JPH1143899A - Recording material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a recording material of which the carrier has low oxygen permeability and can store the images free from surface fogging for a long period of time. SOLUTION: Relating to a recording material having the recording layers on the carrier, the carrier comprises a base paper having the thermoplastic layers containing a laminar inorganic compound on one or both surfaces. The laminar inorganic compound is a swelling synthetic mica and preferably has an aspect ratio of >=20. In a preferred embodiment, one or more layers are formed on the thermoplastic resin layer. In addition, the thermoplastic resin is preferably an olefinic resin layer.

Description

DETAILED DESCRIPTION OF THE INVENTION

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a recording material, and more particularly to a recording material such as a heat-sensitive recording material or a photosensitive material which has a low oxygen permeability of a support and is capable of storing an image with little background fog for a long period of time. .

[0001]

2. Description of the Related Art In a recording material, when it is exposed to sunlight for a long time or when it is posted in a room for a long time,
It has the drawback that the background portion is colored by light and the image portion is discolored or faded. This tendency is large in heat-sensitive recording materials such as multicolor heat-sensitive recording materials. Various methods have been proposed to improve the coloring of the background portion and the discoloration and fading of the image portion, but they have not always achieved a sufficient effect.

[0002]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned drawbacks, and it is possible to reduce the oxygen permeability of a support and preserve an image with less background fog for a long time. To provide a recording material.

[0003]

An object of the present invention is to provide a recording material having a recording layer provided on a support, wherein the support comprises a thermoplastic resin layer containing a layered inorganic compound on one or both sides of atoms. This is achieved by a recording material characterized by comprising: One or more thermoplastic resin layers can be further provided on the thermoplastic resin layer containing the layered inorganic compound. The layered inorganic compound is particularly preferably composed of synthetic mica and having an aspect ratio of 20 or more, and the filling amount of the synthetic mica in the thermoplastic resin layer is desirably 1 to 80% by weight. Is desirably formed by melt laminating an olefin resin such as polyethylene. The recording layer may be a thermosensitive recording layer or a silver halide photosensitive layer.

[0004]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The base paper used for the support of the recording material of the present invention is 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, epoxidized fatty acid amide, What added a sizing agent such as paraffin wax and alkenyl succinic acid, a paper strength enhancer such as polyacrylamide, starch and polyamide polyamine epichlorohydrin, and a fixing agent such as a sulfate band and a cationic polymer 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, and since the recording material is desired to have as high a flatness as possible, a material having excellent surface smoothness and flatness is desirable. Therefore, heat and pressure are applied by a machine calender, soft calender, and super calender. It is preferable to perform surface treatment.

[0006] The support of the recording material of the present invention is desirably one in which a surface sizing agent is applied to both sides of a base paper, and the surface sizing liquid is an aqueous solution of polyvinyl alcohol and / or a modified product thereof. CMC, HE
C, polymer compounds such as sodium alginate and gelatin, metal salts such as calcium chloride, sodium chloride and sodium sulfate, as well as hygroscopic substances such as glycerin and polyethylene glycol, dyes, coloring and whitening substances such as fluorescent brighteners, A pH control agent such as caustic soda, aqueous ammonia, hydrochloric acid, sulfuric acid, and sodium carbonate may be added. 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 a method of impregnating the base paper, it is preferable to impregnate and apply by a size press, a tab size, a gate roll coater or the like.

[0007] The support of the recording material of the present invention is a support in which a thermoplastic resin layer is formed on both sides of the base paper or on one side of the base paper (at least the side of the base paper on which the recording layer is formed). Examples of such a support include, for example, (1) a base paper obtained by applying a thermoplastic resin by melt extrusion coating;
(2) a thermoplastic resin layer provided by a melt extrusion method on a surface of a base paper to which a plastic film is adhered;
Or (3) a material obtained by applying a thermoplastic resin to a base paper by melt extrusion coating and then bonding the plastic film.

[0008] The thermoplastic resin to be melt-extruded and coated on the base paper includes olefin resins, for example, α-olefin homopolymers such as polyethylene and polypropylene, and mixtures of these various polymers, or ethylene and vinyl alcohol. Are preferred. Examples of polyethylene include LDPE (low-density polyethylene), HDPE (high-density polyethylene), L-LDPE
(Linear low-density polyethylene) can be used alone or in combination. In the case of an olefin-based resin, the melt flow rate before processing is 1.2 g / 10 min to 12 g / 1 as a value measured under the condition 4 in Table 1 of JIS 7201.
A time of 0 minutes is desirable. The thickness of the thermoplastic resin to be melt-extruded and coated on the base paper is not particularly limited.
0-60 μm is preferred.

[0009]

In the present invention, the thermoplastic resin layer formed on the base paper contains at least a layered inorganic compound. As the layered inorganic compound in the present invention, a swellable inorganic layered compound is preferable, and as these compounds,
Examples include swellable viscosity minerals such as bentonite, hectorite, saponite, beidellite, nontronite, stevensite, beidellite, and montmorillonite, fluorinated mica, and swellable synthetic smectite. These swellable inorganic layered compounds have a laminated structure composed of a unit crystal lattice layer having a thickness of 10 to 15 angstroms, and the substitution of metal atoms in the lattice is significantly larger than other clay minerals.
As a result, the lattice layer is deficient in positive charge, and cations such as Na ⁺ , Ca ²⁺ , and Mg ²⁺ are adsorbed between the layers to compensate for this. The cations interposed between these layers are called exchangeable cations and exchange with various cations. Especially when the cation between the layers is Li ⁺ , Na ^+, etc.
Due to the small ionic radius, the bond between the layered crystal lattices is weak and swells greatly with water. When shear is applied in this state, it is easily cleaved and forms a stable sol in water.
Bentonite and fluorinated mica have a strong tendency and are preferred for the purpose of the present invention.

The fluorinated mica used in the present invention is particularly preferably a swellable synthetic mica. The fluorinated mica is obtained by using talc as a starting material and intercalating alkali ions with it. The synthesis method is such that an alkali silicofluoride, (K, Na, Li) ₂ Si
O ₄ or ((K, Na, Li) F) is mixed, put into a magnetic crucible, and heat-treated at 800 to 900 ° C. for a short time.
By this treatment, alkali ions are intercalated between the layers of talc, and fluorinated mica is generated.

Examples of the swellable synthetic mica include, for example, Na tetrathick mica NaMg _2.5 (Si ₄ O ₁₀ ) F ₂ Na or Li teniolite (NaLi) Mg ₂ (Si ₄ O)
₁₀₎ F ₂ Na or Li hectorite (NaLi) / 3Mg ₂ / 3L
i _1/3 Si ₄ O ₁₀ ) F _{2 and the} like.

The swellable synthetic mica preferably used in the present invention has a thickness of 1 to 50 nm and an average particle size (planar size) of 1 to 20 μm, more preferably 1 to 10 μm.
m. For diffusion control, the thinner the better, the better, and the planar size is better as long as the smoothness and transparency of the coated surface are not deteriorated. If the plane size is smaller than 1 μm, the oxygen barrier properties are insufficient, and if it is larger than 10 μm, the smoothness of the thermoplastic resin layer containing the swellable synthetic mica is inferior. Further, the aspect ratio of the swellable synthetic mica is 20 or more, preferably 100 or more, preferably 200 or more, and particularly preferably 500 or more. When the aspect ratio of the swellable synthetic mica is less than 20, the oxygen barrier property is insufficient.

The filling amount of the swellable synthetic mica to the thermoplastic resin is desirably 1 to 80% by weight. 1% by weight filling
If the amount is smaller than the above range, the oxygen barrier property becomes insufficient, and the effect of increasing the storage stability of the recording portion cannot be expected.
If the content is more than the weight percentage, it becomes difficult to form a thermoplastic resin layer, and lamination cannot be performed.

As an embodiment of the thermoplastic resin layer containing these swellable synthetic mica, the embodiment shown in FIG. 1 is exemplified. In FIG. 1A, a thermoplastic resin layer is provided on both sides of the base paper, and an olefin-based resin layer 12 such as polyethylene is provided on the back side (the side on which the recording layer is not formed) of the base paper 10. An olefin resin layer 14 such as polyethylene containing a swellable synthetic mica and a white pigment is provided on the front surface (the surface on which the recording layer is formed).

In FIG. 1B, a thermoplastic resin layer is provided on both sides of the base paper, and an olefin-based resin layer 12 such as polyethylene is provided on the back side (the side on which the recording layer is not formed) of the base paper 10. An olefin-based resin layer 16 such as polyethylene containing swellable synthetic mica is provided on the front side of the base paper 10 (the side on which the recording layer is formed), and a polyethylene containing a white pigment is further provided on the thermoplastic resin layer 16. An olefin-based resin layer 18 is provided.

In FIG. 1 (C), a thermoplastic resin layer is provided on both sides of the base paper, and the back side of the base paper 10 (the side on which the recording layer is not formed) is an olefin-based material such as polyethylene containing swellable synthetic mica. A resin layer 20 is provided, and an olefin resin layer 16 such as polyethylene containing swellable synthetic mica is provided on the front side of the base paper 10 (the side on which the recording layer is formed). Further, an olefin resin layer 18 such as polyethylene containing a white pigment is provided.

In the recording material shown in FIG. 1A, since the thermoplastic resin layer 14 contains swellable synthetic mica, the oxygen permeability of the support is reduced and the recording material also contains a white pigment. Therefore, it is possible to prevent the white color of the support from lowering. In the recording material shown in FIG. 1B, since the thermoplastic resin layer 16 contains swellable synthetic mica, oxygen permeability is reduced, and a white pigment is added to the thermoplastic resin layer 18. Therefore, a decrease in white color due to filling of the swelling synthetic cloud can be further prevented as compared with FIG. In the recording material shown in FIG. 1C, both sides of the base paper 10 are sandwiched by the thermoplastic resin 16 and the thermoplastic resin 20 containing swellable synthetic mica.
The oxygen permeability of the support is lower than that of the recording material shown in (B).

Examples of white pigments to be filled in the thermoplastic resin include titanium dioxide, barium sulfate, barium carbonate, calcium carbonate, lithopone, alumina white, zinc oxide, silica antimony trioxide, titanium phosphate and the like. These can be used alone or as a mixture.
Of these, titanium dioxide and zinc oxide, in particular, have whiteness,
It is preferable from the viewpoint of dispersibility and stability. The filling amount of the white pigment in the thermoplastic resin varies depending on the type of the white pigment and the type of the thermoplastic resin and the thickness of the thermoplastic resin layer,
Usually it is chosen to be between 5 and 20% by weight.

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. Further, known additives such as a fluorescent whitening agent and an antioxidant can be added to the thermoplastic resin layer. As the white pigment to be filled,

Before extruding and coating the thermoplastic 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 thermoplastic 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 the 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.

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

The surface of the base paper opposite to the surface on which the recording layer is formed, that is, the thermoplastic resin layer such as polyethylene on the back surface is usually a matte 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 on a thermoplastic resin layer such as polyethylene on the back surface as necessary. It is.

A recording material having excellent image uniformity can be obtained by coating a recording layer on the support obtained as described above as described later. Next, the heat-sensitive recording layer as the recording layer in the recording material of the present invention will be described.

FIG. 2 shows that a transparent cyan thermosensitive layer 22, an intermediate layer 23, a transparent yellow thermosensitive layer 24, an intermediate layer 25, and a transparent magenta thermosensitive layer 26 are sequentially laminated on one side of a sheet-like substrate 21. This is a multicolor heat-sensitive recording material provided with a transparent protective layer 27. In this case, the coloring system of at least the magenta thermosensitive layer and the yellow thermosensitive layer is a diazo system, and the cyan thermosensitive layer may or may not be a diazo system. In this case, the diazo compound is selected so that its decomposition wavelength range becomes longer as it is used in the outer thermosensitive layer.

In the recording, first, the outermost heat-sensitive layer is colored magenta with low heat energy, and then the diazo compound contained in the outermost heat-sensitive layer is decomposed by irradiating light in the decomposition wavelength range from the upper surface. To fix the recorded image on the outermost thermosensitive layer.

Next, a larger amount of thermal energy is applied than in the above-mentioned thermal recording to cause the second heat-sensitive layer to develop a yellow color.
The recorded image of the second layer is fixed by irradiating light in the wavelength range of decomposition of the diazo compound contained in the layer. Further, heat energy higher than the heat energy applied to the second layer is applied to cause the innermost heat-sensitive layer to develop cyan. If the innermost heat-sensitive layer also employs a diazo coloring system, irradiating light in the decomposition wavelength range to fix the recorded image in the innermost layer also prevents the occurrence of background soiling over time. Is preferred.

As described above, cyan, magenta, and yellow can be independently colored, and as a result, cyan, magenta, yellow, cyan + magenta (blue), and magenta + yellow (red), which have conventionally been considered difficult in thermal recording. ), Cyan + yellow (green), cyan + magenta + yellow (black), and a total of seven basic colors are realized with good color separation. In this case, those skilled in the art can easily understand that even if the innermost heat-sensitive layer is opaque, it does not adversely affect color reproduction.

Further, if the outermost heat-sensitive layer has sufficient scratch resistance and sticking resistance, it is natural that the transparent protective layer need not be provided. Those skilled in the art can easily understand that the number of colors that can be realized by mixing colors can be synergistically increased by appropriately controlling the color development of each unit by appropriately adjusting the applied heat energy. .

As described above, the color development system of the innermost heat-sensitive layer may not be a diazo system. As a coloring system other than the diazo system in this case, it is preferable to use a combination (leuco system) of an electron-donating dye precursor and a developer from the viewpoint of thermal sensitivity and color density.

Next, various components used in the multicolor heat-sensitive recording material will be described in detail. Electron-donating dyes are those that have the property of donating electrons or accepting a proton such as an acid to develop color, and are not particularly limited, but are generally colorless, lactone, lactam, sultone, A compound having a partial skeleton such as spiropyran, an ester, or an amide, and opening or cleaving the partial skeleton upon contact with a developer is used. Specifically, crystal violet lactone, benzoyl leucomethylene blue, malachite green lactone, rhodamine B lactam, 1,
3,3-trimethyl-6'-ethyl-8'-butoxyindolinobenzospiropyran and the like.

The developer for these color formers 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. (1
985) pp. 49-54 and 65-70. Among these, those having a melting point of 50 ° C. to 250 ° C. are particularly preferable, and phenol and organic acids having a low solubility in water of 60 ° C. to 200 ° C. are particularly preferable. It is preferable to use two or more developers in combination, since solubility increases. Particularly preferred among the developers are the following general formulas (1) to (1).
It is represented by (4).

General formula (1)

Embedded image m = 0-2, n = 2-11

Formula (2)

Embedded image R ⁷ is an alkyl group, an aryl group, an aryloxyalkyl group or an aralkyl group, particularly preferably a methyl group and a butyl group.

General formula (3)

Embedded image R ⁸ is an alkyl group, particularly a butyl group, a pentyl group,
Heptyl and octyl are preferred. R ⁹ is a hydrogen atom or a methyl group, and n is 0 to 2.

General formula (4)

Embedded image R ¹⁰ is an alkyl group, an aralkyl group or an aryloxyalkyl group.

The developer is used in an amount of 0.3 to 160 parts by weight, preferably 0.3 parts by weight, per part by weight of the electron donating dye precursor.
It is preferable to use up to 80 parts by weight.

The other diazo compound of the color-forming material relating to the multicolor heat-sensitive recording material is a compound which reacts with a developer called a coupler, which will be described later, to form a desired hue and has a specific color before the reaction. When it receives light of a wavelength, it decomposes and no longer has the color-forming ability even when the coupler 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 coupler. 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 coupler, and almost any color hue can be obtained depending on the combination. .

The photodegradable diazo compound mainly indicates an aromatic diazo compound, and more specifically, a compound such as an aromatic diazonium salt, a diazosulfonate compound or a diazoamino compound. Hereinafter, a diazonium salt will be mainly described as an example.

It is generally said that the photolysis wavelength of a diazonium salt is the absorption maximum wavelength. Further, the absorption maximum wavelength of the diazonium salt is 200 n depending on its chemical structure.
It is known to change from the m position to the 700 nm position (“Photodecomposition and chemical structure of photosensitive diazonium salt” by Takahiro Tsunoda and Ao Yamaoka Journal of the Photographic Society of Japan 29 (4) 197-2)
05 (1965)). Further, by changing the chemical structure of the diazonium salt, the hue of the dye generated by the coupling reaction can be changed even when the coupling reaction is performed with the same coupler.

The diazonium salt is a compound represented by the general formula ArN ₂ ⁺ X ⁻ . In the formula, Ar represents a substituted or unsubstituted aromatic moiety, N ₂ ⁺ represents a diazonium group, and X ⁻ represents an acid anion.

Among them, compounds having a photolysis wavelength around 400 nm include 4-diazo-1-dimethylaminobenzene, 4-diazo-1-diethylaminobenzene, 4-diazo-1-dipropylaminobenzene,
Diazo-1-methylbenzylaminobenzene, 4-diazo-1-dibenzylaminobenzene, 4-diazo-1-
Ethylhydroxyethylaminobenzene, 4-diazo-
1-diethylamino-3-methoxybenzene, 4-diazo-1-dimethylamino-2-methylbenzene, 4-diazo-1-benzoylamino-2,5-diethoxybenzene, 4-diazo-1-morpholinobenzene, -Diazo-1-morpholino-2,5-dibutoxybenzene, 4
-Diazo-1-anilinobenzene, 4-diazo-1-toluylmercapto-2,5-diethoxybenzene, 4-
Diazo-1,4-methoxybenzoylamino-2,5-
Diethoxybenzene and the like can be mentioned.

Compounds having a photolysis wavelength of 300 to 370 nm include 1-diazo-4- (N, N-dioctylcarbamoyl) benzene, 1-diazo-2-octadecyloxybenzene, and 1-diazo-4- (4 -Tert
-Octylphenoxy) benzene, 1-diazo-4-
(2,4-di-tert-amylphenoxy) benzene, 1-diazo-2- (4-tert-octylphenoxy) benzene, 1-diazo-5-chloro-2- (4-
tert-octylphenoxy) benzene, 1-diazo-2,5-bis-octadecyloxybenzene, 1-diazo-2,4-bis-octadecyloxybenzene, 1
-Diazo-4- (N-octylteuroylamino) benzene and the like. The aromatic diazonium compounds represented by the above-mentioned examples can widely change the photodecomposition wavelength by arbitrarily changing the substituent.

Specific examples of the acid anion include C _n F _{2n + 1}
COO ⁻ (n represents 3 to 9), C _m F _{2m + 1} SO ₃ ⁻
(M represents 2 to 8), (ClF _{2i + 1} SO ₂ ) ₂ CH
^- (I represents 1 to 18),

[0047]

Embedded image

Specific examples of the diazo compound (diazonium salt) include, for example, the following.

[0049]

Embedded image

[0050]

Embedded image

The diazosulfonate compound which can be used in the present invention has the general formula

Embedded image

Is a compound represented by the formula: Wherein R ₁ is an alkali metal or ammonium compound, R ₂ , R ₃ , R ₅
And R ₆ is hydrogen, halogen, an alkyl group, or an alkoxy group, and R ₄ is hydrogen, a halogen, an alkyl group, an amino group, a benzoylamide group, a morpholino group, a trimercapto group, or a pyrrolidino group.

Many such diazosulfonates are known and can be obtained by treating each diazonium salt with a sulfite.

Among these compounds, preferred are 2-methoxy, 2-phenoxy, 2-methoxy-
4-phenoxy, 2,4-dimethoxy, 2-methyl-4
Benzenediazosulfonic acid salt having a substituent such as -methoxy, 2,4-dimethyl, 2,4,6-trimethyl, 4-phenyl, 4-phenoxy, 4-acetamide, or 4- (N-ethyl, N-benzylamino), 4-
(N, N-dimethylamino), 4- (N, N-diethylamino), 4- (N, N-diethylamino) -3-chloro, 4-pyridinino-3-chloro, 4-morpholino-2
-Methoxy, 4- (4'-methoxybenzoylamino)
-2,5-dibutoxy, 4- (4'-trimercapto)
It is a benzenediazosulfonic acid salt having a substituent such as -2,5-dimethoxy. When these diazosulfonate compounds are used, it is desirable to perform light irradiation for activating the diazosulfonate before printing.

Other diazo compounds that can be used in the present invention include diazoamino compounds. As the diazoamino compound, a diazo group is formed by dicyandiamide, sarcosine, methyltaurine, N-ethylanthranic acid-5-sulfonic acid,
It is a compound coupled with monoethanolamine, diethanolamine, guanidine, or the like.

The coupler used in the present invention forms a dye by coupling with a diazo compound (diazonium salt), and specific examples thereof include resorcin, phloroglucin, sodium 2,3-hydroxynaphthalene-6-sulfonate. , 1-hydroxy-2-naphthoic acid morpholinopropylamide, 1,5-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,3-dihydroxy-6-sulfanylnaphthalene, 2-hydroxy-3-naphthoic acid morpholinopropylamide, 2-hydroxy-3-naphthoic acid-2′-methylamide, 2-hydroxy-3-naphthoic acid ethanolamide, 2-hydroxy-3-naphthoic acid octylamide, 2-hydroxy-3-naphthoic acid-N-dodecyl-oxy -Propylamide, 2-hydroxy Ci-3-naphthoic acid tetradodecylamide, acetanilide, acetoacetoalinide, benzoylacetanilide, 1-phenyl-3-methyl-
5-pyrazolone, 2,4-bis (benzoylacetoamino) toluene, 1,3-bis (bivaloylacetoaminomethyl) benzene, 1- (2 ′, 4 ′, 6′-trichlorophenyl) -3-benzamide- 5-pyrazolone, 1
-(2 ', 4', 6'-trichlorophenyl) -3-anilino-5-pyrazolone, 1-phenyl-3-phenylacetamido-5-pyrazolone and the like.

Further, an image of any color tone can be obtained by using two or more of these couplers. Since the coupling reaction between these diazo compounds and the coupler easily occurs under a basic atmosphere, a basic substance may be added to the 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 include inorganic and organic ammonium salts, organic amines, amides, ureas and thioureas and their derivatives, thiazoles, pyrroles, pyrimidines, piperazines, guanidines, indoles, imidazoles, imidazolines, triazoles. , Morpholines, piperidines, amidines, formazines, pyridines and the like.

These specific examples are described, for example, in Japanese Patent Application No.
No. 132990. Two or more basic substances may be used in combination. The coupler is 0.1 to 10 parts by weight and the basic substance is 0.1 to 20 parts by weight based on 1 part by weight of the diazo compound.
It is preferred to use it in a proportion by weight.

The materials which cause the above color development 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 (prevention of fog), 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 microcapsules used in this case is not particularly limited, but particularly preferred microcapsules in the present invention are those which prevent contact of substances inside and outside the capsules at normal temperature due to 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).

In order to control the glass transition point inherent in the capsule wall, it is necessary to change the type of the capsule wall forming agent. As the wall material of the microcapsules, polyurethane, polyurea, polyester, polycarbonate, urea-formaldehyde resin, melamine resin, polystyrene, styrene methacrylate copolymer, styrene-acrylate copolymer, gelatin, polyvinylpyrrolidone,
Polyvinyl alcohol and the like. In the present invention, two or more of these polymer substances can be used in combination. In the present invention, among the above polymer substances, polyurethane, polyurea, polyamide, polyester, polycarbonate and the like are preferable, and polyurethane and polyurea are particularly preferable.

The microcapsules are preferably microcapsulated by emulsifying a core substance containing a reactive substance such as a color former and then forming a wall of a polymer substance around the oil droplets. The reactant that forms the molecular substance is added inside the oil droplet and / or outside the oil droplet. Details of microcapsules that can be preferably used in the present invention, such as a preferable method for producing microcapsules, are described in, for example, JP-A-59-222716.

Here, the organic solvent for forming the oil droplets can generally be appropriately selected from high-boiling oils. In particular, an organic solvent suitable for dissolving a color developer or a coupler described below. Is preferred because it has excellent solubility in a coloring agent, and can increase the coloring density and coloring speed during thermal printing or reduce fog. When making microcapsules, they can be made from emulsions containing 0.2% by weight or more of the component to be microencapsulated.

Preferred microcapsules produced as described above do not break down by heat or pressure as used in conventional recording materials, and the reactive substance contained in the core and outside of the microcapsules is The reaction can pass through the microcapsule wall.

In the thermosensitive coloring layer, a coloring aid may be used. Here, the coloring aid is a substance that increases the coloring density during heating printing or lowers the minimum coloring temperature, and adjusts the melting point of a coupler, a basic substance, a coloring agent, a developer or a diazo compound. By lowering or lowering the softening point of the capsule wall, diazo, basic substances,
This is for creating a situation where the coupler, the color former, the color developer and the like easily react.

Examples of the coloring aid include phenol compounds, alcoholic compounds, amide compounds, and sulfonamide compounds. Specific examples include p-tert-octylphenol, p-benzyloxyphenol, phenyl p-oxybenzoate, and the like. Benzyl carbanilate, phenethyl carbanilate, hydroquinone dihydroxyethyl ether, xylylene diol, N-hydroxyethyl-
Examples thereof include compounds such as methanesulfonic acid amide and N-phenyl-methanesulfonic acid amide. These may be contained in the core substance, or may be added outside the microcapsules as an emulsified dispersion.

In order to obtain a substantially transparent thermosensitive coloring layer, a developer for the electron-donating dye precursor or a coupler for the diazo compound is dissolved in a water-insoluble or insoluble organic solvent. Is mixed with an aqueous phase containing a surfactant and having a water-soluble polymer as a protective colloid, and used in the form of an emulsified dispersion.

The organic solvent for dissolving the color developer or the coupler can be appropriately selected from high-boiling oils. In particular, it is known as esters and pressure-sensitive oils. Are preferred. Such oils include compounds represented by the following general formulas (5) to (7) and triallylmethane (eg, tritolylmethane, toluyldiphenylmethane), terphenyl compounds, alkyl compounds (eg, terphenyl), alkylated Diphenyl ether (for example, propyl diphenyl ether), hydrogenated terphenyl (for example, hexahydroterfel), and diphenyl ether. Among them, the use of esters is preferred from the viewpoint of the emulsion stability of the developer or the emulsified dispersion of the coupler.

Formula (5)

Embedded image In the formula, R ¹ is hydrogen or an alkyl group having 1 to 18 carbon atoms;
² represents an alkyl group having 1 to 18 carbon atoms. p ¹ , q ¹
Represents an integer of 1 to 4, and the total sum of the alkyl groups is within four. The alkyl groups of R ¹ and R ² have 1 to 1 carbon atoms.
8 alkyl groups are preferred.

Formula (6)

Embedded image In the formula, R ³ is hydrogen or an alkyl group having 1 to 12 carbon atoms;
⁴ represents an alkyl group having 1 to 12 carbon atoms. n represents 1 or 2. p ² and q ² represent an integer of 1 to 4. n =
In the case of 1, the total number of alkyl groups is within 4 and n
When = 2, the total number of alkyl groups is 6 or less.

Formula (7)

Embedded image In the formula, R ⁵ and R ⁶ represent a hydrogen atom or a same or different alkyl group having 1 to 18 carbon atoms. m represents an integer of 1 to 13. p ³ and q ^{3 each} represent an integer of 1 to 3, and
The total number of the alkyl groups is 3 or less. Incidentally, the alkyl group of R ⁵ and R ⁶ is particularly preferably an alkyl group having 2 to 4 carbon atoms.

The compound represented by the formula (5) includes dimethylnaphthalene, diethylnaphthalene, diisopropylnaphthalene and the like.

Examples of the compound represented by the formula (6) include dimethylbiphenyl, diethylbiphenyl, diisopropylbiphenyl and diisobutylbiphenyl.

As an example of the compound represented by the formula (7), 1
-Methyl-1-dimethylphenyl-1-phenylmethane, 1-ethyl-1-dimethylphenyl-1-phenylmethane, 1-propyl-1-dimethylphenyl-1-phenylmethane.

Examples of esters include phosphate esters (for example, triphenyl phosphate, tricresyl phosphate, butyl phosphate, octyl phosphate, cresyl diphenyl phosphate), phthalate esters (dibutyl phthalate, 2-ethylhexyl phthalate, phthalic acid) Ethyl, octyl phthalate, butyl benzyl phthalate), dioctyl tetrahydrophthalate, benzoate (ethyl benzoate, propyl benzoate, butyl benzoate, isopentyl benzoate, benzyl benzoate), abietic acid ester (abietic acid) Ethyl, benzyl abietate), dioctyl adipate, isodecyl succinate, dioctyl azelate, oxalate (dibutyl oxalate, dipentyl oxalate), diethyl malonate, maleate (dimethyl maleate, maleate) Diethyl phosphate, dibutyl maleate, tributyl citrate, sorbate (methyl sorbate, ethyl sorbate, butyl sorbate), sebacate (dibutyl sebacate, dioctyl sebacate), ethylene glycol esters (monoester formate) Monoesters and diesters of butyric acid, monoesters and diesters of lauric acid, monoesters and diesters of palmitic acid, monoesters and diesters of stearic acid, monoesters and diesters of oleic acid), triacetin, diethyl carbonate, diphenyl carbonate, ethylene carbonate, carbonate propylene,
Boric acid esters (tributyl borate, tripentyl borate) and the like. The above oils can be used together or with other oils.

Further, an auxiliary solvent may be added to the above-mentioned organic solvent as a dissolution aid having a lower boiling point. As such auxiliary solvents, for example, ethyl acetate, isopropyl acetate, butyl acetate, methylene chloride and the like can be mentioned as particularly preferable ones.

The water-soluble polymer to be contained as a protective colloid in an aqueous phase mixed with an oil phase in which a color developer or a coupler is dissolved is a known anionic polymer, nonionic polymer,
Although it can be appropriately selected from amphoteric polymers, polyvinyl alcohol, gelatin, cellulose derivatives and the like are preferable.

As the surfactant to be contained in the aqueous phase, a surfactant which does not cause precipitation or aggregation by acting on the protective colloid described above is appropriately selected from anionic or nonionic surfactants. be able to. Preferred surfactants include sodium alkylbenzenesulfonate (eg, sodium lauryl sulfate), dioctyl sodium sulfosuccinate, polyalkylene glycol (eg, polyoxyethylene nonyl phenyl ether), and the like.

The emulsified dispersion of a color developer or a coupler is prepared by mixing an oil phase containing a color developer or a coupler with an aqueous phase containing a protective colloid and a surfactant by ordinary fine particle emulsification such as high-speed stirring and ultrasonic dispersion. Can be easily obtained by mixing and dispersing using the means used for (1).

At this time, the oil droplet size (diameter) of the emulsified dispersion is preferably 7 μm or less in order to obtain a transparent heat-sensitive phase having a haze of 60% or less. More preferably, 0.
It is in the range of 1 to 5μ.

Alternatively, the ratio of the oil phase to the aqueous phase (oil phase weight /
(Water phase weight) is preferably from 0.02 to 0.6, more preferably from 0.1 to 0.4. If it is less than 0.02, the aqueous phase is too large to be diluted, so that sufficient color development cannot be obtained. If it is more than 0.6, the viscosity of the liquid becomes high, which causes inconvenience in handling and a decrease in transparency.

In addition to the above materials, citric acid, tartaric acid, oxalic acid, boric acid, phosphoric acid, pyrophosphoric acid and the like can be added as an acid stabilizer.

The recording material can be applied using an appropriate binder. As the binder, polyvinyl alcohol, methylcellulose, carboxymethylcellulose, hydroxypropylcellulose, gum arabic, gelatin, polyvinylpyrrolidone, casein, styrene-
Various emulsions such as butadiene latex, acrylonitrile-butadiene latex, polyvinyl acetate, polyacrylate and ethylene-vinyl acetate copolymer can be used. The amount used is 0.5 to 5 g / m ² in terms of solid content.

The coating amount of the recording layer is 3 g / m ^{2 to} 20 g / m ^2.
g / m ^2, it is preferable that particularly is between ^{5g / m 2 ~15g / m 2} . If it is 3 g / m ² or less, sufficient sensitivity cannot be obtained, and even if it is applied in an amount of 20 g / m ² or more, no improvement in quality can be seen, which is disadvantageous in cost. In the case of a heat-sensitive recording material, it is preferable to provide an intermediate layer between the heat-sensitive layer and the heat-sensitive layer from the viewpoints of raw storability of the heat-sensitive recording material, improved recorded image storability and improved color separation. It is preferable to use a layer obtained by gelling a water-soluble polyanionic polymer with a polyvalent cation.

Preferred as the water-soluble polyanionic polymer are polymers having a carboxyl group, a sulfonic acid group and a phosphoric acid group, and in particular, a water-soluble polyanionic polymer having a carboxyl group is preferred. Examples of preferred water-soluble polyanionic polymers include natural or synthetic polysaccharide gums (for example, alkali metal alginate,
Guar gum, gum arabic, carrageenan, pectin, tragacanth gum, xanthene gum, etc.), polymers of acrylic acid or methacrylic acid and copolymers thereof, polymers of maleic acid or phthalic acid and copolymers thereof, and cellulose derivatives such as carboxymethyl cellulose , Gelatin and agar, among which alkali metal alginates are preferred. The molecular weight of the water-soluble polyanionic polymer is 5,000
It is preferably from 0 to 10,000, and in particular, from the viewpoint of the barrier properties and production suitability aimed at in the present invention, 10,000.
~ 40,000 is preferred. Examples of the polyvalent cation include salts of alkaline earth metals and other polyvalent metals (for example, CaC
l ₂ , BaCl ₂ , Al ₂ (SO ₄ ) ₃ , ZnSO ₄
And the like, polyamines (eg, ethylenediamine, diethylenetriamine, hexamethylenediamine, etc.) and polyimines.

Another preferred example of the intermediate layer is an ion complex of a water-soluble polyanionic polymer and a water-soluble polycation polymer. In this case, the various water-soluble polyanion polymers described above can be used as the water-soluble polyanion polymer.

As the water-soluble polycationic polymer, proteins having a plurality of reactive nitrogen-containing cationic groups, polypeptides such as polylysine, polyvinylamines, polyethyleneamines, polyethyleneimines and the like are preferable.

When an intermediate layer is formed using these materials, one of a water-soluble polyanionic polymer and a polyvalent cation is used to prevent rapid gelation during coating. It is preferable that the coating be performed while being contained in one of the heat-sensitive layers.
It is also possible to adjust H or to include the one material in the adjacent heat-sensitive layer. Preferred coating weight of the intermediate layer is ^{0.05g / m 2 ~5g / m 2} , more preferably from ^{0.1g / m 2 ~2g / m 2} .

In the heat-sensitive layer, it is necessary that at least the outermost and second heat-sensitive layers are substantially transparent in order to improve color separation. Substantially transparent here means
Haze (%) (Nihon Seimitsu Kogyo Co., Ltd., integrating sphere method HTR
(Measured with a meter), it must be less than 60%. It is preferably 40% or less, and more preferably 3% or less.
0% or less. However, light scattering based on fine irregularities on the surface of the heat-sensitive layer has a great effect on the transparency of the actual heat-sensitive layer test sample. Therefore, when measuring the transparency inherent in the heat-sensitive layer to be a problem, that is, the transparency inside the heat-sensitive layer with a haze meter, a transparent adhesive tape is stuck on the heat-sensitive layer as a simple method to reduce surface scattering. The evaluation is made using the measured values almost completely removed. The transparency as described above can be easily achieved by using a developer or a coupler in the form of the emulsified dispersion.

It is preferable to substantially provide a protective layer on the outermost thermosensitive layer of the thermosensitive recording material in order to improve scratch resistance and prevent sticking. Two or more protective layers may be stacked. The transparent protective layer that can be used in the present invention comprises at least silicon-modified polyvinyl alcohol and colloidal silica.

The silicon-modified polyvinyl alcohol is
It is not particularly limited as long as it contains a silicon atom in the molecule, but the silicon atom usually contained in the molecule is preferably an alkoxyl group, an acyloxyl group or a hydroxyl group obtained by hydrolysis or the like, or an alkali metal salt thereof. It is preferable to use those having a reactive substituent of
Details of such a method for producing a modified polyvinyl alcohol containing a silicon atom in the molecule are described in JP-A-58-193189.
No., published in Japanese Patent Application Publication No.

Colloidal silica is used as a colloid solution in which ultrafine silica particles are dispersed in water using water as a dispersion medium. The size of the colloidal silica particles is 10
Those having a mμ of 100 μm and a specific gravity of 1.1 to 1.3 are preferred. In this case, the pH value of the colloid solution is preferably about 4 to about 10.

When the protective layer is provided on the surface of the thermosensitive recording material, the surface scattering phenomenon is suppressed as in the case where the transparent adhesive tape is applied, and more surprisingly, the transparency of the protective layer is extremely good. It is. Further, since the mechanical strength of the surface of the heat-sensitive layer is improved, the transparency of the entire heat-sensitive material can be further remarkably improved.

An appropriate blending ratio of the silicon-modified polyvinyl alcohol and the colloidal silica is such that 0.5 parts of the colloidal silica is added to 1 part by weight of the silicon-modified polyvinyl alcohol.
To 3 parts by weight, more preferably 1 to 2 parts by weight. When the amount of the colloidal silica is less than 0.5 part by weight, the effect of improving the transparency is small, and when the amount is 3 parts by weight or more, the protective layer film is cracked, and the transparency is rather reduced.

The transparent protective layer may further contain one or more polymers. Specific examples of the polymer that can be used in combination include methyl cellulose, carboxymethyl cellulose,
Hydroxymethylcellulose, starch, gelatin, gum arabic, casein, styrene-maleic anhydride copolymer hydrolyzate, styrene-maleic anhydride copolymer half ester hydrolyzate, polyvinyl alcohol, carboxy-modified polyvinyl alcohol, polyacrylamide derivative Water-soluble polymers such as polyvinylpyrrolidone, sodium polystyrenesulfonate and sodium alginate; styrene-butadiene rubber latex; acrylonitrile-butadiene rubber latex; methyl acrylate;
Water-insoluble polymers such as butadiene rubber latex and polyvinyl acetate emulsion are exemplified. The amount to be used in combination is preferably 0.01 to 0.5 part by weight based on 1 part by weight of the silicon-modified polyvinyl alcohol.

Pigments, metal soaps, waxes, cross-linking agents, and the like are added to the protective layer for the purpose of improving matching with the thermal head during thermal printing and improving the water resistance of the protective layer.

The pigment has a refractive index of 1.4 to 1.55 and a particle size of 1 μm.
The following pigments are preferred. Specific examples thereof include calcium carbonate, talc, limestone, kaolin, aluminum hydroxide, amorphous silica, and the like, and the amount of addition thereof is 0.05 to 0.5 times the total weight of the polymer, particularly preferably 0.1 to 0.1. ０．３0.3 times the amount. If the amount is 0.05 times or less, it is ineffective for improving the matching property with the head, and if the amount is 0.5 times or more, the transparency and sensitivity of the heat-sensitive recording material are remarkably reduced, thereby impairing the commercial value.

Examples of the metal soap include emulsions of higher fatty acid metal salts such as zinc stearate, calcium stearate, and aluminum stearate. 0.5 to 20% by weight, preferably 1 to 10% by weight of the total weight of the protective layer. It is added in an amount.

Examples of the wax include emulsions such as paraffin wax, microcrystalline wax, carnauba wax, methyl roll stearoamide, polyethylene wax, and silicone.
% By weight, preferably 1 to 20% by weight.

In order to uniformly form a protective layer on the heat-sensitive layer, a surfactant is added to the coating liquid for forming a protective layer. Examples of the surfactant include sulfosuccinic acid-based alkali metal salts, fluorine-containing surfactants, and the like.
There are sodium salts and ammonium salts such as (2-ethylhexyl) sulfosuccinic acid and di- (n-hexyl) sulfosuccinic acid. Further, a surfactant, a polymer electrolyte or the like for preventing charging of the heat-sensitive recording material may be added to the protective layer.

The coating amount of the solid content of the protective layer is usually 0.2 to 5 g.
/ M ² are preferred, more preferably from 1 to 3 g / m ^2.

An undercoat layer may be provided between the support and the heat-sensitive layer in order to increase the adhesion between the support and the heat-sensitive layer. As a material for the undercoat layer, gelatin, synthetic polymer latex, nitrocellulose, or the like is used. The amount of undercoat is 0.1 g
/ M ^{2 to} 2.0 g / m ² ,
In particular in the range of 0.2g / m ² ~1.0g / m ² is preferred. If the amount is less than 0.1 g / m ² , the adhesion between the support and the heat-sensitive layer is not sufficient, and even if the amount is increased to 2.0 g / m ² or more, the adhesive force between the support and the heat-sensitive layer reaches saturation. This is disadvantageous in terms of cost.

When the undercoat layer is swelled by water contained in the coating solution when the heat-sensitive layer is applied thereon, the image quality recorded on the heat-sensitive layer may be deteriorated. It is desirable to cure using a hardener. Examples of the hardener include the following.

(1) divinylsulfone-N, N'-ethylenebis (vinylsulfonylacetamide), 1,3-bis (vinylsulfonyl) -2-propanol, methylenebismaleimide, 5-acetyl-1,3-di Acryloyl-hexahydro-s-triazine, 1,3,5-triacryloyl-hexahydro-s-triazine,
Active vinyl compounds such as 5-trivinylsulfonyl-hexahydro-s-triazine.

(2) 2,4-dichloro-6-hydroxy-s-triazine sodium salt, 2,4-dichloro-
6-methoxy-s-triazine, 2,4-dichloro-6
-(4-sulfoanilino) -s-triazine sodium salt, 2,4-dichloro-6- (2-sulfoethylamino) -s-triazine, N-N'-bis (2-chloroethylcarbamyl) piperazine Active halogen compounds.

(3) Bis (2,3-epoxypropyl)
Methylpropylammonium / p-toluenesulfonate, 1,4-bis (2 ′, 3′-epoxypropyloxy) butane, 1,3,5-triglycidyl isocyanurate, 1,3-diglycidyl-5- (γ -Acetoxy-
epoxy compounds such as (β-oxypropyl) isocyanurate.

(4) Ethyleneimino compounds such as 2,4,6-triethylene-s-triazine, 1,6-hexamethylene-NN'-bisethyleneurea and bis-β-ethyleneiminoethylthioether.

(5) Methanesulfonic acid ester compounds such as 1,2-di (methanesulfonoxy) ethane, 1,4-di (methanesulfonoxy) butane, and 1,5-di (methanesulfonoxy) pentane.

(6) dicyclohexylcarbodiimide,
1-cyclohexyl-3- (3-trimethylaminopropyl) carbodiimide-p-toluenesulfonate, 1
A carbodiimide compound such as -ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride.

(7) Isoxazoles such as 2,5-dimethylisoxazole perchlorate, 2-ethyl-5-phenylisoxazole-3'-sulfonate, and 5,5 '-(paraphenylene) bisisoxazole Compound.

(8) Inorganic compounds such as chromium alum and chromium acetate. (9) N-carboethoxy-2-isopropoxy-1,
Dehydration-condensed peptide reagents such as 2-dihydroquinoline and N- (1-morpholinocarboxy) -4-methylpyridinium chloride; N, N'-adipoyldoxydisuccinimide, N, N'-terephthaloyldioxydi Active ester compounds such as succinimide.

(10) Isocyanates such as toluene-2,4-diisocyanate and 1,6-hexamethylene diisocyanate. (11) Dialdehydes such as glutaraldehyde, glyoxal, dimethoxyurea, and 2,3-hydroxy-1,4-dioxane. Among these, dialdehydes such as glutaraldehyde, 2,3-dihydroxy-1,4-dioxane and boric acid are particularly preferred.

The amount of these hardeners to be added ranges from 0.20% by weight to 3.0% by weight with respect to the weight of the undercoating material. You can choose. If the addition amount is less than 0.20% by weight, the degree of curing will be insufficient even if the aging is continued for a long time, and the undercoat layer will swell during application of the heat-sensitive layer. Conversely, 3.0
If the amount is more than 10% by weight, the degree of curing will be too high and the adhesion between the undercoat layer and the support will be rather deteriorated, and the undercoat layer will have a film form and will be peeled off from the support. Depending on the curing agent used, if necessary, add caustic soda, etc.
Can be made alkaline or the pH of the solution can be made acidic with citric acid or the like.

It is also possible to add an antifoaming agent to eliminate bubbles generated at the time of application, or to add an activator to improve the leveling of the liquid and prevent the generation of coating streaks. . Further, it is also possible to add an antistatic agent as needed. Further, the undercoat layer may be made opaque by adding a white pigment.

Before applying the undercoat layer, it is desirable to activate the surface of the support by a known method. As the method of the activation treatment, an etching treatment with an acid, a flame treatment with a gas burner, a corona discharge treatment, a glow discharge treatment, or the like is used. From the viewpoint of cost or simplicity, US Pat. No. 075, No. 2, 8
No. 46,727, No. 3,549,406, No. 3,
The corona discharge treatment described in 590, 107 or the like is most preferably used.

The coating solution can be prepared by a well-known coating method,
For example, dip coating, air knife coating, curtain coating, roller coating, doctor coating,
It can be applied by 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. .

If a pigment dispersant, a thickener, a flow modifier, an antifoaming agent, a foam inhibitor, a release agent, and a colorant are appropriately added to the coating liquid as needed, it is not necessary to impair the characteristics. I can't tell.

The multicolor heat-sensitive recording material as the recording material of the present invention can be used as a multicolor sheet for a facsimile or a printer of an electronic computer which requires high-speed recording. In this case, in the case of the present invention in which a diazo compound is used as a color-forming component, providing an exposure zone for photodecomposition is particularly advantageous for preservation of images and multicoloring.

The arrangement of the print head and the exposure zone can be roughly classified into two types. One prints once and then irradiates with light for photolysis, and before and after this light irradiation, the recording material feed mechanism puts the recording material in a printing standby state so that it can be printed again where it was once printed. Return, then print again, and repeat the operation of returning the recording material to the original, so-called 1
This is a head multiple scan method. Another method is a so-called multi-head one-scan method in which the number of recording heads corresponding to the number of colors to be recorded is provided, and a light irradiation zone is provided between the recording heads.
As the light source for photolysis, various light sources that emit light of a desired wavelength can be used. For example, various fluorescent lamps, xenon lamps, xenon flash lamps, mercury lamps of various pressures, photographic flashes, strobes, etc. Various light sources can be used. Further, in order to make the light fixing zone compact, the light source unit and the exposure unit may be separated using an optical fiber.

The multicolor heat-sensitive recording material reproduces a full-color image as a whole by causing each heat-sensitive layer to develop any one of Y (yellow), M (magenta) and C (cyan). However, it is preferable from the viewpoint of color reproducibility that C, Y, and M or C, M, and Y in order from the support side.

In the above-mentioned recording materials, especially the multicolor heat-sensitive recording material has been described. However, the recording material of the present invention can be applied to recording materials other than the recording material having a multicolor heat-sensitive recording layer. The present invention can be applied to a recording material of a silver halide photosensitive layer. . Even in such a recording material, oxygen reaching the recording layer or the silver halide photosensitive layer through the support is greatly reduced, and the components contained in the recording layer or the silver halide photosensitive layer are hardly oxidized. ,
The coloring of the background portion and the discoloration or fading of the image portion are reduced.

[0123]

The present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. Unless otherwise specified, “parts” means “parts by weight”. Example 1 A wood pulp composed of 100 parts of LBKP was beaten to a Canadian freeness of 300 cc with a double disc refiner, and 0.5 parts of epoxidized behenamide, 1.0 part of anionic polyacrylamide, 0.1 part of polyamide polyamine epichlorohydrin, and cation 0.5 parts of polyacrylamide were added at an absolute dry weight ratio to pulp, and the basis weight was 100 g by a fourdrinier paper machine.
/ M ² base paper, polyvinyl alcohol 1.0g
/ M ² absolute dry weight and surface adjusted to a density of 1.0 by calendering.

On the wire side (back side) of the base paper, a corona
After performing discharge treatment, use a melt extruder to
Coat styrene with a resin thickness of 36 μm.
A resin layer consisting of a cut surface was formed (this surface is referred to as a back surface).
Bu). Corona discharge treatment on the polyethylene coated surface on the back
Aluminum oxide (Nissan Chemical
Industrial Alumina Sol 100) / Silicon dioxide (Nissan)
Snowtex O manufactured by Chemical Industry Co., Ltd.) = 1/2 (weight)
Ratio) in water and 0.2 g / m2 after drying. ^TwoPaint
Clothed. (This is called back PE lami product)

Also, after the corona discharge treatment was performed on the felt surface (front surface) side of the base paper, 10% by weight of swellable synthetic mica having an aspect ratio of 40 and an average particle size (plane size) of 4 μm and 10% by weight of anatase type titanium dioxide And a low-density polyethylene having a MFR (melt flow rate) of 3.8 containing a trace amount of ultramarine blue having a particle size of 50 μm using a hot melt extruder.
m to form a thermoplastic resin layer having a glossy surface. (This surface is referred to as the surface.) After the surface of the polyethylene resin coating layer was subjected to corona discharge treatment, the gelatin undercoat layer was dried to a weight of 0.1 g / m2.
² was applied.

[Embodiment 2] In the same manner as in Embodiment 1, the back P
After preparing an E-laminate product and subjecting the surface of the base paper to a corona discharge treatment, 1.5% by weight of a swellable synthetic mica having an aspect ratio of 40 and an average particle size (plane size) of 4 μm was placed on the surface near the base paper
And a low-density polyethylene resin layer having an MFR of 3.8 (this layer is a lower layer) having a thickness of 5 μm. Further, on this lower layer, an MFR containing 10% by weight of anatase type titanium dioxide and a trace amount of ultramarine is 3.8. A low-density polyethylene resin layer (this layer is an upper layer) of 45 μm is coated at 310 ° C. using a multi-hold type multilayer extrusion die,
A thermoplastic resin layer was provided from the glossy side. Further, after a corona discharge treatment was applied to the surface of the polyethylene resin layer on the upper surface, a gelatin undercoat layer was applied so that the weight after drying was 0.1 g / m ² .

Example 3 A recording material was produced in the same manner as in Example 2 except that the filling amount of the swellable synthetic mica in the lower layer of Example 2 was changed to 20% by weight.

Example 4 A recording material was produced in the same manner as in Example 2 except that the filling amount of the swellable synthetic mica in the lower layer of Example 2 was changed to 70% by weight.

Example 5 Example 3 was repeated except that 30% by weight of a swellable synthetic mica having an average particle size (plane size) of 4 μm and an aspect ratio of 40 was contained in the high-density polyethylene of the back PE lamination product. Similarly, a recording material was prepared.

Example 6 The average particle size (planar size) of the swellable synthetic mica in the lower surface resin layer of Example 2 was 4 μm.
A recording material was produced in the same manner as in Example 2 except that the aspect ratio was 10 and the filling amount was 20% by weight.

Example 7 The average particle size (plane size) of the swellable synthetic mica in the resin layer under the surface of Example 2 was 4 μm.
A recording material was produced in the same manner as in Example 2, except that the aspect ratio was 100 and the filling amount was 0.5% by weight.

Comparative Example 1 A recording material was produced in the same manner as in Example 1 except that the surface resin layer of Example 1 did not contain swellable synthetic mica.

Comparative Example 2 A recording material was produced in the same manner as in Example 2 except that the lower thermoplastic resin layer of Example 2 did not contain swellable synthetic mica.

After supporting corona discharge treatment in Examples 1 to 7 and Comparative Examples 1 and 2, a full-color thermosensitive recording layer of a thermosensitive recording material was 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.

Solution A was added to 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 a developer emulsion dispersion) 1,1- (p
-Hydroxyphenyl) -2-ethylhexane (developer) (5 parts), tricresyl phosphate (0.3 parts) and diethyl maleate (0.1 part) were dissolved in ethyl acetate (10 parts). The obtained solution was mixed with a 6% by weight aqueous solution of gelatin 50.
g and 2 g of a 2% by weight aqueous solution of sodium dodecylsulfonate were added to a mixed solution, and emulsified for 10 minutes using a homogenizer to obtain an emulsified dispersion.

(Preparation of Coating Solution) The capsule solution containing the electron-donating dye precursor / the emulsified developer / dispersing solution was added in a weight ratio of 1 /.
4 to obtain a coating liquid.

(2) Preparation of Magenta Thermal Recording Layer Solution (Preparation of Capsule Solution 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 the diazo compound-containing capsule solution / coupler emulsion at a weight ratio of 2/3.

(3) Preparation of yellow thermosensitive recording layer liquid (Preparation of capsule liquid 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.

The obtained solution was added with 1 part of xylylene diisocyanate / trimethylolpropane 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 emulsion dispersion) 2-chloro-5- (3- (2,4-di-tert-pentyl) phenoxypropylamino) acetoacetanilide 2 parts,
1 part of 1,2,3-triphenylguanidine, 0.3 part of tricresyl phosphate and 0.1 part of diethyl maleate
Parts in 10 parts of ethyl acetate, 6% by weight of gelatin
The mixture was poured into an aqueous solution obtained by mixing 50 g of an aqueous solution and 2 g of a 2% by weight aqueous solution of sodium dodecyl sulfonate, and 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 / an emulsified dispersion of coupler in a weight ratio of 2/3.

(4) Preparation of Intermediate Layer Solution Polyacrylic acid (trade name: Julimer AC-10L: manufactured by 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.). ) Of 15
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 Thermosensitive Recording Material The thermoplastic resin layer of each of the supports of Examples 1 to 7 and Comparative Examples 1 and 2 was supported on a slide using a slide type hopper type bead coating device. From the body, in order from the body, a cyan thermosensitive recording layer solution, an intermediate layer solution, a magenta thermosensitive recording layer solution, an intermediate layer solution, a yellow thermosensitive recording layer solution, and a protective layer solution are coated in multiple layers and dried to obtain a multicolor thermosensitive recording material. Got each.

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 7 and Comparative Examples 1 and 2, and thereafter, oxygen permeability and background fog were evaluated. Thermal recording was performed as follows. Using Kyocera thermal head KST type, (1) Recording energy per unit area is 35mJ
/ Mm ² , the power applied to the thermal head and the pulse width were determined, the thermosensitive recording material was printed, and a yellow image was recorded. (2) The recording material is irradiated for 10 seconds under an ultraviolet lamp having an emission center wavelength of 420 nm and an output of 40 W. (3) The recording energy per unit area is again 6
The power applied to the thermal head and the pulse width were determined so as to be 6 mJ / mm ² , printing was performed, and a magenta image was recorded. Furthermore, (4) irradiation is performed for 15 seconds under an ultraviolet lamp having an emission center wavelength of 365 nm and an output of 40 W, and (5) the power and pulse width applied to the thermal head are determined so that the recording energy per unit area becomes 90 mJ / mm ² again. , And a cyan image was recorded. As a result,
In addition to the yellow, magenta, and cyan color images, the recording portion where the yellow and magenta records overlap is red, the portion where magenta and cyan overlap is blue, the portion where yellow and cyan overlap is green, and the like. The portion where the yellow, magenta and cyan records overlapped was colored black. The unrecorded area was white.

[Evaluation Method] (1) Oxygen Permeability The oxygen permeability is a value measured by the method B of JIS K-7156, and a smaller value means a smaller oxygen permeability. (2) Background fogging Background fogging is based on Weatherometer C1 65 (Atlas Electric
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 ". Table 1 shows the evaluation results.

[0158]

[Table 1]

From Table 1, it can be seen that the heat-sensitive recording materials of Examples 1 to 7 each have a lower oxygen permeability of the support and a lower background fog than the heat-sensitive recording materials of Comparative Examples 1 and 2. In particular, Examples 1 to 5
Indicates that the oxygen permeability is 50 cc / m ² / day or less and the background fog is less.

[0160]

As described above, according to the present invention, there is provided a recording material capable of obtaining an image having a low oxygen permeability of a support of the recording material, an excellent long-term preservation of the image, and a low background fog. be able to.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view showing an embodiment of a support in a recording material of the present invention.

FIG. 2 is a cross-sectional view of a multicolor thermosensitive recording material showing a preferred embodiment of the recording material of the present invention.

[Explanation of symbols]

Reference Signs List 10 base paper 12 olefin resin layer 14 swellable synthetic mica and olefin resin layer containing white pigment 16 swellable synthetic mica containing olefin resin layer 18 white pigment containing olefin resin layer 20 swellable synthetic mica Containing olefin-based resin layer 21 Sheet-like substrate 22 Transparent cyan coloring layer 23 Intermediate layer 24 Transparent yellow coloring layer 25 Intermediate layer 26 Transparent magenta coloring layer 27 Transparent protective layer

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI B41M 5/18 101F

Claims (14)

[Claims] 1. A recording material comprising a support and a recording layer provided thereon, wherein the support is provided on one or both sides of a base paper with a thermoplastic resin layer containing a layered inorganic compound. . 2. The recording material according to claim 1, wherein at least one more thermoplastic resin layer is provided on the thermoplastic resin layer containing the layered inorganic compound. 3. The recording material according to claim 1, wherein the layered inorganic compound comprises fluorinated mica. 4. The recording material according to claim 3, wherein the fluorinated mica comprises a swellable synthetic mica. 5. The recording material according to claim 4, wherein the swellable synthetic mica has an aspect ratio of 20 or more. 6. The recording material according to claim 4, wherein the filling amount of the swellable synthetic mica in the thermoplastic resin layer is 1 to 80% by weight. 7. The recording material according to claim 1, wherein the thermoplastic resin layer is made of an olefin-based resin. 8. The recording material according to claim 7, wherein the thermoplastic resin layer is formed by melt extrusion lamination of an olefin resin. 9. The recording material according to claim 1, wherein the recording layer is formed by laminating recording layers that respectively emit yellow, magenta, and cyan colors. 10. The recording material according to claim 9, wherein said recording layer is a silver halide photosensitive layer. 11. The recording material according to claim 9, wherein said recording layer is a thermosensitive recording layer. 12. The recording material according to claim 11, wherein the heat-sensitive recording layer contains a diazonium salt compound and a coupler that reacts with the diazonium salt compound to form a color. 13. The recording material according to claim 11, wherein the heat-sensitive recording layer contains an electron-donating colorless dye and an electron-accepting compound. 14. A heat-sensitive recording layer containing a diazonium salt compound and a coupler that reacts with the diazonium salt compound to form a color, and a heat-sensitive recording layer containing an electron-donating colorless dye and an electron-accepting compound. The recording material according to claim 11, wherein