JP2021142692A - Recording material for printing - Google Patents

Abstract

To provide: a recording material for printing, which exhibits an excellent artistic property through a deep glossy feeling like a pearl while having glossiness; and a printed matter.SOLUTION: There is provided a recording material for printing, having a glossy layer and an ink receiving layer laminated in this order on at least one surface of a substrate. The glossy layer comprises: a resin binder such as polyvinyl alcohol and the like; and titanium oxide-coated mica which has surface of mica particles coated with titanium oxide, where an average particle diameter of the coated mica is 50 μm to 300 μm and a content thereof based on a total amount of the glossy layer is 20 mass% to 80 mass%. The ink receiving layer comprises a resin binder and inorganic particles such as alumina and the like, an average particle diameter of the inorganic particles is 0.1 μm to 1.0 μm, and a content thereof based on a total amount of the ink receiving layer is 5 mass% to 30 mass%.SELECTED DRAWING: Figure 1

Description

The present invention relates to a printing recording material that has glossiness and exhibits excellent artistic properties due to a deep glossiness like pearls utilizing multi-layer reflection of light and an interference phenomenon.

In recent years, with the remarkable progress of various printing machines such as printers, it has become easy to obtain full-color and high-definition images. Photographs and graphics are often used for exhibition purposes such as photographic prints and graphic work prints by inkjet recording methods and screen printing. It is important how the printing recording material used for such exhibition purposes enhances the artistic quality, and the printing recording has not only the conventional high glossiness but also the artistic pearly luster. The material is desired.

As a recording material having a pearly luster, an inkjet recording sheet (Patent Document 1) in which a pearly luster layer containing mica having an average particle diameter of 30 μm to 150 μm and an ink receiving layer are sequentially provided on a base material, and breathability. Alumina or alumina hydrate having an average particle size of 10 nm or more and 50 nm or less on at least one surface of the support, and an average particle size of 10 μm or more and 200 μm or less in which the surface of mica particles is coated with titanium oxide. An inkjet recording material (Patent Document 2) provided with an ink receiving layer containing a high-intensity pigment, a polyurea compound, and an adhesive has been proposed.

Japanese Unexamined Patent Publication No. 2006-218785 Japanese Unexamined Patent Publication No. 2012-131198

However, in the inkjet recording sheet described in the above patent document, the pearly luster is overemphasized to give a so-called glare, and the artistic quality cannot be enhanced at present. In particular, when a pearl-like gloss layer is provided on the ink receiving layer as in the recording sheet described in Patent Document 1, there arises a problem that printing uniformity is impaired as the mica particles become larger. It lacks print recording characteristics.
In view of the above circumstances, the present invention uses titanium oxide-coated mica as the pearl-like glossy material, selects a specific particle size as the mica, and controls the particle size of the inorganic particles contained in the ink receiving layer. As a result, it is possible to provide a printing recording material which is excellent in coatability and print recording characteristics of a glossy layer, and which exhibits a pearly glossy feeling rich in depth and quality and artistic properties.

According to the present invention, a printing recording material in which a glossy layer and an ink receiving layer are laminated in this order on at least one surface of a base material.
The glossy layer contains a resin binder and titanium oxide-coated mica whose surface of mica particles is coated with titanium oxide, and the average particle size of the titanium oxide-coated mica is 50 μm or more and 300 μm or less, and the titanium oxide-coated mica has an average particle diameter of 50 μm or more and 300 μm or less. The content is 20% by mass or more and 80% by mass or less based on the total amount of the glossy layer (100% by mass).
The ink receiving layer contains a resin binder and inorganic particles, the average particle size of the inorganic particles is 0.1 μm or more and 1.0 μm or less, and the content of the inorganic particles is based on the total amount of the ink receiving layer ( The printing recording material is provided, characterized in that it is 5% by mass or more and 30% by mass or less as 100% by mass).
In the printing recording material of the present invention, the following aspects are preferable.
(1) The solubility of the inorganic particles in water is 0.5 g / 100 g / water or less. (2) The thickness of the glossy layer is 20 μm or more and 400 μm or less, and the thickness of the ink receiving layer is 20 μm or more and 200 μm or less. Further, in the present invention, a printed matter drawn with ink on the printing recording material is provided.

INDUSTRIAL APPLICABILITY According to the present invention, a high-quality and glossy printing recording material that does not glare can be obtained, and in addition, the image printed on the printing recording material becomes a printed matter having excellent depth and rich artistic properties. I think the reason is as follows.
Generally, an ink receiving layer containing a bright pigment such as mica having an average particle size of 50 μm or more has a strong glaring feeling even visually and tends to reduce the artistic property. On the other hand, in the present invention, even when a titanium oxide-coated mica having a large average particle size is used, not only the glare can be suppressed by the light scattering effect of the inorganic particles in the ink receiving layer, but also the printed image can be printed. Since both the surface reflected light on the printed surface and the internally reflected light reflected by the pearl-like gloss layer are visible, it is possible to simultaneously exert a sense of depth and a pearl-like gloss, which enhances the artistic quality of the printed matter. be able to.
The printed matter obtained by the present invention can be applied to various fields. Especially, it is most suitable for the field of photography and graphic printing. Artistic means, for example, the visual sense of depth (depth), fluctuation, luster, transparency, etc., as seen in photographs made by the silver salt photosensitive method and Japanese paintings drawn on foil. An expression of a high-quality state that is evaluated from an objective point of view.

It is a schematic cross-sectional view which shows an example of the printing recording material of this invention.

FIG. 1 shows an example of a printing recording material of the present invention. In the printing recording material 1 of the present invention shown in FIG. 1, a glossy layer 3 is provided on a base material 2, and an ink receiving layer 4 is provided on the glossy layer 3. Hereinafter, the structure and manufacturing method of the printing recording material of the present invention will be described in detail.

<Recording material for printing>
The printing recording material of the present invention is a recording material having a basic structure in which a glossy layer is laminated on at least one surface of a base material and an ink receiving layer is further laminated on the glossy layer.
As long as it has the above basic structure, its mode is not limited. For example, a similar basic structure may be provided on the other side of the substrate to enable double-sided printing.

<Base material>
The base material is not particularly limited as long as it can form a glossy layer on its surface. Specific examples thereof include pulp paper and resin sheets and films made of the following resins.
Vinyl resins such as polyvinyl chloride, polyvinyl alcohol and polyvinyl acetate Poly (meth) Acrylic resins such as acrylate Polyester resins such as polyethylene and polypropylene Polyester resins such as polyethylene terephthalate Further, glass fibers, polyvinyl acetate fibers, vinylon fibers, etc. Woven fabrics or non-woven fabrics made of polyester fibers such as polypropylene fibers and polyethylene terephthalate, and fibrous materials such as acrylic fibers, aramid fibers and carbon fibers can also be used. Furthermore, paper obtained by mixing the above fibers and pulp can also be used.
The base material may be a laminated base material in which two or more types are laminated according to a desired function and purpose.
The base material is preferably flexible and has an appropriate waist strength. Since such a base material is unlikely to form creases even when bent, it is possible to suppress inconveniences such as cracks in the glossy layer and the ink receiving layer provided on the base material.
Suitable substrates are pulp paper such as Japanese paper or art supplies paper; synthetic paper mixed with pulp using chemical fibers such as glass fiber, polyvinyl acetate fiber, polyester fiber, and vinylon fiber as binder fibers; porous polyethylene resin. , Synthetic paper made from the same polypropylene resin and the same polyester resin as a sheet; resin-coated paper on which the surface of pulp paper is coated with polyethylene resin, polypropylene resin, polyester resin, etc .; canvas for painting can be mentioned. Pulp paper is particularly suitable because it has high adhesiveness to the glossy layer laminated on the paper.
The surface of the base material may be subjected to corona treatment or the like to improve hydrophilicity. Thereby, the adhesion between the base material and the glossy layer can be improved.
The thickness of the base material is appropriately set according to the size of the printed matter and the like, but the average thickness is usually 100 μm or more and 400 μm or less. If the substrate is too thick, the printing recording material may not pass through the printer, for example, during inkjet printing. If the substrate is too thin, the strength of the printing recording material tends to decrease. The average thickness of the base material is measured according to JIS P8118. The thickness of each layer described below is also measured in the same manner.

<Glossy layer>
The glossy layer is a layer containing titanium oxide-coated mica and a resin binder as essential components.

<Titanium oxide coated mica>
Titanium oxide-coated mica is a mica coated with fine crystals of titanium oxide on the surface of various mica such as natural mica such as muscovite and phlogopite, or artificial mica such as synthetic phlogopite. It is a plate-like particle of about 1/50 to 1/100. The multiple reflections on the particle surface (titanium oxide) and the interface between titanium oxide and mica, combined with the multiple reflections of mica itself, provide a high-brightness pigment that develops a deep pearly luster. The average particle size of the titanium oxide-coated mica is represented by the volume-based median diameter (d50) (hereinafter, may be referred to as “d50”) of the passage component integrated distribution measured by the laser diffraction / scattering method.
The average particle size (d50) of the titanium oxide-coated mica needs to be 50 μm or more and 300 μm or less. If it is less than 50 μm, the pearl-like gloss brightness is insufficient and the artistic property is impaired, and the coatability at the time of forming the gloss layer described later is inferior. If it exceeds 300 μm, the glaring feeling becomes strong and the artistic property is inferior, the smoothness of the glossy layer surface is impaired, and the scratch resistance after printing is lowered.
The content of the titanium oxide-coated mica in the glossy layer is 20% by mass or more and 80% by mass or less, particularly preferably 30% by mass or more and 70% by mass or less, based on the total amount of the glossy layer. If it is less than 20% by mass, a sufficient pearly deep glossiness cannot be obtained. If it exceeds 80% by mass, the flexibility of the glossy layer is lowered, and cracks and peeling occur.

<Resin binder>
A resin binder is blended in the glossy layer in order to uniformly disperse the titanium oxide-coated mica and to bond the base material and the glossy layer.
In order to exert the glossiness of the titanium oxide-coated mica without impairing it, it is preferable to use a highly transparent binder as a constituent component of the glossy layer other than the titanium oxide-coated mica. Therefore, a resin binder is used in the present invention.
The content of the resin binder in the glossy layer is preferably an amount such that the amount of the binder in the glossy layer after complete solidification is 70% by mass or less and 15% by mass or more. If the resin binder is less than the above lower limit, the adhesiveness between the base material and the glossy layer and the dispersibility in the titanium oxide-coated mica layer may decrease. If the upper limit is exceeded, sufficient pearly luster characteristics cannot be obtained.
Known resins can be used as the resin binder, and specifically, polymers such as acrylic resin, vinyl acetate resin, polyurethane, styrene / butadiene rubber, styrene-acrylic resin, ethylene vinyl acetate resin, and polyvinyl alcohol resin are used. Will be done.

<Formation of glossy layer>
A coating liquid composition for forming a glossy layer is applied to the surface of the base material, and then a glossy layer is formed through a drying and solidifying step.
In addition to the essential components of the titanium oxide-coated mica and the resin binder, the coating liquid composition for forming a glossy layer is a medium for facilitating coating on the surface of the substrate, and the titanium oxide-coated mica in the coating liquid composition. A surfactant for stably and uniformly dispersing the mixture, a thickener for controlling the viscosity of the coating liquid composition, and the like are blended as necessary.

In preparing the coating liquid composition for forming a glossy layer, it is preferable to use an aqueous emulsion in which the particles of the resin are dispersed in an aqueous medium or an aqueous solution in which the resin particles are dissolved, as the resin to be used as a binder.
As the medium, a medium that easily evaporates by heating is beneficially used. Examples of the medium having such properties include water, methyl alcohol, ethyl alcohol, isopropyl alcohol and the like, but water is particularly preferable.
When an aqueous emulsion or aqueous solution of the resin as described above is used, the solvent contained therein can be a part or all of the above medium.
Examples of the surfactant include the following.
Ionic surfactant:
Sodium dodecylbenzene sulfonate, sodium dialkyl sulfosuccinate, sodium lauryl sulfate, sodium polyoxyethylene alkyl ether sulfate, sodium polyoxyethylene alkyl phenyl ether sulfate, ammonium polyoxyethylene alkyl ether sulfate, ammonium polyoxyethylene alkyl phenyl ether sulfate, poly Oxyethylene alkyl ether phosphate, polyoxyethylene alkyl phenyl ether phosphate, lauryl trimethyl ammonium chloride, trimethyl octadecyl ammonium chloride, etc. Amphoteric surfactants:
Nonionic surfactants such as lauryl betaine and lauryl dimethylamine oxide;
Polyoxyethylene alkyl ether, polyoxyethylene alkyl allyl ether, polyoxyethylene oxypropylene block polymer, polyethylene glycol fatty acid ester, polyoxyethylene sorbitan fatty acid ester, etc. Cellulose-based thickeners such as hydroxyethyl cellulose and hydroxypropyl methyl cellulose; Polysaccharide-based such as saccharose and glucose; acrylic-based and the like can be mentioned.
In addition, various auxiliaries such as antifoaming agents, ultraviolet absorbers, antioxidants, and weather resistant agents may be blended according to the properties required for the printing recording material.

The coating liquid composition for forming a glossy layer is prepared by mixing an aqueous emulsion or aqueous solution of a titanium oxide-coated mica and a resin serving as a binder, and an optional component, if necessary, with an appropriate amount of a medium such as water. The materials and the medium may be charged all at once, or the titanium oxide-coated mica and the medium may be mixed and then the remaining materials may be charged. Alternatively, the aqueous emulsion or aqueous solution of the resin and the medium may be mixed and stirred, and then the remaining material may be added. Normally, since an aqueous emulsion or aqueous solution of a resin binder is used, it is not necessary to mix the medium, but a new medium may be added in order to improve wettability and the like. Mixing may be carried out according to a conventionally known method.
The amount of the binder blended in the coating liquid composition for forming a glossy layer is preferably such that the amount of the solid binder component in the glossy layer after complete solidification is 70% by mass or less and 15% by weight or more in consideration of the evaporating medium. Is adjusted so that.
The viscosity of the coating liquid composition for forming a glossy layer can be adjusted by the blending amount of the binder, the medium, and the thickener, and is usually set to 5 to 100 Pa · s.

The coating method for the coating liquid composition for forming a glossy layer can be applied to the surface of the substrate such as a blade coater, an air knife coater, a roll coater, a bar coater, a gravure coater, a rod blade coater, a lip coater, a curtain coater, and a die coater. It is coated using a conventionally known coating device.
The coating liquid composition for forming a glossy layer is usually coated in consideration of evaporation of the medium so that the average thickness of the glossy layer after drying is 20 μm or more and 400 μm or less. The average thickness of the glossy layer and the ink receiving layer described later was measured with a digital micrometer (manufactured by Mitutoyo, model number: MDC-25MX) in accordance with JIS P8118.
The drying after coating may be carried out by a known method such as natural drying or heat drying. Heat drying is preferable from the viewpoint of drying in a short time, and heating at 40 to 120 ° C. is particularly preferable from the viewpoint that the base material and the glossy layer are not deformed.
The glossy layer formed through drying can be subjected to post-treatment such as a pressure press, if necessary.
Since the above-mentioned medium such as water evaporates after the above-mentioned drying, it is basically a component that does not remain in the glossy layer, but depending on the drying conditions, about 1% by mass is glossy immediately after the drying step is carried out. May remain in the layer. However, such a residual medium also becomes more volatilized with the storage and distribution of the printing recording material of the present invention, and substantially disappears at the time of use. Therefore, even if the medium is present in the glossy layer immediately after production, it is excluded when calculating the content ratio of titanium oxide-coated mica or binder.

<Ink receiving layer>
The ink receiving layer is a layer that contains the following specific particle-based inorganic particles and a resin binder as essential components and absorbs ink during printing to form a drawing.

<Inorganic particles>
The average particle size of the inorganic particles needs to be 0.1 μm or more and 1.0 μm or less. The average particle size of the inorganic particles is measured by a laser diffraction / scattering method as in the case of titanium oxide-coated mica.
When the average particle size of the inorganic particles is 0.1 μm or more, even if titanium oxide-coated mica having a large average particle size is used in the glossy layer, the glare is suppressed by the light scattering effect of the inorganic particles in the ink receiving layer. Not only is it possible, but in the printed image, both the surface reflected light on the printed surface and the internally reflected light reflected by the pearl-like gloss layer are visible, so the printed matter exhibits a sense of depth and pearl gloss at the same time. You can enhance the artistic quality. When the thickness is 1.0 μm or less, the composition for forming an ink receiving layer (described later) has good fluidity and dispersibility of inorganic particles, in addition to suppressing glare, so that the surface is smooth on the glossy layer. It is possible to form a high and uniform ink receiving layer.
The inorganic particles preferably have a solubility in water of 0.5 g / 100 g and water or less. When the solubility in water is 0.5 g / 100 g, which is higher than that of water, when the coating liquid composition for forming an ink receiving layer (described later) is applied and then dried, the dissolved inorganic substances are precipitated and are larger than 1 μm. It becomes particles, and the uniformity inside the ink receiving layer may be impaired.
Examples of the inorganic particles include zeolite, calcium silicate, kaolin, clay, barium sulfate, aluminum hydroxide, ceramic sand, glass beads, pearlite, silica, alumina monohydrate, calcium carbonate, calcium hydroxide and the like. can. In particular, silica, aluminum hydroxide, calcium carbonate, calcium hydroxide or alumina monohydrate is preferable because of its high whiteness.
The content of the inorganic particles in the ink receiving layer is 5% by mass or more and 30% by mass or less, particularly preferably 10% by mass or more and 20% by mass or less, based on the total amount of the ink receiving layer. If it is less than 5% by mass, the glossiness with a glaring feeling cannot be sufficiently suppressed. If it exceeds 30% by mass, the glossiness is lowered more than necessary.

<Resin binder>
A resin binder is blended in the ink receiving layer in order to uniformly disperse the inorganic particles and to bond the glossy layer and the ink receiving layer.
In order not to impair the gloss characteristics of the gloss layer, it is preferable that the ink receiving layer located on the gloss layer is also a binder having a certain level of transparency. Therefore, a resin binder is used as the binder in the ink receiving layer.
The content of the resin binder in the ink receiving layer is preferably an amount such that the amount of the binder in the ink receiving layer after complete solidification is 60% by mass or more and 85% by mass or less based on the total amount of the ink receiving layer. .. If the amount of the binder is less than the above lower limit, the adhesiveness between the gloss layer and the ink receiving layer and the dispersibility in the layer of the inorganic particles may decrease. If the upper limit is exceeded, ink penetration may be hindered and a clear image may not be sufficiently obtained.
As the resin binder, the same type as the resin used for the glossy layer described above is used without particular limitation. The resin binder in the glossy layer and the resin binder in the ink receiving layer may have the same resin type or different resin types.

<Formation of ink receiving layer>
The coating liquid composition for forming an ink receiving layer is applied to the surface of the glossy layer described above, and then an ink receiving layer is formed through a drying step.
The coating liquid composition for forming an ink receiving layer has an essential component of inorganic particles and a resin binder, as well as a medium for facilitating coating on the surface of the glossy layer and a high amount for stably and uniformly dispersing the inorganic particles. Molecular dispersant, ink fixer to prevent ink bleeding and improve water resistance, and thickener, defoamer, ultraviolet absorber, antioxidant, weather resistance to be blended in the glossy layer mentioned above. Various auxiliary agents such as sex agents can be used as needed.

As the resin binder and medium to be used, those disclosed in the above-mentioned formation of the glossy layer can be used as they are.
The polymer dispersant is preferably used in an amount of 0.5 to 10.0% by mass per ink receiving layer. If the amount used is too small, the effect of dispersing the inorganic particles may be insufficient, and if it is too large, the viscosity of the coating liquid composition for forming the ink receiving layer may change significantly with time and become unstable.
As the polymer dispersant, conventionally known ones can be used as long as they have a large molecular weight, are hydrophilic, and can effectively disperse inorganic particles.
Representative examples include lignin sulfonate, melamine sulfonate, naphthalene sulfonate, polycarboxylic acid salt, polycarboxylic acid copolymer and the like, and polycarboxylic acid salt or polycarboxylic acid copolymer is particularly preferable. The following can be exemplified as the polycarboxylic acid salt.
A salt of an ethylene-maleic anhydride copolymer or a partial ester thereof (see JP-A-1-92212); a salt of an allyl ether-maleic anhydride copolymer or a derivative thereof (see JP-A-63-285140); Salts of meta) acrylic acid- (meth) acrylic acid ester copolymers or derivatives thereof (see JP-A-58-74552, JP-A 1-2267757, etc.); Isobutylene-maleic anhydride copolymers or derivatives thereof. Salts (see JP-A-60-103062); examples of these polycarboxylic acid salts having an alkylene glycol chain graft-bonded to the side chains (see JP-A-2007-332027), and in particular, alkylene glycol chains. The polycarboxylic acids having the same are preferable, and the polycarboxylic acid salt having a mass average molecular weight of 1,000 to 100,000 is preferable.
The form of the salt includes an alkali metal salt, an alkaline earth metal salt, a lower amine salt, a lower alkanol amine salt and the like.
Typical examples of the ink fixing agent include cationic polymers, and conventionally known ones can be used without any limitation as long as they are dispersed and stable in the coating liquid composition for the ink receiving layer. Of these, a quaternary ammonium salt type cationic polymer is preferable.
Typical quaternary ammonium salt type cationic polymers include polydiallyldimethylammonium chloride; derivatives of diallyldimethylammonium chloride; quaternary ammonium salt type cationic polymers including a polyurethane skeleton; and skeletons of acrylic esters and acrylic ester derivatives. Quaternary ammonium salt type cationic polymers including; and the like. In particular, derivatives of polydiallyldimethylammonium chloride and diallyldimethylammonium chloride are preferable.
The ink fixing agent is preferably used in an amount of 0.2 to 5.0% by mass per ink receiving layer. If the amount used is too small, the effect tends not to be sufficiently exhibited, and if it is too large, the viscosity of the coating liquid composition for forming an ink receiving layer tends to change significantly with time, and various components tend to separate.

The coating liquid composition for forming an ink receiving layer is prepared by mixing inorganic particles, a transparent binder, and an optional component with an appropriate amount of a medium such as water. The mixing method, the viscosity of the liquid composition, and the like are the same as those of the coating liquid composition for forming a glossy layer. The method of applying the coating liquid composition for forming an ink receiving layer to the surface of the glossy layer can be carried out in the same manner as the coating liquid composition for forming a glossy layer.
The coating liquid composition for forming an ink receiving layer is usually coated in consideration of evaporation of the medium so that the average thickness of the glossy layer after drying is 20 μm or more and 200 μm or less. Drying after coating can be performed in the same manner as in the case of forming a glossy layer.
The ink receiving layer formed through drying can be subjected to post-treatment such as a pressure press, if necessary.
The possibility that the medium may remain even after the drying is the same as in the case of forming the glossy layer, and the same applies to the point that the remaining medium is excluded in the content of each component.

<Printing>
The printing recording material of the present invention can be used as an exhibition printed matter such as a photographic print or a graphic work print by printing an image or the like on the surface thereof by various printing methods such as inkjet printing and screen printing. It is particularly preferable to use a non-contact inkjet printer for printing.
As the ink, a dye ink or a pigment ink can be used, and good color development, print density, and a clear image can be obtained, and a water-based pigment ink in which the pigment is dispersed in an aqueous medium is particularly preferable.

Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples. Also, not all combinations of features described in the examples are essential to the solution of the present invention.
The various raw material components, abbreviations, and evaluation methods used in the following examples and comparative examples are as follows.

<Evaluation of artistic quality>
With respect to the printing recording material and the printed matter thereof obtained in Examples and Comparative Examples, pearly glossiness, artistic property, uniformity of printed image, and blurring of printed image (printing unevenness) were evaluated as follows. In the evaluation, printing on the printing recording material was performed using a commercially available inkjet printer (manufactured by Epson, product name: PX-5V, printing mode: photo matte paper / high definition).
[Pearl-like luster]
Ten professional photographers made a two-choice evaluation of "high-quality pearl-like luster" when viewed from an oblique 45-degree perspective on a blank sheet of unprinted paper. The evaluation criteria are as follows.
(Evaluation criteria)
◎ 9 or more positive evaluations ○ 7 to 8 positive evaluations △ 4 to 6 positive evaluations × 3 or less positive evaluations [artistic]
Solid printing of black, cyan, magenta, yellow, red, and blue is performed, and 10 professional photographers perform "light interference" caused by multi-layer reflection of light when viewed from an angle of 45 degrees to the printing surface. A two-choice evaluation was made on the "artistic quality obtained by". The evaluation criteria are as follows. Depth (sense of depth) and fluctuation can be evaluated by the artistic nature.
(Evaluation criteria)
◎ 9 or more positive evaluations ○ 7 to 8 positive evaluations △ 4 to 6 positive evaluations × 3 or less positive evaluations [Uniformity of printed images]
For each color solid printing portion of black, cyan, magenta, yellow, red, and blue, the color uniformity of each printed area was visually evaluated from the line of sight perpendicular to the printing surface according to the following criteria.
◯: Each color is even and uniform.
Δ: Some colors are uneven, but there is no problem in practical use.
×: Most of the colors are uneven and there is a problem in practical use.
[Blur of printed image border]
Five color combinations of black-cyan, magenta-yellow, red-yellow, red-blue, and magenta-blue are printed at 5 cm squares adjacent to each other, and color bleeding at the boundary of each color combination. The degree was visually observed and evaluated according to the following criteria.
◯: No bleeding is seen in each color combination.
Δ: There is slight bleeding in any combination of colors, but there is no problem in practical use.
X: Blurring is seen in any of the color combinations. There is a problem in practical use.

<Ingredients>
[Base material]
Base material A: Resin-coated paper (manufactured by Nippon Paper Papylia Co., Ltd., product name: OPER, average thickness: 0.13 mm, basis weight: 115 g / m ² , pulp paper whose surface is coated with resin)
[Titanium oxide coated mica]
Coated mica A: Synthetic white pearl mica (manufactured by CQV, product name: Reflex Super Crystal White R-900P, average particle size d50: 65 μm)
Coated mica B: Synthetic white pearl mica (manufactured by CQV, product name: Reflex Super Glitter Pearl R-900G, average particle size d50: 100 μm)
Coated mica C: Synthetic white pearl mica (manufactured by CQV, product name: Reflex Ultra Glitter Pearl R-900H, average particle size d50: 230 μm)
[Inorganic particles]
Inorganic particle A: Calcium hydroxide slurry (manufactured by Tokuyama Corporation, product name: calcetter, average particle diameter d50: 0.28 μm, solid content concentration: 45%)
Inorganic particle B: Alumina monohydrate (manufactured by Taimei Chemicals Co., Ltd., product name: boehmite C-01, average particle diameter d50: 0.72 μm)
[binder]
Binder A: Acrylic copolymer emulsion (manufactured by Asahi Kasei Kogyo Co., Ltd., product name: Polytron A1480, solid content concentration: 40% by mass)
Binder B: Polyvinyl alcohol (manufactured by Kuraray Co., Ltd., product name: Kuraray Poval 5-98, saponification degree: 98 to 99 mol%)
[Thickener]
Thickener A: Carboxymethyl cellulose (manufactured by Nippon Paper Industries, Ltd., product name: Sunrose FT-3, powder)
[Ink fixer]
Fixing agent A: Water-soluble quaternary ammonium salt polymer (manufactured by Senka, product name: Papiogen P-105, solid content concentration: 60% by mass)

Example 1
Each raw material component was mixed at the blending ratio shown in Table 1 to prepare a coating liquid composition for forming a glossy layer, and the coating liquid composition was applied onto the base material A using a bar coater. Next, it was placed in a blower constant temperature dryer, heated at 70 ° C. for 2 hours, and dried to prepare a glossy layer laminate (a). Table 1 shows the solid content composition and thickness of the formed glossy layer.

Each raw material component was mixed at the blending ratio shown in Table 2 to prepare a coating liquid composition for forming an ink receiving layer, and the coating was applied onto the glossy layer laminate (a) using a bar coater. Next, it was placed in a blower constant temperature dryer, heated at 70 ° C. for 2 hours, and dried to prepare a printing recording material (A). Table 2 shows the solid content composition and thickness of the formed ink receiving layer.

Various characteristics of the obtained printing recording material (A) were measured according to the evaluation method, and the results are shown in Table 3.

Examples 2-12
Printing recording materials (B to L) were prepared with the material components and compounding ratios shown in Tables 1 and 2, and various characteristics were measured in the same manner, and the results are shown in Table 3.

Comparative Example 1
In Example 1, the coated mica A was changed to synthetic white pearl mica (manufactured by CQV, product name: Reflex Dazzling Standard R-900S, average particle size d50: 22 μm), but the same procedure was carried out in the same manner as for the print recording material (M). ) Was prepared and its characteristics were evaluated. The results are shown in Table 3. The thickness of the glossy layer was 50 μm, and the thickness of the ink receiving layer was 21 μm. Since the average particle size of the titanium oxide-coated mica was small, the pearl-like glossiness was insufficient, and the printed image was poorly artistic.

Comparative Example 2
In Example 1, the coated mica A was changed to synthetic white pearl mica (manufactured by CQV, product name: Reflex Super Ultra Glitter Pearl R-901J, average particle size d50: 413 μm), and the same was performed as the print recording material. (N) was prepared and its characteristics were evaluated. The results are shown in Table 3. The thickness of the glossy layer was 312 μm, and the thickness of the ink receiving layer was 33 μm. Since the average particle size of the titanium oxide-coated mica was large, the glossy layer could not be applied uniformly, and the obtained print recording material lacked the uniformity of the printed image.

Comparative Example 3
In Example 5, the blending amount of the inorganic particles A was reduced, and the solid content composition was 4% by mass of the inorganic particles A, 93% by mass of the binder B, and 3% by mass of the cationic polymer. A print recording material (O) was prepared and its characteristics were evaluated in the same manner except that the material was adjusted. The results are shown in Table 3. The thickness of the glossy layer was 322 μm, and the thickness of the ink receiving layer was 20 μm. If the amount of the inorganic particles added to the ink receiving layer was too small, the obtained print recording material could not suppress the glare of the pearly luster, and the printed image was poor in artistic quality.

Comparative Example 4
In Example 7, except that the solid content composition of the coating liquid composition for forming the ink receiving layer was 46% by mass of the inorganic particles, 51% by mass of the binder, and 3% by mass of the cationic polymer by increasing the blending amount of the inorganic particles. In the same manner, a printing recording material (P) was prepared and its characteristics were evaluated. The results are shown in Table 3. The thickness of the glossy layer was 90 μm, and the thickness of the ink receiving layer was 39 μm. When the inorganic particles were excessively present in the ink receiving layer, the pearly luster was lost and the printed image was poorly artistic.

Comparative Example 5
In Example 7, the printing recording material (Q) was carried out in the same manner except that the inorganic particles B were changed to calcium carbonate (manufactured by Omi Mining Co., Ltd., product name: powdered charcoal LP-200, average particle size d50: 14 μm). ) Was prepared and its characteristics were evaluated. The results are shown in Table 3. The thickness of the glossy layer was 90 μm, and the thickness of the ink receiving layer was 48 μm. Due to the large particle size of the inorganic particles, the pearly glossiness was insufficient, and the printed image was poorly artistic. Further, the ink receiving layer could not be applied uniformly, and the obtained print recording material lacked the uniformity of the printed image, and bleeding occurred.

Comparative Example 6
The same applies to Example 5 except that the inorganic particles are changed to colloidal silica (manufactured by Nissan Chemical Industries, Ltd., product name: Snowtex ST-50-T, solid content concentration: 48% by mass, average particle size d50: 22 nm). A print recording material (R) was prepared and its characteristics were evaluated. The evaluation results are shown in Table 3. The thickness of the glossy layer was 351 μm, and the thickness of the ink receiving layer was 22 μm. If the particle size of the inorganic particles in the ink receiving layer is too small, the obtained print recording material cannot suppress the glaring feeling of pearly luster, and the printed image is poor in artistic quality.

Claims (4)

A printing recording material in which a glossy layer and an ink receiving layer are laminated in this order on at least one surface of a substrate.
The glossy layer contains a resin binder and titanium oxide-coated mica whose surface of mica particles is coated with titanium oxide, and the average particle size of the titanium oxide-coated mica is 50 μm or more and 300 μm or less, and the titanium oxide-coated mica has an average particle diameter of 50 μm or more and 300 μm or less. The content is 20% by mass or more and 80% by mass or less based on the total amount of the glossy layer (100% by mass).
The ink receiving layer contains a resin binder and inorganic particles, the average particle size of the inorganic particles is 0.1 μm or more and 1.0 μm or less, and the content of the inorganic particles is based on the total amount of the ink receiving layer ( The printing recording material, which is 5% by mass or more and 30% by mass or less as 100% by mass). The printing recording material according to claim 1, wherein the solubility of the inorganic particles in water is 0.5 g / 100 g / water or less. The printing recording material according to claim 1 or 2, wherein the thickness of the glossy layer is 20 μm or more and 400 μm or less, and the thickness of the ink receiving layer is 20 μm or more and 200 μm or less. A printed matter drawn with ink on the printing recording material according to any one of claims 1 to 3.

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