JP2009233924A - Inkjet recording medium and inkjet recording method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an inkjet recording medium which can give a feeling of matte-toned coated paper for offset printing at low cost and also, successful printing quality, with superior ink absorbency and fretting resistance. <P>SOLUTION: This inkjet recording medium has an ink receptive layer consisting of a binder containing an acrylonitrile-butadiene-based copolymer with a butadiene content of not less than 50 mass%, and an inorganic pigment, formed on one side or both sides of a base paper composed mainly of wood pulp. In addition, the content ratio of the acrylonitrile-butadiene-based copolymer for 100 pts.mass of the inorganic pigment, is not less than 1 pts.mass to not more than 8 pts.mass, and it is kaolin that accounts for not less than 60 mass% of the inorganic pigment, and contains a particle, measuring not less than 0.4 μm to less than 4.2 μm by the laser diffraction process, which is equivalent to not less than 64% in terms of a squaring value by a volume standard. The inkjet recording medium is not calendered after coating. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a mat-like inkjet recording medium having a texture of matte-coated paper for offset printing and an inkjet recording method for performing inkjet recording using the same.

  The ink jet recording method is easy to make full color and has little printing noise. Therefore, the ink jet recording method has been used in many applications as the printing performance is rapidly improved. These applications include, for example, document recording from document creation software, recording of digital images such as digital photographs, reproduction of beautiful printed materials such as silver halide photographs and books captured by a scanner, and a relatively small number of posters. For example, creating an image for exhibition. In particular, in recent years, in the commercial printing field of small lots and many varieties, printing is often performed by an ink jet recording method instead of an offset printing method.

  Ink jet recording media having configurations suitable for these applications have been proposed. For example, when simply recording characters, a plain paper type medium that directly records on the paper surface is used. In addition, when it is desired to obtain resolution and color reproducibility comparable to silver halide photography, it is necessary to absorb the ink ejected from the printer, so a coated paper type provided with an ink receiving layer as the coating layer is used. . When particularly high glossiness is required, a cast paper type in which a coating layer is formed by, for example, a cast method is used among the coated paper types. On the other hand, in the case of posters and display applications, a roll type having a thick coating layer has been developed and used.

Usually, when obtaining a fine image as a printed matter, a matte ink jet recording paper is used. However, these matte ink jet recording papers have different textures such as glossiness and tactile sensation than offset matte coated paper for offset printing, so that printed matter such as offset printed matter represented by magazines and catalogs can be obtained. difficult. Therefore, there is often a demand for a mat-like ink jet recording paper having a texture of matte-coated paper for offset printing.
Further, in general, in ink jet printing, the amount of ink used increases as the color reproducibility of an image is improved, so a larger ink absorption capacity is required for the ink receiving layer. For this reason, porous materials such as synthetic amorphous silica are often used for the ink receiving layer. In this case, the ink absorbability is improved, but there is a problem that the texture is different from the offset printed matter. Furthermore, these inkjet recording media generally use a large amount of, for example, silica, alumina, polyvinyl alcohol, ethylene vinyl acetate emulsion, ink fixing agents (polyamine, DADMAC, polyamidine, etc.) as expensive raw materials. Compared with coated paper for offset printing, the manufacturing cost is higher.

  On the other hand, when printing on general offset matte coated paper with an inkjet printer, the ink absorption capacity of the coating layer is low, so feathering (bleeding), bleeding (color boundary bleeding), and solid printing Defects such as unevenness (printing density unevenness) and cockling (waviness of the printed part) occur.

Therefore, as an inkjet recording medium having a texture of coated paper for offset printing, the recording layer (coating layer) has an average particle diameter of 0.2 to 2.0 μm and 1 ≦ L / W ≦. The composition has kaolin satisfying 50 (L represents the long diameter of the particle, W represents the short diameter (thickness) of the particle) as a pigment, and the 75 ° glossiness of the recording layer surface according to JIS-Z-8741 is 40% or more Is disclosed (for example, see Patent Document 1).
Moreover, as offset printing paper having ink jet aptitude, it has a pigment coating layer (coating layer) having kaolin as a main component and a predetermined cobb size (water absorption), and a cationic resin is applied to this pigment coating layer. A structure impregnated with coating is disclosed (for example, see Patent Document 2). Also, an inkjet in which a two-layer ink receiving layer comprising a lower layer mainly composed of kaolin and amorphous synthetic silica and an upper layer mainly composed of metal oxide fine particles produced by a vapor phase method is provided on a support. A recording medium is disclosed (for example, see Patent Document 3).

  Further, as an ink jet recording paper containing SBR (styrene butadiene copolymer) in the binder of the ink receiving layer, the film base support contains needle columnar orthorhombic aragonite calcium carbonate as a pigment, and a binder. As a recording sheet provided with an ink receiving layer containing an epoxy resin and a styrene butadiene copolymer resin (see Patent Document 4), 5 to 55% by weight of the binder component in the ink receiving layer is styrene butadiene latex. And 20 to 45% by weight of the recording medium (Patent Document 5) derived from a butadiene monomer, clay as a pigment of the ink receiving layer and calcium carbonate having a specific oil absorption amount, and acrylamide as a binder / Copolymers of diallylamine and styrene butadiene Recording paper containing a polymer (Patent Document 6) have been disclosed.

JP 2004-209965 A JP 2004-270104 A JP 2005-103827 A Japanese Patent Laid-Open No. 4-250092 JP-A-9-11613 JP 2004-82464 A

However, when printing is performed with an inkjet printer using the coated paper described in Patent Document 1, Patent Document 2, and Patent Document 6, the ink absorbability is not sufficient, the scratch resistance of the printed portion is inferior, and the print quality is good. May not be able to get.
In addition, although the ink jet recording medium of Patent Document 3 can provide a texture similar to that of the A2 coat, the manufacturing cost is high because the ink receiving layer has two layers.
Further, the recording paper described in Patent Document 4 has a problem that it completely differs from the texture of matte-coated paper for offset printing because the support is a film. Furthermore, the recording medium described in Patent Document 5 has a problem that it is completely different from the texture of matte coated paper for offset printing because the pigment of the ink receiving layer is silica.
Accordingly, an object of the present invention is to provide an ink jet recording medium that can obtain a texture of matte coated paper for offset printing at low cost, has excellent ink absorbability, has excellent scratch resistance of a printed portion, and provides good print quality. There is to do.

  As a result of intensive studies on a configuration suitable for inkjet printing and capable of obtaining a texture of matte coated paper for offset printing, the present inventors have found that the kind of pigment and binder in the ink receiving layer, the content ratio of pigment and binder, and the ink It has been found that the above problem can be solved by defining the surface roughness of the receiving layer.

  That is, the ink jet recording medium of the present invention contains a binder containing an acrylonitrile butadiene copolymer having a butadiene content of 50% by mass or more on one or both sides of a base paper mainly composed of wood pulp, and an inorganic pigment. An ink receiving layer, wherein the content ratio of the acrylonitrile butadiene copolymer to 100 parts by mass of the inorganic pigment is 1 part by mass or more and 8 parts by mass or less; The ink receiving layer when particles having a particle size of 0.4 μm or more and less than 4.2 μm occupy 64% or more of the integrated value on a volume basis when measured by the above and the hard pressure is used with a clamp pressure of 1000 kPa according to JIS P8151 Is an ink jet recording medium having a surface roughness of more than 1.4 μm and not more than 5 μm.

  The white paper glossiness at a light incident angle of 75 degrees according to JIS Z8741 on the surface of the ink receiving layer is preferably 20% or more and less than 55%.

  The inkjet recording method of the present invention is characterized in that an image is recorded on the inkjet recording medium using an ink containing at least water, a particulate colorant, and a wetting agent.

  According to the present invention, it is possible to obtain an ink jet recording medium which can obtain a texture of (A2) mat coated paper for offset printing at low cost, has excellent ink absorbability, excellent scratch resistance of a printed portion, and good print quality. It is done.

  Hereinafter, embodiments of an ink jet recording medium according to the present invention will be described.

(Base paper)
The base paper is mainly composed of wood pulp. Pulp such as chemical pulp (conifer bleached or unbleached kraft pulp, hardwood bleached or unbleached kraft pulp), mechanical pulp (ground pulp, thermomechanical pulp, chemical thermomechanical pulp, etc.), deinked pulp, etc. Can be used alone or in admixture at any ratio.
The pH at the time of papermaking of the base paper may be any of acidic, neutral and alkaline. Further, since the opacity of the paper tends to improve as the amount of the filler in the base paper increases, it is preferable to contain the filler in the paper. As the filler, known fillers such as hydrated silicic acid, white carbon, talc, kaolin, clay, calcium carbonate, titanium oxide, synthetic resin filler and the like can be used. Furthermore, the base paper may contain auxiliary agents such as a sulfuric acid band, a sizing agent, a paper strength enhancer, a yield improver, a colorant, a dye, an antifoaming agent, and a pH adjuster as necessary. The basis weight of the base paper is not particularly limited.

  Before providing the ink receiving layer, a base press may be impregnated or coated with a size press solution prepared from starch, PVA, sizing agent, etc. for the purpose of enhancing paper strength and imparting size. The impregnation or coating method is not particularly limited, but may be performed by an impregnation method typified by a pound type size press or an application method typified by a rod metering size press, a gate roll coater, or a blade coater. preferable. In addition, the size press liquid is a fluorescent dye, a conductive agent, a water retention agent, a water resistance agent, a pH adjuster, an antifoaming agent, a lubricant, a preservative, as necessary, as long as the effects of the present invention are not impaired. An auxiliary agent such as a surfactant can be mixed in an arbitrary ratio.

(Ink receiving layer)
1. Pigment of ink-receiving layer The pigment of the ink-receiving layer contains kaolin in which particles of 0.4 μm or more and less than 4.2 μm account for 64% or more by volume-based integrated value when measured by a laser diffraction method. Kaolin is a clay containing at least one kind of kaolin mineral such as kaolinite, halloysite, dickite and nacklite, and any known kaolin used for general coated paper for offset printing may be used. Examples of kaolin include Georgia, Brazil, and China, and grades such as grade 1, grade 2, and delami. However, kaolin is not limited to these. Moreover, what mixed 1 type or 2 or more types of kaolin can be selected suitably, and can be used as a pigment.
Measurement of the particle size distribution by the laser diffraction method uses the light scattering phenomenon, and is obtained by Mie theory and the Fraunhofer approximation. However, since the method for calculating the particle size distribution from the scattered light differs depending on the particle size measuring device, in the present invention, the laser method particle size measuring device (Malvern Mastersizer S type, the light source is red light of 633 nm (He-Ne laser) Use the value measured by blue light 466nm (LED)).
As a method for measuring the particle size distribution, a sample dispersion containing a sample slurry containing kaolin in pure water is used as a sample.

  The particle size distribution of kaolin used in general coated paper for offset printing, etc., extends in the range of about 0.05 μm to about 40 μm. For example, the particle size of KCS (product name of Kaolin manufactured by Imeris) Distribution is a volume-based integrated value of 53% of particles having a particle size of 0.4 μm or more and less than 4.2 μm, 21% of particles having a particle size of less than 0.4 μm, and 26% of particles having a particle size of 4.2 μm or more. It is. As a result of intensive studies by the present inventors, when kaolin having a particle size distribution concentrated in a range of 0.4 μm or more and less than 4.2 μm (64% or more) is used, the ink absorbability is higher than that of the general kaolin described above. It turned out to be excellent. This is because if the particle size distribution is concentrated in the above range, the width of the particle size distribution is narrow and the particle diameter is uniform, so that the packing density of the pigment particles is low, and a porous and bulky ink receiving layer can be formed. Conceivable. A porous ink-receiving layer is more excellent in ink absorbency than an ink-receiving layer with a densely packed pigment.

On the other hand, when kaolin having a particle size distribution in which particles of 0.4 μm or more and less than 4.2 μm are less than 64% in terms of volume-based integrated value is used instead of kaolin having the above particle size distribution, the particle size distribution of kaolin is broad. Therefore, kaolin is densely packed in the ink receiving layer, and the ink absorbability is lowered.
That is, kaolin having a particle size distribution in which particles of 0.4 μm or more and less than 4.2 μm are less than 64% in terms of volume-based integrated values, and kaolin containing many particles having a particle diameter of less than 0.4 μm was used. In this case, since the ink receiving layer becomes dense, ink absorbability is lowered.
Further, kaolin having a particle size distribution in which particles of 0.4 μm or more and less than 4.2 μm are less than 64% in terms of volume-based integrated value, and kaolin containing many particles having a particle diameter of 4.2 μm or more was used. In this case, since the number of pores formed on the coated paper surface is reduced, the number of ink absorption channels is reduced, and the ink absorption is inferior.

  When the total amount of inorganic pigments contained in the ink receiving layer is 100 parts by mass, the content of kaolin having the above-described particle size distribution needs to be 60 parts by mass or more. When the kaolin content is less than 60 parts by mass, the above-described effects caused by the kaolin having the particle size distribution described above are hardly exhibited. The kaolin content is preferably 70 parts by mass or more, and the kaolin content is most preferably 100 parts by mass (100% of the inorganic pigment contained in the ink receiving layer is kaolin).

  As the inorganic pigment other than kaolin used in the ink receiving layer, any known inorganic pigment used in general coated paper for offset printing can be used. As inorganic pigments, for example, kaolin different from the particle size distribution described above, heavy calcium carbonate, light calcium carbonate, silica composite calcium carbonate, talc, calcined kaolin obtained by calcining the kaolin, calcium sulfate, barium sulfate, titanium dioxide, zinc oxide In addition, one or more kinds of inorganic pigments such as alumina, magnesium carbonate, magnesium oxide, silica, calcium silicate, bentonite, zeolite, sericite, and smectite can be appropriately selected and used.

2. Binder for ink receiving layer The binder used for the ink receiving layer contains an acrylonitrile butadiene copolymer having a butadiene content of 50% or more. The butadiene content referred to here is the weight percent of the butadiene monomer in the total monomer composition when the acrylonitrile butadiene copolymer is produced.
The acrylonitrile butadiene copolymer used in the present invention is mainly composed of an aliphatic conjugated diene monomer and a vinyl monomer, and a vinyl cyanide compound is mainly used as the vinyl monomer. A vinyl monomer other than the water-soluble ethylene monomer and the vinyl cyanide compound may be contained. The glass transition point of the acrylonitrile butadiene copolymer is at least one in the range of −100 to 50 ° C., and is usually produced as an emulsion having an average particle size of 50 to 150 nm.

Examples of the aliphatic conjugated diene monomer include 1,3-butadiene, isoprene, chloroprene, 2,3-dimethyl-1,3-butadiene, and preferably 1,3-butadiene. These aliphatic conjugated diene monomers can be used alone or in admixture of two or more. Examples of the vinyl cyanide compound include (meth) acrylonitrile, α-chloroacrylonitrile, vinylidene cyanide, and acrylonitrile is particularly preferable.
Examples of the water-soluble ethylene monomer include unsaturated carboxylic acid monomers such as (meth) acrylic acid, maleic acid, fumaric acid, and itaconic acid; (meth) acrylamide, N, N-dimethyl (meth) acrylamide Amide group-containing vinyl monomers such as N, N-dimethylaminopropyl (meth) acrylamide and N-methylol (meth) acrylamide; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3 -Hydroxyl group-containing vinyl monomers such as hydroxypropyl (meth) acrylate; epoxy group-containing vinyl monomers such as glycidyl (meth) acrylate and allyl glycidyl ether. These water-soluble ethylene monomers can be used alone or in admixture of two or more.

  Examples of vinyl monomers other than vinyl cyanide compounds include aromatic vinyl compounds, substituted or unsubstituted alkyl (meth) acrylates, vinyl acetate, and the like. Among these, examples of the aromatic vinyl compound include styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, and the like. In particular, styrene is preferable. Examples of the alkyl (meth) acrylates include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, i -Butyl (meth) acrylate, sec-butyl (meth) acrylate, t-butyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, cyclohexyl (meta ) Acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, 2-cyanoethyl (meth) acrylate and the like, and methyl methacrylate is particularly preferable.Vinyl monomers other than these vinyl cyanide compounds can be used alone or in admixture of two or more.

When the average particle size of the acrylonitrile butadiene copolymer used in the present invention is smaller than 50 nm, the fluidity and glossiness when used as a paper coating material are reduced, while the average particle size is less than 150 nm. Even if it is large, the high-speed fluidity tends to decrease when a paper coating composition is obtained. The average particle size of the acrylonitrile butadiene copolymer can be controlled by adjusting the amount of water, emulsifier, polymerization initiator and the like used during polymerization.
Also, when the glass transition point of the acrylonitrile butadiene copolymer used in the present invention is less than −100 ° C., the adhesive strength becomes strong, but the stickiness is inferior (stickiness is large). There is a concern that this may occur. On the other hand, when the glass transition point is higher than 50 ° C., the stickiness is excellent (stickiness is small), but there is a concern that the adhesive strength becomes insufficient. In particular, the glass transition point is preferably smaller than 0 ° C. in terms of improving the scratch resistance of the printed part. The glass transition point of the acrylonitrile butadiene copolymer can be controlled by the monomer composition at the time of production.

In particular, the greater the butadiene content in the acrylonitrile butadiene-based copolymer, the better the flexibility and elongation of the resulting copolymer, which is preferable in terms of impact resistance and adhesive strength. Since stickiness deteriorates, there is a concern that roll stains or the like may occur during the production of coated paper. This is because the glass transition temperature of butadiene is generally very low (around −90 ° C.), and the stickiness of the coating layer surface increases when used as a binder.
For this reason, the preferable butadiene content rate in an acrylonitrile butadiene type copolymer is 50-60 mass%.
In addition, the acrylonitrile content in the acrylonitrile butadiene-based copolymer is not particularly limited, but the higher the acrylonitrile content, the less the stickiness of the resulting copolymer is prevented. This is preferable. However, when there is too much acrylonitrile content rate, a copolymer will become hard too much and adhesive strength will be inferior. This is presumably because the glass transition temperature of polyacrylonitrile is as high as about 105 ° C. and the adhesive strength is lowered, so that the coating layer strength is weakened.
For this reason, the acrylonitrile content in the acrylonitrile butadiene-based copolymer is preferably 20 to 40%.

  When the total amount of the inorganic pigments contained in the ink receiving layer is 100 parts by mass, the content ratio of the acrylonitrile butadiene copolymer described above needs to be 1 part by mass or more and 8 parts by mass or less, and 2 parts by mass. The amount is preferably 6 parts by mass or less. Since the acrylonitrile butadiene copolymer in the ink receiving layer has a function as a binder, the smaller the content of this polymer, the more voids in the ink receiving layer and the better the ink absorbability. However, when the content of the acrylonitrile butadiene copolymer is less than 1 part by mass, the ink absorbability is good, but the strength of the ink receiving layer is insufficient, and paper dust is generated during cutting. On the other hand, when the content ratio of the acrylonitrile butadiene copolymer exceeds 8 parts by mass, the voids existing in the ink receiving layer are filled with the acrylonitrile butadiene copolymer, and the ink absorption capacity is reduced. It becomes difficult to obtain quality.

In the present invention, in addition to the acrylonitrile butadiene copolymer described above as a binder, other polymer compounds can be used. As a polymer compound, for example, one kind of starch such as oxidized starch, etherified starch, esterified starch, polyvinyl alcohol and modified products thereof, casein, gelatin, carboxymethylcellulose, polyurethane, vinyl acetate, and unsaturated polyester resin Two or more kinds can be appropriately selected and used, but these polymer compounds are preferably less than 30% by mass of the whole binder. When the content ratio of the acrylonitrile butadiene copolymer in the binder is less than 70% by mass, the strength of the ink receiving layer is inferior, paper dust is generated during cutting, and the scratch resistance of the printed part tends to decrease. .
In particular, when starch is blended as a binder, the hardness of the coating layer is improved and the pore structure in the coating layer is not easily destroyed.
When a plurality of polymer compounds are used as the binder of the ink receiving layer in addition to the acrylonitrile butadiene copolymer, the content ratio of the total binder with respect to 100 parts by mass of the inorganic pigment is The amount is preferably 8 parts by mass or less.

  In the present invention, as an inorganic pigment, the main component is kaolin in which particles of 0.4 μm or more and less than 4.2 μm account for 64% or more by volume integration when measured by a laser diffraction method, and the binder is acrylonitrile as described above. By containing a butadiene-based copolymer, it becomes possible to reduce paper dust at the time of cutting, and the scratch resistance of the printed portion when printed by an ink jet printer is improved. The reason for this is not clear, but the reduction of paper dust is because the acrylonitrile butadiene copolymer gives flexibility and elongation to the coating layer. This is considered to be because the binding property with the ink color material is improved due to the property.

(Other ingredients)
For the ink receiving layer, other organic pigments such as plastic pigments, pigment dispersants, printability improvers, thickeners, water retention agents, lubricants, antifoaming agents, foam suppressors, mold release agents, foaming, etc. Auxiliaries such as agents, colored dyes, colored pigments, fluorescent dyes, preservatives, water-resistant agents, surfactants, pH adjusters, and the like can be added as appropriate.
When the total amount of inorganic pigments contained in the ink receiving layer is 100 parts by mass, the proportion of the organic pigment is preferably 20 parts by mass or less.

(Surface roughness)
The surface roughness of the ink receiving layer when a hard backing is used with a clamp pressure of 1000 kPa according to JIS P8151 (paper and paperboard-surface roughness and smoothness test method (air leak method)-print surf tester method). Needs to be more than 1.4 μm and 5.0 μm or less. Here, JIS P8151 defines a method for measuring surface roughness using a Print-surf tester.
The greater the surface roughness, the better the ink absorbency. However, when the surface roughness exceeds 5.0 μm, the surface of the ink receiving layer becomes rough and a texture like A2 mat coated paper cannot be obtained. Further, when the surface roughness is small, the glossiness of the surface becomes too high, and when the surface roughness is 1.4 μm or less, a texture like A2 mat coated paper cannot be obtained. For this reason, the surface roughness of the ink receiving layer is defined within the above range. The surface roughness of the ink receiving layer is more preferably 3.0 μm or less.

As a first method for adjusting the surface roughness, there is a method in which calendar processing is not performed. In the present invention, by using the above-described pigment and binder in the above-mentioned ranges, an inkjet recording medium having a texture similar to that of A2 mat-coated paper and having high printability can be obtained without performing calendar treatment. Therefore, it can be manufactured at a lower cost than the conventional one.
Further, as a second method for adjusting the surface roughness, the pigment used in the ink receiving layer, the concentration of the paint, the coating amount, the coating method, and the like can be appropriately changed. For example, the surface roughness tends to increase by decreasing the coating concentration and decreasing the coating amount. Further, it is easier to increase the surface roughness by using the pre-metering coating method (curtain coating, gate roll coating, etc.) than the post-metering coating method (blade coating, etc.). In the case of the second adjustment method, calendar processing may be performed as necessary.

In general coated offset printing paper used is graded by coating weight, of high-quality paper (100% chemical pulp) based on both sides of the coating amount 20 g / m ² before and after the ones A2 coat It is called paper. Of the A2 coated paper, the one with high gloss is called A2 gloss coated paper, and the one with low gloss is called A2 mat coated paper. Examples of A2 matte coated paper include Oji Paper's New Age, OK Royal Court, Nippon Paper's Silver Diamond, Ulite, and Neptune.

(Air permeability resistance)
The air resistance of the ink jet recording medium of the present invention is not particularly limited, but is preferably 2200 seconds or less per side, particularly 2000 seconds or less. The lower the air resistance, the faster the ink permeates, and the better the ink absorbency. When the air permeation resistance exceeds 2200 seconds, the ink penetration is slow and the ink absorptivity is inferior. The air resistance can be adjusted by the amount of the binder in the ink receiving layer, the coating amount of the ink receiving layer, and the basis weight of the base paper. For example, by increasing the amount of the binder in the ink receiving layer, increasing the coating amount of the ink receiving layer and the basis weight of the base paper, the value of the air resistance increases.

(Coating amount)
The coating amount of the ink receiving layer is not formed in particular limitation, it is possible at one side per 2 g / ^{m 2} or more 40 g / ^{m 2} or less is preferable, and 5 g / ^{m 2} or more 30 g / ^{m 2} or less per side preferable. The greater the coating amount, the greater the amount of voids in the ink receiving layer, and the better the ink absorbability. When the coating amount of the ink receiving layer is less than 2 g / m ² per side, the base paper as a base material cannot be sufficiently coated, and the coated paper surface remains rugged and resembles non-coated paper There is a tendency that the texture of the matte coated paper for offset printing is difficult to obtain. On the other hand, when the coating amount is less than 2 g / m ² per side, the absorption capacity of the ink receiving layer tends to decrease, and printing defects such as feathering and bleeding tend to occur. On the other hand, when the coating amount of the ink receiving layer exceeds 40 g / m ² per side, the drying load during coating is large, so that workability tends to be inferior and the cost tends to be high.

(Coating method)
As a method for providing an ink receiving layer on a base paper, a general coating apparatus, a blade coater, a roll coater, an air knife coater, a bar coater, a gate roll coater, a curtain coater, a gravure coater, a flexographic gravure coater, and a spray coater. Various devices such as a size press can be used on-machine or off-machine. In addition, the ink receiving layer may be provided on one side or both sides, and one or more layers may be provided.

(Blank gloss)

The blank paper glossiness at a light incident angle of 75 degrees according to JIS Z8741 on the surface of the ink receiving layer is preferably 20% or more and less than 55%. In order to improve ink absorbability, the lower the glossiness of blank paper, the better. On the other hand, the glossiness of blank paper should not be too high in order to obtain the texture of matte coated paper for offset printing. Accordingly, the glossiness of blank paper is defined within the above range.
When the blank paper glossiness on the surface of the ink receiving layer is less than 20%, the texture of the matte coated paper for offset printing tends not to be obtained. On the other hand, even when the glossiness of the white paper exceeds 55%, the texture of the matte-coated paper for offset printing tends not to be obtained. More preferably, the blank paper glossiness on the surface of the ink receiving layer is 25% or more and 45% or less.
The white paper glossiness can be adjusted by appropriately selecting the pigment used in the ink demand layer, the paint concentration, the coating amount, the coating method, and the like.

  The ink jet recording medium of the present invention can be used not only as an ink jet recording system recording paper as described above, but also as an electrophotographic recording paper and an offset printing paper.

<Ink>
The ink used in the inkjet recording medium of the present invention contains at least water, a particulate colorant, and a wetting agent, and contains a penetrating agent, a surfactant, and other components as necessary. The thing which becomes.
The ink has a surface tension at 25 ° C. of 20 to 35 mN / m, and more preferably 23 to 34 mN / m. If the surface tension is less than 20 mN / m, bleeding on the recording medium of the present invention becomes noticeable, and stable ink ejection may not be obtained. If the surface tension exceeds 35 mN / m, ink on the recording medium may be obtained. Infiltration may not occur sufficiently, leading to beading and prolonged drying time.
Here, the said surface tension can be measured at 25 degreeC using a platinum plate, for example using a surface tension measuring apparatus (Kyowa Interface Science Co., Ltd. make, CBVP-Z).

(Coloring agent)
As the particulate colorant, it is preferable to use colored fine particles (colored pigment), and in the ink, the colorant is dispersed in a liquid component mainly composed of water and a wetting agent. In the ink jet recording medium of the present invention, a white pigment called kaolin, which has low transparency and high concealment, is used for the ink receiving layer. Therefore, when the so-called dye ink in which the colorant is dissolved in the liquid component in the ink is applied to the ink jet recording medium of the present invention, the colorant in the ink soaked in the ink receiving layer has high concealability. It is hidden by the white pigment, and a high image density does not appear. When ink-jet printing with a dye ink on a recording medium using such a highly concealed white pigment, no matter how much the amount of ink to be applied is increased, only the colorant present near the surface layer contributes to the image density. It becomes a low and non-contrast image, and it is difficult to obtain an image quality close to that of offset printing.

  On the other hand, when the so-called pigment ink in which the colorant is dispersed in the liquid component of the ink is applied to the inkjet recording medium of the present invention, the ink receiving layer serves as a filter that separates the colorant and the liquid component in the ink. In order to work, only the liquid component in the ink is selectively soaked in the inside of the receiving layer or the support, and the colorant in the ink is efficiently retained on the surface of the ink receiving layer, so that a sufficient image density can be obtained even with a small amount of ink. Can be obtained.

As the colored fine particles, an aqueous dispersion of fine polymer particles containing at least one colorant of pigment and dye is preferably used.
Here, the term “containing a color material” means either or both of a state in which the color material is enclosed in the polymer fine particles and a state in which the color material is adsorbed on the surface of the polymer fine particles. In this case, it is not necessary for all of the color material blended in the ink of the present invention to be encapsulated or adsorbed in the polymer fine particles, and the color material is dispersed in the emulsion as long as the effects of the present invention are not impaired. Also good. The color material is not particularly limited as long as it is water-insoluble or hardly water-soluble and can be adsorbed by the polymer, and can be appropriately selected according to the purpose.
Here, the “water-insoluble or hardly water-soluble” means that the coloring material does not dissolve 10 parts by mass or more with respect to 100 parts by mass of water at 20 ° C. Further, “dissolve” means that separation or sedimentation of the coloring material is not observed in the surface layer or the lower layer of the aqueous solution visually.

  The volume average particle diameter of the polymer fine particles (colored fine particles) containing the colorant is preferably 0.01 to 0.16 μm in the ink.

Examples of the colorant include dyes such as oil-soluble dyes, disperse dyes, and water-soluble dyes, and pigments. Oil-soluble dyes and disperse dyes are preferable from the viewpoint of good adsorptivity and encapsulation, but pigments are preferably used from the light resistance of the obtained image.
In addition, from the viewpoint of efficiently impregnating the polymer fine particles, each of the dyes is preferably dissolved in an organic solvent, for example, a ketone solvent in an amount of 2 g / liter or more, and more preferably 20 to 600 g / liter.
The water-soluble dye is a dye classified into an acid dye, a direct dye, a basic dye, a reactive dye, and a food dye in the color index, and preferably has excellent water resistance and light resistance. .

  Examples of the acid dyes and food dyes include C.I. I. Acid Yellow 17, 23, 42, 44, 79, 142; C.I. I. Acid Red 1,8,13,14,18,26,27,35,37,42,52,82,87,89,92,97,106,111,114,115,134,186,249,254 289; I. Acid Blue 9, 29, 45, 92, 249; I. Acid Black 1, 2, 7, 24, 26, 94; I. Food Yellow 3, 4; I. Food red 7, 9, 14; I. Food black 1, 2 etc. are mentioned.

  Examples of the direct dye include C.I. I. Direct yellow 1,12,24,26,33,44,50,86,120,132,142,144; I. Direct red 1,4,9,13,17,20,28,31,39,80,81,83,89,225,227; I. Direct orange 26, 29, 62, 102; I. Direct Blue 1, 2, 6, 15, 22, 25, 71, 76, 79, 86, 87, 90, 98, 163, 165, 199, 202; I. Direct black 19, 22, 32, 38, 51, 56, 71, 74, 75, 77, 154, 168, 171 and the like.

  Examples of the basic dye include C.I. I. Basic yellow 1, 2, 11, 13, 14, 15, 19, 21, 23, 24, 25, 28, 29, 32, 36, 40, 41, 45, 49, 51, 53, 63, 64, 65, 67, 70, 73, 77, 87, 91; C.I. I. Basic Red 2,12,13,14,15,18,22,23,24,27,29,35,36,38,39,46,49,51,52,54,59,68,69,70, 73, 78, 82, 102, 104, 109, 112; I. Basic blue 1,3,5,7,9,21,22,26,35,41,45,47,54,62,65,66,67,69,75,77,78,89,92,93, 105, 117, 120, 122, 124, 129, 137, 141, 147, 155; I. Basic black 2, 8 etc. are mentioned.

  Examples of the reactive dye include C.I. I. Reactive Black 3, 4, 7, 11, 12, 17; C.I. I. Reactive Yellow 1,5,11,13,14,20,21,22,25,40,47,51,55,65,67; I. Reactive Red 1,14,17,25,26,32,37,44,46,55,60,66,74,79,96,97; I. Reactive blue 1, 2, 7, 14, 15, 23, 32, 35, 38, 41, 63, 80, 95, and the like.

There is no restriction | limiting in particular as said pigment, According to the objective, it can select suitably, For example, any of an inorganic pigment and an organic pigment may be sufficient.
Examples of the inorganic pigment include titanium oxide, iron oxide, calcium carbonate, barium sulfate, aluminum hydroxide, barium yellow, cadmium red, chrome yellow, and carbon black. Among these, carbon black is preferable. In addition, as said carbon black, what was manufactured by well-known methods, such as a contact method, a furnace method, and a thermal method, is mentioned, for example.

  Examples of the organic pigment include azo pigments, polycyclic pigments, dye chelates, nitro pigments, nitroso pigments, and aniline black. Among these, azo pigments and polycyclic pigments are more preferable. Examples of the azo pigment include azo lakes, insoluble azo pigments, condensed azo pigments, and chelate azo pigments. Examples of the polycyclic pigment include phthalocyanine pigments, perylene pigments, perinone pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, indigo pigments, thioindigo pigments, isoindolinone pigments, and quinofullerone pigments. Examples of the dye chelates include basic dye chelates and acidic dye chelates.

There is no restriction | limiting in particular as a color of the said pigment, According to the objective, it can select suitably, For example, the thing for black, the thing for color, etc. are mentioned. These may be used individually by 1 type and may use 2 or more types together.
Examples of the black color include carbon black (CI pigment black 7) such as furnace black, lamp black, acetylene black, channel black, copper, iron (CI pigment black 11), oxidation, and the like. Examples thereof include metals such as titanium, organic pigments such as aniline black (CI pigment black 1), and the like.

As for the color, for yellow, for example, C.I. I. Pigment Yellow 1 (Fast Yellow G), 3, 12 (Disazo Yellow AAA), 13, 14, 17, 23, 24, 34, 35, 37, 42 (Yellow Iron Oxide), 53, 55, 74, 81, 83 (Disazo Yellow HR), 95, 97, 98, 100, 101, 104, 108, 109, 110, 117, 120, 128, 138, 150, 153, and the like.
For magenta, for example, C.I. I. Pigment Red 1, 2, 3, 5, 17, 22 (Brilliant First Scarlet), 23, 31, 38, 48: 2 (Permanent Red 2B (Ba)), 48: 2 (Permanent Red 2B (Ca)), 48 : 3 (Permanent Red 2B (Sr)), 48: 4 (Permanent Red 2B (Mn)), 49: 1, 52: 2, 53: 1, 57: 1 (Brilliant Carmine 6B), 60: 1, 63: 1, 63: 2, 64: 1, 81 (Rhodamine 6G Lake), 83, 88, 92, 101 (Bengara), 104, 105, 106, 108 (Cadmium Red), 112, 114, 122 (Dimethylquinacridone), 123, 146, 149, 166, 168, 170, 172, 177, 178, 179, 185, 190, 193, 209, 2 19, etc.
For cyan, for example, C.I. I. Pigment Blue 1, 2, 15 (copper phthalocyanine blue R), 15: 1, 15: 2, 15: 3 (phthalocyanine blue G), 15: 4, 15: 6 (phthalocyanine blue E), 16, 17: 1, 56, 60, 63 and the like.
In addition, as the intermediate colors for red, green and blue, C.I. I. Pigment red 177, 194, 224, C.I. I. Pigment orange 43, C.I. I. Pigment violet 3, 19, 23, 37, C.I. I. Pigment green 7, 36, and the like.

As the pigment, a self-dispersing pigment that can be stably dispersed without using a dispersant in which at least one hydrophilic group is bonded to the surface of the pigment directly or via another atomic group is suitably used. . As a result, unlike the conventional ink, a dispersant for dispersing the pigment becomes unnecessary. As the self-dispersing pigment, those having ionicity are preferable, and those having an anionic charge or those having a cationic charge are suitable.
The volume average particle size of the self-dispersing pigment is preferably 0.01 to 0.16 μm in the ink.

Examples of the anionic hydrophilic group include —COOM, —SO ₃ M, —PO ₃ HM, —PO ₃ M ₂ , —SO ₂ NH ₂ , —SO ₂ NHCOR (wherein M is a hydrogen atom) R represents an alkyl group having 1 to 12 carbon atoms, a phenyl group which may have a substituent, or a naphthyl group which may have a substituent. Can be mentioned. Among these, it is preferable to use those in which —COOM and —SO ₃ M are bonded to the surface of the color pigment.

  Further, “M” in the hydrophilic group includes, for example, lithium, sodium, potassium and the like as an alkali metal. Examples of the organic ammonium include mono to trimethyl ammonium, mono to triethyl ammonium, and mono to trimethanol ammonium. As a method of obtaining the anionically charged color pigment, as a method of introducing —COONa to the color pigment surface, for example, a method of oxidizing the color pigment with sodium hypochlorite, a method of sulfonation, a diazonium salt The method of making it react is mentioned.

  As the cationic hydrophilic group, for example, a quaternary ammonium group is preferable, and one in which any of these is bonded to the pigment surface is suitable as a coloring material.

  The method for producing the cationic self-dispersing carbon black to which the hydrophilic group is bonded is not particularly limited and may be appropriately selected depending on the intended purpose. For example, N— represented by the following structural formula Examples of the method for bonding the ethylpyridyl group include a method of treating carbon black with 3-amino-N-ethylpyridinium bromide.

The hydrophilic group may be bonded to the surface of carbon black through another atomic group. Examples of other atomic groups include an alkyl group having 1 to 12 carbon atoms, a phenyl group which may have a substituent, or a naphthyl group which may have a substituent. Specific examples of the case where the above-described hydrophilic group is bonded to the surface of carbon black via another atomic group include, for example, —C ₂ H ₄ COOM (where M represents an alkali metal, quaternary ammonium), -PhSO ₃ M (however, Ph is a phenyl group, M is an alkali metal, represents a quaternary _{ammonium), - C 5 H 10 NH} 3 + , and the like.

A pigment dispersion using a pigment dispersant can also be used for the ink used in the ink jet recording medium of the present invention.
As the pigment dispersant, as the hydrophilic polymer compound, in the natural system, plant polymers such as gum arabic, tragan gum, guar gum, karaya gum, locust bean gum, arabinogalactone, pectin, quince seed starch, alginic acid, Examples include seaweed polymers such as carrageenan and agar, animal polymers such as gelatin, casein, albumin and collagen, and microbial polymers such as xanthene gum and dextran. For semi-synthetic systems, cellulose polymers such as methylcellulose, ethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, carboxymethylcellulose, starch polymers such as sodium starch glycolate and sodium starch phosphate, sodium alginate, propylene glycol alginate And seaweed polymers such as Pure synthetic systems include polyvinyl polymers such as polyvinyl alcohol, polyvinyl pyrrolidone, and polyvinyl methyl ether, non-crosslinked polyacrylamide, polyacrylic acid or alkali metal salts thereof, acrylic resins such as water-soluble styrene acrylic resins, and water-soluble styrene malees. Acid resin, water-soluble vinyl naphthalene acrylic resin, water-soluble vinyl naphthalene maleic resin, polyvinyl pyrrolidone, polyvinyl alcohol, alkali metal salts of β-naphthalene sulfonic acid formalin condensate, cationic functional groups such as quaternary ammonium and amino groups Examples thereof include a polymer compound having a salt in the side chain and a natural polymer compound such as shellac. Among these, those having a carboxyl group introduced from a homopolymer of acrylic acid, methacrylic acid, styrene acrylic acid or a copolymer of other monomer having a hydrophilic group are particularly preferable as the polymer dispersant.
The weight average molecular weight of the copolymer is preferably 3,000 to 50,000, more preferably 5,000 to 30,000, and still more preferably 7,000 to 15,000.
The mixing mass ratio of the pigment and the dispersant (pigment: dispersant) is preferably 1: 0.06 to 1: 3, and more preferably 1: 0.125 to 1: 3.

  The amount of the colorant added to the ink is preferably 6 to 15% by mass, and more preferably 8 to 12% by mass. When the addition amount is less than 6% by mass, the image density may be lowered due to a decrease in coloring power, or feathering or bleeding may be deteriorated due to a decrease in viscosity. If the nozzle is left unattended, the nozzles will be easy to dry, non-ejection phenomenon will occur, the viscosity will be too high, the permeability will decrease, and the dots will not spread, so the image density will decrease. Or a blurred image.

(Wetting agent)
There is no restriction | limiting in particular as said wetting agent, According to the objective, it can select suitably, For example, at least 1 sort (s) selected from a polyol compound, a lactam compound, a urea compound, and saccharides is suitable.

  Examples of the polyol compound include polyhydric alcohols, polyhydric alcohol alkyl ethers, polyhydric alcohol aryl ethers, amides, amines, sulfur-containing compounds, propylene carbonate, and ethylene carbonate. These may be used alone or in combination of two or more.

Examples of the polyhydric alcohols include ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, polypropylene glycol, 1,3-purpandiol, 1,3-butanediol, 1,4 butanediol, and 3-methyl- 1,3-butanediol, 1,3-propanediol, 1,5-pentanediol, 1,6 hexanediol, glycerol, 1,2,6-hexanetriol, 1,2,4-butanetriol, 1,2, Examples include 3-butanetriol and petriol.
Examples of the polyhydric alcohol alkyl ethers include ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, tetraethylene glycol monomethyl ether, and propylene glycol monoethyl ether. It is done.
Examples of the polyhydric alcohol aryl ethers include ethylene glycol monophenyl ether and ethylene glycol monobenzyl ether.
Examples of the nitrogen-containing heterocyclic compound include N-methyl-2-pyrrolidone, N-hydroxyethyl-2-pyrrolidone, 2-pyrrolidone, 1,3-dimethylimidazolidinone, and ε-caprolactam.
Examples of the amides include formamide, N-methylformamide, formamide, N, N-dimethylformamide and the like.
Examples of the amines include monoethanolamine, diethanolamine, triethanolamine, monoethylamine, diethylamine, and triethylamine.
Examples of the sulfur-containing compounds include dimethyl sulfoxide, sulfolane, thiodiethanol, and the like.

Examples of the lactam compound include at least one selected from 2-pyrrolidone, N-methyl-2-pyrrolidone, N-hydroxyethyl-2-pyrrolidone, and ε-caprolactam.
Examples of the urea compound include at least one selected from urea, thiourea, ethylene urea, and 1,3-dimethyl-2-imidazolidinone. In general, the amount of urea added to the ink is preferably 0.5 to 50% by mass, and more preferably 1 to 20% by mass.

Examples of the saccharide include monosaccharides, disaccharides, oligosaccharides (including trisaccharides and tetrasaccharides), polysaccharides, and derivatives thereof. Among these, glucose, mannose, fructose, ribose, xylose, arabinose, galactose, maltose, cellobiose, lactose, sucrose, trehalose, and maltotriose are preferable, and maltose, sorbitol, gluconolactone, and maltose are particularly preferable.
The polysaccharide means a saccharide in a broad sense and can be used to include substances widely existing in nature such as α-cyclodextrin and cellulose.
Examples of the saccharide derivatives include reducing sugars of the saccharides (for example, sugar alcohols (generally represented by HOCH ₂ (CHOH) _n CH ₂ OH (where n represents an integer of 2 to 5)). , Oxidized sugars (eg, aldonic acid, uronic acid, etc.), amino acids, thioic acids, etc. Among these, sugar alcohols are particularly preferable, and examples of the alcohol include maltitol, sorbit, and the like.

  Among these, glycerin, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1 from the viewpoint of obtaining excellent effects on solubility and prevention of poor jetting characteristics due to water evaporation , 3-butanediol, 2,3-butanediol, 1,4-butanediol, 3-methyl-1,3-butanediol, 1,3-propanediol, 1,5-pentanediol, tetraethylene glycol, 1 , 6-hexanediol, 2-methyl-2,4-pentanediol, polyethylene glycol, 1,2,4-butanetriol, 1,2,6-hexanetriol, thiodiglycol, 2-pyrrolidone, N-methyl- 2-pyrrolidone, N-hydroxyethyl-2- Pyrrolidone are preferred, glycerin, 3-methyl-1,3-butanediol, 2-pyrrolidone is particularly preferred.

  The content of the wetting agent in the ink is preferably 10 to 50% by mass, and more preferably 20 to 35% by mass. If the content is too small, the nozzle is likely to be dried and defective ejection of droplets may occur. If the content is too large, the ink viscosity is increased, and the proper viscosity range may be exceeded.

(Penetration agent)
As the penetrant, a water-soluble organic solvent such as a polyol compound or a glycol ether compound is used. In particular, at least one of a polyol compound having 8 or more carbon atoms and a glycol ether compound is preferably used.
If the polyol compound has less than 8 carbon atoms, sufficient penetrability cannot be obtained, and the recording medium is soiled during double-sided printing, or ink spreading on the recording medium is insufficient, resulting in poor pixel filling. In some cases, character quality and image density may decrease.
Examples of the polyol compound having 8 or more carbon atoms include 2-ethyl-1,3-hexanediol (solubility: 4.2% (25 ° C.)), 2,2,4-trimethyl-1,3-pentanediol. (Solubility: 2.0% (25 ° C.)) is preferable.

  The glycol ether compound is not particularly limited and may be appropriately selected depending on the intended purpose.For example, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, Examples include polyhydric alcohol alkyl ethers such as tetraethylene glycol monomethyl ether and propylene glycol monoethyl ether; polyhydric alcohol aryl ethers such as ethylene glycol monophenyl ether and ethylene glycol monobenzyl ether.

  There is no restriction | limiting in particular in the addition amount of the said penetrant, Although it can select suitably according to the objective, 0.1-20 mass% is preferable, and 0.5-10 mass% is more preferable.

(Surfactant)
The surfactant is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include anionic surfactants, nonionic surfactants, amphoteric surfactants, and fluorosurfactants. ,

  Examples of the anionic surfactant include polyoxyethylene alkyl ether acetate, dodecyl benzene sulfonate, laurate, polyoxyethylene alkyl ether sulfate salt, and the like.

Examples of the nonionic surfactant include acetylene glycol surfactants, polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyoxyethylene alkyl esters, polyoxyethylene sorbitan fatty acid esters, and the like.
Examples of the acetylene glycol surfactant include 2,4,7,9-tetramethyl-5-decyne-4,7-diol, 3,6-dimethyl-4-octyne-3,6-diol, , 5-dimethyl-1-hexyn-3-ol and the like. Examples of commercially available acetylene glycol surfactants include Surfynol 104, 82, 465, 485, and TG manufactured by Air Products (USA).

  Examples of the amphoteric surfactant include lauryl aminopropionate, lauryl dimethyl betaine, stearyl dimethyl betaine, and lauryl dihydroxyethyl betaine. Specific examples include lauryl dimethylamine oxide, myristyl dimethylamine oxide, stearyl dimethylamine oxide, dihydroxyethyl lauryl amine oxide, polyoxyethylene coconut oil alkyl dimethyl amine oxide, dimethyl alkyl (coconut) betaine, dimethyl lauryl betaine, and the like. It is done.

As the fluorine-based surfactant, the following general formula (A)
CF ₃ CF ₂ 2 (CF ₂ CF ₂ ) _m —CH ₂ CH ₂ O (CH ₂ CH ₂ O) _n H (A)
What is represented by these is suitable.
However, in formula (A), m represents an integer of 0 to 10, and n represents an integer of 1 to 40.

  Examples of the fluorosurfactant include a perfluoroalkyl sulfonic acid compound, a perfluoroalkyl carboxylic compound, a perfluoroalkyl phosphate compound, a perfluoroalkyl ethylene oxide adduct, and a perfluoroalkyl ether group in the side chain. And polyoxyalkylene ether polymer compounds. Among these, the polyoxyalkylene ether polymer compound having a perfluoroalkyl ether group in the side chain has a low foaming property, and the bioaccumulation property of a fluorine compound that has been regarded as a problem in recent years is low and highly safe. Particularly preferred.

Examples of the perfluoroalkyl sulfonic acid compound include perfluoroalkyl sulfonic acid, perfluoroalkyl sulfonate, and the like.
Examples of the perfluoroalkyl carboxylic compounds include perfluoroalkyl carboxylic acids and perfluoroalkyl carboxylic acid salts.
Examples of the perfluoroalkyl phosphate compound include perfluoroalkyl phosphate esters, perfluoroalkyl phosphate salts, and the like.
The polyoxyalkylene ether polymer compound having a perfluoroalkyl ether group in the side chain includes a polyoxyalkylene ether polymer having a perfluoroalkyl ether group in the side chain, and a polyoxyalkylene ether having a perfluoroalkyl ether group in the side chain. Examples thereof include a sulfate salt of a polymer and a salt of a polyoxyalkylene ether polymer having a perfluoroalkyl ether group in the side chain.
As counter ions of salts in these fluorosurfactants, Li, Na, K, NH ₄ , NH ₃ CH ₂ CH ₂ OH, NH ₂ (CH ₂ CH ₂ OH) ₂ , NH (CH ₂ CH ₂ OH) ₃ etc. are mentioned.

As said fluorosurfactant, what was synthesize | combined suitably may be used and a commercial item may be used.
As this commercial item, for example, Surflon S-111, S-112, S-113, S-121, S-131, S-132, S-141, S-145 (all manufactured by Asahi Glass Co., Ltd.), Fullrad FC -93, FC-95, FC-98, FC-129, FC-135, FC-170C, FC-430, FC-431 (all manufactured by Sumitomo 3M), MegaFuck F-470, F1405, F-474 (All manufactured by Dainippon Ink & Chemicals, Inc.), Zonyl TBS, FSP, FSA, FSN-100, FSN, FSO-100, FSO, FS-300, UR (all manufactured by DuPont), FT-110, FT- 250, FT-251, FT-400S, FT-150, FT-400SW (all manufactured by Neos Co., Ltd.), PF-151N (manufactured by Omninova), etc. I can get lost. Among these, Zonyl FS-300, FSN, FSN-100, and FSO (manufactured by DuPont) are particularly preferable from the viewpoints of reliability and color development improvement.

(Other ingredients)
The other components are not particularly limited and can be appropriately selected according to need. An ultraviolet absorber, an oxygen absorber, a light stabilizer, etc. are mentioned.

(Resin emulsion)
The resin emulsion is obtained by dispersing resin fine particles in water as a continuous phase, and may contain a dispersant such as a surfactant as necessary.
The content of resin fine particles as the dispersed phase component (content of resin fine particles in the resin emulsion) is generally preferably 10 to 70% by mass. Further, the particle diameter of the resin fine particles is preferably 10 to 1000 nm, more preferably 20 to 300 nm, particularly considering use in an ink jet recording apparatus.

The resin fine particle component of the dispersed phase is not particularly limited and may be appropriately selected according to the purpose. For example, acrylic resin, vinyl acetate resin, styrene resin, butadiene resin, styrene-butadiene resin , Vinyl chloride resins, acrylic styrene resins, acrylic silicone resins, and the like. Among these, acrylic silicone resins are particularly preferable.
As said resin emulsion, what was synthesize | combined suitably may be used and a commercial item may be used.
Examples of the commercially available resin emulsion include Microgel E-1002, E-5002 (styrene-acrylic resin emulsion, manufactured by Nippon Paint Co., Ltd.), and Boncoat 4001 (acrylic resin emulsion, manufactured by Dainippon Ink & Chemicals, Inc.). ), Boncoat 5454 (styrene-acrylic resin emulsion, manufactured by Dainippon Ink & Chemicals, Inc.), SAE-1014 (styrene-acrylic resin emulsion, manufactured by Nippon Zeon Co., Ltd.), Cybinol SK-200 (acrylic resin emulsion, Seiden Chemical Co., Ltd.), Primal AC-22, AC-61 (acrylic resin emulsion, manufactured by Rohm and Haas), Nanoacryl SBCX-2821, 3689 (acrylic silicone resin emulsion, Toyo Ink Co., Ltd.) Company Ltd.), # 3070 (methyl methacrylate polymer resin emulsion, manufactured by Mikuni Color Ltd.).

  The addition amount of the resin fine particle component in the resin emulsion in the ink is preferably 0.1 to 50% by mass, more preferably 0.5 to 20% by mass, and still more preferably 1 to 10% by mass. If the addition amount is less than 0.1% by mass, the effect of improving clogging resistance and ejection stability may not be sufficient, and if it exceeds 50% by mass, the storage stability of the ink may be reduced. There is.

The aminopropanediol compound is a water-soluble organic basic compound, and for example, an aminopropanediol derivative is suitable.
There is no restriction | limiting in particular as said aminopropanediol derivative, According to the objective, it can select suitably, For example, 1-amino-2,3-propanediol, 1-methylamino-2,3-propanediol, 2 -Amino-2-methyl-1,3-propanediol, 2-amino-2-ethyl-1,3-propanediol, etc., among which 2-amino-2-ethyl-1,3-propane Diols are particularly preferred.

  The addition amount of the aminopropanediol compound in the recording ink is preferably 0.01 to 10% by mass, more preferably 0.1 to 5.0% by mass, and still more preferably 0.1 to 2.0% by mass. . If the amount added is too large, disadvantages such as an increase in pH and an increase in viscosity may occur.

  Examples of the antiseptic / antifungal agent include 1,2-benzisothiazolin-3-one, sodium dehydroacetate, sodium sorbate, sodium 2-pyridinethiol-1-oxide, sodium benzoate, and sodium pentachlorophenol. Can be mentioned.

The pH adjusting agent is not particularly limited as long as the pH can be adjusted to 7 or more without adversely affecting the ink, and any substance can be used according to the purpose.
Examples of the pH adjusting agent include amines such as diethanolamine and triethanolamine, hydroxides of alkali metal elements such as lithium hydroxide, sodium hydroxide and potassium hydroxide; ammonium hydroxide and quaternary ammonium hydroxide. Quaternary phosphonium hydroxide, alkali metal carbonates such as lithium carbonate, sodium carbonate, potassium carbonate, and the like.

  Examples of the rust inhibitor include acidic sulfite, sodium thiosulfate, ammonium thiodiglycolate, diisopropylammonium nitrite, pentaerythritol tetranitrate, and dicyclohexylammonium nitrite.

Examples of the antioxidant include phenol-based antioxidants (including hindered phenol-based antioxidants), amine-based antioxidants, sulfur-based antioxidants, phosphorus-based antioxidants, and the like.
Examples of the phenol-based antioxidant (including hindered phenol-based antioxidant) include butylated hydroxyanisole, 2,6-di-tert-butyl-4-ethylphenol, stearyl-β- (3.5) -Di-tert-butyl-4-hydroxyphenyl) propionate, 2,2'-methylenebis (4-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-ethyl-6-tert-butylphenol), 4,4′-Butylidenebis (3-methyl-6-tert-butylphenol), 3,9-bis [1,1-dimethyl-2- [β- (3-tert-butyl-4-hydroxy-5-methylphenyl) ) Propionyloxy] ethyl] 2,4,8,10-tetrixaspiro [5,5] undecane, 1,1,3-tris (2-methyl-4- Hydroxy-5-tert-butylphenyl) butane, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, tetrakis [methylene-3- (3 ′, 5′-di-tert-butyl-4′-hydroxyphenyl) propionate] methane, and the like.

Examples of the amine-based antioxidant include phenyl-β-naphthylamine, α-naphthylamine, N, N′-di-sec-butyl-p-phenylenediamine, phenothiazine, N, N′-diphenyl-p-phenylenediamine. 2,6-di-tert-butyl-p-cresol, 2,6-di-tert-butylphenol, 2,4-dimethyl-6-tert-butyl-phenol, butylhydroxyanisole, 2,2′-methylenebis ( 4-methyl-6-tert-butylphenol), 4,4′-butylidenebis (3-methyl-6-tert-butylphenol), 4,4′-thiobis (3-methyl-6-tert-butylphenol), tetrakis [methylene -3 (3,5-di-tert-butyl-4-dihydroxyphenyl) propionate] methane, 1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, and the like.
Examples of the sulfur-based antioxidant include dilauryl 3,3′-thiodipropionate, distearyl thiodipropionate, lauryl stearyl thiodipropionate, dimyristyl 3,3′-thiodipropionate, distearyl β. , β′-thiodipropionate, 2-mercaptobenzimidazole, dilauryl sulfide and the like.
Examples of the phosphorus antioxidant include triphenyl phosphite, octadecyl phosphite, triisodecyl phosphite, trilauryl trithiophosphite, trinonyl phenyl phosphite, and the like.

Examples of the ultraviolet absorber include benzophenone ultraviolet absorbers, benzotriazole ultraviolet absorbers, salicylate ultraviolet absorbers, cyanoacrylate ultraviolet absorbers, and nickel complex salt ultraviolet absorbers.
Examples of the benzophenone-based ultraviolet absorber include 2-hydroxy-4-n-octoxybenzophenone, 2-hydroxy-4-n-dodecyloxybenzophenone, 2,4-dihydroxybenzophenone, and 2-hydroxy-4-methoxybenzophenone. 2,2 ′, 4,4′-tetrahydroxybenzophenone, and the like.
Examples of the benzotriazole ultraviolet absorber include 2- (2′-hydroxy-5′-tert-octylphenyl) benzotriazole, 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-4′-octoxyphenyl) benzotriazole, 2- (2′-hydroxy-3′-tert-butyl-5′-methylphenyl) -5-chlorobenzotriazole, and the like.
Examples of the salicylate-based ultraviolet absorber include phenyl salicylate, p-tert-butylphenyl salicylate, p-octylphenyl salicylate, and the like.
Examples of the cyanoacrylate ultraviolet absorber include ethyl-2-cyano-3,3′-diphenyl acrylate, methyl-2-cyano-3-methyl-3- (p-methoxyphenyl) acrylate, and butyl-2- And cyano-3-methyl-3- (p-methoxyphenyl) acrylate.
Examples of the nickel complex ultraviolet absorber include nickel bis (octylphenyl) sulfide, 2,2′-thiobis (4-tert-octylferrate) -n-butylamine nickel (II), 2,2′-thiobis. (4-tert-octyl ferrate) -2-ethylhexylamine nickel (II), 2,2′-thiobis (4-tert-octyl ferrate) triethanolamine nickel (II), and the like.

  The ink used in the ink jet recording medium of the present invention has at least water, a colorant, and a wetting agent, and if necessary, a penetrating agent, a surfactant, and other components as necessary dispersed or dissolved in an aqueous medium. Further, it is manufactured by stirring and mixing as necessary. The dispersion can be performed by, for example, a sand mill, a homogenizer, a ball mill, a paint shaker, an ultrasonic disperser, etc., and stirring and mixing are performed by a stirrer using a normal stirring blade, a magnetic stirrer, a high-speed disperser, or the like. be able to.

The viscosity of the ink is preferably 2 mPa · s or more, more preferably 3 to 20 mPa · s at 25 ° C., considering image quality such as character quality when recorded on plain paper. If the viscosity exceeds 20 mPa · s, it may be difficult to ensure ejection stability.
The pH of the ink is preferably 7 to 10, for example.

  There is no restriction | limiting in particular as coloring of the said ink, According to the objective, it can select suitably, Yellow, magenta, cyan, black etc. are mentioned. When recording is performed using an ink set in which two or more of these colorings are used in combination, a multicolor image can be formed. When recording is performed using an ink set in which all colors are combined, a full color image is formed. be able to.

<Example>
EXAMPLES Hereinafter, although an Example demonstrates this invention further in full detail, this invention is not limited by this. Unless otherwise specified, “part” and “%” described below represent “part by mass” and “% by mass”, respectively.
In addition, the volume-based particle size distribution of kaolin was measured by a laser method particle size measuring machine (Mastersizer S type manufactured by Malvern, red light source is 633 nm (He-Ne laser), blue light is 466 nm (LED)). As a method for measuring the particle size distribution, a sample slurry containing kaolin in pure water was dropped and mixed to obtain a uniform dispersion, and charged into a measuring machine.

(Preparation of base paper)
70% by weight of hardwood bleached kraft pulp (freeness 480 ml) and 30% by weight of softwood bleached kraft pulp (freeness 500 ml) were mixed. Ketene dimer was added to 0.05% of pulp, sulfuric acid band was added to 1% of pulp, and calcium carbonate was added to pulp of 10% to obtain a paper stock. Using this stock, a web was formed with a long paper machine, dried by performing a three-stage wet press, and then machine calendered to obtain a base paper having a basis weight of 80 g / m ² .

Kaolin A (product name: Capim DG, manufactured by Rio Capim, the proportion of particles having a volume-based integrated value of 0.4 μm or more and less than 4.2 μm: 71%, the proportion of particles having a particle diameter of less than 0.4 μm: 18%, 100 parts of particles having a particle diameter of 4.2 μm or more: 11%), 5 parts of NB latex A (butadiene content 55%, glass transition temperature −41 ° C.) as a binder, 0.1 part of sodium hydroxide, dispersant As a result, 0.2 part of sodium polyacrylate and dilution water were mixed to obtain a paint having a solid content of 65%.
This paint was coated on both sides of the base paper using a blade coater so that the coating amount per side was 15 g / m ² . After coating, the ink was dried until the moisture content in the paper was 5% to obtain an ink jet recording medium.

100 parts of the above kaolin A, 5 parts of NB latex B as a binder (butadiene content 50%, glass transition temperature -40 ° C.), 0.1 part of sodium hydroxide, 0.2 part of sodium polyacrylate as a dispersant, and dilution Water was mixed to obtain a paint having a solid content of 65%.
This paint was coated on both sides of the base paper using a blade coater so that the coating amount per side was 15 g / m ² . After coating, the ink was dried until the moisture content in the paper was 5% to obtain an ink jet recording medium.

Kaolin B (product name: ECLIPS 650, manufactured by Engelhard, Inc., a volume-based integrated value of 0.4 μm or more and less than 4.2 μm of particles: 66%, a particle diameter of less than 0.4 μm of particles: 25%, (Particle ratio of particle size 4.2 μm or more: 9%) 100 parts, NB latex A 5 parts serving as binder, sodium hydroxide 0.1 part, sodium polyacrylate as a dispersing agent 0.2 part, and dilution water mixed Thus, a paint having a solid content of 65% was obtained.
This paint was coated on both sides of the base paper using a blade coater so that the coating amount per side was 15 g / m ² . After coating, the ink was dried until the moisture content in the paper was 5% to obtain an ink jet recording medium.

Kaolin A75 parts and Kaolin C (product name: KCS, manufactured by Imeris Corporation, the proportion of particles based on volumetric integration of 0.4 μm or more and less than 4.2 μm: 53%, the proportion of particles having a particle diameter of less than 0.4 μm : 21%, ratio of particles having a particle diameter of 4.2 μm or more: 26%) Mixed kaolin mixed with 25 parts (as a particle size distribution of the mixture of each kaolin, 0.4 μm or more and less than 4.2 μm by volume-based integrated value) Ratio of particles: 66%, ratio of particles having a particle diameter of less than 0.4 μm: 19%, ratio of particles having a particle diameter of 4.2 μm or more: 15%) 100 parts, 5 parts of NB latex A serving as a binder Then, 0.1 part of sodium hydroxide, 0.2 part of sodium polyacrylate as a dispersant and dilution water were mixed to obtain a paint having a solid content of 65%.
This paint was coated on both sides of the base paper using a blade coater so that the coating amount per side was 15 g / m ² . After coating, the ink was dried until the moisture content in the paper was 5% to obtain an ink jet recording medium.

75 parts of kaolin A, 25 parts of heavy calcium carbonate (Hydrocurve 90: manufactured by Omiya), 5 parts of NB latex A serving as a binder, oxidized starch, 0.1 part of sodium hydroxide, 0.2 part of sodium polyacrylate as a dispersant In addition, dilution water was mixed to obtain a paint having a solid content of 65%.
This paint was coated on both sides of the base paper using a blade coater so that the coating amount per side was 15 g / m ² . After coating, the ink was dried until the moisture content in the paper was 5% to obtain an ink jet recording medium.

75 parts of kaolin A, 25 parts of light calcium carbonate (TP-123: manufactured by Okutama Kogyo Co., Ltd.), 5 parts of NB latex A serving as a binder, 0.1 part of sodium hydroxide, 0.2 part of sodium polyacrylate as a dispersant, and dilution water Were mixed to obtain a paint having a solid content of 65%.
This paint was coated on both sides of the base paper using a blade coater so that the coating amount per side was 15 g / m ² . After coating, the ink was dried until the moisture content in the paper was 5% to obtain an ink jet recording medium.

100 parts of kaolin A, 2 parts of NB latex A serving as a binder, 0.1 part of sodium hydroxide, 0.2 part of sodium polyacrylate as a dispersing agent and dilution water were mixed to obtain a paint having a solid content of 65%.
This paint was coated on both sides of the base paper using a blade coater so that the coating amount per side was 15 g / m ² . After coating, the ink was dried until the moisture content in the paper was 5% to obtain an ink jet recording medium.

100 parts of kaolin A, 4 parts of NB latex A serving as a binder, 0.1 part of sodium hydroxide, 0.2 part of sodium polyacrylate as a dispersing agent and dilution water were mixed to obtain a paint having a solid content of 65%.
This paint was coated on both sides of the base paper using a blade coater so that the coating amount per side was 15 g / m ² . After coating, the ink was dried until the moisture content in the paper was 5% to obtain an ink jet recording medium.

100 parts of kaolin A, 4 parts of NB latex A serving as a binder, 1 part of oxidized starch (Mermaid 210: manufactured by Shikishima Starch Co., Ltd.), 0.1 part of sodium hydroxide, 0.2 part of sodium polyacrylate as a dispersant and diluting water are mixed. Thus, a paint having a solid content of 65% was obtained.
This paint was coated on both sides of the base paper using a blade coater so that the coating amount per side was 15 g / m ² . After coating, the ink was dried until the moisture content in the paper was 5% to obtain an ink jet recording medium.

100 parts of kaolin A, 8 parts of NB latex A serving as a binder, 0.1 part of sodium hydroxide, 0.2 part of sodium polyacrylate as a dispersing agent and dilution water were mixed to obtain a paint having a solid content of 65%.
This paint was coated on both sides of the base paper using a blade coater so that the coating amount per side was 15 g / m ² . After coating, the ink was dried until the moisture content in the paper was 5% to obtain an ink jet recording medium.

<Preparation of ink set>
An ink set A used for evaluation using an evaluation printer 2 described later was prepared.
(Production Example 1)
-Preparation of polymer solution A-
After sufficiently replacing the inside of a 1 L flask equipped with a mechanical stirrer, thermometer, nitrogen gas introduction tube, reflux tube, and dropping funnel, 11.2 g of styrene, 2.8 g of acrylic acid, 12.0 g of lauryl methacrylate Then, 4.0 g of polyethylene glycol methacrylate, 4.0 g of styrene macromer (manufactured by Toa Gosei Co., Ltd., trade name: AS-6) and 0.4 g of mercaptoethanol were mixed and heated to 65 ° C.
Next, styrene 100.8 g, acrylic acid 25.2 g, lauryl methacrylate 108.0 g, polyethylene glycol methacrylate 36.0 g, hydroxylethyl methacrylate 60.0 g, styrene macromer (manufactured by Toa Gosei Co., Ltd., trade name: AS-6) A mixed solution of 36.0 g, mercaptoethanol 3.6 g, azobismethylvaleronitrile 2.4 g, and methyl ethyl ketone 18 g was dropped into the flask over 2.5 hours. After completion of the dropwise addition, a mixed solution of 0.8 g of azobismethylvaleronitrile and 18 g of methyl ethyl ketone was dropped into the flask over 0.5 hours. After aging at 65 ° C. for 1 hour, 0.8 g of azobismethylvaleronitrile was added and further aging was performed for 1 hour. After completion of the reaction, 364 g of methyl ethyl ketone was added to the flask to prepare 800 g of polymer solution A having a concentration of 50% by mass.

(Production Example 1-1)
-Preparation of copper phthalocyanine pigment polymer fine particle dispersion-
Next, 46 g of the obtained polymer solution A, 33 g of copper phthalocyanine pigment, 13.6 g of 1 mol / L potassium hydroxide aqueous solution, 20 g of methyl ethyl ketone, and 13.6 g of ion-exchanged water were sufficiently stirred, and then a roll mill was used. And kneaded. The obtained paste was put into 200 g of pure water and stirred sufficiently, and then methyl ethyl ketone and water were distilled off using an evaporator, and then glycerin was added to obtain 10.9% by mass of pigment and 7.5% by mass of resin. A copper phthalocyanine pigment polymer fine particle dispersion of Production Example 1-1 containing 18.4% by mass (solid content) and 9.1% by mass of glycerin was produced.

(Production Example 1-2)
-Preparation of aqueous dispersion of magenta pigment polymer fine particles-
In Production Example 1-1, C.I. I. An aqueous dispersion of magenta pigment polymer fine particles of Production Example 1-2 was produced in the same manner as Production Example 1-1 except that Pigment Red 122 was used. The aqueous dispersion of magenta pigment polymer fine particles of Production Example 1-2 contains 13.6% by mass of pigment, 4.5% by mass of resin (solid content: 18.1% by mass), and 9.1% by mass of glycerin. Yes.

(Production Example 1-3)
-Preparation of aqueous dispersion of yellow pigment polymer fine particles-
In Production Example 1-1, C.I. I. An aqueous dispersion of yellow pigment polymer fine particles of Production Example 1-3 was produced in the same manner as Production Example 1-1 except that Pigment Yellow 74 was used. The aqueous dispersion of yellow pigment polymer fine particles of Production Example 1-3 contains 10.9% by mass of pigment, 7.5% by mass of resin (solid content of 18.4% by mass), and 9.1% by mass of glycerin. Yes.

(Production Example 2)
-Preparation of surface-treated black pigment dispersion-
90 g of carbon black having a CTAB specific surface area of 150 m ² / g and DBP oil absorption of 100 ml / 100 g is added to 3,000 ml of 2.5N sodium sulfate solution, stirred at a temperature of 60 ° C. and a speed of 300 rpm, and allowed to react for 10 hours. Oxidation treatment was performed. The reaction solution was filtered, and the carbon black separated by filtration was neutralized with a sodium hydroxide solution and subjected to ultrafiltration. The obtained carbon black was washed with water, dried, and dispersed in pure water so as to have a pigment of 20% by mass (solid content of 20% by mass) to prepare a surface-treated black pigment dispersion of Production Example 2.

(Production Example 3)
-Preparation of acrylic silicone fine particle dispersion B-
After thoroughly replacing nitrogen gas in a 1 L flask equipped with a mechanical stirrer, thermometer, nitrogen gas inlet tube, reflux tube, and dropping funnel, Latemul S-180 (reactive emulsifier with unsaturated carbon, Kao Corporation) 8.0 g of 100% by mass component manufactured by the company and 350 g of ion-exchanged water were added and mixed, and the temperature was raised to 65 ° C. After raising the temperature, 3.0 g of t-butyl peroxobenzoate and 1.0 g of sodium isoascorbate as reaction initiators were added, and after 5 minutes, 45 g of methyl methacrylate, 160 g of 2-ethylhexyl methacrylate, 5 g of acrylic acid, butyl methacrylate 45 g, cyclohexyl methacrylate 30 g, vinyltriethoxysilane 15 g, latem S-180 (reactive emulsifier with unsaturated carbon, manufactured by Kao Corporation, component 100% by mass) 8.0 g, and ion-exchanged water 340 g are mixed, The dropwise addition was performed over 3 hours. Then, after heat-aging at 80 degreeC for 2 hours, it cooled to normal temperature and adjusted pH to 7-8 with sodium hydroxide. Ethanol was distilled off using an evaporator, and the water content was adjusted to prepare 730 g of an acrylic silicone fine particle dispersion B solution of Production Example 3 having a solid content of 40% by mass.

(Preparation example)
<Preparation of ink set A>
Ink set A was prepared by combining the following inks.

-Preparation of cyan ink A-
After preparing an ink composition having the following formulation and adjusting the pH, filtration was performed with a membrane filter having an average pore diameter of 5 μm to prepare a recording ink.
<Ink composition>
-Copper phthalocyanine pigment-containing polymer fine particle dispersion of Production Example 1-1 [pigment 10.9% by mass, resin 7.5% by mass (solid content 18.4% by mass), glycerin 9.1% by mass, the rest being water ] 43.54 mass%
Acrylic silicone emulsion of Production Example 3 (solid content 40% by mass, residual water, volume average particle size 150 nm, glass transition temperature of resin component -15 ° C (differential heat rise) to -6 ° C (inflection point))・ 10% by mass
・ Glycerin as a wetting agent: 3.96% by mass
・ 1,3-Butanediol as a wetting agent: 24.39% by mass
・ 2-Ethyl-1,3-hexanediol as penetrant 2 mass%
・ Fluorine-based surfactant (FS-300, manufactured by DuPont, active ingredient 40% by mass)
・ 2.5% by mass
-Antiseptic and fungicidal agent (Proxel LV, manufactured by Avecia) ... 0.05% by mass
・ PH adjuster (triethanolamine): 0.3% by mass
・ Silicone emulsion antifoaming agent (KM-72F, manufactured by Shin-Etsu Chemical Co., Ltd.)
0.1% by mass
・ Water: the rest

-Preparation of magenta ink A-
After preparing an ink composition having the following formulation and adjusting the pH, filtration was performed with a membrane filter having an average pore diameter of 5 μm to prepare a recording ink.
<Ink composition>
-Magenta pigment-containing polymer fine particle dispersion of Production Example 1-2 [pigment 13.6% by mass, resin 4.5% by mass (solid content 18.1% by mass), glycerin 9.1% by mass, the rest being water] ...
55.74% by mass
Acrylic silicone emulsion of Production Example 3 (solid content 40% by mass, residual water, volume average particle size 150 nm, glass transition temperature of resin component -15 ° C (differential rise) to -6 ° C (inflection point))・ 8% by mass
・ Glycerin as wetting agent: 2.42% by mass
・ 1,3-butanediol as a wetting agent: 23.25% by mass
・ 2-Ethyl-1,3-hexanediol as penetrant 2 mass%
・ Fluorine-based surfactant (FS-300, manufactured by DuPont, active ingredient 40% by mass)
・ 2.5% by mass
-Antiseptic and fungicidal agent (Proxel LV, manufactured by Avecia) ... 0.05% by mass
・ PH adjuster (triethanolamine): 0.3% by mass
・ Silicone emulsion antifoaming agent (KM-72F, manufactured by Shin-Etsu Chemical Co., Ltd.)
0.1% by mass
・ Water: the rest

-Preparation of yellow ink A-
After preparing an ink composition having the following formulation and adjusting the pH, filtration was performed with a membrane filter having an average pore diameter of 5 μm to prepare a recording ink.
<Ink composition>
-Yellow polymer fine particle dispersion of Production Example 1-3 [pigment 10.9% by mass, resin 7.5% by mass (solid content 18.4% by mass), glycerin 9.1% by mass, the rest being water]・ 43.54% by mass
Acrylic silicone emulsion of Production Example 3 (solid content 40% by mass, residual water, volume average particle size 150 nm, glass transition temperature of resin component -15 ° C (differential heat rise) to -6 ° C (inflection point))・ 10% by mass
・ Glycerin as a wetting agent: 3.58% by mass
・ 1,3-butanediol as a wetting agent: 23.25% by mass
・ 2-Ethyl-1,3-hexanediol as penetrant 2 mass%
・ Fluorine-based surfactant (FS-300, manufactured by DuPont, active ingredient 40% by mass)
・ 2.5% by mass
-Antiseptic and fungicidal agent (Proxel LV, manufactured by Avecia) ... 0.05% by mass
・ PH adjuster (triethanolamine): 0.3% by mass
・ Silicone emulsion antifoaming agent (KM-72F, manufactured by Shin-Etsu Chemical Co., Ltd.)
0.1% by mass
・ Water: the rest

-Preparation of black ink A-
After preparing an ink composition having the following formulation and adjusting the pH, filtration was performed with a membrane filter having an average pore diameter of 5 μm to prepare a recording ink.
<Ink composition>
-Carbon black dispersion liquid having hydrophilic groups in Production Example 2 [solid content 20% by mass, remaining is water, colorant / resin (mass ratio) = 10/0 in solid content] 38.00% by mass
Acrylic silicone emulsion of Production Example 3 (solid content 40% by mass, residual water, volume average particle size 150 nm, glass transition temperature of resin component -15 ° C (differential heat rise) to -6 ° C (inflection point))・ 13.75% by mass
・ Glycerin as a wetting agent: 8.5% by mass
・ 3-Methyl-1,3-butanediol as a wetting agent: 17.00% by mass
・ 2-Ethyl-1,3-hexanediol as penetrant 2 mass%
・ Fluorine-based surfactant (FS-300, manufactured by DuPont, active ingredient 40% by mass)
・ 2.5% by mass
-Antiseptic and fungicidal agent (Proxel LV, manufactured by Avecia) ... 0.05% by mass
・ PH adjuster (triethanolamine): 0.3% by mass
・ Silicone emulsion antifoaming agent (KM-72F, manufactured by Shin-Etsu Chemical Co., Ltd.)
0.1% by mass
・ Water: the rest

  Table 1 shows the results of measuring the surface tension, pH, and viscosity of each ink of the obtained ink set A as follows.

<Measurement of pH>
The pH was measured at 23 ° C. using a pH meter (MODEL HM3A, manufactured by Toa Denpa Kogyo Co., Ltd.).

<Measurement of viscosity>
The viscosity was measured at 25 ° C. using a RE500 viscometer (manufactured by Toki Sangyo Co., Ltd.) under conditions of cone 34 × R24, 180 rpm, 3 minutes later.

<Measurement of surface tension>
The surface tension is a static surface tension measured at 25 ° C. using a platinum plate using a surface tension measuring device (CBVP-Z, manufactured by Kyowa Interface Science Co., Ltd.).

<Comparative Example 1>
Mixed kaolin in which 50 parts of kaolin A and 50 parts of kaolin C are mixed (as the particle size distribution of each kaolin mixture, the proportion of particles having a volume-based integrated value of 0.4 μm or more and less than 4.2 μm is 62%, the particle size is 0.8%. The ratio of particles less than 4 μm: 20%, the ratio of particles having a particle diameter of 4.2 μm or more: 18%) 100 parts, NB latex A 5 parts serving as a binder, 0.1 parts of sodium hydroxide, as a dispersant 0.2 parts of sodium polyacrylate and dilution water were mixed to obtain a paint having a solid content of 65%.
This paint was coated on both sides of the base paper using a blade coater so that the coating amount per side was 15 g / m ² . After coating, the ink was dried until the moisture content in the paper was 5% to obtain an ink jet recording medium.

<Comparative Example 2>
50 parts of kaolin A, 50 parts of heavy calcium carbonate (Hydrocurve 90: manufactured by Omiya), 5 parts of NB latex A serving as a binder, 0.1 part of sodium hydroxide, 0.2 part of sodium polyacrylate as a dispersant, and dilution water Thus, a paint having a solid content of 65% was obtained.
This paint was coated on both sides of the base paper using a blade coater so that the coating amount per side was 15 g / m ² . After coating, the ink was dried until the moisture content in the paper was 5% to obtain an ink jet recording medium.

<Comparative Example 3>
50 parts of kaolin A, 50 parts of light calcium carbonate (TP-123: manufactured by Okutama Kogyo Co., Ltd.), 5 parts of NB latex A serving as a binder, 0.1 part of sodium hydroxide, 0.2 part of sodium polyacrylate as a dispersant and dilution water Thus, a paint having a solid content of 65% was obtained.
This paint was coated on both sides of the base paper using a blade coater so that the coating amount per side was 15 g / m ² . After coating, the ink was dried until the moisture content in the paper was 5% to obtain an ink jet recording medium.

<Comparative Example 4>
100 parts of kaolin A, 9 parts of NB latex A serving as a binder, 0.1 part of sodium hydroxide, 0.2 part of sodium polyacrylate as a dispersant and diluting water were mixed to obtain a paint having a solid content of 65%.
This paint was coated on both sides of the base paper using a blade coater so that the coating amount per side was 15 g / m ² . After coating, the ink was dried until the moisture content in the paper was 5% to obtain an ink jet recording medium.

<Comparative Example 5>
100 parts of kaolin A, 15 parts of NB latex A serving as a binder, 0.1 part of sodium hydroxide, 0.2 part of sodium polyacrylate as a dispersing agent and dilution water were mixed to obtain a paint having a solid content of 65%.
This paint was coated on both sides of the base paper using a blade coater so that the coating amount per side was 15 g / m ² . After coating, the ink was dried until the moisture content in the paper was 5% to obtain an ink jet recording medium.

<Comparative Example 6>
100 parts of kaolin C, 5 parts of NB latex A serving as a binder, 0.1 part of sodium hydroxide, 0.2 part of sodium polyacrylate as a dispersing agent and dilution water were mixed to obtain a paint having a solid content of 65%.
This paint was coated on both sides of the base paper using a blade coater so that the coating amount per side was 15 g / m ² . After coating, the ink was dried until the moisture content in the paper was 5% to obtain an ink jet recording medium.

<Comparative Example 7>
Kaolin D (product name: DB PLATE, manufactured by Imeris Co., Ltd., the proportion of particles having a volume-based integrated value of 0.4 μm or more and less than 4.2 μm: 49%, the proportion of particles having a particle diameter of less than 0.4 μm: 13%, The ratio of particles having a particle diameter of 4.2 μm or more: 38%) 100 parts, 5 parts of SB latex A serving as a binder, 0.1 part of sodium hydroxide, 0.2 part of sodium polyacrylate as a dispersing agent and dilution water were mixed. Thus, a paint having a solid content of 65% was obtained.
This paint was coated on both sides of the base paper using a blade coater so that the coating amount per side was 15 g / m ² . After coating, the ink was dried until the moisture content in the paper was 5% to obtain an ink jet recording medium.

<Comparative Example 8>
100 parts of kaolin A, 5 parts of NB latex C serving as a binder (butadiene content 40%, glass transition temperature -18 ° C.), 0.1 part of sodium hydroxide, 0.2 part of sodium polyacrylate as a dispersant and dilution water By mixing, a paint having a solid content of 65% was obtained.
This paint was coated on both sides of the base paper using a blade coater so that the coating amount per side was 15 g / m ² . After coating, the ink was dried until the moisture content in the paper was 5% to obtain an ink jet recording medium.

<Comparative Example 9>
80 parts of synthetic amorphous silica (Fine Seal X-60: manufactured by Tokuyama Corporation), 20 parts of synthetic amorphous silica (Fine Seal X-37B: manufactured by Tokuyama Corporation), polyvinyl alcohol as a binder (PVA 117: manufactured by Kuraray Co., Ltd.) 30 parts, 5 parts of ethylene vinyl acetate emulsion, 10 parts of polyamine dye fixing agent, 0.5 part of antifoaming agent (SN deformer 480: manufactured by San Nopco) and dilution water were added to obtain a paint having a solid content of 15%. .
This paint was coated on both sides of the base paper using a blade coater so that the coating amount per side was 15 g / m ² . After coating, the paper was dried until the moisture content in the paper reached 5% to obtain an ink jet recording medium.

<Comparative Example 10>
Light calcium carbonate (TP-123: manufactured by Okutama Kogyo Co., Ltd.) 100 parts, NB latex A 5 parts as a binder, sodium hydroxide 0.1 parts, sodium polyacrylate as a dispersant, diluting water, etc. are added as appropriate. A paint with a solids content of 65% was obtained.
This paint was coated on both sides of the base paper using a blade coater so that the coating amount per side was 15 g / m ² . After coating, the ink was dried until the moisture content in the paper was 5% to obtain an ink jet recording medium.

<Comparative Example 11>
100 parts of kaolin A, 5 parts of polyvinyl alcohol (PVA110, manufactured by Kuraray Co., Ltd.) serving as a binder, 0.1 part of sodium hydroxide, 0.2 part of sodium polyacrylate as a dispersant and dilution water are mixed to a solid content of 60%. A paint was obtained.
This paint was coated on both sides of the base paper using a blade coater so that the coating amount per side was 15 g / m ² . After coating, the ink was dried until the moisture content in the paper was 5% to obtain an ink jet recording medium.

<Evaluation>
1-1. Blank paper glossiness According to JIS Z8741, the blank paper glossiness (light incident angle of 75 degrees) on the surface of the ink receiving layer was measured using a glossmeter (manufactured by Murakami Color Research Laboratory, True GLOSS GM-26PRO).
1-2. Air permeability resistance JAPAN TAPPI Paper Pulp Test Method No. According to 5-2, the air permeability resistance of the ink jet recording medium was determined using the Oken type air permeability meter (Asahi Seiko Co., Ltd., digital type Oken type air permeability / smoothness tester model EYO-55-1MS). It measured using.
1-3. Surface Roughness According to JIS P8151, the surface roughness of the ink receiving layer when using a hard backing with a clamping pressure of 1000 kPa was measured using a surface roughness meter (manufactured by MESSMER, PAKER PRINT-SURF ROUGHNESS TESTER MODEL NO. ME- 90).

2. Inkjet printing quality Printing was performed using the following two commercially available pigment inkjet printers, and printing evaluation was performed according to the following evaluation method. The evaluation printer 1 printed using genuine ink (pigment ink). The evaluation printer 2 changed the genuine ink to the ink set A and printed it.
Evaluation printer 1: Seiko Epson, PX-G900, “plain paper / clean” mode Evaluation printer 2: Ricoh, IPSiO GX5000, “glossy paper / high speed” mode 2-1. Feathering Using the evaluation printers 1 and 2 above, print out the 0.75 point, 1.5 point, and 2.25 point straight lines so that they do not touch each other, and the lines as close as possible. The ink bleeding (feathering) was visually observed and evaluated according to the following criteria.
○: There is no bleeding and the level is good.
(Triangle | delta): Although there is some bleeding, it is a level which is satisfactory practically.
X: Bleeding is conspicuous and the level is not practical.

2-2. Bleed Using the above-described evaluation printers 1 and 2, printing was carried out so that the red and yellow solid squares were in contact with each other, and bleeding (bleed) at the color boundary portion was visually observed and evaluated according to the following criteria.
◯: There is no color boundary bleeding and a good level.
Δ: There is a slight color boundary bleeding, but there is no practical problem.
X: The color boundary bleeding is conspicuous and the level is not practical.

2-3. Solid printing unevenness Using the evaluation printers 1 and 2, green solid squares were printed, and the density unevenness of the printing part was visually observed and evaluated according to the following criteria.
A: There is no density unevenness in the printed portion, which is a good level.
B: There is almost no density unevenness in the printed part, and the second level is the next best level.
C: Although there is a slight density unevenness in the printed part, it is at a level where there is no practical problem.
D: Density unevenness in the printed portion is conspicuous and is at a level unbearable for practical use.
E: The print portion forms a patch pattern, density unevenness is very conspicuous, and the image cannot be reproduced.

2-4. Drying Using the evaluation printers 1 and 2, a black straight line having a thickness of 1 point was printed, and rubbed with a cotton swab immediately after printing, and drying was evaluated according to the following criteria.
A: Even when rubbed with a cotton swab, the printed part hardly extends, the drying is fast, and it is at a good level.
B: When rubbed with a cotton swab, the printed part is slightly extended and drying is somewhat slow, but it is at a level that causes no problem in practical use.
C: When rubbed with a cotton swab, the printed portion is extended, drying is slow, and it is at a level that cannot withstand practical use.

2-5. Scratch resistance of printed part Using the evaluation printer 2 described above, a solid red square was printed, and after printing, 24 hours had passed, and the friction tester type II (made by Suga Test Instruments Co., Ltd., friction tester model) in accordance with JIS Z0849 FR-2 type), and the solid print portion was reciprocated and rubbed 30 times with a cotton cloth, and the scratch resistance of the print portion was evaluated according to the following criteria.
○: Ink hardly transfers to the cotton cloth, which is a good level.
Δ: Ink slightly transferred to the cotton cloth, but at a level where there is no practical problem.
X: The ink is transferred to the cotton cloth and is not practically usable.

2-5. Texture of matte coated paper for offset printing A predetermined pattern was inkjet printed using the evaluation printers 1 and 2 described above. The same pattern as this was offset printed on matte coated paper for offset printing (Ulite Ultra S: manufactured by Nippon Paper Industries Co., Ltd., basis weight 90.0 g / m ² ). The appearance and feel of the inkjet print were compared with the offset print and evaluated according to the following criteria.
○: The texture such as appearance and touch is close to the matte coated paper for offset printing, and has a texture of offset printed matter.
×: Unlike the offset-printed matte coated paper, the texture such as appearance and touch is not the texture of the offset printed matter.

  The obtained results are shown in Tables 2 and 3.

  As is apparent from Tables 2 and 3, in each example, there is little printing unevenness in image feathering, bleed and solid parts, excellent drying and scratch resistance of the printed parts, and various printing qualities. In addition to being well-balanced, a texture of matte-coated paper for offset printing was also obtained.

  In the case of Comparative Examples 1, 6, and 7 using kaolin in which the proportion of particles having a volume-based integrated value of 0.4 μm or more and less than 4.2 μm is less than 64%, or particles of 0.4 μm or more and less than 4.2 μm In the case of Comparative Examples 2 and 3 in which the content ratio of kaolin occupying 64% or more in terms of the volume-based integrated value is less than 60 parts by mass with respect to 100 parts of the inorganic pigment in the ink receiving layer, solid printing unevenness is also observed. Became prominent. This is thought to be because the width of the particle size distribution of the entire inorganic pigment contained in the ink receiving layer becomes broad, and the amount of voids in the ink receiving layer decreases because the inorganic pigment is finely packed, resulting in a decrease in ink absorbency. It is done. When the ratio of heavy calcium carbonate or light calcium carbonate as the pigment in the ink receiving layer is large, a phenomenon such as bleeding tends to occur.

  Also, in the case of Comparative Examples 4 and 5 in which the content of the acrylonitrile butadiene copolymer relative to the inorganic pigment exceeded 8 parts by mass, the printing unevenness of the solid part became remarkable. This is considered to be because the ink absorbability was lowered.

  In Comparative Example 8 using an acrylonitrile butadiene copolymer having a butadiene content of less than 50% as a binder, the scratch resistance of the printed part was inferior. This is presumably because the amount of butadiene in the acrylonitrile butadiene-based copolymer is small, the stickiness is insufficient, and the adhesion of the colored pigment in the ink is weak.

In the case of Comparative Example 9 in which silica was used as the inorganic pigment and no kaolin was contained, the print quality such as ink absorbability was improved, but the texture of matte coated paper for offset printing could not be obtained.
In the case of Comparative Example 10 in which light calcium carbonate was used as the inorganic pigment and no kaolin was contained, the texture of the matte coated paper for offset printing was obtained, but the printing unevenness in the solid part became remarkable. This is presumably because the ink receiving layer does not contain any kaolin in the particle size range of the example, so that the amount of voids in the ink receiving layer is reduced and the ink absorbency is lowered. Similarly, in the case of Comparative Example 9 which does not contain any kaolin, the reason why the ink absorbency does not decrease is that the silica having a porous structure is used as the coating pigment, so that the amount of voids in the coating layer increases. This is because.
In Comparative Example 11 in which PVA was used as the binder instead of the acrylonitrile butadiene copolymer having a butadiene content of 50% or more, the scratch resistance of the printed portion was inferior. This is presumably because the stickiness of the binder component was insufficient and the adhesion of the colored pigment in the ink was weak.

Claims (3)

  The inorganic pigment having an ink receiving layer containing a binder containing an acrylonitrile butadiene copolymer having a butadiene content of 50% by mass or more on one or both sides of a base paper mainly composed of wood pulp, and an inorganic pigment The content ratio of the acrylonitrile butadiene-based copolymer with respect to 100 parts by mass is 1 part by mass or more and 8 parts by mass or less, and 60% by mass or more of the inorganic pigment is 0.4 μm or more when measured by a laser diffraction method. . Kaolin occupies 64% or more of particles less than 2 μm in volume-based integrated value, and the surface roughness of the ink receiving layer exceeds 1.4 μm when using a hard backing with a clamping pressure of 1000 kPa according to JIS P8151 An inkjet recording medium having a size of 5 μm or less.   2. The inkjet recording medium according to claim 1, wherein the glossiness of the white paper at a light incident angle of 75 degrees according to JIS Z8741 on the surface of the ink receiving layer is 20% or more and less than 55%.   An ink jet recording method comprising: recording an image on the ink jet recording medium according to claim 1 or 2 using an ink containing at least water, a particulate colorant, and a wetting agent.