CN1533913A - Ink jet recording medium - Google Patents
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- CN1533913A CN1533913A CNA03128650XA CN03128650A CN1533913A CN 1533913 A CN1533913 A CN 1533913A CN A03128650X A CNA03128650X A CN A03128650XA CN 03128650 A CN03128650 A CN 03128650A CN 1533913 A CN1533913 A CN 1533913A
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Abstract
An ink-jet record medium with high-precision reproduction of image and high adhesion of image features that on its substrate, there are pigment, water-insoluble adhesive and cationic material chosen from three candidate materials.
Description
Technical field
The present invention relates on recording medium to use the ink-jet recording of water color ink record, and provide have good high precise image repeatability, the good fixed ink jet recording medium of lettering.
Background technology
Adopt the ink-jet recording of water color ink since little, the easy lookization of noise during record and can high-speed record etc. reason, just carrying out at present to aspects such as end print, fax, drawing or the printings of account ticket and using.Good quality paper that uses in the general printing or coated paper need be long-time because the absorbability of printing ink is poor, and the printing ink of lettering is moist on the paper surface, and the polluting device or the thin plate of lettering sometimes continuously stain image sometimes, therefore lack practicality.In order to solve such problem, the low record-paper of so-called use degree of sizing (spy opens clear 52-53012 communique) is disclosed or make in add the motion of the body paper steep water soluble macromolecular (spy opens clear 53-49113 communique) of urea-formaldehyde resin.In addition, high speed, the height that is accompanied by device becomes more meticulous or panchromaticization etc., the raising of ink-jet recording apparatus performance and the expansion of purposes, also can require the characteristic of height for recording medium.
Promptly, as ink jet recording medium, the concentration height of requirement ink-jet, bright, even the outflow of printing ink can not take place yet or ooze profit under the situation fast in absorption of inks, that point is overlapping, can not become big to the peripheral diffusion of printing ink point yet and must surpass needs, and the shape of point smoothly can not be blured, and also prevents from addition to be exposed to fading under the situation in ultraviolet ray or the water at document image.
At such characteristic, the paper used for recording (spy opens clear 55-51583 communique, the spy opens clear 56-148585 communique) that for example applies from the teeth outwards based on the various porous matter inorganic pigment classes of amorphous silica is disclosed.The ink-recording paper of above-mentioned coating sheet type, aspect the repeatability of a footpath and some shape, some concentration and tone, modified, but the printing ink that is used for these recording mediums, majority is to use the water color ink of water-soluble dye, under the situation that water etc. increases in the image that forms,, therefore produce the problem that the value of so-called record thing obviously reduces because dyestuff dissolves once more and ooze out on recording medium.
Therefore, in order to improve these shortcomings, disclose the recording medium (spy opens clear 56-84992 communique) that on the water soluble salt of giving metal on the recording surface (spy opens clear 55-53591 communique), surface, contains the polycation polyelectrolyte, given the dyestuff that forms in the printing ink and the anti-hydrated agent (spy opens clear 55-150696 communique) in color lake etc. in addition.In addition, in order to obtain good resistance to water, light resistance, the anti-hydrated agent that many selections have specific molecular structure (spy open clear 55-83882 communique, spy open clear 59-33176 communique, spy are opened clear 60-49990 communique, the spy opens clear 61-58788 communique etc.) is also disclosed.Having proposed the spy especially opens in the clear 56-99693 communique disclosed as being applicable to that by the interior methods such as cationic surface active agent, coating of freshening base material improves the example of resolution ratio resistance to water, open in the clear 59-198187 communique disclosedly as by selecting quaternary ammonium hydroxide to improve light resistance etc. with the spy, the resistance to water and the weatherability that are identified for lettering have certain effect.
Yet, be accompanied by the popularization of ink mist recording, now studying of the use of ink mist recording thing in various uses, constantly increase with respect to the lettering resistance to water of ink-jet recording paper, the requirement of weatherability.Simultaneously, for base material, also requirement is used to use the paper of being not only main use at present and is the recording use that film of synthetic resin and synthetic paper or nonwoven etc. do not have absorptive base material.Be difficult to from the lettering position to remove the recording medium of the base material that desolvates for use, realize sufficient lettering resistance to water difficulty more, the improvement that above-mentioned all motions brought also may not.
That is, the dye molecule that is used for ink mist recording is the anionic property molecule, by and recording medium in interaction between the cationic molecule that contains, dye molecule is fixed fast.As the cationic material that is used for recording medium, wish to have can effectively catch, molecular structure that fixedly anion is dye molecule, from this point of view, research, the cationic material that proposes various polymer-types be resin cation the fact as mentioned above.Yet, fixing of dye may not be quantitative in general these resin cations that use, if fixing dried printed matter contact with a large amount of water once more, then there is the so-called phenomenon that comprises the lettering outflow of resin cation, can not obtains the problem of sufficient lettering resistance to water.
On the other hand, the motion of so-called use cationic surfactant has also been proposed, one side makes dyestuff as the cationic material with fixing to a certain degree, and one side seeks out the effect that promotes absorption of inks in the recording medium, also can confirm to have improved certain lettering resistance to water thus.Yet,, also may not obtain sufficient resistance to water even use these cationic surfactant classes.
Summary of the invention
The present inventor forms in the ink jet recording medium of document image at the water color ink that contains water-soluble or water dispersible colorant in use, even in using the up-to-date ink-jet printer of a large amount of printing ink, also not only have and do not have the excellent images repeatability of a little oozing out, and lettering resistance to water, the structure of the cationic material that is suitable in the good recording medium of weatherability and the relation of lettering resistance to water have been carried out wholwe-hearted research, found that by using the cationic material of total carbon atom number in particular range of the hydrophobic group that combines with the N of quaternary ammonium salt, can obtain sufficient lettering resistance to water, also find in addition by adopting pigment class and water-insoluble binding agent simultaneously, can obtain the also good ink jet recording medium of image stationarity, thereby realize the present invention.
Promptly, the present invention (1) is an ink jet recording medium, making droplet transfer that the water color ink contain water-soluble or water dispersible colorant spray from small hole, forms to recording medium and form in the ink jet recording medium of document image, it is characterized in that this ink jet recording medium has to contain pigment and water-insoluble binding agent and contain to be selected from the cationic resin that cationic compound that following formula 1 represents and following formula 2, following formula 3 represent at least a kind ink-receiver layer on base material.
(in the formula, satisfy R1～R4 and be hydrophobic group independently separately, and the total carbon atom number of R1～R4 is 16～36.X is a halogen.)
(in the formula, satisfying at least one side of R5, R6 is that carbon number is 12～18 hydrophobic group, and the total carbon atom number of R5 and R6 is 13～36.X is a halogen.M is 20～5000 integer.)
(in the formula, satisfying at least one side of R7, R8 is that carbon number is 12～18 hydrophobic group, and the total carbon atom number of R7 and R8 is 13～36.X is a halogen.N is 20～5000 integer.)
In addition, the present inventor forms in the ink jet recording medium of document image at the water color ink that contains water-soluble or water dispersible colorant in use, even in using the up-to-date ink-jet printer of a large amount of printing ink, also not only have the excellent images repeatability that does not have a little to ooze out with ink bleed, and lettering resistance to water, the material that uses in the good recording medium of weatherability and the rerum natura of recording medium have been carried out wholwe-hearted research, found that, on base material, has the pigment of containing, the ink-receiver layer of the cationic material of total carbon atom number in particular range of binding agent and the hydrophobic group that combines with the N of quaternary ammonium salt, and be 20 (ms) using dynamic scan imbibition instrumentation fixed time of contact
L/2The time be 30ml/m by regulating water to the transfer amount of recording medium
2Above 100ml/m
2Below, can obtain sufficient lettering resistance to water, and obtain the some lettering that repeatability is good, meticulous, color development is good, the ink jet recording medium of ink bleed etc. does not take place, thereby has realized the present invention.
The present invention (2) is an ink jet recording medium, making droplet transfer that the water color ink contain water-soluble or water dispersible colorant sprays from small hole, forms to recording medium and form in the ink jet recording medium of document image, it is characterized in that this ink jet recording medium has in the cationic resins of the cationic compound that contains pigment, binding agent and be selected from following formula 1 expression and following formula 2 and 3 expressions at least a kind ink-receiver layer on base material, and be 20 (ms) using dynamic scan imbibition instrumentation fixed time of contact
1/2The transfer amount of Shi Shuixiang recording medium is 30～100ml/m
2
(in the formula, satisfy R1～R4 and be hydrophobic group independently separately, and the total carbon atom number of R1～R4 is 16～36.X is a halogen.)
(in the formula, satisfying at least one side of R5, R6 is that carbon number is 12～18 hydrophobic group, and the total carbon atom number of R5 and R6 is 13～36.X is a halogen.M is 20～5000 integer.)
(in the formula, satisfying at least one side of R7, R8 is that carbon number is 12～18 hydrophobic group, and the total carbon atom number of R7 and R8 is 13～36.X is a halogen.N is 20～5000 integer.)
Wherein, the cationic compound of formula 1 is preferably following formula 4.
(in the formula, satisfy R1, R2 for independently carbon number is at the alkyl 8 or more separately, R3, R4 are that separately carbon number independently is 1～4 alkyl, and the total carbon atom number of R1～R4 is 18～36.X is a halogen.)
In addition, the cationic compound of formula 1 is preferably following formula 5.
(in the formula, satisfy R1 and be carbon number at the alkyl more than 13, R2, R3, R4 for separately independently carbon number be 1～4 alkyl, and the total carbon atom number of R1～R4 is 16～36.X is a halogen.)
Moreover the cationic compound of formula 2 is preferably following formula 6.
(in the formula, R5 is that carbon number is 12～18 alkyl.X is a halogen.N is 20～5000 integer.)
Moreover what base material was preferably selected from film, synthetic paper, nonwoven is the sheet material of main component with synthetic resin.
In addition, binding agent preferably contains polyacrylic, polyvinyl acetate system, polyethylene-vinylacetate is the water-insoluble binding agent.
The specific embodiment of invention
The present invention (1) is characterised in that, on base material, form contain pigment class, water-insoluble binding agent and be selected from the cationic compound of following formula 1 expression and the cationic resin of following formula 2, following formula 3 expressions at least a kind ink-receiver layer.
(in the formula, satisfy R1～R4 and be hydrophobic group independently separately, and the total carbon atom number of R1～R4 is 16～36.X is a halogen.)
(in the formula, satisfying at least one side of R5, R6 is that carbon number is 12～18 hydrophobic group, and the total carbon atom number of R5 and R6 is 13～36.X is a halogen.M is 20～5000 integer.)
(in the formula, satisfying at least one side of R7, R8 is that carbon number is 12～18 hydrophobic group, and the total carbon atom number of R7 and R8 is 13～36.X is a halogen.N is 20～5000 integer.)
Such cationic compound and cationic resin, has on N quaternary ammonium salt structure in conjunction with hydrophobic group, and the total carbon atom number of hydrophobic group is in specific scope, by can carrying out the fixing of image apace in conjunction with these, and obtain the also good lettering image of repeatability of lettering resistance to water and image.
This reason also may not be understood, but can infer by adjusting and carry out near the interactional quaternary ammonium moiety with the anionic property dye molecule hydrophobicity degree, the dye molecule of catching effectively, fixedly containing in the aqueous ink, and after the lettering drying, even printed matter becomes situation moistening or immersion, because the hydrophobicity of appropriateness also can suppress by the moving of the water generates at fixing of dye position, the result can obtain good lettering resistance to water.Also have, the preferable range of the total carbon atom number of the hydrophobic group that combines with the N of quaternary ammonium salt is 16～36, and preferred scope is 20～30.
As such cationic material, not necessarily limit, but quaternary ammonium salt cationic compounds such as tetrabutylammonium chloride, cetyltrimethylammonium chloride, chlorination four pentyl ammonium, chlorination stearyl trimethyl ammonium, chlorination didecyldimethyl ammonium, chlorination stearyl dimethyl benzyl ammonium, chloro distearyl dimethyl ammonium can illustratively be arranged, or polychlorostyrene diallyl didecyl ammonium etc., on main chain or side chain, contain the polymer class of the structure that hydrophobic group combines with N in the cation property copolymer of quaternary ammonium salt structure.In addition, as hydrophobic group, suitable selection from long-chain monoene, benzyls etc. such as alkyl such as decyl, lauryl, cetyl, stearyl, oil base, but carbon number is the chain alkyl more than 10, since resistance to water to improve effect big especially, especially preferably use.
In addition as required, by import with such hydrophobic residue BTA system, bulky amine cording have ultraviolet radiation absorption can hydrophobic residue, can further improve the keeping quality of record.In addition, these cationic compounds can adopt simultaneously with the normally used polymer-type cationic compound that is called the resin cation class in the ink jet recording medium.As such resin cation, can illustration dicyandiamide condensation-type polymerization thing class, diallylamine type polymer class, PAH class, polyacrylamide etc. such as polychlorostyrene dimethyldiallylammonium.
As mentioned above, can promote the absorption of printing ink, but, produce the disadvantage that so-called lettering oozes profit by the ink-receiver layer that contains above-mentioned cationic compound is set on the base material top layer of ink jet recording medium owing to soaking into of top layer printing ink excessively promoted.
In order to address this problem, in the present invention, in above-mentioned ink-receiver layer, adopt the water-insoluble binding agent to have great feature simultaneously.As the water-insoluble binding agent, general suitable selection use from the aqueous dispersion of polyacrylic, polystyrene, polyurethane series, polyester system, polystyrene-acrylic acid series, polyvinyl acetate system, polyvinyl chloride, polyethylene-vinylacetate system, polyvinyl chloride-water-insoluble resinaes such as vinylacetate system, but these not necessarily just limited.These resinaes, compare with the water-soluble resin class of generally using as binding agent, not only have and suppress the effect that printing ink soaks into, and has an effect of improving the resistance to water of ink-receiver layer own, therefore by with the present invention in the above-mentioned 4 valency cationic materials stipulated adopt simultaneously, can obtain particularly preferred record quality and lettering resistance to water.In addition, in these water-insoluble binding agents, polyacrylic, polyvinyl acetate system, polyethylene-vinylacetate are binding agent, because therefore the xanthochromia that time exposure produces, painted few more preferably uses.
As the pigment class of using in the ink-receiver layer, not necessarily limit, but from the organic pigment class of inorganic pigments such as alumina silicate, calcium silicates, magnesium silicate, amorphous silica, aluminium oxide, aluminium hydroxide, magnesium hydroxide, calcium carbonate, kaolin, talcum, calcium sulfate, barium sulfate, titanium dioxide, zinc oxide, zinc carbonate, satin white, diatomite, polystyrene, acrylic acid series, urea resin system, melamine resin system, benzoguanamine resin system, adopt simultaneously or suitably select separately.Particularly, amorphous silica, aluminium hydroxide, the most kinds of magnesium hydroxide can be easy to select to possess the kind of wishing performance in industrial listing, therefore can preferably use.
Moreover, as binding agent, except above-mentioned water-insoluble binding agent, also can adopt starch and derivative thereof simultaneously, carboxymethyl cellulose, hydroxyethylcellulose, casein, gelatin, natural or semi-synthetic high score subclass such as soybean protein, polyvinyl alcohol and derivative thereof, polyvinyl butyral resin, polymine is a resin, polyvinylpyrrolidone is a resin, poly-(methyl) acrylic resin, the acrylic ester resin, polyamide-based resin, polyacrylamide is a resin, mylar, urea resin, melamine resin, styrene-butadiene-copolymer, the MMB methyl methacrylate butadiene copolymer, the aqueous solution or the aqueous dispersion of vinyl acrylic copolymer resin such as ethylene-vinyl acetate copolymer perhaps import the material known such as polymer-modified of anionic property or cationic residue in above-mentioned resinae.
In ink-receiver layer, also can use pigment dispersing agent, tackifier, defoamer, foam inhibitor, blowing agent, remover, penetrant, wetting agent, Thermogelling agent, lubricant, the known various auxiliary agents of other these technical fields as required in addition.
As base material, suitable use on copying the paper pulp that paper uses add silica, talcum, kaolin as required, fire fillers such as kaolin, calcium carbonate, by the acid or neutral body paper of copying the method modulation of implementing usually in the paper, perhaps dry type or Wet-laid non-woven fabric or film of synthetic resin and synthetic paper etc.As purpose of the present invention, for the ink mist recording thing of realizing having excellent water-resistance, also require the resistance to water of base material itself, therefore as base material, what be preferably selected from the film that has excellent water-resistance, synthetic paper, nonwoven especially is the sheet material of main component with synthetic resin.As the means of the above-mentioned ink-receiver layer of coating on these base materials, can suit to select that size press (サ イ ズ プ レ ス), door roll coating (ゲ-ト ロ-Le), roller coat, rod are coated with, gravure roll apply, air-blade type applies, scraper applies (ロ Star De Block レ-De コ--), scraper type applies normally used coating means such as (Block レ-De コ--), mold pressing coating or the coating of curtain formula.
The coating amount of ink-receiver layer is generally 1～50g/m
2, be preferably 2～30g/m
2The optimised quantity of the above-mentioned cationic compound that contains in the ink-receiver layer according to the condition of the record lettering that uses and therefore difference do not limit especially, but generally suits to be adjusted to 0.05～5g/m
2Scope.That is, be less than 0.05g/m
2Situation under can not get sufficient lettering resistance to water, if more than 5g/m
2, be accompanied by moving of superfluous cationic compound, probably have the disadvantages such as profit accelerates easily of oozing of record.
In the water color ink that the present invention uses, contain in water-soluble direct dyes and the water-soluble acid dyestuff at least a kind as dyestuff, in addition suitable wetting agent, dyestuff lytic agent, anticorrisive agent, the mould inhibitor etc. of containing.As water-soluble direct dyes, can enumerate that CI. is directly black, CI. is directly yellow, CI. is directly blue, CI. is directly red etc., as water-soluble acid dyestuff, can enumerate CI. acid black, CI. Indian yellow, CI. acid blue, CI. acid red etc., but not necessarily be limited to these.
The present invention (2) is characterised in that, on base material, form contain pigment class, binding agent and be selected from the cationic compound of following formula 1 expression and the cationic resin of following formula 2, following formula 3 expressions at least a kind ink-receiver layer, and be 20 (ms) using dynamic scan imbibition instrumentation fixed time of contact
1/2The transfer amount of Shi Shuixiang recording medium is 30～100ml/m
2
(in the formula, satisfy R1～R4 and be hydrophobic group independently separately, and the total carbon atom number of R1～R4 is 16～36.X is a halogen.)
(in the formula, satisfying at least one side of R5, R6 is that carbon number is 12～18 hydrophobic group, and the total carbon atom number of R5 and R6 is 13～36.X is a halogen.M is 20～5000 integer.)
(in the formula, satisfying at least one side of R7, R8 is that carbon number is 12～18 hydrophobic group, and the total carbon atom number of R7 and R8 is 13～36.X is a halogen.N is 20～5000 integer.)
Such cationic compound and cationic resin, has on N quaternary ammonium salt structure in conjunction with hydrophobic group, and the total carbon atom number of hydrophobic group is in specific scope, by can carrying out the fixing of image apace in conjunction with these, and obtain the also good lettering image of repeatability of lettering resistance to water and image.
This reason also may not be understood, but can infer by adjusting and carry out near the interactional quaternary ammonium moiety with the anionic property dye molecule hydrophobic degree, the dye molecule of catching effectively, fixedly containing in the aqueous ink, and after the lettering drying, even printed matter becomes situation moistening or immersion, because the hydrophobicity of appropriateness can suppress moving by the water generates at fixing of dye position.Total carbon atom number by making the hydrophobic group that combines with the N of quaternary ammonium salt in 16～36 scope, preferred scope is 20～30, can carry out the fixing of image apace, and obtain the also good lettering image of repeatability of lettering resistance to water and image.
Yet, contain the ink-receiver layer of such cationic compound or cationic resin, promoted the absorption of printing ink, but since in the top layer soaking into of printing ink excessively promoted, produce the disadvantage that so-called lettering oozes profit.In order to address this problem, in the present invention, being adjusted in and using dynamic scan imbibition instrumentation fixed time of contact is 20 (ms)
1/2The time water be 30ml/m to the transfer amount of recording medium
2Above 100ml/m
2Below, have great feature in this.
As such cationic material, not necessarily limit, but quaternary ammonium salt cationic compounds such as tetrabutylammonium chloride, cetyltrimethylammonium chloride, chlorination four pentyl ammonium, chlorination stearyl trimethyl ammonium, chlorination didecyldimethyl ammonium, chlorination stearyl dimethyl benzyl ammonium, chloro distearyl dimethyl ammonium can illustratively be arranged, or polychlorostyrene diallyl didecyl ammonium etc., on main chain or side chain, contain the polymer class of the structure that hydrophobic group combines with N in the cation property copolymer of quaternary ammonium salt structure.In addition, as hydrophobic group, suitable selection from long-chain monoene, benzyls etc. such as alkyl such as decyl, lauryl, cetyl, stearyl, oil base, but the chain alkyl of carbon number in 10～14 scopes, because the balance of resistance to water effect and ink absorption effect is good, especially preferably use.By the way, if carbon number is too small, the tendency that then has resistance to water to reduce if carbon number is excessive, can be expected the effect that resistance to water improves, but opposite, hydrophobic group greatly probably can appear at the problem that dissolubility reduces in the aqueous coating.
In addition as required, by import with such hydrophobic residue BTA system, bulky amine cording have ultraviolet radiation absorption can hydrophobic residue, can further improve the keeping quality of record.In addition, these cationic compounds can adopt simultaneously with the normally used polymer-type cationic compound that is called the resin cation class in the ink jet recording medium.As such resin cation, can illustration dicyandiamide condensation-type polymerization thing class, diallylamine type polymer class, PAH class, polyacrylamide etc. such as polychlorostyrene dimethyldiallylammonium.
The metastatic adjusting of water in the ink-receiver layer top layer of ink jet recording medium, can contain polyacrylic in the ink-receiver layer by making, polystyrene, polyurethane series, polyester system, polystyrene-acrylic acid series, polyvinyl acetate system, polyvinyl chloride, polyethylene-vinylacetate system, the aqueous dispersion of polyvinyl chloride-water-insoluble resinaes such as vinylacetate system or fluorine system, siloxane-based, hydrophobic materials such as paraffin series are regulated rerum natura or the adjusting pigment (P/B) relevant with absorbability such as oil suction degree of the pigment that uses in the ink-receiver layer and are recently carried out.
Be not limited to above-mentioned method, but adopt the method for the aqueous dispersion of water-insoluble resinae simultaneously, compare with the water-soluble resin class of generally using as binding agent, not only have and suppress the effect that printing ink soaks into, and has an effect of improving the resistance to water of ink-receiver layer own, therefore preferably by with the present invention in the above-mentioned 4 valency cationic materials stipulated adopt simultaneously, can obtain particularly preferred record quality and lettering resistance to water.In addition, in these water-insoluble binding agents, polyacrylic, polyvinyl acetate system, polyethylene-vinylacetate are binding agent, because therefore the xanthochromia that time exposure produces, painted few more preferably uses.
The present invention as use in the ink mist recording that carries out the high speed lettering, ink absorption and the modified recording medium of printing ink stationarity also be useful.The present inventor finds, is aspect the high speed ink jet print adaptability in purpose, and droplets of ink contacts that the absorbability with paper has decisive influence behind about 400ms on the surface.The good recording medium of high speed lettering of the present invention's regulation, being adjusted in time of contact is 20 (ms)
1/2The time distilled water be 30ml/m to the transfer amount of recording medium
2More than, 100ml/m
2Below have great feature, with the relevant rerum natura of recording medium water imbibition in extremely short time of contact that exemplifies here, the dynamic scan imbibition meter (DSA) that all can use the Seiko (strain) of for example coordinating to make is measured.In time of contact is 20 (ms)
1/2The time distilled water be preferably 40ml/m to the transfer amount of recording medium
2More than, on be limited to 100ml/m
2Under the few situation of transfer amount, when playing, droplets of ink can produce the problem that printing ink extends to more than the needs, the fineness of image diminishes, on the other hand, under the too much situation of transfer amount, lettering dims out, and can not obtain good color development, under the situation of using paper and so on absorbability base material, printing ink can move to base material, and ink bleed in most of the cases takes place, and is not preferred therefore.
Dynamic scan imbibition meter (dynamic scanning absorptometer; DSA, paper パ skill association will, the 48th volume, in May, 1994, the 88th～92 page, the idle weight then), be the device that can correctly measure uptake at the utmost point in the short time.Dynamic scan imbibition meter be sample is made discoid, on this, the imbibition head is carried out helical form scanning, make sweep speed change automatically according to predefined mode, the speed of directly reading imbibition that moves by meniscus in the capillary, only measure necessary point in 1 sample, according to the device of described method automatic assay.Head to paper sample supply liquid makes it to be connected with capillary through teflon tube, and the position of meniscus can use optical pickocff to read automatically in the capillary.
As the pigment class of using in the ink-receiver layer, not necessarily limit, but from the organic pigment class of inorganic pigments such as alumina silicate, calcium silicates, magnesium silicate, amorphous silica, aluminium oxide, aluminium hydroxide, magnesium hydroxide, calcium carbonate, kaolin, talcum, calcium sulfate, barium sulfate, titanium dioxide, zinc oxide, zinc carbonate, satin white, diatomite, polystyrene, propylene system, urea resin system, melamine resin system, benzoguanamine resin class, suitably select to adopt simultaneously or separately.Particularly, amorphous silica, aluminium hydroxide, the most kinds of magnesium hydroxide can be easy to select to possess the kind of wishing performance in industrial listing, therefore can preferably use.
As the binding agent that uses in the ink-receiver layer, the suitable polyacrylic that uses, polystyrene, polyurethane series, polyester system, polystyrene-acrylic acid series, polyvinyl acetate system, polyvinyl chloride, polyethylene-vinylacetate system, polyvinyl chloride-water-insoluble binding agents such as vinylacetate system, starch and derivative thereof, carboxymethyl cellulose, hydroxyethylcellulose, casein, gelatin, natural or semi-synthetic high score subclass such as soybean protein, polyvinyl alcohol and derivative thereof, polyvinyl butyral resin, polymine is a resin, polyvinylpyrrolidone is a resin, poly-(methyl) acrylic resin, the acrylic ester resin, polyamide-based resin, polyacrylamide is a resin, mylar, urea resin, melamine resin, styrene-butadiene-copolymer, the MMB methyl methacrylate butadiene copolymer, the aqueous solution or the aqueous dispersion of vinyl acrylic copolymer resin such as ethylene vinyl acetate copolymer perhaps import the material known such as polymer-modified of anionic property or cationic residue in above-mentioned resinae.
In ink-receiver layer, also can use pigment dispersing agent, tackifier, defoamer, foam inhibitor, blowing agent, remover, penetrant, wetting agent, Thermogelling agent, lubricant, the known various auxiliary agents of other these technical fields as required.
As base material, suitable use on copying the paper pulp that paper uses add silica, talcum, kaolin as required, fire fillers such as kaolin, calcium carbonate, by the acid or neutral body paper of copying the method modulation of implementing usually in the paper, perhaps dry type or Wet-laid non-woven fabric or film of synthetic resin and synthetic paper etc.As purpose of the present invention, for the ink mist recording thing of realizing having excellent water-resistance, also require the resistance to water of base material itself, therefore as base material, what be preferably selected from the film that has excellent water-resistance, synthetic paper, nonwoven especially is the sheet material of main component with synthetic resin.
As the means of the above-mentioned ink-receiver layer of coating on these base materials, can suit to select that size press, door roll coating, roller coat, rod are coated with, gravure roll applies, air-blade type applies, scraper applies, scraper type applies, normally used coating means such as mold pressing coating or the coating of curtain formula.
The coating amount of ink-receiver layer is generally 1～50g/m
2, be preferably 2～30g/m
2The optimised quantity of the above-mentioned cationic compound that contains in the ink-receiver layer according to the condition of the record lettering that uses and therefore difference do not limit especially, but generally suits to be adjusted to 0.05～5g/m
2Scope.That is, be less than 0.05g/m
2Situation under can not get sufficient lettering resistance to water, if more than 5g/m
2, be accompanied by moving of superfluous cationic compound, probably have the disadvantages such as profit accelerates easily of oozing of record.
In the water color ink that the present invention uses, contain in water-soluble direct dyes and the water-soluble acid dyestuff at least a kind as dyestuff, in addition suitable wetting agent, dyestuff lytic agent, anticorrisive agent, the mould inhibitor etc. of containing.As water-soluble direct dyes, can enumerate that CI. is directly black, CI. is directly yellow, CI. is directly blue, CI. is directly red etc., as water-soluble acid dyestuff, can enumerate CI. acid black, CI. Indian yellow, CI. acid blue, CI. acid red etc., but not necessarily be limited to these.
Also have, in the present invention (1) and (2), the cationic compound of formula 1 is a following formula 4, the lettering resistance to water to improve effect good, be preferred therefore.
(in the formula, satisfy R1, R2 for independently carbon number is at the alkyl 8 or more separately, R3, R4 are that separately carbon number independently is 1～4 alkyl, and the total carbon atom number of R1～R4 is 18～36.X is a halogen.)
In addition, the cationic compound of formula 1 is a following formula 5, the lettering resistance to water to improve effect good especially, be preferred therefore.
(in the formula, satisfy R1 and be carbon number at the alkyl more than 13, R2, R3, R4 for separately independently carbon number be 1～4 alkyl, and the total carbon atom number of R1～R4 is 16～36.X is a halogen.)
Moreover the cationic compound of formula 2 is following formulas 6, and the resistance to water of lettering not only is enhanced, and the improvement that lettering oozes out under high humility also is desired, is preferred therefore.
(in the formula, R5 is that carbon number is 12～18 alkyl.X is a halogen.N is 20～5000 integer.)
[embodiment]
Below enumerate embodiment and more specifically describe the present invention, but the obvious qualification that is not subjected to these examples.Also have umber and the % shown in the embodiment to be meant mass parts and quality %.
Embodiment 1
" making of the coating body paper that ink jet paper is used (making of base material) "
In the LBKP that 90 parts of freeness are 450mlcsf, mix 10 parts of NBKP that freeness is 480mlcsf, modulate 25 parts of calcium carbonate, 0.1 part of alkyl ketene dimer, 0.05 part of poly-(methyl) acrylamide of cation system, 1 part of cationic starch, 0.5 part of aluminum sulfate, use fourdrinier paper machine to copy slurry paper and heavily be 110g/m
2Body paper, use the starch solution of size press device coating 2% to make the dry back coating amount of every single face be 0.4g/m
2, drying obtains solution degree of sizing according to JIS-P-8122 and is the coating body paper that 100 seconds ink jet paper is used.
" making of ink jet recording medium (formation of ink-receiver layer) "
With 65 parts of amorphous silica pigment (trade name: Off ア イ Application シ-Le X-45; (strain) ト Network ヤ マ system) is dispersed in 1.5% aqueous solution of 600 parts of cetyltrimethylammonium chlorides (total carbon atom number of hydrophobic group is 19), to wherein adding 300 parts of polyvinyl alcohol (trade name: Network ラ レ Port バ-Le PVA-117, (strain) Network ラ レ system), 10% aqueous solution, 35 parts of ethylene vinyl acetate copolymer emulsion (trade names: ス ミ カ Off レ Star Network ス 473 as binding agent; Sumitomo Chemical system 57% aqueous dispersion), make the ink-receiver layer masking liquid.Use マ イ ヤ バ-make that dried coating amount is 5g/m on the coating body paper that above-mentioned ink jet paper is used with the coating of this masking liquid is dry
2Afterwards, carry out the supercalendering processing and obtain ink jet recording medium.
Embodiment 2
" making of the coating body paper that ink jet paper is used (making of base material) "
Obtain the coating body paper that ink jet paper is used similarly to Example 1.
" making of ink jet recording medium (formation of ink-receiver layer) "
Except using chlorination four pentyl ammonium (total carbon atom number of hydrophobic group is 20) to replace cetyltrimethylammonium chloride, the coating drying makes that dried coating amount is 10g/m
2In addition, obtain ink jet recording medium similarly to Example 1.
Embodiment 3
" making of the coating body paper that ink jet paper is used (making of base material) "
Obtain the coating body paper that ink jet paper is used similarly to Example 1.
" making of ink jet recording medium (formation of ink-receiver layer) "
With 75 parts of amorphous silica pigment (trade name: Off ア イ Application シ-Le X-45; (strain) ト Network ヤ マ system) is dispersed in 2% aqueous solution of 600 parts of chlorination didecyldimethyl ammonium (total carbon atom number of hydrophobic group is 22), to wherein adding 300 parts of polyvinyl alcohol (trade name: Network ラ レ Port バ-Le PVA-117, (strain) Network ラ レ system), 10% aqueous solution, 25 parts of ethene vinyl chloride vinyl acetate co-polymer emulsion (trade names: ス ミ カ Off レ Star Network ス 820 as binding agent; Sumitomo Chemical system 50% aqueous dispersion), make the ink-receiver layer masking liquid.
Use マ イ ヤ バ-make dried coating amount be 10g/m this masking liquid coating drying
2Afterwards, carry out the supercalendering processing and obtain ink jet recording medium.
Comparative example 1
" making of the coating body paper that ink jet paper is used (making of base material) "
Obtain the coating body paper that ink jet paper is used similarly to Example 1.
" making of ink jet recording medium (formation of ink-receiver layer) "
Except using polychlorostyrene dimethyldiallylammonium (trade name: ユ ニ セ Application ス CP-103; セ Application カ (strain) system, 40% aqueous solution) replace obtaining ink jet recording medium similarly to Example 1 beyond the cetyltrimethylammonium chloride.
Comparative example 2
" making of the coating body paper that ink jet paper is used (making of base material) "
Obtain the coating body paper that ink jet paper is used similarly to Example 1.
" making of ink jet recording medium (formation of ink-receiver layer) "
Except using chloro distearyl dimethyl ammonium (total carbon atom number of hydrophobic group is 38) replacement cetyltrimethylammonium chloride, obtain ink jet recording medium similarly to Example 1.
Comparative example 3
" making of the coating body paper that ink jet paper is used (making of base material) "
Obtain the coating body paper that ink jet paper is used similarly to Example 1.
" making of ink jet recording medium (formation of ink-receiver layer) "
With 75 parts of amorphous silica pigment (trade name: Off ア イ Application シ-Le X-45; (strain) ト Network ヤ マ system) is dispersed in 1.5% aqueous solution of 625 parts of chlorination didecyldimethyl ammonium (total carbon atom number of hydrophobic group is 22), to wherein adding 300 parts of polyvinyl alcohol (trade name: Network ラ レ Port バ-Le PVA-117 as binding agent, (strain) Network ラ レ system) 10% aqueous solution is made the ink-receiver layer masking liquid.Except using this masking liquid, obtain ink jet recording medium similarly to Example 1.
Embodiment 4
With 65 parts of amorphous silica pigment (trade name: Off ア イ Application シ-Le X-60; (strain) ト Network ヤ マ system) is dispersed in 1.5% aqueous solution of 600 parts of chlorination dilauryl Dimethyl Ammonium (total carbon atom number of hydrophobic group is 26), to wherein adding 300 parts of modified polyvinylalcohols (trade name: Network ラ レ R polymer R-1130, (strain) Network ラ レ system), 10% aqueous solution, 50 parts of ethene vinyl chloride vinyl acetate co-polymer emulsion (trade names: ス ミ カ Off レ Star Network ス 820 as binding agent; Sumitomo Chemical system 50% aqueous dispersion), make the ink-receiver layer masking liquid.
Use マ イ ヤ バ-with the dry white PET film (trade name: テ ト ロ Application U5 type that makes at 100 μ m thickness of this masking liquid coating; Supreme Being people's (strain) system) going up dried coating amount is 15g/m
2, obtain ink jet recording medium.
Embodiment 5
With 60 parts of amorphous silica pigment (trade name: サ イ ロ ジ エ Star ト P-405; グ レ-ス デ ヴ イ ソ Application (strain) system) is dispersed in 3% aqueous solution of 650 parts of chlorination didecyldimethyl ammonium (total carbon atom number of hydrophobic group is 22), to wherein adding 250 parts of polyvinyl alcohol (trade name: Network ラ レ Port バ-Le PVA-117, (strain) Network ラ レ system), 10% aqueous solution, 40 parts of acetate emulsion (trade names: ヨ De ゾ-Le CE60 as binding agent; NSC (strain) makes 50% aqueous dispersion), make the ink-receiver layer masking liquid.
Use マ イ ヤ バ-with the dry synthetic paper (trade name: YUPO FPG-110 that makes at 110 μ m thickness of this masking liquid coating; (strain) ユ Port コ-Port レ-シ ヨ Application system) going up dried coating amount is 15g/m
2, obtain ink jet recording medium.
Embodiment 6
With 60 parts of amorphous silica pigment (trade name: サ イ ロ ジ エ Star ト P-412; グ レ-ス デ ヴ イ ソ Application (strain) system) is dispersed in 3% aqueous solution of 560 parts of chlorination stearyl dimethyl benzyl ammoniums (total carbon atom number of hydrophobic group is 27), to wherein adding 40 parts of polychlorostyrene dimethyldiallylammoniums (trade name: ユ ニ セ Application ス CP-103; セ Application カ (strain) system, 40% aqueous solution) and 300 parts of modified polyvinylalcohols (trade name: Network ラ レ R polymer R-1130, (strain) Network ラ レ system), 10% aqueous solution, 40 parts of acrylic acid emulsion (trade names: リ カ ボ Application De FK-820 as binding agent; Central authorities' physics and chemistry industry (strain) system, 40% aqueous dispersion), make the ink-receiver layer masking liquid.
Except using this masking liquid, obtain ink jet recording medium similarly to Example 5.
Embodiment 7
With 100 parts of amorphous silica pigment (trade name: カ-プ レ Star Network ス BS-304N; Shionogi (strain) system) is dispersed in 4% aqueous solution of 750 parts of chlorination didecyldimethyl ammonium, to wherein adding 150 parts of ethylene vinyl acetate copolymer emulsions (trade name: ス ミ カ Off レ Star Network ス 473 as binding agent; Sumitomo Chemical system 57% aqueous dispersion), make the ink-receiver layer masking liquid.
Use マ イ ヤ バ-with the dry synthetic paper (trade name: YUPO FPG-110 that makes at 110 μ m thickness of this masking liquid coating; (strain) ユ Port コ-Port レ-シ ヨ Application system) going up dried coating amount is 20g/m
2, obtain ink jet recording medium.
Comparative example 4
With 65 parts of amorphous silica pigment (trade name: Off ア イ Application シ-Le X-60; (strain) ト Network ヤ マ system) is dispersed in 635 parts of poly dimethyl amine ammonia エ Port Network ロ Le ヒ De リ Application copolymer (trade names: PAL-2; セ Application カ (strain) system, 20% aqueous solution) in 2% aqueous solution,, make the ink-receiver layer masking liquid to wherein adding 300 parts of modified polyvinylalcohols (trade name: Network ラ レ R polymer R-1130, (strain) Network ラ レ system), 10% aqueous solution as binding agent.
Except using this masking liquid, obtain ink jet recording medium similarly to Example 5.
Comparative example 5
With 60 parts of amorphous silica pigment (trade name: サ イ ロ ジ エ Star ト P-405; グ レ-ス デ ヴ イ ソ Application (strain) system) is dispersed in 3% aqueous solution of 650 parts of ethyl sulfuric acid lanolin fatty acid aminopropyl ethyl alkyl dimethyl ammonium chlorides, to wherein adding 300 parts of modified polyvinylalcohols (trade name: Network ラ レ R polymer R-1130, (strain) Network ラ レ system), 10% aqueous solution, 40 parts of vinyl acetate emulsion (trade names: ヨ De ゾ-Le CE60 as binding agent; NSC (strain) makes 50% aqueous dispersion), make the ink-receiver layer masking liquid.
Except using this masking liquid, obtain ink jet recording medium similarly to Example 5.
Comparative example 6
With 65 parts of amorphous silica pigment (trade name: サ イ ロ ジ エ Star ト P-412; グ レ-ス デ ヴ イ ソ Application (strain) system) is dispersed in 600 parts of dicyandiamide polyamine condensation product (trade names: Neofix RP-70; Solar corona chemistry (strain) system, 70% aqueous solution) in 1.5% aqueous solution, to wherein adding 300 parts of modified polyvinylalcohols (trade name: Network ラ レ R polymer R-1130, (strain) Network ラ レ system) 10% aqueous solution and 35 parts of ethylene vinyl acetate copolymer emulsion (trade names: ス ミ カ Off レ Star Network ス 473 as binding agent; Sumitomo Chemical system 57% aqueous dispersion), make the ink-receiver layer masking liquid.
Except using this masking liquid, obtain ink jet recording medium similarly to Example 5.
The result who estimates lettering concentration, lettering tractability, lettering stationarity, lettering resistance to water at the ink jet recording medium that obtains is presented in the table 1.
" evaluation "
1. evaluation lettering
Use the color inkjet printer EPSON PM750C of company that sells on the market, print black, cyanogen, magenta, yellow monochromatic and red, green, blue heavy look is developed and printed and the image of fine rule.
2. lettering image color
Use Macbeth reflection of the concentration RD914, measure the reflection density that use that the EPSON PM750C of company prints black, cyanogen, magenta, yellow monochrome are developed and printed image lettering part.
3. lettering tractability
What fine rule image lettering part that the EPSON PM750C of company prints judge was used in range estimation oozes profit, tractability.
Metewand
◎: good.
Zero: good
△: poorer a little.
*: poor.
4. lettering stationarity
That lettering uses that the EPSON PM750C of company prints is black, cyanogen, magenta, yellow, redness, green, the blue image of developing and printing, overlapping soon filter paper behind defeated paper, and range estimation is judged that printing ink has or not again and is shifted.
Metewand
◎: good.
Zero: good
△: poorer a little.
*: poor.
The non-constant of * *:.
5. lettering resistance to water
Black, cyanogen, magenta, the yellow monochrome of using that the EPSON PM750C of company prints are developed and printed image that image and redness, green, blue heavy look develop and print be immersed in the flowing water 10 minutes, lettering part change in color and oozing out by lettering partial contour color after the air dry are judged in range estimation.
Metewand
◎: good.
Zero: good
△: poorer a little.
*: poor.
The non-constant of * *:.
[table 1]
| Lettering concentration | The lettering tractability | The lettering anchorage | The lettering resistance to water | Overall merit | |
| Embodiment 1 | ?1.7 | ?○ | ?○ | ?○ | ?○ |
| Embodiment 2 | ?1.7 | ?○ | ?○ | ?○ | ?○ |
| Embodiment 3 | ?1.7 | ?○ | ?○ | ?◎ | ?○ |
| Comparative example 1 | ?1.7 | ?○ | ?△ | ?× | ?× |
| Comparative example 2 | ?1.7 | ?○ | ?○ | ?× | ?× |
| Comparative example 3 | ?1.5 | ?× | ?○ | ?○ | ?× |
| Embodiment 4 | ?1.7 | ?○ | ?○ | ?○ | ?○ |
| Embodiment 5 | ?1.6 | ?○ | ?○ | ?◎ | ?○ |
| Embodiment 6 | ?1.6 | ?◎ | ?○ | ?◎ | ?◎ |
| Embodiment 7 | ?1.7 | ?○ | ?○ | ?○ | ?○ |
| Comparative example 4 | ?1.6 | ?△ | ?△ | ?△ | ?△ |
| Comparative example 5 | ?1.7 | ?○ | ?○ | ?× | ?× |
| Comparative example 6 | ?1.7 | ?△ | ?△ | ?○ | ?△ |
By can finding out obviously in the table 1 that embodiments of the invention compare with comparative example, be lettering concentration, lettering tractability, lettering stationarity, ink jet recording medium that the lettering resistance to water is all good.
Embodiment 8
" making of the coating body paper that ink jet paper is used (making of base material) "
In the LBKP that 90 parts of freeness are 450mlcsf, mix 10 parts of NBKP that freeness is 480mlcsf, modulate 25 parts of calcium carbonate, 0.1 part of alkyl ketene dimer, 0.05 part of poly-(methyl) acrylamide of cation system, 1 part of cationic starch, 0.5 part of aluminum sulfate, use fourdrinier paper machine to copy slurry paper and heavily be 110g/m
2Body paper, use the starch solution of size press device coating 2% to make the dry back coating amount of every single face be 0.4g/m
2, drying, modulation is the coating body paper that 100 seconds ink jet paper is used according to the solution degree of sizing of JIS-P-8122.
" making of ink jet recording medium (formation of ink-receiver layer) "
With 65 parts of amorphous silica pigment (trade name: Off ア イ Application シ-Le X-45; (strain) ト Network ヤ マ system) is dispersed in 1.5% aqueous solution of 600 parts of cetyltrimethylammonium chlorides (total carbon atom number of hydrophobic group is 19), to wherein adding 300 parts of polyvinyl alcohol (trade name: Network ラ レ Port バ-Le PVA-117, (strain) Network ラ レ system), 10% aqueous solution, 35 parts of ethylene-vinyl acetate copolymer emulsion (trade names: ス ミ カ Off レ Star Network ス 473 as binding agent; Sumitomo Chemical system 57% aqueous dispersion), make the ink-receiver layer masking liquid.Use マ イ ヤ バ-make that dried coating amount is 5g/m on the coating body paper that ink jet paper is used with the coating of this masking liquid is dry
2Afterwards, carry out the supercalendering processing and obtain ink jet recording medium.
Embodiment 9
" making of the coating body paper that ink jet paper is used (making of base material) "
In the LBKP that 90 parts of freeness are 450mlcsf, mix 10 parts of NBKP that freeness is 480mlcsf, modulate 25 parts of calcium carbonate, 0.03 part of alkyl ketene dimer, 0.05 part of poly-(methyl) acrylamide of cation system, 1 part of cationic starch, 0.5 part of aluminum sulfate, use fourdrinier paper machine to copy slurry paper and heavily be 110g/m
2Body paper, use the starch solution of size press device coating 2% to make the dry back coating amount of every single face be 0.4g/m
2, drying, modulation is the coating body paper that 10 seconds ink jet paper is used according to the solution degree of sizing of JIS-P-8122.
" making of ink jet recording medium (formation of ink-receiver layer) "
Except using this body paper, use chlorination four pentyl ammonium (total carbon atom number of hydrophobic group is 20) replacement cetyltrimethylammonium chloride, obtain ink jet recording medium similarly to Example 8.
Embodiment 10
With 75 parts of amorphous silica pigment (trade name: Off ア イ Application シ-Le X-45; (strain) ト Network ヤ マ system) is dispersed in 1.5% aqueous solution of 600 parts of chlorination didecyldimethyl ammonium (total carbon atom number of hydrophobic group is 22), to wherein adding 300 parts of polyvinyl alcohol (trade name: Network ラ レ Port バ-Le PVA-117, (strain) Network ラ レ system), 10% aqueous solution, 25 parts of ethene vinyl chloride acetate ethylene copolymer emulsion (trade names: ス ミ カ Off レ Star Network ス 820 as binding agent; Sumitomo Chemical system 50% aqueous dispersion), make the ink-receiver layer masking liquid.
Use マ イ ヤ バ-with this masking liquid coating dry make with embodiment 8 on the coating body paper used of the same ink jet paper used dried coating amount be 5g/m
2Afterwards, carry out the supercalendering processing and obtain ink jet recording medium.
Embodiment 11
With 100 parts of amorphous silica pigment (trade name: カ-プ レ Star Network ス BS-304N; Shionogi (strain) system) is dispersed in 3% aqueous solution of 300 parts of chlorination didecyldimethyl ammonium (total carbon atom number of hydrophobic group is 22), to wherein adding 600 parts of polyvinyl alcohol (trade name: Network ラ レ Port バ-Le PVA-117 as binding agent, (strain) Network ラ レ system) 10% aqueous solution is made the ink-receiver layer masking liquid.
Use マ イ ヤ バ-with this masking liquid coating dry make with embodiment 9 on the coating body paper used of the same ink jet paper used dried coating amount be 10g/m
2Afterwards, carry out the supercalendering processing and obtain ink jet recording medium.
Embodiment 12
With 100 parts of amorphous silica pigment (trade name: Off ア イ Application シ-Le X-45; (strain) ト Network ヤ マ system) is dispersed in 3% aqueous solution of 300 parts of chlorination didecyldimethyl ammonium (total carbon atom number of hydrophobic group is 22), to wherein adding 400 parts of polyvinyl alcohol (trade name: Network ラ レ Port バ-Le PVA-117, (strain) Network ラ レ system) 10% aqueous solution and 200 parts of fluorine are jelly (trade name: ス コ Star チ バ Application FX845 as binding agent; Sumitomo ス リ-エ system system) 5% aqueous dispersions is made the ink-receiver layer masking liquid.
Use マ イ ヤ バ-with this masking liquid coating dry make with embodiment 8 on the coating body paper used of the same ink jet paper used dried coating amount be 10g/m
2Afterwards, carry out the supercalendering processing and obtain ink jet recording medium.
Comparative example 7
With 100 parts of amorphous silica pigment (trade name: Off ア イ Application シ-Le X-45; (strain) ト Network ヤ マ system) is dispersed in 1.5% aqueous solution of 600 parts of cetyltrimethylammonium chlorides (total carbon atom number of hydrophobic group is 19), to wherein adding 300 parts of polyvinyl alcohol (trade name: Network ラ レ Port バ-Le PVA-117 as binding agent, (strain) Network ラ レ system) 10% aqueous solution is made the ink-receiver layer masking liquid.
Use マ イ ヤ バ-with this masking liquid coating dry make with embodiment 9 on the coating body paper used of the same ink jet paper used dried coating amount be 5g/m
2Afterwards, carry out the supercalendering processing and obtain ink jet recording medium.
Comparative example 8
With 100 parts of amorphous silica pigment (trade name: Off ア イ Application シ-Le X-45; (strain) ト Network ヤ マ system) is dispersed in 4% aqueous solution of 400 parts of cetyltrimethylammonium chlorides (total carbon atom number of hydrophobic group is 19), to wherein adding 500 parts of polyvinyl alcohol (trade name: Network ラ レ Port バ-Le PVA-117 as binding agent, (strain) Network ラ レ system) 10% aqueous solution is made the ink-receiver layer masking liquid.
Use マ イ ヤ バ-with this masking liquid coating dry make with embodiment 9 on the coating body paper used of the same ink jet paper used dried coating amount be 5g/m
2Afterwards, carry out the supercalendering processing and obtain ink jet recording medium.
Comparative example 9
Except using polychlorostyrene dimethyldiallylammonium (trade name: ユ ニ セ Application ス CP-103; セ Application カ (strain) system, 40% aqueous solution) replace modulating the masking liquid that ink-receiver layer is used similarly to Example 8 beyond the cetyltrimethylammonium chloride.
Use マ イ ヤ バ-with this masking liquid coating dry make with embodiment 8 on the coating body paper used of the same ink jet paper used dried coating amount be 10g/m
2Afterwards, carry out the supercalendering processing and obtain ink jet recording medium.
Comparative example 10
The coating body paper that the same ink jet paper of using is used, obtain ink jet recording medium equally with comparative example 9 in use and embodiment 9.
Comparative example 5
Except using chloro distearyl dimethyl ammonium replacement cetyltrimethylammonium chloride, obtain ink jet recording medium similarly to Example 8.
Embodiment 13
With 65 parts of amorphous silica pigment (trade name: Off ア イ Application シ-Le X-60; (strain) ト Network ヤ マ system) is dispersed in 1.5% aqueous solution of 600 parts of chlorination dilauryl Dimethyl Ammonium (total carbon atom number of hydrophobic group is 26), to wherein adding 300 parts of modified polyvinylalcohols (trade name: Network ラ レ R polymer R-1130, (strain) Network ラ レ system), 10% aqueous solution, 35 parts of ethene vinyl chloride vinyl acetate co-polymer emulsion (trade names: ス ミ カ Off レ Star Network ス 820 as binding agent; Sumitomo Chemical system 50% aqueous dispersion), make the ink-receiver layer masking liquid.
Use マ イ ヤ バ-with the dry white PET film (trade name: テ ト ロ Application U5 type that makes at 100 μ m thickness of this masking liquid coating; Supreme Being people's (strain) system) going up dried coating amount is 15g/m
2, obtain ink jet recording medium.
Embodiment 14
With 60 parts of amorphous silica pigment (trade name: サ イ ロ ジ エ Star ト P-405; グ レ-ス デ ヴ イ ソ Application (strain) system) is dispersed in 1.4% aqueous solution of 650 parts of chlorination didecyldimethyl ammonium (total carbon atom number of hydrophobic group is 22), to wherein adding 250 parts of polyvinyl alcohol (trade name: Network ラ レ Port バ-Le PVA-117, (strain) Network ラ レ system), 10% aqueous solution, 40 parts of vinyl acetate emulsion (trade names: ヨ De ゾ-Le CE60 as binding agent; NSC (strain) makes 50% aqueous dispersion), make the ink-receiver layer masking liquid.
Use マ イ ヤ バ-with the dry synthetic paper (trade name: YUPO PG-110 that makes at 110 μ m thickness of this masking liquid coating; (strain) ユ Port コ-Port レ-シ ヨ Application system) going up dried coating amount is 15g/m
2, obtain ink jet recording medium.
Embodiment 15
With 60 parts of amorphous silica pigment (trade name: サ イ ロ ジ エ Star ト P-412; グ レ-ス デ ヴ イ ソ Application (strain) system) is dispersed in 1.5% aqueous solution of 580 parts of chlorination stearyl dimethyl benzyl ammoniums (total carbon atom number of hydrophobic group is 27), to wherein adding 20 parts of polychlorostyrene dimethyldiallylammoniums (trade name: ユ ニ セ Application ス CP-103; セ Application カ (strain) system, 40% aqueous solution) and 300 parts of modified polyvinylalcohols (trade name: Network ラ レ R polymer R-1130, (strain) Network ラ レ system), 10% aqueous solution, 40 parts of acrylic emulsion (trade names: リ カ ボ Application De FK-820 as binding agent; Central authorities' physics and chemistry industry (strain) system, 40% aqueous dispersion), make the ink-receiver layer masking liquid.Except using this masking liquid, obtain ink jet recording medium similarly to Example 14.
Embodiment 16
With 100 parts of amorphous silica pigment (trade name: カ-プ レ Star Network ス BS-304N; Shionogi (strain) system) is dispersed in 4% aqueous solution of 750 parts of chlorination didecyldimethyl ammonium, to wherein adding 150 parts of ethylene vinyl acetate copolymer emulsions (trade name: ス ミ カ Off レ Star Network ス 473 as binding agent; Sumitomo Chemical system 57% aqueous dispersion), make the ink-receiver layer masking liquid.
Use マ イ ヤ バ-with the dry synthetic paper (trade name: YUPO FPG-110 that makes at 110 μ m thickness of this masking liquid coating; (strain) ユ Port コ-Port レ-シ ヨ Application system) going up dried coating amount is 20g/m
2, obtain ink jet recording medium.
Comparative example 12
With 60 parts of amorphous silica pigment (trade name: Off ア イ Application ミ-Le X-60; (strain) ト Network ヤ マ system) is dispersed in 1.5% aqueous solution of 580 parts of chlorination stearyl dimethyl benzyl ammoniums (total carbon atom number of hydrophobic group is 27), to wherein adding 20 parts of polychlorostyrene dimethyldiallylammoniums (trade name: ユ ニ セ Application ス CP-103; セ Application カ (strain) system, 40% aqueous solution), 300 parts of (trade name: Network ラ レ R polymer R-1130, (strain) Network ラ レ system) 10% aqueous solution of the modified polyvinylalcohol as binding agent and 140 parts of surfactant polyoxyethylene lauryl ether (trade names: エ マ Le ゲ Application 109P; Flower king (strain) system) 5% aqueous solution is made the ink-receiver layer masking liquid.
Except using this masking liquid, obtain ink jet recording medium similarly to Example 14.
Comparative example 13
With 65 parts of amorphous silica pigment (trade name: Off ア イ Application ミ-Le X-60; (strain) ト Network ヤ マ system) is dispersed in 1.5% aqueous solution of 540 parts of chlorination didecyldimethyl ammonium, to wherein adding 400 parts of modified polyvinylalcohols (trade name: Network ラ レ R polymer R-1130 as binding agent, (strain) Network ラ レ system) 10% aqueous solution is made the ink-receiver layer masking liquid.
Except using this masking liquid, obtain ink jet recording medium similarly to Example 14.
Comparative example 14
With 100 parts of amorphous silica pigment (trade name: サ イ ロ ジ エ Star ト P-405; グ レ-ス デ ヴ イ ソ Application (strain) system) is dispersed in 550 parts of poly dimethyl amine epichlorohydrin copolymer (trade names: PAL-2; セ Application カ (strain) system) in 1.5% aqueous solution, to wherein adding 300 parts of modified polyvinylalcohols (trade name: Network ラ レ R polymer R-1130, (strain) Network ラ レ system), 10% aqueous solution, 50 parts of vinyl acetate emulsion (trade names: ヨ De ゾ-Le CE60 as binding agent; NSC (strain) makes 50% aqueous dispersion), make the ink-receiver layer masking liquid.
Except using this masking liquid, obtain ink jet recording medium similarly to Example 14.
Comparative example 15
With 100 parts of amorphous silica pigment (trade name: サ イ ロ ジ エ Star ト P-412; グ レ-ス デ ヴ イ ソ Application (strain) system) is dispersed in 550 parts of dicyandiamide polyamine condensation product (trade names: Neofix RP-70; Solar corona chemistry (strain) system, 70% aqueous solution) in 1.5% aqueous solution, to wherein adding 300 parts of modified polyvinylalcohols (trade name: Network ラ レ R polymer R-1130, (strain) Network ラ レ system) 10% aqueous solution and 50 parts of ethylene vinyl acetate copolymer emulsion (trade names: ス ミ カ Off レ Star Network ス 473 as binding agent; Sumitomo Chemical system 57% aqueous dispersion), make the ink-receiver layer masking liquid.
Except using this masking liquid, obtain ink jet recording medium similarly to Example 12.
The result who estimates lettering concentration, lettering tractability, lettering stationarity, lettering resistance to water, lettering back displays at the ink jet recording medium that obtains is presented in the table 2.
" evaluation "
1. evaluation lettering
Use the color inkjet printer EPSON PM750C of company that sells on the market, print black, cyanogen, magenta, yellow monochromatic and red, green, blue heavy look is developed and printed and the image of fine rule.
2. lettering image color
Use Macbeth reflection of the concentration RD914, measure the reflection density that use that the EPSON PM750C of company prints black, cyanogen, magenta, yellow monochrome are developed and printed image lettering part.
3. lettering tractability
What fine rule image lettering part that the EPSON PM750C of company prints judge was used in range estimation oozes profit, tractability.
Metewand
◎: good.
Zero: good.
△: poorer a little.
*: poor.
4. lettering stationarity
That lettering uses that the EPSON PM750C of company prints is black, cyanogen, magenta, yellow, redness, green, blue image, overlapping soon filter paper behind defeated paper, and range estimation is judged that printing ink has or not again and is shifted.
Metewand
◎: good.
Zero: good
△: poorer a little.
*: poor.
The non-constant of * *:.
5. lettering resistance to water
With black, cyanogen, the magenta of using that the EPSON PM750C of company prints, yellow monochrome is developed and printed and image red, green, that blue heavy look is developed and printed is immersed in the flowing water 10 minutes, lettering part change in color and oozing out by lettering partial contour color after the air dry are judged in range estimation.
Metewand
◎: good.
Zero: good.
△: poorer a little.
*: poor.
The non-constant of * *:.
6. lettering ink bleed
Black, cyanogen, magenta that observe to use that the EPSON PM750C of company prints, yellow monochrome is developed and printed and red, green, blue heavy look is developed and printed the image reverse side, the disengaging of range estimation judgement printing ink.
Metewand
◎: good.
Zero: good
△: poorer a little.
*: poor.
The non-constant of * *:.
7. the transfer amount of distilled water
Distilled water uses dynamic scan imbibition meter (model: KS350D, consonance Seiko strain formula meeting corporate system) to measure the absorption curve of distilled water with respect to the transfer amount of ink jet recording medium.Absorption curve is with transfer amount (mL/m
2) be the longitudinal axis, the square root of time of contact ((ms)
1/2, perhaps (ms)) and for transverse axis plots, form the straight line that keeps the constant inclination degree, try to achieve at 20 (ms) by interpolation
1/2The value of the transfer amount at place.
[table 2]
| Transfer amount | Lettering concentration | The lettering tractability | The lettering anchorage | The lettering resistance to water | The lettering ink bleed | Overall merit | |
| Embodiment 8 | ?60 | ?1.7 | ?○ | ?○ | ?○ | ○ | ○ |
| Embodiment 9 | ?60 | ?1.7 | ?○ | ?○ | ?○ | ○ | ○ |
| Embodiment 10 | ?90 | ?1.7 | ?○ | ?○ | ?◎ | ○ | ○ |
| Embodiment 11 | ?90 | ?1.6 | ?○ | ?○ | ?○ | ○ | ○ |
| Embodiment 12 | ?90 | ?1.7 | ?○ | ?○ | ?○ | ○ | ○ |
| Comparative example 7 | ?140 | ?1.2 | ?× | ?○ | ?○ | × | × |
| Comparative example 8 | ?175 | ?1.1 | ?× | ?○ | ?○ | × | × |
| Comparative example 9 | ?20 | ?1.7 | ?△ | ?△ | ?× | ○ | × |
| Comparative example 10 | ?40 | ?1.6 | ?△ | ?○ | ?× | × | × |
| Comparative example 11 | ?70 | ?1.7 | ?○ | ?○ | ?○ | × | × |
| Embodiment 13 | ?60 | ?1.7 | ?○ | ?○ | ?○ | - | ○ |
| Embodiment 14 | ?55 | ?1.6 | ?○ | ?○ | ?◎ | - | ○ |
| Embodiment 15 | ?54 | ?1.6 | ?◎ | ?○ | ?◎ | - | ◎ |
| Embodiment 16 | ?50 | ?1.7 | ?○ | ?○ | ?○ | - | ○ |
| Comparative example 12 | ?90 | ?1.6 | ?△ | ?○ | ?× | - | △ |
| Comparative example 13 | ?130 | ?1.4 | ?△ | ?△ | ?○ | - | △ |
| Comparative example 14 | ?35 | ?1.7 | ?○ | ?△ | ?× | × | |
| Comparative example 15 | ?42 | ?1.5 | ?× | ?× | ?○ | - | × |
By finding out obviously in the table 2 that embodiments of the invention compare with comparative example, be image color, lettering stationarity, lettering resistance to water, all good ink jet recording medium of ink bleed.
Like this, the present invention be that the repeatability of high precise image is good, lettering stationarity, the good ink jet recording medium of lettering resistance to water.
Claims (7)
1. ink jet recording medium, making droplet transfer that the water color ink contain water-soluble or water dispersible colorant sprays from small hole, forms to recording medium and form in the ink jet recording medium of document image, it is characterized in that this ink jet recording medium on base material, have contain pigment and water-insoluble binding agent and contain the cationic compound that is selected from following formula 1 expression and the cationic resin of following formula 2, following formula 3 expressions at least a kind ink-receiver layer
In the formula, satisfies R1～R4 and be hydrophobic group independently separately, and the total carbon atom number of R1～R4 is 16～36 that X is a halogen,
In the formula, satisfying at least one side of R5, R6 is that carbon number is 12～18 hydrophobic group, and the total carbon atom number of R5 and R6 is 13～36, and X is a halogen, and m is 20～5000 integer,
In the formula, satisfying at least one side of R7, R8 is that carbon number is 12～18 hydrophobic group, and the total carbon atom number of R7 and R8 is 13～36, and X is a halogen, and n is 20～5000 integer.
2. ink jet recording medium, making droplet transfer that the water color ink contain water-soluble or water dispersible colorant sprays from small hole, forms to recording medium and form in the ink jet recording medium of document image, it is characterized in that this ink jet recording medium has in the cationic resins of the cationic compound that contains pigment, binding agent and be selected from following formula 1 expression and following formula 2 and 3 expressions at least a kind ink-receiver layer on base material, and be 20 (ms) using dynamic scan imbibition instrumentation fixed time of contact
1/2The transfer amount of Shi Shuixiang recording medium is 30～100ml/m
2,
In the formula, satisfies R1～R4 and be hydrophobic group independently separately, and the total carbon atom number of R1～R4 is 16～36 that X is a halogen,
In the formula, satisfying at least one side of R5, R6 is that carbon number is 12～18 hydrophobic group, and the total carbon atom number of R5 and R6 is 13～36, and X is a halogen, and m is 20～5000 integer,
In the formula, satisfying at least one side of R7, R8 is that carbon number is 12～18 hydrophobic group, and the total carbon atom number of R7 and R8 is 13～36, and X is a halogen, and n is 20～5000 integer.
In the claim 1 record ink jet recording medium, the cationic compound of its Chinese style 1 is a following formula 4,
In the formula, satisfy R1, R2 for separately independently carbon number at the alkyl more than 8, R3, R4 be separately independently carbon number be 1～4 alkyl, and the total carbon atom number of R1～R4 is 18～36, X is a halogen.
In the claim 1 record ink jet recording medium, the cationic compound of its Chinese style 1 is a following formula 5,
In the formula, satisfy R1 and be carbon number at the alkyl more than 13, R2, R3, R4 be separately independently carbon number be 1～4 alkyl, and the total carbon atom number of R1～R4 is 16～36, X is a halogen.
In the claim 1 record ink jet recording medium, the cationic compound of its Chinese style 2 is a following formula 6,
In the formula, R5 is that carbon number is 12～18 alkyl, and X is a halogen, and n is 20～5000 integer.
In the claim 1 record ink jet recording medium, wherein base material is selected from film, synthetic paper, nonwoven, is the sheet material of main component with synthetic resin.
7. the ink jet recording medium of record in the claim 1, wherein binding agent contains polyacrylic, polyvinyl acetate system, the polyethylene vinyl acetate ester is the water-insoluble binding agent.
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| WO2001078990A1 (en) * | 1998-10-26 | 2001-10-25 | Dai-Ichi Kogyo Seiyaku Co., Ltd. | Resin composition for ink-jet recording sheet, the recording sheet, method of the recording, and process for producing the recording sheet |
| JP2000318307A (en) * | 1999-03-09 | 2000-11-21 | Konica Corp | Ink jet recording sheet and its manufacture |
| JP2002103799A (en) * | 2000-09-29 | 2002-04-09 | Nisshinbo Ind Inc | Ink jet recording sheet |
| JP3982742B2 (en) * | 2001-09-12 | 2007-09-26 | 信越化学工業株式会社 | Coating agent for inkjet recording sheet |
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