JPH022562A - Photopolymerizable composition - Google Patents

Abstract

PURPOSE:To improve sensitivity to visible light by incorporating at least one kind of ethylenic unsatd. compds. which are non-gaseous at ordinary temp. and specific compd., etc., into the above compsn. CONSTITUTION:At least one kind of the ethylenic unsatd. compds. which are non-gaseous at ordinary temp. and the iron allene complex expressed by formula I and/or the org. peroxide contg. the group expressed by formula II and the compd. expressed by formula III are incorporated into this compsn. In formula R denotes a hydrogen, alkyl group, aryl group, alkoxy group which may form a condensed polycyclic compd. with a benzene ring. X denotes BF4, PF6, AsF6, SbF6. In formula II, Ar denotes a phenyl group or the phenyl group substd. by >=1 kinds among 1-4C alkyl group, 1-4C alkoxy group, phenyl group, amino group, carbonyl group, and halogen atom. In formula III, R1, R2 denote 1-4C alkyl group; R3 denotes a hydrogen atom or methyl group. The high sensitivity to visible light is obtd. in this way.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a novel photopolymerizable composition whose sensitivity extends to the visible light region.

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 many of these known useful photopolymerizable compositions is currently limited because the initiators used are often not activated outside the ultraviolet region of the spectrum. It is.

In addition, there are four image forming techniques that use visible light instead of ultraviolet rays as a light source, or perform scanning exposure with a laser such as an argon ion laser that has a large oscillation intensity in the visible region. For this purpose, a photopolymerizable material with high sensitivity to visible light is required, and a photoinitiator with high sensitivity to visible light is required.

JP-A-54-155292 discloses a system containing hexaarylbisimidazole, JP-A-58-15503 discloses a system containing an active halogen compound and a 3-keto-substituted coumarin compound, and JP-A-56-4604 discloses a system containing a 3-keto-substituted coumarin compound. - Keto-substituted coumarin and N-phenylglycine system, JP-A-81-9765
No. 0 discloses a photoinitiator system of a combination of a 3-substituted coumarin and a quinazolinone derivative, and JP-A-61-123803 discloses a photoinitiator system of a combination of a hexaarylbiimidazole and a 3-keto-substituted coumarin. .

(Problem to be Solved by the Invention) However, the sensitivity of the photoinitiator system described above is only a fraction of the sensitivity, and in order to perform scanning exposure at high speed with a lower output laser, it is necessary to find a photoinitiator with even higher sensitivity. is necessary.

(Means for Solving the Problems) In order to solve the above problems, that is, for the purpose of increasing the sensitivity of a photopolymerizable composition to visible light,
As a result of intensive research and efforts regarding photoinitiator systems, we have finally completed the present invention. That is, the present invention comprises (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) and/or a group represented by the following general formula (II). Photopolymerization characterized by containing an organic peroxide containing and (c) 1,1'dicyano-4-(p-dialkylaminophenyl)-1,3-butadiene represented by the following general formula (III) It is a lukoxy group in the sexual composition, and may form a fused polycyclic compound with a benzene ring. X is BF,,PF
,.

As FB , 5bF6 is shown. ) Ar-C-0-0-(II) (wherein Ar is a phenyl group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a phenyl group, an amino group, a carbonyl group, a halogen atom) (III) (In the formula, RIs R2 represents an alkyl group having 1 to 4 carbon atoms, and R and 1 are a hydrogen atom or a methyl group.) In the present invention The ethylenically unsaturated compounds used are
Monocular bodies suitable for free radical initiated chain growth addition reactions, such as pentaerythritol triacrylate, polyethylene glycol diacrylate, triethylene glycol diacrylate, polyethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, trimethylol Examples include propane triacrylate and trimethylolpropane trimethacrylate.

The second component (b) is an iron allene complex represented by the above general formula (I), and is an iron allene complex represented by J, Imag, Sc1. ．． 30 (4
) 174-177 (198B) and J, Radia
tionCuring 0ctober (198B
) Compounds such as those shown in Nos. 26 to 32 can be mentioned.

Specifically, (η0-Hensen)(η5-cyclopentadienyl)iron(II)-hexafluorophosphate, (
η0-toluene)(η5-cyclopentazinyl)iron(
■) Hexafluorophosphate, (η0-cumene) (
(η-cyclopentagenyl) iron(II) hexafluorophosphate, (η0-benzene) (η5-cyclopentagenyl) iron(II) hexafluoroarsenate, (η0-benzene) (η6-cyclopentagenyl) )
Iron (II) tetrafluoroborate, (η8-naphthalene) (η5-cyclopentadienyl) iron (II) hexafluorophosphate, (η0-anthracene) (η5
-cyclopentagenyl) iron (II) hexafluorophosphate, (η0-pyrene) (η5-cyclopentagenyl) iron (II) hexafluorophosphate, and the like. These compounds are Dokl, Akd,
It can be synthesized from ferrocene by the two methods of Nauk 5SSR149615 (1963).

The organic peroxide containing the group represented by the general formula (II), which is the second component (b), is
40 and Japanese Patent Application Laid-Open No. 60-78503. Specifically, benzoyl peroxide, di(t-butylperoxy)isophthalate, 2,5-dimethyl-2゜5-di(benzoylperoxy)hexane, -butylperoxybenzoate, α, α'-bis(t -Butylperoxyisoprobyl 3,3'4.4'-Tetra(t-butylperoxycarbonyl)benzophenone,3.3' 4.

4'-tetra(t-butylamylperoxycarbonyl)benzophenone, 3.3'4.4'-tetra(t
-octylperoxycarbonyl)benzophenone, etc.

The third component (C) is 1,1'-dicyano-4-(P-dialkylaminophenyl)-1,3-butadiene represented by the general formula (III), and is composed of aldehydes corresponding to arononitrile, Max Coenen a
nd Max Pestermer, Z. EIektro
che+s.

57, 785-95 (1953). Specific compounds include 1,1'-
Dicyano-4-(o-methyl-p-dimethylaminophenyl)-1,3-butadiene, 1,1'-dicyano-4
-(p-dimethylaminophenyl)-1,3-butadiene, 1,1'-dicyano-4-(p-diethylaminophenyl)-1,3-butadiene, and the like.

An organic polymeric binder for thermoplastic polymers may preferably be present in the composition of the invention. Polymeric binder types include copolyesters based on m-terephthalic acid, isophthalic acid, sebacic acid, adipic acid and hexahydroterephthalic acid, (I) polyamide, (Ill) vinylidene chloride copolymer, (Iv) ethylene/vinyl acetate. Jt2 polymer, (v) cellulose ether, (vl)
polyethylene, (v!I) outdoor rubber, (vlil) cellulose ester, (lx) polyvinyl ester, including polyvinyl acetate/acrylate and polyvinyl acetate/methacrylate copolymers, (x) polyacrylate and polyalkyl acrylate ester, e.g. Polymethyl methacrylate and polyethyl methacrylate, (xl) 4,000 to 4,000,000
High molecular weight ethylene oxide polymer (polyethylene glycol) having a weight average molecular weight of
polyurethane, (xvi) polycarbonate and (x
vii) Polystyrene can be mentioned.

In a particularly preferred embodiment of the invention, the photopolymerizable coating is soluble in primarily aqueous solutions, such as alkaline solutions, but relatively insoluble therein after exposure to actinic radiation. Choose a sexual binder. Polymers that typically meet these requirements are carboxylated polymers, such as vinyl addition polymers containing free carboxylic acid groups. A preferred binder is styrene/maleic anhydride (with an acid number of 190, a heavy electric average molecular sacrifice of to, ooo) partially esterified with an inbutanol mixture.
1:l) copolymers and combinations of styrene/maleic anhydride copolymers and ethyl acrylate/methyl methacrylate/acrylic acid terpolymers. Other preferred groups of binders include polyacrylate esters and polyα-alkyl acrylate esters, especially polymethyl methacrylate.

Other inert additives such as non-polymerizable plasticizers, dyes, pigments and fillers are known to those skilled in the art.These additives are generally present in small quantities and this inhibits the exposure of the photopolymerizable layer. It shouldn't be something that forces people to do something.

The preferred blending ratio of the photopolymerizable composition of the present invention is the component (a
), the iron allene complex and/or ifIa peroxide is 0.01 to 50 parts by weight,
Particularly preferably 0.1 to 30 parts by weight, component (C) 1,1'-dicyano-4-(1)-dialkylaminophenyl)-1,3-butadiene, 0.01 to 20 parts by weight, Particularly preferably 0.1 to 20 pupil area, binder 0 to 1
000 parts by weight, preferably 0 to 50 parts by weight.

The photopolymerizable compositions of the present invention can be coated onto a wide variety of substrates.

By "substrate" is meant any natural or synthetic support, preferably in the form of a flexible or rigid film or sheet. For example, the substrate can be a metal sheet or foil, a sheet or film of synthetic organic resin, cellulose paper, file board, etc. or a composite of two or more of these materials.

Specific substrates include alumina-blasted aluminum, anodized aluminum, aluminum-blasted polyethylene terephthalate film, polyethylene terephthalate film such as resin-subbed polyethylene terephthalate film, electrostatic discharge treated polyethylene terephthalate film, polyvinyl alcohol coated paper, cross-linked polyester coated paper. , nylon, glass, cellulose acetate film, and others.

The particular substrate will generally be determined by the application purpose involved. For example, if printed circuits are to be manufactured, the substrate may be a fiberboard plate coated with steel. ≦(In the manufacture of printing plates, the substrate is anodized aluminum.

Preferably the layer of photopolymerizable composition has a thickness of o, ooot inches (
0,00025 cm) to approximately 0.01 inch (0,025
cm) and is adhered with moderate to moderate adhesion to a thin flexible polymeric film support that is transparent to the radiation active in the photopolymerizable layer. A protective cover layer or cover sheet can be adhered thereto. The sheet has a tangent force to the layer that is less than the adhesive force between the film support and the layer.

A particularly preferred support is about 0.001 inch (0.002 inch)
5 cm) to about 0.4 inches (1.0 cm). Also, 0.0005 inch (0,0013 cm)
~0.04 inch (0.10c,) polyethylene is the preferred cover sheet and a polyvinyl alcohol coating is the preferred cover layer.

Common light sources include 405.438 and 546 nm (
Fluorescent lamps, mercury vapor lamps, metal-doped lamps and arc lamps, which provide narrow or broad bands of light centered on Hg) wavelengths. Interference light sources include pulsed xenon, argon ion, helium-cadmium, and ionized neon lasers. Visible light producing cathode ray tubes, commonly used in printout systems, are also useful with the compositions of the present invention. These generally include an ultraviolet or visible light emitting phosphor internal coating as a means for converting electrical energy into optical energy and a fiber optic faceplate as a means for directing radiation to a light sensitive target.

(Function) The sensitizer, that is, component (C) of the present invention originally efficiently absorbs visible light that the photoinitiator, that is, 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, where parts and percentages are based on heavy oil.

Examples 1 to 9, Comparative Examples 1 to 7 - A photosensitive layer coating solution having the following composition was applied onto a transparent polyethylene terephthalate film with a thickness of 100 μm on which the pulling layer was formed, and dried at 90° C. in a hot air dryer. Dry blasting was performed for a minute to obtain a coating film with a thickness of 3 μm. Next, an aqueous solution of 7% polyvinyl alcohol (completely saponified, degree of polymerization 500) was applied thereon and dried in a hot air dryer at 100°C for 1 minute to form a 1 μm overcoat layer to obtain a sensitivity test piece.

(Photosensitive layer coating liquid composition) Poly(methyl methacrylate/methacrylic acid) 52 parts 70/30 molar ratio Tetraethylene glycol diacrylate 40 Compounds shown in Tables 1 and 2 (component b) 5
(Component c) 3 methanol 200 ethyl acetate 80 chloroform
A 21f2 step tablet (gray film scale manufactured by Dainippon Screen Co., Ltd.) was superimposed as a negative film on 1201-sensitivity test piece 1-, and a xenon lamp (UXL-500D-0 manufactured by Ushio Inc.) was applied.
After exposure for 5 minutes from a distance of 15c+* using a light source (490nmA) that combines Toshiba's interference filter KL-49 and the same color glass filter Y-45, it was heated to 30°C at 0.7°C.
% sodium carbonate aqueous solution for 10 seconds, washed with water to remove the uncured portion, and dried. 21. The number of complete curing stages (steps) of the r2 step tablet was investigated and is shown in Tables 1 and 2. Comparative examples are also shown in Table 3. As is clear from Table 1.2, Examples 1 to 9 of the present invention are Comparative Examples 1 to 7.
It can be seen that it is highly sensitive to 490 nm light compared to .

Table 1 The following margins (effects of the invention) The photopolymerizable composition of the present invention exhibits high sensitivity to 11. It has the characteristic that a large number of originals can be exposed and developed within the same space, and since the exposure source can be moved away from the original, the light beam is collimated, and when forming a halftone image, for example, the sides of the reassembled It has various advantages such as being able to form sharp halftone dots.

Claims (1)

[Scope of Claims] (a) At least one ethylenically unsaturated compound that is non-gaseous at room temperature (b) An iron arene complex represented by the following general formula (I) and/or an iron allene complex represented by the following general formula (II) and (c) 1,1'-dicyano-4-(P-dialkylaminophenyl)-1,3-butadiene represented by the following general formula (III). A photopolymerizable composition. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I) (In the formula, R is hydrogen, an alkyl group, an aryl group, an alkoxy group, and may form a fused polycyclic compound with a benzene ring.X is BF_4, PF_6, AsF_6, SbF
Shows _6. ) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II) (In the formula, Ar is a phenyl group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a phenyl group, an amino group, a carbonyl group, a halogen (Indicates a phenyl group substituted with one or more atoms.) ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼ (III) (In the formula, R_1, R_2 represent an alkyl group having 1 to 4 carbon atoms, and R_3 is (Hydrogen atom or methyl group.)