CN100376411C - Sheet for ink-jet recording - Google Patents
Sheet for ink-jet recording Download PDFInfo
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- CN100376411C CN100376411C CNB2003101195973A CN200310119597A CN100376411C CN 100376411 C CN100376411 C CN 100376411C CN B2003101195973 A CNB2003101195973 A CN B2003101195973A CN 200310119597 A CN200310119597 A CN 200310119597A CN 100376411 C CN100376411 C CN 100376411C
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- jet recording
- ink jet
- recording sheet
- receiving layer
- material receiving
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- Ink Jet Recording Methods And Recording Media Thereof (AREA)
Abstract
An ink jet recording medium containing a support and an ink receiving layer on the support, in which the ink receiving layer includes at least a complex formed from a metal with a valence of two or more and an acidic group-containing compound having a substituent group containing a nitrogen atom, an oxygen atom or a sulfur atom. The acidic group-containing compound is preferably a compound represented by the following general formula (I).
Description
Technical field
The present invention relates to a kind ofly adopting liquid ink such as water color ink or oil-based ink or be solid-state at normal temperatures and can be used for shining the employed material that is recorded in the ink mist recording of solid ink etc. of picture after fusion liquefaction, what relate in particular to document image oozes profit less and the good ink jet recording sheet of light resistance.
Background technology
In recent years, be accompanied by the fast development of information technology (IT) industry, recording method and the tape deck having developed various information processing systems and be suitable for various information processing systems, and realized industrial productionization.
In these recording methods, ink-vapo(u)r recording is because it can be at the multiple enterprising line item of material that is recorded, hardware (machine) is relatively more cheap and volume is little, noise is less simultaneously, have good solemn silence, these various advantages make no matter it all is widely used in office still is family.
In addition, along with the high-resolutionization of ink-jet printer, can obtain record in recent years, and, also develop the recording sheet that various ink mist recordings are used along with the progress of these hardware (machine) as the high image quality of photo.
The recording sheet of using for this ink mist recording generally requires it to have following characteristic, (1) quick-drying (infiltration rate to printing ink is very fast), (2) the suitable homogeneous of the particle diameter of ink dot (not oozing profit), (3) graininess is good, (4) the just round property height of ink dot, (5) color density height, (6) chroma height (phenomenon that does not have obfuscation), (7) solarization is as the resistance to water of portion, light resistance and ozone resistance are all good, (8) sheet for recording has higher whiteness, (9) the having good keeping qualities of sheet for recording (even can flavescence through long preservation, the long preservation hypograph can flushing yet, and good long term resists spreading and sinking in property), (10) not yielding, have good dimensional stability (it crispaturas very little), (11) hardware (machine) maneuverability is good, etc.
And then, as the gloss photographic paper with when obtaining record as the high image quality of photo, except above-mentioned various performances, also require it to have the quality of the photographic pape of glossiness and surface smoothing and similar silver halide photography.
In order to improve above-mentioned various performances, developed the ink jet recording sheet that in look material receiving layer, has porous matter structure in recent years gradually.This ink jet recording sheet has porous matter structure, therefore has good printing ink compatibility (quick-drying), and glossiness is higher.
For example, in some patent documentations, propose on supporter, to be provided with and contain inorganic pigment microparticles and water-soluble resin and have ink jet recording sheet (as reference patent documentation 1 or 2) than the look material receiving layer of high voidage.
These sheet for recording, especially be provided with ink jet recording sheet by the look material receiving layer that adopts the porous matter of silica to constitute as inorganic pigment microparticles, has good ink absorption by its porous structure, can form high-resolution image, have higher printing ink compatibility, and demonstrated high gloss.
Have porous matter ink-receiver layers such as containing silicon dioxide microparticle and water-soluble aluminum ink jet recording sheet oneself be disclosed (as reference patent documentation 3), and record when keeping its glossiness and ink absorption, also improved resistance to water, light resistance and surface checking.In addition, ink jet recording sheet with the porous matter ink-receiver layer that contains fumed silica and both sexes or non-ionic surface active agent also is disclosed (as reference patent documentation 4), and record when keeping its glossiness and ink absorption, improved cohesion and surface checking.In addition, ink jet recording sheet with the porous matter look material receiving layer that contains inorganic particles and amphoteric surfactant also is disclosed (as reference patent documentation 5), and record when keeping ink absorption, improved and covered with paint, lacquer, colour wash, etc. inhomogeneous and surface checking and image ooze the problem of spreading and sinking in.
Yet, in above-mentioned any ink jet recording sheet,, can't think to have reached for a long time and can fully satisfy image simultaneously and ooze and spread and sink in and the sunproof level of image though kept glossiness and ink absorption.
[patent documentation 1] spy opens flat 10-119423 communique
[patent documentation 2] spy opens flat 10-217601 communique
[patent documentation 3] spy opens the 2000-309157 communique
[patent documentation 4] spy opens the 2000-351269 communique
[patent documentation 5] spy opens the 2001-246838 communique
As mentioned above, so far fail to provide look material receiving layer to have the good ink absorbability and can form high-definition picture, this imaging simultaneously has resistance to water and the good printing ink compatibility of glossiness, and has well long-term anti-image and ooze and spread and sink in and sunproof ink jet recording sheet.
Summary of the invention
The object of the present invention is to provide and a kind ofly improved anti-image and ooze and spread and sink in and sunproof ink jet recording sheet.
Utilize following ink jet recording sheet can realize purpose of the present invention.
＜1〉a kind of ink jet recording sheet has on supporter in the ink jet recording sheet of look material receiving layer, it is characterized in that: this look material receiving layer contains the complex that is formed by carboxylic acid shown in the following general formula (I) and the above metal of divalent at least.
(R
1)
m-N L-CO
2H)
nGeneral formula (I)
[in the general formula (I), R
1Be hydrogen atom, aliphatic group, aromatic group, heterocyclic group, L is the linking group of divalent.M and n are the integer more than 0, (m+n) are 3 or 4.When this (m+n) was 4, the nitrogen-atoms in the general formula (1) formed quaternary ammonium cation, and a carboxyl in the general formula (I) becomes anion or R of dissociated state
1Contain the anionic property group.]
＜2〉above-mentioned＜1〉described ink jet recording sheet, it is characterized in that: the above metal of described divalent is to be selected from least a in aluminium, titanium, the zirconium.
＜3〉above-mentioned＜1〉or＜2〉described ink jet recording sheet, it is characterized in that: the content of the complex that is formed by described carboxylic acid and the metal more than the divalent is 0.01g/m
2～20g/m
2
＜4〉above-mentioned＜1 〉～＜3 described in ink jet recording sheet, it is characterized in that: also contain water-soluble resin in the described look material receiving layer.
＜5〉above-mentioned＜4〉described ink jet recording sheet, it is characterized in that: described water-soluble resin is from polyvinyl alcohol resin, cellulosic resin, ether-containing key resin, contains the carbamoyl resin, contains select carboxy resin and the gelatin class at least a.
＜6〉above-mentioned＜4〉or＜5 described in ink jet recording sheet, it is characterized in that: contain the crosslinking agent that can make water-soluble resin crosslinked in the described look material receiving layer.
＜7〉above-mentioned＜1 〉～＜6 in any one described ink jet recording sheet, it is characterized in that: also contain particulate in the described look material receiving layer.
＜8〉above-mentioned＜7〉described in ink jet recording sheet, it is characterized in that: described particulate is to be selected from silicon dioxide microparticle, cataloid, alumina particulate and to intend at least a in the boehmite.
＜9〉above-mentioned＜8〉described in ink jet recording sheet, it is characterized in that: described particulate is the fumed silica particulate, and then as containing the fumed silica water dispersion of this fumed silica and dispersant, is used for look material receiving layer.
＜10〉above-mentioned＜9〉described ink jet recording sheet, it is characterized in that: the dispersant of described fumed silica, at least a for what the compound dispersing agent below 2.0, select from the I/O value.
＜11〉above-mentioned＜1 〉～＜10 in any one described ink jet recording sheet, it is characterized in that: also contain mordant in the described look material receiving layer.
＜12〉above-mentioned＜1 〉～＜11 in any one described ink jet recording sheet, it is characterized in that: described look material receiving layer is the layer that the coating layer generation crosslinking curing that is coated with the coating fluid that contains particulate and water-soluble resin is at least formed, and this crosslinking curing be by to described coating fluid or/and down the note alkaline solution add crosslinking agent, and (1) at coating described coating fluid and when forming coating layer, any time point during perhaps this coating layer shows before falling-rate periods of drying speed in the process of (2) coating layer of forming at drying coated described coating fluid provides pH to carry out at the alkaline solution more than 8 to described coating layer.
The specific embodiment
Below, ink jet recording sheet of the present invention is described in detail.
In the ink jet recording sheet of the present invention, contain coloured material receiving layer on supporter, this look material receiving layer contains at least by the complex of remembering that down carboxylic acid shown in the general formula (I) and the above metal of divalent form.
(R
1)
m-N L-CO
2H)
nGeneral formula (I)
Because look material receiving layer contains this kind complex, ink jet recording sheet of the present invention can suppress the light resistance of spreading and sinking in and can improve image greatly of oozing of document image in long-time when having good glossiness and ink absorption.
Explain the formation of ink jet recording sheet of the present invention below.
(with the carboxylic acid of general formula (I) expression)
In the above-mentioned general formula (I), R
1Expression hydrogen atom, aliphatic group, aromatic group, heterocyclic group.
R
1During the expression fat-based, can enumerate alkyl, thiazolinyl, alkynyl, aralkyl etc. as this fat-based, these groups can contain substituting group again.Wherein preferably alkyl, substituted alkyl, thiazolinyl, substituted alkenyl, aralkyl, substituted aralkyl, more preferably alkyl and substituted alkyl.This aliphatic group can be the chain aliphatic group in addition, also can be cyclic aliphatic group, and the chain aliphatic group also can contain side chain again.
As using R
1The abovementioned alkyl of expression also can have substituting group, can enumerate the alkyl of a straight chain shape or a chain, ring-type.The carbon number of this alkyl preferably 1～30, more preferably 1～20.The carbon number of the moieties of substituted alkyl, also preferred in same scope.As the concrete example of this alkyl, can enumerate as methyl, ethyl, propyl group, butyl, amyl group, hexyl, octyl group, 2-ethylhexyl, uncle's octyl group, decyl, dodecyl, octadecyl, cyclohexyl, cyclopenta, neopentyl, isopropyl, isobutyl group etc.
R
1Can enumerate carboxyl as its substituting group during for substituted alkyl, sulfo group, cyano group, halogen atom (fluorine atom for example, the chlorine atom, bromine atoms), hydroxyl, carbon number is at (the methoxycarbonyl group for example of the alkoxy carbonyl group below 30, carbethoxyl group, benzyloxycarbonyl group), carbon number is at the aryloxy carbonyl below 30 (for example carbobenzoxy), carbon number is at (for example, the sulfonyloxy methyl amido carbonyl of the alkylsulfonamido carbonyl below 30, octyl group sulfoamido carbonyl), aryl-sulfonyl amino carbonyl (for example tosyl amido carbonyl), carbon number is at (the Benzamido sulfonyl for example of the amide groups sulfonyl below 30, the acetamido sulfonyl, pivaloyl amido sulfonyl);
Carbon number is at (the methoxyl group for example of the alkoxyl below 30, ethyoxyl, benzyloxy, benzene oxygen ethyoxyl, benzene ethyoxyl etc.), carbon number is at the arylthio below 30, alkylthio group (thiophenyl for example, methyl mercapto, ethylmercapto group, dodecane sulfenyl etc.), carbon number is at (the phenoxy group for example of the aryloxy group below 30, to toloxyl, the 1-naphthoxy, 2-naphthoxy etc.), nitro, carbon number is at the alkyl below 30, alkoxyl carbonyl oxygen base (methoxyl group carbonyl oxygen base for example, octadecane oxygen base carbonyl oxygen base, phenoxy group ethyoxyl carbonyl oxygen base), aryloxy group carbonyl oxygen base (phenoxy group carbonyl oxygen base for example, chloro phenoxy group carbonyl oxygen base);
Carbon number at the acyloxy below 30 (for example, acetoxyl group, propionyloxy etc.), carbon number at the acyl group below 30 (for example, acetyl group, propiono, benzoyl), carbamoyl (for example, carbamoyl, N, the N-formyl-dimethylamino, morpholino carbonyl, piperidino carbonyl etc.), sulfamoyl (for example, sulfamoyl, N, N-dimethylamino sulfonyl, the morpholino sulfonyl, piperidyl sulfonyl etc.), carbon number is at alkane sulfonyl (for example, the mesyl below 30, trifluoromethyl sulfonyl, ethylsulfonyl, the fourth sulfonyl, the dodecyl sulfonyl), arylsulfonyl (benzenesulfonyl for example, tosyl, the naphthalene sulfonyl base, the pyridine sulfonyl, the quinoline sulfonyl), carbon number is at (the phenyl for example of the aryl below 30, dichlorophenyl, toluyl, methoxyphenyl, the diethylin phenyl, the acetamido phenyl, the methoxycarbonyl group phenyl, hydroxyphenyl, uncle's octyl phenyl, naphthyl);
Substituted-amino is (for example amino, alkylamino radical, di alkylamino group, aryl amine, the diaryl-amine base, amide groups etc.), replace phosphono (phosphono for example, diethyl phosphonyl, the diphenylphosphine acyl group), heterocyclic radical (pyridine radicals for example, quinolyl, furyl, thienyl, tetrahydrofuran base, pyrazolyl, different azoles base, isothiazolyl, imidazole radicals, azoles base, thiazolyl, pyridazinyl, pyrimidine radicals, pyrazinyl, triazolyl, tetrazole radical, the benzoxazol base, benzimidazolyl, isoquinolyl, thiadiazolyl group, the morpholino base, piperidyl, piperazinyl, indyl, isoindolyl, thiomorpholine is for base), urea groups (methylurea base for example, the dimethyl urea groups, phenylcarbamido etc.);
The sulfonamides amido (for example; dipropyl sulfonamides amido etc.); alkoxycarbonyl amido (for example carbethoxyl group amino etc.); aryloxy carbonyl amino (for example carbobenzoxy amino); alkyl sulphinyl (for example methylsulfinyl), aryl sulfonyl kia (for example, phenyl sulfinyl etc.); silicyl (for example trimethoxysilyl, triethoxysilyl etc.), siloxy (for example trimethylsiloxy etc.) etc.
Here, as the substituent carboxyl of abovementioned alkyl, sulfo group, hydroxyl, phosphono etc., also can and cation (M
+Thereby) in conjunction with the form that forms salt separately as-COO
-M
+,-SO
3M
+,-O
-M
+,-PO (OH) O
-M
+,-PO (O
-M
+)
2This moment is as the cation that forms salt, relatively be fit to just like organic cation compound, transition metal coordination complex cation (in the special permission 2791143 disclosed compound etc.), perhaps metal cation is (as Na
+, K
+, Li
+, Ag
+, Fe
2+, Fe
3+, Cu
+, Cu
2+, Zn
2+, Al
3+, Ca
2+Deng).
Organic cation compound as above-mentioned for example can use quaternary ammonium cation, level Four pyridine cation, level Four quinoline cation, cation, iodine cation, sulfonium cation, pigment cation etc.
As the concrete example of above-mentioned quaternary ammonium cation, can enumerate as tetraalkylammonium cation (for example tetramethylammonium cation, TBuA cation), four aryl ammonium cations (for example four puratized agricultural spray cations) etc.
As above-mentioned level Four pyridine cation, can enumerate as N-alkyl pyridine cation (for example N-picoline cation), N-aryl-pyridine cation (as N-phenylpyridine cation), N-alkoxy pyridines cation (as 4-phenyl-N-methoxyl group-pyridine cation), N-benzoyl pyridine cation etc.
As level Four quinoline cation, can enumerate as N-alkyl quinoline cation (as N-methylquinoline cation), N-aryl quinoline cation (for example N-phenylchinoline cation) etc.
Above-mentioned cation can be enumerated as four aryl cations (for example tetraphenyl cation) etc.Can enumerate as diaryl iodine cation (as diphenyl iodine cation) etc. as iodine cation.Can enumerate as triaryl sulphur cation (for example triphenyl sulphur cation) etc. as sulfonium cation.
Can enumerate as diaryl iodine cation (as diphenyl iodine cation) etc. as iodine cation.Can enumerate as triaryl sulphur cation (for example triphenyl sulphur cation) etc. as sulfonium cation.
And then, can enumerate as open in the section of flat 9-188686 communique [0020]～[0038] disclosed compound etc. the spy as the cation that forms salt.
As using R
1The above-mentioned thiazolinyl of expression can have substituting group, can enumerate the thiazolinyl of straight chain shape and a chain or ring-type.The carbon number of this thiazolinyl preferably 2～30, more preferably 2～20.The carbon number of the alkenyl part in the substituted alkenyl, also preferred in same scope.As the concrete example of this thiazolinyl, can enumerate as vinyl pi-allyl, prenyl, geranyl, oleyl, cycloalkenyl group (for example 2-cyclopentene-1-base, 2-cyclohexene-1-yl), two ring [2,2,1] hept-2-ene"-1-bases, two ring [2,2,2] oct-2-ene-4-bases etc.
R
1Its substituting group during for substituted alkenyl can be enumerated the group identical with the substituting group of above-mentioned substituted alkyl.
Use R
1The above-mentioned alkynyl of expression can have substituting group, can enumerate the alkynyl of a straight chain shape and a chain, ring-type.The carbon number of this alkynyl preferably 2～30, more preferably 2～20.The carbon number of the alkynyl part of substituted alkynyl, also preferred in same scope.Can enumerate as acetenyl propargyl, trimethyl silyl acetenyl etc. as the concrete example of this alkynyl.
R
1Its substituting group during for substituted alkynyl can be enumerated the group identical with the substituting group of above-mentioned substituted alkyl.
As using R
1The above-mentioned aralkyl of expression can have substituting group, can be the aralkyl of straight chain shape, a chain and ring-type.The carbon number of this aralkyl preferably 7～35, more preferably 7～25.The carbon number of the aralkyl moiety of substituted aralkyl, also preferred in same scope.Can enumerate as benzyl, methyl-benzyl, octyl group benzyl, dodecylbenzyl, cetyl benzyl, dimethyl benzyl, octyloxy benzyl, octadecyl amino carbonyl benzyl, benzyl chloride base etc. as the concrete example of this aralkyl.
R
1Its substituting group during for substituted aralkyl can be enumerated the group identical with the substituting group of above-mentioned substituted alkyl.
R
1During for aromatic radical, can enumerate as aryl, substituted aryl as this aromatic radical.The carbon number of this aryl preferably 6～30, more preferably 6～20.The carbon number of the aryl moiety of substituted aryl is also preferred in same scope.This aryl concrete example is as phenyl, Alpha-Naphthyl, betanaphthyl etc.
R
1During for substituted aryl, can enumerate the group identical with the substituting group of above-mentioned substituted alkyl as its substituting group.
R
1During the expression heterocyclic group, this heterocyclic group can have substituting group, can be to contain nitrogen-atoms, oxygen atom or/and the heterocyclic group of sulphur atom.The concrete example of this heterocyclic group can be enumerated as furyl, thienyl, pyridine radicals, pyrazolyl, different azoles base, isothiazolyl, imidazole radicals, azoles base, thiazolyl, pyridazinyl, pyrimidine radicals, pyrazinyl, triazolyl, tetrazole radical, quinolyl, benzothiazolyl, benzoxazol base, benzimidazolyl, isoquinolyl, thiadiazolyl group, morpholino base, piperidyl, thiomorpholine for base, tetrahydrofuran base, piperazinyl, indyl, isoindolyl etc.
As R
1Its substituting group during for the substituted heterocycle group can be enumerated the group identical with the substituting group of above-mentioned substituted alkyl.
In general formula (I), L represents the linking group of divalent.
As using the represented linking group of L; specifically can enumerate as alkylene (for example methylene, ethylene, trimethylene, fourth support, pentamethylene etc.), arlydene (penylene for example; naphthylene etc.), alkenylene (vinylene for example; propylene support etc.); alkynylene (for example propine support etc.) wherein, can contain hetero atoms such as (1) oxygen atom, sulphur atom, nitrogen-atoms; perhaps heteroatomic bonds such as (2) ehter bond, ester bond, amino key, acid amides base key, sulphonyl base key, urea groups key can also contain substituting group in addition.As this divalent linking group, preferably carbon number is that 6～18 arlydene, carbon number are 2～12 alkenylene and alkynylene at alkylene, the carbon number of 1-12.
When being substituted, L can enumerate the group identical with the substituting group of above-mentioned substituted alkyl as its substituting group.
In the general formula (I), m and n represent the integer more than 0, (m+n) are 3 or 4.When (m+n) was 4, the nitrogen-atoms in the general formula (I) became quaternary ammonium cation, and a carboxyl in the general formula (I) becomes the anion (COO of disassociation state
-), perhaps as abovementioned alkyl (R
1) substituent carboxyl, sulfo group, hydroxyl, phosphono, 1 R
1Contain the anionic property group.
In the represented carboxylic acid of also general formula (I), especially spread and sink in and the light resistance aspect is considered, preferably with the carboxylic acid compound shown in note general formula (II) or the general formula (III) down from further raising image is impervious.
[changing 4]
R
4-N L-CO
2H)
2General formula (III)
In last note general formula (II) or general formula (III), R
2～R
4With the R in the above-mentioned general formula (I)
1Identical, expression hydrogen atom, aliphatic group, aromatic group, heterocyclic group, wherein preferably hydrogen atom or aliphatic group.L have with above-mentioned general formula (I) in the identical meaning of L, its preferred group is also identical.
As the total carbon atom number with the represented carboxylic acid compound of general formula (I), preferably more than 2, more preferential is more than 4, particularly preferably is more than 6.
In addition, when the carboxylic acid compound with general formula (1) expression was uncle's ammonia, this compound also can form salt with the acid combination.
Particular compound shown in the general formula (I) is as follows, and still, the present invention not merely is limited to these compounds.
Glycine, imido-acetic acid, ethylenediamine-N, N '-oxalic acid, N-(2-ethoxy)-imido-acetic acid, the cyano group triacetic acid, methyl amimoacetic acid, dimethylglycine, triein (tricin), alanine, Beta-alanine, valine, leucine, norvaline, isoleucine, aminobutyric acid, amino dodecyl acid, serine, isoerine, homoserine, threonine, proline, the N-nipecotic acid, lysine, aspartic acid, glutamic acid, cysteine, homocysteine, methionine, s-carboxyl methyl cysteine, cystine.
[changing 5]
(1)C
2H
5N(CH
2CO
2H)
2 (2)C
4H
9N(CH
2CO
2H)
2
(3)C
8H
17N(CH
2CO
2H)
2 (4)C
12H
25N(CH
2CO
2H)
2
(5)C
14H
25N(CH
2CO
2H)
2 (6)C
18H
37N(CH
2CO
2H)
2
(7)C
12H
25NHCH
2CO
2H (8)(CH
3)
3N
+(CH
2)
3CO
2 -
(metal that divalent the is above and formation of complex)
Then, to and general formula (I) shown in the carboxylic acid reaction above metal of divalent that forms complex used among the present invention be described in detail.
As these metal kinds more than divalent, can enumerate as magnesium, aluminium, calcium, scandium, titanium, vanadium, manganese, iron, nickel, chromium, copper, zinc, gallium germanium, strontium, yttrium, zirconium, molybdenum, indium, barium, the metal that divalents such as lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, dysprosium, erbium, ytterbium, hafnium, tungsten, bismuth are above.Wherein, as the metal kind more than the divalent of the present invention, the metal that preferred trivalent is above, wherein preferably aluminium, titanium, zirconium, more preferably aluminium and zirconium.
The metal that above-mentioned divalent is above, can with weak acid or strong acid in conjunction with forming salt, also can form hydroxide, hydrogen halides oxygen compound, complex etc., the complex that the carboxylic acid reaction that they and above-mentioned general formula (I) are represented generates can be contained in the look material receiving layer of ink jet recording sheet of the present invention.The concrete example of these slaines, hydroxide, hydrogen halides oxide and complex is as described below.
That is calcium acetate,, calcium chloride, calcium formate, calcium sulfate, barium acetate, barium sulfate, barium phosphate, manganese chloride, manganese acetate, two hydration formic acid manganese, six hydrated manganese sulfate ammoniums, copper chloride, two hydration ammonium chloride copper (II), copper sulphate, cobalt chloride, the thiocyanic acid cobalt, cobaltous sulfate, six hydration nickel sulfate, Nickel dichloride hexahydrate, four hydration nickel acetates, Nickel diammonium disulfate hexahydrate, four hydration nickel sulfamic acids, aluminum sulfate, al alum, aluminium sulfite, thiosulfuric acid aluminium, aluminium polychloride, ANN aluminium nitrate nonahydrate, Aluminium chloride hexahydrate, ferrous bromide, frerrous chloride, iron chloride, ferrous sulfate, ferric sulfate, zinc phenolsulfonate, zinc bromide, zinc chloride, zinc nitrate hexahydrate, zinc sulfate, titanium tetrachloride, tetra isopropyl titanate, the titanium acetylacetone complex, the lactic acid titanium, acetylacetone,2,4-pentanedione zirconium complex, the acetic acid zirconium, zirconium sulfate, zirconium carbonate ammonium, zirconium stearate, zirconium caprylate, zirconium nitrate, basic zirconium chloride, the chlorine zirconium hydroxide, chromic acetate, chromium sulfate, magnesium sulfate, six hydration manganese chlorides, nine hydration manganese citrates, sodium phosphotungstate, natrium citricum tungsten, 12 phosphotungstic acid n hydrates, 12 silico-tungstic acids, 26 hydrates, molybdenum chloride, 12 phosphomolybdic acid n hydrates, gallium nitrate, nitric acid germanium, strontium nitrate, the acetic acid yttrium, yttrium chloride, yttrium nitrate, indium nitrate, lanthanum nitrate, lanthanum chloride, lanthanum acetate, the benzoic acid lanthanum, cerium chloride, cerous sulfate, cerium octoate, praseodymium nitrate, neodymium nitrate, samaric nitrate, europium nitrate, gadolinium nitrate, dysprosium nitrate, erbium nitrate, ytterbium nitrate, hafnium chloride, bismuth nitrate etc.
In above-mentioned compound, preferred compound has aluminum contained compounds such as aluminum sulfate, al alum, aluminium sulfite, thiosulfuric acid aluminium, aluminium polychloride, ANN aluminium nitrate nonahydrate, Aluminium chloride hexahydrate; Titanium-containing compounds such as titanium tetrachloride, tetra isopropyl titanate, titanium acetylacetone complex, lactic acid titanium; And acetylacetone,2,4-pentanedione zirconium, acetic acid zirconium, basic zirconium phosphate, zirconium carbonate ammonium, zirconium stearate, zirconium caprylate, zirconium nitrate, basic zirconium chloride, zirconium-containing compounds such as chlorine zirconium hydroxide, more preferably aluminium polychloride, basic zirconium chloride.
When making ink jet recording sheet of the present invention, elder generation reacts after the generation complex with carboxylic acid shown in the above-mentioned general formula (I) and the above metal of divalent, this complex can be added to look material receiving layer with using in the coating fluid, perhaps also can modulation look material receiving layer with coating fluid or/and during the mordant coating fluid, simultaneously or add carboxylic acid shown in the general formula (I) and the above metal of divalent respectively, these compounds are directly used after forming complex or/and react in the modulated process of mordant coating fluid with coating fluid at look material receiving layer.
In addition, in the present invention, with regard to the complex that is formed by the above metal of the carboxylic acid shown in the general formula (I) and divalent, water-soluble or oil-soluble or solid shape all can.If the oil-soluble complex then can disperse to add or add as organic solvent by emulsification, if solid shape complex then can disperse thing to add as emulsification after micronize.
In the look material receiving layer of ink jet recording sheet of the present invention, the amount of the above-mentioned complex that is formed by the carboxylic acid of general formula (I) and the above metal of divalent is to spread and sink in and the consideration of light resistance aspect, preferably 0.01g/m from further raising image is impervious
2～20g/m
2, 0.1g/m more preferably
2～7g/m
2, 0.5g/m most preferably
2～5g/m
2
If above-mentioned complex contain quantity not sufficient 0.01g/m
2, then image impervious spread and sink in and light resistance to improve effect abundant inadequately, on the other hand.If this content surpasses 20g/m
2, condense easily when then using particulate, thereby can destroy the glossiness of sheet for recording.
In the look material receiving layer of ink jet recording sheet of the present invention, contain the complex that forms by carboxylic acid shown in the general formula (I) and the above metal of divalent, when obtaining this complex, ratio as the reaction mole of above-mentioned carboxylic acid shown in the general formula (I) and the above metal of divalent, preferably 1: 100～100: 1, more preferably 1: 20～20: 1, particularly preferably be 1: 10～10: 1.
In addition, in the look material receiving layer of ink jet recording sheet of the present invention, with the content of the carboxylic moiety shown in the above-mentioned general formula (I), preferably 0.01g/m
2～5g/m
2, 0.05g/m more preferably
2～4g/m
2, particularly preferably be 0.07g/m
2～3g/m
2
In addition, in the look material receiving layer of ink jet recording sheet of the present invention, the content of the above metal of above-mentioned divalent is 0.1g/m preferably
2～20g/m
2, 0.4g/m more preferably
2～10g/m
2, particularly preferably be 0.8g/m
2～5g/m
2
(water-soluble resin)
In the ink jet recording sheet of the present invention, preferably when containing, contain water-soluble resin in its look material receiving layer by carboxylic acid shown in the general formula (I) and the formed complex of the metal more than the divalent.
As above-mentioned water-soluble resin; can enumerate as, the resin that contains hydroxyl as the hydrophilic structure unit is polyvinyl alcohol resin [polyvinyl alcohol (PVA) for example; the acetoacetyl modified PVA; cation-modified PVA; anion-modified PVA; the silanol modified PVA; polyethylene acetal etc.]; cellulosic resin [methylcellulose (MC); ethyl cellulose (EC); hydroxyethylcellulose (HEC); carboxymethyl cellulose (CMC); hydroxypropyl cellulose (HPC); HEMC; hydroxypropyl methylcellulose etc.]; the chitin class; the shitosan class; starch; the ether-containing key resin [for example; PEO (PEO); PPOX (PPO); polyethylene glycol (PEG); polyvinylether (PVE) etc.]; resin [the polyacrylamide (PAAM) for example that contains carbamoyl; polyvinylpyrrolidone (PVP); polyacrylic hydrazide etc.] etc.
In addition, as disassociation property group, also can use carboxylic polypropylene hydrochlorate, maleic acid resin, alginate, gelatin class etc.
Wherein, special preferably polyethylene alcohol (PVA) resinoid.Concrete example as this polyvinyl alcohol, can use disclosed polyvinyl alcohol in the following document, promptly special fair 4-52786 number, special fair 5-67432 number, special fair 7-29479 number, specially permit No. 2537827, special fair 7-57553 number, specially permit No. 2502998, specially permit No. 3053231, the spy opens clear 63-176173 number, specially permit No. 2604367, Te Kaiping 7-276787 number, Te Kaiping 9-207425 number, Te Kaiping 11-58941 number, the spy opens 2000-135858 number, the spy opens 2001-205924 number, the spy opens 2001-287444 number, the spy opens clear 62-278080 number, Te Kaiping 9-39373 number, specially permit No. 2750433, the spy opens 2000-158801 number, the spy opens 2001-213405 number, the spy opens 2001-328345 number, Te Kaiping 8-324105 number, disclosed polyvinyl alcohol in the Te Kaiping 11-348417 grade.
In addition, can also use the water-soluble resin beyond the polyvinyl alcohol resin, for example also can enumerate the spy and open in [0011～0014] section of flat 11-165461 communique disclosed compound etc.
These water-soluble resins may be used alone, used in two or more.In addition, in ink jet recording sheet of the present invention, the content of above-mentioned water-soluble resin is with respect to all solids composition quality of look material receiving layer, preferably 9～40 quality %, more preferably 12～33 quality %.
In addition, polyvinyl alcohol resin also can also be used with other above-mentioned water-soluble resins.With described other water-soluble resins and above-mentioned polyvinyl alcohol time-like, in all water-soluble resins, the content of polyvinyl alcohol resin is preferably more than 50 quality %, more preferably more than 70 quality % also.
(particulate)
In ink jet recording sheet of the present invention, its look material receiving layer is preferably in when containing the complex that is formed by above-mentioned carboxylic acid among the present invention and metal and also contains particulate, particularly preferably is this particulate and above-mentioned water-soluble resin and usefulness.
Because of containing particulate in this look material receiving layer, can obtain porous structure, thereby can improve the absorbent properties of printing ink.Particularly, when the solid component content of this particulate in the look material receiving layer when 50 quality % are above, when more preferably surpassing 60 quality %, can form the higher porous structure of voidage, can obtain to have the ink jet recording sheet of sufficient ink absorption thus, therefore preferred.At this, the solid component content of particulate in look material receiving layer is the content that calculates according to the composition except water in the composition that constitutes look material receiving layer.
As the particulate that uses in the present invention, can enumerate organic fine particles and inorganic particles, but consider from ink absorption and picture steadiness aspect, preferably contain inorganic particles.
As above-mentioned organic fine particles, what preferably use is the polymer particles that obtains through emulsion polymerisation, micro-emulsion polymerization, emulsifier-free emulsion polymerization, seeding polymerization, dispersin polymerization, suspension polymerisation etc., specifically can enumerate the powder of polyethylene, polypropylene, polystyrene, polyacrylate, polyamide, silicones, phenolic resins, natural polymer etc., the polymer particles of latex or emulsion form etc.
As above-mentioned inorganic particles, can enumerate for example silicon dioxide microparticle, cataloid, titanium dioxide, barium sulfate, calcium silicates, zeolite, kaolinite, galapectite, mica, talcum, calcium carbonate, magnesium carbonate, calcium sulfate, plan boehmite, zinc oxide, zinc hydroxide, aluminium oxide, alumina silicate, calcium silicates, magnesium silicate, zirconia, zirconium hydroxide, cerium oxide, lanthana, yittrium oxide etc.Wherein, from forming the viewpoint of good porous structure, preferred silicon dioxide microparticle, cataloid, alumina particulate or plan boehmite.These particulates can use with the state of primary particle, also can use under the state that forms the secondary particulate.The average primary particle diameter of these particulates is preferably below 2 μ m, more preferably below 200nm.
More preferably average primary particle diameter at the cataloid below the 30nm, average primary particle diameter alumina particulate or the average pore radius plan boehmite that is 2～15nm below 20nm, particularly preferably is silicon dioxide microparticle, alumina particulate, plan boehmite at the silicon dioxide microparticle below the 20nm, average primary particle diameter.
Silicon dioxide microparticle roughly is divided into damp process particulate and dry process (vapor phase method) particulate according to manufacture method usually.What mainly adopt in above-mentioned damp process is to decompose the generation active silica by the acid of silicate, and make it to obtain through coagulative precipitation after the appropriate polymerization method of aqueous silicon dioxide.On the other hand, main employing is in the above-mentioned vapor phase method, according to the method (flame hydrolysis) of the high temperature vapor phase hydrolysis that utilizes silicon halide and in electric furnace, utilize the electric arc heated silica sand and coke making it the method (arc process) of reduction and gaseous back with air oxidation, and obtain the method for anhydride silica." fumed silica " just is meant the anhydride silica that utilizes this vapor phase method to obtain.The silicon dioxide microparticle that uses among the present invention, especially preferred is back a kind of " fumed silica " particulate.
Above-mentioned " fumed silica " compared in the density of silane surface alcohol radical or had or not aspect such as hole different with aqueous silicon dioxide, also will show different character thereupon, is fit to form the higher three-dimensional structure of voidage.Though its reason it be unclear that, can be presumed as follows, that is, in aqueous silicon dioxide, the density of the silanol group of microparticle surfaces has 5～8/nm
2More than, thereby the silicon dioxide microparticle ratio is easier to tight cohesion (aggregation), on the other hand, the density of the silanol group of microparticle surfaces has only 2～3/nm in fumed silica
2, therefore forming loose soft cohesion (flocculate), its result can form the higher structure of voidage.
Above-mentioned " fumed silica ", because its specific area is very big, therefore have higher ink absorption and conservation rate, and because its refractive index is low, can give the transparency to receiving layer when being dispersed to suitable particle diameter, have the advantage that can obtain higher colour developing concentration and good colour rendering.Transparent these characteristics of receiving layer are not only extremely important for the purposes such as OHP that necessarily require the transparency, and when being used for the sheet for recording of gloss photographic paper etc., and are also because of obtaining higher color density and well colour rendering and gloss, equally very important.
The average primary particle diameter of above-mentioned " fumed silica " preferably below 30nm, more preferably below 20nm, particularly preferably is below 10nm, most preferably at 3～10nm.In above-mentioned fumed silica, owing to exist, adsorb easily between the particle, if therefore average primary particle diameter is selected in below the 30nm by the formed hydrogen bond of silanol group, then can form the higher structure of voidage, can promote its ink absorption significantly.
In addition, silicon dioxide microparticle also can also be used with other above-mentioned particulate.When these other particulates and above-mentioned fumed silica were share, the content of fumed silica in all particulates was preferably more than 30 quality %, more preferably more than 50 quality %.
As used in the present invention inorganic particles, preferably alumina particulate, hydrated alumina, their mixture or compound.Wherein, hydrated alumina is owing to can absorb printing ink well and carry out photographic fixing, and therefore comparatively desirable, especially preferred is to intend boehmite (Al
2O
3NH
2O).This hydrated alumina can use with various forms, but the angle of the smooth layer that is easy to get calmly considers that preferably the boehmite with the colloidal sol shape uses as raw material.
In the pore structure of above-mentioned plan boehmite, its average pore radius is 1～30nm, more preferably 2～15nm preferably.Preferably 0.3～2.0ml/g, more preferably 0.5～1.5ml/g of its pore volume in addition.Here for the mensuration of described pore radius and pore solvent, can carry out, for example utilize gas adsorption desorption analyzer (for example product of コ one Le one society's system " ォ system ニ ソ-プ 369 ") to measure with nitrogen adsorption desorption method.
In addition, in alumina particulate, preferably has vapor phase method aluminium oxide than bigger serface.The average primary particle diameter of this vapor phase method aluminium oxide is preferably below 30nm, more preferably below 20nm.
When being used in above-mentioned particulate in the ink jet recording sheet, also can be suitable for well under by the disclosed state of following document, for example the spy opens flat 10-81064 number, with 10-119423 number, with 10-157277 number, with 10-217601 number, with 11-348409 number, the spy opens 2001-138621 number, with 2000-43401 number, with 2000-211235 number, with 2000-309157 number, with 2001-96897 number, with 2001-138627 number, Te Kaiping 11-91242 number, with 8-2087 number, with 8-2090 number, with 8-2091 number, with 8-2093 number, with 8-174992 number, with 11-192777 number, the spy opens 2001-301314 number and waits disclosed state in the communique.
The above-mentioned water-soluble resin and the above-mentioned particulate of main composition look material of the present invention receiving layer can be respectively single raw material, also can use the mixed system of plurality of raw materials.
In addition, when the angle that keeps the transparency is considered and the kind of the water-soluble resin that is used in combination of particulate, especially silicon dioxide microparticle very important.When stating fumed silica in the use, as this water-soluble resin polyvinyl alcohol resin preferably, wherein preferably saponification degree is 70～100% polyvinyl alcohol resin, and more preferably saponification degree is 80～99.5% polyvinyl alcohol resin.
Above-mentioned polyvinyl alcohol resin contains hydroxyl in its construction unit, this hydroxyl can form hydrogen bond with the silanol group of above-mentioned silica particle surface, thereby is the tridimensional network of netted chain unit than the secondary particulate that is easier to form with silicon dioxide microparticle.Because the formation of this tridimensional network is thought to form the look material receiving layer that has than the porous structure of high voidage and sufficient intensity.
In ink mist recording, the porous matter look material receiving layer that obtains through said method can promptly absorb printing ink by capillarity, thereby the ink dot that can form " ooze and spread and sink in " that printing ink does not take place and have good just round property.
(the content ratio of particulate and water-soluble resin)
In ink jet recording sheet, the ratio [PB is than (x/y)] of the above-mentioned particulate (x) in the look material receiving layer and the mass content of above-mentioned water-soluble resin (y), the membrane structure of the material receiving layer of can checking colors and film-strength produce very big influence.When the ratio of this mass content [PB than] when becoming big, voidage and pore volume, surface area (each mass unit) change are big, but its density and intensity will descend.
In look material receiving layer of the present invention, for prevent owing to PB than the decline of the excessive film-strength that causes and the checking when dry, thereby and prevent to be stopped up by resin and make the less absorbefacient decline that causes printing ink of voidage because of the too small space that easily causes of the ratio of PB, therefore above-mentioned mass content than [PB is than (x/y)] preferably 1.5/1～10/1.
When passing through the transfer system of ink-jet printer, owing to can on sheet for recording, apply certain force of strain, so look material receiving layer need have sufficient film-strength.In addition, when slabbing is made in cutting processing,, also need to make this look material receiving layer to have sufficient film-strength in order to prevent breaking and peeling off etc. of look material receiving layer.After considering these factors, as the ratio (x/y) of above-mentioned PB more preferably below 5/1, on the other hand, in order to ensure its ink absorption fast in ink-jet printer, preferably more than 2: 1.
Be specially, for example fumed silica and the water-soluble resin of average primary particle diameter below 20nm formed coating fluid after disperseing fully than (x/y) with 2/1～5/1 PB in the aqueous solution, and on supporter, be coated with, make after this coating layer drying, can form with the secondary particle of silicon dioxide microparticle is the 3 D stereo network structure of netted chain, thus can form average fine pore below the 30nm, voidage is 50～80%, the pore specific volume more than 0.5ml/g, specific area is at 100m
2The multiple aperture plasma membrane of the light transmission that/g is above.
(crosslinking agent)
With regard to the look material receiving layer of ink jet recording sheet of the present invention, preferably also contain the crosslinking agent that can make this water-soluble resin crosslinked in the above-mentioned coating layer that contains water-soluble resin, especially preferred is the porous layer state that share above-mentioned particulate and above-mentioned water-soluble resin and finish curing by the cross-linking reaction of crosslinking agent and water-soluble resin.
Particularly preferred in polyvinyl alcohol crosslinked what use is boron compound at above-mentioned water-soluble resin.As this boron compound, can enumerate as borax, boric acid, borate (for example orthoboric acid salt, 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, consider from the angle of quick cross-linking reaction, preferably borax, boric acid, borate, more preferably boric acid.
As the crosslinking agent of water-soluble resin, also can use the compound except above-mentioned boron compound.The aldehyde compounds such as dialdehyde-based derivative of formaldehyde, glyoxal, butanedial, glutaraldehyde, dialdehyde stareh, natural plant gum for example; Ketone compounds such as diacetyl, 1,2-cyclopentanedione, 3-hexene-2,5-diketone; Two (2-chloroethyl) urea, two (2-chloroethyl) sulfone, 2,4-two chloro-6-hydroxyls-s-triazine sodium salt isoreactivity halogen compound; The active vinyl-compound of divinylsulfone, 1, two (the vinylsulfonyl)-2-propyl alcohol of 3-, N, N '-ethylene two (vinylsulfonyl acetamide), divinyl ketones, 1, two (acryloyl group) ureas, 1,3 of 3-, 5-triacryl-six hydrogen-s-triazine etc.; N-such as dimethylol urea, methylol dimethyl hydantion methylol compound; Melamine compounds such as trihydroxy methyl melamine, alkylation methylol melamine, melamine, benzo guanamine, melamine resin; The epoxides such as polyglycidyl ether of ethylene glycol diglycidylether, propylene glycol diglycidylether, polyethyleneglycol diglycidylether, two glycerine polyglycidyl ethers, spiral shell ethylene glycol diglycidylether, phenolic resins;
1,6-HDI, isocyanate ester compounds such as xyxylene vulcabond; No. the 3017280th, US Patent specification, with disclosed aziridine compounds in No. 2983611 etc.; Disclosed carbodiimides compounds in US Patent specification the 3100704th grade; 1,6-hexamethylene-N, N '-two second are embraced second such as urea and are embraced the imido grpup compounds; Halogenation such as mucochloric acid, glue phenoxy chloric acid carboxyl aldehyde compound; 2, two alkyl compounds of 3-dihydroxy two alkane etc.; Containing metal compounds such as lactic acid titanium, aluminum sulfate, chrome alum chromalum, potassium alum, zirconium acetate, chromium acetate; Polyamine compounds such as tetraethylene pentamine; Hydrazide compounds such as adipic dihydrazide; Contain the low molecule of two above azoles quinoline bases or polymer etc.; Disclosed multi-anhydride, sour chloride, disulfonic acid ester compounds in No. the 2725294th, US Patent specification, No. the 2725295th, US Patent specification, No. the 2726162nd, US Patent specification, No. the 3834902nd, the US Patent specification etc.; Disclosed active ester compound etc. in No. the 3542558th, US Patent specification, No. the 3251972nd, the US Patent specification etc.
Above-mentioned crosslinking agent can use separately also and can be used in combination.
Among the present invention, above-mentioned crosslinking curing is or/and add crosslinking agent in the following alkaline solution at the coating fluid (being designated hereinafter simply as " coating fluid A ") that contains particulate and water-soluble resin etc., and when (1) utilizes above-mentioned coating fluid to be coated with to form coating layer or (2) in the dry run of the formed coating layer of the above-mentioned coating fluid of coating, arbitrary time point before this coating layer presents falling-rate periods of drying speed is supplied in the pH value in the above-mentioned coating layer at the alkaline solution more than 8 (being designated hereinafter simply as " coating fluid B ").
When being example with the boron compound, the interpolation of above-mentioned crosslinking agent preferably is performed as follows.That is, when look material receiving layer is, be coated with the coating layer that obtains with the coating fluid (coating fluid A) of the water-soluble resin that contains particulate and polyvinyl alcohol when layer that crosslinking curing forms, this crosslinking curing is finished by following operation.Promptly, (1) when utilizing above-mentioned coating fluid to be coated with to form coating layer or (2) in the dry run of the formed coating layer of the above-mentioned coating fluid of coating, arbitrary time point before this coating layer presents falling-rate periods of drying speed offers the pH value in the above-mentioned coating layer at the alkaline solution more than 8 (being designated hereinafter simply as " coating fluid B ").As the boron compound of crosslinking agent, can be contained among either party of coating fluid A or coating fluid B, also can be contained in simultaneously among coating fluid A and the coating fluid B.
The use amount of above-mentioned crosslinking agent in look material receiving layer of the present invention is with respect to water-soluble resin preferably 1～50 quality %, more preferably 5～40 quality %.
(mordant)
For the resistance to water of improving formed image and anti-through the time ooze the performance of spreading and sinking in, in ink jet recording sheet of the present invention, preferably in look material receiving layer, add mordant.
Above-mentioned mordant is preferably had the polymer organic mordant (cationic mordant) or an inorganic mordant of cationic.By in look material receiving layer, using this mordant, thus can with the anionic property dyestuff as the liquid ink of the look material invariable colour material that interacts, can improve resistance to water and anti-through the time ooze the performance of spreading and sinking in.These organic mordants and inorganic mordant can be used separately separately, but also can be also with organic mordant and inorganic mordant.
As the use of mordant order, can adopt following any method, add it among the above-mentioned coating fluid A that contains particulate and water-soluble resin method, perhaps and might condense between the particulate time, add the method among the above-mentioned coating fluid B to.
As above-mentioned cationic mordant,, also can use the non-polymer mordant of cationic though what be suitable for is to contain polymer mordant just like primary～uncle amino or quaternary ammonium salt group as the cationic group.Consider that from the ink absorption aspect of improving look material receiving layer these mordants preferably use is weight average molecular weight at 500～100000 compound.
As above-mentioned polymer mordant, preferably contain the homopolymers of monomer (mordant dyeing monomer) of primary～uncle amino and salt thereof or quaternary ammonium salt group and the copolymer or the condensation polymer of this mordant dyeing monomer and other monomers (hereinafter to be referred as making " non-mordant dyeing monomer ").In addition, these polymer mordant can be used in any mode in water-soluble polymer or the water dispersible latex particle.
As above-mentioned monomer (mordant dyeing monomer), can enumerate as trimethyl-vinyl benzyl chlorination ammonium, a trimethyl-vinyl benzyl chlorination ammonium, triethyl group-to vinyl benzyl chlorination ammonium, a triethyl group-vinyl benzyl chlorination ammonium, N, N-dimethyl-N-ethyl-N-is to vinyl benzyl chlorination ammonium, N, N-diethyl-N-methyl-N-is to vinyl benzyl chlorination ammonium, N, N-dimethyl-N-n-pro-pyl-N-is to vinyl benzyl chlorination ammonium, N, N-dimethyl-N-n-octyl-N-is to vinyl benzyl chlorination ammonium, N, N-dimethyl-N-benzyl-N-is to vinyl benzyl chlorination ammonium, N, N-diethyl-N-benzyl-N-is to vinyl benzyl chlorination ammonium, N, N-dimethyl-N-(4-methyl) benzyl-N-is to vinyl benzyl chlorination ammonium, N, N-dimethyl-N-phenyl-N-is to vinyl benzyl chlorination ammonium;
Trimethyl-to the vinyl benzyl ammonium bromide, a trimethyl-vinyl benzyl ammonium bromide, trimethyl-to the vinyl benzyl ichthyodin, a trimethyl-vinyl benzyl ichthyodin, trimethyl-to the vinyl benzyl ammonium acetate, a trimethyl-vinyl benzyl ammonium acetate, N, N, N-triethyl group-N-2-(4-ethenylphenyl) ethyl ammonium chloride, N, N, N-triethyl group-N-2-(3-ethenylphenyl) ethyl ammonium chloride, N, N-diethyl-N-methyl-N-2-(4-vinyl phenyl) ethyl ammonium chloride, N, N-diethyl-N-methyl-N-2-(4-ethenylphenyl) ethyl ammonium acetate;
By N, N-dimethylaminoethyl (methyl) acrylate, N, N-diethyllaminoethyl (methyl) acrylate, N, N-dimethylamino-propyl (methyl) acrylate, N, N-lignocaine propyl group (methyl) acrylate, N, N-dimethylaminoethyl (methyl) third rare acid amides, N, N-diethyllaminoethyl (methyl) third rare acid amides, N, N-dimethylamino-propyl (methyl) third rare acid amides, N, the chloromethane of N-lignocaine propyl group (methyl) third rare acid amides, chloric ethane, bromomethane, bromic ether, the level Four thing that iodomethane or iodic etherization etc. obtain perhaps replaces the sulfonate that their anion obtains, alkylsulfonate, acetate or alkyl carboxylate etc.
As concrete compound, can enumerate as the monomethyl diallyl ammonium chloride, trimethyl-2-(methacryloxy) ethyl ammonium chloride, triethyl group-2-(methacryloxy) ethyl ammonium chloride, trimethyl-2-(acryloxy) ethyl ammonium chloride, triethyl group-2-(acryloxy) ethyl ammonium chloride, trimethyl-3-(methacryloxy) propyl ammonium chloride, triethyl group-3-(methacryloxy) propyl ammonium chloride, trimethyl-2-(methacryl amido) ethyl ammonium chloride, triethyl group-2-(methacryl amido) ethyl ammonium chloride, trimethyl-2-(acrylamido) ethyl ammonium chloride, triethyl group-2-(acrylamido) ethyl ammonium chloride, trimethyl-3-(methacryl amido) propyl ammonium chloride, triethyl group-3-(methacryl amido) propyl ammonium chloride, trimethyl-3-(acrylamido) propyl ammonium chloride, triethyl group-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, trimethyl-2-(methacryloxy) ethyl ammonium bromide, trimethyl-3-(acrylamido) propyl group ammonium bromide, trimethyl-2-(methacryloxy) ethylsulfonic acid ammonium, trimethyl-3-(acrylamido) propyl group ammonium acetate etc.
In addition, as monomer that can copolymerization for example N-vinyl imidazole, N-vinyl-glyoxal ethyline etc. are arranged.
In addition, also can use allylamine, diallylamine and derivative and salt etc.Example as these compounds, can enumerate as allylamine, allylamine hydrochloride, allylamine acetate, allylamine sulfate, diallylamine, diallylamine hydrochloride, diallylamine acetate, diallylamine sulfate, diallyl methylamine and its salt (as this salt, can enumerate hydrochloride, acetate, sulfate etc.), diallyl ethamine and its salt (for example hydrochloride, acetate, sulfate etc.), diallyl dimethyl ammonium salt (, chloride ion, acetic acid ion, sulfate ion etc. being arranged) as the balance anion of this salt.In addition,, therefore carry out polymerization, generally carry out corresponding desalting processing in the time of necessary with the form of salt because these allylamines and diallylamine derivative its polymerism when carrying out polymerization with the form of amine are relatively poor.
In addition, also can use monomers such as N-vinyl acetamide, N-vinyl formamide to carry out the vinylamine construction unit that polymerization generates through hydrolysis afterwards, formed thus salt also can use.
Above-mentioned non-mordant dyeing monomer is meant and does not contain primary～tertiary amine groups and alkalescence or cationic parts such as their salt or quaternary ammonium salt group in molecule, and the dyestuff in the discord printing ink takes place to interact or interact very little in fact monomer.
As above-mentioned non-mordant dyeing monomer, can enumerate as (methyl) alkyl acrylate; (methyl) acrylic acid cycloalkyl esters such as (methyl) cyclohexyl acrylate; (methyl) acrylic acid aryl esters such as (methyl) phenyl acrylate; Aralkyl esters such as (methyl) benzyl acrylate; Aromatic vinyl classes such as styrene, vinyltoluene, AMS; Vinyl esters such as vinylacetate, propionate; Allyl ester classes such as acetic acid allyl ester; Halogen such as vinylidene chloride, ethlyene dichloride monomer; Vinyl cyanide classes such as (methyl) acrylonitrile; Olefines such as ethene, propylene etc.
As above-mentioned (methyl) alkyl acrylate, preferably the carbon number of moieties is (methyl) alkyl acrylate of 1～18, for example, can enumerate (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) propyl acrylate, (methyl) isopropyl acrylate, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate, (methyl) Hexyl 2-propenoate, (methyl) 2-ethyl hexyl acrylate, (methyl) 2-EHA, (methyl) acrylic acid dodecane ester, (methyl) acrylic acid octadecane ester.
Wherein preferably methyl acrylate, ethyl acrylate, methyl methacrylate, EMA, hydroxyethyl methacrylate etc.
Above-mentioned non-mordant dyeing monomer can use separately also and can be used in combination.
And then, as above-mentioned polymer mordant, can enumerate as copolymer, diallyldimethylammonium chloride and SO with diallyl dimethyl ammoniumchloride, diallyldimethylammonium chloride and other monomers (mordant dyeing monomer, non-mordant dyeing monomer)
2Copolymer, polydiene propyl methylamine hydrochloride, polydiene propyl group hydrochloride etc. be the cyclic amine resin of representative and derivative (also comprising copolymer) thereof; Poly-diethylmethyl acryloxy ethamine, poly-trimethyl methacryloxyethyl ammonium chloride, poly dimethyl benzyl methacryloxyethyl ammonium chloride, poly dimethyl ethoxy acryloxy ethyl ammonium chloride etc. for the secondary amine of representative, tertiary amine or quaternary ammonium salt substituted alkyl (methyl) acrylate polymer and with the copolymer of other monomers; Second is embraced imines and derivative, polyallylamine and derivative thereof, polyvinylamine and derivative thereof etc. are the polyamine resinoid of representative to gather; With polyamide-polyamino resin, polyamine epichlorohydrin resin etc. is the polyamide of representative; With cationic starch, shitosan and chitosan derivatives etc. is the polysaccharide of representative; With dicyan diamides formaldehyde condensation products, dicyan diamides diethylenetriamines condensation polymer etc. is the dicyan diamide derivatives of representative; With poly-amidine and poly-amidine derivative; With dimethylamine epoxychloropropane addition polymers etc. is the dialkylamine epoxychloropropane addition polymers and the derivative thereof of representative; Contain copolymer of the styrene polymer of quaternary ammonium salt substituted alkyl and it and other monomers etc.
As above-mentioned polymer mordant, can enumerate disclosed material in the following document particularly, open clear 48-28325 number as the spy, with 54-74430 number, with 54-124726 number, with 55-22766 number, with 55-142339 number, with 60-23850 number, with 60-23851 number, with 60-23852 number, with 60-23853 number, with 60-57836 number, with 60-60643 number, with 60-118834 number, with 60-122940 number, with 60-122941 number, with 60-122942 number, with 60-235134 number, wait each communique Te Kaiping 1-161236 number, United States Patent (USP) 2484430, with No. 2548564, with No. 3148061, with No. 3309690, with No. 4115124, with No. 4124386, with No. 4193800, with No. 4273853, with No. 4282305, with No. 4450224, Te Kaiping 1-161236 number, with 10-81064 number, with 10-157277 number, with 10-217601 number, the spy opens 2001-138621 number, with 2000-211235 number, with 2001-138627 number, Te Kaiping 8-174992 number, special fair 5-35162 number, with 5-35163 number, with 5-35164 number, with 5-88846 number, specially permit No. 2648847, wait communique No. 2661677 together.
Also can use inorganic mordant as mordant of the present invention, for example multivalence water-soluble metal salt and hydrophobic metals salt compound etc.
As the inorganic mordant concrete example, can enumerate as from magnesium, aluminium, calcium, scandium, titanium, vanadium, manganese, iron, nickel, copper, zinc, gallium, germanium, strontium, yttrium, zirconium, molybdenum, indium, barium, the salt or the complex of the metal of selecting in the metals such as lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, dysprosium, erbium, ytterbium, hafnium, tungsten, bismuth.
As concrete compound, can enumerate as calcium acetate, calcium chloride, calcium formate, calcium sulfate, barium acetate, barium sulfate, barium phosphate, manganese chloride, manganese acetate, two hydration formic acid manganese, six hydrated manganese sulfate ammoniums, copper chloride, two hydration ammonium chloride copper (II), copper sulphate, cobalt chloride, the thiocyanic acid cobalt, cobaltous sulfate, six hydration nickel sulfate, Nickel dichloride hexahydrate, four hydration nickel acetates, Nickel diammonium disulfate hexahydrate, four hydration nickel sulfamic acids, aluminum sulfate, al alum, the many aluminium hydroxides of alkalescence, aluminium sulfite, thiosulfuric acid aluminium, aluminium polychloride, ANN aluminium nitrate nonahydrate, Aluminium chloride hexahydrate, ferrous bromide, frerrous chloride, iron chloride, ferrous sulfate, ferric sulfate, zinc phenolsulfonate, zinc bromide, zinc chloride, zinc nitrate hexahydrate, zinc sulfate, titanium tetrachloride, tetra isopropyl titanate, the titanium acetylacetone complex, the lactic acid titanium, acetylacetone,2,4-pentanedione zirconium complex, the acetic acid zirconium, zirconium sulfate, zirconium carbonate ammonium, zirconium stearate, zirconium caprylate, zirconium nitrate, basic zirconium chloride, the chlorine zirconium hydroxide, chromic acetate, chromium sulfate, magnesium sulfate, Magnesium dichloride hexahydrate, nine hydration magnesium citrates, sodium phosphotungstate, natrium citricum tungsten, 12 phosphotungstic acid n hydrates, 12 silico-tungstic acids, 26 hydrates, molybdenum chloride, 12 phosphomolybdic acid n hydrates, gallium nitrate, nitric acid germanium, strontium nitrate, the acetic acid yttrium, yttrium chloride, yttrium nitrate, indium nitrate, lanthanum nitrate, lanthanum chloride, lanthanum acetate, the benzoic acid lanthanum, cerium chloride, cerous sulfate, cerium octoate, praseodymium nitrate, neodymium nitrate, samaric nitrate, europium nitrate, gadolinium nitrate, dysprosium nitrate, erbium nitrate, ytterbium nitrate, hafnium chloride, bismuth nitrate etc.
As inorganic mordant of the present invention, the compound (salt or complex) of aluminum contained compound, titanium-containing compound, zirconium-containing compound, periodic table of elements IIIB family row metal preferably.
The content of above-mentioned mordant in look material receiving layer is 0.01g/m preferably
2～5g/m
2, 0.1g/m more preferably
2～3g/m
2
(other compositions)
In case of necessity, can in ink jet recording sheet of the present invention, add various known additives, for example acid, ultra-violet absorber, antioxidant, fluorescent whitening agent, monomer, polymerization initiator, polymerization inhibitor, the impervious agent of spreading and sinking in, anticorrisive agent, viscosity stabiliser, defoamer, surfactant, antistatic additive, delustering agent, anti-roll contract agent, anti-hydrated agent etc.
In the present invention, can in look material receiving layer, add acid.By adding acid, look material receiving layer surface pH value is adjusted to 3～8, preferably be adjusted to 5～7.Can improve the yellowing resistance of blank parts thus well, therefore preferred.The mensuration of surface p H can be carried out according to the A method (rubbing method) in the surface p H assay method of Japanese paper pulp technological associations (J.TAPPI) formulation.For example can use the paper with the upright altogether RIKEN of above-mentioned A method corresponding (strain) system to carry out this mensuration with pH determinator " form MPC ".
As concrete acid, can enumerate as formic acid, acetate, glycolic, ethanedioic acid, propionic acid, malonic acid, butanedioic acid, adipic acid, maleic acid, malic acid, tartaric acid, citric acid, benzoic acid, phthalic acid, M-phthalic acid, glutaric acid, gluconic acid, lactic acid, aspartic acid, glutamic acid, salicylic acid, salicylic acid metal salt (Zn, Al, Ca, salt such as Mg), methanesulfonic acid, itaconic acid, benzene sulfonic acid, toluenesulfonic acid, TFMS, styrene sulfonic acid, trifluoroacetic acid, barbituric acid, acrylic acid, methacrylic acid, cinnamic acid, the 4-Para Hydroxy Benzoic Acid, amino benzoic acid, naphthalenedisulfonic acid, hydroxy benzene sulfonic acid, toluenesulfinic acid, benzenesulfinic acid, sulfanilic acid, sulfamic acid, the alpha-dihydroxy-benzoic acid, β-Er Qiangjibensuan, γ-resorcylic acid, gallic acid, phloroglucin, sulfosalicylic acid, ascorbic acid, arabo-ascorbic acid, diphenolic acid, hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, polyphosphoric acid, boric acid etc.These sour additions are as the criterion between 3～8 with the surface p H value of regulating look material receiving layer.
Above-mentioned acid also can be added use with the form (for example salt of sodium, potassium, calcium, caesium, zinc, copper, iron, aluminium, zirconium, lanthanum, yttrium, magnesium, strontium, cerium etc.) of slaine or the form of amine salt (for example ammonia, triethylamine, tri-n-butylamine, piperazine, 2-methyl piperazine, polyallylamine etc.).
In look material receiving layer of the present invention, preferably contain ultra-violet absorber, antioxidant, the impervious agent of spreading and sinking in etc. and can improve its conservatory reagent.
As these ultra-violet absorbers, antioxidant, the impervious agent of spreading and sinking in, can enumerate as alkylating phenol compound (also comprising hindered phenol compound), alkyl sulfide sylvan compound, the hydroquinones compound, the alkylated hydroquinone compound, tocopherol compound, the sulfo-diphenyl ether compound, the compound that contains two above thioether bonds, bisphenol compound, O-, N-, the S-benzyl compounds, the hydroxybenzyl compound, triaizine compounds, phosphonate compound, the amide groups phenolic compounds, ester compounds, amide compound, ascorbic acid, amine antioxidants, 2-(2-hydroxyphenyl) benzotriazole cpd, 2-hydroxy benzophenone ketonic compound, acrylate, water-soluble or hydrophobic metals salt, organo-metallic compound, metal complex, hindered amine compound (comprising the TEMPO compound), 2-(2-hydroxyphenyl)-1,3, the 5-triaizine compounds, metal deactivation agent, phosphite, phosphonate compound, hydroxylamine compounds, the nitron compound, peroxide scavenger, the polyamide stabilizing agent, polyether compound, the alkalescence auxiliary stabilizer, nucleator, the benzofuran ketonic compound, indolinone compound, phosphine compound, polyamine compounds, thiourea compound, carbamide compound, hydrazide compound, amidine compound, sugar compounds, the Para Hydroxy Benzoic Acid compound, dihydroxy benzoic acid compound, trihydroxy benzoic acid compound etc.
Wherein preferably alkylating phenol compound, the compound that contains two above thioether bonds, bisphenol compound, ascorbic acid, amine antioxidants, water-soluble or hydrophobic metals salt, organo-metallic compound, metal complex, hindered amine compound, hydroxylamine compounds, polyamine compounds, thiourea compound, hydrazide compound, Para Hydroxy Benzoic Acid compound, dihydroxy benzoic acid compound, trihydroxy benzoic acid compound etc.
As concrete compound example, can enumerate disclosed material in following document, for example special hope 2002-13005 number, Te Kaiping 10-182621 number, the spy opens 2001-260519 number, special fair 4-34953 number, special fair 4-34513 number, Te Kaiping 11-170686 number, special fair 4-34512 number, EP1138509 number, the spy opens clear 60-67190 number, Te Kaiping 7-276808 number, the spy opens 2001-94829 number, the spy opens clear 47-10537 number, with 58-111942 number, with 58-212844 number, with 59-19945 number, with 59-46646 number, with 59-109055 number, with 63-53544 number, special public clear 36-10466 number, with 42-26187 number, with 48-30492 number, with 48-31255 number, with 48-41572 number, with 48-54965 number, with 50-10726 number, No. the 2719086th, United States Patent (USP), with No. 3707375, with No. 3754919, with No. 4220711;
Special public clear 45-4699 number, with 54-5324 number, No. the 223739th, Europe publication, with No. 309401, with No. 309402, with No. 310551, with No. 310552, with No. 459416, No. the 3435443rd, Germany's publication, the spy opens clear 54-48535 number, with 60-107384 number, with 60-107383 number, with 60-125470 number, with 60-125471 number, with 60-125472 number, with 60-287485 number, with 60-287486 number, with 60-287487 number, with 60-287488 number, with 61-160287 number, with 61-185483 number, with 61-211079 number, with 62-146678 number, with 62-146680 number, with 62-146679 number, with 62-282885 number, with 62-262047 number, with 63-051174 number, with 63-89877 number, with 63-88380 number, with 63-88381 number, with 63-113536 number;
With 63-163351 number, with 63-203372 number, with 63-224989 number, with 63-251282 number, with 63-267594 number, with 63-182484 number, Te Kaiping 1-239282 number, Te Kaiping 2-262654 number, with 2-71262 number, with 3-121449 number, with 4-291685 number, with 4-291684 number, with 5-61166 number, with 5-119449 number, with 5-188687 number, with 5-188686 number, with 5-110490 number, with 5-1108437 number, with 5-170361 number, special public clear 48-43295 number, with 48-33212 number, No. the 4814262nd, United States Patent (USP), wait disclosed compound in each communique with No. 4980275.
Can use separately as other above-mentioned compositions also can two or more and usefulness.These other compositions can add after water-solubleization, decentralized, polymer dispersed, emulsification, oil dropletization and use, also can in wrap in the microcapsules and use.The above-mentioned addition of other compositions in ink jet recording sheet of the present invention, preferably 0.01～10g/m
2
In addition, in order to improve the dispersiveness of inorganic particles, can utilize silane coupling agent etc. that the surface of inorganic particles is handled.As this silane coupling agent, preferably except that the position of carrying out the coupling processing, also containing organo-functional group (for example vinyl, amino (1 grade～3 grades amino, quaternary ammonium salt bases), epoxy radicals, sulfydryl, chloro, alkyl, phenyl, ester group etc.).
Look material receiving layer of the present invention is with preferably containing surfactant in the coating fluid.Can use in cationic, anionic species, nonionic class, both sexes class, fluorine class, the silicon class surfactant etc. any as this surfactant.
Can enumerate as polyoxyalkylene alkyl and polyoxyalkylene alkylbenzene ethers (carbiphene for example as above-mentioned nonionic class surfactant, diethyl carbitol, the PEO lauryl ether, PEO octadecyl ether, PEO nonyl phenylate etc.), the oxirane propylene oxide block copolymer, sorbitan fatty acid ester class (Span-20 for example, sorbitan monooleate, sorbitan trioleate etc.), PEO sorbitan fatty acid ester class (PEO Span-20 for example, the PEO sorbitan monooleate, PEO sorbitan trioleate etc.), PEO D-sorbite fatty acid ester (for example four oleic acid PEO sorbitol esters etc.), fatty acid glyceride class (for example glycerin mono-fatty acid ester etc.), PEO fatty acid glyceride class (monostearate PEO glyceride for example, single oleic acid PEO glyceride etc.), PEO fatty acid ester (polyethylene glycol monolaurate for example, polyethylene glycol monooleate etc.), the PEO alkylamine, acetylenic diols (for example 2,4,7,9-tetramethyl-5-decine-4, the 7-glycol, and the addition product of oxirane that should alcohol, the addition product of expoxy propane etc.) etc., polyoxyalkylene alkyl class preferably wherein.This nonionic surfactant can use in coating fluid described later (A) and coating fluid (B).Above-mentioned in addition non-ionic surface active agent can use separately, also can be used in combination.
As above-mentioned amphoteric surfactant, can enumerate amino acid pattern, quaternary ammonium carboxylic acid inner salt type, quaternary ammonium acid inner salt type, quaternary ammonium sultones type, imidazoles inner salt type etc., for example No. the 3843368th, United States Patent (USP), spy open clear 59-49535 number, with 63-236546 number, spy open flat 5-303205 number, with 8-262742 number, open 2000-351269 number etc. with 10-282619 number, No. the 2514194th, special permission, No. 2759795, special permission, spy that disclosed material all is fit to use in each communique.In the above-mentioned amphoteric surfactant, preferably amino acid pattern, quaternary ammonium carboxylic acid inner salt type, quaternary ammonium acid inner salt type.Above-mentioned amphoteric surfactant can use separately also and can be used in combination.
As above-mentioned anion surfactant, be fit to use just like soap (for example odium stearate, calcium oleate), alkyl sulfate salt (for example lauryl sodium sulfate, dodecyltriethanolamine sulfate), sulfonate (for example neopelex), alkyl sulfo succinate (for example dioctyl sodium sulphosuccinate), alkyl diphenyl base ether disulfonate, alkylphosphonic etc.
Can enumerate alkylamine salt, quaternary ammonium salt, pyridiniujm, imidazole salts etc. as above-mentioned anionic species surfactant.
As above-mentioned fluorine class surfactant, what can enumerate is the compound that utilizes methods such as electrofluorination, telomerisation, oligomerisation reaction to be derived by the intermediate with perfluoroalkyl.
For example fluorinated alkyl sulfonate, perfluoroalkyl carboxylate, perfluoroalkyl ethylene oxide adduct, perfluoroalkyl trialkyl ammonium salts, the oligomer that contains perfluoroalkyl, perfluoralkyl phosphate etc.
As above-mentioned silicon class surfactant, preferably use the silicone oil of organo-functional group modification, for example the side chain of siloxane main chain structure utilizes the compound of organic group modification, the compound that two end of the chains are modified, the compound that the strand end is modified.That the modification of organo-functional group has is amino modified, polyether-modified, epoxy radicals modification, carboxy-modified, methyl alcohol modification, alkyl-modified, aralkyl modification, phenol modification, fluorine modification etc.
The content of surfactant of the present invention is with respect to look material receiving layer coating fluid, and preferably 0.001～2.0%, more preferably 0.01～1.0%.In addition, when utilizing two or more look material receiving layers to be coated with, preferably in various coating fluids, add surfactant with coating fluid.
For preventing to crispatura the high boiling organic solvent of preferred adding in look material receiving layer of the present invention.This high boiling organic solvent is that boiling point is water-soluble or hydrophobic compound at the organic compound more than 150 ℃ under the normal pressure.They at room temperature be solid or liquid all can, low molecule or polymer all can.
Specifically can enumerate (dibutyl phthalate for example as the aromatic carboxylic acid esters; diphenyl phthalate; benzoic acid phenyl ester etc.); aliphatic carboxylic acid esters,'s (dioctyl adipate for example; dibutyl sebacate; methyl stearate; dibutyl maleate; dibutyl fumarate; CitroflexA-2 etc.); phosphoric acid ester (trioctyl phosphate for example; tricresyl phosphate etc.); epoxies (epoxy radicals soybean oil for example; epoxy radicals fatty acid methyl ester etc.); alcohols (stearyl alcohol for example; ethylene glycol; propane diols; diethylene glycol (DEG); triethylene glycol; glycerine; diglycol monotertiary butyl ester (DEGMBE); the triethylene glycol mono; the glycerine mono-methyl; 1; 2; the 3-butantriol; 1; 2; the 4-butantriol; 1; 2,4-penta triol; 1; 2; the 6-hexanetriol; sulphur support diethanol; triethanolamine; polyethylene glycol etc.); vegetable oil (soybean oil for example; the sunflower seed wet goods); senior aliphatic carboxylic acid (linoleic acid for example; oleic acid etc.).
(supporter)
As supporter used among the present invention, can use the transparent supporting body of making by transparent materials such as plastics, the opaque supporter that also can use opaque materials such as paper to make.Consider that from the transparent aspect of look material receiving layer what preferably use is the opaque supporter of transparent supporting body or high-luster.
Can use the material in above-mentioned transparent supporting body, preferably transparent and have when in OHP and rear projection display, using can radiation hardness heat stable on heating material.As this material, for example can enumerate PET polyesters such as (PET); Polysulfones, polyphenylene oxide, polyimides, Merlon, polyamide etc.Wherein, preferably polyesters, more preferably PET (PET).
Do not limit the thickness of above-mentioned transparent supporting body is special, but from maneuverable angle 50～200 μ m preferably.
As the opaque supporter of high-luster, the supporter that has the glossiness more than 40% at the table that look material receiving layer one side is set preferably.This glossiness is to be the value that standard is tried to achieve with the method put down in writing among the JISP-8142 (75 degree mirror surface luster experimental techniques of paper and paperboard).Specifically be listed below as this supporter.
For example can enumerate at art paper, coated paper, casting coated paper (cast coat paper), silver halide photography with the high-luster paper supporters such as barium oxygen paper that use in the supporter etc.; In PET polyesters such as (PET), cellulose esters such as NC Nitroncellulose, cellulose acetate, cellulose acetate-butyrate add Chinese white make it the to become high-luster film of opaque (perhaps also can implement surperficial press polish handles) in the plastic foils such as polysulfones, polyphenylene oxide, polyimides, Merlon, polyamide; Perhaps at above-mentioned various paper supporters, transparent supporting body or contain on the surface of high-luster film of Chinese white etc., the supporter of the polyolefin coverlay that contains or do not contain Chinese white etc. is set.
The expanded polyester film (for example adding polyolefin fine particle, by the interstitial foaming PET of stretch processing) that contains Chinese white also is fit to use.Also have, also more satisfactory at the resin-coated paper (resin coat paper) that silver halide photography uses in photographic pape.
Do not limit for the thickness of above-mentioned opaque supporter is special, but from maneuverable angle 50～300 μ m preferably.
In addition, for wetability and the adhesiveness of improving above-mentioned supporting body surface, the preferred supporter of handling through Corona discharge Treatment, glow discharge processing, flame treatment, ultraviolet treatment with irradiation etc. that uses.
Then, be described in detail in used body paper in the above-mentioned resin-coated paper.
This body paper is to be primary raw material with the wood pulp, also uses synthetic paper-pulp or synthetic fibers such as nylon or polyester such as polypropylene in case of necessity except that wood pulp, obtains through papermaking.As above-mentioned wood pulp, can use any among LBKP, LBSP, NBKP, NBSP, LDP, NDP, LUKP, the NUKP, preferred use contains the more LBKP of short fiber, NBSP, LBSP, NDP, LDP more.
Wherein, as LBSP or/and the content of LDP, preferably 10 quality %～70 quality %.
The preferred above-mentioned paper pulp that uses is impure less chemical pulp (sulfate pulp and sulfite pulp), and the paper pulp that has improved its whiteness after handling through bleaching is fit to too.In addition in body paper, can suitably add cementing agents such as higher fatty acids, alkyl ketene dimer, Chinese whites such as calcium carbonate, talcum, titanium oxide, paper power reinforcing agents such as starch, polyacrylamide, polyvinyl alcohol, fluorescent whitening agent, water retention agents such as polyethylene glycols, dispersant, gentle softening agent such as quaternary ammonium etc.
Beating degree as the paper pulp that in papermaking, uses, with CSF regulation 200～500ml preferably, in addition the fibre length after the making beating preferably among the JISP-8207 the 24 sieve mesh residue on sieve quality % of defined and the quality % sum of 42 sieve mesh residue on sieves be 30～70%.Further preferably the residue on sieve of 4 sieve meshes is below 20% quality.
As the quality optimization 30～250g of body paper, more preferably 50～200g.As the thickness of body paper 40～250 μ m preferably.This body paper can be given its high flatness through the press polish processing after papermaking stage or papermaking.The density of body paper is generally 0.7～1.2g/m
2(JISP-8118).
And then, as the rigidity of body paper, 20～200g preferably under the JISP-8143 defined terms.
Also can the coating surface cementing agent on the surface of body paper, this surface sizing agent can use with can add above-mentioned body paper in the identical cementing agent of cementing agent.
The pH value of body paper can utilize water hot extraction's method of JISP-8113 regulation to measure, preferably between 5～9.
Cover the polyethylene at the body paper surface and the back side, based on low density polyethylene (LDPE) (LDPE) or/and high density polyethylene (HDPE) (HDPE) can also use a part of LLDPE and polypropylene etc.
Particularly, on the polyethylene layer that forms look material receiving layer one side, can add rutile or anatase-type titanium oxide and fluorescent whitening agent, ultramarine in polyethylene, thereby improve opacity and whiteness and form and aspect, this washes in sensitive paper etc. at photo is the measure of often taking.With respect to polyethylene, preferably about 3～20 quality % of the amount of titanium oxide, more preferably 4～13 quality %.Though the thickness for polyethylene layer is not particularly limited, its surfaces externally and internally layer all is advisable in 10～50 mu m ranges.And then, for give on the polyethylene layer and look material receiving layer between connecting airtight property, priming coat can be set.As this priming coat preferably waterborne polyester and gelatin, PVA.In addition as the thickness of this priming coat, 0.01～5 μ m preferably.
Polyethylene coated paper can be used as glossy paper and uses, in addition, also can use and carry out so-called stamp in the operation that is coated with molten polyethylene being squeezed on the body paper surface and handle and formed as the delustring face of photograph photographic pape and the material of thin,tough silk order face.
The back coating also can be set on supporter, in this bottom, can add Chinese white or water-soluble binder and other composition.
As the above-mentioned Chinese white that is contained in this back coating, can enumerate as precipitated calcium carbonate, powdered whiting, kaolin, talcum, calcium sulfate, barium sulfate, titanium dioxide, zinc oxide, zinc sulphide, zinc carbonate, satin white, alumina silicate, diatomite, calcium silicates, magnesium silicate, synthetic amorphous silica, cataloid, colloidal alumina, plan boehmite, aluminium hydroxide, aluminium oxide, lithopone, zeolite, add white inorganic pigments such as endellite, magnesium carbonate, magnesium hydroxide; Organic pigments such as styrene plastic pigment, acrylics pigment, polyethylene, microencapsulation, Lauxite, melmac etc.
As the above-mentioned water-soluble binder that is used for the back coating, can enumerate as water dispersible macromolecules such as water soluble polymer, styrene butadiene latices, acrylic emulsions such as styrene/maleate copolymer, phenylethylene ethylene/propenoic acid ester copolymer, polyvinyl alcohol, silanol modified polyvinylalcohol, starch, cationic starch, casein, gelatin, carboxymethyl cellulose, hydroxyethylcellulose, polyvinylpyrrolidone etc.
As other compositions that can be contained in the coating of back, can enumerate defoamer, foam inhibitor, dyestuff, fluorescent whitening agent, anticorrisive agent, anti-hydrated agent etc.
(making of ink jet recording sheet)
When producing the look material receiving layer of ink jet recording sheet of the present invention, preferably form by following method, promptly, for example on supporting body surface, be coated with the 1st coating fluid (being called coating fluid A sometimes) that contains particulate and water-soluble resin at least, and (1) is in this coating, perhaps (2) are in being coated with formed coating layer dry run and before coating layer presents falling-rate periods of drying speed by this, in above-mentioned any moment, the pH value that supply contains mordant at least makes the coating layer crosslinking curing (wet-on-wet method) of accepting second coating fluid afterwards at the 2nd coating fluid more than 8 (being called coating fluid B sometimes).Here, by the complex that forms with represented carboxylic acid of general formula of the present invention (1) and the above metal of divalent, preferably be contained at least a in the 1st above-mentioned coating fluid (coating fluid A) or the 2nd coating fluid (coating fluid B), the above metal of perhaps above-mentioned divalent is contained in the 1st above-mentioned coating fluid (coating fluid A) and the carboxylic acid shown in the above-mentioned general formula (I) is contained in above-mentioned the 2nd coating fluid (coating fluid B), and the carboxylic acid shown in the perhaps above-mentioned general formula (I) is contained in the 1st above-mentioned coating fluid (coating fluid A) and the above-mentioned above metal of divalent is contained in above-mentioned the 2nd coating fluid (coating fluid B).In addition, the crosslinked crosslinking agent of above-mentioned water-soluble resin also preferably is contained in above-mentioned coating fluid (A) or coating fluid (B) at least a.
Method through the look material receiving layer of crosslinking curing is set thus, when considering, comparatively desirable from the aspects such as freedom from cracking of ink absorption and film.
After aforesaid processing, have more mordant at look material receiving layer near surface, so the mordant dyeing effect of ink-jet look material is fine, thereby can improves the resistance to water of literal after the lettering and image, thereby comparatively desirable.Also can contain a part of mordant in above-mentioned coating fluid (A), at this moment, the mordant in coating fluid (A) and the coating fluid (B) can be the same or different.
Among the present invention, the look material receiving layer that contains particulate (for example fumed silica) and water-soluble resin (for example polyvinyl alcohol) at least can utilize following method to modulate with coating fluid (coating fluid (A)) and obtain.Promptly, be added to the water fumed silica particulate and dispersant (for example the content of silica is 10～20 quality % in the water), utilize and rotate wet type colloid mill (for example ェ system テ Network ニ Star Network (strain) system " Network レ ア ミ Star Network ス ") at a high speed, under the rotation of the high speed of for example 10000rpm after the dispersion of 20 minutes (preferably 10～30 minutes), add crosslinking agent (boron compound), polyvinyl alcohol (PVA) aqueous solution (PVA that for example adds above-mentioned fumed silica 1/3 quality), and then add this compound when in look material receiving layer coating fluid, containing the complex that forms by carboxylic acid and metal among the present invention again, with on disperse under the identical rotating condition, finish modulation thus.The coating fluid that obtains is the uniform sol state, and is dry by utilizing following coating process that it is coated on the supporter, can form the porous structure look material receiving layer with tridimensional network.
In addition, when modulating the water dispersion of making by above-mentioned fumed silica and dispersant, can modulate the aqueous dispersions of fumed silica in advance, again this aqueous dispersions is added in the aqueous solution of dispersant afterwards, also aqueous dispersant can be joined in the aqueous dispersions of fumed silica, perhaps also can mix simultaneously.In addition, also can use powdered silica, join by aforesaid method in the aqueous solution of dispersant without fumed silica.
Use if utilize dispersant that fumed silica is made water dispersion, then can make ink jet recording sheet obtain better glossiness, thus comparatively desirable.
After mixing above-mentioned fumed silica and dispersant, utilize dispersion machine with this mixed liquor grain refined, just can obtain the aqueous dispersions of average grain diameter at 50～300nm.Though can utilize our known various dispersion machines in order to obtain above-mentioned aqueous dispersions, for example rotate dispersion machine and medium agitating type dispersion machine (ball mill, sand mill etc.), ultrasonic dispersing machine at a high speed, colloidal grinding dispersion machine, high pressure dispersion machine etc., but when the angle of the dispersion that can carry out formed ball particulate was effectively considered, preferred what use was agitating type dispersion machine, colloidal grinding dispersion machine or high pressure dispersion machine.
In addition, as employed solvent in each step, can make water, organic solvent or their mixed solvent.Operable organic solvent has alcohols such as methyl alcohol, ethanol, normal propyl alcohol, isopropyl alcohol, methoxypropanol in this coating; Ketone such as acetone, MEK; Oxolane, acetonitrile, ethyl acetate, toluene etc.
In addition, also can use cation property copolymer as above-mentioned dispersant.Can use above-mentioned mordant example etc. as cation property copolymer.Also have, use silane coupling agent also more satisfactory as dispersant.
For prevent through the time ooze and spread and sink in, preferably use the dispersant of at least a I/O of being selected from value in the compound dispersing agent below 2.0.At this, above-mentioned parameter I/O value is the parameter of expression compound or substituent hydrophily/oil loving yardstick, in first Tian Shansheng work " organic conceptional diagram " (three publish 1984 altogether) detailed explanation is arranged.I represents inorganic nature, and O represents organic property, big more its inorganic nature of expression of I/O value straight big (polarity height, hydrophily is big).
Above-mentioned dispersant is with respect to the addition of particulate preferably 0.1%～30%, and more preferably 1%～10%.
Look material receiving layer of the present invention for example can utilize extrusion die rubbing method (Extrusion die coater), pneumatic knife coating, knife coating, bar to be coated with known coating processes such as method, scraper rubbing method, scraper plate rubbing method, contrary roller rubbing method, bar rubbing method with the coating of coating fluid to carry out.
When coating look material receiving layer is with coating fluid (coating fluid (A)) or after the coating, provide coating fluid (B) to this coating layer, coating fluid (B) applies before also can this coating layer (A) after coating presenting falling-rate periods of drying speed.Promptly at coating look material receiving layer afterwards, during this coating layer shows constant rate of drying speed, import mordant, just can successfully make with coating fluid (coating fluid (A)).
Here, above-mentioned " coating layer shows before the falling-rate periods of drying speed ", typically refer to firm coating look material receiving layer with several minutes process after the coating fluid, during this period, can occur in the coating layer solvent (decentralized medium) content in time and " constant rate of drying speed " phenomenon that reduces.Be the time of " constant rate of drying speed " about this, for example record to some extent in " chemical engineering brief guide " (707～712 pages, ball kind (strain) distribution, clear and on October 25th, 55).
As mentioned above, after coating the 1st coating fluid, this coating layer is dried to and presents falling-rate periods of drying speed, and this drying is generally carried out 0.5～10 minute (preferred 0.5～5 minute) at 50 ℃～180 ℃.This drying time is different along with the difference of coating weight, proper within above-mentioned scope usually certainly.
As presenting the method for handling before the falling-rate periods of drying speed at above-mentioned the 1st coating layer, can use following method, (1) method of further coating coating fluid (B) on coating layer, (2) method of utilizing method such as atomizing to spray, (3) dipping in coating fluid (B) have formed the method etc. of the supporter of this coating layer.
In the said method (1), as the method for coating coating fluid (B), can utilize and be coated with known coating processes such as method, scraper rubbing method, scraper plate rubbing method, contrary roller rubbing method, bar rubbing method as curtain coating method, extrusion die rubbing method, pneumatic knife coating, knife coating, bar.But preferably adopt as the curtain coating method coating process that extrusion die rubbing method, bar rubbing method etc. directly do not contact with the 1st coating layer that has formed.
Providing above-mentioned mordant solution (coating fluid (B)) afterwards, generally under 40 ℃～180 ℃ temperature, heated 0.5～30 minute, to carry out drying and curing.Wherein preferably 40 ℃～150 ℃ heating 1～20 minute.
In addition, when when coating look material receiving layer is with coating fluid (coating fluid (A)), providing above-mentioned mordant solution (coating fluid (B)), look material receiving layer coating fluid (coating fluid (A)) and mordant solution (coating fluid (B)) can be coated on (multiple layer coating) on the support simultaneously, and making this look material receiving layer coating fluid (coating fluid (A)) be contacted with supporter, drying is solidified and just can be formed look material receiving layer afterwards.
Coating in the time of above-mentioned (multiple layer coating) can adopt coating processes such as curtain coating method, extrusion die rubbing method to carry out.Formed coating layer is given drying after the coating simultaneously, and the drying of this moment normally heats coating layer 0.5～10 minute under 40 ℃～150 ℃ temperature, more preferably 40 ℃～100 ℃ heating 0.5～5 minute.
For example utilize the extrusion die rubbing method carry out above-mentioned in during coating (multiple layer coating), Pen Chu two kinds of coating fluids formed multiple layer before promptly moving on the supporter near the ejiction opening of extrusion die coating machine simultaneously, and were coated on the supporter so that this state is overlapping.But overlapping two kinds of coating fluids before coating, in on moving to supporter, owing on two coating fluid interfaces, be easy to generate cross-linking reaction, therefore near the ejiction opening of extrusion die coating machine, two kinds of coating fluids of ejection mix and the thickness that becomes, thereby can hinder the carrying out of coating operation.Therefore, when carrying out multiple simultaneously layer coating as mentioned above, what preferably adopt is in coating look material receiving layer coating fluid (coating fluid (A)) and mordant coating fluid (coating fluid (B)), between above-mentioned 2 liquid, get involved interlayer liquid (intermediate layer coating fluid), thereby carry out three layers of coating simultaneously.
Do not limit for above-mentioned interlayer coating fluid is special.For example can use the aqueous solution that contains the minor amount of water soluble resin or water etc.Above-mentioned water-soluble resin is considered tackifier etc. and is used in order to solve coating, for example can enumerate polymer such as cellulosic resin (for example hydroxypropyl methylcellulose, methylcellulose, HEMC etc.), polyvinylpyrrolidone, gelatin.Also have, in the interlayer coating fluid, also can contain above-mentioned mordant.
On supporter, form after the look material receiving layer, add to depress in heating and utilize supercalender, gloss calender etc. to make this look material receiving layer, can improve its surface smoothing and glossiness, the transparency and coating strength thus handling to carry out press polish by gap.But this press polish processing sometimes can become and causes the descend main cause of (promptly reducing the absorbability of printing ink) of voidage, therefore sets to make descend less condition and to handle be very important of voidage under this condition.
Roll temperature when carrying out press polish and handle is preferably between 30～150 ℃, more preferably between 40～100 ℃.Line pressure when handling as press polish in addition between roller, 50～400kg/cm preferably is more preferably at 100～200kg/cm.
Owing to when carrying out ink mist recording, need have the absorptive capacity that can absorb whole drops, therefore as the thickness of above-mentioned look material receiving layer, must be according to the relation decision between the voidage in it and the layer.For example, quantity of ink is 8nL/mm
2And voidage is 60% o'clock, needs the film of bed thickness more than about 15 μ m so.Consider from this point, as the thickness of its look material receiving layer of ink jet recording sheet preferably in the scope of 10～50 μ m.
In addition, with regard to the fine pore of look material receiving layer, in intermediate value directly, 0.005～0.050 μ m preferably is more preferably at 0.01～0.035 μ m.Above-mentioned voidage and pore intermediate value footpath, (trade name of (strain) Shimadzu Seisakusho Ltd. system " ボ ア サ ィ ザ-9320-PC2 " is measured can to utilize mercury Port ロ シ メ one one.
In constituting the layer of ink jet recording sheet of the present invention (for example look material receiving layer or back coating etc.), also can add the dispersion thing of polymer particles.This polymer particles disperse thing for improve dimensional stability and anti-ly crispatura, the physical property of films such as antiseized pair and anti-film be full of cracks uses.Disperse thing about this polymer particles, the spy open clear 62-245258 number, with 62-1316648 number, on the books in each communique such as 62-110066 number.If add lower (below the 40 ℃) polymer particles of glass transition temperature and disperse thing in above-mentioned contain in the mordant layer in addition, then can prevent the be full of cracks of layer and crispatura.In addition, adding the higher polymer particles of glass transition temperature in the coating of back disperses thing also can prevent to crispatura.
In addition, ink jet recording sheet of the present invention also can utilize the spy open flat 10-81064 number, with 10-119423 number, with 10-157277 number, with 10-217601 number, open with 11-348409 number, spy 2001-138621 number, with 2000-43401 number, with 2000-211235 number, with 2000-309157 number, with 2001-96897 number, open with 2001-138627 number, spy flat 11-91242 number, with 8-2087 number, with 8-2090 number, with 8-2091 number, make with disclosed method in 8-2093 number each communique.
[embodiment]
Below, in conjunction with the embodiments the present invention is carried out specific description, but the present invention is not limited to these embodiment." part " among the embodiment and " % ", all expressions " mass parts " and " quality % " under the situation that does not have special explanation.
(making of supporter)
Utilize the double plate refiner to reach 300ml by wood pulp making beating to the Canadian freeness that 100 parts of LBKP make, then with absolute dry weight ratio with respect to paper pulp, add 0.5 part epoxidation 22 acid amides, 1.0 parts of anionization polyacrylamides, 0.1 part of polyamide polymeric amine epichlorohydrin, 0.5 part cationization polyacrylamide respectively, utilize the fourdrinier machine weighing then, make 170g/m
2Body paper.
In order to adjust the surperficial granularity of above-mentioned body paper, in 4% polyvinyl alcohol water solution, add 0.04% fluorescent whitening agent (Sumitomo Chemical (strain) system " whitex BB "), and be 0.5g/m with the conversion absolute dry weight
2Condition above-mentioned body paper contained be immersed in this solution, further implement calender after dry to handle, being modulated into density is the basic paper of 1.05g/ml.
Silk (wire) face (back side) of gained base paper is carried out after the Corona discharge Treatment, utilize to melt extrude machine to form thickness be the high-density polyethylene ene coatings of 19 μ m, form the resin bed that constitutes by delustring face (below be called resin bed be " reverse side ").The resin bed of this reverse side is further carried out after the Corona discharge Treatment, to be dispersed in made dispersion liquid in the water with 1: 2 mass ratio as aluminium oxide of antistatic additive (daily output chemical industry (strain) system " alumina gel 100 ") and titanium dioxide (daily output chemical industry (strain) is made " ス ノ one テ シ Network ス O "), and be coated with this dispersion liquid to dry mass and reach 0.2g/m
2
And then, felt face (surface) side that resin bed is not set is carried out after the Corona discharge Treatment, utilization melt extrudes machine, and to extrude thickness in its surface be that MFR (melt flow rate) 29 μ m, that contain 10% anatase titanium dioxide, micro-ultramarine and 0.01% fluorescent whitening agent (with respect to polyethylene) is 3.8 low density polyethylene layer, thereby the thermoplastic resin that forms high glaze on the basic paper surface (below, this high glaze face is called " surface "), make supporter.
[embodiment 1]
(modulation of coating fluid A of look material receiving layer)
With the 1. fumed silica particulate of following composition, 2. ion exchange water, 3. " ケ ミ ス シ ト 7005 " mixes, after the dispersion machine " KD-P " of utilization (strain) シ Application マ Le エ Application one プ ラ ィ ゼ ス system disperses, add following metal complex of the present invention 4., advance-go on foot to utilize dispersion machine " KD-P " to disperse.Then add and contain 5. polyvinyl alcohol, 6. boric acid, 7. PEO lauryl ether, the 8. solution of ion exchange water, modulation quality material receiving layer is with coating fluid (A).
Here, and the mass ratio of silicon dioxide microparticle and water-soluble resin (the PB ratio=1./5.) be 4.5/1, this look material receiving layer is 3.5 with the pH value of coating fluid (A), is acid.
(the look material receiving layer composition of coating fluid (A))
1. fumed silica particulate (inorganic particles) is 10.0 parts
((strain) ト Network ヤ マ system " レ ォ ロ シ one Le QS-30 ", average primary particle diameter 7nm)
2. ion exchange water is 51.6 parts
3. " ケ ミ ス Star ト 7005 " (40% aqueous solution) 1.2 parts
(dispersant, Sanyo changes into industry (strain) system, I/O value 1.9)
4. C
12H
25N (CH
2COOH)
2And 1: 1 (mol ratio) of aluminium polychloride (basicity 83%)
1.0 parts of product (complex of the present invention)
5. 8% aqueous solution of polyvinyl alcohol (water-soluble resin) is 27.8 parts
((strain) Network ラ レ system " PVA 124 ", saponification degree 98.5%, the degree of polymerization 2400)
6. boric acid (crosslinking agent) is 0.4 part
7. PEO lauryl ether (surfactant) is 1.2 parts
(flower king (strain) system " ェ マ Le ゲ Application 109P ", 10% aqueous solution, HLP value 13.6)
8. ion exchange water is 32.0 parts
(making of ink jet recording sheet)
After the surface enforcement Corona discharge Treatment to above-mentioned supporter, utilize the extrusion die coating machine to use coating fluid (A) with 200ml/m above-mentioned look material receiving layer
2Coating weight be coated on the surface of supporter (painting process), the solid component concentration that is dried to coating layer 80 ℃ (wind speed 3～8m/ seconds) with air drier reaches 20%.This coating layer has shown constant rate of drying speed during this period.And then in the mordant coating fluid (B) of following composition, flood 30 seconds bracelets, thereby make above-mentioned coating layer be stained with 20g/m
2Coating fluid (B) operation of mordant solution (additional), further in 80 ℃ of dryings 10 minutes (drying process).Obtain being provided with the ink jet recording sheet of the present invention (1) that dry film thickness is the look material receiving layer of 32 μ m thus.
(composition of mordant coating fluid (B))
1. boric acid (crosslinking agent) is 0.65 part
2. 20% aqueous solution of polyallylamine " PAA-03 " is 12.5 parts
(mordant, day east spin (strain) system)
3. ion exchange water is 72.0 parts
4. ammonium chloride (surface p H conditioning agent) is 0.8 part
5. PEO lauryl ether (surfactant) is 10 parts
(flower king (strain) system " エ マ Le ゲ Application 109P ", 2% aqueous solution, HLP value 13.6)
6. メ ガ Off ァ シ " F1405 " (10% aqueous solution) is 2.0 parts
(fluorine of big Japanese ink chemical industry (strain) system is a surfactant)
(embodiment 2)
1.0 parts the 4. product (complex of the present invention) in (look material receiving layer with coating fluid (A) form) in removing embodiment 1, according to obtaining the ink jet recording sheet (2) of comparative example with embodiment 1 same method.
(embodiment 3)
Except the 4. product (complex of the present invention) in 1.0 parts (the look material receiving layer with coating fluid (A) form) among the embodiment 1 being become 1.0 parts 40% aqueous solution of 4. aluminium polychloride (basicity 83%), according to obtaining the ink jet recording sheet (3) of comparative example with embodiment 1 same method.
(embodiment 4)
Except the 4. product (complex of the present invention) in 1.0 parts (the look material receiving layer with coating fluid (A) form) among the embodiment 1 is become 0.65 part 4. C
12H
25N (CH
2COOH) outside 2, according to obtaining the ink jet recording sheet (4) of comparative example with embodiment 1 same method.
(embodiment 5)
Except 2: 1 (mol ratio) product (complexes of the present invention) the 4. product (complex of the present invention) in 1.0 parts (the look material receiving layer with coating fluid (A) form) among the embodiment 1 being become 1.0 parts 4. N-ethoxy di-imidogen acetate and aluminium polychloride (basicity 83%), according to obtaining ink jet recording sheet of the present invention (5) with embodiment 1 same method.
(embodiment 6)
Except the 4. product (complex of the present invention) in 1.0 parts (the look material receiving layer with coating fluid (A) form) among the embodiment 1 is become 1.5 parts of 4. C
14H
29N (CH
2COOH)
2Outside 2: 1 (mol ratio) product (complexes of the present invention) of basic zirconium chloride, according to obtaining ink jet recording sheet of the present invention (6) with embodiment 1 same method.
(embodiment 7)
Except the 4. product (complex of the present invention) in 1.0 parts (the look material receiving layer with coating fluid (A) form) among the embodiment 1 being become 1.0 parts 4. 2: 1 (mol ratio) product (complexes of the present invention) of N-ethoxy di-imidogen acetate and basic zirconium chloride, according to obtaining ink jet recording sheet of the present invention (7) with embodiment 1 same method.
(embodiment 8)
Except the 4. product (complex of the present invention) in 1.0 parts (the look material receiving layer with coating fluid (A) form) among the embodiment 1 is become 1.5 parts of 4. C
12H
25N (CH
2CO
2Na) CH
2CO
2Outside 1: 10 (mol ratio) product (complex of the present invention) of H and aluminium polychloride (basicity 83%), according to obtaining ink jet recording sheet of the present invention (8) with embodiment 1 same method.
(embodiment 9)
Except the 4. product (complex of the present invention) in 1.0 parts (the look material receiving layer with coating fluid (A) form) among the embodiment 1 is become 1.2 parts of 4. C
12H
25N
+(CH
3)
2CH
2CO
2-and 1: 8 (mol ratio) product (complex of the present invention) of aluminium polychloride (basicity 83%) outside, according to obtaining ink jet recording sheet of the present invention (9) with embodiment 1 same method.
(embodiment 10)
Except the 4. product (complex of the present invention) in 1.0 parts (the look material receiving layer with coating fluid (A) form) among the embodiment 1 is become 2.0 parts of 4. C
16H
33N (CH
2CH
2COOH) 2 and 1: 4 (mol ratio) product (complex of the present invention) of aluminium polychloride (basicity 83%) outside, according to obtaining ink jet recording sheet of the present invention (10) with embodiment 1 same method.
(embodiment 11)
Dispersant in removing embodiment 1 in 1.2 parts (look material receiving layer with coating fluid (A) form) is 3. " ケ ミ ス Star ト 7005 ", according to obtaining ink jet recording sheet of the present invention (11) with embodiment 1 same method.
(embodiment 12)
Except 1.2 parts in (look material receiving layer with coating fluid (A) form) among the embodiment 1 3. dispersant " ケ ミ ス Star ト 7005 " become 1.0 parts 3. dispersant " シ ャ ロ one Le DC-902P " (the first industrial pharmacy (strain) system, 51% aqueous solution, I/O value 2.5) outside, according to embodiment 1 in same method obtain ink jet recording sheet of the present invention (12).
(evaluation test)
Utilize following method that the image by the above-mentioned ink jet recording sheet that obtains is oozed and spread and sink in and light resistance is estimated, the result remembers in following table 1.
(1) image oozes the test of spreading and sinking in
Various ink jet recording sheets are contained in the sheet feed section of ink-jet printer " PM-950C " of Seiko Epson (strain) system, use " PM-950C " to use black ink, make the square pattern of four 3cm * 3cmm separate the printed patterns that forms as sphere of movements for the elephants that is spaced of 1mm separately, with this image sample at 25 ℃, humidity is that the environment of 90%RH is preserved after 72 hours down, detect by an unaided eye and spread and sink in the oozing of black ink in blank gap, be being evaluated as below 0.01 " A " in the Bk colour filter that is increased in A condition of the black concentration of blank portion after the printing just, 0.01～0.05 be evaluated as " B ", being evaluated as more than 0.05 " C ".
(2) light resistance evaluation
Various ink jet recording sheets are contained in the sheet feed section of ink-jet printer " PM-950C " of Seiko Epson (strain) system, use " PM-950C " to use ink device, after the image on the spot of printing magenta, by blocking the ultraviolet colour filter of the following wave-length coverage of 365nm, and use Xenon Weather-ometer " Ci65A " (ATLAS society system), 25 ℃ of temperature, humidity is that the lamp that carried out 3.8 hours under the environment of 32%RH shines, afterwards under the state of turning off the light, at 20 ℃, placed under the environmental condition of relative humidity 91% one hour, so through 168 hours cycling.The reflection of the concentration " Xrite938 " that utilizes Xrite society to make before and after test is measured the concentration of pinkish red image, calculates pinkish red survival rate, and estimates according to following benchmark.Further pinkish red image has or not variable color before and after the validation test with the naked eye.
[benchmark]
A ... the concentration survival rate of pinkish red image surpasses 90%.
B ... the concentration survival rate of pinkish red image is 80～90%.
C ... the concentration survival rate of pinkish red image is 70～80%.
D ... the concentration survival rate less than 70% of pinkish red image.
(3) glossiness evaluation
Various ink jet recording sheets are contained in the sheet feed section of ink-jet printer " PM-950C " of Seiko Epson (strain) system, use " PM-950C " to use black ink, carry out the square field printing of 3cm * 3em.Estimate the glossiness of this black printing portion, and estimate according to following benchmark.
[benchmark]
Zero ... the glossiness height, quality is good.
△ ... gloss is more a bit weaker than above-mentioned
* ... gloss is very poor
[table 1]
| The IJ sheet for recording | Black ink is oozed and is spread and sunk in | Pinkish red light resistance | Glossiness | Remarks |
| Embodiment 1 | A | A | ○ | The present invention |
| Embodiment 2 | C | D | ○ | Comparative example |
| Embodiment 3 | C | B | ○ | Comparative example |
| Embodiment 4 | A | D | ○ | Comparative example |
| Embodiment 5 | A | A | ○ | The present invention |
| Embodiment 6 | A | B | ○ | The present invention |
| Embodiment 7 | A | B | ○ | The present invention |
| Embodiment 8 | A | A | ○ | The present invention |
| Embodiment 9 | A | A | ○ | The present invention |
| Embodiment 10 | A | A | ○ | The present invention |
| Embodiment 11 | A | A | △ | The present invention |
| Embodiment 12 | B | A | ○ | The present invention |
From the result of above-mentioned table 1 as can be seen, contain ink jet recording sheet of the present invention (embodiment 1,5～12) by the complex of using represented carboxylic acid of general formula (1) and the above metal of divalent to form, rare the oozing of black ink image spread and sunk in after it was preserved under high humidity environment, concentration survival rate through pinkish red image after the cyclic test under xenon lamp irradiation and high humidity environment is very high, is to have good anti-image to ooze and spread and sink in and sunproof ink jet recording sheet.
In addition, ink jet recording sheet of the present invention also has good ink absorption.
On the other hand, do not contain the ink jet recording sheet (embodiment 2～4) of the comparative example of complex of the present invention, after test, exist image to ooze to spread and sink in and the image color survival rate also lower, its image impervious spread and sink in and light resistance poor.
Utilize the present invention can obtain having high gloss and good printing ink compatibility and can suppress oozing of image for a long time and spread and sink in and improve its sunproof sheet for recording.
Claims (12)
1. an ink jet recording sheet is the ink jet recording sheet that has look material receiving layer on support, it is characterized in that, contains the complex that is formed by carboxylic acid and the above metal of divalent with note general formula (I) expression down in this look material receiving layer at least,
[changing 1]
(R
1)
m-N L-CO
2H)
nGeneral formula (I)
In general formula (I), R
1Expression hydrogen atom, aliphatic group, aromatic group, heterocyclic group, L represents the linking group of divalent, m and n represent the integer more than 0, and be 3 or 4 (m+n), when this (m+n) is 4, nitrogen-atoms in the general formula (I) becomes quaternary ammonium cation, and 1 carboxyl in the general formula (I) becomes anion or 1 R of disassociation state
1Base has the anionic property group.
2. ink jet recording sheet according to claim 1 is characterized in that, the above metal of described divalent is at least a kind that is selected from aluminium, titanium, the zirconium.
3. ink jet recording sheet according to claim 1 and 2 is characterized in that, the content of the complex that is formed by described carboxylic acid and the above metal of divalent is 0.01g/m
2-20g/m
2
4. ink jet recording sheet according to claim 1 and 2 is characterized in that, also contains water-soluble resin in the described look material receiving layer.
5. ink jet recording sheet according to claim 4; it is characterized in that described water-soluble resin is the resin that is selected from polyvinyl alcohol resin, cellulosic resin, ether-containing key, the resin that contains carbamoyl, carboxylic resin, reaches at least a kind in the gelatin class.
6. ink jet recording sheet according to claim 4 is characterized in that, contains in the described look material receiving layer to make water-soluble resin that crosslinked crosslinking agent takes place.
7. ink jet recording sheet according to claim 1 and 2 is characterized in that, also contains particulate in the described look material receiving layer.
8. ink jet recording sheet according to claim 7 is characterized in that, described particulate is to be selected from silicon dioxide microparticle, cataloid, alumina particulate, and to intend in the boehmite at least a kind.
9. ink jet recording sheet according to claim 8 is characterized in that, described particulate is the fumed silica particulate, and then as the fumed silica water dispersion that contains this fumed silica and dispersant, is used for look material receiving layer.
10. ink jet recording sheet according to claim 9 is characterized in that, the dispersant of described fumed silica is to be selected from I/O value at least a kind in the compound dispersing agent below 2.0.
11. ink jet recording sheet according to claim 1 and 2 is characterized in that, also contains mordant in the described look material receiving layer.
12. ink jet recording sheet according to claim 1 and 2, it is characterized in that, described look material receiving layer is the layer that the coating layer generation crosslinking curing that is coated with the coating fluid that contains particulate and water-soluble resin is at least formed, and this crosslinking curing be by to described coating fluid or/and down add crosslinking agent in the note alkaline solution, and (1) at coating described coating fluid and when forming coating layer, perhaps in the process of (2) coating layer of forming at drying coated described coating fluid and this coating layer any time point in showing before falling-rate periods of drying speed, provide pH to carry out at the alkaline solution more than 8 to described coating layer.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002354723 | 2002-12-06 | ||
| JP2002354723 | 2002-12-06 |
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|---|---|
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| CN100376411C true CN100376411C (en) | 2008-03-26 |
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|---|---|---|---|
| CNB2003101195973A Expired - Fee Related CN100376411C (en) | 2002-12-06 | 2003-12-04 | Sheet for ink-jet recording |
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| JP5804731B2 (en) * | 2010-04-20 | 2015-11-04 | キヤノン株式会社 | Inkjet recording medium |
| WO2021140772A1 (en) * | 2020-01-10 | 2021-07-15 | 富士フイルム株式会社 | Image recording method |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0730201A1 (en) * | 1995-02-28 | 1996-09-04 | Eastman Kodak Company | Sensitized photopolymerizable compositions and use thereof in lithographic printing plates |
| EP1251013A2 (en) * | 2001-04-19 | 2002-10-23 | Fuji Photo Film Co., Ltd. | Inkjet recording sheet |
| EP1253021A2 (en) * | 2001-04-27 | 2002-10-30 | Fuji Photo Film Co., Ltd. | Inkjet recording sheet |
| EP1260379A2 (en) * | 2001-05-22 | 2002-11-27 | Fuji Photo Film Co., Ltd. | Inkjet recording sheet |
-
2003
- 2003-12-04 CN CNB2003101195973A patent/CN100376411C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0730201A1 (en) * | 1995-02-28 | 1996-09-04 | Eastman Kodak Company | Sensitized photopolymerizable compositions and use thereof in lithographic printing plates |
| EP1251013A2 (en) * | 2001-04-19 | 2002-10-23 | Fuji Photo Film Co., Ltd. | Inkjet recording sheet |
| EP1253021A2 (en) * | 2001-04-27 | 2002-10-30 | Fuji Photo Film Co., Ltd. | Inkjet recording sheet |
| EP1260379A2 (en) * | 2001-05-22 | 2002-11-27 | Fuji Photo Film Co., Ltd. | Inkjet recording sheet |
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