CN104755272A

CN104755272A - Print media for water-based color ink jet printing and method for manufacturing same

Info

Publication number: CN104755272A
Application number: CN201380048296.8A
Authority: CN
Inventors: 佐佐木信; 樱井爱三; 山田健史; 大石雅敬
Original assignee: 3M Innovative Properties Co
Current assignee: 3M Innovative Properties Co
Priority date: 2012-09-18
Filing date: 2013-09-18
Publication date: 2015-07-01
Anticipated expiration: 2033-09-18
Also published as: JP2014058121A; JP2015529586A; JP6181761B2; AU2013318125A1; TWI651215B; WO2014047200A1; TW201418057A; KR20150053997A; CN104755272B; KR102106933B1; AU2013318125B2

Abstract

A print media for water-based ink comprising a base, and an ink reception layer with a surface not facing the base to be used as the printing surface provided on one side of the base, wherein the ink reception layer includes; a hydrophilic first resin and a second resin having a thermal adhesive property a micro-phase separation structure in the printing surface, which is formed by the first resin and the second resin; and the second resin contains an acrylic polymer with a quaternized amino group.

Description

The printed medium of waterbased color ink jet printing and manufacture method thereof

Technical field

The present invention relates to printed medium, the printed medium of particularly waterbased color ink jet printing and manufacture method thereof.

Background technology

As conventional printed medium, multiple product such as paper, synthetic paper and resin molding are known.These printed mediums are fixed on various object, and by such as providing adhesive on printed medium, applying two-sided tape etc. and using.

In recent years, the configuration of printed medium has become known, and wherein print surface is also used as adhesive surface and does not need to apply adhesive on printing images.Disclosed in illustrative example has in following patent: D1-Japanese Patent Laid-Open No.2004-276613; D2-Japanese Patent Laid-Open No.11-165457; D3-Japanese Patent Laid-Open No.2008-087276; D 4-Japanese Patent Laid-Open No.2008-087324; And D5-Japanese Patent Laid-Open No.2011-255650.

Need that a kind of resistance to image that can show improvement is bleed, the water-based inkjet inks accepting medium of water absorption resistance and resistance to damage by water, especially for the water-based inkjet inks accepting medium of high speed printing application.

Summary of the invention

The ink-jet that the invention provides a kind of improvement accepts printed medium and prepares the method for this medium.

In simple terms, printed medium of the present invention comprises the base portion with first surface and the black receiving layer gone up at least partially at base portion first surface.According to the present invention: (1) black receiving layer has the print surface limited by the microphase-separated of the blend of the first resin Composition composition and the second resin Composition composition; (2) first resin Compositions are hydrophilic; And (3) second resin Compositions comprise the acrylic polymer with quaternized amino groups and show heat adhesive characteristic.Find surprisingly, the black receiving layer with print surface or the region limited by micro phase separation structure as described herein provides beyond thought and favourable result.

As described herein, the first and second resin Compositions are micro phase separation structure in print surface.

Summarize simply, the method for the manufacture of printed medium of the present invention comprises: (1) provides the base portion with first surface; (2) blend of the first resin Composition composition and the second resin Composition composition is provided; (3) to this blend of applying at least partially of the first surface of base portion to form coating thereon; And (4) remove solvent from coating, make the first resin Composition and the second resin Composition generation microphase-separated.

The combination of surprising remarkable advantage is brought by medium provided by the invention, described advantage comprise have that good high-resolution acceptance, resistance to image are bleed to water-based ink, water absorption resistance and resistance to damage by water, and good adhesion characteristics, namely print surface will adhere on required adherend.They are suitable for high speed printing application very much, and can be used for manufacturing the goods with high-quality, high-resolution, durable images thereon.

Up to now, prior art (such as described in bibliography D1-D4) cannot provide the printed medium that can reach desired properties and ability.Bibliography D5 intention openly shows the medium of desired properties and ability, but finds that medium disclosed in it there will be bleeding when water-based ink is to apply more than the high speed spray printing of 25mm/s, and that is it can cause bleeding.

According to the present invention, print surface has multiple first microfacies area of isolation and the second microfacies area of isolation, the first resin Composition that this first microfacies area of isolation comprises is more than the second resin Composition, the second resin Composition that this second microfacies area of isolation comprises is more than the first resin Composition, second microfacies area of isolation with each around in the first microfacies area of isolation of general toroidal shape, and protrudes relatively.

Accompanying drawing explanation

By reference to the accompanying drawings the present invention is further described, wherein:

Fig. 1 is the schematic cross sectional views of the exemplary embodiment that printed medium of the present invention is shown;

Fig. 2 is the schematic cross sectional views of another exemplary embodiment that printed medium of the present invention is shown;

Fig. 3 is the schematic cross sectional views of another exemplary embodiment that printed medium of the present invention is shown;

Fig. 4 be illustrate with observation by light microscope to example 1 in the figure on surface of printed medium that obtains;

Fig. 5 a and Fig. 5 b is the figure of the result when non-planar contact surfaces roughness with the printed medium obtained in measuring instrument practical measuring examples 1 is shown;

Fig. 6 illustrates the figure by the result during printed medium 2 obtained in observation by light microscope comparative example 1 surperficial; And

Fig. 7 a and Fig. 7 b is the figure of the result when non-planar contact surfaces roughness with the printed medium obtained in measuring instrument measurement comparative example 1 is shown;

Fig. 1 to Fig. 3 not drawn on scale, and Fig. 1 to Fig. 7 is only intended to be described and unrestricted.

The key of drawing reference numeral:

Component feature	Drawing reference numeral
		Printed medium	10、20、30
Ink receiving layer	11、21、31
		Base portion	12、22、32
Supporting layer	23、34
		Dirt-proof layer	33
Print surface	F1、F2、F3

Detailed description of the invention

Hereinafter, with reference to while accompanying drawing, the preferred embodiments of the present invention will described.

Except as otherwise noted, otherwise all numerals of the character, reaction condition etc. such as amount, such as molecular weight of expression composition used in description and claims to be all interpreted as in all cases modify by term " about ".Therefore, unless indicated to the contrary, otherwise the numerical parameter listed in above-mentioned description and accessory claim is approximation, and these approximations can use instruction content of the present invention to seek the characteristic of acquisition with those skilled in the art and change.On minimum level, each numerical parameter is not intended to the application of restriction doctrine of equivalents on claims protection domain, at least should explain each numerical parameter according to the significant digit of recorded numerical value with by usual rounding-off method.Although the digital scope set given by broad range of the present invention and parameter are approximation, the numerical value shown in instantiation can be reported as far as possible exactly.But any numerical value contains inherently tests the standard deviation in measuring and some mistake unavoidable separately owing to being present in them.

% weight, % by weight, % (by weight) etc. is synonym, refers to that substance weight takes advantage of 100 material concentrations obtained again divided by composition weight.

The number range stated by end points comprises all numerical value (such as, 1 to 5 comprises 1,1.5,2,2.75,3,3.80,4 and 5) comprised within the scope of this.As used in this specification and attached claims, clearly state in addition except non-content has, the word " " of singulative and " described " comprise the object of plural words and phrases indication.Therefore, such as, this expression way of composition comprising " a kind of compound " comprises the mixture comprising two or more compounds.As used in this specification and attached claims, term "or" generally uses with the meaning comprising "and/or", clearly states in addition except non-content has.

In printed medium of the present invention, print surface is limited by the microphase-separated of the blend of the first resin Composition composition and the second resin Composition composition.Have been found that, gained print surface is made up of the matrix in its most of part to be the first territory of the first resin Composition and its most of part be the second territory of the second resin Composition, and the physical configuration that has of these territories and property combination can bring surprising performance.

In an exemplary embodiment, ink receiving layer has multiple first microfacies area of isolation and the second microfacies area of isolation, the first resin Composition that first microfacies area of isolation comprises is more than the second resin Composition, the second resin Composition that second microfacies area of isolation comprises is more than the first resin Composition, second microfacies area of isolation with general toroidal shape (namely, substantially complete totally enclosed room) each around in the first microfacies area of isolation, and relatively protrude.

Between the first microfacies area of isolation that microphase-separated causes and the second microfacies area of isolation, distinctive uneven surface characteristic makes in printing process, the trend of water-based ink reduces, therefore fuzzy, printing images information clearly not at all can be obtained, also be even like this when the high speed printing more than 25mm/s (such as, 100mm/s).

In some preferred embodiments, the first resin Composition comprises polyalkylene oxide.In this type of embodiment, printing characteristic and the adhesiveness of print surface make moderate progress, because polyalkylene oxide imparts water-based ink acceptance and the cohesive of improvement.

In certain embodiments, the acrylic polymer of the second resin Composition comprises phenyloxy groups.The black receiving layer that the black receiving layer of the gained made by this component provides improvement adheres to the adhesiveness of required adherend, and gives the resistance to water of the image enhancement printed thereon.

In certain embodiments, the relative scale of the first resin Composition and the second resin Composition makes in the black receiving layer of gained, and the first resin Composition accounts for the first resin Composition and the second resin Composition 30 to 60 quality % altogether in 100 quality %.This formula can make to realize between the high speed printing characteristic of print surface and the resistance to water of printing images well balanced.

Another aspect of the present invention relates to the manufacture method of the printed medium being applicable to water-based ink.The manufacture method being applicable to the printed medium of water-based ink comprises the blend comprising the first resin Composition, the second resin Composition and solvent is applied to base portion and forms coating on base portion, from coating, then removes solvent to make the first resin Composition and the second resin Composition generation microphase-separated.

According to this manufacture method, print surface is used as adhesive surface and has good cohesive and the printed medium of printing characteristic, even use dye ink is printed, the printed medium for water-based ink also can easily obtain the printing images with good water resistance and bleed-resistant characteristic.

In certain embodiments, apply solution and can be the suspension comprising the first resin Composition and the second resin Composition.The black receiving layer formed by this applying solution makes the microphase-separated easily formed by use first resin Composition and the second resin Composition in print surface.

Fig. 1 is the schematic cross sectional views of the exemplary embodiment that printed medium of the present invention is shown.Printed medium 10 has base portion 12, and black receiving layer 11 and surperficial F1, surperficial in the illustrated embodiment F1 be not towards base portion 12 (namely with base portion back to), as print surface on its side being arranged on base portion 12.

Ink receiving layer 11 comprises and can substantially be made up of the second resin Composition of hydrophilic first resin Composition and Thermoadhesive, and has the micro phase separation structure formed in print surface F1 by the first resin Composition and the second resin Composition.Second resin Composition comprises the acrylic polymer with quaternized amino groups.

In the print surface F1 of printed medium 10, first resin Composition can be used as water-based ink region of acceptance, there is provided to imaging ink (such as, ink discharge device apply water-based ink) required acceptance, and the second resin Composition can be used as adhesive area, medium is provided to adhere to the required adhesiveness of required adherend.Therefore, the image printing of water-based ink may be positioned on print surface F1, and it is as adhesive surface.

In addition, because printed medium 10 has above-mentioned configuration, its print surface F1 has good cohesive and good high speed printing characteristic, and therefore it is suitable as such as more than the printed medium of the high speed spray printing of 25mm/s.

In addition, in printed medium 10, the printing images using water-based ink to be formed on print surface F1 is very excellent in resistance to water and bleeding resistance.Specifically, conventional printed medium (such as, the printed medium described in bibliography D5) be difficult to occur bleeding in water-based ink as preventing printing images during dye ink, but when using this printed medium 10, even the printing images formed by water soluble dyestuffs ink, bleeding also can be adequately suppressed.Therefore, printed medium 10 can be suitable as the printed medium of water soluble dyestuffs ink.

Although do not wish to be subject to theory constraint, we think as follows.Due to microphase-separated, the small black region of acceptance of being made up of the first resin Composition and the small adhesive area be made up of the second resin Composition complete this labyrinth in print surface F1.Therefore, water-based ink infiltrates black region of acceptance at shock point, but, penetrate into the black region of acceptance beyond shock point from the black region of acceptance of shock point and the expansion (bleeding) caused can be subject to the obstruction of adhesive area.Therefore, it is believed that, in printing, the bleeding of water-based ink can be prevented from, thus can form image clearly.In addition, it is believed that, printing images becomes excellent in resistance to water, even if because after water-based ink is printed, the bleeding of water-based ink is also prevented from because of same cause.

Second resin Composition comprises the quaternized amino groups in print surface F1.Therefore, when using water soluble dyestuffs ink print, the set of dyestuff becomes very excellent, and the interface of black region of acceptance and adhesive area also effectively controls bleeding.It should be noted that and it is believed that, if dyestuff is acid dyes, then the set of dyestuff is even more remarkable, and the control of bleeding is also even more remarkable.Here it is, and printed medium 10 is especially suitable as the reason of the printed medium of acid dyes ink.

In this article, term micro phase separation structure refers to that the first resin Composition and the second resin Composition show micron-scale phase separation structure.Such as, when at least one in the first resin Composition and the second resin Composition forms independent phase in print surface F1, and when the average diameter of this phase place is equal to or less than 100 μm, then micro phase separation structure can be referred to as.It should be noted that the average diameter of phase place can be added together by the arbitrary number of 10 to 100 phase places observed with surface optical micrograph and electron micrograph on average to determine again.

Micro phase separation structure preferably should have the average diameter being equal to or less than the spot diameter of water-based ink on print surface F1 of above-mentioned independent phase.Such as, in ink jet printing, when printing to make the average diameter of ink dot be equal to or less than 30 μm, 20 μm or 10 μm, above-mentioned independent phase should be preferably the microsize of the average diameter being equal to or less than 30 μm, 20 μm or 10 μm.So just can form image even more clearly.

Should be appreciated that the minimum of a value of the average diameter of above-mentioned independent phase is not particularly limited, can more than 0.01 μm, and in certain embodiments even more than 0.1 μm.

Island structure, cylindrical structural, layer structure and Continuum Structure provide as the example of micro phase separation structure.Specifically, the island structure expected is such: wherein having hydrophilic first resin Composition is island shape, and the second resin Composition forms the sea around island.

First resin Composition is hydrophilic.This means, the first resin Composition has the character that can absorb water-based ink.Such as, drop on resin Composition surface when water droplet and fully spread to cover extensive region, and when resin Composition absorbs water droplet in several seconds (such as, 5 seconds), then can say that resin Composition is hydrophilic.

In the exemplary embodiment, the first resin Composition can comprise one or more in polyalkylene oxide, hydrophilic acrylic resin, polyvinyl alcohol, polyvinylpyrrolidone, hydrophilic polyurethane resin, hydrophilic ethylene vinyl alcohol.

Preferably, the first resin Composition comprises polyalkylene oxide.In this case, the printing of print surface F1 and adhesion characteristics become even better, because polyalkylene oxide shows excellent and has cohesive in the acceptance of water-based ink.PEO, PPOX, oxirane and epoxy propane copolymer provide as polyalkylene oxide.

In the first resin Composition, polyalkylene oxide preferably more than 80 quality % of its gross mass, and more preferably beyond 90 quality %.In addition, the first resin Composition can be polyalkylene oxide.

Second resin Composition is heat adhesive resin Composition, and at least comprises the acrylic polymer with quaternized amino groups.

Acrylic polymer also can comprise phenyloxy groups.Thus, the cohesive of print surface and the resistance to water of printing images are further improved.

Acrylic polymer can be the polymer that monomer component comprises the acrylic monomer with quaternized amino groups.In addition, monomer component also can comprise with the acrylic monomer of phenyloxy groups, (methyl) alkyl acrylate or (methyl) acrylic acid.

Such as, provide with the acrylic monomer of quaternized amino groups and the polymer that comprises (methyl) alkyl acrylate and (methyl) the acrylic acid monomer component a kind of form as acrylic polymer, and monomer component can comprise the acrylic monomer with phenyloxy groups.

Here, the ratio of acrylic monomer in monomer component with quaternized amino groups can be 3 to 13 quality %, or it can be 5 to 11 quality %.In addition, the ratio of (methyl) alkyl acrylate in monomer component can be 20 to 90 quality %, should be preferably 25 to 70 quality %, is more preferably 30 to 60 quality %.In addition, (methyl) the acrylic acid ratio in monomer component can be 1 to 8 quality %.In addition, the ratio of acrylic monomer in monomer component with phenyloxy groups can be 0 to 70 quality %, should be preferably 10 to 65 quality %, is more preferably 20 to 60 quality %.

In this embodiment, in monomer component, (methyl) alkyl acrylate and the total amount with the acrylic monomer of phenyloxy groups can be 60 to 94 quality %, should be preferably 70 to 90 quality %.

Such as, provide as quaternized amino groups with the group that following formula (1) represents.

In the formula, R ¹, R ²and R ³be alkyl group or aromatic yl group independently, and X ^-for univalent anion.R ¹, R ²and R ³should be preferably alkyl or phenyl group separately, be more preferably alkyl group, is even more preferably C _1-2alkyl group (being the alkyl group of 1 or 2 containing carbon number).

Represented is X ^-univalent anion be not particularly limited, but can by such as halogen ion (chlorion, bromide ion, iodide ion) as an example.In these ions, chlorion is more preferred because it more easily obtains.

With the quaternised N of methyl chloride, N-dimethyl aminoethyl (methyl) acrylate, the quaternised N of use methyl chloride, N-dimethylaminopropyl (methyl) acrylate, the quaternised N of use methyl chloride, N-dimethyl aminoethyl (methyl) acrylamide and be suitable as the acrylic monomer with quaternized amino groups with methyl chloride quaternised N, N-dimethylaminopropyl (methyl) acrylamide.

Phenoxyethyl (methyl) acrylate provides as the acrylic monomer with phenyloxy groups.As (methyl) alkyl acrylate, C _1-16(methyl) alkyl acrylate is preferred, and C _1-10(methyl) alkyl acrylate is more preferred.Here, " C _1-16" and " C _1-10" represent the carbon number not comprising the alkyl group of (methyl) acryl group.

Second resin Composition can comprise the heat adhesive resin Composition that hydrophobic resin component is used as not comprising acrylic polymer.Such as, the second resin Composition can comprise polyester, hydrophobic polyurethane resin, polyester urethanes resin and ethylene vinyl acetate.It should be noted that having hydrophobicity refers to the character having and repel water-based ink.Such as, if nearly all water droplet is all ostracised when water droplet drops on resin surface, then can say that it is hydrophobic resin.

Preferably, in the second resin Composition, shared by aforesaid propylene acids polymers, ratio is more than 50 quality %, more preferably beyond 60 quality %.In some cases, the second resin Composition can be made up of acrylic polymer substantially.

Be 100 quality % in the gross weight of the first and second resin Compositions, the first resin Composition content in black receiving layer 11 can be 20 to 70 quality %, and can be 30 to 60 quality %.Thus, it is believed that the ratio that exists of black region of acceptance in the micro phase separation structure of print surface F1 and adhesive area becomes suitable, and can realize well balanced between the high speed printing characteristic of print surface F1 and the resistance to water of printing images.Such as, now, even if the printing images clearly not having bleeding also can be obtained in more than the high speed printing of 100mm/s.

In print surface F1, the gross area (S of the black region of acceptance of being made up of the first resin Composition ₁) with the gross area (S of the black region of acceptance of to be made up of the second resin Composition ₂) ratio (S ₁/ S ₂) can be such as 0.2 to 4.0, and can be 0.4 to 1.5.By arranging black region of acceptance and adhesive area with such area ratio, printing characteristic, cohesive and resistance to water become even more excellent.

Ink receiving layer 11 can be set to such as 10 to 40 μm, also can be 20 to 30 μm.When ink receiving layer 11 is manufactured into this kind of thickness, its print surface F1 has even better printing and adhesion characteristics.The reason of this effect is not always clearly, but, it is believed that the bonding strength of the second resin Composition is more effective when thickness is more than 15 μm, and good bonding strength can be guaranteed.Micro phase separation structure is uniform, and is easy to when it is less than 40 μm be formed.

Ink receiving layer 11 should have optical transparency.According to this type of black receiving layer 11, be printed on image on print surface F1 can from the surface observation except print surface F1 to.In this case, preferably add base portion 12 (mentioning after a while), and there is optical transparency.

Ink receiving layer 11 can have the first microfacies area of isolation and the second microfacies area of isolation, the first resin Composition that first microfacies area of isolation comprises is more than the second resin Composition, the second resin Composition that second microfacies area of isolation comprises is more than the first resin Composition, second microfacies area of isolation, and to protrude around the first microfacies area of isolation relatively with general toroidal shape.Like this, by the region (the second microfacies area of isolation) that wherein there is relatively many second resin Compositions being placed on region (the first microfacies area of isolation) surrounding that wherein there is relatively many first resin Compositions, effectively can prevent bleeding at region interface, and significantly improve high speed printing characteristic.

It should be noted that area ratio that " the first resin Composition comprised is more than the second resin Composition " refer to that the surface of being made up of the first resin Composition occupies region is greater than the area ratio on the surface of being made up of the second resin Composition.In addition, " relatively protrusion " refers to this region at least higher than adjacent first orientation area of isolation.

Preferably should have multiple first microfacies area of isolation, and preferably should show greatly each around in the second microfacies area of isolation of annular shape.That is, black receiving layer 11 preferably should have wherein the second microfacies area of isolation and be centered around the structure around the first microfacies area of isolation, and this construction unit has the uneven structure of repetition as a unit in print surface F1.

In other words, in print surface F1, ink receiving layer 11 preferably should have band sunk part and with the uneven structure of general toroidal shape around the projection of this sunk part, its recess forms the first microfacies area of isolation, the first resin Composition that this first microfacies area of isolation comprises is more than the second resin Composition, and projection forms the second microfacies area of isolation, the second resin Composition that this second microfacies area of isolation comprises is more than the first resin Composition.

Like this, it is believed that, by forming the outside of projection around the sunk part of formation first microfacies area of isolation of the second microfacies area of isolation, form the outward flange being similar to volcanic crater, therefore the retentivity of water-based ink in print surface F1 is improved, and printing characteristic also improves further.

In addition, the first microfacies area of isolation comprises more first resin Composition, and has good water-based ink absorbability.It is believed that, the water-based ink kept by sunk part is deposited in black receiving layer 11, this is because the first microfacies area of isolation be made up of sunk part makes the first microfacies area of isolation have high-absorbable.

In addition, the second microfacies area of isolation comprises more second resin Composition, and containing the first relatively less resin Composition.It is believed that, it is contact because the projection of this second microfacies area of isolation is formed by adhering to object that excellent cohesive and resistance to water are achieved.

The shape of the first microfacies area of isolation can be roughly circle, ellipse or polygon, but is generally round-shaped.The diameter of the first microfacies area of isolation can be such as 10 μm to 500 μm or 50 μm to 300 μm.

Second microfacies area of isolation forms protrusion shape relatively; But, the average height h of adjacent first micro phase separation structure ₁with the average height h of the second microfacies area of isolation ₂between difference (h ₂-h ₁) 1 μm to 30 μm can be generally, can be 2 μm to 20 μm in some cases.

It should be noted that the second microfacies area of isolation should preferably with annular shape around the first microfacies area of isolation; But it needs not to be complete circle, as long as the second microfacies area of isolation forms the shape of general toroidal around the first microfacies area of isolation.

Base portion 12 should have the surface that can provide black receiving layer 11.It should be noted that, in printed medium 10, base portion 12 forms the shape of film, but this base portion always need not use with the shape of film in the present invention.

Paper, synthetic paper, resin molding or the resin sheet be made up of resin (such as Corvic, vistanex, acrylic resin, polyester and polyurethane resin) can be used as base portion 12.Base portion can be single or multiple lift, and should have enough dimensional stabilitys for the subsequent treatment and the processing that form black receiving layer and printed medium thereon.Consider required flexibility, tear strength, tensile property, elasticity, weight etc., those skilled in the art can be easy to the suitable material selecting to make base portion.

Base portion 12 preferably has optical transparency.The image be printed on print surface F1 is seen by black receiving layer 11 and base portion 12, and this is because base portion 12 and black receiving layer 11 all have optical transparency.

Purposes according to the printed medium for water-based ink of the present embodiment will be described below.It should be noted that the purposes of the printed medium for water-based ink of the present invention is not limited to following examples.

Utilize printed medium 10, water-based ink can be used to be printed on print surface F1 by picture rich in detail, and print surface F1 is also used as adhesive surface.Therefore, printed medium 10 can easily adhere on object without the need to any extra adhesion process.

Such as, printed medium 10 is suitable as the film be fixed in IC-card, photo identification cards etc.In this case, such as, first will be presented at image printing on IC-card on print surface F1, then heated lamination reciprocally towards print surface F1 and IC-card.

In this kind of purposes, the IC-card with picture rich in detail can be made fast, because printed medium 10 is very excellent in printing characteristic, cohesive and resistance to water.In addition, prepared IC-card also becomes excellent in resistance to water.

In addition, such as, if printed medium 10 will be stripped after being applied to IC-card, then small black region of acceptance will be destroyed, and print content become due to the micro phase separation structure in the print surface F1 of printed medium 10 be difficult to identification.Therefore, according to printed medium 10, can prevent from reusing IC-card for illegal objective.

In addition, printed medium 10 can be adhered to there is unevenness or curved surface object on be used as decorating film.In this case, high-temperature ductility base portion should be preferably used for the base portion 12 of printed medium 10.Such as, this printed medium 10 can stick to there is unevenness or curved surface object on, to form respective shapes in the heating such as dryer printed medium 10.

According to purposes, printed medium 10 can have supporting layer on the region on another surface of base portion 12, improves treatment characteristic with supporting printing medium 10.This situation is shown in Figure 2.

Printed medium 20 shown in Fig. 2 has base portion 22, and black receiving layer 21 and surperficial F2, and supporting layer 23, and surperficial F2 is not towards base portion 22, and be arranged on the side of base portion 22, supporting layer is arranged on the opposite side of base portion 22.It should be noted that base portion 22 in printed medium 20 and black receiving layer 21 are equal to base portion 12 in printed medium 10 and black receiving layer 11.

Printed medium 20 shows excellence in treatment characteristic, because its base portion 22 and black receiving layer 21 are provided support by supporting layer 23.Utilize printed medium 20, such as, supporting layer 23 can be stripped after water-based ink printing images is formed, and only has base portion 22 and black receiving layer 21 can stick on object.

According to purposes, printed medium 10 can have dirt-proof layer on the region on another surface of base portion 12, is adsorbed onto on outermost surface after printed medium 10 has been attached on object to prevent dust and dirt.This situation is shown in Figure 3.

Printed medium 30 shown in Fig. 3 comprises base portion 32, has the black receiving layer 31 of surperficial F3, and dirt-proof layer 33, on the side that surperficial F3 is arranged on base portion 32 and not towards base portion 22, dirt-proof layer is arranged on the opposite side of base portion 32.It should be noted that base portion 32 in printed medium 30 and black receiving layer 21 are equal to base portion 12 in printed medium 10 and black receiving layer 11.Such as, dirt-proof layer 33 can be formed by the resin combination comprising fluorine resin.

In addition, printed medium 30 also can have the supporting layer 34 of support base 32, black receiving layer 31 and dirt-proof layer 33.Utilize printed medium 30, such as, supporting layer 34 can be stripped after water-based ink printing images is formed, and only has base portion 32, black receiving layer 31 and dirt-proof layer 33 can stick on object.

Next the example being used for the printing process of the printed medium of water-based ink according to the present embodiment will be described.

Method for printing water-based ink on the print surface F1 of printed medium 10 is not particularly limited; But ink jet printing is preferred.Adopt ink jet printing can form printing images fast, and above-mentioned IC-card can be prepared even more quickly.

The print speed printing speed of spray printing can be greater than 25mm/s, is greater than 50mm/s or is even greater than 100mm/s.Even if advantage of the present invention comprises under such print speed printing speed, also can on medium of the present invention, form picture rich in detail and there will not be black bleeding, because the print surface F1 of printed medium 10 has excellent high speed printing characteristic.

Water-based ink for printing is not particularly limited, but it can be water soluble dyestuffs ink, or can be acid dyes ink.According to printed medium 10, when using dye ink, bleeding can be adequately controlled.

Next the manufacture method being used for the printed medium of water-based ink according to the present embodiment will be described.It should be noted that the printed medium for water-based ink of the present invention is not limited to the printed medium prepared by following manufacture method.

This manufacture method comprises and the solution comprising the first resin Composition, the second resin Composition and solvent is applied to base portion and on base portion, forms the step of coating, and from coating, removes solvent to make the step of the first resin Composition and the second resin Composition generation microphase-separated.

According to this manufacture method, print surface is used as adhesive surface and has good cohesive and the printed medium of printing characteristic, even use dye ink is printed, the printed medium (with reference to printed medium 10 as object lesson) for water-based ink also can easily obtain the printing images with good water resistance and bleed-resistant characteristic.

In the applying solution of the first step, the first resin Composition and the second resin Composition dissolve in solvent also can be separated into resin Composition particulate in a solvent to form suspension (term " solvent " in this article refers to this type of embodiment that wherein body fluid can be more accurately termed liquid medium, liquid distillate etc.).

Solvent can make the first resin Composition and the second resin Composition be dissolved in apply maybe can be evenly dispersed in solution to apply in solution, and can suitably with an organic solvent.The fragrance same clan, such as benzene, toluene and dimethylbenzene; Ketone, such as acetone and methyl ethyl ketone; Ester, such as ethyl acetate and butyl acetate; Alcohol, such as methyl alcohol and ethanol provide as the example of organic solvent.Can be combined or be used alone these solvents.In addition, the mixture of water or water and alcohol can be used as solvent in this manufacture method.

If necessary, applying solution can be heated.Such as, applying solution can be heated to 30 to 60 DEG C to dissolve to make the first resin Composition and the second resin Composition.

In a kind of situation of this manufacture method, apply liquid and can be the suspension comprising the first resin Composition and the second resin Composition.The black receiving layer formed by this applying solution defines the distinctive uneven shape with sunk part and the peak shape projection around sunk part at print surface, and when it is formed as convex and concave shape, resistance to water and the bleed-resistant characteristic of printing images are further improved.

When the first solution and the second solution being mixed, by using the poor dissolution between the first resin Composition with the second resin Composition and making the first resin Composition and/or the second resin Composition part be separated, thus form resin particle.

Such as, when the first resin Composition is polyalkylene oxide, the first resin Composition can be allowed to be dissolved at 40 DEG C in the mixed solvent of MEK/toluene and methanol (weight ratio 2/1/1).In addition, the acrylic polymer as the second resin Composition can be allowed to be dissolved in the mixed solvent of acetone/methanol under room temperature (such as, 20 DEG C).

Such as, the applying solution comprising above-mentioned resin particle can be obtained by the second solution of the first solution and 20 DEG C that mix 40 DEG C, in the first solution, first resin Composition is dissolved in the mixed solvent (2/1/1) of MEK/toluene and methanol, in the second solution, the second resin Composition is dissolved in the mixed solvent of acetone/methanol under room temperature (20 DEG C).

When the first resin Composition is polyalkylene oxide, the first solution preferably should comprise MEK, toluene and methyl alcohol as solvent, and preferably should be heated to 35 DEG C to 60 DEG C.On the other hand, the second solution preferably should comprise MEK or acetone and methyl alcohol as solvent, and temperature should be preferably 15 DEG C to 30 DEG C.

The density of the first resin Composition in the first solution should be preferably 10 to 20 quality %, and is more preferably 14 to 16 quality %.In addition, the density of the second resin Composition in the second solution should be preferably 30 to 40 quality %, and is more preferably 33 to 38 quality %.

Solution is applied to apply coating by using on the side of base portion.The applying method applying liquid is not particularly limited, and can use known method, such as knife coating, spin-coating method, rolling method, serigraphy rubbing method and gravure coat method.

Preferably, coating should be formed to make the thickness of the black receiving layer formed after second step process be 10 to 40 μm.When coating is formed this kind of thickness, the print surface of black receiving layer to be obtained becomes even more excellent in printing characteristic and cohesive.

In second step process, from coating, remove solvent.Volatilize by heating and remove the method for solvent and airing provides as the method removing organic solvent.In second step process, the solvent in coating need not always be removed completely, and black receiving layer can comprise some in solvent.

Should be appreciated that printed medium of the present invention can be formed as sheet or roll.

Above explain suitable embodiment of the present invention; But the present invention is not limited to above-described embodiment.Such as, utilize the present invention, the printing images be formed on the print surface F1 of printed medium 10 by water-based ink can be decorating film.In addition, the present invention can be decoration (such as, having the IC-card of printing images), and the printed medium 10 with printing images be wherein formed on print surface F1 by water-based ink sticks on object (such as, the main body of IC-card).

example

Hereinafter, in more detail the present invention is described with reference to following explanation.

acrylic polymer B1: by the quaternised N of use methyl chloride of the phenoxy ethyl acrylate (being optionally expressed as below " PhEA ") of the methyl acrylate (being optionally expressed as below " MA ") of 33 quality %, 55% quality, 10 quality %, the acrylic acid (being optionally expressed as below " AA ") of N-dimethyl amino ethyl acrylate (being optionally expressed as below " DMAEA-Q ") and 2 quality % is dissolved in the mixed solvent of the acetone of 148.58 quality % and the methyl alcohol of 34.49 quality % equably, and then solution reacts.It should be noted that packing is that the aqueous solution of 79 quality % is used as DMAEA-Q.Pour in the glass container of pressure-and heat-resistance by this reaction solution, nitrogen, as initiator, is then passed into reaction solution by the azodiisobutyronitrile adding 0.1 quality %, stirs 10 minutes to reduce simultaneously.Then, within being heated to 50 DEG C 20 hours, carry out copolyreaction, obtain the acrylic polymer B1 solution of 35 quality %.

acrylic polymer B2: by the quaternised N of use methyl chloride of the phenoxy ethyl acrylate of the methyl acrylate of 43 quality %, 45 quality %, 10 quality %, the acrylic acid of N-dimethyl amino ethyl acrylate and 2 quality % is dissolved in the mixed solvent of the acetone of 148.58 quality % and the methyl alcohol of 34.49 quality % equably, and then solution reacts.It should be noted that packing is that the aqueous solution of 79 quality % is used as DMAEA-Q.Pour in the glass container of pressure-and heat-resistance by this reaction solution, nitrogen, as initiator, is then passed into reaction solution by the azodiisobutyronitrile adding 0.1 quality %, stirs 10 minutes to reduce simultaneously.Then, within being heated to 50 DEG C 20 hours, carry out copolyreaction, obtain the acrylic polymer B2 solution of 35 quality %.

acrylic polymer B3: by the quaternised N of use methyl chloride of the phenoxy ethyl acrylate of the methyl acrylate of 23 quality %, 65 quality %, 10 quality %, the acrylic acid of N-dimethyl amino ethyl acrylate and 2 quality % is dissolved in the mixed solvent of the acetone of 148.58 quality % and the methyl alcohol of 34.49 quality % equably, and then solution reacts.It should be noted that packing is that the aqueous solution of 79 quality % is used as DMAEA-Q.Pour in the glass container of pressure-and heat-resistance by this reaction solution, nitrogen, as initiator, is then passed into reaction solution by the azodiisobutyronitrile adding 0.1 quality %, stirs 10 minutes to reduce simultaneously.Then, within being heated to 50 DEG C 20 hours, carry out copolyreaction, obtain the acrylic polymer B3 solution of 35 quality %.

acrylic polymer B4: by the quaternised N of use methyl chloride of the phenoxy ethyl acrylate of the methyl acrylate of 73 quality %, 15 quality %, 10 quality %, the acrylic acid of N-dimethyl amino ethyl acrylate and 2 quality % is dissolved in the mixed solvent of the acetone of 148.58 quality % and the methyl alcohol of 34.49 quality % equably, and then solution reacts.It should be noted that packing is that the aqueous solution of 79 quality % is used as DMAEA-Q.Pour in the glass container of pressure-and heat-resistance by this reaction solution, nitrogen, as initiator, is then passed into reaction solution by the azodiisobutyronitrile adding 0.1 quality %, stirs 10 minutes to reduce simultaneously.Then, within being heated to 50 DEG C 20 hours, carry out copolyreaction, obtain the acrylic polymer B4 solution of 35 quality %.

acrylic polymer B5: by the quaternised N of use methyl chloride of the phenoxy ethyl acrylate of the 2-ethylhexyl acrylate (being optionally expressed as below " 2EHA ") of 33 quality %, 55% quality, 10 quality %, the acrylic acid of N-dimethyl amino ethyl acrylate and 2 quality % is dissolved in the mixed solvent of the acetone of 148.58 quality % and the methyl alcohol of 34.49 quality % equably, and then solution reacts.It should be noted that packing is that the aqueous solution of 79 quality % is used as DMAEA-Q.Pour in the glass container of pressure-and heat-resistance by this reaction solution, nitrogen, as initiator, is then passed into reaction solution by the azodiisobutyronitrile adding 0.1 quality %, stirs 10 minutes to reduce simultaneously.Then, within being heated to 50 DEG C 20 hours, carry out copolyreaction, obtain the acrylic polymer B5 solution of 35 quality %.

acrylic polymer B6: by the quaternised N of use methyl chloride of the phenoxy ethyl acrylate of the methyl acrylate of 29 quality %, 55 quality %, 10 quality %, the acrylic acid of N-dimethyl amino ethyl acrylate and 2 quality % is dissolved in the mixed solvent of the acetone of 148.58 quality % and the methyl alcohol of 34.49 quality % equably, and then solution reacts.It should be noted that packing is that the aqueous solution of 79 quality % is used as DMAEA-Q.Pour in the glass container of pressure-and heat-resistance by this reaction solution, nitrogen, as initiator, is then passed into reaction solution by the azodiisobutyronitrile adding 0.1 quality %, stirs 10 minutes to reduce simultaneously.Then, within being heated to 50 DEG C 20 hours, carry out copolyreaction, obtain the acrylic polymer B6 solution of 35 quality %.

acrylic polymer B7: by the quaternised N of use methyl chloride of the methyl acrylate of 88 quality %, 10 quality %, the acrylic acid of N-dimethyl amino ethyl acrylate and 2 quality % is dissolved in the mixed solvent of the acetone of 148.58 quality % and the methyl alcohol of 34.49 quality % equably, and then solution reacts.It should be noted that packing is that the aqueous solution of 79 quality % is used as DMAEA-Q.Pour in the glass container of pressure-and heat-resistance by this reaction solution, nitrogen, as initiator, is then passed into reaction solution by the azodiisobutyronitrile adding 0.1 quality %, stirs 10 minutes to reduce simultaneously.Then, within being heated to 50 DEG C 20 hours, carry out copolyreaction, obtain the acrylic polymer B7 solution of 35 quality %.

acrylic polymer B8: by the quaternised N of use methyl chloride of the phenoxy ethyl acrylate of the methyl acrylate of 58 quality %, 35 quality %, 5 quality %, the acrylic acid of N-dimethyl amino ethyl acrylate and 2 quality % is dissolved in the mixed solvent of the acetone of 148.58 quality % and the methyl alcohol of 34.49 quality % equably, and then solution reacts.Pour in the glass container of pressure-and heat-resistance by this reaction solution, nitrogen, as initiator, is then passed into reaction solution by the azodiisobutyronitrile adding 0.1 quality %, stirs 10 minutes to reduce simultaneously.Then, within being heated to 50 DEG C 20 hours, carry out copolyreaction, obtain the acrylic polymer B8 solution of 35 quality %.

acrylic polymer B9: by the phenoxy ethyl acrylate of the methyl acrylate of 33 quality %, 55% quality, the N of 10 quality %, the acrylic acid of N-dimethyl amino ethyl acrylate (being optionally expressed as the tertiary amine of " DMAEA ") and 2 quality % is dissolved in the mixed solvent of the acetone of 148.58 quality % and the methyl alcohol of 34.49 quality % equably, and then solution reacts.Pour in the glass container of pressure-and heat-resistance by this reaction solution, nitrogen, as initiator, is then passed into reaction solution by the azodiisobutyronitrile adding 0.1 quality %, stirs 10 minutes to reduce simultaneously.Then, within being heated to 50 DEG C 20 hours, carry out copolyreaction, obtain the acrylic polymer B9 solution of 35 quality %.

acrylic polymer B10: the phenoxy ethyl acrylate of the methyl acrylate of 43 quality %, 55% quality and the acrylic acid of 2 quality % are dissolved in equably in the mixed solvent of the acetone of 148.58 quality % and the methyl alcohol of 34.49 quality %, then solution reacts.Pour in the glass container of pressure-and heat-resistance by this reaction solution, nitrogen, as initiator, is then passed into reaction solution by the azodiisobutyronitrile adding 0.1 quality %, stirs 10 minutes to reduce simultaneously.Then, within being heated to 50 DEG C 20 hours, carry out copolyreaction, obtain the acrylic polymer B10 solution of 35 quality %.

acrylic polymer B11: by the quaternised N of use methyl chloride of the phenoxy ethyl acrylate of the methyl acrylate of 28 quality %, 55 quality %, 15 quality %, the acrylic acid of N-dimethyl amino ethyl acrylate and 2 quality % is dissolved in the mixed solvent of the acetone of 148.58 quality % and the methyl alcohol of 34.49 quality % equably, and then solution reacts.Pour in the glass container of pressure-and heat-resistance by this reaction solution, nitrogen, as initiator, is then passed into reaction solution by the azodiisobutyronitrile adding 0.1 quality %, stirs 10 minutes to reduce simultaneously.Then, within being heated to 50 DEG C 20 hours, carry out copolyreaction, obtain the acrylic polymer B5 solution of 35 quality %.

acrylic polymer B12: by the quaternised N of use methyl chloride of the phenoxy ethyl acrylate of the methyl acrylate of 25 quality %, 55 quality %, 10 quality %, the acrylic acid of N-dimethyl amino ethyl acrylate and 10 quality % is dissolved in the mixed solvent of the acetone of 148.58 quality % and the methyl alcohol of 34.49 quality % equably, and then solution reacts.Pour in the glass container of pressure-and heat-resistance by this reaction solution, nitrogen, as initiator, is then passed into reaction solution by the azodiisobutyronitrile adding 0.1 quality %, stirs 10 minutes to reduce simultaneously.Then, within being heated to 50 DEG C 20 hours, carry out copolyreaction, obtain the acrylic polymer B5 solution of 35 quality %.

The ratio (mass ratio) of the monomeric unit of composition acrylic polymer B1 to B10 illustrates in table 1 below.

table 1

Acrylic polymer	MA	2EHA	PhEA	DMAEA-Q	DMAEA	AA
							B1	33	-	55	10	-	2
B2	43	-	45	10	-	2

Acrylic polymer	MA	2EHA	PhEA	DMAEA-Q	DMAEA	AA
							B3	23	-	65	10	-	2
B4	73	-	15	10	-	2
							B5	-	33	55	10	-	2
B6	29	-	55	10	-	6
							B7	88	-	-	10	-	2
B8	58	-	35	5	-	2
							B9	33	-	55	-	10	2
B10	43	-	55	-	-	2

example 1

By AQUA (derive from Sumitomo Seika Co., Ltd (Sumitomo Seika ChemicalsCo., Ltd.) polyalkylene oxide, packing 100 quality %) be dissolved in the mixed solvent (mass ratio 2/1/1) of MEK/toluene and methanol at 40 DEG C, be that the solution A 1 of 15 quality % is as the first resin Composition using the density of solid of preparation.In addition, the solution (hereinafter referred to solution B 1) of the acrylic polymer B1 containing 35 quality % is as the second resin Composition.

The solution A 1 of 40 DEG C and solution B 1 are mixed to make the mass ratio of the first resin Composition and the second resin Composition become 60/40, prepares mixture C 1.

Printed medium 1 is obtained by following steps: use knife coating to be PETG film (PET film) the upper applying solution C 1 of 50 μm at thickness, then make solution C 1 being set in the baking oven of 80 DEG C dry 10 minutes, to form black receiving layer on a pet film.Then, the thickness of the black receiving layer formed after drying is adjusted to 25 μm.It should be noted that by adjustment PET film surface and cutter surperficial between gap adjust the thickness of black receiving layer.

When the printed medium 1 obtained with surface optical microscopic examination, the black receiving layer of printed medium 1 has near uniform micro phase separation structure in print surface.Result is shown in Figure 4.

In addition, non-planar contact surfaces roughness measuring instrument (deriving from Zhai Ke company (Zaygo)) is used to measure the print surface of the black receiving layer of obtained printed medium 1, to measure the surface roughness of print surface.Result is shown in Figure 5.According to the result shown in Fig. 5, unique uneven structural configuration is confirmed, and wherein construction unit is by the first microfacies area of isolation of circular shape and form with the second convex shape microfacies area of isolation of general toroidal shape around the first microfacies area of isolation neighboring.In other words, confirm unique uneven structure to be formed the second micro phase separation structure is risen with peak shape and with circular shape around the first microfacies area of isolation.

The micro phase separation structure of print surface is formed as island structure, and the average diameter of island is about 5 μm.In addition, the diameter of the first microfacies area of isolation of circular shape is about 50 to 300 μm, and the average height h of the first micro phase separation structure ₁with the average height h of the second microfacies area of isolation ₂between difference (h ₂-h ₁) be about 25 to 30 μm.

In addition, according to the result using AFM (AFM) to observe surface, the first resin Composition confirming to exist in the first microfacies area of isolation is more than the second resin Composition, and the second resin Composition existed in the second microfacies area of isolation is more than the first resin Composition.Specifically, according to this existence of crystal orientation state confirmation shown by the first resin Composition.

In addition, the printing characteristic of printed medium 1, resistance to water, normal temperature adhesive intensity and high-temperature bond strength is evaluated according to following evaluation method.Evaluation result is as shown in table 2.

example 2

In addition, except using the solution (hereinafter referred to solution B 2) of the acrylic polymer B2 containing 35 quality % to replace solution B 1 as the second resin Composition, the method being similar to example 1 is adopted to obtain printed medium 2.

When the printed medium 2 obtained with surface optical microscopic examination, the black receiving layer of printed medium 2 has near uniform micro phase separation structure in print surface.

In addition, non-planar contact surfaces roughness measuring instrument (deriving from Zhai Ke company (Zaygo)) is used to measure the print surface of the obtained black receiving layer of printed medium 2, to measure the surface roughness of print surface.According to the measurement result using non-planar contact surfaces roughness measuring instrument, confirm to define the uneven structure of uniqueness of the multiple layout being similar to example 1 in the print surface of the black receiving layer of printed medium 2, this uneven structure has the first microfacies area of isolation, and with the second microfacies area of isolation in convex shape of general toroidal shape around the first microfacies area of isolation neighboring.

In addition, the printing characteristic of printed medium 2, resistance to water, normal temperature adhesive intensity and high-temperature bond strength is evaluated according to following evaluation method.Evaluation result is as shown in table 2.

example 3

In addition, except using the solution (hereinafter referred to solution B 3) of the acrylic polymer B3 containing 35 quality % to replace solution B 1 as the second resin Composition, the method being similar to example 1 is adopted to obtain printed medium 3.

When the printed medium 3 obtained with surface optical microscopic examination, the black receiving layer of printed medium 3 has near uniform micro phase separation structure in print surface.

In addition, non-planar contact surfaces roughness measuring instrument (deriving from Zhai Ke company (Zaygo)) is used to measure the print surface of the black receiving layer of obtained printed medium 3, to measure the surface roughness of print surface.According to the measurement result using non-planar contact surfaces roughness measuring instrument, confirm to define the uneven structure of uniqueness of the multiple layout being similar to example 1 in the print surface of the black receiving layer of printed medium 3, this uneven structure has the first microfacies area of isolation, and with the second microfacies area of isolation in convex shape of general toroidal shape around the first microfacies area of isolation neighboring.

In addition, the printing characteristic of printed medium 3, resistance to water, normal temperature adhesive intensity and high-temperature bond strength is evaluated according to following evaluation method.Evaluation result is as shown in table 2.

example 4

In addition, except using the solution (hereinafter referred to solution B 4) of the acrylic polymer B4 containing 35 quality % to replace solution B 1 as the second resin Composition, the method being similar to example 1 is adopted to obtain printed medium 4.

When the printed medium 4 obtained with surface optical microscopic examination, the black receiving layer of printed medium 4 has near uniform micro phase separation structure in print surface.

In addition, non-planar contact surfaces roughness measuring instrument (deriving from Zhai Ke company (Zaygo)) is used to measure the print surface of the black receiving layer of obtained printed medium 4, to measure the surface roughness of print surface.According to the measurement result using non-planar contact surfaces roughness measuring instrument, confirm to define the uneven structure of uniqueness of the multiple layout being similar to example 1 in the print surface of the black receiving layer of printed medium 4, this uneven structure has the first microfacies area of isolation, and with the second microfacies area of isolation in convex shape of general toroidal shape around the first microfacies area of isolation neighboring.

In addition, the printing characteristic of printed medium 4, resistance to water, normal temperature adhesive intensity and high-temperature bond strength is evaluated according to following evaluation method.Evaluation result is as shown in table 2.

example 5

In addition, except using the solution (hereinafter referred to solution B 5) of the acrylic polymer B5 containing 35 quality % to replace solution B 1 as the second resin Composition, the method being similar to example 1 is adopted to obtain printed medium 5.

When the printed medium 5 obtained with surface optical microscopic examination, the black receiving layer of printed medium 5 has near uniform micro phase separation structure in print surface.

In addition, non-planar contact surfaces roughness measuring instrument (deriving from Zhai Ke company (Zaygo)) is used to measure the print surface of the black receiving layer of obtained printed medium 5, to measure the surface roughness of print surface.According to the measurement result using non-planar contact surfaces roughness measuring instrument, confirm to define the uneven structure of uniqueness of the multiple layout being similar to example 1 in the print surface of the black receiving layer of printed medium 5, this uneven structure has the first microfacies area of isolation, and with the second microfacies area of isolation in convex shape of general toroidal shape around the first microfacies area of isolation neighboring.

In addition, the printing characteristic of printed medium 5, resistance to water, normal temperature adhesive intensity and high-temperature bond strength is evaluated according to following evaluation method.Evaluation result is as shown in table 2.

example 6

Except replacing solution C 1 and using the mixture C 2 (therefore the mass ratio of the first resin Composition and the second resin Composition becomes 50/50) by mixing the solution A 1 of 40 DEG C and solution B 1 and preparation, adopt the method acquisition printed medium 6 being similar to example 1.

When the printed medium 6 obtained with surface optical microscopic examination, the black receiving layer of printed medium 6 has near uniform micro phase separation structure in print surface.

In addition, non-planar contact surfaces roughness measuring instrument (deriving from Zhai Ke company (Zaygo)) is used to measure the print surface of the black receiving layer of obtained printed medium 6, to measure the surface roughness of print surface.According to the measurement result using non-planar contact surfaces roughness measuring instrument, confirm to define the uneven structure of uniqueness of the multiple layout being similar to example 1 in the print surface of the receiving layer of printed medium 6, this uneven structure has the first microfacies area of isolation, and with the second microfacies area of isolation in convex shape of general toroidal shape around the first microfacies area of isolation neighboring.

In addition, the printing characteristic of printed medium 6, resistance to water, normal temperature adhesive intensity and high-temperature bond strength is evaluated according to following evaluation method.Evaluation result is as shown in table 2.

example 7

In addition, except using the solution (hereinafter referred to solution B 6) of the acrylic polymer B6 containing 35 quality % to replace solution B 1 as the second resin Composition, the method being similar to example 1 is adopted to obtain printed medium 7.

When the printed medium 7 obtained with surface optical microscopic examination, the black receiving layer of printed medium 7 has near uniform micro phase separation structure in print surface.

In addition, non-planar contact surfaces roughness measuring instrument (deriving from Zhai Ke company (Zaygo)) is used to measure the print surface of the black receiving layer of obtained printed medium 7, to measure the surface roughness of print surface.According to the measurement result using non-planar contact surfaces roughness measuring instrument, confirm to define the uneven structure of uniqueness of the multiple layout being similar to example 1 in the print surface of the black receiving layer of printed medium 7, this uneven structure has the first microfacies area of isolation, and with the second microfacies area of isolation in convex shape of general toroidal shape around the first microfacies area of isolation neighboring.

In addition, the printing characteristic of printed medium 7, resistance to water, normal temperature adhesive intensity and high-temperature bond strength is evaluated according to following evaluation method.Evaluation result is as shown in table 2.

example 8

By AQUA (derive from Sumitomo Seika Co., Ltd (Sumitomo Seika ChemicalsCo., Ltd.) polyalkylene oxide, packing 100 quality %) be dissolved in the mixed solvent (mass ratio 2/1/1) of MEK/toluene and methanol at 40 DEG C, be that the solution A 2 of 15 quality % is as the first resin Composition using the density of solid of preparation.Except using solution A 2 to replace except solution A 1, the method being similar to example 1 is adopted to obtain printed medium 8.

When the printed medium 8 obtained with surface optical microscopic examination, the black receiving layer of printed medium 8 has near uniform micro phase separation structure in print surface.

In addition, non-planar contact surfaces roughness measuring instrument (deriving from Zhai Ke company (Zaygo)) is used to measure the print surface of the black receiving layer of obtained printed medium 8, to measure the surface roughness of print surface.As the measurement result using non-planar contact surfaces roughness measuring instrument, in the print surface of the black receiving layer of printed medium 8, do not observe the uneven structure of viewed uniqueness in example 1, but form surface texture by the unit of larger chevron shape.

In addition, the printing characteristic of printed medium 8, resistance to water, normal temperature adhesive intensity and high-temperature bond strength is evaluated according to following evaluation method.Evaluation result is as shown in table 2.

example 9

The method being similar to example 8 is adopted to prepare solution A 2.Then, the solution A 2 of 40 DEG C and solution B 1 are mixed to make the mass ratio of the first resin Composition and the second resin Composition become 30/70, prepares mixture C 3.

Except using mixture C 3 to replace except mixture C 1, the method being similar to example 1 is adopted to obtain printed medium 9.

When the printed medium 9 obtained with surface optical microscopic examination, the black receiving layer of printed medium 9 has near uniform micro phase separation structure in print surface.

In addition, non-planar contact surfaces roughness measuring instrument (deriving from Zhai Ke company (Zaygo)) is used to measure the print surface of the black receiving layer of obtained printed medium 9, to measure the surface roughness of print surface.As the measurement result using non-planar contact surfaces roughness measuring instrument, in the print surface of the black receiving layer of printed medium 8, do not observe the uneven structure of viewed uniqueness in example 1, but form surface texture by the unit of larger chevron shape.

In addition, the printing characteristic of printed medium 9, resistance to water, normal temperature adhesive intensity and high-temperature bond strength is evaluated according to following evaluation method.Evaluation result is as shown in table 2.

example 10

The method being similar to example 8 is adopted to prepare solution A 2.In addition, the solution (hereinafter referred to solution B 7) of the acrylic polymer B7 containing 35 quality % is as the second resin Composition.Then, the solution A 2 of 40 DEG C and solution B 7 are mixed to make the mass ratio of the first resin Composition and the second resin Composition become 40/60, prepares mixture mixture C 4.

Except using mixture C 4 to replace except mixture C 1, the method being similar to example 1 is adopted to obtain printed medium 10.

When the printed medium 10 obtained with surface optical microscopic examination, the black receiving layer of printed medium 10 has near uniform micro phase separation structure in print surface.

In addition, non-planar contact surfaces roughness measuring instrument (deriving from Zhai Ke company (Zaygo)) is used to measure the print surface of the black receiving layer of obtained printed medium 10, to measure the surface roughness of print surface.As the measurement result using non-planar contact surfaces roughness measuring instrument, in the print surface of the black receiving layer of printed medium 9, do not observe the uneven structure of viewed uniqueness in example 1, but form surface texture by the unit of larger chevron shape.

example 11

In addition, except using the solution (hereinafter referred to solution B 8) of the acrylic polymer B8 containing 35 quality % to replace solution B 1 as the second resin Composition, the method being similar to example 1 is adopted to obtain printed medium 11.

When the printed medium 11 obtained with surface optical microscopic examination, the black receiving layer of printed medium 11 has near uniform micro phase separation structure in print surface.

In addition, non-planar contact surfaces roughness measuring instrument (deriving from Zhai Ke company (Zaygo)) is used to measure the print surface of the black receiving layer of obtained printed medium 11, to measure the surface roughness of print surface.According to the measurement result using non-planar contact surfaces roughness measuring instrument, confirm to define the uneven structure of uniqueness of the multiple layout being similar to example 1 in the print surface of the black receiving layer of printed medium 11, this uneven structure has the first microfacies area of isolation, and with the second microfacies area of isolation in convex shape of general toroidal shape around the first microfacies area of isolation neighboring.

Comparative example C1

The method being similar to example 8 is adopted to prepare solution A 2.Then, the solution (hereinafter referred to solution B 9) of solution A 2 and the acrylic polymer B9 containing 35 quality % is mixed, makes the mass ratio of the first resin Composition and the second resin Composition become 40/60, prepare mixture D 1.

Except using mixture D 1 to replace except mixture C 1, the method being similar to example 1 is adopted to obtain printed medium 21.

In addition, the printing characteristic of printed medium 21, resistance to water, normal temperature adhesive intensity and high-temperature bond strength is evaluated according to following evaluation method.Evaluation result is as shown in table 2.

It should be noted that when at print surface, there is near uniform micro phase separation structure with confirming printed medium 21 during surface optical microscopic examination.But, according to the measurement result using non-planar contact surfaces roughness measuring instrument (deriving from Zhai Ke company (Zaygo)), in print surface, do not observe the uneven structure of viewed uniqueness in example 1, but form surface texture by the unit of larger chevron shape.The microscopical observed result of surface optical is shown in Figure 6, and the measurement result of non-planar contact surfaces roughness measuring instrument is shown in Figure 7.

comparative example C2

The method being similar to example 1 is adopted to prepare solution A 1.Then, the solution (hereinafter referred to solution B 10) of solution A 1 and the acrylic polymer B10 containing 35 quality % is mixed, makes the mass ratio of the first resin Composition and the second resin Composition become 40/60, prepare mixture D 2.

Except using mixture D 2 to replace except mixture C 1, the method being similar to example 1 is adopted to obtain printed medium 22.

In addition, the printing characteristic of printed medium 22, resistance to water, normal temperature adhesive intensity and high-temperature bond strength is evaluated according to following evaluation method.Evaluation result is as shown in table 2.

It should be noted that when at print surface, there is near uniform micro phase separation structure with confirming printed medium 22 during surface optical microscopic examination.But, according to the measurement result using non-planar contact surfaces roughness measuring instrument (deriving from Zhai Ke company (Zaygo)), in print surface, do not observe the uneven structure of viewed uniqueness in example 1.

comparative example C3

By the AQUA of 40 quality % (deriving from Sumitomo Seika Co., Ltd (SumitomoSeika Chemicals Co., Ltd.), 100 quality % packings), there is the hydrophobic polyester of the 40 quality % as hydrophobic resin of heat adhesive character the polyurethane resin of 670 (deriving from the polyester that Co., Ltd. (Toyobo Co., Ltd.) is spun by Japan) and 20 quality % uR-3200 (derives from Japan and spins Co., Ltd. (Toyobo Co., Ltd.) polyester urethanes resin, glass transition temperature :-3 DEG C, 30 quality % packings) fully stir to make to be scattered at 60 DEG C in the mixed solvent of MEK/toluene (mass ratio 1/1).

Printed medium 23 is obtained by following steps: use knife coating is PETG film (PET film) the upper solution D 3 of 50 μm at thickness, then make solution D 3 being set in the baking oven of 80 DEG C dry 10 minutes, to form black receiving layer on a pet film.Then, the thickness of the black receiving layer formed after drying is adjusted to 25 μm.

It should be noted that when at print surface, there is near uniform micro phase separation structure with confirming printed medium 23 during surface optical microscopic examination.But, according to the measurement result using non-planar contact surfaces roughness measuring instrument (deriving from Zhai Ke company (Zaygo)), in print surface, do not observe the uneven structure of viewed uniqueness in example 1.

In addition, the printing characteristic of printed medium 23, resistance to water, normal temperature adhesive intensity and high-temperature bond strength is evaluated according to following evaluation method.Evaluation result is as shown in table 2.

method of testing

printing characteristic is evaluated: use ink-jet printer p-640L, adopts the water soluble dyestuffs ink of six kinds of colors, is printed on the black receiving layer of printed medium with the picture of the print speed printing speed of 25mm/s or 100mm/s by people and letter.With following 5 grades, visual evaluation is carried out to printing images." D " represents that printing images is the fuzzyyest, and the vividness of printing images represents successively from " C ", " B " to " A " and improves, and " AA " is the mark provided printing images the most clearly.It should be noted that the result obtained under the print speed printing speed of 25mm/s is be evaluated as " printing characteristic ", the result obtained under the print speed printing speed of 100mm/s is be evaluated as " high speed printing characteristic ".

bleeding evaluating characteristics: print image on the black receiving layer of printed medium, adopt printing to evaluate similar method and evaluate.Then, printed medium and vinyl chloride resin card are placed as and make the side of the print surface of printed medium and card facing with each other, then use roll shape heat-laminator to be heated lamination (continuing 1 second at 120 DEG C).Visual Observations Observations is carried out to printing images, check sample at 80 DEG C leave standstill whether exist after 7 days any fuzzy.This evaluation is rated as following 5 grades.

AA: do not change completely.

A: have almost no change compared with tester.

B: have significant change compared with tester.

C: have significantly fuzzy.

D: whole surface exists obviously fuzzy.

normal temperature adhesive intensity evaluation: print image on the black receiving layer of printed medium, adopt printing to evaluate similar method and evaluate.Then, printed medium and vinyl chloride resin card are placed as and make the side of the print surface of printed medium and card facing with each other, then use roll shape heat-laminator to be heated lamination (continuing 1 second at 120 DEG C).

After obtained measurement sample is placed 24 hours at 23 DEG C, use tensile testing machine at 23 DEG C, measure the peel strength (N/25mm) of 180 °.Measuring condition is set to the draw speed of 200mm/min.When being greater than 15N/25mm or when material damage, measurement result is be evaluated as " A "; When between 15-10N/25mm, measurement result is be evaluated as " B "; When being less than 10N/25mm, measurement result is be evaluated as " C ".

high-temperature bond strength is evaluated: adopt the similar method of normal temperature adhesive intensity evaluation to obtain measurement sample.After obtained measurement sample is placed 24 hours at 23 DEG C, use tensile testing machine at 80 DEG C, measure the peel strength (N/25mm) of 180 °.Measuring condition is set to the draw speed of 200mm/min.When being greater than 15N/25mm or when material damage, measurement result is be evaluated as " A "; When between 15-10N/25mm, measurement result is be evaluated as " B "; When being less than 10N/25mm, measurement result is be evaluated as " C ".

resistance to water is evaluated: adopt the similar method of normal temperature adhesive intensity evaluation to obtain measurement sample.Sample will be measured place after 24 hours in water under room temperature (25 DEG C), the change of its outward appearance of visual confirmation.It should be noted that the situation not observing change is rated for " AA " in resistance to water is evaluated; Wherein 3-5mm width is heaved at the edge of laminate, but the situation that can return to original state is rated for " A "; Wherein 3-5mm width is heaved at the edge of laminate, and the situation that can not return to original state is rated for " B "; Wherein the eluted situation of adhesive phase is rated for " C "; Film occurs that the situation of bur is rated for " D ".

table 2

Claims

1. the printed medium for water-based ink, described printed medium comprises the black receiving layer gone up at least partially of the base portion with first surface and the described first surface at described base portion, wherein: (1) described black receiving layer has the print surface limited by the microphase-separated of the blend of the first resin Composition composition and the second resin Composition composition; (2) described first resin Composition is hydrophilic; And (3) described second resin Composition comprises the acrylic polymer with quaternized amino groups and shows heat adhesive characteristic.

2. printed medium according to claim 1, wherein said print surface is made up of the matrix in its most of part to be the first territory of the first resin Composition and its most of part be the second territory of the second resin Composition.

3. printed medium according to claim 1, wherein said second territory is substantially around each first territory, and described second territory is protruded relatively.

4. printed medium according to claim 1, wherein said first resin Composition comprises polyalkylene oxide.

5. printed medium according to claim 1, wherein said acrylic polymer has phenyloxy groups.

6. printed medium according to claim 1, wherein said acrylic polymer is by the obtained product of the polymerization of following component: the acrylic monomer with quaternized amino groups of 3 to 13 quality %; (methyl) alkyl acrylate of 20 to 90 quality %; The acrylic monomer with phenyloxy groups of 0 to 70 quality %; And 1 to 8 (methyl) acrylic acid of quality %.

7. printed medium according to claim 1, the total amount of wherein said first resin and described second resin is in 100 quality %, and the amount of described first resin in described black receiving layer is 20 to 70 quality %.

8. for the manufacture of a method for printed medium according to claim 1, described method comprises: (1) provides the base portion with first surface; (2) blend of the first resin Composition composition and the second resin Composition composition is provided; (3) to the described blend of applying at least partially of the described first surface of described base portion to form coating thereon; And (4) remove solvent from described coating, make described first resin Composition and described second resin Composition generation microphase-separated.

9. method according to claim 8, wherein said applying liquid is the suspension comprising the resin particle be made up of described first resin and described second resin.