method described in JP-A-9, it can be synthesized by condensing an aromatic hydrocarbon or aromatic hetero compound having a corresponding active methyl group and dialkylaminobenzaldehyde or the like with a base or an acid as a catalyst.

Typical examples of the compound represented by the general formula [VI] are shown below. In the following examples, unless otherwise stated, λ = 0 and R ^{23 to} R ²⁵ are the following julolidine ring structures.

[0065]

[Chemical 21]

And R ²⁶ represents a hydrogen atom. [Compound example]

[0067]

[Table 16]

The synthesis method of the general formula [VI] described above is selected depending on the case. For example, first, a methyl-s-triazine derivative is usually prepared, and then a dialkylaminobenzaldehyde or the like is added to the base or It can be synthesized by condensing an acid as a catalyst.

The sensitizers represented by the general formulas [I] to [VI] 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 photopolymerization initiation system of the present invention is a titanocene compound represented by (b) in the present invention, which is capable of generating active radicals when irradiated with light in the coexistence with the above-mentioned sensitizer. .

The titanocene compound is described in, for example, JP-A-59 / 1984.
It can be appropriately selected and used from various titanocene compounds described in JP-A-152396 and JP-A-61-151197. More specifically, di-cyclopentadienyl-Ti-di-chloride, di-cyclopentadienyl-Ti-bis-phenyl, di-cyclopentadienyl-Ti-bis-2,3,4,5 , 6-Pentafluorophen-1-yl (hereinafter referred to as B-1), di-cyclopentadienyl-Ti-bis-2,3,5,6-tetrafluorophen-1-yl, di-cyclopenta Dienyl-Ti-bis-2,4,6-trifluorophenyl-
1-yl, di-cyclopentadienyl-Ti-bis-
2,6-difluorophen-1-yl, di-cyclopenta-dienyl-Ti-bis-2,4-di-fluorophen-1-yl, di-methylcyclopentadienyl-Ti
-Bis-2,3,4,5,6-pentafluorophenyl-
1-yl, di-methylcyclopentadienyl-Ti-bis-2,3,5,6-tetrafluorophen-1-yl, di-methylcyclopentadienyl-Ti-bis-
2,6-difluorophen-1-yl etc. can be mentioned.

The titanocene compound used in the photopolymerizable composition of the present invention can be preferably used alone or in combination of two or more kinds. The suitable use amount of the sensitizer and the titanocene compound constituting the photopolymerization initiation system used in the photopolymerizable composition of the present invention described above is not particularly limited, but the sensitizer is added to 100 parts by weight of the ethylene compound. Preferably 0.05 to 20 parts by weight, more preferably 0.2 to 1
0 parts by weight, preferably a titanocene compound is 0.5 to 10
It is suitable to use 0 parts by weight, more preferably 1 to 50 parts by weight.

In the photopolymerizable composition of the present invention, in addition to the above-mentioned sensitizer and titanocene compound, 2-mercaptobenzthiazole (hereinafter abbreviated as C-2), 2-
Mercaptobenzoxazole (hereinafter abbreviated as C-3),
A mercapto compound such as 2-mercaptobenzimidazole (hereinafter abbreviated as C-4), N-phenylglycine, dialkylaminobenzaldehyde, dialkylaminobenzoic acid ester and the like can be added.

The amount of these additives to be used is not particularly limited, but is 0.0 to 100 parts by weight of the ethylenic compound.
It is 5 to 40 parts by weight, preferably 0.2 to 20 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 in order to modify the composition and improve 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 adhesion, 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; 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%.

The photopolymerizable composition of the present invention may further contain a thermal polymerization inhibitor, a coloring agent, 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 preferred.

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 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 used 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 decrease 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 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 applied more suitably.

[0080]

EXAMPLES The present invention will be described in more detail with reference to Synthesis Examples, Examples, Comparative Examples and Reference Examples, but the present invention is not limited to these Examples unless the gist thereof is exceeded. . Examples 1 to 26, Comparative Examples 1 to 12 Using a whirler, a photosensitive composition coating solution having the following composition was applied on a grained and anodized aluminum sheet to a dry film thickness of 2 μm, and 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 the photosensitive material sample, and a 500 w xenon lamp (USHIO INC. ) OSB-1001A
/ 2) Glass filter (Toshiba Glass Co., Ltd., Y-4)
7 and KL-49) to obtain 480-490 nm
Was irradiated for 10 seconds. The exposed sample was 0.5% by weight of phenyl cellosolve, 1% by weight of sodium silicate, sodium alkylnaphthalene sulfonate (Perex NB
-L: Kao Co., Ltd., development was performed with an aqueous solution containing 0.5% by weight, and the minimum exposure amount necessary for image formation was calculated from the number of step steps of the obtained step-cured image,
The sensitivity of the photosensitive composition was used. The results are shown in Table-1.

[0082]

[Table 17] [Photosensitive composition coating liquid] Sensitizer and activator shown in Table-1 Methyl methacrylate / methacrylic acid / methyl acrylate copolymer 50 parts (weight average molecular weight 50,000, copolymerization ratio 80/10/10) Trimethylolpropane triacrylate 50 parts Victoria Pure Blue BOH 0.1 part Methyl Cellosolve 800 parts Tetrahydrofuran 50 parts

[0083]

[Table 18]

[0084]

[Table 19]

[0085]

[Table 20]

[0086]

[Table 21]

[0087]

[Table 22]

[0088]

[Table 23]

In Table 1, sensitizer: J represents the following julolidine ring structure.

[0090]

[Chemical formula 22]

Activator: C-1 is

[0092]

[Chemical formula 23]

C-5 represents N-phenylglycine, respectively.

Examples 27 to 32 The coated samples prepared in Examples 5, 10, 17, 18, 18, and 24 were stored under high temperature drying conditions of 65 ° C. and a humidity of 5% or less for 7 days and accelerated for aging. Next, these samples were subjected to the same exposure and development treatment as in Examples 1 to 26, and subsequently,
After applying ink with a developing ink (SPO-1, Konica Corp.), the ink adhesion (dirt) to the sample was visually inspected and the developability was evaluated (ink adhered,
The soiled sample shows that the developability of the non-image area decreased with time). As a result of the evaluation, the above sample did not adhere ink at all even after the passage of time, and maintained good developability.

Comparative Examples 13 to 18 Similarly to Examples 28 to 33, except that 20 parts of biimidazole C-1 was used instead of the titanocene compound B-1, deterioration of the non-image area with time was deteriorated. As a result of evaluation, ink adhesion was confirmed in all the samples, and a decrease in developability was observed.

[0096]

The photopolymerizable composition of the present invention is
In particular, it has extremely high sensitivity to a long-wavelength light of 488 nm and is excellent in developability of the non-image area after storage with time. Therefore, the composition is useful in a wide range of application fields, for example, printing plates such as planographic printing, intaglio printing, letterpress printing, photoresists for printed wiring and IC, dry film, images such as relief images and image duplication. It is industrially very useful because it can be used for forming, photocurable ink, paint, adhesive and the like.

Claims (1)

[Claims] 1. A photopolymerizable composition comprising 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) at least one of the sensitizers represented by the following general formulas [I] to [VI].
Seed (In the formula, R ¹ represents a hydrogen atom or an alkyl group, and R ^1
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,
R ⁴ represents a hydrogen atom, an alkyl group, an alkoxy group or a phenyl group, and Q has a mononuclear to pentanuclear fused polycyclic aromatic hydrocarbon residue or a substituent which may have a substituent. Optionally represents a mononuclear to pentanuclear aromatic heterocyclic residue, and α and β each represent 0 or 1. ) [Chemical 2] (In the formula, R ⁵ represents a hydrogen atom or an alkyl group, and R ^5
6 and R ⁷ each represent a hydrogen atom, an alkyl group, an alkoxy group or an alkylthio group, or R ⁵ and R ⁶ may be bonded to each other to form a ring structure,
A represents a mononuclear to trinuclear fused polycyclic aromatic hydrocarbon residue which may have a substituent or a mononuclear to trinuclear aromatic heterocyclic residue which may have a substituent. , X is (Wherein R ^{8 to} R ¹¹ each represent an alkyl group, an alkoxy group or a phenyl group, δ represents an integer of 1 to 3, ε represents an integer of 0 to 2), and γ represents 0 or Represents 1. ) [Chemical 4] (In the formula, R ¹² represents a hydrogen atom or an alkyl group;
¹³ and R ¹⁴ each represent a hydrogen atom, an alkyl group, an alkoxy group or an alkylthio group, or R ¹² and R ¹³ may be bonded to each other to form a ring structure,
B represents a mononuclear to trinuclear fused polycyclic aromatic hydrocarbon residue which may have a substituent or a mononuclear to trinuclear aromatic heterocyclic residue which may have a substituent. , Y represents a divalent atom or a divalent group, and ζ represents 1 or 2. ) [Chemical 5] (In the formula, R ¹⁵ represents a hydrogen atom or an alkyl group, and R ^15
16 represents a hydrogen atom, an alkyl group, an alkoxy group or an alkylthio group, or R ¹⁵ and R ¹⁶ may be bonded to each other to form a ring structure, and T may have a substituent. Represents a mononuclear to pentanuclear fused polycyclic aromatic hydrocarbon residue or a mononuclear to pentanuclear aromatic heterocyclic residue which may have a substituent, and θ and η represent 0 or 1 respectively. . ) [Chemical 6] (In the formula, R ¹⁷ represents a hydrogen atom or an alkyl group,
¹⁸ and R ¹⁹ each represent a hydrogen atom, an alkyl group, an alkoxy group, or an alkylthio group, or R ¹⁷ and R ¹⁸
May be bonded to each other to form a ring structure, R ²⁰ represents a hydrogen atom, an alkyl group, an alkoxy group or a phenyl group, and R ²¹ represents a hydrogen atom, an acetyl group or R ²² represents an alkyl group or an aralkyl group, and κ represents 0 to 2. D represents a mononuclear to trinuclear fused polycyclic aromatic hydrocarbon residue which may have a substituent or a mononuclear to trinuclear aromatic heterocyclic residue which may have a substituent. . ) [Chemical 8] (In the formula, R ²³ represents a hydrogen atom or an alkyl group;
²⁴ and R ²⁵ each represent a hydrogen atom, an alkyl group, an alkoxy group or an alkylthio group, or R ²³ and R ²⁴ may be bonded to each other to form a ring structure,
R ²⁶ represents a hydrogen atom, an alkyl group, an alkoxy group or a phenyl group, and R ²⁷ and R ²⁸ each represent an alkyl group, an aralkyl group, an alkoxy group, an aryloxy group,
Carboalkoxy groups, mononuclear to pentanuclear fused polycyclic aromatic hydrocarbon residues which may have a substituent, or mononuclear to pentanuclear aromatic heterocyclic residues which may have a substituent. A group or And λ represents 0 or 1. And (b) A photopolymerizable composition comprising at least one titanocene compound capable of generating an active radical upon irradiation with light in the coexistence with the ring-increasing agent.