JPH01303430A - 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., org. peroxide contg. a specific group and specific p-aminophenyl unsatd. ketone compd. into the above compsn. CONSTITUTION:This compsn. contains at least one kind of the ethylenic unstad. compds. which are non-gaseous at ordinary temp., the org. peroxide contg. the group expressed by the formula I and the p-aminophenyl unsatd. ketone compd. expressed by the formula II. In the formula I, Ar denotes a phenyl group, etc. In the formula II, m, n are respectively 0 or 1; at least either of R1, R2 is expressed by CH2COOR6 and at least either thereof may be a hydrogen atom or alkyl group of 1-5C. R3 is a methylidine group, etc.; R4 is a hydrocarbon, etc.; R5 is expressed by the formula III. In the formula III, R7, R8 are a hydrogen atom, etc. The high sensitivity to visible light is obtd. in this way.

Description

[Detailed Description of the Invention] (Industrial Utilization) The present invention is a novel light beam whose sensitivity extends to the region of II visual light.
The present invention relates to a composite composition.

(Prior Art) Small compound compositions are widely used in many applications, such as printing, copying, rennost formation, and other applications.

These compositions 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 cutting machine 3 Tf coalescent bonding compound. I am doing it myself. However, many of these known photopolymerizable compositions are not activated outside the ultraviolet region of the spectrum due to the initiator used, which limits their range of application. is the current situation.

In addition, as a light source, the use of ultraviolet rays as a 1-visual beam, and scanning exposure using a laser such as an argon ion laser that emits a large oscillation intensity in the 1-visual region are both recommended as image forming techniques. Therefore, there is a need for a highly compatible material that exhibits high sensitivity to ++J visual rays, and ITI
A photoinitiator that is sensitive to optic potential is required.

JP-A-54-t 55292 z; Publication describes a system containing hexaarylbisimidazole, JP-A-58-155
Publication No. 03 discloses a system of an active/Xrogen compound and a 3-keto-substituted coumarin compound, JP-A-56-4 e 04 S; Publication No. 03 discloses a system of a 3-keto-substituted coumarin and HN-phenylglycine, JP-A-81 -97650 Bow/publication describes the combination of 3-substituted coumarin and quinazolinone derivative, JP-A-61-
No. 123603S discloses a combination photoinitiator system of hexaarylbiimidazole and 3-keto substituted coumarin depletion.

(Problem to be Solved by the Invention) However, the sensitivity of the photoinitiator system described above is inadequate, 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. It is necessary.

(Ding-step for solving the problem) In order to solve the problem 1., that is, in order to increase the sensitivity of the compound composition to visible light, As a result of intensive research and efforts regarding initiator systems, we have finally completed the present invention. In other words, the present invention comprises (21) at least 41 types of ethylenically unsaturated compounds that are gaseous at room temperature; p-Amino Ar reduced with peroxide and (e) Doki-murder (II)
-C-0-0-(I) (wherein Ar is a phenyl group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, phenyl), (, an amino group, a carbonyl group, a halogen group, One or more of the following:
represents a phenyl group substituted with ) The ethylenically unsaturated compounds conveniently used in the present invention are A111 compounds suitable for chain growth addition reactions initiated by free radicals, such as pentaerythritol triacrylate, polyethylene glycol noacrylate, triethylene glycol noacrylate, polyethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate,
Examples include trimethylolpropane triacrylate and trimethylolpropane trimethacrylate.

The second component (b) is a 41-organic peroxide containing a group represented by the above-mentioned --- Noshiro (I), and is
It is disclosed in Japanese Patent Application Laid-open No. 9340/1983 and Japanese Patent Application Laid-Open No. 60-78503. Specifically, benzoyl peroxide, di(t-butylperoxy/)isophthalate, 2
,5-dimethyl-2゜5-no(benzoylperoquibutylperoxy7penzoate, α,α'-his(t-
butylperoxyisopropyl)benzene, 3,3'
, 4.4'-tetra(t-butylenecarbonyl)benzophenone, 3.3', 4.

4′-tetra([-butylamylperoxy7carbonyl)benzophenone, 3.3′ 4.4′-tetra(t
-octylperoxycarbonyl)benzophenone, etc.

The third component (e) is p expressed by Noshiro (II) above.
-Aminophenyl unsaturated ketone compound, specifically 2,5-bis(4'-N-ethyl-N-carbomethquinemethylaminobenzylidene)cyclopentanone, 2
-5-bis(4'-N-ethyl-N-hydroxymethylaminobenzylidene)pentanone and its sodium salt, 2.

5-bis(4'-N-methyl-N-cyanoethylaminobenzylidene)cyclopentanone, 2,5-bis(4
'-N-Ethyl-N-chlorominobenzylidene)cyclopentanone, 2.6-bis(4'-N-ethyl-N-cyanoethylaminobenzylidene)cyclohexanone, 2-(4'-N-ethyl-N -carboxinemethylaminobenzylidene)-1-indanone, 2-
Sodium salt of (4'-N-ethyl-N-carboxymethylaminobenzylidene)-1-tetralone%2-<
Examples include 4'-ethyl-N-cyanoethylaminobenzylidene)-1-indanone.

Preferably, the composition of the present invention contains a thermal ++J plastic polymer I1.
1. A bonding agent may be present. Small coalescent binder types include (1) copolyesters based on terephthalic acid, isophthalic acid, sebacic acid, adipic acid and hexahydroterephthalic acid; (11) polyamides;
Vinylidene chloride copolymer, (lv) ethylene/vinyl acetate J14 +T< union, (V) cellulose ether, (vl) polyethylene, (V) outdoor rubber, hill) cellulose ester, (lx) polyvinyl acetate/acrylate and Polyvinyl esters containing polyvinyl acetate/methacrylate copolymers, (X) polyacrylates and polyα-alkyl acrylate esters such as polymethyl methacrylate and polymethyl methacrylate, (xi) from 4,000
4,000,000 small; 1, 1, 1, 1, 1, 1, 1, 1, 1, 1, 1, 1, 1, 1, 1, 1, 1, 1, 1, 1, 1, 4, 4, 4, 4, 4, 4, 5, 4, 5, 4, 5, 4, 5, 4, 4, 4, 4, 4, 4, 4, 4, 4, 4, 5, 4, 4, 5, 4, and 4 types of polymers (polyethylene glycol), (xli) polyvinyl chloride and its copolymers, ( Xl11) polyvinyl acetal, (xiv) polyformaldehyde, (XV) polyurethane, (XVI) polycarbonate and (xvil)
I can give you polystyrene.

In a particularly preferred embodiment of the present invention, the unexposed small-component coating is 1, such as an Alkalya 1 solution, 1, 1, 1, 1, 1, 1, 1, 2, 1, 2, 1, 2, 3, 3, 3, 3, 3, 3, 3, 3, 3, 3, 3, 3, 3, 3, 3, 3, 3, 3, 3, 3, 3, 3, , 3, , , 3, , , , , , , , , , , , , 1 , , 1 , 1 , 1 , 2 , 2 , 2 , 2 , 2 , 2 , 2 , 2 and 3 , respectively , for example , in an aqueous solution , ljl soluble w 1 , but after exposure to 11ζ radiation , relatively free from oxidation , after exposure to 11ζ radiation . The photopolymerizable binder is chosen so that it is insoluble. Polymers that typically meet these requirements are carboxylated small polymers, such as vinyl adduct polymers containing free carboxylic acid groups. The preferred binder is an isobutanol mixture partially Nisderized with an acid number of about 1.
90, small i + I medium proportion 1' i + I about 109000 styrene/maleic acid (!1 (water (1: 1)) (I
T+' combination, and styrene/maleic acid j1; Mention may be made of acrylate esters and polyalpha-alkyl acrylate esters, especially polymethyl methacrylate.

Other additives such as Jll associative plasticizer dyes,
Pigments and fillers are known to those skilled in the art; these additives are generally present at low iIts, and this is not intended to inhibit exposure of the photopolymerizable layer.

The preferable ratio of the photopolymerizable composition of the present invention is expressed in parts as ton 11 to parts of ethylenically unsaturated compound (1001T<f'+) as component (a). 0.01 to 100,000'' 11 parts, particularly preferably 0.1 to 50 1 part, component (c) p-aminophenyl unsaturated ketone compound 0.01 to 100 1 part;
Salt 1. capital, particularly preferably 0. 1 to 50 cities ++1 copy,
The binder is 0 to 10001 parts il, particularly preferably 0
~500 tons fIt part.

The composition of the present invention can be applied to a wide variety of substrates.

can be coated. Said J, L 41 is any heat input or synthetic support,! Preferably +'
i) i3) Existing in the form of a flexible or rigid film or sheet. For example, the base material may be a composite sheet or foil, a synthetic organic resin sheet or film,
It may be cellulose paper, fiberboard, etc. or an N combination of two or more of these materials. Specific base materials include alumina plasto aluminum;
Anodized aluminum, aluminum paste, polyethylene terephthalate film, polyethylene terephthalate film such as resin-drawn polyethylene terephthalate film, electrostatic discharge treated polyethylene terephthalate film, polyvinyl alcohol coated paper, cross-linked polyester coated paper, nylon, glass, cellulose acetate film, etc. can be given.

The particular J^ material is generally determined by the application purpose involved. For example, if a printed circuit is to be mounted, the substrate can be a copper-coated plate of fiberboard I. - In the production of 1-size printing plates, the substrate is anodized aluminium.

(11') Preferably, the layer of photolabile composition is from o, ooot inch (0,00025 cm) to about 0.01 inch (0.01 inch).
, 025 cm) and is adhered to the photopolymerizable layer with moderate to moderate adhesion properties to a thin 1F (resilient polymeric film support) which is transparent to the active radiation. 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 about 0.001 inch (0.002 inch)
A transparent polyethylene terephthalate film having a thickness ranging from 1" to about 0.4 inches (1,000 cm) to about 0.0005 inches (0,0013
cm) to 0.04 inch inch (0.10 cm) polyethylene is the preferred cover sheet and a polyvinyl alcohol coating is the preferred cover layer.

Typical light sources are 405.43B and 546 ri
Examples include fluorescent lamps, mercury lamps, metal-doped lamps, and arc lamps that produce narrow or wide light bands centered at m (Hg) wavelengths. 11 Step light i%I includes pulsed xenon, argon ion, helium-cadmium, and ionized neon lasers. The composition of the present invention is widely used in print-out systems (IIJ cathode ray tubes are widely used). or one optic phosphor internal coating and a fiber optic faceplate as a means for directing the radiation to the photosensitive target.

(+'+jl) The sensitizer of the present invention, i.e., component (c), has the effect that the photoinitiator, i.e., component (b) used in the present invention, does not absorb or J1 always has a small absorbance. Efficiency (absorbs vision and becomes active P1).

In this state, the sensitizer of the present invention acts on the photoinitiator used in the present invention, resulting in the generation of condensing radicals, which attack the ethylene unsaturated compounds in the composition. It seems that a small meeting will be held.

(Examples) The present invention will now be specifically explained with reference to Examples.

Examples 1 to 8, Comparative Examples 1 to 5 A transparent polyethylene terephthalate film 1'' having a thickness of 100 μ and having a pull layer was coated with a photosensitive layer having the following composition.
'[&' was placed inside and dried in a hot air dryer at 90°C for 1 minute to obtain an inside film with a thickness of 3 μm. Next, 7% polyvinyl alcohol (completely saponified, small group IJII: 500
) and dried in a hot air dryer at 100° C. for 1 minute to form a 1 μm overcoat layer, and a sensitivity test piece was prepared.

(1-liquid composition in photosensitive layer) Poly(methyl methacrylate/methacrylic acid) 52 parts 70/30 molar ratio Tetraethylene glycol diacrylate 40 41 Peroxide (component b) 5 m
<p-aminophenyl unsaturated ketone (1 minute c) 3 methanol 200 ethyl acetate 80 chloroform
1201゛ Sensitivity test piece 21r2 stage as a negative film, Tsubutu tablet (person 11
Marketed gray film scale manufactured by Hon Screen Co., Ltd.
Xenon lamp (Ushio Inc. UXL-500
1) -0) Toshiba L-wata filter K L-4
After exposure for 10 minutes from a distance of 15 cm using a light source (490 nmA) that combines 9 and the same color glass filter Y-45, it was immersed in a 0.7% sodium carbonate aqueous solution at 30°C for lθ seconds and washed with water. After removing the hardened part and drying, 21ff2 step! The number of steps for complete transformation of the tablet was investigated and summarized in Table 1. Comparative examples are also shown in Table 2.

Table 1 Table 2 As is clear from Table 1.2, Examples 1 to 8 of the present invention were compared to Comparative Examples 1 to 5 by 1'+ for the likelihood of 490 nm.
': It turns out that it is 1 m degree.

(Effects of the Invention) The light-sensing v1 composition of the present invention has a high sensitivity of 1!1 to IIl visual light, so it is possible to use a low-energy exposure light, and , a large number of originals can be exposed and developed in a given time. Also, exposure ♂; t is 13;
can be moved away from the plate, so the ray is ・1q
For example, when forming a halftone image, it has various advantages such as being able to form a sharp halftone dot that covers the sides of the small dots.

Claims (1)

[Scope of Claims] (a) at least one ethylenically unsaturated compound that is non-gaseous at room temperature; (b) an organic peroxide containing a group represented by the following general formula (I); and (c) the following general formula: A photopolymerizable composition comprising a p-aminophenyl unsaturated ketone compound represented by formula (II). ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I) (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, or a halogen atom. (Indicates a phenyl group substituted with one or more species.) ▲Mathematical formulas, chemical formulas, tables, etc.▼(II) [In the formula, m and n are each 0 or 1, and R_1, R
At least one of _2 is CH_2COOR_6 (However, R_6 is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms,
Alkali metal, ammonium, amine, or C_2H
_4CF_3C_2H_4I, C_2H_4Br, C_
2H_4Cl, C_2H_4F, C_2H_4CN, C
_2H_4NO_2), and either one of them may be a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. R_3 is a methylidine group or an alkylene-iridine group having 1 to 5 carbon atoms on a carbon atom that can be combined with R_4 to form a ring with a carbonyl group, R_4 is a carbon atom, a substituted or unsubstituted phenyl group, or R_3 and a carbonyl group R_5, a group that forms indanone or tetralone with R_5, has a mathematical formula, chemical formula, table, etc. (However, R_7 and R_8 are hydrogen atoms or carbon atoms with 1 to 1
5 alkyl group, or CH_2COOR_9 (where R_9 is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms,
Alkali metal, ammonium, amine or C_2H_
4CF_3, C_2H_4I, C_2H_4Br, C_
2H_4Cl, C_2H_4F, C_2H_4CN, C
_2H_4NO_2). ]