JPH0662002B2 - Recording material - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a recording material suitably used in an inkjet recording method, and particularly to ink receptivity, recorded image sharpness, water resistance and blocking resistance. An excellent recording material.

(Prior Art) Ink jet recording methods include various ink (recording liquid) ejection methods, such as an electrostatic suction method, a method in which a piezoelectric element is used to mechanically vibrate or displace ink, and ink is heated to foam. By the method of utilizing the pressure, etc., small droplets of ink are generated and ejected, and some or all of them are attached to a recording material such as paper for recording, but there is little noise generation. It is attracting attention as a recording method capable of high-speed printing and multicolor printing.

As the ink for inkjet recording, those mainly containing water are used in terms of safety and recording characteristics, and polyhydric alcohol or the like is added to prevent nozzle clogging and improve ejection stability. There are many cases.

As a recording material used in this ink jet recording method, conventionally, a recording material obtained by providing a porous ink receiving layer on a base material called ordinary paper or ink jet recording paper has been used.

However, with the improvement and spread of the performance of inkjet recording apparatuses such as high-speed recording or multicolor recording, more advanced and wide-ranging characteristics are required for recording materials.

That is, as a recording material for inkjet recording for obtaining a high-resolution and high-quality recorded image, (1) the ink can be received by the recording material as quickly as possible, and (2) ink dots are Even if they overlap, the ink deposited later does not flow into the dots deposited before, (3) the ink droplets do not spread on the accused recording material, and the diameter of the ink dot does not become larger than necessary. (4) The shape of the ink dot is close to a perfect circle and the circumference is smooth, (5) The OD (optical density) of the ink dot is high, and the area around the dot is not blurred. Needs to be met.

Further, in order to obtain a high-resolution recording image quality comparable to that of a color photograph by the multicolor ink jet recording method, in addition to the required performance described above, (6) the coloring component of the ink coloring component is excellent. 7) The ink fixing property is particularly excellent because the same number of liquid droplets as the number of ink colors may be adhered to the same place in a pile, (8) The surface is glossy, (9) Whiteness It is required to be weighted with high performance.

Further, a recorded image by the inkjet recording method has been conventionally used exclusively for observing a surface image, but with the improvement and spread of the performance of an inkjet recording apparatus, a recording material suitable for a purpose other than observing a surface image. Is being demanded.

Other than the surface image observation, the recording material is used to project recorded images on a screen or the like by an optical device such as a slide or an OHP (overhead projector) and observe those images. Examples thereof include a color separation plate when creating a positive plate and a CMF (color mosaic filter) used for a color display such as liquid crystal.

When the recording material is used for surface image observation, diffused light of the recorded image is mainly observed, whereas in the recorded material for these applications, transmitted light of the recorded image is a problem. Become. Therefore, it is required that the material has excellent translucency, particularly linear transmissivity, in consideration of the required performance of the above-mentioned general accused recording material for inkjet recording.

(Problems to be Solved by the Invention) However, the fact is that a recording material satisfying all of these required performances is not yet known.

Further, many conventional recording materials for surface image observation use a method in which a porous ink-receiving layer is provided on the surface and ink is received in the porous voids to fix the recording agent. The surface of the recording material was not glossy because of its good properties.

On the other hand, when the surface of the ink receiving layer is non-porous, non-volatile components such as polyhydric alcohol in the ink remain on the surface of the recording material for a long time after recording, and the drying and fixing time of the ink is long. However, there are drawbacks such that when the recorded image is contacted, the clothes are stained and the recorded image is damaged.

In addition, in the case of a recording material that uses a water-soluble polymer for forming the ink receiving layer in order to enhance the affinity with the ink and the ink receiving property, the surface of the ink receiving layer is tacky under high humidity conditions. Therefore, there is a problem that the recording material cannot be conveyed when attached to a printer feed roller or the like when mounted on the printer, and the recording material is blocked when stacked.

Therefore, an object of the present invention is to resist a recording material for ink jet recording which is particularly excellent in ink receptivity, water resistance and sharpness of recorded images.

Another object of the present invention is to provide a recording material for full-color inkjet recording, which is excellent in ink receptivity, sharpness of recorded images, surface gloss, and does not cause surface stickiness or blocking even under high humidity conditions. It is in.

Another object of the present invention is to use a recorded image for observation by projecting it on a screen or the like with an optical device such as a slide OHP, a color separation plate for making a positive plate for color printing, or a color display such as liquid crystal. CM used for
It is to resist the recording material for inkjet recording which can be used for observation of transmitted light such as F.

The above and other objects of the invention are achieved by the following invention.

DISCLOSURE OF THE INVENTION That is, according to the present invention, in an ink jet recording material in which an ink receiving layer is provided on a substrate, the ink receiving layer comprises a basic polymer and a styrene / (meth) acrylic acid copolymer. It is a recording material for inkjet, which contains a polymer complex. In the present invention, the term “(meth) acrylic acid copolymer” is meant to include both acrylic acid copolymer and methacrylic acid ester.

The present invention will be described in detail. In the recording material of the present invention, the ink receiving layer has a basic polymer and styrene / (meth).
The main feature is that it is composed of a polymer complex with an acrylic acid copolymer, and mainly the purpose of the present invention is achieved thereby.

The recording material of the present invention generally comprises a substrate as a support and a recording surface provided on the surface thereof, that is, an ink receiving layer. For example, (1) substrate and ink receiving layer are particularly preferable embodiments. All of them are translucent and the entire recording material is translucent, and (2) the surface of the ink receiving layer is smooth and glossy.

Further, each of the ink receiving layers may have a function as a support at the same time.

The present invention will be described in more detail by taking some of the preferred embodiments described above as representative examples.

The polymer complex which characterizes the present invention mainly comprises a basic polymer and a styrene / (meth) acrylic acid copolymer.

Conventionally, a polymer complex composed of a basic polymer and an acidic polymer is known in, for example, Japanese Patent Publication Nos. 51-37017 and 55-42744.

The present inventors have found that the polymer complex as described above is soluble in a good solvent such as dimethylformamide and dimethylsulfoxide, and is useful for forming an ink receiving layer of a recording material, and has various properties such as ink fixability and water resistance. It was found that an excellent recording material can be obtained (Japanese Patent Application No. 60-2633).
No. 3 specification).

However, the ink receiving layer thus obtained has low durability against the polyhydric alcohol contained in the ink, and the ink receiving portion that has received high density ink dots adheres to the surface under high temperature and high humidity conditions. A phenomenon such as stickiness appears, and a new problem occurs that blocking and color transfer occur when the films are stacked unless the film is dried for a considerably long time such as printing.

As a result of further research to solve the above problems while retaining various advantages of the prior invention, the present inventors have found that as an acidic polymer forming a polymer complex, a specific polymer, that is, styrene / ( When (meth) acrylic acid copolymer is selected, the ink of the ink receiving portion is strong even in the area where the ink dots are concentrated, and the ink has no blocking or color transfer even when the films are overlapped in a short time after printing. Finding that a receptive layer is obtained,
The present invention has been achieved.

In the present invention, preferable basic polymers include, for example, the followings.

N-vinylpyrrolidone, N-vinyl-3-methylpyrrolidone, N-vinyl-5-methylpyrrolidone, N-vinyl-3,3,5-trimethylpyrrolidone, N-vinyl-3
-Benzylpyrrolidone, N-vinylpiperidone, N-vinyl-4-methylpiperidone, N-vinyl-caprolactam, N-vinylcapryllactam, N-vinyl-3-
Morpholine, N-vinylthiopyrrolidone, N-vinyl-
Homopolymers such as 2-pyridone or random copolymers with other common monomers, block copolymers, graft copolymers, etc .; N-vinyl-2-oxazolidone, N-vinyl-5-methyl-2 -Oxazolidone, N-vinyl-5-ethyl-
2-oxazolidone, N-vinyl-4-methyl-2-oxazolidone, N-vinyl-2-thiooxazolidone,
Homopolymers such as N-vinyl-2-mercaptobenzothiazole or random copolymers with other common monomers, block copolymers, graft copolymers, etc .; N-vinylimidazole, N-vinyl-2- Homopolymers such as methylimidazole and N-vinyl-4-methylimidazole, or random copolymers with other common monomers, block copolymers, graft copolymers, etc .; 2- or 4-vinylpyridine, etc. Homopolymers or random copolymers with other general monomers, block copolymers, graft copolymers, and the like, other copolymerizable monomers that may be used in the above, methacrylate, acrylate, Acrylamide, acrylonitrile, vinyl ether, vinyl acetate, vinyl imidazole, ethylene, styrene and its A common monomers such, particularly useful in the present invention, N- vinylpyrrolidone, N- vinyl piperidone, N- vinyl caprolactam, N- vinyl morpholine, N- vinyl-2-
-Oxazolidone and N-vinyl-5-methyl-2-oxazolidone homopolymers and copolymers. In the case of a copolymer, the nitrogen-containing monomer as described above is preferably contained in an amount of 50 mol% or more.

Further, the styrene / (meth) acrylic acid copolymer capable of forming a polymer complex with the basic polymer is a copolymer of styrene or a styrene derivative and acrylic acid or methacrylic acid, and further, these monomers It may be a terpolymer composed of a third monomer other than the above. As the styrene derivative, in addition to styrene, any styrene derivative such as methylstyrene, dimethylstyrene, trimethylstyrene, α-chlorostyrene, and α-methylstyrene can be used. The third monomer includes olefins such as ethylene, propylene and butylene, vinyl halides such as vinyl chloride and vinyl fluoride, vinyl esters such as vinyl acetate, and (meth) acryl such as alcohol ester of (meth) acrylic acid. Any other monomer that is copolymerizable with styrene and (meth) acrylic acid, such as an acid ester, can be used. Any of the conventional copolymerization methods may be used, and those having various copolymerization ratios can be easily obtained from the market and used.

In the present invention, any copolymerization ratio of styrene / (meth) acrylic acid copolymer can be used, but a preferable one is a styrene / (meth) acrylic acid molar ratio of 1/2 to 2/1. The best one is 5 / 5-6
It is also / 4. In the case of a terpolymer, the third monomer can be included in a ratio of up to about 50 mol% of all the monomers.

The styrene / (meth) acrylic acid copolymers having various molecular weights described above are available and can be used.

The inventors of the present invention have conducted various studies on a mixture of the basic polymer as described above and the styrene / (meth) acrylic acid copolymer as described above. After mixing as above, mixing both solutions causes some interaction between both polymers,
It has been found that both polymers exhibit physical properties that are quite different from their respective properties they had prior to mixing.

For example, in the case of mixing a basic polymer solution and a styrene / (meth) acrylic acid copolymer solution, the following forms were recognized when roughly classified. Needless to say, these examples are general ones, and of course vary depending on, for example, the type of solvent used, the basic polymer used, and the type of styrene / (meth) acrylic acid copolymer.

(1) Although the viscosity increases temporarily, the viscosity decreases with stirring.

(2) The viscosity increased during mixing continues, and almost no decrease in viscosity due to stirring is observed.

(3) It precipitates temporarily, but disappears with stirring.

(4) Precipitates that appeared during mixing do not disappear even if stirring is continued.

[(1) and (3) or (4) and (2) and (3) or (4) may overlap. ] Even if the combination produces a precipitate in the poor liquid agent, the viscosity may increase during mixing in the good solvent,
In some combinations, the viscosity decreased with stirring. It is considered that this is because the solvent permeates into the polymer complex formed at the time of mixing, and solvation proceeds between both molecules in the bound state.

In addition, the combination in which the thickened and precipitated state is maintained is considered to be able to maintain the above state because the intermolecular binding force is stronger than the solvent affinity (provided that the basic polymer and styrene / (meth) acrylic acid are used). When a copolymer and a different solvent are prepared, the solubilities of the respective polymers in the mixed solvent system are also involved in the thickening and precipitation phenomena that occur when the two liquids are mixed).

The present inventor has found that the polymer complex formed in a solution state has properties different from a mere mixture of the respective polymers even after being dried to form a film.

Therefore, the polymer complex used in the present invention means a polymer complex composed of the above-mentioned polymers (the polymer complex composed of these polymers is disclosed in JP-B-51-37017).
It can be prepared by a method similar to that described in JP-B No. 55-42744 and JP-B No. 55-42744. ).

The present inventor further conducted various researches on the use of these polymer complexes. As a result, these polymer compoxes were water-resistant and moisture-resistant despite being remarkably hydrophilic, and the ink receptivity of the recording material for inkjet recording was high. When used to form a layer, it exhibits the same ink receptivity as conventional water-soluble polymers and gives a clear image, and its surface does not become tacky even under high humidity conditions. It has been found that the strength of the ink receiving portion of the ink receiving layer is stronger than that when a polymer is used, and the blocking phenomenon does not occur even when the films are superposed in a short time after printing.

Since the polymer complex as described above is generally insoluble in a relatively poor solvent such as water, alcohol, ester, hydrocarbon, etc., both polymers are respectively dissolved in these poor solvents and both solutions are mixed. By
The polymer complex used in the present invention can be isolated. Further, a solution of the polymer complex can be obtained by mixing in a relatively good solvent such as dimethylformamide, dimethylacetamide, dimethylsulfoxide and the like.

The basic polymer and the styrene / (meth) acrylic acid copolymer preferable for forming the polymer complex as described above have a molecular weight of 1,000 or more, preferably 2,000 or more. By using both molecular weight polymers, it is possible to form an ink receiving layer having high strength and excellent in ink receiving property, image clarity, water resistance, ink resistance and blocking resistance.

The ratio of both polymers to be used is such that the weight ratio of basic polymer / styrene / (meth) acrylic acid copolymer is from 10/1 to 10/3, and preferably the base of each polymer is used. Is the ratio at which the acidity and the acidity are approximately equal. When the weight ratio is out of the above range, the bond between the two polymers becomes insufficient, and the object of the present invention cannot be achieved sufficiently. That is, if the amount of the basic polymer is too large, the water resistance is lowered, and if the amount of the styrene / (meth) acrylic acid copolymer is too large, the ink receptivity is lowered.

Further, as described in JP-A-59-174382, in order to further improve the ink fixing property of the ink receiving layer and the tackiness of the surface of the printed part, the above-mentioned polymer complex is added with D
-The condensation product of sorbitol and benzaldehyde may be added in a proportion of 0.1 to 50% by weight of the polymer complex.

The ink receiving layer of the recording material of the present invention is formed by using the polymer complex as described above. In the present invention, in addition to the polymer complex as described above, for example, another translucent polymer is used as described above. You may use it together with a polymer complex.

Preferred as such other polymers are albumin, gelatin, casein, starch, cationic starch, gum arabic, natural resins such as sodium alginate, polyvinyl alcohol, polyamide, polyacrylamide, quaternized polyvinylpyrrolidone, polyethyleneimine, polyvinyl. Pyridylium halide, melamine resin,
Examples include synthetic resins such as polyurethane, polyester, and sodium polyacrylate, and one or more of these materials may be used in combination if desired.

Further, in order to reinforce the strength of the ink receiving layer and / or improve the adhesion to the substrate, SBR latex, NBR latex, polyvinyl formal, polymethyl methacrylate, polyvinyl butyral, polyacrylonitrile, polyvinyl chloride are added as necessary. Resins such as polyvinyl acetate, phenol resin, and alkyd resin may be used in combination.

Further, in order to enhance the ink absorbency of the ink receiving layer, various fillers in the ink receiving layer, such as silica, clay,
Fillers such as talc, diatomaceous earth, calcium carbonate, calcium sulfate, barium sulfate, aluminum silicate, synthetic zeolite, alumina, zinc oxide, lithopone and satin white can also be dispersed in the ink receiving layer.

Further, as the base material used as the support of the ink receiving layer in the present invention, any conventionally known base materials such as transparency and opacity can be used. Suitable examples of the transparent base material include polyester resins. Examples thereof include diacetate-based resin, triacetate-based resin, acrylic-based resin, polycarbonate-based resin, polyvinyl chloride-based resin, polyimide-based resin, cellophane, film or plate such as celluloid, and glass plate. Preferable examples of the opaque base material include general paper, cloth, wood, metal plate, synthetic paper and the like, as well as the above-mentioned transparent base material subjected to opacity treatment by a known means.

The recording material of the present invention is formed by using the main materials as described above, but the preferable embodiment of the above (1) is that both the base material and the ink receiving layer are translucent and the linear transmittance is 10%.
The above is the mode in which the entire recording material is translucent.

The recording material of this aspect is particularly excellent in translucency, and is an OHP for projecting a recorded image on a screen or the like by an optical device.
It is mainly used in such cases and is useful as a recording material for observation of transmitted light.

In such a translucent recording material, a translucent ink-receiving layer is formed on the translucent substrate as described above from the polymer complex as described above or a mixture with another translucent polymer. Can be prepared by

As a method for forming such an ink receiving layer, a coating solution is prepared by dissolving or dispersing the above-mentioned polymer complex alone or a mixture with other suitable polymer in a suitable solvent, For example, a known method such as a roll coating method, a rod bar coating method, a spray coating method, an air knife coating method or the like is applied on a transparent substrate and then dried quickly or a basic polymer or styrene / (meth ) A method in which one of the solutions of the acrylic acid copolymer is applied and then the other solution is applied to form a polymer complex on the substrate is preferable, and the above-mentioned polymer complex alone or with another polymer is used. A method of hot-melt coating a mixture or a single ink from the above materials. Previously formed containers layer film, the film may be in other ways such as laminated to the substrate.

The recording material of the aspect (1) formed as described above is
It is a translucent recording material having sufficient translucency.

In the present invention, sufficient translucency means that the linear transmittance of the recording material is at least 2%, preferably 10% or more.

If the linear transmittance is 2% or more, for example, it is possible to project the recorded image on the screen with OHP and observe it, and in order to observe the details of the recorded image clearly,
It is desirable that the linear transmittance is 10% or more.

The linear transmittance T (%) referred to here means that the light enters the sample at a right angle, transmits the sample, and is at least 8
The spectral transmittance of the linear light that is received by the detector after passing through the slit on the light receiving side on the extension line of the incident optical path that is distant from cm or more is measured by using, for example, 323 Hitachi self-recording spectrophotometer (manufactured by Hitachi Ltd.). The Y value of the tristimulus value of the color is obtained from the measured spectral transmittance and is the value obtained from the following equation.

T = Y / Y 2 _O × 100 (1) T; linear transmittance Y; Y value of sample Y _O ; Y value of blank Therefore, the linear transmittance referred to in the present invention is for linear light and is diffuse transmittance. (An integrating sphere is provided behind the sample to determine the transmittance including diffused light), opacity (the back of the sample is backed with white and black, and the ratio is calculated). This is different from the method of evaluating translucency using diffused light.

Since the behavior of linear light is a problem in devices that use optical technology, in evaluating the translucency of the recording material to be used in those devices, the linear transmittance of the recording material is Seeking is especially important.

For example, when observing a projected image with OHP, the contrast between the recorded portion and the non-recorded portion is high, and in order to obtain a clear and easy-to-see image, the non-recorded portion in the projected image is bright.
That is, the linear transmittance of the recording material is required to be at a certain level or higher. In the test by the OHP test chart, in order to obtain an image suitable for the above purpose, the linear transmittance of the recording material is 2% or more, and in order to obtain a clearer image, preferably 10% or more. Needed to be. Therefore, the recording material suitable for this purpose needs to have a linear transmittance of 2% or more.

The preferred embodiment of the above (2) is also one embodiment of the above (1), in which the surface of the ink receiving layer is smooth, and JIS Z87
The 45-degree specular gloss based on No. 41 is 30% or more.

The recording material of this type is particularly useful as a recording material for surface image observation, which has excellent surface gloss and full color and sharpness. The recording material in this embodiment may be transparent or opaque, and any of the above-mentioned transparent and opaque substrates can be used. Further, the ink receiving layer formed on these substrates may be transparent or opaque.
Materials and methods used for forming the ink receiving layer are described above.
As in the case of (1), the above-mentioned filler may be used to such an extent that the ink receiving layer becomes opaque as long as the surface of the ink receiving layer can maintain smoothness.

In addition to the above-mentioned coating method, a cast coating method may be used, or a gloss roll may be used for glossing, if necessary.

In the present invention as described above, the thickness of the ink receiving layer formed on the substrate is usually about 1 to 200 μm, preferably about 3 to 100 μm, and more preferably about 5 to 30 μm.

Further, in the present invention, in the recording material of the various aspects as described above, the recording surface is provided with an organic or inorganic fine powder at a rate of about 0.01 to about 1.0 g / m ^2. By doing so, it is possible to further improve the transportability of the obtained recording material in the printer, the blocking resistance during stacking, the fingerprint resistance, and the like.

Although the present invention has been described above by exemplifying typical aspects of the recording material of the present invention, the recording material of the present invention is of course not limited to these aspects. In either case, the ink receiving layer contains a dispersant, a fluorescent dye, and p.
Various known additives such as H regulators, defoamers, lubricants, preservatives and surfactants can be included.

The recording material of the present invention does not necessarily have to be colorless and may be a colored recording material.

The recording material of the present invention as described above exhibits excellent ink receptivity as in the case where the ink receptive layer is formed of a conventional water-soluble polymer, gives a recorded image with excellent sharpness, and under high humidity conditions. However, the surface does not become sticky or sticky.

Therefore, in recording a full-color image as well as a mono-color image, even when inks of different colors are overlapped and adhered to the same place within a short time, there is no phenomenon of ink flowing out or seeping out, and the strength of the ink receiving layer is A clear recorded image with high resolution can be obtained without deterioration.

Moreover, the recording material of the present invention is different from the recording material using the conventional water-soluble polymer, even when the recording as described above is performed under extremely high humidity conditions, the surface of the ink receiving layer becomes tacky or sticky. Since it does not occur at all, problems do not occur in the printer, and blocking and color transfer do not occur even when stacked.

The excellent effect under such high humidity condition is that intermolecular force (for example, electrostatic force between inks, hydrogen bond, van der Waals force, electric charge, etc.) is generated between the two polymers used for forming the ink receiving layer. (Partial movement of the polymer) and some kind of weak bond is generated to form a polymer complex, which shows excellent water resistance and blocking resistance even under high humidity conditions while maintaining high ink receptivity. .

It was totally unexpected that the above excellent effects were achieved by the water-insoluble polymer complex,
This is because the ink is a water-polyhydric alcohol mixed system, and thus the applied ink temporarily dissolves or swells the ink receiving layer of the recording material without lowering the film strength thereof, thereby receiving the ink. It is considered that the ink-accepting layer returns to the original water-insoluble polymer complex by absorption and evaporation of water after the acceleration. still,
Such a theory is merely an imagination and does not limit the present invention in any way.

In the present invention, it is possible to provide a material having an excellent surface gloss which has not been found in the conventional recording material for inkjet, and by recording the recorded image on a screen or the like with an optical device such as a slide or OHP. The present invention can be applied to applications other than conventional surface image observation, such as those used for observation, color separation plates used for making positive plates for color printing, and CMF used for color displays such as liquid crystals.

Hereinafter, the present invention will be described in more detail with reference to Examples. In the text, parts or% are based on weight unless otherwise specified.

Example 1 100 parts of a polyvinylpyrrolidone (PVPK-90, manufactured by GAF) 10% dimethylformamide (hereinafter referred to as DMF) solution and a styrene / acrylic acid copolymer (Oxylac SH2
20 parts of a 10% DMF solution (100, manufactured by Nippon Shokubai Chemical Co., Ltd.) were mixed. The mixture thickens considerably and a polymer complex is formed. This mixed solution is used as a coating solution.

A 100 μm-thick polyethylene terephthalate film (manufactured by Toray) is used as the translucent substrate, and the coating solution having the above composition is applied onto the film by a bar coater method so that the film thickness after drying becomes 8 μm. The coating was applied and dried under the conditions of 140 ° C. for 3 minutes to obtain the translucent recording material of the present invention.

The recording material of the present invention thus obtained was colorless and transparent.

Examples 2 to 4 and Comparative Examples 1 to 3 A coating liquid was prepared in the same manner as in Example 1 with the following compositions, and the same as in Example 1 was applied on the same polyethylene terephthalate film as that used in Example 1. An ink-receiving layer was provided on the above to obtain three kinds of translucent recording materials of the present invention and three kinds of comparative recording materials.

Example 2 Vinylpyrrolidone / dimethylaminoethylmethacrylate copolymer (COPOLYMER 845, manufactured by GAF) (10% ethanol / DMF solution) 100 parts Styrene / acrylic acid copolymer (Oxylac SH2100, manufactured by Nippon Shokubai Kagaku Kogyo) ( 10% DMF solution) 20 parts Example 3 Polyvinylpyrrolidone (PVPK-90, manufactured by GAF) (10% DMF solution) 100 parts Styrene / acrylic acid copolymer (Oxylac SH2200, manufactured by Nippon Shokubai Kagaku Kogyo) (10% DMF) Solution) 20 parts Example 4 Polyvinylpyrrolidone (PVPK-90, manufactured by GAF) (10% DMF solution) 100 parts Styrene / acrylic acid copolymer (Oxylac SH2210, manufactured by Nippon Shokubai Kagaku Kogyo) (10% DMF solution) 20 Part D-sorbitol / benzaldehyde condensation product (ge Luol D, manufactured by Shin Nippon Rika) (10% DMF solution) 5 parts Comparative Example 1 polyvinylpyrrolidone (PVPK-90, manufactured by GAF) 10 parts DMF 90 parts Comparative Example 2 polyvinylpyrrolidone (PVPK-90, manufactured by GAF) (10%) Aqueous solution) 50 parts Polyvinyl alcohol (PVA-217, manufactured by Kuraray) (10% aqueous solution) 50 parts Comparative Example 3 Polyvinylpyrrolidone (PVPK-90, manufactured by GAF) (10% DMF solution) 70 parts Methyl vinyl ether / monoethyl maleic anhydride Ester copolymer (GANTREZ ES-425, manufactured by GAF) (10% ethanol / DMF solution) 30 parts For the recording materials of the above Examples and Comparative Examples, the following 4
On-demand type inkjet recording head (ejection orifice diameter 60 μm, piezo oscillator drive voltage 70) for ejecting ink by a piezo oscillator using one kind of ink.
Inkjet recording was carried out using a recording device having V, frequency 2 KHz).

Yellow ink (composition) CI Direct Yellow 86 2 parts Diethylene glycol 25 parts Polyethylene glycol # 200 15 parts Water 60 parts Red ink (composition) CI Acid Red 35 2 parts Diethylene glycol 25 parts Polyethylene glycol # 200 15 parts Water 60 parts Blue ink (composition) ) CI Direct Blue 86 2 parts Diethylene glycol 25 parts Polyethylene glycol # 200 15 parts Water 60 parts Black ink (composition) CI Food Black 2 2 parts Diethylene glycol 25 parts Polyethylene glycol # 200 15 parts Water 60 parts Examples, Comparative Examples and Reference Examples Table 1 shows the evaluation results of the recording materials.

The measurement of each evaluation item in Table 1 was performed according to the following method.

(1) Ink fixing time is the time when the recording material after recording is left at room temperature (20 ° C. 65% RH) and the recorded image is touched with a finger, the ink dries and does not adhere to the finger. Was measured.

(2) For the dot density, apply JIS K7505 to printing microdots and use Sakura Microdensidometer PDM.
-5 (manufactured by Konishi Rokusha Kogyo Co., Ltd.) was used to measure black dots.

(3) OHP suitability is measured as a typical example of optical equipment, and a recorded image is projected on a screen by OHP,
It was judged by visual observation, the non-recording area was bright, and the OD (optical density) of the recorded image was high.
Good for obtaining clear and easy-to-see projected images with high contrast. ○, slightly dark non-recorded area, slightly low OD of recorded image, and lines with a pitch width of 0.5 mm and thickness of 0.25 mm that cannot be clearly identified. Δ: The non-recorded area is considerably dark, the OD of the recorded image is considerably low, and the line with a pitch width of 1 mm and the thickness of 0.3 mm cannot be clearly discriminated or the non-recorded area and the recorded image cannot be distinguished. did.

(4) For the linear transmittance, a 323 type Hitachi Autograph spectrophotometer (manufactured by Hitachi, Ltd.) was used, the distance from the sample to the light receiving side mud was kept at about 9 cm, and the spectral transmittance was measured.
It was calculated by the equation (1).

(5) Transportability cannot be recorded due to stickiness on the surface of the ink receiving layer when the recording material is mounted on the printer under the condition of 35 ° C. and 85% RH, and the transport roller of the printer cannot transport the recording material. The ones were evaluated as x, and the others were evaluated as o.

(6) Blocking was carried out after 1 hour of printing, by sticking a high-quality paper onto the printed surface and storing it for 12 hours. After the storage, those that did not cause adhesion between the recording material and the high-quality paper were rated as ◯, and those that did not stick were rated as x. Moreover, after the same test was performed 10 minutes after printing, the case where no sticking occurred was marked with ⊚.

(7) As for the film strength, after 5 minutes of printing, when the surface of the solid printed portion of the ink receiving layer was rubbed with a finger, there was no strength of the film, and the film was peeled from the beta film or the image was damaged. ×, those not so were evaluated as ○.

(8) The formation of the polymer complex was evaluated as ◯ when the solution of the basic polymer and the phenolic acidic polymer were rapidly increased or gel was formed when the solutions were mixed, and as x when they did not.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Takashi Akiya 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. (72) Inventor Shigeo Toba 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Incorporated (72) Inventor Masahiko Nikuma 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. (72) Inventor Mamoru Sakaki 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. ( 72) Inventor Ryuichi Arai 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. (56) References JP-A-58-89391 (JP, A) JP-A-56-58869 (JP, A) Special Kai-sho 58-24493 (JP, A) JP-A-61-188181 (JP, A)

Claims (1)

[Claims] 1. A recording material for inkjet having an ink receiving layer provided on a substrate, wherein the ink receiving layer contains a polymer complex of a basic polymer and a styrene / (meth) acrylic acid copolymer. A recording material for inkjet characterized by: