JPS59189340A - Photopolymerization initiator composition having high sensitivity - Google Patents

Abstract

PURPOSE:To attain satisfactory photopolymn. initiating power by combining an org. peroxide with an org. dye compound having a specified structure. CONSTITUTION:This photopolymn. initiator composition contains one or more kinds of org. peroxides (PO) and one or more kinds of org. dye compounds (DY) as effective components in (1-99):(99-1) weight ratio of PO:DY. Most of unsatd. compounds can be photopolymerized under ultraviolet light or visible light in a vary short time by using the initiator composition. Org. compounds each having one or more oxygen-oxygen bonds in the molecule such as methyl ethyl ketone peroxide, cyclohexanone peroxide and 3,3,5-trimethylcyclohexanone peroxide are used as the org. peroxides, and the org. dye compounds include cyanine, merocyanine, xanthene and thiazole dyes each having a specified structure and assuming a color in the range of yellow-red-purple.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a photopolymerization initiator composition for the polymerization of ethylenically unsaturated compounds, and more particularly to a photopolymerization initiator composition that is sensitive to ultraviolet and visible light at low doses and is usable for laser applications. This invention relates to a highly sensitive photopolymerization initiator composition.

It is well known that monomers, oligomers, and polymers containing unsaturated bonds in their molecules undergo photocoagulation in the presence of a photocoagulation initiator. This phenomenon also occurs.

It is widely used as a Kokonegura-type photopolymer and photoresist, which is used in the production of printing plates, printed circuit boards, ICs, etc.

Various substances have been reported and actually used as photo-M@initiators used in these. for example,
Benzoin compounds include benzoin, benzoin methyl ether, benzoin ethyl ether, etc. Carbonyl compounds include benzyl, benzophenone, acetophenone, Micher's ketone, etc. Azo compounds include azobisisobutyronitrile, azodibenzoyl, etc. Sulfur compounds include dibenzothiazolyl sulfide , tetraethylthiuram disulfide, etc., halogen compounds such as carbon tetrabromide, tribromphenyl sulfone, etc. 1.2
- Examples include benzanthraquinone.

However, these photopolymerization initiators are still not completely satisfactory, and when combined with individual unsaturated compounds, they cannot necessarily be said to have good sensitivity as a photopolymer.

In addition, in recent years, methods of forming images using lasers have been studied, and in printing plate production, laser direct plate making, one-north facsimile, holography, etc. are already at the stage of practical application, and many more fields will be developed in the future. Its application is being considered and expected.

Silver salt photosensitive materials, electrophotographic materials, photochromic materials, photopolymers, etc. are used as photosensitive materials for lasers, but among these, photopolymers have extremely high sensitivity compared to silver salt photosensitive materials and electrophotographic materials. It has a low sensitivity to light, and its sensitive wavelength range is from ultraviolet to visible light. For example, the sensitivity of silver halide film (Cogris Orthofilm 2556 Type 3) is Ar + laser wavelength 4.
The amount of energy required for monochromatic light of 88 nm is 0.02 (L
, 5rn J/-, but for photopolymer (Kodak Horimachi Chrysoplate LN -L) it is 7oo
omJ/cJ is also required, wavelength 351/364
Even if ultraviolet light of nm is used] OOm J /
The energy key of ta is required.

As described above, conventional photopolymers are unsatisfactory in both sensitivity and sensitive wavelength range, and are particularly unsuitable as photosensitive materials for visible light lasers.

Against this background, the inventors of the present invention have conducted extensive research keeping in mind the above points, and have found that a combination of an organic peroxide and an organic dye compound with a specific structure is extremely effective even in the visible light region. The present invention was achieved by discovering that the photopolymerization initiator has a high KIA degree close to that of silver salt photosensitive Hamura.

The present invention provides a photopolymerization initiator composition comprising a combination of one or more organic peroxides and one or more organic dye compounds.

The organic peroxide used in the present invention has oxygen in its molecule.
Almost all organic compounds having one or more oxygen bonds are included; examples include methyl ethyl ketone peroxide, cyclohexanone peroxide, 3,
3.5-trimethylcyclohexanone peroxide,
Methylcyclohexanone peroxide, acetylacetone peroxide, 1,1-bis(tert-butylperoxy) -3,3,5-trimethylcyclohexane 51.1-bis(tert-butylperoxy)
Cyclohexane, n-butyl-4,4-bis(tert-butylperoxy)valerate, 2,2-bis(tert-butylperoxy)butane, tert-butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroper oxide, para-menthane hydroperoxide, 2.5-
Dimethylhexane-2,5-cybidrobar oxide, 1.1.3.3. -Tetramethylbutyl hydroperoxide, diside, α,α'-bis(tert-butylbaroxyisopropyl)benzene, 2,5-dimethyl-2
, 5-di(tert-butylperoxy)hexane,
2,5-dimethyl-2゜5-di(tert-butylperoxy)hexyne-3, acetyl peroxide, isobutyryl peroxide, octanoyl peroxide, decanoyl peroxide, lauroyl peroxide, 3,5.5 -Trimethylhexanoyl peroxide, succinic peroxide, benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, meta-toluoyl peroxide, diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, di-n-propyl Peroxydicarbonate, di-2-ethoxyethyl peroxydicarbonate, dimethoxyisopropyl peroxycarbonate, di(3-methyl-3-methoxybutyl)peroxydicarbonate, tert-butyl peroxyacetate, tert-butyl peroxyiso Butyrate, tert-butyl vanioxypiparate, tert-butyl 6-peroxyneodecanoate, tert-butyl peroxyoctanoate, tert-butyl peroxy 3.5.5-)limethylhexanoate, Tertiary butyl peroxylaurate, Tertiary butyl peroxydipenzoate, Ditertiary isoperoxyisophthalate, 2,5-dimethyl-2,5-di(benzoylperoxy)hexane, Tertiary butyl maleic peroxide acids, tert-butyl peroxyisopropyl carbonate, etc.

The organic dye compound used in the present invention has a specific structure as exemplified below and exhibits a color range of yellow to red to violet.

A dianine dye a) B: Merocyanine dye a) 9- c).

1 ■ CH2C-0X I C: xanthene dye = 10- D: thiazole dye a) The photoinitiator composition of the present invention contains the above-mentioned NW peroxide +
It contains one or more of the above organic dye compounds (DYI) and one or more of the organic dye compounds (DYI) as active ingredients.
+1:(DY) is 1-99:99-1, more preferably 3-95:97-5. If the composition is outside this range, the Song Dynasty, which has a talent of 1, will have 11. i"I,... □
The initiator 4i11 composition of the present invention can photopolymerize almost all non-M chlorinated I compounds in a very short time using ultraviolet light and visible light. These unsaturated compounds include monomers, oligomers, and polymers having polymerizable ethylenically unsaturated bonds, such as acrylic acid, methacrylic acid, itaconic acid, maleic acid and its anhydride, phthalic acid and its anhydride, and fumaric acid. Unsaturated acids such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, glycidyl (meth)acrylate, hydroxyethyl (meth)acrylate,
Dimethyl maleate, diethyl maleate.

Dimethyl fumarate, pentaerythritol tri(meth)
Unsaturated acid esters such as acrylate, trimethylolpropane tri(meth)acrylate, ethylene glycol di(meth)acrylate, and brobylene glycol di(meth)acrylate.

and styrene, acrylamide, acrylonitrile,
Examples include N-vinylpyrrolidone, vinyl acetate, unsaturated acid polyesters, unsaturated polyethers, unsaturated polyurethanes, and epoxy (meth)acrylate compounds.

13- A photopolymerizable composition is prepared by adding one or more of these unsaturated compounds and a suitable diluting solvent.

Addition 1 of the photopolymerization initiator composition is O,1 to 4 parts by weight, preferably 05 to 30 parts by weight, per 100 parts by weight of the unsaturated compound.
Parts by weight.

Further, as suitable diluting solvents, any solvent can be used as long as it dissolves the photopolymerization initiator composition of the present invention and the unsaturated compound used, for example.

Water, methanol, ethanol, propatool, butanol, acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl cellosolve, ethyl cellosolve, benzene, toluene, xylene, ethyl acetate, butyl acetate, tetrahydrofuran, dioxane, dichloromethane, chloroform, carbon tetrachloride, trichlor Examples include ethylene, dimethylformamide, and dimethyl sulfoxide.

The photopolymerizable composition thus obtained is irradiated with actinic light in a wide range from ultraviolet to visible light (a polymerization reaction can be achieved in a very short time).

Light sources used include ultra-high pressure, high pressure, medium pressure, and low pressure mercury lamps, chemical lamps, carbon arc lamps, xenon lamps, metal halide lamps, various visible and ultraviolet laser lamps, fluorescent lamps, tungsten lamps, and sunlight. can.

The photopolymerization initiator composition of the present invention can be used not only for ordinary photopolymerization reactions, but also for the production of photocurable paints, printing inks, adhesives and printing plates, as well as photoresists for the production of printed circuit boards, ICs, etc. It can be applied in many fields, and its effects are also very good. In particular, due to the high sensitivity and wide spectral sensitivity characteristics up to the visible light region, which are the features of the photopolymerization initiator composition of the present invention, it has surprisingly good effects when applied to photosensitive materials for visible light lasers such as Ar+ lasers. Get it.

The present invention will be explained in more detail below using Examples and Comparative Examples. Note that parts in the examples are parts by weight.

These examples are provided for illustrative purposes and are not intended to limit the invention in any way.

Examples 1 to 51 Using 100 parts of pentaerythritol triacrylate as an unsaturated compound and 100 parts of poly-N-vinylpyrrolidone as a binder, the photo-N-initiator composition of the present invention was added in the proportions shown in Table 1. and further add these to 1O
It was coated on methyl cello in the flO section using a spinner so that the dry coating thickness was 1 μm.

The photosensitivity test was performed using visible light (wavelength = 488 nm).

Ultraviolet light (wavelength - 36snm) and laser light (wavelength =
= 488 nm) was used for each monochromatic light.

The monochromatic light of 488 nm of visible light is
Obtained by passing through 12 49f7' filters.

Monochromatic light of 365 nm was obtained by using a 45 NW high-pressure mercury lamp as a light source and passing it through a Toshiba color glass filter TI VI]35. The laser beam is a single line with a 25W Ar'' laser wavelength of 488nm and a beam diameter of 125 nm.
I used it at my friend. exposing the photosensitive film using each monochromatic light;
Sensitivity was measured by the cumulative light energy until the coating film was completely photocured.

The results are shown in Table 1, and the amounts of photopolymerization initiator compositions in Table 1 are all pentaerythritol triacrylate 100
This is for the department.

Comparative Examples 1 to 5 Same as in Examples, except that instead of the photopolymerization initiator composition of the present invention, a conventionally known photopolymerization initiator, an organic peroxide, and an organic dye compound were used individually. A photosensitivity test was conducted to measure the sensitivity.

The results are shown in Table 2, and the amounts of photopolymerization initiators in the table are all based on 100 parts of pentaerythritol triacrylate.

17-1 -20- The abbreviations in Table-1 and Table-2 are as follows.

0 Organic peroxide BPO: Penzoyl peroxide PBIF: Ditertiary butyl diperoxyisophthalate POZ: 2,5-dimer-fk-2,5-cy(heysoylperoxy)hexane PBZ: Tertiary butyl peroxybenzoate PXM: α,α′-bis(tert-butylperoxyisopropyl)benzene DCP: dicumyl peroxide O organic dye compound 21- A-3= B-1: B-2: 22- B-6: 1 C2 'F (5 B -8: C1 (2cOOK C-1: C-2: C-3: D -1: D -2: ○ Known photoinitiator BIPE: Benzoin isopropyl ether BP: Benzophenone MK: Micher's ketone 1 .2-BA: 1.2-Benzanthraquinone As is clear from Tables 1 and 2, all of the Examples in which an organic peroxide and an organic dye compound were combined were significantly more effective than the Comparative Examples. It can be seen that the sensitivity is high.

Patent applicant: NOF Corporation 25-

Claims (1)

[Scope of Claims] 1. An initiator composition comprising a combination of one or more organic peroxides and one or more organic dye compounds. 2. The composition according to claim 1, wherein the organic dye compound is a cyanine dye. 3. The composition according to claim 1, wherein the organic dye compound is a merocyanine dye. 4. The composition according to claim 1, wherein the dye compound is a xanthine dye. 5. The composition according to claim 1, wherein the organic dye compound is a thiazole dye.