JP2000226578A - Coloring matter-stabilizing agent and its use - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a coloring matter-stabilizing agent containing a specific ascorbic acid derivative as an active ingredient, being decomposed by a light irradiation or heat in a suitable rate, exhibiting a reducing activity of the ascorbic acid and a radical scavenger activity, and useful for inhibiting a discoloration of the coloring matter. SOLUTION: This coloring matter-stabilizing agent contains a compound of the formula (R1 to R4 are each OH, an ester of OH with an inorganic acid or organic acid or the like) or its salt (preferably ascorbic acid-2-phosphate ester magnesium salt, etc.), as an active ingredient and preferably includes its molecular inclusion complex (preferably a cyclodextrin-based compound). As a substrate to which the coloring matter-stabilizing agent can be applied, a substrate capable of being used by the coloring is sufficient and a paper, wood, woven fabric, etc., can be cited. It is preferable to obtain a coloring composition by containing the coloring matter-stabilizing agent in it. As the coloring matter, an organic coloring matter (e.g.; Acridine orange, Janus green B) is preferred.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a dye stabilizer and its use. More specifically, ascorbic acid 2
Stabilizes ascorbic acid as a derivative having an ester group, a glycoside group, a ketal group with a ketone, an acetal group with an aldehyde, or the like, in which the hydroxyl group at the 3- or 3-position or the 2- and 3-positions has a reducing action or a radical scavenging action Is moderately expressed when coexisting with a dye, a dye stabilizer containing an ascorbic acid derivative that is effective in fading the dye,
The present invention relates to a dye composition and a dye coloring medium containing the dye stabilizer. The dye stabilizers of the present invention allow the stabilized ascorbic acid derivative to increase the stability of the dye when the dye is exposed to electromagnetic radiation (sunlight or artificial light) and heat.

[0002]

BACKGROUND OF THE INVENTION Dyes have the significant disadvantage that they fade when exposed to electromagnetic radiation and heat, such as sunlight or artificial light. It is believed that most of the fading of the dye upon exposure to light and heat is due to the photolysis mechanism and thermal decomposition, and the dye is oxidized or reduced and fades depending on the environmental conditions in which the dye is placed. The fading of dyes also depends on the substrate on which they are located. In particular, it is known that an organic dye compound fades due to electromagnetic radiation and heat and cannot withstand long-term use.

As a light stabilizer, a method using a nitroso compound has conventionally been disclosed in JP-A-2-300287 and JP-A-2-300288.
No. 2,300,289, this nitroso compound has many problems, such as strong toxicity per se or strong toxicity of photodegradation products. Not good for human body.

A method using a compound having a trinitrophenylhydrazine group as a light stabilizer other than a nitroso compound is disclosed in Japanese Patent Application Laid-Open No. Hei 2-304055, and these compounds having a trinitrophenylhydrazine group are disclosed. Has explosive properties and has a major problem in handling.

Further, a method using a metal complex such as a nickel compound having a thio ligand as a light stabilizer is disclosed in JP-A-59-219852, JP-A-62-193891, and JP-A-62-207688.
And JP-A-63-19293 and JP-A-63-199248. However, the stabilizing effect of any of the above methods is still insufficient and unsatisfactory. Accordingly, it is an object of the present invention to provide a means for effectively preventing the discoloration of a dye exposed to electromagnetic radiation such as sunlight or artificial light and heat for a long period of time.

[0006]

As a result of various studies, the present inventors have found that the substance itself is a substance which is very susceptible to oxidation and is unstable, and which may be exposed to electromagnetic radiation such as sunlight or artificial light, heat, and air. Ascorbic acid is stabilized by forming an ascorbic acid derivative in which the hydroxyl group at the 2- or 3-position or the 2- and 3-positions of ascorbic acid which is very easily oxidized and decomposed easily by oxygen therein is protected. Derivatives having a hydroxyl group are decomposed at an appropriate rate by light irradiation or heat, exhibiting a reducing action or a radical scavenger action of ascorbic acid, and have been found to be effective in suppressing the fading of the dye, and have completed the present invention. Reached.

Japanese Unexamined Patent Publication (Kokai) No. 63-113024 discloses colorant polymer particles containing a dye, an ultraviolet absorber and a reducing compound in the particles, and ascorbic acid (sodium), Ascorbic acid sulfate, ascorbic acid phosphate, and divalent iron ions are described as being selected from one or more selected from,
Specifically, the reducing agent described in the Examples is only L-ascorbic acid which cannot be used in the present invention, which is intended for a liquid dye composition, from the viewpoint of stability. Demonstrating ascorbic acid action, ascorbic acid derivatives such as salts of phosphoric acid esters as dye stabilizers used in the present invention by themselves without using in combination with an ultraviolet absorber are substantially said as a completed invention. It is not disclosed in the published gazette.

Japanese Patent Publication No. Hei 10-513502 discloses the invention of a coloring stabilizer comprising a hydrazone derivative, and discloses that ascorbic acid can be used in combination as a reducing agent. This also shows a moderate ascorbic acid action under light irradiation or heating conditions, and suggests the invention of an ascorbic acid derivative as a dye stabilizer used in the present invention by itself without using it in combination with other compounds. is not.

That is, the present invention relates to the following dye stabilizer, dye composition and dye coloring medium. (1) Formula (I)

Embedded image (Wherein R ¹ , R ² , R ³ and R ⁴ are each independently
A hydroxyl group, an ester group of the hydroxyl group and an inorganic acid or an organic acid, a glycoside group of the hydroxyl group and a sugar, a ketal group of the hydroxyl group and a ketone, or an acetal group of the hydroxyl group and an aldehyde. However, R ¹ and R ² do not simultaneously represent a hydroxyl group. A dye stabilizer comprising, as an active ingredient, a compound represented by the formula (1) or a salt thereof.

(2) The dye stabilizer as described in (1) above, wherein in the formula (I), R ¹ does not represent a hydroxyl group or a salt thereof as an active ingredient. (3) The dye stabilizer as described in (1) above, wherein in the formula (I), R ² does not represent a hydroxyl group or a salt thereof as an active ingredient. (4) The dye according to the above (2), wherein in the formula (I), a compound or a salt thereof, in which R ¹ is a hydroxyl group phosphate, sulfate, aliphatic carboxylate, glucoside or a salt thereof, or a salt thereof is used as an active ingredient. Stabilizer. (5) The dye according to the above item 3, wherein in the formula (I), R ² is a compound in which R ² is a phosphoric acid ester, a sulfuric acid ester, an aliphatic carboxylic acid ester, a glucoside or a salt thereof, or a salt thereof as an active ingredient. Stabilizer. (6) The compound of formula (I) is L-ascorbic acid, D
The dye stabilizer according to any one of the above 1 to 5, which is a derivative of ascorbic acid or a mixture of both. (7) The dye stabilizer according to any one of the above (1) to (6), wherein in the formula (I), R ¹ or R ² is a compound which is an alkali metal salt of a hydroxyl group phosphate or a salt thereof as an active ingredient. (8) In the above formula (I), R ¹ or R ² is a compound in which R ¹ or R ² is an alkaline earth metal salt or a transition metal salt of a phosphate ester of a hydroxyl group, or a salt thereof as an active ingredient.
The dye stabilizer according to any one of the above.

(9) Ascorbic acid-2-phosphate, ascorbic acid-2-phosphate magnesium salt, ascorbic acid-2-phosphate sodium salt, ascorbic acid-2-phosphate zinc salt, ascorbic acid -2-phosphate calcium salt, ascorbic acid-2-phosphate potassium salt, ascorbic acid-2-pyrophosphate ester sodium salt, ascorbic acid-2-phosphate potassium calcium salt, ascorbic acid-2-phosphate Ester magnesium potassium salt, ascorbic acid-2-phosphate aluminum salt, ascorbic acid-2-phosphate titanium salt,
Ascorbic acid-2-diphosphate sodium salt,
Ascorbic acid-2-triphosphate, ascorbic acid-2-polyphosphate, ascorbic acid-2-
Triphosphate sodium salt, ascorbic acid-2
-O-glucoside, magnesium ascorbic acid-2-phosphate-6-palmitate, sodium ascorbic acid-2-phosphate-6-palmitate, ascorbic acid-2-O-glucoside-6-palmitate, Ascorbic acid-2-O-glucoside-6-propionate, ascorbic acid-2-phosphate sodium magnesium salt, ascorbic acid-2-sulfate, ascorbic acid-2-sulfate sodium salt, ascorbic acid-2-ethylhydrogen Genphosphate, ascorbic acid-2-dodecyl hydrogen phosphate, ascorbic acid-2-heptyl hydrogen phosphate, ascorbic acid-2-octyl hydrogen phosphate calcium salt, ascorbic acid-2-propyl Contains one or more compounds selected from the group consisting of drogen phosphate, ascorbic acid-2-propylhydrogenphosphate disodium salt, and ascorbic acid-2-trihydrogendiphosphate potassium sodium salt as active ingredients The dye stabilizer according to any one of 1 to 8 above.

(10) Ascorbic acid-3-phosphate, magnesium ascorbic acid-3-phosphate, sodium salt of ascorbic acid-3-phosphate, zinc salt of ascorbic acid-3-phosphate, ascorbic acid -3-phosphate calcium salt, ascorbic acid-3-phosphate potassium salt, ascorbic acid-3-pyrophosphate sodium salt, ascorbic acid-3-phosphate potassium calcium salt, ascorbic acid-3-phosphate Ester magnesium potassium salt, ascorbic acid-3-phosphate aluminum salt, ascorbic acid-3-phosphate titanium salt,
Ascorbic acid-3-diphosphate sodium salt,
Ascorbic acid-3-triphosphate, ascorbic acid-3-polyphosphate, ascorbic acid-3-
Triphosphate sodium salt, ascorbic acid-3
-O-glucoside, magnesium ascorbic acid-3-phosphate-6-palmitate, sodium ascorbic acid-3-phosphate-6-palmitate, sodium ascorbic acid-3-O-glucoside-6-palmitate, Ascorbic acid-3-O-glucoside-6-propionate, ascorbic acid-3-phosphate sodium magnesium salt, ascorbic acid-3-sulfate, ascorbic acid-3-sulfate sodium salt, ascorbic acid-3-ethylhydrogen Genphosphate, ascorbic acid-3-dodecyl hydrogen phosphate, ascorbic acid-3-heptyl hydrogen phosphate, ascorbic acid-3-octyl hydrogen phosphate calcium salt, ascorbic acid-3-propyl Contains, as an active ingredient, one or more compounds selected from the group consisting of drogen phosphate, ascorbic acid-3-propylhydrogenphosphate disodium salt, and ascorbic acid-3-trihydrogendiphosphate potassium sodium salt The dye stabilizer according to any one of 1 to 8 above.

(11) The dye stabilizer according to any one of the above (1) to (10), further comprising a molecular clathrate. (12) The molecular inclusion complex is α-cyclodextrin, β
-Cyclodextrin, γ-cyclodextrin, δ-
Cyclodextrin, hydroxypropyl β-cyclodextrin, hydroxyethyl β-cyclodextrin, hydroxyethyl α-cyclodextrin, carboxymethyl α-cyclodextrin, carboxymethyl β-cyclodextrin, carboxymethyl γ-cyclodextrin, octylsuccinic α- Cyclodextrin, octylsuccinated β-cyclodextrin, octylsuccinated γ-cyclodextrin, sulfated β-
Cyclodextrin, sulfated γ-cyclodextrin,
Hydroxyethyl γ-cyclodextrin, hydroxyisopropyl γ-cyclodextrin, hydroxypropyl γ-cyclodextrin, octyl succinated γ-
12. The dye stabilizer according to the above item 11, which is a cyclodextrin-based compound such as cyclodextrin or carboxymethyl γ-cyclodextrin.

(13) Formula (I)

Embedded image (Wherein R ¹ , R ² , R ³ and R ⁴ are each independently
A hydroxyl group, an ester group of the hydroxyl group and an inorganic acid or an organic acid, a glycoside group of the hydroxyl group and a sugar, a ketal group of the hydroxyl group and a ketone, or an acetal group of the hydroxyl group and an aldehyde. However, R ¹ and R ² do not simultaneously represent a hydroxyl group. A dye composition comprising a dye stabilizer containing a compound represented by the formula (1) or a salt thereof as an active ingredient and a dye.

(14) The dye composition as described in (13) above, which comprises a dye stabilizer containing a compound or a salt thereof in which R ¹ does not represent a hydroxyl group in the formula (I) as an active ingredient, and a dye. (15) The dye composition as described in (13) above, which contains a dye and a dye containing, as an active ingredient, a compound in which R ² does not represent a hydroxyl group or a salt thereof in the formula (I). (16) In the above formula (I), a compound in which R ¹ is a phosphoric acid ester of a hydroxyl group, a sulfate ester, an aliphatic carboxylic acid ester, a glucoside or a salt thereof, or a dye stabilizer and a dye containing the salt thereof as an active ingredient is used. 15. The dye composition according to the above 14, which contains. (17) In the above formula (I), a compound in which R ² is a phosphoric acid ester of a hydroxyl group, a sulfate ester, an aliphatic carboxylic acid ester, a glucoside or a salt thereof, or a dye stabilizer and a dye containing the salt thereof as an active ingredient is used. 16. The dye composition according to the above 15, which contains. (18) The dye composition according to any one of (13) to (17), wherein the compound of the formula (I) is a derivative of L-ascorbic acid, D-ascorbic acid, or a mixture of both. (19) The above-mentioned (1), wherein R ¹ or R ² in the above formula (I) is a compound containing a compound which is an alkali metal salt of a phosphate ester of a hydroxyl group or a dye stabilizer containing the salt as an active ingredient and a dye.
19. The dye composition according to any one of items 3 to 18. (20) A dye stabilizer containing a compound in which R ¹ or R ² in the formula (I) is an alkaline earth metal salt or a transition metal salt of a phosphate ester of a hydroxyl group or a salt thereof as an active ingredient, and a dye. 19. The dye composition according to any one of 13 to 18 above.

(21) Ascorbic acid-2-phosphate, ascorbic acid-2-phosphate magnesium salt, ascorbic acid-2-phosphate sodium salt, ascorbic acid-2-phosphate zinc salt, ascorbic acid -2-phosphate calcium salt, ascorbic acid-2-phosphate potassium salt, ascorbic acid-2-pyrophosphate ester sodium salt, ascorbic acid-2-phosphate potassium calcium salt, ascorbic acid-2-phosphate Ester magnesium potassium salt, ascorbic acid-2-phosphate aluminum salt, ascorbic acid-2-phosphate titanium salt,
Ascorbic acid-2-diphosphate sodium salt,
Ascorbic acid-2-triphosphate, ascorbic acid-2-polyphosphate, ascorbic acid-2-
Triphosphate sodium salt, ascorbic acid-2
-O-glucoside, magnesium ascorbic acid-2-phosphate-6-palmitate, sodium ascorbic acid-2-phosphate-6-palmitate, ascorbic acid-2-O-glucoside-6-palmitate, Ascorbic acid-2-O-glucoside-6-propionate, ascorbic acid-2-phosphate sodium magnesium salt, ascorbic acid-2-sulfate, ascorbic acid-2-sulfate sodium salt, ascorbic acid-2-ethylhydrogen Genphosphate, ascorbic acid-2-dodecyl hydrogen phosphate, ascorbic acid-2-heptyl hydrogen phosphate, ascorbic acid-2-octyl hydrogen phosphate calcium salt, ascorbic acid-2-propyl One or more compounds selected from the group consisting of drogen phosphate, ascorbic acid-2-propylhydrogenphosphate disodium salt and ascorbic acid-2-trihydrogendiphosphate potassium sodium salt as an active ingredient 21. The dye composition according to any one of the above 13 to 20, comprising a dye stabilizer and a dye.

(22) Ascorbic acid-3-phosphate, ascorbic acid-3-phosphate magnesium salt, ascorbic acid-3-phosphate sodium salt, ascorbic acid-3-phosphate zinc salt, ascorbic acid -3-phosphate calcium salt, ascorbic acid-3-phosphate potassium salt, ascorbic acid-3-pyrophosphate sodium salt, ascorbic acid-3-phosphate potassium calcium salt, ascorbic acid-3-phosphate Ester magnesium potassium salt, ascorbic acid-3-phosphate aluminum salt, ascorbic acid-3-phosphate titanium salt,
Ascorbic acid-3-diphosphate sodium salt,
Ascorbic acid-3-triphosphate, ascorbic acid-3-polyphosphate, ascorbic acid-3-
Triphosphate sodium salt, ascorbic acid-3
-O-glucoside, magnesium ascorbic acid-3-phosphate-6-palmitate, sodium ascorbic acid-3-phosphate-6-palmitate, sodium ascorbic acid-3-O-glucoside-6-palmitate, Ascorbic acid-3-O-glucoside-6-propionate, ascorbic acid-3-phosphate sodium magnesium salt, ascorbic acid-3-sulfate, ascorbic acid-3-sulfate sodium salt, ascorbic acid-3-ethylhydrogen Genphosphate, ascorbic acid-3-dodecyl hydrogen phosphate, ascorbic acid-3-heptyl hydrogen phosphate, ascorbic acid-3-octyl hydrogen phosphate calcium salt, ascorbic acid-3-propyl Contains, as an active ingredient, one or more compounds selected from the group consisting of drogen phosphate, ascorbic acid-3-propylhydrogenphosphate disodium salt, and ascorbic acid-3-trihydrogendiphosphate potassium sodium salt 21. The dye composition according to any one of 13 to 20 above.

(23) The above-mentioned 13 containing a molecular clathrate
23. The dye composition according to any one of to 22. (24) The molecular inclusion complex is α-cyclodextrin, β
-Cyclodextrin, γ-cyclodextrin, δ-
Cyclodextrin, hydroxypropyl β-cyclodextrin, hydroxyethyl β-cyclodextrin, hydroxyethyl α-cyclodextrin, carboxymethyl α-cyclodextrin, carboxymethyl β-cyclodextrin, carboxymethyl γ-cyclodextrin, octylsuccinic α- Cyclodextrin, octylsuccinated β-cyclodextrin, octylsuccinated γ-cyclodextrin, sulfated β-
Cyclodextrin, sulfated γ-cyclodextrin,
Hydroxyethyl γ-cyclodextrin, hydroxyisopropyl γ-cyclodextrin, hydroxypropyl γ-cyclodextrin, octyl succinated γ-
24. The dye composition according to the above item 23, which is a cyclodextrin-based compound such as cyclodextrin or carboxymethyl γ-cyclodextrin.

(25) The above 13 which is an organic dye.
25. The dye composition according to any one of items 24 to 24. (26) The organic dye is acridine dye, azine dye, azoic dye, anthraquinone dye, indigo dye, oxazine dye, carminic acid dye, carotenoid dye, xanthene dye, coumarin dye, cyanine dye, diazo dye, diazonium salt dye, sulfonaphtha Selected from rain dyes, thiazine dyes, triarylmethyl dyes, trisazo dyes, naphthalimide dyes, paraquinoidal dyes, phthalocyanine dyes, phenylenediamine dyes, proflavin dyes, fluorescein dyes, benzimidazole dyes, monoazo dyes, and indigo dyes 26. The dye composition according to the above item 25.

(27) Formula (I)

Embedded image (Wherein R ¹ , R ² , R ³ and R ⁴ are each independently
A hydroxyl group, an ester group of the hydroxyl group and an inorganic acid or an organic acid, a glycoside group of the hydroxyl group and a sugar, a ketal group of the hydroxyl group and a ketone, or an acetal group of the hydroxyl group and an aldehyde. However, R ¹ and R ² do not simultaneously represent a hydroxyl group. A) a coloring matter medium containing a coloring matter stabilizer containing a compound represented by the formula (1) or a salt thereof as an active ingredient.

(28) The dye coloring medium according to the above (27), which comprises a dye stabilizer containing, as an active ingredient, a compound in which R ¹ does not represent a hydroxyl group or a salt thereof in the formula (I). (29) The dye coloring medium according to the above 27, further comprising a dye stabilizer containing, as an active ingredient, a compound in which R ² does not represent a hydroxyl group or a salt thereof in the formula (I). (30) In the above formula (I), a compound in which R ¹ is a phosphoric acid ester of a hydroxyl group, a sulfuric acid ester, an aliphatic carboxylic acid ester, a glucoside or a salt thereof or a dye stabilizer containing the salt thereof as an active ingredient is contained. 29. The dye coloring medium according to 28. (31) The above-mentioned formula (I), wherein R ² comprises a compound in which R ² is a phosphoric acid ester of a hydroxyl group, a sulfuric acid ester, an aliphatic carboxylic acid ester, a glucoside or a salt thereof, or a dye stabilizer containing the salt thereof as an active ingredient. 30. The dye coloring medium according to 29. (32) The dye coloring medium according to any one of the above (27) to (31), wherein the compound of the formula (I) is a derivative of L-ascorbic acid, D-ascorbic acid, or a mixture of both. (33) The compounds of the above-mentioned (27) to (32), wherein R ¹ or R ² in the above formula (I) is a compound which is an alkali metal salt of a phosphate ester of a hydroxyl group or a dye stabilizer containing a salt thereof as an active ingredient.
The dye coloring medium according to any one of the above. (34) The above-mentioned (27) wherein R ¹ or R ² in the formula (I) is a compound which is an alkaline earth metal salt or a transition metal salt of a phosphate ester of a hydroxyl group, or a dye stabilizer containing a salt thereof as an active ingredient. 33. The dye-coloring medium according to any one of the above items.

(35) Ascorbic acid-2-phosphate ester, ascorbic acid-2-phosphate magnesium salt, ascorbic acid-2-phosphate sodium salt, ascorbic acid-2-phosphate zinc salt, ascorbic acid -2-phosphate calcium salt, ascorbic acid-2-phosphate potassium salt, ascorbic acid-2-pyrophosphate ester sodium salt, ascorbic acid-2-phosphate potassium calcium salt, ascorbic acid-2-phosphate Ester magnesium potassium salt, ascorbic acid-2-phosphate aluminum salt, ascorbic acid-2-phosphate titanium salt,
Ascorbic acid-2-diphosphate sodium salt,
Ascorbic acid-2-triphosphate, ascorbic acid-2-polyphosphate, ascorbic acid-2-
Triphosphate sodium salt, ascorbic acid-2
-O-glucoside, magnesium ascorbic acid-2-phosphate-6-palmitate, sodium ascorbic acid-2-phosphate-6-palmitate, ascorbic acid-2-O-glucoside-6-palmitate, Ascorbic acid-2-O-glucoside-6-propionate, ascorbic acid-2-phosphate sodium magnesium salt, ascorbic acid-2-sulfate, ascorbic acid-2-sulfate sodium salt, ascorbic acid-2-ethylhydrogen Genphosphate, ascorbic acid-2-dodecyl hydrogen phosphate, ascorbic acid-2-heptyl hydrogen phosphate, ascorbic acid-2-octyl hydrogen phosphate calcium salt, ascorbic acid-2-propyl One or more compounds selected from the group consisting of drogen phosphate, ascorbic acid-2-propylhydrogenphosphate disodium salt and ascorbic acid-2-trihydrogendiphosphate potassium sodium salt as an active ingredient Dye stabilizing agent The dye coloring medium according to any one of the above items 27 to 34.

(36) Ascorbic acid-3-phosphate, ascorbic acid-3-phosphate magnesium salt, ascorbic acid-3-phosphate sodium salt, ascorbic acid-3-phosphate zinc salt, ascorbic acid -3-phosphate calcium salt, ascorbic acid-3-phosphate potassium salt, ascorbic acid-3-pyrophosphate sodium salt, ascorbic acid-3-phosphate potassium calcium salt, ascorbic acid-3-phosphate Ester magnesium potassium salt, ascorbic acid-3-phosphate aluminum salt, ascorbic acid-3-phosphate titanium salt,
Ascorbic acid-3-diphosphate sodium salt,
Ascorbic acid-3-triphosphate, ascorbic acid-3-polyphosphate, ascorbic acid-3-
Triphosphate sodium salt, ascorbic acid-3
-O-glucoside, magnesium ascorbic acid-3-phosphate-6-palmitate, sodium ascorbic acid-3-phosphate-6-palmitate, sodium ascorbic acid-3-O-glucoside-6-palmitate, Ascorbic acid-3-O-glucoside-6-propionate, ascorbic acid-3-phosphate sodium magnesium salt, ascorbic acid-3-sulfate, ascorbic acid-3-sulfate sodium salt, ascorbic acid-3-ethylhydrogen Genphosphate, ascorbic acid-3-dodecyl hydrogen phosphate, ascorbic acid-3-heptyl hydrogen phosphate, ascorbic acid-3-octyl hydrogen phosphate calcium salt, ascorbic acid-3-propyl One or more compounds selected from the group consisting of drogen phosphate, ascorbic acid-3-propylhydrogenphosphate disodium salt and ascorbic acid-3-trihydrogendiphosphate potassium sodium salt as an active ingredient 35. The dye coloring medium according to any one of the above items 27 to 34, comprising a dye stabilizer.

(37) The above-mentioned 27 containing a molecular clathrate
37. The dye coloring medium according to any one of claims to 36. (38) The molecular inclusion complex is α-cyclodextrin, β
-Cyclodextrin, γ-cyclodextrin, δ-
Cyclodextrin, hydroxypropyl β-cyclodextrin, hydroxyethyl β-cyclodextrin, hydroxyethyl α-cyclodextrin, carboxymethyl α-cyclodextrin, carboxymethyl β-cyclodextrin, carboxymethyl γ-cyclodextrin, octylsuccinic α- Cyclodextrin, octylsuccinated β-cyclodextrin, octylsuccinated γ-cyclodextrin, sulfated β-
Cyclodextrin, sulfated γ-cyclodextrin,
Hydroxyethyl γ-cyclodextrin, hydroxyisopropyl γ-cyclodextrin, hydroxypropyl γ-cyclodextrin, octyl succinated γ-
The dye coloring medium according to the above item 37, which is a cyclodextrin-based compound such as cyclodextrin or carboxymethyl γ-cyclodextrin.

(39) The substrates (27) to (3) comprising a substrate containing the dye composition described in any of (13) to (26) above.
8. The dye coloring medium according to any one of 8. (40) The dye coloring medium according to the above item 39, wherein the substrate is paper, wood, fiber, synthetic resin, glass, metal, ceramic, or a composite thereof.

Hereinafter, the present invention will be described in detail. The present invention provides a dye stabilizer for stabilizing a dye against radiation and heat including radiation in the visible wavelength range, a dye composition containing the dye stabilizer and a dye, and a dye coloring medium containing the dye stabilizer. It is a solution to the problem.

The essential component of the dye stabilizer of the present invention is an ascorbic acid derivative represented by the above general formula (I) or a salt thereof.

Embedded image

In the formula, R ¹ , R ² , R ³ and R ⁴ are each independently a hydroxyl group, an ester group of the hydroxyl group and an inorganic or organic acid, a glycoside group of the hydroxyl group and a sugar, It is a ketal group of the hydroxyl group and the ketone, or an acetal group of the hydroxyl group and the aldehyde (hereinafter, sometimes referred to as “ether group” in the present invention), but is not limited thereto.

In the formula (I), R ¹ and R ² are each bonded to the carbon at the 2-position and the 3-position of the ascorbic acid skeleton as a hydroxyl group, or as an ester group or an ether group.

The ester group is an ester group with an inorganic acid or an organic acid. Examples of the inorganic acid include phosphoric acid (monophosphoric acid), pyrophosphoric acid, triphosphoric acid, polyphosphoric acid, derivatives of these phosphoric acids, and sulfuric acid. Is mentioned. Among these, phosphoric acid, pyrophosphoric acid, and triphosphoric acid are preferable from the viewpoint of stability and the like, and phosphoric acid is particularly preferable. Examples of organic acids include saturated fatty acids such as acetic acid, propionic acid, butyric acid, isobutyric acid, pivalic acid, valeric acid, isovaleric acid, lauric acid, myristic acid, palmitic acid, stearic acid, propiolic acid, crotonic acid, oleic acid And unsaturated fatty acids.

The ether group is a glycoside group with sugar, a ketal group with ketone, an acetal group with aldehyde, etc., and glucose is preferable as the glycoside group. Ketones and aldehydes include acetone, methyl ethyl ketone, diethyl ketone, cyclopentanone, cyclohexanone, benzaldehyde and the like.

R ¹ and R ² do not represent a hydroxyl group at the same time, one of them is an ester group or an ether group and the other is a hydroxyl group, or both are an ester group or an ether group. Preferably, one of them is an ester group or an ether group, and the other is a hydroxyl group. More preferably, one is an ester group or glycoside group and the other is a hydroxyl group.

These ester groups or ether groups are
It is converted to a hydroxyl group by light or heat, and shows a stabilizing effect of the dye by the reducing action of ascorbic acid. Also,
The ascorbic acid derivative of the formula (I) is decomposed by light or heat to generate radicals, and exhibits a dye stabilizing effect also by its radical scavenger action.

In the formula (I), R ³ and R ⁴ are bonded to carbons at the 5- and 6-positions of the ascorbic acid skeleton as a hydroxyl group or as an ester group or an ether group, respectively. Specific examples include those described above for R ¹ and R ² , and when both R ³ and R ⁴ represent a hydroxyl group, adjacent hydroxyl groups may form a ketal or an acetal.
Alternatively, a hemiacetal may be formed. In particular, depending on R ¹ and R ^2, if R ³ and R ⁴ represent both hydroxyl groups, can be suitably used for dye stabilization of aqueous medium such as ink, also R ¹ (2-position) When represents a glycoside group, lipophilicity can be enhanced by making R ⁴ (position 6) an ester structure of a higher fatty acid.

When any of R ^{1 to} R ⁴ represents an ester group with an inorganic acid, it may be a salt with an alkali metal, an alkaline earth metal, another metal, ammonia, an amine or the like. Specific examples thereof include alkali metal salts such as sodium salt and potassium salt, alkaline earth metal salts such as calcium salt and magnesium salt, transition metal salts such as zinc salt, titanium salt, and aluminum salt. Alkali metal salts such as salts and potassium salts. Also, these double salts can be preferably used.

The ascorbic acid derivative used in the present invention may be any of D-form, L-form, and a mixture thereof.

Specific examples of the ascorbic acid derivative represented by the general formula (I) and salts thereof include, for example, ascorbic acid-2-phosphate ester, magnesium ascorbic acid-2-phosphate ester, ascorbic acid-2-phosphate Acid ester sodium salt, ascorbic acid-2-phosphate zinc salt, ascorbic acid-2-phosphate calcium salt, ascorbic acid-2-phosphate potassium salt, ascorbic acid-2-pyrophosphate ester sodium salt, ascorbin Acid-2-phosphate potassium calcium salt, ascorbic acid-2-phosphate magnesium potassium salt, ascorbic acid-2-phosphate aluminum salt, ascorbic acid-2-phosphate titanium salt, ascorbic acid-2- Diphosphate sodium salt Ascorbic acid-2-triphosphate ester, ascorbic acid 2-polyphosphate esters, ascorbic acid-2-triphosphate sodium salt,
Ascorbic acid-2-O-glucoside, ascorbic acid-2-phosphate-6-palmitate magnesium salt, ascorbic acid-2-phosphate-6-palmitate sodium salt, ascorbic acid-2-O-glucoside- 6-palmitate, ascorbic acid-2-O-glucoside-6-propionate, ascorbic acid-2-
Sodium magnesium phosphate, ascorbic acid-2-sulfate, sodium ascorbic acid-2-sulfate, ascorbic acid-2-ethyl hydrogen phosphate, ascorbic acid-2-dodecyl hydrogen phosphate, ascorbic acid-2-
Heptyl hydrogen phosphate, ascorbic acid-2-octyl hydrogen phosphate calcium salt, ascorbic acid-2-propyl hydrogen phosphate, ascorbic acid-2-propyl hydrogen phosphate disodium salt, ascorbic acid-2-
Trihydrogen diphosphate potassium sodium salt,

Ascorbic acid-3-phosphate, magnesium ascorbic acid-3-phosphate, sodium ascorbic acid-3-phosphate, zinc ascorbic acid-3-phosphate, ascorbic acid-3-phosphate Phosphate calcium salt, ascorbic acid-3-phosphate potassium salt, ascorbic acid-3
-Sodium pyrophosphate, ascorbic acid-
3-phosphate potassium calcium salt, ascorbic acid-3-phosphate magnesium potassium salt, ascorbic acid-3-phosphate aluminum salt, ascorbic acid-3-phosphate titanium salt, ascorbic acid-3-diphosphate Ester sodium salt, ascorbic acid-3-triphosphate, ascorbic acid-3
Polyphosphate, ascorbic acid-3-triphosphate sodium salt, ascorbic acid-3-O-glucoside, ascorbic acid-3-phosphate-6
Magnesium palmitate, ascorbic acid-3-phosphate-6-palmitate sodium salt, ascorbic acid-3-O-glucoside-6-palmitate, ascorbic acid-3-O-glucoside-6-propionate, ascorbic acid- 3-phosphate sodium magnesium salt, ascorbic acid-3-sulfate, ascorbic acid-3-sulfate sodium salt, ascorbic acid-3-ethyl hydrogen phosphate, ascorbic acid-3-dodecyl hydrogen phosphate, ascorbic acid- 3-heptyl hydrogen phosphate, ascorbic acid-3-octyl hydrogen phosphate calcium salt, ascorbic acid-3-propyl hydrogen phosphate, ascorbic acid-
3-propyl hydrogen phosphate disodium salt, ascorbic acid-3-trihydrogen diphosphate potassium sodium salt and the like can be mentioned.

Of these, preferred are magnesium ascorbic acid-2-phosphate ester sodium salt, ascorbic acid-2-phosphate sodium salt, ascorbic acid-2-phosphate zinc salt, and ascorbic acid-2 phosphate.
-Phosphate potassium salt, ascorbic acid-2-phosphate sodium magnesium salt, ascorbic acid-2-diphosphate sodium salt, ascorbic acid-2-triphosphate sodium salt, ascorbic acid-2-glucoside, ascorbic acid -2-sulfate ester sodium salt, and phosphate ester salt is particularly preferred.

The dye stabilizer of the present invention may contain a molecular clathrate of the above ascorbic acid derivative. The molecular clathrate may be contained in the substrate to which the dye is applied. Here, "contained in the substrate" means present on or in the substrate. Further, the molecular clathrate may be present in the dye composition. Molecular clathrates include clathrates, zeolites, crown ethers, calixarene, valinomycin-type natural antibiotics, various polyether compounds, nigericin-type natural antibiotics, and cyclic compounds containing multiple pyranose rings, It is not limited to these.

The cyclic compound includes, but is not limited to, cyclodextrins, for example, α-cyclodextrin, β-cyclodextrin, γ-cyclodextrin, δ-cyclodextrin, and derivatives thereof. A preferred molecular inclusion is cyclodextrin. A more preferred molecular clathrate is β-cyclodextrin. The substrate to which the dye stabilizer is applied may be any substrate that can be used by coloring, and specific examples include paper, wood, wood products or composite materials, woven fabric, nonwoven fabric, woven fabric, synthetic resin, glass, metal Etc., but are not limited to these.

As used herein, the term "dye composition" is not particularly limited, and an organic substance such as an organic colorant or dye is typically used together with an ascorbic acid derivative as a dye stabilizer. As a substance or 2
Include as a mixture of more than one species. As used herein, the term "dye coloring medium containing a dye stabilizer" refers to a base material to which the dye stabilizer is applied and on which the dye stabilizer is applied. Include both those already colored with a dye and those not colored.

Specific examples of the organic dye used in the present invention include the following, but are not limited thereto. Acridine dyes such as acridine orange, azine dyes such as Janus Green B, azoic diazo dyes such as Fast Blue BB salt,
Anthraquinone dyes such as Disperse Blue 3,
Alizarin Blue Black B, indigo dye, for example,
Indigo blue, oxazine dyes such as lumicrome, carminic acid dyes such as aluminum or calcium-aluminum lake of carminic acid, carotenoid dyes such as food orange 5, xanthene dye,
For example, 2,7-dichloro-fluorescein, a coumarin dye such as 7-hydroxy-4-methyl-coumarin (4-methylumbelliferone), a cyanine dye such as indocyanine green, a diazo dye such as Disperse Orange 13, diazonium salt dyes such as diazo red RC, sulfonaphthalein dyes such as cresol red, thiazine dyes such as methylene green and triarylmethyl dyes such as malachite green and trisazo dyes such as direct blue 71 and naphthalimide Dyes such as Lucifer Yellow CH, paraquinoidal dyes such as hematoxylin, phthalocyanine dyes such as Pigment Blue 15, phenylenediamine dyes such as Solvent Orange 53 or D Perth Yellow 9, a proflavin dye such as 3,6-diaminoacridine hemisulfate, a fluorescent dye such as fluoresceinamine, a benzimidazole dye such as bisbenzoimide, a monoazo dye such as cyanine black, β- Naphthol and Victoria Pure Blue B,
Indigo dyes such as indigo A (3-amino-7- (dimethylamino) phenothiazine-5-ium chloride or 7-
(Dimethylamino) -3-amino-3H-phenothiazine hydrochloride).

The dye stabilizer may be present in the dye composition or on or in the substrate to which the dye is applied (hereinafter the dye stabilizer may be present in or on the substrate). The base material existing in the above is referred to as “treated base material”).

A coloring medium which is a substrate treated with a dye stabilizer is also an object of the present invention. That is, the present invention includes a coloring medium that is a substrate treated with the dye stabilizer (ascorbic acid derivative). In another embodiment of the present invention, the treated substrate comprises a molecular inclusion on or in with the dye stabilizer. The substrate of the coloring medium of the present invention includes any substrate used by coloring, and specific examples include paper, wood, wood products or composite materials, woven fabric, nonwoven fabric,
Fabrics, plastics, glass and the like can be mentioned.

[0046] Plastic substrates include, but are not limited to, plastic films, plastic nonwoven webs, or plastic woven webs. A preferred substrate is paper. Any paper or paper product of existing or future types may be used as a substrate for the coloring media of the present invention. Examples of paper or paper products include printing paper and writing paper, wrapping paper and industrial paper, paperboard and tissue paper.

Printing paper and writing paper include wood-free coated paper, wood-containing coated paper, and wood-free uncoated paper, such as binding paper and writing paper, envelopes, offset paper and opaque circular paper, and carbon-free paper. , Stationery paper, form bond, ledger,
Copy paper, copy paper, copy paper, fax paper, thermal transfer paper, industrial paper, super calendar paper, and special paper; uncoated wood-containing paper, such as super calendar paper, list paper, special paper, etc. Publishing paper, Bristol paper, such as coated Bristol paper, uncoated bleached Bristol paper, tag paper, coated tag paper, file holder, and tabulation paper, and thin paper, such as cigarette paper, Bible paper, lightweight paper, Examples include lightweight specialty paper, copy paper, cotton fiber paper, and specialty thin paper.

Examples of wrapping paper and industrial paper include the following. Bleached kraft papers, such as food bags, transport sacks, wrappers, and processed papers, unbleached kraft papers, such as food bags, transport sacks, wrappers, and envelopes are also used.

Examples of paperboard are container boards,
For example, unbleached liner board, bleached liner board,
Corrugated cardboard as well as chipboard and filter board, folding box paperboard / folding carton paperboard, such as solid bleached sulphite paperboard, bleached and unbleached bristol paper, coated recycled paperboard, coated unbleached kraft paper, milk Paperboard, cupboard, plateboard, and food service base paper (coated or uncoated), folding box paperboard, plaster wall paperboard,
And paperboard for tubes / cans and paperboard for drums; examples of tissue papers include sanitary tissues such as
Bathroom tissue, facial tissue, napkins, towels, wiper base paper, and other sanitary tissue papers.

[0050]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples. In the following examples,% and parts are based on weight unless otherwise specified.

Example 1: Discoloration of azo dyes
Influence of ascorbic acid-2-phosphate sodium salt L-ascorbic acid-2-phosphate sodium salt was added at 1% w / w and 5% w with respect to an ink using an azo dye.
/ W, 10% w / w were added to a commercial water-soluble ink. The sample was stretched on paper to make a test piece for an exposure test. After placing the test piece on the mount and covering half with light-impermeable black paper,
Exposure was performed for 8 hours under the following conditions. After completion of the test, the black paper was removed, and the hues of the light-exposed portion and the unexposed portion were compared to determine the degree of fading. In addition, the non-addition section and the ascorbic acid addition section were also evaluated as a comparison section. Table 1 shows the results.

[0052]

[Table 1]

The light resistance test described above was performed using a high energy xenon weather meter (SC700 manufactured by Suga Test Instruments Co., Ltd.).
-WA) under the following conditions. Measurement conditions Irradiation energy: 150 W / m ² , Inner filter: Borosilicate, Outer filter: Soda lime glass, Temperature in test machine: 40 ° C., Humidity in test machine: 60% RH, Black panel temperature: 83 ° C. Evaluation criteria ：: Almost no fading, ：: Not very fading, Δ: Fading is observed, ×: Fading is severe.

Example 2: Dye composition containing L-ascorbic acid-2-glucoside L-ascorbic acid-2-glucoside was added at 1%, 5%, and 10% in a usual ink manufacturing process to obtain a stabilized dye. The composition was used. The stabilized dye composition was stretched on paper and subjected to a light resistance test for an exposure time of 48 hours under the conditions described above. In addition, the non-addition section and the ascorbic acid addition section were also evaluated as a comparison section. Table 2 shows the results.

[0055]

[Table 2]

Example 3 Effect of L-Ascorbic Acid-2-Phosphate Sodium Salt on Discoloration of Fluorescent Pigment L-ascorbic acid-2-phosphate sodium salt was dissolved in water to prepare a 30% solution. This was added at 10% and 20% to a standard preparation of SW-11 manufactured by Schinleich. After the sample was dyed on a cloth, dried by heating, and subjected to a light resistance test for an exposure time of 48 hours under the conditions described above. In addition, the non-addition section was also evaluated as a comparison section. Table 3 shows the results.

[0057]

[Table 3]

Example 4: Influence of L-ascorbic acid-2-phosphate sodium salt on discoloration of pigment resin color L-ascorbic acid-2-phosphate sodium salt was dissolved in water to prepare a 30% solution. . 10% and 20% of Oriogen Magenta R standard preparation manufactured by Toyo Ink Co., Ltd.
%added. After the sample was dyed on a cloth, heated and dried, a light resistance test was performed under the above-mentioned conditions for an exposure time of 72 hours. In addition, the non-addition section and the ascorbic acid addition section were also evaluated as a comparison section. Table 4 shows the results.

[0059]

[Table 4]

Example 5: Influence of β-cyclodextrin inclusion compound of L-ascorbic acid-2-phosphate magnesium salt on discoloration of pigment resin color 4 parts of β-cyclodextrin, L-ascorbic acid
After heating 12 parts of 2-phosphate magnesium salt, 8 parts of glycerin and 76 parts of purified water to 80 ° C., they were mixed and stirred. Use this clathrate compound with Oriogen Magent manufactured by Toyo Ink
10% and 20% were added to the aR standard preparation. After soaking the sample in the cloth, heating and drying, the exposure time was 7 under the above conditions.
A two-hour lightfastness test was performed. In addition, the non-addition section and the ascorbic acid addition section were also evaluated as a comparison section. Table 5 shows the results.

[0061]

[Table 5]

 ────────────────────────────────────────────────── ─── Continued from the front page (72) Inventor Shinobu Ito 1-13-9 Shibadaimon, Minato-ku, Tokyo Showa Denko KK F-term (reference) 4H025 AA63 AA64 AA82 AA83 AB01 AB02

Claims (24)

[Claims] 1. A compound of the formula (I) (Wherein R ¹ , R ² , R ³ and R ⁴ are each independently
A hydroxyl group, an ester group of the hydroxyl group and an inorganic acid or an organic acid, a glycoside group of the hydroxyl group and a sugar, a ketal group of the hydroxyl group and a ketone, or an acetal group of the hydroxyl group and an aldehyde. However, R ¹ and R ² do not simultaneously represent a hydroxyl group. A dye stabilizer comprising, as an active ingredient, a compound represented by the formula (1) or a salt thereof. 2. The compound of the formula (I) wherein R ¹ does not represent a hydroxyl group or a salt thereof as an active ingredient.
The dye stabilizer according to 1. 3. The compound of the formula (I) wherein R ² does not represent a hydroxyl group or a salt thereof as an active ingredient.
The dye stabilizer according to 1. 4. In the formula (I), R ¹ is a phosphoric acid ester, a sulfuric acid ester, an aliphatic carboxylic acid ester of a hydroxyl group,
The dye stabilizer according to claim 2, comprising a compound that is glucoside or a salt thereof or a salt thereof as an active ingredient. 5. In the above formula (I), R ² is a phosphoric acid ester of a hydroxyl group, a sulfuric acid ester, an aliphatic carboxylic acid ester,
The dye stabilizer according to claim 3, comprising a compound that is a glucoside or a salt thereof or a salt thereof as an active ingredient. 6. The dye according to claim 1, wherein in the formula (I), a compound in which R ¹ or R ² is an alkali metal salt of a phosphoric acid ester of a hydroxyl group or a salt thereof is contained as an active ingredient. Stabilizer. 7. The compound according to claim 1, wherein in the formula (I), R ¹ or R ² is an alkaline earth metal salt or a transition metal salt of a phosphate ester of a hydroxyl group or a salt thereof as an active ingredient. The dye stabilizer according to any one of the above. 8. Ascorbic acid-2-phosphate magnesium salt, ascorbic acid-2-phosphate sodium salt, ascorbic acid-2-phosphate zinc salt, ascorbic acid-2-phosphate calcium salt, ascorbin Acid-2-phosphate ester potassium salt,
Ascorbic acid-2-phosphate potassium calcium salt, ascorbic acid-2-phosphate magnesium potassium salt, ascorbic acid-2-phosphate aluminum salt, ascorbic acid-2-phosphate titanium salt, ascorbic acid-2 -Diphosphate sodium salt, ascorbic acid-2-triphosphate sodium salt, ascorbic acid-2-glucoside, ascorbic acid-2-phosphate-6-palmitate magnesium salt, ascorbic acid-2-phosphate- 6-
One or more selected from the group consisting of sodium palmitate, ascorbic acid-2-glucoside-6-palmitate, sodium magnesium ascorbic acid-2-phosphate and sodium sodium ascorbic acid-2-sulfate The dye stabilizer according to claim 1, which comprises a compound of the formula (1) as an active ingredient. 9. Ascorbic acid-3-phosphate magnesium salt, ascorbic acid-3-phosphate sodium salt, ascorbic acid-3-phosphate zinc salt, ascorbic acid-3-phosphate calcium salt, ascorbin Acid-3-phosphate potassium salt,
Ascorbic acid-3-phosphate potassium calcium salt, ascorbic acid-3-phosphate magnesium potassium salt, ascorbic acid-3-phosphate aluminum salt, ascorbic acid-3-phosphate titanium salt, ascorbic acid-3 -Diphosphate sodium salt, ascorbic acid-3-triphosphate sodium salt, ascorbic acid-3-glucoside, ascorbic acid-3-phosphate-6-palmitate magnesium salt, ascorbic acid-3-phosphate- 6-
One or more selected from the group consisting of palmitate sodium salt, ascorbic acid-3-glucoside-6-palmitate, ascorbic acid-3-phosphate sodium magnesium salt, and ascorbic acid-3-sulfate sodium salt The dye stabilizer according to claim 1, which comprises the compound of the formula (1) as an active ingredient. 10. The method according to claim 1, further comprising a molecular clathrate.
The dye stabilizer according to any one of the above. 11. The dye stabilizer according to claim 10, wherein the molecular clathrate is a cyclodextrin compound. 12. A compound of the formula (I) (Wherein R ¹ , R ² , R ³ and R ⁴ are each independently
A hydroxyl group, an ester group of the hydroxyl group and an inorganic acid or an organic acid, a glycoside group of the hydroxyl group and a sugar, a ketal group of the hydroxyl group and a ketone, or an acetal group of the hydroxyl group and an aldehyde. However, R ¹ and R ² do not simultaneously represent a hydroxyl group. A dye composition comprising a dye stabilizer containing a compound represented by the formula (1) or a salt thereof as an active ingredient and a dye. 13. A dye stabilizer comprising, as an active ingredient, a compound of the formula (I) wherein R ¹ is a phosphoric acid ester of a hydroxyl group, a sulfate ester, an aliphatic carboxylic acid ester, a glucoside or a salt thereof, or a salt thereof. The dye composition according to claim 12, comprising a dye. 14. A dye stabilizer comprising, as the active ingredient, a compound in which R ² in the formula (I) is a phosphoric acid ester of a hydroxyl group, a sulfuric acid ester, an aliphatic carboxylic acid ester, a glucoside or a salt thereof. The dye composition according to claim 12, comprising a dye. 15. The dye composition according to claim 12, further comprising a molecular clathrate. 16. The dye composition according to claim 15, wherein the molecular clathrate is a cyclodextrin compound. 17. The dye composition according to claim 12, wherein the dye is an organic dye. 18. A compound of the formula (I) (Wherein R ¹ , R ² , R ³ and R ⁴ are each independently
A hydroxyl group, an ester group of the hydroxyl group and an inorganic acid or an organic acid, a glycoside group of the hydroxyl group and a sugar, a ketal group of the hydroxyl group and a ketone, or an acetal group of the hydroxyl group and an aldehyde. However, R ¹ and R ² do not simultaneously represent a hydroxyl group. A) a coloring matter medium containing a coloring matter stabilizer containing a compound represented by the formula (1) or a salt thereof as an active ingredient. 19. A dye stabilizer comprising, as an active ingredient, a compound in which R ¹ in the formula (I) is a phosphate, a sulfate, an aliphatic carboxylate, a glucoside or a salt of a hydroxyl group, or a salt thereof. 19. The dye coloring medium according to claim 18, comprising: 20. A dye stabilizer comprising, as an active ingredient, a compound in which R ² is a phosphate, a sulfate, an aliphatic carboxylate, a glucoside or a salt thereof having a hydroxyl group in the formula (I). 19. The dye coloring medium according to claim 18, comprising: 21. The dye coloring medium according to claim 18, further comprising a molecular clathrate. 22. The dye coloring medium according to claim 21, wherein the molecular clathrate is a cyclodextrin compound. 23. A substrate comprising the dye composition according to claim 12. Description:
3. The dye coloring medium according to any one of 2. 24. The dye coloring medium according to claim 23, wherein the substrate is paper, wood, fiber, synthetic resin, glass, metal, ceramic, or a composite thereof.