JPS6057832A - Photopolymerizable composition - Google Patents

Abstract

PURPOSE:To enhance sensitivity by incorporating an additionally polymerizable compd., aminobenzoate, and a compd. having isoalloxazine structure. CONSTITUTION:A photopolymerizable compsn. contains an additionally polymerizable compd., aminobenzoate represented by formula I , and a compd. having an isoalloxazine structure represented by formula II. A photoinitiator is especially important in order to allow a combination of said aminobenzoate and the compd. having said isoalloxazine structure to enhance sensitivity. As said additionally polymerizable compd. contained in the photopolymerizable compsn., one having a b.p. of >=100 deg.C at normal pressure are used. If it is lower than 100 deg.C at normal pressure, a part of said compd. vaporizes in removing solvents contained in the system through heat drying, and adversely affects the characteristics and the operation environment. Said photopolymerizable compd. has high sensitivity to the visible light.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to novel photopolymerizable compositions, and more particularly to photopolymerizable compositions containing a novel photoinitiator system.

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. Especially 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 4'58, 488, and 514 nm, which is its main output wavelength.

Much research has been done in this field on photoinitiator systems for increasing overall 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 that are particularly sensitive to visible light are known. 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 provides (1) an addition polymerizable compound having a boiling point of 100° C. or higher at normal pressure, (2) an amine benzoate ester represented by the following formula [1], and (wherein R1 and R2 are hydrogen or a carbon prime number is 1-3
The alkyl group, R3 is an alcohol residue.

R2 and R3 may be the same) (3) A compound having an alloxazine skeleton represented by the following formula (If) (where R4 and R are hydrogen, a methyl group or an ethyl group, and they may be the same) 2. A photopolymerizable composition comprising:

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. If the boiling point is lower than 100°C at normal pressure, a part of the addition polymerizable compound will volatilize when the solvent contained in the system is removed by heating and drying or when irradiated with active light a, resulting in poor characteristics and This is because it is unfavorable in terms of workability. In addition, the addition polymerizable compound may be acetone, methyl ethyl ketone, or
Toluene, chloroform, methanol.

Those soluble in organic solvents such as ethanol and 1,1.1-trichloroethane are preferred. Examples of addition-polymerizable compounds include compounds obtained by condensing polyhydric alcohols with α, β-, and β-carboxylic acids8, for example, diethylene glycol di(
meth)acrylate (diacrylate means dimethacrylate, the same applies hereinafter), triethylene glycol (meth)acrylate, tetraethylene glycol di(
meth)acrylate, trimethylolpropane triacrylate, trimethylolpropane tri(meth)acrylate, 1,3-propane, 1,3-butanediol di(meth)acrylate, pentaerythritol tetra(
meth)acrylate, dipentaerythritol hexa(
Meta) acrylate.

dipentaerythritol penta(meth)acrylate,
2.2'bis(4-acryloxyshedquinophenyl)
A compound obtained by condensing a polyhydric alcohol such as propane with an α,β-unsaturated carboxylic acid.

Glycidyl group-containing compounds such as those obtained by adding α,β-unsaturated unsaturated norboxic acid to a glycidyl group-containing compound, trimethylolpropane triglycidyl ether tri(meth)acrylate, and bisphenol A diglycidyl ether (meth)acrylate. Compounds obtained by converting a compound to an α,β-unsaturated unsaturated norboxic acid, an unsaturated amide such as methylenebisacrylamide, ethylenebisacrylamide.

1. Unsaturated amides such as 6-hexamethylenebisacrylamide, dipinyl sacunnate, divinyl acyhate,
Examples include vinyl esters such as divinyl phthalate, divinyl terephthalate, and dihynylbenzene-1,3-disulfonate.

One or more addition polymerizable compounds may be used.

The ami7benzoic acid ester used in the present invention is represented by the above formula (1), and in the above formula CI), R1 and R2 are hydrogen or an alkyl group having 1 to 3 carbon atoms, and the island is an alcohol residue. + R1rR2 and R3 may be the same. For example, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, n-propyl 4-dimethylaminebenzoate, isopropyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 4-dimethylaminobenzoic acid. (2-n-butyl)ethyl, methyl 4-diethylaminobenzoate.

Examples include ethyl 4-diethylaminobenzoate, n-propyl 4-diethylaminobenzoate, isoamyl 4-diethylaminobenzoate, and ω-dimethylaminooctadecyl 4-diethylaminobenzoate.

In the present invention, the compound having the isoalloxazine skeleton [B'3 represented by the above formula (ID) has 430 to 460
It has an absorption maximum at nm, and generates active radicals by absorbing light.

Therefore, high sensitivity to visible light such as the main output wavelength of an argon laser can be achieved. For example, riboflavin,
Riboflavin tetrabutyrate.

Riboflavin tetraacetate, riboflavin tetraglobionate, flavin mononucleotide.

Flavin adenine dinucleotide, Lumichrome.

Lumiflavin is preferred, but riboflavin or riboflavin tetraesters such as riboflavin tetraptylate, riboflavin tetraacetate, and riboflavin tetrafluorobutylene are preferred because of their solubility and ease of handling.

The photopolymerizable composition of the present invention may contain one or more types of high molecular weight organic polymers, if necessary. The high molecular weight organic polymer must be thermoplastic.

Preferably, the molecular weight is io, ooo to 700,000. For example, the following are used.

Prisoner copolyester Polyhydric alcohols such as diethylene glycol.

triethylene glycol, tetraethylene glycol,
iJ Methylolpropane, neopentyl glycol, etc. and polyhydric carboxylic acid 1 such as terephthalic acid, isophthalic acid,
A copolyester obtained by condensing sebacic acid, adipic acid, etc.

(Bl vinyl polymer methacrylic acid, acrylic acid, methacrylic acid alkyl ester such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, β-hydroxyethyl (meth)acrylate or °acrylic acid alkyl ester, styrene , vinyl toluene, vinyl chloride, vinyl butyral, etc., homopolymers or copolymers of vinyl monomers.

(C1 Polyformaldehyde ■) Polyurethane (El Polycarbonate W) Polyamide such as nylon (Gl Cellulose ester such as methyl cellulose and ethyl cellulose By adding a high molecular weight organic polymer to a photopolymerizable composition, it is possible to improve adhesion to the substrate, chemical resistance, Characteristics such as film-forming properties can be improved.The content 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 above-mentioned addition polymerizable compound. 80
If the amount exceeds 5% by weight, the photocuring power 5 will not be sufficient, which is undesirable.

The photopolymerizable composition of the present invention also includes: Coloring substances such as dyes and pigments may be contained as necessary.

Known coloring substances are used; for example, fuchsin,
Crystal violet, methyl onnge.

There are Dilpur-2B, Victoria Piyua Blue, Malachite Green, Night Green B, Subiron 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. Examples include p-methoxyphenol, hydroquinone, pyrogallol, nactylamine, phenothiazine, pyridine, nitrobenzene, arylphosphite, and the like.

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 applied as a photoresist for forming circuits by coating on a support and exposing it to actinic radiation to produce a printing plate, etching or plating. The actinic light source used is usually 250
A device that generates actinic rays with a wavelength of nm to 55Qnm is used. In particular, materials sensitive to visible light of 400 to 55 Qnm are useful in that they can be used with laser beams.

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, and insulating plates with copper foil on the surface (glass epoxy base material 9 paper epoxy Base material 1 paper, phenol base material, etc.) are used.

The present invention will be described in detail. Here, 1 part and q represent 9% by weight.

Examples Preparation of photopolymerizable composition Acrylic polymer (methacrylic acid/methyl methacrylate/butyl methacrylate/2-ethylhexyl acrylate = 23151/6/20 parts by weight copolymer 2
40 ethyl cellosolve solution with a weight average molecular weight of approximately 90.000 12
0 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, and a 23 μm thick polyethylene terephthalate film ( The photopolymerizable element was coated on a surface (manufactured by ToV Co., Ltd., trade name: "Lumirror") using a bar coater and dried for about 3 minutes in a hot air convection dryer at 100°C to obtain a photopolymerizable element. 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 and the copper surface are exposed to light on a 1.6 mm thick glass epoxy copper clad laminate with a clean surface. Polymerizable elements were laminated (rubber roll temperature i6oC). A step tablet (manufactured by Dainippon Screen ■) was placed on the polyethylene terephthalate film of the laminated sample.

Trademark Gray School, optical density step 0. i5. A negative film with a minimum optical density of 0.05 and a maximum optical density of 3.05, 21 steps) or a colored glass filter (manufactured by Toshiba Glass ■, "Colored Glass Filter Y-43j, 40
(blocks light of 0 nm or less).

Exposure was performed for 15 seconds using a 3KW ultra-high pressure mercury lamp (trade name: Phoenix 3000, manufactured by Oak Seisakusho).

■Oak Seisakusho “UV illuminance meter UV-MOIJ is 42”
The exposure amount measured using a sensor with a maximum spectral sensitivity at Q nm is 21.2 mW/cm'' without the nine-color glass filter and 6.7 mW/cm'' with the colored glass filter. +3 again
The exposure amount measured using a sensor with a maximum spectral sensitivity at 500 m is 6.0 m without using a colored glass filter.
．． 4 mW/cm", and 0.2 HEW/crn' when a colored glass filter was used. After that, the polyethylene terephthalate film was removed and the untreated film was immersed in a 2-inch Na2CO3 aqueous solution at 30°C for 40 seconds with rocking. The sensitivity of the photopolymerizable composition was determined by elution of the cured portion and the number of steps on the step tablet (75 steps; the higher the sensitivity, the higher the sensitivity). Table 1 shows a comparison of the sensitivity of the compositions. An argon ion laser beam (LEXE
Irradiation was performed using a 2WI 457.9r1m single line mode manufactured by L Company, beam diameter 1.3 mm (expanded to 51 nm at the irradiation surface) using a k optical system.

The exposure amount was measured with a power meter (Photodyne Optical Power Meter 44XLA). After exposure, the polyethylene terephthalate film was removed and the film was heated to 2% at 30°C.
The uncured portion was eluted by rocking immersion in an aqueous Na2CO3 solution for 40 seconds, and the sensitivity was examined by measuring the diameter of the remaining portion.

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 drawings]

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. Frost 1 Quality light amount (Hedari

Claims (1)

[Scope of Claims] 1. (11) An addition polymerizable compound having a boiling point of 100°C or higher at normal pressure (2) An amine benzoate ester represented by the following formula [1] and (where IRII and R2 are hydrogen or carbon Number 1 to 3 alkyl group + Ra is an alcohol residue, R1, R
2 and R3 may be the same) (3) A compound having an alloxazine skeleton represented by the following formula [I[] (wherein 4 and Rs are hydrogen, a methyl group, or an ethyl group, h) may be the same. z Contains a high molecular weight organic polymer, and the high molecular weight organic polymer is 80% by weight or less based on the total amount of the high molecular weight organic polymer and the addition polymerizable compound.Claim 1
The photopolymerizable composition described in . 3. The photopolymerizable composition according to claim 1, wherein the compound having an isoalloxazine skeleton is riboflavin or riboflavin tetraester.