CN100590160C

CN100590160C - Water-based inks for ink-jet printing

Info

Publication number: CN100590160C
Application number: CN 200510089426
Authority: CN
Inventors: 津留功; 水岛龙马; 稻田胜彦; 堤武弘
Original assignee: Kao Corp
Current assignee: Kao Corp
Priority date: 2004-08-06
Filing date: 2005-08-05
Publication date: 2010-02-17
Anticipated expiration: 2025-08-05
Also published as: CN1730575A

Abstract

There are provided a water dispersion for ink-jet printing comprising colorant-containing water-insoluble graft polymer particles in which the water-insoluble graft polymer contains a main chain whichis a polymer chain containing a constitutional unit derived from a salt-forming group-containing monomer (a) and a constitutional unit derived from an aromatic ring-containing (meth)acrylate monomer(b), and a side chain which is a polymer chain containing a constitutional unit derived from a hydrophobic monomer (c); a water-based ink for ink-jet printing using the water dispersion; and an ink-jet printing method using the water-based ink. In accordance with the present invention, printed images or characters formed on a coated paper are excellent in gloss, image clarity and image clarity property including both of the image clarity and the gloss, and printed images or characters formed on an ordinary paper exhibit a high print density.

Description

Water-based ink for use in ink-jet recording

Technical field

The present invention relates to water dispersion for ink-jet printing, contain the water-based ink for use in ink-jet recording of this dispersion and use the recording method of this water color ink.

Background technology

Ink-jet recording is from very tiny nozzle drop directly to be sprayed onto on the recording-member, it is adhered to and obtains the recording mode of writings and image.This mode is owing to have: easy panchromaticization and cheapness, can use common paper as recording-member, and the product that are printed be noncontact etc. many advantages, so very universal.

Particularly in recent years, from the weathering resistance and the water-proof viewpoint of printed matter, using pigment in tinting material is that printing ink becomes main flow gradually.For example, disclose in No. 00/39226 brochure in the world and to disclose a kind of water color ink, it is the water color ink that contains pigment in vinyl polymer, in order to give high printing concentration, this water color ink has used and used the graftomer that macromonomer (macromer) arranged in vinyl polymer.

In addition, open the spy and to disclose the aqueous dispersion that a kind ofly contains insoluble tinting material, has the graft copolymer dispersant of main chain part and at least 1 pendant moiety in the flat 10-87768 communique, two portions of aforementioned dispersion agent obtain from the unsaturated vinyl monomer manufacturing, side in main chain or the part side chain is a wetting ability, and the opposing party is a hydrophobicity; Contain at least a kind of monomer in aryl ester, N-aryl acrylamide, N-arylmethyl acrylamide and the ethenyl aromatic yl ester that is selected from acrylic acid aryl ester, methacrylic acid in the hydrophobic parts, and the gross weight with hydrophobic parts is a benchmark, and this monomer contains 50 weight % at least.

These water color inks are the printing ink of printing concentration and dispersion stabilization excellence, but when plain paper is printed, need higher printing concentration, and when dedicated paper printed, need more excellent glossiness.

Summary of the invention

The invention provides a kind of water dispersion that contains the water-insoluble graftomer particle of tinting material, and it is that this water-insoluble graftomer has the water dispersion for ink-jet printing of following main chain and side chain, and a kind of water-based ink for use in ink-jet recording that contains this water dispersion is provided and uses ink-jet printing apparatus aforementioned water color ink to be printed onto ink jet recording method on the air gap type gloss media with printing ink accommodating layer.

Main chain: be to contain (a) to come from monomeric structural unit that contains salt-forming group and the polymer chain that (b) comes from the structural unit of (methyl) acrylate monomer that contains aromatic nucleus

Side chain: be to contain the polymer chain that (c) comes from the structural unit of hydrophobic monomer

Embodiment

Can excellent glossiness when the present invention relates to realize being printed onto on the special-purpose paper, the distinctiveness of the reconstruction of image (image clarity), image, and the water-based ink for use in ink-jet recording that can realize high printing concentration on being printed onto plain paper the time.

Water-insoluble graftomer used in the present invention has main chain and side chain, and wherein main chain contains (a) and comes from monomeric structural unit that contains salt-forming group and the polymer chain that (b) comes from the structural unit of (methyl) acrylate monomer that contains aromatic nucleus; Side chain contains the polymer chain that (c) comes from the structural unit of hydrophobic monomer, in addition, can also contain the side chain that is formed by other structural unit.

In addition, from the viewpoint of the stability of resulting water dispersion, the water-insoluble graftomer is vinyl polymer preferably.

It is believed that, in the present invention, come from monomeric structural unit that contains salt-forming group and the structural unit that (b) comes from (methyl) acrylate monomer that contains aromatic nucleus because main chain contains (a), so can improve the mobility of salt-forming group.Thus, the water dispersion of water-insoluble graftomer that contains tinting material is on being ejected into as the satin paper of dedicated paper the time from inkjet nozzle, think by relaxing the coherency of salt-forming group, can increase the smoothness of printing surface, improve glossiness, the rub resistance of printed matter.

In main chain, (a) come from the monomeric structural unit that contains salt-forming group and preferably obtain by the monomer that polymerization contains salt-forming group.After polymer polymerizing is finished, can in polymer chain, introduce salt-forming group such as anionic property group, cationic group.

Come from the dispersion stabilization that the monomeric structural unit that contains salt-forming group is used to improve polymkeric substance.As salt-forming group, can list anionic property groups such as carboxyl, sulfonic group, phosphate, cationic groups such as amino, ammonium.

The monomer that contains salt-forming group that comes from the monomeric structural unit that contains salt-forming group as (a) is preferably (a-1) anionic property monomer or (a-2) cationic monomer.

As (a-1) anionic property monomer, can list one or more kinds that are selected from unsaturated carboxylic acid monomer, unsaturated sulfonic acid monomer and the unsaturated phosphorus acid monomer.

As unsaturated carboxylic acid monomer, for example can list vinylformic acid, methacrylic acid, Ba Dousuan, methylene-succinic acid, toxilic acid, fumaric acid, citraconic acid, 2-methacryloxy methylsuccinic acid etc.

As the unsaturated sulfonic acid monomer, for example can list styryl sulfonic acid, 2-acrylamide-2-methyl propane sulfonic acid, 3-sulfo group propyl group (methyl) acrylate, two-(3-sulfo group propyl group)-itaconic ester etc.

As unsaturated phosphoric acid, for example can list vinyl phosphonate, vinyl phosphate, two (methacryloxyethyl) phosphoric acid ester, phenylbenzene-2-acryloxy ethyl phosphonic acid ester, phenylbenzene-2-methacryloxyethyl phosphoric acid ester, dibutyl-2-acryloxy ethyl phosphonic acid ester etc.

In above-mentioned anionic property monomer,, be preferably unsaturated carboxylic acid monomer, acrylic or methacrylic acid more preferably from viewpoints such as ink viscosity, ejection property.

Can list in the vinyl monomer that is selected from unsaturated vinyl monomer that contains tertiary amine and unsaturated ammonium salt-containing a kind or multiple as (a-2) cationic monomer.

As the unsaturated monomer that contains tertiary amine, for example can list N, N-dimethyl aminoethyl (methyl) acrylate, N, N-dimethylaminopropyl (methyl) acrylate, N, N-diethylamino ethyl (methyl) acrylate, N, N-dimethylaminopropyl (methyl) acrylamide, vinyl pyrrolidone, 2-vinyl pyridine, 4-vinylpridine, 2-methyl-6-vinyl pyridine, 5-ethyl-2-vinyl pyridine etc.

Monomer as unsaturated ammonium salt-containing, for example can list, by N, N-dimethyl aminoethyl (methyl) acrylate deutero-quarternary ammonium salt, by N, N-diethylamino ethyl (methyl) acrylate deutero-quarternary ammonium salt, by N, N-dimethylaminopropyl (methyl) acrylate deutero-quarternary ammonium salt etc.

In above-mentioned cationic monomer, be preferably N, N-dimethyl aminoethyl (methyl) acrylate, N, N-dimethylaminopropyl (methyl) acrylamide, vinyl pyrrolidone.

In addition, " (methyl) vinylformic acid " described in this specification sheets is meant " vinylformic acid ", " methacrylic acid " or their mixture.

The above-mentioned monomer that contains salt-forming group may be used alone, can also be used in combination two or more.

(b) structural unit that comes from (methyl) acrylate monomer that contains aromatic nucleus makes up by coming from the monomeric structure monomer that contains salt-forming group with aforementioned (a), can improve glossiness, rub resistance etc.Be preferably the structural unit shown in the following formula (1) as the structural unit that comes from (methyl) acrylate monomer that contains aromatic nucleus.

(in the formula, R ¹Expression hydrogen atom or methyl, R ²It is that 7～22 aralkyl or carbonatoms are 6～22 aryl that expression can have substituent carbonatoms.)

In the formula (1), R ²Expression can have that substituent carbonatoms is 7～22, preferred carbonatoms is 7～18, more preferably carbonatoms is 7～12 aralkyl, perhaps can have substituent carbonatoms and be 6～22, preferred carbonatoms is 6～18, more preferably carbonatoms is 6～12 aryl.

As R ²Object lesson, for example can list benzyl, styroyl (phenylethyl) phenoxy group ethyl, diphenyl-methyl, trityl etc.

In the substituting group that above-mentioned aralkyl or aryl can have, can contain heteroatoms.As heteroatoms, can list nitrogen-atoms, Sauerstoffatom or sulphur atom.

As above-mentioned substituent object lesson, can list preferred carbonatoms and be 1～9 alkyl, alkoxyl group or acyloxy, hydroxyl, ether, ester group, nitro etc.

Structural unit shown in the formula (1) preferably obtains by the monomer polymerization shown in the following formula (1-1).

CH ₂＝CR ¹COOR ² (1-1)

(in the formula, R ¹, R ²As hereinbefore.)

Particularly, by with polymerizations such as (methyl) phenyl acrylate, (methyl) benzyl acrylate, 2-phenylethyl (methyl) acrylate, phenoxy group ethyl (methyl) acrylate, 1-naphthyl acrylate, 2-naphthyl (methyl) acrylate, phthalimide methyl (methyl) acrylate, right-nitrophenyl (methyl) acrylate, 2-hydroxyl-3-phenoxy propyl (methyl) acrylate, 2-methacryloxyethyl-2-hydroxypropyl phthalic ester, 2-acryloxy ethyl phthalic acids, obtain the structural unit shown in the formula (1).Wherein, be preferably (methyl) benzyl acrylate.They may be used alone, can also be used in combination two or more.

From improving viewpoints such as storage stability, printing concentration, can contain and come from and have (methyl) acrylate that carbonatoms is 1～22 alkyl or the monomer shown in the following formula (2) structural unit of (below, be generically and collectively referred to as (d) hydrophobic monomer) in the main chain.

CH ₂＝C(R ³)-R ⁴ (2)

(in the formula, R ³Expression hydrogen atom or carbonatoms are 1～5 alkyl, R ⁴The expression carbonatoms is 6～22 the alkyl that contains aromatic nucleus.)

Come from that to have carbonatoms be that the structural unit of (methyl) acrylate of 1～22 alkyl particularly can be by making (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) vinylformic acid (different) propyl diester, (methyl) vinylformic acid (XOR uncle) butyl ester, (methyl) 2-ethylhexyl acrylate, (methyl) vinylformic acid (different) octyl group ester, (methyl) vinylformic acid (different) decyl ester, (methyl) vinylformic acid (different) dodecyl ester, (methyl) vinylformic acid (different) stearyl, polymerizations such as (methyl) vinylformic acid docosyl ester and obtaining.In addition, described in the present invention " (XOR uncle) and " (different) " be meant, exists with the situation of the branched structure of " different " or " uncle " expression and do not exist the situation of side chain promptly to represent both of " just ".

In the formula (2), R ³Be preferably hydrogen atom or methyl, from viewpoints such as printing concentration, be preferably a kind of being selected from vinylbenzene, vinyl naphthalene, alpha-methyl styrene, Vinyl toluene, vinyl xylene, ethyl vinyl benzene, 4-vinyl biphenyl and the 1 or multiple as the monomer shown in the formula (2).Wherein, from viewpoints such as printing concentration, storage stabilities, more preferably be selected from a kind or multiple styrene monomer in vinylbenzene, alpha-methyl styrene and the Vinyl toluene.

From improving the viewpoint of glossiness, ejection stability, printing concentration etc., preferably in main chain, contain the structural unit that comes from (e) nonionic (methyl) acrylic ester monomer.

As nonionic (methyl) acrylic ester monomer, the represented non-ionic monomer of preferred following formula (3).

CH ₂＝C(R ⁵)COO(R ⁶O) _nR ⁷ (3)

(in the formula, R ⁵Expression hydrogen atom or carbonatoms are 1～3 alkyl, R ⁶The expression carbonatoms is 2～18 alkylidene group, and n represents average addition mole number, is 1～30 number, R ⁷Be preferably hydrogen atom, carbonatoms and be 1～18 alkyl and maybe can have the phenyl that carbonatoms is 1～8 alkyl.)。In the formula (3), from viewpoints such as polymerizabilitys, R ⁵Be preferably hydrogen atom, methyl etc., R ⁶Be preferably carbonatoms and be 2～4 ethylidene, propylidene, butylidene etc.From improving viewpoints such as ejection property, glossiness, R ⁶Be preferably ethylidene, from improving viewpoints such as printing concentration, R ⁶Be preferably propylidene or butylidene.From viewpoints such as printing concentration, storage stabilities, n is preferably 2～25 number, more preferably 4～23 number.N R ⁶Can be the same or different, under situation inequality, can be block addition and random addition.

From the viewpoint of height printing concentration, good storage stability, R ⁷Be preferably carbonatoms and be 1～12 alkyl, more preferably carbonatoms is 1～8 alkyl.In addition, also be preferably and have the phenyl that carbonatoms is 1～8 alkyl.

As carbonatoms is that 1～8 alkyl can list methyl, ethyl, propyl group, sec.-propyl, butyl, the tertiary butyl, hexyl, octyl group, 2-ethylhexyl.

Object lesson as the non-ionic monomer shown in the formula (3) can list hydroxyethyl meth acrylate, methoxy poly (ethylene glycol) list (methyl) acrylate, polyethyleneglycol (methyl) acrylate, methoxyl group polypropylene glycol list (methyl) acrylate, polypropylene glycol list (methyl) acrylate, ethylene glycol propylene glycol (methyl) acrylate, poly-(ethylene glycol propylene glycol) single (methyl) acrylate, octyloxy polyoxyethylene glycol polypropylene glycol list (methyl) acrylate etc.They can distinguish use separately, also can be used in combination two or more.

Viewpoints such as the glossiness when improving printing, rub resistance, in the main chain, (a) come from contain salt-forming group monomer (with unneutralized calculating.Below identical) structural unit and the weight ratio [(a)/(b)] that (b) comes from the structural unit of (methyl) acrylate monomer that contains aromatic nucleus be preferably 1/1～1/20, more preferably 1/1.5～1/15, be preferably 1/2～1/10 especially.In this scope, can give the dedicated paper excellent glossiness.

From improving the viewpoints such as dispersiveness of water-insoluble graftomer, the content that (a) in the main chain comes from the monomeric structural unit that contains salt-forming group is preferably 3～30 weight %, and more preferably 5～20 weight % are preferably 5～15 weight % especially.

From improving viewpoints such as glossiness, rub resistance, the content that (b) in the main chain comes from the structural unit of (methyl) acrylate monomer that contains aromatic nucleus is preferably 10～80 weight %, more preferably 15～75 weight % are preferably 20～70 weight % especially.

From improving viewpoint such as dispersion stabilization, in the main chain, come from that to have carbonatoms be that the content of structural unit of (methyl) acrylate of 1～22 alkyl is preferably 0～10 weight %, more preferably 0～5 weight %; From improving viewpoints such as anti-mark, be preferably 0～30 weight % from the content of the monomeric structural unit shown in the aforementioned formula (2), more preferably 0～15 weight %.From improving viewpoints such as dispersion stabilization, printing concentration, anti-mark, in the main chain, (d) content that comes from the structural unit of hydrophobic monomer is preferably 0～40 weight %, more preferably 0～20 weight %.

From improving viewpoints such as printing concentration, glossiness, ejection, in the main chain, (e) content from the structural unit of nonionic (methyl) acrylic ester monomer is preferably 0～60 weight %, more preferably 10～50 weight %.

From water-insoluble graftomer particle, fully containing tinting material, improve viewpoints such as printing concentration and set out, water-insoluble graftomer used herein contains the structural unit that (c) comes from hydrophobic monomer in side chain.

Come from the hydrophobic monomer in the structural unit of hydrophobic monomer as (c), can list vinyl monomer, can list the monomer of following (c-1)～(c-3) particularly.

(c-1) styrene monomer: as styrene monomer, can list vinylbenzene, alpha-methyl styrene, Vinyl toluene etc., wherein be preferably vinylbenzene especially.The side chain that contains the structural unit that comes from styrene monomer is to obtain by the polystyrene macromonomer that an end is had polymerizable functional groups group (below, be called the polystyrene macromonomer) copolymerization.The polystyrene macromonomer for example can list at an end and has the styrene homopolymers of polymerizable functional groups group or have vinylbenzene and other monomeric multipolymer of polymerizable functional groups group at an end.As the polymerizable functional groups group that end had at, be preferably acryloxy or methacryloxy.As listing (c-2) described later, (c-3) monomer, vinyl cyanide etc. with styrene copolymerized other monomer.From water-insoluble graftomer particle, fully containing tinting material, improving viewpoints such as printing concentration, in the side chain or in the polystyrene macromonomer, the content of structural unit that comes from styrene monomer is the highest, be preferably 60 weight % or more than, more preferably 70 weight % or more than, be preferably especially 90 weight % or more than.

The number-average molecular weight of polystyrene macromonomer is preferably 1,000～10,000 to improve viewpoint such as storage stability from improving copolymerization ratio and suppressing viscosity very low, and more preferably 2,000～8,000.

The number-average molecular weight of polystyrene macromonomer can use polystyrene as reference material, and the tetrahydrofuran (THF) of acetic acid that contains 50mmol/l by use is as the gel permeation chromatography of solvent.

As can the commercial polystyrene macromonomer that obtains, for example can list the commodity AS-6 by name that Toagosei Co., Ltd produces, AS-6S, AN-6, AN-6S, HS-6, HS-6S etc.

(c-2) carbonatoms is 1～22 as having, preferred carbonatoms is 1～18 alkyl, and also can have (methyl) acrylate of hydroxyl, can list (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) vinylformic acid (different) propyl diester, 2-hydroxyethyl (methyl) acrylate, (methyl) vinylformic acid (XOR uncle) butyl ester, (methyl) 2-ethylhexyl acrylate, (methyl) vinylformic acid (different) octyl group ester, (methyl) vinylformic acid (different) decyl ester, (methyl) vinylformic acid (different) stearyl etc. particularly.Contain come from carbonatoms be 1～22 and the side chain of structural unit that also can have (methyl) acrylate of hydroxyl obtain by an end being had polymerizable functional groups group (methyl) alkyl-acrylates macromonomer (below, be called " (methyl) alkyl-acrylates macromonomer ") copolymerization.As (methyl) alkyl-acrylates macromonomer, for example can list methyl methacrylate class macromonomer, butyl acrylate class macromonomer, Propenoic acid, 2-methyl, isobutyl ester class macromonomer, lauryl methacrylate(LMA) class macromonomer etc.Can list the homopolymer that has (methyl) alkyl acrylate of polymerizable functional groups group at an end as (methyl) alkyl-acrylates macromonomer, perhaps have (methyl) alkyl acrylate and other monomeric multipolymer of polymerizable functional groups group at an end; Be preferably acryloxy or methacryloxy as polymerizable functional groups group.Can list monomer of aforesaid (c-1), (c-3) described later etc. as other monomer with (methyl) alkyl acrylate copolymer.In the side chain or in (methyl) alkyl-acrylates macromonomer, the content of monomeric structural unit that comes from (c-2) is the highest, be preferably 60 weight % or above, more preferably 70 weight % or more than, be preferably especially 90 weight % or more than.

(c-3) contain (methyl) acrylate of aromatic nucleus: preferably enumerate the material shown in the aforementioned formula (1-1) as (methyl) acrylate that contains aromatic nucleus, for example can list (methyl) vinylformic acid benzyl ester, phenoxy group ethyl (methyl) acrylate, 2-hydroxyl-3-phenoxy propyl acrylate, 2-methacryloxyethyl-2-hydroxypropyl phthalic ester etc., be preferably (methyl) vinylformic acid benzyl ester.Containing and coming from the unitary side chain of (methyl) acrylate structural that contains aromatic nucleus is that (methyl) esters of acrylic acid macromonomer that contains aromatic nucleus (below, be called " (methyl) esters of acrylic acid macromonomer that contains aromatic nucleus ") copolymerization by having polymerizable functional groups group at an end obtains.As (methyl) acrylate macromonomer that contains aromatic nucleus, can list the homopolymer that has (methyl) acrylate that contains aromatic nucleus of polymerizable functional groups group at an end, perhaps have (methyl) acrylate that contains aromatic nucleus and other monomeric multipolymer of polymerizable functional groups group at an end; Be preferably acryloxy or methacryloxy as polymerizable functional groups group.Can list the monomer of aforesaid (c-1), (c-2) etc. as other monomer with (methyl) acrylic ester copolymer that contains aromatic nucleus.In containing (methyl) esters of acrylic acid macromonomer of aromatic nucleus, the content of monomeric structural unit that comes from (c-3) is the highest.Water-insoluble graftomer of the present invention is owing to the structural unit that has in main chain from (methyl) acrylate that contains aromatic nucleus, thereby play effect of the present invention, so in side chain or contain in (methyl) esters of acrylic acid macromonomer of aromatic nucleus, content from the structural unit of (methyl) acrylate that contains aromatic nucleus is preferably less than 50 weight %, more preferably 40 weight % or following.

In side chain, can also contain to come other monomeric structural unit of self energy and above-mentioned hydrophobic monomer copolymerization.As other monomer, for example can list vinyl cyanide, vinyl naphthalene, EST, 4-vinyl biphenyl, 1.

They can distinguish use separately, also can be used in combination two or more.

From improving viewpoint such as printing concentration, the hydrophobic monomer that comes from as (c) in the structural unit of hydrophobic monomer is preferably (c-1) styrene monomer.

Below, aforementioned polystyrene macromonomer, (methyl) alkyl-acrylates macromonomer, (methyl) esters of acrylic acid macromonomer of containing aromatic nucleus only are generically and collectively referred to as " macromonomer ".

In order to improve printing concentration, glossiness and rub resistance etc., the containing of water-insoluble graftomer used in the present invention (a) comes from the monomeric structural unit that contains salt-forming group and the main chain of the structural unit that (b) comes from (methyl) acrylate monomer that contains aromatic nucleus and contains the weight ratio [main chain/side chain] of side chain that (c) come from the structural unit of hydrophobic monomer and be preferably 1/1～20/1, more preferably 3/2～15/1, be preferably 2/1～10/1 especially.(group is calculated as the material that side chain was contained with polymerizable functional groups.Below identical)

Water-insoluble graftomer used in the present invention can further contain the side chain that is made of other structural unit, for example, can have organopolysiloxane side chain etc.This side chain for example preferably by with shown in the following formula (4), have at an end that the silicone macromonomer copolymerization of polymerizable functional groups group obtains.

CH ₂＝C(CH ₃)-COOC ₃H ₆-[Si(CH ₃) ₂-O] _t-Si(CH ₃) ₃ (4)

(in the formula, t represents 8～40 number)

Water-insoluble graftomer used in the present invention can obtain by containing monomer that (a) contain salt-forming group, (methyl) acrylate monomer that (b) contains aromatic nucleus and the monomer mixture copolymerization of macromonomer.In addition, also preferably with this monomer mixture with contain (d) hydrophobic monomer and/or (e) material that obtains of the monomer mixture of non-ionic monomer (below, they are generically and collectively referred to as " monomer mixture ") copolymerization.

From the dispersion stabilization that improves resulting dispersion, the viewpoints such as glossiness of printed matter, (a) in the monomer mixture contains the monomeric content of salt-forming group (as the content of dosis neutralisata not.Below identical), perhaps be present in the content that (a) in the main chain comes from the monomeric structural unit that contains salt-forming group in the water-insoluble graftomer, be preferably 3～30 weight %, 3～20 weight % more preferably, 5～15 weight %.

From viewpoints such as the glossiness that improves printed matter, wear-resisting wipings, (b) in the monomer mixture contains the content of (methyl) acrylate monomer of aromatic nucleus, perhaps in the water-insoluble graftomer be present in content that (b) in the main chain come from the structural unit of (methyl) acrylate monomer that contains aromatic nucleus be preferably 10～80 weight %, more preferably 15～70 weight %, be preferably 20～60 weight % especially.

From improving the viewpoints such as printing concentration of printed matter, the content of the macromonomer in the monomer mixture, perhaps in the water-insoluble graftomer, be present in content that (c) in the side chain come from the structural unit of hydrophobic monomer be preferably 5～50 weight %, more preferably 5～40 weight %, be preferably 5～35 weight % especially.

From viewpoints such as printing concentration, dispersion stabilization and anti-marks, the content of (d) hydrophobic monomer in the monomer mixture, just in the water-insoluble graftomer, (d) content of coming from the structural unit of hydrophobic monomer is preferably 0～40 weight %, 0～20 weight % more preferably.

From spraying viewpoints such as stability, glossiness and printing concentration, the content of (e) non-ionic monomer in the monomer mixture, just in the water-insoluble graftomer, (c) be preferably 0～60 weight % from the content of the structural unit of non-ionic monomer, 10～50 weight % more preferably.

From dispersion stabilization, viewpoints such as printing concentration are set out, (a) in the monomer mixture contains the weight ratio content of the monomeric content/macromonomer of salt-forming group [(a) contain] of the content of the monomer content of salt-forming group and macromonomer, perhaps in the water-insoluble graftomer, (a) come from the content of the structural unit that contains salt-forming group and be present in the weight ratio [(a) coming from the content that the content of the monomeric structural unit that contains salt-forming group/(c) comes from the structural unit of hydrophobic monomer] of content that (c) in the side chain come from the structural unit of hydrophobic monomer and be preferably 1/5～2/1, more preferably 1/4～2/1.

From glossiness, viewpoints such as printing concentration are set out, (b) in the monomer mixture contains the content and (e) weight ratio of the content of non-ionic monomer [(b) containing the non-ionic monomer of (methyl) acrylate monomer of aromatic nucleus/(e)] of (methyl) acrylate monomer of aromatic nucleus, perhaps in the water-insoluble graftomer, (b) come from (methyl) acrylate monomer that contains aromatic nucleus structural unit content and (e) be preferably 5/1～1/2, more preferably 4/1～1/2 from the weight ratio of the content of the structural unit of non-ionic monomer [(b) from the content of the content of the structural unit of (methyl) acrylate monomer that contains aromatic nucleus/(e)] from the structural unit of non-ionic monomer.

The water-insoluble of water-insoluble graftomer used in the present invention is meant: according to the kind of this salt-forming group, use sodium hydroxide or acetic acid with in this salt-forming group 100% and after, viewpoint from the lowering viscousity of water color ink, the water-insoluble graftomer is preferably 10g or following with respect to the meltage (25 ℃) of 100g water, more preferably 5g or following is preferably below the 1g especially.

Water-insoluble graftomer used in the present invention will use from the monomeric salt-forming group that contains salt-forming group and back by neutralizing agent described later.The degree of neutralization of salt-forming group is preferably 10～200%, and more preferably 20～150%, be preferably 30～100% especially.

Here, when salt-forming group was the anionic property group, degree of neutralization can be tried to achieve by following formula.

[equivalent of the weight of neutralizing agent (g)/neutralizing agent]/[weight (g)/(56 * 1000) of the acid value of polymkeric substance (KOHmg/g) * polymkeric substance] * 100

In addition, when salt-forming group was the cationic group, degree of neutralization can be tried to achieve by following formula.

[equivalent of the weight of neutralizing agent (g)/neutralizing agent]/[weight (g)/(36.5 * 1000) of ammonia valency (the HCLmg/g) * polymkeric substance of polymkeric substance] * 100

Acid value and ammonia valency can calculate from the structural unit of water-insoluble graftomer, also polymkeric substance can be dissolved in appropriate solvent (for example, methylethylketone) after, adopt titrating method to try to achieve.

From viewpoints such as the dispersion stabilization of tinting material, water-repellancy, ejections, the weight-average molecular weight of water-insoluble graftomer used in the present invention is preferably 5,000～500,0000, more preferably 10,000～400,000, be preferably 10,000～300,000 especially.

In addition, the dimethyl formamide of lithiumbromide that the weight-average molecular weight of water-insoluble graftomer can contain the phosphoric acid of 60mmol/L and 50mmol/L by use uses polystyrene to measure as reference material as the gel chromatography of solvent.

Water-insoluble graftomer used in the present invention can pass through known polymerization processs such as mass polymerization, solution polymerization process, outstanding turbid polymerization, emulsion polymerization method, makes the monomer mixture copolymerization and makes.In these polymerization processs, the preferred solution polymerization.

The solvent that uses in the solution polymerization process is preferably polar organic solvent.Polar organic solvent also can mix use with water having when water-soluble.

As polar organic solvent, for example can list carbonatomss such as methyl alcohol, ethanol, propyl alcohol and be 1～3 Fatty Alcohol(C12-C14 and C12-C18), ketones such as acetone, methylethylketone, methyl iso-butyl ketone (MIBK), ester classes such as vinyl acetic monomer etc.Wherein, be preferably methyl alcohol, ethanol, acetone, methylethylketone or a kind or the mixed solvent of multiple and water in them.

When polymerization, can use radical polymerization initiator.Can use 2 as radical polymerization initiator, 2 '-Diisopropyl azodicarboxylate, 2,2 '-azo two (2, the 4-methyl pentane nitrile), dimethyl-2,2 '-azo dibutyrate, 2,2 '-azo two (2-methylbutyronitrile), 1,1 '-azo two azo-compounds such as (1-cyclohexane nitriles).In addition, can also use organo-peroxides such as the peroxidation acid tert-butyl ester, two-tert-butyl peroxide, dibenzoyl base oxide.

With respect to per 1 mole of monomer mixture, the consumption of radical polymerization initiator is preferably 0.001～5 mole, more preferably 0.01～2 mole.

During polymerization, can also further add the polymeric chain transfer agent.Object lesson as the polymeric chain transfer agent can list octyl mercaptan, n-dodecyl mercaptan, uncle's lauryl mercaptan, n-tetradecane base mercaptan, mercaptoethanol, 3-sulfydryl-1, thio-alcohols such as 2-propylene glycol, mercaptosuccinic acid, the thiuram-disulfide class, hydro carbons, the unsaturated cyclic hydrocarbon compound, unsaturated heterocyclic compounds etc., they can distinguish use separately, also can be used in combination two or more.

The polymerizing condition of monomer mixture can not determine without exception that under the common situation, polymerization temperature is preferably 30～100 ℃, more preferably 50～80 ℃ according to employed radical polymerization initiator, monomer, solvent types etc. and different; Polymerization time is preferably 1～20 hour.In addition, polymerization atmosphere is preferably inert atmospheres such as nitrogen atmosphere, argon.

After polyreaction finishes, can by from the reaction soln redeposition, heat up in a steamer known method such as desolvate and isolate the insoluble polymer of generation separately.In addition, resulting insoluble polymer can be removed unreacted monomer etc. and makes with extra care by repeating redeposition, membrane sepn, chromatography, extraction process etc.

(tinting material)

In the present invention, can use hydrophobic dye, pigment as tinting material.In addition, also both can be used in combination with arbitrary proportion.Particularly, in order to show required in recent years stronger high-weatherability, preferably use pigment.

Pigment can use pigment dyestuff or mineral dye.In addition, also they and pigment extender can be used simultaneously.

As pigment dyestuff, for example can list azo pigment, disazo pigment, phthalocyanine pigment, quinoline a word used for translation ketone pigment, isoindoline ketone pigment, triazine dioxin pigment, perylene, purple cyclic ketones (perinone), thioindigo color, anthraquinone pigment, Kui phthalein ketone pigment etc.

Object lesson as preferred pigment dyestuff can list C.I. pigment yellow 13,17,74,83,97,109,110,120,128,139,151,154,155,174,180; C.I. pigment red 48,57:1,122,146,176,184,185,188,202; C.I. pigment violet 19,23; C.I. pigment Blue 15,15:1,15:2,15:3,15:4,16,60; C.I. pigment Green 7,36 etc.

As mineral dye, for example can list carbon black, metal oxide, metallic sulfide, metal chloride etc.Among them, be preferably carbon black as black water printing ink.As carbon black can list that furnace black, thermo-cracking are dim, acetylene black and channel black etc.

Can list silicon-dioxide, lime carbonate, talcum etc. as pigment extender.

As dyestuff, owing to hydrophobic dye can be included in the insoluble polymer, so preferred the use.Example as hydrophobic dye can list oiliness dyestuff, dispersed dye etc.From making dyestuff be contained in viewpoints such as insoluble polymer effectively, hydrophobic dye is to the solubleness of organic solvent, the organic solvent that uses with respect to when making water dispersion, being used to make the hydrophobic dye dissolving, be preferably 2g/L or more than, 20～500g/L (25 ℃) more preferably.

As the oiliness dyestuff, for example can list C.I. solvent black 3,7,27,29,34,45; C.I. solvent yellow 14,16,29,56,82,83:1; C.I. solvent red 1,3, and 8,18,24,27,43,49,51,72,73; C.I. solvent violet 3; C.I. solvent blue 2,4, and 11,44,64,70; C.I. solvent green 3,7; C.I. solvent orange 2 etc.

As can the commercial oiliness dyestuff that obtains, for example can list Nubian BlackPC-0850, Oil black HBB, Oil Black 860, Oil Yellow 129, Oil Yellow105, Oil Pink 312, Oil Red 5B, Oil Scarlet 308, Vali Fast Blue 2606, Oil Blue BOS (more than, Orient KCC, trade(brand)name), Neopen Yellow075, Neopen Mazenta SE1378, Neopen Blue808, Neopen Blue 807, Neopen Blue FF 4012, Neopen Cyan FF4238 (more than, BASF AG, trade(brand)name) etc.

As dispersed dye, for example can list C.I. DISPERSE YELLOW 5,42,54,64,79,82,83,93,99,100,119,122,124,126,160,184:1,186,198,199,204,224,237; C.I. DISPERSE ORANGE 30 200 13,29,31:1,33,49,54,55,66,73,118,119,163; C.I. Disperse Red 54,60, and 72,73,86,88,91,93,111,126,127,134,135,143,145,152,153,154,159,164,167:1,177,181,204,206,207,221,239,240,258,277,278,283,311,323,343,348,356,362; C.I. 63 ,DIS,PER,SE ,Vio,let, 63 33; C.I. Disperse Blue-56,60,73,87,113,128,143,148,154,158,165,165:1,165:2,176,183,185,197,198,201,214,224,225,257,266,267,287,354,358,365,368; C.I. Disperse Green 6:1,9 etc.Wherein, be preferably C.I. solvent yellow 29 and 30, be preferably C.I. solvent blue 70, be preferably C.I. solvent red 18 and 49, be preferably the C.I. solvent black 3,7 and nigrosine class black dyes as black as magenta as cyan as yellow.

From improving viewpoints such as dispersion stabilization, printing concentration, the content of the tinting material in water dispersion of the present invention and the water color ink is preferably 1～30 weight %, more preferably 3～20 weight %.

From improving viewpoints such as printing concentration, for ratio in the amount of water-insoluble graftomer used in the present invention and tinting material, solid state component with respect to the insoluble graftomer of 100 weight parts waters, tinting material is preferably 20～1,000 weight part, more preferably 50～900 weight parts, more preferably 100～800 weight parts.

(water dispersion and the water color ink that contain the water-insoluble graftomer particle of tinting material)

Water dispersion of the present invention preferably obtains by following operation (1) and (2).

Operation (1): the operation that will contain the mixture dispersion treatment of water-insoluble graftomer, organic solvent, neutralizing agent, tinting material, water etc.;

Operation (2): the operation of removing aforementioned organic solvent.

In operation (1), at first, make aforementioned water-insoluble graftomer be dissolved in organic solvent, then, with tinting material, neutralizing agent, water and as required and adding such as the tensio-active agent of selecting and being mixed in the aforementioned organic solvent obtains the oil-in-water-type dispersion.In mixture, the content of tinting material is preferably 5～50 weight %, and the content of organic solvent is preferably 10～70 weight %, and the content of water-insoluble graftomer is preferably 2～40 weight %, and the content of water is preferably 10～70 weight %.There is no particular limitation for degree of neutralization, but the liquid of the water dispersion that finally obtains usually is neutrality, and for example, pH is preferably 4.5～10.Aforementioned water-insoluble graftomer also can be determined pH according to desirable degree of neutralization.In addition, the water-insoluble graftomer also can use in advance with in the neutralizing agent and cross.

Preferably enumerate alcoholic solvent, ketones solvent, ether solvent etc. as organic solvent, preferably the solubleness to water is 50 weight % or following solvent under 20 ℃, more preferably 10 weight % or above solvent.

Can list propyl carbinol, the trimethyl carbinol, isopropylcarbinol, Pyranton etc. as alcoholic solvent.Can list methylethylketone, metacetone, methyl iso-butyl ketone (MIBK) etc. as ketones solvent.Can list dibutyl ether, diox etc. as ether solvent.In these solvents, be preferably methylethylketone.

As neutralizing agent, kind according to the salt-forming group in the water-insoluble graftomer, neutralizing agent can use acid or alkali, operable is alkali such as acid such as hydrochloric acid, acetic acid, propionic acid, phosphoric acid, sulfuric acid, lactic acid, succsinic acid, oxyacetic acid, glyconic acid, R-Glyceric acid, lithium hydroxide, sodium hydroxide, potassium hydroxide, ammonia, methylamine, dimethylamine, Trimethylamine 99, ethamine, diethylamine, triethylamine, trolamine.

There is no particular limitation for the dispersing method of the mixture in the aforementioned operation (1); can be not only and lead dispersion; can also be desirable particle diameter to the median size of insoluble polymer particle with its micronize; preferably after preparation disperses; apply shear-stress again and lead dispersion, thereby the median size of insoluble polymer particle is controlled to be desirable particle diameter.

When the preparation dispersed mixture, can use mixed stirring devices commonly used such as stirring rake such as anchor fluke.Preferred in mixing whipping appts: Ultra Disper (shallow Tian Tiegang Co., Ltd., trade(brand)name), Ebara Milder (ebara corporatlon Co., Ltd., trade(brand)name), TK Homomixer, TK Pipeline Mixer, TK Homo Jetter, TK Homomic Line Flow, Filmix (more than, Tokushu Kika Kogyo K.K, trade(brand)name), Clearmix (M-Technic Co., Ltd., trade(brand)name), K.D.Mill high speeds such as (Kinetics Dispersion company, trade(brand)names) stirs mixing apparatus.

As applying the main device that disperses shear-stress, for example can list rolling mill, ball mill, kneader, milling machines such as extrusion machine, with high-pressure homogenizer (the Izumi FoodMachinery of Co., Ltd., trade(brand)name) and the small test chamber with (Mini-Labo) 8.3H type (Rannie company, trade(brand)name) for homogeneous phase valve formula (homo-valve) high-pressure homogenizer of representative, Micro-Fluidizer (microfluidics company, trade(brand)name), Nanomizer (Nanomizer Co., Ltd., trade(brand)name), Altimizer (Sugino Machine Co., Ltd., trade(brand)name), Genus PY (plain boiled water KCC, trade(brand)name), chamber formula high-pressure homogenizers such as DeBEE2000 (Japanese BEE Co., Ltd., trade(brand)name) etc.Wherein, the viewpoint of the small particle sizeization of the pigment that is contained from mixture is preferably high-pressure homogenizer.

In operation (2), become water-based by heating up in a steamer organic solvent from resulting dispersion, can obtain containing the water dispersion of the water-insoluble graftomer particle of tinting material.The organic solvent that can remove in the water dispersion to be contained by usual ways such as underpressure distillation.Organic solvent in the water dispersion of resulting water-insoluble graftomer particle is removed in fact, and the amount of organic solvent is 0.1 weight % or following, is preferably 0.01 weight % or following.

The water dispersion that contains the water-insoluble graftomer particle of tinting material is to be main solvent with water, and the solid state component that will contain the water-insoluble graftomer of tinting material is scattered in wherein and forms.

Here, there is no particular limitation to contain the form of water-insoluble graftomer particle of tinting material, can be the particle that forms by tinting material and insoluble polymer at least.For example, can be to be included in the particle shape that includes tinting material in the water-insoluble graftomer, be scattered here and there equably in the water-insoluble graftomer particle shape of toner exposes any of particle shape etc. of tinting material at the particle surface of water-insoluble graftomer.

The water dispersion of water-insoluble graftomer particle can directly use as water color ink, but also can add common humectants in the water-based ink for use in ink-jet recording, permeate agent, dispersion agent, viscosity modifier, defoamer, mould inhibitor, rust-preventive agent etc.

From preventing viewpoints such as printer nozzle obstruction, dispersion stabilization, in resulting water dispersion and the water color ink, the median size that contains the water-insoluble graftomer particle of tinting material is preferably 0.01～0.5 μ m, more preferably 0.03～0.3 μ m is preferably 0.05～0.2 μ m especially.In addition, the laser particle analytical system ELS-8000 of median size Shi Yong Da Peng Electronics Co., Ltd (accumulation (cumulants) is analyzed) measures according to following condition.

Temperature: 25 ℃

The angle of incident light and detector: 90 °

Cumulative frequency: 100 times

The specific refractory power of dispersion solvent: the specific refractory power of water (1.333)

Measure concentration: 5 * 10 ^-3Weight %

In addition, from viewpoints such as printing concentration, ejection stability, in water dispersion and the water color ink, the content (solid state component) that contains the water-insoluble graftomer particle of tinting material preferably is adjusted to 1～30 weight %, more preferably is adjusted to 3～25 weight %.

The content of the water in water dispersion of the present invention and the water color ink is preferably 30～90 weight %, more preferably 40～80 weight %.

The surface tension under 20 ℃ for water dispersion of the present invention and water color ink is preferably 30～65mN/m as water dispersion, more preferably 35～60mN/m; Be preferably 25～50mN/m as water color ink, more preferably 27～45mN/m.

Preferred viscosity in order to form as water color ink, the viscosity of 10 weight % of water dispersion of the present invention (20 ℃) is preferably 2～6mPas, more preferably 2～5mPas.In addition, in order to keep good ejection, the viscosity of water color ink of the present invention (20 ℃) is preferably 2～12mPas, more preferably 2.5～10mPas.

Water color ink of the present invention can show higher printing concentration being printed onto on the common paper, and on being printed onto dedicated paper the time, show excellent glossiness, the reconstruction of image and image distinctiveness, the printing concentration of measuring by following standard test (1) be preferably 1.10 or more than, more preferably 1.15 or more than, be preferably especially 1.20 or more than; In addition, the glossiness of measuring by following standard test (2) (60 °) be 65 or above, more preferably 70 or above, especially be preferably 75 or more than.

Standard test (1): with common paper (high quality common paper, Epson's manufacturing, the trade(brand)name: KA4250NT) after placing 24 hours under 25 ℃, measure printing concentration of whole printing (printed solid image) with densitometer.

Standard test (2): with dedicated paper (photography paper, Epson's manufacturing, the trade(brand)name: KA450PSK) after placing 24 hours under 25 ℃, of whole printing with the gloss of fixed 60 ° of gloss instrumentation.

In addition, water color ink of the present invention is preferably following water-based ink for use in ink-jet recording: the reconstruction of image of measuring by following standard test (3) (C%) be preferably 15 or above, more preferably 20 or above, especially be preferably 25 or more than.

Standard test (3): with the dedicated paper (photography paper of whole printing, Epson makes, trade(brand)name: KA450PSK) descending placement after 24 hours at 25 ℃, is 45 ° the reconstruction of image (C%) (word comb (comb) width is 2.0mm) with reconstruction of image tester mensuration input angle.

The described reconstruction of image is distinctiveness, the distortion that is used to estimate when reflecting the image onto on the printed matter, and the image that numerical value greatly then reflects is distinct more, and (distortion) is little in distortion, and then Fan She image seems natural more.

In addition, water color ink of the present invention also is preferably following water color ink: the glossiness that above-mentioned standard test (2) is tried to achieve multiply by the reconstruction of image value that above-mentioned standard test (3) is tried to achieve, with the value that obtains divided by 100 resulting values as the distinct value [glossiness (60 °) * reconstruction of image (C%)]/100 of image, its be preferably 10 or more than, more preferably 15 or more than, be preferably especially 20 or more than.Here, the distinct value of image is to estimate the boldness of image of glossiness and reflection or the value of distortion simultaneously, and it is the index of the gloss of trying to achieve such as photo, distinctiveness, distortion, and this value is high, represents glossyly, seems distinctness and does not have distortion.

In addition, in above-mentioned each standard test, can use C.I. pigment red 122 or C.I. pigment violet 19 as tinting material.

(ink jet recording method)

Ink jet recording method of the present invention is that aforementioned water-based ink for use in ink-jet recording is printed onto on the common paper or dedicated paper as recording medium, thus the method that writes down.Ink-jet recording can hot stamping type or piezo-electric type.

Dedicated paper used in the present invention is the paper that can be used for ink-jet recording, is preferably the air gap type gloss media that comprises paper, plastics and their mixture etc. and have air gap type printing ink accommodating layer.

Here, described air gap type printing ink accommodating layer is the material with the air gap type printing ink accommodating layer that is made of porous matter inorganic particulate such as aluminum oxide, silicon-dioxide and water soluble resin (tackiness agent), can use known material as air gap type gloss media with this air gap type printing ink accommodating layer, for example, can use the material of putting down in writing among the p174～p181 of " application of ink-jet printer and material " (distribution in 2002 of (strain) CMC Cinema Magnetique Communication).

The surface of dedicated paper used in the present invention with specular gloss count 60 ° glossiness be preferably 60 or below, more preferably 55 or below, more preferably 50 or below, and be preferably 15 or above air gap type gloss media.The glossiness here is that (for example, Japanese electric decorations company makes trade(brand)name: HANDYGLOSSMETER, article number: the PG-1) value of Ce Dinging by glossmeter.

As employed dedicated paper among the present invention, can the commercial object lesson that obtains can list photography paper＜gloss that Epson Co., Ltd. makes 〉, the SuperPhoto SP-101 of Canon Co., Ltd. etc.

Ink jet recording method of the present invention is by the use ink-jet recording device water-based ink for use in ink-jet recording of the present invention to be printed onto on the air gap type gloss media with printing ink accommodating layer, thereby has given play to higher glossiness.

By the water-based ink for use in ink-jet recording that contains water dispersion for ink-jet printing of the present invention, can be provided in the high printing concentration of realization when being printed onto on the common paper and realize excellent glossiness, the reconstruction of image, image distinctiveness on being printed onto dedicated paper the time, the water color ink of rub resistance excellence, ejection excellent in stability is provided simultaneously.

Below wait and more specifically to represent the present invention by enumerating embodiment, but entity of the present invention is not subjected to the qualification of embodiment etc.

Production Example 1,2 and comparison Production Example 1

In reaction vessel, add 10 weight % of the monomer mixture shown in 20 weight part methylethylketones, 0.03 weight part polymeric chain transfer agent (2 mercapto ethanol) and the 200 weight part tables 1, mix then, carry out nitrogen replacement fully, obtain mixing solutions.

On the other hand, the monomer mixture shown in the table 1 of the remaining 90 weight % of adding in dropping funnel, add 0.27 weight part polymeric chain transfer agent (2 mercapto ethanol), 60 weight part methylethylketones and 1.2 weight parts 2 again, 2 '-azo two (2, the 4-methyl pentane nitrile), mix then, carry out nitrogen replacement fully, obtain mixing solutions.

Under nitrogen atmosphere, on one side the interior mixing solutions of stirring reaction container, be warmed up to 65 ℃ on one side, the mixing solutions in 3 hours in the slow addition funnel.From drip to finish beginning under 65 ℃ through 2 hours after, add 0.3 weight part 2,2 '-azo two (2, the 4-methyl pentane nitrile) is dissolved in the solution that 5 weight part methylethylketones form, again 65 ℃ of following slakings 2 hours, 70 ℃ of following slakings 2 hours, obtain polymers soln.

The dimethyl formamide of lithiumbromide that the weight-average molecular weight of resulting polymkeric substance can contain the phosphoric acid of 60mmol/L and 50mmol/L by use uses polystyrene to measure as reference material as the gel chromatography of solvent.The result is as shown in table 1.

Table 1

In addition, the numeral weight part shown in the table 1, particular compound is as follows.

The vinylbenzene macromonomer: East Asia Synesis Company makes, trade(brand)name: AS-6S, and number-average molecular weight: 6000, polymerizable functional groups group: methacryloxy

(the average addition mole number of oxyethane: 9): Xin Zhong village chemical company makes polyethylene glycol monomethacrylate, trade(brand)name: Nk esterM-90G

(the average addition mole number of propylene oxide: 9): Nof Corp. makes polypropylene glycol monomethacrylate, trade(brand)name: BLENMER PP-500

Embodiment 1

With Production Example 1 resulting polymers soln drying under reduced pressure, the resulting polymkeric substance of 25 weight parts is dissolved in 70 weight part methylethylketones, add 4.1 weight part neutralizing agents (5N aqueous sodium hydroxide solution) (degree of neutralization 75%) and 230 weight part ion exchanged waters therein, be neutralized into alkali, add 75 weight part dimethyl quinoline a word used for translation ketone pigment (C.I. pigment red 122s again, Ciba SpecialtyChemicals company makes, trade(brand)name: IRGAPHOR MAGENTA DMQ), with disperseing oar to mix 1 hour down at 20 ℃.With resulting miscellany with microjet homogeneous separating apparatus (Microfluidics company makes, trade(brand)name) under the pressure of 200MPa, dispersion treatment 10 times.

In resulting mixing thing, add 250 weight part ion exchanged waters, after the stirring, under reduced pressure, remove methylethylketone under 60 ℃, remove a part of water again, by with 5 μ m strainer (cellulose acetate films are installed, external diameter: 2.5cm, Fuji Photo Film Co., Ltd. makes) capacity be 25ml not with syringe (manufacturings of the Terumo company) filtration of syringe needle, remove thick particle and obtain the water dispersion that solid component concentration is the water-insoluble graftomer particle that contains pigment of 20 weight %.

With the resulting water dispersion that contains the water-insoluble vinyl polymer particle of pigment of 40 weight parts, 10 weight part glycerol, 7 weight part triglycol single-butyl ethers (TEGMBE), 1 weight part SURFINOL 465 (a day letter chemical industrial company makes), 0.3 weight part PROXELXL2 (manufacturing of Avicia company) and 41.7 weight part ion exchanged waters, with resulting mixed solution with 1.2 μ m strainer (cellulose acetate films are installed, external diameter: 2.5cm, Fuji Photo Film Co., Ltd.) capacity be 25ml not with the syringe filtering of syringe needle, remove oversize particle, obtain the water color ink shown in the table 2.

Embodiment 2

Except using unsubstituted quinoline a word used for translation ketone pigment (C.I. pigment violet 19, Clariant Japan company makes, trade(brand)name: Hostaperm Red E5B02) beyond the dimethyl quinoline a word used for translation ketone pigment among the replacement embodiment 1, obtain the water color ink shown in the table 2 similarly to Example 1.

Embodiment 3

Replace Production Example 1 among the embodiment 1 to obtain obtaining the water color ink shown in the table 2 similarly to Example 1 the polymers soln except using Production Example 2 to obtain polymers soln.

Comparative example 1

Replace Production Example 1 among the embodiment 1 to obtain obtaining the water color ink shown in the table 2 similarly to Example 1 the polymkeric substance except using Production Example 1 relatively to obtain polymkeric substance.

In each embodiment, comparative example, the median size of water dispersion is all in the scope of 0.05～0.2 μ m.

Then, measure the performance of the printing ink that obtains respectively by embodiment 1～3 and comparative example 1 according to following method.The result is as shown in table 2.

(1) printing concentration [standard test (1)]

(Epson makes to use ink-jet printer, model: EM-930C), at common paper (high quality common paper, Epson makes, trade(brand)name: and KA4250NT) last whole printing (printing condition: use the paper kind: common paper, pattern is set: photo (photo)), after placing 24 hours under 25 ℃, (Macbeth company makes, article number: RD914) measure 5 times (25 ℃), try to achieve its mean value with the Macbeth densitometer.

(2) glossiness [standard test (2)]

Use aforementioned printer, aforementioned dedicated paper (photography paper＜gloss〉(60 ° glossiness is 41), Epson makes, trade(brand)name: KA450PSK) last whole printing (printing condition: use the paper kind: photo prints paper (photo printing paper), pattern is set: photo), after placing 24 hours under 25 ℃, (Japanese electric decorations company makes with glossmeter, trade(brand)name: HANDY GLOSSMETER, article number: PG-1) measure 60 ° gloss 5 times (25 ℃), try to achieve its mean value.

(3) rub resistance

Use aforementioned printer, whole printing on aforementioned dedicated paper is after under 25 ℃ dry 24 hours, with finger strong friction printing surface.Estimate the degree wiped of this printed patterns according to following metewand.

[metewand]

Zero: almost do not wipe the image that is printed, do not pollute on every side

△: can wipe the image that is printed on a small quantity, ambient contamination is less, and finger also slightly pollutes

*: can wipe the considerable image that is printed, ambient contamination is quite serious, and finger pollutes also quite serious.

(4) ejection stability

Use aforementioned printer, on aforementioned common paper, carry out 5 whole printings, observe the not good nozzle number of ejection, estimate according to following metewand.

[metewand]

Zero: ejection is not good

△: 1～10 nozzle ejection is not good

*: 10 or above ejection are not good

(5) reconstruction of image [standard test (3)]

Use aforementioned printer, aforementioned dedicated paper (photography paper＜light is selected〉(60 ° glossiness is 41), Epson makes, trade(brand)name: KA450PSK) last whole printing (printing condition: use the paper kind: photo prints paper, pattern is set: photo), after placing 24 hours under 25 ℃, (Suga experimental machine Co., Ltd. makes with reconstruction of image tester, trade(brand)name: touch (Touch Panel) formula reconstruction of image tester, article number: ICM-IT) measuring input angle is 45 ° the reconstruction of image 5 times, tries to achieve its mean value.

(6) image distinctiveness

From aforementioned glossiness and reconstruction of image value, try to achieve the distinct value of image=[glossiness (60 °) * reconstruction of image (C%)]/100

Table 2

From the result shown in the table 2 as can be known: the printing ink that is obtained by each embodiment all can form higher printing concentration in common paper, and, higher glossiness, the reconstruction of image and image distinctiveness are also arranged on dedicated paper.In addition, can also know that the printing ink that is obtained by each embodiment can provide the printed matter of ejection excellent in stability, rub resistance excellence.

Claims

1. water dispersion for ink-jet printing, it is the water dispersion that contains the water-insoluble graftomer particle of tinting material, wherein this water-insoluble graftomer has following main chain and side chain,

Main chain: be to contain (a) to come from monomeric structural unit that contains salt-forming group and the polymer chain that (b) comes from the structural unit of (methyl) acrylate monomer that contains aromatic nucleus;

Side chain: be to contain the polymer chain that (c) comes from the structural unit of hydrophobic monomer.

2. the water dispersion for ink-jet printing of putting down in writing according to claim 1, wherein (b) come from (methyl) acrylate monomer that contains aromatic nucleus structural unit with following formula (1) expression,

In the formula, R ¹Expression hydrogen atom or methyl, R ²Expression has substituting group or do not have substituent carbonatoms is that 7～22 aralkyl or carbonatoms are 6～22 aryl.

3. the water dispersion for ink-jet printing of putting down in writing according to claim 1, wherein in the main chain, (a) coming from monomeric structural unit that contains salt-forming group and the weight ratio [(a)/(b)] that (b) comes from the structural unit of (methyl) acrylate monomer that contains aromatic nucleus is 1/1～1/20.

4. the water dispersion for ink-jet printing of putting down in writing according to claim 1, wherein the weight ratio of main chain and side chain [main chain/side chain] is 1/1～20/1.

5. the water dispersion for ink-jet printing of putting down in writing according to claim 1, wherein (c) to come from the structural unit of hydrophobic monomer be the structural unit that comes from styrene monomer.

6. the water dispersion for ink-jet printing of putting down in writing according to claim 5, wherein water-insoluble graftomer (a) that contain 3～30 weight % (b) that come from the monomeric structural unit that contains salt-forming group, 10～80 weight % (c) that come from the structural unit of (methyl) acrylate monomer that contains aromatic nucleus and 5～50 weight % comes from the structural unit of styrene monomer.

7. the water dispersion for ink-jet printing of putting down in writing according to claim 1, wherein tinting material is a pigment.

8. water-based ink for use in ink-jet recording, it contains each water dispersion of being put down in writing of claim 1～7.

9. the water-based ink for use in ink-jet recording of record according to Claim 8, wherein the printing concentration of measuring by following standard test (1) be 1.1 or more than, 60 ° of glossiness measuring by following standard test (2) be 65 or more than,

Standard test (1): the common paper of whole printing after 24 hours, is measured printing concentration with densitometer in placement under 25 ℃, and described common paper is the high quality common paper that the commodity of Epson's manufacturing are called KA4250NT,

Standard test (2): the dedicated paper of whole printing after 24 hours, is decided 60 ° gloss with the gloss instrumentation in placement under 25 ℃, and described dedicated paper is the photography paper that the commodity of Epson's manufacturing are called KA450PSK.

10. the water-based ink for use in ink-jet recording of being put down in writing according to Claim 8, the reconstruction of image C% that wherein following standard test (3) is measured be 15 or more than,

Standard test (3): descend placement after 24 hours at 25 ℃ the dedicated paper of whole printing, measuring input angle with reconstruction of image tester is 45 ° reconstruction of image C%, described dedicated paper is the photography paper of the commodity KA450PSK by name of Epson's manufacturing, and the word comb width of described mensuration is 2.0mm.

11. the water-based ink for use in ink-jet recording of being put down in writing according to Claim 8, wherein the image distinctiveness value of calculating by [60 ° of glossiness measuring of standard test (2) * measure by standard test (3) reconstruction of image C%]/100 be 10 or more than,

Standard test (2): the dedicated paper of whole printing after 24 hours, is decided 60 ° gloss with the gloss instrumentation in placement under 25 ℃, and described dedicated paper is the photography paper that the commodity of Epson's manufacturing are called KA450PSK,

12. an ink jet recording method, it is to use ink-jet recording device, and the water color ink that claim 8 is put down in writing is printed onto on the air gap type gloss media with printing ink accommodating layer.