JP2003012669A - Coumarin derivative - Google Patents

Abstract

PROBLEM TO BE SOLVED: To expand the width of photosensitizers to be selected when preparing a photopolymerizable composition by providing a new organic compound having the absorption maximum in a visual light region. SOLUTION: This coumarin derivative has a specific structure. The method for producing the coumarin derivative includes a step for reacting a phenol compound having a specified atomic group with a naphthylamine compound having a specific atomic group.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a coumarin derivative, and more particularly to a novel coumarin derivative useful as a light absorber or a light emitting agent.

[0002]

2. Description of the Related Art With the advent of the information age, photochemical polymerization has been frequently used in a wide variety of fields, and now its application is beyond the field of synthetic resins, and it is used for paints and printing plates. , The field of information recording and electronic devices such as printed circuits and integrated circuits. Photochemical polymerization is a technique for polymerizing a polymerizable compound by irradiation with light. When roughly classified, photopolymerization is a method of directly irradiating a polymerizable compound with light and activating it to initiate polymerization, and a photosensitizer. There is photosensitization polymerization in which a polymerizable compound is polymerized by irradiating light in the coexisting state to generate active species of the photosensitizer. In any photochemical polymerization, the start and stop of the polymerization can be controlled by blinking the exposure light source, and the degree of polymerization and the polymerization rate can be easily controlled by selecting the intensity and wavelength of the exposure light source. Moreover, since photochemical polymerization generally has low energy for initiating polymerization, it can be polymerized even at a low temperature. In the field of information recording, such as printing plates and holography, such advantages of photochemical polymerization are bought and the visible light such as the second harmonic of argon ion laser, helium neon laser, and Nd-YAG laser is acquired. The demand for photopolymerizable compositions that can be polymerized by irradiation is rapidly increasing.

Most of the polymerizable compounds and polymerization initiators to be incorporated into the photopolymerizable composition absorb only ultraviolet rays, so that when the photopolymerizable composition is polymerized with visible light, it is photosensitized. Agents become an indispensable technical element. The properties that the photosensitizer should have are that it has a large molecular extinction coefficient in the visible region (hereinafter, the molecular extinction coefficient may be abbreviated as “ε”), and that various types of polymerizable compounds and polymerization initiators are added. Sensitivity, high sensitization efficiency, excellent solubility in a solvent and compatibility with other compounding ingredients, and stability. Typical photosensitizers include, for example, merocyanine dyes disclosed in JP-A-54-151024, cyanine dyes disclosed in JP-A-58-29803, and JP-A-59-5640.
No. 3, the stilbene dye disclosed in JP-A-63-2
Coumarin derivatives disclosed in Japanese Patent No. 3901, Japanese Patent Laid-Open No.
Examples thereof include the methylene blue derivative disclosed in JP-A-4-33104 and the pyran derivative disclosed in JP-A-6-329654. However, all of them have advantages and disadvantages, and a plurality of materials such as a polymerizable compound and a binder resin. A photopolymerizable composition consisting of (1) has not yet been found that can always exhibit the above-mentioned various properties. Therefore, in a new application field of photochemical polymerization, for example, in the fields of information recording and electronic devices, a material other than the photosensitizer such as a polymerizable compound and a binder resin is selected first, and then, The current situation is that, from among a wide variety of organic compounds, those that are compatible with those polymerizable compounds and polymerization initiators are searched by trial and error.

[0004]

In view of the above situation, an object of the present invention is to prepare a photopolymerizable composition by providing a novel organic compound having an absorption maximum in the visible region, An object is to widen the range of photosensitizers that can be selected.

[0005]

[Means for Solving the Problem] In order to solve this problem,
The present inventor has created a coumarin ring and a hydrocarbon group in the molecule.
Or, a naphthalene ring having a plurality thereof, and a coumarin derivative which is condensed with the naphthalene ring and contains a hetero five-membered ring that electronically resonates with the coumarin ring and the naphthalene ring are studied and searched. However, since the specific coumarin derivative has a large molecular absorption coefficient in the visible region and efficiently absorbs visible light, it is extremely useful as a material for sensitizing a polymerizable compound or a polymerization initiator in photochemical polymerization. I found that.

That is, the present invention solves the above problems by providing a coumarin derivative represented by either the general formula 1 or the general formula 2.

[0007]

Embedded image General formula 1:

[0008]

Embedded image General formula 2:

(In the general formulas 1 and 2, X is charcoal.
Represents an elementary atom or a hetero atom. R₁To R₁₄Is it
Each independently represents a hydrogen atom or an appropriate substituent. However
And R ₁And / or R_TwoIs the nitrogen atom to which they bind
And R_ThreeOr R_FourA cyclic structure containing a carbon atom to which
May form a structure, in which case R_ThreeAnd / or R
_FourApparently does not exist. Also, R₉To R
₁₄Is one of the hydrocarbon groups, and
The hydrogen group may have a substituent. Furthermore, X is divalent
Or in the case of a trivalent hetero atom, R₇And / or
R₈Does not exist. )

Furthermore, the present invention provides a compound represented by the general formula 5 having R _{1 to} R ₆ corresponding to the general formula 1 or 2, and X and R ₇ corresponding to the general formula 1 or 2.
The above problem is solved by providing a method for producing a coumarin derivative via a step of reacting with a compound represented by any one of formula 6 or formula 7 having R ₁₄ to R ₁₄ .

[0011]

Embedded image General formula 5:

[0012]

Embedded image General formula 6:

[0013]

Embedded image General formula 7:

(In the general formulas 6 and 7, X is 2
When it is a valent or trivalent heteroatom, H ¹ and H ² are absent. )

The coumarin derivatives represented by the general formula 1 or the general formula 2 are all novel organic compounds not described in the literature. The present invention is based on the creation of new organic compounds and the discovery of their industrially useful properties.

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION The embodiments of the present invention will be described. The present invention relates to a coumarin derivative represented by the general formula 1 or the general formula 2.

[0017]

Embedded image General formula 1:

[0018]

Embedded image General formula 2:

In the general formulas 1 and 2, X represents a carbon atom or a hetero atom. As the hetero atom in X, an atom of Group 15 or Group 16 in the periodic table such as a nitrogen atom, an oxygen atom, a sulfur atom, a selenium atom and a tellurium atom is usually selected. Among these carbon atoms and hetero atoms, carbon atoms, in terms of optical characteristics and ease of manufacture,
Nitrogen atom, oxygen atom and sulfur atom are preferred.

R _{1 to} R in the general formulas 1 and 2
_14's each independently represent a hydrogen atom or an appropriate substituent. Examples of the substituent in R _{1 to} R ₁₄ include a methyl group, an ethyl group, a propyl group, an isopropyl group, an isopropenyl group, a 1-propenyl group, a 2-propenyl group, a butyl group, an isobutyl group, a sec-butyl group,
tert-butyl group, 2-butenyl group, 1,3-butadienyl group, pentyl group, isopentyl group, neopentyl group, tert-pentyl group, 1-methylpentyl group, 2
-Methylpentyl group, 2-pentenyl group, hexyl group,
Isohexyl group, 5-methylhexyl group, heptyl group,
Octyl group, nonyl group, decyl group, undecyl group, dodecyl group, octadecyl group and other aliphatic hydrocarbon groups having up to 20 carbon atoms, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cyclohexenyl group, cycloheptyl group Alicyclic hydrocarbon group such as phenyl group, o-tolyl group, m-tolyl group, p-tolyl group, xylyl group, mesityl group, o-cumenyl group, m-cumenyl group, p-cumenyl group, benzyl group , Phenethyl group, aromatic hydrocarbon group such as biphenylyl group, methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, isobutoxy group, sec-butoxy group, tert-
Ether group such as butoxy group, pentyloxy group, phenoxy group, benzyloxy group, methoxycarbonyl group,
Ethoxycarbonyl group, propoxycarbonyl group, acetoxy group, ester group such as benzoyloxy group, fluoro group, chloro group, bromo group, halogen group such as iodo group, hydroxy group, carboxy group, cyano group, nitro group, and further, Substituents may be mentioned as a combination thereof.

Depending on the use, the substituents for R _{1 to} R ₂ include an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and a hydrocarbon group derived from a combination thereof. Examples of the substituent in ₆ include, for example,
Methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-
Short chain long aliphatic hydrocarbon groups such as butyl group, pentyl group, isopentyl group, neopentyl group, tert-pentyl group, methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, isobutoxy group, tert-butoxy group , An ether group such as a pentyloxy group, a phenoxy group and a benzyloxy group, an ester group such as a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, an acetoxy group and a benzoyloxy group, and a cyano group are preferable, and hydrogen in these substituents is preferable. Atom
One or more of them may be substituted with a halogen group such as a fluoro group. As described above, one of the substituents in R _{9 to} R ₁₄ is an aliphatic hydrocarbon group,
It is assumed to be an alicyclic hydrocarbon group, an aromatic hydrocarbon group or a hydrocarbon group derived from a combination thereof, and among them, an aliphatic hydrocarbon group, especially an isopropyl group, an isobutyl group, a sec-butyl group, a tert-butyl group. Group, isopentyl group, neopentyl group, tert-pentyl group, 1-
A branched one having up to 6 carbon atoms such as a methylpentyl group, a 2-methylpentyl group, an isohexyl group and a 5-methylhexyl group is preferable. The substituent for R ₇ and R ₈ is preferably the same aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group as those for R ₁ or R ₂ or a hydrocarbon group derived from a combination thereof. However, when X is a trivalent atom such as a nitrogen atom, R ₇ or R ₈
If any of the above is not present and X is a divalent atom such as an oxygen atom or a sulfur atom, neither R ₇ nor R _{8 is} present. In addition, when the carbon atom to which R ₃ and / or R ₄ is bonded does not form a cyclic structure such as a julolidine ring, R ₃
And / or R ₄ may be a hydrogen atom, or may be appropriately selected from those described above depending on the application. Further, R ₅ is a hydrogen atom or a hydroxy group from the viewpoint of ease of production, or is appropriately selected from the above-mentioned ether group and ester group in consideration of the use.

In applications where light absorption and light emission are important, R ₁ and R ₂ are both aliphatic hydrocarbon groups, and these are the carbon atoms to which R ₃ or R ₄ binds, respectively. A coumarin derivative represented by the general formula 3 or the general formula 4 which is bonded to form a julolidine ring is preferable. In the general formula 3 and the general formula 4, X is the general formula 1 or the general formula 2.
And R _{5 to} R ₁₄ represent a hydrogen atom or an appropriate substituent as in the general formula 1 or 2, and R ₉ to R ₁₄ represent a carbon atom or a hetero atom.
It is assumed that any of ₁₄ is a hydrocarbon group. R ₁₅
To R ₁₈ each independently represent a hydrogen atom or an aliphatic hydrocarbon group, of which, for example, a short-chain long aliphatic hydrocarbon group such as a methyl group, an ethyl group, a propyl group, a butyl group, or a pentyl group is preferable. Among the coumarin derivatives represented by the general formula 3 or the general formula 4, any one of R _{9 to} R ₁₄ is, for example, isopropyl group, isobutyl group or sec.
-Butyl group, tert-butyl group, isopentyl group, neopentyl group, tert-pentyl group, 1-methylpentyl group, 2-methylpentyl group, isohexyl group, 5-
Those that are branched aliphatic hydrocarbon groups such as methylhexyl group are not only excellent in solubility and light absorption ability in a commonly used organic solvent, light emission ability, but also have a high glass transition point, and as a result, , Because it has high thermal stability,
Even in an environment where high temperature is unavoidable, it has a feature that the light absorption ability and the light emission ability are not easily diminished.

[0023]

Embedded image General formula 3:

[0024]

Embedded image General formula 4:

Specific examples of the coumarin derivative according to the present invention include those represented by the chemical formulas 1 to 27. All of these are in the visible region, specifically, around a wavelength of 530 nm, usually 450 to 600 n.
has an absorption maximum at m and a molecular extinction coefficient of 1 × 10 ⁴ or more,
Since it is preferably as large as 5 × 10 ⁴ or more, visible light in such a wavelength range is efficiently absorbed. In addition, most of them are in the visible region, more specifically, near the wavelength of 580 nm, usually,
It has an emission maximum such as a fluorescence maximum at 500 to 650 nm, and when excited, emits visible light in the green yellow to red region. The group of coumarin derivatives represented by the general formula 1 or the general formula 2 has a significantly higher glass transition point than most of the conventionally known related compounds, and most of the glass transition points exceed 130 ° C., for example,
As seen in the coumarin derivative represented by the chemical formula 18, depending on the substituent, the temperature reaches 150 ° C or higher. In addition,
The glass transition point of the coumarin derivative according to the present invention can be determined, for example, by a general-purpose differential scanning calorimetry analysis (hereinafter referred to as “DSC”).
Analysis ”is abbreviated. ) Can be determined by

[0026]

Embedded image Chemical formula 1:

[0027]

Embedded image Chemical formula 2:

[0028]

Embedded image Chemical formula 3:

[0029]

Embedded image Chemical formula 4:

[0030]

Embedded image Chemical formula 5:

[0031]

Embedded image Chemical formula 6:

[0032]

Embedded image Chemical formula 7:

[0033]

Embedded image Chemical formula 8:

[0034]

Embedded image Chemical formula 9:

[0035]

Embedded image Chemical formula 10:

[0036]

Embedded image Chemical formula 11:

[0037]

Embedded image Chemical formula 12:

[0038]

Embedded image Chemical formula 13:

[0039]

Embedded image Chemical formula 14:

[0040]

Embedded image Chemical formula 15:

[0041]

Embedded image Chemical formula 16:

[0042]

Embedded image Chemical formula 17:

[0043]

Embedded image Chemical formula 18:

[0044]

Embedded image Chemical formula 19:

[0045]

Embedded image Chemical formula 20:

[0046]

Embedded image Chemical formula 21:

[0047]

Embedded image Chemical formula 22:

[0048]

Embedded image Chemical formula 23:

[0049]

Embedded image Chemical formula 24:

[0050]

Embedded image Chemical formula 25:

[0051]

Embedded image Chemical formula 26:

[0052]

Embedded image Chemical formula 27:

The coumarin derivative of the present invention can be used in various methods.
Although it can be prepared more,
For example, R corresponding to general formula 1 or general formula 2₁Through
R₆A compound represented by the general formula 5 having
Is X and R corresponding to the general formula 2. ₇To R₁₄Having one
The compound represented by either general formula 6 or general formula 7
A method involving a reaction step is preferable. In addition, general
In formula 6 and general formula 7, X is a divalent or trivalent hetero.
H if it is an atom¹And H^TwoDoes not exist.

[0054]

Embedded image General formula 5:

[0055]

Embedded image General formula 6:

[0056]

Embedded image General formula 7:

That is, a suitable amount of the compound represented by the general formula 5 and the compound represented by the general formula 6 or the general formula 7 is put in a reaction vessel (usually around equimolar), and if necessary,
Dissolved in an appropriate solvent, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, sodium acetate, ammonia, triethylamine, piperidine, pyridine, pyrrolidine, aniline,
Basic compounds such as N, N-dimethylaniline, N, N-diethylaniline, hydrochloric acid, sulfuric acid, nitric acid, acetic acid, acetic anhydride, trifluoroacetic acid, p-toluenesulfonic acid, methanesulfonic acid, trifluoromethanesulfonic acid, etc. After adding an acidic compound, a Lewis acidic compound such as aluminum chloride, zinc chloride, tin tetrachloride, titanium tetrachloride, etc., the mixture is reacted at ambient temperature or a temperature higher than ambient temperature while heating and stirring by heating under reflux.

Examples of the solvent include pentane, hexane, cyclohexane, octane, benzene, toluene,
Hydrocarbons such as xylene, carbon tetrachloride, chloroform, 1,2-dichloroethane, 1,2-dibromoethane, trichloroethylene, tetrachloroethylene, chlorobenzene, bromobenzene, halides such as α-dichlorobenzene, methanol, ethanol, 1- Propanol, 2-propanol, 1-butanol, 2-butanol, isobutyl alcohol, isopentyl alcohol, cyclohexanol, ethylene glycol, propylene glycol, 2-methoxyethanol, 2-ethoxyethanol, phenol, benzyl alcohol, cresol, diethylene glycol, tri Alcohols and phenols such as ethylene glycol and glycerin, diethyl ether, diisopropyl ether, tetrahydrofuran, tetra Doropiran, 1,4-dioxane, anisole, 1,2-dimethoxyethane, diethylene glycol dimethyl ether, dicyclohexyl -
Ethers such as 18-crown-6, methyl carbitol, ethyl carbitol, acetic acid, acetic anhydride, trichloroacetic acid, trifluoroacetic acid, propionic anhydride, ethyl acetate, butyl carbonate, ethylene carbonate, propylene carbonate, formamide, N- Acids and acid derivatives such as methylformamide, N, N-dimethylformamide, N-methylacetamide, N, N-dimethylacetamide, hexamethylphosphoric triamide, trimethyl phosphate, acetonitrile,
Examples include nitriles such as propionitrile, succinonitrile, and benzonitrile, nitro compounds such as nitromethane and nitrobenzene, sulfur-containing compounds such as dimethylsulfoxide and sulfolane, and water.If necessary, these may be used in appropriate combination. To be

When a solvent is used, the reaction efficiency generally decreases as the amount of the solvent increases, and conversely, the amount decreases.
It becomes difficult to uniformly heat and stir, and side reactions easily occur. Therefore, it is desirable that the amount of the solvent is 100 times, usually 5 to 50 times, the weight of the whole raw material compound. The reaction is completed within 10 hours, usually 0.5 to 5 hours, depending on the kind of the raw material compound and the reaction conditions. The progress of the reaction can be monitored by a general-purpose method such as thin layer chromatography, gas chromatography, high performance liquid chromatography and the like. The coumarin derivative according to the present invention can be produced in a desired amount by this method or according to this method.
The compounds represented by the general formulas 5 to 7 can all be obtained by a general-purpose method for preparing a related compound.

Although the coumarin derivative thus obtained may be used as it is as a reaction mixture depending on the application, it is usually dissolved, separated, decanted, filtered, extracted, concentrated, or thin layered before use. It is purified by a general method for purifying related compounds such as chromatography, gas chromatography, high performance liquid chromatography, distillation, sublimation, crystallization, and the like, and if necessary, these methods are applied in combination. The coumarin derivative of this invention,
For example, when it is used as a laser-acting substance in a dye laser, it is preferably highly purified prior to use, for example, by a method such as distillation, crystallization and / or sublimation.

Of these, sublimation can easily obtain a high-purity crystal by one operation, the loss of the coumarin derivative due to the operation is small, and the solvent is not taken into the crystal. Especially excellent. The sublimation method to be applied may be an atmospheric sublimation method or a reduced pressure sublimation method, but the latter reduced pressure sublimation method is usually applied. To sublimate the coumarin derivative of the present invention under reduced pressure, for example, an appropriate amount of coumarin derivative is charged into a sublimation purification device, and the inside of the device is subjected to 10
Reduced pressure below ^-2 Torr, preferably, ^{10 -} 3 To
While keeping the temperature below rr, heating is performed at a temperature as low as possible below the melting point so as not to decompose the coumarin derivative. When the purity of the coumarin derivative to be subjected to sublimation purification is relatively low, the sublimation rate is suppressed by adjusting the pressure reduction degree and the heating temperature so that impurities are not mixed in, and when the coumarin derivative is difficult to sublime, Sublimation is promoted by ventilating an inert gas such as a rare gas into the sublimation purification device. The size of the crystal obtained by sublimation can be adjusted by adjusting the temperature of the condensing surface in the sublimation purification device. When the condensing surface is kept at a temperature slightly lower than the heating temperature and gradually crystallized. Relatively large crystals are obtained.

The use of the coumarin derivative according to the present invention will be described. As described above, the coumarin derivative of the present invention has an absorption maximum in the visible region and a large molecular extinction coefficient. It has a wide variety of uses as a material for polymerizing by exposure, a material for sensitizing a solar cell, a light absorbing material in an optical filter, and a material for dyeing various kinds of clothing. In particular, many of the coumarin derivatives of the present invention have maximum absorption wavelengths, for example, gas lasers such as argon ion laser and krypton ion laser, semiconductor lasers such as CdS laser, distributed feedback type or Bragg reflection type Nd-YAG laser. Wavelength of around 500nm, including solid-state lasers such as
Specifically, since it is close to the oscillation wavelength of a general-purpose visible laser having an oscillation line at 450 to 550 nm, it is possible to add such a visible laser as a photosensitizer to a photopolymerizable composition having an exposure light source. It can be used very advantageously in the field of information recording such as facsimiles, copiers and printers, in the field of printing such as flexo plate making and gravure plate making, and in the field of printed circuits such as photoresists.

The coumarin derivative of the present invention may be used together with one or more other materials that absorb light in the ultraviolet region, visible region and / or infrared region, if necessary, in general clothing or other than clothing. For example, drapes, laces, casements, prints, Venetian blinds, roll screens, shutters, goodwill, blankets, duvets, duvets, duvet covers, sheets, cushions, pillows, pillows, cushions,
Mats, carpets, sleeping bags, tents, car interior materials,
Building bedding products such as windshields and window glasses, paper diapers, diaper covers, eyeglasses, monocles, health products such as ronets, insoles, shoe linings, bags, furoshiki, umbrellas, parasols, plush toys. , Filters for information display devices that use lighting devices, cathode ray tube displays, liquid crystal displays, plasma displays, etc., panels and screens, viewing windows such as sunglasses, sunroofs, microwave ovens, ovens, etc. When used in packaging materials, filling materials, containers, etc. for filling or containing, not only can prevent or reduce obstacles and inconveniences caused by ambient light such as natural light and artificial light in living things and articles, but also the color of the article. Degree, color,
There is a practical benefit in that the colors and textures can be adjusted and the light reflected or transmitted from the article can be adjusted to a desired color balance.

Further, the coumarin derivative of the present invention has an emission maximum such as a fluorescence maximum in the visible region and emits visible light when excited, and therefore requires an organic compound having such a property, for example, It is also useful as a laser acting substance in a dye laser. In order to use the coumarin derivative of the present invention in a dye laser, it is purified in the same manner as in the case of constructing a known dye-based laser oscillator, dissolved in a solvent as appropriate, and if necessary, the pH of the solution was adjusted to an appropriate level. Then, it is sealed in the dye cell in the laser oscillator. The coumarin derivative of the present invention is characterized by not only obtaining an amplification gain in an extremely wide wavelength range in the visible region but also having high heat resistance and light resistance as compared with known related compounds, and being resistant to deterioration even when used for a long time. is there.

Many of the coumarin derivatives according to the invention are
As mentioned above, the glass transition point is high, and as a result,
Since it has a high heat resistance and the light absorbing ability and the light emitting ability are hard to be reduced even in an environment where high temperature is unavoidable, it can be used extremely advantageously in any application because there are few defects caused by heat.

Embodiments of the present invention will be described below based on examples.

[0067]

Example 1 <Coumarin Derivative> A suitable amount of dimethylformamide was placed in a reaction vessel, 0.21 g of the compound represented by the chemical formula 28 and 0.21 g of the compound represented by the chemical formula 29 were added, and the mixture was heated under reflux for 2 hours. After the reaction, the reaction mixture was cooled to room temperature, and an appropriate amount of methanol was added. The precipitated crystals were collected and purified by column chromatography using a mixed solution of chloroform / ethyl acetate as a developing solvent, whereby 0.2 g of orange crystals of the coumarin derivative represented by the chemical formula 18 was obtained.

[0068]

Embedded image Chemical formula 28:

[0069]

Embedded image Chemical formula 29:

A part of the crystal was taken and measured according to a conventional method. As a result, the coumarin derivative of this example was 345 to 351.
It showed a melting point in ° C. Further, the visible absorption spectrum and the fluorescence spectrum in a methylene chloride solution were measured by a conventional method, and the wavelengths were 491 nm and 51, respectively.
An absorption maximum (ε = 5.8 × 10 ⁴ ) and a fluorescence maximum were observed at 8 nm. Furthermore, when a ¹ H-nuclear magnetic resonance spectrum in a chloroform-d solution was measured by a conventional method, a chemical shift δ (ppm, TMS) was 1.37.
(6H, s), 1.56 (9H, s), 1.62 (6
H, s), 1.77 to 1.87 (4H, m), 3.3.
0 (2H, t), 3.39 (2H, s), 7.40 (1
H, s), 7.67 (1H, dd), 7.73 (1H,
d), 7.90 (1H, d), 7.91 (1H, d),
Peaks were observed at the positions of 8.91 (1H, d) and 9.02 (1H, s).

The coumarin derivative of this example having an absorption maximum and a fluorescence maximum in the visible region is used as a light absorber and a luminescent agent in various fields including photochemical polymerization, solar cells, optical filters, dyes and dye lasers. It is useful.

[0072]

[Example 2] <Coumarin derivative> A compound represented by the chemical formula 2 was obtained by reacting according to the method of Example 1 except that the compound represented by the chemical formula 28 was used in place of the compound represented by the chemical formula 28.
A coumarin derivative of the present invention represented by 4 was obtained.

[0073]

Embedded image Chemical formula 30:

The coumarin derivative of this example having an absorption maximum and a fluorescence maximum in the visible region is used in various fields such as photochemical polymerization, solar cells, optical filters, dyes and dye lasers as a light absorber and a luminescent agent. It is useful.

[0075]

Example 3 <Coumarin derivative> Instead of the compounds represented by the chemical formulas 28 and 29, chemical formulas 31 and 31 respectively.
And Example 1 except that the one represented by the chemical formula 32 was used.
When the reaction was conducted according to the method of 1., the coumarin derivative of the present invention represented by the chemical formula 12 was obtained.

[0076]

Embedded image Chemical formula 31:

[0077]

Embedded image Chemical formula 32:

The coumarin derivative of this example having an absorption maximum and a fluorescence maximum in the visible region is used in various fields such as photochemical polymerization, solar cells, optical filters, dyes and dye lasers as a light absorber and a luminescent agent. It is useful.

[0079]

Example 4 <Coumarin derivative> Instead of the compounds represented by the chemical formulas 28 and 29, chemical formulas 33 and 33, respectively.
And Example 1 except that the one represented by the chemical formula 32 was used.
When the reaction was performed according to the method of 1., the coumarin derivative of the present invention represented by the chemical formula 11 was obtained.

[0080]

Embedded image Chemical formula 33:

The coumarin derivative of this example having an absorption maximum and a fluorescence maximum in the visible region is used as a light absorber and a luminescent agent in various fields including photochemical polymerization, solar cells, optical filters, dyes and dye lasers. It is useful.

[0082]

Example 5 <Coumarin derivative> Instead of the compounds represented by the chemical formulas 28 and 29, chemical formulas 34 and 34, respectively.
When the reaction was performed according to the method of Example 1 except that the compound represented by Chemical Formula 35 was used, the coumarin derivative of the present invention represented by Chemical Formula 2 was obtained.

[0083]

Embedded image Chemical formula 34:

[0084]

Embedded image Chemical formula 35:

The coumarin derivative of this example having an absorption maximum and a fluorescence maximum in the visible region is used in various fields including photochemical polymerization, solar cells, optical filters, dyes and dye lasers as a light absorber and a luminescent agent. It is useful.

[0086]

[Example 6] <Coumarin derivative> Examples 1 to 5
Any of the five types of coumarin derivatives obtained by the above method was charged into a water-cooled sublimation purification device, and heated by keeping the inside of the device at a reduced pressure according to a conventional method to perform sublimation purification.

Each of the coumarin derivatives of this example can be advantageously used in various fields in which a high-purity organic compound having a light absorbing ability and a light emitting ability is required.

Although the coumarin derivative of the present invention has a slight difference in the charging conditions and the yield depending on the structure, for example, the coumarin derivatives including those represented by the chemical formulas 1 to 27 other than the above are all used. The desired amount can be produced by the methods of Examples 1 to 6 or by the methods.

Next, experiments on the glass transition point and photosensitizing ability of the coumarin derivative according to the present invention will be described.

[0090]

[Experimental Example 1] <Glass transition point of coumarin derivative> With respect to the coumarin derivative represented by the chemical formula 18 obtained by the method of Example 1, a commercially available DSC analyzer (trade name "DSC") was used.
220U type ”manufactured by Seiko Instruments Inc.) and subjected to DSC analysis according to a conventional method.
A glass transition point was observed at 151 ° C. In parallel, the glass transition point of a known analog compound represented by the chemical formula 36 having no hydrocarbon group on the naphthothiazole ring was measured in the same manner, and it was 129 ° C. By the way, the known related compound represented by the chemical formula 36 has a significantly lower solubility in an organic solvent such as acetone or chloroform than the coumarin derivative according to the present invention represented by the chemical formula 18, but is represented by the chemical formula 18. It exhibited absorption maximum and emission maximum in the same wavelength range as the coumarin derivative of the present invention.

[0091]

Embedded image Chemical formula 36:

As is well known, the glass transition point is one of the important indexes for estimating the thermal stability of organic compounds, and it is said that the higher the glass transition point, the higher the thermal stability. The above experimental results show that the coumarin derivative of the present invention having a fused naphthalene ring in which one or more hydrocarbon groups are bonded in the molecule does not substantially change the desired optical properties of known related compounds. It shows that the heat resistance is remarkably improved.

[0093]

[Experimental Example 2] <Photosensitizing ability of coumarin derivative> According to a conventional method, 900 parts by weight of ethyl cellosolve, 100 parts by weight of pentaerythritol acrylate as a photopolymerizable monomer, and 100 parts of acrylic acid-methacrylic acid copolymer as a binder resin were used. Parts by weight, 3,3 'as a polymerization initiator,
8 parts by weight of 4,4'-tetra (tert-butylperoxycarbonyl) benzophenone were added, and the coumarin derivative of the present invention represented by the chemical formula 18 and obtained as a photosensitizer by the method of Example 1 was used. A photopolymerizable composition was prepared by blending 6 parts by weight.

According to a conventional method, this composition was uniformly applied onto a grained aluminum plate which had been surface-treated to form a photosensitive layer, and then a polyvinyl alcohol layer was formed on the surface of the photosensitive layer in order to prevent polymerization inhibition by oxygen. Was formed. A gray scale was attached to this photosensitive layer, a 3kW ultra-high pressure mercury lamp was installed, and a sharp cut-off filter (trade name "Y47") was installed.
And "Y52", manufactured by Toshiba Glass Co., Ltd., interference filter (trade name "KL49" and "KL54", manufactured by Toshiba Glass Co., Ltd.), and heat ray cut filter (trade name "H").
A30 ", manufactured by Hoya Co., Ltd.)
32 nm (equivalent to the second harmonic of Nd-YAG laser)
Of visible light. Then, after developing with an alkaline developer according to a conventional method, the transmittance T _n and the exposure time t at the nth step of the step tablet are expressed by the formula shown in Formula 1.
When the sensitivity was calculated from the number of steps of the photocuring step by substituting the exposure intensity I ₀ and the exposure intensity I ₀ , the sensitivity of the photopolymerizable composition used in the test was 0.1 mJ / cm ² . As a control, the composition prepared in the same manner as above except that the coumarin derivative was omitted was similarly irradiated with light, but no curing by polymerization was observed.

[0095]

These experimental results show that the coumarin derivative of the present invention is useful as a material for sensitizing a polymerizable compound or a polymerization initiator in photochemical polymerization.

[0097]

As described above, the present invention is based on the creation of new organic compounds and the discovery of their industrially useful properties. Since the coumarin derivative of the present invention has an absorption maximum in the visible region and a large molecular extinction coefficient, it can be advantageously used as a light absorber in the fields of photochemical polymerization, solar cells, optical filters, dyeing and the like. Furthermore, the coumarin derivative of the present invention has a maximum emission in the visible region and emits visible light when excited, and therefore can be advantageously used as a luminescent agent in the field of dye lasers and the like. Many of the coumarin derivatives according to the present invention have a high glass transition point and, as a result, have a high heat resistance, so that the light absorption ability and the light emission ability are hard to decrease even in an environment where high temperature is inevitable.

The useful amount of the coumarin derivative can be obtained in a desired amount by the production method of the present invention via a step of reacting a phenol compound having a specific atomic group with a naphthylamine compound having a specific atomic group. .

It can be said that the present invention, which has such a remarkable effect, is a significant invention that contributes to the field.

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Claims (7)

[Claims] 1. Represented by either general formula 1 or general formula 2.
Coumarin derivative. Embedded image General formula 1: Embedded image General formula 2: (In the general formulas 1 and 2, X is a carbon atom or
Represents a terror atom. R₁To R₁₄Each independently,
It represents a hydrogen atom or an appropriate substituent. However, R ₁as well as/
Or R_TwoIs the nitrogen atom to which they are attached, and R_ThreeOr R
_FourForm a cyclic structure containing the carbon atom to which
And in this case R_ThreeAnd / or R _FourIs apparently
It will not exist. Also, R₉To R₁₄One of
Is a hydrocarbon group, and the hydrocarbon group is a substituent
May have. Furthermore, X is a divalent or trivalent hetero
When it is a b atom, R₇And / or R₈Does not exist
Yes. ) 2. The coumarin derivative according to claim 1, which is represented by the general formula 3 or the general formula 4. Embedded image General formula 3: Embedded image General formula 4: (In the general formulas 3 and 4, X represents a carbon atom or a hetero atom as in the general formula 1 or the general formula 2. R _{5 to} R ₁₄ represent a hydrogen atom as in the general formula 1 or the general formula 2. Or R _{9 to} R, which represents an appropriate substituent.
It is assumed that any of ₁₄ is a hydrocarbon group. R ₁₅
To R ₁₈ each independently represent a hydrogen atom or an appropriate substituent. ) 3. The coumarin derivative according to claim 1, wherein any one of R _{9 to} R _{14 in} the general formula 1 or 2, the general formula 3 or the general formula 4 is a branched aliphatic hydrocarbon group. . 4. An absorption maximum in the visible region,
The coumarin derivative according to 2 or 3. 5. An emission maximum in the visible region,
The coumarin derivative according to 2, 3 or 4. 6. The coumarin derivative according to claim 1, having a glass transition point of higher than 130 ° C. 7. A compound represented by the general formula 5 having R _{1 to} R ₆ corresponding to the general formula 1 or 2, and the general formula 1
Or according to any one of claims 1 to 6 and a general formula 6 or a compound represented by any one of formulas 7 having X and R ₇ to R _{1 4} corresponding to the general formula 2 via the step of reacting A method for producing a coumarin derivative. Embedded image General formula 5: Embedded image General formula 6: Embedded image General formula 7: (In the general formulas 6 and 7, when X is a divalent or trivalent hetero atom, H ¹ and H ² do not exist.)