JPH08169177A - Material for image recording - Google Patents

Abstract

PURPOSE: To provide a material for image recording having good light resistance of an image and a good non-yellowing property of a blank part. CONSTITUTION: A material for image recording in which base paper mainly composed of wood pulp and a filler contains ultraviolet absorbing cationized polymer made from copolymer of a polymerizable vinyl compound having quaternary ammonium base and a polymerizable vinyl compound having a structural unit with ultraviolet absorbing power. Preferably, the structural unit with ultraviolet absorbing power is 2-hydroxybenzophenone residue or 2- hydroxybenzotriazol residue.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a material for image recording, more specifically, transfer paper for electrophotography, ink jet recording paper, thermal recording paper, pressure sensitive recording paper,
The present invention relates to an image recording material which is used for information recording paper such as sublimation type thermal transfer recording image-receiving paper and has excellent light resistance of an image and excellent yellowing resistance of a white paper portion.

[0002]

2. Description of the Related Art In the present age called the information age, how to utilize a huge amount of information for a company will lead to future development. Therefore, it is important to transmit and obtain information quickly and accurately. . The information carried by the electrical signal can be made available to many by presenting it as an image, or hard copy. The hard copy technology has been diversified into various recording methods such as heat-sensitive recording, pressure-sensitive recording, ink jet recording, fusion heat transfer, sublimation-type heat transfer, and electrophotography with the recent progress of telecommunications and electronics technologies.

For example, the heat-sensitive recording system is a heat-sensitive recording paper in which a heat-sensitive recording layer containing an electron-donating, usually colorless or light-colored dye precursor and an electron-accepting developer as main components is provided on a support. It is used and is intended to obtain a recorded image by instantaneously reacting the dye precursor and the developer by heating with a thermal head, a thermal pen, a laser beam or the like. The heat-sensitive recording paper is disclosed in, for example, Japanese Examined Patent Publication No. 43-4160, and No.
It is disclosed in Japanese Patent Publication No. 5-14039. Such a thermal recording paper has the advantages that recording can be obtained with a relatively simple device, that it is easy to maintain, and that it does not generate noise, and that it can be used for measuring recorders, facsimiles, printers, computer terminals, It is used in a wide range of fields such as labels and ticket vending machines.

The ink jet recording system is a system in which minute droplets of ink are ejected and adhered to a recording paper such as paper by various operating principles to record images, characters, etc., but they are high speed, low noise, many It has features such as easy colorization, great flexibility in recording patterns, and no need for development-fixing, and is rapidly spreading in various applications as a recording device for various figures including Kanji and color images. Furthermore, the image formed by the multicolor ink jet system is
It is possible to obtain a comparable record. Further, in applications requiring a small number of copies, it is being widely applied to the field of full-color image recording because it is cheaper than the photographic technique.

In the sublimation type thermal transfer recording system, an image is converted into an electric signal, and the electric signal is converted into a heat signal by using an electric heating element such as a thermal head, or a light absorption heating element is changed by using a laser. The transfer sheet coated with a sublimable dye is converted to a heat signal by generating heat, and the transfer sheet is heated, and the sublimation dye is applied from the transfer sheet to the image receiving paper by sublimation or thermal diffusion in the medium. By transferring to a layer, characters and image information are recorded. With this method, it is possible to obtain an image that is comparable to multicolor printed matter and color photographs.
It is being widely used because it is cheaper than printing technology and photographic technology.

In the electrophotographic recording system, a photosensitive drum having a surface layer of a photoconductive material and a conductive substrate is charged by irradiation of corona discharge ions, and an image pattern is irradiated on the photosensitive drum as an optical image, so that the photosensitive drum is exposed. A toner is attached to the surface charge image formed on the surface of the image to develop the image, and the image is transferred to a recording medium and fixed by heat or pressure to obtain a record. This method is developing from a copying machine, has a wide range of applications such as page printer and facsimile output, and is rapidly growing. In particular, in the field of copying machines, progress has been made from an analog system to a digital system, a digital color laser copying machine has been developed, and a demand for color recording is increasing.

The image recording materials used in the above various recording systems are mainly composed of paper as a base material, and also include those having a base material such as a film or a composite of a paper base material and a film. .

The image recording material can be used as the image recording material itself such as electrophotographic transfer paper or ink jet recording paper, or the image recording material such as thermal recording paper or sublimation type thermal transfer recording image receiving paper. There is one that can be used by providing a functional coating layer on the surface of. In either case, in the image recording material, various improvements have been conventionally made to prevent yellowing of the image recording material itself or to improve the light resistance of the recorded image.

For example, in a thermal recording paper, a method of incorporating a benzophenone or a benzotriazole derivative as an improvement of the discoloration of the background and the discoloration of the image area (Japanese Patent Laid-Open No. 50-1975).
No. 104650, No. 55-55891, No. 5
No. 5-93492, and No. 58-87093) have been proposed. In the case of ink jet recording paper, a method of applying a cationic resin composed of a polyalkylene polyamine dicyandiamide ammonium salt condensate to the surface of the base paper to improve the light resistance of recorded images, the prevention of yellowing of white paper, and the improvement of water resistance. No. 2-35675) has been proposed.

However, the image recording material is often exposed to various environmental conditions such as ultraviolet rays and temperature / humidity during storage or handling of the image recording material before or after recording. Further, the image recording material is stored in a file such as polyethylene, polypropylene, vinyl chloride resin or the like, and an adhesive tape is attached to the image recording material, so that there are various handling methods.

Various materials such as files such as polyethylene, polypropylene, vinyl chloride resin, adhesives, glues, rubbers, etc. are stable against light and heat by the addition of phenolic antioxidants and hindered amine light stabilizers. Have been converted. Many polypropylenes, polyethylenes and the like have kneaded and mixed with an antioxidant having a phenol group in the molecule such as butylhydroxytoluene (hereinafter abbreviated as BHT). These phenolic antioxidants are oxidized to give quinone. It is well known that the structure makes it yellow.

A large amount of a filler (inorganic pigment) is internally added to the base paper, that is, the image recording material, and when the image recording material is in contact with the above material such as a polyethylene file for a long period of time, it is contained in the above material. The phenolic antioxidant that is present is volatilized and is adsorbed by the filler in the image recording material, and this is oxidized to yellow the image recording material itself.

[0013]

SUMMARY OF THE INVENTION In view of the above, an object of the present invention is to provide an image recording material which is excellent in light resistance of an image and yellowing resistance of a white paper portion.

[0014]

As a result of intensive studies in view of the above, the present inventor has come to invent the image recording material of the present invention. That is, the image recording material of the present invention is a copolymer of a polymerizable vinyl compound having a quaternary ammonium salt group bonded to a base paper mainly composed of wood pulp and a filler and a polymerizable vinyl compound having a structural unit having an ultraviolet absorbing ability. It is characterized by containing an ultraviolet-absorbing cationized polymer consisting of

In the image recording material of the present invention, preferably, the structural unit having an ultraviolet absorbing ability is a 2-hydroxybenzophenone residue or a 2-hydroxybenzotriazole residue.

The image recording material of the present invention will be described in detail below. The ultraviolet-absorbing cationized polymer of the present invention has a structure in which a structural unit having an ultraviolet-absorbing ability, that is, a 2-hydroxybenzophenone residue, a 2-hydroxybenzotriazole residue or the like is bonded to the main chain of a polymerizable vinyl compound monomer. It is a copolymer with a polymerizable vinyl compound to which a primary ammonium salt group is bound.

The copolymerization ratio (p / q) in the copolymer of the polymerizable vinyl compound (p) having a structural unit having ultraviolet absorption ability and the polymerizable vinyl compound (q) having a quaternary ammonium salt group is , Can be set appropriately. The water-soluble or self-dispersible UV-absorbing cationized polymer can be obtained by changing the ratio of p and q. For example, when the ratio of the polymerizable vinyl compound to which a quaternary ammonium salt group is bound is reduced, the water-soluble type is shifted to the self-dispersible type.

As the structural unit having an ultraviolet absorbing ability,
A 2-hydroxybenzophenone derivative, a 2-hydroxybenzotriazole derivative, a salicylic acid derivative, a cyanoacrylate derivative, and the like, preferably a 2-hydroxybenzophenone derivative and a 2-hydroxybenzotriazole derivative can be mentioned. For example, they are exemplified as follows. be able to.

1) 2-hydroxybenzophenone derivative 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, 2-hydroxy-4-methoxy-5-sulfo Benzophenone, 2,
4-dihydroxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, bis (2
-Methoxy-4-hydroxy-5-benzoylphenyl) methane, 2-hydroxy-4-acryloyloxybenzophenone, 2-hydroxy-4-methacryloyloxybenzophenone, 2-hydroxy-4- (2-acryloyloxy) ethoxybenzophenone, 2 -Hydroxy-4- (2-methacryloyloxy) ethoxybenzophenone, 2-hydroxy-4- (2-methyl-2)
-Acryloyloxy) ethoxybenzophenone and the like.

2) 2-Hydroxybenzotriazole derivative 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-5'-t-)
Butylphenyl) benzotriazole, 2- (2'-hydroxy-5'-3 ', 5'-di-t-butylphenyl) benzotriazole, 2- (2'-hydroxy-
3'-t-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-
3 ', 5'-di-t-amylphenyl) benzotriazole, 2- {2'-hydroxy-3'-(3 ", 4",
5 ", 6" -tetrahydrophthalimidomethyl) -5 '
-Methylphenyl} benzotriazole, 2,2-methylenebis {4- (1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol}, 2- {2'- Hydroxy-5 '-(methacryloyloxy) phenyl} benzotriazole, 2-
{2'-hydroxy-5 '-(acryloyloxy) phenyl} benzotriazole, 2- {2'-hydroxy-3'-t-butyl-5'-(methacryloyloxy)
Phenyl} benzotriazole, 2- {2'-hydroxy-3'-methyl-5 '-(acryloyloxy) phenyl} benzotriazole, 2- {2'-hydroxy-
5 '-(methacryloyloxypropyl) phenyl}-
5-chlorobenzotritriazole, 2- {2'-hydroxy-5 '-(methacryloyloxyethyl) phenyl} benzotriazole, 2- {2'-hydroxy-
5 '-(acryloyloxyethyl) phenyl} benzotriazole, 2- {2'-hydroxy-3'-t-butyl-5'-(methacryloyloxyethyl) phenyl} benzotriazole, 2- {2'-hydroxy-
3'-methyl-5 '-(acryloyloxyethyl) phenyl} benzotriazole, 2- {2'-hydroxy-5'-(methacryloyloxypropyl) phenyl}
-5-chlorobenzotriazole, 2- {2'-hydroxy-5 '-(acroyloxybutyl) phenyl}-
5-methylbenzotriazole, {2-hydroxy-3
-T-butyl-5- (acryloyloxyethoxycarbonylethyl) phenyl} benzotriazole and the like.

3) Salicylic Acid Derivatives Phenyl salicylate, pt-butylphenyl salicylate, p-octylphenyl salicylate and the like.

4) Cyanoacrylate derivative 2-ethylhexyl-2-cyano-3,3'-diphenyl acrylate, ethyl-2-cyano-3,3'-diphenyl acrylate, etc.

The polymerizable vinyl compound having a quaternary ammonium salt group is a polymerizable vinyl compound having a copolymerizable polymerizable vinyl compound having a tertiary amino group in the molecule as a monomer and a structural unit having an ultraviolet absorbing ability. After being copolymerized with a compound, the amino group is quaternized with an alkylating agent, or the tertiary amino group of the monomer is converted into a quaternary ammonium salt with an alkylating agent in advance, and then this is copolymerized. By doing so, it can be introduced into the ultraviolet absorbing cationized polymer.

The copolymerizable polymerizable vinyl compound having a tertiary amino group in the molecule is, for example, N, N-dimethylaminopropyl acrylate, N, N-diethylaminoethyl acrylate, N, N-dimethylaminoethyl methacrylate. , N, N-diethylaminoethyl methacrylate, N, N-dimethylaminopropyl methacrylate, N, N-dimethylaminobutyl methacrylate, N, N-dimethylaminoethyl acrylate, N,
N-dimethylaminopropyl acrylamide, N, N-
Examples thereof include dimethylaminoethylacrylamide, acryloylmorpholine, N-2-hydroxy-3-acryloyloxypropyl-N, N-dimethylamine, N-3-methacryloyloxy-2-hydroxypropyl-N, N-diethylamine and the like.

Examples of the alkylating agent for converting the amino group of the polymerizable vinyl compound having a tertiary amino group into a quaternary ammonium salt include halogenated alkyls such as benzyl chloride and methyl chloride; sulfuric acid such as dimethylsulfate and diethylsulfate. Examples thereof include esters, and the betaine-type quaternary ammonium group can be obtained by reacting with monochloroacetic acid, β-propiolactone and the like.

Examples of the polymerizable vinyl compound containing a quaternary ammonium salt group include glycidyl trimethyl ammonium chloride, 3-chloro-2-hydroxypropyl trimethyl ammonium chloride, and 3-chloro-2-hydroxypropyl trimethyl ammonium chloride.
Chloro-2-hydroxypropyltriethanolammonium chloride, glycidyldimethylbenzylammonium chloride, glycidyldimethylbutylammonium chloride, N-2-hydroxy-3-acryloyloxypropyl-N, N, N-trimethylammonium chloride, N-methacryloylaminoethyl -N,
N, N-dimethylbenzyl ammonium chloride, N
-Methacryloxy-N, N, N-triethylammonium ethyl sulfuric acid and the like can be mentioned.

As described above, in the image recording material of the present invention, by incorporating the ultraviolet-absorbing cationized polymer into the base paper mainly composed of wood pulp and the filler, the phenomenon of yellowing of the white paper portion of the image recording material occurs. Can be prevented, and the light resistance of the image recorded on the image recording material by various recording methods can be remarkably improved. It is presumed that this is because the cationized polymer strongly adheres to the base paper while maintaining the ultraviolet absorbing ability.

The yellow color change of the image recording material with respect to the blank portion is
BHT dimer (4
4'-methylenebis-2,6-di-t-butylphenol) can be used to easily estimate the yellowing property of the image recording material.

Specifically, a 1% solution of an alcohol (ethanol, isopropyl alcohol, etc.) of a BHT dimer was spotted on the image recording material so that the solid content was 0.5 g / m ^2, and the solution was naturally spotted. Dry, 20 ℃, 65% R
It is left for 3 days under the condition of H, and L ^* a ^* b ^* before and after the leaving ^.
(Colorimetric method according to CIE) is a color difference meter (CR10
0: manufactured by Minolta). Here, the degree of yellowing can be determined from the difference between before and after the treatment b ^* (△ b ^*), small enough yellowing less numerically, △ b ^* is preferably 15 or less, practically if 10 or less It doesn't matter. Such a measuring method has a correlation with the evaluation actually stored in a file or the like.

The base paper used in the present invention will be described below.
explain. The pulp for base paper according to the present invention is LBKP,
Chemical pulp such as NBKP, GP, PGW, RMP, T
Mechanical pulp such as MP, CTMP, CMP, CGP, D
Waste paper pulp such as IP and wood pulp such as can be used.

As the filler used in the base paper according to the present invention, talc, clay, titanium dioxide, heavy calcium carbonate, light calcium carbonate, kaolin, calcined kaolin, calcium sulfate, barium sulfate, calcium silicate, aluminum hydroxide, Fillers which can be usually used for paper such as synthetic silicate and plastic pigment can be used alone or in combination. Further, various pigments such as ferrous oxide, ferric oxide, silicon carbide, silicon nitride and zinc oxide may be used for the purpose of imparting functionality. The content of the filler is 30% by weight, preferably 20% by weight, based on the base paper.

In producing the base paper, various devices such as a fourdrinier paper machine, a cylinder paper machine, an on-top paper machine, and a twin wire paper machine can be used.

In the image recording material of the present invention, a size press process may be provided on the surface of the base paper, and examples of the sizing agent include starch, polyvinyl alcohol,
Latex, various surface sizing agents such as maleic anhydride-based sizes, α-olefin-based sizes, styrene-acrylic acid-based sizes, dimensional stabilizers such as ethylene-urea resins, inorganic conductive agents such as sodium chloride and potassium chloride,
An organic conductive agent such as dimethylaminoethyl methacrylate, a surfactant, a pigment, a dye, a pH adjusting agent, a defoaming agent, a pitch control agent, a slime control agent and the like can be applied as an internal additive for papermaking.

As a method of coating in the size press step, it is of course possible to use an apparatus such as a conventional size press, a gate roll size press, a metering blade type size press, a bill blade or a short dwell coater.

The base paper produced as described above may be used as it is, or a calendering machine such as a machine calender, a TG calender or a soft calender may be used for the purpose of controlling the flatness.

The image recording material of the present invention is used as an image recording sheet such as a printing paper, an electrophotographic transfer paper, a thermal transfer image receiving paper and an ink jet recording paper in a state where the image recording material itself is uncoated. Further, by coating a functional coating layer on the surface of the image recording material, various kinds of coated paper for printing, thermal recording paper, ink jet recording paper, magnetic recording paper, image receiving paper for sublimation type thermal transfer recording, pressure sensitive recording paper, etc. Can be used as a recording medium.

[0037]

The image recording material of the present invention comprises a base paper mainly composed of wood pulp and a filler, and a polymerizable vinyl compound having a quaternary ammonium salt group bonded thereto and a polymerizable vinyl compound having a structural unit having an ultraviolet absorbing ability bonded thereto. By containing a UV-absorbing cationized polymer consisting of a polymer,
It is characterized by excellent light resistance of an image and yellowing resistance of a white paper portion.

It is presumed that the reason is that the structural unit having an ultraviolet absorbing ability is stabilized by being bonded to the polymerizable vinyl compound having a quaternary ammonium salt group, without being affected by external conditions. The polymerizable vinyl compound itself having a quaternary ammonium salt group bonded thereto, when contained in or coated on the base paper, serves as an adhesive in the base paper or on the surface of the base paper, and thus is firmly fixed. As a result, the image recording material of the present invention can have the above characteristics.

On the other hand, conventionally used UV absorbers are mixed with a resin for fixing the UV absorbers to be contained in the coating layer of the base paper, or mixed with pulp slurry to be internally added to the base paper. Since the ultraviolet absorbent itself exists independently, it has a drawback that it migrates to the surface of the base paper or the coating layer over time depending on the external environment and loses its function.

[0040]

EXAMPLES Examples of the present invention will be described below, but the present invention is not limited to these examples. Further, “parts” and “%” shown in the examples represent parts by weight and% by weight, unless otherwise specified.

Preparation examples of the ultraviolet absorbing cationized polymer are shown below in advance. Preparation Example 1 30 g of 2-hydroxy-4-methacryloyloxybenzophenone, 70 g of N, N-dimethylaminopropylacrylamide and 100 g of ethyl cellosolve were placed in a separable flask equipped with a Dimroth, a dropping funnel, a thermometer, a nitrogen introducing tube, and a stirrer. It was charged and the temperature was raised to 80 ° C. while introducing nitrogen from the nitrogen introducing pipe. After that, 0.1 g of azobisisobutyronitrile dissolved in a small amount of ethyl cellosolve was divided into 4 portions and added dropwise over 30 minutes. After completion of the dropping, reaction was carried out for 2 hours in a nitrogen atmosphere to synthesize an ultraviolet absorbent polymer aqueous solution. Subsequently, 30 g of diethyl sulfuric acid
Was added dropwise over 30 minutes, and the reaction was performed for 2 hours under a nitrogen atmosphere. After the reaction is complete, cool to room temperature, dilute with water,
An ultraviolet absorbing cationic polymer aqueous solution (solid content 20% by weight) of Preparation Example 1 was obtained.

Preparation Example 2 UV rays were prepared in the same manner as in Preparation Example 1 using 30 g of 2- [2'-hydroxy-5 '-(methacryloyloxy) phenyl] benzotriazole, 70 g of N, N-diethylaminoethyl acrylate and 100 g of ethyl cellosolve. An absorbent polymer aqueous solution was synthesized. Subsequently, 30 g of monochloroacetic acid was added dropwise over 30 minutes, and the reaction was performed for 2 hours in a nitrogen atmosphere. After completion of the reaction, the mixture was cooled to room temperature and diluted with water to obtain an ultraviolet absorbing cationic polymer aqueous solution (solid content 20% by weight) of Preparation Example 2.

Preparation Example 3 2-Hydroxy-4- (2-methacryloyloxy) ethoxybenzophenone 30 g, N-2-hydroxy-3
-Preparation Example 1 using 70 g of acryloyloxypropyl-N, N-dimethylamine and 100 g of ethyl cellosolve
An ultraviolet absorbent polymer aqueous solution was synthesized in the same manner as in.
Subsequently, 30 g of methyl chloride was added dropwise over 30 minutes, and the reaction was performed in a nitrogen atmosphere for 2 hours. After completion of the reaction, the mixture was cooled to room temperature and diluted with water to obtain an ultraviolet absorbing cationized polymer aqueous solution (solid content 20% by weight) of Preparation Example 3.

Preparation Example 4 2- [2'-hydroxy-5 '-(methacryloyloxy) phenyl] -5-chlorobenzotriazole 30
g, N, N-diethylaminoethyl acrylate 70
g and 100 g of ethyl cellosolve, an ultraviolet absorbent polymer aqueous solution was synthesized in the same manner as in Preparation Example 1. Subsequently, 30 g of benzyl chloride was added dropwise over 30 minutes, and the reaction was performed in a nitrogen atmosphere for 2 hours. After completion of the reaction, the mixture was cooled to room temperature and diluted with water to obtain an ultraviolet absorbing cationic polymer aqueous solution (solid content 20% by weight) of Preparation Example 4.

Example 1 80 parts of LBKP (freezing degree of 400 mlcsf) and NBKP
Pigment 20 in which the ratio of light calcium carbonate / heavy calcium carbonate / talc is 10/10/10 with respect to 100 parts of wood pulp consisting of 20 parts (freeness 480 mlcsf)
Parts, commercially available alkyl ketene dimer 0.10 parts, commercially available cationic acrylamide 0.03 parts, commercially available cationized starch 1.0 part, and sulfuric acid band 0.5 parts are mixed to form a pulp slurry, which is used for Fourdrinier papermaking. Papermaking with a machine, basis weight 85g /
to prepare a base paper of m ^2.

On this base paper, the ultraviolet absorbing cationized polymer prepared in Preparation Example 1 (adjusted to a concentration of 10% aqueous solution)
Was applied by a size press to a coating amount of 3.0 g / m ² to obtain an image recording material of Example 1.

Examples 2 to 4 Each of the UV absorbing cationic polymers prepared in Preparation Examples 2 to 4 (adjusted to a concentration of 10% aqueous solution) was used on the same base paper as that prepared in Example 1 and the size was adjusted. The image recording materials of Examples 2 to 4 were coated with a press so that the coating amount was 1.5 g / m ² .

Example 5 80 parts of LBKP (freezing degree of 400 mlcsf) and NBKP
(Freeness 480 mlcsf) 30 parts of light calcium carbonate, 0.10 part of commercial alkyl ketene dimer, 2.0 parts of the UV absorbing cationized polymer of Preparation Example 1, and sulfuric acid band per 100 parts of wood pulp consisting of 20 parts Pulp slurry was mixed with 0.5 part to make a pulp slurry, which was used for paper making with a Fourdrinier paper machine to obtain an image recording material of Example 5 consisting of base paper having a basis weight of 85 g / m ² .

Example 6 80 parts of LBKP (freezing degree 400 mlcsf) and NBKP
(Freeness 480 mlcsf) 100 parts of wood pulp consisting of 20 parts, 30 parts of light calcium carbonate, 0.10 part of commercial alkyl ketene dimer, 3.0 parts of UV absorbing cationized polymer of Preparation Example 3, sulfuric acid band 0.5 parts of the pulp slurry was mixed to make a pulp slurry, which was used for papermaking with a Fourdrinier paper machine to obtain an image recording material of Example 6 consisting of base paper having a basis weight of 85 g / m ² .

On one surface of the obtained image recording material, synthetic amorphous silica (Fineseal X-37B: manufactured by Tokuyama Soda) 10
Prepare an ink receiving layer coating liquid consisting of 0 parts, 30 parts of polyvinyl alcohol (PVA117: manufactured by Kuraray), and 20 parts of a cationic dye fixing agent (Sumireds resin 1001: manufactured by Sumitomo Chemical Co., Ltd.), and dry coating with an air knife coater. The inkjet recording paper of Example 6 was prepared by coating and drying so that the amount was 5 g / m ² .

Comparative Example 1 The same raw paper as the raw paper prepared in Example 1 was used as the image recording material of Comparative Example 1 without the size press.

Comparative Example 2 2- (2'-hydroxy-) was previously used as an ultraviolet absorber.
5'-t-butylphenyl) benzotriazole (10 parts) was used.
0 part was mixed and dispersed by a ball mill to prepare a dispersion liquid.

Next, the same base paper as that prepared in Example 1 was coated with a size press to a coating amount of 2.5 g / m ² , to obtain an image recording material of Comparative Example 2.

Comparative Example 3 Example 6 was prepared on one side of the same base paper as that prepared in Example 1.
An ink jet recording paper of Comparative Example 3 was prepared by using the ink receiving layer coating liquid prepared in 1. above and coating and drying it with an air knife coater to a dry coating amount of 5 g / m ² .

The ink jet recording papers using the image recording materials obtained in Examples 1 to 5 and Comparative Examples 1 and 2 and the image recording materials obtained in Example 6 and Comparative Example 3 were evaluated by the following evaluation methods. The results are shown in Table 1 below.

1) Yellowing of white paper part [BHT method] BHT dimer (4,4'-methylenebis-
A solution of 2,6-di-tert-butylphenol) in 1% isopyr alcohol was spotted on the image recording material so that the solid content was 0.5 g / m ^2, and the temperature was 65 ° C. at 20 ° C.
L ^* a ^* b ^* (CIE before and after leaving for 3 days under the condition of% RH
The colorimetric method in accordance with (1) was measured with a color difference meter (CR100: manufactured by Minolta). Then, the degree of yellowing of the white paper portion was evaluated by the difference in b ^* before and after the treatment (Δb ^* ). It should be noted that the smaller this value is, the smaller the yellowing change is.

[File Method] A polypropylene plastic file bag (A4 size) containing 1.0% by weight of commercially available BHT was cut into a square of 5 cm × 5 cm in the vicinity of the center of one side, and the coated layer surface had holes. Put it in a file bag so that it touches the existing file side, leave it in the room for one month, take out the sample, and color the image recording material before and after processing L ^* a ^* b ^* (coloring method according to CIE) It was measured with a color difference meter (CR100: manufactured by Minolta). The degree of yellowing of white paper portion, the difference in b ^* before and after the treatment (△ b ^*) can be represented by, as this number is less, indicating that the yellowing is small.

2) Lightfastness of Image The lightfastness of the image was evaluated by recording the image by an ink jet recording system. Using an inkjet printer (MJ-700V2C, manufactured by EPSON), an inkjet printer (EPSON) was used for each image recording material (Examples 1-5 and Comparative Examples 1-2) and inkjet recording paper (Example 6 and Comparative Example 3). Made, MJ-700V
In 2C), solid printing of magenta ink was performed. The color difference of magenta ink color before and after light irradiation of these inkjet recording papers for 30 hours under the environment of a black panel temperature of 63 ° C. and a relative humidity of 65% RH was measured using a xenon arc fade meter and Atlas Ci-35f. did. Color difference is L ^* a ^* b ^* (color specification method according to CIE)
According to the above, based on the result of measuring the color of each inkjet recording paper before and after the light irradiation, it can be defined by the following mathematical expression 1. The larger the color difference, the more the color deterioration occurs. In addition, the measurement was performed using standard light C as CR10 manufactured by Minolta.
0 was used. If the color difference is less than 1.0, visually
It is almost impossible to recognize the difference in color.

[0059]

[Equation 1] ΔE = {(ΔL ^* ) ² + (Δa ^* ) ² + (Δb ^* ) ² } ^1/2 where ΔE is the color difference, ΔL ^* and Δa ^* and Δb ^* Is the difference between L ^* and a ^* and b ^* before and after light irradiation.

3) Electrophotographic suitability Image recording materials (Examples 1 to 5 and Comparative Examples 1 and 2) were subjected to image recording by an electrophotographic system, and electrophotographic suitability was confirmed by an electrophotographic copying machine (SF-9400 manufactured by Sharp Corporation). The following evaluation was carried out using a sample cut into A4 size grain lengths according to (4). [Toner Fixing Property] Commercially available 18 mm wide cellophane adhesive tape (Nichiban Co .; Cellotape) was applied to the image area having an optical density of about 1.4, which was copied by the above copying machine, at a linear pressure of 300 g / cm, and 1 cm. The ratio of the image density after peeling to the image density before peeling when peeling at a speed of / sec (image density after peeling / image density before peeling) was evaluated as an index.
For electrophotographic transfer paper, this ratio is required to be 0.7 or more. The image density was measured by Macbeth reflection densitometer (Macbeth Co .; RD-91).
8) was used.

[Running property] When A4 size paper was passed in the direction perpendicular to the paper making (CD direction), the state of double feed and jam occurrence was observed, and ○ was good, Δ was good, and X was bad. Evaluated as.

[0062]

[Table 1]

Evaluation: From the results shown in Table 1 above, the image recording material of the present invention has excellent characteristics in yellowing resistance of the blank portion, light resistance of the image by the ink jet recording system, fixing property by the electrophotographic system and running property. It was shown.

The image recording materials of Examples 1 to 4 were obtained by size-pressing the ultraviolet-absorbing cationized polymer of the present invention on the surface of the raw paper, and exhibited an excellent effect of yellowing resistance of the white paper portion. Further, the image recording material of Example 5 containing the cationized polymer in the base paper was also better than the image recording material of Comparative Example 1 not containing it. Particularly, in the running property when used in the electrophotographic system, there was a large difference depending on the presence of the cationized polymer due to the antistatic property.

Further, the image recording material of Comparative Example 2 coated alone with the ultraviolet absorbent dispersion had insufficient light resistance of the image, and when this was used in the electrophotographic system, the running property was poor. there were.

On the other hand, in the ink jet recording papers of Example 6 and Comparative Example 3 provided with the same ink receiving layer composition,
Whether the image-recording material as the support contained the ultraviolet-absorbing cationized polymer of the present invention caused a remarkable difference in yellowing of the white paper portion and light resistance of the image.

[0067]

The image recording material of the present invention contains the specific ultraviolet absorbing cationized polymer in the base paper,
It is possible to have both the effect as the ultraviolet absorbing property and the effect as the cationic property, and it is possible to exert a synergistic effect as compared with the case where each is used alone.

Claims (2)

[Claims] 1. Ultraviolet absorption consisting of a copolymer of a polymerizable vinyl compound bound to a quaternary ammonium salt group and a polymerizable vinyl compound bound to a structural unit having ultraviolet absorptivity to a base paper mainly consisting of wood pulp and a filler. An image recording material containing a cationic cationized polymer. 2. A structural unit having an ultraviolet absorbing ability is 2-
A hydroxybenzophenone residue or a 2-hydroxybenzotriazole residue.
The described image recording material.