JPS5953191B2 - heat sensitive recording material - Google Patents

Description

[Detailed description of the invention] The present invention relates to improvements in thermosensitive recording materials.

Various heat-sensitive recording materials have been known.

One of them uses a combination of a metal soap such as silver behenate and an organic ring agent such as protocatechinic acid as a coloring component, which is described in Japanese Patent Publication No. 34-6485. For example, U.S. Patent No. 2,712,507 or U.S. Pat.
The coloring component is a combination of a leuco dye such as crystal violet lactone described in No. 730457, etc., and an organic acidic substance such as diphenol. However, in conventional heat-sensitive recording materials.

There were many inconveniences. For example, when printing with a thermal head, there are many cases in which fogging occurs due to friction with the head, or the head and paper stick together, making it impossible to obtain good recording. Furthermore, due to the poor heat transfer effect, it did not have a sufficient response speed to distant thermal signals, and furthermore, the method for preserving and stabilizing the image area was also insufficient.
As a result of studies aimed at improving these disadvantages, we have arrived at the present invention.

That is, in a heat-sensitive recording material in which a recording layer comprising a heat-sensitive color-forming component dispersed in a binder resin is provided on an arbitrary support, θ further contains at least one type of mica group mineral in the recording layer. It is a heat-sensitive recording medium. For example, an organic acidic substance (2) such as diphenol, a color-forming organic substance (B) such as a lactone compound, and a mica group mineral (O) are dispersed as fine particles and coated with a binder on a support such as paper (5). The obtained heat-sensitive recording material of the present invention can solve the above-mentioned problems due to the layered structure of the mineral (C), good heat insulation and heat retention, and various properties such as dye adsorption properties. Of these, M.Mg.

Si, O,. F. The synthetic mica represented by M-Naf is particularly effective, and among them, M-Naf swells in water to form plate-like fine particles with a size of about 1000 Λ and a thickness of about 30 mm, and when it dries, it is deposited in layers. It improves the flatness and slippage of the layer. Furthermore, this material has the property of adsorbing organic basic dyes and increasing the chemical stability of the dyes, so it is the most important material in the present invention. The amount used is generally in the range of 0.1 to 2 parts by weight per 1 part by weight of the heat-sensitive coloring component in the recording layer. Next, an example of a method for forming the heat-sensitive recording material of the present invention will be described.

The organic acidic substance (2) and the color-forming organic substance (2) are separately ground into desired particle sizes using a ball mill, etc., and dispersed in a suitable binder, and then when the two are mixed, the mica group Mineral (C) is added or previously added to (and in (B)).
C) may be added. The binder used in the present invention is a water-soluble synthetic polymer compound, a natural polymer compound, or an aqueous emulsion type polymer compound, such as polyvinyl alcohol, polyvinyl acrylamide, casein, gelatin, starch, etc. Its derivatives include methylcellulose, gum arabic sodium alginate, sodium canoleboxymethinoreceolose, pectin, co-pentapolymer of styrene and maleic anhydride, copolymer of polyethylene and maleic anhydride, vinyl methyl ether and maleic anhydride. copolymers, polyacrylates and copolymers thereof, and emulsions such as styrene-butadiene, vinyl chloride, acrylic, and vinyl acetate. Furthermore, if necessary, an antifoaming agent, a wetting agent, a whitening/obscuring agent such as talc or titanium oxide, an ultraviolet absorbing whitening agent, etc. can be added to the above.

The mica group mineral used in the present invention (an example of O is 1.1
Shirounmo series (1) (K, Na, Li) (Al
, Mg, V) 2 (Si, Al) 4010 (0H) 2 A natural mica mineral represented by the general formula of Illite et al.

(2) M-Mg,. A synthetic mica mineral represented by the formula 5.Si4.010-F2, where M is, for example, Li, K, Na
,NH4,Ca,Mg,Sn,Ba,Al,Ag,Pb
, Cu, H, etc.

2.2 Kurounmo series (1) K (Mg, FeII, Al) 3 (Si, Al)
40! It is a natural mica mineral represented by the general formula of ◆・(0H,・0), and includes 3.

(2) It is a synthetic mica mineral represented by the formula K-Mg3AlSi3OlOF2.

3 Others Examples include cairionite and celadonite.

In addition, the supports used in the present invention include paper, film,
Glass, metal plates, etc.

The color-forming substance (B) used in the present invention includes a color-forming lactone compound, a leucotriphenylmethane q compound,
Examples include leucodiphenylmethane compounds and acylphenothiazine compounds.

Further, specific examples of these compounds include the following.

Chromogenic lactone compound) Triphenylmethane derivative 3-(P-N,N-dimethylaminophenyl)-3-phenylated 3-(P-N,N-diethylaminophenyl)-3-phenol Phthalide 3-(P-N-ethyl-N-<.ndylaminophenyl)-3-phenylphthalide 3-(P-aminophenyl)-3-phenylphthalide 3-phenylinol-3-(P
-dimethylaminophenyl)phthalide 3,3-bis(P
-dimethylaminophenyl) -6-dimethylaminophthalide (crystal violet lactone) 3,3-bis(P-dimethylaminophenyl)phthalide (malachite green lactone) 3,3-bis(P-diethylaminophenyl) Phthalide 3,3-bis(P-dimethylaminophenyl)-methoxyphthalide 3,3-bis(P-dimethylaminophenyl)-5,6
,7,8-tetrachlorophthalide 3,3-bis(P-dimethylaminophenyl)-5-chlorophthalide 3,3-bis(P-dimethylaminophenyl)-5,6
-dibromophthalide 3,3-bis(P-dimethylaminophenyl)-5-aminophthalide 3,3-bis(P-dimethylaminophenyl)-5-methylaminophthalide 3,63-bis(P-dimethylaminophenyl) enyl)-5-
Dimethylaminophthalide 3,3-bis(3-methyl-4
-dimethylaminophenyl)phthalide 3,3-bis(P
-methylaminophenyl)phthalide 3,-03-bis(
P-methylaminophenyl)-5-acetylaminophthalide 3-(4″-dimethylamino-6″-aminophenyl)-3-(4″-dimethylaminophenyl)-5-
Acetylaminophthalide 3-(4″-dimethylaminophenyl)-3-(4″″-hydroxyphenyl)phthalide 3-(P-dimethylaminophenyl)-3(acridin-2-yl)-6- dimethylaminophthalide
B3-(P-dimethylaminophenyl)-3(9-ethycanolebazo-3-ynole)-6 dimethylaminophthalide 3,3-bis-(9-
Ethinolecanolebazonole-3-yl) phthalide
13,3-bis-(9-ethynole-6-chlorocarbazol-3-yl)phthalide 3,3
-bis-(9-ethynolecanolebazonole-3-yl)
-6-dimethylaminophthalide (2) fluorane derivative
13-dimethylamino-5,
7-dimethyl-fluorane 3-diethylamino-5,7
-dimethyl-fluorane 3-diethylamino-6,7-
Dimethinolef 2luorane 3-diethylamino-5,6
-dimethyl-fluorane 3-diethylamino-5,7-
dimethyl-fluorane
23-Diethylamino-5,8-dimethyl-fluorane 3-diethylamino-6-methynofluorane 3-diethylamino-6,7-dimethyl-fluoran 3-diethylamino-6,8-dimethylfluoran 3- Diethylamino-7,8-dimethyl-fluorane 53,6
-bis-(N-methyl-N-phenylamino)-4″,
5″,6″,7″-tetrachlorofluoran 3,6-bis-(N-ethyl-Nphenylamino)-4″,5″,
6″,7″-tetrachlorofluorane 3,6-bis-[
N-methyl-N-(P-chlorophenyl)amino]-4
″,7″-dichlorofluorane 3,6-bis-(N-isoamyl-N-phenylamino)-5-iodofluoran 3,6-bis-[N-methynole-N-(P-chlorophenyl)amino] -5'-bromo-6'-chlorofluorane 3,6-bis-(N,N-diethylamino)-4
″, 5″, 6″, 7″-tetrachlorofluorane-3,
6-bis-(N-phenylamino)-4″, 5″, 6″
,7″-tetrachlorofluorane 3,6-bis-(N,
N-diethylamino) fluorane (Rhodamine B lactone) 3,4--1<N-6-dimethylaminofluorane 2,7-diaminofluorane 3) Naphthalide derivative 3,3-bis-(P-dimethylaminophenyl ) Naphthalide 3,3-bis-(P-dimethylaminophenyl)naphthalide 3-(4''-diethylamino-2''-methylphenyl)-3-(4''-diethylamino-2''-methylphenyl)naphthalide 3,3 -Bis-(P-N,N
-dibenzylaminophenyl) naphthalide 3,3-bis-[P-(N--1<N-ethylamino)
phenyl]naphthalide 3-(3″-methyl-4″-dimethylaminophenyl)-3-(3″″-methyl-4″″
-dimethylaminophenyl)-6(or 7)-nitronaphthalide3-(3″-chloro-4″-dimethylaminophenyl)-3-(3″-chloro-4″-dimethylaminophenyl) )-5(or 8)-chlornaphthalide 3,
3-bis-(P-dimethylaminophenyl)-6(or 7)-dimethylaminonaphthalide 4) Azaphthalide derivative 3-(4″-diethylaminophenyl)-3-(2″″
-Chlor-4''-dimethylaminophenyl)-J me[azaphthalide 3-(4''-diethylaminophenyl)-3
-(2″″-methoxy-4″″-dimethylaminophenyl)-4-azaphthalide 3-(4″-dimethylaminophenyl)-3 Class I (2″″-methyl-4″″-diethylaminophenyl) -J me[azaphthalide 3-(4''-diethylaminophenyl)-3(2''-methyl-4''''-
diethylaminophenyl)-4-azaphthalide 3,3-
Bis-(P-dimethylaminophenyl)-J-[azaphthalide 3,3-bis-(P-diethylaminophenyl)-
J Me[Azaphthalide 3,3-bis-(0-phenoxy-P)
-dimethylaminophenyl) -J me[azaphthalide 3,3
-Bis-(0-tolylthio-P-dimethylaminophenyl)-J-[azaphthalide 3-(4″-diethylaminophenyl)-3-[4″″-(N-phenyl-N-methyl)aminophenyl]- J Me[Azaphthalide 3-(4″-N
, N-chloromethyl-aminophenyl)-3-(4″″
-dimethylaminophenyl) -J me[azaphthalide 3-(
4″-dibenzylamino-2″-methoxyphenyl)-
3-(4″″-dimethylamino-2″″-chlorophenyl)-J me[azaphthalide 5 and 6-
azaphthalide (5) heterocyclic allyldiphenylmethane derivative 3-(P-dimethylaminophenyl)-3-(1
-methylpyrrol-2-yl)-6-dimethylaminophthalide 3-(P-dimethylaminophthalide)-3-(1
-phenylpyronot-2-yl)-6-dimethylaminophthalide 3-(P-dimethylaminophenyl)-3-(
2-Methylindol-3-yl)-6-dimethylaminophthalide 3-(P-dimethylaminophenyl)-3-
(1,2-dimethylindol-3-yl)-5-diethylaminophthalide (6) Pyromellitic anhydride derivative cis-3,5-bis-(P-diethylaminophenyl)
-3,5-bis-(1,2-dimethylindole-3=
il) pyromellitide trans-3,7-bis-(P-
dimethylamino゜phenyl)-3,7-bis-(1,2
-dimethylindol-3-yl)pyromellitide trans-3,3,7,7-tetrakiz-(1,2-dimethylindol-3-yl)pyromellitide (7) diphenylmethane derivative 4-dimethylaminophenyl-4' -dimethylamino-
2"-Lactone of carboxyphenylhydroxymethane 9-ethylcarbazonot-3-yl-9'-ethyno-2'-1-carboxyphenyl-hydroxymethane lactone 6-chloro-19- Metinorecanorebazonore1 3-Inole16'-Chronore19'-
Methinole-2'-carboxyphenylhydroxymethane lactone 6-furom-9-ethynolecanolebazonol-3-yl-4''-dimethylamino-2'-carboxyphenylhydroxymethane lactone Chromogenic lactam compound 9-paranitroanilino-3,6-bis-(diethylamino)-9-xanthenyl-orthobenzoic acid lactam 9-anilino-3,6-bis-(dimethylamino)-9
-lactam bis-(P) of xanthenyl-orthobenzoic acid
-dimethylaminophenyl)-p-dimethylamino-9-canoleboxyphenylanilinomethane, and lactams: Color-forming sultone compound 3,6-bis-(diethylamino )-9-hydroxy-
3 sultones derived from the lactone compounds described in 1, such as the sultone of 9-xanthenoylbenzenesulfonic acid; Chromogenic spiropyran compound 1,3,3-trimethylindolino-8''-methoxybenzopyrylspirane 1,3 ,3-trimethylindolino-8''-ethoxybenzopyrylspirane 1-ethyl-3
, 3-dimethylindolino-18''-methoxybenzopyrylspirane 1-amyl-3,3-dimethylindolino-18''-ethoxybenzopyrylspirane 1,3-dimethynolyl-3(or 5 or 7)-phenyl -8"-Methoxybenzopyrylspirane 1,3,3-trimethyl-5-chloroindolino -18"-Ethoxybenzopyrylspirane 1
,3,3-trimethyl-5,8(or 7,8)-dimethoxyindolinobenzopyrylspirane 1,3,3-trimethyl-4,7-dimethoxyindolino-18''-ethoxybenzopyrylspirane 1, 3,3-trimethyl-5,
7(or 4,7)-dimethoxyindolino-8″-methoxybenzopyrylspirane 1,3,3-trimethyl-5
-B-Hydroxyethylindolino-8"-methoxybenzopyrylspirane 1,3,,3-trimethylindolino-6"-bromo-8"methoxybenzopyrylspirane 1,3,3-trimethylindolino-5 '',6''-dichloro-8''-ethoxybenzopyrylspirane 1-ethyl-3,3-dimethylindolino 6''-chloro-8''-ethoxybenzopyrylspirane 1-butyl-3,3-dimethylindolino -6''-promo8''-methoxybenzopyrylspirane 1,3-dimethyl-3-propylindolino6''-chloro-8''-methoxybenzopyrylspirane 1-phenyl-3-methyl-3-propylindolino -8″-methoxybenzopyrylspirane 1-phenyl-3,3-dimethylindolino 5″,6″-dichloro-8
″Monoethoxybenzopyrylspirane 1-methynolyl-3-
Propyl-3-phenylindolino-18''-ethoxybenzopyrylspirane 1-methynolyl-3-amylu (
P-dimethylaminophenyl)methanebis(P-diethylaminophenyl)phenylmethanebis(P-N-
Hydroxyethyl-N-methylaminophenyl)-P-
Dimethylamino-0 chloromethane 9,9″-diethyl-
3,3″-dicarbazolylphinylmethane bis-(P-
dimethylaminophenyl)-Pdimethylamino-0-carboxyphenylmethanebis-(3-methyl-4-hydroxy-5-carboxyphenyl)-2,6-dichlorophenylmethanebis(3-methyl-4 -Hydroxy-5-carboxyphenyl)-4-diethylaminophenylmethane: Color-forming leucodiphenylmethane compound bis(P-dimethylaminophenyl)methane dipyrylmethane tryptophan 9,9''-diethyl-6,6 ″-dichlor-3,3″-
Dicanolebazolinolemethaneleucoauramine N,N-diethylleucoauramine phenylsulfonamide bis-(P-dimethylaminophenyl)methane bis-(P-dimethylaminophenyl)
benzotriacylmethane bis-(P-diethylaminophenyl)morpholinylmethane bis-(P-dimethylaminophenyl)-N-benzotriazolylmethane bis-(
P-diethylaminophenyl)-N-indolylmethanebis-(P-dimethylaminophenyl)-N-pyrrolylmethanebis-(P-dimethylaminophenyl)-Ncanolebazolinolemethanel Color-forming acylphene Notiazine compound 3,7-bis-dimethylamino-10-acetylphenothiazine 3,7-bis-diethylamino-10-bezolfetchazine 3,7-diethylamino-2.8-
Dimethyl-10-propionylphenothiazine 3-N-
Methyl-N-ethylamino-10-0-chlorobenzoylphenothiazine 2-Methyl-3-amino-10-P-methoxybenzoylphenothiazine As described above Chromogenic substance 8
Phenolic acidic substances and organic acids are preferable as the acidic substance that develops color when in contact with water.These substances are solid at room temperature, desirably have physical properties such that they liquefy or vaporize at 50°C or higher, and are insoluble or poorly soluble in water. Must be molten.

Next, specific examples of these acidic substances will be shown.

1 Phenolic acidic substance 4-tert-butylphenol, 4-hydroxydiphenooxide, α-naphthol, β-ophthol, methyl-4-hydroxybenzoate, 4-hydroxyacetophenone, 4-tert-octylcatechol, 2
, 2"-dihydroxydiphenyl, 4-hydroxydiphenyl oxide 2,2"-methylenebis(4-chlorophenol), 2,2"methylenebis(4-methyl-6
-tertiarybutylphenol), 4,4''-isopropylidene diphenol, 4,4''-isopropylidene bis(2-chlorophenol), 4,4''-isopropylidene bis(2,6-dichlorophenol), 4 ,4
″-isopropylidene bis(2-methylphenol),
4,4'-isopropylidene bis(2,6-dimethylphenol), 4,4''-isopropylidene bis(2-
tert-butylphenol), 4,4″-secondary butylidene bis(2-methylphenol), 4,4
″-cyclohexylidene diphenol, 4,4″-cyclohexylidene bis(2-methylphenol), 2,2
'-thio. Bis(4,6-dichlorophenol), P,
P-(1-methyln-hexylidene) diphenolic acid stearic acid, 10-oxystearic acid, myristic acid, valmitic acid, behenic acid, gallic acid, benzoic acid, salicylic acid, 1-oxy-2-naphthoric acid, succinic acid,
2-oxy-P-toluic acid, m-oxybenzoic acid, p
-Oxybenzoic acid, 4-oxyphthanoleic acid, chlorognoresincanolebonic acid, dioxytartaric acid, 2,6-dioxybenzoic acid, zorpic acid The present invention will be explained in more detail below with reference to Examples.

Example 1 4 and 5 were each pulverized and mixed in a ball mill to have a particle size of 1 to 3μ.
I made it so that

Next, 5 parts by weight of 3 and 25 parts by weight of 5 were added with Na-Mg.
2.5si4OlO-F2 (manufactured by Surface Research Institute, swelling starch ink colloid GM) 2.0wt% aqueous solution
After adding 0 parts by weight, it was coated on paper using Miyaba Ikkuro 5 and dried with hot air at about 80°C. The resulting heat-sensitive recording paper had a smooth, pure white surface with no ground covering, and was smooth and smooth, like plain paper. When the recording layer of this thermosensitive recording paper and the back side of the original were overlapped and heated with infrared rays from the front side of the original, a blue colored copy was obtained. Furthermore, when a thermal pen or thermal head was brought into contact with a thermal recording paper prepared in the same manner, it developed a bright blue color similar to the one above, and the paper did not stick to the thermal head or cause background fog due to rubbing with the head. Good recorded images were obtained. Example 2 3 and 5 were pulverized and mixed using a ball mill to obtain particles with a particle size of 1 μm to 3 μm.
It was made to be μ.

Next, 50 parts by weight of water was added to 5 parts by weight of 3 and 25 parts by weight of 5, and the mixture was applied onto paper weighing approximately 50 g/M2 using Miyaba's 5, and dried with hot air at approximately 80°C. did. When the resulting thermosensitive recording paper was subjected to recording in the same manner as in Example 1, the same results as in Example 11 were obtained. Example 3 From the recording paper of the present invention obtained in the same manner as in Example-1 and the recording paper of Example-1, Na.Mg2.5.Si4OlO-
Table 1 shows the test results regarding thermal response and storage stability of the colored area compared to conventional thermal paper except F2.

(However, the surface temperature of the thermal head was approximately 350° C.) These results clearly demonstrated the effectiveness of the present invention.

Example 4 Recording paper was prepared in the same manner as in Example-1 using 3-diethylamino-6-methyl-meanilinofluorane in place of the crystal violet lactone in Example-1, and recording was performed in the same manner. , a good black-on-white image was obtained.

Example 5 The experiment was carried out in the same manner as in Example 1 except that crystal violet lactone was replaced with silver behenate and 4,4''-isopropylidene diphenol was replaced with protocatechic acid.

Example 6 The same procedure as in Example 1 was carried out except that ferric stearate was used for crystal violet lactone and gallic acid was used for 4,4''-isopropylidene diphenol.

Example 7 The experiment was carried out in the same manner as in Example 1 except that crystal violet trataton was replaced with zinc stearate and 4,4''-isopropylidene diphenol was replaced with catechol.

Example 8 In Example 2, K-Mg3AlSi3OlO-F2
The same procedure was carried out except that the amount of addition was 50 parts by weight in each of the compositions 3 and 5.

Example 9 K-Mg3AlSi4OlO-F2 in Example-2
The experiment was carried out using mica group minerals as shown in Table 2 instead.

Claims (1)

[Claims] 1. A heat-sensitive recording material in which a recording layer comprising a heat-sensitive color-forming component dispersed in a binder resin is provided on an arbitrary support, and the recording layer further contains at least one type of mica group mineral. A heat-sensitive recording material characterized by: