JP3263524B2 - Polymer dye having xanthene skeleton and aqueous ink composition using the dye - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a polymer dye having a xanthene structural unit, which is useful as various inks for animal and vegetable fibers, ink jet recording, and the like.

[0002]

BACKGROUND ART Conventionally, as a polymeric dye, those having an azo dye derived from polyvinyl amine in the side chain are known (e.g. J.A.C.S. 98 .5996 P
[1976]). Japanese Patent Application Laid-Open No. Sho 63-30567 discloses a compound having an azo dye derived from polyallylamine in a side chain of the present applicant. However, although the water resistance of the dye is improved, it is further improved. A dye which has been used is desired. One use of dyes is in water-based inks. In addition to use in writing instruments and the like, in recent years, it has been expected to be used in high-performance color printers with the development of OA equipment and the like, and further in inkjet printers that are inexpensive and have improved image characteristics. In particular, in combination with the growing demand for plain paper, which was not good at the inkjet recording method, it can respond to plain paper, that is, color tone, storability, stability and light resistance even when used on plain paper. -There is a need for inks having excellent water resistance. Various water-soluble dyes are known as ink compositions, but in order to obtain a high color tone of magenta, they must be of a low molecular weight acidic dye type, and these have the presence of a sulfonic acid group or the like for dissolving in water. However, there is a disadvantage that the water resistance when printing on paper is poor. Also, JP-A-59-7
5964 and JP-A-57-70166 aim at improving the water resistance.

Embedded image It has been proposed that various types of bonding groups are bonded, but since these have some conjugation properties, the absorption spectrum tends to be broad and the color tone as magenta tends to be unclear. As an example, it is known that xanthene dyes generally have a high color tone and, when a phenyl group is attached to the nitrogen atom at the 3- or 6-position, have excellent light fastness (Japanese Patent Laid-Open No. 59-5978). 133273). But,
The water resistance is not satisfactory and some improvement is needed. In some cases, a bleeding inhibitor is added to the ink for the purpose of suppressing print bleeding that occurs during image formation. However, the aging stability of the ink is impaired by interaction with a dye or the like.

[0003]

An object of the present invention is to provide an aqueous ink composition which can be used for aqueous inks such as writing instruments and is particularly suitable for recording by an ink jet recording method.

[0004]

The present invention relates to a polymer dye having a xanthene structural unit represented by the following formula (1).

Embedded image The polymer dye having a xanthene-based chromophore represented by the above formula (1) of the present invention exhibits a high color magenta color when dissolved in water, and also has excellent light fastness. In particular, the dye has a higher solubility than conventional polymer dyes, so that it has excellent storage stability and can provide high reliability as an inkjet ink, and has a higher molecular weight than conventional acid dyes. Therefore, it was found that the image characteristics were excellent. In the polymer dye represented by the above formula (1), n
Is less than 20, it is difficult to obtain the expected effect of preventing bleeding. Conversely, if n is greater than 300, the solubility in water is poor.
The type of the substituent of the groups R ¹ , R ² , R ³ and R ^{4 in} the formula (1) is not particularly limited as long as the properties of the polymer dye of the present invention are not lost. For example, halogen such as chlorine, bromine, and fluorine can be used.

The dye of the present invention is obtained, for example, by the following production method. (I) Chlorsulfonation of xanthene dye 4.0 g of Acid Red 289 represented by the following formula (2)
Is dispersed in 50.0 g of thionyl chloride, and 2.0 ml of dimethylformamide is added with stirring. After stirring for 1 hour and pouring into ice, a brown precipitate represented by the following formula (3) is obtained. The reaction is represented by the following reaction formula (A).

Embedded image (Ii) Bonding with polyallylamine 0.12 g of polyallylamine represented by the following formula (4) is dissolved in 140 cc of water, and 70 ml of tetrahydrofuran is further dissolved.
1 and 0.8N aqueous sodium hydroxide solution to add
Adjust to 11. While stirring the above polyallylamine solution, 0.33 g of the product of the formula (3) is added, and 70 ml of tetrahydrofuran is added. After a certain period of time while maintaining the pH constant, the same amounts of the product of the formula (3) and tetrahydrofuran are added. The same treatment is performed once more, and after stirring for one hour, a product represented by the above formula (1) is obtained by filtration. The product is subjected to a conventional method such as acid precipitation and salting out to remove inorganic salts. The reaction is represented by the following reaction formula (B).

Embedded image (In the formula, X is the same as described above.) By changing the types of the xanthene dye and the polyallylamine that react in the above synthesis examples, various types of polymer dyes can be synthesized.

When an aqueous ink is prepared using the dye, the amount of the dye used is not particularly limited, but is generally 0.1 to 15 parts by weight based on the total weight of the ink.
The range of weight% is suitable, more preferably 0.1 to 10% by weight. When preparing an ink using the dye, the ink can be prepared using a known material. Such materials include humectants, pH adjusters, chelating agents, preservatives, fungicides, bactericides, buffers and the like. In the ink composition using the dye of the present invention, as a wetting agent, for example, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, glycerin, thioglycol, polyglycerin, hexa Specific examples include methylene diol, 1,5-pentanediol, 1,6-hexanediol, 2,5-hexanediol, and 2,4-hexanediol. In the present invention, it is preferable to use the above-mentioned polyhydric alcohol, but it is preferable to use a conventionally known wetting agent selected from the following compounds without mixing with the above-mentioned polyhydric alcohol or with the polyhydric alcohol. Can be. That is, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, tetraethylene glycol monomethyl ether, propylene glycol monomethyl ether, diethylene glycol monoethyl ether, triethylene glycol monoethyl ether Ethers of polyhydric alcohols such as tetraethylene glycol monoethyl ether and propylene glycol monoethyl ether; heterocyclic compounds such as N-methyl-2-pyrrolidone, 1,3-dimethylimidazolidinone, and ε-caprolactam; Alcohol amines such as ethanolamine, diethanolamine and triethanolamine Kind, and the like. The content of the above wetting agent is generally expressed as a percentage by weight based on the total weight of the ink.
Is preferably 1% to 40%, more preferably 3% to 30%.
% Range. The water content in the ink is 30
It is used in the range of ~ 95% by weight. As a pH adjuster,
Examples include lower alkanolamines such as diethanolamine and triethanolamine, alkali metal hydroxides such as lithium hydroxide and sodium hydroxide, alkali metal carbonates such as sodium carbonate, and ammonium hydroxide. As preservatives and fungicides, sodium pentachlorophenol, sodium dihydroacetate, 1,2-benzisothizarin-3-oneamine salt, 6-acetoxy-2,4-dimethyl-m-dioxane, 2- (4- Thiazolyl) -benzimidazole, 2-pyridinethiol-1-oxide zinc salt, 2-pyridinethiol-1-oxide sodium salt and the like. As chelating reagents, ethylenediaminetetraacetic acid sodium salt, nitrilotriacetic acid sodium salt,
Hydroxyethyl ethylenediamine triacetate sodium salt, diethylene triamine pentaacetate sodium salt, uramil diacetate sodium salt and the like. When an image is formed on a recording sheet using the ink, a surfactant may be added to improve the drying property. That is, an ionic (anionic or cationic), amphoteric, nonionic, or fluorine-based, silicon-based, or polymer-based surfactant can be added. For example, as an anionic surfactant,
Higher fatty acid salts, higher alkyl dicarboxylates, higher alcohol sulfates, higher alkyl sulfonates, condensates of higher fatty acids and amino acids, sulfosuccinates, naphthenates and the like. Examples of the cationic surfactant include an aliphatic amine salt, a quaternary ammonium salt, a sulfonium salt, and a phosphonium salt. Specific examples thereof include octadecylamine acetate, alkyltrimethylammonium chloride, polyoxyethylene octadecylamine, and polyoxyethylene. Alkylamines, high molecular amines, and the like. The amphoteric surfactant is a betaine type such as dimethylalkyl betaine. Further, as the nonionic surfactant, a fatty acid ester type of a polyoxyethylene compound, a polyethylene oxide condensation type, or the like can be used. In addition, various known materials other than those described above can be added, but the aqueous ink containing the polymer dye of the present invention does not require special addition of a bleeding inhibitor such as sodium alginate due to its characteristics. Further, the dye of the present invention,
It can be used by mixing with known acid dyes, direct dyes and the like. In this case, the polymer dye of the present invention has an effect as a bleeding inhibitor with respect to the mixed dye.

The following are specific examples of dyes. Acid dyes include C.I. I. Acid Yellow 17, C.I. I. Acid Yellow 23,
C. I. Acid Yellow 42, C.I. I. Acid
Yellow 44, C.I. I. Acid Yellow 79, C.I.
I. Acid Yellow 142, C.I. I. Acid Red 35, C.I. I. Acid Red 42, C.I. I. Acid Red 52, C.I. I. Acid Red 82,
C. I. Acid Red 87, C.I. I. Acid Red 92, C.I. I. Acid Red 134, C.I. I.
Acid Red 249, C.I. I. Acid Red 2
54, C.I. I. Acid Red 289, C.I. I. Acid Blue 1, C.I. I. Acid Blue 9, C.I.
I. Acid Blue 15, C.I. I. Acid Blue 59, C.I. I. Acid Blue 93, C.I. I. Acid Blue 249, C.I. I. Acid Black 2,
C. I. Food Black 2 and the like can be exemplified. Direct dyes include C.I. I. Direct Yellow 33, C.I.
I. Direct Yellow 44, C.I. I. direct·
Yellow 50, C.I. I. Direct Yellow 86,
C. I. Direct Yellow 144, C.I. I. Direct Orange 26, C.I. I. Direct orange 1
02, C.I. I. Direct Red 4, C.I. I. Direct Red 95, C.I. I. Direct Red 24
2, C.I. I. Direct Red 9, C.I. I. Direct Red 17, C.I. I. Direct Red 28,
C. I. Direct Red 81, C.I. I. Direct Red 83, C.I. I. Direct Red 89, C.I.
I. Direct Red 225, C.I. I. direct·
Red 227, C.I. I. Direct Blue 15, C.I.
I. Direct Blue 76, C.I. I. Direct Blue 86, C.I. I. Direct Blue 200, C.I.
I. Direct Blue 201, C.I. I. direct·
Blue 202, C.I. I. Direct Black 22,
C. I. Direct Black 32, C.I. I. Direct Black 51, C.I. I. Direct Black 15
4 and the like. The dyes that can be used in the method of the present invention are not limited to those described in the above Color Index.

[0008]

Next, an example of producing an ink using the dye of the present invention will be described. All parts are parts by weight. Example 1 C.I. I. Acid Red 289 and X in equation (4)
= -CH ₂ - polyallylamine (n = 80, Nitto Boseki Ltd., PAA · HCl-3S) based on from the above manufacturing method, after synthesizing the polymeric dye A, were prepared ink by the following composition. Dye A of the present invention 4 parts Diethylene glycol 22.5 parts Glycerin 7.5 parts Preservative and fungicide (trade name: Deltop, manufactured by Takeda Pharmaceutical Co., Ltd.) 0.3 parts Water 65.7 parts And filtered with a 0.2 μm filter to obtain an ink.

Embodiment 2 C.I. I. Acid Violet 9 and X in Formula (4) are-
Dye B of the present invention was produced in the same manner as in Example 1 from that of CH ₂ —CO— (n = 30). Inventive dye B 3 parts Triethylene glycol 10 parts Ethylene glycol 20 parts Antiseptic / fungicide (sodium omazine) 0.3 parts Water 66.7 parts The above composition was adjusted to pH 10 with sodium hydroxide, and 0.2 μm The ink was filtered through a filter.

Example 3 In Example 1, Dye A and C.I. I. Using Direct Blue 86, an ink was prepared with the following composition. Inventive dye A 2.5 parts C.I. I. Direct Blue 86 1.5 parts Diethylene glycol 22.5 parts Glycerin 7.5 parts Antiseptic / antifungal agent 0.3 parts (trade name: Deltop, manufactured by Takeda Pharmaceutical Co.) Water 65.7 parts

Comparative Example 1 In Example 1, C.I. I. An ink composition was prepared in the same manner except that Acid Red 289 was used.

Comparative Example 2 In Example 2, C.I. I. An ink composition was prepared in the same manner except that Acid Violet 9 was used.

Using the inks of the above Examples and Comparative Examples, images formed by a piezo-type ink jet recording apparatus were tested for water resistance, light resistance, and image bleeding. Table 1 shows the results. In Table 1, the waterfastness is represented by a main color density fading rate (%) after immersing the image sample in water at 30 ° C. for 1 minute, and the lightfastness is a main color density after irradiating the image sample with a fade meter for 3 hours. It is represented by the fading rate (%).

[0014]

[Table 1] Note: Image bleeding ◎ No image bleeding ○ Some image bleeding △ Image bleeding × Many image bleeding

[0015]

【effect】

(1) Since the dye of the present invention having a xanthene structural unit is excellent in water solubility, it can be dyed on cotton or animal and plant fibers like conventional direct dyes and acid dyes.
Further, since it is a polymer, it has good water resistance and the like, and is also excellent in safety. (2) Since the dye is excellent in water solubility, it is suitable without clogging when used as an aqueous ink for a writing instrument or the like. (3) When the dye is prepared as an ink for ink jet recording, while maintaining the high color tone of the xanthene dye,
It is possible to improve the water resistance on a recording sheet including plain paper, and suppress the occurrence of bleeding during image formation. Also, known materials can be added for various purposes. In particular, when mixed with a known direct dye or acid dye, the polymer dye provided by the present invention has an effect of preventing bleeding with respect to other dyes, so that an image excellent in both color tone and image quality can be obtained.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-63-30567 (JP, A) JP-A-5-194476 (JP, A) JP-A-5-2955312 (JP, A) JP-A-60-1985 190478 (JP, A) JP 438956 (JP, B1) (58) Fields investigated (Int. Cl. ⁷ , DB name) C09B 69/10 C09D 11/00 CA (STN) REGISTRY (STN)

Claims (4)

(57) [Claims] 1. A polymer dye having a xanthene structural unit represented by the following formula (1). Embedded image 2. An aqueous ink composition comprising the polymer dye according to claim 1. 3. The aqueous ink composition according to claim 2, which is used for recording by an ink jet recording method. 4. The aqueous ink composition according to claim 2, wherein the aqueous ink composition contains a polymer dye having a xanthene structural unit represented by the formula (1) and a mixture of other dyes. .