CN1532070A - Ink jet recording method - Google Patents

Abstract

An ink-jet recording method using an ink set for forming an image on an ink-jet recording medium, wherein the ink-jet recording medium has an ink-receiving layer which contains a sulfur-containing compound and is disposed on a support, the ink set contains a yellow ink containing a yellow dye, a magenta ink containing a magenta dye, and a cyan ink containing a cyan dye, as essential components, and the magenta dye has an oxidation potential of higher than 0.8 V (vs SCE).

Description

Ink jet recording method

Technical field

The present invention relates to form the ink jet recording method of ozone resistance excellent images.

Background technology

In recent years, as image recording material, be main flow to form the coloured image material especially, extensively utilize recording materials, transfer-type photosensitive silve halide material, printing-ink and the stylus etc. of ink jet type recording materials, thermographic transfer type image recording material, employing electrofax mode.

In order to reproduce or to write down full-colour image, though use the three primary colours pigment (dyestuff and pigment) of so-called subtractive mixture of colours method in these coloured image recording materials, but present present situation is still to lack to have the strong pigment that can realize the preferred color of choice reproduction regions and can tolerate various working conditionss, so the strong hope of people is improved.

Ink jet recording method has to be made continuous processing that drop circles in the air continuously and makes two kinds of the ejection methods as required that drop circles in the air according to image information signal, its ejection mode has the mode of utilizing the piezoelectric element pressurization to make the drop ejection, utilize heat to make produces bubble ejection drop in the printing ink mode, utilizes hyperacoustic mode or utilizes the mode of electrostatic attraction ejection drop.And, can use water color ink, oil-based ink or solid (fusion) printing ink as ink for ink-jet recording.

For the tinting material in being used in this ink for ink-jet recording, require it that solvent is had good solubility or dispersiveness, can be with the high density record, tone is good, and (oxidizing gas such as NOx, ozone and other SOx etc.) is strong to the reactive gas in light, heat, the environment, moisture content and medicine there is good fastness, display material is had good tack and is difficult to infiltration, and the keeping quality of printing ink is good, and is nontoxic, the purity height, and can obtain with cheapness etc.Yet searching can be extremely difficult with the tinting material that high level satisfies these requirements.So people urgently wish to have a kind of good three primary colors tone that particularly has, good to the fastness of light, humidity and heat, on display material with printing ink accommodating layer during lettering to the strong tinting material of oxidizing gas such as ozone in the environment.

As existing rosaniline dyes, widely used all the time is to adopt the azoic dyestuff as the coupling composition such as phenol, naphthols, aniline.Though but there is the problem of light fastness difference in the azoic dyestuff that tone is good known (for example referring to patent documentation 1 and 2).As its improved goods, developed the dyestuff (referring to patent documentation 3) that has good tone and improved light fastness recently.But known dyestuff in these patents, which kind of is all very not enough for the fastness of oxidizing gas such as ozone.

And be representative with phthalocyanine pigment and triphenylmethane dye as cyan dye.By the phthalocyanine pigment of the most extensive utilization is with C.I.Direct Blue 86, with 87 be representative with 199, these dyestuffs are compared with yellow dyes with pinkish red, though have the good feature of photostabilization, but by oxidizing gas such as nitrogen oxide gas that usually proposes as environmental problem up to now and ozone and significantly variable color and fading.

Up to now, though the phthalocyanine based dye (referring to patent documentation 4～6) that has the people to report to give ozone resistance, the improvement effect of its oxidizing gas fastness is all insufficient, and people wish further to be improved.

On the other hand, though be that the tone of tritane based dye of representative is good with Acid Blue 9, photostabilization and ozone resistance are but very poor.

As yellow dyes, using with Direct Yllow 86 with heterocycle azo dyestuffs such as 120 pyrazolin-5-one azoic dyestuffs, pyridone azoic dyestuffs as the nitrogen benzide based dye of representative or Acid Yllow 17 and so on always.And Kui phthalein ketone based dye proposed repeatedly.Yet these are known dyestuff in the past, as Kui phthalein ketone dyes, its tone, particularly the long wave side curve of absorption spectrum does not trail, but it is not but often strong to ozone and light, and though but the hangover of the strong long wave side of nitrogen benzide based dye curve is serious etc., so present present situation is still to lack the dyestuff that the color harmony fastness has both.

In order to obtain the good and strong full-colour image of colorrendering quality, the dyestuff of composing images there is following requirement:

Each dyestuff of three primary colors should have the excellent absorption characteristic,

Be used to realize the best of breed of the tricolor dye in extensive color reproduction zone,

Each dyestuff of three primary colors should have high fastness,

Fastness does not worsen because of the interaction of dyestuff,

The fastness of tricolor dye is balance mutually.

Yet, for fastness, particularly for the problem that in ink jet printing, becomes big problem so far to the fastness of oxidizing gas such as ozone, still do not have and have this reports that relate to dye property such as fastness which kind of structure or physical property can solve ozone effectively, occur as yet so present present situation is the guiding viewpoint of relevant dye selection.Then more difficult if will select to have concurrently the dyestuff of light fastness in addition.

On the other hand, the colorant receiving layer of ink jet recording medium has and comprises the water soluble resin particulate.This colorant receiving layer obtains vesicular structure because of containing particulate, can improve the receptivity of printing ink like this.Yet owing to be porous, so there is the ozone resistance problem.

To use sulfur-bearing be additive in order to improve ozone resistance, and the someone reports (for example referring to patent documentation 7～10), though its ozone resistance with do not use comparing of this additive good, may not necessarily satisfy the level of present requirement.

Patent documentation 1: the spy opens flat 11-209673 communique

Patent documentation 2: spy's communique of passing the imperial examinations No. 3020660

Patent documentation 3: the spy opens the 2000-220649 communique

Patent documentation 4: the spy opens flat 3-103484 communique

Patent documentation 5: the spy opens flat 4-39365 communique

Patent documentation 6: the spy opens the 2000-303009 communique

Patent documentation 7: the spy opens the 2002-86904 communique

Patent documentation 8: the spy opens the 2002-36717 communique

Patent documentation 9: the spy opens the 2001-260519 communique

Patent documentation 10: the spy opens flat 7-314882 communique

Summary of the invention

To reach following purpose be problem to solve above-mentioned existing problem in the present invention.That is to say, the object of the present invention is to provide a kind of ink jet recording method good the fastness of ozone gas.

In view of this present situation, the inventor etc. study the back to the good ink jet recording method of ozone resistance and find, the printing ink group of forming by ink jet recording medium that will have the colorant receiving layer that contains sulfocompound and the dyestuff of not known as yet by the past with specific oxidizing potential is made up, can see that ozone resistance obtains unexpected significance and improves, thereby finish the present invention.

That is to say, the invention provides following technical scheme:

＜1〉a kind of ink jet recording method, it is characterized in that using a kind of cyan ink that contains a kind of magenta ink of rosaniline dyes and contain at least a cyan dye with the Yellow ink that contains a kind of yellow dyes at least, at least is the oxidizing potential ink for ink-jet recording group higher than 0.8V (vsSCE) of minimum integrant and described rosaniline dyes, on support, form image having on the ink jet recording medium that contains sulfocompound colorant receiving layer.

＜2〉above-mentioned＜1〉ink jet recording method of record, the oxidizing potential that it is characterized in that described cyan dye is also higher than 0.8V (vs SCE).

＜3〉above-mentioned＜1〉or＜2 the record ink jet recording method, it is characterized in that described sulfocompound is one or more compounds that are selected from thioether based compound, thiocarbamide based compound, sulfoxide based compound, thiocyanic acid based compound,-sulfinic acid based compound, disulphide based compound and the sulfur heterocyclic compound.

Embodiment

＜ink for ink-jet recording 〉

-dyestuff-

Can adopt oxidizing potential than the high rosaniline dyes of 0.8V (vs SCE) among the present invention.Oxidizing potential is high more good more, preferred oxidizing potential is higher than 1.0V (vs SCE), more preferably be higher than 1.1V (vs SCE), especially preferably is higher than 1.15V (vs SCE), preferably is higher than 1.2V's (vs SCE).

In addition, if with dyestuff and oxidizing potential than high cyan dye and the usefulness of 0.8V (vs SCE), can obtain gray scale balance, so be ideal.

The easy degree that oxidizing potential value representation electronics moves to electrode from sample, this value big more (oxidizing potential is high more) electronics just is difficult to move to electrode from sample more, in other words, represents oxidized difficulty.With regard to the structure of compound, attract the group of electronics to make oxidizing potential become higher by importing, will make oxidizing potential become lower by importing the group of supplying with electronics.

The oxidizing potential value is described as follows, and is meant the current potential that compound attracts out with the electronics of compound when the anode in voltammetry, it is believed that the HOMO energy level when this numerical value is in ground state with this compound is similar to consistent.

The inventor etc. find that to the ozone fastness research back of rendered image rendered image is relevant with the ozone fastness with the oxidizing potential of compound, by using the oxidizing potential value than the higher compound of saturated calomel electrode (SCE), can improve the ozone fastness.

Utilize the HOMO (the highest occupied orbital) of compound and ozone gas and the relation between the LUMO (lowest unoccupied molecular orbital) that the reason that the ozone fastness of rendered image is improved can be described.That is to say, since be considered between the LUMO of HOMO by tinting material and ozone gas reaction and with the tinting material oxidation, its result reduces the ozone fastness of rendered image, can reduce reactivity with ozone gas by the HOMO that reduces tinting material so will improve the ozone fastness.

The numerical value of oxidizing potential (Eox) can be measured easily by those of ordinary skills.About this measuring method, for example be documented in " the new instrumental measurement in the electrochemistry " (Interscience Publishers in 1954), A.J.Bard work " electrochemical method " (JohnWiley ﹠amp in 1980 of P.Delahay work; Sons) and clear his work " electrochemical determination " (1984, a skill newspaper hall press) of rattan bird.

Below specify the mensuration of oxidizing potential.Sample is dissolved in the dimethyl formamide or acetonitrile equal solvent that contains sodium perchlorate and this supporting electrolyte of mistake chloric acid tetrapropyl ammonium salt, makes concentration reach 1 * 10 ^-4～1 * 10 ^-6Mol dm ^-3, adopt the potential value of cyclic voltammetry measurement method or DC polarography mensuration, as oxidizing potential with respect to SCE (saturated calomel electrode).

Supporting electrolyte that uses and solvent can suitably be selected according to the oxidizing potential of sample and solvability.About the supporting electrolyte and the solvent that can use, be documented on 101～118 pages in clear his work " electrochemical determination " (1984, skill newspaper hall press) of rattan bird.

The oxidizing potential value has the deviation about tens of millivolts under the influence of the fluid impedance of potential difference between the liquid and sample solution etc., but by proofreading and correct with standard model (for example quinhydrones), can guarantee the reproducibility of potential value.

Oxidizing potential among the present invention is to contain 0.1mol dm ^-3The tetrapropyl ammonium perchlorate is as the N of supporting electrolyte, and (compound concentration is 1 * 10 to dinethylformamide ^-3Mol dm ^-3) in, as reference electrode, as active electrode, as counter electrode, adopt the numerical value of DC polarography mensuration with SCE (saturated calomel electrode) with platinum electrode with Graphite Electrodes.

Dyestuff that the present invention uses as long as can satisfy above-mentioned oxidizing potential requirement, just can use any structure.Particularly yellow dyes is owing to its original oxidizing potential just high (HOMO is low), so restriction structurally is few.Below elaborate with regard to satisfying the required dye structure of above-mentioned oxidizing potential.

For reducing and reactivity, preferably attract electron group to improve oxidizing potential among the present invention by on the dye molecule skeleton, importing as the ozone of electrophilic reagent.Therefore we can say; if adopt the special substituent constant σ of Hamann p value explanation as the yardstick of weighing substituting group electrophilic and electron donability; then, can make oxidizing potential become higher by importing nitro, cyano group, sulfinyl, alkylsulfonyl, sulfamyl and so on the big substituting group of σ p value.

The special substituent constant σ of Hamann p value below is described.The special rule of Hamann is for reaction or the equilibrated influence of substituting group to benzene derivative is discussed, the empirical rule in nineteen thirty-five by the L.P.Hammentt proposal, and this regular adaptability is extensively admitted now.The substituent constant of being obtained by the special rule of Hamann has σ p value and σ m value, these numerical value can find in most of general monographs, for example see " the Lange chemistry handbook the 12nd edition that J.A.Dean writes for details, 1979 (Mc Graw-Hill) and " chemical field " supplementary issue, No. 122, the 96th～103 page, 1979 (Nan Guangtang).

Except that above-mentioned substituting group, generally speaking, the atom that the Electronic Negative that contains as chromophoric structure atom is electrically high is many more, and oxidizing potential is high more.Therefore as chromophoric integrant, for example can use unsaturated heterocycle and oxidizing potential is increased than using aryl.As the electrical strong heteroatoms of Electronic Negative, can enumerate nitrogen-atoms, Sauerstoffatom and sulphur atom, special preferred nitrogen atom.

Therefore, the dyestuff that the present invention uses, preferred chromophoric group by heteroatoms constitute, contain unsaturated heterocycle, contain electron-withdrawing group.

As the preferred chromophoric group that constitutes by heteroatoms, can enumerate azoic dyestuff, azomethine dyes, phthalocyanine pigment etc., preferred especially azoic dyestuff.

As unsaturated heterocycle preferred five yuan or hexa-atomic unsaturated heterocycle, can enumerate thiphene ring, furan nucleus, pyrrole ring, thiazole ring, oxazole ring, imidazole ring, isothiazole ring, isoxazole ring, pyrazoles ring, thiadiazoles Huan, oxadiazole ring, triazole ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring etc. as an example.Unsaturated heterocycle also can be the fused rings that forms with hydrocarbon ring or heterocycle.Under nitrogenous heterocyclic occasion, nitrogen-atoms also can be by quaternary ammoniated.And about forming tautomeric heterocycle, both can be the occasion of only putting down in writing a tautomer, also can comprise with other tautomers combining.Preferably thiazole ring, isothiazole ring, isoxazole ring, pyrazoles ring, thiadiazoles ring, pyridine ring, pyrimidine ring, pyrazine ring in the above-mentioned heterocycle.Most preferably isothiazole ring, pyrazoles ring, 1,2,4-thiadiazoles ring, 1,3,4-thiadiazoles ring, pyrazine ring.

As preferred electron-attracting substituent, be the special σ p of Hamann value greater than 0.40 substituting group, preferred substituting group more than 0.45, the most preferably substituting group more than 0.50.In addition, as the substituting group on the chromophoric group, when having a plurality of electrophilic group, the summation of the σ p value of preferred substituents is more than 0.50, more preferably more than 0.60, most preferably more than 0.70.The substituting group of the electrophilic of the special σ p value of relevant Hamann more than 0.40, can enumerate " the Lange chemistry handbook the 12nd edition that above-mentioned J.A.Dean writes, 1979 (Mc Graw-Hill) and " chemical field " supplementary issue, No. 122, the 96th～103 page, cited substituting group in 1979 (Nan Guangtang).

Preferred coloring agent of the present invention is that the combinations of substances with following general formula (I) expression forms.

(ch)-(EWG) n general formula (I)

In the general formula (I), ch represents to contain the chromophoric group of unsaturated heterocycle, and EWG represents that σ p value described later is the electron-attracting substituent more than 0.40, and n represents 1～8 integer.

As ch, can enumerate azoic dyestuff, phthalocyanine pigment, azomethine dyes, quinone based dye (anthraquinone dye, Anthrapyridone dyes etc.), carbonium dye (triphenylmethane dye, xanthene dye, acridine dye etc.) and azine based dye (oxazine that chromophoric group contains unsaturated heterocycle, thiazine etc.) various chromophoric grouies.Preferred chromophoric group has azoic dyestuff, phthalocyanine pigment, azomethine dyes and the Anthrapyridone dyes of unsaturated heterocycle, and preferably chromophoric group has azoic dyestuff, the phthalocyanine pigment of unsaturated heterocycle.

Can be used as the preferred azoic dyestuff that rosaniline dyes and yellow dyes use, is the dyestuff by following general formula (II) expression.

Het (A)-N=N-Het (B) general formula (II)

In the general formula (II), Het (A) and Het (B) expression five yuan or hexa-atomic unsaturated heterocycle.By five yuan or the example of hexa-atomic unsaturated heterocycle of Het (A) and Het (B) expression, can enumerate thiphene ring, furan nucleus, pyrrole ring, thiazole ring, oxazole ring, imidazole ring, isothiazole ring, isoxazole ring, pyrazoles ring, thiadiazoles Huan, oxadiazole ring, triazole ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring etc.These unsaturated heterocycles can also have substituting group.Under the situation of interosculating between the substituting group on the unsaturated heterocycle, also can form the fused rings with hydrocarbon ring or unsaturated heterocycle, on fused rings, also substituting group can be arranged.Under the occasion of nitrogenous unsaturated heterocycle, nitrogen-atoms also can be by quaternary ammoniated.And about forming tautomeric heterocycle, both can comprise and only put down in writing a tautomer, also can comprise with other tautomers combining.

When dyestuff is under the occasion of water-soluble dye, further preferably has ionic hydrophilic group as substituting group.As substituent ionic hydrophilic radical, comprise sulfo group, carboxyl, phosphoryl and quaternary amine base etc.

By Het (A) and the represented heterocyclic preferred embodiment of Het (B), can enumerate thiazole ring, isothiazole ring, pyrazoles ring, thiadiazoles ring, pyridine ring, pyrazine ring etc.More preferably isothiazole ring, pyrazoles ring, thiadiazoles ring, pyridine ring.It would be desirable pyrazoles ring, 1,2,4-thiadiazoles ring, pyridine ring.

Het (A) and Het (B) also can have substituting group.As substituting group, for example can enumerate halogen atom; alkyl (comprising cycloalkyl); alkenyl (comprising cycloalkenyl); alkynyl; aryl; heterocyclic group; cyano group; hydroxyl; nitro; carboxyl; alkoxyl group; aryloxy; siloxy-; heterocyclic oxy group; acyloxy; carbamoyloxy; alkyl oxy carbonyl oxygen; virtue oxygen carbonyl oxygen base; amino (comprising anilino); acyl amino; amino carbonyl amino; alkoxycarbonyl amido; aryloxy carbonyl amino; sulfamyl amino; the sulfoamido of alkyl and aryl; sulfydryl; alkylthio; arylthio; the heterocycle sulfenyl; sulfamyl; sulfo group; the sulfinyl of alkyl and aryl; the alkylsulfonyl of alkyl and aryl; acyl group; aryloxy carbonyl; carbalkoxy; formamyl; aryl and heterocycle azo base; imide; inferior phosphoryl; phosphoryl; inferior phosphoryl; inferior phosphorus acyloxy; inferior phosphinylidyne amino; silyl etc.Though wherein can list alkylsulfonyl, acyl group, aryloxy carbonyl, carbalkoxy, formamyl, imide, phosphoryl, phosphono, phosphino-, phosphonyl, phosphine oxygen base and phosphine amino and so on the substituting group etc. of sulfinyl, alkyl and the aryl of halogen atom, heterocyclic group, cyano group, nitro, carboxyl, acyloxy, carbamoyloxy, alkyl oxy carbonyl oxygen, aryloxy carbonyl oxygen base, sulfamyl, sulfo group, alkyl and aryl; but wherein preferred electrophilic group, preferred especially σ p value are the substituting group more than 0.40.As σ p value is substituting group more than 0.40; except alkylsulfonyl, acyl group, aryloxy carbonyl, carbalkoxy, formamyl, imide, phosphoryl and the phosphono of sulfinyl, alkyl and the aryl of cyano group, nitro, carboxyl, sulfamyl, alkyl and aryl, alkenyl (tricyano vinyl etc.), the quaternary salt substituting group (sulfonium base, ammonium, Phosphonium base) that can also enumerate the alkyl (trihalogenmethyl, perfluoroalkyl, dicyano methyl, iminomethyl etc.) that replaced by the electrophilic group, be replaced by the electrophilic group.In the above-mentioned functional group, have also can being replaced of hydrogen atom by above-mentioned substituting group.This substituent example can be enumerated alkyl-carbonyl-amino alkylsulfonyl, aryl-amino-carbonyl alkylsulfonyl, alkyl sulfonyl-amino carbonyl, aryl sulfonyl amino carbonyl etc.

And under bonded occasion between the substituting group on the heterocycle, both can form condensed ring with heterocycle, also substituting group can be arranged on condensed ring.

As preferred rosaniline dyes, be material by general formula (M-I) expression.

[changing 1]

General formula (M-I)

In the general formula (M-I), A represents five-membered ring two azo composition A-NH ₂Residue.B ¹And B ²Expression-CR respectively ¹=and-CR ²=, perhaps one of them represents nitrogen-atoms, and another expression-CR ¹=and-CR ²=.R ⁵And R ⁶Independent separately expression hydrogen atom, aliphatic group, aromatic group, heterocyclic group, acyl group, carbalkoxy, aryloxy carbonyl, formamyl, alkyl or aryl alkylsulfonyl or sulfamyl, each group also can have substituting group.

G, R ¹And R ²Independent separately expression hydrogen atom; halogen atom; aliphatic group; aromatic group; heterocyclic group; cyano group; carboxyl; formamyl; carbalkoxy; aryloxy carbonyl; heterocycle oxygen carbonyl; acyl group; hydroxyl; alkoxyl group; aryloxy; heterocyclic oxy group; siloxy-; acyloxy; carbamoyloxy; alkyl oxy carbonyl oxygen; virtue oxygen carbonyl oxygen base; amino (comprises heterocyclic amino group; anilino); acyl amino; urea groups; sulfamyl amino; alkoxycarbonyl amido; aryloxy carbonyl amino; the alkyl or aryl sulfonamido; the heterocycle sulfonamido; nitro; the alkyl or aryl sulfenyl; the alkyl or aryl alkylsulfonyl; the heterocycle alkylsulfonyl; the alkyl or aryl sulfinyl; the heterocycle sulfinyl; sulfamyl; sulfo group or heterocycle sulfenyl, each substituting group also can be substituted.R ¹And R ²Perhaps R ⁵And R ⁶Also can interosculate and form five yuan or six-ring.

In general formula (M-I), A represents five-membered ring two azo composition A-NH ₂Residue.Heteroatomic example can be enumerated N, O and S on the heterocycle.Preferred nitrogenous five-membered ring, heterocycle also can with aliphatics ring, aromatic ring or other heterocycle condensations.The preferred heterocycle example of A can be enumerated pyrazoles ring, imidazole ring, thiazole ring, isothiazole ring, thiadiazoles ring, benzothiazole ring, benzoxazole ring and benzisothiazole ring.Each heterocyclic group can also have substituting group.Wherein preferably by pyrazoles ring, imidazole ring, isothiazole ring, thiadiazoles ring and the benzothiazole ring of following general formula (a) to (f) expression.

[changing 2]

General formula (a)～(f)

In above-mentioned general formula (a)～(f), from R ⁷To R ²⁰The expression with at G, R ¹And R ²The identical substituting group of substituting group of middle explanation.In general formula (a)～(f), preferred pyrazoles ring and the isothiazole ring of being represented by the general formula (a) and (b) is most preferably by the pyrazoles ring of general formula (a) expression.

In the general formula (M-I), B ¹And B ²Though expression-CR respectively ¹=and-CR ²=, perhaps one of them represents nitrogen-atoms, and another expression-CR ¹=and-CR ²=, but more preferably expression-CR respectively ¹=and-CR ²=.

R ⁵And R ⁶Independent separately expression hydrogen atom, aliphatic group, aromatic group, heterocyclic group, acyl group, carbalkoxy, aryloxy carbonyl, formamyl, alkyl or aryl alkylsulfonyl, sulfamyl, each group also can have substituting group.R ⁵And R ⁶The preferred substituents of expression can be enumerated hydrogen atom, aliphatic group, aromatic group, heterocyclic group, acyl group, alkyl or aryl alkylsulfonyl.More preferred substituents is hydrogen atom, aromatic group, heterocyclic group, acyl group, alkyl or aryl alkylsulfonyl.Most preferably hydrogen atom, aryl, heterocyclic group.Each group can also have substituting group.But R ⁵And R ⁶Can not be hydrogen atom simultaneously.

G, R ¹And R ²Independent separately expression hydrogen atom; halogen atom; aliphatic group; aromatic group; heterocyclic group; cyano group; carboxyl; formamyl; carbalkoxy; aryloxy carbonyl; heterocycle oxygen carbonyl; acyl group; hydroxyl; alkoxyl group; aryloxy; heterocyclic oxy group; siloxy-; acyloxy; carbamoyloxy; alcoxyl carbonyl oxygen amino; virtue oxygen carbonyl oxygen amino; amino (comprises anilino; heterocyclic amino group); acyl amino; urea groups; sulfamyl amino; alkoxycarbonyl amido; aryloxy carbonyl amino; the alkyl or aryl sulfonamido; the heterocycle sulfonamido; nitro; the alkyl or aryl sulfenyl; the heterocycle sulfenyl; the alkyl or aryl alkylsulfonyl; the heterocycle alkylsulfonyl; the alkyl or aryl sulfinyl; the heterocycle sulfinyl; sulfamyl or sulfo group, each substituting group also can be substituted.

The substituting group of representing as G; preferred hydrogen atom, halogen atom, aliphatic group, aromatic group, hydroxyl, alkoxyl group, aryloxy, acyloxy, heterocyclic oxy group, amino (comprising anilino, heterocyclic amino group), acyl amino, urea groups, sulfamyl amino, alkoxycarbonyl amido, aryloxy carbonyl amino, alkyl and artyl sulfo or heterocycle sulfenyl; more preferably hydrogen atom, halogen atom, alkyl, hydroxyl, alkoxyl group, aryloxy, acyloxy, amino (comprising anilino, heterocyclic amino group) or acyl amino, wherein most preferably hydrogen atom, anilino, acyl amino.Each substituting group also can have substituting group.

As R ¹And R ²The preferred substituents of expression can be enumerated hydrogen atom, alkyl, halogen atom, carbalkoxy, carboxyl, formamyl, hydroxyl, alkoxyl group and cyano group.Each substituting group also can have substituting group.R ¹And R ²Perhaps R ⁵And R ⁶Also can interosculate and form five yuan or six-ring.

By A, R ¹, R ², R ⁵, R ⁶, each substituting group of representing of G, have the substituting group under the substituting group occasion, can enumerate above-mentioned G, R ¹, R ²In the substituting group enumerated.

When dyestuff of the present invention is under the occasion of water-soluble dye, at A, R ¹, R ², R ⁵, R ⁶, preferably have with ionic hydrophilic radical as substituting group on any position on the G.As substituent ionic hydrophilic radical, comprise sulfo group, carboxyl, phosphono and quaternary amines.As the above-mentioned preferred carboxyl of ionic hydrophilic radical, phosphono and sulfo group, preferred especially carboxyl and sulfo group.Carboxyl, phosphono and sulfo group can be in the salt state, and shape is salifiable to comprise ammonium ion, alkalimetal ion (for example lithium ion, sodium ion, potassium ion) and organic cation (for example tetramethyl ammonium, tetramethyl guanidine ion, tetramethyl phosphonium ion) to the ion example.

Aliphatic group described in this specification sheets is meant the aralkyl of alkynyl, aralkyl and replacement of alkenyl, alkynyl, the replacement of alkyl, alkenyl, the replacement of alkyl, replacement.Aliphatic group both can have side chain, also can form ring.The carbon atom number of aliphatic group is preferred 1～20, and more preferably 1～16.The aryl moiety of aralkyl and substituted aralkyl, preferred phenyl or naphthyl, more preferably phenyl.The example of aliphatic group can be enumerated methyl, ethyl, butyl, sec.-propyl, the tertiary butyl, hydroxyethyl, methoxyethyl, cyano ethyl, trifluoromethyl, 3-sulfo group propyl group, 4-sulfo group butyl, cyclohexyl, benzyl, 2-styroyl, vinyl and allyl group.

Aromatic group described in this specification sheets is meant the aryl of aryl or replacement.The preferred phenyl or naphthyl of aryl, preferred especially phenyl.Preferred 6～20 of the carbon atom number of aromatic group, more preferably 6～16.The example of aromatic group comprises phenyl, p-methylphenyl, p-methoxyphenyl, Chloro-O-Phenyl and (3-sulfo group propyl group amino) phenyl.

Heterocyclic group includes substituent heterocyclic group and unsubstituted heterocyclic group.Heterocycle also can with aliphatics ring, aromatic ring or other heterocycle condensations.Described heterocyclic group preferred five yuan or hexa-member heterocycle group.Described substituent example comprises aliphatic group, halogen atom, alkyl and aryl sulfonyl, acyl group, acyl amino, sulfinyl, formamyl, ionic hydrophilic radical etc.The example of described heterocyclic radical comprises 2-pyridyl, 2-thienyl, 2-thiazolyl, 2-[4-morpholinodithio base, 2-benzoxazolyl and 2-furyl.

Comprise in alkyl and the aryl sulfonyl and have substituent alkyl and aryl sulfonyl, unsubstituted alkyl and aryl sulfonyl.As the example of alkyl and aryl sulfonyl, can enumerate methyl sulphonyl and benzenesulfonyl respectively.

Comprise in alkyl and the aryl sulfinyl have substituent alkyl and aryl sulfinyl, the alkyl and the aryl sulfinyl of unsubstituted.As the example of alkyl and aryl sulfinyl, can enumerate methyl sulfinyl and phenyl sulfinyl respectively.

Acyl group comprises having substituent acyl group and unsubstituted acyl.As described acyl group, preferred carbon atom is 1～20 acyl group.Comprise ionic hydrophilic radical in the described substituent example.Described acyl group example comprises ethanoyl and benzyl acyl group.

Can enumerate fluorine atom, chlorine atom and bromine atoms as halogen atom.

Comprise the amino that is replaced by alkyl, aryl or heterocyclic group in the amino, described alkyl, aryl or heterocyclic group can also have substituting group.It as the preferred carbonatoms of alkylamino 1～20 alkylamino.Described substituent example comprises ionic hydrophilic radical.The example of described alkylamino comprises methylamino and diethylamino.

Arylamino includes substituent arylamino and unsubstituted arylamino.It as the preferred carbonatoms of described arylamino 6～20 arylamino.Described substituent example comprises halogen atom and ionic hydrophilic radical.The example of described arylamino comprises phenyl amino and 2-chloro-phenyl-amino.

Heterocyclic amino group includes substituent heterocyclic amino group and unsubstituted heterocyclic amino group.It as the preferred carbonatoms of described heterocyclic amino group 2～20 heterocyclic amino group.Described substituent example comprises alkyl, halogen atom and ionic hydrophilic radical.

Alkoxyl group includes substituent alkoxyl group and unsubstituted alkoxyl group.It as the preferred carbonatoms of described alkoxyl group 1～20 alkoxyl group.Described substituent example comprises alkoxyl group, hydroxyl and ionic hydrophilic radical.Described alkoxyl group example comprises methoxyl group, oxyethyl group, isopropoxy, methoxyethoxy, hydroxyl-oxethyl and 3-carboxyl propoxy-.

Aryloxy includes substituent aryloxy and unsubstituted aryloxy.It as the preferred carbonatoms of described aryloxy 6～20 aryloxy.Described substituent example comprises alkoxyl group and ionic hydrophilic radical.Described aryloxy example comprises phenoxy group, to methoxy phenoxy and o-methoxyphenyl.

As the preferred carbonatoms of siloxy-is 1～20 aliphatic group, the siloxy-that aromatic group replaces.Described siloxy-example comprises trimethylsiloxy and diphenyl methyl siloxy-.

Heterocyclic oxy group includes substituent heterocyclic oxy group and unsubstituted heterocyclic oxy group.It as the preferred carbonatoms of described heterocyclic oxy group 2～20 heterocyclic oxy group.Described substituent example comprises alkyl, alkoxyl group and ionic hydrophilic radical.Described heterocyclic oxy group example comprises 3-pyridyloxy, 3-thianthrene oxygen base.

Alkyl oxy carbonyl oxygen includes substituent alkyl oxy carbonyl oxygen and unsubstituted alkyl oxy carbonyl oxygen.It as the preferred carbonatoms of described alkyl oxy carbonyl oxygen 2～20 alkyl oxy carbonyl oxygen.Described alkyl oxy carbonyl oxygen example comprises methoxy carbonyl oxygen base, the different third oxygen carbonyl oxygen base.

Virtue oxygen carbonyl oxygen base includes substituent fragrant oxygen carbonyl oxygen base and unsubstituted fragrant oxygen carbonyl oxygen base.It as the preferred carbonatoms of described fragrant oxygen carbonyl oxygen base 7～20 fragrant oxygen carbonyl oxygen base.Described fragrant oxygen carbonyl oxygen base example comprises carbonyl phenoxy oxygen base.

Acyl amino includes substituent acyl amino and unsubstituted acyl amino.It as the preferred carbonatoms of described acyl amino 2～20 acyl amino.Described substituent example comprises ionic hydrophilic radical.Described acyl amino example comprises kharophen, propionamido, benzyl amido, N-phenyl kharophen and 3,5-disulfo 7 benzyl amidos.

Urea groups includes substituent urea groups and unsubstituted urea groups.It as the preferred carbonatoms of described urea groups 1～20 urea groups.Described substituent example comprises alkyl and aryl.Described urea groups example comprises 3-methyl urea groups, 3,3-dimethyl urea groups and 3-phenyl urea groups.

Sulfamoylamino group includes substituent sulfamoylamino group and unsubstituted sulfamoylamino group.Described substituting group example comprises alkyl.The example of described sulfamoylamino group comprises N, N-dipropyl sulfamoylamino group.

Alkoxycarbonyl amido includes substituent alkoxycarbonyl amido and unsubstituted alkoxycarbonyl amido.It as the preferred carbonatoms of described alkoxycarbonyl amido 2～20 alcoxyl carbonyl amino base.Described substituting group example comprises ionic hydrophilic radical.Described alkoxycarbonyl amido example comprises ethoxycarbonyl amino.

Alkyl and arlysulfonylamino include substituent alkyl and arlysulfonylamino and unsubstituted alkyl and arlysulfonylamino.The sulfuryl amino of the preferred carbonatoms 1～20 of the example of described sulfuryl amino.Described substituting group example comprises ionic hydrophilic radical.Described sulfuryl amino example comprises methyl sulphonyl amino, N-phenyl-methyl sulphonyl amino, phenyl sulfonyl amino and 3-carboxyl phenyl sulfuryl amino.

Carbamyl includes substituent carbamyl and unsubstituted carbamyl.Described substituting group example comprises alkyl.Described carbamyl comprises methyl carbamyl and dimethylamino formyl radical.

Sulfamyl includes substituent sulfamyl and unsubstituted sulfamyl.Described substituting group example comprises alkyl.The amino example of described sulfamyl comprises dimethylamino alkylsulfonyl and two-(2-hydroxyethyl) sulfamyl.

Carbalkoxy includes substituent carbalkoxy and unsubstituted carbalkoxy.It as the preferred carbonatoms of described carbalkoxy 2～20 carbalkoxy.Described substituting group example comprises ionic hydrophilic radical.Described carbalkoxy example comprises methoxycarbonyl and ethoxycarbonyl.

Acyloxy includes substituent acyloxy and unsubstituted acyloxy.As described acyloxy, preferably has the acyloxy of 1～20 carbon atom.Described substituent example comprises ionic hydrophilic radical.Described acyloxy example comprises acetoxyl group and benzoyloxy group.

Carbamoyloxy includes substituent carbamoyloxy and unsubstituted carbamoyloxy.Described substituting group example comprises alkyl.Described carbamoyloxy example comprises N-methylamino methanoyl.

Aryloxy carbonyl includes substituent aryloxy carbonyl and unsubstituted aryloxy carbonyl.Aryloxy carbonyl as the preferred carbonatoms 7～20 of described aryloxy carbonyl.Described substituting group example comprises ionic hydrophilic radical.Described aryloxy carbonyl example comprises carbobenzoxy.

Aryloxy carbonyl amino includes the amino and unsubstituted aryloxy carbonyl amino of substituent aryloxy carbonyl.Aryloxy carbonyl as the amino preferred carbonatoms 7～20 of described aryloxy carbonyl.Described substituting group example comprises ionic hydrophilic radical.The amino example of described aryloxy carbonyl comprises carbobenzoxy amino.

Alkyl, aryl and heterocycle sulfenyl include substituent alkyl, aryl and heterocycle sulfenyl and unsubstituted alkyl, aryl and heterocycle sulfenyl.As described alkyl, aryl and the preferred carbonatoms 1～20 of heterocycle sulfenyl.Described substituting group example comprises ionic hydrophilic radical.Described alkyl, aryl and heterocycle sulfenyl example comprise methylthio group, thiophenyl and 2-pyridine sulfenyl.

Heterocycle oxygen carbonyl includes substituent heterocycle oxygen carbonyl and unsubstituted heterocycle oxygen carbonyl.Heterocycle oxygen carbonyl as the preferred carbonatoms 2～20 of described heterocycle oxygen carbonyl.Described substituting group example comprises ionic hydrophilic radical.Described heterocycle oxygen carbonyl example comprises 2-pyridyl oxo carbonyl.

The heterocycle sulfonamido includes substituent heterocycle sulfonamido, unsubstituted heterocycle sulfonamido.The heterocycle sulfonamido that preferably has 1～12 carbon atom as the heterocycle sulfonamido.Described substituting group example comprises ionic hydrophilic radical.Described heterocycle sulfonamido example comprises 2-thiophene sulfonamido and 3-pyridine sulfonamido.

The heterocycle alkylsulfonyl includes substituent heterocycle alkylsulfonyl, unsubstituted heterocycle alkylsulfonyl.The heterocycle alkylsulfonyl that preferably has 1～12 carbon atom as the heterocycle alkylsulfonyl.Described substituting group example comprises ionic hydrophilic radical.Described heterocycle alkylsulfonyl example comprises 2-thiophen sulfuryl and 3-pyridine alkylsulfonyl.

The heterocycle sulfinyl includes substituent heterocycle sulfinyl, unsubstituted heterocycle sulfinyl.Heterocycle sulfinyl as preferred 1～20 carbon atom of heterocycle sulfinyl.Described substituting group example comprises ionic hydrophilic radical.Described heterocycle sulfinyl example comprises 4-pyridine sulfinyl.

The dyestuff of being represented by general formula (M-I) among the present invention is preferably by the dyestuff of remembering general formula (M-II) expression down.

[changing 3]

General formula (M-II)

In the general formula (M-II), Z ₁The special substituent constant σ of expression Hamann p value is the electrophilic group more than 0.20.Z ₁Though preferred σ p value is the electrophilic group more than 0.30, more preferably σ p value is the electrophilic group more than 0.45, and preferred especially σ p value is the electrophilic group more than 0.60, but should be no more than 1.0.Though can enumerate electrophilic group described later about preferred concrete substituting group, wherein acyl group, the alkoxy carbonyl of carbonatoms 2～20, nitro, cyano group, the alkyl sulphonyl of carbonatoms 1～20, the carbon number of preferred carbonatoms 2～20 are that 6～20 aryl sulfonyl, carbon number are 1～20 formamyl, the haloalkyl of carbonatoms 1～20.Particularly preferably be the alkyl sulphonyl of cyano group, 1～20 carbon atom, the aryl sulfonyl of 6～20 carbon atoms, wherein cyano group most preferably.

R ¹, R ², R ⁵, R ⁶With general formula (M-I) synonym.R ³And R ⁴Independent separately expression hydrogen atom, aliphatic group, aromatic group, heterocyclic group, acyl group, carbalkoxy, aryloxy carbonyl, formamyl, alkyl or aryl carbonyl or sulfamyl.Wherein preferred hydrogen atom, aromatic group, heterocyclic group, acyl group, alkyl or aryl carbonyl, preferred especially hydrogen atom, aromatic group, heterocyclic group.Z ₂Expression hydrogen atom, aliphatic group, aromatic group or heterocyclic group.Q represents atom, aliphatic group, aromatic group or heterocyclic group.Wherein Q is preferably by for forming the group that the required non-metallic atom group of 5～8 former rings is constituted.Described 5～8 yuan of rings also can be substituted, even saturated rings also can have unsaturated link(age).Wherein special optimization aromatic group and heterocyclic group.Preferred non-metallic atom can be enumerated nitrogen-atoms, Sauerstoffatom, sulphur atom or carbon atom.Specific examples with this ring structure for example can be enumerated phenyl ring, pentamethylene ring, cyclohexane ring, cyclodecane ring, cyclooctane ring, cyclohexene ring, pyridine ring, pyrimidine ring, pyrazine ring, pyridazine ring, triazine ring, imidazole ring, benzoglyoxaline Huan, oxazole ring, benzoxazole ring, thiazole ring, benzothiazole Huan, oxane ring, tetramethylene sulfone ring and thianthrene ring etc.

Each group that is illustrated by general formula (M-II) also can have substituting group.These groups have under the substituent occasion, and described substituting group can be enumerated the substituting group of explanation in the general formula (M-I) and at G, R ¹, R ²Cited group and ionic hydrophilic radical.

The special substituent constant σ of Hamann p value is the electrophilic group more than 0.60, can enumerate cyano group, nitro, alkyl sulphonyl (for example methylsulfonyl), aryl sulfonyl (for example benzenesulfonyl).

The special substituent constant σ of Hamann p value is the electrophilic group more than 0.45; except that above-mentioned, can also enumerate acyl group (for example ethanoyl), carbalkoxy (for example dodecyloxy carbonyl), aryloxy carbonyl (m-chloro phenyloxycarbonyl), alkyl sulfinyl (for example n-propyl sulfinyl), aryl sulfinyl (for example inferior sulphur sulfenyl of phenyl), sulfamyl (for example N-ethyl sulfamyl, N, N-dimethylamino alkylsulfonyl), haloalkyl (for example trifluoromethyl).

The special substituent constant σ of Hamann p value is the electrophilic group more than 0.30; except that above-mentioned; can enumerate acyloxy (for example acetoxyl group); formamyl (N-ethylamino formyl radical for example; N; N-dibutylamino formyl radical); halogenated alkoxy (for example trifluoromethoxy); halo aryloxy (for example penta fluoro benzene oxygen base); sulfonyloxy (for example mesyloxy); halogenated alkylthio (for example difluoro methylthio group); by two above σ p values be the aryl that replaces of the electrophilic group more than 0.15 (for example 2, the 4-dinitrophenyl; five chlorophenyl) and heterocyclic group (2-benzoxazolyl for example; the 2-[4-morpholinodithio base; 1-phenyl-2-benzimidazolyl-).σ p value is the specific examples of the electrophilic group more than 0.20, can enumerate halogen atom except that above-mentioned.

Make up as the particularly preferred substituting group of azopigment, wherein R by above-mentioned general formula (M-I) expression ⁵And R ⁶Preferred hydrogen atom, alkyl, aryl, heterocyclic group, alkylsulfonyl and acyl group, more preferably hydrogen atom, aryl, heterocyclic group and alkylsulfonyl, preferably hydrogen atom, aryl and heterocyclic group.But R ⁵And R ⁶Can not be hydrogen atom simultaneously.

The preferred hydrogen atom of G, halogen atom, alkyl, hydroxyl, amino, acyl amino, more preferably hydrogen atom, halogen atom, amino and acyl amino, preferably hydrogen atom, amino and acyl amino.

Preferred pyrazoles ring, imidazole ring, isothiazole ring, thiadiazoles ring, benzothiazole ring, more preferably pyrazoles ring, isothiazole ring, preferably pyrazoles ring among the A.

B ¹And B ²Expression-CR respectively ¹=and-CR ²=, R ¹And R ²Independent separately preferred hydrogen atom, alkyl, halogen atom, cyano group, formamyl, carboxyl, hydroxyl, alkoxyl group, carbalkoxy, more preferably hydrogen atom, alkyl, carboxyl, cyano group, formamyl.

Preferred cyan dye can be enumerated the dyestuff by following general formula (C-I) expression.

In the general formula (C-I), X ₁, X ₂, X ₃And X ₄Independent separately expression σ p value is the electrophilic group more than 0.40.Y ₁, Y ₂, Y ₃And Y ₄Independent separately expression monovalence substituting group.M represents hydrogen atom, metallic element or its oxide compound, oxyhydroxide or halogenide.a ₁～a ₄, b ₁～b ₄Represent X respectively ₁～X ₄, Y ₁～Y ₄The substituting group number.a ₁～a ₄Independent separately 0～4 integer, the b of representing ₁～b ₄Independent separately 0～4 the integer of representing.But wherein preferred a ₁～a ₄Sum is more than 2, more preferably more than 3, and preferred especially a ₁=a ₂=a ₃=a ₄=1.When dyestuff is under the water miscible occasion, preferably at X ₁, X ₂, X ₃, X ₄, Y ₁, Y ₂, Y ₃, Y ₄On any position on also have ionic hydrophilic radical as substituting group.Substituent ionic hydrophilic radical comprises sulfo group, carboxyl, phosphono and quaternary ammonium group etc.

In phthalocyanine pigment, more preferably has phthalocyanine pigment by the structure of general formula (C-II) expression by above-mentioned general formula (C-I) expression.Below be elaborated with regard to the phthalocyanine pigment by general formula (C-II) expression of the present invention.

[changing 5]

General formula (C-II)

In the general formula (C-II), X ₁₁～X ₁₄Independent separately expression-SO-Z ,-SO ₂-Z ,-SO ₂NR ₁R ₂, sulfo group ,-CONR ₁R ₂Or-CO ₂R ₁Y ₁₁～Y ₁₈Independent separately expression monovalence substituting group.M represents hydrogen atom, atoms metal or its oxide compound, oxyhydroxide or halogenide.a ₁₁～a ₁₄Represent X respectively ₁₁～X ₁₄The substituting group number, the integer of independent expression 1 or 2.

Z independently represents replacement or unsubstituted alkyl, replacement or unsubstituted cycloalkyl, replacement or unsubstituted alkenyl, replacement or unsubstituted aralkyl, replacement or unsubstituted aryl, replacement or unsubstituted heterocyclic group separately.R ₁, R ₂Independent separately hydrogen atom, replacement or unsubstituted alkyl, replacement or unsubstituted cycloalkyl, replacement or unsubstituted alkenyl, replacement or unsubstituted aralkyl, replacement or unsubstituted aryl, replacement or the unsubstituted heterocyclic group of representing.

In the general formula (C-II), a ₁₁～a ₁₄The integer of independent expression 1 or 2 particularly preferably is 4≤a respectively ₁₁+ a ₁₂+ a ₁₃+ a ₁₄≤ 6.A preferably wherein ₁₁=a ₁₂=a ₁₃=a ₁₄=1 o'clock.

X ₁₁, X ₁₂, X ₁₃And X ₁₄Both can be identical separately substituting group, or work as X ₁₁, X ₁₂, X ₁₃And X ₁₄Be-SO ₂The situation that each Z is mutually different during-Z is such, can be that substituent kind is identical but its part is different mutually, or-SO ₂-Z and-SO ₂NR ₁R ₂Replace like that simultaneously, contain different substituting groups.

In the phthalocyanine pigment by general formula (C-II) expression, particularly preferred substituting group combination is as follows.

As X ₁₁～X ₁₄Separately independently preferably-SO-Z ,-SO ₂-Z ,-SO ₂NR ₁R ₂Or-CONR ₁R ₂, especially preferably-SO ₂-Z or-SO ₂NR ₁R ₂, preferably-SO ₂-Z.

Z is preferably replacement or unsubstituted alkyl, replacement or unsubstituted aryl or replacement or unsubstituted heterocyclic group independently of one another, wherein the alkyl that preferably replaces, the aryl of replacement, the heterocyclic group of replacement.From the solvability of raising dyestuff and the stability of printing ink, preferably in substituting group, contain the occasion of unsymmetrical carbon (using) especially with racemic modification.And, preferably include hydroxyl, ether, ester group, cyano group, amide group, sulfoamido in the substituting group from improving the viewpoint of concentration and fastness.

R ₁, R ₂Preferably represent hydrogen atom, replacement or unsubstituted alkyl, replacement or unsubstituted aryl, replacement or unsubstituted heterocyclic group independently of one another, wherein the heterocyclic group of the aryl of the alkyl of hydrogen atom, replacement, replacement, replacement most preferably.But R ¹, R ²Each can not be a hydrogen atom simultaneously.From the solvability of raising dyestuff and the stability of printing ink, preferably contain unsymmetrical carbon (using) in the substituting group especially with racemic modification.And, preferably include hydroxyl, ether, ester group, cyano group, amide group, sulfoamido in the substituting group from improving the viewpoint of concentration and fastness.

Y ₁₁～Y ₁₈Preferred hydrogen atom, halogen atom, alkyl, aryl, cyano group, alkoxyl group, amide group, urea groups, sulfonamido, formamyl, sulfamyl, carbalkoxy, carboxyl and sulfo group; preferred especially hydrogen atom, halogen atom, cyano group, carboxyl and sulfo group, most preferably hydrogen atom.a ₁₁～a ₁₄Preferably represent 1 or 2 respectively independently, especially preferably be 1.M represents hydrogen atom, metallic element or its oxide compound, oxyhydroxide or halogenide, preferred especially Cu, Ni, Zn, Al, wherein Cu most preferably.

When by above-mentioned (C-I) or (C-II) expression phthalocyanine pigment be under the water miscible occasion, preferably have ionic hydrophilic radical.Ionic hydrophilic radical comprises sulfo group, carboxyl, phosphono or quaternary ammonium group etc.As described ionic hydrophilic radical, preferred carboxyl, phosphono and sulfo group, preferred especially carboxyl and sulfo group.Carboxyl, phosphono and sulfo group can be in the state of salt, and shape is salifiable to have ammonium ion, alkalimetal ion (for example lithium ion, sodium ion, potassium ion) and organic cation (for example tetramethyl ammonium, tetramethyl guanidine ion, tetramethyl phosphonium ion) to the ionic example.To preferred as alkali salt in the ion, from the wherein preferred especially lithium salts of the stability of the solvability that can improve dyestuff and printing ink.

The number of ionic hydrophilic radical preferably has at least more than two in a phthalocyanine pigment molecule, preferably has two above sulfo groups and/or carboxyl especially.

About making up by preferred substituted in the compound of above-mentioned general formula (C-II) expression, having one in the preferred various substituting group at least is the compound of above-mentioned preferred substituents, it is the compound of above-mentioned preferred substituents that multiple substituting group is more preferably arranged, and most preferably all substituting group is the compound of above-mentioned preferred substituents.

The chemical structure of the preferred phthalocyanine pigment that uses among the present invention; preferably on each phenyl ring in four phenyl ring of phthalocyanine molecule; at least respectively import a sulfinyl, alkylsulfonyl, sulfamyl and so on electron-attracting substituent, make on the phthalocyanine frame all substituent total σ p values more than 1.60.

Phthalocyanine derivates by above-mentioned general formula (C-I) expression, unavoidably be the mixture of the importing position of substituent X n (n=1～4) and Ym (m=1～4) analogue different because of its synthetic method generally speaking, so general formula is represented the mixture of these analogues mostly with the form of adding up equalization with importing number.Among the present invention,, then found particularly preferred specific mixture if the mixture of these analogues is categorized into following three kinds.That is to say, according to the position of substitution with above-mentioned general formula (C-I) and (C-II) mixture of phthalocyanine based dye analogue of expression be defined as following three classes.

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

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

(3) α, substituted type is mixed in β-position: the phthalocyanine pigment that specified substituent is irregularly arranged on 1～16

Under the occasion of the phthalocyanine pigment of description architecture difference in this specification sheets (particularly the position of substitution difference), use above-mentioned β-position substituted type, alpha-position substituted type, α, substituted type is mixed in β-position

The phthalocyanine derivates of Shi Yonging in the present invention, can collaborate record on " phthalocyanine-chemistry and function-" (1～62 page) of ア ィ ピ-シ-Co., Ltd.'s distribution and " phthalocyanine-character and application-" (1～54 page) that C.C.Leznoff-A.B.P.Lever collaborates according to for example white well-holt, synthesize after quoting or itself and similar approach being made up.

Phthalocyanine compound of the present invention by above-mentioned general formula (C-I) expression; as WO00/17275, WO00/08103, WO00/08101, WO98/41853, spy open record on the flat 10-36471 equal sign communique, for example can make unsubstituted phthalocyanine compound synthetic through oversulfonate, chlorosulfonylation, amidate action.Under this occasion, even on any position of phthalocyanine nucleus, can both produce sulfonation reaction, the also restive number that is sulfonated.Therefore importing under the occasion of sulfo group under this reaction conditions, can not specificly be directed to the position and the number of the sulfo group on the resultant, must generate the substituent number mixture different with the position of substitution.Therefore; when with it being the synthetic compound of the present invention of raw material; owing to can not make the number and the position specialization of heterocyclic substituted sulfamyl, so that obtain as compound of the present invention is the α that contains several substituting group numbers compound different with the position of substitution, β-position substituted type mixture.

As mentioned above, for example in case import the electrophilic group of a plurality of sulfamyl etc. on phthalocyanine nucleus, oxidizing potential will increase, and ozone resistance is improved.So,, just sneak into the lower phthalocyanine pigment of oxidizing potential inevitably in case the number of the electrophilic group that imports is few if according to above-mentioned synthetic method.Therefore be the raising ozone resistance, the synthetic method that more preferably adopts the lower compound of energy inhibited oxidation current potential to generate.

In contrast to this, by the phthalocyanine compound of general formula (C-II) expression, for example can obtain with the metal derivative reaction of representing by (C-III) by phthalonitrile derivative (Compound P) and/or the diimino isoindoline (compound Q) that following general formula is represented.Perhaps can be to derive the four sulfo group phthalocyanine compounds that obtain from reacting with the metal derivative of representing with general formula (C-III) with the represented 4-sulfosalicylic phthalate derivative (compound R) of following general formula.

[changing 6] Compound P compound Q compound R

Above-mentioned various in, Xp is equivalent to the X in the above-mentioned general formula (C-II) ₁, X ₂, X ₃, X ₄And Yq, Yq ' are equivalent to the Y in the above-mentioned general formula (C-II) respectively ₁₁, Y ₁₂, Y ₁₃, Y ₁₄, Y ₁₅, Y ₁₆, Y ₁₇, Y ₁₈M ' expression positively charged ion in the compound R.

General formula (C-III): M-(Y) d

In the general formula (C-III), M is identical with M in the above-mentioned general formula (C-II), and Y represents the ligand of monovalencies such as halogen atom, acetate negatively charged ion, acetylacetonate, oxygen or divalence, and d represents 1～4 integer.

That is to say, can only import the required substituting group of given number according to above-mentioned synthetic method.Especially as the present invention, will import under the occasion of a plurality of electrophilic groups for improving oxidizing potential, compare with the synthetic method of general formula (C-I), above-mentioned synthetic method is very good method.

The phthalocyanine compound that obtains like this by above-mentioned general formula (C-II) expression, will form usually a kind of each the position of substitution as Xp isomer by the mixture of remembering general formula (a)-1～(a)-4 expression down, i.e. β-position substituted type compound.

[changing 7]

General formula (a)-1 general formula (a)-3

General formula (a)-2 general formula (a)-4

If use the identical substituting group of Xp, then can obtain X in the above-mentioned synthetic method ₁₁, X ₁₂, X ₁₃And X ₁₄Be identical substituent β-position substituted type phthalocyanine pigment.On the other hand, if be used in combination the different substituting group of Xp, be the mutual different substituent dyestuff of its part of similar substituting group though then can have, perhaps can synthesize and have the substituent dyestuff of mutual different sorts.These dyestuffs that have mutually different electron-attracting substituents in the dyestuff of general formula (C-II), preferred especially owing to also can adjust solvability, the aggregation of dyestuff, the ageing stability of printing ink etc.

Which kind of substituted type no matter find among the present invention, be, oxidizing potential is very important greater than 0.8V (vs SCE) for improving fastness, and the size of its effect can not be imagined from prior art fully.Though and relevant its reason is still not fully aware of, and α, β-position mixing substituted type is compared, and β-position substituted type all demonstrates obviously good trend in each side such as tone, light fastness and ozone resistances.

Above-mentioned by general formula (C-I) and (C-II) represented phthalocyanine pigment, can be synthetic according to above-mentioned patented method, promptly can adopt the method for putting down in writing in the special 2001-226275 of hope, the special 2001-96610 of hope, the special 2001-47013 of hope and the patent application of the special 2001-193638 of hope equal sign synthetic.And be not limited to wherein stipulate about original raw material, dyestuff intermediate and synthetic route those.

The rosaniline dyes that the present invention uses is characterized in that oxidizing potential is than 0.8V height.And the phthalocyanine that is widely used as cyan dye, because of forming aggregate, even so how many reductions of oxidizing potential also can compensate fastness, but for rosaniline dyes, do not form aggregate, so preferably set oxidizing potential higher than cyan dye in order to improve the fastness height owing to it.

Below enumerate the preferred coloring agent example that can use in the present invention, but these examples only are used to describe in detail the present invention, so the present invention is not subjected to any restriction of these examples.The oxidizing potential of the numeral dyestuff in its brace.

At first enumerate the specific examples that can be used in yellow dyes of the present invention (Y-1～Y-35).

[changing 8]

Y-11??R＝-S(CH ₂) ₂SO ₃Na

(1.20)

Y-12??R＝-Me?????(1.19)

Y-13??R＝-H?????(1.20)

Y-14??R＝-Ph?????(1.18)

Secondly, enumerate the specific examples that can be used in rosaniline dyes of the present invention (M-1～M-26).

[changing 15]

Then enumerate the specific examples that can be used in cyan dye of the present invention (C-1～C-50).

[changing 23]

(Y in the table ¹¹, Y ¹²), (Y ¹³, Y ¹⁴), (Y ¹⁵, Y ¹⁶), (Y ¹⁷, Y ¹⁸) respectively concrete example of group is different in regular turn independently respectively.

Cu-Pc-(SO ₂R ¹) _m(SO ₂R ²) _n

Cu-Pc-(SO ₂R ¹) _m(SO ₂R ²) _n

[changing 31]

The examples of compounds that can use in the present invention, in addition also be documented in spy's hope 2001-96610 number, spy's hope 2001-24352 number, spy's hope 2001-47013 number, spy's hope 2001-57063 number, spy's hope 2001-76689 number, spy's hope 2001-193638 number, spy's hope 2001-15614 number, spy's hope 2001-110457 number, the patent application of spy's hope 2001-110335 equal sign, still be not limited to these.And each above-mentioned compound can adopt the method for putting down in writing in the patent of enumerating synthetic easily here.

-ink for ink-jet recording-

Ink for ink-jet recording group of the present invention, the cyan ink that contains a kind of magenta ink of rosaniline dyes and contain a kind of cyan dye at least is minimum integrant with the Yellow ink that contains a kind of yellow dyes at least, at least.Contained dyestuff in each printing ink can use above-mentioned various dyestuffs.Various printing ink are normally with dyestuff dissolving and/or be dispersed in and make in lipophilicity medium and the aqueous medium.The preferred aqueous medium that adopts.

Can in the scope of not damaging effect of the present invention, add other additives in case of necessity.As other additives, for example can enumerate that drying prevents agent (wetting agent), known additives such as preventing agent, emulsion stabilizer, penetration enhancer, UV light absorber, sanitas, mould inhibitor, pH regulator agent, surface tension modifier, defoamer, viscosity modifier, dispersion agent, dispersion stabilizer, rust-preventive agent, sequestrant fades.Under the occasion of water-based ink, these various additives are directly added in the printing ink liquid.To disperse the thing form to use under the occasion of oil-soluble colourant, generally after the preparation dyestuff disperses thing, add to and disperse in the thing, but also can be added on oil phase or aqueous phase.

Above-mentioned drying prevents agent, can be used to prevent that the printing ink ejiction opening at the employed nozzle of ink-jet recording from being stopped up by this ink for inking drying.

Prevent the water-miscible organic solvent that the preferred vapour pressure of agent is lower than water as drying.Its specific examples can be enumerated with ethylene glycol, propylene glycol, glycol ether, polyoxyethylene glycol, the sulfo-glycol, the dithio glycol, the 2-methyl isophthalic acid, ammediol, 1,2, the 6-hexanetriol, the acetylenediol derivative, glycerine, TriMethylolPropane(TMP)s etc. are the polyalcohols of representative, glycol monomethyl first (or second) ether, diglycol monotertiary first (or second) ether, the low alkyl group ethers of polyvalent alcohols such as triglycol list second (or fourth) ether, 2-Pyrrolidone, the N-N-methyl-2-2-pyrrolidone N-, 1,3-dimethyl-2-imidazolinedione, heterocyclic such as N-ethylmorpholine, tetramethylene sulfone, methyl-sulphoxide, sulfocompounds such as 3-tetramethylene sulfone, diacetone alcohol, polyfunctional compounds such as diethanolamine, and urea derivative.More preferably polyvalent alcohol such as glycerine and glycol ether wherein.And above-mentioned drying prevents that agent from can use separately or two or more and usefulness.These dryings prevent that agent from preferably containing 10～50 weight % in printing ink.

Above-mentioned penetration enhancer can be used to make printing ink to permeate paper better.Above-mentioned penetration enhancer can use ethanol, Virahol, butanols, two (three) glycol monobutyl ethers, 1, alcohols such as 2-hexylene glycol, and sodium laurate, sodium oleate and nonionic surface active agent etc.These materials content in printing ink then can produce effect of sufficient usually if reach 5～30 weight %, preferably uses in the addition scope that the infiltration that does not produce lettering and seal are worn.

Above-mentioned ultraviolet ray prevents that agent can be used to improve the keeping quality of image.Above-mentioned ultraviolet ray prevents agent, can use the spy to open clear 58-185677, the spy opens clear 61-190537, Te Kaiping 2-782, Te Kaiping 5-197075, the benzotriazole based compound of putting down in writing on the Te Kaiping 9-34057 equal sign communique, the spy opens clear 46-2784, Te Kaiping 5-194483, the benzophenone based compound of putting down in writing in the US3214463 equal sign communique, special public clear 48-30492, special public clear 56-21141, the TRANSCINNAMIC ACID based compound of putting down in writing in the Te Kaiping 10-88106 equal sign communique, Te Kaiping 4-298503, Te Kaiping 8-53427, Te Kaiping 8-239368, Te Kaiping 10-182621, the triazine based compound of putting down in writing in the Te Biaoping 8-501291 equal sign communique, be numbered No. 24239 sieve Jie Shi (ロ one ジ ャ one) retrieval above-mentioned year compound of CD and with 1,2-toluylene system; the benzoxazole based compound is the compound of emitting fluorescence after the absorption ultraviolet ray of representative, promptly can use so-called white dyes.

Above-mentioned fading prevents that agent from can use improving under the conservatory purpose of image.Described fading prevents that agent from can use various organic systems and metal complex system to fade and preventing agent.Prevent that as organic fading agent from having hydroquinones, alkoxy benzene phenols, dialkoxy phenol, phenol, phenyl amines, amine, indenes class, coumarins, alkoxy benzene amine, thioether class, Thiourea, heterocyclic etc. (for example special open 2002-36717, spy open 2002-86904 equal sign communique put down in writing), has nickel complex, zinc complex etc. as metal complex.More particularly, can use the VII of numbering sieve Jie Shi of 17643 retrieval CD I～J item, with No. 15162, with No. 18716 the 650th page of Zuo Lan, with No. 36544 527 pages, with No. 307105 872 pages, with the compound of putting down in writing in the patent of quoting on No. 15162, and special 127 pages～137 pages of opening clear 62-215272 communique are gone up the general formula of representative compounds of record and the compound that examples of compounds is comprised.

Above-mentioned mould inhibitor can be enumerated Sodium dehydroacetate, Sodium Benzoate, pyridine sulfo--1-oxide sodium salt, ethyl p-hydroxybenzoate, 1,2-benzisothiazole-3-ketone and salt thereof etc.These materials preferably use 0.02～1.00 weight % in printing ink.

Above-mentioned pH regulator agent can be used above-mentioned neutralizing agent (organic bases, mineral alkali).Above-mentioned pH regulator agent purpose is to improve the storage stability of ink for inking, preferably adds to such an extent that make this ink for inking pH6～10 in summer, more preferably adds pH7～10 to.

Above-mentioned surface tension modifier can be enumerated non-ionic type, cationic and aniorfic surfactant.The surface tension of the ink for inking that the present invention relates in addition is preferably 25～70mPas.More preferably 25～60mN/m.And the viscosity of the ink for inking that the present invention relates to preferably adjusts to below the 30mPas, more preferably adjusts to below the 20mPas.The example of tensio-active agent, aniorfic surfactant such as preferred fat hydrochlorate, alkyl sulfuric ester salt, alkylbenzene sulfonate, sulfonated alkyl naphathalene, dialkyl sulfosuccinates, alkyl phosphate salt, naphthalene sulfonic acidformaldehyde condensation product, polyxyethylated sulfuric acid, and nonionic surface active agent such as Voranol EP 2001, polyxyethylated allyl ethers, polyoxyethylene fatty acid ester, sorbitan-fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene alkyl amine, glycerin fatty acid ester, oxygen ethylene oxy propylene-based block copolymer.But also preferred use itself is that acetylene is the SURFYNOLS (air products and chemical company manufacturing) of polyoxyethylene oxide surface promoting agent.Also preferably use N in addition, N-dimethyl-N-alkyl amine oxide and so on amine oxide type and contain N, the betaine type amphoteric surfac-tant of N-dimethyl-quaternary amines such as N-lauryl carbonyl ammonium methyl etc.Can also use the spy to open (37)～(38) page of clear 59-157, No. 636 in addition and be numbered on 308119 (1989) sieve Jie Shi retrieval CD tensio-active agent as the tensio-active agent record.

As above-mentioned defoamer, also can use fluorine-containing system, silicone compound in case of necessity, be sequestrant of representative etc. with EDTA.

The dyestuff that the present invention relates to is under the oil-soluble occasion, as the method that it is dispersed in the aqueous medium, preferably as the special flat 11-286637, spy of opening open 2001-240763, spy and open 2001-262039, spy and open the disclosed toner that will contain dyestuff and oil-soluble polymers such as 2001-247788 and be dispersed in the aqueous medium, open as the spy perhaps that 2001-262018, spy open 2001-240763, the spy opens record among 2001-335734, the special 2000-203857 of hope etc., the dyestuff that the present invention relates to that is dissolved in the high boiling organic solvent is dispersed in the aqueous medium.About dyestuff of the present invention being dispersed in the concrete grammar in the aqueous medium, oil-soluble polymers, high boiling organic solvent, additive and the consumption thereof of use, can preferably adopt those that put down in writing in the above-mentioned patent.Perhaps dyestuff directly can be dispersed into graininess with solid form.Can use dispersion agent or tensio-active agent when disperseing.As diverting device, can use simple stirring rake or propeller agitation mode, online (inline) alr mode, lapping mode (for example colloidal mill, ball mill, sand mill, masher, roller mill, agitator mill etc.), ultrasonic wave mode, high-pressure emulsification dispersing mode (high pressure homogenizer, concrete commercial device has go-リ Application clarifixator, little fluidizator, DeBEE2000 etc.).Preparation method about above-mentioned ink for ink-jet recording, except that above-mentioned patent, also by write up open flat 5-148436, same 5-295312, same 7-97541, same 7-82515, same 7-118584 the spy, the spy opens on flat 11-286637, the special 2000-87539 of the hope equal sign communique preparation of the ink for ink-jet recording that these also can be used to the present invention relates to.

Above-mentioned aqueous medium is main component with water, can use the mixture that has added water Combination organic solvent in case of necessity.Above-mentioned water Combination organic solvent comprises alcohols (methyl alcohol for example, ethanol, propyl alcohol, Virahol, butanols, isopropylcarbinol, sec-butyl alcohol, the trimethyl carbinol, amylalcohol, hexanol, hexalin, phenylcarbinol), polyalcohols (ethylene glycol for example, glycol ether, triglycol, polyoxyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, butyleneglycol, hexylene glycol, pentanediol, glycerine, hexanetriol, the sulfo-glycol), 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, the dipropylene glycol monomethyl ether, triethylene glycol monomethyl ether, glycol diacetate, ethylene glycol monomethyl ether acetate, triethylene glycol monomethyl ether, triglycol list ether, the glycol monomethyl phenyl ether), amine (thanomin for example, diethanolamine, trolamine, N methyldiethanol amine, the N-ethyldiethanolamine, morpholine, N-ethylmorpholine, 1, the 2-quadrol, Diethylenetriamine, triethylenetetramine, polymine, tetramethyl-trimethylene diamines) and other polar solvents (methane amide for example, N, dinethylformamide, N, the N-N,N-DIMETHYLACETAMIDE, dimethyl sulfoxide (DMSO), tetramethylene sulfone, 2-Pyrrolidone, the N-N-methyl-2-2-pyrrolidone N-, N-vinyl-2-Pyrrolidone, 2-oxazoline ketone, 1,3-dimethyl-2-imidazolinedione, acetonitrile, acetone).Above-mentioned in addition water Combination organic solvent also can two or more and usefulness.

The printing ink that ink-jet sets of the present invention is used preferably contains more than dyestuff 0.1 weight part below 20 weight parts with respect to 10 weight part printing ink.And various printing ink yellow, cyan also can be also with two or more dyestuffs.Magenta ink is as long as oxidizing potential can and be used two or more dyestuffs than 0.8V higher position.And under the occasion with two or more dyestuffs, the total amount of contained dyestuff is in the above-mentioned scope.

For reaching high image qualityization, each printing ink such as yellow, magenta, cyan often is made up of the different two or more printing ink of dye strength in recent years, in the present invention, employed dyestuff in deep or light different various printing ink, preferably its oxidizing potential is all worked as greater than 0.8V.

Use two or more different printing ink as under the occasion with tone printing ink among the present invention, a kind of concentration of printing ink is preferably 0.05～0.5 times of another kind of printing ink concentration.

Though printing ink group of the present invention is used to form full-colour image, also can use black ink in order to adjust tone.Can except that two azos, trisazo-and Tetrakisazo dyes, can also enumerate the sooty dispersion as the material of black.

＜ink jet recording medium 〉

Ink jet recording medium among the present invention has the colorant receiving layer that contains sulfocompound on support.

Sulfocompound

There is no particular restriction for the sulfocompound that the present invention uses, and for example can enumerate one or more compounds of selecting as preferred compound from thioether based compound, thiocarbamide based compound, sulfoxide based compound, thiocyanic acid based compound,-sulfinic acid based compound, disulphide based compound and sulfur heterocyclic compound.

The thioether based compound

The thioether based compound both can be that water miscible compound also can be oil-soluble compound.And both can be that low molecule also can be a polymer, can be the material that contains an above sulfide group in the molecule.

The preferred carbonatoms of thioether based compound is plural, is more preferably more than four.

The thioether based compound preferably also contains and comprises the right atom of isolated electron (for example Sauerstoffatom, sulphur atom, nitrogen-atoms and phosphorus atom) except that containing sulphur atom, carbon atom and hydrogen atom.

As the thioether based compound, for example can enumerate the represented material of following general formula (1).

R ₁-(S-R ₃) m-S-R ₂General formula (1)

In the general formula (1), R ₁And R ₂Represent hydrogen atom, replacement or unsubstituted alkyl, replacement or unsubstituted aryl respectively independently or contain their group, R ₁And R ₂Can be identical or different, also can interosculate into ring.But R ₁And R ₂In at least one by hydrophilic radicals such as hydroxyl, sulfo group, carboxyl, (gathering) vinyloxy group or the group (for example this substituted alkyl can also pass through divalent linkers such as formamyl, carbonyl, carbonyl oxygen base and combine with the sulphur atom of thioether) that contained the alkyl that group replaced of basic nitrogen atom or contain them by amino, amide group, ammonium, nitrogen heterocyclic ring group, aminocarboxyl, sulfamyl etc.R ₃Also can be substituted, expression sometimes contains the alkylidene group of Sauerstoffatom.M represents 0～10 integer, when m greater than 1 occasion under and R ₃At least one sulphur atom of bonded also can be sulfoxide group, alkylsulfonyl.And R ₁And R ₂It also can be each polymer residue.

Particularly preferred compound in the general formula (1) is R ₁And R ₂In at least one is the compound with the alkyl that is replaced by hydroxyl, carboxyl, amino, ammonium.And, comprise the amino of amino, monoalkyl (alkyl of preferred 1～5 carbon atom) replacement, the amino that dialkyl group (alkyl of preferred 1～5 carbon atom) replaces by the amino in the amino alkyl that replaces, also can be the nitrogen heterocyclic ring group.What below enumerate is the specific examples of general formula (1) compound, but the present invention is not limited to these.

[changing 32]

(1)HO(CH ₂) ₃S(CH ₂) ₃OH

(4)HO(CH ₂) ₂S(CH ₂) ₂OH

(5)CH ₃S(CH ₂) ₂CH(NH ₂)COOH

(6)HO(CH ₂) ₂SCH ₂S(CH ₂) ₂OH

(7)HO(CH ₂) ₂S(CH ₂) ₂S(CH ₂) ₂OH

(8)HO(CH ₂) ₂S(CH ₂) ₃S(CH ₂) ₂OH

(9)C ₂H ₅S(CH ₂) ₂SCH ₂CHOHCH ₂OH

(10)HOOCCH ₂SCH ₂SCH ₂COOH

(12)HO(CH ₂) ₂S(CH ₂) ₂SO ₂(CH ₂) ₂S(CH ₂) ₂OH

(13)HO(CH ₂) ₃S(CH ₂) ₂S(CH ₂) ₃OH

(14)HOOCCH ₂SCH ₂COOH

(15)HOOCCH ₂S(CH ₂) ₃SCH ₂COOH

(16)HOOCCH ₂S(CH ₂) ₂SCH ₂COOH

(17)HO(CH ₂) ₂S(CH ₂) ₄S(CH ₂) ₂OH

(18)HO(CH ₂) ₂S(CH ₂) ₂S(CH ₂) ₂S(CH ₂) ₂OH

(19)HOOC(CH ₂) ₂S(CH ₂) ₂S(CH ₂) ₂COOH

(20)HOOC(CH ₂) ₂S(CH ₂)S(CH ₂) ₂COOH

(21)(HO(CH ₂) ₂S(CH ₂) ₂) ₂O

(22)H ₂NCO(CH ₂) ₂S(CH ₂) ₂S(CH ₂) ₂CONH ₂

(23)HOOC(CH ₂) ₂S(CH ₂) ₂COOH

(24)(HOCH ₂CHOHCH ₂SCH ₂) ₂

(25)HOOC(CH ₂) ₂S(CH ₂) ₃S(CH ₂) ₂COOH

(26)C ₂H ₅S(CH ₂) ₂S(CH ₂) ₂NHCO(CH ₂) ₂COOH

(27)HO(CH ₂) ₃S(CH ₂) ₂O(CH ₂) ₃O(CH ₂) ₂S(CH ₂) ₂OH

(28)HO(CH ₂) ₅S(CH ₂) ₅S(CH ₂) ₅OH

The thiocarbamide based compound

The thiocarbamide based compound both can be that water miscible compound also can be oil-soluble compound, and both can be that polymer also can be low molecule.Can enumerate the compound that more than one "＞N-C (=S)-N＜" represented structure is arranged in the molecule.

This thiocarbamide based compound; can enumerate thiocarbamide, N-methylthiourea, N-ethanoyl thiocarbamide, 1; 3-diphenyl thiourea, tetramethyl thiourea, amidinothiourea, 4-methyl thiosemicarbazide, 1; two (methylol)-2 (3H) of 3-benzoglyoxaline thioketones, 6-hydroxyl-1-phenyl-3; 4-dihydro pyrazine-2 (1H) thioketones, 1-allyl group-2-thiocarbamide, 1; 3-dimethyl-2-thiocarbamide, 1,3-diethyl-2-thiocarbamide, ethylene thiourea, trimethyl thiourea, 1-carboxymethyl-2-thio-hydantoin and thiosemicarbazide etc.

The disulphide based compound

The disulphide based compound both can be that water-soluble cpds also can be an oil-soluble compounds, and both can be that polymer also can be low molecule.The for example preferred compound of representing by following general formula, preferred especially DL-alpha-lipoic acid, 4,4 '-dithio morpholine, 4,4 '-dithio, two butyric acid.

R ₁-S-S-R ₂

(in the formula, R ₁And R ₂Be respectively, contain with disulphide in the organic group of sulphur atom bonded carbon atom or nitrogen-atoms.This organic group both can be, with with disulphide in sulphur atom bonded carbon atom or nitrogen-atoms form and replace or the group of unsubstituted aliphatic group, replacement or unsubstituted aromatic group or replacement or unsubstituted heterocyclic group, also can be with the sulphur atom bonded carbon atom of disulphide or nitrogen-atoms on combine and replace or the organic group of unsubstituted aliphatic group, aromatic group, heterocyclic group or amino and imino-, Sauerstoffatom, sulphur atom etc.And R ₁And R ₂Can be identical or different, also can be in conjunction with forming ring.R ₁And R ₂Above-mentioned substituting group, be alkyl, aryl, heterocyclic group, amino, amide group, imino-, ammonium, hydroxyl, sulfo group, carboxyl, aminocarboxyl or substituting groups such as amino-sulfonyl, halogen atom.)

Sulfinic acid compound

Sulfinic acid compound, both can be water miscible also can be oil-soluble, and both can be that polymer also can be low molecule, can contain an above-sulfinic acid skeleton structure at intramolecularly.

As the sulfinic acid compound that uses among the present invention, the compound that preferred following general formula is represented.

R-SO ₂M

(in the formula, R represents to replace or unsubstituted alkyl (preferred 6～30 carbon atoms), replacement or unsubstituted aryl (phenyl, naphthyl etc., preferred 6～30 carbon atoms), polymer residue.M represents atoms metal, alkali metal atom, ammonium.)

The substituting group of the group of representing by above-mentioned R; can enumerate for example straight chain; side chain or cyclic alkyl (1～20 of preferred carbonatoms); aralkyl (preferred monocycle or dicyclo; the carbonatoms of moieties is 1～3); alkoxyl group (preferred 1～20 carbon atom); one or the disubstituted amido (alkyl of preferred 1～20 carbon atom; acyl group; the alkyl or aryl alkylsulfonyl; under dibasic occasion; the total number of carbon atoms in the substituting group is in below 20); 1～3 replaces or unsubstituted urea groups (preferred 1～20 carbon atom); replace or unsubstituted aryl (monocycle of preferred 6～29 carbon atoms or the aryl of dicyclo); replace or unsubstituted arylthio (preferred 6～29 carbon atoms); replace or unsubstituted alkylthio (preferred 1～29 carbon atom); replace or unsubstituted alkyl sulfenyl (preferred 1～29 carbon atom); replace or unsubstituted aryl sulfenyl (preferred carbon atom is 6～29 the monocycle or the group of dicyclo); replace or unsubstituted alkyl alkylsulfonyl (preferred 1～29 carbon atom); replace or unsubstituted aryl sulfonyl (preferred carbon atom be 6～29 monocycle or the group of dicyclo); aryloxy (preferred carbon atom is 6～29 the monocycle or the group of dicyclo); formamyl (preferred 1～29 carbon atom); sulfamyl (preferred 1～29 carbon atom); hydroxyl, halogen atom (fluorine; chlorine; bromine; iodine); sulfonic group or carboxylic acid group etc.

These substituting groups also can have substituting groups such as alkyl, aryl, alkoxyl group, aryloxy, alkylthio, arylthio, alkyl sulphonyl, aryl sulfonyl, carboxylic acyloxy amido, sulfonic acid amides base, formamyl, sulfamyl, alkyl sulfoxylic acid base, aryl sulfoxylic acid base, ester group, hydroxyl, carboxyl, sulfo group, halogen atom.These groups also can interconnection formation ring.And these groups can also form the part of homopolymer or homopolymer chain.

The specific examples of-sulfinic acid based compound is expressed as follows.

[changing 37]

The thiocyanic acid based compound

The thiocyanic acid based compound can be enumerated methylthiocyanide methylthiocyanate, Thiocyanic Acid Ethyl ester, Sodium Thiocyanate 99, potassium sulfocyanate, calcium thiocyanide etc.

The sulfur heterocyclic ring compound

The sulfur heterocyclic ring compound; can enumerate the compound that the sulfydryl as the sulfhydryl compound of sulfhydryl compound that constitutes compound that one of heterocyclic atom contains sulphur atom, heterocyclic substituted and heterocyclic substituted is replaced by alkyl, aryl, acyl group, alkylsulfonyl etc., wherein the compound of preferably representing by following general formula

[changing 38]

(in the formula, X represents to form 5～7 yuan of non-metallic atom groups that ring is required.This non-metallic atom group can have substituting group, and described substituting group can be enumerated alkyl, alkenyl, aryl, alkoxyl group, aryloxy, alkylthio, arylthio, hydroxyl, amino, sulfydryl, carboxyl, acyl group, formamyl, sulfamyl, halogen atom and cyano group etc.These substituting groups also can further have substituting group.

M represents hydrogen atom, ammonium ion or atoms metal.And comprise and the group of 5～7 yuan of rings of X formation also can form condensed ring with other integrant condensations.)

The specific examples of above-mentioned heterocyclic substituted sulfhydryl compound can be enumerated the compound that the spy opens 0027～0032 section record of 2000-94829 communique (1-1～1-32) etc.

The sulfoxide based compound

The sulfoxide based compound can be water-soluble cpds or oil-soluble compounds, and both can be that polymer also can be low molecule, also can be that intramolecularly contains an above sulfoxide radicals structure.

The sulfoxide based compound preferably has two above carbon atoms, more preferably four above carbon atoms.

The sulfoxide based compound preferably also contains and to comprise the right atom of isolated electron (for example Sauerstoffatom, sulphur atom, nitrogen-atoms, phosphorus atom) except that containing sulfoxide group, carbon atom and hydrogen atom.

Concrete compound is listed below.

[changing 39]

HOCH ₂CH ₂SOCH ₂CH ₂OH

HOCH ₂CH ₂(SOCH ₂CH ₂) ₂OH

OS(CH ₂CO ₂H) ₂

(CH ₃) ₂NCH ₂CH ₂SOCH ₂CH ₂N(CH ₃) ₂

In addition, the sulfocompound that can use in the present invention can be enumerated sulfone based compound, sulfanilamide (SN) based compound, monothioester based compound, thioamides based compound, sulfonic acid based compound, thiosulfonic acid based compound, sulfo--sulfinic acid based compound, sulphonamide based compound, thiocarbamate based compound, sulfurous acid based compound etc.

In the sulfocompound that the present invention uses, preferred thioether based compound, thiocarbamide based compound, sulfoxide based compound, heterocyclic substituted sulfhydryl compound, sulfur heterocyclic ring formula compound etc.

The sulfocompound that the present invention uses can hang down molecule or polymer, can be water-soluble or oil-soluble, but also can be coated with the emulsification form.Particularly preferably be thioether based compound, thiocarbamide based compound, sulfoxide based compound.

The sulfocompound that the present invention uses is accepted content in the material layer, preferred 0.1～5 gram/m at tinting material ², more preferably 0.3～3 gram/m ²

The colorant receiving layer of the ink jet recording medium that the present invention uses both can be to absorb ink type in the space between particulate, also can be that water soluble resin absorbs ink type.

Below mainly be illustrated with regard to the receiving layer of former type.

Such ink jet recording medium is to have on support in the ink jet recording medium of colorant receiving layer, and described colorant receiving layer contains particulate and water soluble resin at least except that containing sulfocompound.The colorant receiving layer forms vesicular structure by containing particulate, can improve the absorptive character of printing ink like this.Particularly the solid shape when the particulate described in the colorant receiving layer divides content greater than 50 weight %, better when surpassing 60 weight %, owing to can form the higher vesicular structure of porosity, thereby can obtain to have the ink-jet recording medium of sufficient ink absorption, so be preferred.Particulate described here solid shape in the colorant receiving layer is divided content, is meant the content that calculates according to the one-tenth branch except that moisture content in the composition that constitutes the colorant receiving layer.

(particulate)

As the particulate that uses among the present invention, can enumerate organic fine particles and inorganic particles, but, preferably contain inorganic particles from ink absorption and picture steadiness viewpoint.

As above-mentioned organic fine particles, for example preferred is the polymer particles that polymerization, emulsifier-free polymerization, seeding polymerization, dispersion polymerization, suspension polymerization etc. obtain through letex polymerization, microemulsion, specifically can enumerate the powder of polyethylene, polypropylene, polystyrene, polyacrylic ester, polymeric amide, silicone resin, phenol resins, natural polymer etc., and the polymer particles of latex or emulsion state etc.

As above-mentioned inorganic particles, for example can enumerate silicon-dioxide (precipitation, colloid, gel, colloidal sol or pyrolysated), cation-modified silicon-dioxide (for example in illustration and nonrestrictive embodiment through oxidation two silicon of alumina treatment), silicon-dioxide through the cation high molecular adhesive treatment, aluminum oxide, magnesium oxide, magnesiumcarbonate, lime carbonate, intend boehmite, barium sulfate, clay, titanium dioxide, gypsum, Calucium Silicate powder, zeolite, kaolin, halloysite, mica, talcum, calcium sulfate, zinc oxide, zinc hydroxide, pure aluminium silicate, Calucium Silicate powder, Magnesium Silicate q-agent, zirconium white, zirconium hydroxide, cerium oxide, lanthanum trioxide, yttrium oxide etc.Wherein from forming good vesicular structure viewpoint, preferred silicon dioxide microparticle, colloid silica, alumina particulate or plan boehmite.These particulates both can directly use with the primary particle form, also can use under the state that forms secondary particle.The average primary particle diameter of these particulates preferably is in below 2 microns, more preferably below 200 nanometers.

In addition, the following silicon dioxide microparticle of preferred especially average primary particle diameter 30 nanometers, average primary particle diameter are the plan boehmite that alumina particulate below 20 nanometers or average pore radius are 2～15 nanometers in the colloid silica below 30 nanometers, average primary particle diameter, wherein more preferably silicon dioxide microparticle, alumina particulate and plan boehmite.

Silicon dioxide microparticle can be divided into wet method silicon dioxide microparticle and dry method (vapor phase process) silicon dioxide microparticle according to its manufacture method usually.The main stream approach of previous wet method is that silicate generates active silica through thermolysis, will obtain the method for silicon oxide behind its suitable polymerization flocking settling then.On the other hand, the main stream approach of latter's vapor phase process is, utilize the method (flame hydrolysis) of the high temperature vapor phase hydrolysis of silicon halide, and in electric furnace, silica sand and coke are added thermal revivification gasification and with its method (arc process) with atmospheric oxidation, obtain the method for anhydride silica with electric arc.So-called " fumed silica " is meant the anhydride silica that utilizes vapor phase process to obtain.The silicon dioxide microparticle that uses among the present invention preferably should " fumed silica " particulate.

Above-mentioned " fumed silica " compared with aqueous silicon dioxide, there are differences aspect the having or not of the silanol group density on surface or hole, and demonstrates different character, is suitable for forming the big three-dimensional structure of porosity.Though not necessarily clear about its reason, according to inferring, under the occasion of aqueous silicon dioxide, the silanol group density on the microparticle surfaces is up to 5～8/nm ², the easy intensive gathering of silicon dioxide microparticle (aggregation block), under the occasion of fumed silica, the silanol group density on the microparticle surfaces is low to moderate 2～3/nm on the other hand ²So, forming loose soft aggregate (floss), its result forms the high structure of porosity.

Above-mentioned " fumed silica " is because of the absorptivity and the conservation rate height of the big especially printing ink of specific surface area, and because specific refractory power is low, if fine dispersion can be proceeded to suitable particle diameter, then can give the colorant receiving layer with the transparency, have the advantage that can obtain high color development concentration and good tone.Like this, why say that the colorant receiving layer is transparent, be because not only in the purposes such as OHP of the needs transparency, and be used under the occasion of paper used for recording such as photograph glossy paper that to be in harmonious proportion the glossy viewpoint all very important from obtaining high depth of shade and good color.

Below preferred 30 nanometers of the average primary particle diameter of above-mentioned " fumed silica ", more preferably below 20 nanometers, below preferred especially 10 nanometers, be preferably 3～10 nanometers.This fumed silica makes between the particle easily under the effect of silanol group hydrogen bond and adheres to mutually, if the average primary particle diameter is decided to be below 30 nanometers, then can form the big structure of porosity, can effectively improve the absorption characteristic of printing ink.

And silicon oxide particle also can and be used with above-mentioned other particulates.Under the occasion of described other particulates and usefulness, the content of fumed silica in whole particulates is preferably more than 30 weight %, more preferably more than 50 weight %.

As the inorganic particles that the present invention uses, the hydrate of also preferred alumina particulate, aluminum oxide, its mixture or mixture.Wherein the hydrate of aluminum oxide preferably, is especially preferably intended boehmite (Al owing to can adsorb fixedly printing ink well ₂O ₃NH ₂O).Though this hydrated alumina can use various forms, the viewpoint of the smooth layer that is easy to get calmly preferably uses colloidal sol shape boehmite as raw material.

About the pore structure of above-mentioned plan boehmite, preferred 1～30 nanometer of its average pore radius, more preferably 2～15 nanometers.And preferred 0.3～2.0 milliliter/gram of this pore volume, more preferably 0.5～1.5 milliliter/gram.Wherein,, can adopt for example gas adsorption desorb analyser (trade(brand)name of コ one Le one company " ォ system ニ ソ one プ 369 " etc.) mensuration owing to can adopt the nitrogen adsorption method to measure about the mensuration of above-mentioned pore radius and pore volume.

And preferred vapor phase process alumina particulate specific surface area is big in the alumina particulate.Preferred 30 nanometers of the average primary particle diameter of this vapor phase process aluminum oxide are following, and more preferably 20 nanometers are following.

Use in the ink jet recording medium receiving layer under the occasion of above-mentioned particulate, can preferably use disclosed various forms in the following patent gazette: for example the spy opens flat 10-81064, same 10-119423, same 10-157277, same 10-217601, same 11-348409, the spy opens 2001-138621, same 2000-43401, same 2000-211235, same 2000-309157, same 2001-96897, same 2001-138627, Te Kaiping 11-91242, same 8-2087, same 8-2090, same 8-2091, same 8-2093, same 8-174992, same 11-192777, the spy opens those disclosed in the 2001-301314 equal sign communique.

(water soluble resin)

Ink jet recording medium of the present invention, its colorant receiving layer preferably contains water soluble resin simultaneously with above-mentioned particulate.

As above-mentioned water soluble resin; for example can enumerate with the hydroxyl be the unitary resin of hydrophilic structure promptly, polyvinyl alcohol resin (polyvinyl alcohol (PVA) for example; the PVA of acetyl vinyl modification; cation-modified PVA; anion-modified PVA; the PVA of silanol modification; polyvinylacetal etc.); cellulose-based resin (methylcellulose gum (MC) for example; ethyl cellulose (EC); Natvosol (HEC); carboxymethyl cellulose (CMC); hydroxypropylcellulose (HPC); hydroxyethylmethyl-cellulose; Vltra tears etc.); chitosan kind; the chitosan class; resin (polyethylene oxide (PEO) for example with ehter bond; poly(propylene oxide) (PPO); polyoxyethylene glycol (PEG); polyvingl ether (PVE) etc.) and have a resin (polyacrylamide (PAAM) for example of formamyl; polyvinylpyrrolidone (PVP); polyacrylic acid hydrazides etc.) etc.

And can utilize with carboxyl as the polyacrylate of dissociating property group, maleic acid resin, alginate, gelatin class etc.

Special preferably polyethylene alcohol (PVA) is resin in the above-mentioned substance.The example of this polyvinyl alcohol, can use and put down in writing in the following communique, promptly special fair 4-52786, special fair 5-67432, special fair 7-29479, specially permit the 2537827th, special fair 7-57553, specially permit the 2502998th, specially permit the 3053231st, the spy opens clear 63-176173, specially permit the 2604367th, Te Kaiping 7-276787, Te Kaiping 9-207425, Te Kaiping 11-58941, the spy opens 2000-135858, the spy opens 2001-205924, the spy opens 2001-287444, the spy opens clear 62-278080, Te Kaiping 9-39373, specially permit the 2750433rd, the spy opens 2000-158801, the spy opens 2001-213045, the spy opens 2001-328345, Te Kaiping 8-324105, the spy opens 11-348417, the spy opens clear 58-181687, Te Kaiping 10-259213, the spy opens 2001-72711, the spy opens 2002-103805, the spy opens 2000-63427, the spy opens 2002-308928, the spy opens 2001-205919, the spy opens those that put down in writing in the 2002-264489 equal sign communique.

And as the example of the water soluble resin beyond the polyvinyl alcohol resin, can also enumerate the spy and open the compound that record such as 2002-264489 communique is opened in 2001-205919 number, spy, and open the compound that flat 11-165461 communique (0011～0014) is put down in writing the spy.

These water soluble resins can be used alone or two or more and usefulness.And the content of above-mentioned water soluble resin in the ink jet recording medium of the present invention, preferably account for 9～40 weight % for all shape is divided admittedly with respect to the colorant receiving layer, more preferably account for 12～33 weight %.

In addition, polyvinyl alcohol resin also can and be used with above-mentioned other water soluble resins.Under the occasion of described other water soluble resins and above-mentioned polyvinyl alcohol resin and usefulness, the content of polyvinyl alcohol resin in whole water soluble resins preferably accounts for more than the 50 weight %, more preferably accounts for more than the 70 weight %.

As the main composition composition of colorant receiving layer of the present invention, above-mentioned water soluble resin and above-mentioned particulate, can be respectively single-material, perhaps can use the mixed system of most materials.

From keeping the viewpoint of the transparency, the kind that is combined to the water soluble resin in the particularly silicon dioxide microparticle in the particulate is very important.Use under the occasion of above-mentioned fumed silica, described aqueous resin preferably polyethylene alcohol is resin, and wherein more preferably saponification deg is 20～100% polyvinyl alcohol resin, and preferred especially saponification deg is 30～99.5% polyvinyl alcohol resin.

Above-mentioned polyvinyl alcohol resin, though in its structural unit, hydroxyl is arranged, but because the silanol on this hydroxyl and the above-mentioned silica particle surface forms hydrogen bond, so the secondary particle that forms with silicon dioxide microparticle is the three dimensional network ocular structure of mesh chain unit easily.It is believed that because the formation of this three dimensional network ocular structure, and can form the porosity height, have the colorant receiving layer of the vesicular structure of abundant intensity.

During ink-vapor recording, the porousness colorant receiving layer that obtains in the above described manner because of capillary phenomenon rapid absorption printing ink, can form the just round good ink dot of property that printing ink " oozes out " can not take place.

(particulate compares with the content of water soluble resin)

In the ink jet recording medium, the above-mentioned particulate (x) in the colorant receiving layer and the weight content ratio (PB is than (x/y)) of above-mentioned water soluble resin (y) have a significant impact the membrane structure and the film toughness of this colorant receiving layer.That is to say that this weight content ratio (PB than) is excessive, though porosity and pore volume, surface-area (per unit mass) increase, density and intensity have the trend of reduction.

In the colorant receiving layer of the present invention, for above-mentioned weight content ratio (PB is than (x/y)), film toughness is reduced and crack when dry than excessive because of this PB from preventing, and prevent from described space to be stopped up easily by resin because of this weight content ratio is too small, thereby make porosity reduce the viewpoint that absorptivity reduces, preferred 1.5～10.

Under the occasion of the delivery system of passing through the ink-vapor recording printing press, owing on sheet for recording, be applied with stress, so the colorant receiving layer must have enough film toughnesss.And from preventing when shearing when being processed into sheet, the viewpoint that the colorant receiving layer cracks and peels off etc. is set out, and the colorant receiving layer also must have enough film toughnesss.Consider these situations, above-mentioned PB preferably is in below 5 than (x/y).On the other hand, from guaranteeing the high speed ink absorption viewpoint of ink-vapor recording printing press, more preferably be in more than 2.

Specifically, for example be that fumed silica particulate and water soluble resin below 20 nanometers is dispersed in the coating fluid that obtains in the aqueous solution fully with 2～5 PB than (x/y) with average primary particle diameter, be coated on the support, after this coating layer drying, can form with the secondary particle of silicon dioxide microparticle is the three dimensional network ocular structure of mesh chain, can form described average pore diameter easily and be that 30 nanometers are following, porosity 50～80%, pore specific volume be 0.5 milliliter/gram is above, specific surface area is 100m ²The porous-film of the light transmission that/g is above.

(linking agent)

The colorant receiving layer of ink jet recording medium of the present invention, preferably make the coating layer that contains above-mentioned water soluble resin contain the linking agent that can make this water soluble resin crosslinked, a kind of particularly preferred embodiment is to make above-mentioned particulate and above-mentioned water soluble resin and usefulness, and is the solidified porous layer by the crosslinking reaction of linking agent and water soluble resin.

The preferred boron compound that adopts makes above-mentioned water soluble resin, makes polyvinyl alcohol crosslinked especially.Described boron compound for example can be enumerated borax, boric acid, borate (for example ortho-borate, InBO ₃, ScBO ₃, YBO ₃, LaBO ₃, Mg ₃(BO ₃) ₂, Co ₃(BO ₃) ₂), biborate (Mg for example ₂B ₂O ₅, Co ₂B ₂O ₅), metaborate (LiBO for example ₂, Ca (BO ₂) ₂, NaBO ₂, KBO ₂), tetraborate (Na for example ₂B ₄O ₇10H ₂O), pentaborate (KB for example ₅O ₈4H ₂O, Ca ₂B ₆O ₁₁7H ₂O, CsB ₅O ₅) etc.Wherein from producing crosslinking reaction fast, preferred borax, boric acid and borate, special preferred boric acid.

As the linking agent of water soluble resin, can also use the compound outside the above-mentioned boron compound.For example; can enumerate: formaldehyde; oxalic dialdehyde; suceinic aldehyde; glutaraldehyde; dialdehyde starch; aldehyde compounds such as two aldehyde derivatives of plant gum; di-acetyl; 1; the 2-cyclopentanedione; 3-hexene-2; ketone compounds such as 5-diketone; two (2-chloroethyl) urea; two (2-chloroethyl) sulfone; 2; 4-two chloro-6-hydroxyl cis triazine sodium salt isoreactivity halogenide; divinylsulfone; 1; two (the vinylsulfonyl)-2-propyl alcohol of 3-; N; N '-ethylene two (vinylsulfonyl ethanamide); divinyl ketone; 1; two (acryl) ureas of 3-; 1; 3; 5-triacryl-six hydrogen cis triazine isoreactivity vinyl compound; dimethylolurea; N-methylol compounds such as methylol dimethyl hydantion; tri methylol melamine; alkylating methylol melamine; melamine; the benzo guanamine; melamine compounds such as melamine resin; ethylene glycol diglycidylether; propylene glycol diglycidylether; polyethyleneglycol diglycidylether; two glycerine polyglycidyl ethers; the spiral shell ethylene glycol diglycidylether; epoxide such as the polyglycidyl ether of phenol resins

1, the 6-hexamethylene diisocyanate, isocyanic ester based compounds such as xylylene vulcabond, US Patent specification the 3017280th, the ethylenimine based compound of putting down in writing in No. 2983611 grades, the phosphinylidyne diimine compounds of putting down in writing in No. 3100704 grade of US Patent specification, 1,6-hexa-methylene-N, N '-ethyleneimine based compounds such as two ethylene-ureas, mucochloric acid, the glue phenoxy chloric acid waits halo carboxyl aldehyde based compound, 2, diox based compounds such as 3-Er Qiang Ji diox, the lactic acid titanium, Tai-Ace S 150, chromium alum, potassium alum, zirconium acetate, metallic compounds such as chromium acetate, polyamine compounds such as tetracthylene pentamine, hydrazide compounds such as adipic dihydrazide, contain the low molecule of 2 above oxazoline groups or polymkeric substance etc., US Patent specification the 2725294th, 2725295,2726162, the acid anhydrides of the polyprotonic acid of record in 3834902 equal signs etc., acyl chlorides, the disulfonic acid ester cpds, US Patent specification the 3542558th, active ester compound of putting down in writing in No. 3251972 grades etc.

Above-mentioned linking agent can be used alone, and perhaps is used in combination of two or more.

Among the present invention, above-mentioned crosslinking curing preferably adopt the coating fluid (following often be called " coating fluid A ") that will contain particulate and water soluble resin etc. and/or under remember and add linking agent in the basic solution, and (1) when the above-mentioned coating fluid of coating forms coating layer, perhaps the above-mentioned coating fluid of (2) coating forms in the drying process of coating layer, in any time before this coating layer shows falling rate of drying speed, the mode that the basic solution more than the pH8 (following often be called " coating fluid B ") is given on this coating layer is carried out.

In the above-mentioned basic solution more than pH8 (" coating fluid B "), except that the polymer mordant with primary amine groups～tertiary amine groups described later, can also use organic compound, mineral compound (comprising metal complex or organic acid salt) or the alkaline precursor etc. that show alkalescence as alkali.As such compound, for example can enumerate and the oxyhydroxide of oxyhydroxide, nitrogen-containing heterocycle compound, basic metal and the alkaline earth metal class of the salifiable ammonium salt based compound of ammonia shape, low-grade polymer～oligomer compounds, quaternary amine or the salt of acid etc. with primary amine groups～tertiary amine groups.

Specifically can enumerate ammonium salt, trolamine, triethylamine, sodium acetate, guanidine of ammoniacal liquor, volatile salt, ammonium acetate, zirconium carbonate ammonium, ammonium chloride, ammonium sulfate, ammonium tosylate, polymkeric substance, latex etc. with acidic-group.

Wherein as alkali, from adjusting the pH viewpoint of ink jet recording medium paper, preferred at least a is the ammonium salt based compound.

Giving as if being example with the boron compound of above-mentioned linking agent then preferably carried out in such a way.Promptly after the colorant receiving layer is coating fluid (" coating fluid the A ") coating that will contain the water soluble resin of particulate and polyvinyl alcohol, coating layer through crosslinking curing and the occasion of material layer under, described crosslinking curing, (1) when the above-mentioned coating fluid of coating forms coating layer, perhaps the above-mentioned coating fluid of (2) coating forms in the drying process of coating layer, in any time before this coating layer demonstrates falling rate of drying speed, the mode that the basic solution more than the pH8 (" coating fluid B ") is given on the above-mentioned coating layer is carried out.As the boron-containing compound of linking agent, both can in coating fluid A or coating fluid B, contain, also can in coating fluid A and coating fluid B, contain simultaneously.

The consumption of above-mentioned linking agent in the colorant receiving layer of the present invention preferably is in for water soluble resin in 1～50 weight % scope, more preferably is in 5～40 weight % scopes.

(mordant)

In the ink jet recording medium of the present invention, for improve the water tolerance that forms image and anti-through the time ooze lubricant nature, preferably contain mordant in the colorant receiving layer.

Described mordant preferred cationic type polymer organic mordant (cationic mordant) or inorganic mordant.By this mordant is present in the colorant receiving layer, and have as colorant under the interaction between the liquid ink of anionic dyestuff, can improve colorant stability, water tolerance and anti-through the time ooze lubricant nature.Like this organic mordant and inorganic mordant can be used separately, also can and use organic mordant and inorganic mordant.

Use order about mordant can adopt the method for adding in the above-mentioned coating fluid A that contains particulate and water soluble resin, perhaps when worrying to add the method for back coating etc. in above-mentioned coating fluid B under the occasion of generation cohesion between the particulate.

As above-mentioned cationic mordant,, also can use cationic non-polymer mordant though can suitably use the polymer mordant that contains primary amino～uncle's amino or quaternary ammonium group as cation group.These mordants, from improving the absorptivity of colorant receiving layer to printing ink, preferable weight-average molecular weight is 500～100000 compound.

As described polymer mordant, the preferred homopolymer that uses monomer (mordant dyeing monomer) with primary amino～uncle's amino and salt or quaternary ammonium group, and by the multipolymer or the polycondensate of mordant dyeing monomer and other monomers (following also be called " non-mordant dyeing monomer ").And these polymer mordant can be used under any form of water-soluble polymers or water dispersible latex particle.

As above-mentioned monomer (mordant dyeing monomer), can enumerate: trimethylammonium-right-vinyl benzyl chlorination ammonium for example, 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 sulfate, trimethylammonium--vinyl benzyl ammonium sulfate, 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;

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, N, the methyl chloride of N-diethylamino propyl group (methyl) acrylamide, chloric ethane, methyl bromide, bromic ether, the season thing that methyl iodide or iodic ether form, or the sulfonate that its negatively charged ion is replaced, alkylsulfonate, acetate or alkyl carboxylate etc.

As concrete compound, for example can enumerate 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-(methacryloyl amido) ethyl ammonium chloride, triethyl-2-(methacryloyl amido) ethyl ammonium chloride, trimethylammonium-2-(acrylamido) ethyl ammonium chloride, triethyl-2-(acrylamido) ethyl ammonium chloride, trimethylammonium-3-(methacryloyl amido) propyl ammonium chloride, triethyl-3-(methacryloyl amido) 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 ammonium chloride, trimethylammonium-3-(acrylamido) propyl ammonium chloride, trimethylammonium-2-(methacrylic acid group) ethylsulfonic acid ammonium, trimethylammonium-3-(acrylamido) propyl group ammonium acetate etc.

As the monomer of energy copolymerization, can enumerate N-vinyl imidazole and N-vinyl-glyoxal ethyline etc. in addition.

But also can utilize allylamine, diallylamine or derivatives thereof and salt thereof etc.Such examples of compounds, for example can enumerate allylamine, allylamine hydrochloride, allylamine acetate, allylamine vitriol, diallylamine, diallylamine hydrochloride, diallylamine acetate, diallylamine vitriol, diallyl methylamine and salt thereof (as this salt for example hydrochloride, acetate, vitriol etc.), diallyl ethamine and salt thereof (as this salt for example hydrochloride, acetate, vitriol etc.), diallyl dimethyl salt (as this salt to negatively charged ion, for example chlorion, acetato-, sulfate ion etc.).In addition, these allylamines and diallylamine derivative are because polymerizability is poor under the form of amine, so generally with salt form polymerization, desalination in case of necessity.

In addition, also can be used with monomer (monomer) polymerizations such as N-vinyl acetamide, N-vinyl formamides, after the polymerization, the material after hydrolysis is made the vinyl-amine structural unit and is made into salt.

So-called above-mentioned non-mordant dyeing monomer is meant wherein not contain primary amino～uncle's amino and alkalescence or cationic parts such as salt or quaternary amine, does not interact with dyestuff in the jetted ink or interacts very little in fact monomer.

As above-mentioned non-mordant dyeing monomer, for example can enumerate (methyl) alkyl acrylate, (methyl) vinylformic acid cycloalkyl esters such as (methyl) vinylformic acid cyclohexyl ester, (methyl) vinylformic acid aryl esters such as (methyl) phenyl acrylate, the aralkyl ester of (methyl) vinylformic acid benzyl ester etc., vinylbenzene, Vinyl toluene, aromatic vinyl classes such as alpha-methyl styrene, vinyl acetate, vinyl esters such as propionate, allyl ester classes such as acetic acid allyl ester, vinylidene chloride, Halogen monomers such as vinylchlorid, cyano group ethene such as (methyl) vinyl cyanide, ethene, olefines such as propylene etc.

As above-mentioned (methyl) alkyl acrylate, preferred alkyl part carbonatoms is (methyl) alkyl acrylate of 1～18, for example can enumerate (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) dodecylacrylate, (methyl) vinylformic acid stearyl etc.

Wherein preferred methyl acrylate, ethyl propenoate, methyl methacrylate, Jia Jibingxisuanyizhi, hydroxyethyl methylacrylate etc.

Above-mentioned non-mordant dyeing monomer can be used alone or be used in combination of two or more.

In addition, as above-mentioned polymer mordant, for example can suitably enumerate multipolymer, diallyldimethylammonium chloride and the SO of diallyl dimethyl ammoniumchloride, diallyldimethylammonium chloride and other monomers (mordant dyeing monomer, non-mordant dyeing monomer) ₂Multipolymer, the PDMA hydrochloride, with polydiene propyl group hydrochloride etc. is the cyclic amine resin and the derivative (also comprising multipolymer) thereof of representative, with poly-diethylmethyl acryloxy ethylamine, poly-trimethylammonium methacryloxyethyl ammonium chloride, polydimethyl benzyl methacryloxyethyl ammonium chloride, polydimethyl hydroxyethyl acryloxy ethyl ammonium chloride etc. is the secondary amine of representative, alkyl (methyl) acrylic ester polymer that tertiary amine or quaternary amine replace and with other monomeric multipolymer, with polyethylene imine based and derivative, PAH and derivative thereof, polyvinylamine and derivative etc. thereof are resin for the polyamine of representative, with polymeric amide-versamid 900, polyamide epichlorohydrin resins etc. are the polyamide resin of representative, with cationic starch, chitosan and chitosan derivatives are the polyose of representative, with dicyano diamide formaldehyde condensation products, dicyano diamide diethylenetriamine polycondensate etc. is the dicyano diamide derivatives of representative, poly-amidine and poly-amidine derivative, with dimethyl amine Epicholorohydrin addition polymer etc. is the dialkylamine Epicholorohydrin addition polymer and the derivative thereof of representative, has the styrene polymer of the alkyl that quaternary amine replaces and with other monomeric multipolymers etc.

Above-mentioned polymer mordant specifically can be enumerated the spy and open clear 48-28325, same 54-74430, same 54-124726, same 55-22766, same 55-142339, same 60-23850, same 60-23851, same 60-23852, same 60-23853, same 60-57836, same 60-60643, same 60-118834, same 60-122940, same 60-122941, same 60-122942, same 60-235134, Te Kaiping 11-161236 equal sign communique, United States Patent (USP) 2484430, with 2548564, with 3148061, with 3309690, with 4115124, with 4124386, with 4193800, with 4273853, with 4282305, with 4450224, Te Kaiping 1-161236, same 10-81064, same 10-15277, same 10-217601, the spy opens 2001-138621, same 2000-211235, same 2001-138627, Te Kaiping 8-174992, special fair 5-35162, same 5-35163, same 5-35164, same 5-88846, specially permit the 2648847th, the mordant of putting down in writing in the same 2661677 equal sign communiques etc.

Mordant of the present invention also can use inorganic mordant, can enumerate multivalence water-soluble metal salt and hydrophobic metals salt compound etc.

As the specific examples of inorganic mordant, can enumerate metal-salt or the complex compound for example from 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, bismuth, selected.

Concrete compound can be enumerated for example calcium acetate, calcium chloride, calcium formiate, calcium sulfate, barium acetate, barium sulfate, barium phosphate, Manganous chloride tetrahydrate, manganese 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, the nickel acetate tetrahydrate, the nickel ammonium sulfate hexahydrate, amide group single nickel salt tetrahydrate, Tai-Ace S 150, al alum, 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 etheric acid titanium, the lactic acid titanium, the etheric acid zirconium, the acetic acid zirconium, zirconium sulfate, zirconium carbonate ammonium, zirconium stearate, zirconium caprylate, zirconium nitrate, basic zirconium chloride, zirconyl hydroxychloride, chromium acetate, chromium sulphate, sal epsom, magnesium chloride hexahydrate, the magnesium citrate nonahydrate, Tungstophosphoric acid, sodium salt, Trisodium Citrate tungsten, 12 phospho-wolframic acid n hydrates, 12 phospho-wolframic acids, 26 hydrates, molybdenum chloride, 12 phospho-molybdic acid n hydrates, gallium nitrate, nitric acid germanium, strontium nitrate, the acetic acid yttrium, Yttrium trichloride, Yttrium trinitrate, indium nitrate, lanthanum nitrate, Lanthanum trichloride, lanthanum acetate, the phenylformic acid lanthanum, Cerium II Chloride, cerous sulfate, cerium octoate, praseodymium nitrate, neodymium nitrate, samaric nitrate, europium nitrate, Gadolinium trinitrate, Dysprosium trinitrate, Erbium trinitrate, ytterbium nitrate, hafnium chloride, Bismuth trinitrate etc.

As inorganic mordant of the present invention, the compound (salt or complex compound) of preferred aluminum contained compound, titanium-containing compound, zirconium-containing compound and periodic table of elements IIIB family metal.

The contained above-mentioned mordant content of colorant receiving layer among the present invention, preferred 0.01～10 gram/square metre, more preferably 0.1～5 restrains/square metre.

(other compositions)

Ink jet recording medium of the present invention, can also contain various known additives in case of necessity, for example UV light absorber, antioxidant, white dyes, monomer, polymerization starter, stopper, permeability-reducing admixture, sanitas, viscosity stabilizer, defoamer, tensio-active agent, static inhibitor, flatting agent, anti-roll agent, anti-hydrated agent etc.

Among the present invention, the colorant receiving layer also can contain acid.Adjust to 3～8 by adding sour pH, preferably adjust to 4～7 colorant receiving layer surface.Preferred because of the yellowing resistance that can improve the white background part like this.The mensuration of surface p H is carried out according to A method (coating method) in the surface p H mensuration of Japanese paper pulp technological associations (J.TAPPI) regulation.The paper pH metering equipment " MPC type " that for example can use (strain) suitable with above-mentioned A method upright altogether RIKEN to make is measured.

As the example of specific acid, can enumerate formic acid, acetate, oxyacetic acid, oxalic acid, propionic acid, propanedioic acid, Succinic Acid, hexanodioic acid, toxilic acid, oxysuccinic acid, tartrate, citric acid, phenylformic acid, phthalic acid, m-phthalic acid, pentanedioic acid, gluconic acid, lactic acid, aspartic acid, L-glutamic acid, Whitfield's ointment, salicylic acid metal salt (Zn, Al, Ca, the salt of Mg etc.), methylsulfonic acid, methylene-succinic acid, Phenylsulfonic acid, toluenesulphonic acids, trifluoromethanesulfonic acid, styrene sulfonic acid, trifluoroacetic acid, malonylurea, vinylformic acid, methacrylic acid, TRANSCINNAMIC ACID, the 4-hydroxy-benzoic acid, benzaminic acid, naphthalene disulfonic acid, hydroxyl phenol sulfonic acid, toluenesulfinic acid, benzene sulfinic acid, Sulphanilic Acid, thionamic acid, α-Resorcinol formic acid, β-Resorcinol formic acid, γ-Resorcinol formic acid, gallic acid, the chloro glycine, sulphosalicylic acid, xitix, saccharosonic acid, diphenolic acid, hydrochloric acid, nitric acid, sulfuric acid, polyphosphoric acid, boric acid, sym.-diisopropylideneacetone acid and show tart material etc. at above-mentioned mordant.These sour additions can reach 3～8 according to the pH on colorant receiving layer surface, preferably reach 4～7 and determine.

Above-mentioned acid also can be used metal-salt (for example salt of sodium, potassium, calcium, caesium, zinc, copper, iron, aluminium, zirconium, lanthanum, yttrium, magnesium, strontium, cerium etc.) or amine salt forms such as (for example salt of ammonia, triethylamine, Tributylamine, piperazine, 2-methylpiperazine, PAH etc.).

Among the present invention, the colorant receiving layer preferably contains UV light absorber, antioxidant, infiltration and prevents that agent etc. from improving conservatory reagent.

As these UV light absorber; antioxidant; infiltration prevents agent; can enumerate for example alkylated benzenes phenolic compound (comprising hindered phenol compound); alkylthio methylphenol compound; hydroquinone compound; the alkylation hydroquinone compound; tocopherol compound; the sulfo-diphenyl ether compound; compound with thioether bond; bisphenol cpd; the O-benzyl compounds; the N-benzyl compounds; the S-benzyl compounds; the hydroxybenzyl compound; triaizine compounds; phosphate compounds; the acyl aminophenols compound; ester compound; amide compound; xitix; amine is antioxidant; 2-(2-hydroxy phenyl) benzotriazole cpd; 2-hydroxy benzophenone ketone compound; acrylate; water-soluble or hydrophobic metal-salt; organometallic compound; metal complex; hindered amine compound (compound that contains so-called TEMPO); 2-(2-hydroxy phenyl)-1; 3, the 5-triaizine compounds; the metal inert agents; phosphite compound; phosphonate compound; hydroxylamine compound; the nitro-n-compound; peroxide scavenger; the polymeric amide stablizer; polyether compound; the alkalescence auxiliary stabilizer; the nuclear agent; benzofuran compound; dihydroindole ketone; phosphine compound; polyamino compound; thiourea compound; urea compounds; hydrazide compound; amidine compound; sugar compounds; hydroxybenzoic acids; the resorcylic acid compound; trihydroxybenzoic acid compound etc.

Wherein preferred alkyl oxybenzene compound, the compound with thioether bond, bisphenol cpd, ascorbic acid cpds, amine are antioxidant, water-soluble or hydrophobic metal-salt, organometallic compound, metal complex, hindered amine compound, hydroxylamine compounds, polyamino compound, thiourea compound, urea compounds, hydrazide compound, hydroxybenzoic acids, resorcylic acid compound, trihydroxybenzoic acid compound etc.

As the particular compound example, can enumerate and be documented in the spy and open 2002-240421, the spy opens 2002-13005, Te Kaiping 10-182621, the spy opens 2001-260519, special fair 4-34953, Te Kaiping 4-34513, Te Kaiping 11-170686, special fair 4-34512, EP1138509, the spy opens clear 60-67190, Te Kaiping 7-276808, the spy opens 2001-94829, the spy opens clear 47-10537, same 58-111942, same 58-212844, same 59-19945, same 59-46646, same 59-109055, same 63-53544, special public clear 36-10466, same 42-26187, same 48-30492, same 48-31255, same 48-41572, same 48-54965, same 50-10726, United States Patent (USP) the 2719086th, with 3707375, with 3754919, with No. 4220711;

Special public clear 45-4699, same 54-5324, Europe openly speciallys permit the 223739th, with the 309401st, with the 309402nd, with the 310551st, with the 310552nd, with the 459416th, Germany's publication the 3435443rd, the spy opens clear 54-48535, same 60-107384, same 60-107383, same 60-125470, same 60-125471, same 60-125472, same 60-287485, same 60-287486, same 60-287487, same 60-287488, same 61-160287, same 61-185483, same 61-211079, same 62-146678, same 62-146680, same 62-146679, same 62-282885, same 62-262047, same 63-051174, same 63-89877, same 63-88380, same 63-88381, same 63-113536;

Same 63-163351, same 63-203372, same 63-224989, same 63-251282, same 63-267594, same 63-182484, Te Kaiping 1-239282, Te Kaiping 2-262654, same 2-71262, same 3-121449, same 4-291684, same 4-291685, same 5-61166, same 5-119449, same 5-188687, same 5-188686, same 5-110490, same 5-1108437, same 5-170361, special public clear 48-43295, same 48-33212, United States Patent (USP) the 4814262nd, those that put down in writing in same the 4980275th equal sign communique.

As above-mentioned other compositions, can be used alone or two or more and usefulness.Other compositions so both can add with water-solubleization, decentralized, polymer dispersed, emulsification, oil droplet mode, also it can be wrapped in the microcapsule.In ink jet recording medium of the present invention, preferred 0.01～10 gram of the addition of above-mentioned other compositions/square metre.

And, also can handle the inorganic particles surface with silane coupling agent in order to improve the dispersiveness of inorganic particles.As this silane coupling agent, preferably except that the position of carrying out the coupler processing, also has the silane coupling agent of organo-functional group (for example vinyl, amino (primary amino～uncle's amino, quaternary ammonium group), epoxy group(ing), sulfydryl, alkyl, phenyl, ester group).

Among the present invention, the colorant receiving layer preferably contains tensio-active agent with coating fluid.That described tensio-active agent can use is cationic, anionic, non-ionic type, both sexes, fluorine system, silicon are tensio-active agent etc.

Described nonionic surface active agent, for example can enumerate polyoxyalkylene alkyl and polyoxyalkylene alkyl phenyl ethers (diethylene glycol monoethyl ether for example, two sweet diethyl ether, the polyoxyethylene lauryl ether, the polyoxyethylene stearyl ether, polyoxyethylene nonylplenyl ether etc.), ethylene oxide-propylene oxide block copolymer, sorbitan-fatty acid ester (Span-20 for example, sorbitan monooleate, sorbitan trioleate etc.), polyoxyethylene sorbitan fatty acid ester (Tween-20 for example, polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan trioleate etc.), polyoxyethylene sorbitol fatty acid ester (for example polyoxyethylene sorbitol four oleic acid esters etc.), glycerol fatty acid ester class (for example glyceryl monooleate etc.), polyoxyethylene glycerol fatty acid ester class (Stearinsaeure polyoxyethylene glyceride for example, single oleic acid polyoxyethylene glyceride etc.), polyoxyethylene fatty acid ester class (polyethylene glycol monolaurate for example, polyethylene glycol monooleate etc.), polyoxyethylene alkyl amine, acetylenediol class (for example 2,4,7,9-tetramethyl--5-decine-4, the 7-glycol, and the ethylene oxide adduct of this glycol, propylene oxide adduct etc.), wherein preferred polyethylene oxide alkyl ethers class.Described nonionic surface active agent can use in coating fluid described later (A) and coating fluid (B).And above-mentioned nonionic surface active agent can use separately or two or more and usefulness.

As above-mentioned amphoterics, can enumerate amino acid pattern, carboxylic acid ammonium's betaine type, ammonium sulphonate betaine type, ammonium sulfuric ester betaine type, imidazoles betaine type etc., for example can suitably use United States Patent (USP) the 3843368th, spy to open that clear 59-49535, same 63-236546, spy open flat 5-303205, same 8-262742, same 10-282619, special permission the 2514194th, special permission the 2759795th, the spy opens the material of putting down in writing in the 2000-351269 equal sign communique.In the above-mentioned amphoterics, preferred amino acid type, carboxylic acid ammonium's betaine type, ammonium sulphonate betaine type.Above-mentioned amphoterics can use a kind of or two or more and use.

As above-mentioned aniorfic surfactant, can suitably enumerate soap (for example sodium stearate, sodium oleate), alkyl sulfuric ester salt (for example Sodium Lauryl Sulphate BP/USP, triethanolamine lauryl sulfate), sulfonate (for example Sodium dodecylbenzene sulfonate), alkyl sulfo succinate (for example dioctyl sodium sulphosuccinate), alkyl diphenyl base ether stilbene-4,4'-bis-(1-azo-3, 4-dihydroxy-benzene)-2,2'-disulfonate, alkylphosphonic etc.

Above-mentioned cats product can be enumerated alkylamine salt, quaternary amine, pyridinium salt, imidazole salts etc.

Above-mentioned fluorochemical surfactant can be enumerated methods such as adopting electrofluorination, telomerized polymer reaction, oligomerization, the compound that derivative comes out through having the intermediate of perfluoroalkyl.

For example can enumerate fluorinated alkyl sulfonate, perfluoroalkyl carboxylate, perfluoroalkyl ethylene oxide adduct, perfluoroalkyl trialkyl ammonium salts, the oligopolymer that contains perfluoroalkyl, perfluoralkyl phosphate etc.

As above-mentioned silicon is tensio-active agent, preferably through the silicone oil of organo-functional group modification, the side chain that described silicone oil can be enumerated the siloxane main chain structure through the organic group modification, two terminal-modified with one terminal-modified.Described organo-functional group modification can be enumerated amino modified, polyether-modified, epoxide modified, carboxy-modified, Trivalin SF modification, alkyl-modified, aralkyl modification, phenol-modified and fluorine element modification etc.

The content of tensio-active agent among the present invention preferably accounts for 0.001～2.0% with respect to the colorant receiving layer for coating fluid, more preferably account for 0.01～1.0%.And described colorant receiving layer with coating fluid with under two occasions that are coated with more than the solution, preferably in each coating fluid, add tensio-active agent respectively.

Among the present invention, the colorant receiving layer preferably contains the anti-roll high boiling organic solvent of using.Described high boiling organic solvent is that boiling point is in organic compound more than 150 ℃ under the normal pressure, is water-soluble or hydrophobic compound.This compound at room temperature can be a liquid or solid, can be polymer or low molecule.

Specifically can enumerate aromatic carboxylic acid esters's (dibutyl phthalate for example; diphenyl phthalate; phenol benzoate etc.); aliphatic carboxylic acid esters,'s class (Octyl adipate for example; Uniflex DBS; methyl stearate; dibutyl maleinate; dibutyl fumarate; CitroflexA-2 etc.); phosphoric acid ester (trioctyl phosphate for example; tritolyl phosphate etc.); epoxies (epoxidized soybean oil for example; epoxidation aliphatics methyl esters etc.); alcohols (Stearyl alcohol for example; 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; 4-penta triol; 1; 2, the 6-hexanetriol; the sulfo-glycol ether; trolamine; polyoxyethylene glycol etc.); vegetables oil (soybean oil for example; the sunflower seed wet goods); senior aliphatic carboxylic acid (linolic acid for example; oleic acid etc.) etc.

(support)

The support that the present invention uses can use transparent support that is made of transparent materials such as plastics and the opaque support that is made of opaque materials such as paper.Produce the transparency from the colorant receiving layer, preferably use the opaque support of transparent support or high-luster.And can also use CD-ROM, DVD-ROM etc. to read Worm type optical disks such as special-purpose cd, CD-R, DVD-R and rewriting type optical disk as support, give the colorant receiving layer in index face one side.

As the operable material of above-mentioned transparent support, when preferably using with OHP and demonstration backlight, the transparency can stand radiating thermotolerance material.As this material, for example can enumerate polyethylene terephthalate polyester such as (PET), polysulfones, polyphenylene oxide, polyimide, polycarbonate, polymeric amide etc.Preferred polyester class wherein, preferred especially polyethylene terephthalate (PET).

The thickness of above-mentioned transparent support is not particularly limited, but from easy processing preferred 50～200 microns.

As the opaque support of high gloss, preferably be provided with and have 40% above glossiness on the side surface of colorant receiving layer.

Above-mentioned glossiness is the numerical value of obtaining according to the method for JIS P-8142 (75 degree specular gloss test methods of paper and cardboard) record.This support can specifically be enumerated following support.

For example can enumerate enamelled paper, White Board, Die plate paper, the paper support of the high-lusters such as barium oxide paper that silver halide photography uses with support etc., polyethylene terephthalate polyester such as (PET), nitrocellulose, rhodia, cellulose esters such as cellulose acetate butyrate, polysulfones, polyphenylene oxide, polyimide, polycarbonate, contain whitewash on the plastics films such as polymeric amide and make opaque (also can implement surperficial calender process) high-luster film, perhaps at above-mentioned various paper supports, above-mentioned transparent support or the high-luster film that contains white pigment etc. are provided with support of the polyolefine coating that contains or do not contain white pigment etc.

Can also suitably enumerate the expanded polyester film (for example make it to contain polyolefin fine particle, utilize the interstitial foaming PET that stretches) that contains white pigment.More preferably can be as the resin-coated paper of silver halide photography with photographic pape.

The thickness of above-mentioned opaque support is not particularly limited, but from the easy to handle viewpoint preferred 50～300 microns.

And in order to improve wet characteristic and cohesiveness, the preferred support of above-mentioned support surface having been implemented Corona discharge Treatment, glow discharge processing, flame treating, UV treatment etc. that uses.

Below elaborate with regard to the above-mentioned employed body paper of resin-coated paper.

As this body paper, be main raw material with the wood pulp, except that wood pulp, copy paper with synthetic pulps such as polypropylene or synthon such as nylon and polyester in case of necessity.And in body paper, also can use any material among LBKP, LBSP, NBKP, NBSP, LDP, NDP, LUKP, the NUKP, but preferably use staple fibre composition many LBKP, NBSP, LBSP, NDP, LDP more as above-mentioned wood pulp.

Preferred 10～70 weight % of the content of LBSP and/or LDP wherein.

Above-mentioned paper pulp preferably adopts the few dissolving pulp of impurity (sulfate pulping or sulfite cellulose), handles the paper pulp that improves whiteness through bleaching and also is suitable for.But also can in body paper, suitably add cementing agents such as higher fatty acid, alkyl ketene dimer, white pigments such as lime carbonate, talcum, titanium oxide, paper power tougheners such as starch, polyacrylamide, polyvinyl alcohol, white dyes, moisture content retention agents such as polyoxyethylene glycol, dispersion agent, gentle tenderizer such as quaternary amine etc.

Copy the freeness of paper, stipulate preferred 200～500 milliliters according to CSF with paper pulp, and the staple length after the making beating, according to JIS P-8207 regulation, remaining branch of 24 orders and the remaining weight % sum of dividing of 42 orders are preferably 30～70 weight %.In addition, 4 orders preferably are in below the 20 weight % remaining the branch.

Preferred 30～250 grams of the weight of body paper, preferred especially 50～200 grams.Preferred 40～250 microns of the thickness of body paper.Body paper can also be given high smoothness by calender process after copying the paper stage or copying paper.Body paper density is generally 0.7～1.2 gram/square metre (JIS P-8118).

The rigidity of body paper is preferably 20～200 grams under JIS P-8143 defined terms in addition.

Can also be on the body paper surface coating surface cementing agent, can use and the same cementing agent that can in above-mentioned body paper, add as the surface sizing agent.

Body paper pH is according to the numerical value preferred 5～9 of water hot extraction's method mensuration of stipulating among the JIS P-8113.

Cover the polyethylene at the body paper surface and the back side,, also can use a part of LLDPE or polypropylene etc. though mainly be new LDPE (film grade) (LDPE) and/or high density polyethylene(HDPE) (HDPE).

Form the polyethylene layer of colorant receiving layer one side, as taking a picture with frequent enforcements such as photographic pape, particularly preferably in having added rutile or anatase-type titanium oxide and white dyes, ultramarine in the polyethylene, opaqueness and whiteness and tone are improved.Wherein titanium oxide content accounts for 3～20 weight % with respect to the polyethylene preferably approximately, more preferably accounts for 4～13 weight %.There is no particular restriction for the thickness of polyethylene layer, is suitable but surface and back layer are 10～50 micron thickness.In order to give the adherence of polyethylene layer and colorant receiving layer, also undercoat can be set in addition.As this undercoat, preferred waterborne polyester and gelatin, PVA.And preferred 0.01～5 micron of the thickness of this undercoat.

Polyethylene coats paper, both can be used as glossy paper and used, also can use the various paper that formed calendering face and thin,tough silk face, this calendering face and thin,tough silk face, be on the body paper surface, in the poly painting process of extrusion molten, to have carried out obtaining with common photograph photographic pape after so-called excipient is handled.

The back side can also be set on support be coated with (back coat) layer, the composition that can add in this backing coat can be enumerated white pigment and water-soluble binder and other compositions.

As the contained above-mentioned white pigment of backing coat, for example can enumerate 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 amorphous silicas, colloid silica, colloidal alumina, intend boehmite, aluminium hydroxide, aluminum oxide, lithopone, zeolite, the aquation halloysite, magnesiumcarbonate, white inorganic pigments such as magnesium hydroxide, the polystyrene plastic pigment, the acrylic acid series plastic pigment, polyethylene, microcapsule, urea resin, pigment dyestuffs such as melamine resin etc.

The above-mentioned water-soluble binder that uses as coating overleaf, for example can enumerate water-soluble polymers such as vinylbenzene/maleate copolymer, styrene/acrylic salt copolymer, polyvinyl alcohol, silanol modified polyethylene alcohol, starch, cationic starch, casein, gelatin, carboxymethyl cellulose, Natvosol, polyvinylpyrrolidone, water dispersible polymers such as styrene butadiene latices, acrylic latex etc.

As other contained compositions of backing coat, can enumerate defoamer and suds suppressor, dyestuff, white dyes, sanitas, anti-hydrated agent etc.

(making of ink jet recording medium)

The colorant receiving layer of ink jet recording medium of the present invention, the following method of for example preferred employing forms, promptly adopt and on the support surface, be coated with first coating fluid (following also often be called " coating fluid A ") that contains particulate and water soluble resin etc. at least, (1) in this coating, (2) by in this coating layer drying process of forming of coating before this coating layer demonstration falling rate of drying speed, any time, will contain the method (wet method-wet method) of the coating layer crosslinking curing after second coating fluid (following often be called " coating fluid B ") is given more than the pH8 of mordant at least.The above-mentioned sulfocompound that wherein the present invention relates to preferably is included in above-mentioned first coating fluid (coating fluid A) or second coating fluid (coating fluid B) at least.And preferably make the linking agent of the above-mentioned water soluble resin of crosslinkable, be also contained among at least one side in above-mentioned first coating fluid (coating fluid A) or second coating fluid (coating fluid B).

From ink absorption and the viewpoint that prevents the film be full of cracks, preferably be provided with the colorant receiving layer of such crosslinking curing.

Like this, because mordant is present in the near surface of colorant receiving layer mostly, the colorant of ink-jet can be effectively by mordant dyeing, and the water tolerance of writings and image improves behind the lettering, thereby preferred.Part mordant also can be contained in the above-mentioned coating fluid (A), and the mordant of coating fluid under this occasion (A) and coating fluid (B) can be identical or different.

Among the present invention, the colorant receiving layer that contains particulate (for example fumed silica) and water soluble resin (for example polyvinyl alcohol) at least can prepare in accordance with the following methods with coating fluid (coating fluid (A)).That is,

Fumed silica particulate and dispersion agent are added (for example 10～20 weight % of the silicon dioxide microparticle content in the water) in the entry, use high speed rotating wet type colloidal mill (for example " the Network レ ア ミ Star Network ス " that makes by ェ system テ Network ニ Star Network (strain)), for example 10000 (under preferred 5000～20000rpm) the rpm high speed rotating velocity conditions, after it is for example disperseed 20 minutes (preferred 10～30 minutes), add linking agent (boron compound), polyvinyl alcohol (PVA) aqueous solution (for example adding the PVA that is about as much as above-mentioned fumed silica weight 1/3), and the colorant receiving layer contains with coating fluid under the occasion of the above-mentioned sulfocompound that the present invention relates to and also should add this compound, under rotating condition same as described above, disperse, in this way preparation.The coating fluid that obtains is the collosol state of homogeneous, with remembering that down coating process is coated on after drying on the support with it, can form the colorant receiving layer of the vesicular structure with three dimensional network ocular structure.

And the preparation of the water dispersion of forming by above-mentioned fumed silica and dispersion agent, adopt prepared beforehand fumed silica aqueous dispersions, both this aqueous dispersions can be joined in the aqueous dispersant, also aqueous dispersant can be added in the fumed silica aqueous dispersions, can also the two mix simultaneously.In addition, can also use the fumed silica powder, join in the aqueous dispersant like that according to above-mentioned without the fumed silica aqueous dispersions.

After above-mentioned fumed silica and dispersant, utilize dispersion machine with this mixed solution grain refined, can access the aqueous dispersions of median size 50～300 nanometers like this.Obtain the required dispersion machine of this aqueous dispersions, though can use known various dispersion machines in the past such as high speed rotating dispersion machine and medium stirring-type dispersion machine (for example ball mill, sand mill etc.), ultrasonic dispersing machine, colloid mill disperser, high pressure dispersion machine, but from the viewpoint of the pearl microparticulate that can make formation effectively, preferred stirring-type dispersion machine, colloid mill disperser or high pressure dispersion machine.

And, can make water, organic solvent or its mixed solvent as the solvent in each operation.Can be used in the organic solvent in this coating, can enumerate alcohols such as methyl alcohol, ethanol, n-propyl alcohol, Virahol, methoxy propane, ketones such as acetone, butanone, tetrahydrofuran (THF), acetonitrile, ethyl acetate, toluene etc.

Can use cation type polymer as above-mentioned dispersion agent.Described cation type polymer can be enumerated the example of above-mentioned mordant etc.And dispersion agent preferably uses silane coupling agent.

Above-mentioned dispersion agent is with respect to the addition of particulate, and is preferred 0.1～30%, and more preferably 1～10%.

Colorant receiving layer of the present invention is with the coating of coating fluid, for example can adopt overflow mould spreader, airblade coating device, blade coating device, rod (rod) to be coated with device, cutter is coated with known coating processes such as device, extrusion coated device, contrary roll-coater, bar (bar) coating machine and carries out.

When coating colorant receiving layer is with coating fluid (coating fluid (A)) or after the coating, (B) gives this coating layer with coating fluid, give this coating fluid (B) before showing falling rate of drying speed but also can the coating layer (A) after coating become.That is to say employing, after coating colorant receiving layer is with coating fluid (coating fluid (A)), during this coating layer shows constant rate drying speed in, the manufacture method that imports mordant is suitable.

" coating layer after the coating becomes and shows before the falling rate of drying speed " described here, be meant several minutes time courses that after the colorant receiving layer is with the coating fluid coating, begin, the proportional in time minimizing of content of solvent (dispersion medium) in the applied coating layer in during this shows the phenomenon of " constant rate drying speed ".The time of this about showing " constant rate drying speed ", for example be documented in " chemical engineering brief guide " (the 707th～712 page, ball kind (strain) distribution, on October 25th, 1980).

As mentioned above, this coating layer can be dried to after first coating fluid coating show before the falling rate of drying speed till, this drying is generally carried out 0.5～10 minute (preferred 0.5～5 minute) at 50～180 ℃.This time of drying is different because of glue spread certainly, is suitable but be in usually in the above-mentioned scope.

Show falling rate of drying speed adding method before as above-mentioned first coating layer, can enumerate (1) is coated with coating fluid (B) again on coating layer method, (2) utilize the method for spraying method spraying and the method for support impregnation in coating fluid (B) that (3) will form coating layer etc.

In aforesaid method (1), as the method for coating coating fluid (B), for example can utilize curtain formula curtain coater, overflow mould spreader, airblade coating device, blade coating device, rod to be coated with device, cutter and be coated with known coating processes such as device, extrusion coated device, contrary roll-coater, bar coating machine.But preferred the utilization is coated with machine etc. as extrusion coated device, curtain formula curtain coater, rod, the method that spreader and first coating layer that has formed directly do not contact.

After giving above-mentioned mordant solution (coating fluid (B)), the general employing in 0.5～30 minute method of 40～180 ℃ of heating carried out drying and curing.Wherein preferably 40～150 ℃ of heating 1～20 minute.

And in coating colorant receiving layer coating fluid (coating fluid (A)), give under the occasion of above-mentioned mordant solution (coating fluid (B)), can on support, be coated with (double-layer coating) colorant receiving layer coating fluid (coating fluid (A)) and mordant solution (coating fluid (B)) simultaneously, this colorant receiving layer coating fluid (coating fluid (A)) is contacted with support, pass through dry solidification then, form the colorant receiving layer.

Above-mentioned coating (double-layer coating) simultaneously for example can adopt the coating process of overflow mould spreader, curtain formula curtain coater to carry out.Though the coating back can be with the coating layer drying that forms simultaneously, but the drying under this occasion, generally adopt under 40～150 ℃ of temperature 0.5～10 minute method of coating layer heating is carried out, preferably adopt under 40～100 ℃ of temperature 0.5～5 minute method of coating layer heating is carried out.

For example adopt the overflow mould spreader to carry out under the occasion of above-mentioned coating (double-layer coating) simultaneously, two kinds of coating fluids that sprayed simultaneously are near the ejiction opening of overflow mould spreader, form double-layer before promptly moving on the support, under this state, on support, carry out the double-layer coating.But coating is preceding by the two-layer coating fluid of double-layer, on support when mobile, owing to produce crosslinking reaction easily on the interface of two kinds of liquid, near two kinds of liquid that are ejected the ejiction opening of overflow mould spreader are because of mixing tackify, often obstruction coating operation easily.Therefore, carry out double-layer when coating while as described above, in coating colorant receiving layer coating fluid (coating fluid (A)) and mordant solution (coating fluid (B)), preferably carry out the triple layer coating simultaneously, so that sealing coat liquid (middle layer liquid) separates above-mentioned two kinds of liquid.

Can select ad lib about above-mentioned sealing coat liquid.For example can enumerate the aqueous solution that contains the minor amount of water soluble resin and water etc.Described water soluble resin can be taken into account coating and use under the purpose of tackify, so can enumerate polymkeric substance such as cellulose-based resin (for example Vltra tears, methylcellulose gum, hydroxyethylmethyl-cellulose etc.), polyvinylpyrrolidone, gelatin.Also can contain above-mentioned mordant in the sealing coat liquid in addition.

After forming the colorant receiving layer on the support, for example adopt supercalender, bright roller calender etc., make this colorant receiving layer under heating and pressurizing, pass through to improve its surperficial smoothness and glossiness, the transparency and coating strength by means of this calender process between the roll jaw.Yet make porosity reduce the major cause of (promptly reducing the absorptivity of printing ink) because this calender process often becomes, carry out so importantly can make under the few condition of the reduction of porosity in setting.

The temperature of roll when carrying out calender process, preferred 30～150 ℃, more preferably 40～100 ℃.And preferred 50～400 kg/cm of linear pressure of roll shop building during calender process, more preferably 100～200 kg/cm.

The bed thickness of above-mentioned colorant water receiving layer, under the occasion of ink-vapor recording, owing to must have the absorptive capacity of the whole drops of nearly absorption, so must be according to determining with the relation of layer mesoporosity rate.For example if ink ejection amount is 8 to receive liter/square millimeter, porosity is 60% o'clock, and it is about more than 15 microns that bed thickness must reach.Consider this point, under the occasion of ink jet recording medium, preferred 10～50 microns of the bed thickness of colorant receiving layer.

And the pore aperture of colorant receiving layer, preferred 0.005～0.050 micron of its median particle diameter, more preferably 0.01～0.035 micron.Above-mentioned porosity and pore median particle diameter can adopt mercury bore measuring instrument (commodity that (strain) Shimadzu Seisakusho Ltd. makes: " ボ ア サ ィ ザ-9320-PC2 ") to measure.

Though and colorant accepts should preferably transparent goodly, as standard, the turbidity value on the transparent film supporter during formation colorant receiving layer preferably is in below 30%, more preferably is in below 20%.This turbidity value can use turbidometer (for example " HGM-2DP " of ス ガ trier (strain) manufacturing) to measure.

Can also in constituting the layer (for example colorant receiving layer or backing coat) of ink jet recording medium of the present invention, add the dispersion thing of polymer particles.This polymer particles disperses thing, can be at size stabilization and prevent to curl, prevent to adhere, prevent that film be full of cracks etc. from improving under the purpose of film character uses.Disperse thing about described polymer particles, be documented in the spy open clear 62-245258, same 62-1316648, with on the 62-110066 equal sign communique.In addition, in containing the layer of above-mentioned mordant, add low (below the 40 ℃) polymer particles of glass transformation temperature and disperse under the situation of thing, can prevent the be full of cracks of layer and curl.And add the high polymer particles dispersion thing of glass transformation temperature in the coating overleaf, also can prevent to curl.

Ink jet recording medium of the present invention, in the colorant receiving layer or the superiors of colorant receiving layer give thermoplastic resin, after the printing,, perhaps can form equal one deck with the solvent in the printing ink etc. by heating and pressurization.Can improve glossiness and ozone resistance like this.

Processing example before and after the aforesaid way printing can be enumerated and is documented in special permission 3352414, special fair 5-50396, special fair 7-39206, special permission 2908518, special permission 2868840, special permission 3359217, spy and opens 2002-225415, spy and open 2002-127248, spy and open method in the 2002-264266 equal sign communique etc.

And ink jet recording medium of the present invention, can also utilize to be documented in the spy and to open that flat 10-81064, same 10-119423, same 10-157277, same 10-217601, same 11-348409, spy open 2001-138621, same 2000-43401, same 2000-211235, same 2000-309157, same 2001-96897, same 2001-138627, the spy opens flat 11-91242, same 8-2087, same 8-2090, same 8-2091, makes with the method in the 8-2093 equal sign communique.

-ink jet recording method-

In the ink jet recording method of the present invention, to ink-jet recording and unrestricted, can adopt known mode to carry out, for example utilize electrostatic attraction ejection printing ink the electric charge control mode, utilize the mode of drippage as required (pressure pulse mode) of the vibration pressure of piezoelectric element, electrical signal is transformed into acoustic beam after irradiation printing ink utilize the sound wave ink-jetting style of radiation pressure ejection printing ink and heating printing ink to form bubble, utilize the hot ink-jetting style of the pressure that produces etc.In the ink-jet recording, comprise with the many spray regimes that are called the low printing ink of concentration of gloss oil China ink of small volume ejection, utilize tone identical in fact but most printing ink that concentration is different improve the mode of image quality and the mode that adopts water white transparency printing ink.

Embodiment

Embodiments of the invention below are described, but the present invention is not subjected to any restriction of these embodiment.Wherein " part " described in the embodiment and " % " are meant " weight part " and " quality % " respectively.

(embodiment 1)

(preparation of water color ink)

Under remember in the composition that adding deionized water makes 1 liter after, on one side stir on one side 30～40 ℃ of heating.KOH with 10 mol adjusts to 9 with pH then, uses the micro-strainer filtration under diminished pressure of 0.25 micron of mean pore size, has made light magenta printing ink.

By rosaniline dyes (T-1) 7.5 grams per liters of remembering that down structural formula is represented

Glycol ether 50 grams per liters

Urea 10 grams per liters

Glycerine 200 grams per liters

Triglycol monobutyl ether 120 grams per liters

2-Pyrrolidone 20 grams per liters

Trolamine 6.9 grams per liters

Benzotriazole 0.08 grams per liter

サ one Off ィ ノ one Le 465 10.5 grams per liters

(tensio-active agent, ェ ア one プ ロ ダ Network ス Japan makes)

PROXEL XL-2 (sterilant: ICI Japan makes) 3.5 grams per liters

Further change dyestuff kind and additive, prepared magenta ink, pale cyan ink, cyan ink, Yellow ink and black ink, made the printing ink group of concentration shown in the table 1.

Table 1 (composition of printing ink group 101)

	Light magenta	Pinkish red	Nattierblue	Cyan	Yellow	Black
							Dyestuff (g/L)	T-1(7.5)	T-1(30.0)	T-2(8.75)	T-2(35.0)	T-3(29.0)	T-4(20.0) T-5(20.0) T-6(20.0) T-3(21.0)
Glycol ether (g/L)	50	80	170	110	90	10
							Urea (g/L)	10	70	-	-	-	-
Glycerine (g/L)	200	150	170	150	150	160
							Triglycol monobutyl ether (g/L)	120	120	130	130	130	-
Diethylene glycol monobutyl ether (g/L)	-	-	-	-	-	110
							2-Pyrrolidone (g/L)	20	-	-	-	-	50
サ one Off ィ ノ one Le 465 (g/L)	10.5	10	9.8	10.5	-	-
							サ one Off ィ ノ one Le STG (g/L)	-	-	-	-	8.5	9.8
Trolamine (g/L)	6.9	7	6	6	0.9	15
							Benzotriazole (g/L)	0.08	0.07	0.08	0.08	-	0.06
PROXEL?XL-2(g/L)	3.5	1.5	1.1	1.2	1.5	1.1

Below change the kind of light magenta, magenta, nattierblue, cyan and yellow each ink dye of relevant printing ink group 101 according to table 2, made printing ink group 102～106.In addition, under the occasion of change dyestuff, each has adjusted dye strength to wait mole to replace then to use to benchmark, makes the penetrating concentration of each printing ink liquid equate with printing ink group 101.And and with a mole dyestuff such as respectively having used under the occasion of dyestuff.

[table 2]

The printing ink group	Light magenta	Pinkish red	Nattierblue	Cyan	Yellow
						??101	????T-1	????T-1	????T-2	??T-2	??T-3
??102	????T-1	????T-1	????C-10	??C-10	??T-3
						??103	????M-11	????M-11	????T-2	??T-2	??T-3
??104	????M-11	????M-11	????C-10	??C-10	??T-3
						??105	????M-10	????M-10	????C-40	??C-40	??Y-4
??106	????M-6	????M-3	????C-42	??C-40	??Y-24 ??Y-25

(making of support)

To pull an oar to 300 milliliters of Canadian freenesss by the wood pulp that 100 parts of LBKP form with two disk refiners, each material all with respect to the adiabatic drying mass ratio of wood pulp than adding 0.5 part of epoxidation docosanoic acid acid amides, 1.0 parts of anionic polyacrylamides, 0.1 portion of polymeric amide polyamine Epicholorohydrin and 0.5 part of cationic polyacrylamide, with fourdrinier paper machine manufactured paper with pulp weighing 170 grams/square metre body paper.

In order to adjust the surface size of above-mentioned body paper, in 4% polyvinyl alcohol water solution, add 0.04% white dyes (Sumitomo Chemical (strain) is made " Whitex BB "), with its contain be immersed in make in the above-mentioned body paper its according to adiabatic drying weight convert reach 0.5 gram/square metre, after the drying, implement calender process again, obtained the basic paper that density is adjusted to 1.05 grams per milliliters.

After metal wire face (back side) side of the basic paper that obtains carried out Corona discharge Treatment, utilize melt extruded machine coating high density polyethylene(HDPE) to make thickness reach 19 microns, formed the resin layer that constitutes by matt surface (following the resin aspect is called " back side ").And then the resin layer at this back side carried out Corona discharge Treatment, be coated with then with 1: 2 weight ratio aluminum oxide (" alumina sol 100 " that daily output chemical industry (strain) is made) and silicon-dioxide (" ス ノ one テ Star Network ス O " that daily output chemical industry (strain) is made) are dispersed in dispersion liquid in the water as static inhibitor, dry weight is reached 0.2 restrain/square metre.

After then front (surface) side that the resin layer side is not set being implemented Corona discharge Treatment, utilize the extruding of melt extruded machine wherein to contain the new LDPE (film grade) of 10% anatase titanium dioxide, micro-ultramarine and 0.01% (with respect to polyethylene) white dyes and MFR (melt flow rate (MFR)) 3.8, make it thickness and reach 29 microns, form the thermoplastic resin (following this high gloss face is called " surface ") of high gloss in the face side of basic paper, obtained the purpose support.

[making of ink jet recording sheet (1)]

(preparation of coating fluid A of colorant receiving layer)

(1) fumed silica particulate in the following composition, (2) ion exchanged water and (3) dispersion agent (シ ャ ロ one Le DC-902P) are mixed, after KD-P ((strain) シ Application マ Le ェ Application one プ ラ ィ ズ manufacturing) dispersion, add (4) poly aluminium chloride, (5) acetic acid zirconium and (6) boric acid water, with dissolver after stirring 10 minutes under 2000 rev/mins of rotating speeds, add (7) polyvinyl alcohol, stirred 10 minutes down in 2000 rev/mins of rotating speeds again.And then add and to contain (8) tensio-active agent and (9) ion exchanged water, after 2000 rev/mins of rotating speeds stir 5 minutes down, made purpose colorant receiving layer with coating fluid (A).

＜colorant receiving layer the composition of coating fluid (A) 〉

(1) the fumed silica particulate is 10 parts

(" the レ ォ ロ シ one Le QS-30 " that (strain) ト Network ャ マ makes, average primary particle diameter 7 nanometers)

(2) ion exchanged water is 51.6 parts

(3) dispersion agent is 1 part

(the first industrial pharmacy (strain) is made for シ ャ ロ one Le DC-902P, 51% the aqueous solution)

(4) poly aluminium chloride is 0.6 part

(40% aqueous solution, basic structure formula: AL ₂(OH) ₅Cl, basicity 83%, mordant)

(5) acetic acid zirconium (25% aqueous solution, mordant) is 0.3 part

(6) boric acid water (5% aqueous solution, linking agent) is 8 parts

(7) vinyl alcohol (8% aqueous solution, water soluble resin) is 27.8 parts

((strain) Network ラ レ makes " PVA235 ", 88 moles of % of saponification deg, the polymerization degree 3500)

(8) tensio-active agent is 0.1 part

(ォ Le Off ィ Application PD-101, day letter chemical industry (strain) is made)

(9) ion exchanged water is 25.6 parts.

(making of ink jet recording sheet)

After the surface enforcement Corona discharge Treatment to above-mentioned support, utilize the overflow mould spreader the above-mentioned colorant receiving layer that obtains to be coated on 200 milliliters of/square metre glue spreads with coating fluid (A) on the surface of support (painting process), the solid shape branch concentration that (wind speed 3～8 meter per seconds) are dried to coating layer under 80 ℃ in the heat-sealing drying machine is 20%.This coating layer shows constant rate drying speed during this period.Be immersed in down then and remember 30 seconds in the mordant coating fluid of forming (B), make and adhere to 20 gram/square metre these materials (mordant is given operation) on the above-mentioned coating layer at once, and then at 80 ℃ of down dry 10 minutes (drying processes).Made the ink jet recording sheet of the present invention (1) of the colorant receiving layer that is provided with 32 microns dry film thickness by this way.

The composition of＜mordant coating fluid (B) 〉

(1) boric acid (linking agent) is 0.65 part

(2) zirconium carbonate ammonium is 6.5 parts

(" ジ Le コ ゾ one Le AC-7 ", 28% aqueous solution of first rare element chemistry industry (strain) system)

(3) volatile salt is 6.0 parts

(4) ion exchanged water is 83.8 parts

(5) tensio-active agent is 0.2 part

(メ ガ Off ア Star Network F-1405, big Japanese ink chemical industry (strain) is made)

[making of ink jet recording sheet (2)]

In [making of ink jet recording sheet (1)],, made ink jet recording sheet (2) equally with [making of ink jet recording sheet (1)] except having added 0.3 part in coating fluid (A) at the colorant receiving layer down the note compound (1).

[changing 42]

HOCH ₂CH ₂SCH ₂CH ₂SCH ₂CH ₂OH

[making of ink jet recording sheet (3)]

In [making of ink jet recording sheet (1)], note compound (2) and 0.1 part are remembered down and have been made ink jet recording sheet (3) equally with [making of ink jet recording sheet (1)] the compound (2 ') down except added 0.6 part in coating fluid (A) at the colorant receiving layer.

[changing 43]

HO ₂C(CH ₂) ₃SCH ₂CH ₂S(CH ₂) ₃CO ₂H

HO ₂CCH ₂SSCH ₂CO ₂H

[making of ink jet recording sheet (4)]

In [making of ink jet recording sheet (1)],, made ink jet recording sheet (4) equally with [making of ink jet recording sheet (1)] except having added 0.5 part in coating fluid (A) at the colorant receiving layer down the note compound (3).

[changing 44]

HOCH ₂CH ₂SOCH ₂CH ₂OH

[making of ink jet recording sheet (5)]

In [making of ink jet recording sheet (1)],, made ink jet recording sheet (5) equally with [making of ink jet recording sheet (1)] except the colorant receiving layer has added 0.4 part of amidinothiourea in coating fluid (A).

[making of ink jet recording sheet (6)]

In [making of ink jet recording sheet (1)], except having added 0.4 part in coating fluid (A) at the colorant receiving layer down note compound (4) and the 0.1 part of toluenesulfinic acid sodium, made ink jet recording sheet (6) equally with [making of ink jet recording sheet (1)].

[changing 45]

[making of ink jet recording sheet (7)]

In [making of ink jet recording sheet (1)], except in mordant coating fluid (B), having added 2 parts of Sodium Thiocyanate 99s, made ink jet recording sheet (7) equally with [making of ink jet recording sheet (1)].

(record images and evaluation)

Printing ink group 101～106 is contained in the print cartridge of ink-jet printer PM900C (Seiko Epson Corp's manufacturing), after print image is gone up in above-mentioned ink jet recording sheet (1)～(7), has carried out following evaluation.

＜ozone resistance 〉

About ozone resistance, made pinkish red monochrome and grey printed sample after, carried out following evaluation.

(test 1)

Pinkish red reflection density is 1.0 o'clock, and sample was preserved two days in ozone concn is set at the box of 5ppm.Measure the reflection density of this image then.And then calculate the survival rate of rosaniline dyes according to following formula, by aftermentioned A, B and C benchmark evaluation.

Rosaniline dyes survival rate=(the pinkish red concentration before the pinkish red concentration/test after the test) * 100

The rosaniline dyes survival rate:

Be decided to be A more than 80%

Be lower than 80% more than 70% and be decided to be B

Be lower than 70% and be decided to be C.

(test 2)

Carried out following evaluation after making gray lettering sample.

Utilize following method to estimate sample is set at the aberration of preserving in the box of 0.5ppm before and after seven days at ozone concn.

That is to say, after the SPM100-III that makes with グ レ グ Co., Ltd. measures colourity (a*1, b*1) and brightness (L1) behind the firm lettering, the weather resisteant tester that utilizes ア ト ラ ス Co., Ltd. to make shone xenon light (8500 lux) after seven days, measure colourity (a*2, b*2) and brightness (L2) once more, obtain the mode of the aberration (Δ E) of irradiate light front and back according to following mathematical expression (I) and estimate.

Δ E={ (a*1-a*2) ²+ (b*1-b*2) ²+ (L1-L2) ²} ^1/2Mathematical expression (I)

About the dyestuff survival rate, reflection density be 1.0,1.3 and 1.6 3 estimate, aberration under any concentration all is lower than 10 situation and is decided to be A, be decided to be B because of change in concentration comprises the situation that is lower than 10 and 10 above two kinds of evaluation results, situation about being more than 10 in whole concentration is decided to be C.In addition, the concentration of ozone gas in the box is to set with the ozone gas monitor (OZG-EM-01 type) that APPLICS makes.

Above test-results is shown among table 3 and the table 4.

[table 3]

The printing ink group	Ink jet recording sheet	Ozone resistance (magenta)	Remarks
				??101	??(1)	C	Reference examples
??102	??(1)	C	Reference examples
				??103	??(1)	B	Reference examples
??104	??(1)	B	Reference examples
				??105	??(1)	B	Reference examples
??106	??(1)	B	Reference examples
				??101	??(2)	C	Reference examples
??101	??(3)	C	Reference examples
				??101	??(4)	C	Reference examples
??101	??(5)	C	Reference examples
				??102	??(6)	C	Reference examples
??102	??(7)	C	Reference examples
				??103	??(2)	A	The present invention
??104	??(2)	A	The present invention
				??105	??(3)	A	The present invention
??106	??(4)	A	The present invention
				??104	??(5)	A	The present invention
??105	??(6)	A	The present invention
				??106	??(7)	A	The present invention

[table 4]

The printing ink group	Ink jet recording sheet	Ozone resistance (grey)	Remarks
				????101	??(1)	C	Reference examples
????101	??(2)	C	Reference examples
				????101	??(3)	C	Reference examples
????104	??(2)	A	The present invention
				????105	??(3)	A	The present invention
????106	??(4)	A	The present invention
				????104	??(5)	A	The present invention
????105	??(6)	A	The present invention
				????106	??(7)	A	The present invention

Shown in the last table, can access the ozone resistance excellent images according to the inventive method.And can obtain the image that concentration, ink absorption and gloss are good, infiltration is few.

The invention effect

Can provide a kind of image the ink jet recording method good to the fastness of ozone gas according to the present invention.

Claims (3)

1. ink jet recording method, the cyan ink that it is characterized in that using with the Yellow ink that contains a kind of yellow dyes at least, contains a kind of magenta ink of rosaniline dyes at least and contain a kind of cyan dye at least is as the oxidizing potential of minimum integrant and the described rosaniline dyes ink for ink-jet recording group higher than 0.8V (vsSCE), on support, on ink jet recording medium, form image with the colorant receiving layer that contains sulfocompound.

2. ink jet recording method according to claim 1 is characterized in that the oxidizing potential of described cyan dye is also higher than 0.8V (vs SCE).

3. ink jet recording method according to claim 1 and 2 is characterized in that described sulfocompound is one or more compounds of selecting from thioether based compound, thiocarbamide based compound, sulfoxide based compound, thiocyanic acid based compound,-sulfinic acid based compound, disulphide based compound and sulfur heterocyclic compound.