CN1272185C - Image recording medium - Google Patents
Image recording medium Download PDFInfo
- Publication number
- CN1272185C CN1272185C CNB028108124A CN02810812A CN1272185C CN 1272185 C CN1272185 C CN 1272185C CN B028108124 A CNB028108124 A CN B028108124A CN 02810812 A CN02810812 A CN 02810812A CN 1272185 C CN1272185 C CN 1272185C
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- China
- Prior art keywords
- ink
- image recording
- recording media
- receiver layer
- cationic
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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
- B41M5/52—Macromolecular coatings
- B41M5/5245—Macromolecular coatings characterised by the use of polymers containing cationic or anionic groups, e.g. mordants
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
- B41M5/502—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording characterised by structural details, e.g. multilayer materials
- B41M5/508—Supports
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
- B41M5/502—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording characterised by structural details, e.g. multilayer materials
- B41M5/506—Intermediate layers
Landscapes
- Ink Jet Recording Methods And Recording Media Thereof (AREA)
- Ink Jet (AREA)
- Photographic Developing Apparatuses (AREA)
- Holo Graphy (AREA)
- Paper (AREA)
Abstract
Provided is an image-recording medium, which can form a high quality image thereon without yellowing (the shift of color tone) or the blotting of the ink with both the dye ink and the pigment ink. An image-recording medium having a support having breathing micropores, the surfaces and the micropores of which are made hydrophilic, and an ink-receptive layer which is provided on the surface of the support and comprises a binder and a coagulant, characterized in that the ink-receptive layer contains a cationic organic oligomer having a cationic functional group in the molecule, or a cationic polymer having a cationic functional group in the molecule as a coagulant.
Description
Technical field
The present invention relates to the printing process image recording media of ink jet printing method recording ink image for example.In specific words, the present invention relates to pigment ink and dye ink all are suitable for and can write down the image recording media of high quality graphic.
Background technology
Known a kind of image recording media, it comprises that the carrier with gas permeability micropore is a porous carrier, can be used as for example image recording media of ink jet printing paper, the back side of described carrier and micropore are hydrophilic.Disclosed this class image recording media at US-A-560750, WO99/03685 and WO01/10650.
For example, WO99/03685 discloses a kind of image recording media, and surfactant and multivalent metal salt are arranged in this medium, and these two kinds of materials are included in the micropore as the perforated membrane of carrier.Because surfactant makes the micropore inwall have hydrophily, applied the liquid that contains multivalent metal salt after, this multivalent metal salt just is fixed in the micropore.When getting on, printing ink just is fixed on the carrier surface ink printing (or record).
On carrier, can provide one deck ink-receiver layer.Therefore, contained pigment is just stayed rising on the fixation surface of ink-receiver layer in the printing ink, can prevent effectively that pigment from moving in hole, improves painted and the quick-drying energy.WO01/10650 (corresponding to JP-2001-47734 A) has proposed to use the layer that contains water soluble salt and organic adhesion agent as the ink-receiver layer that forms on the carrier with gas permeability micropore.
When applying printing ink (by printing) on dielectric surface (surface of ink-receiver layer), the water soluble salt in the ink-receiver layer just plays coagulating agent, makes the pigment rapid condensation (or fixing) on the ink-receiver layer.Therefore, effectively prevented to improve the quick-drying energy in the hole of pigment migration in the medium.
The effect of organic adhesion agent is binding agent to be fixed (or combination) in ink-receiver layer with effective means.Therefore, the cooperative effect of the coagulation by water soluble salt and the adhesive effect of adhesive has effectively improved the water proofing property of fixing ink image.
The coagulating agent consumption is generally per 100 weight portion adhesive polymers 1-70 weight portion coagulating agent.
JP-A-10-86505 has disclosed a kind of ink printing paper, its manufacture method is to apply the waterproofing agent that is used for ink jet printing paper that comprises the certain cationic urethane oligomer on common paper or coated paper, but this printing paper be not have its surface and micropore be the image recording media of hydrophilic carrier.When using a kind of paper as ink-jet print medium, the problem of dyestuff stain can appear causing such as the viscosity owing to printing back water.So, just inquire into the use problem of waterproofing agent below.
Known resin cation such as two cyanogen diamines condensation product, polyamine and polymine can be used as waterproofing agent, but also there are some defectives in they, as water proofing property deficiency, tone can change, the white portion of paper can yellowing, the printing ink spot.Cation amino Ethyl formate oligomer can improve the water proofing property of printing image, can prevent the yellowing of tone variations and paper white color part when using the dye ink printing sheets basically.
The preparation method is as follows for cation amino Ethyl formate oligomer: make following compounds (A), (B) and (C) carry out sudden reaction to obtain polyurethane, use again in the acid and polyurethane at least a portion tertiary amine groups, or make at least a portion tertiary amine groups quaternized with quaternizing agent:
(A) have the polyalcohol of at least two energy and NCO reactive activity hydrogen atom, molecular weight is 300-5,000;
(B) dihydroxylic alcohols, trihydroxylic alcohol, the diamines that a tertiary amine groups is arranged or triamine, molecular weight is less than 300;
(C) organic isocyanate of at least two isocyanate groups is arranged.
According to the disclosed detailed description of this JP-A, the weight average molecular weight of cation amino Ethyl formate oligomer is less than 10,000 (about 1,000 to 8,000).
Recently, switch the large-scale ink-jet printer commercialization that pigment ink and dye ink type are used to print with finger manipulation.Therefore, the requirement of the user of this ink-jet printer nature can not change used image recording media with these two kinds of ink printings.Yet, on conventional recording medium, be difficult to not only can both print out high-quality image with dye ink but also with pigment ink.
For example,, can print out the image of fine quality, but tone changes easily, so the color of color printing image can change to yellow hue with pigment ink if usefulness is the above-mentioned ink-receiver layer that contains water soluble salt and organic adhesion agent.
The ink jet printing paper that contains cation amino methyl ethyl oligomer can print well with dye ink.Yet when printing with pigment ink, the spot phenomenon at printing position can obviously take place.Partly cause is that the colouring component (pigment) in the printing ink can be moved in the hole of medium inside.
Summary of the invention
The invention provides a kind of image recording media, this medium comprises that (i) has the carrier of gas permeability micropore, the surface and the micropore of this carrier are made hydrophily, the (ii) ink-receiver layer on above-mentioned carrier surface, this layer comprises adhesive and coagulating agent, is characterized in containing in the described ink-receiver layer in the cation organic oligomer that has Cationic functional groups in the molecule or the molecule having the cationic polymer of Cationic functional groups as coagulating agent.
Image recording media of the present invention comprises that its surface and micropore are hydrophilic porous carrier, and the ink-receiver layer on described carrier surface, and this layer comprises adhesive and be the coagulating agent of cationic oligomeric thing or polymer.Therefore, can both print high-quality image, the obvious spot phenomenon on yellowing (hue shift) or the printed matter can not take place with dye ink and pigment ink.So, the invention provides and a kind ofly can satisfy the image recording media of user can also requiring with dye ink with the medium of pigment ink printing.
Therefore, purpose of the present invention provides and a kind ofly can satisfy the user to can also using the pigment ink printing with dye ink, and does not need to change the image recording media of the requirement of used image recording media type.
More specifically, the object of the invention provides and a kind ofly can both print out high quality graphic with dye ink and pigment ink, and the image recording media of yellowing (hue shift) and the obvious spot phenomenon of printing ink does not take place.
When using water soluble salt as coagulating agent, if use the dye ink printing, tone can change.Disclose as JP-A-10-86505, the cation organic oligomer is good waterproofing agent, can improve the picture quality that forms with dye ink.Yet its coagulation of cation organic oligomer itself is more a little than the coagulating agent difference of water-soluble alkali.So, should further improve the cation organic oligomer, can make the pigment rapid condensation on ink-receiver layer surface, thereby prevent that pigment migration is in the hole of carrier inside.
The invention provides a kind of image recording media, comprising:
(i) have the carrier of gas permeability micropore, its surface and micropore have been made hydrophily, the (ii) ink-receiver layer on above-mentioned carrier surface, and this layer comprises adhesive and coagulating agent,
It is characterized in that, in described adhesive is 100 weight portions, and described ink-receiver layer comprises in the cation organic oligomer that has Cationic functional groups in the 1-40 weight portion molecule or the molecule and has the cationic polymer of Cationic functional groups as described coagulating agent.
In a preferred embodiment of the present invention, described ink-receiver layer comprises weight average molecular weight 10,000-1, the cationic polymer of 000,000 scope.
The specific embodiment
According to the present invention, use the carrier of possess hydrophilic property surface and micropore, remedy the weakness that the cation organic oligomer occurs when printing with pigment ink,, so improved the compatibility of medium and pigment ink.
Such synergy details are not clear at present, but can think following reason:
Generally, improve coagulation, it is favourable having the dissociate low molecular weight compound of performance of macroion, as water soluble salt.The molecular weight of this compound is influential to the ion populations that can dissociate on the per unit volume ion receiving layer.Therefore, the cation organic oligomer that the ionic dissociation performance is low can not improve coagulation.On the other hand, the printed matter with dye ink increases and easier generation yellowing with the dissociating ions number.This may be because dyestuff and ionic reaction form the complex like the complex material, so the skew of the absorbing wavelength of light.Therefore, from preventing the yellowing consideration, the cation organic oligomer is better than water soluble salt.Can remedy the cation organic oligomer in the weakness aspect the coagulation with hydrophilic porous carrier.When the distributes ink medium can be retained in the printing position for a long time the time, suppressed the congealing reaction of cation organic oligomer, because the interaction of organic oligomer and pigment is less than water soluble salt for pigment.Can think that the decentralized medium of hydrophilic porous carrier energy fast Absorption printing-ink can and quicken the effect of the congealing reaction of organic oligomer and pigment thereby have the quick-drying of raising.
Ink-receiver layer can be a simple layer that comprises adhesive polymer and cationic polymer (or oligomer) mixture.Be preferably, ink-receiver layer has two-layer stepped construction as described below:
That is, ink-receiver layer comprises (ii-1) basic unit, and its back side also has a front back to this back side facing to carrier, contains adhesive; (ii-2) upper strata, it comprises coagulating agent, and its part is immersed in the basic unit, is positioned at the front near basic unit.
When using such ink-receiver layer, can more effectively improve the effect that prevents with yellowing and spot in the printed matter of dye ink and pigment ink.
Coagulating agent
Coagulating agent is the cation organic oligomer (cationic oligomeric thing) that Cationic functional groups is arranged in a kind of molecule, or the cationic organic polymer (cationic polymer) of Cationic functional groups is arranged in the molecule.
The cationic oligomeric thing has the intermediate molecular weight between low-molecular-weight coagulating agent such as water soluble salt and polymer.The weight average molecular weight of cationic oligomeric thing is generally 500-10, and 000.
Used cationic oligomeric thing or polymer have at least one Cationic functional groups, are selected from cationic nitrogenous functional group, sulfonium salt (as-S
+R
2X
-, wherein, R is methyl or hydrogen atom, X is halide ion) with phosphonium salt (as-P
+R
2X
-, wherein, R is methyl or hydrogen atom, X is a halide ion).
Cationic nitrogenous functional group is selected from following at least a group: amine salt, quaternary ammonium salt (as-N
+R
3X
-, wherein, R is methyl or hydrogen atom, X is a halide ion), pyridiniujm is (as-N
+C
5H
5X
-, wherein, X is a halide ion) and polyethylene polyamine (as-NH (C
2H
4NH)
mH, wherein, m is the number of 2-4).
When cationic oligomeric thing or polymer when the mixture with adhesive polymer is included in the ink-receiver layer, in its molecule, should comprise at least one and be selected from following cationic salts functional group: sulfonium salt, phosphonium salt, quaternary ammonium salt and pyridiniujm.Such cationic salts functional group helps preventing yellowing, because they have medium ionic dissociation performance, also has coagulation, makes under hydrophilic porous carrier situation to prevent the spot phenomenon when printing with pigment ink.When the adhesive of ink-receiver layer comprises a kind of ion modification polymer, when especially having anionic functional group's polymer, this cationic polymer not can with the ion modification interpolymer interaction in the coating that is used for forming ink-receiver layer, therefore, this cationic polymer can keep stable dispersion or dissolved state, does not condense.Consider especially preferably have the polymer or the oligomer of quaternary ammonium salt from this point.
As cationic polymer, can use the polymer that comprises polyamines, polyurethane, polyureas, polyester or polyoxyalkylene ether in the main chain, contain Cationic functional groups in each comfortable its molecule of these polymer.Equally, comprise polyamines, polyurethane, polyureas, polyester or polyoxyalkylene ether in the main chain, and the oligomer that contains Cationic functional groups in each comfortable molecule can be used as the cationic oligomeric thing.
The cation polyurethane that will use among the present invention can be by the method preparation of conventional synthesis of polyurethane.For example, react with the polyol blends that comprises polyalcohol by polyisocyanates and prepare with Cationic functional groups such as quaternary ammonium group.
When Cationic functional groups is quaternary ammonium group, cation polyurethane can precursor is quaternized to be prepared by making, and described precursor is to carry out prepared in reaction by the mixture of compound that has reactive hydrogen and tertiary amine group in (1) molecule and polyalcohol and (2) polyisocyanates.Such reaction can be carried out according to following process:
At first, adding has the solvent that at least two polyalcohols with isocyanate groups energy reactive activity hydrogen atom form the material oligomer of main chain as formation and do not contain reactive hydrogen in a reactor, and this reactor is replaced with nitrogen.The weight average molecular weight of polyalcohol is generally 300-5, and 000.
Then, in this reactor, add polyisocyanates,, polyisocyanates and material oligomer are reacted 60 ℃ or higher temperature heating a few hours with at least two isocyanate groups.The product that obtains in this reaction is cooled to 50 ℃ or lower, in this product, adds the amino-contained compound that contains reactive hydrogen and tertiary amine groups.This mixture is heated again, at 60 ℃ or higher temperature stoichiometric number hour.Acquisition is as the polyurethane prepolymer of cationic oligomeric thing precursor.Can use separately and have glycol, triol, diamines or the triamine of reactive hydrogen and tertiary amine groups as the amino-contained compound in the molecule.The weight average molecular weight of this compound is generally less than 300.
Polyurethane prepolymer and a kind of acid reaction with obtaining make tertiary amine groups quaternized.
At last, in total reaction mixture, add excessive water, make unreacted isocyanate groups inactivation (kill), carry out afterreaction a few hours at about 50 ℃ subsequently, obtain to contain the aqueous solution of the cationic oligomeric thing (cationic urethane oligomers) of requirement.
The example of above-mentioned polyalcohol comprises: the addition polymers of the addition polymers of polypropylene glycol, polytetramethylene glycol, polyethylene glycol, bisphenol-A and expoxy propane, bisphenol S and expoxy propane, adipic acid base polyester, M-phthalic acid base polyester.
The example of above-mentioned amino-contained compound comprises: N-methyl-N, N-diethanol amine, N-ethyl-N, N-diethanol amine, N-isobutyl group-N, N-diethanol amine, triethanolamine, methylene imine base di-n-propylamine, butyl imido grpup di-n-propylamine, three (2-amido ethyl) amine.
As polyisocyanates, can use those polyisocyanates that are commonly used to synthesis of polyurethane.Polyisocyanates example commonly used comprises aliphatic vulcabond, as fourth vulcabond, 1, and hexamethylene-diisocyanate, dodecyl vulcabond, trimethyl hexamethylene diisocyanate.
The object lesson that is used for cationic polymer of the present invention has: the cationic polyamine that contains quaternary ammonium salt group is (with trade name NEOFIX IJ-450 from NIKKAChemical Co., Ltd. buy) and cationic polyamide (from NIPPON PMC Co., Ltd. buys with trade name WSSERIES ).
The object lesson that is used for cationic oligomeric thing of the present invention has: contain quaternary ammonium salt group cation polyurethane (from NIKKAChemical Co., Ltd. buys with trade name NEOFIX IJ-150), contain the organic oligomer (buying from Witco Chemical) of quaternary amine group with trade name Emcol CC-9, Emcol CC-36 or Emcol CC-42.
In ink-receiver layer,, be 100 weight portions, be generally the 1-40 weight portion, be preferably the 3-35 weight portion, preferably the 5-30 weight portion in adhesive polymer as the cationic oligomeric thing or the polymer content of coagulating agent.When cationic oligomeric thing or polymer content were too low, congealing activity descended, and the ink image spot can occur on the printed matter of pigment ink.When this content is too high, on the printed matter of dye ink yellowing can appear.
Can use cationic oligomeric thing or polymer and anion organic oligomer simultaneously, only otherwise damage effect of the present invention.The anion organic oligomer has and comprises the main chain that polyurethane, polyureas, polyester or polyoxyalkylene ether and a kind of anion palace can be rolled into a ball.Anionic functional group's example has: carboxylate groups, sulfonate groups, phosphate ester salt group.
Can also use two oligomers, as betaine or sulfobetaines oligomer.
The weight average molecular weight of the anionic oligomer that uses with cationic oligomeric thing or polymer is generally 500-8,000.
Carrier
Carrier can be film or the sheet material (being referred to as " perforated membrane " here) with gas permeability micropore, and its surface and micropore are made possess hydrophilic property.The kind of perforated membrane is not limit, as long as can obtain above-mentioned effect, the conventional any carrier that uses all can use in image recording media.For example, better use extension resin molding such as TESLIN perforated membrane (the extension porous resin film of PPGIndustries).
According to the Gurley osmolarity tester, the porous permeability of the membrane is generally 10-3, and 000 second/100 milliliters, better 50-2,500 seconds/100 milliliters, best 100-2,000 second/100 milliliters.
At this, the Gurley permeability is according to JIS P-8117-1980, measures with the Gurley osmolarity tester, with the value of 100 milliliters of air by sample required time (second) expression.
The example of porous film material comprises: polyethylene, polypropylene, polymethylpentene-1, polyvinyl chloride, polyvinylidene chloride, polystyrene, styrene-butadiene-acrylonitrile copolymer, polyamide, Merlon, acrylic resin, polyester, copolymer polyester etc.They can use with two or more mixture.From water proofing property and cost consideration, wherein better be common resin such as polyolefin (as polypropylene, high density polyethylene (HDPE)).
Also can contain inorganic fine powder in the perforated membrane, in order that improve the porosity of film.The inorganic fine powder example comprises: calcium carbonate, aluminium oxide, calcined clay, silica etc.The granularity of fine powder is generally the 0.3-10 micron, better the 0.8-5 micron.In addition, perforated membrane also can contain other additives, as heat stabilizer, UV absorbent, dispersant, antistatic additive, antioxidant, oil (as mineral oil) etc.
Perforated membrane can prepare by the composition that stretching comprises above-mentioned resin and available inorganic fine powder and other additives.The example of stretcher comprises: the inflation film forming machine, be equipped with inner axis of heart the inflation forming machine, the T pattern film shaping machine of stenter or longitudinal extension roller and stenter is equipped with.Can carry out single shaft or biaxial stretch-formed.
The porosity of perforated membrane (being the percentage of film cumulative volume mesopore cumulative volume) is generally 10-90 volume %, better 20-80 volume %.When porosity was too low, the quick-drying of recording medium can variation.When porosity was too high, the solidity of carrier (mechanical strength) descended, and recording medium can not be supplied with and take out smoothly.
The pore diameter that records on the cross section perpendicular to film wall thickness direction (being the horizontal direction of extension film) is generally the 0.01-3 micron, better 0.02-2 micron, better 0.03-1 micron.
The gross thickness of carrier is 30-1,000 micron, and better 50-500 micron.When carrier thickness was too thin, the ink setting performance can variation.When thickness was too big, recording medium is handled can be inconvenient.Image recording media of the present invention can print with various types of ink-jet printers, but the too big medium of thickness can not print with some printing machine.
In the better embodiment of the present invention, the surface of carrier and micropore are handled and the acquisition hydrophily with surfactant.When forming ink-receiver layer, in the coating that forms ink-receiver layer, add surfactant, then this coating is applied on the carrier surface, just can carry out hydrophily like this and handle.Yet, before forming ink-receiver layer, carry out such hydrophily and be treated to.
At first, the liquid that will contain surfactant is applied on the carrier surface, or carrier is immersed in the liquid that contains surfactant, makes the surface of carrier and micropore become hydrophilic.Then, the liquid that will contain adhesive resin and cationic oligomeric thing is applied to the carrier surface of handling through hydrophily, forms ink-receiver layer.This method is made the image recording media with rapid draing performance easily.
Surfactant can be any in anion, cation, both sexes or the nonionic surface active agent.Anion surfactant comprises carboxylic acid type, sulfonate type and phosphate type.Cationic surfactant comprises amine salt type and quaternary.Amphoteric surfactant comprises betaine type and sulfonation betaine type, and ionic surfactant pack is drawn together polyoxyalkylene type (as polyethylene glycol), sorbitan type and D-sorbite type.
When by applying and the dry liquid that contains surfactant carries out hydrophily when handling, its liquid medium better is water or alcohols such as ethanol.The concentration of surfactant in liquid is generally 1-30 weight %, is preferably 5-25 weight %.
Can use conventional coating apparatus as wind the line excellent coating machine, knife type coater, roll-coater, die coater as applicator device.
Contain quite a large amount of amorphous silica particles when whole porous membrane or near the part of film surface, when the carrier hydrophily is provided, handles and to omit with the hydrophily that surfactant carries out.The general 0.3-10 micron of silica dioxide granule granularity, better 0.8-5 micron.In the film gross weight is benchmark, the general 30-60 weight of silica dioxide granule content %, better 35-55 weight %.
Image receiving layer
The example of the adhesive polymer of image receiving layer comprises: polyurethane, polyolefin, polyvinyl chloride, polyvinylidene chloride, polystyrene, styrene-butadiene-acrylonitrile copolymer, polyamide, acrylic polymer, polyester etc.Be preferably, use the ion modification polymer.Ion modification polymer and cationic oligomeric thing or polymer are collaborative, and pigment or dyestuff are stayed the printing zone of carrier, and have the function that raising prevents the spot effect.From this viewpoint, better be the combination of ion modification polymer and cationic polymer.Usually, use water dispersible ion modification polymer.
Being used on ion modification polymer of the present invention is a kind of cation-modified polymer, as cation modified polyurethane, cation-modified polyester.The ink-receiver layer coating of cation dry polymer is particularly conducive to the water proofing property of the image that improves ink jet printing.
An object lesson of ion modification polymer is the ion modification polyurethane that discloses among the JP-A-10-181189, and this polymer comprises the mixture that has sulfonic polyurethane and chloropropylene oxide-polyamide in its molecule.Chloropropylene oxide-polyamide can be by adipic acid and the preparation of diethylenetriamines dehydrating condensation.There is sulfonic polyurethane not have sulfonic second kind of two pure and mild vulcabond to carry out polymerization in sulfonic first kind of glycol, the molecule to prepare in the molecule by making to have in the molecule.First kind of glycol can prepare by the ester exchange of dimethyl disulfide for isophthalic acid sodium and a kind of glycol.
The object lesson of commercially available ion modification polymer has: PATERACOL IJ-170 (coating of cation modified polyurethane and inorganic fine powder) and PATERACOL IJ-21 (cation modified polyurethane but do not have the coating of inorganic fine powder), all can be from DAINIPPON INK AND CHEMICALS, INC. buys.
Ink-receiver layer contains inorganic fine powder preferably, with the porosity of raising ink-receiver layer, and further improves the ink setting performance.Can use calcium carbonate, aluminium oxide, calcined clay, silica (comprising amorphous silica) as inorganic fine powder.The granularity of fine powder is generally the 0.3-10 micron, better the 0.8-5 micron.
The consumption of inorganic fine powder is 100 weight portions in the adhesive gross weight, is the 15-65 weight portion, better the 25-55 weight portion.The inorganic fine powder amount too hour, the ink setting performance can not get improving.When the inorganic fine powder amount is too big, the mechanical strength deficiency of ink-receiver layer.
Ink-receiver layer can also comprise other additives, as heat stabilizer, UV absorbent, dispersant, antistatic additive, antioxidant.
Ink-receiver layer can be by applying the liquid of cation oligomer and adhesive polymer at carrier surface, dry then this liquid forms.In this case, suitable water of solvent or alcohols.
Perhaps, form the layer that contains adhesive earlier, then, apply the liquid that contains coagulating agent such as cationic polymer, the dry then ink-receiver layer that forms.Specifically be when coagulating agent is good material of filming performance such as cationic polymer, is formed up to the small part upper strata easily and is immersed in ink-receiver layer in the basic unit.That is, at first, form the basic unit that contains the adhesive polymer that is useful on basic unit, apply the coating that contains coagulating agent then in this basic unit, the dry then upper strata that contains coagulating agent that forms makes this upper strata be positioned at the surface of close basic unit.After having formed the layer (basic unit) that contains adhesive in the ban, just apply the coating that contains coagulating agent on this one deck, coagulating agent is located on the surface portion of the ink-receiver layer of accepting printing ink, therefore, helps improving the effect of coagulating agent.Under the situation, be preferably like this, make basic unit contain inorganic fine powder, at least a portion upper strata is immersed in the basic unit easily.
The apparatus for coating that uses in the formation method of image receiving layer has conventional coating apparatus, as wind the line excellent coating machine, knife type coater, roll coater, die coater etc.
Be used for cationic oligomeric thing (polymer) concentration that the coating on upper strata comprises and be generally 0.5-30 weight %, better 1-25 weight %.
The gross thickness of image receiving layer can be in the relative broad range difference.On the one hand, ink-receiver layer should have sizable thickness, and is fuzzy to prevent ink image.On the other hand, ink-receiver layer should be thinner, to suppress to influence owing to avale (sinking) of printing ink coloured material the demonstration of color.Consider that from these factors the thickness of ink-receiver layer is generally the 5-100 micron, is preferably the 10-50 micron.
When ink-receiver layer comprised basic unit and upper strata, groundwork thickness was generally the 4.7-99 micron, better-the .5-49 micron, and selected upper thickness, make groundwork thickness in above-mentioned scope and ink-receiver layer gross thickness in above-mentioned scope.For example, comprise the upper thickness that a part is immersed in the basic unit and be generally the 0.3-40 micron.Upper thickness is generally less than groundwork thickness.
The application of recording medium
Image recording media of the present invention can be used for adopting printing machine such as ink-jet printer recording ink image.
Printing ink generally contains the solvent of the colouring agent of pigment or dyestuff and so on and water, alcohol and so on.Recording medium of the present invention has good especially performance when use printing ink (containing aqueous solvent) and ink-jet printer write down, can effectively improve quick-drying energy and water proofing property.Can be when conventional record-paper the is printed used condition of its printing condition is identical.Therefore, one of advantage of recording medium of the present invention need not to adopt special printing condition exactly.
Recording medium of the present invention can be used as the structural material of decorating glue bonded sheet and so on.For example; can be opposing on the surface of printing ink fixed surface at carrier; the adhesive layer that contains adhesive such as pressure-sensitive adhesive is provided, and the liner of the surface of pressure-sensitive adhesive of protection adhesive layer is provided, form the sandwich of forming by recording medium, adhesive layer and liner.This sandwich can for example be printed on decorative pattern on the printing ink stationary plane (ink-receiver layer surface) of the recording medium of this sandwich as the recording medium press printing, obtains the adhesive sheet that is used to decorate.Adhesive sheet of the present invention can be adhered to that for example wall, sign board, sign, car body, glass pane etc. are decorated it above the object.
Embodiment
Embodiment 1
The carrier that this embodiment uses is the perforated membrane that contains amorphous silica, and its thickness is 350 microns, and porosity is 65 volume %, and the aperture is the 0.01-1 micron.This perforated membrane is the Teslin SP1400 of PPG Industries.
On a surface of carrier, apply coating with the excellent coating machine of a coiling with following composition, drying forms ink-receiver layer, obtains the recording medium of this embodiment.The layer that applies up dry 3 minutes at 100C.Ink-receiver layer thickness is 17 microns.
＜the coating that is used for ink-receiver layer is formed 〉
-adhesive: PATERCOL IJ-170 100 weight portions
-coagulating agent: NEOFIX IJ-150 13 weight portions
PATERCOL IJ-170 comprises the water dispersible cation-modified polyurethane and the coating composition of about 50 weight % silica dioxide granules, can buy from DAINIPPON INK AND CHEMICALS INC..NEOFIX IJ-150 contains the coating composition that the cation of quaternary ammonium salt group organic oligomer is arranged in the molecule, can be from NIKKA Chemical Co., and Ltd. buys.
In adhesive polymer weight is 100 weight portions, and the content that is used for the coating coagulating agent component (cation organic oligomer) of ink-receiver layer is 20 weight portions.
Embodiment 2
This embodiment relates to the ink-receiver layer of the partial structurtes with upper strata and basic unit.
At first, prepare the coating that basic unit uses, on carrier, form this basic unit according to the mode identical with embodiment 1.Then, on the surface of this basic unit, apply the coating that the upper strata that comprises coagulating agent is used, in addition the dry ink-receiver layer that forms.
The coagulating agent that this embodiment uses is a kind of cationic polymer that quaternary ammonium salt group is arranged, can NEOFIX IJ-450 trade name buy (a kind of coating that contains 60 weight % cationic polymers, it is diluted to the cationic polymerization substrate concentration is to use behind the 3 weight %).Apply the coating that the upper strata is used with the excellent coating machine of a coiling, then 100 ℃ of dryings 3 minutes.The ink-receiver layer gross thickness is 18 microns.
Embodiment 3
Make the recording medium of this embodiment according to the mode identical with embodiment 2, difference is to use following material instead as the coagulating agent in the upper strata:
WS 535 (cationic polyamide resins, available from NIPPON PMC Co., Ltd.), WS 535 is a kind of coating compositions that contain 35 weight % cationic polymers, cationic polymer is 5 weight % in this coating concentration that is used for the upper strata.
Comparative example 1
Make the recording medium of this comparative example according to the mode identical with embodiment 1, difference is not add coagulating agent in the coating that receiving layer is used.
Comparative example 2
Make the recording medium of this comparative example according to the mode identical with embodiment 1, difference is to use aluminum sulfate 14-18H
2The coagulating agent of the coating that O uses as receiving layer.In adhesive polymer weight is 100 weight portions, and aluminum sulfate content is 15 weight portions.
Comparative example 3
Make the recording medium of this comparative example according to the mode identical with embodiment 1, difference is to use nonporous film as carrier.The nonporous film that uses is that thickness is 75 microns white PET film (Crysper K1211 can buy from TOYOBO).
Print under the condition below on the ink-receiver layer surface (printing ink fixed surface) of the image recording media that each embodiment and comparative example are made, and method is estimated printing performance below adopting.
Evaluation result is listed in table 1 and table 2.
Printing condition and appreciation condition
(A) print with dye ink
The printing machine of-use: Canon BJ F8500
The printing ink of-use: BCI-8C (cyan), BCI-8M (magenta), BCI-8Y (yellow), BCI-8PC (light cyan (photocyan)), BCI-8PM (light magenta), BCI-8PBK (light black)
-printing condition:
-printing mode: best in quality pattern; Paper: high quality paper
The evaluation of-printing quality
Print out iso standard image N2 (restaurant image automatically) under these conditions, and observe the spot situation.
-color density
Print out the monochromatic pattern of cyan, magenta, yellow or black, measure the color density of the pattern of printing with a color densitometer Spectrodensitometer (available from X-Rite).
-Se changes
Print out the monochromatic pattern of cyan, magenta, yellow or black, and with the color of the printed patterns of comparative example 1 (no coagulating agent) as standard, measure the aberration of all kinds (Δ E) of the printed patterns of embodiment 1-2 and comparative example 2.
-drying time
Be determined at and mix four kinds of colors, the color region of cyan, magenta, yellow and black (400%) loses the time of lustrous surface.
-water proofing property
Print out the monochromatic pattern of cyan, magenta, yellow or black, it was immersed in 20 ℃ of water 1 hour.Then, measure color density and compare, draw reducing of color density with the color density before the dipping.Also observe the printing ink spot or the situation of dipping back printed patterns.
(B) print with pigment ink
The printing machine of-use: Noajet III (from Encad)
The printing ink of-use: pigment ink 8500 series (from 3M)
-printing condition:
Jet speed: 5,000Hz; Print direction: unidirectional; Number of pass times: 4
The evaluation of-printing quality
Print out embedded (built-in) pattern in the above under the condition, observe bleeding (obscurity boundary) and rocket (single fuzzy) situation.-water proofing property
Print out the pattern of cyan, magenta, yellow or black, it was immersed in 40 ℃ of water 1 hour.Then, measure color density and compare, draw the minimizing of color density with the color density before the dipping.Also observe the printing ink spot or the situation of dipping back printed patterns.
Measure color density and drying time according to the mode identical with the dye ink printing.
Table 1
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative example 1 | Comparative example 2 | Comparative example 3 | |
| Printing quality | Fine | Fine | Fine | Fine | Color quite is offset to yellow | The serious spot of black ink |
| Drying time (second) | 5 | 5 | 5 | 5 | 5 | 120 |
| Color density | C：1.50 M：1.38 Y：0.87 B：1.65 | C：1.46 M：1.38 Y：0.94 B：1.55 | C：1.65 M：1.42 Y：0.98 B：1.64 | C：1.57 M：1.36 Y：0.88 B：1.56 | C：1.47 M：1.26 Y：0.82 B：1.63 | C：1.43 M：1.39 Y：0.88 B：1.54 |
| Look changes (with respect to the Δ E of comparative example 1) | C：0.87 M：0.55 Y：0.61 B：0.53 | C：2.38 M：2.60 Y：2.61 B：1.88 | C：1.43 M：3.70 Y：3.04 B：0.43 | C：0.00 M：0.00 Y：0.00 B：0.00 | C：11.30 M：3.90 Y：3.44 B：0.67 | C： M： Y： B： |
| Water proofing property (dipping back color density) | C：1.57 M：1.39 Y：0.88 B：1.61 | C：1.45 M：1.38 Y：0.92 B：1.59 | C：1.65 M：1.38 Y：0.94 B：1.61 | C：1.60 M：1.35 Y：0.87 B：1.52 | C：1.57 M：1.36 Y：0.82 B：1.62 | C：1.39 M：1.20 Y：0.77 B：1.39 |
| No spot | No spot | No spot | No spot | No spot | Many spots |
Table 2
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative example 1 | Comparative example 2 | Comparative example 3 | |
| Printing quality | Fine | Fine | Fine | Many single fuzzy and obscurity boundaries | Fine | At CMYB (400%) color region crackle is arranged |
| Drying time (second) | 100 | 100 | 100 | 100 | 100 | About 60 minutes |
| Color density | C：1.36 M：1.06 Y：0.91 B：1.42 | C：1.39 M：1.07 Y：0.94 B：1.39 | C：1.35 M：1.05 Y：0.94 B：1.34 | C：1.37 M：1.08 Y：0.93 B：1.39 | C：1.48 M：1.06 Y：0.92 B：1.47 | C：1.26 M：1.01 Y：0.88 B：0.85 |
| Water proofing property (dipping back color density) | C：1.36 M：1.04 Y：0.89 B：1.40 | C：1.38 M：1.05 Y：0.92 B：1.40 | C：1.35 M：1.03 Y：0.93 B：1.32 | C：1.36 M：1.06 Y：0.92 B：1.39 | C：1.48 M：1.05 Y：0.90 B：1.47 | C：1.24 M：0.99 Y：0.85 B：1.36 |
| No spot | No spot | No spot | No spot | No spot | No spot |
Claims (15)
1. image recording media comprises:
(i) have the carrier of gas permeability micropore, its surface and micropore have been made hydrophily, the (ii) ink-receiver layer on above-mentioned carrier surface, and this layer comprises adhesive and coagulating agent,
It is characterized in that, in described adhesive is 100 weight portions, and described ink-receiver layer comprises in the cation organic oligomer that has Cationic functional groups in the 1-40 weight portion molecule or the molecule and has the cationic polymer of Cationic functional groups as described coagulating agent.
2. image recording media as claimed in claim 1, the Cationic functional groups that it is characterized in that described cationic oligomeric thing or polymer are to be selected from following at least a functionalized cationic salt group: sulfonium salt, phosphonium salt, quaternary ammonium salt and pyridiniujm.
3. image recording media as claimed in claim 1 is characterized in that described carrier comprises amorphous silica particles, for the surface and the micropore of described carrier provides hydrophily.
4. image recording media as claimed in claim 1 is characterized in that, described ink-receiver layer comprises:
(ii-1) basic unit has in the face of the back side of carrier and the front of reverse side, (ii-2) upper strata overleaf, comprise described coagulating agent, its part is immersed in the described basic unit, is positioned at the front near described basic unit, described coagulating agent comprises described organic oligomer, or described cationic polymer.
5. image recording media as claimed in claim 4 is characterized in that the adhesive of described ink-receiver layer comprises a kind of polymer of ion modification.
6. image recording media as claimed in claim 1, the adhesive that it is characterized in that described ink-receiver layer are polyurethane, polyolefin, polyvinyl chloride, polyvinylidene chloride, polystyrene, styrene-butadiene-acrylonitrile copolymer, polyamide, acrylic polymer, polyester or ion modification polymer.
7. image recording media as claimed in claim 1, the adhesive that it is characterized in that described ink-receiver layer are cation-modified polyurethane or cation-modified polyester.
8. image recording media as claimed in claim 1 is characterized in that described ink-receiver layer comprises weight average molecular weight at 500-10, the cation organic oligomer of 000 scope.
9. image recording media as claimed in claim 1 is characterized in that described ink-receiver layer comprises weight average molecular weight 10,000-1, the cationic polymer of 000,000 scope.
10. image recording media as claimed in claim 1 is characterized in that described ink-receiver layer comprises the cation of polyamines, polyurethane, polyureas, polyester or polyoxyalkylene ether organic oligomer or polymer are arranged in the main chain.
11. image recording media as claimed in claim 1, it is characterized in that described ink-receiver layer also comprises the anion organic oligomer, described anion organic oligomer has the main chain that (i) comprises polyurethane, polyureas, polyester or polyoxyalkylene ether, (ii) the anionic functional group is selected from carboxylate groups, sulfonate groups, phosphate ester salt group.
12. image recording media as claimed in claim 1 is characterized in that described carrier comprises polyethylene, polypropylene, polymethylpentene-1, polyvinyl chloride, polyvinylidene chloride, polystyrene, styrene-butadiene-acrylonitrile copolymer, polyamide, Merlon, acrylic resin, polyester, copolymer polyester or their mixture.
13. image recording media as claimed in claim 1, the porosity that it is characterized in that described carrier are 20-80 volume %.
14. image recording media as claimed in claim 1 is characterized in that described carrier surface and micropore coating surface activating agent before the described ink-receiver layer of coating.
15. image recording media as claimed in claim 1, the porosity that it is characterized in that described carrier are 10-90 volume %.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001162314A JP2002362005A (en) | 2001-05-30 | 2001-05-30 | Image recording medium |
| JP162314/2001 | 2001-05-30 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1512941A CN1512941A (en) | 2004-07-14 |
| CN1272185C true CN1272185C (en) | 2006-08-30 |
Family
ID=19005464
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB028108124A Expired - Fee Related CN1272185C (en) | 2001-05-30 | 2002-05-23 | Image recording medium |
Country Status (8)
| Country | Link |
|---|---|
| EP (1) | EP1395437B1 (en) |
| JP (1) | JP2002362005A (en) |
| KR (1) | KR20040004660A (en) |
| CN (1) | CN1272185C (en) |
| AT (1) | ATE292020T1 (en) |
| DE (1) | DE60203497T2 (en) |
| ES (1) | ES2237674T3 (en) |
| WO (1) | WO2002096657A1 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100450786C (en) * | 2006-04-07 | 2009-01-14 | 南通科兴化工有限公司 | Waterproof colored digital image spray-painting and printing medium |
| CN101454164A (en) * | 2006-04-18 | 2009-06-10 | 株式会社理光 | Inkjet media, recording method, recording apparatus, ink-media set, and ink recorded matter |
| JP5363227B2 (en) * | 2009-03-19 | 2013-12-11 | 富士フイルム株式会社 | Electronic circuit board manufacturing method |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5605750A (en) | 1995-12-29 | 1997-02-25 | Eastman Kodak Company | Microporous ink-jet recording elements |
| JP2845832B2 (en) | 1996-09-12 | 1999-01-13 | 日華化学株式会社 | Waterproofing agent for inkjet recording paper |
| JP3882244B2 (en) | 1996-12-26 | 2007-02-14 | 大日本インキ化学工業株式会社 | Inkjet recording material and printed matter |
| US5897961A (en) * | 1997-05-07 | 1999-04-27 | Xerox Corporation | Coated photographic papers |
| US6020058A (en) * | 1997-06-13 | 2000-02-01 | Ppg Industris Ohio, Inc. | Inkjet printing media |
| US6632510B1 (en) | 1997-07-14 | 2003-10-14 | 3M Innovative Properties Company | Microporous inkjet receptors containing both a pigment management system and a fluid management system |
| US6228475B1 (en) * | 1998-09-01 | 2001-05-08 | Eastman Kodak Company | Ink jet recording element |
| US6086985A (en) * | 1998-10-19 | 2000-07-11 | Eastman Kodak Company | Ink jet recording element |
| JP2001047734A (en) * | 1999-08-06 | 2001-02-20 | Three M Innovative Properties Co | Image recording medium |
-
2001
- 2001-05-30 JP JP2001162314A patent/JP2002362005A/en active Pending
-
2002
- 2002-05-23 AT AT02726918T patent/ATE292020T1/en not_active IP Right Cessation
- 2002-05-23 ES ES02726918T patent/ES2237674T3/en not_active Expired - Lifetime
- 2002-05-23 WO PCT/US2002/016437 patent/WO2002096657A1/en active IP Right Grant
- 2002-05-23 CN CNB028108124A patent/CN1272185C/en not_active Expired - Fee Related
- 2002-05-23 EP EP02726918A patent/EP1395437B1/en not_active Expired - Lifetime
- 2002-05-23 DE DE60203497T patent/DE60203497T2/en not_active Expired - Fee Related
- 2002-05-23 KR KR10-2003-7015479A patent/KR20040004660A/en not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| WO2002096657A1 (en) | 2002-12-05 |
| CN1512941A (en) | 2004-07-14 |
| ATE292020T1 (en) | 2005-04-15 |
| EP1395437A1 (en) | 2004-03-10 |
| ES2237674T3 (en) | 2005-08-01 |
| JP2002362005A (en) | 2002-12-18 |
| EP1395437B1 (en) | 2005-03-30 |
| DE60203497D1 (en) | 2005-05-04 |
| DE60203497T2 (en) | 2006-01-26 |
| KR20040004660A (en) | 2004-01-13 |
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