JP4365198B2 - Aqueous colorant resin composition, process for producing the same, fine particle water-insoluble dye dispersion, and ink for inkjet printer - Google Patents

Description

The present invention is, for aqueous colorant resin composition and relates to a manufacturing method thereof, further relates to an ink for particulate water-insoluble dye dispersion aqueous and ink jet printer using the aqueous colorant resin composition.

  In inks and paints, it has been desired to reduce fading caused by light or an oxidizing gas in coated materials and printed materials. For this reason, there is an increasing demand for inks and paints that use a pigment-based color material in which molecules are gathered, instead of a dye-based color material in which the pigment is present in a molecular state, as a colorant. Although pigment-based color materials have high weather resistance, they tend to be inferior to dye-based color materials in terms of hue because of the large individual particles. Therefore, how to make the color material particles fine and how to stably disperse the fine particles is a big problem. In particular, in view of safety and environmental considerations, dispersion in a medium mainly composed of water rather than an organic solvent is often required. In particular, in an inkjet printer that has been rapidly spreading in recent years, measures such as stirring the ink before use of the ink cannot be taken, and since it is necessary to discharge the ink from a minute nozzle, the dispersibility of the pigment in the ink can be reduced. The requirements are very strict.

  In order to stably disperse the pigment in the aqueous medium, a so-called self-dispersing pigment in which the pigment surface is modified to make the particle surface of the originally hydrophobic pigment hydrophilic is used. Although this self-dispersing pigment is excellent in dispersion stability, the printed matter formed using the ink has low water resistance, and the ink easily penetrates into a recording medium such as paper, and the color of the formed image. There may be a problem such as insufficient density.

  In order to solve these problems, attempts have been made to coat pigment particles with a resin. For example, in Patent Documents 1 to 4, a block copolymer containing a hydrophobic part that easily adheres to a pigment and a hydrophilic part that has a high affinity for an aqueous medium is attached to the pigment particle surface, Patent Document 5 discloses an example using a graft copolymer having similar properties. According to these methods, it is said that an ink having high dispersion stability and improved water resistance of printed matter can be realized. However, the dispersion stability mentioned here is a period of about several months during which the ink or pigment dispersion is used. If these inks are used immediately after production, there is no problem. For example, assuming that the products are manufactured and stored in large quantities and then sequentially provided to the market, sufficient ink storage stability is achieved. It is difficult to do.

  On the other hand, in the field of resin moldings and the like, it is practiced to manufacture and store a solid colored resin in which a coloring material is dispersed, and to mold and process the product as necessary (see Patent Document 6). . In this case, since the colored resin is stored in a solid state, the dispersion state of the coloring material can be maintained semipermanently for an extremely long time. It is conceivable to apply the same method to the field of water-based color material dispersions and water-based inks. However, since the resin for molding processing shown in these examples is not soluble in an aqueous medium, The colored resin cannot be used for an aqueous color material dispersion or an aqueous ink. On the other hand, Patent Document 7 discloses a composition using a block copolymer in consideration of application to ink and lacquer. However, the resin used here is a general block copolymer such as acrylic, methacrylic, styrene, maleic acid, and the dispersion stability of the pigment particles when the pigment dispersion or ink is finally obtained. Further improvement is desired with respect to image fastness of printed matter by ink.

  As for the miniaturization of coloring material particles, which is another problem, various improvements have been attempted in the process of producing pigments. However, at present, pigments are formed as secondary particles in which primary particles having a diameter of several tens to 100 nm are further aggregated. As long as a normal pigment is used, there is a limit to miniaturization of pigment particles. Therefore, a method of using oil-soluble dyes as fine particles in an aqueous medium has been studied (see Patent Document 8 and Patent Document 9). In these examples, the oil-soluble dye is first made into an organic solvent solution, and this is mixed with water in the presence of the block copolymer, so that the oil-soluble dye is precipitated as particles and simultaneously coated with the block copolymer. This is the basic idea. However, the block copolymers exemplified here are acrylic or methacrylic, and further improvement is required for the dispersion stability of the colorant particles in the dispersion or ink, the water resistance of the printed matter, and the like. . Further, if it is possible to manufacture and store a large amount as described above even in the system of dispersing the fine particle color material, the advantage is great.

JP-A-5-179183 Japanese Patent Laid-Open No. 6-136411 JP 7-53841 A Japanese Patent Laid-Open No. 11-228891 JP-A-9-188732 JP-A-6-88009 JP 2003-49110 A JP 2002-97395 A JP 2002-332441 A

In view of the above situation, the present invention is provided for the preparation of an aqueous color material dispersion or water-based ink that can stably form an image (printed matter) with excellent color fastness in which the color material is stably dispersed in the form of fine particles. It is an object to provide a resin composition for an aqueous colorant that can be stored for a long period of time.

The above object can be achieved by the present invention described below. That is, the present invention is polyvinyl with a water-insoluble dye, a hydrophobic moiety represented by at least the following general formula (1), and a moiety represented by the following general formula having a carboxyl group unneutralized (2) After mixing the block copolymer having an ether structure in a solvent that dissolves the block copolymer, the solvent is distilled off to solidify the fine particle water-insoluble dye surface with the block copolymer. A resin composition for aqueous colorants (hereinafter sometimes referred to as “colored resin composition”) is provided.
_{^{- (CH 2 -CH (OR 1}} )) - (1)
(In the general formula (1), R ¹ is an alkyl group having 1 to 18 carbon atoms.)
_{^{- (CH 2 -CH (OR 6}} )) - (2)
(In the above general formula (2), R ⁶ represents — (CH ₂ ) _m — (O) _n —CH ₂ —COOH or — (CH ₂ ) _m — (O) _n —C ₆ H ₄ —COOH. M is 1 to 36, and n is 0 or 1.)

  In the present invention, the block copolymer having a polyvinyl ether structure has a tough and stable main chain skeleton, and by selecting a side chain bonded to the main chain, the block copolymer has a hydrophobic moiety and It can have a hydrophilic part. By using the block copolymer as a dispersion medium for the water-insoluble dye, the hydrophobic portion interacts with the water-insoluble dye, and the water-insoluble dye can be stably held in the resin for a long time.

Further, the present invention is polyvinyl with a water-insoluble dye, a hydrophobic moiety represented by at least the following general formula (1), and a moiety represented by the following general formula having a carboxyl group unneutralized (2) After mixing the block copolymer having an ether structure in a solvent that dissolves the block copolymer , the solvent is distilled off to solidify the fine particle water-insoluble dye surface with the block copolymer. to provide a method for producing an aqueous colorant resin composition characterized that.
_{^{- (CH 2 -CH (OR 1}} )) - (1)
(In the general formula (1), R ¹ is an alkyl group having 1 to 18 carbon atoms.)
_{^{- (CH 2 -CH (OR 6}} )) - (2)
(In the above general formula (2), R ⁶ represents — (CH ₂ ) _m — (O) _n —CH ₂ —COOH or — (CH ₂ ) _m — (O) _n —C ₆ H ₄ —COOH. M is 1 to 36, and n is 0 or 1.)
According to the above method, once the water-insoluble dye and the block copolymer are uniformly dissolved in the solvent and then the solvent is removed, the hydrophobic portion in the block copolymer and the water-insoluble dye are mixed at the molecular level. A highly uniform colored resin composition is obtained.

In the colored resin composition and a production method of the present invention, the water-insoluble dye, be oil-soluble dyes; the water-insoluble dye, it a water-soluble dye is obtained by water insolubilization treatment; and pre Symbol abundance of mosquitoes carboxyl groups, the block copolymer per 1g, it is preferable that 1~200mg in sodium hydroxide terms.

  The present invention also provides a fine particle water-insoluble dye dispersion (hereinafter sometimes simply referred to as “coloring material dispersion”) obtained by dispersing the colored resin composition in an aqueous medium, and further providing the coloring material dispersion. Ink for inkjet printers (hereinafter sometimes simply referred to as “ink”).

  When the colored resin composition of the present invention is introduced into an aqueous medium, the water-insoluble dye precipitates as fine particles in the aqueous medium as it is mixed with the aqueous medium. At that time, the hydrophobic portion of the block copolymer existing in the immediate vicinity of the water-insoluble dye covers the fine particle surface of the water-insoluble dye. On the other hand, since the block copolymer of the present invention has an acidic group that develops hydrophilicity upon neutralization, the colored resin composition of the present invention is dispersed in an aqueous medium in the presence of a suitable neutralizing agent. When this is done, this hydrophilic portion is compatible with the aqueous medium. As a result, the block copolymer is stably dispersed in the aqueous medium with the hydrophilic portion facing outward while the fine particles of the water-insoluble dye are held inside.

  The finely divided water-insoluble dye has higher weather resistance than when the dye molecule is present alone. In addition to the effect of enhancing the weather resistance by being coated with the block copolymer, water resistance by the polyvinyl ether structure block copolymer of the present invention is also imparted to the printed matter, so that the image fastness is extremely high. Is obtained.

  ADVANTAGE OF THE INVENTION According to this invention, the colored resin composition in which the water-insoluble dye was hold | maintained uniformly which can be stored for a long term can be provided. Further, it is possible to provide an aqueous color material dispersion and ink that can form an image (printed matter) excellent in dispersion stability and fastness of the fine particle water-insoluble dye using the colored resin composition. it can.

Next, the present invention will be described in more detail with reference to preferred embodiments.
The block copolymer used in the present invention includes at least one hydrophobic block (A, A ′) and at least one block (B, B ′) having an acidic group that exhibits hydrophilicity by neutralization. Consists of. In addition to this, other types of hydrophilic blocks (C), for example, nonionic hydrophilic blocks may be included.

  The arrangement of each block in the block copolymer is not particularly limited, but from the viewpoint of enhancing the dispersibility of the water-insoluble dye when the colored resin composition is dispersed in an aqueous medium, the acidity that exhibits hydrophilicity by neutralization is exhibited. Those having a group-containing block at the end of the polymer chain are preferred. For example, AB type, BAB 'type, AA'B type, ABB' type (A and A ', B and B' may be the same or different), ACB type and the like. A, A ', B, B', and C are homopolymer or copolymer blocks.

  A preferred block copolymer used in the present invention has a hydrophobic block made of a homopolymer or copolymer of a vinyl ether monomer and an acidic group that develops hydrophilicity by neutralization, made of a homopolymer or copolymer of a vinyl ether monomer. Including at least blocks. It may also contain other types of hydrophilic blocks consisting of homopolymers or copolymers of vinyl ether monomers.

It is preferable that blocks other than the part which has an acidic group in these polymers have a repeating unit shown by following General formula (1), for example.
^{_{- (CH 2 -CH (OR 1}} )) - (1)
In the general formula (1), R ¹ represents an aliphatic hydrocarbon such as an alkyl group, an alkenyl group, a cycloalkyl group, or a cycloalkenyl group, a phenyl group, a pyridyl group, a benzyl group, a toluyl group, a xylyl group, An aromatic hydrocarbon group in which a carbon atom may be substituted with a nitrogen atom, such as an alkylphenyl group, a phenylalkylene group, a biphenyl group, and a phenylpyridyl group. Moreover, the hydrogen atom on the aromatic ring may be substituted with a hydrocarbon group. R ¹ preferably has 1 to 18 carbon atoms. These structures are generally hydrophobic.

R ¹ may be a group represented by — (CH (R ² ) —CH (R ³ ) —O) _p —R ⁴ or — (CH ₂ ) _m — (O) _n —R ⁴ . In this case, R ² and R ³ each independently represent a hydrogen atom or a methyl group, and R ⁴ represents an aliphatic hydrocarbon such as an alkyl group, an alkenyl group, a cycloalkyl group, or a cycloalkenyl group, a phenyl group, Aromatic hydrocarbon groups in which carbon atoms may be substituted with nitrogen atoms, such as pyridyl group, benzyl group, toluyl group, xylyl group, alkylphenyl group, phenylalkylene group, biphenyl group, phenylpyridyl group (aromatic The hydrogen atom on the ring may be substituted with a hydrocarbon group), —CHO, —CH ₂ CHO, —CO—CH═CH ₂ , —CO—C (CH ₃ ) ═CH ₂ , —CH ₂ —CH═CH ₂ , —CH ₂ —C (CH ₃ ) ═CH ₂ , —CH ₂ —COOR ^5, etc., and the hydrogen atom in these groups is fluorine, as long as it is chemically possible. salt , It may be substituted with a halogen atom such as bromine. R ⁴ preferably has 3 to 18 carbon atoms. R ⁵ is an alkyl group. p is preferably 1 to 18, m is preferably 1 to 36, and n is preferably 0 or 1. These structures are generally hydrophilic, but are hydrophobic when R ⁴ is a hydrocarbon having a large number of carbon atoms, when m is large, or when n is 0.

In R ¹ and R ⁴ , examples of the alkyl group or alkenyl group include methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, t-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl. , Tetradecyl, hexadecyl, octadecyl, oleyl, linoleyl and the like, and examples of the cycloalkyl group or cycloalkenyl group include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, cyclohexenyl and the like.

On the other hand, the block having an acidic group preferably has a repeating unit represented by the following general formula (2), for example.
^{_{- (CH 2 -CH (OR 6}} )) - (2)
In the above general formula (2), R ⁶ represents — (CH (R ⁷ ) —CH (R ⁸ ) —O) _p —CH ₂ —COOH, — (CH (R ⁷ ) —CH (R ⁸ ) — _{O) p -C 6 H 4 -COOH} , - (CH 2) m - (O) n -CH 2 -COOH, - (CH 2) m - (O) n -C 6 H 4 -COOH, is like . In this case, R ⁷ and R ⁸ each independently represent a hydrogen atom or a methyl group, and the hydrogen atom in the chemical formula is substituted with a halogen atom such as fluorine, chlorine, bromine or the like as long as it is chemically possible. May be. p is preferably 1 to 18, m is preferably 1 to 36, and n is 0 or 1.

  Below, the monomer (Ia-Io) which comprises the repeating unit represented by general formula (1) and (2) demonstrated above, and the block copolymer (II-a-II) which consists of this monomer Although the structure of -c) is illustrated, the monomer and block copolymer of the polyvinyl ether structure used for this invention are not limited to these.

  Among these exemplified monomers, (Ia), (Ib), (If), (Ig) and (Ih) are monomers having strong hydrophilicity, and (Id ), (Ie), (Ii), (Ij) and (In) are highly hydrophobic monomers, and (Ik), (Im) and (Io) ) Is a typical monomer having an acidic group.

  In addition, the number of repeating units of each block [in the above (II-a) to (II-c), m, n, l] is preferably independently 1 to 10,000. Further, the total [in the above (II-a) to (II-c), m + n or m + n + l] is more preferably 10 to 20,000. The number average molecular weight is preferably 500 to 20,000,000, more preferably 1,000 to 5,000,000, and most preferably 2,000 to 2,000,000. Further, these block copolymers may be those obtained by graft-bonding them to other polymers, or may be those copolymerized with other repeating units (monomers). Each block also includes a copolymer of a vinyl ether monomer and other monomers.

  The method for synthesizing the copolymer having the vinyl ether polymer block is not particularly limited, and cation living polymerization by Aoshima et al. (Japanese Patent Laid-Open Nos. 11-322942 and 11-322866) is preferably used. By using the cationic living polymerization method, we can synthesize various polymers such as homopolymers with exactly the same length (molecular weight), copolymers of two or more monomers, and block copolymers, graft copolymers, and gradation copolymers. be able to. Moreover, a polyvinyl ether block can introduce | transduce various functional groups into the side chain.

  The ratio of these block copolymers to the total mass of the resin composition in the colored resin composition of the present invention is preferably 10 to 90 mass%, more preferably 20 to 70 mass%. If the amount of the block copolymer is less than 10% by mass, the water-insoluble dye in the composition is difficult to dissolve uniformly. On the other hand, if the amount of the block copolymer exceeds 90% by mass, the resin is not sufficiently colored. Become.

The water-insoluble dye used in the present invention is preferably an oil-soluble dye. Specifically, it is as follows, but the present invention is not limited to these.
(Yellow oil-soluble dye)
C. I. Solvent Yellow-1, C.I. I. Solvent Yellow-2, C.I. I. Solvent Yellow-3, C.I. I. Solvent Yellow-13, C.I. I. Solvent Yellow-19, C.I. I. Solvent Yellow-21, C.I. I. Solvent Yellow-22, C.I. I. Solvent Yellow-29, C.I. I. Solvent Yellow-36, C.I. I. Solvent Yellow-37, C.I. I. Solvent Yellow-38, C.I. I. Solvent Yellow-39, C.I. I. Solvent Yellow-40, C.I. I. Solvent Yellow-43, C.I. I. Solvent Yellow-44, C.I. I. Solvent Yellow-45, C.I. I. Solvent Yellow-47, C.I. I. Solvent Yellow-62, C.I. I. Solvent Yellow-63, C.I. I. Solvent Yellow-71, C.I. I. Solvent Yellow-76, C.I. I. Solvent Yellow-81, C.I. I. Solvent Yellow-85, C.I. I. Solvent yellow-86, etc .;

(Red oil-soluble dye)
C. I. Solvent Red-35, C.I. I. Solvent Red-36, C.I. I. Solvent Red-37, C.I. I. Solvent Red-38, C.I. I. Solvent Red-39, C.I. I. Solvent Red-40, C.I. I. Solvent Red-58, C.I. I. Solvent Red-60, C.I. I. Solvent Red-65, C.I. I. Solvent Red-69, C.I. I. Solvent Red-81, C.I. I. Solvent Red-86, C.I. I. Solvent Red-89, C.I. I. Solvent Red-92, C.I. I. Solvent Red-97, C.I. I. Solvent Red-99, C.I. I. Solvent Red-100, C.I. I. Solvent Red-109, C.I. I. Solvent Red-118, C.I. I. Solvent Red-119, C.I. I. Solvent Red-122 etc .;

(Blue oil-soluble dye)
C. I. Solvent Blue-14, C.I. I. Solvent Blue-24, C.I. I. Solvent Blue-26, C.I. I. Solvent Blue-34, C.I. I. Solvent Blue-37, C.I. I. Solvent Blue-39, C.I. I. Solvent Blue-42, C.I. I. Solvent Blue-43, C.I. I. Solvent Blue-44, C.I. I. Solvent Blue-45, C.I. I. Solvent Blue-48, C.I. I. Solvent Blue-52, C.I. I. Solvent Blue-53, C.I. I. Solvent Blue-55, C.I. I. Solvent Blue-59, C.I. I. Solvent Blue-67 etc .;

(Black oil-soluble dye)
C. I. Solvent Black-5, C.I. I. Solvent Black-8, C.I. I. Solvent Black-14, C.I. I. Solvent Black-17, C.I. I. Solvent Black-19, C.I. I. Solvent Black-20, C.I. I. Solvent Black-22, C.I. I. Solvent Black-24, C.I. I. Solvent Black-26, C.I. I. Solvent Black-28, C.I. I. Solvent Black-43 etc.

In the present invention, water-insoluble dyes obtained by water-insolubilizing various water-soluble dyes can also be used. As a method for insolubilizing the water-soluble dye, a method of forming an ion complex such as binding a cationic surfactant to an anionic dye is preferable. Examples of water-soluble dyes that can be used in the present invention include the following.
(Black direct dye)
C. I. Direct Black-17, C.I. I. Direct Black-19, C.I. I. Direct Black-22, C.I. I. Direct Black-32, C.I. I. Direct Black-38, C.I. I. Direct Black-51, C.I. I. Direct Black-62, C.I. I. Direct Black-71, C.I. I. Direct Black-108, C.I. I. Direct Black-146, C.I. I. Direct black-154, etc .;

(Yellow direct dye)
C. I. Direct Yellow-12, C.I. I. Direct Yellow-24, C.I. I. Direct Yellow-26, C.I. I. Direct Yellow-44, C.I. I. Direct Yellow-86, C.I. I. Direct Yellow-87, C.I. I. Direct Yellow-98, C.I. I. Direct Yellow-100, C.I. I. Direct Yellow-130, C.I. I. Direct Yellow-142 etc .;

(Red direct dye)
C. I. Direct Red-1, C.I. I. Direct Red-4, C.I. I. Direct Red-13, C.I. I. Direct Red-17, C.I. I. Direct Red-23, C.I. I. Direct Red-28, C.I. I. Direct Red-31, C.I. I. Direct Red-62, C.I. I. Direct Red-79, C.I. I. Direct Red-81, C.I. I. Direct Red-83, C.I. I. Direct Red-89, C.I. I. Direct Red-227, C.I. I. Direct Red-240, C.I. I. Direct Red-242, C.I. I. Direct Red-243 etc .;

(Blue direct dye)
C. I. Direct Blue-6, C.I. I. Direct Blue-22, C.I. I. Direct Blue-25, C.I. I. Direct Blue-71, C.I. I. Direct Blue-78, C.I. I. Direct Blue-86, C.I. I. Direct Blue-90, C.I. I. Direct Blue-106, C.I. I. Direct Blue-199 etc .;

(Other color direct dyes)
C. I. Direct Orange-34, C.I. I. Direct Orange-39, C.I. I. Direct Orange-44, C.I. I. Direct Orange-46, C.I. I. Direct Orange-60 etc .;
C. I. Direct Violet-47, C.I. I. Direct violet-48 etc .;
C. I. Direct Brown-109, C.I. I. Direct Green-59 etc .;

(Black acid dye)
C. I. Acid Black-2, C.I. I. Acid Black-7, C.I. I. Acid Black-24, C.I. I. Acid Black-26, C.I. I. Acid Black-31, C.I. I. Acid Black-52, C.I. I. Acid Black-63, C.I. I. Acid Black-112, C.I. I. Acid Black-118, C.I. I. Acid Black-168, C.I. I. Acid Black-172, C.I. I. Acid Black-208 etc .;

(Yellow acid dye)
C. I. Acid Yellow-11, C.I. I. Acid Yellow-17, C.I. I. Acid Yellow-23, C.I. I. Acid Yellow-25, C.I. I. Acid Yellow-29, C.I. I. Acid Yellow-42, C.I. I. Acid Yellow-49, C.I. I. Acid Yellow-61, C.I. I. Acid Yellow-71 etc .;

(Red acid dye)
C. I. Acid Red-1, C.I. I. Acid Red-6, C.I. I. Acid Red-8, C.I. I. Acid Red-32, C.I. I. Acid Red-37, C.I. I. Acid Red-51, C.I. I. Acid Red-52, C.I. I. Acid Red-80, C.I. I. Acid Red-85, C.I. I. Acid Red-87, C.I. I. Acid Red-92, C.I. I. Acid Red-94, C.I. I. Acid Red-115, C.I. I. Acid Red-180, C.I. I. Acid Red-254, C.I. I. Acid Red-256, C.I. I. Acid Red-289, C.I. I. Acid Red-315, C.I. I. Acid Red-317 etc .;

(Blue acid dye)
C. I. Acid Blue-9, C.I. I. Acid Blue-22, C.I. I. Acid Blue-40, C.I. I. Acid Blue-59, C.I. I. Acid Blue-93, C.I. I. Acid Blue-102, C.I. I. Acid Blue-104, C.I. I. Acid Blue-113, C.I. I. Acid Blue-117, C.I. I. Acid Blue-120, C.I. I. Acid Blue-167, C.I. I. Acid Blue-229, C.I. I. Acid Blue-234, C.I. I. Acid Blue-254 etc .;

(Other color acid dyes)
C. I. Acid Orange-7, C.I. I. Acid Orange-19, C.I. I. Acid Violet-49 etc .;

(Black reactive dye)
C. I. Reactive Black-1, C.I. I. Reactive Black-5, C.I. I. Reactive Black-8, C.I. I. Reactive Black-13, C.I. I. Reactive Black-14, C.I. I. Reactive Black-23, C.I. I. Reactive Black-31, C.I. I. Reactive Black-34, C.I. I. Reactive Black-39 etc .;

(Yellow reactive dye)
C. I. Reactive Yellow-2, C.I. I. Reactive Yellow-3, C.I. I. Reactive Yellow-13, C.I. I. Reactive Yellow-15, C.I. I. Reactive Yellow-17, C.I. I. Reactive Yellow-18, C.I. I. Reactive Yellow-23, C.I. I. Reactive Yellow-24, C.I. I. Reactive Yellow-37, C.I. I. Reactive Yellow-42, C.I. I. Reactive Yellow-57, C.I. I. Reactive Yellow-58, C.I. I. Reactive Yellow-64, C.I. I. Reactive Yellow-75, C.I. I. Reactive Yellow-76, C.I. I. Reactive Yellow-77, C.I. I. Reactive Yellow-79, C.I. I. Reactive Yellow-81, C.I. I. Reactive Yellow-84, C.I. I. Reactive Yellow-85, C.I. I. Reactive Yellow-87, C.I. I. Reactive Yellow-88, C.I. I. Reactive Yellow-91, C.I. I. Reactive Yellow-92, C.I. I. Reactive Yellow-93, C.I. I. Reactive Yellow-95, C.I. I. Reactive Yellow-102, C.I. I. Reactive Yellow-111, C.I. I. Reactive Yellow-115, C.I. I. Reactive Yellow-116, C.I. I. Reactive Yellow-130, C.I. I. Reactive Yellow-131, C.I. I. Reactive Yellow-132, C.I. I. Reactive Yellow-133, C.I. I. Reactive Yellow-135, C.I. I. Reactive Yellow-137, C.I. I. Reactive Yellow-139, C.I. I. Reactive Yellow-140, C.I. I. Reactive Yellow-142, C.I. I. Reactive Yellow-143, C.I. I. Reactive Yellow-144, C.I. I. Reactive Yellow-145, C.I. I. Reactive Yellow-146, C.I. I. Reactive Yellow-147, C.I. I. Reactive Yellow-148, C.I. I. Reactive Yellow-151, C.I. I. Reactive Yellow-162, C.I. I. Reactive yellow-163, etc .;

(Red reactive dye)
C. I. Reactive Red-3, C.I. I. Reactive Red-13, C.I. I. Reactive Red-16, C.I. I. Reactive Red-21, C.I. I. Reactive Red-22, C.I. I. Reactive Red-23, C.I. I. Reactive Red-24, C.I. I. Reactive Red-29, C.I. I. Reactive Red-31, C.I. I. Reactive Red-33, C.I. I. Reactive Red-35, C.I. I. Reactive Red-45, C.I. I. Reactive Red-49, C.I. I. Reactive Red-55, C.I. I. Reactive Red-63, C.I. I. Reactive Red-85, C.I. I. Reactive Red-106, C.I. I. Reactive Red-109, C.I. I. Reactive Red-111, C.I. I. Reactive Red-112, C.I. I. Reactive Red-113, C.I. I. Reactive Red-114, C.I. I. Reactive Red-118, C.I. I. Reactive Red-126, C.I. I. Reactive Red-128, C.I. I. Reactive Red-130, C.I. I. Reactive Red-131, C.I. I. Reactive Red-141, C.I. I. Reactive Red-151, C.I. I. Reactive Red-170, C.I. I. Reactive Red-171, C.I. I. Reactive Red-174, C.I. I. Reactive Red-176, C.I. I. Reactive Red-177, C.I. I. Reactive Red-183, C.I. I. Reactive Red-184, C.I. I. Reactive Red-186, C.I. I. Reactive Red-187, C.I. I. Reactive Red-188, C.I. I. Reactive Red-190, C.I. I. Reactive Red-193, C.I. I. Reactive Red-194, C.I. I. Reactive Red-195, C.I. I. Reactive Red-196, C.I. I. Reactive Red-200, C.I. I. Reactive Red-201, C.I. I. Reactive Red-202, C.I. I. Reactive Red-204, C.I. I. Reactive Red-206, C.I. I. Reactive Red-218, C.I. I. Reactive red-221 etc .;

(Blue reactive dye)
C. I. Reactive Blue-2, C.I. I. Reactive Blue-3, C.I. I. Reactive Blue-5, C.I. I. Reactive Blue-8, C.I. I. Reactive Blue-10, C.I. I. Reactive Blue-13, C.I. I. Reactive Blue-14, C.I. I. Reactive Blue-15, C.I. I. Reactive Blue-18, C.I. I. Reactive Blue-19, C.I. I. Reactive Blue-21, C.I. I. Reactive Blue-25, C.I. I. Reactive Blue-27, C.I. I. Reactive Blue-28, C.I. I. Reactive Blue-38, C.I. I. Reactive Blue-39, C.I. I. Reactive Blue-40, C.I. I. Reactive Blue-41, C.I. I. Reactive Blue-49, C.I. I. Reactive Blue-52, C.I. I. Reactive Blue-63, C.I. I. Reactive Blue-71, C.I. I. Reactive Blue-72, C.I. I. Reactive Blue-74, C.I. I. Reactive Blue-75, C.I. I. Reactive Blue-77, C.I. I. Reactive Blue-78, C.I. I. Reactive Blue-79, C.I. I. Reactive Blue-89, C.I. I. Reactive Blue-100, C.I. I. Reactive Blue-101, C.I. I. Reactive Blue-104, C.I. I. Reactive Blue-105, C.I. I. Reactive Blue-119, C.I. I. Reactive Blue-122, C.I. I. Reactive Blue-147, C.I. I. Reactive Blue-158, C.I. I. Reactive Blue-160, C.I. I. Reactive Blue-162, C.I. I. Reactive Blue-166, C.I. I. Reactive Blue-169, C.I. I. Reactive Blue-170, C.I. I. Reactive Blue-171, C.I. I. Reactive Blue-172, C.I. I. Reactive Blue-173, C.I. I. Reactive Blue-174, C.I. I. Reactive Blue-176, C.I. I. Reactive Blue-179, C.I. I. Reactive Blue-184, C.I. I. Reactive Blue-190, C.I. I. Reactive Blue-191, C.I. I. Reactive Blue-194, C.I. I. Reactive Blue-195, C.I. I. Reactive Blue-198, C.I. I. Reactive Blue-204, C.I. I. Reactive Blue-211, C.I. I. Reactive Blue-216, C.I. I. Reactive blue-217 etc .;

(Orange reactive dye)
C. I. Reactive Orange-5, C.I. I. Reactive Orange-7, C.I. I. Reactive Orange-11, C.I. I. Reactive Orange-12, C.I. I. Reactive Orange-13, C.I. I. Reactive Orange-15, C.I. I. Reactive Orange-16, C.I. I. Reactive Orange-35, C.I. I. Reactive Orange-45, C.I. I. Reactive Orange-46, C.I. I. Reactive Orange-56, C.I. I. Reactive Orange-62, C.I. I. Reactive Orange-70, C.I. I. Reactive Orange-72, C.I. I. Reactive Orange-74, C.I. I. Reactive Orange-82, C.I. I. Reactive Orange-84, C.I. I. Reactive Orange-87, C.I. I. Reactive Orange-91, C.I. I. Reactive Orange-92, C.I. I. Reactive Orange-93, C.I. I. Reactive Orange-95, C.I. I. Reactive Orange-97, C.I. I. Reactive Orange-99 etc .;

(Purple reactive dye)
C. I. Reactive Violet-1, C.I. I. Reactive Violet-4, C.I. I. Reactive Violet-5, C.I. I. Reactive Violet-6, C.I. I. Reactive Violet-22, C.I. I. Reactive Violet-24, C.I. I. Reactive Violet-33, C.I. I. Reactive Violet-36, C.I. I. Reactive violet-38, etc .;

(Green reactive dye)
C. I. Reactive Green-5, C.I. I. Reactive Green-8, C.I. I. Reactive Green-12, C.I. I. Reactive Green-15, C.I. I. Reactive Green-19, C.I. I. Reactive Green-23 etc .;

(Brown reactive dye)
C. I. Reactive Brown-2, C.I. I. Reactive Brown-7, C.I. I. Reactive Brown-8, C.I. I. Reactive Brown-9, C.I. I. Reactive Brown-11, C.I. I. Reactive Brown-16, C.I. I. Reactive Brown-17, C.I. I. Reactive Brown-189, C.I. I. Reactive Brown-21, C.I. I. Reactive Brown-24, C.I. I. Reactive Brown-26, C.I. I. Reactive Brown-31, C.I. I. Reactive Brown-32, C.I. I. Reactive Brown-33 etc .;

(Food dyes)
C. I. Food Black-1, C.I. I. Food Black-2, C.I. I. Food Yellow-3, C.I. I. Food Red-87, C.I. I. Food Red-92, C.I. I. Food Red-94 etc.

  In addition, as the cationic surfactant that insolubilizes the dye in combination with the anionic dye, primary, secondary and tertiary amine salts having a hydrophobic group, quaternary ammonium salts, and the like can be used. . In particular, a quaternary ammonium salt having a linear alkyl group having 10 or more carbon atoms is preferred. Specifically, decyltrimethylammonium, dodecyltrimethylammonium, tetradecyltrimethylammonium, hexadecyltrimethylammonium, octadecyltrimethylammonium, didodecyldimethylammonium, dimethylditetradecylammonium, dimethyldioctadecylammonium, dimethyldipalmitylammonium, dodecyl Examples include chlorides and bromides such as dimethylbenzylammonium and benzalkonium. The addition amount of such a cationic surfactant is 0.5 to 5 times, more preferably 1 to 3 times in molar ratio to the anionic dye.

  The colored resin composition of the present invention is preferably produced, for example, as follows. That is, the block copolymer of the present invention and the water-insoluble dye are dissolved in a solvent to obtain a uniform solution. When the solvent is distilled off from this solution by drying under reduced pressure, a colored resin composition in which a water-insoluble dye is uniformly mixed is obtained. The solvent to be used may be an amount that sufficiently dissolves the block copolymer and the water-insoluble dye. Since the colored resin composition thus obtained is in a solid state, the water-insoluble dye retained therein does not aggregate and can maintain a uniform state semipermanently. Therefore, a large amount of the colored resin composition may be produced and stored, and a part of the colored resin composition may be used as an ink or a paint if necessary.

  A liquid dispersion can be prepared by dispersing the colored resin composition of the present invention in an appropriate aqueous medium. For example, if the colored resin composition of the present invention is put into an alkaline aqueous solution and dispersed by a bead mill, a ball mill or the like, a color material dispersion applicable to various uses can be obtained. As the alkali to be used, sodium hydroxide, potassium hydroxide, lithium hydroxide, tetraalkylammonium hydroxide and the like can be used, but sodium hydroxide, potassium hydroxide and lithium hydroxide are preferable. At this time, the hydrophobic block of the block copolymer is firmly attached to the surface of the water-insoluble dye particle, and the acidic group is ionized by neutralization with an alkali to express hydrophilicity. Affinity forms a colorant dispersion that is stably dispersed in water. Since the fine-particle water-insoluble dye is dispersed in a state of being coated with the block copolymer, when coating or printing is performed using this dispersion, the coated or printed matter may contain a finely divided water-insoluble dye. In addition to the weather resistance, the effect of the coating of the block copolymer is added to provide higher weather resistance.

  If there is no hydrophobic block in the block copolymer, it is difficult to uniformly mix with the water-insoluble dye at the stage of producing the colored resin composition, and the fine particle water-insoluble dye is dispersed when dispersed in an aqueous medium. The surface is exposed and the water-insoluble dye particles are aggregated. On the other hand, if there is no acidic group that develops hydrophilicity by neutralization in the block copolymer, the block copolymer precipitates or aggregates when the colored resin composition is dispersed in an aqueous medium. . In addition, when a block copolymer having a hydrophilic block from the beginning is used instead of a block that exhibits hydrophilicity by neutralization, the solubility of the resin in the solvent during the process of producing the colored resin composition It becomes insufficient, and a uniform dispersion cannot be obtained. Therefore, the block copolymer used in the present invention must have a hydrophobic block and a block having an acidic group that develops hydrophilicity by neutralization. Further, the acidic group in the block copolymer is preferably a carboxyl group, and the abundance of the carboxyl group in the block copolymer is preferably 1 to 200 mg in terms of sodium hydroxide per 1 g of the block copolymer. More preferably, it is 2 to 150 mg. If the abundance of the carboxyl group is less than the above range, there may be the same disadvantage as the case where there is no acidic group as described above, while if the abundance of the carboxyl group exceeds the above range, the hydrophobicity There is a possibility of causing the same inconvenience as when the block does not exist.

  The color material dispersion can be further made into an ink for an ink jet printer by adding an appropriate water-soluble organic substance or the like as necessary. The amount of the water-insoluble dye in the ink is preferably 0.1 to 20% by mass, more preferably 1 to 10% by mass. If the amount of the water-insoluble dye is less than 0.1% by mass, a sufficient density cannot be obtained in the printed image. If the amount of the water-insoluble dye exceeds 20% by mass, the image density does not increase greatly. Ink discharge stability such as clogging is reduced.

  The organic substance added to the ink mainly serves to prevent the ink from solidifying due to drying at the nozzle portion of the ink jet printer and stabilize the ejection. Specifically, alcohols such as isopropanol and butanol; ethylene glycol , Diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, thiodiglycol, neopentyl glycol Diols such as 1,4-cyclohexanediol and polyethylene glycol; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether , Alkylene glycol monoalkyl ethers such as ethylene glycol monoallyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether Polyols such as glycerin, 1,2,4-butanetriol, 1,2,5-pentanetriol, 1,2,6-hexanetriol, trimethylolethane, trimethylolpropane, pentaerythritol; tetrahydrofuran, dioxane, etc. Cyclic ethers of dimethyl sulfoxide, diacetone alcohol, Serine monoallyl ether, N-methyl-2-pyrrolidone, 2-pyrrolidone, γ-butyrolactone, 1,3-dimethyl-2-imidazolidinone, sulfolane, urea, β-dihydroxyethylurea, acetonylacetone, dimethylformamide, Examples thereof include dimethylacetamide and phenoxyethanol.

  Such an organic substance may be solid or liquid as long as it is water-soluble. Further, since it is required to remain in the ink even under conditions where water evaporates, the boiling point is preferably higher than that of water, and preferably 120 ° C. or higher. Since it has an effect, it is harder to evaporate than a single substance, so that it is not necessarily limited to a high boiling point substance. These organic substances may be used alone or in combination of two or more. The proportion of these organic substances in the ink is 5 to 50% by mass, preferably 10 to 30% by mass, based on the total mass of the ink. In addition to the above components, for example, various additives such as a surfactant, a pH adjuster, an antioxidant, and an antifungal agent are added to the colored resin composition, the color material dispersion, and the ink of the present invention. Also good.

  The ink of the present invention can be suitably used in an ink jet recording method in which energy is applied to the ink to cause it to fly. As energy, thermal energy or mechanical energy can be used, but a method using thermal energy is particularly preferable. As a printer for inkjet recording, it can be applied to a printer for general households mainly using A4 size paper, a printer for printing business cards and cards, or a large printer for business use. It is suitably used for large machines that require a large amount of ink. As a recording medium for recording with the ink of the present invention, plain paper without special coating, so-called ink jet exclusive paper coated with a layer for receiving ink on at least one side, postcard, business card paper, label paper, cardboard paper And an inkjet film.

Specific examples of the present invention will be described below. However, the present invention is not limited by these examples. In the following description, all “parts” are based on mass.
Synthesis of diblock copolymer (Polymer 1):
After replacing the inside of the glass container fitted with the three-way cock with nitrogen, the adsorbed water was removed by heating at 250 ° C. in a nitrogen gas atmosphere. After returning the system to room temperature, 12 mmol of isobutyl vinyl ether, 16 mmol of ethyl acetate, 0.1 mmol of 1-isobutoxyethyl acetate, and 11 ml of toluene were added, and when the internal temperature reached 0 ° C., ethyl aluminum sesquichloride was added. Polymerization was started by adding 0.2 mmol to synthesize a hydrophobic block as the first component of the diblock copolymer.

  2- (Ethoxycarbonyl) which becomes the raw material of the acidic group-containing block after the polymerization of the first component is completed by monitoring the molecular weight in a time-sharing manner using gel permeation chromatography (GPC, HLC-8220 manufactured by Tosoh Corporation). The second component was synthesized by adding 10 mmol of ethyl vinyl ether, and the polymerization reaction was stopped by adding a 0.3 mass% ammonia / methanol solution to the system. For the identification of the obtained diblock copolymer, a nuclear magnetic resonance absorption measuring device (NMR, DPX400 manufactured by Bruker BioSpin) and GPC were used, and both obtained results indicating that the target substance was synthesized. It was. The number average molecular weight (Mn) of the obtained diblock copolymer is 25,000 in terms of standard polystyrene, and the weight average molecular weight (Mw) / number average molecular weight ratio (Mw / Mn) indicating the degree of molecular weight distribution is 1.3. Met. The ester portion of the second component of the diblock copolymer is hydrolyzed in a mixed solvent of 5 times equivalent amount of sodium hydroxide and methanol and then free of carboxyl groups, and the solvent is distilled off to obtain a carboxylic acid type polymer 1 Got.

Synthesis of triblock copolymer (Polymer 2):
After replacing the inside of the glass container fitted with the three-way cock with nitrogen, the adsorbed water was removed by heating at 250 ° C. in a nitrogen gas atmosphere. After returning the system to room temperature, 12 mmol of 1-isobutyl vinyl ether, 16 mmol of ethyl acetate, 0.1 mmol of 1-isobutoxyethyl acetate, and 11 ml of toluene were added. Polymerization was started by adding 0.2 mmol of sesquichloride, and a hydrophobic block that was the first component of the triblock copolymer was synthesized.

  The molecular weight was monitored in a time-sharing manner using gel permeation chromatography (GPC, HLC-8220 manufactured by Tosoh Corporation). After the polymerization of the first component was completed, 12 mmol of 2-methoxyethyl vinyl ether was added. Polymerization of the hydrophilic block as a component was performed, and monitoring was performed using GPC in the same manner as described above to confirm the completion of polymerization of the second component. Next, 10 mmol of 4- [2-vinyloxyethoxy] benzoate, which is a raw material for the acidic group-containing block, was added to synthesize the third component, and the polymerization reaction was stopped by 0.3% by mass in the system. Performed by adding ammonia / methanol solution.

  For the identification of the obtained triblock copolymer, a nuclear magnetic resonance absorption measuring apparatus (NMR, DPX400 manufactured by Bruker BioSpin) and GPC were used, and both obtained results indicating that the target substance was synthesized. It was. The number average molecular weight (Mn) of the obtained triblock copolymer is 30,000 in terms of standard polystyrene, and the weight average molecular weight (Mw) / number average molecular weight ratio (Mw / Mn) indicating the degree of molecular weight distribution is 1.3. Met. The ester part of the third component of this triblock copolymer is hydrolyzed in a mixed solvent of 5 times equivalent amount of sodium hydroxide and methanol and then freed of carboxyl groups, the solvent is distilled off, and the carboxylic acid type polymer 2 Got.

Determination of the amount of alkali required for neutralization of polymers 1 and 2:
Polymers 1 and 2 are dissolved in tetrahydrofuran at a concentration of 2% by mass and various concentrations of aqueous sodium hydroxide solution are added, and then the solution is dropped on a calcium fluoride single crystal plate and dried. The infrared absorption spectrum was measured with (FT / IR5300 manufactured by JASCO Corporation). In each of the above two types of block copolymers to which alkali has been added, absorption of carboxylate ions is observed at 1547 cm ⁻¹ , and the absorption intensity increases with the amount of alkali added, but the amount of alkali addition exceeds a certain value. And no more increase. This alkali amount was regarded as equivalent. The obtained equivalent was 55 mg-NaOH for polymer 1 and 60 mg-NaOH for polymer 2 with respect to 1 g of the block copolymer.

Water insolubilization of water-soluble dyes:
(Water-insoluble dye 1)
1 part of C.I. in 20 parts of water. I. Direct yellow 44 was dissolved, 1.15 parts of hexadecyltrimethylammonium bromide was gradually added, and the mixture was stirred with an ultrahomogenizer. The resulting precipitate was collected by filtration and dried under reduced pressure to obtain water-insoluble dye 1.

(Water-insoluble dye 2)
1 part of C.I. in 20 parts of water. I. Direct Blue 86 was dissolved, and 1.01 part of octadecyltrimethylammonium bromide was gradually added, followed by stirring with an ultrahomogenizer. The resulting precipitate was collected by filtration and dried under reduced pressure to obtain water-insoluble dye 2.

[Examples 1-7]
Preparation of colored resin composition:
One part of the above polymer 1 or polymer 2 was added to 18 parts of tetrahydrofuran together with 1 part of the water-insoluble dye listed in Table 1 and dissolved. This liquid was put into a vacuum container, tetrahydrofuran was distilled off, and it was dried at room temperature in a vacuum drier to obtain colored resin compositions of Examples 1 to 7. Table 1 shows the composition of the produced colored resin composition.

Preparation of aqueous colorant dispersion:
To 1 part of each colored resin composition, 9 parts of water containing a carboxyl group and an equivalent amount of sodium hydroxide of the block copolymer in each colored resin composition are added and mixed for 5 hours in a bead mill. A corresponding aqueous colorant dispersion was obtained.

Ink preparation:
1 part of diethylene glycol and 1 part of glycerin were added to 8 parts of each of the above water-based color material dispersions to obtain water-based inks corresponding thereto.

[Comparative Examples 1-4]
Using a styrene-maleic acid copolymer (polymer 3) having a number average molecular weight of 10,000 as a polymer, colored resin compositions of Comparative Examples 1 to 4 having the compositions shown in Table 2 were prepared in the same manner as in the above Examples.

  In addition, using the colored resin compositions in Table 2, aqueous color material dispersions and inks corresponding to the respective colored resin compositions were prepared in the same manner as in the Examples.

[Evaluation]
Storage stability of colored resin composition:
When each of the colored resin compositions of Examples 2 and 5 and Comparative Example 2 was used, an aqueous color material dispersion was prepared by the above method immediately after the preparation of the composition, and each of the colored resin compositions was 100 ° C. The average particle size of the water-insoluble dye particles in the dispersion was compared with the case where the aqueous colorant dispersion was prepared after storing for 4 weeks. A PAR-III dynamic light scattering measuring device manufactured by Otsuka Electronics Co., Ltd. was used for measurement of the average particle size. The results are shown in Table 3.

なお、他の実施例および他の比較例も表３と同様の結果であった。

The results of other examples and other comparative examples were the same as in Table 3.

Dispersion stability of aqueous colorant dispersion:
Regarding the aqueous color material dispersions of Examples and Comparative Examples, the average particle size was measured immediately after preparation and after storage at 60 ° C. for 4 weeks using a PAR-III dynamic light scattering measurement apparatus manufactured by Otsuka Electronics Co., Ltd. The results are shown in Table 4.

Weatherability:
Each of the inks of the examples and comparative examples is mounted on an ink-jet recording apparatus BJF-660 (manufactured by Canon) having an on-demand type multi-recording head that ejects ink by applying thermal energy corresponding to a recording signal to the ink. did. The water resistance and gas resistance of the glossy paper SP101 made by Canon were evaluated using a recording medium on which a 100% solid image was printed at 5 ° C. in an environment with a relative humidity of 10%.

<Water resistance>
The reflection density (X) of the printed recording medium was measured using an optical reflection densitometer (Macbeth densitometer RD-918). After leaving the printed matter for 12 hours after printing, leave the printed matter in tap water for 5 minutes, measure the reflection density (Y) of the print after drying the water, and before and after the water resistance test. The residual ratio of the reflection density (the following formula) was used as a measure of water resistance. The evaluation criteria were as follows.
Residual rate = [XY] / X × 100%
○: The residual ratio of reflection density is 90% or more.
Δ: The residual ratio of reflection density is 80% or more and less than 90%.
X: The residual ratio of reflection density is less than 80%.
The evaluation results are shown in Table 5.

<Gas resistance>
The reflection density (X) of the printed recording medium was measured using an optical reflection densitometer (Macbeth densitometer RD-918). The printed recording medium is put into an ozone exposure tester (made by Suga Test Instruments Co., Ltd., special order), exposed to ozone at a concentration of 1 ppm for 4 hours under the conditions of 40 ° C. and 55% RH, and the reflection density after exposure (Y ) Was measured and used as a measure of gas resistance as the residual ratio of reflection density (the following formula) before and after the gas resistance test. The evaluation criteria were as follows.
Residual rate = [XY] / X × 100%
○: The residual ratio of reflection density is 90% or more.
Δ: The residual ratio of reflection density is 85% or more and less than 90%.
X: The residual ratio of reflection density is less than 85%.
The evaluation results are shown in Table 5.

Ink ejection characteristics:
Each of the inks of the examples and comparative examples is mounted on an ink-jet recording apparatus BJF-660 (manufactured by Canon) having an on-demand type multi-recording head that ejects ink by applying thermal energy corresponding to a recording signal to the ink. did. A 100% solid image was printed on Canon glossy paper SP101 at 5 ° C in an environment with a relative humidity of 10%, and after resting for 1 minute, the image on which the 100% solid image was printed again was evaluated according to the following evaluation criteria. did.
(Double-circle): There is no white stripe and it is printed normally.
○: Slight white streaks are observed at the beginning of printing.
Δ: White streaks are observed in the entire image.
X: An image is hardly printed.
The evaluation results are shown in Table 6.

As described above, according to the present invention, it is possible to provide a colored resin composition that can be stored for a long period of time and in which a water-insoluble dye is uniformly held. Further, it is possible to provide an aqueous color material dispersion and ink that can form an image (printed matter) excellent in dispersion stability and fastness of the fine particle water-insoluble dye using the colored resin composition. it can.

Claims (10)

And a water-insoluble dye, a hydrophobic moiety represented by at least the following general formula (1), a block copolymerization of polyvinyl ether structure having a moiety represented by the following general formula (2) having a carboxyl group unneutralized The surface of the fine particle water-insoluble dye is coated with the block copolymer by mixing the mixture in a solvent that dissolves the block copolymer, and then solidifying the solvent by distilling off the solvent. A resin composition for an aqueous colorant.
_{^{- (CH 2 -CH (OR 1}} )) - (1)
(In the general formula (1), R ¹ is an alkyl group having 1 to 18 carbon atoms.)
_{^{- (CH 2 -CH (OR 6}} )) - (2)
(In the above general formula (2), R ⁶ represents — (CH ₂ ) _m — (O) _n —CH ₂ —COOH or — (CH ₂ ) _m — (O) _n —C ₆ H ₄ —COOH. M is 1 to 36, and n is 0 or 1.) The resin composition for an aqueous colorant according to claim 1, wherein the water-insoluble dye is an oil-soluble dye. The resin composition for an aqueous colorant according to claim 1, wherein the water-insoluble dye is obtained by water-insolubilizing a water-soluble dye. Before abundance hear carboxyl groups, the block copolymer per 1g, aqueous colorant resin composition according to claim 1 which is 1~200mg in sodium hydroxide terms. And a water-insoluble dye, a hydrophobic moiety represented by at least the following general formula (1), a block copolymerization of polyvinyl ether structure having a moiety represented by the following general formula (2) having a carboxyl group unneutralized The surface of the fine particle water-insoluble dye is coated with the block copolymer by mixing the mixture in a solvent that dissolves the block copolymer, and then solidifying the solvent by distilling off the solvent. A method for producing a resin composition for an aqueous colorant.
_{^{- (CH 2 -CH (OR 1}} )) - (1)
(In the general formula (1), R ¹ is an alkyl group having 1 to 18 carbon atoms.)
_{^{- (CH 2 -CH (OR 6}} )) - (2)
(In the above general formula (2), R ⁶ represents — (CH ₂ ) _m — (O) _n —CH ₂ —COOH or — (CH ₂ ) _m — (O) _n —C ₆ H ₄ —COOH. M is 1 to 36, and n is 0 or 1.) The method for producing a resin composition for an aqueous colorant according to claim 5, wherein the water-insoluble dye is an oil-soluble dye. The method for producing a resin composition for an aqueous colorant according to claim 5, wherein the water-insoluble dye is obtained by water-insolubilizing a water-soluble dye. Before abundance hear carboxyl groups, the block copolymer per 1g, method for producing an aqueous colorant resin composition according to claim 5 which is 1~200mg in sodium hydroxide terms. Aqueous colorant resin composition, particle water-insoluble dye dispersion characterized by comprising dispersed in an aqueous-alkaline medium according to claim 1.   An ink for an inkjet printer, comprising the fine-particle water-insoluble dye dispersion according to claim 9.