JP6181761B2 - Aqueous color ink jet printing medium and method for producing the same - Google Patents

Description

  The present invention particularly relates to an aqueous color ink jet printing medium and a method for producing the same.

  Various products such as paper, synthetic paper, and resin films are known as conventional print media. These print media are affixed to various objects, and are used, for example, by applying an adhesive to the print medium and applying a double-sided adhesive tape.

  In recent years, there has been known a configuration of a print medium that functions as a pressure-sensitive adhesive surface and without having to apply an adhesive on a printed image. Examples of such are disclosed in the following documents: D1-JP 2004-276613; D2-JP 11-165457; D3-JP 2008-087276; D4-JP 2008-. 087324; and D5- JP 2011-255650.

  There is a need for media that can accept aqueous ink jets and have improved resistance to image bleeding, moisture absorption and resistance to moisture damage, and in particular, media used in high speed printing applications.

  The present invention provides an improved print medium capable of accepting ink jets and a method of manufacturing such a medium.

  Briefly summarized, the print medium of the present invention comprises a substrate having a first surface and an ink receptive 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 defined by microphase separation of a mixture of the first resin component composition and the second resin component composition, and (2) the first One resin component is hydrophilic, and (3) the second resin component contains an acrylic polymer having a quaternary amino group and exhibits thermal adhesive properties. It has been surprisingly found that an ink receptive layer having a printing surface, or area defined by a microphase separation structure as described herein, provides unexpected and advantageous results.

  As described herein, the first resin component and the second resin component exhibit a microphase separation structure on the printed surface.

  Briefly summarized, there is provided a method of producing a print medium of the present invention, the method comprising: (1) providing a substrate having a first surface; (2) a first resin component composition and a second. Providing a mixture of resin component compositions; (3) applying the mixture to at least a portion of the first surface of the substrate to form a coating thereon; and (4) the above Removing the solvent from the coating such that microphase separation of the first resin component and the second resin component occurs.

  The media provided by the present invention provides a surprising combination of important advantages. They include good, high resolution, water-based ink acceptance, resistance to image bleeding, moisture absorption and resistance to moisture damage, and good tack, i.e. printing surface Is to adhere to the desired adherend. Such media are particularly suitable for use in high speed printing applications, on which can be used to make articles having high quality, high resolution durable images.

  So far, for example, the prior art described in the references D1 to D4 has not provided a print medium that realizes the desired performance and function. Reference D5, according to its claim, discloses a medium that exhibits the desired performance and function. However, it has been found that the medium disclosed therein exhibits color flow when jetted at a speed higher than 25 mm / sec with aqueous ink.

  According to the present invention, the printing surface has a plurality of first microphase separation regions containing more first resin components than the second resin components, and contains more second resin components than the first resin components. One second microphase separation region surrounds each of the plurality of microphase separation regions in a substantially ring shape, and has a relatively convex shape.

The present invention will be further described with reference to the drawings.
FIG. 3 is a schematic cross-sectional view illustrating one exemplary embodiment of a print medium of the present invention. It is a typical sectional view showing other exemplary embodiments of the printing medium of the present invention. FIG. 6 is a schematic cross-sectional view showing still another exemplary embodiment of the print medium of the present invention. It is a figure which shows the surface observed with the optical microscope of the printing medium obtained in Example 1. FIG. It is a figure which shows the result of having measured the non-contact surface roughness of the printing medium obtained in Example 1 with the measuring device. It is a figure which shows the result of having measured the non-contact surface roughness of the printing medium obtained in Example 1 with the measuring device. It is a figure which shows the result of having observed the surface of the printing medium 2 obtained by the comparative example 1 with the optical microscope. It is a figure which shows the result of having measured the non-contact surface roughness of the printing medium obtained in the comparative example 1 with the measuring device. It is a figure which shows the result of having measured the non-contact surface roughness of the printing medium obtained in the comparative example 1 with the measuring device.

  1-3 are not drawn to scale. Also, FIGS. 1-7 are intended to be illustrative only and are not intended to be limiting.

  Reference number table

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

  Unless otherwise indicated, all numerical values representing amounts and characteristics of components such as molecular weight and reaction conditions used herein and in the appended claims are in any case referred to as “about”. It should be understood as being modified. Accordingly, unless otherwise disputed, the numerical parameters set forth in the foregoing specification and the appended claims are not construed to the desired properties sought to be obtained by those skilled in the art using the techniques of the present invention. Approximate that can change accordingly. At least, and not as an attempt to limit the application of equivalent theory to the claims, each numerical parameter is interpreted at least by considering the number of significant figures reported and applying normal rounding. There must be. Although the numerical ranges and parameters described broadly in the present invention are approximations, the numerical values set forth in the specific examples are reported as accurately as possible. Any numerical value, however, inherently contains certain errors necessarily resulting from the standard deviation found in their respective testing measurements.

  The weight percent, percent by weight, weight percent (% by weight), and the like are calculated by dividing the weight of the material by the weight of the composition and multiplying by 100. A synonym for concentration.

  An enumeration by the end of a numerical range includes all numbers that fall within that range (eg 1 to 5 includes 1, 1.5, 2, 2.75, 3, 3.80, 4, and 5). ). As used herein and in the appended claims, the singular forms “a”, “an”, and “the” refer to a plurality of referents unless the content clearly dictates otherwise. Is included. Thus, for example, reference to a composition containing “a compound” includes a mixture of two or more compounds. As used herein and in the appended claims, the term “or” is generally employed in its sense including “and / or” unless the content clearly dictates otherwise. It is done.

  In the printing medium of the present invention, the printing surface is defined by microphase separation of a mixture of the first resin component composition and the second resin component composition. The resulting printed surface consists of a matrix of a first domain whose major part is the first resin component and a second domain whose major part is the second resin component, and these domains are: It has already been found to have a combination of physical configuration and properties that provide surprising performance.

  In an exemplary embodiment, the ink receiving layer has a plurality of first microphase separation regions that include more first resin components than second resin components, and more second resins than first resin components. A second microphase separation region containing components surrounds each of the plurality of first microphase separation regions in a substantially ring (ie, substantially completely enclosed cell) shape, and the second microphase separation region The region is relatively convex.

  No blurring even when the tendency of aqueous ink to decrease during printing as a result of the unique non-uniform surface characteristics between the first and second microphase separation regions resulting from the microphase separation Clearly printed image information is achieved as a result, and even high speed printing examples faster than 25 mm / sec (eg 100 mm / sec) are achieved.

  In some preferred embodiments, the first resin component comprises a polyalkylene oxide. In such embodiments, the printing properties and tackiness of the printing surface are improved because the polyalkylene oxide, combined with tackiness, provides improved acceptability for aqueous inks.

  In some embodiments, the acrylic polymer of the second resin component includes phenoxy groups. The ink-receiving layer made of this compound has improved adhesion to the desired adherend and can improve the moisture resistance of the image printed thereon.

  In some embodiments, the relative ratio between the first resin component and the second resin component is such that, in the resulting ink receiving layer, the sum of the first resin component and the second resin component is 100% by weight. The first resin component occupies 30 to 60% by mass. In this formulation, it is possible to achieve a good balance between the high speed printing properties of the printed surface and the water resistance of the printed image.

  Another embodiment of the present invention relates to a method for producing a print medium for aqueous ink. The method for producing a printing medium for water-based ink includes: applying a mixture including a first resin component, a second resin component, and a solvent to a substrate to form a coating on the substrate; Removing from the coating to cause microphase separation of the first resin component and the second resin component.

  According to this manufacturing method, the printing surface is a printing medium that functions as an adhesive surface and has both good adhesiveness and printing characteristics. In addition, even when printed with aqueous dye ink, the printed surface is printed. Thus, a print medium for water-based ink can be easily obtained in which the printed image has good water resistance and bleeding characteristics.

  In some embodiments, the coating liquid may be a suspension including a first resin component and a second resin component. The ink receiving layer formed by such a coating liquid facilitates the formation of the microphase separation structure on the printing surface using the first resin component and the second resin component.

  FIG. 1 is a schematic cross-sectional view illustrating one exemplary embodiment of a print medium of the present invention. The print medium 10 has a substrate 12, an ink receiving layer 11, and a surface F1, and the surface F1 does not face the substrate 12, that is, in the illustrated embodiment, It exists in the other side and is provided in the one side of the base material 12 as a printing surface.

  The ink receiving layer 11 includes a hydrophilic first resin component and a heat-adhesive second resin component, and consists essentially of them. The ink receiving layer 11 has a micro phase separation structure formed on the printing surface F1 by the first resin component and the second resin component. The second resin component includes an acrylic polymer having a quaternary amino group.

  On the printing surface F <b> 1 of the print medium 10, the first resin component can provide a desired receptivity to an image forming ink such as a water-based ink used in inkjet, and can function as a water-based ink receiving area. Further, the second resin component can provide a desired adhesiveness to a desired adherend of the medium and function as an adhesive area. Therefore, image printing with water-based ink is possible on the printing surface F1, and the printing surface F1 functions as an adhesive surface.

  Furthermore, since the printing medium 10 has the above-described configuration, it has good adhesiveness and good high-speed printing characteristics on the printing surface F1, for example, as a printing medium for high-speed jet printing faster than 25 mm / second. Suitable for use.

  In addition, the print image formed on the printing surface F1 using the water-based ink in the print medium 10 is excellent in water resistance and bleeding resistance. In particular, in a conventional print medium (for example, a print medium described in Reference Document D5), when a dye ink is used as a water-based ink, it is difficult to prevent a color flow of a printed image. However, according to the present print medium 10, the blur can be sufficiently suppressed even in a printed image formed using the aqueous dye ink. Therefore, the printing medium 10 can be suitably used as a printing medium for aqueous dye ink.

  Without being bound by theory, the following can be considered. A fine ink receiving area made of the first resin component and a fine adhesive area made of the second resin component realize this complicated structure on the printing surface F1 by microphase separation. Therefore, the water-based ink penetrates into the ink receiving area at the landing point, but on the other hand, the expansion (bleeding) due to the penetration of the landing point from the ink receiving area to the ink receiving area other than the landing point is hindered by the adhesive area. It is done. Therefore, it is considered that bleeding of the water-based ink in the printed matter can be prevented and a clear image can be formed. In addition, since the bleeding of the water-based ink can be prevented for the same reason, the printed image is considered to be excellent in water resistance even after the water-based ink is printed.

  The second resin component includes a quaternary amino group on the printing surface F1. Therefore, when printed with water-based dye ink, the fixing force of the dye is very excellent, and the color flow is suppressed at the interface between the ink receiving area and the adhesive area. When the dye is an acid dye, this fixing force can be obtained more remarkably and bleeding can be suppressed more remarkably. For this reason, the printing medium 10 can be used especially suitably as a printing medium for acidic dye inks.

  Here, the term microphase separation structure means that the first resin component and the second resin component exhibit a fine phase separation structure. For example, when 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 micrometers or less, it is said to have a microphase separation structure. May be. In addition, the average diameter of a phase is obtained by adding arbitrary number, and the average diameter of the layer of 10-100 can be observed with a surface optical micrograph and an electron micrograph.

  The microphase-separated structure should have an average diameter of the above-mentioned independent phase, which is preferably equal to or less than the dot diameter of the aqueous ink provided on the printing surface F1. For example, in inkjet printing, when the average diameter of the ink dots is 30 micrometers or less, 20 micrometers or less, or 10 micrometers or less, the above independent phase is preferably 30 micrometers, 20 micrometers, or 10 micrometers. Should be a fine size below the average diameter. Thereby, a clearer image can be formed.

  As can be appreciated, the minimum average diameter of the above independent phase is not particularly limited and may be greater than 0.01 micrometers, and in some embodiments, greater than 0.1 micrometers. May be.

  Island-like structures, cylindrical structures, lamellar structures, and co-continuous structures are examples of microphase separation structures. Specifically, an island-like structure in which the first resin component having hydrophilicity has an island shape and the second resin component forms the sea around it is desirable.

  The first resin component is hydrophilic. This means that the first resin component has an attribute that makes it possible to absorb water-based ink. For example, if water droplets fall on the resin component surface in an amount sufficient to cover a large area and the resin component absorbs the water droplets within a few seconds (eg, 5 seconds), the resin component is hydrophilic. It can be said that there is sex.

  In an exemplary embodiment, the first resin component includes one or more of polyalkylene oxide, hydrophilic acrylic resin, polyvinyl alcohol, polyvinyl pyrrolidone, hydrophilic polyurethane resin, and hydrophilic ethylene vinyl alcohol. You can leave.

  Preferably, the first resin component contains a polyalkylene oxide. In this case, since the polyalkylene oxide is excellent in the acceptability of the water-based ink and has adhesiveness, the printing characteristics and the adhesive characteristics of the printing surface F1 are further improved. Polyethylene oxide, polypropylene oxide, ethylene oxide, and propylene oxide copolymers are listed as polyalkylene oxides.

  In the first resin component, the polyalkylene oxide is preferably more than 80% by mass of the total mass, more preferably more than 90% by mass. The first resin component may be a polyalkylene oxide.

  The second resin component is a heat-adhesive resin component and contains at least one kind of acrylic polymer having a quaternary amino group.

  The acrylic polymer may further contain phenoxy groups. Thereby, the adhesiveness of the printing surface and the water resistance of the printed image are further improved.

  The acrylic polymer may be a polymer that includes an acrylic monomer whose monomer component has a quaternary amino group. The monomer component may further contain an acrylic monomer having a phenoxy group, an alkyl (meth) acrylate, or (meth) acrylic acid.

  For example, an acrylic monomer having a quaternary amino group, and a polymer having a monomer component containing alkyl (meth) acrylate and (meth) acrylic acid are listed as one form of the acrylic polymer, and the monomer component is a phenoxy group An acrylic monomer having the following may be included.

  Here, the ratio in the monomer component of the acryl-type monomer which has a quaternary amino group may be 3-13 mass% or 5-11 mass%. Further, the ratio of the alkyl (meth) acrylate in the monomer component may be 20 to 90% by mass, preferably 25 to 70% by mass, more preferably 30 to 60% by mass. Furthermore, the ratio of the monomer component (meth) acrylic acid may be 1 to 8% by mass. Furthermore, the ratio of the acrylic monomer having a phenoxy group in the monomer component may be 0 to 70% by mass, preferably 10 to 65% by mass, more preferably 20 to 60% by mass. .

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

  For example, a group represented by the following formula (1) is exemplified as a quaternary amino group.

In the formula, R ¹ , R ² , and R ³ are each independently an alkyl group or an allyl group, and X ⁻ is a monovalent anion. R ¹ , R ² , and R ³ should each preferably be an alkyl group or a phenyl group, more preferably an alkyl group, still more preferably a C _1-2 alkyl group (an alkyl having 1 or 2 carbon atoms). Group).

The monovalent anion as X ⁻ in the above formula is not particularly limited, and examples thereof include halide ions (chloride ions, bromide ions, iodide ions). Of these, chloride ions are more preferred because they are readily available.

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

Phenoxyethyl (meth) acrylate is an example of an acrylic monomer having a phenoxy group. As alkyl (meth) acrylate, _C1-16 alkyl (meth) acrylate is preferable and _C1-10 alkyl (meth) acrylate is more preferable. Here, “C _1-16 ” and “C _1-10 ” indicate the number of carbon atoms of the alkyl group excluding the (meth) acryloyl group.

  The second resin component may contain a hydrophobic resin component as a heat-adhesive resin component other than the acrylic polymer. For example, the second resin component may contain polyester, hydrophobic polyurethane resin, polyester urethane resin, and ethylene vinyl acetate. “Hydrophobic” means having a property of repelling water-based ink. For example, when almost all the water droplets that fall on the surface of a resin are repelled, the resin can be said to be a hydrophobic resin.

  Preferably, in the second resin component, the above-mentioned acrylic polymer occupies a ratio of more than 50% by mass, more preferably occupies a ratio of more than 60% by mass. In some examples, 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% by mass, but when the total weight of the first resin component and the second resin component is 100% by mass, the content of the first resin component is 30 to 70% by mass. It may be 60% by weight. As a result, the abundance ratio of the ink receiving area and the adhesive area in the microphase separation structure of the printing surface F1 becomes suitable, and the high-speed printing characteristics of the printing surface F1 and the water resistance of the printed image are between. A good balance is considered achievable. At this time, for example, a clear print image without blur can be obtained even at high speed printing faster than 100 mm / second.

On the printing surface F1, the ratio (S ₁ / S ₂ ) between the total area (S ₁ ) of the ink receiving area made of the first resin component and the total area (S ₂ ) of the ink receiving area made of the second resin component is For example, it may be 0.2 to 4.0 and it may be 0.4 to 1.5. Printing characteristics, adhesiveness, and water resistance are further improved by setting the ink receiving area and the adhesive area to the area ratio as described above.

  The ink receiving layer 11 can be set to, for example, 10 to 40 micrometers and 20 to 30 micrometers. The ink receiving layer 11 manufactured to such a thickness has further excellent printing characteristics and adhesiveness of the printing surface F1. The reason for such an effect is not necessarily clear, but when the thickness exceeds 15 micrometers, it is considered that the adhesive force of the second resin component is effectively exhibited and a good adhesive force can be secured. When the thickness is less than 40 micrometers, a homogeneous microphase separation structure can be easily formed.

  The ink receiving layer 11 should be optically transparent. According to such an ink receiving layer 11, an image printed on the printing surface F1 can be viewed from a surface other than the printing surface F1. In this case, it is preferred that a substrate 12 (described below) is added and it is optically transparent.

  The ink receiving layer 11 includes a first microphase separation region containing more first resin components than the second resin component, and a second microphase separation region containing more second resin components than the first resin component. And may have. In addition, the second microphase separation region surrounds the first microphase separation region in a substantially ring shape and is relatively convex. As described above, the region where the relatively large amount of the second resin component exists (second microphase separation region) is arranged around the region where the relatively large amount of the first resin component exists (first microphase separation region). As a result, bleeding is effectively prevented at the interface between the regions, and the high-speed printing characteristics are greatly improved.

  Note that “containing more first resin component than second resin component” means that the ratio of the area of the surface made by the first resin component occupying the region is the surface made by the second resin component. Is larger than the area ratio. Further, “relatively convex” means that the region is at least higher than the adjacent first aspect separation region.

  Preferably there should be a plurality of first microphase separation regions and they should be generally ring-shaped, preferably surrounding each of the second microphase separation regions. That is, the ink receiving layer 11 should preferably have a structure in which the second microphase separation region is surrounded around the first microphase separation region. In addition, this structural unit has an inhomogeneous repeating structure on the printing surface F1 as one unit.

  In other words, on the printing surface F1, the ink receiving layer 11 should preferably have a heterogeneous structure having a concave portion and a convex portion surrounding the concave portion in a substantially ring shape. The concave portion forms a first microphase separation region containing more first resin component than the second resin component, and the convex portion contains more second resin component than the first resin component. Forming a second microphase separation region.

  In this way, the retention of water-based ink on the printing surface F1 is improved, similar to the outer ring part of a volcanic crater that creates a second microphase separation region that surrounds the outside of the concave portion that forms the first microphase separation region. In addition, it is considered that the printing characteristics are further improved by the convex portion.

  In addition, the first microphase separation region contains a larger amount of the first resin component and has good absorbability with respect to the water-based ink. It is considered that the water-based ink held by the concave portion is fixed to the ink receiving layer 11 due to the increased first micro phase separation region absorption by forming the micro phase separation region with the concave portion.

  Furthermore, the second microphase separation region contains more second resin component, and the first resin component is relatively little present. It is believed that excellent tackiness and water resistance are achieved by the convex portion with which this type of second microphase separation region is brought into contact when bonded to the object.

  The shape of the first microphase separation region may be a circle, an ellipse, or a polygon, but is typically a circle. The diameter of the first microphase separation region may be, for example, 10 micrometers to 500 micrometers, or 50 micrometers to 300 micrometers.

The second microphase separation region has a relatively convex shape. However, the first difference between the height h ₁ of the average of the micro-phase separation structure (h 2 _{-h 1)} is usually adjacent to the height h ₂ of the average of the second microphase separation region, 1 micrometer to 30 micro It may be a meter, and in some examples may be between 2 micrometers and 20 micrometers.

  The second microphase separation region should preferably surround the first microphase separation region with a ring shape. However, as long as the second microphase separation region is formed in a substantially ring shape around the first microphase separation region, it is not necessary to form a complete circle.

  The substrate 12 should have a surface on which the ink receiving layer 11 can be provided. In the printing medium 10, the base material 12 has a film shape, but the base material used in the present invention does not necessarily have a film shape.

  Resin films or resin sheets made from paper, synthetic paper, and resins such as polyvinyl chloride resin, polyolefin resin, acrylic resin, polyester, and polyurethane resin can be used as the substrate 12. The substrate may be either a single layer or a multilayer. The substrate should also be capable of providing sufficient dimensional stability to form an ink receptive layer thereon, undergo subsequent handling, and further undergo processing as a print medium. One skilled in the art will always be able to select a suitable material for the substrate in view of the desired flexibility, tear strength, stretchability, elasticity, weight, etc.

  It is preferable that the base material 12 has optical transparency. Since both the substrate 12 and the ink receiving layer 11 have optical transparency, the image printed on the printing surface F <b> 1 can be viewed through the ink receiving layer 11 and the substrate 12.

  A method for using the aqueous ink printing medium according to the present embodiment will be described below. The usage of the aqueous ink printing medium of the present invention is not limited to the following.

  If the printing medium 10 is used, a clear image can be printed on the printing surface F1 using water-based ink. Further, the printing surface F1 also functions as an adhesive surface. Therefore, the print medium 10 can be easily adhered to an object without requiring an additional process for increasing the tackiness.

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

  In such a usage, since the printing medium 10 is excellent in printing characteristics, adhesiveness, and water resistance, an IC card having a clear image can be quickly made. In addition, the IC card thus produced is also excellent in water resistance.

  Further, for example, when the print medium 10 is to be peeled after being attached to the IC card, the fine ink receiving area is destroyed by the microphase separation structure of the print surface F1 of the print medium 10. , Print contents become unreadable. Therefore, according to the print medium 10, the IC card can be prevented from being reused for an illegal purpose.

  In addition, the print medium 10 can be adhered to an object having an uneven surface or a curved surface for use as a decorative film. In this case, preferably a heat extensible substrate should be used as the substrate 12 of the print medium 10. For example, such a print medium 10 can be bonded to an object having an uneven surface or a curved surface so as to be in the shape while the print medium 10 is heated with a dryer or the like.

  Depending on the application, the print medium 10 may have a support layer on the other surface side of the substrate 12 on the area to support the print medium 10 and facilitate handling. Such a situation is illustrated in FIG.

  The print medium 20 shown in FIG. 2 has a base material 22, an ink receiving layer 21 and a surface F <b> 2 provided on one side of the base material 22, and a support layer 23 provided on the other side of the base material 22. . Here, the surface F <b> 2 does not face the base material 22. The base material 22 and the ink receiving layer 21 in the print medium 20 are equivalent to the base material 12 and the ink receiving layer 11 in the print medium 10.

  The print medium 20 is easy to handle. This is because the substrate 22 and the ink receiving layer 21 are supported by the support layer 23. When the printing medium 20 is used, for example, the support layer 23 can be peeled off after an image printed with water-based ink is formed. As a result, only the base material 22 and the ink receiving layer 21 are used as objects. Can be glued.

  Depending on the application, the print medium 10 may be placed on other surfaces of the substrate 12 in the area to prevent dust and dirt from adhering to the outermost surface after the print medium 10 is adhered to the object. The dust prevention layer may be provided. Such a situation is illustrated in FIG.

  The print medium 30 shown in FIG. 3 has an ink receiving layer 31 provided as a printing surface on one side of the substrate 32, which has a surface F 3 that does not oppose the substrate 32 and the substrate 22, and the other of the substrate 32. And a dust layer 33 provided on the side. The substrate 32 and the ink receiving layer 21 in the print medium 30 are equivalent to the substrate 12 and the ink receiving layer 11 in the print medium 10. For example, the dust prevention layer 33 can be made from a resin composition containing a fluororesin.

  In addition, the print medium 30 may also include a support layer 34 for supporting the substrate 32, the ink receiving layer 31, and the dust prevention layer 33. When the print medium 30 is used, for example, the support layer 34 can be peeled off after an image printed with water-based ink is formed. As a result, the substrate 32, the ink receiving layer 31, and the dust prevention layer 33 can be removed. Only can be glued to the object.

  Next, one example of a printing method for the aqueous ink print medium according to the present embodiment will be described.

  A method for printing the aqueous ink on the printing surface F1 of the printing medium 10 is not particularly limited, but inkjet printing is preferable. When ink jet printing is performed, a printed image can be quickly formed. In addition, the above-described IC card can be manufactured more quickly.

  The printing speed of jet printing can be faster than 25 mm / second, faster than 50 mm / second, or even faster than 100 mm / second. An advantage of the present invention is that a clear image can be formed on the medium of the present invention without suffering from ink bleeding and at such a high printing speed. This is because the printing medium 10 is excellent in high-speed printing characteristics on the printing surface F1.

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

  Next, a method for producing a water-based ink print medium according to the present embodiment will be described. The print medium for water-based ink of the present invention is not limited to a print medium manufactured by the following manufacturing method.

  The present manufacturing method comprises a step 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, removing the solvent from the coating, Causing a microphase separation between the resin component and the second resin component.

  According to this production method, the printing surface is a printing medium that functions as an adhesive surface and has both good adhesiveness and printing characteristics. And even if it prints with a water-based dye ink, the printing medium for water-based inks (refer to the printing medium 10 for a specific example) which has the favorable water resistance and bleeding characteristic of a printed image can be obtained easily.

  In the coating liquid of the first step, the first resin component and the second resin component may be dissolved in the solvent, and may be dispersed in the solvent as fine particles of the resin component to form a suspension. (The term “solvent” is used herein to refer to embodiments in which the subject fluid is more precisely referred to as a liquid medium, liquid fraction, etc.).

  The solvent may be one in which the first resin component and the second resin component are dissolved in the coating solution or can be uniformly dispersed in the coating solution, and an organic solvent is preferably used. Also good. Examples of organic solvents include: aromatics 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. These may be used in combination or individually. Further, water or a mixture of water and alcohol may be used as a solvent in the production method.

  You may heat a coating liquid as needed. For example, the coating solution may be heated to 30 to 60 ° C. in order to dissolve the first resin component and the second resin component.

  In one situation of the manufacturing method, the coating liquid may be a suspension containing the first resin component and the second resin component. The ink receiving layer formed of such a coating liquid creates a characteristic inhomogeneous shape on the printing surface having a concave portion and a pointed convex portion surrounding the concave portion. In addition, when such an ink receiving layer is formed in a convex shape and a concave shape, it further improves the water resistance and bleeding characteristics of the printed image.

  Using the difference in solubility between the first resin component and the second resin component, and when mixing the solution and the second solution, partial separation of the first resin component and / or the second resin component is performed. It is possible to form fine particles of resin.

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

  For example, 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 acetone / methanol at room temperature (20 ° C.). By mixing the second solution at 20 ° C. dissolved in the mixed solvent, a coating solution containing the resin fine particles described above is obtained.

  When the first resin component is a polyalkylene oxide, the first solution should preferably contain methyl ethyl ketone, toluene, and methanol as solvents. Also, the first solution should preferably be heated to 35-60 ° C. On the other hand, the second solution should preferably contain methyl ethyl ketone or acetone and methanol as solvents. The temperature should preferably be 15-30 ° C.

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

  The coating can be applied by applying a coating solution on one side of the substrate. The coating method of the coating solution is not particularly limited, and known methods such as knife coating, spin coating, roll coating, silk screen coating, and gravure coating can be used.

  Preferably, the coating should be formed so that the thickness of the ink receiving layer formed after the second step is 10-40 micrometers. When the coating is formed with the above thickness, the printing surface of the obtained ink receiving layer is further excellent in printing characteristics and adhesiveness.

  The solvent is removed from the coating in a second step. A method for volatilizing and removing the solvent by heating and an air drying method are examples of the method for removing the organic solvent. In the second step, the solvent of the coating need not be completely removed and the ink receiving layer may contain some solvent.

  As can be appreciated, the print media of the present invention may be formed in sheet or roll form.

  As described above, one preferred embodiment of the present invention has been described, but the present invention is not limited to the above-described embodiment. For example, in the present invention, the print image formed on the print surface F1 of the print medium 10 with the aqueous ink may be a decorative film. In addition, the present invention provides a modified article (for example, printing) in which a print medium 10 having a print image formed on the printing surface F1 with water-based ink is adhered to an object (for example, an IC card main body). IC card having an image).

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

  Acrylic polymer B1: N quaternized with 33% by weight methyl acrylate (hereinafter “MA”), 55% by weight phenoxyethyl acrylate (hereinafter sometimes “PhEA”), 10% by weight methyl chloride , N-dimethylaminoethyl acrylate (hereinafter “DMAEA-Q” in some cases), and 2% by weight acrylic acid (hereinafter “AA” in some cases) are 148.58% acetone and 34.49% by weight. Was uniformly dissolved in a mixed solvent of methanol and the solution was reacted. An aqueous solution having a solid content of 79% by mass was used as DMAEA-Q. This reaction solution is poured into a pressure-resistant and heat-resistant glass container, and 0.1 mass% azobisisobutyronitrile is added as an initiator to perform deoxidation, and then nitrogen is stirred while stirring for 10 minutes. Passed through. Next, the copolymerization reaction was carried out for 20 hours after warming to 50 ° C. to obtain a 35 mass% solution of acrylic polymer B1.

  Acrylic polymer B2: 43% by weight methyl acrylate, 45% by weight phenoxyethyl acrylate, 10% by weight N, N-dimethylaminoethyl acrylate quaternized with methyl chloride, and 2% by weight acrylic acid are 148 It was uniformly dissolved in a mixed solvent of .58 mass% acetone and 34.49 mass% methanol, and the solution was reacted. An aqueous solution having a solid content of 79% by mass was used as DMAEA-Q. This reaction solution is poured into a pressure-resistant and heat-resistant glass container, and 0.1 mass% azobisisobutyronitrile is added as an initiator to perform deoxidation, and then nitrogen is stirred while stirring for 10 minutes. Passed through. Next, the copolymerization reaction was carried out for 20 hours while warming to 50 ° C., and a 35 mass% solution of acrylic polymer B2 was obtained.

  Acrylic polymer B3: 23% by weight methyl acrylate, 65% by weight phenoxyethyl acrylate, 10% by weight N, N-dimethylaminoethyl acrylate quaternized with methyl chloride, and 2% by weight acrylic acid are 148 It was uniformly dissolved in a mixed solvent of .58 mass% acetone and 34.49 mass% methanol, and the solution was reacted. An aqueous solution having a solid content of 79% by mass was used as DMAEA-Q. This reaction solution is poured into a pressure-resistant and heat-resistant glass container, and 0.1 mass% azobisisobutyronitrile is added as an initiator to perform deoxidation, and then nitrogen is stirred while stirring for 10 minutes. Passed through. Next, the copolymerization reaction was carried out for 20 hours after warming to 50 ° C. to obtain a 35 mass% solution of acrylic polymer B3.

  Acrylic polymer B4: 73% by weight methyl acrylate, 15% by weight phenoxyethyl acrylate, 10% by weight N, N-dimethylaminoethyl acrylate quaternized with methyl chloride, and 2% by weight acrylic acid are 148 It was uniformly dissolved in a mixed solvent of .58 mass% acetone and 34.49 mass% methanol, and the solution was reacted. An aqueous solution having a solid content of 79% by mass was used as DMAEA-Q. This reaction solution is poured into a pressure-resistant and heat-resistant glass container, and 0.1 mass% azobisisobutyronitrile is added as an initiator to perform deoxidation, and then nitrogen is stirred while stirring for 10 minutes. Passed through. Next, the copolymerization reaction was carried out for 20 hours after warming to 50 ° C. to obtain a 35 mass% solution of acrylic polymer B4.

  Acrylic polymer B5: N, N-dimethylaminoethyl acrylate quaternized with 33% by weight of 2-ethylhexyl acrylate (hereinafter sometimes “2EHA”), 55% by weight of phenoxyethyl acrylate, 10% by weight of methyl chloride And 2% by mass of acrylic acid were uniformly dissolved in a mixed solvent of 148.58% by mass of acetone and 34.49% by mass of methanol, and the solution was reacted. An aqueous solution having a solid content of 79% by mass was used as DMAEA-Q. This reaction solution is poured into a pressure-resistant and heat-resistant glass container, and 0.1 mass% azobisisobutyronitrile is added as an initiator to perform deoxidation, and then nitrogen is stirred while stirring for 10 minutes. Passed through. Next, the copolymerization reaction was carried out for 20 hours after warming to 50 ° C., and a 35 mass% solution of acrylic polymer B5 was obtained.

  Acrylic polymer B6: 29% by weight methyl acrylate, 55% by weight phenoxyethyl acrylate, 10% by weight N, N-dimethylaminoethyl acrylate quaternized with methyl chloride, and 2% by weight acrylic acid are 148 It was uniformly dissolved in a mixed solvent of .58 mass% acetone and 34.49 mass% methanol, and the solution was reacted. An aqueous solution having a solid content of 79% by mass was used as DMAEA-Q. This reaction solution is poured into a pressure-resistant and heat-resistant glass container, and 0.1 mass% azobisisobutyronitrile is added as an initiator to perform deoxidation, and then nitrogen is stirred while stirring for 10 minutes. Passed through. Next, the copolymerization reaction was carried out for 20 hours while warming to 50 ° C., and a 35 mass% solution of acrylic polymer B6 was obtained.

  Acrylic polymer B7: N, N-dimethylaminoethyl acrylate quaternized with 88% by weight methyl acrylate, 10% by weight methyl chloride, and 2% by weight acrylic acid with 148.58% by weight acetone and 34% It was uniformly dissolved in a mixed solvent with 49% by mass of methanol, and the solution was reacted. An aqueous solution having a solid content of 79% by mass was used as DMAEA-Q. This reaction solution is poured into a pressure-resistant and heat-resistant glass container, and 0.1 mass% azobisisobutyronitrile is added as an initiator to perform deoxidation, and then nitrogen is stirred while stirring for 10 minutes. Passed through. Next, the copolymerization reaction was carried out for 20 hours while warming to 50 ° C., and a 35 mass% solution of acrylic polymer B7 was obtained.

  Acrylic polymer B8: 58% by weight methyl acrylate, 35% by weight phenoxyethyl acrylate, 5% by weight N, N-dimethylaminoethyl acrylate quaternized with methyl chloride, and 2% by weight acrylic acid are 148 It was uniformly dissolved in a mixed solvent of .58 mass% acetone and 34.49 mass% methanol, and the solution was reacted. This reaction solution is poured into a pressure-resistant and heat-resistant glass container, and 0.1 mass% azobisisobutyronitrile is added as an initiator to perform deoxidation, and then nitrogen is stirred while stirring for 10 minutes. Passed through. Next, the copolymerization reaction was carried out for 20 hours by warming to 50 ° C., and a 35 mass% solution of acrylic polymer B8 was obtained.

  Acrylic polymer B9: 33% by weight methyl acrylate, 55% by weight phenoxyethyl acrylate, 10% by weight N, N-dimethylaminoethyl acrylate (sometimes a tertiary amine expressed as “DMAEA”), and 2% by weight % Acrylic acid was uniformly dissolved in a mixed solvent of 148.58 mass% acetone and 34.49 mass% methanol, and the solution was reacted. This reaction solution is poured into a pressure-resistant and heat-resistant glass container, and 0.1 mass% azobisisobutyronitrile is added as an initiator to perform deoxidation, and then nitrogen is stirred while stirring for 10 minutes. Passed through. Next, the copolymerization reaction was carried out for 20 hours while warming to 50 ° C., and a 35 mass% solution of acrylic polymer B9 was obtained.

  Acrylic polymer B10: 43% by weight methyl acrylate, 55% by weight phenoxyethyl acrylate, and 2% by weight acrylic acid are homogeneous in a mixed solvent of 148.58% by weight acetone and 34.49% by weight methanol. And the solution was allowed to react. This reaction solution is poured into a pressure-resistant and heat-resistant glass container, and 0.1 mass% azobisisobutyronitrile is added as an initiator to perform deoxidation, and then nitrogen is stirred while stirring for 10 minutes. Passed through. Next, the copolymerization reaction was carried out for 20 hours while warming to 50 ° C., and a 35 mass% solution of acrylic polymer B10 was obtained.

  Acrylic polymer B11: 28% by weight methyl acrylate, 55% by weight phenoxyethyl acrylate, 15% by weight methyl chloride quaternized N, N-dimethylaminoethyl acrylate, and 2% by weight acrylic acid are 148 It was uniformly dissolved in a mixed solvent of .58 mass% acetone and 34.49 mass% methanol, and the solution was reacted. This reaction solution is poured into a pressure-resistant and heat-resistant glass container, and 0.1 mass% azobisisobutyronitrile is added as an initiator to perform deoxidation, and then nitrogen is stirred while stirring for 10 minutes. Passed through. Next, the copolymerization reaction was carried out for 20 hours after warming to 50 ° C., and a 35 mass% solution of acrylic polymer B5 was obtained.

  Acrylic polymer B12: 25% by weight methyl acrylate, 55% by weight phenoxyethyl acrylate, 10% by weight N, N-dimethylaminoethyl acrylate quaternized with methyl chloride, and 10% by weight acrylic acid are 148 It was uniformly dissolved in a mixed solvent of .58 mass% acetone and 34.49 mass% methanol, and the solution was reacted. This reaction solution is poured into a pressure-resistant and heat-resistant glass container, and 0.1 mass% azobisisobutyronitrile is added as an initiator to perform deoxidation, and then nitrogen is stirred while stirring for 10 minutes. Passed through. Next, the copolymerization reaction was carried out for 20 hours after warming to 50 ° C., and a 35 mass% solution of acrylic polymer B5 was obtained.

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

Example 1
Aqua Coke (registered trademark) (available from Sumitomo Seika Co., Ltd., polyalkylene oxide, solid content concentration of 100% by mass) is 40 ° C. in a mixed solvent of methyl ethyl ketone / toluene / methanol (mass ratio 2: 1: 1). And a solution A1 having a solid density of 15% by mass was produced as the first resin component. Also, a 35% by mass solution of acrylic polymer B1 (hereinafter, solution B1) was used as the second resin component.

  The solution A1 and the solution B1 were mixed at 40 ° C. so that the mass ratio of the first resin component and the second resin component was 60:40, thereby producing a mixed solution C1.

  The solution C1 was applied to a polyethylene terephthalate film (PET film) having a thickness of 50 micrometers by a knife coating method, and the solution C1 was dried in an oven set at 80 ° C. for 10 minutes to place the ink receiving layer on the PET film. The print medium 1 was obtained. Next, the thickness of the ink receiving layer formed after drying was adjusted to 25 micrometers. The adjustment of the thickness of the ink receiving layer was performed by adjusting the gap between the PET film surface and the knife surface.

  When the print medium 1 was obtained, the print medium 1 was observed with a surface optical microscope. The ink receiving layer of the printing medium 1 had a substantially homogeneous microphase separation structure on the printing surface. The results are shown in Table 4.

  Moreover, the printing surface of the ink receiving layer of the obtained printing medium 1 was measured using a non-contact surface roughness measuring device (Zaygo) for measuring the surface roughness of the printing surface. The results are shown in Table 5. From the results shown in FIG. 5, a unique non-circular structure having a structural unit comprising a substantially circular first microphase separation region and a substantially ring-shaped convex second microphase separation region surrounding the outer periphery thereof. A homogeneous structural arrangement was confirmed. In other words, it was confirmed that the second microphase separation structure in which a unique inhomogeneous structure was formed rose to a pointed shape and surrounded the substantially circular first microphase separation region.

The microphase separation structure on the printed surface formed an island structure, and the average diameter of the islands was about 5 micrometers. Further, substantially the diameter of the circular first microphase separation region is approximately 50 to 300 micrometers, the height h ₁ of the average of the first microphase separation structure, the average of the second microphase separation region height The difference from h ₂ (h ₂ −h ₁ ) was approximately 25 to 30 micrometers.

  Further, from surface observation using an atomic force microscope (AFM), more first resin components than the second resin components are present in the first microphase separation region and more second than the first resin components. It was confirmed that the resin component was present in the second microphase separation region. Specifically, such existence was confirmed from the crystal orientation state indicated by the first resin component.

  Moreover, about the printing medium 1, the printing characteristic, water resistance, the adhesive force in normal temperature, and the adhesive force in high temperature were evaluated in accordance with the below-mentioned evaluation method. The evaluation results are shown in Table 2.

(Example 2)
Further, a printing medium 2 was obtained in the same manner as in Example 1 except that a solution of 35% by mass of acrylic polymer B2 (hereinafter, solution B2) was used as the second resin component instead of the solution B1. .

  The obtained printing medium 2 was observed with a surface optical microscope. The ink receiving layer of the printing medium 2 had a substantially homogeneous microphase separation structure on the printing surface.

  Moreover, the printing surface of the ink receiving layer of the obtained printing medium 2 was measured using a non-contact surface roughness measuring device (Zaygo) for measuring the surface roughness of the printing surface. From the result of measurement using a non-contact surface roughness measuring device, a first micro phase separation region and a convex second micro phase separation region that surrounds the outer periphery of the first micro phase separation region with a substantially ring shape, It was confirmed that a large number of arranged and unique heterogeneous structures were formed in the same manner as in Example 1 even on the printing surface of the ink receiving layer of the printing medium 2.

  Moreover, about the printing medium 2, the printing characteristic, water resistance, the adhesive force in normal temperature, and the adhesive force in high temperature were evaluated in accordance with the below-mentioned evaluation method. The evaluation results are shown in Table 2.

(Example 3)
Further, a printing medium 3 was obtained in the same manner as in Example 1, except that a solution of 35% by mass of acrylic polymer B3 (hereinafter, solution B3) was used as the second resin component instead of the solution B1. .

  The obtained printing medium 3 was observed with a surface optical microscope. The ink receiving layer of the printing medium 3 had a substantially homogeneous microphase separation structure on the printing surface.

  Further, the printing surface of the ink receiving layer of the obtained printing medium 3 was measured using a non-contact surface roughness measuring device (Zaygo) for measuring the surface roughness of the printing surface. From the result of measurement using a non-contact surface roughness measuring device, a first micro phase separation region and a convex second micro phase separation region that surrounds the outer periphery of the first micro phase separation region with a substantially ring shape, It was confirmed that a multi-arrayed and unique heterogeneous structure having the same structure as that of Example 1 was formed even on the printing surface of the ink receiving layer of the printing medium 3.

  Moreover, about the printing medium 3, printing characteristics, water resistance, the adhesive force in normal temperature, and the adhesive force in high temperature were evaluated in accordance with the below-mentioned evaluation method. The evaluation results are shown in Table 2.

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

  The obtained printing medium 4 was observed with a surface optical microscope. The ink receiving layer of the printing medium 4 had a substantially homogeneous microphase separation structure on the printing surface.

  Moreover, the printing surface of the ink receiving layer of the obtained printing medium 4 was measured using a non-contact surface roughness measuring instrument (Zaygo) for measuring the surface roughness of the printing surface. From the result of measurement using a non-contact surface roughness measuring device, a first micro phase separation region and a convex second micro phase separation region that surrounds the outer periphery of the first micro phase separation region with a substantially ring shape, It was confirmed that a large number of arranged and unique heterogeneous structures were formed in the same manner as that of Example 1 even on the printing surface of the ink receiving layer of the printing medium 4.

  Moreover, about the printing medium 4, printing characteristics, water resistance, the adhesive force in normal temperature, and the adhesive force in high temperature were evaluated in accordance with the below-mentioned evaluation method. The evaluation results are shown in Table 2.

(Example 5)
Further, a printing medium 5 was obtained in the same manner as in Example 1 except that a 35% by mass acrylic polymer B5 solution (hereinafter, solution B5) was used as the second resin component instead of the solution B1. .

  The obtained printing medium 5 was observed with a surface optical microscope. The ink receiving layer of the printing medium 5 had a substantially homogeneous microphase separation structure on the printing surface.

  Moreover, the printing surface of the ink receiving layer of the obtained printing medium 5 was measured using a non-contact surface roughness measuring device (Zaygo) for measuring the surface roughness of the printing surface. From the result of measurement using a non-contact surface roughness measuring device, a first micro phase separation region and a convex second micro phase separation region that surrounds the outer periphery of the first micro phase separation region with a substantially ring shape, It was confirmed that a large number of arranged and unique heterogeneous structures having the same structure as that of Example 1 were formed even on the printing surface of the ink receiving layer of the printing medium 5.

  Moreover, about the printing medium 5, the printing characteristic, water resistance, the adhesive force in normal temperature, and the adhesive force in high temperature were evaluated in accordance with the below-mentioned evaluation method. The evaluation results are shown in Table 2.

(Example 6)
Except for using the mixed liquid C2 obtained by mixing the solution A1 and the solution B1 at 40 ° C. as a substitute for the solution C1 so that the mass ratio of the first resin component and the second resin component is 50:50, A print medium 6 was obtained in the same manner as in Example 1.

  The obtained printing medium 6 was observed with a surface optical microscope. The ink receiving layer of the printing medium 6 had a substantially homogeneous microphase separation structure on the printing surface.

  Moreover, the printing surface of the ink receiving layer of the obtained printing medium 6 was measured using a non-contact surface roughness measuring device (Zaygo) for measuring the surface roughness of the printing surface. From the result of measurement using a non-contact surface roughness measuring device, a first micro phase separation region and a convex second micro phase separation region that surrounds the outer periphery of the first micro phase separation region with a substantially ring shape, It was confirmed that a large number of arranged and unique heterogeneous structures were formed in the same manner as in Example 1 even on the printing surface of the ink receiving layer of the printing medium 6.

  Moreover, about the printing medium 6, the printing characteristic, water resistance, the adhesive force in normal temperature, and the adhesive force in high temperature were evaluated in accordance with the below-mentioned evaluation method. The evaluation results are shown in Table 2.

(Example 7)
Further, a printing medium 7 was obtained in the same manner as in Example 1 except that a 35% by mass solution of acrylic polymer B6 (hereinafter, solution B6) was used as the second resin component instead of the solution B1. .

  The obtained printing medium 7 was observed with a surface optical microscope. The ink receiving layer of the printing medium 7 had a substantially homogeneous microphase separation structure on the printing surface.

  Further, the printing surface of the ink receiving layer of the obtained printing medium 7 was measured using a non-contact surface roughness measuring device (Zaygo) for measuring the surface roughness of the printing surface. From the result of measurement using a non-contact surface roughness measuring device, a first micro phase separation region and a convex second micro phase separation region that surrounds the outer periphery of the first micro phase separation region with a substantially ring shape, It was confirmed that a multi-arrayed and unique heterogeneous structure having the same structure as that of Example 1 was formed even on the printing surface of the ink receiving layer of the printing medium 7.

  Moreover, about the printing medium 7, the printing characteristic, water resistance, the adhesive force in normal temperature, and the adhesive force in high temperature were evaluated in accordance with the below-mentioned evaluation method. The evaluation results are shown in Table 2.

(Example 8)
Aqua Coke (registered trademark) (available from Sumitomo Seika Co., Ltd., polyalkylene oxide, solid content concentration of 100% by mass) is 40 ° C. in a mixed solvent of methyl ethyl ketone / toluene / methanol (mass ratio 2: 1: 1). The solution A2 having a solid phase density of 15% by mass was produced as the first resin component. A printing medium 8 was obtained in the same manner as in Example 1 except that the solution A2 was used instead of the solution A1.

  The obtained printing medium 8 was observed with a surface optical microscope. The ink receiving layer of the printing medium 8 had a substantially homogeneous microphase separation structure on the printing surface.

  Moreover, the printing surface of the ink receiving layer of the obtained printing medium 8 was measured using a non-contact surface roughness measuring device (Zaygo) for measuring the surface roughness of the printing surface. As a result of the measurement by the non-contact surface roughness measuring instrument, the unique inhomogeneous structure observed in Example 1 is not observed on the printing surface of the ink receiving layer of the print medium 8, and forms a surface structure. There was a large mountain-shaped cell.

  Moreover, about the printing medium 8, printing characteristics, water resistance, the adhesive force in normal temperature, and the adhesive force in high temperature were evaluated in accordance with the below-mentioned evaluation method. The evaluation results are shown in Table 2.

Example 9
Solution A2 was prepared as in Example 8. Next, the solution A2 and the solution B1 were mixed at 40 ° C. so that the mass ratio of the first resin component and the second resin component was 30:70, thereby producing a mixed solution C3.

  A printing medium 9 was obtained in the same manner as in Example 1 except that the mixed liquid C3 was used instead of the mixed liquid C1.

  The obtained printing medium 9 was observed with a surface optical microscope. The ink receiving layer of the printing medium 9 had a substantially homogeneous microphase separation structure on the printing surface.

  Further, the printing surface of the ink receiving layer of the obtained printing medium 9 was measured using a non-contact surface roughness measuring device (Zaygo) for measuring the surface roughness of the printing surface. As a result of the measurement by the non-contact surface roughness measuring instrument, the unique inhomogeneous structure observed in Example 1 is not observed on the printing surface of the ink receiving layer of the print medium 8, and forms a surface structure. There was a large mountain-shaped cell.

  Moreover, about the printing medium 9, the printing characteristic, water resistance, the adhesive force in normal temperature, and the adhesive force in high temperature were evaluated in accordance with the below-mentioned evaluation method. The evaluation results are shown in Table 2.

(Example 10)
Solution A2 was prepared as in Example 8. Further, a 35% by mass solution of acrylic polymer B7 (hereinafter, solution B7) was used as the second resin component. Next, the solution A2 and the solution B7 were mixed at 40 ° C. so that the mass ratio of the first resin component and the second resin component was 40:60, thereby producing a mixed solution C4.

  A printing medium 10 was obtained in the same manner as in Example 1 except that the mixed liquid C4 was used instead of the mixed liquid C1.

  The obtained printing medium 10 was observed with a surface optical microscope. The ink receiving layer of the printing medium 10 had a substantially homogeneous microphase separation structure on the printing surface.

  Moreover, the printing surface of the ink receiving layer of the obtained printing medium 10 was measured using a non-contact surface roughness measuring device (Zaygo) for measuring the surface roughness of the printing surface. As a result of the measurement by the non-contact surface roughness measuring device, the unique inhomogeneous structure observed in Example 1 is not observed on the printing surface of the ink receiving layer of the printing medium 9, but forms a surface structure. There was a large mountain-shaped cell.

(Example 11)
In addition, a printing medium 11 was obtained in the same manner as in Example 1, except that a solution of 35% by mass of acrylic polymer B8 (hereinafter, solution B8) was used as the second resin component instead of the solution B1. .

  The obtained printing medium 11 was observed with a surface optical microscope. The ink receiving layer of the printing medium 11 had a substantially homogeneous microphase separation structure on the printing surface.

  Moreover, the printing surface of the ink receiving layer of the obtained printing medium 11 was measured using a non-contact surface roughness measuring device (Zaygo) for measuring the surface roughness of the printing surface. From the result of measurement using a non-contact surface roughness measuring device, a first micro phase separation region and a convex second micro phase separation region that surrounds the outer periphery of the first micro phase separation region with a substantially ring shape, It was confirmed that a large number of arranged and unique heterogeneous structures were formed in the same manner as that of Example 1 even on the printing surface of the ink receiving layer of the printing medium 11.

  Moreover, about the printing medium 9, the printing characteristic, water resistance, the adhesive force in normal temperature, and the adhesive force in high temperature were evaluated in accordance with the below-mentioned evaluation method. The evaluation results are shown in Table 2.

Comparative Example C1
Solution A2 was prepared as in Example 8. Next, the solution A2 and a 35 mass% acrylic polymer B9 solution (hereinafter referred to as solution B9) are mixed so that the mass ratio of the first resin component and the second resin component is 40:60. Liquid D1 was prepared.

  A printing medium 21 was obtained in the same manner as in Example 1 except that the mixed liquid D1 was used instead of the mixed liquid C1.

  Moreover, about the printing medium 21, the printing characteristic, water resistance, the adhesive force in normal temperature, and the adhesive force in high temperature were evaluated in accordance with the below-mentioned evaluation method. The evaluation results are shown in Table 2.

  In addition, when the printing medium 21 observed using the surface optical microscope that it had the substantially homogeneous micro phase-separation structure in the printing surface was confirmed. However, from the result of measurement by a non-contact surface roughness measuring device (Zaygo), the unique heterogeneous structure observed in Example 1 is not observed on the printed surface, but forms a surface structure. There was a large mountain-shaped cell. The observation result by the surface optical microscope is shown in FIG. 6, and the measurement result by the non-contact surface roughness measuring device is shown in FIG.

Comparative Example C2
Solution A1 was prepared as in Example 1. Next, the solution A1 and a 35% by mass acrylic polymer B10 solution (hereinafter, solution B10) are mixed so that the mass ratio of the first resin component and the second resin component is 40:60. Liquid D2 was prepared.

  A printing medium 22 was obtained in the same manner as in Example 1 except that the mixed liquid D2 was used instead of the mixed liquid C1.

  Moreover, about the printing medium 22, printing characteristics, water resistance, the adhesive force in normal temperature, and the adhesive force in high temperature were evaluated in accordance with the below-mentioned evaluation method. The evaluation results are shown in Table 2.

  In addition, when the printing medium 22 observed using the surface optical microscope that it had the substantially homogeneous micro phase-separation structure in the printing surface was confirmed. However, from the result of measurement by a non-contact surface roughness measuring device (Zaygo), the unique inhomogeneous structure observed in Example 1 was not observed on the printed surface.

Comparative Example C3
40% by mass Aqua Coke (registered trademark) (available from Sumitomo Seika Co., Ltd., 100% by mass in the solid phase), 40% by mass hydrophobic polyester as a heat-sensitive hydrophobic resin, Byron (registered) (Trademark) 670 (polyester available from Toyobo Co., Ltd.), 20% by mass polyurethane resin, Byron (registered trademark) UR-3200 (polyester urethane resin available from Toyobo Co., Ltd., glass transition temperature is -3 ° C, A solid content concentration of 30% by mass was sufficiently stirred and dispersed at 60 ° C. in a mixed solvent of methyl ethyl ketone / toluene (mass ratio of 1: 1).

  The solution D3 is poured into a polyethylene terephthalate film (PET film) having a thickness of 50 micrometers by a knife coating method, and the solution D3 is dried in an oven set at 80 ° C. for 10 minutes to form an ink receiving layer on the PET film. As a result, a print medium 23 was obtained. Next, the thickness of the ink receiving layer formed after drying was adjusted to 25 micrometers.

  In addition, when the printing medium 23 observed using the surface optical microscope that it had the substantially homogeneous micro phase-separation structure in the printing surface was confirmed. However, from the result of measurement by a non-contact surface roughness measuring device (Zaygo), the unique inhomogeneous structure observed in Example 1 was not observed on the printed surface.

  Moreover, about the printing medium 23, the printing characteristic, water resistance, the adhesive force in normal temperature, and the adhesive force in high temperature were evaluated in accordance with the below-mentioned evaluation method. The evaluation results are shown in Table 2.

Test method Evaluation of printing characteristics: Using CANON (registered trademark) ink jet printer p-640L, water color ink printing of 6 colors, printing speed of 25 mm / sec or 100 mm / sec, and printing of portraits and characters on print media Printed on the ink receiving layer. The printed images were visually evaluated for the following five ranks. “D” means that the printed image was the most unclear, and the vividness of the printed image is shown as being gradually improved in this order with “C”, “B”, and “A”. Furthermore, “AA” was the score given to the clearest printed image. The results obtained at a printing speed of 25 mm / second were evaluated as “printing characteristics”, and the results obtained at a printing speed of 100 mm / second were evaluated as “high-speed printing characteristics”.

  Evaluation of bleeding property: An image was printed on the ink receiving layer of the printing medium, and the evaluation was performed in the same manner as the evaluation of the printing property. Next, the printing medium and the vinyl chloride resin card were placed so that the printing surface of the printing medium and one side of the card face each other, and they were laminated with heat using a roll-type thermal laminator ( At 120 ° C. for 1 second). After the samples were allowed to stand for 7 days at 80 ° C., the printed images were visually observed to look for blur. The evaluation was ranked into five ranks described below.

AA: No change at all.
A: Almost no change compared to the control.
B: There is a noticeable change compared to the control.
C: There is a noticeable blur.
D: There is a very obvious noticeable blur over the entire surface.

  Evaluation of adhesive strength at normal temperature: An image was printed on the ink receiving layer of the printing medium, and the evaluation was performed in the same manner as the evaluation of printing characteristics. Next, the printing medium and the vinyl chloride resin card were placed so that the printing surface of the printing medium and one side of the card face each other, and they were laminated with heat using a roll-type thermal laminator ( At 120 ° C. for 1 second).

  The obtained sample for measurement was allowed to stand at 23 ° C. for 24 hours, and then the peel strength (N / 25 mm) at an angle of 180 ° was measured at 23 ° C. using a pull tester. As measurement conditions, the tensile speed was set to 200 mm / min. The measurement result is an evaluation when “A” is larger than 15 N / 25 mm or the material is broken, and an evaluation when “B” is 15 to 10 N / 25 mm, and an evaluation when “C” is smaller than 10 N / 25 mm. Met.

  Evaluation of adhesive strength at high temperature: A sample for measurement was obtained by a method similar to the evaluation of adhesive strength at normal temperature. The obtained sample for measurement was allowed to stand at 23 ° C. for 24 hours, and then the peel strength (N / 25 mm) at an angle of 180 degrees was measured at 80 ° C. using a pull tester. As measurement conditions, the tensile speed was set to 200 mm / min. The measurement result is an evaluation when “A” is larger than 15 N / 25 mm or the material is broken, and an evaluation when “B” is 15 to 10 N / 25 mm, and an evaluation when “C” is smaller than 10 N / 25 mm. Met.

  Evaluation of water resistance: A sample for measurement was obtained by a method similar to the evaluation of adhesive strength at room temperature. After the measurement sample was allowed to stand in water at room temperature (25 ° C.) for 24 hours, a change in appearance was visually confirmed. In the water resistance evaluation, “AA” was ranked when no change was observed, and “A” was ranked when the end of the laminate was 3 to 5 mm wide. Although it is swollen, it was a case where it was possible to return to the original state, and it was ranked “B” that the end of the laminate was swollen with a width of 3 to 5 mm and returned to the original state. It was a case where it was impossible, and it was ranked “C” when the adhesive layer had eluted, and “D” was ranked when the film was turned upside down Is the case.

Claims (3)

A substrate having a first surface, an aqueous ink for a printing medium comprising an ink receiving layer, a that is on at least a portion of the first surface of the substrate,
(1) The ink receiving layer has a printing surface defined by microphase separation of a mixture of the first resin component composition and the second resin component composition;
(2) The first resin component is hydrophilic,
(3) the second resin component comprises an acrylic polymer having quaternized amino groups, it shows the thermal bonding properties,
The printing surface is composed of a matrix of first domains and second domains, a majority part of the first domains is a first resin component, a main part of the second domain is a second resin component, The second domain substantially surrounds each first domain, and the second domain is relatively convex . A method for producing a print medium according to claim 1, comprising:
(1) providing a substrate having a first surface;
(2) providing a mixture of the first resin component composition and the second resin component composition;
(3) applying the mixture to at least a portion of the first surface of the substrate to form a coating thereon ;
(4) Ri is microphase separation of the first resin component and a second resin component to put in so that resulting printing surface composed of a matrix of the first and second domains, a step of removing the solvent from the coating The majority of the first domain is a first resin component, the main part of the second domain is a second resin component, and the second domain substantially surrounds each first domain. And wherein the second domain is relatively convex . Coating coating solution is a suspension containing fine resin particles composed of the first resin and the second resin The method of claim 2.

Images