CN104755272B - The printed medium and its manufacture method of waterbased color ink jet printing - Google Patents

Abstract

The invention provides a kind of printed medium for water-based ink, the printed medium includes base portion and black receiving layer, the black receiving layer has not towards the surface of the base portion for use as the printing surface being arranged on the side of the base portion, wherein the black receiving layer includes；Micro phase separation structure in the resin of hydrophily first and the second resin with heat adhesive property, the printing surface, wherein the micro phase separation structure is formed by first resin and second resin；And second resin includes the acrylic polymer with quaternized amino groups.

Description

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

Technical field

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

Background technology

As conventional printed medium, multiple product such as paper, synthetic paper and resin film are known.These printed mediums are consolidated Determine onto various objects, and for example, by providing adhesive on printed medium, apply two-sided tape etc. to use.

In recent years, the configuration of printed medium has turned into known, wherein printing surface also serves as adhesive surface and is not required to To apply adhesive on printing image.Illustrative example has disclosed 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.

The water-based inkjet inks of a kind of bleed resistance to image that can show to improve, water absorption resistance and water-fast damage are needed to receive Jie Matter, the water-based inkjet inks accepting medium applied in particular for high speed printing.

The content of the invention

Receive printed medium and the method for preparing this medium the invention provides a kind of improved ink-jet.

In simple terms, printed medium of the invention include with first surface base portion and in base portion first surface extremely Black receiving layer in a few part.According to the present invention：(1) black receiving layer has by the first resin Composition composition and the second resin The printing surface that the microphase-separated of the blend of components composition is limited；(2) first resin Compositions are hydrophilic；And (3) Second resin Composition includes the acrylic polymer with quaternized amino groups and shows heat adhesive characteristic.Make People surprisingly it has been found that, with by micro phase separation structure as described herein limit printing surface or region black receiving layer provide Unexpected and favourable result.

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

Simply summarize, include for manufacturing the method for printed medium of the present invention：(1) base with first surface is provided Portion；(2) blend of the first resin Composition composition and the second resin Composition composition is provided；(3) to the first surface of base portion At least a portion apply the blend to be formed on coating；And (4) remove solvent from coating so that the first resin Microphase-separated occurs for component and the second resin Composition.

Medium provided by the present invention brings the combination of surprising remarkable advantage, and the advantage is included to water-based ink With good high-resolution acceptance, bleed resistance to image, water absorption resistance and water-fast damage, and good adhesion characteristics, I.e. printing surface will be adhered on required adherend.They are highly suitable for high speed printing application, and exist available for manufacture There is high-quality, high-resolution, the product of durable images thereon.

So far, prior art (such as described in bibliography D1-D4) can not provide can reach needed for performance and The printed medium of ability.The medium of performance and ability needed for bibliography D5 is intended to open show, but find wherein disclosed Bleeding occurs when water-based ink is applied with the high speed spray printing more than 25mm/s in medium, that is to say, that it can cause bleeding.

According to the present invention, printing surface has multiple first microfacies area of isolation and the second microfacies area of isolation, and this The first resin Composition that one microfacies area of isolation is included is more than the second resin Composition, the second microfacies area of isolation include second Resin Composition is more than the first resin Composition, and the second microfacies area of isolation is surrounded in the first microfacies area of isolation with generally annular in shape It is each, and relative protrude.

Brief description of the drawings

The present invention is further described with reference to accompanying drawing, wherein：

Fig. 1 is the schematic cross sectional views for an exemplary embodiment for showing the printed medium of the present invention；

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

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

Fig. 4 is the figure on the surface of printed medium for showing to obtain in the example 1 observed with light microscope；

Fig. 5 a and Fig. 5 b are when showing the non-planar contact surfaces roughness with the printed medium obtained in measuring instrument practical measuring examples 1 Result figure；

Fig. 6 is the figure of result when showing the surface with the printed medium 2 obtained in observation by light microscope comparative example 1； And

Fig. 7 a and Fig. 7 b are the non-planar contact surfaces roughness for showing to be measured the printed medium obtained in comparative example 1 with measuring instrument When result figure；

Fig. 1 to Fig. 3 is not drawn on scale, and Fig. 1 is merely intended to be illustrative and not limiting to Fig. 7.

The key of drawing reference numeral：

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

Embodiment

Hereinafter, the preferred embodiments of the present invention will be described while refer to the attached drawing.

Except as otherwise noted, otherwise the amount of expression composition used in specification and claims, such as molecular weight All numerals of property, reaction condition etc. should be understood as being modified by term " about " in all cases.Therefore, unless there are Opposite explanation, the numerical parameter otherwise listed in description above and accessory claim is approximation, and these are approximate Value can seek the characteristic of acquisition using the teachings of the present invention content with those skilled in the art and change.In minimum level On, each numerical parameter is not intended to limit application of the doctrine of equivalents on claims protection domain, at least should root Each numerical parameter is explained according to the significant digit of the numerical value recorded and by usual rounding-off method.Although setting is originally Digital scope and parameter given by the broad range of invention are approximation, but the numerical value shown in instantiation can be as accurate as possible Really report.However, any numerical value inherently contain due to be present in each of which test measure in standard deviation and nothing Some mistakes that method is avoided.

% weight, weight %, % (by weight) etc. are synonym, refer to substance weight divided by composition weight multiplied by 100 Obtained material concentration.

The number range stated by end points include this in the range of include all numerical value (for example, 1 to 5 include 1,1.5,2, 2.75th, 3,3.80,4 and 5).As used in this specification and attached claims, except non-content has in addition clearly Statement, the word " one " of singulative and " described " object signified comprising plural words and phrases.Thus, for example, including " one kindization This expression way of the composition of compound " includes the mixture comprising two or more compounds.Such as this specification and attached Plus claims used in, term "or" is typically used with the meaning comprising "and/or", except non-content have in addition it is clear Statement.

In the printed medium of the present invention, printing surface is by the first resin Composition composition and the second resin Composition composition Blend microphase-separated limit.It has been found that it is the of the first resin Composition that gained, which prints surface by most of its part, One domain and its most of part for the second domain of the second resin Composition matrix composition, and the physical configuration that has of these domains and Property combination can bring surprising performance.

In an exemplary embodiment, black receiving layer has multiple first microfacies area of isolation and the second microfacies isolated area Domain, the first resin Composition that the first microfacies area of isolation is included is more than the second resin Composition, what the second microfacies area of isolation was included Second resin Composition is more than the first resin Composition, and the second microfacies area of isolation (that is, is substantially completely closed with generally annular in shape Room) surround each in the first microfacies area of isolation, and relative protrude.

Distinctive uneven surface between first microfacies area of isolation and the second microfacies area of isolation caused by microphase-separated Characteristic causes in printing process, the trend reduction of water-based ink, thus can be obscured not at all, clearly print image Information, or even in the case of the high speed printing more than 25mm/s (for example, 100mm/s) be also such.

In some preferred embodiments, the first resin Composition includes polyalkylene oxide.In such embodiment, surface is printed Printing characteristic and adhesiveness make moderate progress because polyalkylene oxide imparts improved water-based ink acceptance and cohesive.

In certain embodiments, the acrylic polymer of the second resin Composition includes phenyloxy groups.With the component system Into the black receiving layer of gained provide the adhesiveness of adherend needed for improved black receiving layer is adhered to, and assign and being printed thereon The water resistance of the image enhancement of brush.

In certain embodiments, the relative scale of the first resin Composition and the second resin Composition make it that the ink in gained receives In layer, the first resin Composition accounts for 30 to the 60 quality % of the first resin Composition and the second resin Composition altogether in 100 mass %.Should Realized between the water resistance for being formulated the high speed printing characteristic that may be such that printing surface and printing image well balanced.

Another aspect of the present invention is related to the manufacture method of the printed medium suitable for water-based ink.Suitable for water-based ink The manufacture method of printed medium includes the blend comprising the first resin Composition, the second resin Composition and solvent being applied to base portion And coating is formed on base portion, solvent is then removed from coating the first resin Composition and the second resin Composition are occurred Microphase-separated.

According to the manufacture method, printing surface is used as adhesive surface and has good cohesive and printing characteristic Printed medium, even being printed with water soluble dyestuffs ink, the printed medium for water-based ink can be also readily available with good The printing image of good water resistance and bleed-resistant characteristic.

In certain embodiments, it can be the suspension comprising the first resin Composition and the second resin Composition to apply solution.By This black receiving layer for applying solution formation is made it easy to by using the first resin Composition and the formation printing of the second resin Composition Microphase-separated in surface.

Fig. 1 is the schematic cross sectional views for an exemplary embodiment for showing the printed medium of the present invention.Printed medium 10 With base portion 12, and black receiving layer 11 and surface F1, in the illustrated embodiment surface F1 not towards base portion 12 (i.e. and base portion Back to), it is arranged on the side of base portion 12 as printing surface.

Black receiving layer 11 includes and can be substantially by hydrophilic first resin Composition and the second resin of Thermoadhesive Component is constituted, and with the microphase-separated knot formed by the first resin Composition and the second resin Composition in printing surface F1 Structure.Second resin Composition includes the acrylic polymer with quaternized amino groups.

In the printing surface F1 of printed medium 10, the first resin Composition can as water-based ink region of acceptance there is provided into As the required acceptance of ink (for example, ink discharge device apply water-based ink), and the second resin Composition can be carried as adhesive area The required adhesiveness of adherend needed for being adhered to for medium.Therefore, the image printing of water-based ink is likely located on printing surface F1, And it is used as adhesive surface.

Further, since printed medium 10 has above-mentioned configuration, it, which prints surface F1, has good cohesive and good High speed printing characteristic, therefore it is suitable as the printed medium of the high speed spray printing for example more than 25mm/s.

In addition, in printed medium 10, the printing image formed on printing surface F1 using water-based ink in water resistance and It is very excellent in terms of bleeding resistance.Specifically, conventional printed medium (for example, printed medium described in bibliography D5) is difficult To prevent printing image from bleeding occur when water-based ink is as dye ink, but when using this printed medium 10, even by water Property dye ink formation printing image, bleeding can also be adequately suppressed.Therefore, printed medium 10 can be suitable as water soluble dyestuffs ink Printed medium.

While not wishing to be bound by theory, it is believed that as follows.Due to microphase-separated, by the first resin Composition system Into small black region of acceptance and by the small adhesive area that the second resin Composition is made complete printing surface F1 in this answer Miscellaneous structure.Therefore, water-based ink penetrates into black region of acceptance in shock point, however, penetrating into impact from the black region of acceptance of shock point Extension (bleeding) can be hindered by adhesive area caused by black region of acceptance beyond point.Therefore, it is believed that, print reclaimed water The bleeding of base ink can be prevented from, so as to form clearly image.In addition, it is thought that printing image becomes in terms of water resistance It is excellent, because even after water-based ink is printed, the bleeding of water-based ink is also prevented from because of same cause.

Second resin Composition includes the quaternized amino groups in printing surface F1.Therefore, inked when using water soluble dyestuffs During brush, the set of dyestuff becomes very excellent, and black region of acceptance and the interface of adhesive area also effectively control bleeding.Should Work as attention, it is believed that, if dyestuff is acid dyes, the set of dyestuff is even more notable, and bleeding control also very To more notable.Here it is the reason for printed medium 10 is particularly suitable as the printed medium of acid dyes ink.

Herein, term micro phase separation structure refers to that the first resin Composition and the second resin Composition show microcosmic phase point From structure.For example, when at least one in the first resin Composition and the second resin Composition forms independent phase in printing surface F1 Position, and the phase average diameter be equal to or less than 100 μm when, then can be referred to as micro phase separation structure.It should be noted that phase The Arbitrary Digit for 10 to 100 phases that the average diameter of position can be observed by using surface optical micrograph and electron micrograph Mesh is added together averagely to be determined again.

Micro phase separation structure should be equal to or less than water-based ink on printing surface F1 preferably with above-mentioned independent phase The average diameter of spot diameter.For example, in ink jet printing, when printing with cause the average diameter of ink dot be equal to or less than 30 μm, At 20 μm or 10 μm, above-mentioned independent phase should be preferably the small of the average diameter equal to or less than 30 μm, 20 μm or 10 μm Size.Even more clearly image can thus be formed.

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

Island structure, cylindrical structural, layer structure and Continuum Structure are provided as the example of micro phase separation structure. Specifically it would be desirable to island structure be such：It is in island shape wherein to have hydrophilic first resin Composition, and Second resin Composition is constituted around the sea of island.

First resin Composition is hydrophilic.It means that the first resin Composition, which has, can absorb water-based ink Property.For example, when water is dropped in resin Composition surface and fully spreads to cover extensive region, and resin Composition was at several seconds When absorbing water droplet in (for example, 5 seconds), then it may be said that resin Composition is hydrophilic.

In the exemplary embodiment, the first resin Composition may include polyalkylene oxide, hydrophilic acrylic resin, polyethylene One or more in alcohol, polyvinylpyrrolidone, hydrophilic polyurethane resin, hydrophilic ethylene vinyl alcohol.

Preferably, the first resin Composition includes polyalkylene oxide.In this case, printing surface F1 printing and adhesion are special Property become even better because polyalkylene oxide shows excellent and with cohesive in terms of the acceptance of water-based ink.Polycyclic oxygen Ethane, PPOX, oxirane and epoxy propane copolymer are provided as polyalkylene oxide.

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

Second resin Composition is heat adhesive resin Composition, and including at least the acrylic acid with quaternized amino groups Birds of the same feather flock together compound.

Acrylic polymer may also include phenyloxy groups.Thus, print the cohesive on surface and print the resistance to of image It is aqueous to be further improved.

Acrylic polymer can include the polymerization of the acrylic monomer with quaternized amino groups for monomer component Thing.In addition, monomer component may also include the acrylic monomer with phenyloxy groups, (methyl) alkyl acrylate or (first Base) acrylic acid.

For example, acrylic monomer with quaternized amino groups and including (methyl) alkyl acrylate and (methyl) The polymer of the monomer component of acrylic acid is provided as a kind of form of acrylic polymer, and monomer component may include band There is the acrylic monomer of phenyloxy groups.

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

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

For example, the group represented with following formula (1) is provided as quaternized amino groups.

In the formula, R¹、R²And R³It independently is alkyl group or aromatic yl group, and X^-For univalent anion.R¹、R²With R³Alkyl or phenyl group should be preferably respectively, more preferably alkyl group is even more preferably still C_1-2Alkyl group (containing the alkyl group that carbon number is 1 or 2).

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 easier to be more highly preferred to obtaining because of it.

With the quaternized N of methyl chloride, N- dimethyl aminoethyls (methyl) acrylate, with the quaternized N of methyl chloride, N- Dimethylaminopropyl (methyl) acrylate, with the quaternized N of methyl chloride, N- dimethyl aminoethyls (methyl) acryloyl Amine and with the quaternized N of methyl chloride, N- dimethylaminopropyls (methyl) acrylamide is suitable as carrying quaternized amino The acrylic monomer of group.

Phenoxyethyl (methyl) acrylate is provided as the acrylic monomer with phenyloxy groups.It is used as (first Base) alkyl acrylate, C_1-16(methyl) alkyl acrylate is preferred, and C_1-10(methyl) alkyl acrylate is more It is preferred that.Here, " C_1-16" and " C_1-10" represent the carbon number of alkyl group not including (methyl) acryl group.

Second resin Composition can be used as comprising hydrophobic resin component does not include the heat adhesive of acrylic polymer Resin Composition.For example, the second resin Composition can comprising polyester, hydrophobic polyurethane resin, polyester urethanes resin and Ethylene vinyl acetate.It should be noted that referring to hydrophobicity with the property for repelling water-based ink.If for example, when water drippage Nearly all water droplet is all ostracised when on resin surface, then it may be said that it is hydrophobic resin.

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

Counted by 100 mass % of the gross weight of the first and second resin Compositions, the first resin Composition in black receiving layer 11 Content can be 20 to 70 quality %, and can also be 30 to 60 quality %.Thus, it is believed that printing surface F1 microphase-separated knot The presence ratio of black region of acceptance and adhesive area in structure becomes suitable, and can print surface F1 high speed printing characteristic Realized between water resistance with printing image well balanced.Now, for example, in the high speed printing more than 100mm/s The clearly printing image of no bleeding can be obtained.

In printing surface F1, the gross area (S for the black region of acceptance being made up of the first resin Composition₁) and by the second resin The gross area (the S for the black region of acceptance that component is made₂) ratio (S₁/S₂) can be such as 0.2 to 4.0, and can be 0.4 ratio 1.5.By the way that with such area, than setting black region of acceptance and adhesive area, printing characteristic, cohesive and water resistance become very To more excellent.

Black receiving layer 11 can be arranged to such as 10 to 40 μm, or 20 to 30 μm.Black receiving layer 11 is manufactured into this During class thickness, it, which prints surface F1, has even preferably printing and adhesion characteristics.The reason for this effect, is simultaneously not always clear , but, it is believed that the bonding strength of the second resin Composition is more effective when thickness is more than 15 μm, and may insure good Bonding strength.Micro phase separation structure is uniform, and is easily formed when it is less than 40 μm.

Black receiving layer 11 should have optical transparency.According to such black receiving layer 11, the image on printing surface F1 is printed on Can from except print surface F1 in addition to surface observation to.In this case, it is preferred that addition base portion 12 (mentioning later), And with optical transparency.

Black receiving layer 11 can have the first microfacies area of isolation and the second microfacies area of isolation, the first microfacies area of isolation Comprising the first resin Composition it is more than the second resin Composition, the second resin Composition that the second microfacies area of isolation is included is than the first tree Fat component is more, and the second microfacies area of isolation surrounds the first microfacies area of isolation, and relative protrusion with generally annular in shape.This , there is phase wherein by the way that the region (the second microfacies area of isolation) that wherein there are relatively many second resin Compositions is placed in sample Around the region (the first microfacies area of isolation) of more first resin Composition, bleeding can be effectively prevented in region interface, and And significantly improve high speed printing characteristic.

It should be noted that " the first resin Composition included is more than the second resin Composition " refer to what is be made up of the first resin Composition Surface occupies the area in region than the area ratio more than the surface being made up of the second resin Composition.In addition, " relative protrusion " refers to The region is at least above adjacent first orientation area of isolation.

Should preferably have multiple first microfacies area of isolation, and it is micro- around second preferably to show annular shape greatly It is isolated each in region.That is, black receiving layer 11 preferably should have wherein the second microfacies area of isolation to be centered around Structure around first microfacies area of isolation, and the construction unit in printing surface F1 there is the uneven structure repeated to make For a unit.

In other words, in printing surface F1, black receiving layer 11 should preferably have band sunk part and with general toroidal Shape is around the uneven structure of the projection of the sunk part, and its recess the first microfacies area of isolation of formation should The first resin Composition that first microfacies area of isolation is included is more than the second resin Composition, and projection formation the second microfacies every From region, the second resin Composition that the second microfacies area of isolation is included is more than the first resin Composition.

So, it is believed that, by constituting the projection of the second microfacies area of isolation around the first microfacies isolated area of composition The outside of the sunk part in domain, forms the outward flange similar to volcanic crater, therefore retentivity of the water-based ink in printing surface F1 It is improved, and printing characteristic is also further improved.

In addition, the first microfacies area of isolation includes more first resin Compositions, and absorbed with good water-based ink Property.It is thought that the water-based ink kept by sunk part is deposited in black receiving layer 11, because be made up of sunk part One microfacies area of isolation causes the first microfacies area of isolation to have high-absorbable.

In addition, the second microfacies area of isolation includes more second resin Compositions, and contain relatively small number of first tree Fat component.It is thought that excellent cohesive and water resistance is achieved in that the protuberance of this second microfacies area of isolation Divide and form contact by adhering to object.

The shape of first microfacies area of isolation can generally circular, oval or polygon, but generally circular shape. The diameter of 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 is relative to form convex shape；However, the average height of adjacent first micro phase separation structure h₁With the average height h of the second microfacies area of isolation₂Between difference (h₂-h₁) can be usually 1 μm to 30 μm, in certain situation Under can be 2 μm to 20 μm.

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

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

It is made up of resin (such as Corvic, vistanex, acrylic resin, polyester and polyurethane resin) Paper, synthetic paper, resin film or resin sheet can be used as base portion 12.Base portion can be single or multiple lift, and should have enough chis Very little stability is for being formed on subsequent treatment and the processing of black receiving layer and printed medium.In view of it is required it is flexible, Tear strength, tensile property, elasticity, weight etc., those skilled in the art will readily be able to the suitable material that selection makes base portion Material.

Base portion 12 preferably has optical transparency.The image being printed on printing surface F1 can be by black receiving layer 11 and base See that this is due to that base portion 12 and black receiving layer 11 are respectively provided with optical transparency in portion 12.

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

Using printed medium 10, it can be used water-based ink that picture rich in detail is printed on printing surface F1, and print surface F1 also serves as adhesive surface.Therefore, printed medium 10 is readily adhered on object without any extra adhesion process.

For example, printed medium 10 is suitable as the film being fixed in IC-card, photo identification cards etc..In such case Under, for example, the image printing on IC-card will be shown in first on printing surface F1, then heated lamination ground opposite each other To printing surface F1 and IC-card.

In this kind of purposes, the IC-card with picture rich in detail can quickly be made, because printed medium 10 is in printing characteristic, viscous It is very excellent in terms of conjunction property and water resistance.In addition, prepared IC-card also becomes excellent in terms of water resistance.

If in addition, for example, printed medium 10 will be stripped after IC-card is applied to, small black region of acceptance is broken It is bad, and print content becomes to be difficult to recognize due to the micro phase separation structure in the printing surface F1 of printed medium 10.Therefore, According to printed medium 10, it can prevent from reusing IC-card for illegal objective.

In addition, printed medium 10 can be adhered on the object with uneven or curved surface for use as decorating film. In this case, high-temperature ductility base portion should be preferably used for the base portion 12 of printed medium 10.For example, this printed medium 10 can glue It is attached on the object with uneven or curved surface, to form corresponding shape when printed medium 10 are heated with dryer etc. Shape.

According to purposes, printed medium 10 can have supporting layer on the region on another surface of base portion 12, to support print Brush medium 10 and improve treatment characteristic.Such case figure 2 illustrates.

The printed medium 20 shown in Fig. 2 has base portion 22, and black receiving layer 21 and surface F2, and supporting layer 23, Surface F2 is not towards base portion 22, and on the side for being arranged on base portion 22, supporting layer is arranged on the opposite side of base portion 22.It should note Base portion 22 and black receiving layer 21 in meaning, printed medium 20 are equal to base portion 12 and black receiving layer 11 in printed medium 10.

Printed medium 20 shows excellent in terms for the treatment of characteristic, because its base portion 22 and black receiving layer 21 are carried by supporting layer 23 For support.Using printed medium 20, for example, supporting layer 23 can be stripped after water base ink print image is formed, only base portion 22 It is may adhere to black receiving layer 21 on object.

According to purposes, printed medium 10 can have dirt-proof layer on the region on another surface of base portion 12, to prevent Dust and dirt are adsorbed onto on outermost surface after printed medium 10 has been attached on object.Such case is in figure 3 Show.

The printed medium 30 shown in Fig. 3 includes base portion 32, the black receiving layer 31 with surface F3, and dirt-proof layer 33, surface F3 are arranged on the side of 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 the base portion 32 and black receiving layer 21 in printed medium 30 are equal to base portion 12 and black receiving layer in printed medium 10 11.For example, dirt-proof layer 33 can be formed by the resin combination comprising fluorine resin.

In addition, printed medium 30 can also have the supporting layer 34, black receiving layer 31 and dirt-proof layer 33 of support base 32. Using printed medium 30, for example, supporting layer 34 can be stripped after water base ink print image is formed, only base portion 32, ink receive Layer 31 and dirt-proof layer 33 may adhere on object.

It is described below the example of the printing process of the printed medium for water-based ink according to the present embodiment.

Method for printing water-based ink on the printing surface F1 of printed medium 10 is not particularly limited；However, ink-jet Printing is preferred.Printing image can quickly be formed using ink jet printing, and even can prepare above-mentioned IC-card more quickly.

The print speed printing speed of spray printing can be more than 25mm/s, more than 50mm/s or even greater than 100mm/s.The advantage of the present invention Including that under such print speed printing speed, also can form picture rich in detail on the medium of the present invention and be not in black bleeding, Because the printing 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.

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

The manufacture method includes the solution comprising the first resin Composition, the second resin Composition and solvent being applied to base portion simultaneously And the step of form coating on base portion, and solvent is removed to cause the first resin Composition and the second resin Composition from coating The step of generation microphase-separated.

According to the manufacture method, printing surface is used as adhesive surface and has good cohesive and printing characteristic Printed medium, even being printed with water soluble dyestuffs ink, the printed medium for water-based ink (is used as tool with reference to printed medium 10 Style) it can also be readily available the printing image with good water resistance and bleed-resistant characteristic.

In the application solution of the first step, the first resin Composition and the second resin Composition dissolve in solvent and can be in solvents In be separated into resin Composition particulate (term " solvent " in this article refers to wherein body fluid can be by more accurate to form suspension Ground is referred to as such embodiment of liquid medium, liquid distillate etc.).

Solvent may be such that the first resin Composition and the second resin Composition are dissolved in application solution or can be evenly dispersed in Apply in solution, and organic solvent can be suitably used.The fragrant 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 methanol and ethanol are given as the example of organic solvent Go out.It may be used in combination or be used alone these solvents.In addition, the mixture of water or water and alcohol can be used as in the manufacture method Solvent.

If it is necessary, application solution can be heated.For example, can will apply solution is heated to 30 to 60 DEG C so that the first resin group Divide and the dissolving of the second resin Composition.

In the case of one kind of the manufacture method, it can be comprising the first resin Composition and the second resin Composition to apply liquid Suspension.The black receiving layer formed by this application solution is formd with sunk part and around depressed part on printing surface The distinctive uneven shape of the peak shape projection divided, and in the case where it is formed as convex and concave shape, printing The water resistance and bleed-resistant characteristic of image are further improved.

When the first solution and the second solution are mixed, by using the first resin Composition and the second resin Composition Between poor dissolution and the first resin Composition and/or the second resin Composition are partially separated, so as to form resin particle.

For example, when the first resin Composition is polyalkylene oxide, the first resin Composition can be allowed to be dissolved in first at 40 DEG C The in the mixed solvent of ethyl ketone/toluene and methanol (weight compares 2/1/1).In addition, being used as the acrylic polymer of the second resin Composition The in the mixed solvent of acetone/methanol can be allowed to be dissolved under room temperature (for example, 20 DEG C).

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

When the first resin Composition is polyalkylene oxide, the first solution should preferably include MEK, toluene and methanol conduct Solvent, and 35 DEG C to 60 DEG C should be preferably heated to.On the other hand, the second solution should preferably include MEK or third Ketone and methanol are as solvent, and temperature should be preferably 15 DEG C to 30 DEG C.

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

Coating can be applied by applying application solution on the side of base portion.Apply the applying method of liquid not by specific Limitation, and known method can be used, such as knife coating, spin-coating method, rolling method, silk-screen printing rubbing method and intaglio process are brushed Cloth method.

Preferably, coating should be formed so that the thickness of the black receiving layer formed after second step processing is 10 to 40 μm.When coating is formed this kind of thickness, the printing surface of black receiving layer to be obtained is in terms of printing characteristic and cohesive Become even more excellent.

In second step processing, solvent is removed from coating.Volatilized by heating and remove the method and sky of solvent Gas seasoning is provided as the method for removing organic solvent.In second step processing, the solvent in coating always need not be gone completely Remove, black receiving layer can include some in solvent.

It should be appreciated that the printed medium of the present invention is formed as sheet or roll.

Above explain the suitable embodiment of the present invention；However, the present invention is not limited to above-described embodiment.For example, Using the present invention, the printing image formed by water-based ink on the printing surface F1 of printed medium 10 can be decorating film.In addition, this Invention can be decoration (for example, IC-card with printing image), wherein forming having on printing surface F1 by water-based ink The printed medium 10 of printing image is sticked on object (for example, main body of IC-card).

Example

Hereinafter, the present invention will be more fully described with reference to following explanation.

Acrylic polymer B1：By 33 mass % methyl acrylate (being optionally expressed as below " MA "), 55% matter The phenoxy ethyl acrylate (being optionally expressed as below " PhEA ") of amount, 10 mass % use methyl chloride quaternized N, N- Dimethyl amino ethyl acrylate (being optionally expressed as below " DMAEA-Q ") and 2 mass % acrylic acid (are regarded below Situation is expressed as " AA ") in the mixed solvent of 148.58 mass % acetone and 34.49 mass % methanol is dissolves uniformly in, Then solution is reacted.It should be noted that compactness is used as DMAEA-Q for the 79 mass % aqueous solution.By the reaction solution In the glass container for pouring into pressure-and heat-resistance, 0.1 mass % azodiisobutyronitrile is added as initiator, then nitrogen is passed through Reaction solution, while stirring 10 minutes to be reduced.Then, 20 hours are heated at 50 DEG C to carry out copolyreaction, Obtain 35 mass % acrylic polymer B1 solution.

Acrylic polymer B2：By 43 mass % methyl acrylate, 45 mass % phenoxy ethyl acrylate, The quaternized N of 10 mass % use methyl chloride, N- dimethyl amino ethyl acrylates and 2 mass % acrylic acid are uniform Ground is dissolved in the in the mixed solvent of 148.58 mass % acetone and 34.49 mass % methanol, and then solution is reacted.Should Work as attention, compactness is used as DMAEA-Q for the 79 mass % aqueous solution.The glass that the reaction solution is poured into pressure-and heat-resistance holds In device, 0.1 mass % azodiisobutyronitrile is added as initiator, nitrogen is then passed through reaction solution, while stirring 10 Minute to be reduced.Then, 20 hours are heated at 50 DEG C to carry out copolyreaction, 35 mass % acrylic acid is obtained Birds of the same feather flock together compound B2 solution.

Acrylic polymer B3：By 23 mass % methyl acrylate, 65 mass % phenoxy ethyl acrylate, The quaternized N of 10 mass % use methyl chloride, N- dimethyl amino ethyl acrylates and 2 mass % acrylic acid are uniform Ground is dissolved in the in the mixed solvent of 148.58 mass % acetone and 34.49 mass % methanol, and then solution is reacted.Should Work as attention, compactness is used as DMAEA-Q for the 79 mass % aqueous solution.The glass that the reaction solution is poured into pressure-and heat-resistance holds In device, 0.1 mass % azodiisobutyronitrile is added as initiator, nitrogen is then passed through reaction solution, while stirring 10 Minute to be reduced.Then, 20 hours are heated at 50 DEG C to carry out copolyreaction, 35 mass % acrylic acid is obtained Birds of the same feather flock together compound B3 solution.

Acrylic polymer B4：By 73 mass % methyl acrylate, 15 mass % phenoxy ethyl acrylate, The quaternized N of 10 mass % use methyl chloride, N- dimethyl amino ethyl acrylates and 2 mass % acrylic acid are uniform Ground is dissolved in the in the mixed solvent of 148.58 mass % acetone and 34.49 mass % methanol, and then solution is reacted.Should Work as attention, compactness is used as DMAEA-Q for the 79 mass % aqueous solution.The glass that the reaction solution is poured into pressure-and heat-resistance holds In device, 0.1 mass % azodiisobutyronitrile is added as initiator, nitrogen is then passed through reaction solution, while stirring 10 Minute to be reduced.Then, 20 hours are heated at 50 DEG C to carry out copolyreaction, 35 mass % acrylic acid is obtained Birds of the same feather flock together compound B4 solution.

Acrylic polymer B5：33 mass % 2- ethylhexyl acrylates (are optionally expressed as below " 2EHA "), the phenoxy ethyl acrylate of 55% mass, the 10 mass % quaternized N of use methyl chloride, N- dimethylaminos Ethyl propylene acid esters and 2 mass % acrylic acid are dissolves uniformly in 148.58 mass % acetone and 34.49 mass % The in the mixed solvent of methanol, then solution reacted.It should be noted that compactness is used as the 79 mass % aqueous solution DMAEA-Q.In the glass container that the reaction solution is poured into pressure-and heat-resistance, 0.1 mass % azodiisobutyronitrile conduct is added Initiator, is then passed through reaction solution by nitrogen, while stirring 10 minutes to be reduced.Then, it is heated at 50 DEG C Carry out copolyreaction within 20 hours, obtain 35 mass % acrylic polymer B5 solution.

Acrylic polymer B6：By 29 mass % methyl acrylate, 55 mass % phenoxy ethyl acrylate, The quaternized N of 10 mass % use methyl chloride, N- dimethyl amino ethyl acrylates and 2 mass % acrylic acid are uniform Ground is dissolved in the in the mixed solvent of 148.58 mass % acetone and 34.49 mass % methanol, and then solution is reacted.Should Work as attention, compactness is used as DMAEA-Q for the 79 mass % aqueous solution.The glass that the reaction solution is poured into pressure-and heat-resistance holds In device, 0.1 mass % azodiisobutyronitrile is added as initiator, nitrogen is then passed through reaction solution, while stirring 10 Minute to be reduced.Then, 20 hours are heated at 50 DEG C to carry out copolyreaction, 35 mass % acrylic acid is obtained Birds of the same feather flock together compound B6 solution.

Acrylic polymer B7：By the quaternized N of the use methyl chloride of 88 mass % methyl acrylate, 10 mass %, N- dimethyl amino ethyl acrylates and 2 mass % acrylic acid be dissolves uniformly in 148.58 mass % acetone and The in the mixed solvent of 34.49 mass % methanol, then solution reacted.It should be noted that compactness is 79 mass % water Solution is used as DMAEA-Q.In the glass container that the reaction solution is poured into pressure-and heat-resistance, 0.1 mass % azo two is added Then nitrogen is passed through reaction solution by isobutyronitrile as initiator, while stirring 10 minutes to be reduced.Then, by itself plus Heat carried out copolyreaction to 20 hours at 50 DEG C, obtained 35 mass % acrylic polymer B7 solution.

Acrylic polymer B8：By 58 mass % methyl acrylate, 35 mass % phenoxy ethyl acrylate, The quaternized N of 5 mass % use methyl chloride, N- dimethyl amino ethyl acrylates and 2 mass % acrylic acid are equably The in the mixed solvent of 148.58 mass % acetone and 34.49 mass % methanol is dissolved in, then solution is reacted.Should Reaction solution is poured into the glass container of pressure-and heat-resistance, is added 0.1 mass % azodiisobutyronitrile as initiator, then will Nitrogen is passed through reaction solution, while stirring 10 minutes to be reduced.Then, 20 hours are heated at 50 DEG C to be total to Poly- reaction, obtains 35 mass % acrylic polymer B8 solution.

Acrylic polymer B9：By 33 mass % methyl acrylate, the phenoxy ethyl acrylate of 55% mass, 10 mass % N, N- dimethyl amino ethyl acrylates (tertiary amine for being optionally expressed as " DMAEA ") and 2 mass % Acrylic acid be dissolves uniformly in the in the mixed solvent of 148.58 mass % acetone and 34.49 mass % methanol, it is then molten Liquid is reacted.In the glass container that the reaction solution is poured into pressure-and heat-resistance, 0.1 mass % of addition azodiisobutyronitrile is made For initiator, nitrogen is then passed through reaction solution, while stirring 10 minutes to be reduced.Then, 50 DEG C are heated to Carry out copolyreaction within lower 20 hours, obtain 35 mass % acrylic polymer B9 solution.

Acrylic polymer B10：By 43 mass % methyl acrylate, the phenoxy ethyl acrylate of 55% mass The mixed solvent of 148.58 mass % acetone and 34.49 mass % methanol is dissolves uniformly in 2 mass % acrylic acid In, then solution is reacted.In the glass container that the reaction solution is poured into pressure-and heat-resistance, 0.1 mass % azo is added Then nitrogen is passed through reaction solution by bis-isobutyronitrile as initiator, while stirring 10 minutes to be reduced.Then, by it It is heated at 50 DEG C 20 hours to carry out copolyreaction, obtains 35 mass % acrylic polymer B10 solution.

Acrylic polymer B11：By 28 mass % methyl acrylate, 55 mass % acrylic acid Phenoxyethyl The quaternized N of use methyl chloride of ester, 15 mass %, N- dimethyl amino ethyl acrylates and 2 mass % acrylic acid are equal The in the mixed solvent of 148.58 mass % acetone and 34.49 mass % methanol is dissolved in evenly, and then solution is reacted. In the glass container that the reaction solution is poured into pressure-and heat-resistance, 0.1 mass % azodiisobutyronitrile is added as initiator, so Nitrogen is passed through reaction solution afterwards, while stirring 10 minutes to be reduced.Then, 20 hours are heated at 50 DEG C to enter Row copolyreaction, obtains 35 mass % acrylic polymer B5 solution.

Acrylic polymer B12：By 25 mass % methyl acrylate, 55 mass % acrylic acid Phenoxyethyl The quaternized N of use methyl chloride of ester, 10 mass %, N- dimethyl amino ethyl acrylates and 10 mass % acrylic acid The in the mixed solvent of 148.58 mass % acetone and 34.49 mass % methanol is dissolves uniformly in, then solution carries out anti- Should.In the glass container that the reaction solution is poured into pressure-and heat-resistance, 0.1 mass % of addition azodiisobutyronitrile is used as starting Agent, is then passed through reaction solution by nitrogen, while stirring 10 minutes to be reduced.Then, 20 are heated at 50 DEG C small When carry out copolyreaction, obtain 35 mass % acrylic polymer B5 solution.

The ratio (mass ratio) for constituting acrylic polymer B1 to B10 monomeric unit is shown 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 Chemicals Co., Ltd. polyalkylene oxide), the mass % of compactness 100) mixed solvent (quality of MEK/toluene and methanol is dissolved at 40 DEG C In 2/1/1), the density of solid of preparation is regard as the first resin Composition for 15 mass % solution A 1.In addition, containing 35 matter The solution (hereinafter referred to solution B 1) for measuring % acrylic polymer B1 is used as the second resin Composition.

40 DEG C of solution A 1 and solution B 1 are mixed the mass ratio of the first resin Composition and the second resin Composition is become For 60/40, mixture C 1 is prepared.

Printed medium 1 is obtained by following steps：Using knife coating in the polyethylene terephthalate that thickness is 50 μm Apply solution C 1 on ester film (PET film), then solution C 1 is dried 10 minutes in 80 DEG C of baking oven is set to, with PET Black receiving layer is formed on film.Then, the thickness of the black receiving layer formed after drying is adjusted to 25 μm.It should be noted that passing through The gap between PET film surface and knife surface is adjusted to adjust the thickness of black receiving layer.

When the printed medium 1 obtained with the micro- sem observation of surface optical, the black receiving layer of printed medium 1 is in printing table There is near uniform micro phase separation structure in face.As a result figure 4 illustrates.

In addition, measuring obtained print using non-planar contact surfaces roughness measuring instrument (deriving from Zhai Ke companies (Zaygo)) The printing surface of the black receiving layer of brush medium 1, to measure the surface roughness on printing surface.As a result figure 5 illustrates.According to figure The result shown in 5, unique uneven structure arrangement is confirmed, and wherein construction unit is by the first micro- of circular shape It isolates region and is isolated with the second convex shape microfacies generally annular in shape for surrounding the first microfacies area of isolation neighboring Region is constituted.In other words, it is thus identified that unique uneven structure is formed so that the second micro phase separation structure with peak shape Rise and the first microfacies area of isolation is surrounded with circular shape.

The micro phase separation structure on printing surface is formed as island structure, and the average diameter of island is about 5 μm.In addition, big Cause a diameter of about 50 to 300 μm of round-shaped the first microfacies area of isolation, and the first micro phase separation structure is averaged Height h₁With the average height h of the second microfacies area of isolation₂Between difference (h₂-h₁) it is about 25 to 30 μm.

In addition, according to the result that surface is observed using AFM (AFM), it is thus identified that in the first microfacies area of isolation The first resin Composition existed is more than the second resin Composition, and the second resin Composition present in the second microfacies area of isolation compares the One resin Composition is more.Specifically, according to the crystal orientation state confirmation existence shown by the first resin Composition.

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

Example 2

In addition, except solution (the hereinafter referred to solution B 2) generation using the acrylic polymer B2 containing 35 mass % For solution B 1 as the second resin Composition, printed medium 2 is obtained using the method similar to example 1.

When the printed medium 2 obtained with the micro- sem observation of surface optical, the black receiving layer of printed medium 2 is in printing table There is near uniform micro phase separation structure in face.

In addition, measuring obtained print using non-planar contact surfaces roughness measuring instrument (deriving from Zhai Ke companies (Zaygo)) The printing surface of the black receiving layer of brush medium 2, to measure the surface roughness on printing surface.According to use non-planar contact surfaces roughness The measurement result of measuring instrument, confirmation is formd similar to the multiple of example 1 in the printing surface of the black receiving layer of printed medium 2 The uneven structure of uniqueness of arrangement, the uneven structure has the first microfacies area of isolation, and is surrounded with generally annular in shape The second microfacies area of isolation in convex shape of first microfacies area of isolation neighboring.

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

Example 3

In addition, except solution (the hereinafter referred to solution B 3) generation using the acrylic polymer B3 containing 35 mass % For solution B 1 as the second resin Composition, printed medium 3 is obtained using the method similar to example 1.

When the printed medium 3 obtained with the micro- sem observation of surface optical, the black receiving layer of printed medium 3 is in printing table There is near uniform micro phase separation structure in face.

In addition, measuring obtained print using non-planar contact surfaces roughness measuring instrument (deriving from Zhai Ke companies (Zaygo)) The printing surface of the black receiving layer of brush medium 3, to measure the surface roughness on printing surface.According to coarse using non-planar contact surfaces The measurement result of measuring instrument is spent, confirmation is formd similar to many of example 1 in the printing surface of the black receiving layer of printed medium 3 The uneven structure of uniqueness of rearrangement, the uneven structure has the first microfacies area of isolation, and is enclosed with generally annular in shape The second microfacies area of isolation in convex shape around the first microfacies area of isolation neighboring.

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

Example 4

In addition, except solution (the hereinafter referred to solution B 4) generation using the acrylic polymer B4 containing 35 mass % For solution B 1 as the second resin Composition, printed medium 4 is obtained using the method similar to example 1.

When the printed medium 4 obtained with the micro- sem observation of surface optical, the black receiving layer of printed medium 4 is in printing table There is near uniform micro phase separation structure in face.

In addition, measuring obtained print using non-planar contact surfaces roughness measuring instrument (deriving from Zhai Ke companies (Zaygo)) The printing surface of the black receiving layer of brush medium 4, to measure the surface roughness on printing surface.According to coarse using non-planar contact surfaces The measurement result of measuring instrument is spent, confirms to form similar to the multiple of example 1 in the printing surface of the black receiving layer of printed medium 4 The uneven structure of uniqueness of arrangement, the uneven structure has the first microfacies area of isolation, and is surrounded with generally annular in shape The second microfacies area of isolation in convex shape of first microfacies area of isolation neighboring.

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

Example 5

In addition, except solution (the hereinafter referred to solution B 5) generation using the acrylic polymer B5 containing 35 mass % For solution B 1 as the second resin Composition, printed medium 5 is obtained using the method similar to example 1.

When the printed medium 5 obtained with the micro- sem observation of surface optical, the black receiving layer of printed medium 5 is in printing table There is near uniform micro phase separation structure in face.

In addition, measuring obtained print using non-planar contact surfaces roughness measuring instrument (deriving from Zhai Ke companies (Zaygo)) The printing surface of the black receiving layer of brush medium 5, to measure the surface roughness on printing surface.According to coarse using non-planar contact surfaces The measurement result of measuring instrument is spent, confirmation is formd similar to many of example 1 in the printing surface of the black receiving layer of printed medium 5 The uneven structure of uniqueness of rearrangement, the uneven structure has the first microfacies area of isolation, and is enclosed with generally annular in shape The second microfacies area of isolation in convex shape around the first microfacies area of isolation neighboring.

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

Example 6

Except replace solution C 1 and using by mix 40 DEG C solution A 1 and solution B 1 and preparation mixture C 2 (because The mass ratio of this first resin Composition and the second resin Composition is changed into 50/50), being printed using the method similar to example 1 Medium 6.

When the printed medium 6 obtained with the micro- sem observation of surface optical, the black receiving layer of printed medium 6 is in printing table There is near uniform micro phase separation structure in face.

In addition, measuring obtained print using non-planar contact surfaces roughness measuring instrument (deriving from Zhai Ke companies (Zaygo)) The printing surface of the black receiving layer of brush medium 6, to measure the surface roughness on printing surface.According to coarse using non-planar contact surfaces The measurement result of measuring instrument is spent, confirmation is formd similar to the multiple of example 1 in the printing surface of the receiving layer of printed medium 6 The uneven structure of uniqueness of arrangement, the uneven structure has the first microfacies area of isolation, and is surrounded with generally annular in shape The second microfacies area of isolation in convex shape of first microfacies area of isolation neighboring.

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

Example 7

In addition, except solution (the hereinafter referred to solution B 6) generation using the acrylic polymer B6 containing 35 mass % For solution B 1 as the second resin Composition, printed medium 7 is obtained using the method similar to example 1.

When the printed medium 7 obtained with the micro- sem observation of surface optical, the black receiving layer of printed medium 7 is in printing table There is near uniform micro phase separation structure in face.

In addition, measuring obtained print using non-planar contact surfaces roughness measuring instrument (deriving from Zhai Ke companies (Zaygo)) The printing surface of the black receiving layer of brush medium 7, to measure the surface roughness on printing surface.According to coarse using non-planar contact surfaces The measurement result of measuring instrument is spent, confirmation is formd similar to many of example 1 in the printing surface of the black receiving layer of printed medium 7 The uneven structure of uniqueness of rearrangement, the uneven structure has the first microfacies area of isolation, and is enclosed with generally annular in shape The second microfacies area of isolation in convex shape around the first microfacies area of isolation neighboring.

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

Example 8

By AQUA(derive from Sumitomo Seika Co., Ltd (Sumitomo Seika Chemicals Co., Ltd. polyalkylene oxide), the mass % of compactness 100) mixed solvent (quality of MEK/toluene and methanol is dissolved at 40 DEG C In 2/1/1), the density of solid of preparation is regard as the first resin Composition for 15 mass % solution A 2.Except using solution A 2 Outside solution A 1, printed medium 8 is obtained using the method similar to example 1.

When the printed medium 8 obtained with the micro- sem observation of surface optical, the black receiving layer of printed medium 8 is in printing table There is near uniform micro phase separation structure in face.

In addition, measuring obtained print using non-planar contact surfaces roughness measuring instrument (deriving from Zhai Ke companies (Zaygo)) The printing surface of the black receiving layer of brush medium 8, to measure the surface roughness on printing surface.As coarse using non-planar contact surfaces The measurement result of measuring instrument is spent, observed by being not observed in the printing surface of the black receiving layer of printed medium 8 in example 1 The uneven structure of uniqueness, but surface texture is formed by the unit of larger chevron shape.

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

Example 9

Solution A 2 is prepared using the method similar to example 8.Then, by 40 DEG C of solution A 2 and solution B 1 mix with So that the mass ratio of the first resin Composition and the second resin Composition is changed into 30/70, mixture C 3 is prepared.

In addition to replacing mixture C 1 using mixture C 3, printed medium 9 is obtained using the method similar to example 1.

When the printed medium 9 obtained with the micro- sem observation of surface optical, the black receiving layer of printed medium 9 is in printing table There is near uniform micro phase separation structure in face.

In addition, measuring obtained print using non-planar contact surfaces roughness measuring instrument (deriving from Zhai Ke companies (Zaygo)) The printing surface of the black receiving layer of brush medium 9, to measure the surface roughness on printing surface.As coarse using non-planar contact surfaces The measurement result of measuring instrument is spent, observed by being not observed in the printing surface of the black receiving layer of printed medium 8 in example 1 The uneven structure of uniqueness, but surface texture is formed by the unit of larger chevron shape.

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

Example 10

Solution A 2 is prepared using the method similar to example 8.In addition, the acrylic polymer containing 35 mass % B7 solution (hereinafter referred to solution B 7) is used as the second resin Composition.Then, by 40 DEG C of solution A 2 and solution B 7 mix with So that the mass ratio of the first resin Composition and the second resin Composition is changed into 40/60, mixture mixture C 4 is prepared.

In addition to replacing mixture C 1 using mixture C 4, printed medium 10 is obtained using the method similar to example 1.

When the printed medium 10 obtained with the micro- sem observation of surface optical, the black receiving layer of printed medium 10 is in printing There is near uniform micro phase separation structure in surface.

In addition, measuring obtained print using non-planar contact surfaces roughness measuring instrument (deriving from Zhai Ke companies (Zaygo)) The printing surface of the black receiving layer of brush medium 10, to measure the surface roughness on printing surface.As thick using non-planar contact surfaces The measurement result of rugosity measuring instrument, observed by being not observed in the printing surface of the black receiving layer of printed medium 9 in example 1 The uneven structure of uniqueness arrived, but surface texture is formed by the unit of larger chevron shape.

Example 11

In addition, except solution (the hereinafter referred to solution B 8) generation using the acrylic polymer B8 containing 35 mass % For solution B 1 as the second resin Composition, printed medium 11 is obtained using the method similar to example 1.

When the printed medium 11 obtained with the micro- sem observation of surface optical, the black receiving layer of printed medium 11 is in printing There is near uniform micro phase separation structure in surface.

In addition, measuring obtained print using non-planar contact surfaces roughness measuring instrument (deriving from Zhai Ke companies (Zaygo)) The printing surface of the black receiving layer of brush medium 11, to measure the surface roughness on printing surface.According to thick using non-planar contact surfaces The measurement result of rugosity measuring instrument, confirmation is formd similar to example 1 in the printing surface of the black receiving layer of printed medium 11 Many rearrangements the uneven structure of uniqueness, the uneven structure has the first microfacies area of isolation, and with general toroidal shape Shape surrounds the second microfacies area of isolation in convex shape of the first microfacies area of isolation neighboring.

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

Comparative example C1

Solution A 2 is prepared using the method similar to example 8.Then, the propylene by solution A 2 and containing 35 mass % Acids polymers B9 solution (hereinafter referred to solution B 9) mixing so that the quality of the first resin Composition and the second resin Composition Than being changed into 40/60, mixture D 1 is prepared.

In addition to replacing mixture C 1 using mixture D 1, printed medium 21 is obtained using the method similar to example 1.

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

It should be noted that confirming that printed medium 21 has almost on printing surface when sem observation micro- with surface optical Even micro phase separation structure.However, according to the survey using non-planar contact surfaces roughness measuring instrument (deriving from Zhai Ke companies (Zaygo)) Result is measured, unique unevenness structure what is observed in example 1 is not observed in printing surface, but by larger chevron The unit formation surface texture of shape.Figure 6 illustrates non-planar contact surfaces roughness concentration for the microscopical observation result of surface optical The measurement result of instrument figure 7 illustrates.

Comparative example C2

Solution A 1 is prepared using the method similar to example 1.Then, the propylene by solution A 1 and containing 35 mass % Acids polymers B10 solution (hereinafter referred to solution B 10) mixing so that the matter of the first resin Composition and the second resin Composition Amount ratio is changed into 40/60, prepares mixture D 2.

In addition to replacing mixture C 1 using mixture D 2, printed medium 22 is obtained using the method similar to example 1.

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

It should be noted that confirming that printed medium 22 has almost on printing surface when sem observation micro- with surface optical Even micro phase separation structure.However, according to the survey using non-planar contact surfaces roughness measuring instrument (deriving from Zhai Ke companies (Zaygo)) Result is measured, unique unevenness structure what is observed in example 1 is not observed in printing surface.

Comparative example C3

By 40 mass % AQUA(derive from Sumitomo Seika Co., Ltd (Sumitomo Seika Chemicals Co., Ltd.s), 100 mass % compactness), 40 matter as hydrophobic resin with heat adhesive property Measure % hydrophobic polyester670 (deriving from the polyester that Co., Ltd. (Toyobo Co., Ltd.s) is spun by Japan) and 20 Quality % polyurethane resinUR-3200 (derives from the polyester that Co., Ltd. (Toyobo Co., Ltd.s) is spun by Japan Urethane resin, glass transition temperature：- 3 DEG C, 30 mass % compactness) it is sufficiently stirred for divide at 60 DEG C Dissipate in the in the mixed solvent of MEK/toluene (mass ratio 1/1).

Printed medium 23 is obtained by following steps：Using knife coating in the polyethylene terephthalate that thickness is 50 μm Ester film (PET film) upper solution D 3, then causes solution D 3 to be dried 10 minutes in 80 DEG C of baking oven is set to, with PET Black receiving layer is formed on film.Then, the thickness of the black receiving layer formed after drying is adjusted to 25 μm.

It should be noted that confirming that printed medium 23 has almost on printing surface when sem observation micro- with surface optical Even micro phase separation structure.However, according to the survey using non-planar contact surfaces roughness measuring instrument (deriving from Zhai Ke companies (Zaygo)) Result is measured, unique unevenness structure what is observed in example 1 is not observed in printing surface.

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

Method of testing

Printing characteristic is evaluated：UseInk-jet printer p-640L, using the water soluble dyestuffs ink of six kinds of colors, The picture of people and letter are printed on the black receiving layer of printed medium with 25mm/s or 100mm/s print speed printing speed.With following 5 Individual grade carries out visual evaluation to printing image." D " represent printing image be it is most fuzzy, print image vividness from " C ", " B " to " A " represents to be improved successively, and " AA " is to most clearly printing the fraction that image is provided.It should be noted that in 25mm/s Print speed printing speed under the result that obtains be evaluated as " printing characteristic ", the result obtained under 100mm/s print speed printing speed is commented Valency is " high speed printing characteristic ".

Bleeding evaluating characteristics：Print image on the black receiving layer of printed medium, similar method is evaluated using printing To be evaluated.Then, printed medium and vinyl chloride resin card are placed such that to the printing surface and the one of card of printed medium Side is facing with each other, is then heated lamination (continuing 1 second at 120 DEG C) using roll shape heat-laminator.Printing image is carried out Visual Observations Observations, check sample after standing 7 days at 80 DEG C with the presence or absence of any fuzzy.The evaluation is rated as following 5 grades.

AA：Do not change completely.

A：Had almost no change compared with tester.

B：There is significant change compared with tester.

C：Have obvious fuzzy.

D：Exist in whole surface and obviously obscure.

Normal temperature adhesive intensity evaluation：Print image on the black receiving layer of printed medium, evaluate similar using printing Method is evaluated.Then, printed medium and vinyl chloride resin card are placed such that to printing surface and the card of printed medium Side it is facing with each other, be then heated lamination (continuing 1 second at 120 DEG C) using roll shape heat-laminator.

In the measurement sample obtained after being placed 24 hours at 23 DEG C, measured using tensile testing machine at 23 DEG C 180 ° of peel strength (N/25mm).Measuring condition is set to 200mm/min draw speed.In the feelings more than 15N/25mm Under condition or when material damage, measurement result is be evaluated as " A "；In the case of between 15-10N/25mm, measurement result It is be evaluated as " B "；In the case of less than 10N/25mm, measurement result is be evaluated as " C ".

High-temperature bond strength is evaluated：Measurement sample is obtained using the similar method of normal temperature adhesive intensity evaluation.Obtained Measurement sample after being placed 24 hours at 23 DEG C, 180 ° of peel strength is measured at 80 DEG C using tensile testing machine (N/25mm).Measuring condition is set to 200mm/min draw speed.In the case of more than 15N/25mm or when material is damaged Bad when, measurement result is be evaluated as " A "；In the case of between 15-10N/25mm, measurement result is be evaluated as " B "； In the case of 10N/25mm, measurement result is be evaluated as " C ".

Water resistance is evaluated：Measurement sample is obtained using the similar method of normal temperature adhesive intensity evaluation.Will measurement sample in After being placed 24 hours in water under room temperature (25 DEG C), the change of its outward appearance of visual confirmation.It should be noted that in water resistance evaluation In, the situation that change is not observed is rated for " AA "；3-5mm width is heaved at the edge of wherein laminate, but can recover Situation to original state is rated for " A "；3-5mm width is heaved at the edge of wherein laminate, and can not return to initial The situation of state is rated for " B "；The situation that wherein adhesive phase is eluted is rated for " C "；There is the situation of bur in film It is rated for " D ".

Table 2

Claims (7)

1. a kind of printed medium for water-based ink, the printed medium includes the base portion with first surface and in the base Black receiving layer at least a portion of the first surface in portion, wherein：(1) the black receiving layer has by the first resin group It is grouped the printing surface that the microphase-separated of the blend of compound and the second resin Composition composition is limited；(2) first resin Component is hydrophilic；And (3) second resin Composition includes the acrylic polymer with quaternized amino groups And show heat adhesive characteristic；First domain and Qi Duo of the wherein described printing surface by its most part for the first resin Composition Number part constitutes for the matrix in the second domain of the second resin Composition, and wherein described second domain surrounds each first domain, and Second domain is relative to protrude.

2. printed medium according to claim 1, wherein first resin Composition includes polyalkylene oxide.

3. printed medium according to claim 1, wherein the acrylic polymer has phenyloxy groups.

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

5. printed medium according to claim 1, wherein first resin Composition and second resin Composition is total Amount is in terms of 100 mass %, and amount of first resin Composition in the black receiving layer is 20 to 70 quality %.

6. a kind of method of printed medium for described in manufacturing claims 1, methods described includes：(1) providing has first The base portion on surface；(2) blend of the first resin Composition composition and the second resin Composition composition is provided；(3) to the base At least a portion of the first surface in portion applies the blend to be formed on coating；And (4) are from the coating Middle removal solvent so that microphase-separated occurs for first resin Composition and second resin Composition, to produce printing surface, The printing surface is that the first domain and its most part of the first resin Composition are the of the second resin Composition by its most part The matrix composition in two domains, wherein second domain surrounds each first domain, and the relative protrusion in second domain.

7. method according to claim 6, wherein it is to include by first resin Composition and described second to apply liquid The suspension of the resin particle of resin Composition composition.