JP2008260900A - Dye for inkjet recording, ink for inkjet recording using the same, and recording method using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a dye, an ink and a recording method that can inhibit the color change or discoloration of an image formed by inkjet recording, and thus can stably maintain the images. <P>SOLUTION: The dye for inkjet recording has a residual group of a stabilized ascorbic acid derivative, for example, represented by the structural formula of the figure. The ink for inkjet using the dye and a recording method using the ink are provided. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to an ink jet recording dye and the like, and more particularly to an ink jet recording ink that gives an image excellent in gas resistance and light resistance (hereinafter sometimes simply referred to as “ink”).

  The ink jet recording method records images, characters, and the like by causing ink droplets to fly according to various operating principles and attaching them to a recording medium such as paper. The recording method is easy to print at high speed and multicolor, and has a great flexibility in recording patterns. In addition, there is a feature that development and fixing are unnecessary, and in recent years, it has been rapidly spread in various applications including information equipment as a recording apparatus for various images. Furthermore, an image formed by the multicolor ink jet method can obtain an image superior to the multicolor printing by the plate making method or the color photographic method. For this reason, when the number of created copies is small, it is cheaper than ordinary multi-color printing and printing, and is therefore widely applied to the field of full-color image recording.

  In recent years, inkjet printers that can be printed easily have become widespread, and image quality surpassing silver salt prints has been obtained. However, water-based dyes tend to discolor or fade, have poor storage stability compared to silver salt photographs, and have a problem in maintaining the formed high-quality image quality for a long time. As a solution, various methods for preventing the deterioration of the dye have been proposed. For example, Patent Documents 1 to 4 disclose a method for preventing discoloration and fading by containing ascorbic acid or the like in an ink.

  Ascorbic acid or an inorganic salt thereof is relatively stable in a crystal dry state, but is colored and decomposes due to moisture absorption. Further, under neutral to alkaline conditions, oxidation by oxygen in the air is promoted, and it is easily decomposed. Furthermore, it is not stable against light and heat. Therefore, it is difficult to use the antioxidant action of ascorbic acid. As an improvement method, Patent Document 5 discloses a method of preventing discoloration and fading by using a stabilized ascorbic acid derivative as an additive. However, in the method using addition, the solubility differs between the coloring material and the antioxidant in the ink, and the distance between the coloring material and the antioxidant is separated on the recording medium. Depending on the properties of the recording medium, sufficient effect may be obtained. There was a problem that could not be obtained.

JP-A-2-228379 JP 7-331150 A Japanese Patent Laid-Open No. 9-95634 JP-A-9-302294 JP 2000-226543 A

  Accordingly, an object of the present invention is to provide a dye, an ink, and a recording method capable of preventing discoloration and fading of an image formed by ink jet recording and stably maintaining the image.

  In order to solve the problems associated with the prior art, the inventors of the present invention directly bind a stabilized ascorbic acid derivative to a dye used for ink jet recording, and use this as a coloring material in an ink. Has been found to be significantly improved.

  That is, the present invention provides a dye for inkjet recording having a residue of a stabilized ascorbic acid derivative, an ink containing the dye, and an inkjet recording method using the ink.

  By using the dye of the present invention, an ink and a recording method that give an image with improved weather resistance can be provided.

Hereinafter, the present invention will be described in more detail with reference to preferred embodiments of the present invention.
The dye of the present invention is characterized in that a stabilized ascorbic acid derivative is bound to a generally known dye.

  The stabilized ascorbic acid derivative used in the present invention has an ascorbic acid skeleton, and at least any hydroxyl group at the 2- or 3-position forms an ester with an inorganic acid or an organic acid or a glycoside with a sugar. Protected by The derivative is a stabilized ascorbic acid derivative that is not easily decomposed by light or heat. Such a stabilized ascorbic acid derivative becomes a free hydroxyl group at the 2nd or 3rd position in a required scene, and can exhibit ascorbic acid activity such as reducing property, antioxidant property, radical scavenging and the like.

  In the stabilized ascorbic acid derivative used in the present invention, at least one hydroxyl group at the 2-position or 3-position of ascorbic acid has an ester structure with an inorganic acid or an organic acid or a glycoside structure with a sugar. Here, examples of the inorganic acid include phosphoric acid (monophosphoric acid), pyrophosphoric acid, triphosphoric acid, polyphosphoric acid, derivatives of these phosphoric acids, sulfuric acid, and the like. Phosphoric acid, pyrophosphoric acid, and triphosphoric acid are preferable from the viewpoint of stability and the like, and phosphoric acid is more preferable. 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, Examples include unsaturated fatty acids. As the sugar, glucose is preferred.

  The stabilized ascorbic acid derivative is not particularly limited, such as D-form, L-form, DL-form, and racemate. Specific examples include the following, but are not limited to the following. Ascorbic acid-2-phosphate, Ascorbic acid-2-sodium phosphate, Ascorbic acid-2-potassium phosphate, Ascorbic acid-2-magnesium phosphate, Ascorbic acid-2-calcium phosphate, Ascorbic acid-2-phosphate zinc . Ascorbic acid-2-sodium pyrophosphate, ascorbic acid-2-triphosphoric acid, ascorbic acid-2-polyphosphoric acid, ascorbic acid-2-sulfuric acid, ascorbic acid-2-sodium sulfate, ascorbic acid-3-phosphate. Ascorbic acid-3-phosphate sodium, ascorbic acid-3-phosphate potassium, ascorbic acid-3-magnesium phosphate, ascorbic acid-3-sulfate, ascorbic acid-2-O-glucoside and the like.

  Preferably, from the viewpoint of compatibility with ink, etc., alkali metal salts of ascorbic acid-2-phosphate such as sodium ascorbate-2-phosphate and potassium ascorbate-2-phosphate, ascorbic acid-2-O-glucoside Ascorbic acid 2-position glycoside and the like. More preferred are sodium ascorbate-2-phosphate and potassium ascorbate-2-phosphate. The bond between the dye and the stabilized ascorbic acid derivative is made by forming an ester bond between the hydroxyl group at the 5th or 6th position of the stabilized ascorbic acid derivative and the carboxyl group or the sulfone group of the dye.

  Examples of the dye include azo dyes having at least one sulfone group or carboxyl group, phthalocyanine dyes, anthrapyridone dyes, anthraquinone dyes, and the like.

  Typical examples of the dye of the present invention are shown below as chemical formula (1), chemical formula (2), chemical formula (3) and chemical formula (4). These examples are merely illustrative and do not limit the invention.

(Wherein R ₁ represents a residue of the stabilized ascorbic acid derivative, R _{2 to} R ₅ represent a hydrogen atom, a sulfone group, a carboxyl group or a hydroxyl group, R ₆ represents a hydrogen atom or an alkyl group, R ₇ represents a hydrogen atom, A sulfone group, a carboxyl group or a hydroxyl group; R ₈ and R ₁₄ are —COO— groups or —SO ₃ — groups; R ₉ and R ₁₀ are halogen atoms; R ₁₁ is a hydrogen atom, sulfone group, carboxyl group or hydroxyl group; R ₁₂ and R ₁₃ represent an amino group or a nitro group.)

  The ink of the present invention comprises the dye of the present invention and a liquid medium. The addition amount of the dye in the ink of the present invention is determined by a desired color and color density, and is 0.1% by mass or more and 12% by mass or less with respect to the total amount of the ink of the present invention. More preferably, they are 0.5 mass% or more and 10 mass% or less, More preferably, they are 1 mass% or more and 8 mass% or less.

  Although the liquid medium which melt | dissolves or disperse | distributes the said dye is not specifically limited, The example is as follows. Water, alcohols (for example, methanol, ethanol, n-propyl alcohol, butanol, 1,2,6-hexanetriol, glycerin, etc.). Ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.). Ethers (diethyl ether, tetrahydrofuran, 1,4-dioxane and the like). Amides (N, N-dimethylformamide, N-methylformamide, N, N-dimethylacetamide, N-methylpropionamide, etc.). Pyrrolidinones (1-methyl-2-pyrrolidinone, 2-pyrrolidinone, etc.). Aromatic hydrocarbons (benzene, toluene, xylene, etc.). Aliphatic hydrocarbons (n-pentane, n-hexane, cyclohexane, etc.). Glycols (ethylene glycol, propylene glycol, butylene glycol, trimethylene glycol, diethylene glycol, etc.). Glycol ethers (2-methoxyethanol, 2-ethoxyethanol, diethylene glycol monomethyl ether, etc.) and the like. These compounds can be used individually or in combination of 2 or more types in arbitrary ratios. The amount of the liquid medium used is not particularly limited, but the total content in the ink is preferably 50% by mass or more and 98% by mass or less.

  When dispersing the ink, a dispersant (for example, sodium hexametaphosphate, condensed sodium naphthalene sulfonate, ionic surfactant, polymer substance, nonionic surfactant, etc.) is used as necessary. May be. When added, there is no particular limitation, but the addition amount is preferably in the range of 0.01% by mass to 10% by mass.

  In addition, antiseptic / antifungal agents, chelating agents, rust inhibitors, pH adjusters, antifoaming agents, viscosity modifiers, penetrants, nozzle drying inhibitors, etc. may be added as necessary. There is no limitation. The ink composition preferably has a pH in the range of 7-12.

  The ink of the present invention is suitably used for inkjet recording. For this reason, a suitable range for the physical properties of the ink of the present invention is a pH range of 3 to 12, more preferably 4 to 10 at around 25 ° C. The surface tension is preferably in the range of 10 to 60 mN / m (dyn / cm), more preferably 15 to 50 mN / m (dyn / cm). The viscosity is preferably in the range of 1 to 30 cps (mPa · s), more preferably 1 to 10 cps (mPa · s).

  The ink jet recording method of the present invention is characterized by using the ink of the present invention. The ink of the present invention is used in a bubble jet (registered trademark) recording head among ink jet recording methods, and is also effective as an ink storage container in which the ink is stored or as a filling ink. is there. The present invention provides excellent effects in a bubble jet (registered trademark) type recording head and recording apparatus.

  As for the typical configuration and principle, for example, those performed using the basic principle disclosed in US Pat. Nos. 4,723,129 and 4,740,796 are preferable. . This method can be applied to both a so-called on-demand type and a continuous type. In particular, in the case of the on-demand type, the electrothermal transducer disposed corresponding to the sheet or liquid path holding the ink is subjected to a rapid temperature rise corresponding to the recorded information and exceeding the nucleate boiling. By applying at least one drive signal, heat energy is generated in the electrothermal transducer and the film is boiled on the heat acting surface of the recording head, resulting in a one-to-one correspondence to this drive signal and bubbles in the ink. Is effective.

  By the growth and contraction of the bubbles, ink is ejected through the ejection openings to form at least one droplet. It is more preferable that the drive signal has a pulse shape, because the bubble growth and contraction is performed immediately and appropriately, and thus ink discharge with particularly excellent responsiveness can be achieved. As this pulse-shaped drive signal, those described in US Pat. Nos. 4,463,359 and 4,345,262 are suitable. Further excellent recording can be performed by employing the conditions described in US Pat. No. 4,313,124 of the invention relating to the temperature rise rate of the heat acting surface.

  As the configuration of the recording head, in addition to the combination configuration (linear liquid channel or right-angle liquid channel) of the discharge port, the liquid channel, and the electrothermal transducer as disclosed in each of the above-mentioned specifications, the heat acting part The present invention is also effective for configurations using US Pat. No. 4,558,333 and US Pat. No. 4,459,600, which disclose configurations in which the lens is disposed in a bending region. In addition, the present invention is also effective for a configuration (JP-A-59-123670, etc.) in which a common discharge port is used as a discharge portion of the electrothermal converter for a plurality of electrothermal converters. .

  Furthermore, as a full-line type recording head having a length corresponding to the width of the maximum recording medium that can be recorded by the recording apparatus, the length of the recording head is a combination of a plurality of recording heads as disclosed in the above specification. Any of a configuration satisfying the above and a configuration as a single recording head formed integrally may be used, but the present invention can exhibit the above-described effects more effectively.

  In addition, it is mounted on the main body of the device so that it can be electrically connected to the main body of the device and supplied with ink from the main body of the device. The present invention is also effective when a cartridge type recording head is used.

  In the present invention, it is preferable to add recovery means for the recording head, preliminary auxiliary means, etc. provided as the configuration of the recording apparatus to be applied, because the effects of the present invention can be further stabilized. . Specifically, the capping means, the cleaning means, the pressurizing or suction means for the recording head, the preheating means by the electrothermal converter or another heating element or a combination thereof, and the recording This is a preliminary discharge mode in which another discharge is performed.

  EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further more concretely, this invention is not limited to these. Unless otherwise specified, “parts” and “%” are based on mass, and “parts” and “%” are in terms of solid content. The “remainder” means a remainder obtained by subtracting each component from 100% as a whole.

<Example 1>
Evaluation was performed by printing with an ink produced using the dye of the present invention to which ascorbic acid-2-phosphate was bound. Preferable examples of the ink used in this embodiment include the following. That is, an ink can be obtained by mixing the following components containing a water-soluble dye and further pressure-filtering with a membrane filter having a pore size of 0.22 μm.
・ Water-soluble dye 1.5%
・ Thiodiglycol 10%
・ Product name: Acetylenol EH
(Kawaken Fine Chemical Co., Ltd.) 0.05%
・ Water balance

  Conjugation of the stabilized ascorbic acid derivative to the dye was carried out by a general esterification reaction. In particular, the sulfonic acid esterification was synthesized by the following method. However, it may be synthesized by other general methods.

1) Sulfonic acid esterification The dye is sulfonated with POCl ₃ . Next, 0.05 to 0.5 mol of ascorbic acid-2-phosphate is dissolved in a basic solvent, for example, 50 to 200 ml of pyridine, and cooled to 0 to 5 ° C. Next, a solution obtained by dissolving 0.05 to 0.5 mol of a sulfonic acid chloride dye in 50 to 500 ml of pyridine at 0 to 5 ° C. in a nitrogen atmosphere is added dropwise. Stirring is continued for ˜2 hours, and if necessary, stirring is continued at room temperature for 1 to 6 hours to complete the reaction. The reaction solution is poured into ice water, and the deposited precipitate is thoroughly washed with a weakly acidic aqueous solution having a pH of 4 to 6, and then recrystallized from an organic solvent such as ethanol as necessary, thereby stabilizing the ascorbic acid derivative 6. A dye having a hydroxyl group at the position and a sulfonate bond can be obtained.

The dyes used in this example are shown below.
[Azo dye]
Dye with ascorbic acid-2-phosphate bound to CIDirect Red 33

[Phthalocyanine dye]
Dye with ascorbic acid-2-phosphate bound to CIDirect Blue 199

[Anthrapyridone dye]
Dye with ascorbic acid-2-phosphate bound to CIAcid Red 80

[Anthraquinone dye]
Dye with ascorbic acid-2-phosphate bound to CIAcid Red91

  The ink having the above composition was mounted on an ink jet printer (PIXUS 850i, Canon Inc.), and printing was performed on professional photo paper PR101 (Canon Inc.).

<Other examples>
Although it is preferable to use a full multi-format ink jet recording apparatus in which ink jet nozzles are arranged and printed, this is not restrictive. The recording medium may be a material other than paper, such as a plate.

<Comparative Example 1>
The ink used in this comparative example will be described. Preferred examples of the ink used in this comparative example include the following. That is, an ink can be obtained by mixing the following components containing a water-soluble dye and further pressure-filtering with a membrane filter having a pore size of 0.22 μm.
・ Water-soluble dye 1.4%
・ Antioxidant 0.6%
・ Thiodiglycol 10%
・ Product name: Acetylenol EH
(Kawaken Fine Chemical Co., Ltd.) 0.05%
・ Water balance

The following commercially available dyes were used as water-soluble dyes.
・ Azo dyes: CIDirect Red33
-Phthalocyanine dye: CIDirect Blue 199
・ Anthrapyridone dye: CIAcid Red80
Anthraquinone dye: CIAcid Red91
Ascorbic acid-2-phosphate was used as an antioxidant.
The same ink jet printer and recording medium as those in the example were used.

<Example 2>
Evaluation was performed by printing with an ink prepared using a dye combined with ascorbic acid-2-sodium sulfate of the present invention. The same dye and ink composition as those used in Example 1 were used to bind ascorbic acid-2-sodium sulfate. The ink having the above composition was mounted on an ink jet printer (PIXUS 850i, Canon Inc.), and printing was performed on professional photo paper PR101 (Canon Inc.).

(Other forms)
It is preferable to use a full multi-format ink jet recording apparatus in which ink jet nozzles are arranged side by side, but this is not restrictive. The recording medium may be a material other than paper, such as a plate.

<Comparative example 2>
The same ink composition and dye as in Comparative Example 1 were used. Ascorbic acid-2-sodium sulfate was used as an antioxidant. The same ink jet printer and recording medium as those in the example were used.

<Example 3>
Evaluation was performed by printing with an ink prepared using a dye combined with ascorbic acid-2-(-4-) vinylbenzoic acid of the present invention. The same dye and ink composition as those used in Example 1 were used to bind ascorbic acid-2-(-4-) vinylbenzoic acid. The ink having the above composition was mounted on an ink jet printer (PIXUS 850i, Canon Inc.), and printing was performed on professional photo paper PR101 (Canon Inc.).

(Other forms)
Although it is preferable to use a full multi-format ink jet recording apparatus in which ink jet nozzles are arranged and printed, this is not restrictive. The recording medium may be a material other than paper, such as a plate.

<Comparative Example 3>
The same ink composition and dye as in Comparative Example 2 were used. Ascorbic acid-2-(-4-) vinylbenzoic acid was used as an antioxidant. The same ink jet printer and recording medium as those in Example 1 were used.

<Comparative Example 4>
The ink used in this comparative example will be described. Preferred examples of the ink used in this comparative example include the following. That is, an ink can be obtained by mixing the following components containing a water-soluble dye and further pressure-filtering with a membrane filter having a pore size of 0.22 μm.
・ Water-soluble dye 1.6%
・ Thiodiglycol 10%
・ Product name: Acetylenol EH
(Kawaken Fine Chemical Co., Ltd.) 0.05%
-Water remainder The same water-soluble dye as in Comparative Example 1 was used. The same ink jet printer and recording medium as in the example were used.

[Preparation of samples for weather resistance measurement]
The ink of the embodiment of the present invention obtained as described above, and the ink of the comparative example are O.D. D. The applied duty was adjusted so that the value was in the range of 0.9 to 1.1 to form a yellow single color patch (1.5 cm square).

<Ozone resistance evaluation>
The sample (yellow single color patch) was exposed to ozone for a predetermined time (6 hours, 12 hours) using an ozone weather meter OMS-H manufactured by Suga Test Instruments Co., Ltd. The temperature, humidity and ozone concentration at the time of exposure are 24 ° C., 60% and 2 ppm, respectively. After the exposure, each printed matter was evaluated by sensory evaluation based on the following criteria.
Evaluation A: Nine or more of 10 subjects are determined to have no change in concentration. Evaluation B: 7 or more of 10 subjects are determined to have no change in concentration. Evaluation C: 5 or more of 10 subjects are determined to have no change in concentration. Evaluation D : Nine or more of 10 subjects are judged to have a concentration change

<Light resistance evaluation>
The surface of the sample (yellow single color patch) was covered with a colorless glass plate, and then exposed to light for a predetermined time (6 hours, 12 hours) using a Xenon Weather Meter XL-75S type manufactured by Suga Test Instruments Co., Ltd. The temperature and humidity at the time of exposure are 24 ° C. and 60%, respectively. The irradiation condition is BPT (black panel temperature) 40 ° C .: illuminance of 34 W / m ² between 300 to 400 nm. After the exposure, each printed matter was evaluated by sensory evaluation based on the following criteria.
Evaluation A: Nine or more of 10 subjects are determined to have no change in concentration. Evaluation B: 7 or more of 10 subjects are determined to have no change in concentration. Evaluation C: 5 or more of 10 subjects are determined to have no change in concentration. Evaluation D : Nine or more of 10 subjects are judged to have a concentration change

  As shown in Table 1, as a result of recording according to the embodiment of the present invention, it was found that a printed matter having excellent ozone resistance and light resistance was obtained.

Claims (6)

  An ink jet recording dye having a residue of a stabilized ascorbic acid derivative.   The stabilized ascorbic acid derivative, wherein at least one hydroxyl group at the 2-position or the 3-position is a glycoside with an ester or a sugar with an inorganic acid or an organic acid, and either the 5-position or the 6-position hydroxyl group; The dye according to claim 1, which is bonded to the dye by an ester bond with a sulfone group or a carboxyl group of the dye.   The dye according to claim 1, wherein the dye is an azo dye having at least one sulfone group or carboxyl group, a phthalocyanine dye, an anthrapyridone dye, or an anthraquinone dye. The dye according to claim 1, which is represented by the following chemical formula (1), the following chemical formula (2), the following chemical formula (3), or the following chemical formula (4).

Wherein R ₁ is the residue of the stabilized ascorbic acid derivative, R _{2 to} R ₅ are hydrogen atoms, sulfone groups, carboxyl groups, hydroxyl groups or amino groups, R ₆ is a hydrogen atom or alkyl group, and R ₇ is A hydrogen atom, a sulfone group, a carboxyl group, a hydroxyl group or an alkyl group, R ₈ and R ₁₄ are —COO— groups or —SO ₃ — groups, R ₉ and R ₁₀ are halogen atoms, R ₁₁ is a hydrogen atom, sulfone A group, a carboxyl group or a hydroxyl group, R ₁₂ and R ₁₃ represent an amino group or a nitro group.)   An ink for ink-jet recording comprising the dye according to claim 1.   An ink jet recording method using the ink for ink jet recording according to claim 5.