JPH09151342A - Aqueous dispersion for recording liquid containing anionic microencapsulated pigment and recording liquid - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject dispersion liquid produced by coating an organic pigment or carbon black with a prescribed amount of an organic polymer compound having anionic group, giving excellent fineness and color density, having excellent color rendering property and transparency and useful for water-based ball-pointed pen, etc. SOLUTION: This dispersion is produced by coating (A) an organic pigment or (B) carbon black with (C) an organic polymer compound having anionic group (e.g. organic amine salt) and contains 35-80wt.% of the component A or the component B. Preferably, the maximum particle diameter of the primary particle of the component A or the component B is <=200nm and the average particle diameter is 10-100nm. The maximum particle diameter of the produced anionic microencapsulated pigment is <=1,000nm and the average particle diameter is <=300nm. The dispersion may be incorporated with a curing agent and/or a polymer.

Description

Detailed Description of the Invention

[0001]

The present invention relates to an aqueous ballpoint pen,
Pigments in microencapsulated pigments that are useful as materials for producing water-based recording liquids for writing instruments such as fountain pens, water-based felt-tip pens, water-based markers, and on-demand type inkjet printers such as bubble jet method, thermal jet method and piezo method. The present invention relates to an aqueous dispersion for a recording liquid containing a highly concentrated anionic microencapsulated pigment, and a recording liquid containing the dispersion.

[0002]

2. Description of the Related Art Conventionally, dyes have been used in recording liquids requiring high definition. A recording liquid using a dye has characteristics such as high transparency, high definition, and excellent color rendering properties, but has problems such as light resistance and water resistance.

In recent years, in order to solve the problems of light resistance and water resistance, recording liquids using organic pigments or carbon black instead of dyes have been manufactured.

However, when an organic pigment or carbon black is used, there is a problem that if the pigment is not finely dispersed and stabilized, a high definition and a high color rendering cannot be obtained as a recording liquid. Particularly, in a recording liquid for an ink jet printer, if the pigment is not finely dispersed and stabilized, it directly leads to a problem of nozzle clogging. Further, when an organic pigment is used for an OHP sheet or the like for projecting with a backlight, there is a problem that a colorful OHP projected image cannot be obtained unless the pigment is finely dispersed to ensure high transparency. It was

In particular, the organic pigments and carbon blacks used in these are smaller in primary particle size and stronger in secondary aggregation than the commonly used organic pigments and carbon blacks in paints and inks. A large amount of energy is required to disperse these pigments into primary particles. Also, even if these pigments can be dispersed up to primary particles,
Various measures are required to keep the pigment in the dispersion stable.

In order to solve these problems, a method of using microcapsules has been disclosed as shown below. For example, JP-A-62-95366 discloses a method of using a microcapsule containing a dye ink in polymer particles as a recording liquid, JP-A-1-170672.
Japanese Patent Laid-Open Publication No. 2004-242242 discloses a method in which a dye is dissolved or dispersed in a solvent which is substantially insoluble in water, and this is emulsified and dispersed in water using a surfactant, and a dye microcapsulated by a conventional method is used as a recording liquid. Japanese Patent Application Laid-Open No. 5-39447,
A method of using a microcapsule in which a sublimable disperse dye is dissolved or dispersed in at least one of water, a water-soluble solvent and a polyester resin in a recording composition, as disclosed in JP-A-6-313141. Discloses an aqueous ink composition comprising colored emulsion-polymerized particles and various aqueous materials.

[0007]

However, the one in which the dye is encapsulated has a problem that it is inferior in the light resistance, and the microencapsulated pigment produced by the conventional method has a large particle size, and therefore it is transparent. There is a problem in that it is inferior in properties, color development and color rendering properties. In addition, since the resin concentration in the capsule is high (the pigment concentration is low), the selectivity of the material used for the recording liquid is low, the versatility is lacking, and the recording liquid loses the feeling of concentration. Was. Furthermore, when the pigment concentration is excessively high, it is difficult to produce a fine microencapsulated pigment only with a resin, and therefore, a surfactant has to be used in combination, and therefore water resistance is not always satisfied. The recorded image was not obtained.

The problem to be solved by the present invention is to realize labor saving in the step of finely dispersing the pigment in the dispersion medium of the recording liquid in the production of the recording liquid using the aqueous pigment dispersion liquid.
To provide a microencapsulated pigment-containing aqueous dispersion that can reduce the manufacturing cost of a recording liquid by saving a great deal of labor, equipment, energy, etc., and also to select a resin for recording liquid, various additives or solvents, etc. Providing an aqueous dispersion containing a microencapsulated pigment that is highly versatile and highly versatile, and further provides the density, high definition, color rendering properties, transparency, and water resistance required for the recording liquid. Another object of the present invention is to provide a microencapsulated pigment-containing aqueous dispersion for a recording liquid having excellent redispersibility and a recording liquid using the aqueous dispersion.

[0009]

Means for Solving the Problems The inventors of the present invention have made extensive studies to solve the above-mentioned problems, and as a result, have made an organic pigment or carbon black coated with an anionic group-containing organic polymer compound. An anionic microencapsulated pigment-containing aqueous dispersion having an organic pigment or carbon black content of 35 in the anionic microencapsulated pigment.
When an anionic microencapsulated pigment-containing aqueous dispersion liquid in the range of up to 80% by weight is processed into a recording liquid, there is no limitation on selection and addition amount of resin, solvent or various additives at the time of production, and versatility is high. Since it can be used by simply mixing an aqueous dispersion containing an anionic microencapsulated pigment, the conventional manufacturing cost can be reduced, and the definition, color rendering and transparency of the recording liquid can be improved more than ever. Since it is not necessary to use a surfactant, a base for neutralizing the anionic group-containing organic polymer compound which is a resin for enhancing the water resistance of a recorded image and further for microencapsulation is used as a non-volatile base. The present invention has been completed by finding that it is possible to improve the redispersibility and the reliability of the recording liquid by using a resin (alkali metal) having high properties.

That is, in order to solve the above-mentioned problems, the present invention provides an organic pigment or carbon black together with an anionic group-containing organic polymer compound (hereinafter referred to as "anionic polymer", if necessary, together with a curing agent and a polymer compound. It is abbreviated as "organic polymer compounds"), and is an aqueous dispersion containing an anionic microencapsulated pigment, wherein the content of the organic pigment or carbon black in the anionic microencapsulated pigment is 35 to 80. Provided is an anionic microencapsulated pigment-containing aqueous dispersion for a recording liquid and a recording liquid containing the aqueous dispersion, which are in the range of wt%.

The aqueous dispersion for a recording liquid containing the anionic microencapsulated pigment of the present invention is an anionic organic polymer compound containing an organic pigment or carbon black, optionally together with a curing agent and a polymer compound. In addition, the content of the organic pigment or carbon black is 35 to 80% by weight, the maximum particle size of primary particles of the organic pigment or carbon black is 200 nm or less, and the average particle size is 10 to 10. The maximum particle size of the anionic microencapsulated pigment is 10 nm.
Those having an average particle diameter of 00 nm or less and an average particle diameter of 300 nm or less are particularly preferable. Further, it is preferable to use a form in which anionic organic polymer compounds are neutralized with a base, and it is particularly preferable to use an alkali metal.

Furthermore, it is more preferable that the anionic microencapsulated pigment is in a form in which the organic pigment is coated with anionic organic polymer compounds containing a curing agent and a polymer compound.

Furthermore, in the capsule of the microencapsulated pigment of the present invention, an inorganic substance such as titanium or aluminum, a pigment derivative, a pigment dispersant, a pigment wetting agent, an organic solvent, a plasticizer, an ultraviolet absorber or an antioxidant is used. Alternatively, other substances such as a vehicle for the recording liquid can be included.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION As a method for producing an anionic microencapsulated pigment contained in the aqueous dispersion for recording liquid of the present invention, physical and mechanical methods are used as conventional methods,
There are two methods including chemical methods such as a coacervation method, an interfacial polymerization method and an in-situ method.

However, even if the particle size of the microencapsulated pigment obtained by these conventional methods is submicron (μm) or less, the particle size is large, and the pigment in the microcapsule occupies it. Since the proportion is low, when a recording liquid is produced using this microencapsulated pigment, it is not always possible to obtain satisfactory definition, color rendering, transparency or color density. It is necessary to produce microencapsulated pigments that are finer and have a high proportion of the pigment in the microcapsules.

Further, since the resin concentration in the capsule is high (the pigment concentration is low), the materials used for the recording liquid are limited, and the water resistance is poor due to the use of the surfactant.

The method for producing the anionic microencapsulated pigment contained in the aqueous dispersion for recording liquid of the present invention includes:
Basically, a mixture (composite or composite) of anionic organic polymer compounds having a self-dispersing ability or a dissolving ability with water and an organic pigment or carbon black, or an organic pigment or carbon black is used. A mixture of a curing agent and an anionic organic polymer compound is used as an organic solvent phase, and water is added to the organic solvent phase, or the organic solvent phase is added to water and self-dispersed (phase inversion emulsification). The method of converting (hereinafter referred to as "phase inversion method") is preferable.

Alternatively, a step of neutralizing a part or all of the anionic groups of the anionic group-containing organic polymer compound with a basic compound and kneading with an organic pigment or carbon black in an aqueous medium, and P with acidic compounds
A water-containing cake obtained by a process comprising a step of precipitating anionic group-containing organic polymer compounds by making H neutral or acidic and fixing them to a pigment is used to form a part of anionic groups by using a basic compound or A method of obtaining by neutralizing all (hereinafter, referred to as "acid deposition method") is also preferable.

By doing so, it is possible to produce an aqueous dispersion liquid containing an anionic microencapsulated pigment that is finer and has a higher pigment content than the conventional method.

In the above phase inversion method, there is no problem even if the vehicle for the recording liquid and the additive are mixed in the organic solvent phase. In particular, it is more preferable to mix the vehicle for the recording liquid from the viewpoint that the dispersion liquid for the recording liquid can be directly produced.

The organic pigment or carbon black contained in the microcapsules of the anionic microencapsulated pigment has the following properties in order to obtain a feeling of density, transparency and color rendering of the recording liquid.
Alternatively, in order to produce a fine microencapsulated pigment having an average particle diameter of 300 nm or less, the maximum particle diameter is 200
nm or less and the average particle size of the primary particles is 10 to 10
Organic pigments or carbon black in the 0 nm range are preferred.

The type of the organic pigment used in the present invention is not particularly limited, but if only representative ones are exemplified,
Quinacridone pigments, quinacridone quinone pigments, dioxazine pigments, phthalocyanine pigments, anthrapyrimidine pigments, anthanthrone pigments, indanthrone pigments, flavanthrone pigments, perylene pigments, diketopyrrolopyrrole pigments, perinone Examples thereof include pigments, quinophthalone pigments, anthraquinone pigments, thioindigo pigments, benzimidazolone pigments, isoindolinone pigments, azomethine pigments and azo pigments.

Carbon black is neutral, acidic,
Examples thereof include basic carbon.

Examples of the curing agent that may be contained together with the pigment in the microcapsules of the anionic microencapsulated pigment include, for example, amino resins such as melamine resin, benzoguanamine resin, and urea resin, trimethylolphenol, and its condensates. Phenol resin, tetramethylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate (HDI), naphthalene diisocyanate (NDI),
Isophorone diisocyanate (IPDI), xylylene diisocyanate (XDI), polyisocyanates such as modified isocyanates and blocked isocyanates, aliphatic amines, aromatic amines, N-methylpiperazine, triethanolamine, morpholine, dialkylaminoethanol, benzyl Amine such as dimethylamine, polycarboxylic acid, phthalic anhydride, maleic anhydride,
Hexahydrophthalic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic acid anhydride, acid anhydrides such as ethylene glycol bistrimellitate, bisphenol A type epoxy resin, phenolic epoxy resin, glycidyl methacrylate copolymer, glycidyl ester of carboxylic acid Resins, epoxy compounds such as alicyclic epoxies, polyether polyols, polybutadiene glycols, polycaprolactone polyols, alcohols such as trishydroxyethylisocyanate (THEIC), unsaturated groups used for radical curing with peroxide or UV curing or electron beam curing Examples of the contained compound include polyvinyl compounds, polyallyl compounds, vinyl compounds such as reaction products of glycol or polyol with acrylic acid or methacrylic acid, and the like.

These curing agents are used to cure the walls of the anionic microencapsulated pigment or to enhance the strength of the coating film when used in a recording liquid, and if necessary, photoinitiated. It is more preferable to promote the curing by adding an agent, a polymerization initiator or a catalyst.

Examples of the photoinitiator used for such a purpose include, but are not limited to, benzoins, anthraquinones, benzophenones, sulfur-containing compounds and dimethylbenzyl ketal.

Similarly, as the polymerization initiator, for example, t
Peroxides such as -butylperoxybenzoate, di-t-butyl peroxide, cumene peroxide, acetyl peroxide, benzoyl peroxide, lauroyl peroxide; azobisisobutylnitrile, azobis-2,4-dimethylvalero Examples include azo compounds such as nitrile and azobiscyclohexanecarbonitrile.

Similarly, as the catalyst, for example, Co
Examples thereof include compounds and Pb compounds.

The polymer compound which may be contained together with the pigment in the microcapsules of the anionic microencapsulated pigment can be used without particular limitation as long as it has a number average molecular weight of 1,000 or more. Considering the film strength of the recording liquid and the production of capsules, the number average molecular weight is 3,
The range of 000-100,000 is preferable.

The type of such a high molecular compound is not particularly limited, but examples thereof include polyvinyl type such as vinyl chloride, vinyl acetate, polyvinyl alcohol and polyvinyl butyral, polyester type such as alkyd resin and phthalic acid resin,
Amino resins such as melamine resin, melamine formaldehyde resin, aminoalkyd co-condensation resin, urea resin, urea resin, thermoplastic, thermosetting or modified acrylic, epoxy, polyurethane, polyether, polyamide, unsaturated Examples thereof include polyester-based, phenol-based, silicone-based and fluorine-based polymer compounds, or copolymers or mixtures thereof.

The anionic organic polymer compounds used to produce the anionic microencapsulated pigment are:
There is no particular limitation as long as it has a self-dispersing ability or a dissolving ability in water and is anionic (acidic), but in order to obtain a sufficient one as a capsule film or a coating film of a recording liquid, it is usually several Average molecular weight of 1,000 to 100,000
The range of 0 is preferable and 3,000 to 50,000
Those in the range are particularly preferable, and those which are dissolved in an organic solvent to form a solution are preferable.

The self-dispersing ability or the dissolving ability of the anionic organic polymer compound itself is not particularly limited. For example, anions such as a carboxyl group, a sulfonic acid group and a phosphonic acid group in the anionic organic polymer compound can be used. The functional group is imparted by neutralizing with an organic amine such as ammonia or triethylamine or an alkali metal such as sodium hydroxide, potassium hydroxide or lithium hydroxide. Particularly desirable self-dispersing ability or dissolving ability is to introduce a carboxyl group into these organic polymer compounds,
It is a form that can be neutralized with a base. The anionic organic polymer compounds may have two or more of these anionic groups.

The amount of the carboxyl group in the anionic polymer compound having a carboxyl group is such that the acid value is 30 KOH.
It is preferably at least mg / g, more preferably in the range of 50 to 250. The acid value of the anionic polymer compounds is 250
If it exceeds, the hydrophilicity tends to be too high, so that the storage stability of the capsule tends to be impaired and the water resistance of the recorded image tends to be remarkably reduced. If the acid value is lower than 30, the stability of the capsule will be poor. It is not preferable because it tends to be damaged or the particle size tends to increase.

Examples of such anionic organic polymer compounds include polyvinyl type such as vinyl chloride, vinyl acetate, polyvinyl alcohol, polyvinyl butyral, etc., polyester type such as alkyd resin, phthalic acid resin, etc.
Amino materials such as melamine resin, melamine formaldehyde resin, aminoalkyd co-condensation resin, urea resin, urea resin; thermoplastic, thermosetting or modified acrylic, epoxy, polyurethane, polyether, polyamide, Examples thereof include materials having an anionic group such as unsaturated polyester-based, phenol-based, silicone-based, fluorine-based polymer compounds, and copolymers or mixtures thereof.

The anionic organic polymer compounds used in the present invention have a sufficient molecular weight as a capsule wall material,
Although it does not particularly require an operation of forming a wall, in order to further improve the properties such as solvent resistance and durability of the capsule wall, or to increase the film strength of the recording liquid after film formation, By making the anionic organic polymer compound itself used pendant with a reactive active group such as a glycidyl group, an isocyanate group, a hydroxyl group or α, β-ethylenically unsaturated double bond (vinyl group), Alternatively, a cross-linking agent having a reactive active group, for example, melamine resin, urethane resin epoxy resin, by mixing a photo-curing agent such as ethylenically unsaturated monomers and oligomers, during or after the formation of the capsule, Alternatively, after forming the coating film of the recording liquid, by utilizing these reactive active groups and functional groups, an anionic organic polymer compound for a capsule wall material is used. It is more preferable to increase the molecular weight of the class itself, or to impart the ability to crosslink and gel.

Among the anionic organic polymer compounds, the anionic acrylic resin is, for example, an acrylic monomer having an anionic group (hereinafter, abbreviated as anionic group-containing acrylic monomer) and, if necessary, these monomers. It is obtained by polymerizing in a solvent, another monomer copolymerizable with. Examples of the anionic group-containing acrylic monomer include, for example, an acrylic monomer containing one or more anionic groups selected from the group consisting of a carboxyl group, a sulfonic acid group, and a phosphone group, and among these, an acrylic monomer having a carboxyl group Is particularly preferred.

Examples of the acrylic monomer having a carboxyalkyl group include acrylic acid, methacrylic acid, crotonic acid, ethacrylic acid, propylacrylic acid, isopropylacrylic acid, itaconic acid, fumaric acid and the like. Among these, acrylic acid and methacrylic acid are preferred.

Examples of the acrylic monomer having a sulfonic acid group include sulfoethyl methacrylate and butyl acrylamide sulfonic acid.

Examples of the acrylic monomer having a phosphon group include phosphoethyl methacrylate and the like.

Other monomers that can be copolymerized with the anionic group-containing acrylic monomer include, for example, methyl acrylate, ethyl acrylate, isopropyl acrylate, -n-propyl acrylate, -n-butyl acrylate, acrylic acid- t-butyl, 2-ethylhexyl acrylate, -n-octyl acrylate, lauryl acrylate,
Benzyl acrylate, methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, methacrylic acid
n-propyl, n-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate, n-octyl methacrylate, lauryl methacrylate, stearyl methacrylate,
(Meth) acrylic acid ester such as tridecyl methacrylate and benzyl methacrylate; addition reaction product of oil fatty acid and (meth) acrylic acid ester monomer having oxirane structure such as addition reaction product of stearic acid and glycidyl methacrylate; carbon Addition reaction product of (meth) acrylic acid with an oxirane compound containing an alkyl group having 3 or more atoms; styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-
styrenic monomers such as tert-butyl styrene; itaconic acid esters such as benzyl itaconate;
Maleic acid esters such as dimethyl maleate; fumaric acid esters such as dimethyl fumarate; acrylonitrile, methacrylonitrile, vinyl acetate, isobornyl acrylate, isobornyl methacrylate, aminoethyl acrylate, aminopropyl acrylate, methyl acrylate Aminoethyl, methylaminopropyl acrylate, ethylaminoethyl acrylate, ethylaminopropyl acrylate, aminoaminoamide acrylate, aminopropylamide acrylate, methylaminoethylamide acrylate, methylaminopropylamide acrylate, ethyl acrylate Aminoethylamide, acrylic acid ethylaminopropylamide, methacrylic acid amide, aminoethyl methacrylate, aminopropyl methacrylate, methacrylic acid methyl ester Aminoethyl, methylaminopropyl methacrylate, ethylaminoaminomethacrylate, ethylaminopropyl methacrylate, aminomethacrylic acid aminoethylamide, methacrylic acid aminopropylamide, methacrylic acid methylaminoethylamide, methacrylic acid methylaminopropylamide, ethyl methacrylate Aminoethylamide, methacrylic acid ethylaminopropylamide, hydroxymethyl acrylate, acrylic acid-
Examples thereof include 2-hydroxyethyl, 2-hydroxypropyl acrylate, hydroxymethyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, N-methylol acrylamide and allyl alcohol.

As the monomer having a crosslinkable functional group,
Listed below.

The polymerizable monomer having a blocked isocyanate group has a polymerizable monomer having an isocyanate group such as 2-methacryloyloxyethylisocyanate, which is added with a known blocking agent, or has the above-mentioned hydroxyl group and carboxyl group. It can be easily produced by adding a compound having an isocyanate group and a blocked isocyanate group to the vinyl copolymer. A compound having an isocyanate group and a blocked isocyanate group can be easily obtained by subjecting a diisocyanate compound and a known blocking agent to an addition reaction at a molar ratio of about 1: 1.

Examples of the monomer having an epoxy group include glycidyl (meth) acrylate and (meth) acrylate monomer having an alicyclic epoxy group.

Examples of the monomer having a 1,3-dioxolan-2-one-4-yl group include 1,3-dioxolan-2-on-4-ylmethyl (meth) acrylate and 1,3-dioxolane-2. Examples include-on-4-ylmethyl vinyl ether.

Examples of the polymerization initiator include t-butyl peroxybenzoate, di-t-butyl peroxide, cumene per hydroxide, acetyl peroxide,
Examples thereof include peroxides such as benzoyl peroxide and lauroyl peroxide; and azo compounds such as azobisisobutylnitrile, azobis-2,4-dimethylvaleronitrile and azobiscyclohexanecarbonitrile.

Examples of the solvent used for polymerizing the anionic group-containing acrylic monomer and, if necessary, other monomer copolymerizable with these monomers include aliphatic solvents such as hexane and mineral spirits. Hydrocarbon solvent; aromatic hydrocarbon solvent such as benzene, toluene, xylene, etc .; ester solvent such as butyl acetate; ketone solvent such as methyl ethyl ketone, isobutyl methyl ketone, etc .; methanol, ethanol, butanol, isopropyl alcohol, etc. Alcoholic solvents such as; dimethylformamide, dimethylsulfoxide, N
-Aprotic polar solvents such as methylpyrrolidone, pyridine, etc. may be mentioned. These solvents can be used in combination of two or more kinds.

The anionic microencapsulated pigment-containing aqueous dispersion by the phase inversion method is produced as follows.

In the phase inversion method, a mixture (composite or composite) of anionic organic polymer compounds having self-dispersing ability or dissolving ability with water and organic pigment or carbon black, or organic pigment or carbon The organic solvent used when the mixture of the black, the curing agent and the anionic organic polymer compound is used as the organic solvent phase is not particularly limited, and can dissolve the anionic organic polymer compounds. As long as any of them can be used, from the viewpoint of easy removal of the solvent at the time of production, ketone-based solvents such as acetone and methyl ethyl ketone; ester-based solvents such as ethyl acetate; alcohol-based solvents such as ethanol and isopropyl alcohol; benzene. Solvents having a low boiling point such as aromatic hydrocarbon solvents such as

The ratio of the anionic organic polymer compounds is
The range of 25 to 186 parts by weight is preferable with respect to 100 parts by weight of the organic pigment or carbon black.
A range of 0 parts by weight is especially preferred.

In particular, what is desirable for the mixture (composite or composite) which is an organic phase is that the pigment is finely and uniformly dispersed in the organic polymer compound without any aggregation and stabilized. At the same time, the cross-linking agent and the polymer compound are compatible with the anionic organic polymer compound, but the invention is not limited thereto.

The method for stabilizing the dispersion of the mixture is not particularly limited, but if only typical ones are exemplified, (1) powdered organic pigment or carbon black By using various dispersers such as a bead mill, a roll mill and a sand mill.
A method of finely dispersing in anionic organic polymer compounds and then dissolving or dispersing a curing agent or polymer compound, or (2) a wet cake after synthesis of an organic pigment or A wet cake of carbon black, that is, a state in which a pigment is dispersed in water, is flushed with an anionic organic polymer compound before neutralization by using various dispersing machines such as a kneader. To make it finely dispersed, and then
Examples include a method of dissolving or dispersing a curing agent and a polymer compound. In these dispersion methods, in order to obtain ultrafine particles, a method of bead mill dispersion or flushing is more preferable.

The latter method, in particular, uses a wet cake and therefore does not require a step of drying the organic pigments, which saves energy and does not cause strong agglomeration at all during the drying step. Therefore, it is extremely useful.

Further, for the purpose of stabilizing the dispersion, a pigment derivative having a dialkylaminomethyl group, a sphonsan group, a sphonamide group, a phthalimide group, etc .; "BYK-160", "BYK-166" manufactured by Big Chemie, manufactured by Zeneca. The dispersion time and the like can be shortened by using a pigment dispersant such as "Solspers 24000".

In order to facilitate self-dispersion (phase inversion emulsification) and to simplify the solvent removal operation, it is desirable to keep the amount of the solvent used in the mixture as low as possible,
As such, the viscosity of these mixtures is 1000
It is desirable to adjust it to 0 CP or less.

By introducing water into the organic phase of the mixture or by introducing the organic phase into water, self-dispersion (phase inversion emulsification) can be carried out. By slowly adding one of them to the other while appropriately stirring them, the desired microencapsulated pigment can be instantly formed.

In such stirring, the type and speed of the stirrer do not affect the size of the particles to be formed, so that the type and speed of the stirrer are not particularly limited.

In such a production method, it is possible to produce a sufficiently fine microencapsulated pigment even by the above-mentioned procedure, but as a method for producing a finer pigment, ultrasonic waves are applied while applying ultrasonic waves to the organic phase. It is to emulsify each other.
The frequency of the ultrasonic wave is not particularly limited, but is preferably 10 to 200 KHz.

When using so-called neutralizing type anionic organic polymer compounds, it is necessary to previously dissolve a necessary amount of neutralizing bases in the organic phase or the aqueous phase. In particular, it is more preferable to dissolve the bases in the aqueous phase in consideration of the aggregation of the pigment in the organic phase.

The cross-linking agent used for gelling the formed capsule wall or for increasing the film strength of the recording liquid after film formation is, for example, a water-soluble compound such as polyamines. Even when using it,
Only the required amount needs to be dissolved in the organic phase.

The anionic microencapsulated pigment-containing aqueous dispersion obtained by these various methods can be used as it is, or it can be used as an aqueous dispersion by removing the solvent, depending on the form for practical use. You can also

Examples of the method for removing the solvent include a general distillation method and a vacuum distillation method.

On the other hand, a water-containing cake consisting of anionic group-containing organic polymer compounds and an organic pigment or carbon black was prepared by using the same materials as described above, and a basic compound was used to prepare a part or all of the anionic groups. The method (acid precipitation method) for obtaining an anionic microencapsulated pigment-containing aqueous dispersion by neutralizing the following is the following procedure. (1) Anionic organic polymer compounds and a pigment are dispersed in an alkaline aqueous medium. In addition, heat treatment is performed as necessary to achieve gelation of the resin. (2) The resin is made hydrophobic by making the pH neutral or acidic, and the resin is strongly fixed to the pigment. (4) Filter and wash with water as needed. (5) Neutralize the carboxyl group with a basic compound and redisperse it in an aqueous medium. In addition, heat treatment is performed as necessary to achieve gelation of the resin.

The following two methods are suitable for dispersing the anionic organic polymer compound and the pigment in the step (1) in an alkaline aqueous medium. (1) The pigment is kneaded in an organic solvent medium and then dispersed in an aqueous medium. (2) Mix or knead the pigments in an aqueous medium.

In the above (1) method, first, a pigment and
An organic solvent solution of anionic organic polymer compounds is finely dispersed using a known dispersing machine such as a ball mill, a sand mill, a colloid mill.

At this time, as the organic solvent to be used, all commonly used organic solvents can be used, but those having good solubility in the resin and having no problem in the synthesis of the resin, having a higher vapor pressure than water, Those that are easy to do and those that are miscible with water are preferred. As such a solvent, for example,
Acetone, methyl ethyl ketone, methanol, ethanol, n-propanol, isopropanol, ethyl acetate, tetrahydrofuran and the like can be mentioned. Low miscibility with water, but methyl isopropyl ketone, methyl-n-
Propyl ketone, isopropyl acetate, n-propyl acetate, methylene chloride, benzene and the like can also be used in this method.

To disperse a dispersion comprising a pigment and an anionic organic polymer compound dispersed in an organic solvent medium in an aqueous medium, (1) the carboxyl group of the anionic organic polymer compound is basic. A method of neutralizing with a compound to make anionic organic polymer compounds hydrophilic and dispersing them in water, or (2) from anionic organic polymer compounds and pigments neutralized with a basic compound And a method of dispersing the resulting dispersion in water.

The following method is suitable for dispersing in water. (A) A dispersion comprising an anionic organic polymer compound and a pigment is neutralized with a basic compound, and then water is added dropwise. (B) Water is added dropwise to a dispersion composed of an anionic organic polymer compound and a pigment neutralized with a basic compound. (C) Water containing a basic compound is added dropwise to a dispersion composed of anionic organic polymer compounds and a pigment. (D) A dispersion comprising an anionic organic polymer compound and a pigment is neutralized with a basic compound and added to an aqueous medium. (E) A dispersion composed of an anionic organic polymer compound and a pigment neutralized with a basic compound is added to an aqueous medium. (F) A dispersion comprising an anionic organic polymer compound and a pigment is added to an aqueous medium containing a basic compound.

When dispersed in water, it may be carried out by ordinary low shear stirring, high shear stirring with a homogenizer, or ultrasonic waves. Further, for the purpose of assisting dispersion in an aqueous medium, a surfactant, a protective colloid or the like may be used in combination within a range that does not significantly reduce the water resistance of the coating film.

Examples of the basic compound include alkali metals such as sodium hydroxide, potassium hydroxide and lithium hydroxide; organic amines such as ammonia, triethylamine, tributylamine, dimethylethanolamine, diisopropanolamine and morpholine. To be

A method of kneading a resin and a pigment in an aqueous medium, which is a method (2) applicable to the step (1) of dispersing an anionic organic polymer compound and a pigment in an alkaline aqueous medium, is First, the carboxyl groups of anionic organic polymer compounds are neutralized with the above-mentioned basic compound, and mixed or kneaded with the pigment in an aqueous medium. At this time, the resin dissolved or dispersed in water may contain an organic solvent, or the solvent may be removed to be a medium substantially containing only water. Pigments include powder pigments, aqueous slurries,
Any of the press cakes can be used. When the pigment is dispersed in an aqueous medium, it is preferable to use an aqueous slurry or a press cake with less secondary aggregation of the pigment particles in order to simplify the production process. As the kneading method, the organic solvent and the basic compound, the same method and the same material as those in the case of dispersion in an organic solvent medium can be used.

In either case of kneading with an organic solvent system or an aqueous system, a pigment dispersant or a wetting agent is used for the purpose of assisting the dispersion of the pigment, as long as the water resistance of the recorded image is not deteriorated. You can also

When the pigment is kneaded or after kneading and before acid precipitation, substances other than the pigment, for example, dyes, antioxidants, ultraviolet absorbers, coating catalyst binder curing catalysts, rust preventives, etc. Agents, fragrances, drugs, etc. can also be added.

The proportion of the anionic organic polymer compound used is appropriately 25 to 186 parts by weight, preferably 30 to 150 parts by weight, per 100 parts by weight of the organic pigment. The use ratio of anionic organic polymer compounds is 2
When it is less than 5 parts by weight, it tends to be difficult to disperse the pigment in a sufficiently fine manner, and when it is more than 186 parts by weight, the proportion of the pigment in the dispersion becomes small and the aqueous pigment dispersion is used as a recording liquid. When used, it is not preferable because there is a tendency for the composition design margin to be exhausted.

Furthermore, when the anionic organic polymer compounds are gelled by heat treatment after kneading the pigment, the non-volatile content of the kneading dispersion should be 15% or less, preferably 10% or less. Is preferred.

There is no problem as long as the heating temperature is higher than the temperature at which the crosslinking of the resin proceeds, but the preferable temperature range is 7
0 ° C to 200 ° C. If the heating temperature is less than 70 ° C, it takes too long to crosslink, and if the heating temperature exceeds 200 ° C,
Depending on the type of pigment, crystal growth or dispersion stability may be impaired, and it tends to be difficult to encapsulate, which is not preferable.

The acid precipitation carried out for the purpose of strongly fixing the resin to the pigment finely dispersed in the aqueous medium is carried out by removing the carboxyl group of the anionic organic polymer compounds neutralized by the basic compound from the acidic compound. In addition, by making the pH neutral or acidic, the resin is made hydrophobic.

The acidic compound used is, for example,
Inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid; formic acid, acetic acid,
Organic acids such as propionic acid can be used, but hydrochloric acid or sulfuric acid, which has a small amount of organic substances in the waste water and has a large acid precipitation effect, is preferred. The pH at the time of acid precipitation is preferably in the range of 2 to 6, but some pigments are decomposed by an acid. In the case of such a pigment, the acid precipitation is preferably in the range of pH 4 to 7. Before carrying out acid precipitation, it is preferable to remove the organic solvent present in the system in advance by using a method such as vacuum distillation.

After acid precipitation, filtration and washing with water are carried out if necessary to obtain a water-containing cake of dispersed pigment. As the filtration method, known methods such as suction filtration, pressure filtration, and centrifugal separation can be adopted.

This water-containing cake was not dried,
By re-neutralizing the carboxyl group with the basic compound while keeping the water content, the pigment particles are re-dispersed in the aqueous medium while maintaining the fine state without agglomeration. As the basic compound, in consideration of redispersibility and water resistance of the recording liquid, alkali metal such as sodium hydroxide, potassium hydroxide and lithium hydroxide, and organic amine compounds such as triethanolamine and diethanolamine which are hard to volatilize Alone, or with these, ammonia,
It is preferably used in combination with a volatile amine compound such as triethylamine or dimethylethanolamine.

As described above, the anionic microencapsulated pigment used in the present invention is capable of encapsulating fine particles without using any so-called auxiliary material such as an emulsifier. Thus, microcapsules can be prepared.

The average particle size of the organic pigment in the microencapsulated pigment used in the present invention is a measured value obtained by averaging the major axis and minor axis of several tens of samples using a photograph taken with an electron microscope. To use.

The average particle size of the microencapsulated pigment used in the present invention is slightly different depending on the particle size measuring method, and therefore it is preferable to use the actual measurement value measured by an electron microscope, but the laser Doppler system particle size measurement It can also be measured using an apparatus.

The thus obtained anionic microencapsulated pigment-containing aqueous dispersion has improved pigment dispersion stability more than ever before, and when used as a coloring material for a recording liquid, the fineness of the recording liquid and the There is an advantage that performances such as light resistance, color rendering and transparency are improved. In addition, since the pigment concentration in the microcapsules is high, the versatility is high, and the labor for dispersing the pigment can be saved. Therefore, there is an advantage that labor for dispersing energy and labor can be saved. In addition, water resistance is also improved because no surfactant is used. Furthermore, since an oil-based curing agent and a vehicle for recording liquid, which cannot be used conventionally, can be contained in the capsules of the microencapsulated pigment, the range of materials that can be used is widened, and the recording liquid can be directly produced.

As defined in claim 1, the content of the organic pigment in the anionic microencapsulated pigment is 35 to 8
A range of 0% by weight is preferred. When the content of the organic pigment in the anionic microencapsulated pigment is less than 35%, the resin concentration in the capsule becomes high, and therefore the compatibility with the resin for the recording liquid, the solvent, the additive such as the auxiliary agent, etc. There is a possibility that it is limited, or the amount of its additives is limited, it lacks versatility, and since the pigment concentration in the capsule becomes low, when used as an aqueous dispersion as a recording liquid, However, the color density cannot be increased or the proportion of the microencapsulated pigment used in the recording liquid must be increased in order to increase the color density, resulting in an increase in the viscosity of the recording liquid, which is not preferable. The content of the organic pigment in the anionic microencapsulated pigment is 80% by weight.
If it is more than the above range, it tends to be difficult to finely disperse the organic pigment, which is not preferable.

Further, when the maximum particle size of the anionic microencapsulated pigment is larger than 1000 nm, the nozzle of the jet ink printer may be clogged, and thus the anionic microencapsulated pigment is defined. The maximum particle size of the pigment is 1000 nm or less,
It is more preferably 500 nm or less.

The average particle size of the organic pigment in the anionic microencapsulated pigment is preferably 300 nm or less, and particularly preferably 250 nm or less. When the average particle diameter of the organic pigment used is larger than 300 nm, when the microencapsulated pigment in the dispersion is stored for a long period of time,
When used as a recording liquid, it is inferior in color developability, transparency or fineness because it is settled or encapsulated in a state where pigments are aggregated during microencapsulation.
Recording on a P sheet or the like is not preferable because it tends to obstruct the transmission of light and fail to project a clean color. .

The anionic organic polymer compounds in the anionic microencapsulated pigment of the present invention are preferably used in the form of a salt of an alkali metal or an organic amine. When used in the form of a salt of an alkali metal such as sodium hydroxide, potassium hydroxide or lithium hydroxide, the inorganic base remains in the recorded image, so that the recorded image tends to have poor water resistance, It is preferable because the redispersibility is excellent and the reliability of the recording liquid is high.

Examples of the organic amine include volatile amine compounds such as ammonia, triethylamine, tributylamine, dimethylethanolamine, diisopropanolamine and morpholine; diethanolamine,
Examples thereof include high boiling organic amines that are difficult to volatilize, such as triethanolamine.

The content of the anionic microencapsulated pigment contained in the aqueous dispersion containing anionic microencapsulated pigment for recording liquid of the present invention is preferably 70 parts by weight or less based on 100 parts by weight of the aqueous dispersion. The range of 60 to 60 parts by weight is more preferable, and the range of 10 to 50 parts by weight is particularly preferable. When the content of the microencapsulated pigment in the aqueous dispersion is higher than 70 parts by weight, since the aqueous dispersion substantially tends to exhibit a solid state, aggregation of the microcapsules occurs and the dispersion needs to be performed again. Is not preferred.
If the content of the microencapsulated pigment in the aqueous dispersion is less than 2 parts by weight, the color density tends to be insufficient when used in the recording liquid, which is not preferable. Considering that an additive for improving the performance is added to the recording liquid, if the content of the microencapsulated pigment in the aqueous dispersion is less than 10 parts by weight, the additive amount tends to be limited. Therefore, it is not preferable.

The recording liquid containing the aqueous dispersion containing the anionic microencapsulated pigment of the present invention is a mixture of the anionic microencapsulated pigment-containing aqueous dispersion described above, a water-soluble organic solvent, water and the like. Prepared. Further, if necessary, a water-soluble resin, an organic amine, a surfactant,
Preservatives, viscosity modifiers, pH modifiers, chelating agents and the like can also be added.

The content ratio of the anionic microencapsulated pigment-containing aqueous dispersion in the recording liquid of the present invention is 1 to 100 in consideration of color density, definition, transparency, hue saturation and the like as the recording liquid. A range of 5% by weight is preferable, and a range of 5 to 100% by weight is particularly preferable. It is needless to say that 100% by weight is particularly preferable in view of directly providing the recording liquid.

As the water-soluble organic solvent used for the recording liquid,
For example, alcohols such as methyl alcohol, ethyl alcohol, n-butyl alcohol, isobutyl alcohol, tert-butyl alcohol, n-propyl alcohol and isopropyl alcohol; amides such as dimethylformaldehyde and dimethylacetamide; acetone,
Ketones such as methyl ethyl ketone; tetrahydrofuran, dioxane, ethylene glycol methyl ether,
Ethers such as ethylene glycol ethyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, triethylene glycol monomethyl ether, triethylene ethylene glycol monoethyl ether; ethylene glycol, propylene glycol, butylene glycol, triethylene glycol,
1,2,6-hexanetriol, thiodiglycol,
Polyhydric alcohols such as diethylene glycol, polyethylene glycol, polypropylene glycol, glycerin; N-methyl-pyrrolidone, 1,3-dimethyl-2-
Examples thereof include imidazolidinone. Among these water-soluble organic solvents, polyhydric alcohols and ethers are preferable.

The content ratio of the water-soluble organic solvent in the recording liquid is
It is preferably 95% by weight or less, particularly preferably in the range of 0 to 80% by weight.

Examples of the water-soluble resin used in the recording liquid as necessary include natural proteins such as glue, gelatin, casein, albumin, gum arabic, and fish glue, alginic acid, methyl cellulose, carboxymethyl cellulose, polyethylene oxide, hydroxyethyl cellulose, Examples thereof include synthetic polymers such as polyvinyl alcohol, polyacrylamide, aromatic amide, polyacrylic acid, polyvinyl ether, polyvinylpyrrolidone, acryl and polyester.

The water-soluble resin is used as necessary for the purpose of improving fixability, viscosity control, and quick-drying property.
When used in the recording liquid, the content ratio of the water-soluble resin in the recording liquid is preferably 30% by weight or less, and particularly preferably 20% by weight or less.

Examples of the organic amine used as necessary in the recording liquid include ethanolamine, diethanolamine, triethanolamine, N-methylethanolamine, N-ethyldiethanolamine and 2-amino-2-.
Methylpropanol, 2-ethyl-2-amino-1,3
-Propanediol, 2- (aminoethyl) ethanolamine, tris (hydroxymethyl) aminomethane, ammonia, piperidine, morpholine and the like.

The method for producing a recording liquid of the present invention does not require a disperser for dispersing pigments, and can be used with a simple stirrer such as a disperser to prepare an aqueous dispersion containing an anionic microencapsulated pigment and a water-soluble organic solvent. It can also be produced only by stirring and mixing water, water-soluble resin and the like. If necessary, a surfactant, a preservative, a viscosity adjusting agent, a pH adjusting agent, a chelating agent, etc. are added at the time of stirring for production.

The recording liquid thus produced is excellent in definition of recorded images, color developability, transparency, water resistance and redispersibility by using image recording in a jet printer or the like, and labor saving in the dispersion process. As a result, the manufacturing cost of the recording liquid can be significantly reduced.

[0099]

The present invention will be described below in more detail with reference to Examples and Comparative Examples. In the following, "part" and "%"
Represents "parts by weight" and "% by weight" unless otherwise specified.

<Synthesis Example 1> (Synthesis of Anionic Group-Containing Organic Polymer Compounds) 175 parts of n-butyl methacrylate, 10.7 parts of n-butyl acrylate, 37.5 parts of β-hydroxyethyl methacrylate and 26 of methacrylic acid. A mixed solution of 8 parts and 5.0 parts of "perbutyl O" (tert-butyl peroxyoctoate manufactured by NOF CORPORATION) was prepared.

Next, 250 parts of methyl ethyl ketone was charged into a flask, and the mixture was stirred under a nitrogen blanket while stirring to 7
After the temperature was raised to 5 ° C, the above mixed solution was added dropwise over 2 hours and further reacted at the same temperature for 15 hours to obtain a solution of vinyl resin having an acid value of solid content of 70 and a number average molecular weight of 12,500. Got The nonvolatile content of this resin solution was 48%.
Hereinafter, this is abbreviated as resin solution (A-1).

<Synthesis Example 2> (Synthesis of organic polymer compounds containing anionic group) 43 parts of styrene, 87.5 parts of n-butyl acrylate,
A mixed solution of 37.5 parts of β-hydroxyethyl methacrylate, 19.5 parts of methacrylic acid and 5.0 parts of “perbutyl O” was prepared.

Next, 250 parts of methyl ethyl ketone was charged into a flask, and the mixture was stirred under a nitrogen blanket while stirring to 7
After the temperature was raised to 5 ° C, the above mixed solution was added dropwise over 2 hours and further reacted at the same temperature for 15 hours to obtain a solution of a vinyl resin having a solid content acid value of 48 and a number average molecular weight of 14,000. Got The nonvolatile content of this resin solution was 49%.
Hereinafter, this is abbreviated as a resin solution (A-2).

<Synthesis Example 3> (Synthesis of organic polymer compounds containing anionic group) 100 parts of styrene, 40.3 of n-butyl acrylate
Parts, 37.5 parts of β-hydroxyethyl methacrylate,
A mixed solution containing 9.7 parts of methacrylic acid and 5.0 parts of "perbutyl O" was prepared.

Next, after 250 parts of methyl ethyl ketone was charged into the flask, it was stirred under a nitrogen blanket while stirring to 7
After the temperature was raised to 5 ° C., the above mixed solution was added dropwise over 2 hours and further reacted at the same temperature for 15 hours to obtain a solution of vinyl resin having a solid content acid value of 24 and a number average molecular weight of 15,000. Got The nonvolatile content of this resin solution was 49%.
Hereinafter, this is abbreviated as resin solution (A-3).

<Synthesis Example 4> (Synthesis of anionic group-containing organic polymer compounds) 175 parts of n-butyl methacrylate, 10.7 parts of n-butyl acrylate, 37.5 parts of β-hydroxyethyl methacrylate and 26 of methacrylic acid. A mixed solution of 0.8 parts and 20.0 parts of "Perbutyl O" was prepared.

Next, after 250 parts of methyl ethyl ketone was charged into the flask, it was stirred under a nitrogen blanket while stirring to 7
After the temperature was raised to 5 ° C., the above mixed solution was added dropwise over 2 hours and further reacted at the same temperature for 15 hours to obtain a solution of vinyl resin having a solid content acid value of 68 and a number average molecular weight of 5600. Got The nonvolatile content of this resin solution was 50%. Hereinafter, this is abbreviated as resin solution (A-4).

<Synthesis Example 5> (Synthesis of anionic group-containing organic polymer compounds) 153.8 parts of n-butyl methacrylate, 20.4 parts of n-butyl acrylate, 37.5 parts of β-hydroxyethyl methacrylate, methacryl A mixed solution consisting of 38.3 parts of acid and 5.0 parts of "perbutyl O" was prepared. Next, 250 parts of methyl ethyl ketone was charged into a flask, and then, under a nitrogen seal.

After the temperature was raised to 75 ° C. with stirring, the above mixed solution was added dropwise over 2 hours and further reacted at the same temperature for 15 hours to give an acid value of solid content of 98 and number average. A solution of vinyl resin having a molecular weight of 12,500 was obtained. The nonvolatile content of this resin solution was 51%. Hereinafter, this is abbreviated as resin solution (A-5).

<Synthesis Example 6> (Synthesis of anionic group-containing organic polymer compounds) 171.4 parts of n-butyl methacrylate, 6.3 parts of n-butyl acrylate, 37.5 parts of β-hydroxyethyl methacrylate, acrylic A mixed solution consisting of 34.8 parts of acid and 20.0 parts of "perbutyl O" was prepared.

Next, 250 parts of methyl ethyl ketone was charged into a flask, and the mixture was stirred at 75 ° C. under a nitrogen blanket.
After the temperature is raised to 0, the above mixed solution is added dropwise over 2 hours and further reacted at the same temperature for 15 hours to obtain a solution of vinyl resin having an acid value of solid content of 95 and a number average molecular weight of 8800. It was The nonvolatile content of this resin solution was 50%. Less than,
This is abbreviated as resin solution (A-6).

<Synthesis Example 7> (Synthesis of organic polymer compounds containing anionic group-for gelation treatment) 83.8 parts of n-butyl methacrylate, 89.4 parts of n-butyl acrylate, and β-hydroxyethyl methacrylate 37 0.5 parts, methacrylic acid 26.7 parts, glycidyl methacrylate 12.5 parts and "perbutyl O" 2
A mixture of 0.0 parts was prepared.

Next, 250 parts of methyl ethyl ketone was charged into a flask, and the mixture was stirred while stirring under a nitrogen blanket.
After the temperature was raised to 5 ° C., the above mixed solution was added dropwise over 2 hours and further reacted at the same temperature for 15 hours to obtain a solution of vinyl resin having a solid content acid value of 69 and a number average molecular weight of 10400. Got The nonvolatile content of this resin solution was 50%.
Hereinafter, this is abbreviated as a resin solution (A-7).

[0114]

[Table 1]

<Production Example 1> (Production of an aqueous dispersion containing copper phthalocyanine blue anionic microencapsulated pigment) 22.1 parts of the resin solution (A-5) obtained in Synthesis Example 5, "Fastogen Blue. TGR "(Dainippon Ink and Chemicals
C.I. I. Pigment Blue 15, average particle diameter 50 nm, maximum particle diameter 100 nm) 14.25 parts, dimethylaminomethyl copper phthalocyanine 0.
75 parts, methyl ethyl ketone 78.2 parts, "Super.
Beckamine L-109-60 "(a melamine resin manufactured by Dainippon Ink and Chemicals, Inc.) 4.7 parts and ceramic beads 300 parts were placed in a stainless steel container, and the mixture was mixed using a bead mill disperser. And dispersed to prepare a paste for microencapsulated pigment.

Next, 40.0 parts of the above microencapsulated pigment paste and 0.4 parts of dimethylaminoethanol were placed in a polycup and mixed with a stirrer to form an organic phase. While stirring and irradiating the organic phase with ultrasonic waves of 45 KHz, 50 parts of ion-exchanged water was dropped into the organic phase over 12 minutes to carry out self-dispersion (phase inversion emulsification) and to form anionic microcapsules. An aqueous pigment-containing dispersion was obtained.

Further, this microcapsulated pigment-containing aqueous dispersion was distilled at 85 ° C. to distill off the solvent, and then held at the same temperature for 5 hours to perform gelation treatment on the capsule wall.

The particle size of the microencapsulated pigment in the thus obtained aqueous dispersion containing anionic microencapsulated pigment (MC-1) was measured by "UPA-150" (laser Doppler system particle size distribution measurement manufactured by Nikkiso Co., Ltd.). Machine), the volume average particle diameter of the microencapsulated pigment was 148 nm, and 0% of the particles had a maximum particle diameter of 1000 nm or more. The aqueous dispersion containing the microencapsulated pigment had a nonvolatile content of 24.5%, and the content of the pigment in the microcapsules was 51.7%.

<Production Example 2> (Production of an aqueous dispersion containing anionic microencapsulated pigment of copper phthalocyanine blue) (1) Pigment kneading step A resin solution (A-4 prepared in Synthesis Example 4 was placed in a glass bottle having a capacity of 250 ml). ) 15.0 parts, dimethylethanolamine 0.8 part and "Fastgen Blue TGR" 15 parts were added, and ion-exchanged water was added to make the total amount 75 parts, and then the average particle size was 0. After adding 250 g of 5 mm zirconia beads, kneading was performed for 4 hours using a paint shaker. After the completion of the kneading, the glass beads were filtered off to obtain a dispersion of a resin and a pigment having a carboxyl group neutralized with a base, dispersed in water.

(2) Acid precipitation A dispersion of a resin having a carboxyl group having a carboxyl group neutralized with a base and a pigment is dispersed in water, and water is added to the mixture to dilute it. Normal hydrochloric acid was added until the resin became insoluble and fixed to the pigment. P at this time
H was 3-5.

(3) Filtration and Washing With water, the aqueous medium containing the pigment to which the resin had been fixed was suction filtered, and then the salt was washed with water to obtain a wet cake.

(4) Neutralization and Redispersion in Aqueous Medium While stirring the water-containing cake using a disper, a 10% aqueous solution of dimethylethanolamine was added until the pH of the dispersion became 8.5 to 9.5. Was added. After continuing stirring for 1 hour, water was added to adjust the nonvolatile content to 20% to obtain an anionic microencapsulated pigment-containing aqueous dispersion (MC-2).

The particle size of the microencapsulated pigment in the anionic microencapsulated pigment-containing aqueous dispersion (MC-2) was measured in the same manner as in Production Example 1, and as a result, the volume average particle size of the microencapsulated pigment was 170 nm. And 1000
Particles with a size of nm or more were 0%. The content of the pigment in the microcapsules was 67%.

<Production Example 3> (Production of copper phthalocyanine blue anionic microencapsulated pigment-containing aqueous dispersion with an inorganic salt) (1) Pigment kneading step In the same manner as in Production Example 2, a carboxyl neutralized with a base is prepared. A dispersion of a resin having a group and a pigment in water was obtained.

(2) Acid precipitation To a dispersion of a resin having a carboxyl group neutralized with a base and a pigment dispersed in water, water is added and diluted twice, and then stirred with a disper while Normal hydrochloric acid was added until the resin became insoluble and fixed to the pigment. P at this time
H was 3-5.

(3) Filtration and Washing With water, the aqueous medium containing the pigment to which the resin had been fixed was suction filtered, and then the salt was washed with water to obtain a wet cake.

(4) Neutralization and Redispersion in Aqueous Medium While stirring the water-containing cake using a disper, a 10% sodium hydroxide aqueous solution was added until the pH of the dispersion became 8.5 to 9.5. added. After continuing stirring for 1 hour, water is added to adjust the nonvolatile content to 20%, and the anionic microencapsulated pigment-containing aqueous dispersion (MC
-3) was obtained.

The particle size of the microencapsulated pigment in the anionic microencapsulated pigment-containing aqueous dispersion (MC-3) was measured in the same manner as in Production Example 1, and as a result, the volume average particle size of the microencapsulated pigment was 182 nm. And 1000
Particles with a size of nm or more were 0%. The content of the pigment in the microcapsules was 67%.

<Production Example 4> (Production of copper phthalocyanine blue anionic microencapsulated pigment-containing aqueous dispersion) The resin having a carboxyl group in the resin solution (A-2) obtained in Synthesis Example 2 was replaced with dimethylethanol. With amine 1
Pigment kneading, acid precipitation, filtration and washing with water, neutralization and redispersion were carried out in the same manner as in Production Example 2 except that a 100% neutralized anionic microencapsulated pigment having a nonvolatile content of 20% was contained. An aqueous dispersion (MC-4) was obtained.

The particle size of the microencapsulated pigment in the anionic microencapsulated pigment-containing aqueous dispersion (MC-4) was measured in the same manner as in Production Example 2. As a result, the volume average particle size of the microencapsulated pigment was 218 nm. And 1000
Particles with a size of nm or more were 0%. The content of the pigment in the microcapsules was 67%.

<Production Example 5> (Production of copper phthalocyanine blue anionic microencapsulated pigment-containing aqueous dispersion using anionic organic polymer compounds having an acid value of 25) (1) Pigment kneading step In Synthesis Example 3 The resin having a carboxyl group in the obtained resin solution (A-3) was treated with dimethylethanolamine to give 1
It was 00% neutralized. In a 250 ml glass bottle, 7.5 parts of the neutralized resin in terms of solid content and "Fastgen
After adding 15 parts of "Blue TGR", a resin-soluble amount of methyl ethyl ketone, and adding ion-exchanged water so that the total amount becomes 75 parts, 250 g of zirconia beads having an average particle diameter of 0.5 mm is added, Kneading was performed for 4 hours using a paint shaker. After the completion of the kneading, the glass beads were filtered off to obtain a dispersion of a resin and a pigment having a carboxyl group neutralized with a base, dispersed in water.

(2) Acid Deposition: A dispersion of a resin and a pigment having a carboxyl group which has been neutralized with a base is dispersed in water, water is added to the mixture to double the dilution, and the mixture is stirred with a disper to 1 N. Hydrochloric acid was added until the resin became insoluble and fixed to the pigment. PH at this time
Was 3-5.

(3) Filtration and Washing With water, the aqueous medium containing the pigment to which the resin had been fixed was suction filtered, and then the salt was washed with water to obtain a wet cake.

(4) Neutralization and Redispersion in Aqueous Medium While stirring the water-containing cake using a disper, a 10% aqueous solution of dimethylethanolamine was added until the pH of the dispersion became 8.5 to 9.5. Was added. After continuing stirring for 1 hour, water was added to adjust the nonvolatile content to 20% to obtain an anionic microencapsulated pigment-containing aqueous dispersion (MC-5).

The particle size of the microencapsulated pigment in the anionic microencapsulated pigment-containing aqueous dispersion (MC-5) was measured in the same manner as in Production Example 1, and as a result, the volume average particle size of the microencapsulated pigment was 650 nm. And 1000
The number of particles having a size of nm or more was 17%. The content of the pigment in the microcapsules was 67%.

<Production Example 6> (Production of magenta anionic microencapsulated pigment-containing aqueous dispersion) 23.4 parts of the resin solution (A-1) obtained in Synthesis Example 1, "Fastgen Super Magenta"・ RTS "(CI Pigment Red 12 manufactured by Dainippon Ink and Chemicals, Inc.
2, average particle diameter 45nm, maximum particle diameter 100nm) 1
4.25 parts, 0.75 parts of dimethylaminomethylquinacridone as a dispersion aid, 76.9 parts of methyl ethyl ketone,
After 4.7 parts of "Super Beckamine L-109-60" (a melamine resin manufactured by Dainippon Ink and Chemicals, Inc.) and 300 parts of ceramic beads were placed in a stainless steel container, the mixture was dispersed in a bead mill. A paste for microencapsulated pigment was prepared by dispersing using a machine.

Next, 40.0 parts of the above microencapsulated pigment paste and 0.4 parts of dimethylaminoethanol were placed in a polycup and mixed with a stirrer to form an organic phase. While stirring, and irradiating the organic phase with ultrasonic waves of 45 KHz, 50 parts of ion-exchanged water was dropped into the organic phase over 12 minutes to perform self-dispersion (phase inversion emulsification). A chemical pigment-containing aqueous dispersion was obtained.

Furthermore, the solvent was distilled off from the aqueous dispersion containing the microencapsulated pigment at 85 ° C., and the temperature was kept at the same temperature for 5 hours to perform gelation treatment on the capsule wall.

The particle size of the microencapsulated pigment in the thus-obtained anionic microencapsulated pigment-containing aqueous dispersion (MC-6) was measured in the same manner as in Production Example 1, and as a result, the microencapsulated pigment was obtained. Has a volume average particle size of 1
At 45 nm, the maximum particle size is 0 for particles with a diameter of 1000 nm or more.
%Met. The nonvolatile content concentration of the microcapsule-containing pigment-containing aqueous dispersion was 23.2%, and the pigment content in the microcapsules was 51.7%.

<Production Example 7> (Production of magenta-colored anionic microencapsulated pigment-containing aqueous dispersion) (1) Pigment kneading step A resin solution (A-4) obtained in Synthesis Example 4 was placed in a glass bottle having a capacity of 250 ml. 15.0 parts, dimethylethanolamine 0.8 parts and "Fastgen Super Magenta R"
TS "(CI Pigment Red 122 manufactured by Dainippon Ink and Chemicals, Inc., average particle diameter 45 nm, maximum particle diameter 100 nm) 15 parts, and ion-exchanged water is added so that the total amount becomes 75 parts. The average particle size is 0.5 mm
After adding 250 g of the zirconia beads of the above, the mixture was kneaded for 4 hours with a paint shaker. After the completion of the kneading, the glass beads were filtered off to obtain a dispersion of a resin and a pigment having a carboxyl group neutralized with a base, dispersed in water.

(2) Acid precipitation A dispersion of a resin and a pigment having a carboxyl group neutralized with a base is dispersed in water, and water is added to the mixture to double the dilution. Hydrochloric acid was added until the resin became insoluble and fixed to the pigment. PH at this time
Was 3-5.

(3) Filtration and Washing With water, the aqueous medium containing the pigment to which the resin was fixed was suction-filtered, and then the salt was washed with water to obtain a wet cake.

(4) Neutralization and Redispersion in Aqueous Medium While stirring the water-containing cake using a disper, a 10% aqueous solution of dimethylethanolamine was added until the pH of the dispersion became 8.5 to 9.5. Was added. After continuing stirring for 1 hour, water was added to adjust the nonvolatile content to 20% to obtain an anionic microencapsulated pigment-containing aqueous dispersion (MC-7).

The particle diameter of the microencapsulated pigment in the anionic microencapsulated pigment-containing aqueous dispersion (MC-7) was measured in the same manner as in Production Example 1, and as a result, the volume average particle diameter of the microencapsulated pigment was found to be 100 at 176 nm
Particles of 0 nm or more were 0%. The content of the pigment in the microcapsules was 67%.

<Production Example 8> (The content of the organic pigment is 83%.
Production of Aqueous Dispersion Containing Magenta Anionic Microencapsulated Pigment) Production Example 7 except that the amount of the resin solution (A-4) used in the pigment kneading step was 6.0 parts. 7
The pigment kneading, acid precipitation, filtration, washing with water, neutralization and redispersion were carried out in the same manner as in 1. to obtain an anionic microencapsulated pigment-containing aqueous dispersion (MC-8) having a nonvolatile content of 20%.

The particle size of the microencapsulated pigment in the anionic microencapsulated pigment-containing aqueous dispersion (MC-8) was measured in the same manner as in Production Example 1, and as a result, the volume average particle size of the microencapsulated pigment was 250 nm. And 1000
Particles with a size of nm or more were 0%. The pigment content in the microcapsules was 83%.

<Production Example 9> (The content of the organic pigment is 75%.
Production of Magenta Anionic Microencapsulated Pigment-Containing Aqueous Dispersion Liquid) In Production Example 7, the amount of the resin solution (A-4) used in the pigment kneading step was 10.0 parts, and the resin solution (A-
Pigment kneading, acid precipitation, filtration and washing, neutralization and redispersion were carried out in the same manner as in Production Example 7 except that 5.0 parts of ethyl ethyl ketone was used together with 4), and the non-volatile content was 20%. Aqueous dispersion containing microencapsulated pigment (MC
-9) was obtained.

The particle size of the microencapsulated pigment in the anionic microencapsulated pigment-containing aqueous dispersion (MC-9) was measured in the same manner as in Production Example 1, and as a result, the volume average particle size of the microencapsulated pigment was 180 nm. And 1000
Particles with a size of nm or more were 0%. The pigment content in the microcapsules was 75%.

<Production Example 10> (The content of the organic pigment is 33
% Magenta Anionic Microencapsulated Pigment-Containing Aqueous Dispersion (1) Pigment Dispersion Step A glass bottle having a capacity of 250 ml was charged with 20.0 parts of the resin solution (A-4) obtained in Synthesis Example 4 and dimethylethanol. 1.1 parts amine and "Fastgen Super Magenta R"
5.0 parts of "TS" was added, and ion-exchanged water was added to bring the total amount to 7
After adjusting the amount to 5 parts, 250 g of zirconia beads having an average particle diameter of 0.5 mm was added, and then kneading was performed for 4 hours using a paint shaker. After the completion of the kneading, the glass beads were filtered off to obtain a dispersion of a resin and a pigment having a carboxyl group neutralized with a base, dispersed in water.

Then, acid precipitation, filtration and washing with water, neutralization and redispersion were carried out in the same manner as in Production Example 7 to obtain a nonvolatile content of 20%.
Anionic microencapsulated pigment-containing aqueous dispersion (MC-10) was obtained.

The particle size of the microencapsulated pigment in the anionic microencapsulated pigment-containing aqueous dispersion (MC-10) was measured in the same manner as in Production Example 1, and as a result, the volume average particle size of the microencapsulated pigment was found to be 10 at 224 nm
Particles with a size of 00 nm or more were 0%. The pigment content in the microcapsules was 33%.

<Production Example 11> (average particle size is 250 nm
Of Magenta Color Anionic Microencapsulated Pigment-Containing Aqueous Dispersion Using Organic Pigment) In Production Example 7, instead of "Fastgen Super Magenta RTS", "Chromophtal Red DP" was used.
P-BO "(CI Pigment Red 254 manufactured by Ciba Geigy, average particle size 250 nm, maximum particle size 4)
Aqueous dispersion containing anionic microencapsulated pigment having a non-volatile content of 20% was carried out in the same manner as in Production Example 7, except that the pigment kneading, acid precipitation, filtration and washing with water, neutralization and redispersion were carried out in the same manner as in Production Example 7. (MC-11) was obtained.

The particle size of the microencapsulated pigment in the anionic microencapsulated pigment-containing aqueous dispersion (MC-11) was measured in the same manner as in Production Example 1, and as a result, the volume average particle size of the microencapsulated pigment was found to be At 283 nm, the maximum particle size was 0% for particles of 1000 nm or larger. The content of the pigment in the microcapsules was 67%.

<Production Example 12> (Production of Aqueous Dispersion Containing Yellow Anionic Microencapsulated Pigment) 23.4 parts of the resin solution (A-1) obtained in Synthesis Example 1, “Shimla Fast Yellow 8GTF”. (CI Pigment Yellow 17, manufactured by Dainippon Ink and Chemicals, Inc., average particle diameter 60 nm, maximum particle diameter 120 nm) 15.0
Part, 76.9 parts of methyl ethyl ketone, "Super Beckamine L-109-60" (Dainippon Ink and Chemicals, Inc.)
4.7 parts of melamine resin manufactured by Co., Ltd.) and 300 parts of ceramic beads are placed in a stainless steel container, and the mixture is dispersed using a bead mill disperser to prepare a paste for microencapsulated pigment. did.

Next, 40.0 parts of the above microencapsulated pigment paste and 0.4 parts of dimethylaminoethanol were placed in a polycup and mixed with a stirrer to form an organic phase. While stirring, and irradiating the organic phase with ultrasonic waves of 45 KHz, 50 parts of ion-exchanged water was dropped into the organic phase over 12 minutes to perform self-dispersion (phase inversion emulsification). A chemical pigment-containing aqueous dispersion was obtained.

Further, the aqueous solution containing the microencapsulated pigment was distilled at 85 ° C. to distill off the solvent, and then kept at the same temperature for 5 hours to gel the capsule wall.

The particle diameter of the microencapsulated pigment in the anionic microencapsulated pigment-containing aqueous dispersion (MC-12) thus obtained was measured in the same manner as in Production Example 1, and as a result, the microencapsulated pigment was obtained. The volume average particle diameter was 191 nm, and the maximum particle diameter was 0% for particles having a diameter of 1000 nm or more. The nonvolatile content concentration of the microcapsule-containing pigment-containing aqueous dispersion was 23.8%, and the pigment content in the microcapsules was 51.7%.

<Production Example 13> (Production of yellow-colored anionic microencapsulated pigment-containing aqueous dispersion) (1) Pigment kneading step A resin solution (A-1) obtained in Synthesis Example 1 was placed in a glass bottle having a capacity of 250 ml. 15.6 parts, dimethyl ethanolamine 0.8 parts and "Shimler First Yellow 8GT"
F ”(15 parts) was added, ion-exchanged water was added to adjust the total amount to 75 parts, 250 g of zirconia beads having an average particle diameter of 0.5 mm was added, and then kneading was performed for 4 hours using a paint shaker. It was After the completion of the kneading, the glass beads were filtered off to obtain a dispersion of a resin and a pigment having a carboxyl group neutralized with a base, dispersed in water.

(2) Acid precipitation A dispersion of a resin and a pigment having a carboxyl group which has been neutralized with a base is dispersed in water, water is added to the mixture, and the mixture is diluted twice. Hydrochloric acid was added until the resin became insoluble and fixed to the pigment. PH at this time
Was 3-5.

(3) Filtration and washing with water The aqueous medium containing the pigment to which the resin had been fixed was suction-filtered, and then the salt was washed with water to obtain a wet cake.

(4) Neutralization and Redispersion in Aqueous Medium While stirring the water-containing cake using a disper, a 10% aqueous solution of dimethylethanolamine was added until the pH of the dispersion became 8.5 to 9.5. Was added. After continuing stirring for 1 hour, water was added to adjust the non-volatile content to 20% to obtain a yellow anionic microencapsulated pigment-containing aqueous dispersion (MC-13).

The particle size of the microencapsulated pigment in the anionic microencapsulated pigment-containing aqueous dispersion (MC-13) was measured in the same manner as in Production Example 1, and as a result, the volume average particle size of the microencapsulated pigment was found to be 10 at 183 nm
Particles with a size of 00 nm or more were 0%. The content of the pigment in the microcapsules was 67%.

<Production Example 14> (average particle size is 220 nm
Production of Yellow Anionic Microencapsulated Pigment-Containing Aqueous Dispersion Using Organic Pigment of) In Production Example 13, “Shimla Fast Yellow.
Instead of "8 GTF", "Shimla Fast Yellow
4192 ”(CI Pigment Yellow 154, manufactured by Dainippon Ink and Chemicals, Inc., average particle size 220 nm, maximum particle size 350 nm) was used in the same manner as in Production Example 13 except that the pigment kneading and the acid were mixed. The precipitation, filtration, washing with water, neutralization and redispersion were carried out to obtain an anionic microencapsulated pigment-containing aqueous dispersion (MC-14) having a nonvolatile content of 20%.

The particle size of the microencapsulated pigment in the anionic microencapsulated pigment-containing aqueous dispersion (MC-14) was measured in the same manner as in Production Example 1, and as a result, the volume average particle size of the microencapsulated pigment was found to be 10 at 245 nm
Particles with a size of 00 nm or more were 0%. The content of the pigment in the microcapsules was 67%.

<Production Example 15> (Production of cyan-colored anionic microencapsulated pigment-containing aqueous dispersion using a non-volatile base) (1) Pigment kneading step Obtained in Synthesis Example 6 in a glass bottle having a capacity of 250 ml. After adding 15.0 parts of the resin solution (A-6), 1.1 parts of dimethylethanolamine and 15 parts of "Fastgen Blue TGR", and adding ion-exchanged water so that the total amount becomes 75 parts, After adding 250 g of zirconia beads having an average particle diameter of 0.5 mm, kneading was performed for 4 hours using a paint shaker. After the completion of the kneading, the glass beads were filtered off to obtain a dispersion of a resin and a pigment having a carboxyl group neutralized with a base, dispersed in water.

(2) Acid precipitation [0166] A dispersion of a resin having a carboxyl group and a pigment neutralized with a base and a pigment is dispersed in water, water is added to the mixture, and the mixture is double diluted. Hydrochloric acid was added until the resin became insoluble and fixed to the pigment. PH at this time
Was 3-5.

(3) Filtration and Washing With water, the aqueous medium containing the pigment to which the resin had been fixed was suction filtered, and then the salt was washed with water to obtain a wet cake.

(4) Neutralization and Redispersion in Aqueous Medium While stirring the water-containing cake with a disper, a 10% sodium hydroxide aqueous solution was added until the pH of the dispersion became 8.5 to 9.5. added. After continuing stirring for 1 hour, water was added to adjust the nonvolatile content to 20% to obtain a blue anionic microencapsulated pigment-containing aqueous dispersion (MC-15).

The particle size of the microencapsulated pigment in the anionic microencapsulated pigment-containing aqueous dispersion (MC-15) was measured in the same manner as in Production Example 1, and as a result, the volume average particle size of the microencapsulated pigment was found to be 10 at 152 nm
Particles with a size of 00 nm or more were 0%. The content of the pigment in the microcapsules was 67%.

<Production Example 16> (Production of magenta anionic microencapsulated pigment-containing aqueous dispersion using a non-volatile base) In Production Example 15, "Fastgen Blue TG" was used.
Instead of "R", "Fastgen Super Magenta
RTS "and further using a 10% aqueous potassium hydroxide solution instead of the 10% aqueous sodium hydroxide solution for neutralization in the same manner as in Production Example 15 for pigment kneading, acid precipitation, filtration and washing with water. Sum and re-disperse, 20% non-volatile
Anionic microencapsulated pigment-containing aqueous dispersion (MC-16) was obtained.

The particle size of the microencapsulated pigment in the anionic microencapsulated pigment-containing aqueous dispersion (MC-16) was measured in the same manner as in Production Example 1, and as a result, the volume average particle size of the microencapsulated pigment was found to be At 178 nm, 1
The number of particles of 000 nm or more was 0%. The content of the pigment in the microcapsules was 67%.

Production Example 17 (Production of Aqueous Dispersion Containing Yellow Anionic Microencapsulated Pigment Using Nonvolatile Base) In Production Example 15, “Fastgen Blue TG” was used.
Instead of "R", "Shimla Fast Yellow 8GT"
F ”was used, and a 10% aqueous solution of lithium hydroxide was used instead of the 10% aqueous solution of sodium hydroxide for neutralization, in the same manner as in Production Example 15: pigment kneading, acid precipitation, filtration and washing with water. Aqueous dispersion containing anionic microencapsulated pigment having a nonvolatile content of 20% (M
C-17) was obtained.

The particle size of the microencapsulated pigment in the anionic microencapsulated pigment-containing aqueous dispersion (MC-17) was measured in the same manner as in Production Example 1, and as a result, the volume average particle size of the microencapsulated pigment was found to be 10 at 182 nm
Particles with a size of 00 nm or more were 0%. The content of the pigment in the microcapsules was 67%.

<Production Example 18> (Production of an anionic microencapsulated pigment-containing aqueous dispersion of carbon black having a capsule wall gelled) (1) Pigment kneading step Obtained in Synthesis Example 7 in a glass bottle having a capacity of 250 ml. 15.0 parts of the resin solution (A-7), 0.8 part of dimethylethanolamine and 15 parts of "MA-600 (medium-grade carbon black manufactured by Mitsubishi Chemical Corporation: average particle diameter 18 nm)" are added,
After adding ion-exchanged water so that the total amount becomes 75 parts, zirconia beads 250 having an average particle diameter of 0.5 mm
After adding the parts, kneading was performed for 4 hours using a paint shaker. After the completion of the kneading, the glass beads were filtered off to obtain a dispersion of a resin and a pigment having a carboxyl group neutralized with a base, dispersed in water.

(2) Gelation Treatment A dispersion of a resin having a carboxyl group having a carboxyl group neutralized with a base and a pigment was dispersed in water, and water was added to the mixture to dilute it three times. It heat-gelled with.

(3) Acid precipitation After gelation treatment, 1N hydrochloric acid was added at room temperature with stirring with a disper until the resin was insolubilized and fixed to the pigment. The pH at this time was 3-5.

(4) Filtration and Washing With water, the aqueous medium containing the pigment to which the resin had been fixed was suction-filtered, and then the salt was washed with water to obtain a wet cake.

(5) Neutralization and Redispersion in Aqueous Medium While stirring the water-containing cake with a disper, a 10% dimethylaminoethanol aqueous solution was added until the pH of the dispersion became 8.5 to 9.5. added. After continuing stirring for 1 hour, water was added to adjust the non-volatile content to 20% to obtain an anionic microencapsulated pigment-containing aqueous dispersion of carbon black (MC-18).

The particle size of the microencapsulated pigment in the anionic microencapsulated pigment-containing aqueous dispersion (MC-18) was measured in the same manner as in Production Example 1, and as a result, the volume average particle size of the microencapsulated pigment was found to be 10 at 149 nm
Particles with a size of 00 nm or more were 0%. The content of the pigment in the microcapsules was 67%.

[0180]

[Table 2]

[0181]

[Table 3]

Abbreviations in Tables 2 and 3 are as follows. TGR: "Fastgen Blue TGR" (CI Pigment Blue 1 manufactured by Dainippon Ink and Chemicals, Inc.)
5) RTS: "Fastgen Super Magenta RT
S "(CI Pigment Red 122 manufactured by Dainippon Ink and Chemicals, Inc.) DPP:" Chromophtal Red DPP-BO "
(Ci Pigment Red 2 manufactured by Ciba Geigy)
54) 8GTF: "Shimla Fast Yellow 8GTF"
(C.I. pigment manufactured by Dainippon Ink and Chemicals, Inc.)
Yellow 17) 4192: "Shimla Fast Yellow 4192"
(C.I. pigment manufactured by Dainippon Ink and Chemicals, Inc.)
Yellow 154) CB: Carbon black DMAE: Dimethylaminoethanol Particle diameter: Volume average particle diameter of microencapsulated pigment N.I. V. : Nonvolatile content coarse particle: Microencapsulated pigment particle size 1000 nm
Percentage of particles above Pigment content: Percentage of pigment contained in microcapsules

<Example 1> (Production of recording liquid using a microencapsulated pigment dispersion having a pigment content of 67% in the microencapsulated pigment) The anionic microencapsulation of phthalocyanine blue obtained in Production Example 2 Pigment-containing aqueous dispersion (MC-2) 37.
To 5 parts, 7.5 parts of ethylene glycol and 5.
0 parts, diethylene glycol monobutyl ether 0.5
Part, ethylene glycol monomethyl ether 15.0
Parts, isopropyl alcohol 3.0 parts, diethanolamine 3.0 parts and ion-exchanged water 28.5 parts,
A cyan recording liquid having a pigment content of 5.0% was prepared.

<Example 2> (Production of recording liquid using a microencapsulated pigment dispersion having a pigment content of 67% in the microencapsulated pigment) In Example 1, the phthalocyanine blue obtained in Production Example 2 was prepared. Instead of the anionic microencapsulated pigment-containing aqueous dispersion (MC-2), the magenta anionic microencapsulated pigment-containing aqueous dispersion (MC) obtained in Production Example 7 was used.
A magenta recording liquid was prepared in the same manner as in Example 1 except that -7) was used.

<Example 3> (Production of recording liquid using a microencapsulated pigment dispersion having a pigment content of 67% in the microencapsulated pigment) In Example 1, the phthalocyanine blue obtained in Production Example 2 was used. Instead of the anionic microencapsulated pigment-containing aqueous dispersion (MC-2), the yellow anionic microencapsulated pigment-containing aqueous dispersion (M-2) obtained in Production Example 13 was obtained.
A yellow recording liquid was prepared in the same manner as in Example 1 except that C-13) was used.

[0186] In Examples 1, 2 and 3, the recording liquid was prepared by simply mixing without using a dispersing machine such as a bead mill or a roll.
No dispersal equipment is required, the dispersal process and labor can be shortened, the manufacturing time can be shortened, and the dispersive energy can be saved, and the productivity can be greatly increased and the manufacturing cost can be reduced. Further, the aqueous dispersion containing anionic microencapsulated pigment used in these had a pigment content in the anionic microencapsulated pigment as high as 67%, and the pigment content in the aqueous dispersion was 13.4% or more. It is high, and other materials such as a water-soluble resin and a water-soluble organic solvent used for improving the performance as a recording liquid can be added in a considerable amount, and the versatility was high.

Table 4 shows the volume average particle diameters of the microencapsulated pigments in the cyan, magenta and yellow recording liquids and the volume average particle diameters and the sedimentation properties of the particles after storage at room temperature for 30 days. It was shown to. The volume average particle diameters of the anionic microencapsulated pigments in the recording liquids obtained in Examples 1, 2 and 3 showed almost the same values before and after storage, and no sedimentation of the particles was observed. It is apparent that the storage stability and the dispersion stability are extremely excellent as compared with the encapsulated pigment.

Next, using the above recording liquid, a cyan, magenta and yellow color recording image was recorded on an OHP sheet and a copy paper by using a commercially available printer of bubble jet system. As shown in Table 6, this recorded image had high definition and high color density, and was excellent in color rendering and transparency. In addition, the image recorded on the OHP sheet showed a colorful projection because it was excellent in transparency. O
The recorded image on the HP sheet did not disappear even if it was rubbed with water, and it was excellent in water resistance. In addition, the nozzle for ejecting ink was not clogged even after repeated use.

<Comparative Example 1> (Production of recording liquid using a microencapsulated pigment dispersion liquid having an average particle size of 650 nm and a maximum particle size of more than 1000 nm of the microencapsulated pigment) Instead of the obtained phthalocyanine blue anionic microencapsulated pigment-containing aqueous dispersion (MC-2), the phthalocyanine blue anionic microencapsulated pigment-containing aqueous dispersion (MC-5) obtained in Production Example 5 was used. A cyan recording liquid was prepared in the same manner as in Example 1 except for the above.

Table 8 shows the volume average particle size of the microencapsulated pigment in the cyan recording liquid obtained in Comparative Example 1 and the volume average particle size and the sedimentation property of the particles after storage at room temperature for 30 days.
It was shown to. The volume average particle size of the anionic microencapsulated pigment in the recording liquid of this comparative example was almost the same before and after storage, but sedimentation of the particles was observed and the dispersion stability was poor.

Then, using the above recording liquid, a cyan color recording image was recorded on an OHP sheet and a copy paper by using a commercially available bubble jet printer. As shown in Table 9, this recorded image was low in definition and color density, and lacked in color rendering and transparency. In addition, the image recorded on the OHP sheet does not show an opaque and colorful projection,
It could not be used for P sheet. Further, during repeated use, the nozzle for ejecting ink was clogged, and the printer could not be used.

<Example 4> (Production of recording liquid using a microencapsulated pigment dispersion liquid having a pigment content of 51.7% in the microencapsulated pigment) The anionic micro of phthalocyanine blue obtained in Production Example 1 Aqueous dispersion containing encapsulated pigment (MC-1) 47.
20 parts of ethylene glycol, 3.0 parts of diethanolamine and 29.6 parts of deionized water were mixed with 4 parts to prepare a cyan recording liquid having a pigment content of 6%.

<Example 5> (Production of recording liquid using a microencapsulated pigment dispersion having a pigment content of 51.7% in the microencapsulated pigment) The magenta anionic micro pigment obtained in Production Example 6 50.0 parts of the encapsulated pigment-containing aqueous dispersion (MC-6) was mixed with 20 parts of ethylene glycol, 3.0 parts of diethanolamine and 27.0 parts of ion-exchanged water to obtain a pigment content of 6%.
To prepare a magenta recording liquid.

<Example 6> (Production of recording liquid using a microencapsulated pigment dispersion having a pigment content of 51.7% in the microencapsulated pigment) The yellow anionic micro color obtained in Production Example 12 48.8 parts of the encapsulated pigment-containing aqueous dispersion (MC-12) was mixed with 20 parts of ethylene glycol, 3.0 parts of diethanolamine and 28.2 parts of ion-exchanged water to give a yellow color having a pigment content of 6%. A recording liquid was prepared.

In these Examples 4, 5 and 6, when the recording liquid was prepared, a dispersing machine such as a bead mill or a roll was not particularly required, and the recording liquid could be prepared simply by mixing. The dispersion process and labor can be shortened,
The manufacturing time could be shortened or the distributed energy could be saved, which greatly increased the productivity and the manufacturing cost. Further, the anionic microencapsulated pigment-containing aqueous dispersion used for these had a high pigment content of 51.7% in the anionic microencapsulated pigment,
In addition, the pigment content in the aqueous dispersion is as high as 10% or more, and it is possible to add a considerable amount of other materials such as a water-soluble organic solvent used for improving the performance as a recording liquid, which makes it versatile. it was high.

Table 4 shows the volume average particle diameters of the microencapsulated pigments in the cyan, magenta and yellow recording liquids and the volume average particle diameters and the sedimentability of the particles after storage at room temperature for 30 days. . The volume average particle size of the anionic microencapsulated pigment in the recording liquid of this example is
It shows almost the same value before and after storage, and further, no sedimentation of particles is observed, and it is clear that the storage stability and dispersion stability are very excellent as compared with the conventional microencapsulated pigment.

Next, using the recording liquid described above, a cyan color ink was obtained by using a commercially available piezo system ink jet printer.
Color recorded images of magenta color and yellow color are OHP
Recorded on sheets and copy paper. This recorded image is shown in Table 6.
As shown in, the definition and the color density were high, and the color rendering properties and transparency were excellent. Also, the image recorded on the OHP sheet is
Due to its excellent transparency, it showed a colorful projection. The recorded image on the OHP sheet did not disappear even if it was rubbed with water, and it was excellent in water resistance. In addition, the nozzle for ejecting ink was not clogged even after repeated use.

<Example 7> (Production of recording liquid using a microencapsulated pigment dispersion having a pigment content of 67% in the microencapsulated pigment) Anionic microencapsulation of phthalocyanine blue obtained in Production Example 2 Pigment-containing aqueous dispersion (MC-2) 44.
8 parts, acid value 163, non-volatile content of molecular weight 25,000 5
Aqueous ammonia solution of 0% styrene acrylic acid resin 5.
A cyan recording liquid having a pigment content of 6% was prepared by mixing 0 parts (corresponding to 2.5 parts of resin solid content), 20 parts of ethylene glycol, 3.0 parts of diethanolamine and 27.2 parts of deionized water. did.

<Example 8> (Production of recording liquid using a microencapsulated pigment dispersion having a pigment content of 67% in the microencapsulated pigment) In Example 7, the phthalocyanine blue obtained in Production Example 2 was prepared. Instead of the anionic microencapsulated pigment-containing aqueous dispersion (MC-2), the magenta anionic microencapsulated pigment-containing aqueous dispersion (MC) obtained in Production Example 7 was used.
A magenta recording liquid was prepared in the same manner as in Example 7 except that (-7) was used.

<Example 9> (Production of recording liquid using a microencapsulated pigment dispersion having a pigment content of 67% in the microencapsulated pigment) In Example 7, the phthalocyanine blue obtained in Production Example 2 was prepared. Instead of the anionic microencapsulated pigment-containing aqueous dispersion (MC-2), the yellow anionic microencapsulated pigment-containing aqueous dispersion (M-2) obtained in Production Example 13 was obtained.
C-13) was used in the same manner as in Example 7, except that
A yellow recording liquid was prepared.

<Example 10> (Production of recording liquid using microencapsulated pigment dispersion liquid containing 75% of pigment in microencapsulated pigment) Magenta anionic microencapsulation obtained in Production Example 9 To 40.0 parts of the pigment-containing aqueous dispersion (MC-9), 5.0 parts of an aqueous ammonia solution of the styrene acrylic acid resin used in Example 7 (corresponding to 2.5 parts of resin solid content), 20 parts of ethylene glycol, 3.0 parts of diethanolamine and 32.0 parts of ion-exchanged water were mixed to prepare a magenta recording liquid having a pigment content of 6%.

<Example 11> (Production of recording liquid using a microencapsulated pigment dispersion having a pigment content of 67% in the microencapsulated pigment) In Example 7, the phthalocyanine blue obtained in Production Example 2 was prepared. Except that the anionic microencapsulated pigment-containing aqueous dispersion (MC-4) obtained in Production Example 4 was used instead of the anionic microencapsulated pigment-containing aqueous dispersion (MC-2). A cyan recording liquid was prepared in the same manner as in Example 7.

In Examples 7, 8, 9, 10 and 11, the recording liquid was prepared without any disperser such as a bead mill or a roll, and simply by mixing. It is not necessary, and the dispersion process and labor can be shortened, the manufacturing time can be shortened, and the distributed energy can be saved, and the productivity can be greatly increased and the manufacturing cost can be reduced. In addition, the anionic microencapsulated pigment-containing aqueous dispersion used in these had a high pigment content of 67% or more in the anionic microencapsulated pigment, and the pigment content in the aqueous dispersion was 13.4% or more. It was possible to add a considerable amount of other materials such as a water-soluble resin and a water-soluble organic solvent used for improving the performance as a recording liquid, and the versatility was high.

Table 5 shows the volume average particle diameters of the microencapsulated pigments in the cyan, magenta and yellow recording liquids and the volume average particle diameters and the sedimentability of the particles after storage at room temperature for 30 days. . The volume average particle size of the anionic microencapsulated pigment in the recording liquid of the present example shows almost the same value before and after storage, and further, no sedimentation of particles is observed, and compared with the conventional microencapsulated pigment, it is stored. It is clear that the stability and dispersion stability are very excellent.

Next, using the above recording liquid, a cyan ink of
Color recorded images of magenta color and yellow color are OHP
Recorded on sheets and copy paper. This recorded image is shown in Table 6.
7 and 7, the definition and color density were high, and the color rendering properties and transparency were excellent. In addition, the image recorded on the OHP sheet showed a colorful projection because it was excellent in transparency. The recorded image on the OHP sheet did not disappear even if it was rubbed with water, and it was excellent in water resistance. In addition, the nozzle for ejecting ink was not clogged even after repeated use.

<Comparative Example 2> (Production of recording liquid using a microencapsulated pigment dispersion having a pigment content of 33% in the microencapsulated pigment) The magenta anionic microencapsulation obtained in Production Example 10 To 90.1 parts of the pigment-containing aqueous dispersion (MC-10), 5.0 parts of an aqueous ammonia solution of the styrene acrylic acid resin used in Example 7 (corresponding to 2.5 parts of resin solid content),
1.9 parts of ethylene glycol and 3.0 parts of diethanolamine were mixed to prepare a magenta recording liquid having a pigment content of 6%.

The anionic microencapsulated pigment-containing aqueous dispersion used for this purpose had a low pigment content of 33% in the anionic microencapsulated pigment, and a pigment content of 6.6% in the aqueous dispersion. Low, lacking versatility due to the limited amount of other materials such as water-soluble resins and water-soluble organic solvents used to improve the performance of the recording liquid while maintaining the color density of the recording liquid. Met. Further, since the amount of resin used in the microcapsules is large, there is a problem in compatibility with other materials.

Table 8 shows the volume average particle size of the microencapsulated pigment in the magenta recording liquid, and the volume average particle size and the sedimentation property of the particles after storage at room temperature for 30 days. The volume average particle diameter of the anionic microencapsulated pigment in the recording liquid of this comparative example shows almost the same value before and after storage, and further, no sedimentation of particles is observed, and the storage stability and dispersion stability are very high. Was excellent.

Next, a magenta color recording image was recorded on an OHP sheet or a copy paper using the above recording liquid by using a commercially available piezo type ink jet printer. Since the amount of ethylene glycol added to the recording liquid is small, bleeding and repelling occur on copy paper and OHP sheets, and the recorded image has low definition, color rendering and transparency as shown in Table 9. Was lacking in. Further, the image recorded on the OHP sheet did not show an opaque and colorful projection view and could not be used for the OHP sheet. The recorded image on the OHP sheet will not disappear even if it is rubbed with water,
It was excellent in water resistance. When used repeatedly,
Sometimes the nozzles that eject ink were clogged.

<Comparative Example 3> (Production of recording liquid using a microencapsulated pigment dispersion having a pigment content of 83% in the microencapsulated pigment) Magenta anionic microencapsulation obtained in Production Example 8 To 36.1 parts of the pigment-containing aqueous dispersion (MC-8), 5.0 parts of an aqueous ammonia solution of the styrene acrylic acid resin used in Example 7 (corresponding to 2.5 parts of resin solid content), 20 parts of ethylene glycol, 3.0 parts of diethanolamine and 35.9 parts of ion-exchanged water were mixed to prepare a magenta recording liquid having a pigment content of 6%.

Table 8 shows the volume average particle size of the microencapsulated pigment in the magenta recording liquid, and the volume average particle size and the sedimentation property of the particles after storage at room temperature for 30 days. The anionic microencapsulated pigment in the recording liquid of this comparative example cannot keep the pigment stable in a fine state due to the low resin concentration, and the anionic microencapsulated pigment causes aggregation after storage, The volume average particle diameter was increased, particles were also precipitated, and storage stability and dispersion stability were poor.

Next, a magenta color recording image was recorded on the OHP sheet and the copy paper using the above recording liquid by using a commercially available piezo system ink jet printer. As shown in Table 9, this recorded image was low in definition and color density, and lacked in color rendering and transparency because the capsules were agglomerated. Further, the image recorded on the OHP sheet did not show an opaque and colorful projection view and could not be used for the OHP sheet. Further, during repeated use, the nozzle for ejecting ink was clogged, and the printer could not be used.

<Comparative Example 4> (Production of recording liquid using a microencapsulated pigment dispersion liquid having an average particle diameter of the microencapsulated pigment of 650 nm and a maximum particle diameter of more than 1000 nm) of the phthalocyanine blue obtained in Production Example 5 Anionic microencapsulated pigment-containing aqueous dispersion (MC-5) 44.
In 8 parts, 5.0 parts of an aqueous ammonia solution of the styrene acrylic acid resin used in Example 7 (corresponding to 2.5 parts of resin solids), 20 parts of ethylene glycol, 3.0 parts of diethanolamine and 27.2 of deionized water. The parts were mixed to prepare a cyan recording liquid having a pigment content of 6%.

Table 8 shows the volume average particle size of the microencapsulated pigment in the cyan recording liquid, and the volume average particle size after storage at room temperature for 30 days and the sedimentation property of the particles.
The volume average particle diameter of the anionic microencapsulated pigment in the recording liquid of this comparative example showed almost the same value before and after storage, but particle sedimentation was observed, and storage stability and dispersion stability were poor. .

Next, using the above recording liquid, a cyan color recording image was recorded on an OHP sheet or a copy paper by using a commercially available piezo system ink jet printer. As shown in Table 9, this recorded image was low in definition and color density, and lacked in color rendering and transparency. OHP
The images recorded on the sheet did not show an opaque, colorful projection and could not be used on OHP sheets. Further, during repeated use, the nozzle for ejecting ink was clogged, and the printer could not be used.

<Comparative Example 5> (The average particle diameter of the organic pigment is 2
Production of Recording Liquid Using Microencapsulated Pigment Dispersion Exceeding 00 nm) In 44.8 parts of the magenta anionic microencapsulated pigment-containing aqueous dispersion (MC-11) obtained in Production Example 11, Example 7 was added. 5.0 parts of aqueous ammonia solution of styrene acrylic acid resin used in (corresponding to 2.5 parts of resin solid content),
Ethylene glycol 20 parts, diethanolamine 3.0
And 27.2 parts of ion-exchanged water are mixed to obtain a pigment content of 6
% Magenta recording liquid was prepared.

Table 8 shows the volume average particle size of the microencapsulated pigment in the magenta recording liquid, and the volume average particle size and the sedimentation property of the particles after storage at room temperature for 30 days. The volume average particle size of the anionic microencapsulated pigment in the recording liquid of this comparative example showed almost the same value before and after storage, no sedimentation of particles was observed, and storage stability and dispersion stability were excellent. .

Next, a magenta color recording image was recorded on the OHP sheet and the copy paper by using the above recording liquid and a commercially available piezo type ink jet printer. As shown in Table 9, this recorded image was low in definition and color density, and lacked in color rendering and transparency. In particular, OHP
The images recorded on the sheet did not show an opaque, colorful projection and could not be used on OHP sheets. Moreover, the nozzle for ejecting ink was not clogged even after repeated use.

<Comparative Example 6> (The average particle diameter of the organic pigment is 2
Production of Recording Liquid Using Microencapsulated Pigment Dispersion of More Than 00 nm) In 44.8 parts of the yellow color anionic microencapsulated pigment-containing aqueous dispersion (MC-14) obtained in Production Example 14, Example 7 was added. 5.0 parts of aqueous ammonia solution of styrene acrylic acid resin used in (corresponding to 2.5 parts of resin solid content),
Mixing 20 parts of ethylene glycol, 3.0 parts of diethanolamine and 27.2 parts of deionized water, the pigment content is 6%.
To prepare a yellow recording liquid.

Table 8 shows the volume average particle size of the microencapsulated pigment in the yellow recording liquid, and the volume average particle size and the sedimentation property of the particles after storage at room temperature for 30 days. The volume average particle size of the anionic microencapsulated pigment in the recording liquid of this comparative example showed almost the same value before and after storage, no sedimentation of particles was observed, and storage stability and dispersion stability were excellent. .

Next, a magenta color recording image was recorded on the OHP sheet and the copy paper by using the above recording liquid and a commercially available piezo type ink jet printer. As shown in Table 9, this recorded image was low in definition and color density, and lacked in color rendering and transparency. In particular, OHP
The images recorded on the sheet did not show an opaque, colorful projection and could not be used on OHP sheets. Moreover, the nozzle for ejecting ink was not clogged even after repeated use.

<Example 12> (Production of recording liquid using non-volatile base microencapsulated pigment dispersion) An aqueous dispersion of phthalocyanine blue containing anionic microencapsulated pigment (MC- 15) 3
7.5 parts, 5 parts ethylene glycol, 1 glycerin
A cyan recording liquid having a pigment content of 5.0% was prepared by mixing 0.0 part, 3.0 parts of diethanolamine and 44.5 parts of ion-exchanged water.

<Example 13> (Production of recording liquid using non-volatile base microencapsulated pigment dispersion) [0223] In Example 12, the aqueous solution containing the anionic microencapsulated pigment of phthalocyanine blue obtained in Production Example 15 was used. Magenta was prepared in the same manner as in Example 12 except that the magenta anionic microencapsulated pigment-containing aqueous dispersion (MC-16) obtained in Production Example 16 was used in place of the dispersion (MC-15). A color recording liquid was prepared.

<Example 14> (Production of recording liquid using a non-volatile base microencapsulated pigment dispersion) In Example 12, phthalocyanine blue anionic microencapsulated pigment-containing aqueous solution obtained in Production Example 15 was used. Yellow was prepared in the same manner as in Example 12 except that the yellow anionic microencapsulated pigment-containing aqueous dispersion (MC-17) obtained in Production Example 17 was used instead of the dispersion (MC-15). A color recording liquid was prepared.

In Examples 12, 13 and 14, the recording liquid was prepared without any dispersing machine such as a bead mill or a roll, and it could be prepared simply by mixing. The process and labor can be shortened,
The manufacturing time could be shortened or the distributed energy could be saved, which greatly increased the productivity and the manufacturing cost. Further, the aqueous dispersion containing anionic microencapsulated pigment used in these had a pigment content in the anionic microencapsulated pigment as high as 67%, and the pigment content in the aqueous dispersion was 13.4% or more. It is high, and other materials such as a water-soluble resin and a water-soluble organic solvent used for improving the performance as a recording liquid can be added in a considerable amount, and the versatility was high.

Table 5 shows the volume average particle diameters of the microencapsulated pigments in the cyan, magenta and yellow recording liquids and the volume average particle diameters and the sedimentation properties of the particles after storage at room temperature for 30 days. It was shown to. Examples 12, 13
The volume average particle diameters of the anionic microencapsulated pigments in the recording liquids obtained in Nos. 14 and 14 showed almost the same values before and after storage, and further, no sedimentation of particles was observed, which was higher than that of conventional microencapsulated pigments. It is clear that the storage stability and dispersion stability are very good.

Next, using the above-mentioned recording liquid, a cyan, magenta and yellow color recording image was recorded on an OHP sheet and a copy paper by using a commercially available piezo type printer. As shown in Table 7, these recorded images were high in definition and color density and excellent in color rendering and transparency. In addition, this recorded image showed a colorful projection because of its excellent transparency. Further, the recorded image on the OHP sheet is easily erased by rubbing it with water, but even if a few drops of water are dripped on the recorded image on the copy paper, the recorded image does not bleed and disappears, and it has excellent water resistance. Was there.

When the nozzles filled with these cyan, magenta and yellow inks were left at room temperature for 15 days and then used for cleaning, cleaning was performed as compared with the case where volatile amine was used. Since the number of times was 3 or less, the redispersibility of the ink was very excellent.

<Example 15> (Production of recording liquid using gelled microencapsulated pigment dispersion) [0229] The carbon black anionic microencapsulated pigment-containing aqueous dispersion (MC-18 obtained in Production Example 18). ) 37.
5 parts ethylene glycol 5 parts, glycerin 10.0
Parts, diethanolamine 3.0 parts and deionized water 4
4.5 parts of carbon black was mixed to prepare a recording liquid of carbon black having a pigment content of 5.0%.

Next, Table 5 shows the volume average particle size of the microencapsulated pigment in the recording liquid of carbon black, and the volume average particle size and the sedimentation property of the particles after storage at room temperature for 30 days. The volume average particle diameter of the anionic microencapsulated pigment in this recording liquid shows almost the same value before and after storage, and further, no sedimentation of particles is observed, and storage stability and storage stability are improved as compared with conventional microencapsulated pigments. It is clear that the dispersion stability is very good.

Next, a black-color recorded image was recorded on the OHP sheet and the copy paper by using a commercially available piezo system ink jet printer using the above recording liquid.
As shown in Table 7, these recorded images had jet blackness and had high definition and high color density. Further, the recorded image on the OHP sheet was hard to erase even if it was rubbed with water, and it was excellent in water resistance.

When the nozzle filled with this recording liquid was left standing at room temperature for 15 days and then cleaned and used,
Since the number of cleaning times was 6 times, the redispersibility of the ink was excellent.

Further, this recording liquid was put in a glass bottle, sealed, and subjected to a solvent resistance test in a high temperature bath at 80 ° C. for 10 days. As a result, the volume average particle diameter was 189 nm, and there was no change as compared with that before the test. Was very good without.

Example 16 (Production of Recording Liquid Using Nonvolatile Base Microencapsulated Pigment Dispersion) An aqueous dispersion of phthalocyanine blue containing anionic microencapsulated pigment (MC- 3) 44.
In 8 parts, 5.0 parts of an aqueous ammonia solution of the styrene acrylic acid resin used in Example 7 (corresponding to 2.5 parts of resin solids), 20 parts of ethylene glycol, 3.0 parts of diethanolamine and 27.2 of deionized water. The parts were mixed to prepare a cyan recording liquid having a pigment content of 6%.

Table 5 shows the volume average particle diameter of the microencapsulated pigment in the cyan recording liquid, and the volume average particle diameter and the sedimentation property of the particles after storage at room temperature for 30 days.
The volume average particle size of the anionic microencapsulated pigment in the recording liquid of this comparative example showed almost the same value before and after storage, no sedimentation of particles was observed, and storage stability and dispersion stability were excellent. .

Next, using the above recording liquid, a cyan color recorded image was recorded on an OHP sheet or a copy paper by using a commercially available piezo system ink jet printer. As shown in Table 7, this recorded image had high definition and high color density, and was excellent in color rendering and transparency. In particular, OHP
The image recorded on the sheet showed a transparent and colorful projection. Furthermore, although the recorded image on the OHP sheet is easily erased by rubbing it with water, even if a few drops of water are dripped onto the recorded image on the copy paper, the recorded image will not be blurred and cannot be seen, and it has excellent water resistance. Was there.

When the nozzle filled with the cyan recording liquid is left to stand at room temperature for 15 days and then used for cleaning, the number of times of cleaning is 3 or less. Therefore, redispersibility of the ink is very high. Was excellent.

[0238]

[Table 4]

[0239]

[Table 5]

Abbreviations in Tables 4 and 5, evaluation methods and evaluation criteria are as follows. Volume average particle diameter: Volume average particle diameter (nm) of anionic microencapsulated pigment Sedimentation property: Sedimentation state of particles after storage ○ = good × = sedimentation observed

[0241]

[Table 6]

[0242]

[Table 7]

Abbreviations in Tables 6 and 7, evaluation methods and evaluation criteria are as follows. BJ: Bubble jet ink jet printer PJ: Piezo ink jet printer Redispersibility: Evaluated by the ease of reprinting after leaving the ink filled room for 15 days at room temperature. ○ = Printing is possible within 3 cleanings △ = 4-9 cleanings × = 10 times or more −: Not evaluated Water resistance: ○ = Not erased even with OHP sheet △ = Little bleeding on copy paper × = Copy paper Blurred image cannot be read Fineness: ○ = good × = bad Color density: ○ = high × = low Transparency: ○ = transparent × = opaque

[0244]

[Table 8]

The abbreviations in Table 8, the evaluation methods and the evaluation criteria are as follows. Volume average particle diameter: Volume average particle diameter (nm) of anionic microencapsulated pigment Sedimentation property: Sedimentation state of particles after storage ○ = good × = sedimentation observed

[0246]

[Table 9]

The abbreviations, evaluation methods and evaluation criteria in Table 9 are as follows. BJ: Bubble jet ink jet printer PJ: Piezo ink jet printer Redispersibility: Evaluated by the ease of reprinting after leaving the ink filled room for 15 days at room temperature. ○ = Printing is possible within 3 cleanings △ = 4-9 cleanings × = 10 times or more −: Not evaluated Water resistance: ○ = Not erased even with OHP sheet △ = Little bleeding on copy paper × = Copy paper Blurred image cannot be read Fineness: ○ = good × = bad Color density: ○ = high × = low Transparency: ○ = transparent × = opaque

[0248]

The anionic microencapsulated pigment-containing aqueous dispersion for recording liquid of the present invention is a very fine pigment dispersion and is excellent in storage stability, and therefore has high definition and high color density. It has excellent color rendering properties and transparency, and labor saving in the dispersion process can reduce manufacturing costs and recording liquid costs.
Further, since the anionic microencapsulated pigment-containing aqueous dispersion for a recording liquid of the present invention has a high pigment content, when processed into a recording liquid, there is a room in which various materials can be used in the formulation, and the versatility is high. It has the advantage of being expensive.

Furthermore, since the non-volatile base is excellent in redispersibility, there is an advantage that the reliability of the recording liquid is enhanced.

Claims (18)

[Claims] 1. An aqueous dispersion containing an anionic microencapsulated pigment, which is obtained by coating an organic pigment or carbon black with an anionic group-containing organic polymer compound, wherein the organic pigment in the anionic microencapsulated pigment or An aqueous dispersion for recording liquid, wherein the content ratio of carbon black is in the range of 35 to 80% by weight. 2. The maximum particle size of the anionic microencapsulated pigment is 1000 nm or less, and the average particle size is 30.
The aqueous dispersion for a recording liquid according to claim 1, which is 0 nm or less. 3. An anionic microencapsulated pigment containing an organic pigment or carbon black having a maximum particle size of 200 nm or less and an average particle size of primary particles in the range of 10 to 100 nm. Item 3. An aqueous dispersion for recording liquid according to item 1 or 2. 4. An anionic microencapsulated pigment in which a curing agent and / or a polymer compound and an organic pigment are coated with an anionic group-containing organic polymer compound, 1. 3. The aqueous dispersion for recording liquid according to 3. 5. The aqueous dispersion for a recording liquid according to claim 1, 2, 3 or 4, wherein the anionic group-containing organic polymer compound is an organic amine salt. 6. The aqueous dispersion for a recording liquid according to claim 1, 2, 3 or 4, wherein the anionic group-containing organic polymer compound is an alkali metal salt. 7. The acid value of the anionic group-containing organic polymer compound is 30 KOH mg / g or more,
The aqueous dispersion for recording liquid according to 3, 4, 5 or 6. 8. The aqueous dispersion for recording liquid according to claim 7, wherein the anionic group is a carboxyl group. 9. The aqueous dispersion for a recording liquid according to claim 7, wherein the anionic group-containing organic polymer compound has a number average molecular weight of 2000 or more. 10. An anionic microencapsulated pigment obtained by introducing water into an organic solvent phase containing an anionic group-containing organic polymer compound and an organic pigment or carbon black. 3, 5,
An aqueous dispersion for recording liquid according to 6, 7, 8 or 9. 11. An anionic group-containing organic polymer compound, an organic pigment or carbon black, and a curing agent and / or
Alternatively, the aqueous dispersion for a recording liquid according to claim 4, 5, 6, 7, 8 or 9, which uses an anionic microencapsulated pigment obtained by introducing water into an organic solvent phase containing a polymer compound. 12. An anionic group-containing organic polymer compound and an anionic microencapsulated pigment obtained by introducing water into an organic solvent phase containing an organic pigment or carbon black while irradiating ultrasonic waves are used. The aqueous dispersion for recording liquid according to claim 10 or 11. 13. An anionic microencapsulated pigment obtained by adding an anionic group-containing organic polymer compound and an organic solvent phase containing an organic pigment or carbon black to water is used. 3, 5,
An aqueous dispersion for recording liquid according to 6, 7, 8 or 9. 14. An anionic group-containing organic polymer compound, an organic pigment or carbon black, and a curing agent and / or
Alternatively, the aqueous dispersion for recording liquid according to claim 4, 5, 6, 7, 8 or 9, wherein an anionic microencapsulated pigment obtained by introducing an organic solvent phase containing a polymer compound into water is used. 15. An anion obtained by neutralizing a part or all of an anionic group of a water-containing cake composed of an anionic group-containing organic polymer compound and an organic pigment or carbon black with a basic compound. A micro-encapsulated pigment is used, wherein
An aqueous dispersion for recording liquid according to 6, 7, 8 or 9. 16. A step of neutralizing a part or all of anionic groups of anionic group-containing organic polymer compounds with a basic compound and kneading with an organic pigment or carbon black in an aqueous medium, and The water-containing cake obtained by a method comprising the steps of: precipitating anionic group-containing organic polymer compounds by fixing the pH to neutral or acidic with an acidic compound and fixing them to the pigment. Aqueous dispersion for liquids. 17. The method of claim 1, 2, 3, 4, 5, 6, 7,
8, 9, 10, 11, 12, 13, 14, 15, or 16
A recording liquid containing the aqueous dispersion for a recording liquid as described above. 18. The recording liquid according to claim 17, which is for an inkjet printer.