JPH0365541B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a photopolymerization initiator composition for polymerizing ethylenically unsaturated compounds, and more particularly to a highly sensitive photopolymerization initiator composition that is sensitive to ultraviolet light and visible light at low doses and can be used for laser applications. It is related to. It is well known that monomers, oligomers, and polymers containing unsaturated bonds in their molecules are photopolymerized in the presence of a photoinitiator. This phenomenon is also widely used in photopolymerizable photopolymers and photoresists used in the production of printing plates, printed circuit boards, ICs, and the like. Various substances have been reported and actually used as photopolymerization initiators for these. For example, benzoin compounds include benzoin, benzoin methyl ether, and benzoin ethyl ether; carbonyl compounds include benzyl, benzophenone, acetophenone, and Michael's ketone; azo compounds include azobisisobutyronitrile and azodibenzoyl; and sulfur compounds include dibenzothia Examples of halogen compounds include zolyl sulfide and tetraethylthiuram disulfide, carbon tetrabromide, tribromphenyl sulfone, and 1,2-benzanthraquinone. However, these photopolymerization initiators are not yet fully satisfactory, and when combined with various unsaturated compounds, they cannot necessarily be said to have good sensitivity as photopolymers. In addition, in recent years, methods of forming images using lasers have been studied, and methods such as direct laser engraving, laser facsimile, and holography for printing plate production are already at the stage of practical application, and they are expected to be applied in many other fields in the future. Considered and expected. The laser photosensitive materials used in this case include silver salt photosensitive materials, electrophotographic materials, photochromic materials, and photopolymers, but photopolymers are extremely sensitive compared to silver salt photosensitive materials and electrophotographic materials. Furthermore, its sensitivity wavelength range is from ultraviolet to visible light. For example, silver halide film (Kodalis orthofilm)
2556 type 3) sensitivity is Ar ⁺ laser wavelength 488nm
The amount of energy required for monochromatic light is 0.0205 mJ/ ^cm2 , but 7000 mJ/ ^cm2 is required for photopolymer (Kodatsu Polymatic Clean Plate LN-L), and even if ultraviolet light with a wavelength of 351/364 nm is used.
Energy of 100mJ/cm ³ 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 it has the ability to initiate photopolymerization and has a high sensitivity close to that of silver salt photosensitive materials. The present invention combines one or more organic peroxides with one or more organic dye compounds selected from the group consisting of cyanine dyes, merocyanine dyes, and thiazole dyes. This is a photopolymerization initiator composition for ethylenically unsaturated compounds. The organic peroxide used in the present invention includes almost all organic compounds having one or more oxygen-oxygen bonds in the molecule; examples thereof include methyl ethyl ketone peroxide, cyclohexanone peroxide, , 3,5-trimethylcyclohexanone peroxide, methylcyclohexanone peroxide, acetylacetone peroxide
Oxide, 1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane,
oxy)cyclohexane, n-butyl-4,4-
Bis(tertiary butyl peroxy) valerate, 2,2-bis(tertiary butyl peroxy) butane, tertiary butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, para-menthane hydroperoxide, 2,5-
Dimethylhexane-2,5-dihydroperoxide, 1,1,3,3-tetramethylbutylhydroperoxide, ditertiarybutyl peroxide, tertiarybutylcumyl peroxide, dicumyl peroxide, a, a' -bis(tert-butylperoxyisopropyl)benzene, 2,5-dimethyl-2,5-di(tert-butylperoxy)hesisane, 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, methanoltoluoyl peroxide, diisopropyl peroxydicarbonate, di-2- Ethylhexyl peroxydicarbonate, di-n-propyl peroxydicarbonate, di-2-ethoxyethyl peroxydicarbonate, dimethoxyisopropyl peroxycarbonate, di(3-methyl-3-methoxybutyl)peroxydicarbonate, Tersia tertiary butyl peroxy acetate, tertiary butyl peroxy isobutyrate, tertiary butyl peroxy pivalate, tertiary butyl peroxy neodecanoate, tertiary butyl peroxy octanoate, tertiary butyl peroxy 3,5 , 5-trimethyl hexaate, tert-butyl peroxylaurate,
Tertiary butyl peroxybenzoate, ditertiary diperoxy isophthalate,
Examples include 2,5-dimethyl-2,5-di(benzoylperoxy)hexane, tert-butyl peroxymaleic acid, tert-butyl peroxyisopropyl carbonate, and the like. The organic dye compound used in the present invention is yellow to
It has a specific structure as exemplified below and exhibits a red to violet color range. A: Cyanine dye [R ₁ is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms,
Represents an aryl group, alkoxy group or dialkylamino group, R ₂ is a hydrogen atom, and has 1 to 10 carbon atoms
represents an alkyl group or an aryl group, X represents a halogen group, and n represents an integer from 1 to 3. Y is

【formula】

【formula】

[expression] or

Represents [formula]. ] [R ₁ and R ₂ each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group, and X represents a halogen,

【ceremony

【formula】

【formula】

【formula】

[expression] or

Represents [formula]. ] [R ₁ is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms,
Represents an aryl group or an alkoxy group, R ₂
represents a hydrogen atom, an alkyl group or an aryl group having 1 to 10 carbon atoms, X represents a halogen,
n represents an integer from 1 to 3. Y is

【formula】

【formula】

[expression] or

Represents [formula]. ] B: Merocyanine dye [R ₁ and R ₂ represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, n represents an integer of 1 to 3, and X is

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

[expression] or

Represents [formula]. (Ph- represents a phenyl group)] [R ₁ , R ₂ and R ₃ represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an aryl group. ] [R ₁ , R ₂ and R ₃ represent a hydrogen atom, an alkyl group or an aryl group having 1 to 6 carbon atoms, and X represents a hydrogen atom or an alkali metal. ] D: Thiazole dye [R is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms,
It represents an aryl group, an alkoxy group, a nitro group or an amino group, and X represents an amino group or a phenylamino group. ] [R ₁ , R ₂ , R ₃ , and R ₄ each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an aryl group, and R ₅ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an aryl group. or represents a sulfonic acid group, and X represents a halogen or a hydroxyl group. ] The photoinitiator composition of the present invention contains one or more of the above organic peroxides (PO) and one or more of the above organic dye compounds (DY) as active ingredients. The weight ratio of (PO):(DY) is 1 to 99:99 to 1, more preferably 3 to 95:97 to 5.
Excellent effects cannot be obtained with compositions outside this range. The photopolymerization initiator composition of the present invention can photopolymerize ethylenically unsaturated compounds with ultraviolet light and visible light in a very short time. These ethylenically unsaturated compounds include monomers, oligomers, and polymers having polymerizable ethylenically unsaturated bonds, such as acrylic acid, methacrylic acid,
Unsaturated acids such as itaconic acid, maleic acid and its anhydride, phthalic acid and its anhydride, fumaric acid, methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, (meth)acrylate Glycidyl acid, hydroxyethyl (meth)acrylate, dimethyl maleate, diethyl maleate, dimethyl fumarate, pentaerythritol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, ethylene glycol di(meth)acrylate, propylene glycol Unsaturated acid esters such as di(meth)acrylate, and styrene, acrylamide, acrylonitrile, N-vinylpyrrolidone, vinyl acetate,
Furthermore, there are various unsaturated acid polyesters, unsaturated polyethers, unsaturated polyurethanes, and epoxy (meth)acrylate compounds. 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, ordinary dyes, pigments, additives, binders, inhibitors, etc. and a suitable diluting solvent are added. is added to prepare a photopolymerizable composition. The amount of the photopolymerization initiator composition added is based on the unsaturated compound.
0.1 to 40 parts by weight per 100 parts by weight, preferably
It is 0.5 to 30 parts by weight. Further, as a suitable diluting solvent, any solvent that dissolves the photopolymerization initiator composition of the present invention and the unsaturated compound used can be used, for example,
Water, methanol, ethanol, propanol, 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, trichlorethylene , dimethylformamide, dimethyl sulfoxide, etc. The photopolymerizable composition thus obtained undergoes a polymerization reaction within a very short time by irradiating it with active light in a wide range from ultraviolet to visible light.
As light sources, 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 be used. . The photopolymerization initiator composition of the present invention can be used in ordinary photopolymerization reactions, as well as in the production of photocurable paints, printing inks, adhesives, and printing plates, as well as printed circuit boards,
It can be applied in many ways, such as as a photoresist in the production of ICs, etc., and its effects are also very good. In particular, the photopolymerization initiator composition of the present invention has surprisingly good effects when applied to photosensitive materials for visible light lasers such as Ar ⁺ laser due to its high sensitivity and wide spectral sensitivity characteristics that extend to the visible light region. is obtained. 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 1-51 100 parts of pentaerythritol triacrylate as unsaturated compound, poly-N as binder
- Using 100 parts of vinylpyrrolidone, the photopolymerization initiator composition of the present invention was added thereto in the proportions shown in Table 1, and these were further uniformly dissolved in 1000 parts of methyl cellosolve to prepare a photosensitive liquid. These sensitivity solutions were applied onto an anodized aluminum plate using a spinner so that the dry film thickness was 1 μm. The photosensitivity test uses visible light (wavelength = 488nm), ultraviolet light (wavelength = 365nm) and laser light (wavelength =
488 nm) was used for each monochromatic light. visible light
The 488nm monochromatic light uses a 500W xenon lamp as the light source.
It was obtained by passing it through two filters: Toshiba colored glass filters Y-47 and KL-49. Also 365nm
The monochromatic light was obtained by using a 450W high-pressure mercury lamp as the light source and passing it through a Toshiba color glass filter UVD35. Laser light is 2.5W Ar ⁺ laser wavelength
A single line of 488 nm was used with a beam diameter of 1.25 mm. The photoresist film was exposed to each monochromatic light, and the 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 the photopolymerization initiator composition in the table are all based on 100 parts of pentaerythritol triacrylate. Comparative Examples 1 to 15 The same procedures as in Examples were carried out in cases where a conventionally known photoinitiator, an organic peroxide, and an organic dye compound were used instead of the photoinitiator composition of the present invention. A photosensitivity test was conducted to measure sensitivity. The results are shown in Table 2, and all amounts of photopolymerization initiator in the table are based on 100 parts of pentaerythritol triacrylate.

【table】

【table】

【table】

[Table] Wasu.
The abbreviations in Table-1 and Table-2 are as follows. ΓOrganic peroxide BPO: benzoyl peroxide PBIF: ditertiarybutyldiperoxyisophthalate POZ: 2,5-dimethyl-2.5-di(benzoylperoxy)hexane PBZ: tertiarybutylperoxybenzoate PXM: a, a′-bis(tert-butylperoxyisopropyl)benzene DCP: dicumyl peroxide Γ organic dye compound ΓKnown photopolymerization initiator BIPE: benzoin isopropyl ether BP: benzophenone MK: Michael's ketone 1,2-BA: 1,2-benzanthraquinone As is clear from Tables 1 and 2, organic peroxides and organic dyes It can be seen that all of the Examples in which these compounds were combined had significantly higher sensitivity than the Comparative Examples.

Claims (1)

[Claims] 1. Ethylenically unsaturated, which is a combination of one or more organic peroxides and one or more organic dye compounds selected from the group consisting of cyanine dyes, merocyanine dyes, and thiazole dyes. Photopolymerization initiator composition for compounds.