JP2003165267A - Method for ink jet recording, recorder, ink media set and recorded matter - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for ink jet recording capable of imparting excellent discharge stability and storage stability, the fastness of an image such as (1) good color tone, (2) high image density, (3) a recorded image having a high sharpness without bringing about a fog or bleeding on the peripheral part of a character or an image, (4) bleeding (color bleeding) in a boundary between different colors, (5) an image having no unevenness, (6) a water resistance, a light resistance, scuff resistance or the like to provide a recorder, an ink media set and a recorded matter. <P>SOLUTION: The method for ink jet recording comprises the steps of imparting the ink containing a polymer emulsion obtained by incorporating a color material insoluble or slightly soluble in water in polymer fine particles in response to recording information on the surface of the porous layer side of a recording medium having one or more porous layers containing inorganic particles on the base, and recording the ink thereon. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an inkjet recording method using a pigment ink, a recording apparatus, an ink / media set, and a recorded matter, and particularly, a high-quality image having a good color tone excellent in ink absorbability and fixing property. An ink jet recording method, a recording device, and an ink which can obtain an image excellent in image fastness such as water resistance and light resistance, have excellent storage stability, and have excellent ejection stability without clogging of the head during printing. -It relates to media sets and recorded materials.

[0002]

2. Description of the Related Art Inkjet printers have spread remarkably due to their advantages of low noise and low running cost, and color printers capable of printing on plain paper as well as recording media exclusively for ink jet have been actively introduced to the market. . However, it satisfies all required characteristics such as image color reproducibility, durability, light resistance, image dryness, character bleeding (feathering), color boundary bleeding (color bleed), double-sided printability, and ejection stability. It is very difficult to do so, and the ink to be used is selected from the characteristics that are prioritized according to the application. In particular, it is difficult to satisfy these characteristics in a printer that performs high-speed printing on plain paper.

The ink used for ink jet recording generally contains water as a main component and a coloring agent and a wetting agent such as glycerin for the purpose of preventing clogging. As the colorant, a dye is used because of its excellent color developability and stability. However, the light resistance and water resistance of the image obtained using the dye-based ink are inferior. Although the water resistance has been improved to some extent by improving the inkjet recording medium having an ink absorbing layer, it is not satisfactory for plain paper.

In recent years, in order to improve these problems,
Pigment inks using organic pigments or pigments such as carbon black as colorants instead of dyes have been studied. Since the pigment is insoluble in water, it is used as an aqueous ink in which the pigment is mixed and dispersed with a dispersant and stably dispersed in water. Water resistance and light resistance are imparted by using a pigment, but other properties cannot be achieved at the same time. In particular, when high-speed printing is performed on plain paper, it is difficult to obtain high image density and color developability, and character bleeding, color boundary bleeding, and double-sided printability are not sufficiently satisfactory.

Further, in ink jet recording, stable ink droplets are required to be ejected from fine nozzles of the ink jet recording head. Therefore, it is necessary that the solidification of ink does not occur due to the drying of the orifice of the ink jet recording head. . However, when the ink containing the above-mentioned dispersant is used for inkjet recording, the resin forming the dispersant is not redissolved after adhering to the orifice or the like, and clogging or ink failure. Ejection may occur. In particular, when printing is stopped for a long period of time, the nozzles and the like are likely to be clogged, and the thickened ink is accumulated in the nozzle cap and the maintenance mechanism such as the suction tube, which may impair the function of the maintenance mechanism. It was something. In addition, when printing is paused for the first time, or when a blank document or image is being printed and a nozzle corresponding to the blank is used for a printing pause period, defective printing due to disturbance of the ink droplet ejection direction (intermittent printing) Problems such as defective ejection occurred frequently. In addition, the aqueous pigment ink containing the dispersant is viscous, and when performing continuous ejection and high-speed printing for a long time, resistance is generated in the path to the nozzle tip, and ejection becomes unstable, making smooth recording difficult. There was also the problem of becoming.

As an attempt to improve these problems,
Japanese Patent Application Laid-Open No. 2000-212486 discloses a pigment, a pigment concentration,
Inks containing a water-soluble dispersant and a penetrant, and further inks containing a specific polyhydric alcohol alkyl ether derivative, and these ink sets are disclosed. Since the disclosed ink is super permeable, the drying property is sufficient even at high-speed printing and ejection stability is secured, but the image density and color reproducibility on plain paper are better than those of dye-based inks. It is inferior in appearance, and although character bleeding, color boundary bleeding, and double-sided printability are improved compared to conventional ink jet recording images, it can be used for electrophotographic recording images used in plain paper printing in the market. It was inferior to the comparison and needed further improvement.

Further, an ink containing a colorant-containing resin dispersion in which a colorant is encapsulated in a water-insoluble and dispersible resin is disclosed as a means for improving the durability of an image. However, there is a problem that sufficient image density cannot be obtained when carbon black is used as the colorant. When a color organic pigment is used as the colorant, the conventionally known ink formulation is inferior in image density and color reproducibility on plain paper as compared with dye ink. Further, the color boundary blurring between black and yellow is not satisfactory in the ink set in which the colorant-encapsulating resin-dispersed black ink and the color ink are combined.

As another dispersion method, there is a so-called self-dispersion pigment ink which can be stably dispersed without using a dispersant. Japanese Patent Application Laid-Open No. 5-
As described in JP-A-186704 and JP-A-8-3498, by introducing a hydrophilic group to the surface of carbon, a so-called self-dispersion type can be stably dispersed without using a dispersant. Carbon black is being developed. Furthermore, as for color pigment-based inks, as described in JP-A-2000-513396, color pigments that can be stably dispersed without using a dispersant have been developed.

When these self-dispersion pigment inks were combined, the saturation of the color image on plain paper was low, and the scratch resistance on a dedicated recording medium such as glossy paper was poor. When a resin emulsion is added to improve the scratch resistance, there is a drawback that the dispersion stability of the ink is lowered and the ejection stability is impaired.

In addition, as an ink set consisting of black ink and color ink, a black ink having self-dispersion type carbon black and a color ink containing a coloring material having a polarity opposite to that of the coloring material of the black ink are used. Such an ink set is disclosed in JP-A-10-140064. Also, Japanese Patent Laid-Open No. 2000-191972
Japanese Patent Publication discloses an ink set in which the colorant-containing resin-dispersed ink has different ionic properties. However, although prints using these ink sets have improved color boundary bleeding, other plain paper properties are still unsatisfactory.

Efforts to improve suitability for pigment inks have also been made in coated paper type ink jet recording media having a coating layer on a substrate. As the one having an ink receiving layer mainly composed of a water-soluble resin,
JP-A No. 11-342669 discloses that the ink receiving layer contains hydroxypropylmethylcellulose and the ink receiving layer is N-type.
An inkjet recording material containing a homopolymerization resin of vinylpyrrolidone or a copolymerization resin of N-vinylpyrrolidone and another polymerizable monomer is described, and JP-A 2000-108 is disclosed.
JP-A-10-3294 describes an ink jet recording sheet containing a water-soluble cellulose derivative having a methoxyl group and a water-soluble cationic resin.
Japanese Patent Publication No. 05 describes an ink jet recording sheet containing a hydrophilic polymer resin and a specific anionic fluorosurfactant.

The ink-receiving layer containing an inorganic pigment and a binder as main components is disclosed in JP-A-10-119417.
JP-A-10-329417 describes an ink jet recording sheet in which an ink permeation layer containing an inorganic filler as a main component and an ink swelling layer containing a water-soluble resin as a main component are provided on a base sheet. And (A) an ink receiving layer containing a water-soluble resin, a surface-roughening agent and a crosslinking agent,
(B) In a recording film having a recording layer in which a dot shape adjusting agent-containing layer is sequentially laminated, at least two kinds of synthetic silicas having different oil absorptions are used as the surface-roughening forming agent of (A), and the amounts thereof are used. The recording film for inkjet is characterized in that the standard wiping number of the recording layer is adjusted to 20 to 100 times and the ink fixing time is adjusted to 5 minutes or less. JP-A No. 11-99739 discloses the first ink receiving film. A layer and a second ink receiving layer, the first ink receiving layer contains a resin component that is dissolved or swollen by the second ink receiving layer coating liquid, and the pigment content in the second ink receiving layer is An ink jet recording sheet is described which is characterized by having a pigment content higher than that of the first ink receiving layer. JP-A-11-245502 discloses a water-absorbent polyurethane. Further a water-absorbing polyurethane 15-90% by weight of the total coating agent, the average particle size of 10 to 30 wt% of silica 6～9Myuemu an average particle size of 10~15μm
15 to 40% by weight of silica for light diffusion and an average particle size of 10
15 to 40% by weight of porous silica having a particle size of 22 μm, and a silica mixture consisting of
An ink jet coating agent containing 0% by weight is described, and in JP-A No. 11-291619, an adhesive containing (A) a binder, (B) a coating film forming auxiliary agent and (C) a cross-linking agent as main components is described. Layer and the same binder as the above component (A),
(D) a roughening agent, a cross-linking agent same as the component (C), and a catalyst (E) as main components, and the weight ratio of the binder to the roughening agent is 2: 3 to 1: 3. An inkjet recording film in which an ink receiving layer is sequentially laminated is described. JP-A No. 11-301093 discloses an inkjet recording material having an ink solvent permeable layer on the ink receiving layer, which is permeable to a solvent but not permeable to a pigment. Is stated,
Japanese Unexamined Patent Publication No. 2000-1043 describes a recording material for an aqueous ink, which is formed of a polyvinyl acetal resin, a urea / glyoxal / acrylamide polycondensate and / or an epoxy compound, and a resin composition containing fine particles. 2000-197952 discloses an inkjet recording material containing silica or the like and a cationic resin having a cation strength of 1.5 meq / g or more and 6 meq / g or less. 2000-79754, the ink receiving layer,
A partially erasable recording sheet carrying an inkjet printing pattern with a non-compatible pigment ink is described, and JP-A-2000-127610 discloses a porous sheet in which inorganic or organic fine particles are embedded. An inkjet recording sheet comprising starch particles and a binder resin is described. JP-A-2000-141476 discloses a polyvinyl acetal resin as a main component, a polyvinylpyrrolidone resin, and a urea / glyoxal / acrylamide polycondensate and / or an epoxy compound. And an ink receiving layer containing an inorganic pigment, a water-insoluble resin, and a metal salt having a ionic valence of 2 or more are formed in JP-A 2000-190622. An ink jet recording material is described, and JP-A-2000-
JP-A-238420 discloses that the pigment and the binder are 10 to 50 parts by weight relative to 100 parts by weight of the pigment, and the recording layer is a synthetic silica having an average particle diameter of 3 to 15 μm as the pigment and a saponification degree as the binder. Is 96 mol% or more of polyvinyl alcohol as a main component, and the quaternary ammonium salt polymer is contained in an amount of 1 to 40 parts by weight per 100 parts by weight of the pigment and a curing agent in an amount of 20 to 100 parts by weight per 100 parts by weight of the binder. An ink jet recording sheet is described in Japanese Patent Application Laid-Open No. 2000-
Japanese Patent No. 247014 has a polyvinyl acetal resin obtained by acetalizing polyvinyl alcohol using an aromatic aldehyde as a main component, and a water-soluble acrylic acid resin, a water-soluble epoxy compound, and
A recording material for water-based inks containing fine particles of at least one selected from the group consisting of silicic acid, silica, kaolin, clay, alumina, calcium carbonate, zeolite, titanium oxide, talc and spherical polymers is described. 20
No. 00-318298, a resin film, an amorphous synthetic silica and a water-insoluble resin-containing lower layer, and an amorphous synthetic silica, a water-insoluble resin and a silanol-modified polyvinyl alcohol-containing upper layer, and a smoothness of 5 seconds or more and 40 seconds or less. An inkjet recording sheet is described.

As the aluminum oxide type receptive layer, JP-A-2000-37945 discloses that the ink receptive layer is composed of aluminum oxide fine particles having two kinds of particle sizes and a partial saponification having a polymerization degree of 1000 or more and a saponification degree of 80 to 95 mol%. An ink jet recording sheet, which is a layer formed by fixing with a binder containing a poly (vinyl alcohol) as a main component, is described, and JP-A No. 11-198520 discloses a layer of γ-type or δ-type aluminum oxide, water-soluble or water-swellable. Ink-jet recording materials, which are formed by sequentially stacking polymer-containing layers, are described, but all of them are sufficiently satisfied with inkjet suitability such as ink absorbency, image density, beading, and fixability (scratch resistance). It wasn't something that let me.

[0014]

SUMMARY OF THE INVENTION The present invention provides an ink jet recording method, a recording apparatus, an ink / media set, and a recorded matter that solve the above-mentioned conventional drawbacks. In particular, the discharge stability and the storage stability are improved. Excellent and good color tone, high image density, characters, blurring around the image,
An ink jet recording method capable of giving a recorded image with high sharpness that does not cause bleeding, an image with less color bleeding at the boundary between different colors (color bleed), unevenness, image fastness such as water resistance, light resistance, and scratch resistance. It is an object of the present invention to provide a recording apparatus, an ink / media set, and a recorded matter.

[0015]

As a result of intensive studies on the above problems, the inventors of the present invention have found that it is difficult to solve the above problems by improving only a recording medium or ink alone. On the surface of the recording medium having one or more porous layers containing particles on the porous layer side, according to the recorded information,
By applying an ink containing a polymer emulsion containing a water-insoluble or sparingly soluble coloring material to polymer fine particles to perform recording, the above problems, in particular, an image having high absorptivity of a pigment ink and a uniform image can be obtained. It was found that the scratch resistance of the recorded image was improved, and the present invention was accomplished.

That is, the above-mentioned problem is solved by (1) of the present invention.
According to recording information, polymer fine particles contain a water-insoluble or sparingly soluble coloring material on the surface of the recording medium having one or more porous layers containing inorganic particles on a substrate. Inkjet recording method characterized in that recording is performed by applying an ink containing the polymer emulsion described above, (2) "on the porous layer side of a recording medium having a porous layer of alumina hydrate on a substrate. An ink jet recording method characterized in that an ink containing a polymer emulsion in which a water-insoluble or sparingly soluble coloring material is contained in polymer fine particles is applied on the surface according to recording information to perform recording ", (3 ) "The ink jet recording method according to the item (2), wherein the recording medium comprises a porous layer of hydrated alumina and a porous layer containing inorganic particles provided on the porous layer. (4) “The peak of the pore radius distribution curve of the uppermost porous layer of the recording medium is 20 nm or less, according to any one of the above items (1) to (3). Inkjet recording method ", (5)
"An ink containing a polymer emulsion obtained by containing a water-insoluble or sparingly-soluble coloring material in the polymer fine particles is glycerin, 1,3-butanediol, triethylene glycol, 1,6-hexanediol, propylene glycol, 1 1,5-pentanediol, diethylene glycol, dipropylene glycol, trimethylolpropane, and trimethylolethane, containing at least one or more kinds of wetting agents and having 1 or more carbon atoms.
Contain at least 1 or less polyol or glycol ether, anionic or nonionic surfactant, water-soluble organic solvent, and water, and have an ink viscosity at 25 ° C. of 5 mP
a · sec or more, the inkjet recording method according to any one of the items (1) to (4) above, (6) “the polymer forming the polymer emulsion of the ink is vinyl. Inkjet recording method according to any one of items (1) to (5) above, wherein the ink is the wetting agent in an amount of 10 to 50.
The ink-jet recording method according to any one of the items (1) to (6), characterized in that the ink contains a polymer emulsion containing a coloring material. The inkjet recording method according to any one of (1) to (7) above, wherein the solid content is 8 to 20% by weight, and (9) "containing the coloring material in the ink. The inkjet recording method according to any one of (1) to (8) above, wherein the average particle diameter of the polymer emulsion thus obtained is 0.16 μm or less. Weight ratio of the wetting agent and the solid content of the polymer emulsion (wetting agent /
(Emulsion solid) is 2 to 5, wherein the ink jet recording method according to any one of (1) to (9) above, (11) "the viscosity of the ink is 8 to 8".
20 mPa · sec (25 ° C.), the inkjet recording method according to any one of the above items (1) to (10) ”, (12)“ the number of carbon atoms in the ink is 8 or more and 11 The following polyol or glycol ether is 2-ethyl-1,3-hexanediol, wherein the inkjet recording method described in any one of (1) to (11) above, (13).
“The polyol or glycol ether having 8 or more carbon atoms and 11 or less carbon atoms in the ink is composed of 2,2,4-trimethyl-1,3-pentanediol. (1) to (11) Item 14. The inkjet recording method according to any one of items 1 to 14, wherein (14) "heat energy is applied to the ink to eject the ink. Inkjet recording method according to any one of (1) to (13) above, characterized in that mechanical energy is applied to the ink to eject the ink. , (16) “Mj is 5 to 5
35 pl, Vj is 6 to 20 m, frequency is 1 KHz or more, resolution is 300 dpi or more, and recording is performed under one-pass printing conditions. (1) to (1)
5) The inkjet recording method according to any one of the items 5).

Further, the above-mentioned problems are (17) of the present invention, "the ink containing portion or the ink cartridge used in the ink jet recording method according to any one of the above (1) to (16), and the energy of the ink. Inkjet recording apparatus characterized by comprising a head unit or a recording unit for dropping and discharging by the action of "
(18) "Ink media set characterized by being used by the recording method according to any one of the items (1) to (16)", (19) "Items (1) to () 16) The recorded matter characterized by being recorded by the recording method according to any one of the items 16).

The recording medium used in the ink jet recording method of the present invention is a recording medium having one or more porous layers containing inorganic particles on a substrate. It is considered that since the void structure of the porous layer of the recording medium and the physical properties of the ink are matched, the ink absorbency is excellent and a high image density can be obtained. Further, it has a high affinity with the vinyl-based polymer, the polyester-based polymer and the polyurethane-based polymer used as a polymer forming the polymer emulsion of the following ink with the porous layer of the recording medium, and is effective as a binder for the coloring material. It is presumed that the scratch resistance of the recorded image is excellent because the above is sufficiently expressed.

The base material of the recording medium used in the recording method of the present invention is not particularly limited and various materials can be used. Specifically, polyester resins such as polyethylene terephthalate, polycarbonate resins, ET
Plastics such as fluorocarbon resin such as FE, and various papers such as plain paper, art paper and coated paper can be preferably used. Furthermore, cloth, glass or metal can also be used.
These substrates may be subjected to corona discharge treatment or various undercoats for the purpose of improving the adhesive strength with the porous layer. When a transparent plastic film is used as a base material, a transparent recorded material that can be used as an OHP (overhead projector) sheet or the like can be obtained. When an opaque plastic film containing a white pigment, paper, or the like is used as the base material, a recorded matter comparable to a silver salt photograph can be obtained.

The alumina hydrate porous layer has sufficient absorbability when the average pore radius is 1 to 15 nm and the pore volume is 0.3 to 1.0 cc / g, and the alumina water The Japanese layer is also preferable because it has transparency. At this time, if the substrate is transparent, a recording medium having high transparency can be obtained. Even when the base material is opaque, it is possible to obtain a recording medium capable of obtaining an image with high quality and high color density without impairing the texture of the base material. The average pore diameter of the alumina hydrate porous layer is 3 to
More preferably, it is 10 nm. The pore radius distribution is measured by the nitrogen desorption method.

In the present invention, the porous layer of the recording medium functions as an ink absorbing layer and / or a coloring material fixing layer. When the porous layer is composed of one layer, it serves as an ink absorbing layer and a coloring material fixing layer. When the porous layer has a plurality of layers, the lower layer serves as an ink absorbing layer and the upper layer serves as a coloring material fixing layer. Functions as a layer.

The inorganic particles contained in the porous layer are preferably silica, alumina, and fine particles of a composite of silica and alumina. Alumina, especially pseudo-boehmite, is preferred for obtaining a transparent porous layer. Here, pseudo-boehmite is A
It is an aggregate of alumina hydrate represented by the composition formula of l ₂ O ₃ .nH ₂ O (n = 1 to 1.5).

A binder is preferably contained in the porous layer. As the binder, starch or a modified product thereof, polyvinyl alcohol or a modified product thereof,
Organic substances such as SBR latex, NBR latex, carboxymethyl cellulose, hydroxymethyl cellulose and polyvinylpyrrolidone can be used.

The amount of the binder used is 5 to 5 of the inorganic particles.
It is preferable to employ about 0% by weight. If the amount of the binder used is less than 5% by weight, the strength of the alumina hydrate layer may be insufficient, and if it exceeds 50% by weight, the ink absorption may be insufficient. Therefore, it is not preferable. Further, spherical particles may be mixed in order to impart automatic transportability to the recording sheet.
In addition, organic particles may be mixed.

The uppermost porous layer preferably has a pore structure such that the peak of the pore radius distribution curve is 20 nm or less. With such a porous layer, a high image density can be obtained and an image having a glossy feeling can be obtained. This is because the coloring material in the ink is fixed on or near the surface of the uppermost porous layer. When the peak of the pore radius distribution curve of the uppermost porous layer is larger than this range, the ink absorption rate is excellent, but the dot diameter becomes too small and the image density becomes low.

The measurement of the pore radius distribution in the present invention will be described. In order to exclude the influence of the substrate and the lower porous layer, the porous layer was provided on the film, and then the porous layer was peeled off and used for the measurement. It is also possible to provide a porous layer on the film and measure it as it is. The pore size distribution can be calculated by using the void volume distribution curve obtained by the mercury intrusion method.

In the recording medium used in the recording method of the present invention, a layer containing particles and a binder as main components is provided on the base material (back surface) on the side opposite to the side where the porous layer is provided for improving transportability. May be provided.

As a method for forming a porous layer on a substrate, a binder and a solvent are added to inorganic particles to prepare a coating solution,
A preferred method is to apply this to a substrate and then dry it. The coating method is, for example, a die coater, a roll coater,
It is preferable to use an air knife coater, a blade coater, a rod coater, a bar coater, a comma coater or the like. As a solvent for the coating liquid, either an aqueous system or a non-aqueous system can be adopted.

The thickness of the porous layer is appropriately selected according to the specifications of each printer and the like, and it is generally preferable to adopt 5 to 50 μm. If the thickness of the porous layer is less than 5 μm, the ink may not be sufficiently absorbed, which is not preferable. When the thickness of the porous layer exceeds 50 μm,
It is not preferable because the transparency of the porous layer may be impaired or the strength of the layer may be reduced.

As a method of forming a plurality of porous layers,
Add a solvent to inorganic particles, binder, etc. to make a coating liquid,
A preferred method is to apply this to the lower porous layer and then dry it. The coating method is the same as in the case of forming the lower porous layer.
Die coater, roll coater, air knife coater,
A blade coater, rod coater, bar coater, comma coater, etc. can be adopted. As a solvent for the coating liquid, either an aqueous system or a non-aqueous system can be adopted.

When forming a plurality of porous layers, the thickness of the uppermost layer is appropriately selected according to the specifications of each printer,
Generally, it is preferable to adopt 0.2 to 15 μm. If the thickness of the uppermost layer is less than 0.2 μm, the fixing property of the ink may not be sufficiently improved, which is not preferable. If the thickness of the uppermost layer exceeds 15 μm, the ink absorbability may be deteriorated, which is not preferable.

The first characteristic of the ink used in the recording method of the present invention is an aqueous ink having a low surface tension of 40 dyne / cm or less at 25 ° C.
To use the ink set. This is because the present inventors have studied various means for improving the drying property of a recorded image, and as a result, the surface tension of the ink is 40 dy.
It is based on the finding that it is possible to rapidly permeate and dry almost all recording materials by adjusting so as to be ne / cm or less. In addition, by setting the surface tension of the ink to 40 dyne / cm or less, the wetting of the ink on the head member is improved, the frequency response is improved even with high viscosity ink of 8 cps (25 ° C.) or more, and the ejection stability is significantly improved. Due to the improvement. This low surface tension ink can be achieved by using a polyol or glycol ether having 8 or more and 11 or less carbon atoms and an anionic or nonionic surfactant.

The second feature is that the printing quality is remarkably improved by using a high viscosity ink or ink set having a viscosity of 5 cps or more, preferably 8 cps (25 ° C.) or more. The low viscosity ink of about 3 cps (25 ° C.) used in the conventional ink jet printer has a water content of about 70%, but the high viscosity ink of about 8 cps (25 ° C.) has a water content of about 50% or less. When the ink droplets land on the paper surface, the water evaporation rate becomes 2.0 to 3.0 times higher. For this reason, the high-concentration pigment aggregates on the paper surface at a high speed, and bleeding is almost eliminated.

The third characteristic is that the concentration of the polymer emulsion containing the coloring material in the ink is 8% by weight or more, preferably 10% by weight or more in terms of solid content. By increasing the polymer emulsion concentration or pigment concentration,
The viscosity of the ink becomes high, the pigment easily aggregates and remains on the surface of the ink receiving layer of the recording medium, the color density and color tone are improved, and the bleeding is almost eliminated.

The fourth characteristic is that glycerin, 1,3-
High-viscosity wet of at least one selected from butanediol, triethylene glycol, 1,6-hexanediol, propylene glycol, 1,5-pentanediol, diethylene glycol, dipropylene glycol, trimethylolpropane, and trimethylolethane. It is to use a high-viscosity wetting agent that is a mixture of an agent and glycerin. When a high viscosity wetting agent is used, a high viscosity ink can be obtained in combination with a high pigment concentration.

The ink composition used in the present invention has an ink viscosity of 5 cps or more, preferably 8 cp, having the following constitution.
A recording ink of s (25 ° C.) or higher. A coloring material for printing, water for dispersing it as an essential component, a wetting agent added as necessary, a water-soluble organic solvent,
Anionic or nonionic surfactant, emulsion,
It is composed of preservatives and pH adjusters. The wetting agents 1 and 2 are mixed to utilize the characteristics of each wetting agent and to adjust the viscosity, but the wetting agents 1 and 2 are not necessarily included together.

Coloring agent Wetting agent 1 (glycerin) Wetting agent 2 (1,3-butanediol, triethylene glycol, 1,6-hexanediol, propylene glycol, 1,5-pentanediol, diethylene glycol, dipropylene glycol, tri At least one or more selected from methylolpropane and trimethylolethane) Water-soluble organic solvent anion or nonionic surfactant Polyol or glycol ether preservative having 8 or more and 11 or less carbon atoms pH adjusting agent Pure water

The components of each ink will be described below. As the coloring material, a polymer emulsion in which water-insoluble or sparingly soluble coloring material is contained in fine polymer particles is used. In the present invention, “containing a coloring material” means either or both of a state in which the coloring material is encapsulated in the polymer particles and a state in which the coloring material is adsorbed on the surface of the polymer particles. In this case, it is not necessary that all of the coloring materials mixed in the ink of the present invention are encapsulated or adsorbed in the polymer fine particles, and the coloring materials are dispersed in the emulsion as long as the effects of the present invention are not impaired. Good. As the coloring material, any coloring material that is water-insoluble or sparingly water-soluble and can be adsorbed by the polymer can be used without particular limitation. In the present invention, the term "water-insoluble or sparingly water-soluble" means that the coloring material is 10 parts with respect to 100 parts by weight of water at 20.
It means that at least parts by weight is not dissolved, and that dissolved means that no separation or sedimentation of the coloring material is visually observed in the surface layer or lower layer of the aqueous solution. Examples of the coloring material include dyes such as oil-soluble dyes and disperse dyes, and pigments. Oil-soluble dyes and disperse dyes are preferable from the viewpoint of good adsorption / encapsulation properties, but pigments are preferably used from the viewpoint of light resistance of the image obtained.

Each of the above dyes used in the present invention is an organic solvent, from the viewpoint of efficiently impregnating fine polymer particles.
For example, 2 g / liter or more is preferably dissolved in the ketone solvent, and more preferably 20 to 600 g / liter is dissolved.

The pigment used in the present invention includes carbon black as a black pigment, and the color pigments include anthraquinone, phthalocyanine blue, phthalocyanine green, diazo, monoazo, pyranthrone, perylene, heterocyclic yellow, quinacridone and (thio). ) Including indigoid. Representative examples of phthalocyanine blue include copper phthalocyanine blue and its derivatives (Pigment Blue 15). Typical examples of quinacridone are Pigment Orange 48 and Pigment Orange 4
9, Pigment Red 122, Pigment Red 19
2, Pigment Red 202, Pigment Red 20
6, Pigment Red 207, Pigment Red 20
9, Pigment Violet 19 and Pigment Violet 42. Representative examples of anthraquinones include Pigment Red 43, Pigment Red 194 (Perinone Red), Pigment Red 216 (Brominated Pyrantron Red) and Pigment Red 226 (Pyrantron Red). Typical examples of pyrelin are Pigment Red 123 (Bermillion) and Pigment Red 1
49 (Scarlet), Pigment Red 179 (Maroon), Pigment Red 190 (Red), Pigment Violet, Pigment Red 189 (Yellow Shade Red) and Pigment Red 224.
Pigment Red 8 is a typical example of thioindigoide.
6, Pigment Red 87, Pigment Red 88, Pigment Red 181, Pigment Red 198, Pigment Violet 36 and Pigment Violet 38. Representative examples of heterocyclic yellow include Pigment Yellow 117 and Pigment Yellow 138. Examples of other suitable color pigments are The Color Index, Third Edition (The Society of Dyers and Colorists, 1982).
It is described in.

When the pigment is used as a colorant, the above dyes can be used together for complementary colors and toning.
The blending amount of the coloring material is about 10 to 200% by weight based on the weight of the polymer in relation to the blending amount of the polymer.
It is particularly preferably about 25 to 150% by weight.

As the polymer forming the polymer emulsion, for example, a vinyl polymer, a polyester polymer and a polyurethane polymer can be used. Polymers particularly preferably used are vinyl-based polymers and polyester-based polymers.
The polymers disclosed in 000-53897 and 2001-139849 are mentioned.

According to a preferred embodiment of the present invention, the average particle diameter of the polymer fine particles containing these coloring materials is most preferably 0.16 μm or less in the ink. The content of polymer fine particles in the ink is preferably about 8 to 20% by weight, more preferably about 8 to 12% by weight in terms of solid content.

Regarding the wetting agent and the water-soluble organic solvent, the ink of the present invention uses water as a liquid medium, but in order to make the ink have desired physical properties, prevent the ink from drying, and disperse the ink. For the purpose of improving stability,
For example, the following water-soluble organic solvents are used. A plurality of these water-soluble organic solvents may be mixed and used.

Specific examples of the wetting agent and the water-soluble organic solvent include the followings. Ethylene glycol, diethylene glycol, triethylene glycol,
Propylene glycol, dipropylene glycol, tripropylene glycol, tetraethylene glycol, hexylene glycol, polyethylene glycol, polypropylene glycol, 1,5-pentanediol, 1,
6-hexanediol, glycerol, 1,2,6-hexanetriol, 1,2,4-butanetriol,
Polyhydric alcohols such as 1,2,3-butanetriol and petriol; ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, tetraethylene glycol monomethyl ether, propylene glycol Polyhydric alcohol alkyl ethers such as monoethyl ether; Polyhydric alcohol aryl ethers such as ethylene glycol monophenyl ether and ethylene glycol monobenzyl ether; 2
-Nitrogen-containing heterocyclic compounds such as pyrrolidone, N-methyl-2-pyrrolidone, N-hydroxyethyl-2-pyrrolidone, 1,3-dimethylimidinazolidinone, ε-caprolactam, γ-butyrolactone; formamide, N-methyl Amides such as formamide, N, N-dimethylformamide; monoethanolamine, diethanolamine,
Amines such as triethanolamine, monoethylamine, diethylamine and triethylamine; sulfur-containing compounds such as dimethyl sulfoxide, sulfolane and thiodiethanol; propylene carbonate and ethylene carbonate.

Among these organic solvents, particularly diethylene glycol, thiodiethanol, polyethylene glycol 200 to 600, triethylene glycol, glycerol, 1,2,6-hexanetriol, 1,2,4-
Butanetriol, petriol, 1,5-pentanediol, 2-pyrrolidone and N-methyl-2-pyrrolidone are preferred. These have excellent effects on solubility and prevention of defective ejection characteristics due to water evaporation.

The other wetting agent preferably contains sugar. Examples of sugars include monosaccharides, disaccharides,
Examples thereof include oligosaccharides (including trisaccharides and tetrasaccharides) and polysaccharides, preferably glucose, mannose, fructose, ribose, xylose, arabinose, galactose, maltose, cellobiose, lactose, sucrose, trehalose and maltotriose. To be Here, the polysaccharide means a sugar in a broad sense, and is meant to include substances widely existing in the natural world such as α-cyclodextrin and cellulose.

The derivatives of these saccharides include reducing sugars of the above-mentioned saccharides (for example, sugar alcohol (general formula H
OCH ₂ (CHOH) nCH ₂ OH (where n = 2-5
Represents the integer. ). ), Oxidized sugars (eg, aldonic acid, uronic acid, etc.), amino acids, thioacids and the like. Sugar alcohol is particularly preferable, and specific examples thereof include maltitol, sorbitol and the like.
The content of these saccharides is appropriately in the range of 0.1 to 40% by weight, preferably 0.5 to 30% by weight of the ink composition.

The ratio of the pigment to the wetting agent has a great influence on the stability of ink ejection from the head. If the solid content of the pigment is high but the amount of the wetting agent is small, the evaporation of water in the vicinity of the ink meniscus of the nozzle will occur, resulting in ejection failure. The content of the wetting agent is 10 to 50% by weight, whereas the amount of the polymer particles containing the coloring material is 8% by weight or more, preferably 8 to 2%.
Since it is 0% by weight, the ratio of both the wetting agent and the solid polymer fine particles is 0.5 to 6.25, more preferably 2.0 to 6.0, and most preferably 3.0 to 6. 5.0
Is the range. Inks in this range are very good in drying property, storage test and reliability test.

As the surfactant, an anionic surfactant or a nonionic surfactant is used. A surfactant that does not impair the dispersion stability is selected depending on the combination of the coloring material, the wetting agent, and the water-soluble organic solvent. Examples of the anionic surfactant include polyoxyethylene alkyl ether acetate, dodecylbenzene sulfonate, lauryl salt, and salt of polyoxyethylene alkyl ether sulfate.

Examples of the nonionic surfactant include, for example,
Examples thereof include polyoxyethylene alkyl ether, polyoxyethylene alkyl ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene alkylphenyl ether, polyoxyethylene alkylamine, and polyoxyethylene alkylamide.

The acetylene glycol surfactant is
2,4,7,9-Tetramethyl-5-decyne-4,7-
Diol, 3,6-dimethyl-4-octyne-3,6-
Acetylene glycols such as diol and 3,5-dimethyl-1-hexyn-3-ol (for example, Surfynol 104, 82, 46 manufactured by Air Products (USA)).
5, 485 or TG) can be used, but Surfynol 465, 104 and TG show particularly good print quality. The surfactants may be used alone or in combination of two or more.

In the present invention, the use of a surfactant can improve the wettability to recording paper. Preferred surfactants include interfacial polyoxyethylene alkyl ether acetate, dialkyl sulfosuccinate, polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene polyoxypropylene block copolymer, acetylene glycol surfactant Agents. More specifically, examples of the anionic surfactant include polyoxyethylene alkyl ether acetate (I), and / or dialkylsulfosuccinic acid (II) having a branched alkyl chain having a carbon chain of 5 to 7, By using these, the properties of plain paper are also improved, and the dissolution and dispersion stability of the colorant can be obtained.

[0054]

Embedded image R ₁ —O— (CH ₂ CH ₂ O) mCH ₂ COOM ... (I) (R ₁ : an alkyl group having 6 to 14 carbon atoms which may be branched,
m: 3 to 12, M: alkali metal ion, quaternary ammonium, quaternary phosphonium, alkanolamine)

[0055]

[Chemical 2] _{(R 2:} branched alkyl group having 5 to 16 carbon atoms, M: an alkali metal ion, quaternary ammonium, quaternary phosphonium, alkanolamine)

[0056]

[Chemical 3] (R is a 6-14 carbon chain which may be branched, k: 5-2
0)

[0057]

Embedded image R- (OCH ₂ CH ₂ ) nOH (IV) (R is a carbon chain having 6 to 14 carbon atoms which may be branched, n: 5
~ 20)

[0058]

[Chemical 5] (R ′ is a carbon chain having 6 to 14 carbon atoms, m ≦ 20, n ≦ 2
0)

[0059]

[Chemical 6] (P and q are 0-40)

Further, the use of lithium ion as a counter ion of the surfactant of the present invention and quaternary ammonium or quaternary phosphonium represented by the following general formula makes the surfactant exhibit excellent solubility stability.

Preferred nonionic surfactants include polyoxyethylene alkylphenyl ethers of the general formula (III) and acetylene glycol surfactants of the general formula (VI). When these are used in combination, the synergistic effect is further enhanced in penetrability, whereby an ink with less color boundary bleeding and less character bleeding can be obtained.

By setting the pH of the ink to 6 or more, the storage stability of the ink can be obtained, and most of the copy paper, sticky notes and the like used in the office have a pH of 5 to 6, ink to fly at 5 to 20 m / s as droplets of weight 3ng~50ng discharged finer discharge port of 9~60μm in these recording sheet, 30 g of the adhesion amount of a single color from 1.5 g / ^{m 2} / M ² as JIS P-8
It is possible to provide a recording method for forming a recorded image of high image quality and high resolution by recording on so-called plain paper having a Steckigt sizing degree of 3 seconds or more by the 122 test method. However,
When the pH is 9 or more, the property of the activator of (II) is apt to change due to decomposition at the time of storage.
It is preferable that H is 6 to 9.

(I) and (I which can be used in the present invention
The addition amount of I), (III), (IV), (V), and (VI) was 0.
It is possible to give the desired penetration for the ink properties required by the printer system between 05 and 10% by weight. If 0.05% or less, it is 2 in any case.
Bleeding occurs at the boundary of the color overlapping portion, and when 10% by weight or more is added, the compound itself tends to precipitate at low temperature, resulting in poor reliability. Table 1 specifically shows the surfactants (I) and (II) used in the present invention in a free acid form.

[0064]

[Table 1]

The surface tension in the present invention is an index showing the penetrability into paper, and in particular, shows the dynamic surface tension in a short time of 1 second or less after the surface is formed, and the static surface tension measured at the saturation time. Is different from. As a measuring method, JP-A-63-31
Although it is possible to use any method capable of measuring a dynamic surface tension of 1 second or less by a conventionally known method described in Japanese Patent No. 237, etc.
In the present invention, the measurement was performed using a Wilhelmy hanging plate type surface tensiometer. The surface tension is preferably 40 mJ / ^{m 2} or less, more preferably dry can be obtained with excellent fixability and 35 mJ / ^{m 2} or less.

The polyol or glycol ether having 8 or more and 11 or less carbon atoms used in the present invention is a partially water-soluble polyol having a solubility of 0.1 to less than 4.5% by weight in water at 25 ° C. 0.1 to 1 based on the total weight of the recording ink.
It was found that the addition of 0.0% by weight improves the wettability of the ink to the thermal element, and discharge stability and frequency stability can be obtained even with a small addition amount. 2-Ethyl-1,3-hexanediol Solubility:
4.2% (20 ° C) 2,2,4-trimethyl-1,3-pentanediol Solubility: 2.0% (25 ° C)

Penetrants having a solubility of between 0.1 and less than 4.5% by weight in water at 25 ° C. have the advantage of having a very high permeability at the expense of low solubility. Therefore,
Combining penetrants with solubilities between 0.1 and 4.5% by weight in water at 25 ° C. with other solvents and with other surfactants to make very highly penetrative inks. It becomes possible.

To the ink of the present invention, conventionally known additives can be added in addition to the colorant, solvent and surfactant. For example, as antiseptic / antifungal agents, sodium dehydroacetate, sodium sorbate, sodium 2-pyridinethiol-1-oxide, sodium benzoate, sodium pentachlorophenol and the like can be used in the present invention.

As the pH adjuster, any substance can be used as long as it can adjust the pH to 7 or more without adversely affecting the ink to be prepared. Examples thereof include amines such as diethanolamine and triethanolamine, hydroxides of alkali metal elements such as lithium hydroxide, sodium hydroxide and potassium hydroxide, ammonium hydroxide, quaternary ammonium hydroxide and quaternary phosphonium. Examples thereof include hydroxides, carbonates of alkali metals such as lithium carbonate, sodium carbonate and potassium carbonate.

Examples of the chelating agent include sodium ethylenediaminetetraacetate, sodium nitrilotriacetate, sodium hydroxyethylethylenediaminetriacetate, sodium diethylenetriaminepentaacetate and sodium uramildiacetate.

Examples of the rust preventive agent include acid sulfite,
There are sodium thiosulfate, ammonium thiodiglycolate, diisopropylammonium nitrite, pentaerythritol tetranitrate, dicyclohexylammonium nitrite and the like. A water-soluble ultraviolet absorber, a water-soluble infrared absorber or the like can be added depending on the purpose.

Next, the ink / media set of the present invention will be described. The ink / media set of the present invention is
It is a set of ink and a recording medium used in the recording method of the present invention. At least three inks of yellow, magenta, and cyan are set. Black ink is used as needed.

[0073]

BEST MODE FOR CARRYING OUT THE INVENTION A recording liquid cartridge containing a recording liquid of the present invention and an ink jet recording apparatus equipped with the recording liquid cartridge will be described with reference to the drawings. It does not impose any limitation on the invention.

FIG. 1 is a schematic front view of a mechanical portion of a serial type ink jet recording apparatus equipped with an ink cartridge having a recording liquid storage portion for storing the recording liquid of the present invention. The mechanism portion of this ink jet recording apparatus has a main support guide rod (3) and a sub support guide rod (4) which are laterally bridged between the side plates (1) and (2) on both sides,
The carriage unit (5) is slidably supported in the main scanning direction by the main supporting guide rod (3) and the sub supporting guide rod (4). The carriage unit (5) has four heads (6) for respectively ejecting yellow (Y) ink, magenta (M) ink, cyan (C) ink, and black (Bk) ink, and its ejection surface (nozzle). The surface (6a) is mounted downward, and above the heads (6) of the carriage unit (5) are ink supply members of respective colors for supplying ink to the four heads (6). 4 ink cartridges (7y),
(7m), (7c), and (7k) are exchangeably mounted. The carriage unit (5) has a timing belt (11) stretched between a driving pulley (driving timing pulley) (9) rotated by a main scanning motor (8) and a driven pulley (idler pulley) (10). Connected to
By driving and controlling the main scanning motor (8), the carriage (5), that is, the four heads (6) are moved in the main scanning direction.

Subframes (13) and (14) are erected on the bottom plate (12) connecting the side plates (1) and (2), and the paper (1
A conveyance roller (15) for feeding 6) in the sub scanning direction orthogonal to the main scanning direction is rotatably held. And
A sub-scanning motor (17) is arranged on the side of the sub-frame (14), and in order to transmit the rotation of the sub-scanning motor (17) to the conveying roller (15), the sub-scanning motor (17) has a rotating shaft. It has a fixed gear (18) and a gear (19) fixed to the shaft of the transport roller (15).

Furthermore, the side plate (1) and the sub-frame (1
A reliability maintaining / restoring mechanism (hereinafter referred to as a “subsystem”) (21) for the head (6) is arranged between the head and the head (2). The subsystem (21) holds four cap means (22) for capping the ejection surface of each head (6) by a holder (23), and the holder (23) can be swung by a link member (24). The carriage unit (5) abuts on the engaging portion (25) provided on the holder (23) by the movement of the carriage unit (5) in the main scanning direction. The holder (23) is lifted up, the ejection surface (6a) of the inkjet head (6) is capped by the cap means (22), and the carriage unit (5) moves to the printing area side, whereby the carriage unit (5). ), The holder (23) is lifted down to move the cap means (2).
2) is separated from the ejection surface (6a) of the inkjet head (6).

The cap means (22) is connected to the suction pump (27) via the suction tube (26) and forms an atmosphere opening port, and the atmosphere is opened via the atmosphere opening tube and the atmosphere opening valve. Is in communication with. The suction pump (27) discharges the sucked waste liquid to a waste liquid storage tank (not shown) via a drain tube or the like. Further, on the side of the holder (23), a fiber member for wiping the ejection surface (6a) of the inkjet head (6),
A wiper blade (28), which is a wiping means made of an elastic member such as a foam member or rubber, is attached to the blade arm (2
9), the blade arm (29) is pivotally supported so that it can be pivoted by the rotation of a cam pivoted by a driving means (not shown).

Next, the ink cartridge (7) will be described with reference to FIGS. Here, in FIG.
FIG. 3 is an external perspective view of the ink cartridge before being loaded in the recording apparatus, and FIG. 3 is a front sectional view of the ink cartridge. As shown in FIG. 3, the ink cartridge (7) comprises an ink absorber (42) which absorbs ink of a desired color in a cartridge body (41). The cartridge body (41) is formed by adhering or welding an upper lid member (44) to the upper opening of a case (43) having a wide opening at the top, and is made of, for example, a resin molded product. The ink absorber (42) is made of a porous material such as urethane foam, and absorbs ink after being compressed and inserted into the cartridge body (41). An ink supply port (4) for supplying ink to the recording head (6) is provided at the bottom of the case (43) of the cartridge body (41).
5) is formed, and a seal ring (46) is fitted on the inner peripheral surface of the ink supply port (45). Further, the upper lid member (44) is formed with an atmosphere opening port (47). And, in the cartridge body (41) in the state before loading,
The ink supply port (45) is closed, and the case (43) is prevented from being compressed and deformed by the pressure applied to the wide side wall at the time of cartridge handling such as loading or transportation, or at the time of vacuum packaging to leak the ink inside. Therefore, the cap member (50) is attached.

Further, as shown in FIG. 2, the atmosphere opening port (47) is sealed by attaching a film-like sealing member (55) having an oxygen permeability of 100 ml / m ² or more to the upper lid member (44). ing. The seal member (55) is provided with a plurality of grooves (48) formed around the atmosphere opening port (47).
It is also sized to seal even. By thus sealing the atmosphere opening port (47) with the sealing member (55) having an oxygen permeability of 100 ml / m ² or more, the ink cartridge (7) is made of a non-air permeable packaging material such as an aluminum laminate film. When the ink is packed in a reduced pressure state, gas is contained in the ink due to the atmosphere in the space (A) (see FIG. 3) generated when the ink is filled and between the ink absorber (42) and the cartridge body (41). Even when dissolved, the air in the ink is discharged through the seal member (55) to the space between the cartridge body (41) having a high degree of vacuum and the packaging member, and the degassing degree of the ink is improved.

Further, FIG. 4 shows an example of the construction of a recording cartridge having a recording liquid storage portion for storing the recording liquid of the present invention and a head portion for ejecting recording liquid droplets. That is, the recording unit (30) is of a serial type, and includes an inkjet head (6), an ink tank (41) containing a recording liquid supplied to the inkjet head (6), and the ink tank (4).
1) The main part is composed of a lid member that seals the inside. The inkjet head (6) has a large number of nozzles (32) for ejecting a recording liquid. The recording liquid is guided from the ink tank (41) to the common liquid chamber (not shown) through the ink supply pipe (not shown), and the electrode (3
It is ejected from the nozzle (32) in response to an electric signal from the recording apparatus main body input from 1). Such a type of recording unit has a structure suitable for a type of head that can be manufactured at low cost, that is, a so-called thermal type or bubble type head that uses thermal energy as a driving power source. The recording liquid of the present invention improves wettability to a thermal element by adding a C _{8 to} C ₁₁ polyol or glycol ether in a recording method such as a bubble method or a thermal method. Ejection stability and frequency stability are obtained, and safety is high, which is very suitable.

Here, the serial type ink jet recording apparatus as described above has been described. However, the recording liquid of the present invention has the nozzles in an arbitrary arrangement such as a staggered pattern and has the same resolution as a target image or a fraction thereof. It is also possible to apply the present invention to a recording apparatus having a so-called line head, which is integrated in the density of 1 and is arranged over the width of the recording medium. Further, the recording device mentioned here may be not only an output printer for a PC or a digital camera, but also a device having a composite function in combination with a fax, a scanner, a telephone or the like.

[0082]

EXAMPLES Examples and comparative examples of the present invention will be shown below, but the present invention is not limited thereto. <Preparation of Recording Medium 1> Preparation of Silica Fine Particles for Recording Medium [Silica Fine Particle A] Synthetic amorphous silica having an average secondary particle diameter of 2 μm (manufactured by Nippon Silica Industry Co., Ltd., trade name: Nip
sil HD, average primary particle diameter: 13 nm), and after dispersing with a sand grinder, further dispersing with an ultrasonic homogenizer to obtain secondary particles having an average particle diameter of 250 nm.
The dispersion operation of the sand grinder and the ultrasonic homogenizer was repeated until it became, and a 15% aqueous solution was produced as a prototype.

[Silica fine particles B] Synthetic amorphous silica having an average secondary particle diameter of 2.2 μm (manufactured by Nippon Silica Industry Co., Ltd., trade name: Nipsil K-300, average primary particle diameter: 15 nm) was used. After dispersing with a sand grinder, further dispersing with an ultrasonic homogenizer, repeating the dispersing operation of the sand grinder and ultrasonic homogenizer until the average particle size of the secondary particles becomes 90 nm, 12%
An aqueous solution of

[Silica fine particles C] Synthetic amorphous silica having an average secondary particle diameter of 2 μm (manufactured by Nippon Silica Industry Co., Ltd., trade name: Nipsil HD, average primary particle diameter: 13 n
m) is dispersed by a sand grinder, then further dispersed by an ultrasonic homogenizer, and the dispersion operation of the sand grinder and the ultrasonic homogenizer is repeated until the average particle size of the secondary particles reaches 40 nm, to make an 8% aqueous solution as a trial. did.

(Recording medium 1) Average particle size of secondary particles 4.
5 μm synthetic amorphous silica (manufactured by Tokuyama Corp., trade name: Fineseal X-45, average primary particle size: about 15)
nm) 100 parts, PVA (Kuraray Co., Ltd., trade name: PV
A-117, degree of polymerization: 1800, degree of saponification: 98.5
%) 40% of a 15% aqueous solution was mixed and coated with a wire bar on resin-coated paper (polyethylene 18 μm laminated on the surface of coated paper) so that the coating amount was 15 g / m ² and dried. , A lower porous layer was provided. Next, PVA (manufactured by Kuraray Co., Ltd.
Trade name: PVA-135H) A 12% aqueous solution mixed with 40 parts is coated with a wire bar to a coating amount of 5 g / m ² and dried to provide a porous layer of the uppermost layer, and the recording medium of the present invention. Got The peak of the pore radius distribution curve of the uppermost porous layer was 44 nm.

(Recording medium 2) On the lower porous layer of the recording medium 1, 100 parts of silica fine particles B and 40 parts of PVA (trade name: PVA-135H manufactured by Kuraray Co., Ltd.) were mixed.
A 2% aqueous solution was applied with a wire bar to a coating amount of 5 g / m ² and dried to provide a porous layer as the uppermost layer, and a recording medium 2 was obtained. The peak of the pore radius distribution curve of the uppermost porous layer was 19 nm.

(Recording medium 3) On the lower porous layer of the recording medium 1, 100 parts of silica fine particles C and 40 parts of PVA (trade name: PVA-135H, manufactured by Kuraray Co., Ltd.) were mixed.
% Aqueous solution is coated with a wire bar to a coating amount of 5 g / m ² and dried to form the uppermost porous layer.
Got The peak of the pore radius distribution curve of the uppermost porous layer was 8 nm.

(Recording medium 4) Silica sol 100 having an average primary particle diameter of 15 nm is formed on the lower porous layer of recording medium 1.
Polyvinyl alcohol copolymer having a silanol group in its part (Kuraray Co., Ltd., trade name: R-Polymer R-1130)
A 10% aqueous solution mixed with 35 parts was applied by a wire bar to a coating amount of 5 g / m ² and dried to provide a porous layer as the uppermost layer to obtain a recording medium 4. The peak of the pore radius distribution curve of the uppermost porous layer was 4 nm.

(Recording Medium 5) (Comparative Example 1) A polyvinyl acetal resin obtained by acetalizing polyvinyl alcohol having a polymerization degree of 2,000 and a saponification degree of 88 mol% with benzaldehyde (acetalization degree of 9 mol%) was used. , Water and isopropyl alcohol were dissolved in a mixed solvent containing a weight ratio of 6: 4, and urea / gluoxal / acrylamide polycondensate (SUMIREZ RESIN 5004; manufactured by Sumitomo Chemical Co., Ltd.) was added to a polyvinyl acetal resin solid content of 0. 4% by weight was added and mixed. The obtained mixed solution is applied on resin-coated paper (polyethylene 18 μm laminated on the surface of coated paper) and dried, and the coating weight after drying is 12 g / m ² ink-free layer containing no inorganic particles. A recording medium having

<Preparation of Recording Medium 2> (Recording Medium 6) Hydrolysis of Aluminum Alkoxide
Alumina sol having a solid content of 18% by weight synthesized by the peptization method 10
0 g, polyvinyl alcohol 6.2 wt% aqueous solution 32 g
To prepare a coating liquid. This coating liquid was applied onto a polyethylene terephthalate film (thickness 100 μm, white),
A bar coater is used to apply a coating amount of 26 g / m ² after drying, and a pseudo-boehmite layer is formed by drying.
A heat treatment was performed at 140 ° C. to obtain a recording medium 6. The peak of the pore radius distribution curve of the uppermost porous layer was 8 nm.

(Recording medium 7) 100 g of alumina sol having a solid content of 18% by weight synthesized by hydrolysis / peptization of aluminum alkoxide, 6.2% by weight of polyvinyl alcohol
A coating solution was prepared by mixing 32 g of the aqueous solution. A polyethylene terephthalate film (thickness 100 μm,
It was coated on a white layer using a bar coater so that the coating amount after drying was 26 g / m ² , and dried to form a pseudo-boehmite layer. Furthermore, a polyvinyl alcohol copolymer having a primary particle size of 10 to 20 nm and a silanol group and a silanol group (Kuraray Co., Ltd., trade name R-Polymer R-
1130) and a solid content of 5% by weight (the copolymer /
SiO ₂ = 0.3) silica sol coating solution is applied and dried so that the thickness of the dried silica gel layer is 1 μm, and 1
A heat treatment was performed at 40 ° C. to obtain a recording medium 7. The peak of the pore radius distribution curve of the uppermost porous layer was 3 nm.

(Recording medium 8) On the pseudo-boehmite layer of the recording medium 6, 100 g of an alumina sol having a solid content of 18% by weight synthesized by the hydrolysis / peptization method of aluminum alkoxide,
A coating liquid was prepared by mixing 60 g of a 6.2 wt% aqueous solution of polyvinyl alcohol. The coating amount after drying this coating solution is 1g
The coating medium was dried so as to have a thickness of / m ² and heat-treated at 140 ° C. to obtain a recording medium 8. The peak of the pore radius distribution curve of the uppermost porous layer was 6 nm.

(Recording Medium 9) (Comparative Example 2) A polyvinyl acetal resin obtained by acetalizing polyvinyl alcohol having a polymerization degree of 2,000 and a saponification degree of 88 mol% with benzaldehyde (acetalization degree of 9 mol%) was used. , Water and isopropyl alcohol were dissolved in a mixed solvent containing a weight ratio of 6: 4, and urea / gluoxal / acrylamide polycondensate (SUMIREZ RESIN 5004; manufactured by Sumitomo Chemical Co., Ltd.) was added to a polyvinyl acetal resin solid content of 0. 4% by weight was added and mixed. The obtained mixed solution was added to a polyethylene terephthalate film (thickness 1
After being coated on 100 μm, white), it was dried at 120 ° C. for 5 minutes to obtain a recording medium 9 having an ink receiving layer having a coating weight of 12 g / m ² after drying.

(Recording medium 10) A recording medium 10 was obtained in the same manner as the recording medium 7, except that the base material was changed to a polyethylene terephthalate film (thickness 100 μm, transparent).
The peak of the pore radius distribution curve of the uppermost porous layer is 3 nm
Met.

<Preparation of Ink><Reference Example 1> Preparation of Polymer Fine Particle Dispersion Containing Phthalocyanine Pigment Preparation Example 3 described in JP 2001-139849 A was additionally tested to obtain a blue polymer fine particle dispersion. The average particle diameter (D50%) of the polymer particles measured by Microtrac UPA was 93 nm.

Reference Example 2 Preparation of Polymer Fine Particle Dispersion Containing Dimethylquinacridone Pigment The phthalocyanine pigment of Reference Example 1 was used as Pigment Red 12
A reddish purple polymer particle dispersion was obtained in the same manner as in Reference Example 1 except that the number was changed to 2. The average particle size (D50%) of the polymer particles measured by Microtrac UPA is 127.
was nm.

Reference Example 3 Preparation of Monoazo Yellow Pigment-Containing Polymer Fine Particle Dispersion The phthalocyanine pigment of Reference Example 1 was used in Pigment Yellow 7
A yellow polymer particle dispersion was obtained in the same manner as in Reference Example 1 except that the number was changed to 4. The average particle size (D50%) of the polymer particles measured by Microtrac UPA is 76 nm.
Met.

<Reference Example 4> Preparation of polymer fine particle dispersion containing carbon black A black polymer fine particle dispersion was prepared in the same manner as in Reference Example 1 except that the phthalocyanine pigment of Reference Example 1 was changed to carbon black (FW100 manufactured by Degussa). Obtained. Average particle size of polymer particles measured by Microtrac UPA (D5
0%) was 104 nm.

Reference Example 5 Carbon black dispersion 1 treated with diazo compound 1 (for black ink for self-dispersion) 100 g of carbon black having a surface area of 230 m ² / g and a DBP oil absorption of 70 ml / 100 g, and p-amino- 34 g of N-benzoic acid and 7 g of water
Mix and disperse in 50 g, and add 16 g of nitric acid dropwise to 70
Stirred at ° C. After 5 minutes, a solution prepared by dissolving 11 g of sodium nitrite in 50 g of water was added, and the mixture was further stirred for 1 hour.
The obtained slurry was diluted 10 times, centrifuged to remove coarse particles, and the pH was adjusted with diethanolamine to adjust the pH to 8 to 8.
9, and the mixture was desalted and concentrated with an ultrafiltration membrane to obtain a carbon black dispersion having a pigment concentration of 15%. This was made into a carbon black dispersion liquid 1 using a polypropylene 0.5 μm filter. The average particle size (D50%) measured by Microtrac UPA was 99 nm.

(Ink 1) An ink composition having the following formulation was prepared and adjusted to a pH of 9 with a 10% aqueous solution of lithium hydroxide. Then, filtration was performed with a membrane filter having an average pore size of 0.8 μm to obtain an ink composition. Phthalocyanine pigment-containing polymer fine particles of Reference Example 1 8.0 wt% (as solid content) Triethylene glycol 22.5 wt% Glycerol 7.5 wt% 2-Pyrrolidone 5.0 wt% Specific example (I-1) described in Table 1 Activator 2.0 wt% 2-Ethyl-1,3-hexanediol 2.0 wt% Proxel LV (preservative) 0.2 wt% Ion-exchanged water Remaining amount

(Ink 2) An ink composition was prepared in the same manner as Ink 1 except that the following composition was used, and the pH was adjusted to 9 with sodium hydroxide. Dimethylquinacridone pigment-containing polymer fine particles of Reference Example 2 8.0 wt% (as solid content) Propylene glycol 30.0 wt% Glycerol 10.0 wt% N-methyl-2-pyrrolidone 2.0 wt% Specific examples described in Table 1 (I -2) activator 2.0 wt% 2,2,4-trimethyl-1,3-pentanediol 2.0 wt% Proxel LV (preservative) 0.2 wt% Ion-exchanged water Remaining amount

(Ink 3) An ink composition was prepared in the same manner as Ink 1 except that the following composition was used, and the pH was adjusted to 9 with lithium hydroxide. Monoazo yellow pigment-containing polymer fine particles of Reference Example 3 8.0 wt% (as solid content) 1,3-butanediol 22.5 wt% Glycerol 7.5 wt% 2-pyrrolidone 5.0 wt% Specific examples described in Table 1 (I -4) Activator 2.0 wt% 2,2,4-trimethyl-1,3-pentanediol 2.0 wt% Proxel LV (preservative) 0.2 wt% Ion-exchanged water Remaining amount

(Ink 4) Black Pigment Ink An ink composition was prepared in the same manner as Ink 1 except that the following composition was used, and the pH was adjusted to 9 with sodium hydroxide. Carbon black-containing polymer particles of Reference Example 4 8.0 wt% (as solid content) Dipropylene glycol 20.0 wt% Glycerol 10.0 wt% N-hydroxyethyl-2-pyrrolidone 5.0 wt% Specific examples shown in Table 1 ( I-3) Activator 2.0 wt% 2-Ethyl-1,3-hexanediol 2.0 wt% Proxel LV (preservative) 0.2 wt% Ion-exchanged water Remaining amount

(Ink 5) An ink composition was prepared in the same manner as Ink 1 except that the following composition was used, and the pH was adjusted to 9 with lithium hydroxide. Phthalocyanine pigment-containing polymer fine particles of Reference Example 1 12.0 wt% (as solid content) 2,3-butanediol 22.5 wt% Glycerol 7.5 wt% N-methyl-2-pyrrolidone 3.0 wt% Specific examples shown in Table 1 Example (I-5) Activator 2.0 wt% 2-Ethyl-1,3-hexanediol 2.0 wt% Proxel LV (preservative) 0.2 wt% Ion-exchanged water Remaining amount

(Ink 6) An ink composition was prepared in the same manner as Ink 1 except that the following composition was used, and the pH was adjusted to 9 with lithium hydroxide. Dimethylquinacridone pigment-containing polymer particles of Reference Example 2 12.0 wt% (as solid content) Dipropylene glycol 15.0 wt% Glycerol 15.0 wt% N-hydroxyethyl-2-pyrrolidone 5.0 wt% Specific examples shown in Table 1 Activator of (I-6) 2.0 wt% 2,2,4-trimethyl-1,3-pentanediol 2.0 wt% Proxel LV (preservative) 0.2 wt% Ion-exchanged water Remaining amount

(Ink 7) An ink composition was prepared in the same manner as Ink 1 except that the following composition was used, and the pH was adjusted to 9 with lithium hydroxide. Monoazo yellow pigment-containing polymer particles of Reference Example 3 12.0 wt% (as solid content) 1,3-propanediol 22.5 wt% Glycerol 7.5 wt% 2-pyrrolidone 5.0 wt% Specific examples shown in Table 1 (II -1) Activator 2.0 wt% 2-Ethyl-1,3-hexanediol 2.0 wt% Proxel LV (preservative) 0.2 wt% Ion-exchanged water Remaining amount

(Ink 8) (Comparative Example 3) An ink composition was prepared in the same manner as Ink 1 except that the following composition was used, and the pH was adjusted to 9 with lithium hydroxide. Carbon black dispersion 1 treated with the diazo compound of Reference Example 5 8.0 wt% (as solid content) 1,4-butanediol 22.5 wt% Glycerol 7.5 wt% N-methyl-2-pyrrolidone 2.0 wt% Table 1 Activator of the specific example (II-2) described in 2. 2.0 wt% 2,2,4-trimethyl-1,3-pentanediol 2.0 wt% Emulsion 3.0 wt% Proxel LV (preservative) 0.2 wt% Deionized water remaining

(Ink 9) An ink composition was prepared in the same manner as Ink 1 except that the following composition was used, and the pH was adjusted to 9 with lithium hydroxide. Phthalocyanine pigment-containing polymer fine particles of Reference Example 1 15.0 wt% (as solid content) 1,5-pentanediol 15.0 wt% Glycerol 15.0 wt% N-hydroxyethyl-2-pyrrolidone 2.0 wt% Specific example (II- 3) Activator 2.0 wt% 2-Ethyl-1,3-hexanediol 2.0 wt% Proxel LV (preservative) 0.2 wt% Ion-exchanged water Remaining amount

(Ink 10) An ink composition was prepared in the same manner as Ink 1 except that the following composition was used, and the pH was adjusted to 9 with lithium hydroxide. Dimethylquinacridone pigment-containing polymer fine particles of Reference Example 2 15.0 wt% (as solid content) 1,6-hexanediol 22.5 wt% Glycerol 7.5 wt% 2-Pyrrolidone 3.0 wt% Activity of Specific Example (II-4) Agent 2.0 wt% 2,2,4-trimethyl-1,3-pentanediol 2.0 wt% Proxel LV (preservative) 0.2 wt% Ion-exchanged water Remaining amount

(Ink 11) An ink composition was prepared in the same manner as Ink 1 except that the following composition was used, and the pH was adjusted to 9 with sodium hydroxide. Monoazo yellow pigment-containing polymer fine particles of Reference Example 3 15.0 wt% (as solid content) 2-methyl-2,4-pentanediol 22.5 wt% glycerol 7.5 wt% N-methyl-2-pyrrolidone 5.0 wt% General Activator of formula (III) (R = C6, k = 5) 2.0 wt% 2-Ethyl-1,3-hexanediol 2.0 wt% Proxel LV (preservative) 0.2 wt% Ion-exchanged water Remaining amount

(Ink 12) An ink composition having the following formulation was prepared and adjusted to a pH of 9 with a 10% aqueous solution of lithium hydroxide. Then, filtration was performed with a membrane filter having an average pore size of 0.8 μm to obtain an ink composition. Phthalocyanine pigment-containing polymer particles of Reference Example 1 5.0 wt% Ethylene glycol 15.0 wt% Glycerol 5.0 wt% 2-Pyrrolidone 2.0 wt% ECTD-3NEX (Nikko Chemicals anionic surfactant) 1.0 wt% 2- Ethyl-1,3-hexanediol 2.0 wt% Emulsion 3.0 wt% Proxel LV (preservative) 0.2 wt% Ion-exchanged water Remaining amount

(Ink 13) An ink composition was prepared in the same manner as Ink 12 except that the following composition was used, and the pH was adjusted to 9 with lithium hydroxide. Dimethylquinacridone pigment-containing polymer fine particles of Reference Example 2 6.0 wt% Diethylene glycol 15.0 wt% Glycerol 5.0 wt% N-Methyl-2-pyrrolidone 2.0 wt% ECTD-6NEX (Nikko Chemicals anionic surfactant) 1. 0 wt% 2,2,4-trimethyl-1,3-pentanediol 2.0 wt% Proxel LV (preservative) 0.2 wt% Ion-exchanged water Remaining amount

(Ink 14) An ink composition was prepared in the same manner as Ink 12 except that the following composition was used, and the pH was adjusted to 9 with lithium hydroxide. Monoazo yellow pigment-containing polymer fine particles of Reference Example 3 5.0 wt% triethylene glycol 15.0 wt% glycerol 5.0 wt% N-hydroxyethyl-2-pyrrolidone 2.0 wt% Dispanol TOC (Nonionic surfactant Agent) 1.0 wt% 2-ethyl-1,3-hexanediol 2.0 wt% Emulsion 3.0 wt% Proxel LV (preservative) 0.2 wt% Ion-exchanged water Remaining amount

(Ink 15) (Comparative Example 4) An ink composition was prepared in the same manner as in Ink 1 except that the following composition was used, and the pH was adjusted to 9 with sodium hydroxide. Dispersion of carbon black treated with diazo compound of Reference Example 1 4.0 wt% (pigment solid content) Ethylene glycol 15.0 wt% Glycerol 5.0 wt% 2-Pyrrolidone 2.0 wt% ECTD-6NEX (Nikon Chemicals anionic interface Activator) 1.0 wt% 2,2,4-trimethyl-1,3-pentanediol 2.0 wt% Proxel LV (preservative) 0.2 wt% Ion-exchanged water Remaining amount

The pigment concentration, the wetting agent concentration and the ink viscosity of the ink compositions of Inks 1 to 15 are shown in Table 2 below.

[0116]

[Table 2]

Next, the following tests were carried out on the recording medium and the inks 1 to 15 with the ink sets 1 to 4 of cyan, magenta, yellow and black shown in Table 2. The results are shown in Tables 3 and 4.

1) Image sharpness With an inkjet printer EM-900 (manufactured by Seiko Epson Corporation), head drive voltage, frequency,
Printing was performed on the following papers with different pulse widths. With respect to the print pattern, the color pigment inks of yellow, magenta, and cyan were printed at 100% duty, and the black ink filled with the black ink of the present invention printed characters at the same time. The printing conditions were 35 pl for Mj, 20 m / sec for Vj, a frequency of 1 kHz, a recording density of 720 dpi, and one-pass printing. Ricoh inkjet printer IPSIO Je
At t300, the drive voltage, frequency, and pulse width of the head were changed, and under the same conditions, solid and characters were printed by one-pass printing. After the print was dried, the bleeding at the boundary between the two-color overlapping portions and the image bleeding were visually evaluated, and judged according to the evaluation criteria. Further, the scratch resistance of the printed portion was judged by the degree of coloring of the cotton cloth by making a clock meter attached to the cotton cloth reciprocate 5 times.

The printing test papers used are shown below. My paper (manufactured by NBS Ricoh Co., Ltd.) Paper source S / recycled paper (manufactured by NBS Ricoh Co., Ltd.) PB paper (manufactured by Canon Inc.) Multi-ace (manufactured by Fuji Xerox Office Supply Co., Ltd.) Yamayuri paper (manufactured by Honshu Paper Co., Ltd.) Recycled paper) LH paper (manufactured by Fuji Xerox Office Supply Co., Ltd.) Xerox 4024 paper (manufactured by Fuji Xerox Office Supply Co., Ltd.) Neenah Bond paper (manufactured by Kimberly Clark Co., Ltd.)

Judgment Criteria <Bleeding at Boundary of Two-Color Overlap Area> A: Clear printing without bleeding. ◯: There is slight bleeding. Δ: Whisker-like bleeding occurs. X: Blurring occurs so that the outline of the character is not clear. <Drying property of image> The filter paper was pressed against the image after printing under a certain condition, and the time until the ink was not transferred to the filter paper was measured. The case where it took 5 minutes or more was judged as x. <Scratch resistance> A: The cotton cloth is hardly colored. . ◯: Slightly colored. Δ: Clearly colored. X: There is deep coloring.

<Image glossiness> The image was judged visually. A: Excellent. ◯: Good. Δ: Slightly inferior X: Inferior

[0122]

[Table 3-1]

[0123]

[Table 3-2]

[0124]

[Table 3-3]

[0125]

[Table 3-4]

[0126]

[Table 4]

[0127]

As is clear from the detailed and specific description above, the recording medium used in the ink jet recording method of the present invention is a recording having one or more porous layers containing inorganic particles on a substrate. It is a medium, has a void structure of a porous layer of inorganic particles, and has excellent ink absorbability because it matches the physical properties of the ink. Therefore, an even image can be obtained and the drying property is excellent. Highly compatible with vinyl-based polymers, polyester-based polymers, and polyurethane-based polymers that are used as polymers that form a porous layer of inorganic particles and polymer emulsions for ink, and fully exhibit the effect as a binder for coloring materials. Therefore, the scratch resistance of the recorded image is excellent. The peak of the pore radius distribution curve of the uppermost porous layer of the recording medium is 20 n
When the pore structure is set to m or less, a clear image with high image density can be obtained and a glossy image can be obtained.
According to the present invention, it is possible to provide a recording liquid cartridge containing a recording liquid which enables high reliability, safety and excellent image characteristics, and a recording apparatus equipped with this cartridge.

[Brief description of drawings]

FIG. 1 is a schematic front view showing a configuration example of a serial type ink jet recording apparatus equipped with an ink cartridge containing a recording liquid to which the present invention is applied.

FIG. 2 is an external perspective view of an ink cartridge before being loaded in the recording apparatus of the present invention.

FIG. 3 is a front sectional view of the ink cartridge of the present invention.

FIG. 4 is an external perspective view of a recording unit integrated with the recording head of the present invention.

[Explanation of symbols]

1 side plate 2 side plates 3 Main support guide rod 4 Secondary support guide rod 5 Carriage unit 6 heads 6a Discharge surface (nozzle surface) 7 ink cartridges 7y yellow ink cartridge 7m magenta ink cartridge 7c cyan ink cartridge 7k black ink cartridge 8 Main scanning motor 9 Drive pulley (drive timing pulley) 10 Driven pulley (idler pulley) 11 Timing belt 12 Bottom plate 13 subframes 14 subframes 15 Conveyor roller 16 sheets 17 Sub-scanning motor 18 gears 19 gears 21 Reliability maintenance and recovery mechanism (subsystem) 22 Cap means 23 Holder 24 Link member 25 Engagement part 26 Suction tube 27 Suction pump 28 Wiping means (wiper blade) 29 blade arm 30 recording units 31 electrodes 32 nozzles 41 Cartridge body 42 ink absorber 43 cases 44 Upper lid member 45 ink supply port 46 seal ring 47 Atmosphere opening 48 grooves 50 Cap member 55 Film seal member A space

Continued front page    (72) Inventor Masayuki Oyano             1-3-3 Nakamagome, Ota-ku, Tokyo Stocks             Company Ricoh F-term (reference) 2C056 EA05 EA13 FA03 FC02 FC06                 2H086 BA01 BA02 BA15 BA33 BA41                       BA53 BA55 BA59 BA60 BA61                       BA62                 4J039 AD20 AE06 BC09 BC10 BC11                       BD04 BE01 BE02 BE12 BE22                       CA03 CA06 EA35 EA36 EA38                       EA44 EA47 GA24

Claims (19)

[Claims] 1. A coloring material which is water-insoluble or sparingly soluble in polymer fine particles according to recording information on the surface of a recording medium having one or more porous layers containing inorganic particles on a substrate, on the side of the porous layer. An ink jet recording method, wherein recording is performed by applying an ink containing a polymer emulsion containing the above. 2. A fine particle of a polymer containing a water-insoluble or sparingly soluble coloring material on the surface of the recording medium having a porous layer of hydrated alumina on the side of the porous layer on the substrate, according to the recorded information. An ink jet recording method, wherein recording is performed by applying an ink containing a polymer emulsion as described above. 3. The inkjet recording method according to claim 2, wherein the recording medium comprises a porous layer of alumina hydrate and a porous layer containing inorganic particles provided on the porous layer. 4. The ink jet recording method according to claim 1, wherein a peak of a pore radius distribution curve of the uppermost porous layer of the recording medium is 20 nm or less. 5. An ink containing a polymer emulsion obtained by containing a water-insoluble or sparingly soluble coloring material in the polymer fine particles is glycerin, 1,3-butanediol, triethylene glycol, 1,6-hexanediol, Propylene glycol, 1,5-pentanediol, diethylene glycol, dipropylene glycol,
Containing at least one or more wetting agents selected from trimethylolpropane and trimethylolethane,
It is characterized by containing at least a polyol or glycol ether having 8 or more carbon atoms and 11 or less, an anionic or nonionic surfactant, a water-soluble organic solvent and water, and having an ink viscosity at 25 ° C. of 5 mPa · sec or more. Item 5. The inkjet recording method according to any one of Items 1 to 4. 6. The ink jet recording method according to claim 1, wherein the polymer forming the polymer emulsion of the ink is a vinyl polymer or a polyester polymer. 7. The ink contains 10 to 50 of the wetting agent.
7. The ink jet recording method according to claim 1, wherein the ink is contained in a weight percentage. 8. The ink jet recording method according to claim 1, wherein the ink contains a polymer emulsion containing a coloring material in a solid content of 8 to 20% by weight. 9. The ink jet recording method according to claim 1, wherein the polymer emulsion containing the coloring material in the ink has an average particle diameter of 0.16 μm or less. 10. The inkjet according to claim 1, wherein a weight ratio (wetting agent / emulsion solid) of the wetting agent and the solid content of the polymer emulsion in the ink is 2 to 5. Recording method. 11. The viscosity of the ink is 8 to 20 mPa.multidot.
11. The inkjet recording method according to claim 1, wherein the recording time is sec (25 ° C.). 12. The ink according to claim 1, wherein the polyol or glycol ether having 8 to 11 carbon atoms in the ink comprises 2-ethyl-1,3-hexanediol. Inkjet recording method. 13. The polyol or glycol ether having 8 or more carbon atoms and 11 or less carbon atoms in the ink is
The inkjet recording method according to claim 1, wherein the inkjet recording method comprises 4-trimethyl-1,3-pentanediol. 14. The ink is ejected by applying thermal energy to the ink.
4. The inkjet recording method according to any one of 3 above. 15. The ink jet recording method according to claim 1, wherein the ink is ejected by applying mechanical energy to the ink. 16. Mj is 5 to 35 pl and Vj is 6 to 20.
m, frequency 1 kHz or higher, resolution 300 dpi or higher,
The ink jet recording method according to claim 1, wherein recording is performed under a one-pass printing condition. 17. An ink accommodating portion or an ink cartridge used in the ink jet recording method according to any one of claims 1 to 16, and a head portion or a recording unit for dropping and ejecting the ink by the action of energy. An ink jet recording apparatus characterized by the above. 18. An ink used by the recording method according to any one of claims 1 to 16.
Media set. 19. A recorded matter, which is recorded by the recording method according to any one of claims 1 to 16.