JPH0244058B2 - HIKARIJUGOSE ISOSEIBUTSU - Google Patents

Description

[Detailed description of the invention]

FIELD OF THE INVENTION This invention relates to novel photopolymerizable compositions, and more particularly to photopolymerizable compositions containing novel photoinitiator systems. Photopolymerizable compositions generally use a UV light source and are widely applied to letterpress printing, relief images, photoresists, etc., but systems with higher sensitivity are desired. In particular, when the purpose is scanning exposure using a laser beam, it is highly sensitive, and at the same time,
For example, in the case of an argon ion laser, it is necessary to have sufficient sensitivity to visible light such as 458488514 nm, which is its main output wavelength. Much research has been done in this field on photoinitiator systems to increase sensitivity. Many substances are already known as photoinitiators, such as benzoin and its derivatives, benzophenone and its derivatives, and substituted or unsubstituted polynuclear quinones, but none are known that have sufficient sensitivity, especially in visible light. do not have. The present invention was made in response to this demand, and was made based on the discovery, as a result of various studies, that a combination of an aminobenzoic acid ester and an isoalloxazine skeleton-containing compound is particularly effective. That is, the present invention comprises (1) an addition polymerizable compound having a boiling point of 100°C or higher at normal pressure; (2) an aminobenzoic acid ester represented by the following formula []; (In the formula, R ₁ and R ₂ are hydrogen or have 1 to 1 carbon atoms.
The alkyl group of 3, R ₃ is an alcohol residue,
(R ₁ , R ₂ and R ₃ may be the same) (3) A compound having an isoalloxazine skeleton represented by the following formula [] (In the formula, R ₄ and R ₅ are hydrogen, methyl group, or ethyl group, and these may be the same). The addition polymerizable compound contained in the photopolymerizable composition of the present invention has a boiling point of 100° C. or higher at normal pressure. Boiling point is 100 at normal pressure
If the temperature is lower than ℃, part of the addition polymerizable compound will volatilize when the solvent contained in the system is removed by heat drying or when irradiated with actinic rays, which is unfavorable in terms of properties and workability. It is from.
In addition, the addition polymerizable compound should be soluble in organic solvents such as acetone, methyl ethyl ketone, toluene, chloroform, methanol, ethanol, and 1,1,1-trichloroethane in order to form a uniform composition with the photoinitiator. preferable. Examples of addition-polymerizable compounds include those obtained by condensing polyhydric alcohols with α,β-unsaturated carboxylic acids, such as diethylene glycol di(meth)acrylate (meaning diacrylate or dimethacrylate,
(same hereinafter), triethylene glycol (meth)acrylate, tetraethylene glycol di(meth)acrylate, trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, 1,3-propane,
1,3-butanediol di(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)
A compound obtained by condensing a polyhydric alcohol such as acrylate, dipentaerythritol penta(meth)acrylate, 2,2'bis(4-acryloxydiethoxyphenyl)propane with an α,β-unsaturated carboxylic acid, Glycidyl group-containing compounds such as those obtained by adding α,β-unsaturated carboxylic acid to glycidyl group-containing compounds, trimethylolpropane triglycidyl ether tri(meth)acrylate, and bisphenol A diglycidyl ether (meth)acrylate. Compounds obtained by adding α,β-unsaturated carboxylic acids, unsaturated amides such as methylenebisacrylamide, ethylenebisacrylamide, 1,6-hexamethylenebisacrylamide, divinylsuccinate, divinyladipate, divinyl Examples include vinyl esters such as phthalate, divinyl terephthalate, and divinylbenzene-1,3-disulfonate. One type or two or more types of addition polymerizable compounds are used. The aminobenzoic acid ester used in the present invention is represented by the above formula [], and in the above formula [], R ₁ and R ₂ are hydrogen or have 1 to 3 carbon atoms.
alkyl group, R ₃ is an alcohol residue, R ₁ ,
R ₂ and R ₃ may be the same. For example, methyl 4-dimethylaminobenzoate, 4-dimethylaminobenzoic acid ester, n-propyl 4-dimethylaminobenzoate, isopropyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 4-dimethylaminobenzoic acid (2-n-Butyl)ethyl, methyl 4-diethylaminobenzoate, ethyl 4-diethylaminobenzoate, n-propyl 4-diethylaminobenzoate, isoamyl 4-diethylaminobenzoate, ω-dimethylaminooctadecyl 4-diethylaminobenzoate etc. In the present invention, the compound having an isoalloxazine skeleton [] represented by the above formula [] is 430-
It has an absorption maximum at 460 nm and can generate active radicals by absorbing light. Therefore, it is possible to provide high sensitivity to visible light such as the main output wavelength of an argon laser. For example, riboflavin, riboflavin tetrabutyrate,
Riboflavin tetraacetate, riboflavin tetrapropionate, flavin mononucleotide, flavin adenine dinucleotide, lumichrome, lumiflavin, etc. Riboflavin or riboflavin tetrabutyrate, riboflavin tetraacetate, riboflavin tetrapropionate is used because of its solubility and ease of availability. Riboflavin tetraesters such as are preferred. The photopolymerizable composition of the present invention may contain one or more high molecular weight organic polymers, if necessary. the high molecular weight organic polymer is thermoplastic;
The molecular weight is preferably 10,000 to 700,000.
For example, the following are used. (A) Copolyester A polyhydric alcohol such as diethylene glycol, triethylene glycol, tetraethylene glycol, trimethylolpropane, neopentyl glycol, etc., and a polyhydric carboxylic acid such as terephthalic acid, isophthalic acid, sebacic acid, adipic acid, etc. are condensed together. copolyester obtained by (B) Vinyl polymer methacrylic acid, acrylic acid, methyl (meth)
Acrylate, ethyl (meth)acrylate,
Homopolymers or copolymers of vinyl monomers such as methacrylic acid alkyl esters or acrylic acid alkyl esters such as butyl (meth)acrylate and β-hydroxyethyl (meth)acrylate, styrene, vinyltoluene, vinyl chloride, and vinyl butyral. (C) Polyformaldehyde (D) Polyurethane (E) Polycarnate (F) Polyamide such as nylon (G) Cellulose ester such as methyl cellulose and ethyl cellulose By adding a high molecular weight organic polymer to a photopolymerizable composition, it can be applied to a substrate. Properties such as adhesion, chemical resistance, and film formability can be improved. The amount of this high molecular weight organic polymer is preferably 80% by weight or less based on the total weight of the high molecular weight organic polymer and the addition polymerizable compound. If the amount exceeds 80% by weight, photocuring will not proceed sufficiently, which is not preferable. The photopolymerizable composition of the present invention may also contain coloring substances such as dyes and pigments, if necessary.
Known coloring substances are used, such as fuchsin, crystal violet, methyl orange, Nile Blue 2B, Victoria Pure Blue,
There are Malachite Green, Night Green B, Spilon Blue, etc. In addition, the photopolymerizable composition of the present invention may contain a radical polymerization inhibitor or a radical polymerization inhibitor to improve stability during storage. For example, p
-Methoxyphenol, hydroquinone, pyrogallol, naphthylamine, phenothiazine, pyridine, nitrobenzene, aryl phosphite, etc. The photopolymerizable composition of the present invention may also contain other additives known to be used in photopolymerizable compositions,
For example, additives such as plasticizers and adhesion promoters may be included. The photopolymerizable composition of the present invention can be coated on a support and exposed to actinic rays to produce printing plates, or can be used as a photoresist for forming circuits by etching or plating. The actinic ray source used usually generates actinic rays with a wavelength of 250 nm to 550 nm. Especially from 400
Materials sensitive to visible light at 550 nm are useful in that they can be used with laser light. Such light sources include carbon arc lamps, mercury lamps, xenon arc lamps, argon glow lamps, argon ion lasers, and the like. Supports include organic polymer films such as polyethylene film, polypropylene film, and polyethylene terephthalate film; metal plates such as copper plates, aluminum plates, and iron plates;
An insulating plate (glass epoxy base material, paper epoxy base material, paper phenol base material, etc.) with a copper foil pasted on the surface is used. Examples of the present invention will be described. Here, parts and % indicate parts by weight and % by weight. Example: Preparation of photopolymerizable composition 40% of acrylic polymer (copolymer of methacrylic acid/methyl methacrylate/butyl methacrylate/2-ethylhexyl acrylate = 23/51/6/20 parts by weight ratio, weight average molecular weight approximately 90,000)
% ethyl cellosolve solution 120 parts Tetraethylene glycol diacrylate 25 parts Hydroquinone 0.04 parts Photoinitiator (compounds in Table 1) 4 parts Victoria Pure Blue 0.8 parts Methyl ethyl ketone 20 parts The above materials were stirred and dissolved to form a 23 μm thick polyethylene terephthalate film. (manufactured by Toray Industries, Inc., product name "Lumirror") using a bar coater.
A photopolymerizable element was obtained by drying for about 3 minutes in a hot air convection dryer at 100°C. The thickness of the dried photopolymerizable composition layer was 30 μm. Next, using a laminator that applies pressure and heat with a rubber roll to laminate the photopolymerizable composition layer, the photopolymerizable composition layer is placed on a 1.6 mm thick glass epoxy copper clad laminate with a clean surface so that the photopolymerizable composition layer and the copper surface are in contact with each other. Elements were laminated (rubber roll temperature 160℃). A step tablet (manufactured by Dainippon Screen Co., Ltd., trademark gray scale, optical density step 0.15, minimum optical density 0.05, maximum optical density 3.05, negative film with 21 step differences) or further on the polyethylene terephthalate film of the laminated sample. Colored glass filter (manufactured by Toshiba Glass Co., Ltd., "Colored Glass Filter Y-43", 400nm
3KW ultra-high pressure mercury lamp (manufactured by Oak Seisakusho Co., Ltd., trademark Phoenix)
3000) for 15 seconds. The exposure amount measured using the Oak Manufacturing Co., Ltd.'s "Ultraviolet irradiance meter UV-MO1" with a sensor with maximum spectral sensitivity at 420 nm is
21.1 mW/cm ² , 6.7 mW/cm ² when using a colored glass filter, and 6.4 mW/cm when not using a colored glass filter, measured using a sensor with maximum spectral sensitivity at 350 nm ² ,
0.2mW/when using colored glass filter
It was warm in ^cm2 . After that, the polyethylene terephthalate film was removed and placed in a 2% Na ₂ CO ₃ aqueous solution at 30°C.
The uncured portion was eluted by rocking immersion for 40 seconds, and the number of steps on the step tablet was determined to be the sensitivity of the photopolymerizable composition (the higher the number of steps, the higher the sensitivity). Table 1 shows a comparison of the sensitivity of the compositions.

【table】

[Table] In addition, an argon ion laser beam (manufactured by LEXEL, 2W, 457.9nm single line mode, beam diameter 1.3mm by optical system,
(Magnified to 5 mm on the irradiated surface) was irradiated.

[Table] The exposure amount was measured with a power meter (Photodyne Optical Power Meter 44XLA).
After exposure, the polyethylene terephthalate film was removed and immersed in a 2% Na ₂ CO ₃ aqueous solution at 30°C for 40 seconds to elute the uncured portion, and the sensitivity was determined by measuring the diameter of the remaining portion. Examined.
The results are shown in FIG. FIG. 1 shows that the photopolymerizable composition of the present invention polymerizes with a smaller amount of exposure than the comparative example and has high sensitivity. The photopolymerizable composition of the present invention has high sensitivity to visible light.

[Brief explanation of the drawing]

FIG. 1 is a diagram showing the change in residual film diameter with respect to the exposure amount of a laser beam for the compositions of Examples and Comparative Examples.

Claims (1)

[Scope of Claims] 1 (1) Addition polymerizable compound having a boiling point of 100°C or higher at normal pressure (2) An aminobenzoic acid ester represented by the following formula [] and (In the formula, R ₁ and R ₂ are hydrogen or have 1 to 3 carbon atoms.
an alkyl group, R ₃ is an alcohol residue,
(R ₁ , R ₂ and R ₃ may be the same) (3) A compound having an isoalloxazine skeleton represented by the following formula [] (In the formula, R ₄ and R ₅ are hydrogen, a methyl group, or an ethyl group, and these may be the same.) A photopolymerizable composition comprising: 2. The light according to claim 1, which contains a high molecular weight organic polymer, and the high molecular weight organic polymer is 80% by weight or less based on the total weight of the high molecular weight organic polymer and the addition polymerizable compound. Polymerizable composition. 3. The photopolymerizable composition according to claim 1, wherein the compound having an isoalloxazine skeleton is riboflavin or riboflavin tetraester.