JPS63132902A - Photo-polymerization initiator composition - Google Patents

Abstract

PURPOSE:To obtain a photo-polymerization initiator composition for unsaturated compound, having extremely excellent photopolymerization initiation capability and high sensitivity and stability, by combining an organic peracid ester compound having a specific structure with an organic dye compound. CONSTITUTION:The objective composition can be produced by compounding (A) an organic peracid ester compound having benzene skeleton or benzophenone skeleton in the molecule (e.g. t-butyl peroxybenzoate, di-t-butyl diperoxyisophthalate, etc.) and (B) one or more kinds of organic dye compounds of formula I-III (R1, R2, R3 and R5 are 1-4C alkyl; R4 is 1-4C alkylene) usually at a weight ratio (A:B) of 1:30-10:1. The initial rate of polymerization is increased in the photopolymerization of an unsaturated compound. The composition is useful for photopolymer and photo-resist.

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Field of Application> The present invention relates to a photopolymerization initiator composition for polymerizing unsaturated compounds.

It is well known that monomers, oligomers, and polymers containing unsaturated bonds in their molecules are photopolymerized in the presence of a photoinitiator, and so-called photobombers are used to create printing plates, printed circuit boards, ICs, etc. It is widely used as a photoresist.

<Prior art> As photopolymerization initiators used in these, various substances have been reported and actually used1. For example, benzoin-based compounds include benzoin, benzoin alkyl ether (USP No. 2448282), etc. Carbonyl compounds include benzyl, benzophenone, acetophenone, pendyl ketal, etc.; azo compounds include azobisisobutyronitrile azodibenzoyl; and sulfur compounds include dibenzothiazolyl sulfide and tetraethylthiuram disulfide.

<Problems to be Solved by the Invention> However, photopolymerizable compositions comprising these photopolymerization initiators and various unsaturated compounds do not necessarily have good sensitivity as photopolymers; There is a strong demand for highly sensitive and highly stable photopolymerization initiators.

In addition, there are many types of organic peroxides that have peroxide bonds in their molecules, such as hydroperoxides, dialkyl peroxides, diacyl peroxides, peracid esters, and percarbonate esters, and these can be decomposed by heat. It is well known that active radicals are generated by oxidation, and it is widely used as a thermal polymerization initiator, a thermal polymerization catalyst, a thermal polymerization crosslinking agent, etc. for unsaturated compounds. Furthermore, it has been reported that organic peroxides are also decomposed by light energy and similarly generate active radicals. However, these organic peroxides have low photopolymerization initiating ability for use as photopolymerization initiators for unsaturated compounds, and generally have low thermal stability, so they are not suitable for practical use on the side bottom, and therefore are not suitable for use as polymerization type initiators. There have been no known examples of using organic peroxides as photopolymerization initiators for photopolymers.

<Means for Solving the Problems> Against this background, the present inventors conducted extensive research and found that a combination of an organic peracid ester compound having a specific structure and an organic dye compound has extremely good photopolymerization. The present invention was achieved by discovering that it has initiation ability and increases the initial polymerization rate in the photopolymerization of unsaturated compounds, and that by using it, a highly sensitive photosensitive resin can be obtained.

That is, the present invention provides an organic peracid ester compound having a benzene skeleton or benzophenone skeleton in the molecule, and a compound represented by the following general formulas (1) to ([1) (R represents a furkyl group having 1 to 4 carbon atoms). Display]CRY-
Rs is an alkyl group having 1 to 4 carbon atoms, and R4 is an alkyl group having 1 to 4 carbon atoms.
R represents an alkylene group, and R represents an alkyl group having 1 to 4 carbon atoms. .

The present invention will be explained in more detail below.

As the organic peracid ester compound used in the present invention,
Those having a 10-hour half-life temperature of 70° C. or higher are preferred, such as tert-butyl peroxybenzoate, tert-butyl peroxymethoxy benzoate, tert-butyl peroxynitrobenzoate, tert-butyl peroxyethyl benzene-1-, phenylisopropyloxybenzoate. , ditertiary butyl diperoxy isophthalate, tritertiary butyl triperoxytritate, tritertiary butyl triperoxy trimellitate, tritertiary butyl triperoxy trimellitate, tetratertiary butyl tetratraoxypyromellitate, 2 , 5-dimethyl-2,5-di(benzoylperoxy)hexane, 3.3'.

4.4'-tetra(tertiarybutylperoxycarbonyl)benzophenone, 3.3',4'-tetra(tertiaryamylperoxycarbonyl)benzophenone, 3.3',4.4'-tetra(tert. xylperoxycarbonyl)benzophenone, etc.

The organic dye compound used in the present invention is represented by the following formulas (If) and (III): merocyanine dye represented by the following formula, [R represents an alkyl group having 1 to 4 carbon atoms] Thioxanthin dye, (R2-R3 represents an alkyl group having 1 to 4 carbon atoms, R4 represents an alkylene group having 1 to 4 carbon atoms.) CRs represents a carbon number 1
~4 alkyl groups], and these organic dye compounds may be used alone or in combination of two or more,
Any commercially available products can be used as appropriate.

The photopolymerization initiator composition of the present invention consists of the above-mentioned (A) organic peracid ester compound and (B) organic dye compound, and the blending ratio of both (A) and (B) is determined by the weight ratio. in(
The ratio of A):(B) is preferably 1:100 to 100:1, more preferably 1:30 to 10:1.

The reason why the photopolymerizable Ug initiator composition of the present invention can serve as a good photopolymerization initiator for unsaturated compounds is thought to be due to the effective sensitized photodecomposition of the organic peracid ester compound by the organic dye compound. By selecting an organic dye compound, it is possible to exhibit photopolymerization initiation ability in the range from ultraviolet light to visible light, so any light source can be used, and it can also be used as a photopolymerization initiator for photosensitive materials for visible light lasers. Available.

The photopolymerization initiator of the present invention can photopolymerize almost all unsaturated compounds. That is, the unsaturated compound can be applied to polymers, oligomers, or polymers having polymerizable ethylenically unsaturated bonds, such as acrylic acid, methacrylic acid, itaconic acid, maleic acid, and their anhydrides.

Unsaturated acids such as phthalic acid and its anhydride, fumaric acid, methyl (meth)acrylate, ethyl (meth)acrylate, (
Butyl meth)acrylate, glycidyl (meth)acrylate, hydroxyethyl (meth)acrylate, dimethyl maleate, diethyl maleate, dimethyl fumarate, pentaerythritol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, Unsaturated acid ester compounds such as ethylene glycol di(meth)acrylate and propylene glycol di(meth)acrylate, monomers such as acrylamide, acrylonitrile, N-vinylpyrrolidone, and vinyl acetate, as well as unsaturated polyesters and unsaturated polyethers. It can be used for photopolymerization of unsaturated polyurethane, epoxy (meth)acrylate compounds, etc.

The photopolymerization initiator composition of the present invention is added to one or a mixture of two or more of these unsaturated compounds, and if necessary, a suitable diluting solvent is added to prepare a photopolymerization composition.

The amount of the photopolymerization initiator composition added is 0.1 to 30 parts by weight, preferably 0.5 to 2 parts by weight, per 100 parts by weight of the unsaturated compound.
0 parts by weight is desirable.

Further, a suitable diluting solvent is any solvent that can dissolve the photopolymerization initiator composition and unsaturated compound of the present invention.
For example, water, methanol, ethanol, propatool,
These include butanol, acetone, methyl ethyl ketone, methyl isobutyl ketone, toluene, xylene, ethyl acetate, butyl acetate, cellosolve, tetrahydrofuran, dioxane, dichloromethane, chloroform, carbon tetrachloride, trichloroethylene, dimethylformamide, dimethyl sulfoxide, and the like.

The photopolymerizable composition thus obtained undergoes a polymerization reaction by irradiating it with actinic light such as ultraviolet rays or visible light. Ultra-high pressure as a light source.

Various high pressure, medium pressure and low pressure mercury lamps, chemical lamps,
Carbon arc lamps, canon lamps, metal halide lamps, fluorescent lamps, tungsten lamps, sunlight, and various laser lamps can be used.

<Effects of the Invention> Since the photopolymerization initiator composition of the present invention uses the above-mentioned organic peracid ester compound and organic dye compound in combination, it has significantly higher sensitivity than conventional photopolymerization initiators, and has a weak It is also excellent in terms of workability and economy, as it is sufficiently exposed to light from any light source.

The photopolymerization initiator composition of the present invention can be used in ordinary photopolymerization reactions, and can also be applied to a variety of fields such as photocurable paints, printing inks, adhesives, printing plate preparation, and photoresists. The effect is also very good, and the highest sensitivity can be obtained.

<Examples> The present invention will be explained in more detail below using Examples and Comparative Examples. Note that parts indicate parts by weight.

Large lid ■ Upper two main parts ± Poly (methyl methacrylate/ethyl acrylate/methacrylic acid) (mole ratio 5/4/1: molecular weight 100,000) 100
The photopolymerization initiator composition of the present invention shown in Table 1 was added to 100 parts of pentaerythritol triacrylate (manufactured by Shin Nakamura Chemical ■: A-TMM-3L) in the proportions shown in Table 1. A photosensitive solution was obtained by uniformly dissolving in 1000 parts of ethyl cellosolve.

Each of these photosensitive solutions was applied onto an anodized aluminum plate using a hoarer so that the dry coating thickness was 2 μm, and dried to obtain a photosensitive test plate. Grayscale (Step Tablet Nα2 manufactured by Kodak Corporation) was vacuum-adhered to this photosensitive test plate, and after exposure for 1.5 seconds using a KW ultra-high pressure mercury lamp from a distance of 60 am,
Commercially available alkaline developer (Fuji Photo Film-IllON
-3C) and the sensitivity was measured by reading the number of gray scale steps in the cured area. The results are shown in Table-1. Note that the number of steps indicates that the sensitivity is doubled when there is a difference of two steps, and the larger the number, the higher the sensitivity.

Example 11: For comparison, examples were conducted using commercially available photopolymerization initiators, organic dye compounds, or organic peracid ester compounds shown in Table 2 instead of the photopolymerization initiator composition of the present invention. A photosensitive solution was obtained in the same manner as above, and the same measurements as in Examples were performed. The results are shown in Table-2.

PBZ: tert-butyl peroxybenzoate PBIF tertiary-butyl diperoxyisophthalate BTTB: 3,3',4,4'-tetra(tert-butylperoxycarbonyl)benzophenone TMT tertiary-butyl triperoxytrimelitate B-1 : Su B-2: Su C-1: C-2: C-3: BIBE: Benzoin isobutyl ether Irgacure 651 Nidimethoxyphenylacetophenone (Ciba Geigy Il) Irgacure 907: 2-Methyl-1-(4 −(
Methylthio)phenyl]-2 Monomorpholinopropanone-1 (manufactured by Ciba Geigy) Darocure 1173: 3-Hydroxy-2-methyl-1-phenyl-propan-1-one (Merck Company 11) Other abbreviations are listed in Table-1 From the results in Table 19 and Table 2, it is clear that the sensitivity of the examples is extremely higher than that of the comparative examples.

Claims (1)

[Claims] An organic peracid ester compound having a benzene skeleton or benzophenone skeleton in the molecule, and the following general formulas (I) to (
Compounds represented by III) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (I) [R_1 represents an alkyl group having 1 to 4 carbon atoms] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (II) [R_2, R_3 is an alkyl group having 1 to 4 carbon atoms, R_4
represents an alkylene group having 1 to 4 carbon atoms. ] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (III) Photopolymerization initiator in combination with one or more organic dye compounds selected from [R_5 represents an alkyl group having 1 to 4 carbon atoms] agent composition.