JPS63288776A - Recording material - Google Patents

Abstract

PURPOSE:To contrive higher color developing properties and higher stability of developed color images, by using a compound having a specified functional group, in a recording material utilizing a phenomenon of color formation upon contact of a colorless dye with an electron-acceptive compound. CONSTITUTION:A compound of the formula Ar1XRAr2 is used in a recording material utilizing color development upon contact of an electron-donative colorless dye with an electron-acceptive compound. Among the compounds of the formula, one that has a melting point of 50-190 deg.C and up to 30 carbon atoms is preferred. When the recording material is to be used as a thermal recording paper, the compound of the formula, the dye and the electron-acceptive compound are used after being dispersed by grinding to s particle diameter of not more than 5 mum in a dispersant. The dispersant is an about 0.2-10% aqueous solution of a water-soluble high molecular weight substance. The dye and the electron-acceptive compound are preferably used in a weight ratio of 1:10-1:0.1, and the weight ratio of the compound of the formula to the electron-acceptive compound is preferably 1:0.1-1:15. In the formula, each of Ar1 and Ar2 is an aromatic ring which may have a substituent group, R is a divalent group including -SO-, -SO2-, or -OCOO-, and X is oxygen or sulfur.

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 electron-donating colorless dyes and electron-accepting compounds are already known as pressure-sensitive paper, heat-sensitive paper, light-sensitive pressure-sensitive paper, current-carrying heat-sensitive recording paper, heat-sensitive transfer paper, and the like. For example, British Patent No. 2/μθμμ, U.S. Patent No. 100!
7-/7ri.

13&, 60-/23. rtat, same 60-/23, evening! I am familiar with 7 etc.

Performances that the recording material should have include (11) sufficient color density and color development sensitivity, (2) no fogging, and (3) sufficient fastness of the color former.

In recent years, research has been intensively conducted to improve these characteristics.

The present inventors have discovered that specific compounds are effective in improving these properties.

(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 colorless dye is colored when it comes into contact with an electron-accepting compound, in which a compound having a specific functional group is used. This was achieved by developing materials. Compounds of the invention are of formula I
It is indicated by.

ArIXRAr2 In formula I, Ar
1, A r 2 is an aromatic ring which may have a substituent, R is -5O-1-802- or -OCOO-1j
! : A divalent group containing X represents an oxygen atom or a sulfur atom.

It takes a ceremony! Among the compounds represented by the above, those having a melting point of oOc to tyooC and a carbon atom number of 30 or less are preferable. In addition, the two aromatic rings have one or more halogen atoms,
It may be substituted with a group having up to r carbon atoms, such as an alkoxy group, an alkylthio group, a hydroxy group, an alkoxycarbonyl group, an acyloxy group, an acyl group, an alkyl group, an aryl group, and a cyano group. The alkyl moiety herein may also be an alkoxy, halogen, acyl, aryloxy, or alkoxycarbonyl group. The most preferred case is a group in which the number of carbon atoms is not more than ≠, and the case is a compound with a melting point of 70C to 0C.

Among these compounds, Ar1 or A
This is the case when r2 is a naphthalene ring or benzene ring having a group selected from a hydrogen atom, an alkyl group, a halogen atom, an alkoxy group, and an alkylthio group.

Also, R is -CHH211RICmHzmYp- In the above formula, n is an integer from 1 to da, m is an integer from O to λ,
R1 is -5O-1-, - or -OCOO-, Y is -0
- or -8-f (p represents 0 or l).

The case shown in is preferable.

More specifically, the compound of the present invention is represented by the following formula (2).

In the formula, R2 to R7 represent a hydrogen atom or the above-mentioned substituent.

Further, R2 and R3, R5 and R6 may be combined with each other to form a J- or T-membered saturated or unsaturated compound.

Particularly preferred is n is 2 or 3, m is O or l, and R
5. R2 is selected from a hydrogen atom, an alkyl group, an alkoxy group, an alkylthio group, and a halogen atom. This is the case when the total number of carbon atoms is 2 or less and 1 or more.

A specific example is as follows.

β-naphthyl-<2)-oxyethylphenyl carbonate, β-naphthyl(co)-oxyethylbenzyl carbonate, β-naphthyl-(-2)-oxypropyl-
p-methoxyphenyl carbonate, β-naphthyl-(
-2)-Oxyethyl-p-methylphenyl carbonate, β-naphthyl-(-2)-oxyethyl-p-methylphenyl carbonate, β-p-methoxyphenoxyethyl-p'-methoxyphenylcarbo'$-1', β
-p-methoxyphenoxyethyltolyl carbonate,
β-p-Phenylphenoxyethyl tolyl carbonate, β-naphthyl-(2)-oxyethylnaphthyl-(λ
)-carbonate, β-p-methoxyphenoxyethylna7tyl-<2)-carbonate, β-μm methoxy-
Naphthyl-(1)-oxyethylphenyl carbonate, β-μm chloro-naphthyl-(1)-oxyethylnaphthyl-(2)-carbonate, β-naphthyl-(2)
-thiooxyethylnaphthyl-(2)-carbonate,
β-dermethoxynaphthyl(1)-oxyethylbenzyl carbonate.

Colorless dyes include the well-known triphenylmethane phthalide compounds, fluoran compounds, phenothiazine compounds, indolyl phthalide compounds, leucoolamine compounds, rhodamine lactam compounds,
It is selected from one or more of triphenylmethane compounds, triazene compounds, spiropyran compounds, fluorene compounds, and the like.

Regarding these, for example, specific examples of phthalides are U.S. Reissue Patent No. 23.0214, U.S. Pat.
No. 1, No. 3. ≠ri/, //, No. 1, same 3.4c/, 7
No. 14 and J,! 09. /7μ, specific examples of fluorans are 3.6λμ, 107, J, 1,27,7
．． Same as r7! , 617/.

0// issue, same J, 4cAJ, Iλ issue and same 3゜tr
t, Jri No. 0, same 3, 2 Ko, zto No., same 3, Rij?
, No. 571, same≠, 226. 12, specific examples of subirodipyrans are 3.27/, No. 101, and pyridine and pyrazines are 3.77/.

44.244 and 3. rzJ, No. 142, μ, 2
≠No. 6.31I, fluorescein/class is described in Japanese Patent Application No. 1988-λμO, etc.

For example, some fluorans are represented by the following formula.

In the formula, R9 to R12 represent a hydrogen atom, an alkyl group, an aryl group or an acyl group; may be substituted with a group, a nitro group, a cyano group, etc.

R13 to R17 are hydrogen atoms, alkyl groups, aryl groups,
Indicates a group selected from an acyl group, a halogen atom, a nitro group, an acyl group, an aryloxy group, an alkoxy group, a nitro group, a carbamoyl group, an amino group, an acyloxy group, a cyano group, etc., and these are substituents as described above. Further substitutions may be made.

Also, Ro and Ro. , Ro and R□7, R13 and R□4, R
14 and RR and R engineering, that of 12% 11 It is interconnected and! It may form a shell or a six-membered ring.

Ro, R□. It is particularly preferable that R11, R16 and R17 are hydrogen atoms, R13, R14 and R15 are hydrogen atoms, halogen atoms or alkyl groups, and R1□ is an alkyl group or an aryl group.

Y represents an oxygen atom or a sulfur atom. These are Ro, R
, □ or at6 may be used to form a screw body.

Specific examples include co-anilino 3-methyl-6-dinithylaminofluorane, co-anilino 3-methyl-6-cyclohexylmethylaminofluorane, and λ-p-chloroanilino 3.
-Methyl-4-dibutylaminofluorane, co-anilino 3-methyl-6-cyoctylaminofluorane, 2
-anilino-3-chloro-6-diethylaminofluorane, pyridyl blue, co-anilino-3-methyl-6-
Dibutylaminofluorane, nophenyl-6-diethylaminofluorane, λ-anilino-3-methyl-4-N-ethyl-N-ynamylaminofluorane, λ
-Anilino 3-methyl-6-dinithylamino-7-methylfluorane, λ-anilino 3-methoxy-6-cyptylaminofluorane, λ-0-chloroanilino-6
-Cyptylaminofluorane, x-p-chloroanilino-3-ethyl-4-N-ethyl-N-ynamylaminofluoran/, λ-0-chloroanilino 6-p-butylanilinofluorane, co-anilino J-Sytadecyl-t-diethylaminofluorane, 2-anilino-3-
Ethyl-6-fluoraminofluorane, co-anilino 3-methyl-≠'.

s'-dichlorofluorane, λ-〇-toluidino 3-
Methyl-6-diitupropylaminohiro'.

j'-dimethylaminofuranthin, 2-anilino-3-
Ethyl-6-N-ethyl-N-isoamylaminofluorane, co-anilino 3-methyl-+-N-ethyAN
-1-pyridylpropylaminofluorane, co-anilino-3-chloro-4-N-ethyl-N-isoamylaminofluorane, or rhodamine-B-anilinolactam, rhodami/(p-nitroanilino)lactam,
Examples include rhodamine B (p-chloroanilino)lactam and λ-anilino-6-dinithylaminofluorane.

Some examples of other colorless dyes include triarylmethane compounds such as 3,3-bis(p-dimethylaminophenyl)-6-dimethylaminophthalide (i.e., crystal violet lactone), J, J- Bis(p-dimethylaminophenyl) phthalide, etc., and diphenylmethane compounds include ≠ p/-bis-dimethylaminobenzhythrine benzyl ether, N-halo7enyl leukoolamine, N-2, μ, ! - trichlorophenyl leuco auramine, etc.; thiazine compounds include benzoyl leucomethylene blue, p-nitrobenzoyl leucomethylene blue, etc.; spiro compounds include 3-methyl-spiro-dinaphthopyran, 3-ethyl-spiro- dinaphthopyran, 3.3'-
Cyclolosespirodinaphthopyran, 3-benzylspiro-dinaphthopyran, 3-methyl-naphtho-(3-methoxy-benzo)spiropyran, 3-propyl-spiro-
There are dibenzopyrans, etc., and it is desirable to use two or more of them in combination.

Electron-accepting compounds that provide color upon contact with colorless dyes include inorganic and organic Lewis and Brønsted acids. For example, compounds having acidic hydrogen atoms such as phenolic hydroxyl groups, carboxyl groups, and imide groups, or metal complexes are useful. For example, phenol derivatives, salicylic acid derivatives, metal salts of aromatic carboxylic acids, acid clay, bentonite, novolac resins, residual volume treatment novolac resins, such as cochrochloride phenylphenol, 2.2-bis(μm hydroxyphenyl)furonone, Hiroshi, μ'-isopropylidene bis(co-methylphenol), '+'-bis(3-chloro-μ
m-hydroxyphenyl)cyclohexane, λ12-bis(J-chloro-Hydroxyphenyl)-3-methylbutane, μ, 4L'-secondary inoctylidene diphenol, da, μ'-5ec-butylidenephenol, μ-cyano Phenylphenol, μ, μ′-isopentylidene diphenol, g, <1-methylcyclohexylidene diphenol, /, g-bis≠′-hydroxycumylbenzene, /, 4C-bisμ′-hydroxybenzoylbenzene, μ, μ′-thiobis(j,4-dimethylphenol), μ, ψ′-dihydroxydiphenylsulfone, phloroglycine monobenzyl ether, μ
mm human cibenzophenone, J, u-dihydroxyhiro'-butoxybenzophenone, 3. J'-methylenebis-μm hydroxybenzoic acid benzyl ester, polyvinylphenol, '* '' e ``e san''
-tetrahydroxydiphenylsulfone, μm dimethyl hydroxyphthalate, μm isobutyl hydroxybenzoate, λ, 4c, l -trihydroxyco'-benzyloxydiphenylsulfone, 1, terbis-p-hydroxyphenylpentane, /, 4-bis- p-hydroxyphenoxyhexane, dihydroxybenzoic acid) Cumyl benzyl, μm hydroxybenzoic acid-cinnamyl ester, μm hydroxybenzoic acid benzyl ester, μm hydro* Cybenzoic acid-m-7
0 lobenzyl ester, ≠-hydroxybenzoic acid-cumyl ester, e, u'-hydroxyco', λ'-dibutylphenyl sulfone, β-phenethyl orseinate, cinnamyl orseinate, 〇-chlorophenoxyethyl orselate Estelle s re! '-Meflene bis-λ, 4L-dihydroxybenzoic acid benzyl ester, 0-phenylphenoxyethyl orselinate, m-phenylphenoxyethyl orselinate, co, ≠-dihydroxybenzoic acid-β-3'-t-
Butyl-ψ′-hydroxyphenoxyethyl ester,
Bisphenol A bis p-hydroxybenzoic acid ester! -β-p-methoxyphenoxyethoxy-2-hydroxybenzoic acid, λ,4L-dihydroxybenzoic acid-p
-Methylbenzyl ether, λ, 4cm dihydroxybenzoic e-β-phenoxyethyl ester, λ.

-dihydroxy-6-methylbenzoic acid 0-methylbenzyl ester, bis≠-hydroxyphenylacetic acid phenoxyethyl ester, μ'-diacetyldiphenylthiourea, 3-phenylsalicylic acid, J-p-α-
Methylbenzyl-α-methylbenzylsalicylic acid, j-
p-methoxyphenoxyethyloxysalicylic acid! −
Phenoxyethoxysalicylic acid! -p-benzyru α
-Methylbenzylsalicylic acid, 3-xylyl-! −(α
, α-dimethylbenzyl) salicylic acid, 3°! -G (
α-Methylbenzyl) salicylic acid, co-hydroxyl
- Organic color developers such as aromatic carboxylic acids such as α-ethylbenzyl-3-naphthoic acid, phenolic resins such as J,J-dicyclopentadienylsalicylic acid, para-phenylphenol-formalin resin, and the like. Complexes of zinc rhodan and molybdic acid, such as imidazole complexes of zinc rhodan, cophenylimidazole complexes, picoline complexes,
Cobenzylimidazole complex, benzimidazole complex, λ, 3-dimethyl-l-phenyl-3-pyrazoline-! -one complex L/-722-comethyl-3-benzyl-! -Hit 7''') One-one complex, /-
Phenyl-λ-methyl-3-(2-ethylhexyl)-
3-Virasorin! -one complex L/-phenyl-comethyl-3-isopropyl-3-pyrazoline-! -one complex, l-phenyl-2,3-dibenzyl-pyrazoline-! -: A-7 complex, /-phenyl-Kobeysilu J-methyl-pyrazoline-! -one complex, β-diketone molybdate complex, for example, as a ligand, acetylacetone, benzoylacetone, thenoyltrifluoroacetone, acetylacetylacetone):/, EDTA, ethyl benzoylacetate, bipyridyl, oxine, etc. Furthermore, salts of these organic color developers with polyvalent metals such as zinc, magnesium, aluminum, and calcium, aliphatic carboxylic acids such as oxalic acid, maleic acid, sulfosuccinic acid, and stearic acid, benzoic acid, and paratertiary acids are also available. One or more types of milbenzoic acid, phthalic acid, gallic acid, etc. are used. When the specific compounds of formula I, their colorless dyes and electron-accepting compounds are applied to recording materials, they are used in the form of fine dispersions or microdroplets.

When used in thermal paper, the compound of formula I, the electron-donating colorless dye and the accepting compound are in a dispersion medium! It is used after being pulverized and dispersed to a particle size of μ or less, preferably λμ or less. A water-soluble polymer aqueous solution having a concentration of about 0.2 to io% is generally used as the dispersion medium, and dispersion is carried out 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 to the electron-accepting compound used is preferably between 1:IQ and 20.1 by weight;
Furthermore l:! Particularly preferred is a ratio of 2:3. The compound of formula l has a ratio of l:0 to the electron-accepting compound. From l/:/
Preferably between j.

In the original text, aromatic ether compounds such as JP-A-Sho! rl
-3-7, Riri issue, same! rl-17,0914, 61-/23. Aromatic alkyl or substituted alkyl ethers disclosed in No. j1' etc. may be used in combination. Examples of such ether compounds include phenoxyethyl biphenyl ether, phenethyloxybiaenyl, benzyloxynaphthalene, benzylbiphenyl, di-m-
Tolyloxyethane, β-phenoxyethoxyanine, l-phenoxyco-p-ethylphenoxyethane, bis(p-methoxyphenoxy)ethoxymethane, his-β-(p-methoxyphenoxy)ethyl ether,
l-methylphenoxy-λ-ethylphenoxyethane,
l-tolyloxy-2-p-methylphenoxyethane,
1. -2-diphenoxyethane, 1ltA-diphenoxybutane, bis-β-(p-ethoxyphenoxy)ethyl ether, l-7 dinoxy 2-p-chlorophenoxyethane, l,! - β-Naphthoxy 3-Thiokiape 7p: /, /-μ'-Methylphenoxy Cohiro
-Fluorophenoxyethane%'#'-bis-p-methoxyphenylthioethoxyethane, l-fe/*'
/ -2-p-natoxyphenylthioethyl ether,
'+'-bis-p-methoxyphenylthioethane, l-
tolyloxy-2-p-methoxydiphenylthioethane,
It is preferable to use a compound having a melting point of 7z@C to /3j'C in combination.

In this case, it is preferable to use an aliphatic amide or ureido in combination.

Stearic acid amide, methylene bis stearamide, stearyl urea, cyclohexyl urea, stearic acid anisidide, benzoylstearylamine, phenoxyacetobenzylamide, phenylacetyl benzyl amide, butoxyethyl benzyl amide, furfuryl benzyl amide, etc. to the above-mentioned ethers It is particularly effective to use it in combination with

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 0% or more and 300% or less, particularly preferably 10% or more and iro% or less, based on the electron-accepting compound.

Furthermore, in the present invention, the particle size is 0. / to /θμ pigments such as kaolin, calcined kaolin, talc, calcium carbonate, aluminum hydroxide, magnesium hydroxide, calcined gypsum, silica, magnesium carbonate, zinc oxide, alumina, barium carbonate, barium sulfate, mica, microballoon, It is preferable to use urea-formalin filler, polyethylene particles, cellulose filler, etc., and hindered phenol in combination. Examples of the hindered phenol include phenol derivatives in which at least one of the λ or 6-positions is substituted with a branched alkyl group, such as /, l-bis(-2-methyl-der-hydroxy-
5-t-i tylphenyl)butane, 'e's'-)lis(3-methyl-μmhydroxy-r-t-7'tylphenyl)butane, bis(λ-hydroxy-j-t-butyl-yylphenyl) ) methane, bis(2-methyl-μ
-Hydroxy-t-t-butylphenyl) sulfide, and the like.

Examples of ultraviolet absorbers include cinnamic acid derivatives, benzophenone derivatives, benzotriazolylphenol derivatives, etc. For example, α-cyano-β-phenylbutyl cinnamate, 0-benzotriazolylphenol Q ++ <nzotriazolylphenol Examples include p-chlorophenol, 0-benzotriazolyl-20 μm dibutylphenol, and O-benzotriazolyl-p-chlorophenol.

These materials are also detailed in the patents mentioned above.

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

Examples of additives include dispersing an oil-absorbing substance Y such as polyurea filler in the binder in order to prevent the recording head from becoming dirty during recording, and adding metal to improve the releasability of the head. Soap etc. are added. Therefore, in addition to colorless dyes and electron-accepting compounds that contribute to color development, wax, antistatic agents, ultraviolet absorbers, antifoaming agents, conductive agents, fluorescent dyes, surfactants, etc. are generally applied to the recording material. will be constructed.

Waxes include paraffin wax, carboxy-modified halafine wax, polyethylene wax,
Examples include higher fatty acid esters.

Examples of the metal soap include higher fatty acid polyvalent metal salts, ie, zinc stearate, zinc oleate, and the like.

These are dispersed and applied in a binder.

Water-soluble binders are generally used, such as hollyhinyl alcohol, hydroxyethyl cellulose, hydroxypropyl cellulose, epichlorohydrin-modified polyamide, ethylene-maleic anhydride copolymer, styrene-maleic anhydride copolymer, and isobutylene-anhydride. Examples include maleic acid copolymers, polyacrylic acid amide, polyacrylic acid, methylol-modified polyacrylamide, starch derivatives, casein, and seratin. In addition, in order to impart water resistance to these binders, water-resistant agents (gelling agents, cross-linking agents) are added, or emulsions of hydrophobic polymers, specifically styrene-butadiene rubber latex, acrylic resin emulsions, etc. You can also add

Furthermore, 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) are added. A layer of about 2μ can also be provided.

The coating is most commonly applied on base paper, acid-free paper, wood-free paper or synthetic paper, preferably on acid-free paper coated with a white pigment such as synthetic calcium carbonate.

In this case, it is preferable to use a pigment and a thermoplastic or thermofusible substance in combination.

Generally, the coating amount is about 2 to 10,777 m'' in terms of solid content.

In addition, when used for thermal paper, 0L822.21rlI
No., same, ziiorzu, special public show J-2-20/4t2
We will take the form of konnin described in et al. Alternatively, operations such as preheating, humidity control, or stretching of coated paper may be added prior to recording.

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

Example/(li) Preparation of Sample 1 2 g of 4-anilino-3-methyl-N-ethyl-N-propylaminofluorane and 2 g of 2-anilino-3-chloro-6-dinithylaminofluorane were added in 3.
5% polyvinyl alcohol (Ken moderation Tatata%, polymerization degree 1
000) was dispersed with an aqueous solution λjI using a sand mill to have an average particle size of μ.

On the other hand, bisphenol A/ill, β-naphthoxy-(
-2)-3% polyvinyl alcohol aqueous solution of ethyl phenyl carbonate/19! Distributed day and night in the mail mill with Og. Furthermore, /, /.

J-) 17S λ'-methyl-μ'-human qxy! '-t-Butylphenylbutane O6/9! % polyvinyl alcohol water bath solution 207%/day and night.

After mixing this well, add Joshia Kaolin λO1 fine particle silica 69 and disperse it well to create a paraffin wax emulsion! O% dispersion (Middle East oil cellosol #u2t) Hiro,! I was added to prepare a coating liquid.

The support is made of synthetic carbon and benzyloxynaphthalene.
1777 m2 was applied to the area of 0;/(W I ratio). Neutral paper with a basis weight of rOp/m'' was used.

The coating liquid is applied as solid content on this support! 9/m
2, and after drying for 1 minute at 0C,
A coated paper was obtained by applying a super calender at a linear pressure of 60 kgW/cm.

Coated paper is heated by facsimile with energy of 3 mJ/
When the color was developed by heating at mm2 and the color density was determined, it showed / and Q in the Macbeth reflection-change direction.

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

Example 2.3 'AMAlO2-naphthoxy-(-2)-ethyl phenyl carbonate replaced with β-naphthoxy-(2)-ethylbenzyl carbonate and l-phenoxy-λ-
p-ethylphenoxyethanejlc91jlHIJλ]
, β-naphthyl-(2)-oxyethylnaphthyl carbonate (6 g) and phenylacetylindylamide (Example 3) were used.

A coating liquid was obtained in the same manner as above. This coating solution was applied onto a high-quality paper coated with synthetic fine carbon (brilliant lj) using carboxy-modified SBR as a binder, i, and zfl/m2 on neutral paper.

When color was developed according to the method of Example 1, a clear black image was obtained, and the reflection densities were both o and r or higher.

This black image was clear and did not discolor or fade even when exposed to oil or sunlight.

Claims (1)

[Scope of Claims] A recording material that utilizes color development due to contact between an electron-donating colorless dye and an electron-accepting compound, which is characterized by containing a compound represented by formula I. Ar_1
In the divalent group containing -, X represents an oxygen atom or a sulfur atom.