JPH0676402B2 - 9-pyridyl acridine compound - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a 9-pyridyl acridine compound useful as a photopolymerization initiator.

It is known that a suitable photopolymerization initiator is added to an unsaturated monomer or an unsaturated polymer (prepolymer) and polymerized by irradiation with light, and such a photopolymerizable composition has a wide range of applications. It is used in fields such as printing plates such as flat plates, convex plates, and concave plates, photocurable inks, paints, printed circuit boards, and adhesives.

Various compounds have been proposed as photopolymerization initiators, and for example, benzophenone compounds and benzoin compounds are known as typical compounds.

However, these aromatic ketone compounds have the drawback of giving coloring to the polymer, and also have the drawback that they require long-time light irradiation because their effect is small, so that they are not practically satisfactory. Absent.

Therefore, in JP-A-47-4126, a 9-substituted acridine compound is proposed as a compound having high photosensitivity, but the effect of the compound is insufficient, and JP-A-59-22 is used.
6002 proposes to use a specific thiol compound together with a 9-substituted acridine compound.

However, the improvement effect by the combined use is not yet satisfactory, and it has been strongly desired to find a compound having a larger effect alone.

The present inventor has conducted extensive studies in view of the above-mentioned circumstances, and as a result, a 9-pyridylacridine compound represented by the following general formula (I) has a very large effect as a photopolymerization initiator and can be irradiated with light for a short time. It has been found that the polymerization can proceed to the required extent and that the polymer is not colored. Furthermore, the photopolymerizable composition containing the compound represented by the following general formula (I) has excellent storage stability,
It also has the advantage that it does not deteriorate even after long-term storage.

Examples of the compound represented by the general formula (I) include 9- (2
-Pyridyl) acridine, 9- (3-pyridyl) acridine and 9- (4-pyridyl) acridine.

These compounds can be easily produced, for example, by reacting diphenylamine with the corresponding pyridinecarboxylic acid in the presence of polyphosphoric acid.

The thus-obtained compound represented by the general formula (I) of the present invention can be used alone as a highly effective photosensitizer, but if necessary, it may be used in combination with other conventionally known photosensitizers. You can also

Hereinafter, the present invention will be described in more detail with reference to Examples.

Example 1 Synthesis of 9- (3-pyridyl) acridine Diphenylamine 273 g (1.62 mol), nicotinic acid 100 g
(0.81 mol) and 1400 g of polyphosphoric acid were mixed, and the mixture was stirred at 205 to 240 ° C. for 4 hours under a nitrogen gas stream. After cooling, the mixture was poured onto crushed ice and water 8 was added. The aqueous layer is removed, the insoluble matter is filtered off, and a 50% aqueous potassium hydroxide solution is added to adjust the pH to 10
And The resulting oily substance was extracted with chloroform 2, washed thoroughly with water, and dried with anhydrous sodium sulfate. After distilling off chloroform, the residue was recrystallized from ethanol to obtain a pale yellowish brown powder product having a melting point of 204 to 207 ° C.

The results of elemental analysis of the product are as follows, and they were in good agreement with the target product.

C% H% N% Measured value 84.58 4.63 10.79 Calculated value 84.35 4.72 10.93 Also, as a result of infrared spectroscopic analysis, 3050, 1410, 760 and 720 cm
^-1 has a characteristic absorption and was confirmed to be the target product.

Moreover, the result of having measured the ultraviolet absorption spectrum of the obtained compound is shown below.

λ _max = 359 nm, ε = 9.98 × 10 ³ Example 2 Synthesis of 9-4-pyridyl) acridine By the same procedure as in Example 1 except that pyridine-4-carboxylic acid was used instead of nicotinic acid, the melting point was 195. The title compound was synthesized as a pale tan powder at ˜205 ° C.

The results of elemental analysis of the product are as follows, and they were in good agreement with the target product.

C% H% N% Measured value 84.66 4.59 10.75 Calculated value 84.35 4.72 10.93 Also, as a result of infrared spectroscopic analysis, 3050, 1600, 760 and 750 cm
There was absorption at ^-1 and was confirmed to be the target product.

Moreover, the result of having measured the ultraviolet absorption spectrum of the obtained compound is shown below.

λ _max = 359 nm, ε = 8.86 × 10 ³ The compound of the present invention is useful as a photopolymerization initiator used when an unsaturated compound is polymerized by irradiation with light as described above, and can be polymerized by the compound of the present invention. The unsaturated compound is a compound having at least one ethylenic double bond, and is a monomer or a side chain which gives a cured product which is cured by addition polymerization when exposed to actinic rays to be substantially insolubilized. It is a polymer having an ethylenically unsaturated double bond in the chain or main chain.

Examples of such unsaturated compounds include unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid and fumaric acid; esters of the unsaturated carboxylic acid with a monohydric or polyhydric alcohol, or Amides with polyhydric amines; (meth) acrylates of polyhydroxyesters obtained from monohydric or polyhydric carboxylic acids and polyhydric alcohols; unsaturated dicarboxylic acids (and other dicarboxylic acids) with polyhydric alcohols or polyamines Unsaturated polyesters or polyamides obtained from
Urethane acrylate obtained by reaction of urethane compound having terminal isocyanate obtained from diisocyanate and polyhydric alcohol with hydroxyalkyl (meth) acrylate; obtained by reaction of polyglycidyl ether of bisphenol or polyol with (meth) acrylic acid Epoxy acrylate; Linear polyester obtained by reaction of dicarboxylic acid anhydride and glycidyl (meth) acrylate; Di (meth) obtained by reacting polyester or polyamide having carboxyl groups at both ends with glycidyl (meth) acrylate
Examples thereof include acrylic acid-modified polyester or polyamide.

In these unsaturated compounds, examples of monohydric or polyhydric alcohols include methanol, ethanol, butanol, allyl alcohol, octanol, N, N-dimethylethanol, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, neopentyl. Glycol, 1,3-butanediol,
1,4-butanediol, 1,6-hexanediol, glycerin, trimethylolpropane, trimethylolethane, tris (2-hydroxyethyl) isocyanurate, pentaerythritol, diglycerin, ditrimethylolpropane, dipentaerythritol, etc. As the monovalent or polyvalent amine, for example, ammonia, methylamine, butylamine, octylamine, diethylamine, dibutylamine, ethylenediamine, diethylenetriamine, morpholine, piperazine, 1,6-
Hexamethylenediamine, melamine and the like, and polyvalent carboxylic acids other than unsaturated dicarboxylic acids include phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, tetrahydrophthalic acid, succinic acid, adipic acid, Examples of the diisocyanate include toluene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, isocyanatomethylcyclohexane isocyanate, hexanemethylene diisocyanate, and isophorone diisocyanate.

Therefore, among the unsaturated compounds photopolymerized by the compound of the present invention, specific examples of the unsaturated carboxylic acid ester or amide include, for example, methyl-, ethyl-,
Butyl-, isooctyl-, 2-hydroxyethyl- or N, N-dimethylaminoethyl-acrylate, methyl- or ethyl-methacrylate, ethylene glycol diacrylate, triethylene glycol diacrylate, 1,4-butanediol diacrylate, tri- Methylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, tris (2-acryloyloxyethyl) isocyanurate, dipentaerythritol-tetra-hexaacrylate, glycerin diacrylate, triethylene glycol dimethacrylate, trimethylolpropane triacrylate Methacrylate, pentaerythritol trimethacrylate, ethylene glycol dicrotonate, diallylmate, bis Acryloyloxy-ethoxyphenyl) propane, acrylamide, methacrylamide, morpholide acrylate, ethylene bisacrylamide, hexamethylene bisacrylamide, methylene bis-methacrylamide, and the like.

As the unsaturated compound photopolymerized by the compound of the present invention, in addition to these, diallyl phthalate, diallyl malonate, divinyl adipate, divinyl phthalate, vinyl acetate, isobutyl vinyl ether, ethylene glycol divinyl ether, styrene, acrylonitrile, triallyl Other examples include isocyanurate and triallyl phosphate.

The amount of the 9-pyridyl acridine compound of the present invention used as a photopolymerization initiator varies depending on the type of unsaturated compound used, but is generally 0.01 to 10 parts by weight with respect to 100 parts by weight of the unsaturated compound. It is preferable.

When the compound of the present invention is used as a photopolymerization initiator, its effect can be further increased by using it in combination with various organic amine compounds or organic sulfur compounds.

Examples of these organic amine compounds include triethanolamine, triisopropanolamine, methyldiethanolamine, octyldiethanolamine, octadecyldiethanolamine, dibutylethanolamine, dioctylethanolamine, diethanolaniline, diethanolamine, methylethanolamine, butylethanolamine, tetrahydroxyl. Ethylethylenediamine, tetrahydroxyethylhexamethylenediamine, triethylamine, tributylamine, dimethylaminopropylamine, dimethylaniline, 4-dimethylaminotoluene, 4-diethylaminotoluene, 4
-Dimethylaminocyanobenzene, 4-diethylaminocyanobenzene, 4-dimethylaminobromobenzene,
4-diethylaminobromobenzene, 4-dimethylaminonitrobenzene, 4-diethylaminonitrobenzene, 4-dimethylaminobenzoic acid alkyl ester, 4
-Diethylaminobenzoic acid alkyl ester, 4-dimethylaminopyridine, 4-diethylaminopyridine, 4
-Pyrrolidinopyridine, phenylglycine, diethylaniline, diethylamine, dioctylamine, tetramethylethylenediamine, Michler's ketone, anthranilic acid and the like.

As the organic sulfur compound, 2-mercaptoimidazole, 2-mercaptooxazole, 2-mercaptothiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 6-chloro-2-mercaptobenzimidazole, 5-methylmercapto-1- Examples thereof include phenyltetrazole, 6-methoxy-2-mercaptobenzimidazole, 2-mercaptonaphthoimidazole, 2-mercaptonaphthoxazole and 3-mercapto-1,2,4-triazole.

If necessary, a conventional additive such as a thermal polymerization inhibitor, a colorant, a plasticizer, a surface protective agent, a smoothing agent and the like can be added to the photopolymerizable composition containing the compound of the present invention.

Examples of the thermal polymerization inhibitor include hydroquinone, p-methoxyphenol, pyrogallol, catechol, 2,6-di-tert-butyl-p-cresol, β-naphthol, tert-butylhydroquinone and the like.

Examples of the colorant include carbon black; metal powder such as silver powder, copper powder, and aluminum powder; extender pigments such as yellow lead, titanium white, talc, and alumina; inorganic pigments such as milori blue and chrome vermillion; Hansa yellow; Organic pigments such as Vulcan Orange, Permanent Orange, Lake Red C, Brilliant Carmine B, Rhodamine Lake, Eosin, Phloxine, Victoria Blue Lake, Phthalocyanine Blue, Phthalocyanine Green, Quinacridone Red, Dioxazine Bio Red; Alkali Blue Toner, Methyl Bio Examples include dyes such as red.

As the exposure light source applicable to the photopolymerizable composition containing the compound of the present invention, carbon arc, high pressure mercury lamp, xenon lamp, metal halide lamp, tungsten lamp, argon laser, helium-cadmium laser, etc. Can be used.

Hereinafter, the effect of the compound of the present invention as a photopolymerization initiator will be described in more detail by use examples.

Use Example 1 [Blending] Epoxy acrylate (Molecular weight 1500) 80 (Shin-Nakamura Chemicals: NK ester U-108A) 1,6-hexanediol diacrylate 20 Cyanine blue (Dainippon Seika: SR-5020) 22 Sample compound 0.12 Combined auxiliary agent Table-1 The above ingredients were thoroughly kneaded and then uniformly coated on a paper to a thickness of 10 µm using a bar coater. This was transferred onto another paper using a rubber roller.

Pass this transfer paper under a high-pressure mercury lamp (Toshiba: H-400P) at a conveyor speed of 20 m / min under conditions of a lamp output of 160 w / cm and an irradiation distance of 10 cm, until it becomes tack-free. I checked the number of times. The results are shown in Table-1.

Use Example 2 [Compounding] Parts by weight Urethane acrylate (Molecular weight 1500) 80 (Shin-Nakamura Chemicals: NK ester U-1080) Trimethylolpropane triacrylate 20 (Shin-Nakamura Chemicals: NK ester A-TMPT) Sample compound 0.12 Combination aid Agent Table-2 The above ingredients were thoroughly kneaded and then uniformly applied to a glass plate at a thickness of 20 μm using a doctor knife. This glass plate was exposed to light of 50 mJ using a high pressure mercury lamp.

A No. 2 dumbbell test piece specified in JIS K-7113 was taken from this coated product, and STM-H-5 manufactured by Toyo Goldfin Co., Ltd.
A tensile test was performed using a 00 tester, Young's modulus at the time of 50% elongation was calculated, and the cured state of the coated material was examined.

The results are shown in Table-2. In the table, the larger the Young's modulus is, the more the curing progresses.

As shown in Tables 1 and 2, it is clear that the pyridine acridine compound of the present invention is more effective as a photopolymerization initiator than the conventionally known 9-phenyl acridine compound.

Front Page Continuation (72) Inventor Naohiro Kubota 5-2-13 Shirahata, Urawa-shi, Saitama Adeka Argus Chemical Co., Ltd.・ In Argus Chemical Co., Ltd.

Claims (1)

[Claims] 1. A 9-pyridyl acridine compound represented by the following general formula (I).