JP2003113333A - Aqueous colored particle dispersion for ink-jet recording solution, method for producing the same and ink-jet recording solution - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an aqueous colored particle resin dispersion for ink-jet recording solution, which has high concentration, can provide an image, etc., having high-quality image quality free from bleeding and excellent water resistance and weather resistance standing even outdoor uses and has stable dispersion of colored resin particles in an aqueous medium, to provide a method for producing the same and to obtain an ink-jet recording solution. SOLUTION: This aqueous colored particle dispersion for ink-jet recording solution comprises a colored resin obtained by dispersing a pigment into a polyester resin prepared by neutralizing a part or the whole of the carboxy group of a carboxy group-containing polyester resin composed of oils and fats and/or a fatty acid, a polybasic acid and a polyhydric alcohol. This ink-jet recording solution comprises the dispersion. This method for producing the aqueous colored particle dispersion for ink-jet recording solution comprises mixing the solution of the colored resin with a basic compound-containing aqueous medium, neutralizing the carboxy group of the polyester resin and dispersing the colored resin into the aqueous medium.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention can be suitably used for an ink jet recording liquid for ejecting liquid droplets of a recording liquid (ink) from a recording head to record character information, images and the like on a recording medium such as paper. The present invention relates to an aqueous colored particle dispersion, a method for producing the same, and an inkjet recording liquid containing the aqueous colored particle dispersion as an essential component.

[0002]

2. Description of the Related Art In the field of conventional ink jet recording methods, as a recording liquid used for image formation, a recording liquid prepared by dissolving a dye in water and optionally adding an organic solvent or a water-soluble polymer. Has been widely used. However, in such a method, since the recording liquid is water-soluble, the water resistance of the formed image is poor, and since it easily penetrates into a fibrous recording medium such as paper, the image density is not high and bleeding or the like occurs. The current situation is that high quality images cannot be obtained due to problems. Furthermore, since the dye is used as a colorant, the weather resistance of images and the like is poor and it cannot be used for outdoor applications.

In order to solve the above-mentioned drawbacks of the prior art, a technique of encapsulating a dye or a pigment with a polyester resin to form colored resin particles is disclosed in JP-A-6-340835. However, the weather resistance of the polyester resin itself was not sufficient, and the water resistance of the obtained images and the like was also insufficient. Further, since the dye or pigment is not sufficiently encapsulated, the stability of the colored resin particles themselves is deteriorated, aggregation or sedimentation of the colored resin particles occurs, clogging of the recording head, image unevenness, etc. There was a problem.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide an image having a high density and high quality without bleeding, an image having water resistance and weather resistance that can be used outdoors, and coloring. Dispersion of resin particles in an aqueous medium is stable,
An object is to provide an aqueous colored particle dispersion for an inkjet recording liquid, a method for producing the same, and an inkjet recording liquid.

[0005]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that fats and / or fatty acids (a1), polybasic acids (a2), and polyhydric alcohols. Coloring in which the pigment (B) is dispersed in a polyester resin obtained by neutralizing a part or all of the carboxyl groups of the carboxyl group-containing polyester resin (A) containing (a3) as an essential component with a basic compound. The resin is characterized in that it is dispersed in a particulate form in an aqueous medium, the aqueous colored particle dispersion, good dispersion of the colored resin particles in the dispersion, there is no precipitation or aggregation, The inkjet recording liquid containing the dispersion as an essential component has a high concentration, high-quality image quality without bleeding, images having water resistance and weather resistance that can be used outdoors, and the like, and Polyester tree A colored resin solution prepared by dissolving a colored resin in which the pigment (B) is dispersed in (A) in an alcohol solvent and / or a glycol ether solvent is mixed with an aqueous medium containing a basic compound to prepare a polyester. The above-mentioned dispersion is easily prepared by a method for producing an aqueous colored resin particle dispersion characterized by neutralizing a part or all of the carboxyl groups in the resin (A) with a basic compound and dispersing the colored resin in an aqueous medium. The present invention has been completed by finding out that it can be manufactured.

That is, according to the present invention, a carboxyl group-containing polyester resin (A) containing, as essential components, an oil and / or a fatty acid (a1), a polybasic acid (a2) and a polyhydric alcohol (a3). Polyester resin (A) obtained by neutralizing a part or all of the groups with a basic compound
The colored resin in which the pigment (B) is dispersed in the polyester resin obtained by neutralizing a part or all of the carboxyl groups of the above with a basic compound is dispersed in an aqueous medium in the form of particles. And an aqueous colored particle dispersion for an inkjet recording liquid.

Further, the present invention provides a carboxyl group-containing polyester resin (A) containing, as essential components, oils and / or fatty acids (a1), polybasic acids (a2) and polyhydric alcohols (a3). A colored resin solution prepared by dissolving a colored resin in which the pigment (B) is dispersed in an alcohol solvent and / or a glycol ether solvent is mixed with an aqueous medium containing a basic compound to produce a polyester resin (A). A method for producing an aqueous colored particle dispersion for an inkjet recording liquid, comprising neutralizing a part or all of the carboxyl groups with a basic compound and dispersing the colored resin in an aqueous medium. It is a thing.

The present invention further provides an ink jet recording liquid containing the above-mentioned aqueous colored particle dispersion as an essential component.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention is described in detail below. The polyester resin (A) which is an essential component used in the present invention contains a carboxyl group containing fats and / or fatty acids (a1), polybasic acids (a2) and polyhydric alcohols (a3) as essential components. There is no particular limitation as long as it is a polyester resin. As the raw material used when preparing the polyester resin (A), various raw materials constituting the polyester resin can be used.

The fats and oils and / or the fatty acids (a1) used for producing the polyester resin (A) include, for example, milk fat, beef fat, pork oil, sardine oil, mackerel oil, tuna oil. , Shark liver oil, linseed oil, safflower oil, sunflower oil, soybean oil, corn oil, peanut oil,
Fats and oils such as cottonseed oil, sesame oil, rapeseed oil, olive oil, palm oil, coconut oil, castor oil;

The fatty acids are those obtained by saponification of the above-mentioned fats and oils, and specifically, palmitoleic acid, oleic acid, linoleic acid, linolenic acid, moroctic acid, eicosenoic acid, arachidonic acid, eicosapentaenoic acid, erucic acid. Unsaturated monobasic acids such as acids, docosapentaenoic acid, docosahexaenoic acid, cerakolenic acid and eleostearic acid; saturated monobasic acids such as caprylic acid, capric acid, lauric acid and myristic acid; and the like. The above oils and fats and fatty acids may be used alone or in combination of two or more.

The oil and fat and / or the fatty acid (a1) has a good dispersion of the pigment (B) when the pigment is dispersed in the polyester resin (A) and does not cause aggregation or precipitation of the colored resin particles with each other. The oil length is preferably 1 to 50% from the viewpoint of improving the storage stability of the dispersion and the inkjet recording liquid and imparting weather resistance to images and the like.
-30% is more preferable. Here, the oil length referred to in the present invention refers to the ratio of the resin to the oil in the polyester resin in which the polyester resin is modified with fats and / or fatty acids.

Examples of the polybasic acids (a2) include polybasic acids such as dicarboxylic acids, anhydrides thereof or reactive derivatives such as lower alkyl esters thereof.

Among the above polybasic acids (a2), examples of the dicarboxylic acid include maleic acid, maleic anhydride,
Fumaric acid, itaconic acid, itaconic anhydride, oxalic acid, malonic acid, succinic acid, succinic anhydride, dodecyl succinic acid, dodecyl succinic anhydride, dodecenyl succinic acid, dodecenyl succinic anhydride, adipic acid, azelaic acid, sebacic acid, Aliphatic dibasic acids such as decane-1,10-dicarboxylic acid; phthalic acid, phthalic anhydride, tetrahydrophthalic acid and its anhydride, hexahydrophthalic acid and its anhydride, tetrabromophthalic acid and its anhydride, tetra Chlorphthalic acid and its anhydride, Het's acid and its anhydride, Hymic acid and its anhydride, Isophthalic acid,
Terephthalic acid, cyclohexanedicarboxylic acid, 2,6-
Aromatic or alicyclic dibasic acids such as naphthalenedicarboxylic acid;

Further, as one of the polybasic acids having three or more functional groups, a carboxylic acid having three or more carboxyl groups in one molecule and a reactive derivative thereof can also be used. Typical examples thereof include trimellitic acid, trimellitic anhydride, methylcyclohexene tricarboxylic acid, methylcyclohexene tricarboxylic acid anhydride, pyromellitic acid and pyromellitic dianhydride.

These polybasic acids may be used alone or in combination of two or more.

Further, as the above-mentioned polybasic acids, those in which a part or all of the carboxyl group thereof is an alkyl ester, an alkenyl ester or an aryl ester can be used.

When the polyester resin (A) is prepared, as a raw material component, for example, dimethylolpropionic acid, dimethylolbutanoic acid, 6-hydroxyhexanoic acid, a hydroxyl group and a carboxyl group are contained in one molecule. Compounds having both or reactive derivatives thereof can also be used.

Further, a monobasic acid such as benzoic acid or p-tert-butylbenzoic acid can be used together within a range that does not impair the effects of the present invention.

Next, as the polyvalent alcohols (a3), for example, ethylene glycol, 1,2-propylene glycol, 1,4-butanediol, 1,5-pentanediol, Aliphatic diols such as 1,6-hexanediol, diethylene glycol, dipropylene glycol, triethylene glycol and neopentyl glycol; bisphenols such as bisphenol A and bisphenol F Bisphenol A alkylene oxide adducts such as ethylene oxide adducts of bisphenol A and propylene oxide adducts of bisphenol A; xylylene diglycol, 1,4-cyclohexane dimethanol, Aralkylene glycol such as hydrogenated bisphenol A
And alicyclic diols; and the like.

Compounds having three or more hydroxyl groups can also be used as the trifunctional or more polyhydric alcohols, and typical examples thereof include glycerin, trimethylolethane, trimethylolpropane, and sorbite.
1,2,3,6-hexanetetrol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, 2-methylpropanetriol, 1,3,5-trihydroxy Examples thereof include benzene and tris (2-hydroxyethyl) isocyanurate.

Further, the following polyepoxy compounds can also be used as polyfunctional alcohols having three or more functional groups. For example, ethylene glycol, hexanedio-
, Neopentyl glycol, trimethylolpropane, trimethylolethane, glycerin, pentaerythritol, sorbitol, hydrogenated bisphenol A, etc.
Polyglycidyl ethers of various aliphatic or alicyclic polyols;

Hydroquinone, catechol, resorcin,
Polyglycidyl ethers of compounds containing 2 of various phenolic hydroxyl groups such as bisphenol A, bisphenol S, bisphenol F; ethylene oxide or propylene oxide addition of compounds containing 2 of the above phenolic hydroxyl groups Diglycidyl ethers of body derivatives;

Polyglycidyl ethers of various polyether polyols such as polyethylene glycol, polypropylene glycol and polytetramethylene glycol;
Polyglycidyl ethers of tris (2-hydroxyethyl) isocyanurate; polyglycidyl of aliphatic or aromatic polycarboxylic acids such as adipic acid, butanetetracarboxylic acid, propanetricarboxylic acid, phthalic acid, terephthalic acid and trimellitic acid Esters;

Butadiene, hexadiene, octadiene, dodecadiene, cyclooctadiene, α-pinene,
Bisepoxides of hydrocarbon-based dienes such as vinylcyclohexene; alicyclic polyepoxy compounds such as bis (3,4-epoxycyclohexylmethyl) adipate and 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate; Epoxidized products of diene polymers such as polybutadiene and polyisoprene; and the like.

These polyvalent alcohols may be used alone or in combination of two or more. Further, in addition to these polyvalent alcohols, monovalent higher alcohols such as stearyl alcohol can be used together within the range not impairing the features of the present invention.

Next, a method for preparing the polyester resin (A) will be described. Various methods can be used for preparing the polyester resin (A). For example, the oil and / or fatty acid (a1) as a raw material component, the polybasic acid (a2) and the polyhydric alcohol (a2) are used. In general, a method of dehydrating and condensing) under heat in a nitrogen atmosphere is used. As the apparatus used at that time, for example, a batch-type production apparatus such as a reaction vessel equipped with a nitrogen inlet, a thermometer, a stirrer, and a rectification column can be preferably used, and a degassing port is provided. An extruder, a continuous reaction device, a kneader, or the like can also be used. Further, during the dehydration condensation, the esterification reaction can be promoted by reducing the pressure of the reaction system, if necessary. Further, in order to accelerate the esterification reaction, a known and commonly used catalyst may be added.

The polyester resin (A) can be used without particular limitation as long as it is a carboxyl group-containing polyester resin containing oils and / or fatty acids (a1), polybasic acids (a2) and polyhydric alcohol (a3) as essential components. I can, but
Since the colored resin in which the pigment (B) is dispersed is stably dispersed in the form of particles in an aqueous medium, the polyester resin (A) contains a carboxyl group and an alkyl group having 4 to 20 carbon atoms and / or carbon. It is preferably a polyester resin having an alkenyl group having 4 to 20 atoms.

An alkyl group having 4 to 20 carbon atoms and /
Or, as the alkenyl group having 4 to 20 carbon atoms, for example, butyl group, isobutyl group, sec-butyl group, t
Examples thereof include alkyl groups or alkenyl groups such as ert-butyl group, dodecyl group and dodecenyl group. These alkyl groups or alkenyl groups may be linear or branched.

The method for preparing a polyester resin having a carboxyl group and an alkyl group having 4 to 20 carbon atoms and / or an alkenyl group having 4 to 20 carbon atoms is not particularly limited. For example, in the case of a carboxyl group The carboxyl group derived from the polybasic acids constituting the polyester resin can be used as it is, and in the case of an alkyl group and / or an alkenyl group, polyvalent alcohols having the alkyl group or the alkenyl group (epoxy compounds are also available. And a polybasic acid having an alkyl group or an alkenyl group (including polybasic acid anhydride) as a raw material and prepared by utilizing dehydration condensation or addition reaction.

Further, as the polyester resin having a carboxyl group and the above-mentioned alkyl group and / or alkenyl group, the terminal carboxyl group of the polyester resin having a carboxyl group at the end is an alkyl group and / or a carbon atom having 4 to 20 carbon atoms. The terminal hydroxyl group of the polyester resin (A1) having a terminal structure formed by ring-opening addition of an aliphatic monoepoxy compound having an alkenyl group of 4 to 20 atoms or a terminal hydroxyl group of a polyester resin having a hydroxyl group at the terminal,
Examples thereof include a polyester resin (A2) having a terminal structure obtained by ring-opening addition of an acid anhydride having an alkyl group having 4 to 20 carbon atoms and / or an alkenyl group having 4 to 20 carbon atoms. These polyester resins have an alkyl group having 4 to 20 carbon atoms and / or an alkenyl group having 4 to 20 carbon atoms, and a hydroxyl group or a carboxyl group at their ends to disperse the pigment in an aqueous medium and the pigment. Is preferable and the weather resistance is improved, and the polyester resin (A
1) is particularly preferable.

The method for producing the polyester resin (A1) is as follows:
There is no particular limitation, but for example, under conditions where a polyester resin having a carboxyl group at the terminal does not substantially undergo a condensation reaction and only an addition reaction occurs, for example, a carder
An alkyl group having 4 to 20 carbon atoms such as E10 (glycidyl ester of branched fatty acid manufactured by Shell Chemical Co.) and /
Alternatively, there may be mentioned a production method in which an aliphatic monoepoxy compound having an alkenyl group having 4 to 20 carbon atoms is subjected to a ring-opening addition reaction at a ratio such that the carboxyl group becomes excessive.

Examples of the aliphatic monoepoxy compound having an alkyl group having 4 to 20 carbon atoms and / or an alkenyl group having 4 to 20 carbon atoms used here include:
Examples thereof include monoglycidyl esters of saturated or unsaturated fatty acids such as castor oil fatty acid, coconut oil fatty acid, soybean oil fatty acid, and tung oil fatty acid, and monoglycidyl esters of branched fatty acids such as isononanoic acid and versatic acid.

The polyester resin (A1) is more preferably a polyester resin having a terminal structure represented by the following general formula (1) and / or (2).

[Chemical 3] (R in the formula represents an alkyl group having 4 to 20 carbon atoms or an alkenyl group having 4 to 20 carbon atoms.)

The method for producing the polyester resin (A2) is not particularly limited, but for example, a polyester resin having a hydroxyl group is heated and melted, and the acid anhydride having an alkyl group or an alkenyl group is added thereto. However, a method of ring-opening addition may be used.

Examples of the acid anhydride having an alkyl group or an alkenyl group used here include n-butyl succinic anhydride, n-pentyl succinic anhydride, neopentyl succinic anhydride, n-hexyl succinic anhydride and n-heptyl. Succinic anhydride, n-octyl succinic anhydride, isooctyl succinic anhydride, 2-ethylhexyl succinic anhydride, n-dodecyl succinic anhydride, isododecyl succinic anhydride, n-
Examples thereof include dodecenyl succinic anhydride, isododecenyl succinic anhydride, 6-butyl-1,2,4-benzenetricarboxylic acid anhydride, 6-n-octyl-1,2,4-benzenetricarboxylic acid anhydride and the like. Of these, isododecyl succinic anhydride and dodecenyl succinic anhydride are particularly preferable.

Further, the above polyester resin (A2)
In the production of, it is necessary to carry out a ring-opening addition reaction under the condition that the carboxyl group formed by ring-opening of the acid anhydride does not undergo a dehydration condensation reaction with another hydroxyl group, and a ring-opening addition reaction that does not cause a dehydration condensation reaction. The reaction conditions are not particularly limited, but for example, the reaction system in which the temperature of the ring-opening addition reaction is lowered to about 200 ° C. from the temperature of about 240 ° C. at which dehydration occurs, the stirring rotation speed is reduced to suppress the evaporation of water If an inert gas such as nitrogen gas is introduced, the amount is minimized.If a depressurization reaction is performed and dehydration condensation is performed, the depressurization reaction is stopped and the reaction is returned to normal pressure. The method of is common.

Next, the properties of the polyester resin (A) will be described. The polyester resin (A) has good pigment dispersion when a pigment is dispersed to prepare a colored resin,
Gel permeation chromatography (G) is used because the colored resin particles can be stably dispersed in an aqueous medium without being precipitated or aggregated, and can impart water resistance and weather resistance to images and the like.
PC) method has a weight average molecular weight of 5,000 to 300,
It is preferably in the range of 000, and further 7,000
It is preferably in the range of 0 to 100,000.

In the polyester resin (A), a part or all of the carboxyl groups in the resin are neutralized with a basic compound, whereby the colored resin can be easily made into particles, and the particles are in an aqueous medium. Exists stably. Therefore, it is essential that the polyester resin (A) has a carboxyl group, but the acid value of the polyester resin (A) is
The range of 5 to 100 mgKOH / g is preferable, and the range of 10 to 50 mgKOH / g is particularly preferable.

As the basic compound used for neutralizing a part or all of the carboxyl groups in the polyester resin (A), alkali compounds such as sodium hydroxide, potassium hydroxide and lithium hydroxide, their carbonates, Those acetates; ammonia water; alkylamines such as methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine and triethylamine; alkanolamines such as diethanolamine can be used. These may be used alone or in combination of two or more. Of these, ammonia water is preferred.

The basic compound is used in an amount of 1.0 to 1.0 with respect to the equivalent amount of the carboxyl group in the polyester resin (A).
2.0 times equivalent is preferable, and 1.05-1.3 times equivalent is more preferable.

Next, the pigment (B) used in the present invention will be described. In the present invention, the “pigment” is a colorant, which is a fine particle solid insoluble in water, oil, organic solvent and the like. Typical examples of the pigment (B) that can be used include, but are not limited to, polycyclic pigments such as azo type, phthalocyanine type, perylene type, quinacridone type; titanium oxide, zinc oxide, iron oxide, Metal oxides such as cobalt oxide; various carbon blacks produced by thermal black method, acetylene black method, channel black method, furnace black method, lamp black method and the like. These may be used alone or in combination of two or more.

The amount of the pigment (B) used in the production method of the present invention is not particularly limited, but in the colored resin it is possible to disperse the colored resin in the aqueous medium well and to obtain a high quality image. The content of the pigment (B) is preferably in the range of 0.2 to 40 parts by weight, with the total weight of the polyester resin (A) and the pigment (B) being 100 parts by weight.

In the present invention, other components may be added in addition to the polyester resin (A) and pigment (B) which are essential components constituting the aqueous colored particle dispersion. Other components that can be used include, for example, antioxidants, ultraviolet absorbers, light stabilizers, leveling agents, additives such as pigment dispersants, acrylic resins, melamine resins, polystyrenes, polyethylenes, polypropylenes, polycarbonates. And resins such as petroleum resin, polyethylene oxide, and polypropylene oxide.

Next, the production method of the present invention will be described more specifically. As a preferred method for producing the aqueous colored particle dispersion for an inkjet recording liquid of the present invention, for example, step (a) polyester resin (A), pigment (B) and, if necessary, additives such as water retention agent, A dispersion aid and the like are mixed together, and the mixture is mixed in the polyester resin (A) using various uniaxial or biaxial kneaders or extruders, pressure kneaders, two or three rolls, etc. Coloring process in which the pigment (B) is dispersed, Process (b) Coloring process in which the coloring resin is dissolved in an alcohol and / or glycol ether solvent to obtain a colored resin solution The resin solution and, if necessary under pressure, containing a basic compound, and mixed with a heated aqueous medium, the colored resin is dispersed in the aqueous medium in the form of particles by mechanical means, and thereafter, Preferably by quick freezing , To obtain an aqueous colored particle dispersion, consisting of.

The alcohol and / or used in the step (b)
Alternatively, the glycol ether type solvent can be used without particular limitation as long as it can dissolve the polyester resin (A).

Typical examples of these alcohols are methanol, ethanol, propanol, butanol, amyl alcohol, hexanole and octanole.
, Cyclohexanol, benzyl alcohol, and other monovalent alcohols, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol
And glycols such as glycerin. In the present invention, the glycol ether solvent is a generic name for alkyl ethers of glycols or alkyl ether esters of glycols. The glycol ether solvent is not particularly limited as long as it can dissolve the polyester resin (A), and ethylene glycol
Rumonomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol dimethyl ether, ethylene glycol
Rudiethyl ether, ethylene glycol dibutyl ether
Ter, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether
Ter, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol
Examples thereof include rumonobutyl ether, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, and propylene glycol monoethyl ether acetate. These alcohol and / or glycol ether type solvents may be used alone or in combination of two or more kinds. Of these, triethylene glycol monobutyl ether is preferred.

The above alcohol and / or glycol ether
Since the tellurium solvent can be used as it is as a component of the inkjet recording liquid, it is not necessary to remove these solvents in the process of the production method of the present invention, the production process is significantly simplified, and -It also has a significant cost advantage.

In the present invention, the device that can be used as a mechanical means for dispersing the colored resin solution in an aqueous medium is not particularly limited, but an ordinary device capable of mechanical stirring can be used. You can The apparatus is not particularly limited, but representative examples of commercially available products include Manton-Gorin high-pressure homogenizer (Gorin Co., Ltd.), continuous ultrasonic homogenizer (Nippon Seiki Co., Ltd.), and nanomizer (nanomizer). -Company), Microfluidizer (Mizuho Kogyo Co., Ltd.), Harrel-type homogenizer, Slasher (Mitsui Mining Co., Ltd.), Cavitron (Yourotech Co., Ltd.), and the like. "Cavitron" which is a continuous disperser of the type is preferred.

In the rotary type continuous dispersion device Cavitron, the stator having the ring-shaped projections having the slits and the rotor having the ring-shaped projections having the slits mesh with each other with a space therebetween. As described above, it is a rotary type continuous dispersion device having a structure provided on the same axis, and the colored resin solution and an aqueous medium containing a basic compound are supplied to the stator and the central portion of the rotor of the dispersion device. The colored resin can be dispersed in the aqueous medium in the form of particles by allowing the colored resin to flow in the direction from the central portion to the outer periphery through the slits and the gap while rotating the rotor.

The manufacturing method of the present invention using the above-mentioned rotary type continuous dispersing device will be described in detail below with reference to the drawings.

FIG. 1 is a perspective view showing an example of a stator of a rotary type continuous dispersion device used in the manufacturing method of the present invention, and FIG. 2 is a rotor of a rotary type continuous dispersion device used in the manufacturing method of the present invention. FIG. 3 is a cross-sectional view showing an example of a main part of the rotary type continuous dispersion device used in the manufacturing method of the present invention, and FIG. 4 is a side view of the AA ′ cross section of FIG. 3. It is a figure showing the combination state of a stator projection and a rotor projection at the time of standing.

As shown in FIGS. 1 to 4, the stator 1 of the rotary type continuous dispersion device is installed at the center and has the liquid inlet 2 at the center. On the circular surface of the stator 1, there are one or two protrusions 3 arranged in a ring shape in a concentric circle with the stator.
It is provided in a multi-stepped shape having more than steps, and therefore, a circumferential groove 4 is formed in the gap between the protrusions. A plurality of slits 5 are formed between the protrusions.

A drive shaft 6 is installed at the center of the inner wall facing the stator 1 in this dispersing device, and there is a rotor 7 connected to the drive device and rotated. The rotor 7 is fixed to the tip of the drive shaft 6 so that the rotor 7 is parallel to the stator 1 and the centers thereof are aligned. On the surface of the rotor 7 facing the stator 1, projections 8 arranged concentrically with the rotor on a ring are provided in a single step or in a multistep shape of two or more steps. Therefore, like the stator, an annular groove 9 is formed in the gap between the protrusions. A plurality of slits 10 are formed between the protrusions.

The stator 1 and the rotor 7 are arranged so that the projection 3 of the stator 1 and the projection 8 of the rotor 7 maintain a slight gap.
It is used in the occluded state.

An aqueous medium containing the colored resin solution and the heated basic compound is supplied to the liquid inlet portion 2 of this dispersing device, and a mixture of these is rotated by the rotor 7.
It enters into the slit 10 of the protrusion 8 of the rotor 7 located at the innermost side, is discharged from the outside of the protrusion 8 of the rotor 7 into the annular groove 9 by centrifugal force, and then the stator 1 located at the innermost side.
Goes into the slit 5 of the protrusion 3 of FIG. Furthermore, this slit 5
The mixture that has flowed into is extruded into the annular groove 4 of the stator 1.

In this way, the mixture is subjected to centrifugal force due to the rotation of the rotor 7, and flows in the slit from the liquid inlet to the outlet. On the other hand, due to the deviation of the slits between the rotor 7 and the stator 1, the centrifugal flow of the mixture is contained and released repeatedly to generate a differential pressure. Further, a shearing force acts on the mixed liquid in the minute gap between the rotor 7 and the stator 1. The flow from the center to the outer circumferential direction and the flow in the circumferential direction collide at a right angle, which causes a strong stirring and crushing effect, whereby the colored resin in the colored resin solution becomes particulate in the aqueous medium. Dispersion gives an aqueous colored particle dispersion.

The rotation speed of the rotor 7 of this dispersing device is controlled by a drive motor connected to the drive shaft. The larger the rotational speed and the higher the peripheral speed, the larger the centrifugal force and the shearing force, and the smaller the particle size of the colored resin dispersed in the aqueous medium becomes. The average particle size is 100 nm using a rotor with a diameter of 10 cm.
In the case of producing the following aqueous colored particle dispersion for inkjet recording liquid, the preferable rotation number is 3,000 to 10,000.
It is 0 rpm.

When such a rotary continuous dispersing device is used, it is preferable to install a jacket for keeping heat in order to maintain good fluidity of the colored resin solution. Then, the temperature in the dispersing device is controlled to a constant temperature by balancing the temperature of the colored resin solution, the temperature of the aqueous medium to be supplied, and the heat retaining effect of the jacket and the amount of heat generated by shearing in the device. It

The pressure in the dispersing device is determined by the vapor pressure of the aqueous medium in the device and the discharge pressure of the rotor rotating at high speed. Further, for taking out the dispersion obtained by cooling the aqueous dispersion of the colored resin solution, an automatic pressure control valve is provided at the take-out port to keep the internal pressure constant and continuously disperse the dispersion under atmospheric pressure. It is preferable to take it out.

Next, the properties of the aqueous colored particle dispersion of the present invention will be described. The aqueous colored particle dispersion of the present invention is one in which the colored resin in which the pigment is dispersed in the polyester resin is stably present in the form of particles in the aqueous medium. The weight average particle diameter of the resin particles is 5 to 1000 nm (nanometer) in order to prevent clogging of the recording head.
Is preferably in the range, and more preferably in the range of 10 to 100 nm.

The aqueous medium used in the present invention may be any liquid containing water as a main component, and as a component other than water,
Various water-soluble salts, water-insoluble salts, polyvinyl alcohol
, Water-soluble polymers such as carboxymethyl cellulose, hydroxymethyl cellulose, polyacrylic acid, polymethacrylic acid, various surfactants, methanol, ethanol
A water-soluble solvent such as alcohol, diacetone alcohol, acetone, ethylene glycol or diethylene glycol may be contained.

Next, the ink jet recording liquid of the present invention will be described. The ink jet recording liquid of the present invention is prepared by using the above aqueous colored particle dispersion as an essential component and further adding various additives and the like as necessary. As these additives, wetting agents such as polyhydric alcohols, various surfactants as surface tension adjusting agents, defoaming agents such as silicone compounds, and the like can be suitably used.

[0064]

EXAMPLES Next, the present invention will be specifically described with reference to synthesis examples, examples and comparative examples. However, the technical scope of the present invention is not limited to the following examples. In the examples, "part" and "%" are based on weight unless otherwise specified. The weight average molecular weight is measured by GPC using Sho
dex GPC SYSTEM-21 [Showa Denko KK
Manufactured] (the same applies hereinafter).

Synthesis Example 1 [Synthesis of Polyester Resin (A)] An ethylene oxide adduct of bisphenol A (in an inner volume of 5 liter flask equipped with a stirrer, a nitrogen inlet tube, a temperature sensor, and a rectification column) Average addition mole number 2.2, hydroxyl value 360 mg KOH / g) 1511 parts, diethylene glycol 163 parts, 1,4-cyclohexane dimethano-
169 parts of coconut oil and 163 parts of coconut oil fatty acid were charged, the temperature was raised to 130 ° C. over 1 hour while introducing nitrogen gas into the gas phase in the flask, and it was confirmed that the contents were dissolved. , 1.5 parts of dibutyltin oxide and 1,241 parts of isophthalic acid were added, and the temperature was raised to 240 ° C. over a further 5 hours. Then, the reaction was carried out at the same temperature for 6 hours to prepare a polyester resin intermediate having an acid value of 5.2 mgKOH / g and a softening point of 110 ° C. according to the ring and ball method. Next, 125 parts of dodecenyl succinic anhydride was added at the same temperature, and finally the weight average molecular weight by the GPC method was 15,
At 600, the acid value is 13.7 mg KOH / g and the oil length is 5.
5% polyester resin was obtained. This is abbreviated as polyester resin (a-1).

Synthesis Example 2 (Same as above) In a flask having an internal capacity of 5 liters equipped with a stirrer, a nitrogen inlet tube, a temperature sensor, and a rectification column, an ethylene oxide adduct of bisphenol A (average number of moles added: 2. 2, hydroxyl value 360 mgKOH / g) 1511 parts, diethylene glycol 163 parts, 1,4-cyclohexanedimethanol 169 parts, and coconut oil fatty acid 163 parts were charged, while introducing nitrogen gas into the gas phase in the flask. It took 1 hour to raise the temperature to 130 ° C., and after confirming that the contents were dissolved, 1.5 parts of dibutyltin oxide, 600 parts of terephthalic acid and 641 parts of isophthalic acid were added,
The temperature was raised to 240 ° C. over a further 5 hours. Then, the mixture was reacted at the same temperature for 4 hours to give an acid value of 24.0 mg KO.
H / g, when the softening point by the ring and ball method reached 90 ° C,
135 parts of KURURA E10 [Glycidyl ester of branched fatty acid (10 carbon atoms) manufactured by Shell Chemical Co.] was added, and the reaction was continued for 30 minutes at the same temperature, and finally GPC
Has a weight average molecular weight of 8,000 and an acid value of 13.
A polyester resin having 0 mgKOH / g and an oil length of 5.5% was obtained. This is abbreviated as polyester resin (a-2).

Synthesis Example 3 [Synthesis of polyester resin (A ') for comparison] In a flask having an internal volume of 5 liters equipped with a stirrer, a nitrogen inlet tube, a temperature sensor, and a rectification column, ethylene of bisphenol A was added. Oxide adduct (average number of moles added 2.2, hydroxyl value 360 mgKOH / g) 1936 parts, 1,4-cyclohexanedimethanol 188 parts were charged, and nitrogen gas was introduced into the gas phase in the flask for 1 hour. The temperature was raised to 130 ° C, and after confirming that the contents were dissolved, 1.5 parts of dibutyltin oxide and 99 parts of terephthalic acid were added.
7 parts and 117 parts of isophthalic acid were added, and the temperature was raised to 240 ° C. over a further 5 hours. Next, the mixture was reacted at the same temperature for 6 hours to prepare a polyester resin intermediate having an acid value of 4.4 mgKOH / g and a softening point of 117 ° C. according to the ring and ball method. Then, dodecenyl succinic anhydride 12 at the same temperature
5 parts were added, and finally a polyester resin having a weight average molecular weight of 16,000 and an acid value of 12 mgKOH / g was obtained by the GPC method. This is a polyester resin (a'-
Abbreviated as 1).

Synthesis Example 4 (same as above) In a flask having an internal volume of 5 liters equipped with a stirrer, a nitrogen inlet tube, a temperature sensor, and a rectification column, an ethylene oxide adduct of bisphenol A (average number of moles added: 2. 2, hydroxyl value 360mgKOH / g) 2018 parts were charged, and while introducing nitrogen gas into the gas phase in the flask, the temperature was raised to 130 ° C over 1 hour, and after confirming that the contents were dissolved, Dibutyltin oxide (1.5 parts) and terephthalic acid (857 parts) were added, and the temperature was raised to 2 after 5 hours.
Raised to 40 ° C. Next, 95 parts of isophthalic acid was added and reacted at the same temperature for 6 hours. Finally, the weight average molecular weight by GPC method was 15,600 and the acid value was 11.8 mg.
A polyester resin having KOH / g and a softening point of 116 ° C. according to the ring and ball method was obtained. This is abbreviated as polyester resin for comparison (a'-2).

Example 1 900 parts of polyester resin (a-1) and 100 parts of carbon black [MA-100 manufactured by Mitsubishi Chemical Co., Ltd.] were premixed with a Henschel mixer and then a twin-screw continuous kneader (barrel). Melt kneading was performed at a temperature of 100 ° C.) to obtain a colored resin.
Next, the colored resin 50 was placed in a flask having an internal volume of 2 liters.
0 parts and triethylene glycol monobutyl ether 25
0 part was charged and the temperature was raised to 80 ° C. with stirring to obtain a colored resin solution. The colored resin solution was heated to 80 ° C. and transferred to Cavitron CD1010 (rotary continuous dispersion device manufactured by Eurotech) at a rate of 100 g / min. Into a separately prepared aqueous medium tank, a 4.1% concentration triethylamine aqueous solution prepared by diluting triethylamine with ion-exchanged water was placed, heated to 80 ° C. in a heat exchanger, and the above colored resin solution was added at a rate of 0.1 liter / min. At the same time, it was transferred to the cavitron, and the cavitron was rotated at a rotor speed of 7500.
By operating under the conditions of rpm, an aqueous colored particle dispersion having a solid content of 33.0% was obtained.

To 80 parts of this aqueous colored particle dispersion, 7 parts of glycerin, 12.5 parts of ion-exchanged water, and Demol N [Naphthalene sulfonic acid type surfactant manufactured by Kao Corporation] 0.5 were added.
Parts were added and mixed to obtain an inkjet recording liquid. The weight average particle diameter of the colored resin dispersed in the ink jet recording liquid in a particulate form was 56 nm (nanometer). This is abbreviated as inkjet recording liquid (J-1).

Examples 2 to 4 and Comparative Examples 1 and 2 In the same manner as in Example 1 except that the polyester resin and pigment (carbon black) were used in the composition shown in Table 1,
Aqueous colored particle dispersion for inkjet recording liquid and inkjet recording liquid (J-2 to J-4, and j-1 to j
-2) was prepared.

[0072]

[Table 1]

Footnote KB123 of Table 1: Copper Phthalocyanine Nimble-type blue pigment "KET BLUE 12" manufactured by Dainippon Ink and Chemicals, Inc.
3 ”. TYHG: Benzimidazolone type yellow pigment of Clariant Japan KK TOM E02: Quinacridone red pigment manufactured by Clariant Japan KK

Test Examples 1-4 and Comparative Test Examples 1-2 Ink jet recording liquids (J-1)-(J-4) and (j-1) -prepared in Examples 1-4 and Comparative Examples 1-2. (J
-2) (measurement of weight average particle size, stability of recording liquid, evaluation of print image quality, evaluation of water resistance, evaluation of light resistance,
Evaluation of easiness of clogging of recording head) was performed as follows. The results are shown in Tables 2 and 3.

(1) Measurement of weight average particle diameter; Microtrac UPA150 (Leeds plus Nort)
The value (nm) of the weight average particle diameter was determined using a light scattering type particle size distribution meter manufactured by hlop.

(2) Evaluation of stability of recording liquid: The inkjet recording liquid was evaluated by the weight average particle diameter after storing at 70 ° C. for 14 days. The closer this value is to the initial value, the better the storage stability.

(3) Evaluation of print image quality: Using an ink jet printer-MJ-830C manufactured by EPSON, Japanese characters (Mincho, 14 points) mixed with Chinese characters were printed on A4 size plain paper, and the sharpness of the characters was improved. And the degree of whisker-like bleeding was visually evaluated on a scale of 5 according to the following criteria. 5: Clear and no bleeding. 4: Almost clear but partially bleeding. 3: Complex kanji is unclear. 2: There are many blurs in the kana characters. 1: Blurred overall.

(4) Evaluation of water resistance: Plain paper printed at the time of evaluation of print image quality was left at 20 ° C. for 24 hours, then immersed in still water for 1 minute, pulled up, and naturally dried, and then printed image. Was visually evaluated on a scale of 5 according to the following criteria. 5: Clear and almost no bleeding. 4: Some bleeding is observed. 3: The image area is widened. 2: It is difficult to read the characters. 1: Almost all characters disappeared.

(5) Evaluation of weather resistance: Using a test piece solidly printed on plain paper, xenon weather meter-Ci35A
[Accelerated weathering tester manufactured by Atlas, irradiation intensity 0.5 J / sec / m ² , black panel temperature 63.
C., relative humidity 55%] was used to evaluate the color difference (ΔE) between the test piece and the unirradiated test piece after 150 hours of continuous irradiation.
The larger this value is, the worse the weather resistance is.

(6) Evaluation of easiness of clogging of recording head; ink jet printer (MJ-830 manufactured by EPSON)
After continuous printing for 10 minutes with C), stop the printer,
It was left for 10 days in an environment of 40 ° C. and 25% relative humidity.
After leaving, the printing was restarted, and the number of recovery operations required until printing with the same quality as before leaving was evaluated. The larger the number of times, the more the recording head is clogged.

[0081]

[Table 2]

[0082]

[Table 3]

As shown in Examples and Comparative Examples, when an ink jet recording liquid comprising the aqueous colored particle dispersion of the present invention is used, a high quality printed image can be obtained, and the water resistance and weather resistance of the image can be obtained. It is clear that the performance is also good. Further, the ink jet recording liquid of the present invention has good storage stability, hardly causes clogging of the recording head, and is extremely useful, and can be used for writing instruments such as fountain pens and water-based ball pens.

[Brief description of drawings]

FIG. 1 is a perspective view showing an example of a stator of a rotary type continuous dispersion device used in the present invention.

FIG. 2 is a perspective view showing an example of a rotor of the rotary type continuous dispersion device used in the present invention.

FIG. 3 is a cross-sectional view showing an example of a main part of a rotary continuous dispersion device used in the present invention.

FIG. 4 is a diagram showing a combined state of a stator protrusion and a rotor protrusion when the AA ′ portion of FIG. 3 is viewed from the side surface.

[Explanation of symbols]

1 stator 2 liquid inlet 3 Stator protrusion 4 Stator circumferential groove 5 Stator protrusion slit 6 Rotor drive shaft 7 rotor 8 Rotor protrusion 9 Rotor circumferential groove 10 Rotor protrusion slit

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Shinka Shirai             3-1-9 Nijigaoka, Aso-ku, Kawasaki City, Kanagawa Prefecture             501 F-term (reference) 2C056 EA13 FC01                 2H086 BA55 BA59 BA60                 4J037 AA02 AA08 AA11 AA15 AA22                       CA08 CB04 CB07 CC24 CC29                       DD11 DD23 EE28 EE43 EE48                       FF15 FF23                 4J039 AE06 AF05 BA04 BA13 BA35                       BA37 BA38 BC39 BC60 BE01                       CA06 EA34 EA38 EA44 EA47                       GA24

Claims (11)

[Claims] 1. A part of a carboxyl group of a carboxyl group-containing polyester resin (A) containing, as essential components, an oil and / or a fatty acid (a1), a polybasic acid (a2) and a polyhydric alcohol (a3). An inkjet recording liquid, characterized in that a colored resin in which the pigment (B) is dispersed in a polyester resin obtained by neutralizing all or all of them with a basic compound is dispersed in the aqueous medium in the form of particles. Aqueous colored particle dispersion. 2. The polyester resin (A) is a polyester resin having a carboxyl group and an alkyl group having 4 to 20 carbon atoms and / or an alkenyl group having 4 to 20 carbon atoms. Aqueous colored particle dispersion for inkjet recording liquid. 3. The polyester resin (A) is an aliphatic compound in which a terminal carboxyl group of a polyester resin having a terminal carboxyl group has an alkyl group having 4 to 20 carbon atoms and / or an alkenyl group having 4 to 20 carbon atoms. The aqueous colored particle dispersion for inkjet recording liquid according to claim 1, which is a polyester resin having an acid value of 5 to 100 mgKOH / g and having a terminal structure obtained by ring-opening addition of a monoepoxy compound. 4. The inkjet according to claim 1, wherein the polyester resin (A) is a polyester resin having an acid value of 5 to 100 mgKOH / g and having a terminal structure represented by the following general formulas (1) and / or (2). Aqueous colored particle dispersion for recording liquid. [Chemical 1] (R in the formula represents an alkyl group having 4 to 20 carbon atoms or an alkenyl group having 4 to 20 carbon atoms.) 5. The polyester resin (A) has an oil length of 1
The water-based colored particle dispersion for inkjet recording liquid according to any one of claims 1 to 4, which is -50%. 6. A pigment (B) is contained in a carboxyl group-containing polyester resin (A) which comprises oils and / or fatty acids (a1), polybasic acids (a2) and polyhydric alcohols (a3) as essential components. Is mixed with an aqueous medium containing a basic compound to dissolve a colored resin solution in which a colored resin in which is dispersed in an alcohol-based solvent and / or a glycol ether-based solvent. A method for producing an aqueous colored particle dispersion for an inkjet recording liquid, which comprises performing neutralization with a part or all of a basic compound and dispersing the colored resin in an aqueous medium. 7. A stator provided with a ring-shaped projection having a slit and a rotor provided with a ring-shaped projection having a slit are coaxially provided so as to bite each other at intervals. Using a rotary type continuous dispersion device having a structure,
The central portion of the stator and rotor of this dispersion device, by supplying an aqueous medium containing a colored resin solution and a basic compound,
By rotating the rotor while flowing through the slits and the gap in the direction from the central portion to the outer periphery, neutralization of some or all of the carboxyl groups of the polyester resin (A) with the basic compound and the coloring resin The method for producing an aqueous colored particle dispersion for an inkjet recording liquid according to claim 6, wherein the dispersion is carried out in an aqueous medium. 8. The polyester resin (A) is a polyester resin having a carboxyl group and an alkyl group having 4 to 20 carbon atoms and / or an alkenyl group having 4 to 20 carbon atoms. A method for producing an aqueous colored particle dispersion for an inkjet recording liquid as described above. 9. The polyester resin (A) is an aliphatic having a terminal carboxyl group of a polyester resin having a carboxyl group at a terminal and having an alkyl group having 4 to 20 carbon atoms and / or an alkenyl group having 4 to 20 carbon atoms. The method for producing an aqueous colored particle dispersion for an inkjet recording liquid according to claim 6, which is a polyester resin having an acid value of 5 to 100 mgKOH / g and having a terminal structure obtained by ring-opening addition of a monoepoxy compound. 10. The inkjet according to claim 6, wherein the polyester resin (A) is a polyester resin having an acid value of 5 to 100 mgKOH / g and having a terminal structure represented by the following general formulas (1) and / or (2). A method for producing an aqueous colored particle dispersion for a recording liquid. [Chemical 2] (R in the formula represents an alkyl group having 4 to 20 carbon atoms or an alkenyl group having 4 to 20 carbon atoms.) 11. An inkjet recording liquid, comprising the aqueous colored particle dispersion for inkjet recording liquid according to claim 1 as an essential component.