JPH06301208A - Photopolymerizable composition - Google Patents

Abstract

PURPOSE:To obtain a photopolymerizable compsn. having high sensitivity for long wavelength rays such as visible rays by using an addition-polymerizable compd. having an ethylene-type unsatd. double bond. CONSTITUTION:The photopolymerizable compd. has at least an addition- polymerizable compd. and a photopolymn. initiating system. The addition- polymerizable compd. has at least one ethylene-type unsatd. double bond. The photopolymn. initiating system contains (a) a sensitizer expressed by formula I and (b) a titanocene compd. which can produce active radicals during irraditioan of light in the presence of the sensitizer. In formula I, R<1>, R<2> are hydrogen atoms, alkyl groups, alkoxy groups, R<3>, R<4> are alkyl groups, and X is a cyan group or group expressed by formula II. In formula II, ring A is a residue of one- or two-nucleus condensed polycyclic aromatic hydrocarbon or one- or two-nucleus aromatic heterocyclic residue, and Y is a bivalent atom or bivalent group.

Description

Detailed Description of the Invention

[0001]

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

[0002]

2. Description of the Related Art Conventionally, many image forming methods utilizing a photopolymerization system are known. For example, a photopolymerizable composition comprising a compound containing an addition-polymerizable ethylenic double bond, a photopolymerization initiator, and an organic polymer binder optionally used is prepared, and the photopolymerizable composition is supported. A photosensitive material having a layer of 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, there is a method of forming an image by peeling the support, and an image forming method utilizing the change of toner adhesion of the photopolymerizable composition layer due to light. Conventionally, benzoyl, benzoin alkyl ether, benzyl ketal, benzophenone, anthraquinone, benzyl, Michler's ketone, etc. have been used as the photopolymerization initiator of the photopolymerizable composition applied to these methods. However, these photopolymerization initiators have a photopolymerization initiation ability of 4 nm or less in the ultraviolet region of 400 nm or less.
It is significantly lower for light in the visible region above 00 nm and thus has limited the range of applications of photopolymerizable compositions containing them.

In recent years, with the development of image forming technology, there has been a strong demand for photopolymers having a high sensitivity 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 oscillating beam of visible light of an argon ion laser is considered to be one of the most promising techniques in the future.

Several proposals have hitherto been made for a photopolymerizable composition containing a photopolymerization initiation system which is sensitive to light rays in the visible light region. For example, a system of hexaarylbiimidazole, a radical generator and a dye (Japanese Patent Publication No.
5-37377), a system of hexaarylbiimidazole and (p-dialkylaminobenzylidene) ketone (JP-A-47-2528, JP-A-54-155292).
Each of the above publications), a system of a cyclic cis-α-dicarbonyl compound and a dye (JP-A-48-84183), a system of a substituted triazine and a merocyanine dye (JP-A-54-151024).
No.), a system of ketocoumarin and an activator (JP-A-52-1).
12681, JP-A-58-15503, JP-A-60
-88005), a system of substituted triazine and a sensitizer (JP-A-58-29803, JP-A-58-40302).
Each of the above publications), biimidazole, a styrene derivative, a thiol system (JP-A-59-56403), an organic peroxide-dye system (JP-A-59-140203, JP-A-59-140203).
9-189340), and examples of using titanocene in a photopolymerization initiation system include JP-A-59-152396,
JP-A-61-151197, JP-A-63-10602
JP-A-63-41484, JP-A-2-291,
JP-A-3-12403, JP-A-3-20293, JP-A-3-27393, and JP-A-3-52050, as well as titanocene and xanthene dyes, and addition-polymerizable ethylenic saturated diamine having an amino group or a urethane group. A system in which a compound containing a heavy bond is combined (JP-A-4-221958
And Japanese Patent Application Laid-Open No. 4-219756), systems of titanocene and 3-ketocoumarin dyes (Japanese Patent Application Laid-Open No. 63-22110), and the like.

[0005]

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

[0006]

Means for Solving the Problems As a result of intensive investigations by the present inventors to overcome such difficulties and obtain an excellent photopolymerizable composition, the present inventors have found that at least a compound capable of addition polymerization and a photopolymerization initiation system are included. A photopolymerizable composition in which the addition-polymerizable compound has at least one ethylenically unsaturated double bond, and the photopolymerization initiation system has a specific ketocoumarin skeleton. Further, they have found that by containing at least one titanocene compound capable of generating an active radical upon irradiation with light in the coexistence with the sensitizer, high sensitivity and high practicality are achieved, and the present invention has been accomplished.

That is, an object of the present invention is to provide a photopolymerizable composition which is more sensitive to long wavelength light such as visible light. Another object of the present invention is to provide a photopolymerizable composition that enables a higher speed plate making operation 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. It is in.

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) Sensitizer represented by the following general formula [I]

[0009]

[Chemical 3] (In the formula, R ¹ and R ² each represent a hydrogen atom, an alkyl group, an alkoxy group or an alkylthio group, and R ³
And R ⁴ each represents an alkyl group, R ¹ and R ³ and / or R ² and R ⁴ may be bonded to each other to form a ring structure, and X is a cyan group or

[0010]

[Chemical 4] Represents a mononuclear or dinuclear fused polycyclic aromatic hydrocarbon residue or a mononuclear or dinuclear aromatic heterocyclic residue, and Y represents a divalent atom or a divalent group. ) And (b) a photopolymerizable composition containing a titanocene compound capable of generating an active radical upon irradiation with light in the coexistence with the sensitizer. Easily achieved by. Less than,
The present invention will be described in detail. The addition-polymerizable compound having at least one ethylenically unsaturated double bond contained as the first essential component in the photopolymerizable composition of the present invention (hereinafter abbreviated as “ethylenic compound”) is When the polymerizable composition is irradiated with actinic rays, 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,
It includes dimers, trimers, and oligomers in addition to the narrowly defined monomers.

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

The ester of the aliphatic polyhydroxy compound and the unsaturated carboxylic acid is not limited, but specific examples thereof include ethylene glycol diacrylate, triethylene glycol diacrylate, trimethylolpropane triacrylate, trimethylolethane triacrylate. Acrylic esters such as pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, glycerol acrylate, etc. Methacrylic acid ester replaced, Itaconic acid ester similarly replaced with itaconate Crotonate is maleic acid ester, and was replaced with crotonic acid ester or maleate was replaced.

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

Other examples of the ethylenic compound used in the present invention include acrylamides such as ethylenebisacrylamide; allyl esters such as diallyl phthalate;
Vinyl group-containing compounds such as divinyl phthalate are useful. The polymer having an ethylenically unsaturated bond in the main chain described above is, for example, a polyester obtained by a polycondensation reaction of an unsaturated divalent carboxylic acid and a dihydroxy compound,
There are polyamides and the like obtained by polycondensation reaction of unsaturated divalent carboxylic acid and diamine. The polymer having an ethylenically unsaturated bond in the side chain is a condensation polymer of a dicarboxylic acid having an unsaturated bond in the side chain, such as itaconic acid, propylidene succinic acid, ethylidene malonic acid, etc. and a dihydroxy or diamine compound. . Further, a polymer having a functional group having a reactive activity such as a hydroxy group or a methyl halide group in its side chain, for example, polyvinyl alcohol, poly (2-hydroxyethyl methacrylate), polyepichlorohydrin, etc. and acrylic acid, methacrylic acid, crotonic acid, etc. Polymers obtained by the macromolecular reaction with the unsaturated carboxylic acid can also be suitably used.

Of the above-mentioned ethylenic compounds, acrylic acid ester or methacrylic acid ester monomers can be particularly preferably used. Next, the photopolymerization initiation system which is the second essential component of the photopolymerization composition of the present invention will be described. The photopolymerization initiation system of the present invention is composed of a combination of two kinds of components, and the first component thereof is the compound represented by the above general formula [I] represented as (a) in the present invention. These sensitizers include, but are not limited to, for example, the following (1) and (2), as described in JP-B-37-10186, JP-B-37-23738 and JP-A-48-80122. A synthetic method such as (3) is known.

[0016]

[Chemical 5]

[0017]

[Chemical 6]

[0018]

[Chemical 7]

When R ^{1 to} R ³ in the general formula [I] each represent an alkyl group, it preferably has 1 to 6 carbon atoms, particularly preferably 1 to 3 carbon atoms, and is linear. Or it may have a side chain. R ¹ , R
^{When 2} represents an alkoxy group or an alkylthio group, the number of carbon atoms on the carbon chain side is particularly preferably 1 to 3, respectively. Y represents a divalent atom or a divalent group, and it is common to use an oxygen atom or a sulfur atom as the divalent atom, and the divalent group is not particularly limited, but for example, an alkylene group, An alkyleneoxy group or the like is used, and when it is an alkylene group, it has 1 to 5 carbon atoms.
Is preferred, and it may be a straight chain or may have a side chain. From the viewpoint of spectral suitability for an emission wavelength of 488 nm of an argon ion laser, when the ring A represents a condensed polycyclic aromatic hydrocarbon residue or an aromatic heterocyclic residue, it is 1 to 3 nuclei. Preferably, R ¹ and R ³ and R ² and R ⁴ are bonded to each other to form the following julolidine ring structure.

[0020]

[Chemical 8] Typical examples of the sensitizer represented by the general formula [I] are shown below, but the sensitizer represented by the general formula [I] used in the present invention is not limited to these specific examples. In the following examples, when R ¹ , R ² , R ³ and R ⁴ have the following structures,

[0021]

[Chemical 9] R ^{1 to} R ⁴ ; represented by julolidine ring.

[0022]

[Table 1]

In the present invention, at least one of the above-mentioned sensitizers is selected for use. The second component constituting the photoinitiating system of the present invention is a titanocene compound capable of generating an active radical when irradiated with light in the coexistence with the sensitizer represented by (b) in the present invention. The titanocene compound is described in, for example, JP-A-59-152.
It can be appropriately selected from various titanocene compounds described in JP-A No. 396 and JP-A No. 61-151197. More specifically, dicyclopentadienyl-Ti-di-chloride, dicyclopentadienyl-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-cyclopentadi Enyl-Ti-bis-2,4,6-trifluorophen-1-
Di-cyclopentadienyl-Ti-bis-2,6
-Difluorophen-1-yl, di-cyclopentadienyl-Ti-bis-2,4-di-fluorophen-1-
Di-methylcyclopentadienyl-Ti-bis-
2,3,4,5,6-pentafluorophen-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 suitable amounts of the sensitizer and the titanocene compound constituting the photopolymerization initiation system used in the above-described photopolymerizable composition of the present invention are not particularly limited, but 100 parts by weight of the ethylenic compound is used. The sensitizer is preferably 0.
05 to 20 parts by weight, more preferably 0.2 to 10 parts by weight, the titanocene compound is preferably 0.5 to 20 parts by weight, more preferably 0.5 to 10 parts by weight.

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

To improve the film strength and adhesion, a polyether of epichlorohydrin and bisphenol A; soluble nylon; polyalkyl methacrylate 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 coated on a support and dried. Examples of the solvent include methyl ethyl ketone, cyclohexanone, butyl acetate, amyl acetate, ethyl propionate, toluene, xylene, monochlorobenzene, carbon tetrachloride, trichloroethylene,
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. visible light of 400 nm or more. A general-purpose light source can be used more suitably.

[0032]

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

Examples 1 to 6 and Comparative Examples 1 to 6 On a grained and anodized aluminum sheet, using a whirler, a photosensitive composition coating solution having the following composition was applied to a dry film thickness of 2 μm. Then, a polyvinyl alcohol aqueous solution was applied on the surface so that the dry film thickness was 3 μm to prepare a photosensitive material sample.

Next, a xenon lamp; UI-501C manufactured by USHIO INC. Was used as a sample of this light-sensitive material, and a spectral sensitivity measuring device manufactured by Narumi Co., Ltd. was used so that the horizontal axis shows wavelength and the vertical axis shows logarithmically weak light intensity. For 10 seconds. The exposed sample was developed with an aqueous solution containing 2% by weight of butyl cellosolve and 1% by weight of sodium silicate, and the minimum exposure amount required for forming a photocured image was calculated from the height of the obtained cured image. And the sensitivity. The results are shown in Table-1.

[0035]

[Table 2] [Photosensitive composition coating liquid] Methyl methacrylate / methacrylic acid / methyl acrylate copolymer ... 50 parts (weight average molecular weight 45,000, copolymerization ratio 70/10/20 ... 50 parts) trimethylolpropane Triacrylate: 50 parts Victoria Pure Blue BOH: 0.1 part Methyl cellosolve: 800 parts Tetrahydrofuran: 50 parts Sensitizer: (described in Table-1) Titanocene compound: (described in Table-1)

[0036]

[Table 3] In Table 1, sensitizers [S-1], [S-2], and [S-3] are respectively

[0037]

[S-1] Eosin Yellow Issue

[0038]

[Chemical 11]

[0039]

[Chemical 12] Represents an active radical generator [C-1], [C-
2] and [C-3] are respectively

[0040]

[Chemical 13]

[0041]

[Chemical 14]

[0042]

[Chemical 15] Represents

[0043]

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

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Claims (1)

[Claims] 1. A photopolymerizable composition containing at least an addition-polymerizable compound and a photopolymerization initiation system, wherein the addition-polymerizable compound has at least one ethylenically unsaturated double bond, The polymerization initiation system is (a) a sensitizer represented by the following general formula [I]: (In the formula, R ¹ and R ² each represent a hydrogen atom, an alkyl group, an alkoxy group or an alkylthio group, and R ³
And R ⁴ each represent an alkyl group, and R ¹ and R ³
And / or R ² and R ⁴ may be bonded to each other to form a ring structure, and X is a cyano group or Represents a mononuclear or dinuclear fused polycyclic aromatic hydrocarbon residue or a mononuclear or dinuclear aromatic heterocyclic residue, and Y represents a divalent atom or a divalent group. ) And (b) a photopolymerizable composition containing a titanocene compound capable of generating an active radical upon irradiation with light in the coexistence with the sensitizer.