KR20150053997A - Print media for water-based color ink jet printing and method for manufacturing same - Google Patents

Abstract

A printing medium for a water-based ink comprising a base material and an ink receiving layer provided on one side of the base material and having a surface that does not face the base material to be used as a printing surface, wherein the ink receiving layer comprises a hydrophilic first resin, And a second resin comprises an acrylic polymer having a quaternized amino group, wherein the printing resin has a micro-phase separation structure formed by the first resin and the second resin, and the second resin contains an acrylic polymer having a quaternized amino group.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a color inkjet printing medium,

The present invention relates to a printing medium, in particular, a printing medium for water-based color inkjet printing, and a method of manufacturing the same.

As a conventional print medium, various products such as paper, synthetic paper, and resin film are known. Such print media are attached to a variety of objects, for example, by providing an adhesive on a print medium, applying a double-sided adhesive tape, or the like.

In recent years, the construction of print media is well known, in which the print surface also functions as an adhesive surface and it is not necessary to apply the adhesive onto the print image. An illustrative example is disclosed below: D1 - Japanese Patent Application Laid-Open No. 2004-276613; D2 - Japanese Patent Application Laid-Open No. 11-165457; D3 - Japanese Patent Application Laid-Open No. 2008-087276; D4 - Japanese Patent Application Laid-Open No. 2008-087324; And D5 - Japanese Patent Laid-Open Publication No. 2011-255650.

There is a need for aqueous inkjet receptive media for use in high speed printing applications, which exhibit improved image to bleed resistance, water absorption and resistance to water damage.

The present invention provides improved inkjet water-soluble print media and methods of making such media.

Briefly summarized, the printing medium of the present invention comprises a base having a first surface and an ink receiving layer on at least a portion of the first surface of the substrate. According to the present invention: (1) the ink receiving layer has a printing surface formed by micro-phase separation of the blend of the first resin component composition and the second resin component composition; (2) the first resin component is hydrophilic; (3) The second resin component contains an acrylic polymer having a quaternized amino group and exhibits thermal adhesiveness. Surprisingly, an ink receiving layer having a printing surface or area formed by a micro-phase separation structure as described herein has been shown to provide unexpected beneficial results.

As described herein, the first and second resin components exhibit a micro-phase separation structure at the print surface.

Briefly summarized, a method of producing a print medium of the present invention comprises the steps of: (1) providing a substrate having a first surface; (2) providing a blend of a first resin component composition and a second resin component composition; (3) applying the blend to at least a portion of the first surface of the substrate to form a coating thereon; And (4) removing the solvent from the coating to cause micro-phase separation of the first resin component and the second resin component.

The media provided by the present invention can be used for a wide range of applications, including good high resolution water solubility, image bleed resistance, water absorption and water resistance to waterborne inks, and good adhesion properties, i.e. the print surface will be adhered to the desired adherend It offers a remarkable combination of significant benefits including: The media of the present invention is well suited for use in high speed printing applications and can be used to produce articles having high quality, high resolution, durable images thereon.

Previously, for example, prior art techniques such as those described in references D1 to D4 failed to provide print media capable of the desired performance and function. Reference D5 claims to disclose a medium exhibiting the desired performance and function, but the media disclosed therein are found to exhibit dye bleeding when dye inks as aqueous inks are applied with high speed jet printing in excess of 25 mm / sec lost.

According to the present invention, the printing surface contains a plurality of first micro-phase separation regions containing a larger amount of the first resin component than the second resin component, and a second resin component more than the first resin component, And has a second convex micro-phase separation region surrounding the micro-phase separation region approximately in the shape of a ring.

The invention is further described with reference to the drawings.
1 is a schematic sectional view showing one exemplary embodiment of a print medium of the present invention;
2 is a schematic sectional view showing another exemplary embodiment of the print medium of the present invention.
3 is a schematic cross-sectional view showing another exemplary embodiment of the print medium of the present invention.
4 is a view showing the surface of the print medium obtained in Example 1 when observed with an optical microscope.
5A and 5B are diagrams showing the results of measurement of the non-contact surface roughness of the print medium obtained in Example 1 with a measuring instrument.
6 is a view showing the result of observing the surface of the print medium 2 obtained in Comparative Example 1 with an optical microscope.
7A and 7B are diagrams showing the results of measurement of the non-contact surface roughness of the print medium obtained in Comparative Example 1 with a measuring instrument.
1 to 3 are not drawn to scale, and FIGS. 1 to 7 are intended to be illustrative only and not limiting.
Explanation of reference numerals

Hereinafter, preferred embodiments of the present invention will be described with reference to the accompanying drawings.

Unless otherwise indicated, all numbers expressing quantities, characteristics, e.g., molecular weights, reaction conditions, etc., of the components used in the specification and claims are to be understood as being modified in all instances by the term "about. &Quot; Accordingly, unless indicated to the contrary, the numerical parameters set forth in the foregoing specification and attached claims are approximations, which may vary depending upon the desired properties desired by one of ordinary skill in the art using the teachings of the present invention. At the very least, and without wishing to restrict the application of the doctrine of equivalents to the scope of the claims, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques. Numerical ranges and parameters describing the broad scope of the invention are approximations, but numerical values set forth in the specific examples are reported as precisely as possible. However, any numerical value inherently includes certain errors necessarily resulting from the standard deviation found in the respective test measurements.

Percent by weight, percent by weight, percent by weight, etc. are synonyms that divide the weight of the material by the weight of the composition and multiply it by 100 as the concentration of the material.

A reference to a numerical range by an endpoint includes all numbers contained within that range (e.g., 1 to 5 include 1, 1.5, 2, 2.75, 3, 3.80, 4, and 5). As used in this specification and the appended claims, the singular forms "a", "an," and "the" include plural referents unless the content clearly dictates otherwise. Thus, reference to a composition containing, for example, a "compound" includes a mixture of two or more compounds. As used in this specification and the appended claims, the term "or" is generally used to include "and / or" in its meaning unless the context clearly dictates otherwise.

In the printing medium of the present invention, the printing surface is formed by micro-phase separation of the blend of the first resin component composition and the second resin component composition. The resulting printed surface is formed with a matrix of a first domain, which is mostly the first resin component and a second domain, which is mostly the second resin component, and these domains have a physical configuration And combinations thereof.

In an exemplary embodiment, the ink receiving layer contains a plurality of first micro-phase separation regions containing more of the first resin component than the second resin component, and a second resin component more than the first resin component, Phase separation region in the shape of a substantially ring (i.e., a substantially fully surrounding cell) and has a relatively convex second micro-phase separation region.

As a result of the characteristic non-uniform surface properties between the first micro-phase separation region and the second micro-phase separation region resulting from the micro-phase separation, the tendency of aqueous inks during printing is reduced and even exceeding 25 mm / sec , 100 mm / sec), a sharp print image without any blurring is formed.

In some preferred embodiments, the first resin component comprises a polyalkylene oxide. In such embodiments, the printing properties and adhesion of the printed surface are improved because the polyalkylene oxide imparts improved water solubility with adhesion properties to aqueous inks.

In some embodiments, the acrylic polymer of the second resin component comprises a phenoxy group. The resulting ink receptive layer, made of such components, provides improved adhesion of the ink receptive layer to the desired adherend and imparts improved water resistance to the printed image thereon.

In some embodiments, the relative proportions of the first resin component and the second resin component are such that the first resin component accounts for 30 to 60 mass% of the total amount of the first resin component and the second resin component in the resulting ink receiving layer, %. In such a formulation, a good balance between the high-speed printing properties of the printing surface and the water resistance of the printing image can be achieved.

Another aspect of the present invention relates to a method for producing a printing medium for an aqueous ink. A method for producing a print medium for aqueous ink includes coating a substrate with a blend containing a first resin component, a second resin component, and a solvent to form a coating on the substrate, and removing the solvent from the coating to form a first resin Phase separation of the first resin component and the second resin component.

According to this manufacturing method, the printing surface is a printing medium which functions as an adhesive surface and has both good adhesion properties and printing properties, and even when printed with water-based dye ink, the printing medium for water- Can be easily obtained.

In some embodiments, the coating liquid may be a suspension comprising a first resin component and a second resin component. The ink receiving layer formed by such a coating liquid makes it easy to form a micro-phase separation structure at the printing surface by using the first resin component and the second resin component.

1 is a schematic sectional view showing one exemplary embodiment of a printing medium of the present invention. The print medium 10 has a substrate 12 and an ink receiving layer 11 provided on one side of the substrate 12 which does not face the substrate 12, Has a surface F1 on the opposite side thereof as a printing surface.

The ink receiving layer 11 may comprise essentially a hydrophilic first resin component and a thermally adhesive second resin component and may be formed on the printing surface F1 by a first resin component and a second resin component Lt; / RTI > structure. The second resin component comprises an acrylic polymer having a quaternized amino group.

On the printing surface F1 of the printing medium 10, the first resin component may function as an aqueous ink receiving area for providing desired water solubility for the imaging ink, for example, an inkjet applied aqueous ink, The component can function as an adhesive zone to provide the desired adhesion of the media to the desired adherend. Therefore, image printing using aqueous inks is possible on the printing surface F1, and the printing surface also functions as an adhesive surface.

In addition, since the print medium 10 has the above-described configuration, it has good adhesion properties and good high-speed print characteristics on the print surface F1, and is suitable for printing on high-speed jet printing media . ≪ / RTI >

Further, in the print medium 10, the print image formed using the aqueous ink on the print surface F1 has excellent water resistance and bleed resistance. In particular, in the case of using a dye ink as an aqueous ink, it is difficult to prevent dye bleeding in a print image in a conventional print medium (for example, a print medium described in Reference D5) , Bleeding can be sufficiently inhibited even in printed images formed using aqueous dye inks. Therefore, the printing medium 10 can be suitably used as a printing medium for an aqueous dye ink.

Although not intended to be bound by these theories, it is believed to be the following. The fine ink receiving area of the first resin component and the fine adhesive area of the second resin component achieve this complicated structure due to the micro-phase separation at the printing surface (F1). Therefore, the water-based ink penetrates into the ink containing area at the impact point, but expansion (bleeding) due to penetration from the ink containing area of the impact point to the ink containing area other than the impact point is blocked by the adhesive area. Therefore, it is considered that bleeding of the water-based ink in printing can be prevented, and a clear image can be formed. Further, even after the water-based ink is printed, it is considered that the water resistance of the printed image is improved because the water-based ink is prevented from bleeding for a similar reason.

The second resin component comprises a quaternized amino group at the printing surface (F1). Therefore, when printed with an aqueous dye ink, fixation of the dye becomes very excellent at the interface of the ink receiving area and the adhesion area, and dye bleeding is suppressed. It is noted that in the case where the dye is an acid dye, it is believed that such anchoring is much more noticeable and the bleed is much more markedly inhibited. This is the reason why the printing medium 10 may be particularly suitable for use as a print medium for an acid dye ink.

Here, the term "micro-phase separation structure" means that the first resin component and the second resin component exhibit a microscopic phase-separated structure. For example, a case where at least one of the first resin component and the second resin component forms an independent phase on the printing surface F1 and the average diameter of the phase is 100 탆 or less can be referred to as a micro-phase separation structure. Note that the average diameter on the surface can be determined by summing and averaging any number of 10 to 100 diameters observed by surface optical microscopy and electron microscope photographs.

The micro-phase separation structure should preferably have an average diameter of the independent phase described above equal to or less than the dot diameter of the water-based ink provided on the printing surface F1. For example, in the case of printing such that the average diameter of ink dots in inkjet printing is 30 [mu] m, 20 [mu] m, or 10 [mu] m or less, the independent image described above is preferably 30 [mu] m, It should be a fine size smaller than the average diameter. Thereby making it possible to form a much sharper image.

As will be appreciated, the minimum value of the average diameter of the independent phases described above is not particularly limited, may be greater than 0.01 μm, and in some embodiments may even be greater than 0.1 μm.

Examples of micro-phase separation structures include island structures, cylinder structures, lamellar structures, and cocontinuum structures. Specifically, the first resin component having hydrophilicity is an island shape, and the second resin component is an island structure constituting the sea around the first resin component.

The first resin component is hydrophilic. This means that the first resin component has a property capable of absorbing the water-based ink. For example, when water is dripped onto the resin component surface to cover a large area and the resin component absorbs water droplets within a few seconds (for example, 5 seconds), the resin component may be said to be hydrophilic.

In an exemplary embodiment, the first resin component may include at least one of a polyalkylene oxide, a hydrophilic acrylic resin, a polyvinyl alcohol, a polyvinyl pyrrolidone, a hydrophilic polyurethane resin, and a hydrophilic ethylene vinyl alcohol.

Preferably, the first resin component contains a polyalkylene oxide. In this case, since the polyalkylene oxide is excellent in the water-soluble property of the water-based ink and has the adhesive property, the printing and adhesion properties of the printing surface F1 are much better. Polyethylene oxide, polypropylene oxide, ethylene oxide, and propylene oxide copolymer are given as polyalkylene oxide.

Within the first resin component, the polyalkylene oxide is preferably greater than 80 weight percent, and more preferably greater than 90 weight percent, of the total mass of the first resin component. In addition, the first resin component may be a polyalkylene oxide.

The second resin component is a thermally adhesive resin component and contains an acrylic polymer having at least a quaternized amino group.

The acrylic polymer may further comprise a phenoxy group. This further improves the adhesive properties of the printing surface and the water resistance of the printed image.

The acrylic polymer may be a polymer of a monomer component comprising an acrylic monomer having a quaternized amino group. Further, the monomer component may further include an acrylic monomer having a phenoxy group, alkyl (meth) acrylate, or (meth) acrylic acid.

For example, an acrylic monomer having a quaternized amino group and a polymer of a monomer component comprising alkyl (meth) acrylate and (meth) acrylic acid are given as one type of acrylic polymer, and the monomer component is an acrylic monomer having a phenoxy group .

Here, the ratio of the acrylic monomer having a quaternized amino group in the monomer component may be 3 to 13 mass%, or it may be 5 to 11 mass%. The proportion of the alkyl (meth) acrylate in the monomer component may be 20 to 90 mass%, preferably 25 to 70 mass%, and more preferably 30 to 60 mass%. In addition, the ratio of the (meth) acrylic acid in the monomer component may be 1 to 8 mass%. The ratio of the acrylic monomer having a phenoxy group in the monomer component may be from 0 to 70 mass%, preferably from 10 to 65 mass%, and more preferably from 20 to 60 mass%.

In this embodiment, the total amount of the acrylic monomer having an alkyl (meth) acrylate and a phenoxy group in the monomer component may be 60 to 94 mass%, preferably 70 to 90 mass%.

For example, a group represented by the following formula (1) is provided as a quaternized amino group:

[Chemical Formula 1]

Wherein R ¹ , R ² , and R ³ are independently an alkyl group or an aryl group and X ^- is an anion. R ¹ , R ² , and R ³ are preferably each an alkyl or phenyl group, more preferably an alkyl group, and still more preferably a C _{1 -2} alkyl group (an alkyl group having 1 or 2 carbon atoms ).

The monovalent anion represented by X < ^- > is not particularly limited, but examples thereof include halide ions (chloride ion, bromide ion, iodide ion). Of these, chloride ions are more preferable because of their easy availability.

N, N-dimethylaminoethyl (meth) acrylate quaternized with methyl chloride, N, N-dimethylaminopropyl (meth) acrylate quaternized with methyl chloride, N, N- Dimethylaminoethyl (meth) acrylamide and N, N-dimethylaminopropyl (meth) acrylamide quaternized with methyl chloride are suitable for use as an acrylic monomer having a quaternized amino group.

Phenoxyethyl (meth) acrylate is given as an acrylic monomer having a phenoxy group. As the alkyl (meth) acrylate, C _1-16 alkyl (meth) acrylate is preferable, and C _1-10 alkyl (meth) acrylate is more preferable. Here, "C _1-16 " and "C _1-10 " represent the number of carbon atoms of the alkyl group except for the (meth) acryloyl group.

The second resin component may contain a hydrophobic resin component as a thermally adhesive resin component other than the acrylic polymer. For example, the second resin component may contain a polyester, a hydrophobic polyurethane resin, a polyester urethane resin, and ethylene vinyl acetate. Note that hydrophobicity means that the hydrophobic property has a property of repelling water-based ink. For example, when water drops onto the resin surface, almost all of the water drops are repelled, it can be said to be a hydrophobic resin.

Preferably, within the second resin component, the acrylic polymer described above constitutes more than 50% by weight of the second resin component, and more preferably more than 60% by weight. In some cases, the second resin component may consist essentially of an acrylic polymer.

The content of the first resin component in the ink receiving layer 11 may be 20 to 70 mass% with respect to 100 mass% of the total weight of the first and second resin components, and may be 30 to 60 mass%. By this, the abundance ratio of the ink receiving area and the adhesion area in the micro-phase separation structure of the printing surface F1 becomes suitable, and a good balance between the high speed printing property of the printing surface F1 and the water resistance of the printing image can be achieved . At this time, a clear print image without bleeding can be obtained even at high-speed printing, for example, even exceeding 100 mm / sec.

In the printing surface F1, the ratio (S ₁ / S ₂ ) of the total area (S ₁ ) of the ink containing area of the first resin component to the total area of the ink containing area of the second resin component (S ₂ ) , For example from 0.2 to 4.0, which may be from 0.4 to 1.5. By providing the ink receiving area and the adhesive area at such an area ratio, printing properties, adhesive properties and water resistance are much better.

The ink receiving layer 11 can be set to, for example, 10 to 40 占 퐉 as well as 20 to 30 占 퐉. The ink receiving layer 11 made to have such a thickness has much better printing and adhesion properties of the printing surface F1. Although the reason for such an effect is not always clear, it is believed that the adhesion strength of the second resin component is effectively exhibited at a thickness of more than 15 [mu] m and a good bond strength can be ensured. When the thickness is less than 40 탆, a homogeneous micro-phase separation structure is easily formed.

The ink receiving layer 11 should have optical transparency. According to such an ink receiving layer 11, the image printed on the printing surface F1 can be seen from the surface other than the printing surface F1. In this case, it is preferable that the substrate 12 (to be mentioned below) also has optical transparency.

The ink receiving layer 11 contains a first micro-phase separation region that contains more of the first resin component than the second resin component, and a second micro-phase separation region that contains more of the second resin component than the first resin component, And may have a relatively convex second micro-phase separation region. In this way, by arranging the relatively large area of the second resin component (the second micro-phase separation area) around the area where the first resin component is relatively large (the first micro-phase separation area) And the high-speed printing characteristic is greatly improved.

It is noted that "the first resin component contains more of the first resin component than the second resin component" means that the area ratio of the surface composed of the first resin component occupying such a region is larger than the area ratio of the surface composed of the second resin component . In addition, "relatively convex" means that such region is at least higher than the adjacent first phase-separation region.

Preferably, there should be a plurality of first micro-phase separation regions, and preferably each of these should surround the second micro-phase separation region approximately in the shape of a ring. In other words, the ink receiving layer 11 should preferably have a structure in which the second micro-phase separation region surrounds the first micro-phase separation region, and this structural unit is repeatedly printed on the printing surface F1 as one unit .

In other words, in the printing surface F1, the ink receiving layer 11 should preferably have a non-uniform structure having convex portions that surround the concave portions and the concave portions in the shape of a ring, 1 < / RTI > resin component, and the convex portion forms a second micro-phase-separation region containing more of the second resin component than the first resin component.

In this way, the convex portion forming the second micro-phase separation region encloses the outer side of the crumb portion forming the first micro-phase separation region similar to the outer edge of the volcanic crater, And the printing characteristics are further improved.

In addition, the first micro-phase separation region contains more of the first resin component and absorption of the water-based ink is good. By forming the micro-phase separation region by the concave portion, it is considered that the water-based ink held by the concave portion is fixed to the ink receiving layer 11 due to the high absorbency of the first micro-phase separation region.

In addition, the second micro-phase separation region comprises more of the second resin component, and the first resin component is relatively less. It is believed that excellent adhesion properties and water resistance are realized because of the convexity of this type of second micro-phase-separation region coming into contact with the object by adhesion.

The shape of the first micro-phase separation region may be approximately circular, elliptical, or polygonal, but is typically circular. The diameter of the first micro-phase separation region may be, for example, 10 [mu] m to 500 [mu] m or 50 [mu] m to 300 [mu] m.

The second micro-phase separation region forms a relatively convex portion; The difference between the phase separation zone average height h ₂ adjacent to the first micro-Average height of the phase separation structure, h ₁ and the second micro (h ₂ - h ₁₎ typically may be 1 μm to 30 μm, 2 in some cases mu] m to 20 [mu] m.

The second micro-phase separation region preferably surrounds the first micro-phase separation region in the shape of a ring; Note that it is not necessary that the second micro-phase separation region be formed in a substantially circular shape around the first micro-phase separation region, but a complete circular shape.

The substrate 12 should have a surface capable of providing the ink receiving layer 11. It should be noted that, in the print medium 10, the substrate 12 is in the form of a film, but the substrate need not always be in the shape of a film used in the present invention.

paper; Synthetic paper; A resin film or a resin sheet made from a resin such as polyvinyl chloride resin, polyolefin resin, acrylic acid resin, polyester, and polyurethane resin can be used as the substrate 12. [ The substrate may be a single layer or a multilayer and should provide sufficient dimensional stability for the formation of the ink receptive layer thereon and subsequent handling and processing of the printing medium. Those skilled in the art will readily be able to select materials suitable for the substrate in view of the desired flexibility, tear strength, stretchability, elasticity, weight, and the like.

The substrate 12 preferably has optical transparency. The image printed on the printing surface F1 can be seen through the ink receiving layer 11 and the substrate 12 because both the substrate 12 and the ink receiving layer 11 have optical transparency.

Uses of a printing medium for an aqueous ink according to an embodiment of the present invention will be described below. Note that the use of the printing medium for an aqueous ink of the present invention is not limited to the following embodiments.

According to the printing medium 10, a clear image can be printed on the printing surface F1 using an aqueous ink, and the printing surface F1 also functions as an adhesive surface. Therefore, the print medium 10 can be easily adhered to the object without any special adhesive treatment.

For example, the print medium 10 is suitable for use as a film adhered to an IC card, a photo identification card, or the like. In this case, for example, first, the image to be displayed on the IC card is printed on the printing surface F1, and then the printed surface F1 and the IC card are opposed to each other and heat laminated.

In such an application, since the printing property, the adhesive property, and the water resistance of the printing medium 10 are excellent, an IC card having a clear image can be rapidly produced. In addition, the manufactured IC card is also excellent in water resistance.

Further, for example, when the print medium 10 is peeled off after being applied on the IC card, the fine ink receiving area is destroyed and the print medium 10 is peeled off due to the micro-phase separation structure in the print surface F1 of the print medium 10 The contents become unreadable. Therefore, according to the print medium 10, the IC card can be prevented from being reused for an unjust purpose.

In addition, the print medium 10 can be used as a decorative film by adhering to an object having a non-uniform or curved surface. In such a case, preferably a heat-stretchable substrate should be used for the substrate 12 of the print medium 10. For example, such print media 10 may be adhered to a target having a non-uniform or curved surface while heating the print media 10 with a dryer or the like.

The print media 10 may have a support layer on the other surface of the substrate 12 to support the print media 10 and improve handling characteristics, depending on the application. Such a situation is shown in Fig.

The printing medium 20 shown in Fig. 2 comprises a substrate 22, an ink receiving layer 21 provided on one side of the substrate 22 and having a surface F2 not facing the substrate 22, (23) provided on the other side of the substrate (22). Note that the base material 22 and the ink receiving layer 21 in the printing medium 20 are equivalent to the base material 12 and the ink receiving layer 11 in the printing medium 10. [

The print medium 20 is excellent in handling characteristics because the substrate 22 and the ink receiving layer 21 are supported by the support layer 23. [ According to the print medium 20, for example, the support layer 23 can be peeled off after the aqueous ink print image is formed, and only the substrate 22 and the ink receiving layer 21 can be adhered to the object.

The printing medium 10 may be provided on the other surface of the substrate 12 in order to prevent dust and contaminants from adhering to the outermost surface after the printing medium 10 is adhered to the object, Lt; / RTI > Such a situation is shown in Fig.

The printing medium 30 shown in Fig. 3 comprises a base material 32, an ink receiving layer 31 provided on one side of the base material 32, having a surface F3 not facing the base material 22 as a printing surface, And a contamination-preventing layer 33 provided on the other side of the substrate 32. The anti- Note that the base material 32 and the ink receiving layer 21 in the printing medium 30 are equivalent to the base material 12 and the ink receiving layer 11 in the printing medium 10. [ For example, the anti-contamination layer 33 may be formed from a resin composition containing a fluororesin.

The print medium 30 may also have a support layer 34 that supports the substrate 32, the ink receiving layer 31, and the anti-contamination layer 33. According to the print medium 30, the support layer 34 can be peeled off, for example, after the aqueous ink print image is formed, and only the substrate 32, the ink receiving layer 31 and the pollution- Can be adhered to the object.

Next, an example of a printing method for a water-based ink for a water-based ink according to this embodiment will be described.

The method of printing the aqueous ink on the printing surface F1 of the printing medium 10 is not particularly limited; Inkjet printing is preferable. When inkjet printing is performed, a printed image can be formed quickly, and the IC card described above can be manufactured much more quickly.

The printing speed of inkjet printing may be greater than 25 mm / sec, greater than 50 mm / sec, or even greater than 100 mm / sec. An advantage of the present invention is that a sharp image can be formed on the medium of the present invention without occurrence of ink bleeding even at such a printing speed because the printing medium 10 is excellent in high speed printing property on the printing surface F1 .

The water-based ink used for printing is not particularly limited, but may be an aqueous dye ink, or it may be an acid dye ink. According to the printing medium 10, when the dye ink is used, the bleeding can be sufficiently suppressed.

Next, a method for producing a printing medium for an aqueous ink according to this embodiment will be described. Note that the printing medium for an aqueous ink of the present invention is not limited to a printing medium produced by the following production method.

This manufacturing method includes the steps of applying a solution containing a first resin component, a second resin component and a solvent to a substrate to form a coating on the substrate, and removing the solvent from the coating to form a first resin component and a second resin component Lt; RTI ID = 0.0 > micro-phase < / RTI >

According to this manufacturing method, the printing surface is a printing medium which functions as an adhesive surface and has both good adhesion properties and printing properties, and even when printed with water-based dye ink, the printing medium for water- (See the print medium 10 as a concrete example) can be easily obtained.

In the coating liquid of the first step, the first resin component and the second resin component may be dissolved in a solvent and may be dispersed as resin component fine particles in a solvent to form a suspension (the term "solvent" Is used to refer to such an embodiment where the subject fluid is more specifically referred to as a liquid medium, a liquid fraction, etc.).

The solvent may be such that the first resin component and the second resin component are uniformly dissolved or dispersed in the coating liquid, and an organic solvent may suitably be used. Aromatic types such as benzene, toluene, and xylene; Ketones such as acetone and methyl ethyl ketone; Esters such as ethyl acetate, and butyl acetate; Alcohols such as methanol and ethanol are given as examples of organic solvents. These may be formulated together or may be used individually. Further, in this production method, water or a mixture of water and alcohol can be used as a solvent.

The coating liquid can be heated if necessary. For example, the coating liquid may be heated to 30 to 60 DEG C to dissolve the first resin component and the second resin component.

In one situation of this manufacturing method, the coating liquid may be a suspension containing the first resin component and the second resin component. The ink receiving layer formed using such a coating liquid has a characteristic non-uniform shape having a concave portion and a peak-shaped convex portion surrounding the concave portion on the printing surface. When the ink receiving layer is formed into a convex or concave shape, And bleed characteristics are further improved.

The resin fine particles are prepared by using the difference in solubility between the first resin component and the second resin component so that the first resin component and / or the second resin component are partially separated when the first solution and the second solution are mixed together .

For example, when the first resin component is polyalkylene oxide, the first resin component may be dissolved in a mixed solvent of methyl ethyl ketone / toluene / methanol (weight ratio 2/1/1) at 40 ° C. Further, the acrylic polymer as the second resin component can be dissolved in a mixed solvent of acetone / methanol at room temperature (for example, 20 占 폚).

For example, when the first resin component is dissolved in a mixed solvent of methyl ethyl ketone / toluene / methanol (2/1/1) at 40 ° C and the second resin component is dissolved in a mixed solvent of acetone / methanol The second solution at 20 占 폚 is mixed at room temperature (20 占 폚) to obtain a coating liquid containing the resin fine particles described above.

When the first resin component is a polyalkylene oxide, the first solution should preferably contain methyl ethyl ketone, toluene and methanol as a solvent, which should preferably be heated to 35 to 60 占 폚. On the other hand, the second solution should preferably contain methyl ethyl ketone or acetone and methanol as solvent, and the temperature should preferably be 15 to 30 占 폚.

The concentration of the first resin component in the first solution is preferably 10 to 20 mass%, and more preferably 14 to 16 mass%. The concentration of the second resin component in the second solution is preferably 30 to 40% by mass, and more preferably 33 to 38% by mass.

The coating can be applied by applying a coating liquid on one side of the substrate. The application method of the coating liquid is not particularly limited, but well known methods can be used, for example, a knife coating method, a spin coating method, a roll coating method, a silk screen coating method and a gravure coating method.

Preferably, the coating should be formed such that the thickness of the ink receiving layer formed after the second step is 10 to 40 占 퐉. When the coating is formed to have such a thickness, the printing surface of the resulting ink receiving layer becomes much more excellent in printing properties and adhesion properties thereof.

In a second step the solvent is removed from the coating. A method of volatilizing and removing the solvent by heating and an air-drying method are given as a method of removing the organic solvent. In the second step, it is not absolutely necessary to completely remove the solvent of the coating, and the ink receiving layer may contain some solvent.

As will be understood, the printing medium of the present invention can be formed in the form of a sheet or a roll.

Although a preferred embodiment of the present invention has been described above, as described above; The present invention is not limited to the embodiments described above. For example, in the present invention, the print image formed by the aqueous ink on the print surface F1 of the print medium 10 may be a decorative film. The present invention also provides a decorative item (for example, a decorative sheet) on which a print medium 10 on which a print image is formed by aqueous ink on a print surface F1 is adhered to an object (for example, An IC card having a print image).

Example

Hereinafter, the present invention will be described in more detail with reference to the following examples.

Acrylic polymer B1: methyl acrylate, 33% by weight (indicated as "MA" in some cases hereinafter), phenoxyethyl acrylate 55% by mass (hereinafter, in some cases, as represented by "PhEA"), N-dimethylaminoethyl acrylate quaternized with methyl chloride (hereinafter referred to as "DMAEA-Q" as occasion demands) and 2 mass% acrylic acid (hereinafter referred to as "Quot; AA ") was uniformly dissolved in a mixed solvent of 148.58 mass% of acetone and 34.49 mass% of methanol, and the solution was reacted. Note that an aqueous solution having a solid content of 79% by mass was used as DMAEA-Q. This reaction solution was poured into a pressure resistant heat-resistant glass container, 0.1% by mass of azobisisobutyronitrile was added as an initiator, and then deoxidized by passing nitrogen through the reaction solution while stirring for 10 minutes. Then, the copolymerization reaction was carried out by heating at 50 DEG C for 20 hours to obtain a 35 mass% solution of acrylic polymer B1.

Acrylic polymer B2: 43% by mass of methyl acrylate, 45% by mass of phenoxyethyl acrylate, 10% by mass of N, N-dimethylaminoethyl acrylate quaternized with methyl chloride, and 2% Was homogeneously dissolved in a mixed solvent of 148.58% by mass of acetone and 34.49% by mass of methanol, and the solution was reacted. Note that an aqueous solution having a solid content of 79% by mass was used as DMAEA-Q. This reaction solution was poured into a pressure resistant heat-resistant glass container, 0.1% by mass of azobisisobutyronitrile was added as an initiator, and then deoxidized by passing nitrogen through the reaction solution while stirring for 10 minutes. Then, the copolymerization reaction was carried out by heating at 50 DEG C for 20 hours to obtain a 35 mass% solution of acrylic polymer B2.

Acrylic polymer B3: 23% by mass of methyl acrylate, 65% by mass of phenoxyethyl acrylate, 10% by mass of N, N-dimethylaminoethyl acrylate quaternized with methyl chloride, and 2% Was homogeneously dissolved in a mixed solvent of 148.58% by mass of acetone and 34.49% by mass of methanol, and the solution was reacted. Note that an aqueous solution having a solid content of 79% by mass was used as DMAEA-Q. This reaction solution was poured into a pressure resistant heat-resistant glass container, 0.1% by mass of azobisisobutyronitrile was added as an initiator, and then deoxidized by passing nitrogen through the reaction solution while stirring for 10 minutes. Then, the copolymerization reaction was carried out by heating at 50 DEG C for 20 hours to obtain a 35 mass% solution of acrylic polymer B3.

Acrylic polymer B4: methyl methacrylate of 73 mass%, phenoxyethyl acrylate of 15 mass%, N, N-dimethylaminoethyl acrylate quaternized with methyl chloride, 10 mass% of acrylic acid and 2 mass% Was homogeneously dissolved in a mixed solvent of 148.58% by mass of acetone and 34.49% by mass of methanol, and the solution was reacted. Note that an aqueous solution having a solid content of 79% by mass was used as DMAEA-Q. This reaction solution was poured into a pressure resistant heat-resistant glass container, 0.1% by mass of azobisisobutyronitrile was added as an initiator, and then deoxidized by passing nitrogen through the reaction solution while stirring for 10 minutes. Then, the copolymerization reaction was carried out by heating at 50 DEG C for 20 hours to obtain a 35 mass% solution of acrylic polymer B4.

Acrylic polymer B5: 33% by mass of 2-ethylhexyl acrylate (hereinafter sometimes referred to as "2EHA"), 55% by mass of phenoxyethyl acrylate, 10% by mass of N , N-dimethylaminoethyl acrylate, and 2 mass% acrylic acid were homogeneously dissolved in a mixed solvent of 148.58 mass% of acetone and 34.49 mass% of methanol, and the solution was reacted. Note that an aqueous solution having a solid content of 79% by mass was used as DMAEA-Q. This reaction solution was poured into a pressure resistant heat-resistant glass container, 0.1% by mass of azobisisobutyronitrile was added as an initiator, and then deoxidized by passing nitrogen through the reaction solution while stirring for 10 minutes. Then, the copolymerization reaction was carried out by heating at 50 DEG C for 20 hours to obtain a 35 mass% solution of acrylic polymer B5.

Acrylic polymer B6: 29% by weight of methyl acrylate, 55% by weight of phenoxyethyl acrylate, 10% by weight of N, N-dimethylaminoethyl acrylate quaternized with methyl chloride, and 2% , 148.58% by mass of acetone and 34.49% by mass of methanol, and the solution was reacted. Note that an aqueous solution having a solid content of 79% by mass was used as DMAEA-Q. This reaction solution was poured into a pressure resistant heat-resistant glass container, 0.1% by mass of azobisisobutyronitrile was added as an initiator, and then deoxidized by passing nitrogen through the reaction solution while stirring for 10 minutes. The copolymerization reaction was then carried out by heating at 50 DEG C for 20 hours to obtain a 35 mass% solution of acrylic polymer B6.

Acrylic polymer B7: 88% by weight of methyl acrylate, 10% by weight of N, N-dimethylaminoethyl acrylate quaternized with methyl chloride, and 2% by weight of acrylic acid, 148.58% by weight of acetone and 34.49% % Methanol, and the solution was allowed to react. Note that an aqueous solution having a solid content of 79% by mass was used as DMAEA-Q. This reaction solution was poured into a pressure resistant heat-resistant glass container, 0.1% by mass of azobisisobutyronitrile was added as an initiator, and then deoxidized by passing nitrogen through the reaction solution while stirring for 10 minutes. Then, the copolymerization reaction was carried out by heating at 50 DEG C for 20 hours to obtain a 35 mass% solution of acrylic polymer B7.

Acrylic polymer B8: 58% by mass of methyl acrylate, 35% by mass of phenoxyethyl acrylate, 5% by mass of N, N-dimethylaminoethyl acrylate quaternized with methyl chloride, and 2% Was homogeneously dissolved in a mixed solvent of 148.58% by mass of acetone and 34.49% by mass of methanol, and the solution was reacted. This reaction solution was poured into a pressure resistant heat-resistant glass container, 0.1% by mass of azobisisobutyronitrile was added as an initiator, and then deoxidized by passing nitrogen through the reaction solution while stirring for 10 minutes. Then, the copolymerization reaction was carried out by heating at 50 DEG C for 20 hours to obtain a 35 mass% solution of acrylic polymer B8.

Acrylic polymer B9: 33% by mass of methyl acrylate, 55% by mass of phenoxyethyl acrylate, 10% by mass of N, N-dimethylaminoethyl acrylate (tertiary amine, sometimes referred to as "DMAEA" And 2% by mass of acrylic acid were homogeneously dissolved in a mixed solvent of 148.58% by mass of acetone and 34.49% by mass of methanol, and the solution was reacted. This reaction solution was poured into a pressure resistant heat-resistant glass container, 0.1% by mass of azobisisobutyronitrile was added as an initiator, and then deoxidized by passing nitrogen through the reaction solution while stirring for 10 minutes. Then, the copolymerization reaction was carried out by heating at 50 DEG C for 20 hours to obtain a 35 mass% solution of acrylic polymer B9.

Acrylic Polymer B10: 43% by mass of methyl acrylate, 55% by mass of phenoxyethyl acrylate and 2% by mass of acrylic acid were homogeneously dissolved in a mixed solvent of 148.58% by mass of acetone and 34.49% by mass of methanol, Lt; / RTI > This reaction solution was poured into a pressure resistant heat-resistant glass container, 0.1% by mass of azobisisobutyronitrile was added as an initiator, and then deoxidized by passing nitrogen through the reaction solution while stirring for 10 minutes. Then, the copolymerization reaction was carried out by heating at 50 DEG C for 20 hours to obtain a 35 mass% solution of acrylic polymer B10.

Acrylic polymer B11: 28% by mass of methyl acrylate, 55% by mass of phenoxyethyl acrylate, 15% by mass of N, N-dimethylaminoethyl acrylate quaternized with methyl chloride, and 2% Was homogeneously dissolved in a mixed solvent of 148.58% by mass of acetone and 34.49% by mass of methanol, and the solution was reacted. This reaction solution was poured into a pressure resistant heat-resistant glass container, 0.1% by mass of azobisisobutyronitrile was added as an initiator, and then deoxidized by passing nitrogen through the reaction solution while stirring for 10 minutes. Then, the copolymerization reaction was carried out by heating at 50 DEG C for 20 hours to obtain a 35 mass% solution of acrylic polymer B5.

Acrylic polymer B12: 25% by mass of methyl acrylate, 55% by mass of phenoxyethyl acrylate, 10% by mass of N, N-dimethylaminoethyl acrylate quaternized with methyl chloride, and 10% Was homogeneously dissolved in a mixed solvent of 148.58% by mass of acetone and 34.49% by mass of methanol, and the solution was reacted. This reaction solution was poured into a pressure resistant heat-resistant glass container, 0.1% by mass of azobisisobutyronitrile was added as an initiator, and then deoxidized by passing nitrogen through the reaction solution while stirring for 10 minutes. Then, the copolymerization reaction was carried out by heating at 50 DEG C for 20 hours to obtain a 35 mass% solution of acrylic polymer B5.

The ratio (mass ratio) of the monomer units constituting the acrylic polymer B1 to the acrylic polymer B10 is shown in Table 1 below.

[Table 1]

Example 1

AQUA COKE (a product of Sumitomo Seika Chemicals Co., Ltd., polyalkylene oxide, solid content 100% by mass) was dissolved in methyl ethyl ketone / toluene / Methanol (mass ratio 2/1/1) to prepare Solution A1 having a solid content concentration of 15 mass% as a first resin component. Further, a solution having an acrylic polymer B1 of 35 mass% (hereinafter referred to as solution B1) was used as the second resin component.

The solution A1 and the solution B1 at 40 DEG C were mixed so that the mass ratio of the first resin component and the second resin component was 60/40 to prepare a mixture C1.

Solution C1 was applied onto a polyethylene terephthalate film (PET film) having a thickness of 50 μm using a knife coating method, and solution C1 was dried in an oven set at 80 ° C for 10 minutes to form an ink receiving layer on the PET film Thereby obtaining the print medium 1. At that time, the thickness of the ink receiving layer formed after drying was adjusted to be 25 mu m. Note that the thickness of the ink receiving layer is adjusted by adjusting the gap between the PET film surface and the knife surface.

When the obtained print medium 1 was observed with a surface optical microscope, the ink receiving layer of the print medium 1 had a micro-phase separation structure almost uniform at the print surface. The results are shown in FIG.

Further, the print surface of the ink receiving layer of the obtained print medium 1 was measured using a non-contact surface roughness-measuring instrument (from Zaygo), and the surface roughness of the print surface was measured. The results are shown in Fig. From the results shown in Fig. 5, a unique non-uniform structure arrangement was confirmed, wherein a first micro-phase separation region of approximately circular shape and a second micro-phase separation region of convex shape surrounding the outer peripheral portion thereof in the shape of a ring Structural units were present. In other words, it was confirmed that the second micro-phase separation structure rises to the shape of the peak, and a unique heterogeneous structure is formed so as to surround the first micro-phase separation region of the approximately circular shape.

The micro-phase separation structure of the printing surface formed an island structure, and the average diameter of the islands was about 5 μm. In addition, the first micro the shape of substantially circle-diameter of the phase separation zone was approximately 50 to 300 μm, the first micro-difference between the mean height of the phase separation zone h ₂ (- average height of the phase separation structure, h ₁ and the second micro- h ₂ - h ₁ ) was approximately 25 to 30 μm.

Further, from the surface observation using the atomic force microscope (AFM), the first resin component is larger in the first micro-phase separation region than the second resin component, and the second resin component is larger in the second micro-phase separation region than the first resin component Respectively. Specifically, such an abundance ratio was confirmed from the crystal orientation state represented by the first resin component.

Further, printing characteristics, water resistance, room temperature bonding strength, and high temperature bonding strength were evaluated for printing medium 1 according to the following evaluation method. The evaluation results are shown in Table 2.

Example 2

Print medium 2 was also obtained in the same manner as in Example 1 except that a solution having 35 mass% of acrylic polymer B2 instead of solution B1 (hereinafter referred to as solution B2) was used as the second resin component .

When the obtained print medium 2 was observed with a surface optical microscope, the ink receiving layer of the print medium 2 had a micro-phase separation structure almost uniform at the print surface.

In addition, the print surface of the ink receiving layer of the obtained print medium 2 was measured using a non-contact surface roughness-measuring instrument (from Jiji) to measure the surface roughness of the print surface. From the results of the measurement using the non-contact surface roughness measuring device, it was confirmed that the outer surface of the first micro-phase separation region and the outer periphery of the first micro- It was confirmed that a plurality of arranged uneven heterogeneous structures having a convex second micro-phase separation region surrounded by the ring shape were formed.

In addition, printing characteristics, water resistance, room temperature bonding strength, and high-temperature bonding strength of the printing medium 2 were evaluated according to the following evaluation methods. The evaluation results are shown in Table 2.

Example 3

Print medium 3 was also obtained similarly to Example 1, except that a solution having 35 mass% of acrylic polymer B3 instead of solution B1 (hereinafter referred to as solution B3) was used as the second resin component .

When the obtained print medium 3 was observed with a surface optical microscope, the ink receiving layer of the print medium 3 had a micro-phase separation structure almost uniform at the print surface.

In addition, the print surface of the ink receiving layer of the obtained print medium 3 was measured using a non-contact surface roughness-measuring instrument (from Jiji) to measure the surface roughness of the print surface. From the results of the measurement using the non-contact surface roughness measuring device, similarly to Example 1, in the printing surface of the ink receiving layer of the printing medium 3, the first micro-phase separation region and the outer peripheral portion of the first micro- It was confirmed that a plurality of arranged uneven heterogeneous structures having a convex second micro-phase separation region surrounded by the ring shape were formed.

Further, printing characteristics, water resistance, room temperature bonding strength, and high temperature bonding strength of the printing medium 3 were evaluated according to the following evaluation methods. The evaluation results are shown in Table 2.

Example 4

Further, print medium 4 was obtained in the same manner as in Example 1, except that a solution having 35 mass% of acrylic polymer B4 (hereinafter referred to as Solution B4) was used as the second resin component instead of Solution B1 .

When the obtained print medium 4 was observed with a surface optical microscope, the ink receiving layer of the print medium 4 had a micro-phase separation structure almost uniform at the print surface.

In addition, the print surface of the ink receiving layer of the obtained print medium 4 was measured using a non-contact surface roughness-measuring instrument (manufactured by Zeon), and the surface roughness of the print surface was measured. From the results of the measurement using the non-contact surface roughness measuring device, it was confirmed that the outer surface of the first micro-phase separation region and the outer periphery of the first micro- It was confirmed that a plurality of arranged uneven heterogeneous structures having a convex second micro-phase separation region surrounded by the ring shape were formed.

Further, printing characteristics, water resistance, room temperature bonding strength, and high-temperature bonding strength of the printing medium 4 were evaluated according to the following evaluation methods. The evaluation results are shown in Table 2.

Example 5

Print medium 5 was obtained similarly to that of Example 1, except that a solution having 35 mass% of acrylic polymer B5 (hereinafter referred to as Solution B5) was used instead of Solution B1 as the second resin component .

When the obtained print medium 5 was observed with a surface optical microscope, the ink receiving layer of the print medium 5 had a micro-phase separation structure which was almost uniform at the print surface.

In addition, the print surface of the ink receiving layer of the obtained print medium 5 was measured using a non-contact surface roughness-measuring instrument (from Jiji) to measure the surface roughness of the print surface. From the results of the measurement using the non-contact surface roughness measurement device, it was confirmed that the outer surface of the first micro-phase separation region and the outer periphery of the first micro- It was confirmed that a plurality of arranged uneven heterogeneous structures having a convex second micro-phase separation region surrounded by the ring shape were formed.

In addition, printing characteristics, water resistance, room temperature bonding strength, and high-temperature bonding strength of the printing medium 5 were evaluated according to the following evaluation methods. The evaluation results are shown in Table 2.

Example 6

Except that the mixture C2 prepared by mixing the solution A1 and the solution B1 at 40 DEG C such that the mass ratio of the first resin component and the second resin component was 50/50 was used instead of the solution C1. The print medium 6 was obtained.

When the obtained print medium 6 was observed with a surface optical microscope, the ink receiving layer of the print medium 6 had an almost uniform micro-phase separation structure at the print surface.

In addition, the print surface of the ink receiving layer of the obtained print medium 6 was measured using a non-contact surface roughness-measuring instrument (from Jiji) to measure the surface roughness of the print surface. From the results of the measurement using the non-contact surface roughness measurement device, it was confirmed that the print surface of the ink receiving layer of the print medium 6 had the first micro-phase separation region and the outer periphery of the first micro- It was confirmed that a plurality of arranged uneven heterogeneous structures having a convex second micro-phase separation region surrounded by the ring shape were formed.

In addition, printing characteristics, water resistance, room temperature bonding strength, and high temperature bonding strength of the printing medium 6 were evaluated according to the following evaluation methods. The evaluation results are shown in Table 2.

Example 7

Print medium 7 was obtained similarly to Example 1, except that a solution having 35 mass% of acrylic polymer B6 instead of solution B1 (hereinafter referred to as solution B6) was used as the second resin component .

When the obtained print medium 7 was observed with a surface optical microscope, the ink receiving layer of the print medium 7 had a micro-phase separation structure almost uniform at the print surface.

In addition, the print surface of the ink receiving layer of the obtained print medium 7 was measured using a non-contact surface roughness-measuring instrument (manufactured by Zeon), and the surface roughness of the print surface was measured. From the results of the measurement using the non-contact surface roughness measurement device, it was confirmed that the outer surface of the first micro-phase separation region and the outer periphery of the first micro- It was confirmed that a plurality of arranged uneven heterogeneous structures having a convex second micro-phase separation region surrounded by the ring shape were formed.

In addition, printing characteristics, water resistance, room temperature bonding strength, and high temperature bonding strength of the printing medium 7 were evaluated according to the following evaluation methods. The evaluation results are shown in Table 2.

Example 8

(Mass ratio 2/1/1) at 40 占 폚 in a mixed solvent of methyl ethyl ketone / toluene / methanol (manufactured by Sumitomo Seika Chemical Co., Ltd., polyalkylene oxide, solid content 100 mass% To prepare Solution A2 having a solid content concentration of 15 mass% as a first resin component. Print medium 8 was obtained similarly to Example 1, except that solution A2 was used instead of solution A1.

When the obtained print medium 8 was observed with a surface optical microscope, the ink receiving layer of the print medium 8 had a micro-phase separation structure almost uniform at the print surface.

In addition, the print surface of the ink receiving layer of the obtained print medium 8 was measured using a non-contact surface roughness-measuring instrument (manufactured by Zeon), and the surface roughness of the print surface was measured. As a result of the measurement using the non-contact surface roughness measuring device, the unique non-uniform structure observed in Example 1 was not observed on the printing surface of the ink receiving layer of the printing medium 8, and the large acid shaped cells formed the surface structure.

In addition, printing properties, water resistance, room temperature bonding strength, and high-temperature bonding strength of the printing medium 8 were evaluated according to the following evaluation methods. The evaluation results are shown in Table 2.

Example 9

Solution A2 was prepared analogously to Example 8. Subsequently, the solution A2 and the solution B1 at 40 占 폚 were mixed so that the mass ratio of the first resin component and the second resin component was 30/70 to prepare a mixture C3.

Print medium 9 was obtained similarly to Example 1, except that the mixture C3 was used instead of the mixture C1.

When the obtained printing medium 9 was observed with a surface optical microscope, the ink receiving layer of the printing medium 9 had a micro-phase separation structure that was almost uniform at the printing surface.

In addition, the print surface of the ink receiving layer of the obtained print medium 9 was measured using a non-contact surface roughness-measuring instrument (manufactured by Zeon), and the surface roughness of the print surface was measured. As a result of the measurement using the non-contact surface roughness measuring device, the unique non-uniform structure observed in Example 1 was not observed on the printing surface of the ink receiving layer of the printing medium 8, and the large acid shaped cells formed the surface structure.

The printing characteristics, water resistance, room temperature bonding strength, and high temperature bonding strength of the printing medium 9 were evaluated according to the following evaluation methods. The evaluation results are shown in Table 2.

Example 10

Solution A2 was prepared analogously to Example 8. Further, a 35 mass% solution of acrylic polymer B7 (hereinafter referred to as solution B7) was used as the second resin component. Subsequently, the solution A2 and the solution B7 at 40 占 폚 were mixed so that the mass ratio of the first resin component and the second resin component was 40/60 to prepare a mixture C4.

Print medium 10 was obtained similarly to Example 1, except that the mixture C4 was used instead of the mixture C1.

When the obtained print medium 10 was observed with a surface optical microscope, the ink receiving layer of the printing medium 10 had a micro-phase separation structure which was almost uniform at the printing surface.

In addition, the print surface of the ink receiving layer of the obtained print medium 10 was measured using a non-contact surface roughness-measuring instrument (from Jiji) to measure the surface roughness of the print surface. As a result of the measurement using the non-contact surface roughness measuring instrument, the unique non-uniform structure observed in Example 1 was not observed on the printing surface of the ink receiving layer of the printing medium 9, and the large acid shaped cells formed the surface structure.

Example 11

Further, a print medium 11 was obtained in the same manner as in Example 1, except that a solution having 35 mass% of acrylic polymer B8 (hereinafter referred to as Solution B8) was used instead of Solution B1 as a second resin component .

When the obtained print medium 11 was observed with a surface optical microscope, the ink receiving layer of the print medium 11 had a micro-phase separation structure almost uniform at the print surface.

In addition, the print surface of the ink receiving layer of the obtained print medium 11 was measured using a non-contact surface roughness-measuring instrument (from Jiji) to measure the surface roughness of the print surface. From the results of the measurement using the non-contact surface roughness measurement device, similarly to Example 1, the first micro-phase separation region and the outer periphery of the first micro-phase separation region were roughly It was confirmed that a plurality of arranged uneven heterogeneous structures having a convex second micro-phase separation region surrounded by the ring shape were formed.

The printing characteristics, water resistance, room temperature bonding strength, and high temperature bonding strength of the printing medium 9 were evaluated according to the following evaluation methods. The evaluation results are shown in Table 2.

Comparative Example C1

Solution A2 was prepared analogously to Example 8. Subsequently, the solution A2 and a 35 mass% solution of the acrylic polymer B9 (hereinafter referred to as solution B9) were mixed so that the mass ratio of the first resin component and the second resin component was 40/60 to prepare the mixture D1.

A print medium 21 was obtained similarly to Example 1, except that the mixture D1 was used instead of the mixture C1.

Further, printing characteristics, water resistance, room temperature bonding strength, and high temperature bonding strength were evaluated for the printing medium 21 according to the following evaluation method. The evaluation results are shown in Table 2.

Note that when viewed with a surface optical microscope, print medium 21 was found to have a nearly uniform micro-phase separation structure at the print surface. However, from the measurement results using the non-contact surface roughness measuring device (from Zeon), the unique heterogeneous structure observed in Example 1 was not observed on the printing surface, and a large acid-like cell formed the surface structure. The observation results of the surface optical microscope are shown in Fig. 6, and the measurement results of the non-contact surface roughness measuring instrument are shown in Fig.

Comparative Example C2

Solution A1 was prepared similarly to that of Example 1. Subsequently, the solution A1 and a 35 mass% solution of the acrylic polymer B10 (hereinafter referred to as solution B10) were mixed so that the mass ratio of the first resin component and the second resin component was 40/60 to prepare a mixture D2.

Print medium 22 was obtained similarly to Example 1, except that the mixture D2 was used instead of the mixture C1.

In addition, printing characteristics, water resistance, room temperature bonding strength, and high-temperature bonding strength of the printing medium 22 were evaluated according to the following evaluation methods. The evaluation results are shown in Table 2.

Note that when viewed with a surface optical microscope, print medium 22 was found to have a nearly uniform micro-phase separation structure at the print surface. However, from the measurement results using the non-contact surface roughness measuring instrument (from Jiji), the unique nonuniform structure observed in Example 1 was not observed on the printed surface.

Comparative Example C3

(Manufactured by Sumitomo Seika Chemical Co., Ltd., solids content of 100% by mass) of 40% by mass and a hydrophobic polyester Byron (registered trademark) of 40% by mass as a hydrophobic resin having heat- ) 670 (manufactured by Toyobo Co., Ltd., polyester) and 20% by mass of polyurethane resin Vyron 占 UR-3200 (manufactured by Toyobo Co., Ltd., polyester Urethane resin, glass transition temperature: -3 캜, solid content 30% by mass) was sufficiently stirred and dispersed in a mixed solvent of methyl ethyl ketone / toluene (mass ratio 1/1) at 60 캜.

Solution D3 was cast on a polyethylene terephthalate film (PET film) having a thickness of 50 占 퐉 using a knife coating method, and solution D3 was dried in an oven set at 80 占 폚 for 10 minutes to form an ink receiving layer on the PET film Whereby a print medium 23 was obtained. At that time, the thickness of the ink receiving layer formed after drying was adjusted to be 25 mu m.

Note that when viewed with a surface optical microscope, print media 23 was found to have a nearly uniform micro-phase separation structure at the print surface. However, from the measurement results using the non-contact surface roughness measuring instrument (from Jiji), the unique nonuniform structure observed in Example 1 was not observed on the printed surface.

Further, printing characteristics, water resistance, room temperature bonding strength, and high temperature bonding strength were evaluated for the printing medium 23 according to the following evaluation method. The evaluation results are shown in Table 2.

Test Methods

Evaluation of printing properties: Using a 6-color aqueous dye ink printing, at a printing speed of 25 mm / sec or 100 mm / sec, with a Canon (R) inkjet printer p-640L, And printed characters and letters. The printed image was visually evaluated in five grades described below. "D" indicates that the printed image is the most vivid, and the sharpness of the printed image is indicated by "C", "B", and "A" AA ". The results obtained at a printing speed of 25 mm / sec were evaluated as "printing characteristics ", and the results obtained at a printing speed of 100 mm / sec were evaluated as" high speed printing characteristics ".

Evaluation of the bleeding characteristics: An image was printed and evaluated on the ink receiving layer of the printing medium similarly to the evaluation of printing characteristics. The print medium and the vinyl chloride resin card were then placed so that the printing surface of the print medium and one side of the card were facing each other and then heat laminated using a roll type thermal laminator (120 ° C for 1 second). After the sample was allowed to stand at 80 캜 for a period of 7 days, the printed image was visually observed for any blurring. And evaluated by the five grades described below.

AA: No change at all.

A: There is almost no change compared to the control group.

B: Significant changes compared to the control group.

C: There is a significant smear.

D: A very distinct and prominent smear over the entire surface.

Evaluation of the room temperature bonding strength: An image was printed and evaluated on the ink receiving layer of the printing medium similarly to the printing property evaluation. The print medium and the vinyl chloride resin card were then placed so that the printing surface of the print medium and one side of the card were facing each other and then heat laminated using a roll type thermal laminator (120 ° C for 1 second).

After the obtained measurement sample was allowed to stand at 23 占 폚 for 24 hours, a 180 占 peel strength (N / 25 mm) was measured at 23 占 폚 using a tensile tester. The measurement conditions were set at a tensile rate of 200 mm / min. The measurement results were rated "A" for 15 N / 25 mm or more, "B" for 15 to 10 N / 25 mm, and "C" for less than 10 N / 25 mm.

Evaluation of high-temperature bonding strength: A measurement sample was obtained in a similar manner to the evaluation of the room-temperature bonding strength. After the obtained measurement sample was allowed to stand at 23 占 폚 for 24 hours, a 180 占 peel strength (N / 25 mm) was measured at 80 占 폚 using a tensile tester. The measurement conditions were set at a tensile rate of 200 mm / min. The measurement results were rated "A" for 15 N / 25 mm or more, "B" for 15 to 10 N / 25 mm, and "C" for less than 10 N / 25 mm.

Evaluation of water resistance: A measurement sample was obtained in a similar manner to the evaluation of the bonding strength at room temperature. After the measurement sample was allowed to stand in water at room temperature (25 캜) for 24 hours, the appearance change was visually confirmed. In the water resistance evaluation, when the change was not observed, it was rated "AA" and when the end of the laminate was swollen by 3 to 5 mm width but could be restored to its original state, it was rated "A" D "grade when the film had a burr, and " D " grade when the film had a burr, when the adhesive layer was swollen by 5 mm width and could not be restored to its original state, .

[Table 2]

Claims (9)

A printing medium for aqueous ink, comprising: a base having a first surface; and an ink receiving layer on at least a portion of the first surface of the substrate, wherein (1) 1 having a printing surface formed by micro-phase separation of a blend of a resin component composition and a second resin component composition; (2) the first resin component is hydrophilic; (3) the second resin component comprises an acrylic polymer having a quaternized amino group and exhibits thermal adhesiveness. 2. The printing medium of claim 1, wherein the printing surface is formed of a matrix of a first domain, the majority of which is a first resin component, and a second domain, the majority of which is a second resin component. 2. The print medium of claim 1, wherein the second domain substantially surrounds each first domain and the second domain is relatively convex. The print medium of claim 1, wherein the first resin component comprises a polyalkylene oxide. The print medium of claim 1, wherein the acrylic polymer has a phenoxy group. 2. The composition of claim 1, wherein the acrylic polymer comprises: 3 to 13% by weight of an acrylic monomer having a quaternized amino group; From 20 to 90 mass% of alkyl (meth) acrylate; 0 to 70% by mass of an acrylic monomer having a phenoxy group; And 1 to 8% by weight of (meth) acrylic acid. The print medium according to claim 1, wherein the amount of the first resin in the ink receiving layer is 20 to 70% by mass based on 100% by mass of the total amount of the first resin and the second resin. A method for producing the print medium of claim 1 comprising the steps of: (1) providing a substrate having a first surface; (2) providing a blend of a first resin component composition and a second resin component composition; (3) applying the blend to at least a portion of the first surface of the substrate to form a coating on the substrate; And (4) removing the solvent from the coating to cause micro-phase separation of the first resin component and the second resin component. 9. The method of claim 8, wherein the coating liquid is a suspension comprising the resin microparticles of the first resin and the second resin.

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