JPH0649358A - Actinic ray-sensitive polymer composition - Google Patents

Abstract

PURPOSE:To obtain an actinic ray-sensitive polymer composition having a high transmission even to light of a short wavelength and being capable of forming a practical image by mixing a specified polymer with a specified compound. CONSTITUTION:The composition comprises a polymer comprising structural units of the formula (wherein R<1> is a 2 C or higher tri- or tetra-valent organic group; R<2> is a 2 C or higher bivalent organic group; R<3> is H, an alkali metal ion or an ammonium ion; and n is 1-2) and a compound containing an electron- accepting group and an amino group or a quaternized salt thereof (e.g. dimethylaminoethyl-3,5-dinitrobenzene).

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to an actinic radiation-sensitive polymer composition, and more particularly to a photosensitive polyimide coating agent composition having excellent sensitivity.

[0002]

2. Description of the Related Art As a photosensitive polyimide composition, a polyamic acid, which can be dimerized or polymerized by actinic radiation, is used.
A composition containing a compound containing a carbon double bond and an amino group or a quaternized salt thereof (for example, JP-B-59-5282).
2) or a polyimide precursor composition obtained by introducing photosensitivity to a polyamic acid with an ester group (for example, USP39575).
12, USP 4040831).

On the other hand, semiconductor devices have been highly integrated,
Accordingly, the required pattern is required to be as fine as 1 μm or less. Accordingly, the exposure wavelength for forming the pattern is 436 nm to 365 nm,
Furthermore, exposure by an exposure device that emits deep ultraviolet light such as 308 nm and 248 nm is under study. Therefore, it is considered that short wavelength exposure is applied to the photosensitive polyimide composition used for the interlayer insulating film and the protective film of the semiconductor device.

However, such a conventional composition has a drawback in that when the exposure wavelength is short, the sensitivity of the composition is lowered due to the decrease of reactivity of the photosensitive component.

The present inventors have conducted a detailed study on the photoreaction of a conventional photosensitive polyimide in order to improve the sensitivity. As a result, the light absorption of the polyimide precursor is large in the short wavelength exposure as described above. , It was found that the energy available for the photosensitive component is very low.

In view of the above facts, the present inventors have studied the photoreaction of a photosensitive polyimide in order to improve the reactivity. As a result, a completely new photoreaction utilizing the photoreaction of a polyimide precursor has been conducted. The present invention has led to the discovery of a photosensitive polyimide which is insolubilized.

[0007]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide a novel actinic radiation-sensitive polymer composition which has a high transmittance even for a light ray having a short wavelength and can form a practical image. Especially.

[0008]

The object of the present invention is achieved by the following constitution.

(1) A polymer (A) having a structural unit represented by the general formula [I],

[Chemical 3] (However, R ¹ is a trivalent or tetravalent organic group having at least 2 or more carbon atoms, R ² is a divalent organic group having at least 2 or more carbon atoms, R ³ is hydrogen or an alkali metal ion. Or represents an ammonium ion, n is 1
Or 2. ) A compound (B) containing an electron-accepting group and an amino group or a quaternized salt thereof, and an actinic radiation-sensitive polymer composition.

(2) The compound (B) containing an electron-accepting group and an amino group or a quaternized salt thereof is a compound represented by the general formula [II]. Actinic radiation-sensitive polymer composition.

[0011]

[Chemical 4] (However, R ⁴ is a phenyl group, naphthyl group, anthryl group, pyridyl group or quinolyl group, P is a hydroxyl group, —OR
⁵ (however, R ⁵ is an organic group having 1 to 3 carbon atoms), an alkyl group having 1 to 3 carbon atoms, an amino group, a halogen atom or a halogenated methyl group, Q is a nitro group, -COR
⁶ (provided that R ⁶ is an organic group having 1 to 12 carbon atoms),
Aldehyde group, carboxyl group, -COOR ⁷ (provided that R ⁷ is an organic group having 1 to 10 carbon atoms), sulfonic acid group, -SO ₂ R ⁸ (provided that R ⁸ has 1 to 10 carbon atoms).
Up to organic groups) or cyano groups, X is —COO—, —O
_{-, - CH 2 -, -} SO 2 -, - SO-, or -CO
-, T is an alkylamino group having 1 to 6 carbon atoms, a dialkylamino group, a pyridine ring, or a quinoline ring. p is an integer from 0 to 5, q is an integer from 0 to 5, p + q <6, u is an integer from 0 to 6, r is an integer from 1 to 10, and s is an integer from 1 to 5. . ) The polymer (A) having the structural unit represented by the general formula [I] in the present invention has the structure represented by the above general formula [I], and has an imide ring or a ring formed by heating or a suitable catalyst.
Other examples include polymers that can be a polymer having a ring structure (hereinafter referred to as a polyimide-based polymer).

In the above general formula [I], R ¹ is at least 2
It is a trivalent or tetravalent organic group having one or more carbon atoms. From the heat resistance of the polyimide-based polymer, R ¹ preferably has a structure in which the bond with the carbonyl group of the polymer main chain is directly formed from the aromatic heterocycle. Therefore, R ¹ is preferably a trivalent or tetravalent group containing an aromatic ring or an aromatic heterocycle and having 6 to 30 carbon atoms.

Specific preferred examples of R ¹ include pyromellitic acid residue, 3,3 ', 4,4'-benzophenonetetracarboxylic acid residue, 3,3', 4,4'-biphenyltetracarboxylic acid residue. Acid residue, 3,3 ', 4,4'-diphenyl ether tetracarboxylic acid residue, 3,3', 4,4
Examples thereof include, but are not limited to, '-diphenylsulfone tetracarboxylic acid residue.

In the polymer (A), R ¹ is ^one of these.
It may be composed of one kind or a copolymer composed of two or more kinds.

In the above general formula [I], R ² is at least 2
It is a divalent organic group having one or more carbon atoms. Similar to R ¹ , in view of the heat resistance of the polyimide-based polymer, R ² preferably has a structure in which the bond with the carbonyl group of the polymer main chain is directly formed from the aromatic ring. Therefore, R ² is preferably a divalent group containing an aromatic ring or an aromatic heterocycle and having 6 to 30 carbon atoms.

Specific preferred examples of R ² include diaminodiphenyl ether residue, diaminodiphenyl sulfide residue, diaminodiphenylmethane residue, diaminodiphenyl sulfone residue, phenylenediamine residue, benzidine residue and bisaminophenoxypropane residue. Groups and the like, but are not limited thereto.

In the polymer (A), R ² may be composed of only one of these, or may be a copolymer composed of two or more.

Further, in order to improve the adhesiveness of the polyimide-based polymer, it is possible to copolymerize an aliphatic group having a siloxane bond as R ² within a range that does not lower the heat resistance. A preferred specific example is bis (3
-Aminopropyl) tetramethyldisiloxane residue and the like.

In the above general formula [I], R ³ is hydrogen, alkali metal ion or ammonium ion, and n is 1
Or 2.

The polymer (A) may be composed of only the structural unit represented by the general formula [I], or may be a copolymer or a blend with another structural unit.
In that case, it is preferable that 90% or more of the structural unit represented by the general formula [I] is contained. It is desirable to select the type and amount of the structural unit used for the copolymerization so long as the heat resistance of the polyimide polymer obtained by the final heat treatment is not significantly impaired.

Specific examples of the polymer (A) include pyromellitic dianhydride and 4,4'-diaminodiphenyl ether, 3,3 ', 4,4'-benzophenone tetracarboxylic dianhydride and 4,4'-diaminodiphenyl ether. 4'-diaminodiphenyl ether, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride and 4,4'-diaminodiphenyl ether,
Pyromellitic dianhydride and 3,3 '(or 4,4')
-Diaminodiphenyl sulfone, pyromellitic dianhydride and 3,3 ', 4,4'-benzophenone tetracarboxylic dianhydride and 3,3' (or 4,4 ')-diaminodiphenyl sulfone, 3,3' , 4,4'-benzophenone tetracarboxylic dianhydride and 3,3 '(or 4,4')-diaminodiphenyl sulfone, 3,3 ',
4,4'-biphenyltetracarboxylic acid dianhydride and 3,
3 '(or 4,4')-diaminodiphenyl sulfone, pyromellitic dianhydride and 4,4'-diaminodiphenyl sulfide, 3,3 ', 4,4'-benzophenone tetracarboxylic dianhydride and 4, 4'-diaminodiphenyl sulfide, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride and 4,4'-diaminodiphenyl sulfide, 3,3', 4,4'-benzotetracarboxylic dianhydride Thing and para-phenylenediamine, 3,3 ',
4,4'-biphenyltetracarboxylic acid dianhydride and paraphenylenediamine, pyromellitic acid dianhydride and 3,3 ', 4,4'-benzophenonetetracarboxylic acid dianhydride and paraphenylenediamine, pyromellitic acid 2
Anhydrous and 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride and paraphenylenediamine, 3,3
′, 4,4′-Diphenyl ether tetracarboxylic acid 2
Anhydrous and 4,4'-diaminodiphenyl ether, 3,
3 ', 4,4'-diphenyl ether tetracarboxylic acid dianhydride, paraphenylenediamine, pyromellitic acid 2
A polyamic acid synthesized from an anhydride, 4,4′-diaminodiphenyl ether, bis (3-aminopropyl) tetramethyldisiloxane, etc. is preferably used.

Electron-accepting group and amino group or its 4
As the compound (B) containing a quaternized salt, a compound containing an electron-accepting group and an amino group or a quaternized salt thereof in one molecule is used.

As the electron-accepting group, carbon-carbon double bond, polyene, benzene ring, pyridine ring, quinoline ring,
A group formed by connecting π electrons such as a naphthalene ring is preferably bonded to an electron-withdrawing group such as a nitro group, a carboxyl group, an alkoxycarbonyl group, a sulfonic acid group, an aldehyde group, an acyl group or a cyano group. In addition, weak electron-donating groups such as alkoxy group, alkyl group, allyl group, halogen atom, and halogenated methyl group are bonded to the group formed by the connection of these π electrons to increase the conjugated state of π electrons. Those more preferably used. In addition to such an electron-accepting group, an amino group such as an alkylamino group, a dialkylamino group, a pyridine ring, a quinoline ring, a trialkylamino group hydrochloride, an alkylpyridinium group tosyl salt, or a quaternized salt thereof is used. By being present in the compound, the object of the present invention can be achieved.

In the compound (B), when the amino group is not quaternized, it is preferred that R ^{3 in the} general formula [I] is combined with the hydrogen polymer (A). When the amino group is quaternized, it is preferable to combine R ³ with a polymer (A) of an alkali metal ion or an ammonium ion.

As such a compound (B), for example,
The compound represented by the following general formula [II] can be mentioned.

[0026]

[Chemical 5] In the above general formula [II], R ⁴ is a phenyl group, a naphthyl group, an anthryl group, a pyridyl group or a quinolyl group. Of these, phenyl, naphthyl and anthryl groups are particularly preferable.

P is a hydroxyl group, -OR ⁵ (wherein R ⁵ is an organic group having 1 to 3 carbon atoms), an alkyl group, an amino group,
It is a halogen atom or a halogenated methyl group. Specifically, a methoxy group, an ethoxy group, a methyl group, an ethyl group,
Examples thereof include a dimethylamino group, a fluorine atom, a chlorine atom, and a trifluoromethyl group. Of these, particularly preferred are alkoxy groups such as a methoxy group and an ethoxy group. p is an integer from 0 to 5, and when p is 2 or more,
P may be the same as or different from each other.

Q is a nitro group, --COR ⁶ (provided that R
⁶ is an organic group having 1 to 12 carbon atoms), an aldehyde group,
Carboxyl group, -COOR ⁷ (where R ⁷ is an organic group having 1 to 10 carbon atoms), sulfonic acid group, -SO ₂ R
⁸ (wherein R ⁸ is an organic group having 1 to 10 carbon atoms) or a cyano group. Specifically, nitro group, benzophenone group, methyl ketone group, ethyl ketone group, aldehyde group, carboxyl group, methyl carboxyl group, ethyl carboxyl group, phenyl carboxyl group, sulfonic acid group, methyl sulfonic acid group, p-toluene sulfonic acid group ,
Examples thereof include a cyano group. Of these, a nitro group, a cyano group and a benzophenone group are particularly preferable. q
Is an integer from 0 to 5, but the sum of p and q must be smaller than 6. As in the case of P, when q is 2 or more, Q may be the same or different.

X is --COO--, --O--, --CH ₂ -,-
SO ₂ -, - SO-, or -CO-. Of these, particularly preferred are -COO- and -O-.

T is an alkylamino group having 1 to 6 carbon atoms, a dialkylamino group, a pyridine ring, or a quinoline ring. Specific examples thereof include a methylamino group, a dimethylamino group, a diethylamino group, a pyridyl group, a methylpyridyl group, and a quinolyl group. Among these, a particularly preferable one is a dimethylamino group, a diethylamino group,
It is a pyridyl group.

U is an integer from 0 to 6, r is an integer from 1 to 10, and s is an integer from 1 to 5.

Examples of the compound represented by the above general formula [II] include dimethylaminoethylbenzoate, dimethylaminoethyl-nitrobenzoate, dimethylaminoethyl-dinitrobenzoate, dimethylaminoethyl-cyanobenzoate and dimethylaminoethyl-dimethoxy. Benzoate, dimethylaminoethyl naphthalate, dimethylaminoethyl-phenyl acetate, dimethylaminoethyl-nitrophenyl acetate, dimethylaminoethyl-cyanophenyl acetate, dimethylaminoethyl-methoxyphenyl acetate, diethylaminoethyl-nitrobenzoate, diethylaminoethyl-methoxybenzoate , Diethylaminopropyl-nitrobenzoate, diethylaminopropyl-methoxybenzoate, Propylaminohexyl-methoxybenzoate, dibutylaminobutyl-cyanobenzoate, dimethylaminoethyl benzyl ether, dimethylaminoethyl phenyl sulfone, dimethylaminoethyl chloroanthracenecarboxylate, dimethylaminoethyl nitropyridinecarboxylate, diethylaminopropyl fluoroquinolinecarboxylate, chloro Such as dimethylaminobutyl methylpyridine sulfonate, nitrophenyldimethylaminoethyl ketone, dimethylaminoethyl cyanonaphthyl sulfonate, 1-dinitrophenyl-2-pyridylethane, 1-methoxybenzaldehyde-2-quinolylethane, dimethylaminoethylsulfonemethylbenzophenone Other than these, electron accepting group and amino group As long as it is a compound which can be preferably used.

The compound (B) is used in an amount of 0.05 times or more, preferably 0.3 times or more and not more than 2 times the equivalent of all carboxyl groups (or salts thereof) of the polymer (A). It is preferable to mix with. This is because if the amount of the compound (B) is too small, the photosensitivity is likely to deteriorate, and if it is too large, the allowable range of developing conditions such as developing time and temperature may be narrowed.

The composition of the present invention further comprises a photoreactive carbon-carbon 2 such as dimethylaminoethylmethacrylate, diethylaminoacrylate, dimethylacrylamide, dimethylaminopropylmethacrylamide, dimethylaminoethylcinnamate and vinylpyridine.
An amino compound having a heavy bond can be added.
By adding these amino compounds, it is also possible to improve the photosensitivity during long-wavelength exposure. The addition amount thereof is preferably 0 to 90% by weight with respect to the compound (B). If it is more than 90% by weight, the sensitivity at short wavelength exposure is lowered.

If desired, a sensitizer may be added to the composition of the present invention. Examples of the sensitizer suitable for the present invention include aromatic amines such as N-phenyldiethanolamine, N-phenylglycine, dimethylaminophenylacetophenone and Michler's ketone, aromatic monoazides such as azidoanthraquinone and azidobenzalacetophenone, 3, 3 '. -Carbonylbis (7-diethylaminocoumarin), 3- (2'-benzimidazoyl) -N,
A coumarin compound having an amino group such as N-diethylaminocoumarin, which is generally used for photocurable resins, and other bis (diethylaminophenyl)-
1,3,4-oxadiazole, diphenylbenzidine, 2,3-bis (dimethylaminophenyl) -4-
(2-chlorophenyl) oxazole, N, N, N ',
N'-tetrakis (3-methylphenyl) -metaphenylenediamine, α-phenyl-4-N, N'-diphenylaminostilbene, para-diethylaminophenyl-diphenylhydrozide, etc., usually used as a positive charge transfer agent for electrophotography. And the like.

Such a sensitizer is preferably added in an amount of 0.01 to 30% by weight based on the polymer (A).
More preferably, it is 1 to 10% by weight. If it is too small, effective sensitivity does not appear, and if it is too large, it remains after the polymer is heated to form a polyimide, which may adversely affect electrical properties, mechanical properties, adhesiveness, and the like.

These sensitizers may be used alone or in admixture of two or more.

As other additives, a copolymerization monomer or a material for improving adhesion to a substrate may be contained within the range where sensitivity and heat resistance are not significantly lowered.

An example of the method for producing the composition of the present invention will be described. First, a diamine component and an acid dianhydride are reacted in a solvent to obtain a polymer (A) containing the structural unit [I] as a main component. Next, the compound (B) and, if necessary, an additive such as a sensitizer are dissolved and prepared in this solution to obtain a composition. As the polymer (A), a solid polyamic acid polymer or a polymer separated and purified from a solution after the reaction may be redissolved and used.

The solvent used in the above production method is preferably a polar solvent from the viewpoint of polymer solubility, and particularly preferably an aprotic polar solvent. As the aprotic polar solvent, N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, hexamethylphosphorotriamide, γ-
Butyrolactone and dimethylaminoacrylamide are preferably used.

Next, the method of using the composition of the present invention will be described. The composition of the present invention can be patterned by a known fine processing technique using actinic radiation.

First, the composition of the present invention is coated on a suitable support. Examples of the material of the support include metal, glass, semiconductor, metal oxide insulator, silicon nitride and the like.

As a coating method, spin coating using a spinner, spray coating using a spray coater, dipping, printing, roll coating and the like can be used. The coating film thickness can be adjusted by the coating means, the solid content concentration of the composition, and the viscosity, but normally the film thickness after drying is from 1 to 3.
It is applied so as to be in the range of 0 μm.

An adhesion aid may be appropriately used in order to improve the adhesion between the support and the coating film of the composition of the present invention or the polyimide coating after heat treatment.

Adhesion aids include oxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-
Organosilicon compounds such as methacryloxypropyltrimethoxysilane, aluminum chelate compounds such as aluminum monoethylacetoacetate diisopropylate, aluminum tris (acetylacetonate), or titanium bis (acetylacenate)
Titanium chelate compounds and the like are preferably used.

Next, the composition of the present invention formed into a coating film on the support is irradiated with actinic rays in a desired pattern. Examples of actinic rays include X-rays, electron rays, ultraviolet rays, and visible rays, but ultraviolet rays and visible rays of short wavelength, that is, those having a wavelength range of 200 to 500 nm are preferable.

Then, the unirradiated portion is dissolved and removed with a developing solution to obtain a relief pattern. The developing solution may be appropriately selected depending on the structure of the polymer, but N-methyl-2-pyrrolidone, N-acetyl-2-pyrrolidone, N, N-dimethylformamide, which is a solvent for the composition, N, N-dimethylacetamide, dimethylsulfoxide, hexamethylphosphortriamide, etc., alone or in methanol, ethanol, isopropanol, water,
Methyl carbitol, ethyl carbitol, toluene,
It can be used as a mixed solution of a composition such as xylene with a non-solvent. In many cases, aqueous ammonia or other alkaline aqueous solution can be used.

The development can be carried out by spraying the above-mentioned developing solution on the surface of the coating film, immersing in the developing solution, or applying ultrasonic waves while immersing.

The relief pattern formed by development is then preferably washed with a rinse liquid. As the rinse liquid, methanol, ethanol, isopropanol, butyl acetate or the like, which has good miscibility with the developer, is preferably used.

The polymer of the relief pattern obtained by the above treatment is a heat-resistant polyimide polymer precursor, and becomes a heat-resistant polymer having an imide ring or other cyclic structure by heat treatment. The heat treatment temperature is 135-
It is preferable to carry out at 400 ° C. The heat treatment is usually performed while raising the temperature stepwise or continuously.

The actinic radiation-sensitive polymer composition of the present invention is used for a semiconductor passivation film, a buffer coat film for a passivation film, an interlayer insulating film for a multilayer integrated circuit, an interlayer insulating film or a surface protective film for a hybrid integrated circuit, and a printed circuit. It is used to form the soldering protective film, the liquid crystal alignment film, the interlayer insulating film of the mounting substrate, and the like. Further, it can be applied to metal adhesion and dry etching process as a highly heat resistant photoresist. It can be applied to other known uses of polyimide.

[0052]

EXAMPLES The present invention will be described below with reference to examples.

Examples 1 to 9 and Comparative Example 1 <Polymerization of Polyamic Acid (Polyimide Precursor)>4,4'-diaminodiphenyl ether 20.
Add 0 g and dissolve in 150 g of N-methyl-2-pyrrolidone. Here, 21.0 g of pyromellitic dianhydride is N-
Methyl-2-pyrrolidone (30 g) was added at once and the mixture was vigorously stirred for 1 hour in an ice bath. Then, the temperature of the bath was raised to 50 ° C. and the reaction was carried out for 3 hours to obtain a solution of polyamic acid (1).

21.6 g of 4,4'-diaminodiphenyl sulfide was placed in a four-necked flask, and N-methyl-2-
Dissolve in 180 g of pyrrolidone. Here 3, 3 ',
4,4′-benzophenone tetrocarboxylic acid 2 anhydride 3
2.0 g was added at once along with 50 g of N-methyl-2-pyrrolidone and stirred vigorously in an ice bath for 1 hour. afterwards,
The bath temperature was raised to 50 ° C. and the reaction was carried out for 3 hours to obtain a solution of polyamic acid (2).

<Preparation of Photosensitive Solution> 100 g of the solution of the polyamic acid (1) or (2) contains an electron-accepting group and an amino group or a quaternized salt thereof in the same amount as the carboxyl group of the polyamic acid. Compound (B) was added as a photosensitizer. This is shown in Table 1. When a sensitizer was added here, 4% by weight of the sensitizer was added to the polyamic acid to prepare a photosensitive solution. This is shown in Table 2.

<Pattern processing> The solution was spin coated on a silicon wafer with a spinner, and then a vacuum adsorption type hot plate (SCW636 manufactured by Dainippon Screen Co., Ltd.).
Type) was dried at 90 ° C. and 95 ° C. for 3 minutes each. The film thickness of this coating film was 10 μm. Next, the coating film was exposed to a far-ultraviolet exposure machine (VIS-500C manufactured by USHIO INC.).
Set to grayscale (Kodak Photograph
1 with ultraviolet light through ics step tablet No2 21 steps)
J exposure was performed. With this gray scale mask, exposure with different exposure amounts can be performed, and the sensitivity can be measured. In addition,
The intensity of ultraviolet rays at this time is 7 mW / cm ² (254 nm)
Met.

The development was carried out by immersion development using a mixed solvent of N-methylpyrrolidone (70 parts) and xylene (30 parts). The development time is 1 more immediately after the unexposed area is dissolved.
Development was continued for 0 seconds. Then 20 with isopropanol
Rinse for 2 seconds and spin dry with a spinner. After the development, the sensitivity was judged from the exposure amount of the remaining portion of the image.

The results of the examination are shown in Table 3.

[0059]

[Table 1]

[Table 2]

[Table 3]

[0060]

According to the present invention, heretofore unseen,
It is possible to obtain a novel actinic radiation-sensitive polymer composition having a high sensitivity at a short wavelength and capable of forming a practical image.

Claims (2)

[Claims] 1. A polymer (A) having a structural unit represented by the general formula [I]: (However, R ¹ is a trivalent or tetravalent organic group having at least 2 or more carbon atoms, R ² is a divalent organic group having at least 2 or more carbon atoms, R ³ is hydrogen or an alkali metal ion. Or represents an ammonium ion, n is 1
Or 2. ) A compound (B) containing an electron-accepting group and an amino group or a quaternized salt thereof, and an actinic radiation-sensitive polymer composition. 2. An electron-accepting group and an amino group or its 4
The actinic radiation-sensitive polymer composition according to claim 1, wherein the compound (B) containing a quaternized salt is a compound represented by the general formula [II]. [Chemical 2] (However, R ⁴ is a phenyl group, naphthyl group, anthryl group, pyridyl group or quinolyl group, P is a hydroxyl group, —OR
⁵ (however, R ⁵ is an organic group having 1 to 3 carbon atoms), an alkyl group having 1 to 3 carbon atoms, an amino group, a halogen atom or a halogenated methyl group, Q is a nitro group, -COR
⁶ (provided that R ⁶ is an organic group having 1 to 12 carbon atoms),
Aldehyde group, carboxyl group, -COOR ⁷ (provided that R ⁷ is an organic group having 1 to 10 carbon atoms), sulfonic acid group, -SO ₂ R ⁸ (provided that R ⁸ has 1 to 10 carbon atoms).
Up to organic groups) or cyano groups, X is —COO—, —O
_{-, - CH 2 -, -} SO 2 -, - SO-, or -CO
-, T is an alkylamino group having 1 to 6 carbon atoms, a dialkylamino group, a pyridine ring, or a quinoline ring. p is an integer from 0 to 5, q is an integer from 0 to 5, p + q <6, u is an integer from 0 to 6, r is an integer from 1 to 10, and s is an integer from 1 to 5. . )