JPH0874196A - Defluorescence treatment of cellulose fiber, coumarin compound, aqueous liquid composition containing the compound and coloring of paper and pulp - Google Patents

Abstract

PURPOSE: To easily carry out the hitherto difficult defluorescence treatment of a cellulosic fiber in the presence of an alkali by using a specific coumarin- based fluorescent dye in the fluorescent brightening of a cellulosic fiber such as paper or pulp. CONSTITUTION: Paper, pulp, etc., are colored to obtain a brightened paper having excellent color value by using an aqueous solution containing a brightening agent consisting of a 7-triazinylamino-3-substituted coumarin derivative expressed by formula I [Z is phenyl, etc.; X and Y are each a 1-5C alkoxy, morpholino, cyclohexanol, OH, group of formula II (R2 and R3 are each H, a 1-5C alkyl, a 1-8C alkoxyalkyl, a 1-8C alkylanainoalkyl, etc.) or formula III (aromatic ring A is benzene or naphthalene ring; B is O, S or NH; (n) is 0-3) and the total number of sulfonic acid groups in X and Y is 1-3]. The fluorescent brightener enables the defluorescence treatment with an alkaline agent and optionally hydrogen peroxide and, accordingly, it is preferable for extremely reducing the environmental pollution in the reutilization of resources.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for defluorescence treatment of cellulose fibers, a coumarin compound, an aqueous liquid composition containing the same, and a method for coloring paper and pulp.

[0002]

BACKGROUND OF THE INVENTION Many fluorescent whitening agents for paper and pulp are known, but those actually used are, for example, Japanese Patent Publication No.
No. 4,164 'disclosed in Japanese Patent No. 7-16429, Japanese Patent Publication No. 50-33814, Japanese Patent Publication No. 2-54867.
It is a bistriazinylaminostilbene-2,2'-disulfonic acid type compound and exhibits a sufficient whitening effect. However, from the viewpoint of recent environmental problems and recycling of resources, the recycling of waste paper has been emphasized, and deinking and defluorescence treatment have been carried out, but the conventional 4,4'-bistriazinylaminostilbene- Defluorescence treatment is extremely difficult for paper treated with a 2,2'-disulfonic acid-based optical brightener.

[0003]

DISCLOSURE OF THE INVENTION Cellulosic materials, especially paper and pulp, have a high affinity, and the coloring of the coloring matter is excellent in whiteness, and it is easy to be water-based from the viewpoint of dust prevention and simplification of weighing. Moreover, there is a demand for the development of a fluorescent whitening agent capable of defluorescence treatment by a treatment method that does not use a chlorine-based bleaching agent.

[0004]

Means for Solving the Problems The present inventors have accomplished the present invention as a result of intensive studies to solve the above problems. That is, the present invention provides (1) a method for defluorescence treatment of cellulose fiber, which comprises immersing a cellulose fiber colored with a coumarin-based fluorescent dye decomposable by treatment with an alkali agent in a liquid containing an alkali agent, (2) A method for defluorescence treatment of cellulose fibers, which comprises immersing cellulose fibers colored with a coumarin-based fluorescent dye that can be decomposed by treatment with an alkaline agent in a liquid containing an alkaline agent and an active oxygen generator. (3) The defluorescence treatment method of the preceding item (2), wherein the active oxygen generator is hydrogen peroxide or ozone, (4) the preceding item (1), wherein the coumarin-based fluorescent dye is a coumarin-based fluorescent dye having a sulfonic acid group. 2) or the defluorescence treatment method of (3), (5) the number of sulfonic acid groups in the coumarin-based fluorescent dye having a sulfonic acid group is 1 to 3
(6) 7-triazinylamino-3-substituted coumarin-based fluorescent dye having 1 to 3 sulfonic acid groups having 1 to 3 sulfonic acid groups The defluorescence treatment method of the above (5), which is a coumarin derivative,
(7) The defluorescence treatment method according to the above item (6), wherein the sulfonic acid group in the 7-triazinylamino-3-substituted coumarin derivative is bonded to a substituent on the triazinyl group excluding the coumarin nucleus, (8) A 7-triazinylamino-3-substituted coumarin derivative having 1 to 3 sulfonic acid groups has the formula (1)

[Chemical 3] (In the formula (1), Z is a phenyl group which may have a substituent, —COOR ₁ (wherein R ₁ is a hydrogen atom, and has 1 to 5 carbon atoms).
Represents an alkyl group), X and Y are each independently an alkoxy group having 1 to 5 carbon atoms which may have a substituent, a morpholino group, a cyclohexanol group, a hydroxyl group,
Group represented by the following formula (2): —N (R ₂ ) R ₃ (2) (In the formula (2), R ₂ and R ₃ may each independently have a hydrogen atom or a substituent. Alkyl group having 1 to 5 carbon atoms, alkoxyalkyl group having 1 to 8 carbon atoms which may have a substituent, and 1 to 8 carbon atoms which may have a substituent
Of the formula (3), or a group represented by the following formula (3):

[Chemical 4] (In the formula (3), the aromatic ring A represents a benzene ring or a naphthalene ring which may have a substituent, and B is —O— or —S.
-Or-NH-, n represents an integer of 0 to 3),
And the total number of sulfonic acid groups in X and Y is 1 to 3). ) Is a coumarin compound represented by the above (6) defluorescence treatment method, (9) the cellulose fiber is a paper or pulp defluorescence treatment method (1) or (2), (10) the preceding paragraph (8) ) A coumarin compound represented by the formula (1) described above, (11) an aqueous liquid composition containing at least one coumarin compound represented by the formula (1) according to the above item (8),
(12) A method for coloring paper or pulp, which comprises using the coumarin compound of the formula (1) according to item (8).

To carry out the defluorescence treatment method of the cellulose fiber of the present invention, the cellulose fiber colored with a coumarin type fluorescent dye decomposable by an alkaline agent is subjected to the defluorescence treatment by an alkali decolorization method known per se. For example,
As an alkaline agent, for example, caustic soda, caustic potash, or sodium silicate is used, and immersed in an aqueous solution thereof at 10 to 70 ° C., preferably 30 to 60 ° C. for 0.5 to 5 hours, or stirred if necessary. do it. In this case, the concentration of the alkaline agent is usually 0.01 to 3% by weight, preferably 0.5 to 2% by weight. It is also possible to add an active oxygen generating agent to an aqueous solution of an alkaline agent for defluorescence treatment. Examples of the active oxygen generating agent include hydrogen peroxide, ozone, and agents capable of generating ozone. These are used as, for example, an aqueous hydrogen peroxide solution or an aqueous solution of a chemical capable of generating ozone. The active oxygen in the liquid containing the active oxygen generator is the concentration of active oxygen present in the aqueous solution having a hydrogen peroxide concentration of 1 to 8% by weight and an alkali concentration of 0 to 3% by weight in the hydrogen peroxide-based aqueous solution. A concentration equivalent to If necessary, a deinking agent may be added to the treatment bath in the defluorescence treatment method of the present invention, and the defluorescence treatment and the carbon removal treatment may be carried out simultaneously. Examples of the cellulose fibers targeted in the defluorescence treatment method of the present invention include paper and pulp. The concentration of the cellulose fiber in the alkaline agent aqueous solution to be used for the defluorescence treatment is 2 to 10% by weight, preferably 3 to.
About 6% by weight is preferable. The coumarin fluorescent dye is not particularly limited as long as it can be decomposed with an alkaline agent,
Having a sulfonic acid group, preferably 1 to 3 sulfonic acid groups
One having 1 to 3, more preferably 1 to 3 sulfonic acid groups
A 7-triazinylamino-3-substituted coumarin derivative or the like having a high coloring ability for cellulose fibers is used. Particularly preferred are the coumarin-based compounds represented by the above formula (1).

Z of the coumarin compound represented by the formula (1)
Examples of the substituent of the phenyl group which may have a substituent include an alkyl group having 1 to 5 carbon atoms such as a methyl group, an ethyl group, a propyl group, a butyl group and a pentyl group, a fluorine atom, a chlorine atom, Examples thereof include halogen atoms such as bromine atom and iodine atom. Specific examples of the phenyl group which may be substituted in Z include a phenyl group, a p-methylphenyl group, a p-chlorophenyl group and the like. Examples of the alkyl group having 1 to 5 carbon atoms for R ₁ in Z include a methyl group, an ethyl group, a propyl group, a butyl group and a pentyl group. -COO in Z
Specific examples of R ₁ include a carboxyl group, a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a butoxycarbonyl group and the like.

The substituent of the alkoxy group having 1 to 5 carbon atoms which may have a substituent in X and Y is, for example, 1 to 1 carbon atoms such as hydroxyl group, methoxy group and ethoxy group.
5 alkoxy group, hydroxyalkoxy group having 1 to 5 carbon atoms such as hydroxyethoxy, dimethylamino group,
Examples thereof include a di (alkyl group having 1 to 5 carbon atoms) amino group such as a diethylamino group, a phenyl group and a sulfonic acid group. Substituents of an alkyl group having 1 to 5 carbon atoms which may have a substituent, and R ₁ and R ₃ which have a substituent and have 1 to 8 carbon atoms, which are optionally substituted. 1 to 8 carbon atoms which may have a substituent and a substituent of the alkyl group
Examples of the substituent of the alkylaminoalkyl group include a hydroxyl group, a sulfonic acid group, a carboxyl group, a cyano group, an aminocarbonyl group, a phenyl group and a sulfophenyl group.

Specific examples of the C 1-5 alkoxy group which may have a substituent in X and Y include, for example, methoxy group, ethoxy group, propoxy group, butoxy group, t-butoxy group, hexyl group. Oxy group, 2-hydroxyethoxy group, 2-hydroxypropoxy group, 4-hydroxybutoxy group, 2-methoxyethoxy group, 2-ethoxyethoxy group, 2-methoxypropoxy group, 2- (2
-Hydroxyethoxy) ethoxy group, 2-dimethylaminoethoxy group, 2-diethylaminoethoxy group, phenylethoxy group, 2-sulfoethoxy group, 3-sulfopropoxy group and the like. Specific examples of the alkyl group having 1 to 5 carbon atoms which may have a substituent in R ₂ and R ₃ of the formula (2) include, for example, methyl group, ethyl group, propyl group, butyl group, t -Butyl group, hexyl group, hydroxyethyl group, dihydroxyethyl group, hydroxypropyl group, dihydroxypropyl group, sulfomethyl group,
Examples thereof include 2-sulfoethyl group, sulfophenylmethyl group, carboxyethyl group, cyanoethyl group, 2-aminocarbonylethyl group, benzyl group, phenethyl group and the like, and optionally substituted alkoxy having 1 to 8 carbon atoms. Specific examples of the alkyl group include, for example, a methoxyethyl group, a dimethoxyethyl group, an ethoxyethyl group, a diethoxyethyl group, an ethoxypropyl group, a diethoxypropyl group, and a butoxyethyl group, which have a substituent. Specific examples of the alkylaminoalkyl group having 1 to 8 carbon atoms include a methylaminoethyl group, a dimethylaminoethyl group, an ethylaminoethyl group, a diethylaminoethyl group, a methylaminopropyl group, an ethylaminopropyl group and the like. To be

Specific examples of the group represented by the formula (2) in X and Y include, for example, amino group, methylamino group, ethylamino group, propylamino group, butylamino group and t.
-Butylamino group, hexylamino group, dimethylamino group, diethylamino group, dipropylamino group, dibutylamino group, hydroxyethylamino group, dihydroxyethylamino group, hydroxypropylamino group, dihydroxypropylamino group, sulfomethylamino group, Carboxyethylamino group, N-ethyl-N- (cyanoethyl) amino group, N-ethyl-N- (2-aminocarbonylethyl) amino group, benzylamino group, phenethylamino group, N-ethyl-N-benzylamino group , N-ethyl-N- (sulfophenylmethyl) amino group, 2-sulfoethylamino group, N-methyl-N- (2-sulfoethyl) amino group, methoxyethylamino group, dimethoxyethylamino group, ethoxyethylamino group , Diethoxyethylamino group, eth Shi propylamino group, di-ethoxypropyl group, butoxyethyl group, methylamino ethylamino group, dimethylamino ethylamino group,
Examples include ethylaminoethylamino group, diethylaminoethylamino group, di (methylaminoethyl) amino group, di (ethylaminoethyl) amino group, methylaminopropylamino group, ethylaminopropylamino group, allylamino group and diallylamino group. To be

Specific examples of the group represented by the formula (3) in X and Y include, for example, phenoxy group, 2-, 3- or 4-methylphenoxy group, 3- or 4-ethylphenoxy group, 2- , 3- or 4-chlorophenoxy group,
2,4-dimethylphenoxy group, 4-methoxyphenoxy group, 4-ethoxyphenoxy group, 2- or 4-carboxyphenoxy group, 4-methoxycarbonylphenoxy group, 4-ethoxycarbonylphenoxy group, 2-, 3
-Or 4-sulfophenoxy group, 2-methyl-4-sulfophenoxy group, 4-methyl-2-sulfophenoxy group, 4-methyl-3-sulfophenoxy group, 4-chloro-2-sulfophenoxy group, 2, 4-disulfophenoxy group, 2,5-disulfophenoxy group, 1-naphthoxy group, 2-naphthoxy group, 4-methoxy-1-naphthoxy group, 4-carboxy-1-naphthoxy group, 3-carboxy-6- Carboxy-2-naphthoxy group, 2-, 3-,
4-, 5-, 6-, 7- or 8-sulfo-1-naphthoxy group, 1-, 4-, 5-, 6-, 7- or 8-sulfo-2-naphthoxy group, 2,4-di -, 3, 6-ji-,
3,7-di-, 3,8-di- or 4,7-di-1-naphthoxy group, 3,6-di-, 6,8-di- or 4,8
-Di-sulfo-2-naphthoxy group, 3,6,8-trisulfo-1-naphthoxy group, 3,6,8-trisulfo-2
-Naphthoxy group, anilino group, 2-, 3- or 4-methylanilino group, 2-, 3- or 4-ethylanilino group, 2,4-dimethylanilino group, 2,6-dimethylanilino group, 2,4 , 6-trimethylanilino group, 3- or 4-methoxyanilino group, 2-, 3- or 4-chloroanilino group, 4-carboxyanilino group, 4-methoxycarbonylanilino group, 2-, 3-or 4-sulfoanilino group, 2,4-disulfoanilino group, 2,5-
Disulfoanilino group, 4-methyl-2-sulfoanilino group, 4-methyl-3-sulfoanilino group, 2-methyl-
4-sulfoanilino group, 4-chloro-2-sulfoanilino group, 4-chloro-3-sulfoanilino group, thiophenol group, 2-, 3- or 4-methylthiophenol group, 1-thionaphthol group and the like can be mentioned.

Of these substituents, preferred are, for example, Z is phenyl group, p-methylphenyl group,
p-chlorophenyl group, carboxyl group, methoxycarbonyl group, ethoxycarbonyl group, etc., X is phenoxy group, amino group, cyclohexanol group, morpholino group, hydroxyl group, allylamino group, diallylamino group, methoxy group, ethoxy group, 2- Hydroxyethoxy group, 2-methoxyethoxy group, 2-ethoxyethoxy group, 2-methoxypropoxy group, 2-dimethylaminoethoxy group, 2
-Diethylaminoethoxy group, 2-sulfoethoxy group,
Methylamino group, dimethylamino group, ethylamino group,
Diethylamino group, hydroxyethylamino group, dihydroxyethylamino group, dimethylaminopropylamino group, sulfomethylamino group, N-ethyl-N- (cyanoethyl) amino group, diethylaminopropylamino group,
N-ethyl-N- (sulfophenylmethyl) amino group,
N-methyl-N- (2-sulfoethyl) amino group is Y
Is a p-sulfophenylamino group, 2-, 3- or 4-
Sulfophenoxy group, 2-methyl-4-sulfophenoxy group, 4-methyl-2-sulfophenoxy group, 4-methyl-3-sulfophenoxy group, 4-chloro-2-sulfophenoxy group, 2,4-disulfo Phenoxy group, 2,5
-Disulfophenoxy group, 1-naphthoxy group, 2-naphthoxy group, 2-, 3-, 4-, 5-, 6-, 7- or 8-sulfo-1-naphthoxy group, 1,-, 4-, 5 -, 6
-, 7- or 8-sulfo-2-naphthoxy group, 2,4
-Di-, 3,6-di-, 3,7-di-, 3,8-di- or 4,7-di-1-naphthoxy group, 3,6-di-,
6,8-di- or 4,8-di-sulfo-2-naphthoxy group, 3,6,8-trisulfo-1-naphthoxy group,
3,6,8-trisulfo-2-naphthoxy group, 2-, 3
-Or 4-sulfoanilino group, 2,4-disulfoanilino group, 2,5-disulfoanilino group, 4-methyl-2
-Sulfoanilino group, 4-methyl-3-sulfoanilino group, 2-methyl-4-sulfoanilino group, 4-chloro-
Examples thereof include 2-sulfoanilino group.

Specific examples of the coumarin-based compound represented by the formula (1) of the present invention include the following compounds. In each embodiment, the sulfonic acid group shall be represented in the form of the free acid.

[0017]

[Chemical 5]

[0018]

[Chemical 6]

[0019]

[Chemical 7]

[0020]

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[0021]

[Chemical 9]

[0022]

[Chemical 10]

[0023]

[Chemical 11]

[0024]

[Chemical 12]

[0025]

[Chemical 13]

[0026]

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The coumarin compound represented by the formula (1) of the present invention is a 7-aminocoumarin compound and cyanuric chloride, amine compound, alcohol compound, for example, according to the method described in Japanese Patent Publication No. 43-17296. It can be produced by sequentially condensing with a compound or the like. More specifically, the compound of formula (1) of the present invention has the formula (4)

[0028]

[Chemical 15]

7-aminocoumarin compounds and X-H,
It is obtained by condensing the compound of Y-H (X and Y have the same meanings as described above) with cyanuric chloride in an arbitrary order in a molar ratio of 1 each. This condensation reaction is carried out using an aqueous solvent or an inert organic solvent such as acetone or dimethylformamide, alone or in a mixture. When sufficient solubility cannot be obtained, a surfactant or the like can be used in combination. Since hydrogen chloride is liberated in the condensation reaction, it is preferable to add a neutralizing agent, and hydroxides, carbonates and bicarbonates of alkali metals such as lithium, sodium and potassium are advantageously used. If necessary, organic amines can also be used. The reaction temperature varies depending on the reactivity of each raw material compound used, but is usually 0 to 20 ° C for the primary condensation reaction, 20 to 70 ° C for the secondary condensation reaction, and 50 to 12 for the tertiary condensation reaction.
It is carried out at 0 ° C. After the completion of the reaction, the coumarin-based compound of the formula (1) can be isolated by a generally known method (for example, salting out, aciding out, etc.) and, if necessary, purified.

In order to advantageously obtain an aqueous liquid composition of the coumarin-based compound of the formula (1), an inorganic base or (and ) It can be prepared by adding an organic base to a pH value of 7 to 13 and dissolving it, and a solubilizing agent can be added if necessary. Examples of inorganic or organic bases that can be used here include lithium, sodium, potassium, ammonium, and other hydroxides, carbonates,
Bicarbonate, monoethanolamine, diethanolamine, triethanolamine, 3-propanolamine, 2-propanolamine, dipropanolamine,
Tripropanolamine, triisopropanolamine, diethylamine, triethylamine, methyldiethanolamine, ethyldiethanolamine, N-methylethanolamine, N-ethylethanolamine, N,
Examples thereof include organic amines such as N-dimethylethanolamine, N, N-diethylethanolamine and N-phenylethanolamine, but are not limited thereto. Examples of solubilizers that can be used include
Urea, alkylurea, acid amide compounds such as ε-caprolactam, ethylene glycol, diethylene glycol,
Triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, butylene glycol, methyl cellosolve, carbitol, methyl carbitol, ethylene glycol dimethyl ether, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, Triethylene glycol monomethyl ether, propylene glycol monomethyl ether, butyl polyglycol, phenyl glycol, hexylene glycol, thioglycol, glycerin, tetrahydrofuran, dioxane, butyrolactone, N-methyl-2-pyrrolidone,
Examples thereof include water-soluble organic solvents such as formamide, dimethylformamide, methyl alcohol, ethyl alcohol, propyl alcohol and butyl alcohol. These solubilizers can be used alone or in combination of two or more. Incidentally, in order to facilitate liquefaction, when the reaction completed liquid is treated with an ultrafiltration membrane and a reverse osmosis membrane for desalting,
A thick solution is easily obtained.

The aqueous liquid composition of the present invention usually comprises 5 to 35% by weight of a coumarin compound represented by the formula (1) and 0 to a solubilizer.
It is prepared by mixing 30% by weight, a base for adjusting the pH value of the solution to 7 to 13 and water (the balance).
If necessary, the mixed composition can be filtered. In addition to the above, a surfactant, a fungicide and the like are added to the aqueous liquid composition of the present invention as required. The aqueous liquid composition of the coumarin-based compound of the formula (1) of the present invention is suitable for coloring cellulosic materials, especially paper and pulp.
As a coloring method for paper and pulp, an internal addition method is used in which a dye is added during or after beating of the pulp until the paper is made, and a dye is added to the size press liquid in the size press step after paper making. It is roughly classified into addition methods, but other methods such as overcoating the surface of the paper with a coating liquid prepared from a dye, an inorganic white pigment, a binder and the like are also adopted.
The aqueous liquid composition of the present invention can be applied to any method, but the more preferable method is the internal addition method.

In the internal addition method, pulp is first beaten with a pulper, a refiner or the like to a predetermined beating degree to form a pulp slurry, which is usually 0.01 to 2.0% (dry) at a temperature of 10 to 40 ° C. After adding an aqueous liquid composition of the coumarin-based compound of the formula (1) (purity amount per paper weight), and further adding an ordinary sizing agent, a sulfuric acid band, a paper strengthening agent, a sticking agent, etc., if necessary. A fluorescent whitening colored paper is obtained through a papermaking process and a drying process by a conventional method. In addition, in the external addition method, first, pulp is beaten with a pulper, a refiner or the like to a predetermined beating degree to form a pulp slurry, and ordinary fillers, sizing agents, sulfuric acid bands, fixing agents and the like are appropriately added, and then a conventional method is used. Make paper. Then, in the step of drying with a cylinder dryer, a large-sized (typically 20 to 60) cylinder dryer is used to contain an aqueous liquid composition of the coumarin-based compound of the formula (1) by a size press machine installed in the middle part of the cylinder dryer. A fluorescent whitened colored paper is obtained by applying the size press coating solution described above and then drying. The size press coating liquid in the above is the aqueous liquid composition of the present invention and starch, PV
A, CMC, a surface sizing agent, water, etc. are appropriately mixed and prepared, and the content of the coumarin-based compound of the formula (1) in the size press coating liquid is usually 0.04 to 2.0%. (Pure content), and the coating amount of the size press coating liquid is usually 1 to 3 g / m ² (solid content) per dry papermaking paper. Since the aqueous liquid composition of the coumarin-based compound of the formula (1) of the present invention has a high affinity for paper (cellulose fiber), it is excellent in color value (coloring density) and the fluorescent whitening effect of the obtained colored paper is high. It is good. Since the coumarin-based compound of the formula (1) of the present invention has a high affinity for paper, an ink for ink jet recording intended for recording on paper, and
It can also be applied to stationery ink by a conventional method.

[0033]

EXAMPLES Next, the present invention will be described more specifically by way of examples. In the examples, “parts” means “parts by weight”, and%
Represents% by weight. Example 1 19.0 parts of cyanuric chloride were dissolved in 80 parts of acetone to prepare 3 parts.
Pour into 00 parts ice water with stirring. This suspension at 5 ° C
Keeping below, 400 parts of an aqueous solution of 34.8 parts of disodium 2-naphthol-3,6-disulfonate dissolved in 10% lithium hydroxide aqueous solution for 30 minutes while maintaining a pH value of 3-4. And drip. Then, after reacting for 1 hour, the mixture is heated to 30 ° C., and a solution obtained by dissolving 22.5 parts of 7-amino-3-phenylcoumarin in 600 parts of acetone is dropped into this reaction solution over 30 minutes. Then 10%
The reaction is carried out for 3 hours while maintaining the temperature at 50 ° C. while maintaining the pH value at 6 to 7 with an aqueous lithium hydroxide solution. After that, 21.0 parts of diethanolamine is added and heated while distilling off acetone to react at a temperature of 80 ° C. for 2 hours. To the reaction solution thus obtained, 2 parts of activated carbon was added for purification treatment, 20% of sodium chloride was added to the filtered filtrate for salting out, and the precipitated solid was separated by filtration and dried,
55.0 parts of the No. 1 coumarin compound of the present invention was obtained (maximum absorption wavelength in water (the same applies hereinafter); λ _max = 356 n)
m). This was added to a mixture of 120 parts of water, 30 parts of urea and 30 parts of ethylene glycol, lithium hydroxide was added while raising the temperature to 60 ° C., the pH value was adjusted to 8.5 and dissolved, and a small amount of insoluble The fraction was filtered off to obtain an aqueous liquid composition of the present invention containing the coumarin compound of No. 1.

Example 2 19.0 parts of cyanuric chloride were dissolved in 80 parts of acetone to give 80 parts.
Add with stirring to a mixture of 1 part ice and 80 parts water. While maintaining this suspension at 5 ° C. or lower, 300 parts of a neutral aqueous solution in which 27.5 parts of 2,5-disulfoaniline monosodium was dissolved was added with a 10% sodium carbonate aqueous solution to obtain a pH value of 3 to
While maintaining at 4, add dropwise over 30 minutes. Then, after reacting for 3 hours, the mixture is heated to 30 ° C. and placed in the reaction solution.
A solution prepared by dissolving 22.5 parts of amino-3-phenylcoumarin in 70 parts of DMF solvent is added dropwise over 30 minutes. afterwards,
The reaction is carried out for 2 hours while maintaining the temperature at 50 ° C. while maintaining the pH value at 6 to 7 with a 10% sodium carbonate aqueous solution. Then, 160 parts of 70% ethylamine aqueous solution is added, and the mixture is heated while distilling off acetone and reacted at a temperature of 80 ° C. for 2 hours. To the reaction solution thus obtained, 2 parts of activated carbon was added for purification treatment, hydrochloric acid was added to the filtered filtrate for acid precipitation, and the precipitated solid was filtered off to obtain No. 2 coumarin compound 53.8 of the present invention.
(Maximum absorption wavelength; λ _max = 358 nm). Add this to a mixture of 120 parts of water, 30 parts of urea and 30 parts of ethylene glycol, add lithium hydroxide while raising the temperature to 60 ° C., adjust the pH value to 8.5 and dissolve, and insoluble in a small amount. The fraction was separated by filtration to obtain an aqueous liquid composition of the present invention containing No. 2 coumarin compound.

Examples 3 and 4 In the same manner as in Example 1 except that sodium p-phenolsulfonate was used instead of disodium 2-naphthol-3,6-disulfonate in Example 1, the present invention was carried out.
No. 3 coumarin compound was obtained (maximum absorption wavelength; λ _max =
349 nm). Further, morpholine was used in place of the 70% ethylamine aqueous solution in Example 2 and the coumarin compound of No. 4 of the present invention was obtained by the same operation as in Example 2 (maximum absorption wavelength; λ _max = 361 nm). In addition, Example 1
By the same operation as above, an aqueous liquid composition of the present invention containing the coumarin compound of No. 3 or 4 was obtained. These aqueous liquid compositions were stable at room temperature for 6 months and at −5 ° C. for 1 month, and were free from crystal precipitation and solidification, and did not decrease in concentration or change in hue.

Example 5 2 containing 19.0 parts of cyanuric chloride and 0.5 part of surfactant
Disperse by adding to 00 parts of ice water with stirring. While keeping this suspension at 5 ° C or lower, 1 part of an aqueous solution of 300 parts in which 29.7 parts of 2,5-disulfoaniline disodium was dissolved was added.
While maintaining the pH value of 3 to 4 with a 0% aqueous solution of sodium carbonate, the solution is added dropwise over 30 minutes. Then, after reacting for 3 hours, the mixture was heated to 30 ° C., and 7-amino-3-
A solution prepared by dissolving 22.5 parts of phenylcoumarin in 600 parts of acetone is added dropwise over 30 minutes. Then, the reaction is carried out for 3 hours while maintaining the temperature at 50 ° C. while maintaining the pH value at 6 to 7 with a 10% sodium carbonate aqueous solution. After that, 21.0 parts of diethanolamine is added and heated while distilling off acetone to react at a temperature of 80 ° C. for 2 hours. The reaction solution thus obtained was subjected to a purification treatment by adding 2 parts of activated carbon, 20% sodium chloride was added to the filtered filtrate for salting out, and the precipitated solid was filtered out to obtain No. 5 of the present invention. Coumarin compound 6
6.5 parts (maximum absorption wavelength; λ _max = 360 nm) was obtained. Add this to a mixture of 120 parts of water, 30 parts of urea and 30 parts of ethylene glycol, add sodium hydroxide while raising the temperature to 60 ° C., adjust the pH value to 8.0 and dissolve, and dissolve a small amount of insolubles. The fraction was filtered off to obtain the aqueous liquid composition of the present invention containing the coumarin compound of No. 5. The aqueous liquid composition was stable at room temperature for 6 months and at −5 ° C. for 1 month, and was free from crystal precipitation and solidification, and did not decrease in concentration or change in hue.

Example 6 In Example 1, cyanuric chloride was condensed with 2-sodium disodium 2-naphthol-3,6-disulfonate and 7-amino-3-phenylcoumarin, and then acetone was distilled off under reduced pressure. Salt out with 10% sodium chloride, filter and dehydrate. This cake is suspended in 500 parts of ethylene glycol, heated to about 120 ° C. and reacted for 4 hours. During this time 4
The pH value is kept at 8-9 with 0% aqueous sodium hydroxide solution.
Then, the mixture was allowed to cool, the precipitated crystals were separated by filtration and dried to obtain the present invention.
White crystals of the coumarin compound of No. 6 were obtained. (Maximum absorption wavelength; λ _max = 351 nm)

Examples 7 to 38 According to Examples 1 to 6, a coumarin compound of the formula (1) and an aqueous liquid composition containing it were prepared. Table 1 shows the coumarin compound of the formula (1) and its content (%), the solubilizer and its content (%), the type of base and the adjusted pH value, and the fluorescence maximum absorption wavelength (nm) of the obtained compound. , Using it, Example 3
The hue when the paper was colored according to 9 or 40 was shown. still,
In the table, EG is ethylene glycol, DG is diethylene glycol, TG is triethylene glycol, PEG is polyethylene glycol, PG is propylene glycol, M
A means monoethanolamine, DA means diethanolamine, and TA means triethanolamine.

[0037]

[Table 1] Table 1 Example No. Coumarin of formula (1) Solubilizer, type of base, λ _max and color (Compound No.) Content of compound Content content pH value Phase 7 6 Urea 5 LiOH 348 DG15 pH 8.0 Medium White 8 6 Urea 13 NaOH 352 PG5 pH 8.5 Medium White 9 5 Urea 10 NaOH 348 TG10 pH 9.0 Medium White 10 5 Urea 10 LiOH 346 DG15 pH 9.0 D 10 Medium 10 349 pH 9.0 Medium white 12 10 Urea 5 TA 349 EG20 pH 9.0 Medium white 13 6 Urea 10 TA and NaOH 348 DG10 pH 8.5 Medium white 14 10 Urea 10 LiOH 347 DG15 pH 8.5 15 medium white. PEG 15 MA 350 pH 8.5 Medium white

16 6 Urea 10 NaOH 351 PG15 pH 9.0 Medium white 17 8 Urea 10 NaOH 355 TG10 pH 9.0 Medium white 18 8 Urea 10 LiOH 354 DG15 pH 8.5 Medium white 19 10 35 pH 5 D 5 NaOH 5 NaOH .0 Medium White 20 7 Urea 13 LiOH 356 PG5 pH 9.0 Medium White 21 8 Urea 5 NaOH 353 TG10 pH 8.5 Medium White 22 10 Urea 5 TA 349 DG15 pH 8.5 Medium White 15 23 15 15 Urea 23 23 15 15 pH 8.5 Medium white 24 10 Urea 5 NaOH 351 EG5 pH 9.0 Medium white 25 5 Urea 10 TA 349 EG10 pH 9.0 Medium white 26 12 Urea 5 LiOH 353 DG15 pH 8.5 Medium 5 urea 27 8 Three 9 EG15 pH8.0 patina taste white 28 10 Urea 10 NaOH 356 EG10 pH 9.0 Aoajishiro 29 10 Urea 10 TA 351 DG10 pH 8.0 Aoajishiro 30 8 Urea 10 LiOH 357 DG15 pH8.5 Aoajishiro

31 10 urea 10 LiOH 357 EG15 pH 8.0 bluish white 32 12 urea 10 NaOH 355 EG10 pH 9.0 bluish white 33 10 urea 10 TA 353 DG10 pH 8.0 bluish white 34.8 8 urea 10 LiOH 359 DG15 pH8 .5 bluish white 35 10 urea 5 LiOH 355 EG15 pH 8.0 bluish white 36 8 urea 13 NaOH 354 PG5 pH 9.0 bluish white 37 5 urea 10 NaOH 356 TG10 pH 9.0 bluish white 38 12 urea 10 LiOH 361 DG15 pH 8.5 patina white

Example 39 (coloring example) 0.02 part of the aqueous liquid composition prepared in Example 5 (No.
An aqueous solution comprising 50 parts of water and 0.005 parts of the compound of (5) was prepared, and 2 parts (dry weight) of bleached hardwood kraft pulp (beating degree of 35 ° SR) was added thereto, and the mixture was mixed at 10 at room temperature.
After stirring for minutes, 0.04 parts of rosin-based sizing agent (RF
Size 880L-50, Misawa Ceramic Chemicals KK
Manufactured). After further stirring for 5 minutes, 0.05 part of crystalline aluminum sulfate was added and stirred for 10 minutes. Then JIS
Paper making and drying are carried out according to the method described in P-8209 (Preparation method for hand test paper for pulp test). The paper thus obtained showed a fluorescent whitening effect with color value. The white water coloring after papermaking showed almost no fluorescence.

Example 40 (coloring example) 20.0 parts of the aqueous liquid composition prepared in Example 2 (No.
An anionic surface sizing agent (Polymaron 38) was added to an aqueous solution containing 5.0 parts of the compound (2) and 976.0 parts of water.
(2, manufactured by Arakawa Chemical Industry Co., Ltd.), and then the pH value of the solution is adjusted to 9.0 to obtain a size press coating solution. This solution was sent to a size press to color weak size paper having a Steckigt sizing degree of 7 seconds to obtain fluorescent whitening paper with good color uniformity and color value.

Example 41 (coloring example) Clay 8 was added to 20 parts of the aqueous liquid composition prepared in Example 1.
00 parts, heavy calcium carbonate 200 parts, acrylic dispersant (Kayacryl Resin C-220N, manufactured by Nippon Kayaku Co., Ltd.) 3 parts, phosphate esterified starch (MS-4)
600 Nippon Food Kako Co., Ltd. 50 parts, Latex (styrene-butadiene type L-1622 Asahi Kasei Co., Ltd.) 120 parts, Water-proofing agent (Sumirez Re)
For a mixture consisting of 4 parts of sin 636 and Sumitomo Chemical Co., Ltd., water was added to prepare a coating solution prepared so as to have a solid content of 55%, which was coated on high-quality paper, dried and fluorescent whitened. Got a piece of paper. This product was a fluorescent whitening paper with a high color value. Also, using the aqueous liquid composition of the coumarin compound described in Examples 1-38, Examples 39-41 were used.
When a fluorescent whitening paper was obtained according to the coloring method described in 1., the fluorescent whitening effect with high color value was exhibited in each case.

Example 42 (Example of defluorescence treatment) 2 parts of the colored brightening paper obtained in Example 39 was added with 0.08 part of sodium metasilicate, 0.02 part of caustic soda, and hydrogen peroxide solution (35% product). 12 parts, deinking agent (Lipotol LH-1
00, Nika Kagaku Co., Ltd.), treated with 66 parts of an aqueous solution containing 0.003 parts at a temperature of 50 ° C. for 3 hours, and then with JISP-8
According to the method described in 209 (Preparation method for handmade paper for pulp test), papermaking and drying were performed to obtain a paper without fluorescent whitening property, and defluorescence treatment was completed. Further, using the coumarin compound obtained in Examples 1 to 38, the paper colored by the operation of the coloring method of Examples 39 to 40 was subjected to the same defluorescence treatment as in Example 42. A paper having no fluorescent whitening property was obtained, and the defluorescence treatment was completed.

[0044]

By selecting a specific coumarin-based fluorescent dye as a fluorescent colorant for cellulose fibers such as paper and pulp, it is possible to treat with a solution containing an alkaline agent and, if necessary, an active oxygen generator. Since the fluorescent colorant can be easily removed from the cellulose fiber, the influence on the environment is extremely small. Further, by using the coumarin-based fluorescent dye of the present invention, it is possible to obtain a fluorescent whitening paper having a high color value from paper, pulp and the like. Furthermore, the aqueous liquid composition of the coumarin-based fluorescent dye of the present invention,
It is chemically and physically stable and extremely easy to handle.

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Claims (12)

[Claims] 1. A method for defluorescence treatment of cellulose fibers, which comprises immersing cellulose fibers colored with a coumarin-based fluorescent dye that can be decomposed by treatment with an alkaline agent in a liquid containing an alkaline agent. 2. A defluorescence treatment of cellulose fibers, which comprises immersing cellulose fibers colored with a coumarin-based fluorescent dye that can be decomposed by treatment with an alkali agent in a liquid containing an alkali agent and an active oxygen generator. Method 3. The defluorescence treatment method according to claim 2, wherein the active oxygen generator is hydrogen peroxide or ozone. 4. The defluorescence treatment method according to claim 1, 2 or 3, wherein the coumarin fluorescent dye is a coumarin fluorescent dye having a sulfonic acid group. 5. The defluorescence treatment method according to claim 4, wherein the coumarin-based fluorescent dye having a sulfonic acid group has 1 to 3 sulfonic acid groups. 6. The defluorescence of claim 5, wherein the coumarin-based fluorescent dye having 1 to 3 sulfonic acid groups is a 7-triazinylamino-3-substituted coumarin derivative having 1 to 3 sulfonic acid groups. Processing method 7. The defluorescence treatment method according to claim 6, wherein the sulfonic acid group in the 7-triazinylamino-3-substituted coumarin derivative is bonded to a substituent on the triazinyl group excluding the coumarin nucleus. 8. A 7-triazinylamino-3-substituted coumarin derivative having 1 to 3 sulfonic acid groups is represented by the formula (1): (In the formula (1), Z is a phenyl group which may have a substituent, —COOR ₁ (wherein R ₁ is a hydrogen atom, and has 1 to 5 carbon atoms).
Represents an alkyl group), X and Y are each independently an alkoxy group having 1 to 5 carbon atoms which may have a substituent, a morpholino group, a cyclohexanol group, a hydroxyl group,
Group represented by the following formula (2): —N (R ₂ ) R ₃ (2) (In the formula (2), R ₂ and R ₃ may each independently have a hydrogen atom or a substituent. Alkyl group having 1 to 5 carbon atoms, alkoxyalkyl group having 1 to 8 carbon atoms which may have a substituent, and 1 to 8 carbon atoms which may have a substituent
(Representing an alkylaminoalkyl group or an allyl group), or a group represented by the following formula (3): (In the formula (3), the aromatic ring A represents a benzene ring or a naphthalene ring which may have a substituent, and B is —O— or —S.
-Or-NH-, n represents an integer of 0 to 3),
And the total number of sulfonic acid groups in X and Y is 1 to 3). The defluorescence treatment method according to claim 6, which is a coumarin compound represented by 9. The defluorescence treatment method according to claim 1, wherein the cellulose fiber is paper or pulp. 10. A coumarin compound represented by the formula (1) according to claim 8. 11. An aqueous liquid composition containing at least one coumarin compound of formula (1) according to claim 8. 12. A method for coloring paper or pulp, which comprises using the coumarin compound of the formula (1) according to claim 8.