JPH0818460B2 - 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 a colorless dye and an electron-accepting compound is
It is already well known as pressure-sensitive paper, heat-sensitive paper, light-sensitive pressure-sensitive paper, electric heat-sensitive recording paper and the like. For example, British Patent 2140449, US Patent 4480052, US Patent No. 4436920, JP-B-60-23922, and JP-A-57
Details on -179836, 60-123556, 60-123557, etc.

The recording material should have the following properties: (1) sufficient color density and color sensitivity, (2) sufficient color fastness, and (3) high S / N ratio. ) The safety of the materials used is taken into consideration.

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 a fine particle polymer compound in which an electron-accepting compound is emulsified and dispersed in a recording material utilizing a phenomenon that a colorless dye is colored by contacting with the electron-accepting compound. This has been achieved by developing a recording material featuring the above.

The recording material in the present invention preferably has a protective layer made of a polymer compound.

Examples of the colorless dye include compounds that give a colored product by an electron-accepting compound such as Lewis acid or protonic acid.

Examples of colorless dyes include triphenylmethanephthalide compounds, fluorane compounds, phenothiazine compounds, indolylphthalide compounds, leucoauramine compounds, rhodaminelactam compounds, triphenylmethane compounds, triazene compounds. , Various compounds such as spiropyran compounds.

Regarding these various colorless dyes, for example, specific examples of phthalides are U.S. Reissue Patent 23024, U.S. Pat.
Specific examples of 3491112, 3491116, 3509174, and fluoranes are U.S. Patents 3624107, 3627787, 3641011, 34628.
28, 3681390, 3920510, 3959571, specific examples of spirodipyrans are U.S. Pat.No. 3971808, pyridine-based and pyrazine-based compounds are U.S. Pat.Nos. 3775424, 3853869,
U.S. Pat.No. 4246318, etc. or U.S. Pat.
The colorless dyes disclosed in 936 and 4622565 are used.

Examples of some of the colorless dyes include, as triarylmethane compounds, 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, 2-
Dibenzylamino-6-diethylaminofluorane, 2
-Anilino-6-diethylaminofluorane, 2-anilino-3-methyl-6-diethylaminofluorane, 2
-2,4-Dimethylanilino-3-methyl-6-N-hexylmethylaminofluorane, 2-o-chloroanilino-6-diethylaminofluorane, 2- (3,4-dimethylanilino) -3-methyl -6-diethylaminofluorane, 2-octylamino-6-diethylaminofluorane, 3,6-dibutoxyfluorane, 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-p-
Dimethylaminoanilino-6-diethylaminofluorane, 2-anilino-3-methyl-6-β-pyridylethylaminofluorane, 2-phenyl-6-diethylaminofluorane, 2-anilino-3-methyl-6-N -Ethyl-N-isoamylaminothiofluorane, 2-anilino-3-methyl-5-chloro-6-diethylaminofluorane, 2-anilino-3-methyl-6-diethylamino-7-methylfluorane, 2-anilino -3-Methoxy-6-dibutylaminothiofluorane, 2-o-chloroanilino-6-dibutylaminofluorane, 2-o
-Chloroanilino-6-p-butylanilinofluorane, 2-anilino-3-pentadecyl-6-diethylaminofluorane, 2-anilino-3-methyl-4 ', 5'
-Dichlorofluorane, 2-o-toluidino-3-methyl-6-N-methylisopentylamino-4 ', 5'-dimethylaminodiazafluorane, 2-anilino-3-ethyl-6-N- Ethyl-N-isoamylaminofluorane, 2-anilino-3-methyl-6-N-ethyl-N-
There are γ-butoxypropylaminofluorane, 2-anilino-3-chloro-6-N-ethyl-N-isoamylaminofluorane, and the like, and thiazine-based compounds include benzoylleuco methylene blue, p-nitrobenzoylleucomethylene blue, and the like. As the spiro compound,
3-Methyl-spiro-dinaphthopyran, 3-ethyl-spiro-dinaphthopyran, 3,3'-dichloro-spiro-dinaphthothiopyran, 3-benzylspiro-dinaphthopyran, 3-methyl-naphtho- (3-methoxy-benzo) There are spiropyran, 3-propyl-spiro-dibenzopyran and the like, and it is desirable to use two or more kinds in combination.

Furthermore, the monomer or polymer of the colorless dye proposed by the present inventors can be used.

The colorless dye polymer is a copolymer of a colorless dye having a polymerizable functional group such as vinyl, (meth) acrylic, and allyl.

Triphenyl methanephthalide compounds having the above-mentioned functional groups, fluoran compounds, phenothiazine compounds, indolylphthalide compounds, leuco auramine compounds, rhodamine lactam compounds, triphenyl methane compounds, triazene compounds, Examples thereof include copolymers such as spiropyran compounds.

Preferred examples of the colorless dye having an addition-polymerizable group are as follows.

1) 2-p-vinylbenzoylamino-6-diethylaminofluorane 2) 2-p- (4'-vinylbenzoylamino) anilino-3-methyl-6-dibutylaminofluorane 3) 2-p (4'- Vinylbenzylamino) anilino-
3-chloro-6-N-ethyl-N-isoamylaminofluorane 4) 2-vinylbenzylideneamino-6-diethylaminofluorane 5) 2-β- (p-vinylbenzoylamino) ethylamino-3-chloro-6 -Diethylaminofluorane 6) 2-β- (p-vinylbenzoylaminoethylamino) ethylamino-6-diethylaminofluorane 7) 2-p-vinylbenzenesulfonylamino-3-isoamyl-6-diethylaminofluorane 8) 2 -Anilino-3-methyl-6-N-ethyl-N-
β-p-vinylbenzoylaminoethylamino-fluorane 9) (p-vinylbenzoylamino) benzoylleucomethylene blue 10) 4-diethylaminophenyl-4′-N-ethyl-
N-vinylbenzylaminophenylphthalide 11) 2-p-vinylbenzoyloxy-4-diethylaminophenyl-2'-p-vinylbenzoyloxy-
4'-Methyl-5'-anilinophenylphthalide 12) 2-p-vinylphenylureido-6-diethylaminofluorane 13) 2-p-vinylanilino-3-methyl-6-diethylaminofluorane 14) 2- Anilino-4-γ-p-vinylbenzoylaminobutyl-6-diethylaminofluorane 15) 2-β-hydroxy-γ-p-vinylphenoxy-
Propylamino-6-diethylaminofluorane 16) 3- (4-diethylamino-2-methacryloxyphenyl) -3- (1-ethyl-2-methylindol-3-yl) phthalide 17) 3- [4-diethylamino -2-p-Vinylbenzyloxyphenyl] -3- (1-ethyl-2-methylindol-3-yl) (diaza) phthalide 18) 3- [4-diethylamino-2- (4-vinylbenzoyloxy) Phenyl] -3- (1-ethyl-2-methylindol-3-yl) phthalide 19) 3- [4-diethylamino-2- (vinyloxyethyloxy) phenyl] -3- (1-ethyl-2-methyl Indole-3-yl) phthalide 20) 3- [4-diethylamino-2- (β-acryloxyethoxy) phenyl] -3- (1-ethyl-2-me Ruindol-3-yl) phthalide 21) 3- (4-dibutylamino-2-β-acrylamidoethoxyphenyl) -3- (1-ethyl-2-methylindol-3-yl) phthalide 22) 3- ( 4-Diethylamino-2-vinylbenzyloxyphenyl) -3- (1,2-dimethylindole-3
-Yl) phthalide 23) 3- (4-diethylamino-2-β, γ-dimethacryloxypropoxyphenyl) -3- (1-ethyl-2)
-Phenylindol-3-yl) phthalide 24) 3- [4-diethylamino-2- (β-acryloxypropyloxy) phenyl] -3- (1-ethyl-2)
-Methylindol-3-yl) 4-azaphthalide 25) 3- [4-diethylamino-2-vinylbenzenesulfonyloxy) phenyl] -3- (1-ethyl-2-
Methylindol-3-yl) -4-azaphthalide 26) 3- [4-diethylamino) -2- (β-vinylphenoxy) phenyl] -3- (1-ethyl-2-pentylindol-3-yl) -4- Azaphthalide 27) 2-acrylamido-6-diethylaminofluorane 28) 2-acrylamino-6-dibutylaminofluorane 29) 2-acrylamino-6-N-cyclohexyl-N
-Methylaminofluorane 30) 2-acrylamino-3-chloro-6-diethylaminofluorane 31) 2-acrylamino-3-methyl-6-diethylaminothiafluorane 32) 2-methacrylamino-3-ethyl-6- Dibutylaminofluorane 33) 2-p-methacrylaminoanilino-6-diethylaminofluorane 34) 2-p-acrylaminoanilino-6-dibutylaminofluorane 35) 2-β-acrylaminobutylamino-6- Dibutylaminofluorane 36) 2-β-acrylaminopropylamino-3-chloro-6-diethylaminofluorane 37) 2-anilino-3-β-acrylaminobutyl-6
-Diethylaminofluorane 38) 2-p-chloroanilino-3-β-methacrylaminopropyl-6-dibutylaminofluorane 39) 2-anilino-3-methyl-6-N-ethyl-N-
p-acrylaminoanilino-fluorane 40) 2-dibenzylamino-6-N-acrylamino-
N-Ethylfluorane 41) 2-Hexylamino-6-N-methacrylaminobutyl-N-ethylfluorane 42) 3,3-Bis (p-dimethylaminophenyl) -6-
N-Ethyl-N-β-methacryloxyethylaminophthalide 43) 3,3-bis (p-diethylaminophenyl) -6-
N-ethyl-N-vinylbenzylaminophenylphthalide 44) 3,6-bis-β-methacryloxyethoxyfluorane 45) 3,6-bis-p-vinylbenzyloxyfluorane and the like can be mentioned.

It is convenient to copolymerize one or more of these colorless dyes having a vinyl group with another monomer having a vinyl or vinylidene group. For example, examples of the monomer include amides, ethers, esters, and aromatics having an addition polymerizable group. Preferred compounds are those obtained by reacting polyamines, polyols, amino alcohols and the like with allyl halides, (meth) acrylic acid chlorides or (meth) acrylic acid esters.

The particle size, solubility, tackiness, dispersion stability, color developability and the like can be freely controlled by selecting these amounts, types and combinations. However, in the case of copolymerization, it is preferable that the color-forming agent component, which is colored by contact with an acidic substance, is contained in an amount of at least 5 mol% or more.

Examples of such copolymerization partners include acrylamide, cellosolve acrylate, styrene, vinyl acetate, vinylidene chloride, butadiene, isoprene, methyl methacrylate, acrylonitrile, vinylcarbazole, octyl acrylate, sodium acrylamidopropanesulfonate, isobutyl. Methacrylate, ethyl acrylate, divinylbenzene, vinyldioxolane,
Epichlorohydrin, allyl methacrylate, cinnamoyloxyethyl methacrylate, vinyl benzophenone, ethylene glycol diacrylate, diethylene glycol diacrylate, diethylene glycol monoacrylate, chloromethylstyrene, methacrylamide, cellosolve acrylate, chlorostyrene, oleyl methacrylate, methacrylonitrile, 6 -Cyanovinylcarbazole, triethylene glycol (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate, β-phenylureidoethyl acrylate, 2-ethylhexyl acrylate, calcium acrylamidopropanesulfonate, Butyl methacrylate, isobutyl acrylate, dibi Rutoruen, ethyl cellosolve acrylate, methallyl methacrylate, alpha-cyano cinnamonitrile acetoxyphenyl butyl methacrylate, beta-phenoxyethanol methacrylate, include triethylene glycol allyl ether acrylate, one or more kinds are selected.

Among these, at least one is preferably an acrylic ester or a methacrylic ester.

Regarding these, U.S. Patents 4623557, 3799915 and 38
74947, Imai "Functional Coating" Nikkan Kogyo Shinmasha,
Also detailed.

As a method of the polymerization reaction, radical polymerization, ionic polymerization, solution polymerization, emulsion polymerization, suspension polymerization and the like are preferable.

More specifically, for example, the radical polymerizations preferred according to the invention can be initiated by radical initiators.
Persulfate (part of base agent), oily or aqueous azo compound,
A peroxide, a metal-based catalyst or the like can be used. The polymerization reaction is preferably carried out in an inert gas atmosphere, and when heated, it is 120 ° C or lower, particularly 90 ° C.
The following are preferred.

When a solvent is used, polar solvents such as water, esters, ethers, halides, ketones, amides, alcohols, etc., and nonpolar solvents such as hydrocarbons, aromatics etc. can be used alone or in combination.

It is also possible to improve the hue and the coloring efficiency by allowing various colorless dyes to coexist during the polymerization reaction. Among them, particularly preferable are those polymerized by a radical polymerization catalyst in an aqueous solvent, and among them, a copolymer obtained by latex polymerization.

The fine particle polymer compound of the electron accepting compound will be described.

The term "fine particles" refers to particles having a particle size of 3μ or less, particularly 1.5μ or less. Above all, 0.5 μm or less is preferable.

To obtain the emulsion-dispersed particulate polymer compound of the present invention, for example, (1) a method of once synthesizing a polymer compound and then emulsifying and dispersing in water using a solvent (2) by emulsion polymerization in an aqueous medium A method of obtaining an emulsified dispersion can be used.

As described above, the synthesis of the polymer compound is performed by (a) a method of copolymerizing an electron-accepting compound having an addition-polymerizable group with another monomer, and (b) a polymer compound having a reactive group to an electron-accepting compound. There is a method of combining.

Examples of the monomer having an electron-accepting group used in the method (a) include compounds having an addition-polymerizable group and a phenolic hydroxyl group, a carboxyl group, a sulfo group, and the like, particularly phenols, salicylic acids, and metal compounds thereof. There is a combination of or metal salts.

The addition-polymerizable electron-accepting compound can be obtained, for example, by the following synthetic method.

Most simply, a vinyl compound having a hydroxyl group is once converted into a sulfonate and then reacted with an electron-accepting compound having a hydroxyl group, an amino group or a carboxyl group.

 For example, such a compound is represented by the following formula.

In the above formula, R ₁ is a hydrogen atom, an alkyl group, and divalent R ₂ is a group having 16 or less carbon atoms, which is saturated or unsaturated and has an ether bond, an ester bond, a urethane bond, an amide bond, or the like. May be.

Preferred examples of R ₂ are -CnHzm-, -X-, —X—C _n H ₂ m—, etc., and R ₅ is a group described for R ₃ such as a hydrogen atom,
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, and the like, such as a hydroxy group, an alkyl group, an acyloxy group, a halogen atom, and an aryl group. To
n and m represent an integer of 0 to 8. For example, −CONHC ₂ H ₄ −, −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-, OCH 2 -, −C ₂ H ₄ OCH ₂ OC ₂ H ₄ −, −C ₂ H ₄ COC ₂ H ₄ −, −CO ₂ C ₂ H ₄ −, _{-CONHCH 2 -, - CO 2 C} 2 H 4 OC 2 H 4 -, - C 2 H 4 SC 2 H 4 -, CH
₂ CH ₂ O ₂ C ₂ H ₄ −, −C ₂ H ₄ NA _C C ₂ H ₄ −, −CONHC ₂ H ₄ −, −C
O ₂ C ₃ H ₆ −, −CO ₂ C ₃ H ₅ cl−, _{-C 3 H 5 clO -, -} C 4 H 6 -, - C 3 H 5 (OH) O -, - C 3 H 6 OC 3 H 6
-, Are particularly preferred specific examples. Particularly, having 7 or less carbon atoms is advantageous in synthesis.

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

As described above, the compound represented by the formula I can be converted into an addition-polymerizable electron-accepting compound by reaction with a compound having a phenolic hydroxyl group or a carboxyl group.

The compound having a phenolic hydroxyl group or a carboxyl group is represented by the following formula, for example.

In the above formula, R ₃ and R ₄ are hydrogen atom, halogen atom, hydroxy group, alkoxy group, aryl group, alkyl group, aryloxy group, thioalkoxy group, alkoxycarbonyl group, optionally substituted amino group, and acyloxy. Base,
It is selected from cyano group, nitro group, acyl group, carbamoyl group, sulfamoyl group, aralkyl group, carboxyl group, sulfo group and the like. At least one of R ₃ and R ₄ represents a hydroxyl group or a carboxyl group.

 Specific examples of such compounds are as follows.

Hydroxybenzoic acid, bisphenol S, bisphenol A ₁ C, p-carbomethoxyphenol, p-carboxymethylthiophenol, 2,4-dihydroxyphenoxyacetic acid, p-hydroxyphenylacetic acid, diphenolic acid, α, α- Bis-4-hydroxyphenylacetic acid, β-
Resorcinic acid, hydroxychlorobenzoic acid, salicylic acid, hydroxynaphthoic acid, 4-hydroxyphenylthiopropionic acid, orseric acid, mercaptobenzoic acid,
Hydroxyanilinoacetic acid, 3-methoxy-4-hydroxyphenylacetic acid, dihydroxynaphthoic acid, phloroglucincarboxylic acid, p-carbomethoxybenzoic acid, thiohydroquinone, benzoylresorcinol, 4-carboxy-2-benzotriazolyl- Phenol, hydroxymethylphenol, phenolsulfonic acid, phenolsulfonamide, cresolphthalein, naphtholsulfonic acid, hydroxysulfonaphthoic acid, phenolphthalein, hydroxyphthalic acid, fluorescein,
Is one example.

Chloromethylstyrene, α-chloro-2-methacryloxyethyl acetate and the like also react with an electron-accepting compound having a phenolic hydroxyl group and a carboxyl group under the same reaction conditions as the above-mentioned sulfonate.

As the base, an organic base, an inorganic base such as dimethylaminopyridine, dabco, pyridine, pyrazine, triethylamine, caustic potassium, caustic soda, sodium methylate, carbonate carbonate, sodium carbonate, lithium hydroxide, magnesium hydroxide, magnesia, etc. can be used. However, above all, inorganic bases, especially derivatives of sodium or potassium, give good results. Particularly, carbonate is advantageous in terms of reactivity and ease of post-treatment.

Moreover, the presence of a polar solvent during this reaction gives favorable results.

The above-mentioned sulfonic acid ester having an addition polymerizable group,
It is conveniently synthesized by the reaction of an alcohol having an addition-polymerizable group with an aromatic sulfonyl chloride, preferably p-toluenesulfonyl chloride. It is also possible to use it for the reaction of the next step without once taking out the aromatic sulfonic acid ester. In that case, as alkali,
Lithium, sodium or potassium hydroxide, carbonate, alcoholate and the like are advantageous, and an aqueous solution of hydroxide is particularly effective.

These bases are used in an amount necessary to neutralize the sulfonic acid generated by the reaction. It is preferably 0.5 to 1.5 times the amount of the sulfonic acid ester.

The polar solvent is preferably a solvent having a hydrophilic group such as ether, carbonyl, sulfonyl, hydroxy, ester, cyano or amide.

For example, acetone, methyl ethyl ketone, dimethylformamide, dimethyl sulfoxide, acetonitrile, butyrolactone, N-methylmorpholine, dimethylacetamide, acrylonitrile, N-methylpyrrolidone, N-acetylmorpholine, hexamethylphosphoramide, sulfolane, cyclohexanone and the like are preferable, and particularly, A water-soluble solvent is preferable from the viewpoint of easy post-treatment.

These solvents have a solid content concentration of 10% or more, preferably 20%.
It is used so that it becomes more than%.

It is also preferable to use a small amount of water together, from the viewpoints of dissolving the inorganic base and the sulfonate and preventing by-products from coloring. Furthermore,
Performing the reaction in an inert gas atmosphere is also a preferable method from the viewpoint of preventing coloration of the liquid.

In addition, crown ether, phase transfer catalyst and polymerization inhibitor may be used in the reaction.

It is particularly preferable to use a polymerization inhibitor in an amount of about 0.005 to 0.1%.

Further, it is preferable to control the reaction temperature of the system to 110 ° C. or lower, and it is particularly preferable to carry out the sulfonylation reaction step at 70 ° C. or lower and the esterification reaction step at 60 ° C. or higher.

Also, a method using a normal acid halide, a method by transesterification, etc. can be used.

Examples of the compound obtained by the method of the present invention include the following compounds. 1) Styrenesulfonylaminosalicylic acid 2) Vinylbenzyloxyphthalic acid 3)
β-methacryloxyethoxysalicylate 4) Vinyloxyethyloxybenzoic acid 5) β-methacryloxyethoxysalicylic acid 6) β-methacryloxyethyl orsellinate 7) β-methacryloxyethoxyphenol 8) β-methacryloxyethyl-β -Resorcinate 9) Hydroxystyrenesulfonic acid-N-ethylacrylamide 10) β-methacryloxypropyl-p
-Hydroxybenzoate 11) Methacryloxymethylphenol 12) Methacrylamide amidopropanesulfonic acid
13) β-methacryloxyethoxy-dihydroxybenzene 14) γ-styrenesulfonylamino-β-methacryloxypropanecarboxylic acid 15) γ-acryloxypropyl-α-hydroxyethyloxysalicylic acid 16)
β-hydroxyethoxycarbonylphenol 17) β
-Methacryloxyethyl-3,4-dihydroxycinnamate 18) 3,5 distyrene sulfonic acid amide phenol
19) Methacryloxyethoxyphthalic acid 20) Methacrylic acid 21) Methacryloxyethoxyhydroxynaphthoic acid 22) 3-β-methacryloxyethoxyphenol
23) β-methacryloxyethyl-p-hydroxybenzoate 24) β ¹ -acryloxyethyl-β resorcinate 25) β-methacryloxyethyloxycarbonylhydroxybenzoic acid 26) N, N-di-β-methacryloxyethylamino Salicylic acid 27) N, N-diβ-methacryloxyethylaminosulfonylsalicylic acid, 28) Gallic acid-β-methacryloxyethyl ester 29) 3-
Chloro-4-hydroxybenzoic acid-β-acryloxyethylamide 30) Vinylbenzyloxyphthalimide
31) p-Hydroxyphenylacetic acid vinylbenzyl ester 32) 3,5-diβmethacryloxyethoxybenzenesulfonic acid 33) 3,5-diβ-methacryloxyethoxybenzenesulfonic acid zinc 34) trimellitic acid mono-β-
Methacryloxyethyl ester and the like and metal salts thereof such as zinc salt are particularly preferable.

In the polymerization of these electron-accepting monomers, it is convenient to further copolymerize with one or more other monomers having one or more vinyl or vinylidene groups. For example, examples of the monomer include amides, halides, ethers, esters, and aromatics having an addition-polymerizable group as described above. These can be copolymerized under the same conditions as the above-mentioned monomers. The monofunctional monomer has been described above.

Examples of polyfunctional monomers include polyamines, polyols, amino alcohols and allyl halides, (meth)
By reaction with acrylic acid chloride or (meth) acrylic acid ester Polyvinylbenzene and the like are preferred compounds.

For example, ethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, trimethylolpropane di (meth) acrylate,
β (meth) acrylamidoethyl (meth) acrylate, 1,6-di (meth) acrylamidehexane, divinylbenzene, butanediol diglycidyl ether, 1,
3-di-β- (meth) acryloxyethoxybenzene,
Polyethylene glycol poly (meth) acrylate, allyl (meth) acrylate and the like are examples thereof. These are about 60% by weight or less, preferably 10% by weight in the polymer.
Used below. These effects are mentioned above.

In the polymerization reaction as described above, for the emulsification method, the degassing method, the reaction temperature control, the handling method of the metal catalyst, the post-treatment method after the completion of the polymerization reaction, the purification method of the obtained polymer compound, etc. It is convenient to operate with reference to. For example, see Sorensen “Polymer Synthesis Experimental Method”, Tokyo Kagaku Dojin, 1966 for general procedures.
Familiar with.

Next, the method for obtaining the target polymer by binding the electron-accepting compound to the polymer compound (b) having a reactive group will be described below.

The method of using a polymer compound having a reactive group has already been studied in several fields, and for example, a method of binding a photocrosslinkable compound is well known. The target electron-accepting compound can be obtained by changing the material used therein from the photocrosslinking compound to the electron-accepting compound.

For example, U.S. Patents 2756143, 2861057, 3257664, 332
9664, 3560465, 3635720, 3696072, 3737319, 374813
1, 3767737, 3817876, etc. to maleic anhydride copolymer, vinyl acetate copolymer saponified product, hydroxyethyl (meth) acrylate copolymer, chloromethylstyrene copolymer, diacetone acrylamide copolymer, glycidyl (meth ) A reaction example using an acrylate copolymer or the like is shown.

The electron-accepting compound convenient for the method (b) of the present invention is an electron-accepting compound having an aliphatic hydroxyl group or an amino group, an electron-accepting compound having an acid halide group, an acetic acid group such as a phenolic hydroxyl group or a carboxyl group. Examples include a combination of groups or an electron-accepting compound having one or more of these groups.

The present inventors have already examined some of these and have applied for a patent.

On the other hand, the above-mentioned emulsion dispersion will be described. Conventionally, it is used as a fine dispersion when a colorless dye and an electron-accepting compound are applied to a recording material.

This is an important technique for increasing the surface area of the material that contributes to the color development reaction, increasing the frequency and opportunity of contact between the colorless dye and the electron acceptor, and increasing the sensitivity of the recording material. Usually, the electron-donating colorless dye and the electron-accepting compound are used by pulverizing and dispersing in a dispersion medium to a particle size of 10 μm or less, preferably 3 μm or less.

As the dispersion medium, a water-soluble polymer aqueous solution having a concentration of about 0.2 to 10% is generally used, and the dispersion is performed using a ball mill, a sand mill, a model sand mill attritor, or the like.

However, the dispersion method using media such as these balls, sands, or flint stones has a major drawback.

The reason is that in order to disperse and atomize the particles, it is essential to make the space between these media as small as possible, and increase the load, enlarging the equipment, cumbersome handling, and the media due to the lapse of processing time. This is because wear is inevitable.

For example, an electron-accepting compound dispersion liquid obtained by making fine particles by using a sand mill is obtained as follows.

Using the sand of fine particles, the sand and the sand and the electron-accepting compound are impacted by high-speed rotation to prepare a water-dispersed acid dispersed in fine particles.

Therefore, in the dispersion, sand, an electron-accepting compound,
Fine particles and worn sand or shards of sand coexist.

In order to obtain only the desired product from these dispersions, a special separation operation is required, which is industrially difficult to employ. In addition, it is very inconvenient for hard sand to be mixed in the coating liquid. On the other hand, on the other hand, making the recording material into fine particles is important as a technique for increasing the sensitivity.

The method of the present invention is characterized in that a remarkably finely divided dispersion liquid can be easily obtained without such a mechanical fine dispersion process using media.

As for the method of emulsifying and dispersing, (1) a method of emulsifying and dispersing into fine particles using a solvent, (2) a method of emulsion-polymerizing an addition-polymerizable material, and (3) a method of dissolving in an emulsified and dispersed polymer such as latex. There are such things, and these methods themselves are already known. What is emulsified and dispersed into fine particles using the solvent of (1) is one in which an electron-accepting compound dissolved in a water-soluble solvent is added to water in the presence of a protective colloid and vigorously stirred to emulsify and disperse. If necessary, a small amount of hydrophobic solvent can be used together.

As the water-soluble solvent, those having a polar group such as alcohol, ether, ketone and nitrile and having a boiling point of 150 ° C. or less are preferable.

Hydrophobic solvents include esters, hydrocarbons and halides.

The protective colloid and the surfactant are selected from the following, for example.

Examples of the protective colloid include polyvinyl alcohol, carboxy-modified polyvinyl alcohol, hydroxyethyl or propylcellulose, maleic anhydride copolymer alkylamine salt, and acrylamide copolymer carboxylated starch.

As the surfactant, fatty acid salt, higher alcohol sulfate ester salt, alkylbenzene sulfonate, alkylnaphthalenesulfonate, naphthalenesulfonic acid formalin condensate, dialkylsulfosuccinate, alkylphosphate salt, polyoxyethylene sulphate Anionic surfactants such as salts; nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkylphenol ethers, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene acyl esters; Cationic surfactants such as alkyl amine salts, quaternary ammonium salts, polyoxyethylene alkyl amines, etc .;
Alternatively, one or more water-soluble polymers such as polyvinyl alcohol may be used alone or as a mixture, and among them, emulsions having non-ionic surfactants having HLB of 10 or more, which have outstanding stability, may be used. Most suitable in terms of bringing.

These surfactants are generally used in the range of 0.01% to 20% by weight, particularly preferably in the range of 0.05% to 10% by weight, based on the colorless dye and / or the electron-accepting compound.

The method of emulsion-polymerizing or latex-polymerizing the addition-polymerizable material (2) will be described below.

The addition-polymerizable electron-accepting compound has a phenolic hydroxyl group and the like, and can be emulsion-polymerized despite being considered to suppress radical polymerization, emulsion-polymerization, Latex-polymerization, without agglomeration, using a normal stirrer. Even with the emulsion polymerization used, it is surprising to give a polymer with a particle size below 1 μ.

It is essential that the electron-accepting compound having an addition-polymerizable group and the comonomer are polymerized at pH 11 or less, preferably pH 9.5 or less using a radical polymerization catalyst in the presence of a surfactant and a protective colloid.

If the pH exceeds 11, the water solubility of the electron-accepting compound will sharply increase and the emulsion will become unstable.

Further, the surfactant and protective colloid must coexist at 10 ⁻⁵ wt% (relative to the monomer weight), preferably 10 ⁻³ wt% or more, or the stability of the obtained emulsion over time will not be sufficient.

For emulsion polymerization, 5 wt% of electron-accepting compound is used.
It is preferable to use monomers and / or solvents that are% soluble.

In the copolymerization reaction, the solid content concentration is preferably 5 wt% or more.

The water-soluble solvent described above is also effective in emulsion polymerization.

The addition-polymerizable electron-accepting compound having a (meth) acrylic acid ester bond is easier to emulsify and disperse and is easier to handle than a highly crystalline and hardly soluble monomer having an acrylic acid amide type bond. It is easy to use and does not easily aggregate.

The combined use of a small amount of acrylic acid or methacrylic acid is also effective in improving the dispersion stability.

Further, as described above, various electron-accepting compounds can be used together during the copolymerization reaction or the preparation of the recording material dispersion liquid.

As such an electron-accepting compound, a generally known compound such as a phenol derivative, a salicylic acid derivative,
Examples include metal salts of aromatic carboxylic acids and acid clay.

For example, 4-tert-butylphenol, 4-phenylphenol, 2,2-bis (4-hydroxyphenyl) propane (bisphenol A), 4,4'-isopropylidenebis (2-methylphenol), 1, 1-bis-
(3-chloro-4-hydroxyphenyl) cyclohexane, 1,1-bis (3-chloro-4-hydroxyphenyl) -2-ethylbutane, 4,4'-secondary-isooctylidenediphenol, 4-octyl Phenol, 4,
4'-sec-butylidene diphenol, 4-chlorophenyl diphenol, 4,4'-isopentylidene diphenol, 4,4'-methylcyclohexylidene diphenol,
4,4'-dihydroxydiphenyl sulfide, bis-
4'-hydroxycumylbenzene, 4,4'-thiobis (6-butyl-3-methylphenol), 4,4'-dihydroxydiphenyl sulfone, hydroquinone monobenzyl ether, 4-hydroxybenzophenone, 2, 4-
Dihydroxybenzophenone, vinylbenzyloxycarbonylphenol, 2,2 ', 4,4'-tetrahydroxybenzophenone, dimethyl 4-hydroxyphthalate, 4
-Methyl hydroxybenzoate, 2,4,4'-trihydroxydiphenyl sulfone, 1,5-bis-p-hydroxyphenyl pentane, bisphenol S monoisopropyl ether, 4-hydroxybenzoic acid p-butylbenzyl ester, Phenylpropyl 4-hydroxybenzoate, 4
-Phenethyl hydroxybenzoate, p-fluorobenzyl 4-hydroxybenzoate, p-methoxybenzyl 4-hydroxybenzoate, benzyl 4-hydroxybenzoate, 4-hydroxy-2 ', 4'-dimethyldiphenyl sulfone , Β-phenethyl orsellinate, cinnamyl orsellinate, orsellic acid-o-chlorophenoxyethyl ester, o-ethylphenoxyethyl orsellinate, o-phenylphenoxyethyl orsellinate, 2,4-dihydroxybenzoic acid-β-3′-t
-Butyl-4'-hydroxyphenoxyethyl ester, stearyl gallate, 2-ethylhexylamide gallate, 4-N-benzylsulfamoylphenol,
2,4-dihydroxybenzoic acid-β-phenoxyethyl ester, 2,4-dihydroxy-6-methylbenzoic acid benzyl ester, bis-4-hydroxyphenylacetic acid allyl, ditolylthiourea, 4,4′-diacetyl Diphenylthiourea, 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, 3,5-di-
(Α-Methylbenzyl) salicylic acid, 2-hydroxy-
1-α-ethylbenzyl-3-naphthoic acid, 3,5-di-
Cyclopentadienyl salicylic acid, p-hydroxybenzoic acid β-phenoxybutyl ester, p-hydroxybenzoic acid δ-phenoxybutyl ester, 2,4,6-tri-
Hydroxybenzoic acid β-p-butoxyphenoxyethyl ester, p-hydroxybenzoic acid β-phenoxyethoxyethyl ester, p-hydroxybenzoic acid-β-p
-Butoxyphenoxyisopropyl ester, 2,4-dihydroxybenzoic acid-β-p-methoxyphenoxyethoxyethyl ester, thiodiethanoldi-β-resorcinate orseric acid phenoxybutyl ether, β-
Resorcinic acid-p-methoxyphenoxyethyl ether, orseric acid β-p-methoxyphenoxyethoxyethyl ether, orseric acid β-o-methoxyphenoxyether, orseric acid-β-p-methoxyphenoxypropyl Organic developers such as esters, β-resorcinic acid phenoxyethyl ether, β-resorcinic acid δ-p-methoxyphenoxybutyl ester, phenylphenol-formalin resin, and the like, and further these organic developers Coloring agent and acid clay of polyvalent metal salt such as zinc, magnesium, aluminum, calcium, etc.,
There are inorganic developers such as activated clay, attapulgite, aluminum silicate, magnesium silicate, zinc rhodanide, its complex, and zinc chloride.

 Alternatively, a complex salt represented by the following formula.

(R) ₂ Zn (A) _{2 In the} above formula, R is a monodentate or polydentate colorless organic ligand which is bound to a zinc ion through a hetero atom to form a complex,
A represents SCN, cl, or a benzoic acid anion having an electron-withdrawing group.

Among the colorless organic ligands represented by R, pyridine, imidazole, quinoline, benzothiazole, benzimidazole or antipyrine ligands are preferable, and these are alkyl groups, cyano groups, alkoxy groups, aryl groups,
It may be substituted with a substituted amino group or the like. A screw body is also preferable. Among these organic ligands, those having 6 or more carbon atoms, preferably 10 or more carbon atoms are advantageous from the viewpoint of improving hydrophobicity and oil solubility. For example, rhodan zinc 2-benzylimidazole complex, benzimidazole complex, 2,3-dimethyl-1-
p-ethylphenyl-3-pyrazolin-5-one complex,
1-phenyl-2-methyl-3-benzyl-3-pyrazolin-5-one complex, 1-phenyl-2-methyl-3-
(2-Ethylhexyl) -3-pyrazolin-5-one complex, 1-phenyl-2-methyl-3-isopropyl-3
-Pyrazolin-5-one complex, 1-phenyl-2,3-dibenzyl-pyrazolin-5-one complex, 1-phenyl-
2-benzyl-3-methyl-pyrazolin-5-one complex, methylenebisantipyrine complex, laurylimidazole complex and the like can be mentioned.

You may use 2 or more types of these. Furthermore, inorganic developers such as iron stearate, cobalt naphthenate, nickel peroxide, ammonium nitrate, oxalic acid, maleic acid, tartaric acid,
It can also be used in combination with one or more of aliphatic carboxylic acids such as citric acid, succinic acid, stearic acid, benzoic acid, para-tert-butylbenzoic acid, phthalic acid and gallic acid.

Among these electron-accepting compounds, a combination of compounds selected from bisphenols, salicylic acid derivative metal salts, especially zinc salts, and / or rhodan zinc complexes is particularly useful in the present invention.

For these, British Patents 1018793, 2166882, 216595
Detailed on 3, 2162650, 2156535, 2154014 etc.

The electron-accepting compound polymer of the present invention by such various means has a physiologically active group such as a phenolic hydroxyl group and a skin irritating group (for example, those of phenols and cresols are already well known). Nevertheless,
It is also unexpected that the properties are remarkably reduced due to being polymerized.

The emulsified and dispersed electron-accepting compound polymer is brought into contact with a colorless dye to give a color material having high fastness.

Therefore, it is a useful emulsion dispersion which can be applied to various recording materials such as heat-sensitive paper, pressure-sensitive paper, photosensitive pressure-sensitive paper, electric recording paper or thermal transfer paper.

When used for thermal paper, for example, an electron-accepting compound polymerized into fine particles by an emulsion polymerization method is coated on a support together with a colorless dye and a binder to form a recording material.

The ratio of the colorless dye and the electron-accepting compound polymer used is preferably between 1:10 and 1: 0.1 by weight, and further
Particularly preferred is between 1: 5 and 2: 3. At that time, aromatic ether compounds such as aromatic alkyl or substituted alkyl ethers disclosed in JP-A Nos. 58-57989 and 58-87094 and British Patent 2169553 may be used in combination. Examples of such ether compounds include phenoxyethyl biphenyl ether, phenethyl biphenyl, benzyloxynaphthalene, benzyl biphenyl, di-m-tolyloxyethane, β-phenoxyethoxyanisole, 1-phenoxy. -2-p-ethylphenoxyethane, bis-β- (p
-Methoxyphenoxy) ethoxymethane, 1-tolyloxy-2-p-methylphenoxyethane, 1,2-diphenoxyethane, 1,4-diphenoxybutane, bis-β-
(P-Methoxyphenoxy) ethyl ether, 1-phenoxy-2-p-chlorophenoxyethane, 1-4'-
Methylphenoxy-2-4 ″ -fluorophenoxyethane, 1-phenoxy-2-p-methoxyphenyl thioether, 1,2-bis-p-methoxyphenylthioethane, 1-tolyloxy-2-p-methoxyphenyl Nylthioethane, phenyl hydroxynaphthoate, phenoxypropionamide, p-xylylenediol, stearylphenylurea, β-naphthoxyacetic acid-β′-phenoxyethyl ester, phenoxyacetic acid anilide, phenoxyacetic acid benzylamide, 1-tolyloxy-2-p-
Methoxyphenyl thioether, stearic acid amide,
Ethylene bis stearamide, stearic acid aniside,
A compound such as anilide stearate and stearyl urea is preferably used in combination. These are used simultaneously with the colorless dye or finely dispersed at the same time as the electron accepting compound. The amount of these used is 300% or less by weight of 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 meet 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, in general, in addition to colorless dyes and electron-accepting compounds that directly contribute to color development, pigments, waxes, antistatic agents, ultraviolet absorbers, defoamers, conductive agents,
Additives such as a fluorescent dye and a surfactant are coated on the support to form a recording material.

Specifically, kaolin as a pigment, calcined kaolin,
Talc, zinc oxide, amorphous silica, calcium carbonate, aluminum hydroxide, magnesium oxide, calcined stone, silica, magnesium carbonate, titanium oxide, alumina, barium carbonate, barium sulfate, mica, microballoon,
Urea-formalin filler, polyethylene particle, cellulose filler and the like having a particle size of 0.1 to 15 .mu.m.

As waxes, paraffin wax, carboxy-modified paraffin wax, carnauba wax wax,
In addition to microcrystalline wax, polyethylene wax, higher fatty acid esters and the like.

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

Hindered phenols include compounds having at least one bulky group adjacent to a phenolic hydroxyl group, such as polybutylated bisphenol A and 1,1,3-tris-3-t-butyl-4-hydroxy-6. -Methylphenyl butane and the like.

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 copolymer, polyacrylic acid, polyacrylic acid amide,
Methylol modified polyacrylamide, starch derivative,
Examples include casein and gelatin. In addition, a water resistance agent (gelling agent,
Cross-linking agent), hydrophobic polymer emulsion,
Specifically, styrene-butadiene rubber latex, acrylic resin emulsion and the like can be added.

In order to impart chemical resistance and scratch resistance to the coating layer surface, it is preferable to provide a layer made of a polymer compound. At that time, 0.2 to 10μ in combination with inorganic pigment and gelling agent
It is desirable that the layer has a thickness of about 2 to 5 μm. Such materials include polymer compounds that have already been studied and include the following.

Polyvinyl alcohol, hydroxyethyl starch or epoxy modified polyacrylamide acetoacetyl modified polyvinyl alcohol, polyurethane, silicon modified polyvinyl alcohol, polyhydroxyethyl (meth)
Acrylate modified product, acetoacetyl modified polyhydroxyethyl (meth) acrylate-butyl methacrylate copolymer, polyacrylic acid glyoxal modified product, casein, polyvinylpyrrolidone, styrene-butadiene latex, polyvinyl alcohol / acrylamide / acrylonitrile copolymer, carboxy Methylcellulose glyoxal modified product, hydroxyethyl cellulose acetoacetyl modified product, etc.

For example, water-soluble polymer-crosslinking agent-pigment is exemplified by polyvinyl alcohol / boric acid or methylol compound / colloidal silica, acetoacetyl-modified PVA / methylol compound /
Kaolin, polyacrylic acid glyoxal modified product / polyacrylamide epichlorohydrin modified product / colloidal silica, acetoacetyl modified polyvinyl alcohol / styrene butadiene latex / colloidal silica, styrene butadiene latex / casein / methylol compound / urea formalin resin, carboxy modified PVA / Urea formalin resin / amorphous silica and the like are preferable. Alternatively, a transparent resin layer such as a polyethylene film or a polyacetonitrile film may be provided in a thickness of about 0.1 to 10 μm by a technique such as laminating, plasma polymerization or sputtering.

The coating liquid is applied on base paper, high-quality paper, transparent plastic film, laminated paper, art paper, aluminum foil or synthetic paper, preferably neutral paper. When a transparent plastic film is used, it preferably has a thickness of about 30 to 150 μm, especially 2
Axial stretch heat-fixed polyethylene terephthalate has excellent handling and transparency.

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

When used for pressure-sensitive paper, U.S. Pat.
71, 2505489, 2548366, 2712507, 2730456, 2
It can take various forms as described in the prior patents such as 2730457, 3103404, 3418250 and 4010038. Most commonly it consists of at least a pair of sheets containing separately a colorless dye and an electron-accepting compound.

For a method of manufacturing capsules, US Patent 2800457,
Method using coacervation of hydrophilic colloid sol described in the same 2800458, British Patent 867797, 95044
3, the method described in US Pat. No. 3,103,404, and the interfacial polymerization method described in JP-A-992664 and 1091076.

In general, colorless dyes, alone or in combination, are used as solvents (synthetic oils such as alkylated naphthalene, alkylated diphenyl, alkylated diphenylmethane, alkylated terphenyl, and chlorinated paraffin: vegetable oil such as cotton oil, castor oil: animal oil: mineral A color former by dissolving it in oil or a mixture thereof, including it in microcapsules, and then applying it to a transparent or opaque smooth support such as paper, woodfree paper, plastic sheet, resin coated paper, etc. Get the sheet.

Further, an electron-accepting compound alone or in a mixture or together with other electron-accepting compounds is dispersed in a binder such as styrene butadiene latex or polyvinyl alcohol, and a pigment, which will be described later, is used for paper, plastic sheet, resin coated paper, etc. A color developer sheet is obtained by applying it to a support. The amounts of the colorless dye and the electron-accepting compound used depend 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.

The electric thermal paper is manufactured by the method described in, for example, JP-A-49-11344 and 50-48930. In general, conductive materials,
The coating solution in which the colorless dye and the electron-accepting compound of the present invention are dispersed together with a binder is applied to a support such as paper, or a conductive material is applied to the support to form a conductive layer, on which a colorless dye and an electron are applied. The electrothermal paper is manufactured by applying a coating liquid in which a receptive substance and a binder are dispersed. 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, which is exposed to an image and then colored by being brought into contact with a color developer by utilizing a colorless dye in an unexposed area.

Upon coating on the support, a binder such as PVA or latex and a protective agent such as fine particles are used. Further, various additives, binders, antioxidants, anti-stripes agents, surfactants or coating methods, methods of use, etc. which have been conventionally used in recording systems are well known.
2711375, 3625736, British Patent 1232347, JP-A-50-4401
2, 50-50112, 50-127718, 50-30615, U.S. Patent 38
There are disclosures in 36383 and 3846331, and those methods can also be used.

For example, the coating may be performed on the recording layer and the protective layer by an air knife, a bar, a roll, a blade, a curtain, etc. at any time or simultaneously.

The protective layer also has an advantage that it is possible to prevent staking at the time of recording, dust adhesion to the thermal head, and bleeding.

Therefore, the recording material of the present invention which gives an image having high toughness is suitable for applications requiring storage stability, stability, and tamper resistance.

For example, recording materials for automatic ticket vending machines, coupon tickets, commuter tickets,
It is extremely effective for POS label paper, magnetic ticket paper, etc.

In the case of a label sheet, a release liner may be attached to the opposite surface of the recording layer via an adhesive layer, and in the case of a magnetic ticket paper, a magnetic recording layer composed of a ferromagnetic material and a binder is used. It should be provided.

The handling and form of the recording material are known in the fields of thermal paper, pressure-sensitive paper, and photosensitive paper. For example, OLS2228581, 2121854, and Japanese Examined Patent Publication 52-2014.
2. Various modes described in JP-A-57-179836 and JP-A-60-123556 can be adopted. Alternatively, operations such as preheating, humidity adjustment, or stretching of the coated paper can be added prior to recording.

Furthermore, U.S. Patents 2505470, 2505471, 2505489, 2
548366, 2712507, 2730456, 2730457, 310340
4, various forms can be adopted as described in 4, 3418250, 4010038 and the like.

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

Example 1 A three-necked flask was equipped with a thermometer, a stir bar, a condenser nitrogen introducing tube and a dropping funnel, and 2% polyvinyl alcohol.
250 ml was added.

A solution prepared by dissolving 5 g of 2-ethylhexyl acrylate, 5 g of 2-tacryloxyethyl-β-resorcinate and 0.02 g of butylene glycol dimethacrylate in 30 ml of ethanol and 10 ml of acetonitrile was gradually added with vigorous stirring while passing nitrogen gas through, and emulsified. Ammonium persulfate is added to the solid content of 1wt%, 70 ℃ ～ 75 ℃
Held for 6 hours.

 Most of the solvent was removed out of the system during the polymerization reaction.

Thus, an emulsion copolymer dispersion of the polymerizable electron-accepting compound and the monomer was obtained.

 The particle size was 85 mμ.

 This is referred to as an emulsified dispersion (A).

On the other hand, 3- (4-diethylamino-2-β-methacryloxyethoxyphenyl) -3- (1-ethyl-2-
0.5 g of methylindol-3-yl) phthalide and 0.5 g of crystal violet oletolactone were dispersed together with 25 g of a 3.5% aqueous solution of polyvinyl alcohol (saponification degree: 99%, polymerization degree: 1000) in an average particle diameter of 2 μ using a sand mill.

 This is called dispersion liquid (B).

β-p-methoxyphenoxyethyloxysalicylic acid
8 g, zinc oxide 10 g, 1-phenoxy-2-p-ethylphenoxyethane 13 g and 1,1,3-tris-2'-methyl-4'-hydroxy-5'-t-butylphenylbutane 0.1 g Was dispersed with 60 g of a 5% polyvinyl alcohol aqueous solution overnight.

 This is called dispersion liquid (C).

The emulsified dispersion liquids (A), (B) and (C) have a solid content ratio of 1.5:
Mix well to get 1: 0.5. Furthermore, 15 g of diiodia kaolin and 6 g of fine particle silica are added and well dispersed, and further, a mixed solution of 4 g of Paraffin Wax emulsion 50% dispersion liquid (Chukyo Yushi-Serosol # 428) is added so that the solid content is 3.5. It was used as a coating liquid.

The coating liquid was applied onto neutral paper having a basis weight of 45 g / m ^{2 so} that the solid component coating amount was 5.5 g / m ² . Further, the following surface protective layer dispersion liquid (E) or (F) was applied so as to have a thickness of 2 μm, dried at 60 ° C. for 1 minute, and then coated with a super calender at a linear pressure of 60 kgW / cm to obtain a coated paper.

Surface protection layer dispersion (E) 200 parts of 10% aqueous polyvinyl alcohol solution, 10 parts of 20% aqueous solution of polyacrylic acid modified glyoxal (molar ratio of acrylic acid to glyoxal 1/2), modified polyacrylamide epichlorohydrin modified (kaimen) 557H) 12 of
% Aqueous solution 10 parts, fine calcium carbonate 30 parts, water 600 ml, finely dispersed with a ball mill.

Surface protective layer dispersion (F) Polyvinyl alcohol acetoacetyl modified product (Nippon Gosei Kagaku, Gohseheimer Z-200) 10% aqueous solution 1000 parts,
A liquid in which 250 parts of calcium carbonate (Brilliant 15) are finely dispersed with 500 ml of water.

The color density of all the coated papers was 0.93 by Macbeth reflection densitometer when the color density was calculated by heating and coloring with heating energy of 35 mJ / mm ² by Facsimile.

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

Example 2 A polymer dispersion was obtained in the same manner except that 2-ethylhexyl acrylate used in the synthesis of the polymer of Example 1 was replaced with isobutyl methacrylate and ammonium persulfate was replaced with potassium persulfate.

 The colorless dye dispersion was prepared as follows.

2-anilino-3-methyl-6-N-ethyl-N-propylaminofluorane 2g, 2-anilino-3-chloro-6-diethylaminofluorane 2g each 3.5%.
This was dispersed with 25 g of an aqueous solution of polyvinyl alcohol (saponification number: 99%, polymerization degree: 1000) using a sand mill to an average particle size of 2 μm. These were thoroughly mixed so that the solid content ratio was 2: 1, and the dispersion liquid (C) was added in the same manner as in Example 1.

The coating solution was applied to a high-quality paper obtained by applying calcium carbonate on neutral paper so as to have a concentration of 6 g / m ² , and a protective layer was further provided, followed by drying 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 Diiodia kaolin of the coating solution of Example 2 was reduced to 1/20,
Undercoat transparent polyethylene terephthalate 75 as support
Images were obtained in the same manner except that the μ product was used.

The obtained image was effective as an overhead original.

Example 4 250 ml of water was placed in a three-necked flask equipped with a stirrer thermometer, and 5 g of butyl acrylate and 3- (4-diethylamino-2-β-methacryloxyethoxyphenyl) -3- (1- Octyl-2-methylindole-3
-Yl) Phthalide (5 g) dissolved in ethanol (45 ml) was added and emulsified and dispersed. As the emulsifier, 1 g of methyl oil taurate was used. While introducing nitrogen gas into this,
1% by weight of radical polymerization initiator K ₂ S ₂ O ₈ was added under vigorous stirring, and the mixture was kept at 65 to 70 ° C. for 4 hours. Ethanol was removed from the system during the polymerization reaction.

Thus, an emulsion copolymer dispersion of the polymerizable colorless dye and the monomer was obtained. The particle size was 81 mμ.

 This is designated as emulsion (D).

 The solution was concentrated under reduced pressure to a solid content concentration of 10 wt%.

The emulsified dispersion liquid (A) was well mixed with this so that the solid content ratio was 1: 1.7.

Then, synthetic calcium carbonate, amorphous silica, and zinc stearate were added in a solid content of 1.5 parts and 0.5 parts, respectively.
It was added to 0.2 parts and stirred well.

This solution was applied to a smooth surface on which fine calcium carbonate was applied so as to be 6 g / m ² on neutral paper so as to be 5 g / m ² .

When a color was developed by heating with Facsimile in the same manner as in Example 1, a clear blue image was obtained.

Example 5 The electron-accepting copolymer composition of Example 4 was prepared by mixing 3 g of 2-ethylhexyl acrylate, 1 g of acrylic acid, 3 g of 2-methacryloxyethyl-β-resorcinate, and resorcinic acid-β-.
Methacryloxyethyl ether 2g, divinylbenzene 0.
A coated paper was obtained in the same manner except that the amount was 01 g, and a color image was obtained in the same manner as in Example 1.

The obtained blue image was clearer than that obtained in Example 4, and the resistance was also excellent.

Claims (1)

[Claims] 1. A recording material comprising a support and a recording layer provided with a recording layer utilizing the phenomenon that a colorless dye is brought into contact with an electron-accepting compound to color the fine particles in which the electron-accepting compound is emulsified and dispersed. A recording material characterized by being a polymer compound of