JP2000158802A - Ink jet recording sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To facilitate recording with excellent light resistance durable against a long period preservation by incorporating a gelatin, an ultraviolet absorbent and an antioxidant in an ink receptive layer provided at least on one surface of a support. SOLUTION: The ink jet recording sheet comprises an ink receptive layer containing a gelatin, an ultraviolet absorbent and an antioxidant. The gelatin, absorbent and antioxidant are preferably contained in the same layer and uppermost layer. Particularly, in a preferred embodiment, two or more layers are constituted, and the uppermost layer contains the gelatin, the absorbent and the antioxidant. When a benzotriazole derivative or hindered amine derivative is used as the absorbent, its light resistance is particularly upgraded. As the antioxidant, a phenol antioxidant is preferable. Further, the antioxidant/ ultraviolet absorbent ratio (by weight) is preferably about 1/20 to 1/5. Thus, the light resistance is remarkably improved.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an ink jet recording sheet mainly using a coloring material, and more particularly to an ink jet recording sheet excellent in light resistance of a recorded image.

[0002]

2. Description of the Related Art Ink jet recording is free of noise and is capable of high-speed printing. Further, by using a plurality of ink nozzles, it is easy to perform multi-color recording, and multi-color ink jet recording is performed by various ink jet recording methods. In particular, use of an ink jet printer capable of forming a complex image quickly and accurately has attracted attention as a hard copy creation device for image information such as characters, various figures, and photographs created by a computer. Further, image information created by these computers is recorded on a transparent recording sheet by an ink jet printer, and this is also used as a document such as an OHP (overhead projector). In recent years, the application fields of inkjet printers, which have attracted special attention, include the use of color printing in the printing field where image quality close to photographs is required, the output of design images in the design department, and the use of large ink jet plotters. Large format posters that can be easily created,
Display, flag, etc. Furthermore, in recent years, digital photographic images have become familiar, as represented by digital cameras, and attempts have been made to output these images with inexpensive inkjet printers. Inkjet printers equipped with a dedicated mode and ink for photography have also been released. I have.

[0003] Ink-jet recording papers are required to have not only high-speed absorptivity, high absorption capacity, high-density printing and improved image quality of ink, but also higher characteristics of light resistance and water resistance of printed matter. Was.

In particular, large-sized ink jet recording paper for ink jet plotters is often posted indoors or outdoors after laminating, and light resistance that can withstand long-term storage has been regarded as important.

[0005] Recording sheets used in the ink jet recording method are described in JP-A-55-51583, JP-A-56-157, JP-A-57-107879, and JP-A-57-1.
No. 07880, No. 59-230787, No. 62-16
Nos. 0277, 62-184879, 62-183
As disclosed in JP-A-382-382 and JP-A-64-11877, a recording material obtained by applying a silicon-containing pigment such as silica having excellent ink absorption and retention properties to a paper support together with an aqueous binder has been proposed. ing.

Further, all of the above-mentioned methods can improve the ink absorbency and the coloring ability, but are inferior in water resistance. As a method for solving such a defect, a polycationic polymer electrolyte as disclosed in JP-A-56-84792 and a basic latex or the like as disclosed in JP-A-57-36692 are used in an ink image receiving layer. Is known. However, the light resistance was poor because the cationic substance accelerated the photodecomposition of the ink dye.

[0007] In order to improve such a disadvantage, a method of incorporating a cationic substance with low photodecomposition is disclosed in JP-A-60-1138.
Japanese Patent Application Laid-Open No. 57-741 discloses a method of incorporating an ultraviolet absorber such as a benzophenone type or a benzotriazole type in JP-A-9-79.
No. 93, JP-A-57-87988, JP-A-9-2
Japanese Patent Application Laid-Open No. Sho 61-146913 discloses a method of incorporating a hindered amine-based antioxidant in Japanese Patent No. 54522, and Japanese Patent Application Laid-Open No. 9-309260 discloses a method of incorporating a UV absorber and silicone oil. It has not yet achieved a sufficient effect.

[0008]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide an ink-jet recording sheet which can withstand long-term storage and which provides ink-jet recording with excellent light resistance.

[0009]

An object of the present invention is to provide an ink jet recording sheet having an ink receiving layer provided on at least one surface of a support, wherein the ink receiving layer contains gelatin, an ultraviolet absorber and an antioxidant. This is achieved by an ink jet recording sheet characterized in that:

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
In the ink jet recording sheet of the present invention, it was found that the ink receiving layer contained gelatin, an ultraviolet absorber and an antioxidant in the ink receiving layer, thereby significantly improving the light fastness when printing with a water-soluble dye ink. Invented the invention.

It is preferable that gelatin, an ultraviolet absorber and an antioxidant are contained in the same layer, and more preferably that they are contained in the uppermost layer. In the present invention, a particularly preferred embodiment is a two- or more-layer structure, and gelatin,
Including an ultraviolet absorber and an antioxidant.
In this case, it is best to use a combination of gelatin, an ultraviolet absorber and an antioxidant only in the uppermost layer.

In the case of the above-mentioned two or more layer constitution, a layer mainly composed of a water-soluble polymer (eg, gelatin, carboxymethylcellulose, polyvinylpyrrolidone, etc.) or a pigment (eg, silicon oxide, aluminum oxide) , Zeolite, etc.). From the viewpoint of light resistance, the lower ink receiving layer is preferably a layer using a water-soluble polymer.

Usually, since the ultraviolet absorber and the antioxidant are insoluble in water, they are dissolved in a high-boiling solvent or the like and contained in a form emulsified and dispersed using a protective colloid.
This is a factor that lowers ink absorbency and gloss. Therefore,
It is preferable that the light resistance can be effectively improved with a small amount of the ultraviolet absorber and the antioxidant, and such effects can be obtained by using the ultraviolet absorber and the antioxidant in the uppermost layer. Further, by using gelatin as a binder, the light resistance is effectively improved, so that the amounts of the ultraviolet absorber and the antioxidant can be reduced. In addition, it was found that in combination of gelatin, an ultraviolet absorber and an antioxidant, the ratio of antioxidant / ultraviolet absorber (weight ratio) is preferably 1/20 to 1/5.

Further, when the support is a transparent film, the support is affected by ultraviolet rays, sunlight and the like not only from the ink receiving layer side but also from one side different from the ink receiving layer. Therefore, in the present invention, when the support is a transparent film,
It is preferable to include an ultraviolet absorber on one side different from the ink receiving layer. In this case, the structure may be the same as the uppermost layer on the ink receiving layer side. That is, a layer containing gelatin, an ultraviolet absorber and an antioxidant is provided on the back surface. Thereby, the same coating liquid can be used.

In the present invention, an ultraviolet absorber refers to a substance that absorbs ultraviolet light, converts its energy into mainly harmless heat energy, and does not alter itself.

The UV absorbers include 2- (5-methyl-2)
-Hydroxyphenyl) benzotriazole, 2-
(3,5-di-t-butyl-2-hydroxyphenyl)
Benzotriazole (TINUVIN320, manufactured by Ciba Specialty Chemicals), 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3-dodecyl-5-methyl-) 2-hydroxyphenyl) benzotriazole (T
Benzotriazole derivatives such as INUVIN171, manufactured by Ciba Specialty Chemicals), benzophenone derivatives such as 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, and 2-hydroxy-4-n-octyloxybenzophenone;
There are salicylic acid derivatives such as phenyl salicylate and acrylate derivatives such as 2-ethylhexyl-2-cyano-3,3′-diphenyl acrylate. The hindered amine derivatives include N, N'-bis (3-aminopropyl) ethylenediamine-2,4-bis [N-butyl-N- (1,2,2,6,6-pentamethyl-4-). Piperidyl) amino] -6-chloro-1,3,5-triazine condensate (CHIMASSORB 119, manufactured by Ciba Specialty Chemicals), bis (1,2,2,2)
6,6-pentamethyl-4-piperidinyl) sebacate, bis (1,2,2,2- (3,5-di-t-butyl-4-hydroxybenzyl) -2-n-butylmalonate)
6,6-pentamethyl-4-piperidyl) (TINUV
IN144, Ciba Specialty Chemicals)
and so on.

In the present invention, light resistance is particularly improved when a benzotriazole derivative or a hindered amine derivative is used.

As the antioxidant, known antioxidants can be used, and phenolic antioxidants as shown below are particularly preferable. Specific examples of the phenolic antioxidant include relatively low-molecular-weight 2,5-bis (1 ′, 1 ′, 3 ′, 3′-tetramethylbutyl) hydroquinone (88HQ, manufactured by Fuji Film) and the like. Hydroquinone derivative, triethylene glycol-bis [3- (3-t-butyl-5-methyl-hydroxyphenyl) propionate] (IRGANOX245, manufactured by Ciba Specialty Chemicals), pentaerythrityl-tetrakis [3- (3 , 5-Di-t-butyl-
4-hydroxyphenyl) propionate] (IRGA
NOX1010, manufactured by Ciba Specialty Chemicals) 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl)
Benzene (IRGANOX1330, manufactured by Ciba Specialty Chemicals), isooctyl-3- (3,5
And hindered phenol derivatives such as -di-t-butyl-4-hydroxyphenyl) propionate (IRGANOX1135, manufactured by Ciba Specialty Chemicals). In addition, these phenolic antioxidants,
Further, a phosphorus-based antioxidant such as tris (2,4-di-t-butylphenyl) phosphite and a sulfur-based antioxidant such as 3,3′-thiobispropionic acid didodecyl ester can be used in combination.

The antioxidant / ultraviolet absorber ratio (weight ratio) used in the present invention is preferably from 1/20 to 1/5, and a small amount of the antioxidant to the ultraviolet absorber is contained in the same layer. By doing so, a synergistic effect is achieved and the light fastness is much improved compared to the case where the ultraviolet absorber is used alone.

These ultraviolet absorbers and antioxidants are:
After being dissolved in a high boiling point solvent, it is mixed with an emulsifier and a protective colloid, and coated in an emulsified and dispersed form. When the ultraviolet absorber or antioxidant is originally oily, it is not necessary to dissolve it in a solvent having a high boiling point.

The high boiling solvent used in the present invention includes di-n-butyl phthalate, benzyl phthalate, triphenyl phosphate, triphenyl phosphate, etc., but is not particularly limited.

The protective colloid is, for example, gelatin,
Polyvinyl alcohol, oxidized starch, hydroxyethylcellulose, carboxymethylcellulose, methylcellulose, sodium polyacrylate, guar gum and the like are used. In the present invention, gelatin having good light resistance is used.

The ink jet recording sheet of the present invention comprises:
An ink receiving layer containing gelatin is provided on at least one side of the support as described above, and after the applied ink receiving layer coating liquid is once brought into a gel state, it is dried by a so-called cold drying method of drying at a low temperature. An ink receiving layer.

As the gelatin to be used in the present invention, any gelatin can be used as long as it is made of animal collagen, but gelatin made of collagen made of pig skin, cow skin and cow bone is preferred. There is no particular limitation on the kind of gelatin, but lime-treated gelatin, acid-treated gelatin, and gelatin derivatives (for example, Japanese Patent Publication No. Sho 38-4)
No. 854, No. 39-5514, No. 40-1223
7, No. 42-26345, U.S. Pat.
No. 53, No. 2594293, No. 2614928
No. 2763639, No. 3118766, No. 3132945, No. 3186846, No. 33
12553, British Patent Nos. 8661414 and 103
3189) can be used alone or in combination thereof. Particularly preferably, the ratio of the α-chain component in the molecular weight distribution of gelatin is 4%.
0% or more gelatin.

The gelatin used in the present invention has a jelly strength (based on a PAGI method and a bloom-type jelly strength meter) of preferably 150 g or more, particularly preferably 200 to 300 g.

In the present invention, the coating amount of gelatin contained in the ink receiving layer is 3 to 50 g / solid content.
m ² is preferable, and more preferably 5 to 30 g / m ² . If the ink receiving layer is less than 3 g / m ² , the ink receiving property is poor, and the ink overflows from the receiving layer after printing. Further, when the amount exceeds 50 g / m ² , the ink receptivity is improved, but problems such as cracking and curling occur.

In the present invention, the following water-soluble polymer can be used in combination with gelatin as a binder for the purpose of improving ink receptivity and dot reproducibility in the ink receiving layer. Examples of the water-soluble polymer to be used in combination include, for example, polyvinyl formal such as polyvinyl alcohol, polyvinyl pyrrolidone, polyvinyl pyridinium halide, various modified polyvinyl alcohols and derivatives thereof (JP-A-60-145879, JP-A-60-220750,
No. 61-143177, No. 61-235182
No. 61-235183 and No. 61-23768
No. 1, No. 61-26089), polyacrylamide, polydimethylacrylamide, polydimethylaminoacrylate, sodium polyacrylate, methacrylic acid copolymer salt, polysodium methacrylate, vinyl acrylate copolymer Polymers containing an acryl group such as a salt (Japanese Patent Application Laid-Open Nos.
Natural polymers such as starch, oxidized starch, carboxyl starch, dialdehyde starch, cationized starch, dextrin, sodium alginate, gum arabic, casein, pullulan, dextran, methylcellulose, ethylcellulose, carboxymethylcellulose, and hydroxypropylcellulose. Or derivatives thereof (JP-A-59-174382, JP-A-60-262885,
No. 61-143177, No. 61-181679
No. 61-193879, No. 61-28778
No. 2), synthetic polymers such as polyethylene glycol, polypropylene glycol, polyvinyl ether, polyglycerin, alkyl vinyl ether maleate copolymer, N-vinyl pyrrole maleate copolymer, styrene maleic anhydride copolymer, and polyethylene imine. JP-A-61-32787, JP-A-61-237680 and JP-A-61-277483).

In the present invention, the ratio (weight ratio) of the water-soluble polymer used in combination with gelatin varies depending on the type of the water-soluble polymer used in combination. The polymer / gelatin ratio (weight ratio) is preferably 5/95 to 80/20, more preferably 10/90 to 70/30, and the light fastness is not deteriorated.

In the present invention, a surfactant may be added to the ink receiving layer in order to improve dot reproducibility in addition to the binder. The surfactant used may be any of anionic, cationic, nonionic and betaine types, and may be of low molecular weight or high molecular weight. One or two or more surfactants are added to the ink receiving layer coating liquid. When two or more surfactants are used in combination, an anionic surfactant and a cationic surfactant are used in combination. It is not preferable. The addition amount of the surfactant is preferably 0.001 g to 5 g, more preferably 0.01 to 3 g, per 100 g of the binder constituting the ink receiving layer.

As described above, in the present invention, a pigment can be used in the lower ink receiving layer in a two or more layer structure. As a specific example, zeolite, kaolinite, diatomaceous earth, silicic anhydride, aluminum silicate, calcium silicate, silicon oxide or porous silicon oxide, aluminum oxide or porous aluminum oxide can be used.

Examples of the pigment adhesive include sodium polyacrylate, styrene-maleic anhydride copolymer, ethylene-maleic anhydride copolymer, polyvinyl alcohols,
Polyethyleneimine, methylcellulose, polyvinylpyrrolidone, basic latex polymer and the like can be used.

In the present invention, the ink receiving layer may be added with a fixing agent or hardened with an appropriate hardening agent for the purpose of improving water resistance and dot reproducibility. Specific examples of the hardener include aldehyde compounds such as formaldehyde and glutaraldehyde, ketone compounds such as diacetyl and chloropentanedione, bis (2-chloroethylurea), 2-hydroxy-4,6-dichloro-1. ,
3,5 triazine, a compound having a reactive halogen as described in U.S. Pat. No. 3,288,775, divinyl sulfone, a compound having a reactive olefin as described in U.S. Pat. No. 3,635,718, N-type as described in U.S. Pat. No. 2,732,316. Methylol compounds, U.S. Pat.
Isocyanates as described in No. 37, US Pat.
Aziridine compounds as described in US Pat. Nos. 7280 and 2983611, carbodiimide-based compounds as described in US Pat. No. 3,100,704, epoxy compounds as described in US Pat. No. 3,091,537, aziridine derivatives, halogen carboxaldehydes such as mucochloric acid, There are dioxane derivatives such as dihydroxydioxane, inorganic hardeners such as chrome alum, potassium alum, and zirconium sulfate, and these can be used alone or in combination of two or more. The addition amount of the hardener is preferably 0.01 g to 10 g, more preferably 0.1 to 5 g, per 100 g of the binder constituting the ink receiving layer.

In the present invention, in addition to the above-mentioned surfactant and hardener, an inorganic pigment, a coloring dye,
Color pigments, ink dye fixing agents, pigment dispersants, defoamers, leveling agents, preservatives, fluorescent brighteners, viscosity stabilizers,
Various known additives such as a pH adjuster can also be added.

Although the ink receiving layer is provided on at least one surface of the support, it may be provided on both surfaces of the support for the purpose of preventing curling.

As the support used in the present invention, a transparent support and an opaque support can be used. As the transparent support, any conventionally known ones can be used, for example, polyester resin, diacetate resin, triacetate resin, acrylic resin, polycarbonate resin, polyvinyl chloride, polyimide resin, cellophane, film or plate of celluloid and the like and A glass plate and the like can be mentioned.

Such a transparent support has a thickness of about 1
It is preferably about 0 to 200 μm. Further, when such a transparent support is used, gelatin, a UV absorber and an antioxidant are added to the ink receiving layer alone by including a gelatin, an ultraviolet absorber and an antioxidant layer on one side different from the ink receiving layer. Light resistance is improved as compared with the case where an agent layer is included. In this case, the UV absorber and the antioxidant layer may be different from those used in the ink receiving layer.

As the opaque support, any conventionally known opaque supports such as paper, coated paper, synthetic paper, resin-coated paper, opaque film containing pigment, and foamed film can be used. Gloss,
Synthetic paper, resin-coated paper, and various films are more preferable from the viewpoint of smoothness, but resin-coated paper similar to a photographic support is more preferable from the feeling of touch and luxury.

The base paper constituting the resin-coated paper preferably used in the present invention is not particularly limited, and generally used paper can be used. More preferably, for example, a base paper used for a photographic support is used. Smooth base paper is preferred. As the pulp constituting the base paper, natural pulp, recycled pulp, synthetic pulp or the like may be used alone or in combination of two or more. This base paper contains sizing agents, paper strength agents, fillers, antistatic agents, fluorescent whitening agents,
Additives such as dyes are blended.

Further, a surface sizing agent, a surface strengthening agent, a fluorescent whitening agent, an antistatic agent, a dye, an anchoring agent and the like may be coated on the surface.

The thickness of the base paper is not particularly limited, but preferably has good surface smoothness, such as compressing the paper by applying pressure during or after paper formation with a calender or the like. 30 to 250 g / m ² is preferred.

As the resin of the resin-coated paper, a polyolefin resin or a resin curable by an electron beam can be used.
Examples of the polyolefin resin are low-density polyethylene, high-density polyethylene, polypropylene, polybutene, a homopolymer of an olefin such as polypentene or a copolymer of two or more olefins such as an ethylene-propylene copolymer and a mixture thereof, Those having various densities and melt viscosity indices (melt index) can be used alone or in combination.

In the resin of the resin-coated paper, white pigments such as titanium oxide, zinc oxide, talc and calcium carbonate; fatty acid amides such as stearic acid amide and arachidic acid amide; zinc stearate; calcium stearate; Aluminum, fatty acid metal salts such as magnesium stearate, antioxidants such as Irganox 1010 and Irganox 1076, blue pigments and dyes such as cobalt blue, ultramarine blue, cecilian blue, and phthalocyanine blue, cobalt violet, fast violet, and manganese purple It is preferable to add various additives such as magenta pigments and dyes, fluorescent brighteners and ultraviolet absorbers in an appropriate combination.

The resin-coated paper, which is preferably used in the present invention, is produced by a so-called extrusion coating method in which a heated and melted resin is cast on a running base paper in the case of a polyolefin resin. Coated. In the case of a resin that is cured by an electron beam, the resin is applied by a commonly used coater such as a gravure coater or a blade coater, and then irradiated with an electron beam to cure and coat the resin. Further, before coating the resin on the base paper, the base paper is preferably subjected to an activation treatment such as a corona discharge treatment or a flame treatment. The surface (surface) of the support on which the ink receiving layer is applied has a glossy surface, a matte surface, and the like, depending on the application, and the glossy surface is used particularly favorably. It is not necessary to coat the back surface with a resin, but it is preferable to coat the resin from the viewpoint of curling prevention. The back surface is usually a matte surface, and the front surface or, if necessary, both front and back surfaces can be subjected to an activation treatment such as a corona discharge treatment or a flame treatment. The thickness of the coating resin layer is not particularly limited, but is generally 5 to 50 μm thick on the surface or on both sides.

The support in the present invention may be coated with various back coat layers for antistatic properties, transport properties, curling prevention properties, and the like. The back coat layer can contain an inorganic antistatic agent, an organic antistatic agent, a hydrophilic binder, a latex, a curing agent, a pigment, a surfactant and the like in an appropriate combination.

[0045]

EXAMPLES The present invention will be described below in detail with reference to examples, but the contents of the present invention are not limited to the examples.
In addition, "parts" means parts by weight.

Example 1 As a support, LBKP (50 parts) and LBSP (50 parts) were used.
Of a pulp blend of 100 g / m ² , a resin composition comprising low-density polyethylene (70 parts), high-density polyethylene (20 parts) and titanium oxide (10 parts) is applied at 25 g / m ^2. And high-density polyethylene (5
0 part) and a resin composition comprising low-density polyethylene (50 parts) at 25 g / m ² was prepared.

The following ink-receiving layer coating solution was applied on the above support using a bar coater so as to have a dry weight of 10 g / m ^2, and dried to prepare an ink jet recording sheet.

<Ink receiving layer coating liquid> 3 parts of TINUVIN 171 as an ultraviolet absorber, 8 parts of ethyl acetate and 0.3 part of IRGANOX 1330 as an antioxidant were added and dissolved, and 3 parts of a 5% nonionic surfactant were added. A solution obtained by adding 30 parts of 10% lime-processed gelatin and adding pure water to make the whole 80 parts was emulsified and dispersed by a homomixer, and further added pure water to obtain 1 part.
00 parts as an ultraviolet absorber emulsion. 10 parts of this UV absorber emulsion and 900% of 10% lime-processed gelatin
Parts and 2 parts of a 5% nonionic surfactant in 100 parts of pure water.
Was dissolved in an ink receiving layer coating solution.

Example 2 The ultraviolet absorber of Example 1 was replaced with TINUVIN 171.
An ink jet recording sheet was prepared in the same manner as in Example 1 except that 5 parts, 0.5 part of TINUVIN 320 and 0.3 part of IRGANOX1335 were used instead of the antioxidant.

Example 3 An ink jet recording sheet was prepared in the same manner as in Example 1 except that the UV absorber in Example 1 was replaced by 3 parts of TINUVIN 171 and the antioxidant was replaced by 0.3 parts of 88HQ.

Example 4 An ink jet recording sheet was prepared in the same manner as in Example 1 except that the UV absorber in Example 1 was replaced by 3 parts of TINUVIN 144 and the antioxidant was replaced by 0.3 part of IRGANOX1010.

Example 5 The 10% lime-treated gelatin of Example 1 was replaced with 10% lime-treated gelatin / 10% carboxymethylcellulose (CMC
5A: 50/5 ratio (by weight) manufactured by Daiichi Kogyo Seiyaku Co., Ltd.
An ink jet recording sheet was prepared in the same manner as in Example 1 except that the value was set to 0.

Comparative Example 1 10% lime-treated gelatin of Example 1 was replaced with 10% carboxymethyl cellulose (CMC5A: Daiichi Kogyo Seiyaku Co., Ltd.)
Except for the above, an ink jet recording sheet was prepared in the same manner as in Example 1.

Comparative Example 2 An ink jet recording sheet was prepared in the same manner as in Example 1 except that the 10% lime-treated gelatin in Example 1 was replaced with 10% polyvinyl alcohol (PVA117: manufactured by Kuraray Co., Ltd.).

Comparative Example 3 An ink jet recording sheet was prepared in the same manner as in Example 1 except that the 10% lime-treated gelatin in Example 1 was replaced with 10% polyvinylpyrrolidone (PVPK90: manufactured by BASF).

Comparative Example 4 Example 1 was repeated except that the emulsion of the ultraviolet absorbent of Example 1 was omitted.
In the same manner as described above, an ink jet recording sheet was prepared.

Comparative Example 5 The antioxidant IRG was prepared from the UV absorbent emulsion of Example 1.
An ink jet recording sheet was prepared in the same manner as in Example 1 except that ANOX1130 was omitted.

Comparative Example 6 From the ultraviolet absorbent emulsion of Example 1, the TI
An ink jet recording sheet was prepared in the same manner as in Example 1 except that NUVIN 171 was omitted.

Comparative Example 7 10% lime-treated gelatin of Example 1 was replaced with 10% carboxymethyl cellulose (CMC5A: Daiichi Kogyo Seiyaku Co., Ltd.)
Ink-jet recording sheet was prepared in the same manner as in Example 1 except that 30 parts by weight of an ultraviolet absorbent emulsified liquid was used instead of the above-mentioned method.

Example 6 On the same support as in Example 1, the following ink-receiving layer coating solution-1 (lower layer) and ink-receiving layer coating solution-2 (upper layer; ultraviolet absorber emulsified solution) were respectively dried by weight. Is 6 g / m ² , 2
g / m < ² >, and coated simultaneously with a slide bead coater and dried to prepare an ink jet recording sheet. <Ink receiving layer coating solution-1> 10% lime-treated gelatin 9
100 parts and 2 parts of a 5% nonionic surfactant were added to 100 parts of pure water.
Dissolves in the part. <Ink receiving layer coating liquid-2 (ultraviolet absorber emulsion)> 0.2 parts of TINUVIN171 as an ultraviolet absorber, 8 parts of ethyl acetate, and IRGANOX1 as an antioxidant
0.03 part of 330 was added and dissolved, 3 parts of 5% nonionic surfactant, 80 parts of 10% lime-processed gelatin, and 7 parts of pure water
The solution to which 00 parts was added was emulsified and dispersed by a homomixer to obtain an ultraviolet absorbent emulsion.

Example 7 The UV absorber of Example 6 was replaced with 0.1 UV of TINUVIN171.
An ink jet recording sheet was prepared in the same manner as in Example 6, except that 15 parts, 0.05 parts of TINUVIN 320 and 0.03 parts of IRGANOX1335 were used instead of the antioxidant.

Example 8 The UV absorber of Example 6 was replaced with 0.1 UV of TINUVIN171.
An ink jet recording sheet was prepared in the same manner as in Example 6, except that 2 parts and the antioxidant were changed to 0.03 part of 88HQ.

Comparative Example 8 The 10% lime-treated gelatin of Example 6 was replaced with 10% carboxymethyl cellulose (CMC5A: Daiichi Kogyo Seiyaku Co., Ltd.)
Except for the above, an ink jet recording sheet was prepared in the same manner as in Example 6.

COMPARATIVE EXAMPLE 9 From the UV absorber emulsion in the upper layer of Example 6, IRGANO
An ink jet recording sheet was prepared in the same manner as in Example 6 except that X1330 was omitted.

COMPARATIVE EXAMPLE 10 From the UV absorber emulsion in the upper layer of Example 6, TINUVI
An ink jet recording sheet was prepared in the same manner as in Example 6 except that N171 was omitted.

For each sheet obtained as described above, a CMYK single-color solid print image was recorded using a Novajet Pro (manufactured by ENCAD) ink jet plotter (GA ink), and the light resistance was evaluated by the following light resistance test. evaluated. Table 1 shows the results.

Light fastness: The solid image area was irradiated with a fedometer (manufactured by Suga Test Instruments Co., Ltd.) for 24 hours, and the percentage of the value obtained by dividing the color density after irradiation by the color density before irradiation was expressed as light fastness ( (Residual rate).

[0068]

[Table 1]

From the above results, it can be seen that the light resistance is remarkably improved by combining gelatin, an ultraviolet absorber and an antioxidant. Particularly higher effects can be obtained by forming the ink receiving layer into a two-layer structure and using gelatin, an ultraviolet absorber and an antioxidant in combination as the uppermost layer. On the other hand, in Comparative Example 7 as compared with Comparative Example 1, the ultraviolet absorber emulsified liquid was used in three times the amount, but the light resistance was not so much improved, and the glossiness (not shown in the table) was reduced. .

Next, a test was performed in which the ink-receiving layer was replaced with a pigment from a water-soluble polymer. Example 9 10 parts of the ultraviolet absorbent emulsion of Example 1, 40 parts of PVA117, 100 parts of Silicia 445 (average particle size of 3.5 μm) manufactured by Fuji Silysia Chemical Ltd. as silica particles, and a cationic fixing agent P601 ( An ink-receiving layer coating solution prepared by dissolving 10 parts of Showa Kogaku Kogyo Co., Ltd.) was applied to the same support as in Example 1 using a bar coater to a dry weight of 10 g / m ² and dried to form an ink jet recording sheet. It was created.

Comparative Example 11 An ink jet recording sheet was prepared in the same manner as in Example 9 except that the emulsion of the ultraviolet absorbent was omitted from Example 9.

Comparative Example 12 The gelatin of the emulsion of the ultraviolet absorbent of Example 9 was replaced with carboxymethyl cellulose (CMC5A: Daiichi Kogyo Seiyaku Co., Ltd.).
Inkjet recording sheet was prepared in the same manner as in Example 9 except that the above-described method was used.

Comparative Example 13 An ink jet recording sheet was prepared in the same manner as in Example 9 except that the gelatin in the ultraviolet absorbent emulsion of Example 9 was changed to polyvinyl alcohol (PVA117: manufactured by Kuraray Co., Ltd.).

Example 10 The ink receiving layer coating solution-1 (lower layer) of Example 6 was applied to PVA
117, 40 parts of Silicia Particles 1 of Silicia 445 (average particle size 3.5 μm) manufactured by Fuji Silysia Chemical Ltd.
00 parts and cationic fixing agent P601 (Showa High Polymer Co., Ltd.)
Example 6 except that 10 parts of the above-described product were replaced with a dissolved coating solution.
In the same manner as described above, an ink jet recording sheet was prepared.

Comparative Example 14 The gelatin of the emulsion of the ultraviolet absorbent of Example 10 was replaced with carboxymethyl cellulose (CMC5A: Daiichi Kogyo Seiyaku Co., Ltd.)
The ink jet recording sheet was prepared in the same manner as in Example 10 except that the above-described method was used.

The light resistance of the above ink jet recording sheet was evaluated in the same manner as described above. Table 2 shows the results.

[0077]

[Table 2]

From the above results, it can be seen that the combination of gelatin, an ultraviolet absorber and an antioxidant has an effect on light resistance even when the ink receiving layer is a pigment type.

Next, a test was conducted using a transparent plastic film as a support. Example 11 An ink jet recording sheet was produced in the same manner as in Example 1 except that the support in Example 1 was replaced with a 100 μm polyethylene terephthalate film. Further, the ultraviolet ray absorbing sheet of Example 1 was provided on the surface opposite to the ink receiving layer. Agent emulsion,
It was applied to a dry weight of 6 g / m ² using a bar coater and dried.

Irradiating light from both sides of the recording sheet,
The light resistance was evaluated in the same manner as described above, but almost no fading of the printed portion was observed as in Example 1.

[0081]

According to the present invention, an ink jet recording sheet having excellent light fastness can be obtained.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) B32B 9/02 B32B 9/02 B41J 2/01 B41J 3/04 101Y F-term (Reference) 2C056 EA13 FC06 2H086 BA01 BA15 BA16 BA19 BA24 BA35 BA38 4D075 AC22 AE24 CA35 CA50 DA04 DB18 DC27 EA33 EB07 EB13 EC02 EC47 EC49 4F100 AA21C AJ09B AK05C AK05D AK06C AK06D AL05C AL05D AT00A BA04 BA07 BA10B BA10C CA00BJAJB10 JCAB

Claims (3)

[Claims] 1. An ink jet recording sheet having an ink receiving layer provided on at least one surface of a support, wherein the ink receiving layer contains gelatin, an ultraviolet absorber and an antioxidant. 2. The ink jet recording sheet according to claim 1, wherein the ink receiving layer comprises at least two layers, and the uppermost layer contains gelatin, an ultraviolet absorber and an antioxidant. 3. The support according to claim 1, wherein the support is a transparent film, and a layer containing an ultraviolet absorbent is provided on the surface of the support opposite to the surface on which the ink receiving layer is applied. 3. The ink jet recording sheet according to 1 or 2.