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

Definitions

• the present invention relates to a print media, particularly for water-based color ink jet printing, and a method for manufacturing the same.
• print media various products such as paper, synthetic paper, and a resin film are known. These print media are affixed to various objects, and used by, for example, providing adhesive on the print media, applying double-sided adhesive tape, etc.
• the present invention provides improved ink jet receptive print media and methods for making such media.
• a print media of the invention comprises a base having a first surface and an ink reception layer on at least a portion of the first surface of the base.
• the ink reception layer has a printing surface defined by micro-phase separation of a blend of a first resin component composition and a second resin component composition
• the first resin component is hydrophilic
• the second resin component comprises an acrylic polymer with a quaternized amino group and exhibits thermal adhesive characteristics.
• the method for manufacturing print media of the invention comprises: (1) providing a base having a first surface; (2) providing a blend of a first resin component composition and a second resin component composition; (3) applying the blend to at least a portion of the first surface of the base to form a coating thereon; and (4) removing solvent from the coating such that micro-phase separation of the first resin component and second resin component occurs.
• the media provided by the invention offer a surprising combination of significant advantages, including good, high resolution receptivity to water-based inks, resistance to image bleed, resistance to water absorption and water damage, and good adhesion properties, i.e., the printing surface will adhere to desired adherends. They are well suited for use in high speed printing applications and can be used to make articles with high quality, high resolution, durable images thereon.
• References D1-D4 did not provide print media capable of desired performance and capability.
• Reference D5 purports to disclose media exhibiting desired performance and capabilities, but the media disclosed therein were found to exhibit dye bleeding with water-based ink was applied with a high-speed jet printing of more than 25 mm/sec, it caused dye bleeding.
• the printing surface has a plurality of first micro-phase isolation regions that contain more of the first resin component than the second resin component and a second micro-phase isolation region which contains more of the second resin component than the first resin component, surrounds each of the micro-phase isolation regions in approximately the shape of a ring, and is relatively convex.
• Fig. 1 is a schematic cross-sectional view showing one illustrative embodiment of a print media of the present invention
• Fig. 2 is a schematic cross-sectional view showing another illustrative embodiment of a print media of the present invention
• Fig. 3 is a schematic cross-sectional view showing yet another illustrative embodiment of a print media of the present invention.
• Fig. 4 is a figure showing the surface of the print media obtained in Example 1 as observed with an optical microscope
• Figs. 5a and 5b are figures showing the result when the non-contact surface coarseness of the print media obtained in Example 1 is measured with a measuring instrument;
• Fig. 6 is a figure showing the result when the surface of the print media 2 obtained in Comparison Example 1 as observed with an optical microscope;
• Figs. 7a and 7b are figures showing the result when the non-contact surface coarseness of the print media obtained in Comparison Example 1 is measured with a measuring instrument.
• Figs. 1-3 are not to scale and Figs. 1-7 are intended to be merely illustrative and not limiting.
• Weight percent, percent by weight, % by weight, and the like are synonyms that refer to the concentration of a substance as the weight of that substance divided by the weight of the composition and multiplied by 100.
• the printing surface is defined by micro-phase separation of the blend of the first resin component composition and the second resin component composition. It has been discovered that the resultant printing surface is made up of a matrix of first domains the majority fraction of which is first resin component and second domains the major fraction of which is second resin component and that these domains have a physical configuration and combination of characteristics which result in surprising performance.
• the ink reception layer has a plurality of first micro-phase isolation regions that contain more of the first resin component than the second resin component and a second micro-phase isolation region which contains more of the second resin component than the first resin component, surrounds each of the first micro-phase isolation regions in approximately the shape of a ring (i.e., the substantially completely enclosing cells), and is relatively convex.
• the first resin component comprises polyalkylene oxide.
• the print characteristics and adhesion of the printing surface are improved because the polyalkylene oxide imparts improved receptiveness to water-based inks in conjunction with an adhesive property.
• the acrylic polymer of the second resin component comprises a phenoxy group. Resultant ink reception layers made with this component provide improved adhesion of the ink reception layer to desired adherends and impart improved water resistance to images printed thereon.
• the relativfe proportions of first resin component and second resion component is such that in the resultant ink reception layer the first resin component constitutes 30 to 60 mass % with respect to a 100 mass % of the total of the first resin component and the second resin component.
• this formulation a good balance between the high-speed printing characteristic of the printing surface and water resistance of the printed image can be achieved.
• the other aspect of the present invention relate to the method for manufacturing a print media for water-based ink.
• the method for manufacturing a print media for water-based ink comprises applying a blend containing the first resin component, the second resin component, and a solvent to the base and form a coating on the base, and removing solvent from the coating such that micro-phase separation of the first resin component and the second resin component occurs.
• the printing surface is the print media which functions as the adhesion surface and has both good adhesive property and print characteristics, and a print media for water-based ink with good water resistance and bleed characteristics of the printed image even when printed with aqueous dye ink can be easily obtained.
• the application solution may be a suspension including the first resin component and the second resin component.
• the ink reception layer formed by such an application solution makes it easy to form the micro-phase separation structure in the printing surface by using the first resin component and the second resin component.
• Fig. 1 is a schematic cross-sectional view showing one illustrative embodiment of the print media of the present invention.
• the print media 10 has a base 12, and an ink reception layer 11 and a surface Fl, which does not face the base 12, i.e., is opposite thereto in the embodiment show, provided on one side of base 12 as the printing surface.
• the ink reception layer 11 comprises, and may consist essentially of, a hydrophilic first resin component and a thermal adhesive second resin component, and has a micro-phase separation structure formed by the first resin component and the second resin component in the printing surface Fl .
• the second resin component comprises an acrylic polymer with a quaternized amino group.
• the first resin component can function as the water-based ink reception area, providing desired receptivity to imaging ink, e.g., ink jet applied water-based inks, and the second resin component can function as the adhesion area, providing desired adhesion of the media to a desired adherend. Therefore, an image print with the water-based ink is possible on the printing surface Fl, and it functions as the adhesion surface.
• the print media 10 has the configuration described above, it has good adhesive property and good high-speed printing characteristic in the printing surface Fl, it is suitable for use as a print media for high-speed jet printing of more than 25 mm/sec, for example.
• the print media 10 the printed image formed by using the water-based ink on the printing surface Fl becomes superior in water resistance and bleed resistance.
• the conventional print media for example, the print media described in Reference D5
• the minute ink reception area made by the first resin component and the minute adhesion area made by the second resin component accomplish this complicated structure in the printing surface Fl due to the micro-phase separation. Therefore, the water-based ink infiltrates the ink reception area in points of impact, however the expansion (bleeding) due to the penetration from the ink reception area of the points of impact to the ink reception area other than the points of impact is obstructed by the adhesion area. Therefore is it thought that bleeding of the water-based ink in the print can be prevented, and a clear image can be formed. In addition, it is thought that the printed image becomes superior in water resistance since bleeding of the water-based ink is prevented for a similar reason even after water-based ink has been printed.
• the second resin component comprises a quaternized amino group in the printing surface Fl . Therefore, the fixation of the dye becomes very superior, and dye bleeding is controlled in the interface with the ink reception area and the adhesion area when printed with aqueous dye ink. Note that, it is thought that if the dye is an acid dye, then this fixation is obtained even more conspicuously, and the bleed is controlled even more conspicuously. This is why the print media 10 can be particularly suitable for use as a print media for acid dye ink.
• micro-phase separation structure means the first resin component and the second resin component exhibit a microscopic phase separation structure.
• the average diameter of the phase can be found by adding together the arbitrary number and the average diameter of 10 to 100 phases observed with a surface optics micrograph and electron micrograph.
• the micro-phase separation structure should preferably have an average diameter of the independent phase described above which is equal to or less than the dot diameter of water-based ink provided in the printing surface F 1.
• the independent phase described above should preferably be a minute size equal to or less than average a diameter of 30 ⁇ , 20 ⁇ , or 10 ⁇ .
• the minimum of the average diameter of the independent phase described above is not particularly limited, and may be more than 0.01 ⁇ and in some embodiments even more than 0.1 ⁇ .
• Island structure, cylinder structure, lamellar structure, and cocontinuum structures are given as examples of micro-phase separation structures. Specifically, an island structure where the first resin component having the hydrophilicity is in the shape of an island, and the second resin component constitutes the sea around it is desirable.
• the first resin component is hydrophilic. What this means is that, the first resin component has a property to make it capable of absorbing water-based ink. For example, when water has been dripped on the resin component surface to sufficiently to cover a wide area, and the resin component absorbs the drops of water within a few seconds (for example, five seconds), it can be said that the resin component is hydrophilic.
• the first resin component may comprise one or more of a polyalkylene oxide, hydrophilic acrylic acid resin, polyvinyl alcohol, polyvinylpyrrolidone, hydrophilic polyurethane resin, hydrophilic ethylene vinyl alcohol.
• the first resin component contains a polyalkylene oxide.
• the print and adhesion characteristics of printing surface Fl become even better, since the polyalkylene oxide is superior in the receptiveness of the water-based ink and has an adhesive property.
• Polyethylene oxide, polypropylene oxide, ethylene oxide, and propylene oxide co-polymer, are given as the polyalkylene oxide.
• polyalkylene oxide is preferably more than 80 mass %, and more preferably, more than 90 mass % of the total mass thereof.
• first resin component may be a polyalkylene oxide.
• the second resin component is a thermal adhesive resin component and contains at least an acrylic polymer with a quaternized amino group.
• the acrylic polymer may further include a phenoxy group.
• the acrylic polymer may be a polymer of which the monomer component includes an acrylic monomer with a quaternized amino group.
• the monomer component may further include an acrylic monomer with a phenoxy group, alkyl (meth)acrylate, or (meth)acrylic acid.
• an acrylic monomer with a quaternized amino group and a polymer of the monomer component including alkyl (meth)acrylate and (meth)acrylic acid are given as one form of the acrylic polymer, and the monomer component may include an acrylic monomer with a phenoxy group.
• the ratio of acrylic monomer with a quaternized amino group in the monomer component can be a 3 to 13 mass % or it can be 5 to 1 1 mass %.
• the ratio of alkyl (meth)acrylate in the monomer component can be 20 to 90 mass %, and should preferably be 25 to 70 mass %, and more preferably be 30 to 60 mass %.
• the ratio of the (meth)acrylic acid of the monomer component may be 1 to 8 mass %.
• the ratio of the acrylic monomer with the phenoxy group in the monomer component may be 0 to 70 mass %, and should preferably be 10 to 65 mass %, and more preferably be 20 to 60 mass %.
• the total of the alkyl (meth)acrylate and acrylic monomer with the phenoxy group in the monomer component may be 60 to 94 mass %, and should preferably be 70 to 90 mass %.
• R 1 , R 2 , and R 3 are independently an alkyl group or aryl group and the X is the monovalent anion.
• R 1 , R 2 , and R 3 should preferably each be an alkyl or phenyl group, more preferably an alkyl group, and even more preferably an alkyl group of Ci_2 (an alkyl group with a carbon number of one or two).
• the expressed monovalent anion which is an X is not particularly limited, however examples such as a halogenide ion (a chloride ion, a bromide ion, an iodide ion) is given. Of these, a chloride ion is more preferable due to its easily availability. ⁇ , ⁇ -Dimethylaminoethyl (meth)acrylate quaternized with methyl chloride,
• ⁇ , ⁇ -dimethylamino propyl (meth)acrylate quaternized with methyl chloride N,N-dimethylamino ethyl (meta)acrylic amide quaternized with methyl chloride, and ⁇ , ⁇ -dimethylamino propyl (meta)acrylic amide quaternized with methyl chloride are suitable for use as an acrylic monomer with a quaternized amino group.
• Phenoxy ethyl (meth)acrylate is given as the acrylic monomer with the phenoxy group.
• Ci_i6 alkyl (meth)acrylate is preferable, and Ci_io alkyl (meth)acrylate is more preferable as the alkyl (meth)acrylate.
• Ci_i 6 " and "Cuo” shows the carbon number of the alkyl group excluding the (meth)acryloyl group.
• the second resin component may contain hydrophobic resin component as the thermal adhesive resin component excluding the acrylic polymer.
• the second resin component may contain polyester, hydrophobic polyurethane resin, polyester urethane resin, and ethylene vinyl acetate.
• hydrophobic means to have a property to repel water-based ink. For example, it could be said that it is a hydrophobic resin if almost all of the drops of water are repelled when the water is dropped on the resin the surface.
• the acrylic polymer described above constitutes more than 50 mass %, and more preferably more than 60 mass % thereof.
• the second resin component may consist essentially of the acrylic polymer.
• the first resin component content in the ink reception layer 11 can be a 20 to 70 mass %, and can also be 30 to 60 mass % with regards to the gross weight of a 100 mass % of the first and the second resin component.
• the ratio (Si/S 2 ) of the total area (Si) of the ink reception area made by the first resin component and total area (S2) of the ink reception area made by the second resin component may be, for example, 0.2 to 4.0, and it may be 0.4 to 1.5. Print characteristics, adhesive property and water resistance become even more superior by being provided with an ink reception area and adhesion area at such area ratio.
• the ink reception layer 11 can be set to 10 to 40 ⁇ as well as 20 to 30 ⁇ for example.
• the ink reception layer 11 manufactured to become such a thickness has even better print and adhesion characteristics of printing surface Fl .
• the reason for such an effect is not always clear, however, it is thought that the adhesive strength of the second resin component is effectively expressed with a thickness of more than 15um, and good adhesive strength can be secured.
• the micro-phase separation structure that is homogeneous, and is formed easily when it is less than 40 ⁇ .
• the ink reception layer 11 should have optical transparency. According to such ink reception layer 11, the image printed on the printing surface Fl can be viewed from surfaces other than the printing surface F 1. In this case, it is preferable for a base 12 (to mentioned later) to be added, and to have optical transparency.
• the ink reception layer 11 may have a first micro-phase isolation region that contains more of the first resin component than the second resin component, and a second micro-phase isolation region that contains more of the second resin component than the first resin component, surrounds the first micro-phase isolation region in approximately the shape of a ring and is relatively convex. In this way, bleeding is prevented effectively in the region interface, and high-speed printing characteristics are largely improved by placing the region (the second micro-phase isolation region) where there is relatively a lot of the second resin component around the region (the first micro-phase isolation region) where there is relatively a lot of the first resin component.
• to contain more of the first resin component than the second resin component means that the area ratio of the surface made by the first resin component occupying the region is bigger than the area ratio of the surface made by the second resin component.
• relatively convex means that the region is at least higher than the adjacent first aspect isolation region.
• the ink reception layer 11 should preferably have a structure where the second micro-phase isolation region is surrounded around the first micro-phase isolation region and that this structural unit has a repeated unevenness structure in the printing surface Fl as one unit.
• the ink reception layer 11 should preferably have an unevenness structure with a concave part and a convex part surrounding the concave part in approximately the shape of a ring, wherein the concave part forms the first micro-phase isolation region that contains more of the first resin component than the second resin component, and the convex part forms the second micro-phase isolation region that contains more of the second resin component than the first resin component.
• the first micro-phase isolation region includes more of the first resin component and has good absorption of the water-based ink. It is thought that the water-based ink maintained by concave part settles in the ink reception layer 11 due to the high absorbency of the first micro-phase isolation region by making the micro-phase isolation region with the concave portion.
• the second micro-phase isolation region includes more of the second resin component, and there is relatively little of the first resin component. It is thought that the superior adhesive property and water resistance are realized due to the convex portion where this kind of second micro-phase isolation region comes into contact by being adhered on the object.
• the shape of the first micro-phase isolation region may be approximately in the shape of a circle, oval or polygon, but is typically circular in shape.
• the diameter of the first micro-phase isolation region may be for example, 10 ⁇ to 500 ⁇ or 50 ⁇ to 300 ⁇
• the second micro-phase isolation region relatively forms a convex; however the difference (h 2 - hi) between the average height hi of the adjacent first micro-phase separation structure and the average height h 2 of the second micro-phase isolation region may typically be 1 ⁇ to 30 ⁇ , and in some instances may be 2 ⁇ to 20 ⁇ .
• the second micro-phase isolation region should preferably surround the first micro-phase isolation region in the shape of a ring; however it does not have to be in a completed circle, as long as the second micro-phase isolation region is formed around the first micro-phase isolation region in approximately the shape of a ring.
• the base 12 should have a surface where it is possible to provide an ink reception layer 11. Note that, in the print media 10, the base 12 makes the shape of film, but the base does not always have to be shape of film used in the present invention.
• Paper, synthetic paper, resin film or a resin sheet made from resins such as polyvinyl chloride resin, polyolefin resin, acrylic acid resin, polyester, and polyurethane resin can be used as the base 12.
• the base may be single layer or multilayer and should provide sufficient dimensional stability for formation of a ink reception layer thereon and subsequent handling and processing of the print media.
• suitable material for the base taking into account desired flexibility, tear strength, stretch properties, elasticity, weight, etc.
• base 12 it is preferable for base 12 to have optical transparency.
• the image printed on the printing surface F 1 can be seen through the ink reception layer 11 and the base 12 due to both the base 12 and the ink reception layer 11 having optical transparency.
• print media for water-based ink Uses of the print media for water-based ink according to the present embodiment will be described below. Note that, the use of a print media for water-based ink of the present invention is not a limited to the following embodiment.
• the print media 10 With the print media 10, a clear image can be printed on the printing surface Fl using water-based ink and the printing surface Fl also functions as the adhesion surface. Therefore, the print media 10 can be adhered to an object easily without any extra adhesion processing.
• the print media 10 is suitable for uses as a film affixed to IC cards, photo identification cards, etc.
• IC cards photo identification cards
• the print media 10 is suitable for uses as a film affixed to IC cards, photo identification cards, etc.
• first an image to be displayed on an IC card is printed on the printing surface Fl, and then heat laminated with the printed surface Fl and IC card facing opposite of one another.
• IC cards having a clear image can be produced quickly because the print media 10 is superior in print characteristics, adhesive property and water resistance. In addition, the produced IC cards also become superior in water resistance.
• the minute ink reception area gets destroyed, and the print content becomes illegible due to the micro-phase separation structure in the printing surface Fl of the print media 10.
• the IC cards can be prevented from being reused for unauthorized purposes.
• the print media 10 can be adhered on objects having unevenness or curved surfaces to be used as a decorative film.
• a heat extensibility base should preferably be used for the base 12 of the print media 10.
• such a print media 10 can be adhered on objects having unevenness or curved surfaces to take the shape while heating the print media 10 with a dryer or the like.
• the print media 10 may have a support layer on the other surface of the base 12 on the area, depending on the use, to support the print media 10 and improve the handling characteristics. Such a situation is shown Fig. 2.
• the print media 20 shown in Fig. 2 has a base 22, and an ink reception layer 21 and a surface F2, which does not face the base 22, provided on one side of base 22, and a support layer 23 provided on the other side of the base 22.
• the base 22 and the ink reception layer 21 in the print media 20 is equivalent to the base 12 and the ink reception layer 11 in the print media 10.
• the print media 20 is superior in the handling characteristics because the base 22 and the ink reception layer 21 are supported by the support layer 23.
• the support layer 23 can be peeled after the water-based ink printed image has been form and only the base 22 and the ink reception layer 21 can be adhered on the object.
• the print media 10 may have an anti-grime layer on the other surface of the base 12 on the area, depending on the use, to prevent dirt and grime from getting attached to most outer surface after the print media 10 has been adhered on the object. Such the situation is shown Fig. 3.
• the print media 30 shown in Fig. 3 has a base 32, an ink reception layer 31 with a surface F3 that is not faced with the base 22 that is provided on one side of base 32 as the printing surface, and grime layer 33 provided on the other side of the base 32.
• the base 32 and the ink reception layer 21 in the print media 30 is equivalent to the base 12 and the ink reception layer 11 in the print media 10.
• the anti-grime 33 can be formed from a resin composition containing fluoric resin.
• the print media 30 may also have a support layer 34 to support the base 32, ink reception layer 31 and anti-grime 33.
• the support layer 34 can be peeled after the water-based ink printed image has been formed and only the base 32, ink reception layer 31 and anti-grime 33 can be adhered on the object.
• the method to print water-based ink on the printing surface Fl of the print media 10 is not particularly limited; however ink jet printing is preferable.
• a printed image can be formed quickly if ink jet printing is performed, and the above-described IC card can be produced even more quickly.
• the printing speed of the jet printing may be more than 25 mm/sec, more than 50 mm/sec, or even more than 100 mm/sec.
• Advantages of the present invention include that clear images can be formed on media of the invention without suffering bleeding of the ink even with such a printing speed since the print media 10 is superior in high-speed printing characteristics in the printing surface Fl .
• the water-based ink to be used for print is not limited in particular, but it may be aqueous dye ink, or it may be acid dye ink. According to the print media 10, when dye ink is used, bleeding can be sufficiently controlled.
• the manufacturing method of the print media for water-based ink according to this embodiment will be described.
• the print media for water-based ink of the present invention is not limited to the print media produced by the following manufacturing method.
• This manufacturing method comprises a step to apply a solution containing the first resin component, the second resin component and a solvent to the base and form a coating on the base, and a step to remove the solvent from the coating and allow micro-phase separation of the first resin component and the second resin component.
• the printing surface is the print media which functions as the adhesion surface and has both good adhesive property and print characteristics, and a print media for water-based ink (refer to print media 10 for a specific example) with good water resistance and bleed characteristics of the printed image even when printed with aqueous dye ink can be easily obtained.
• the first resin component and the second resin component may be dissolved in a solvent and may be dispersed as resin component fine particles in the solvent to form the suspension (the term "solvent" is used herein to refer to such embodiments wherein the subject fluids would more precisely be referred to as liquid media, liquid fraction, etc.).
• the solvent may be such that the first resin component and the second resin component are dissolved or capable of being dispersed uniformly in the application solution, and an organic solvent may be suitably used.
• Aromatic types such as benzene, toluene, and xylene; ketones such as acetone, and methyl ethyl ketone; esters such as ethyl acetate, and butyl acetate; alcohols such as methanol, and ethanol are given as examples of the organic solvent. These can be combined together or used individually.
• a mixture of water or water and alcohol can be used as a solvent in this manufacturing method.
• the application solution may be heated if necessary.
• the application solution may be heated to 30 to 60°C to let the first resin component and the second resin component dissolve.
• the application liquid may be a suspension including the first resin component and the second resin component.
• the ink reception layer formed with such an application solution makes the characteristic unevenness shape having the concave part and the peak-shaped convex part surrounding the concave part in the printing surface, and further improves the water resistance and bleeds characteristics of the printed image if it is formed to a convex and concave shape.
• the resin fine particles can be formed by using the lytic difference between the first resin component and the second resin component and allowing the partial separation of the first resin component and/or the second resin component when mixing the first solution and the second solutions together.
• the first resin component when the first resin component is a polyalkylene oxide, the first resin component can be allowed to dissolve at 40°C in the mixture solvent of methyl ethyl ketone / toluene / methanol (weight ratio 2/1/1).
• the acrylic polymer which is the second resin component can be allowed to dissolve at room temperature (for example, 20°C) in a mixture solvent of the acetone / methanol.
• the first solution should preferably contain methyl ethyl ketone, toluene and methanol as a solvent, and it should preferably be heated to 35 to 60°C.
• the second solution should preferably contain methyl ethyl ketone or acetone and methanol as a solvent, and the temperature should preferably be 15 to 30°C.
• the density of the first resin component in the first solution should preferably be 10 to 20 mass %, and more preferably be 14 to 16 mass %.
• the density of the second resin component in the second solution should preferably be 30 to 40 mass %, and more preferably be 33 to 38 mass %.
• the coating can be applied by applying the application solution on one side of the base.
• the application method of the application liquid is not particularly limited, and well known methods such as the knife coat method, spin coat method, roll coat method, silkscreen coat method, and gravure coat method can be used.
• the coating should be formed so that the thickness of the ink reception layer formed after the second process becomes 10 to 40 ⁇ .
• the coating is formed to become such a thickness, the printing surface of the ink reception layer to be obtained becomes even more superior in print characteristics and its adhesive property.
• the solvent is removed from the coating in the second process.
• a method to volatilize and remove the solvent by heating, and an air-drying method are given as methods to remove the organic solvent.
• the solvent of the coating does not always have to be entirely removed, and the ink reception layer may contain some of the solvent.
• print media of the invention may be formed in sheet or roll form.
• the printed image formed with the water-based ink on the printing surface Fl of the print media 10 may be a decorative film.
• the present invention may be a decorative item (for example, an IC card having a printed image) wherein the print media 10 with the printed image formed by the water-based ink on the printing surface Fl is adhered on the object (for example, main body an IC card).
• Acrylic Polymer Bl 33 mass % of methyl acrylate (below expressed as "MA” depending on the case.), 55 mass % of phenoxy ethyl acrylate (below expressed as “PhEA” depending on the case), 10 mass % of ⁇ , ⁇ -dimethylamino ethyl acrylate quaternized with methyl chloride (below expressed as "DMAEA-Q” depending on the case), and 2 mass % of acrylic acid (below expressed as "AA” depending on the case) was uniformly dissolved in a mixture solvent of 148.58 acetone mass % and 34.49 methanol mass % and the solution was reacted.
• MA mass methyl acrylate
• PhEA phenoxy ethyl acrylate
• DMAEA-Q 10 mass % of ⁇ , ⁇ -dimethylamino ethyl acrylate quaternized with methyl chloride
• AA acrylic acid
• Acrylic Polymer B2 43 mass % of methyl acrylate, 45 mass % of phenoxy ethyl acrylate, 10 mass % of ⁇ , ⁇ -dimethylamino ethyl acrylate quaternized with methyl chloride, and 2 mass % of acrylic acid was uniformly dissolved in a mixture solvent of 148.58 acetone mass % and 34.49 methanol mass % and the solution was reacted. Note that, a water solution of 79 mass % for the solidity was used as DMAEA-Q.
• This reaction solution was poured into a pressure and heat-resisting glass container, and nitrogen was passed through the reaction solution while stirring it for 10 minutes to performed deoxidation after having added 0.1 mass % of azobisisobutyronitrile as a start agent. Then, an interpolymerization reaction was performed by warming it at 50°C for 20 hours, and a 35 mass % solution of the acrylic polymer B2 was obtained.
• Acrylic Polymer B3 23 mass % of methyl acrylate, 65 mass % of phenoxy ethyl acrylate, 10 mass % of ⁇ , ⁇ -dimethylamino ethyl acrylate quaternized with methyl chloride, and 2 mass % of acrylic acid was uniformly dissolved in a mixture solvent of 148.58 acetone mass % and 34.49 methanol mass % and the solution was reacted. Note that, a water solution of 79 mass % for the solidity was used as DMAEA-Q.
• This reaction solution was poured into a pressure and heat-resisting glass container, and nitrogen was passed through the reaction solution while stirring it for 10 minutes to performed deoxidation after having added 0.1 mass % of azobisisobutyronitrile as a start agent. Then, an interpolymerization reaction was performed by warming it at 50°C for 20 hours, and a 35 mass % solution of the acrylic polymer B3 was obtained.
• Acrylic Polymer B4 73 mass % of methyl acrylate, 15 mass % of phenoxy ethyl acrylate, 10 mass % of ⁇ , ⁇ -dimethylamino ethyl acrylate quaternized with methyl chloride, and 2 mass % of acrylic acid was uniformly dissolved in a mixture solvent of 148.58 acetone mass % and 34.49 methanol mass % and the solution was reacted. Note that, a water solution of 79 mass % for the solidity was used as DMAEA-Q.
• This reaction solution was poured into a pressure and heat-resisting glass container, and nitrogen was passed through the reaction solution while stirring it for 10 minutes to performed deoxidation after having added 0.1 mass % of azobisisobutyronitrile as a start agent. Then, an interpolymerization reaction was performed by warming it at 50°C for 20 hours, and a 35 mass % solution of the acrylic polymer B4 was obtained.
• Acrylic Polymer B5 33 mass % of 2-ethyl hexyl acrylate (below expressed as "2EHA" depending on the case.), 55 mass % of phenoxy ethyl acrylate, 10 mass % of N,N-dimethylamino ethyl acrylate quaternized with methyl chloride, and 2 mass % of acrylic acid was uniformly dissolved in a mixture solvent of 148.58 acetone mass % and 34.49 methanol mass % and the solution was reacted. Note that, a water solution of 79 mass % for the solidity was used as DMAEA-Q.
• This reaction solution was poured into a pressure and heat-resisting glass container, and nitrogen was passed through the reaction solution while stirring it for 10 minutes to performed deoxidation after having added 0.1 mass % of azobisisobutyronitrile as a start agent. Then, an interpolymerization reaction was performed by warming it at 50°C for 20 hours, and a 35 mass % solution of the acrylic polymer B - 5 was obtained.
• Acrylic Polymer B6 29 mass % of methyl acrylate, 55 mass % phenoxy ethyl acrylate,
• Acrylic Polymer B7 88 mass % of methyl acrylate, 10 mass % of N,N-dimethylamino ethyl acrylate quaternized with methyl chloride, and 2 mass % of acrylic acid was uniformly dissolved in a mixture solvent of 148.58 acetone mass % and 34.49 methanol mass % and the solution was reacted. Note that, a water solution of 79 mass % for the solidity was used as DMAEA-Q. This reaction solution was poured into a pressure and heat-resisting glass container, and nitrogen was passed through the reaction solution while stirring it for 10 minutes to performed deoxidation after having added 0.1 mass % of azobisisobutyronitrile as a start agent. Then, an interpolymerization reaction was performed by warming it at 50°C for 20 hours, and a 35 mass % solution of the acrylic polymer B7 was obtained.
• Acrylic Polymer B8 58 mass % of methyl acrylate, 35 mass % of phenoxy ethyl acrylate, 5 mass % of ⁇ , ⁇ -dimethylamino ethyl acrylate quaternized with methyl chloride, and 2 mass % of acrylic acid was uniformly dissolved in a mixture solvent of 148.58 acetone mass % and 34.49 methanol mass % and the solution was reacted.
• This reaction solution was poured into a pressure and heat-resisting glass container, and nitrogen was passed through the reaction solution while stirring it for 10 minutes to performed deoxidation after having added 0.1 mass % of azobisisobutyronitrile as a start agent. Then, an interpolymerization reaction was performed by warming it at 50°C for 20 hours, and a 35 mass % solution of the acrylic polymer B8 was obtained.
• Acrylic Polymer B9 33 mass % of methyl acrylate, 55 mass % of phenoxy ethyl acrylate, 10 mass % of ⁇ , ⁇ -dimethylamino ethyl acrylate (third grade amine expressed as
• Acrylic Polymer B10 43 mass % of methyl acrylate, 55 mass % of phenoxy ethyl acrylate and 2 mass % of acrylic acid was uniformly dissolved in a mixture solvent of 148.58 acetone mass % and 34.49 methanol mass % and the solution was reacted.
• This reaction solution was poured into a pressure and heat-resisting glass container, and nitrogen was passed through the reaction solution while stirring it for 10 minutes to performed deoxidation after having added 0.1 mass % of azobisisobutyronitrile as a start agent. Then, an interpolymerization reaction was performed by warming it at 50°C for 20 hours, and a 35 mass % solution of the acrylic polymer B 10 was obtained.
• Acrylic Polymer B 11 28 mass % of methyl acrylate, 55 mass % of phenoxy ethyl acrylate, 15 mass % of ⁇ , ⁇ -dimethylamino ethyl acrylate quaternized with methyl chloride, and 2 mass % of acrylic acid was uniformly dissolved in a mixture solvent of 148.58 acetone mass % and 34.49 methanol mass % and the solution was reacted.
• This reaction solution was poured into a pressure and heat-resisting glass container, and nitrogen was passed through the reaction solution while stirring it for 10 minutes to performed deoxidation after having added 0.1 mass % of azobisisobutyronitrile as a start agent. Then, an interpolymerization reaction was performed by warming it at 50°C for 20 hours, and a 35 mass % solution of the acrylic polymer B5 was obtained.
• Acrylic Polymer B12 25 mass % of methyl acrylate, 55 mass % of phenoxy ethyl acrylate, 10 mass % of ⁇ , ⁇ -dimethylamino ethyl acrylate quaternized with methyl chloride, and 10 mass % of acrylic acid was uniformly dissolved in a mixture solvent of 148.58 acetone mass % and 34.49 methanol mass % and the solution was reacted.
• This reaction solution was poured into a pressure and heat-resisting glass container, and nitrogen was passed through the reaction solution while stirring it for 10 minutes to performed deoxidation after having added 0.1 mass % of azobisisobutyronitrile as a start agent. Then, an interpolymerization reaction was performed by warming it at 50°C for 20 hours, and a 35 mass % solution of the acrylic polymer B5 was obtained.
• the ratios (mass ratios) of the monomer unit which constitutes the acrylic polymers B 1 to B 10 are shown in following Table 1.
• AQUA COKE® (from Sumitomo Seika Chemicals Co., Ltd., a polyalkylene oxide, 100 mass % for solidity) was dissolved at 40°C in a mixture solvent (mass ratio 2/1/1) of the methyl ethyl ketone / toluene / methanol and a solution Al with a solid density of 15 mass % was produced as the first resin component.
• a solution with 35 mass % of the acrylic polymer Bl (hereinafter referred to as the solution Bl) was used as the second resin component.
• a print media 1 was obtained by applying the solution C 1 on a polyethylene terephthalate film (a PET film) having a thickness of 50um using the knife coat method, and allowing the solution C 1 to dry for 10 minutes in an oven set to 80°C to form the ink reception layer on the PET film. Then, the thickness of the ink reception layer formed after drying was adjusted to become 25 ⁇ . Note that, the thickness of the ink reception layer is adjusted by adjusting the gap between the PET film surface and the knife surface.
• the ink reception layer of print media 1 had a near uniform micro-phase separation structure in the printing surface. The result is shown in Fig. 4.
• the printing surface of the ink reception layer of the obtained print media 1 was measured with a non-contact surface coarseness-measuring instrument (from Zaygo) to measure the surface coarseness of the printing surface.
• a non-contact surface coarseness-measuring instrument from Zaygo
• the unique unevenness structural arrangement was confirmed, wherein the structural unit consisting of the first micro-phase isolation region approximately in the shape of a circle, and the second convex-shaped micro-phase isolation region surrounding that outer periphery in approximately a ring shape.
• the unique unevenness structure was formed such that the second micro-phase separation structure rose up in the shape of a peak and surrounded the first micro-phase isolation region in approximately the shape of a circle.
• the micro-phase separation structure of the printing surface formed the island structure, and the average diameter of the island was about 5 ⁇ .
• the diameter of the first micro-phase isolation region in approximately the shape of a circle was roughly 50 to 300 ⁇
• the difference (h 2 - h t ) between the average height hi of the first micro-phase separation structure and average height h 2 of the second micro-phase isolation region was roughly 25 to 30 ⁇ .
• the print media 2 was obtained similar to that of Example 1.
• the ink reception layer of print media 2 had a near uniform micro-phase separation structure in the printing surface.
• the printing surface of the ink reception layer of the obtained print media 2 was measured with a non-contact surface coarseness measuring instrument (from Zaygo) to measure the surface coarseness of the printing surface. From a result of the measurement with the non-contact surface coarseness measuring instrument, it was confirmed that a multiple arranged unique unevenness structures with a first micro-phase isolation region, and a second convex-shaped micro-phase isolation region surrounding the outer periphery of the first micro-phase isolation region in approximately a ring shape was formed similar to that of Example 1 even in the printing surface of the ink reception layer of the print media 2.
• the print media 3 was obtained similar to that of Example 1.
• the ink reception layer of print media 3 had a near uniform micro-phase separation structure in the printing surface.
• the printing surface of the ink reception layer of the obtained print media 3 was measured with a non-contact surface coarseness measuring instrument (from Zaygo) to measure the surface coarseness of the printing surface. From a result of the measurement with the non-contact surface coarseness measuring instrument, it was confirmed that a multiple arranged unique unevenness structures with a first micro-phase isolation region, and a second convex-shaped micro-phase isolation region surrounding the outer periphery of the first micro-phase isolation region in approximately a ring shape was formed similar to that of Example 1 even in the printing surface of the ink reception layer of the print media 3.
• the print media 4 was obtained similar to that of Example 1.
• the ink reception layer of print media 4 had a near uniform micro-phase separation structure in the printing surface.
• the printing surface of the ink reception layer of the obtained print media 4 was measured with a non-contact surface coarseness measuring instrument (from Zaygo) to measure the surface coarseness of the printing surface. From a result of the measurement with the non-contact surface coarseness measuring instrument, it was confirmed that a multiple arranged unique unevenness structures with a first micro-phase isolation region, and a second convex-shaped micro-phase isolation region surrounding the outer periphery of the first micro-phase isolation region in approximately a ring shape was formed similar to that of Example 1 even in the printing surface of the ink reception layer of the print media 4.
• the print characteristics, water resistance, normal temperature adhesive strength and high temperature adhesive strength were evaluated for the print media 4 according to the following evaluation method. The evaluation results are as shown in Table 2.
• the print media 5 was obtained similar to that of Example 1.
• the ink reception layer of print media 5 had a near uniform micro-phase separation structure in the printing surface.
• the printing surface of the ink reception layer of the obtained print media 5 was measured with a non-contact surface coarseness measuring instrument (from Zaygo) to measure the surface coarseness of the printing surface. From a result of the measurement with the non-contact surface coarseness measuring instrument, it was confirmed that a multiple arranged unique unevenness structures with a first micro-phase isolation region, and a second convex-shaped micro-phase isolation region surrounding the outer periphery of the first micro-phase isolation region in approximately a ring shape was formed similar to that of Example 1 even in the printing surface of the ink reception layer of the print media 5.
• the print media 6 was obtained similar to that of Example 1.
• the ink reception layer of print media 6 had a near uniform micro-phase separation structure in the printing surface.
• the printing surface of the ink reception layer of the obtained print media 6 was measured with a non-contact surface coarseness measuring instrument (from Zaygo) to measure the surface coarseness of the printing surface. From a result of the measurement with the non-contact surface coarseness measuring instrument, it was confirmed that a multiple arranged unique unevenness structures with a first micro-phase isolation region, and a second convex-shaped micro-phase isolation region surrounding the outer periphery of the first micro-phase isolation region in approximately a ring shape was formed similar to that of Example 1 even in the printing surface of the ink reception layer of the print media 6.
• the print media 7 was obtained similar to that of Example 1.
• the ink reception layer of print media 7 had a near uniform micro-phase separation structure in the printing surface.
• the printing surface of the ink reception layer of the obtained print media 7 was measured with a non-contact surface coarseness measuring instrument (from Zaygo) to measure the surface coarseness of the printing surface. From a result of the measurement with the non-contact surface coarseness measuring instrument, it was confirmed that a multiple arranged unique unevenness structures with a first micro-phase isolation region, and a second convex-shaped micro-phase isolation region surrounding the outer periphery of the first micro-phase isolation region in approximately a ring shape was formed similar to that of Example 1 even in the printing surface of the ink reception layer of the print media 7.
• AQUA COKE® (from Sumitomo Seika Chemicals Co., Ltd., a polyalkylene oxide, 100 mass % for solidity) was dissolved at 40°C in a mixture solvent (mass ratio 2/1/1) of the methyl ethyl ketone / toluene / methanol and a solution A2 with a solid density of 15 mass % was produced as the first resin component.
• the print media 8 was obtained similar to that of Example 1.
• the ink reception layer of print media 8 had a near uniform micro-phase separation structure in the printing surface.
• the printing surface of the ink reception layer of the obtained print media 8 was measured with a non-contact surface coarseness measuring instrument (from Zaygo) to measure the surface coarseness of the printing surface.
• a non-contact surface coarseness measuring instrument from Zaygo
• the unique unevenness structure observed with Example 1 was not observed in the printing surface of the ink reception layer of print media 8, and there were large mountain-shaped cells forming the surface structure.
• the solution A2 was prepared similar to that of Example 8. Then, a solution A2 and a solution B 1 , which were 40°C, were mixed so that the mass ratio of the first resin component and the second resin component became 30/70, and a mixture C3 was prepared.
• the print media 9 was obtained similar to that of Example 1.
• the ink reception layer of print media 9 had a near uniform micro-phase separation structure in the printing surface.
• the printing surface of the ink reception layer of the obtained print media 9 was measured with a non-contact surface coarseness measuring instrument (from Zaygo) to measure the surface coarseness of the printing surface.
• a non-contact surface coarseness measuring instrument from Zaygo
• the unique unevenness structure observed with Example 1 was not observed in the printing surface of the ink reception layer of print media 8, and there were large mountain-shaped cells forming the surface structure.
• the solution A2 was prepared similar to that of Example 8.
• a 35 mass % solution of the acrylic polymer B7 (hereinafter referred to as solution B7) was used as the second resin component.
• the print media 10 was obtained similar to that of Example 1.
• the ink reception layer of print media 10 had a near uniform micro-phase separation structure in the printing surface.
• the printing surface of the ink reception layer of the obtained print media 10 was measured with a non-contact surface coarseness measuring instrument (from Zaygo) to measure the surface coarseness of the printing surface.
• a non-contact surface coarseness measuring instrument from Zaygo
• the unique unevenness structure observed with Example 1 was not observed in the printing surface of the ink reception layer of print media 9, and there were large mountain-shaped cells forming the surface structure.
• the print media 11 was obtained similar to that of Example 1.
• the ink reception layer of print media 11 had a near uniform micro-phase separation structure in the printing surface.
• the printing surface of the ink reception layer of the obtained print media 11 was measured with a non-contact surface coarseness measuring instrument (from Zaygo) to measure the surface coarseness of the printing surface. From a result of the measurement with the non-contact surface coarseness measuring instrument, it was confirmed that a multiple arranged unique unevenness structures with a first micro-phase isolation region, and a second convex-shaped micro-phase isolation region surrounding the outer periphery of the first micro-phase isolation region in approximately a ring shape was formed similar to that of Example 1 even in the printing surface of the ink reception layer of the print media 11.
• the solution A2 was prepared similar to that of Example 8. Then, a solution A2 and a 35 mass % solution of acrylic polymer B9 (hereinafter referred to as solution B9) were mixed so that the mass ratio of the first resin component and the second resin component became 40/60, and a mixture D 1 was prepared.
• the print media 21 was obtained similar to that of Example 1.
• the print media 21 had a near uniform micro-phase separation structure in the printing surface when observed with a surface optical microscope.
• a non-contact surface coarseness measuring instrument from Zaygo
• the unique unevenness structure observed with Example 1 was not observed in the printing surface, and there were large mountain- shaped cells forming the surface structure.
• the observation result of the surface optical microscope is shown in Fig. 6, and the measurement result of the non-contact surface coarseness measuring instrument is shown in Fig. 7.
• the solution A 1 was prepared similar to that of Example 1. Then, a solution A 1 and a 35 mass % solution of acrylic polymer BIO (hereinafter referred to as solution BIO) were mixed so that the mass ratio of the first resin component and the second resin component became 40/60, and a mixture D2 was prepared.
• solution BIO acrylic polymer BIO
• the print media 22 was obtained similar to that of Example 1.
• the print media 22 had a near uniform micro-phase separation structure in the printing surface when observed with a surface optical microscope.
• a non-contact surface coarseness measuring instrument from Zaygo
• the unique unevenness structure observed with Example 1 was not observed in the printing surface.
• a print media 23 was obtained by casting the solution D3 on a polyethylene terephthalate film (a PET film) having a thickness of 50 ⁇ using the knife coat method, and allowing the solution D3 to dry for 10 minutes in an oven set to 80°C to form the ink reception layer on the PET film. Then, the thickness of the ink reception layer formed after drying was adjusted to become 25 ⁇ .
• a PET film polyethylene terephthalate film
• the print media 23 had a near uniform micro-phase separation structure in the printing surface when observed with a surface optical microscope.
• a peel strength of 180° (N/25 mm) was measured with a pull test machine at 23°C after the obtained measurement sample was left to stand for 24 hours at 23°C.
• the measurement condition was set at a tension speed of 200 mm/min.
• a measurement result was evaluated as "A” in a case of more than 15 N/25 mm or when the materials were damages, "B” in a case of between 15 - 10 N/25 mm, and "C” in cases of less than 10 N/25 mm.
• the measurement sample was obtained by the method similar to the evaluation of the normal temperature adhesive strength. A peel strength of 180° (N/25 mm) was measured with a pull test machine at 80°C after the obtained measurement sample was left to stand for 24 hours at 23°C. The measurement condition was set at a tension speed of 200 mm min. A measurement result was evaluated as "A” in a case of more than 15 N/25 mm or when the materials were damages, "B” in a case of between 15 - 10 N/25 mm, and "C” in cases of less than 10 N/25 mm.

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