CN1769065A - Ink-jet recording sheet - Google Patents
Ink-jet recording sheet Download PDFInfo
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- CN1769065A CN1769065A CN200510092314.XA CN200510092314A CN1769065A CN 1769065 A CN1769065 A CN 1769065A CN 200510092314 A CN200510092314 A CN 200510092314A CN 1769065 A CN1769065 A CN 1769065A
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- recording sheet
- ink
- water
- jet recording
- polyvalent metal
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
- B41M5/52—Macromolecular coatings
- B41M5/5218—Macromolecular coatings characterised by inorganic additives, e.g. pigments, clays
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
- B41M5/52—Macromolecular coatings
- B41M5/5254—Macromolecular coatings characterised by the use of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
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- Inorganic Chemistry (AREA)
- Ink Jet Recording Methods And Recording Media Thereof (AREA)
Abstract
A ink-jet recording sheet comprising on a support an ink absorptive layer containing minute silica particles, hydrophilic binder and water-soluble multivalent metal compounds; wherein said ink absorptive layer is composed of at least tow layers, and the peak of distribution of the amount of the water-soluble multivalent compounds in the depth direction is located within 10 m from the uppermost surface, and the weight ratio of the water-soluble multivalent metal compounds to minute silica particles in the uppermost layer of the ink absorptive layer, and the dried coating thickness of the uppermost layer, have specific ranges.
Description
Technical field
The present invention relates to a kind of novel ink-jet recording sheet, and relate to a kind of high-quality ink-jet recording sheet in more detail, it shows good absorption of inks ability and good bleeding resistance between the storage life that prolongs, produce high image density, and makes the variable density minimum after printing.
Background technology
In recent years, the photographs quality of routine has been improved and just approached to the picture quality of ink mist recording day by day.Picture quality in order to obtain by ink mist recording to compare with the photographs quality of routine has realized the improvement in performance to ink-jet recording sheet (also abbreviating recording sheet hereinafter as).
For example, made a kind of wherein by for example gelatin or PVA are coated to the recording sheet that forms ink absorbing layer on the extremely smooth carrier with hydrophilic adhesive.Such recording sheet utilizes the swellability of adhesive to absorb printing ink, and is known as the swelling type ink-jet recording sheet.Because the use water-soluble resin is as the adhesive of composition, therefore the swelling ink absorbing layer above has the feature of the high grade of transparency and effective color formation.Yet printing ink is not dry as desired after the printing.Be subjected to the influence of water in addition easily owing to image that forms and layer, the water-fast fastness that therefore obtains is lost.Especially, because the increase of the printing speed of present ink-jet printer, therefore in the swelling type ink-jet recording sheet, because the absorption of inks of adhesive swelling does not match mutually with the spray volume and the speed of printing ink.The result is because too much printing ink and spot problem occurring aspect the flying print adaptability.
On the other hand, the cavity type ink-jet recording sheet that has the porous layer with small void structure shows high glossiness, produced bright color, and showing good absorption of inks ability and good drying property, this void structure combines the extremely smooth carrier that contains small inorganic particle and hydrophilic polymer thereon.Therefore, the cavity type ink-jet recording sheet is just becoming a kind of in the sheet material of picture quality that generation approaches conventional radiography most.Especially, during carrier that-water non-when using absorbs, what can not cause occurring in the carrier of water absorption after printing heaves or so-called " wrinkling ", and can keep extremely smooth surface, can make the printed matter of better quality thus.
The cavity type recording sheet shows high absorption of inks ability and high speed drying property.On the other hand, owing to be subjected to the influence of the refractive index of small inorganic particle, the layer transparency that obtains is lower than the layer transparency of swelling type recording sheet.Therefore, having occurred wherein, color forms invalid problem.In the method that the color that improves the cavity type recording sheet forms, importantly realize a kind ofly improving the method for layer transparency and realizing a kind of wherein with the method for the fixing of dye in the printing ink in higher part.Because the former naturally and understandably is subjected to the restriction of the refractive index of small inorganic particle, therefore the more important thing is in a kind of method in back and realize improving.
Up to the present, many researchs have been carried out to overcome the above defective of cavity type recording sheet.Usually the method that adopts be wherein by with introduce porous layer in cationic substance combine a kind of method that firmly fixes anionic dye.Yet,, therefore cationic substance is simply introduced making in the porous layer and be difficult to the fixing of dye not realize thus that on top desirable color forms efficient because cationic substance is present in the whole porous layer.
Openly described the water soluble salt that will be selected from aluminium salt, magnesium salts, sodium salt, sylvite and zinc salt and introduced in the superiors, be fixed in the surface layer part of ink-receiver layer by colouring component thus and obtained high density and preferred color rendition pigment ink for open (the being called JP-A hereinafter) No.2001-287451 of the Japan Patent of public inspection.
In addition, JP-A No.2002-160442 has described following content.Employing is applied near the carrier the part, introduces the liquid coating composition of zirconium compounds or aluminium compound with relatively little amount, and adopts and be applied on the farther part of carrier, introduce the liquid coating composition of zirconium compounds or aluminium compound and carry out two-layer at least multiple coating with big relatively amount.As selection, zirconium compounds or aluminium compound can be coated to outward on the preformed ink absorbing layer, and make zirconium compounds or aluminium compound be present in carrier part far away by dipping, can make the bleeding minimum thus and can realize higher image density with higher amount.
In addition, JP-A No.2000-351267 has described absorbability and the crystallized ability that improves pigment ink by this way: will adopt pH be 3-11 the liquid coating composition, introduce alumina particle that average particulate diameter is 10-200nm or oxide particle for example silicon oxide particle, its surface with layer being coated on the porous ink-receiver layer in conjunction with boehmite that aluminium salt was handled.JP-ANo.2001-328340 described by with divalence or more the high price water-soluble metal salt introduce in the colouring agent receiving layer and improve water-fast fastness and light resistance, JP-A No.2004-114459 has described on ink-receiver layer and provide colloidal silica, its surface of being combined with as key component to be modified into the layer of cationic from carrier part farthest, has adopted pigment ink to obtain the desirable color formation of printing image, storage stability, drying property and wearability thus simultaneously.
Consider the absorption of inks ability, be described among the top JP-A No.2001-287451 ink-jet recording sheet with respect to 100 weight portion pigment for example silica be that the amount of 0.5-10 weight portion is used water-soluble metal salt.As shown in the following examples, can not realize the high ink absorption and the fixing of dye based on above embodiment.
In addition, as passing through shown in the following examples, because wherein causing the zirconium compounds or the aluminium compound of the q.s of effective fixing of dye is not fully to be present in this supposition on the effective surface, therefore the recording sheet that is described among the top JP-A No.2002-160442 can not obtain desirable bleeding resistance, desirable high density and desirable storage stability.
Summary of the invention
According to the present invention, a kind of ink-jet recording sheet is provided, this sheet material includes the ink absorbing layer that contains small silica granule, hydrophilic adhesive and water-soluble polyvalent metal compounds on carrier.Described ink absorbing layer is by two-layer composition at least, the amount distribution peak value of water-soluble multivalent compounds on depth direction is positioned at 10 μ m from the upper space, water-soluble polyvalent metal compounds and the small silica granule weight ratio when all changing into its separately oxide satisfies the qualification of following formula (1) in the superiors of ink absorbing layer, and the dry coating thickness of the superiors is the 2-20% of ink absorbing layer gross thickness
Formula (1)
3≤SiO
2/MO
x/2≤7
Wherein M represents to be combined in divalence or the high-valency metal atom more in the water-soluble polyvalent metal compounds, and x represents divalence or the chemical valence of high-valency metal atom M more.
In one embodiment, the weight (A) that changes into the water-soluble polyvalent metal compounds of its oxide in the superiors is at least 0.50 with the ratio A/ (A+B) that changes into the gross weight (A+B) of the water-soluble polyvalent metal compounds of its oxide.
In another embodiment, water-soluble polyvalent metal compounds can be selected from water miscible aluminium compound and zirconium compounds.
Description of drawings
Fig. 1 is the figure that shows an example of the secondary ion intensity curve of measuring by time of flight secondary ion massspectrometry method (TOF-SIMS) that is obtained from water-soluble polyvalent metal compounds.
Fig. 2 is the aluminum ions distribution measuring figure on the depth direction of ink absorbing layer that measures acquisition by the TOF-SIMS of the recording sheet 2 that is used as comparative example.
Fig. 3 is the aluminum ions distribution measuring figure on depth direction that measures acquisition by the TOF-SIMS of recording sheet 4 of the present invention.
The specific embodiment
The present inventor's supposition is by making water-soluble polyvalent metal compounds be positioned in the outmost surf zone with high concentration, can improve image density significantly, and further can make the variable density minimum after the printing as the particular problem of cavity type recording sheet.Find then,, use by this way, the small silica granule that adopts the vapour phase processes preparation is disperseed and the small cationic particle dispersion for preparing in the presence of water-soluble polyvalent metal compounds by forming the outmost surface of ink absorbing layer.PH during dispersion changes, and makes water soluble metallic compound is positioned in 10 μ m of outmost surface, and can obtain higher image density, realizes the present invention thus.
Then, adopt flight time type secondary ion mass spectrometry (TOF-SIMS) to analyze, can confirm that thus water-soluble polyvalent metal compounds is positioned in the outmost surface with higher concentration.
Incidentally, with determine based on following formula (1), water-soluble polyvalent metal compounds and the small silica granule weight ratio when all changing into their separately oxides is above under 7 the situation, can not realize that density strengthens effect, and this ratio less than 3 situation under, occur condensing between the layer, paintability is degenerated, produce striped.
Also find in addition, by increasing the MO in the superiors' liquid coating composition
X/2Ratio and be the 2-20% of dry ink absorbing layer gross thickness with the dry coating THICKNESS CONTROL, the THICKNESS CONTROL of gained can be arrived 10 μ m at the most, and, can realize the preferred distribution of the amount of water-soluble multivalent compounds by top weight ratio A/ (A+B) is controlled at least 0.50.
Incidentally, by dipping or outside apply and provide under the situation of the solution that contains water-soluble polyvalent metal compounds, be proved the indefinite zone, upper space that is arranged in of water-soluble polyvalent metal compounds.
The invention is characterized in, the content distribution peak value of water-soluble polyvalent metal compounds on depth direction is positioned at 10 μ m from the upper space, and the water-soluble polyvalent metal compounds that is combined in the upper space of ink absorbing layer changes into the weight of oxide and ratio that small silica granule changes into the weight of oxide satisfies the condition that limits with following formula (1).
Can following mensuration by the present invention's explanation, the quantity of water-soluble polyvalent metal compounds on the depth direction of ink absorbing layer.Adopt the side section of slicer with ink-jet recording sheet.Subsequently, for the sample that obtains, adopt EPMA (EPMA) or time of flight secondary ion massspectrometry instrument (TOF-SIMS) to obtain on depth direction to the specific element of polyvalent metal or the distribution of secondary ion segment.
In the present invention, the flight time type secondary ion mass spectrometry (TOF-SIMS) above adopting has determined that effectively whether water-soluble polyvalent metal compounds is positioned checking in the upper space with Cmax.About secondary ion mass spectrometry, can reference example such as TOF-SIMS:, edit with " Niji Ion Shitsuryo Bunseki Ho (secondary ion mass spectrometry) (Hyomen Bunseki GijutsuSensho (surface analysis technique book series)) (Maruzen) by John C.Vickerman and David Briggs by the surface analysis (publishing) of mass spectrography by Surface Spectra Co..
Be a kind of practical methods that is used to measure below.Adopt slicer that ink absorbing layer is cut so that expose flat cross section, and make the ink absorbing layer that obtains carry out the TOF-SIMS measurement.Preferred during TOF-SIMS measures is for example Au of metal ion as primary ions
+, In
+, Cs
+Or Ga
+, preferred In in the middle of these
+And Ga
+Incidentally, select preferred secondary ion to be tested based on the SIMS of previous mensuration.
The primary ions accelerating potential is preferably 20-30kV.Preferably carry out various adjustings so that the beam diameter of measuring by knife-edge method is at most 0.25 μ m.Conditions of exposure for example choose wantonly by beam current and time for exposure.As the exemplary of preferred measuring condition and what enumerate is that the primary ions beam electronic current is 0.9nA, and the time for exposure is 20 minutes.Incidentally, because ink-jet recording sheet or ink absorbing layer have caused low conductance, therefore preferably aptly by carrying out the static neutralization with electron gun in adopting.
During measuring, the primary ions bundle is in the scope interscan in the whole zone that can measure ink absorbing layer.Based on the scanning position and the detected secondary ion of primary ions bundle, can on ink absorbing layer, obtain the image of chemical species.In the superincumbent scanning area, preferably on 256 * 256 point, measure the mass spectrum of secondary ion, and obtain the image of chemical species based on the mass spectrum that obtains by the intensity at record object secondary ion peak.In addition, by peak intensity integration, can obtain the curve of secondary ion specific on thickness direction based on the image of gained with the part at same thickness place.Utilize the function of the software that is accompanied by the data processing that is used for ion microprobe usually to carry out the formation of the image and the curve of secondary ion.In the present invention, the function above preferred the employing.
In the present invention, in the polyvalent metal curve on thickness direction, the secondary ion intensity that wherein is obtained from the polyvalent metal in the ink absorbing layer is that 1.5 times part of its minimum of a value is defined as the part that polyvalent metal exists in the above.In addition, position and the thickness with the mode regulation ink absorbing layer identical with polyvalent metal ion is wherein to detect the zone that is combined in the metallic particles in the small silica granule that is present in the ink absorbing layer.Incidentally, the position of each layer is 50% position of the ionic strength of integration in the curve on thickness direction.
In the present invention, adopt the TRIFT-II that produces by Physical Electronics Co., the abundance of polyvalent metal compounds on actual measurement thickness direction under the condition of In ionic species and 25kV accelerating potential.
Fig. 1 be show measure by TOF-SIMS, owing to the figure of an example of the secondary ion intensity curve of water-soluble polyvalent metal compounds.
In Fig. 1, the measuring distance (in μ m) from outmost surface on depth direction is drawn into abscissa, and adopt that TOF-SIMS measures at each depth location, be drawn into ordinate owing to the intensity level of the secondary ion of polyvalent metal compounds.Curve B is to be presented in to have the exemplary of the peaked state of ionic strength clearly in the 10 μ m.By a dotted line the expression, by the curve A of polyvalent metal compounds being introduced the ink absorbing layer that makes in the conventional ink absorbing layer liquid coating composition in, maximum owing to the secondary ion intensity of polyvalent metal compounds is present in inside (in Fig. 1, in the degree of depth of about 15 μ m).Therefore, be deposited on the inside that printing ink on the outmost surface is fixed on ink absorbing layer, can not obtain high image density thus.
With top opposite, therein ink absorbing layer by two-layer at least form and outermost layers incorporate in the curve B according to ink absorbing layer of the present invention of polyvalent metal compounds of higher concentration, maximum owing to the secondary ion intensity of polyvalent metal compounds is present in outmost surface 10 μ m (in Fig. 1, at the depth location of about 6 μ m).Therefore, be deposited on the surf zone that printing ink on the outmost surface is fixed on ink absorbing layer, can obtain high image density thus.
What enumerate as water-soluble polyvalent metal compounds is for example aluminium, calcium, magnesium, zinc, iron, strontium, barium, nickel, copper, scandium, gallium, indium, titanium, zirconium, tin or plumbous chloride, sulfate, nitrate, acetate, formates, succinate, malonate and chloracetate of metal.In the middle of these, the water soluble salt of preferred aluminium, calcium, magnesium, zinc and zirconium is because their metal ion is colourless.In addition, preferred especially water miscible aluminium and zirconium compounds are because they have caused good bleeding resistance between the storage life that prolongs.
Can be Polychlorinated aluminium (aluminium chloride), aluminum sulfate, basic aluminium sulphate, alum (alum), alum (ammonium alum), aluminum sodium sulfate, aluminum nitrate, aluminum phosphate, aluminium carbonate, many sulfate alumina silicate (aluminum polysulfate silicate), aluminium acetate and alkali formula aluctyl as what the object lesson of water soluble aluminum compound was enumerated.The water-soluble of water-soluble polyvalent metal compounds is meant as described herein, and they are with at least 1 weight %, but more preferably the amount of at least 3 weight % is dissolved in 20 ℃ the water.
Consider oil absorbency, most preferred water soluble aluminum compound is that basicity is at least 80% aluminium chloride, and can be represented by following molecular formula.
[Al
2(OH)
nCl
6-n]
m(condition is 0＜n＜6 and m≤10)
Basicity is by n/6 * 100 expressions (in percentage).
The object lesson of preferred water-soluble zirconium compound comprises zirconyl carbonate, ammonium zirconyl carbonate, zirconyl acetate, zirconyl nitrate, acid chlorization zirconium (zirconium acid chloride), lactic acid oxygen zirconium and zirconyl acetate.In the middle of these, consider the bleeding resistance between the storage life in the duration that prolongs, special preferred acidic zirconium chloride and zirconyl acetate.
The preferred wet method silica that adopts the precipitation method or gel method to use sodium metasilicate to make as raw material simultaneously that uses perhaps uses the silica that adopts vapour phase processes to make to prepare according to small silica granule of the present invention.
The wet method silica of commercially available acquisition comprises, the product F INESEAL of TOKUYAMA Corp. for example, and it adopts the product NIPGEL of precipitation method preparation and Nippon Silica Industry Co., and it adopts the gel method preparation.Precipitation method silica is characterised in that so that the primary granule of the about 10nm of about 3-forms the silica granule that the mode of secondary aggregation forms.
The rudimentary primary particle size of wet method silica is not particularly limited.Consider the stable preparation of silica granule, diameter is 3nm at least preferably, considers a layer transparency simultaneously, and it is 50nm at the most preferably.Generally speaking, the wet method silica that adopts gel method to make is more more preferred than what adopt intermediate processing to make, because the former primary particle size can be littler.
The vapour phase silica is meant as described herein, by adopting silicon tetrachloride and hydrogen as the synthetic silica of the combustion method of raw material, and Nippon Aerosil Co. for example, the title of the product A EROSILSERIES of Ltd is commercially available.
In the present invention, consider during the small cationic particle dispersion of preparation, to obtain higher hole ratio and coarse aggregate still less that preferred especially vapour phase processes silica prepares small silica granule.In addition, the vapour phase processes silica is characterised in that because secondary aggregation forms under than the more weak relatively interaction of wet method silica, so it can be with disperseing than wet method silica energy still less.
The small silica granule that adopts vapour phase processes to make is to be preferred under the 3-50nm at the average primary particle diameter, yet this diameter more preferably is at most 20nm.When the average primary particle diameter is at most 50nm, can realize the desirable high gloss of recording sheet, and because the I of the reduction of the surface reflection of diffusion by making maximal density obtains more clear and brighter image.The average particulate diameter of the above molecule of following measurement.Adopt the cross section or the surface of electron microscope observation particle and porous ink absorbing layer, and measure the particle diameter of the particle of many random chooses.Subsequently, calculate simple and easy mean value (number average).In this article, represent particle diameter by having with the projected area of particle diameter of a circle of the same area.
Be particularly preferred embodiment below.Form secondary or higher grade particles, prepare porous ink absorbing layer then.In this case, consider that preparation shows the high ink absorption and the recording sheet of high gloss, average particulate diameter is preferably 20-200nm.
In addition, preferably store the moisture of controlling the vapour phase processes silica at least over 3 days in 20-60% relative humidity by the small silica granule that will adopt the vapour phase processes preparation.
The hole that the addition of small silica granule depends on desired absorption of inks amount, porous ink absorbing layer than and the kind of hydrophilic adhesive and changing widely, but be generally 5-30g/m
2Recording sheet, and be preferably 10-25g.The small vapour phase processes silica granule and the ratio of hydrophilic adhesive are generally 2: 1-20: 1, but be preferably 3: 1-10: 1.
Along with the addition increase of small silica granule, the absorption of inks capacity also increases.Yet the degeneration that performance may occur is for example curled and the formation of crackle.Therefore, preferred a kind of method that wherein recently improves capacity by the control hole.Preferred hole is than being 40-75%.It can be according to the kind of selected small silica granule and adhesive, and perhaps the quantity based on its mixing ratio and other additives controls the hole ratio.
" hole ratio " is meant the ratio of total cavity volume and cavitation layer volume as described herein.Can calculate the hole ratio based on the cumulative volume and the layer thickness of cambial material.In addition, easily obtain total cavity volume by measuring the water uptake.
Can be prepared as follows top small cationic particle dispersion.In fact, be that the small vapour phase processes silica granule of anionic property adds and contains in the aqueous solution of water-soluble polyvalent metal compounds with its surface, and make the mixture of gained disperse (becoming elementary dispersion).Subsequently, the pH controlling agent is added in the elementary dispersion of gained and make the mixture of gained disperse (becoming secondary dispersion).As selection, will be by elementary dispersion that top small vapour phase processes silica granule is scattered in make in the water and the aqueous solution blend that contains water-soluble polyvalent metal compounds, and subsequently the pH controlling agent is added the mixture of gained.After this, make this mixture carry out secondary dispersion.
Can be any commonsense method known in the field as elementary process for dispersing.Can also such mode prepare elementary dispersion: adopt the injection stream inductor mixer of for example producing to make small vapour phase processes silica granule aspirate (suction) and be distributed to mainly in the decentralized medium of forming by water-soluble multivalent compounds and water by Mitamura Riken Kogyo Inc..Subsequently, in the elementary dispersion above the pH controlling agent added and the gained mixture is disperseed,, can prepare small as described herein cationic particle dispersion thus to cause forming small particle.
In secondary process for dispersing, can adopt the homogenizer of multiple prior art for example to rotate homogenizer, medium agitating type homogenizer (for example ball mill or sand mill), ultrasonic homogenizer, colloid mill homogenizer, roll mill homogenizer or high pressure homogenisers at a high speed.For the small vapour phase processes silica granule that is in coherent condition that makes generation effectively disperses, preferably adopt ultrasonic homogenizer or high pressure homogenisers.
Ultrasonic homogenizer is applied on the solid-liquid interface ultrasonic wave of 20-25kHz so that concentration of energy is disperseed thus.This has caused very effective dispersion and has been suitable for preparing a spot of dispersion.On the other hand, in high pressure homogenisers, provide one or two can control the homogenizing valve in its gap by screw rod or oil pressure in the exit of the high-pressure pump that 3 or 5 pistons are housed, and narrow down by the homogenizing valve that produces high pressure by the liquid medium stream that high-pressure pump is carried, and small arbitrarily aggregation is pulverized.This system is particularly preferred for preparing a large amount of dispersions, because it can disperse the liquid of high volume continuously.The pressure that puts on homogenizing valve is generally 5-100MPa.Can be only once by or repeat repeatedly to finish dispersion.
Incidentally, water soluble compound is joined by small vapour phase silica being added in the medium based on water, the small cationic particle dispersion that such mode prepares in the slurry of following blend when stirring and making has caused the increase of viscosity or gel, can not make the target liq coating composition thus.
Preferably prepare small cationic particle dispersion by the pH that adopts the pH controlling agent to change elementary dispersion.By this operation, the small silica granule dispersion that uniform cation transforms has been carried out in preparation.In addition, can make the stable liquid coating composition that during following ink absorbing layer liquid coating preparation of compositions process, does not show turbidity and viscosity variation.More preferably prepare small cationic particle dispersion by during dispersion increasing pH.Therefore, can improve the absorbability and the crystallized ability of printing ink.The excursion of pH is preferably 0.20-1.0." during dispersion " is meant between elementary dispersed phase as described herein, i.e. the stage between the end of the end of elementary dispersion and secondary dispersion.
As the acid of pH controlling agent and can be of enumerating, for example organic acid such as formic acid, acetate, glycolic, oxalic acid, propionic acid, malonic acid, butanedioic acid, adipic acid, maleic acid, malic acid, tartaric acid, citric acid, benzoic acid, phthalic acid, M-phthalic acid, terephthalic acid (TPA), glutaric acid, gluconic acid, lactic acid, aspartic acid, glutamic acid, pimelic acid or suberic acid and inorganic acid example hydrochloric acid, nitric acid, boric acid and phosphoric acid.That enumerates as alkali can be NaOH, potassium hydroxide, calcium hydroxide, ammoniacal liquor, potash, sodium carbonate, sodium tripolyphosphate or triethanolamine.Consider owing to disperse the degree of every kind of bronsted lowry acids and bases bronsted lowry of progression (progression) performance and dispersion stabilization, the addition of each of necessary definite these acid or alkali.
In the superincumbent pH controlling agent, preferred boron compound.Boron compound is meant boric acid and its salt as described herein.Example comprises borax, boric acid and borate (for example, ortho-borate, InBO
3, ScBO
3, YBO
3, LaBO
3, Mg
3(BO
3)
2, Co
3(BO
3)
2), biborate (diborate) (Mg for example
2B
2O
5And Co
2B
2O
5), metaborate (LiBO for example
2, Ca (BO
2)
2, NaBO
2And KBO
2), tetraborate (Na for example
2B
4O
710H
2O), pentaborate (KB for example
5O
84H
2O, Ca
2B
6O
117H
2O and CsB
5O
5).Moisture boron compound solution can comprise independent a kind of boron compound or theirs is multiple.Particularly preferably be the mixed solution of borax and boric acid.Boric acid only forms the aqueous solution separately with borax under relative low concentration.Yet, when both are mixed, can make the aqueous solution of relative high concentration, can make dispersion concentration thus.In addition, advantage is presented in: depend on the mixing ratio of borax and boric acid, can relatively freely control pH.
Consider absorption of inks ability and layer intensity, can use the cationic polymer that contains quaternary ammonium salt group simultaneously between superincumbent dispersed phase.Particularly preferably be the homopolymers of the monomer that contains quaternary ammonium salt group or the copolymer of one or more copolymerisable monomers.When being used in combination, preferably between secondary dispersed phase, use boron-containing compound simultaneously.
As can be that the monomer that contains quaternary ammonium salt group is enumerated, for example be described in JP-ANo.11-301096 [0028] and [0029] section in compound.Can be the compound that contains olefinic (ethylenic) unsaturated group with the monomer of above quaternary ammonium salt group copolymerization, its example comprises the instantiation compound in [0031] section that is described in JP-ANo.11-301096.
Especially, be under the situation of copolymer at the cationic polymer that contains quaternary ammonium salt group, the ratio of cationic monomer is preferably at least 10 moles of %, at least 20 moles of % more preferably, but at least 30 moles of % most preferably.
Containing the monomer of quaternary ammonium salt group can be separately or with at least two kinds be used in combination.
Can be compound in [0035]-[0038] section that is described in JP-A No.11-301096 as what the object lesson of preferred cationic polymer that use, that contain quaternary ammonium salt group was in the present invention enumerated.
Can prepare small cationic particle by adding various additives.If desired, what suit to use is for example various nonionics or cationic surfactant, defoamer, nonionic, hydrophilic polymers (organic solvent of polyvinyl alcohol, polyvinylpyrrolidone, PEO, polyacrylamide, various types of carbohydrate, gelatin and amylopectin, nonionic or cationic latex dispersion, water compatible (ethyl acetate, methyl alcohol, ethanol, isopropyl alcohol, normal propyl alcohol and acetone) and inorganic salts.
Especially, when the solvent of water compatible be combined with its surface when being the aqueous solution blend of small vapour phase processes silica granule of anion and water-soluble polyvalent metal compounds, preferably hinder the formation of small aggregation.The organic solvent of this water compatible is preferably with 0.1-20 weight %, but more preferably the scope of 0.5-10 weight % is used for dispersion.
In the present invention, water-soluble polyvalent metal compounds and the small silica granule ratio when all changing into its separately oxide satisfies the condition that is limited by following formula (1):
Formula (1)
3≤SiO
2/MO
x/2≤7
Wherein M represents to be combined in divalence or the high-valency metal atom more in the water-soluble polyvalent metal compounds, and x represents divalence or the chemical valence of high-valency metal atom M more.
Water-soluble as described herein polyvalent metal compounds is by the MO in the following formula (1)
X/2Expression.That enumerate as bivalent metal oxide is CaO, MgO and ZnO, and as what trivalent metal oxide was enumerated is, for example Al
2O
3In addition, as what the tetravalent metal oxide was enumerated be, for example ZrO
2Based on MO according to formula 1
X/2, in having the valent metallic atom of odd number, the number of oxygen atom becomes mark.In this case, according to the convention of being accepted, it is expressed as integer.For example, according to the method for expressing of formula 1, aluminium oxide obtains AlO
1.5Yet in this case, it is expressed as Al
2O
3
What enumerate as the hydrophilic adhesive that is used for the present invention is, for example polyvinyl alcohol, gelatin, PEO, polyvinylpyrrolidone, casein, starch, agar, carrageenan, polyacrylic acid, polymethylacrylic acid, polyacrylamide, PMAm, polystyrolsulfon acid, cellulose, hydroxyethylcellulose, carboxymethyl cellulose, glucan, dextrin, amylopectin and water-soluble poval butyral.These hydrophilic adhesives can at least two kinds be used in combination.
Being preferred for hydrophilic adhesive of the present invention is polyvinyl alcohol.Except passing through common polythene alcohol with polyvinyl acetate hydrolysis preparation, also comprise modified polyethylene alcohol for example its end by anion-modified polyvinyl alcohol, contain the anion-modified polyvinyl alcohol of anionic group, perhaps ultraviolet radiation cross-linking type modified polyethylene alcohol.
Preferably be at least 1,000 by average degree of polymerization with the polyvinyl alcohol of polyvinyl acetate hydrolysis preparation, but more preferably 1,500-5,000.In addition, saponification number is preferably 70-100%, but most preferably is 80-99.5%.
The example of cation-modified polyvinyl alcohol comprise as be described among the JP-A No.61-10483 on its main chain or side chain, contain primary, the second month in a season or uncle's amino or quaternary ammonium group those, its ethylenically unsaturated monomer by will containing cation group and the copolymer saponification of vinyl acetate prepare.
As the ethylenically unsaturated monomer that contains cation group and can be of enumerating, trihydroxy methyl-(2-acrylamido-2 for example, the 2-dimethyl ethyl) ammonium chloride, trimethyl-(3-acrylamido-3, the 3-dimethyl propyl) ammonium chloride, N-vinyl imidazole, N-vinyl-methylimidazole, N-(3-dimethylamino-propyl) Methacrylamide, ethoxy trimethyl ammonium chloride, trimethyl-(2-methacrylamido propyl group) ammonium chloride and N-(1,1-dimethyl-3-dimethylamino-propyl) acrylamide.
Contain the monomer of cation-modified group of cation-modified polyvinyl alcohol and the ratio of vinyl acetate and be generally 0.1-10 mole %, but be preferably 0.2-5 mole %.
What enumerate as anion-modified polyvinyl alcohol is, for example be described in the polyvinyl alcohol that contains anionic group among the JP-A No.1-206088, be described in the copolymer of vinyl alcohol and the vinyl compound that contains water soluble group among JP-A Nos.61-237681 and the 63-307979 and be described in the modified polyvinylalcohol that contains water soluble group among the JP-ANo.7-285265.
In addition, what enumerate as nonionic modified polyvinyl alcohol is, the part passed through that for example is described among the JP-ANo.7-9758 adds the polyvinyl alcohol derivative that the polyalkylene oxide hydrocarbyl group prepares and is described among the JP-A No.8-25795 and the block copolymer vinyl compound that contains hydrophobic group.
What enumerate as ultraviolet radiation cross-linked type polyethylene alcohol is for example to be described in the modified polyvinylalcohol with photoreaction side chain among the JP-ANo.2004-262236.
What in addition, the polyvinyl alcohol that the aforesaid degree of polymerization is different with the modification degree can at least two kinds is used in combination.
In ink-jet recording sheet of the present invention, there is not the fragility of layer in order to realize high glossiness and high hole ratio, preferably make the polyvinyl alcohol sclerosis by curing agent.
Can be used for curing agent of the present invention normally contain with the group of polyvinyl alcohol reaction those or promote to be combined between the different groups in the polyvinyl alcohol react to each other those.The curing agent of enumerating as the example of this curing agent that is based on epoxy (for example, 2-glycidyl benzyl ethyl ether, ethylene glycol diglycidylether, 1,4-butanediol diglycidyl ether, 1,6-diglycidyl cyclohexane, N, N-diglycidyl-4-glycidyl oxygen base aniline, D-sorbite polyglycidyl ether and glycerine polyglycidyl ether); Curing agent (for example formaldehyde and glyoxal) based on aldehyde; Based on the curing agent of reactive halogen (for example, 2,4-two chloro-4-hydroxyls-1,3,5-s-triazine); Based on the compound of active ethylene group (for example, 1,3,5-triacryl-six hydrogen (hxahydro)-s-triazine and bi-vinyl sulfonyl methyl ether); Boric acid and its salt, borax, al alum and isocyanate compound.In the middle of these, preferred boric acid and its salt, based on the curing agent and the isocyanate compound of epoxy.
Boric acid and its salt are meant and contain boron atom oxyacid and its salt as central atom that its object lesson comprises ortho-boric acid, hypoboric acid, metaboric acid, tetraboric acid, five boric acid, eight boric acid and its salt.
The consumption of curing agent depends on the kind of polyvinyl alcohol, curing agent and small silica granule and with respect to the ratio of polyvinyl alcohol and change, and is generally 5-500mg, but is preferably the 10-300mg/g polyvinyl alcohol.
During the coating of formation, above curing agent directly can be added in the above liquid coating composition according to the ink absorbing layer of liquid coating composition of the present invention.As selection, can provide curing agent in such a way:, the solution that combines curing agent is applied outward in the ink absorbing layer coating that will form liquid coating composition (special) and after subsequently with the coating drying not in conjunction with curing agent.
In ink-jet recording sheet of the present invention, be preferably 2-20% according to the thickness of the uppermost surface layer of drying of the present invention with respect to the gross thickness of the ink absorbing layer of drying, but 5-15% more preferably.Promptly, by the superiors that apply at least two ink absorbing layers and top water-soluble polyvalent metal compounds is introduced ink absorbing layer with high concentration, can be at the ink absorbing layer that in nearer zone, surface, obtains to form owing to the secondary ion maximum of intensity of polyvalent metal compounds, as shown in fig. 1.
Preferably surfactant is introduced in the superiors according to ink absorbing layer of the present invention.Use as the surfactant that can be used for ink absorbing layer can be cationic, based on betaine, perhaps based on nonionic alkylene, based on fluorine and based on any one of the surfactant of siloxanes.In the middle of these, consider coating quality for example the coating problem tolerance and the adaptability of multiple coating simultaneously, preferably be described in cationic among the JP-A No.2003-312134 and based on the surfactant of betaine.The consumption of those surfactants is preferably 0.0001-1.0g/m
2, but 0.001-0.5g/m more preferably
2
Cationic polymer can be introduced according in the ink absorbing layer of the present invention.
Cationic polymer be on main chain or side chain, contain primary, the second month in a season or tertiary amine, quaternary ammonium salt group, perhaps those of quaternary alkylphosphonium salt group, and adopt the compound that is used for ink-jet recording sheet of prior art.Consider to be easy to preparation a preferred water miscible class.
As the example of cationic polymer and what enumerate is polymine; polyallylamine; polyvinylamine; dicyano diamido polyalkylene polyamine condensation product; polyalkylene polyamine dicyano diamido ammonium salt condensation product; dicyano diamido formalin condensation product; chloropropylene oxide-dialkylamine addition polymer; the diallyldimethylammonium chloride polymer; diallyldimethylammonium chloride-SO2 copolymer; polyvinyl imidazol; vinylpyrrolidone-vinyl imidazole copolymer; polyvinylpyridine; many amidines (polyamidine); shitosan; cationic starch; vinyl benzyl trimethyl ammonium chloride polymer; (2-methacryl (acroyl) oxygen base ethyl) trimethyl ammonium chloride polymer and dimethylaminoethyl methacrylate polymer.
In addition, example also comprises and is described in the cationic polymer of Kagaku Jiho (chemical industry news) in 15 days and 25 days August in 1998 and is described in (787 pages of polymeric dye fixatives on " Kobunshi Yakuzai Nyumon (polymeric medicine introduction (Introduction to Polymer Medicine)) " 787 pages, by Sanyo Chemical Industies, Ltd. publishes 1992).
The mean molecule quantity of cationic polymer is preferably 2,000-500, and 000, but more preferably 10,000-100,000.
Mean molecule quantity is meant number-average molecular weight as described in the present invention, and also refers to the polyethylene glycol conversion values by the measurement of gel displacement (permuation) chromatography.
In addition, cationic polymer is being introduced under the situation of liquid coating composition in advance, they can added the liquid coating composition equably, and also can adopt the form of the composite particles of small silica granule preparation to add wherein.The method that is used to adopt small silica granule and cationic polymer to prepare composite particles comprises wherein cationic polymer and small silica granule blend to produce absorption and the method that covers, wherein make the particle of the covering of gained condense with the method for the more senior composite particles of preparation and wherein to adopt homogenizer will change into the method for more uniform composite particles by the coarse granule of blend preparation.
Because the existence of water soluble group, cationic polymer is normally water miscible.Yet, depending on the composition of copolymer component, some in them are water insoluble.Consider to be easy to preparation, they are preferably water miscible.Yet, even they almost can not be water-soluble, also can be by using them in their water-soluble compatible organic solvents.
As described herein the organic solvent of water compatible be meant can about 10% amount organic solvent soluble in water, and comprise alcohol for example methyl alcohol, ethanol, isopropyl alcohol or normal propyl alcohol; Glycol is ethylene glycol, diethylene glycol (DEG) or glycerine for example; Ester is ethyl acetate and propyl acetate for example; Ketone is acetone and methyl ethyl ketone for example; With acid amides N for example, dinethylformamide.In this case, the consumption of organic solvent preferably is less than water.
The consumption of cationic polymer is generally 0.1-10g, but is preferably 0.2-5g/m
2Ink-jet recording sheet.
Can will introduce in the ink absorbing layer of ink-recording sheet material of the present invention, and introduce as required and in other layers of providing except above-mentioned various additives those.Preferably introduce image especially and keep reinforcing agent for example ultraviolet radiation absorber, antioxidant and antiseepage toner.
As these ultraviolet radiation absorber, antioxidant and antiseepage toner and what enumerate is alkylphenol compound (comprising hindered phenol), alkylthio cresols compound, the hydroquinones compound, alkylating hydroquinones compound, tocopherol (tocophenol) compound, sulfo-hexichol (thiodipenyl) ether compound, the compound that contains at least two thioether bonds, bisphenol compound, O-, N-and S-benzyl compounds, the hydroxybenzyl compound, triaizine compounds, phosphonate compounds, the acylamino-phenolic compounds, ester compounds, amide compound, ascorbic acid, antioxidant based on amine, 2-(2-hydroxyphenyl) benzotriazole cpd, 2-hydroxy benzophenone ketonic compound, acrylate, water-soluble or hydrophobicity slaine, organo-metallic compound, metal complex, hindered amine compound (comprising so-called TEMPO compound), 2-(2-hydroxyphenyl) 1,3, the 5-triaizine compounds, matal deactivator, phosphite compound, the phosphinate compound, hydroxylamine compound, nitrone compound, peroxide scavenger, the polyamide stabilizing agent, polyether compound, the alkalescence auxiliary stabilizer, nucleator, the benzofranone compound, indolinone compound, phosphine compound, polyamine compounds, thiourea compound, carbamide compound, hydrazide compound, amidine compound, saccharide compound, hydroxybenzoic acids, dihydroxy-benzoic acid compound and trihydroxybenzoic acid compound.
In the middle of these, the phenolic compounds of preferred alkylization, the compound that contains at least two thioether bonds, bisphenol compound, ascorbic acid, antioxidant, water-soluble or hydrophobicity slaine, organo-metallic compound, metal complex, hindered amine compound, hydroxylamine compound, polyamine compounds, thiourea compound, carbamide compound, hydrazide compound, hydroxybenzoic acids and dihydroxy-benzoic acid compound based on amine.
What introduce in addition can be for example polystyrene of various additive well known in the art, polyacrylate, polymethacrylates, polyacrylamide, polyethylene, polypropylene, polyvinyl chloride, polyvinylidene chloride, or its copolymer, carbamide resin, small organic latex particle of forming by melamine resin for example, atoleine, dioctyl phthalate, tricresyl phosphate, for example the small fluid of being made up of silicone oil drips, various cations or non-ionic surface active agent, be described in JP-A Nos.-74193, ultraviolet radiation absorber among 57-87988 and the 62-261476, be described in JP-A Nos.57-74192,57-87989,60-71785,61-146591, anti-decolorizer among 1-95091 and the 3-13376, be described in JP-A Nos.59-42993,59-52689,62-280069, fluorescent whitening agent among 61-242871 and the 4-219266, the pH controlling agent is sulfuric acid for example, phosphoric acid, citric acid, NaOH, potassium hydroxide and potash, defoamer, anticorrisive agent, thickener, antistatic additive or delustering agent.
Can be used for carrier of the present invention is not particularly limited.When adopting the water imbibition carrier for example during paper, the water that spills makes their smoothness degenerate, and can produce wrinkling thus.In addition, the water imbibition carrier has caused wherein dyestuff and zirconium compounds or aluminium compound to be diffused into such problem in the middle of their, makes water-fast fastness degenerate, bleeding occur and reduced image density thus.Therefore, consider and show the desirable effect of the present invention and preferably adopt non-absorptive carrier.
What enumerate as can be used for water imbibition carrier of the present invention is, for example, and common cardboard, common fabric and wooden sheet material and plate.Paper especially most preferably in the middle of these, because paper material shows good water imbibition, and cost is another advantage.As paper carrier can be to adopt wood pulp as primary raw material, comprise chemical pulp for example LBKP and NBKP, mechanical pulp for example GP, CGP, RMP, TMP, CTMP, CNP or PGW and recovery fiber for example DIP make those.In addition, if desired, that then effectively uses can be various fibrous materials for example synthetic paper-pulp, synthetic fibers and inorfil.
If desired, can be with the prior art additive of various routines in the paper carrier above for example sizing agent (sizing agent), pigment, paper intensity reinforcing agent, fixative, fluorescent whitening agent, l Water Paper reinforcing agent or cation modifier are introduced.
Can make paper carrier by this way: with for example wood pulp and various additive blend of fibrous substance, and for example fourdrinier wire (Fourdrinier) paper machine, cylinder mould machine or twin-wire paper-machine make the mixture of gained carry out papermaking to adopt various paper machines.In addition, if desired, can in paper machine, adopt size press (size press) processing of starch and polyvinyl alcohol, various coating processing or calendering to handle during the papermaking.
What enumerate as preferred non-water imbibition carrier is plastic resin thin-film carrier and the carrier of using the covering of plastic resin film on the two sides of cardboard.
What enumerate as the plastic resin thin-film carrier is polyester film, polyvinyl chloride film, polypropylene film, cellulose triacetate film and polystyrene film, and the thin-film carrier by those laminations are made.Can use those transparent or translucent plastic resin films.
In the present invention, particularly preferred carrier is the paper that covers with plastic resin on the two sides, most preferred a kind of be the carrier that makes by the two sides that covers cardboard with vistanex.
Can adopt such method to make ink-jet recording sheet: use the coating system that is selected from common coating system aptly will comprise that the formation layer of ink absorbing layer is coated on the carrier separately or simultaneously, and subsequent drying.What be preferably used as coating system is, for example rolling method, rod cladding process, air knife knife coating, spraying process, curtain coating method, and be described in United States Patent(USP) Nos. 2,761, the sliding pearl cladding process in 419 and 2,761,791 and extrude cladding process.
When applying at least two simultaneously when constituting layer and adopting sliding pearl coating system, the viscosity of each liquid coating composition is preferably 5-100mPas, but 10-50mPas more preferably.In addition, when adopting curtain coating, above viscosity is preferably 5-1,200mPas, but 25-500mPas more preferably.
In addition, be preferably 100mPas at least in the viscosity of 15 ℃ of following liquid coating compositions, 100-30 more preferably, 000mPas, more more preferably 3,000-30,000mPas, but most preferably be 10,000-30,000mPas.
Preferred apply and drying means makes that being heated to 30 ℃ or higher liquid coating composition carries out multiple coating simultaneously, and after this under 1-15 ℃, the gained coating temporarily cooled off and 10 ℃ or relative superiority or inferiority drying more.Preferably carry out liquid coating preparation of compositions, coating and drying under the Tg of thermoplastic resin being equal to or less than, so that the above resin that is combined in the superficial layer can film forming.Preferred drying condition is under the laminar surface temperature of 5-50 ℃ wet-bulb temperature and 10-50 ℃.In addition, consider the uniformity of gained coating, preferably after applying the system of usage level adjustment immediately as the cooling system.
In addition, preferably above preparation process comprises 24 hours-60 days the stage that wherein stores under 35-70 ℃.
Heating condition is not particularly limited, as long as temperature is 35-70 ℃ and to store the duration be 24 hours-60 days.Preferred example is included in 36 ℃ of following 3 days-4 weeks, 40 ℃ of following 2 days-2 weeks or at 55 ℃ of following 1-7 days.By adopting heat treatment, can strengthen sclerous reaction or its crystallization of water-soluble binder, obtain desirable ink absorption.
In order to improve adhesiveness, can on the surface of the ink absorbing layer side of above carrier, provide subsurface stratum (sublayer) to ink absorbing layer.The subsurface stratum adhesive is for example gelatin or polyvinyl alcohol of hydrophilic polymer preferably, and the latex polymer under-30 to 60 ℃ Tg.These adhesive consumption are 0.001-2g/m
2Recording medium.In order to make static defective minimum, for example a spot of cationic polymer of a small amount of antistatic additive well known in the art can be introduced in the subsurface stratum.
Also can provide bottom, to improve sliding capability and static characteristic the apparent surface of the ink absorbing layer of above carrier.Adhesive in the bottom is for example gelatin or polyvinyl alcohol of hydrophilic polymer preferably, and the latex polymer under-30 to 60 ℃ Tg.In addition, can introduce antistatic additive for example cationic polymer and various surfactant, and the delustering agent under the about 20 μ m of the about 0.5-of average particulate diameter.The thickness of bottom is generally 0.1-1 μ m.So that curl hour, thickness is generally 1-20 μ m when bottom is provided.Bottom can be by two-layer composition at least.
Embodiment
Describe the present invention now with reference to embodiment, yet the present invention is not limited to this.Incidentally, " % " among the embodiment is weight %, unless otherwise indicated.
" preparation of recording sheet "
[preparation of recording sheet 1]
(preparation of silica dispersion D-1)
3, when 000rpm stirs down, at room temperature 400L being contained 25% homodisperse in advance primary particle size is about the vapour phase processes silica of 0.007 μ m (AEROSIL 300, produce by NipponAerosil Corp.) silica dispersion B-1 (pH 2.6 times, contain 0.5% ethanol) and 0.6L anionic optical brighteners (UVITEX NFW LIQUID, produce by Ciba Specialty ChemicalsCo.) join 110L and contain 12% cationic polymer HP-1, the aqueous solution C-1 of 10% normal propyl alcohol and 2% ethanol is (pH 2.5 times, contain 2g defoamer SN381, produce by San Nobuko Co.) in.Subsequently, when stirring, add 54L gradually and contain the aqueous mixture solution A 1 (under the concentration of each comfortable 3 weight %) that weight ratio is 1: 1 boric acid and borax.
Adopt the Co. by Sanwa Industry subsequently, the high pressure homogenisers that Ltd produces is at 3kN/cm
2Pressure under the mixture of gained is disperseed.Making cumulative volume by the adding pure water then is 630L, makes almost transparent silica dispersion D-1 thus.
Cationic polymer (HP-1)
(preparation of silica dispersion D-2)
Prepare silica dispersion D-2 in the mode identical, except omitting the anionic property fluorescent whitening agent with above silica dispersion D-1.
(preparation of silica dispersion D-3)
Prepare silica dispersion D-3 in the mode identical, except (TAKIBINE#1500, by Taki Chemical Co., Ltd. produces, and presses Al under 83.5% basicity with moisture aluminium chloride solution with above silica dispersion D-2
2O
3Meter contains 23.75%) replace outside the cationic polymer HP-1.
The method that employing is described among the JP-A No.11-321079 is measured silica dispersion D-1, the D-2 of as above preparation and the dispersity of D-3.Susceptible of proof has formed the composite particles that highly stable cation transforms as a result.
In addition, adopt by Advantec Toyo Co., the TCP-30 type filter that Ltd. produces under the filtering accuracy of 30 μ m with each filtration of dispersion D-1, D-2 and D-3.
(ink absorbing layer liquid coating preparation of compositions)
The additive that each is following add successively as above preparation silica dispersion each and mix with it, preparation is used for the ink absorbing layer liquid coating composition of porous layer thus.Incidentally, each addition is expressed as the quantity of every liter of liquid coating composition.
＜ground floor ink absorbing layer liquid coating composition: lowermost layer 〉
Silica dispersion D-1 650ml
8.0% moisture polyvinyl alcohol (average degree of polymerization and saponification degree are 88%) solution 250ml
4% moisture surfactant (FUTERGENT 400S, by Neos Co., Ltd. prepares) solution 2.0ml
Pure water 1000ml
＜second layer ink absorbing layer liquid coating composition 〉
Silica dispersion D-1 670ml
8.0% moisture polyvinyl alcohol (average degree of polymerization be 3,800 and saponification degree be 88%) solution 240ml
Acryloyl group copolymer emulsion method resin (Vinysol 1083, by Daido Chemical Corp. preparation)
30ml
Pure water 1000ml
＜the three layer of ink absorbing layer liquid coating composition 〉
Silica dispersion D-2 630ml
8.0% moisture polyvinyl alcohol (average degree of polymerization be 3,800 and saponification degree be 88%) solution 250ml
Pure water 1000ml
＜the four layer of ink absorbing layer liquid coating composition: lowermost layer 〉
Silica dispersion D-2 630ml
8.0% moisture polyvinyl alcohol (average degree of polymerization be 3,800 and saponification degree be 88%) solution 250ml
6% aqueous surfactant (QUARTAMIN 25P is by Kao Corp. preparation) 3.0ml
4% aqueous surfactant (FUTERGENT 400S, by Neos Co., the Ltd. preparation) solution
1.0ml
Pure water 1000ml
Each ink absorbing layer liquid coating composition that will as above prepare under the filtering accuracy of 20 μ m by the TCPD-30 filter of being produced by Advantec Toyo filters, and filters by the TCPD-10 filter subsequently.
(preparation of recording sheet)
Subsequently, adopt sliding hopper type coating machine to be coated to simultaneously and be coated with on the two sides on the poly paper carrier (RC paper), to obtain wet coating layer thickness described below at 40 ℃ of four kinds of ink absorbing layer liquid coating compositions that will as above prepare down.
＜wet coating layer thickness 〉
Ground floor: the 42 μ m (SiO of coating
2: 4.33g/m
2)
The second layer: the 42 μ m (SiO of coating
2: 4.57g/m
2)
The 3rd layer: the 40 μ m (SiO of coating
2: 4.40g/m
2)
The 4th layer: the 40 μ m (SiO of coating
2: 4.40g/m
2)
Incidentally, be respectively about 1.5m and about 4 as the width of the RC paper of carrier and length above, 000m, as described below with its winding rolling.
Be prepared as follows employed RC paper.With the polyethylene that combines 6% anatase titanium dioxide to moisture be 8% and basic weight be that the surface of the photographic base paper of 170g melt extrudes coating, to obtain the thickness of 35 μ m, with polyethylene the back side is melt extruded coated with the thickness that obtains 40 μ m simultaneously.On face side, apply after the corona discharge, subsurface stratum is coated on the gained surface so that the coat weight of the polyvinyl alcohol on the RC paper (PVA235, by Kuraray Co., Ltd. prepares) reaches 0.05g/m
2Subsequently, also corona discharge is put on the back side that is coated with bottom, this bottom combines latex adhesive, 0.1g antistatic additive (cationic polymer) and the 0.1g of the about 80 ℃ styrene-based-acrylate of the about 0.4g Tg about 2 μ m silica granules as delustering agent.
The following drying of carrying out after applying ink absorbing layer liquid coating composition.By means of making the temperature of coating surface be reduced to 13 ℃ in 15 seconds by the cooling zone that remains on 5 ℃, a plurality of dry sections of setting aptly by temperature wherein carry out drying subsequently.After this gained coating is twined rolling, make recording sheet 1 thus.As above the gross thickness of the ink absorbing layer of Zhi Bei drying is 42.5 μ m, and the thickness of the 4th layer (the superiors) is 11.5 μ m.In addition, do not have in conjunction with water-soluble polyvalent metal compounds in recording sheet 1 one deck in office.
(preparation of recording sheet 2)
So that with moisture aluminium chloride (TAKIBINE#1500, by Taki Chemical Co., Ltd. preparation, under 83.5% basicity as Al
2O
3Be combined with 23.75%) on the 4th layer of the outer recording sheet 1 that is coated to as above preparation, to obtain by Al
2O
3The coat weight of meter is 0.5g/m
2Such mode prepares recording sheet 2.This outer coating of passing through that is equivalent to be described among the JP-A No.2002-160442 is introduced water-soluble polyvalent metal compounds.
(preparation of recording sheet 3)
Prepare recording sheet 3 in the mode identical, except replace the silica dispersion D-2 in the 4th layer with silica dispersion D-3 with recording sheet 1.Incidentally, the SiO that applies in the 4th layer
2Weight is 4.40g/m
2, Al
2O
3Coat weight is 0.5g/m
2(SiO
2/ Al
2O
3=8.8), simultaneously dry coating layer thickness is 11.5 μ m (total drying layer thickness 27%).The A/ of recording sheet 3 (A+B) is 1.0.This is equivalent to be described in the multilayer recording materials among the JP-A No.2002-160442.
(preparation of recording sheet 4)
Prepare recording sheet 4 in the mode identical, except with being modified into SiO with above recording sheet 3
2/ Al
2O
3=4 silica dispersion replaces being used for outside the 4th layer the silica dispersion D-3, other the 4th layer SiO
2Coat weight becomes 2.0g/m
2, Al
2O
3Coat weight becomes 0.5g/m
2, and dry layer thickness becomes 4.0 μ m (total drying layer thickness 9.4%).Incidentally, be equivalent to 2.40g/m
2Small silica granule equally distributed by three layers, its each be provided for each of three layers of ground floor-Di, keep total SiO thus
2Coat weight.The A/ of recording sheet 4 (A+B) is 1.
(preparation of recording sheet 5)
Prepare recording sheet 5 in the mode identical, except replace the silica dispersion D-2 in the 3rd layer with silica dispersion D-3 with recording sheet 1.Incidentally, the SiO of the 3rd layer coating
2Weight is 4.4g/m
2, the Al of coating
2O
3Weight is 0.5g/m
2(SiO
2/ Al
2O
3=8.8), simultaneously dry layer thickness is 11.5 μ m (total drying layer thickness 27%).The A/ of recording sheet 5 (A+B) is 0.
(preparation of recording sheet 6)
Prepare recording sheet 6 in the mode identical,, make the SiO of coating except be used for the silica dispersion of recording sheet 4 by use with above recording sheet 5
2Weight becomes 2.0g/m
2, the Al of coating
2O
3Weight becomes 0.5g/m
2(SiO
2/ Al
2O
3)=4, and dry layer thickness is become outside the 4.0 μ m (total drying layer thickness 9.4%).Incidentally, be equivalent to 2.40g/m
2Small silica granule equally distributed by three layers, its each be provided for each of ground floor, the second layer and the 4th layer, keep total SiO thus
2Coat weight.The A/ of recording sheet 6 (A+B) is 0.
(preparation of recording sheet 7)
Prepare recording sheet 7 in the mode identical with above recording sheet 4, except with moisture aluminium chloride solution (TAKIBINE#1500, by Taki Chemical Co., the Ltd. preparation, under 83.5% basicity as Al
2O
3Contain 23.75%) join the ink absorbing layer liquid coating composition that is used for the 3rd layer, to obtain by Al
2O
3Count 0.05g/m
2Coat weight outside.The A/ of recording sheet 7 (A+B) is 0.9.
(preparation of recording sheet 8)
Prepare recording sheet 8 in the mode identical with above recording sheet 4, except with moisture aluminium chloride solution (TAKIBINE#1500, by Taki Chemical Co., the Ltd. preparation, under 83.5% basicity as Al
2O
3Contain 23.75%) join the ink absorbing layer liquid coating composition that is used for the 3rd layer, to obtain by Al
2O
3Count 0.75g/m
2Coat weight outside.The A/ of recording sheet 8 (A+B) is 0.4.
(preparation of recording sheet 9)
Prepare recording sheet 9 in the mode identical with above recording sheet 1, except with moisture aluminium chloride solution (TAKIBINE#1500, by Taki Chemical Co., the Ltd. preparation, under 83.5% basicity as Al
2O
3Contain 23.75%) join the ink absorbing layer liquid coating composition that is used for the 4th layer, to obtain by Al
2O
3Count 0.5g/m
2Coat weight, simultaneously with the SiO that applies
2Weight control is at 2.0g/m
2, and the layer thickness of drying is controlled at 4.0 μ m.Incidentally, be equivalent to 2.40g/m
2Small silica granule equally distributed by three layers, its each be provided for each of three layers of ground floor-Di, keep total coating SiO thus
2Weight.The A/ of recording sheet 9 (A+B) is 1.0.
(preparation of recording sheet 10)
Prepare recording sheet 10 in the mode identical with above recording sheet 1, except just before applying, passing through feed pipe (in-line) with moisture aluminium chloride solution (TAKIBINE#1500, by TakiChemical Co., Ltd. preparation, under 83.5% basicity as Al
2O
3Contain 23.75%) join the ink absorbing layer liquid coating composition that is used for the 4th layer, to obtain by Al
2O
3Count 0.5g/m
2Coat weight outside.Incidentally, with the 4th layer coating SiO
2Weight control is at 2.0g/m
2, and the layer thickness of drying is controlled at 4.0 μ m, and be equivalent to 2.40g/m
2Small silica granule equally distributed by three layers, its each be provided for each of three layers of ground floor-Di, keep total coating SiO thus
2Weight.The A/ of recording sheet 10 (A+B) is 1.0.
(preparation of recording sheet 11)
Prepare recording sheet 11 in the mode identical with above recording sheet 4, except just before applying by feed pipe with zirconyl acetate (ZIRCOSOL ZA, by Daiichi Kigenso Kagaku-Kogyo Co., Ltd. preparation) join the ink absorbing layer liquid coating composition that is used for the 3rd layer, to obtain by ZrO
2Count 0.08g/m
2Coat weight outside.The A/ of recording sheet 11 (A+B) is 0.86.
(preparation of recording sheet 12)
Prepare recording sheet 12 in the mode identical, except controlling to SiO with above recording sheet 4
2/ Al
2O
3=20 silica dispersion is used for the 4th layer and make the 4th layer SiO
2Coat weight, Al
2O
3Coat weight and dry layer thickness become 2.0g/m respectively
2, 0.1g/m
2Outside 4.0 μ m (total drying layer thickness 9.4%).Incidentally, be equivalent to 2.40g/m
2Small silica granule equally distributed by three layers, its each be provided for each of three layers of ground floor-Di, keep total coating SiO thus
2Weight.The A/ of recording sheet 12 (A+B) is 1.0.The recording sheet 12 of gained is equivalent to be described in the recording sheet among the JP-A No.2001-287451.
(preparation of recording sheet 13)
Prepare recording sheet 13 in the mode identical, except controlling to SiO with above recording sheet 4
2/ Al
2O
3=2.5 silica dispersion is used for the 4th layer and make the 4th layer SiO
2Coat weight, Al
2O
3Coat weight and dry layer thickness become 2.0g/m respectively
2, 0.8g/m
2Outside 4.0 μ m (total drying layer thickness 9.4%).Incidentally, be equivalent to 2.40g/m
2Small silica granule equally distributed by three layers, its each be provided for each of three layers of ground floor-Di, keep total coating SiO thus
2Weight.The A/ of recording sheet 13 (A+B) is 1.0.
(preparation of recording sheet 14)
Prepare recording sheet 14 in the mode identical, except controlling to SiO with above recording sheet 4
2/ Al
2O
3=6.5 silica dispersion is used for the 4th layer and make the 4th layer SiO
2Coat weight, Al
2O
3Coat weight and dry layer thickness become 2.0g/m respectively
2, 0.308g/m
2Outside 4.0 μ m (total drying layer thickness 9.4%).Incidentally, be equivalent to 2.40g/m
2Small silica granule equally distributed by three layers, its each be provided for each of three layers of ground floor-Di, keep total coating SiO thus
2Weight.The A/ of recording sheet 14 (A+B) is 1.0.
(preparation of recording sheet 15)
Prepare recording sheet 15 in the mode identical, except controlling to SiO with above recording sheet 4
2/ Al
2O
3=7.5 silica dispersion is used for the 4th layer and make the 4th layer SiO
2Coat weight, Al
2O
3Coat weight and dry layer thickness become 2.0g/m respectively
2, 0.267g/m
2Outside 4.0 μ m (total drying layer thickness 9.4%).Incidentally, be equivalent to 2.40g/m
2Small silica granule equally distributed by three layers, its each be provided for each of three layers of ground floor-Di, keep total coating SiO thus
2Weight.The A/ of recording sheet 15 (A+B) is 1.0.The recording sheet 15 of gained is equivalent to be combined with the recording sheet of water-soluble polyvalent metal compounds than the present invention less amount.
" evaluation of recording sheet characteristic "
(measuring the distribution of polyvalent metal compounds in ink absorbing layer)
Each recording sheet section of using slicer as above to prepare, the TRIFT-II that employing is produced by PhysicalElectronics Co. makes the cross section of the ink absorbing layer of gained partly carry out TOF-SIMS under the condition of In as ionic species and 25kV accelerating potential and measures, and measures aluminum ions distribution on depth direction.Susceptible of proof as a result, in recording sheet of the present invention, the maximum that is obtained from aluminum ions secondary ion intensity be present on the depth direction in surperficial 10 μ m.
Fig. 2 and 3 each naturally as the recording sheet 2 of the comparative example of the representative example of polyvalent metal compounds distribution measuring and the polyvalent metal compounds distribution measuring figure of recording sheet of the present invention 4.
Fig. 2 represents the aluminum ions distribution measuring figure of ink absorbing layer on depth direction that measures by TOF-SIMS.In Fig. 2, the outmost surface layer segment is at the right-hand member of figure, and length 0 (μ m) expression carrier surface.Based on Fig. 2 as can be seen, more be obtained from the inside that aluminum ions secondary singal is distributed in ink absorbing layer, more thus aluminium chloride is distributed in inside.
Fig. 3 represents the aluminium ion distribution measuring figure of ink absorbing layer on the depth direction of recording sheet 4 of the present invention that measures by TOF-SIMS.In Fig. 3, in as above identical mode, the outmost surface layer segment is at the right-hand member of figure, and length 0 (μ m) expression carrier surface.
In recording sheet 4 of the present invention, significantly a large amount of aluminum ions secondary ion signals that are obtained from are created in the zone of dividing from the upper space part to 10 μ m deeps, find out that thus aluminium chloride is distributed in the surf zone.
(color forms the evaluation of performance)
By using pure printing ink, adopt the ink-jet printer PM-950C that produces by Seiko Epson Corp. to print the solid image of black.After allowing to keep dry 3 hours, adopt opacimeter to measure the black density of gained and form the scale that performance is used as color.
(evaluation of bleeding resistance after the storage that prolongs)
By using pure printing ink, adopt the ink-jet printer PM-950C that produces by Seiko Epson Corp. under 23 ℃ and 55% relative humidity, on blue solid image as a setting, to print the black line that live width is about 0.3mm.After allowing to keep dry 1 hour, be inserted in the transparent file clearly.Under 40 ℃ and 80% relative humidity, allow this clearly file kept for 1 week.Adopt microdensitometer to measure before above storage and the width of black line (specifying the width of 50% reflection density part of maximal density is live width) afterwards.Subsequently, the variation of the live width that obtains being expressed from the next ratio, and with the scale of income value as bleeding resistance between the storage life that prolongs.Along with this value reduces, bleeding resistance increases.Commercial durability degree is at most 130.
Line width variation ratio=(storing the live width of the preceding black line of live width/storage of back black line) * 100
(evaluation of ink absorption)
The ink-jet printer PM-950C that employing is produced by Seiko Epson Corp. is the solid blue image of printing under 23 ℃ and 80% relative humidity.Immediately with the surface of the solid image of finger friction and the stain on the image that detects by an unaided eye, the while is based on following standard evaluation ink absorption after printing.
A: through not noticing the image stain with the finger friction
B: the part in friction is noticed slight image stain
C: in the image of friction, produce tangible stain.
(printing the evaluation of the density stabilized property in back)
By using pure printing ink, adopt the ink-jet printer PM-950C that produces by Seiko Epson Corp. to print the solid image of yellow, magenta and cyan, and maintenance 0.5 hour and 24 hours under 23 ℃ and 55% relative humidity subsequently.Adopt reflection-densitometer to measure each yellow, magenta and cyan density after 0.5 hour and 24 hours, and respectively by color density D (0.5) and color density D (24) expression.Subsequently, calculate D (the 24)/D (0.5) * 100 of each coloured image, and be assigned therein as density reduction ratio.The averag density that obtains each yellow, magenta and cyan image reduces ratio D (on average), and as the scale of printing the density stabilized property in back.Because the variable density after D (on average) near 100, therefore prints reduces, and obtains good density stabilized property.
Following table is represented the evaluation result except the distribution measuring of the polyvalent metal compounds of ink absorbing layer.
| Recording sheet number | Single | Note | |||||
| *1 | Color forms performance (black image) | Bleeding resistance (line width variation ratio) | Ink absorption | Density stabilized property (Δ D (on average)) | |||
| 1 | Do not have | 2.03 | 185 | A | 82.5 | Comp. | |
| 2 | Do not have | 2.08 | 155 | B | 85.8 | Comp. | |
| 3 | Do not have | 2.20 | 130 | C | 93.4 | Comp. | |
| 4 | Exist | 2.38 | 125 | A | 98.0 | Inv. | |
| 5 | Do not have | 2.07 | 145 | C | 90.6 | Comp. | |
| 6 | Do not have | 2.15 | 135 | A | 92.8 | Comp. | |
| 7 | Exist | 2.35 | 120 | A | 97.4 | Inv. | |
| 8 | Do not have | 2.18 | 120 | B | 93.7 | Comp. | |
| 9 | Exist | 2.32 | 125 | A | 97.2 | Inv. | |
| 10 | Exist | 2.33 | 125 | A | 96.9 | Inv. | |
| 11 | Exist | 2.35 | 115 | A | 98.5 | Inv. | |
| 12 | Exist | 2.25 | 130 | A | 95.8 | Comp. | |
| 13 | Exist | 2.37 | 120 | B | 98.0 | Comp. | |
| 14 | Exist | 2.34 | 125 | A | 97.0 | Inv. | |
| 15 | Exist | 2.28 | 128 | A | 97.0 | Comp. | |
Comp.: comparative example
Inv.: the present invention
*1: in the peaked existence of secondary ion intensity in surperficial 10 μ m on the depth direction
As can clearly finding out from the result of last table, the density stabilized property that recording sheet of the present invention forms at color after bleeding resistance, ink absorption and the printing between storage life of performance, prolongation is good aspect all.
Embodiment 2
Prepare recording sheet 16-19 in the mode identical with the recording sheet 4 of embodiment 1, except adopting alkali formula aluctyl (TAKICERUM G-17L respectively, by Taki Chemical Co., Ltd. produce, under 72% basicity), zirconyl acetate (ZIRCOSOL ZA, by Daiichi Kigenso KagakuKogyo Co., Ltd. produce), acid chlorization oxygen zirconium (zirconyl acid chloride) (ZIRCOSOLZC-2, by Daiichi Kigenso Kagaku Kogyo Co., Ltd. produce) and the moisture aluminium chloride solution (TAKIBINE#1500 of magnesium chloride replacement, by Taki Chemical Co., the Ltd. preparation is pressed Al under 83.5% basicity
2O
3Meter contains 23.79%) outside, and adopt the same procedure that is described among the embodiment 1 to estimate each project.Each of recording sheet 16-18 can show and be described in those suitable good results of the recording sheet 4 in the table 1.Wherein magnesium chloride is formed performance and bleeding resistance as the color that the recording sheet 19 of water-soluble polyvalent metal shows with recording sheet 3 pars, and the result of ink absorption that obtains and density stabilized property is identical with recording sheet 4.
Claims (10)
1. ink-jet recording sheet that includes the ink absorbing layer on carrier, this ink absorbing layer contains small silica granule, hydrophilic adhesive and water-soluble polyvalent metal compounds; Wherein
Described ink absorbing layer is by two-layer composition at least, the amount distribution peak value of water-soluble multivalent compounds on depth direction is positioned at 10 μ m from the upper space, water-soluble polyvalent metal compounds and the small silica granule weight ratio when all changing into its separately oxide satisfies following formula (1) in the superiors of ink absorbing layer, and the dry coating thickness of the superiors is the 2-20% of ink absorbing layer gross thickness
Formula (1)
3≤SiO
2/MO
x/2≤7
Wherein M represents to be combined in divalence or the high-valency metal atom more in the water-soluble polyvalent metal compounds, and x represents divalence or the chemical valence of high-valency metal atom M more.
2. the ink-jet recording sheet of claim 1, the weight (A) that wherein changes into the water-soluble polyvalent metal compounds of its oxide in the superiors is at least 0.50 with the ratio A/ (A+B) that changes into the gross weight (A+B) of the water-soluble polyvalent metal compounds of its oxide.
3. the ink-jet recording sheet of claim 1, wherein water-soluble polyvalent metal compounds is selected from water miscible aluminium compound and zirconium compounds.
4. the ink-jet recording sheet of claim 2, wherein water-soluble polyvalent metal compounds is selected from water miscible aluminium compound and zirconium compounds.
5. the ink-jet recording sheet of claim 1 wherein adopts vapor-phase process to prepare small silica granule.
6. the ink-jet recording sheet of claim 2 wherein adopts vapor-phase process to prepare small silica granule.
7. the ink-jet recording sheet of claim 1, wherein hydrophilic adhesive is a polyvinyl alcohol.
8. the ink-jet recording sheet of claim 2, wherein hydrophilic adhesive is a polyvinyl alcohol.
9. the ink-jet recording sheet of claim 1 wherein prepares carrier by the two sides that covers cardboard with vistanex.
10. the ink-jet recording sheet of claim 2 wherein prepares carrier by the two sides that covers cardboard with vistanex.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/JP2004/016375 WO2006046312A1 (en) | 2004-10-28 | 2004-10-28 | Inkjet recording paper |
| WOPCT/JP2004/016375 | 2004-10-28 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1769065A true CN1769065A (en) | 2006-05-10 |
Family
ID=36215471
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200510092314.XA Pending CN1769065A (en) | 2004-10-28 | 2005-08-26 | Ink-jet recording sheet |
Country Status (3)
| Country | Link |
|---|---|
| EP (1) | EP1658994A1 (en) |
| CN (1) | CN1769065A (en) |
| WO (1) | WO2006046312A1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103707673A (en) * | 2012-10-09 | 2014-04-09 | 佳能株式会社 | Recording medium |
| CN104245339A (en) * | 2012-05-02 | 2014-12-24 | 伊斯曼柯达公司 | Inkjet receiving medium and pre-treatment composition for inkjet printing |
| CN107921806A (en) * | 2015-10-02 | 2018-04-17 | 惠普发展公司，有限责任合伙企业 | Glueing composition |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060210729A1 (en) * | 2005-03-18 | 2006-09-21 | Konica Minolta Photo Imaging, Inc. | Ink-jet recording sheet |
| US8053044B2 (en) | 2007-07-31 | 2011-11-08 | Hewlett-Packard Development Company, L.P. | Media for inkjet web press printing |
| EP3341210A4 (en) | 2015-11-06 | 2018-10-31 | Hewlett-Packard Development Company, L.P. | Printable recording media |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61237681A (en) | 1985-04-15 | 1986-10-22 | Teijin Ltd | Recording sheet |
| JP2750433B2 (en) | 1988-02-12 | 1998-05-13 | 日本合成化学工業株式会社 | Inkjet recording paper |
| JPH07285265A (en) | 1994-04-18 | 1995-10-31 | Sekisui Chem Co Ltd | Recording material for aqueous ink |
| JP3834998B2 (en) | 1998-04-20 | 2006-10-18 | コニカミノルタホールディングス株式会社 | Inkjet recording paper |
| JP4086417B2 (en) * | 1999-06-11 | 2008-05-14 | 三菱製紙株式会社 | Recording medium for pigment ink and recording method |
| JP3986258B2 (en) * | 2000-01-31 | 2007-10-03 | 日本製紙株式会社 | Inkjet recording medium suitable for pigment ink |
| JP2001328340A (en) * | 2000-05-19 | 2001-11-27 | Fuji Photo Film Co Ltd | Ink jet recording sheet |
| JP2002160442A (en) * | 2000-11-27 | 2002-06-04 | Konica Corp | Ink jet recording paper |
| JP2004114459A (en) * | 2002-09-25 | 2004-04-15 | Mitsubishi Paper Mills Ltd | Method for ink jet recording |
-
2004
- 2004-10-28 WO PCT/JP2004/016375 patent/WO2006046312A1/en active Application Filing
-
2005
- 2005-08-11 EP EP05107398A patent/EP1658994A1/en not_active Withdrawn
- 2005-08-26 CN CN200510092314.XA patent/CN1769065A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104245339A (en) * | 2012-05-02 | 2014-12-24 | 伊斯曼柯达公司 | Inkjet receiving medium and pre-treatment composition for inkjet printing |
| CN104245339B (en) * | 2012-05-02 | 2015-12-02 | 伊斯曼柯达公司 | Inkjet receptive media, printing process, ink jet printing pretreatment coating composition |
| CN103707673A (en) * | 2012-10-09 | 2014-04-09 | 佳能株式会社 | Recording medium |
| CN103707673B (en) * | 2012-10-09 | 2015-11-11 | 佳能株式会社 | Recording medium |
| CN107921806A (en) * | 2015-10-02 | 2018-04-17 | 惠普发展公司，有限责任合伙企业 | Glueing composition |
| CN107921806B (en) * | 2015-10-02 | 2020-07-14 | 惠普发展公司，有限责任合伙企业 | Sizing composition |
| US11255048B2 (en) | 2015-10-02 | 2022-02-22 | Hewlett-Packard Development Company, L.P. | Sizing compositions |
Also Published As
| Publication number | Publication date |
|---|---|
| EP1658994A1 (en) | 2006-05-24 |
| WO2006046312A1 (en) | 2006-05-04 |
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