JPH01168487A - Recording material - Google Patents

Abstract

PURPOSE:To obtain a recording material having favorable color forming properties and stability of developed color images by incorporating a specified salicylic acid derivative or a metallic salt thereof as an electron-acceptive compound. CONSTITUTION:A salicylic acid derivative or a metallic salt thereof, of formula I, is incorporated as an electron-acceptive compound. In the formula, R is a divalent group, X is hydrogen, an alkyl, phenyl, alkoxyl or halogen, M is an n-valent metal, and n is an integer. The salicylic acid derivative can be easily obtained by, for example, bringing a salicylic acid derivative having a chloromethyl group and a phenol derivative into reaction. At least one such salicylic acid derivative or metallic salt thereof is used singly or in combination, in the state of a finely dispersed material or minute droplets, for a recording material.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of the Invention) The present invention relates to a recording material, and more particularly to a recording material with improved color development and stability of colored images.

(Prior Art) Recording materials using an electron-donating colorless dye and an electron-accepting compound are already well known as pressure-sensitive paper, thermal paper, light-sensitive pressure-sensitive paper, current-carrying thermal recording paper, thermal transfer paper, and the like. The analogy is U.S. Patent J, 30! , ≠ No. 70, same λ, soj,
Hiro♂ri issue, same λ, jta01lA7/ issue, same 2. j11.
l, No. 366, same, 7/2.307, same, 2,730
．． Hirojz issue, same λ.

730.4Ljt No. 7, same 3. Hiroshi/♂, 2! ;No. 0, Tokukai Sho≠ter2ryo, Hiro//No., Tokukai Sho, 10-Hiroshi≠.

No. 009, British Patent 2/≠ol! Hiro issue, US Patent Hiro,
≠10.0! No. 2, same≠, ≠36. ri No. 20, Tokuko Sho I
No. 10-23, 222, Tokukai Sho! ;7-/7ri, 136
No. tO-/23. ! Jt issue, same Otsu 0-/23. Taj
I am familiar with issue 7 etc.

The performance that a recording material should have is (1) sufficient color density and color development sensitivity, (2) no fogging, (3) sufficient fastness of color body, and (4) color development. It has an appropriate hue and is suitable for copying machines, f5) a high S/N ratio, and (6) sufficient chemical resistance of the coloring body.

Particularly in pressure-sensitive recording materials, if the color-forming area is filed on a vinyl chloride sheet or the like, the color-forming area will be erased by the plasticizer or the like, which significantly reduces its commercial value.

In addition, heat-sensitive recording materials have the disadvantage that fogging occurs due to solvents and the like, and the color formers undergo discoloration and fading due to oils, fats, chemicals, etc. Therefore, when it comes into contact with water-based inks, oil-based inks, fluorescent pens, ink ink, adhesives, glue, diazo developer, and other supplies and office supplies, or cosmetics such as hand cream and emulsion, the white parts may develop color. The coloring part was discolored and faded, resulting in a significant loss of product value. The present inventors investigated the oil solubility, water solubility, partition coefficient, and p Ka for each of the electron-donating colorless dye and the electron-accepting compound.

We have pursued the development of good recording material materials and recording materials by focusing on characteristics such as the polarity of the substituent, the position of the substituent, and changes in crystalline solubility when mixed.

(Object of the Invention) Therefore, an object of the present invention is to provide a recording material using a material that has good color development properties and stability of color images, and also satisfies other requirements.

(Structure of the Invention) An object of the present invention is to provide a recording material that utilizes the phenomenon in which a point colored dye is colored when it comes into contact with an electron-accepting compound, in which the electron-accepting compound is represented by the following general formula (I). This was achieved using a recording material characterized by containing a salicylic acid derivative or a metal salt thereof.

(I) In the above formula, R is a divalent group, X is a hydrogen atom, an alkyl group,
A phenyl group, an alkoxy group, or a norogen atom,
M represents a zero-valent metal atom, and n represents an integer.

Among the divalent groups represented by R in the above formula, the following general formula (II
) to (■) are preferred.

In the above general formulas (II) to (IV), R1 and R
2 may be the same or different and represents a hydrogen atom, an alkyl group, an alkoxy group,...a rogene atom, an aryl group or a hydroxyl group, an R' alkylene residue or an aralkylene residue. Among the substituents represented by
-20 alkoxy groups, phenyl groups, chlorine atoms and fluorine atoms are preferred, and among the groups represented by M, zinc, aluminum, magnesium and calcium are preferred.

Specific examples of the divalent group represented by R include (Y represents a hydrogen atom, an alkyl group, an aryl group, or a halogen atom).

In the above general formula CI), the substitution position of the substituted methyl group substituted on the salicylic acid skeleton is preferably the meta position with respect to the C00M group. Also, the substitution position of substituent X is C00
The meta position relative to the M group is preferred.

The salicylic acid derivative according to the present invention can be easily obtained, for example, by reacting a salicylic acid derivative having a chloromethyl group with a phenol derivative.

Next, specific examples of salicylic acid derivatives according to the present invention are shown,
The present invention is not limited to these.

C3H17(t) C12H25(t) I 9H19 H3 Ol CsHx7(t) Old) H3 H3 and their metal salts, etc., and these are used alone or in mixtures.

Further, the salicylic acid derivative according to the present invention may be used in combination with well-known electron-accepting compounds other than the present invention, such as salicylic acid derivatives, phenol derivatives, phenol resins, and acid clay.

To illustrate some of these, ≠-ternary butylphenol, Hiro-phenylphenol, ≠-hydroxydiphenoxide α-naphthol, β-naphthol, hexyl-Hiro-hydroxybenzoate, λ xl )
Hydroxybiphenyl, λ, 2-bis(Hiro-hydroxyphenyl)propane (bisphenol A), +C, ≠
′ -isopropylidene bis(co-methylphenol)
, /, /'-His(3-=chloro-guhydroxyphenyl)cyclohexane, /,/-bis(3-10rho≠-hydroxyphenyl)-2-ethylbutane, Hiro.

μ'-Secondary octylidene diphenol, tert-octylphenol, ψ.

II'-5ec-butylizo/diphenol, Hiro-p-methylphenylphenol, ≠, 4"-iapentylidenephenol, ≠, ≠'-methylchlorohexylidene diphenol, '7.4"-dihydroquine diphenyl sulfide, /, Hiro-bis-(ri'-hydroxycumyl)benzene, /, 3-bis-(≠'-hydroxycumyl)benzene, Hiro.

μ'-thiobis(J-1ert-butyl-3-methylphenol), ≠, ≠'-dihydroxydiphenylsulfone, hydroquinone monobenzyl ether, ≠-hydroxybenzophenone, 21≠-dihydroquinobenzophenone, polyvinylbenzyloxyl Luponylphenol, +2. F, ≠′-trihydroxybenzopheno/
,λ,2′,≠.

ψ'-tetrahydroxybenzopheno/, ≠-hydroxyphthalic acid, dimethyl-≠-methyl hydroxybenzoate, 2. II, 'l'-)lihydroxydiphenylsulfone, /, j-bis-p-hydroxyphenyl methane, /, 6-bis-p-hydroxyphenoxyhexane, ≠-hydroxybenzoic tolyl, hydroxybenzoic acid α-phenylbenzyl ester, ≠-hydroxybenzoate phenylpropyl, phenethyl hydroxybenzoate, p-chlorobenzyl hydroxybenzoate, p-methoxybenzyl hydroxybenzoate, ≠
-Hydroxybenzoic acid benzyl ester, Hiro-hydroxybenzoic acid-m-chlorobenzyl ester, Gu-hydroxybenzoic acid-β-phenethyl ester, Hiro-hydroxy-λ', Hiro'-dimethyldiphenylsulfone-β
- phenethyl orselinate, cinnamyl orselinate, orserin rll-o-chlorophenoxyethyl ester, 0-ethylphenoxyethyl orselinate,
0-Phenylphenoxyethyl orselinate, m-phenylphenoxyethyl orselinate, co,≠-dihydroxybenzoic acid-β-J'-t-butyl-Hiroshi'-
Hydroxyphenoxyethyl ester, /-t-7'thyl-≠-p-hydroxyphenylsulfonyloxybenzene, ψ-N-be/silsulfamoylphenol, 2
．． Hiro-dihydroxy'/benzoic acid-β-phenoxyethyl ester, co,≠-dihydroxy-6-methylbenzoic acid benzyl ester, bis-gu-hydroxyphenylacetate methyl, ditolylthiourea, tA, ψ'-diacetyldiphenylthiourea, 3 -Phenylsalicylic acid, 3
-cyclohexylsalicyl R13,3-tert
-Methylsalicylic acid, 3-methyl-t-benzylsalicylic acid, lophenyl-t-(α,α-dimethylbenzyl)salicylic acid, 3°yo-di(α-methylbenzyl)
salicylic acid, j-[-octylsalicylic acid, 3. j-di-t-butylsalicylic acid, 3-chloro-yo-cumylsalicylic acid, 3-methyl-1-1-octylsalicylic acid, 3
-Methyl-yo-α-methylbenzylsalicylic acid, 3-methyl-j-cumylsalicylic acid3. ! -di-t-amylsalicylic acid, 3-phenyl-yo-benzylsalicylic acid, 3
-Phenyl-rt-octylsalicylic acid, 3-phenyl-j-α-methylbenzylsalicylic acid, 3. j-ji-
t-octylsalicylic acid, 3. j-bis(α-methylbenzyl)salicylic acid, 3. ! -Dicumylsalicylic acid, cumethyl-yo-(α-methylbenzyl)salicylic acid, ≠
-Methyl-turcumylsalicylic acid, 3-(α-methylbenzyl)-6-methylsalicylic acid, 3-(α-methylbenzyl)-6-phenylsalicylic acid, 3-triphenylmethylsalicylic acid, 3-diphenylmethylsalicylic acid,
p-n-dodecylsalicylic acid, ≠-1-dodecylsalicylic acid, Hiro-n-dodecylsalicylic acid, Hiro-n-pentadecylsalicylic acid, p-n-heptadecylsalicylic acid,!
-(/,J-diphenylbutyl)-salic acid, t-n-octadecylsalicylic acid,! -Dodecylsulfonylsalicylic acid,! -dodecylsulfosalicylic acid, 3
-Methyl-y-dodecylsulfosalicylic acid and the like.

The electron-accepting compound is the 30-3 electron-donating dye precursor.
000% by weight, more preferably 100 to 2000% by weight.

The electron-accepting compound described above is preferably mixed with the salicylic acid derivative, which is the electron-accepting compound according to the present invention, in a proportion of 200 to 10% by weight.

Further, two or more of the above electron-accepting compounds may be used in combination.

Electron-donating colorless dyes according to the present invention include triphenylmethane phthalide compounds, fluoran compounds, phenothiazine compounds, indolyl phthalide compounds, leucoolamine compounds, rhodami/lactam compounds, and triphenylmethane compounds. There are various compounds such as triazene compounds, spiropyran compounds, and fluorocarbon compounds.

Specific examples of phthalides can be found in U.S. Patent Reissue Specification Box 23.0
No. 21tL-, US patent specification cylinder 3. μri/.

ll1 No. 3. Hiroshi/, No. 112, No. 3゜≠ri/
, //A No. 3. No. 77≠, specific examples of fluoranes can be found in U.S. Patent Specification No. 3, 4211-. 10
No. 7, No. 3,427,717, No. 3.6/,
0// No. 3. ≠62. ! No. 2r and No. J,
tl/, 370, U.S. Patent Specification No. 3,6♂/, 3
No. 90, U.S. Pat. No. 3,220,310, U.S. Pat. 7/, No. 101; pyridine-based and pyrazine-based color-forming compounds are described in U.S. Pat. ♂j3゜r62
No., U.S. Patent Specification No. 2≠6, . No. 3/1, specific examples of fluorene compounds are described in Japanese Patent Application No. 1983/-λ≠Ori♂R, etc. To illustrate these - parts, as a triarylmethane compound, 3,3-bis(p-dimethylaminophenyl)-6-dimethylaminophthalide (
crystal violet lactone), 3,3-bis(p-dimethylaminophenyl)phthalide, 3-(≠-
diethylaminoλ-ethquinphenyl) -3-(/-
Octyl-2-methylindol-3-yl)phthalide, 3-(≠-diethylaminoλ-ethoxyphenyl)-
J-(/-ethyl J-methylindol-3-yl)phthalide, etc., diphenylmethane compounds include ≠, ψ′-bis-dimethylaminobenzhydrin pendyl ether, N-halophenyl-leuco, t Examples of xanthine compounds include rhodamine-B-anilinolactam, 3-diethylamino-7,
-ni/zofluorane, B-anilinolactam, rhodamine (p-nitroanilino)lactam, rhodami/B (
p-chloroanilino)lactam, 2-be/dylamino-
6-ethylaminofluorane, co-anilino-diethylaminofluorane, 2-anilino-3-methyl-
6-diethylaminofluorane, λ-anilino 3-methyl-6-cyclohexylmethylaminofluorane 7.2
-Q-chloroanilino-t-diethylaminofluorane, 2-m-chloroanilino-6-diethylaminofluorane, λ-(3,≠-dichloroanilino)-ot-diethylaminofluorane, λ-octylamino-6-dinityl Aminofluorane, λ-Regihexylamino-6-diethylaminofluoran 2-m-t')fluoromethylanilino-6-diethylaminofluorane, 2-butylamino-3-chloro-6-diethylaminofluorane,
λ-ethoxyethylamino-3-chloro-6-diethylaminofluorane, 2-p-chloroanilino-3-methyl-6-cyptylaminofluorane, rhoanilino 3
-Methyl-6-sioctylaminofluorane, -1anilino-3-chloro-6-dinithylaminofluorane, 2
-diphenylamino-6-diethylaminofluorane,
λ-anilino 3-methyl-6-diphenylaminofluorane, λ-phenyl-6-dinithylaminofluorane, λ-anilino 3-methyl-A -N-ethyl-N-
Isoamylaminofluorane, 2-anilino-3-methyl-j-chloro-6-diethylaminofluorane, 2-
Anilino-3-methyl-6-dinithylamine-7-methylfluoran, λ-anilino 3-methoxy-6-cyptylaminofluorane, λ-0-chloroanilino 6=
Dibutylaminofluorane, λ-p-chloroani IJ
/ -3-ethquin-g -N-ethyl-N-ynamylaminofluorane, λ-0-chloroanilino+-p
-butylanilinofluorane, λ-anilino 3-pentadecyl-6-diethylaminofluorane, λ-anilino 3-ethyl-6-cyptylaminofluoran/, 2-
Anilino-3-methyl-≠', j'-dichlorofluoran isotonic acid, indolyl phthalide compound: 3.
3-bis(/-ethyl-1-methylindol-3-yl)phthalide, 3,3-bis(/-octyl-nomethylindol-3-yl)phthalide, 3-(2-ethoxy-≠-diethylaminophenyl) )-J-(/-ethyl-2-methylindol-3-yl)phthalide, 3-(
2-ethoxy-goo-dibutylaminophenyl)-3-(
/-ethyl-2-methylindol-3-yl)phthalide, 3-(2-amyloxy-≠-diethylaminophenyl)-3-(/-ethyl-2-methylindole-3
-yl) phthalide, 3-(2-ethoxy-goodiethylaminophenyl) -J -(/ -:A-rif-2
-methylindol-3-yl) phthalide, etc., and examples of pyridine compounds include 3-(2-ethoxy-goodiethylaminophenyl)-3-(/-octyl-2-methylindol-3-yl, -hiro or 7 -Azaphthalide, 3-(,2-ethoxy-goodiethylaminophenyl)-3-(/-ethyl-z-methylindole-3-
yl)-Hiroshi or 7-azaphthalide, 3-(λ-hexyloxy-Hiro-diethylaminophenyl)-3-(/-ethyl-λ-methylindol-3-yl)-≠ or 7-
azaphthalide, 3-(λ-ethoxy≠-diethylaminophenyl)-3-(/-ethyl-2-phenylindol-3-yl)-4' or 7-azaphthalide, 3-(
,2-butquin-goodiethylaminophenyl)-3-
(/-ethyl-λ-phenylindole-3-yl)-
≠ Also, there are Hafu 79 phthalide, 3-(2-ethoxy-Hiro-diethylaminophenyl)-3-(/-octyl-2-phenylindol-3-yl)-≠ or 7-azaphthalide, etc., and the fluorene compounds include: 3', t'
-bisdiethylamino-terdiethylaminospiro(inbensiffuran-/,ri'-fluorene)-3-one, 3',t'-bisdiethylamino-7-diethylamine-2-methylspiro(/,3-benzoxazine-
Hiroshi, ri'-fluorene), J', A'-bisdiethylamino-7-ethylaminospiro (2-hydro/, 3-benzoxazine-≠, ri'-fluorene)
- There are coon etc.

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

The recording material according to the present invention has extremely stable colored images, and this effect is remarkable in pressure-sensitive and heat-sensitive recording materials.

When used with pressure sensitive paper, the US patent tube 2. SO, ≠7
No. 0, 2.30! , 4L7/issue, same co.

30! , ≠♂ri issue, same λ,! ≠1, 3 Otsu No., 2.
7/co, No. 507, same λ, 730. ≠! No. 6, No. 2,
730. Kou No. 57, No. 3103≠0≠, No. 3. ≠／
It can take various forms as described in prior patents such as No. 1,2jO and No. 010031. Most commonly they consist of at least one pair of sheets containing separately an electron-donating colorless dye and an electron-accepting compound.

A method for manufacturing capsules is described in U.S. Pat. No. 2.100.
Method using coacervation of hydrophilic colloid sol described in 1tjt No. 7, 2, 100, 11-31, British Patent No. 7,727, same! 0. Hiroshi ≠ No. 3, same r ri, 26 ≠ No. 3, same /.

Examples include the interfacial polymerization method described in U.S. Pat.

In general, electron-donating colorless dyes are used alone or in combination as solvents (alkylated naphthalene, alkylated diphenyl, alkylated diphenylmethane, alkylated terphenyl, alkylated terphenyl, etc.).
Synthetic oils such as chlorinated paraffin; Vegetable oils such as cotton oil and castor oil; Animal oils; Mineral oils and mixtures thereof)
After dissolving it in a bath and incorporating it into microcapsules,
A color forming agent sheet is obtained by coating it on a support such as paper, high quality paper, plastic sheet, resin coated paper, etc.

In addition, an electron-accepting compound alone or in combination with other electron-accepting compounds is dispersed in a binder such as styrene-butadiene latex or polyvinyl alcohol, and the electron-accepting compound is dispersed in a binder such as styrene-butadiene latex or polyvinyl alcohol.
A developer sheet is obtained by coating a support such as resin-coated paper.

The amounts of the electron-donating colorless dye and the electron-accepting compound to be 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 depending on the conditions. It is easy for one skilled in the art to determine this amount to use.

When used in thermal paper, the electron-donating colorless dye and electron-accepting compound are pulverized and dispersed in a dispersion medium to a particle size of 10 μm or less, preferably 3 μm or less.

As a dispersion medium, a water-soluble polymer aqueous solution having a concentration of about 0.0 to 10 parts is generally used, and the dispersion is carried out using a ball mill,
This is done using a sand mill, horizontal sand mill, attritor, colloid mill, etc.

The ratio of the electron-donating colorless dye to the electron-accepting compound used is preferably between /:10 and /:/, and particularly preferably between /:j and 2=3. At that time, fatty acid amide, acetoacetanilide, diphenylamine,
Nitrogen-containing organic compounds such as penzamide, stearamide, stearylureastearanilide, carbazole, etc. or co,3-di-m-)lylbutane, 0-fluorobenzoyldurene, chlorobenzoylmesitylene, 4',4''-dimethylbiphenyl , or carboxylic acid esters such as dimethyl isophthalate, diphenyl phthalate, dimethyl terephthalate, methacryloxybiphenyl, etc., or ether compounds such as di-m-tolyloxyethane, copenzyloxynaphthalene, /, J-diphenoxyethane, /, 2
-bis-m-tolyloxyethane, /-phenoxyco-p-chlorophenoxyethane/, β-7enethyloxy-p-biphenyl, β-phenoxyethoxyanisole, /-phenoxy-J-p-ethylphenoxyethane,
Bis-β-(p-methoxyphenoxy)ethoxymethane, /-j'-methylphenoxy-2''-ethylphenoxyethane /), lJ-2-p-methylphenoxyethane, /.

λ-diphenoxyethane, /, 4(-diphenoxybutane, bis-β-(p-ethoxyphenoxy)ethyl ether, l-phenoxy-2-p-chlorophenoquinethane, /-2'-methylphenoxy-2 -≠"-Ethyloxyphenoxyethane, /-≠'-Methylphenoxyλ-≠"-Fluorophenoxyethane, etc. Melting point 7!
A compound having a temperature of °C to /300C may be used in combination.

Among these, it is particularly preferable to use those having an amide bond in the molecule. These are used in finely dispersed form at the same time as a colorless dye or at the same time as an electron-accepting compound. In particular, it is preferable to disperse the colorless dye at the same time from the viewpoint of preventing fogging. The amount of these to be used is added at a weight ratio of 300 parts or less in relation to the electron-accepting compound, with a weight ratio of 100 parts or more to 300 parts or less being particularly preferable.

The coating liquid obtained in this way may further be added with other additives to meet various requirements.

Examples of additives include dispersing oil-absorbing substances such as inorganic pigments and polyurea fillers in the binder in order to prevent the recording head from becoming dirty during recording, and also to improve releasability from the head. For this purpose, fatty acids, metal soap, etc. are added. Therefore, in addition to colorless dyes and electron-accepting compounds that contribute to color development, pigments, waxes, antistatic agents, ultraviolet absorbers, antifoaming agents, conductive agents, fluorescent dyes, surfactants, hindered phenols, etc. The additives are applied onto the support to constitute the recording material.

Specifically, pigments such as kaolin, calcined kaolin, talc, waxite, diatomaceous earth, calcium carbonate, aluminum hydroxide, magnesium hydroxide, calcined gypsum, limestone, magnesium carbonate, titanium oxide, alumina, barium carbonate, and sulfuric acid are used as pigments. Barium, mica, microballoon, urea-formalin filler-1, polyethylene particles,
The cellulose filler is selected from those having a particle size of o, i to /jμ. Examples of waxes include paraffin wax, carboquine-modified paraffin wax, Kaunaburow wax, microcrystalline wax, polyethylene wax, and higher fatty acid esters.

Examples of the metal soap include polyvalent metal salts of higher fatty acids, such as zinc stearate, aluminum stearate, calcium stearate, and zinc oleate.

As the hindered phenol, at least 6 or 6
Phenol derivatives in which seven or more of the positions are substituted with dispersed alkyl groups are preferred. Examples of preferred hindered phenols include /, /, 3-tris (2-metallic acid),
Hydroxy! -tert-butylphenyl)butane,
/, /, J-tris(2-ethyl-≠-hydroxy-j
-tert-butylphenyl)butane, /, /, J-tris(3,!-di-tert-butyl≠-hydroxyphenyl)butane, l, /13-tris(2-methyl-
μmhydroxy-j-1ert-butylphenyl)furopane, 2,2'-methylene-bis(4-1ert-butyl-≠-methylphenol), co,2'-methylene-
Bis(6-1ert-buf-lou-hiro-ethylphenol), S.

Hiro'-butylidene bis(4-Lert-butyl-3-
methylphenol)≠<27-thio-bis(3-methyl-1r-tert-butylphenol),
β-(Hiro-hydroxy-3,j-di[-butylphenyl)propionic acid stearyl ester, /.

Examples thereof include j-bis(β-(≠-hydroxy-3+y-di-t-butylphenyl)ethylcarbonyloxy)-3-theapentane. The amount of the hindered phenol compound to be used is preferably /~200% by weight relative to the electron-accepting compound, and the more preferable amount is j-!
; 0% by weight.

These are dispersed and applied in a binder.

Water-soluble binders are generally used, such as polyvinyl alcohol, hydroxyethyl cellulose, hydroxypropyl cellulose, epichlorohydrin-modified polyamide, ethylene-maleic anhydride copolymer, styrene-maleic anhydride copolymer, and imbutylene. Examples include maleic anhydride copolymer, polyacrylic acid, polyacrylic acid amide, methylol-modified polyacrylamide, starch derivatives, casein, and gelatin. In addition, water-resistant agents (gelling agents, cross-linking agents) are added to these binders for the purpose of imparting water resistance, and emulsions of hydrophobic polymers, specifically styrene-butadiene rubber latex, acrylic resin emulsions, etc. You can also use tl-caro. The coating liquid is applied to base paper, high-quality paper, composite paper, plastic sheet, or neutral paper at λ~10? /m2 is applied.

Furthermore, a retention layer of about 0.2 to 2 μm consisting of a water-soluble or water-dispersible polymer compound such as polyvinyl alcohol, hydroxyethyl starch, or epoxy-modified polyacrylamide and a crosslinking agent is provided on the coating surface layer to improve resistance. You can also do that.

When used in thermal paper, various embodiments may be adopted such as those described in 0L82221jr1, 0L82221jr1, 0L82221j4', and Japanese Patent Publication No. Shoju-207≠2. Alternatively, operations such as preheating, humidity control, or stretching of the ω cloth paper may be added prior to recording.

Electric thermal paper is, for example, published by Akihirota No. 73≠≠ and 5O.
-II♂730 and the like. Generally, a conductive layer is formed by coating a support such as paper with a coating liquid in which a conductive substance, a basic dye mainly composed of fluoran derivatives, and an electron-accepting compound are dispersed together with a binder, or by coating a conductive substance on the support. The electrically conductive thermal paper of the present invention is produced by applying thereon a coating liquid in which a colorless dye, an electron-accepting substance, and a binder are dispersed.

Note that the sensitivity can also be improved by using the thermofusible substance described above in combination.

An example of photosensitive and pressure sensitive paper is Tokkai Sho! ; 7-/7-13t, etc. In general, photopolymerization initiators such as silver iodobromide, silver bromide, silver behenate, Michler's ketone, indiyne derivatives, and benzophenone derivatives and crosslinking agents such as polyfunctional monomers such as polyallyls, poly(meth)acrylates, and poly(meth)acrylamides A synthetic resin wall such as polyether urethane or polyurea is encapsulated in the capsule together with a colorless dye and optionally a solvent. After imagewise exposure, the colorless dye in the unexposed area is brought into contact with a color developer to be colored.

(Examples of the Invention) Examples are shown below, but the present invention is not limited thereto. In the examples, unless otherwise specified, weight is expressed.

Example 1 - Preparation of color former goldstone capsule sheet Partial sodium salt of polyvinylbenzenesulfonic acid (manufactured by National Starch, VER8A).

TL! 00) is dissolved in 9j parts of hot water and then cooled.

Add 8 mW of sodium hydroxide solution to this, pt-i≠,
It was set as O. On the other hand, 100 parts of diinoprobyl naphthalene containing 3.5% crystal violet lactone (C, V, L) as a coloring agent was emulsified and dispersed in 100 parts of a JL aqueous solution of a partial sodium salt of the polyvinylbenzenesulfonic acid. Diameter Hiromu.

An emulsion with a particle size of θμ was obtained. Separately, 6 parts of melamine, 71 parts of formaldehyde aqueous solution by weight of 37 parts, 3 parts of water
After 30 minutes, a transparent aqueous solution of melamine, formaldehyde and melamine-formaldehyde initial condensate was obtained.

This aqueous solution was mixed with the above emulsion. While stirring, adjust p)-1 to t, o with a 2M phosphoric acid solution, and bring the temperature of the solution to +t.
The mixture was raised to 'c' and stirring was continued for 6 hours. This capsule liquid was cooled to room temperature, and the pH was adjusted to O with an aqueous sodium hydroxide solution.

To this dispersion, 200 parts of IO heavy layer ribinyl alcohol water bath liquid and SO parts of starch particles were added and water was added to prepare a coating liquid with a solid content concentration of 20% of the microcapsule dispersion.

This coating liquid was coated on J'Og/m2 base paper using an air knife coater so that the solid content was 5 g/m2, and dried to obtain a color former-containing capsule sheet.

■ Preparation of color developer sheet 10 parts of the color developer shown in Table 1, 20 parts of Jilton clay,
A dispersion liquid consisting of 60 parts of calcium carbonate, 20 parts of zinc oxide, 1 part of sodium hexametaphosphate and 200 parts of water was dispersed using a sand grinder so that the average particle size was 3 μm.

To this dispersion, 76 parts of 104 PVA aqueous solution, 10% PVA
Ioo parts of the aqueous solution and 10 parts of carboxy-modified SBR latex (as solid content) were added with vinegar until the solid content concentration was 204.
Water was added to obtain a coating solution.

This coating liquid is j O? / 3.097m2 on m2 base paper
The color developer sheet was coated using an air knife coater and dried to obtain a color developer sheet.

Comparative Example A developer sheet was obtained by changing only the developer in the developer sheet to the developer shown in Table 1.

Performance comparison (1) Color developer ability The surface of the color former goldstone microcapsule sheet was layered on the color developer sheet obtained in Examples and Comparative Examples at a weight of 600 kg/Cr.
A load of n2 was applied to develop color. After color development, the density of the color material at tloH was measured using Hitachi Color Analyzer Model 307.
The color development ability was measured after 1 minute.

(2) Light resistance After 70 minutes of color development obtained in (1), the colored bodies of Examples and Comparative Examples were irradiated with a fluorescent lamp fading tester (33,0001 ux) for a period of time, and then the density at t10 nm was measured. The ratio of concentration after light lamp irradiation to concentration before irradiation was taken as the original value.

(3) Plasticizer resistance After 70 minutes of color development obtained in (1), a soft polyvinyl chloride sheet (thickness O0j, dibutyl phthalate as a plasticizer) was placed on the color formers of Examples and Comparative Examples after 70 minutes of color development. ; heavy i1
% and dioctyl phthalate (containing 7% by weight),
jto 0 parts% RIIjθ% atmosphere 1007/2
After applying a load of 7.2 hours and leaving it for 7.2 hours, the concentration of ionm was measured, and the concentration ratio of the concentration after stacking the polyvinyl chloride sheets and the concentration before stacking was taken as the plasticizer resistance value.

As shown in Table 1, it can be seen that the color developer sheet of the present invention has better fastness of the color image to plasticizers than the comparative color developer sheet.

Example j Electron-donating colorless dyes co-anilino 3-chloro-2-diethylaminofluorane and 2=anilino 3-
Equal weight mixture of methyl-A-N-ethyl-N-isoamylaminofluorane Salicylic acid derivative and stearic acid amide derivative shown in Compound Example (2) 209 each
1009 J% polyvinyl alcohol (Clan PVA
-10r) into the aqueous solution with stirring, and after thoroughly defoaming, Su/Domil (manufactured by WEB, Dynomil KD
L type) was used for dispersion treatment to reduce the volume average particle size to 3 μm or less.

On the other hand, an equal weight mixture of pigment calcium carbonate and zinc oxide r
O2, sodium hexametaphosphate solution/602
It was used after being dispersed with a homogenizer. The dispersions prepared as described above are electron-donating colorless dye dispersion j7, salicylic acid derivative dispersion 109, and stearic acid amide dispersion! 1. Pigment dispersion liquid, mixed at a ratio of 2 cores,
Furthermore, emulsion of zinc stearate ≠ 2 and 2 (
An aqueous solution j7 of sodium 2-ethylhexyl)sulfosuccinate was added to obtain a coating liquid.

The basis weight of the coating liquid obtained in this way! The mixture was coated with a wire bar to a dry coating weight of 79/m2 on a high-quality paper of 0.09/m2, dried in a jo 0C oven, and calendered to obtain a heat-sensitive recording material.

When color was developed using Fujitsu High Speed Facsimile FF-2ooo, a black printed image was obtained. This image had excellent light resistance and chemical resistance.

Claims (1)

[Scope of Claims] In a recording material that utilizes color development due to contact between an electron-donating colorless dye and an electron-accepting compound, the electron-accepting compound is a salicylic acid derivative represented by the following general formula (I) or a metal salt thereof. A recording material characterized by containing. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I) In the above formula, R represents a divalent group, and X represents a hydrogen atom, an alkyl group, a phenyl group, an alkoxy group, or a halogen atom.