JPH1052908A - Recording medium and recording method using the recording medium - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve the fixability of a coloring material without changing ink characteristics, to improve the quality of a printed image, and also to suppress the splash of liquid from a printing medium to a printing head side. Provide a recording ink that can be used. SOLUTION: A cationic substance is held on a recording medium side, and an alicyclic nitrogen-containing heterocyclic ring which causes a reaction to form an aggregate at high speed together with the cationic substance and the coloring material is compounded in the coloring ink containing the coloring material. And record.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a recording method in which a cationic substance held on a recording medium is combined with a water-soluble polymer compound having specific properties contained in a recording ink, and the recording method. The present invention relates to a recording medium to be used for:

[0002]

2. Description of the Related Art Conventionally, image formation by recording with ink includes image formation by contact type ink supply in which an ink supply means is brought into contact with a desired portion of a recording medium to form an image.
2. Description of the Related Art Image formation by non-contact type ink supply in which an ink is applied to a desired position on a recording medium with an ink supply unit and a recording medium in a non-contact state to form an image is mainly known. In particular, the latter has been widely used in recent years as an ink jet system. Note that this inkjet system is roughly classified into a bubble jet system using thermal energy for ink ejection and a piezo system using mechanical fluctuation.

[0003] The inks used for these include paper and OH.
Compositional improvements have been added for the purpose of clearly recording images on recording media such as P paper, or for stabilizing the ejection state of ink jet heads and the behavior of ink in the heads. Is common. In recent years, in the application of ink-jet systems to various fields, various advanced demands have been made on the performance of inks, and these improved technologies are becoming more sophisticated. . However, many ink-jet inks maintain the ink-jet characteristics due to a delicate balance of various physical properties, and when the desired characteristics are attempted to be improved, the other characteristics often deteriorate. In such a case, the degree of improvement of the desired characteristics is limited so that the degree of deterioration of the characteristics does not become a practical problem. As described above, there are advantages and disadvantages in improving the ink-jet ink itself.

Therefore, various attempts have been made to obtain good recording characteristics without improving the physical properties of the ink itself. For example, a technique for insolubilizing a coloring material in ink on a recording medium has been proposed for the purpose of improving the water resistance of an image.

As a specific example, see, for example,
JP-A-60783 discloses a method in which a liquid having a basic polymer is adhered to a recording medium and then an ink containing an anionic dye is applied to perform recording.
No. 2,681 discloses a recording method in which a first liquid containing a reactive chemical species and a second liquid containing a compound causing a reaction with the reactive chemical species are mixed on a recording medium. Furthermore,
JP-A-63-2999971 discloses a method of recording an ink containing an anionic dye after adhering a liquid containing an organic compound having two or more cationic groups per molecule. . Also, JP-A-64-92
No. 79 discloses a method in which an acidic liquid containing succinic acid is attached, and then an ink containing an anionic dye is applied to perform recording.

Further, Japanese Patent Application Laid-Open No. 64-63185 discloses a method in which a liquid for insolubilizing a dye (insolubilizing agent) is applied to a recording medium prior to applying ink. As a method using this insolubilizing agent, European Patent Publication 633299 by the applicant of the present application discloses that high-quality image formation using a recording ink in combination with a liquid composition containing a cationic substance or a nonionic substance as an insolubilizing agent is possible. An image recording method is disclosed.

[0007]

However, according to the study of the present inventors, after the application of the insolubilizing agent to the recording medium in order to improve the water resistance, the contact with the insolubilizing agent is required as in the prior art. When the ink is applied to the recording medium such that the subsequent ink droplet lands on the droplet of the insolubilizing agent that first adheres to the surface of the recording medium, if the speed of the ink droplet that lands is high, To some extent, a phenomenon was observed in which droplets were splashed due to the rebound of the droplets due to these collisions, and the droplets adhered to the recording head. The main range of the rebound varied from 500 μm to 1000 μm. It has been newly found that this rebound phenomenon may contribute to a problem such as an ink ejection failure or an ink ejection failure in an ink head. That is, if the repelling droplet contains an insolubilizing agent, it reacts integrally with the extremely small ink mist generated when ink is ejected from the ink recording head. In the worst case, the lump of the insoluble matter of the ink component (mainly the color material) generated by these reactions grows near the ink discharge port, and narrows or closes the ink discharge port, so that the ink discharge direction is reduced. May be bent in an undesired direction or the ink ejection may be temporarily interrupted.

That is, the conventional insolubilizer and ink
In a recording method using a liquid, it has been found that when the ink droplet is made to act at a higher speed in order to further increase the recording speed, the above-described problem is likely to occur. Then, in order to achieve good recording at a higher speed, it was concluded that a technique for suppressing the generation of the splash due to the above-mentioned rebound was necessary.

The present inventors have further studied ink and its insolubilizing agent for the purpose of achieving a new problem in such a two-liquid recording method. In that process, if the composition was changed within the range of various known components used as the components of the conventional ink and the insolubilizing agent, a sufficiently satisfactory result could not be obtained. In such a situation, when one of the present inventors is conducting various studies on the reactivity of two substances in water, a stable turbid state is obtained by putting two types of reactive substances in a beaker. A phenomenon was observed in which a turbid solution became transparent and a reactant adhered to the glass rod when the glass rod was formed and stirred with a glass rod inserted therein. From this phenomenon, a substance that is inert in the ink, has no effect on the physical properties of the ink, or is negligibly small, and causes a rapid agglutination reaction of the coloring material in contact with the insolubilizing agent, I gained a hint that it is effective in achieving the above tasks. Further, as a result of further study based on such hints, a new finding that, for example, a water-soluble polymer compound having an alicyclic nitrogen-containing heterocycle has such properties has been obtained.

The present invention has been made based on such new findings by the present inventors, and its purpose is to maximize the recording characteristics of a recording method using an insolubilizing agent without changing the ink characteristics. Accordingly, it is an object of the present invention to provide a recording ink capable of improving the quality of a recorded image and suppressing the liquid rebound described above.

Another object of the present invention is to provide a recording medium capable of stably recording a high-quality image and a recording method using the recording medium.

[0012]

A recording medium according to one embodiment of the present invention that can solve the above-mentioned object has a nonionic property in a coloring material and ink and has an alicyclic nitrogen-containing heterocyclic ring. A recording medium used for recording with a recording ink containing a water-soluble polymer compound, wherein a cationic substance is held on a recording surface.

According to a recording method as one embodiment of the present invention, the recording surface of a recording medium holding a cationic substance has a nonionic property in a coloring material and ink and has an alicyclic nitrogen-containing heterocyclic ring. The recording is performed using a recording ink containing a water-soluble polymer compound.

According to the present invention, when a recording ink is applied to a recording medium, a water-soluble polymer compound having an alicyclic nitrogen-containing heterocyclic ring contained in the recording ink and exhibiting nonionic properties in a liquid. However, it reacts with the cationic substance held on the surface side of the recording medium in the coexistence of the coloring material, and the immobilization of the coloring material component starts instantaneously. As a result, image quality may be reduced,
For example, feathering in which a feather-like pattern is generated around the circumference of the dot due to the recording ink bleeding along the fibers of the recording medium and the dot contour is blurred,
It is possible to prevent bleeding in which color mixing occurs at the boundary between dots of different colors when adjacent dots are hit.

In the present invention, the above-mentioned action by using a water-soluble polymer compound having an alicyclic nitrogen-containing heterocyclic ring and exhibiting nonionic properties in a liquid is, for example, an anionic dye or an alicyclic nitrogen-containing heterocyclic ring. From the phenomenon that these reactions occur at a high speed when a water-soluble polymer compound having a ring and a cationic substance coexist, it can be estimated as follows.

That is, in the water-soluble polymer compound having an alicyclic nitrogen-containing heterocyclic ring, a positively polarized site is formed in the branched chain to which the alicyclic nitrogen-containing heterocyclic ring is bonded. However, since this polarization is weak, even if the anionic dye is slightly localized in the positive electrode portion in the recording ink, the anionic dye and the water-soluble polymer compound are not bonded, and the water-soluble Since the polymer compound exhibits nonionic properties in a solution, there is no significant change in the properties of the recording ink due to the addition of the water-soluble polymer compound. When the recording ink in such a state is brought into contact with the cationic substance on the recording medium side, an ionic bond between the cationic substance and the anionic dye occurs, and the movement of the anionic dye in these reaction liquids is regulated. At the same time, the reactivity of the anionic dye in the state of being ionic-bonded to the cationic substance changes, so that it easily reacts with the polarized portion of the water-soluble polymer compound. As a result, a giant water-insoluble aggregate in the form of a cationic substance and a water-soluble polymer substance bound via an anionic dye is formed.

The reaction for forming the aggregate is much faster than the formation of the aggregate in the conventional two-part recording method in which the water-soluble polymer compound having an alicyclic nitrogen-containing heterocycle is not added to the recording ink. And therefore this reaction, for example,
When applied to the image recording method used in the ink jet recording method, these aggregate formation reactions start instantly from the moment the recording ink comes into contact with the cationic substance held on the recording surface of the recording medium, and Formation promotes immobilization of the coloring material.

That is, the instantaneous formation of the water-insoluble aggregates causes a rapid separation of the coloring material applied thereto and the aqueous medium component of the recording ink on the recording medium, thereby causing bleeding and feathering. It is possible to effectively suppress the formation of high-quality images. In addition, since the aggregate is insoluble in water, the resulting image has extremely excellent water resistance.

The above presumption is based on, for example, the fact that the formation of the above-mentioned aggregates is not observed even when the cationic substance and the water-soluble polymer compound having an alicyclic nitrogen-containing heterocycle are simply reacted. If you look at it, you think it's right.

In the present invention, it is more effective to use two kinds of cationic substances having a molecular weight of 1,000 or less and those having a molecular weight of more than 1,000 in combination. The reason is that the presence of a cationic substance having a small molecular weight accelerates the initiation of an agglutination reaction due to the ionic interaction between the dye and the cationic substance, and the cationic substance having a large molecular weight promotes insolubilization by the growth of the aggregate. It is thought to be done.

Further, in the present invention, a component necessary for insolubilizing the coloring material, that is, a cationic substance is held on the recording medium side, so that the insolubilizing agent for the coloring material is used as in the conventional two-liquid recording method. It is possible to effectively avoid the problem caused by splashing when the droplets are applied to the recording medium.

[0022]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The recording ink used in the recording method of the present invention comprises at least a water-soluble polymer compound having an alicyclic nitrogen-containing heterocycle and a coloring material. Further, in order to maintain the liquid property of the recording ink, water or
An aqueous medium comprising a mixed solvent of water and a water-soluble organic solvent can be contained. Furthermore, various additives can be included depending on the type of application method to the recording medium. For example, when used in an inkjet system, various components commonly used in inkjet inks, for example, a viscosity adjuster, a pH adjuster, a preservative, a surfactant, an antioxidant, and the like are appropriately selected and used. Can be. In addition,
The water-soluble polymer compound having an alicyclic nitrogen-containing heterocycle to be added to the recording ink in the present invention, although having a polarized portion, has low reactivity in the recording ink, and is usually different from other ink components. The reaction does not substantially change the ink properties. However, depending on the type of other ink components, if these react to greatly reduce the characteristics of the ink, the combination may be changed to another combination avoiding such a combination.

The water-soluble polymer compound having an alicyclic nitrogen-containing heterocyclic ring can be used without any particular limitation as long as it enables high-speed formation of aggregates as described above while maintaining recording characteristics. it can. As an example of such a compound, the following general formula (1)

[0024]

Embedded image (However, R ¹ represents a hydrogen atom, a methyl group, an ethyl group or any one of the following alicyclic nitrogen-containing heterocycles,
R ⁵ represents any one of the following alicyclic nitrogen-containing heterocycles,

[0025]

Embedded image R ^{2 to} R ⁴ independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and L ^{1 to} L ⁴ independently represent each other

[0026]

Embedded image (Wherein, R ^{6 to} R ⁹ each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms), and represents a divalent group having a structure represented by the following formula. And the sum of s and t is 90 to 99% by weight of the whole water-soluble polymer compound, q is 1 to 10% by weight, n and k are integers, and the sum is in the range of 10 to 30. , M is an integer of 15 to 30, and p is an integer of 1 to 5).

Among the compounds of the general formula (1),
(A) an acrylic acid ester of an ethylene oxide or propylene oxide adduct of substituted morpholine, (b) acrylic acid and (c) the following general formula (2)

[0028]

Embedded image (In the above formula, R ¹ , R ² , L ^{2 to} L ⁴ , n, m and k are defined in the same manner as in the general formula (1)). It can be mentioned as.

R ¹ and R ⁵ are both a morpholine ring:

[0030]

Embedded image Is a cationic substance contained in a liquid composition containing a cationic substance (hereinafter referred to as a cation-containing liquid composition), and a water-soluble polymer having an alicyclic nitrogen-containing heterocycle in a recording ink. The reactivity with the compound and the coloring material becomes extremely good, and the stability of the recording ink itself becomes more excellent, so that it is more preferable.

The water-soluble polymer compound having an alicyclic nitrogen-containing heterocyclic ring can be obtained by gel permeation chromatography (GPC) (GPC column TSG-gel GMHX).
The upper limit of the molecular weight (weight average molecular weight) measured by L polystyrene conversion is preferably 300,000, and the lower limit thereof is preferably 5,000, more preferably the upper limit of the molecular weight is 50,000. This is because, when using those having a molecular weight within these ranges, the formation of aggregates at the time of contact between the recording ink and the cationic substance is performed at a higher speed, and bleeding can be almost completely prevented. It is considered that the technical problem of preventing the problem can be more sufficiently achieved. Furthermore, even when applied to an ink-jet recording method using a heating element, that is, a recording ink containing one having these molecular weight ranges, that is, a recording method by a bubble ink-jet method in which a liquid is ejected by applying thermal energy, the ink is also applied on the heating element. It is possible to more effectively prevent the problem that the deposits are attached and that the recording ink is not ejected. That is, a recording ink using such a molecular weight range is particularly suitable when an ink jet recording method using a heating element is applied.

The amount of the water-soluble polymer compound having an alicyclic nitrogen-containing heterocycle to be incorporated into the recording ink is appropriately selected according to the type of the method of applying the recording ink to the recording medium. Is preferably approximately the same as the concentration of the coloring material, because the insolubilization of the coloring material by the reaction between the recording ink and the cationic substance on the recording medium side can be more effectively achieved.

The coloring material to be contained in the recording ink is a material capable of forming an aggregate by a reaction with the above-mentioned water-soluble polymer having a cationic substance and an alicyclic nitrogen-containing heterocycle. It can be used without limitation as long as the desired recording characteristics can be obtained. As such dyes, various dyes can be used. For example, water-soluble acid dyes, direct dyes, reactive dyes described in the Color Index (COLOR INDEX), and those not listed in the Color Index Among them, for example, a water-soluble dye having an anionic group such as a sulfonic acid group and a carboxyl group can be used. The water-soluble dyes mentioned here include those having a pH dependency in solubility. As the coloring material, an anionic dye is particularly preferable. The composition of the coloring material may be selected according to the desired color of the ink.For example, by selecting the coloring material, it is possible to prepare a yellow, magenta, cyan, black, red, blue or green ink. These at least one color recording ink can be used as an ink set in combination with a cation-containing liquid composition. The content of the coloring material is usually preferably 1 to 8% by weight, and is preferably 3 to 10% by weight for recording on cloth, metal (alumite) or the like. 01-1
0% by weight is preferred.

On the other hand, as the aqueous medium for forming the recording ink used in the present invention, water, a mixed solvent of water and a water-soluble organic solvent, or the like can be used. As the water, ion exchange water or deionized water is preferable.

Other water-soluble organic solvents used by mixing with water include, for example, methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol. C1 such as butyl alcohol
To 4 alkyl alcohols: dimethylformamide,
Amides such as dimethylacetamide: ketones or ketoalcohols such as acetone and diacetone alcohol;
Ethers such as tetrahydrofuran and dioxane; polyalkylene glycols such as polyethylene glycol and polypropylene glycol; ethylene glycol;
Alkylene glycols having an alkylene group containing 2 to 6 carbon atoms, such as 2,6-hexanetriol, thiodiglycol, hexylene glycol, diethylene glycol, etc .: glycerin, ethylene glycol monomethyl (or ethyl) ether, diethylene glycol methyl (or ethyl) ) Lower alkyl ethers of polyhydric alcohols such as ether, triethylene glycol monomethyl (or ethyl) ether; N-methyl-2-pyrrolidone;
2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone and the like. Of these many water-soluble organic solvents, lower alkyl ethers of polyhydric alcohols such as diethylene glycol are preferred.

Further, in order to obtain ejection stability, it is effective to add ethanol or isopropyl alcohol in an amount of 1% by weight or more. This is because, for example, when the recording ink is applied to a recording medium by an ink jet recording method using a heating element, by adding these solvents, the foaming of the recording ink on the thin film resistor (heating element) can be improved. It is considered that it can be performed stably. However, if these solvents are added in excess, the print quality of the printed matter is impaired, so that a more appropriate concentration of these solvents is 3 to 10% by weight. Further, as an effect of these solvents, by adding these solvents to the dispersion liquid, generation of bubbles during dispersion can be suppressed, and effective dispersion can be performed.

The content of the water-soluble organic solvent in the recording ink of the present invention is generally 3 to 5 times the total amount of the recording ink.
The amount of water used is 10 to 9% by weight of the total weight of the recording ink.
0% by weight, preferably in the range of 30 to 80% by weight.

The recording medium used in combination with the recording ink having the above-described configuration can be formed by holding a cationic substance on the recording surface (the surface on which recording is performed) of the substrate.

As the base material, for example, copy paper, bond paper, recycled paper, high quality paper, medium quality paper, art paper, baryta paper,
Examples include various types of paper such as cast coated paper, corrugated paper, glossy paper, and coated paper for inkjet, cloth, a sheet made of metal, and a sheet or film made of plastic.

As a method for retaining the cationic substance on the recording surface, there is a method in which a coating liquid containing the cationic substance is prepared, applied to the recording surface, and dried. Bar coating method, play coating method,
Size press method, roll coat method, blade coat method,
Air knife coating, gate roll coating, gravure coating, curtain coating, and the like can be used.

The amount of the cationic substance held on the recording medium is:
Preferably from 0.01 to 3.0, based on the dry weight of the substrate.
It is desirable that the content be adjusted to be about weight%, and the upper limit is 2.0 weight%, and the lower limit is more preferably 0.05 weight%. When the holding amount is 0.01% by weight or more, the effect of the present invention can be further enhanced. When the holding amount exceeds 3.0% by weight, the reaction time becomes longer, and image blurring and the like occur. There is a risk.

In the present invention, when the molecular weight distribution of the cationic substance held by the recording medium is measured by GPC (gel permeation chromatography), fractions are given to both a region having a molecular weight of 1,000 or less and a region having a molecular weight exceeding 1,000. Mixtures are preferred. As such a mixture of cationic substances, a substance that gives a plurality of fractions when its molecular weight is measured by GPC, for example, is preferable. As shown in FIGS. 10 and 11, regions having different molecular weights, specifically, for example, a molecular weight of 1000 Giving fractions both below and over 1000 areas,
Those having a molecular weight peak in each of these two regions, and those having a molecular weight of 1000 as shown in FIGS.
Fractions are applied to both the following and more than 1000 regions, with one having a molecular weight peak in one of these regions.

In practicing the present invention, the use of a cationic polymer having a large molecular weight as used in the prior art can be avoided in some cases. Since the viscosity of the liquid does not increase, it is possible to prepare a coating liquid that is easy to apply.

In the mixture having a molecular weight distribution as shown in FIG. 10, as the cationic substance contained in the fraction on the low molecular side among a plurality of fractions, for example, the molecular weight distribution of the mixture is 1000 or less, especially 200 or more and 800 or less, furthermore 300 or more and 8
It is preferable to use a substance contained in a fraction of 00 or less in order to obtain a high-quality ink image.

This can be achieved quickly when a mixture of a coloring material contained in the recording ink, for example, a water-soluble dye having an anionic group and a water-soluble polymer compound having an alicyclic nitrogen-containing heterocycle and a cationic substance is contacted. To rapidly restrict the mobility of the ink and suppress the diffusion and penetration of the recording ink into the recording medium following the penetration of the aqueous medium component of the recording ink into the recording medium. It is thought that it is possible.

As the low-molecular component, those having a molecular weight distribution close to monodispersion can be suitably used. For example, those having a peak in a region having a molecular weight of 1,000 or less are preferably used. When a substance having no molecular weight distribution is used as the low molecular component of the cationic substance, the molecular weight obtained from the chemical formula is regarded as the position of the peak of the molecular weight distribution.

Next, specific examples of the low molecular weight component of the cationic substance include, for example, compounds of primary to tertiary amine salt type, specifically, hydrochlorides such as laurylamine, cocoamine, stearylamine, and rosinamine; In addition to acetates and the like, there are quaternary ammonium salt type compounds, specifically lauryl trimethyl ammonium chloride, lauryl dimethyl benzyl ammonium chloride, benzyl tributyl ammonium chloride, benzalkonium chloride, cetyl trimethyl ammonium chloride, and the like. , Pyridinium salt type compounds, specifically cetylpyridinium chloride, cetylpyridinium bromide, etc.,
There are imidazoline-type cationic compounds, specifically, 2-heptadecenyl-hydroxyethylimidazoline and the like,
Further, ethylene oxide adducts of secondary alkylamines, specifically, dihydroxyethylstearylamine and the like are mentioned as preferable examples.

Further, in the present invention, an amphoteric surfactant showing cationicity in a certain pH range can also be used, and specifically, an amino acid type amphoteric surfactant, RNHCH ₂ —CH ₂ C
There are OOH-type compounds, and betaine-type compounds such as stearyldimethylbetaine and lauryldihydroxyethylbetaine. Of course, when using these amphoteric surfactants, the pH below their isoelectric point
It is preferable to take either of the following methods: adjusting the coating liquid so that the pH becomes equal to or lower than the isoelectric point when mixed with the recording ink on the recording medium.

As described above, examples of the low molecular component of the cationic substance have been given, but it goes without saying that the cationic substance that can be used in the present invention is not necessarily limited to these.

Examples of other low molecular weight components of the cationic substance include, for example, monomers and oligomers of the cationic high molecular components described later.

Next, as a polymer component of the cationic substance, a fraction in a region where the molecular weight exceeds 1,000 when the molecular weight distribution is measured by GPC, particularly in a region of 1500 or more, and further in a range of 1500 to 10,000 is used. Is preferable in order to fix the recording ink at a high speed and to obtain a high-quality ink image.

Here, as the high molecular component of the cationic substance, for example, those close to monodispersion having a molecular weight peak in a region having a molecular weight of 1500 or more can be suitably used.

Specific examples of the polymer component of the cationic substance include polyallylamine, polyamine sulfone, polyvinylamine, chitosan, and neutralized or partially neutralized products thereof with acids such as hydrochloric acid and acetic acid. Needless to say, the present invention is not limited to these. For example, the position of the peak of the molecular weight distribution of these polymer substances is 1000
As long as there is at least one in a region exceeding the number, for example, 1500 or more and 10,000 or less, the effect is sufficient when the present invention is carried out.

In the present invention, the molecular weight of the polymer substance means an average molecular weight obtained by using GPC and a weight average molecular weight in terms of polyethylene oxide unless otherwise specified.

Further, as another specific example of the cationic polymer substance, a compound obtained by partially cationizing a nonionic polymer substance may be used. Specific examples thereof include a copolymer of vinylpyrrolidone and a quaternary salt of aminoalkylalkylate, and a copolymer of acrylamide and a quaternary salt of aminomethylacrylamide, but of course, are not limited to these compounds. Needless to say, it will not be done. Further, this cationic polymer substance is satisfactory if it is water-soluble, but may be a dispersion such as latex or emulsion.

Next, a mixture of cationic substances having a molecular weight distribution as shown in FIGS. 12 and 13 will be described.

The mixture having the molecular weight distribution shown in FIG. 12 has a peak of the molecular weight distribution at a molecular weight of 1,000 or less and gives a fraction also to a region exceeding the molecular weight of 1,000. As such a mixture of cationic substances, a mixture whose molecular weight is widely distributed from a low molecular weight region to a high molecular weight region is suitably used. Specifically, when the molecular weight distribution of the mixture is measured, a fraction having a molecular weight of 1,000 or less, particularly a molecular weight of about 800, and further a molecular weight of about 300 is given on the low molecular weight side, and a molecular weight of 1000 is given on the high molecular weight side. Exceeding area, especially 15
Those which give a fraction of 00 or more, more preferably 1500 or more and 10,000 or less are preferable. And such a mixture of cationic substances comprises one having a single repeating unit.
May be achieved with a kind of cationic polydisperse polymer,
Alternatively, it may be achieved by a mixture of two or more cationic polymers having different structures. Examples of such a cationic substance include a polymer used as a polymer component of the above-mentioned cationic substance, which is synthesized so as to have a wide molecular weight distribution, or a mixture of a polymer and an oligomer.

In the mixture of the cationic substances, the mixing ratio between the low molecular weight component and the high molecular weight component of the cationic substance may be appropriately selected according to the material.
0: 1 to 1:10, particularly 5: 1 to 1: 5, and even 1:
It is desirable to set it in the range of 1-1: 5.

Next, the coating solution of the cationic substance can be prepared by dissolving or dispersing the cationic substance in an appropriate solvent or dispersant. As the solvent, for example,
Examples include water, a mixture of water and a water-soluble organic solvent, and an organic solvent. Examples of the water-soluble organic solvent include amides such as dimethylformamide and dimethylacetamide, ketones such as acetone, ethers such as tetrahydrofuran and dioxane, polyalkylene glycols such as polyethylene glycol and polypropylene glycol, ethylene glycol, propylene glycol, and butylene. Glycol, triethylene glycol, 1,2,6-hexanetriol, thiodiglycol, hexylene glycol,
Alkylene glycols such as diethylene glycol, lower alkyl ethers of polyhydric alcohols such as ethylene glycol methyl ether, diethylene glycol monomethyl ether, and triethylene glycol monomethyl ether; monohydric alcohols such as ethanol, isopropyl alcohol, n-butyl alcohol, and isobutyl alcohol Glycerin, N-methyl-2-pyrrolidone,
Examples thereof include 1,3-dimethylimidazolidinone, triethanolamine, sulfolane, and dimethyl sulfoxide.

The composition of the coating solution, for example, the amount of the cationic substance may be appropriately selected according to the desired coating amount.

The coating liquid may further contain additives such as a viscosity adjuster, a pH adjuster, a preservative, a surfactant and an antioxidant, if necessary.

In the present invention, the method of applying the recording ink to the recording medium can be appropriately selected according to the intended image formation. When an ink jet method is used to apply a recording ink to a recording medium, for example, various ink jet methods can be used. Specifically, a so-called on-demand method in which droplets are ejected using bubbles generated by thermal energy, Type bubble ink jet system or an ink jet system using a piezo element. In the present invention, the bubble inkjet method is particularly preferably used.

Next, a recording apparatus used in the present invention will be described. In the present invention, a so-called on-demand type bubble ink jet system in which a recording signal is applied to recording ink of a recording head and droplets are ejected by generated thermal energy is preferable. 1, 2 and 3 show the configuration of a recording head, which is a main part of the apparatus. The head 13 includes a heating head 15 (a head is shown in the figure, but is not limited to a heating head including a glass, ceramic, plastic, or the like forming a flow path of the recording ink and a heating resistor used for thermal recording. Is not obtained. The heating head 15 includes a protective film 16 formed of silicon oxide or the like,
An aluminum electrode 17-1, 17-2, a heat-generating low antibody layer 18 made of nichrome or the like, a heat storage layer 19, and a substrate 20 having good heat dissipation such as alumina.

The recording ink 21 reaches the discharge orifice 22 and forms a meniscus 23 by the pressure P. Here, when an electric signal is applied to the electrodes 17-1 and 17-2, an area indicated by n of the heating head 15 generates heat rapidly, and bubbles are generated in the ink 21 in contact with the area, and the meniscus is generated by the pressure. Is ejected, becomes a recording ink droplet 24 from the orifice 22, and flies toward the recording medium 25. FIG. 3 is a schematic view of a recording head in which a number of nozzles shown in FIG. 1 are arranged. The recording head is formed by closely contacting a glass plate 27 having a large number of channels and a heating head 28 similar to that described with reference to FIG. 1 is a cross-sectional view of the head 13 along the ink flow path, and FIG. 2 is a cross-sectional view taken along a line AB in FIG.

FIG. 4 shows an example of an ink jet recording apparatus incorporating the head. In FIG. 4, reference numeral 61 denotes a blade as a wiping member, one end of which is held by a blade holding member to become a fixed end, and has a form of a wrench lever. The blade 61 is arranged at a position adjacent to the recording area of the recording head, moves in a direction perpendicular to the moving direction of the recording head, comes into contact with the ejection port surface, and performs capping. Further, an ink absorber 63 is provided adjacent to the blade 61, and is held in a form protruding into the movement path of the recording head, similarly to the blade 61. The blade 61, the cap 62, and the absorber 63 constitute an ejection recovery section 64, and the blade 61 and the absorber 63 remove moisture, dust, and the like from the ink ejection port surface.

Reference numeral 65 denotes a discharge energy generating means,
A recording head 66 that discharges recording ink onto a recording medium facing a discharge port surface provided with discharge ports, and a carriage 66 on which the recording head 65 is mounted to move the recording head 65. The carriage 66 is slidably engaged with the guide shaft 67, and a part of the carriage 66 is connected to a belt 69 driven by a motor 68 (not shown). As a result, the carriage 66 can move along the guide shaft 67, and the recording head 65 can move the recording area and the adjacent area. Reference numeral 51 denotes a paper feed unit for inserting a recording medium, and 52 denotes a feed roller driven by a motor (not shown). With these configurations, the recording medium is fed to a position facing the ejection port surface of the recording head,
As the recording progresses, the sheet is discharged to a discharge section provided with a discharge roller 53.

In the above configuration, when the recording head 65 returns to the home position at the end of recording or the like, the head recovery section 64
Is retracted from the moving path of the recording head 65, while the blade 61 protrudes into the moving path.
As a result, the ejection port surface of the recording head 65 is wiped. When capping is performed with the cap 62 in contact with the ejection opening surface of the recording head 65, the cap 62 moves so as to protrude into the movement path of the recording head. When the recording head 65 moves from the home position to the recording start position, the cap 62 and the blade 61 are at the same position as the position at the time of wiping. As a result, the ejection port surface of the recording head 65 is also wiped during this movement. The movement of the print head to the home position is performed not only at the end of printing or at the time of ejection recovery, but also at predetermined intervals while the print head moves through the printing area for printing to the home position adjacent to the printing area. Then, the wiping is performed along with this movement.

FIG. 5 is a diagram showing an example of an ink cartridge containing recording ink supplied to the head via an ink supply member, for example, a tube. Here, reference numeral 40 denotes an ink storage unit that stores recording ink for supply, for example, an ink bag, and a rubber stopper 42 is provided at the end thereof. By inserting a needle (not shown) into the stopper 42, the recording ink in the ink bag 40 can be supplied to the head. Reference numeral 44 denotes an absorber for receiving the waste ink. The ink container preferably has a liquid contact surface with the recording ink formed of polyolefin, particularly polyethylene.

The ink-jet recording apparatus used in the present invention is not limited to the above-described apparatus in which the recording head and the ink cartridge are separated from each other, but also preferably an apparatus in which they are integrated as shown in FIG. Used for In FIG. 6, reference numeral 70 denotes a recording unit, in which an ink storage unit for storing recording ink, for example, an ink absorber is stored, and a recording head in the ink absorber has a plurality of orifices. The recording ink is ejected from 71 as recording ink. As a material of the ink absorber, for example, polyurethane can be used. 7
Reference numeral 2 denotes an atmosphere communication port for communicating the inside of the recording unit with the atmosphere. This recording unit 70 is used in place of the recording head shown in FIG.
6 is detachable. In the recording apparatus used in the present invention, an ink jet recording apparatus in which thermal energy is applied to the recording ink to eject droplets of the recording ink has been described above as an example. The present invention can be similarly applied to a system-type ink jet recording apparatus.

The image recording method according to the present invention includes, for example,
A printing apparatus in which five print heads shown in FIG. 3 are arranged on a carriage can be used. FIG. 7 shows an example. 81, 82, 83, 84 are yellow,
This is a recording head for ejecting recording ink of each color of magenta, cyan, and black.

This head is arranged in the above-described recording apparatus, and discharges recording ink of each color according to a recording signal.
FIG. 7 shows an example in which four print heads are used. However, the present invention is not limited to this. As shown in FIG. 8, one print head uses yellow ink, magenta ink,
It is also preferable that the cyan ink and the black ink are ejected in separate liquid flow paths.

[0072]

The present invention will be described more specifically below with reference to examples and comparative examples. Example 1 (1) Preparation of Recording Ink The recording ink components for each ink set shown in Tables 1 to 6 were individually mixed, and a membrane filter having a pore size of 0.22 μm (trade name: Fluoropore Filter, manufactured by Sumitomo Electric Industries, Ltd.) ), And the recording inks (yellow ink (Y), magenta ink (M), cyan ink (C), black ink (B
K)) were obtained. The dyes 1 and 2 in Table 1 were used.
Contains a dye having the following structure,

[0073]

Embedded image Dye 1 can be obtained according to the method described in JP-A-59-78273, and Dye 2 can be obtained according to the method described in JP-A-3-91577.

The polymers A to F are as follows. The molecular weight of each polymer was determined by gel permeation chromatography (GPC column TSG-gel).
GMHXL (in terms of polystyrene). Polymer A: molecular weight (Mw) = 27,000 copolymer of the following monomers A-1 to A-3 (compound weight ratio, A
-1: A-2: A-3 = 90: 8: 2) Monomer A-1: 2-morpholinoethyl methacrylate Monomer A-2:

[0075]

Embedded image Monomer A-3: Methacrylic acid Polymer B Molecular weight (Mw) = 50,000 A copolymer of the following monomers B-1 to B-3 (compound weight ratio, B
-1: B-2: B-3 = 50: 48: 2) Monomer B-1: 2-morpholinoethyl methacrylate Monomer B-2:

[0076]

Embedded image Monomer B-3: Methacrylic acid Polymer C Molecular weight (Mw) = 15,000 A copolymer of the following monomers C-1 to C-3 (compound weight ratio, C
-1: C-2: C-3 = 90: 8: 2) Monomer C-1: 2-morpholinoethyl methacrylate Monomer C-2:

[0077]

Embedded image Monomer C-3: Methacrylic acid Polymer D Molecular weight (Mw) = 5,000 A copolymer of the following monomers D-1 to D-3 (compound weight ratio, D
-1: D-2: D-3 = 80: 15: 5) Monomer D-1: 2-morpholinobutyl methacrylate Monomer D-2:

[0078]

Embedded image Monomer D-3: Methacrylic acid Polymer E Molecular weight (Mw) = 10,000 A copolymer of the following monomers E-1 to E-3 (compound weight ratio, E
-1: E-2: E-3 = 80: 15: 5) Monomer E-1: 2-morpholinobutyl methacrylate Monomer E-2:

[0079]

Embedded image Monomer E-3: Methacrylic acid Polymer F Molecular weight (Mw) = 300,000 A copolymer of the following monomers F-1 to F-3 (compound weight ratio, F
-1: F-2: F-3 = 80: 15: 5) Monomer F-1: 2-morpholinobutyl methacrylate Monomer F-2:

[0080]

Embedded image Monomer F-3: methacrylic acid The above polymer was obtained by the following method. That is, the three kinds of monomers for preparing each polymer are mixed at a predetermined weight ratio, and 0.1 parts by weight of 2,2′-azobis (2,4-dimethyl) valeronitrile is further used as a polymerization catalyst. Put the mixture in an ampoule, freeze, deaerate, and seal tightly.
Polymerization was carried out at 0 ° C. for 8 hours to obtain a desired polymer.

Further, the monomers (A-2, B-2, D-
2, E-2 and F-2) were synthesized according to the following method. That is, first, an alkylene oxide (ethylene oxide, propylene oxide, etc.) is sequentially added to a nitrogen-containing alicyclic compound at 50 to 200 ° C. and 1 to 10 atm in the presence of an alkali metal catalyst, and then ethylene oxide is added to form a polyether. A monol is synthesized, and the polyether monol and methacrylic acid or acrylic acid are reacted in the presence of an acidic catalyst (sulfuric acid, paratoluenesulfonic acid, etc.) for 50 minutes.
The desired monomer was obtained by esterification at ２００200 ° C. and 1-10 atm or esterification at -10-50 ° C. and normal pressure with an esterification reagent (dicyclohexylcarbodiimide). The monomer C-2 was synthesized in the same manner as in A-2 except that methanol was used instead of the nitrogen-containing alicyclic compound.

[0082]

[Table 1]

[0083]

[Table 2]

[0084]

[Table 3]

[0085]

[Table 4]

[0086]

[Table 5]

[0087]

[Table 6] The dyes in Tables 1 to 6 above are shown below. DY142: C.I. I. Direct Yellow 142 DB199: C.I. I. Direct Blue 199 FB2: C.I. I. Food Black 2 AY23: C.I. I. Acid Yellow 23 AR289: C.I. I. Acid Red 289 AB9: C.I. I. Acid Blue 9 DY86: C.I. I. Direct Yellow 86 AR52: C.I. I. Acid Red 52 DB86: C.I. I. Direct Blue 86 DB154: C.I. I. Direct Black 154 (2) Preparation of Recording Medium After mixing and dissolving the following components, NP-SK paper (manufactured by Canon Inc.) was coated by a bar coating method at a coating amount of 1.0% by weight. It was applied and dried in a thermostat at 60 ° C. for 5 minutes to obtain recording media a to f. Coating solution for recording medium a: 2 parts by weight of stearyltrimethylammonium chloride (trade name: electrostripper QE, manufactured by Kao Corporation / Mw = 340) 2 parts by weight of polyamine sulfone hydrochloride (trade name: PAS-A-1 / Nitto) Spinning Co., Ltd./Peak position of molecular weight distribution 2000) 10 parts by weight-10 parts by weight of thiodiglycol-85 parts by weight of ion-exchanged water Coating solution for recording medium b:-Stearyl trimethyl ammonium chloride (trade name: Electrostripper QE) 2 parts by weight Polyamine sulfone hydrochloride (trade name: PAS-A-5 / manufactured by Nitto Boseki Co., Ltd./ peak position of molecular weight distribution 3500) 6 parts by weight Thiodiglycol 10 parts by weight ・ Ion-exchanged water 82 parts by weight Coating solution for recording medium c: ・ Stearyl trimethylammo 2 parts by weight of sodium chloride (trade name: Electrostripper QE, manufactured by Kao Corporation / Mw = 340) Polyamine sulfone hydrochloride (trade name: PAS-92 / manufactured by Nitto Boseki Co., Ltd./peak of molecular weight distribution Position 5000) 4 parts by weight ・ Thiodiglycol 10 parts by weight ・ Ion-exchanged water 84 parts by weight Coating solution for recording medium d: ・ Stearyltrimethylammonium chloride (trade name: Electrostripper QE, manufactured by Kao Corporation / Mw = 340) 2 parts by weight ・ Polyallylamine hydrochloride ¹⁾ (peak position of molecular weight distribution 8500) 4 parts by weight ・ Thiodiglycol 10 parts by weight ・ Ion-exchanged water 84 parts by weight Coating solution for recording medium e: ・ Polyallylamine hydrochloride ²⁾ (Peak position of molecular weight distribution 800) 3 parts by weight Polyamine sulfone hydrochloride (trade name: PAS-A-1 / day) Spinning Co. / peak position of the molecular weight distribution 2000) 10 parts by weight thiodiglycol 10 parts by weight Ion-exchanged water 77 parts by weight recording medium f Coating solution: Polyallylamine hydrochloride ³⁾ (the peak position of the molecular weight distribution 650) 5 parts by weight ・ Polyamine sulfone hydrochloride ⁴⁾ (Peak position of molecular weight distribution 8500) 3 parts by weight ・ 10 parts by weight of thiodiglycol ・ 82 parts by weight of ion-exchanged water The compounds of 1) to 4) are “functions” Materials ", Volume 5,
Synthesized by the method described on page 29, 1986. Example 2 Recording was performed using a combination of the recording ink set and the recording medium prepared in Example 1 shown in the following Table 7 in a recording apparatus of a bubble ink jet system.

[0088]

[Table 7] The images obtained by recording with the above samples were evaluated by the following methods, and the obtained results are shown in Table 8. (1) Image Density On a paper of A4 size, a pattern in which five black solid portions are printed with a black (BK) recording ink of a square having a side of 5 mm, and the optical density of each solid portion after 30 minutes or more has elapsed. Was measured with a Macbeth reflection densitometer RD914, and the average value was defined as an OD value, and the following evaluation was performed based on the obtained OD value. The solid recording ink ejection amount is 12 nl / mm ² . ：: OD of 1.30 or more Δ: OD of 1.25 or more and less than 1.30 ×: OD of less than 1.25 (2) Fixability After forming a red solid image using yellow and magenta recording inks Then, another blank sheet is superimposed on the recorded image by its own weight, the transfer time of the image recorded on the back side of the overlapped blank sheet disappears, and the time until the background stain does not occur is defined as the recording end time as time zero, and the fixing property is determined. The scale was used. The evaluation criteria are as follows. ：: less than 10 seconds △: 10 to 30 seconds ×: 30 seconds or more (3) Feathering The dots of the print sample that have been thinned out on every A4 size paper every other nozzle of the recording head and passed 30 minutes or more Was observed with a magnifying glass, and the following five grades were evaluated. 5: Perfect circle 4: "Smear" is seen or deformed in 1/4 of the circumference. 3: "Smear" is seen or deformed in 1/2 of the circumference, but almost Good 2: "Bleeding" is observed in 3/4 of the circumference or deformed and slightly defective. 1: Arc is not observed and defective. (4) Bleeding. BJC-82 manufactured by Canon Inc.
In the same print mode as print mode E (1PASS, one-way print) of 0 (product name), the pattern of FIG. 9 is printed using each color of yellow, magenta, cyan, and black.
The degree of bleeding (color mixture) at the boundary of each color was visually observed and evaluated according to the following criteria. ：: Bleeding hardly occurs. ：: Slightly generated, but no problem in practical use. ×: Other than that. (5) Water resistance. Solid image of each color of yellow, magenta, cyan, and black and print with alphanumeric characters printed. After leaving the sample for 1 hour after printing, the sample was immersed in tap water at a water temperature of 20 ° C. for 10 seconds. Then, it was taken out of the water, air-dried as it was, and the water resistance was visually evaluated according to the following criteria. A: Ink (dye) does not flow into the margins, and almost no soiling is observed. Almost no alphanumeric bleeding has occurred. ：: Dye bleeds into the margin part slightly, and alphanumeric characters are slightly blurred, but there is no practical problem. X: The dye flowed out to the margin was severe, and the background stain was remarkable. Also, the spread of alphanumeric characters is terrible. Table 8 shows the lowest result among the colors.

Comparative Example 1 Sample No. Comparative Sample No. 1 was obtained by performing the same printing test on a recording medium a using a recording ink having the same composition except that Polymer A was not added. 7 was set. In addition, the sample No. In Comparative Sample N, the same printing test was performed on the recording medium b using the recording ink having the same composition except that the polymer A was not added.
o. And 8.

Further, the sample No. A coating liquid having the same composition was prepared except that polyvinyl alcohol (trade name: PVA117, manufactured by Kuraray) was used instead of stearyltrimethylammonium chloride and polyaminesulfone hydrochloride of the coating liquid in 3, and the same printing was performed using ink set C. The sample subjected to the test is referred to as Comparative Sample No. It was set to 9. Table 8 shows the obtained results.

[0091]

[Table 8]

[0092]

According to the present invention, a cationic substance is retained on the recording surface of a recording medium used in combination with a recording ink containing a water-soluble polymer compound having an alicyclic nitrogen-containing heterocyclic ring. High-speed fixing is possible, high-speed printing quality, bleeding (no bleeding)
Thus, an image with higher water resistance can be obtained.

In addition, since the recording is performed in a one-liquid system by holding the cationic substance on the recording medium side,
When two liquids are used, the recording head surface is stained due to the rebound of the liquid when the next liquid is overlaid on the liquid previously injected on the recording medium, and particularly, ink ejection failure or non-ejection due to fixation of aggregates. Problem can be avoided.

[Brief description of the drawings]

FIG. 1 is a longitudinal sectional view of a head section of an ink jet recording apparatus.

FIG. 2 is a cross-sectional view of a head section of the inkjet recording apparatus.

FIG. 3 is an external perspective view of a head unit of the inkjet recording apparatus.

FIG. 4 is a perspective view illustrating an example of an ink jet recording apparatus.

FIG. 5 is a vertical sectional view of the ink cartridge.

FIG. 6 is a perspective view of a recording unit.

FIG. 7 is a perspective view showing a recording unit in which a plurality of recording heads are arranged in parallel.

FIG. 8 is a perspective view showing another configuration of the recording head.

FIG. 9 is a diagram showing a bleeding evaluation pattern.

FIG. 10 is a diagram showing an example of the molecular weight distribution of a mixture of cationic substances.

FIG. 11 is a diagram showing an example of the molecular weight distribution of a mixture of cationic substances.

FIG. 12 is a diagram showing an example of the molecular weight distribution of a mixture of cationic substances.

FIG. 13 is a diagram showing an example of the molecular weight distribution of a mixture of cationic substances.

[Explanation of symbols]

 13 Head 15, 28 Heating Head 21 Ink 25 Recording Medium 40 Ink Bag 44 Ink Absorber 45 Ink Cartridge 61 Wiping Member 65 Recording Head 66 Carriage 70 Recording Unit 71 Head 72 Air Atmosphere

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code Agency reference number FI Technical indication location C08F 290/06 MRS C08F 290/06 MRS B41J 3/04 101Z

Claims (26)

[Claims] 1. A recording medium used for recording with a recording ink containing a water-soluble polymer compound having a nonionic property in a coloring material and an ink and having an alicyclic nitrogen-containing heterocyclic ring, wherein the recording surface has a cation. A recording medium characterized by holding a volatile substance. 2. The recording medium according to claim 1, wherein the water-soluble polymer compound is capable of forming an aggregate with the cationic substance in the presence of the coloring material. 3. The recording medium according to claim 1, wherein the coloring material is an anionic dye. 4. The recording medium according to claim 1, wherein said water-soluble polymer compound has a carboxyl group. 5. The water-soluble polymer compound represented by the following general formula (1): (However, R ¹ represents a hydrogen atom, a methyl group, an ethyl group or any one of the following alicyclic nitrogen-containing heterocycles,
R ⁵ represents any one of the following alicyclic nitrogen-containing heterocycles: R ^{2 to} R ⁴ each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and L ^{1 to} L ⁴ each independently represent the following formula: (Wherein, R ^{6 to} R ⁹ each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms), and represents a divalent group having a structure represented by the following formula. And the sum of s and t is 90 to 99% by weight of the whole water-soluble polymer compound, q is 1 to 10% by weight, n and k are integers, and the sum is in the range of 10 to 30. , M is an integer of 15 to 30, and p is an integer of 1 to 5).
The recording medium according to any one of the above. 6. The water-soluble polymer compound comprises: (a) an acrylate ester of an ethylene oxide or propylene oxide adduct of a substituted morpholine, (b) acrylic acid, and (c) a compound represented by the following general formula (2): (Wherein R ¹ , R ² , L ^{2 to} L ⁴ , n, m and k are defined in the same manner as in the general formula (1)). A recording medium according to claim 1. 7. The water-soluble polymer compound represented by the following general formula (3): (Where R ^{2 to} R ⁴ , L ^{1 to} L ⁴ , k, n, m, p,
q, s and t are defined in the same manner as in the general formula (1).
The recording medium according to claim 6, which is a water-soluble polymer compound having a repeating unit represented by the following formula: 8. The water-soluble polymer compound has a molecular weight of 50 as measured by gel permeation chromatography.
The recording medium according to any one of claims 5 to 7, wherein the number is from 100,000 to 300,000. 9. The water-soluble polymer compound has a molecular weight of 50 as measured by gel permeation chromatography.
The recording medium according to claim 8, wherein the number is from 00 to 50,000. 10. The ink jet printer according to claim 1, which is used for ink jet.
The recording medium according to any one of the above. 11. The cationic substance has a molecular weight of 1000 or less and a molecular weight of 100 when its molecular weight distribution is measured by gel permeation chromatography (GPC).
Claim 1 which gives a fraction exceeding 0.
11. The recording medium according to any one of items 10. 12. The recording medium according to claim 1, wherein said cationic substance is applied to the entire recording surface of a substrate. 13. A recording ink containing a water-soluble polymer compound having a nonionic property in a coloring material and an ink and having an alicyclic nitrogen-containing heterocycle on a recording surface of a recording medium holding a cationic substance. A recording method characterized in that recording is performed by using a recording method. 14. The recording method according to claim 13, wherein the water-soluble polymer compound is capable of forming an aggregate with the cationic substance in the presence of the coloring material. 15. The recording method according to claim 13, wherein the coloring material is an anionic dye. 16. The recording method according to claim 13, wherein the water-soluble polymer compound has a carboxyl group. 17. The water-soluble polymer compound represented by the following general formula (1): (However, R ¹ represents a hydrogen atom, a methyl group, an ethyl group or any one of the following alicyclic nitrogen-containing heterocycles,
R ⁵ represents any one of the following alicyclic nitrogen-containing heterocycles: R ^{2 to} R ⁴ each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and L ^{1 to} L ⁴ each independently represent the following formula: (Wherein, R ^{6 to} R ⁹ each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms), and represents a divalent group having a structure represented by the following formula. And the sum of s and t is 90 to 99% by weight of the whole water-soluble polymer compound, q is 1 to 10% by weight, n and k are integers, and the sum is in the range of 10 to 30. , M is an integer of 15 to 30, and p is an integer of 1 to 5).
16. The recording method according to any one of items 16. 18. The water-soluble polymer compound comprises: (a) an acrylate of an ethylene oxide or propylene oxide adduct of a substituted morpholine, (b) acrylic acid, and (c) a compound represented by the following general formula (2): (Wherein R ¹ , R ² , L ^{2 to} L ⁴ , n, m and k are defined in the same manner as in the general formula (1)). Recording method described in 1. 19. The water-soluble polymer compound represented by the following general formula (3): (Where R ^{2 to} R ⁴ , L ^{1 to} L ⁴ , k, n, m, p,
q, s and t are defined in the same manner as in the general formula (1).
The recording method according to claim 18, wherein the recording method is a water-soluble polymer compound having a repeating unit represented by the following formula: 20. The water-soluble polymer compound having a molecular weight of 5 as measured by gel permeation chromatography.
The recording method according to claim 19 or 20, wherein the number is from 000 to 300,000. 21. The water-soluble polymer compound having a molecular weight of 5 as measured by gel permeation chromatography.
21. The record according to claim 20, which is between 000 and 50,000. Method 22. The cationic substance has a molecular weight of not more than 1000 and a molecular weight of 100 when its molecular weight distribution is measured by gel permeation chromatography (GPC).
14. Gives a fraction greater than 0.
22. The recording method according to any one of claims 21 to 21. 23. The recording method according to claim 13, wherein the cationic substance is applied to the entire recording surface of a base material. 24. The recording method according to claim 13, wherein the recording with the recording ink is performed by an ink jet recording method. 25. The recording method according to claim 24, wherein the inkjet recording method is an on-demand type inkjet recording method. 26. The recording method according to claim 24, wherein the ink jet recording method applies heat energy to the recording ink to apply the recording ink to the recording medium.