JP2002012799A - Ink jet recording ink composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an ink jet recording ink composition having ease of color compensation and good powder characteristics and, part of the image formed by allowing the composition to adhere on to a member to record an image thereon being hardly transferred to the superposed member even on storage of the members having the image superposed on one another. SOLUTION: The inkjet recording ink composition is obtained by adding a water-soluble dye to polymeric fine particles containing an oil-soluble dye obtained by polymerizing (a) 0.5-10 mass% unsaturated monomer having a carboxyl group in the molecule, (b) 1-20 mass% unsaturated monomer having a glycidyl group, and (c) other unsaturated monomers.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an ink composition for ink jet recording containing polymer fine particles, and more particularly to an ink composition for ink jet recording used for a recording sheet for recording using a coloring material. The present invention relates to an ink composition for inkjet recording, which has good storage stability and granularity.

[0002]

2. Description of the Related Art In an ink-jet system, heat is applied to a colored liquid called an ink composition for ink-jet recording (hereinafter, also simply referred to as ink for ink-jet recording, ink composition or ink) to generate air bubbles and generate air bubbles. This is a method in which small droplets of ink are ejected from nozzles by the pressure generated when printing, the pressure of a piezoelectric element, or the like, and adhered to a recording member such as paper, film, or cloth to perform recording.

As inks applied to this method, there are aqueous inks containing a water-soluble dye, inks containing a pigment, wax inks containing a low-melting solid wax containing a dye, and inks containing an oil-soluble dye. A water-based ink containing a water-soluble dye tends to bleed a formed image and has poor water resistance. An ink containing a pigment is less likely to bleed and has relatively excellent water resistance, but has relatively poor image sharpness (sharpness and granularity).

A wax ink containing a low-melting solid wax containing a dye is complicated by attaching it to a recording member and then fusing it to complete an image. There are two types of inks containing oil-soluble dyes: those using an oily medium such as an organic solvent and those using an aqueous medium.The former has limited use in terms of the environment, so the latter has excellent water resistance without bleeding. In particular, inks in which oil-soluble ink is impregnated in polymer fine particles have excellent water resistance without bleeding,
It is expected that nozzle clogging is unlikely to occur.

As such an ink, for example, Japanese Unexamined Patent Publication No.
No. 4-58504 discloses a latex obtained by emulsion polymerization of a vinyl monomer such as acetoacetoxyethyl methacrylate having an active methylene group and n-butyl acrylate and sodium 2-acrylamide-2-methylpropane sulfonate as an organic fine particle in an organic solvent. There is disclosed an ink using polymer fine particles impregnated with an oil-soluble dye by adding an oil-soluble dye, stirring and evaporating an organic solvent.

Japanese Patent Application Laid-Open No. 55-139471 discloses a polymer fine particle obtained by adding an oil-soluble dye to a latex obtained by emulsion-polymerizing a vinyl monomer such as glycidyl acrylate and butyl methacrylate with a low molecular surfactant and heating and stirring. The disclosed ink compositions are disclosed.

JP-A-58-45272 discloses an ink composition using a polyurethane polymer particle impregnated with a dye. JP-A-62-17207
No. 6 discloses an ink in which a vinyl polymer fine particle having a nonionic stabilizer is impregnated with an oil-soluble dye. JP-A-62-184072 discloses an ink in which an oil-soluble dye is impregnated in vinyl polymer fine particles using a vinyl monomer having two or more vinyl groups as a copolymerization component.

In Japanese Patent Application Laid-Open No. 8-231907, 1,4-divinylbenzene, a bi-based monomer having two or more vinyl groups, is used as a copolymer component in the presence of an oil-soluble dye.
There is disclosed an ink in which a vinyl polymer fine particle such as ethylhexyl acrylate, n-butyl acrylate, methyl methacrylate, styrene, or acrylic acid is emulsion-polymerized and impregnated with an oil-soluble dye.

However, the ink composition obtained by impregnating these oil-based inks with polymer fine particles is excellent in bleeding and water resistance and is unlikely to cause nozzle clogging. When stored, depending on the storage conditions, a part of the adhered image is easily transferred to the superposed member, and there has been a demand for an ink composition for inkjet recording having a lower transferability after storage.

[0010]

SUMMARY OF THE INVENTION It is an object of the present invention to facilitate color correction, improve graininess, and adhere to a member to be recorded, record the member, and store the member in a superimposed state. An object of the present invention is to provide an ink composition for inkjet recording in which a part of an image is difficult to be transferred to a superimposed member.

[0011]

The above object of the present invention has been attained by the following constitutions.

1. 0.5 to 10% by weight of an unsaturated monomer having a carboxyl group in the molecule (a), 1 to 20% by weight of an unsaturated monomer having a glycidyl group (b) and another unsaturated monomer (c) An ink composition for ink jet recording, characterized by adding a water-soluble dye to polymer fine particles containing an oil-soluble dye obtained by polymerizing the above.

2. 0.5 to 10% by weight of an unsaturated monomer having a carboxyl group in the molecule (a), 1 to 20% by weight of an unsaturated monomer having a glycidyl group (b) and another unsaturated monomer (c) An ink composition for ink-jet recording, characterized in that a pigment is added to polymer fine particles containing an oil-soluble dye obtained by polymerizing (i).

3. 0.5 to 10% by weight of an unsaturated monomer having a carboxyl group in the molecule (a), 1 to 20% by weight of an unsaturated monomer having a glycidyl group (b) and another unsaturated monomer (c) A) a water-soluble dye and a pigment are added to polymer fine particles containing an oil-soluble dye obtained by polymerizing the above (a).

4. The other unsaturated monomer (c) is an unsaturated monomer (c-1) having an acetoacetyl group in the molecule.
4. The ink composition for ink jet recording according to any one of the above items 1 to 3, wherein

5. The ink composition for inkjet recording according to any one of the above items 1 to 4, wherein the ink composition contains a high boiling point solvent. Hereinafter, the present invention will be described in more detail.

The polymer fine particles referred to in the present invention are those in which a water-insoluble hydrophobic polymer is dispersed as fine particles in a water-soluble dispersion medium. The dispersion state is such that the hydrophobic polymer is emulsified in the dispersion medium, emulsion-polymerized, micelle-dispersed, or has a partially hydrophilic structure in the hydrophobic polymer molecule and the molecular chain itself is Any of those having molecular dispersion may be used.

The average particle size of the dispersed particles is not particularly limited.
Preferably from 10 to 5000 nm, more preferably from 50 to
A range of about 500 nm is preferable. The particle size distribution of the dispersed particles is not particularly limited, and may have a wide particle size distribution or a monodispersed particle size distribution. The average particle size here is measured by a dynamic light scattering method.

As the polymer fine particles of the present invention, so-called core / shell type fine particles may be used other than the polymer fine particles having a uniform structure having no difference in polymer composition between the inside and the surface of the particles.
In this case, it may be preferable for the core / shell to have a different glass transition temperature. The minimum film formation temperature (MFT) of the polymer fine particles of the present invention is preferably from -30C to 90C, more preferably from 0C to 70C. A film-forming auxiliary may be added to control the minimum film-forming temperature. The film forming aid is an organic compound (usually an organic solvent) which is also called a plasticizer and lowers the minimum film forming temperature of the polymer fine particles. For example, "Synthesis of synthetic latex (Souichi Muroi, published by Kobunshi Kankokai (197)
0)) ".

In the case of a copolymer, it may be a random copolymer or a block copolymer. The molecular weight of the hydrophobic polymer is not particularly limited, but is preferably 50 in number average molecular weight.
00-1,000,000, more preferably 10,000-1
00000.

The polymer fine particles (polymer of polymer latex) of the present invention preferably have an equilibrium water content at 25 ° C. and 60% RH of usually 2% by mass or less, more preferably 1% by mass or less.

The definition and measurement method of the equilibrium moisture content can be referred to, for example, “Lecture of Polymer Engineering 14, Test Method for Polymer Materials (edited by the Society of Polymer Science, Jinjinshokan)”.

As the unsaturated monomer (a) having a carboxyl group in the molecule of the present invention, one containing one or more carboxylic acids in the molecule, for example, acrylic acid, methacrylic acid, Maleic acid, maleic anhydride, fumaric acid, crotonic acid, itaconic acid, citraconic acid, cinnamic acid and the like can be suitably used.

The amount of the unsaturated monomer (a) used is 0.5 to 10% by mass, based on 100% by mass of the total amount of the unsaturated monomer.
Preferably it is 1-7 mass%.

Examples of the unsaturated monomer (b) having a glycidyl group in the molecule of the present invention include glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, glycidyl vinyl ether,
3,4-epoxycyclohexyl vinyl ether, glycidyl (meth) allyl ether, 3,4-epoxycyclohexyl (meth) allyl ether, and the like.

The amount of the unsaturated monomer (b) used is 1 to 20% by mass, preferably 2 to 15% by mass, based on 100% by mass of the total amount of the unsaturated monomer.

Other unsaturated monomers (c) used for synthesizing the polymer fine particles of the present invention include, for example, methyl acrylate, ethyl acrylate, butyl acrylate, i-butyl acrylate, octyl acrylate,
C1-C12 linear or branched alkyl esters of acrylic acid such as i-octyl acrylate, 2-ethylhexyl acrylate, nonyl acrylate, i-nonyl acrylate, decyl acrylate and dodecyl acrylate; for example, methyl methacrylate, ethyl methacrylate, C1-C12 linear or branched alkyl esters of methacrylic acid such as butyl methacrylate, 2-ethylhexyl methacrylate, and sil methacrylate; for example, styrene, α-methylstyrene, t-butylstyrene, p-chlorostyrene, chloromethylstyrene Monovinyl monomers such as vinyl and toluene; vinyl cyanide monomers such as acrylonitrile and methacrylonitrile; vinyl formate, vinyl acetate, vinyl propionate Sachikku acid vinyl, and the like.

As the unsaturated monomer (c-1) having an acetoacetyl group in the molecule preferably used in the present invention, a monomer represented by the following general formula (2) can be used.

[0029]

Embedded image

In the formula, R ¹ and R ³ are a hydrogen atom or an alkyl group (eg, a methyl group, an ethyl group, an octyl group, etc.), X is a single bond, an alkylene group (eg, a methylene group, an ethylene group), —COOZ ₁ —. , -CONNZ _2- ,
Z ₁ and Z ₂ are an alkylene group having 1 to 6 carbon atoms, and Y ¹ is a hydrogen atom or a nitrile group.

As the monomer (c-1), for example,
Alkenyl esters of acetoacetic acid such as vinyl acetoacetate and (meth) allyl acetoacetate; for example, 2-acetoacetoxyethyl (meth) acrylate, 2-acetoacetoxypropyl (meth) acrylate, 3-acetoacetoxypropyl (meth) acrylate (Meth) acrylic alkylene glycols such as, 2-acetoacetoxybutyl (meth) acrylate, 2-acetoacetoxybutyl (meth) acrylate, 3-acetoacetoxybutyl (meth) acrylate, and 4-cyanoacetoacetoxyethyl (meth) acrylate Diesters of acids and (substituted) acetoacetic acids; for example, alkylene glycols such as 2-acetoacetoxyethyl crotonate, 2-acetoacetoxypropyl crotonate, 3-acetoacetoxypropyl crotonate Diesters of crotonic acid and acetoacetic acid; for example, N- acetoacetoxy methyl (meth)
Acrylamide, N-acetoacetoxyethyl (meth)
Examples include acetoacetate of N-alkylol (meth) acrylamide such as acrylamide.

Further, as the monomer (c-1), 2
Hydroxyalkyl (meth) such as -hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate
A lactone-modified hydroxyalkyl (meth) acrylate comprising an adduct of an acrylate and a lactone such as caprolactone is esterified with acetoacetic acid, or the lactone-modified hydroxyalkyl (meth) acrylate is acetoacetylated with diketene. The resulting lactone-modified hydroxyalkyl glycol (meth) acrylate acetoacetic acid diester can also be used.

Among these monomers (c-1), 2-acetoacetoxyethyl (meth) acrylate, 2-acetoacetoxypropyl (meth) acrylate, 3-acetoacetoxypropyl (meth) acrylate, and 4-acetoacetoxybutyl (meth) acrylate Meth) acrylates are preferred.

These monomers (c-1) can be used alone or in combination of two or more.

In polymerizing the polymer fine particles of the present invention, anionic and / or nonionic surfactants can be used as long as they do not adversely affect the performance of the resulting aqueous dispersion of the copolymer.

The nonionic surfactants are not particularly restricted but include, for example, polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether and polyoxyethylene stearyl ether; for example, polyoxyethylene octyl phenyl ether, polyoxyethylene Polyoxyethylene alkyl phenyl ethers such as nonylphenyl ether; sorbitan higher fatty acid esters such as sorbitan monolaurate, sorbitan monostearate and sorbitan trioleate; polyoxyethylene such as polyoxyethylene sorbitan monolaurate Sorbitan higher fatty acid esters;
For example, polyoxyethylene higher fatty acid esters such as polyoxyethylene monolaurate and polyoxyethylene monostearate; for example, glycerin higher fatty acid esters such as oleic acid monoglyceride and stearic acid monoglyceride; for example, polyoxyethylene polyoxyethylene Propylene block copolymer and the like can be mentioned.

Examples of the anionic surfactants include higher fatty acid salts such as sodium oleate; alkylaryl sulfonates such as sodium dodecylbenzenesulfonate; alkyl sulfates such as sodium lauryl sulfate; Salts; for example, polyoxyethylene alkyl ether sulfates such as sodium polyethoxyethylene lauryl ether sulfate; polyoxyethylene alkyl aryl ether sulfates such as sodium polyoxyethylene nonylphenyl ether sulfate; sodium monooctyl sulfosuccinate; Alkyl sulfosuccinate salts such as sodium dioctyl sulfosuccinate and sodium polyoxyethylene lauryl sulfosuccinate, and derivatives thereof. Can.

When the polymer fine particles of the present invention are subjected to emulsion polymerization or suspension polymerization, a water-soluble polymer may be used as an emulsifier, for example, polyvinyl alcohol such as partially saponified polyvinyl alcohol, fully saponified polyvinyl alcohol, and modified polyvinyl alcohol. Alcohols and the like, as natural polymers or semi-synthetic water-soluble polymers,
Alginic acid or a salt thereof, dextran, dextran sulfate, glycogen, gum arabic, albumin, agar, starch, carboxymethylcellulose or a salt thereof, hydroxycellulose, natural polysaccharides such as cellulose sulfate and guar gum, and derivatives thereof are also included. .

The polymer fine particles of the present invention are polymerized in a water-soluble dispersion medium in the presence of an oil-soluble dye. Polymerization in a water-soluble dispersion medium in the presence of an oil-soluble dye means that an aqueous medium, a dispersant, an oil-soluble dye, a monomer, and a polymerization initiator are put into a reaction vessel, and the mixture in the reaction vessel is heated to carry out polymerization. It is.

Examples of the oil-soluble dyes include monoazo oil-soluble dyes, anthraquinone oil-soluble dyes, diazo-based oil-soluble dyes, phthalocyanine-based oil-soluble dyes, metal complex salt-type monoazo-based oil-soluble dyes, and triallylmethane-based oil-soluble dyes. Can be mentioned. One of these dyes may be used, or two or more oil-soluble dyes may be used in combination.

The addition amount of these oil-soluble dyes is preferably from 0.1 to 20% by mass of the aqueous ink composition. Further, the present invention is characterized in that at least one selected from water-soluble dyes and pigments is added to the polymer particles of the present invention.

The water-soluble dispersion medium preferably used in the present invention is a liquid containing water as a main component, but may contain a water-soluble organic solvent if necessary. Examples of the water-soluble organic solvent include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, and 2-methyl-2-
Propanol, 1-pentanol, 2-pentanol,
3-pentanol, 2-methyl-1-butanol, 3-
Monoalcohol compounds such as methyl-1-butanol, 2-methyl-2-butanol and 3-methyl-2-butanol, ethylene glycol, polyethylene glycol, propylene glycol, triethylene glycol, polytriethylene glycol, tetraethylene glycol, polytetra Examples include polyhydric alcohol compounds such as ethylene glycol, 1,3-butanediol, glycerin, and 1,2,6-hexanetriol. One of these water-soluble organic solvents may be used, or two or more water-soluble organic solvents may be used in combination. The addition amount of these water-soluble organic solvents is 0.1 to 0.1 of the ink composition for inkjet.
20.0% by mass is preferred.

In the polymerization reaction, it goes without saying that the polymerization initiator, the concentration, the polymerization temperature, the reaction time and the like can be varied widely and easily according to the purpose.

Further, the polymerization reaction may be carried out by putting a monomer, a surfactant, a water-soluble polymer, and a medium in advance in a container and adding an initiator thereto, or, if necessary, a part of each component. Alternatively, the polymerization may be carried out while dropping the whole amount.

In the emulsion polymerization, usually, for example,
Persulfates such as sodium persulfate, potassium persulfate and ammonium persulfate; t-butyl hydroperoxide;
Polymerization initiators such as organic peroxides such as cumene hydroperoxide and p-menthane hydroperoxide; hydrogen peroxide; These polymerization initiators can be used either in one kind or in a combination of two or more kinds. These polymerization initiators, based on a total of 100 parts by mass of the monomer,
It is preferred to use an amount of 0.1 to 1 part by weight.

In the emulsion polymerization, a reducing agent may be used together with the polymerization initiator, if desired. Examples of such a reducing agent include ascorbic acid, tartaric acid, citric acid, and glucose. Reducing organic compounds such as formaldehyde sulfoxylate metal salts; and reducing inorganic compounds such as sodium thiosulfate, sodium sulfite, sodium bisulfite, and sodium metabisulfite;
These reducing agents are preferably used in an amount of 0.1 to 1 part by mass based on 100 parts by mass of the total of the monomers.

Further, a chain transfer agent can be used in the emulsion polymerization. Examples of such a chain transfer agent include dodecyl mercaptan, t-dodecyl mercaptan, butyl mercaptan, 2-ethylhexyl thioglycolate, 2-mercaptoethanol, and trichlorobromomethane. These chain transfer agents are used in an amount of 0 to 100 parts by mass in total of the monomers.
It is preferable to use an amount of about 1 part by mass.

In the emulsion copolymerization of the acrylic copolymer preferably used in the present invention, the preferable copolymerization temperature is 40 to
The temperature is 100 ° C, more preferably 60 to 90 ° C.

Next, the water-soluble dye will be described. Examples of the water-soluble dye of the present invention include a water-soluble direct dye, an acid dye, a reactive dye, and a basic dye. The typical ones are as follows. These are typical, and other dyes having structures similar to these may be used.

<Direct Dye> C.I. I. Direct Yellow: 1, 4, 8, 11, 1
2, 24, 26, 27, 28, 33, 39, 44, 5,
0, 58, 85, 86, 100, 110, 142, 14
4 C. I. Direct Red: 1, 2, 4, 9, 11, 1
3, 17, 20, 23, 24, 28, 31, 33, 3
7, 39, 44, 47, 48, 51, 62, 63, 7
5, 79, 80, 81, 83, 89, 90, 94, 9
5, 99, 220, 224, 227, 243 C.I. I. Direct Blue: 1, 2, 6, 8, 15, 2
2, 25, 71, 76, 78, 80, 86, 87, 9
0, 98, 106, 108, 120, 123, 163,
165, 192, 193, 194, 195, 196, 1
99, 200, 201, 202, 203, 207, 23
6, 237 C.I. I. Direct black: 2, 3, 7, 17, 1
9, 22, 32, 38, 51, 56, 62, 71, 7
4, 75, 77, 105, 108, 112, 117, 1
54 <Acid dye> C.I. I. Acid Yellow: 2, 3, 7, 17, 19,
23, 25, 29, 38, 42, 49, 59, 61, 7
2,99 C.I. I. Acid Orange: 56, 64 C.I. I. Acid Red: 1, 8, 14, 18, 26,
32, 37, 42, 52, 57, 72, 74, 80, 8
7, 115, 119, 131, 133, 134, 14
3, 154, 186, 249, 254, 256 C.I. I. Acid Violet: 11, 34, 75 C.I. I. Acid Blue: 1, 7, 9, 29, 87, 1
26, 138, 171, 175, 183, 234, 23
6, 249 C.I. I. Acid Green: 9, 12, 19, 27, 4
1 C. I. Acid Black: 1, 2, 7, 24, 26,
48, 52, 58, 60, 94, 107, 109, 11
0, 119, 131, 155 <Reactive dye> C.I. I. Reactive Yellow: 1, 2, 3, 13, 1
4, 15, 17 C.I. I. Reactive Red: 2, 6, 11, 23, 3
6 C. I. Reactive violet: 2, 4, 8, 9 C.I. I. Reactive Blue: 7, 14, 15, 18,
21, 25 <Basic dye> C.I. I. Basic Yellow: 11, 14, 21, 32 C.I. I. Basic Red: 1, 2, 9, 12, 13 C.I. I. Basic violet: 3, 7, 14 C.I. I. Basic Blue: 3, 9, 24, 25 Other examples of the water-soluble dye of the present invention include a chelate dye and an azo dye used in a so-called silver dye bleaching light-sensitive material (for example, Cibachrome manufactured by Ciba Geigy).

As the chelate dye, for example, the chelate dye described in British Patent 1,077,484 can be used.

As the azo dye for the silver dye bleaching photosensitive material,
For example, British Patent Nos. 1,039,458 and 1,004,
957, 1,077,628, U.S. Pat.
Azo dyes described in 2,448 can be used.

As the water-soluble dye of the present invention, known water-soluble dyes are selected singly or in combination, and it is a preferred embodiment to use a mixture of a plurality of known water-soluble dyes.

As the pigment of the present invention, known organic and inorganic pigments can be used alone or in combination. The term "pigment" as used herein means an insoluble colorant. For example, carbon black, inorganic pigments such as titanium oxide, azo pigments, phthalocyanine pigments,
Organic pigments such as quinacridone pigments, anthraquinone pigments and dioxazine pigments can be mentioned.

The pigment particles need to be small enough to allow free flow of the ink in the ink jet printer device, especially in the injection nozzle, which usually has a diameter in the range of 10 to 50 microns. Also, the size of the particles has an effect on the dispersion stability of the pigment, which is important throughout the life of the ink. It is preferable that the particle size be small in order to prevent the Brownian motion of the fine particles from agglomerating.
It is also desirable to use small particles for maximum color strength and gloss. Useful particle size ranges are typically from 0.003 microns to 10 microns. Preferably, the particle size ranges from 0.005 to 1.0 micron, most preferably from 0.005 to 0.2 micron.

The typical ones are as follows. Permanent Yellow DHG, Permanent Yellow GR, Permanent Yellow G, Permanent Yellow NCG-71, Permanent Yellow GG, Hansa Yellow RA, Hansa Brilliant Yellow 5GX-
02, Dalamar R Yellow YT-858-02, Dalamar R Yellow YT-858-D, Hansa Yellow X, Novo Palm R Yellow HR, Chromophtal R Yellow 3G, Chromophthal R Yellow GR, Novo Palm R Yellow FGL, Hansa Brilliant Yellow 10G
X, Permanent Yellow G3R-1, Chromophtal R Yellow 3G, Irgazine R Yellow 5GT, Hosta Palm R Yellow H4G, Hosta Palm R Yellow H3
G, L74 1357 yellow, L75 1331 yellow, L75 2377 yellow, Hostaperm R orange GR, Paliogen R orange, Irgarit R Rubin 4BL, Kind R Magenta, India First R
Brilliant Scarlet, Hosta Palm R Scarlet GO, Permanent Rubin F6B, Monastral R Magenta, Monastral R Scarlet, Heliogen R Blue L6901F, Heliogen R Blue NBD7
010, Heliogen R Blue K7090, Heliogen R
Blue L7101F, Pariogen R Blue L6470,
Hokoftal R Blue G, XBT-583D, Heliogen R Green K8863, Heliogen R Green L9
140, Monastral R Violet R, Monastral R Red B, Quind R Red R6700, Quind R Red R6713, India First R Violet, Monastral R Violet Malone B, Reaiben R1170, Special Black 4A, Sterling RNS Black, Sterling RNSX76, Chipure RR- 101, Mogul L, BK8200 Hokoftal R Blue BF-585-P, Toluidine Red Y, Kind R Magenta, Magenta RV-6831 Press Cake, Sun First R Magenta 122, India R Brilliant Scarlet, Toluidine Red B, Watchang R Red B , Permanent rubin F6B13-
1731, Hansa R Yellow, Dalamar R Yellow YT-839-P, Sun Bright R Yellow 17
(Sun Chemical Corp., Cincinnati, OH), Toluidine Yellow G, Pigment Scarlet, Auric Brown, black pigment, carbon black.

Next, specific examples of the high boiling water-soluble organic solvent preferably used in the present invention will be described. The water-soluble organic solvent in the present invention can be roughly classified into a high-boiling water-soluble organic solvent and other water-soluble organic solvents.

Specific examples of the high boiling water-soluble organic solvent include glycerin, 1,2,6-hexanetriol, ethylene glycol, diethylene glycol, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, Propylene glycol monobutyl ether, diethylene glycol diethyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, N-methylpyrrolidone,
-Pyrrolidone, propylene glycol, 2-methyl-
2,4-pentanediol, tetraethylene glycol, thioglycol, thiodiglycol, monoacetin, diacetin, 1,3-propanediol, triethylene glycol, 2-phenoxyethanol, 1,2-
And propanediol and 1,4-butanediol.

Specific examples of other water-soluble organic solvents include alkyl alcohols having 1 to 4 carbon atoms (eg, methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl). Alcohols, tert-butyl alcohol, isobutyl alcohol, etc.), amides (eg, dimethylformamide, dimethylacetamide, etc.), ketones or keto alcohols (eg, acetone, diacetone alcohol, etc.), ethers (eg, tetrahydrofuran, dioxane, etc.), poly Alkylene glycols (eg, polyethylene glycol, polypropylene glycol, etc.) and alkylene glycols having an alkylene group containing 2 to 6 carbon atoms (eg, ethylene glycol, propylene glycol, etc.) Butylene glycol, triethylene glycol, 1,2,6-hexanetriol, thiodiglycol, hexylene glycol, diethylene glycol, etc.), glycerin, lower alkyl ethers of polyhydric alcohols (ethylene glycol methyl ether, diethylene glycol methyl Or ethyl) ether, triethylene glycol monomethyl (or ethyl) ether, and the like. Among these organic solvents, preferred are high-boiling organic solvents.

Other additives can be added to the ink composition for ink jet recording of the present invention according to the respective purposes. Examples include a thickener, a fluidity improver, a surfactant, a conductivity adjuster, a pH adjuster, an antioxidant, an ultraviolet absorber, a preservative, a bactericide, a defoamer, and a penetrant.

A surfactant can be used in the ink composition for ink jet recording of the present invention in order to accelerate the penetration of ink droplets after ejection into a medium. Surfactants that can be used include non-cationic surfactants that do not adversely affect the ink such as storage stability.

Further, an electric conductivity adjusting agent can be contained. Examples of the electric conductivity adjusting agent include inorganic salts such as potassium chloride, ammonium chloride, sodium sulfate, sodium nitrate and sodium chloride, and triethanolamine. And water-soluble amines.

[0063]

EXAMPLES The present invention will now be described specifically with reference to examples, but embodiments of the present invention are not limited thereto.

Example 1 <Preparation of Polymer Fine Particles> 2.1 g of acrylic acid, 4.2 g of glycidyl methacrylate, 33.6 g of styrene, n
-AizenS in a mixture of 2.1 g of butyl acrylate
8.0 g of pilon Black MH special (oil-soluble dye manufactured by Hodogaya Chemical Industry Co., Ltd.) and 1.0 g of azobisdimethylvaleronitrile were dissolved, and 0.5 g of sodium dodecylbenzenesulfonate was dissolved in 340 g of ion-exchanged water. It was added to the aqueous solution and dispersed by ultrasonic waves. Temperature controller, heating device, stirrer, reflux cooler,
20 g of ion-exchanged water was put into a container having a nitrogen gas inlet tube, the inside of the container was replaced with nitrogen gas, and heated to 80 ° C.
The dispersion was added over 3 hours with stirring. After the addition, the dispersion was stirred while maintaining the same temperature for 2 hours, and then cooled to obtain polymer fine particles (P-1).

Polymer fine particles (P-2 to 11) were prepared in the same manner except that the monomer composition was changed as shown in the table.

Here, AA is acrylic acid, MAA is methacrylic acid, GMA is glycidyl methacrylate, MMA
Is methyl methacrylate, St is styrene, n-BA is n-butyl acrylate, c-1 is 2-acetoacetoxyethyl methacrylate, c-2 is 3-methacryloxypropyltrimethoxysilane, and c-3 is monohydroxy phosphate. Methyl (meth) acrylate, c-4 represents 2-hydroxylethyl methacrylate, c-5 represents methacrylamide, and c-6 represents N, N-dimethylaminoethyl methacrylate.

<Preparation of Ink for Inkjet Recording> A liquid was prepared in the following manner.

Compound Addition amount Polymer fine particles Described in Table 2 Water-soluble dyes Described in Table 2 Kao Revenol WX 0.3% Proxel GXL (manufactured by Zeneca) 0.01% Deionized water Remaining <Transfer evaluation> Transfer evaluation of ink Was performed as follows.
One hour after the end of printing, the surfaces on the image receiving side were overlapped, the sample was sandwiched between metal plates, placed on a flat table, a load was applied from above, and further stored in a thermostat kept at 40 ° C. for 24 hours. The transfer of the ink was evaluated and evaluated as follows.

：: No transfer Δ: Transfer is slightly recognized X: Transfer is clearly recognized XX: 10% or more of the image is transferred The results are shown in Table 2.

<Evaluation of Water Resistance> One hour after the end of printing, 15
Three samples cut into a size of 0 × 10 mm are prepared, two of which are used for the test, and the other one is kept as an original test specimen until the test is completed. The test is performed as follows. Two test pieces are immersed in ion-exchanged water and placed for 5 minutes. The water resistance of the ink was visually evaluated and determined as follows.

：: No change in ink is observed. 変 化: Change in gloss and discoloration of ink. X: Clearly thinned ink. The results are shown in Table 2.

[0072]

[Table 1]

[0073]

[Table 2]

Example 2 <Preparation of Ink for Inkjet Recording> A liquid was prepared in the following manner.

Compound Addition amount Polymer fine particles Described in Table 3 Pigments Described in Table 3 Kao Revenol WX 0.3% Proxel GXL (manufactured by Zeneca) 0.01% Ion-exchanged water Remaining Transfer evaluation and water resistance as in Example 1. Sex evaluation was performed.

[0076]

[Table 3]

Example 3 <Preparation of Inkjet Recording Ink> A liquid was prepared in the following manner.

Compound Addition amount Polymer fine particles Described in Table 4 Water-soluble dyes Described in Table 4 Pigments Described in Table 4 Water-soluble solvents Described in Table 4 Kao Levenol WX 0.3% Proxel GXL (manufactured by Zeneca) 0.01% Ion Remaining water exchange <Granularity evaluation> The obtained ink was packed in a cartridge of an inkjet printer MJ500V2 manufactured by Epson Corporation, and a lattice-type linear pattern was printed on an inkjet OHP sheet. With respect to the printed sample, 20 subjects were observed at a distance of 60 cm from the observation distance, and the number of persons who could not identify the dots was examined. Table 4 shows the obtained results. The transfer evaluation and the water resistance evaluation were performed in the same manner as in Example 1.

[0079]

[Table 4]

[0080]

As has been demonstrated in the examples, the ink composition for ink jet recording according to the present invention can easily perform color correction,
Even when the members are superimposed and stored after being adhered to the recording member and recorded after being adhered to the recording member, a part of the adhered image is hardly transferred to the superimposed member and has an excellent effect.

Continued on front page F-term (reference) 2C056 EA13 FC01 FC02 2H086 BA52 BA55 BA56 BA62 4J039 AB01 AB07 AD03 AD06 AD08 AD09 AD10 AD11 BE02 BE06 BE07 BE22 CA06 EA21 EA44 EA46 GA24

Claims (5)

[Claims] 1. An unsaturated monomer having a carboxyl group (a) in a molecule of 0.5 to 10% by weight, an unsaturated monomer having a glycidyl group (b) of 1 to 20% by weight and other unsaturated monomers. An ink composition for inkjet recording, comprising adding a water-soluble dye to polymer fine particles containing an oil-soluble dye obtained by polymerizing the monomer (c). 2. An unsaturated monomer having a carboxyl group in the molecule (a) 0.5 to 10% by mass, an unsaturated monomer having a glycidyl group (b) 1 to 20% by mass and other unsaturated monomers An ink composition for inkjet recording, comprising adding a pigment to polymer fine particles containing an oil-soluble dye obtained by polymerizing the monomer (c). 3. An unsaturated monomer having a carboxyl group in the molecule (a) 0.5 to 10% by mass, an unsaturated monomer having a glycidyl group (b) 1 to 20% by mass and other unsaturated monomers An ink composition for ink jet recording, comprising adding a water-soluble dye and a pigment to polymer fine particles containing an oil-soluble dye obtained by polymerizing the monomer (c). 4. The method according to claim 1, wherein the other unsaturated monomer (c) is an unsaturated monomer having an acetoacetyl group in the molecule (c-1). The ink composition for inkjet recording according to claim 1 or 2. 5. The ink composition for ink jet recording according to claim 1, further comprising a high boiling point solvent.