TWI338708B - Process for producing water-borne pigment dispersion for ink jet recording - Google Patents

Description

[Technical Field] The present invention relates to a method for producing an aqueous pigment dispersion for inkjet recording, and an aqueous pigment dispersion for inkjet recording produced by the method. [Prior Art] For the purpose of environmental protection, safety of work, and improvement of stability, the demand for water-based printing of oil-based inks and oil-based paints has been increasing. On the other hand, in order to increase the water resistance and light resistance of printed images, the requirement to convert the dye of the original aqueous ink colorant into a pigment is also mentioned: and it is used as an ink for the production of various image forming applications. The development and improvement of aqueous pigment dispersions for intermediate materials have also been carried out. The ink-based recording ink-based ink is more stringent than other applications in terms of stability (spittling stability) when ejected from an ink ejection port, long-term storage stability, and the like. In other words, it is necessary to form a fine pigment having a particle diameter as uniform as possible so as to be coated with the resin so as to be stably dispersed in the liquid solvent for a long period of time. Further, in order to satisfy these requirements, it is necessary to have good dispersion stability and dispersion stability which may be stored for a long period of time in the stage of the aqueous pigment dispersion. Therefore, regarding the aqueous pigment dispersion liquid, various studies have been recently conducted for a composition suitable for inkjet recording use, a dispersion method of a pigment, and the like. The applicant discloses a styrene acrylic 1338708 resin having an acid value of 50 to 280 (for example, refer to Japanese Laid-Open Patent Publication No. Hei 8-1 83920 (Application No.)) as a coloring agent by the phase inversion emulsification method. It is microencapsulated to form a preferred resin composition of colored resin particles; and has 60 to 90 moles of styrene monomer, 5 to 15 moles of acrylic monomer, and 5 to 25 moles of methacrylic monomer. The resin composed of the monomer exhibits excellent dispersion stability and spoutability. In the production method using such a resin by the phase inversion emulsification method, it is necessary to distill the solvent for dissolving the resin, so that the manufacturing steps are complicated, so that it is not suitable for stable mass production. Further, when the solvent which cannot be distilled remains in the aqueous ink for inkjet recording, 'the amount is required because of the solvent odor and the aggregation of the Aliz in the ink-based ink for inkjet recording. A method for producing an aqueous pigment dispersion which is excellent in productivity and relatively good in dispersibility. For example, a method for producing such a method is known, in which a water-soluble resin and an alkali component are dissolved in water to prepare an aqueous solution, and a pigment is added thereto. After the mixture is sufficiently stirred, it is further dispersed by using a high-speed sand mill having a high dispersion efficiency to obtain an aqueous pigment dispersion liquid (for example, see JP-A-2001-262038). However, the step of using a sand mill to produce an aqueous pigment dispersion is usually carried out by using a dispersion of a low viscosity of a pigment or the like having a small solid content. Therefore, it is difficult to apply strong shear to the pigment, so it takes more time to pulverize the coarse particles of the pigment. Further, in the aqueous pigment dispersion obtained by this method, a large amount of coarse particles 8 1338708 having a particle diameter of 1 μm or more is contained even after dispersion. In addition, since it is not possible to ensure that the discharge from the ink discharge port as it is is further required to be removed by centrifugation, filtration, or the like, and the production efficiency is lowered and the yield is lowered, by one use In the method of producing a bead machine similar to the sand mill, the applicant uses the resin having a weight average molecular weight of 7,200 to disperse into an aqueous pigment dispersion using the composition as recited in the above-mentioned Patent Publication No. 1 (for example, refer to JP-A-10-8042 § Please patent scope, examples)). According to the aqueous pigment dispersion method, it is possible to produce an aqueous ink for inkjet recording having a fine dispersed particle size and good dispersion, and the discharge property of the ink is also, and the production method is applied to a general dispersion. In the case of difficult materials or quinacridone pigments, no dispersibility can be obtained in terms of carbon black. Further, it is not possible to mass-produce a pigment dispersion liquid with a small-scale production method. On the other hand, before the dispersing step, the resin and the compound, or a mixture of a resin, water, a fat solution formed of a water-soluble organic solvent, and a pigment may be preliminarily produced by a roll by a roll. The mixture is kneaded into a solid fine piece, and the solid fine piece is added to a solvent mainly composed of water and water, and a dispersing pigment dispersion liquid is used by a high-speed mixer, a homomixer or the like (for example, reference Kaiping bulletin (pages 2, 3, 5, 6), special open 2000-80299, page 3)). In order to make the production of the resin solution easier, stability and stability of the particles are also caused. The lacquer is mixed with the resin carbon to produce the tiger's bulletin (the manufacturer's manufacturer has excellent stability and stability. The azo pigment is well-mixed to form a water-based mixture of water pigments. The water is obtained by the soluble organic pigment of the double pigment. 5-1 57954 (2nd, with the addition of 9 1338708 mechanamine) (for example, refer to JP-A-2001-81 390 (p. 5)). For example, a bulletin having a special opening No. 8-1 83920 is used. The styrene acrylic resin having a weight average molecular weight of 50,000 in the resin composition described above is kneaded by a double-roller to produce an aqueous pigment dispersion liquid (for example, JP-A-2002-256201 (Example)). In this method, although the pigment is actually subjected to the shear force between the rolls to become a fine pulverized material, since it is carried out in an open system before sufficient honing, water and a water-soluble organic solvent are given in honing. Evaporation, and finally a solid fine film having a high ratio of solid matter. Therefore, in the subsequent dispersion step, water, a water-soluble organic solvent must be further added, and then The solid fine piece is pulverized, dissolved, and dispersed in the pigment. Thus, 'the dispersion time is not only long-term, but also, if it is dispersed for a long time, because it needs to be connected to the step of dispersing by roller honing. There is a possibility that coarse particles remain. In other words, the surface of the pigment of the solid fine piece after the roller honing by the resin is used, since the solid fine piece is passed through the pulverization, dissolution and dispersion step, so that it is in the water-based material. ·The resin coating on the surface of the pigment after the dispersion is produced is often insufficient. Moreover, when honing with a double-roller, the honing in the honing becomes a flaky shape between the rolls, and it is necessary not to make it It is detached from the roll, and the blending ratio of the pigment, the resin, the water-soluble organic solvent, and the like, and the kneading property of the resin which is colored by the thermal properties of the resin are not completed, and the raw materials and the raw materials are also used. The possibility of blending is limited. [Summary of the Invention] 10 1338708 Hereinafter, various raw materials used in kneading will be described. (1) Resin used in the present invention The ethylene acrylic resin, although the content of the styrene monomer unit is usually from 50 to 90% by mass, is preferably from 70 to 90% by mass. When the content of the styrene monomer unit is 50% by mass or more, The hydrophobicity of the styrene acrylic resin is increased, and it is the most desirable state in which the resin coating of the pigment can be performed. This results in excellent dispersion stability in an aqueous solvent, and pigment dispersion which is difficult to cause nozzle clogging can be obtained. Furthermore, when printing on plain paper using such ink-jet recording with aqueous ink, good water resistance of the printed image can be obtained, and good color development can be obtained even at high image density. When the total content of the styrene acrylic resin exceeds 90% by mass, the content of the monomer unit having an anionic group imparting dispersibility may be inevitably lowered, and the dispersion stability and long-term storage stability of the pigment particles in the aqueous solvent may be lowered. It will inevitably be reduced. The styrene acrylic resin used in the present invention is preferably three kinds of monomer units containing a styrene monomer unit, an acrylic monomer unit, and a methacrylic monomer unit. By containing these three kinds of monomer units', an aqueous pigment dispersion having an excellent dispersion stability and long-term storage stability of a higher layer can be obtained. When three monomer units as described above are contained, the content of the acrylic monomer unit is preferably from 3 to 15% by mass, and further, the content of the methacrylic monomer unit is preferably from 4 to 25 mass. /. . In addition, when the total content of the styrene monomer unit, the acrylic monomer unit, and the methacrylic monomer unit is 95% by mass or more based on the total amount of all the monomer units, the dispersion stability is better. The effect of sex is therefore preferred. A well-known compound can be used for the styrene monomer unit which comprises such a styrene acrylic resin. For example, it may be, for example, styrene, α-methylstyrene 'cold-methylstyrene, 2,4-dimethylstyrene, α-ethylstyrene, α-butylstyrene, hexyl Alkyl styrene of styrene, halogenated styrene of 4-chlorostyrene, 3-chlorostyrene, 3-brominated styrene, etc., and 3-nitrostyrene, 4-methoxystyrene, ethylene Toluene, etc. In addition to the styrene monomer unit 'acrylic monomer unit and the methacrylic monomer unit described above, the styrene acrylic resin used in the present invention can be used arbitrarily to produce an aqueous dispersion for inkjet recording. The known monomer unit used at the time is used as a monomer unit other than the above monomer unit. Examples of such monomer units may, for example, be methacrylate, methyl methacrylate, η-propyl acrylate, isopropyl acrylate, η-butyl acrylate, second Butyl acrylate, third butyl acrylate, 2-ethyl butyl acrylate '1ι3_dimethyl butyl acrylate 'hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, ethyl Methacrylates η-butyl methacrylate, 2-methylbutyl methacrylate, amyl methacrylate, heptyl methacrylate, mercapto methacrylate, acrylates and methyl groups Acrylates: 3- 15 1338708 ethoxypropyl acrylate, 3-ethoxybutyl acrylate, dimethyl ethyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxybutyl acrylate, Ethyl hydroxymethyl) acrylate 'dimethylaminoethyl methyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate acrylate derivative and methacrylate derivative; phenyl Benzyl acrylate, phenylethyl propylene Acrylate aryl acrylates such as esters, phenylethyl methyl propyl vinegar, and aryl acrylates; monopropyl acrylates of polyethylene glycol, polyethylene glycol, glycerin, and biphenol A Class or monomethacrylate; dimethyl maleate, dialkyl maleate of maleic acid diacetate, vinyl acetate, and the like. One or two or more of these may be added as a monomer component. The styrene acrylic resin to be used in the present invention preferably has an acid value of 3 Å in order to obtain a water dispersibility which is stable by neutralization of a base compound. When the acid value is less than 50, the hydrophilicity becomes small, and the dispersion stability of the pigment decreases. On the other hand, when the acid value is more than 300, aggregation of the pigment is liable to occur, and the printability of the ink composition using the ink composition is inevitably lowered. The acid value is preferably 60 to 250, more preferably: to the range of 200. The styrene acrylic resin used in the present invention is preferably a weight average molecular weight of 5,000 to 40,000. When the weight average molecular weight is 5,000, the long-term storage stability tends to be low, and when the ink jet recording liquid is used, in particular, the ink jet recording liquid of the thermal jet type, the discharge stability tends to decrease. Preferably, the weight average molecular weight is an ester of a base amide propylene or the like, an enoic acid alcohol, an ethylenic acid ethyl monomer, and a water resistance of 70 by a material having a capacity of less than 70, which is 7500 1338708 to 3000 0', More preferably, it is from 7500 to 20000 ° and the glass transition temperature of the 'styrene acrylic resin is preferably from 90 ° C to 150 ° C, more preferably from 100 ° C to 150 ° C. When the glass transition temperature is above 90 ° C, the thermal stability of the aqueous ink for ink jet recording increases. Therefore, when the aqueous inkjet recording ink produced by the aqueous pigment dispersion described above is used for inkjet recording by a thermal jet method, it is difficult to cause a change in characteristics such as poor discharge due to repeated heating, which is preferable. . Further, the glass transition temperature of the styrene acrylic resin used in the present invention is determined by measurement using a differential scanning calorimeter. In the first step of the present invention, the styrene acrylic resin may be added as an aqueous solution or a solvent solution and then kneaded. However, the added solvent is also liable to cause a decrease in the viscosity of the component, and when the resin is dissolved. When the solvent is high, the residual solvent may damage the resin coating film which has been coated on the surface of the pigment after kneading. Therefore, it is preferred to use a powdery or granular material which is not an aqueous solution or a solvent solution. By doing so, since the pigment and the resin are subjected to high shearing force at the same time, the decomposition and breakage of the pigment, and the swelling or dissolution of the styrene acrylic resin by the base compound or the wetting agent are simultaneously performed, so that Since the decomposed and broken pigment is directly coated on the resin, the kneading can be performed efficiently and satisfactorily. (2) Pigment The pigment can be a known one, and is not particularly limited. For example, an inorganic pigment such as carbon black, titanium black, titanium white 'zinc sulfide or iron red, or an azo pigment such as a monoazo type or a bisazo type, a phthalocyanine type pigment, or a quinacridine type pigment can be used. Organic pigments such as the color of the temple. The pigment may be a dry pigment such as a powder, granule or lumps, or may be in the form of a wet cake or slurry, but is preferably in the form of a powdery granule. When a combination of black, blue, and red 'yellow four-color pigments is selected to select an ink-based ink image for inkjet recording, in addition to the basic physical properties of the ink, it is necessary to consider the color development of the ink, The color balance between the ink and other inks is used to determine the pigment. The following is a description of the preferred ink jet recording pigments for various colors when the ink composition used in the production method of the present invention is used. For the black pigment, a carbon black black pigment such as furnace black, channel black, acetylene black 'light black, or the like can be used. It is not particularly limited as long as it has a pH of 2 to 8. Blue or cyan pigment, suitable for phthalocyanine blue pigments, for example, pigment blue 15: 1, pigment blue 15: 2' pigment blue 15: 3, pigment blue 15: 4, pigment blue 15: 6 Wait. A blue or cyan pigment is preferably a quinacridine red pigment. For example, a dimethyl quinacridane pigment such as C·丨·Pigment Red 1 2 2 or the like, CI Pigment Red 202, may be used. CI pigment red 209 and other quinacridine pigments, C · I. Pigment red 1 9 and other non-substituted acridine pigments, and CI pigment red 206 'CI pigment red 207 and the like holding acridine structure A solid solution of at least two or more pigments of the pigment or a mixture of at least two of the pigments. These quinacridine pigments are preferably c·丨.Pigment red 1 2 2 in terms of the specificity of hue 18 1338708. The yellow pigment is more suitable as an azo yellow pigment. For example, C.1. Pigment Yellow 74, CI Pigment Yellow 120, CI Pigment Page 128, c·丨 Pigment Yellow 155, and CI·Pigment can be used. Yellow 180 and so on. Further, in addition to the above-mentioned pigment, it may be used together with a derivative of various pigments as a dispersing aid. The above pigment is preferably blended in a mixture of 35 mass. /. Above, it is more suitable for 40 mass. /. the above. Generally, the aqueous pigment dispersion is diluted to obtain a certain concentration of aqueous ink for inkjet recording, thereby increasing the concentration of the aqueous dispersion to the maximum extent of production because a relatively large ink composition can be produced, Productivity is important. However, when the concentration of the pigment rises, the storage stability of the aqueous pigment dispersion deteriorates, so it is actually limited to 60 mass. /. Hereinafter, it is preferably limited to 50% by mass or less. Regarding the mass ratio of the pigment and the resin, it is preferred that there is a resin having a minimum amount necessary to stably coat the surface of the pigment, and when it contains more than the same amount of the resin, it is needless to say that it is not good. of. When there is an excess amount of the resin, since the free resin which does not adsorb the pigment increases when the aqueous dispersion is produced and the aqueous ink is recorded by the ink jet recording, the resin is solid when used for the ink jet recording ink. The ink jet nozzle is likely to cause a discharge failure, and in particular, there is a high risk of occurrence of a problem of discharge failure in a thermal jet printer. Therefore, among the colored kneaded materials for producing the aqueous dispersion of the present invention, the mass ratio of the resin/pigment varies depending on the kind of the pigment and the particle size and surface state of the 19 1338708, but it is preferably set to 1 / 彳〇 to 1 / 彳, more preferably set to 1/10 to 1/2. When the blending ratio of the pigment is too small relative to the resin, the problem of the above-mentioned free resin is liable to occur; and when the blending ratio of the pigment is too large, the pigment is not sufficiently covered by the resin, and thus the dispersion stability and long-term storage stability are satisfied. Sex will inevitably fall. (3) Base compound The base compound can be any of an inorganic base compound and an organic base compound. However, it is easy to adjust the alkali strength, and it is preferably an inorganic base. Sex compounds. The organic base compound may, for example, be an amine or the like, and examples thereof include methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, and triethylamine. Amines. Since it is usually 'liquid' in the case of an amine, it can be used in its original form. Examples of the inorganic base compound may, for example, be a hydroxide of an alkali metal such as potassium or sodium, or an alkali earth metal carbonate such as an alkali metal carbonate such as potassium 'sodium': Ammonium hydroxide and the like. Among these, the strong base has an effect of improving the dispersibility of the resin by neutralizing the styrene acrylic resin, and is preferably, specifically, potassium oxyhydride, sodium oxysulfide, or the like. The metal hydroxide is tested. The blending amount of the base compound is preferably set to 80% of the styrene acrylic resin neutralization rate according to the characteristics of the dispersion speed in the aqueous solvent, the dispersion stability, and the long-term storage stability. Above 20 l3387〇8. When the upper limit is 値, the dispersion stability and unevenness in long-term storage are preferably 200% or less 'more preferably 120% or less. For example, the mixture can be mixed by previously mixing benzene resin, water and basic compounds. It is produced by mixing and adding it to other blending components such as pigments, etc., but the base compound and other are used in order to efficiently carry out the above-mentioned benzene resin to the surface of the pigment. The blended ingredients are blended together as a mixture. In addition, the neutralization ratio herein is a number of bases which is a few percent (a few times) of the total amount of the neutralized styrene acrylic resin, and is expressed by the following formula. Neutralization ratio (%) = (mass of base compound (g) X 5 6 X valence X equivalent of base compound X resin (g)) χ (4) Wetting agent used in the present invention It is possible to record a known wetting agent used on an aqueous ink. Examples of the humectant are, for example, organic materials which may be polyols such as ethylene glycol, diethylene glycol, triethylene glycol, polyglycol, glycidol, etc.; 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( In the case of inkjet compounds, such as ethylene glycol, polypropylene ether, ethylene glycol 1338708, it is preferred to be a liquid polyol at room temperature, low volatility, and high surface tension, especially diethylene glycol, triethyl The diol or the like has a boiling point of i7 (the alcohol of rc or more is more preferable. Further, although the humectant varies depending on the resin to be used, it is usually preferably 10 to 50 mass in the mixture to be charged. The blending is more preferably 20 to 40% by mass. Although the amount of the addition varies depending on the solubility of the humectant used, it is preferably about 1/2 to 5 times the amount of the resin, more preferably The amount of resin is about 1 to 4 times. When the amount of humectant is less than the resin When the amount is 1/2, the resin cannot be dissolved, partially dissolved, or swollen, so that the dispersion stability of the pigment is inevitably lowered. Also, when it exceeds 5 times, the viscosity of the mixture during mixing is lowered. The kneading is sufficiently performed, so that the dispersibility of the pigment is lowered, and when the ink for inkjet recording is produced, it is inevitable that the discharge quality is deteriorated, and the image quality is deteriorated. In the case of a substance other than the role of the solvent, it is preferable to consider the situation and then determine the blending amount of the wetting agent. Further, the wetting agent is preferably blended with 1-5 to the mass ratio of the pigment body. 1 time, more preferably 1/3 to 1 times of blending, whereby the surface of the pigment can be sufficiently wetted, and at the same time the resin is in a relatively dissolved state or in a swelled state, the resin is coated on the surface of the pigment. When the amount of the wetting agent is less than 1 / 5 times, in the initial stage of the kneading, not only the surface of the pigment is not sufficiently wetted, but also the resin does not swell, and it is inevitable that sufficient effect is not obtained. (5) Kneading method 2 3 1338708 In the production method of the present invention, the styrene acrylic resin is made into a swollen state or a dissolved state by kneading a base compound and a wetting agent, and at the same time, a mixture having a good kneading viscosity with the pigment is formed. Therefore, if the kneading is continued while maintaining the state, it is not necessary to dissolve the styrene acrylic resin for kneading, and it is not necessary to add a solvent in order to dissolve the resin. After the kneading, the step of distilling off the solvent is not required, so the production efficiency is high. Although the kneading can be performed under a high shearing force, the kneading temperature (M t ) needs to be appropriately adjusted in accordance with the temperature characteristics of the resin, but it is preferable. It is kneaded below the glass transition temperature (Tg) of the phenylethyl acrylate resin. Further, by kneading at a temperature of 5 ° C or less at a difference from (Tg), the kneading step after the integration of the resin and the pigment in the initial stage of kneading can be performed extremely efficiently. That is to say, it is preferable to carry out kneading in a temperature range in which the kneading temperature (M t) and the glass transition temperature (Tg) of the styrene acrylic resin satisfy the following formula.

Tg-50^Mt^Tg is kneaded at a kneading temperature that satisfies such a relationship, and since kneading is performed at a low temperature away from the melting point of the styrene acrylic resin, for example, even when the kneading temperature in the kneading rises, It also does not at least exceed the melting point of the resin. Therefore, as the kneading temperature rises, the kneading viscosity of the colored kneaded material containing the resin is reduced, so that the shearing force is lowered. 24 1338708 Very little. Further, since the kneading temperature is lowered, it is difficult to increase the solid content ratio of the color kneaded material after the kneading is completed, and since the liquid component is contained in a large amount, it is easy to disperse the colored kneaded material after the kneading in the aqueous solvent. The manufacturing method of the present invention which is kneaded at a temperature lower than the glass transition temperature of the resin is applicable to the production of an aqueous ink for ink jet recording on the ink jet recording by thermal spraying. Namely, by dispersing a resin having a high glass transition temperature Tg which is very suitable for the hot-spraying method in an aqueous solvent, an aqueous pigment dispersion having good heat stability can be easily produced. Further, the glass transition temperature used in the production method of the present invention is measured by using a differential scanning calorimeter. In the production method of the present invention, the styrene acrylic resin is kept in a swollen state or a dissolved state by using a basic compound and a wetting agent. However, the solid content ratio of the kneaded product containing benzene and the pigment in kneading is preferably It is in the range of 50 to 80% by mass, more preferably in the range of 60 to 80% by mass. When the solid content ratio is less than 50% by mass, since the viscosity of the mixture is lowered, the kneading cannot be sufficiently performed, and the decomposition of the pigment tends to be incomplete. On the other hand, by maintaining the solid content ratio in the range of 50 to 80% by mass, it is possible to ensure that the viscosity of the colored kneaded material during kneading is appropriately increased, and application from the kneading machine during kneading is ensured. The shearing force on the colored kneaded material becomes large, so that the pulverization of the pigment in the coloring kneading can be simultaneously performed, and the pigment can be coated with the resin. However, when the solid content ratio exceeds 80% by mass, for example, even if the resin is heated to a temperature of 25 1338708, the kneading is likely to become difficult. In addition, when the aqueous pigment dispersion liquid is produced in the second step, the colored kneaded material is dissolved and dispersed in the aqueous solvent, and it becomes inevitable that the viscosity is low due to the aqueous solvent. Further, in the kneading step, as appropriate, in addition to the addition of suitable water for kneading. In this way, in order to adjust the ratio of the solid matter in the kneading to one and always apply a stable shearing force to the colored kneaded material, a closed system capable of controlling the volatilization of the humectant, or a kneading machine for controlling the vulcanization agent to be used is used. A mixing machine for agitating blades of a groove and a shaft of a stirring tank. The number of the agitating blades is not determined, but it is preferable to use a kneading machine having two blades for obtaining a high kneading action. When a kneading machine having such a configuration is used, the initial kneading can be carried out directly after diluting the kneaded material with the aqueous kneading material, and the aqueous pigment dispersion liquid can be produced in accordance with H dispersion. of. As an example of such a device, for example, a hybrid mixer, a pressure kneader, a Banbury mixer, a planetary type, and a planetary mixer are particularly suitable. Planetary Mixer A kneading device is a stirring paddle that operates like a planet. (The following is called "planetary mixer"). In the manufacturing method of the present invention, in order to carry out the ratio of the solid content of the pigment, it is not only difficult to make it, but also the humectant is not limited to the inside, and it is preferably a closed system, a single shaft or a mixture having a specific limit or more. The dispersion is used in a stirred tank (the sample can be a Henscher mixer, etc.; it is a mixture of planetary leaves and a solid mixture of stems and solids 26 1338708. The viscosity is Widely varied with the kneading state of the kneaded material, since the planetary mixer can cope with a wide range from a particularly low viscosity to a high viscosity, so the wide range from the start of the kneading to the dilution after the kneading In particular, when preparing a colored kneaded material for an aqueous pigment dispersion, the kneaded product needs to be dispersed in an aqueous solvent, so that a coloring knead can be uniformly dispersed and low-viscosity. The stagnation step of dispersion is important. However, when using a planetary mixer, the mixing step from the high viscosity to the viscous phase of the dispersion step is It can be continuously implemented in the same model, thus preventing the occurrence of coarse particles and having an excellent effect of increasing production efficiency. The one shown in Figures 1 to 3 is an example of the composition of a planetary mixer. In the figure, reference numeral 1 denotes a stirring tank in which a hollow cylindrical stirring tank 1 is roughly divided into upper and lower portions, and an upper inner portion of the upper portion 2 of the stirring tank 1 is an enlarged view of Fig. 2 As shown, the agitating blades 4 and 5 formed of a grid plate are provided. Further, during agitation, the upper unit 2 and the lower unit 3 are integrated to form a closed system. Further, as shown in Fig. 3, The rotating shafts of the stirring blades 4 and 5 are themselves rotated in the same direction around the common shaft with the rotator 6 in the same direction (revolution) by 180°, while the two stirring blade propellers 4 '5 While rotating (rotating, that is, performing planetary motion (Planetary movement)), the object is kneaded in the kneading 27 1338708 which is mounted inside the agitation tank 1. Further, as shown in Fig. 3, it is in the agitation tank. 1 revolution, 1 rotation, The trajectory of the front end of the two mixing blades 4 and 5. It can be understood that there are few dead angles. It is also possible to further reduce the movement of the stirring blade and the mixing device using the rotating shaft of the stirring blade. Therefore, it is more suitable for producing a colored kneaded material for an aqueous dispersion for inkjet recording which requires refining of a pigment and fine dispersion into an aqueous solvent. In the case of a planetary mixer, the shearing force acts strongly on the agitating blades 4, 5, and the agitating blades 4, 5 and the agitating tank 1 by planetary motion such as agitating blades 4'5. Between the faces, a high degree of agitation, kneading, and dispersion can be obtained. The blades used in the planetary mixer have been proposed in various blade shapes such as hook type, grid type, and flex type. However, in the present invention, any type of paddle can be used, and is not particularly limited, but it is necessary to have the strength to withstand the viscosity of the kneaded material, and it is preferable from the viewpoints of strength, kneading, and the like. Grid type. In addition, in terms of rotation and revolution, although they have the same direction and different directions, they can be divided into various operation modes according to the characteristics of raw materials used. Although there are various combinations in terms of the number of revolutions of rotation and revolution, various types of revolutions and enthalpy can be selected depending on the characteristics of the raw materials used. And when using a kneading machine that can make a planetary mixer or the like into a closed system, when mixing in a closed system, slowly increase the current consumption by 28 1338708 with time, and reach a maximum within about 30 minutes to reduce it. . That is, when the mixture is heated to 40 to the side and mixed, since the resin becomes sticky, and the skin is so that the stirring blades 4 and 5 are rotated, it takes a large load to mix the blades 4 and 5 with each other. And the agitating blades 4, which exert a large shearing force on the material, can be effectively pulverized, and the pigment is sufficiently dispersed and mixed to be coated with the grease. Then, the resin is almost completely mixed within about 30 minutes, so that the stirring blades 4, 5 become smaller. Therefore, the current consumption is gradually reduced. In the present invention, when a kneader such as a planetary mixer is used for mixing, it is found that a certain solid matter ratio is maintained in the relationship between the kneading time and the kneading machine (planetary mixer). More than one feature of the big cockroach. When kneading in a closed system like this, the quality of the kneaded material in the mixing and kneading in the kneading device such as the open system of the two rolls is substantially constant, and the aqueous pigment of the same composition is dispersed. The use of liquid can improve the stability of manufacturing. Further, the material constituting the colored kneaded material is put into a stirring or the form of the colored kneaded material in the kneading, and after being subjected to the kneading, the mixture is slowly mixed at a temperature of 7 ° C. At this time, in the stirring material and the stirring tank, the load applied to the tree material and the wetting agent is mixed, and the system is closed, and the current consumption of the power consumption is extremely high. In order to obtain the color mixture, and the form of the groove, the mechanical property of 29 1338708 is the least restrictive, which increases the degree of freedom of resin, pigment selection and blending ratio, and can be used in a kneading occasion. Come to mix. For example, a resin having a Tg of 90 ° C or higher, a resin having a molecular weight of 5,000 Å, a styrene monomer component of a styrene acrylic resin, and the like are each suitably suitable for use as (especially) for printing. The inkjet recording machine uses a resin for water-based ink, but it is not easy to mix it with two, especially when it is difficult to improve the discharge property and the pigment concentration of the fat/pigment 値 is 1 or less. In the method for producing an aqueous pigment dispersion of the present invention, the method for producing an aqueous pigment dispersion according to the present invention is kneaded in a state of a pigment concentration and a high solid concentration in the initial stage of high kneading. The pigment is decomposed and broken into coarse particles which are not dispersed, thereby being reduced. As a result, it is possible to alleviate the process of removing coarse particles in the step, so that the yield is improved. (B) Production of aqueous pigment dispersion Liquid-colored kneaded material for aqueous pigment dispersion, usually at a normal temperature. Therefore, the aqueous pigment dispersion liquid is dispersed to produce an aqueous pigment dispersion liquid. Further, since the pigment in the colored kneaded material for aqueous dispersion is decomposed and broken in the production of the kneading, the dispersion time for obtaining the aqueous pigment can be shortened, and the production efficiency can be increased. Further, the resin of the coloring and kneading material of the present invention is selected from the 2,000 to 40% of the resin, and the heat-spraying roller is used to cause the tree to be crushed and used in the following. The following is the liquid separation of the pigments in the solid color mixing, which is based on the interaction between the styrene acrylic resin and the base compound by 30 1338708, and the solubility and dispersibility to water are good' and quickly Dissolved and dispersed. Such a rapid dispersing, dissolving in water, and maintaining it in a stable manner is one of the great features of the colored kneaded material for the aqueous pigment dispersion of the present invention. In the present invention, the so-called aqueous solvent is composed of water, water or a wetting agent. As the humectant used herein, the same thing as that used in the kneading in the first step can be used. As the dispersing machine, a known one can be used, for example, it can be a paint shaker using a medium, a pulverizer, a basket honing machine, a sand mill, a dynamic honing machine, a distributed honing machine. Pad, SC honing machine, super honing machine, Aditech honing machine, etc. Further, the medium is not used, and for example, it may be an ultrasonic mixer, a defogging disperser, a reverse dissolving disperser, a dispersing machine, a high-speed mixing dispersing machine, etc., in which a dispersing machine using a medium is dispersed. High ability and suitable. Further, when the aqueous pigment dispersion liquid is required to be adjusted as needed, various known additives such as an alkali agent can be further blended, and when the alkali agent is added, the dispersion stability can be improved, which is preferable. In addition, it is preferable to add and mix an aqueous solvent in the colored kneading liquid for the aqueous pigment dispersion liquid as needed, before the dispersion by the disperser (the present dispersion), etc. Dilute and then moderately treat with the aforementioned disperser to adjust the viscosity. For example, when a sand mill is used, it is preferable to carry out a dilute release solid concentration of 1338708 to 10 to 40% by mass, adjust the viscosity to tens to hundreds of decibels, and then drive the sand mill to disperse. In the present invention, for example, after kneading by a kneading machine equipped with the above-mentioned stirring tank and stirring blade, a colored kneaded material is obtained, and then an aqueous solvent is added to the kneaded material in the stirring tank, and mixing can be performed. Adjustment of viscosity. Thus, the manufacturing efficiency can be improved by starting from the manufacture of the colored kneaded material to the viscosity adjustment in one apparatus. Further, in order to adjust the viscosity of the colored kneaded material for the aqueous pigment dispersion, the dilution is carried out. Therefore, in order to improve the dispersion efficiency and the production efficiency, it is preferred to carry out the dilution without lowering the temperature of the kneaded material. For example, it is preferred to continuously add a small amount of warm water of 60 degrees or more in batches while stirring the colored mixture prepared by using a kneading device such as a planetary mixer. Further, the "viscosity adjusting material" is taken out from the stirring tank as needed, for example, and dispersed by the above dispersing machine to obtain an aqueous pigment dispersion liquid. Further, it may be adjusted in a stirring tank so as to reach a predetermined viscosity, and further taken out from the stirring tank, and mixed with an aqueous solvent to adjust the viscosity to obtain a viscosity adjuster, and further, further The aqueous pigment dispersion is prepared by dispersing in an aqueous solvent. (C) Manufacture of ink-based ink-based ink for ink-jet recording, which can be produced by dissolving an aqueous pigment dispersion obtained as described above and further diluting it in an aqueous solvent at 32 1338708. . It is preferably contained in an aqueous ink for inkjet recording in an amount of about 2 to 10% by weight. When it is blended in an aqueous solvent for diluting the aqueous pigment dispersion liquid, it is preferable to impart an anti-adhesion adjustment, a concentration adjustment, and the like to the ink-based ink for ink-jet recording. As the aqueous solvent, the same ones as those used for the dispersion of the above aqueous pigment dispersion can be used. Further, when a water agent exhibiting permeability to a recording medium is blended, it is preferably a permeability which can impart an aqueous ink to the ink composition, and is used to adjust the water-based ink. Record the permeability of the media and the necessary characteristics of the hour in the recording medium. The water-soluble organic aqueous solution exhibiting permeability may, for example, be a lower alcohol such as ethanol or isopropanol, an epoxide addition product of an alkyl alcohol such as ethylene glycol hexyl butyl ether or the like, and an alkyl alcohol of propylene glycol. The propylene oxide compound and the like. In the aqueous ink for inkjet recording, in addition to the aqueous pigment dispersion of the aqueous ink for aqueous media, for example, a known additive of hydrazine or the like. Examples of the substance which can be blended, for example, a agent, a ruthenium adjuster, a surfactant 'preservative, a chelating agent oxidation preventive agent, an ultraviolet absorbing agent, an ultraviolet ray hardener, are, for example, By adding the water-based pigment, the concentration is more than that of the humectant, and the extracting agent is dissolved, for example, the coloring mixture is dissolved organically. Ink jet recording In the ink jet recording, the dot diameter is large, for example, it can be mixed with an ink jet recording such as ether, diethyl propylene glycol ether or the like, and it may be an alkali, a plasticizer, a gluten or the like. Dispersion, 33 1338708 Aqueous solvent 'Additional additives are added as needed, and they are mixed into a water-based ink for inkjet recording. Such an ink jet recording aqueous ink is a very suitable ink for ink jet recording. The ink jet method to be applied is not particularly limited. However, it may be, for example, a continuous spray type (charge control type, spray type, etc.), a demand response type (induction type, heat injection method, electrostatic attraction type, etc.). Then, such an ink-jet recording aqueous ink can be used to discharge ink in an extremely stable manner when used in various ink-jet methods, and is particularly suitable for ink jet recording by thermal spraying. [Embodiment] Hereinafter, the present invention will be described in more detail by way of examples. In addition, if it is not particularly limited, "parts" is "mass parts" and "%" is "mass%". Further, the resins A and B used in the examples of the present invention are as described below. Resin A is a monomer group ratio: styrene / methacrylic acid / acrylic acid = 77 / 1 3 / 1 〇 (mass ratio), molecular weight is 7500 in mass average molecular weight, acid value is 145, glass transition temperature is i14 〇C, a resin having a melting point of 155 ° C. Resin B is a monomer group ratio: styrene/methacrylic acid/acrylic acid = 77/13/10 (mass ratio), molecular weight is 12000 in terms of mass average molecular weight, acid value is 157, and glass transition temperature is 1彳. 8 〇c 'Resin with a melting point of 155 °C. Resin C is a monomer group ratio: styrene/methacrylic acid/acrylic acid 34 1338708 = 77/13/10 (mass ratio), molecular weight is 46000 in mass average molecular weight, acid value is 140, glass transition temperature is 128 ° C resin. Here, the weight average molecular weight means a ruthenium measured by a GPC (Gel dialysis chromatography) method, that is, a ruthenium converted into a polystyrene used as a standard material. Further, the measurement was carried out using the following apparatus and conditions.

Transfer liquid pump: LC-9A

System Controller: SCL-6B

Automatic injector: SIL-6B

Detector: RID-6A and above are manufactured by Tsusho. Data processing software: Sic480 Π data workstation (system based in Sluman) Pipe column: GL-R-400 (kad column) + GL-R440 + GL-R450 + GL-R4 00M (made by Hitachi Chemical Co., Ltd.) )

Dissolution solvent: T H F Dissolution flow rate: 2 ml / min

Column temperature: 3 5 °C (Example 1) • Production of colored kneaded material A mixture of the following composition was placed in a planetary mixer PLM-V-50V (manufactured by Inoue Co., Ltd.) with a capacity of 50L. The ejector is heated, and the mixture is kneaded at a low speed (rotation number: 35 1338708 2 1 rpm, revolution number: 14 rpm) before the temperature of the content 尙 does not reach 60 ° C, when the content temperature reaches 60 ° After C, 'switch to high speed (rotation revolution: 35 rp m·' revolutions: 24 rpm) to continue the kneading. Resin A 250 parts quickly to Enlan TGR (manufactured by Dainippon Ink Co., Ltd.) 500 parts of 34% by mass aqueous potassium hydroxide solution (<0^) 110.3 parts of diethylene glycol (DEG) 239 parts switched to high-speed planetary mixing The current of the machine is 7A. The maximum current displayed by the planetary mixer is 115 A, and the current 1 after 15 minutes is 7.5 A. In this state, the color-mixed kneaded material obtained in the stirring tank was continuously kneaded for 3 hours, and the total amount of ion-exchanged water was added in a total amount of 00 parts while continuing to knead, and the kneading was continued, and further added. A total of 400 parts of ion-exchanged water was used to produce a viscosity adjuster. In a sealable container of 2,500 ml of polyethylene, 400 g of zirconium beads of φ1·2 mm were charged, and 30.7 g of the removed viscosity adjuster, 12.2 g of DEG, and 10_1 g were added. The ion-exchanged water was treated with a paint conditioner (Toyo Seiki Co., Ltd.) for 2 hours to obtain a pigment dispersion liquid Α1. The solid concentration of Α1 was 24% by mass. The pigment concentration was 15.2% by mass. (Example 2) A mixture of the following composition was blended in a stainless steel container, heated to 60 ° C and stirred well, and then heated to 130 ° C and kneaded in two rolls. Resin A 2 5 5 parts 36 1338708 Quickly give Enlan TGR (made by Dainippon Ink Co., Ltd.) 51 0 parts of 34% by mass aqueous potassium hydroxide solution (K〇H) 11 3 parts of diethylene glycol (DEG) 1 22 parts mixture After completing the mixing for 15 minutes after completion, the colored kneaded material was taken out. After the mixture is cooled, after the pulverizer, the powder of a size of 1 mm or less is used. At this time, the solid matter of the kneaded material was concentrated [degree of the mass of 87% by mass. • Production of pigment dispersion Powder-like kneaded material 276 parts DEG 271 parts Ion-exchanged water 453 parts A mixture of the above composition was prepared, and mixed and stirred in a dispersing mixer for 2 hours to prepare a preliminary dispersion. In a 250 ml polyethylene sealable container, load 400 g of ρ1·2 mm pin beads, and add 53 g of the prepared dispersion to the paint conditioner (Toyo Seiki) The solid concentration of the pigment dispersion liquid & 2 " Α 2 was 24.1% by mass, and the pigment concentration was 15 _ 5 mass%. (Comparative Example 1) • Preparation of aqueous resin solution The methyl ethyl ketone solution was prepared by blending as follows: methyl ethyl ketone (ΜΕΚ) 500 parts of resin A 500 parts of 779.4 parts of ion-exchanged water, 34 A mass % of hydrogen oxygen 37 1338708 hydrazine (ΚΟ Η), 220.6 parts of an aqueous solution, was well stirred to obtain a resin a solution. The resin A solution was subjected to removal of MEK at a water bath temperature of 45 ° C under a reduced pressure of 40 hPa to obtain 11.35 parts of a resin-dissolved aqueous alkali solution H1. 865 parts of ion-exchanged water was added to the resin-dissolved aqueous alkali solution to prepare 2000 parts of the resin-dissolved aqueous alkali solution H1. 572 parts, 286 parts, 572 parts, 4 4, 6.9 parts, dispersion of 2 + • pigment dispersion, resin, dissolved alkali solution, H1, fast, Enlan TGR (manufactured by Dainippon Ink Co., Ltd.), diethylene glycol ion exchange water, the above blend A pigment dispersion liquid was produced after mixing in a dispersing mixer. The pigment dispersion liquid was further dispersed in a ball honing machine (manufactured by Asada Iron Works Co., Ltd., NJ-G2L) under the following conditions to obtain a pigment dispersion liquid B1. • Dispersion condition disperser ball ball charge cooling water temperature rotation number nano honing machine NM-G2L (Asada Iron Works) Φ1·2 mm pin stone 85% 1 or 2660 rpm (disc speed: 12.5 mm Ft/sec, the amount of liquid to be transported: 200 g/min) 38 1338708 Further, the dispersion was carried out through a four-stage dispersing machine under the above conditions (4 times). When the pigment dispersion liquid was dispersed for the first time, that is, the pressure of the liquid to be supplied to the disperser was increased, the liquid was transported at 200 ml/min, and the amount of the transport liquid was reduced to 50 ml/min. After the second time, the liquid was transported at 200 ml/min, and the liquid dispersion liquid b1 was obtained four times. The pigment dispersion B1 had a solid concentration of 24% by mass and a pigment concentration of 15.2% by mass. (Example 3) • Production of a colored kneaded material A mixture of the following composition was placed in a planetary mixer PLM-V-50V (manufactured by Inoue Co., Ltd.) having a capacity of 50 L, and the same operating conditions as in the examples. Mix and practice. Resin A 1 50 parts Carbon black (manufactured by Mitsubishi Chemical #960) 500 parts DEG 380 parts 34% by mass aqueous potassium hydroxide solution 66.6 parts The current 値 of the planetary mixer was switched to 5A at a high speed. From the maximum current of 行星1 5 Α 3 3 3 行星 行星 行星 行星 混合 混合 继续 继续 继续 继续 继续 继续 继续 继续 继续 继续 继续 继续 继续 继续 继续 继续 继续 继续 继续 继续 继续 继续 继续 继续 继续 继续 继续 继续 继续 继续 继续 继续 继续 继续 继续 继续 继续 继续A total of 100 parts of ion-exchanged water was mixed for about 2 hours. • Manufacture of Pigment Dispersion 39 1338708 Next, the kneading was continued, and 50 parts of ion-exchanged water was added for a total of 400 parts, and the colored kneaded material was taken out from the planetary mixer. The solids concentration of the kneaded product was 38.1 weight. /. . To the 1000 parts of the colored mixture obtained, 352.6 parts of DEG and 159.3 parts of ion-exchanged water were added, and the mixture was stirred with a dispersing mixer, and added in a small amount for 30 minutes to obtain a viscosity adjuster. The viscosity-adjusting material was dispersed in a ball honing machine (manufactured by Asada Iron Works, Nippon Honing Machine NM-G2L) under the same dispersion conditions as in Comparative Example 1, to obtain a pigment dispersion liquid 3. Further, the dispersion was carried out by a four-stage dispersing machine under the above conditions (four times). The solid concentration of the pigment dispersion A3 was 25 mass. /. The pigment concentration was 彳8.7 mass. /. . (Comparative Example 2) • Production of pigment dispersion liquid Resin dissolved in aqueous solution Η 1 572 parts of carbon black (manufactured by Mitsubishi Chemical #960) 476.7 parts of diethylene glycol 9 53.4 parts of ion-exchanged water 686.7 parts of the above mixture in a dispersing mixer After mixing, • Dispersion was carried out for 2 hours to prepare a pigment dispersion. This pigment dispersion liquid was dispersed under the same conditions as in Comparative Example 1. When the pigment dispersion liquid was dispersed for the first time, that is, the pressure of the liquid to be supplied to the dispersing machine was increased, and the liquid was not transported at 2 〇〇 ml/min, and the amount of the transport liquid was reduced to 5 〇 ml/min. After the second time, the liquid was transported at 2 〇〇 ml/min, and the mixture was applied 4 times for a total of 40 1338708 to obtain a pigment dispersion liquid B 2 . The pigment dispersion B 2 had a solid concentration of 25 mass% and a pigment concentration of 18.7 mass%. (Comparative Example 3) • Production of colored kneaded material The mass of 34 in Example 3 was obtained. /. The potassium hydroxide aqueous solution was replaced with 44 parts of pure water, and a planetary mixer PLM-V-50V (manufactured by Inoue Co., Ltd.) having a capacity of p 〇1 was placed in the same manner as in Example 3, and Example 3 was used. The same operating conditions are mixed. The current 値 of the planetary mixer when switching to high speed is 6A. Continue to mix the current of the planetary mixer without showing the maximum current 値 and continue mixing for 30 minutes. The contents at this time are not blocky but powdery. In the same manner, 25 parts of diethylene glycol (D EG) was added to the colored mixture obtained in the stirring tank until it was homogeneous. In the same way, add 25 parts of DEG each time, and add a total of 1 part of DEG, and mix for about 2 hours. While continuing the kneading, 50 parts of DEG were added in the same time as in Example 3, and a total of 450 parts of DEG was added, and the mixture was kneaded for about 2 hours. • Production of Pigment Dispersion The diluted solid color kneaded material has a solid matter ratio of 38.9% in a state in which the resin and the pigment are not dispersed. /. . 1 part of 41 1338708 diethylene glycol and 556.5 parts of ion-exchanged water '39.8 parts of 34% by mass potassium hydroxide aqueous solution were added to one part of the above-mentioned post-release color mixing mixture to disperse The stirrer was stirred and added in a small amount for 30 minutes and dispersed to obtain a preliminary dispersion. This preliminary dispersion was subjected to a ball honing machine (manufactured by Asada Iron Works, Nippon Honing Machine NM-G2L) under the same dispersion conditions as in Example 3, and the dispersion was carried out. The liquid pressure was delivered to the disperser until the amount of liquid delivered was reduced to 40 gram ml/min. After the second time, the dispersion was usually carried out at 200 g/min to obtain a pigment dispersion liquid B3. The solid concentration of the pigment dispersing liquid B 3 was 2 5.1 mass. /. The pigment concentration was 18.7% by mass. (Comparative Example 4) • Production of Resin Aqueous Solution A methyl ethyl ketone solution of Resin C was prepared in accordance with the following blending. Methyl ethyl ketone (MEK) 500 parts Resin C 500 parts A 900 parts of ion-exchanged water, 50% by mass of sodium hydroxide (NaOH), and an aqueous solution of 1 part by weight were added thereto, and the mixture was well stirred to obtain a resin hydrazine solution. The resin B solution was subjected to removal of Μ E K at a water bath temperature of 45 ° C under a reduced pressure of 40 hPa to obtain 1 1 3 5 parts of a resin-dissolved aqueous alkali solution. 1910 parts of ion-exchanged water was added to the resin-dissolved aqueous alkali solution to prepare 3 1 2 5 parts of a resin-dissolved aqueous alkali solution Η 2 . • Production of pigment dispersion Resin dissolved in aqueous solution Η 2 5 1 0 parts 42 1338708 Carbon black (manufactured by Mitsubishi Chemical #45L) 163 parts of 327 parts of diethylene glycol in a 250 ml polyethylene sealable container 4 g of 1.2 mm zircon beads were placed, and 53 g of the above blend was added, and treated with a paint conditioner (Toyo Seiki) for 4 hours to obtain a pigment dispersion B4. The solid concentration of B4 was 25% by mass' and the pigment concentration was 16.3% by mass. (Comparative Example 5) • Preparation of Resin Aqueous Solution A methyl ethyl ketone solution of Resin A was prepared in accordance with the following blending. Methyl ethyl ketone (hereinafter, abbreviated as MEK) 500 parts of Resin A 500 parts of which were added 874 parts of ion-exchanged water, 30% by mass of sodium hydroxide (Na〇H>, 180 parts of aqueous solution, and stirred well to obtain Resin A The solution A was removed by removing the Μ EK at a water bath temperature of 45 ° C under a reduced pressure of 40 hPa to obtain 1 107 parts of a resin-dissolved aqueous alkali solution. The ion-exchanged water was added to the obtained resin to dissolve. In the aqueous alkali solution, a total mass of 1 554 parts of the resin is dissolved in the aqueous alkali solution Η3. • The production of the pigment dispersion liquid is dissolved in the aqueous alkali solution Η 2 51 0 parts carbon black (Mitsubishi Chemical #45L) 1 63 parts Alcohol 3 27 parts 43 1338708 In the same manner as in Example 1, 400 g of zirconium beads of *1.2 mm were placed in a 250 ml polyethylene sealable container, and 53 g of the following doping was further added. The mixture was treated with a paint conditioner (Toyo Seiki) for 2 hours to obtain a pigment dispersion Β 5. Resin dissolved in an aqueous solution Η 3 17.7 parts carbon black (Mitsubishi Chemical #45L) 19.0 parts ion exchange water 25.4 parts DEG 37.9 parts Income The solid concentration of B 5 was 25 mass%, and the carbon black concentration was 19 mass%. (Example 4) A mixture of the following composition was put into a planetary mixer PLM-V-50V having a capacity of 50 L (in the well The product was kneaded in the same conditions as in Example 1. Resin B 75 parts quickly gave Super Super Magenta RTS (manufactured by Dainippon Ink Co., Ltd.) 500 parts DEG 350 parts 34% by mass aqueous potassium hydroxide solution When 33.3 parts of ion-exchanged water are switched to high speed, the current of the planetary mixer is 5A. After that, the mixing is continued, and the maximum current 値 is 20 自 from the planetary mixer, and the mixing is continued for 1 hour. The current of the planetary mixer 値For the same procedure, 'add 20 parts of ion 44 1338708 exchange water every time in the color mixing mixture obtained in the stirring tank, and mix evenly, add a total of 1 part of ion exchange. Then, while continuing to knead the mixture, the ion-exchanged water was added in an amount of 50 parts/time, and it was confirmed that the total amount of ion-exchanged water was 400 in total. After the completion of the addition of the ion-exchanged water, the product was taken out from the planetary mixer, and further, 439 parts of diethylene glycol and 543 parts of ion-exchanged water were added in a small amount of the extracted 1,000 parts of the product. A viscosity adjuster was produced, and the viscosity adjuster was dispersed in a paint conditioner (Toyo Seiki Co., Ltd.) under the same dispersion conditions as in Comparative Example 1. Further, the dispersion was passed under the above conditions. The secondary disperser is carried out (4 times). The pigment dispersion P 1 had a solid concentration of 20% by mass and a pigment concentration of 17% by mass. (Comparative Example 6) The kneading of the following composition mixture was carried out in the same manner as in Example 1. Resin B 75 parts Quickly give Super Pink Magenta RTS (manufactured by Otsuka Ink Co., Ltd.) 500 parts DEG 3 50 parts Ion exchange water 20 parts The current 値 of the planetary mixer is 5A when switching to high speed. After the subsequent mixing, the planetary mixer showed a maximum current of 6A. After the practice of mixing, 'continue mixing for 1 hour, the current of the planetary mixer is not changed. 45 1338708 The same approach' Add 20 parts of ion-exchanged water each time in the color mixing mixture obtained in the stirring tank, while uniformly In the kneading, a total of 1 part of the ion-exchanged water is added. Then, while mixing, the ion-exchanged water is added in an amount of 50 parts/time, and it is confirmed that the mixture is uniformly mixed as described above, and the total amount is added. It is 400 parts of ion exchange water. After the ion exchange water is added, the product is taken out from the planetary mixer. Further, a product obtained by adding 439 parts of diethylene glycol and 520.8 parts of ion-exchanged water '22.24 parts of 34% by mass of potassium hydroxide solution to the obtained 1 part of the product was stirred and stirred. Viscosity adjuster. The viscosity adjuster was dispersed in a paint conditioner (Toyo Seiki Co., Ltd., NM-G2L) under the same dispersion conditions as in Example 1, and when the second dispersion was carried out, the conveyance to the ball honing machine was improved. The liquid pressure was carried out because the liquid could not be delivered at 200 ml/min, which was reduced to 50 g/min. After the second time, since the liquid can be transported at 200 g/min, the pigment dispersion liquid is obtained by performing a total of four times. The pigment dispersion had a solid concentration of 19.8% by mass and a pigment concentration of 17.1% by mass. (Comparative Example 7) - While stirring 100 g of a methyl ethyl ketone solution containing styrene acrylic resin A having a solid concentration of 50%, 25 ml of a commercially available 1 equivalent of KOH, and 75 ml of ion-exchanged water were added to the solution. , neutralizing styrene acrylic resin A. Methyl ethyl ketone was distilled off under reduced pressure, and ion exchange 46 1338708 was added to change water to obtain an aqueous solution Η 4 containing styrene acrylic resin A having a solid concentration of 20%. Next, the following composition was placed in a container having a capacity of 250 ml, and then subjected to dispersion treatment for 4 hours using a paint conditioner. After the end of the dispersion treatment, 1 1.5 parts of ion-exchanged water was further added, and then the chrome beads were separated by filtration to obtain an aqueous pigment dispersion Β 7 having a pigment concentration of 14.5%. Styrene Acrylic Resin Solution Η4 7.5 parts CI Pigment Red 122 (trade name: Fast 恩恩超品 10.0 parts Red RTS (made by Dainippon Ink Co., Ltd.) Diethylene glycol 20 parts Ion exchange water 20 parts Zircon beads (1.25 (Millimeter diameter) 400 parts (Example 5) A mixture of the following composition was placed in a planetary mixer PL Μ - V - 50 V (manufactured by Inoue Co., Ltd.) having a capacity of 50 L, in the same manner as in Example 1. Conditions for kneading. Resin Β Fast Yellow 7410 (Pigment Yellow 74) (manufactured by Shanyang Pigment Co., Ltd.) 34% by mass of potassium hydroxide aqueous solution Diethylene glycol 240 parts 60 0 parts 11 1.8 parts 300 parts At this time, planetary mixing The current of the machine 値 'in the initial stage is 7 Α, then reaches the maximum of 14 Α ' and slowly decreases as the mixing continues. 47 1338708 Next, in the color mixing mixture obtained in the stirring tank, '- continue to mix' side 1 0 0 Part of the ion-exchanged water. Then, while continuing to mix, add 800 parts of ion-exchanged water. Further, add 200 parts of ion-exchanged water to prepare a viscosity adjuster and take it out. In the stagnation adjustment, 477.9 parts of diethylene glycol and 105.1 parts of ion-exchanged water were added in a small amount while mixing, and dispersed. Further, 'further in a ball honing machine (Asada Iron Works, Nylon) In the mill NM-G 2 L ), dispersion was carried out under the same dispersion conditions as in Comparative Example 1, to obtain a pigment dispersion liquid A5. The pigment dispersion liquid A5 had a solid concentration of 25.3% by mass and a pigment concentration of 17.3% by mass. (Comparative Example 8) A mixture of the following composition was placed in a planetary mixer PLM-V-50V (manufactured by Inoue Co., Ltd.) having a capacity of 50 L, and kneaded under the same conditions as in Example 1. Resin B 240 parts Fast yellow 741 0 (pigment yellow 74) 600 parts (manufactured by Shanyang Pigment Co., Ltd.) 34% by mass of potassium hydroxide aqueous solution 1 1 1 · 8 parts of diethylene glycol 300 parts At this time, the load current of the planetary mixer At the beginning of the high speed, it is 6A. The kneading is carried out at high speed for 30 minutes, and then 200 parts of diethyl -2- is added. During this period, the load current 8 of 8A is stably displayed. In this state, after 48 1338708 continues to be mixed for 1 hour, Add diethylene glycol / ion Change the water = 3 parts / 350 parts of the mixture. After the mixture is added, continue mixing for 30 minutes and remove the viscosity adjuster. Add 1 part of the viscosity adjustment with a small amount of stirring. 1 90·31 parts of diethylene glycol, 420.1 parts of ion-exchanged water, 51.06 parts of 34% by mass of hydrazine aqueous solution, and dispersed and liquefied. Further, further in a ball honing machine (Asada Iron Works, In the nano honing machine NM-G2L), the same dispersion conditions as in Comparative Example 1 were carried out to obtain a pigment dispersion liquid Α5. The pigment dispersion liquid 5 had a solid concentration of 2 5 · 3 mass% and a pigment concentration of 17.3 mass. /. . Although the dispersion obtained was carried out in the same manner as in Comparative Example 1 by the ball honing machine, the pressure of the transfer liquid 11 to the disperser was increased, and since the liquid could not be transported at 500 ml/min, The dispersion was carried out by reducing the amount of the transport liquid to 50 ml/min to obtain a pigment dispersion liquid Β8. The pigment dispersion liquid 8 had a solid concentration of 25.3% by mass and a pigment concentration of 17.3 mass. (Evaluation of Dispersibility of Aqueous Pigment Dispersion) In the pigment fractions and solutions obtained in the examples and the comparative examples, ion-exchanged water was added to adjust the concentration so that the respective pigment concentrations were 14 · 5 mass%. For the pigment dispersion having the adjusted pigment concentration, the particle size measurement was carried out by using a micro-track U ΡΑ particle 49 1338708 degree analyzer (manufactured by Lai & Noske Co., Ltd.). At this time, the sample having the particle size measurement was adjusted to a concentration at which the particle diameter measurement was carried out by using ion-exchanged water. Further, a small amount of the adjusted pigment dispersion liquid is placed on the glass slide, and the air is not allowed to enter the dispersed liquid droplets on the slide glass, so that the cover glass is placed in a state where the thickness of the dispersion liquid film is constant. Observation by a light microscopy at 200 times magnification was carried out and observation of large particles was carried out. The results are shown in Table 1. 50 1338708

Table 1 Item Giant Pigment Average Particle Size (Nano) Microscopic Observation Dispersion Judgment Example 1 Cyanamide 126 There are almost no coarse particles of 1 μm or more.实施 Example 2 153 has a small amount of coarse particles of 1 μm or more. Δ Comparative Example 1 149 Most of them are coarse particles of 1 μm or more. There are no particles above 5 microns. X Example 3 Carbon V 1 > 78 There are almost no coarse particles of 1 μm or more. 〇 Comparative Example 2 125 Most of them are coarse particles of 1 μm or more. There are a small amount of coarse particles of 5 microns or more. X Comparative Example 3 184 Most of them are coarse particles of 1 μm or more. There are a small amount of coarse particles of 5 microns or more. X Comparative Example 4 85 A small amount of coarse particles of 1 μm or more. Δ Comparative Example 5 98 A small amount of coarse particles having a small amount of 1 μm or more. Δ Example 4 Magenta 124 There are almost no coarse particles of 1 μm or more. 〇 Comparative Example 6 167 Most of them are coarse particles of 1 μm or more. There are a small amount of coarse particles of 5 microns or more. X Comparative Example 7 113 A small amount of coarse particles having a small amount of 1 μm or more. Δ Example 5 Yellow 144 There are almost no coarse particles of 1 μm or more. 〇 Comparative Example 8 202 Most of them are coarse particles of 1 μm or more. There are a small amount of coarse particles of 5 microns or more. The criterion for determining the X dispersion determination is as follows. 51 1338708 〇: There are almost no coarse particles larger than 1 μm in the microscope observation field. △: A small amount of coarse particles of 1 μm or more was observed in the microscope observation field, but coarse particles of 5 μm or more were hardly present. X: Most of the coarse particles of 1 μm or more are observed in the microscope observation field. Alternatively, a small amount of coarse particles of 5 μm or more are present. From the measurement results of the particle size of the dispersion and the results of microscopic observation, the following can be found. In other words, in the state where the resin is in a low solid content, 0 is compared with the aqueous pigment dispersion liquid produced by dispersion by a ball honing machine, and the base compound which is not added with a pigment and a resin, and is kneaded by a ball 硏. When the aqueous pigment dispersion liquid produced by the method of dispersing the mill is used, the particle diameter of the aqueous pigment dispersion liquid exemplified in the examples can be remarkably reduced, and the residual amount of the coarse particles can be drastically reduced. (Evaluation of heat dispersion stability (storage stability)) In the pigment dispersion liquids of the examples and the comparative examples, the evaluation of the dispersion liquid was carried out in the same manner, and ion exchange water was added to adjust the respective pigment concentrations to φ 1 4 · 5 % »About the dispersion that has been adjusted to adjust the pigment concentration, seal it tightly. In a glass container such as a spiral tube, heat it in a thermostat at 60 ° C for 1 week, and observe the heating test by visual observation. The dispersion stability was evaluated by the dispersion of the particle size before and after, and the presence or absence of the sediment. The results are shown in Table 2. 52 1338708 Table 2 Project Pigment Initial Particle Size (Nano) Initial Particle Size (Nano) Change Rate (%) Settlement Example 1 126 125 -0.8 实施 Example 2 Cyanide 153 155 1.3 No Comparative Example 1 Amine 149 140 - 6.0 Example 3 78 79 1.3 Button/1 Comparative Example 2 125 133 6.4 Comparative Example 3 Carbon 184 211 14.7 Comparative Example 4 Black 85 86 1.1 Μ Comparative Example 5 98 114 16.3 Example 4 124 147 18.5 and /» %% Comparative Example 6 Magenta 167 278 66.5 Comparative Example 7 113 151 33.0 实施 Example 5 144 162 12.5 fit /* w Comparative Example 8 Yellow 202 263 30.2 Observing the average particle from the storage of the dispersion in a warmed state As a result of the change in the diameter and the presence or absence of the sediment, it is attempted to compare the examples and the comparative examples. 'In the first embodiment, the second embodiment, and the comparative example 1, although the difference in the particle diameter change rate is not significant, However, the presence or absence of the sediment recognizes a significant difference' and thus the dispersion of the embodiment is superior. With respect to the dispersion of the examples, the average particle diameter after the heating test was remarkably increased. Further, it was confirmed with respect to the dispersion of the comparative example that the sediment was not produced in the dispersion of Example 53 1338708. Further, from the comparison of Example 4 and Comparative Example 6, Example 5 and Comparative Example 8, it is shown in the examples of the present invention that the dispersion has extremely dispersion stability, and thus it can be judged that it is a good dispersion. (Adjustment of ink-based ink for ink-jet recording) The dispersions obtained in the above Examples and Comparative Examples were blended with the following to prepare a pigment concentration of 3 to 5 by mass. /. The inkjet recording uses a water-based ink. The composition table is shown in Table 3. 54 Pigment cyanide project example 1 ZZli I ^ Γ liquid diethylene glycol (parts) glycerin (parts) Trinix GP-600* (parts) ion exchange water (parts) pigment concentration (%) number blending amount (parts A1 19.7 5.0 0.0 5.0 70.3 3.0 Monthly Example 2 A2 19.5 5.0 0.0 5.0 70.5 3.0 Comparative Example 1 A B1 — 19.7 5.0 0.0 5.0 70.3 3.0 Example 3 A3 26.5 5.0 0.0 5.0 63.5 5.0 Carbon Comparative Example 2 B2 26.5 5.0 0.0 5.0 63.5 5.0 Comparative Example 3 B3 26.7 5.0 0.0 5.0 63.3 5.0 Comparative Example 4 B4 30.4 5.0 0.0 5.0 59.6 5.0 Comparative Example 5 B5 26.3 5.0 0.0 5.0 63.7 5.0 Example 4 A4 23.5 5.0 3.0 5.0 63.5 4.0 Magenta Comparative Example 6 — B6 23.4 5.0 3.0 5.0 63.6 4.0 Comparative Example 7 B7 27.6 2.0 3.0 5.0 62.4 4.0 Example 5 A5 23.1 5.0 3.0 5.0 63.9 4.0 Comparative Example 8 B8 23.1 5.0 3.0 5.0 63.9 4.0 1,338708 . Diacetylation system (unit: part) (Printing test) The ink-based ink for inkjet recording obtained in Table 3 was mounted on a NOVA JET PRO (hot-jet type inkjet printer) manufactured by ENCAD Co., Ltd., and a printing test was carried out. Specifically, the printing of $printing and fine-line printing is continuously performed on the printing paper (UB inkjet paper) 55 1338708 of 1 sheet A, and the discharge state of the ink is confirmed. The results are not in Table 4. Table 4

Item Pigment Printing Test Evaluation Results Example 1 ◎ Example 2 Cyanide 〇 Comparative Example 1 Amine X Example 3 ◎ Comparative Example 2 X Comparative Example 3 Carbon X Comparative Example 4 Black △ Comparative Example 5 △ Example 4 ◎ Comparative Example 6 Red X Comparative Example 7 △ Example 5 ◎ Comparative Example 8 The evaluation criteria of the yellow X printing test are as follows. ◎: All the print samples can be printed uniformly, even if the thin line portion is not defective in discharge, and the printing position is not deviated. 〇: All the printed samples can be printed uniformly. Although the thin line is also not punctured, the printing position can be seen with a slight deviation. △: Although there was no problem in the initial printing, the printing was found to be defective in the middle of printing (several times), and the printing density was uneven, and the printing of the thin line portion was spread. X: It was found that the cold printing was performed when the initial stage of the discharge was poor and the density was uneven. Even in the case of the thin line portion, the printing is dissipated due to poor ejection at the beginning of the initial stage, and the continuous printing is deteriorated. From the results of Table 4, in the first embodiment, the third embodiment, and the fourth embodiment of the fifth embodiment of the present invention, it is possible to obtain an image having no problem at all for initial printing and repeated printing. Further, in the second embodiment, at least an image having no problem in initial printing can be obtained, and even if the printing is repeated, the position is slightly deviated, but there is no problem in practical use. On the other hand, in Comparative Example 1, Comparative Example 2, Comparative Example 3, Comparative Example 6, and Comparative Example 8, when the initial printing was started, the discharge was unstable, and the discharge stability of the ink was greatly deteriorated. Further, in Comparative Example 4, Comparative Example 5, and Comparative Example 7, although there was no problem in the initial printing, the discharge of the ink at the time of repeated printing after several sheets became unstable, and the image quality was deteriorated, so that it was confirmed. The continuous discharge stability of the ink is greatly deteriorated, and it can be determined that the ink produced by the production method exemplified in the examples has particularly excellent discharge stability. [Possibility of Industrial Use] As described above, in the present invention, coarse particles in each stage can be reduced by the action of a base compound or the like, and a high level can be obtained without special separation of coarse particles. Dispersion-stabilized aqueous pigment dispersion. 57 1338708 In particular, in the case where the ink for inkjet recording is suitable, the present invention can produce an ink-based recording with high reliability with respect to the ink-based recording of inkjet recording manufactured by a conventional method. Ink. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a perspective view showing an example of the configuration of a planetary mixer. Figure 2 is a partial enlarged view of the planetary mixer. Fig. 3 is an explanatory view showing the trajectory of the stirring blade in the planetary mixer. [Component Symbol Comparison Table] 1 Stirring tank 2 Upper assembly 3 Lower assembly 4 Mixing paddle 5 Stirring paddle 6 Rotator 58

Claims (1)

1338.708 ^ • l\\^ b- -3⁄43⁄4 Amendment No. 92 1 2 1978 "Preparation method for aqueous pigment dispersion for inkjet recording" Patent case (amended on October 12, 2001) Pick up and apply for a patent Scope: 1. A method for producing an aqueous pigment dispersion for inkjet recording, comprising: (1) a styrene acrylic resin having a mass of from 50 to 90%. /. a styrene monomer unit, and at least one unit selected from the group consisting of an acrylic monomer unit and a methacrylic monomer unit, and having an acid value of 50 to 300 '(2) pigment, (3) a base compound, and 4) a first step of mixing the humectant into a colored colored kneaded product and a second step of dispersing the above-mentioned solid colored kneaded material in an aqueous solvent composed of water or water and a wetting agent; 3) the base compound is an alkali metal hydroxide, and (4) the wetting agent is selected from the group consisting of ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, polypropylene glycol, glycidol; Alcohol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, tetraethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol single Phenyl ether, ethylene glycol monobenzyl ether, N-methyl-2-pyrrolidone, N. hydroxyethyl-2-pyrrolidone, 1,3-dimethylimidazolidone, ε-caprolactam , r-butyrolactone, formamide, methylformamide, hydrazine, hydrazine-dimethylformamide, monoethanolamine, diethanolamine, triethanolamine, monoethylamine, Triethylamine, dimethylmethylene Sa, Sa sulfolane, thiodiethanol 'propylene carbonate (propylene carbonate), one of the group consisting of ethylene carbonate, organic compound, or a mixture of plural kinds. The method for producing an aqueous pigment dispersion for inkjet recording according to the first aspect of the invention, wherein the styrene acrylic resin of (1) has a mass average molecular weight of 5,000 to 40,000, (2) The pigment is at least one selected from the group consisting of an azo yellow pigment, a quinacridone red pigment, a phthalocyanine blue pigment, and a carbon black-based black pigment. 3. The method for producing an aqueous pigment dispersion for inkjet recording according to the second aspect of the patent application, wherein in the first step, (1) the quality of the styrene acrylic resin, (2) the pigment, and (4) the wetting agent The ratio is (1) 1 to 100, (2) 100, and (4) 20 to 100. 4. The method for producing an aqueous pigment dispersion for inkjet recording according to any one of claims 1 to 3, wherein in the first step, the planetary kneading device is used for kneading. 5. The method for producing an aqueous pigment dispersion for inkjet recording according to the fourth aspect of the invention, wherein the kneading temperature of the first step is below (1) the glass transition temperature of the styrene acrylic resin. 6. A method for producing an aqueous pigment dispersion for inkjet recording, comprising: (1) a styrene acrylic resin having a styrene monomer unit of 50 to 90% by mass, and at least - The unit is selected from the group consisting of an acrylic monomer unit and a methacrylic monomer unit, and has an acid value of 50 to 300, (2) a pigment, a (3) base compound, and (4) a wetting agent, which is kneaded to form a solid. The first step of coloring the kneaded material, and dispersing the above-mentioned solid colored kneaded material. 60- IX ^38708 The second step in the aqueous solvent consisting of water or water and a wetting agent, wherein the base compound of (3) is an alkali metal hydroxide, and the wetting agent of (4) has a boiling point of 170 ° C The above polyols. The method for producing an aqueous pigment dispersion for inkjet recording according to any one of claims 1 to 3, wherein the blending amount of the base compound of (3) is equivalent to neutralization (1> benzene The amount of all the carboxyl groups in the ethylene acrylic resin is 0.8 to 1.2 times. 8' is an ink-based recording ink-based ink containing the production method according to any one of claims 1 to 3. The aqueous pigment dispersion produced is used as a main component. 9. The ink-based ink for inkjet recording according to the scope of claim 8 is used for inkjet recording of a thermal spray method. The ink is a method for producing an aqueous pigment dispersion liquid, wherein the styrene acrylic resin of (1) has a mass average molecular weight of 5,000 to 40,000, and the pigment of (2) is an azo yellow pigment or a quinacridine red pigment. a pigment selected from the group consisting of a phthalocyanine blue pigment and a carbon black black pigment. 11. A method for producing an aqueous pigment dispersion for inkjet recording according to claim 10 of the patent application, Its benzene in the first step The mass ratio of ethylene acrylic resin, (2) pigment, and (4) wetting agent is (1 μ〇 to 100 parts, (2) 100 parts ', and (4) 20 to 100 parts. 6, 1 〇 and 1 1 of the inkjet -61 - 1338.708 Month i>q Corrector This is a manufacturing method for recording an aqueous pigment dispersion. In the third step, a planetary kneading device is used for mixing. 13. The method for producing an aqueous pigment dispersion for inkjet recording according to the scope of claim 2, wherein the kneading temperature of the first step is equal to or lower than the glass transition temperature of the (1) styrene acrylic resin. 14. The method for producing an aqueous pigment dispersion for inkjet recording according to any one of claims 6, wherein the compounding amount of the base compound of (3) is equivalent to neutralization. (1) An amount of 0.8 to 1.2 times the total amount of carboxyl groups in the styrene acrylic resin. An ink-based recording ink-based ink containing an aqueous pigment dispersion liquid produced by the production method according to any one of claims 6, 10 and 11 as a main component. 16. The ink-based ink for ink jet recording according to the fifteenth aspect of the patent application, which is used for ink jet recording by a thermal jet method. -62· 1338708 (4) Nitrogen miscellaneous pick up, pattern: 63 I338J08 Figure 2 64 1338708 \c> 65