JPH1180639A - Ink jet recording ink - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an ink which can form a highly driable less blotting good image even on plain paper by including a water-soluble colorant, a water-soluble organic solvent, water and a specified compound. SOLUTION: 3-30 wt.%, desirably 5-17 wt.% water-soluble colorant, 1-10 wt.% compound having an HLB of 7 or above and represented by formula I (wherein R<11> to R<14> are each a 1-6C alkyl; A and B are ethyleneoxy and/or propyleneoxy, provided that either A or B contains at least one propyleneoxy, and the total number of ethyleneoxy groups and propyleneoxy groups is 2-60), 0.5-30 wt.% compound represented formula II (wherein one of R<21> and R<22> is H, and the other is CH3 or H; one of R<22> and R<24> is H, and the other is CH3 or H; R<25> is a 4-16C alkyl; and 2<=m+n<=6) or 3-30 wt.% compound represented by formula III (wherein R<31> is a 4-10C alkyl; and p is 3-6) and 1-30 wt.% water- soluble glycol are dissolved in an aqueous medium comprising water and 1-30 wt.%, desirably 3-15 wt.% water-soluble organic solvent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION Field of the Invention The present invention relates to various recording media, for example, plain paper, recycled paper,
Alternatively, the present invention relates to an ink jet recording ink and an ink jet recording method capable of obtaining high print quality on coated paper.

Background prior art ink jet recording, the ink composition from a fine nozzle and ejected as droplets, a method of recording characters or figures on a recording medium surface. As an ink jet recording method, a method of converting an electric signal into a mechanical signal using an electrostrictive element, intermittently discharging an ink composition stored in a nozzle head portion, and recording characters or symbols on a recording medium surface or The ink composition stored in the nozzle head portion is heated rapidly at a location very close to the discharge portion to generate bubbles, and the bubbles are expanded intermittently to discharge characters and symbols on the recording medium surface by intermittent discharge. Methods have been developed and put into practical use.

[0003] The ink composition used for such ink-jet recording has good drying properties of the print, low bleeding of the print, good printing on various recording media, and multicolor printing. Characteristics such as color mixing are required.

[0004] Above all, it is important to suppress bleeding in order to realize a high quality image. Paper is susceptible to bleeding because it consists of fibers of different permeability. In particular, since recycled paper is made of various types of fibers, the permeability of the fibers varies. Therefore, various proposals have been made to suppress the penetration of the ink composition into a recording medium or to improve the drying property in order to suppress bleeding.

For example, use of glycol ether as a wetting agent as described in Japanese Patent Publication No. 2-2907,
The use of a water-soluble organic solvent as described in JP-B-1-15542 and the use of glycol ether as a dye dissolution promoter as described in JP-B-2-3837 are disclosed.

Further, in order to improve the permeability of the ink for ink-jet recording, diethylene glycol monobutyl ether is added as described in US Pat. No. 5,156,675, and acetylene glycol-based as described in US Pat. No. 5,183,502. Adding Surfynol 465 (manufactured by Nissin Chemical Co., Ltd.), or adding both diethylene glycol mono-n-butyl ether and Surfynol 465 as described in US Pat. No. 5,196,056. U.S. Pat. No. 2,083,372 discusses and teaches the use of diethylene glycol ethers as an ink composition. It should be noted that diethylene glycol mono-n-butyl ether is referred to by those skilled in the art as butyl carbitol, and its content is described in, for example, US Pat. No. 3,291,580.

When a pigment is used as an ink composition,
As a method for controlling the permeability of an ink composition, Japanese Patent Application Laid-Open
Use of triethylene glycol monomethyl ether as a pigment as described in JP-A-6-147865, use of ethylene glycol, diethylene glycol, or ethers of triethylene glycol as a pigment as described in JP-A-9-111165, etc. , Are disclosed.

On the other hand, there has also been proposed a method of printing an ink composition on a heated recording medium, rapidly evaporating a solvent component, and fixing the ink composition promptly. Paper may be adversely affected. This method also has a disadvantage of increasing power consumption due to heating.

[0009]

SUMMARY OF THE INVENTION The present inventors have now reported that an ink composition containing a compound having a specific structure has good drying properties and good image quality with little bleeding on various recording media, especially recycled paper, by an ink jet recording method. Can be realized,
Obtained knowledge.

Accordingly, an object of the present invention is to provide an ink composition capable of realizing a good image on various recording media, especially plain paper.

The ink jet recording ink according to the present invention contains a water-soluble coloring material, a water-soluble organic solvent, water, and at least a compound represented by the following formula (I), (II) or (III). It consists of

[0012]

Embedded image (In the above formula, R ¹¹ , R ¹² , R ¹³ , and R ¹⁴ each independently represent a C _1-6 alkyl group, and A and B are
Independently represents a group consisting of an ethyleneoxy group and / or a propyleneoxy group, wherein one of A and B contains at least one propyleneoxy group, and the total of the ethyleneoxy group and the propyleneoxy group is 2 to 60;
Is)

[0013]

Embedded image (In the above formula, one of R ²¹ and R ²² is H, the other is CH ₃ or H, and one of R ²³ and R ²⁴ is H and the other is CH ₃ or H, However, R ²¹ , R ²² , R ²³ , and R ²⁴ do not all represent H at the same time, and when one of R ²¹ and R ²² is H, both R ²³ and R ²⁴ are H, ²¹ and R
When both ²² are H, at least one of R ²³ and R ²⁴
One is CH ₃ , R ²⁵ represents a C _4-10 alkyl group, m
And n satisfy 2 ≦ m + n ≦ 6)

[0014]

Embedded image (In the above formula, R ³¹ represents a C _4-10 alkyl group, and p is 3 to
6 is an integer)

[0015]

DETAILED DESCRIPTION OF THE INVENTION Ink for inkjet recording Ink for inkjet recording in the present invention means black ink when performing monochrome printing, and color ink when performing color printing. Yellow ink, magenta ink, and cyan ink, and in some cases, black ink are meant.

The ink-jet ink used in the present invention comprises a water-soluble coloring material, a water-soluble organic solvent, water and a compound represented by the formula (I), (II) or (III). Things.

Formula (I), Formula (II), or Formula (III)
Compound above-mentioned formula (I), Formula (II), or according to the ink composition of the present invention comprising formula (III), various recording media,
In particular, even on plain paper, especially recycled paper, it is possible to realize a good quality image with good drying properties and little bleeding. The compound of the above formula (I), formula (II), or formula (III) seems to function as a surfactant in the ink composition. It is considered that by adding these compounds, the permeability of the ink composition to the recording medium can be set to an appropriate range for giving good drying properties and suppressing bleeding. Further, the addition of the above compound can provide an advantage that stable inkjet recording can be performed.

In the formula (I), R ¹¹ , R ¹² , R ¹³ and R
¹⁴ independently represents a C _1-6 alkyl group, preferably a C _1-4 alkyl group, and this alkyl group may be linear or branched.

A and B independently represent a group consisting of an ethyleneoxy group and / or a propyleneoxy group, and one of A and B contains at least one propyleneoxy group. The total of the ethyleneoxy group and the propyleneoxy group is preferably 2 to 60,
More preferably, it is 4-10.

The number of carbon atoms of the alkyl group represented by R ¹¹ , R ¹² , R ¹³ and R ¹⁴ and the combination thereof, the structures and combinations of A and B, and the total of the ethyleneoxy group and the propyleneoxy group are represented by the formula (I) May be appropriately determined in consideration of the HLB value of the compound of formula (1).

According to a preferred embodiment of the present invention, formula (I)
The HLB value of the compound is preferably 7 or more. Compounds of the formula (I) that give such HLB values include:
R ¹¹ represents t-butyl, R ¹² represents methyl, R ¹³ represents t-butyl, and R ¹⁴ represents methyl, and A and B are — (CH ₂ —CH ₂ —O) _j — _(CH 2 -CH
A compound of the formula (CH ₃ ) —O) _k —, wherein j represents 10 and k represents 2, R ¹¹ represents ethyl, R ¹² represents methyl, R ¹³ represents ethyl, and R ¹⁴ represents methyl, and A and B represent —CH ₂ —CH (CH ₃ ) —O) _j
— (CH ₂ —CH ₂ —O) _k — (where j is 1, k
Represents 10), R ¹¹ represents isopropyl, R ¹² represents ethyl, R ¹³ represents isopropyl,
And R ¹⁴ represents ethyl, A and B - (CH ₂ -
CH ₂ —O) _j — (CH ₂ —CH (CH ₃ ) —O—) _k
-(CH ₂ -CH ₂ -O) _1- (where j is 20,
k represents 1 and l represents 4).

The use of the compound represented by the formula (I) has an advantage that foaming of the ink composition can be effectively suppressed. Bubbling of the ink composition is preferably suppressed because it leads to occurrence of missing prints in the ink jet recording method. In particular, the ink composition to which the emulsion described below is added may easily foam, but the addition of the compound represented by the formula (I) can effectively suppress the foaming even in the ink composition to which the emulsion is added.

The amount of the compound of the formula (I) in the ink for inkjet recording according to the present invention is 0.1% by weight.
Preferably, the content is about 10 to 10% by weight.

Since the ink jet recording ink of the present invention is water-soluble, it is preferable that the surfactant used is water-soluble and that the HLB value is high.
In particular, the compound of formula (I) preferably has an HLB value of 7 or more, and particularly preferably has an HLB value of 9 or more. When the compound of the formula (I) has a low HLB value, it is preferable to use another surfactant or a water-soluble organic solvent.

In the formula (II), one of R ²¹ and R ²² is H, the other is CH ₃ or H, one of R ²³ and R ²⁴ is H, and the other is CH ₃ or H Provided that R ²¹ , R ²² , R ²³ and R ²⁴ do not all represent H at the same time, and when one of R ²¹ and R ²² is H, R ²³ and R ²⁴ are both H And
When R ²¹ and R ²² are both H, at least one of R ²³ and R ²⁴ is CH ₃ , and R ²⁵ represents a C _4-10 alkyl group, which may be linear or branched. And it is preferably a branched one.

M and n satisfy 2 ≦ m + n ≦ 6, and preferably satisfy 2 ≦ m + n ≦ 3 in order to achieve low viscosity of the ink.

Preferred examples of the compound represented by the formula (II) are as follows: R ²¹ represents H, R ²² represents methyl;
²³ represents H, R ²⁴ represents methyl, R ²⁵ represents a butyl, compound m + n is 3, R ²¹ represents H, R ²² represents methyl, R ²³ represents methyl, R ²⁴ Represents H,
A compound wherein R ²⁵ represents butyl and m + n is 2, R ²¹ represents methyl, R ²² represents H, R ²³ represents methyl,
Compounds in which R ²⁴ represents H, R ²⁵ represents butyl, and m + n is 6, and the like.

The use of the compound represented by the formula (II) has an advantage that the viscosity of the ink composition can be kept low. As a result of keeping the ink composition at a low viscosity, the amount of the coloring material added to the ink composition can be increased. As a result, an image having a higher print density can be obtained.

In the ink jet recording ink of the present invention, the amount of the compound of the formula (II) is 0.5 to 3
A range of 0% by weight is preferred.

In the formula (III), R ³¹ represents a C _4-10 alkyl group, and this alkyl group may be linear or branched. According to a preferred embodiment of the present invention,
In the inkjet recording ink, R ³¹ is an isobutyl group,
Alternatively, it is preferable to use a compound of the formula (III) represented by a t-butyl group.

The use of the compounds of the formula (III) is
As in the case of the compound of the above, there is an advantage that the viscosity of the ink composition can be kept low, and as a result, the amount of the coloring material added can be increased.

In some cases, the compound of the formula (III) exhibits low water solubility. In such a case, the solubility of the ink composition of the compound of the formula (III) can be improved by adding a glycol ether, a nonionic surfactant, or an amphoteric surfactant or a mixture thereof. . Particularly, diethylene glycol mono-n-butyl ether, triethylene glycol mono-
The addition of n-butyl ether is preferred.

In the ink jet recording ink of the present invention, the amount of the compound of the formula (III) is 3% by weight.
The range is preferably about 30% by weight.

Further, according to a preferred embodiment of the present invention, it is preferable that a plurality of compounds of the formula (III) are mixed and added to the ink composition as the compound of the formula (III).

Water-soluble colorant The water-soluble colorant contained in the ink of the present invention is a dye,
Any of pigments may be used.

The dyes include direct dyes, acid dyes, food dyes, basic dyes, reactive dyes, disperse dyes, vat dyes,
Various dyes used for inkjet recording, such as a soluble vat dye and a reactive disperse dye, can be used.

As pigments, inorganic pigments and organic pigments can be used without any particular limitation. As the inorganic pigment, in addition to titanium oxide and iron oxide, carbon black produced by a known method such as a contact method, a furnace method, and a thermal method can be used. Examples of organic pigments include azo pigments (including azo lakes, insoluble azo pigments, condensed azo pigments, chelated azo pigments, etc.) and polycyclic pigments (for example, phthalocyanine pigments, perylene pigments, perinone pigments, anthraquinone pigments, quinacridone pigments, dioxazines) Pigments, thioindigo pigments, isoindolinone pigments, quinofuralone pigments, etc., dye chelates (eg, basic dye chelates, acid dye chelates, etc.), nitro pigments, nitroso pigments, aniline black and the like can be used.

The pigment preferably used in the present invention is a pigment having no dispersant by a surface treatment in which at least one functional group of a carbonyl group, a carboxyl group, a hydroxyl group, or a sulfone group or a salt thereof is bonded. Can be dispersed and / or dissolved in water. Specifically, it can be obtained by grafting a functional group or a molecule containing a functional group to the surface of carbon black by physical treatment or chemical treatment such as vacuum plasma. In the present invention, the functional groups grafted to one carbon black particle may be single or plural. The type and the degree of the functional group to be grafted may be appropriately determined in consideration of the dispersion stability in the ink composition, the color density, the drying property on the front surface of the inkjet head, and the like.

In the present invention, the state where the pigment is stably present in water without a dispersant is referred to as "dispersant and / or dissolution". In many cases, it is difficult to clearly distinguish whether a substance is dissolved or dispersed.
In the present invention, as long as the pigment can be stably present in water without a dispersant, such a pigment can be used irrespective of whether the pigment is dispersed or dissolved. Therefore, in this specification, a pigment that can be stably present in water without a dispersant is sometimes referred to as a water-soluble pigment, but does not mean that pigments in a dispersed state are excluded.

According to a preferred embodiment of the present invention, it is preferably used as a pigment dispersion having an average particle size of 50 to 200 nm and a degree of dispersion of 10 or less.

The pigment preferably used in the present invention can be obtained, for example, by the method described in JP-A-8-3498. In addition, a commercially available product can be used as the pigment, and a preferable example is MicroJet CW1 manufactured by Orient Chemical Industries, Ltd.

The amount of the pigment added to the ink composition is 3 to 3
It is preferably 0% by weight, more preferably about 5 to 17% by weight.

[0043] Examples of the water-soluble organic solvent contained in the ink composition of the water-soluble organic solvent present invention, ethanol, methanol, butanol, propanol, alkyl alcohols from C 1 to 4 carbon atoms such as isopropanol, ethylene glycol monomethyl ether , Ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, ethylene glycol mono-iso-propyl ether, diethylene glycol mono-iso-propyl Ether, ethylene glycol mono-n-butyl ether, diethylene glycol mono-n-butyl Alkyl ether, triethylene glycol mono-n-butyl ether, ethylene glycol mono-t-butyl ether, diethylene glycol mono-t-butyl ether, 1-methyl-1-methoxybutanol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono- t-butyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-iso-propyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono- iso-propyl ether, propylene glycol mono-n-butyl ether, dipropylene glyco Glycol ethers such as mono -n- butyl ether, formamide, acetamide, dimethyl sulfoxide, sorbitol, sorbitan, acetin, diacetin, triacetin, and sulfolane.

The amount of the aqueous organic solvent added to the ink composition is preferably 1 to 30% by weight, more preferably 3 to 1% by weight.
It is about 5% by weight.

Water and Other Ingredients In the ink composition according to the present invention, water is the main solvent. As the water, pure water such as ion-exchanged water, ultrafiltration water, reverse osmosis water, or distilled water, or ultrapure water can be used. In addition, it is preferable to use water sterilized by ultraviolet irradiation, addition of hydrogen peroxide, or the like, since the generation of mold and bacteria can be prevented when the ink composition is stored for a long period of time.

According to a preferred embodiment of the present invention, it is preferable to add a water-soluble glycol to the ink. Preferred examples of the water-soluble glycols include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, polyethylene glycol having a molecular weight of 2000 or less, 1,3-propylene glycol, isopropylene glycol, and isobutylene. Glycol, 1,4-butanediol, 1,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, glycerin, mesoerythritol, pentaerythritol and the like. The water-soluble glycols have an effect of suppressing drying of the ink on the front surface of the nozzle.

The amount of the glycol added to the ink composition is preferably 1 to 30% by weight, more preferably 3 to 1% by weight.
It is about 5% by weight.

According to a preferred embodiment of the present invention, many kinds of sugars can be used in the ink. Preferred examples of the saccharide used include monosaccharides and polysaccharides, and more specifically, glucose, mannose, fructose,
Ribose, xylose, arabinose, lactose, galactose, aldonic acid, glucitolose, maltose,
In addition to cellobiose, sucrose, trehalose, maltotriose and the like, there are alginic acid and its salts, cyclodextrins, celluloses and the like. The amount of the saccharide added to the ink is preferably about 0.05% to 30%.

By adding the saccharide, the clogging phenomenon that the ink dries and clogs at the tip of the head can be avoided. In addition. In the above examples, the amount of monosaccharides and polysaccharides, which are general saccharides, added to the ink is preferably about 3 to 20%. Alginic acid and its salts in the above examples,
The amount of cyclodextrins and celluloses added to the ink needs to be such that the ink has low viscosity and can be printed properly.

According to a preferred embodiment of the present invention, the ink composition may contain a surfactant. The surfactant is preferably one having good compatibility with other components of the ink composition, and among the surfactants, those having high permeability and high stability are preferred. Preferred examples thereof include amphoteric surfactants and nonionic surfactants. Examples of amphoteric surfactants include betaine lauryldimethylaminoacetate, 2-alkyl-N-carboxymethyl-N
-Hydroxyethylimidazolinium betaine, coconut oil fatty acid amidopropyldimethylaminoacetic acid betaine, polyoctylpolyaminoethylglycine and other imidazoline derivatives. Examples of the nonionic surfactant include polyoxyethylene nonyl phenyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene dodecyl phenyl ether, polyoxyethylene alkyl allyl ether, polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, and polyoxyethylene lauryl ether. Ethers such as oxyethylene alkyl ether and polyoxyalkylene alkyl ether, polyoxyethylene oleic acid, polyoxyethylene oleate, polyoxyethylene distearate, sorbitan laurate, sorbitan monostearate, sorbitan monooleate, sorbitan Esters such as sesquiolate, polyoxyethylene monooleate, and polyoxyethylene stearate Fluoroalkyl esters, such as fluorine-containing surfactants such as perfluoroalkyl carboxylate are exemplified. It is also possible to use an acetylene glycol-based surfactant, for example, Surfynol 465, TG, 104
(Air Products) and their modified products can be added. By adding a surfactant, the permeability of the ink composition can be controlled more efficiently, and the water solubility of the compounds of the formulas (I), (II) and (III) can be improved. The advantage that can be obtained is obtained.

The amount of the surfactant added to the ink composition is as follows:
The content is preferably 0.01 to 5% by weight, more preferably 0.1% by weight.
About 3% by weight.

According to a preferred embodiment of the present invention, when the water-soluble coloring material according to the present invention is a pigment, the ink preferably further comprises an emulsion. The addition of this emulsion can improve the fixability and abrasion resistance of the print. This emulsion is preferably one in which the continuous phase is water and the dispersed phase is an acrylic resin, a methacrylic resin, a styrene resin, a urethane resin, an acrylamide resin, an epoxy resin, or a mixed form thereof. Especially,
Preferably, the dispersed phase is made of a resin containing acrylic acid and / or methacrylic acid as a main component. These resins are not limited by the mode of copolymerization, and may be, for example, a block copolymer, a random copolymer, or the like. Further, the emulsion used in the ink according to the present invention has a film-forming ability, and preferably has a minimum film-forming temperature of room temperature or lower, and more preferably a temperature of 0 ° C or higher and 20 ° C or lower.

According to a preferred embodiment of the present invention, the resin component of the emulsion is preferably a resin particle having a core-shell structure comprising a core and a shell surrounding the core. For example, it is possible to adopt a configuration in which a resin component capable of improving the touch property and fixability of the ink is introduced into the core portion, and a resin component that causes the resin particles to be stably present in the ink is introduced into the shell portion. According to a preferred embodiment of the present invention, the shell portion is preferably made of a resin having a crosslinked structure or a structure having more benzene nuclei than the core portion.

As the material forming the shell portion, styrene, tetrahydrofurfuryl acrylate, butyl methacrylate, (α, 2, 3 or 4) -alkylstyrene, (α, 2, 3 or 4) -alkoxystyrene,
3,4-dimethylstyrene, α-phenylstyrene, divinylbenzene, vinylnaphthalene, dimethylamino (meth) acrylate, dimethylaminoethyl (meth)
Acrylate, dimethylaminopropylacrylamide, N, N-dimethylaminoethyl acrylate, acryloymorpholine, N, N-dimethylacrylamide, N-isopropylacrylamide, N, N-diethylacrylamide, methyl (meth) acrylate, ethyl (meth) Acrylate, propyl (meth) acrylate, ethylhexyl (meth) acrylate, other alkyl (meth) acrylate, methoxydiethylene glycol (meth) acrylate, diethylene glycol or polyethylene glycol ethyl ester, propyl ester or butyl ester (meth) acrylate, cyclohexyl ( Meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, isobonyl ( Data) acrylate, hydroxyalkyl (meth) acrylate, fluorine-containing, chlorine-containing,
Examples thereof include silicon-containing (meth) acrylate, (meth) acrylamide, and maleic amide.

When a crosslinked structure is introduced in addition to the above (meth) acrylic acid, (mono, di, tri, tetra, poly) ethylene glycol di (meth) acrylate, 1,1,
4-butanediol, 1,5-pentanediol, 1,
(Meth) acrylates such as 6-hexanediol, 1,8-octanediol and 1,10-decanediol, trimethylolpropane tri (meth) acrylate, glycerin (di, tri) (meth) acrylate, bisphenol A or F Ethylene oxide adduct di (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like can be used.

In the formation of the core portion, the above-mentioned material for forming the shell portion can be used.

As the emulsifier used to form such polymer fine particles, commonly used sodium lauryl sulfate, potassium lauryl sulfate, anionic surfactant, nonionic surfactant and amphoteric surfactant are used. Can be.

As the polymerization initiator, potassium persulfate, ammonium persulfate, hydrogen persulfate, azobisisobutyronitrile, benzoyl peroxide, dibutyl peroxide, peracetic acid,
Cumene hydroperoxide, t-butyl hydroxy peroxide, paramenthan hydroxyperoxide and the like can be used.

As chain transfer agents for polymerization, t-dodecyl mercaptan, n-dodecyl mercaptan, n-
Octyl mercaptan, xanthogens such as dimethyl xanthogen disulfide, diisobutyl xanthogen disulfide, dipentene, indene, 1,4-cyclohexadiene, dihydrofuran and xanthene can be used.

According to a preferred embodiment of the present invention, the molecular weight of the emulsion is preferably at least 1,000, more preferably about 10,000 to 100,000.

A commercially available emulsion can be used as the emulsion used in the present invention, and examples thereof include Z116 manufactured by Mitsui Toatsu.

The addition amount of this emulsion may be determined as appropriate, but is preferably, for example, about 0.5 to 10% by weight.
More preferably, it is about 3 to 5% by weight.

The ink composition according to the present invention comprises, as components other than the above, a preservative, an antioxidant, an ultraviolet absorber, a conductivity adjuster, a pH adjuster, a viscosity adjuster, a surface tension adjuster,
It may further include an oxygen absorbent, an agent for preventing clogging of a nozzle, and the like.

In the present invention, sodium benzoate, sodium pentachlorophenol and 2-pyridinethiol-1-yl are used as preservatives or fungicides in the ink.
Sodium oxide, sodium sorbate, sodium dehydroacetate, 1,2-dibenzothiazoline-3-
ON (Proxel CRL, Proxel BD from ICI)
N, Proxel GXL, Proxel XL-2, Proxel TN) and the like can be used.

In the ink, amines such as diethanolamine, triethanolamine, propanolamine, morpholine and the like and modified products thereof as a pH adjuster, a dissolution aid or an antioxidant, potassium hydroxide, sodium hydroxide, lithium hydroxide, etc. Inorganic salts, ammonium hydroxides, quaternary ammonium hydroxides (such as tetramethylammonium), potassium carbonate, sodium carbonate, carbonates such as lithium carbonate, and other phosphates, or N-
L-ascorbic acid and salts thereof, such as ureas such as methyl-2-pyrrolidone, urea, thiourea, and tetramethylurea; allohanates such as allohanate and methyl allohanate; Etc. can be used. Examples of antioxidants and UV absorbers include Ciba-Geigy's Tinuvin 328, 900, 113
0, 384, 292, 123, 144, 622, 77
0, 292, Irgacor 252, 153, Irga
Nox 1010, 1076, 1035, MD1024, or the like, or a lanthanide oxide or the like can be given. Rosins, alginic acids, polyvinyl alcohol, hydroxypropylcellulose, carboxymethylcellulose, hydroxyethylcellulose, methylcellulose, polyacrylate, polyvinylpyrrolidone, gum arabic starch, and the like can be used as the viscosity modifier.

Ink Jet Recording Method and Apparatus Therefor The ink jet recording method using the ink composition according to the present invention means a recording method in which droplets of the ink composition are ejected and the droplets are attached to a recording medium to perform printing. I do.
Examples of such an ink jet recording method include, for example, converting an electric signal into a mechanical signal using an electrostrictive element, intermittently discharging ink stored in a nozzle head portion, and printing characters and symbols on the surface of a recording medium. In the method of recording, the ink stored in the nozzle head is heated rapidly at a location very close to the ejection part to generate bubbles, and the bubbles are expanded intermittently to discharge characters and symbols on the surface of the recording medium. Recording method. According to a preferred embodiment of the present invention, the ink composition according to the present invention is preferably used for an inkjet recording method using an electrostrictive element. This is because, in the method of heating the head, the coloring agent and other components contained in the ink may be decomposed and the head may be easily clogged.

In the case of an ink having a relatively large amount of a solid that can use a pigment as a colorant, such as the ink according to the present invention, a nozzle that does not discharge for a long time tends to dry and thicken the ink on the front surface of the nozzle, causing a phenomenon that printing is disturbed. Easy. Then, by slightly moving the ink so as not to be ejected on the front surface of the nozzle, the ink is stirred and the ink can be ejected stably. The fine movement method can be generated by controlling the pressure of the pressurizing means for discharging the ink so that the ink is not discharged. When such control is performed, it is preferable to use an electrostrictive element as the pressurizing means because of easy control. Further, by using this mechanism, the pigment concentration in the ink can be increased, so that the pigment ink has a high color density and can stably eject the ink.

When the fine movement is performed on the nozzle surface in the ink jet recording apparatus, it is effective for an ink composition having a pigment content of about 5% to 15% by weight, more preferably 7% to 10% by weight. % Of the ink composition.

Further, the ink composition according to the present invention may be filled with a polyurethane foam and filled in an ink tank having a structure in which the ink and the urethane foam are in contact with each other for use. In this case, a glycol ether or an acetylene glycol-based surfactant which is preferably used in the present invention is adsorbed on the urethane foam. Therefore, it is preferable to add excessively in consideration of the amount to be adsorbed. Further, the urethane foam can secure a negative pressure by using the ink composition according to the present invention, and can be clogged by being decomposed or generating foreign matter by each component of the ink used in the present invention. Less is. As the curing catalyst for this urethane foam, a catalyst containing a metal salt or a cationic system is not used, and polyfunctional isocyanates such as tolylene diisocyanate and meta-xylylene diisocyanate and glycols such as polypropylene glycol and polyethylene glycol having an average molecular weight of about 300 to 3000 are used. , Glycerin, pentaerythritol, dipentaerythritol, neopentyl glycol, propylene glycol, 1,3-butanediol, 1,4-
It is preferable to use a urethane foam made of a substance having a plurality of hydroxy groups such as butanediol and 1,5-pentanediol from the viewpoint of securing negative pressure due to the stability of the foam shape and the chemical stability.

When an acetylene glycol-based surfactant is used, the polyurethane foam adsorbs a part of the acetylene glycol-based surfactant. Therefore, when an acetylene glycol-based surfactant is added to the ink composition, it should be noted that the composition of the ink composition needs to be determined in consideration of the amount adsorbed on the urethane foam.

Further, according to a preferred embodiment of the present invention, the ink composition according to the present invention is preferably printed using a nozzle having a water-repellent surface tip as a nozzle for discharging ink droplets. More specifically, the tip of the nozzle has a structure in which a stainless steel material is used as a base material, eutectoid plating of tetrafluoroethylene and nickel is performed thereon, and heat treatment is performed to form a water-repellent layer. preferable.
Also, instead of nickel, chromium, titanium, gold, platinum,
It is also preferable to use eutectoid plating with a metal having high oxidation resistance such as silver or iridium. By combining the ink composition according to the present invention with such a nozzle, stable continuous printing can be realized for a long time.

According to a more preferred embodiment of the present invention, the contact angle of the ink composition with respect to the water-repellent surface at the tip of the nozzle is adjusted to the normal operating temperature of the printer (for example, from 15 ° C. to
(0 ° C.), it is preferably 50 ° or more. According to this aspect, the printing quality can be improved and continuous printing can be performed.

[0073]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.

Preparation of Ink Composition The water-soluble pigments 1-4 in the following examples have particle sizes of 10-3.
Obtained by applying the method described in JP-A-8-34981 to carbon black having a dispersity of 10 or less at 00 nm.
It means a water-soluble pigment having a group having a terminal having a carbonyl group, a carboxyl group, a hydroxyl group, a sulfone group or the like on its surface. The average particle size of the water-soluble pigment was as shown in parentheses in units of nm.

The water-soluble dye represented by the formula (IV) and the water-soluble dye represented by the formula (V) in the following examples are those represented by the following formula (IV) or (V). is there.

Embedded image (In the above formula, D represents PO (OM) ₂ or COOM, X or Y each independently represents an alkoxy group or an alkyl group, M represents an alkali metal, H, N
H ₄ , or organic amine)

Embedded image (In the above formula, M represents an alkali metal, H, NH ₄ , or an organic amine, m is an integer of 1 or 2, and n is 0
Or an integer of 1) In the following description, the following abbreviations are used.

DEGmBE: diethylene glycol mono-n-butyl ether DMI: 1,3-dimethyl-2-imidazolidinone PGmBE: propylene glycol mono-n-butyl ether MPD: 2-methyl-2,4-pentanediol DPGmBE: dipropylene Glycol mono-n-butyl ether TEGmBE: triethylene glycol mono-n-butyl ether In the following description, an emulsion is a resin emulsion in which water is dispersed in fine polymer particles, and is prepared as follows. .

100 parts of ion-exchanged water is placed in a reaction vessel equipped with a dropping device, a thermometer, a water-cooled reflux condenser, and a stirrer. 0.2 parts were added. 0.05 parts of sodium lauryl sulfate, 10 parts of styrene, and tetrahydrofurfuryl acrylate 2 in 7 parts of ion-exchanged water
, A monomer solution containing 5 parts of butyl methacrylate and 0.02 part of t-dodecylmercaptan was prepared, and this solution was added dropwise to the reaction vessel at 70 ° C to prepare a primary substance. To the primary substance, 2 parts of a 10% solution of ammonium peroxy acid was added and stirred, and then 30 parts of ion-exchanged water, 10 parts of diethylene glycol monobutyl ether, 0.2 parts of potassium lauryl sulfate, 30 parts of styrene, and 15 parts of butyl methacrylate were added. Part, butyl acrylate 16 parts, acrylic acid 3 parts, 1,6-hexanediol dimethacrylate 1
And a reaction liquid consisting of 0.5 part of t-dodecylmercaptan at 70 ° C. with stirring to carry out a polymerization reaction. Thereafter, the mixture is neutralized with ammonia to pH 8 to 8.5 and 0.3
The solution was filtered through a μm filter to obtain an aqueous solution of fine polymer particles as an emulsion.

Further, in all the following ink compositions, 0.1 to 1% of Proxel XL-2 for preventing corrosion of the ink, and 0.001 to 0.1% of benzotriazole for preventing corrosion of the ink jet head member. 05% was added.

Example A Example A1 Amount (% by weight) Water-soluble pigment 1 (105) 5.0 Compound of formula (I) 1 1.0 Emulsion 3.0 DEGmBE 7.0 Glycerin 6.0 1.5 -Pentanediol 5.0 triethanolamine 0.8 ion-exchanged water balance In compound 1 of the above formula (I), R ¹¹ and R ¹² represent a methyl group, R ¹³ and R ¹⁴ represent an isobutyl group, A and B are compounds each representing a group having an average of 4 units of propylene oxide groups and an average of 6 units of ethylene oxide groups and a total of 10 units.

Example A2 Amount (% by weight) Water-soluble pigment 2 (85) 3.0 Compound of formula (I) 2 1.2 Emulsion 1.0 DEGmBE 10.0 Dipropylene glycol 5.0 Triethanolamine 1 0.0 Potassium hydroxide 0.1 Ion-exchanged water Remaining amount of compound 2 of the above formula (I) is that R ¹¹ and R ¹² are ethyl groups, R ¹³ and R ¹⁴ are methyl groups, and A and B
Is a compound having a mean of 2 units of a propylene oxide group, a mean of 6 units of an ethylene oxide group, and a total of 10 units.

Example A3 Amount (% by weight) Water-soluble pigment 3 (90) 5.5 Compound 3 of formula (I) 1.4 Emulsion 10.0 Propylene glycol 7.0 Triethylene glycol 3.0 Ion-exchanged water Remaining amount In the compound 3 of the above formula (I), R ¹¹ , R ¹² , R ¹³ , and R ¹⁴ are methyl groups, and A and B each have an average value of 4 units of a propylene oxide group and an average value of an ethylene oxide group of 4 units. And 10 units, and the sum of the groups is 14 on average.

Example A4 Addition amount (% by weight) Water-soluble pigment 4 (80) 5.0 Compound 4 of formula (I) 4 0.8 Emulsion 3.0 1,6-hexanediol 5.0 Tripropylene glycol 2. 0 compound 4 DMI 2.0 sodium benzoate 0.1 ion-exchanged water Balance formula (I) above, R11 and R12 are methyl groups, R ¹³ and R ¹⁴ is isopropyl group,
A and B are compounds each representing a group having an average of 3 units of a propylene oxide group, an average of 9 units of an ethylene oxide group, and a total of 12 units.

Example A5 Addition amount (% by weight) Water-soluble pigment 1 3.0 Water-soluble dye A1 1.0 Compound 5 of formula (I) 5 1.2 Emulsion 3.5 PGmBE 2.0 MPD 3.0 1, 5-pentanediol 3.0 triethanolamine 0.9 ion-exchanged water balance In compound 5 of the above formula (I), R ¹¹ and R ¹² are methyl groups, R ¹³ and R ¹⁴ are isobutyl groups, A and B are compounds each representing a propylene oxide group having an average of 4 units, an ethylene oxide group having an average of 12 units, and a total of 16 units. The water-soluble dye A1 is a compound represented by the above formula (IV), wherein A is COOK, X and Y are methyl groups, and M is potassium.

Example A6 Addition amount (% by weight) Water-soluble dye A2 5.0 Compound of formula (I) 6 0.5 Emulsion 4.0 DPGmBE 2.0 DEGmBE 10.0 Neopentyl glycol 5.0 Ion-exchanged water compounds of remaining above formula (I) 6, R ¹¹ and R ¹² are methyl groups, R ¹³ and R ^{1 4} is a n- propyl group, 2 a and B is the average value of the propylene oxide group, respectively It is a compound that represents a unit having 4 units of ethylene oxide groups on average and a total of 6 units on average. Also,
The water-soluble dye A2 is a compound represented by the formula (V),
A compound in which m is 1, n is 1, and M is potassium.

Example A7 Addition amount (% by weight) Direct Blue 86 5.0 Compound 7 of formula (I) 1.6 Emulsion 5.0 TEGmBE 10.0 Glycerin 5.0 Trimethylolpropane 5.0 Triethanolamine 0 compound 7 .1 ion-exchanged water Balance formula (I) above, R ¹¹ and R ¹² are methyl groups, R ¹³ and R ^{1 4} is isobutyl group, the average of a and B are each propylene oxide groups It is a compound that represents a group with a value of 10 units, an average of 40 units of ethylene oxide groups and a total of 50 on average.

Example A8 Addition amount (% by weight) Acid Red 52 5.5 Compound 8 of formula (I) 1.0 Emulsion 5.0 DPGmBE 5.0 DEGmBE 5.0 Diethylene glycol 5.0 Dodecylbenzenesulfonic acid Na 0 .2 Residual ion-exchanged water In compound 8 of the above formula (I), R ¹¹ and R ¹² are methyl groups, R ¹³ and R ¹⁴ are isobutyl groups, and A and B are each a propylene oxide group on average. 1 unit,
It is a compound that represents an ethylene oxide group having an average of 1 unit and a total of 2 units on average.

Comparative Example A In the following Comparative Examples, a pigment dispersion means carbon black dispersed using a random copolymerizable styrene acrylic acid as a dispersant, and the average particle size is shown in parentheses in nm units. It was as shown by.

Comparative Example A1 Amount (% by weight) Pigment dispersion liquid (90) 5.0 Dispersant 3.0 Nonionic surfactant 0.8 2-Pyrrolidone 3.0 Polyethylene glycol 1000 4.0 Ion-exchanged water Remaining amount

Comparative Example A2 Amount (% by weight) Food Black 2 5.5 Glycerin 10.0 Ethyl carbitol 10.0 2-Pyrrolidone 5.0 Ion-exchanged water Remaining amount

Comparative Example A3 Amount (% by weight) Pigment dispersion liquid (110) 5.5 Water-soluble dye (food black 2) 2.5 Diethylene glycol 10.0 Nonionic surfactant 1.0 Ion-exchanged water Remaining amount

Printing Evaluation Test Character printing was performed using the ink compositions of the above Examples and Comparative Examples using an ink jet printer MJ-930C (manufactured by Seiko Epson Corporation). The paper used for evaluation was Conquero, a plain paper marketed in Europe, the United States, and Japan.
r paper, Favorite paper, Modo copy paper, Ra
pid Copy paper, EPSON EPP paper, Xero
x 4024 paper, Xerox 10 paper, Neenha
Bond paper, Riccopy 6200 paper, Yamayuri paper,
And Xerox R paper. The degree of bleeding of the obtained printed matter was evaluated according to the following criteria.

In the evaluation, assuming that a spherical ink droplet of 10 to 50 mg spreads in a circle on the paper surface, the radius r ₁ of the inscribed circle and the radius r of the circumscribed circle of the shape formed by the ink droplet are determined.
Comparing the value of the ratio r ₂ / r ₁ and _2.

Evaluation A: r ₂ / r ₁ ≦ 2.0 Evaluation B: 2.0 <r ₂ / r ₁ ≦ 4.0 Evaluation C: 4.0 <r ₂ / r ₁ ≦ 6.0 Evaluation D: 6.0 <r ₂ / r ₁ The results were as shown in the table below.

[0094]

[Table 1]

Example B Example B1 Addition amount (% by weight) Water-soluble pigment 1 (105) 5.0 Compound 1 of formula (II) 8.0 Emulsion 3.0 Glycerin 6.0 1,5-pentanediol 5 0.0 triethanolamine 0.8 ion-exchanged water remaining amount In the compound 1 of the formula (II), R ²¹ and R ²² are both H, one of R ²³ and R ²⁴ is a methyl group, and the other is H
Wherein R ²⁵ is a butyl group and m + n is 2.

Example B2 Amount (% by weight) Water-soluble pigment 2 (85) 4.5 Compound 2 of formula (II) 10.0 Emulsion 3.0 Dipropylene glycol 5.0 Surfynol 465 1.2 Triethanol Amine 0.1 ion-exchanged water remaining amount In compound 2 of the above formula (II), one of R ²¹ and R ²² is a methyl group, the other is H, and both R ²³ and R ²⁴ are H
Wherein R ²⁵ is a butyl group and m + n is 2.

Example B3 Amount (% by weight) Water-soluble pigment 3 (90) 5.5 Compound 3 of formula (II) 10.0 Emulsion 10.0 Propylene glycol 7.0 Triethylene glycol 3.0 1.6 -Hexanediol 5.0 Potassium hydroxide 0.1 Ion-exchanged water Remaining In compound 3 of the above formula (II), R ²¹ and R ²² are both H, and one of R ²³ and R ²⁴ is a methyl group. The other is H
, And the compound R ²⁵ is a butyl group, R ²¹ and R
²² is a mixture with a compound in which one is a methyl group, the other is H, R ²³ and R ²⁴ are H, and R ²⁵ is a butyl group, and the average value of m + n is 2.

Example B4 Amount (% by weight) Water-soluble pigment 4 (80) 5.0 Water-soluble dye B1 1.0 Compound 4 of formula (II) 8.0 Emulsion 1.0 Tripropylene glycol 2.0 Dimethyl -2-imidazolidinone 2.0 sodium benzoate 0.1 ion-exchanged water balance In compound 4 of the above formula (II), R ²¹ and R ²² are both H, and one of R ²³ and R ²⁴ is methyl. a group the other is H, with a compound R ²⁵ is a butyl group, R ²¹ and R ²²
Is a methyl group and the other is H, R ²³ and R
Both ²⁴ are H and a mixture with a compound in which R ²⁵ is a butyl group, and the average of m + n is 3.
The water-soluble dye B1 is a compound represented by the formula (IV), wherein A is COOK, X and Y are methyl groups, and M is potassium.

Example B5 Addition amount (% by weight) Water-soluble pigment 1 (105) 3.0 Water-soluble dye B2 1.0 Compound 5 of formula (II) 7.0 Emulsion 1.0 Triethanolamine 0.9 ion Exchange Water Remaining In the compound 5 of the above formula (II), R ²¹ and R ²² are both H, one of R ²³ and R ²⁴ is a methyl group and the other is H
, And the compound R ²⁵ is a butyl group, R ²¹ and R
²² is a mixture with a compound in which one is a methyl group, the other is H, R ²³ and R ²⁴ are both H, and R ²⁵ is a butyl group, and the average value of m + n is 4. .
The water-soluble dye B2 is a compound represented by the formula (IV), wherein A is COONa, X and Y are methyl groups, and M is sodium.

Example B6 Addition amount (% by weight) Water-soluble dye 2 5.0 Compound 6 of the formula (II) 6.0 Glycerin 15.0 Triethanolamine 0.9 Ion-exchanged water Remaining amount of the above formula (II) In compound 6, R ²¹ and R ²² are both H, one of R ²³ and R ²⁴ is a methyl group and the other is H
, And the compound R ²⁵ is a butyl group, R ²¹ and R
²² is a mixture with a compound in which one is a methyl group, the other is H, R ²³ and R ²⁴ are both H, and R ²⁵ is a butyl group, and the average value of m + n is 2.5. It is. The water-soluble dye 2 is a compound represented by the formula (V), wherein m is 1, n is 1, and M is potassium.

Example B7 Amount (wt%) Direct Blue 86 5.0 Compound 7 of formula (II) 10.0 Glycerin 5.0 Trimethylolpropane 5.0 Trimethylolethane 5.0 Surfynol 465 1.0 Triethanolamine 0.1 ion-exchanged water remaining amount In the compound 7 of the above formula (II), R ²¹ and R ²² are both H, one of R ²³ and R ²⁴ is a methyl group, and the other is H
, And the compound R ²⁵ is a butyl group, R ²¹ and R
²² is a mixture of compounds in which one is a methyl group, the other is H, R ²³ and R ²⁴ are both H, and R ²⁵ is a butyl group, and the average value of m + n is 6.

Example B8 Addition amount (% by weight) Acid Red 52 5.5 Compound of the formula (II) 8 6.0 Diethylene glycol 5.0 Tetrapropylene glycol 5.0 Ion-exchanged water Remaining amount Compound of the above formula (II) 8, R ²¹ and R ²² are both H, one of R ²³ and R ²⁴ is a methyl group and the other is H
Wherein R ²⁵ is a butyl group and m + n is 3.

Comparative Example B In the following Comparative Examples, the pigment dispersion means carbon black dispersed using random copolymerizable styrene acrylic acid as a dispersant, and the average particle size is indicated in parentheses in nm units. It was as shown by.

Comparative Example B1 Amount Added (% by Weight) Pigment Dispersion (90) 5.0 Glycerin 10.0 Dispersant 3.0 Nonionic Surfactant 1.0 Deionized Water Remaining

Comparative Example B2 Addition amount (% by weight) Food Black 2 5.5 DEGmME 7.0 Diethylene glycol 10.0 2-Pyrrolidone 5.0 Ion-exchanged water Remaining amount

Comparative Example B3 Addition amount (% by weight) Water-soluble pigment 11 (110) 5.5 Food black 2 2.5 Diethylene glycol 10.0 Nonionic surfactant 1.0 Ion-exchanged water Remaining amount

Print Evaluation Test The ink compositions of Examples B1 to B8 and Comparative Examples B1 to B3 were evaluated for bleeding of printed matters obtained in the same manner as in Examples A1 to 8 and Comparative Examples B1 to B3. The results were as shown in the table below.

[0108]

[Table 2]

Example C Example C1 Amount (% by weight) Water-soluble pigment 1 (105) 5.0 Compound 1 of formula (III) 8.0 DEGmBE 2.0 Emulsion 3.0 Glycerin 6.0 1.5 -Pentanediol 5.0 triethanolamine 0.8 ion-exchanged water remaining amount Compound 1 of the above formula (III) is a compound wherein R ³¹ is a neopentyl group and p is 3.

Example C2 Amount (% by weight) Water-soluble pigment 2 (85) 4.5 Compound 2 of formula (III) 10.0 Emulsion 3.0 Dipropylene glycol 5.0 Surfynol 465 1.2 Triethanol Amine 0.9 Ion-exchanged water Remaining Compound 2 of the above formula (III) is a compound wherein R ³¹ is a t-butyl group and p is 3.

Example C3 Amount (% by weight) Water-soluble pigment 3 (90) 5.5 Compound 3 of formula (III) 10.0 Emulsion 10.0 Diethylene glycol 7.0 Thiodiglycol 3.5 1,6- Hexanediol 5.0 Triethanolamine 1.0 Potassium hydroxide 0.1 Ion-exchanged water Remaining Compound 3 of the above formula (III) is a compound in which R ³¹ is an n-hexyl group and p is 3. .

Example C4 Addition amount (% by weight) Water-soluble pigment 4 (80) 5.0 Water-soluble dye C1 1.0 Compound of formula (III) 4 8.0 TEGmBE 3.0 Emulsion 1.0 Diethylene glycol 0 1,5-pentanediol 2.0 dimethyl-2-imidazolidinone 2.0 sodium benzoate 0.1 triethanolamine 0.7 ion-exchanged water remaining amount In the compound 4 of the above formula (III), R ³¹ The compound is an isobutyl group and p is 3. The water-soluble dye C1
Is a compound represented by the formula (IV), wherein A is COOK, X and Y are methyl groups, and M is potassium.

Example C5 Amount (% by weight) Water-soluble pigment 1 (105) 3.0 Water-soluble dye C2 1.0 Compound 5 of formula (III) 7.0 DEGmBE 2.0 Emulsion 1.0 Glycerin 0 Triethanolamine 0.9 Ion-exchanged water Remaining Compound 5 of the above formula (III) is a compound in which R ³¹ is an n-hexyl group and p is 3, 50% of the compound, and R ³¹ is an n-pentyl group. And a mixture with 50% of the compound in which p is 3. The water-soluble dye C2 is a compound represented by the formula (IV), wherein A is COONa, X and Y are methyl groups, and M is sodium.

Example C6 Amount (% by weight) Water-soluble dye 2 5.0 Compound 6 of formula (III) 6.0 TEGmBE 4.0 Glycerin 15.0 Thiodiglycol 2.0 1, 5-Pentanediol 1 0.0 triethanolamine 0.9 ion-exchanged water remaining amount Compound 6 of the above formula (III) is a compound in which R ³¹ is a 1,1-dimethylbutyl group and p is 3. The water-soluble dye 2 is a compound represented by the formula (V), wherein m is 1, n is 1, and M is potassium.

Example C7 Amount (% by weight) Direct Yellow 132 5.0 Compound 7 of the formula (III) 10.0 DEGmBE 3.0 Glycerin 5.0 Trimethylolpropane 5.0 Trimethylolethane 5.0 Surfy No. 465 1.0 Triethanolamine 0.5 KOH 0.05 Ion-exchanged water Remaining 50% of the compound 4 of the above formula (III) is a compound in which R ³¹ is a 1,3-dimethylbutyl group and p is 3. And 50% of a compound in which R ³¹ is a 1,2-dimethylbutyl group and p is 3.

Example C8 Addition amount (% by weight) Acid Blue 9 5.5 Compound 8 of the formula (III) 6.0 Glycerin 5.0 Diethylene glycol 5.0 Tetrapropylene glycol 5.0 Triethanolamine 0.9 KOH 0 compound 8 .1 ion-exchanged water Balance the above formula (III), R ³¹ is a neopentyl group, p 3 and compound 50% is that, R ³¹ is n- pentyl group, p is 3 It is a mixture of 30% of the compound and 20% of the compound in which R ³¹ is an isopentyl group and p is 3.

Comparative Example C In the following Comparative Examples, the term “pigment dispersion liquid” means carbon black dispersed using a random copolymerizable styrene acrylic acid as a dispersant, and the average particle size is shown in parentheses in nm units. It was as shown by.

Comparative Example C1 Addition amount (% by weight) Water-soluble pigment 9 (90) 5.0 Glycerin 10.0 Dispersant 3.0 Nonionic surfactant 1.0 Ion-exchanged water Remaining amount

Comparative Example C2 Addition amount (% by weight) Food Black 2 5.5 DEGmME 7.0 Diethylene glycol 10.0 2-Pyrrolidone 5.0 Ion-exchanged water Remaining amount Comparative Example C3 Addition amount (% by weight) Water-soluble pigment 11 (110) 5.5 Food black 2 2.5 Diethylene glycol 10.0 Nonionic surfactant 1.0 Ion exchange water Remaining

Printing Evaluation Test The ink compositions of Examples C1 to C8 and Comparative Examples C1 to C3 were evaluated for bleeding of printed matters obtained in the same manner as in Examples A1 to C8 and Comparative Examples B1 to B3. The results were as shown in the table below.

[0121]

[Table 3]

Claims (17)

[Claims] An ink jet recording ink comprising a water-soluble coloring material, a water-soluble organic solvent, water, and at least a compound represented by the following formula (I), (II) or (III). Embedded image (Wherein, R ¹¹ , R ¹² , R ¹³ , and R ¹⁴ each independently represent a C _1-6 alkyl group, and A and B each independently represent an ethyleneoxy group and / or a propyleneoxy group. A group consisting of A and B
Has at least one propyleneoxy group, and the total of ethyleneoxy groups and propyleneoxy groups is 2
~ 60) (In the above formula, one of R ²¹ and R ²² is H and the other is CH ₃
Or H, one of R ²³ and R ²⁴ is H and the other is CH ₃ or H, provided that R ²¹ , R ²² , R ²³ , and R ²⁴ are all H at the same time.
Not represent a, R ²³ and R ²⁴ when either one is H in R ²¹ and R ²² are both H, at least one of R ²³ and R ²⁴ when R ²¹ and R ²² are both H One is CH ₃ , R ²⁵ represents a C _4-10 alkyl group, and m and n satisfy 2 ≦ m + n ≦ 6. (In the above formula, R ³¹ represents a C _4-10 alkyl group, and p is 3 to
6 is an integer) 2. The compound represented by the formula (I) having an HLB value of 7
The ink for inkjet recording according to claim 1, which is the above. 3. The method according to claim 1, wherein the amount of the compound represented by the formula (I) is 0.
The ink for inkjet recording according to claim 1, which is 1 to 10% by weight. 4. The method according to claim 1, wherein the amount of the compound represented by the formula (II) is 0.
The ink for inkjet recording according to claim 1, which is 5 to 30% by weight. 5. The amount of the compound represented by the formula (III) is 3
The ink for inkjet recording according to claim 1, wherein the amount is from 30% by weight to 30% by weight. 6. The ink for ink-jet recording according to claim 1, wherein the water-soluble coloring material is a water-soluble dye and / or a water-soluble pigment dispersible in water. 7. The ink-jet recording ink according to claim 6, wherein when the water-soluble coloring material is a water-soluble pigment, the ink further comprises an emulsion. 8. The ink jet recording ink according to claim 7, wherein the amount of the emulsion added is 1 to 10% by weight. 9. The emulsion according to claim 7, wherein the emulsion has a core-shell structure comprising a core portion and a shell portion surrounding the core portion, and the shell portion comprises a crosslinked resin.
3. The ink for inkjet recording according to item 1. 10. An ink jet recording method for performing printing by discharging droplets of an ink composition and attaching the droplets to a recording medium, wherein the ink composition is used as an ink composition. An ink-jet recording method using the ink composition described in 1. 11. The ink jet recording method according to claim 10, wherein a droplet of the ink composition is discharged from a tip of a nozzle having a water-repellent surface. 12. The ink jet recording method according to claim 11, wherein the tip of the nozzle having a water-repellent surface has a eutectoid plating surface of tetrafluoroethylene and an oxidation-resistant metal. 13. The ink jet recording method according to claim 11, wherein an ink jet recording ink having a contact angle of 50 ° or more with the water-repellent surface at the tip of the nozzle is used. 14. When the droplet of the ink composition is ejected by the electrostrictive element and the ink composition is not ejected, the electrostrictive element is slightly moved so as not to eject the droplet of the ink composition from the nozzle. An inkjet recording method according to any one of claims 10 to 13. 15. The ink jet recording method according to claim 14, wherein an ink composition containing the added amount of the water-soluble coloring material in the range of 3 to 15% by weight is used. 16. The ink jet recording method according to claim 10, wherein an ink contained in an ink cartridge filled with a polyurethane foam is used as the composition. 17. A recorded matter recorded by the ink jet recording method according to claim 10. Description: