JPS6260686A - Recording material - Google Patents

Abstract

PURPOSE:To provide a recording material giving a sufficient developed color density and having an enhanced preservability in raw state and with time, by using a specified compound as an electron-accepting compound. CONSTITUTION:An electron-donating colorless dye and an electron-accepting compound consisting of a compound of general formula (I), wherein an alcohol residue constituting the ester linkage has an unsaturated bond and wherein R is a 3-18C group having an unsaturated bond, are used. When the electron- accepting compound is used for a thermal recording material, it is preferably one that has a melting point of 90-200 deg.C. The thermal recording material is produced by a method wherein the dye, the electron-accepting compound and, optionally, a heat-fusible substance are sufficiently finely pulverized and mixed into a liquid obtained by dissolving or dispersing a binder in a solvent or dispersant, and an oil-absorptive pigment is added to the resultant material to prepare a coating liquid. A sensitizer, a metallic soap, an antioxidant, a UV absorber, an image preservability enhancing agent or the like may be added to the coating liquid, as required. The coating liquid is applied to a base such as a neutral paper, a woodfree paper and a plastic film, followed by drying.

Description

[Detailed description of the invention] <Field of application of the invention> The present invention relates to recording materials.

The recording material according to the present invention utilizes a color-forming reaction between an electron-donating colorless dye and an electron-accepting compound.

The electron-accepting compound according to the present invention is an extremely useful compound as an electron-accepting compound for pressure-sensitive recording materials and heat-sensitive recording materials, and is also particularly useful as an electron-accepting compound for pressure-sensitive recording materials and heat-sensitive recording materials. sheet, electron beam recording sheet,
It is a compound that can be applied to electrostatic recording sheets, photosensitive printing plate materials, stamping materials, type ribbons, ballpoint pen inks, crayons, etc.

<Prior art> The use of phenolic compounds in food as electron-receptive compounds in pressure-sensitive recording materials or heat-sensitive recording materials is disclosed in Japanese Patent Publication No. tO-9309, Japanese Patent Publication No. Although disclosed in Kosho S/-29730 and the like, these phenol compounds cannot necessarily be said to be satisfactory electron-accepting compounds. In other words, when used in combination with an electron-donating colorless dye, the coloring Si may not be sufficient, or
After recording, there are problems such as a decrease in the density of one image on the coloring surface over time, and a concentration of white powdery substances on the surface called so-called dusting.

<Object of the Invention> Therefore, the object of the present invention is to provide a recording material which has a sufficient degree of color development when used in combination with an electron-donating colorless dye and which has improved storage stability both raw and over time. .

<Structure of the Invention> The object of the present invention is to provide a compound represented by the following general formula (1) as an electron-donating colorless dye and an electron-accepting compound, in which the alcohol moiety residue forming the ester bond has an unsaturated bond. Compounds that are! This was achieved through the recording materials used.

In the above formula, 几 has 3 carbons or /? represents a group having an unsaturated oro bond.

When the electron-accepting compound according to the present invention is used as an electron-accepting compound for heat-sensitive recording materials,
Those having a melting point of 2000 C' are preferred.

The characteristics of the electron-accepting compound according to the present invention include the following.

By combining (1) with a child-donating colorless dye, a colored image with daytime density is produced.

(Ill background and colored 1fiI image have good storage stability.

(iii) Stable without sublimation.

The compounds of the present invention can be easily produced by a reaction that forms an ester bond between the corresponding carboxylic acid, carboxylic acid halide, carboxylic acid g4 salt, carboxylic acid lower alkyl ester, etc., and a halide, alcohol, or ester having an unsaturated bond. can be synthesized into

In the present invention, the second example is an unsaturated bond! Examples of the alcohol include propargyl alcohol, crotonyl alcohol, cinnaral alcohol, /-butene-3-
Examples include chain or cyclic alcohols such as alcohol, copten-/-ol, i-butyn-3-ol, citronellol, and oleyl alcohol; It's okay.

Below is an example of the synthesis method! show.

Synthesis example / /, /-bis(terhydroxyphenyl)acetic acid pronoξ
Add 1. 1, /-bis(gu-hydroxyphenyl) hexaacid, /JP's propargyl bromide, Vlg-'s caustic apron, and 60ml of dimethylformamide were weighed out and stirred at ♂0°C to 10θ0C for 7 hours. The reaction mixture was developed with ethyl-normal hexane using silica gel as a carrier. Melting point: 37-9°C Synthesis example: i-bis(l-hydroxyphenyl) sulfuric acid cinnabal ester! 00 m6 flask l knee V, ri 1 i, i-bis(gu-hydroxyphenyl)acetic acid, /≦,♂? cinnamyl chloride, LItll caustic prodrome and tOrrt
Weigh out 1 liter of dimethylformamide and stir on a hot water bath for 7 hours. The reaction mixture was developed with acetic acid and ethyl normal hexane using silica gel as a carrier.

Melting point/2j''-jθ0C Next, specific examples of the electron-accepting compound of the present invention will be shown, but the present invention is not limited thereto.

(1) /,/-his(gu-hydroxyphenyl) acetic acid phlopargyl ester (2) /,/-bis(l-hydroxyphenyl)
Acetic acid cinnaval ester (j) /, /-bis(couhydroxyphenyl)
Acetic acid crotonyl ester (<t) /, /-His(gu-hydroxyphenyl) #W-p-methoxycinnal ester (r)
i,i-bis(gu-hydroxyphenyl)acetic acid-p-
Butyl cinnamyl ester (≦) /,/-bis(q-hydroxyphenyl)acetic acid oleyl ester (7) /,/-bis(V-hydroxyphenyl)acetic acid citronellol ester (♂)/,/-his (G=- Hydroxyphenyl)acetic acid indanol ester (9) /, l-bis(V-hydroxyphenyl)acetic acid geraniol ester (10) /, /-bis[l-hydroxyphenyl]acetic acid-/-butyn-3-ol ester, etc. be.

These may be used singly or in combination or with other electron-accepting compounds (e.g. bisphenol A, <t-hydroxybenzoic acid benzyl ester, /, /-his-[couhydroxyphenyl)cyclohexane, 31 terbis-(α-methylbenzyl)salicylic acid. (zinc, activated clay, etc.).

As the 1-child donating colorless nest material used in the present invention, triarylmethane compounds, diphenylmethane compounds, xanthine compounds, thiazine thread compounds, and spiropyran thread compounds are used.

To give some examples of these, triarylmethane compounds include 3.3-bis(p-dimethylaminophenyl)-6-dimethylaminophthalide (partially crystal violet lactone), 3゜3-bis( p-dimethylagonophenyl) phthalide, 3-(p-dimethylaminophenyl)-3-(/,3-dimethylindol-3-yl)phthalide, 3-(p-dimethylaminophenyl)-3
-(2-methylindol-3-yl)phthalide, etc., and diphenylmethane thread compounds include tx, g'-
hissodimenalaminobenzhydrin benzyl ether, hehalophenyl leukoolamine, N-x, u,
There are tartrichlorophenyl leukoora ε-ran, etc., and xanthine compounds include rhodamine-B-anilinolactam, rhodamine (p-nitroanilino)lactam, rhodamine B (p-chloroanilino)lactam, and -1-dibenzyl-a-no-6. -diethylaminofluorane, co-anilino-2-diethylaminofluorane, -1-anilino-3-methyl-6-ethylaminofluorane, -
1 anilino 3-methyl-3-N-cyclohexyruhemethylanofluorane, nianilino 3-menalu-g-N-ethylheisoamylaminofluorane,
2-0-chloroanilino-6-diethylaminofluorane, 2-m-chloroanilino-6-diethylaminofluorane, 2-(3,t,t-dichloroaniυ))-6-
Diethylaminofluorane, ;-octylamino-B-
Diethylaminofluoran, 2-dihexylamino-ot-diethylaminofluoran 1.2-m-trichloromethylanilino-ot-diethylaminofluoran, coptylamino-3-chloro-6-diethylaminofluoran, 2-ethoxyethylamino -3-chloro-3-
Diethylaminofluorane, -anilino-3-chloro-6-dinithylaminofluorane, no-diphenylamino-6-diethylamino-6-diethylaminofluorane, =-anilino-6-diethylaminofluorane, -anilino-6-diethylaminofluorane, -anilino-3- Methyl-terchloro-diethylaminofluorane, anilino-3-methyl-diethylamino-7-methylfluorane, anilino-3-methoxy-dibutylaminofluorane, co-0-chloroanilino-g-dibutylaminofluoran , 2-p-chloroanilino-3-ethoxy-6-ethylaminofluorane, -1-phenylene-diethylaminofluorane 1, 2-0-chloroayu-11-6-p-butylanilinofluorane, -1-anilino-3-pentadecyl B-
Diethylaminofluorane, λ-anilino-3-methyl-4-N-ethyl-N-tetrahydrofurfurylaminofluorane, -1-anilino-3-methyl-g-N-phthyl-N-tetrahydrofurfurylaminofluorane, 2
-anilino-3-methyl-+-N-ethylheisobutylaminofluorane, noanilino-3-ethylbu-
dibutylaminofluoran, no-anilino-3-ethyl-6-N-ethylheisoadylamine fluoran,
2-Ayu 1tsuno 3-methyl-6-N-ethyl-gamma
-Methoxypropyl adnofluorane, noanilino-
There are 3-phenyl-4-diethylaminofluorane, colaethylamino-3-phenyl-ot-diethylaminofluoran, etc. Thiazine thread compounds include pensoyl leucomethylene blue, p-nitropencil leucomethylene blue, etc., and spiro-based compounds. Examples include 3-methyl-spiro-dinaphthopyran, 3-ethyl-spiro-
dinaphthopyran, 3゜゛3'-cyclolosevirodinaphthopyran, 3-benzylspiro-dinaphthopyran, 3
-Methyl-naphtho-(3-methoxy-benzo)-spiropyran, 3-propyl-spiro-dibenzopyran, and the like. These may be used alone or in combination.

Next, present invention C: a specific method for manufacturing such a recording material will be described.

The pressure-sensitive copying paper according to the present invention is disclosed in US Pat.
No. 0, the same one! Of, Gua No. 1, Same λ.

Ta 0! , Hiro J" No. 9, 2, j'At!', 34
No. 4, same co, 7i2. Ta 07, same prefecture, 730.44 Taro, same prefecture, 730. Hirotafu No. 3. Prior patents such as No. 1, No. 1, No. 2, etc. (2) take various forms as described above. (1) consists of at least one pair of sheets containing electron-donating colorless dyes alone or in combination; After dissolving and initially dispersing the i″L in a binder or containing it in microcapsules, paper,
A coloring agent sheet can be applied to a support such as a plastic sheet or resin-coated paper, and an electron-accepting compound can be used alone or in combination with other electron-accepting compounds, such as styrene-butadiene latex or polyhinyl alcohol. A developer sheet is obtained by dispersing the developer in a suitable binder and coating it on a support such as paper, plastic sheet, or resin-coated paper.

The amount of the electron-donating colorless dye and the electron-accepting compound to be used depends on the desired coating thickness, the form of the pressure-sensitive copying paper, the capsule manufacturing method, and other conditions, and may be selected as appropriate depending on the conditions. Determining this usage amount is easy.

A method of manufacturing capsules is described in a US patent.

700, tl! No. 7, same, zoo, method using coacervation of hydrophilic colloid sol described in <tjy issue, British watch? , 4; No. 7.797, 9j
fO, LIL, t3, same 9♂9.2t'1. No., same l
.

Examples include the interfacial polymerization method described in θri/, Q77, and the like.

The heat-sensitive recording material is made of a liquid i'''- in which a binder is dissolved or dispersed in a solvent or a dispersion medium, an electron-accepting compound such as a child-donating crude colorless dye, and, if necessary, a heat-fusible substance. Finely ground and mixed with Sara, Kaolin,
Old absorbing pigments such as calcined kaolin, Merck, waxite, diatomaceous earth, calcium carbonate, aluminum hydroxide, magnesium hydroxide, magnesium carbonate, titanium oxide, barium carbonate, urea-formalin filler, cellulose filler, etc.! In addition, a coating liquid is applied. (2) If necessary, it can be added with a rough-in-wax emulsion, a latex binder, a sensitivity improver, a metal soap, an antioxidant, an ultraviolet absorber, an image preservation improver, etc.

The coating liquid is applied to a support such as neutral paper, high-quality paper, or plastic film and dried. When preparing the coating liquid, all ingredients
They may be mixed and pulverized at the same time from the beginning, or they may be mixed in an appropriate combination and separately (after pulverization and dispersion).

Further, the coating liquid may be poured into the support.

As the support, neutral paper is particularly preferable from the viewpoint of fogging in the raw state and over time.

The components constituting the heat-sensitive recording material include 7 to 7 parts by weight of an adult-donating colorless dye, 7 to 6 parts by weight of an electron-accepting compound, 0 to 30 parts by weight of a thermofusible substance, and 0 parts by weight of a thermofusible substance. ~75 parts by weight, binder ~7~no! Consisting of a small amount of weight and other additives, a dispersant.

One or more electron-donating colorless dyes may be used in combination. Water is most desirable as the dispersion medium (solvent).

Examples of binders used in the present invention include styrene-butadiene copolymers, alkyd resins, acrylate epsilon copolymers, vinyl chloride-hinyl acetate copolymers, styrene-maleic anhydride acupoint 11-mers, synthetic rubbers, gum arabic, polyvinyl Examples include alcohol, hydroxyethylcellulose, and the like.

In particular, water-soluble binders such as gum arabic, polyvinyl alcohol, hydroxymethyl cellulose, and carboxymethyl cellulose are desirable in relation to the dispersion medium (solvent).

Thermofusible substances include phosphoric acid, stearic acid, behenic acid, palmitic acid, and stearic acid amide.
, behenic acid adb', stearic acid anilide, stearic acid toluicide, N-<ristoyl-p-anisidine,
N-<ristoyl-p = 7enetidine, /-methoxysulfonyl% -N-stearylcarbamoylbenzene, N-octadecylurea, hehexatecylurea, N,N-didotecylurea, phenylcarbamoyloxidedodecane, pt-butylphenol Phenoxy acetate, p-phenylphenol-p-chlorophenoxy acetate, rt, l-isofuroylidene bismethoxybenzene, β-phenylethyl-p-phenyl phenyl ether, 2-p-penzyloxynaphthalene, cobenzyl Oxynaphthalene, /-benzyloxynaphthalene, J-phenoxyacetyloxina7talene, diphenyl phthalate, /-hydroxyconaphthoic acid phenyl ester, copenzoyloxynanthalene, p-benzyloxybenzoic acid benzyl ester, hydroquinone acetate , /-phenoxy-p-ethylphenoxyethane, /, 4t-diphenoxybutane, /-phenoxy-2-p-methoxyphenoxyethane, etc. are used.

These substances are colorless solids at room temperature and have sharp melting points at temperatures that pass through the heating temperature for copying, that is, around 70 to 600C.

Waxes include noni rough-in socks, carnauba wax, microcrystalline wax, polyethylene wax, and higher fat FV3 acid abates such as atearine acetate, enalenhistearoate, and higher fatty acids. Examples include esters.

Examples of metal minerals include ten-grade fatty acid polyvalent metal salts, e.g.
Examples include zinc stearate, aluminum stearate, calcium stearate, zinc oleate, and the like.

Examples of image storage improvers include phenols or derivatives thereof in which at least 7 or more of the 2nd or 3rd positions are substituted with alkyl groups, among which 7 or more of the 2nd or 3rd positions are substituted with branched alkyl groups. phenol or its derivatives are preferred. It is preferable to have multiple phenol groups in the molecule, especially those with 22 to 3 phenol groups. 3,3-bis=(St' -hydroxy-3
'-tert-butylphenyl)butanoic acid coglycol ester, bis-[3,3-bis-(4t'-hydroxy-3'g'-di-tert-butylphenyl)butanoic acid]g IJ call ester, bis-[3,3-bis-(2'-methyl-v'-hydroxyta'-tert-butylphenyl)-butanoic acid coglycol ester, /, /, 3-
Tris(2-methyl-9-hydroxy-tertcrt-
phthylphenyl)butane, 9g'-thiobis(3-methyl-ot-tert-butylphenol), Hiroshi, \'-naobis(2-methyl-6-tert-butylphenol), 2.2'-thiobis(Dermenalu/5- tert-butylphenol), co,2'-methylenebis(St-methyl-6-(er
t-butylphenol), -1J'-methylenebis(9-ethyl-6-tert-
butylphenol), -K+-butyritenebis(3-menal-tert-
butylphenol), K, 1-mefl/”/bi,'((J, 4-dite
rt-butylphenol), λ-tert-butyl-u-tert-butoxyphenol.

Co, +2-dimenaluda inbrovir-7-ter
t-Butyl-6-chromanol, 2,2-dimethyl-+
-1-Butyl-3'-penzofuranol, e[[<t, t-bis[tertbutylthio)-s-
)・Reajin-Ile〕Ryo Mino〕2・Otsu-G-t e
r t-phthylphenol, etc.

In order to further improve the storage stability of colored images, powder blowing, etc., it is especially preferable to use these hindered phenols in combination with 7b.

The use of these compounds in the fecal matter is effective against phlegm-receptive compound cough! 00MR percent, l1f-E L (Ha2
0~yoo*accumulation percentage.

Examples will be shown below, but the present invention is by no means limited to these examples.

Examples/1 Preparation of color forming agent sheet Koani 1-3-methyl-6-diebur-minofluorane 79-, an electron-donating colorless dye, was dissolved in alkylated naphthalene 30-. This solution was emulsified by adding it to a water tank in which gelatin and gum arabic had been dissolved in a bath, with vigorous stirring, and oil droplets with a diameter of 7 to 10 microns were added thereto, followed by two drops of water. Add acetic acid with a little stirring to bring the pH up (to bring about coacervation,
/[lIγRANU) A wall of gelatin and gum arabic was made around it, formalin was added, and the pH was raised to 7 to harden the wall.

The thus obtained microcapsule dispersion was dried on paper to obtain a coloring agent sheet.

■ Preparation of color developer sheet Electron-accepting compound /,/-bis(l-hydroxyphenyl)acetic acid cinnamyl ester 2゜z! % polyvinyl alcohol water rllJ, 00P, and further added kaolin (Jossia kaolin) 2Of to ensure good dispersion and obtain a value of 2. The resulting coating solution was applied to paper, dried, and applied to a developer sheet.

When the color forming agent sheet and the color developing agent sheet were brought into contact with each other in this way and pressure or impact was applied, an instantaneous (two-black) image was obtained. They were separated.

Examples Co-electron-donating colorless dye co-anilino 3-methyl-
+-N-Methyl-to-cyclohexylanofluorantha 1 in 5% polyvinyl alcohol (Width: Ken measure 99, degree of polymerization/Li: 00) aqueous solution! .

I was dispersed all day and night with F and Ball I. On the other hand, similarly (
/,/-bis(l-hydroquinphenyl)acetic acid pupargyl ester 109-, which is a myotropic compound! Dispersion was carried out for one day in two bowls with superior polyvinyl alcohol water (1001), and after mixing these kinds of dispersion liquids, kaolin (Georgia 11th grade) was added and dispersed well. Paraffin wax emulsion θ% dispersion (Chukyo Yushi Seven Rosol #2, 2J') was added to prepare a coating liquid.

The coating liquid! Apply the solid content to neutral paper with a basis weight of θ9-/ln2 to give t y / m 2 , dry it at 0°C for 2 minutes, and then apply it to the coated paper. .

Coated paper is factor ε (monthly heat energy key vOm
When heated and colored at J/rrrm, a black impression was obtained. The color density was /,Qz.

Furthermore, after this coated paper was left at 90°C and 90% RH for 2 hours, the density of the colored image on the coated paper was 0.99.
The density of the non-image area was 0.06.

Example 3 Co-anilino 3-chloroj-diethylaminofluorane 2. was used as an electron-donating colorless dye instead of the electron-donating colorless dye of Example i. ! 1 and co-anilino 3-methyl-+-N-nonal-N-cyclohexylaminofluorane+2. evening? , for the 1 electron-accepting compound,
A coated paper was obtained in the same manner as in Example 2 except that i,t-his(l-hydroxyphenyl)r-fraudic acid cinnagol ester 109- was used as the electron-accepting compound.

Apply coated paper to 0 heat energy by applying 7 aximum 1.
A black I:lJ image was obtained when color was developed between J/lJ.

The color density was /.02.

Comparative Example/In place of the electron-accepting compound in Example A, co, 2-bis-(gu-hydroxyphenyl) was used as an electron-accepting compound.
A coated paper was obtained in the same manner as in Example 3 using propane 10f.

When the coated paper was heated and colored at a heating energy/I/key of 10 mJ/fi using a factor of 5 + 1, the color density was 0.53.

A comparison between Example 2.3 and Comparative Example shows that the electron-accepting compound of the present invention has extremely high coloring properties.

l-Hydroxybenzoic acid benzyl ester 10 was used as an electron-accepting compound instead of the electron-accepting compound in Comparative Example and Example U.
A coated paper was obtained in the same manner as in Example 2 using f. When the C color was developed in the same manner as in Example 2, the degree of color development was 7.03.
Met.

This coated paper again? Color development of coated paper after being left for C2Z time in 0% RH! ! The density of the I image is 0°2! Met.

Comparing Example λ and Comparative Example λ, it is clear that the recording paper using the electron-accepting compound of the present invention has excellent m-image storage stability.

Patent applicant Fuji Photo Film Co., Ltd. Procedural amendment (Blade side Showa to phantom (, F)

Claims (1)

[Scope of Claims] A recording material using an electron-donating colorless dye and an electron-accepting compound, characterized in that the electron-accepting compound is a compound represented by the following general formula. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the above formula, R represents a group having 3 to 18 carbon atoms and having an unsaturated bond.