JP3275439B2 - Photopolymerizable composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a photopolymerizable composition. In particular, the present invention relates to a photopolymerizable composition exhibiting 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 a compound containing an addition-polymerizable 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 A method in which a layer of a photopolymerizable composition is provided between two supports in which at least one of the above-mentioned photosensitive materials is transparent, and image exposure is performed from the transparent support side to cause a change in adhesive strength due to light. A method for forming an image by peeling the support after the application, a photosensitive material having a microcapsule layer provided by applying a microcapsule having a color material such as a photopolymerizable composition and a leuco dye in the content to the support 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 of forming a colored image, an image forming method utilizing a change in toner adhesion due to light of the photopolymerizable composition layer, and the like.

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

In recent years, with the development of image forming technology, there has been a strong demand for photopolymers having high adaptability to light rays in the visible region. It is a photosensitive material suitable for, for example, non-contact type projection exposure plate making or laser plate making using a visible light laser. Among these techniques, a 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 been made for photopolymerizable photosensitive materials containing a photopolymerization initiation system that can respond to light in the visible light range. For example, a system of hexaarylbiimidazole, a radical generator and a dye (Japanese Patent Publication No.
No. 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)
No. 3), a system of a substituted triazine and a merocyanine dye (Japanese Patent Application Laid-Open No. 54-115024), a system of a ketocoumarin and an activator (Japanese Patent Application Laid-Open Nos. 52-112681 and 58).
-15503, JP-A-60-88005),
System of a substituted triazine and a sensitizer (JP-A-58-29803)
JP-A-58-40302), a system of biimidazole, a styrene derivative, and a thiol (JP-A-59-56).
403), a system of an organic peroxide and a dye (JP-A-59
-140203 and JP-A-59-189340).

Examples of the use of titanocene in a 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 and JP-A-3-12403), a system of titanocene and a 3-ketocoumarin dye (JP-A-63-221110), and a titanocene and a xanthene dye further having an amino group or a urethane group. A system in which an addition-polymerizable ethylenically saturated double bond-containing compound is combined (JP-A-4-221958).
And JP-A-4-219756).

[0007]

However, these prior arts are certainly effective for visible light, but have the drawback of the prior art that the sensitivity is not so high and still insufficient from a practical point of view. Was. Further, a system of a sensitizing dye having a julolidine skeleton in a molecule and a hexaarylbiimidazole is described in, for example, JP-A-2-69. Although these systems are highly sensitive to 488 nm argon ion laser light, the non-image area (unexposed portion) developability decreases with storage over time, and a small amount of the photosensitive layer remains in the non-image area after development. Tend to.

[0008]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to overcome such difficulties and to obtain an excellent photopolymerizable composition. As a result, it has been found that addition polymerization having at least one ethylenic double bond is possible. And 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 presence of the sensitizer. As a result, the inventors have found that the sensitivity and the practicality are improved, and arrived at the present invention.

That is, an object of the present invention is to provide a photopolymerizable composition having higher sensitivity to visible light, especially to long wavelength light such as 488 nm. It is a further object of the present invention to provide a photopolymerizable composition having excellent developability even after storage over time. Another object of the present invention is to provide a photopolymerizable composition that enables higher-speed plate-making operations using a lower-power laser, for example, an air-cooled argon laser, for example, in the case of laser plate making with an argon ion laser. It is in.

[0010] Another object of the present invention is to provide a photopolymerizable composition which enables a plate-making operation which is extremely advantageous in terms of cost and time. Thus, 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
At least one sensitizer represented by I]

[0011]

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(Wherein R ¹ represents a hydrogen atom or an alkyl group, and R ² and R ³ each represent a hydrogen atom, an alkyl group, an alkoxy group or an alkylthio group;
R ¹ and R ² may be mutually bonded 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 each represent 0 or 1 . )

[0013]

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(Wherein, R ⁵ represents a hydrogen atom or an alkyl group; R ⁶ and R ⁷ each represent a hydrogen atom, an alkyl group, an alkoxy group or an alkylthio group;
R ⁵ and R ⁶ may be bonded to each other to form a ring structure, and A represents a mononuclear group which may have a substituent;
X represents a nuclear condensed polycyclic aromatic hydrocarbon residue or a mononuclear to trinuclear aromatic heterocyclic residue which may have a substituent;

[0015]

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

[0017]

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(Wherein 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 be bonded to each other to form a ring structure, and B represents 3 to 3 nuclei which may have a substituent.
Represents a condensed polycyclic aromatic hydrocarbon residue 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 Represents 1 or 2. )

[0019]

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(Wherein, 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 mutually bonded 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]

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(Wherein, 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 represent each other R ²⁰ may represent a hydrogen atom, an alkyl group, an alkoxy group or a phenyl group, and R ²¹ may represent a hydrogen atom, an acetyl group or

[0023]

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Wherein R ²² represents an alkyl group or an aralkyl group, and κ represents 0-2. 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]

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(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;
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 condensed polycyclic aromatic hydrocarbon residue which may have a substituent, or a substituent which may have a substituent Nuclear to pentanuclear aromatic heterocyclic residue or

[0027]

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

Hereinafter, the present invention will be described in detail. The compound capable of addition polymerization 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 is referred to as a photopolymerizable compound. When the active composition is irradiated with actinic rays, it is a compound having an ethylenically unsaturated double bond such as addition-cured and cured by the action of a photopolymerization initiation system as a second essential component, for example, The above-mentioned monomer having a double bond or a polymer having an ethylenically unsaturated double bond in a side chain or a main chain. Incidentally, the meaning of the monomer in the present invention is a concept corresponding to a so-called polymer substance, and therefore, a dimer other than the monomer in a narrow sense,
It also includes trimers and oligomers.

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

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. Acrylates such as pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, glycerol acrylate, and the acrylates of these exemplified compounds as methacrylates Methacrylic acid ester replaced with 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 the aromatic polyhydroxy compound with the unsaturated carboxylic acid include hydroquinone diacrylate, hydroquinone dimethacrylate, resorcin diacrylate, resorcin dimethacrylate, and pyrogallol triacrylate. The ester obtained by the esterification reaction between the unsaturated carboxylic acid and the polyhydric carboxylic acid and the polyhydric hydroxy compound is not necessarily a single substance, but typical examples include acrylic acid, phthalic acid and ethylene glycol. 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, and the like.

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

The polymer having an ethylenically unsaturated bond in the side chain is obtained by condensation polymerization of a divalent carboxylic acid having an unsaturated bond in the side chain such as itaconic acid, propylidene succinic acid, ethylidene malonic acid and 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 a side chain, for example, polyvinyl alcohol, poly (2-hydroxyethyl methacrylate), polyepichlorohydrin, etc. and acrylic acid,
A polymer obtained by a polymer reaction with an unsaturated carboxylic acid such as methacrylic acid or crotonic acid can also be suitably used.

Of the ethylenic compounds described above, 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 present invention is composed of a combination of two kinds of components, the first component of which is the above-mentioned general formula [I] to [VI] represented as (a) in the present invention.
A compound represented by the structural formula:

It has been found that all of these sensitizers have a tetrahydroquinoline structure in the molecule, thereby significantly increasing the sensitivity to visible light. This effect is particularly remarkable for the compounds represented by the aforementioned general formulas [I] to [VI], and as described later in Examples and Comparative Examples, an N, N-dialkylaniline structure in a molecule is converted to a derivative having a tetrahydroquinoline structure. A significant increase in sensitivity to 488 nm light was observed by substitution. The usefulness of this effect indicates that it is possible to apply an air-cooled argon laser having a low output in an image forming method using argon ion laser scanning.

In formulas (I) to (VI) of the sensitizer, R¹
~ R²⁸Each represents an alkyl group, or R
^Two~ R^Four, R⁶~ R¹¹, R¹³, R¹⁴, R¹⁶, R¹⁸~
R²⁰, R ^{twenty four}~ R²⁸Is an alkoxy group or an alkyl group, respectively.
When representing a luthio group, it preferably has 1 to 10 carbon atoms.
Particularly preferably, it has 1 to 5 carbon atoms.
Or may have a side chain. R^{twenty two}, R²⁷, R²⁸
Each represents an aralkyl group;
And the condensed polycyclic aromatic residue or aromatic heterocyclic residue is 1
It is preferably a nucleus to a trinuclear. R²⁷, R²⁸Is aryl
When representing an oxy group, a condensed polycyclic aromatic residue or aromatic
Preferably, the aromatic heterocyclic residue is mono- to tri-nuclear,
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. 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 be linear or have a side chain.

From the viewpoint of the spectral sensitivity 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. When A, B, and D each represent a condensed polycyclic aromatic hydrocarbon residue or an aromatic heterocyclic residue, it is preferably mononuclear to trinuclear. Further, preferred substituents of Q, T, A, B and D are alkyl groups, alkoxy groups having 1 to 10 carbon atoms, particularly preferably 1 to 5 carbon atoms, or bromine atoms or chlorine atoms. .

The 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 unless they exceed the gist. In the examples of the general formula [I], α = 0, β = 0, R ⁴ represents a hydrogen atom, and R ^{1 to} R ³ represent the following julolidine ring structures unless otherwise specified.

[0041]

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It is assumed that (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 general formula [I] described above is selected depending on the case. For example, it can be synthesized by condensing a corresponding acetyl compound with dialkylaminobenzaldehyde or the like using a base or an acid as a catalyst. I can do it. Next, for the compound represented by the general formula (II),
Typical examples thereof are as follows, unless otherwise specified in the following examples: γ = 0, x; a methylene group and R ^{5 to} R ^{7 each} have the following julolidine structure:

[0050]

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A represents that the two carbon atoms at the right end of the ring structure are shared with a ring containing a ketone structure in the following representation. (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 an aromatic hetero compound having a cyclic skeleton containing an active methine group adjacent to the corresponding carbonyl group And a dialkylaminobenzaldehyde or the like with a base or an acid as a catalyst.

The 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 they exceed the gist thereof. Absent. (Compound example)

[0057]

[Table 10]

[0058]

[Table 11]

[0059]

[Table 12]

[0060]

[Table 13]

[0061]

[Table 14]

[0062]

[Table 15]

The synthesis methods of the general formulas [III] to [V] described above are selected depending on the case.
No. 9 can be synthesized by condensing an aromatic hydrocarbon or an aromatic hetero compound having a corresponding active methyl group with a dialkylaminobenzaldehyde or the like using a base or an acid as a catalyst.

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

[0065]

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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, usually, first, a methyl-s-triazine derivative is prepared, and then a dialkylaminobenzaldehyde or the like is added thereto with a base or It can be synthesized by condensation using 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 suitably used alone or in combination of two or more. The second component constituting the photopolymerization initiation system of the present invention is a titanocene compound represented by (b) in the present invention and capable of generating an active radical when irradiated with light in the presence of the aforementioned sensitizer. .

The titanocene compound is disclosed in, for example, JP-A-59
And the like. Any of various titanocene compounds described in JP-A-152396 and JP-A-61-151197 can be appropriately selected and used. More specifically, di-cyclopentadienyl-Ti-di-chloride, di-cyclopentadienyl-Ti-bis-phenyl, di-cyclopentadienyl-Ti-bis-2,3,4,5 , 6-Pentafluorophenyl-1-yl (hereinafter referred to as B-1), di-cyclopentadienyl-Ti-bis-2,3,5,6-tetrafluorophenyl-1-yl, di-cyclopenta Dienyl-Ti-bis-2,4,6-trifluorophenyl-
1-yl, di-cyclopentadienyl-Ti-bis-
2,6-difluorophenyl-1-yl, di-cyclopenta-dienyl-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 and the like can be mentioned.

The titanocene compound used in the photopolymerizable composition of the present invention can be suitably used alone or in combination of two or more. Suitable amounts of the sensitizer and titanocene compound constituting the photopolymerization initiation system used in the above-described photopolymerizable composition of the present invention are not particularly limited, but the sensitizer is preferably 100 parts by weight of the ethylenic compound. Preferably 0.05 to 20 parts by weight, more preferably 0.2 to 1 part by weight.
0 parts by weight, preferably 0.5 to 10 parts by weight of the titanocene compound
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 sensitizer and the titanocene compound, 2-mercaptobenzthiazole (hereinafter abbreviated as C-2),
Mercaptobenzoxazole (hereinafter abbreviated as C-3),
Mercapto compounds such as 2-mercaptobenzimidazole (hereinafter abbreviated as C-4), N-phenylglycine, dialkylaminobenzaldehyde, dialkylaminobenzoic acid esters, and the like can be added.

The use amount of these additives is not particularly limited, but may be 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, it is preferable to further add an organic polymer substance as a binder for modifying the present composition and improving physical properties after photocuring, in addition to the above-mentioned core component. The binder may be appropriately selected according to the purpose of improving compatibility, film forming property, developability, adhesiveness and the like. Specifically, for example, for improving aqueous developability, acrylic acid copolymer, methacrylic acid copolymer, itaconic acid copolymer, partially esterified maleic acid copolymer, modified acidic cellulose having a carboxyl group in a side chain, Examples include polyethylene oxide and polyvinylpyrrolidone.

Polyether of epichlorohydrin with bisphenol A; soluble nylon; polyalkyl methacrylate or polyalkyl acrylate such as polymethyl methacrylate; alkyl methacrylate and acrylonitrile, acrylic acid for improving film strength and adhesiveness Copolymer of acrylonitrile with vinyl chloride, vinylidene chloride; copolymer of vinylidene chloride, chlorinated polyolefin, copolymer of vinyl chloride and vinyl acetate; poly with methacrylic acid, vinyl chloride, vinylidene chloride, styrene, etc. Vinyl acetate; copolymer of acrylonitrile and styrene; copolymer of acrylonitrile with butadiene and styrene; polyvinyl alkyl ether; polyvinyl alkyl ketone; polystyrene; polyamide; Phthalate; acetyl cellulose and polyvinyl butyral, and the like. These binders are preferably not more than 500% by weight based on the ethylenic compound, more preferably not more than 200%.
% Can be added and mixed.

The photopolymerizable composition of the present invention may further contain, if necessary, a thermal polymerization inhibitor, a coloring agent, a plasticizer, a surface protective agent, a leveling agent,
Coating aids and other additives can be added. Examples of the thermal polymerization inhibitor include hydroquinone, p-methoxyphenol, pyrogallol, catechol, and 2,6-di-
There are t-butyl-p-cresol, β-naphthol, and the like. Examples of the coloring agent include phthalocyanine pigments, azo pigments, carbon black, pigments such as titanium oxide, ethyl violet, crystal violet, azo dyes, and 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% and the amount of the coloring agent is 0.1% to 3% based on 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, and triacetyl glycerin. When is used, 10% or less can be added to the total weight of the ethylenic compound and the binder.

When using the photopolymerizable composition of the present invention,
The light-sensitive material can be prepared by forming a light-sensitive material without a solvent or dissolving it in a suitable solvent to form a solution, coating the solution on a support and drying. 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 two or more kinds can be used in combination.

The support applied when preparing the photosensitive material using the photopolymerizable composition of the present invention may be any of those commonly used. For example, sheets of metals such as aluminum, magnesium, copper, zinc, chromium, nickel, iron or alloys containing these as main components; fine paper, art paper,
Papers such as release paper; inorganic sheets such as glass and ceramics; polyethylene terephthalate, polyethylene, polymethyl methacrylate, polyvinyl chloride, vinyl chloride
There are polymer sheets such as vinylidene chloride copolymer, polystyrene, 6-nylon, cellulose triacetate, cellulose acetate butyrate, and the like.

Further, the photopolymerizable composition of the present invention may be further provided with a known technique for preventing adverse effects such as sensitivity reduction and storage stability deterioration due to oxygen, for example, providing a peelable transparent cover sheet on a photosensitive layer. A low oxygen permeable waxy substance,
A coating layer of a water-soluble polymer or the like may be provided.
The exposure light source applicable to the composition of the present invention is not particularly limited, but 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, and a visible light of 400 nm or more such as an argon ion laser. General-purpose light sources can be more suitably applied.

[0080]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to Synthesis Examples, Examples, Comparative Examples, and Reference Examples, but the present invention is not limited to these Examples unless it exceeds the gist thereof. . Examples 1-26, Comparative Examples 1-12 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 as to have a dry film thickness of 3 μm.

Next, a step tablet (manufactured by Kodak Co., Ltd.) in which the light intensity is attenuated by 1 / √2 for each additional step is brought into close contact with the photosensitive material sample, and a 50 cm to 500 w xenon lamp (USHIO Inc.) OSB-1001A
/ 2) Glass filter (Y-4, manufactured by Toshiba Glass Co., Ltd.)
7 and 480-490 nm obtained through KL-49)
For 10 seconds. Exposure samples were phenyl cellosolve 0.5% by weight, sodium silicate 1% by weight, 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 required for image formation was calculated from the number of steps in the obtained step-cured image,
The sensitivity of the photosensitive composition was used. Table 1 shows the results.

[0082]

[Table 17] [Coating solution for photosensitive composition] 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 a julolidine ring structure shown below.

[0090]

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Activator: C-1 is

[0092]

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C-5 represents N-phenylglycine, respectively.

Examples 27 to 32 The coated samples prepared in Examples 5, 10, 17, 18, 21, and 24 were stored for 7 days under high-temperature drying conditions of 65 ° C. and a humidity of 5% or less, and accelerated with time. Next, these samples were subjected to the same exposure and development processing as in Examples 1 to 26.
After the ink was applied with a developing ink (SPO-1, Konica Corporation), the ink adhesion (dirt) to the sample was visually inspected, and the developability was evaluated.
The stained sample indicates that the developability of the non-image area decreased with time.) As a result of the evaluation, no ink adhered to the above sample even after the elapse of time, and good developability was maintained.

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

[0096]

The photopolymerizable composition of the present invention has a visible light,
In particular, it has extremely high sensitivity to long wavelength light of 488 nm, and has excellent developability of non-image areas after storage over time. Therefore, the composition is useful in a wide range of application fields, for example, for the preparation of printing plates such as lithographic, intaglio, letterpress, photoresist for dry wiring and ICs, dry films, images such as relief images and image reproduction. It is industrially extremely useful because it can be used for forming, photocurable inks, paints, adhesives and the like.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-2-69 (JP, A) JP-A-54-155292 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) G03F 7/031

Claims (1)

(57) [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. The photopolymerization initiation system is (a) at least one of sensitizers represented by the following general formulas [I] to [VI].
Species 1 (Wherein, R ¹ represents a hydrogen atom or an alkyl group;
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 mutually bonded 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 condensed polycyclic aromatic hydrocarbon residue or a substituent which may have a substituent. Represents a mononuclear to pentanuclear aromatic heterocyclic residue, and α and β each represent 0 or 1. ) (Wherein, R ⁵ represents a hydrogen atom or an alkyl group;
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. ) (Wherein 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 mutually bonded 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. ) (Wherein, R ¹⁵ represents a hydrogen atom or an alkyl group;
¹⁶ represents a hydrogen atom, an alkyl group, an alkoxy group or an alkylthio group, or R ¹⁵ and R ¹⁶ may be mutually bonded 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 each represent 0 or 1 . ) (Wherein, 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 Wherein 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. . ) (Wherein 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 mutually bonded 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 condensed polycyclic aromatic hydrocarbon residue which may have a substituent, or a mononuclear to pentanuclear aromatic heterocyclic residue which may have a substituent 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 presence of the ring-enhancing agent.