JPH02157761A - Photopolymerizable composition - Google Patents

Abstract

PURPOSE:To allow exposing by a low-output laser by incorporating an ethylenic unsatd. compd. which is nongaseous at ordinary temp., specific iron allene complex, specific xanthene or thioxanthene compd., specific compd. and/or specific cyclic diketone compd. CONSTITUTION:This compsn. contains the ethylenic unsatd. compd. which is nongaseous at ordinary temp., the iron allene complex expressed by the formula I, the xanthene or thioxantene compd. expressed by the formula II, and the compd. expressed by the formula III and/or the cyclic diketone compd. expressed by the formula IV. In the formulas I to IV R<1>, R<2>, R<5> to R<7> are groups; R<2>, R<5> to R<7> may form a condensed polycyclic compd. with a benzene ring; X in the formula I denotes BF4, PF6, etc.; X in the formula III denotes S, Se, etc.; A denotes oxygen or sulfur; X' denotes hydrogen or halogen; Y denotes carbon or nitrogen; Z denotes oxygen, alkoxy group, etc.; R<3> denotes an alkyl group, hydroxy alkyl group, etc.; R<4> denotes hydrogen, alkoxy group, etc.; R<9> denotes hydrogen or aralkyl group, etc.; G denotes a bivalent org. group. The use of low-energy exposing light source is possible in this way.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a novel photopolymerizable composition that is sensitive to visible light.

BACKGROUND OF THE INVENTION Photopolymerizable compositions are widely used in numerous applications, including commercial use in printing, copying, resist formation, and others.

These compositions generally contain an ethylenically unsaturated compound or other type of polymerizable compound, a photoinitiator or photoinitiator system, and preferably a solvent-soluble or aqueous or alkali-soluble organic polymeric binder compound. However, the range of application of these known useful photopolymerizable compositions is limited because the initiators used are often not activated outside the ultraviolet region of the spectrum. This is the current situation.

Furthermore, image forming techniques are required to use visible light instead of ultraviolet rays as a light source, or to perform scanning exposure with a laser such as an argon ion laser that has a large oscillation intensity in the visible region. Therefore, a photopolymerizable material that is highly sensitive to visible light is required, and a photoinitiator that is highly sensitive to visible light is required.

Japanese Patent Publication No. 5. i-155292 discloses a system containing hexaarylbisimidazole, JP-A-58-15503.
No. 4604 discloses a system of an active halogen compound and a 3-keto-substituted coumarin compound, JP-A-56-4604 discloses a system of a 3-keto-substituted coumarin and N-phenylglycine, and JP-A-61-97 discloses a system of a 3-keto-substituted coumarin and N-phenylglycine.
No. 650 discloses a photoinitiator system of a combination of a 3-substituted coumarin and a quinazolinone derivative, and JP-A-61-123603 discloses a photoinitiator system of a combination of a hexaarylbisimidazole and a 3-keto-substituted coumarin. .

(NM problem to be solved by the invention) However, the sensitivity of the photoinitiator system described above is insufficient, and in order to perform scanning exposure at high speed with a lower output laser, a photoinitiator with even higher sensitivity must be found. It is necessary.

(Means for Solving the Problems) In order to solve the above problems, that is, for the purpose of improving the sensitivity of photopolymerizable compositions to visible light, the present inventors have made extensive efforts regarding photoinitiator systems. As a result of research and efforts, we have finally completed the present invention. That is, the present invention provides (al) at least one ethylenically unsaturated compound that is non-gaseous at room temperature,
(b) Below - an iron allene complex represented by formula (1) and (c1 below - a xanthene or 1,000-ochinanthene compound represented by formula (II) and/or (d) below - a compound represented by formula (III) and/or Alternatively, it is a photopolymerizable composition characterized by containing a cyclic diketone compound represented by the following formula (IV).

(In the formula, R Ra is the same or different group, and R2 may form a fused polycyclic compound with a benzene ring. X is BF4, P F & AsFaSbFh F
eCff145nC1* 5bC1b, BiCj! h
shows. ) ^ [In the formula, A is an oxygen atom or a sulfur atom, X' is a hydrogen atom or a halogen atom, and Y is a carbon atom or a nitrogen atom (however, if Y is a carbon atom, there is a
The dotted line) is a double bond, and when Y is a nitrogen atom, the bond with the adjacent carbon is a single bond. ), Z
is an oxygen atom (in this case, there is a double bond between adjacent carbon atoms) an alkoxy group or an alkanoyloxy group, R3 is an alkyl group, a hydroxyalkyl group, an alkoxyalkyl group, a dialkylaminoalkyl group, or an aryl group , R4 is a hydrogen atom, an alkoxy group, an alkyl group, or a dialkylamino group. )R' (In the formula, R5, R4, and R'l are the same or different groups, R5 may form a fused polycyclic compound with a benzene ring, and R6SR1 is bonded with a benzene ring to form a ring.) (wherein R' is hydrogen or a substituted or unsubstituted alkyl or aralkyl group, , G is a divalent organic group.) The ethylenically unsaturated compound used in the present invention is
Monomers suitable for chain growth addition reactions initiated by iu# radicals, such as pentaerythritol triacrylate, polyethylene glycol diacrylate, triethylene glycol diacrylate, polyethylene glycol diacrylate, tetraethylene glycol dimethacrylate, Examples include trimethylolpropane triacrylate and trimethylolpropane trimethacrylate.

The second component (b) is an iron allene complex represented by the above-mentioned formula (1), and is
108(11) 345-354 (1984).

RI R” is a C, ~C12 alkyl group, C2~
C12 alkenyl group, C2-C1□ alkynyl group,
C5-C alkoxy group, cyano group, alkylthio group, phenoxy group, 02-C1 monocarboxylic acid and ester and amide, phenyl group, C2-C3 alkanoyl group, ammonium salt, pyridinium group, nitro group, alkylsulfinyl group, alkylsulfonyl group,
selected from sulfamoyl groups.

Specifically, (η6-benzene)(η5-cyclopentadienyl)iron(Iri-hexafluorophosphate, (η
6-toluene)(η5-cyclopentasuel)iron(I
I) Hexafluorophosphate, (η6-cumene) (
η5-cyclopentadienyl) iron(n) hexafluorophosphate, (η6-hensen)(η5-cyclopentagenyl) iron(II) hexafluoroarsenate,
(η6-Hensen) (ηS-cyclopentadienyl) iron(II) tetrafluoroborate, (ηb naphthalene)
(η5-cyclopenkdienyl) (■) hexafluorophosphate, (η6-anthracene) (η5-cyclopentadienyl) iron (n) hexafluorophosphate
1., (η6-pyrene) (η5-cyclopentadienyl) iron (II) hexafluorophosphate (η Hatake-benzene) (η5-cyanocyclopentadienyl) iron (■)
Hexafluorophosphate, (η“-toluene) (η
5-acetylcyclopentadienyl) iron (b) hexafluorophosphate, (η nicumene) (η5-chlorocyclopentagenyl) iron (■) tetrafluoroborate, (η-benzene) (η5-carboethyl) Kinshikurohexagenil)! (II) Hexafluorophosphate -
(η6-benzene)(η'-1,3-dichlorocyclohexagenyl)iron(II) hexafluorophosphate, (η4-cyanobenzene)(η5cyclohexagenyl)iron(I[)hexafluorophosphate, (η
1-acetophenone) (η5-cyclohexagenyl)
Iron (II) hexafluorophosphate, (η“-methylbenzoate) (η5-cyclopentagenyl) iron (
I[)hexafluorophosphate, (η6-benzenesulfonamide) (η5-cyclopentadienyl) (
■) Tetrafluoroborate, (η6-henzamide)
(η5-Cyclopentadienyl)a(n)hexafluorophosphate-1. )(η5-cyclopentadienyl)iron(II)hexafluorophosphate-1., (η6-anthracene)(η5-cyanocyclopentagenyl)iron(■)hexafluorophosphate, etc. The compound of Dokl, A
kd, Nauk 5SSR149615 (1963).

Specifically, as the third component (c), the xanthene or thioxanthene compound represented by the general formula (II), in (V), X is hydrogen, chlorine, bromine, etc., and Z is methoxy, ethoxy, propoxy, Acetyloxy, propionyloxy, etc., R1 is methyl, ethyl, propyl, hydroxymethyl, hydroxyethyl, methoxomethyl, methoxyconityl, dimethylaminomethyl, diethylaminopropyl, phenyl, xylyl, tolyl, phenyl, etc., R4 is hydrogen, methoxy , ethoxy, methyl, ethyl, propyl, dimethylamino, diethylamino, and the like.

Examples of the compound represented by the general formula (III), which is the fourth component (dl), include N-phenylglycine, N(p-
methylphenyl)chrycine, N-(p-methoxyphenyl)glycine, 1l-(p-cyanophenyl)glycine, N-(p-chlorophenyl)glycine, N-(rn-
Examples include cyanophenyl)glycine, N-methyl-N-phenylglycine, indoleacetic acid, N-methylindoleacetic acid, and 6-diathindoleacetic acid.

The cyclic diketone compound/product which is the fourth component (d) is represented by the above general formula (IV) and is a cyclic β-dicarbonyl compound having an active methylene group having an unstable hydrogen atom.

In the formula, R9 is hydrogen, alkyl, substituted alkyl, or aralkyl, and G is a divalent organic group which may contain a beta atom on the side of the group and optionally one or more carbon or hetero atoms. Both may have a substituent. In the above, the alkyl group is an alkyl having C, %C, □, and examples of the substituted alkyl include hydroxylalkyl, cyanoalkyl, haloalkyl, alkoxyalkylene, alkylene thioether, and aryloxyalkylene. The aryl portion of the aralkyl group may contain 6 to 10 carbon atoms. The divalent organic group G completes the ring. This moiety may contain heteroatoms such as nitrogen, oxygen and sulfur. Specific examples of these compounds include 5,5-dimethyl-
1,3-cyclohexanedione, 2-methyl-13cyclohexanedione, 2-methyl-1,3-cyclobentanedione, 2,4-diethyl-1,3-cyclobutanedione, 2-methyl-13-cyclobutanedione, 5 -Methyl-2-thiobarbylic acid, barbylic acid, 3-
ethylte]・ronic acid, 2,4-dimethyl-3-oxo-
5-Hydroxy-5-methoxypentenoic acid δ-lactone, 13.5-trimethylbarbital acid, l 3-dimethyl 5-ethylbarbital acid, 2-methyldimedone, l,3-indanedione, 2- Methylindandione, bis-(5-(13-dimethylbarbituryl))methane, 1,5-diphenyl 3-(2-(phenylthio)
ethyl)-24-pyrrolidinedione, ■-phenyl-3
, 5-digate 4-n-butyltetrahydropyrazole, 2゜2-dimethyl-m-dioxane-4,6-dione, 2.2.5-)dimethyl-m-dioxane-4゜6-
Examples include Zeon.

A thermoplastic high molecular weight organic polymeric binder may preferably be present in the composition of the invention. Polymeric binder types include (1) copolyesters based on terephthalic acid, isophthalic acid, sebacic acid, adipic acid and hexahydroterephthalic acid, (11) polyamides, (iii) vinylidene chloride copolymers, (1v) ethylene/ vinyl acetate copolymer, (■) cellulose ether, (vi
) polyethylene; (vi) synthetic rubber; (vi) cellulose ester; Methacrylate and polyethyl methacrylate, (xi) 4,000 to 4,000,0
High molecular weight ethylene oxide polymer (polyethylene glycol) having a weight average molecular weight of 0.00, (xii) polyvinyl chloride and its copolymers, (xiii) polyvinyl acecool, (xiv) polyformaldehyde, (X
V) polyurethane, (xvi) polycarbonate and (xvii) polystyrene.

Particularly preferred photopolymerizable binders in the compositions of the invention include those in which the unexposed photopolymerizable coating is a predominantly aqueous solution, for example an alkaline solution.

Preferred are photopolymerizable binders that are soluble in, but become relatively insoluble in after exposure to actinic radiation. Polymers that typically meet these requirements are carboxylated polymers, such as vinyl addition polymers containing free carboxylic acid groups. A preferred binder is a styrene/maleic anhydride (1:
1) and a combination of a styrene/maleic anhydride copolymer and an ethyl acrylate/methyl methacrylate/acrylic acid terpolymer. Other preferred binders include polyacrylate esters and polyalpha-alkyl acrylate esters, especially polymethyl methacrylate.

Other inert additives such as non-polymerizable plasticizers, dyes, pigments and fillers may be added to the extent that they do not inhibit the exposure of the photopolymerizable layer.

The preferred blending ratio of the photopolymerizable composition of the present invention is the component (a
Expressed in parts by weight based on 100 parts by weight of the ethylenically unsaturated compound which is component (), the iron allene complex which is component The xanthene or thioxanthene compound c1 contains 0.01 to 201 parts, particularly preferably 0.1 to 20 parts by weight, and the component (d) the compound represented by the general formula (II) or the cyclic diketone compound contains 0.01 to 20 parts by weight, particularly preferably 0.01 to 20 parts by weight, respectively.
．． 1 to 20 parts by weight, and the binder is 0 to 1000 parts by weight, preferably 0 to 50 parts by weight.

The photopolymerizable composition of the present invention can be coated on a wide variety of Go boards.

By "substrate" is meant any natural or synthetic support, preferably present in the form of a flexible or rigid film or sheet. For example, the substrate can be a metal sheet or pipe, a sheet or film of synthetic organic resin, cellulose paper, fiberboard, etc. or a composite of two or more of these materials. Specific 4+A's include alumina blasted aluminum, anodized aluminum, aluminum blasted polyethylene terephthalate film, polyethylene terephthalate film, electrostatic discharge treated polyethylene terephthalate film, polyvinyl alcohol coated paper, crosslinked polyester coach ink paper, nylon, glass, cellulose acetate. Examples include film and others.

The particular ridge material will generally be determined by the application purpose involved. For example, if printed circuits are to be manufactured, the substrate may be a copper coated plate on fibreboard. In the manufacture of lithographic printing plates, the substrate is 7-node treated aluminum.

Preferably, the layer of photopolymerizable composition has a thickness of about 0,000 cm to about 0.01 cm.
. A protective cover layer or cover sheet can be adhered thereto, which sheet has an adhesive force to the layer that is less than the adhesive force between the film support and the layer.A particularly preferred support is Approximately 0.001 inch (0,0025C11) to approximately 0.4 inch (1
, 0 cm). Also, 0.0005 inch (0,0013 CI) to 0.04 inch (0, l
Ocm ) polyethylene is the preferred cover sheet and a polyvinyl alcohol coating is the preferred cover layer.

When exposing the composition of the present invention, the usual light source is 405
．． Fluorescent lamps, mercury lamps, giving narrow or broad bands of light centered at 436 and 546 nm (Ilg) wavelengths;
Mention may be made of metal-doped lamps and arc lamps. The interference light source is pulsed xenon, argon ion, helium.
Visible light generating cathode ray tubes commonly used in printout systems, such as cadmium and ionizing neon lasers, are also useful with the compositions of the present invention. These generally include an internal coating of ultraviolet or visible light-emitting phosphor as a means to convert electrical energy into light energy and direct the radiation to a light-sensitive target.・Lead to (
A fiber optic faceplate is included as a means for this purpose.

(Function) The aggravating agent of the present invention, that is, the component (c) originally effectively absorbs visible light that the photoinitiator, that is, the component (b) used in the present invention cannot absorb or exhibits a very small absorbance. absorbed and activated. In that state, the sensitizer of the present invention acts on the photoinitiator used in the present invention, resulting in generation of active radicals, which attack ethylenically unsaturated compounds in the composition, This causes polymerization.

(Example) The present invention will be specifically explained below with reference to Examples, in which parts and percentages are based on weight.

Examples 1 to 25, Comparative Examples 1 to 8 A photosensitive layer coating solution having the following composition was applied onto a 100 μ thick transparent polyethylene terephthalate film having an undercoat layer, and dried for 1 minute at 90″C in a hot air dryer. and thickness 3
After obtaining a coating film of μ, an aqueous solution of 7% polyvinyl alcohol (completely saponified, degree of polymerization 500) was applied on top of the coating, and dried in a hot air dryer at 100°C for 1 minute to form an overcoat layer with a thickness of 1μ. A sensitivity test piece was obtained.

(Composition of photosensitive layer coating liquid) Poly(methyl methacrylate/methacrylic acid) 52 parts 70/30 molar ratio Tetraethylene glycol diacrylate 40 Component (b) 5 Component (c) 3 Component (d) 3 Methanol 200 Ethyl acetate 8゜Chloroform
120 A 21,/1'-step tablet (clay film scale manufactured by Dainippon Screen Co., Ltd.) was placed as a negative film on the above sensitivity test piece, and a xenon lamp (tJX L-5 manufactured by Ushio Inc.
00D-0) 4. : Toshiba interference filter KL-4
Light i combining 9 and the same color glass filter Y-45
After exposure for 5 minutes from a distance of 15 cm with fQ (490 nmA), 10
After soaking for seconds, washing with water to remove uncured parts, and drying,
The number of steps for complete curing of the 21-part step tablet was investigated and is shown in Tables 1 to 3. Further, as is clear from Tables 1 to 4, which show comparative examples in Table 4, Examples 1 to 25 of the present invention are more sensitive to light of 490 nm than Comparative Examples 1 to 8.

(Effects of the Invention) Since the photopolymerizable composition of the present invention exhibits high sensitivity to visible light, a low energy exposure light source can be used, and a large number of originals can be exposed and exposed within a given time. Can be developed.

In addition, since the exposure source can be moved away from the original, the light rays are collimated, which has various advantages such as the ability to form sharp halftone dots with vertical sides when forming halftone images, for example. .

Patent applicant: Toyobo Co., Ltd.

Claims (1)

[Scope of Claims] (a) at least one ethylenically unsaturated compound that is non-gaseous at room temperature; (b) an iron allene complex represented by the following general formula (I); (c) an iron allene complex represented by the following general formula (II). and/or (d) a compound represented by the following general formula (III) and/or a cyclic diketone compound represented by the following general formula (IV). . ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, R^1 and R^2 are the same or different groups, and R
^2 may form a fused polycyclic compound with a benzene ring. X is BF_4, PF_6, AsF_6, SbF_6
, FeCl_4, SnCl_6, SbCl_6, BiC
Indicates l_6. ) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (II) [In the formula, A is an oxygen atom or a sulfur atom, X' is a hydrogen atom or a halogen atom, and Y is a carbon atom or a nitrogen atom (however, if Y is a carbon atom) between adjacent carbon atoms (
The dotted line) is a double bond, and when Y is a nitrogen atom, the bond with the adjacent carbon is a single bond. ), Z
is an oxygen atom (in this case, there is a double bond between adjacent carbon atoms) an alkoxy group or an alkanoyloxy group, R^3 is an alkyl group, a hydroxyalkyl group, an alkoxyalkyl group, a dialkylaminoalkyl group, or The aryl group R^4 is a hydrogen atom, an alkoxy group, an alkyl group, or a dialkylamino group. ] ▲There are mathematical formulas, chemical formulas, tables, etc.▼(III) (In the formula, R^5, R^6, and R^7 are the same or different groups, and R^5 forms a fused polycyclic compound with a benzene ring. R^6 and R^7 can also be combined with a benzene ring to form a ring. X'' is S, Se, N-R^8
Here, R^8 represents hydrogen or an alkyl group of C_1 to C_6. ) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(IV) (In the formula, R^9 is hydrogen or a substituted or unsubstituted alkyl or aralkyl group, and G is a divalent organic group.)