JPH02206585A - Thermal recording paper - Google Patents

Abstract

PURPOSE:To obtain thermal recording paper having a special color tone by a method wherein a coating layer containing a pigment is laminated on a thermal color-forming layer formed on a sheet substrate by applying thereon at least one of titanium oxide and iron oxide on the surface of a natural mica. CONSTITUTION:A thermal color-forming layer 14 which produces color by heating is formed on a sheet substrate 12, and thereon a coating layer 16 containing a pigment is further laminated by applying thereon at least one of titanium oxide and iron oxide on the surface of a natural mica. Then, thermal recording paper 10 is formed. As the aforesaid sheet substrate 12, paper, synthetic resin sheet, or the like is used. The thermal color-forming layer 14 to be formed thereon is formed by applying a mixture of a color former, a color developer, and a binder and drying the same. In this manner, a part of an incident light to the coating layer 16 is reflected, the other light having the complementary color is transmitted, and these lights respectively form a reflected color and a transmitted color. Thus, the color tone of the recording paper 10 can be seen different according to the background color of coating layer 16.

Description

[Detailed description of the invention] (Industrial application field) This invention relates to thermal recording paper.

(Prior Art) In this type of conventional thermosensitive recording paper, a thermosensitive coloring layer that develops color when heated is formed on the surface of a sheet base material. Therefore, by heating the thermosensitive coloring layer of this thermosensitive recording paper, the heated portion can be colored. This type of thermal recording paper is used for facsimile,
Computer.

Widely used for recording paper in recorders, ticket issuing machines, etc.

(Problems to be Solved by the Invention) For example, white paper is used as the sheet base material of conventional thermosensitive recording paper, and by heating the thermosensitive coloring layer, characters and figures in tones of black, red, blue, etc. are formed. There was a hailstorm.

Therefore, the main object of the present invention is to provide a thermal recording paper having an unprecedented color tone.

(Means for Solving the Problems) This invention comprises a sheet base material, a heat-sensitive coloring layer formed on the surface of the sheet base material that develops color by heating, and a coating layer formed on the heat-sensitive coloring layer. It is a heat-sensitive recording paper containing a pigment coated with at least one of titanium oxide and iron oxide on the surface of natural mica.

(Function) Light incident on the coating layer undergoes regular multiple reflections by pigments made of natural mica coated with titanium oxide, iron oxide, etc.

(Effects of the Invention) According to the present invention, the colored portion of the thermosensitive coloring layer appears to have a different color from the color of the thermosensitive coloring layer due to regular multiple reflections in the coating layer. Moreover, the non-color-forming portion of the thermosensitive color-forming layer has pearlescent luster due to regular multiple reflections in the coating layer.

The above objects, other objects, features and advantages of the present invention will become more apparent from the following detailed description of embodiments with reference to the drawings.

(Example) The figure is a sectional view showing an embodiment of the present invention.

This thermosensitive recording paper 10 includes a sheet base material I2.

This sheet base material 12 is formed of a sheet material such as paper 2 synthetic resin, for example.

On one main surface of the sheet base material 12, a thermosensitive coloring layer 1''4, which develops color when heated, is formed.

The heat-sensitive coloring layer I4 is formed by, for example, applying a mixture of a coloring agent, a coloring agent, and a binder to the surface of the sheet base material 12 and drying it.

In this case, the coloring agent is, for example, 3,3-bis(
p-dimethylaminophenyl)-6-dimethylaminophthalide, 3,3-bis(p-dimethylaminophenyl)
Phthalide, 3-(p-dimethylaminophenyl)-3-
(1,2-dimethylindol-3-yl)phthalide,
3-(p-dimethylaminophenyl)-3-(2-methylindol-3-yl)phthalide, 3,3-bis(1
2-dimethylindol-3-yl)-5-dimethylaminophthalide, 3,3-bis(1,2-dimethylindol-3-yl)-6-dimethylaminophthalide, 3.
3-bis(9-ethylcarbazol-3-yl)-6-
Dimethylaminophthalide, 3.3-bis(2-phenylindol-3-yl)-6-dimethylaminophthalide, 3-p-dimethylaminophenyl-3-(1-methylpyrrol-3-yl)-6 - triallylmethane dyes such as dimethiaminophthalide, 4,4'-bis-dimethylaminobenzhydryl benzyl ether, N-halophenyl-leucoolamine, N2.4.5-)lichlorophenylicoolamine, etc. diphenylmethane dye,
Thiazine dyes such as benzoylleucomethylene blue and p-nitrobenzoylleucomethylene blue, 3-methyl-spiro-dinaphthopyran, 3-ethyl-spiro-
Dinaphthopyran, 3-phenyl-spirodinaphthopyran, 3-benzyl-spiro-dinaphthopyran, 3-methyl-naphtho(6'-methoxybenzo)spiropyran, 3-
spiro dyes such as propyl-spiro-dibenzobilane, rhodamine-β-anilinolactam, rhodamine (p
- Lactam dyes such as nitroanilino)lactam, rhodamine (0-chloroanilino)lactam, 3-dimethylamino-7-methoxyfluorane, 3-diethylamino-6-methoxyfluorane, 3-diethylamino-7-
Methoxyfluorane, 3-diethylamino-7-nichlorofluorane, ethylamino-6-methyl-7-chlorofluorane, 3-diethylamino-6,7-dimethylfluorane, 3-(N-ethyl-p-+luidino) ) Near-methylfluorane, 3-diethylamino-7-N-acetyl-N-methylaminofluorane, 3-diethylamino-7-N-methylaminofluorane, 3-diethylamino-7-dibenzylaminofluorane, 3 -diethylamino-? -N-methyl-N-benzylaminofluorane,
3-diethylamine-7-N-chloroethyl-N-methylaminofluorane, 3-diethylamino-7-N-sheralaminofluorane, 3-(N-ethyl-p-)luidino)-6-methyl-7- Phenylaminofluorane, 3-(N-ethyl-p-toluidino)-6-methyl-
7-(p-)luidino)fluorane, 3-diethylamino-6-methyl 7-phenylaminofluorane, 3-
Diethylamino-7-(2-carbomethoxy-phenylamino)fluoran, 3-(N-ethyl-N-isO-
amylnamino)-6-methyl-7-phenylaminofluorane, 3-(N-cyclohexyl N-methylamino)
-6-methyl-7-phenylaminofluorane, 3-pyrrolidino-6-methyl-7-phenylaminofluorane,
3-Piperidino-6-methyl-7-phenylaminofluorane, 3-diethylamino-6-methyl-7-phosyridinofluorane, 3-diethylamino-7-(o-chlorophenylamino)fluorane, 3-dibutylamino-
Examples include fluoran dyes such as 7-(O-chlorophenylamino)fluoran and 3-pyrrolidino-6-methyl-7-p-butylphenylaminofluoran.

In addition, as a coloring agent, for example, activated clay, acid clay, attapulgite, bentonite, colloidal silica, inorganic acid substances such as aluminum silicate, 4-ter
t-butylphenol, 4-hydroxydiphenoxide,
α-naphthol, β-naphthol, 4-hydroxyacetophenol, 4-tert-octylcatechol, 2
．． 2-dihydroxydiphenol, 2,2'-methylenebis(4-methyl-5-tert-isobutylphenol), 4,4'-isopropylidenebis(2-tert
-butylphenol), 4.4-sec-butylidene diphenol, 4-phenylphenol, 4.4'-isopropylidene diphenol (bisphenol A), 2.
2'-methylenebis(4-chlorophenol), hydroquinone, 4.4'-cyclohexylidene diphenol, benzyl 4-hydroxybenzoate, dimethyl 4-hydroxyphthalate, hydroquinone monobenzyl ether,
Phenolic compounds such as novolac type phenolic resins and phenol polymers, benzoic acid, p-tert-butylbenzoic acid, trichlorobenzoic acid, terephthalic acid, 3-s
ec-butyl-4-hydroxybenzoic acid, 3-cyclohexyl-4-hydroxybenzoic acid, 3.5-dimethyl-
4-hydroxybenzoic acid, salicylic acid, 3-isopropylsalicylic acid, 3-tert-butylsalicylic acid, 3-
Benzylsalicylic acid, 3-(α-methylbenzyl)salicylic acid, 3-chloro-5-(α-methylbenzyl)salicylic acid, 3.5-di-tert-7′tylsalicylic acid,
Aromatic carboxylic acids such as 3-phenyl-5-(α,α-dimethylbenzyl)salicylic acid, 3,5-di-α-methylbenzylsalicylic acid, and these phenolic compounds, aromatic carboxylic acids such as zinc, magnesium,
Examples include organic acidic substances such as salts with polyvalent metals such as aluminum, calcium, titanium, manganese, tin, and nickel.

Furthermore, examples of binders include polyvinyl alcohol, methylcellulose, methoxycellulose, hydroxyethylcellulose, carboxymethylcellulose,
Examples include modified starch, polyvinylpyrrolidone, acrylic ester, and polyacrylamide.

Therefore, this thermosensitive coloring layer 14 can develop color by heating it.

In addition, in the mixture for forming the thermosensitive coloring layer 14,
If necessary, fillers such as inorganic fillers and organic fillers may be added in order to arbitrarily color the heat-sensitive coloring layer 14, and a sensitizer may be added to increase the sensitivity of the heat-sensitive coloring layer 14 to heat. good.

In this case, examples of inorganic fillers include aluminum hydroxide, heavy calcium carbonate, light calcium carbonate, titanium oxide, barium sulfate, silica gel, activated clay, talc, clay, kaolinite, diatomaceous earth, magnesium carbonate, Examples include alumina, aluminum oxide, etc.
Examples of organic fillers include polystyrene resin particles,
Examples include urea-formalin resin particles and polyolefin particles.

Examples of sensitizers include amides such as stearamide, palmitamide, oleic acid amide, lauric acid amide, ethylene bis stearamide, methylene bis stearamide, and methylol stearamide, paraffin wax, and Examples include alcohol.

Furthermore, the mixture that is the material of the thermosensitive color forming layer 14 includes a curing agent for curing the binder in the mixture, and a curing agent that prevents the heat sensitive color forming layer 14 from adhering to the head in the printer and improves its running properties. A lubricant or the like may be added.

Furthermore, as the material for the thermosensitive coloring layer 14, a mixture of an aromatic isocyanate and an imino compound may be used. Examples of aromatic isocyanates include 2,5-dimethoxy-4,4',4'-triisocyanate-triphenylamine. This isocyanate is
If necessary, it can also be used in the form of so-called blocked isocyanates, which are addition compounds with phenols, lactams, oximes, etc.

In addition, examples of imino compounds include 3-iminoisoindolin-1-one, 3-imino-45,6,7-tetrachloroisoindolin-1-one, 3-imino-4,
5,6,7-chitrapromoisoindolin-1-one,
3-imino-45,6,7-titrafluoroisoindolin-1-one, 3-imino-5,6-dichloroisoindolin-1-one, 1,3-diiminoisoindoline, 1,3-diimino- 4,5,6,7-titrachloroisoindoline, 1,3-diimino4.5,6.7-titrafluoroisoindoline, 1,3-diimino-5,6-
Examples include dichloroisoindoline.

Further, as the material for the thermosensitive coloring layer 14, a mixture of a methine dye and an oxidizing organic compound may be used. Examples of methine dyes include the following compounds.

(A) As the triaminotriphenylmethane dye, 4.4',4"-tris-dimethylamino-triphenylmethane, 4.4',4"-)lis-diethylamino-
Triphenylmethane, 4.4'bismethylamino-4"
-dimethylamino-triphenylmethane, 4.4'-bisdimethylamino-4-methylamino-triphenylmethane, 4゜4'-bis-diethylamino-4"-ethylamino-triphenylmethane, 4.4"-bis -diethylamino-4#-amino-triphenylmethane, 4.4'
-bisdimethylamino-3"-methyl-4"-amino-
Triphenylmethane, 4,4'bisdimethylamino-3
#-Methyl-4#-methylamino-triphenylmethane, 4.4',4"-trisphenylamino-triphenylmethane, 4.4',4'-tris(N-methyl-N-
phenylamino)-triphenylmethane, 4.4'bismorpholino-4"-dimethylaminotriphenylmethane, 4.4',4'-)lis-dimethylamino-2,2'
-dimethyl-triphenylmethane, 4.4',4"-tris-dimethylamino-3,3'-dimethyl-triphenylmethane, 4°4',4"-tris-dimethylamino-2-methoxy-triphenyl Methane, 4.4", 4'
-Tris-dimethylamino-3-methyl-triphenylmethane, 4,4'-bis-dimethylamino-4-N-benzylamino-triphenylmethane, 4,4'-bis-
Dimethylamino-4#-N-benzylamino-3"-methoxytriphenylmethane, 4.4'-bis-dimethylamino-4#-Nbenzylamino-3"-methyltriphenylmethane, 4.4'-bis -dimethylamino-3#
Chlor-4'-N-benzylaminotriphenylmethane, 4,4'-bis-dimethylamino-4"-(N-benzyl-N-methylamino)-triphenylmethane, 4,
4′-bis-dimethylamino 4″-(N-0-chlorobenzyl-N-methylamine)-triphenylmethane, 4
．． 4'-bisdimethylamino-4"-(N-p-chlorobenzyl-N-methylamine)-triphenylmethane,
4.4'-bis-dimethylamino-4''-(N-p-methylbenzyl-N-methyl)-triphenylmethane, 4
, 4'-bis-dimethylamino-4-(N,N-dibenzylamino)-triphenylmethane, 4.4'-bis-
Dimethylamino-4-(N-phenyl-N-methylamino)-triphenylmethane, 4.4'-bis-dimethylamino-4#-morpholino-triphenylmethane, 44
'-Bis-N-benzylamino-4"-dimethylamino-triphenylmethane, 4,4'-bis(N-benzyl-N-methylamino)-4"dimethylaminotriphenylmethane, 4,4'bis( N-parachlorobenzyl-N
-methylamino)-41-dimethylamino-triphenylmethane, 4,4'-bis(N-parabromobenzyl-
N-ethylamino)-4"-diethylamino-triphenylmethane, 4.4'-bis-pyrrolidyl-4#-dimethylaminotriphenylmethane, 44'-bis(N-orthochlorobenzyl-N-methylamino)- 4"-dimethylamino-triphenylmethane, 4.4'-bis-pyrrolidyl-4-(N-benzyl-N-methylamino)-
Triphenylmethane, 3,3'-dichloro-4,4'-
Bis(N-benzylamino)-4#-dimethylamino-
Triphenylmethane, 4.4'-bis(N-p-methylbenzyl-N-methylamino)-4"-dimethylamino-triphenylmethane, 44'-bis(N-p-methylbenzyl-N-ethylamino) )-4″-diisopropylamino-triphenylmethane, 3,3-dimethyl-4,
4'-bis(p-methylbenzylamino)-4"-dimethylaminotriphenylmethane, 3,3-dimethyl-4
, 4'-bis(N-benzylamino)-4#-dimethylamino-triphenylmethane, 33-dibutyl-4,4
'-bis-N-benzylamino-4''-diethylamino-triphenylmethane and the like.

(B) As a diaminotriphenylmethane dye, 4.4
'-bis-dimethylamino-triphenylmethane, 4.
4'-bis-dimethylamino-4-methyl-triphenylmethane, 4,4'-bis-(N-benzyl-N-ethylamino)triphenylmethane, 4,4'-bisdimethylamino-2-chloro- Triphenylmethane, 4.4'
-bisdiisopropylamino-3"-bromotriphenylmethane, 4,4'-bisdimethylamino-4methoxytriphenylmethane, 4,4'-bisdimethylamino-
4#-Ethoxytriphenylmethane, 4.4'-bisdimethylamino-3#methyl-4#-methoxytriphenylmethane, 44'-bisdimethylamino-3"-methyl-4ethoxytriphenylmethane, 4.4 "-bisdimethylamino-3#, 4"-dimethoxytriphenylmethane, 4.4'-bisdimethylamino 2"4"-dimethoxytriphenylmethane,4.4'-bis-diethylamino-3"-ethyl4# -ethoxy-triphenylmethane, 4,4-bis-methylamino-3,3'-dimethyl-3#-butyl-4#-butoxytriphenylmethane, 4,4'-bis-dimethylamino-3 "Cyclohexyl-4#-methoxy-triphenylmethane, 4,4'-
Bis-propylamino-3"phenyl-4"-propoxy-triphenylmethane, 4,4'-bis(N-benzyl-N-methylamino)-3"-propyl-4"-methoxytriphenylmethane, 4. 4"-bis(N-benzyl-N-methylamino)-3#-methyl-4"ethoxytriphenylmethane, 4.4'-bisN-pyrrolidyl-
3″-methyl-4″-methoxytriphenylmethane, 4
．． 4'-bis-N-piperidyl-3"-methyl-4"-
Ethoxy-triphenylmethane, 4,4'-dimethylamino-3tert-butyl-4#-methoxy-triphenylmethane, etc.

(C) As the monoaminotriphenylmethane dye, 4.4'-dimethoxy-4"-dimethylaminotriphenylmethane, 4.4'-dimethoxy-3-methyl-4"
-methylaminotriphenylmethane, 4,4"-jethoxy-4"-diethylaminotriphenylmethane, 4,
4"-dimethoxy-4"-(N-benzyl-N-methylamino)-triphenylmethane, 3.3'-dimethyl-
4゜4'-dimethoxy-4-dimethylaminotriphenylmethane, 4.4'-dimethoxy-4#-pyrrolidinotriphenylmethane, 4.4'-dimethyl 4''-diethylaminotriphenylmethane, 4-methoxy-4 '-dimethylamino-triphenylmethane, etc.

(D) As a naphthyl-methane dye, bis(4-dimethylamino-naphthyl-1)-4'-dimethylaminophenylmethane, bis(4-ethylaminonaphthyl-1)
)-4'-dimethylaminophenylmethane, bis(4-
N-paratolyl-N-methylamino-naphthyl-1)-
4'-isopropylaminophenylmethane, tris(4
-dimethylamino-naphthyl-1)methane, bis(4-
Dimethylamino-naphthyl-1)-4'-N-morpholinophenylmethane, bis(4-diethylaminophenyl)-4'-N-phenylaminonaphthyl-1'-methane, bis(4-diethylaminophenyl)-4'- Ethylaminonaphthyl-1'-methane, bis(4-N-phenyl-N-methylaminonaphthyl-1)-β-styrylmethane, bis(4-dimethylamino-naphthyl-1)-p
-Chlorstyrylmethane, bis(4-dimethylaminophenyl)-2'-methoxynaphthyl-1'-methane, bis(4-dimethylaminophenyl)-4'-methoxynaphthyl-1'-methane, bis(4-dimethyl aminophenyl)-naphthyl 2'-methane, bis(4-N-propylaminophenyl)-4'-propoxynaphthyl-2-
Methane, bis(4-dimethylaminonaphthyl-1)-2
'-pyridylmethane, bis(4-dimethylaminonaphthyl-1)-2'-pyrazylmethane, bis(4-dibenzylaminonaphthyl-1)-quinolin-31-yl-methane, and the like.

(E) diphenyl-β-styrylmethane dyes, bis(4-dimethylaminophenyl)-β-styrylmethane, bis(3-methyl-4-N-phenylaminophenyl)-β-styrylmethane, bis( 4-N-benzyl-N-methylaminophenyl)-β-styrylmethane,
Bis(4-dimethylaminophenyl)-β-(4'-dimethylaminostyryl amethane, bis(4-dimethylaminophenyl)-β-(4'-methoxystyryl)-methane, bis(4-diethylaminophenyl)- β-(3
'-Methyl-4'-ethoxystyryl)methane, bis(
3-Methyl-4-ethoxyphenyl)-β-(4'-diethylaminostyryl)-methane, 4-methylphenyl-4'-diethylaminophenyl-β-(3'-te
rt-butyl-4'dimethylaminostyryl)-methane, etc.

(F) As the indolylmethane dye, phenyl-bis(1-ethyl-2-methyl-indol-3-yl)methane, 4-methoxyphenyl-bis(1'-ethyl-2
1-methylindol-3'-yl)methane, 3-methyl-4-methoxyphenyl-bis(1'-ethyl-2'
-methylindol-3'-yl)methane, 3,4-dimethoxyphenyl-bis(1'-ethyl-2'-methylindol-3'-yl)methane, 2゜4-dimethoxyphenyl-bis(1'- Ethyl 2'-methylindol-3'-yl)methane, 3,4-jethoxyphenyl-
Bis(1'-ethyl-2'-methylindole-3'-
yl)methane, 3-butyl-4-methoxyphenyl-bis(1'-butyl-2'-methylindol-3'yl)methane, 4-ethoxyphenyl-bis(1-ethyl-
2'-phenylindol-3'yl)methane, 4-ethoxyphenyl-bis(1-ethyl-2'-methyl-indol-3'yl)methane, phenyl-bis(1'-
n-butyl-2'-methyl-indol-3'-yl)
Methane, phenyl-bis(1'-methyl-2'-phenylindol-3'-yl)methane, bis(4-dimethylaminophenyl)-(1'-ethyl-2'-methyl-
indol-3'-yl)methane, bis(l-ethyl-
2-Methyl-indol-3-yl)-2'-naphthylmethane, bis(1-ethyl-2-methyl-indole-
3-yl)-1'-naphthylmethane, tris(1-ethyl-2-methyl-indol-3-yl)methane, tris(1-n-butyl-2-methylindol-3-yl)
Methane, bis(1-ethyl-2-methyl-indole-
3-yl)-3'-chloro-4'-methoxyphenylmethane, bis(1-propyl-2-phenyl-indol-3-yl)-phenylmethane, bis(1-octyl-
2-methyl-indol-3-yl)phenylmethane,
Bis(1-benzyl-2-methyl-indol-3yl)phenylmethane, bis(1-ethyl-2-methyl-indol-3-yl)-2'-methylphenylmethane,
Bis(1-ethyl-2-methyl-indol-3-yl)-3'-methylphenylmethane, bis(1-ethyl-
2-Methyl-indol-3-yl)-4'-methylphenylmethane, bis(1-ethyl-2-methyl-indol-3-yl)-2'-methoxyphenylmethane, bis(l-ethyl-2- methyl-indol-3-yl)
-4'-florphenylmethane, bis(l-ethyl-2
-methyl-indol-3-yl)-4'-bromphenylmethane, bis(1-hexyl-indol-3-yl)-phenylmethane, bis(1-ethyl-2-methyl-indol-3-yl) -3'-nitrophenylmethane, bis(1-ethyl-2-methyl-indol-3yl)-3',4'-dichlorophenylmethane, bis(1
-ethyl-2-methyl-indol-3yl)-2'-
Thienylmethane, bis(1-ethyl-2-methyl-indol-3-yl)-4methyl-2'-thienylmethane, bis(1-butyl-2-methyl-indol-3-yl)-4'-pyridyl such as methane.

(G) Other leucomethine pigments include 3,6-bis-dimethylamino-9-phenylxanthine, 3,6
-bis-diethylamino-9-phenylxanthine, 3
．． 6-bis-dimethylamino-9-(3'-methyl-4
'-dimethylaminophenyl)xanthine, 3-diethylamino-6,7-dimethyl-9-phenylxanthine, 3,6-simethoxy9-(4'-dimethylaminophenyl)xanthine, 3,6-thiethoxy9-(4'
-dimethyl-naphthyl-1')xanthine, 3,6-bis(N-methyl-N-phenylamino)-9-(3',
4'-dimethoxyphenyl)xanthine, 3,6-bis-dimethylamino 9-phenylthioxanthine, 3,6
-Simethylamino-9-(4'-methoxyphenyl)-
10-Methyl-9,IO-dihydroacridine, 36-
Examples include pisdimethylamino-9-(4'-dimethylaminophenyl)fluorene, but are not limited to these exemplified compounds.

The oxidizing organic compound is one that melts into contact with the methine dye by heating and oxidizes the methine dye to give an oxidized colored image, and for example, quinone derivatives are used. As this quinone derivative, for example, 2.3-
dicyano-5,6-dichloro-1,4-benzoquinone,
2.3.56-tetracyano-1,4-benzoquinone,
3゜4-dibromo-5,6-dicyano-1,2-benzoquinone, 3,4,5.6-titracyano 1゜2-benzoquinone, 2,3,5.6-tetrabromo-1,4-benzoquinone, 2 ,3,5.6-tetraiodo-1,4-
Benzoquinone, 2,3.56-thitramethoxycarbonyl-1,4-benzoquinone, 2.3.5.6-thitraethoxycarbonyl-1,4-benzoquinone, 2,3.
a.

6-Chitora i-butoxycarbonyl-1,4benzoquinone, 2,3,5,6-tetra-nhexyloxycarbonyl-1,4-benzoquinone, 2,3,5,6-Chitora (2'-ethylhexyl oxycarbonyl)-1,
4-benzoquinone, 2,3,5,6-titradodecyloxycarbonyl-1,4-benzoquinone, 2,3,5
．． 6-titraphenoxycarbonyl-1,4-benzoquinone, 2,3,5.6-tetra-p-tolyloxycarbonyl-1,4-benzoquinone, 2.35.6-titrabenzyloxycarbonyl-14-benzoquinone ,2
,3,5.6-titranaphthoxycarbonyl-1,4-
pen7'-1-/n, 34.5.6-chitraprobyloxycarbonyl-1,2-benzoquinone, 3,4.5
．． 6-tetra-n-butoxycarbonyl-1,2-benzoquinone, 2,5-dimethoxycarbonyl-3,6dichloro-1,4-benzoquinone, 2,5-jethoxycarbonyl-3,6-dipromo-1,4-benzoquinone ,2
．． 5-di-me-butoxycarbonyl-3,6-dipromo-1,4-benzoquinone, 2,5-di-n-octoxycarbonyl-3゜6-dipromo-1,4-benzoquinone, 2,5-diphenoxycarbonyl- 3,6-diiodo-14-benzoquinone, 2,5-dibenzyloxy-3
, 4-dichloro-19,2-benzoquinone, 36-';
-n-pentyloxycarbonyl-3゜4-dichloro-
1,4-benzoquinone, 2,5-benzyloxycarbonyl-1,4-benzoquinone, 2,5-dibenzoyl-
3,6-dichloro-1,4-benzoquinone, 2,5-dibenzoyl-3,6-dipromo-1,4-benzoquinone, 2゜5-dibenzoyl-3-bromo-1,4-benzoquinone, 2,5-diacetyl -3,6-dipromu1.
4-benzoquinone, 2,5-jethoxycarbonyl-3
, 6-cyphenylsulfonyl-1°4-benzoquinone,
2,5-di-n-butoxycarbonyl-3,6-di4
'-Tolylsulfonyl-1,4-benzoquinone, 2.5
-di-n-hexyloxycarbonyl-3,6-siphenylsulfonyl-1,4-benzoquinone, 2,5-di-i-brobyloxycarbonyl-3,6-di-p-tolylsulfonyl-1,4-benzoquinone , 2゜5-di-mybutoxycarbonyl-3,6-di-p-cyclohexylphenylsulfonyl-1,4-benzoquinone, 2,5
-di(2'-ethylhexyloxycarbonyl)-3
, 6-di-4'-diphenylylsulfonyl-1,4-benzoquinone, 2,5-di-n-propyloxycarbonyl-36-di-4'-chlorophenylsulfonyl-14-
Benzoquinone, 2,5-jethoxycarbonyl-3,6
-';-4'-methoxyphenylsulfonyl-1,4-
Benzoquinone, 2,5-di-benzyloxycarbonyl-3,6-di4'-tolylsulfonyl-1,4-benzoquinone, 2,5-di-n-octyloxycarbonyl-3,6-ethylsulfonyl-1 , 4-benzoquinone, 2,5-jethoxycarbonyl-3,6-(2'-
naphthylsulfonyl)-1,4-benzoquinone, 2.5
-di-methoxycarbonyl-3-tolylsulfonyl-
1,4-benzoquinone, 3.6-jethoxycarbonyl-4,5-diphenylsulfonyl-1,2-benzoquinone, 2.3,5.6-tetra-4'-tolylsulfonyl-1,4-benzoquino. 2,3.5.6-thitraphenylsulfonyl-1,4-benzoquinone, 2.
3. 5.6-thitraethylsulfonyl-1,4-benzoquinone, 3,4,5.6-thitraethylsulfonyl-1,2-benzoquinone, 2,3.56-tetra-n-octylsulfonyl-14- Benzoquinone, 2.
3.5.6-chitrapenzyloxysulfonyl-1,
4-benzoquinone, 2,5-di-n-propyloxycarbonyl-36-dibenzoyl-1,4-benzoquinone, 25-di-butoxycarbonyl-3-benzoyl-1,4-benzoquinone, 2,3-dichloro- 1,4-
Benzoquinone-5,6-dicarboxylic acid butylimide, 1
．． 4-benzoquinone-2,3゜5.6-tetracarboxylic acid-diphenylimide, 1,2-benzoquinone-3,4
, 5,6-tetracarboxylic acid-di-n-octylimide, 2,5-di-ethoxysulfonyl-1,4-benzoquinone, 2,5-diphenoxysulfonyl-3,6-dichloro-1,4-benzoquinone, 2,5-di-n-butoxycarbonyl-3,6-diptoxysulfonyl-1,4-
Benzoquinone, 2,5-di-lytolylsulfonyl-3
, 6-dipromo-1,4-benzoquinone, 2,5-di-n-hexylsulfonyl-3,6-dichloro-1,4-
Benzoquinone derivatives such as benzoquinone, 3.3', 5
．． 5-tetrachlor-4,4'-diphenoquinone, 3.
3', 5°, 5'-tetracyano-4,4'-diphenoquinone, 2.2', 3.3', 5.5'6.6'-octachlor-4,4'-diphenoquinone, 2.2', 3.3
'-tetracyanol 55', 6.6'-tetrabromo-
4,4'-diphenoquinone, 3.3',5.5'-tetraethoxycarbonyl-4,4'-diphenoquinone, 3
3',5,5'-tetrabenzyloxycarbonyl-2
,2',6.6'-tetrabromo-4°4'-diphenoquinone, 3.3',5.5'-te)cyp-tolylsulfonyl-4,4'-diphenoquinone, 3.3',5.
5'-tetra-ethoxysulfonyl-4,41-diphenoquinone, 33'-dibentyloxysulfonyl-5,
5'-Dibentyloxycarbonyl-4,4'-diphenoquinone, 3.3',5.5'-tetra-n-propyloxycarbonyl-2,2',6.6'-tetrachloro-4,4'-stilbene Quinone, 2.2', 3.3',
Diphenoquinone derivatives or stilbenequinone derivatives such as 5.5',6.6'-octachlor-4,4'-stilbenequinone, 2,3-dichloro-4,4'-diphenoquinone, and 2'3'-dicarboxylic acid ethyl imide; Oxidizing quinone derivatives (electron acceptors) such as naphthoquinone derivatives, naphthoquinone derivatives, anthradiquinone derivatives, and 2,3-dicyano-1,4-naphthoquinone are used, but the compounds are not limited to these exemplified compounds. do not have.

Additionally, at least one of an alkanolamine and a sequestering agent is used to stabilize the methine dye.
Different types may be mixed. As an alkanolamine,
Examples include the following compounds.

(1) As alkanolamines having a tertiary amino group, tris-N-(2-hydroxyethyl)amine,
Tris-N-(2-hydroxypropyl)amine, Tris-N-(3-hydroxypropyl)amine, Tris-
N-(hydroxybutyl)amine, N,N-dimethyl-
N=(2-hydroxyethyl)amine, N, N-diethyl-N-(2-hydroxyethyl)amine, N, N-dipropyl-N-(2-hydroxyethyl)amine, N,
N-dibutyl-N-(2-hydroxyethyl)amine,
N-Methyl-N-phenyl-N-(2-hydroxyethyl)amine, N,N-diphenyl-N-(2-hydroxyethyl)amine, N.

N-dimethyl-N-(2-hydroxypropyl)amine, N,N-diethyl-N-(2-hydroxypropyl)
Amine, N,N-dipropyl-N-(2-hydroxypropyl)amine, N,N-dibutyl-N-(2-hydroxypropyl)amine, N,N-diphenyl~N=(2
-hydroxypropyl)amine, N-methyl-N,N-
di(2-hydroxyethyl)amine, N-ethyl-N,
N-di(2-hydroxyethyl)amine, N-phenyl-N, N-di(2-hydroxyethyl)amine, N-
Methyl-N,N-di(2-hydroxypropyl)amine, N-acetyl-N,N-di(2-hydroxyethyl)
Amine, N-acetyl-N, N-di(2-hydroxypropyl)amine, N-hydroxyethylmorpholine,
N-hydroxypropylmorpholine, N-tetradecyl-N, N-di(ω-hydroxyethylpolyoxyethylene)amine, N-dodecyl-N, N-di(ω-hydroxyethylpolyoxyethylene)amine, N-octadecyl- N,N-di(ω-hydroxyethylpolyoxyethylene)amine, N,N-dodecyl-N(ω-hydroxyethylpolyoxyethylene)-amine, N,N-di(
cis-octadecenyl)-N-(ω-hydroxyethylpolyoxyethylene)amine, N,N-dioctadecyl-N-(.

ω-hydroxyethylpolyoxyethylene) amines, compounds obtained by adding alkylene oxide to aliphatic diamines, N,N-ω-hydroxyalkylpolyoxyalkylene substituted products of aliphatic amide, reaction products of ammonia and glycidol (2-amino -propylene glycol derivatives), etc.

(2) As alkanolamines having a secondary amino group, N,N-di(2-hydroxyethyl)amine, N
, N-di(2-hydroxypropyl)amine, N, N-
Di(hydroxybutyl)amine, N-methyl-N-(2
-hydroxyethyl)amine, N-butyl-(2-hydroxyethyl)amine, N-dodecyl-N-(2-hydroxyethyl)amine, N-phenyl-N(2-hydroxypropyl)amine, N-acetyl-N -(2-hydroxyethyl)amine, N-acetyl-N(2-hydroxypropyl)amine, N-(2-hydroethyl)-piperazine, N-(2-hydroxypropyl)piperazine, and the like.

(3) As alkanolazines having a primary amino group, N-(2-hydroxyethyl)amine, N-(2-hydroxyethyl)amine,
-hydroxypropyl)amine, N-(hydroxybutyl)amine, N-(1,3-dihydroxy-2-methyl-propyl-2)amine, N-(2,3-dihydroxypropyl)amine, N-(2, 3-dihydroxy-propyl-2)amine, N-(1,3-dihydroxy-2-
butyl)amine, N-(1-aminomethyl-2-hydroxyethyl)amine, N-(2-hydroxy-3-amino-propyl)amine, etc.

In addition, as a metal ion sequestering agent, ethylenediaminetetraacetic acid, N-hydroxyethyl-ethylenediamine-
N,N',N'-) diacetic acid, diethylenetriaminepentaacetic acid, triethylenetetraminepentaacetic acid, nitrilotriacetic acid, N-hydroxyethyl-iminodiacetic acid, jetanolglycine, ethylenediamine-N,N'-diacetic acid, glycol ether diamine Tetraacetic acid, 1.3-
Organic water-soluble sequestering agents such as diaminopropan-2-ol tetraacetic acid, tartaric acid, citric acid, gluconic acid, sugar acids and their alkali metal salts, polyacrylates, metal salts of ligninsulfonic acid, N,N '-Schiff bases such as disalicylidene ethylene diamine, 1,3-diketones such as trifluoroacetylacetone, thenoyl trifluoroacetone, pivaloyl trifluoroacetone,
Examples include organic metal ion sequestering agents soluble in dye solvents such as higher amide derivatives of ethylenediaminetetraacetic acid, and polymerized phosphates such as sodium tripolyphosphate, sodium polymetaphosphate, sodium pyrophosphate, and sodium dihydrogen birophosphate.

Furthermore, a covering layer 16 is formed on the thermosensitive coloring layer 14. The coating layer 16 includes a pigment in which the surface of natural mica is coated with at least one of titanium oxide and iron oxide.

- When light enters a laminate of transparent thin films while fishing on a boat, multiple reflections occur, and light interference occurs due to the optical thickness (product of geometric thickness and refractive index) of the transparent thin film material. By forming a thin film of titanium oxide or iron oxide on the surface of natural mica, a portion of the incident light (for example, the green component) is reflected, and its complementary color (for example, the red component) is transmitted, resulting in reflected and transmitted colors, respectively. Becomes a color. Therefore, the color tone of the thermosensitive recording paper 10 appears different depending on the color of the background of the coating layer 16. For example, if the background is white, the transmitted color will be reflected and both the reflected color and the transmitted color will be visible. Furthermore, when the background is black, the transmitted color is absorbed and only the reflected color is visible. In this way, in this thermal recording paper 10, depending on the color of the background of the coating layer 16, it is possible to obtain a recording paper having an unprecedented color tone.

Example 1 In 100 parts by weight of a 5% aqueous solution of polyvinyl alcohol as a water-soluble binder, a black leuco dye (PSD-T manufactured by Nisso Kako Co., Ltd.) was added.
121) 7 parts by weight, 10 parts by weight of clay, and 3 parts by weight of stearic acid amide powder were mixed and dispersed in a centrifugal rotating ball mill for 5 hours to prepare Solution A. Furthermore, in 100 parts by weight of a 5% aqueous solution of water-soluble binder polyvinyl alcohol,
7 parts by weight of bisphenol A, 10 parts by weight of clay, and 3 parts by weight of stearic acid amide powder were mixed and dispersed in a centrifugal rotating ball mill for 5 hours to prepare liquid B. Then, liquid A and liquid B were mixed and stirred at a ratio of 1:3 to obtain a uniformly dispersed paint. The obtained paint was 64g/rrl with a Mayer bar.
Coat it on high-quality paper so that the dry coating amount is 8 g / d,
The paper was air-dried at 60° C. for 3 minutes to obtain thermal paper.

In addition, 5 parts by weight of Iriodin 200 manufactured by Merck Japan Co., Ltd. was added to 100 parts by weight of a 5% polyvinyl alcohol aqueous solution.
Parts by weight were added and stirred for 30 minutes using a homomixer to obtain a coating layer coating material. Then, coating layer paint was applied on the above-mentioned thermal paper so that the dry weight was 5 g/rrr, and
It was dried at ℃ for 3 minutes to obtain the thermal recording paper of the present invention.

This thermosensitive recording paper was colored for 1 second at a temperature of 130° C. and a pressure of 2 kg/cni using a recuperating gradient tester manufactured by Toyo Seiki Seisakusho. At this time, the colored area exhibited an unprecedented golden color tone, and the non-colored area exhibited pearlescent luster.

Example 2 A thermosensitive recording paper was obtained in the same manner as in Example 1, except that Iriodin 100 manufactured by Merck Japan Co., Ltd. was used as the material for the coating layer coating material. In this thermosensitive recording paper, the colored areas exhibited silver color, and the non-colored areas exhibited pearlescent luster.

Example 3 A thermosensitive recording paper was obtained in the same manner as in Example 1, except that Iriodin 219 manufactured by Merck Japan Co., Ltd. was used as the material for the coating layer coating material. In this thermosensitive recording paper, the colored areas exhibited purple color, and the non-colored areas exhibited pearlescent luster.

[Brief explanation of the drawing]

The figure is a sectional view showing an embodiment of the present invention. In the figure, 10 is thermal recording paper, 12 is a sheet base material, 1
4 represents a thermosensitive coloring layer, and 16 represents a covering layer.

Claims (1)

[Scope of Claims] A sheet base material, a heat-sensitive coloring layer formed on the surface of the sheet base material and developing color by heating, and a covering layer formed on the heat-sensitive coloring layer, wherein the covering layer is made of natural A heat-sensitive recording paper comprising a pigment coated with at least one of titanium oxide and iron oxide on the surface of mica.