JPS62160274A - Material to be recorded - Google Patents

Abstract

PURPOSE:To provide a material to be recorded for full-color ink jet recording excellent in ink receptivity, imparting a recording image excellent in sharpness and surface gloss and generating no surface stickiness or blocking even under a high humidity condition, by containing a polymer complex consisting of a basic polymer and an epoxy resin in an ink receiving layer. CONSTITUTION:As a polymer forming a polymer complex along with a basic polymer, an epoxy resin is selected to obtain a material to be recorded showing excellent ink receptivity and imparting a recording image excellent in sharpness and water resistance even under short-time heating. As the pref. basic polymer, there are a homopolymer and a copolymer etc. of N-vinyl pyrrolidone, N-vinyl piperidone, N-vinyl caprolactam, N-vinyl morpholine, N-vinyl-2-oxazolidone and N-vinyl-5-methyl-2-oxazolidone.

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, particularly in terms of ink receptivity, clarity of recorded images, water resistance, blocking resistance, etc. Regarding excellent recording materials.

(Prior Art) Inkjet recording methods include various ink (recording liquid) ejection methods, such as an electrostatic suction method, a method that applies mechanical vibration or displacement to the ink using a piezoelectric element, and a method that heats the ink to foam it. This method utilizes the pressure to generate and fly ink droplets, and some or all of them adhere to a recording material such as paper to perform recording, but it generates little noise and It is attracting attention as a recording method that allows high-speed printing and multicolor printing.

Ink for inkjet recording is mainly composed of water for safety and recording characteristics, and polyhydric alcohols are added to prevent nozzle clogging and improve ejection stability. In many cases.

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 faster recording speeds and multicolor recording, more advanced 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 its circumference should be smooth; (5) The OD (optical density) of the ink dot should be high and the periphery of the dot should not be blurred. There is.

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 fixation properties are particularly excellent, as the same number of droplets as the number of ink colors may adhere to the same spot, (8) The surface must be glossy, (9) Whiteness A high level of performance, etc., is required.

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

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 for creating positive plates, CMF C color mosaic filters used for color displays such as liquid crystals, etc.

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, especially linear light transmittance, in addition to the above-mentioned performance requirements of the general recording material for inkjet recording.

(The problem that the invention is trying to solve) However,
The reality is that there is still no known recording material that satisfies 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, and the drying and fixing time of the ink is long. There are disadvantages in that clothing may get dirty or the recorded image may be damaged if it comes into contact with the recorded image.

In addition, in recording materials that use water-soluble polymers for the ink-receiving layer in order to improve ink affinity and ink receptivity, the surface of this ink-receiving layer' becomes sticky under high humidity conditions. Therefore, there is a problem that when the recording material is attached to the printer, it adheres to the printer's feed roller, etc., making it impossible to convey the recording material, and that the recording material may block when stacked.

Therefore, the object of the present invention is particularly ink receptivity.

An object of the present invention is to provide a recording material for inkjet recording that has excellent water resistance and clarity of recorded images.

Another object of the present invention is to provide excellent ink receptivity, sharpness of recorded images, and surface gloss even under high humidity conditions.

An object of the present invention is to provide a recording material for full-color inkjet recording that does not cause surface stickiness, blocking, etc.

Another object of the present invention is to use an optical device such as a slide or OHP to project a recorded image onto a screen for observation, a color separation plate for creating a positive plate for color printing, or a color separation plate for liquid crystal display. C used for display
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.

(Disclosure of the Invention) That is, the present invention provides an inkjet recording material in which an ink-receiving layer is provided on a base material, wherein the ink-receiving layer contains a basic polymer and an epoxy resin. It is a recording material for use.

To explain the present invention in detail, the recording material of the present invention is mainly characterized in that its ink receiving layer is composed of a basic polymer and an epoxy resin, and the object of the present invention is mainly achieved thereby. It is.

The recording material of the present invention generally consists of a base material as a support and a recording surface provided on the surface thereof, that is, an ink-receiving layer.1 For example, as a particularly preferred embodiment, (1) 2Ji material and an 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 above preferred embodiments as representative examples.

The mixture forming the ink-receiving layer, which mainly characterizes the present invention, is composed of a basic polymer and an epoxy resin. It is thought that these mixtures produce some kind of complex different from the original components due to intermolecular forces acting between them (hereinafter referred to as polymer complex).

Conventionally, polymer complexes consisting of a basic polymer and an acidic polymer are known, for example, in Japanese Patent Publication No. 37017/1982 and Japanese Patent Publication No. 42744/1989.

The present inventor has discovered that the above polymer complex is soluble in good solvents such as dimethylformamide and dimethyl sulfoxide, is useful for forming an ink receiving layer of recording materials, and has various properties such as ink fixability and water resistance. It was discovered that an excellent recording material could be obtained (patent application 1986-2600).
(See specification No. 0).

A liquid absorption medium consisting of a combination of a water-soluble polymer such as polyvinyl alcohol and a reaction product of an epoxidized water-insoluble neutral rubbery polymer and a water-soluble secondary monoamine was also disclosed in the US patent USP) No. 4,225,65
It is known in No. 2.

In addition, the present inventor has discovered that in a combination of an epoxy resin and a substance that is reactive with the epoxy resin, at least one of the surrounding components is water-soluble, and the reaction product is water-insoluble without losing its wood-philicity. It has also been found that by selecting the circumferential component so that

However, the ink-receiving layer obtained in this way has low durability against the polyhydric alcohol contained in the ink, and the ink-receiving layer that has received a high-density ink (y) tends to stick to its surface under humid conditions. Phenomena such as curing and stickiness appeared, and a new problem arose in that blocking and color transfer occurred when the films were stacked unless they were soaked in vinegar for a considerable period of time after printing.

Furthermore, the combination of the above-mentioned epoxy resin and curing agent has the drawback that the reaction requires a long period of heating, resulting in low production efficiency.

As a result of further research to solve the above-mentioned problems while retaining various advantages of the prior invention, the present inventors have determined that a certain specific polymer, namely epoxy resin or epoxy The present invention was based on the discovery that when a substance that is reactive with resin is selected, a recording material with excellent ink receptivity, recorded image clarity, and water resistance can be obtained even when heated for a short time. It is.

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

N-vinylpyrrolidone, N-vinyl-3-methylpyrrolidone, N-vinyl-5-methylpiperidone, N-vinyl-3,3,5-)limethylpyrrolidone, 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-oxacylidone, N-vinyl-5-methyl-2 -Oxacylidone, N-vinyl-5-ethyl-
2-oxazolidone, N-vinyl-4-methyl-2-oxazolidone, N-vinyl-2-thioxazolidone,
Homopolymers such as N-vinyl-2-mercaptobenzothiazole or random copolymers, block copolymers, graft copolymers, etc. with other common monomers; N-vinylimidazole, N-vinyl-2-mercaptobenzothiazole, etc. Homopolymers of methylimidazole, N-vinyl-4-methylimidazole, etc., or random copolymers, block copolymers, graft copolymers, etc. with other common 7-mers; 2- or 4-vinylpyridine and other copolymerizable polymers that may be used in the above. are methacrylate and acrylate.

acrylamide, acrylonitrile, vinyl ether,
Vinyl acetate, vinylimidazole, ethylene, styrene and other common monomers, among which are particularly useful in the present invention are N-vinylpyrrolidone, N-vinylpiperidone, N-vinylcaprolactam, N-vinylmorpholine.

Homopolymer of N-vinyl-2-oxacylidone and N-vinyl-5-methyl-2-oxazolidone.

Copolymers, etc. 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.

The epoxy resin that mainly characterizes the present invention is a low to high molecular weight organic compound having two or more epoxy groups in its main chain and/or side chain.

Such epoxy resins react with any compound having active hydrogen such as a hydroxyl group, an amide group, a carboxyl group, a carboxamide group, a sulfamide group, etc. to produce a higher molecular weight polymer, and there are a wide variety of epoxy resins. These are known and easily available on the market, and can be easily manufactured as needed.

In the present invention, any conventionally known epoxy resin can be used, but those suitable for the present invention are bisphenols such as bisphenol A, ethylene glycol,
Epichlorohydrin in polyhydric alcohols such as diethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, glycerin, diglycerin, pentaerythritol, trimethylene glycol, tetramethylene gelicol, pentamethylene glycol, polyester polyol, polyether polyol, etc. Alternatively, it is an epoxy resin obtained by reacting shrimp bromohydrin.

These epoxy resins can be obtained from low molecular weight ones to high molecular weight ones depending on the reaction ratio with epichlorohydrin or shrimp bromohydrin.Epoxy resins made of bisphenols were particularly useful in the present invention. .

The present inventors have been conducting various research on mixtures of basic polymers and epoxy resins, and found that after preparing both polymers as solutions in the same solvent system, when the two solutions are mixed, there is a gap between the two polymers. It has been found that some kind of interaction occurs between the two polymers, and both polymers come to exhibit physical properties that are completely different from their respective properties before being mixed.

For example, in the case of mixing a basic polymer solution and an epoxy resin solution, the following forms were observed when broadly classified. Of course, these examples are general ones; for example,
Naturally, it varies depending on the type of solvent used and the type of basic polymer and epoxy resin used.

(1) The viscosity increases temporarily, but the viscosity decreases when stirred.

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

(3) Temporarily precipitates, but disappears when stirred.

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

[(1) and (3) or (4), (2) and (3) or (4) may overlap. (5) Even if a combination exhibits the above properties in one solvent system, it may show almost no change in another solvent system.

Also, even if a combination produces a precipitate in a poor solvent, the viscosity will increase during mixing in a good solvent.
In some combinations, the viscosity decreased as the mixture was stirred. This is thought to be because the solvent permeates into the polymer complex formed during mixing, and solvation progresses between both molecules in a bonded state.

Also, combinations that maintain a thickening and precipitation state are due to the bonding force between molecules being stronger than the affinity of the solvent.

It is considered that the above state can be maintained. However, when the basic polymer and epoxy resin are prepared using different solvents, the solubility of each polymer in the mixed solvent system also plays a role in the thickening and precipitation phenomena that occur when the two components are mixed.

In a dissolved state, the coating obtained from such combinations that can form polymer complexes naturally exhibits new functions that are completely different from the properties that each polymer had before mixing. there were.

Therefore, the polymer complex used in the present invention means a polymer complex made of the above polymers (polymer complexes made of these polymers are disclosed in Japanese Patent Publication No. 51-37017
It can be prepared by a method similar to that described in 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 wood-friendly, they do not have water resistance,
It is moisture resistant, and when used to form the ink-receptive layer of inkjet recording materials, it showed ink-receptivity equivalent to that of conventional water-soluble polymers, giving clear images, and its surface remained stable even under high humidity conditions. does not become sticky at all, and the strength of the ink-receiving part of the ink-receiving layer is stronger than when other general acidic polymers are used, and there is no blocking phenomenon even when the films are overlapped for a long time after printing. It was discovered that this does not occur.

Polymer complexes such as those described above generally do not dissolve in relatively strong solvents such as water, alcohols, esters, hydrocarbons, etc., so both polymers are dissolved in these poor solvents and the two solutions are mixed. By this,
Polymer complexes for use in the present invention can be isolated. Alternatively, a solution of the polymer complex can be obtained by mixing in a relatively good solvent such as dimethylformamide, dimethylacetamide, dimethylsulfoxide, or the like.

The present inventor conducted further research on these polymer complexes and found that among substances that are reactive with epoxy resins (hereinafter referred to as curing agents), when a certain curing agent is combined with an epoxy resin, It has been found that an ink-receiving layer with excellent coating strength can be obtained while retaining the property that the epoxy resin cures with short heating.

In the present invention, any conventionally known curing agent for epoxy resin can be used, but those suitable for the present invention are ethylenediamine, diethylenetriamine, triethylenetetramine, tetramethylenepentamine, diethylaminopropylamine, nanthanediamine, and biherizine. , aminoethylpiperazine, dicyandiamide, benzyldimethylamine, diaminodiphenylmethane, m-phenyl diamine, diaminodiphenylsulfone, xylylene diamine, maleic anhydride, phthalic anhydride, hexahydrophthalic anhydride.

2 Pyromellitic anhydride, trimellitic anhydride, dichloromaleic anhydride, methylnadic anhydride, dodecyl succinic anhydride,
Tetrachlorophthalic anhydride, pyrometic dianhydride, chlorendic anhydride, etc., but one or more are typical examples, and other than these, aliphatic amines, aromatic amines, modified amines, amine adducts, thiocols, Combinations of phenolic precondensates and acid anhydrides may also be used. Particularly useful in the present invention were acid anhydrides such as phthalic anhydride, trimellitic anhydride, and pyromellitic anhydride.

As described above, in the recording material of the present invention, the ink-receiving layer is formed by a polymer complex formed from a combination of a basic polymer and an epoxy resin, preferably a basic polymer, an epoxy resin, and a curing agent. It is characterized by

When using the above curing agents together, the timing and method of mixing the epoxy resin and curing agent are as follows: (1) Mix before coating.

(2) Mix at the time of coating.

(3) Apply either one (and the mixture of basic polymer) first, then the other.

(4) Apply one, then the other (and the mixture of basic polymer).

(5) Apply a mixture of either one and a basic polymer, and then apply a mixture of the other and a basic polymer.

(6) Apply the basic polymer, then apply the epoxy resin and curing agent mixture.

(7) Apply a mixture of epoxy resin and hardener.

A basic polymer is then applied.

However, any method can be used in the present invention. Separate application of each of the three components can also be used if a polymer complex is formed. When the mixing method is (1), care should be taken so that the resulting reaction product does not have an excessively crosslinked structure. Excessive crosslinking causes loss of hydrophilicity and solubility in organic solvents, making it difficult to form an ink-receiving layer.

Moreover, in either case, it is desirable to select and use both reaction components to such an extent that the resulting reaction product becomes water-insoluble without losing hydrophilicity.

Preferred basic polymers and epoxy resins for forming the above polymer complexes each have a molecular weight of 1.000 or more, preferably 5.000.
By using both polymers with these molecular weights, an ink-receiving layer with high strength, excellent ink-receptivity, image clarity, water resistance, ink resistance, and blocking resistance can be formed. can do.

In addition, the ratio of both polymers used is within a range of 10/l to 10/l to 10/l of basic polymer/epoxy resin in terms of weight ratio, and the ratio of epoxy resin to curing agent is generally determined by the epoxy equivalent and the activity. Although the hydrogen equivalent can be used as a guideline, the performance of the film was better when the curing agent used in the present invention was added in a slightly smaller order.

The reaction between these epoxy resins and the curing agent is very easy, but if necessary, conventionally known catalysts such as potassium hydroxide, sodium hydroxide, various tertiary
The reaction may be promoted using a catalyst such as a secondary amine, a quaternary ammonium salt, an alcohol, a tin chloride, or a borofluoride salt.

Curing is generally carried out by heating, but may also be carried out by irradiation with ultraviolet rays or electron beams, and the ratio of epoxy resin to basic polymer or epoxy resin and curing agent used is 10:1 to 10:5 by weight. Yes, preferably
This is the ratio at which the basicity and acidity of each polymer are approximately equal. If the weight ratio deviates from the above range, the bond between the two components 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 epoxy resin or the epoxy resin and curing agent are too large, the ink receptivity will be reduced.

Furthermore, as disclosed in Japanese Patent Application Laid-Open No. 59-174382, D
- Condensation products of sorbitol and benzaldehyde may be added in proportions 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 using one or more polymer complexes such as those described above, but in the present invention, in addition to the polymer complexes described above, other light-transmitting polymers such as It may also be used in combination with polymer complexes.

Preferred examples of such other polymers include albumin, gelatin, casein, starch, cationic starch, gum arabic, natural resins such as sodium alginate, polyvinyl alcohol, polyamide, polyacrylamide, quaternized polyvinylpyrrolidone, polyethyleneimine,
Synthetic resins such as polyvinyl bilicylium halide, melamine resin, polyurethane, polyester, and sodium polyacrylate may be mentioned, 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, alkyd 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.
Fillers such as talc, diatomaceous earth, calcium carbonate, calcium sulfate, barium sulfate, aluminum silicate, synthetic zeolites, alumina, zinc oxide, lithopone, satin white, and the like 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 examples of the opaque substrate include, for example, general paper, cloth, wood, metal plates, synthetic paper, and the like, 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, and 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.

Such a translucent recording material is produced by forming a translucent ink-receiving layer on the translucent base layer from the above-mentioned polymer complex alone or a mixture with other translucent polymers. It can be prepared.

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 polymers in a suitable solvent, and the coating solution is prepared by: For example, a method in which a transparent substrate is coated on the Murakami surface 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 method in which a solution of a basic polymer or epoxy resin is applied is applied. It is preferable to apply one of the above solutions and then apply another solution to form a polymer complex on the substrate. Other methods may also 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.

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 possible to project the recorded image onto a screen and observe it using an OHP, and furthermore, in order to clearly observe the details of the recorded image,
It is desirable that the in-line transmittance is 10% or more.

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

T=Y/Y, ) and opacity (
The white and black backings are placed on the back of the sample and the ratio is calculated. ), which evaluates translucency using diffused light.

Since the behavior of straight-line light is a problem with devices that use optical technology, it is important to evaluate the straight-line transmittance of the recording material when evaluating the translucency of the recording material to be used in these devices. 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 the test using the OHP test chart.

In order to obtain an image suitable for the above purpose, the in-line transmittance of the recording material needs to be 2% or more, and in order to obtain a clearer image, it is preferably 10% or more. 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 either the above-mentioned transparent or opaque base materials can be used. The ink receiving layer formed on these base materials 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 thickness of the ink receiving layer formed on the base material is usually about 0.5 to 100 gm, preferably about 1 to 50 gm, more preferably 3 to 30 gm.
It is about Lm.

Further, 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 1 dispersant, fluorescent dye, P
Various known additives such as H regulators, antifoaming agents, lubricants, preservatives, and surfactants can be included.

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 recorded images with excellent clarity, and furthermore, 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 is repeatedly deposited on the same spot within a short period of time, there will be no ink waving or seeping phenomenon, and the ink-receiving layer will not be affected. Clear recorded images with high resolution can be obtained without any decrease in intensity.

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.

This superior performance under high humidity conditions is due to the intermolecular forces (e.g., intermolecular electrostatic forces, hydrogen bonds, van der Waalska, charge It is thought that some kind of weak bonding occurs to form a polymer complex, which exhibits excellent water resistance, blocking resistance, etc. 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 without reducing its film strength, allowing it to accept the ink. This is believed to be because the ink-receiving layer returns to its original water-insoluble polymer complex by absorption and evaporation of water after receiving the water. It should be noted that such a theory is just imagination and does not limit the present invention in any way.

The present invention can also be used to provide excellent surface gloss not seen in conventional inkjet recording materials, and can also be used to project recorded images onto a screen, etc. using optical equipment such as slides and OHPs. It can be applied to applications other than conventional surface image observation, such as those used for observation, color separation plates when creating positive plates for color printing, and CMF used for color displays such as liquid crystals.

Hereinafter, the present invention will be explained in more detail with reference to Examples. In addition, parts and percentages in the text are based on weight unless otherwise specified.

Example 1 Polyvinylpyrrolidone (PVPK-90, made by GaP) 1
100 parts of 0% dimethylformamide (hereinafter referred to as DNF) solution and 20 parts of 11N of 33% DMF solution (Epoxy resin I18 < Epicote 1255, manufactured by Yuka Shell Epoxy) were mixed. The mixture thickens and a polymer complex is formed. When this mixed solution is stirred, the viscosity decreases slightly and becomes a fluid solution, which is used as a coating solution.

A polyethylene terephthalate film (manufactured by Toshi) with a thickness of 1100 JL was used as a translucent base material, and a coating solution with the above composition was applied onto this film using a bar coater method so that the film thickness after drying was 8 gm. It was coated and dried at 140° C. for 3 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 4 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 three types of transparent recording materials of the present invention and three types of recording materials for comparison.

Vinylpyrrolidone/dimethylaminoethyl methacrylate copolymer (COPOLYMER845, manufactured by GAF)
10% ethanol/DMF solution) 100 parts Epoxy resin (Epicor) 1001. Yuka shell epoxy) (1
0% DMF solution) 17 parts 2 Pyromellitic anhydride (10% DMF solution) 3 parts U Polyvinylpyrrolid 7 (PVPK-90, made by GAF) (10% DMF solution) 100 parts Epoxy resin (Epicote 1007, oil (manufactured by Shell Epoxy) (10% DMF solution) 8 parts 2 pyromellitic anhydride (10% DNF solution) 2 parts 1 Special A Polyvinylpyrrolid y (PVPK-90, manufactured by GAF) (10% DMF solution) 100 parts epoxy Resin (Epicoat 1255, manufactured by Yuka Shell Epoxy) (33% DMF solution) 20 parts D-lysorbitol/benzaldehyde condensate (Gelol D, manufactured by Shinnihon Rika) (10% DMF solution)
5 parts Salt Shibori Isamu" Polyvinylpyrrolid y (PVPK-90, made by GAF) 10 parts DMF 90 parts Kojibori 1λ Polyvinylpyrrolid 7 (PVPK-90, made by GAF) (
10% aqueous solution) 50 parts Polyvinyl alcohol (PVA-217, manufactured by Kuraray) (10%
Aqueous solution) 50 parts ± Comparison 1” Polyvinylpyrrolidone (PVPK-90, manufactured by GAF)
(10% DMF solution) 70 parts methyl vinyl ether/M water maleic monoethyl ester copolymer (GANTREZ ES-425, manufactured by GAF) (
30 parts of 10% ethanol/DMF solution Diameter 60pm, piezo vibrator drive voltage 70V, frequency 2KH
Inkjet recording was carried out using a recording apparatus having the following.

Nine! (Composition) C, 1, Direct Yellow 86 2 parts diethylene glycol 25 parts polyethylene glycol #200 15 parts water
60 parts L Shieno (composition) C, 1, Acid Red 35 2 parts Diethylene glycol 25! Polyethylene glycol #200 15 parts water
60 parts Biel (composition) C, 1, Direct Blue 86 2 parts diethylene glycol 25 parts polyethylene glycol #200 15 parts water
60 parts 1e! (Composition) C, 1, Food Black 2 2 parts diethylene glycol 25 parts polyethylene glycol #200 15 parts water
Table 1 shows the evaluation results of the recording materials of 60 copies Examples and Comparative Examples.

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

(1) Ink fixation time is determined by leaving the recording material after recording at room temperature (20°C, 65% RH) and touching the recorded image with your finger, the ink will dry and will no longer stick to your finger. The time was measured.

(2) Dot density can be determined by applying JIS K7505 to a printing microtooth using the Sakura Microdensidometer P.
The black dots were measured using DM-5 (manufactured by Konishiroku Photo Industry Co., Ltd.).

(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 recorded image has a high 00 (optical density), and a clear and easy-to-see projected image with high contrast is obtained, and 0 indicates that the non-recorded area is slightly dark and the recorded image is high. If the OD of the image is rather low and the line of 0.25 m thick with a pitch width of 0.5 m cannot be clearly distinguished, Δ, the non-recorded area is quite dark, the OD of the recorded image is quite low, and the pitch width is 11 mm. A case where the line of the colic with a thickness of 0.3 could not be clearly distinguished or a case where the non-recorded part and the recorded image could not be distinguished was designated as X.

(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 90 mm, and measuring the spectral transmittance as described above ( 1) It was calculated using the formula.

(5) Machine runability is measured under the conditions of 35°C and 85% RH, when the recording material is loaded into the printer, the printer's feed roller cannot run due to the stickiness of the surface of the ink-receiving layer. Those that cannot be done are marked with an X, and those that cannot be marked as a 0.

(6) For blocking, after 1 hour 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 rated as O, and those in which no adhesion occurred were rated as ×. Further, when a similar test was conducted 10 minutes after printing, those in which no adhesion occurred were rated as 0.

(7) Film strength: After 5 minutes of printing, when the surface of the solid printed area of the ink-receiving layer was rubbed with a finger, there was no strength of the film, and it was from the base film! Items with 4# or damaged images were rated X, and those with no damage were rated O.

(8) Formation of a polymer complex was determined by preparing basic polymer and epoxy resin as solutions of the same type, and when mixing the two, a case where there was a sudden increase in viscosity or formation of gel was marked as 0, and a case where no gel was formed was marked as ×. .

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Claims (2)

[Claims] (1) An inkjet recording material comprising an ink-receiving layer provided on a base material, wherein the ink-receiving layer contains a basic polymer and an epoxy resin. (2) Claim No. 1 (2) containing a basic polymer, an epoxy resin, and a substance reactive with the epoxy resin.
The recording material described in item 1).