JPH0463882B2 - - Google Patents

Description

[Detailed description of the invention]

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. Additionally, this phenomenon is widely used in 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 such as benzoin and benzoin methyl ether, carbonyl compounds such as benzyl, benzophenone, acetophenone, and Michael's ketone, azo compounds such as azobisisobutyronitrile and azodibenzoyl, and sulfur compounds such as dibenzothiazolyl sulfide. , decyl phenyl sulfide, tetraethyl thiuram disulfide, etc.; halogen compounds include carbon tetrabromide, tribromo phenyl sulfone, and 1,2-benzanthraquinone. However, these photopolymerization initiators are still not fully satisfactory, and photopolymerization compositions with various unsaturated compounds cannot necessarily be said to have good sensitivity as photopolymers, and even higher sensitivity and Furthermore, there is a strong demand for photopolymerization initiators with good storage stability. In addition, there are many types of organic peroxides having a peroxide bond in the molecule, such as hydroperoxides, dialkyl peroxides, diacyl peroxides, peroxyketals, peroxyesters, peroxycarbonates, etc. It is well known that there are compounds that decompose thermally to produce active radical species. For this reason, organic peroxides are widely used as thermal polymerization initiators, thermal polymerization catalysts, thermal polymerization curing agents, thermal polymerization crosslinking agents, etc. for unsaturated compounds. Furthermore, it has been reported that organic peroxides are also decomposed by light energy and similarly generate active radical species. However, these have low photopolymerization initiating ability for use as photopolymerization initiators for unsaturated compounds, and are therefore not suitable for practical use. Therefore, there have been almost no examples of using organic peroxides as photopolymerization initiators for polymerizable photopolymers. Against this background, the present inventors conducted extensive research and found that a combination of a specific organic peroxide and an aromatic carbonyl compound has a much better ability to initiate photopolymerization than either of them alone. The inventors have discovered that the method has a good storage stability, increases the initial polymerization rate in the photopolymerization of unsaturated compounds, and can provide a product with extremely high sensitivity.The present invention was thus achieved. That is, the present invention is based on the general formula () (In the formula, Ar is an unsubstituted phenyl group, or an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a phenyl group, a nitro group, an amino group, a hydroxyl group,
Photopolymerization consisting of a benzoylperoxy compound having a partial structure represented by (representing a phenyl group substituted with any halogen atom) and an aromatic carbonyl compound selected from xanthones, anthrones, and acridones. An initiator composition is provided. Examples of the benzoyl peroxy compound represented by the general formula () used in the present invention include benzoyl peroxide, toluyl peroxide, chlorobenzoyl peroxide, hydroxybenzoyl peroxide, 2,5-dimethyl-2,
5-dibenzoylperoxyhexane, 2,5-
Dimethyl-2,5-di(peroxybenzoyl)
Examples include hexyne-3, tertiary butyl peroxybenzoate, ditertiary butyl diperoxy isophthalate, and the like. The aromatic carbonyl compound used in the present invention includes xanthone, 1-hydroxysanthone, 2-hydroxyxanthone, 3-hydroxyxanthone,
Hydroxanthone, 4-hydroxyxanthone, 1,3-dihydroxyxanthone, 1,3-
Dihydroxy-7-methoxyxanthone, 1,
6,8-trihydroxy-3-methylxanthone, 1,3,6,7-tetrahydroxyxanthone, 2-chlorxanthone, 3-nitroxanthone, 1,6-dinitroxanthone, 2,7-dinitroxanthone, 2- Aminoxanthone, 3-aminoxanthone, 1,2-benzoxanthone,
There are 2,3-benzoxanthone, 1,8-diisopropenylxanthone, etc., and thioxanes include thioxanthone, 1-methylthioxanthone, 2-diisopropenylxanthone, etc.
-Methylthioxanthone, 1,2-dimethylthioxanthone, 1,8-dimethylthioxanthone,
1-hydroxythioxanthone, 2-hydroxythioxanthone, 1-chlorothioxanthone, 2
-Chlorthioxanthone, 1-chloro-2,5-
Diisopropenylthioxanthone, 2-chloro-
3,6-diisopropenylthioxanthone, 1,
There are 2-benzthioxanthone, 2,3-benzthioxanthone, etc., and further anthrones include 1-hydroxyanthrone, 2-hydroxyanthrone, 1-chloranthrone, 2-chloranthrone, 1,2-benzanthrone, 2,3- Benzanthrone, 1-hydroxy-2-chloro-
4,5-benzanthrone, acridones such as 1-methylacridone, 2-methylacridone,
3-methylacridone, 4-methylacridone,
1-chloracridone, 2-chloracridone,
4-chloroacridone, 2-bromoacridone,
2,4-dichloroacridone, 2,7-dibromoacridone, 2,4,5,7-tetrabromoacridone, 1-nitroacridone, 2-nitroacridone, 2,4,7-tri Nitroacridone, 1
-aminoacridone, 2-aminoacridone, 3
-aminoacridone, 4-aminoacridone, acridone-2-sulfonic acid, acridone-4-sulfonic acid, and the like. The photopolymerization initiator composition of the present invention is a mixture of the above-mentioned benzoyl peroxy compound and an aromatic carbonyl compound, and its composition is such that the amount of the benzoyl peroxy compound is 0.1% of the total photopolymerization initiator composition.
~99.9% by weight, preferably 1-95% by weight. If the composition is outside this range, a synergistic effect between the two cannot be obtained. The photopolymerization initiator composition of the present invention can photopolymerize almost all unsaturated compounds. That is, 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, glycidyl (meth)acrylate, hydroxyethyl (meth)acrylate, dimethyl maleate, diethyl maleate, dimethyl fumarate, pentaerythritol Unsaturated acid ester compounds such as tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, and styrene, acrylamide, acrylonitrile, N-vinylpyrrolidone, Examples include monomers such as vinyl acetate, unsaturated 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 a suitable diluting solvent is added as needed to prepare a photopolymerization composition. The amount of the photopolymerization initiator composition added is based on the unsaturated compound.
0.1 to 30 parts by weight per 100 parts by weight, preferably
It is 0.5 to 20 parts by weight. Further, any suitable diluting solvent can be used as long as it dissolves the photopolymerization initiator composition and unsaturated compound of the present invention. For example, water, methanol, ethanol, propanol, butanol, acetone,
Methyl ethyl ketone, methyl isobutyl ketone,
Toluene, xylene, ethyl acetate, butyl acetate,
cellosolve, tetrahydrofuran, dioxane,
These include dichloromethane, chloroform, carbon tetrachloride, trichloroethylene, dimethylformamide, and dimethyl sulfoxide. The photopolymerizable composition thus obtained undergoes a polymerization reaction by irradiating it with actinic light such as ultraviolet rays or visible light. As the light source, ultra-high pressure, high pressure, medium pressure, and low pressure mercury lamps, chemical lamps, carbon arc lamps, xenon lamps, metal halide lamps, fluorescent lamps, tungsten lamps, sunlight, and the like can be used. The photopolymerization initiator composition of the present invention can be used in ordinary photopolymerization reactions, and can also be applied to a wide range of applications such as photocurable paints, printing inks, adhesives, printing plate preparation, and photoresists. The effect is very good, and the highest sensitivity can be 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 to 20 Using 100 parts of an epoxy acrylate compound (trade name: Epoxy Ester 3002A, Kyoeisha Yushi Co., Ltd.) as an unsaturated compound, 20 types of photopolymerization initiator compositions of the present invention shown in Table 1 were added to it. The selected materials were added to form a photopolymerizable composition, which was coated onto a glass substrate to a thickness of 9 μm. A polyethylene cover film is adhered to the paint film and the output is 450W.
The photocurability of the coating was investigated by irradiating it with a high-pressure mercury lamp from a distance of 15 cm and measuring the irradiation time until the coating film was cured. The results are shown in Table-1. Comparative Examples 1 to 12 For comparison with Examples 1 to 20, when each of the organic peroxide and the aromatic carbonyl compound was used alone,
Furthermore, the photocurability of other photopolymerization initiators was examined in the same manner as in Examples 1-20. Display the results -
Shown in 2.

[Table] Minimum irradiation time until the coating film no longer adheres to the ilm
while.

[Table] (Note) *1: Same as Table-1.
The abbreviations in Table-1 and Table-2 are as follows. BPO: Benzoyl peroxide POZ: 2,5-dimethyl-2,5-di(benzoylperoxy)hexane PBZ: Tertiary butyl peroxybenzoate PBIF: Ditertiary butyl diperoxyisophthalate BAQ: 1,2-benz Anthraquinone XT: Xanthone AC: Acridone CHBA: 1-Hydroxy-2-chloro-3,4
-Benzanthrone CXT: 2-Chlorthioxanthone DITX: 2-chloro-3,6-diisopropenylthioxanthone As is clear from Tables 1 and 2, the examples are generally better than the comparative examples. The curing time is short, especially when considering the same aromatic carbonyl compound, the curing time of the present invention in combination with an organic peroxide is shortened by a factor of several to several tenths. For example, Comparative Example 9, which has the highest sensitivity alone
(CTX) cures in 8 seconds, while Examples 13 to 16 corresponding to this cure in 1 to 2 seconds, and Comparative Example 6
In Examples 1 to 4, the curing time is significantly shortened to 7 to 12 seconds, compared to 540 seconds for (XT). Examples 21-40 90 parts of mercaptoethanolated polybutadiene acrylate and acrylamide as unsaturated compounds
This was dissolved in 1000 parts of dioxane, and the photopolymerization initiator composition of the present invention was added to prepare a photopolymerization composition. This was coated onto a polished aluminum plate to a thickness of 0.5 μm using a rotary coater, and the gray scale was adhered to the coated aluminum plate, which was then exposed to light from a chemical lamp from a distance of 20 cm for 5 minutes. Next, the film was developed with a 10% aqueous sodium carbonate solution, washed with water, and the remaining cured film was stained with a crystal violet methanol solution, and the sensitivity was measured by reading the gray scale step number. The results are shown in Table-3. Furthermore, from the optical density of each step of the gray scale and the distance of 20 cm, 5
Table 5 shows the amount of transmitted light energy of the chemical lamp exposed for one minute. Comparative Examples 13-25 For comparison with Examples 21-40, in the case of each of the organic peroxide and the aromatic carbonyl compound alone,
Furthermore, the sensitivity of other photopolymerization initiators was measured in the same manner as in Examples 21-40. Table 4 shows the results.
Shown below.

【table】

【table】

【table】

[Table] There is no scale, but it does not cure even after 5 minutes of exposure without scale.
The abbreviations in Table-3 and Table-4 are the same as in Table-1 and Table-2.

【table】

[Table] From the results in Tables 3 and 4, the number of steps in the example is 7 to 14, and the number of steps in the comparison example is 1 (0) to 14.
The value is larger than 7, and especially when comparing the same aromatic carbonyl compounds, the difference in the number of steps is 6 to 14, as compared to 7 in Comparative Example 21 (CTX) and 13 to 14 in Examples 33 to 36. There are also 7. Also,
Even if a common organic peroxide and a photosensitizer are used in combination, the number of steps does not improve much as in Comparative Example 25. Therefore, as is clear from the relationship between the number of steps and the amount of transmitted light energy in Table 5, it can be seen that the samples of the Examples are cured with several fewer light energies than those of the Comparative Examples. Next, as a result of testing for storage stability, the photopolymerization initiator compositions and photopolymerization compositions used in Examples 1 to 20 showed that their physical and chemical properties remained stable even after 3 months at 40°C in the dark. Almost no change was observed in
All had good photopolymerization initiation ability and photopolymerization ability.

Claims (1)

[Claims] 1 General formula () (In the formula, Ar is an unsubstituted phenyl group, or an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a phenyl group, a nitro group, an amino group, a hydroxyl group,
Photopolymerization consisting of a benzoylperoxy compound having a partial structure represented by (representing a phenyl group substituted with any halogen atom) and an aromatic carbonyl compound selected from xanthones, anthrones, and acridones. Initiator composition.