JPH04201594A - Material to be recorded and ink jet recording method - Google Patents

Abstract

PURPOSE:To enable an image which is excellent in both lightfastness and waterproof to be obtained by a method wherein hyperfine powder of transition metal oxides is contained in an ink accepting layer provided on a base material. CONSTITUTION:Hyperfine powder, forming constituent of an ink accepting layer provided on a base material 20, is the hyperfine powder of transition metal oxides. For instance, a cerium oxide, a zinc oxide, a titanium oxide, an yttrium oxide, etc., are exemplified. Its particle size is 0.1mum or under and is preferably within a range of 0.001 to 0.01mum. Further, an amount of the hyperfine powder of the transition metal oxides contained in the ink accepting layer is preferably within a range of 0.01g/m<2> to 3.0g/m<2>. Further, when required, a fluorescent whitening agent, a surface active agent, an antifoaming agent, a pH regulator, a mildewproof agent, an ultraviolet absorbent, an oxidation inhibitor, etc., may be contained in the ink accepting layer. An image which is excellent in both waterproof and light-fastness can be obtained thereby.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a recording material (recording paper) used for recording with ink, and in particular, the present invention relates to a recording material (recording paper) used for recording with ink, and in particular, the ink has excellent color development and color properties, and has high resolution, light resistance and The present invention relates to a recording material and an inkjet recording method that form recorded images with excellent water resistance.

(Prior Art) Conventionally, recording materials for inkjet use include: (1) ordinary paper whose main component is valves, made into paper of low size to make it like filter paper or absorbent paper; (2) As disclosed in Japanese Patent Application Laid-Open No. 56-148585, it is known that an ink-absorbing layer is provided using a porous inorganic pigment on a base paper with low ink-absorbing properties such as general high-quality paper. ing.

On the other hand, especially in the inkjet recording method for forming high-quality, high-resolution color images, the following requirements are required for the recording material used.

(1) Good color development of the ink when applied to a recording material.

(2) Good roundness of ink dots.

(3) Good ink absorption capacity so that even if multiple ink droplets are applied to the same spot, they will not flow out.

(4) Good ink fixability that does not smear even if the attached ink droplets are rubbed immediately afterwards.

(5) Good image storage properties such as light resistance and water resistance of the formed image.

(Problems to be Solved by the Invention) However, the reality is that there is still no known recording material for inkjet that satisfies all of the above required performances.

In other words, it is thought that the main cause of the light fastness problem of inkjet recorded images is discoloration and fading due to photodecomposition of the dye, so in order to improve the light fastness of recorded images, it is necessary to use dyes with excellent light fastness in the ink. It should be used for.

However, at the same time, inkjet ink must not clog the inkjet nozzle.
Not all dyes can be used in inkjet inks because they must also satisfy conditions such as having a clear color tone. Conventionally, acid dyes and direct dyes have been used as inkjet inks, but the light resistance of these dyes cannot be said to be sufficient.

On the other hand, JP-A-57-74193 proposes an inkjet ink containing at least one type of ultraviolet absorber, and JP-A-57-87,987 proposes an inkjet ink containing at least one type of ultraviolet absorber, and JP-A-57-87,987 proposes an inkjet ink containing at least one type of ultraviolet absorber. We have proposed a recording material containing at least one of
No. 88 proposes a recording material containing an ultraviolet absorber such as 2-hydroxy-4-octoxybenzophenone and phenylsalicylic acid. Furthermore, JP-A-60-72
Publication No. 785 introduces a recording material containing a quaternary ammonium compound of polyethyleneimine, an antioxidant and/or an ultraviolet absorber. However, even with the recording materials described above, the light resistance and image density of recorded images and the long-term storage stability of the recording materials are not necessarily sufficient.

That is, since organic ultraviolet absorbers themselves deteriorate by absorbing ultraviolet rays, there is a problem that the effect of suppressing photodeterioration is not sustained.

In addition, the addition of metal salts often changes the pigment of the recorded image (furthermore, the metal oxides disclosed so far do not have a sufficient effect of inhibiting ultraviolet rays, and these all affect the light resistance of the recorded image. The effect of improving is not sufficient.

Accordingly, an object of the present invention is to provide a recording material suitable for inkjet recording that satisfies the above-mentioned requirements and provides images with particularly good light resistance and water resistance.

'Furthermore, another object of the present invention is to improve the color development of ink,
An object of the present invention is to provide a recording material that provides images with excellent color properties and a recording method using the same.

(Means for solving problems) The above object is achieved by the present invention as follows.

That is, the present invention provides a recording material having a base material and an ink receiving layer provided on the base material, wherein the ink receiving layer contains ultrafine powder of a transition metal oxide. A recording material and a recording method using the same.

(Function) The recording material of the present invention provides recorded images with excellent light resistance and water resistance due to the ultraviolet absorbing action of the specific transition metal oxide contained in the ink receiving layer provided on the base material. Moreover, the ink has excellent color development and color properties.

(Preferred Embodiments) Next, the present invention will be described in detail by citing preferred embodiments.

The ultrafine powder that is a forming component of the ink-receiving layer used in the present invention is an ultrafine powder of transition metal oxides, such as cerium oxide, zinc oxide, titanium oxide, yttrium oxide, etc. It will be done.

Moreover, the particle size is 0.1 μm or less, more preferably O, O
1 um or less, more preferably 0°001 to 0.0
It is in the range of 1 μm.

Specific examples of ultrafine powder of transition metal oxides are shown below.

For example, yttrium oxide (y2os) is manufactured using xenotime (YPO4), uranium slag, etc. as main raw materials,
It is used for applications such as phosphors and ceramic additives, and the powder with an average particle size of about 1.8 LLm is a cubic crystalline white powder, and its specific gravity is 5.03.

Examples of the ultrafine powder of yttrium oxide used in the present invention include yttrium oxide sol, which is an amorphous powder with an average particle size of 40 mm.

In addition, titanium oxide (TiOa) has a high refractive index, so
It is widely used as a white pigment with high brightness, coloring power, and hiding power because it has high light scattering, high reflectance, high opacity, and excellent chemical and physical stability. Depending on the type, there are anatase type and rutile type.

Anatase-based powders exhibit high reflectivity for short-wavelength light, so the whiteness of the powder is superior to rutile-based powders, but their crystal structure is unstable and they are photochemically active.
In terms of light resistance, it is inferior to the Lucifle type. Both have a tetragonal crystal form, and the average particle size is 0.1 to Q, 2 gm for anatase type, and 0.2 to 2 gm for rutile type.
0.3 μm, and the specific gravity of both is around 4.0.

The ultrafine titanium oxide powder used in the present invention is produced, for example, by hydrolyzing titanium tetrachloride vapor in an oxyhydrogen flame.

Mainly showing anatase type crystal structure, average particle size 0.
011. Examples include white powder titanium oxide sol with Lm and specific gravity of 1.04. This type of ultrafine titanium oxide powder has a higher chemical purity than titanium oxide with a larger particle size.
Fine particle size, bulk specific gravity, high dispersibility (no agglomeration)
The distinction comes from points such as 8.

In addition, zinc oxide is naturally produced as red zinc acid, but the one obtained by air oxidation of zinc vapor is generally used, but this shows a hexagonal wurtzite crystal form and its Average particle size is 0.5 to 1.0 μm, specific gravity is 5.47 to 5.7
8 white powder.

The ultrafine zinc oxide used in the present invention has, for example, an average particle size of 0.005 to 0.015 μm and a specific gravity of 5.0 μm.
The white powder of No. 78 can be mentioned, but it is preferable because it exhibits a wider range of superior ultraviolet absorption properties than the titanium oxide described above, and exhibits a good white color because it absorbs almost no visible light.

In addition, cerium oxide (SeO□) can be obtained by, for example, heating carbonate, sulfur salt, nitrate, cerium (IV) ammonium nitrate, etc. to a high temperature and then washing it with dilute nitric acid to remove other dilute salt oxides. is obtained by heating metallic cerium in air, and is a white or pale yellow powder exhibiting an equiaxed or fluorite crystal structure. In addition, since it is possible to store a large amount of oxygen in a powder state, it has various catalytic effects.

Examples of the ultrafine cerium oxide powder used in the present invention include 21 Doral (manufactured by Tamoto Kagaku Kogyo), which has an average particle size of 50 mm and a specific gravity of 1.21.

Needral is ultra-fine particles and has good dispersibility, so it has good transparency (also, its ultraviolet absorption ability in the ultraviolet region (380 mm or less) is superior to conventional titanium oxide,
This is preferable.

The first feature of the present invention is that by using the above-described ultrafine transition metal oxide powder as a forming component of the ink-receiving layer of the recording material, high-definition, high-density recorded images can be produced. Another advantage is that sufficient light resistance and water resistance can be obtained.

That is, as a result of the present invention containing a specific transition metal oxide as a light resistance improver in the ink receiving layer of a recording material, it is extremely stable against ultraviolet light, has excellent light resistance, and has water resistance. A recording material with sufficient image density and ink absorbency can be obtained.

The recording material of the present invention is composed of a base paper as a base material and a surface layer which is an ink receiving layer mainly composed of a pigment and a binder.

Although the pigment used in the present invention is not particularly limited, it is preferable to use a cationic pigment for the purpose of improving the density and water resistance of an image.

In other words, the cationic pigment here refers to one whose zeta potential exhibits a positive value, but in boat fishing, powder with a positive zeta potential adsorbs anionic substances on its surface. easy. For this reason, when used in inkjet recording using anionic dyes, it is particularly effective because high-density recorded images can be obtained and it is thought to play an auxiliary role as a waterproofing agent.

Specifically, examples of such cationic pigments used in the present invention include aluminum oxide, magnesium oxide, magnesium hydroxide, and basic magnesium carbonate.

The above-mentioned zeta potential (ξ) is a value determined from the potential (flowing potential) generated when an electrolyte solution is caused to flow through the powder bed using the following formula 0.

E: Flow potential P: Pressure for flowing the liquid η: Viscosity coefficient of the liquid λ: Electrical conductivity of the liquid ε: Direction of the dielectric constant of the liquid In the present invention, a potassium chloride solution of 1/1000 normality is flowed. The value found from the streaming potential at that time was defined as the zeta potential.

Further, the preferred BET specific surface area of the cationic pigment used in the present invention is 170rr? /g or less. This is because if it exceeds 170 rrr/g, a new problem related to image fastness, which is called indoor discoloration of images, occurs, which is different from the problem of light fastness.

As described above, by forming the ink-receiving layer of the recording medium of the present invention mainly from a cationic pigment, it is possible to improve water resistance and obtain an image having light resistance.

Furthermore, in the present invention, in order to obtain more sufficient water resistance and light resistance, an ink-receiving layer may be formed by using the above-mentioned ultrafine particulate powder of a transition metal oxide together with the above-mentioned cationic pigment. is more desirable.

Further, the method for producing the recording material of the present invention includes (1) coating a coating liquid containing ultrafine powder of a transition metal oxide and a pigment on a substrate to form an ink-receiving layer; (2) applying an aqueous dispersion or solvent solution of ultrafine transition metal oxide powder onto a surface layer pre-constituted with a pigment and a binder, or (3) immersing it in these solutions. There are methods of forming an ink-receiving layer by providing a coating layer on the surface layer, and the like.

According to the findings of the present inventors, method (1) is more desirable in order to obtain a high-density image, and method (2) or (3) is more desirable in order to enhance ultraviolet shielding properties and further improve light resistance. The following method is preferable.

Further, the amount of ultrafine powder of transition metal oxide loaded in the ink receiving layer of the recording material of the present invention is 0.01 g.
/Go~3. Preferably, the range is Og/ni. If this amount is less than 0.01 g/rrr, the effect of the ultrafine powder cannot be expected and the light resistance of the resulting recorded image will not improve. On the other hand, if it exceeds 3.0 g/rrr, the ink absorbency, dye color development, and color reproducibility will deteriorate, which is not preferable.

In the present invention, other components contained in the ink receiving layer include highly water-soluble materials such as starch, cationic starch, gelatin, casein, gum arabic, sodium alginate, carboxymethyl cellulose, polyvinyl alcohol, polyvinylpyrrolidone, and sodium polyacrylate. Molecule: Synthetic resin latex such as synthetic rubber latex, polyvinyl butyral,
Organic solvent soluble resin such as polyvinyl chloride;
Various additives such as a dispersant, a fluorescent dye, a pH adjuster, an antifoaming agent, a lubricant, a preservative, and a surfactant can be mentioned, and these can be arbitrarily selected and used.

Furthermore, it is also possible to use a mixture of the ultrafine powder of the transition metal oxide described above and a conventionally known cationic polymer (water resistant agent).

Water-resistant agents are added to solve the problem of inkjet recording methods, which use water-based inks, which cause the recorded images to lack water resistance and become unreadable due to ink smearing when exposed to water. be done. Examples of such water resistance agents include halogenated quaternary ammonium as disclosed in JP-A-56-99693, and JP-A-56-99693.
84992, JP 59-20696, JP 59-'33176, JP 61-5878
Primary to tertiary amines or tertiary amines as disclosed in Publication No. 8
Compounds containing ammonium salts are known.

Further, a water-insoluble compound containing an amorphous basic aluminum salt, etc. may be used as the waterproofing agent.

The recording material of the present invention may have a multilayer structure using an ink-absorbing base material as the base material on which the ink-receiving layer as described above is provided.

The ink-receiving layer referred to in the present invention is a layer that constitutes the recording surface, and is not capable of absorbing and retaining the entire amount of ink that adheres to it (it mainly adsorbs the dye in the received ink, It has the function of transmitting most of the ink solvent and transferring it to the ink-absorbing base paper.

For this reason, the recording material of the present invention has a recording surface in which a pigment forming a surface layer and a fibrous substance of a base paper are mixed, and/or a recording surface having a maximum thickness of 20 μm, more preferably 15 μm.
It has an aspect in which it is covered with an ink-receiving layer having a size of .mu.m or less.

Further, the preferred coating amount of the ink receiving layer in the present invention is within the range of 0.3 to 7 g/rrr as the total amount of pigment. If the coating amount is less than Q, 3g/r+f, there will be no effect compared to the case where no ink-receiving layer is provided.On the other hand, if the coating amount is more than 7g/d, If the maximum thickness exceeds 20 um, problems such as a significant decrease in ink absorbency and generation of paper dust will occur.

In the present invention, the pigment coating amount of the ink receiving layer is more preferably 1 to 7 g/rrf, and even more preferably 2 to 7 g/rrf.

In the present invention, the maximum thickness of the ink-receiving layer refers to the maximum thickness of the surface layer in the depth direction in the cross section of the recording material, and the pigment coating amount refers to the amount of pigment applied as the ink-receiving layer. It's the amount. In addition, the amount of pigment applied is according to JIS-P-8128.
It can be obtained as a value obtained by subtracting the ash content of the base paper determined by the same method from the ash content of the entire recording material determined by the method.

The base paper, which is the base material on which the ink-receiving layer is provided, is preferably ink-absorbing, and its preferred Steckigt sizing range is from 0 to 15 seconds, more preferably from 0 to 1.
0 seconds, more preferably 0 to 8 seconds. If a base paper with a Steckigt sizing degree of more than 15 seconds is used, the ink absorbency of the recording material as a whole will be insufficient, which is undesirable.

In the present invention, the bulbs constituting the base paper are not particularly limited, and are mainly wood bulbs such as conventionally known LBKP and NBKP, but synthetic fibers or glass fibers may be mixed as necessary. .

Specific examples of fillers for the base paper used in the present invention include clay, talc, kaolinite, titanium oxide, calcium carbonate, etc., which are used for boat fishing. It is contained in a range of 1 to 30 g/d, more preferably 2 to 10 g/rrr in terms of conversion. Among these fillers, calcium carbonate is particularly preferred because it provides good dot shape and color development.

The base paper used in the present invention is made by using the above-mentioned materials and conventionally known paper making aids, sizing agents, retention improvers, paper strength enhancers, etc. as necessary.

Furthermore, when using an ink-absorbing base paper, the basis weight of the base paper is also an important factor that affects printing quality, and in this case, the basis weight should be within the range of 60 to 120 g/rrr. is preferred. In order for the base paper to absorb ink, the basis weight of the base paper is 6.
If it is less than 0 g/rrr, there is a problem that print-through or scratching occurs when high-density printing is performed. On the other hand, if it exceeds 120 g/rrr, the stiffness of the paper becomes too strong, causing problems in conveyance within the recording apparatus.

In preparing the recording material of the present invention, a coating liquid containing the above-mentioned components is coated using a known method such as a roll coater method, a blade coater method, an air knife coater method, a gate roll coater method, Coat onto the surface of the base material using a size press method or the like.

Furthermore, after applying the aqueous coating liquid consisting of pigment and binder onto the substrate, it may be dried using a conventionally known drying method, such as a hot air drying oven,
The recording material of the present invention is obtained by drying using a hot drum or the like.

Further, in order to smooth the surface of the ink and the receiving layer, or to increase the surface strength of the ink receiving layer, a supercalender may be used in the process.

Furthermore, in the present invention, the ink-receiving layer may contain a fluorescent brightener, a surfactant, an antifoaming agent, a pH adjuster, a fungicide, an ultraviolet absorber, an antioxidant, etc., if necessary.

The method of the present invention is a recording method using the recording material of the present invention, and in this recording method, the ink itself applied to the specific recording material as described above by an inkjet recording method may be a known one (for example, The recording agent is a water-soluble dye such as a direct dye, an acid dye, a basic dye, a reactive dye, or a food coloring.

It is particularly suitable as an ink for inkjet recording, and is preferable in combination with the recording material of the present invention to provide an image that satisfies required properties such as fixability, color development, clarity, stability, and light fastness. For example, C,1, Direct Black 17.19.32.51.
71.108.146, C,1, Direct Blue 6.22.25.71.86
, '90.106.199, C,1, Direct Red 1.4.17.28°83, C,1, Direct Yellow 12.24.26.86.
98.142, C, 1, Direct Orange 34.39.44.46.
60, C01, Direct Violet 47.48, C,1,
Direct dyes such as Direct Brown 109 and C,1, Direct Green 59, C,1, Acid Black2.
7.24.26.31.52.63.112.118, C,1, Acid Blue 9.22.40.59.93.
102.104.113.117.120.167.2
29.234, C, 1, Acid Red 1.6, 32.37.51.5
2.80.85.87.92.94.115.180.
256.317.315, C, 1, Acid Yellow 11.17.23.25.29
．． Acidic dyes such as C,1, Acid Orange 7.19 and C,1, Acid Violet 49 are preferred, as well as C,1, Basic Black 2, C,1, Basic Blue 1.3. 5.7.9.24.
25.26.28.29, C, 1, Basic Red 1, 2.9.12.13.1
4, 37, CI, Basic Violet 7.14.27 and C,
1, Food Black 1, 2 etc. also come in use 8.

The above-mentioned examples of dyes are particularly preferable for the ink applied to the recording method of the present invention, but the dyes for the ink used in the present invention are not limited to these dyes.

Such water-soluble dyes are generally used in a proportion of about 0.1 to 20% by weight in conventional inks, and this proportion may be the same in the present invention.

The solvent used in the aqueous ink used in the present invention is water or a mixed hot medium of water and a water-soluble organic solvent, and particularly preferred is a mixed solvent of water and a water-soluble organic solvent, and a water-soluble organic solvent is particularly suitable. It contains a polyhydric alcohol which has the effect of preventing ink from drying. Further, the water is not ordinary water containing various ions (it is preferable to use deionized water).

The content of the water-soluble organic solvent in the ink is generally in the range of 0 to 95% by weight, preferably 10 to 80% by weight, more preferably 15 to 50% by weight based on the total weight of the ink. be.

In addition to the above-mentioned components, the ink used in the present invention may also contain a surfactant, a viscosity modifier, a surface tension modifier, etc., as necessary.

Further, the method for performing recording by applying the above-mentioned ink to the recording material of the present invention is preferably an inkjet recording method, and this method effectively removes the ink from a nozzle and uses a projectile. Any method may be used as long as it can apply ink to the recording medium.

In particular, the method described in Japanese Unexamined Patent Publication No. 54-59936 is an inkjet jet in which ink subjected to the action of thermal energy causes a sudden change in volume, and the acting force due to this change in state causes the ink to be ejected from a nozzle. The method can be used effectively.

An example of an inkjet recording device suitable for recording using the recording material of the present invention will be described below. Examples of the head configuration, which is the main part of the device, are shown in Figures 1(a) and 1(a).
b) and shown in FIG.

The head 13 is made by bonding a glass, ceramic, or plastic plate, etc., having grooves 14 through which ink passes, and a heat-generating head 15 (the head is shown in the figure, but is not limited thereto) used for thermal recording. It can be obtained by

The heat generating head 15 has a protective film 1 formed of silicon oxide or the like.
6. It consists of aluminum electrodes 17-1, 17-2, a heat generating low antibody layer 18 formed of nichrome or the like, a heat storage layer 19, and a substrate 20 with good heat dissipation properties such as alumina.

The ink 21 has reached a discharge orifice (micropore) 22, and a meniscus 23 is formed by the pressure P.

Now, when an electric signal is applied to the electrodes 17-1 and 17-2, the area indicated by n of the heating head 15 suddenly generates heat.
Bubbles are generated in the ink 21 that is in contact with this, and the meniscus 23 is suddenly compressed by the pressure of the bubbles, and the ink 21 is ejected and becomes recording droplets 24 from the orifice 22, flying toward the recording material 25. FIG. 2 shows an external view of a multi-head in which a large number of heads shown in FIG. 1(a) are arranged. The multi-head is manufactured by closely adhering a glass plate 27 having multi-grooves 26 and a heating head 28 similar to that explained in FIG. 1(a).

Note that FIG. 1(a) is a cross-sectional view of the head 13 along the ink flow path, and FIG. 1(b) is a cross-sectional view taken along line AB in FIG. 1(a).

FIG. 3 shows an example of an ink jet recording apparatus incorporating such a head.

In FIG. 3, 61 is a blade as a wiping member, one end of which is held by a blade holding member and becomes a fixed end, forming a cantilever shape. The blade 61 is disposed adjacent to the recording area of the recording head, and in this example, is held in a protruding form in the movement path of the recording head. A cap 62 is disposed at a home position adjacent to the blade 61, and is configured to move in a direction perpendicular to the moving direction of the recording head and come into contact with the ejection port surface to perform capping. Furthermore, 63 is an ink absorber provided adjacent to the blade 61, and like the blade 61, it is held in a protruding form in the moving path of the recording head. The blade 61, cap 6
2. The absorber 63 constitutes an ejection recovery section 64, and the blade 61 and the absorber 63 remove moisture, dust, etc. from the ink ejection orifice surface.

Reference numeral 65 is a recording head that has an ejection energy generating means and performs recording by ejecting ink onto a recording material facing the ejection orifice surface on which ejection ports are arranged, and 66 is a recording head that mounts the print head 65 and moves the print head 65. It is a carriage for carrying out. The carriage 66 is slidably engaged with a guide shaft 67, and a portion of the carriage 66 is connected to a belt 6 driven by a motor 68.
9 (not shown). As a result, carriage 6
6 can be moved along the guide shaft 67, and the recording head 65 can move the recording area and its adjacent area.

Reference numeral 51 is a paper feeder for inserting recording material, and 52 is a paper feed roller driven by a motor (not shown). With these configurations, the recording material is fed to a position facing the ejection opening surface of the recording head, and as recording progresses, it is ejected to a paper ejection section provided with a paper ejection roller 53.

In the above configuration, when the recording head 65 returns to the home position after recording is completed, the cap 62 of the head recovery section 64
is retracted from the moving path of the recording head 65, but the blade 61 protrudes into the moving path. As a result, the ejection port surface of the recording head 65 is wiped. When the cap 62 comes into contact with the ejection surface of the recording head 65 to perform capping, the cap 62 moves so as to protrude into the movement path of the recording head.

When the recording head 65 moves from the home position to the recording start position, the cap 62 and the blade 61 are in the same position as the wiping position described above. As a result,
During this movement as well, the ejection orifice surface of the recording head 65 is wiped.

The above-mentioned movement of the print head to the home position is not limited to the end of printing or recovery of ejection, but also the movement of the print head to the home position adjacent to the print area at predetermined intervals while the print head moves across the print area for printing. However, along with this movement, the above-mentioned wiping is performed.

(Example) Next, the present invention will be explained in more detail by giving examples and comparative examples.

In the text, parts or percentages are based on weight unless otherwise specified.

Examples 1 to 4, Comparative Examples 1 and 2 The base material had a Steckicht sizing degree of 5 seconds and a basis weight of 66 g.
/nf, ash content is 9.0% (J I 5-P-8128
A base paper with a

A coating solution (A) having the following composition was applied onto this base paper using a bar coater method so that the dry coating amount was 5 g/rd, and then dried at 110° C. for 3 minutes. -4 and Comparative Examples 1 and 2 were obtained. The types and amounts of transition metal oxides used in each case are listed in Table 1.

Nagi Nioka/Yu A/Silica (Fine Seal X-37, manufactured by Tokuyama Soda ■)
100 parts polyvinyl alcohol (PVA117, manufactured by Kuraray ■)
32 parts/transition metal oxide ultrafine particle powder X parts/water (747+5.
7X) Section Examples 5 and 6, Comparative Example 3 Example 1 except that the coating liquid (A) was changed to the following (B).
- 4 and Comparative Examples 1 and 2, recording materials of Examples 5 and 6 of the present invention and Comparative Example 3 were obtained, respectively.

The types and amounts of transition metal oxides used at that time are also listed in Table 1.

``Koi'' J Hikinori U Koichi *Converted to solid content・Aluminum oxide particles (AKP-G, manufactured by Sumitomo Chemical ■) 100 parts・Polyvinyl alcohol (PVA105, manufactured by Kuraray ■)
32 parts/Transition metal oxide ultrafine particle powder X parts/Water (747+5
．． 7X) Section Examples 7 and 8, Comparative Example 4 Steckigt size degree is 5 seconds as base paper, embedment is 66 g
/G, having an ash content of 9.0% (according to J I 5-P-8128) was used.

Coating the following on this base paper? ff1 (C-1) was applied using a bar coater method to a dry coating amount of 5 glrd, and dried at 110°C for 3 minutes.

Next, coating liquid (C-2) was overcoated on this by a bar coater method, and re-dried for 3 minutes at 110°C. I got it. still,
As in the other examples, the types and amounts of transition metal oxides used in each case are listed in Table 1.

゛ Engineering C-1) - Aluminum oxide particles (AKP-G, manufactured by Sumitomo Chemical ■) 100 parts - Polyvinyl alcohol (PVA105, manufactured by Kuraray ■)
32 parts, 2 m long, 2 m long, transition metal oxide ultrafine particle powder, part X, water
Example 9 On the recording material formed in Comparative Example 1, ultrafine zinc oxide powder ZR-35ONE manufactured by Sumitomo Cement ■ was applied. A film was formed to a thickness of 4 um to form a recording material of the present invention. During film formation, 6 wt % of a curing agent was added to the ZR-350RE emulsion, and the film was dried at 180°C.

Example 10 Example 9 Using ultrafine zinc oxide powder ZR-35ONE manufactured by Sumitomo Cement ■ on the recording material formed in Comparative Example 3
A recording material of the present invention was formed in the same manner as described above.

(Evaluation) The inkjet recording suitability of each recording material formed as described above was 128 mm at a nozzle spacing of 16 nozzles per 1 mm.
Y, M, C inkjet head with book nozzle
Using an inkjet printer equipped with four colors of , Bk, inkjet recording was performed using ink having the following composition and evaluated.

En no ■ Precepts, dye 5 parts, diethylene glycol 30 parts, water
68 parts Y: C, 1, Direct Yellow 86 M: C, 1, Acid Red 35 8: C, 1, Direct Blue 199 C: C, 1, Direct Black 2 Evaluations were made on the following items, and the results are listed below. It is shown in Table 2.

(1) Image density The image density of the black printed area printed solidly using the above-mentioned inkjet printer was measured using the Macbeth densitometer RD-9.
18 was used for evaluation.

(2) Light resistance The printed matter was irradiated for 150 hours using a xenon fade meter (Ci-35 Atlas Co., Ltd.) under the conditions of a black panel temperature of 63°C and humidity of 70% RH, and the color of the M printed area before and after irradiation was The difference in CIE LAB was determined and evaluated using a color analyzer (CA-35 manufactured by Murakami Color Science).

As a result, as shown in Table 2, the recording materials of the present invention had high image density (and excellent light resistance).Furthermore, these materials do not contain transition metal oxides in the ink-receiving layer. Water resistance was also improved compared to the original.

The recording materials of Comparative Examples 1 to 4 had poor light resistance. or,
The recording material of Comparative Example 2 had poor ink absorbency.

(Hereinafter referred to as margin) (Effects) As described above, according to the present invention, the ink-receiving layer of the recording material is formed mainly of a porous cationic inorganic pigment,
Furthermore, by containing ultrafine particle powder of transition metal oxide having ultraviolet absorbing properties, ink is quickly absorbed into the interior thereof.

Furthermore, even when inks of different colors are deposited overlappingly on the same location on the recording material within a short period of time, there is no ink flow or oozing phenomenon, and a clear image with high resolution can be provided.

Furthermore, the resulting image has excellent light resistance and water resistance, and is suitable as a recording material for inkjet recording.

[Brief explanation of the drawing]

FIGS. 1(a) and 1(b) are a longitudinal cross-sectional view and a cross-sectional view of a head portion of an inkjet recording apparatus used in the method of the present invention. FIG. 2 is an external perspective view of a multi-head head shown in FIG. 1. FIG. 3 is a perspective view showing an example of an inkjet recording device. 61: Wiping member 62: Cap 63: Ink absorber 64: Ejection recovery section 65: Recording head 66: Carriage Patent applicant Canon Corporation Fig. 1(a) B Fig. 1(b) Fig. 2 Fig. 3

Claims (7)

[Claims] (1) A recording material having a base material and an ink-receiving layer provided on the base material, wherein the ink-receiving layer contains ultrafine powder of a transition metal oxide. (2) The recording material according to claim 1, wherein the ultrafine transition metal oxide powder contains at least one of cerium oxide, zinc oxide, titanium oxide, and yttrium oxide. (3) The average particle size of the transition metal oxide ultrafine powder is 0.
．． The recording material according to claim 1, which has a thickness of 1 μm or less. (4) The recording material according to claim 1, wherein the ink-receiving layer mainly comprises a pigment. (5) The average particle size of the transition metal oxide ultrafine powder is 0.
．． 2. The recording material according to claim 1, which has a thickness of 0.001 to 0.01 μm. (6) An inkjet recording method, characterized in that recording is performed on the recording material according to claim 1 by ejecting ink from an orifice of an inkjet recording head in accordance with a recording signal. (7) The inkjet recording method according to claim 3, wherein the ink is ejected using thermal energy.