CN101258036A - Ink jet recording medium - Google Patents

Ink jet recording medium Download PDF

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Publication number
CN101258036A
CN101258036A CNA2006800325967A CN200680032596A CN101258036A CN 101258036 A CN101258036 A CN 101258036A CN A2006800325967 A CNA2006800325967 A CN A2006800325967A CN 200680032596 A CN200680032596 A CN 200680032596A CN 101258036 A CN101258036 A CN 101258036A
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CN
China
Prior art keywords
recording medium
ink jet
jet recording
coating composition
lower floor
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CNA2006800325967A
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Chinese (zh)
Inventor
加藤真
名越応昇
五十岚宏二
渡部由理
织田秀次
山口辉史
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Mitsubishi Paper Mills Ltd
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Mitsubishi Paper Mills Ltd
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Publication of CN101258036A publication Critical patent/CN101258036A/en
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Abstract

This invention provides an ink jet recording medium, which is small in coverage and, at the same time, can simultaneously realize high gloss and ink absorption. The ink jet recording medium is produced by coating a lower layer comprising a water-absorptive pigment, a latex, and boric acid or its salt and an upper layer comprising a submicron pigment and polyvinyl alcohol, and conducting casting.

Description

Ink jet recording medium
Technical field
The present invention relates to a kind of ink jet recording medium, even particularly hour also have the ink jet recording medium of high gloss and ink absorption at the overlay capacity of coating.
Background technology
Recently along with the fast development of ink jet printing machine technology, can obtain the record that image quality is equal to or higher than the picture quality of the record that is obtained by general photographic silver halide forme method.Therefore, ink jet recording medium also needs to have and is similar to the quality that is used for photographic silver halide forme method.In order to make ink jet recording medium satisfy above-mentioned needs, people are provided by the quality that comprises such as the ink absorbing layer of the base material of paper or plastic foil and the porous that provides on base material.
People have used in non-patent literature 1-3 disclosed chromium light art paper as the ink jet recording medium with gloss.Non-patent literature 2 is meant the specific embodiment of patent documentation 1-3.Yet,, from sensuously, be lower than the standard of the one-tenth phase paper that is used for photographic silver halide forme method by the recording medium of the technology preparation that proposes in the above-mentioned patent documentation as pointed in the non-patent literature 3 (the 43rd page).That is because when producing ink jet recording medium with above-mentioned technology, in order to obtain enough ink absorptions, needs to adopt a kind of meeting to cause forming the embodiment of hair check on the recording medium surface, and this is with the quality of deface.
In order to address these problems, patent documentation 4 suggestions are by producing ink jet recording medium with the electromagnetic wave solidified coating.Yet the electronic radiation solidifying instrument is on a grand scale usually, and its maintenance and control ten minutes trouble, and needs high management from the labor safety angle.
In this case, patent documentation 5 proposes a kind of lower floor that comprises pigment and adhesive by coating, provide the intermediate layer of containing boric acid then, and coating comprises sub-micron pigment and such as preparing the method for ink jet recording medium with the upper strata of adhesive the crosslinked polyvinyl alcohol of boric acid on the intermediate layer.According to this method, the surperficial less crackle that occurs on the upper strata, and can obtain and the identical reflecting feel of one-tenth phase paper level that is used for photographic silver halide forme method.
Yet, when producing ink jet recording medium,, must provide very thick coating in order to obtain enough glossiness or ink absorption with the method, such as in the embodiment of patent documentation 5, the thickness of coating is that lower floor and upper strata amount to 35g/m 2On base material, provide so big overlay capacity coating be uneconomic, and exist further problem, coating to be easy to peel off (to form dust), compare with adopting photographic silver halide forme method record, this just needs careful operation.
Patent documentation 5 is further open, and the upper strata preferably is provided when the coating composition in intermediate layer has specific water content.Because inventor's probe in this respect has been found that the glossiness of casting rear surface is not enough when the water content in intermediate layer is hanged down.Just, when producing ink jet recording medium with the method that proposes in the patent documentation 5, the degree of drying of the coating composition in intermediate layer is subjected to the influence such as the factors such as slight variation of the water absorbing properties of the temperature and humidity of production site and lower floor, and this finally can influence the reflecting feel of the ink jet recording medium that makes inevitably.
Patent documentation 1:JA-A-2001-010220
Patent documentation 2:JA-A-2001-071635
Patent documentation 3: No. the 2938380th, Japan Patent
Patent documentation 4:JA-A-2004-330725
Patent documentation 5:JA-A-2003-231342
Non-patent literature 1: author Kunio Nohara, " Ink Jet Gloss Paper According to CastingMethod (1) ", Convertech periodical, the 32nd volume, 11 phases, the 61st page.
Non-patent literature 2: author Kunio Nohara, " Ink Jet Gloss Paper According to CastingMethod (2) ", Convertech periodical, the 32nd volume, 12 phases, the 46th page.
Non-patent literature 3: author Kunio Nohara, " Ink Jet Gloss Paper According to CastingMethod (3) ", Convertech periodical, the 33rd volume, 1 phase, the 43rd page.
Summary of the invention
The purpose of this invention is to provide the almost irrealizable up to now ink jet recording medium that a kind of coating overlay capacity is little, glossiness is high, ink absorption is enough.
The method of dealing with problems
The result of the research of implementing for dealing with problems, make by lower floor's coating composition and the main upper strata coating composition of forming by sub-micron pigment and polyvinyl alcohol mainly formed of coating successively on ventilative supporting mass, and coating cast obtain the little and ink jet recording medium that have high gloss and an enough ink absorption of coating overlay capacity and become possibility by absorptive inorganic pigment, latex and boric acid or its salt.
And, in the present invention, can be by the wet method synthetic silica be obtained gratifying ink absorption as the absorptive pigment in the lower floor.
And, in the present invention, can carry out the dust formation that calender process obtains higher glossiness and less amount to lower floor subsequently by coating and dry lower floor.
And, in the present invention, can make glossiness and low amounts of dust form the balance that reaches height with ink absorption second by in to lower floor's calender process, Bake paper smoothness (Bekksmoothness) being controlled at 50-300.
And, in the present invention, can be by in lower floor's coating composition, containing the dust formation that glue silicon obtains higher ink absorption and less amount.
And, in the present invention, can be by polyurethane resin latex be obtained better glossiness as the latex in lower floor's coating composition.
And, in the present invention, can obtain at better ink jet recording medium aspect the low amounts of dust formation as the latex in lower floor's coating composition as the polyurethane resin latex of initial feed preparation by using polyether polyol.
And, in the present invention, can by will be among the JIS K 7311 tensile strength of regulation be that 30-70MPa, percentage elongation are that the polyurethane resin latex of 300-800% obtains at good especially ink jet recording medium aspect the low amounts of dust formation as the latex in lower floor's coating composition.
And, in the present invention, can be by will being that the polyurethane resin latex of 10-60nm obtains at better ink jet recording medium aspect the low amounts of dust formation as the latex in lower floor's coating composition with the particle diameter of dynamic light scattering determination.
And, in the present invention, can obtain ink jet recording medium by hydrated alumina is cast as the sub-micron pigment in the coating composition of upper strata and with wetting again good especially aspect the glossiness.
And, in the present invention, when with hydrated alumina as the sub-micron pigment in the coating composition of upper strata and so that wetting is cast again, can obtain higher glossiness and abrasion resistance by behind coating and dry upper strata, carrying out calender process.
And, in the present invention, when with hydrated alumina as the sub-micron pigment in the coating composition of upper strata and after coating and dry upper strata and calender process subsequently so that wetting is cast again, can obtain the highly glossiness and the abrasion resistance of balance second by after calender process, the Bake sheet smoothness of upper surface being adjusted to 50-300.
And, in the present invention, when with hydrated alumina as the sub-micron pigment in the coating composition of upper strata and so that wetting is cast again, can carry out the rewetting profit by liquid and handle the ink jet recording medium that obtains high abrasion resistance with the water-based that contains silica gel.
And, in the present invention, when hydrated alumina is handled when carrying out the casting of rewetting profit and handling as the sub-micron pigment in the coating composition of upper strata and the rewetting profit of liquid that contains the water-based of silica gel by use, the rewetting profit of liquid that can be by using the water-based that contains silica gel is handled the ink jet recording medium that obtains higher glossiness and abrasion resistance.
And, in the present invention, can obtain good ink jet recording medium aspect gradation of drop-out colour and low amounts of dust formation by the cation water-based dispersion that in the coating composition of upper strata, contains at least a resin that is selected from (1) (methyl) acrylate polymer, (2) styrene-(methyl) acrylate copolymer and (3) polyurethane, the particle diameter of described dispersion is 150nm or littler, this particle diameter dynamic light scattering determination.
And, in the present invention, can obtain at ink jet recording medium excellent especially aspect the ink absorption by in supporting mass, containing resin cation.
Advantage of the present invention
According to the present invention, even the high-quality ink jet recording medium that under prepared paint overlay capacity (coverage ofcoating) situation, also can have high gloss and enough ink absorption overlay capacity that may obtain not obtain so far.
Best mode for carrying out the invention
In the present invention, paper is often used as ventilative supporting mass, if desired, also can use the supporting mass of other non-paper, such as adhesive-bonded fabric.
The paper pulp that constitutes the paper (body paper) that is used as supporting mass among the present invention is without particular limitation, can be individually or with the mode of any combination use the kraft pulp made by cork and hardwood, such as the chemical pulp of sulfite pulp, such as the mechanical pulp of wood-ground pulp, such as the semichemical wood pulp of semichemical wood pulp and half wood-ground pulp and by non-wooden fiber such as, various paper pulp that bagasse, mestha and straw, old paper stock are made.
The body paper that uses among the present invention can contain the filler that has or not special restriction.Just, can be individually or the mode of combination arbitrarily use inorganic pigment and various organic Chinese white solid or hollow such as calcium carbonate, calcium bicarbonate, talcum, kaolin, calcium sulfate, barium sulfate and the titanium oxide of precipitation.When the content of filler was increased to a certain degree, ink absorption increased, and this is that we are desirable, but when the content of filler was too high, the mechanical strength of supporting mass was damaged sometimes.Especially, be used as the content of filler in the paper of supporting mass of the present invention more preferably in 4-25 quality % scope.
Except above-mentioned paper pulp and filler, the body paper that uses among the present invention can randomly contain the chemical reagent of adhesive and various paper grade (stock)s, such as sizing agent, fixative, volume increase agent, cationic reagent, reinforcing agent, the reagent treatment of turning blue, fluorescer, brightening agent, pH conditioning agent, defoamer, regulation by pitch agent and stickiness controlling agent.Above-mentioned raw material is suitable for being dispersed or dissolved in the water, can use various instruments, such as fourdrinier machine, two-wire (paper) machine, for example Aladdin former and hybrid shaping device, cylinder mould machine and combined paper machine are made the paper that is used as supporting mass in the present invention by these raw materials.
And the body paper of Shi Yonging can carry out the top sizing processing with various starch, various Cypres etc. in the present invention.
Lower floor of the present invention is the coating that forms near the ink jet recording medium supporting mass, in case and the coating composition of lower floor be a kind of dry fluid composition that just forms lower floor.And the upper layer group compound among the present invention is the coating that forms away from supporting mass, in case and the upper strata coating composition be a kind of dry fluid composition that just forms the upper strata.Generally the liquid form with water-based uses these coating compositions, and this waterborne liquid is with the above-mentioned raw materials dissolving or is dispersed in the water and makes.In the present invention, lower floor and upper strata are adjacent usually, and one deck or two-layer or multilayer intermediate layer can be provided between lower floor and upper strata, as long as the interaction on lower floor and upper strata is not subjected to strong obstruction.And, one deck or two-layer or laminated coating also can be provided between lower floor and the supporting mass and between upper strata and recording medium surface.
It is that being coated with of moisture state is laminated on the specular surface of heating specular surface is transferred to the surface of coating that casting among the present invention is handled, and removes the moisture in the coating so that recording medium has the processing of gloss by drying simultaneously.Handle for casting, usually adopt device with a fixed structure, this structure can be rolled up on the outer surface of the metallic cylinder that continuously pending roll web (web) is pressed onto heating by the elasticity of being made by rubber or analog, and the device (non-patent literature 2) of the structure of when reaching required drying regime roll web being peeled off from cylinder is implemented as above other device of same operation but also can use.
Being used to produce the non-limiting example that the casting of ink jet recording medium of the present invention handles is made of following method:
(1) behind the coating composition composition, coating will be coated with (wetting again) on the specular surface that is laminated to pouring device then in case drying just applies water on coating.
(2) coating upper strata coating composition or upper strata and lower floor's coating composition is pressed onto it when coating is not dried on the specular surface of pouring device (wet method (direct method)) then.
(3) coating upper strata coating composition or upper strata and lower floor's coating composition by removing moisture part dry coating, are laminated to being coated with of leather hard on the specular surface of pouring device then then.
Absorptive pigment of the present invention be have water absorbability can pigment, the example of these pigment is the calcium carbonate, wet method synthetic silica, diatomite, calcium silicates, talcum, magnesium hydroxide, halloysite, activated clay, acid clay, hydrotalcite, hydrated alumina, aluminium hydroxide, bentonite, zeolite, kaolin, calcined kaolin, gypsum, titanium oxide, barium sulfate of calcium bicarbonate, precipitation etc.In these pigment, the pigment with 1ml/g or more oil absorption that describes in detail among the preferred JISK 5101 is because can obtain to have the absorbefacient recording medium of good ink like this.
In these absorptive pigment, preferred especially wet method synthetic silica is even because use very little coating overlay capacity, also can obtain the ink jet recording medium of the good overlay capacity of ink absorption.Wet method synthetic silica among the present invention is by the silicate such as sodium metasilicate is mixed with the acid of sulfuric acid and so on, then to the mixture silica of the porous that obtains such as wash, wear out, mill.Their main preparation method, the precipitation method and gel method are known, these two kinds of methods are preferred for lower floor of the present invention coating composition.
From the ink absorption angle, the oil absorption of wet method synthetic silica that is used for lower floor of the present invention coating composition is more preferably higher, if but oil absorption is too high, when cutting, be easy to produce dust, and this does not wish to take place.Especially, be used for the oil absorption of wet method synthetic silica of lower floor of the present invention coating composition more preferably for 1-5ml/g, more preferably 2-4ml/g.For the particle diameter of the wet method synthetic silica that is used for lower floor of the present invention coating composition, if too little, the viscosity of coating composition can increase, and the coating operation can become difficult, and this does not wish to take place; If too big, after handling, casting is difficult to manifest the gloss of recording medium sometimes, and this does not wish to take place yet.Especially, the particle diameter that first-selection is used for the wet method synthetic silica of lower floor of the present invention coating composition more preferably is the 2-20 micron, more preferably, the 3-15 micron, described particle diameter is measured by Ma Erwen (Malvern) method.
Latex among the present invention is wherein to have disperseed the fluent material of the water of water-fast thermoplastic polymer compounds basically a kind of comprising, and this is with the different of aqueous solution of water-soluble polymer compound: even the former does not dissolve in hot water after drying basically yet.The particle diameter of polymer compound is generally 500nm or littler in water.The example that can be used for the latex of lower floor's coating composition among the present invention is the synthesized polymer compounds, such as vinyl acetate resin, ethylene vinyl acetate resin, (methyl) acid allyl ester resin, styrene-(methyl) acid allyl ester resin, styrene-butadiene resin, propylene cyanogen-butadiene resin, isoprene olefine resin, chloropropene resin, polyurethane resin with comprise the water-borne dispersions of copolymer with these polymer of grafting or block form combination, natural rubber latex etc.In the present invention, for example vinyl acetate resin is the resinous polymer that mainly is made of vinyl acetate, comprises not only that homopolymers also comprises to comprise as the vinyl acetate of Main Ingredients and Appearance and the copolymer of one or more other monomers.These latex can use separately or two or more latex are combined use.
In the present invention, for the amount that is added into the latex in lower floor's coating composition, when the latex amount too hour, sometimes when the cutting ink jet recording medium, be easy to produce dust, and when the latex amount was too big, ink absorption can be not enough sometimes, or can not obtain enough glossiness sometimes after casting is handled.Therefore, the latex amount makes the mass ratio of latex and (water imbibition pigment+silica gel) be 10/100-60/100 more preferably, more preferably, and 15/100-40/100.
In the present invention, as the latex that is used for lower floor's coating composition, polyurethane resin latex is preferred especially, because can obtain extra high glossiness thus.Polyurethane resin among the present invention is by the compound with two or more NCOs and has the polymer that the sudden reaction of two or more functional groups''s (such as alcoholic extract hydroxyl group, phenolic hydroxyl group or amino) with reactive hydrogen compound obtains, and comprise also that wherein the key that the reaction by isocyanates and reactive hydrogen obtains is to be different from amino-formate bond, such as the polymer of the key of urea key.
Be used for the two or more compound bearing active hydrogen of having of polyurethane resin and comprise that these compounds can use separately or two or more compounds are combined use such as the compound of PEPA, PPG, poly-carbonic acid polyalcohol, polyacetals polyalcohol, polyacrylate polyol, polyamide polyalcohol and polybutadiene polyol.
Some ink-jet printers have the mechanism that with cutter the ink jet recording medium of drum is cut into sheet after being completed for printing.Because precision mechanism such as print head may be subjected to the adverse effect of dust, the paper that is used to have the printing machine of cutting mechanism need not generate dust basically when cutting.As the polyurethane resin latex that is used for lower floor's coating composition, be preferred by the polyurethane rubber latex that PPG is prepared as initial feed, because the dust that forms is less like this.
As the PPG that is used as the initial feed of polyurethane resin in the present invention, for example can use by using appropriate catalyst to make one or more cyclic ethers the polymer that obtains such as oxirane, expoxy propane, epoxy butane, oxolane and styrene oxide opened loop polymerization.These polymer can use separately or two or more are combined use.
In the present invention, can be that 30-70MPa, percentage elongation are that the latex of the polyurethane resin of 300-800% obtains high gloss simultaneously as the latex of lower floor and low dust forms by comprising tensile strength.If less than 300%, manifesting of back gloss is handled in casting so sometimes can be not enough greater than 70MPa or percentage elongation for tensile strength.On the other hand, if tensile strength less than 30MPa or percentage elongation greater than 800%, so almost can not obtain gratifying low dust and form.
In the present invention, the tensile strength of polyurethane resin and percentage elongation are to be measured by the method for regulation among the JIS K 7311, the sample that will be used to test downcuts from film, described film obtains in the following manner: latex is spread on the polyester film, making dried thickness is 150 μ m, under 23 ℃ and 65% relative humidity dry 24 hours then, then at 150 ℃ of dry 5min down.
Can obtain more gratifying low dust formation rate as the polyurethane resin latex of 10-60nm by using by the particle diameter of dynamic light scattering determination.If particle diameter is less than 10nm, the ink absorption of prepared ink jet recording medium can be damaged sometimes.
For the boric acid in the adding lower floor coating composition of the pH that may depend on coating composition or the amount of its salt, if addition is too little, may if addition is too big, when the cutting coating, be easy to produce dust in the upper strata, occurring crackle after the drying to cause glossiness impaired.Especially, according to boric acid (H based on the molal quantity of boron 3BO 3), addition more preferably is: 0.2 quality %-10 quality % of water imbibition pigment.
In the present invention, can obtain higher glossiness and more gratifying low dust formation by after coating lower floor and before the coating upper strata, the supporting mass with lower floor and upper strata being carried out calendering.
As the calender apparatus of using in the present invention, soft calender apparatus and super calender apparatus are representational, but also can use gloss calender apparatus, base (shoe) calender apparatus etc.After the calender process of operating after the coating lower floor, if the Bake paper smoothness of following laminar surface is too low, sometimes be not enough by calender process to the effect that improves the formation of glossiness and low dust so, if the Bake paper smoothness is too high, ink absorption sharply descends sometimes, therefore preferably makes smoothness be controlled at 50-300 second by the condition of regulating such as nip pressure, temperature and processing speed.
In the present invention, lower floor's coating composition more preferably contains silica gel, and ink absorption and low dust form good ink jet recording medium because can obtain particularly like this.Silica gel among the present invention is to remove metal ion by acid such as sulfuric acid is acted on such as the aqueous silicate solution of sodium silicate solution or with cationic ion-exchange resin from aqueous solution, the silicate polymer water-borne dispersions that wears out then and produce, silica gel comprises the spherical silicate particle that particle diameter is generally 10-200nm.
When the specific area of the silica gel that is used to form coating composition too hour, improving the effect that low dust forms can be not enough, when specific area was too big, ink absorption may be destroyed.Therefore, the specific area of being measured by the BET method more preferably is 50-500m 2/ g, more preferably, 100-400m 2/ g.And, the amount of the silica gel in lower floor of the present invention coating composition too hour, the effect that improves ink absorption is not enough sometimes, when the amount of silica gel is too big, is difficult to manifest gloss sometimes after casting is handled.Therefore, the amount of silica gel more preferably is based on the 10-100 quality % of the amount of water imbibition pigment, more preferably, and 15-60 quality %.
Can in lower floor of the present invention coating composition, add water-soluble polymer compound, such as polyoxyethylene, vinyl pyrrolidone polymer, (methyl) acrylate copolymer and its salt, (methyl) acrylamide polymer, water-soluble cellulose ether, such as methylcellulose and hydroxyethylcellulose, with water-soluble polymer compound, such as starch, or comprise water-soluble polymer compound with these polymer of the form combination of random, grafting or block.Yet when the amount of the water-soluble polymer compound that contains in the coating composition was too big instantly, the ink absorption of the ink jet recording medium that makes may be subjected to extreme destruction.The amount of the water-soluble polymer compound that contains in lower floor's coating composition more preferably is 5 quality % or littler based on the amount of absorptive pigment.Especially, have the water miscible polymer compound of high-crystallinity, such as polyvinyl alcohol, the glossiness of casting being handled the ink jet recording medium of back acquisition causes significant destruction, preferably is substantially devoid of such compound.
Sub-micron pigment among the present invention is the inorganic pigment with following characteristic: when the dispersion with it is sprayed on suitable substrate, such as on glass and when observing with electronic scanner microscope, long edge lengths be 1 μ m or littler particle account for area that the particle in the field of view occupies 80% or more.The sub-micron pigment that uses in the coating composition of upper strata is without particular limitation, and their example is gel method silica, precipitated silica, silica gel, fumed silica, vapor phase method aluminium oxide, pseudobochmite etc.By using wherein long edge lengths to account for 80% or more inorganic pigment of the area that the particle in the field of view occupies as 400nm or littler particle, can obtain extra high surface gloss, preferably use such inorganic pigment.And, using wherein long edge lengths to account for as 100nm or bigger particle under the situation of 80% or more inorganic pigment of the particle footprint area in the field of view, even the skin of upper strata coating composition becomes dry rapidly, also produce the defective such as coating is split hardly after coating.
When in the coating composition of upper strata of the present invention, using specific area, can obtain high gradation of drop-out colour, but when the excessive inorganic pigment of use specific area, ink absorption can be damaged sometimes greater than to a certain degree sub-micron pigment.Especially, the specific area of the pigment of measuring with the BET method more preferably is 60-600m 2/ g, more preferably, 90-400m 2/ g.
Under the situation of using again wet method to cast in the present invention to handle, preferably use hydrated alumina as being used for the sub-micron pigment of upper strata coating composition, because can obtain extra high glossiness like this.In the present invention, hydrated alumina is by forming general formula Al 2O 3NH 2The compound of O representative is divided into types such as zirlite (n=3), bialite (n=3), diaspore (n=1), boehmite (n=1), amorphous alumina hydrate according to difference (value of n) or the crystalline form formed.Being used for only hydrated alumina of the present invention is the hydrated alumina with so-called pseudobochmite form, it is characterized in that having greater than 1 less than 3 n and the X-ray diffractogram that is similar to boehmite, but each corresponding peak broad.
Condition material, aging temperature and the ageing time that coexists when the aluminium salt that the method that production is used for hydrated alumina of the present invention has the hydrolysis of aluminium-alcohol salt, realized by neutralization or the degraded of aluminate and the pH when changing such as reaction, reaction temperature, reaction is controlled the physical property such as particle diameter, pore space and specific area.In order to obtain these hydrated aluminas, will add in the dispersion such as the acid nitric acid, hydrochloric acid, formic acid, acetate or the lactic acid usually as stable submicron particles.
In the process that ink jet recording medium transports in ink-jet printer, printing surface produces friction with the back side of other paper or the various devices of transport establishment sometimes.Ink-jet printer is designed to usually by optimizing pressure or adopting low-friction material that friction is minimized the influence of recording medium, and still the vestige of friction can remain as the difference of the surface texturisation in (as high gloss of the present invention) recording medium sometimes.Sometimes according to the purposes needs, ink jet recording medium can not leave the vestige (being exactly to have burnish resistance) of friction.In the present invention, when adopting wetting to cast processing, can obtain higher glossiness and obtain high burnish resistance simultaneously by behind the coating upper strata and before casting the supporting mass with lower floor and upper strata being carried out calender process, this is preferred again.
In the present invention, if the Bake paper smoothness of upper surface is too low after the calender process of implementing behind the coating upper strata, not enough sometimes with the effect that improves glossiness and burnish resistance by calender process so, if the Bake paper smoothness is too high, ink absorption sharply descends sometimes.Therefore, preferably regulate the condition such as pressure, temperature and processing speed so that the surface has the Bake paper smoothness in 50-300 scope second.
In the present invention, when using again wetting to cast to handle and hydrated alumina when being used as the sub-micron pigment that is used for the upper strata coating composition, the preferred use contained the moistening liquid of silica gel, because can obtain to have the ink jet recording medium of very high glossiness and very gratifying burnish resistance thus.
Particularly when the average primary particle diameter with dynamic light scattering determination be 40nm or littler anion silica gel when being used as the silica gel that adds moistening liquid, silica gel engages with the upper strata, causes very high glossiness, this is preferred.
As the polyvinyl alcohol that is used for upper strata of the present invention coating composition, can use polyvinyl alcohol with 70 moles of various saponification degrees between % to 100 mole of %, and when using that wetting is cast again, preferred use saponification degree is 95 moles of % or bigger polyvinyl alcohol, because the easy like this gloss that manifests.And; also can use by introduce various such as silicyl, carboxylic acid group, amino and acetoacetyl the functional group or introduce the polyvinyl alcohol of the modification that other monomer such as ethene prepares with the form of random, grafting or block; and, also can use by adding the polyvinyl alcohol that a spot of material that makes the polyvinyl alcohol gelling such as boric acid increases its viscosity.
If the amount of the polyvinyl alcohol in the coating composition of adding upper strata very little, the burnish resistance that may occur crackle or ink jet recording medium in dry run may be not enough, if too big, ink absorption may descend.Especially, the amount of polyvinyl alcohol more preferably is based on the 2-40 quality % of the amount of sub-micron pigment, more preferably, and 5-25 quality %.
The polyvinyl alcohol that is used for the upper strata coating composition is preferred, for example its viscosity in aqueous solution is higher, because even the amount of polyvinyl alcohol is less, in the dry run of coating composition coating, also crack hardly, therefore, can use a small amount of polyvinyl alcohol, can improve ink absorption with this, this is preferred.On the other hand, if the viscosity of aqueous solution is too high, the viscosity of the coating composition that makes among the present invention becomes too high so, makes sometimes to apply to operate the difficulty that becomes.Especially, more preferably be 15-400mPas with the viscosity in aqueous solution of 4 quality % of Ubbelohde (Ubbelohde) viscometer determining according to the method for JIS Z8803 down at 25 ℃, more preferably, 30-200mPas.These polyvinyl alcohol can be used alone or two kinds or the polyvinyl alcohol that the viscosity of multiple saponification degree, aqueous solution is different with decorating state are combined use.
Upper strata of the present invention coating composition more preferably contains the cation water-based dispersion that is selected from following at least a resin: the particle diameter of being measured by the dynamic light scattering method is 150nm or littler (1) (methyl) acrylate bond, (2) styrene-(methyl) acrylate copolymer and (3) polyurethane, because can obtain higher gradation of drop-out colour thus.Can be with these polymer and various vinyl monomer, allyl monomer or analog combined polymerization, only otherwise execution gets final product.
If desired, each coating of the present invention can contain various additives such as surfactant, defoamer, thickener, blueing agent, fluorescent whitening agent, antioxidant and UV absorbers.
In the present invention, the method that is coated with the coating composition of each coating has no particular limits, can adopt various apparatus for coating, such as Kohler coater, knife type coater, rod-type knife type coater (rod-bladecoater), metering bar coater, reverse roll coater, arc knife type coater (comma coater), gate roll coater, film transfer coater, lip be coated with machine (lip coater), mould is coated with machine (die coater) and curtain coater.Wherein, preferably be coated with coating with curtain coater, upper strata coating composition particularly because the coating uniformity height of gained like this, and when the coating upper strata, thus coating composition hardly porous enter lower floor and obtain remarkable gratifying surface quality.
If the overlay capacity of each coating is too little, ink absorption is not enough sometimes, if overlay capacity is too big, the character that low dust forms is destroyed sometimes, and the overlay capacity of usually preferred the upper and lower coating is respectively 5-20g/m 2, the overlay capacity of two-layer total coating is 10-30g/m 2Exceptionally, when needs absorb a large amount of especially printing ink, such as, when the ink-jet printer that is used to print put on ink-jet print medium with a large amount of especially printing ink, the total overlay capacity of preferred sometimes two coatings was about 50g/m 2Even, but in this case,, adopt the coating overlay capacity littler than conventional method according to the present invention, also the ink absorption that can obtain to be equal to forms with relative gratifying low dust.
In order to improve the ability of the demoulding on the specular surface from pouring device, can with comprise the releasing agent of oily material, the water-borne dispersions or the analog of oily material adds in the coating composition of the present invention.And, when before casting is handled, being coated with or using again wetting as casting method, can be by realizing long-term steady production to being used for carrying out again moistening water adding releasing agent.Effective examples of material as the releasing agent component is a senior alkylamines, such as dimethyl octylame and dimethyl stearyl amine or their salt, the senior alkyl quaternary ammonium salt, such as hot ammonium of chlorination trimethyl and chlorination trimethyl octadecylammonium, the high carboxylic acid is such as oleic acid, stearic acid and sad or their salt, higher alcohol, such as octanol and octadecanol, hydrocarbon compound is such as atoleine, solid paraffin, microcrystalline wax and polyvinyl paraffin wax, silicone oil etc.
When containing resin cation in the supporting mass of the present invention, can obtain higher ink absorption, this is preferred.Especially, copolymer such as dimethylamine-chloropropylene oxide condensation product, dialkylamine-ammonia-chloropropylene oxide condensation product, acrylamide-diallylamine copolymer and copolymer with amidine structure (disclosing an example of amidine structure in No. the 2624089th, Japan Patent) are for improving that ink absorption has very big effect and being particularly preferred.
Also can provide the back coating that contains pigment, adhesive or analog to suppress curling or to adjust sliding property, whiteness and tone at the back side of ink jet recording medium of the present invention.
To show embodiments of the invention below.In these embodiments, " part " is " mass parts ".
Embodiment 1
[preparation lower floor coating composition]
6 parts of sodium tetraborate decahydrates (are equivalent to 0.97 part of H 3BO 3) be dissolved in 350 parts of water, in this solution, add 100 parts of wet method synthetic silicas (FINESEAL X-37B is produced by moral mountain Co., Ltd (TokuyamaCo.Ltd.)), fully disperse with dispersion machine then with saw blade.Then, be 50 quality %, glass transition temperature for-15 ℃, gel content are that the styrene-butadiene latex of 85 quality % adds in the dispersion with the solids content of 80 parts (solids contents: 40 parts), mix subsequently to obtain lower floor's coating composition.
[preparation fumed silica dispersion]
Under agitation be that (according to the BET method, specific area is 90m for the aqueous solution of 50% chlorination dimethyldiallylammonium polymer of 400mPasec and 100 parts of fumed silicas with the viscosity of 8 parts (solids contents: 4 parts) 2/ g) add in 329 parts of water, carry out initial dispersion with cutter type dispersion machine then.The initial dispersion body of processing gained with colloid mill is 20.8% fumed silica dispersion with the acquisition solid concentration.Water is with 100 times (mass ratio) of this dispersion dilution, be injected on the glass substrate and and observe with electronic scanner microscope, find 90% or the long limit of the particle of more (quantity) be 500nm or littler, and long limit be 150nm or bigger particle occupy whole particle area occupied in the field of view 80% or more.
[preparation upper strata coating composition]
With the saponification degree of 30 parts of (solids content: 3 parts) 10 quality % be 88 moles of %, viscosity 25 ℃ the time is that the polyvinyl alcohol water solution of 95mPasec (solution to its 4 quality % records) adds in the fumed silica dispersion that makes more than 100 parts (solids contents: 20.8 parts) with preparation upper strata coating composition.
[preparation ink jet recording medium]
Being 10g/m after the drying 2Overlay capacity lower floor's coating composition is coated on Substance is 157g/m 2Body paper (papermaking Co., Ltd of Mitsubishi (Mitsubishi Paper Mills Limited) produce DIAFORM (trade mark)) on, use the air drier drying then.In this case, the Bake paper smoothness is 18 seconds.Then, with 8g/m after the drying 2Overlay capacity coating upper strata coating composition, and before water evaporates, will be coated with on the cylinder that is laminated to the chromium plating that is heated to 90 ℃ in the pouring device and be dried to the coating automatic demoulding, obtain ink jet recording medium with this with the speed of the linear pressure of 20kN/m and 5m/min.
Embodiment 2
Produce ink jet recording medium with the method identical with embodiment 1, difference is to handle this layer with soft calender after coating and dry lower floor, to obtain 35 seconds Bake paper smoothness.
Embodiment 3
Produce ink jet recording medium with the method identical with embodiment 2, difference is, after coating and dry lower floor, handles this layer with soft calender, to obtain 400 seconds Bake paper smoothness.
Embodiment 4
Produce ink jet recording medium with the method identical with embodiment 2, difference is after coating and dry lower floor, handles this layer to obtain 50 seconds Bake paper smoothness with soft calender.
Embodiment 5
Produce ink jet recording medium with the method identical with embodiment 2, difference is to handle this layer with soft calender after coating and dry lower floor, to obtain 100 seconds Bake paper smoothness.
Embodiment 6
Produce ink jet recording medium with the method identical with embodiment 2, difference is, after coating and dry lower floor, handles this layer with soft calender, to obtain 300 seconds Bake paper smoothness.
Embodiment 7
Produce ink jet recording medium with the method identical with embodiment 1, difference is that the specific area that 75 parts (solids contents: 30 parts) are measured by the BET method is 220m 2/ g, solids content are that the silica gel of 40 quality % adds in lower floor's coating composition.
Embodiment 8
Produce ink jet recording medium with the method identical with embodiment 5, difference is, with the identical silica gel adding lower floor coating composition of silica gel that uses among 75 parts (solids contents: 30 parts) and the embodiment 7.
Embodiment 9
Produce ink jet recording medium with the method identical with embodiment 1, difference is, uses 89 parts of (solids content: 40 parts) tensile strength to be 350%, to be that the polyurethane rubber latex of 45 quality % replaces styrene-butadiene latex by the particle diameter of dynamic light scattering determination as 140nm and the solids content of using PEPA to prepare as polyalcohol as 20MPa, percentage elongation in lower floor's coating composition.
Embodiment 10
Produce ink jet recording medium with the method identical with embodiment 1, difference is, uses 100 parts (solids contents: 40 parts) to contain tensile strength in lower floor's coating composition and is 680%, is that the polyurethane rubber latex of 40 quality % replaces styrene-butadiene latex by the particle diameter of dynamic light scattering determination as 120nm and the solids content of using PPG to prepare as polyalcohol as 22MPa, percentage elongation.
Embodiment 11
Produce ink jet recording medium with the method identical with embodiment 1, difference is, uses 100 parts of (solids content: 40 parts) tensile strength to be 480%, to be that the polyurethane rubber latex of 40 quality % replaces styrene-butadiene latex by the particle diameter of dynamic light scattering determination as 80nm and the concentration of using PPG to prepare as polyalcohol as 35MPa, percentage elongation in lower floor's coating composition.
Embodiment 12
Produce ink jet recording medium with the method identical with embodiment 7, difference is, uses 114 parts of (solids content: 40 parts) tensile strength to be 750%, to be that the polyurethane rubber latex of 40 quality % replaces styrene-butadiene latex by the particle diameter of dynamic light scattering determination as 50nm and the concentration of using PPG to prepare as polyalcohol as 40MPa, percentage elongation in lower floor's coating composition.
Embodiment 13
Produce ink jet recording medium with the method identical with embodiment 5, difference is, uses 100 parts (solids contents: 40 parts) carbamate identical with the carbamate latex of use among the embodiment 10 to replace styrene-butadiene latex in lower floor's coating composition.
Embodiment 14
Produce ink jet recording medium with the method identical with embodiment 5, difference is, uses 114 parts (solids contents: 40 parts) carbamate identical with the carbamate latex of use among the embodiment 12 to replace styrene-butadiene latex in lower floor's coating composition.
Embodiment 15
Produce ink jet recording medium with the method identical with embodiment 8, difference is, uses 100 parts (solids contents: 40 parts) carbamate identical with the carbamate latex of use among the embodiment 10 to replace styrene-butadiene latex in lower floor's coating composition.
Embodiment 16
Produce ink jet recording medium with the method identical with embodiment 8, difference is, uses 114 parts (solids contents: 40 parts) carbamate identical with the carbamate latex of use among the embodiment 12 to replace styrene-butadiene latex in lower floor's coating composition.
Embodiment 17
Produce ink jet recording medium with the method identical with embodiment 8, difference is, uses 114 parts of (solids content: 40 parts) tensile strength to be 600%, to be that the polyurethane rubber latex of 35 quality % replaces styrene-butadiene latex by the particle diameter of dynamic light scattering determination as 50nm and the concentration of using PPG to prepare as polyalcohol as 50MPa, percentage elongation in lower floor's coating composition.
Embodiment 18
Produce ink jet recording medium with the method identical with embodiment 16, difference is that the overlay capacity of lower floor is 10g/m 2, the upper strata is 15g/m 2
Embodiment 19
[preparation hydrated alumina colloidal sol]
299 parts of water and 1 part of acetate are mixed, 100 parts of hydrated aluminas with pseudobochmite structure (by spreading the DISPERAL HP14 that Sauer GmbH (Sasol Co.Ltd.) produces) are joined in this mixture, and making mixture become colloidal solution by the 2hr that stirs the mixture then is 25% hydrated alumina colloidal sol to obtain solid concentration.Water is with 100 times of this dispersion dilutions, be injected on the glass substrate, and observe with electronic scanner microscope, find 90% or the long limit of more (in quantitative terms) particle be 400nm or littler, and grow the limit be 100nm or bigger particle occupy all particle area occupied in the field of view 80% or bigger.
[preparation upper strata coating composition]
Viscosity was that the polyvinyl alcohol water solution of 95mPasec (measuring the solution gained of its 4 quality %) adds in the hydrated alumina colloidal sol that 100 parts (solids contents: 25 parts) make with preparation upper strata coating composition when the saponification degree of 20 parts of (solids content: 2 parts) 10 quality % was 88%, 25 ℃.
[production ink jet recording medium]
Use Kohler coater, with 10g/m after the drying 2Overlay capacity the lower floor's coating composition among the embodiment 12 is coated on Substance is 157g/m 2Body paper (papermaking Co., Ltd of Mitsubishi (Mitsubishi PaperMills Limited) produce DIAFORM (trade mark)) on, use the air drier drying then.In this case, the Bake paper smoothness is 20 seconds.Then, with Kohler coater with drying after 15g/m 2Overlay capacity coating upper strata coating composition, use the air drier drying subsequently.Make the applied surface of coated paper contact with water 5s with wetting should the surface, will be coated with the speed of the linear pressure of 20kN/m and 5m/min then and be laminated on the cylinder that is heated to 95 ℃ to obtain ink jet recording medium.
Embodiment 20
With with embodiment 19 in identical method produce ink jet recording medium, difference is, after coating and dry lower floor, with calender processing coating so that the Bake paper smoothness is 100 seconds.
Embodiment 21
With with embodiment 20 in identical method produce ink jet recording medium, difference is, behind coating and dry upper strata, with calender processing coating so that the Bake paper smoothness is 35 seconds.
Embodiment 22
With with embodiment 20 in identical method produce ink jet recording medium, difference is, behind coating and dry upper strata, with calender processing coating so that the Bake paper smoothness is 400 seconds.
Embodiment 23
With with embodiment 20 in identical method produce ink jet recording medium, difference is, behind coating and dry upper strata, with calender processing coating so that the Bake paper smoothness is 50 seconds.
Embodiment 24
With with embodiment 20 in identical method produce ink jet recording medium, difference is, behind coating and dry upper strata, with calender processing coating so that the Bake paper smoothness is 150 seconds.
Embodiment 25
With with embodiment 20 in identical method produce ink jet recording medium, difference is, behind coating and dry upper strata, with calender processing coating so that the Bake paper smoothness is 300 seconds.
Embodiment 26
[preparation surface coating material composition]
It is that 22nm, solid concentration are that 50 quality %, pH are 9.0 and use Na that 240 parts of water are added 60 parts of average grain diameters +Ion is that the anion silica gel of stabilisation ion is to prepare moistening liquid.
[coating top layer]
With 5g/m 2(0.5g/m 2Solids content) with the intaglio plate coating machine above surface coating material composition is coated among the embodiment 24 as composition on the ink jet recording medium surface that produces, then, with heated-air drying to produce ink jet recording medium.
Embodiment 27
[preparing moistening liquid]
It is that 75nm, solid concentration are that 40 quality %, pH are 9.5 and use Na that 292.5 parts of water are joined 7.5 parts of average grain diameters +Ion is to prepare moistening liquid in the anion silica gel of stabilisation ion.
[production ink jet recording medium]
With with embodiment 24 in identical method produce ink jet recording medium, difference is, uses above moistening liquid to replace the moistening liquid of water in handling as casting.In this case, the overlay capacity of moistening liquid is 50g/m 2(0.5g/m 2Silica gel).
Embodiment 28
[preparing moistening liquid]
It is that 12nm, solid concentration are that 30 quality %, pH are 4.5 and use Cl that 290 parts of water are joined 10 parts of average grain diameters -Ion is to prepare moistening liquid 1 in the cationic silica of stabilisation ion.
[production ink jet recording medium]
With with embodiment 24 in identical method produce ink jet recording medium, difference is, uses above moistening liquid to replace the moistening liquid of water in handling as casting.In this case, the overlay capacity of moistening liquid is 50g/m 2(0.5g/m 2Silica gel).
Embodiment 29
[preparing moistening liquid]
It is that 22nm, solid concentration are that 50 quality %, pH are 9.0 and use Na that 294 parts of water are joined 6 parts of average grain diameters +Ion is to prepare moistening liquid in the anion silica gel of stabilisation ion.
[production ink jet recording medium]
With with embodiment 24 in identical method produce ink jet recording medium, difference is, uses above moistening liquid to replace the moistening liquid of water in handling as casting.In this case, the overlay capacity of moistening liquid is 50g/m 2(0.5g/m 2Silica gel).
Embodiment 30
With with embodiment 16 in same procedure produce ink jet recording medium, difference is, cationic styrene-acrylate copolymer dispersion (solids content: 27 quality % that 22 parts (solids content: 5.94 parts) is commercially available, dispersion particle diameters by light scattering determining is 50nm, and the Tg of resin is 65 ℃) add in the coating composition of upper strata.
Embodiment 31
With with embodiment 29 in identical method produce ink jet recording medium, difference is, will add in the coating composition of upper strata with used identical thermoplastic resin dispersion among the embodiment 30.
Embodiment 32
[preparation treated cation solution]
In the aqueous solution and 150 parts (solids content: 15 parts) oxidized starch aqueous solution by dimethyl amine-chloropropylene oxide condensation product that 90 parts of water are added 60 parts of (solids content: 30 parts) concentration is 50 quality %, prepared treated cation solution with 10 quality % of conventional method dissolving.
[body paper of production treated cation]
Before dry with each face 20g/m 2The two sides of the body paper that in embodiment 1, uses of overlay capacity all be coated with the solution of above treated cation.
[production ink jet recording medium]
With with embodiment 16 in identical method produce ink jet recording medium, difference is, with the body paper of treated cation as supporting mass.
Embodiment 33
With with embodiment 29 in identical method produce ink jet recording medium, difference is, the body paper of treated cation that will be identical with embodiment 32 is as supporting mass.
[comparing embodiment 1]
[preparation lower floor coating composition]
2 parts of dissolution of sodium hydroxide in 350 parts of water, are added 100 parts of wet method synthetic silicas (FINESEAL (trade mark) X-37B is produced by moral mountain Co., Ltd) in this solution, fully disperse with spreading machine then with saw blade.Then, with 200 parts of saponification degrees be 98.5%, viscosity is 25mPasec (measuring its aqueous solution gained of 4%) polyvinyl alcohol (R POLYMER 1130 that 12% silicyl modifies, Kuraray Co., Ltd (Kuraray Co.Ltd.) production) aqueous solution adds in the dispersion, mixes subsequently to obtain lower floor's coating composition.
[preparation intermediate layer coating composition]
4 parts of sodium tetraborate decahydrates are added in 96 parts of water, stir then and dissolve with preparation intermediate layer coating composition.
[production ink jet recording medium]
With 10g/m after the drying 2Overlay capacity with Kohler coater above lower floor's coating composition to be coated on Substance be 157g/m 2Body paper (papermaking Co., Ltd of Mitsubishi (Mitsubishi Paper Mills Limited) produce DIAFORM (trade mark)) on, use the air drier drying then.The Bake paper smoothness of the coated paper of gained is 20 seconds.Then, handle the coated paper that makes with soft calender, and with 0.2g/m after the drying 2Overlay capacity coating intermediate layer coating composition, use the air drier drying subsequently.And making dried matter with the upper strata coating composition of Kohler coater coating embodiment 1 is 8g/m 2, use the air drier drying then.In addition, handle the coated paper that makes with soft calender.By contact the applied surface that 5s comes wetting coated paper with water, with the speed of the linear pressure of 20kN/m and 5m/min this surface is pressed onto then and has specular surface in the pouring device and be heated on 95 ℃ the cylinder of chromium plating, dry back coated paper from the cylinder the demoulding to obtain ink jet recording medium.
[comparing embodiment 2]
[preparation intermediate layer coating composition]
2 parts of boric acid are added in 98 parts of water, stir then and dissolve with preparation intermediate layer coating composition.
[production ink jet recording medium]
Produce ink jet recording medium as the method in the comparing embodiment 1, difference is, replaces the midcoat composition in the comparing embodiment 1, with 0.1g/m after the drying 2The above intermediate layer coating composition of overlay capacity coating.
[comparing embodiment 3]
Produce ink jet recording medium as the method in the comparing embodiment 1, difference is that the overlay capacity on upper strata, dry back is 15g/m 2
[comparing embodiment 4]
Produce ink jet recording medium as the method in the comparing embodiment 1, difference is that the overlay capacity that coating is gone up in dry back is 20g/m 2
[comparing embodiment 5]
Produce ink jet recording medium as the method in the comparing embodiment 4, difference is, after coating and dry lower floor, handles lower floor so that the Bake paper smoothness after handling is 100 seconds with soft calender.
[comparing embodiment 6]
Produce ink jet recording medium as the method in the comparing embodiment 1, difference is, with embodiment 16 in identical method prepare lower floor's coating composition, but and will not add sodium tetraborate as lower floor's coating composition.
[comparing embodiment 7]
With 10g/m after the drying 2Overlay capacity with Kohler coater comparing embodiment 1 lower floor's coating composition to be coated on Substance be 157g/m 2Body paper (papermaking Co., Ltd of Mitsubishi (Mitsubishi Paper MillsLimited) produce DIAFORM (trade mark)) on, use the air drier drying then.Then, handle the coated paper that makes with soft calender, and with 0.2g/m after the drying 2The intermediate layer coating composition of overlay capacity coating comparing embodiment 1, use the air drier drying subsequently.On the intermediate layer, with 15g/m after the drying 2The upper strata coating composition of overlay capacity coating embodiment 19.Before water evaporates, with the speed of the linear pressure of 20kN/m and 5m/min will be coated be laminated to have in the pouring device specular surface, be heated on 90 ℃ the cylinder of chromium plating, dry back coated paper from the cylinder the demoulding to obtain ink jet recording medium.
[comparing embodiment 8]
With with comparing embodiment 7 in identical method prepare the upper strata ink jet recording medium, difference is that the intermediate layer coating composition in the comparing embodiment 1 replaces with the intermediate layer coating composition in the comparing embodiment 2, with 0.1g/m after the drying 2Overlay capacity coating.
[comparing embodiment 9]
With with comparing embodiment 7 in identical method prepare the upper strata ink jet recording medium, difference is that the overlay capacity that coating is gone up in dry back is 25g/m 2
[comparing embodiment 10]
With with comparing embodiment 7 in identical method prepare the upper strata ink jet recording medium, difference is that the dry back overlay capacity of coating down is 25g/m 2
[comparing embodiment 11]
With with comparing embodiment 7 in identical method produce ink jet recording medium, difference is that the dry back overlay capacity of coating down is 20g/m 2, the overlay capacity that coating is gone up in dry back is 20g/m 2
[comparing embodiment 12]
With with comparing embodiment 7 in identical method produce ink jet recording medium, difference is, with embodiment 16 in identical method prepare lower floor's coating composition, do not add sodium tetraborate as lower floor's coating composition.
[glossiness evaluation]
Carry out the evaluation of glossiness by measuring with the image definition of vision height correlation.In order to measure, be that 60 °, gap width are to use the image definition analyzer under the condition of 1.0mm at angle of reflection.
[evaluation of ink absorption]
Use the PM-G800 type ink-jet printer printing given image of producing by Seiko-Yi Pusen Co., Ltd (Seiko Epson Corporation) to be evaluated, the ink absorption of each recording medium is according to following five standard evaluation: A (very good), B (good), C (generally), D (can accept) and E (unacceptable).When ink absorption is in level higher on the same grade, just with such as B +Represent, when ink absorption is in level lower on the same grade, use such as B -Represent.
[assessment that low dust forms]
With cutting the long otch of ten 2cm in the ink jet recording medium of the cutter with blade Telescopic (by the A-300 of NT Co., Ltd production) on black paper.Collect the dust that forms,, dust formation is divided into A (very little), B (little), C (generally), D (greatly) and E (very big) according to the amount of dust.When low dust forms is in the same grade when less, uses such as B +Expression when the formation of low dust is in the same grade when bigger, is used such as B -Expression.
[burnish resistance evaluation]
The ink jet recording medium of each above embodiment and comparing embodiment is placed on the platform, is recorded and faces up, will be placed on the face of being recorded with the identical body paper that uses among the embodiment 1.Placing a quality on it is that 1kg, diameter are the columnar weight of 53mm, velocity level with 5cm/sec drags this weight, the surface of observed and recorded medium, according to the variation of surface texturisation with the state on surface according to following five standard evaluation: A (not seeing variation) to E (see clearly and changing).
The evaluation result of the ink jet recording medium that obtains in embodiment and comparing embodiment is presented in the table 1.
By comparing " embodiment " and " comparing embodiment ", especially, embodiment 1 and comparing embodiment 1,2 and 6, embodiment 19 and comparing embodiment 7,8 and 12, can see, can obtain to have the ink jet recording medium of high gloss and enough ink absorption according to the present invention with the dead small overlay capacity.By according to as comparing embodiment 4 and 5 and comparing embodiment 9 and 11 in used routine techniques increase the overlay capacity of time coating and last coating, can obtain ink absorption and the glossiness identical with glossiness with the ink absorption that obtains according to the present invention.Yet, use routine techniques to be difficult to obtain low dust and form.
By difference comparing embodiment 1 and embodiment 2-6, embodiment 7 and embodiment 8, embodiment 10 and embodiment 13, embodiment 12 and embodiment 16, embodiment 19 and embodiment 20 can see that calender process can obtain higher glossiness and more senior low dust forms by carrying out in the present invention after coating and dry lower floor.
Can see by comparing embodiment 2,3 and embodiment 4-6, when carrying out lower floor's calender process when making the Bake paper smoothness in the 50-300 scope of second, can obtain glossiness simultaneously, low dust forms and ink absorption.
By comparing embodiment 1 and embodiment 7, embodiment 5 and embodiment 8, embodiment 13 and embodiment 15, and embodiment 14 and embodiment 16, can see,, can obtain higher ink absorption and lower dust formation in the present invention by in lower floor's coating composition, containing silica gel.
By comparing embodiment 1 and embodiment 9-11, embodiment 7 and embodiment 12, embodiment 5 and embodiment 13,14, embodiment 8 and embodiment 13-18, can see, can obtain the good especially ink jet recording medium of glossiness as the latex in the lower floor of the present invention coating composition by using polyurethane resin.
Can see by comparing embodiment 9 and embodiment 10, by using the ink jet recording medium that can obtain to have good low dust formation with PPG as the latex of the polyurethane resin of polyalcohol preparation as the latex that is used for lower floor of the present invention coating composition.
By comparing embodiment 9,10 and embodiment 11, embodiment 13 and embodiment 14, embodiment 15 and embodiment 16,17 can see, can obtain at good especially ink jet recording medium aspect the low dust formation as the latex that is used for lower floor of the present invention coating composition as the latex of the polyurethane resin of 300-800% as 30-70MPa, percentage elongation by using tensile strength.
Can see by comparing embodiment 11 and 12, by the poly-particle diameter by dynamic light scattering determination that uses as the latex of the ammonia ester resin of 10-60nm as the latex that is used for lower floor of the present invention coating composition can obtain low dust form aspect further good ink jet recording medium.
Can see by comparing embodiment 18 and embodiment 20, can obtain the good especially ink jet recording medium of glossiness by also using again wetting to cast to handle as the sub-micron pigment in the coating composition of upper strata of the present invention hydrated alumina.
Can see by comparing embodiment 20 and embodiment 21-25, under situation about handling that hydrated alumina is cast as the sub-micron pigment in the coating composition of upper strata of the present invention and with wetting again, can obtain high gloss and burnish resistance by behind coating and dry upper strata, carrying out calender process.
Can see by comparing embodiment 21,22 and embodiment 23-25, with hydrated alumina as the sub-micron pigment in the coating composition of upper strata of the present invention and under the situation of the processing of casting with wetting again after the calender process of carrying out behind coating and the dry upper strata, can obtain ink absorption and burnish resistance simultaneously by after calender process, the Bake paper smoothness of upper surface being adjusted in the 50-300 scope of second.
Can see by comparing embodiment 24 and embodiment 26-29, under situation about handling that hydrated alumina is cast as the sub-micron pigment in the coating composition of upper strata of the present invention and with wetting again, handle the ink jet recording medium that can obtain high burnish resistance by carry out the rewetting profit with the moistening liquid that contains silica gel.
Can see by comparing embodiment 26-28 and embodiment 29, carry out under the situation that the casting of rewetting profit handles in that hydrated alumina is handled as the sub-micron pigment in the coating composition of upper strata of the present invention and with the rewetting profit of carrying out with the waterborne liquid that contains silica gel, handle and to obtain the further high glossiness and the ink jet recording medium of burnish resistance by carry out the rewetting profit with the waterborne liquid that contains anion silica gel.
Can see by comparing embodiment 16 and embodiment 30 and embodiment 29 and embodiment 31, can obtain the ink jet recording medium that good gradation of drop-out colour and low dust form by in the coating composition of upper strata, containing thermoplastic resin in the present invention.
Can see by comparing embodiment 16 and embodiment 32 and embodiment 29 and embodiment 33, can obtain the good especially ink jet recording medium of ink absorption by in supporting mass, containing resin cation in the present invention.
Table 1
Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4 Embodiment 5 Embodiment 6
Glossiness 65 68 73 70 71 72
Ink absorption C C E C- C- D+
Low dust forms D- D+ C+ C- C- C+
Burnish resistance A- A- A- A- A- A-
Gradation of drop-out colour 2.02 2.05 2.15 2.08 2.1 2.13
Embodiment 7 Embodiment 8 Embodiment 9 Embodiment 10 Embodiment 11 Embodiment 12
Glossiness 67 73 69 70 70 72
Ink absorption A+ A C C C A+
Low dust forms D+ C+ C- C+ B A-
Burnish resistance A- A- A- A- A- A-
Gradation of drop-out colour 1.98 2.07 2.05 2.06 2.06 2.07
Table 2
Embodiment 13 Embodiment 14 Embodiment 15 Embodiment 16 Embodiment 17 Embodiment 18
Glossiness 76 77 77 78 77 79
Ink absorption C- C- A A A A
Low dust forms B A B+ A+ A+ A-
Burnish resistance A- A- A- A- A- A-
Gradation of drop-out colour 2.11 2.12 2.09 2.11 2.10 2.05
Embodiment 19 Embodiment 20 Embodiment 21 Embodiment 22 Embodiment 23 Embodiment 24
Glossiness 82 84 88 92 90 91
Ink absorption A+ A A B- A- A
Low dust forms A- A+ A+ A+ A+ A+
Burnish resistance D D C- B+ C+ B-
Gradation of drop-out colour 2.15 2.17 2.18 2.25 2.20 2.22
Table 3
Embodiment 25 Embodiment 26 Embodiment 27 Embodiment 28 Embodiment 29 Embodiment 30
Glossiness 92 71 91 91 95 78
Ink absorption B+ B- A A A A+
Low dust forms A+ A+ A+ A+ A+ A+
Burnish resistance B A- A- A- A+ A-
Gradation of drop-out colour 2.23 2.20 2.20 2.20 2.23 2.20
Embodiment 31 Embodiment 32 Embodiment 33
Glossiness 96 77 95
Ink absorption A A+ A+
Low dust forms A+ A+ A+
Burnish resistance A+ A- A+
Gradation of drop-out colour 2.27 2.08 2.21
Table 4
Comparing embodiment 1 Comparing embodiment 2 Comparing embodiment 3 Comparing embodiment 4 Comparing embodiment 5 Comparing embodiment 6
Glossiness 50 51 55 60 65 57
Ink absorption D- D- D+ C B- C
Low dust forms D D- E+ E E- E-
Burnish resistance A+ A+ A A A A
Gradation of drop-out colour 1.95 1.97 1.88 1.82 1.79 1.80
Comparing embodiment 7 Comparing embodiment 8 Comparing embodiment 9 Comparing embodiment 10 Comparing embodiment 11 Comparing embodiment 12
Glossiness 48 48 65 53 62 50
Ink absorption D- D- B- C C+ D+
Low dust forms D D E- E- E- D
Burnish resistance D- D- D- D- D- D-
Gradation of drop-out colour 1.93 1.91 1.83 1.83 1.75 1.92

Claims (16)

1. handle the ink jet recording medium of producing by lower floor and upper strata being provided and described layer being cast for one kind on the breathable supporting mass, wherein lower floor comprises and contains water imbibition pigment, latex and boric acid or boratory coating composition, and the upper strata comprises the coating composition that contains sub-micron pigment and polyvinyl alcohol.
2. ink jet recording medium as claimed in claim 1 is characterized in that, the water imbibition pigment in the lower floor is the wet method synthetic silica.
3. ink jet recording medium as claimed in claim 1 is characterized in that, after coating lower floor and before the coating upper strata supporting mass with lower floor is carried out calender process.
4. ink jet recording medium as claimed in claim 3 is characterized in that, the Bake paper smoothness that carries out the following laminar surface after the calender process is 50-300 second.
5. ink jet recording medium as claimed in claim 1 is characterized in that lower floor's coating composition contains cataloid.
6. ink jet recording medium as claimed in claim 1 is characterized in that, the latex in lower floor's coating composition is polyurethane resin latex.
7. ink jet recording medium as claimed in claim 6 is characterized in that, prepares polyurethane resin latex with PPG as initial feed.
8. ink jet recording medium as claimed in claim 6 is characterized in that, according to the regulation among the JIS K 7311, the tensile strength of polyurethane resin is 30-70MPa, and percentage elongation is 300-800%.
9. ink jet recording medium as claimed in claim 6 is characterized in that, is 10-60nm by the particle diameter of the polyurethane resin of dynamic light scattering determination.
10. be coated with the described ink jet recording medium of claim 1, it is characterized in that, the sub-micron pigment in the coating composition of upper strata is hydrated alumina, and with wetting again to the upper strata processing of casting.
11. ink jet recording medium as claimed in claim 10 is characterized in that, behind the coating upper strata and before the processing of casting the supporting mass with lower floor and upper strata is carried out calender process.
12. ink jet recording medium as claimed in claim 11 is characterized in that, carry out calender process after, the Bake paper smoothness of upper surface is 50-300 second.
13. ink jet recording medium as claimed in claim 10 is characterized in that, with the rewetting profit liquid rewetting profit upper strata of containing cataloid.
14. ink jet recording medium as claimed in claim 13 is characterized in that, the cataloid in the rewetting profit liquid is that average primary particle diameter is 40nm or littler anionic colloidal silica.
15. ink jet recording medium as claimed in claim 1, it is characterized in that, the upper strata coating composition contains the cation water-based dispersion of at least a resin that is selected from (1) (methyl) acrylate polymer, (2) styrene-(methyl) acrylate copolymer and (3) polyurethane, and described dispersion is 150nm or littler by the particle diameter of dynamic light scattering determination.
16. ink jet recording medium as claimed in claim 1 is characterized in that, described supporting mass contains resin cation.
CNA2006800325967A 2005-09-07 2006-09-07 Ink jet recording medium Pending CN101258036A (en)

Applications Claiming Priority (8)

Application Number Priority Date Filing Date Title
JP2005258906A JP4638307B2 (en) 2005-09-07 2005-09-07 Inkjet recording medium
JP258906/2005 2005-09-07
JP284178/2005 2005-09-29
JP296008/2005 2005-10-11
JP302607/2005 2005-10-18
JP313348/2005 2005-10-27
JP317136/2005 2005-10-31
JP317135/2005 2005-10-31

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Cited By (3)

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Publication number Priority date Publication date Assignee Title
CN102958703A (en) * 2010-07-02 2013-03-06 Omya发展股份公司 Paper for inkjet recording
CN111094006A (en) * 2017-09-05 2020-05-01 日本制纸株式会社 Ink jet recording medium
CN114541170A (en) * 2022-02-24 2022-05-27 岳阳林纸股份有限公司 Coating composition for papermaking, gravure light coated paper and manufacturing method thereof

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JP4536082B2 (en) * 2007-03-30 2010-09-01 三菱製紙株式会社 Method for manufacturing ink jet recording medium
JP5096945B2 (en) * 2008-01-30 2012-12-12 三菱製紙株式会社 Inkjet recording medium

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Publication number Priority date Publication date Assignee Title
WO2003101746A1 (en) * 2002-06-04 2003-12-11 Canon Kabushiki Kaisha Recording medium having ink receptive layer and process for producing the same
EP1795365B1 (en) * 2002-06-04 2008-10-08 Canon Kabushiki Kaisha Method for producing an ink-jet recording material.
JP2005305686A (en) * 2004-04-19 2005-11-04 Fuji Photo Film Co Ltd Sheet for inkjet recording, and recording method
JP4449943B2 (en) * 2005-07-01 2010-04-14 王子製紙株式会社 Method for producing ink jet recording sheet

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102958703A (en) * 2010-07-02 2013-03-06 Omya发展股份公司 Paper for inkjet recording
CN102958703B (en) * 2010-07-02 2015-03-04 Omya国际股份公司 Paper for inkjet recording
CN111094006A (en) * 2017-09-05 2020-05-01 日本制纸株式会社 Ink jet recording medium
CN114541170A (en) * 2022-02-24 2022-05-27 岳阳林纸股份有限公司 Coating composition for papermaking, gravure light coated paper and manufacturing method thereof

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