CN100523100C - Ink for inkjet printing, ink set for inkjet printing, inkjet recording material and producing method for inkjet recording material, and inkjet recording method. - Google Patents

Abstract

At lease one of an ink for inkjet printing and an inkjet recording material contains a compound represented by formula (A):wherein R1, R2, and R3 each represents an alkyl group, an aryl group or a heterocylic group, and at least two of R1, R2 and R3 are mutually connected to form a cyclic structure; L represents a divalent connecting group; and at least one of R1, R2, R3 and L is a group having 8 or more carbon atoms.

Description

Be used for ink jet printing ink, be used for the manufacture method and the ink jet recording method of ink group, ink jet recording materials and the ink jet recording materials of ink jet printing

Technical field

The present invention relates to form the ink that is used for ink jet printing of image and be used for the ink group of ink jet printing with excellent durability.

The invention still further relates to and be used for the recording materials of ink jet printing, liquid ink such as water-base ink (adopting dyestuff or pigment as colorant) or oily ink are used in described ink jet printing, or solid ink, described solid ink is solid at normal temperatures, but be molten into liquid state when being used to print, and more specifically, the present invention relates to form the ink jet recording materials and the ink jet recording method of image with excellent durability.

Background technology

Recently the quick progress of information technology has stimulated the exploitation of various information processing systems, and has developed with commercialization recording method and the recording unit that is complementary with this information processing system.

In these recording methods, ink jet recording method has not only obtained utilization widely in office but also in so-called household application, reason is following advantage: the cheap and compactedness of the possibility that writes down on various recording materials, hardware (device), and excellent record quietness.

In ink jet recording method, known have a following method: thus produce the method that pressure is discharged drop by piezoelectric element; Thereby produce the method that bubble is discharged drop by heat; The method of using hyperacoustic method and drop being discharged by the suction of electrostatic force.For these ink ejecting methods, use water-base ink, oily ink or solid (fusing type) ink.In these, consider manufacturing, manipulative capability, smell, security etc., mainly use water-base ink.

Requirement has high solubleness at the colorant that this ink that is used for ink jet printing adopts in solvent, high density record, satisfied tone, light, heat, air, water and chemical there is excellent anti-jail property, the satisfied stationarity of image receiving material is not oozed out, excellent ink storage property, nontoxicity, high purity and cheaply acquired.But, be difficult to especially find that high level satisfies the colorant of these requirements.

Propose various dyestuffs and pigment and be used for ink jet printing, and be used for practice, still, in fact, also do not had to find to satisfy the colorant of all these requirements.As by in those of color index (C.I.) number expression, be difficult to obtain simultaneously being used for the anti-jail property of the desired color harmony of ink of ink jet printing at known dyestuff and pigment.For the satisfied colorant that is used for ink jet printing, researched and developed dyestuff with the anti-fastness of satisfied color harmony.But, compare with halogenation money base photograph, find that this material has significantly not good anti-jail property of ozone and the anti-jail property of light.

On the other hand,, can obtain the record of the so-called photo sample of high image quality, and develop various ink jet recording papers, thereby be complementary with this progress of hardware (device) because ink-jet printer is towards the more latest developments of high definition.

Generally include for this desired character of recording paper that is used for ink jet printing: (1) rapid drying (high ink absorption speed), (2) suitable and uniform inkspot diameter (nothing is oozed out), (3) Man Yi size of particles, (4) high some circularity, (5) high colour density, (6) high saturation ratio (no color turbidity), that (7) is satisfied with in printing is water-fast, light and ozone, (8) the high whiteness of recording paper, (9) the satisfied storage (prolonging does not have flavescence and prolong do not have image to ooze out (the satisfied anti-time is exudative) when storing when storing) of recording paper, (10) Man Yi dimensional stability and operating performance in hardware of not distortion (fully little curls) and (11) satisfaction.

In addition, at the photo glossy paper that is used for obtaining so-called phase sheet high quality record, except character recited above, also requirement is similar to the texture of gloss, surface flatness and the photograph pattern of halogenation money base photo.

Be intended to improve characteristic recited above, exploitation and commercialization recently have an ink jet recording materials of the ink receiving layer of vesicular structure.This ink jet recording materials is because this vesicular structure has satisfied ink receptivity (rapid drying performance) and high gloss.

For example, JP-A-10-119423 and JP-A-10-217601 have proposed a kind of ink jet recording materials, and it comprises, on base material, contain mineral dye particulate and water soluble resin and have the ink receiving layer of high porosity (porerate).

This ink jet recording materials, utilize silicon-dioxide to have the ink jet recording materials of the ink receiving layer of vesicular structure as inorganic pigment particles thereby particularly have, demonstration is by the ink absorption performance of the satisfaction of its structure, thereby the high ink receptivity of the image that can form high definition and high gloss is provided.

But the gas of trace, particularly ozone in air may become the reason that the image of record fades in time.Recording materials with vesicular structure ink receiving layer recited above make the image fade of record easily owing to airborne ozone gas, reason is that it has many apertures.Therefore, for top described recording materials with vesicular structure ink receiving layer, anti-airborne ozone (ozone resistants) is a very important character.

Summary of the invention

One object of the present invention be to be provided for ink jet printing ink, be used for ink group, ink jet recording materials and manufacture method thereof and the ink jet recording method of ink jet printing, thereby can form image with excellent durability.

In order to reach purpose recited above, the inventor has carried out intensive research, and finds that a kind of betaine compound is effectively, a kind of sultaine compound of particularly describing among the present invention.

More specifically, purpose of the present invention is realized by the ink that is used for ink jet printing, the ink group, ink jet recording materials and the manufacture method thereof that are used for ink jet printing and ink jet recording method described in following 1 to 18:

1) a kind of ink that is used for ink jet printing, it comprises:

At least a in water and the water miscibility organic solvent;

Dyestuff; With

Compound by formula (A) expression:

R wherein ₁, R ₂And R ₃Represent alkyl, aryl and heterocyclic group separately, and R ₁, R ₂And R ₃In at least two formation ring texturees that mutually combine; L represents divalent linker, and R ₁, R ₂, R ₃With among the L at least one be the group that contains 8 or more a plurality of carbon atoms.

2) according to the ink that is used for ink jet printing of item (1), wherein said dyestuff is to be selected from least a in the group of being made up of the dyestuff of following formula (1) to (4) expression:

Formula (1): (A ₁₁-N=N-B ₁₁) _n-L

Formula (2)

Formula (3)

Formula (4):

A ₄₁-N＝N-A ₄₂-N＝N-A ₄₃

Wherein in formula (1),

A ₁₁And B ₁₁Expression can substituted heterocyclic group independently of one another;

N represents 1 or 2; And

L represents hydrogen atom, monovalence substituting group, singly-bound or divalent linker;

Wherein when n was 1, L represented hydrogen atom or monovalence substituting group and A ₁₁And B ₁₁It all is the monovalence heterocyclic group; And

When n was 2, L represented singly-bound or divalent linker, A ₁₁Expression monovalence heterocyclic group, and B ₁₁It is divalent heterocyclic group;

In formula (2),

X ₂₁, X ₂₂, X ₂₃And X ₂₄Expression-SO-Z independently of one another ₂,-SO ₂-Z ₂,-SO ₂NR ₂₁R ₂₂, sulfo group ,-CONR ₂₁R ₂₂Or-COOR ₂₁, Z wherein ₂Represent alkyl, cycloalkyl, thiazolinyl, aralkyl, aryl or heterocyclic group independently, its each can further be substituted; And R ₂₁And R ₂₂Represent hydrogen atom, alkyl, cycloalkyl, thiazolinyl, aralkyl, aryl or heterocyclic group independently of one another, its each can further be substituted;

Y ₂₁, Y ₂₂, Y ₂₃And Y ₂₄Represent the monovalence substituting group independently of one another;

a ₂₁, a ₂₂, a ₂₃And a ₂₄Represent X respectively ₂₁, X ₂₂, X ₂₃And X ₂₄Number, and represent that independently of one another 0 to 4 number, precondition are all a ₂₁, a ₂₂, a ₂₃And a ₂₄Be not 0 simultaneously, wherein work as a ₂₁, a ₂₂, a ₂₃And a ₂₄Any one is 2 or when bigger, a plurality of X ₂₁, X ₂₂, X ₂₃And X ₂₄Identical or different mutually;

b ₂₁, b ₂₂, b ₂₃And b ₂₄Represent Y respectively ₂₁, Y ₂₂, Y ₂₃And Y ₂₄Number, and represent 0 to 4 number independently of one another, wherein work as b ₂₁, b ₂₂, b ₂₃And b ₂₄Any one is 2 or when bigger, a plurality of Y ₂₁, Y ₂₂, Y ₂₃And Y ₂₄Identical or different mutually; And

M represents hydrogen atom, atoms metal, metal oxide, metal hydroxides or metal halide; In formula (3),

A ₃₁Represent 5 yuan of heterocycles;

B ₃₁And B ₃₂Expression=CR separately ₃₁-or-CR ₃₂=, or B ₃₁And B ₃₂In any expression nitrogen-atoms, and another expression=CR ₃₁-or-CR ₃₂=;

R ₃₅And R ₃₆Represent hydrogen atom, aliphatic group, aromatic group, heterocyclic group, acyl group, alkoxy carbonyl, aryloxycarbonyl, formamyl, alkyl sulphonyl, aryl sulfonyl or sulfamyl independently of one another, its each can also contain substituting group;

G ₃, R ₃₁And R ₃₂Represent hydrogen atom independently of one another, halogen atom, aliphatic group, aromatic group, heterocyclic group, cyano group, carboxyl, formamyl, alkoxy carbonyl, aryloxycarbonyl, the heterocyclic oxy group carbonyl, acyl group, hydroxyl, alkoxyl group, aryloxy, heterocyclic oxy group, siloxy-, acyloxy, carbamoyloxy, alkoxy-carbonyl oxy, aryloxycarbonyl oxygen base, amino, virtue is amino, heterocyclic amino group, amido, urea groups, sulfamoylamino group, alkoxycarbonyl amino, aryloxycarbonyl amino, alkyl sulfonyl amino, Arenesulfonyl amino, the heterocycle sulfonamido, nitro, alkylthio, arylthio, alkyl sulphonyl, aryl sulfonyl, the heterocycle alkylsulfonyl, alkyl sulphinyl, aryl sulfonyl kia, the heterocycle sulfinyl, sulfamyl, sulfo group or heterocycle sulfenyl, its each can further be substituted; And

R ₃₁And R ₃₅, or R ₃₅And R ₃₆Each can be interconnected to form 5-or 6-unit ring; And in formula (4),

A ₄₁, A ₄₂And A ₄₃Represent aromatic group or heterocyclic group independently of one another, its each can further be substituted; A ₄₁And A ₄₃It is univalent perssad; And A ₄₂It is divalent group.

In described in front, the dyestuff of preferred formula (3) expression.

3) according to the ink that is used for ink jet printing of item (2), wherein the dyestuff by formula (2) expression is the dyestuff of being represented by formula (5):

Wherein, X ₅₁, X ₅₂, X ₅₃, X ₅₄And M ₁Has the X in the formula (2) respectively ₂₁, X ₂₂, X ₂₃, X ₂₄The implication identical with M; Y ₅₁And Y ₅₂Has the Y in the formula (2) ₂₁Identical implication; Y ₅₃And Y ₅₄Has the Y in the formula (2) ₂₂Identical implication; Y ₅₅And Y ₅₆Has the Y in the formula (2) ₂₃Identical implication; Y ₅₇And Y ₅₈Has the Y in the formula (2) ₂₄Identical implication; And a ₅₁, a ₅₂, a ₅₃And a ₅₄Represent 1 or 2 integer independently of one another.

4) a kind of ink group that is used for ink jet printing, it comprises according to any one ink of item (1) to (3).

5) a kind of ink jet recording materials, it comprises: base material; With the ink receiving layer on base material,

Wherein said ink receiving layer comprises the compound by formula (A) expression:

R wherein ₁, R ₂And R ₃Represent alkyl, aryl and heterocyclic group separately, and R ₁, R ₂And R ₃In at least two formation ring texturees that mutually combine; L represents divalent linker, and R ₁, R ₂, R ₃With among the L at least one be the group that contains 8 or more a plurality of carbon atoms.

6) according to the ink jet recording materials of item (5), wherein said ink receiving layer also contains water soluble resin.

7) according to the ink jet recording materials of item (6), wherein said water soluble resin be selected from down the group at least a: the resin of polyvinyl alcohol resin, celluosic resin, ether-containing key, the resin that comprises formamyl, carboxylic resin and gelatin.

Described water soluble resin is polyvinyl alcohol resin preferably.

8) according to the ink jet recording materials of item (6) or (7), wherein said ink receiving layer comprise can crosslinked described water soluble resin linking agent.

9) according to any one ink jet recording materials of item (5) to (8), wherein said ink receiving layer also comprises particulate.

10) according to the ink jet recording materials of item (9), wherein said particulate be selected from down the group at least a: fine particles of silica, colloid silica, aluminum oxide particulate and pseudobochmite.

11) according to any one ink jet recording materials of item (5) to (10), wherein said ink receiving layer also contains mordant.

12) according to any one ink jet recording materials of item (5) to (11), wherein said ink receiving layer is the cured layer that forms by following method:

First kind of solution of coating forms coating layer on base material, and described first kind of solution contains particulate, water soluble resin and linking agent; With

Second kind of solution of coating on described coating layer, the pH of described second kind of solution is 8 or higher, so that by crosslinking reaction described coating layer is solidified, forms cured layer,

Second kind of solution of wherein said coating is undertaken by one of following dual mode:

(1) time identical with the coating of first kind of solution; With

(2) during drying, and before coating layer begins to show the drying rate of decline.

13) a kind of ink jet recording method, this method comprises: discharging is according to any one ink droplet of item (1) to (3), to form image or character on ink jet recording materials.

14) a kind of ink jet recording method, this method comprises: discharge ink is dripped on according to any one ink jet recording materials of item (5) to (12), to form image or character.

15) according to the ink jet recording method of item (14), wherein at least a ink contains betaine compound.

16) according to the ink jet recording method of item (15), wherein said betaine compound is by according to the item (compound of 5 formula (A) expression.

17) according to the ink jet recording method of item (15), wherein at least a ink is according to any one ink of item (1) to (3).

18) a kind of method of making ink jet recording materials, this method comprises:

First kind of solution of coating forms coating layer on base material, and described first kind of solution contains particulate, water soluble resin and linking agent; With

Second kind of solution of coating on described coating layer, the pH of described second kind of solution is 8 or higher, so that by crosslinking reaction described coating layer is solidified, forms the ink receiving layer,

Second kind of solution of wherein said coating is undertaken by one of following dual mode:

(1) time identical with the coating of first kind of solution; With

(2) during drying, and before coating layer begins to show the drying rate of decline.

The present invention can obtain having the image of the anti-jail property of excellent weather resistance, particularly light, hot anti-jail property and ozone resistants.

By the compound of formula (A) expression, by with the interaction of dyestuff, cause the dyestuff mordant dyeing state in image receiving material or the change of electronic state, thereby have the weathering resistance of improvement, particularly the positive effect of ozone resistants.

Detailed Description Of The Invention

Below, will explain the present invention in detail.

The invention is characterized at least a compound that comprises by formula recited above (A) expression at ink that is used for ink jet printing and ink jet recording materials.

Except by the compound of formula (A) expression, can also contain and the different betaine compound of representing by formula (A) of compound, and in described betaine compound, preferably contain the compound of sulfo group.

In the formula (A), R ₁To R ₃Represent that separately (it can be substituted alkyl, and preferably contain 1 to 20 carbon atom, for example methyl, ethyl, propyl group, butyl, hexyl, octyl group, dodecyl, hexadecyl, stearyl or oleyl), (it can be substituted aryl, and preferably contain 6 to 20 carbon atoms, for example phenyl, tolyl, xylyl, naphthyl, cumyl or dodecylphenyl), or heterocyclic group (it can be substituted, and preferably contain 2 to 20 carbon atoms, for example pyridyl or quinolyl), and the formation ring texture that can mutually combine.In these, special preferred alkyl.L represents divalent linker, and is preferably and comprises that alkylidene group or arylidene are as the unitary divalent linker of basic comprising.It can partly contain heteroatoms such as Sauerstoffatom, sulphur atom or nitrogen-atoms at the connection main chain.R ₁To R ₃Or L can contain various substituting groups, for example, alkyl (preferably contains 1 to 20 carbon atom, more preferably 1 to 12 carbon atom, preferred especially 1 to 8 carbon atom, methyl for example, ethyl, sec.-propyl, the tertiary butyl, n-octyl, positive decyl, n-hexadecyl, cyclopropyl, cyclopentyl or cyclohexyl), thiazolinyl (preferably contains 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, preferred especially 2 to 8 carbon atoms, vinyl for example, allyl group, crotyl or 3-pentenyl), alkynyl (preferably contains 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, preferred especially 2 to 8 carbon atoms, for example propargyl or 3-pentynyl), aryl (preferably contains 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, preferred especially 6 to 12 carbon atoms, phenyl for example, p-methylphenyl or naphthyl), amino (preferably contains 0 to 20 carbon atom, more preferably 0 to 12 carbon atom, preferred especially 0 to 6 carbon atom, for example amino, methylamino-, dimethylamino, diethylin, diphenyl amino or dibenzyl amino), alkoxyl group (preferably contains 1 to 20 carbon atom, more preferably 1 to 12 carbon atom, preferred especially 1 to 8 carbon atom, methoxyl group for example, oxyethyl group or butoxy), aryloxy (preferably contains 6 to 20 carbon atoms, more preferably 6 to 16 carbon atoms, preferred especially 6 to 12 carbon atoms, for example phenoxy group or 2-naphthyloxy), acyl group (preferably contains 1 to 20 carbon atom, more preferably 1 to 16 carbon atom, preferred especially 1 to 12 carbon atom, ethanoyl for example, benzoyl, formyl radical or valeryl), alkoxy carbonyl (preferably contains 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, preferred especially 2 to 12 carbon atoms, for example methoxycarbonyl or ethoxy carbonyl), aryloxycarbonyl (preferably contains 7 to 20 carbon atoms, more preferably 7 to 16 carbon atoms, preferred especially 7 to 10 carbon atoms, phenyloxycarbonyl for example), acyloxy (preferably contains 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, preferred especially 2 to 10 carbon atoms, for example acetoxyl or benzoyloxys), amido (preferably contains 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, preferred especially 2 to 10 carbon atoms, for example kharophen or benzamidos), alkoxycarbonyl amino (preferably contains 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, preferred especially 2 to 12 carbon atoms, methoxycarbonyl amino for example), aryloxycarbonyl amino (preferably contains 7 to 20 carbon atoms, more preferably 7 to 16 carbon atoms, preferred especially 7 to 12 carbon atoms, phenyloxycarbonyl amino for example), sulfonamido (preferably contains 1 to 20 carbon atom, more preferably 1 to 16 carbon atom, preferred especially 1 to 12 carbon atom, for example methanesulfonamido or phenylsulfonamido), sulfamyl (preferably contains 0 to 20 carbon atom, more preferably 0 to 16 carbon atom, preferred especially 0 to 12 carbon atom, for example sulfamyl, the methyl sulfamyl, dimethylamino alkylsulfonyl or phenyl sulfamoyl base), formamyl (preferably contains 1 to 20 carbon atom, more preferably 1 to 16 carbon atom, preferred especially 1 to 12 carbon atom, formamyl for example, the methylamino formyl radical, diethylamino formyl radical or phenyl amino formyl radical), alkylthio (preferably contains 1 to 20 carbon atom, more preferably 1 to 16 carbon atom, preferred especially 1 to 12 carbon atom, for example methylthio group or ethylmercapto group), arylthio (preferably contains 6 to 20 carbon atoms, more preferably 6 to 16 carbon atoms, preferred especially 6 to 12 carbon atoms, for example thiophenyls), alkylsulfonyl (preferably contains 1 to 20 carbon atom, more preferably 1 to 16 carbon atom, preferred especially 1 to 12 carbon atom, for example methylsulfonyl or tosyl group), sulfinyl (preferably contains 1 to 20 carbon atom, more preferably 1 to 16 carbon atom, preferred especially 1 to 12 carbon atom, for example methanesulfinyl or benzenesulfinyl), urea groups (preferably contains 1 to 20 carbon atom, more preferably 1 to 16 carbon atom, preferred especially 1 to 12 carbon atom, urea groups for example, methyl urea groups or phenyl urea groups), the phosphoamide base (preferably contains 1 to 20 carbon atom, more preferably 1 to 16 carbon atom, preferred especially 1 to 12 carbon atom, for example diethyl phosphoamide or phosphenylic acid acid amides), hydroxyl, sulfydryl, halogen atom (fluorine atom for example, the chlorine atom, bromine atoms or iodine atom), cyano group, sulfo group, carboxyl, nitro, the hydroxamic acid base, sulfino, diazanyl, imino-, heterocyclic group (preferably contains 1 to 30 carbon atom, more preferably 1 to 12 carbon atom contains for example as heteroatomic nitrogen-atoms, Sauerstoffatom or sulphur atom; As imidazolyl, pyridyl, quinolyl, furyl, thienyl, piperidyl, morpholino, benzoxazolyl, benzimidazolyl-, benzothiazolyl, carbazyl and azepines base), or silyl (preferably contains 3 to 40 carbon atoms, more preferably 3 to 30 carbon atoms, preferred especially 3 to 24 carbon atoms, for example trimethyl silyl or triphenyl silyl).These substituting groups can further be substituted.When having two or more substituting groups, they can be identical or different.If this structure if possible, they also can interosculate and form ring.A plurality of betaine structures can also pass through R ₁To R ₃Or L interconnects.

Compound of the present invention (A) (that is the compound of being represented by formula (A)) is included in R ₁To R ₃With the group that contains 8 or more a plurality of carbon atoms among the L at least one.Particularly, at R ₁To R ₃At least one in preferably include the chain alkyl that contains 8 or more a plurality of carbon atoms.Preferred L is unsubstituted alkylidene group (alkylidene group that preferably contains 2 to 4 carbon atoms).

R ₁To R ₃With the preferred composition of L be: R ₁To R ₃At least one be the chain alkyl that contains 8 or more a plurality of carbon atoms, and L is the unsubstituted alkylidene group that contains 2 to 4 carbon atoms.

The preferred embodiment of compound of the present invention (A) is shown in as follows, but the present invention is not limited to these examples certainly.

In ink, the content of compound of the present invention (A) in ink is preferably 0.01 to 20 quality %, 0.1 to 10 quality % more preferably, and 0.5 to 5 quality % more preferably.

The ink that uses in ink group of the present invention preferably forms in water or the organic solvent by dyestuff is dissolved in.Particularly, it is preferably the aqueous solution type ink that utilizes water-soluble dye.

The content of the compound of formula of the present invention (A) on ink jet recording paper (recording materials) is preferably 0.0001 to 10g/m ², more preferably 0.001 to 5g/m ², and be preferably 0.01 especially to 2g/m ²Be used to prepare under the situation of ink jet recording paper employing being used for two-layer coating fluid, this compound can be added in arbitrary layer, but consider coating character, preferably be added in the superiors.

In the ink receiving layer, comprise under the situation of compound of formula of the present invention (A), it can add with the state of increase with the avidity of water by the mixing water solubleness organic solvent, described organic solvent as alcohol (as methyl alcohol, ethanol, Virahol, 1,2-ethylidene glycol, glycol ether, diethylene glycol monobutyl ether, polyoxyethylene glycol, polypropylene glycol, glycerine, Glycerol dimer, TriMethylolPropane(TMP) or tri hydroxy methyl butane), ether (as tetrahydrofuran (THF) Huo diox), acid amides (as dimethyl formamide, N,N-DIMETHYLACETAMIDE or N-Methyl pyrrolidone), or ketone (as acetone).

Under the insufficient situation of the solubleness of compound in water of formula of the present invention (A), can also add hydrophobic organic solvent, for example, ester is (as ethyl acetate, Octyl adipate, butyl phthalate, methyl stearate, Tritolyl Phosphate), ether is (as phenylmethylether, hydroxyl-oxethyl benzene or quinhydrones dibutyl ether), hydrocarbon is (as toluene, dimethylbenzene or diisopropyl benzene), acid amides (as N-butylbenzenesulfonamide or stearyl acid amides), alcohol is (as 2-Ethylhexyl Alcohol, benzylalcohol or phenylethyl alcohol), ketone is (as hydroxy acetophenone, benzophenone or pimelinketone), or the form of mixtures of water-miscible organic solvent recited above.Can carry out this adding with the form of oil droplet, latex, solid dispersion or polymeric dispersions.

Below, with the explanation that provides the dyestuff that comprises at the ink that is used for ink jet printing of the present invention.

Consider anti-jail property or to the anti-jail property of ozone, the oxidizing potential of the dyestuff that adopts among the present invention preferably is higher than 1.0V (SCE relatively), more preferably be higher than 1.1V (SCE relatively), and especially preferably be higher than 1.2V (SCE relatively).As for the type of dyestuff, preferred especially azoic dyestuff or the metal chelate dye that satisfies top described condition is as phthalocyanine pigment.

Those skilled in the art can easily measure oxidizing potential (E _Ox).The method of this measurement for example is described in: P.Delahay, " New Instrumental Methods in Electrochemistry " (Interscience Pulishers, 1954), A.J.Bard etc., " Electrochemical Methods " (JohnWiley ﹠amp; Sons, 1980) and Akira Fujishima etc., " Denki Kagaku Sokuteiho " (Gihodo-Shuppansha, 1984).

More specifically, oxidizing potential by following method and by cyclic voltammetry as measuring with respect to the value of SCE (saturated calomel electrode): with the sample measured with 1 * 10 ^-2To 1 * 10 ^-6Mol is dissolved in the solvent such as dimethyl formamide or acetonitrile that contains supporting electrolyte such as sodium perchlorate or perchloric acid tetrapropylammonium.Because the liquid of sample solution and the potential difference or the liquid resistance of liquid, the deviation of this value can be tens of approximately millivolts, but, can guarantee the reproducibility of current potential by adopting standard model (for example quinhydrones).

In order to limit current potential uniquely, the present invention is by containing 0.1 mole/dm ³The perchloric acid tetrapropylammonium (dye strength is 0.001 mole/dm as the dimethyl formamide of supporting electrolyte ³) in observed value define the oxidizing potential of dyestuff.

Value Eox represents that electronics is passed to the easiness of electrode from sample, and big more value (high more oxidizing potential) expression electronics is difficult to be passed to electrode from sample more, or sample is more difficult oxidized.For the structure of this compound, oxidizing potential is owing to the introducing of electron withdrawing group becomes higher, or owing to the introducing of electron-donating group becomes lower.In the present invention, in order reducing and reactivity, preferably in the dyestuff skeleton, to introduce electron withdrawing group, thereby realize higher oxidizing potential as the ozone of electrophilic reagent.

In dyestuff of the present invention, preferably have the satisfied anti-jail property or the dyestuff that is used to form coloured image of color shades, and preferably have satisfied absorption spectrum by (cut-off) in long wavelength side.For this reason, for example under the situation of yellow dyes, with respect to λ _Max, the I (λ of preferred coloring agent _Max+ 70nm)/I (λ _Max), promptly at λ _MaxAbsorbancy I (λ under the+70nm wavelength _Max+ 70nm) with at λ _MaxAbsorbancy I (λ under the wavelength _Max) ratio be 0.2 or littler, be preferably 0.1 or littler.

On the other hand, the dyestuff that is preferred for forming black image covers spectral range as far as possible widely, and preferably to adopt the half-peak scope be 100nm or bigger dyestuff.

(yellow dyes)

Below, will explain in detail to be used for yellow dyes of the present invention.

Consider anti-jail property or to the anti-jail property of ozone, the oxidizing potential of the yellow dyes that adopts among the present invention preferably is higher than 1.0V (SCE relatively), more preferably be higher than 1.1V (SCE relatively), and especially preferably be higher than 1.15V (SCE relatively).As for the type of dyestuff, the preferred especially azoic dyestuff that satisfies top described condition.

In the present invention, in order reducing and reactivity, preferably in the yellow dyes skeleton, to introduce electron withdrawing group, thereby realize higher oxidizing potential as the ozone of electrophilic reagent.

In dyestuff of the present invention, preferably have the satisfied anti-jail property or the dyestuff of color shades, and end particularly preferably in having satisfied absorption spectrum than long wavelength side.For this reason, the λ of yellow dyes _MaxBe preferably 390 to 470nm, and I (λ _Max+ 70nm)/I (λ _Max), promptly at λ _MaxAbsorbancy I (λ under the+70nm wavelength _Max+ 70nm) with at λ _MaxAbsorbancy I (λ under the wavelength _Max) ratio be 0.20 or littler, more preferably 0.15 or littler, and more preferably 0.10 or littler.Ding Yi absorbing wavelength and absorbancy are the values that obtains in solvent (water of ethyl acetate) herein.

As for the dyestuff that satisfies this oxidizing potential and absorption characteristic, preferably by the dyestuff of following formula (1) expression:

(A ₁₁-N＝N-B ₁₁) _n-L

A wherein ₁₁And B ₁₁Expression can substituted heterocyclic group independently of one another.This heterocycle is preferably 5 yuan or 6 yuan of heterocycles, can have single ring architecture or two or more ring condensed polynuclear planes wherein, and can be aromatics or non-aromatic heterocyclic.Constitute the heterocyclic heteroatoms and be preferably N, O or S atom.N represents to be selected from the integer in 1 and 2, is preferably 2.L represents hydrogen atom, monovalence substituting group, singly-bound or divalent linker.But, represent that at n L represents hydrogen atom or monovalence substituting group, and A under 1 the situation ₁₁And B ₁₁It all is the monovalence heterocyclic group.Represent that at n L represents singly-bound or divalent linker, A under 2 the situation ₁₁Expression monovalence heterocyclic group, and B ₁₁It is divalent heterocyclic group.

Represent that at L L can be bonded to A at an arbitrary position under hydrogen atom or the substituent situation of monovalence ₁₁Or B ₁₁On.Represent at L under the situation of singly-bound or divalent linker that L can be bonded to A at an arbitrary position ₁₁Or B ₁₁On, but preferred combination is to constituting heterocyclic group A ₁₁Or B ₁₁The carbon atom or heteroatoms (preferred nitrogen atom) of ring on.

In the formula recited above (1), by A ₁₁The heterocycle of expression is preferably: 5-pyrazolone, pyrazoles, triazole, azolactone, isoxazolidinone, malonylurea, pyridone, pyridine, rhodanine, pyrazolidinedione, Pyrazolopyridine ketone, Meldrum ' s acid or condensed heterocycle, wherein this heterocycle and aromatic hydrocarbon ring or heterocyclic fused.In these, preferred 5-pyrazolone, 5-amino-pyrazol, pyridone, 2,6-diamino-pyridine or pyrazoloazole coupler (pirazoloazole), preferred especially 5-amino-pyrazol, 2-hydroxyl-6-pyridone and Pyrazolotriazole.

By B ₁₁The heterocycle of expression can be pyridine, pyrazine (pyridine), pyrimidine, pyridazine, triazine, quinoline, isoquinoline 99.9, quinazoline, cinnolines, 2, quinoxaline, pyrroles, indoles, furans, cumarone, thiophene, thionaphthene, pyrazoles, imidazoles, benzoglyoxaline, triazole, oxazole, isoxazole, benzoxazole, thiazole, benzothiazole, isothiazole, benzisothiazole, thiadiazoles, benzoisoxazole, tetramethyleneimine, piperidines, piperazine (piperadine), tetrahydroglyoxaline or thiazoline.In these, preferred pyridine, quinoline, thiophene, thionaphthene, pyrazoles (pirazole), imidazoles, benzoglyoxaline, triazole, oxazole, isoxazole, benzoxazole, thiazole, benzothiazole, isothiazole, benzisothiazole, thiadiazoles or benzoisoxazole, more preferably quinoline, thiophene, pyrazoles, thiazole, benzoxazole, benzoisoxazole, isothiazole, imidazoles, benzothiazole or thiadiazoles, preferred especially pyrazoles, benzothiazole, benzoxazole, imidazoles, 1,2,4-thiadiazoles or 1,3, the 4-thiadiazoles.

A ₁₁And B ₁₁On substituent example comprise halogen atom; alkyl; cycloalkyl; aralkyl; thiazolinyl; alkynyl; aryl; heterocyclic group; cyano group; hydroxyl; nitro; alkoxyl group; aryloxy; siloxy-; heterocyclic oxy group; acyloxy; carbamoyloxy; alkoxy-carbonyl oxy; aryloxycarbonyl oxygen base; amino; amido; amino carbonyl amino; alkoxycarbonyl amino; aryloxycarbonyl amino; sulfamoylamino group; alkyl-or aryl-sulfonamido; sulfydryl; alkylthio; arylthio; the heterocycle thio group; sulfamyl; alkyl-or aryl-sulfinyl; alkyl-or aryl-alkylsulfonyl; acyl group; aryloxycarbonyl; alkoxy carbonyl; formamyl; imino-; phosphino-; phosphinyl; phosphinyl oxygen base; phosphinyl amino; silyl and following ionic hydrophilic group.

The monovalence substituting group of being represented by L can be top described A ₁₁And B ₁₁On substituting group or following ionic hydrophilic group.Equally, the divalent linker of representing by L be alkylidene group, arylidene, heterocycle residue ,-CO-, SO _n-(n is 0,1 or 2) ,-NR-(R represents hydrogen atom, alkyl or aryl) ,-O-or connect the divalent radical that base forms by merging these, and this group can also contain and is used for A ₁₁And B ₁₁Those identical substituting groups or following ionic hydrophilic group.

Dyestuff in the formula (1) preferably contains the negatively charged ion dissociation group in molecule, and this negatively charged ion dissociation group preferably comprises ionic hydrophilic group at least.The example of ionic hydrophilic group comprises sulfo group, carboxyl, phosphono and quaternary ammonium group.Preferred described ionic hydrophilic group is carboxyl, phosphono or sulfo group, particularly carboxyl or sulfo group.Particularly, most preferably at least one is a carboxyl.Described carboxyl, phosphono and sulfo group can be the state of salt, and the counter ion that form this salt can be ammonium ion, alkalimetal ion (for example lithium ion, sodium ion or potassium ion) or organic ion (for example tetramethyl ammonium, tetramethyl guanidine ion or tetramethyl phosphonium ion).In these, most preferably be alkalimetal ion.

In dyestuff by formula (1) expression, preferred part A wherein _I1-N=N-B ₁₁Corresponding to formula (Y2), (Y3) or dyestuff (Y4):

Formula (Y2)

In the formula (Y2), R1 and R3 respectively represent hydrogen atom, cyano group, alkyl, cycloalkyl, aralkyl, alkoxyl group, alkylthio, arylthio, aryl or ionic hydrophilic group; R2 represents hydrogen atom, alkyl, cycloalkyl, aralkyl, formamyl, acyl group, aryl or heterocyclic group; And R4 represents heterocyclic group.

Formula (Y3)

In formula (Y3), R5 represents hydrogen atom, cyano group, alkyl, cycloalkyl, aralkyl, alkoxyl group, alkylthio, arylthio, aryl or ionic hydrophilic group; Za represents-N=,-NH-or-C (R11)=; Zb and Zc represent independently of one another-N=or-C (R11)=; R11 represents hydrogen atom or nonmetal substituting group; And R6 represents heterocyclic group.

Formula (Y4)

In formula (Y4), R7 and R9 independently represent hydrogen atom, cyano group, alkyl, cycloalkyl, aralkyl, aryl, alkylthio, arylthio, alkoxy carbonyl, formamyl or ionic hydrophilic group separately; R8 represents hydrogen atom, halogen atom, alkyl, alkoxyl group, aryl, aryloxy, cyano group, amido, sulfonamido, alkoxyl group carbonyl amino, urea groups, alkylthio, arylthio, alkoxy carbonyl, formamyl, sulfamyl, acyl group, amino, hydroxyl or ionic hydrophilic group; And R10 represents heterocyclic group.

In formula (Y2), (Y3) with (Y4), the alkyl that R1, R2, R3, R5, R7, R8 and R9 represent can be to contain substituent alkyl or unsubstituted alkyl.This alkyl preferably contains the alkyl of 1 to 20 carbon atom.This substituent example comprises hydroxyl, alkoxyl group, cyano group, halogen atom and ionic hydrophilic group.Above the example of described alkyl comprise methyl, ethyl, butyl, sec.-propyl, the tertiary butyl, hydroxyethyl, methoxy ethyl, cyano ethyl, trifluoromethyl, 3-sulfo group propyl group and 4-sulfo group butyl.

The cycloalkyl that R1, R2, R3, R5, R7, R8 and R9 represent can be to contain substituent cycloalkyl and unsubstituted cycloalkyl.This cycloalkyl preferably contains the cycloalkyl of 5 to 12 carbon atoms.This substituent example comprises ionic hydrophilic group.The example of cycloalkyl comprises cyclohexyl.

The aralkyl that R1, R2, R3, R5, R7, R8 and R9 represent can be to contain substituent aralkyl or unsubstituted aralkyl.This aralkyl preferably contains the aralkyl of 7 to 20 carbon atoms.This substituent example comprises ionic hydrophilic group.The example of aralkyl comprises benzyl and 2-styroyl.

The aryl that R1, R2, R3, R5, R7, R8 and R9 represent can be to contain substituent aryl or unsubstituted aryl.This aryl preferably contains the aryl of 6 to 20 carbon atoms.This substituent example comprises alkyl, alkoxyl group, halogen atom, alkylamino, ionic hydrophilic group.The example of aryl comprise phenyl, p-methylphenyl, right-p-methoxy-phenyl, Chloro-O-Phenyl and-(3-sulfo group third amino) phenyl.

The alkylthio that R1, R2, R3, R5, R7, R8 and R9 represent can be to contain substituent alkylthio or unsubstituted alkylthio.This alkylthio preferably contains the alkylthio of 1 to 20 carbon atom.This substituent example comprises ionic hydrophilic group.The example of alkylthio comprises methylthio group and ethylmercapto group.

The arylthio that R1, R2, R3, R5, R7, R8 and R9 represent can be to contain substituent arylthio and unsubstituted arylthio.This arylthio preferably contains the arylthio of 6 to 20 carbon atoms.This substituent example comprises alkyl and ionic hydrophilic group.The example of arylthio comprises thiophenyl and to the toluene sulfenyl.

R2 and the R that explains after a while ²²The heterocyclic group of expression is 5 yuan or 6 yuan of heterocycles preferably, and this heterocycle can also contain the condensed ring structure.Constitute heterocyclic heteroatoms preferably N, S or O.Heterocycle can be aromatic heterocycle or non-aromatic heterocyclic.Heterocycle can further be substituted, and substituent example is identical with the substituting group of above-described aryl.Heterocycle is 6 member heterocyclic ring containing nitrogens preferably, and particularly preferred example comprises triazine, pyrimidine and 2.

The halogen atom that R8 represents can be fluorine atom, chlorine atom or bromine atoms.

The alkoxyl group that R1, R3, R5 and R8 represent can be to contain substituent alkoxyl group or unsubstituted alkoxyl group.This alkoxyl group preferably contains the alkoxyl group of 1 to 20 carbon atom.This substituent example comprises hydroxyl and ionic hydrophilic group.The example of alkoxyl group comprises methoxyl group, oxyethyl group, isopropoxy, methoxy ethoxy, hydroxyl-oxethyl and 3-carboxyl propoxy-.

The aryloxy that R8 represents can be to contain substituent aryloxy or unsubstituted aryloxy.This aryloxy preferably contains the aryloxy of 6 to 20 carbon atoms.This substituent example comprises alkoxyl group and ionic hydrophilic group.The example of aryloxy comprises phenoxy group, to methoxyl group phenoxy group and O-methoxy phenoxy group.The amido that R8 represents can be to contain substituent amido or unsubstituted amido.This amido preferably contains the amido of 2 to 20 carbon atoms.This substituent example comprises ionic hydrophilic group.The example of amido comprises ethanamide, propionic acid amide, benzamide and 3,5-disulfobenzene methane amide.

The sulfonamido that R8 represents can be to contain substituent sulfonamido or unsubstituted sulfonamido.This sulfonamido preferably contains the sulfonamido of 1 to 20 carbon atom.The example of sulfonamido comprises methanesulfonamido and ethanesulfonamido.

The alkoxyl group carbonyl amino that R8 represents can be to contain substituent alkoxyl group carbonyl amino or unsubstituted alkoxyl group carbonyl amino.This alkoxyl group carbonyl amino preferably contains the alkoxyl group carbonyl amino of 2 to 20 carbon atoms.This substituent example comprises ionic hydrophilic group.The example of alkoxyl group carbonyl amino comprises the oxyethyl group carbonyl amino.

The urea groups that R8 represents can be to contain substituent urea groups or unsubstituted urea groups.This urea groups preferably contains the urea groups of 1 to 20 carbon atom.This substituent example comprises alkyl and aryl.The example of urea groups comprises 3-methyl urea groups, 3,3-dimethyl urea groups and 3-phenyl urea groups.

The alkoxy carbonyl that R7, R8 and R9 represent can be to contain substituent alkoxy carbonyl or unsubstituted alkoxy carbonyl.This alkoxy carbonyl preferably contains the alkoxy carbonyl of 2 to 20 carbon atoms.This substituent example comprises ionic hydrophilic group.The example of above-mentioned alkoxy carbonyl comprises methoxycarbonyl and ethoxy carbonyl.

The formamyl that R2, R7, R8 and R9 represent can be to contain substituent formamyl or unsubstituted formamyl.This substituent example comprises alkyl.The example of formamyl comprises methylamino formyl radical and formyl-dimethylamino.

The sulfamyl that R8 represents can be to contain substituent sulfamyl or unsubstituted sulfamyl.This substituent example comprises alkyl.The example of sulfamyl comprises dimethylamino alkylsulfonyl and two-(2-hydroxyethyl) sulfamyl.

The alkylsulfonyl that R8 represents can be alkyl sulphonyl, aryl sulfonyl or heterocycle alkylsulfonyl, and it can also contain substituting group.This substituent example comprises ionic hydrophilic group.The example of alkylsulfonyl comprises methyl sulphonyl and phenyl sulfonyl.

The acyl group that R2 and R8 represent can be to contain substituent acyl group or unsubstituted acyl.This acyl group preferably contains the acyl group of 1 to 20 carbon atom.This substituent example comprises ionic hydrophilic group.The example of acyl group comprises ethanoyl and benzoyl.

The amino that R8 represents can be to contain substituent amino or unsubstituted amino.This substituent example comprises alkyl, aryl and heterocyclic group.Amino example comprises methylamino-, diethylin, anilino and 2-chloroanilino.

The heterocyclic group that R4, R6 and R10 represent can substituted heterocyclic group B with formula (1) ₁₁Identical, and its preferred examples, preferred example and particularly preferred example are also identical.Substituent example comprises that the alkyl that contains 1 to 12 carbon atom, aryl, alkyl-or virtue-sulfenyl, halogen atom, cyano group, sulfamyl, sulfonamido, formamyl and amido, wherein alkyl recited above, aryl etc. can also contain substituting group.

In the superincumbent formula (Y3), Za represents-N=,-NH-or-C (R11)=, Zb and Zc separately independently expression-N=or-C (R11)=, and R11 represents hydrogen atom or nonmetal substituting group.The nonmetal substituting group that R11 represents is cyano group, cycloalkyl, aralkyl, aryl, alkylthio, arylthio or ionic hydrophilic group preferably.Substituting group recited above is similar to each substituting group of being represented by R1 separately, and its preferred examples is also identical.The heterocyclic example that contains is as follows in that formed by two 5 yuan rings and the superincumbent formula (3):

Can also contain in the substituent substituting group above-mentioned, this substituent example can be the A in formula (1) ₁₁And B ₁₁On can substituted those substituting groups.

Dyestuff in formula (Y2) to (Y4) expression preferably contains at least one ionic hydrophilic group in molecule.This dyestuff comprises: any is that the dyestuff of ionic hydrophilic group and the R1 to R11 in its Chinese style (Y2) to (Y4) contain ionic hydrophilic group as substituent dyestuff to R1, R2, R3, R5, R7, R8 and the R9 in its Chinese style (Y2) to (Y4) at least.

In formula (Y2), (Y3) with (Y4), preferred formula (2), and especially preferably by the dyestuff of following formula (Y2-1) expression:

Formula (Y2-1):

In the formula (Y2-1), R ²¹And R ²³Represent hydrogen atom, alkyl, cycloalkyl, aralkyl, alkoxyl group or aryl separately; R ²²Expression hydrogen atom, aryl or heterocyclic group; One of X and Y represent nitrogen-atoms, and another expression-CR ²⁴R ²⁴Expression hydrogen atom, halogen atom, cyano group, alkyl, alkylthio, alkyl sulphonyl, alkyl sulphinyl, alkyl oxy carbonyl, formamyl, alkoxyl group, aryl, arylthio, aryl sulfonyl, aryl sulfonyl kia, aryloxy or amido; And each substituting group can further be substituted.

In the formula (Y2-1), preferably contain the dyestuff of ionic hydrophilic group.

Among the present invention preferred dyestuff be included in Japanese patent application Nos.2002-229222,2003-286844 (based on Japanese patent application No.2002-229222), 2002-211683 and 2002-124832, JP-A Nos.2003-128953 and 2003-41160 described those, and the compound shown in below preferred especially.But, can be used for dyestuff of the present invention and be not limited to these examples.These compounds can synthesize by reference Japanese patent application Nos.2002-229222,2003-286844,2002-211683 and 2002-124832, JP-A Nos.2003-128953,2003-41160,2-24191 and 2001-279145.

Below the specific examples of the preferred coloring agent that adopts among the present invention will be shown in, but the dyestuff that can be used for the present invention is not limited to following specific examples:

The ink that is used for ink jet printing preferably contains 0.2 to 20 quality %, more preferably the above-mentioned yellow dyes of 0.5 to 15 quality %.

(cyan dye)

It is phthalocyanine pigment that the present invention is used for the cyan dye that the composition for ink of ink jet printing uses, particularly by the dyestuff of formula (2) expression.Known phthalocyanine pigment is non-fading dyestuff, but under the situation used as the dyestuff that is used for ink jet printing, known have poor anti-jail property to ozone gas.In the present invention,, preferably electron withdrawing group is introduced in the phthalocyanine frame, thereby obtains being higher than the oxidizing potential of 1.0V (SCE relatively) in order to reduce and reactivity as the ozone of electrophilic reagent.Preferred this oxidizing potential is high as far as possible, more preferably is higher than 1.1V (SCE relatively), and most preferably is higher than 1.15V (SCE relatively).

In the present invention, in order reducing and reactivity, preferably electron withdrawing group to be introduced in the phthalocyanine frame, thereby to obtain higher oxidizing potential as the ozone of electrophilic reagent.Therefore, utilize Hammett substituent constant σ p, this constant is an index of the substituting group electrophilic performance or the sub-performance of powering, and can think the introducing of substituting group such as sulfinyl, alkylsulfonyl or sulfamyl by big σ p value can make oxidizing potential higher.

For the adjusting of this current potential, the preferred especially in the present invention phthalocyanine pigment that adopts by formula (2) expression.

Below, will explain phthalocyanine pigment in detail by formula (2) expression.

In formula (2), X ₂₁, X ₂₂, X ₂₃And X ₂₄Expression-SO-Z independently of one another ₂,-SO ₂-Z ₂,-SO ₂NR ₂₁R ₂₂, sulfo group ,-CONR ₂₁R ₂₂Or-SO ₂NR ₂₁In these substituting groups, preferred-SO-Z ₂,-SO ₂-Z ₂,-SO ₂NR ₂₁R ₂₂With-CONR ₂₁R ₂₂, and especially preferably-SO ₂-Z ₂With-SO ₂NR ₂₁R ₂₂, most preferably-SO ₂-Z ₂A at expression substituting group number ₂₁To a ₂₄Any one be 2 or bigger situation under, the X that in a plurality of unit, exists ₂₁To X ₂₄In any one can be identical or different mutually, it represents any of group recited above independently of one another.In addition, X ₂₁, X ₂₂, X ₂₃And X ₂₄Can all be identical substituting group, perhaps can be the substituting group of same type but partly different mutually, for example such situation, wherein X ₂₁, X ₂₂, X ₂₃And X ₂₄All be-SO ₂-Z ₂, but contain different Z ₂, and can comprise mutually different substituting groups (for example ,-SO ₂-Z ₂With-SO ₂NR ₂₁R ₂₂).

Z ₂Each represents alkyl, cycloalkyl, thiazolinyl, aralkyl, aryl or heterocyclic group independently, it can further be substituted, preferably it is replacement or unsubstituted alkyl, replacement or unsubstituted aryl or replacement or unsubstituted heterocyclic group, in these, the heterocyclic group of the aryl of the alkyl of Qu Daiing, replacement or replacement most preferably.

R ₂₁And R ₂₂Represent hydrogen atom, alkyl, cycloalkyl, thiazolinyl, aralkyl, aryl or heterocyclic group independently of one another, it can further be substituted.In these, preferred hydrogen atom, replacement or unsubstituted alkyl or replacement or unsubstituted aryl or replacement or unsubstituted heterocyclic group, and further preferred hydrogen atom, the alkyl of replacement, the aryl of replacement or the heterocyclic group of replacement.But, not preferred R ₂₁And R ₂₂It all is hydrogen atom.

By R ₂₁, R ₂₂And Z ₂The alkyl that the replacement of expression or unsubstituted alkyl preferably contain 1 to 30 carbon atom.Particularly, for the solvability of improving dyestuff and the stability of ink, preferred branched-chain alkyl, and preferably include the situation (use of racemic modification) of asymmetric carbon especially.Substituent example be with at the Z that explains after a while ₂, R ₂₁, R ₂₂, Y ₂₁, Y ₂₂, Y ₂₃Or Y ₂₄Can also contain identical those of substituting group under the substituent situation.Particularly, thereby for the association that improves dyestuff improves anti-jail property, preferred hydroxyl, ether, ester group, cyano group, amide group or sulfamyl.In addition, can also comprise halogen atom or ionic hydrophilic group.The carbonatoms of alkyl does not comprise substituent carbon atom, and this also is applied to other group.

By R ₂₁, R ₂₂And Z ₂The cycloalkyl that the replacement of expression or unsubstituted cycloalkyl preferably contain 5 to 30 carbon atoms.Particularly, for the solvability of improving dyestuff and the stability of ink, preferably include the situation (use of racemic modification) of asymmetric carbon especially.Substituent example be with at the Z that explains after a while ₂, R ₂₁, R ₂₂, Y ₂₁, Y ₂₂, Y ₂₃Or Y ₂₄Can also contain identical those of substituting group under the substituent situation.Particularly, thereby for the association that improves dyestuff improves anti-jail property, preferred hydroxyl, ether, ester group, cyano group, amide group or sulfamyl.In addition, can also comprise halogen atom or ionic hydrophilic group.

By R ₂₁, R ₂₂And Z ₂The thiazolinyl that the replacement of expression or unsubstituted thiazolinyl preferably contain 2 to 30 carbon atoms.Particularly, for the solvability of improving dyestuff and the stability of ink, preferred branched-chain alkenyl, and preferably include the situation (use of racemic modification) of asymmetric carbon especially.Substituent example be with at the Z that explains after a while ₂, R ₂₁, R ₂₂, Y ₂₁, Y ₂₂, Y ₂₃Or Y ₂₄Can also contain identical those of substituting group under the substituent situation.Particularly, thereby for the association that improves dyestuff improves anti-jail property, preferred hydroxyl, ether, ester group, cyano group, amide group or sulfamyl.In addition, can also comprise halogen atom or ionic hydrophilic group.

By R ₂₁, R ₂₂And Z ₂The aralkyl that the replacement of expression or unsubstituted aralkyl preferably contain 7 to 30 carbon atoms.Particularly, for the solvability of improving dyestuff and the stability of ink, preferred branched aralkyl groups, and preferably include the situation (use of racemic modification) of asymmetric carbon especially.Substituent example be with at the Z that explains after a while ₂, R ₂₁, R ₂₂, Y ₂₁, Y ₂₂, Y ₂₃Or Y ₂₄Can also contain identical those of substituting group under the substituent situation.Particularly, thereby for the association that improves dyestuff improves anti-jail property, preferred hydroxyl, ether, ester group, cyano group, amide group or sulfamyl.In addition, can also comprise halogen atom or ionic hydrophilic group.

By R ₂₁, R ₂₂And Z ₂The aryl that the replacement of expression or unsubstituted aryl preferably contain 6 to 30 carbon atoms.Substituent example be with at the Z that explains after a while ₂, R ₂₁, R ₂₂, Y ₂₁, Y ₂₂, Y ₂₃Or Y ₂₄Can also contain identical those of substituting group under the substituent situation.Particularly, preferred electron withdrawing group because it has realized the dyestuff of high oxidation potential, thereby has improved anti-jail property.Electron withdrawing group can be Hammett substituent constant σ p on the occasion of substituting group.In this substituting group; further preferred halogen atom, heterocyclic group, cyano group, carboxyl, amido, sulfoamido, sulfamyl, formamyl, alkylsulfonyl, imide, acyl group, sulfo group or quaternary ammonium group, further preferred cyano group, carboxyl, sulfamyl, formamyl, alkylsulfonyl, imide, acyl group, sulfo group or quaternary ammonium group.

By R ₂₁, R ₂₂And Z ₂The heterocyclic group of expression is 5 yuan or 6 yuan of heterocycles preferably, and it can also contain the condensed ring structure.It can be aromatics or non-aromatic heterocyclic.Below, provided by R with the heterocycle form of not indicating the position of substitution ₂₁, R ₂₂And Z ₂The example of the heterocyclic group of expression, and to the position of substitution without limits, for example, pyridine can replace at 2-, 3-or 4-position.Example comprises: pyridine, pyrazine (pyradine), pyrimidine, pyridazine, triazine, quinoline, isoquinoline 99.9, quinazoline, cinnolines, 2, quinoxaline, pyrroles, indoles, furans, cumarone, thiophene, thionaphthene, pyrazoles, imidazoles, benzoglyoxaline, triazole, oxazole, isoxazole, benzoxazole, thiazole, benzothiazole, isothiazole, benzisothiazole, thiadiazoles, isoxazole, benzoisoxazole, tetramethyleneimine, piperidines, piperazine (piperadine), tetrahydroglyoxaline and thiazoline.Wherein preferred aromatic heterocycle, and its preferred examples, shown in mode same as described above, comprise pyridine, pyrazine (pyradine), pyrimidine, pyridazine, triazine, pyrazoles, imidazoles, benzoglyoxaline, triazole, thiazole, benzothiazole, isothiazole, benzisothiazole and thiadiazoles.These can contain substituting group, and substituent example be with at the Z that explains after a while ₂, R ₂₁, R ₂₂, Y ₂₁, Y ₂₂, Y ₂₃Or Y ₂₄Can also contain identical those of substituting group under the substituent situation.Preferred substituted is identical with above-mentioned preferred substituted for aryl, and more preferred substituents is identical with above-mentioned more preferred substituents for aryl.

Y ₂₁, Y ₂₂, Y ₂₃And Y ₂₄Represent hydrogen atom independently of one another; halogen atom; alkyl; cycloalkyl; thiazolinyl; aralkyl; aryl; heterocyclic group; cyano group; hydroxyl; nitro; amino; alkylamino; alkoxyl group; aryloxy; amido; virtue is amino; urea groups; sulfamoylamino group; alkylthio; arylthio; alkoxycarbonyl amino; sulfoamido; formamyl; sulfamyl; alkylsulfonyl; alkoxy carbonyl; heterocyclic oxy group; azo-group; acyloxy; carbamyl amino; siloxy-; aryloxycarbonyl; aryloxycarbonyl amino; imide; the heterocycle sulfenyl; phosphoryl; acyl group; carboxyl or sulfo group, its each can further have substituting group.

In these; preferred hydrogen atom, halogen atom, alkyl, aryl, cyano group, alkoxyl group, amide group, urea groups, sulfoamido, formamyl, sulfamyl, alkoxy carbonyl, carboxyl or sulfo group; preferred especially hydrogen atom, halogen atom, cyano group, carboxyl or sulfo group, and hydrogen atom most preferably.

Z ₂, R ₂₁, R ₂₂, Y ₂₁, Y ₂₂, Y ₂₃Or Y ₂₄, can also contain under the situation of substituent group in expression, can also contain following substituting group.

Example comprises: contain 1 to 12 carbon atom the straight or branched alkyl, contain 7 to 18 carbon atoms the straight or branched aralkyl, contain 2 to 12 carbon atoms the straight or branched thiazolinyl, contain the straight or branched alkynyl of 2 to 12 carbon atoms and contain the straight or branched cycloalkyl of 3 to 12 carbon atoms and contain the straight or branched cycloalkenyl group of 3 to 12 carbon atoms that (group recited above preferably contains side chain, with the solvability of improving dyestuff and the stability of ink, and especially preferably contain asymmetric carbon; The specific examples of group recited above comprises: methyl; ethyl; propyl group; sec.-propyl; sec-butyl; the tertiary butyl; the 2-ethylhexyl; 2-methyl sulphonyl ethyl; the 3-phenoxy propyl; trifluoromethyl and cyclopentyl); halogen atom (as chlorine atom or bromine atoms); aryl is (as phenyl; 4-tert-butyl-phenyl or 2; the 4-di-tert-pentyl-phenyl); heterocyclic group is (as imidazolyl; pyrazolyl; triazolyl; the 2-furyl; the 2-thienyl; 2-pyrimidyl and 2-[4-morpholinodithio base); cyano group; hydroxyl; nitro; carboxyl; amino; alkoxyl group is (as methoxyl group; oxyethyl group; 2-methoxy ethoxy or 2-methylsulfonyl oxyethyl group); aryloxy is (as phenoxy group; the 2-methylphenoxy; 4-tertiary butyl phenoxy group; the 3-nitro-phenoxy; 3-tert.-butoxy carbamyl phenoxyl or 3-methoxyl group formamyl); amido is (as acetamido; benzoylamino or 4-(3-tertiary butyl-4-hydroxy phenoxy group) butyramide); alkylamino is (as methylamino-; fourth amino; diethylin or methyl fourth amino); anilino (as phenyl amino or 2-chloroanilino); urea groups is (as the phenyl urea groups; methyl urea groups or N; N-dibutyl urea groups); sulfamoylamino group is (as N; N-dipropyl sulfamoylamino group); alkylthio is (as methylthio group; hot sulfenyl or 2-phenoxy group ethylmercapto group); arylthio is (as thiophenyl; 2-butoxy-uncle's octyl group thiophenyl or 2-carboxyl thiophenyl); alkoxycarbonyl amino (as methoxycarbonyl amino); sulfoamido is (as the methylsulfonyl amido; benzene sulfonamido or tolysulfonyl amido); formamyl is (as N-ethylamino formyl radical or N; N-dibutylamino formyl radical); sulfamyl is (as N-ethyl sulfamyl; N; N-dipropyl sulfamyl or N-phenyl sulfamoyl base); alkylsulfonyl is (as methylsulfonyl; hot alkylsulfonyl; benzenesulfonyl or tosyl group); alkoxy carbonyl (as methoxycarbonyl or butoxy carbonyl); heterocyclic oxy group (as 1-phenyltetrazole-5-oxygen base or 2-THP trtrahydropyranyl oxygen base); azo-group is (as phenylazo-; 4-p-methoxy-phenyl azo-group; 4-pivalyl aminophenyl azo-group or 2-hydroxyl-4-propionyl phenylazo); acyloxy (as acetoxyl group); formamyl oxygen base (as N-methylamino formyl radical oxygen base or N-phenyl amino formyl radical oxygen base); siloxy-(trimethylsiloxy or dibutylmethyl siloxy-); aryloxycarbonyl amino (as phenyloxycarbonyl amino); imide (as N-succinimide or N phlhalimide); the heterocycle sulfenyl is (as 2-[4-morpholinodithio base sulfenyl; 2; 4-hexichol Oxy-1; 3; 5-triazole-6-sulfenyl or 2-pyridyl sulfenyl); sulfinyl (as 3-phenoxy propyl sulfinyl); phosphono is (as the phenoxy group phosphono; octyloxy phosphono or Phenylphosphine acyl group); aryloxycarbonyl (as phenyloxycarbonyl); acyl group is (as ethanoyl; 3-phenyl propionyl or benzoyl) and ionic hydrophilic group (as carboxyl; sulfo group; phosphono or quaternary ammonium group).

At the phthalocyanine pigment by following formula (2) expression is under the water miscible situation, and preferably it contains ionic hydrophilic group.Ionic hydrophilic group comprises sulfo group, carboxyl, phosphono and quaternary ammonium group.The preferred ion hydrophilic group is carboxyl, phosphono or sulfo group, and is preferably carboxyl or sulfo group especially.Carboxyl, phosphono or sulfo group can be the states of salt, and the counter ion that constitute this salt comprise ammonium ion, alkalimetal ion (as lithium ion, sodium ion or potassium ion) and organic cation (as tetramethylammonium ion, tetramethyl guanidine ion or tetramethyl phosphonium ion).In these counter ion, preferred as alkali ion, and solvability and the stability of ink, preferred lithium ion especially in order to improve dyestuff.Most preferred ionic hydrophilic group is the lithium salts of sulfo group.

As for the quantity of ionic hydrophilic radical, preferred phthalocyanine pigment comprises at least two such groups in molecule, and more preferably comprises at least two sulfo groups and/or carboxyl.

In the formula (2), a ₂₁To a ₂₄And b ₂₁To b ₂₄Represent substituent X respectively ₂₁To X ₂₄And Y ₂₁To Y ₂₄Number.a ₂₁To a ₂₄Represent 0 to 4 integer independently of one another, but they do not get 0 simultaneously.b ₂₁To b ₂₄Represent 0 to 4 integer independently of one another.At a ₂₁To a ₂₄And b ₂₁To b ₂₄Any one expression is equal to or greater than under the situation of 2 integer, X ₂₁To X ₂₄And Y ₂₁To Y ₂₄Any one exist with a plurality of unit forms, it can be identical or different.

a ₂₁And b ₂₁Satisfy and concern a ₂₁+ b ₂₁=4, wherein preferred especially a ₂₁Expression 1 or 2 and b ₂₁Expression 3 or 2 combination, and a most preferably ₂₁Expression 1 and b ₂₁The combination of expression 3.

a ₂₂And b ₂₂, a ₂₃And b ₂₃And a ₂₄And b ₂₄Combination have and a ₂₁And b ₂₁Combination in identical relation, and preferred combination is also identical.

M represents hydrogen atom, atoms metal, metal oxide, metal hydroxides or metal halide.

Preferred M is hydrogen atom, metallic element such as Li, Na, K, Mg, Ti, Zr, V, Nb, Ta, Cr, Mo, W, Mn, Fe, Co, Ni, Ru, Rh, Pd, Os, Ir, Pt, Cu, Ag, Au, Zn, Cd, Hg, Al, Ga, In, Si, Ge, Sn, Pb, Sb or Bi, or oxide compound such as VO or GeO.

The preferred embodiment of oxyhydroxide comprises: Si (OH) ₂, Cr (OH) ₂And Sn (OH) ₂

In addition, halid example comprises: AlCl, SiCl ₂, VCl, VCl ₂, VOCl, FeCl, GaCl and ZrCl.

In these, preferred Cu, Ni, Zn, Al etc., and Cu most preferably.

In addition, in the phthalocyanine pigment by formula (2) expression, phthalocyanine ring (Pc) can pass through L (divalent linker) and form dimer (for example Pc-M-L-M-Pc) or tripolymer, and a plurality of M in this case can be same to each other or different to each other.

In this case, the divalent linker of being represented by L is preferably oxygen base-O-, sulfenyl-S-, carbonyl-CO-, alkylsulfonyl-SO ₂-, imino--NH-, methylene radical-CH ₂-or by merging the group that these groups form.

As for substituent preferably combination in by the compound of formula (2) expression, preferably: wherein various substituent at least one be the compound of preferred group recited above, more preferably: wherein various substituent greater amounts are compounds of preferred group recited above, and most preferably: wherein all substituting groups are compounds of preferred group recited above.

In the phthalocyanine pigment by formula (2) expression, more preferably by the phthalocyanine pigment of the structure of following formula (5) expression.Below, will explain phthalocyanine pigment in detail by formula (5) expression.

In the formula (5), X ₅₁To X ₅₄Has the X in the formula (2) respectively ₂₁To X ₂₄Identical implication, and have identical preferred embodiment.Y ₅₁And Y ₅₂Has the Y in the formula (2) ₂₁Identical implication, and have identical preferred embodiment.Y ₅₃And Y ₅₄Has the Y in the formula (2) ₂₂Identical implication, and have identical preferred embodiment.Y ₅₅And Y ₅₆Has the Y in the formula (2) ₂₃Identical implication, and have identical preferred embodiment.Y ₅₇And Y ₅₈Has the Y in the formula (2) ₂₄Identical implication, and have identical preferred embodiment.In addition, M ₁Have the identical implication of M in the formula (2), and have identical preferred embodiment.

In the formula (5), a ₅₁To a ₅₄Represent integer 1 or 2 independently of one another, the preferred satisfied 4≤a that concerns ₅₁+ a ₅₂+ a ₅₃+ a ₅₄≤ 6.The preferred especially satisfied a51=a that concerns ₅₂=a ₅₃=a ₅₄=1.

X ₅₁, X ₅₂, X ₅₃And X ₅₄Can all be identical substituting group, perhaps can be the substituting group of same type but partly different mutually, for example such situation, wherein X ₅₁, X ₅₂, X ₅₃And X ₅₄All be-SO ₂-Z ₅, but contain different Z ₅, and can comprise that mutually dissimilar substituting groups is as-SO ₂-Z ₅With-SO ₂NR ₅₁R ₅₂

In the phthalocyanine pigment by formula (5) expression, particularly preferred substituting group combination is as follows:

X ₅₁To X ₅₄Independently of one another and preferred expression-SO-Z ₅,-SO ₂-Z ₅,-SO ₂NR ₅₁R ₅₂With-CONR ₅₁R ₅₂, and especially preferably-SO ₂-Z ₅With-SO ₂NR ₅₁R ₅₂, most preferably-SO ₂-Z ₅

Z ₅Preferred expression replacement or unsubstituted alkyl, replacement or unsubstituted aryl or replacement or unsubstituted heterocyclic group, in these, the heterocyclic group of the aryl of the alkyl of Qu Daiing, replacement or replacement most preferably.Particularly, for the solvability of improving dyestuff and the stability of ink, particularly preferably in the situation that contains asymmetric carbon in the substituting group (use of racemic modification).Particularly, thus for the association that improves dyestuff improves anti-jail property, have the situation of hydroxyl, ether, ester group, cyano group, amide group or sulfoamido in the preferred substituents.

R ₅₁And R ₅₂Represent hydrogen atom, replacement or unsubstituted alkyl or replacement or unsubstituted aryl or replacement or unsubstituted heterocyclic group independently of one another and preferably, be preferred, and the alkyl of more preferably hydrogen atom, replacement, the aryl of replacement or the heterocyclic group of replacement.But, not preferred R ₅₁And R ₅₂It all is hydrogen atom.For the solvability of improving dyestuff and the stability of ink, particularly preferably in the situation that contains asymmetric carbon in the substituting group (use of racemic modification).Particularly, thus for the association that improves dyestuff improves anti-jail property, have the situation of hydroxyl, ether, ester group, cyano group, amide group or sulfoamido in the preferred substituents.

Y ₅₁To Y ₅₈Expression independently of one another and preferred hydrogen atom, halogen atom, alkyl, aryl, cyano group, alkoxyl group, amide group, urea groups, sulfoamido, formamyl, sulfamyl, alkoxy carbonyl, carboxyl or sulfo group; preferred especially hydrogen atom, halogen atom, cyano group, carboxyl or sulfo group, and hydrogen atom most preferably.

a ₅₁To a ₅₄Represent 1 or 2 independently of one another and preferably, and especially preferably all be 1.

M ₁Expression hydrogen atom, metallic element, metal oxide, metal hydroxides or metal halide, preferred Cu, Ni, Zn or Al, and preferred especially Cu.

At the phthalocyanine pigment by formula (5) expression is under the water miscible situation, and preferably it contains ionic hydrophilic group.Ionic hydrophilic group comprises sulfo group, carboxyl, phosphono and quaternary ammonium group.The preferred ion hydrophilic group is carboxyl, phosphono or sulfo group, and is preferably carboxyl or sulfo group especially.Carboxyl, phosphono or sulfo group can be the states of salt, and the counter ion that constitute this salt comprise ammonium ion, alkalimetal ion (as lithium ion, sodium ion or potassium ion) and organic cation (as tetramethylammonium ion, tetramethyl guanidine ion or tetramethyl phosphonium ion).In these counter ion, preferred as alkali ion, and solvability and the stability of ink, preferred lithium ion especially in order to improve dyestuff.Most preferred ionic hydrophilic group is the lithium salts of sulfo group.

As for the quantity of ionic hydrophilic radical, preferred phthalocyanine pigment comprises at least two such groups in molecule, and more preferably comprises at least two sulfo groups and/or carboxyl.

As for substituent preferably combination in by the compound of formula (5) expression, preferably: wherein various substituent at least one be the compound of preferred group recited above, more preferably: wherein various substituent relatively large be the compound of preferred group recited above, and most preferably: wherein all substituting groups are compounds of preferred group recited above.

Chemical structure as for the compound of representing by formula (5); in preferably being introduced in four phenyl ring of phthalocyanine each to major general's electron withdrawing group such as sulfinyl, alkylsulfonyl and sulfamyl, the mode of introducing makes that total σ p value of replacement of whole phthalocyanine frame is 1.6 or higher.

Now, the explanation of Hammett substituent constant σ p will be provided.Hammett's rule is the thumb rule that is proposed in nineteen thirty-five by the LP. Hammett, and purpose is to discuss quantitatively reaction or the equilibrated influence of substituting group to benzene derivative, and this thumb rule is extensively admitted at present.Substituent constant based on Hammett's rule comprises σ p and σ m, these values are described in many reference, for example at J.A.Dean, " Lange ' s Handbook of Chemistry ", the 12nd edition, 1979 (McGraw-Hill), " Kagaku no Ryoiki ", Zoukan, 122, the 96-103 page or leaf, 1979 (Nankodo).Among the present invention, limit or describe each substituting group by Hammett substituent constant σ p, but this description is not limited to the substituting group that its constant is known in the above referred-to references, even will fall into the substituting group of suitable scope in according to the measurement of Hammett's rule but its constant is not described in reference.In addition, the dyestuff that adopts among the present invention comprises following those: it is not the derivative of benzene, but σ p is used as the index of the substituent electronic efficiency of indication, and has nothing to do with the position of substitution.Among the present invention, σ p is described by the implication of explaining above.

By the phthalocyanine pigment of formula (2) the expression mixture of congener normally, in congener, substituent X n (n=21 to 24) is different in the position of introducing with quantitative aspects with Ym (m=21 to 24) owing to its synthetic method inevitably, and the mixture of this congener of this formula ordinary representation statistical average.The present invention is based on following discovery: be divided into following three types by the mixture with this congener, a preferred especially particular mixtures.More specifically, according to the position of substitution, will be divided into following three types by the mixture of the congener of the phthalocyanine pigment of formula (2) and formula (5) expression, wherein with Y ₅₁, Y ₅₂, Y ₅₃, Y ₅₄, Y ₅₅, Y ₅₆, Y ₅₇And Y ₅₈Be defined as 1-, 4-, 5-, 8-, 9-, 12-, 13-and 16-position respectively:

(1) β-position replaces type: the phthalocyanine pigment that specified substituent is arranged on 2-and/or 3-position, 6-and/or 7-position, 10-and/or 11-position and 14-and/or 15-position.

(2) alpha-position replaces type: the phthalocyanine pigment that specified substituent is arranged on 1-and/or 4-position, 5-and/or 8-position, 9-and/or 12-position and 13-and/or 16-position.

(3) α, β-position replaces type: the phthalocyanine pigment that does not have to have regularly specified substituent on 1-to 16-position.

In the present invention, β recited above-position replaces type, alpha-position replaces type and α, and β-position replaces the derivative that type will be used to explain structure difference (particularly the position of substitution is different) phthalocyanine pigment.

Used phthalocyanine pigment can be by Shirai and the Kobayashi that for example publishes in IPC company among the present invention, " Phthalocyanine-Chemistryand Function-" (1-62 page or leaf), with C.C.Leznoff and the A.B.P.Lever that VCH publishes, combined method or the similar approach describing in " Phthalocyanines-Properties andApplications " (1-54 page or leaf) or quote are synthesized.

For example WO Nos.00/17275,00/08103,00/08101 and 98/41853 and JP-A No.10-36471 described in, sulfonation reaction, sulfonating chlorinating reaction and amidate action by substituted phthalocyanine compound not can synthesize the phthalocyanine compound of the present invention by formula (2) expression.In this case, sulfurization can occur on arbitrary position of phthalocyanine nucleus, and is difficult to control sulfonated quantity.Therefore, under such reaction conditions, introduce sulfo group and can not limit the position and the quantity of the sulfo group of introducing, and the mixture of the different congener of substituting group quantity or the position of substitution is provided inevitably.Therefore; utilizing this mixture as in raw material synthetic; can not be limited to quantity or the position of substitution of the sulfamyl on the heterocycle, and the phthalocyanine pigment that obtains is as containing α, substituting group quantity some compound different with the position of substitution of β-position mixing substituted type obtains.

As mentioned above, the introducing of introducing a large amount of electron withdrawing groups such as sulfamyl in phthalocyanine nucleus provides higher oxidizing potential, thereby has improved ozone resistants.Described in the above synthetic in, the quantity that has the electron withdrawing group of introducing inevitably still less, i.e. the lower phthalocyanine pigment of oxidizing potential.Therefore, in order to improve ozone resistants, more preferably adopt the synthetic method of the formation of can the inhibited oxidation current potential lower compound.

The present invention for example can derive from four sulfo group phthalocyanine compounds by the phthalocyanine compound of formula (5) expression, described four sulfo group phthalocyanine compounds are by the O-phthalic carbonitrile derivatives (Compound P) that is expressed from the next and/or diimino isoindoline derivative (compound Q) and the metal derivative reaction of being represented by formula (6), perhaps obtain by following formula 4-sulfo group O-phthalic carbonitrile derivatives of representing (compound R) and the metal derivative reaction of being represented by formula (6).

Compound P compound Q compound R

In these formulas, Xp is equivalent to the X in the formula (5) ₅₁, X ₅₂, X ₅₃Or X ₅₄Y _qAnd Y _q' correspond respectively to the Y in the formula (5) ₅₁, Y ₅₂, Y ₅₃, Y ₅₄, Y ₅₅, Y ₅₆, Y ₅₇Or Y ₅₈And the M ' in compound R represents positively charged ion.

M ' positively charged ion is represented alkalimetal ion such as Li, Na and K, or organic cation such as triethyl ammonium ion and pyridinium ion.

Formula (6): M-(Y) d

In formula (6), the M in M in M and the formula (2) or the formula (5) ₁Has identical implication; Y represents monovalence or divalence part, as halogen atom, and acetic acid anion, methyl ethyl diketone acid ion or oxygen; And d represents 1 to 4 integer.

Above-mentioned synthetic method can be introduced the required substituting group of specific quantity.Under as the situation of a large amount of electron withdrawing groups of the introducing among the present invention with the acquisition high oxidation potential, this synthetic method that is much better than the phthalocyanine compound of above-mentioned synthesis type (2).

So obtain by the represented phthalocyanine compound of formula (5) normally by the mixture of following formula (a)-1 to the compound of (a)-4 expression, these compounds are the isomer among the position of substitution Xp, i.e. β-position replacement type.

Formula (a)-1 formula (a)-2

Formula (a)-3 formula (a)-4

In above-mentioned synthesizing,, can obtain β-position and replace type phthalocyanine pigment, wherein X by adopting all identical Xp ₅₁, X ₅₂, X ₅₃And X ₅₄It is identical substituting group.On the other hand, adopt different Xp, can synthesize the substituting group that contains identical type but the substituting group different dyestuff of part each other, or contain the substituent dyestuff of the kind that differs from one another by combination.In dyestuff by formula (5) expression, especially preferably contain this class dyestuff of different mutually electron-withdrawing substituents, because it can regulate the solubleness or the association performance of dyestuff, and the time stability of ink.

In the present invention, find that replace in the type at all, the oxidizing potential that is higher than 1.0V (with respect to SCE) is very important for improving fastness, and the importance that should act on fully can not be from above-mentioned background technological prediction.In addition, although reason is still unknown in detail, β-position replaces type and obviously is better than α at aspects such as tone, the anti-jail property of light, ozone resistantss, and β-position is mixed and replaced type.

Below show specific examples (exemplifying Compound I-1), but the phthalocyanine pigment of the present invention's use not will be understood that and is confined to these examples to I-12 and 101-190 by the phthalocyanine pigment of formula (2) and (5) expression:

Compound 146-190 is by M-Pc (X _P1) _m(X _P2) _nThe phthalocyanine compound of expression has following structure:

X independently of one another wherein _P1=X _P1Or X _P2

According to above-mentioned references, can synthesize phthalocyanine pigment by formula (2) expression.In addition, except above-mentioned synthetic method, can be by the phthalocyanine pigment of formula (5) expression according to synthesizing in method described in JP-A Nos.2001-226275,2001-96610,2001-47013 and the 2001-193638.Starting material, dyestuff intermediate and synthetic method be not limited to recited above those.

Among the present invention, the phthalocyanine pigment of being represented by formula (2) can use separately, and perhaps with another kind of dyestuff, particularly another kind of phthalocyanine pigment is used in combination.This being used in combination can be realized by dyestuff of the present invention is mixed with another kind of phthalocyanine pigment, but can be when the dyestuff of formula (5) synthetic, mix with O-phthalic carbonitrile derivatives (Compound P) and diimino isoindoline derivative (compound Q) by the similar compound that will not have substituent X p and to prepare phthalocyanine, thus at this mixture that obtains when synthetic.

The content of phthalocyanine pigment in ink by formula (2) expression is preferably 0.2 to 20 quality %, more preferably 0.5 to 15 quality %.

(magenta dye)

The dyestuff that incarnadines that adopts among the present invention preferably has maximum absorption and has the azoic dyestuff that is higher than 1.0V (with respect to SCE) oxidizing potential in the spectral range of 500-580nm in aqueous medium.As explaining in the above, preferred oxidizing potential is high as much as possible, and more preferably is higher than 1.1V (with respect to SCE), and further preferably is higher than 1.15V (with respect to SCE).

This first preferred coloring agent constitutional features that has as the azoic dyestuff of magenta dye is: contain the chromophore that is expressed from the next: (heterocycle A)-N=N-(heterocycle B).In this case, heterocycle A and B can have same structure.Each is selected from the 5-or the 6-unit heterocycle of and the following naturally heterocycle A and B: pyrazoles, imidazoles, triazole, oxazole, thiazole, selenazoles, pyridone, pyrazine, pyrimidine and pyridine.Specific examples is described in for example Japanese patent application Nos.2000-15853 and 2001-15614, among JP-ANo.2002-309116 and the Japanese patent application No.2001-195014.

In addition, second preferred structure of azoic dyestuff is characterised in that: azo group directly is connected on its at least one side, and wherein the nitrogenous 6 yuan of heterocycles of aromatics are as the coupling composition, and specific examples is described in Japanese patent application No.2001-110457.

The 3rd preferred structure is characterised in that: auxochromous group has aromatic ring amino or heterocyclic amino group structure, particularly anilino or assorted amino (heterylamino).

The 4th preferred structure is characterised in that: the existence of three-dimensional arrangement, it specifically describes in Japanese patent application No.2002-12015.

Providing constitutional features recited above to azoic dyestuff can improve the oxidizing potential of dyestuff and improve ozone resistants.The means that are used to improve oxidizing potential can be the eliminations of even oxygen dyestuff α-hydrogen.Consider the raising oxidizing potential, the azoic dyestuff of formula (3) also is preferred.The means that are used for improving oxidizing potential are described in Japanese patent application No.2001-254878.

The λ max (wavelength of maximum absorption) of magenta ink that utilization of the present invention has the even oxygen dyestuff of top described feature presses tintometer preferably in 500 to 580nm scope, and longer wavelength survey and shorter wavelength side in maximum absorption have little half-peak width, promptly sharp-pointed absorption.Specific descriptions award among the Japanese patent application No.2002-309133.Can also obtain more sharp-pointed absorption by the azoic dyestuff of employing formula (3) and at its alpha-position introducing methyl.

In addition, the fuchsin gas that utilizes this azoic dyestuff is preferably 5.0 * 10 to the pressure fading rate constant of ozone gas ^-2[hour ^-1] or lower, more preferably 3.0 * 10 ^-2[hour ^-1] or lower, and be preferably 1.5 * 10 especially ^-2[hour ^-1] or lower.

In measurement for the pressure fading rate constant of ozone gas, be in the image of 0.90-1.10 by only on the reflected image receiver media, printing reflection density that magenta ink obtains and that measure by state A spectral filter, the painted areas of the color of the principal spectrum absorption region of magenta ink is selected as the initial density point, and this initial density is got do beginning density (=100%).In the face of in the trier of ozone this image is faded, described trier keeps the ozone concn of 5mg/L unchangeably, the needed time when reaching 80% density of initial density with mensuration, and fade density and the relation between the time of supposition follow first order reaction speed equation, determine this time inverse [hour ^-1], and it is got make the fading rate constant.

The printing sheet that is used to test can be to be printed on the printing sheet of black square sign, a kind of gradient color chips of Macbeth chart according to JIS code 2223, or a kind of any gradient density of measuring the zone that can provide is printed sheet.

The reflection density of the reflection density of printing for measurement (gradient color chips) is the density of surveying by state A spectral filter in the densometer that meets international standard ISO5-4 (how much states of reflection density).

The testing laboratory that is used to measure to the pressure fading rate constant of ozone gas is equipped with ozonizer (as the high-voltage release type, be used for dry air is applied alternating current voltage), this ozonizer can maintain 5mg/L unchangeably with inner concentration of ozone gas, and Exposure Temperature is remained on 25 ℃.

This pressure fading rate constant is the complexity of having indicated by oxidizing atmosphere oxidation in the environment, oxidizing atmosphere such as photo-chemical smog, vehicle exhaust, from gas that produces in the organic steam of furniture coatingsurface or carpet and the photo frame in the daylight room etc., wherein represent this oxidizing atmosphere by ozone gas.

Having the magenta dye that advantageously adopts among feature recited above and the present invention is to comprise 5 yuan of heterocycles and the nitrogenous 6 yuan of heterocyclic azoic dyestuffs of aromatics, and the dyestuff of preferably being represented by formula (3).Below, will explain dyestuff by formula (3) expression.

In the formula (3), A ₃₁Represent 5 yuan of heterocyclic groups.

B ₃₁And B ₃₂Expression=CR respectively ₃₁-or-CR ₃₂=, perhaps any one represents nitrogen-atoms and another expression=CR ₃₁-or-CR ₃₂=.

R ₃₅And R ₃₆Represent hydrogen atom or substituting group independently of one another, described substituting group is represented aliphatic group, aromatic group, heterocyclic group; acyl group, alkoxy carbonyl, aryloxycarbonyl, formamyl; alkyl sulphonyl, aryl sulfonyl, or sulfamyl, and the hydrogen atom in each substituting group can be substituted.

G ₃, R ₃₁And R ₃₂Represent hydrogen atom or substituting group independently of one another, described substituting group is represented halogen atom, aliphatic group, aromatic group; heterocyclic group, cyano group, carboxyl, formamyl; alkoxy carbonyl, aryloxycarbonyl, heterocyclic oxy group carbonyl, acyl group; hydroxyl, alkoxyl group, aryloxy, heterocyclic oxy group; siloxy-, acyloxy, formamyl oxygen base, alkoxy-carbonyl oxy; aryloxycarbonyl oxygen base, amino, acyl amino, urea groups; sulfamyl amino, alkoxycarbonyl amino, aryloxycarbonyl amino, alkyl sulfonyl-amino; arlysulfonylamino, heterocycle sulfuryl amino, nitro; alkylthio, arylthio, heterocycle sulfenyl; alkyl sulphonyl, aryl sulfonyl, heterocycle alkylsulfonyl; alkyl sulphinyl, aryl sulfonyl kia, heterocycle sulfinyl; sulfamyl, or sulfo group, and each substituent hydrogen atom can further be replaced.

R ₃₁And R ₃₅, or R ₃₅And R ₃₆Can be in conjunction with forming 5-or 6-unit ring.

In formula (3), A ₃₁Expression 5-unit heterocyclic group, and its heteroatoms can be N, O or S.Its preferably nitrogenous 5-unit heterocycle, and heterocycle can encircle with aliphatic series, aromatic ring or other heterocyclic fused.Heterocycle A ₃₁Preferred embodiment comprise the pyrazoles ring, imidazole ring, thiazole ring, isothiazole ring, thiadiazoles ring, benzothiazole ring, benzoxazole ring and benzisothiazole ring.Each heterocyclic group can contain substituting group in addition.In these, pyrazoles ring, imidazole ring, isothiazole ring, thiadiazoles ring and the benzothiazole ring of preferably representing by following formula (a)-(g).

At following formula (a) in (g), R ₃₀₇To R ₃₂₂G in expression and the formula (3) ₃, R ₃₁And R ₃₂Identical substituting group.

In formula (a) in (g), preferably by formula (a) and (b) the pyrazoles ring and the isothiazole ring of expression, most preferably the pyrazoles ring of formula (a) expression.

In formula (3), B ₃₁And B ₃₂Expression=CR separately ₃₁-or-CR ₃₂=, perhaps any one represents nitrogen-atoms and another expression=CR ₃₁-or-CR ₃₂=, but each expression=CR more preferably ₃₁-or-CR ₃₂=situation.

R ₃₅And R ₃₆Can be preferably hydrogen atom separately, aliphatic group, aromatic group, heterocyclic group, acyl group, alkyl-or aryl-alkylsulfonyl.More preferably it is a hydrogen atom, aryl, and heterocyclic group, acyl group, alkyl-or aryl-alkylsulfonyl.Most preferably it is hydrogen atom, aryl or heterocyclic group.Each substituent hydrogen atom can be substituted.Yet, R ₃₅And R ₃₆Be not hydrogen atom simultaneously.

G ₃Be preferably hydrogen atom, halogen atom, aliphatic group, aromatic group, hydroxyl, alkoxyl group, aryloxy, acyloxy, heterocyclic oxy group, amino, acyl amino, urea groups, sulfamyl amino, alkoxycarbonyl amino, aryloxycarbonyl amino, alkylthio, arylthio, or heterocycle sulfenyl; More preferably hydrogen atom, halogen atom, alkyl, hydroxyl, alkoxyl group, aryloxy, acyloxy, amino, or acyl amino; And hydrogen atom most preferably, amino (preferred anilino) or acyl amino.Hydrogen atom on each substituting group can be substituted.

R ₃₁And R ₃₂Each is hydrogen atom preferably, alkyl, halogen atom, alkoxy carbonyl, carboxyl, formamyl, hydroxyl, alkoxyl group or cyano group.Each substituent hydrogen atom can be substituted.

Equally, R ₃₁And R ₃₅, or R ₃₅And R ₃₆Can be in conjunction with forming 5-or 6-unit ring.

Contain substituting group or substituent R at A ₃₁, R ₃₂, R ₃₅, R ₃₆Or G ₃Contain in addition under the substituent situation, this substituting group can be at above-mentioned G ₃, R ₃₁And R ₃₂In the substituting group quoted.

At the dyestuff by formula (3) expression is that preferred coloring agent is at G under the situation of water-soluble dye ₃, R ₃₁, R ₃₂, R ₃₅, R ₃₆Or G ₃Any position also contain ionic hydrophilic group as substituting group.As substituent ionic hydrophilic group can be sulfo group, carboxyl, phosphono or quaternary ammonium group.Preferred this ionic hydrophilic group is a carboxyl, phosphono or sulfo group, especially preferably carboxyl or sulfo group.Carboxyl, phosphono or sulfo group can be the forms of salt, and the counter ion that form this salt can be ammonium ions; alkalimetal ion (for example lithium ion, sodium ion, or potassium ion); or organic cation (for example tetramethyl ammonium, tetramethyl guanidine ion or tetramethyl phosphonium).

Now, will be given in the explanation of employed term " substituting group " in the explanation of formula (3).These terms are identical in the formula (3-A) of formula (3) and explanation after a while.

Halogen atom comprises fluorine atom, chlorine atom and bromine atoms.

Aliphatic group is meant alkyl, the alkyl of replacement, alkenyl, the alkenyl of replacement, alkynyl, the alkynyl of replacement, the aralkyl of aralkyl or replacement.In used term " replacement " expression such as for example " alkyl of replacement ": exist the hydrogen atom on " alkyl " etc. to be used in above-mentioned G ₃, R ₃₁Or R ₃₂The middle substituting group of being quoted replaces.

Aliphatic group can be side chain or can Cheng Huan.Aliphatic group preferably contains 1 to 20 carbon atom, further preferred 1 to 16 carbon atom.Aryl moiety in the aralkyl of aralkyl or replacement is preferably phenyl or naphthyl, preferred especially phenyl.The example of aliphatic group comprises methyl, ethyl, butyl, sec.-propyl, the tertiary butyl, hydroxyethyl, methoxy ethyl, cyano ethyl, trifluoromethyl, 3-sulfo group propyl group, 4-sulfo group butyl, cyclohexyl, benzyl, 2-styroyl, vinyl and allyl group.

Aromatic group is meant the aryl of aryl and replacement.Aryl is preferably phenyl or naphthyl, preferred especially phenyl.Preferred aromatic group contains 6 to 20 carbon atoms, more preferably 6 to 16 carbon atoms.

The example of aromatic group comprises phenyl, p-methylphenyl, p-methoxyphenyl, neighbour-chloro-phenyl-and-(3-sulfo group propyl group amino) phenyl.

Heterocyclic group comprises the heterocyclic group of replacement.Heterocyclic group can have and aliphatic series ring, aromatic ring or other heterocyclic fused heterocycle structure.Described heterocyclic group is preferably 5-or 6-unit heterocycle.Described substituent example comprises aliphatic group, halogen atom, alkyl sulphonyl, aryl sulfonyl, acyl group, acyl amino, sulfamyl, formamyl and ionic hydrophilic group.The example of described heterocyclic group comprises the 2-pyridyl, 2-thienyl, 2-thiazolyl, 2-[4-morpholinodithio base, 2-benzoxazolyl and 2-furyl.

Formamyl comprises the formamyl of replacement.Described substituent example comprises alkyl.In addition, the example of described formamyl comprises methylamino formyl radical and formyl-dimethylamino.

Alkoxy carbonyl comprises the alkoxy carbonyl of replacement.Described alkoxy carbonyl preferably contains 2 to 20 carbon atoms.Described substituent example is ionic hydrophilic group.The example of described alkoxy carbonyl comprises methoxycarbonyl and ethoxy carbonyl.

Aryloxycarbonyl comprises the aryloxycarbonyl of replacement.Described aryloxycarbonyl preferably contains 7 to 20 carbon atoms.Described substituent example comprises ionic hydrophilic group.The example of described aryloxycarbonyl comprises phenyloxycarbonyl.

The heterocyclic oxy group carbonyl comprises the heterocyclic oxy group carbonyl of replacement.Heterocycle can be the heterocycle of quoting for heterocyclic group.Described heterocyclic oxy group carbonyl preferably contains 2 to 20 carbon atoms.Described substituent example comprises ionic hydrophilic group.The example of described heterocyclic oxy group carbonyl comprises 2-pyridyl oxygen base carbonyl.

Acyl group comprises the acyl group of replacement.Described acyl group preferably contains 1 to 20 carbon atom.Described substituent example is ionic hydrophilic group.The example of described acyl group comprises ethanoyl and benzoyl.

Alkoxyl group comprises the alkoxyl group of replacement.Described alkoxyl group preferably contains 1 to 20 carbon atom.Described substituent example comprises alkoxyl group, hydroxyl and ionic hydrophilic group.The example of described alkoxyl group comprises methoxyl group, oxyethyl group, isopropoxy, methoxy ethoxy, hydroxyl-oxethyl and 3-carboxyl propoxy-.

Aryloxy comprises the aryloxy of replacement.Described aryloxy preferably contains 6 to 20 carbon atoms.Described substituent example comprises alkoxyl group and ionic hydrophilic group.The example of described aryloxy comprises phenoxy group, to methoxyl group phenoxy group and O-methoxy phenoxy group.

Heterocyclic oxy group comprises the heterocyclic oxy group of replacement.Heterocycle can be above-mentioned in heterocyclic group quote those.Described heterocyclic oxy group preferably contains 2 to 20 carbon atoms.Described substituent example comprises alkyl, alkoxyl group and ionic hydrophilic group.The example of described heterocyclic oxy group comprises 3-pyridyl oxygen base and 3-thienyl oxygen base.

Siloxy-is preferably the siloxy-that aliphatic group or aromatic group replaced that is contained 1 to 20 carbon atom.The example of described siloxy-comprises trimethylsiloxy and diphenyl methyl siloxy-.

Acyloxy comprises the acyloxy of replacement.Described acyloxy preferably contains 1 to 20 carbon atom.Described substituent example comprises ionic hydrophilic group.The example of described acyloxy comprises acetoxyl group and benzoyloxy.

Formamyl oxygen base comprises the formamyl oxygen base of replacement.Described substituent example comprises alkyl.The example of described formamyl oxygen base comprises N-methylamino formyl radical.

Alkoxy-carbonyl oxy comprises the alkoxy-carbonyl oxy of replacement.Described alkoxy-carbonyl oxy preferably contains 2 to 20 carbon atoms.The example of described alkoxy-carbonyl oxy comprises methoxycarbonyl oxygen base and isopropoxy carbonyl oxygen base.

Aryloxycarbonyl oxygen base comprises the aryloxycarbonyl oxygen base of replacement.Described aryloxycarbonyl oxygen base preferably contains 7 to 20 carbon atoms.The example of described aryloxycarbonyl oxygen base comprises phenyloxycarbonyl oxygen base.

Amino comprises the amino of replacement.Substituting group can be an alkyl, aryl or heterocyclic group, and alkyl, and aryl or heterocyclic group can also contain substituting group.Alkylamino comprises the alkylamino of replacement.Alkylamino preferably contains 1 to 20 carbon atom.Described substituent example comprises ionic hydrophilic group.The example of described alkylamino comprises methylamino-and diethylin.

Arylamino comprises the arylamino of replacement.Described arylamino preferably contains 6 to 20 carbon atoms.Described substituent example comprises halogen atom and ionic hydrophilic group.The example of described arylamino comprises phenyl amino and 2-chloro-phenyl-amino.

Heterocyclic amino group comprises the heterocyclic amino group of replacement.Heterocycle can be above-mentioned in heterocyclic group quote those.Described heterocyclic amino group preferably contains 2 to 20 carbon atoms.Substituent example comprises alkyl, halogen atom and ionic hydrophilic group.

Amido comprises the amido of replacement.Described amido preferably contains 2 to 20 carbon atoms.Described substituent example comprises ionic hydrophilic group.The example of described amido comprises kharophen, propionamido, benzamido, N-phenyl kharophen and 3,5-disulfo benzoyl-amido.

Urea groups comprises the urea groups of replacement.Described urea groups preferably contains 1 to 20 carbon atom.Described substituent example comprises alkyl and aryl.The example of described urea groups comprises 3-methyl urea groups, 3, and 3-dimethyl urea groups and 3-phenyl urea groups.

Sulfamyl amino comprises the sulfamyl amino of replacement.Described substituent example comprises alkyl.The example of described sulfamyl amino comprises N, N-dipropyl sulfamyl amino.

Alkoxycarbonyl amino comprises the alkoxycarbonyl amino of replacement.Described alkoxycarbonyl amino preferably contains 2 to 20 carbon atoms.Described substituent example comprises ionic hydrophilic group.The example of described alkoxycarbonyl amino comprises ethoxy carbonyl amino.

Aryloxycarbonyl amino comprises the aryloxycarbonyl amino of replacement.Described aryloxycarbonyl amino preferably contains 7 to 20 carbon atoms.Described substituent example comprises ionic hydrophilic group.The example of described aryloxycarbonyl amino comprises phenyloxycarbonyl amino.

Alkyl sulfonyl-amino and arlysulfonylamino comprise the alkyl sulfonyl-amino of replacement and the arlysulfonylamino of replacement.Described alkyl sulfonyl-amino and arlysulfonylamino preferably contain 1 to 20 carbon atom.Described substituent example comprises ionic hydrophilic group.The example of described alkyl sulfonyl-amino and arlysulfonylamino comprises methyl sulphonyl amino, N-phenyl-methyl sulphonyl amino, phenyl sulfonyl amino and 3-carboxyl phenyl-sulfuryl amino.

The heterocycle sulfuryl amino comprises the heterocycle sulfuryl amino of replacement.Heterocycle can be above-mentioned in heterocyclic group quote those.Described heterocycle sulfuryl amino preferably contains 1 to 12 carbon atom.Described substituent example comprises ionic hydrophilic group.The example of described heterocycle sulfuryl amino comprises the amino and 3-pyridyl sulfonyl amino of 2-thienyl sulphonyl base.

Alkylthio, arylthio and heterocycle sulfenyl comprise the alkylthio of replacement, the heterocycle sulfenyl of the arylthio of replacement and replacement.Heterocycle can be above-mentioned in heterocyclic group quote those.Described alkylthio, arylthio and heterocycle sulfenyl preferably contain 1 to 20 carbon atom.Described substituent example comprises ionic hydrophilic group.Described alkylthio, the example of arylthio and heterocycle sulfenyl comprises methylthio group, thiophenyl and 2-pyridyl sulfenyl.

Alkyl sulphonyl and aryl sulfonyl comprise the alkyl sulphonyl of replacement and the aryl sulfonyl of replacement.The example of alkyl sulphonyl and aryl sulfonyl comprises methylsulfonyl and benzenesulfonyl.

The heterocycle alkylsulfonyl comprises the heterocycle alkylsulfonyl of replacement.Described heterocycle alkylsulfonyl preferably contains 1 to 20 carbon atom.Described substituent example comprises ionic hydrophilic group.The example of described heterocycle alkylsulfonyl comprises 2-thienyl sulphonyl base and 3-pyridyl sulfonyl.

Alkyl sulphinyl and aryl sulfonyl kia comprise the alkyl sulphinyl of replacement and the aryl sulfonyl kia of replacement.The example of alkyl sulphinyl and aryl sulfonyl kia comprises methylsulfinyl and phenyl sulfinyl.

The heterocycle sulfinyl comprises the heterocycle sulfinyl of replacement.Heterocycle can be above-mentioned in heterocyclic group quote those.Described heterocycle sulfinyl preferably contains 1 to 20 carbon atom.Described substituent example comprises ionic hydrophilic group.The example of described heterocycle sulfinyl comprises 4-pyridyl sulfinyl.

Sulfamyl comprises the sulfamyl of replacement.Described substituent example comprises alkyl.The example of described sulfamyl comprises dimethylamino alkylsulfonyl and two-(2-hydroxyethyl) sulfamyl.

In the formula (3), particularly preferred structure is represented by following formula (3-A):

Wherein, R ₃₁, R ₃₂, R ₃₅And R ₃₆Has identical implication in the formula (3).

R ₃₃And R ₃₄Represent hydrogen atom or substituting group independently of one another, this substituting group can be aliphatic group, aromatic group, heterocyclic group, acyl group, alkoxy carbonyl, aryloxycarbonyl, formamyl, alkyl sulphonyl, aryl sulfonyl or sulfamyl.Among these, preferred hydrogen atom, aryl, heterocyclic group, acyl group, alkyl sulphonyl or aryl sulfonyl, and preferred especially hydrogen atom, aryl or heterocyclic group.

Z ₃₁Expression Hammett substituent constant σ p is 0.20 or higher electron withdrawing group.Preferred Z ₃₁Be that σ p is 0.30 or bigger electron withdrawing group, more preferably σ p is 0.45 or bigger electron withdrawing group, and preferred especially σ p is 0.60 or bigger electron withdrawing group, but σ p preferably is no more than 1.0.

More specifically, Hammett substituent constant σ p be 0.60 or the example of bigger electron withdrawing group comprise: cyano group, nitro, alkyl sulphonyl (as methyl sulphonyl) or aryl sulfonyl (as phenyl sulfonyl).

Hammett substituent constant σ p be 0.45 or the example of bigger electron-withdrawing group except above-mentioned group; also comprise acyl group (as ethanoyl), alkoxy carbonyl (as dodecyloxy carbonyl), aryloxycarbonyl (as the m-chloro phenyloxycarbonyl), alkyl sulphinyl (as the n-propyl sulfinyl), aryl sulfonyl kia (as the phenyl sulfinyl), sulfamyl (as N-ethyl sulfamyl, N, N-dimethylamino alkylsulfonyl), reach haloalkyl (as trifluoromethyl).

Hammett substituent constant σ p be 0.30 or the example of bigger electron-withdrawing group except above-mentioned group; also comprise acyloxy (as acetoxyl group); formamyl is (as N-ethylamino formyl radical; N; N-dibutylamino formyl radical); halogenated alkoxy (as trifluoromethoxy); halo aryloxy (as penta fluoro benzene oxygen base); sulfonyloxy (as sulfonyloxy methyl oxygen base); halogenated alkylthio (as the difluoro methylthio group); by two or more σ p be 0.15 or the aryl that replaces of bigger electron-withdrawing group (as 2, the 4-dinitrophenyl; pentafluorophenyl group); and heterocyclic group is (as the 2-benzoxazolyl; the 2-[4-morpholinodithio base; or 1-phenyl-2-benzimidazolyl-).

Hammett substituent constant σ p be 0.20 or the specific examples of bigger electron-withdrawing group except above-mentioned group, also comprise halogen atom.

Preferred Z ₃₁It in above-mentioned those acyl group that contains 2 to 20 carbon atoms; the alkoxy carbonyl that contains 2 to 20 carbon atoms; nitro, cyano group, contain the alkyl sulphonyl of 1 to 20 carbon atom; the aryl sulfonyl that contains 6 to 20 carbon atoms; contain the formamyl of 1 to 20 carbon atom, or contain the haloalkyl of 1 to 20 carbon atom.Preferred especially cyano group contains the alkyl sulphonyl of 1 to 20 carbon atom, or contains the aryl sulfonyl of 6 to 20 carbon atoms, most preferably cyano group.

Z ₃₂Expression hydrogen atom or substituting group, this substituting group can be aliphatic group, aromatic group or heterocyclic group.Z ₃₂Be preferably aliphatic group, more preferably contain the alkyl of 1 to 6 carbon atom.

Q represents hydrogen atom or substituting group, and substituting group can be aliphatic group, aryl or heterocyclic group.Among these, Q is preferably to comprise and forms 5 to 8 yuan of groups that encircle required non-metal atom group.This 5 to 8 yuan of rings can be substituted or be saturated, and can contain unsaturated link(age).Among these, preferred especially aromatic group and heterocyclic group.Preferred non-metallic atom can be nitrogen-atoms, Sauerstoffatom, sulphur atom or carbon atom.The specific examples of this ring structure comprises phenyl ring, pentamethylene ring, cyclohexane ring, suberane ring, the cyclooctane ring, cyclohexene ring, pyridine ring, pyrimidine ring, pyrazine ring, pyridazine ring, triazine ring, imidazole ring, benzoglyoxaline ring oxazole ring, benzoxazole ring, thiazole ring, benzothiazole Huan ， oxane ring, tetramethylene sulfone ring and thiane ring.

Each substituent hydrogen atom of being explained by formula (3-A) can be substituted.This substituting group can be those that explained in formula (3), for G ₃, R ₃₁And R ₃₂Group of being quoted and ionic hydrophilic radical.

As for substituent special preferred combination in the azo of representing by formula (3), preferred R ₃₅And R ₃₆Respectively do for oneself hydrogen atom, alkyl, aryl, heterocyclic group, alkylsulfonyl or acyl group, more preferably hydrogen atom, aryl, heterocyclic group or alkylsulfonyl most preferably are hydrogen atom, aryl or heterocyclic group.But, R ₃₅And R ₃₆All not hydrogen atom simultaneously.

Preferred G ₃Be hydrogen atom, halogen atom, alkyl, hydroxyl, amino or acyl amino, more preferably hydrogen atom, halogen atom, amino or acyl amino most preferably are hydrogen atom, amino or acyl amino.

Preferred A is pyrazoles ring, imidazole ring, isothiazole ring, thiadiazoles ring or benzothiazole ring, and more preferably pyrazoles ring or isothiazole ring most preferably are the pyrazoles ring.

B ₃₁And B ₃₂Respectively do for oneself=CR ₃₁-or-CR ₃₂=, wherein preferred R ₃₁And R ₃₂Respectively do for oneself hydrogen atom, alkyl, halogen atom, cyano group, formamyl, carboxyl, hydroxyl, alkoxyl group or alkoxy carbonyl are more preferably hydrogen atom, alkyl, carboxyl, cyano group or formamyl.

As for substituent preferred combination in the compound of representing by formula (3), preferred such compound, at least one substituting group in the wherein various substituting groups is above-mentioned preferred group, more preferably such compound, more a plurality of in the wherein various substituting groups are above-mentioned preferred groups, and most preferably such compound, wherein all each substituting group all is above-mentioned preferred group.

Below being shown in by the specific examples of the azoic dyestuff of formula (3) expression, but the present invention is not subjected to the restriction of these examples.

The content of azoic dyestuff in ink by formula (3) expression is preferably 0.2 to 20 quality %, more preferably 0.5 to 15 quality %.In addition, its solubleness (or the dispersity under the steady state) in 20 ℃ water is 5 quality % or higher, more preferably 10 quality % or higher.

(black dyes)

In the black dyes of Cai Yonging, adopted dyestuff (L) in the present invention, its wavelength X max in 500 to 700nm scopes, and in the absorption spectrum of the dilute solution that is normalized to 1.0 optical densitys, half-peak width (W λ, _1/2) be 100nm or bigger (be preferably 120 to 500nm, more preferably 120 to 350nm).

Can realize at this dyestuff (L) under the situation of " (deeply) black " of high image quality, promptly regardless of the light source of observing, strengthen hardly under the situation of any black of B, G and R, it can be used alone as the dyestuff of black ink, but this dyestuff uses with the another kind of dye combinations that can cover the low zone that absorbs of dyestuff demonstration usually.It is usually preferred to be used in combination with the dyestuff (S) that has main absorption in yellow (λ max be 350 to 500nm).Also may prepare and the black ink of another dye combinations again.

In the present invention, black ink prepares by being dissolved or dispersed in the aqueous medium with dyestuff recited above or separately or with form of mixtures, and the preferred ink that satisfies following condition, purpose is to satisfy the preferred performance of black ink institute be used to spray black printing, that is: 1) and excellent weathering resistance and/or 2) even also keep well balanced state at the back black that fades.

At first, with the size of black ink with 48 of the black square code printings of JIS flip-flop 2223, and the reflection density (D that will measure with state A spectral filter (vision spectral filter) _Vis) be defined as initial density.The reflection densitometer that is equipped with state A spectral filter can be an X-Rite photodensitometer for example.For " black " density measurement, will measure D on duty _VisReflection density as the standard observation.This printed matter is forced to fade in the ozone armpit color testing machine of the ozone that can produce 5ppm unchangeably, and based on reflection density (D _Vis) reach 80% needed time (t) of initial reflection density, by concerning 0.8=exp (k _VisT) obtain forcing fading rate constant (k _Vis).

Velocity constant (the k of preferred black ink _Vis) be 5.0 * 10 ^-2[hour ^-1] or lower, more preferably 3.0 * 10 ^-2[hour ^-1] or lower, and to be preferably especially be 1.0 * 10 ^-2[hour ^-1] or lower (condition 1).

Equally, with the size of black ink with 48 of the black square code printings of JIS flip-flop 2223, and by the reflection density (D with three kinds of color C (cyan), M (fuchsin) and Y (yellow) _R, D _G, D _B) replacement D _Vis, will be defined as initial density with the reflection density that state A spectral filter is measured.(D _R, D _G, D _B) expression (by the C reflection density of red filter, by the M reflection density of green filter, by the Y reflection density of blue filter).As explained above, this printed matter is forced to fade in the ozone armpit color testing machine of the ozone that can produce 5ppm unchangeably, and based on each reflection density (D _R, D _G, D _B) reach 80% needed time of initial reflection density, obtain forcing fading rate constant (k in a similar fashion _R, k _G, k _B).The maximum value of these three kinds of rate constants and the ratio of minimum value (R) (for example, k _RMaximum and k _GMinimum, R=k _R/ k _G) be preferably 1.2 or littler, more preferably 1.1 or littler, and be preferably 1.05 or littler (condition 2) especially.

" printing has the printed matter of black square sign indicating number of the JIS flip-flop 2223 of 48 sizes " is the size printed images of cover butter machine aperture fully, to be provided for enough sizes of density measurement.

In addition, in black ink, the oxidizing potential of the use therein at least a dyestuff 1.0V (with respect to SCE) that is higher than as explained above, preferably be higher than 1.1V (with respect to SCE), further preferably be higher than 1.2V (with respect to SCE), and most preferably be higher than 1.25V (with respect to SCE), and the λ max of at least a dyestuff is preferably in 500nm or bigger (condition 3).

In addition, the black dyes that adopts in black ink of the present invention preferably satisfies following physical properties, to reach the tone in preferable range, anti-jail property or package stability:

Character 1: satisfied 680nm 〉=λ max (the DMF) 〉=570nm that concerns of the maximum absorption wavelength λ max (DMF) of the absorption spectrum in DMF;

Character 2: oxidizing potential is higher than 1.0V (with respect to SCE);

Character 3: the maximum absorption wavelength λ max (water) of the absorption spectrum in water satisfies relation | λ max (DMF)-λ max (water) | and 〉=30nm;

Character 4: molar absorption coefficient ε (DMF) in DMF and satisfied ε (the water)/ε (DMF)≤0.9 that concerns of the molar absorption coefficient ε (water) in water; With

Character 5: the associated complex in the absorption spectrum of measuring in water satisfies at the absorbance A bs (monomer) of the maximum absorption wave strong point of absorbance A bs of maximum absorption wave strong point (associated complex) and the monomer absorption spectrum measured in DMF and concerns Abs (monomer)/Abs (associated complex)≤0.75.

These character are preferred, because they in ink, provide have preferred black tone, the black dyes of the anti-jail property of excellent light and ozone resistance and excellent package stability, these character are according to limiting described in Japanese patent application No.2003-353498.

The black dyes that satisfies these physical propertiess comprises the dyestuff of being represented by formula (4).Below, will explain dyestuff by formula (4) expression:

Formula (4): A ₄₁-N=N-A ₄₂-N=N-A ₄₃

In the formula (4), A ₄₁, A ₄₂And A ₄₃Expression independently of one another can substituted aromatic group or can substituted heterocyclic group (A ₄₁And A ₄₃Be univalent perssad, and A ₄₂Be divalent group).

By the azoic dyestuff of formula (4) expression especially preferably by the dyestuff of following formula (4-A) expression:

In the formula (4-A), B ₄₁And B ₄₂Expression=CR respectively ₄₁-or-CR ₄₂=, perhaps any one represents nitrogen-atoms and another expression=CR ₄₁-or-CR ₄₂=.

G ₄, R ₄₁And R ₄₂Represent hydrogen atom independently of one another, halogen atom, aliphatic group, aromatic group; heterocyclic group, cyano group, carboxyl, formamyl; alkoxy carbonyl, aryloxycarbonyl, heterocyclic oxy group carbonyl, acyl group; hydroxyl, alkoxyl group, aryloxy; heterocyclic oxy group, siloxy-, acyloxy; formamyl oxygen base, alkoxy-carbonyl oxy, aryloxycarbonyl oxygen base; amino (comprises alkylamino; arylamino and heterocyclic amino group), acyl amino, urea groups; sulfamyl amino, alkoxycarbonyl amino, aryloxycarbonyl amino; alkyl-or aryl-sulfuryl amino, heterocycle sulfuryl amino, nitro; alkylthio or arylthio, the heterocycle sulfenyl, alkyl-or aryl-alkylsulfonyl; the heterocycle alkylsulfonyl, alkyl-or aryl-sulfinyl, the heterocycle sulfinyl; sulfamyl, or sulfo group, and it can further be replaced.

R ₄₅And R ₄₆Represent hydrogen atom independently of one another, aliphatic group, aromatic group, heterocyclic group, acyl group, alkoxy carbonyl, aryloxycarbonyl, formamyl, alkyl-or aryl-alkylsulfonyl, or sulfamyl, it can also contain substituting group.

R ₄₁And R ₄₅, or R ₄₅And R ₄₆Can be in conjunction with forming 5-or 6-unit ring.

A ₄₁And A ₄₂Have with formula (4) in identical meanings.

By the azoic dyestuff of formula (4-A) expression further preferably by the following formula (4-B1) or (4-B2) dyestuff of expression:

In formula (4-B1) with (4-B2), R ₄₇And R ₄₈Have with formula (4-A) in R ₄₁Identical implication.A ₄₁, R ₄₅, R ₄₆, B ₄₁, B ₄₂And G ₄Have with formula (4-A) in identical meanings.

Now, will be given in formula (4), formula (4-A) and constitute the explanation of employed term (substituting group) in the explanation of formula (4-B) (below, formula (4-B1) and (4-B2) unify to be expressed as formula (4-B)) of its subordinate concept.These terms will be used for the formula (4-C) explained after a while and (4-D) jointly.

Halogen atom comprises fluorine atom, chlorine atom and bromine atoms.

Aliphatic group is meant alkyl, the alkyl of replacement, alkenyl, the alkenyl of replacement, alkynyl, the alkynyl of replacement, the aralkyl of aralkyl or replacement.Aliphatic group can be side chain or can Cheng Huan.Aliphatic group preferably contains 1 to 20 carbon atom, further preferred 1 to 16 carbon atom.Aryl moiety in the aralkyl of aralkyl or replacement is preferably phenyl or naphthyl, preferred especially phenyl.The example of aliphatic group comprises methyl, ethyl, butyl, sec.-propyl, the tertiary butyl, hydroxyethyl, methoxy ethyl, cyano ethyl, trifluoromethyl, 3-sulfo group propyl group, 4-sulfo group butyl, cyclohexyl, benzyl, 2-styroyl, vinyl and allyl group.

The monovalence aromatic group is meant the aryl of aryl and replacement.Aryl is preferably phenyl or naphthyl, preferred especially phenyl.Preferred monovalence aromatic group contains 6 to 20 carbon atoms, more preferably 6 to 16 carbon atoms.The example of monovalence aromatic group comprises phenyl, p-methylphenyl, p-methoxyphenyl, neighbour-chloro-phenyl-and-(3-sulfo group propyl group amino) phenyl.The divalent aromatic base is that this monovalence aromatic group is formed divalent state, and example comprises: phenylene, inferior p-methylphenyl, and to the methoxyl group phenylene, neighbour-chlorine phenylene ,-(3-sulfo group propyl group amino) phenylene and naphthylidene.

Heterocyclic group comprises the heterocyclic group and the unsubstituted heterocyclic group of replacement.Heterocyclic group can contain and aliphatic series ring, aromatic ring or other heterocyclic fused heterocycle structure.Described heterocyclic group is preferably 5-or 6-unit heterocycle, and the heteroatoms in heterocycle can be N, O or S.Described substituent example comprises aliphatic group, halogen atom, and alkyl-and aryl-alkylsulfonyl, acyl group, acyl amino, sulfamyl, formamyl and ionic hydrophilic group.The example of monovalence heterocyclic group comprises the 2-pyridyl, 2-thienyl, 2-thiazolyl, 2-[4-morpholinodithio base, 2-benzoxazolyl and 2-furyl.Thereby divalent heterocyclic group forms another key by hydrogen atom of removal from the monovalence heterocycle and forms.

Formamyl comprises the formamyl and the unsubstituted formamyl of replacement.Described substituent example comprises alkyl.In addition, the example of described formamyl comprises methylamino formyl radical and formyl-dimethylamino.

Alkoxy carbonyl comprises the alkoxy carbonyl and the unsubstituted alkoxy carbonyl of replacement.Described alkoxy carbonyl preferably contains 2 to 20 carbon atoms.Described substituent example comprises ionic hydrophilic group.The example of described alkoxy carbonyl comprises methoxycarbonyl and ethoxy carbonyl.

Aryloxycarbonyl comprises the aryloxycarbonyl and the unsubstituted aryloxycarbonyl of replacement.Described aryloxycarbonyl preferably contains 7 to 20 carbon atoms.Described substituent example comprises ionic hydrophilic group.The example of described aryloxycarbonyl comprises phenyloxycarbonyl.

The heterocyclic oxy group carbonyl comprises the heterocyclic oxy group carbonyl and the unsubstituted heterocyclic oxy group carbonyl of replacement.Described heterocyclic oxy group carbonyl preferably contains 2 to 20 carbon atoms.Described substituent example comprises ionic hydrophilic group.The example of described heterocyclic oxy group carbonyl comprises 2-pyridyl oxygen base carbonyl.

Acyl group comprises the acyl group and the unsubstituted acyl of replacement.Described acyl group preferably contains 1 to 20 carbon atom.Described substituent example comprises ionic hydrophilic group.The example of described acyl group comprises ethanoyl and benzoyl.

Alkoxyl group comprises the alkoxyl group and the unsubstituted alkoxyl group of replacement.Described alkoxyl group preferably contains 1 to 20 carbon atom.Described substituent example comprises alkoxyl group, hydroxyl and ionic hydrophilic group.The example of described alkoxyl group comprises methoxyl group, oxyethyl group, isopropoxy, methoxy ethoxy, hydroxyl-oxethyl and 3-carboxyl propoxy-.

Aryloxy comprises the aryloxy and the unsubstituted aryloxy of replacement.Described aryloxy preferably contains 6 to 20 carbon atoms.Described substituent example comprises alkoxyl group and ionic hydrophilic group.The example of described aryloxy comprises phenoxy group, to methoxyl group phenoxy group and O-methoxy phenoxy group.

Heterocyclic oxy group comprises the heterocyclic oxy group and the unsubstituted heterocyclic oxy group of replacement.Described heterocyclic oxy group preferably contains 2 to 20 carbon atoms.Described substituent example comprises alkyl, alkoxyl group and ionic hydrophilic group.The example of described heterocyclic oxy group comprises 3-pyridyl oxygen base and 3-thienyl oxygen base.

Siloxy-is preferably the aliphatic group that contained 1 to 20 carbon atom or by siloxy-that aromatic group replaced.The example of described siloxy-comprises trimethylsiloxy and diphenyl methyl siloxy-.

Acyloxy comprises the acyloxy and the unsubstituted acyloxy of replacement.Described acyloxy preferably contains 1 to 20 carbon atom.Described substituent example comprises ionic hydrophilic group.The example of described acyloxy comprises acetoxyl group and benzoyloxy.

Formamyl oxygen base comprises the formamyl oxygen base and the unsubstituted formamyl oxygen base of replacement.Described substituent example comprises alkyl.The example of described formamyl oxygen base comprises N-methylamino formyl radical.

Alkoxy-carbonyl oxy comprises the alkoxy-carbonyl oxy and the unsubstituted alkoxy-carbonyl oxy of replacement.Described alkoxy-carbonyl oxy preferably contains 2 to 20 carbon atoms.The example of described alkoxy-carbonyl oxy comprises methoxycarbonyl oxygen base and isopropoxy carbonyl oxygen base.

Aryloxycarbonyl oxygen base comprises the aryloxycarbonyl oxygen base and the unsubstituted aryloxycarbonyl oxygen base of replacement.Described aryloxycarbonyl oxygen base preferably contains 7 to 20 carbon atoms.The example of described aryloxycarbonyl oxygen base comprises phenyloxycarbonyl oxygen base.

Amino comprises uses alkyl, the amino that aryl or heterocyclic group replace, and it can also contain substituting group.Alkylamino preferably contains 1 to 20 carbon atom.Described substituent example comprises ionic hydrophilic group.The example of described alkylamino comprises methylamino-and diethylin.

Arylamino comprises the arylamino and the unsubstituted arylamino of replacement.Described arylamino preferably contains 6 to 20 carbon atoms.Described substituent example comprises halogen atom and ionic hydrophilic group.The example of described arylamino comprises phenyl amino and 2-chloro-phenyl-amino.

Heterocyclic amino group comprises the heterocyclic amino group and the unsubstituted heterocyclic amino group of replacement.Described heterocyclic amino group preferably contains 2 to 20 carbon atoms.Substituent example comprises alkyl, halogen atom and ionic hydrophilic group.

Acyl amino comprises the acyl amino and the unsubstituted acyl amino of replacement.Described acyl amino preferably contains 2 to 20 carbon atoms.Described substituent example comprises ionic hydrophilic group.The example of described acyl amino comprises kharophen, propionamido, benzamido, N-phenyl kharophen and 3,5-disulfo benzoyl-amido.

Urea groups comprises the urea groups and the unsubstituted urea groups of replacement.Described urea groups preferably contains 1 to 20 carbon atom.Described substituent example comprises alkyl and aryl.The example of described urea groups comprises 3-methyl urea groups, 3, and 3-dimethyl urea groups and 3-phenyl urea groups.

Sulfamyl amino comprises the amino and unsubstituted sulfamyl amino of the sulfamyl of replacement.Described substituent example comprises alkyl.The example of described sulfamyl amino comprises N, N-dipropyl sulfamyl amino.

Alkoxycarbonyl amino comprises the alkoxycarbonyl amino and the unsubstituted alkoxycarbonyl amino of replacement.Described alkoxycarbonyl amino preferably contains 2 to 20 carbon atoms.Described substituent example comprises ionic hydrophilic group.The example of described alkoxycarbonyl amino comprises ethoxy carbonyl amino.

Aryloxycarbonyl amino comprises the amino and unsubstituted aryloxycarbonyl amino of the aryloxycarbonyl of replacement.Described aryloxycarbonyl amino preferably contains 7 to 20 carbon atoms.Described substituent example comprises ionic hydrophilic group.The example of described aryloxycarbonyl amino comprises phenyloxycarbonyl amino.

Alkyl-and aryl-sulfuryl amino comprise the alkyl of replacement-and aryl-sulfuryl amino and unsubstituted alkyl-and aryl-sulfuryl amino.Described sulfuryl amino preferably contains 1 to 20 carbon atom.Described substituent example comprises ionic hydrophilic group.The example of these sulfuryl aminos comprises methyl sulphonyl amino, N-phenyl-methyl sulphonyl amino, phenyl sulfonyl amino and 3-carboxyl phenyl-sulfuryl amino.

The heterocycle sulfuryl amino comprises the heterocycle sulfuryl amino and the unsubstituted heterocycle sulfuryl amino of replacement.Described heterocycle sulfuryl amino preferably contains 1 to 12 carbon atom.Described substituent example comprises ionic hydrophilic group.The example of described heterocycle sulfuryl amino comprises the amino and 3-pyridine sulfuryl amino of 2-thiophen sulfuryl.

The heterocycle alkylsulfonyl comprises the heterocycle alkylsulfonyl and the unsubstituted heterocycle alkylsulfonyl of replacement.Described heterocycle alkylsulfonyl preferably contains 1 to 20 carbon atom.Described substituent example comprises ionic hydrophilic group.The example of described heterocycle alkylsulfonyl comprises 2-thiophen sulfuryl and 3-pyridine alkylsulfonyl.

The heterocycle sulfinyl comprises the heterocycle sulfinyl and the unsubstituted heterocycle sulfinyl of replacement.Described heterocycle sulfinyl preferably contains 1 to 20 carbon atom.Described substituent example comprises ionic hydrophilic group.The example of described heterocycle sulfinyl comprises 4-pyridyl sulfinyl.

Alkylthio, arylthio and heterocycle sulfenyl comprise the alkylthio of replacement, the arylthio of replacement and heterocycle sulfenyl and unsubstituted alkylthio, unsubstituted arylthio and the unsubstituted heterocycle sulfenyl of replacement.Described alkylthio, arylthio or heterocycle sulfenyl are preferably and contain 1 to 20 carbon atom.Described substituent example comprises ionic hydrophilic group.Described alkylthio, the example of arylthio and heterocycle sulfenyl comprises methylthio group, thiophenyl and 2-pyridyl sulfenyl.

Alkyl-and aryl-alkylsulfonyl comprise the alkyl of replacement-and aryl-alkylsulfonyl and unsubstituted alkyl-and aryl-alkylsulfonyl.Alkyl-and the example of aryl-alkylsulfonyl comprise methyl sulphonyl and phenyl sulfonyl respectively.

Alkyl-and aryl-sulfinyl comprise the alkyl of replacement-and aryl-sulfinyl and unsubstituted alkyl-and aryl-sulfinyl.Alkyl-and the example of aryl-sulfinyl comprise methanesulfinyl and benzenesulfinyl respectively.

Sulfamyl comprises the sulfamyl and the unsubstituted sulfamyl of replacement.Described substituent example comprises alkyl.The example of described sulfamyl comprises dimethylamino alkylsulfonyl and two-(2-hydroxyethyl) sulfamyl.

Below, will further explain formula (4), (4-A) and (4-B).

In the following description, top description is applied to group and substituting group.

In the formula (4), A ₄₁, A ₄₂And A ₄₃Expression can substituted aromatic group (A independently of one another ₄₁And A ₄₃Be monovalence aromatic group such as aryl, and A ₄₂Be divalent aromatic base such as arylidene), or can substituted heterocyclic group (A ₄₁And A ₄₃Be the monovalence heterocyclic group, and A ₄₂Be divalent heterocyclic group).The example of aromatic ring comprises phenyl ring and naphthalene nucleus, and the heterocyclic heteroatoms can be N, O or S.Heterocycle can be heterocyclic fused with aliphatic series ring, aromatic ring or another.

Substituting group can be arylazo base or heterocycle azo base.Therefore, the dyestuff by formula (4) expression comprises trisazo dye and Tetrakisazo dyes.

In addition, A ₄₁, A ₄₂And A ₄₃In at least two be preferably heterocyclic group.

For A ₄₃, preferred heterocyclic group is 6 yuan of nitrogenous heterocycles of aromatics.Particularly preferably be wherein A ₄₃By 6 yuan of nitrogenous heterocycles of aromatics of following formula (4-C) expression, and in this case, formula (4) is corresponding to formula (4-A):

In the formula (4-C), B ₄₁And B ₄₂Expression=CR respectively ₄₁-or-CR ₄₂=, perhaps any one represents nitrogen-atoms and another expression=CR ₄₁-or-CR ₄₂=, but more preferably they are represented respectively=CR ₄₁-and-CR ₄₂=situation.

R ₄₅And R ₄₆Be hydrogen atom independently of one another, aliphatic group, aromatic group, heterocyclic group, acyl group, alkoxy carbonyl, aryloxycarbonyl, formamyl, alkyl-or aryl-alkylsulfonyl, or sulfamyl, it can also contain substituting group.

By R ₄₅And R ₄₆The substituting group of expression is preferably hydrogen atom, aliphatic group, aromatic group; heterocyclic group, acyl group, alkyl-or aryl-alkylsulfonyl; or sulfamyl, hydrogen atom more preferably, aromatic group; heterocyclic group; acyl group, alkyl-or aryl-alkylsulfonyl, or sulfamyl; and most preferably be hydrogen atom, aryl or heterocyclic group.Each group can also contain substituting group.

G ₄, R ₄₁And R ₄₂Represent hydrogen atom independently of one another, halogen atom, aliphatic group, aromatic group; heterocyclic group, cyano group, carboxyl, formamyl; alkoxy carbonyl, aryloxycarbonyl, heterocyclic oxy group carbonyl, acyl group; hydroxyl, alkoxyl group, aryloxy; heterocyclic oxy group, siloxy-, acyloxy; formamyl oxygen base, alkoxy-carbonyl oxy, aryloxycarbonyl oxygen base; amino (comprises alkylamino; arylamino and heterocyclic amino group), acyl amino, urea groups; sulfamyl amino, alkoxycarbonyl amino, aryloxycarbonyl amino; alkyl-or aryl-sulfuryl amino, heterocycle sulfuryl amino, nitro; alkylthio or arylthio, the heterocycle sulfenyl, alkyl-or aryl-alkylsulfonyl; the heterocycle alkylsulfonyl, alkyl-or aryl-sulfinyl, the heterocycle sulfinyl; sulfamyl, or sulfo group, and it can further be replaced.

By G ₄The substituting group of expression is preferably hydrogen atom; halogen atom, aliphatic group, aromatic group; hydroxyl, alkoxyl group, aryloxy; acyloxy, heterocyclic oxy group, amino (comprises alkylamino; arylamino and heterocyclic amino group); acyl amino, urea groups, sulfamyl amino; alkoxycarbonyl amino, aryloxycarbonyl amino, alkylthio or arylthio; or heterocycle sulfenyl; hydrogen atom more preferably; halogen atom, alkyl, hydroxyl; alkoxyl group; aryloxy, acyloxy, amino (comprises alkylamino; arylamino and heterocyclic amino group) or acyl amino; and most preferably be hydrogen atom or acyl amino, and every kind of group can also contain substituting group.

By R ₄₁And R ₄₂The substituting group of expression is preferably hydrogen atom, alkyl, aryl, heterocyclic group, halogen atom, carbalkoxy, carboxyl, formamyl, hydroxyl, alkoxyl group or cyano group.Every kind of group can also contain substituting group.R ₄₁And R ₄₅, or R ₄₅And R ₄₆Can be in conjunction with forming 5-or 6-unit ring.By A ₄₁, R ₄₁, R ₄₂, R ₄₅, R ₄₆And G ₄The substituting group of expression also contains under the substituent situation, and substituting group can be in the above for G ₄, R ₄₁And R ₄₂Those that quoted.In addition, preferably at A ₄₁, R ₄₁, R ₄₂, R ₄₅, R ₄₆And G ₄On any position provide ionic hydrophilic group as substituting group.

As substituent ionic hydrophilic group can be sulfo group, carboxyl, phosphono or quaternary ammonium group.Preferred this ionic hydrophilic group is a carboxyl, phosphono or sulfo group, especially preferably carboxyl or sulfo group.Carboxyl, phosphono or sulfo group can be the forms of salt, and the counter ion that form this salt can be ammonium ions; alkalimetal ion (for example lithium ion, sodium ion, or potassium ion); or organic cation (for example tetramethyl ammonium, tetramethyl guanidine ion or tetramethyl phosphonium ion).

By A ₄₂The heterocyclic ring of expression is preferably thiphene ring, thiazole ring, imidazole ring, benzothiazole ring or thieno-thiazole ring.Every kind of heterocyclic group can also contain substituting group.In these, especially preferably by thiphene ring, thiazole ring, imidazole ring, benzothiazole ring and the thieno-thiazole ring of formula (h) to (l) expression.At A ₄₂Be thiphene ring and A by (h) expression ₄₃Have under the situation by the structure of formula (4-C) expression, formula (4) is corresponding to formula (4-B1), and at A ₄₂Be thiazole ring and A by (i) expression ₄₃Have under the situation by the structure of formula (4-C) expression, formula (4) is corresponding to formula (4-B2):

Formula (h) in (l), R ₄₀₉To R ₄₁₇G in expression and the formula (4-C) ₄, R ₄₂And R ₄₃Identical substituting group.

Among the present invention, particularly preferred structure is (formula (4-D1) and (4-D2) unified by formula (4-D) expression) expression by formula (4-D1) or (4-D2).

In formula (4-D1), Z ₄Expression Hammett substituent constant σ p is 0.20 or higher electron withdrawing group.Preferred Z ₄Be that σ p is 0.30 or bigger electron withdrawing group, more preferably σ p is 0.45 or bigger electron withdrawing group, and preferred especially σ p is 0.60 or bigger electron withdrawing group, but σ p preferably is no more than 1.0.

More specifically, Hammett substituent constant σ p be 0.60 or the example of bigger electron withdrawing group comprise: cyano group, nitro, alkyl sulphonyl (as methyl sulphonyl) or aryl sulfonyl (as phenyl sulfonyl).

Hammett substituent constant σ p be 0.45 or the example of bigger electron-withdrawing group except above-mentioned group; also comprise acyl group (as ethanoyl), alkoxy carbonyl (as dodecyloxy carbonyl), aryloxycarbonyl (as the m-chloro phenyloxycarbonyl), alkyl sulphinyl (as the n-propyl sulfinyl), aryl sulfonyl kia (as the phenyl sulfinyl), sulfamyl (as N-ethyl sulfamyl, N, N-dimethylamino alkylsulfonyl), reach haloalkyl (as trifluoromethyl).

Hammett substituent constant σ p be 0.30 or the example of bigger electron-withdrawing group except above-mentioned group; also comprise acyloxy (as acetoxyl group); formamyl is (as N-ethylamino formyl radical; N; N-dibutylamino formyl radical); halogenated alkoxy (as trifluoromethoxy); halo aryloxy (as penta fluoro benzene oxygen base); sulfonyloxy (as sulfonyloxy methyl oxygen base); halogenated alkylthio (as the difluoro methylthio group); by two or more σ p be 0.15 or the aryl that replaces of bigger electron-withdrawing group (as 2, the 4-dinitrophenyl; pentafluorophenyl group); and heterocyclic group is (as the 2-benzoxazolyl; the 2-[4-morpholinodithio base; or 1-phenyl-2-benzimidazolyl-).

Hammett substituent constant 6p be 0.20 or the specific examples of bigger electron-withdrawing group except above-mentioned group, also comprise halogen atom.

Preferred Z ₄It in above-mentioned those acyl group that contains 2 to 20 carbon atoms; the alkoxy carbonyl that contains 2 to 20 carbon atoms; nitro; cyano group; the alkyl sulphonyl that contains 1 to 20 carbon atom; the aryl sulfonyl that contains 6 to 20 carbon atoms contains the formamyl of 1 to 20 carbon atom, or contains the haloalkyl of 1 to 20 carbon atom.Preferred especially cyano group contains the alkyl sulphonyl of 1 to 20 carbon atom, or contains the aryl sulfonyl of 6 to 20 carbon atoms, most preferably cyano group.

Wherein the Hammett substituent constant σ p of Cai Yonging is described in the JP-A-2003-306623 0059-0060 section.

R ₄₁, R ₄₂, R ₄₅, R ₄₆And R ₄₇Have with formula (4-B) in identical implication.R ₄₃And R ₄₄Be hydrogen atom independently of one another, aliphatic group, aromatic group, heterocyclic group, acyl group, alkoxy carbonyl, aryloxycarbonyl, formamyl, alkyl-or aryl-alkylsulfonyl, or sulfamyl.In these, preferred hydrogen atom, aromatic group, heterocyclic group, acyl group, or alkyl-or aryl-alkylsulfonyl, and preferred especially hydrogen atom, aromatic group or heterocyclic group.

Every kind of group that formula (4-D) is explained can also contain substituting group.Also contain under the substituent situation at this group, this substituting group can be those that explain in formula (4-A), G ₄, R ₄₅And R ₄₆In the group quoted, or ionic hydrophilic radical.

A ₄₁Can be aromatic ring or heterocycle, and preferably phenyl ring, naphthalene nucleus, pyridine ring, imidazole ring, pyrazoles ring, thiazole ring, isothiazole ring, thiadiazoles ring, benzothiazole ring or benzisothiazole ring, be more preferably phenyl ring, naphthalene nucleus, pyridine ring, pyrazoles ring, imidazole ring, isothiazole ring or benzothiazole ring, and most preferably be phenyl ring or naphthalene nucleus.

Black dyes of the present invention, in order to ensure at the aqueous solution or the package stability in ink, preferably have aromatic group or aromatic heterocyclic group as substituting group, its mode makes azoic dyestuff directly and in the azo group bonded aromatic ring not contain altogether above 12 conjugated pi electron.Directly be meant all and azo group bonded aromatic ring with azo group bonded aromatic ring, and directly with azo group bonded aromatic ring be not meant direct combine with azo group but on the chromophoric group of formation azoic dyestuff as the aromatic ring of substituting group existence.For example, naphthalene nucleus directly with azo group bonded situation under, not only in naphthalene nucleus directly and azo group bonded phenyl ring, and whole naphthalene nucleus is considered to direct and azo group bonded aromatic ring.Under xenyl and azo group bonded situation, be considered to directly and azo group bonded aromatic ring with azo group bonded phenyl, and other phenyl is thought not directly bonded aromatic ring.Aromatic ring not only comprises aryl but also comprises aromatic heterocycle.The azoic dyestuff that adopts among preferred the present invention directly and in the azo group bonded aromatic ring is not containing above 12 conjugated pi electron.For example, contain directly and azo group bonded phenyl ring and naphthalene nucleus as the azoic dyestuff of aromatic ring, conjugated pi electron is calculated as 6+10=16.In addition, the conjugated pi electron in aromatic ring is meant the conjugated pi electron that contains in aromatic ring (comprise heterocycle and be not limited only to 6 yuan of rings).By having such aromatic ring as substituting group, dyestuff shows preferred association character, improves package stability thus.The replacement position of aromatic ring is preferably: R ₄₁, R ₄₂, R ₄₃, R ₄₄, R ₄₅, R ₄₆Or R ₄₇, be preferably R especially ₄₃, R ₄₄, R ₄₅, R ₄₆Or R ₄₇

The preferred coloring agent of using for the black ink that adopts among the present invention, in substituent special preferably combination, R ₄₅And R ₄₆Be preferably hydrogen atom, alkyl, aryl, heterocyclic group, alkylsulfonyl or acyl group separately, more preferably hydrogen atom, aryl, heterocyclic group or alkylsulfonyl, and most preferably be hydrogen atom, aryl or heterocyclic group.But, R ₄₅And R ₄₆Be not hydrogen atom simultaneously.

G ₄Be preferably hydrogen atom, halogen atom, alkyl, hydroxyl, amino or acyl amino, more preferably hydrogen atom, halogen atom, amino or acyl amino, and most preferably be hydrogen atom, amino or acyl amino.

A ₄₁Be preferably phenyl ring, naphthalene nucleus, pyridine ring, imidazole ring or pyrazoles ring, most preferably be phenyl ring or naphthalene nucleus.

B ₄₁And B ₄₂Expression=CR separately ₄₁-or-CR ₄₂=, and preferred R ₄₁And R ₄₂Can be hydrogen atom, alkyl, halogen atom, cyano group, formamyl, carboxyl, hydroxyl, alkoxyl group or alkoxy carbonyl, more preferably hydrogen atom, alkyl, carboxyl, cyano group or formamyl separately.

As for substituent preferably combination in by the compound of formula (4) expression, preferably: wherein various substituent at least one be the compound of preferred group recited above, more preferably: wherein various substituent greater amounts are compounds of preferred group recited above, and most preferably: wherein all substituting groups are compounds of preferred group recited above.

Below, show specific examples, but the azoic dyestuff that can adopt among the present invention is not limited to these examples by the azoic dyestuff of formula (4) expression.Equally, carboxyl, phosphono or sulfo group can be the forms of salt; and the counter ion that form this salt can be ammonium ions, alkalimetal ion (lithium ion for example, sodium ion; or organic cation (for example tetramethyl ammonium, tetramethyl guanidine ion or tetramethyl phosphonium ion) or potassium ion).In these, preferred ammonium ion, organic cation or lithium ion, and lithium ion most preferably.

Black dyes by formula (4) expression can synthesize by the coupled reaction of two azo compositions and coupling composition.These are described among JP-A-2003-306623 and the Japanese patent application No.2003-353498, and synthetic can the realization by the method for wherein describing.

As for the dyestuff (S) of λ max in 350 to 500nm, can advantageously adopt yellow dyes and slightly and the yellow ultramarine of explaining.

The content of azoic dyestuff in ink by formula (4) expression is preferably 0.2 to 20 quality %, is preferably 0.5 to 15 quality %.

In ink of the present invention, another kind of dyestuff and dye combinations recited above can be used, to obtain full-colour image or to regulate tone.Below the dyestuff that can be used in combination is shown in.

Yellow dyes for example can be: aryl or heteroaryl (heteryl) azoic dyestuff, and it has as the phenol of coupling composition, naphthols, aniline, pyrrolinone (pirazolone), pyridone or open chain activity methene compound; Azomethine dyes, it has the open chain activity methene compound as the coupling composition; Methine dyes is as Ben Yajiaji dyestuff or single methyl oxonol dye; The quinone dyestuff is as anthraquinone dye; And other dyestuff comprises quinophthalones (quinophthalone) dyestuff, nitro-nitroso-dyestuff, acridine dye, dihydroketoacridine dyestuff etc.This class dyestuff can only provide yellow after the part disassociation of chromophore, and counter cation in this case can be inorganic cation such as alkalimetal ion or ammonium, organic cation such as pyridinium ion or quaternary ammonium salt, or in part-structure, contain these cationic polymer cations.

Magenta dye for example can be: aryl or heteroaryl azoic dyestuff, and it contains the phenol as the coupling composition, naphthols or aniline; Azomethine dyes, it contains pyrazolone or Pyrazolotriazole as the coupling composition; Methine dyes such as arylidene dyestuff, styryl dye, merocyanine (melocyanine dye) dyestuff or oxonol dye; Carbonium dye such as diphenyl methane dye, triphenylmethane dye, or xanthene dye; Quinone dyestuff such as naphthoquinones, anthraquinone, or anthrapyridone; With fused polycycle dyestuff such as dioxazine dyestuff.These dyestuffs can only provide carmetta after the part disassociation of chromophore, and counter cation in this case can be inorganic cation such as alkalimetal ion or ammonium, organic cation such as pyridinium ion or quaternary ammonium salt, or in part-structure, contain these cationic polymer cations.

Cyan dye for example can be: azomethine dyes such as indoaniline dyes or indophenol dye; Polymethin dye such as cyanine dyes, oxonol dye, or merocyanine dyes; Carbonium dye such as diphenyl methane dye, triphenylmethane dye or xanthene dye; Phthalocyanine pigment; Anthraquinone dye; Aryl or heteroaryl azoic dyestuff, it contains for example phenol, and naphthols or aniline are as the coupling composition; And indigo-thioindigo(id)dyes.These dyestuffs can only provide cyan after the part disassociation of chromophore, and counter cation in this case can be inorganic cation such as alkalimetal ion or ammonium, organic cation such as pyridinium ion or quaternary ammonium salt, or in part-structure, contain these cationic polymer cations.

In addition, also can use black dyes such as polyazo dye.

Also can be used in combination water-soluble dye such as substantive dyestuff, matching stain, food dye, basic dyestuff or reactive dyestuffs.Particularly preferred dyestuff example comprises:

C.I. directly red 2,4,9,23,26,31,39,62,63,72,75,76,79,80,81,83,84,89,92,95,111,173,184,207,211,212,214,218,21,223,224,225,226,227,232,233,240,241,242,243,247;

C.I. direct purple 7,9,47,48,51,66,90,93,94,95,98,100,101;

C.I. direct yellow 8,9,11,12,27,28,29,33,35,39,41,44,50,53,58,59,68,86,87,93,95,96,98,100,106,108,109,110,130,132,142,144,161,163;

C.I. sun blue 1,10,15,22,25,55,67,68,71,76,77,78,80,84,86,87,90,98,106,108,109,151,156,158,159,160,168,189,192,193,194,199,200,201,202,203,207,211,213,214,218,225,229,236,237,244,248,249,251,252,264,270,280,288,289,291;

C.I. directly deceive 9,17,19,22,32,51,56,62,69,77,80,91,94,97,108,112,113,114,117,118,121,122,125,132,146,154,166,168,173,199;

C.I. acid red 35,42,52,57,62,80,82,111,114,118,119,127,128,131,143,151,154,158,249,254,257,261,263,266,289,299,301,305,336,337,361,396,397;

C.I. acid violet 5,34,43,47,48,90,108,126;

C.I. turmeric yellow 17,19,23,25,49,40,42,44,49,60,64,76,79,110,127,135,151,159,169,174,190,195,196,197,199,218,219,222,227;

C.I. acid blue 9,25,40,41,62,72,76,78,80,82,92,106,112,113,120,127:1,129,138,143,175,181,205,207,220,221,230,232,247,258,260,264,271,277,278,279,280,288,290,326;

C.I. erie black 7,24,29,48,52:1,172;

C.I. reactive red 3,13,17,19,21,22,23,24,29,35,37,40,41,43,45,49,55;

C.I. REACTIVE VIOLET 1,3,4,5,6,7,8,9,16,17,22,23,24,26,27,33,34;

C.I. reactive yellow 2,3,13,14,15,17,18,23,24,25,26,27,29,35,37,41,42;

C.I. Reactive blue 2,3,5,8,10,13,14,15,17,18,19,21,25,26,27,28,29,38;

C.I. reactive black 4,5,8,14,21,23,26,31,32,34;

C.I. alkali red 1:1 2,13,14,15,18,22,23,24,25,27,29,35,36,38,39,45,46;

C.I. alkaline purple 1,2,3,7,10,15,16,20,21,25,27,28,35,37,39,40,48;

C.I. basic yellow 1,2,4,11,13,14,15,19,21,23,24,25,28,29,32,36,39,40;

C.I. alkali blue 1,3,5,7,9,22,26,41,45,46,47,54,57,60,62,65,66,69,71; With

C.I. basic black 8.

Can also be used in combination pigment.

The pigment that can be used for ink of the present invention except can be purchased those, can also be the known pigment of describing in the various reference.Reference comprises: " Color Index " (The Society ofDyers and Colourists edits), edit " the Kaitei shimpan Ganryo Binran " of (1989) by Japanese Pigment Technology Society, " Saishi nGanryo Ouyou Gijutu " CMC (1986), " Printing Ink Technology " CMC (1984), with W.Herbst and K.Hunger, " Industrial Organic Pigments ", (VCH Verlagsgesellschaft, 1993).The specific examples of pigment dyestuff comprises: azo pigment (as azo lake pigment, insoluble azo colour condenses azo pigment and chelating azo pigment), many ring pigment (as phthalocyanine pigment, anthraquinone pigment ， perylene Huo perylene ketone (perynone) pigment, indigo pigment, quinacridone pigment ， triazine dioxin pigment, isoindolinone pigment, quinophthalones pigment and diketopyrrolo-pyrrole pigment), mordant color lake (rake) pigment (for example, the pigment lake of acidity or basic dyestuff) and azine pigment, and those examples of mineral dye comprise: yellow ultramarine such as C.I. pigment yellow 34,37,42,53 etc., red pigment such as C.I. Pigment red 101,108 etc., blue pigments such as C.I. pigment blue 27,29,17:1 etc., black pigment such as C.I. Pigment black 7, magnetite etc. and white pigment such as C.I. Pigment white 4,6,18,21 etc.

As pigment with the tone that preferably is used to form image, preferred pigment comprises for the pigment of blueness to cyan: phthalocyanine pigment, anthraquinone type indanthrone blue dyestuff (for example C.I. pigment blue 60), triaryl carbon pigment with the mordant pigment lake, and most preferably phthalocyanine pigment (the preferably copper phthalocyanine, as the C.I. pigment Blue 15: 1,15:2,15:3,15:4,15:6, chlorine or low chlorine copper phthalocyanine, the aluminium phthalocyanine pigment of in European patent 860475, describing, metal-free phthalocyanine such as C.I. pigment blue 16 contain central metal Zn, the phthalocyanine of Ni or Ti, in these, C.I. pigment Blue 15 most preferably: 3 and 15:4 and aluminium phthalocyanine).

For redness to violet pigment, preferred pigment comprises: (preferred embodiment comprises the C.I. pigment red 3 to azoic dyestuff, 5,11,22,38,48:1,48:2,48:3,48:4,49:1,52:1,53:1,57:1,63:2,144,146,184 etc., among these, particularly preferred pigment is C.I. Pigment red 57:1,146 and 184), (preferred embodiment comprises the C.I. pigment red 122 to quinacridone pigment, 192,202,207, with 209, C.I. pigment violet 19 and 42, among these, particularly preferred pigment is pigment red 122), (preferred embodiment comprises xanthene type C.I. pigment red 81 to mordant pigment lake type triaryl carbon pigment: 1 and the C.I. pigment violet 1,2,3,27 and 39 etc.) triazine dioxin pigment (C.I. pigment Violet 23 for example, 37 etc.), diketopyrrolo-pyrrole pigment (for example C.I. Pigment red 254 etc.) perylene dye (C.I. pigment violet 5:1 for example, 31,33 etc.), and thioindigo color (for example, the C.I. pigment red 38,88 etc.).

For yellow ultramarine, preferred pigment comprises that (preferred embodiment comprises monoazo pigment C.I. Pigment Yellow 73 1 to azo pigment, 3,74,98, disazo pigment C.I. pigment Yellow 12,13,14,16,17,83, the C.I. Pigment Yellow 73 93 of compound azo pigment, 94,95,128,155, benzimidazolone C.I. pigment Yellow 12 0,151,154,156,180, among these, most preferred pigment is to utilize p-diaminodiphenyl as those of raw material), (preferred embodiment comprises C.I. Pigment Yellow 73 109 to isoindoline-isoindolinone pigment, 110,137,139), quinophthalones pigment (preferred embodiment comprises C.I. pigment yellow 13 8) and flavanthrone pigment (for example the C.I. Pigment Yellow 73 24).

The preferred embodiment of black pigment comprises mineral dye (preferred carbon black and magnetite) or nigrosine.

In addition, can also use orange pigments (for example C.I. pigment Orange 13 or 16), or veridian (as the C.I. pigment Green 7).

The pigment that can be used for ink of the present invention can be untreated as mentioned above pigment or carry out surface-treated pigment.The surface-treated method comprises the method for surface coated resin or wax, the method of adhesive surface activator, make active substance (as silane coupling agent, epoxy compounds, the free radical that polymeric polyisocyanate or diazonium salt produce), and be described in the following reference and patent with surface of pigments link coupled method:

[1)Property and Application of Metal Soaps(Saiwai Shobo)；

[2]Insatsu Ink Insatsu(CMC，1984)；

[3]Saishin Ganryo Ouyou Gijutsu(CMC，1986)；

[4] United States Patent (USP) 5,554, and 738 and 5,571,311;

[5] JP-ANos.9-151342,10-140065,10-292143 and 11-166145.

Particularly, in United States Patent (USP) [4], describe what making diazonium salt preparation with the carbon black reaction is effective from pigment dispersion and by the capsule pigment of the preparation of the method described in the patent [5] because under the situation of not using other dispersion agent, can in ink, obtain dispersion stabilization.

In ink of the present invention, pigment can disperse by using dispersion agent.Dispersion agent can be the various known type dispersion agents according to used pigment, the low dispersal agent molecule of surfactant type for example, or macromolecule dispersing agent for example.The example of dispersion agent is included in those that describe in JP-A No.3-69949 and the European patent 549486.In addition, when using dispersion agent, can also add the pigment derivative that is called synergistic agent, to promote the absorption of dispersion agent to pigment.

The size of particles of pigment after dispersion that can be used for ink of the present invention is preferably 0.01 to 10 μ m, more preferably 0.05 to 1 μ m.

For dispersed color, can use the known dispersion technology that in ink preparation or toning agent preparation, uses.Diverting device can be to comprise horizontal or vertical mixer grinder, attritor, colloidal mill, ball mill, three-roll grinder, ball mill, super grinding machine, impeller, dispersion machine, KD shredder, dynatron (dynatron) or pressure kneader.Details is described in " Saishin Ganryo OuyouGijutsu " (CMC, 1986).

The example of the water miscibility organic solvent (comprising water-miscible organic solvent) that adopts among the present invention comprising: alcohol (methyl alcohol for example, ethanol, propyl alcohol, Virahol, butanols, isopropylcarbinol, sec-butyl alcohol, the trimethyl carbinol, amylalcohol, hexanol, hexalin or phenylcarbinol), polyvalent alcohol (for example 1, the 2-ethylidene glycol, glycol ether, triglycol, polyoxyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, butyleneglycol, hexylene glycol, pentanediol, glycerine, hexanetriol or thiodiglycol), diol, derivatives (ethylene glycol monomethyl ether for example, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, triethylene glycol monomethyl ether, glycol diacetate, ethylene glycol monomethyl ether acetate, triethylene glycol monomethyl ether, triglycol list ether or ethyleneglycol monophenylether), amine is (as thanomin, diethanolamine, trolamine, N methyldiethanol amine, the N-ethyldiethanolamine, morpholine, N-ethylmorpholine, quadrol, diethylenetriamine, Triethylenetetramine (TETA), polymine or 4-methyl-diaminopropane), with other polar solvents (as methane amide, N, dinethylformamide, N,N-dimethylacetamide, methyl-sulphoxide, tetramethylene sulfone, 2-Pyrrolidone, the N-N-methyl-2-2-pyrrolidone N-, N-vinyl-2-Pyrrolidone, the 2-oxazolidone, 1,3-dimethyl-2-imidazolone, acetonitrile or acetone).Can be with two or more be used in combination the water miscibility organic solvent.In these, in the present invention, preferably adopting boiling point is the water miscibility organic solvent (preferably water solubleness organic solvent) of 150 ℃ or higher (preferred 200 ℃ or higher).

Below, will be explained in other component that composition for ink that the present invention is used for ink jet printing can contain:

The ink (composition) that is used for ink jet printing can contain tensio-active agent, and the adjusting of the composition for ink physical properties that obtains can improve the discharging stability of composition for ink, and provide excellent effect, as the improvement of image water-repellancy, and preventing of oozing out of the composition for ink of printing.

As for tensio-active agent, advantageously adopt anion surfactant such as sodium lauryl sulphate, sodium laurylsulfonate or benzene sulfonamide acid esters, cats product such as pyrisept, trimethylammonium pyrisept or tetrabutylammonium chloride, or nonionogenic tenside such as polyoxyethylene nonylplenyl ether, polyoxyethylene naphthyl ether, or polyoxyethylene octyl phenyl ether.Among these, preferably use nonionogenic tenside.

The content of tensio-active agent in composition for ink is 0.001 to 15 quality %, preferred 0.005 to 10 quality %, and 0.01 to 5 quality % more preferably.

The composition for ink that is used for ink jet printing in the present invention, can adopt the additive of sufficient quantity, as be used to prevent that the ink discharge mouth is owing to the dry drying that causes blocking prevents agent, is used to strengthen strong penetration enhancer, UV light absorber, antioxidant, defoamer, viscosity modifier, surface tension modifier, dispersion agent, dispersion stabilizer, mould inhibitor, rust-preventive agent and the pH regulator agent of ink infiltration paper.

The drying that adopts among the present invention prevents that agent is preferably the water-miscible organic solvent that vapour pressure is lower than water.Specific examples comprises polyvalent alcohol such as ethylene glycol, propylene glycol, glycol ether, polyoxyethylene glycol, thiodiglycol, disulfide group glycol ether, 2-methyl isophthalic acid, ammediol, 1,2,6-hexanetriol, acetylenediol derivative, glycerine or TriMethylolPropane(TMP), the lower alkyl ether of polyvalent alcohol such as glycol monomethyl methyl (or ethyl) ether, diglycol monotertiary methyl (or ethyl) ether or triglycol list ethyl (or methyl) ether; Heterogeneous ring compound such as 2-Pyrrolidone, N-N-methyl-2-2-pyrrolidone N-, 1,3-dimethyl-2-imidazolone or N-methylmorpholine, sulfocompound such as tetramethylene sulfone, dimethyl sulfoxide (DMSO) or 3-cyclobufene sultone (sulfolene), polyfunctional compound such as Pyranton or diethanolamine, and urea derivative.Among these, more preferably polyvalent alcohol such as glycerine or glycol ether.Above-mentioned drying prevent that agent from can use separately or they two or more be used in combination.Preferably use this drying to prevent agent with the amount of 10 to 50 quality % of ink.

The penetration enhancer that adopts among the present invention can be that alcohol is as ethanol, Virahol, butanols, two (three) glycol single-butyl ethers or 1,2-hexanetriol, sodium laurylsulfonate, sodium oleate or nonionogenic tenside etc.This material provides enough effects with the content of 10 to 30 quality % in ink, and preferably do not cause printing ooze out or the degree of print through on paper in use.

As for the UV light absorber that adopts in order to improve image to keep quality among the present invention, can adopt for example at JP-A Nos.58-185677,61-190537,2-782, the benzotriazole cpd that 5-197075 and 9-34057 describe, for example at JP-ANos.46-2784,5-194483 and United States Patent (USP) 3,214,463 benzophenone cpds of describing, for example at JP-B Nos.48-30492, the cinnamate compound that 56-21141 and JP-A No.10-88106 describe, for example at JP-A Nos.4-298503,8-53427,8-239368, the triaizine compounds that 10-182621 and JP-T No.8-501291 describe, the disclosed compound of Research Disclosure No.24239, or the compound of the absorption of representing by stilbene and benzoazole compounds ultraviolet ray and emitting fluorescence, promptly so-called white dyes.

Antioxidant as for using in order to improve image storage property among the present invention can adopt the anti-decolourant of various organic types and metal compounding material type.Organic anti-decolourant comprises quinhydrones, alcoxyl phenol, and dialkoxy phenol, phenol, aniline, amine, indane, chroman, alcoxyl aniline and heterogeneous ring compound, and metal complexes comprises nickel complex and Zn complex.More clearly, can adopt No.17643, VII, I-J item at ReserchDisclosure; No.15162; No.18716, the 650th page, left hurdle; No.36544, the 527th page; No.307105, the 872nd page; With the compound of describing in the patent of quoting among the No.15162; With at JP-ANo.62-215272, included compound in the formula of described representative compounds of 127-137 page or leaf and examples of compounds.

The defoamer that adopts among the present invention is the multipolymer of dimethyl polysiloxane and polyoxyalkylene, and it exists with side chain type, terminal groups modification type and NBA type, in these, and the preferential side chain.This polymkeric substance can be used as FZ-2203 ,-2207 ,-2222 and-2166 (trade(brand)name is made by Nippon Unicar Co.) and obtains.

The mould inhibitor that adopts among the present invention can be a Sodium dehydroacetate, Sodium Benzoate, pyrithione-1-sodium oxide, ethyl p-hydroxybenzoate, 1,2-benzisothiazole-3-ketone and salt thereof.This material preferably uses with the amount of 0.02 to 5.0 quality % in ink.

The details of these materials for example is described among " the Bokin-Bokunzai Jiten " of (Japan Antibacterial-antimold Society, Dictionary Editing Committee edits).

In addition, rust-preventive agent can be for example acid accumulator sulfite, Sulfothiorine, THIOGLYCOLLIC ACID ammonium, nitrous acid di-isopropyl ammonium, four pentaerythritol tetranitrates, nitrous acid dicyclohexyl ammonium or benzotriazole.This material preferably uses with the amount of 0.02 to 5.00 quality % in ink.

Can be with sharply the pH regulator agent of using among the present invention being used to regulate pH regulator and being used to provide dispersion stabilization, and preferably with ink at 25 ℃ pH regulator 8 to 11.PH less than 8 reduces the solubleness of dyestuff, thereby tends to cause nozzle blockage, and tends to make water-repellancy to worsen above 11 pH.The pH regulator agent can be used as the organic bases or the mineral alkali of alkaline matter, or as the organic acid or the mineral acid of acidic substance.

Organic bases can be trolamine, diethanolamine, N methyldiethanol amine or dimethylethanolamine.Mineral alkali can be alkali-metal oxyhydroxide (for example sodium hydroxide, lithium hydroxide or a potassium hydroxide), carbonate (for example yellow soda ash or sodium bicarbonate) or ammonium.In addition, organic acid can be acetate, propionic acid, trifluoroacetic acid or alkylsulphonic acid.Mineral acid can be hydrochloric acid, sulfuric acid or phosphoric acid.

In the present invention, except the betaine compound that comprises above-mentioned tensio-active agent, can be with nonionic, positively charged ion or anion surfactant as surface tension modifier.Anion surfactant can be for example soap, alkyl sulfuric ester salt, alkylbenzene sulfonate, sulfonated alkyl naphathalene, dialkyl sulfosuccinates, alkyl phosphate salt, naphthene sulfonic acid-formaldehyde condensation products or polyxyethylated sulphonate salt.Nonionogenic tenside can be Voranol EP 2001, polyxyethylated allyl ethers, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene alkyl amine, glycerol fatty acid ester, oxyethylene oxypropylene polymer etc.Also preferably use Surfynols (Air Products ﹠amp; Chemicals Co.), it is an acetylene type polyoxyethylene oxide surface promoting agent.

Below, will explain ink jet recording materials of the present invention.

Ink jet recording materials of the present invention is included in the ink receiving layer on the group at least, and described ink receiving layer contains the compound of formula (A).The preferred ink receiving layer also contains water soluble resin, and more preferably also contains particulate, and further preferably contains mordant.Containing under the situation of water soluble resin, more preferably it contain can with the crosslinked linking agent of water soluble resin.

(base material)

The base material that the present invention is used for ink jet recording materials can be the transparent substrate that comprises transparent material such as plastics, or comprises the opaque group of opaque material such as paper.In order to manifest the benefit of the ink receiving layer transparency, the opaque base material of preferably transparent group or high glossiness.

As for the material that can be used for transparent substrate, be preferably the material that when being used for overhead projection or demonstration backlight, can tolerate irradiation heat.This material for example can be: polyester such as polyethylene terephthalate, polysulfones, polyphenylene oxide, polyimide, polycarbonate or polymeric amide.In these, preferred polyester, and preferred especially polyethylene terephthalate.

Thickness to transparent substrate has no particular limits, and considers the easiness of processing, preferably in the scope of 50 to 200 μ m.

The opaque base material of high glossiness is 40% or higher material providing glossiness on that side surface of ink receiving layer preferably.Glossiness recited above is to determine according to the method described in the JISP-8142 (75 ° of mirror surface luster test methods of paper and plate).More specifically, can adopt following base material.

Example comprises: the paper base material of high glossiness such as art paper, White Board, glazed coated paper or be used for the halogenation money base and take a picture with the employed barytage paper of base material; (it can be surperficial calendering) film of the high glossiness that forms by following method: at plastic film for example polyester such as polyethylene terephthalate (PET), cellulose ester such as Nitrocellulose, rhodia, cellulose acetate butyrate, polysulfones, polyphenylene oxide, polyimide contains adularescent face material in polycarbonate or the polymeric amide; Perhaps, at above-mentioned paper base material, above-mentioned transparent substrate or contain the base material that contains or do not contain the polyolefin coating of white face material on the film surface of high glossiness of adularescent face material.

In addition, contain adularescent face material the expanded polyester film (for example, wherein contain the polyolefine particulate and by stretching and interstitial foaming PET) be favourable, and to be used for the resin-coated paper that the halogenation money base takes a picture with photo paper also be favourable.

Thickness to above-mentioned opaque base material has no particular limits, and considers that handling property is preferably 50 to 300 μ m.

In addition, also can carry out Corona discharge Treatment, glow discharge processing, flame treating or ultraviolet irradiation, to improve wet performance and bond properties to substrate surface.

Below, will provide detailed explanation to the body paper that adopts in the resin-coated paper.

This body paper mainly with wood pulp for grinding, and as required, except wood pulp, use synthetic paper-pulp, as the synthon of polyacrylic synthetic paper-pulp or synthon such as nylon and polyester.Wood pulp can be any among LBKP, LBSP, NBKP, NBSP, LDP, NDP, LUKP and the NUKP, and preferred vast scale ground uses staple fibre many LBKP, NBSP, LBSP, NDP or LDP.

But ratio LBSP and/or LDP are preferably 10 to 70 quality %.

As for above-mentioned paper pulp, preferably use the dissolving pulp (as sulfate pulping or sulfite pulp) of low impurity content, and also be useful by the paper pulp that bleaching improves whiteness.

In the body paper, can add sizing agent such as higher fatty acid or alkyl ketene dimer aptly, white face material such as lime carbonate, talcum or titanium oxide, paper intensity reinforcing agent such as starch, polyacrylamide or polyvinyl alcohol, white dyes, water retention agent such as polyoxyethylene glycol, dispersion agent, tenderizer such as quaternary ammonium salt etc.

The water filtration degree that is preferred for making the paper pulp of paper is 200 to 500ml in the CSF standard, and the quality % of 24 screen residues stipulated in JIS P-8207 of the staple length after the making beating and the quality % sum of 42 screen residues are 30 to 70%.In addition, 4 screen residues are preferably 20 quality % or lower.

Body paper quantitatively be preferably 30 to 250g/m ², be preferably 50 especially to 200g/m ²The thickness of body paper is preferably 40 to 250 μ m.Body paper is in system during paper or carry out calender process afterwards and can obtain high slickness.Body paper density is generally 0.7 to 1.2g/m ²(JIS P-8118).

In addition, the rigidity of body paper is preferably 20 to 200g under the defined terms in JIS P-8143.

Body paper also can the surface coated Surface Size, and described Surface Size can be identical with the sizing agent that adds in the body paper.

The pH value that body paper is measured by the hot-water extraction method that limits among the JIS P-8113 is preferably 5 to 9.

The polyethylene that is used to apply the body paper end face and the back side mainly is new LDPE (film grade) (LDPE) and/or high density polyethylene(HDPE) (HDPE), but also can partly adopt LLDPE or polypropylene etc.

Especially, form the polyethylene layer of that side of ink receiving layer, what preferably institute carried out usually in photo paper, by being added to, the native indigo plant of rutile or anatase titanium oxide, white dyes or general Shandong improves opaqueness, whiteness and tone in the polyethylene.Titanium oxide preferably is about 3 to 20 quality % with respect to poly content, more preferably 4 to 13 quality %.Thickness to polyethylene layer is not particularly limited, but all is preferably 10 to 50 μ m in top layer and backing layer.On polyethylene layer, undercoat can be provided, think that the ink receiving layer provides bond properties.This undercoat is preferably formed by waterborne polyester, gelatin or PVA.The thickness of preferred undercoat is 0.01 to 5 μ m.

Polyethylene coated paper can be used as the paper with high glossiness and uses, and perhaps, extrudes operation by melt extruding at polyethylene to be applied on the body paper surface, may form the tarnish or the thread surface that are used for common photo paper.

Base material can also provide back coating, and the component that can be added to this back coating comprises white pigment, aqueous binder etc.

The example of the white pigment that contains in back coating comprises inorganic white pigment such as light calcium carbonate, water-ground limestone, kaolin, talcum, calcium sulfate, barium sulfate, titanium dioxide, zinc oxide, zinc sulphide, zinc carbonate, stain white, pure aluminium silicate, diatomite, Calucium Silicate powder, Magnesium Silicate q-agent, synthetic soft silica, colloid silica, colloidal alumina, pseudobochmite, aluminium hydroxide, aluminum oxide, lithopone, zeolite, hydrated halloysite, magnesiumcarbonate or magnesium hydroxide and pigment dyestuff such as styrene plastic pigment, acrylics pigment, polyethylene, microcapsule, urea resin or melamine resin.

The aqueous binder that adopts in back coating can be for example water-soluble polymers such as vinylbenzene/maleate copolymer, styrene/acrylic salt copolymer, polyvinyl alcohol, silanol-modified polyethylene alcohol, starch, cationic starch (caolinated starch), casein, gelatin, carboxymethyl cellulose, Natvosol or polyvinylpyrrolidone and aqueous dispersion polymers such as styrene-butadiene latex or acryl emulsion.

Other component that can contain in back coating comprises: defoamer, antifoams, dyestuff, white dyes, sanitas and water repellent agent.

In recording materials of the present invention, its ink receiving layer preferably contains water soluble resin.

The example of water soluble resin comprises: comprise that polyvinyl alcohol resin as the unitary hydroxyl of hydrophilic structure is [as polyvinyl alcohol (PVA); acetate ethanoyl modified polyethylene alcohol; cation-modified polyvinyl alcohol; anion-modified polyvinyl alcohol; silanol modified polyethylene alcohol or polyvinyl acetal]; celluosic resin is [as methylcellulose gum (MC); ethyl cellulose (EC); Natvosol (HEC); carboxymethyl cellulose (CMC); hydroxypropylcellulose (HPC); hydroxyethylmethyl-cellulose or Vltra tears]; chitin; chitosan; starch; the resin of ether-containing key [polyethylene oxide (PEO); poly(propylene oxide) (PPO); polyoxyethylene glycol (PEG) or polyvingl ether (PVE)] and the resin that contains formamyl [as polyacrylamide (PAAM); Polyvinylpyrolidone (PVP) (PVP) or polyacrylic acid hydrazine].

Having of also comprising contains polyacrylate, maleic acid resin, alginate and the glue of carboxyl as dissociable group.

In these, special preferably polyethylene alcohol resin.The example of polyvinyl alcohol resin is included in following middle those that describe: JP-B Nos.4-52786,5-67432 and 7-29479, Japanese Patent No.2537827, JP-B No.7-57553, Japanese Patent Nos.2502998 and 3053231, JP-A No.63-176173, Japanese Patent No.26-4367, JP-A Nos.7-276787,9-207425,11-58941,2000-135858,2001-205924,2001-287444,62-278080 and 9-29373, Japanese Patent No.2750433, JP-A Nos.2000-158801,2001-213045,2001-328345,8-324105 and 11-348417.

In addition, the example of the water soluble resin except that polyvinyl alcohol resin is included in those described in the JP-A No.11-165461 0011-0014 section.

This class water soluble resin can use separately or two or more are used in combination.

With respect to all solids quality of ink receiving layer, the content of water soluble resin of the present invention is preferably 9 to 40 quality %, more preferably 12 to 33 quality %.

(particulate)

In recording materials of the present invention, further the preferred ink receiving layer contains particulate.The existence of particulate in the ink receiving layer can provide vesicular structure, thereby improves the ink absorption performance.Particularly, this particulate preferably the solid content in the ink receiving layer be equal to or higher than 50 quality %, more preferably be higher than under the situation of 60 quality %, can form again better vesicular structure, thereby offer the enough ink absorption performances of recording materials.The solids content of particulate in the ink receiving layer is based on that component outside dewatering in the composition that constitutes the ink receiving layer calculates.

Particulate of the present invention can be organic particulate or fine inorganic particle, but considers ink absorption performance and picture steadiness, preferred fine inorganic particle.

Organic particulate preferably for example obtains polymer particle by letex polymerization, micro-emulsion polymerization, soap-free polymerization, seeding polymerization, dispersion polymerization or suspension polymerization, and can be the polymer particle of powder, latex or the emulsion attitude of polyethylene, polypropylene, polystyrene, polyacrylic ester, polymeric amide, silicone resin, phenol-formaldehyde resin or natural polymer.

Fine inorganic particle can be inorganic white pigment powder such as SiO 2 powder, colloid silica, titanium dioxide, barium sulfate, Calucium Silicate powder, zeolite, kaolinite, halloysite, mica, talcum, lime carbonate, magnesiumcarbonate, calcium sulfate, pseudobochmite, zinc oxide, zinc hydroxide, aluminum oxide, pure aluminium silicate, Calucium Silicate powder, Magnesium Silicate q-agent, zirconium white, zirconium hydroxide, cerium oxide, lanthanum trioxide or yttrium oxide.In these, consider satisfied vesicular structure, preferred fine particles of silica, colloid silica, aluminum oxide fines grain or pseudobochmite.Particulate can be the state employing with the state of primary particle or formation secondary particle.The average primary particle size of this particulate is preferably 2 μ m or littler, more preferably 200nm or littler.

Further preferred average primary particle size is preferably 20nm or littler fine particles of silica; average primary particle size is preferably 30nm or littler colloid silica; average primary particle size is preferably 20nm or littler aluminum oxide particulate; or average pore radius is 2 to 15nm pseudobochmite, preferred especially fine particles of silica, aluminum oxide particulate or pseudobochmite.

According to the preparation method, fine particles of silica is divided into wet method particle and dry method (vapor phase process) particle.Wet method is carried out the acidolysis of silicate usually, obtains active silica, and polymerization and deposition obtain aqueous silicon dioxide aptly for they.On the other hand, vapor phase process adopts the method for the halid high temperature vapor phase hydrolysis of silicon (flame hydrolysis) usually, or in electric furnace with reduction and gaseous silicon-dioxide and coke under the electric-arc heating, use the method (arc process) of atmospheric oxidation then, and " fumed silica " is meant the anhydride silica particle that obtains by this vapor phase process.The fine particles of silica that adopts among preferred especially the present invention is the fumed silica particulate.

Whether etc. fumed silica is different from aqueous silicon dioxide in the aspect in the existence of the silanol base density on surface, emptying aperture, thereby demonstrates different character, and is suitable for forming the three-dimensional structure of high voidage.The reason of this behavior is unclear, but infers, aqueous silicon dioxide at the silanol base density of particle surface up to 5 to 8/nm ², and form the fine and close aggregate of particulate easily, and fumed silica is low at the silanol base density of particle surface, is 2 to 3/nm ², therefore form more unsound flock, thereby cause forming the more structure of high voidage.

Fumed silica has following feature: extra high specific surface area, cause high ink absorption and high ink to keep efficient, with low refractive index, when being separated into suitable size of particles, it provides the ink receiving layer transparency, thereby high colour density and satisfied color developing is provided.The transparency of ink receiving layer is important for the Application Areas that requires transparency as OHP paper not only, and is important for ink jet recording materials as photo shape glossy paper, to obtain high colour density and satisfied color developing and glossiness.

The average primary particle size of preferred fumed silica is 30nm or littler, is preferably 20nm or littler, is preferably 10nm or littler especially, and most preferably is 3 to 10nm.Fumed silica owing to the hydrogen bond based on the silanol base makes between the particle adherent trend mutually, is under 30nm or the lower situation in average primary particle size, can form the structure of high voidage, thereby improve the ink absorption performance effectively.

Fine particles of silica can be used in combination with other particulate recited above.Under the situation that is used in combination other particulate of this class and fine particles of silica, the content of aerosil particulate in all particulates is preferably 30 quality % or higher, more preferably 50 quality % or higher.

As for fine inorganic particle of the present invention, also preferred aluminum oxide particulate, hydrated alumina, its mixture or mixture.In these, preferred hydrated alumina, reason is that it absorbs and the fixing ability of ink satisfactorily, and preferred especially pseudobochmite (Al ₂O ₃NH ₂O).Can adopt hydrated alumina with various forms, but the preferred boehmite of dissolved colloidal state that adopts is as raw material, because can easily obtain smooth layer.

As for the pore structure of pseudobochmite, preferably its average pore radius is 1 to 30nm, and more preferably 2 to 15nm.In addition, preferred pore volume is 0.3 to 2.0ml/g, and more preferably 0.5 to 1.5ml/g.Pore radius and pore volume are to be recorded by nitrogen adsorption-desorption method with for example gas adsorption-desorption analysis instrument (for example, the Omnisorp 369 (trade(brand)name) that is made by Coulter Inc.).

In the aluminum oxide particulate, preferred vapor phase process aluminum oxide particulate, reason is the specific surface area that it is big.The average primary particle size of preferred this vapor phase process aluminum oxide is 30nm or littler, more preferably 20nm or littler.

Under the situation of the above-mentioned particulate that in recording materials, adopts, can advantageously adopt in for example pattern described in the following patent: JP-A Nos.10-81064,10-119423,10-157277,10-217601,11-348409,2001-138621,2000-43401,2000-211235,2000-309157,2001-96897,2001-137$8627,11-91242,8-2087,8-2090,8-2091,8-2093,8-174992,11-192777 and 2001-301314.

In the ink receiving layer of the present invention, water soluble resin and particulate can be single material or multiple mixtures of material separately.In order to keep transparency, with particulate, particularly the type of the water soluble resin of fine particles of silica combination is important.Adopting under the situation of fumed silica, the preferably water soluble resin is a polyvinyl alcohol resin, is more preferably saponification deg and is 70 to 100% polyvinyl alcohol resin, and special preferably saponification deg is 80 to 99.5% polyvinyl alcohol resin.

Polyvinyl alcohol resin contains hydroxyl in its structural unit, and the silane surface alcohol radical of this hydroxyl and fine particles of silica forms hydrogen bond, thereby promote the formation of tridimensional network, in tridimensional network, the secondary particle of fine particles of silica constitutes netted chain unit.Estimate that this tridimensional network can form the ink receiving layer of the vesicular structure with high porosity and sufficient intensity.

In ink-vapor recording, the porous ink receiving layer that obtains thus absorbs ink apace by capillary phenomenon, and can form the point that does not have the satisfied circularity that ink oozes out.

In addition, polyvinyl alcohol resin can be used in combination with other water soluble resin recited above.Under the situation that other water soluble resin of this class and polyvinyl alcohol resin are used in combination, the content of polyvinyl alcohol resin in whole water soluble resins is preferably 50 quality % or higher, more preferably 70 quality % or higher.

The content ratio of＜particulate and water soluble resin 〉

The mass content ratio of particulate (x) and water soluble resin (y) [PB ratio (x/y)] also influences the membrane structure and the film toughness of ink receiving layer significantly.More specifically, higher mass content ratio (PB ratio) improves porosity, pore volume and surface-area (per unit mass), but tends to make density and intensity to degenerate.

The mass content ratio of preferred ink receiving layer of the present invention (PB ratio) is in the scope of 1.5:1 to 10:1, with the loss of the film toughness that prevents to cause or the crackle when dry by too high PB ratio, and prevent that the resin that caused by too low PB ratio from stopping up the porosity of aperture and reduction, thereby cause the ink absorption performance that worsens.

Require the ink receiving layer to have sufficiently high film toughness, reason is to have applied stress to ink jet recording materials by the delivery system in the ink-jet printer time.Also require in the enough film toughnesss of ink receiving layer, with prevent its in the operation that cuts into paper crackle or peel off.Consider these requirements, quality ratio (x/y) is preferably 5:1 or littler, and 2:1 or higher more preferably, to guarantee beating high speed ink receptivity on the machine machine in ink-jet.

By using the coating fluid coated substrate, in the described coating fluid, being 20nm or littler fumed silica particulate and water soluble resin with average primary particle size is scattered in the aqueous solution with the quality ratio (x/y) of 2:1 to 5:1 fully, and by drying coated layer, form tridimensional network by secondary particle as the fine particles of silica of netted chain, and can easily obtain translucent porous-film, its mean pore size is 30nm or littler, porosity is 50-80%, specific pore volume is 0.5ml/g or bigger, and specific surface area is 100m ²/ g or bigger.

(linking agent)

In recording materials of the present invention, preferably the ink receiving layer that constitutes by the coating layer that comprises particulate and water soluble resin further comprise can the cross-linked, water-soluble resin linking agent, and constitute by the crosslinking reaction of linking agent and water soluble resin the solidified porous layer.

Preferably boron compound is used for cross-linked, water-soluble resin, particularly polyvinyl alcohol.The example of boron compound comprises: borax, boric acid, borate such as orthoboric acid salt are (as InBO ₃, ScBO ₃, YBO ₃, LaBO ₃, Mg ₃(BO ₃) ₂Or Co ₃(BO ₃) ₂, biborate is (as Mg ₂B ₂O ₅Or Co ₂B ₂O ₅), metaborate is (as LiBO ₂, Ca (BO ₂) ₂, NaBO ₂Or KBO ₂), tetraborate is (as Na ₂B ₄O ₇10H ₂O) and pentaborate (as KB ₅O ₈4H ₂O, Ca ₂B ₆O ₁₁7H ₂O or CsB ₅O ₅).In these, aspect induced cross-linking reaction apace, preferred borax, boric acid or borate, and special preferred boric acid.

In addition, the linking agent that the following compounds different with boron compound can be used as water soluble resin.

Example comprises: aldehyde cpd such as formaldehyde, oxalic dialdehyde or glutaraldehyde; Ketone compound such as di-acetyl or cyclopentanedione; Active halogen compound is as two (2-chloroethyl urea)-2-hydroxyls-4,6-two chloro-1,3,5-triazines or 2,4-two chloro-6-S-triazine sodium salts; Active vinyl-compound such as divinyl sulfonic acid, 1,3-vinylsulfonyl-2-propyl alcohol, N, N '-ethene two (vinylsulfonyl ethanamide) or 1,3,5-triacryl-six hydrogen-S-triazine; N-methylol compound such as dihydroxymethyl urea or methylol dimethyl hydantion; Melamine resin (as melamine methylol or alkylation melamine methylol); Resins, epoxy; Isocyanate compound such as hexamethylene diisocyanate; United States Patent(USP) Nos. 3,017,280 and 2,983, the aziridine cpd of describing in No. 611; U.S. Patent No. 3,100, the carboxylic imide compound of describing in 704; Epoxy compounds such as glycerine triglycidyl group ether; Ethylidene imino-compounds is as 1,6-hexa-methylene-N, N '-diethylidene urea etc.; Halogenation carboxyl aldehyde cpd such as mucochloric acid, glue phenoxy chloric acid; The diox compound is as 2,3-Er Qiang Ji diox; Metallic compound such as lactic acid titanium, Tai-Ace S 150, chromium alum, potassium alum, zirconyl acetate or chromium acetate; Polyamine compounds such as tetren; Hydrazide compound such as adipic dihydrazide; With the low-molecular weight compound or the polymkeric substance that contain Liang or Duo Ge oxazolinyl.

These linking agents can adopt separately or two or more are used in combination.

For example, on the situation of boron compound, can preferably provide linking agent in the following manner.This by as be issued to: the ink receiving layer be by form by the cross linking reaction and solidification coating layer the layer situation under, described coating layer is to contain particulate by coating, comprise the water soluble resin of polyvinyl alcohol and the coating solution of boron compound (below be also referred to as first coating solution), and crosslinking curing is undertaken by following: (1) and coating coating solution while, or (2) forming in the process of coating layer (being also referred to as coated film) and before coating layer begins to show the rate of drying of decline by applying coating solution recited above, and applying pH to this coating layer or coated film is 8 or higher basic solution (below be also referred to as second coating fluid).

Linking agent is preferably 1 to 50 quality % with respect to the amount of water soluble resin, and 5 to 40 quality % more preferably.

(mordant)

Among the present invention, the preferred ink receiving layer contains mordant, with the water tolerance that improve to form image and anti-through the time exudative.

Preferred mordant is cationic polymers (cationic mordant) or the inorganic mordant as organic mordant.Be present in this in the ink receiving layer and mordant caused with comprising the liquid ink as the anionic dyestuff of colorant interact, thereby make colorant stable, and improve water tolerance and through the time exudative.Can adopt organic mordant and inorganic mordant alone or in combination.

Mordant can be added in the coating fluid (first coating fluid) that contains particulate and water soluble resin, or under worry and particulate agglomerative situation, be added in second coating fluid and coating.

As for cationic mordant, can advantageously adopt contain uncle to uncle's amino or quaternary ammonium salt base as the polymer mordant of cation group, still, also can use positively charged ion non-polymer mordant.

Polymer mordant preferably contains the homopolymer of uncle's ammonia to the monomer (mordant monomer) of uncle's amino, its salt or quaternary ammonium salt, or the multipolymer or the polycondensate of this mordant dyeing monomer and other monomers (hereinafter referred to as " non-mordant monomer ").In addition, these polymer mordant also can be used with the form of water-soluble polymers or water dispersible latex particle.

The example of monomer (mordant monomer) comprising: trimethylammonium-right-vinyl benzyl chlorination ammonium, trimethylammonium--vinyl benzyl chlorination ammonium, triethyl-right-vinyl benzyl chlorination ammonium, triethyl--vinyl benzyl chlorination ammonium, N, N-dimethyl-N-ethyl-N-is right-vinyl benzyl chlorination ammonium, N, N-diethyl-N-methyl-N-is right-vinyl benzyl chlorination ammonium, N, N-dimethyl-N-n-propyl-N-is right-vinyl benzyl chlorination ammonium, N, N-dimethyl-N-n-octyl-N-is right-vinyl benzyl chlorination ammonium, N, N-dimethyl-N-benzyl-N-is right-vinyl benzyl chlorination ammonium, N, N-diethyl-N-benzyl-N-is right-vinyl benzyl chlorination ammonium, N, N-dimethyl-N-(4-methyl) benzyl-N-is right-vinyl benzyl chlorination ammonium, N, N-dimethyl-N-phenyl-N-is right-vinyl benzyl chlorination ammonium, trimethylammonium-right-vinyl benzyl brometo de amonio, trimethylammonium--the vinyl benzyl brometo de amonio, trimethylammonium-right-vinyl benzyl ammonium sulphonate, trimethylammonium--the vinyl benzyl ammonium sulphonate, trimethylammonium-right-vinyl benzyl ammonium acetate, trimethylammonium--the vinyl benzyl ammonium acetate, N, N, N-triethyl-N-2-(4-ethenylphenyl) ethyl ammonium chloride, N, N, N-triethyl-N-2-(3-ethenylphenyl) ethyl ammonium chloride, N, N-diethyl-N-methyl-N-2-(4-ethenylphenyl) ethyl ammonium chloride, N, N-diethyl-N-methyl-N-2-(4-ethenylphenyl) ethyl acetic acid ammonium;

By N, N-dimethyl aminoethyl (methyl) acrylate, N, N-diethylamino ethyl (methyl) acrylate, N, N-dimethylaminopropyl (methyl) acrylate, N, N-diethylamino propyl group (methyl) acrylate, N, N-dimethyl aminoethyl (methyl) acrylamide, N, N-diethylamino ethyl (methyl) acrylamide, N, N-dimethylaminopropyl (methyl) acrylamide or N, N-diethylamino propyl group (methyl) acrylamide and methyl chloride, ethyl chloride, monobromomethane, monobromoethane, quaternized thing that methyl-iodide or iodoethane form and the sulfonate that its negatively charged ion replacement is formed, alkylsulfonate, acetate or alkyl carboxylate.

Concrete example comprises: the monomethyl diallyl ammonium chloride, trimethylammonium-2-(methacryloxy) ethyl ammonium chloride, triethyl-2-(methacryloxy) ethyl ammonium chloride, trimethylammonium-2-(acryloxy) ethyl ammonium chloride, triethyl-2-(acryloxy) ethyl ammonium chloride, trimethylammonium-3-(methacryloxy) propyl ammonium chloride, triethyl-3-(methacryloxy) propyl ammonium chloride, trimethylammonium-2-(methacrylamido) ethyl ammonium chloride, triethyl-2-(methacrylamido) ethyl ammonium chloride, trimethylammonium-2-(acrylamido) ethyl ammonium chloride, triethyl-2-(acrylamido) ethyl ammonium chloride, trimethylammonium-3-(methacrylamido) propyl ammonium chloride, triethyl-3-(methacrylamido) propyl ammonium chloride, trimethylammonium-3-(acrylamido) propyl ammonium chloride, triethyl-3-(acrylamido) propyl ammonium chloride, N, N-dimethyl-N-ethyl-2-(methacryloxy) ethyl ammonium chloride, N, N-diethyl-N-methyl-2-(methacryloxy) ethyl ammonium chloride, N, N-dimethyl-N-ethyl-3-(acrylamido) propyl ammonium chloride, trimethylammonium-2-(methacryloxy) ethyl brometo de amonio, trimethylammonium-3-(acrylamido) propyl group brometo de amonio, trimethylammonium-2-(methacryloxy) ethylsulfonic acid ammonium and trimethylammonium-3-(acryloxy) propyl-acetic acid ammonium.

But the monomer of other copolymerization comprises N-vinyl imidazole and N-vinyl-glyoxal ethyline.

Can also use allyl amine, diallyl amine, its derivative or salt.This examples for compounds comprises: allyl amine, allylamine hydrochloride, the allyl amine acetate, allyl amine vitriol, diallyl amine, the diallyl amine hydrochlorate, the diallyl amine acetate, diallyl amine vitriol, diallyl methylamine and salt thereof (example hydrochloric acid salt, acetate or vitriol), diallyl ethylamine and salt thereof (example hydrochloric acid salt, acetate or vitriol) and diallyl dimethyl ammonium salt (counter ion are chlorions, acetate ion or sulfate ion).These derivatives that show the allyl amine of oligomerization performance or diallyl amine under the amine attitude are usually with the form polymerization of salt, and carry out desalination if desired.

Can also utilize by polymerization N-vinyl acetamide or the N-vinyl formamide vinyl amine unit that forms of hydrolysis then, or this unitary salt.

Above-mentioned non-mordant monomer is meant such monomer, its do not contain alkalescence or cationic moiety as uncle to uncle's amino, its salt, or quaternary ammonium salt group, and not with or do not interact basically with the dyestuff of the ink that is used for ink jet printing.

Non-mordant monomer comprises: (methyl) alkyl acrylate; (methyl) vinylformic acid cycloalkyl ester is as (methyl) cyclohexyl acrylate; (methyl) vinylformic acid aryl ester is as (methyl) phenyl acrylate; Aralkyl ester is as (methyl) benzyl acrylate; Aromatic vinyl compound such as vinylbenzene, Vinyl toluene or alpha-methyl styrene; Vinyl ester such as vinyl-acetic ester, propionate or vinyl versatate ester (vinylversatate); Allyl ester such as allyl acetate; Halogen containing monomer is as 1,1-vinylidene chloride or vinylchlorid; Vinyl cyanide is as (methyl) vinyl cyanide; With alkene such as ethene or propylene.

(methyl) alkyl acrylate is preferably (methyl) alkyl acrylate that contains 1 to 18 carbon atom in moieties, as (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) propyl acrylate, (methyl) isopropyl acrylate, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate, (methyl) Ethyl acrylate, (methyl) Octyl acrylate, (methyl) 2-EHA, (methyl) lauryl acrylate or (methyl) stearyl acrylate ester.In these, preferred methyl acrylate, ethyl propenoate, methyl methacrylate, Jia Jibingxisuanyizhi, hydroxyethyl methylacrylate.

In addition, the non-mordant monomer of this class can use separately, also can two or more be used in combination.

In addition, the preferred embodiment of polymer mordant comprises: diallyl dimethyl ammoniumchloride, polymethyl acyloxy ethyl-beta-hydroxyethyl alkyl dimethyl ammonium chloride, polymine, PAH and derivative thereof, polymeric amide-polyamide resin, cationic starch, Dyhard RU 100-formalin condenses, dimethyl-2-hydroxypropyl ammonium salt polymkeric substance, poly-amidine, polyvinylamine, the dicyanogen methyl isophorone resin cation (R.C.) of representing by Dyhard RU 100-formalin condenses, the polyamine resin cation (R.C.) of representing by Dyhard RU 100-diethyl triamine polycondensate, Epicholorohydrin-dimethyl amine addition polymer, dimethyl diallyl ammonium chloride-SO ₂Multipolymer, diallyl amine salt-SO ₂Multipolymer, contain the polymkeric substance (it contains the alkyl that is replaced by quaternary ammonium salt group in ester moiety) of (methyl) acrylate and contain the styrene-based polymer of the alkyl that is replaced by quaternary ammonium salt group.

The specific examples of polymer mordant is described in for example following patent: JP-A Nos.48-28325,54-74430,54-124726,55-22766,55-142399,60-23850,60-23851,60-23852,60-23853,60-57836,60-60643,60-118834,60-122940,60-122941,60-122942,60-235134 and 1-161236, United States Patent(USP) Nos. 2,484,430,2,548,564,3,148,061,3,309,690 and 4,115,124,4,124,324, JP-A Nos.1-161236,10-81064,10-119423,10-157277,10-217601,11-348409,2001-138621,2000-4301,2000-211235,2000-309157,2001-96897,2001-138627,11-91242,8-2087,8-2090,8-2091,8-2093,8-174992,11-192777 and 2001-301314, JP-B Nos.5-35162,5-35163,5-36164 and 5-88846, JP-A Nos.7-118333 and 2000-344990, and Japanese Patent Nos.2648847 and 2661677.In these, particularly preferably be PAH and derivative thereof.

As for the organic mordant among the present invention, for preventing that along with the oozing out of time special preferable weight-average molecular weight is 100,000 PAH and derivative thereof.

As for the PAH or derivatives thereof that adopts among the present invention, can be various known allylamine polymers and derivative thereof.This derivative comprises that (acid can be mineral acid example hydrochloric acid, sulfuric acid, phosphoric acid or nitric acid for PAH and acid, organic acid such as methylsulfonic acid, toluenesulphonic acids, acetate, propionic acid, styracin or (methyl) vinylformic acid, or their combination, or the salt that only in a PAH part, forms) salt, the derivative that polymer reaction by polyallylamine forms, the multipolymer of polyallylamine and another kind of copolymerisable monomer (this class monomer for example can be (methyl) acrylate, vinylbenzene, (methyl) acrylamide, vinyl cyanide or vinyl ester).

The specific examples of PAH and derivative thereof is included in the compound described in the following patent: JP-B Nos.62-31722,2-14364,63-43402,63-43403,63-45721,63-29881,1-26362,2-56365,2-57084,4-41686,6-2780,6-45649,6-15592 and 4-68622, Japanese Patent Nos.3199227 and 3008369, JP-A Nos.10-330427,11-21321,2000-281728,2001-106736,62-256801,7-173286,7-213897,9-235318,9-302026 and 11-21321, WO Nos.99/21901 and 99/19372, JP-A No.5-140213 and JP-T No.11-506488.

As for mordant of the present invention, also can use inorganic mordant, it can be polyvalent water-soluble metal salt or hydrophobic metals salt compound.The specific examples of inorganic mordant comprises salt or the title complex that is selected from down the metal in the group: magnesium, aluminium, calcium, scandium, titanium, vanadium, manganese, iron, nickel, copper, zinc, gallium, germanium, strontium, yttrium, zirconium, molybdenum, indium, barium, lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, dysprosium, erbium, ytterbium, hafnium, tungsten and bismuth.

Example comprises more specifically: lime acetate, calcium chloride, calcium formiate, calcium sulfate, barium acetate, barium sulfate, barium phosphate, Manganous chloride tetrahydrate, manganous acetate, formic acid manganese dihydrate, the ammonium manganous sulfate hexahydrate, cupric chloride, ammonium chloride copper (II) dihydrate, copper sulfate, cobalt chloride, cobaltous thiocyanate, rose vitriol, the nickel sulfate hexahydrate compound, nickel chloride hexahydrate, Nickel diacetate tetrahydrate, the nickel ammonium sulfate hexahydrate, amide group single nickel salt tetrahydrate, Tai-Ace S 150, al alum, the many aluminium hydroxides of alkalescence, aluminium sulfite, thiosulfuric acid aluminium, POLY ALUMINIUM CHLORIDE, the aluminum nitrate nonahydrate, aluminum chloride hexahydrate, ferrous bromide, iron protochloride, iron(ic) chloride, ferrous sulfate, ferric sulfate, zinc paraphenol sulfonate, zinc bromide, zinc chloride, the zinc nitrate hexahydrate, zinc sulfate, titanium tetrachloride, titanium isopropylate, the acetylacetonate titanium, the lactic acid titanium, zirconium acetylacetonate, zirconyl acetate, zirconyl sulfate, zirconium carbonate ammonium, zirconyl stearate, zirconyl octoate, Zircosol ZN, zirconyl chloride, zirconyl hydroxychloride, chromium acetate, chromium sulphate, sal epsom, magnesium chloride hexahydrate, the magnesium citrate nonahydrate, Tungstophosphoric acid, sodium salt, Trisodium Citrate tungsten, 12 tungstophosphoric acid n hydrates, 12 tungstosilicic acids, 26 hydrates, molybdenum chloride, 12 molybdophosphate n hydrates, gallium nitrate, nitric acid germanium, strontium nitrate, yttium acetate, Yttrium trichloride, Yttrium trinitrate, indium nitrate, lanthanum nitrate, Lanthanum trichloride, lanthanum acetate, the phenylformic acid lanthanum, Cerium II Chloride, cerous nitrate, cerium octoate, praseodymium nitrate, neodymium nitrate, samaric nitrate, europium nitrate, Gadolinium trinitrate, Dysprosium trinitrate, Erbium trinitrate, ytterbium nitrate, hafnium chloride and Bismuth trinitrate.

Preferred inorganic mordant of the present invention is the metallic compound (salt or title complex) of aluminum contained compound, titanium-containing compound, zirconium-containing compound, periodic table of elements IIIB family.

Among the present invention, the amount of the mordant that is contained in the ink receiving layer is preferably 0.01g/m ²To 5g/m ², 0.1g/m more preferably ²To 3g/m ²

(other component)

Recording materials of the present invention can also contain various known additives as required as acid, UV light absorber, antioxidant, white dyes, monomer, polymerization starter, polymerization retarder, exudation, sanitas, viscosity stabilizer, defoamer, tensio-active agent, static inhibitor, matting agent, curling agent, the water repellent agent etc. of preventing.

Among the present invention, the ink receiving layer can comprise acid.The adding of acid is adjusted to 3-8 with the surface p H of ink receiving layer, preferred 5-7.5.

This adding is preferred, because it has improved the anti-yellow of white background.The method A that is used for surface p H measurement that is determined by J.TAPPI comes surface measurements pH.According to method A, this measurement can for example use the paper surface p H measuring apparatus of being made by Kyoritsu Rikagaku Kenkyusho " FormMPC " to carry out.

The specific examples of acid comprises: formic acid, acetate, oxyacetic acid, oxalic acid, propionic acid, propanedioic acid, succsinic acid, hexanodioic acid, toxilic acid, oxysuccinic acid, tartrate, citric acid, phenylformic acid, m-phthalic acid, pentanedioic acid, glyconic acid, lactic acid, aspartic acid, L-glutamic acid, methylsulfonic acid, methylene-succinic acid, Phenylsulfonic acid, toluenesulphonic acids, trifluoromethayl sulfonic acid, styrene sulfonic acid, trifluoroacetic acid, barbituric acid, vinylformic acid, methacrylic acid, styracin, the 4-hydroxy-benzoic acid, benzaminic acid, naphthalene disulfonic acid, hydroxy benzenesulfonic acid, toluenesulfinic acid, benzene sulfinic acid, sulfanilic acid (sulfanylic acid), thionamic acid, alpha-dihydroxy-phenylformic acid (resorcic acid), beta-resorcylic acid, γ-resorcylic acid, gallic acid, the fluoro glycine, sulphosalicylic acid, xitix, saccharosonic acid, diphenolic acid, hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, Tripyrophosphoric acid, boric acid and boronic acid.The add-on that can determine this class acid obtains the surface p H of ink receiving layer in 3 to 8 scopes.

Acid recited above can be used with the form of metal-salt (for example salt of sodium, potassium, calcium, caesium, zinc, copper, iron, aluminium, zirconium, lanthanum, hundred million, magnesium, strontium or cerium) or amine salt (for example salt of ammonia, triethylamine, Tributylamine, piperidines, pipecoline or PAH).

Among the present invention, the preferred ink receiving layer comprises stores the property improvement agent, as UV light absorber, antioxidant or exudation.

This UV light absorber, the example of antioxidant and exudation comprises alkylated benzenes phenolic compound (comprising hindered phenol compound), alkylthio methylphenol compound, hydroquinone compound, alkylation hydroquinone compound, tocopherol compound, sulfo-diphenyl ether compound contains the compound of two or more thioether bonds, bisphenol cpd, O-, N-or S-benzyl compounds, the hydroxybenzyl compound, triaizine compounds, phosphonate compound, the amido oxybenzene compound, ester cpds, amide compound, xitix, the amine antioxidant, 2-(2-hydroxy phenyl) benzotriazole cpd, 2-hydroxy benzophenone ketone compound, acrylate, water-soluble or hydrophobic metals salt, organometallic compound, metal complexes, hindered amine compound (comprising the TEMPO compound), 2-(2-hydroxy phenyl)-1,3,5-triaizine compounds, metal inactivator, phosphite compound, the phosphonite compound, hydroxylamine compound, nitro-n-compound, peroxide scavenger, the polymeric amide stablizer, polyether compound, alkaline auxiliary stabilizer, nucleator, the cumarone ketone compound, indolinone compound, phosphine compound, polyamine compounds, thiourea compound, carbamide compound, hydrazide compound, amidine compound, sugar compounds, hydroxybenzoic acids, hydroxybenzoic acids and trihydroxybenzoic acid compound.

In these, the preferred alkyl oxybenzene compound contains the compound of two or more thioether bonds, bisphenol cpd, xitix, amine antioxidant, water-soluble or hydrophobic metals salt, organometallic compound, metal complexes, hindered amine compound, hydroxylamine compound, polyamine compounds, thiourea compound, hydrazide compound, hydroxybenzoic acids, resorcylic acid compound and trihydroxybenzoic acid compound.

The specific examples of described compound is described in the following patent: Japanese patent application No.2002-13005, JP-A Nos.10-182621 and 2001-260519, JP-B Nos.4-34953 and 4-34513, JP-A No.11-170686, JP-B No.4-34512, EP No.1138509, JP-A Nos.60-67190,7-276808,2001-94829,47-10537,58-111942,58-212844,59-19945,59-46646,59-109055 and 63-53544, JP-B Nos.36-10466,42-26187,48-30492,48-31255,48-41572,48-54965 and 50-10726, United States Patent(USP) Nos. 2,719,086,3,707,375,3,754,919 and 4,220,711, JP-B Nos.45-4699 and 54-5324, EP-A Nos.223739,309401,309402,310551,310552 and 459416, DP-A No.3435443, JP-A Nos.54-48535,60-107384,60-107383,60-125470,60-125471,60-as5472,60-287485,60-287486,60-287487,60-287488,61-160287,61-185483,61-211079,62-146678,62-146680,62-146679,62-282885,62-262047,63-051174,63-89877,63-88380,66-88381,63-113536,63-163351,63-203372,63-224989,63-251282,63-267594,63-182484,1-239282,2-262654,2-71262,3-121449,4-291685,4-291684,5-61166,5-119495-188687,5-188686,5-110490,5-1108437 and 5-170361, JP-B Nos.48-43295 and 48-33212, and United States Patent(USP) Nos. 4,814,262 and 4,980,275.

Other component recited above can use separately or two or more are used in combination.These other components can be added in the aqueous solution, dispersion liquid, polymer dispersion liquid, emulsion or the oil droplet, maybe can be combined in the microcapsule.In recording materials of the present invention, the add-on of these other components is preferably 0.01 to 10g/m ²

In addition, in order to improve the dispersiveness of fine inorganic particle, can handle its surface with silane coupling agent.This silane coupling agent preferably except having the part that is used for linked reaction, also has organo-functional group (as vinyl, amino (uncle is to uncle's amino or quaternary ammonium salt base), epoxy group(ing), thin base, chloro, alkyl, phenyl or ester group).

Among the present invention, the coating fluid that is preferred for the ink receiving layer comprises tensio-active agent.This tensio-active agent can be positively charged ion, negatively charged ion, nonionic, fluoridize or silicone-type.

The example of nonionogenic tenside comprises: polyoxyalkylene alkyl and polyoxyalkylene alkyl phenyl ether are (as carbiphene, diethylene glycol diethyl ether, polyoxyethylene lauryl ether, polyoxyethylene stearyl base ether or polyoxyethylene nonylplenyl ether), oxygen ethene-oxypropylene segmented copolymer, sorbitan-fatty acid ester is (as Span-20, sorbitan monooleate or sorbitan trioleate), polyoxyethylene sorbitan fatty acid ester is (as Tween-20, polyoxyethylene sorbitan monooleate or polyoxyethylene sorbitan trioleate), polyoxyethylene sorbitol fatty acid ester (as polyoxyethylene sorbitol four oleic acid esters), polyoxyethylene glycerol fatty acid ester (as polyoxyethylene Zerol or Polyoxyethylene glycerol monooleate), polyoxyethylene fatty acid ester (as polyethylene glycol monolaurate or polyethylene glycol monooleate), polyoxyethylene alkyl amine and acetylene series triol are (as 2,4,7,9-tetramethyl--5-decyl-4, the 7-glycol, its ethylene oxide adduct, and preferred polyoxyalkylene alkyl or its propylene oxide adduct).This nonionic surface active agent can use in first coating fluid and second coating fluid.In addition, this nonionic surface active agent can use separately, or two or more are used in combination.

Anion surfactant can be soap (as sodium stearate or potassium oleate), alkyl sulfonic ester salt (as sodium laurylsulfonate or trolamine lauryl sulfonate), sulfonate (as dioctyl sodium sulphosuccinate), alkyl diphenyl base ether stilbene-4,4'-bis-(1-azo-3, 4-dihydroxy-benzene)-2,2'-disulfonate or alkyl phosphonate.

Cats product can be alkylamine salt, quaternary ammonium salt, pyridinium salt or imidazole salts.

Fluorinated surfactant can be to utilize electrofluorination, telomerization or oligomerization and derived from the compound of the intermediate that contains perfluoroalkyl.

Example comprises: fluorinated alkyl sulfonate, perfluoroalkyl carboxylate, perfluoroalkyl ethylene oxide adduct, perfluoroalkyl trialkyl ammonium salts, the oligopolymer that contains perfluoroalkyl and perfluoralkyl phosphate.

Silicone surfactant is preferably used the silicone oil of organic group modification, and can have the structure that the side chain of siloxane structure wherein is modified by the structure of organic group modification, wherein two structures that end group is modified, or one of them end group.The organic group modification can be amino modified, polyester modification, epoxy group(ing) modification, carboxy-modified, methyl alcohol modification, alkyl-modified, aralkyl modification, phenol-modified or fluorine modification.

Among the present invention, tensio-active agent is preferably 0.001 to 20% with respect to the content of the coating fluid that is used for the ink receiving layer, and more preferably 0.01 to 1.0%.In that two or more are planted under the situation of liquid with the coating fluid that acts on the ink receiving layer, can preferably tensio-active agent be added in every kind of coating fluid.

Among the present invention, the preferred ink receiving layer comprises and is used to prevent the high boiling organic solvent that curls that this high boiling organic solvent is that boiling point is 150 ℃ or higher water-soluble or hydrophobic organic compound under normal pressure.This compound can be a liquid or solid in room temperature, and can be lower molecular weight or high-molecular weight.

Specific examples comprises: aromatic carboxylic acid ester is (as dibutyl phthalate; diphenyl phthalate or phenol benzoate); alphatic carboxylic acid ester is (as Octyl adipate; Uniflex DBS; methyl stearate; dibutyl maleinate; dibutyl fumarate or ethanoyl (acedtyl) triethyl citrate); phosphoric acid ester (as trioctyl phosphate or Tritolyl Phosphate); epoxy compounds (as epoxidized soybean oil or epoxidized fatty acid methyl esters); alcohol is (as stearyl alcohol; ethylene glycol; propylene glycol; glycol ether; triglycol; glycerine; diethylene glycol monobutyl ether (DEGMBE); the triglycol monobutyl ether; the glycerine monomethyl ether; 1; 2; the 3-trihydroxybutane; 1; 2; the 4-trihydroxybutane; 1; 2; 4-penta triol; 1; 2, the 6-hexanetriol; the sulfo-glycol ether; trolamine; or polyoxyethylene glycol); vegetables oil (as soya-bean oil or the last of the ten Heavenly stems caul-fat) and higher aliphatic carboxylic acid (as linolic acid or oleic acid).

(preparations of recording materials)

In the recording materials of the present invention, preferably form the ink receiving layer by following method (wet (wet-on-wet) method of wet cover): coating comprises particulate at least on substrate surface, first coating fluid (or solution) of water soluble resin and linking agent (below be called " coating fluid (A) "), then with second coating fluid, it is that pH is 8 or higher basic solution (below be called " coating fluid (B) "), in (1) and described coating while, or in the drying process of the coating layer that forms by coating and before coating layer begins to show the rate of drying of decline, be applied to described coating layer (under situation (1)) or to coated film (under situation (2)), and by making the coating layer that applies second coating fluid or coated film is crosslinked solidifies.

Preferably the present invention is included at least a in coating fluid recited above (A) and the coating fluid (B) by the compound of formula (A) expression.In addition, linking agent that preferably can the cross-linked, water-soluble resin is included at least a in coating fluid (A) and the coating fluid (B).

For the ink absorption performance with for preventing the film crackle, preferably exist this by crosslinked and hardened ink receiving layer.

In the described in the above mode, and mordant solution is being used as under the situation of coating fluid (B), this mordant exists in a large number at ink receiving layer near surface, thereby makes colorant (tinting material) mordant dyeing of ink fully, and the character after advantageously improvement is printed or the water-repellancy of image.The part mordant can be contained in the coating fluid (A), and in this case, at coating fluid (A) and the mordant (B) can be identical or different.

Coating fluid (B) is preferably by being dissolved in mordant the mordant solution that solvent forms, and can regulate the pH value by selecting mordant aptly.

Among the present invention, can be prepared the coating fluid (coating fluid (A)) that is used for the ink receiving layer by following mode, described coating fluid comprises particulate (as fumed silica), water soluble resin (as polyvinyl alcohol) and linking agent (as boric acid) at least.

It can prepare by following method: fumed silica particle and dispersion agent (for example are added to water, silicon dioxide granule is 10 to 20 quality % in water), (for example utilize high speed rotating wet type colloidal mill, the Clearmix that M-Technic Co. makes) for example 10,000rpm (preferred 5,000 to 20,000rpm) get off to disperse with the high speed rotating condition of for example 20 minutes (preferred 10 to 30 minutes), add linking agent (as boron compound) then, and polyvinyl alcohol (PVA) (for example, account for the PVA of about 1/3 quality of fumed silica) the aqueous solution, in addition, under the situation that will be added to by the compound of formula (A) expression in the coating fluid (A), add this compound and under aforesaid identical rotating condition, disperse.The coating fluid that obtains is the uniform sol shape, and by being coated with on base material and dry this coating fluid by following method, can obtain having the porous ink receiving layer of tridimensional network.

Comprise in the aqueous liquid dispersion of fumed silica and dispersion agent in preparation, the aqueous liquid dispersion that can prepare fumed silica in advance, and this aqueous liquid dispersion is added in the aqueous solution of dispersion agent, perhaps the aqueous solution with dispersion agent is added in the aqueous liquid dispersion of fumed silica, or both are mixed simultaneously.In addition, can will replace the Powdered fumed silica of fumed silica aqueous liquid dispersion to be added in the aqueous solution of dispersion agent.

After fumed silica and dispersant, make mixed solution thinner with decollator, be 50 to 300nm aqueous liquid dispersion thereby obtain average particle size.

In order to obtain this aqueous liquid dispersion, can adopt various dispersion machine known in the art, as high speed rotating dispersion machine, medium stirring dispersion machine (as ball mill or sand mill), ultrasonic dispersing machine, colloid mill disperser or high pressure dispersion machine, but, for disperse particles effectively, preferred stirring dispersion machine, colloid mill disperser or high pressure dispersion machine.

In addition, as for the solvent in these steps, can adopt water, organic solvent or their mixed solvent.The organic solvent that is used to be coated with can be for example pure as methyl alcohol, ethanol, n-propyl alcohol, Virahol or methoxypropanol, ketone such as acetone or methyl ethyl ketone, tetrahydrofuran (THF), acetonitrile, ethyl acetate or toluene.

As for dispersion agent, can adopt cationic polymers.Cationic polymers regards to those that mordant quotes on can being.In addition, preferably silane coupling agent is used as dispersion agent.

Preferred dispersants is 0.1 to 30% with respect to the add-on of particulate, more preferably 1 to 10%.

Can be coated with known coating process such as overflow mould coating, airblade coating, scraper coating, rod, cutter is coated with, extrusion coated, contrary roller coat cloth or bar rod are coated with the coating fluid that is used for the ink receiving layer.

With the coating fluid that is used for the ink receiving layer (coating fluid (A)) coating in or afterwards, (B) is coated on the coating layer with coating fluid, and be coated with coating fluid (B) before can beginning to show the rate of drying of decline at the coating layer after the coating.More specifically, coating layer shows constant rate of drying by introduce mordant after the coating fluid that is used for the ink receiving layer (coating fluid (A)) coating, can reach preferred manufacturing.

" before coating layer begins to show the rate of drying of decline " be meant usually after the coating fluid coating that is used for the ink receiving layer immediately several minutes during, and during this period, show " constant rate of drying " phenomenon, wherein the content and the time of the solvent in coating layer (dispersion medium) descend pro rata.Be described in for example Chemical EngineeringHandbook (the 707-712 page or leaf is published on October 25th, 1980 by Maruzen) during this " constant rate of drying ".

As mentioned above, after the coating of first coating fluid, drying coated layer show the rate of drying that descends up to it, and this drying is carried out 0.5 to 10 minute (preferred 0.5 to 5 minute) at 50 to 180 ℃ usually.Certainly change according to glue spread this time of drying, but carry out in the described in the above usually scope.

Begin to show that the coating method before the rate of drying of decline can be at first coating layer: the base material that the method that [1] is coated with coating fluid (B) on coating layer method, [2] sprayed with for example injector or [3] will have coating layer impregnated in the method in the coating fluid (B).

In method [1], coating fluid (B) can be coated with by known coating process, as be coated with a curtain flow coat cloth, overflow mould coating, airblade coating, scraper coating, rod, cutter is coated with, extrusion coated, contrary roller coat cloth or bar rod are coated with.But, preferably adopt the wherein not direct method that contacts with first coating layer that has formed of spreader, as overflow mould coating, curtain flow coat cloth or the coating of bar rod.

After mordant solution (coating fluid (B)) applies, usually by carrying out drying and sclerosis in 0.5 to 30 minute 40 to 180 ℃ of heating.Preferably heated 1 to 20 minute at 40 to 150 ℃.

In addition, when being coated with, apply under the situation of mordant solution (coating fluid (B)) with the coating fluid that is used for the ink receiving layer (coating fluid (A)), can form the ink receiving layer by on base material, being coated with the coating fluid (coating fluid (A)) and the mordant solution (coating fluid (B)) (stack coating) that are used for the ink receiving layer simultaneously, its mode makes the coating fluid (coating fluid (A)) that is used for the ink receiving layer contact with base material, dry then and sclerosis.

Can realize being coated with simultaneously (stack coating) by the coating process that utilizes overflow mould spreader for example or curtain stream spreader.After the coating, with the coating layer drying, and this drying is normally by heating coating layer 0.5 to 10 minute at 40 to 150 ℃ at the same time, preferably heats at 40 to 100 ℃ and carries out in 0.5 to 5 minute.

Under the situation that for example is coated with (stack coating) simultaneously with the overflow mould spreader, near the discharge outlet of overflow mould spreader, promptly be transferred to before the base material, two kinds of coating fluids that discharge simultaneously formed superimposed layer, and be coated on the base material with stacked system with such state.Synergetic two-layer coating fluid tends to when being transferred to base material before coating, two kinds of liquid cause crosslinking reaction at the interface, thereby cause the mixing of two kinds of liquid discharging and the increase of viscosity, thereby hinder the coating operation.Therefore, under the situation of coating simultaneously as explained above, preferably, between these two kinds of liquid, provide blocking layer liquid (middle layer liquid), be coated with three layers thus simultaneously with coating fluid that is used for the ink receiving layer (coating fluid (A)) and mordant solution (coating fluid (B)).

Can be without any especially restrictedly selecting this blocking layer liquid.For example, it can be the aqueous solution or the water that contains the trace water soluble resin.Consider coating performance, this water soluble resin can for example be used as viscosity intensifier, and can be celluosic resin (as Vltra tears or hydroxyethylmethyl-cellulose), or polymkeric substance such as polyvinylpyrrolidone or gelatin.Can also there be mordant recited above in the liquid of blocking layer.

On base material, form after the ink receiving layer, can be with this ink receiving layer by under heat and pressure, carrying out calender process, to improve surface flatness, transparency and coated film intensity by the roll gap in super calender or the gloss roller calender.But this calender process may cause the decline (being the decline of ink receptivity) of porosity, must carry out under such condition not causing that porosity significantly descends.

In calender process, the roller temperature is preferably 30 to 150 ℃, more preferably 40 to 100 ℃.

In addition, the line pressure between the calender process central roll is preferably 50 to 400kg/cm, and more preferably 100 to 200kg/cm.

The thickness of ink receiving layer must be determined according to the porosity in the layer, because ink-vapor recording requires to be used to absorb the receptivity of all drops.At 8nL/mm ²Quantity of ink and the situation of 60% porosity under, need about 15 μ m or bigger layer thickness.

Given this, the thickness that is used for the ink receiving layer of ink-vapor recording is preferably 10 to 50 μ m.

In addition, the pore size of ink receiving layer is preferably 0.005 to 0.030 μ m by middle footpath, more preferably 0.01 to 0.025 μ m.

Can measure footpath in pore size and the hole with mercury porosity meter (Poresizer 9320-PC2 (trade mark) is made by Shimadzu Mfg.Co.).

In addition, the preferred ink receiving layer has excellent transparency, and it is measured by haze value and provides, and when forming the ink receiving layer on the transparent film base material, it is 30% or littler, and more preferably 20% or littler.

Haze value can use haze meter (HGM-2DP is made by Suga Shikenki Co.) to measure.

Recording materials of the present invention can also provide back coating, and the component that can be added to this back coating comprises white pigment, aqueous binder and other component.

The example of the white pigment that contains in back coating comprises inorganic white pigment such as light calcium carbonate, water-ground limestone, kaolin, talcum, calcium sulfate, barium sulfate, titanium dioxide, zinc oxide, zinc sulphide, zinc carbonate, stain white, pure aluminium silicate, diatomite, Calucium Silicate powder, Magnesium Silicate q-agent, synthetic soft silica, colloid silica, colloidal alumina, pseudobochmite, aluminium hydroxide, aluminum oxide, lithopone, zeolite, hydrated halloysite, magnesiumcarbonate or magnesium hydroxide and pigment dyestuff such as styrenic pigment, acrylics pigment, polyethylene, microcapsule, urea resin or melamine resin.

The aqueous binder that adopts in back coating can be for example water-soluble polymers such as vinylbenzene/maleate copolymer, styrene/acrylic salt (actylate salt) multipolymer, polyvinyl alcohol, silanol-modified polyethylene alcohol, starch, caolinated starch, casein, gelatin, carboxymethyl cellulose, Natvosol or polyvinylpyrrolidone and aqueous dispersion polymers such as styrene-butadiene latex or acryl emulsion.Other component that can contain in back coating comprises defoamer, antifoam agent, dyestuff, white dyes, sanitas and water repellent agent.

The layer (as ink receiving layer or backing layer) that constitutes recording materials of the present invention can comprise polymer fine particles dispersion (polymer latex).This polymer fine particles dispersion is used for improving physical properties such as dimensional stabilizing, prevents to curl, prevents bonding and prevent the film crackle.The polymer fine particles dispersion is described among JP-ANos.62-245258,62-1316648 and the 62-110066.The polymer fine particles dispersion that adds lower glass transition temperatures (40 ℃ or lower) in the layer that contains mordant can prevent the crackle of layer or curl.The polymer fine particles dispersion that adds high glass-transition temperature to the back side can prevent to curl.

In addition, recording materials of the present invention can be by preparing in the method described in JP-A Nos.10-81064,10-119423,10-157277,10-217601,11-348409,2001-138621,2000-43401,2000-211235,2000-309135,2001-96897,2001-138627,11-91242,8-2087,8-2090,8-2091 and the 8-2093.

Among the present invention, to ink jet recording method without limits, and can be any known method, as the electric charge control method, wherein utilize the electrostatic attraction discharge ink, following as required method, wherein utilize the vibration pressure of piezoelectric element, the sound ink ejecting method, wherein change electronic signal into acoustic beam, described acoustic beam irradiation ink is coming discharge ink by irradiation pressure, or hot ink-jet (bubble jet (bubble jet) (trade(brand)name)), heating ink wherein is used to utilize the bubble of the pressure that obtains with generation.

Ink jet recording method comprises: a kind of method of discharging the low density inks that is called the photo ink of many small volumes, the multiple ink that a kind of utilization has a substantially the same tone of different densities improves method and a kind of method of utilizing the water white transparency ink of picture quality.

The ink of the present invention that is used for spray ink Printing can also be used for the application except that ink-vapor recording.It can be used to form the material of indoor decoration image and be used to form the material of exterior decoration with image for example as the material of display image.

Picture display comprises: placard, wallpaper, decorative articles (ornament or rag baby), commercial advertisement volume, wrapping paper, lapping, paper bag, plastics bag, wrapping material, sign board, draw or adhere to the vehicles (automobile, passenger vehicle or train) sidewall, have the clothes of sign etc.Under the situation of the material that dyestuff of the present invention is used as the formation display image, this image comprises that all can not only be comprised the image of narrow sense by the pattern that the people discerned, and comprises abstract design, character, geometric scheme etc.

House decorative material comprises: the design component of the assembly of wallpaper, decorative articles (ornament or rag baby), illumination instrument, assembly, floor or the top ceiling of furniture etc.Under the situation of material that dyestuff of the present invention is used for indoor ornamentation, this image comprises that all can not only be comprised the image of narrow sense by the pattern that the people discerned, and comprises abstract design, character, geometric scheme etc.

The exterior decoration material comprises: the assembly of walling material, roof cladding, sign board, gardening material, exterior decoration article (ornament or rag baby), illumination instrument etc.Dyestuff of the present invention is being used under the situation of material as exterior decoration, and this image comprises that all can not only be comprised the image of narrow sense by the pattern that the people discerned, and comprises abstract design, character, geometric scheme etc.

In these were used, the medium that forms pattern on it comprised: paper, fiber, fabric (comprising nonwoven fabric), plastics, metal, pottery etc.Dyeing can by mordant dyeing, pattern dyestuff or by by introducing active group with the form of reactive dyestuffs with dyestuff fixing.In these, the preferably dyeing by mordant dyeing.

Below, the present invention will be explained by embodiment, but the present invention is not subjected to the restriction of these embodiment.

Embodiment 1

Adding resistance in following component is 18,000,000 (mega) Ω or higher deionized water, makes it become 1 liter, stirs 1 hour under 30 to 40 ℃ heating.Then, be the microfilter filtering mixt under reduced pressure of 0.25 μ m with mean pore size, to obtain light magenta ink LM-101.

(prescription of light magenta ink LM-101)

(solid)

Magenta dye a-36 10g/l

Urea 17g/l

(liquid ingredient)

Triglycol (TEG) 110g/l

Glycerine (GR) 150g/l

Triglycol monobutyl ether (TGB) 120g/l

Trolamine (TEA) 8g/l

Sufrinol STG(SW) 10g/l

Equally, magenta dye prepares magenta ink M-101 in the aforesaid prescription by improving.

(prescription of magenta ink M-101)

(solid)

Magenta dye a-36 30g/l

Urea 37g/l

(liquid ingredient)

Triglycol (TEG) 120g/l

Glycerine 8gr9 150g/l

Triglycol monobutyl ether (TGB) 130g/l

Trolamine (TEA) 6.9g/l

Sufrinol STG(SW) 10g/l

The additive below in LM-101 and M-101, adding, also use identical formulation ink LM-102 to 110 and M-102 to 110.

Table 1

	Additive
		LM-101, M-101 (comparative example)	Do not have
LM-102, M-102 (comparative example)	POEP-110g/ rises to LM-101, M-101
		LM-103, M-103 (comparative example)	POEN-110g/ rises to LM-101, M-101
LM-104, M-104 (the present invention)	X-110g/ rises to LM-101, M-101
		LM-105, M-105 (the present invention)	X-310g/ rises to LM-101, M-101
LM-106, M-106 (the present invention)	X-710g/ rises to LM-101, M-101
		LM-107, M-107 (the present invention)	X-1010g/ rises to LM-101, M-101
LM-108, M-108 (the present invention)	X-1310g/ rises to LM-101, M-101
		LM-109, M-109 (the present invention)	X-1515g/ rises to LM-101, M-101
LM-110, M-110 (the present invention)	X-310g/ rises to LM-101, M-101

POEP-1: polyoxyethylene nonylplenyl ether (PEO chain average 30)

POEN-1: polyoxyethylene naphthyl ether (PEO chain average 50)

With being filled in these inks in the EPSON ink-jet printer PM-980-C print cartridge that magenta ink/light magenta ink is used and other inks of PM-980-C, be used for printing the fuchsin monochrome image.The ink-jet photo glossy paper " Kassai " that use is produced by Fuji Photo Film Co.Ltd. is accepted paper as image and is come print image, and assessment comprises the anti-jail property of image of ozone resistants.

(evaluation test)

[1] by the following anti-jail property of method assessment light: after printing, use X-Rite 310 measurement image density Ci immediately, use senile experiment machine (weather meter) that Atlas company makes with xenon light (85 then, 000lux) irradiance pattern was as 25 days, and then measurement image density Cf, and remaining ratio center C f/Ci * 100 of calculating dyestuff.Be the remaining ratio of three point measurement dyestuffs of 1,1.5 and 2 in reflection density, and the remaining ratio of dyestuff in all density be 70% or higher situation under, be A with result evaluation; Be lower than at the remaining ratios of 2 middle dyestuffs under 70% the situation and be B; Have a few in the remaining ratio of dyestuff all be lower than under 70% the situation and be C.

[2] assess hot anti-jail property by following method:,, determine the remaining ratio of dyestuff with X-Rite 310 measuring densitys before storing 10 days under the condition of 80 ℃ and 70% RH and afterwards with sample.Be the remaining ratio of three point measurement dyestuffs of 1,1.5 and 2 in reflection density, and in all density the remaining ratio of dyestuff be 90% or higher situation under, be A with result evaluation; Be lower than at the remaining ratios of 2 middle dyestuffs under 90% the situation and be B; Have a few in the remaining ratio of dyestuff all be lower than under 90% the situation and be C.

[3] assess ozone resistants by following method by the remaining ratio of dyestuff: photo glossy paper with image is placed in concentration of ozone gas is set at the box of 5ppm, use reflection densitometer (X-Rite 310TR) to measure and place before and image density afterwards, and the remaining ratio of definite dyestuff.In reflection density is the remaining ratio of 1,1.5 and 2 three point measurement dyestuff.With ozone gas watch-dog (by the OZG-EM-01 model of APPLICS Co. preparation) concentration of ozone gas in the box is set.

With the level evaluation result, in all density the remaining ratio of dyestuff be 80% or higher situation under be A; Be lower than at the remaining ratios of 2 middle dyestuffs under 80% the situation and be B; Have a few in the remaining ratio of dyestuff all be lower than under 70% the situation and be C.

Table 2

	The anti-jail property of light	The anti-jail property of heat	Ozone resistants
				EPSON ink (PM-950C)	C	B	C
LM-101, M-101 (comparative example)	B	A	B
				LM-102, M-102 (comparative example)	B	A	B
LM-103, M-103 (comparative example)	B	A	B
				LM-104, M-104 (the present invention)	A	A	A
LM-105, M-105 (the present invention)	A	A	A
				LM-106, M-106 (the present invention)	A	A	A
LM-107, M-107 (the present invention)	A	A	A
				LM-108, M-108 (the present invention)	A	A	A
LM-109, M-109 (the present invention)	A	A	A
				LM-110, M-110 (the present invention)	A	A	A

From the result shown in the table 2, show that the system that utilizes ink group of the present invention is being better than all comparative examples aspect the image storage of M dyestuff.

Embodiment 2

Adding resistance in following component is 18,000,000 Ω or higher deionized water, makes it become 1 liter, and stirs 1 hour under 30-40 ℃ of heating.Be the microfilter filtering mixt under reduced pressure of 0.25 μ m with average cell size then, obtain photo magenta ink LM-201.

(prescription of photo magenta ink LM-201)

(solid)

Magenta dye a-36 7g/l

Urea 22g/l

(liquid ingredient)

Triglycol (TEG) 40g/l

Glycerine (GR) 100g/l

Triglycol monobutyl ether (TGB) 50g/l

1,5-pentanediol 40g/l

Virahol 20g/l

Trolamine (TEA) 8g/l

Sufrinol STG(SW) 10g/l

Magenta dye prepares magenta ink M-201 in the aforesaid prescription by improving.

(prescription of magenta ink M-201)

(solid)

Magenta dye a-36 24g/l

Urea 37g/l

(liquid ingredient)

Triglycol (TEG) 40g/l

Glycerine (GR) 110g/l

Triglycol monobutyl ether (TGB) 50g/l

1,5-pentanediol 50g/l

Virahol 20g/l

Trolamine (TEA) 6.9g/l

Sufrinol STG(SW) 10g/l

The additive below in LM-201 and M-201, adding, also prepare ink LM-202 to 208 and M-202 to 208 with same recipe.

Table 3

	Additive
		LM-201, M-201 (comparative example)	Do not have
LM-202, M-202 (comparative example)	POEP-1 10g/ rises to LM-201, M-201
		LM-203, M-203 (comparative example)	POEN-1 10g/ rises to LM-201, M-201
LM-204, M-204 (the present invention)	X-1 10g/ rises to LM-201, M-201
		LM-205, M-205 (the present invention)	X-4 10g/ rises to LM-201, M-201
LM-206, M-206 (the present invention)	X-8 10g/ rises to LM-201, M-201
		LM-207, M-207 (the present invention)	X-9 10g/ rises to LM-201, M-201
LM-208, M-208 (the present invention)	X-12 10g/ rises to LM-201, M-201

POEP-1: polyoxyethylene nonylplenyl ether (PEO chain average 30)

POEN-1: polyoxyethylene naphthyl ether (PEO chain average 50)

With being filled in these inks in the print cartridge that magenta ink/the silver dollar red ink is used of CANON ink-jet printer PIXUS-950i and other inks of PIXUS-950i, be used for printing the fuchsin monochrome image.The ink-jet photo glossy paper " Kassai " that use is produced by Fuji Photo Film Co.Ltd. is accepted paper as image and is come print image, and assesses the anti-jail property of the image that comprises ozone resistants in the mode identical with embodiment 1.

The results are shown in as follows.

Table 4

	The anti-jail property of light	The anti-jail property of heat	Ozone resistants
				CANON ink PIXUS950i	C	B	C
LM-201, M-201 (comparative example)	B	A	B
				LM-202, M-202 (comparative example)	B	A	B
LM-203, M-203 (comparative example)	B	A	B
				LM-204, M-204 (the present invention)	A	A	A
LM-205, M-205 (the present invention)	A	A	A
				LM-206, M-206 (the present invention)	A	A	A
LM-207, M-207 (the present invention)	A	A	A
				LM-208, M-208 (the present invention)	A	A	A

From the result shown in the table 4, show that the system that utilizes ink group of the present invention is being better than all comparative examples aspect the image storage of M dyestuff.

Embodiment 3

(preparation of the coating fluid A that the ink receiving layer is used)

In the prescription below, mix [1] fumed silica particulate, [2] ion exchanged water and [3] PAS-M-1, with KD-P (making) by Shinmaru Enterprises Co. 10, the revolution of 000rpm disperseed 20 minutes down, add the solution that contains [4] polyvinyl alcohol, [5] boric acid, [6] polyoxyethylene lauryl ether and [7] ion exchanged water then, and 10, redispersion is 20 minutes under the revolution of 000rpm, obtains being used for the coating fluid A of ink receiving layer.

The quality ratio of fine particles of silica and water soluble resin (PB ratio=[1]: [4]) is 4.5:1, and the coating fluid A that is used for the ink receiving layer is for acid, wherein pH=3.5.

(prescription of the coating fluid A that the ink receiving layer is used)

[1] fumed silica particulate

(fine inorganic particle) " Leoseal QS-30,

Make by Tokuyama Co.,

Average primary particle size 7nm 10.0 weight parts

[2] ion exchanged water 51.7 weight parts

[3] PAS-M-1 (60% aqueous solution)

(by the dispersion agent of Nittobo Co. manufacturing) 0.83 weight part

[4] polyvinyl alcohol (water soluble resin)

8% aqueous solution (PVA124 is made by Kuraray Co.,

Saponification deg 98.5%, the polymerization degree are 400) 27.8 weight parts

[5) boric acid (linking agent) 0.4 weight part

[6] polyoxyethylene lauryl ether (tensio-active agent)

(Emergen109P is made by Kao Inc.) 1.2 weight parts

[7) ion exchanged water 33.0 weight parts

(preparation of ink jet recording materials)

To base material, on its front surface, carry out Corona discharge Treatment, and on the front surface of base material, with the extrusion die coating machine coating coating fluid A that is used for the ink receiving layer recited above, wherein glue spread is 200ml/m ²(application step), and dry in 80 ℃ hot air dryer (air velocity was 3 to 8m/ seconds) reaches 20% solids concn up to coating layer.Constant drying rate during coating layer is presented at during this period.After this, be impregnated among the mordant coating fluid B that forms below 30 seconds immediately, with coating solution 20g/m on coating layer ²(mordant coating fluid application step), and in 80 ℃ of dryings 10 minutes (drying step), the ink jet recording materials R-1 that to prepare ink receiving layer dry thickness of the present invention thus be 32 μ m.

(prescription of mordant coating fluid B)

[1] boric acid (linking agent) 0.65 weight part

[2] PAH PAA-10C, 10% aqueous solution

(mordant is made by Nittobo Co.) 25 weight parts

[3] ion exchanged water 59.7 weight parts

[4] ammonium chloride (surface p H conditioning agent) 0.8 weight part

[5] polyoxyethylene lauryl ether (tensio-active agent)

(Emergen109P is made by Kao Inc.) 10 weight parts

[6] Megafac F1405,10% aqueous solution,

Make by Dai-Nippon Inks and Chemicals Ltd.

Fluorinated surfactant 2.0 weight parts

The additive below in ink jet recording paper R-1, adding, also use the formulation ink jet recording paper R-2 to R-8 identical with R-1.

The pH that is used to prepare the mordant coating fluid of recording paper R-1 to R-9 is 8.0 or higher independently of one another.

Table 5

	Additive
		R-1 (comparative example)	Do not have
R-2 (comparative example)	The POEP-12.5 weight part is being used for the liquid B of R-1
		R-3 (the present invention)	The POEN-12.5 weight part is being used for the liquid B of R-1
R-4 (the present invention)	The X-12.5 weight part is being used for the liquid B of R-1
		R-5 (the present invention)	The X-32.5 weight part is being used for the liquid B of R-1
R-6 (the present invention)	The X-92.5 weight part is being used for the liquid B of R-1
		R-7 (the present invention)	The X-112.5 weight part is being used for the liquid B of R-1
R-8 (the present invention)	The X-122.5 weight part is being used for the liquid B of R-1

POEP-1: polyoxyethylene nonylplenyl ether (PEO chain average 30)

POEN-1: polyoxyethylene naphthyl ether (PEO chain average 50)

These ink jet recording papers are placed in the continuous paper unit of EPSON ink-jet printer PM-980C, and print the standard chart of Gazou Denshi Gakkai with PM-980C ink group.The chart that obtains is used for the anti-jail property of evaluate image.

Also similarly test with CANON ink-jet printer PIXUS-950i.

(evaluation test)

[1] by the following anti-jail property of method assessment light: after printing, use X-rite 310 measurement image density Ci immediately, use senile experiment machine that Atlas company makes with xenon light (85 then, 000lux) irradiance pattern was as 25 days, and then measurement image density Cf, and remaining ratio Cf/Ci * 100 of calculating dyestuff.Be the remaining ratio of three point measurement dyestuffs of 1,1.5 and 2 in reflection density, and the remaining ratio of dyestuff in all density be 70% or higher situation under, be A with result evaluation; Be lower than at the remaining ratios of 2 middle dyestuffs under 70% the situation and be B; Have a few in the remaining ratio of dyestuff all be lower than under 70% the situation and be C.

[2] assess hot anti-jail property by following method:,, determine the remaining ratio of dyestuff with X-rite 310 measuring densitys before storing 10 days under the condition of 80 ℃ and 70% RH and afterwards with sample.Be the remaining ratio of three point measurement dyestuffs of 1,1.5 and 2 in reflection density, and in all density the remaining ratio of dyestuff be 90% or higher situation under, be A with result evaluation; Be lower than at the remaining ratios of 2 middle dyestuffs under 90% the situation and be B; Have a few in the remaining ratio of dyestuff all be lower than under 90% the situation and be C.

[3] assess ozone resistants by following method by the remaining ratio of dyestuff: photo glossy paper with image is placed in concentration of ozone gas is set at the box of 5ppm, use reflection densitometer (X-rite 310TR) to measure and place before and image density afterwards, and the remaining ratio of definite dyestuff.In reflection density is the remaining ratio of 1,1.5 and 2 three point measurement dyestuff.With ozone gas watch-dog (by the OZG-EM-01 model of APPLICS Co. preparation) concentration of ozone gas in the box is set.

With the level evaluation result, in all density the remaining ratio of dyestuff be 80% or higher situation under be A; Be lower than at the remaining ratios of 2 middle dyestuffs under 80% the situation and be B; Have a few in the remaining ratio of dyestuff all be lower than under 70% the situation and be C.

What obtain the results are shown in the table.

Table 6 test of EPSON ink

	The anti-jail property of light	The anti-jail property of heat	Ozone resistants
				EPSON PM printing paper	B	B	B
R-1 (comparative example)	B	B	B
				R-2 (comparative example)	B	B	B
R-3 (comparative example)	B	B	B
				R-4 (the present invention)	A	A	A
R-5 (the present invention)	A	A	A
				R-6 (the present invention)	A	A	A
R-7 (the present invention)	A	A	A
				R-8 (the present invention)	A	A	A

Table 7 test of CANON ink

	The anti-jail property of light	The anti-jail property of heat	Ozone resistants
				CANON printing paper	B	B	B
R-1 (comparative example)	B	B	B
				R-2 (comparative example)	B	B	B
R-3 (comparative example)	B	B	B
				R-4 (the present invention)	A	A	A
R-5 (the present invention)	A	A	A
				R-6 (the present invention)	A	A	A
R-7 (the present invention)	A	A	A
				R-8 (the present invention)	A	A	A

By these results, effect of the present invention is conspicuous.

In detail and by having described the present invention, but to those skilled in the art, it is evident that and in scope and spirit of the present invention, to carry out various modifications and change with reference to specific embodiment.

The application is based on the Japanese patent application (2003-337852) of Japanese patent application of submitting on September 29th, 2003 (2003-336992) and submission on September 29th, 2003, and the application comprises its content as a reference.

Industrial usability

The present invention can be applied to ink jet recording method without any particular limitationly. The present invention can be used for any known method, such as the electric charge control method, wherein utilize the electrostatic attraction discharge ink, lower method is as required wherein utilized the vibration pressure of piezoelectric element, the sound ink ejecting method, wherein change electronic signal into acoustic beam, described acoustic beam irradiation ink is coming discharge ink by irradiation pressure, or hot ink-jet (bubble jet), heating ink wherein is to produce the bubble that is used for utilizing the pressure that obtains. Ink jet recording method also comprises: a kind of method of discharging the low density inks that is called the photo ink of many small sizes, the multiple ink that a kind of utilization has a substantially the same tone of different densities improves the method for picture quality, with a kind of method of utilizing the water white transparency ink, and the present invention can be applied to any in these methods.

Claims (17)

1. ink that is used for ink jet printing, it comprises:

At least a in water and the water miscibility organic solvent;

Dyestuff; With

Compound by formula (A) expression:

R wherein ₁, R ₂And R ₃Represent alkyl, aryl and heterocyclic group separately, and R ₁, R ₂And R ₃In at least two be interconnected to form ring texture; L represents divalent linker, and R ₁, R ₂, R ₃With among the L at least one be the group that contains 8 or more a plurality of carbon atoms.

2. according to the ink that is used for ink jet printing of claim 1, wherein said dyestuff is to be selected from least a in the group of being made up of the dyestuff of following formula (1) to (4) expression:

Formula (1):

(A ₁₁-N＝N-B ₁₁) _n-L

Formula (2):

Formula (3):

Formula (4):

A ₄₁-N＝N-A ₄₂-N＝N-A ₄₃

Wherein in formula (1),

A ₁₁And B ₁₁Expression can substituted heterocyclic group independently of one another;

N represents 1 or 2; And

L represents hydrogen atom, monovalence substituting group, singly-bound or divalent linker;

Wherein when n was 1, L represented hydrogen atom or monovalence substituting group and A ₁₁And B ₁₁It all is the monovalence heterocyclic group; And

When n was 2, L represented strand or divalent linker, A ₁₁Expression monovalence heterocyclic group, and B ₁₁It is divalent heterocyclic group;

In formula (2),

X ₂₁, X ₂₂, X ₂₃And X ₂₄Expression-SO-Z independently of one another ₂,-SO ₂-Z ₂,-SO ₂NR ₂₁R ₂₂, sulfo group ,-CONR ₂₁R ₂₂Or-COOR ₂₁, Z wherein ₂Represent alkyl, cycloalkyl, thiazolinyl, aralkyl, aryl or heterocyclic group independently, its each can further be substituted; And R ₂₁And R ₂₂Represent hydrogen atom, alkyl, cycloalkyl, alkenyl, aralkyl, aryl or heterocyclic group independently of one another, its each can further be substituted;

Y ₂₁, Y ₂₂, Y ₂₃And Y ₂₄Represent the monovalence substituting group independently of one another;

a ₂₁, a ₂₂, a ₂₃And a ₂₄Represent X respectively ₂₁, X ₂₂, X ₂₃And X ₂₄Number, and represent that independently of one another 0 to 4 number, precondition are all a ₂₁, a ₂₂, a ₂₃And a ₂₄Be not 0 simultaneously, wherein work as a ₂₁, a ₂₂, a ₂₃And a ₂₄In any one is 2 or when bigger, a plurality of X ₂₁, X ₂₂, X ₂₃And X ₂₄Identical or different mutually;

b ₂₁, b ₂₂, b ₂₃And b ₂₄Represent Y respectively ₂₁, Y ₂₂, Y ₂₃And Y ₂₄Number, and represent 0 to 4 number independently of one another, wherein work as b ₂₁, b ₂₂, b ₂₃And b ₂₄Any one is 2 or when bigger, a plurality of Y ₂₁, Y ₂₂, Y ₂₃And Y ₂₄Identical or different mutually; And

M represents hydrogen atom, atoms metal, metal oxide, metal hydroxides or metal halide; In formula (3),

A ₃₁Represent 5 yuan of heterocycles;

B ₃₁And B ₃₂Expression=CR separately ₃₁-or-CR ₃₂=, or B ₃₁And B ₃₂In any expression nitrogen-atoms, and another expression=CR ₃₁-or-CR ₃₂=;

R ₃₅And R ₃₆Represent hydrogen atom, aliphatic group, aromatic group, heterocyclic group, acyl group, alkoxy carbonyl, aryloxycarbonyl, formamyl, alkyl sulphonyl, aryl sulfonyl or sulfamyl independently of one another, its each can also contain substituting group;

G ₃, R ₃₁And R ₃₂Represent hydrogen atom independently of one another, halogen atom, aliphatic group, aromatic group, heterocyclic group, cyano group, carboxyl, formamyl, alkoxy carbonyl, aryloxycarbonyl, the heterocyclic oxy group carbonyl, acyl group, hydroxyl, alkoxyl group, aryloxy, heterocyclic oxy group, siloxy-, acyloxy, carbamoyloxy, alkoxy-carbonyl oxy, aryloxycarbonyl oxygen base, amino, virtue is amino, heterocyclic amino group, amido, urea groups, sulfamoylamino group, alkoxycarbonyl amino, aryloxycarbonyl amino, alkyl sulfonyl amino, Arenesulfonyl amino, the heterocycle sulfonamido, nitro, alkylthio, arylthio, alkyl sulphonyl, aryl sulfonyl, the heterocycle alkylsulfonyl, alkyl sulphinyl, aryl sulfonyl kia, the heterocycle sulfinyl, sulfamyl, sulfo group or heterocycle sulfenyl, its each can further be substituted; And

R ₃₁And R ₃₅, or R ₃₅And R ₃₆Each can be connected to form 5-or 6-unit ring; And

In formula (4),

A ₄₁, A ₄₂And A ₄₃Represent aromatic group or heterocyclic group independently of one another, its each can further be substituted; A ₄₁And A ₄₃It is univalent perssad; And A ₄₂It is divalent group.

3. according to the ink that is used for ink jet printing of claim 2, wherein the dyestuff by formula (2) expression is the dyestuff of being represented by formula (5):

Wherein, X ₅₁, X ₅₂, X ₅₃, X ₅₄, and M ₁Have respectively with formula (2) in X ₂₁, X ₂₂, X ₂₃, X ₂₄, the implication identical with M; Y ₅₁And Y ₅₂Have with formula (2) in Y ₂₁Identical implication; Y ₅₃And Y ₅₄Have with formula (2) in Y ₂₂Identical implication; Y ₅₅And Y ₅₆Have with formula (2) in Y ₂₃Identical implication; Y ₅₇And Y ₅₈Have with formula (2) in Y ₂₄Identical implication; And a ₅₁, a ₅₂, a ₅₃And a ₅₄Represent 1 or 2 integer independently of one another.

4. ink group that is used for ink jet printing, it comprises the ink according to claim 1.

5. ink jet recording materials, it comprises: base material and the ink receiving layer on base material,

Wherein said ink receiving layer comprises the compound by formula (A) expression:

R wherein ₁, R ₂And R ₃Represent alkyl, aryl or heterocyclic group separately, and R ₁, R ₂And R ₃In at least two be interconnected to form ring texture; L represents divalent linker, and R ₁, R ₂, R ₃With among the L at least one be the group that contains 8 or more a plurality of carbon atoms.

6. according to the ink jet recording materials of claim 5, wherein said ink receiving layer also contains water soluble resin.

7. according to the ink jet recording materials of claim 6, wherein said water soluble resin is to be selected from down at least a in the group: the resin of polyvinyl alcohol resin, celluosic resin, ether-containing key, the resin that contains formamyl, carboxylic resin and gelatin.

8. according to the ink jet recording materials of claim 6 or 7, wherein said ink receiving layer comprise can crosslinked described water soluble resin linking agent.

9. according to the ink jet recording materials of claim 5, wherein said ink receiving layer also comprises particulate.

10. according to the ink jet recording materials of claim 9, wherein said particulate is to be selected from down at least a in the group: fine particles of silica, colloid silica, aluminum oxide particulate and pseudobochmite.

11. according to the ink jet recording materials of claim 5, wherein said ink receiving layer also contains mordant.

12. according to the ink jet recording materials of claim 5, wherein said ink receiving layer is the cured layer that forms by following method:

First kind of solution of coating is to form coating layer on base material, and described first kind of solution contains particulate, water soluble resin and linking agent; With

Second kind of solution of coating on described coating layer, the pH of described second kind of solution is 8 or higher, so that by crosslinking reaction described coating layer is solidified, forms cured layer,

Second kind of solution of wherein said coating is undertaken by one of following dual mode:

(1) in first kind of solution of coating; With

(2) during drying coated layer, and before coating layer begins to show the drying rate of decline.

13. an ink jet recording method, this method comprises: discharging is according to the ink droplet of claim 1, to form image or character on ink jet recording materials.

14. an ink jet recording method, this method comprises: discharge ink is dripped on according to the ink jet recording materials of claim 5, to form image or character.

15. according to the ink jet recording method of claim 14, wherein at least a ink contains betaine compound.

16. according to the ink jet recording method of claim 15, wherein said betaine compound is the compound of representing by according to the formula (A) of claim 5.

17. according to the ink jet recording method of claim 15, wherein at least a ink is the ink according to claim 1.