CN100413699C - Paper for ink mist recording - Google Patents
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- CN100413699C CN100413699C CNB031427928A CN03142792A CN100413699C CN 100413699 C CN100413699 C CN 100413699C CN B031427928 A CNB031427928 A CN B031427928A CN 03142792 A CN03142792 A CN 03142792A CN 100413699 C CN100413699 C CN 100413699C
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Abstract
The present invention provides ink jet recording paper which uses supporting bodies with low air permeability or non air permeability, has the advantages of high surface gloss, reproducibility of high points, favorable ink absorbency and high recording density of sliver salt photos, and can not be corrugated resulted from an ink solvent. The ink jet recording paper has the supporting bodies with low air permeability or non air permeability, at least one ink receiving layer which is coated and formed on the supporting bodies, a bright layer which is further coated and formed on the ink receiving layer, and an ink receiving layer which contacts the bright layer. The diameter of the specific surface area of fine hole distribution in a standard mode is smaller than 100 nm. The present invention takes a pigment, the average secondary particle diameter of which is smaller than 1.3 mu m, as a main component, and the bright layer takes a pigment, the average primary particle diameter of which is 5 nm to 100 nm, as a main component.
Description
Technical field
The present invention relates to ink-jet recording paper, particularly have good outward appearances such as high gloss, high flatness, and the ink-jet recording paper with quick ink absorption and good recording characteristics such as high some repeatability, high record concentration.
Background technology
Water-base ink is sprayed and is formed the ink jet recording method of image on paper used for recording by fine nozzle, because noise is low when record, colorize is easy, can high-speed record, and compare reasons such as low price with other printing equipment, be widely used in terminal with in printer, facsimile machine, draught machine or the printing of account ticket etc.
In recent years, along with popularizing rapidly and high meticulous, high speed of printer, appearing on the market of digital camera requires paper used for recording used in the ink jet recording method to have high characteristic in addition.
That is to say that strong request realizes having concurrently recording characteristics such as ink absorption fast, high record concentration, good resistance to water and keeping quality, particularly the image quality that is complementary with the silver salt photo and the ink-jet recording paper of lustrous surface.
Usually, as the method for giving ink-jet recording paper gloss, known have by adopting device such as supercalendering, exert pressure and the roller of temperature between allow paper pass to make the method (satinage) of coating surface smoothing.
But by the paper used for recording that satinage obtains, except the glossiness deficiency, also reduce in the space of coating, so ink absorption is low, and there is the problem that is easy to generate the lettering bleeding in the result.
Except above-mentioned satinage, in order to improve glossiness, also proposed on the surface of smooth plastic film with gloss or resin-coated paper, setting is by many schemes of the method for the ink receiving layer of ink absorption resins such as starch, gelatin, water-soluble cellulose resin, polyvinyl alcohol, polyvinylpyrrolidone, modified polyurethane.
But the paper used for recording that is obtained by these methods is though obtain to a certain degree glossiness, but ink absorption is insufficient, and ink dried is slow, therefore has difficult treatment, it is irregular that ink absorption takes place easily, all poor problem of resistance to water and texture (カ one Le).
In addition, open flat 2-274587 communique, spy the spy and open flat 8-67064 communique, spy and open flat 8-118790 communique, spy and open during 2000-37944 communique, spy open 2001-353957 number etc., proposed to be provided with the ultramicron pigment such as silica gel of small particle diameter method as the coating of principal component.
Yet the paper used for recording that is obtained by these methods though have to a certain degree glossiness, owing to use ultramicron pigment, can not form enough spaces on the coating, still can not obtain satisfiable ink absorption.
Open in the 2000-37944 communique the spy, propose to begin by a side near supporting mass, have the average grain diameter that contains primary particle at least and be 50nm layer following, by the synthetic silica of vapor phase method and contain silica gel layer ink-jet recording paper.Though glossiness, scratch resistance improve, because the voidage step-down of the primary particle body resemble silica gel, so the easy step-down of ink absorption.If reduce coating weight in order to keep ink absorption, then produce interference stripes, the quality of glassy surface reduces, and can not obtain sufficient glossiness.
In addition, open proposition in 2001-353957 number the spy, on supporting mass, be the ink-jet recording paper of layer of 30nm layer following, by the synthetic silica of vapor phase method and cation colloidal particle by beginning near a side of this supporting mass, having the average grain diameter that contains primary particle at least.Though by using the cationic colloidal particle to improve to take a picture the anti-timeliness infiltration and the resistance to water of back image, to open the 2000-37944 communique same with the spy, has the problem of ink absorption reduction.
As mentioned above, open flat 2-274587 communique, spy the spy and open flat 8-67064 communique, spy and open flat 8-118790 communique, spy and open during 2000-37944 communique, spy open 2001-353957 number etc., all do not put down in writing any method that need not to reduce ink absorption speed as far as possible and improve glossiness.
Give the method for gloss as other, by having the attached wetting coating of pressure and dry on the hot roll of minute surface, obtain what is called casting that this minute surface obtains to be coated with method (for example, specification and the spy with reference to U.S. Pat 5275846 opens flat 7-89220 communique) be known by duplicating.
Be coated with method as casting:
(1) will be coated on the body paper with pigment and the adhesive color compositions as principal component, and afterwards during coating is in moisture state, use the felt wrapped roll through the heating of mirror finish to carry out pressure welding, the wet type casting of drying glazing is coated with method;
(2) by acid, salt and heat, make the coating of moisture state become gel state, on the felt wrapped roll of heating it is carried out pressure welding, the gelation casting of drying glazing is coated with method;
(3) coating of moisture state is carried out pressure welding to it in case drying uses wetting solution with its wetting plasticizing afterwards again on the felt wrapped roll of heating, and the rewetting profit casting Tu Fa of drying glazing etc. all are conventional, well-known.
These wet type castings are coated with method, between the practitioner, though be familiar with as each technology, they carry out pressure welding at the coating surface that will be in moistening plastifying state on felt wrapped roll, drying, it is identical duplicating the aspect that obtains minute surface by the demoulding on the felt wrapped roll of heating.
Be coated with the cast-coated paper that method obtains by the casting of such wet type, compare,, can access good printing effect, therefore be dedicated to the purposes of senior printed matter etc. owing to have high-surface gloss and good surface smoothing with common paper used for recording through satinage.
But when as ink-jet recording paper, there are all difficulties in this kind cast-coated paper.For example, shown in the specification of US5275846 like that, in the above-mentioned cast-coated paper, constitute the film forming materials such as adhesive in the color compositions of its coating, obtain the calender roll surface that casting is coated with device and obtain high gloss by duplicating, the existence of this film forming material makes the porous forfeiture of coating, and the ink absorption during ink mist recording extremely reduces.Therefore, in order to improve the ink absorption of cast-coated paper, be important thereby make the coating porous materialization can easily absorb ink.On the one hand, in order to obtain the high image quality that the silver salt photo is had, coating homogeneous film forming is necessary, does not reproduce so that the ink of the minute nozzle of ink-jet printer ejection can have ground, crack.But, in the casting of existing wet type is coated with, the homogeneous film in no crack and porous matter the two to get both be very difficult.
In addition, for cast-coated paper,, need make moisture in the coating become steam and deviate from from the inside for moistening coating is contacted and dry with felt wrapped roll.For this reason, resemble significantly low supporting mass of such gas permeability such as resin-coated paper and film if use, then steam is trapped in coating inside.Because it is very big that the volume of steam is compared with the volume of the preceding water of evaporation, there is not local steam of discharging to promote supporting mass.At this moment, partial destruction that can coating is the most weak.
For example, coating is with respect to a little less than the adhesion of mirror finish felt wrapped roll of heating the time, and coating and felt wrapped roll are being peeled off at the interface, can not fully duplicate the minute surface of obtaining felt wrapped roll, cause the bonding bad phenomenon of what is called.On the other hand, because the bonding force between felt wrapped roll and coating under the situation a little less than undried coating one side's bonding force, breaks in coating inside, the part of coating remains on the surface of felt wrapped roll, causes felt wrapped roll contaminated.Be coated with face no matter all can not form perfect the casting under which kind of situation, thereby cause on the quality, operational fault.
Therefore, use to resemble the such low-permeable of resin-coated paper and film or the supporting mass of non-gas permeability, obtain cast-coated paper and be unusual difficulty.
Secondly, during ink mist recording, during known printing, be subjected to the influence of contained humidity equal solvent in the ink, observe paper used for recording and stretch and fluctuate the defective of promptly so-called wrinkling (コ Star Network リ Application グ).Wrinkling outward appearance that not only damage to print thing, wrinkling paper used for recording and write head contact stain paper used for recording, even paper used for recording breakage sometimes, and cause the situation of write head fault in addition.
In order to suppress wrinkling, use the supporting mass that stretching, extension does not take place to be caused by the solvent in the ink, perhaps between ink receiving layer and supporting mass, the solvent that is provided with in the ink is not effective through layer.For example, as supporting mass,, then can effectively suppress wrinkling if use the supporting mass of low-permeables such as resin-coated paper and film or non-gas permeability.
That is to say, problem of the present invention provides a kind of supporting mass that uses low-permeable or non-gas permeability, have high surface gloss and some repeatability that the silver salt photo has, ink absorption and ink absorption speed are good, record concentration height, and, the wrinkling ink-jet recording paper that is caused by ink solvent does not take place.
The explanation of invention
The result that the present inventor further investigate is, at least one deck ink receiving layer is set on the supporting mass of low-permeable or non-gas permeability, on this ink receiving layer, supply with the coating fluid that is used to form gloss layer, during the above-mentioned coating fluid of supplying with is in moisture state or partial desiccation state, making to supply with has the one side of this coating fluid to contact with felt wrapped roll, when between above-mentioned felt wrapped roll and pressure roll, pressurizeing above-mentioned supporting mass is passed through, after forming the coating liquid layer, peeled off from above-mentioned felt wrapped roll by being coated with liquid layer immediately, obtain having high surface gloss that the silver salt photo had and the coating that does not have the crack, point repeatability and ink absorption, ink absorption speed is good, record concentration height, and the wrinkling ink-jet recording paper that caused by ink solvent does not take place, thereby finished the present invention.
That is to say, the present invention includes following embodiment.
[1] a kind of ink-jet recording paper, the supporting mass with low-permeable or non-gas permeability is coated with the gloss layer that forms again at the ink receiving layer of one deck at least of coating formation on this supporting mass with on this ink receiving layer,
This ink-jet recording paper is characterised in that,
The ink receiving layer that contacts with above-mentioned gloss layer only be below the 100nm with the mode standard diameter (benchmark モ-De diameter) of the specific area that pore distributes, and average aggregate particle size be pigment below the 1.3 μ m as principal component,
Above-mentioned gloss layer is to be that the pigment of 5～100nm is principal component with average primary particle diameter.
[2] ink-jet recording paper as putting down in writing in [1], 75 ° of surface glosses (JIS P8142) on above-mentioned gloss layer surface are more than 70%, and the mapping (writing the picture property) (JIS H 8686-2) when using the optical comb (optics く) of width 2.0mm is more than 55%.
[3] as the ink-jet recording paper of record in [1], the voidage a% of above-mentioned ink receiving layer and the voidage b% of above-mentioned gloss layer satisfy following formula:
a＞b、a-b＞25、45＜a＜80、10＜b≤45。
[4] as the ink-jet recording paper of record in [1], the thickness of above-mentioned gloss layer is 0.02～4 μ m, and is below 1/10 of above-mentioned ink receiving layer gross thickness.
[5] as the ink-jet recording paper of record in [1], one deck at least of above-mentioned ink receiving layer contains pigment and adhesive, and above-mentioned adhesive is that the degree of polymerization is 3000～5000 polyvinyl alcohol.
[6] as the ink-jet recording paper of record in [1], above-mentioned supporting mass is film or resin-coated paper.
[7] as the ink-jet recording paper of any record in [1]～[6], above-mentioned gloss layer forms by felt wrapped roll.
The simple declaration of drawing
Fig. 1 is the schematic diagram of an embodiment preferred of the present invention.
The best mode that carries out an invention
Ink-jet recording paper of the present invention, preferably the manufacture method of the embodiment by following (a)～(e) is made.
(a) a kind of manufacture method of ink-jet recording paper, this ink-jet recording paper be at the gloss layer that has one deck ink receiving layer at least on the supporting mass of low-permeable or non-gas permeability and be provided with on above-mentioned ink receiving layer,
It is characterized in that this method comprises:
On above-mentioned supporting mass, form the ink receiving layer formation operation of one deck ink receiving layer at least,
On above-mentioned ink receiving layer, supply with the coating fluid of the coating fluid that is used to form gloss layer and supply with operation, and
Making to supply with has the one side of above-mentioned coating fluid to contact with felt wrapped roll, when between above-mentioned felt wrapped roll and pressure roll, pressurizeing above-mentioned supporting mass is passed through, after forming the coating liquid layer, during this coating liquid layer is moisture state or partial desiccation state, the pressurization operation of peeling off from above-mentioned felt wrapped roll.
(b) as the manufacture method of the ink-jet recording paper of record in (a), after above-mentioned pressurization operation, also comprise the drying process of dry above-mentioned coating liquid layer.
(c) as the manufacture method of the ink-jet recording paper of record in (a), above-mentioned gloss layer contains the pigment that average primary particle diameter is 5～100nm.
(d) as the manufacture method of the ink-jet recording paper of record in (a), the specific area mode standard diameter that the pore of the above-mentioned ink receiving layer that contacts with above-mentioned gloss layer distributes is only for below the 100nm.
(e) as the manufacture method of the ink-jet recording paper of record in (a), above-mentioned supporting mass is film or resin-coated paper.
An embodiment preferred of the present invention has been shown among Fig. 1.
According to the present embodiment, at first, ink receiving layer 3 (ink receiving layer formation operation) is set on the supporting mass 2 of low-permeable or non-gas permeability.Then, contact with felt wrapped roll 5, supporting mass 2 is placed between felt wrapped roll 5 and the pressure roll 6 for making ink receiving layer 3.Secondly, on ink receiving layer 3, supply with the coating fluid 4 that is used to form gloss layer, concentrate place's (coating fluid supply operation) at the felt wrapped roll 5 and the tangent line top formation coating fluid of pressure roll 6.Then, during coating fluid 4 is moisture state or partial desiccation state, there is the face of coating fluid 4 to contact for making to supply with felt wrapped roll 5, when being pressurizeed between felt wrapped roll 5 and pressure roll 6, passes through supporting mass 2, after forming coating liquid layer 7, will be coated with liquid layer 7 immediately and peel off (pressurization operation) from felt wrapped roll 5.After this, carry out drying (damping), obtain comprising the ink-jet recording paper 1 of supporting mass 2, ink receiving layer 3, gloss layer 8 with drier 9.
Below, each operation is elaborated.
＜ink receiving layer forms operation 〉
In the manufacture method of ink-jet recording paper of the present invention, at first, the ink receiving layer that is formed up to few one deck ink receiving layer 3 on the supporting mass 2 of low-permeable or non-gas permeability forms operation.
(supporting mass)
In the present invention, the supporting mass of low-permeable or non-gas permeability is meant that air permeability was preferably more than 500 seconds, more preferably the supporting mass more than 1000 seconds.Usually, gas permeability is by as the porous project of estimating paper and nonwoven etc. and known air permeability is represented.Air permeability is to be 645mm by the 100ml air by area
2Test film required time representation, stipulate by JIS P 8117 (the air permeability test method of paper and cardboard).
As mentioned above, in casting was coated with, when the casting coating was dry, the moisture of coating became steam, passed supporting mass and discharged from the inside in the past, and the air permeability height that therefore is used to cast the supporting mass that is coated with is preferred.But, in the present invention, be not subjected to the restriction of air permeability.On the contrary, in order to suppress wrinkling, supporting mass does not allow moisture and water vapour by being preferred.Therefore, the supporting mass that the present invention uses so long as have the low-permeable or the non-poromeric material of smooth surface, then need not special material.
As preferred supporting mass, what can exemplify has, for example, oriented polypropylene, the special processing of process, with ユ Port (ユ Port コ-Port レ-シ ヨ Application company produces) is the synthetic paper of representative, the film of glassine paper, polyethylene, polypropylene, soft PVC, RPVC, polyester etc., and use such as the resin-coated paper of resins such as polyvinyl resin, acrylic resin in the lining of substrate surfaces such as paper.Particularly, being equal to the smart outward appearance and the photosensitive paper of resin-coated paper after fine finishining that is mixed with the polyvinyl resin lining paper surface of titanium oxide, is preferred especially the use.Supporting mass is under the situation of resin-coated paper, and the thickness of resin bed has no particular limits, and for example, under the resin-coated paper situation of polyvinyl resin lining, the thickness of polyvinyl resin layer is preferably 3～50 μ m, more preferably 5～40 μ m.Under the situation of the thickness less than 3 μ m of polyvinyl resin layer, form defectives such as hole when resin-coated in the polyvinyl resin layer easily, the situation that is difficult to control thickness becomes many, nor obtains flatness easily.On the contrary, if surpass 50 μ m, then cost increases, and the effect that obtains is little, is uneconomic.
In addition,, on resin layer surface, carry out the Ke Luona discharge process, binder course preferably is set for the cohesive that makes itself and following ink receiving layer improves.
And, use as the base material of resin-coated paper under the situation of paper, as paper base material, the preferred use makes as main material with wood pulp.The wood pulp that be fit to use can be various chemical pulps, mechanical pulp, regenerated paper pulp etc., for paper power and the flatness of adjusting these paper pulp, copy paper adaptability etc., can adjust beating degree by beater.Beating degree is not particularly limited, and what be generally 250～550ml (CSF:JIS-P-8121) degree is preferred range.Can preferably use not chloride paper pulp such as so-called ECF, TCF paper pulp.In addition, in case of necessity, can in wood pulp, add pigment.As pigment, preferably use talcum, calcium carbonate, clay, kaolin, fire kaolin, silica, zeolite etc.By adding pigment, though can improve opacity and flatness,, the situation of paper power reduction is arranged then if add superfluously, the addition of pigment is that the degree of 1～20 quality % is preferred with respect to wood pulp.
(ink receiving layer)
In the present invention, on the supporting mass of low-permeable or non-gas permeability, form one deck ink receiving layer at least.One deck at least of ink receiving layer contains pigment and adhesive, and is necessary, can also contain cationic compound.
In the present invention, the ink receiving layer of formation can be one deck, also can be multilayer.Ink receiving layer is under the situation of multilayer, and employed pigment and adhesive can change at each ink receiving layer.At this moment, for example, ink receiving layer is by two-layer when constituting, if in the ink receiving layer that contacts with gloss layer (the 1st layer),, use very fine pigment in order to improve glossiness, and the ink receiving layer that contacts with supporting mass (the 2nd layer) uses the pigment of greater particle size by comparison, even then the 1st layer ink absorption is low, the 2nd layer ink absorption also can uprise, and therefore can keep or improve glossiness and ink absorption simultaneously.
In ink receiving layer, as with ink receiving layer that gloss layer contacts in the pigment that uses, what can exemplify is, cataloid, amorphous silica, aluminium oxide, aluminium hydroxide, magnesium carbonate, calcium carbonate, kaolin, fire transparent or Chinese white such as kaolin, can independent or two or more mixing use.
Particularly preferred pigment is cataloid, aluminium oxide or amorphous silica.Wherein, amorphous silica is an offspring, and its inside has the space, therefore compare with the situation of using primary particle cataloid and aluminium oxide, even the ratio of pigmental resin is low, also be difficult to cause the problem of ink absorption aspect, therefore be preferred especially the use.
As amorphous silica, the specific area that will record by nitrogen adsorption method is 300m
2/ g～1000m
2/ g, pore volume is that the liquid that disperses with the colloid shape of the silicon dioxide particles of 0.4ml/g～2.0ml/g is as inoculation liquid (シ-De liquid), in this inoculation liquid, in the presence of alkali, add the feed liquid that comprises the active silicic acid aqueous solution and/or alkoxy silane in the mode of a small amount of increase, make the silicon dioxide particles growth, also can use the specific area that records by nitrogen adsorption method to be 100m
2/ g～400m
2/ g, average aggregate particle size is 20nm～300nm, and pore volume is the silicon dioxide particles dispersion liquid of the silicon dioxide particles of 0.5ml～20ml/g with the dispersion of colloid shape.
Use at the ink receiving layer that contacts with gloss layer under the situation of amorphous silica, preferably using average primary particle diameter is 3～70nm, more preferably 5～40nm.In addition, amorphous silica preferably uses below the average aggregate particle size 1.3 μ m, more preferably the silica of 10～700nm.If average aggregate particle size is below the 13 μ m, the surface area mode standard diameter that pore is distributed is below the 100nm, thereby obtains not having the coating in crack easily, and some repeatability, ink absorption are good, and the raising of the transparency of ink receiving layer, it is also high therefore to write down concentration.
Herein, average aggregate particle size is meant, coating with 5% silica dispersions with equal phase mixer at the dispersion liquid of dispersed with stirring after 30 minutes under the 5000rpm, as sample, observe with electron microscope (SEM and TEM), take 10,000～400,000 times electron micrograph, the coupling (マ-チ ソ) of measuring the aggregate particle size in the 5cm square directly, averaging obtains that (" particulate Ha Application De Off Star Network " is towards storehouse bookstore, p52 published in 1991).
Manufacture method to the pigment of average aggregate particle size below 1.3 μ m is not particularly limited, for example, can be for passing through generally commercially available block raw materials such as synthetic amorphous silica, obtain sediment by liquid-phase chemical reaction, method through the mechanical system pulverizing, metal alkoxide is added the sol-gel process of water decomposition, and the high temperature of gas phase adds method preparation such as water decomposition.As mechanical system, what can exemplify is that ultrasonic wave, high speed are rotated mill, tumbling mill, container drive medium mill, medium stirring mill, aeropulverizer, sand mill, nanocone drill bit (Na ノ マ イ ザ-) etc.
In addition, be not particularly limited, be preferably 150m for the specific area of micro pigment
2More than/the g.Herein, the specific area of micro pigment is, with micro pigment drying under 105 ℃, with the SA3100 type of Coulter company preparation, under 200 ℃, after vacuum outgas in 2 hours, the nitrogen adsorption of the powder sample that mensuration obtains, the specific area that calculates by the t method.Specific area is the surface area of micro pigment unit mass, and this value is big more, and primary particle is more little, and it is complicated that the shape of offspring becomes easily, and it is big that the capacity in the pore becomes, and can think the ink absorption raising.
The specific area mode standard diameter that pore distributes refers to, and tries to achieve the specific area pore diameter by following method and distributes, and is represented by maximum wherein.
In the present invention, pore diameter distributes and to refer to, and the diameter in the space (pore) that forms between particle in the recording layer of measuring by mercury injection method distributes.Pore diameter distribute can by the pore volume distribution curve of trying to achieve by mercury injection method as calculated pore diameter distribute (differential curve) try to achieve.Mercury injection method also be known as mercury Port ロ シ メ ト リ-, as refractory body 41 volume, described in No. 6 297～303 pages/1989, be meant the method for measuring porous body pore structure (pore diameter and pore volume) that is widely used in.The principle of this mensuration is, utilizes the surface tension of mercury big, if therefore do not exert pressure, then can not invade in the pore of porous body.That is to say, will represent with following general formula (1) the relation between mercury applied pressure and this moment pore diameter that can invade of mercury.
P＝-4σcosθ/D (1)
Herein, P: mercury is invaded required pressure (psi) in the pore
σ: the surface tension of mercury (480dyn/cm)
θ: the contact angle of mercury (140 °)
D: pore diameter (μ m).
In the above-mentioned formula of value substitution (1), obtain being used to try to achieve the general formula (2) of pore diameter D with σ, θ.
D＝213/P (2)
It is to utilize above-mentioned principle that pore diameter distributes, change gradually to mercury applied pressure P, the volume of the mercury of invading in mensuration pore this moment is pore capacity V just, depict according to the pore diameter D of above-mentioned (2) formula conversion and the relation of pore capacity V, the differential coefficient (dV/dD) of trying to achieve this relation curve is obtained as transverse axis with pore diameter D as the longitudinal axis.This pore diameter distribution curve has 1～2 maximum usually.
Among the present invention,, after on the film ink receiving layer being set, peel off down ink receiving layer, measure with cutter etc. for fear of the influence of supporting mass.When on film, measuring, use the pore of the film negligible film that distributes itself.
Pore diameter is more little, and the glossiness of recording layer is high more.In the present invention, in order to obtain the such high gloss inkjet recording material of silver salt photo, the maximum that the pore diameter of existence distributes is below the 100nm, is preferably below the 80nm, more preferably below the 70nm.If there be the maximum bigger than 100nm, then glossiness and some repeatability reduce, and recording layer is easy to generate the crack.
In addition, when ink receiving layer is a multilayer, under for example two-layer situation, not with the ink receiving layer that ink receiving layer also can contain with gloss layer contacts of gloss layer contact in the identical pigment of pigment that uses.
At particularly preferred pigment is amorphous silica, with in the ink receiving layer that gloss layer contacts do not use under the situation of amorphous silica, average primary particle diameter is that 3～70nm and average aggregate particle size are to be preferred below the 20 μ m, and average primary particle diameter is that 5～40nm and average aggregate particle size are more preferred below the 1.3 μ m.
And, not with ink receiving layer that gloss layer contacts in the amorphous silica that uses average aggregate particle size than with ink receiving layer that gloss layer contacts in the average aggregate particle size of the amorphous silica that uses be greatly preferred.This be because, not with ink receiving layer that gloss layer contacts in the average aggregate particle size of the amorphous silica that uses, with with ink receiving layer that gloss layer contacts in the average aggregate particle size of the amorphous silica that uses compare under the little situation ink absorption reduction sometimes.
As the adhesive that in ink receiving layer, uses, be not particularly limited, for example, can from following substances, suitably select to use: water-soluble resins such as polyvinyl alcohol (below be called PVA), Pioloform, polyvinyl acetal, polymine, polyvinylpyrrolidone, polyacrylamide, the water-dispersed resin of the polyvinyl latex of acrylic polymer latex, ethylene-vinyl acetate copolymer etc. etc.Wherein, from the good angle of bonding effect, PVA is preferred.
As adhesive, to use under the situation of PVA for example, the degree of polymerization is preferably 3000～5000.By using the PVA of the degree of polymerization in above-mentioned scope, can reduce the crack in the ink receiving layer, and also reduce, so the decline of ink absorption speed also reduces by the swelling that ink solvent causes.In addition, the saponification degree preferred range of PVA is 90～100%, more preferably 95～100%.If saponification degree is lower than 90%, then because the PVA swelling that causes of ink solvent, ink absorption speed might reduce.
As the content of adhesive, for pigment, be preferably 3～100 quality %, more preferably about 5～30 quality %.If adhesive is lower than 3 quality %, be easy to generate the crack in the ink receiving layer, if greater than 100 quality %, then adhesive will stop up the pore that is formed by pigment, and the possibility that causes the ink absorption capacity to descend is arranged.
In ink receiving layer, identical with following gloss layer in case of necessity, the dyestuff in the set ink provides resistance to water, and improves record concentration, can add cationic compound.As described below as cationic compound, can exemplify those that can in gloss layer, add.In addition, in gloss layer and ink receiving layer, can suitably select different types of cationic compound, even can also use multiple cationic compound simultaneously.
In ink receiving layer, identical with gloss layer, for the paper used for recording surface is stripped down reposefully, can add release agent in case of necessity from felt wrapped roll.Will be described later about release agent, can exemplify and to add in the gloss layer those to.In gloss layer and ink receiving layer, can suitably select different types of release agent, even can also use multiple release agent simultaneously.
In addition, in ink receiving layer, except that above-mentioned, also can be added on various auxiliary agents such as various pigment that common coated paper uses in making, dispersant, tackifier, defoamer, colouring agent, antistatic agent, anticorrisive agent.
Ink receiving layer is, be coated on the supporting mass by the coating liquid that will be dispersed with composition such as above-mentioned pigment in solvent, and is dry and form.Solvent as coating liquid is not particularly limited, and owing to reasons such as coating characters, water is preferred.
The coated weight of ink receiving layer adds up to 5～70g/m
2Be preferred, 10～50g/m
2Be preferred, 15～40g/m
2More preferred.In addition, it is preferred that the thickness of coating adds up to 7～105 μ m, and 15～75 μ m are preferred, and 22～60 μ m are more preferred.At the not enough 5g/m of coated weight
2Situation under, not only gloss layer can not fully form, and by the time ink absorption reduction, it is bad that recordability becomes, and if coated weight surpasses 70g/m
2, then strength of coating reduces, and when cutting out of paper used for recording adds man-hour and transmit paper used for recording etc. with printer, may cause fault easily.
Apply operation carry out once also can, but also can carry out repeatedly.Carry out repeatedly if apply operation, then ink receiving layer also can be multilayer.In addition, apply, suppressing to apply more coating liquid when the crack takes place, can make the ink absorption capacity of ink receiving layer become big by coating liquid being divided into repeatedly.
Coating unit as ink receiving layer can use various known coating units such as scraper-type coating machine, air knife doctor knife coater, roll coater, drawdown rod, gravure coating machine, compression mod (ダ イ) coating machine, curtain formula coating machine.Particularly, for corresponding to width wide coating physical property, coated weight, the air knife doctor knife coater is suitable for.In addition, for the homogeneity that makes coated weight is good, particularly for the gloss type ink-jet recording paper of the meticulous record purpose of height, compression mod coating machine and curtain formula coating machine are preferred painting methods.
As the drying means of filming, be not particularly limited, various heat drying modes such as existing public heated-air drying, gas heater drying, dielectric drying, electric heater drying, infrared heater drying, laser drying, electron beam drying all are suitable for.
＜coating fluid is supplied with operation 〉
Below, on ink receiving layer 3, supply with the coating fluid of the coating fluid 4 that is used to form gloss layer and supply with operation.
(gloss layer)
In the present invention, gloss layer as principal component, contains any other compositions such as release agent with pigment.
If use primary particles such as cataloid and aluminium oxide in gloss layer, then because voidage reduces, ink absorption speed reduces easily.For this reason, the thickness of preferred gloss layer is 0.02～4 μ m, more preferably 0.05～2 μ m.In addition, the angle that has both from ink absorption capacity and ink absorption speed considers that what the thickness of gloss layer accounted for the ink receiving layer general thickness is preferred below 1/10.More preferably below 1/20, also preferred below 1/30.
Be used to form the coating fluid of gloss layer, allocate by these compositions are dispersed in the suitable decentralized medium.
As pigment contained in the gloss layer, can exemplify, cataloid, amorphous silica, aluminium oxide, aluminium hydroxide, magnesium carbonate, calcium carbonate, kaolin, fire transparent or Chinese whites such as kaolin.Wherein particularly preferred pigment is cataloid, aluminium oxide or amorphous silica.
Use cataloid or aluminium oxide, because the glossiness raising is therefore preferred especially.The average primary particle diameter of cataloid or aluminium oxide is preferably 5～100nm, more preferably 10～80nm.20～70nm more preferably.Under the situation of the not enough 5nm of average grain diameter, ink absorption reduction sometimes, and when average grain diameter surpassed 100nm, because the transparency reduces, lettering concentration might descend.
Use under the situation of amorphous silica, preferred average primary particle diameter is 5～100nm, more preferably 5～40nm.In addition, it is below the 1 μ m that amorphous silica preferably uses average aggregate particle size, more preferably 10～700nm.
Though water-base resin might make ink absorption decline, also can use resin system gloss under the necessary situation.
As what water-base resin can exemplify be, polyvinyl alcohol, cation-modified polyvinyl alcohol, polyvinylpyrrolidone and copolymer thereof, poly-methyl hydroxylated cellulose, cellulose derivatives such as carboxy methyl cellulose, oxidized starch, modified starch series such as cationic starch, casein, soybean protein, synthetic proteinses etc. are protein-based, polystyrene resin, polybutadiene, polyurethane resin, polyacrylic resin, polyvinyl acetate resin, water-base resin and copolymers thereof such as Corvic, modifier etc., they can separately or be used in combination, particularly, the copolymer of styrene acrylic system is preferred.
The average grain diameter of water-base resin is to be preferred in the scope of 20～150nm, under the situation of not enough 20nm, and ink absorption reduction sometimes, and surpass under the situation of 150nm, the transparency reduces sometimes, and lettering concentration descends.
The glass transition temperature of water-base resin is preferred in 50～150 ℃ of scopes.When glass transition temperature was lower than 50 ℃, the film forming of gloss layer was excessive when drying sometimes, and the porous of gloss layer reduces, ink absorption decline.Be higher than under 150 ℃ the situation, sometimes film forming deficiency, gloss and undercapacity.
With respect to the pigment of 100 mass parts, the use level of water-base resin is preferably 0～50, more preferably in 0～10 scope.
In case of necessity, identical with ink receiving layer in gloss layer, the dyestuff in the set ink provides resistance to water, improves record concentration, can add cationic compound.
As what cationic compound can exemplify be: the polynary amine of polyalkylene or its derivatives such as poly-ethylidene polyamine and polytrimethylene polyamine, contain secondary amine, the acrylic resin of tertiary amine groups and quaternary ammonium group, the polyethylene amine, polyethylene amidine class, the dicyano resin cation of dicyandiamide-formalin condensation polymer representative, the polyamine cation resin of dicyandiamide-diethylenetriamines condensation polymer representative, epichlorohydrine-dimethyl amine addition polymers, diallyldimethylammonium chloride-sulfur dioxide copolymer, diallylamine salt-sulfur dioxide copolymer, the diallyldimethylammonium chloride polymer, the polymer of allyl amine salt, dialkylamine (methyl) acrylate quaternary salt polymer, acrylamide-cationic compounds such as diallylamine salt copolymer, acrylonitrile and N-vinyl acrylic amidine salt acid polymer, and add the water decomposition thing, poly-amidine is a resin, they can use separately, also can multiplely be used in combination.
In addition, consider that the cationization cataloid is preferred especially the use from ink absorption speed and the good angle of lettering concentration.
In being used to form the coating fluid of gloss layer, except that mentioned component, in order from felt wrapped roll, successfully to peel off on the surface of the coating liquid layer that will form the also preferred release agent that adds.
As what release agent can exemplify be: stearic acid, oleic acid, fatty acids such as palmitic acid, and their sodium, potassium, calcium, zinc, the salt of ammonium etc., stearmide, fatty acid acyl amines such as ethylenebisstearamide and di-2-ethylhexylphosphine oxide stearmide, microwax, paraffin, aliphatic hydrocarbons such as Tissuemat E, cetanol, senior alcohols such as stearyl alcohol, refined oil (ロ-ト oil), grease class and lipids such as lecithin, fluorine-containing various surfactants such as surfactant, fluorine such as tetrafluoroethylene fluorocarbon polymer and ethene-tetrafluoroethylene fluorocarbon polymer based polymer etc.
Wherein, particularly preferably be aliphatic hydrocarbon or derivatives thereof and modifier, aliphatic acid or its salt, lipid, but wherein preferably use Tissuemat E, preferably use stearic acid or oleic acid, preferably use lecithin as lipid as aliphatic acid as aliphatic hydrocarbon.
In addition, in the gloss layer, except that above-mentioned, also can suitably be added on common removing and cover various auxiliary agents such as the various pigment of use in the paper manufacturing, dispersant, tackifier, defoamer, colouring agent, antistatic agent, anticorrisive agent.
As in order to allocate the decentralized medium that the coating fluid that is dispersed with mentioned component is used, be not particularly limited, but based on reasons such as coatings, water is preferred.
The concentration of the total solid in coating fluid is preferably 0.1～15 quality %, more preferably 0.5～10 quality %.
The coating weight of gloss layer is counted 0.01～3g/m with dry mass
2Be preferred, 0.03～2g/m more preferably
2, also be preferably 0.05～1g/m
2The not enough 0.01g/m of coating weight
2The time, be difficult to form enough gloss layers, so the easy step-down of glossiness.Surpass 3g/m and work as coating weight
2The time, obtain glossiness easily, but ink absorption and the easy step-down of record concentration.
(voidage)
Voidage is because can be by above-mentioned mercury injection method mensuration pore volume, and can easily measure.
For ink can fully be absorbed, the voidage a of ink receiving layer, preferred 45＜a＜80%.55≤a≤75 more preferably.If voidage a is lower than 45%, then ink absorption speed reduces, and when it surpassed 80%, the layer of ink receiving layer itself became fragile, and therefore problems such as coating stripping are arranged.
For making gloss become enough high, the voidage b of gloss layer is preferably 10＜b≤45%.20≤b≤40 more preferably.If voidage b is lower than 10%, then ink absorption is obstructed, so ink absorption speed reduces significantly.In addition, if voidage b surpasses 45%, then surface smoothing reduction, so gloss might descend.
And, a＞b, and a-b＞25.A-b≤25, then glossiness and ink absorption can not average out, and therefore problem is arranged.
＜pressurization operation 〉
Secondly, the operation of pressurizeing, promptly during the coating fluid of supplying with 4 is wetting state or partial desiccation state, for the face of supplying with coating fluid 4 is contacted with felt wrapped roll 5, when being pressurizeed between felt wrapped roll 5 and pressure roll 6, passes through support 2, after forming coating liquid layer 7, release-coated liquid layer 7 from the felt wrapped roll 5 immediately.
For the face of supplying with coating fluid 4 is contacted with felt wrapped roll 5,, between the felt wrapped roll 5 and pressure roll 6 of heating,, on ink receiving layer 3, form coating liquid layer 7 by pressure roll 6 pressurizations with the coating fluid 4 under wetting or the partial desiccation state.At this moment, make coating liquid layer 7 closely attached on the ink receiving layer 3, formed the homogeneous film in no crack by pressure and temperature.
After the pressurization operation, also can carry out coating liquid layer 7 at dry in addition drying process such as the dry section of drier 9 grades.
From the operability of drying condition etc., the cohesive of ink receiving layer, the glossiness on gloss layer surface is set out, and the surface temperature of felt wrapped roll is preferably in 40～130 ℃ of scopes, is preferably in 70～120 ℃ the scope.Under the situation that the surface temperature deficiency of felt wrapped roll is 40 ℃, the adhesive film forming difficulty in the coating liquid layer, the surface strength of ink-jet recording paper might reduce, with the cohesive deterioration of ink receiving layer.Surpass under 130 ℃ the situation, the film forming of the adhesive in the coating liquid layer is carried out excessively, so the ink absorption reduction, coating fluid 4 boilings, and glassy surface might worsen.
In addition, from good heat resistance, can obtain good specularity aspect, felt wrapped roll is preferably metallic roll.And, give on the surface under the situation of the so-called semi-glossy paper that fine concavo-convex making glossiness reduces, also can on metallic roll, give fine concavo-convex.The average line center roughness Ra of felt wrapped roll changes according to the gloss of target, for example, and below the 10 μ m.
For make and above-mentioned felt wrapped roll between pressurization more even, the material of pressure roll is preferably heat stable resin system.
Pressurization by pressure roll is to make the line pressure between felt wrapped roll and the pressure roll be preferably 50～3500N/cm, and more preferably 200～3000N/cm carries out.Under the situation of the not enough 50N/cm of line pressure between felt wrapped roll and the pressure roll, line pressure is difficult to the homogeneous that becomes, glossiness descends, coating liquid layer 7 descends with respect to the cohesive of ink receiving layer 3, the crack might appear in the surface, when surpassing under the situation of 3500N/cm, because ink-jet recording paper excessively pressurizes, destroyed the space of ink receiving layer and gloss layer, so ink absorption might descend.
＜dry (damping) operation 〉
In the present invention, the moisture in the ink-jet recording paper 1 after peeling off from felt wrapped roll 5 (supporting mass 2, ink receiving layer 3 and coating liquid layer 7) is in wetting state or partial desiccation state.The moisture of coating is subjected to the influence of the coating weight of ink receiving layer and gloss layer greatly, for such as 7～100%.
After peeling off from felt wrapped roll 5, during batching, reach under the situation of equilibrium water conten with reel, do not need the damping drying device, but it is fast at coating speed, in the supporting masses such as paper 2 under the moisture high situation, after peeling off from felt wrapped roll 5, during batching with reel, the drying process that has the damping operation of humidity control device or have a drying device is necessary.The ability of damping or drying device and specification are suitably set according to the moisture that ink-jet recording paper is contained when felt wrapped roll 5 is peeled off and the difference between the equilibrium water conten and coating speed.
And, the surface of the gloss layer 8 of above-mentioned formation, in order to obtain the such feel of silver salt photo, 75 ° of surface glosses (JIS P 8142) are preferably more than 70%, more preferably more than 75%, also be preferably more than 80%, and the mapping (JIS H 8686-2) when using width as the optical comb of 2.0mm is preferably more than 55%, more preferably more than 57%, also be preferably more than 60%, most preferably be more than 65%.
And, among Fig. 1, felt wrapped roll 5 disposes side by side with pressure roll about 6, felt wrapped roll 5 forms the concentrated place of coating fluid with the tangent line top of pressure roll 6, supporting mass longitudinally passes through, but also can supply with coating fluid 4 from ink receiving layer 3 for example with felt wrapped roll 5 and pressure roll 6 configuration side by side up and down, supporting mass is along laterally passing through.
Below exemplify embodiment so that the present invention more specifically to be described, still not as limitation of the present invention.In addition, part and % among the embodiment are mass parts and quality % except that specifying.
(silicon dioxide gel A)
Commercially available sedimentation silica (trade name: Off ア イ Application シ-Le X-45, ト Network ヤ マ corporate system, average primary particle diameter is 10nm, specific area is 280m
2/ g, average aggregate particle size is 4.5 μ m) carry out aqueous dispersion and pulverize by sand mill after, with the nanocone drill bit (trade name: Na ノ マ イ サ-, Na ノ マ イ ザ-corporate system), grinding dispersion after the classification, is modulated 10% dispersion liquid that is obtained by average aggregate particle size 80nm repeatedly.In this dispersion liquid, add 10 parts of diallyldimethylammonium chlorides (trade name: ユ ニ ヤ Application ス CP-103 as cationic compound, セ Application カ corporate system), after causing the tackify of the aggegation of pigment and dispersion liquid, reuse the nanocone drill bit, grinding dispersion repeatedly, modulation obtains silicon dioxide gel A by 8% dispersion liquid that average aggregate particle size 250nm forms.
(silicon dioxide gel B)
Commercially available sedimentation silica (trade name: Off ア イ Application シ-Le X-45, ト Network ヤ マ corporate system, average primary particle diameter is 10nm, specific area is 280m
2/ g, average aggregate particle size is 4.5 μ m) carry out aqueous dispersion and pulverize by sand mill after, with the nanocone drill bit (trade name: Na ノ マ イ ザ-, Na ノ マ イ サ-corporate system), grinding dispersion after the classification, is modulated 10% dispersion liquid that is obtained by average aggregate particle size 80nm repeatedly.In this dispersion liquid, add 10 parts of diallyldimethylammonium chlorides (trade name: ユ ニ ヤ Application ス CP-103 as cationic compound, セ Application カ corporate system), after causing the tackify of the aggegation of pigment and dispersion liquid, reuse the nanocone drill bit, grinding dispersion repeatedly, modulation obtains silicon dioxide gel B by 8% dispersion liquid that average aggregate particle size 1.3 μ m form.
(silicon dioxide gel C)
Commercially available gel method silica (trade name: ニ Star プ ジ エ Le AZ600, Japanese シ リ カ corporate system, average primary particle diameter is 10nm, specific area is 300m
2/ g) carry out aqueous dispersion and pulverize by sand mill after, with the nanocone drill bit (trade name: Na ノ マ イ ザ-, Na ノ マ イ ザ-corporate system), grinding dispersion repeatedly, after the classification, 10% dispersion liquid that modulation is obtained by average aggregate particle size 80nm.In this dispersion liquid, add 10 parts of diallyldimethylammonium chlorides (trade name: ユ ニ ヤ Application ス CP-103 as cationic compound, セ Application カ corporate system), after causing the tackify of the aggegation of pigment and dispersion liquid, reuse the nanocone drill bit, grinding dispersion repeatedly, modulation obtains silicon dioxide gel C by 8% dispersion liquid that average aggregate particle size 300nm obtains.
(silicon dioxide gel D)
Commercially available fumed silica (trade name: レ オ ロ シ-Le QS-30, ト Network ヤ マ corporate system, average primary particle diameter is 10nm, specific area is 300m
2/ g) carry out aqueous dispersion and pulverize by sand mill after, with the nanocone drill bit (trade name: Na ノ マ イ ザ-, Na ノ マ イ ザ-corporate system), grinding dispersion repeatedly, after the classification, 10% dispersion liquid that modulation is obtained by average aggregate particle size 80nm.In this dispersion liquid, add 10 parts of diallyldimethylammonium chlorides (trade name: ユ ニ ヤ Application ス CP-103 as cationic compound, セ Application カ corporate system), after causing the tackify of the aggegation of pigment and dispersion liquid, reuse the nanocone drill bit, grinding dispersion repeatedly, modulation obtains silicon dioxide gel D by 8% dispersion liquid that average aggregate particle size 300nm obtains.
(silicon dioxide gel E)
Commercially available sedimentation silica (trade name: Off ア イ Application シ-Le X-45, ト Network ヤ マ corporate system, average primary particle diameter is 10nm, average aggregate particle size is 4.5 μ m) carry out aqueous dispersion and pulverize by sand mill after, with the nanocone drill bit (trade name: Na ノ マ イ ザ-, Na ノ マ イ ザ-corporate system), grinding dispersion repeatedly, after the classification, modulation obtains silicon dioxide gel E by 20% dispersion liquid that average aggregate particle size 500nm obtains.
(alumina sol A)
Commercial alumina particle (trade name: AKP-G020, BET specific area 200m
2/ g, gama-alumina, sumitomo chemical company system) by after the sand mill grinding dispersion, use the grinding dispersion of マ イ Network ロ Off Le イ ダ イ ザ-repeatedly again, modulation obtains alumina sol by 10% dispersion liquid that average aggregate particle size 200nm obtains.
(supporting mass A)
To pull an oar, to shine kraft pulp (NBKP) to CSF (JIS P-8121) for the coniferous tree of 250ml be that the broad leaf tree of 250ml is shone kraft pulp (LBKP) with pulling an oar to CSF, mixes at 2: 8 with mass ratio, and modulation concentration is 0.5% pulp.In this pulp, with respect to the absolute dry mass of paper pulp, add cationic starch 2.0%, alkyl ketene dimer 0.4%, anionization polyacrylamide resin 0.1%, polyamide polyamine epichlorohydrine resin 0.7%, fully stir and make it dispersion.
The pulp of above-mentioned composition is copied paper with fourdrinier, and by drier, size presser, calender, making quantitatively is 180g/m
2, density 1.0g/cm
3Body paper.To be carboxy-modified polyvinyl alcohol and sodium chloride mix with 2: 1 mass ratio the size press liquid that uses in the above-mentioned size press operation, carried out heat of solution to wherein adding entry, and to be modulated into concentration be 5% solution, and this size press liquid is to add up to 25ml/m
2Amount in the two sided coatings of paper, thereby supported body A (air permeability: 300 seconds).
(supporting mass B)
On the two sides of the body paper of above-mentioned supporting mass A with section's roller discharge process after, will mix the following polyolefine resin composition 1 of dispersion with coated weight 25g/m with Banbury banburying device
2Be coated to felt face one side of supporting mass A, and with following polyolefine resin composition 2 with coated weight 20g/m
2With wire side one side that machine (320 ℃ of melt temperatures) is coated to supporting mass A that melt extrudes with T pattern head, the felt face one side chill roll of minute surface, wire side one side is carried out cooling curing with the chill roll of asperities, obtain smoothness (Wang Yan formula, J.TAPPI No.5) be 6000 seconds, opacity (JIS P8138) is 93% resin-coated supporting mass B (air permeability:＞10000 seconds).
(polyolefine resin composition 1)
With long chain type ldpe resin (density 0.926g/cm
3, melt index (MI) 20g/10 branch) and 35 parts, ldpe resin (density 0.919g/cm
3Melt index (MI) 2g/10 branch) 50 parts, 15 parts of anatase titanium dioxides (trade name: A-220, the former industry corporate system of stone), 0.1 part of zinc stearate, 0.03 part of antioxidant (trade name: Irganox 1010, チ バ ガ イ ギ-corporate system), ultramarine (trade name: blue or green mouthful of ultramarine NO.2000, first changes into corporate system) 0.09 part, fluorescent whitening agent (trade name: UVITEXOB, チ バ ガ イ ギ-corporate system) mixes for 0.3 part mutually, as polyolefine resin composition 1.
(polyolefine resin composition 2)
With high-density polyethylene resin (density 0.954g/cm
3, melt index (MI) 20g/10 branch) and 65 parts, ldpe resin (density 0.919g/cm
3, melt index (MI) 2g/10 branch) and 35 parts of phase melting mixing, as polyolefine resin composition 2.
(supporting mass C)
To pull an oar, to shine kraft pulp (NBKP) to CSF (JIS P-8121) for the coniferous tree of 250ml be that the broad leaf tree of 250ml is shone kraft pulp (LBKP) with pulling an oar to CSF, mixes at 2: 8 with mass ratio, and modulation concentration is 0.5% pulp.In this pulp, with respect to the absolute dry mass of paper pulp, add polyacrylamide resin 0.1%, the polyamide polyamine epichlorohydrine resin 0.7% of cationic starch 2.0%, alkyl ketene dimer 0.4%, cloudy sonization, fully stir and make it dispersion.
The pulp of above-mentioned composition is copied paper with fourdrinier, and by drier, size presser, calender, making quantitatively is 150g/m
2, density 0.75g/cm
3Body paper, supported body C (air permeability: 35 seconds).
Embodiment 1
Be mixed into 24 part 5% polyvinyl alcohol (trade name: PVA-135H, Network ラ レ corporate system, the degree of polymerization: 3500, saponification degree: more than 99%) in 100 parts of silicon dioxide gel A, be coated with on supporting mass B with the Meyer excellent coating machine that winds the line, coating weight is 25g/m
2(coating layer thickness is 38 μ m), drying is provided with ink receiving layer.Secondly, cataloid (trade name: ス ノ-テ Star Network ス 50 with average grain diameter 25nm, daily output chemical company system) is diluted to 10%, as shown in Figure 1, on ink receiving layer, applies, on the minute surface cylinder in the chromium plating calendering of 100 ℃ of surface temperatures during the wetting state, with line pressure 2000N/cm pressure welding, form gloss layer, at 100 ℃, dry 15 minutes, obtain ink-jet recording paper.In addition, the coated weight of gloss layer is 0.5g/m
2, thickness is 1 μ m.
Except that replace the silicon dioxide gel A of 100 parts of embodiment 1 with 100 parts of silicon dioxide gel B, identical with embodiment 1, obtain ink-jet recording paper.
Except that replace the silicon dioxide gel A of 100 parts of embodiment 1 with 100 parts of silicon dioxide gel C, identical with embodiment 1, obtain ink-jet recording paper.
Embodiment 4
Except that replace the silicon dioxide gel A of 100 parts of embodiment 1 with 100 parts of silicon dioxide gel D, identical with embodiment 1, obtain ink-jet recording paper.
Except that replace the silicon dioxide gel A of 100 parts of embodiment 1 with 100 parts of alumina sol A, identical with embodiment 1, obtain ink-jet recording paper.
Embodiment 6
Sneak into 24 part of 5% polyvinyl alcohol (trade name: PVA-135H, Network ラ レ corporate system, the degree of polymerization: 3500, saponification degree: more than 99%) in 100 parts of silicon dioxide gel E, apply on supporting mass B with the Meyer excellent coating machine that winds the line, coated weight is 20g/m
2, drying is provided with the 2nd ink receiving layer.On the 2nd ink receiving layer, in 100 parts of silicon dioxide gel A, sneak into 24 part of 5% polyvinyl alcohol (trade name: PVA-135H, Network ラ レ corporate system, the degree of polymerization: 3500, saponification degree: more than 99%), apply with the Meyer excellent coating machine that winds the line, coated weight is 5g/m
2, drying is provided with the 1st ink receiving layer.The gross thickness of ink receiving layer is 38 μ m.Secondly, with cataloid (trade name: ス ノ-テ Star Network ス 50, daily output chemical company system) dilution is 10%, is coated on the 1st ink receiving layer, during wetting state, on the chromium plating calendering minute surface cylinder of 100 ℃ of surface temperatures, with line pressure 2000N/cm pressure welding, form gloss layer, at 100 ℃, dry 15 minutes, obtain ink-jet recording paper.In addition, the coated weight of gloss layer is 0.5g/m
2, thickness is 1 μ m.
Embodiment 7
In the formation of the 2nd ink receiving layer of embodiment 6, remove (Network レ-ス デ PVC ソ Application corporate system, specific area: 280m with サ イ ロ ジ エ Star ト 703A
2/ g, average aggregate particle size 300nm) replace beyond 100 parts of silicon dioxide gel E, identical with embodiment 6, obtain ink-jet recording paper.
Embodiment 8
Except cataloid (trade name: ス ノ-テ Star Network ス AK with average grain diameter 15nm, daily output chemical company system) cataloid (trade name: ス ノ-テ Star Network ス 50 of replacement embodiment 6, daily output chemical company system) in addition, identical with embodiment 6, obtain ink-jet recording paper.
Except the cataloid (trade name: ス ノ-テ Star Network ス 50, daily output chemical company system) that replaces embodiment 6 with silicon dioxide gel A in addition, identical with embodiment 6, obtain ink-jet recording paper.
Embodiment 10
Except aluminium oxide (trade name: silicon dioxide gel 520 with average grain diameter 15nm, daily output chemical company system) cataloid (trade name: ス ノ-テ Star Network ス 50 of replacement embodiment 6, daily output chemical company system) in addition, identical with embodiment 6, obtain ink-jet recording paper.
Embodiment 11
Except cataloid (trade name: ス ノ-テ Star Network ス CM with average grain diameter 25nm, daily output chemical company system) cataloid (trade name: ス ノ-テ Star Network ス 50 of replacement embodiment 6, daily output chemical company system) in addition, identical with embodiment 6, obtain ink-jet recording paper.
Embodiment 12
Except cataloid (trade name: ス ノ-テ Star Network ス O40 with average grain diameter 25nm, daily output chemical company system) cataloid (trade name: ス ノ-テ Star Network ス 50 of replacement embodiment 6, daily output chemical company system) in addition, identical with embodiment 6, obtain ink-jet recording paper.
Embodiment 13
In the formation of the gloss layer of embodiment 12, except replacing line pressure 2000N/cm to carry out pressure welding, form beyond the gloss layer with line pressure 3500N/cm, identical with embodiment 12, obtain ink-jet recording paper.The thickness of ink receiving layer is 35 μ m, and the thickness of gloss layer is 0.8 μ m.
Embodiment 14
In the formation of the gloss layer of embodiment 12, except replacing line pressure 2000N/cm to carry out pressure welding, form beyond the gloss layer with line pressure 50N/cm, identical with embodiment 12, obtain ink-jet recording paper.The thickness of gloss layer is 1.5 μ m.
Embodiment 15
In the formation of the gloss layer of embodiment 12, except the chromium plating calendering minute surface cylinder with 100 ℃ of the chromium plating calendering minute surface cylinder substitution list surface temperatures of 40 ℃ of surface temperatures carries out pressure welding, form beyond the gloss layer, identical with embodiment 12, obtain ink-jet recording paper.
Embodiment 16
Beyond supporting mass B with commercially available Dampler Ace (trade name: ユ Port GWG-140, ユ Port コ-Port レ-シ ヨ Application corporate system) replacement embodiment 12, identical with embodiment 12, obtain ink-jet recording paper.
Comparative example 1
Except replace the supporting mass B of embodiment 12 with supporting mass C, identical with embodiment 12, obtain ink-jet recording paper.
Comparative example 2
In embodiment 1, identical with embodiment 1 except not forming gloss layer, obtain ink-jet recording paper.
Embodiment 17
To 100 parts of gel method silica (trade name: サ イ ロ ジ エ Star ト P612, グ レ-ス デ PVC ソ Application corporate system, average primary particle diameter: 10nm, average aggregate particle size: sneak into 35 parts of silyl-modified polyvinyl alcohol (trade name: Network ラ レ Port バ-Le PVA R-1130 7.5 μ m), Network ラ レ corporate system, the degree of polymerization 1700), making it become concentration is 15% the 2nd ink receiving layer coating, with this coating with dried coated weight 15g/m
2Be coated on the supporting mass B with the compression mod coating machine.
Before the 2nd ink receiving layer of coating is used the coating drying, with dried coated weight 5g/m
2In 100 parts of silicon dioxide gel A, sneak into 30 parts of polyvinyl alcohol (trade name: Network ラ レ Port バ-Le PVA 135H with the coating of compression mod coating machine, Network ラ レ corporate system, the degree of polymerization 3500), the 1st ink receiving layer coating of concentration 8%, drying forms the 1st and the 2nd ink receiving layer.The thickness of the ink receiving layer of this moment is 28 μ m.
Secondly, with glass transition point 100 parts of 50 50 the compounds of the cataloid of 85 ℃ styrene-2-ethylhexyl acrylate copolymer resin and average grain diameter 30nm, as 5 parts of the alkyl vinyl ether maleic acid derivatives resins of viscosity modifier, 3 parts in lecithin and water as release agent are mixed together, disperse, the gloss layer coating of solid portion concentration 10% is coated on the 1st ink receiving layer, gloss layer coating is during wetting state, immediately on the minute surface cylinder of the chromium plating calendering of 100 ℃ of surface temperatures with line pressure 50kg pressure welding, obtain ink-jet recording paper.This moment, the dried coated weight of gloss layer coating was 2g/m
2The thickness of the gloss layer of this moment is 2.5 μ m.
Embodiment 18
In the 2nd ink receiving layer of embodiment 17, identical except replacing the 2nd ink receiving layer with the coating with coating with embodiment 17 with the 1st ink receiving layer, obtain ink-jet recording paper.The thickness of the ink receiving layer of this moment is 30 μ m.
Embodiment 19
Beyond supporting mass B with commercially available Dampler Ace (trade name: ユ Port GWG-140, ユ Port コ-Port レ-シ ヨ Application corporate system, air permeability:＞10000 seconds) replacement embodiment 17, identical with embodiment 17, obtain ink-jet recording paper.
Comparative example 3
Except replace the supporting mass B of embodiment 17 with supporting mass C, identical with embodiment 17, obtain ink-jet recording paper.
Embodiment 20
In 100 parts of silicon dioxide gel D, sneak into 24 part of 5% polyvinyl alcohol (trade name: PVA-135H, Network ラ レ corporate system, the degree of polymerization 3500, saponification degree: more than 99%), wind the line excellent coating machine with 25g/m with Meyer
2Coated weight on supporting mass B, apply dryly, ink receiving layer is set.The thickness of the ink receiving layer of this moment is 37 μ m.Secondly, cataloid (trade name: ス ノ-テ Star Network ス O40 with average grain diameter 25nm, daily output chemical company system) is diluted to 10%, is coated on the ink receiving layer, during wetting state, on the chromium plating calendering minute surface cylinder of 100 ℃ of surface temperatures, with line pressure 2000N/cm pressure welding, form gloss layer, then, 100 ℃ of dryings 15 minutes, obtain ink-jet recording paper.The thickness of the gloss layer of this moment is 1 μ m.
Embodiment 21
In 100 parts of silicon dioxide gel D, sneak into 24 part of 5% polyvinyl alcohol (trade name: PVA-135H, Network ラ レ corporate system, the degree of polymerization 3500, saponification degree: more than 99%), wind the line excellent coating machine with 25g/m with Meyer
2Coated weight on supporting mass B, apply dryly, ink receiving layer is set.The thickness of the ink receiving layer of this moment is 37 μ m.Secondly, cataloid (trade name: ス ノ-テ Star Network ス O40 to average grain diameter 25nm, daily output chemical company system) sneaks into 1 part of 2% polyvinyl alcohol (trade name: Network ラ レ Port バ-Le PVA R-1130 in, Network ラ レ corporate system, the degree of polymerization: 1170), be coated on the ink receiving layer with the Meyer excellent coating machine that winds the line,, obtain ink-jet recording paper 100 ℃ of dryings 15 minutes.The thickness of the gloss layer of this moment is 1.5 μ m.
Embodiment 22
Except cataloid (trade name: ス ノ-テ Star Network ス MP1040 with average grain diameter 100nm, daily output chemical company system) cataloid (trade name: ス ノ-テ Star Network ス O40 of replacement embodiment 20, daily output chemical company system) in addition, identical with embodiment 20, obtain ink-jet recording paper.
Embodiment 23
Except cataloid (trade name ス ノ-テ Star Network ス 20L with average grain diameter 45nm, daily output chemical company system) cataloid (trade name: ス ノ-テ Star Network ス O40 of replacement embodiment 20, daily output chemical company system) in addition, identical with embodiment 20, obtain ink-jet recording paper.
Embodiment 24
Except cataloid (trade name: ス ノ-テ Star Network ス XS with average grain diameter 5nm, daily output chemical company system) cataloid (trade name: ス ノ-テ Star Network ス 50 of replacement embodiment 20, daily output chemical company system) in addition, identical with embodiment 20, obtain ink-jet recording paper.
Embodiment 25
In the ink receiving layer of embodiment 20, except using polyvinyl alcohol (trade name: PVA-117, Network ラ レ corporate system, the degree of polymerization: 1700, saponification degree: more than 99%) replacement 24 parts of polyvinyl alcohol (trade name: PVA-135H, Network ラ レ corporate systems, the degree of polymerization 3500, saponification degree: more than 99%) in addition, identical with embodiment 20, obtain ink-jet recording paper.
＜test example 1 〉
75 kilsyth basalt face glossiness of the ink-jet recording paper that obtains by embodiment and comparative example, mapping property, wrinkling, the lettering reflecting feel, what ink absorption and lettering concentration were estimated the results are shown in the table 1.Measure with following method about each evaluation.
(75 ° of surface glosses)
With the method for record among the JIS P 8142, measure 75 ° of glossiness of ink-jet recording paper.
(mapping)
With the method for putting down in writing among the JIS H 8686-2, measure the blank sheet of paper mapping partly of the optical comb of 45 ° of reflections, 2.0mm with mapping property mensuration machine (I CM-1DP, ス カ testing machine corporate system), coating direction and slit meet at right angles.Numeral shown in the table is 5 mean values of measuring.
(wrinkling)
Wrinklingly measure with ink-jet printer BJF870 (manufacturing of キ ヤ ノ Application company).BCI-6C, BCI-6M, BCI-6Y, BCI-Bk, BCI-6PC and BCI-6PM Off オ ト that the ink cartridge uses キ ヤ ノ Application company to make.The wrinkling visual assessment of using that partly takes place at the printing writing of 2 mixture of colours of cyanogen ink and magenta ink.
Zero: do not have wrinkling, in good condition fully.
△: have wrinkling, the level that can go wrong according to the operating position difference.
*: wrinkling remarkable, out of use level.
(lettering reflecting feel)
Above-mentioned by the wrinkling printing writing that obtains partly with the range estimation estimate.
Zero: range estimation lettering reflecting feel is arranged, in good condition.
△: range estimation lettering reflecting feel has the state of reduction slightly.
*: range estimation lettering reflecting feel is low, the state of imperceptible gloss.
(ink absorption)
Above-mentioned by the wrinkling printing writing that obtains partly with the range estimation estimate.
Zero: partly can't see spot at ベ , in good condition.
△: partly see some spots at ベ , the level that can go wrong according to the operating position difference.
(lettering concentration)
Lettering concentration is measured with ink-jet printer BJF870 (manufacturing of キ ヤ ノ Application company).BCI-6C, BCI-6M, BCI-6Y, BCI-Bk, BCI-6PC and BCI-6PM Off オ ト that the ink cartridge uses キ ヤ ノ Application company to make.Evaluation is that (マ Network ベ ス company makes, and RD-914) the black printing of mensuration writing partly carries out with マ Network ベ ス reflection of the concentration.The numeral of representing in the table is 5 mean values of measuring.
(voidage and specific area standard pore mode diameter)
Use マ イ Network ロ メ ト リ Star Network ス Port ア ザ イ ザ-9320 (manufacturing of Tianjin, island manufacturing company),, measure whole pore specific area and whole pore volume, try to achieve voidage and specific area standard pore mode diameter by mercury injection method.
All ink-jet recording papers of making by embodiment 1～25 (the present invention) also all have high lustrous surface and mapping property under the situation that ink receiving layer is only arranged, particularly, if in gloss layer, be the pigment of 5～100nm with average primary particle diameter, then have high 75 ° of surface glosses and 55% above height mapping property more than 70%, in addition, wrinkle resistant fully.And, because lettering reflecting feel and ink absorption are good, so lettering concentration height.
That is to say that all are the glossiness height by the ink-jet recording paper that embodiment 1～25 (the present invention) makes, and have unruffled excellent appearance, and, therefore have the high good recording characteristic of record concentration because lettering reflecting feel and ink absorption are good.
If embodiment 12 and comparative example 1 are compared, even have the comparative example 1 of the supporting mass C of highly-breathable (air permeability 35 seconds) compares with use, use the ink-jet recording paper of the embodiment 12 of low-permeable (air permeability:＞10000 seconds) supporting mass B, all items is also all good.
If embodiment 1 and comparative example 2 are compared, the ink-jet recording paper that the comparative example 2 of gloss layer is not set equates aspect ink absorption, but other all items in addition is all inferior than the ink-jet recording paper of embodiment 1.
If embodiment 17 (using supporting mass B as supporting mass) is compared with comparative example 3 (supporting mass uses supporting mass A), use other all items such as the 75 ° of surface glosses of ink-jet recording paper (embodiment) of low-permeable supporting mass B and mapping property all to be better than comparative example.
In addition, the aggregate particle size of the micro pigment that uses in the ink receiving layer is constant, if the average primary particle diameter of the micro pigment that uses in the gloss layer diminishes, then glossiness improves, if become 8nm, and then ink absorption reduction.And big if average primary particle diameter becomes, then lettering concentration slowly descends.
If embodiment 1,3,4 and embodiment 2 are compared, using average aggregate particle size is the embodiment 1,3 of the following silicon dioxide gel of 1.3 μ m and 4 ink-jet recording paper, and its 75 ° of surface glosses and lettering reflecting feel, lettering concentration are good.
If embodiment 20 and embodiment 25 are compared, find to use the degree of polymerization be 3500 PVA than using the degree of polymerization is the ink absorption raising of 1700 PVA, and lettering concentration uprises.
The possibility of industrially utilizing
As mentioned above, the manufacture method of existing cast-coated paper is the wetting plastic shape of pressure welding on the felt wrapped roll of heating Coating surface under the attitude, drying, form gloss layer after, release copying obtained minute surface from the felt wrapped roll, and this Invention is by supplying with the coating fluid that is used to form gloss layer at ink receiving layer, being in profit at this coating fluid During wet condition or the partial desiccation state, this coating fluid supply range is contacted with felt wrapped roll, make supporting mass in press polish Pass through when pressurizeing between roller and the pressure roll, behind the formation coating liquid layer, peel off from above-mentioned felt wrapped roll immediately This is coated with liquid layer, thereby gloss layer is set.
The ink absorption of ink-jet recording paper of the present invention and ink absorption speed do not reduce basically, have High surface gloss, and have no crack and put the good ink mist recording adaptability of repeatability.
Claims (6)
1. ink-jet recording paper, this paper used for recording have the supporting mass of low-permeable or non-gas permeability, the ink receiving layer of one deck at least that forms in coating on this supporting mass and the gloss layer that coating forms on this ink receiving layer again, it is characterized in that:
With the ink receiving layer that above-mentioned gloss layer is connected, the specific area mode standard diameter that its pore distributes only is below the 100nm, and with average aggregate particle size be pigment below the 1.3 μ m as principal component,
Above-mentioned gloss layer with average primary particle diameter be the pigment of 5～100nm as principal component,
Wherein the voidage b% of the voidage a% of above-mentioned ink receiving layer and above-mentioned gloss layer satisfies following formula:
a＞b、a-b＞25、45＜a＜80、10＜b≤45。
2. according to the ink-jet recording paper of claim 1 record, 75 ° of surface glosses on wherein above-mentioned gloss layer surface are more than 70%, and the mapping when using the optical comb of wide 2.0mm is more than 55%.
3. according to the ink-jet recording paper of claim 1 record, wherein the thickness of above-mentioned gloss layer is 0.02～4 μ m, and is below 1/10 of gross thickness of above-mentioned ink receiving layer.
4. according to the ink-jet recording paper of claim 1 record, wherein one deck at least of above-mentioned ink receiving layer contains pigment and adhesive, and above-mentioned adhesive is the polyvinyl alcohol of the degree of polymerization 3000～5000.
5. according to the ink-jet recording paper of claim 1 record, wherein above-mentioned supporting mass is film or resin-coated paper.
6. according to the ink-jet recording paper of each record in the claim 1～5, wherein above-mentioned gloss layer forms with felt wrapped roll.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB031427928A CN100413699C (en) | 2003-04-30 | 2003-04-30 | Paper for ink mist recording |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB031427928A CN100413699C (en) | 2003-04-30 | 2003-04-30 | Paper for ink mist recording |
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| CN1541851A CN1541851A (en) | 2004-11-03 |
| CN100413699C true CN100413699C (en) | 2008-08-27 |
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1918120B1 (en) * | 2005-08-25 | 2010-07-21 | Oji Paper Co., Ltd. | Transparent thermal recording medium |
| WO2011008218A1 (en) * | 2009-07-17 | 2011-01-20 | Hewlett-Packard Development Company, L.P. | Print media for high speed, digital inkjet printing |
| CN102501674A (en) * | 2011-10-14 | 2012-06-20 | 江苏格美高科技发展有限公司 | Glossy waterproof polypropylene photo paper applicable for aqueous ink and its preparation method |
| CN103643590B (en) * | 2013-12-25 | 2016-01-20 | 山东鲁南新材料股份有限公司 | A kind of sizing material and preparation method thereof and the application in pre-gum dipped paper is produced |
| CN106480777A (en) * | 2016-11-28 | 2017-03-08 | 南通华润新材料有限公司 | Glazing layer masking liquid of a kind of high glaze is water-fast printing paper and preparation method thereof |
| JP6531204B1 (en) * | 2018-06-29 | 2019-06-12 | セーレン株式会社 | Printed matter, method for providing gloss and method for producing printed matter |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1370687A (en) * | 2001-02-16 | 2002-09-25 | 三菱制纸株式会社 | Ink jetting record material |
| JP2002347337A (en) * | 2001-03-21 | 2002-12-04 | Asahi Glass Co Ltd | Ink jet recording medium |
| CN1394170A (en) * | 2000-10-24 | 2003-01-29 | 三菱制纸株式会社 | Recording material for ink-jet |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1394170A (en) * | 2000-10-24 | 2003-01-29 | 三菱制纸株式会社 | Recording material for ink-jet |
| CN1370687A (en) * | 2001-02-16 | 2002-09-25 | 三菱制纸株式会社 | Ink jetting record material |
| JP2002347337A (en) * | 2001-03-21 | 2002-12-04 | Asahi Glass Co Ltd | Ink jet recording medium |
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