CN1717332A - Ink-jet recording material - Google Patents
Ink-jet recording material Download PDFInfo
- Publication number
- CN1717332A CN1717332A CN 200380104347 CN200380104347A CN1717332A CN 1717332 A CN1717332 A CN 1717332A CN 200380104347 CN200380104347 CN 200380104347 CN 200380104347 A CN200380104347 A CN 200380104347A CN 1717332 A CN1717332 A CN 1717332A
- Authority
- CN
- China
- Prior art keywords
- recording materials
- ink
- silica
- jet recording
- ink jet
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Ink Jet Recording Methods And Recording Media Thereof (AREA)
- Ink Jet (AREA)
Abstract
The present invention discloses an ink-jet recording material having a support and at least two ink-receptive layers containing inorganic fine particles and a hydrophilic binder, which comprises an ink-receptive layer A nearer to the support containing precipitated silica fine particles having an average secondary particle diameter 500 nm or less, or precipitated silica fine particles having an average secondary particle diameter 500 nm or less and fumed silica fine particles having an average secondary particle diameter 500 nm or less, and containing less than 20 parts by weight of a polyvinyl alcohol based on 100 parts by weight of the whole silica fine particles in the ink-receptive layer A, and an ink-receptive layer B farther from the support containing at least one kind of fine particles selected from fumed silica, alumina and alumina hydrate and less than 25 parts by weight of a polyvinyl alcohol based on 100 parts by weight of the fine particles.
Description
Technical field
The present invention relates in ink-jet printer etc. the ink jet recording materials that uses when writing down with ink-jet recording, say in further detail, relate to the good and less ink jet recording materials of bleeding that in the preservation process, produce with dye ink typewriting back of high glaze and colour rendering, the ink absorption of this material, anti-crooked disruptiveness and marresistance are also good, and be less with the blemish that multiple layer coating produces.
Background technology
As the recording materials that are used for ink-jet recording, known have at common paper or be known as the recording materials that the porous matter ink absorbing layer that is made of hydrophilic adhesive such as pigment such as amorphous silica and polyvinyl alcohol forms are set on the supporter of ink-jet recording paper.
For example, that uses at present has, siliceous pigment such as silica are coated on the paper supporter with hydrophilic adhesive and recording materials.Also disclose use with the sedimentation silica aggregate with mechanical means pulverize the silicon dioxide microparticle that forms as 10-300nm method (for example, with reference to the spy open flat 9-286165 communique, the spy opens flat 10-181190 communique).But,, still fail to satisfy the lustrous surface and the colour rendering of the recording materials that are similar to photo that the present invention will reach so far with regard to these recording materials.
On the other hand, proposed also that ink-receiver layer forms double-layer structure and be provided with the recording materials of glossiness on the upper strata than higher layer.For example, known be provided with on based on the ink absorbing layer of inorganic pigment etc. the layer that contains colloidal silica or aluminium oxide or hydrated alumina as the recording materials of gloss presentation layer (for example, with reference to the spy open the 2000-37944 communique, the spy opens flat 7-89216 communique).In addition, also proposed to be provided with lower floor contain pulverize the layer that noncrystalline synthetic silica and upper strata contains fumed silica recording materials (for example, open the 2001-80204 communique with reference to the spy), be provided with lower floor contain the gel method silica of pulverizing and upper strata contain fumed silica or aluminium oxide layer recording materials (for example, open the 2001-277712 communique with reference to the spy), in addition, the recording materials (for example, with reference to the WO02/34541A1 communique) on the upper strata that is provided with the lower floor that contains fumed silica and salic or hydrated alumina are also disclosed.
On the other hand, by the high image qualityization of ink-jet printer, can finish the printing that is equal to silver halide photography.For example, in order to realize being similar to the picture quality of photo (photo-like) etc., can use the light color printing ink be called photograph printing ink (photoink) etc. or Neutral colour printing ink such as grey, dead color etc. in ink-jet printer one side, realize more high image quality thus, this recording method also existing people propose.
Use recording materials as taking a picture, even above-mentioned recording materials can not be satisfied the demand fully, therefore urgent expectation improves glossiness and colour rendering further.In addition, when printing with dye ink, the recording materials that the bleeding of urgently expecting to produce in the preservation process further is improved.In addition, also require higher ink absorption.Though making the ink-receiver layer thickening is the effective means that realizes high ink absorption, even the curvature of a little also can make on the ink-receiver layer problem that cracks (bending is broken) when existence is handled recording materials.This be because in order to ensure the high ink absorption of recording materials on the basis of the ink-receiver layer that originally just forms high fragility, further make the cause of the high coating thickening of this fragility.
As solving the method that above-mentioned bending is broken, effectively dwindle inorganic pigment in the ink-receiver layer/adhesive ratio or minimizing as the boric acid of the crosslinking agent adding of adhesive or the method for boratory addition.But, can variation with regard to its ink absorption of method that dwindles inorganic pigment/adhesive ratio.In addition, even in the method that reduces boric acid or boratory addition, ink absorption also can variation, and then causes glossiness to descend or produce the inhomogeneous of gloss.
In addition, there is the problem that the coating faults such as crackle in the manufacturing process increase in these recording materials with double-layer structure.The mechanism of production of coating fault is still not fully aware of, and different two-layer of rate of drying produce because of multiple layer is coated with but can be speculated as.Open in the 2003-211824 communique the spy, disclose the technology of using sedimentation silica and fumed silica of mixing.But wherein disclosed is by making the coating solution high concentrationization that the method for ink jet recording materials cheaply is provided, and for how to avoid because the fault that multiple layer coating produces does not have any open or prompting.
Summary of the invention
It is good and print the few ink jet recording materials of bleeding that the back produces with dye ink in the preservation process to the purpose of this invention is to provide high glaze and colour rendering; The 2nd purpose provides ink absorption, colour rendering and anti-crooked disruptiveness good and glossiness and the also good ink jet recording materials of marresistance; The 3rd purpose provides the ink jet recording materials of the few surface defects that produces along with multiple layer coating.
Purpose of the present invention can be realized by following ink jet recording materials.
1. ink jet recording materials, coating is provided with in the ink jet recording materials of the two-layer at least ink-receiver layer that contains inorganic particles and hydrophilic adhesive on supporter, ink-receiver layer A near supporter contains the sedimentation silicon dioxide microparticle of average aggregate particle size below 500nm, perhaps contain average aggregate particle size simultaneously at sedimentation silicon dioxide microparticle below the 500nm and the average fumed silica particulate of aggregate particle size below 500nm, and with respect to all silicon dioxide microparticle 100 weight portions of ink-receiver layer A, the polyvinyl alcohol that contains less than 20 weight portions contains from supporter ink-receiver layer B far away and to be selected from fumed silica, at least a particulate in aluminium oxide and the hydrated alumina and with respect to the polyvinyl alcohol of these particulate 100 weight portion less thaies 25 weight portions.
2. the ink jet recording materials of record in above-mentioned 1, the sedimentation silicon dioxide microparticle of above-mentioned average aggregate particle size below 500nm be, sedimentation silica is ground into the particulate that the size of average aggregate particle size below 500nm forms in aqueous medium.
3. the ink jet recording materials of record in above-mentioned 2, the above-mentioned particulate that the pulverizing of sedimentation silica is formed is, the sedimentation silica that will have the above average aggregate particle size of 5 μ m is in the presence of cationic compound, and working medium pulverizer in aqueous medium (media mill) is pulverized the particulate that forms.
4. the ink jet recording materials of record in above-mentioned 3, the oil absorption of above-mentioned sedimentation silica is below the 210ml/100g.
5. the ink jet recording materials of record in above-mentioned 1, the fumed silica particulate of above-mentioned average aggregate particle size below 500nm is, in the presence of cationic compound, pulverizing is the particulate of the size of average aggregate particle size below 500nm in aqueous medium with fumed silica.
6. the ink jet recording materials of record in above-mentioned 1, the sedimentation silicon dioxide microparticle that contains in above-mentioned ink-receiver layer A and the weight ratio of vapor phase method silicon dioxide microparticle are 30: 70～70: 30.
7. the ink jet recording materials of record in above-mentioned 1, above-mentioned ink-receiver layer A contains boric acid or borate.
8. the ink jet recording materials of record in above-mentioned 1, the drying coated amount that contains the ink-receiver layer B of above-mentioned fumed silica is counted 4g/m with the amount of fumed silica
2Below.
9. the ink jet recording materials of record in above-mentioned 1, above-mentioned ink-receiver layer B contains boric acid or borate.
10. the ink jet recording materials of record in above-mentioned 1, above-mentioned hydrated alumina are that shape is the tabular hydrated alumina more than 2 than (aspect ratio).
11. the ink jet recording materials of record in above-mentioned 1, above-mentioned hydrated alumina is imitative-boehmite.
12. the ink jet recording materials of record in above-mentioned 1, above-mentioned aluminium oxide is a gama-alumina.
13. the ink jet recording materials of record in above-mentioned 1 has the layer that colloidal silica is contained as main body on above-mentioned ink-receiver layer B.
14. the ink jet recording materials of record in above-mentioned 1, above-mentioned supporter is the resistance to water supporter.
The specific embodiment
Below, explain the present invention.
Can use films such as polyethylene, polypropylene, polyvinyl chloride, diacetate esters resin, triacetate resin, glassine paper, acrylic resin, PET, PEN as being used for supporter of the present invention, resistance to water supporters such as resin-coating paper, water imbibition supporters such as good quality paper, art paper, coated paper, mold (cast) art paper etc.The preferred resistance to water supporter that uses.Especially the thickness of these supporters is preferably about 50～250 μ m.
Being used for silicon dioxide microparticle of the present invention is the noncrystalline synthetic silica, and the noncrystalline synthetic silica can roughly be divided into fumed silica, damp process silica and other according to manufacture method.Fumed silica also is called dry process silica, makes of flame hydrolysis usually.Specifically, generally be known that burn the together method of preparation of silicon tetrachloride and hydrogen and oxygen, the QS type of the commercially available Aerosil that Japanese Aerosil (strain) arranged, Tokuyama (strain).
Damp process silica also can be divided into sedimentation silica, gel method silica, sol method silica according to manufacture method.Sedimentation silica can be made by sodium metasilicate and sulfuric acid are reacted under alkali condition, and the silicon dioxide granule that particle is grown up is assembled, sedimentation, carries out commercialization through filtration, washing, process dry, crushing and classification then.The silica offspring of being made by this method is loose aggregate particles, thereby can obtain relatively to be easy to the particle pulverized.As sedimentation silica, for example commercially available Nipsil, Tokusil, the Finesil of Tokuyama society system that Japanese silica society system is arranged.Gel method silica can be made by sodium metasilicate and sulfuric acid are reacted under acid condition.At this moment, because silicon dioxide granule dissolving in the ageing process small-medium size, and separate out once more in the mode that between the predecessor of macroparticle, connects predecessor, therefore clear and definite predecessor will disappear, and formed is the harder aggregate particles with internal voids structure.For example, commercially available Mizukasil, the Sylojet of Grace Japan society system that marshy land chemistry society system is arranged.Sol method silica is also referred to as colloidal silica, can obtain by the double decomposition that sodium metasilicate takes place under the effect of acid etc., perhaps will obtain the commercially available SNOWTEX that daily output chemical industry society system is for example arranged through the silicon dioxide gel heat ageing that obtains behind the resinbed.
In ink-receiver layer A of the present invention, contain the sedimentation silica of average aggregate particle size below 500nm.Has average aggregate particle size more than the 1 μ m with the sedimentation silica of usual way manufacturing, so use the particulate that is crushed into the following size of 500nm.As breaking method, can preferably use to be scattered in the wet type dispersion method that the silica in the aqueous medium is mechanically pulverized.As the wet type dispersion machine, can use medium pulverizers such as ball mill, ball mill (beads mill), sand mill; High-pressure homogenizer, super-pressure homogenizer equal pressure formula dispersion machine; Ultrasonic dispersing machine and film rotation (spin) type dispersion machine etc., but medium pulverizer such as ball mill especially preferably used among the present invention.
The preferred average primary particle diameter of sedimentation silica that is used for ink-receiver layer A of the present invention is below the 50nm, preferred especially 3-40nm.In addition, the oil absorption of sedimentation silica of the present invention is preferably the scope of 120-210ml/100g, further is preferably the scope of 160-210ml/100g especially.Oil absorption is to measure according to the record of JISK-5101.
The pulverizing of sedimentation silica of the present invention is preferably carried out in the presence of cationic compound.If add cationic compound in the silica in being scattered in water, then tend to produce aggregation, but by it is carried out pulverization process, can obtain the dispersion of higher concentration when only being scattered in the water, its as a result dispersion efficiency can rise, can further pulverize and be fine particulate.In addition,, can make the coating fluid high concentrationization during modulation coating fluid, further improve production efficiency by using the high concentration dispersion liquid.Especially, be the above sedimentation silica of 5 μ m if use average aggregate particle size this moment, the viscosity that then can suppress to be produced by the initial stage condensation product rises, and can disperse with higher concentration, so more favourable.The upper limit to average aggregate particle size has no particular limits, but the average aggregate particle size of sedimentation silica is below the 200 μ m usually.
As cationic compound, can use cation property copolymer or water soluble metallic compound.As cation property copolymer, the poly-second of preferred use is embraced imines, the polydiene propylamine, polyallylamine, poly-alkylamine, the spy opens clear 59-20696 number, the spy opens clear 59-33176 number, the spy opens clear 59-33177 number, the spy opens clear 59-155088 number, the spy opens clear 60-11389 number, the spy opens clear 60-49990 number, the spy opens clear 60-83882 number, the spy opens clear 60-109894 number, the spy opens clear 62-198493 number, the spy opens clear 63-49478 number, the spy opens clear 63-115780 number, the spy opens clear 63-280681 number, Te Kaiping 1-40371 number, Te Kaiping 6-234268 number, Te Kaiping 7-125411 number, record has primary～uncle amino in the Te Kaiping 10-193776 communiques etc., the polymer of quaternary ammonium salt base.And these polymer also can be salt such as ammonium chloride under possible situation.Especially preferably use the diallylamine derivative as cation property copolymer.The molecular weight of these cationic polymers is preferably about 2000～100,000, especially preferably about 2000-3 ten thousand.If molecular weight is greater than 100,000, then dispersion liquid viscosity becomes too high easily, so not preferred.
As water soluble metallic compound, can enumerate for example water miscible multivalent metal salt.Can enumerate the water soluble salt of the metal that is selected from calcium, barium, manganese, copper, cobalt, nickel, aluminium, iron, zinc, zirconium, titanium, chromium, magnesium, tungsten, molybdenum.Can enumerate for example calcium acetate particularly, calcium chloride, calcium formate, calcium sulfate, barium acetate, barium sulfate, barium phosphate, manganese chloride, manganese acetate, formic acid manganese dihydrate, the ammonium manganous sulfate hexahydrate, copper chloride, copper ammonium chloride (II) dihydrate, copper sulphate, cobalt chloride, cobalt thiocyanate, cobaltous sulfate, the nickel sulfate hexahydrate compound, nickel chloride hexahydrate, Nickel diacetate tetrahydrate, the ammonium nickel sulfate hexahydrate, acid amides nickelous sulfate tetrahydrate, aluminum sulfate, aluminium sulfite, thiosulfuric acid aluminium, aluminium polychloride, the aluminum nitrate nonahydrate, aluminum chloride hexahydrate, ferrous bromide, frerrous chloride, iron chloride, ferrous sulfate, ferric sulfate, zinc bromide, zinc chloride, the zinc nitrate hexahydrate, zinc sulfate, p-phenolsulfonic acid's zinc, titanium chloride, titanium sulfate, the lactic acid titanium, zirconium acetate, zirconium chloride, zirconyl chloride eight hydrates, hydroxide chlorination zirconium, chromium acetate, chromium sulfate, magnesium sulfate, magnesium chloride hexahydrate, the magnesium citrate nonahydrate, sodium phosphotungstate, natrium citricum tungsten, phosphoric acid 12 tungsten n hydrates, silicic acid 12 tungsten 26 hydrates, molybdenum chloride, phosphoric acid 12 molybdenum n hydrates etc.
In above-mentioned water-soluble polyvalent metal compounds, the compound of preferably forming also by aluminium or periodic table of elements 4A family metal (for example zirconium, titanium).Particularly preferably be water soluble aluminum compound.As water soluble aluminum compound, known for example have as the aluminium chloride of inorganic salts or its hydrate, aluminum sulfate or its hydrate, ammonium vanadium etc.The poly-aluminum hydroxide compound of the also known alkalescence that contains the aluminium cations polymer as mineral-type.
The poly-aluminum hydroxide compound of above-mentioned alkalescence is that principal component can stably contain for example (Al with what following general formula 1,2 or 3 was represented
6(OH)
15)
3+, (Al
8(OH)
20)
4+, (Al
13(OH)
34)
5+, (Al
21(OH)
60)
3+Deng alkalescence and the water-soluble poly aluminium hydroxide of the big multinuclear condensation ion of molecular weight.
(Al
2(OH)
nCl
6-n)
mGeneral formula 1
(Al (OH)
3)
nAlCl
3General formula 2
Al
n(OH)
mCl
(3n-m)0＜m＜3n general formula 3
Have as these materials, many wooden chemistries (strain) are run after fame as the commercially available product of water treatment agent with polyaluminium chloride (PAC), shallow field chemistry (strain) is with poly-aluminium hydroxide (Paho) the commercially available product of running after fame, and (strain) reason is ground Green with the Pyurakemu WT commercially available product of running after fame, other manufacturer also has similar products to sell, thereby obtains the material of various grades easily.
As being used for the water soluble compound that contains periodic table 4A family element of the present invention, the more preferably water soluble compound of titaniferous or zirconium.As the water soluble compound of titaniferous, can enumerate titanium chloride, titanium sulfate.As the water soluble compound that contains zirconium, can enumerate acetic acid zirconium, zirconium chloride, basic zirconium chloride, chloration hydro-oxidation zirconium, zirconium nitrate, alkaline carbonic acid zirconium, zirconium hydroxide, zirconium lactate, zirconium carbonate ammonium, potassium zirconium carbonate, zirconium sulfate, zirconium fluoride compound etc.Among the present invention, the so-called water-soluble character more than the dissolving 1 weight % in water at normal temperatures and pressures that is meant.
Obtaining average aggregate particle size of the present invention is in the concrete grammar of the following sedimentation silicon dioxide microparticle of 500nm, at first in water, add at least a of silica and cation property copolymer and/or cationic metallic compound, use zigzag blade type dispersion machine, helical blade type dispersion machine or the rotor stator type dispersion machine five equilibrium at least a acquisition pre-dispersed liquid of putting in bulk.Wherein, preferably at first in the water that contains cationic compound, add the sedimentation silicon dioxide granule with powder type as the adding method.Also can add the low boiling point solvent of appropriateness etc. as required again.The amount of cation property copolymer or water soluble metallic compound is preferably the 0.5-20 weight portion with respect to 100 weight portion silica, more preferably the 2-10 weight portion.Owing to make it in this scope, it is too high that the viscosity of silica pre-dispersed liquid can not become, thereby can improve the concentration of solid constituent.The solid component concentration of the pre-dispersed thing of silica of the present invention is high more good more, if but excessive concentrations, then can not disperse, so preferred range is 20-60 weight %, more preferably 30-50 weight %.
To carry out pulverization process with ball mill (beads mill) by the pre-dispersed thing of the silica that said method obtains.So-called ball mill is meant, after filling globule in the container that has agitating device in inside, by adding liquid material and make the agitating device rotation that globule is collided each other in container, gives the liquid material shearing force thus and the device handled.The particle diameter of globule is generally 0.1-10mm, preferred 0.2-1mm, more preferably 0.3-0.6mm.As globule bead, ceramic bead, bead etc. are arranged, but from the preferred zirconium oxide bead of the viewpoint of wear-resisting wiping and dispersion efficiency.In addition, the adding filling rate of globule is generally 40-80 capacity % in the container, preferred 55-80 capacity %.According to above-mentioned dispersion condition, can disperse thing to be ground into average aggregate particle size silica with high efficiency be particle below the 500nm, the also generation of the remaining and aggregation of rare coarse grain simultaneously.When the pre-dispersed thing of continuous processing, if through also residual seedy after the single treatment, then more than the preferred process secondary.With regard to the present invention, in the scope that does not produce coarse grain, the high more high concentrationization that helps coating fluid more of concentration.It is 20-60 weight %, more preferably 30-50 weight % that silica of the present invention disperses the preferable range of the solid component concentration of thing.Can enumerate nano mill, the ultravisco mill of AIMEX society system of shallow field ironworker society system and the Annular type OB grinder of MATSUBO society system, dyno mill of Shinmaru Enterprises society system etc. as commercially available ball mill.
When as one of embodiments of the present invention, employing in ink-receiver layer A except above-mentioned average aggregate particle size is sedimentation silicon dioxide microparticle below the 500nm, when also using average aggregate particle size as the fumed silica particulate below the 500nm, both usage rates are preferably 30: 70～70: 30 scope according to the weight ratio meter.In ink-receiver layer A, mix and use the reason of sedimentation silica and fumed silica to be, compare with the situation of only using sedimentation silica, can reduce blemish, particularly crackle during with ink-receiver layer A and multiple layer coating of ink-receiver layer B and drying.
Average primary particle diameter at ink-receiver layer A of the present invention and the fumed silica that contains in ink-receiver layer B as one of embodiments of the present invention is preferably below the 50nm, more preferably 5-30nm.When in ink-receiver layer, using fumed silica, preferably fumed silica is ground into average aggregate particle size and is the particle below the 500nm in the presence of cationic compound, in aqueous medium.As the example of cationic compound, can be set forth in cation property copolymer and the water soluble metallic compound enumerated in the pulverizing explanation of sedimentation silica.In the pulverizing, preferably use high-pressure homogenizer or medium pulverizer to make below the fine 300nm of turning to of average aggregate particle size.
Sedimentation silica and the fumed silica that is used for ink-receiver layer A also can disperse simultaneously, pulverize simultaneously, but often advantageously is treated to best separately average aggregate particle size respectively independently.
The appearance of the ink absorption downward trend of considering the rising of cost of energy in the miniaturization process and causing along with the close average primary particle diameter of average aggregate particle size, the lower limit of the average aggregate particle size of sedimentation silica and fumed silica is preferably about 50nm.
Aluminium oxide that contains among the ink-receiver layer B of the present invention and hydrated alumina are aluminium oxide and moisture thing thereof, can be that crystal also can be noncrystal, can use material amorphous and that have form such as spherical, tabular.Can use any in the two, also can be used in combination.
As aluminium oxide of the present invention preferably as the gama-alumina of the γ type crystal of aluminium oxide, wherein also preferred δ crystalloid.The predecessor of gama-alumina can be contracted to about 10nm, is the particle of about 50-300nm but can preferably use thousands of offspring crystal to tens thousand of nm usually with pulverizing such as ultrasonic wave or high-pressure homogenizer, opposed collision type jet mills.
Hydrated alumina of the present invention can be used general formula Al
2O
3NH
2O represents.Hydrated alumina is according to forming and crystal form different are divided into gibbsite, magnesium goyazite, norstrandite, boehmite, boehmite gel (imitating boehmite), diaspore (diaspore), amorphous noncrystal etc.Wherein, in the above-mentioned formula, when the n value is 1, represent the hydrated alumina of boehmite structure, when n greater than 1 hydrated alumina of representing imitative boehmite structure less than 3 time, when n 3 represents the hydrated alumina of non-crystal structure when above.Particularly preferred hydrated alumina is n greater than 1 hydrated alumina less than 3 imitative boehmite structure among the present invention.Hydrated alumina can be by aluminum alkoxide such as aluminium isopropoxides hydrolysis, with in the alkali and the known manufacture methods such as hydrolysis of aluminium salt, aluminate obtain.
The shape of the hydrated alumina that uses among the present invention also can be tabular, fibrous, needle-like, any shape such as spherical, bar-shaped, is that shape is than the tabular more than 2 from the viewpoint preferred shape of ink absorption.Preferred average shape is than being 3-6.Shape is represented the ratio of " diameter " than " thickness " of available particle.Wherein the diameter of so-called particle is meant, the diameter of a circle of the particle projected area when equaling with the electron microscope observation hydrated alumina.When shape than less than 2 the time, the fine pore distribution narrow of ink-receiver layer, ink absorption descends.When the shape ratio surpasses 8, be difficult to make the uniform hydrated alumina of particle diameter on the other hand.
The average primary particle diameter of fumed silica of the present invention, sedimentation silica, aluminium oxide and hydrated alumina, can be by behind the particle that disperses with electron microscope observation, the mean value of each diameter of a circle that equates with each projected area of 100 predecessors in being present in certain area of area is obtained as the particle diameter of predecessor.The average aggregate particle size of fumed silica of the present invention, aluminium oxide and hydrated alumina can be by measuring rare dispersion liquid and obtain with laser diffraction/diffuse transmission type particle size distribution device.
In the present invention, be polyvinyl alcohol as the main body of the hydrophilic adhesive that in ink-receiver layer, uses with inorganic particles, the polyvinyl alcohol or the cation-modified polyvinyl alcohol of preferred saponification completely or partially.
The polyvinyl alcohol of described preferred saponification completely or partially is that saponification degree is the polyvinyl alcohol of the saponification completely or partially more than 80%, and its average degree of polymerization is preferably 200-5000.In addition, as cation-modified polyvinyl alcohol, can enumerate for example special and open polyvinyl alcohol record in clear 61-10483 number, that on the main chain of polyvinyl alcohol or side chain, have primary～tertiary amine groups or quaternary ammonium group.
Among the present invention also can and with other the hydrophilic adhesive beyond above-mentioned, be below 20 weight portions preferably still with respect to 100 weight account polyethylene alcohol.
Among the present invention, preferably use crosslinking agent (hard coat agent) with above-mentioned hydrophilic adhesive.Object lesson as hard coat agent, just like formaldehyde, the aldehyde compound of glutaraldehyde and so on, as diacetyl, the ketone compounds of chloro pentanedione and so on, two (2-chloroethyl) urea, 2-hydroxyl-4,6-two chloro-1,3, the 5-triazine is as United States Patent (USP) the 3rd, 288, the compound with reactive halogen of No. 775 records, divinylsulfone is as United States Patent (USP) the 3rd, 635, the compound with reactive olefin of No. 718 records is as United States Patent (USP) the 2nd, 732, the N-methylol compound of No. 316 records, as United States Patent (USP) the 3rd, 103, the isocyanates of No. 437 records, as United States Patent (USP) the 3rd, 017, No. 280, United States Patent (USP) the 2nd, 983, the aziridine cpd class of No. 611 records, as United States Patent (USP) the 3rd, 100, the carbodiimides based compound class of No. 704 records, as United States Patent (USP) the 3rd, the epoxide of 091, No. 537 record is as the halo carboxyl aldehydes of mucochloric acid (mucochloric acid) and so on, dioxane derivative as dihydroxy dioxane and so on, as chrome alum chromalum, zirconium sulfate, boric acid, borate, the inorganic crosslinking agents of borax and so on etc. can use a kind in them, perhaps are used in combination more than 2 kinds.Wherein, special preferred boric acid or borate.The boric acid that uses among the present invention can be enumerated orthoboric acid, metaboric acid, hypoboric acid etc., can enumerate their sodium salt, sylvite, ammonium salt etc. as borate.
By in downside ink-receiver layer A, using polyvinyl alcohol and as the boric acid or the borate of hard coat agent, can obtain surface of good gloss, high ink absorption, the bleeding after the printing reduces.By adding boric acid or borate, can suppress crackle small in the downside ink-receiver layer, may be the lustrous surface that this point has had influence on upside ink receiving layer B, thereby become recording materials with high lustrous surface.
In ink receiving layer A of the present invention, the use amount of polyvinyl alcohol should be less than 20 weight portions with respect to sedimentation silicon dioxide microparticle or sedimentation silicon dioxide microparticle+fumed silica particulate 100 weight portions, is preferably the 8-19 weight portion.By making it, can obtain high ink absorption in above-mentioned scope.In addition, in ink receiving layer A of the present invention, boric acid or borate are preferably the 0.02-50 weight portion with respect to the content of polyvinyl alcohol 100 weight portions, more preferably the 0.5-35 weight portion.
In ink receiving layer B of the present invention, the use amount of polyvinyl alcohol should be less than 25 weight portions with respect to fumed silica, aluminium oxide or hydrated alumina 100 weight portions, more preferably the 8-24 weight portion.By making it, can obtain high lustrous surface, enough surface strength and good ink absorption in above-mentioned scope.Ink absorption will significantly descend when adding 25 weight portions are above.In ink receiving layer B of the present invention, boric acid or borate are preferably the 0.005-50 weight portion with respect to the content of polyvinyl alcohol 100 weight portions, more preferably the 0.01-30 weight portion.
The scope of the drying coated amount of ink receiving layer A is preferably 8-40g/m
2, 10-30g/m more preferably
2Preferred this scope in bleeding aspect from ink absorption, colour rendering and after printing.In addition, the scope of the drying coated amount of ink receiving layer B is preferably 0.5-18g/m
2, 1-10g/m more preferably
2From lustrous surface, colour rendering and the preferred above-mentioned scope in bleeding aspect after printing.The scope of the drying coated amount of ink receiving layer B is preferably 0.2-4g/m in the amount of fumed silica when wherein, containing fumed silica in ink receiving layer B
2, be preferably 0.5-4g/m especially
2The preferred above-mentioned scope from the aspect of ink absorption, colour rendering, anti-crooked disruptiveness.
The total amount of the drying coated amount of ink receiving layer A and ink receiving layer B is preferably 12-45g/m
2, 15-30g/m more preferably
2From the preferred above-mentioned scope in the intensity aspect of ink absorption and ink receiving layer.
In order to improve resistance to water, more preferably contain cationic compound in each layer of ink receiving layer of the present invention.As the example of cationic compound, can be set forth in cation property copolymer and the water soluble metallic compound enumerated in the pulverizing explanation of sedimentation silica.The cation property copolymer of the special about 5000-10 ten thousand of preferred molecular weight and the compound of forming by aluminium or periodic table 4A family metal (for example zirconium, titanium).Cation property copolymer can use a kind of, also can multiple compound use.
Among the present invention, in each ink-receiver layer except that surfactant, hard coat agent, can also further add illuminating colour, coloring pigment, ink dye fixer, ultra-violet absorber, antioxidant, dispersing of pigments agent, defoamer, be coated with known various additives such as flat agent, anticorrisive agent, fluorescent whitening agent, viscosity stabiliser, pH conditioning agent.
Among the present invention, except that printing ink receiving layer A, B, also ink receiving layer can be set again, but must be the layer that does not damage ink absorption this moment.For example, in order to improve marresistance, preferably be provided with on ink receiving layer the protective layer of colloidal silica as main body, prerequisite is not influence ink absorption, and for example its coating weight is counted about 5g/m according to solid constituent
2Below.The average grain diameter of the general predecessor of colloidal silica is about 5-100nm, is preferably formed the offspring of average grain diameter for about 10-500nm from the viewpoint of ink absorption.As commercially available spherical colloidal silica can enumerate the system SNOWTEX of daily output chemical industry society 20 grades, catalyst changes into the industrial system cataloidUSB of society etc., the system SNOWTEXUP of daily output chemical industry society etc. can be enumerated as the colloidal silica of chain, the system SNOWTEX PS-M of daily output chemical industry society etc. can be used as peart necklace shaped colloidal silica.In addition, also preferably use the colloidal silica of the surface modification of colloidal silica as cationic, wherein also preferred is the colloidal silica of cationic with surface modification with aluminium compound.Can enumerate the system SNOWTEX AK-L of daily output chemical industry society, SNOWTEX AK-UP, SNOWTEX PS-M-AK etc. as alumina modified colloidal silica.
In the present invention, the coating method that constitutes each layer of ink-receiver layer can adopt known coating method.For example sliding pearl (slide bead) mode, curtain coating mode, fashion of extrusion, air knife mode, roll coating model, rod are coated with mode etc.
Among the present invention, by as sliding pearl mode etc. under the condition that drying process is not set almost coating simultaneously constitute each layer of ink-receiver layer A, B etc., obtain the desired characteristic of each layer effectively, this is also ideal comparatively from the production efficiency aspect.That is to say that by stacked each layer under wetting state, thereby the composition that contains in each layer is difficult to be impregnated into lower floor, the formation of the composition of each layer of therefore dry back keeps good.
When on film support body, resin-coating paper, applying the coating liquid of ink-receiver layer, before coating, preferably carry out Corona discharge Treatment, flame treatment, ultraviolet treatment with irradiation, plasma treatment etc.
Among the present invention, using supporter, during particularly as the film of resistance to water supporter or resin-coating paper, preferably the priming coat that is provided with on the face of ink-receiver layer based on natural polymer or synthetic resin is being set.By the coating ink-receiver layer that contains inorganic particles of the present invention on this priming coat, cool off then, and under lower temperature, carry out drying, can further improve the transparency of ink-receiver layer.
The priming coat that is provided with on supporter is based on natural polymer or synthetic resin such as gelatin, caseins.As described synthetic resin, can enumerate acrylic resin, mylar, permalon, vinyl chloride resin, vinylacetate resin, polystyrene, polyamide, polyurethane resin etc.
Above-mentioned priming coat is arranged on the supporter with the thickness (dry film thickness) of 0.01～5 μ m.The scope of preferred 0.05～5 μ m.
In order to make supporter of the present invention have record property, static electricity resistance, carrying, prevent edge-rolling etc., can apply various back coatings are set.In back coating, can appropriate combination contain inorganic anti-electrostatic agent, organic antistatic agent, hydrophilic adhesive, latex, pigment, curing agent, surfactant etc.
Embodiment
Below, describe the present invention in detail by embodiment, but content of the present invention is not subjected to the restriction of embodiment.In addition, unless part and % explanation in advance, otherwise represent weight portion and weight % respectively.
Embodiment 1
＜vistanex coats the preparation of paper supporter 〉
1: 1 mixture of bleached hardwood sulfate pulp (LBKP) and coniferous tree bleaching sulfite pulp (NBSP) is pulled an oar to 300ml the preparation pulp slurry with Canadian Standard Freeness (Canadian Standard Freeness).To wherein adding with respect to paper pulp is that the alkyl ketene dimer of 0.5 weight % is as sizing agent (sizing agent), interpolation with respect to paper pulp be 1.0 weight % polyacrylamide, be the cationic starch of 2.0 weight %, be that the polyamide epichlorohydrin resin of 0.5 weight % is as reinforcing agent with respect to paper pulp with respect to paper pulp, dilute with water is made concentration and is 1% slurries.With fourdrinier machine these slurries are copied the weight of starching to paper and reach 170g/m
2, carry out dry damping, make the body paper that vistanex coats paper.Melting with respect to density down at 320 ℃ is 0.918g/cm
3Ldpe resin evenly be dispersed with the polyethylene resin composition of the Detitanium-ore-type titanium of 10 weight %, carry out extrusion coating on the body paper with 200m/ minute speed copying slurry, make thickness reach 35 μ m, the chilling roll that little asperities processing has been carried out in use pushes covering, forms the surface of resin-coating paper (resin-coated paper).On the other hand, melting density down at 320 ℃ equally is 0.962g/cm
370 parts of high-density polyethylene resins and density be the blended resin composition of 30 parts of 0.918 ldpe resins, in another side extrusion coating, reach 30 μ m thickness, use the chill roll that has carried out little asperities processing to push covering, form the back side of resin-coating paper.
The high-frequency corona discharge process is carried out on said polyolefins resin-coating paper surface, and coating contains the coating liquid for undercoat layer and the drying of following composition then, makes gelatin reach 50mg/m
2Thereby, make supporter.
＜priming coat is formed 〉
100 parts in lime treatment gelatin
2 parts of sulfosuccinic acids-2-ethylhexyl salt
10 parts of chrome alum chromalum
＜sedimentation silica dispersions 1 〉
Xiang Shuizhong adds chlorination dimethyldiallylammonium homopolymers 4 parts of (molecular weight 9000) and 00 part of (average primary particle diameter 15nm of sedimentation silica 1, average aggregate particle size 23 μ m, oil absorption 185ml/100g), use zigzag blade type dispersion machine (blade speed 30m/s) to make pre-dispersed liquid.Make then the pre-dispersed thing that obtains be filled with zirconia bead, filling rate that diameter is 0.3mm be 80 capacity %, disk circumference speed be under the condition of 10m/s by ball mill once, thereby the sedimentation silica dispersions 1 of making solid component concentration 30%, average aggregate particle size 200nm.
＜sedimentation silica dispersions 2 〉
Xiang Shuizhong adds chlorination dimethyldiallylammonium homopolymers 4 parts of (molecular weight 9000) and 00 part of (average primary particle diameter 11nm of sedimentation silica 1, average aggregate particle size 3 μ m, oil absorption 220ml/100g), use zigzag blade type dispersion machine (blade speed 30m/s) to make pre-dispersed liquid.Make then the pre-dispersed thing that obtains be filled with zirconia bead, filling rate that diameter is 0.3mm be 80 capacity %, disk circumference speed be under the condition of 10m/s by ball mill once, solid component concentration is 15%, average aggregate particle size is the sedimentation silica dispersions 2 of 200nm thereby make.
＜fumed silica dispersion liquid 〉
Xiang Shuizhong adds chlorination dimethyldiallylammonium homopolymers 4 parts of (molecular weight 9000) and 00 part of vapor phase method silica 1 (average primary particle diameter 7nm), uses zigzag blade type dispersion machine (blade speed 30m/s) to make pre-dispersed liquid.Make the pre-dispersed thing that obtains pass through pressure homogenizer once then under the condition of 40MPa, solid component concentration is 20%, on average aggregate particle size is the fumed silica dispersion liquid of 150nm thereby make.
Recording materials 1 (the present invention)
The ink receiving layer A1 that uses sliding pearl apparatus for coating to be coated with simultaneously on the surface of above-mentioned supporter to contain following composition carries out drying with coating fluid and ink receiving layer B1 after with coating fluid, so that the drying coated amount of silica is 23g/m in ink receiving layer A1
2, be 2g/m among the ink receiving layer B1
2, make recording materials 1.And ink receiving layer A1 is the lower floor near supporter, and ink receiving layer B1 is the upper strata.Drying condition after the coating is, 0 ℃ of cooling after 30 seconds down, carries out drying under 42 ℃, 10%RH, then carries out drying under 35 ℃, 10%RH, reaches 90% up to the solid constituent total concentration.
＜ink receiving layer A1 forms 〉
100 parts of sedimentation silica dispersions 1 (as the silica solid composition)
2.5 parts of boric acid
15 parts of polyvinyl alcohol (saponification degree 88%, average degree of polymerization 3500)
0.1 part in surfactant
3 parts of methylol melamine based compounds
(the big system BECKAMINE PM-N of Japanese ink chemical industry society)
＜ink receiving layer B1 forms 〉
100 parts of fumed silica dispersion liquids (as the silica solid composition)
5 parts of boric acid
20 parts of polyvinyl alcohol (saponification degree 88%, average degree of polymerization 3500)
0.5 part in surfactant
Recording materials 2 (the present invention)
Except coating ink receiving layer A1 coating fluid and ink receiving layer B1 coating fluid, so that the drying coated amount of silica is 18g/m in ink receiving layer A1
2, be 7g/m among the ink receiving layer B1
2In addition, make recording materials 2 in the same manner with recording materials 1.
Recording materials 3 (the present invention)
Except in ink receiving layer A1 forms, using sedimentation silica-coating liquid 2 replacement sedimentation silica-coating liquid 1, make recording materials 3 in the same manner with recording materials 1.
Recording materials 4 (comparative example)
Only be coated with ink receiving layer B1 coating fluid with coating fluid except not being coated with ink receiving layer A1, and be coated with 25g/m in the drying coated amount of silica
2In addition, make recording materials 4 in the same manner with recording materials 1.
Recording materials 5 (comparative example)
Only be coated with ink receiving layer A1 coating fluid with coating fluid except not being coated with ink receiving layer B1, and be coated with 25g/m in the drying coated amount of silica
2In addition, make recording materials 5 in the same manner with recording materials 1.
Recording materials 6 (comparative example)
Except in ink receiving layer A1 forms, the polyvinyl alcohol addition is defined as 25 parts, the boric acid addition is defined as beyond 4.2 parts, makes recording materials 6 in the same manner with recording materials 1.
Recording materials 7 (comparative example)
Except in ink receiving layer B1 forms, the polyvinyl alcohol addition is defined as 27 parts, the boric acid addition is defined as beyond 6 parts, makes recording materials 7 in the same manner with recording materials 1.
Recording materials 8 (comparative example)
＜sedimentation silica dispersions 3 〉
Except in sedimentation silica pre-dispersed liquid, the diameter that makes zirconia bead is transformed to by 0.3mm beyond the 3mm, the sedimentation silica dispersions 3 of making solid component concentration 30%, average aggregate particle size 800nm in the same manner with sedimentation silica pre-dispersed liquid 1.
Then, except in ink receiving layer A1 forms, using sedimentation silica dispersions 3 replacement sedimentation silica dispersions 1, make recording materials 8 in the same manner with recording materials 1.
The ink jet recording materials of making is as mentioned above carried out following evaluation, and it the results are shown in the table 1.
＜ink absorption 〉
With ink-jet printer (Seiko Epson society system, PM-880C) print cyan, magenta, yellow monochromatic 100% and 3 looks 300% respectively, just printed the back at the overlapping PPC paper of printing portion, crimping gently, detecting by an unaided eye is transferred to the degree of PPC with the quantity of ink on the paper, according to following standard overall merit.
Zero: do not have transfer printing fully.
△: 100% part does not have transfer printing, and 300% part has transfer printing slightly.
*: 100% part does not have transfer printing, and 300% part printing ink overflows, clearly transfer printing PPC with paper on.
* *: 100% part has transfer printing.
＜colour rendering 〉
(Seiko Epson society system PM-880C) is printed the image that comprises landscape and bust, according to following standard determination presentation quality with ink-jet printer.
Zero: have the quality as the photochrome.
△: be inferior to photochrome slightly.
*: obviously be inferior to photochrome.
* *: compared very inferior with photochrome.
And recording materials 6 fail to carry out these evaluations because printing ink overflows.
＜anti-crooked disruptiveness 〉
With recording materials dry (seasoning) 24 hours under 10 ℃, the condition of 20%RH, and under this temperature and humidity conditions, judge crooked disruptiveness.In the decision method, it is long that recording materials are cut to 12cm, and measuring with the ink receiving layer is that outside curve is heard the arc diameter when breaking when becoming circular-arc.Numerical value is little, and promptly diameter is more for a short time shows that anti-crooked disruptiveness is good more, is difficult to bending and breaks.Owing to be wound on the products of cylinder shape of 2 inches volume hearts sale is arranged also, so say the numerical value that need illustrate at least below the 50mm from practical aspect.
Table 1
| Ink absorption | Colour rendering | Anti-crooked disruptiveness (mm) | |
| Recording materials 1 (the present invention) | ◎ | ○ | 38 |
| Recording materials 2 (the present invention) | ◎ | ○ | 45 |
| Recording materials 3 the present invention) | ◎ | △ | 40 |
| Recording materials 4 (comparative example) | ◎ | ○ | 67 |
| Recording materials 5 (comparative example) | ◎ | × | 35 |
| Recording materials 6 (comparative example) | × | ○ | 34 |
| Recording materials 7 (comparative example) | ×× | 42 | |
| Recording materials 8 (comparative example) | ○ | ×× | 32 |
By The above results as can be known, ink jet recording materials of the present invention has good ink absorption and colour rendering, and anti-crooked disruptiveness is good.
Recording materials 9 (the present invention)
Making contains the ink receiving layer C1 coating fluid of following composition, after being coated with simultaneously with cunning pearl apparatus for coating with the order of coating fluid with coating fluid, ink receiving layer C1 with coating fluid, ink receiving layer B1 according to ink receiving layer A1, carrying out drying on the surface of supporter near a side of supporter, thus making recording materials 9.Temperature conditions when dry is identical with recording materials 1.Through coating, making the drying coated amount of silica of each layer reach ink receiving layer A1 respectively is 23g/m
2, ink receiving layer B1 is 2g/m
2, ink receiving layer C1 is 1g/m
2
＜ink receiving layer C1 forms 〉
100 parts of colloidal silicas (as the silica solid composition)
(daily output chemical industry society system, SNOWTEX AK-L, average primary particle diameter 40nm)
5 parts of polyvinyl alcohol
(saponification degree 88%, average degree of polymerization 3500)
0.3 part in surfactant
The ink absorption of above-mentioned recording materials 9, colour rendering are identical with recording materials 1 with anti-crooked disruptiveness.Not worse about glossiness and marresistance in addition than recording materials 1.When measuring marresistance, after ink jet recording materials is cut into 3cm * 4cm, weight at the additional 1200g of the one side opposite with printing surface, the sample that has added this weight is placed on PPC with on the paper to print prone mode, and will add the sample stretching 20cm of this weight with the speed of 50cm/min, with the naked eye judge, estimate the random line of printing portion image this moment and to the transfer printing degree of PPC usefulness paper.
By The above results as can be known, by have the layer that contains based on colloidal silica on supporter layer farthest, can have good ink absorption, colour rendering and anti-crooked disruptiveness, glossiness height, and marresistance in addition is also good.
Embodiment 2
Recording materials 10 (the present invention)
Carry out drying with coating fluid and ink receiving layer B2 after with coating fluid at the ink receiving layer A2 that uses sliding pearl apparatus for coating to be coated with simultaneously on the surface of above-mentioned supporter to contain following composition, the solid constituent coating weight when making drying is 20g/m in ink receiving layer A2
2, be 4g/m among the ink receiving layer B2
2Thereby, make recording materials 10.Ink receiving layer A2 is the lower floor near supporter, and ink receiving layer B2 is the upper strata.Drying condition after the coating is, 5 ℃ of coolings after 30 seconds down, carries out drying under 45 ℃, 10%RH, then carries out drying under 35 ℃, 10%RH, reaches 90% up to the solid constituent total concentration.
＜ink receiving layer A2 forms 〉
100 parts of sedimentation silica dispersions 1 (as the silica solid composition)
3 parts of boric acid
15 parts of polyvinyl alcohol (saponification degree 88%, average degree of polymerization 3500)
0.3 part in surfactant
＜ink receiving layer B2 forms 〉
100 parts of imitative boehmites
(average primary particle diameter 14nm, average aggregate particle size 160nm, flat column particle)
0.5 part of boric acid
12 parts of polyvinyl alcohol (saponification degree 88%, average degree of polymerization 3500)
0.3 part in surfactant
Recording materials 11 (the present invention)
Changing into ink receiving layer A2 except the solid constituent coating weight during with drying in embodiment 1 is 12g/m
2, ink receiving layer B2 is 12g/m
2In addition, make recording materials 11 in the same manner with recording materials 10.
Recording materials 12 (the present invention)
Except the condition of the non-alkali glass pearl of the globule condition of milling being changed into diameter 1mm, filling rate 70%, disk circumference speed 10m/s, the sedimentation silica dispersions 4 of making solid component concentration 30%, average aggregate particle size 320nm in the same manner with sedimentation silica pre-dispersed liquid 1.
Then, except in ink receiving layer A2 forms, sedimentation silica dispersions 1 being changed into sedimentation silica dispersions 4, make recording materials 12 in the same manner with recording materials 10.
Recording materials 13 (the present invention)
Except in ink receiving layer B2 forms, to change into average primary particle diameter be 15nm and shape imitates beyond the boehmite than the tabular that is 5 with imitative boehmite, makes recording materials 13 in the same manner with recording materials 10.
Recording materials 14 (the present invention)
Except in ink receiving layer B2 forms, imitative boehmite is changed into beyond the gama-alumina that average primary particle diameter is 13nm, make recording materials 14 in the same manner with recording materials 10.
Recording materials 15 (the present invention)
Except in ink receiving layer A2 forms, using sedimentation silica dispersions 2 replacement sedimentation silica dispersions 1, make recording materials 15 in the same manner with recording materials 10.
Recording materials 16 (the present invention)
Except the composition of ink receiving layer A2 being changed into following composition, make recording materials 16 in the same manner with recording materials 10.
The composition of＜ink receiving layer A3 〉
100 parts of sedimentation silica dispersions 1 (as the silica solid composition)
3 parts of boric acid
15 parts of polyvinyl alcohol (saponification degree 88%, average degree of polymerization 3500)
3 parts in the poly-aluminium hydroxide of alkalescence
0.3 part in surfactant
Recording materials 17 (the present invention)
Making contains the ink receiving layer C2 coating fluid of following composition, carrying out drying with sliding after the pearl apparatus for coating is coated with simultaneously with the order of coating fluid, thereby making recording materials 17 with coating fluid, ink receiving layer C2 with coating fluid, ink receiving layer B2 according to ink receiving layer A2 from a side on the surface of above-mentioned supporter near supporter.Temperature conditions when dry is identical with recording materials 10.Through coating, the solid constituent coating weight is as follows respectively when making each layer dry: be 20g/m in ink receiving layer A2
2, be 3g/m among the ink receiving layer B2
2, be 1g/m among the ink receiving layer C2
2
＜ink receiving layer C2 forms 〉
100 parts of colloidal silicas (as the silica solid composition)
(daily output chemical industry society system, SNOWTEXAK-L, average primary particle diameter 40nm)
5 parts of polyvinyl alcohol
(saponification degree 88%, average degree of polymerization 3500)
2 parts of boric acid
0.3 part in surfactant
Recording materials 18 (comparative example)
Be not coated with ink receiving layer B2 coating fluid, only be coated with ink receiving layer A2 coating fluid, the solid constituent coating weight was counted 24g/m when it measured according to drying
2, in addition, make recording materials 18 in the same manner with recording materials 10.
Recording materials 19 (comparative example)
Be not coated with ink receiving layer A2 coating fluid, only be coated with ink receiving layer B2 coating fluid, the solid constituent coating weight was counted 24g/m when it measured according to drying
2, in addition, make recording materials 19 in the same manner with recording materials 10.
Recording materials 20 (comparative example)
Except in ink receiving layer A2 forms, under the condition of not pulverizing, use sedimentation silica (average aggregate particle size 2 μ m) to replace silica dispersions 1 (silica solid composition) in addition, make recording materials 20 in the same manner with recording materials 10.
Recording materials 21 (comparative example)
Except in ink receiving layer A2 forms, use gel method silica (average aggregate particle size 300nm) to replace silica dispersions 1 (silica solid composition) in addition, make recording materials 21 in the same manner with recording materials 10.
Recording materials 22 (the present invention)
Except ink receiving layer A2 composition being changed into following composition, make recording materials 22 in the same manner with recording materials 10.
＜ink receiving layer A4 forms 〉
100 parts of fumed silicas (average primary particle diameter 20nm)
4 parts of chlorination dimethyl two allyl ammonium homopolymers
4 parts of boric acid
20 parts of polyvinyl alcohol (saponification degree 88%, average degree of polymerization 3500)
0.1 part in surfactant
The ink jet recording materials of making is as described above carried out following evaluation, and it the results are shown in the table 2.
＜ink absorption 〉
With commercially available ink-jet printer (society of Canon system, BJF-870) the full version of carrying out redness, blueness, green, black is respectively printed (solid printing), just printed the back at the overlapping PPC paper of printing portion, crimping gently, detecting by an unaided eye is transferred to the degree of PPC with the quantity of ink on the paper.According to following standard overall merit.
◎: do not have transfer printing fully.
Zero: transfer printing is arranged slightly, but can use.
△: transfer printing is arranged, use difficulty.
*: major part is carried out transfer printing, can not use.
＜colour rendering 〉
Carry out cyan, magenta, yellow, the versicolor full version printing of black,, and express versicolor optical density total value with Macbeath reflection densitometer measuring light density.What numerical value was little means that colour rendering is good.
＜plain pape part glossiness 〉
With the reflecting feel before the printing of skew ray observed and recorded material, estimate according to following standard.
◎: the high glaze sense as the chromatic colour photo.
Zero: the high glaze sense is arranged, but poorer slightly than ◎.
△: the reflecting feel as art paper, the coated paper is arranged.
*: the reflecting feel that the obfuscation as the good quality paper is arranged.
＜ooze profit when preserving 〉
Detecting by an unaided eye after one week is kept at photo behind the print image with the sample in the photo album, estimates according to following standard.
◎: do not ooze profit.
Zero: see that the profit of oozing is arranged slightly.
△: see and ooze profit.
*: have and obviously ooze profit.
Table 2
| Ink absorption | Colour rendering | Plain pape part glossiness | Ooze profit during preservation | |
| Recording materials 10 (the present invention) | ◎ | 9.0 | ◎ | ○ |
| Recording materials 11 (the present invention) | ○ | 8.7 | ◎ | ○ |
| Recording materials 12 (the present invention) | ◎ | 8.1 | ○ | ○ |
| Recording materials 13 (the present invention) | ◎ | 8.9 | ◎ | ◎ |
| Recording materials 14 the present invention) | ◎ | 8.5 | ○ | ○ |
| Recording materials 15 (the present invention) | ◎ | 7.9 | ◎ | ○ |
| Recording materials 16 (the present invention) | ◎ | 9.0 | ◎ | ◎ |
| Recording materials 17 (the present invention) | ◎ | 8.9 | ◎ | ◎ |
| Recording materials 18 (comparative example) | ◎ | 7.8 | ○ | △ |
| Recording materials 19 (comparative example) | × | 8.9 | ◎ | × |
| Recording materials 20 (comparative example) | ◎ | 6.9 | × | × |
| Recording materials 21 (comparative example) | ○ | 7.8 | ○ | △ |
| Recording materials 22 (comparative example) | ◎ | 8.0 | ◎ | × |
By the The above results decidable, ink jet recording materials of the present invention has good ink absorption, plain pape part glossiness, and colour rendering is good, and the profit of oozing during preservation is lacked.
Embodiment 3
Recording materials 23 (the present invention)
Carry out drying with coating fluid and ink receiving layer B1 after with coating fluid at the ink receiving layer A5 that uses sliding pearl apparatus for coating to be coated with simultaneously on the surface of above-mentioned supporter to contain following composition, so that the solid constituent coating weight is 20g/m during drying in ink receiving layer A5
2, be 4g/m among the ink receiving layer B1
2Thereby, make recording materials 23.Ink receiving layer A5 is the lower floor near supporter, and ink receiving layer B1 is the upper strata.Drying condition after the coating is, 5 ℃ of coolings after 30 seconds down, carries out drying under 45 ℃, 10%RH, then carries out drying under 35 ℃, 10%RH, reaches 90% up to the solid constituent total concentration.
＜ink receiving layer A5 forms 〉
50 parts of sedimentation silica dispersions 1 (as the silica solid composition)
50 parts of fumed silica dispersion liquids (as the silica solid composition)
3 parts of boric acid
15 parts of polyvinyl alcohol (saponification degree 88%, average degree of polymerization 3500)
0.3 part in surfactant
Recording materials 24 (the present invention)
The sedimentation silica dispersions 1 in ink receiving layer A5 is formed and the ratio of vapor phase method silica dispersions were made as 30: 70 according to solid constituent, make recording materials 24 in the same manner with recording materials 23.
Recording materials 25 (the present invention)
The sedimentation silica dispersions 1 in ink receiving layer A5 is formed and the ratio of vapor phase method silica dispersions were made as 70: 30 according to solid constituent, make recording materials 25 in the same manner with recording materials 23.
Recording materials 26 (the present invention)
Except ink receiving layer B1 composition being transformed to ink receiving layer B2 composition, make recording materials 26 in the same manner with recording materials 23.
Recording materials 27 (the present invention)
Except in ink receiving layer B2 forms, imitative boehmite is changed into beyond the gama-alumina that average primary particle diameter is 13nm, make recording materials 27 in the same manner with recording materials 26.
Recording materials 28 (the present invention)
Silica dispersions in ink receiving layer A5 is formed only is set at 100 parts of the sedimentation silica dispersions 1 (as the silica solid composition), makes recording materials 28 in the same manner with recording materials 23.
Recording materials 29 (comparative example)
＜sedimentation silica dispersions 5 〉
Xiang Shuizhong adds chlorination dimethyldiallylammonium homopolymers 4 parts of (molecular weight 9000) and 00 part of (average primary particle diameter 18nm of sedimentation silica 1, average aggregate particle size 2 μ m, oil absorption 200ml/100g), use zigzag blade type dispersion machine (blade speed 30m/s) to make the sedimentation silica dispersions 5 of solid component concentration 30%, average aggregate particle size 1.8 μ m.
Then, the silica dispersions in ink receiving layer A5 is formed only is set at 100 parts of the sedimentation silica dispersions 5 (as the silica solid composition), makes recording materials 29 in the same manner with recording materials 23.
Recording materials 30 (comparative example)
Silica dispersions in ink receiving layer A5 is formed only is set at 100 parts of the fumed silica dispersion liquids (as the silica solid composition), makes recording materials 30 in the same manner with recording materials 23.
Recording materials 31 (comparative example)
Silica dispersions in ink receiving layer A5 is formed only is set at 100 parts of the fumed silica dispersion liquids (as the silica solid composition), makes recording materials 31 in the same manner with recording materials 26.
The ink jet recording paper of making is as described above carried out evaluation and the following evaluation identical with embodiment 2.It the results are shown in the table 3.
＜superficiality 〉
◎: no problem fully.
Zero: point defect is arranged a little, but do not see crackle.
△: see crackle.
*: the defective that comprises crackle is many, not anti-use.
Table 3
| Ink absorption | Colour rendering | Plain pape part glossiness | Ooze profit during preservation | Superficiality | |
| Recording materials 23 (the present invention) | ◎ | 8.6 | ○～◎ | ○ | ◎ |
| Recording materials 24 (the present invention) | ◎ | 8.7 | ○～◎ | ○ | ◎ |
| Recording materials 25 (the present invention) | ◎ | 8.4 | ○ | ○ | ○～◎ |
| Recording materials 26 (the present invention) | ○ | 9.0 | ◎ | ◎ | ◎ |
| Recording materials 27 (the present invention) | ○ | 8.9 | ◎ | ◎ | ◎ |
| Recording materials 28 (the present invention) | ◎ | 7.9 | ○ | ○ | △～○ |
| Recording materials 29 (comparative example) | ◎ | 7.5 | × | ×～△ | △～○ |
| Recording materials 30 (comparative example) | ◎ | 8.5 | ○ | (×) | × |
| Recording materials 31 (comparative example) | ○ | 8.9 | ◎ | (×) | × |
Annotate: before the preservation in (*) one week of expression begins the thread profit of oozing is arranged
By the The above results decidable, recording material for ink-jet of the present invention has good ink absorption, plain pape part glossiness, and colour rendering is good, and the profit of oozing during preservation is lacked few surface defects.
Industrial utilizability
According to the present invention, can obtain high glaze and ink absorption, colour rendering, anti-crooked disruptiveness is good and when preserving printing portion ooze the few ink jet recording materials of profit, this material also has good marresistance, and can reduce the coating defects such as crackle.
Claims (14)
1. ink jet recording materials, coating is provided with in the ink jet recording materials of the two-layer at least ink-receiver layer that contains inorganic particles and hydrophilic adhesive on supporter, ink-receiver layer A near supporter contains the sedimentation silicon dioxide microparticle of average aggregate particle size below 500nm, perhaps contain average aggregate particle size simultaneously at sedimentation silicon dioxide microparticle below the 500nm and the average fumed silica particulate of aggregate particle size below 500nm, and with respect to all silicon dioxide microparticle 100 weight portions of ink-receiver layer A, the polyvinyl alcohol that contains less than 20 weight portions contains from supporter ink-receiver layer B far away and to be selected from fumed silica, at least a particulate in aluminium oxide and the hydrated alumina and with respect to the polyvinyl alcohol of these particulate 100 weight portion less thaies 25 weight portions.
2. ink jet recording materials as claimed in claim 1, wherein, the sedimentation silicon dioxide microparticle of described average aggregate particle size below 500nm is sedimentation silica to be ground into the particulate of the size of average aggregate particle size below 500nm in aqueous medium.
3. ink jet recording materials as claimed in claim 2, wherein, the described particulate that the pulverizing of sedimentation silica is formed is, the sedimentation silica that will have the above average aggregate particle size of 5 μ m is in the presence of cationic compound, and the working medium pulverizer is pulverized the particulate that forms in aqueous medium.
4. ink jet recording materials as claimed in claim 3, wherein, the oil absorption of described sedimentation silica is below 210ml/100g.
5. ink jet recording materials as claimed in claim 1, wherein, the fumed silica particulate of described average aggregate particle size below 500nm is, in the presence of cationic compound, in aqueous medium, the fumed silica pulverizing is the particulate of the size of average aggregate particle size below 500nm.
6. ink jet recording materials as claimed in claim 1, wherein, the sedimentation silicon dioxide microparticle that contains in described ink-receiver layer A and the weight ratio of vapor phase method silicon dioxide microparticle are 30: 70～70: 30.
7. ink jet recording materials as claimed in claim 1, wherein, described ink-receiver layer A contains boric acid or borate.
8. ink jet recording materials as claimed in claim 1, wherein, the drying coated amount that contains the ink-receiver layer B of described fumed silica is counted below the 4g/m2 with the amount of fumed silica.
9. ink jet recording materials as claimed in claim 1, wherein, described ink-receiver layer B contains boric acid or borate.
10. ink jet recording materials as claimed in claim 1, wherein, described hydrated alumina is that the shape ratio is at the tabular hydrated alumina more than 2.
11. ink jet recording materials as claimed in claim 1, wherein, described hydrated alumina is imitative boehmite.
12. ink jet recording materials as claimed in claim 1, wherein, described aluminium oxide is a gama-alumina.
13. ink jet recording materials as claimed in claim 1 wherein, has the layer that colloidal silica is contained as main body on described ink-receiver layer B.
14. ink jet recording materials as claimed in claim 1, wherein, described supporter is the resistance to water supporter.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP343238/2002 | 2002-11-27 | ||
| JP2002343238A JP2004174876A (en) | 2002-11-27 | 2002-11-27 | Ink jet recording material |
| JP045753/2003 | 2003-02-24 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1717332A true CN1717332A (en) | 2006-01-04 |
| CN100346987C CN100346987C (en) | 2007-11-07 |
Family
ID=32705053
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2003801043470A Expired - Fee Related CN100346987C (en) | 2002-11-27 | 2003-11-27 | Ink-jet recording material |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP2004174876A (en) |
| CN (1) | CN100346987C (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102470681A (en) * | 2009-08-12 | 2012-05-23 | 三菱制纸株式会社 | Inkjet recording material |
| CN101490184B (en) * | 2006-08-09 | 2012-05-30 | 花王株式会社 | Aqueous ink for inkjet recording |
| CN103991302A (en) * | 2013-02-19 | 2014-08-20 | 佳能株式会社 | Recording medium |
| CN104768769A (en) * | 2012-06-04 | 2015-07-08 | 惠普发展公司，有限责任合伙企业 | Fabric print media |
| CN108642908A (en) * | 2018-05-17 | 2018-10-12 | 江苏鑫林创世新材料科技有限公司 | A kind of high glaze people cotton inkjet printing canvas and preparation method thereof |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008246756A (en) * | 2007-03-29 | 2008-10-16 | Fujifilm Corp | Inkjet recording medium and manufacturing method thereof |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5521002A (en) * | 1994-01-18 | 1996-05-28 | Kimoto Tech Inc. | Matte type ink jet film |
| JP3438625B2 (en) * | 1998-12-10 | 2003-08-18 | マックス株式会社 | Prevention of looseness of reel wound wire for reinforcing bar binding |
| JP2000263924A (en) * | 1999-03-17 | 2000-09-26 | Mitsubishi Paper Mills Ltd | Ink jet recording paper and manufacture thereof |
| EP1120281B1 (en) * | 2000-01-28 | 2006-05-24 | Oji Paper Company Limited | Ink jet recording material |
-
2002
- 2002-11-27 JP JP2002343238A patent/JP2004174876A/en active Pending
-
2003
- 2003-11-27 CN CNB2003801043470A patent/CN100346987C/en not_active Expired - Fee Related
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101490184B (en) * | 2006-08-09 | 2012-05-30 | 花王株式会社 | Aqueous ink for inkjet recording |
| CN102470681A (en) * | 2009-08-12 | 2012-05-23 | 三菱制纸株式会社 | Inkjet recording material |
| CN102470681B (en) * | 2009-08-12 | 2014-01-01 | 三菱制纸株式会社 | Inkjet recording material |
| CN104768769A (en) * | 2012-06-04 | 2015-07-08 | 惠普发展公司，有限责任合伙企业 | Fabric print media |
| US9682587B2 (en) | 2012-06-04 | 2017-06-20 | Hewlett-Packard Development Company, L.P. | Fabric print media |
| CN104768769B (en) * | 2012-06-04 | 2017-08-04 | 惠普发展公司，有限责任合伙企业 | Cloth print medium |
| CN103991302A (en) * | 2013-02-19 | 2014-08-20 | 佳能株式会社 | Recording medium |
| CN103991302B (en) * | 2013-02-19 | 2016-06-01 | 佳能株式会社 | Recording medium |
| CN108642908A (en) * | 2018-05-17 | 2018-10-12 | 江苏鑫林创世新材料科技有限公司 | A kind of high glaze people cotton inkjet printing canvas and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2004174876A (en) | 2004-06-24 |
| CN100346987C (en) | 2007-11-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1238202C (en) | Recording material for ink-jet | |
| CN1262429C (en) | Ink jetting record material | |
| CN1169675C (en) | Ink jet recording paper | |
| CN1277692C (en) | Ink-jet recording medium and method for production thereof | |
| CN1826394A (en) | Pigment for use in inkjet recording medium coatings and methods | |
| CN1328504A (en) | Formulation suitable ink receptive coatings | |
| CN1729105A (en) | Ink jet recording material | |
| CN1642854A (en) | Composite sol, process for producing the same and ink-jet recording medium | |
| CN1663813A (en) | Ink jet recording sheet | |
| CN1929926A (en) | Process for producing coated sheet | |
| CN100346987C (en) | Ink-jet recording material | |
| CN1802262A (en) | Ink jet recording sheet | |
| CN1608031A (en) | Inorganic porous fine particles | |
| CN1616244A (en) | Method for preparing ink-jet recording material | |
| CN1723132A (en) | Inkjet recording medium | |
| CN101056770A (en) | Ink jet recording medium | |
| CN1319757C (en) | Ink jet recording sheet | |
| CN1906041A (en) | Method for producing ink-jet recording material | |
| CN1298351A (en) | Ink jet recording paper | |
| WO2006057290A1 (en) | Inkjet recording medium and method for producing same | |
| CN101049774A (en) | Jet ink recording body | |
| JP2008012774A (en) | Inkjet recording material | |
| CN1613659A (en) | Ink jet recording sheet and method for producing thereof | |
| JP4303740B2 (en) | Method for producing ink jet recording sheet | |
| CN1826232A (en) | Inkjet recording material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20071107 Termination date: 20091228 |