JP2003300376A - Recording medium - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a recording medium which moderates the color fading/ discoloration of a recorded image over time for a long period and makes available a recorded material with a comparatively well maintained color balance in the image, and a method for manufacturing the recording medium. <P>SOLUTION: In the recording medium comprising a base material and an ink receiving layer which contains at least an ink-absorptive microparticle and a cationic polymer, an ageing treatment such as light exposure and/or oxidation which moderates a change in the optical density to time of the image recorded in a dye or a pigment contained in an ink absorbed in the ink receiving layer, is applied. The image recorded in the recording medium subjected to the ageing treatment is kept in a high-quality image condition where its qualitative deterioration is moderated for a long time and its color balance is retained as a whole. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention provides a recorded matter which is excellent in light resistance and gas resistance and which shows a stable state of characters and / or images (hereinafter referred to as “image”) for a long period of time. The present invention relates to a possible recording medium and a manufacturing method thereof.

[0002]

2. Description of the Related Art In recent years, due to the innovative progress of ink jet recording technology, the quality of images printed on a printing medium by an ink jet printing apparatus has been improved and it has become possible to output high quality images comparable to silver halide photographs. Has become. But,
Dyes or pigments which are coloring materials used in the output of high-quality images, ultraviolet light, light, ozone, such as visible light, NO _X, S
O _X, disadvantage of easily degraded by an oxidizing gas such as H ₂ S, i.e., have the disadvantage of poor weatherability (light resistance and gas resistance). For this reason, a recorded matter in which an image is inkjet-recorded on a recording medium using an ink containing a dye and / or a pigment has poor weather resistance and is not only in an environment exposed to strong light, but also strong in a room or the like. There is a problem that fading / discoloration of a recorded image with time occurs even in an environment where it is hardly exposed to light, that is, storage stability is inferior, and in this respect it still falls short of silver salt photography. In particular, an image recorded using color ink has a drawback that the color balance is lost during recording and after being stored for a long period of time because the state of deterioration varies depending on the color material, resulting in deterioration of image quality. It was Conventionally, as a method for solving the problem of the storability of recorded matter as described above, a method has been performed in which the ink contains a light resistance improver such as an ultraviolet absorber and a gas resistance improver such as an antioxidant. ing.

On the other hand, an ink jet recording medium has conventionally been formed with an ink receiving layer containing ink-absorbing fine particles, a cationic polymer, etc. on a substrate.
In recent years, in order to increase the ink absorbency of a recording medium in response to the increase in the speed of ink jet recording, the ink absorbable fine particles contained in the ink receiving layer have been further miniaturized. Therefore, the permeation of the above-mentioned oxidizing gas through the ink receiving layer is improved, and it becomes more susceptible to the deterioration of the dye or pigment in the ink absorbed by the oxidizing gas. Therefore, a method of allowing a similar weather resistance improver to exist in the ink receiving layer is also used.

[0004]

However, the methods using these weather resistance improvers have not been able to achieve a sufficient effect. On the other hand, it was found that the cationic polymer contained in the ink receiving layer had some influence on the deterioration of the dye or pigment in the ink absorbed in the ink receiving layer. In particular, it was found that the influence of the ink-absorbing fine particles contained in the ink receiving layer increased as the particles became finer.
It has been found that such deterioration of the dye or pigment due to the cationic polymer can be alleviated to some extent by subjecting the recording medium having the ink receiving layer to an aging treatment.

Therefore, the present invention has been made in view of the above knowledge, and the purpose thereof is to:
It is an object of the present invention to provide a recording medium and a method for producing the same, which can provide a recorded matter in which fading / discoloration of a recorded image over time is alleviated and the color balance of the image is relatively maintained. .

[0006]

The present inventors have found that when a dye or pigment in the ink absorbed in the ink receiving layer comes into contact with a cationic polymer present in the ink receiving layer, the dye or the pigment is absorbed between the two. Some reaction occurs, and as a result, the dye or pigment is gradually deteriorated. Such deterioration is caused by irradiation of the ink receiving layer with ultraviolet light, infrared light, visible light, and / or ozone, NO. _The present invention has been completed by discovering that it can be relaxed by subjecting an oxidizing gas such as _X , SO _X and H ₂ S to an oxidizing treatment, and the present invention has been completed. By performing the above, it is possible to obtain a recorded matter in which fading / discoloration with time is alleviated and the color balance of the image is maintained.

That is, the recording medium according to the present invention is a recording medium having a substrate and at least an ink receiving layer, and the time of an image recorded by the dye or pigment in the ink absorbed in the ink receiving layer. Is subjected to an aging treatment for alleviating a change in optical density with respect to.

Further, the recording medium according to the present invention is characterized in that the aging process is a process performed until a change in optical density with time of a recorded image is substantially eliminated.

The recording medium according to the present invention is characterized in that the aging treatment is light irradiation and / or oxidation treatment.

The recording medium according to the present invention is characterized in that the oxidation treatment is a treatment with an oxidizing gas.

Further, the recording medium according to the present invention is characterized in that the ink receiving layer contains at least ink absorbing fine particles and a cationic polymer.

Further, the method for producing a recording medium according to the present invention provides an image recorded on a recording medium having a substrate and at least an ink receiving layer by the dye or pigment in the ink absorbed in the ink receiving layer. It is characterized in that an aging treatment is carried out to reduce a change in optical density with respect to time.

Further, the method of manufacturing a recording medium according to the present invention is characterized in that the aging treatment is performed until the change in the optical density with respect to the time of the recorded image is substantially eliminated.

The method of manufacturing a recording medium according to the present invention is characterized in that the aging treatment is light irradiation and / or oxidation treatment.

Further, the method for producing a recording medium according to the present invention is characterized in that the aging treatment is light irradiation and / or oxidation treatment in the process of forming the ink receiving layer.

The recorded matter according to the present invention is characterized by being recorded on any one of the above recording media.

[0017]

BEST MODE FOR CARRYING OUT THE INVENTION According to the present invention, a recording medium is subjected to aging treatment such as light irradiation and / or oxidation treatment so that the dye or pigment is deteriorated by the cationic polymer contained in the ink receiving layer. That is, it is characterized by alleviating a change in optical density with respect to time. It is preferable to perform the aging treatment on the recording medium until "a state in which the change in the optical density with time of the recorded image is substantially eliminated". The "state in which the change in the optical density with respect to the time of the recorded image is substantially eliminated" was placed under the condition that the light energy irradiation amount was 10 kJ / m ² or the exposure amount of the oxidizing gas was 1 ppm. When the optical density is measured in the state, the change in the optical density per time required to reach each condition is 0.02 or less.
For example, when the time under which the light energy irradiation amount is 10 kJ / m ² is 10 hours, the change in the optical density per 10 hours is 0.02 or less. When exposed to both light energy and exposed to oxidizing gas, when the optical density is measured under the conditions of half each, it is necessary to reach each condition. The change in optical density per sum of the
It means a state of 0.02 or less.

The recording medium to be subjected to aging treatment such as light irradiation and / or oxidation treatment of the present invention has at least a substrate and an ink receiving layer containing ink-absorbing fine particles, cationic polymer and the like. The medium may have a gloss layer, an ultraviolet absorbing layer, and the like in addition to the medium.

As the base material of the recording medium, a sheet-like material made of paper or plastic is used, and either a light-transmitting material or a light-impermeable material is used. As such a substrate, any conventionally known substrate can be used,
For example, the paper is a sheet containing a fibrous substance and, if necessary, a filler, and any of the papers produced by the conventionally known acidic papermaking method or neutral papermaking method with an appropriate sizing agent within the above range can be used. . Further, as the plastic sheet, a sheet made of polyester resin, diacetate resin, triacetate resin, acrylic resin, polycarbonate resin, polyvinyl chloride resin, polyimide resin, cellophane, celluloid, etc. The thing of the shape is mentioned.

The ink receiving layer formed on the substrate contains known fine particles for improving the ink absorbability of the film-forming material, and a cationic polymer for capturing and fixing the dye or pigment in the ink. However, it may be formed by adding other additives such as an ultraviolet absorber, a surfactant, a penetrant, a water retention agent, a foam suppressor, and a colorant, if necessary. The ink receiving layer may have a single-layer structure or a multi-layer structure.

As the film forming material, the following natural resins and synthetic resins are used. That is, polyvinyl alcohol, albumin, gelatin, casein, starch, khaotin starch, gum arabic, natural resin such as sodium alginate, polyamide, polyacrylamide, polyvinylpyrrolidone, polyvinylpyrrolidone tetrachloride, polyethyleneimine, polyvinylpyridium halide, melamine resin, Synthesis of polyurethane, carboxymethyl cellulose, polyvinyl alcohol, polyester, sodium polyacrylate, RBS latex, NBR latex, polyvinyl formal, polymethyl methacrylate, polyvinyl butyral, polyacrylonitrile, polyvinyl chloride, polyvinyl acetate, phenol resin, alkyd resin, etc. Resin is used.

The fine particles for further improving the ink absorbability include, for example, light calcium carbonate, heavy calcium carbonate, magnesium carbonate, kaolin, talc, calcium sulfate, barium sulfate, titanium dioxide, zinc oxide, zinc sulfide. , Zinc carbonate, chisan white, aluminum silicate, diatomaceous earth, calcium silicate, magnesium silicate, synthetic amorphous silica, colloidal silica, alumina, colloidal alumina, pseudo-boehmite, aluminum hydroxide, lithopone, zeolite, hydrohalloysite, magnesium hydroxide White inorganic fine particles such as styrene plastic pigment, acrylic plastic pigment, polyethylene, microcapsule, melamine resin,
Examples include organic fine particles such as urea resin.

As the cationic polymer, a known polymer which dissociates when it is dissolved in water and exhibits a cationic property can be used, but a polymer having a tertiary amino group or a quaternary ammonium group is used. However, acrylic resins with quaternary ammonium groups and sometimes acrylic amines,
A copolymer of (meth) acrylamide and a vinyl-based monomer copolymerizable therewith and containing no carboxyl group is used.

As the aging treatment of light irradiation, ultraviolet ray irradiation treatment, infrared ray irradiation treatment, natural light (sunlight) treatment, X
A treatment with light such as a ray irradiation treatment can be used. This aging treatment of light irradiation may be performed under heating or may be performed in the process of forming the ink receiving layer. The light irradiation is preferably carried out in a state where the surface of the ink receiving layer is uniformly irradiated with energy of 10 to 100 J / m ² , although it depends on the kind of the cationic polymer, the kind of light, and the processing condition.

The aging treatment of the oxidation treatment is preferably carried out by leaving it in an oxidizing gas, spraying an oxidizing gas or the like, but any oxidizing treatment may be used. The oxidizing gas used in the oxidation treatment, ozone, active oxygen, NO _X, SO _X, but H ₂ S and the like, may be performed by other oxidizing gases. The aging treatment of this oxidation treatment may be performed under heating,
It may be performed in the process of forming the ink receiving layer.

Aging treatment such as light irradiation or oxidation treatment
By being performed under heating and / or in the process of forming the ink receiving layer, the effect of aging treatment such as light irradiation or oxidation treatment is enhanced, and the recording medium is in a state where “the change in the optical density with time substantially disappears”. It can be said that. Of course, the light irradiation and the aging treatment of the oxidation treatment may be performed together.

The recording medium that has been subjected to the aging treatment of light irradiation and / or oxidation treatment as described above is also preferable as a recording medium for ink jet recording. A printed matter recorded using such a recording medium maintains a stable image state with color balance as a whole because fading / discoloration is alleviated over a long period of time.

The ink used for recording on the recording medium of the present invention includes dyes such as C.I. I. Direct Red 2,4,9,23,26,31,39,
62, 63, 72, 75, 76, 79, 80, 81, 8
3,84,89,92,95,111,173,18
4,207,211,212,214,218,22
1,223,224,225,226,227,23
2,233,240,241,242,243,24
7, C.I. I. Direct Violet 7,9,47,4
8, 51, 66, 90, 93, 94, 95, 98, 10
0, 101, C.I. I. Direct Yellow 8, 9, 1
1, 12, 27, 28, 29, 33, 35, 39, 4
1,44,50,53,58,59,68,86,8
7,93,95,96,98,100,106,10
8, 109, 110, 130, 132, 142, 14
4,161,163, C.I. I. Direct Blue 1,1
0,15,22,25,55,67,68,71,7
6,77,78,80,84,86,87,90,9
8, 106, 108, 109, 151, 156, 15
8, 159, 160, 168, 189, 192, 19
3,194,199,200,201,202,20
3,207, 211, 213, 214, 218, 22
5,229,236,237,244,248,24
9,251,252,264,270,280,28
8,289,291, C.I. I. Direct black 9,
17, 19, 22, 32, 51, 56, 62, 69, 7
7, 80, 91, 94, 97, 108, 112, 11
3,114,117,118,121,122,12
5,132,146,154,166,168,17
8,199,

C. I. Acid Red 35, 42, 5
2,57,62,80,82,111,114,11
8,119,127,128,131,143,15
1,154,158,249,254,257,26
1,263,266,289,299,301,30
5,336,337,361,396,397, C.I.
I. Acid Violet 5,34,43,47,4
8, 90, 103, 126, C.I. I. Acid Yellow 17, 19, 23, 25, 39, 40, 42, 44, 4
9, 50, 61, 64, 76, 79, 110, 127,
135,143,151,159,169,174,1
90, 195, 196, 197, 199, 218, 21
9, 222, 227, C.I. I. Acid Blue 9,2
5,40,41,62,72,76,78,80,8
2, 92, 106, 112, 113, 120, 127:
1,129,138,143,175,181,20
5,207,220,221,230,232,24
7,258,260,264,271,277,27
8, 279, 280, 288, 290, 326, C.I.
I. Acid Black 7,24,29,48,52:
1,172,

C. I. Reactive Red 3,13,1
7, 19, 21, 22, 23, 24, 29, 35, 3
7, 40, 41, 43, 45, 49, 55, C.I. I. Reactive Violet 1,3,4,5,6,7,8,
9, 16, 17, 22, 23, 24, 26, 27, 3
3,34, C.I. I. Reactive Yellow 2,3,1
3,14,15,17,18,23,24,25,2
6,27,29,35,37,41,42, C.I. I. Reactive blue 2,3,5,8,10,13,14,
15, 17, 18, 19, 21, 25, 26, 27, 2
8, 29, 38, C.I. I. Reactive black 4,
5,8,14,21,23,26,31,32,34,
C. I. Food black 1, 2,

C. I. Basic Red 12,13,1
4,15,18,22,23,24,25,27,2
9, 35, 36, 38, 39, 45, 46, C.I. I. Basic Violet 1,2,3,7,10,15,1
6,20,21,25,27,28,35,37,3
9, 40, 48, C.I. I. Basic Yellow 1, 2,
4,11,13,14,15,19,21,23,2
4, 25, 28, 29, 32, 36, 39, 40, C.I.
I. Basic Blue 1,3,5,7,9,22,2
6,41,45,46,47,54,57,60,6
2,65,66,69,71, C.I. I. Examples of the ink include Basic Black 8 and the like.

As the pigment, for example, titanium oxide,
In addition to iron oxide, inorganic pigments such as carbon black produced by known methods such as contact method, furnest method and thermal method; azo pigments (including azo lake, insoluble azo pigment, condensed azo pigment, chelate azo pigment, etc.) , Polycyclic pigments (for example, phthalocyanine pigments, berylene pigments,
Berynone pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, thioindigo pigments, isoindolinone pigments, quinofuraron pigments, etc.), dye chelates (for example, basic dye type chelates, acid dye type chelates, etc.), nitro pigments, nitroso pigments, aniline An ink containing an organic pigment such as black may be used.

[0033]

Next, examples of the present invention will be given together with comparative examples.
The present invention will be specifically described, but the present invention is not limited to the following examples.

(Preparation of Recording Medium) The following coating liquid for forming an ink receiving layer was applied to a high-quality paper having a basis weight of 100 g / m ^{2 so} that the dry film thickness was 20 μm, and dried to form an inkjet recording. Medium A was prepared. Silica fine particles (Mizukasil P-50: manufactured by Mizusawa Chemical Co., Ltd.) 15 parts by weight Polyvinyl alcohol (PVA217: manufactured by Kuraray Co., Ltd.) 10 parts by weight Cationic polymer (PAL-2 (solid content 20%) manufactured by Senka Co.) 25 parts by weight Ion-exchanged water 170 parts by weight

Example 1 The inkjet recording medium A was irradiated with UV light until the total irradiation energy amount reached 500 kJ / m ^2, and the aging-processed recording medium 1 was recorded.
Got

[Example 2] An aging-processed recording medium 2 was obtained in the same manner as in Example 1 except that the irradiation with UV light was carried out under heating at 70 ° C.

Example 3 The inkjet recording medium A was left in an ozone atmosphere of 10 ppm for 24 hours to obtain an aging-treated recording medium 3.

Example 4 An aging-processed recording medium 4 was obtained in the same manner as in Example 3 except that an active oxygen atmosphere was used instead of an ozone atmosphere.

[Embodiment 5] NO in place of ozone atmosphere
An aging-processed recording medium 5 was obtained in the same manner as in Example 3 except that the atmosphere was ₂ atmospheres.

[Embodiment 6] SO in place of ozone atmosphere
An aging-processed recording medium 6 was obtained in the same manner as in Example 3 except that the atmosphere was changed to ₂ .

[Embodiment 7] H ₂ instead of ozone atmosphere
An aging-processed recording medium 7 was obtained in the same manner as in Example 3 except that the S atmosphere was used.

[Comparative Example 1] The above-mentioned ink jet recording medium A (non-aging treated recording medium).

The following tests were conducted on the aging-processed recording media obtained in each of the above examples and the non-aging-processed recording media of the comparative examples, and the results are shown in Table 1. <Weather resistance test> Using the inkjet printer FM800C manufactured by Seiko Epson Co., Ltd., printing was performed on the aging-treated recording media 1 to 8 and the non-aging-treated recording media of Comparative Examples so that the magenta color had a reflection optical density of 1.0.
The UV light dose per day for each printed sample is 10 kJ /
Irradiate for 10 days as m ² , total irradiation energy 100k
A weather resistance test was conducted on two cases, one for UV light irradiation up to J / m ² and the other for 10 hours in an ozone atmosphere of 1 ppm, and the change in reflection optical density before and after the test was measured by the Gretag spectrophotometer. It was observed using a total SPM100-II.

[0044]

[Table 1]

From the results shown in Table 1, the recorded matter using the aging-treated recording medium of the example of the present invention was irradiated with light and oxidized gas as compared with the recorded matter using the unaged-treated recording medium of the comparative example. It can be seen that there is little influence, there is substantially no deterioration of the image, and the high quality image state in which the color balance as a whole is maintained is maintained.

[0046]

INDUSTRIAL APPLICABILITY As described in detail above, the present invention provides a recording medium having at least an ink-absorbing layer containing a substrate and at least ink-absorbing fine particles and a cationic polymer. By performing aging treatment such as / or oxidization treatment, it is possible to obtain a recording medium in which deterioration due to light and oxidizing gas is mitigated. In addition, the recorded matter recorded using the recording medium subjected to such an aging treatment, image deterioration is mitigated over a long period of time,
It has an excellent effect of maintaining a high-quality image state in which the color balance as a whole is maintained.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) B41J 2/01 B41J 3/04 101Y F term (reference) 2C056 EA13 FC06 2H086 BA01 BA02 BA05 BA15 BA33 BA35 BA37 4D075 BB21Z BB41Z BB73Z BB78Z CA32 CA33 CA35 CA47 DA04 DB18 DB32 DB38 DB40 DB43 DB48 DB53 DC27 EB07 EB12 EB13 EB14 EB15 EB22 EB32 EB36 EB39 EC03

Claims (15)

[Claims] 1. A recording medium having a base material and at least an ink receiving layer, wherein a change in optical density with time of an image recorded by a dye or pigment in the ink absorbed in the ink receiving layer is mitigated. A recording medium which has been subjected to an aging treatment. 2. The recording medium according to claim 1, wherein the aging process is a process that is performed until a change in optical density with time of a recorded image is substantially eliminated. 3. The recording medium according to claim 1, wherein the aging treatment is light irradiation and / or oxidation treatment. 4. The recording medium according to claim 1, wherein the aging treatment is light irradiation under heating and / or oxidation treatment. 5. The aging treatment is light irradiation and / or oxidation treatment in the ink receiving layer forming process.
Or the recording medium according to 2. 6. The recording medium according to claim 3, wherein the oxidation treatment is a treatment with an oxidizing gas. 7. The oxidizing gas is ozone, active oxygen,
The recording medium according to claim 6, which is NO _X , SO _X , or H ₂ S. 8. The recording medium according to claim 1, wherein the ink receiving layer contains at least ink absorbing fine particles and a cationic polymer. 9. The inkjet recording method according to claim 1,
The recording medium described in. 10. An aging treatment for reducing a change in optical density with time of an image recorded on a recording medium having a substrate and at least an ink receiving layer by the dye or pigment in the ink absorbed in the ink receiving layer. A method for manufacturing a recording medium, which comprises: 11. The method of manufacturing a recording medium according to claim 10, wherein the aging process is a process performed until a change in optical density with time of a recorded image is substantially eliminated. 12. The aging treatment comprises light irradiation and / or
Alternatively, the method for producing a recording medium according to claim 10 or 11, which is an oxidation treatment. 13. The method for producing a recording medium according to claim 10, wherein the aging treatment is light irradiation and / or oxidation treatment in the ink receiving layer forming process. 14. The method of manufacturing a recording medium according to claim 12, wherein the oxidation treatment is a treatment with an oxidizing gas. 15. A recorded matter recorded on the recording medium according to claim 1.