JPS62146674A - Material to be recorded - Google Patents

Abstract

PURPOSE:To provide a material to be recorded for ink jet recording excellent in ink receptivity, water resistance, the sharpness of a recorded image and light fastness, by a method wherein an ink receiving layer is constituted of two layers, that is, an upper layer containing cation modified polyvinyl alcohol and a lower layer comprising a polymer complex of a basic polymer and an acidic polymer. CONSTITUTION:A material to be recorded has an ink receiving layer consisting of a lower layer comprising a polymer complex of a basic polymer and an acidic polymer and an upper layer containing cation modified PVA. Both of a base material and the ink receiving layer have light perviousness showing linear transmissivity of 10% or more and the light pervious material to be recorded having light perviousness as the whole of the material to be recorded is prepared by a method wherein the lower layer of the light pervious ink receiving layer is formed on the base material from the polymer complex alone or a mixture of said complex and other light pervious polymer and the upper layer of cation modified PVA is formed thereon.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a recording material suitably used in an inkjet recording method, and in particular a recording material that has excellent ink receptivity, sharpness of recorded images, water resistance, and light resistance. Regarding recording materials.

(Prior Art) Inkjet recording methods include various ink (recording liquid) ejection methods, such as an electrostatic suction method.

A method that uses a piezoelectric element to apply mechanical vibration or displacement to the ink, a method that heats the ink to foam, and uses the resulting pressure to generate and fly ink droplets, and some or all of them are transferred to the paper. This recording method is attracting attention as a recording method that generates little noise and can perform high-speed printing and multicolor printing.

As ink for inkjet recording, there are safety and
In terms of # properties, those containing water as a main component are used, and polyhydric alcohols and the like are often added to prevent nozzle clogging and improve ejection stability.

The recording material used in this inkjet recording method has conventionally been a recording material consisting of a base material called ordinary paper or inkjet recording paper on which a porous ink receiving layer is provided.

However, as the performance of inkjet recording apparatuses increases and becomes more widespread, such as higher recording speeds and multicolor recording, more sophisticated and wide-ranging properties are being required of recording materials.

In other words, the recording material for inkjet recording to obtain high-resolution, high-quality recorded images must (1) be able to receive ink as quickly as possible on the recording material, and (2) have overlapping ink dots. (3) Ink droplets do not spread on the recording material and the diameter of the ink dot does not become larger than necessary, (4) ) The shape of the ink dot should be close to a perfect circle, and the circumference should be smooth.

(5) The OD (optical density) of the ink dot is high and the periphery of the dot is not blurred.

It is necessary to satisfy basic requirements such as:

Furthermore, in order to obtain high-resolution recorded image quality comparable to color photography using a multicolor inkjet recording method, in addition to the above-mentioned required performance, (6) the coloring components of the ink must have excellent color development; 7) The ink fixability is particularly excellent since the same number of droplets as the number of ink colors may adhere to the same location in an overlapping manner.

(8) The surface must be glossy, □ (9) High whiteness; etc. are required in a weighted manner.

In addition, images recorded by the inkjet recording method have traditionally been used exclusively for surface image observation, but as the performance of inkjet recording devices has improved and become more widespread, recording materials suitable for purposes other than surface image observation have become available. is becoming required.

Applications of recording materials other than surface image observation include those used to project recorded images onto a screen etc. using optical equipment such as slides and OHP (overhead projectors) for observation, and color printing. Examples include color separation plates used to create positive plates, and CMF (color mosaic filters) used in color displays such as liquid crystals.

When a recording material is used for surface image observation, the diffused light of the recorded image is mainly observed, whereas for recording materials used in these applications, the problem is mainly the transmitted light of the recorded image. Become. Therefore, it is required to have excellent light transmittance, particularly in linear light transmitting flux, in addition to the above-mentioned performance requirements of the recording material for general ink jet recording.

(The problem that the invention is trying to solve) However,
The reality is that there is still no known recording material that meets all of these required performances.

In addition, many conventional recording materials for surface image observation use a method in which a porous ink-receiving layer is provided on the surface, and the ink is received in the porous voids to fix the recording material. The surface of the recording material was not glossy due to the nature of the recording material.

On the other hand, when the surface of the ink-receiving layer is non-porous, non-volatile components such as polyhydric alcohols in the ink remain on the surface of the recording material for a long time after recording.

Since the drying and fixing time of the ink is long, there is a drawback that when the ink comes into contact with the recorded image, clothes are stained and the recorded image is damaged.

In addition, in the case of recording materials that use water-soluble polymers to form the ink-receiving layer in order to improve affinity with ink and ink receptivity, the surface of this ink-receiving layer becomes sticky under high humidity conditions. Therefore, when it is installed in a printer, it adheres to the printer's feed roller, etc., and there is a problem that the recording material cannot be conveyed, and the recording material may block when stacked. Furthermore, there is also the problem that the dye on the recording material changes color and fades when exposed to OHP light or room light.

Therefore, an object of the present invention is to provide a recording material for inkjet recording which is particularly excellent in ink receptivity, water resistance, and clarity of recorded images, and furthermore has excellent light resistance.

Another object of the present invention is to provide a recording material for full-color inkjet recording that has excellent ink receptivity, recorded image brightness, and surface gloss, and does not cause surface stickiness or blocking even under high humidity conditions. There is a particular thing.

Another purpose that has not yet been invented is to use optical devices such as slides and OHPs to project recorded images onto screens for observation, color separation plates for creating positive plates for color printing, or color separation plates for liquid crystals, etc. C used for displays
An object of the present invention is to provide a recording material for inkjet recording that can be used for observation of transmitted light such as MF.

These and other objects of the invention are achieved by the invention as follows.

(Disclosure of the Invention) That is, the present invention provides an inkjet recording material comprising a base material and an ink-receiving layer, in which the ink-receiving layer is composed of two layers, and the upper layer is made of cation-modified polyvinyl alcohol (hereinafter referred to as cation-PVA). This is an inkjet recording material characterized in that the lower layer is made of a polybu complex of a basic polymer and an acidic polymer.

To explain the present invention in detail, in the recording material of the Wood invention, the lower layer of the ink-receiving layer is made of a polymer complex of a basic polymer and an acidic polymer, and the upper layer is a layer containing Kachin PVA. This is the main feature and is primarily by which the objects of the invention are achieved.

The recording material of the present invention generally consists of a base material as a support and a recording surface provided on the surface of the base material, that is, an ink receiving layer. For example, as a particularly preferred embodiment, (1) the base material and the ink receiving layer. Examples include (2) an embodiment in which all of the recording materials are translucent and the recording material as a whole is translucent, and (2) an embodiment in which the surface of the ink-receiving layer is smooth and glossy.

Further, each ink receiving layer may also function as a support at the same time.

The present invention will be explained in more detail using the following preferred embodiments as representative examples.

The polymer complex that characterizes the present invention is composed of a basic polymer and an acidic polymer, and is described, for example, in Japanese Patent Publication No. 51-37017 and Japanese Patent Publication No. 55-4.
It is already known as such from the publication No. 2744.

In the present invention, preferred basic polymers include, for example, the following.

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, block copolymers, graft copolymers, etc. with other common monomers: N-vinyl-2-oxazolidone, N-vinyl-5-methyl-2 -Oxazolidone, N-vinyl-5-methyl-
2-Oxazolidone.

N-vinyl-5-ethyl-2-oxasilidone, N-vinyl-4-methyl-2-oxazolidone, N-vinyl-
Homopolymers such as 2-thousand oxazolidone and N-vinyl-2-mercaptobenzothiazole, or random copolymers, block copolymers, graft copolymers, etc. with other common heptamers; N-vinyl Homopolymers of imidazole, N-vinyl-2-methylimidazole, N-vinyl-4-methylimidazole, etc., or random copolymers with other common monomers, block copolymers, graft copolymers, etc. Homopolymers such as 2- or 4-vinylpyridine or lantam copolymers with other common monomers, block copolymers, graft copolymers, etc.; Copolymerizable monomers include methacrylate, acrylate, acrylamide, acrylonitrile, vinyl ether, vinyl acetate, vinyl imidazole,
Ethylene, styrene, and other common monomers that are particularly useful in the present invention include N-vinylpyrrolidone, N-vinylpiperidone, N-vinylcaprolactam, N-vinylmorpholine, N-vinyl-2-oxacylidone, These include homopolymers and copolymers of N-vinyl-5-methyl-2-oxacylidone. In the case of a copolymer, it is preferable that the above-mentioned nitrogen-containing polymer is included in an amount of 50 mol % or more.

In addition, an acidic polymer that can form a polymer complex with the above basic polymer (in the present invention, the term "acidic polymer" refers to a sulfonic acid group, a carboxylic acid group, a sulfuric acid ester group, a phosphoric acid ester group, or a phenolic acid group in its molecule). In addition to those having a hydroxyl group, the examples also include those having an alcoholic hydroxyl group.) include, for example, the following.

1. Polymer with carboxylic acid group Terminal carboxyl obtained by reacting a polyhydric carboxylic acid such as citric acid, tartaric acid, phthalic acid, etc. with a polyhydric alcohol such as ethylene glycol, 1.4-butanediol, diethylene glycol in excess of acid. Base polyester: Acidic cellulose derivative modified with various polyhydric carboxylic acids (
Homopolymers such as vinyl ether ester monomers of polyhydric carboxylic acids, random copolymers, block copolymers, graft copolymers, etc. with other common monomers (see Japanese Patent Publication No. 35-5093); Kosho 35-849
Homopolymers of monomers such as acrylic acid or methacrylic acid or random copolymers with other common monomers,
Block copolymers, graft copolymers, etc. Homopolymers of α, β-unsaturated vinyl monomers such as maleic anhydride and itaconic acid, or random copolymers and block copolymers with other common heptamers Polymers, graft copolymers, etc. (citrus, red, reorganized, synthetic polymers (m) P, 25
0-257 and P, 374-380, Asakura Shoten (19
71)); 2 Polymers with sulfonic acid groups 0-Ethylcellulose hydrogen acetate hydrogen sulfate phthalate, cellulose hydrogen acetate hydrogen sulfate phthalate, ethylcellulose hydrogen-O-sulfobenzoate, 0-P-sulfonebenzylcellulose acetate ,0-ethyl-
〇-Cellulose derivatives such as P-sulfoethyl cellulose acetate (see Japanese Patent Publication No. 35-5093)
; Sulfonic acid-modified polymers of polyvinyl alcohol or vinyl alcohol copolymers with sulfonic acid compounds (e.g., 0-sulfobenzoic acid, sulfopropionic acid, sulfoparelic acid, sulfobenzaldehyde, sulfophthalic acid, etc.); 3. Polymers with hydroxylation Ethyl cellulose, benzyl cellulose.

Hydroxyethylcellulose, hydroxyethyl/ethylcellulose, hydroxyethyl/benzylcellulose, etc. Other heptad homopolymers containing sulfonic acid or phenol groups, or random copolymers and block copolymers with other common monomers.

Graft copolymers, etc.; Acidic modified products of various polymers with other carboxyl group-, sulfonic acid-, or phenol-containing compounds; Any of the above acidic polymers can be used, but particularly preferred in the present invention are: These include homopolymers, random copolymers, block copolymers, and graft copolymers of α,β-unsaturated acids, and particularly preferred are copolymers of alkyl vinyl ether and maleic anhydride.

The present inventor has been conducting various research on mixtures of ffi-based polymers and acidic polymers as described above, and found that by mixing these polymers in a solution, both polymers interact with each other in some way. If both polymers are mixed in a relatively good solvent, the polymer complex will precipitate, and if mixed in a relatively good solvent, a significant increase in viscosity will occur. It has been found that the polymer has different properties than the simple mixture of both polymers used.

Therefore, the polymer complex used in the present invention means a polymer complex made of the above-mentioned polymers (details of basic polymers, acidic polymers, and polymer complexes made of these polymers can be found in Japanese Patent Publication No. 51-37017). (Please refer to Japanese Patent Publication No. 55-42744).

The present inventor further conducted various studies on the uses of these polymer complexes, and found that although these polymer complexes are extremely hydrophilic, they do not have water resistance,
It has a 1g resistance, and when used to form an ink-receiving layer of an inkjet recording material, it showed ink-receptivity equivalent to that of conventional water-soluble polymers and gave clear images.
It was discovered that the surface did not become sticky even under high humidity conditions.

As mentioned above, polymer complexes generally contain water,
Since both polymers are not soluble in relatively poor solvents such as alcohols, esters, hydrocarbons, etc., the polymer complex used in the present invention can be prepared by dissolving both polymers in these poor solvents and mixing the two solutions. Can be isolated. Further, a solution of the polymer complex can be obtained by mixing in a relatively good solvent such as dimethylformamide, dimethylacetamide, dimethyl sulfoxide, etc. with a thickness of 1 μm.

Preferred basic polymers and acidic polymers for forming the above polymer complexes each have a molecular weight of 500 or more, preferably 1,000 or more, and - is used for both polys with these molecular weights. Accordingly, it is possible to form an ink-receiving layer that has high strength, excellent brightness of an ink-receptive image, and excellent water resistance.

Furthermore, the ratio of both polymers used is in a range such that the basic polymer/S polymer is 20/1 to 1/10 at a weight ratio of 1, and preferably, the basicity and acidity of each polymer are approximately equal. It is a percentage. If the weight ratio deviates from the above range, the bond between both polymers will be insufficient and the object of the present invention will not be fully achieved. That is, if the basic polymer is too large, the water resistance will be reduced, and if the acidic polymer is too large, the ink receptivity will be reduced.

Furthermore, the cationically modified PVA that characterizes the present invention refers to PVA having primary to tertiary amino groups, quaternary ammonium bases, etc. in the main chain or side chain.

Generally, PVA is obtained by saponifying polyvinyl acetate by an acid saponification method or an alkali saponification method, but PVA is used in the present invention and mainly characterizes the present invention.
The cationically modified products of VA are vinyloxyethyltrimethylammonium chloride, 2,3-dimethyl-1-vinylimidazolinium chloride, trimethyl-(3-acrylamide-3,3- dimethylpropyl) ammonium chloride, trimethyl-(3-methacrylamidopropyl) ammonium chloride, N-(1,1-dimethyl-3-dimethylaminopropyl) acrylamide, N-(3
-dimethylaminopropyl) methacrylamide, trimethyl (3-acrylamidopropyl) ammonium chloride, l-vinyl-2-methyl (or ethylphenyl) imidazole.

Quaternary ammonium salts (or their precursor groups,
(i.e., vinyl heptamers containing primary to tertiary amino groups)
or 0-1m-1p-aminostyrene, monoalkyl or dialkyl derivatives thereof, or quaternary cationic groups thereof in the main chain or side chain.

Generally, PVA is obtained by saponifying polyvinyl acetate by an acid saponification method or an alkali saponification method, but PVA is used in the present invention and mainly characterizes the present invention.
The cationic modified product of VA is used when polymerizing polyvinyl acetate as a raw material.

Vinyloxyethyltrimethylammonium chloride, 2,3-dimethyl-1-vinylimidazolinium chloride, trimethyl-(3-acrylamide-3,3-
4, such as dimethylpropyl)ammonium chloride, trimethyl-(3-methacrylamidopropyl)ammonium chloride, N-(1,1-dimethyl-3-dimethylaminopropyl)acrylamide, N-(3-dimethylaminepropylmethacrylamide, etc.) or o-, m-, p-aminostyrene or these seven aminostyrenes. Noalkyl, dialkyl derivatives or quaternary ammonium salts thereof; 0-1m-1p-vinylbenzylamine or monoalkyl or dialkyl derivatives thereof or quaternary ammonium salts thereof; N-
(vinibenzyl)hyrolidine, N-(vinylbenzyl)
Piperidine; N-vinylpyrrolidone; α-1β-vinylpyridine or quaternary ammonium salts thereof; α-1
Other nitrogen-containing heterocyclic vinyl compounds such as β-piperidine or their quaternary ammonium salts; 2-14-vinylquinoline or their quaternary ammonium salts, or their nitro derivatives, which can easily be converted into cationic groups. It can be obtained by copolymerizing a variable vinyl compound monomer with vinyl acetate and saponifying the resulting copolymer by a conventional method. In addition, vinyl acetate and a hexamer having other reactive groups are copolymerized, and after saponification, such reactive groups are used to react with a cationic group-containing compound to cationically modify PVA. It's okay. Furthermore, by utilizing the hydroxyl group in PVA, a group capable of reacting with the hydroxyl group and 1 to
PVA may be directly cationized using a compound that simultaneously has a tertiary amine group or a quaternary ammonium group, such as glycidyltrimethylammonium chloride.

The amount of cationic groups present in such a cationically modified PVA is expressed as a molar fraction of one monomer unit in the polymer.
The amount ranges from 20 mol%, more preferably from 0.1 to 10 mol%. If the amount of the cationic modified group is less than 0.0-5 mol%, the inkjet recording properties such as water resistance, resolution, and color development of the ink-receiving layer will not be sufficiently effective compared to unmodified ones; If it exceeds 20 mol%, it is not preferable because the adhesion of the ink-receiving layer to the base material and film-forming properties become poor.

The degree of saponification of PVA, which is the backbone polymer, should be selected depending on the intended use of the recording material, but generally when it is used as a binder for fillers, etc., which will be described later, added to the ink-receiving layer, the degree of saponification is 85 mol. % or more, or about 80 to 93 mol % when used as the main material of the ink-receiving layer. Further, the degree of polymerization of the cationically modified PVA is preferably 500 to 5,000, and 800 to 5,000.
3.000 is more suitable. Furthermore, in any case, materials having different degrees of polymerization and saponification may be mixed and used.

The ink receiving layer of the recording material of the present invention is formed using one or more of the above polymer complexes and cationic PVA. In the present invention, in addition to the above-mentioned polymer complexes and cationic PVA, for example, other Transparent polymers may be used in combination with the polymer complexes described above and cationic P/A.

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

Furthermore, in order to reinforce the strength of the ink-receiving layer and/or improve the adhesion with the base material, SBR latex, NBR latex, polyvinyl formal, polymethyl methacrylate, polyvinyl butyral, polyacrylonitrile, polyvinyl chloride may be added as necessary. , polyvinyl acetate, phenol resin, altkyd resin, etc. may be used in combination.

In addition, in order to improve the ink absorbency of the ink receiving layer, various fillers such as silica, clay, etc. are added to the ink receiving layer.
Tartar, diatomaceous earth, calcium carbonate, calcium sulfate, barium sulfate.

Fillers such as aluminum silicate, synthetic zeolite, alumina, zinc oxide, lithopone, and satin white can also be dispersed in the ink-receiving layer.

In addition, as the base material used as the support for the ink receiving layer in the present invention, any conventionally known base material such as transparent or opaque can be used, and suitable examples of the transparent base material include, for example, polyester resin. , diacetate resins, triacetate resins, acrylic resins, polycarbonate resins, polyvinyl chloride resins, polyimide resins, films or plates of cellophane, celluloid, and glass plates. Preferred opaque substrates include 1, for example, general paper, cloth, wood, metal plates, synthetic paper, etc., as well as the above-mentioned transparent substrates treated to make them opaque by known means. .

The recording material of the present invention is formed using the above-mentioned main materials, and in the preferred embodiment (1) above, both the base material and the ink receiving layer are translucent, and the in-line transmittance is 10.
% or more.

This is an embodiment in which the recording material as a whole is translucent.

The recording material of this embodiment is particularly excellent in translucency, and is used in OHP applications in which recorded images are projected onto a screen or the like using an optical device.
It is mainly used in cases such as the following, and is useful as a recording material for transmitted light observation.

In such a light-transmitting recording material, a lower layer of a light-transmitting ink-receiving layer is formed on a light-transmitting base material as described above, using the above-mentioned polymer complex alone or in a mixture with other light-transmitting polymers. and cation-modified PV as the upper layer.
It can be prepared by forming a layer of A.

The method for forming such an ink-receiving layer is to first prepare a coating solution by dissolving or dispersing the above-mentioned polymer complex alone or a mixture with other suitable polymers in a suitable solvent as the lower layer. A method in which a coating solution is coated on a transparent substrate by a known method such as a roll coating method, a rod bar coating method, a spray coach ink method, an air knife coating method, etc., and then quickly dried, or a basic polymer or A preferred method is to apply one of the acidic polymer solutions and then apply the other solution to form a Motomurakami Tevolimer complex.Alternatively, the above polymer complex alone or in a mixture with other polymers is hot coated. Alternatively, other methods may be used, such as forming a single ink-receiving layer film from the above-mentioned materials and then laminating the film to the above-mentioned substrate.

Furthermore, a two-layer ink-receiving layer is formed by forming layers using the above-described method using cation-modified PVA as an upper layer.

The recording material of the embodiment (1) formed as described above is a light-transmitting recording material having sufficient light-transmitting properties.

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

If the in-line transmittance is 2% or more, it is 1. For example, in order to project a recorded image onto a screen using an OHP and observe it clearly, the in-line transmittance is preferably 10% or more.

The linear transmittance T (%) here refers to the incident perpendicular to the sample, transmitted through the sample, and at least 8
An example is the spectral transmittance of straight light that passes through the light-receiving side slit on the extension line of the incident optical path that is separated by more than cm and is received by the detector.Using a Hitachi type 323 self-recording spectrophotometer (newly manufactured by Hitachi), etc. Then, from the measured spectral transmittance, the Y value of the tristimulus value of the color is determined, and the value is determined by the following formula.

T=Y/Y, x l 00 (1)T;
Linear transmittance Y: Y value of sample Y; Y value of blank Therefore, the linear transmittance referred to in the present invention is for straight light, and the diffuse transmittance (an integrating sphere is installed behind the sample to capture diffused light) ) and opacity (
on the back of the sample.

Calculate the white and black backings and calculate their ratio. )
This is different from the method of evaluating translucency using diffused light.

Since the problem with devices that use optical technology is the behavior of straight-line light, in step 7, when evaluating the translucency of the recording material to be used in these devices, we evaluate the straight-line transmittance of the recording material. Asking is especially important.

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

The preferred embodiment of (2) above is also one of the embodiments of (1) above, in which the surface of the ink receiving layer is smooth and JISZ
It is characterized by a 45 degree specular gloss based on 8741 of 30% or more.

This type of recording material has particularly excellent surface gloss, and is particularly useful as a recording material for observing surface images in full color and excellent clarity. The recording material in this embodiment may be transparent or opaque, and both the transparent and opaque base materials described above can be used. The ink receiving layer formed on these Omuras may also be transparent or opaque.
The materials and methods used to form the ink-receiving layer are the same as those in embodiment (1) above, but the filler, etc., can be used to make the ink-receiving layer opaque as long as the surface of the ink-receiving layer can maintain smoothness. You may use it to the extent that it suits you.

If necessary, a cast coating method may be used in addition to the above-mentioned coating method, or glossing may be performed using a gloss roll.

In the present invention as described above, the total thickness of the two ink receiving layers formed on Omura is usually about 1 to 2004 m, preferably about 3 to 100 gm, more preferably 5 to 100 gm.
At about 30pm.

Ru.

Furthermore, the thickness of the upper layer of cationically modified PVA is usually 0.
The thickness is 3 to 15 μLm, preferably 0.5 to 10 gm, and more preferably 1 to 7 gm. If it is thinner than 0.3 JLm, the light resistance will not be sufficient, and if it is thicker than 15 μm, the water resistance will decrease.

Furthermore, in the present invention, fine organic or inorganic powder is applied to the recording surface of the recording materials of various embodiments as described above at a rate of about 0.01 to about 1.0 g/rn'. By doing so, it is possible to further improve the transportability in the printer, the blocking resistance during stacking, the fingerprint resistance, etc. of the obtained recording material.

The present invention has been explained above by illustrating typical aspects of the recording material of the present invention, but of course the recording material of the present invention is not limited to these aspects. Also, the ink-receiving layer contains a dispersant, fluorescent dye, P
This can be achieved by including various known additives such as H regulators, antifoaming agents, lubricants, preservatives, and surfactants.

Note that 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 similar to those in which the ink receptive layer is formed from a conventional water-soluble polymer, provides a recorded image with clear clarity, and also under high humidity conditions. However, the surface does not become sticky or sticky.

Therefore, when recording monochrome as well as full-color images, even if ink of different colors adheres to the same location within a short period of time, there will be no ink flow or seepage phenomenon, and high-resolution, clear images will be recorded. A recorded image is obtained.

Moreover, unlike recording materials using conventional water-soluble polymers, the recording material of the present invention does not cause the surface of the ink-receiving layer to become sticky or sticky even when the above-mentioned recording is performed under extremely high humidity conditions. Since this does not occur at all, there is no problem in the printer, and even when stacked, there is no blocking or color transfer.

The excellent effect under such high humidity conditions is due to the fact that the two types of polymers used to form the ink-receiving layer have strong bonds between their molecules, such as interionic electrostatic force, hydrogen bonding, van der's bond, etc.
It is thought that some weak bonds occur due to Waalska, partial transfer of charges, etc., forming a polymer complex, which exhibits excellent water resistance even under high humidity conditions while maintaining high ink receptivity.

It was completely unexpected that such excellent effects as described above could be achieved by a water-insoluble polymer complex.
This is because the ink is a mixture of water and polyhydric alcohol, so the applied ink temporarily dissolves or swells the ink-receiving layer of the recording material to facilitate ink reception. This is thought to be because the ink-receiving layer returns to its original water-impossible polymer complex by absorption and evaporation of the ink. It should be noted that such a theory is just imagination and does not limit the present invention in any way.

Furthermore, surprisingly, the present inventors added a layer of 0.3 to 20 g of cationically modified PVA on the upper layer of the polymer complex.
It has been found that by forming a film with a thickness of 1.5 mm, light resistance can be significantly improved without impairing water resistance.

With the present invention, it is possible to provide an excellent surface gloss that has not been seen with conventional inkjet recording materials, and it is also possible to provide recorded images by projecting them onto a screen or the like using an optical device such as a slide or OHP. It can be applied to applications other than conventional surface image observation, such as those used for observation, color separation plates when creating a positive plate for color printing, or CMF used for color displays such as liquid crystals.

Hereinafter, the present invention will be explained in more detail according to Examples. Note that parts in the text are based on weight.

Example 1 Polyvinylpyrrolidone 10% aqueous solution (pv pK-90
, manufactured by GAF) and 66 parts of methyl vinyl ether/maleic anhydride copolymer (GANTREZ AN-169, G
34 parts of a 10% aqueous solution (manufactured by AF) were mixed. The mixed solution gels to form a polymer complex, and 100 parts of N,N-dimethylformamide is added to this mixed solution.
When heated to 90°C, it becomes a solution, which is used as the coating liquid for the lower layer.

A polyethylene terephthalate film (Toshi V) with a thickness of 1100 AL was used as a translucent base material, and the lower layer coating liquid of the above composition was applied onto this film so that the film thickness after drying was 81 parts m. −, coated by coater method, 80°
After drying at C for 10 minutes, cation-modified PVA (
An upper layer coating solution consisting of 10 parts of PVA-C-318 (manufactured by Kuraray) and 90 parts of water was applied using a bar coater method so that the upper layer thickness after drying was 3 mm.

It was dried at 80° C. for 10 minutes to obtain a translucent recording material of the present invention.

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

Examples 2 to 5 and Comparative Examples 1 to 3 Coating solutions were prepared in the same manner as in Example 1 using the following compositions, and coated on the same polyethylene terephthalate film as in Example 1. An ink-receiving layer was provided to obtain four types of translucent recording materials of the present invention and seven types of recording materials for comparison.

The thickness of each upper layer (cationic PVA) is as follows.

Polyvinyl alcohol (PVA-217, manufactured by Kuraray) 10 parts*
qO Rahi JlヱPolyvinylpyrrolidone water
90 parts polyvinylpyrrolidone (PVPK-90, manufactured by GAF)
10% aqueous solution> 50 parts Polyvinyl alcohol (PVA-220, manufactured by Kuraray) 50 parts Le Jro 1
A: Only the lower layer of Example 1, no upper layer Arashi-Ko-o" Only the lower layer of Example 2, no upper layer The thickness of the upper layer of Example 4 is 20 g. For the recording materials of the above examples and comparative examples, the following 4
On-demand inkjet recording head that uses seed ink to eject ink using a piezo vibrator (discharge orifice diameter 60 pm, piezo vibrator drive voltage 70 V)
, frequency 2 KHz).

1ヱ Top l (composition) C, 1, Direct Yellow 86 2 parts diethylene glycol 20 parts polyethylene glycol #200 10 parts water
70 copies LLL! (Composition) C, 1, Acid Red 35 2 parts diethylene glycol 20 parts polyethylene glycol #200 10 parts water
7 o part LLLi (composition) C, 1, Direct Blue 86 2 parts diethylene glycol 20 parts polyethylene glycol #200 10 parts water
70 parts LLLi (composition) C, 1, Food Black 2 2 parts diethylene glycol 20 parts polyethylene glycol #200' 10 parts water
70 copies The evaluation results of the recording materials of the Examples and Comparative Examples are shown in Table 1.

Each evaluation item in Table 1 was measured according to the following method.

(1) The ink fixation time is calculated by leaving the recording material after recording at room temperature (20°C, 65% R) and touching the recorded image with your finger.The ink dries and sticks to your finger. The time it took to disappear was measured.

(2) Dot density was measured for black dots using Sakura Microdensidometer PDM-5 (manufactured by Konishiroku Photo Industry Co., Ltd.) by applying JIS K2SO3 to printed microdots.

(3) OHP suitability was measured as a representative example of optical equipment, and the recorded image was projected onto a screen using OHP.
Judgment is made by visual observation. 0 indicates that the non-recorded area is bright, the OD (optical density) of the recorded image is high, and a clear and easy-to-see projected image with high contrast is obtained, while the non-recorded area is slightly dark and the recorded image is 0. If the OD of the image is very low and lines with a pitch width of 0.5 mm and a thickness of 0.25 mm cannot be clearly distinguished, Δ is used, the non-recorded area is quite dark, the OD of the recorded image is quite low, and the pitch is A line with a width of 1 mm and a thickness of 0.3 mm could not be clearly distinguished, or it was difficult to distinguish between a non-recorded area and a recorded image, which was rated as "×".

(4) Linear transmittance was measured using a 323-type Hitachi self-recording spectrophotometer (manufactured by Hitachi, Ltd.), keeping the distance from the sample to the light-receiving side at approximately 9 cm, and measuring the spectral transmittance.
It was determined using the above formula (1).

(5) Transportability: When the recording material is loaded into the printer under conditions of 35°C and 85% RH, it cannot be transported by the printer's feed roller due to the stickiness of the surface of the ink receiving layer.
Those that could not be recorded were marked as ×, and those that were not recorded were marked as O.

(6) For blocking, after 12 hours of printing, high-quality paper was brought into close contact with the printed surface and stored for 12 hours.

After storage, those in which no adhesion occurred between the recording material and the high-quality paper were designated as O, and those in which no adhesion occurred were designated as X.

(7) Regarding the formation of a polymer complex, when the basic polymer and acidic polymer solutions were mixed, cases where there was a sudden increase in viscosity or formation of gel were marked as O, and cases where no gel was formed were marked as ×.

(8) #Lightness is fade meter (black panel 6
3°C x 65% R) I) After 30 hours of irradiation, ΔE of the black solid printed area was measured.

Work and noodles U village rules 7 minutes 4 minutes 2 minutes 8 minutes 2 minutes and E-L (Watari 21210! and o o oo ○ Ranji” L going! 73% 78% 76% 77% 7
To 3%-” L-5 oooo ○ Blocking oooo.

Polymer kelp ward Mugen Soyeon 000 0 0 One wrinkle [-sha 22323 Comparative example M21 retroactive sentence 3 minutes 5 minutes 1 minute 10 minutes 5 minutes 6 minutes 9
Minute■! Two melons 1.1 1.1 1.1 1.1 1
．． 1 1.1 1.1B o o o o
o o.

L1 co[1] 82% 80% 801 74%
79% 78%? 8%! LJ, -sex x x
xooox blocking Q x x OOO,
X-polymer kelp has a lot to do with it --xooo.

Claims (1)

[Claims] In an inkjet recording material comprising an ink-receiving layer provided on a base material, the ink-receiving layer is composed of two layers, the upper layer is a layer containing cation-modified polyvinyl alcohol, and the lower layer is a layer containing a basic polymer and an acidic polyvinyl alcohol. An inkjet recording material comprising a polymer complex with a polymer.