JPH0725197B2 - Recording material - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a recording material, and more particularly to a recording material having improved color developability, raw storability, and stability of a color image.

(Prior Art) A recording material using an electron-donating colorless dye and an electron-accepting compound is already well known as a pressure-sensitive paper, a thermal paper, a light-sensitive pressure-sensitive paper, a heat-sensitive recording paper and the like. For example, US Patent 2,14
0,449, U.S. Pat.Nos. 4,480,052, 4,436,920, JP-B-60-23,922, JP-A-57-179,836, and JP-A-60-123,556.
No. 60, 123, 557, etc.

The recording material should have (1) sufficient color density and color sensitivity, (2) no fog, and (3) sufficient fastness of the color body after color development.
(4) Appropriate color hue and suitability for copying machines, (5)
For example, the S / N ratio is high, and (6) the color former has sufficient chemical resistance.

In recent years, with the speeding up of recording systems and the diversification of requirements, research has been earnestly conducted to improve these characteristics.

The present inventors have found that the characteristics of the recording material are significantly improved by incorporating a unique device into the electron-accepting compound. In particular, as will be described later, its properties are remarkably improved by using it together with a specific ether compound.

(Object of the Invention) Accordingly, it is an object of the present invention to provide a recording material which has good color developability, raw storability and stability of a color image, and which satisfies other requirements.

(Structure of the Invention) An object of the present invention is to provide an electron donating colorless dye and an alkoxysalicylic acid skeleton represented by the following general formula (I) in the side chain at 10%.
This has been achieved by a recording material utilizing coloring by contact with an electron-accepting polymer compound as described above.

In the above formula, R ₁ is a hydrogen atom, an alkyl group, R ₂ is a divalent group having 16 or less carbon atoms, R ₃ and R ₄ are hydrogen atoms, halogen atoms, hydroxy groups, alkoxy groups, aryl groups, Alkyl group, aryloxy group, thioalkoxy group, alkoxycarbonyl group, optionally substituted amino group, acyloxy group, cyano group, nitro group, acyl group, carbamoyl group, sulfamoyl group, aralkyl group, substituted aryl group , An alkyl group having a substituted aryl group,
It is selected from a carbonyl group, a carboxyl group and a sulfo group.

R ₃ and R ₄ may combine with each other to form a 5- or 6-membered saturated or unsaturated ring.

R ₃ and R ₄ may combine with each other to form a 5- or 6-membered saturated or unsaturated ring. A benzene ring, a pyridine ring, an anthraquinone ring and the like are examples thereof.

R ₂ is a group having 16 or less carbon atoms, which may be saturated or unsaturated, and may have an ether bond, an ester bond, a urethane bond, an amide bond, or the like.

Preferred examples of R ₂ are -CnH ₂ m-, -X-, CH ₂ nXCH ₂ m, —X—CnH ₂ m— and the like, wherein R ₅ is a group described for R ₃ such as a hydrogen atom, a hydroxy group, an alkyl group, an acyloxy group, a halogen atom or an aryl group. , X is a group selected from an oxygen atom, a sulfur atom, an arylene group, an alkenylene group, a branched alkylene group, a carbonyl group, —OCOO—, an amide group, n,
m represents an integer of 0 to 8. For example −C ₂ H ₄ −, −C ₃ H ₆ −, −C ₄ H ₈ −, −C ₈ H ₈ −, −C ₂ H ₄ OC ₂ H
_{4 -, - C 3 H 6} O -, - C 3 H 5 ClO -, - C 4 H 6 -, - C 3 H 6 (O
_{H) O -, - C 3} H 6 OC 3 H 6 -, Are particularly preferred specific examples.

Preferred examples of R ₁ are hydrogen atom and methyl group.

Specific examples of the alkoxysalicylic acid skeleton include Etc. are an example of a preferable skeleton.

These compounds are synthesized by methods such as 1) vinyl polymerization reaction or 2) polymer reaction.

The vinyl polymerization reaction is carried out by homopolymerizing or copolymerizing the compound represented by the following general formula (II). Copolymerization is a well-known method in the art, for example, Polymer
Detailed in r Handbook, Iohn Wiley, etc.

Styrene, (meth) acrylate, acrylamide, etc. are used as a copolymerization partner, but the above-mentioned units are
It is used so as to be about 10% or more, preferably about 40% or more.

By selecting this monomer, it is possible to freely control the particle size, solubility, tackiness, dispersion stability, color developability, etc. of the polymer compound obtained.

Examples of such copolymerization partners include acrylamide, cellosolve acrylate, styrene, methyl methacrylate, acrylonitrile, vinylcarbazole, octyl acrylate, sodium acrylamide propane sulfonate, butyl methacrylate, ethyl acrylate,
Examples include divinylbenzene, vinyldioxolane, epichlorohydrin, allyl methacrylate, cinnamoyloxyethyl methacrylate, vinylbenzophenone, ethylene glycol acrylate, diethylene glycol diacrylate, and diethylene glycol acrylate butyrate.

The polymerization reaction methods include radical polymerization, ionic polymerization,
Various methods such as solution polymerization, emulsion polymerization, suspension polymerization and solventless polymerization can be selected.

More specifically, for example radical polymerization can be initiated by radical initiators. Persulfate-reducing agent,
Oily or aqueous azo compounds, peroxides, metal catalysts and the like can be used. In the polymerization reaction,
It is preferable to carry out in an inert gas atmosphere, and when heating, 120 ° C. or lower, particularly 90 ° C. or lower is preferable.

When a solvent is used, water, ester, ether,
Polar solvents such as halides, ketones, amides, alcohols,
Nonpolar solvents such as hydrocarbons and aromatics may be used alone or in combination.

Further, it is possible to improve the hue and the coloring efficiency by allowing the above-mentioned various colorless dyes to coexist during the polymerization reaction.

For the emulsification method, degassing method, reaction temperature control, metal catalyst handling method, post-treatment method after completion of the polymerization reaction, and purification method of the obtained polymer compound, etc. It is convenient to operate with reference to. For example, see Sore for general operations.
He is familiar with nsen, a polymer synthesis experimental method (Tokyo Kagaku Dojin). Of these, products obtained by methods such as suspension polymerization and emulsion polymerization are particularly preferable.

The polymer reaction is carried out by reacting a compound having a unit represented by the following general formula (III) with a compound represented by the general formula (IV).

However, Y represents an active group selected from a chlorine atom, —OH, a tosyloxy group, an alkoxy group, an α-bromoacetyl group, an alkoxycarbonyl group and the like.

A unit operation for forming an ether bond or an ester bond is well known, and those techniques can be referred to in the reaction.

The compound having an alkoxysalicylic acid in the side chain of the present invention may be used as a metal salt or may be formed in the recording layer. For example, the metals include Ca, Zn, Ba, Mg, Al,
There are K, Sn, etc., but especially Zn salt exhibits good performance.

The colorless dye colored with the electron-accepting compound as described above will be described below.

As the colorless dye, a triphenylmethylphthalide compound, a fluoran compound, a phenothiazine compound, an indolylphthalide compound, a leukoauramine compound, a rhodamine lactam compound, which are already well known,
Various compounds such as triphenylmethane compounds, triazene compounds and spiropyran compounds can be mentioned.

Regarding these various existing colorless dyes, for example, specific examples of phthalides are US Reissue Patent No. 23,024 and US Patent 3,493.
1,111, 3,491,112, 3,491,116, 3,509,174
And specific examples of fluoran compounds are U.S. Pat.
3,627,787, 3,641,011, 3,462,828, 3,68
No. 1,390, No. 3,920,510, No. 3,959,571, specific examples of spirodipyrans are U.S. Pat.No. 3,971,808, pyridine compounds and pyrazine compounds are U.S. Pat.Nos. 3,775,424, No. 3,83.
No. 53,869, US Pat. No. 4,246,318 and the like.

Some examples of colorless dyes are triarylmethane compounds such as 3,3-bis (p-dimethylaminophenyl) -6-dimethylaminophthalide (that is, crystal violet letolactone) and 3,3-bis. (P-Dimethylaminophenyl) phthalide, 3- (p-dimethylaminophenyl) -3- (1,3-dimethylindol-3-yl)
Phthalide, 3- (p-dimethylaminophenyl) -3-
(2-methylindol-3-yl) phthalide, and the like. Examples of diphenylmethane compounds include 4,4′-bis-dimethylaminobenzhydrin benzyl ether and N.
-Halophenyl-leuco auramine, N-2,4,5-trichlorophenyl leuco auramine, etc., and xanthene compounds include rhodamine-B-anilinolactam, rhodamine (p-nitroanilino) lactam, rhodamine B ( p-chloroanilino) lactam, 2-dibenzylamino-6-diethylaminofluorane, 2-anilino-6-diethylaminofluorane, 2-anilino-
3-methyl-6-diethylaminofluorane, 2-anilino-3-methyl-6-cyclohexylmethylaminofluorane, 2-o-chloroanilino-6-diethylaminofluorane, 2-m-chloroanilino-6-diethylaminofluorane, 2- (3,4-dichloroanilino)-
6-diethylaminofluorane, 2-octylamino-
6-diethylaminofluorane, 2-dihexylamino-6-diethylaminofluorane, 2-m-trifluoromethylanilino-6-diethylaminofluorane, 2-
Butylamino-3-chloro-6-diethylaminofluorane, 2-ethoxyethylamino-3-chloro-6-diethylaminofluorane, 2-p-chloroanilino-3
-Methyl-6-dibutylaminofluorane, 2-anilino-3-methyl-6-dioctylaminofluorane, 2
-Anilino-3-chloro-6-diethylaminofluorane, 2-diphenylamino-6-diethylaminofluorane, 2-anilino-3-methyl-6-diphenylaminofluorane, 2-phenyl-6-diethylaminofluorane, 2 -Anilino-3-methyl-6-N-ethyl-
N-isoamylaminofluorane, 2-anilino-3-
Methyl-5-chloro-6-diethylaminofluorane,
2-anilino-3-methyl-6-diethylamino-7-
Methylfluorane, 2-anilino-3-methoxy-6-
Dibutylaminofluorane, 2-o-chloroanilino-
6-dibutylaminofluorane, 2-p-chloroanilino-3-ethoxy-6-N-ethyl-N-isoamylaminofluorane, 2-o-chloroanilino-6-p-butylanilinofluorane, 2-anilino- 3-pentadecyl-6-diethylaminofluorane, 2-anilino-
3-ethyl-6-dibutylaminofluorane, 2-anilino-3-methyl-4 ', 5'-dichlorofluorane, 2
-O-toluidino-3-methyl-6-diisopropylamino-4 ', 5'-dimethylaminofluorane, 2-anilino-3-ethyl-6-N-ethyl-N-isoamylaminofluorane, 2-anilino- 3-methyl-6-N-
Ethyl-N-γ-methoxypropylaminofluorane,
2-anilino-3-chloro-6-N-ethyl-N-isoamylaminofluorane and the like, and thiazine-based compounds include benzoylleuco methylene blue- and p-nitrobenzoylleucomethylene blue, and spiro-based compounds. , 3-methyl-spirodinaphthopyran, 3
-Ethyl-spirodinaphthopyran, 3,3'-dichloro-spirodinaphthopyran, 3-benzylspirodinaphthopyran, 3-methyl-naphtho-3 (-methoxy-benzo) spiropyran, 3-propyl-spiro-dibenzo There are pyran and the like, and it is desirable to use two or more kinds in combination.

As the electron-accepting compound which is fused with a colorless dye to give a color, in addition to the above-mentioned compounds, known compounds such as phenol derivatives, salicylic acid derivatives, metal salts of aromatic carboxylic acids, acid clay, bentonite, and novolak are included. Resin, metal-treated novolak resin, 4-tert-butylphenol, 4-phenylphenol, 2,2-bis (4
-Hydroxyphenyl) propane (bisphenol A), 4,4'-isopropylidene bis (2-methylphenol), 1,1-bis- (3-chloro-4-hydroxyphenyl) cyclohexane, 1,1- Bis (3-chloro-
4-hydroxyphenyl) -2-ethylbutane, 4,4 '
-Secondary-isooctylidene diphenol, 4-te
rt-octylphenol, 4,4'-sec-butylidene diphenol, 4-chlorophenylphenol, 4,4'-isopentylidene diphenol, 4,4'-methylcyclohexylidene diphenol, 4,4'-dihydroxy Diphenyl sulfide, 1,4-bis'-hydroxycumylbenzene, 1,3-bis-4'-hydroxycumylbenzene, 4,4'-thiobis (6-tert-butyl-3-methylphenol), 4,4'-dihydroxydiphenyl sulfone, hydroquinone monobenzyl ether, 4-hydroxybenzophenone, 2,4-dihydroxybenzophenone, polyvinylbenzyloxycarbonylphenol,
2,4,4'-trihydroxybenzophenone, 2,2 ', 4,4'
-Tetrahydroxybenzophenone, dimethyl 4-hydroxyphthalate, methyl 4-hydroxybenzoate, 2,4,
4'-trihydroxydiphenyl sulfone, 1,5-bis-
p-hydroxyphenylpentane, 1,6-bis-p-hydroxyphenoxyhexane, 4-hydroxybenzoic acid tolyl, 4-hydroxybenzoic acid α-phenylbenzyl ester, 4-hydroxybenzoic acid phenylpropyl,
4-Hydroxybenzoic acid phenethyl, 4-hydroxybenzoic acid-p-chlorobenzyl, 4-hydroxybenzoic acid-p-methoxybenzyl, 4-hydroxybenzoic acid benzyl ester, 4-hydroxybenzoic acid-m-fluorobenzyl ester, 4 -Hydroxybenzoic acid β-phenethyl ester, 4-hydroxy-2 ', 4'-dimethyldiphenyl sulfone, β-phenethyl orserinate, cinnamyl orserinate, orseric acid-o-chlorophenoxyethyl ester , O-ethylphenoxyethyl orserinate, o-phenylphenoxyethyl orserinate, m-phenylphenoxyethyl orserinate, 2,4-dihydroxybenzoic acid-β-3'-t -Butyl-4'-hydroxyphenoxyethyl ester, 1-
t-Butyl-4-p-hydroxyphenylsulfonyloxybenzene, 4-N-benzylsulfamoylphenol, 2,4-dihydroxybenzoic acid-p-methylbenzyl ester, 2,4-dihydroxybenzoic acid-β-phenyl Enoxyethyl ester, 2,4-dihydroxy-6-methylbenzoic acid benzyl ester, methyl bis-4-hydroxyphenylacetate, ditolylthiourea, 4,4'-diacetyldiphenylthiourea, 3-phenylsalicylic acid,
5-p-α-methylbenzyl-α-methylbenzyl salicylic acid, 5-p-methoxyphenoxyethyloxysalicylic acid, 5-phenoxyethoxysalicylic acid, 5-p-
Benzyl-α-methylbenzyl salicylic acid, 3-xylyl-5- (α, α-dimethylbenzyl) salicylic acid, 3,
Aromatic carboxylic acids such as 5-di- (α-methylbenzyl) salicylic acid, 2-hydroxy-1-α-ethylbenzyl-3-naphthoic acid, acids such as 3,5-di-cyclopentadienylsalicylic acid, or Zinc salt, p-hydroxybenzoic acid β-phenoxybutyl ester, p-hydroxybenzoic acid δ-phenoxybutyl ester, 2,4,6-tri-
Hydroxybenzoic acid β-p-methoxyphenoxyethyl ester, p-hydroxybenzoic acid β-phenoxyethoxyethyl ester, p-hydroxybenzoic acid-β-p
-Butoxyphenoxyisopropyl ester, 2,4-dihydroxybenzoic acid-β-p-methoxyphenoxyethoxyethyl ester, orseric acid phenoxybutyl ether, β-resorcinic acid-p-methoxyphenoxyethyl ether, orserine Acid β-p-methoxyphenoxyethoxyethyl ether, orseric acid β-o-methoxyphenoxyethyl ether, orseric acid tolyloxyethyl ester, orserinic acid-β-p-methoxyphenoxypropyl ester, β-resorcinol Organic developers such as phenols such as acid phenoxyethyl ether, β-resorcinic acid δ-p-methoxyphenoxybutyl ester, para-phenylphenol-formalin resin, para-butylphenol-acetylene resin, and these organic compounds For example with a developer Zinc, magnesium, aluminum, calcium, titanium, manganese, tin, polyvalent metal salts such as nickel, inorganic acid, acid clay, activated clay, attapulgite, bentonite, colloidal silica, aluminum silicate, magnesium silicate, zinc silicate, tin silicate, Inorganic developer such as zinc rhodanide, zinc chloride, iron stearate, cobalt naphthenate, nickel peroxide and ammonium nitrate, aliphatic carboxylic acid such as oxalic acid, maleic acid, tartaric acid, citric acid, succinic acid and stearic acid, benzoic One or more of acid, paratertiarybutylbenzoic acid, phthalic acid, gallic acid and the like may be used in combination with the electron-accepting compound of the present invention.

When these colorless dyes and electron-accepting compounds are applied to recording materials, they are used as fine dispersions or fine droplets.

When used for pressure-sensitive paper, U.S. Pat.
2,505,471, 2,505,489, 2,548,366, 2,71
2,507, 2,730,456, 2,730,457, 3,103,4
It can take various forms as described in the prior patents such as 04, 3,418,250 and 4,010,038. Most commonly, it consists of at least a pair of sheets containing separately an electron-donating colorless dye and an electron-accepting compound.

See US Pat. No. 2,800,457 for capsule manufacturing method.
No. 2,800,458, a method utilizing coacervation of hydrophilic colloid sol, British Patent 867,797
No. 950,443, No. 989,264, No. 1,091,076, and the like, and the method described in US Pat. No. 3,103,404.

Generally, an electron-donating colorless dye is used alone or as a mixture, and a solvent (alkylated naphthalene, alkylated diphenyl, alkylated diphenylmethane, alkylated terphenyl,
Synthetic oils such as chlorinated paraffin: cotton oil, vegetable oil such as castor oil: animal oil: mineral oil or mixtures thereof)
After being dissolved in a microcapsule,
A color former sheet can be obtained by applying it to a transparent or opaque smooth support such as paper, wood free paper, plastic sheet, resin coated paper.

Further, an electron-accepting compound alone or in combination, or together with another electron-accepting compound, is dispersed in a binder such as styrene butadiene latex or polyvinyl alcohol, and a pigment, which will be described later, paper, a plastic sheet,
A developer sheet is obtained by applying it to a support such as resin coated paper.

The amount of the electron-donating colorless dye and the electron-accepting compound used depends on the desired coating thickness, the form of the pressure-sensitive copying paper, the capsule manufacturing method, and other conditions, and may be appropriately selected according to the conditions. A person skilled in the art can easily determine this usage amount.

When used in thermal paper, the electron-donating colorless dye and the electron-accepting compound should be 10μ or less in the dispersion medium, preferably 3μ.
It is used by pulverizing and dispersing to the following particle size. As the dispersion medium, a water-soluble polymer aqueous solution having a concentration of about 0.25 to 10% is generally used, and the dispersion is performed using a ball mill, a sand mill, a horizontal sand mill attritor, a colloid mill or the like.

The ratio of the electron-donating colorless dye and the electron-accepting compound used is preferably 1:10 to 1: 0.1 by weight, and further,
Particularly preferred is between 1: 5 and 2: 3. At that time, further aromatic ether compounds such as JP-A-58-57,989 and JP-A-58-87,094 are used.
Aromatic alkyl or substituted alkyl ethers disclosed in, for example, JP. Examples of such ether compounds include phenoxyethyl biphenyl ether,
Phenethyl biphenyl, benzyloxynaphthalene,
Benzylbiphenyl, di-m-tolyloxyethane, β
-Phenoxyethoxyanisole, 1-phenoxy-2
-P-ethylphenoxyethane or bis-β- (p
-Methoxyphenoxy) ethoxymethane, 1-2'-methylphenoxy-2-4 "-ethylphenoxyethane,
1-tolyloxy-2-p-methylphenoxyethane,
1,2-diphenoxyethane, 1,4-diphenoxybutane,
Bis-β- (p-ethoxyphenoxy) ethyl ether, 1-phenoxy-2-p-chlorophenoxyethane, 1-2'-methylphenoxy-2-4 "-ethyloxyphenoxyethane, 1-4 ′ -Methylphenoxy-
Ether such as 2-4 ″ -fluorophenoxyethane or 1-phenoxy-2-p-natoxyphenyl thioether, 1,2-bis-p-methoxyphenyl thioether, 1-tolyloxy-2-p-methoxyphenyl ether It is preferable to use a compound such as an enyl thioether in combination, which is used simultaneously with the colorless dye or finely dispersed at the same time as the electron-accepting compound, and particularly preferably dispersed simultaneously with the colorless dye from the viewpoint of preventing fog. The amount used is added in a weight ratio of 300% or less with respect to the electron-accepting compound, and particularly preferably 10% or more and 150% or less.

Additives are further added to the coating liquid thus obtained in order to satisfy various requirements.

As an example of the additive, in order to prevent the recording head from being soiled at the time of recording, an inorganic pigment, an oil-absorbing substance such as polyurea filler is dispersed in the binder, and the releasability to the head is further improved. Therefore, fatty acids and metal soaps are added. Therefore, generally, in addition to colorless dyes and electron-accepting compounds that directly contribute to color development, addition of pigments, waxes, antistatic agents, ultraviolet absorbers, defoamers, conductive agents, fluorescent dyes, surfactants, etc. The agent is coated on the support to form the recording material.

Specifically, kaolin as a pigment, calcined kaolin, talc, zinc oxide, diatomaceous earth, calcium carbonate, aluminum hydroxide, magnesium hydroxide, calcined gypsum, silica, magnesium carbonate, titanium oxide, alumina, barium carbonate, sulfuric acid. Barium, mica, microballoon, urea-formalin filler, polyethylene particle,
It is selected from those having a particle size of 0.1 to 15μ such as a cellulose filler. In particular, zinc oxide is very advantageous for improving image resistance.

Examples of the paraffin waxes include paraffin wax, carboxy-modified paraffin wax, kauna barow wax, microcrystalline wax, polyethylene wax, and higher fatty acid esters.

Examples of the metal soap include higher fatty acid polyvalent metal salts, that is, zinc stearate, aluminum, calcium salt, zinc oleate and the like.

As a hindered phenol, at least 2 or 6
Phenol derivatives in which one or more of the positions are substituted with branched alkyl groups are preferred.

For example, 1,1-bis (2-methyl-4-hydroxy-
5-t-butylphenyl) butane, 1,1,3-tris (3
-Methyl-4-hydroxy-5-t-butylphenyl)
Butane, bis (2-hydroxy-3-t-butyl-5-
Methylphenyl) methane, bis (2-methyl-4-hydroxy-5-t-butylphenyl) sulfide and the like.

Examples of the ultraviolet absorber include a cinnamic acid derivative, a benzophenone derivative, a benzotriazolylphenol derivative, and the like, for example, butyl α-cyano-β-phenylcinnamate, o-benzotriazolylphenol, o-benzotriazolyl-p- Chlorophenol, o-benzotriazolyl-2,
4-dibutylphenol, o-benzotriazolyl-p
-Chlorophenol, etc.

These materials are also detailed in the aforementioned patents.

These are dispersed and applied in a binder. Water-soluble binders are generally used, and polyvinyl alcohol, hydroxyethyl cellulose, hydroxypropyl cellulose, epichlorohydrin-modified polyamide, ethylene-maleic anhydride copolymer, styrene-maleic anhydride copolymer, isobutylene-maleic anhydride. Examples thereof include copolymers, polyacrylic acid, polyacrylic acid amide, methylol-modified polyacrylamide, starch derivatives, casein, gelatin and the like. Further, a water-proofing agent (gelling agent, cross-linking agent) is added for the purpose of imparting water resistance to these binders, or emulsion of hydrophobic polymer, specifically, styrene-butadiene rubber latex, acrylic resin emulsion, etc. It can also be added.

Further, for the purpose of imparting chemical resistance to the surface of the coating layer, a water-soluble polymer compound such as polyvinyl alcohol, hydroxyethyl starch or epoxy modified polyacrylamide and a gelling agent (hardening agent) of about 0.2 to 2 μm. Can also be provided.

The coating solution is most commonly applied on base paper, fine paper or synthetic paper, preferably neutral paper.

Generally, the coating amount is about ² to 10 g / m ² as a solid content.

When used for thermal paper, OLS2228581 and 211085
No. 4, Japanese Patent Publication No. 52-20142 and the like can be adopted. Alternatively, operations such as preheating, humidity adjustment, or stretching of the coated paper can be added prior to recording.

The electric thermal paper is manufactured by the method described in, for example, JP-A-49-11344 and 50-48930. Generally, a conductive material, a basic dye mainly composed of the fluorane derivative of the present invention, and an electron-accepting compound dispersed together with a binder are applied to a support such as paper, or a conductive material is applied to the support to conduct electrical conductivity. The current-carrying thermal paper of the present invention is produced by forming a layer and applying a coating liquid in which a colorless dye, an electron-accepting substance and a binder are dispersed on the layer. The sensitivity can be improved by using the above-mentioned heat-fusible substance in combination.

The light and pressure sensitive paper is manufactured, for example, by the method described in JP-A-57-179836. Generally, a photopolymerization initiator such as silver iodobromide, silver bromide, silver behenate, Michler's ketone, a benzoin derivative, a benzophenone derivative and a polyfunctional monomer such as polyallylized product, poly (meth) acrylate,
A cross-linking agent such as poly (meth) acrylamide is encapsulated with a colorless dye and optionally a solvent in a synthetic resin wall capsule such as polyether urethane, polyurea. It is developed by the inventors of the present invention after being image-exposed and then colored by contacting with a color developer using a colorless dye in the unexposed area.

(Examples of the Invention) Examples will be shown below, but the present invention is not limited to these examples.

Example 1 (1) Preparation of sample 2-anilino-3-methyl-6-N-ethyl-N-propylaminofluorane 2 g, 2-anilino-3-chloro-
2 g of 6-diethylaminofluorane was dispersed together with 25 g of a 3.5% aqueous solution of polyvinyl alcohol (saponification number: 99%, polymerization degree: 1000) in an average particle size of 2 μ using a sand mill. On the other hand, it was obtained by reacting a copolymer of β-tosyloxyethyl methacrylate and butyl methacrylate with β-resorcinic acid dipotassium salt in the presence of a base. β-3
10 g of a copolymer having a hydroxy-4-carboxyphenoxyethyloxycarbonyl group in the side chain, 10 g of β-naphthol benzyl ether and 20 g of zinc oxide are dispersed together with 50 g of a 3% aqueous solution of polyvinyl alcohol in a ball mill overnight. Further, β-p-methoxyphenoxyethyloxysalicylic acid 8 g, zinc oxide 6 g and 1-phenoxy-2
13 g of -p-ethylphenoxyethane is dispersed with 50 g of a 3% aqueous solution of polyvinyl alcohol in a ball mill overnight. Further, 0.1 g of 1,1,3-tris-2'-methyl-4'-hydroxy-5'-t-butylphenylbutane is dispersed with 20 g of a 5% polyvinyl alcohol aqueous solution for 24 hours. After mixing this well, 15 g of diiodia kaolin,
6 g of fine particle silica was added and well dispersed, and 4 g of Paraffin wax emulsion 50% dispersion liquid (Chukyo Yushi Fat Cerosol # 428) was added to prepare a coating liquid.

The coating solution was applied onto neutral paper having a basis weight of 45 g / m ^{2 so} that the solid content was 6.1 g / m ² , dried at 60 ° C for 1 minute, and then super-cured at a linear pressure of 60 kgW / cm. Rendering was applied to obtain coated paper.

The coated paper was heat-colored with a heating energy of 35 mJ / mm ² to obtain the color density, and the Macbeth reflection densitometer showed 1.01.

The obtained recording material had no fog during raw storage and had excellent stability over time. On the other hand, the color image obtained was a clear black color and showed good resistance to chemicals, water, sunlight and the like.

Example 2 The polymer of Example 1 was changed to β-3-oxy-4-carboxyphenoxymethylstyrene / butyl methacrylate / styrene / methacrylic acid (purchasing ratio 4: 2: 1: 0.2) to give β-
A coating liquid was obtained in the same manner except that naphthol benzyl ether was replaced with stearic acid amide. The coating liquid was applied to a high-quality paper obtained by coating calcium carbonate on neutral paper at 6 g / m ² and dried in the same manner as in Example 1.

When the color was developed according to the method of Example 1, a clear black image was obtained, and the reflection density was 0.95 or more.

This black image was clear, and the discoloration or fading was remarkable even when exposed to oil and fat or sunlight.

Example 3 The colorless dye of Example 1 was prepared using 2-anilino-3-methyl-6-
N-ethyl-N-isoamylaminofluorane 2.5 g, 2
-Anilino-3-chloro-6-diethylaminofluorane 0.5 g and 3 ', 6'-bisdiethylamino-5-diethylaminospiro (isobenzofuran-1,9'-fluorene) -3'-one 1.5 g When a color was developed in the same manner, a black impression was obtained. This image had high density and excellent light resistance and heat resistance. This image also had optical absorption in the near infrared region.

Claims (1)

[Claims] 1. A recording material utilizing coloring by contact with an electron-donating colorless dye and an electron-accepting polymer compound having 10% or more of an alkoxysalicylic acid skeleton represented by the following general formula (I) in a side chain. In the above formula, R ₁ is a hydrogen atom, an alkyl group, R ₂ is a divalent group having 16 or less carbon atoms, R ₃ and R ₄ are hydrogen atoms, halogen atoms, hydroxy groups, alkoxy groups, aryl groups, Alkyl group, aryloxy group, thioalkoxy group, alkoxycarbonyl group, optionally substituted amino group, acyloxy group, cyano group, nitro group, acyl group, carbamoyl group, sulfamoyl group, aralkyl group, substituted aryl group , An alkyl group having a substituted aryl group,
It is selected from a carbonyl group, a carboxyl group and a sulfo group. R ₃ and R ₄ may combine with each other to form a 5- or 6-membered saturated or unsaturated ring.