JP3355753B2 - Photopolymerizable composition and photosensitive material - 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 high sensitivity to light in the visible region.

[0002]

2. Description of the Related Art Conventionally, many image forming methods using a photopolymerization system are known. For example, a photopolymerizable composition comprising an addition-polymerizable compound containing an ethylenic double bond, a photopolymerization initiator, and an organic polymer binder used as desired is prepared, and the photopolymerizable composition is supported. Create a light-sensitive material with a layer of photopolymerizable composition applied to the body, image-expose the desired image, polymerize and cure the exposed part, and dissolve and remove the unexposed part to form a cured relief image Wherein the photosensitive material is provided with a layer of a photopolymerizable composition between two supports, at least one of which is transparent, and is subjected to image exposure from the transparent support side to cause a change in adhesive strength due to light. After that, there is a method of forming an image by peeling off the support, and an image forming method utilizing a change in toner adhesion of the photopolymerizable composition layer due to light. Conventionally, benzoin, benzoin alkyl ether, benzyl ketal, benzophenone, anthraquinone, benzyl, or Michler's ketone has been used as a photopolymerization initiator of the photopolymerizable composition applied to these methods.

[0003] However, these photopolymerization initiators are 4
Compared with the photopolymerization initiation ability for light in the ultraviolet region of 00 nm or less, that for light in the visible region of 400 nm or more is remarkably low, thus limiting the application range of the photopolymerizable compositions containing them.

In recent years, with the development of image forming technology, there has been a strong demand for photopolymers having high sensitivity 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.

[0005] Several proposals have heretofore been made with respect to a photopolymerizable composition containing a photopolymerization initiation system capable of responding to light in the visible light region. For example, a system of hexaarylbiimidazole and (p-dialkylaminobenzylidene) ketone (JP-A-47-2528, JP-A-54-155)
No. 292, JP-A-56-166154), a system of ketocoumarin and an activator (JP-A-52-112681,
JP-A-58-15503 and JP-A-60-88005), and a system of a substituted triazine and a sensitizer (JP-A-54-15803).
No. 15,1024, JP-A-58-29803, JP-A-58-29803
Nos. 8-40302), a system of biimidazole, a styrene derivative, and a thiol (JP-A-59-56403), and a system of an organic peroxide and a dye (JP-A-59-1402).
03, JP-A-59-189340) and others,
A system of a titanocene compound and a sensitizer (JP-A-63-2211)
No. 10, JP-A-4-26154, JP-A-4-2197
No. 56, each publication). Although these are effective to some extent, they are still not sufficiently sensitive from a practical point of view, and improved techniques have been desired.

Although various photopolymerization initiators containing a titanocene compound have been known, many of them have been directed to light in a short wavelength region. On the other hand, as the starting system sensitive to light in the visible region, a system combined with ketocoumarin as described above (Japanese Patent Laid-Open No. 63-221110)
Or a system combined with a soluble substance of eosin alcohol (Japanese Unexamined Patent Publication No.
-26154 and JP-A-4-219756). However, they were still insufficiently sensitive.

On the other hand, techniques for adding a tertiary amine such as triethanolamine or a derivative thereof to a titanocene-containing composition have been suggested in some literatures (for example, JP-A-63-163452, JP 63
These publications have photosensitivity mainly in a short wavelength region. Normally, the tertiary amines used in these compounds have their main absorption at short wavelengths, and therefore their effectiveness in the long wavelength region cannot always be expected. In fact, almost no reports have been found in which they have been confirmed. Absent.

[0008]

DISCLOSURE OF THE INVENTION The present inventors investigated the effect of a system in which a titanocene compound and various sensitizers for visible light were combined by further adding various tertiary amine derivatives. As a result, many of the above amine derivatives were actually ineffective or only showed a desensitizing effect,
Surprisingly, it has been found that only very specific dialkylaminobenzoic acid ester compounds are effective, and the present invention has been achieved.

[0009] That is, an object of the present invention is to provide a photopolymerizable composition having higher sensitivity to long wavelength light such as visible light. Thus, an object of the present invention is to provide at least one ethylenically unsaturated double bond capable of addition polymerization.
In a photopolymerizable composition containing a compound having two or more compounds and a photopolymerization initiation system, the photopolymerization initiation system has a wavelength of 450 nm in the coexistence of (a) a titanocene compound and (b) the titanocene compound.
A sensitizer having a main photosensitive region or an absorption maximum at a longer wavelength, and (c) at least one compound represented by the following general formula (i), (ii) or (iii)

[0010]

Embedded image

Wherein R ¹ -R ² and R ⁴ -R ¹¹ are
Each represents an alkyl group having 1 to 4 carbon atoms, and R ³ represents an alkyl group having 1 to 20 carbon atoms. ) Is easily achieved by a photopolymerizable compound characterized by containing Hereinafter, the present invention will be described in detail.

The compound having at least one addition-polymerizable ethylenically unsaturated double bond (hereinafter abbreviated as "ethylenic compound") contained as a first essential component in the photopolymerizable composition of the present invention. When the photopolymerizable composition is irradiated with actinic rays, it is a compound having an ethylenically unsaturated double bond that is addition-polymerized and cured by the action of a photopolymerization initiation system, which is the second essential component. And a polymer having an ethylenically unsaturated double bond in the side chain or main chain, for example. The meaning of the monomer in the present invention is a concept corresponding to a so-called polymer substance, and therefore includes not only a monomer in a narrow sense but also a dimer, a trimer, and an oligomer. .

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, and 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 and the unsaturated carboxylic acid include hydroquinone diacrylate, hydroquinone dimethacrylate, resorcin diacrylate, resorcin dimethacrylate, and pyrogallol triacrylate.

The ester obtained by the esterification reaction of the unsaturated carboxylic acid with the polyvalent carboxylic acid and the polyvalent hydroxy compound is not always a single ester, but typical examples include acrylic acid, phthalic acid, and the like. Examples include condensates of ethylene glycol, condensates of acrylic acid, maleic acid, and diethylene glycol, condensates of methacrylic acid, terephthalic acid, and pentaerythritol, and condensates of acrylic acid, adipic acid, butanediol, and glycerin.

In addition to the above ester (meth) acrylates, there are so-called urethane (meth) acrylates and epoxy (meth) acrylates. The former can be prepared by an addition reaction between a polyvalent isocyanate and a hydroxyacrylic ester, and the latter can be prepared by an addition reaction between a polyvalent epoxy compound and a hydroxyacrylic ester.

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, or a polymer obtained by mixing an unsaturated divalent carboxylic acid with a diamine. There is a polyamide obtained by a polycondensation reaction. Polymers having an ethylenically unsaturated bond in the side chain are divalent carboxylic acids having an unsaturated bond in the side chain, such as itaconic acid, propylidene succinic acid,
There is a condensation polymer of ethylidenemalonic acid or the like with 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 a side chain, for example, polyvinyl alcohol, poly (2-hydroxyethyl methacrylate), polyepichlorohydrin, etc., and acrylic acid, methacrylic acid, crotonic acid, etc. A polymer obtained by a polymer reaction with an unsaturated carboxylic acid of formula (I) can also be suitably used.

Of the 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 photopolymerization composition of the present invention, will be described. The photopolymerization initiation system of the present invention is composed of a combination of three components,
The first component is a titanocene compound represented as (a) in the present invention. The titanocene compound is
Although not particularly limited, for example, JP-A-59-152396
And various titanocene compounds described in JP-A-61-151197 and the like. More specifically, di-cyclopentadienyl-Ti-di-chloride, di-cyclopentadienyl-
Ti-bis-phenyl, di-cyclopentadienyl-T
i-bis-2,3,4,5,6-pentafluorophenyl-1-yl, dicyclopentadienyl-Ti-bis-
2,3,5,6-tetrafluorophenyl-1-yl, di-cyclopentadienyl-Ti-bis-2,4,6-trifluorophenyl-1-yl, di-cyclopentadienyl-Ti- Bis-2,6-di-fluorophenyl-1-yl, di-cyclopentadienyl-Ti-bis-2,4-
Di-fluorophenyl-1-yl, di-methylcyclopentadienyl-Ti-bis-2,3,4,5,6-pentafluorophenyl-1-yl, di-methylcyclopentadienyl-Ti-bis -2,3,5,6-tetrafluorophenyl-1-yl, di-methylcyclopentadienyl-
Ti-bis-2,6-difluorophenyl-1-yl, di-cyclopentadienyl-Ti-bis-2,6-difluoro-3- (pyr-1-yl) -phenyl-1-yl (hereinafter, referred to as A-1).

Next, the sensitizer which is the second component (b) of the photopolymerization initiation system of the present invention will be described. The sensitizer has a wavelength of 450 nm in the presence of the titanocene compound.
Any substance having a main photosensitive region or an absorption maximum at a longer wavelength can be used. In the present invention, the main photosensitive area means a main photosensitive area which is not the absorption maximum.

Specific examples of preferred sensitizers include, for example, 2,6-diethyl-1,3,5,7,8-pentamethylpyrromethene-BF ₂ described in JP-A-5-241338. Complex (hereinafter abbreviated as B-1), 1,
3,5,7,8- pyromethene complexes such as pentamethyl pyro main polymethylpentene -BF ₂ complex; eosin, ethyl eosin (hereinafter, B-2 for short), erythrosine, fluorescein,
Xanthene dyes such as rose bengal; 1- (1-methylnaphtho [1,2-d] thiazole-2 (1H) -ylidene-4- (2,3,6,7) tetrahydro-1H,
5H-benzo [ij] quinolin-9-yl) -3-buten-2-one, 1- (3-methylbenzothiazole-
2 (3H) -ylidene-4- (p-dimethylaminophenyl) -3-buten-2-one (hereinafter abbreviated as B-3)
Ketothiazoline compounds described in JP-A-2-69; 2- (p-dimethylaminostyryl)
-Naphtho [1,2-d] thiazole, 2- [4- (p-
Dimethylaminophenyl) -1,3-butadienyl]-
JP-B-2-55446, JP-B-2-303 such as naphtho [1,2-d] thiazole (hereinafter abbreviated as B-4)
No. 21, styryl or phenylbutadienyl heterocyclic compound; 2,4-diphenyl-6- (p
-Dimethylaminostyryl) -1,3,5-triazine (hereinafter abbreviated as B-5), 2,4-diphenyl-6-
(([2,3,6,7] tetrahydro-1H, 5H-benzo [ij] quinolinidin-9-yl) -1-ethene-2
JP-A-5-yl such as 1,3,5-triazone
A triazine compound described in JP-A-07761; 9-
Phenanthryl-(([2,3,6,7] tetrahydro-1H, 5H-benzo [ij] quinolinidin-9-yl)
Japanese Patent Application No. 4-288818 such as -1-ethen-2-yl) ketone (hereinafter abbreviated as B-6), 2,5-bis (p-dimethylaminocinnamylidene) cyclopentanone.
Aminophenyl unsaturated ketone compounds described in JP-A No. 47-2528 and 5,10,15,20-
Examples thereof include porphyrins such as tetraphenylporphyrin and hematoporphyrin (hereinafter abbreviated as B-7). As described above, preferred sensitizers have been exemplified, and among them, a pyromethene complex is particularly preferred.

Next, the compound of the third component (c) of the photopolymerization initiation system of the present invention will be described. As described above, one or more of the compounds represented by the general formulas (i), (ii) and (iii) are used. General formula (i)
In (iii), R ^{1 to} R ² and R ^{4 to} R ¹¹ are
Each represents an alkyl group having 1 to 4 carbon atoms, and R ³ represents an alkyl group having 1 to 20 carbon atoms, each of which may be linear or have a branched structure. R ³ preferably has 1 to 8 carbon atoms, especially 1 carbon atom.
-4 is preferred.

Specific examples of the compounds represented by formulas (i) to (iii) include, for example, ethyl p-dimethylaminobenzoate (hereinafter abbreviated as C-1),
-Diethylaminobenzoic acid ethyl ester, p-dimethylaminobenzoic acid isopropyl ester (hereinafter referred to as C-2
Abbreviated), p-dimethylaminobenzoic acid-n-butyl ester, p-dimethylaminobenzoic acid-n-octyl ester or p-di-n-butylaminobenzoic acid ethyl ester, etc .; alkyl esters of dialkylaminobenzoic acid; Bisaminobenzophenones such as 4,4'-bis (dimethylamino) benzophenone (hereinafter abbreviated as C-3), 4,4'-bis (diethylamino) benzophenone or 4,4'-bis (diisopropylamino) benzophenone; And bisaminobenzyl such as' -bis (dimethylamino) benzyl (hereinafter abbreviated as C-4) or 4,4'-bis (diethylamino) benzyl. Among them, dialkylaminobenzoic acid alkyl esters are particularly preferred.

The components (a), (b) and (c) of the photopolymerization initiation system of the present invention described above are used in an amount of 0.1 to 20% by weight based on the ethylenic compound. 0.1% to 15% by weight of component (b) and 0.1% by weight of component (c).
Generally, it is in the range of 1 to 40% by weight.

The photopolymerizable composition of the present invention may further comprise an organic polymer substance as a binder for modifying the composition and improving physical properties after photocuring, in addition to the above-mentioned components. it can. 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 and bisphenol A for improving film strength and adhesion; soluble nylon; polyalkyl methacrylate and polyalkyl acrylate such as polymethyl methacrylate; alkyl methacrylate and acrylonitrile, acrylic acid, methacrylic acid Copolymer of acrylonitrile with vinyl chloride and vinylidene chloride; copolymer of vinylidene chloride, chlorinated polyolefin, copolymer of vinyl chloride and vinyl acetate; polyvinyl acetate; Copolymer of acrylonitrile and styrene; copolymer of acrylonitrile and butadiene, styrene; polyvinyl alkyl ether; polyvinyl alkyl ketone; polystyrene; polyamide; polyurethane; polyethylene terephthalate isophthalate Mention may be made of acetyl cellulose and polyvinyl butyral. These binders can be added and mixed in a weight ratio of generally 500% or less, preferably 200% or less with respect to the ethylenic compound.

The photopolymerizable composition of the present invention may further contain, if necessary, a thermal polymerization inhibitor, a coloring agent, a plasticizer, a 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 or the coloring agent is 0.01 to 3% based on the total weight of the ethylenic compound and the binder, and the amount of the coloring agent is 0.1 to 0.1%. ~ 2
0% 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, it is common to add 20% or less based on the total weight of the ethylenic compound and the binder.

When using the photopolymerizable composition of the present invention,
A light-sensitive material can be formed without a solvent or dissolved in an appropriate solvent to form a solution, which is coated on a support and dried to prepare a light-sensitive material. Examples of the solvent include methyl ethyl ketone, cyclohexanone, butyl acetate, amyl acetate, ethyl propionate, toluene, xylene,
Monochlorobenzene, carbon tetrachloride, trichloroethylene, trichloroethane, dimethylformamide, methyl cellosolve, ethyl cellosolve, tetrahydrofuran,
There is bentoxone and the like, and one kind or two or more kinds can be used in combination.

The support applied when preparing a light-sensitive material using the photopolymerizable composition of the present invention may be any commonly used support. 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, vinyl chloride, vinyl chloride-vinylidene chloride copolymer, polystyrene, 6-nylon, cellulose triacetate, cellulose acetate butyrate, etc. Polymer sheet.

Further, the photopolymerizable composition of the present invention may further be a known technique for preventing adverse effects such as a decrease in sensitivity and a deterioration in storage stability due to oxygen, such as 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, an argon ion laser, a YAG laser and the like. 400
A general-purpose light source containing visible light of nm or more can be more preferably used.

[0034]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples, but the present invention is not limited to these examples unless it exceeds the gist thereof.

Examples 1 to 12 and Comparative Examples 1 to 12 2 g of a methyl methacrylate / methacrylic acid copolymer (weight average molecular weight: 45,000, polymerization ratio: 85/15) and 2 g of trimethylolpropane triacrylate in 36 g of methyl ethyl ketone Was dissolved. 80 mg of the photoinitiating system component, that is, the titanocene compound A-1 as the component (a) was added.
Was added, and 80 mg of the sensitizer of the component (b) and 200 mg of the compound of the component (c) described in Table 1 were further added and dissolved to obtain a sample photosensitive solution. This was coated on a grained and anodized aluminum sheet using a wheeler to a dry film thickness of 2 μm, and further, an aqueous solution of polyvinyl alcohol was applied to the surface thereof to a dry film thickness of 3 μm.
m to prepare a photosensitive material sample.

Next, a xenon lamp UXL-1000-DO manufactured by Ushio Electric Co., Ltd. was used as the photosensitive material sample, and the light intensity was weakly logarithmically on the horizontal axis and logarithmically on the vertical axis using a spectral sensitivity measuring device manufactured by Narumi. Irradiated for 10 seconds. The exposed sample is developed with an aqueous solution containing 2% by weight of butyl cellosolve and 1% by weight of sodium silicate, and the minimum exposure required for photocured image formation is calculated from the height of the cured image corresponding to each wavelength obtained. The sensitivity of each wavelength of the photosensitive composition was determined. The results are shown in Table 1. The wavelengths shown in the table indicate the main photosensitive region or the maximum absorption wavelength at which the measurement was performed.

[0037]

[Table 1]

[0038]

The photopolymerizable composition of the present invention has extremely high sensitivity to visible light and is excellent in 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 front page (72) Inventor Masaaki Tsuchiyama 1000 Kamoshita-cho, Midori-ku, Yokohama-shi, Kanagawa Pref. Mitsubishi Chemical Research Institute (56) References JP-A-5-241338 (JP, A) 2-69 (JP, A) JP-A-5-107761 (JP, A) JP-A-47-2528 (JP, A) JP-A-63-243102 (JP, A) JP-A-5-281734 (JP, A A) JP-A-63-258903 (JP, A) JP-A-3-27393 (JP, A) JP-A-59-172641 (JP, A) JP-A-6-256409 (JP, A) JP-A-6 -289611 (JP, A) JP-A-7-199465 (JP, A) JP 2-30321 (JP, B2) JP 2-55446 (JP, B2) (58) Fields investigated (Int. .7, DB name) G03F ^7/ 00-7/42

Claims (3)

(57) [Claims] 1. A photopolymerizable composition comprising a compound having at least one ethylenically unsaturated double bond capable of addition polymerization and a photopolymerization initiation system, wherein the photopolymerization initiation system is (a) a titanocene compound , b) Pyromethene complex, oxa
Dyes, ketothiazoline compounds, styryl complex
Ring compound, phenylbutadienyl heterocyclic compound, tria
A gin compound, an aminophenyl unsaturated ketone compound, and
Any one selected from the group consisting of porphyrins
Thus, a sensitizer having a main photosensitive region or an absorption maximum at a wavelength longer than 450 nm in the presence of the titanocene compound, and (c) a compound represented by the following general formula (i), (ii) or (iii): At least one of the following compounds: (Wherein, R ^{1 to} R ² and R ^{4 to} R ¹¹ each represent an alkyl group having 1 to 4 carbon atoms, and R ³ represents 1 to 20 carbon atoms.
Represents an alkyl group. A) a photopolymerizable composition comprising: 2. The method of claim 1, wherein (b) the sensitizer is a pyromethene complex,
Dyes, ketothiazoline compounds, styryl complex
Ring compound, phenylbutadienyl heterocyclic compound, amino
From phenyl unsaturated ketone compounds and porphyrins
The method according to claim 1, which is any one selected from the group consisting of:
Photopolymerizable composition. 3. A light-sensitive material having a layer containing a photopolymerizable composition according to claim 1 or 2 on a support.