JPH08230310A - Recording medium and ink jet recording method using the medium - Google Patents

Abstract

PURPOSE: To perform high-grade recording even when any aq. ink is used by forming the ink receiving layer provided on at least one surface of a base material from an aq. resin, a resin containing a tertiary amine salt in its molecule and a resin containing a quaternary ammonium salt in its molecule. CONSTITUTION: A recording medium 25 suitably used in an ink jet recording system generating and flying small droplets of ink 21 by a system foaming the ink 21 by heating to utilize the foaming pressure of the ink 21 to bond them to a recording medium 25 to perform recording has an ink receiving layer on at least one surface of a base material. In this case, the ink receiving layer is prepared from an aq. resin, a resin containing a tertiary amine salt in its molecule and a resin containing a quaternary ammonium salt in its molecule. In this case, the sum total of the resin having the tertiary amine salt in its molecule and the resin having the quaternary ammonium salt in its molecule is set to 1-100 pts.wt. per 100 pts.wt. of the aq. resin.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a recording medium preferably used for ink jet recording and an ink jet recording method using the same.

[0002]

2. Description of the Related Art Ink jet recording methods include various ink ejection methods, for example, an electrostatic suction method, a method in which a piezoelectric element is used to mechanically vibrate or displace the ink, the ink is heated to foam, and its pressure is changed. Depending on the method used,
A small amount of ink is generated and ejected, and some or all of them are attached to a recording medium, which is a recording medium such as paper or a plastic film coated with an ink receiving layer, for recording. It is attracting attention as a method capable of high-speed printing and multi-color printing with less occurrence of printing.

As an ink used in the ink jet recording system, a so-called water-based ink containing water as a main component is generally used from the viewpoint of safety and recording characteristics. In order to prevent nozzle clogging and improve ejection stability. Polyhydric alcohols are often added.

Conventionally, as a recording medium used for ink jet recording, as described in Japanese Patent Publication No. 3-26665, a coating layer containing fine powder silica and a water-soluble binder such as polyvinyl alcohol is provided on a base paper. The recording paper provided, or a glossy paper obtained by forming a coating film containing a polyvinyl alcohol having a valence of 50 to 90 mol% and a crosslinking agent on a cast coated paper, as described in JP-B-3-25352. As described in JP-A-60-220750, a recording sheet for an overhead projector (OHP) in which a hydrophilic film made of a water-soluble polyvinyl alcohol having a saponification degree of 70 to 90 mol% is provided on a polyester film. And so on.

[0005]

In recent years, speeding up of recording,
Along with the improvement in the performance of the inkjet recording apparatus in multi-color printing, more advanced and broader characteristics are required for the inkjet recording medium.

That is, (1) high ink absorption capacity (large ink absorption capacity, fast absorption time),
(2) The optical density of the dots is high, the periphery of the dots is not blurred, (3) The shape of the dots is close to a perfect circle, and the periphery is smooth, (4) The image is stable for long-term storage and does not deteriorate. (Especially under high temperature and high humidity environment), (5) Change in characteristics is small due to changes in temperature and humidity, and curling does not occur.
(6) No blocking occurs, (7) the recording medium itself is stable and does not deteriorate even after long-term storage (especially in a high temperature and high humidity environment), (8) images are printed on the printed matter for a long period of time. Does not fade (good light resistance), and other characteristics are required at the same time.

In OHP recording sheets and the like, it is also required that the recording medium itself has excellent transparency.

Further, in glossy films and the like, it is further required that the ink receiving layer does not impair the glossiness of the glossy film itself.

These various characteristics are often in a trade-off relationship, and it has been impossible to satisfy them at the same time with the conventionally known technology.

For example, the exemplified recording medium of the prior art is
Ink absorbability, image density, dot shape and blocking resistance are all reasonable,
The image was not satisfactory in terms of long-term storage stability and light resistance.

When the printed matter is displayed for a long period of time, the image bleeds in the secondary color portion and the portion where the ink ejection amount corresponds to the secondary color portion, the image quality is remarkably deteriorated, and a certain color solid portion is present. When printed in different colors on the above, color stains were caused by mixed colors, and when characters were printed in different colors, it was unreadable.

Recently, it has been reported that black ink and color inks having different surface tension physical properties are used to reduce bleeding between black and color colors. However, there are few examples of recording media showing good recording characteristics for inks having different physical property values.

Further, in the case of OHP recording media, in consideration of other performances such as fixability, there is still no one satisfying the overall performance.

As described above, as the speed of ink jet recording, the density of images, the use of color, and the diversification of ink have progressed, poor fixing of ink, deterioration of image quality, and deterioration of storability of printed matter are serious. Has become a problem.

The recording medium provided with an ink receiving layer mainly composed of polyvinylpyrrolidone described in Japanese Patent Publication No. 3-29596 has a relatively good ink absorbing capacity in a room temperature and normal humidity environment. Ink dries very slowly in a high-humidity environment and tends to cause blocking. Also,
It has a drawback that the recording surface has weak mechanical strength and is easily scratched.

The above-mentioned recording medium provided with an ink receiving layer mainly composed of polyvinyl alcohol has relatively good blocking resistance and recording surface mechanical strength, but the recording medium is long-lived in a high temperature and high humidity environment. If left unattended for a period of time, the recording medium itself is altered and the ink absorption capacity is reduced. Further, when the image is left in a high temperature and high humidity environment for a long time, there is a drawback that the dots are blurred and the sharpness of the image is lowered.

Further, as described in JP-A-63-221077, the use of polyvinyl acetal as a material for the ink receiving layer solves the problem of ink absorption capacity to some extent, but particularly recording When the image is left under a high temperature and high humidity environment for a long time, the image sharpness is not maintained.

Further, in the case of the recording method using the above-mentioned ones having different physical properties such as surface tension between the black ink and the color ink, JP-A 61-10483, JP-A 60-171143 or JP-A-61-2
As described in JP-A-35182 and the like, by using a cation-modified polyvinyl alcohol as a constituent material of the ink receiving layer, quite satisfactory printing characteristics can be obtained, but the ink fixing property, the stickiness of the surface of the ink receiving layer, and the like. Sufficient performance has not been obtained in terms of stickiness and long-term image stability.

Further, JP-A-59-95188, JP-A-57-93193, or JP-A-62-1952.
As described in Japanese Patent No. 170383 and the like, there is a report that an aqueous resin emulsion is used as a constituent material of the ink receiving layer.
It is not possible to solve the above problems comprehensively, and the most important performance is image quality, especially in areas with high image density, that is, in areas with a large amount of ink shot, image stains and uneven density due to ink overflow. Will cause.

Further, JP-A-60-11389, JP-A-61-252189, or JP-A-61-61
As described in, for example, JP-A-293886, 4
There is also a report that it contains only a resin containing a quaternary ammonium salt, but even this composition cannot be a means for comprehensively solving the above problems, and exhibits a sufficient effect in terms of image storability. When the image is stored under high temperature and high humidity, bleeding occurs and the image quality is remarkably deteriorated.

The present invention has been made to solve the above problems, and an object of the present invention is to provide a recording medium which simultaneously satisfies the above-mentioned various characteristics in a well-balanced manner, and an ink jet recording method using the same. , The recording medium itself or the image recorded on the recording medium does not deteriorate even if it is left in a high temperature and high humidity environment for a long time without impairing the ink absorbency, and it has excellent light resistance, and it can be loaded with a recorded matter. It is to provide a recording medium having excellent properties and an inkjet recording method using the recording medium.

[0022]

To achieve the above object, the present invention provides a recording medium having a substrate and an ink receiving layer provided on at least one surface of the substrate, wherein the ink receiving layer is an aqueous resin. Recording medium and substrate containing a resin having a quaternized amine salt in the molecule and a resin having a quaternized ammonium salt in the molecule, and an ink receiving member provided on at least one surface of the substrate A recording medium having a layer, wherein the ink receiving layer contains an aqueous resin and a resin having a tertiary amine salt and a quaternary ammonium salt in the same molecule. The total amount of the aqueous resin in the ink receiving layer, the resin having a tertiary amine salt in the molecule and the resin having a quaternary ammonium salt in the molecule is 100 parts by weight of the aqueous resin. versus And the total amount of the resin having the tertiary amine salt in the molecule and the resin having the quaternary ammonium salt in the molecule is 1 to 100 parts by weight, and the tertiary amine salt in the ink receiving layer is added to the molecule. The ratio of the combined use of the resin contained in the resin and the resin having a quaternized ammonium salt in the molecule is 4
The amount of the resin having a tertiary amine salt in the molecule is more than 0 parts by weight and 100 parts by weight or less with respect to 100 parts by weight of the resin having a quaternary ammonium salt in the molecule, and the aqueous resin is cation-modified. The resin used in the ink receiving layer has a combination ratio of the water-based resin in the ink receiving layer and the resin having a tertiary amine salt and a quaternary ammonium salt in the same molecule, based on 100 parts by weight of the aqueous resin. 3 in the same molecule
The resin having the quaternized amine salt and the quaternized ammonium salt is in the range of 1 to 100 parts by weight, and the ratio of the units of the quaternized ammonium salt and the quaternized amine salt in the ink receiving layer is quaternized. The number of units of the tertiary amine salt is in the range of more than 0 and 100 or less with respect to 100 units of ammonium salt, the aqueous resin is a cation-modified resin, and the substrate is a plastic film. That is, the base material is paper.

Further, the present invention is an ink jet recording method characterized in that ink is ejected from an orifice of a recording head in accordance with a recording signal to perform recording on the above recording medium, wherein the liquid medium components of the ink are water and water-miscible. That contains water-soluble glycols or glycol ethers, the ink is cyan, magenta, yellow or black ink, and the surface tension of black ink is higher than that of cyan, magenta, and yellow inks. , Which includes ejecting ink by the action of thermal energy.

The present invention is also a printed matter in which an image is held on the above recording medium.

[0025]

The present inventor is developing a recording paper suitable for ink jet recording and a transparency film for an overhead projector, and a recording medium coated with the composition has an extremely high ink absorbing ability. The dots are clear and sharp, have excellent blocking resistance, have little change in performance with changes in environmental conditions such as temperature and humidity, and are recording media that are stable for long-term storage especially in high temperature and high humidity environments. The inventors have found that a stable image can be formed for long-term storage under a high temperature and high humidity environment, and that they are excellent in ink fixing property and printed matter loading property, and have completed the present invention.

That is, by containing an aqueous resin in the ink receiving layer, the affinity with respect to the different properties of each ink, particularly with respect to water and water-miscible glycols or glycol ethers, is increased, It is considered that the absorption capacity of the is greatly enhanced, and a clear image with sharp dots can be obtained. In addition, recording characteristics against changes in environmental conditions such as temperature and humidity,
Changes in performance such as physical properties are reduced.

Further, by mixing a resin containing a tertiary amine salt in the molecule and a resin containing a quaternary ammonium salt in the molecule with the aqueous resin, the load of recorded matter on the aqueous resin, In addition to solving problems such as light resistance and storability of images, the above performance is dramatically improved,
It is possible to satisfy the overall performance as a recording medium having an ink receiving layer such as an OHP film and a glossy film.

Further, similar performance can be improved by mixing a resin containing a tertiary amine salt and a quaternary ammonium salt in the same molecule with an aqueous resin.

Next, the present invention will be described in more detail with reference to preferred embodiments.

The water-based resin used in the present invention includes water-soluble resin and water-dispersible resin.

The water-soluble resin may be any resin as long as it can accept a so-called aqueous ink and exhibits solubility or affinity with the aqueous ink, such as unmodified polyvinyl alcohol, anion-modified polyvinyl alcohol and cation-modified polyvinyl alcohol. Polyvinyl alcohol, unmodified hydroxyethyl cellulose, anion modified hydroxyethyl cellulose, cation modified hydroxyethyl cellulose, polyurethane, carboxymethyl cellulose, acetal, polyester, polyacrylic acid (ester),
Examples thereof include hydroxymethyl cellulose, melamine resin, or synthetic resins such as modified products thereof, and natural resins such as albumin, gelatin, casein, starch, cationized starch, gum arabic, and sodium alginate, but are not limited thereto. Not something.

As the water-dispersible resin, polyvinyl acetate,
Ethylene-vinyl acetate copolymer, polystyrene, styrene- (meth) acrylic acid ester copolymer, (meth) acrylic acid ester-based polymer, vinyl acetate- (meth) acrylic acid (ester) copolymer, poly (meth ) Acrylamide, (meth) acrylamide copolymer, styrene-
Isoprene copolymer, styrene-butadiene copolymer,
Ethylene-propylene copolymer, polyvinyl ether,
A large number of silicone-acrylic polymers and the like can be listed, but of course the present invention is not limited to these. Further, it may be a copolymer containing a monomer unit such as N-methylolacrylamide and having a self-crosslinking property.

It is also possible to mix a plurality of these aqueous resins and use them simultaneously.

The resin having a tertiary amine salt in the molecule which forms an ink receiving layer with the above aqueous resin is not limited as long as the resin having a tertiary amine is neutralized with an acid. Examples of the resin having a tertiary amine include dimethylethanolamine, diethylethanolamine, trimethylamine, methyldiethanolamine, dibutylethanolamine, methylethanolamine, triethanolamine, triallylamine, dibutylaminopropylamine, tetramethylethylenediamine, lauryl. Dimethylamine, stearyldimethylamine, dimethylamine and the like can be listed, but not limited to these.

As the acid for neutralizing the resin having a tertiary amine, a strongly acidic inorganic acid such as hydrochloric acid or sulfuric acid, or a relatively weakly acidic lower fatty acid such as formic acid or acetic acid is used. However, the present invention is not limited to this.

Further, the resin having a quaternized ammonium salt in its molecule which forms an ink receiving layer together with the above aqueous resin is limited as long as it is a quaternized resin having a tertiary amine. As the resin having a tertiary amine, dimethylethanolamine, diethylethanolamine, trimethylamine, methyldiethanolamine, dibutylethanolamine, methylethanolamine, triethanolamine, triallylamine, dibutylaminopropylamine, tetramethylethylenediamine , Lauryldimethylamine, stearyldimethylamine, dimethylamine, etc. can be listed,
It is not limited to these.

Substances for quaternizing a resin having a tertiary amine include alkyl halides such as methyl chloride, methyl bromide and benzyl chloride, epichlorohydrin, dimethylsulfate, diethylsulfate and ethylene oxide. It can be illustrated.

Further, a tertiary amine salt and 4 in the same molecule are used together with the above water-soluble resin to form an ink receiving layer.
The resin containing a quaternary ammonium salt is not limited as long as it is a quaternized resin obtained by quaternizing a resin having a tertiary amine and further neutralizing the resin with an acid. As the resin having, dimethylethanolamine,
Diethylethanolamine, trimethylamine, methyldiethanolamine, dibutylethanolamine, methylethanolamine, triethanolamine, triallylamine, dibutylaminopropylamine, tetramethylethylenediamine, lauryldimethylamine, stearyldimethylamine, dimethylamine, etc. can be listed. It is not limited to.

The methods for tertiary and quaternizing a tertiary amine include the above-mentioned methods, but are not limited thereto.

The weight ratio of the above-mentioned aqueous resin to the total of the resin containing the tertiary amine salt and the resin containing the quaternary ammonium salt is within the range from 1/1 to 100/1. Preferably there is. Mixing ratio of water-based resin is 1
When it is more than 00/1, sufficient effect cannot be obtained in terms of long-term stability of the image under high temperature and high humidity, and when the mixing ratio of the water-based resin is less than 1/1, image quality and fixing of ink are fixed. Property, and further, the light resistance is apt to be deteriorated, and it is not possible to obtain a sufficient effect only by mixing the resin containing the quaternized amine salt and the resin containing the quaternized ammonium salt.

The mixing ratio by weight of the aqueous resin described above and the resin containing a tertiary amine salt and a quaternary ammonium salt in the same molecule in terms of solid content is from 1/1 to 100/1.
It is preferably within the following range. When the mixing ratio of the water-based resin is more than 100/1, a sufficient effect cannot be obtained in terms of long-term stability of the image, and the mixing ratio of the water-based resin is 1/1.
When the amount is less than 1, the image quality is poor, the fixing property of the ink is not sufficient, and further, the light fastness is likely to decrease, and a resin containing a tertiary amine salt and a quaternary ammonium salt is mixed in the same molecule. You can't get the full effect you've done.

Further, the ratio of the quaternized ammonium salt unit to the quaternized ammonium salt unit is more than 0 with respect to 100 units of the quaternized ammonium salt unit. It is desirable that the range is 100 or less.

The effect obtained by mixing a resin containing a quaternized amine salt and a resin containing a quaternized ammonium salt, and a resin containing a ternary amine salt and a quaternized ammonium salt in the same molecule The effect obtained by mixing is greater in the cation-modified resin than in the unmodified resin.

In the present invention, a generally well-known cationic compound may be further contained, if necessary.

The cationic compound is not limited as long as it contains a cationic moiety in the molecule, and examples of the low molecular weight compound include monoalkylammonium chloride, dialkylammonium chloride, tetramethylammonium chloride and trimethylphenyl. Quaternary ammonium salt-type cationic surfactants such as ammonium chloride and ethylene oxide-added ammonium chloride, or amine salt-type cationic surfactants, and further alkyl betaines and imidazolium betaines containing cationic moieties. A double-sided surfactant such as an alanine-based surfactant may be used.

As the polymer or oligomer, a cation-modified polyacrylamide or a copolymer of acrylamide and a cationic monomer,
Examples thereof include polyallylamine, polyamine sulfone, polyviramine, polyethyleneimine, polyamide-epichlorohydrin resin, polyvinylpyridinium halide and the like.

Further, vinyl oxazolidone type monomers alone or copolymers with other general monomers,
Examples thereof include vinyl imidazole-based monomers alone or copolymers with other general monomers.

Examples of the above-mentioned general monomer include methacrylate, acrylate, acrylonitrile, vinyl ether, vinyl acetate, ethylene and styrene. Also, cation-modified cellulose or the like may be used.

The above-mentioned cation-modified compounds are preferably used, but of course, the cationic compounds are not limited to these.

Of course, in the constitution according to the present invention, the above-mentioned cationic compound is not an essential component but merely shows an auxiliary role.

Further, but not limited to, methylolated melamine, methylolated urea, methylolated hydroxypropylene urea, and isocyanate.
A cross-linking agent may be included.

In the present invention, the above-mentioned aqueous resin, a resin containing a tertiary amine salt and a resin containing a quaternary ammonium salt, or a tertiary amine salt and a quaternary ammonium salt in the same molecule. A composition containing a resin containing as an essential component is coated on at least one surface of the substrate to form a recording medium having an ink receiving layer on the substrate surface. In addition, various fillers and further additives can be used in combination as long as the object of the present invention is not impaired.

Examples of the filler include silica, alumina, aluminum silicate, magnesium silicate, basic magnesium carbonate, talc, hadodaltalsite, calcium carbonate, titanium oxide, zinc oxide, and polyethylene, polystyrene, poly Examples thereof include, but are not limited to, plastic pigments such as acrylate.

Specific examples of the additives include various surfactants, dye fixing agents (waterproofing agents), antifoaming agents, antioxidants, optical brighteners, ultraviolet absorbers, dispersants, clay modifiers. ,
Examples thereof include pH adjusters, antifungal agents and plasticizers. These additives and their addition amounts may be arbitrarily selected from conventionally known compounds according to the purpose.

The base material constituting the recording medium of the present invention includes high-quality paper, medium-quality paper, art paper, bond paper, recycled paper, baryta paper, cast-coated paper, cardboard paper, polyethylene terephthalate, and diterephthalate. Films made of plastics such as acetate, triacetate, cellophane, celluloid, polycarbonate, polyimide, polyvinyl chloride, polyvinylidene chloride, polyacrylate, polyethylene, polypropylene, or plates, glass plates, or cotton, rayon, acrylic, nylon, silk Cloths such as polyester and the like can be used, but are not limited thereto.

Further, those having an uneven surface, those obtained by vapor-depositing metal such as aluminum on paper or film,
In the substrate depending on the recording purpose of the recording medium, the use of the recorded image, or the adhesiveness with the composition coated on top of it, such as those processed with holograms and those using the flip-flop effect. The substrate may be transparent, semi-transparent, or opaque.

If a transparent material such as a plastic film is used as the base material, an OHP film can be formed,
A glossy paper can be formed by using paper or an opaque material such as white polyethylene terephthalate as the base material.

In preparing the recording medium of the present invention, the composition is dissolved or dispersed in water or alcohol, polyhydric alcohol or other suitable organic solvent together with other additives, if necessary, and coated. Adjust the working fluid.

The obtained coating liquid is, for example, a roll coater method, a blade coater method, an air knife coater method, a gate roll coater method, a bar coater method, a size press method, a spray coat method, a gravure coater method or a curtain coater method. To coat the surface of the substrate. Then, for example, it is dried using a hot air drying oven, a hot drum, etc., and the recording medium of the present invention is obtained.

The coating amount of the ink receiving layer on the base material is in the range of 0.2 to 50 g / m ² , more preferably 1 to 30 g / m ² in total (dry state). When the coating amount is small, a part of the base material may be exposed on the surface. When this coating amount is less than 0.2 g / m ² , sufficient effect cannot be obtained in terms of color developability of the coating as compared with the case where the ink receiving layer is not provided, while 50 g / m ²
When the ink receiving layer is provided over the range, curling is likely to occur especially in a low temperature and low humidity environment. When the coating amount is expressed by thickness, the coating amount is preferably in the range of 0.5 to 100 μm.

As the ink itself for carrying out ink jet recording on the recording medium described above, known inks can be used without any problems. As the recording agent, a direct dye, an acid dye, a basic dye, a reactive dye, a water-soluble dye typified by an edible dye, a dispersible dye, and a pigment can be used. If there is no particular limitation, it can be used. Such water-soluble dyes or dispersible dyes and pigments are generally used in a proportion of about 0.1 to 20% by weight in conventional inks, and the same may be applied to the present invention. .

The solvent used in the water-based ink used in the present invention is water or a mixed solvent of water and a water-soluble organic solvent, and a particularly preferable solvent is a mixed solvent of water and a water-soluble organic solvent. As the organic solvent, a polyhydric alcohol having an effect of preventing ink drying is contained.

The method for applying the above-mentioned ink to the above-mentioned recording medium for recording is preferably an ink jet recording method, and this method is a range in which the ink is effectively separated from the nozzle. Any method may be used as long as it can apply ink to the recording medium.

Particularly, in the method described in Japanese Patent Laid-Open No. 54-59936, the ink subjected to the action of thermal energy causes a rapid volume change, and the action force due to this state change ejects the ink from the nozzle. The inkjet method can be effectively used.

An example of an ink jet recording apparatus suitable for recording using the recording medium of the present invention will be described below. An example of a head configuration that is a main part of the apparatus is shown in FIGS.
And shown in FIG.

The head 13 is a heating head 15 (a head is shown in the drawing, but not limited to this, which is a glass, ceramics, or plastic plate having a groove 14 through which ink passes, and is used for thermal recording. ) Is obtained by bonding and. The heating head 15 includes a protective film 16 made of silicon oxide, an aluminum electrode 17-1,
17-2, heating resistor layer 1 formed of nichrome or the like
8, heat storage layer 19, substrate 20 having good heat dissipation such as alumina
Has become

The ink 21 is a discharge orifice (fine hole).
22 and the meniscus 23 is formed by the pressure P.

Now, when an electric signal is applied to the electrodes 17-1 and 17-2, the area indicated by n of the heating head 15 rapidly generates heat, and bubbles are generated in the ink 21 in contact therewith,
The pressure causes the meniscus 23 to project, and the ink 21 is ejected from the orifice 22 to form a recording droplet 24, which flies toward the recording medium 25. FIG. 3 shows an external view of a multi-head in which many heads shown in FIG. 1 are arranged. The multi-head is manufactured by closely adhering a glass plate 27 having a multi-groove 26 and a heating head 28 similar to that described in FIG.

FIG. 1 is a sectional view of the head 13 taken along the ink flow path, and FIG. 2 is a sectional view taken along the line AB of FIG.

An example of an ink jet recording apparatus incorporating the head shown in FIG. 4 is shown.

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, which is in the form of a cantilever. The blade 61 is arranged at a position adjacent to the recording area by the recording head, moves in a direction perpendicular to the moving direction of the recording head, contacts the ejection port surface, and performs capping. Further, 63 is an ink absorber provided adjacent to the blade 61, and like the blade 61,
The cap 62 and the absorber 63 form an ejection recovery unit 64, and the blade 61 and the absorber 63 remove water and dust from the ink ejection port surface.

Reference numeral 65 has a discharge energy generating means,
A recording head 66 for performing recording by ejecting ink onto a recording medium facing the ejection port surface provided with the ejection port, 66 is the recording head 6
5 is a carriage for carrying the recording head 65 and moving the recording head 65. The carriage 66 slidably engages with the guide shaft 67, and a part of the carriage 66 is connected (not shown) to a belt 69 driven by a motor 68.
As a result, the carriage 66 can move along the guide shaft 67, and the recording head 65 can move the recording area and its adjacent area.

Reference numeral 51 is a paper feed section for inserting a recording medium, and 52 is a paper feed roller driven by a motor (not shown). With these configurations, the recording medium is fed to the position facing the ejection port surface of the recording head, and as the recording progresses, the sheet discharge roller 53 is arranged and the sheet is discharged.

In the above structure, when the recording head 65 returns to the home position due to the end of recording, the head recovery section 64
The cap 62 is retracted from the moving path of the recording head 65, but the blade 61 is projected in the moving path.
As a result, the ejection port surface of the recording head 65 is wiped. When the cap 62 comes into contact with the protruding surface of the recording head 65 to perform capping, the cap 62 moves so as to protrude into the moving 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 in the same position as the above-mentioned position during wiping. As a result, the ejection opening surface of the recording head 65 is wiped even during this movement.

The above-mentioned movement of the recording head to the home position is performed not only at the end of recording or at the time of ejection recovery, but also at the home adjacent to the recording area at a predetermined interval while the recording head moves in the recording area for recording. The wiper is moved to the position, and the wiping is performed along with the move.

[0077]

The present invention will be described in more detail with reference to the following examples. In the text, “part” or “%” is based on weight unless otherwise specified. (Example 1) Polyvinyl alcohol (Brand name: PVA2)
17, manufactured by Kuraray, polymerization degree about 1700, saponification degree about 88 mol%) 100 parts, copolymer of methyl methacrylate and dimethylaminoethyl methacrylate (unit ratio:
Tertiary amine salt / quaternary ammonium salt = 100/1)
A composition of 20 parts was mixed.

The obtained coating solution was applied using a wire bar.
Polyethylene terephthalate film (trade name: Lumirror, manufactured by Toray, thickness 100 μm), coating thickness after drying is 1
After coating so as to have a thickness of 0 μm, the recording medium of the present invention was prepared by drying at 120 ° C. for 3 minutes.

Color recording was carried out on the above recording medium under the following conditions using an ink jet recording apparatus in which the ink having the following composition was used and the ink was foamed by thermal energy to eject the ink.

Ink composition: BK (black) C.I. I. Direct Black 19 3 parts Glycerin 6 parts Ethylene glycol 5 parts Urea 5 parts Isopropyl alcohol 3 parts Water 78 parts The surface tension of this ink was about 45 dyne / cm.

Ink composition: Y. M. C (yellow, magenta, cyan) dye 3 parts glycerin 7 parts thiodiglycol 7 parts urea 7 parts acetylene glycol 1.5 parts water 73.5 parts The surface tension of this ink was about 35 dyne / cm.

Dye Y: C.I. I. Direct Yellow 86 M: C.I. I. Acid Red 23 C: C.I. I. Direct Blue 199 Recording conditions Ejection frequency: 4 KHz Ejection droplet capacity: 45 pl Recording density: 360 dpi Maximum single-color ink application amount: 8 nl / mm ² (Example 2) Aqueous resin is cation-modified polyvinyl alcohol (trade name: CM-318, Made by Kuraray, polymerization degree about 17
00, saponification degree about 89%, cationization degree about 2 mol%), and a recording medium was prepared in the same manner as in Example 1.
Color recording was performed. (Example 3) A recording medium was prepared and color recording was performed in the same manner as in Example 1 except that polyvinyl acetal (trade name: KW-1, manufactured by Sekisui Chemical Co., Ltd.) was used as the aqueous resin. (Example 4) A recording medium was prepared and color recording was performed in the same manner as in Example 1 except that an aqueous resin and hydroxyethyl cellulose (trade name: AL-15, manufactured by Fuji Chemical) were used. (Example 5) A recording medium was prepared and color recording was carried out in the same manner as in Example except that the aqueous resin was cationized hydroxycellulose (manufactured by Fuji Chemical). (Example 6) The copolymer used in Example 1 was used as a quaternized ammonium salt as a specially modified polyamine (trade name: Polyfix 610, Showa High Polymer Co., Ltd.) 15 parts, and as a tertiary amine salt shown below (I ) Was adjusted and 5 parts were used, and a recording medium was prepared in the same manner as in Example 1, and color recording was performed.

[0083]

Embedded image (Example 7) Cation-modified polyvinyl alcohol (trade name: CM-318, manufactured by Kuraray, polymerization degree of about 17)
00, saponification degree: about 89 mol%, cationization degree: about 2 mol%), a recording medium was prepared in the same manner as in Example 6, and color recording was carried out. (Example 8) A recording medium was prepared and color recording was performed in the same manner as in Example 6 except that polyamine sulfone (trade name: PAS-A-120, manufactured by Nitto Kagaku Co., Ltd.) was used as the quaternized ammonium salt. . (Example 9) A recording medium was prepared and color recording was performed in the same manner as in Example 7 except that polyamine sulfone (trade name: PAS-A-120, manufactured by Nitto Kagaku Co., Ltd.) was used as the quaternized ammonium salt. . (Examples 10, 11, 12, 13, 14) Recording medium in the same manner as in Example 1 except that art paper, white polyethylene terephthalate film, semitransparent film, aluminum vapor deposition film, and acrylic plate were used as the base material, respectively. Was prepared and color recording was performed. (Comparative Example 1) Polyvinyl alcohol (Product name: PVA2
17, manufactured by Kuraray Co., Ltd., having a polymerization degree of about 1700 and a saponification degree of about 88 mol%), a recording medium was prepared in the same manner as in Example 1 and color recording was performed. (Comparative Example 2) As in Example 1 except that only cation-modified polyvinyl alcohol (trade name: CM-318, manufactured by Kuraray, polymerization degree of about 1700, saponification degree of about 89 mol%, cationization degree of about 2 mol%) was used. A recording medium was prepared in the same manner and color recording was performed. (Comparative Example 3) Polyvinyl acetal (trade name: KW-
1, manufactured by Sekisui Chemical Co., Ltd., and a recording medium was prepared in the same manner as in Example 1 and color recording was performed. (Comparative Example 4) Hydroxycellulose (trade name: AL-1
No. 5, manufactured by Fuji Chemical Co., Ltd.), a recording medium was prepared and color recording was performed in the same manner as in Example 1. (Comparative Example 5) A recording medium was prepared and color recording was performed in the same manner as in Example 1 except that only cationized hydroxycellulose (manufactured by Fuji Chemical Co., Ltd.) was used. (Comparative Example 6) Polyvinyl alcohol (Product name: PVA2
17, manufactured by Kuraray, having a degree of polymerization of about 1700 and a degree of saponification of about 88 mol%) was mixed with 10 parts of a specially modified polyamine (trade name: Polyfix 610, manufactured by Showa High Polymer Co., Ltd.). The recording medium was prepared and color recording was performed. (Comparative Example 7) 100 parts of a cation-modified polyvinyl alcohol (trade name: CM-318, manufactured by Kuraray, polymerization degree of about 1700, saponification degree of about 89 mol%, cationization degree of about 2 mol%) and special modified polyamine (trade name: Polyfix 61
Example 1 except that 10 parts (0, Showa High Polymer) were mixed.
A recording medium was prepared in the same manner as in 1. and color recording was performed. (Comparative Example 8) Polyvinyl alcohol (Brand name: PVA2)
17, manufactured by Kuraray Co., Ltd., polymerization degree of about 1700, saponification degree of about 88 mol%) and 100 parts of the above amine (I) were mixed to prepare a recording medium in the same manner as in the example, and color recording was carried out. It was (Comparative Example 9) 100 parts of a cation-modified polyvinyl alcohol (trade name: CM-318, manufactured by Kuraray, polymerization degree of about 1700, saponification degree of about 89 mol%, cationization degree of about 2 mol%) and the amine (I) 10 were added. A recording medium was prepared and color recording was carried out in the same manner as in Example 1 except that parts were mixed.

The color print samples obtained were evaluated for the following items.

(1) Ink fixing property In an environment of 25 ° C./60%, after recording with full dots of black and yellow, two colors of cyan and magenta, and leaving for 2 minutes, black and color portions, that is, yellow PBPaper (manufactured by Canon) was placed on each of the two full-color areas, cyan, magenta, and magenta, and rubbed from above with a pressure of 4 kg / cm ² , and when the paper was peeled off, the ink was clearly transferred to the paper. The presence of X was marked, the mark of slight transfer was marked with Δ, and the mark of no transfer was marked with O.

(2) Stickiness When the surface of the ink-receiving layer was touched with a hand, the one with obvious stickiness was marked with X, the one with slight stickiness was marked with Δ, and the one without stickiness was marked with ◯.

(3) Image storability The obtained color print sample was stored in an environment of 30 ° C./80% for 7 days, and then compared with the color print sample before storage, and bleeding, thickening of characters, and blank characters ( 18 points, Mincho typeface crushing occurred and the image quality was remarkably inferior. ×, bleeding, thickening of characters, and outline characters (18 points, Mincho typeface) crushing occurred, but the characters were legible. Possible samples were evaluated as Δ, and those without problems were evaluated as ○.

(4) Image quality Visual judgment is made. The obtained color print sample has a high optical density and is excellent in gradation and is clear, and ○ is slightly inferior in optical density, gradation and clarity, and is clearly low in optical density and gradation. Those that were not clear and were unclear were rated as x.

(5) Light resistance After irradiation with a xenon lamp for 30 hours using an Atlas fade meter (Toyo Seiki), the printed matter before and after the test was compared. The printed matter uses solid printing portions of black, yellow, magenta, and cyan. When the residual image density ratio is less than 50% even with one color, x is given; It was set as Δ.

The evaluation results are summarized in Table 1.

[0091]

[Table 1]

[0092]

As described above, according to the present invention, various inks having different characteristics are excellent in ink absorption, the dots are clear, the optical density is high, the gradation is high and the gradation is high. Not only is it possible to form an image, but also the ink fixability to the ink receiving layer is good, and no image deterioration is observed when the printed matter is stored for a long period of time in a high temperature and high humidity environment.
It has become possible to supply a recording medium with excellent light resistance and ideal performance requirements.

[Brief description of drawings]

FIG. 1 is a vertical sectional view of a head portion of an inkjet recording apparatus.

FIG. 2 is a cross-sectional view of a head portion of an inkjet recording device.

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

FIG. 4 is a perspective view showing an example of an inkjet recording apparatus.

[Explanation of symbols]

 13 heads 15 and 28 heat generating head 21 ink 25 recording medium 61 wiping member 65 recording head 66 carriage

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location B41J 2/21 C09D 11/00 PSZ 2/01 B41J 3/04 101A // C09D 11/00 PSZ 101Y

Claims (16)

[Claims] 1. A recording medium having a base material and an ink receiving layer provided on at least one surface of the base material, wherein the ink receiving layer comprises an aqueous resin and a resin having a tertiary amine salt in its molecule. A recording medium comprising a resin having a graded ammonium salt in its molecule. 2. A recording medium having a base material and an ink receiving layer provided on at least one surface of the base material, wherein the ink receiving layer comprises an aqueous resin, a tertiary amine salt and a quaternary ammonium salt in the same molecule. A recording medium containing a resin having a salt. 3. The combined ratio of the aqueous resin in the ink receiving layer, the total amount of the resin having a tertiary amine salt in the molecule and the resin having a quaternary ammonium salt in the molecule is 100 weight% of the aqueous resin. The recording medium according to claim 1, wherein the total amount of the resin having the quaternized amine salt in the molecule and the resin having the quaternized ammonium salt in the molecule is 1 to 100 parts by weight based on parts. 4. A resin having a quaternary ammonium salt in the molecule in a combination ratio of a resin having a quaternary amine salt in the molecule and a resin having a quaternary ammonium salt in the molecule in the ink receiving layer. The recording medium according to claim 1, wherein the amount of the resin having a tertiary amine salt in the molecule is more than 0 parts by weight and 100 parts by weight or less with respect to 100 parts by weight. 5. The recording medium according to claim 1, wherein the aqueous resin is a cation-modified resin. 6. The combination ratio of the aqueous resin in the ink receiving layer and the resin having a tertiary amine salt and a quaternary ammonium salt in the same molecule is the same with respect to 100 parts by weight of the aqueous resin. The recording medium according to claim 2, wherein the resin having a tertiary amine salt and a quaternary ammonium salt in the molecule is in the range of 1 to 100 parts by weight. 7. The ratio of the units of the tertiary amine salt and the quaternary ammonium salt in the ink receiving layer is 100 relative to 100 units of the quaternary ammonium salt, and the number of units of the tertiary amine salt is 0. The recording medium according to claim 6, which is in a range of more than 100. 8. The recording medium according to claim 2, wherein the aqueous resin is a cation-modified resin. 9. The recording medium according to claim 1, wherein the substrate is a plastic film. 10. The recording medium according to claim 1, wherein the base material is paper. 11. The recording medium according to claim 1 or 2,
An ink jet recording method, wherein recording is performed by ejecting ink from an orifice of a recording head according to a recording signal. 12. The ink jet recording method according to claim 11, wherein the liquid medium component of the ink contains water and water-miscible glycols or glycol ethers. 13. The ink jet recording method according to claim 11, wherein the ink is cyan, magenta, yellow, or black ink. 14. The surface tension of black ink is cyan,
The ink jet recording method according to claim 13, which has a higher surface tension than that of magenta and yellow ink. 15. The ink jet recording method according to claim 11, wherein the ink is ejected by the action of thermal energy. 16. A printed matter in which an image is held on the recording medium according to claim 1 or 2.