JPS61110585A - Thermal recording material - Google Patents

Abstract

PURPOSE:To prevent sticking or head scumming from occurring, by sequentially providing on a base a thermal color forming layer comprising a leuco dye, a color developer and a zirconium compound and a protective layer to produce a thermal recording material. CONSTITUTION:A coating liquid is prepared by dissolving a leuco dye, a color developer and a zirconium compound in a solvent, and the liquid is applied to a base such as a paper, a synthetic paper and a plastic film, followed by drying to provide the thermal color forming layer. Then, a liquid for forming a protective layer is applied to the color forming layer, followed by drying to provide the protective layer, thereby obtaining the thermal recording material. The zirconium compound may be Na2ZrSiO5, ZrCOl2.8H2O or the like, and the amount thereof is about 2-20wt% based on the amount of the color devel oper, preferably, 5-10wt%. The leuco dye may be one based on triphenylmethane, fluoran or the like.

Description

[Detailed description of the invention] Technique-minute? F The present invention relates to a heat-sensitive recording material in which a protective layer is provided on a leuco-type thermochromic layer.

Accordingly, heat-sensitive recording materials using American technology leuco dyes are not used in various recording devices due to their high-speed recording properties. However, it is possible to improve the sensitivity of the heat-sensitive coloring layer. Along with this, the heat application means, molten material 1
81 (Hetkasu) and sticking ino phenomenon became noticeable, and the image 81R (4 became O (I) was criticized. 9 Such defects are caused by heat-sensitive recording t, which has l+A-, i@ layer in heat-sensitive coloring layer 1, <Recognize it as a fee.

In order to eliminate the drawbacks mentioned above, the conventional heat-sensitive recording material contains carbonic acid in the heat-sensitive coloring layer. 1st class %'rL (
'It has been proposed in I that CI ingredients be added, but the linofruit is not sufficient.

The present invention provides a heat-sensitive recording material in which a heat-sensitive coloring layer is provided on a support and a heat-sensitive coloring layer that blurs leuco dye ↑2F and a color developer, and a protective layer is further laminated.
An object of the present invention is to provide a heat-sensitive recording material (47) which is free from sticking and head scum and has improved image reliability. layer and a resin layer serving as a protective layer are sequentially provided (also referred to as a thermal recording material ((1)), which is characterized by containing a Zircola compound in the thermal coloring layer.

In the present invention, various known silconium-11 compounds can be used, but the following are preferred.

Nrr, 7. rSiOs, Zr0ch・81hO1
ZrO5Oa ・n1120, ZrO(N(Crll+
502)>, Zr5iOq, Zr0z, etc.

The weight ratio of zirconium to the color developer of the heat-sensitive coloring layer is 2 to 20%, preferably 5 to 10%, depending on the use of the zirconium compound. If the amount used is less than 2%, sticking and head residue will occur.

If it exceeds 20%, the color density will decrease.

As the leuco dye in the heat-sensitive coloring layer, leuco dyes that are used in this type of heat-sensitive recording material (S') are arbitrarily selected, and may be used singly or in combination.
"Inserts" - use in combination. For example, leuco dyes such as triphenylmethane type, fluoran type, phenothiazine type, auramine type and spiropyran type can be used. Specific examples include those shown below.

3.3-bis(p-dimethylaminophenyl)-phthalide.

3.3-bis(P-dimethylami, nof-L-l)-6-
Dimethylaminophthali 1-Ul1 name Crystal Bio L
3.3-bis(r-dimethylaminophyl)-6-
Dibutylaminophthali 1-1 3.3-His(p-dimethylaminophenyl 16-chlorophthalide, 3.3-bis(p-dibutylaminophenyl)phthalide, 3-cyclohexylamino-6-chlorofluorane, 3-dimethyl Amino-5,7-dimethylfluoranino 3
-diethylamino-7-talolofluran.

3-diethylamino-7-methylfluorane, 3-diethylamino-7,8-benzfluorane, 3-diethylamino-6-methyl-7-chlorofluorane, 3-(N-p-l heli-ethylamino) -6-Methyl-7-anilinofluorane, 3-pyrrolidino-b-methyl-7-anili, nofluorane, 2-(N-(3'-trifluoromethylphenyl)amino)-6-dinithylaminofluorane , 2- (
3.6-bis(diethylamino)-9-(o-chloroanilino)xantylbenzoic acid lactam), 3-diethylamino-6-methyl-7-(m-1-lichloromethylanilino)fluoran, 3-diethylamino-7- (o-chloroanilino)0fluorane, 3-dibutylamino-7-(o-chloroanilino)fluorane, 3-N-methyl-N-amylamino-6-methyl=7-
Anilinofluorane, 3-N-methyl-N-cyclohexylamino-6-methyl-7-anilinofluorane, 3-diethylamino-6-methyl-7-anilinofluorane.

3-(N,N-diethylamino)-5-methyl-7-(
N.

N-dibenzylamino)fluoran, benzoylleucomethylene blue, 6'-chloro-8'-methoxy-benzoin 1-linopyrillospiran, 6'-bromo-3'-methoxy-benzo, indolino-
Pyrillospiran, 3-(2'-hydroxy-4'-dimethylami, Nopheni J)-3-(2'-me]xy-5'-chlorphenyl)phthalide, 3-(2'-hydroxy-4'- dimethylaminophenyl)-3-(2'-methoxy-5'-nitrophenyl)
Phthalide, 3-(2'-hydroxy-4'-dibutylaminophenyl)-3-(2'-methoxy-5'-methylpheny)phthalide ((, 3'(2'-methoxy-4'-ditylami, nophenyl) -3-(2'-hydroxyl 4'-chloro-5'-methylphenyl 3-morpholino-7-(N-propyl-trifluoromethylanilino)fluorane, 3-pyrrolidino-7-trifluoromethylanilinofluorane 3-silica , 3-diethylamino-5-chloro-7-(α 3-(N-Ethyl-p-toluidino)-7-(α-)Dylethylamino)fluoran; t-Diethylamino-7-(o-methoxycarbonylphenylamino)Fluorane , 3-diethylamino-5-methyl-7-(α-phenylethylamino)fluoran, 3-diethylamino-7-piperidinofluorane, 2-
Chloro-3-(N-methyltoluidino)-7-(p-〇-butylanilino)fluoran, 3-(N-benzyl-cyclohexylamino)-5.

6-Beyunozo7-alpha naphthylamino-4'-bromofluorane.

3-diethylamino-6-methyl-7-mesitidino 4
',5'-benzofluorane etc.

Further, as the color developer, any known color developer may be used, but the following are preferred.

Benzoic acid, salicylic acid, 3,5-xy1/,nol.

Thymol, p-LerL-butylphenol, 4-hydroxyphenoxyto, methyl-4-hydroxyacetophenone, α-naphthol, β-naphthol, catechol, L/Fluoranhi-1-heloxy, non, 4-1. arL-
Octylcatechol, 4.4'-sec-butyritenephenol, 2,2-dihydroxydiphenyl, 2.

2-Methyl nonbis(4-methyl-6-1.crt-butylphenol), 2,2'-bis(4'-hydroxyphenol).

Nylpropane, 4,4'-isopropyritenebis(2
Lert-butylphenol), 4.4′-se
e-butyritene diphenol, pyrogallol, fluorocurcin, etc.

In the present invention, in order to fix the leuco dye and color developer to the support, known binders used in heat-sensitive recording materials can be used, such as polyhydric alcohol, starch and derivatives thereof. , cellulose derivatives such as methylcellulose, hydroxyethylcellulose, carboxymethylcellulose, methylcellulose, and ethylcellulose, sodium polyacrylate, polyvinylpyrrolidone, acrylic amide/acrylic ester copolymer,
Acrylic acid amide/acrylic ester/methacrylic 1
Ternary copolymer, styrene/maleic anhydride copolymer alkali salt, isobutylene/maleic anhydride/inic acid copolymer alkali salt, polyacrylamide 1~, sodium alginate,
In addition to water-soluble polymers such as gelatin and casein, polyvinyl acetate, polyurethane/tan, styrene/butadiene copolymer, polyacrylic acid, polyacrylic acid ester, vinyl chloride/vinyl acetate copolymer, polybutyl methacrylate,
Latexes such as ethylene/vinyl acetate copolymers and stylinone/butadiene/acrylic copolymers may be used.

The amounts of leuco dye, developer and binder used in the heat-sensitive coloring layer are 5 to 30% by weight, 40 to 80% by weight, and 2% by weight, respectively.
~20% is suitable, and the adhesion amount of the heat-sensitive coloring layer is 1-! in terms of solid content! Thermosensitive coloring layer with appropriate Og/rrf
As the protective layer, the binder resin used in the heat-sensitive coloring layer is used, and the solid content of the protective layer is preferably 0.5 to 1/rrr. .

Furthermore, in the present invention, in addition to the leuco dye and color developer, various auxiliary additive components can be optionally used in the heat-sensitive coloring layer.7 These auxiliary additive components are known ones, such as calcium carbonate, , inorganic fine powder such as silica, organic fine powder such as urea-formalin resin, higher fatty acid or its ester.

Examples include various thermofusible substances such as amides.

The heat-sensitive recording material of the present invention can be applied to paper, synthetic paper, plastic film 11 and
It can be produced by applying the protective layer forming solution onto a support such as "H" and drying it, and then applying the protective layer forming solution onto the heat-sensitive color forming layer and drying it. In addition,
The heat-sensitive coloring layer can have various layer configurations, such as laminating leuco dye and color developer as separate layers.

Effects Due to the above-described structure, the heat-sensitive recording material of the present invention does not generate sticking or head dregs even during high-speed recording, and has high image reliability.

Example The present invention will be explained in more detail with reference to Examples.

Note that the parts shown below are based on weight.

Example 1 [Liquid A] 20 parts of 3-N-methyl-N-cycloxylamino
6-MethiJ-ray 7-anilinofluoranhi 1-roxyethylcellulose 20 parts water
60 parts of the composition described above was dispersed in a ball mill for 24 hours to prepare a dispersion Δ.

[Liquid B]

Hisphenol A 155 parts Calcilla carbonate, 5 parts Polyhinyl alcohol (10% aqueous solution) 20 parts Water
6
0 parts” - Disperse the composition in a ball mill for 24 hours 1.
Dispersion B was prepared.

[Liquid C]

Polyvinyl alcohol (10% aqueous solution) 200 parts Calcilla carbonate 5 parts Zr5i04
(10% solution) 5 parts water

Dispersion C was prepared by dispersing 60 parts of the above composition in 7 triters for 10 hours.

The dispersion liquids A, B, and C were mixed and coated on high-quality paper (511 g/
, 7) at a concentration of 2 g/m (solid content) and dried.

Furthermore, polyvinyl alcohol (10% aqueous solution) was added to the layer at a concentration of 0.5 g/n (solid content).
The heat-sensitive recording material of the present invention was obtained by drying.Example 2 The ZrSiO4 used in the C solution of Example 1 was replaced with NazZrS.
The uninvented thermosensitive record 1 was prepared in the same manner as in Example 1 except that i(ls was replaced with 11t).

Example 3 A heat-sensitive recording material F of the present invention was obtained in the same manner as in Example 1 except that Zr5in< used in Solution C in Example 1 was replaced with Zr04.

Comparative Example 1 A comparative heat-sensitive recording material was obtained in the same manner as in Example 1, except that the C liquid of Example 1 was omitted.

Comparative Example 2 A comparative heat-sensitive recording material was obtained in the same manner as in Example 1 except that Zr5iO used in the C liquid of Example 1 was removed.

The heat-sensitive recordings of the present invention and the comparative heat-sensitive records obtained as described above were compared with G equipped with a thin-film thermal spatula.
A sticking and head scum test was carried out by printing in solid black using an Ill mode facsimile machine (power supply time to heating resistor: 2.2 rr+scc, 0.5 W/I dot).

The results are shown in Table-1.

Claims (1)

[Claims] A heat-sensitive recording material comprising a heat-sensitive coloring layer containing a leuco dye and a color developer and a resin layer serving as a protective layer sequentially provided on a support, the heat-sensitive recording material containing a zirconium compound in the heat-sensitive coloring layer. .