JP5154018B2 - Method for producing aqueous pigment ink composition and aqueous pigment ink composition - Google Patents

Description

  The present invention relates to a method for producing an aqueous pigment ink composition and an aqueous pigment ink composition produced by the method. More specifically, the present invention relates to a method for producing an aqueous pigment ink composition that can be suitably used in an ink jet printer, and an aqueous pigment ink composition produced by the method. More specifically, since the nozzles are not clogged when printing with an ink jet printer, a printed matter preferable in terms of print quality can be obtained, an appropriate drying speed of printing can be obtained, and an excellent color expression can be obtained. Relates to the composition.

Conventionally, many water-based pigment ink compositions for ink-jet printing using various solvents have been proposed. When a printed matter is produced using such a pigment ink composition by an ink-jet printer, the nozzle of the ink-jet printer is clogged. As a result, a printed matter that is not preferable in terms of print quality is obtained, or even if a printed matter is prepared using such an aqueous pigment ink composition, the color development is not always sufficient (for example, Patent Document 1). ).
Japanese Patent Laid-Open No. 5-247370

  The present invention has been made in order to solve the above-described problems. Since printing with an ink jet printer does not cause clogging of nozzles, a printed matter preferable in terms of print quality can be obtained, and the printing can be performed appropriately. An object of the present invention is to provide an aqueous pigment ink composition which can obtain a drying speed and is excellent in color development.

  As a result of intensive studies to achieve the above object, the present inventors have found that an excellent aqueous pigment ink composition can be obtained by using a solution having a specific composition as a mixed solution in which a colored pigment is dispersed. Completed the invention.

That is, the method for producing the aqueous pigment ink composition of the present invention comprises:
(I) (a) mixing a solution comprising a coloring pigment 100 parts by weight of (b) a pigment dispersant or the (b) pigment dispersing agent and (c) vinyl copolymer resins 5-300 parts by chloride and (d) a solvent In which a non-aqueous pigment dispersion (i) is produced , wherein (b) the pigment dispersant reacts with an acid-terminated polyester resin and a polyamine compound having two or more amino groups in one molecule. A process which is a polyester polyamide resin obtained by
(II) mixing the non-aqueous pigment dispersion (i) with 1 to 1000 parts by weight of the (c) vinyl chloride copolymer resin to produce a non-aqueous pigment ink (ii);
(III) A step of emulsifying and dispersing the non-aqueous pigment ink (ii) by mixing an aqueous solution of (e) 2 to 200 parts by mass of an emulsifier and ion-exchanged water,
Consists of.

  By using the water-based pigment ink composition of the present invention, nozzle clogging does not occur when printing with an ink jet printer, so that a printed matter preferable in terms of print quality is obtained, an appropriate drying speed of printing is obtained, and excellent Color expression is obtained.

  Below, the manufacturing method of the water-based pigment ink composition of this invention and the water-based pigment ink composition manufactured by this method are demonstrated concretely.

  Pigment Yellow 12, 13, 14, 17, 20, 24, 31, 55, 74, 83, 86, 93, 109, 110, 117 are used as the (a) colored pigment used in the aqueous pigment ink composition of the present invention. 125, 128, 129, 137, 138, 139, 147, 148, 150, 153, 154, 155, 166, 168, 180, 181, 185, Pigment Orange 16, 36, 38, 43, 51, 55, 59 61, 64, 65, 71, Pigment Red 9, 48, 49, 52, 53, 57, 97, 122, 123, 149, 168, 177, 180, 192, 202, 206, 215, 216, 217, 220 223, 224, 226, 227, 228, 238, 240, 244, 254, pigment violet 19, 23, 29 30, 32, 37, 40, 50, Pigment Blue 15, 15: 1, 15: 3, 15: 4, 15: 6, 22, 30, 64, 80, Pigment Green 7, 36, Pigment Brown 23, 25, 26, pigment black 7, 26, 27, 28, carbon black, titanium oxide, iron oxide, ultramarine, yellow lead, zinc sulfide, cobalt blue, barium sulfate, calcium carbonate, and the like. The blending amount of the pigment can be arbitrarily determined depending on the kind of the pigment to be used and the like, but is usually 0.1 to 15% by mass, preferably 0.5 to 10% by mass of the ink composition.

  As the pigment dispersant (b) used in the aqueous pigment ink composition of the present invention, acidic, basic, amphoteric and nonionic resins can be used. For example, a polyester polyamide resin having two or more amide groups in one molecule and having a number average molecular weight of 2,000 to 15,000 can be mentioned. The blending amount of the pigment dispersant is determined depending on the kind of the pigment used and the like, but is usually 0.1 to 15% by mass, preferably 0.5 to 10% by mass of the ink composition.

  A typical pigment dispersant is produced by reacting an acid-terminated polyester resin with a polyamine compound having two or more amino groups in one molecule. For example, Sol Sparse 32000, Sol Sparse 32500, Sol Sparse 32600, Sol Sparse 33500, Sol Sparse 34750, Sol Sparse 35100, Sol Sparse 37500, Dispersic 9077, etc. can be mentioned.

  In addition, when the number of amino groups is 1 or less per molecule, the pigment dispersibility is poor, which is not preferable. Further, when the number average molecular weight is less than 2,000, the pigment dispersion stability tends to decrease, and when the number average molecular weight exceeds 15,000, the dispersibility in the ink tends to decrease.

  As the binder resin used in the aqueous pigment ink composition for inkjet printing of the present invention, at least (c) a water-insoluble resin is used. In the present invention, such a water-insoluble resin is particularly preferably a vinyl chloride copolymer resin, and the vinyl chloride copolymer resin may be used alone, but other resins are used together with the vinyl chloride copolymer resin. You can also. The blending amount of the water-insoluble resin is determined in consideration of the ink adhesion, the viscosity of the ink composition, the surface tension, etc., but is usually 0.5 to 15% by mass of the ink composition, preferably 1 to 10% by mass.

  Various vinyl chloride copolymer resins can be used, and examples thereof include copolymer resins of vinyl chloride and other monomers such as vinyl acetate, vinylidene chloride, acrylic, and maleic acid. Preferred vinyl chloride copolymer resins include vinyl chloride vinyl acetate copolymer resins obtained by copolymerizing vinyl chloride and vinyl acetate, particularly copolymer resins having a weight average molecular weight of 50,000 or less.

  There is no restriction | limiting in particular as resin other than the said vinyl chloride copolymer resin, Any resin used for a normal ink composition can be used. For example, epoxy resin, phenol resin, novolak resin, acrylic resin, rosin-modified phenol resin, polyester resin, amino resin such as melamine, benzoguanamine, polyamide resin, polyester polyamide resin, cellulose diacetate, cellulose triacetate, nitrocellulose, cellulose nitrate, Cellulose ester resins such as cellulose propionate and cellulose acetate butyrate, cellulose ether resins such as methyl cellulose, ethyl cellulose, benzyl cellulose, trityl cellulose, cyanethyl cellulose, carboxymethyl cellulose, carboxyethyl cellulose, aminoethyl cellulose, vinyl acetate copolymer resins, etc. be able to.

  The solvent (d) used in the aqueous pigment ink composition for inkjet printing of the present invention is used as a medium in which (a) is dispersed in (b). The solvent is not particularly limited, and specifically, alcohols such as methyl alcohol and ethyl alcohol, ketones such as acetone and methyl ethyl ketone, ethers such as tetrahydrofuran and dioxane, esters such as ethyl acetate and ethyl lactate, ethylene Examples thereof include polyhydric alcohols such as glycol and diethylene glycol, and glycol ethers such as ethylene glycol monomethyl ether and diethylene glycol monomethyl ether.

  Examples of the lactone compound include γ-butyrolactone, γ-valerolactone, γ-caprolactone, ε-valerolactone, and mixtures thereof.

  (E) As an emulsifier used in the aqueous pigment ink composition of the present invention, anionic surfactants such as fatty acid salts and alkyl sulfate esters, nonionic interfaces such as polyoxyethylene alkyl ether and polyoxyethylene alkylphenyl ether Examples of the surfactant include a cationic surfactant, an amphoteric surfactant, and the like, and it is preferable to use an ethylene oxide propylene oxide block polymer.

  In addition, the aqueous pigment ink composition of the present invention can be adjusted to a pH of 6 to 11 with a basic compound such as an organic amine.

  In addition, the aqueous pigment ink composition of the present invention can contain a conductivity adjusting agent, and the blending amount of the conductivity adjusting agent is usually 0.1 to 10% by mass of the ink composition, preferably 0. 0.5 to 5% by mass.

Further, the water-based pigment ink composition of the present invention needs to have characteristics adapted to the ink jet printing method in the same manner as a normal ink composition for ink jet printing. For that purpose, the viscosity of the ink composition is set to 1 to 1. It is desirable that 100 cP (20 ° C.), surface tension be 2 × 10 ^{−2 to} 6 × 10 ⁻² N / m, and specific gravity be in the range of 0.8 to 1.2.

  Next, a method for producing an aqueous pigment ink will be described.

Although the manufacturing method of the non-aqueous pigment dispersion liquid of process (I) is not specifically limited, According to the following method, it can obtain efficiently. That is, (a) a pigment, (b) a pigment dispersant, and (d) a solvent are mixed and stirred, and then processed by a disperser to disperse the pigment into fine particles. Examples of the disperser used for the treatment include a paint shaker, a ball mill, a sand mill, and a nano mill. When (c) vinyl chloride copolymer resin is further added to the suspension and treated with a disperser, the pigment is coated with a water-insoluble resin, so that dispersion stability is improved and film properties such as water resistance are also improved. It tends to improve.

In step (II), (c) vinyl chloride copolymer resin is uniformly mixed with the non-aqueous pigment dispersion obtained in step (I).

In step (III), neutralizing agent in a non-aqueous pigment ink obtained in step (II), ion-exchanged water was added thereto, and (e) an emulsifier, obtained by emulsifying and dispersing an aqueous dispersion by 撹拌. Typical examples of the neutralizing agent include triethylamine, triethanolamine, dimethylethanolamine, monoethanolamine, N-methyldiethanolamine, N, N-dimethylethanolamine, morpholine and the like.

  The aqueous pigment ink can be prepared by filtering through a filter having a pore size of about 1/10 or less of the nozzle diameter of the ink jet printer to be used and purifying it.

  The aqueous pigment ink composition of the present invention can be used in various ink jet printers. As such an ink jet printer, for example, a method of ejecting an ink composition by a charge control method or an ink on demand method can be exemplified. The aqueous pigment ink composition of the present invention can be suitably applied particularly to printing by a large inkjet printer using a large format, for example, printing by an inkjet printer for the purpose of printing on an outdoor article such as a sign display. Further, the contrast is clear in the color graphic printing portion and the video recording drawing, and the reproducibility of the image is remarkably improved.

  The printed surface (ink composition) after inkjet printing is dried at room temperature to several hundred degrees C to form a dry film. In addition, about the base material used as the object of printing by this invention, if it does not deform | transform or change in quality on the conditions which dry a printing surface (ink composition), it will not restrict | limit in particular. Examples of such a substrate include the surface of a substrate such as metal, glass and plastic, paper coated with a resin on the surface, a transparent sheet for an overhead project, and outdoor articles such as a sign display.

  Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples.

[ Reference Example 1]
Carbon black pigment (trade name: Monarch (M) 1000: (manufactured by Cabot)) 100.0 parts by mass, pigment dispersant (trade name: Solsperse 32000: (Lubrisol)) 60.0 parts by mass, diethylene glycol diethyl ether 870 A non-aqueous pigment dispersion was obtained by treating the mixture of parts by mass with a nanomill filled with 80% of 0.5 mm diameter zirconia beads. In this dispersion, 120 parts by mass of binder 1 was dissolved to obtain a non-aqueous pigment ink. After this non-aqueous pigment ink was adjusted to pH 8.5 with dimethylethanolamine, 1850 parts by mass of ion-exchanged water and 10 parts by mass of an emulsifier (trade name: Emulgen 420 (manufactured by Kao Corporation)) were mixed and emulsified and dispersed. , 164 parts by mass of glycerin, 82 parts by mass of ethylene glycol, 56 parts by mass of 2-pyrrole, 58 parts by mass of Surfinol 104E, 16.85 parts by mass of antiseptic (trade name: Proxel XL2 (S): (manufactured by Avicia)) To obtain an aqueous pigment ink.

[ Reference Examples 2 to 4, Examples 1 to 2 and Comparative Examples 1 to 2 ]
An aqueous pigment ink containing the raw materials shown in Table 1 as components was prepared in the same procedure as in Reference Example 1.

(Materials in Table 1)
Color pigment:
Carbon black (trade name: Monarch (M) 1000, manufactured by Cabot)
Pigment dispersant:
SL32000 (trade name: Solsperse 32000, manufactured by Lubrizol)
Water-insoluble resin:
Vinyl chloride copolymer resin (trade name: VYHD, manufactured by Dow Chemical Company)
Vinyl chloride copolymer resin (trade name: Solvine M, manufactured by Nissin Chemical)
Binder 1 other than vinyl chloride copolymer resin (manufactured from 1,6-hexanediol, neopentyl glycol, isophthalic acid and trimellitic anhydride, 71.93 g of polyester having a hydroxyl number of 87 and an acid number of 30 was added to butyl cellosolve 28. 07g added resin solution)
emulsifier:
Emulgen 420 (trade name, manufactured by Kao Corporation)
RO-451 (trade name, manufactured by Nippon Emulsifier Co., Ltd.)
Solvent other:
Surfynol 104E (trade name, manufactured by Air Products)
Proxel XL2 (S) (trade name, manufactured by Avicia)

For the inks of Reference Examples 1 to 4, Examples 1 to 2 and Comparative Examples 1 to 2 , the dispersibility of the non-aqueous pigment dispersion (step I), the dispersibility of the aqueous pigment ink (step III), and storage of the aqueous pigment ink Stability (Step III), adhesion, water resistance, and alcohol resistance were measured by the following methods, respectively, and evaluated according to the following criteria.

<Dispersibility of non-aqueous pigment dispersion>
The particle size of the non-aqueous pigment dispersion was measured using Microtrac UPA (Nikkiso Co., Ltd.) and evaluated according to the following criteria.
A: The particle size distribution is within the range of 30 nm to 200 nm.
○: The particle size distribution is within the range of 30 nm to 500 nm.
X: When the upper limit of the particle size distribution exceeds 500 nm.

<Dispersibility of water-based pigment ink>
The particle diameter of the water-based pigment ink was measured using Microtrac UPA (manufactured by Nikkiso) and evaluated according to the following criteria.
A: The particle size distribution is within the range of 30 nm to 400 nm.
○: The particle size distribution is within the range of 30 nm to 500 nm.
X: When the upper limit of the particle size distribution exceeds 500 nm.

<Storage stability of water-based pigment ink>
The viscosity and particle size after the aqueous pigment ink was stored at 60 ° C. for 1 month were measured and evaluated according to the following criteria.
A: Changes in viscosity and particle size after storage for 1 month at 60 ° C. are within ± 5%.
○: Viscosity and particle size change after storage at 60 ° C. for 1 month are more than 5% and 10% or less, respectively.
X: Any of changes in viscosity and particle size after storage at 60 ° C. for 1 month exceeds 10%.

<Adhesion>
An image was printed with a large format inkjet printer, and a cello tape (registered trademark) (manufactured by NICHIBAN) having a width of 24 mm was adhered to the image, and then the tape was peeled off and evaluated visually.
A: No change at all.
○: Some ink peels off.
X: The ink peels and the substrate is visible.
The evaluation results were as shown in Table 1.

<Water resistance>
Images were printed with a large format ink jet printer, scraped with a cotton swab soaked in water, and visually evaluated.
A: No change at all.
○: Some ink peels off.
X: The ink peels and the substrate is visible.
The evaluation results were as shown in Table 1.

<Alcohol resistance>
Images were printed with a large format inkjet printer, and the images were rubbed with a cotton swab soaked in 50% by weight ethanol water and evaluated visually.
A: No change at all.
○: Some ink peels off.
X: The ink peels and the substrate is visible.
The evaluation results were as shown in Table 1.

As is clear from the evaluation results shown in Table 1, the inks of Examples 1 and 2 of the present invention obtained good evaluation results for each test item, and good inks were obtained.

Claims (3)

(I) (a) mixing a solution comprising a coloring pigment 100 parts by weight of (b) a pigment dispersant or the (b) pigment dispersing agent and (c) vinyl copolymer resins 5-300 parts by chloride and (d) a solvent In which a non-aqueous pigment dispersion (i) is produced , wherein (b) the pigment dispersant reacts with an acid-terminated polyester resin and a polyamine compound having two or more amino groups in one molecule. A process which is a polyester polyamide resin obtained by
(II) mixing the non-aqueous pigment dispersion (i) with 1 to 1000 parts by weight of the (c) vinyl chloride copolymer resin to produce a non-aqueous pigment ink (ii);
(III) A step of emulsifying and dispersing the non-aqueous pigment ink (ii) by mixing an aqueous solution of (e) 2 to 200 parts by mass of an emulsifier and ion-exchanged water,
A method for producing an aqueous pigment ink composition, comprising:
The method for producing an aqueous pigment ink composition according to claim 1, wherein the emulsifier (e) is an ethylene oxide propylene oxide block polymer. Claim 1 or 2 aqueous pigment ink composition characterized in that it is manufactured by the manufacturing method of the aqueous pigment ink composition according to.