CN1704257A - Ink jet recording sheet - Google Patents
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- CN1704257A CN1704257A CN 200510076275 CN200510076275A CN1704257A CN 1704257 A CN1704257 A CN 1704257A CN 200510076275 CN200510076275 CN 200510076275 CN 200510076275 A CN200510076275 A CN 200510076275A CN 1704257 A CN1704257 A CN 1704257A
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Abstract
Ink jet recording sheet has excellent coloring properties for dye ink as well as pigment ink, a high degree of brightness, and excellent preservability for white paper portions. The ink jet recording sheet includes: a paper supporting medium made by machining pulp; an undercoating layer including at least a pigment and an adhesive; and an ink receiving layer including at least a pigment and an adhesive, the undercoating layer and the ink receiving layer being disposed on at least one surface of the paper supporting medium, and the ink receiving layer being located outermost thereof, wherein the undercoating layer includes titanium dioxide as the pigment and at least one emulsion type adhesive selected from acryl polymers, ethylene-vinyl acetate copolymers, or vinyl acetate polymers; and the ink receiving layer includes silica having an average secondary particle size of 3 to 11 m as the pigment, and a cationic ink fixing agent.
Description
Technical field
The printed matter that the present invention relates to ink-jet recording paper and use it.At length, the present invention relates to when using dye ink or pigment ink, also to have good ink mist recording adaptability (colour rendering), the high ink-jet recording paper of keeping quality whiteness good, that paper is surperficial of blank sheet of paper part.Further, even the present invention relates to use to mix the base material of the paper pulp that paper reclaims of haveing been friends in the past, also without detriment to the ink-jet recording paper of above-mentioned performance.
Background technology
Spray water color ink from fine nozzle to the record surface, and writing down the ink jet recording method that forms image on the surface, because noise is low when record, form full-colour image easily, can high-speed record, and compare reasons such as recorded cost is low with other printing equipment, be widely used in printer, facsimile machine, plotter or ticket printing etc.
Water color ink is divided into dye ink that uses dyestuff and the pigment ink that uses pigment, and this puts from clarity, mainly uses dye ink.But, because the large-scale placard of showing out of doors etc. is also using ink jet recording method in recent years, therefore, point out the following shortcoming of this water color ink: if dye ink is showed for a long time, will be by oxidations such as ultraviolet ray, ozone, image fade, surperficial impaired, printing portion is not well preserved.
On the other hand, though pigment ink has the photostability of printing portion, the ozone resistance of printing portion, the good feature in resistance to water aspect of printing portion, but there is such problem: owing to compare with the dyestuff size of dye ink, the pigment particles of pigment ink is very big, therefore, when ink mist recording that dye ink is always used uses pigment ink to print on drawing, can not get print image clearly.
Therefore, the ink mist recording used with drawing, pigment ink of the ink mist recording of respectively dye ink being used is developed with drawing, and it is very high dye ink and pigment ink to be had the demand of ink-jet recording paper of good colour rendering.
In addition, except the conservatory improvement of printing portion, the keeping quality of blank parts (blank sheet of paper part) promptly when the time, the environmental condition that stand according to the preservation of ink-jet recording paper or printed matter or use, is also kept whiteness well and is become very important.Because printed matter partly is made up of printing portion and blank sheet of paper, therefore,,, also require the whiteness and the keeping quality thereof of blank sheet of paper part good except satisfying above-mentioned colour rendering in order to keep clearly to discern printing.
During as use dye ink or pigment ink printing, also show the ink-jet recording paper of good colour rendering, proposed in coating liquid, to contain the ink-jet recording paper of water-soluble metal salt and aerosil (for example, with reference to patent documentation 1.), the ink-jet recording paper of ink-receiver layer more than 2 layers is set (for example, with reference to patent documentation 2～4.), control ink-receiver layer surface becomes the ink-jet recording paper of certain roughness (for example, with reference to patent documentation 5.), ink-receiver layer contains the ink-jet recording paper of the pigment of regulation particle diameter (for example, with reference to patent documentation 6.) etc.
In recent years, the demand of paper is opposite with prediction, is increasing constantly, and the demand of this raw material paper pulp sharply increases at world wide.The stationery that contains in the municipal refuse increases especially, and from the protection viewpoint of the earth environmental protection and the forest reserves, intention enlarges old paper and reclaims, and need make great efforts to increase operation rate.For ink-jet recording paper, just proposing to mix old paper and reclaiming paper pulp (for example, patent documentation 7～9).
[patent documentation 1] spy opens the 2002-274022 communique
[patent documentation 2] spy opens the 2000-168228 communique
[patent documentation 3] spy opens the 2002-347330 communique
[patent documentation 4] spy opens flat 10-278411 communique
[patent documentation 5] spy opens the 2000-158804 communique
[patent documentation 6] spy opens the 2001-270238 communique
[patent documentation 7] spy opens flat 10-278416 communique
[patent documentation 8] spy opens the 2003-191616 communique
[patent documentation 9] spy opens flat 9-142007 communique
Summary of the invention
The problem that invention will solve
But patent documentation 1～6 described ink-jet recording paper is that the colour rendering of can not saying so attains full and complete satisfaction, and does not finish the conservatory improvement for the blank sheet of paper part.
In addition, patent documentation 7～9 described ink-jet recording papers all fully do not satisfy the keeping quality and the whiteness of blank sheet of paper part.
That is, can not say and state the described ink-jet recording paper of patent documentation and all satisfy keeping quality fully corresponding to the colour rendering and the blank sheet of paper part of dye ink and pigment ink.Thereby situation of today is: even use dye ink or pigment ink, all can not get having good colour rendering and satisfy the keeping quality of blank sheet of paper part, the ink-jet recording paper of whiteness.Certainly, when using the old paper of mixing to reclaim the paper pulp base material, also be same situation.
In view of the foregoing, the invention provides all good ink-jet recording paper of keeping quality of, whiteness all good and blank sheet of paper part for dye ink or pigment ink colour rendering.Especially, the invention provides when the paper pulp base material that uses old paper to reclaim colour rendering height, the good blank sheet of paper keeping quality partly of maintenance, the high ink-jet recording paper of whiteness on paper surface simultaneously.The present invention especially be provided at coating amount few and 60 the degree minute surfaces glossiness in the ink-jet recording paper of matt type such below 15%, satisfy the paper used for recording of above-mentioned character.
The method of dealing with problems
Be that the present invention is:
(1) a kind of ink-jet recording paper, be provided with priming coat and ink-receiver layer, wherein priming coat is to be positioned on the one side at least of paper base material of papermaking slurry, and contain pigment and adhesive at least, ink-receiver layer is positioned at outermost, and contain pigment and adhesive at least, it is characterized in that: aforementioned priming coat contains titanium dioxide as pigment, and contain and be selected from acrylic polymer, it is silica and the cationic printing ink fixative of 3～11 μ m that at least a adhesive of ethylene-vinyl acetate lipin polymer and vinyl acetate esters polymer, aforementioned ink-receiver layer contain as the average aggregate particle size of pigment.
(2) (1) described ink-jet recording paper contains the paper pulp that the old paper more than the 10 quality % reclaims at aforementioned paper pulp.
(3) (1) or (2) described ink-jet recording paper is characterized in that: contain cdicynanmide-polyvinylamine copolymer and acrylamide-diallyl amine polymer in the ionic printing ink fixative of aforementioned male.
(4) (3) described ink-jet recording paper is characterized in that: the ionic printing ink fixative of aforementioned male also contains zinc sulfate.
(5) each described ink-jet recording paper of (1)～(4) is characterized in that: contain acrylic polymer in the adhesive of ink-receiver layer at least.
(6) each described ink-jet recording paper of (1)～(5) is characterized in that: aforementioned silica has at least a part to be to use surfactant that surface treated processing silica is carried out on the surface.
(7) each described ink-jet recording paper of (1)～(6) is characterized in that: the glossiness of minute surfaces is spent below 15% according to 60 of JIS-Z8741 defined in aforementioned ink-receiver layer surface.
(8) use dye ink, the printed matter that on each described ink-jet recording paper of (1)～(7), prints.
(9) use pigment ink, the printed matter that on each described ink-jet recording paper of (1)～(7), prints.
The invention effect
According to the present invention, can provide for pigment ink, dye ink both, ink mist recording adaptability (colour rendering) is all good, can clearly print the image of high-resolution, the good ink-jet recording paper of blank sheet of paper part keeping quality (particularly preventing the blank sheet of paper flavescence of being heated).Further, can be provided as and used Limited resources effectively and use old paper, the paper surface has high whiteness, the matt type ink-jet recording paper that the ink-jet recording paper that the keeping quality of above-mentioned colour rendering, blank sheet of paper is good, particularly coating amount are few simultaneously.
Description of drawings
The generalized section of an embodiment of [Fig. 1] expression ink-jet recording paper of the present invention.
[symbol description]
10 ink-jet recording papers
12 paper substrates
14 priming coats
16 ink-receiver layers
The specific embodiment
Ink-jet recording paper
(layer structure)
Ink-jet recording paper of the present invention, be provided with priming coat and ink-receiver layer, priming coat is on the one side at least of the paper base material of papermaking slurry, at least contain titanium dioxide as pigment and the adhesive that is selected from least a emulsion-type of acrylic polymer, ethylene-vinyl acetate lipin polymer and vinyl acetate esters polymer, ink-receiver layer is to contain the silica that average aggregate particle size is 3～11 μ m at least, adhesive and cationic printing ink fixative.
Fig. 1 represents an example of the layer structure of ink-jet recording paper of the present invention.
In ink-jet recording paper shown in Figure 1 10, be provided with ink-receiver layer 16 in the one side of paper base material 12, intervenient is priming coat 14.
In addition, the another side at paper base material of the present invention also can be provided with same priming coat and ink-receiver layer.In this case, can print clearly on the two sides of ink-jet recording paper.
In addition, priming coat and ink-receiver layer also can be made up of multilayer respectively.At this moment, ink-receiver layer is positioned at the outermost of paper base material, priming coat.
(paper base material)
The paper pulp that uses as the main component of paper base material, can enumerate LBKP (bleached hardwood kraft pulp) or NBKP chemical pulps such as (coniferous tree bleached kraft pulps), GP (ground wood pulp), TMP mechanical pulps such as (thermomechanical paper pulp), and old paper reclaims paper pulp.These independent uses are also passable, and two or more mixing are used also passable.Wherein, preferably mix LBKP as the main component in the paper pulp.In addition, freedom has no particular limits, preferably pull an oar to freedom (freeness) be (CSF:JIS-P-8121) about 200～500ml.If freedom is little, the piston ring during printing (コ ッ Network リ Application グ) possible deviation; If freedom is big, may not obtain flatness.
Ink-jet recording paper of the present invention, because of having the priming coat that contains certain material, usually, paper pulp as ink-jet recording paper, even old paper recovery paper pulp or the mechanical pulp avoiding using are blended in the paper base material, also can access the ink-jet recording paper that keeping quality is good and whiteness is high of blank sheet of paper part.
In the used paper pulp 100 quality % of paper base material papermaking, reclaim paper pulp part more than 10 quality % by making old paper, can utilize old paper, effectively utilize resource.According to the present invention, when old paper reclaims paper pulp and accounts for 100～100 quality % of paper pulp, the having good keeping qualities of the whiteness of ink-jet recording paper and blank sheet of paper part.
Reclaim the old paper of the raw material of paper pulp as old paper, can be for example old paper of newspaper, the old paper of magazine, the old paper of cardboard, the old paper of wrapping paper, the old paper of carton, the old paper of printing etc., the waste paper that also can comprise in the paper producing further, the good quality paper that produces, lacquer-coated paper etc.
The paper pulp that old paper reclaims, generally make by making up following operation aptly: by low concentration pulper or high concentration pulper to the disassociation operation of old paper and waste paper, utilize screen cloth or water filter roughly select operation and selected operation, utilize floatation or WATER-WASHING METHOD the deinking operation, utilize chlorine bleaching, ClO 2 bleaching, sodium hypochlorite bleaching, the bleaching process of oxygen bleaching etc. etc.
In paper base material, except above-mentioned paper pulp, go back mixed fillers.The purpose of mixed fillers is: regulate paper base material gas permeability, give opacity etc., adjust ink absorption.As filler, suitable use is clay, kaolin, calcined kaolin, talcum, calcium carbonate, magnesium carbonate, aluminium hydroxide, calcium hydroxide, silica, titanium dioxide etc. for example.It is, therefore preferred because if use calcium carbonate wherein can obtain the high paper base material of whiteness.
With respect to 100 parts of above-mentioned all paper pulp, filler preferably has 1～35 part.If filler is few, there is the tendency that not only whiteness reduces but also the absorbability of printing ink reduces, if too much, the tendency that paper toughness (rigidity) reduces, paper power reduces is arranged, the calcium carbonate that additional mixing is excessive is the reason that flavescence takes place on the ink-jet recording paper surface.
During paper base material papermaking, in the paper material that contains above-mentioned paper pulp and filler, in the scope of not damaging effect of the present invention, as required, the suitable volume increase agent of selecting to use always employed various anionic properties, nonionic, cationic or both sexes, draining promoter, paper power reinforcing agent or in add adding assistant in the various paper grade (stock)s such as adhesive.And, as required, the also suitable interior adding assistant of paper grade (stock)s such as dyestuff, pH conditioning agent, defoamer, pitch control additive, the agent of sizing mixing that adds.Ink-jet recording paper of the present invention if mix fluorescent whitening agent in large quantities, the situation of the keeping quality reduction of blank sheet of paper part described later occurs so.
As papermaking process, can use known paper machines such as fourdrinier wire formula paper machine, cylinder paper machine, two net type paper machines to produce.According to the pH of papermaking base material (paper base material), can be divided into acidic paper and neutralized paper, as being used for paper base material of the present invention, consider that from the long preservation aspect neutralized paper is preferred.
In addition, utilize size press etc., at surface applied, dippings such as starch, polyvinyl alcohol or resin cations, can regulate surperficial smoothness, improve intensity, improve printing, write down adaptability.And, in order to improve the flatness of paper base material, can use rolling process etc. to carry out flatness and handle.In addition, quantitative (the level ground amount) of paper base material if having no particular limits, is 20～400g/m
2About.
(priming coat)
Priming coat contain at least titanium dioxide as pigment, be selected from least a emulsion-type adhesive of acrylic polymer, ethylene-vinyl acetate lipin polymer and vinyl acetate esters polymer as adhesive.
Titanium dioxide can be divided into rutile-type and Detitanium-ore-type owing to the difference of structure, the general preferred rutile-type that can obtain high whiteness, and for the present invention, any kind is all effective.The preferred 0.1 μ m of the aggregate particle size of titanium dioxide～2 μ m is more preferably 0.3 μ m～1 μ m.If particle diameter is little, there is intensity to reduce, the absorbability of printing ink reduces, and the tendency that colour rendering reduces if particle diameter is big, has the tendency of clear picture reduction, can not obtain level and smooth and uniform face in addition.
The present invention can realize that the keeping quality of blank sheet of paper part is good, whiteness height, and gradation of drop-out colour height by forming the priming coat of titanium dioxide and specific binder combination.About bringing into play the reason of this action effect, can do following consideration.
Promptly, there is such problem: as the used pigment of ink-jet recording paper, silica is known, and still, silica is compared with other pigment, because the trafficability characteristic height of light, water, gas, therefore, when for example on the paper base material that uses old paper recovery paper pulp, directly forming ink-receiver layer, have to low whiteness, because whiteness is low, can not print distinct image.Between paper base material and ink-receiver layer,, can not obtain sufficient whiteness even further form thisly with the priming coat of silica as main component.
In addition, in order to improve the whiteness of ink-jet recording paper, if priming coat uses calcium carbonate, or mix fluorescent whitening agent in a large number, the keeping quality of blank sheet of paper part reduces so.Infer thus: owing to be alkaline matter as the stilbene derivative of calcium carbonate or fluorescent whitening agent etc., oxidation is blended in the cationic printing ink fixative of ink-receiver layer, impels the surperficial flavescence of ink-jet recording paper.
Therefore think: because the light scattering property height of titanium dioxide, and can not cause the oxidation of cationic printing ink fixative, therefore, form priming coat as pigment by using titanium dioxide, can be so that the having good keeping qualities of the whiteness of graphite paper used for recording and blank sheet of paper part.
The present invention is used in combination titanium dioxide and as at least a emulsion-type adhesive that is selected from acrylic polymer, ethylene-vinyl acetate lipin polymer and vinyl acetate esters polymer of adhesive.
Use titanium dioxide as pigment, compare, as mentioned above, can form the difficult reduction of keeping quality of blank sheet of paper part, the ink-jet recording paper that whiteness is high with other pigment such as kaolin, precipitated calcium carbonate, talcums.And, by combination titanium dioxide and these adhesives, can reduce amount of binder (gluing dosage).By reducing the amount of binder in the priming coat, the ink absorption of priming coat (mainly being the solvent absorbing of printing ink) increases, and the ink-jet recording paper of gained has been realized the image repetition of high-resolution.In addition, reduce amount of binder, can help the whiteness of ink-jet recording paper to improve.
Employed acrylic polymer in the emulsion type adhesive of priming coat can be enumerated the polymer that acrylic acid, methacrylic acid, acrylate, methacrylate etc. contain (methyl) acrylic compounds unit.Acrylic polymer can be the independent polymer of (methyl) acrylic compounds unit, and copolymer contains the copolymer of other component units.As acrylic polymer, can enumerate and for example gather (methyl) methyl acrylate etc.
As ethylene-vinyl acetate lipin polymer principal component is ethene and vinyl acetate, other monomers are fatty acid vinyl esters beyond such vinyl acetate such as (methyl) acrylate, the ethene tertiary carbon acid esters (PVC ニ one Le バ one サ テ one ト) of for example acrylic acid-2-ethyl hexyl ester etc., further, be to contain the monomer copolymerization of this functional group of acrylic acid and obtain.
As the vinyl acetate esters polymer can be the polymer that contains vinyl acetate unit, preferred polyvinyl acetate.
General known emulsion-type adhesive or the water-soluble binder that has beyond above-mentioned of adhesive, but, if priming coat uses the conjugated diene resinoid of styrene-butadiene resin, methyl methacrylate-butadiene copolymer etc., can not obtain colour rendering, and the flavescence in time of blank sheet of paper part.In addition, when using water-soluble binder such as starch, polyvinyl alcohol, when regulating the coating liquid that priming coat uses, can not be adjusted to the coating liquid of high concentration, if the coating amount is few during coating, the keeping quality of the whiteness that can not realize ideal, blank sheet of paper part and printing concentration.
The invention is characterized in: by use titanium dioxide and the emulsion-type adhesive that is selected from acrylic polymer, ethylene-vinyl acetate lipin polymer and vinyl acetate esters polymer at priming coat, can obtain having the whiteness height, the keeping quality of blank sheet of paper part is good, and the ink-jet recording paper of high printing concentration.This proportioning is relative 100 parts of titanium dioxide, and preferred about 2～30 parts of adhesive is more preferably about 5～20 parts.If the amount of adhesive is few, the intensity of priming coat reduces, and the amount of adhesive is many, has uptake and reduces, and it is poor to develop the color, perhaps the tendency of whiteness reduction.
In addition, in the scope that does not hinder effect of the present invention, priming coat can mix for example inorganic pigment of silica, calcium carbonate, kaolin, talcum, calcium sulfate, barium sulfate, zinc oxide, zinc sulphide, zinc carbonate, satin white, alumina silicate, diatomite, calcium silicates, magnesium silicate, aluminium hydroxide, aluminium oxide, plan boehmite, shovel barium white, zeolite, hydrated halloysite, magnesium carbonate, magnesium hydroxide etc.
When mixing these inorganic pigments, with respect to this inorganic pigment and titanium dioxide total amount 100 quality %, preferred titanium dioxide is more than the 70 quality %.
In addition, in the scope that does not hinder effect of the present invention, the general always known adhesive of using as ink mist recording such as the conjugated diene resinoid of cellulose derivatives such as various starch based, polyvinyl alcohol and derivative thereof, carboxymethyl cellulose, methylcellulose such as priming coat can be protein-based with for example casein, soybean protein, synthetic proteins etc., starch or oxidized starch, styrene-butadiene resin, methyl methacrylate-butadiene copolymer merges and uses.
In addition, in the scope that does not hinder effect of the present invention, priming coat suits to be added on various auxiliary agents such as employed thickener, defoamer, wetting agent, colouring agent, fluorescent whitening agent, fluorescent pigment, antistatic agent, photostability auxiliary agent, ultra-violet absorber, antioxidant, anticorrisive agent in the general lacquer-coated paper manufacturing.
Priming coat can form like this: the priming coat coating liquid that will contain the inorganic pigment etc. of above-mentioned pigment, adhesive and expectation is coated on the surface of paper base material and dry.The coating amount of priming coat (Gu shape branch) is 3～20g/m
2About, preferred 5～15g/m
2, be more preferably 7～13g/m
2If coating amount is very little, can not obtain high whiteness, and also flavescence easily, if too many, the oversaturated tendency that not only produces effect, and the tendency that has interlaminar strength to weaken.
As the applying device that is used to form priming coat, can enumerate vane type coating machine, strength coating machine, roll coater, rod and be coated with various known applying devices such as machine, notch board coating machine, rod-type coating machine, lip coating machine, curtain formula coating machine and mould coating machine.After the coating, it is also passable to use calenders such as machine calender, TG calender, multi-rolling mill, soft calender to carry out fine finishining.
(ink-receiver layer)
Ink-receiver layer contains silica, adhesive and the cationic printing ink fixative that average aggregate particle size is 3～11 μ m at least.
The preferred amorphous silica of silica.The method for making of silica has no particular limits, any one method preparation of use arc process, dry method, wet method (for example precipitation method, gel method) can, but wet method silica is therefore preferred owing to being applicable to pigment ink ink-jet recording paper, dye ink any one of ink-jet recording paper.
Silica uses the average aggregate particle size (average grain diameter of offspring; Below also claim " average grain diameter ") be 3～11 μ m, be more preferably 4～10 μ m's.When if average grain diameter less than 3 μ m, is used it for ink-jet recording paper so and printed by dye ink, the absorbability of dye ink reduces, and, because light transmission becomes higher, use the photostability of the printing of dye ink to reduce, coating strength reduces.In addition, when using it for ink-jet recording paper and printing by pigment ink, the stationarity that produces pigment ink reduces such harmful effect.
On the other hand, if the average grain diameter of the offspring of silica surpasses 11 μ m, use the dye ink printing, reach when using the pigment ink printing, because printing concentration is low, the clarity that produces image reduces or surface significantly coarse, causes inhomogeneous these problems of printing easily.
In addition, in the present invention, the average aggregate particle size of silica is to measure by counting method (コ one Le カ ゥ Application ), and expression disperses silica ultrasonic in distilled water 30 seconds and volume average particle size that the particle that obtains is measured as sample.
In addition, the colour rendering during owing to use dye ink and pigment ink record is good, and silica is according to the preferred 210～250cm of oil absorption of JIS K-5101 standard
3/ 100g.
In the present invention, the silica that contains of ink-receiver layer preferably uses at least a portion to pass through the silica of surfactant treatment surface (surface treatment silica).That is, all silica are that surface treatment silica is also passable, use surface treatment silica and do not have the silica of processing also passable.Do not have the silica of handling since be to use the front describe, in invention employed silica, therefore omit and describe.
(handling the silica on surface with surfactant)
The silica of handling the surface with surfactant is to use previously described silica and its analog.
Handle the surfactant of silica surface, can examples example such as nonionic surfactant, cationic surfactant, anionic surfactant, amphoteric surfactant, preferably use nonionic surfactant.The object lesson of nonionic surfactant can be enumerated polyoxyethylene alkyl ether, poloxalkol, polyoxyethylene polyoxy-propylene etc.Also preferred in these HLB value (hydrophilic-the lipophilic balance value) is 8.0～15.0 surfactant, is more preferably 10.0～12.0 surfactant.If the HLB value less than 8.0, has the tendency that is difficult to obtain sufficient absorption of inks speed,, be easy to generate infiltration if the HLB value surpasses 15.0.
The surfactant facture of silica surface can adopt for example special method that flat 9-25440 communique is put down in writing of opening.That is, can adopt by flow at high speed agitator mixed silica wet method silica and the surfactant dry-mix process of multichain type nonionic surfactant for example for example.At this moment, can in silica, directly add and mixed surfactant, also can add and mix surfactant by the dilution of volatile catalysts such as ethanol.
In addition, also can adopt in advance at silica and for example add in the emulsification slurries of wet method silica and mix for example nonionic surfactant of quantitative surfactant, then carry out wet processed methods such as spray-drying.During the wet processed method, when surfactant is insoluble in water, preferably acutely disperses this surfactant with formation emulsion in advance, and this emulsion is added in the emulsification slurries of pigment, fully mix the dry processing in back.
Think and use surfactant to handle the state that surperficial its surface of silica is covered by surfactant by this method.
Relative silica, 0.1～30 part of the preferred per 100 parts of silica of the addition of surfactant are more preferably 0.5～20 part.If in preferred this scope, cooperate the silica that is covered by surfactant, can improve colour rendering, obtain distinct image.
(adhesive)
The employed adhesive of this ink-receiver layer has no particular limits, can enumerate water-soluble binders such as starch, polyvinyl alcohol, acrylic polymer, ethylene-vinyl acetate lipin polymer, vinyl acetate esters polymer, polyurethane polymer, styrene-butadiene type copolymer or their emulsion-type adhesive etc. usually as ink mist recording with employed always known adhesive.Can be used alone adhesive, also can two or more merging use.
Wherein, the emulsion type adhesive of preferred acrylic polymer.Acrylic polymer can be enumerated the polymer that acrylic acid, methacrylic acid, acrylate, methacrylate etc. contain (methyl) acrylic compounds unit.Acrylic polymer can be single polymers of (methyl) acrylic compounds unit, also can be copolymer or the copolymer that contains other component units.Acrylic polymer can be enumerated and for example gather (methyl) methyl acrylate etc.
In addition, the emulsion-type adhesive of preferred acrylic polymer merges use with polyvinyl alcohol, and this is because good with the cohesive of pigment.
The also suitable polyvinyl alcohol derivatives such as silanol modified polyvinylalcohol or cationization polyvinyl alcohol that use of polyvinyl alcohol.
In addition, merge when using acrylic polymer and polyvinyl alcohol or derivatives thereof, preferably use, be more preferably with 1: 5～1: 1 ratio merging and use with 1: 10～2: 1 ratio merging.
The silica of relative 100 mass parts of the content of acrylic polymer, preferred 1～50 mass parts is more preferably 5～40 mass parts.
Usually adhesive is most known adhesives such as emulsion-type adhesive or water-soluble binder, through studying intensively, the inventor finds: if use the emulsion-type adhesive of acrylic polymer, no matter by dye ink or pigment ink printing, all obtain distinct image, and the keeping quality of blank sheet of paper part is also good.
By the way, the employed representational emulsion-type adhesive ethylene-vinyl acetate lipin polymer of ink-jet recording paper, vinyl acetate esters polymer, polyurethane polymer, styrene-butadiene type copolymer etc., any all is being not so good as acrylic polymer aspect printing colour rendering, and there are the problem of the flavescence easily of blank sheet of paper part, keeping quality difference in polyurethane polymer, styrene-butadiene type copolymer.
In addition, if only use water-soluble binders such as starch, polyvinyl alcohol, can not obtain sufficient coating strength, perhaps when the coating liquid of preparation ink-receiver layer, the coating liquid that can not prepare high concentration, if when coating coating amount few, can not obtain distinct image.
(cationic printing ink fixative)
The employed cationic printing ink of this ink-receiver layer fixative has no particular limits, and can enumerate
1) polyalkylenepolyamines class or derivatives thereof such as polyethylene polyamine or many propylidene polyamines,
2) have the acrylate copolymer of secondary amine, tertiary amine or quaternary ammonium group,
3) polyvinylamine, polyethylene amidine, 5 yuan of ring amidine classes,
4) be representative dicyano cationoid resin with cdicynanmide-copolyoxymethylenes,
5) with cdicynanmide-polyvinylamine copolymer be the polyamine cation resin of representative,
6) dimethylamine-epihalohydrin copolymer,
7) diallyl dimethyl ammonium-SO
2Copolymer,
8) diallyl amine salt-SO
2Copolymer,
9) chlorination dimethyldiallylammonium polymer,
10) allyl amine salt polymer,
11) dialkyl amido ethyl (methyl) acrylate quaternary salt copolymer,
12) acrylamide-diallylamine salt copolymer,
13) aluminium salt such as aluminium polychloride, polyacetic acid aluminium,
14) water-soluble metal salt such as zinc sulfate
Deng general commercially available fixative, can use or use two or more separately.
Wherein, cationic printing ink fixative, the preferred merging used cdicynanmide-polyvinylamine copolymer and acrylamide-diallylamine copolymer.Owing to use cdicynanmide-polyvinylamine copolymer and acrylamide-diallylamine copolymer by merging, the keeping quality of the colour rendering when using the pigment ink record, the colour rendering when using the dye ink record and printing is good, and is therefore preferred.In addition, use zinc sulfate by merging, the colour rendering when particularly using pigment ink to print significantly improves, and therefore is more preferably.
Cationic printing ink fixative combined amount, the silica of relative 100 mass parts, preferred 5～60 mass parts are controlled at the scope of 20～50 mass parts that are more preferably.If the cationic fixative, causes the colour rendering of image easily less than 5 mass parts and reduces, or the reduction of the keeping quality of printing, if surpass 60 mass parts, ink absorption reduces, causes easily inhomogeneous, the clear picture reduction of printing.
Suit in ink-receiver layer, to be added on various auxiliary agents such as employed thickener, defoamer, wetting agent, surfactant, colouring agent, antistatic agent, photostability auxiliary agent, ultra-violet absorber, antioxidant, anticorrisive agent in the general lacquer-coated paper manufacturing.
Even ink-jet recording paper of the present invention does not contain fluorescent whitening agent in fact at ink-receiver layer, also can obtain high whiteness.Therefore, can obtain the good keeping quality of blank sheet of paper part.
Such ink-receiver layer can be on the priming coat surface that is formed on the paper base material, the ink-receiver layer coating liquid that coating contains above-mentioned silica, adhesive, cationic printing ink fixative and contains auxiliary agent as required, and dry and form.
The coating amount of ink-receiver layer has no particular limits, preferred 2～30g/m
2, be more preferably 5～20g/m
2
If coating amount lacks than above-mentioned lower limit, ink absorption, clear picture, printing keeping quality reduce easily, if coating amount is more than the above-mentioned upper limit, the clarity of coating strength or image reduces easily.
In addition, ink-receiver layer such as above-mentioned can the be made up of multilayer, at this moment, the ink-receiver layer component of interlayer can be different.
Ink-receiver layer can be coated with various known applying device preparations such as machine, notch board coating machine, rod-type coating machine, lip coating machine, curtain formula coating machine and mould coating machine by vane type coating machine, air knife coating machine, roll coater, rod.After the coating, also can use calenders such as machine calender, TG calender, multi-rolling mill, soft calender to carry out fine finishining.
[printed matter]
On ink-jet recording paper described above, use printing equipments such as printer, use dye ink or pigment ink to print, can prepare printed matter.
Here, no matter use dye ink or pigment ink can obtain good colour rendering, enough printing concentration, realize the clarity of image.And, no matter use dye ink or pigment ink, can obtain the keeping quality (for example photostability, ozone resistance, resistance to water) of printing, the good printed matter of keeping quality (for example hear resistance, photostability, ozone resistance) of blank sheet of paper, this printed matter is very suitable for being widely used in outdoor displaying etc.
Below more specifically describe the present invention by enumerating embodiment, the invention is not restricted to these embodiment certainly.In addition, if part and % among the embodiment are not particularly limited, expression removes the solid shape branch that anhydrates and represents mass parts and quality % respectively.In addition, following " aggregate particle size " is meant average secondary grade.
Embodiment 1
[paper base material A]
20 parts of precipitated calcium carbonates join in the slurry of 100 parts of bleached hardwood kraft pulps (freeness is 400ml CSF), add 1 part of cationic starch, 0.2 part of anhydrous alkenyl succinic acid class inert filler, fully mix to form paper making raw material, using fourdrinier wire multi-cartridge paper machine to be dried to moisture content is 10%, applies 4g/m with squeezer on the two sides
27% oxidized starch solution, being dried to moisture is 7%, prepares paper weight 200g/m
2Paper base material A.
[priming coat coating liquid A]
100 parts of titanium dioxide (Sakai chemical company system, trade name: R-21, aggregate particle size .0.5 μ m, rutile-type) are dispersed in the water as adhesive as pigment, 10 parts of acrylic polymers (ロ one system ァ Application De Ha one ス corporate system, trade name: プ ラ イ マ Le P-376, emulsion type adhesive) and 5 parts of oxidized starch (prince コ one Application ス one チ corporate system, trade name: エ one ス A, water-soluble binder), obtain priming coat coating liquid A.
[ink-receiver layer coating liquid A]
100 parts of wet silicon dioxides (ト Network ャ マ society system, trade names: マ ァ イ Application シ one Le X-60, aggregate particle size 6.2 μ m, oil absorption 240cm
3/ 100g) as pigment, 20 parts of silicyl modified polyvinyl alcohols (Network ラ レ society system, trade names: R-1130) with 20 parts of acrylic polymers (ロ one system ァ Application De Ha one ス society system, trade names: プ ラ イ マ Le P-376) as adhesive, 15 parts of acrylamide-diallylamine copolymers (Sumitomo Chemical society system, trade names: SR1001) with 15 parts of cdicynanmide-polyvinylamine copolymers (solar corona chemistry society system, trade names: ネ ォ Off イ ッ Network ス I J-117) be dispersed in the water, obtain ink-receiver layer coating liquid A as the printing ink fixative.
[manufacturing of ink-jet recording paper]
On paper base material A, be 10g/m with the coating amount
2Coating priming coat coating liquid A after the drying, is 10g/m with the coating amount
2Coating ink-receiver layer coating liquid A, drying is made ink-jet recording paper.The blank sheet of paper part on the ink-receiver layer surface of the ink-jet recording paper that obtains in addition, is 3% according to 60 degree mirror surface lusters of JIS-Z8741 defined.
Embodiment 2
[paper base material B]
20 parts of precipitated calcium carbonates join 70 parts of bleached hardwood kraft pulps (freeness is 400ml CSF) and 30 parts and handle in the mixed slurry of paper pulp (freeness is 250ml CSF) of the old paper of newspaper through deinking, add 1 part of cationic starch, 0.2 part of anhydrous alkenyl succinic acid class inert filler, fully mix to form paper making raw material, using fourdrinier wire multi-cartridge paper machine to be dried to moisture content is 10%, applies 4g/m with squeezer on the two sides
27% oxidized starch solution, being dried to moisture is 7%, prepares paper weight 200g/m
2Paper base material B.
[manufacturing of ink-jet recording paper]
Except the paper base material A of embodiment 1 becomes paper base material B, make ink-jet recording paper similarly to Example 1.The blank sheet of paper part on the ink-receiver layer surface of the ink-jet recording paper that obtains in addition, is 3% according to 60 degree mirror surface lusters of JIS-Z8741 defined.
Embodiment 3
[paper base material C]
20 parts of precipitated calcium carbonates join 70 parts of bleached hardwood kraft pulps (freeness is 400ml CSF) and 30 parts and handle in the mixed slurry of the paper pulp (freeness is 250ml CSF) of redying old paper (redying old paper: also contain art paper in the paper that does not contain wood pulp in colored printing) through deinking, add 1 part of cationic starch, 0.2 part of anhydrous alkenyl succinic acid class inert filler, fully mix to form paper making raw material, using fourdrinier wire multi-cartridge paper machine to be dried to moisture content is 10%, applies 4g/m with squeezer on the two sides
27% oxidized starch solution, being dried to moisture is 7%, prepares paper weight 200g/m
2Paper base material C.
[manufacturing of ink-jet recording paper]
Except the paper base material A of embodiment 1 becomes paper base material C, make ink-jet recording paper similarly to Example 1.The blank sheet of paper part on the ink-receiver layer surface of the ink-jet recording paper that obtains in addition, is 3% according to 60 degree mirror surface lusters of JIS-Z8741 defined.
Embodiment 4
[paper base material D]
20 parts of precipitated calcium carbonates join 70 parts of bleached hardwood kraft pulps (freeness is 400ml CSF) and the 30 parts of old paper of first-class white (old paper of first-class white: binding printing factory of handling through disassociation, white printing by generations such as cut-off parts do not contain wood pulp paper do not have cut paper wood and waste paper) the mixed slurry of paper pulp (freeness is 250ml CSF) in, add 1 part of cationic starch, 0.2 part anhydrous alkenyl succinic acid class inert filler, fully mix to form paper making raw material, using fourdrinier wire multi-cartridge paper machine to be dried to moisture content is 10%, applies 4g/m with squeezer on the two sides
27% oxidized starch solution, being dried to moisture is 7%, prepares paper weight 200g/m
2Paper base material D.
[manufacturing of ink-jet recording paper]
Except the paper base material A of embodiment 1 becomes paper base material D, make ink-jet recording paper similarly to Example 1.The blank sheet of paper part on the ink-receiver layer surface of the ink-jet recording paper that obtains in addition, is 3% according to 60 degree mirror surface lusters of JIS-Z8741 defined.
Embodiment 5
[priming coat coating liquid B]
100 parts of titanium dioxide (Sakai chemical company system, trade name: R-21, aggregate particle size .0.5 μ m, rutile-type) are dispersed in the water as adhesive as pigment, 10 parts of ethylene-vinyl acetate lipin polymers (clear and macromolecule corporate system, trade name: Port リ ゾ one Le AM-3000, emulsion type adhesive) and 5 parts of oxidized starch (prince コ one Application ス one チ corporate system, trade name: エ one ス A, water-soluble binder), obtain priming coat and apply liquid B.
[manufacturing of ink-jet recording paper]
On paper base material B, be 10g/m with the coating amount
2Coating priming coat coating liquid B after the drying, is 10g/m with the coating amount
2Coating ink-receiver layer coating liquid A, drying is made ink-jet recording paper.The blank sheet of paper part on the ink-receiver layer surface of the ink-jet recording paper that obtains in addition, is 3% according to 60 degree mirror surface lusters of JIS-Z8741 defined.
Embodiment 6
[priming coat coating liquid C]
100 parts of titanium dioxide (Sakai chemical company system, trade name: R-21, aggregate particle size .0.5 μ m, rutile-type) are dispersed in the water as adhesive as pigment, 10 parts of vinyl acetate esters polymers (day letter chemical industrial company system, trade name: PVC ニ Block ラ Application 1080, emulsion-type adhesive) and 5 parts of oxidized starch (prince コ one Application ス one チ corporate system, trade name: エ one ス A, water-soluble binder), obtain priming coat coating liquid C.
[manufacturing of ink-jet recording paper]
On paper base material B, be 10g/m with the coating amount
2Coating priming coat coating liquid C after the drying, is 10g/m with the coating amount
2Coating ink-receiver layer coating liquid A, drying is made ink-jet recording paper.The blank sheet of paper part on the ink-receiver layer surface of the ink-jet recording paper that obtains in addition, is 3% according to 60 degree mirror surface lusters of JIS-Z8741 defined.
Embodiment 7
[manufacturing of surface treatment silica]
Suspension 900g wet silicon dioxide (ト Network ャ マ corporate system, trade name: Yu Shuizhong Off ァ イ Application シ one Le X-60), pulp (about 10～15%), on this slurry, add the aqueous suspension of 100g surfactant (poly-alcoxyl ethane lauryl ether, the first industrial drugmaker system, trade name: ノ イ グ Application ET-102, HLB:10.8), mixed 1 hour.Then, spray-drying, crushing and classification obtains surface treatment silica.The average aggregate particle size of the surface treatment silica of gained is 6 μ m.
[ink-receiver layer coating liquid B]
80 parts of wet silicon dioxide (ト Network ャ マ corporate systems, trade name: マ ァ イ Application シ one Le X-60, aggregate particle size 6.2 μ m) as pigment, 20 parts of surface treatment silica by above-mentioned gained, 20 parts of silicyl modified polyvinyl alcohol (Network ラ レ corporate systems, trade name: R-1130) with 20 parts of acrylic polymer (ロ one system ァ Application De Ha one ス corporate systems, trade name: プ ラ イ マ Le P-376) as adhesive, 15 parts of acrylamide-diallylamine copolymer (sumitomo chemical company systems, trade name: SR1001) with 15 parts of cdicynanmide-polyvinylamine copolymer (solar corona chemical company systems, trade name: ネ ォ Off イ ッ Network ス I J-117) be dispersed in the water, obtain ink-receiver layer coating liquid B as the printing ink fixative.
[manufacturing of ink-jet recording paper]
On paper base material B, be 10g/m with the coating amount
2Coating priming coat coating liquid A after the drying, is 10g/m with the coating amount
2Coating ink-receiver layer coating liquid B, drying is made ink-jet recording paper.The blank sheet of paper part on the ink-receiver layer surface of the ink-jet recording paper that obtains in addition, is 3% according to 60 degree mirror surface lusters of JIS-Z8741 defined.
Embodiment 8
[ink-receiver layer coating liquid C]
100 parts of wet silicon dioxide (ト Network ャ マ corporate systems, trade name: マ ァ イ Application シ one Le X-60, aggregate particle size 6.2 μ m) as pigment, 20 parts of silicyl modified polyvinyl alcohol (Network ラ レ corporate systems, trade name: R-1130) with 20 parts of acrylic polymer (ロ one system ァ Application De Ha one ス corporate systems, trade name: プ ラ イ マ Le P-376) as adhesive, 25 parts of acrylamide-diallylamine copolymer (sumitomo chemical company systems, trade name: SR1001) with 5 parts of cdicynanmide-polyvinylamine copolymer (solar corona chemical company systems, trade name: ネ ォ Off イ ッ Network ス I J-117) the printing ink fixative is dispersed in the water, obtains ink-receiver layer coating liquid C.
[manufacturing of ink-jet recording paper]
On paper base material B, be 10g/m with the coating amount
2Coating priming coat coating liquid A after the drying, is 10g/m with the coating amount
2Coating ink-receiver layer coating liquid C, drying is made ink-jet recording paper.The blank sheet of paper part on the ink-receiver layer surface of the ink-jet recording paper that obtains in addition, is 3% according to 60 degree mirror surface lusters of JIS-Z8741 defined.
Comparative example 1
[manufacturing of ink-jet recording paper]
On paper base material B, be 10g/m with the coating amount
2Coating ink-receiver layer coating liquid A, drying is made the ink-jet recording paper that does not have priming coat.The blank sheet of paper part on the ink-receiver layer surface of the ink-jet recording paper that obtains in addition, is 3% according to 60 degree mirror surface lusters of JIS-Z8741 defined.
Comparative example 2
[priming coat coating liquid D]
100 parts of wet silicon dioxides (ト Network ャ マ corporate system, trade name: マ ァ イ Application シ one Le X-60, aggregate particle size 6.2 μ m) are as pigment,, 10 parts of acrylic polymers (ロ one system ァ Application De Ha one ス corporate system, trade name: プ ラ イ マ Le P-376, emulsion-type adhesive) and 5 parts of oxidized starch (prince コ one Application ス one チ corporate system, trade name: エ one ス A, water-soluble binder) are dispersed in the water as adhesive, obtain priming coat coating liquid D.
[manufacturing of ink-jet recording paper]
On paper base material B, be 10g/m with the coating amount
2Coating priming coat coating liquid D, drying is 10g/m with the coating amount
2Coating ink-receiver layer coating liquid A, drying is made ink-jet recording paper.The blank sheet of paper part on the ink-receiver layer surface of the ink-jet recording paper that obtains in addition, is 3% according to 60 degree mirror surface lusters of JIS-Z8741 defined.
Comparative example 3
[ink-receiver layer coating liquid D]
100 parts of wet silicon dioxides (ト Network ャ マ corporate system, trade name: マ ァ イ Application シ one Le X-60, aggregate particle size 6.2 μ m) as pigment, 20 parts of silicyl modified polyvinyl alcohol (Network ラ レ corporate systems, trade name: R-1130) with 20 parts of acrylic polymer (ロ one system ァ Application De Ha one ス corporate systems, trade name: プ ラ イ マ Le P-376) as adhesive, 30 parts of polydiene propyl-dimethyl ammonium chloride (セ Application カ corporate systems, trade name: ュ ニ セ Application ス CP101) printing ink fixative printing ink fixative is dispersed in the water, obtains ink-receiver layer coating liquid D.
[manufacturing of ink-jet recording paper]
On paper base material B, be 10g/m with the coating amount
2Coating priming coat coating liquid D, drying is 10g/m with the coating amount
2Coating ink-receiver layer coating liquid D, drying is made ink-jet recording paper.The blank sheet of paper part on the ink-receiver layer surface of the ink-jet recording paper that obtains in addition, is 3% according to 60 degree mirror surface lusters of JIS-Z8741 defined.
Comparative example 4
[priming coat coating liquid E]
100 parts of calcium carbonate (Ao Duomo industrial group system, trade name: TP-121, shape: spindle shape, basic particle diameter: 0.5 * 1.5 μ m) as pigment, 10 parts of acrylic polymers (ロ one system ァ Application De Ha one ス corporate system, trade name: プ ラ イ マ Le P-376, emulsion-type adhesive) and 5 parts of oxidized starch (prince コ one Application ス one チ corporate system, trade name: エ one ス A, water-soluble binder) are dispersed in the water as adhesive, obtain priming coat coating liquid E.
[manufacturing of ink-jet recording paper]
On paper base material B, be 10g/m with the coating amount
2Coating priming coat coating liquid E, drying is 10g/m with the coating amount
2Coating ink-receiver layer coating liquid A, drying is made ink-jet recording paper.The blank sheet of paper part on the ink-receiver layer surface of the ink-jet recording paper that obtains in addition, is 3% according to 60 degree mirror surface lusters of JIS-Z8741 defined.
Comparative example 5
[priming coat coating liquid F]
100 parts of titanium dioxide (Sakai chemical company system, trade name: R-21, aggregate particle size .0.5 μ m, rutile-type) are dispersed in the water as adhesive as pigment, 10 parts of SBR (JSR corporate system, trade name: 0589, Tg:0 ℃, emulsion-type adhesive) emulsion and 5 parts of oxidized starch (prince コ one Application ス one チ corporate system, trade name: エ one ス A, water-soluble binder), obtain priming coat coating liquid F.
[manufacturing of ink-jet recording paper]
On paper base material B, be 10g/m with the coating amount
2Coating priming coat coating liquid F, drying is 10g/m with the coating amount
2Coating ink-receiver layer coating liquid A, drying is made ink-jet recording paper.The blank sheet of paper part on the ink-receiver layer surface of the ink-jet recording paper that obtains in addition, is 3% according to 60 degree mirror surface lusters of JIS-Z8741 defined.
Comparative example 6
[ink-receiver layer coating liquid E]
100 parts of wet silicon dioxides (ト Network ャ マ corporate system, trade name: Off ァ イ Application シ one Le F80, aggregate particle size 1.8 μ m, oil absorption 240cm
3/ 100g) as pigment, 20 parts of silicyl modified polyvinyl alcohols (Network ラ レ corporate system, trade names: R-1130) with 20 parts of acrylic polymers (ロ one system ァ Application De Ha one ス corporate system, trade names: プ ラ イ マ Le P-376) as adhesive, 15 parts of acrylamide-diallylamine copolymers (sumitomo chemical company system, trade names: SR1001) with 15 parts of cdicynanmide-polyvinylamine copolymers (solar corona chemical company system, trade names: ネ ォ Off イ ッ Network ス I J-117) be dispersed in the water, obtain ink-receiver layer coating liquid E as the printing ink fixative.
[manufacturing of ink-jet recording paper]
On paper base material B, be 10g/m with the coating amount
2Coating priming coat coating liquid A, drying is 10g/m with the coating amount
2Coating ink-receiver layer coating liquid E, drying is made ink-jet recording paper.The blank sheet of paper part on the ink-receiver layer surface of the ink-jet recording paper that obtains in addition, is 4% according to 60 degree mirror surface lusters of JIS-Z8741 defined.
Comparative example 7
[ink-receiver layer coating liquid F]
With 100 parts of wet silicon dioxides (marshy land corporate system, trade name: ミ ズ カ シ Le P-78F, aggregate particle size 12.5 μ m, oil absorption 230cm
3/ 100g) as pigment, 20 parts of silicyl modified polyvinyl alcohols (Network ラ レ corporate system, trade names: R-1130) with 20 parts of acrylic polymers (ロ one system ァ Application De Ha one ス corporate system, trade names: プ ラ イ マ Le P-376) as adhesive, 15 parts of acrylamide-diallylamine copolymers (sumitomo chemical company system, trade names: SR1001) with 15 parts of cdicynanmide-polyvinylamine copolymers (solar corona chemical company system, trade names: ネ ォ Off イ ッ Network ス I J-117) be dispersed in the water, obtain ink-receiver layer coating liquid F as the printing ink fixative.
[manufacturing of ink-jet recording paper]
On paper base material B, be 10g/m with the coating amount
2Coating priming coat coating liquid A, drying is 10g/m with the coating amount
2Coating ink-receiver layer coating liquid F, drying is made ink-jet recording paper.The blank sheet of paper part on the ink-receiver layer surface of the ink-jet recording paper that obtains in addition, is 3% according to 60 degree mirror surface lusters of JIS-Z8741 defined.
Embodiment 9
[ink-receiver layer coating liquid G]
With 100 parts of wet silicon dioxides (ト Network ャ マ corporate system, trade name: マ ァ イ Application シ one Le X-60, aggregate particle size 6.2 μ m, oil absorption 240cm
3/ 100g) as pigment, 20 parts of silicyl modified polyvinyl alcohol (Network ラ レ corporate systems, trade name: R-1130) with 20 parts of acrylic polymer (ロ one system ァ Application De Ha one ス corporate systems, trade name: プ ラ イ マ Le P-376) as adhesive, 15 parts of acrylamide-diallylamine copolymer (sumitomo chemical company systems, trade name: SR1001), 15 parts of cdicynanmide-polyvinylamine copolymer (solar corona chemical company systems, trade name: ネ ォ Off イ ッ Network ス I J-117) and 10 parts of zinc sulfate solutions (with the pure pharmaceutical worker's industry of light corporate system: use water-soluble formed 5% solution of 7 zinc sulphate hydrates, molecular weight 287.56) is dispersed in the water as the printing ink fixative, obtains ink-receiver layer coating liquid G.
[manufacturing of ink-jet recording paper]
On paper base material B, be 10g/m with the coating amount
2Coating priming coat coating liquid A, drying is 10g/m with the coating amount
2Coating ink-receiver layer coating liquid G, drying is made ink-jet recording paper.The blank sheet of paper part on the ink-receiver layer surface of the ink-jet recording paper that obtains in addition, is 3% according to 60 degree mirror surface lusters of JIS-Z8741 defined.
[evaluation]
Estimate the keeping quality (photostability, ozone resistance, resistance to water) of the whiteness of the ink-jet recording paper of each embodiment, comparative example gained, the keeping quality of blank sheet of paper part (flavescence that prevents to be heated, prevent, prevent), gradation of drop-out colour, ink absorption, printing ink stationarity, printing portion because of the ozone flavescence because of the light flavescence in order to following method.
In addition, when estimating, to the printing of ink-jet recording paper, use commercially available dye ink-jet printer (EPSON society system, trade name: PM-G800, printing type: radiation is unglazed, and coarse paper (Off ォ ト マ ッ ト Paper)/height is meticulous), commercially available pigment inkjet printer (EPSON society system, trade name: PX-G900, printing type: radiation is unglazed, and coarse paper/height is meticulous), commercially available pigment inkjet printer (EPSON society system, trade name: PM-4000PX, printing type: radiation is unglazed, and coarse paper/height is meticulous), and commercially available pigment inkjet printer (EPSON society system, trade name: PX-V600, printing type: radiation is unglazed, and coarse paper/height is meticulous) four types carry out.
[whiteness]
Measure the blank sheet of paper whiteness partly on the ink-receiver layer next door of ink-jet recording paper according to the method for JIS-P8123 defined.
[keeping quality (preventing the flavescence of being heated) of blank sheet of paper part]
Ink-jet recording paper left standstill for 1 week under 80 ℃ of 50% environment.Before leaving standstill and after leaving standstill, measure the tone b of ink-receiver layer one side of paper
*Value.Use X-rite corporate system 938 spectrodensitometers to measure.Then, calculate Δ b according to following relational expression
*Value.
Δ b
*Value=| the Δ b after leaving standstill
*Value |-| the Δ b before leaving standstill
*Value |
Keeping quality (preventing the flavescence of being heated) according to following standard evaluation blank sheet of paper part
Zero: Δ b
*Value does not almost have flavescence less than 3.
△: Δ b
*Value is greater than 3 less than 6, flavescence.
*: Δ b
*Value is greater than 6, obviously flavescence.
[keeping quality (preventing) of blank sheet of paper part] because of the light flavescence
Ink-jet recording paper is under 60 ℃ of 50% environment, with xenon lamp (100,000 lux) irradiation 3 days.Measure the tone b of ink-receiver layer one side of pre-irradiation and irradiation back paper
*Value.Use X-rite society system 938 spectrodensitometers to measure.Then, calculate Δ b according to following formula
*Value.
Δ b
*Value=| postradiation Δ b
*Value |-| the Δ b of pre-irradiation
*Value |
Keeping quality (preventing) according to following standard evaluation blank sheet of paper part because of the light flavescence
Zero: Δ b
*Value does not almost have flavescence less than 3.
△: Δ b
*Value is greater than 3 less than 6, flavescence.
*: Δ b
*Value is greater than 6, obviously flavescence.
[keeping quality (preventing) of blank sheet of paper part] because of the ozone flavescence
Ink-jet recording paper is under 24 ℃ of 60% environment, and ozone concentration is in the 10ppm atmosphere, places 24 hours.Measure the tone b of ink-receiver layer one side of placing preceding and placement back paper
*Value.Use X-rite society system 938 spectrodensitometers to measure.Then, calculate Δ b according to following formula
*Value.
Δ b
*Value=| postradiation Δ b
*Value |-| the Δ b of pre-irradiation
*Value |
Keeping quality (preventing) according to following standard evaluation blank sheet of paper part because of the ozone flavescence
Zero: Δ b
*Value does not almost have flavescence less than 3.
△: Δ b
*Value is greater than 3 less than 6, flavescence.
*: Δ b
*Value is greater than 6, obviously flavescence.
[printing concentration]
Use image (" high meticulous colorful digital standard picture XYZ/JIS-SCID ", identification sign: S6, the image name: カ ラ one チ ャ one ト) of above-mentioned four types printer prints juridical person JSA distribution, utilize GretagMacbeth corporate system RD-914, measure the printing concentration of the most dark color part of black.
[ink absorption]
When estimating above-mentioned printing concentration, observe the most dark color part of black by commercially available dye ink-jet printer (EPSON corporate system, trade name: PM-G800, printing type: radiation is unglazed, and coarse paper/height is meticulous) print record body.
Zero: printing ink does not overflow, bleeding, color spot.
*: printing ink produces bleeding, color spot.
[printing ink stationarity]
When estimating above-mentioned printing concentration, the most dark color part of black by commercially available pigment inkjet printer (EPSON society system, trade name: PM-4000PX, printing ink: unglazed coarse carbon black (マ ッ ト Block ラ ッ Network), printing type: radiation is unglazed, and coarse paper/height is meticulous) hard copy body, in printing after one day, rub with the hands with finger.
Zero: promptly use finger to rub with the hands, printing does not change yet, and the stationarity of printing ink is good.
*: if rub with the hands with finger, printing peels off, and the stationarity of printing ink is poor.
[keeping quality of printing (photostability)]
Use commercially available dye ink-jet printer (EPSON corporate system, trade name: PM-G800, printing type: radiation is unglazed, and coarse paper/height is meticulous), print the peony gradation of drop-out colour and be 1.0 record body, under 24 ℃ of 60%RH environment, with the fluorescent lamp of illumination 70Klux 500 hours, measure gradation of drop-out colour.But, on the record body, the thick glass of 2mm is set.
Keeping quality (photostability) according to following standard evaluation printing.
◎: change in concentration is less than 15%
Zero: change in concentration more than 15% less than below 20%
△: change in concentration more than 20% less than below 30%
*: change in concentration is more than 30%
[keeping quality of printing (ozone resistance)]
Use commercially available dye ink-jet printer (EPSON society system, trade name: PM-G800, printing type: radiation is unglazed, and coarse paper/height is meticulous), print the peony gradation of drop-out colour and be 1.0 record thing, under 24 ℃ of 60%RH environment, in ozone concentration 10ppm atmosphere, placed 24 hours, measure printing concentration.
Keeping quality (ozone resistance) according to following standard evaluation printing.
Zero: change in concentration is less than 15%
△: change in concentration more than 15% less than below 30%
*: change in concentration is more than 30%
[keeping quality of printing (resistance to water)]
Use commercially available dye ink-jet printer (EPSON society system, trade name: PM-G800, printing type: radiation is unglazed, and coarse paper/height is meticulous), the literal that the maximum concentration of printing black is 30 drips air dry in the above.
According to following standard evaluation
The keeping quality of printing (resistance to water)
◎: do not ooze out fully.
Zero: take place a bit to ooze out, the differentiation of literal does not have obstacle.
△: ooze out, the differentiation of literal has obstacle
*: oozing out of considerable part taken place, and the differentiation of literal is had any problem.
[table 1]
Result by above-mentioned table 1, can learn: priming coat of the present invention contains titanium dioxide as pigment, and contain at least a acrylic polymer that is selected from, the emulsion-type adhesive of ethylene-vinyl acetate lipin polymer and vinyl acetate esters polymer is as adhesive, it is the ink-jet recording paper of the silica of 3～11 μ m as pigment and cationic printing ink fixative that ink-receiver layer contains average aggregate particle size, its whiteness, the keeping quality of blank sheet of paper part and the keeping quality of printing are good, and dye ink, pigment ink has good colour rendering simultaneously.And consider environmental protection, and reclaim paper pulp even in paper base material, mix various old paper, also can keep this performance.In addition, when particularly merging the cationic printing ink fixative that uses cdicynanmide-polyvinylamine copolymer and acrylamide-diallylamine polymer, the keeping quality of printing is good especially.And can learn: when using zinc sulfate or handling surperficial surface treatment silica by surfactant, colour rendering is good especially.
On the other hand, can prove: when priming coat pigment used silica, calcium carbonate, when perhaps the adhesive of priming coat used SBR, when ink-receiver layer used fluorescent whitening agent in addition, the keeping quality of blank sheet of paper part is variation significantly.Can learn: the average aggregate particle size of the silica of ink-receiver layer is at less than 3 μ m or when surpassing 11 μ m, shown that ink absorption reduces or stationarity variation, colour rendering such as reduce significantly at preferred performance.
Claims (9)
1. ink-jet recording paper, one side at least with paper making pulp paper base material is provided with priming coat and ink-receiver layer, and wherein priming coat contains pigment and adhesive at least, and ink-receiver layer is positioned at outermost, at least contain pigment and adhesive, it is characterized in that:
Aforementioned priming coat contains titanium dioxide as pigment, and the adhesive that contains at least a emulsion-type that is selected from acrylic polymer, ethane-acetic acid ethyenyl ester analog copolymer and vinyl acetate esters polymer is as adhesive,
It is that the silica of 3～11 μ m is as pigment and cationic printing ink fixative that aforementioned ink-receiver layer contains average aggregate particle size.
2. the described ink-jet recording paper of claim 1 is characterized in that: contain the paper pulp that the old paper more than the 10 quality % reclaims at aforementioned paper pulp.
3. claim 1 or 2 described ink-jet recording papers, it is characterized in that: the ionic printing ink fixative of aforementioned male contains cdicynanmide-polyvinylamine copolymer and acrylamide-diallyl amine polymer.
4. the described ink-jet recording paper of claim 3, it is characterized in that: the ionic printing ink fixative of aforementioned male also contains zinc sulfate.
5. claim 1 or 2 described ink-jet recording papers is characterized in that: contain acrylic polymer at least in the adhesive of ink-receiver layer.
6. claim 1 or 2 described ink-jet recording papers is characterized in that: aforementioned silica has at least a part to be to use surfactant that surface treated is carried out on the surface to handle silica.
7. claim 1 or 2 described ink-jet recording papers is characterized in that: aforementioned ink-receiver layer surface according to the glossiness of 60 degree minute surfaces of JIS-Z8741 defined below 15%.
8. use dye ink, the printed matter that on each described ink-jet recording paper of claim 1～7, prints.
9. use pigment ink, the printed matter that on each described ink-jet recording paper of claim 1～7, prints.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61435/04 | 2004-03-04 | ||
| JP2004061435 | 2004-03-04 | ||
| JP371091/04 | 2004-12-22 |
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| CN1704257A true CN1704257A (en) | 2005-12-07 |
| CN100467281C CN100467281C (en) | 2009-03-11 |
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| Application Number | Title | Priority Date | Filing Date |
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| CNB2005100762754A Expired - Fee Related CN100467281C (en) | 2004-03-04 | 2005-03-02 | Ink jet recording sheet |
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| CN (1) | CN100467281C (en) |
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| CN102152679A (en) * | 2009-12-18 | 2011-08-17 | 理想科学工业株式会社 | Oil-based inkjet printing method, ink set, and coating treatment liquid |
| CN101537748B (en) * | 2008-03-17 | 2012-05-30 | 精工爱普生株式会社 | Ink jet treatment liquid, ink jet recording method, and recorded matter |
| CN103201116A (en) * | 2010-10-29 | 2013-07-10 | 惠普发展公司有限责任合伙企业 | Photo paper |
| CN104629553A (en) * | 2013-11-08 | 2015-05-20 | 上海纳尔数码喷印材料股份有限公司 | Environment-friendly paint for spray-painting, preparation method and applications thereof |
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| CN101537748B (en) * | 2008-03-17 | 2012-05-30 | 精工爱普生株式会社 | Ink jet treatment liquid, ink jet recording method, and recorded matter |
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| CN102152679A (en) * | 2009-12-18 | 2011-08-17 | 理想科学工业株式会社 | Oil-based inkjet printing method, ink set, and coating treatment liquid |
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| CN109689392A (en) * | 2016-05-06 | 2019-04-26 | R.R.当纳利父子公司 | The composition and its method of absorbable ink-jet |
| CN109689392B (en) * | 2016-05-06 | 2021-06-04 | 克里奥瓦克有限公司 | Absorbable inkjet composition and method thereof |
| CN111655929A (en) * | 2017-11-14 | 2020-09-11 | Aw品牌有限公司 | Recyclable and repulpable translucent or transparent paper and packaging applications thereof |
| CN111636242A (en) * | 2020-04-17 | 2020-09-08 | 仙鹤股份有限公司 | Micro-coating sublimation thermal transfer paper and preparation method thereof |
| CN111636242B (en) * | 2020-04-17 | 2022-06-21 | 仙鹤股份有限公司 | Micro-coating sublimation thermal transfer paper and preparation method thereof |
| CN113910721A (en) * | 2021-08-20 | 2022-01-11 | 浙江雅洲铝箔纸业有限公司 | Production process of BOPP laser film |
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