JP3483372B2 - Water based fine particle dispersed ink - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a water-based fine particle dispersion ink using a disperse dye, which is useful as a fabric dyeing solution or an ink jet printing ink.

[0002]

2. Description of the Related Art Conventionally, a technique for dispersing fine particles of a disperse dye in an aqueous medium has been known. Typical dispersants for dispersing disperse dyes in water include formalin condensates of naphthalene sulfonic acid, lignin sulfonic acid, and the like, and as surfactants, JP-A-48-14
888 (Hoechst), Japanese Patent Laid-Open No. 50-100386.
JP-A-54-2484 (Toho Kagaku), JP-A-55-54353 (ICI), JP-A-61-213273 (Toray) and the like. Technology is known.

The selection of these dispersants or surfactants is made on the basis of the physical properties of the disperse dye to be dispersed, but the specific material combination and selection method have not necessarily been clarified as industrial technology. Not a thing. Specifically, even if the average particle size is in a fine particle state of 0.3 μm or less and the solid content is about 10 to 20% by weight,
It is difficult to obtain a low-viscosity and stable aqueous fine particle-dispersed ink having a viscosity of 3 centipoise or less with a high yield by using these conventional dispersants or surfactants. However, these conventional dispersants or surfactants have high solubilities in both acidic and alkaline regions, and therefore the dispersants can be easily removed after dyeing.

On the other hand, according to the test by the present inventors, when the disperse dye is dispersed in an aqueous system by using an alkali-soluble water-soluble resin used for dispersing a pigment, it is possible to obtain a certain level of fine particles. , Such a polymer dispersant has a small reaching particle size but a low yield (a large coarse particle ratio) as compared with a dispersant for a typical disperse dye such as a formalin condensate of naphthalene sulfonic acid, It cannot reach an effective level for industrialization. And, importantly, those alkali-soluble water-soluble resins are polymers having a carboxyl group as a water-soluble group, and when applied to printing, it is necessary to wash after dyeing, that is, to remove the dispersant. However, there is a practical drawback that it is difficult to do so, the resin is likely to remain on the cloth to be dyed, and the texture of the cloth is deteriorated.

As described above, with the conventionally known dispersants, it is the current situation that the fineness of the disperse dye and the detergency after dyeing are not compatible with each other. Therefore, a dispersant for a disperse dye having a new property is required in order to print on a cloth to be dyed by an ink jet recording method and to process it in the same dyeing process as the conventional one.

[0006]

SUMMARY OF THE INVENTION Therefore, the object of the present invention is to disperse a disperse dye in the form of fine particles having a desired particle size, have a low viscosity even at a high solid content concentration, and provide a stable long-term aqueous disperse dye. An object of the present invention is to provide a water-based fine particle ink of a disperse dye, which is a fine particle dispersed ink and is excellent in detergency in a post-process performed after dyeing.

[0007]

The above object can be solved by the present invention described below. That is, the present invention is at least water,
Water-soluble organic solvent, met aqueous fine particle dispersion ink containing a disperse dye and a water-soluble urethane polymer, distributed processing of the dispersion dye by the water-soluble urethane polymer
Is, the water-soluble urethane polymer has an acryloyl group at a molecular chain terminal, and is copolymerizable with the water-soluble urethane polymer comprising a water-soluble urethane compound and hydrophobic acrylic monomers having a sulfonic acid group as a dissociative group is water-based fine particle dispersion ink you characterized. Preferred of the present invention
As a preferred form, in the above, the dispersed processing is performed.
Dyes having an average particle size of 0.3 μm or less, dispersion treatment
The dispersed dye has a particle size distribution in the range of 0.01 to 1 μm.
And the above copolymerization was carried out in an emulsified state
Form, and acid value of the above water-soluble urethane polymer
Is 100 to 160, the above disperse dye and water.
The weight ratio of the soluble urethane polymer is 100: 30 to 10
0: 200 range, ink pH 4-9
Shall have been adjusted to the range, also further Noni in addition to the
Containing an on-anionic surfactant,
In addition to the above, it also contains alcohol amine
, And ink-jet inks
It

According to the present invention, the disperse dye is finely dispersed in a desired particle size by dispersing the disperse dye with a specific polymer dispersant, and the disperse dye has a low viscosity even at a high solid content concentration. Further, it is a water-based fine particle dispersion ink of a disperse dye that is stable for a long period of time, and provides a water-based fine particle ink of a disperse dye that is also excellent in detergency in a post-process after dyeing. More specifically, in the water-based fine particle-dispersed ink of the present invention, the dispersed dye has a particle size distribution in the range of 0.01 to 1 μm and an average particle size of 0.3 μm or less, and the dispersion stability in the fine particle state. Excellent in removing dispersant after dyeing (washability) especially in dyeing process. In conventional textile printing process, dispersant removing process such as washing with warm water after dyeing, reduction washing, etc. It is used as a recording ink having aptitude. Further, the water-based fine particle-dispersed ink of the present invention is an ink excellent in particle dispersibility in the submicron region, storage stability, ejection characteristics, color of dyed product, and fastness necessary for recording them.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in more detail below with reference to preferred embodiments. The main feature of the present invention is that the disperse dye is dispersed in an aqueous dispersion medium using a specific water-soluble urethane polymer. 1. Water-Soluble Urethane Polymer First, the water-soluble urethane polymer used in the present invention will be described. In the present invention, a urethane compound having an acryloyl group at the terminal of the molecular chain and having a sulfonic acid group as a solubilizing group is emulsion-copolymerized with a hydrophobic acrylic monomer to obtain a desired water-soluble urethane polymer. Is used as a dispersant for the disperse dye. This water-soluble urethane polymer can be obtained by the following synthetic method.

A. In the case of a graft-type water-soluble polymer A-2 Preparation or synthesis of a compound having two hydroxyl groups and one sulfonic acid group. A- Synthesis of a water-soluble urethane oligomer having isocyanate groups at both ends and having a large number of sulfonic acid groups in the side chains. A- If necessary, a diamine may be used for chain extension.
The individual oligomers are chain-extended under the condition that both ends become isocyanate. A-One isocyanate group is blocked with a hydroxyl group-containing acrylic monomer to form a half-urethane (one end is an acryloyl group). A- The remaining isocyanate group is blocked with amines (formation of water-soluble macromonomer). A- Using the water-soluble macromonomer as an emulsifier, the water-soluble macromonomer and the hydrophobic monomer are emulsion-copolymerized (formation of a graft-type water-soluble polymer).

B. In the case of block type water-soluble polymer B-2 Preparation or synthesis of a compound having two hydroxyl groups and one sulfonic acid group. B- Synthesis of a water-soluble urethane oligomer having isocyanate groups at both ends and having a large number of sulfonic acid groups in the side chains. B- If necessary, 2 with diamines for chain extension
The individual oligomers are chain-extended under the condition that both ends become isocyanate. B— A hydroxyl group-containing acrylic monomer is bonded to the isocyanate groups at both ends (acryloyl group at both ends → generation of bifunctional water-soluble macromonomer). B- Using the water-soluble macromonomer as an emulsifier, the water-soluble macromonomer and the hydrophobic monomer are emulsion-copolymerized (formation of a block-type water-soluble polymer).

Each of these reactions is not particularly new as a synthetic technique. The graft-type water-soluble polymer will be described in more detail in terms of materials used. A-2 Preparation or synthesis of a compound having two hydroxyl groups and one sulfonic acid group. Examples of these compounds include the following existing compounds, all of which can be used in the present invention.

(F-1) N, N-Bis (2-hydroxyethyl) -2-aminoethane sulfonic aci
d (F-2) 3- [N, N-Bis (2-hydroxyethyl) amino] -2-hydroxypropane
sulfonic acid

(F-3) 2,3-Dihydroxynaphthalene-6-sulfonic acid monosodiu
m salt (F-4) 1,8-Dihydroxynaphthalene-3,6-disulfonic acid disod
ium salt

(F-5) 2,7-Dihydroxynaphthalene-3,6-disulfonic acid disod
ium salt (F-6) 1,7-Dihydroxynaphthalene-3-sulfonic acid monosodiu
m salt

The compound of F-2 has three hydroxyl groups. However, even such a substance can be used in a small amount in the case of having a branched structure and is useful. did. Of course, since many other compounds having two hydroxyl groups and one sulfonic acid group exist in one molecule, the present invention is not limited to the above compounds. Among the above compounds, a compound having an aromatic skeleton gives preferable results in terms of dispersibility in a disperse dye.

A-Synthesis of a water-soluble urethane oligomer having a sulfonic acid group on the side chain. As the diisocyanates to be reacted with the compound having two hydroxyl groups and one sulfonic acid group, basically, difunctional 2,4-tolylene diisocyanate,
2,6-tolylene diisocyanate, hexamethylene diisocyanate, m-phenylene diisocyanate, p
- phenylene diisocyanate, 4,4'-diphenylmethane diisocyanate, tetramethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, bis (Isoshiana over Tomechiru) cyclohexane, dicyclohexylmethane diisocyanate, lysine diisocyanate Examples thereof include nato, trimethylhexamethylene diisocyanate, 3,3′-dichloro-4,4′-biphenylene diisocyanate, 1,5-naphthalene diisocyanate, and 1,5-tetrahydronaphthalene diisocyanate.

Further, a compound having three or more isocyanate groups, such as an adduct of tolylene diisocyanate and hexamethylene diisocyanate, a urethane modified product, an allophanate modified product, a buret modified product, an isocyanurate modified product, is obtained as a water-soluble compound. It is also possible to use a small amount for the purpose of imparting a branched structure to the water-soluble urethane polymer if necessary.

The reaction ratio between the hydroxyl group-containing compound and the isocyanate compound is set so that the urethane oligomer thus produced has an isocyanate at the end of the molecular chain as the subsequent reaction site. The target molecular weight of the resulting oligomer is in the range of 1,000 to 3,000, and the calculated acid value of the oligomer itself is the compound having two hydroxyl groups and one sulfonic acid group used and the isocyanate. It depends on the reaction ratio with
A range of 0 is obtained. If this acid value is smaller than this range, the acid value of the finally obtained water-soluble urethane polymer will be too low, and the water solubility will be reduced, such being undesirable. In principle, it is impossible to increase the acid value beyond this range.

In the urethanization reaction, the above-mentioned compound having two hydroxyl groups and one sulfonic acid group in one molecule is selected under the condition that the sulfonic acid group does not react when the hydroxyl group reacts with the isocyanate. There is a need. For that purpose, the sulfonic acid group is preferably made into a salt such as a soda salt or an amine salt. In such a case, the reaction solvent is an aprotic polar solvent, that is, N-methyl-2-pyrrolidone, 2-
Pyrrolidone, γ-butyrolactone, 1,3-dimethyl-
2-Imidazolidinone and the like are suitable.

A-A reaction in which one of the isocyanate groups is blocked to form a half urethane. Here, a hydroxyl group-containing monomer is additionally bonded to one of the total two isocyanates at both ends using the hydroxyl group to acryloylate or vinylate the terminal. Examples of the monomer to be used include 2-hydroxyethyl acrylate (2-HEA), 2-hydroxyethyl methacrylate, 3-chloro-2-hydroxyethyl (meth) acrylate, and a hydroxyl group in the side chain such as an ethylene oxide adduct thereof. And vinyl or acrylic monomers having In this reaction, it is preferable to slow the dropping rate of the monomer so that the reaction proceeds uniformly.

A- The remaining isocyanate groups are blocked with amines. Subsequent to the above reaction, the remaining isocyanate group is blocked with amines. Specific examples of the amine used for the blocking include amines such as monoethanolamine, diethanolamine, triethanolamine, dimethylamine, diethylamine, triethylamine and aminomethylpropanol. Of these, alcohol amines are preferable, and monoethanolamine is particularly preferable, from the viewpoints of reactivity and water solubility of the product. At this stage the solvent is removed under reduced pressure and heating. At that time,
A base is added as a neutralizing agent for the sulfonic acid group so that the pH remains basic. Thus, a urethane-based water-soluble macromonomer having a polymerizable unsaturated group at the terminal and a large number of sulfonic acid groups at the side chains is produced.

A-Emulsion Copolymerization. Since the water-soluble macromonomer has both a hydrophobic portion and a hydrophilic portion, the macromonomer is used as an emulsifying agent, and the macromonomer contains, for example, styrene, α-methylstyrene, methyl (meth) acrylate, It is a step of copolymerizing a hydrophobic monomer such as ethyl (meth) acrylate, t-butyl (meth) acrylate and n-butyl (meth) acrylate. Since the water-soluble macromonomer from which most of the solvent has been removed has surface activity, the water-soluble macromonomer is used as a reaction agent and an emulsifier, and the N-methylpyrrolidone / water system is used as a solvent system to obtain the above-mentioned hydrophobic property. Of the polymerizable monomer and the macromonomer are emulsified and copolymerized. Other emulsifiers may or may not be used to emulsify the monomers. As the polymerization initiator, a water-soluble initiator such as potassium persulfate is used. The balance between hydrophilicity and hydrophobicity of the resulting water-soluble urethane polymer changes depending on the copolymerization ratio of the water-soluble macromonomer and the hydrophobic monomer.

The weight ratio of water-soluble macromonomer to hydrophobic monomer is in the range of 1: 1 to 4: 1, preferably 2.5: 1.
Used in the range of ~ 3.5: 1. As a result, an almost transparent water-soluble resin solution having an acid value of 80 to 130 is obtained. If the polymerization solution becomes cloudy during the polymerization process, a non-volatile base such as monoethanolamine is replenished. A volatile base such as ammonia may be used depending on the application. As described above, a graft type water-soluble urethane polymer having a sulfonic acid group as a solubilizing group is obtained. The obtained aqueous solution is in the state of microemulsion,
Although it is suspended depending on the composition, if the usage ratio of the water-soluble macromonomer is within the above range, a generally transparent solution is obtained.

On the other hand, step A- and step A- of "A. In the case of graft type water-soluble polymer" are not taken, but the water-soluble urethane having a block structure is obtained by the procedure of "B. In the case of block type water-soluble polymer". Oligomers can be produced. That is, following "B-Synthesis of Water-Soluble Urethane Oligomer Having Sulfonic Acid Group in Side Chain", "B- If necessary, two oligomers are converted into isocyanates at both ends with diamines for chain extension. Chain extension under the following conditions "is performed.

Chain extension is carried out by reaction with diamines,
Then, both ends are reacted with a hydroxyl group-containing acrylic monomer to acryloylate both ends. A water-soluble macromonomer having an acryloyl group at both ends is produced. Chain extension with diamines is not essential and is performed as needed. After this, the step "B-emulsion polymerization" is performed. However, in this method, since both ends of the water-soluble macromonomer are polymerizable, the step B is performed so that the crosslinking does not proceed excessively.
It is desirable to prevent the gelation of the product by using ethyl acetate or a monohydric alcohol together as a reaction solvent in the emulsion copolymerization of-.

C. Hydrophobic monomer Examples of the hydrophobic monomer that constitutes the graft-type or block-type water-soluble urethane polymer described above include styrene, α-methylstyrene, vinyltoluene,
Aromatic vinyl compounds such as vinylnaphthalene, methyl (meth) acrylate, ethyl (meth) acrylate, n-
Propyl (meth) acrylate, isopropyl (meth)
Examples thereof include (meth) acrylic acid esters having a hydrocarbon group such as acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, and t-butyl (meth) acrylate in the side chain. Among these monomers, several kinds can be used together.

As described above, a water-soluble urethane polymer having a graft type or block structure is produced. Incidentally, the polymerization in the above-mentioned production method has been described as an emulsion polymerization method as a preferred example, but the polymerization is not limited to emulsion polymerization, and for example, other polymerization methods such as solution polymerization and suspension polymerization may be adopted. It is possible.

2. Disperse Dyes Examples of the disperse dyes used as the coloring material of the aqueous fine particle dispersion ink of the present invention include the following disperse dyes. Yellow disperse dye CIDisperse Yellow 5, CIDisperse Yellow 42,
CIDisperse Yellow 54, CIDisperse Yellow 6
4, CIDisperse Yellow 79, CIDisperse Yellow
82, CIDisperse Yellow 83, CIDisperse Yello
w 93, CIDisperse Yellow 99, CIDisperse Yel
low 100, CIDisperse Yellow 119, CIDisper
se Yellow 122, CI Disperse Yellow 124, CI
Disperse Yellow 126, CI Disperse Yellow 16
0, CIDisperse Yellow 184: 1, CIDisperse Y
ellow 186, CIDisperse Yellow 198, CIDisp
erse Yellow 199, CI Disperse Yellow 204, C.
I. Disperse Yellow 224, CI Disperse Yellow 23
7,

Orange disperse dyes CIDisperse Orange 13 and CIDisperse Orange 2
9, CIDisperse Orange 31: 1, CIDisperse Ora
nge 33, CIDisperse Orange 49, CIDisperse O
range 54, CIDisperse Orange 55, CIDisperse
Orange 66, CIDisperse Orange 73, CIDisper
se Orange 118, CIDisperse Orange 119, CID
isperse Orange 163,

Red disperse dyes CIDisperse Red 54, CIDisperse Red 72, CI
Disperse Red 73, CIDisperse Red 86, CIDisp
erse Red 88, CIDisperse Red 91, CIDisperse
Red 92, CIDisperse Red 93, CIDisperse Red
111, CIDisperse Red 126, CIDisperse Red
127, CIDisperse Red 134, CIDisperse Red
135, CIDisperse Red 143, CIDisperse Red
145, CIDisperse Red 152, CIDisperse Red
153, CIDisperse Red 154, CIDisperse Red
159, CIDisperse Red 164, CIDisperse Red
167: 1, CIDisperse Red 177, CIDisperse
Red 181, CIDisperse Red 204, CIDisperse
Red 206, CIDisperse Red 207, CIDisperse
Red 221, CIDisperse Red 239, CIDisperse
Red 240, CIDisperse Red 258, CIDisperse
Red 277, CIDisperse Red 278, CIDisperse
Red 283, CIDisperse Red 311, CIDisperse
Red 323, CIDisperse Red 343, CIDisperse
Red 348, CIDisperse Red 356, CIDisperse R
ed 362,

Purple disperse dye CIDisperse Violet 33, blue disperse dye CIDisperse Blue 56, CIDisperse Blue 60, C.I.
I. Disperse Blue 73, CI Disperse Blue 87, CI
Disperse Blue 113, CIDisperse Blue 128, C.
I. Disperse Blue 143, CIDisperse Blue 148,
CIDisperse Blue 154, CIDisperse Blue 15
8, CIDisperse Blue 165, CIDisperse Blue 1
65: 1, CIDisperse Blue 165: 2, CIDisper
se Blue 176, CIDisperse Blue 183, CIDisp
erse Blue 185, CIDisperse Blue 197, CIDi
sperse Blue 198, CIDisperse Blue 201, CI
Disperse Blue 214, CI Disperse Blue 224, C.
I.Disperse Blue 225, CIDisperse Blue 257,
CIDisperse Blue 266, CIDisperse Blue 26
7, CIDisperse Blue 287, CIDisperse Blue 3
54, CIDisperse Blue 358, CIDisperse Blue
365, CIDisperse Blue 368, green disperse dye CIDisperse Green 6: 1, CIDisperse Green 9.

Among the above dyes, more preferable dyes are as follows. Yellow disperse dye CIDisperse Yellow 5, CIDisperse Yellow 42,
CIDisperse Yellow83, CIDisperse Yellow 9
3, CIDisperse Yellow 99, CIDisperse Yellow
198, CIDisperse Yellow 224, orange disperse dye CIDisperse Orange 29, CIDisperse Orange 4
9, CIDisperse Orange 73

Red disperse dyes CIDisperse Red 92, CIDisperse Red 126, C.I.
I. Disperse Red 145, CIDisperse Red 152, C.
I. Disperse Red 159, CI Disperse Red 177, C.I.
I. Disperse Red 181, CIDisperse Red 206, C.
I. Disperse Red 283 Blue disperse dye CIDisperse Blue 60, CIDisperse Blue 87, C.I.
I. Disperse Blue 128, CIDisperse Blue 154,
CIDisperse Blue 201, CIDisperse Blue 21
4, CIDisperse Blue 224, CIDisperse Blue 2
57, CIDisperse Blue 287, CIDisperse Blue
368

Incidentally, these dyes are preferable examples,
The present invention is not limited to the dyes exemplified above,
Further, it may be a newly synthesized one. In dispersing the fine particles of these disperse dyes, it is preferable to use the product taken out in the form of a wet cake during the production of the dye in the dispersion treatment step for efficient fine particle formation.
The use of wet cake is basically a problem of work efficiency and does not have a great influence on the ultimate performance, so that it is not an essential condition for the present invention.

3. Production of Water-Based Fine Particle Dispersion Ink The water-based fine particle dispersion ink in the present invention is obtained by dispersing the disperse dye with the water-soluble urethane polymer. For the dispersion, the disperse dye and the water-soluble urethane polymer are mixed in a weight ratio of 100: 30 to 100: 200, premixed and then dispersed. For dispersion, a dispersion method using glass beads, silica-alumina ceramic beads, zirconia beads or the like as a medium is preferable.

The disperser used in the present invention may be any disperser which is generally used, so long as the disperse dye has an average particle diameter of efficiently in a desired range. Examples thereof include a ball mill and a sand mill. Among them, a high speed type sand mill is preferable, and examples thereof include a super mill, a sand glider, a bead mill, an agitator mill, a grain mill, a dyno mill, a pearl mill, and a cobol mill (all are trade names).
Further, it is efficient to use a roll mill, a jet mill, or the like together as a device that can apply high shear stress without using beads.

In the present invention, as a method for obtaining a dye-dispersed ink having a desired particle size distribution, the size of the pulverized media in the disperser is reduced, after dispersion, classification is carried out by pressure filtration or centrifugation, and aging treatment. A method such as pressure filtration may be used. Bubbles are generated during dispersion, and suppressing them as much as possible is also important for obtaining a dispersion having a small particle size. Therefore, a minimum amount of antifoaming agent may be added. The aqueous fine particle-dispersed ink of the present invention is manufactured as described above.

When the water-based fine particle-dispersed ink is used as an ink jet ink, it is desirable that impurities such as silica and heavy metals are as small as possible. The beads used as media in the dispersion of beads are ceramics, zirconium, etc. Those made of the same material are preferable.

4. Preparation of water-based fine particle-dispersed ink The liquid medium of the water-based fine particle-dispersed ink of the present invention is adjusted to have a necessary medium constitution according to the purpose of use. The medium used here is usually a water-miscible humectant used in an aqueous fine particle dispersion ink. According to the classification of the inventors, they can be divided into the following three groups. Group 1: Highly moisturizing solvent that is hard to evaporate and has excellent hydrophilicity. Group 2: Solvent that has a hydrophobic atomic group at the end and has good wettability to a hydrophobic surface and also has evaporative drying property. Group 3: Solvents (monohydric alcohols) having appropriate viscosity and low viscosity.

Specific examples of the solvent belonging to the first group include ethylene glycol, diethylene glycol, triethylene glycol, tripropylene glycol, glycerin, 1,2,4-butanetriol, 1,2,6-.
Hexanetriol, 1,2,5-pentanetriol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, dimethylsulfoxide,
Diacetone alcohol, glycerin monoallyl ether, propylene glycol, butylene glycol, polyethylene glycol 300, thiodiglycol, N-methyl-2-pyrrolidone, 2-pyrrolidone, γ-butyrolactone, 1,3-dimethyl-2-imidazolidinone , Sulfolane, trimethylolpropane, trimethylolethane, neopentyl glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoallyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, triethylene glycol Monomethyl ether, triethylene glycol monoethyl ether, propylene glycol Glycol monomethyl ether, dipropylene glycol monomethyl ether, bis β- hydroxyethyl sulfone, bis β- hydroxyethyl urea, urea, acetonyl acetone, pentaerythritol, and 1,4-cyclohexane diol.

Specific examples of the solvent belonging to the second group include hexylene glycol, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monoisobutyl ether, ethylene glycol monophenyl ether, diethylene glycol diethyl ether, diethylene glycol mono. Butyl ether, diethylene glycol monoisobutyl ether, triethylene glycol monobutyl ether,
Triethylene glycol dimethyl ether, triethylene glycol diethyl ether, tetraethylene glycol dimethyl ether, tetraethylene glycol diethyl ether, propylene glycol monobutyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, tripropylene glycol Monomethyl ether, glycerin monoacetate, glycerin diacetate, glycerin triacetate, ethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether acetate, cyclohexanol, 1,2-cyclohexanediol, 1-butanol, 3-methyl-1,5-pentanediol, 3-hex 2,5-diol, 2,3
Butanediol, 1,5-pentanediol, 2,4-
Examples include pentanediol and 2,5-hexanediol.

Specific examples of the solvent belonging to the third group include ethanol, n-propanol, 2-propanol, 1-methoxy-2-propanol, furfuryl alcohol and tetrahydrofurfuryl alcohol. The total amount of the water-soluble solvent as described above is generally in the range of 5 to 40% by weight with respect to the entire water-based fine particle-dispersed ink.

5. pH adjuster The pH of the water-based fine particle-dispersed ink in the present invention can be adjusted within a wide range of about 4-9. The pH range is the dissolution region itself of the water-soluble urethane polymer which is the dispersant, which is the main element of the present invention, but is determined according to the individual application from the dyeability.

The sulfonic acid group of the water-soluble urethane polymer is neutralized and used as an aqueous solution. Specific examples of the neutralizing agent therefor include ethanolamine, diethanolamine, triethanolamine, N-methylethanolamine, N-ethyldiethanolamine and 2-
Amino-2-methylpropanol, 2-ethyl-2-amino-1,3-propanediol, 2- (2-aminoethyl) ethanolamine, tris (hydroxymethyl)
Aminomethane, ammonia, glycine, glycylglycine, histidine, L-lysine, L-arginine, piperidine, morpholine, organic bases such as β-dihydroxyethylurea, and bases such as sodium hydroxide, potassium hydroxide and lithium hydroxide Is mentioned. It is preferable to select alcohol amine among these bases in order to obtain the storage stability of the ink and the stable ejection property on the ink jet recording apparatus.

6. Surfactant It is practical to add a surfactant to the water-based fine particle-dispersed ink of the present invention for the purpose of imparting dyeability to cloth and improving ejection efficiency when used in a bubble-jet type fine particle-dispersion inkjet device. May be advantageous to. Examples of such surfactants include anionic surfactants such as sodium dodecylbenzene sulfonate and sodium lauryl sulfate; nonionic surfactants such as ethylene oxide adducts of acetylene glycol and polyoxyethylene long-chain alkyl ethers; Nonionic-anionic surfactants such as polyoxyethylene alkyl ether having HLB of 10 or more and an anionic dissociative group selected from acids and carboxylic acids, and polyoxyethylene alkylphenyl ethers are mentioned.

The addition of these surfactants to the water-based fine particle-dispersed ink in the present invention is selected and added as necessary in consideration of foaming property. Particularly preferred compounds are nonionic-anionic surfactants. The nonionic-anionic surfactant is a surfactant which is excellent in both ejection sustainability and foaming property with respect to the water-based fine particle dispersed ink of the present invention.

7. Other additives In order to improve the dispersion stability of the dispersion particles in the ink, as a leveling agent at the time of dyeing the fabric, a naphthalene sulfonic acid formalin condensate, an alkali salt of lignin sulfonic acid,
Furthermore, an alkali salt of polystyrene sulfonic acid can be used in combination.

[0049]

EXAMPLES The present invention will be described more specifically below with reference to examples and comparative examples. In the following Examples and Comparative Examples, unless otherwise specified, parts represent weight percentages, the weight average molecular weight is a value measured by the GPC method using a styrene polymer as a standard, and the average particle size is It is the value measured by the dynamic light scattering method.

Synthesis Example 1 Block-type urethane polymer Compound F-1 (N, N-Bis (2-hydroxyethyl) -2-aminoe)
118 g of sodium salt of thane sulfonic acid (0.5
Mol) in 200 ml of N-methylpyrrolidone,
The solution was maintained at 45 ° C. with stirring, and under a nitrogen atmosphere, 122.3 g of isophorone diisocyanate (0.
55 mol) of a 50% by weight solution of N-methylpyrrolidone in 1
The solution was added dropwise over a period of time and the reaction was continued for 4 hours. When the hydroxyl value completely disappeared, the temperature was lowered to stop the urethanization reaction. The NCO equivalent of the product was 2300 (vs solids). To this reaction solution, 20 g (about 0.17 mol) of 2-hydroxyethyl acrylate was added and reacted at 60 ° C. for 6 hours. After completion of the reaction, the reaction oligomer was added to ethanol to precipitate the reactive oligomer, and unreacted substances were removed. Then, monoethanolamine and water were added to the product to obtain a water / N-methylpyrrolidone solution having a solid content of 25% by weight. In this way, the water-soluble urethane macromonomer 1 used in the present invention was obtained.

120% of water-soluble urethane macromonomer 1
20 parts by weight of styrene, 20 parts by weight of t-butyl methacrylate, and 2 parts of potassium persulfate were added to parts by weight, and the mixture was emulsified with an ultra homogenizer. The suspension was subjected to radical polymerization at 70 ° C. for 5 hours while stirring at 1000 rpm. The resulting solution has a viscosity of 240
It was a light yellow transparent colloidal solution of cps. The number average molecular weight of the produced polymer was 8,900. Compound F-1

Synthesis Example 2 Graft-type urethane polymer Compound F-3 (2,3-Dihydroxynaphthalene-6-sulfo)
131.8 g (0.5 mol) of nic acid monosodium salt) was dissolved in 300 ml of N-methylpyrrolidone, and the solution was maintained at 45 ° C. with stirring, and 69.3 g of hexamethylene diisocyanate under a nitrogen atmosphere ( 0.55
50% by weight solution of N) -methylpyrrolidone (mol) was added dropwise over 1 hour, and the reaction was continued for 4 hours. When the hydroxyl value completely disappeared, the temperature was lowered to stop the urethanization reaction. The NCO equivalent weight of the product was 3100 (vs. solids). To this reaction solution, 0.03 mol (1.83 g) of ethanolamine was added, and the mixture was stirred and reacted at room temperature for 1 hour, then 0.06 mol (7 g) of 2-hydroxyethyl acrylate was added, and the mixture was heated at 60 ° C. The reaction was carried out for 3 hours. After the reaction was completed, the solution was poured into ethanol to precipitate the generated reactive oligomer, and unreacted substances were removed. Then, monoethanolamine and water were added to the product to obtain a water / N-methylpyrrolidone solution having a solid content of 35% by weight. In this way, the water-soluble urethane macromonomer 2 used in the present invention was obtained.

120 of the water-soluble urethane macromonomer 2
20 parts by weight of ethyl methacrylate, t
20 parts by weight of butyl methacrylate and 2 parts of potassium persulfate were added, and the mixture was emulsified with an ultra homogenizer.
This suspension was subjected to radical emulsion polymerization at 70 ° C. for 5 hours while stirring at 1000 rpm. The resulting solution was a pale yellow transparent colloidal solution with a viscosity of 250 cps. The number average molecular weight of the produced polymer was 13,500. Compound F-3

Synthetic Examples 3 to 6 Water-soluble urethane polymers of Synthetic Examples 3 to 6 were synthesized in the same manner as in Synthetic Examples 1 and 2 using the materials shown in Table 1 below.

Here, the HM / LM ratio represents the weight ratio of the hydrophobic monomer and the urethane macromonomer. The amine in the table represents the amine used for blocking one end in the case of grafting. For acryloylation, 2-
Hydroxyethyl acrylate was used. IPDI is isophorone diisocyanate, HMDI is hexamethylene diisocyanate, amine A is monoethanolamine, St is styrene, t-BMA is t-butyl methacrylate, n-BMA is n-butyl methacrylate, EM.
A represents ethyl methacrylate.

Example 1 Dispersion DBL-1 and aqueous fine particle dispersion inks BL-1 and BL-2 of Example 1 were prepared by the following method. (Dispersion DBL-1) -Water-soluble urethane polymer of Synthesis Example 1 (45% by weight aqueous solution, pH 7.8) 10 parts-C.I. I. Disperse Blue 79 Wet cake prototype (solid content) 25 parts ・ Isopropyl alcohol 10 parts ・ Antifoaming agent Surfynol 104E Some amount (<1 part) ・ Water 140 parts Charge these materials to a zirconium batch type vertical sand mill After premixing for 30 minutes, 250 ml in volume using 1 mm diameter zirconium beads as media.
It was filled and dispersed with water at 15000 rpm for 5 hours. The viscosity of the liquid after dispersion was 4.5 cps. The dispersion was centrifuged at 8000 rpm for 20 minutes to remove coarse particles, and the solid content was 14.0% by weight.
Average particle size 135 mμ, surface tension 45 dyne / cm, p
A dispersion DBL-1 of H7.5 was obtained.

(Water-based fine particle dispersion ink BL-1) -Dispersion DBL-1 50 parts-Ethylene glycol 15 parts-Isopropyl alcohol 4 parts-Monoethanolamine 1 part-Water 30 parts. Pressure filtration was performed using a 25 μm membrane filter to prepare a blue water-based fine particle dispersion ink BL-1 having a viscosity of 2.2 cps, a surface tension of 40 dyne / cm, and a pH of 8.3.

(Aqueous fine particle dispersion ink BL-2) Dispersion DBL-1 50 parts Diethylene glycol 15 parts Isopropyl alcohol 5 parts Fasphanol RE410 monoethanolamine salt (manufactured by Toho Kagaku) 0.6 parts Mono Ethanolamine 1 part / water 25 parts These components are mixed well and pressure filtered using a 0.25 μm membrane filter to give a viscosity 2.4 cps, surface tension 36.5 dyne / cm, pH 9.3 blue water system. A fine particle dispersion ink BL-2 was prepared.

Example 2 Dispersion DBL-2 and aqueous fine particle dispersion inks BL-3 and BL-4 of Example 2 were prepared by the following method. (Dispersion DBL-2) -Water-soluble urethane polymer of Synthesis Example 2 (solid content 50% by weight aqueous solution, pH 8.8) 8 parts-C.I. I. Disperse Blue 60 wet cake prototype (solid content) 37.5 parts, diethylene glycol 7 parts, water 120 parts These materials were placed in a zirconium batch vertical sand mill, and after 30 minutes of premixing, zirconium with a diameter of 1 mm. 250 ml by volume using beads as media
After filling and cooling with water, dispersion treatment was performed at 2000 rpm for 5 hours. The viscosity of the liquid after dispersion was 8 cps. This dispersion was centrifuged at 8000 rpm for 20 minutes to remove coarse particles, and solid content 20% by weight, average particle size 12
A dispersion DBL-2 having 0 mμ, a surface tension of 45 dyne / cm and a pH of 8.4 was obtained.

(Aqueous fine particle dispersion ink BL-3) -Dispersion DBL-2 50 parts-Thiodiglycol 10 parts-Glycerin 10 parts-Monoethanolamine 1 part-Water 29 parts Mix well with these components, Pressure filtration was performed using a 25 μm membrane filter to obtain a blue water-based fine particle dispersion ink BL-3 having a viscosity of 2.2 cps, a surface tension of 42 dyne / cm, and a pH of 9.2.

(Aqueous fine particle dispersion ink BL-4) Dispersion DBL-2 40 parts-Thiodiglycol 10 parts-Glycerin 10 parts-Monoethanolamine 1 part-Diethanolamine salt of carboxylated ethylene oxide adduct of lauryl alcohol ( Nonionic part HLB = 12) Prototype manufactured by San Nopco Co., Ltd. 1.0 part, water 36 parts Mixing these components well, pressure filtering using a 0.25 μm membrane filter, viscosity 2.4 cps, A blue water-based fine particle dispersion ink BL-4 having a surface tension of 45 dyne / cm and a pH of 9.5 was prepared.

Example 3 Dispersion DY-1 of Example 3 and aqueous fine particle dispersion inks Y-1 and Y-2 were prepared by the following method. (Dispersion DY-1) 7 parts of water-soluble urethane polymer of Synthesis Example 3 (solid content 45% by weight aqueous solution, pH 8.0) C.I. I. Disperse Yellow 64 wet cake prototype (solid content) 24 parts, ethylene glycol 10 parts, water 100 parts A dispersion liquid having a viscosity of 4.5 cps was prepared using these materials in the same manner as in Example 1. Was produced. This dispersion was subjected to a centrifugal separation treatment in the same manner as in Example 1 to prepare a dispersion DY-1 having a solid content of 20% by weight, an average particle size of 157 mμ, a surface tension of 47 dyne / cm and a pH of 8.0.

(Aqueous Fine Particle Dispersion Ink Y-1) Dispersion DY-1 45 parts / Ethylene glycol 15 parts / Triethylene glycol 10 parts / Ethanol 3 parts / Water 27 parts Mixing well with these components, 0.25 μm Was filtered under pressure using a membrane filter of No. 1 to obtain a yellow water-based fine particle dispersion ink Y-1 having a viscosity of 2.2 cps, a surface tension of 45 dyne / cm, and a pH of 8.0.

[0064] These components were mixed well and filtered under pressure using a 0.25 μm membrane filter to obtain a yellow water-based fine particle dispersion ink Y-2 having a viscosity of 2.2 cps, a surface tension of 37 dyne / cm and a pH of 8.0.

Comparative Example 1 In the dispersion formulation of Example 1, as a dispersant, Synthesis Example 1 was used.
Instead of the water-soluble urethane polymer (45% by weight aqueous solution), Namolene sulfonic acid type dispersant, Demol N
Dispersion treatment was carried out in the same manner as in Example 1 except that a monoethanolamine salt (manufactured by Kao Corporation) was used to obtain dispersion DC-1 of Comparative Example 1. The dispersion DC-1 obtained after centrifugation had a solid content of 18% by weight and a pH of
7.5, surface tension 56 dyne / cm, viscosity 5.8 cp
The average particle size was 250 mμ. This dispersion DC-1
By using the following water-based fine particle dispersion ink C-1
Was produced. (Aqueous fine particle dispersion ink C-1) -Dispersion DC-1 43 parts-Diethylene glycol 15 parts-Isopropyl alcohol 4 parts-Monoethanolamine 1 part-Water 37 parts Mix well with these components and use a 1 μm membrane filter. And filtered under pressure to prepare a blue water-based fine particle dispersion ink C-1 having a viscosity of 2.2 cps, a surface tension of 46 dyne / cm and a pH of 9.0.

Comparative Example 2 Synthesis Example 2 was used as a dispersant in the dispersion formulation of Example 2.
Water-soluble urethane polymer (50 wt% solids aqueous solution)
A lignin sulfonic acid type water-soluble resin (copartin soda Kop-44, manufactured by Kojin Co., Ltd.) was used in place of the above, and the dispersion treatment was performed in the same manner as in Example 2 to obtain the dispersion of Comparative Example 2. It was set to DC-2. The dispersion obtained after the centrifugal treatment had a solid content of 22% by weight, a pH of 7.7 and a surface tension of 50.
dyne / cm, viscosity 8.5 cps, average particle size 300 m
It was μ. Using this dispersion DC-2, a water-based fine particle dispersion ink C-2 of the following comparative example was produced. (Aqueous fine particle dispersion ink C-2) -Dispersion DC-2 45 parts-Diethylene glycol 10 parts-Glycerin 10 parts-Monoethanolamine 1 part-Water 33 parts These components were mixed well and a 1 μm membrane filter was used. Pressure filtration was performed to prepare a blue water-based fine particle dispersion ink C-2 having a viscosity of 2.8 cps, a surface tension of 46 dyne / cm, and a pH of 8.8.

Comparative Example 3 In the dispersion formulation of Example 2, as a dispersant, Synthesis Example 2 was used.
Water-soluble urethane polymer (50 wt% solids aqueous solution)
Instead of styrene-acrylic acid-ethyl acrylate copolymer resin (carboxylic acid type water-soluble resin, acid value 19
Dispersion treatment was carried out in the same manner as in Example 2 except that No. 5, weight average molecular weight 8500, manufactured by Hoshiko Kagaku Co., Ltd. was used to obtain dispersion DC-3 of Comparative Example 3. The dispersion obtained after the centrifugal treatment had a solid content of 18% by weight, a pH of 9.0, a surface tension of 48 dyne / cm, a viscosity of 8.5 cps, and an average particle diameter of 125 mμ. Using this dispersion DC-3, a water-based fine particle dispersion ink C-3 of the following comparative example was produced. (Aqueous fine particle dispersion ink C-3) -Dispersion DC-3 45 parts-Diethylene glycol 10 parts-Glycerin 10 parts-Isopropyl alcohol 2 parts-Diethanolamine salt of carboxylate of ethylene oxide adduct of lauryl alcohol (nonionic portion HLB = 12) ) Prototype manufactured by San Nopco Co., Ltd. 1.0 part / water 32 parts These components are mixed well and pressure filtered using a 0.2 μm membrane filter to give a viscosity of 2.5 cps, a surface tension of 46 dyne / cm, A blue water-based fine particle dispersion ink C-3 having a pH of 9.0 was obtained.

[Performance Evaluation] The performance evaluation methods of the respective water-based fine particle dispersed inks of Examples and Comparative Examples are shown below. Printing Durability Test At 360 dpi, an ink jet recording apparatus equipped with a bubble jet recording head having 64 nozzles was filled with each ink of Examples and Comparative Examples through an ink supply tube. The drive frequency of the recording apparatus is 6.2 kHz, and the amount of droplets of a single dot is 80 ng. Under this condition, a continuous discharge test of 3 × 10 ⁸ pulses using every 32 nozzles was performed. For the determination, a test document including a document, a solid pattern, and ruled lines was printed at the initial stage and after the ejection of 3 × 10 ⁸ pulses, and the deterioration of printability was evaluated. Show the result
2 shows. (Evaluation rank) ○: Vivid characters, uniform and vivid solid printing, and ruled line printing without wobbling. Δ: Somewhat faint characters, solid printing with a decrease in density, and ruled line printing with warpage. ×: Characters that are faint and difficult to read, uneven and thin solid printing, irregular ejection, and irregular ruled line printing.

Storage stability test 50 ml of each water-based fine particle-dispersed ink of Examples and Comparative Examples was filled in a shot heat-resistant bottle having an internal volume of 100 ml and tightly stoppered.
An accelerated storage test was performed at 0 ° C for 1 month. For the determination, the viscosity after storage was measured to determine whether the storability was good or bad. Show the result
2 shows. (Evaluation rank) Good: The increase in viscosity is within 10% of the initial level, and almost no precipitation is observed. Δ: The change in viscosity was 10 to 50% of the initial value, and precipitation occurred. X: Gelled or hard precipitate.

Textile printing test Bubble jet printer BJC-600 (manufactured by Canon Inc.)
Was used to make a color recording on the fabric. The cloth used was polyester decyne, which was padded with a 1% by weight aqueous solution of polyvinylpyrrolidone, dried (squeezing ratio: 80%), and then stuck on a Mylar film with a double-sided adhesive tape and recorded by a printer. After the color printing, the fabric was peeled from the mylar film, and then HT steaming treatment was performed at 180 ° C. for 5 minutes. After that, reduction printing, water washing, and drying were carried out by a conventional method to obtain a polyester print. The obtained printed material was judged by -1: printability (color density, color tone, sharpness, and wash fastness), and -2: texture (washability). The results are shown in Table 2 .

(Evaluation Rank) -1: Printability (coloring density, color tone, sharpness, washing fastness) ◎: All good ○: Boundary between different colors is slightly blurred Δ: Coloring density is slightly low and bleeding ×: Coloring Concentration is slightly low and bleeding is poor, and washing fastness is poor -2: Texture (detergency) ◯: Good Δ: Slight decrease X: Poor

[0072]

[0073]

As described above, when the aqueous fine particle dispersion ink of the present invention is used, excellent storage stability can be obtained in the ink jet recording method, and bleeding is caused when color recording is performed on the cloth. A printed matter which does not cause feathering, is excellent in fixability, and has good color developability and fastness is provided. In particular, excellent washability after dyeing is provided, and a good quality dyed product is provided under the same processing conditions as in the conventional process, even if an inkjet method is used, without impairing the texture of the fabric.

The water-based fine particle-dispersed ink of the present invention is used in a writing instrument ink, an ink jet ink, especially in an ink jet recording apparatus using a bubble jet system.
The disperse dye can be used for an aqueous fine particle dispersion ink for use as a recording agent. Specifically, stationery,
These include color printers, color plotters, poster printing, signboard printing, light printing, textile printing, and color printers for liquid crystal displays. Also, by using a disperse dye,
Provided are recording, printing and dyeing excellent in water resistance, light resistance and color resistance.

─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor, Clothing Shirota 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. (72) Inventor, Tomoya Yamamoto 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon (72) Inventor Mariko Suzuki 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. (72) Inventor Shinichi Hakama 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. ( 56) References JP-A-56-38316 (JP, A) JP-A-5-194688 (JP, A) JP-A-9-111173 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C09D 11/00-11/20 D06P 5/00 C08G 18/00-18/87

Claims (10)

(57) [Claims] 1. A least water, a water-soluble organic solvent, met aqueous fine particle dispersion ink containing a disperse dye and a water-soluble urethane polymer, the disperse dye is dispersed by the water-soluble urethane polymers, water-soluble urethane polymer has an acryloyl group at a molecular chain terminal, you being a and water-soluble urethane polymer and water-soluble urethane compound and hydrophobic acrylic monomers by copolymerizing having a sulfonic acid group as a dissociative group water-based fine particle dispersion ink. 2. The water-based fine particle dispersed ink according to claim 1, wherein the disperse dye subjected to the dispersion treatment has an average particle diameter of 0.3 μm or less. 3. The dispersion-processed disperse dye is from 0.01 to
The water system according to claim 2, which has a particle size distribution in the range of 1 μm.
Fine particle dispersed ink. 4. The aqueous fine particle dispersion ink according to claim 1, wherein the copolymerization is performed in an emulsified state. 5. The acid value of the water-soluble urethane polymer is 100.
The water-based fine particle dispersed ink according to claim 1, wherein 6. The water-based fine particle dispersed ink according to claim 1, wherein the weight ratio of the disperse dye and the water-soluble urethane polymer is in the range of 100: 30 to 100: 200. 7. The aqueous fine particle dispersion ink according to claim 1, wherein the pH is adjusted to a range of 4 to 9. 8. The aqueous fine particle dispersion ink according to claim 1, further containing a nonionic-anionic surfactant. 9. A contract further containing an alcohol amine.
The water-based fine particle-dispersed ink according to claim 1. 10. The ink is an ink jet ink.
The water-based fine particle component according to any one of claims 1 to 9.
Ink.