JP2000297236A - Ink using disperse dye - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject ink for ink jet printing excellent in dispersion stability and color developability/dyeability, having good long-term preservability and environmental stability, and causing no clogging in a filter or nozzle during continuous issue thereof by binding a disperse dye to a specific block copolymer with a specific bond. SOLUTION: This ink is obtained by binding (A) a disperse dye such as C.I. Disperse Red 53 to (B) a block copolymer having hydrophilic segment and hydrophobic segment and preferably represented by e.g. the formula (D is a disperse dye residue; X is a bond cleavable with heat, or the like; R1 and R2 are each H or a 1-3C alkyl; (m) is 2-6; (p) is 1-5; (n) and (q) are each 0-100; Y is H, a 1-10C alkyl, a 6-18C allyl, or the like) with a bond cleavable with the action of heat, acid or alkali. The component A prior to binding the component B has a mean particle diameter of preferably <=0.35 μm and a maximum particle diameter of preferably <=0.7 μm.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an ink containing a disperse dye (hereinafter, simply referred to as "disperse dye ink"), which is mainly used for printing a fabric by an ink jet printer system.

[0002]

2. Description of the Related Art Conventional printing is mainly lithographic or cylindrical screen printing. In such screen printing, first, a printing plate such as a copper plate or a screen plate for printing is manufactured, and then the printing is performed. Book production using a plate, that is, printing and dyeing are performed. Usually, the production of the template requires a lot of time, labor, money, and the like, and it takes about one to four months from the receipt of an order to the production of the template and the start of actual production. Therefore, in production by screen printing, the cost is not paid unless there is an order of a certain amount or more, which is not suitable for small-scale production.

[0003] On the other hand, in the garment industry, how quickly designs that anticipate fashion can be put on the market is a very important factor in maintaining competitiveness in the industry.
Especially for the dyeing and apparel industries,
So-called small-lot / multi-product production, such as rapid sample making in anticipation of fashion trends in wear, and production of many varieties in small quantities at the beginning of the season and increasing production at appropriate rates according to the subsequent sales of each product. In recent years, there has been a strong demand for measures to address this. In order to respond to the demands of these industries, a number of plateless printing techniques such as ink-jet printing, thermal transfer printing, electrostatic printing, electrophotographic printing, and magnetic printing are provided as printing techniques that replace the screen printing described above. . Above all, inkjet printing is the most efficient and economical printing technology in that dyes can be supplied directly to fabric without the need for intermediate toner or ink transfer. In addition, it is relatively easy to change designs such as patterns and color schemes, and if this ink jet printing is employed, it is possible to quickly and accurately respond to user requests.

There are two types of the ink jet printing, a thermal system in which ink is ejected by foaming based on rapid overheating of a heater corresponding to an output signal, and a piezo system in which ink is ejected by vibration of a piezo element. In either case, the ink is still discharged through the fine flow path inside the nozzle, and the inside of the nozzle is in a state where clogging is likely to occur.

[0005]

In general, when printing a highly hydrophobic fabric such as polyester, a disperse dye having a similar hydrophobicity is used. The disperse dye,
The disperse dye ink obtained by dispersing this disperse dye in water has a poor hydrophobic stability as it has a high hydrophobicity with a solubility in water of about 0.1 g / l (liter). The inside of the nozzle is easily clogged.

Therefore, when the disperse dye is used for ink-jet printing, the dispersion of the disperse dye particles is usually stabilized by the following steps.

That is, first, a suitable wetting agent is added to the secondary aggregate of the disperse dye to improve the wettability with water, and a mechanical impact force and a shear force are applied thereto to make the disperse dye into fine particles. I do. Next, in order to prevent the re-aggregation of the finely dispersed disperse dye particles, the surface energy gap between the particles and water is obtained by adsorbing a dispersant such as a polymer activator on the surface of each particle to make the particles hydrophilic. To stabilize the dispersion state.

[0008] In order to maintain the dispersion state stabilized as described above for a long period of time, it is important to prevent the polymer activator and the like from falling off from the dispersed dye particles. In particular, ink-jet printers usually have a temperature of around 10
It is used at ４０40 ° C., but -20 in consideration of transportation etc.
It is required that the dispersibility be maintained in a temperature range of up to 70 ° C.

However, the above-mentioned activator having a strong wetting action generally has a high hydrophilicity and has a poor affinity for a disperse dye, so that it is easily desorbed when the temperature exceeds about 60 ° C. The disperse dye particles from which the activator has been removed are promoted for re-aggregation, particularly in a high-temperature environment, the solubility of the dye is increased, the bonding between the particles is further promoted, and the dispersibility is caused by the sedimentation of the particles. Declines rapidly.

Many attempts have been made to solve the problem of maintaining the above-mentioned dispersion state, and as a dispersant having improved affinity with a disperse dye, for example, Japanese Unexamined Patent Publication No.
No. 0-133076, JP-A-60-229969, JP-A-61-215783, JP-A-61-241371.
JP-A-61-247762, JP-A-62-101
No. 73, JP-A-62-1780, JP-A-62-12
1776, JP-A-63-15944, JP-A-61-1
No. 31,469, JP-A-61-213273 and JP-A-4-59282 disclose disperse dye inks using a nonionic dispersant obtained by adding ethylene oxide to a styrenated phenol or an anionic dispersant obtained by sulfonating the same. It has been disclosed. However, since the nonionic dispersant does not impart a charge to the surface of the nonionic dispersant after being adsorbed on the disperse dye particles, good dispersion performance based on electrostatic repulsion cannot be expected. Further, the polyethylene oxide segment in the nonionic dispersant forms a complex with the disperse dye and dissolves the disperse dye. Accordingly, these dispersants can be suitably used in conventional screen printing, but as a dispersant for a disperse dye ink for inkjet printing, the dispersant has high solubility as described above, and thus is preferable in terms of storage stability. Absent.

Further, JP-A-6-41878 and JP-A-61-148275 disclose disperse dye inks using a formalin condensate of naphthalenesulfonic acid as a dispersant. However, since this dispersant does not have a functional group capable of hydrogen bonding with the functional group of the disperse dye, it is detached from the surface of the disperse dye particles at a high temperature of 60 ° C. or higher,
Settling of the disperse dye occurs.

In addition, JP-A-8-143802, JP-A-8-143803, and JP-A-8-143804 disclose a copolymer of styrene-acrylic acid-methyl methacrylate as a dispersant, and ethylene oxide and A disperse dye ink suitable for thermal ink jet printing using a copolymer type nonionic activator of propylene oxide is disclosed. However, these have poor high-temperature stability because they do not have a hydrogen-bondable functional group similarly to the above-mentioned dispersants, and the nonionic activator of the copolymer type of ethylene oxide and propylene oxide is complexed with a disperse dye. Is formed, which dissolves the disperse dye, which is not preferable in terms of storage stability.

JP-A-8-176482 discloses a disperse dye ink in which a disperse dye dissolved in a water-soluble high-boiling solvent is reprecipitated and dispersed. This is because the balance between the solubility of the disperse dye and the precipitability greatly affects the dispersibility. As a result, the dispersion of the quality becomes large, and it cannot be said that this is a practical method.

JP-A-8-67848 discloses styrene-
Although a method of dispersing a disperse dye using a maleic anhydride copolymer has been disclosed, the styrene-maleic anhydride copolymer has a low affinity for the disperse dye and is required to achieve long-term storage stability. Does not reach.

In Japanese Patent Application Laid-Open No. H10-330661, a dispersant having a hydrophobic moiety similar in structure to a disperse dye is selected to increase the adsorptive power, and the hydrophobic moiety is bonded to a functional group of the disperse dye by a hydrogen bond or the like. It has long-lasting stability under extreme environmental conditions such as high and low temperatures by having a functional group with strong interaction, and more efficient by using a polymer activator with a long molecular chain length. After covering the surface of the dye particles, specifically, using an anionic oligomer dispersant having a functional group capable of hydrogen bonding with the functional group of the disperse dye, the water-soluble high-boiling organic solvent used in combination is The tension is 46 dyne / cm or more, the ratio of inorganic / organic is 2 to 6, and the viscosity at 25 ° C. is 10 cps.
The following disperse dye inks are disclosed. Although this disperse dye ink is certainly improved as compared with the case where a large number of dispersants are used, although the functional groups of the disperse dye and the dispersant are bonded, they are hydrogen-bonded. Also, long-term storage stability cannot be maintained because the resin is desorbed from the dispersant due to temperature changes at high and low temperatures.

The present invention has been made in view of the above situation, has excellent dispersion stability, good long-term storage stability and environmental stability, and has no clogging of filters and nozzles during continuous discharge, and has a high color development. -It is intended to provide a disperse dye ink having excellent dyeing properties for inkjet printing.

[0017]

Means for Solving the Problems The inventors of the present invention have made intensive studies to solve the above-mentioned problems, and as a result, have constructed the following disperse dye ink.

That is, the present invention provides a disperse dye ink characterized in that a block copolymer having both a hydrophilic segment and a hydrophobic segment is bonded to a disperse dye by a bond cleavable by heat, acid or alkali. provide.

Here, the block copolymer is preferably one having the following general formula (1).

[0020]

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In the formula (1), D is a disperse dye residue, X is a bond cleavable by heat or acid or alkali, for example,
-N = C-, -N = N-, -OC (= O)-, -NHC (= O)-, -OC (= O) O-
Or -NHC (= O) O-, R ¹ and R ² are a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, m is an integer of 2 to 6, and p is 1
N is an integer of 0 or 1 to 100, Y is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an allyl group having 6 to 18 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms. And particularly preferably q is zero. ]

Also, the block copolymer is preferably one having the following general formula (2).

[0023]

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[In the formula (2), D is a disperse dye residue, and X is-
OH, an alkoxy group having 1 to 10 carbon atoms, 6 to 18 carbon atoms
Aryloxy group or aralkoxy group having 7 to 20 carbon atoms
And R ¹And R^TwoIs a hydrogen atom or an alkyl having 1 to 3 carbon atoms
M is an integer of 2 to 6, p is an integer of 1 to 5, n
And q are 0 or an integer of 1 to 100, Y is nothing and D
Directly connected or -CH_TwoCH (OH) CH_Two-, -NH-, -NHNH- or
Represents -NHCO-, respectively. ]

Further, it is preferable that the average particle size of the disperse dye particles before binding of the block polymer is 0.35 μm or less, and the maximum particle size is 0.7 μm or less.

It is preferable that a compound that generates an acid or an alkali by the action of heat is blended in the ink.

Hereinafter, the present invention will be described in more detail.

Generally, in order to improve the dispersibility of the disperse dye and prevent clogging of the nozzle head in the ink jet printer, it is necessary to make the dye particles as fine as possible. However, as the particle size of the dye particles progresses, the surface area of the dye particles increases and the dye particles are activated, so that the ratio of reaggregation and dissolution increases, and the particle size easily increases due to environmental changes during storage, and conversely. Settling easily.

The disperse dye ink of the present invention has a block copolymer having a hydrophilic segment and a hydrophobic segment represented by the general formula (1) or (2) on the surface of the disperse dye (hereinafter, simply referred to as "block copolymer"). By grafting (1), re-aggregation and dissolution due to the disperse dye becoming fine particles can be prevented, and it is possible to sufficiently cope with environmental changes during storage.

Since the bond between the block copolymer and the functional group on the surface of the dye particle is a bond that is cleaved by the action of heat or an acid or alkali, the bond is thermally cleaved in the heat treatment step at the time of dyeing. If a compound capable of generating / regenerating an acid or an alkali by heat is added to the ink in advance, the bond is cleaved by the acid or the alkali to regenerate the disperse dye in the same manner. I do. Therefore, the disperse dye ink of the present invention exhibits not only excellent dispersion stability and storage stability, but also excellent dyeing properties and coloring properties.

The disperse dye ink of the present invention has a reactive terminal represented by the general formula (3) or (4) at the time when the disperse dye particles reach a desired particle size when the particles are reduced to fine particles. The disperse dye is semi-permanently dispersed irrespective of an environmental change or a storage period by adding a block copolymer having the compound and grafting the block copolymer to the particle surface and covalently bonding the block copolymer to the particle surface.

[0032]

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In the formula (3), Z is -NR ³ R ^4, wherein R ³ and R ⁴ are a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a trialkylsilyl group such as a trimethylsilyl group, or a phthalimide group. Represents ｝, -CHO, -COOH, -SH, -NHC
(= O) ONa or —OR ⁵ ｛where R ⁵ represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an allyl group having 6 to 18 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms. Ｒ, R ¹ and R ² represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms,
m is an integer of 2 to 6, p is an integer of 1 to 5, n and q are 0 or an integer of 1 to 100, Y is a hydrogen atom, and the number of carbon atoms is 1.
Represents an alkyl group having 10 to 10 carbon atoms, an allyl group having 6 to 18 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms. ]

[0034]

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In the formula (4), A represents —OH, —ONa, an alkyl group having 1 to 10 carbon atoms, an allyloxy group having 6 to 18 carbon atoms or an aralkoxy group having 7 to 20 carbon atoms, R ¹ and R ^Two
Is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and m is 2
An integer of 1 to 6, p is an integer of 1 to 5, n and q are 0 or an integer of 1 to 100, B is -OH,

[0036]

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Represents an allyl group having 6 to 18 carbon atoms or an aralkyl group having 7 to 20 carbon atoms. ]

The conditions for grafting the block copolymer onto the dye surface differ depending on the type of the terminal functional group.
The block copolymer having the structure represented by the general formula (3) and Z is an aldehyde group is referred to as “The Reactive Polymeric Microcel”.
le Based on An Aldehyde-Ended Poly (ethylne glycol)
/ Poly (lactide) Block Copoltmer "K.Kataoka et al.M
acromolecules 31,1473,1998.

In the structure represented by the general formula (3), Z
In the case where a block copolymer having an aldehyde group at the end is used, 0.01 to 200% by weight based on all disperse dye particles,
Preferably, 0.5 to 100% by weight of a block copolymer is added and reacted. The reaction of the disperse dye with a hydroxyl group or an amino group is carried out by adjusting the pH of the dispersion to 1 to 6 or 8 to 12, preferably 2 to 5 or 9 to 11, and the reaction temperature to 0 to 100.
° C, preferably 10 to 60 ° C, and a reaction time of 0.1 to
The time is set to 10 hours, preferably 0.5 to 5 hours. The bond between the disperse dye reacted and grafted under the above conditions and the block copolymer is an acetal or Schiff base bond. These bonds are stable under storage conditions of −20 to 70 ° C., but are cleaved by acid or alkali or the heat treatment at the time of dyeing to regenerate the disperse dye.

In the structure represented by the general formula (3),
As an example of a method for synthesizing a block copolymer having an amino group at the terminal, for example, after adding ε-caprolactam or lactide to an ethylene oxide adduct of potassium (trimethylsilyl) amide shown in Japanese Patent No. 2593032, the trimethylsilyl group is deprotected. Obtained. The reaction between the hydroxyl group or amino group of the disperse dye and the block copolymer having an amino group at the Z-terminus is bonded using a dialdehyde such as glutaraldehyde. The amount of the block copolymer to be added is the same as in the case of the aldehyde terminal, and the amount of the dialdehyde is 2/1 to 1/10, preferably 1/1 to 1/5, based on the number of moles of the block copolymer added. The reaction conditions for the disperse dye may be in accordance with the reaction conditions for the block copolymer having an aldehyde at the Z-terminal. The bond that occurs in this case is an acetal or a Schiff-base bond, as before.

In the structure represented by the general formula (3), Z
In the case of using a block copolymer having a mercapto group at the terminal, the condition may be such that the amino group of the general formula (3) is reacted with the amino group of the disperse dye described above. Usually, the hemiacetal formed by adding a mercapto group to an aldehyde group is very stable. In this reaction, the addition ratio of the block copolymer to the dye and the addition ratio of the dialdehyde to the block copolymer are the same as described above.

Next, in the structure represented by the general formula (4),

[0043]

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The block copolymer can be obtained by reacting epichlorohydrin with a block copolymer having a -ONa B-terminal. In the reaction between the block copolymer and the disperse dye, the pH, temperature, time, and the molar ratio of the disperse dye to the disperse dye are determined in accordance with the above-described case where the Z-terminal is an aldehyde.

In the structure represented by the general formula (4), B
When using a block copolymer having an -OH terminal, 1-ethyl-3- (3-dimethylaminopropyl)
It is also possible to use a water-soluble carbodiimide such as carbodiimide to react with an amino group of a disperse dye and draw a graph by an amide bond.

When the present block copolymer is grafted on the surface of the disperse dye particles, the particle size of the dye particles greatly affects the graft efficiency of the block copolymer to the dye particles and the dispersion stability after grafting.

The average particle size of the disperse dye suitable for grafting the block copolymer is 0.7 μm or less, preferably
It is 0.05 to 0.5 μm. The clogging of the nozzle or the filter has a great influence not only on the average particle but also on the maximum particle diameter. The maximum particle size is 0.8 μm or less, preferably,
0.6 μm. These maximum particle diameters can be controlled by selecting a pulverizing time and a filter.

The reaction between the block copolymer and the disperse dye is carried out at a temperature, except that the reaction is carried out at a pH of 8 to 11.
The time and the molar ratio to be added to the disperse dye are determined in accordance with the case where the Z-terminal is aldehyde.

Using a method as described above, a dispersion obtained by grafting a block copolymer onto disperse dye particles to improve dispersibility is added with an alcohol such as ethylene glycol, diethylene glycol, triethylene glycol, or glycerin in an amount of 1 to 3%. 45% by weight, preferably 5 to 40% by weight
It may be added.

Also, if necessary, other existing dispersants,
For example, a nonionic dispersant such as an ethylene oxide / propylene oxide copolymer, or an anionic dispersant such as a formalin condensate of ligninsulfonic acid and phenolsulfonic acid may be added. The amount of these dispersants added is
0.1 to 50% by weight, preferably 1 to 20% by weight, and a molecular weight of 200 to 20,000, preferably 100
0 to 10,000.

Hydrotropes such as urea, thiourea, buret, semicarbazide, dimethylol urea and the like may be added, and the amount of addition is 0.5 to 10% by weight, preferably 1 to 5% by weight.

A wetting agent such as sodium dodecylbenzenesulfonate, sodium 2-ethylhexylsulfosuccinate, sodium alkylnaphthalenesulfonate and ethylene oxide adduct of nonylphenol may be used in combination. About 2.0% by weight is preferable.

Compounds that generate an acid or an alkali by heat treatment include onium salts such as phosphonium salts, ammonium salts, sulfonium salts and oxonium salts, and onium complexes, and organic carboxylic acids such as ammonium acetate, trimethylamine acetate and ammonium formate. Amine salts of acids and Schiff base compounds,
The addition amount is 0.1 to 50.0% by weight based on the dye,
Preferably, it is 0.5 to 30.0% by weight.

As the disperse dye for grafting the block copolymer, any conventionally known disperse dye can be used. For example, CI Disperse Yellow 3, 4, 5, 7, 9, 13,
24, 30, 33, 34, 42, 44, 49, 50, 5
1, 54, 56, 58, 60, 63, 64, 66, 6
8, 71, 74, 76, 79, 82, 83, 85, 8
6, 88, 90, 91, 93, 98, 99, 100, 1
04, 114, 116, 118, 119, 124, 12
6, 135, 140, 141, 149, 160, 16
2,163,164,165,179,180,18
2,183,186,192,198,199,20
2, 204, 210, 211, 215, 216, 21
8, 224; CI Disperse Orange 1, 3, 5, 7, 1
1, 13, 17, 20, 21, 25, 29, 30, 3
1, 32, 33, 37, 38, 4, 43, 44, 45,
47, 48, 49, 50, 53, 54, 55, 56, 5
7, 58, 59, 61, 66, 67, 71, 73, 7
6, 78, 80, 89, 90, 91, 93, 96, 9
7, 119, 127, 130, 139, 142; CIDi
sperse Red 1,4,7,11,12,13,15,1
7, 27, 43, 44, 50, 52, 53, 54, 5
5, 56, 58, 59, 60, 65, 72, 73, 7
4, 75, 76, 78, 81, 82, 86, 88, 9
0, 91, 92, 93, 96, 103, 105, 10
6, 107, 108, 110, 111, 113, 11
7, 118, 121, 122, 126, 127, 12
8, 131, 132, 134, 135, 137, 14
3, 145, 146, 151, 152, 153, 15
4, 157, 159, 164, 167, 169, 17
7, 179, 181, 183, 184, 185, 18
8, 189, 190, 191, 192, 200, 20
1, 202, 203, 295, 206, 207, 21
0, 221, 224, 225, 227, 229, 23
9, 240, 257, 258, 277, 278, 27
9, 281, 288, 298, 302, 303, 31
0, 311, 312, 320, 324, 328; CIDi
sperse Violet 1, 4, 8, 23, 26, 27, 28,
31, 33, 35, 36, 38, 40, 43, 46, 4
8, 50, 51, 52, 56, 57, 59, 61, 6
3, 69, 77; CIDisperse Green 9; CIDisper
se Brown 1, 2, 4, 9, 13, 19; CI Disperse
Blue 3, 7, 9, 14, 16, 19, 20, 26, 2
7, 35, 43, 44, 54, 55, 56, 58, 6
0, 62, 64, 71, 72, 73, 75, 79, 8
1, 82, 83, 87, 91, 93, 94, 95, 9
6, 102, 106, 108, 112, 113, 11
5, 118, 120, 122, 125, 128, 13
0, 130, 141, 142, 143, 146, 14
8, 149, 153, 154, 158, 165, 16
7, 171, 173, 174, 176, 181, 18
3, 185, 186, 187, 189, 197, 19
8, 200, 201, 205, 207, 211, 21
4, 224, 225, 257, 259, 211, 21
4, 224, 225, 257, 259, 267, 26
8, 270, 284, 285, 287, 288, 29
1, 293, 295, 297, 301, 315, 33
0, 333; CI Disperse Black 1, 3, 10, 2
4; and the like.

[0055]

Next, the present invention will be described in detail with reference to examples, but embodiments of the present invention are not limited thereto. In the following examples, “parts” means parts by weight.

(Example 1)

[0057]

[Table 1]

The above mixture was mixed with the system zeta LMZ1.
Type 0 (made by Ashizawa) 0.3 mm in diameter (filling ratio 80%)
Using a ceramic bead, pulverization was performed continuously for 2 hours at a processing flow rate of 101 / min and a pin tip speed of 7 m / sec. At this point, it was confirmed that the dye particle diameter in the dispersion was 1 μm or less (Shimadzu) Laser diffraction particle size distribution analyzer SAL
D2100), and in the following general formula (3),
Z is an aldehyde group, Y is -Na, R ¹ is a hydrogen atom, R ² is a methyl group, m is 2, p is 1, n and q are average values of block copolymers of 4.2 and 3.7, respectively. 5 parts of block copolymer A) was added, and acetic acid was added to adjust the pH of the dispersion to 3.

[0059]

Embedded image

The liquid temperature was adjusted to 50 ° C., and the other conditions were kept as it was, and the mixture was further pulverized for 2 hours to continue the graft reaction of the block copolymer on the particle surface. After the completion of the reaction, the dispersion was cooled to room temperature, and the pH was adjusted to 7 by adding triethanolamine.

This dispersion is diluted with a mixed solvent of water / glycerin at a weight ratio of 2/1 so that the dye concentration becomes 5%, adjusted, and then filtered using a 1 μm filter. To prepare an ink.

The ink was degassed by performing vacuum (15 mmHg) ultrasonic degassing at 50 ° C. for 1 hour, and then discharged using a Kaleida 36PR (piezo method) ink jet printer manufactured by Fuji Film Co., Ltd.

200 million dots were continuously discharged from 13 nozzles having an inner diameter of 50 μm and having a substantially semicircular shape, and the discharge amount was accurately weighed.

Further, the ink was stored in a thermostat at 60 ° C. for 2 weeks, and the particle size of the dye particles dispersed in the ink before and after storage was measured, and the high-temperature dispersion stability of the ink was examined.

After printing, heat treatment was performed at 170 ° C. for 3 minutes to develop color. After washing and drying, it was immersed in dimethylformamide / trichloroethylene (mixed solvent in a 1/1 volume ratio) at 50 ° C. overnight to extract the dyed dye, and its concentration was measured by a spectrophotometer. The results are shown in Table 9.

Except not using the block copolymer A,
The dye concentration was compared with the dye concentration extracted from the printed matter performed in the same manner as in Example 1.

Example 2 After dispersing a dye with the same composition as in Example 1, 10 parts of block copolymer A was added, and the reaction, adjustment and measurement were performed in the same manner as in Example 1. . The results are also shown in Table 9.

(Embodiment 3)

[0069]

[Table 2]

The mixture shown in Table 2 was dispersed in the same manner as in Example 1 and, after reaching a predetermined particle size, in the above formula (3), Z was an amino group, Y was -Na, R ¹ Is a hydrogen atom, R ² is a methyl group, m is 2, p is 1, n and q each have an average value of 11 and 5.5, respectively, and 10 parts of a block copolymer (hereinafter, referred to as “block copolymer B”) and glutaraldehyde. 0.5 part was added, and the pH of the dispersion was adjusted to 3 with acetic acid. Thereafter, the reaction, adjustment, and measurement were performed in the same manner as in Example 1. The results are also shown in Table 9.

(Embodiment 4)

[0072]

[Table 3]

The mixture shown in Table 3 was dispersed in the same manner as in Example 1 and, after reaching a predetermined particle size, in the following general formula (4), A represents a hydroxyl group and B represents a hydroxyl group.

[0074]

Embedded image

R ¹ is a hydrogen atom, R ² is a methyl group, m is 2, p is 1, n and q are respectively 8 and 10 on average (hereinafter referred to as “block copolymer C”) 8 And 1 part of ammonium chloride, and the pH of the dispersion was adjusted to 3 with acetic acid.

[0076]

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Then, the reaction, adjustment and measurement were carried out in the same manner as in Example 1. The results are also shown in Table 9.

(Embodiment 5)

[0079]

[Table 4]

The mixture shown in Table 4 was dispersed in the same manner as in Example 1 and, after reaching a predetermined particle size, in the above formula (4), A was a hydroxyl group, B was -ONa, and R ¹ was 5 parts of a hydrogen atom, R ² is a methyl group, m is 2, p is 1, n and q are 12 and 6 on average respectively (hereinafter referred to as “block copolymer D”) and 1-ethyl-3 -(3-
Dimethylaminopropyl) carbodiimide (0.2 part) was added and the pH was adjusted using ethanolamine / hydrochloric acid buffer.
Was adjusted to 10. Thereafter, the reaction, adjustment, and measurement were performed in the same manner as in Example 1. The results are also shown in Table 9.

(Embodiment 6)

[0082]

[Table 5]

The mixture shown in Table 5 was dispersed in the same manner as in Example 1 and, after reaching a predetermined particle size, in the general formula (3), Z was an aldehyde group, Y was a hydrogen atom, R ¹ Is a hydrogen atom, m is 2, n is an average value of 12, and q is zero (hereinafter referred to as “block copolymer E”).
Was added and the pH of the dispersion was adjusted to 3 with acetic acid. Then, the reaction, adjustment, and measurement were performed in the same manner as in Example 1. The results are also shown in Table 9.

(Embodiment 7)

Dispersion was carried out in the same composition as in Example 1, 10 parts of block copolymer A and 2 parts of diammonium adipic acid were added, and the pH of the dispersion was adjusted to 3 with acetic acid. Then, the reaction, adjustment, and measurement were performed in the same manner as in Example 1. The results are also shown in Table 9.

(Embodiment 8)

Dispersion was carried out with the same composition as in Example 3, 10 parts of block copolymer B, 0.5 parts of glutaraldehyde and 1 part of ammonium chloride were added, and the pH of the dispersion was adjusted to 3 using acetic acid. It was adjusted. Then, the reaction, adjustment, and measurement were performed in the same manner as in Example 1. The results are also shown in Table 9.

(Comparative Example 1)

[0089]

[Table 6]

The mixture shown in Table 6 was pulverized in the same manner as in Example 1 except that the pulverization time was changed to 4 hours. Without treating the block copolymer, this dispersion was prepared by mixing water / glycerin with 2/1. The mixture was diluted with a mixed solvent at a weight ratio so that the dye concentration became 5%, adjusted, and then filtered using a 1 μm filter to prepare an ink.
Table 9 shows the results of evaluation and measurement in the same manner as in the above examples. Note that Comparative Example 1 is a representative example in which a nonionic dispersant was added instead of not treating the block copolymer corresponding to Example 1.

(Comparative Example 2)

[0092]

[Table 7]

The mixture shown in Table 7 was prepared and treated in the same manner as in Comparative Example 1, and the results are shown in Table 9. Comparative Example 2
This is a representative example using an anionic oligomer dispersant instead of not treating the glock polymer B corresponding to Example 3.

(Comparative Example 3)

[0095]

[Table 8]

The mixture shown in Table 8 was prepared and treated in the same manner as in Comparative Example 1, and the results are shown in Table 9. Comparative Example 3 is a known technique up to now, and was carried out in accordance with the dispersion conditions disclosed in Japanese Patent Application Laid-Open No. H10-330661, which was previously cited as a conventional technique.

[0097]

[Table 9]

In Table 9, "use of an auxiliary agent" means addition of a compound which generates an acid or alkali by heat treatment, and "particle size after storage" means that the particles were stored at 60 ° C. for 2 weeks. The subsequent particle size is shown. In addition, “discharge reduction” indicates a decrease in the discharge amount after continuous discharge of 200 million drops, and “dyeing rate”
The dyeing ratio is shown by comparing the dyeing ratio of the ink not treated with the block copolymer with 100%.

As described above, according to Table 9 showing the results of Examples 1 to 8 and Comparative Examples 1 to 3, when the block copolymer according to the present invention was grafted onto the surface of the disperse dye particles, the particle size was small and the dispersion stability was good. Even after storage for two weeks in an environment at 60 ° C., little change in particle size due to secondary aggregation is observed, and good storage stability is exhibited. This is supported by the result of the decrease in the nozzle discharge amount.

In Example 6, only poly (ethylene oxide) having no polyester portion was grafted. In this case, good dispersibility was maintained.
Good dyeing rate.

Examples 7 and 8 are examples in which a graft copolymer is grafted using the block copolymer A or the block copolymer B, and a compound which generates an acid or an alkali by heat is added. In this case, it can be seen that the dyeing rate is clearly improved as compared with Examples 1 to 3 in which the compound is not used.

On the other hand, in the case of Comparative Examples 1 to 3 in which a nonionic, anionic or anionic dispersant having a strong interaction with a disperse dye was simply added, when stored for 2 weeks in an environment of 60 ° C., Although there is a difference, it can be seen that in each case, aggregation occurs and the ejection ability is reduced.

From the above results, it can be seen that the disperse dye ink of the present invention can be stored for two weeks under a severe environment of 60 ° C.
It can be seen that the dispersion state can be stably maintained, the discharge amount after the continuous discharge of 200 million drops hardly decreases, and no clogging occurs inside the nozzle. Further, it was proved that the decrease in the dyeing rate which was anxious due to the grafting of the block polymer was also small, and as in Examples 7 and 8, a compound which generates acid or alkalinity by heat was added, thereby further increasing the dyeing rate. It was also proved that it improved. Also,
The disperse dye ink of the present invention exhibited excellent color development inherent in the dye because the block copolymer was released from the disperse dye by heat treatment after dyeing.

[0104]

According to the disperse dye ink of the present invention, since the hydrophobic-hydrophilic block copolymer having a dispersing function is bonded to the surface of the disperse dye particles, the disperse dye ink has excellent dispersion stability and long-term storage. It has excellent properties and environmental stability, and also has excellent coloring and dyeing properties because the bond between the block copolymer and the disperse dye is a bond that is cleaved by heat or acid or alkali.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Masakazu Tanaka 212, Kuromon-dori Oikegami Le Textile Shop, Kyoto, Nakagyo-ku, Kyoto F-term in Upepo & Maji Co., Ltd. 2C056 FC02 4H057 AA01 BA08 BA22 DA01 DA34 GA06 4J039 AD17 AE06 AE07 BA15 BA17 BA18 BA19 BC19 BC33 BC54 BC58 BE08 CA06 EA41 EA42 EA43 EA44 FA03 GA24

Claims (7)

[Claims] 1. An ink using a disperse dye, wherein a block copolymer having a hydrophilic segment and a hydrophobic segment is bonded to the disperse dye by a bond cleavable by the action of heat, an acid or an alkali. 2. The ink according to claim 1, wherein the block copolymer comprises a compound represented by the following general formula (1). Embedded image [In the formula (1), D represents a disperse dye residue, X represents a bond cleavable by heat or acid or alkali, and R ¹
And R ² are a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, m is an integer of 2 to 6, p is an integer of 1 to 5, n and q are 0 or an integer of 1 to 100, and Y is It represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an allyl group having 6 to 18 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms, respectively. ] 3. In the general formula (1), X is -N = C-, -N
= N-, -OC (= O)-, -NHC (= O)-, -OC (= O) O- or-
The ink using the disperse dye according to claim 2, which is NHC (= O) O-. 4. The ink according to claim 2, wherein q in formula (1) is zero. 5. The ink according to claim 1, wherein the block copolymer comprises a compound represented by the following general formula (2). Embedded image [In the formula (2), D represents a disperse dye residue, X represents —OH, an alkoxy group having 1 to 10 carbon atoms, and 6 to 18 carbon atoms.
An aryloxy group or an aralkoxy group having 7 to 20 carbon atoms, R ¹ and R ² are a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, m is an integer of 2 to 6, and p is an integer of 1 to 5 , N
And q are 0 or an integer of 1 to 100, Y is nothing and D
Either directly connected to _{the, -CH 2 CH (OH) CH} 2 -, - NH -, - NHNH
-Or -NHCO- respectively. ] 6. The method according to claim 1, wherein the average particle size of the disperse dye particles before bonding to the block copolymer is 0.35 μm or less and the maximum particle size is 0.7 μm or less.
13. An ink using the disperse dye described in the above item. 7. The ink using the disperse dye according to claim 1, wherein a compound that generates an acid or an alkali by the action of heat is blended in the ink.