JPH10100539A - Support for recording material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a support having excellent fadability, light resistance and image long preservability by forming the support of a material containing paper and/or plastic as a base material and pullulan of specific amount in a recording material having a recording layer containing color developing components on the support. SOLUTION: The support containing paper and/or plastic as a base material and pullulan of 1 to 30g/m is used for the recording material such as a thermosensitive recording material, silver halide photographic recording material or electrophotographic recording material. In the case of its execution, it is formed in the state that paper is used as the base material and the pullulan is contained in the paper or the state that a laminate containing layers each formed of the base material made of paper and/or plastic film and the layer contains the pullulan. Oxygen permeability of the support is preferably 50cc/m<2> / day or less. As the pullulan, polymer of grape sugar known similarly as cellulose of component of dextran or nate de coco is used.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a support for a recording material, and more particularly, to the fading property of a recorded image of a recording material having a recording layer containing a coloring component on the support.
The present invention relates to a recording material support having excellent light fastness and long-term storage properties.

[0002]

2. Description of the Related Art Various recording materials, for example, heat-sensitive recording materials,
In the case of recording materials such as silver halide photographic recording materials and electrophotographic recording materials, when exposed to sunlight for a long period of time, or when posted in a room for a long period of time, the background is colored by light or the recording formed. The image portion had a disadvantage of discoloration or fading.

Various methods have been proposed to improve the coloring of the background portion and the discoloration and fading of the image portion.

For example, JP-A-6-214341 discloses that
The method of impregnating a paper sheet with an aqueous solution of amylose starch that has been hydrophobically substituted is described in Japanese Patent Application Laid-Open No. 6-502026 and Japanese Patent Application Laid-Open No. 8-106140. A method of treating a paper sheet with a solution having a specific amount of polyvinyl alcohol is disclosed. Although some improvement in light resistance can be seen by these methods, the effect was not always sufficient.

[0005]

SUMMARY OF THE INVENTION The present inventors have previously found that by reducing the oxygen permeability of a support, it is possible to achieve an improvement in image stability, and to provide the support with ethylene / ethylene.
By means of coating vinyl alcohol copolymer, polyvinylidene chloride, etc., or laminating polyethylene terephthalate film or ethylene / vinyl alcohol copolymer film, it is possible to control the oxygen permeability to obtain a heat-sensitive recording material that achieves long-term storage of images. Japanese Patent Application 08-
No. 100504 was proposed.

[0006] Although the above-mentioned support was suitable for use in heat-sensitive recording materials, the present invention is a further improvement of this technique. An object of the present invention is to provide a support for a recording material which can be applied to various recording materials and is excellent in fading property, light resistance and long-term storage of images.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to provide a paper and / or plastic substrate having a pullulan weight of 1 to 30 g.
/ M ² .

[0008] The support for the recording material is an embodiment in which the base material is paper and pullulan is contained in the paper, or a laminate comprising a layer composed of paper and / or a plastic film, which contains pullulan. Preferably, at least one layer is provided.

Further, the support for recording material preferably has a plastic film layer provided on at least the surface of the base paper on which the recording layer is provided, and the plastic film layer is made of a polyester film, a vinylidene chloride film, a polycarbonate film. , A polyvinyl chloride film, or a random copolymer film of ethylene and vinyl alcohol.

The physical properties of these recording material supports include:
It is preferable that the oxygen permeability is 50 cc / m ² / day or less.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The support for recording material of the present invention is based on a general paper and / or plastic, and has a solid content, that is, pullulan of 1 to 30 as a dry weight.
g / m ² . Furthermore, 3 to 20 g / m
It is preferable to contain ² . Pullulan content is 1g /
and deteriorates fogging, etc. is less than m ^2, not be achieved long-term storage of the images, is not preferable from the viewpoint of production suitability and cost more than 30 g / m ^2.

[0012] Pullulan used in the recording material support of the present invention is a kind of polysaccharide produced by microorganisms, and is known as a polymer of glucose as well as cellulose, which is a component of dextran and nata de coco. Pullulan is generally an incomplete bacterium called Anreobasidium, also known as black yeast.
It is a viscous polysaccharide obtained by Pullulans and produced extracellularly by this microorganism. Also, triglucose A, pullulan P
It is also available as a commercial product under a name such as I-20 (trade name: manufactured by Hayashibara Biochemical Laboratory).

The structure of pullulan is represented by the following structural formula:
Maltotriose in which three glucoses are linked by a-1,4 forms one unit, and the next maltotriose has a
It is a linear glucan repeatedly bonded with -1,6 bonds. The degree of polymerization of glucose per pullulan molecule is several hundred or more.
Thousands.

[0014]

Embedded image

In the formula, n is an integer indicating the number of pullulan units bonded, and is preferably about 5 to 5,000.

There is no particular limitation on the mode of incorporating pullulan in the recording material support of the present invention, and it may be included during the production of the base material. A layer composed of pullulan or a layer containing pullulan may be added to any of the supports. It may be arranged at a position, when the support has a laminated structure, pullulan may be used for bonding between layers, and when the substrate is paper, it may be contained in the sizing agent of the paper substrate .

Pullulan is usually in the form of a white powder. When it is contained in a support for recording material, it may be dissolved in a solvent when it is contained in the production of a base material or as a component of a sizing agent. Depending on the characteristics of the components, they can be blended as they are. As a solvent when used in a solution state, it is preferable to use water because it is easily dissolved in hot or cold water. In addition, glycerin formamide, dimethyl formamide, dimethyl sulfoxide and the like can also be used as the solvent.

When forming a layer made of pullulan or a layer containing pullulan, after dissolving pullulan in a solvent,
A uniform layer can be formed by coating the desired surface with a known coating method such as spray coating or bar coating and then drying. The layer made of pullulan is a colorless and transparent layer and does not impair light transmittance, so that it can be used as a surface layer. Further, the layer made of pullulan is impermeable to oxygen and has excellent oil resistance.

As described above, pullulan alone can form a tough layer alone, but if desired, pullulan can be used in combination with other water-soluble polymers such as gelatin, amylose, and polyvinyl alcohol (PVA). It can also be a layer containing.

Further, pullulan has good affinity with cellulosic substances such as wood and glass and the like, and also has excellent adhesiveness. Therefore, when forming a support having a laminated structure, pullulan is also used for bonding between layers. Can be.

In the support for recording material of the present invention, general paper and / or plastic are used as the base material. When using paper as the substrate, suitable papers may be selected from commonly used materials. That is, softwood, a natural pulp selected from hardwood to the main raw material, if necessary, clay, talc, TiO _2, CaCO _3, filler rosin, alkyl ketene dimer as urea resin fine particles, a higher fatty acid,
A resin to which a sizing agent such as epoxidized fatty acid amide, paraffin wax, alkenyl succinic acid, etc., a paper strength enhancer such as polyacrylamide, starch, polyamide polyamine epichlorohydrin, a fixing agent such as a sulfate band and a cationic polymer, and the like are used. Further, a softening agent such as an epoxidized fatty acid amide and a surfactant may be added.
Further, synthetic pulp may be used in place of the above natural pulp, or natural pulp and synthetic pulp may be mixed in an arbitrary ratio.

Although the type and thickness of the base paper substrate are not particularly limited, the basis weight is 40 g / m ² to 200 g / m ^2.
g / m ² is desirable. Further, as the support for the recording material is desired to have as high a surface smoothness and flatness as possible, it is preferable to apply a heat and pressure by calendering such as a machine calender, a soft calender, and a super calender to perform the surface smoothing treatment. .

The support of the present invention may be a base paper having both sides coated with a surface size liquid. As the surface size liquid, an aqueous solution of polyvinyl alcohol and / or a modified product thereof, which is usually used, can be used.
Other starch, CMC, HEC, sodium alginate,
High molecular compounds such as gelatin, calcium chloride, sodium chloride, metal salts such as sodium sulfate, further glycerin,
Hygroscopic substances such as polyethylene glycol, dyes, coloring such as fluorescent whitening agents, whitening substances, caustic soda, aqueous ammonia,
You may add pH control agents, such as hydrochloric acid, sulfuric acid, and sodium carbonate. Further, a softening agent such as an epoxidized fatty acid amide and a surfactant may be added. Further, a pigment or the like can be added as needed.

As an embodiment of including pullulan in the support according to the present invention, it is preferable to incorporate pullulan in the size liquid. Since pullulan is easily dissolved in the aqueous solution of these water-soluble polymers, pullulan can be directly blended in the size liquid, but of course, the aqueous solution can be prepared in advance and blended. The amount of pullulan added is preferably 1 g / m ² to 30 g / m ² after drying.
It is more preferable that the amount is ２０20 g / m ² .

As a method for impregnating the base paper with the size liquid, it is preferable to impregnate and apply the liquid by a known means such as a size press, a tab size or a gate roll coater.

The substrate of the recording material support of the present invention is preferably a substrate in which a thermoplastic resin layer is formed on both sides of the base paper, or at least the side on which the recording is performed on the base paper. Examples of such supports include, for example,
(1) A thermoplastic resin is melt-extruded and coated on a base paper to laminate a plastic layer. (2) A gas barrier layer is further coated and laminated on a thermoplastic resin layer melt-extruded and coated on a base paper. (3) a plastic film layer laminated by bonding a plastic film to base paper; and (4) a plastic film bonded to the base paper, and a thermoplastic resin layer is further provided on the plastic film layer by a melt extrusion method. And (5) a method in which a thermoplastic resin is melt-extrusion coated on a base paper to laminate a plastic layer, and then the plastic film is adhered.

As a method of incorporating pullulan in these embodiments, the method of (1) forming a layer made of pullulan or a layer containing pullulan (hereinafter, appropriately referred to as a pullulan-containing layer) on the surface of the plastic layer, (2) ) To (5), a method of using pullulan as an adhesive component when bonding each layer of the laminate, and incorporating the same into a support, and a method of applying a pullulan-containing layer to a desired position of such a laminate. And the like. In any case, it is necessary to consider that the content of pullulan is in the above-mentioned preferable range.

As a part of the base material of the recording material support of the present invention, the thermoplastic resin which is melt-extruded and coated on base paper includes polyolefin resins, for example, α-olefin homopolymers such as polyethylene and polypropylene, and A mixture of these various polymers or a random copolymer of ethylene and vinyl alcohol is preferred. The thickness of the thermoplastic resin to be melt-extruded and coated on the base paper is not particularly limited, but is usually preferably 10 to 60 μm. When a thermoplastic resin such as polyethylene, for example, LDPE (low-density polyethylene), HDPE (high-density polyethylene), or L-LDPE (linear low-density polyethylene) is used alone or as a mixture, these thermoplastic resins are used. It is preferable to form a pullulan-containing layer having excellent gas barrier properties adjacent to the plastic resin layer.

If a random copolymer of ethylene and vinyl alcohol is mixed with the above-mentioned polyethylene as a thermoplastic resin or melt-extruded and coated on base paper by co-extrusion, a support having a smaller oxygen permeability can be obtained. You can also get Thus, the oxygen permeability of cardboard is 100cc
When a plastic film having a thickness of not more than / m ² / day is bonded (laminated), the resin of the plastic film may be a polyester film, a polyvinylidene chloride film, a polycarbonate film, a polyvinyl chloride film, or a random copolymer of ethylene and vinyl alcohol. Polymer films and the like are preferred. Particularly preferred are a polyester film, a polyvinylidene chloride film, and a random copolymer film of ethylene and vinyl alcohol. More preferably, the polyester film is, for example, a polyethylene terephthalate film, and the other films are, in particular, a random copolymer film of ethylene and vinyl alcohol, which can reduce the oxygen permeability.

The random copolymer of ethylene and vinyl alcohol preferably has an ethylene content of 20 to 60 mol%, more preferably 25 to 50 mol%, and a saponification degree of 90 mol% or more, more preferably Is 95 mol%
The above is desirable from the viewpoint of moldability and oxygen permeability.

The thickness of these plastic films is 8
It is preferable to set it to 60 μm. Regarding film formation processing of these plastic films, see “Plastic Film Processing and Applications”, Plastic Film Research Council.
Any of known film forming methods such as a casting method, an extrusion method, a calendar method, and a stretching method described in (Gihodo) can be used.

Further, the plastic film may be filled with a white pigment. Examples of the white pigment to be filled include titanium dioxide, barium sulfate, calcium carbonate, and zinc oxide. These can be used alone or as a mixture. The filling amount of the white pigment in the plastic film varies depending on the type of the white pigment and the type and thickness of the plastic film, but is usually selected to be between 5 and 20%.

Further, an antistatic layer may be provided in order to prevent dust from adhering to the surface of the plastic film and prevent charging failure in a later step. As the antistatic layer, it is possible to use a generally known technique such as providing an ionic organic antistatic agent such as an alkali metal salt of a polymerizable carboxylic acid or an electronic conductive antistatic layer such as tin oxide. .

In the present invention, the method of laminating the base paper and the plastic film can be appropriately selected from the known lamination methods described in, for example, "Handbook of New Laminating Processes" edited by Processing Technology Research Group, and adopted. However, it is preferable to employ so-called dry lamination, solvent-free dry lamination, dry lamination using an electron beam or ultraviolet curable resin, or hot lamination, and more preferably, dry lamination or solvent-free dry lamination. It is desirable to do.

Dry lamination means plastic
After applying the adhesive to the film, it is dried and then about 100
Method of heat-pressing base paper and plastic film at ℃
In this case, the adhesive used is a solvent type urethane
Resin, vinyl resin, acrylic resin, polyamide resin
5 to 15 g / m of fat, epoxy resin, rubber resin, etc. ^Two
It can be used, but instead of these adhesives,
Uses pullulan as an adhesive component in addition to the adhesive
Is preferred.

Solvent-free dry lamination is a method in which a plastic film is coated with a reaction-curable adhesive such as a one-component moisture-curable urethane adhesive or a two-component urethane adhesive.
The adhesive is reactively hardened by applying -2.0 g / m < ² > and pasting it on cardboard and then aging, so that the adhesion between the plastic film and the base paper can be made strong.

In the present invention, the resin layer formed on the support is formed on at least the front surface, that is, the surface on which recording is performed. Therefore, the resin layer may be formed on both surfaces of the support, or the resin layer may be formed only on the support surface side on which recording is performed. However, the front side,
That is, the resin layer on the side on which the heat-sensitive recording layer is coated preferably contains a white pigment, but the type and amount of the white pigment can be appropriately selected from known ones.

Further, known additives such as a fluorescent whitening agent and an antioxidant can be added to the resin constituting the plastic film. As the white pigment to be filled,
Examples include titanium dioxide, barium sulfate, barium carbonate, calcium carbonate, lithopone, alumina white, zinc oxide, silica antimony trioxide, and titanium phosphate. These can be used alone or as a mixture. Among these, titanium dioxide and zinc oxide are particularly preferred from the viewpoint of whiteness, dispersibility and stability.

Titanium dioxide may be rutile or anatase, and they may be used alone or as a mixture. Further, those manufactured by the sulfuric acid method or those manufactured by the chlorine method may be used. Examples of titanium dioxide include those subjected to surface coating with an inorganic substance such as hydrated alumina treatment, hydrated silicon dioxide-based treatment, or zinc oxide treatment, trimethylolmethane, trimethylolethane, trimethylolpropane, and 2,4-dihydroxy-2-methyl. A material that has been surface-coated with an organic substance such as pentane or a material that has been treated with a siloxane such as polydimethylsiloxane can be used as appropriate. The filling amount of the white pigment in the resin layer varies depending on the white pigment used and the thickness of the resin layer, and is usually selected so as to be between 5% by weight and 20% by weight.

As the extrusion coating equipment for extruding and coating a thermoplastic resin such as polyolefin, an ordinary extruder for polyolefin and a laminator are used. The thickness of the resin layer coated on the base paper is desirably thicker on the surface on which the heat-sensitive recording layer is formed (the front surface side) than on the surface on which the heat-sensitive recording layer is not formed (the back surface).

Before extruding and coating the resin layer on the base paper, it is preferable to pre-treat the base paper in order to strengthen the adhesion between the base paper and the resin coating layer. Examples of the pretreatment of the base paper include an acid etching treatment with a chromic sulfate mixed solution, a flame treatment with a gas flame, an ultraviolet irradiation treatment, a corona discharge treatment, a glow discharge treatment, an anchor coat treatment such as alkyl titanate, and the like, which can be freely selected. In particular, corona treatment is advantageous from the viewpoint of simplicity. In the case of corona treatment, it is necessary to perform treatment so that the contact angle with water becomes 70 ° or less.

As an anchor coating agent, organic titanium-based, isocyanate-based (urethane-based) polyethyleneimine-based, polybutadiene-based and the like are known. Specifically, as an organic titanium-based compound, tetraisopropyl titanate, tetrabutyl titanate, alkyl titanates such as tetrastearyl titanate, titanium acylates such as butoxytitanium stearate, and titanium chelates such as titanium acetylacetonate are known. . As the isocyanate (urethane), toluene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate (HMDI), xylylene diisocyanate (XD
I), isophorone diisocyanate (IPDI) and the like are known.

In order to improve the adhesiveness between the resin layer of polyolefin or the like and the recording layer provided thereon,
The surface of the resin layer may be subjected to a surface treatment such as a corona discharge treatment, or the surface of the resin layer may be provided with an undercoat layer mainly composed of gelatin after the corona discharge treatment.

The surface opposite to the surface on which the recording of the base paper is performed, that is, the thermoplastic resin layer such as polyethylene on the back surface side is usually a mat surface. On these thermoplastic resin layers such as polyethylene on the back surface, it is possible to provide an ionic organic antistatic agent such as an alkali metal salt of a polymerizable carboxylic acid or an antistatic layer containing colloidal silica or the like as necessary. It is possible.

The support in the present invention is as described above.
1 to 30 g / m in the support^TwoPullulan
Contains, but contains pullulan with excellent oxygen barrier properties
In the support of the present invention, JIS
 Oxygen permeability measured by the K-7126B method is 50 cc /
m^Two/ Day or less is preferable. Support oxygen
The lower the transmittance, the better, but it contains pullulan and contains oxygen
Transmittance is 50cc / m ^TwoWhat if it is less than / day
Long-term storage, fading,
Light resistance can be maintained to the extent that there is no problem in practical use
You.

The recording material support of the present invention obtained as described above can be suitably used for various recording materials.

Next, the recording material to which the recording material support of the present invention can be applied will be described. The recording material applicable to the recording material support of the present invention is not particularly limited, and has a recording layer containing a coloring component, that is, (1) a substantially colorless coloring component A and a coloring component A Having a recording layer containing a substantially colorless color-forming component B, which forms a color by reacting with, and (2) denaturation by applying energy such as light, heat, pressure, etc. It can be applied to all of those having a recording layer containing a coloring component which develops a color when reacted, and (3) a recording material (for example, copy paper) in which a coloring material such as toner is fixed on the surface by a suitable means. )) Can also be suitably used. Specifically, for example, (1) may be a heat-sensitive recording material, (2) may be a silver halide photographic recording material, and (3) may be an electrophotographic recording material.

Next, the components of the recording layer constituting the recording material according to the present invention will be described. In the support of the present invention,
As a recording layer formed on a support, (1) a color-forming layer contains at least a substantially colorless color-forming component A, and the color-forming component A reacts to form a substantially colorless color-forming component B; What is done will be described. The color-forming component A and the color-forming component B used here are components that cause a color-forming reaction when they come into contact with each other. Examples of the combinations thereof include the following (A) to (W). (A) A combination of a photodegradable diazo compound and a coupler. (B) A combination of an electron-donating dye precursor and an electron-accepting compound. (C) A combination of a metal salt of an organic acid such as silver behenate and silver stearate with a reducing agent such as protocatechinic acid, spiroindane and hydroquinone. (D) A combination of iron salts of long-chain fatty acids such as ferric stearate and ferric myristate with phenols such as tannic acid, gallic acid and ammonium salicylate. (E) Organic acid heavy metal salts such as nickel, cobalt, lead, copper, iron, mercury, and silver salts such as acetic acid, stearic acid, and palmitic acid; and alkaline earth metals such as calcium sulfide, strontium sulfide, and potassium sulfide. A combination with a sulfide, or a combination of the organic acid heavy metal salt with an organic chelating agent such as s-diphenylcarbazide or diphenylcarbazone. (F) A combination of a heavy metal sulfate such as a sulfate of silver, lead, mercury, sodium and the like, and a sulfur compound such as sodium tetrathionate, sodium thiosulfate and thiourea. (G) ferric fatty acid salts such as ferric stearate;
Combinations with aromatic polyhydroxy compounds such as 3,4-hydroxytetraphenylmethane. (H) A combination of an organic acid metal salt such as oxalate and mercury oxalate and an organic polyhydroxy compound such as polyhydroxy alcohol, glycerin and glycol. (Ii) A combination of a ferric fatty acid salt such as ferric pelargonic acid or ferric laurate, and a thiocesylcarbamide or isothiocesylcarbamide derivative. (N) A combination of a lead salt of an organic acid such as lead caproate, lead pelargonate or lead behenate with a thiourea derivative such as ethylenethiourea or N-dodecylthiourea. (R) A combination of a heavy metal salt of a higher fatty acid such as ferric stearate and copper stearate with zinc dialkyldithiocarbamate. (Ii) Those that form an oxazine dye, such as a combination of resorcinol and a nitroso compound. (W) A combination of a formazan compound and a reducing agent and / or a metal salt.

Among them, (a) a combination of a photodegradable diazo compound and a coupler, (b) a combination of an electron-donating dye precursor and an electron-accepting compound, and (c) a combination of an organic metal salt and a reducing agent. Since the combinations are widely used, the representative combinations (a) to (c) of the color forming components will be described below.

The photo-decomposable diazo compound in the combination of the photo-decomposable diazo compound and the coupler in the above (a) is a compound which reacts with a developer called a coupling component to be described later to form a desired hue. It is a diazo compound that decomposes upon receiving light of a specific wavelength before the reaction, and has no color developing ability even when a coupling component acts.

The hue in this color forming system is mainly determined by the diazo dye formed by the reaction between the diazo compound and the coupling component. Therefore, as is well known,
The color hue can be easily changed by changing the chemical structure of the diazo compound or the chemical structure of the coupling component, and a substantially arbitrary color hue can be obtained depending on the combination.

The photodegradable diazo compound in the present invention mainly refers to an aromatic diazo compound, and more specifically refers to an aromatic diazonium salt, a diazosulfonate compound, and a diazoamino compound.

[0053] The diazonium salt of the general formula ArN ₂ ⁺ X ^-
(Wherein Ar represents a substituted or unsubstituted aromatic moiety, N ₂ ⁺ represents a diazonium group, and X ⁻ represents an acid anion.) Usually, the light of a diazonium salt The resolution wavelength is said to be the absorption maximum wavelength. The maximum absorption wavelength of the diazonium salt ranges from about 200 nm to 700 nm depending on its chemical structure.
It is known to change to the order of nm [“Photodecomposition and chemical structure of photosensitive diazonium salts” by Takahiro Tsunoda and Ao Yamaoka
Journal of the Photographic Society of Japan 29 (4) 197-205 (196
5)]. That is, when a diazonium salt is used as a photodecomposable compound, it is decomposed by light having a specific wavelength according to its chemical structure, and when the chemical structure of the diazonium salt is changed, a coupling reaction with the same coupling component occurs. The hue of the dye also changes.

Many diazosulfonate compounds that can be used in the present invention are known, and are obtained by treating each diazonium salt with a sulfite.
The diazoamino compound that can be used in the present invention is obtained by coupling a diazo group with dicyandiamide, sarcosine, methyltaurine, N-ethylanthranic acid-5-sulfonic acid, monoethanolamine, jetanolamine, guanidine, or the like. Compound.

The details of these diazo compounds are described in, for example, JP-A-2-136286.

The diazo compound develops a predetermined hue upon reaction with a color developer, and decomposes upon receiving light of a specific wavelength before the reaction, and after that the coupler is no longer acted upon. Since it has no color-forming ability, it is used in a multicolor heat-sensitive recording material in combination with (b) an electron-donating colorless dye and an electron-accepting compound described later.

As a light source for photolysis of a diazo compound,
Various light sources that emit light of a desired wavelength can be used. For example, various light sources such as various fluorescent lamps, xenon lamps, xenon flash lamps, mercury lamps of various pressures, photographic flashes, and strobes can be used. or,
In order to make the light fixing zone compact, the light source unit and the exposure unit may be separated using an optical fiber.

Coupling components which form a dye by coupling with a diazo compound used in the present invention include, for example, 2-hydroxy-3-naphthoic acid anilide, resorcinol and JP-A-62-146678. Can be mentioned.

Further, an image of an arbitrary color tone can be obtained by using two or more of these coupling components in combination. Therefore, the present invention is not limited to a single-color recording material.

Since the coupling reaction between the diazo compound and the coupling component easily occurs in a basic atmosphere, a basic substance may be added to the heat-sensitive layer.

As the basic substance, a water-insoluble or water-insoluble basic substance or a substance which generates an alkali by heating is used. Examples thereof are inorganic and organic ammonium salts, organic amines, amides, ureas and thioureas and their derivatives, thiazoles, viroles, pyrimidines,
Examples include nitrogen-containing compounds such as piperazines, guanidines, indoles, imidazoles, imidazolines, triazoles, morpholines, piperidines, amidines, pharmazins, and pyridines. Specific examples thereof are described in, for example, JP-A-61-291183. Incidentally, two or more basic substances may be used in combination.

In the combination of the electron-donating colorless dye (b) and the electron-accepting compound (developing agent), the electron-donating colorless dye refers to a compound that donates electrons or receives a proton such as an acid. Having a partial skeleton of lactone, lactam, sultone, spiropyran, ester, amide, etc., and these partial skeletons are brought into contact with the developer, Ring opening or cleavage compounds are used.

A developer for these color formers is as follows.
It can be appropriately selected from known ones and used. For example, developers for leuco dyes include phenol compounds, sulfur-containing phenol compounds, carboxylic acid compounds, sulfone compounds, urea or thiourea compounds, and the like. (1985) pp. 49-54 and 65-70.

Further, for 1 part by weight of the colorless electron-donating dye, 0.3 to 160 parts by weight of a developer,
It is preferable to use up to 80 parts by weight.

When a combination of the electron-donating dye precursor and the electron-accepting compound is used, it is possible to use a recording material capable of reversibly repeating decoloring and coloring. JP-A-5-124360).

Further, the combination of a di- and tri-arylmethane dye precursor (thiolactone) with an organic silver salt is also good (Japanese Patent Application Laid-Open No. 63-501941).

Examples of the organic metal salt in the combination of the organic metal salt and the reducing agent shown in (c) include silver laurate, myristic acetic acid, silver palmitate, silver stearate, silver arachiate and Silver salts of organic compounds having an imino group such as silver salts of long-chain aliphatic carboxylic acids such as silver behenate, silver salts of benzotriazole, silver salts of benzimidazole, silver salts of carbazole and phthalazinone, s
Silver salts of sulfur-containing compounds such as alkylthioglycolates, silver salts of aromatic carboxylic acids such as silver benzoate and silver phthalate, silver salts of sulfonic acids such as silver ethanesulfonate, o-toluenesulfinic acid Silver salts of sulfinic acid such as silver, silver salts of phosphoric acid such as silver phenylphosphate,
There are silver barbiturates, silver saccharinates, silver salts of salicylaldoxime and any mixtures thereof. Among these compounds, long-chain aliphatic carboxylic acid silver salts are preferred, and silver behenate is particularly preferred. Further, behenic acid may be used together with silver behenate.

The reducing agent that can be used in the present invention is
JP-A-53-1020, page 227, lower left column, line 14 to page 229, upper right column, line 11 can be used as appropriate, but in particular, mono, bis, tris or tetrakisphenol , Mono- or bisnaphthols, di- or polyhydroxynaphthalenes, di- or polyhydroxybenzenes, hydroxymonoethers, ascorbic acids, 3-pyrazolidones, pyrazolines, pyrazolones, reducing sugars, phenylenediamines, hydroxyl It is preferable to use amines, reductones, hydroxamines, hydrazides, amide oximes, N-hydroxyureas and the like. Of these compounds, particularly preferred are aromatic organic reducing agents such as polyphenols, sulfonamidephenols, and naphthols.

The color-forming components are usually dispersed separately, generally together with an aqueous solution of a water-soluble polymer such as polyvinyl alcohol, to a size of several microns or less by a ball mill, sand mill or the like. These dispersions are mixed after dispersing, and further, if necessary, an oil-absorbing pigment, a binder, a wax, a metal soap, an antioxidant, an ultraviolet absorber, a surfactant, an antistatic agent, an antifoaming agent, a conductive agent, and a fluorescent agent. A coloring layer coating solution is prepared by adding a dye, a coloring dye and the like. The obtained coating liquid is applied to the support of the present invention, dried, and then imparted with a smoothness by a calendering treatment, thereby forming a recording material.

Materials which cause the above-described color-forming reaction include the viewpoint of improving the transparency of the heat-sensitive layer, the viewpoint of raw preservability such as preventing the contact between the color former and the developer at room temperature (anti-fogging), and the desired applied heat. It is preferable to encapsulate some of the components indispensable for color development from the viewpoint of controlling color development sensitivity such as color development with energy.

The type of the microcapsules used in this case is not particularly limited, but particularly preferred microcapsules in the present invention are those which prevent the contact of substances inside and outside the capsules at room temperature by the substance sequestering action of the microcapsule wall. The permeability of the substance is increased only while being heated to a certain temperature or higher, and the permeation start temperature can be freely controlled by appropriately selecting the capsule wall material, the capsule core substance, and the additives. Things.
The permeation start temperature in this case corresponds to the glass transition temperature of the capsule wall (for example, JP-A-59-91438).
No., Japanese Patent Application No. 59-190886, and Japanese Patent Application No. 59-994.
No. 90).

Further, a protective layer can be provided on the surface of these recording layers. The protective layer contains a pigment and a binder as main components.

Examples of the binder component that can be used in the protective layer include water-soluble polymers such as methylcellulose, carboxymethylcellulose, hydroxyethylcellulose, starches, gelatin, gum arabic, casein,
Examples include styrene-maleic anhydride copolymer hydrolyzate, ethylene-maleic anhydride copolymer hydrolyzate, isobutylene-maleic anhydride copolymer hydrolyzate, polyvinyl alcohol, modified polyvinyl alcohol, and polyacrylamide. However, the combined use of a water-soluble polymer may cause a decrease in water resistance, and care must be taken regarding the amount and type used.

The water-insoluble binder is generally a synthetic rubber latex or a synthetic resin emulsion, such as styrene-butadiene rubber latex, acrylonitrile-butadiene rubber latex, methyl acrylate-butadiene rubber latex, and vinyl acetate emulsion. Can be The amount of the binder used is 10 to 500% by weight, preferably 50 to 400% by weight, based on the pigment contained in the protective layer.

As the pigment that can be used in the protective layer of the recording material of the present invention, all general organic or inorganic pigments can be used. Specific examples include calcium carbonate, aluminum hydroxide, barium sulfate, titanium oxide, talc, wax, kaolin, calcined kaolin, amorphous silica, urea formalin resin powder, polyethylene resin powder, and benzoguanamine resin powder. These are used alone or in combination of two or more.

The coating solution for the protective layer of the present invention comprises a dispersion of the above pigment.
It is obtained by mixing a liquid, a binder and the like. If necessary
First add a release agent, surfactant, wax, water repellent, etc.
Is also good. Apply the obtained protective layer coating solution on the thermosensitive coloring layer with a bar.
Coater, air knife coater, blade coater, mosquito
Apply and dry using a device such as a ten coater to protect
Layers can be obtained. However, apply the protective layer simultaneously with the color-forming layer.
After applying the coloring layer, dry the coloring layer once.
And apply it on it. Dry coating amount of protective layer
Is 0.5 to 5 g / m^TwoIs preferred, and more preferably
0.8-2g / m ^TwoIt is. Low sensitivity with large application amount
If the coating amount is low, the water resistance decreases,
This is not preferred either. After applying the protective layer, carry
(2) To be given energy such as light, heat, pressure, etc.
More denatured and develops color by reacting other developed components
Having a recording layer containing a coloring component,
Is a silver halide photographic recording material. this is,
An undercoat layer is provided on the support to provide a silver halide emulsion
An emulsion layer containing a light-sensitive photographic emulsion is used as a recording layer.
Representative of silver halide contained in silver halide emulsion
As for silver chloride, silver chlorobromide, silver iodide and
And the like in accordance with the purpose. Also,
The recording material of the present invention can also be used as a photographic paper support as a true material
A material support can be used.

Further, when the present invention is applied to a recording material for fixing (fixing) a color material, such as an electrophotographic recording material, the support itself can be used as the recording material if the surface smoothness is good. However, it is also preferable to provide a surface layer in order to improve heat resistance and affinity with coloring materials such as toner and pigment.

Further, if necessary, a back coat layer may be provided on the surface of the support of the present invention opposite to the surface on which recording is performed. As the back coat layer, any known back coat layer of a recording material can be used.

When a recording layer, a protective layer, a surface layer and the like are formed on the recording material support of the present invention, an undercoat layer may be provided on the support in order to improve the affinity between the layers. It is also possible to add an antifoaming agent to various coating solutions to eliminate bubbles generated at the time of application when forming these layers, or to improve the leveling of the solution and to prevent the generation of coating streaks. It is also possible to add activators. Further, it is also possible to add an antistatic agent as needed. Furthermore,
The undercoat layer may be made opaque by adding a white pigment.

When the above-mentioned recording layer, protective layer and the like are formed on the support of the present invention, generally known coating methods such as dip coating, air knife coating, curtain coating, roller coating, The coating can be performed by a doctor coating method, a wire bar coating method, a slide coating method, a gravure coating method, or an extrusion coating method using a hopper described in U.S. Pat. No. 2,681,294. U.S. Pat. Nos. 2,761,791 and 3,508,947 as required.
No. 2,941,898, and No. 3,526,
No. 528, Yuji Harazaki, "Coating Engineering" 25
It is also possible to divide into two or more layers and apply simultaneously by the method described on page 3 (published by Asakura Shoten in 1973) or the like, and an appropriate method can be selected according to the application amount, application speed, and the like. .

[0081]

(Surface size liquid composition)

· Pullulan as (Hayashibara Biochemical Laboratories Ltd., Toriguruko A) 25 parts adhesion amount CaCl ₂ 2 parts Fluorescent whitening agent 0.3 parts surface sizing solution pullulan at 38 cc / m ² as a liquid (solid content) 9 It was 0.5 g / m ² . Thereafter, it was dried by a steam dryer to make the water content 7%, and then a base paper having a density of 1.0 g / cm ³ was obtained by a calender.

After performing a corona discharge treatment on the wire side of the base paper, high-density polyethylene was coated using a melt extruder so as to have a resin thickness of 30 μm to form a resin layer composed of a mat surface (this surface). Is called the back surface).
After the polyethylene resin-coated surface of the back surface is subjected to corona discharge treatment, aluminum oxide (alumina sol 100 manufactured by Nissan Chemical Industries, Ltd.) / Silicon dioxide (Snowtex O manufactured by Nissan Chemical Industries, Ltd.) = 1/1 as an antistatic agent. 2 (weight ratio) was dispersed in water, and 0.2 g / m ² of the weight after drying was applied. (This is called a back PE lamination product.) Also, the felt side of the base paper is subjected to corona discharge treatment, and low density polyethylene containing 10% by weight of titanium dioxide and a trace of ultramarine blue is melt-extruded to a resin thickness of 30 μm. Then, a resin layer having a glossy surface was formed (this surface is referred to as a front surface). After a corona discharge treatment was applied to the front side of the polyethylene resin-coated surface, a gelatin undercoat layer was applied so that the weight after drying was 0.1 g / m ² .

The oxygen permeability of the support obtained as described above was measured using OX-TRAN2 / 20MH manufactured by MOCON in accordance with JIS K-7126B.
The oxygen transmission rate was 21 cc / m ² / day.

FIG. 1 shows a recording material support 10 according to the first embodiment.
FIG. The recording material support 10 has a size liquid 14 containing pullulan permeating the base paper 12, a low-density polyethylene resin layer 16 containing titanium dioxide or the like on the front side, and a high-density polyethylene resin layer 16 on the back side. The layer 18 is configured by being laminated. Example 2 A support was obtained in the same manner as in Example 1 except that the composition of the surface size liquid was as described below.

[Surface size liquid composition] Pullulan (Trigluco A, manufactured by Hayashibara Biochemical Laboratory) 21 parts CaCl ₂ 2 parts Fluorescent whitening agent 0.3 parts The amount of pullulan deposited on this support was 7.3 g / m ² . When the oxygen permeability of the support was measured in the same manner as in Example 1, the oxygen permeability was 32 cc / m ² / day. Example 3 A support was obtained in the same manner as in Example 1 except that the composition of the surface size liquid was changed as follows.

[Surface size liquid composition] 17 parts of pullulan (Trigluco A, manufactured by Hayashibara Biochemical Laboratory) 2 parts of CaCl ₂ 0.3 parts of fluorescent whitening agent The amount of pullulan adhered to this support was 6.0 g / m ² . Further, when the oxygen permeability of the support was measured in the same manner as in Example 1, the oxygen permeability was 48 cc / m ² / day. Example 4 A support was obtained in the same manner as in Example 1 except that the composition of the surface size liquid was changed as follows.

[Surface size liquid composition] 15 parts of pullulan (manufactured by Hayashibara Biochemical Laboratory, Trigluco A) 5 parts of polyvinyl alcohol (manufactured by Kuraray Co., Ltd., PVA-203) 5 parts CaCl_Two 2 parts-Optical brightener 0.3 parts Pullulan adhesion amount of this support is 5.5 g / m^Two, PVA
1.3 g / m ^TwoMet. Also the support oxygen
When the transmittance was measured in the same manner as in Example 1, the oxygen transmittance was measured.
Is 39cc / m^Two/ Day. [Comparative Example 1] The composition of the surface size liquid was changed as follows.
Was obtained in the same manner as in Example 1.

[Surface size liquid composition] Starch (manufactured by Japan Food Processing Co., Ltd., MS ^# 3800) 16 parts CaCl ₂ 2 parts Fluorescent whitening agent 0.3 parts The amount of starch adhering to this support was 16 g / m ² .
Further, when the oxygen permeability of the support was measured in the same manner as in Example 1, the oxygen permeability was 380 cc / m ² / day. Comparative Example 2 A support was obtained in the same manner as in Example 1 except that the composition of the surface size liquid was changed as follows.

[Surface size liquid composition] 5 parts of carboxymethylcellulose (Daiichi Kogyo Seiyaku Co., Ltd., Cellogen 5A) 2 parts of CaCl ₂ 0.3 parts of fluorescent whitening agent
It was 3 g / m ² . When the oxygen permeability of the support was measured in the same manner as in Example 1, the oxygen permeability was 1100 c.
c / m ² / day. Comparative Example 3 A support was obtained in the same manner as in Example 1 except that the composition of the surface size liquid was changed as follows.

[Surface size liquid composition] 6 parts of polyvinyl alcohol (manufactured by Kuraray Co., Ltd., PVA-117) 2 parts of CaCl ₂ 0.3 parts of fluorescent whitening agent PVA adhesion amount of this support is 1.3 g / M ² .
Further, when the oxygen permeability of the support was measured in the same manner as in Example 1, the oxygen permeability was 970 cc / m ² / day. Comparative Example 4 A support was obtained in the same manner as in Example 1 except that the surface sizing liquid was not applied to the base paper.

The oxygen transmission rate of this support was measured in the same manner as in Example 1. The oxygen transmission rate was 1250 cc / m ² /
It was day. Example 5 Corona discharge treatment was again performed on the gelatin-undercoated surface of the support obtained in Comparative Example 3, and a 10% aqueous solution of pullulan was applied by a bar coater at 30 cc / m ² to obtain a support of Example 5. .

FIG. 2 shows a recording material support 20 according to the fifth embodiment.
FIG. In the recording material support 20, a low-density polyethylene resin layer 16 containing titanium dioxide or the like is laminated on the front side of the base paper 12 and a high-density polyethylene resin layer 18 is laminated on the back side. A layer 22 made of pullulan is formed on the polyethylene resin layer 16.

The amount of pullulan deposited on this support was 3 g / m ^2.
Met. When the oxygen permeability of the support was measured in the same manner as in Example 1, the oxygen permeability was 19 cc / m ² / da.
y. [II] Evaluation of Support Next, after performing corona discharge on the supports of Examples 1 to 5 and Comparative Examples 1 to 4, the following full-color heat-sensitive recording layers were provided. Hereinafter, a production example of a full-color heat-sensitive recording material will be described. (1) Preparation of Cyan Thermosensitive Recording Layer Solution (Preparation of Capsule Solution Containing Electron Donating Dye Precursor) Solution A 3- (o-methyl-p-dimethylaminophenyl) -3
-(1'-ethyl-2'-methylindol-3-yl) phthalide (electron-donating dye precursor)
After dissolving in 0 parts, 20 parts of alkylnaphthalene (high boiling point solvent) was added, and the mixture was heated and uniformly mixed.

To the obtained solution, 20 parts of a 1/3 adduct of xylylene diisocyanate / trimethylolpropane was added, and the mixture was stirred uniformly to prepare solution A. 2. Solution B Liquid B was prepared by adding 2 parts by weight of a 2% by weight aqueous solution of sodium dodecyl sulfonate to 54 parts of a 6% by weight aqueous solution of phthalated gelatin.

The solution A was added to the solution B and emulsified and dispersed using a homogenizer to obtain an emulsified dispersion. 68 parts of water is added to the obtained emulsified dispersion, mixed and homogenized, and then the mixture is heated to 50 ° C. while stirring to encapsulate the microcapsules so that the average particle size of the microcapsules becomes 1.2 μm. The reaction was performed for 3 hours to obtain a capsule liquid. (Preparation of developer emulsified dispersion) 5 parts of 1,1- (p-hydroxyphenyl) -2-ethylhexane (developer), 0.3 parts of tricresyl phosphate and 0.1 part of diethyl maleate were added. Dissolved in 10 parts of ethyl acetate. The obtained solution was mixed with 50 g of a 6% by weight aqueous solution of gelatin and 2% by weight.
Was added to a mixed solution of 2 g of an aqueous sodium dodecyl sulfonate solution, and emulsified for 10 minutes using a homogenizer to obtain an emulsified dispersion. (Preparation of coating liquid) A coating liquid was obtained by mixing the capsule liquid containing the electron-donating dye precursor / the emulsified developer / dispersing liquid so as to have a weight ratio of 1/4. (2) Preparation of magenta thermosensitive recording layer liquid (preparation of capsule liquid containing diazo compound) 4-N-
2.0 parts of (2- (2,4-di-tert-amylphenoxy) butyryl) piperazinobenzenediazonium hexafluorophosphate (diazo compound: decomposed by light having a wavelength of 365 nm) was dissolved in 20 parts of ethyl acetate. Thereafter, 20 parts of alkylnaphthalene was further added, and the mixture was heated and uniformly mixed. To the obtained solution, 15 parts of an adduct (capsule wall material) of xylidine isocyanate / trimethylolpropane 1/3 was added and uniformly mixed to obtain a diazo compound solution.

The obtained solution of the diazo compound was added to a solution obtained by mixing 54 parts of a 6% by weight aqueous solution of phthalated gelatin and 2 parts of a 2% by weight aqueous solution of sodium dodecylsulfonate, and emulsified and dispersed using a homogenizer. .

68 parts of water was added to the obtained emulsified dispersion, mixed uniformly, and heated to 40 ° C. with stirring to carry out an encapsulation reaction for 3 hours so that the average particle size of the capsules was 1.2 μm. Thus, a capsule solution was obtained.

(Preparation of Coupler Emulsion Dispersion) 1- (2 ′
-Octylphenyl) -3-methyl-5-pyrazolone (coupler) 2 parts, 1,2,3-triphenylguanidine 2 parts, tricresyl phosphate 0.3 part and diethyl maleate 0.1 part Dissolved in all parts. The obtained solution was mixed with 50 g of a 6% by weight aqueous solution of gelatin.
And 2 g of a 2% by weight aqueous solution of sodium dodecyl sulfonate
Was added to the mixed aqueous solution, and then emulsified for 10 minutes using a homogenizer to obtain an emulsified dispersion.

(Preparation of Coating Solution) A coating solution was obtained by mixing a capsule solution containing a diazo compound / a coupler emulsion at a weight ratio of 2/3.

(3) Preparation of Yellow Thermosensitive Recording Layer Solution (Preparation of Capsule Solution Containing Diazo Compound)
Dibutoxy-4-tolylthiobenzenediazonium hexafluorophosphate (diazo compound: 420 nm
3.0 parts were dissolved in 20 parts of ethyl acetate, and alkylnaphthalene 2 was added as a high boiling point solvent.
0 parts were added and mixed by heating.

In the resulting solution, 1 part of xylylene diisocyanate / trimethylolpropane was used as a capsule wall material.
15 parts of the / 3 adduct was added and mixed uniformly to obtain a diazo compound solution.

The obtained solution of the diazo compound was added to a solution obtained by mixing 54 parts of a 6% by weight aqueous solution of phthalated gelatin and 2 parts of an aqueous solution of sodium dodecylsulfonate, and emulsified and dispersed using a homogenizer.

68 parts of water was added to the obtained emulsified dispersion, and the uniformly mixed solution was heated to 40 ° C. while further stirring.
An encapsulation reaction was performed for 3 hours so that the average particle diameter of the capsules was 1.3 μm, to obtain a capsule solution. (Preparation of coupler emulsified dispersion) 2-chloro-5- (3-
(2,4-di-tert-pentyl) phenoxypropylamino) acetoacetanilide (2 parts), 1,2,3-triphenylguanidine (1 part), tricresyl phosphate (0.3 parts), and diethyl maleate (0.1 parts) were dissolved in acetic acid. Dissolved in 10 parts of ethyl, poured into an aqueous solution obtained by mixing 50 g of a 6% by weight aqueous solution of gelatin and 2 g of a 2% by weight aqueous solution of sodium dodecylsulfonate, and emulsified for 10 minutes using a homogenizer to obtain an emulsified dispersion. Was. (Preparation of coating liquid) Capsule liquid containing diazo compound /
The coupler emulsified dispersion was mixed at a weight ratio of 2/3 to obtain a coating liquid. (4) Preparation of Intermediate Layer Solution Polyacrylic acid (trade name: Julimer AC-10L: Nippon Pure Chemical Co., Ltd.) was added to 10 parts of a 15% by weight aqueous solution of gelatin (# 750: trade name of Nitta Gelatin Co., Ltd.).
A 3% by weight aqueous solution was added and uniformly mixed to obtain an intermediate layer liquid. (5) Preparation of protective layer solution Itaconic acid-modified polyvinyl alcohol (KL-318:
100 g of a 6% by weight aqueous solution of Kuraray Co., Ltd.)
And 10 g of a 30% by weight dispersion of epoxy-modified polyamide (FL-71: trade name, manufactured by Toho Chemical Co., Ltd.), and a 40% by weight dispersion of zinc stearate (Hydrin Z: manufactured by Chukyo Yushi Co., Ltd.) 15 g of trade name was added to obtain a protective layer liquid. (6) Preparation of heat-sensitive recording material On the polymer layer of each of the sheet-like substrates of Examples 1 to 5 and Comparative Examples 1 to 4, using a slide type hopper type bead coating device, cyan was sequentially formed on the slide from the support. A multi-layer heat-sensitive recording material was obtained by applying a multi-layered heat-sensitive recording layer liquid, an intermediate layer liquid, a magenta heat-sensitive recording layer liquid, an intermediate layer liquid, a yellow heat-sensitive recording layer liquid, and a protective layer liquid.

The coating amount was 6.1 g / m ^{2 for} the cyan thermosensitive recording layer, 1.0 g / m ^{2 for} the intermediate layer, and 7.8 g / m ^{2 for} the magenta thermosensitive recording layer in that order from the support side in terms of solid content after drying. m
^2. Each coating solution was applied such that the intermediate layer became 1.0 g / m ² , the yellow heat-sensitive recording layer became 7.2 g / m ^2, and the protective layer became 2.0 g / m ² .

Thermal recording was performed on each of the multicolor heat-sensitive recording materials of Examples 1 to 5 and Comparative Examples 1 to 4, and thereafter, light resistance and background fog were evaluated. Thermal recording was performed as follows.

Using a Kyocera thermal head KST type,
(1) Recording energy per unit area is 35 mJ / m
The power applied to the thermal head and the pulse width were determined so as to obtain m ² , the thermosensitive recording material was printed, and a yellow image was recorded. (2) Using the recording material as the light emission center wavelength 42
Irradiate for 10 seconds under an ultraviolet lamp of 0 nm and output of 40 W,
(3) The recording energy per unit area is 66 mJ again
/ Mm ² , the power applied to the thermal head and the pulse width were determined, printing was performed, and a magenta image was recorded. (4) Emission center wavelength 365 nm, output 40
Irradiate for 15 seconds under a UV lamp of W, (5) determine the power and pulse width to be applied to the thermal head so that the recording energy per unit area becomes 90 mJ / mm ² again, print and record a cyan image. did. As a result, in addition to the yellow, magenta, and cyan color images, the recording portion where the yellow and magenta recordings overlap is red, the portion where magenta and cyan overlap is blue, and the portion where yellow and cyan overlap is green. And yellow, magenta,
The portion where the cyan records overlapped was colored black. The unrecorded area was white. [Evaluation method] (1) Light fastness (residual rate of image) The light fastness was evaluated using a Weatherometer C165 (Atlas Blectric)
Devices Co.) illuminated at 0.9 W / m ² for 48 hours. In the non-printed area, the evaluation was made based on the reflection density (yellow component) measured using "Reflection Densitometer RD918" manufactured by Macbeth. Also,
In the image part, evaluation was made based on the residual ratio of cyan density.

Residual rate of image part (%) = [(Weatheromete
r Reflection density after irradiation) / (reflection density before irradiation with Weatherometer)] × 100 to determine and evaluate the residual ratio of the dye in the image area. This image residual ratio is required to be 85% or more for practical use. (2) Background fogging Background fogging is based on Weatherometer C1 65 (Atlas Blectric
Devices Co.), the reflection density (yellow component) of the non-printed portion of the sample irradiated at 0.9 W / m ² for 48 hours.
Was evaluated. The reflection density was measured using a Macbeth “reflection densitometer”.
RD918 ". This background fog needs to be 0.15 or less for practical use.

The evaluation results of Examples 1 to 5 and Comparative Examples 1 to 4 were evaluated together with the previously measured oxygen permeability.
The results are shown in Table 1 below.

[0109]

[Table 1]

From Table 1, it can be seen that the thermal recording materials of Examples 1 to 5 all have an oxygen permeability of the support of 50 cc / m ^2.
/ Day or less, the image remaining rate is 85% or more,
The background fog is 0.15 or less, which indicates that it has the characteristics required for practical use. On the other hand, Comparative Example 4, which did not contain pullulan, had a high oxygen permeability, and the background fog was at a level that would cause a practical problem. Further, with respect to Comparative Examples 1 to 3 using size liquids containing conventionally known components such as starch and PVA, although slight improvements are seen respectively from Comparative Example 4, both light resistance and background fogging become practical problems. Level.

[0111]

As described above, according to the present invention, there is provided a recording material support which can be applied to various recording materials and is excellent in the fading property, light resistance and long-term preservation of images. can do.

[Brief description of the drawings]

FIG. 1 is a schematic sectional view showing a recording material support of Example 1 according to the present invention.

FIG. 2 is a schematic sectional view showing a recording material support of Example 5 according to the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 10 Recording material support 12 Base paper 14 Size liquid containing pullulan 20 Recording material support 22 Layer composed of pullulan

Claims (4)

[Claims] 1. A paper and / or plastic base material,
A recording material support comprising 1 to 30 g / m ^{2 of} pullulan. 2. The recording material support according to claim 1, wherein the base material is paper, and the pullulan is contained in the paper. 3. The recording according to claim 1, wherein the recording material support is a laminate including a layer made of paper and / or a plastic film, and has at least one layer containing pullulan. Support for materials. 4. An oxygen transmission rate of the recording material support is 5
4. The recording material support according to claim 1, wherein the support is 0 cc / m ² / day or less.