JP3315831B2 - Reversible thermosensitive recording material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a reversible thermosensitive recording material capable of forming and erasing an image, wherein a stable image can be formed by heating / coloring / erasing many times by heating.

[0002]

2. Description of the Related Art A thermosensitive recording material generally comprises a support provided with a thermosensitive recording layer mainly comprising an electron-donating usually colorless or pale-color dye precursor and an electron-accepting developer. By heating with a thermal head, a hot pen, a laser beam, or the like, the dye precursor and the color developer react instantaneously to obtain a recorded image. JP-B-43-4160, JP-B-45-14039 And so on.

In general, it is impossible for such a heat-sensitive recording material to form an image once and erase that portion and return to the state before image formation. There was no choice but to add to the formation. For this reason, when the area of the heat-sensitive recording portion is limited, there has been a problem that the recordable information is limited and all necessary information cannot be recorded.

In recent years, reversible thermosensitive recording materials capable of repeatedly forming and erasing images have been devised to address such problems. For example, JP-A-54-119377 and JP-A-63-119377 disclose a reversible thermosensitive recording material. 39377, JP-A-63-4
Japanese Patent No. 1186 describes a heat-sensitive recording material composed of a resin base material and an organic low-molecular compound dispersed in the resin base material. However, in this method, the transparency of the heat-sensitive recording material is reversibly changed by heat energy, so that the contrast between the image forming portion and the non-image forming portion is insufficient.

In the methods described in Japanese Patent Application Laid-Open Nos. 50-81157 and 50-105555, since the image to be formed changes according to the environmental temperature, the image forming state and the erasing state are changed. Are different from each other, and these two states cannot be maintained for an arbitrary period at room temperature.

Further, Japanese Patent Application Laid-Open No. Sho 59-120492 discloses that an image forming state is controlled by keeping a recording material in a hysteresis temperature range by utilizing a hysteresis characteristic of a coloring component.
Although a method for maintaining the erased state is described, this method requires a heating source and a cooling source for image formation and erasure, and the temperature range in which the image formation state and the erased state can be maintained is limited to the hysteresis temperature range. However, it is still insufficient for use in the temperature environment of daily life.

On the other hand, JP-A-2-188293, JP-A-2-188294, and International Publication No.
No. 11898 describes a reversible thermosensitive recording medium comprising a leuco dye and a color-reducing agent which causes the leuco dye to develop and decolor the color by heating. The color-developing agent is an amphoteric compound having an acidic group for coloring the leuco dye and a basic group for decolorizing the colored leuco dye, and has a coloring effect by an acidic group or a decolorizing effect by a basic group by controlling thermal energy. One is preferentially generated to perform color development and decoloration. However, in this method, it is impossible to completely switch between the coloring reaction and the decoloring reaction only by controlling the heat energy, and since both reactions occur at a certain ratio at the same time, a sufficient coloring density cannot be obtained. Can't do it perfectly. Therefore, sufficient image contrast cannot be obtained.

Further, since the decolorizing action of the basic group also acts on the color-developed portion at room temperature, a phenomenon that the density of the color-developed portion decreases with time cannot be avoided. Further, JP-A-5-124360 describes a reversible thermosensitive recording medium that develops and decolorizes a leuco dye by heating, and as an electron accepting compound, an organic phosphoric acid compound, an α-hydroxy aliphatic carboxylic acid, Specific phenolic compounds such as fatty acid dicarboxylic acids and alkylthiophenols having an aliphatic group having 12 or more carbon atoms, alkyloxyphenols, alkylcarbamoylphenols, and alkyl gallates are exemplified. However, even with this recording medium, the two problems of low color density or incomplete erasing cannot be solved at the same time.

On the other hand, image formation with good contrast
A novel reversible developer capable of being erased and capable of maintaining a stable image over time in an environment of daily life has been found, and has been previously proposed in Japanese Patent Application No. Hei 4-347032. . However, although the reversible thermosensitive recording material obtained by this method can form and erase images with good contrast, it has a drawback that the erased portion turns yellow when color development / erasure is repeated many times. Was.

[0010]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a reversible thermosensitive device capable of forming an image and erasing the image by heating, stably performing color development / erasing many times, and not causing yellowing of an erased portion. It is to provide a recording material.

[0011]

Means for Solving the Problems The inventors of the present invention have conducted research to solve this problem, and as a result, have found that one or more intermediate layers provided directly above the reversible thermosensitive recording layer or directly above the reversible thermosensitive recording layer. Immediately above, dihydrophobicized with an organosilicon compound
-Hydrophobic with n-butylamine value of 100 meq / kg or less
Ri Do a UV-curable or electron beam curable resin containing particles of hydrophobic silica having a gender, by constituting the protective layer ing by curing this stable images in printing / erasing multi number formed can, and erasing unit was able to made create a yellowing not reversible heat-sensitive recording material.

[0012] Hydrophobic silica is a compound in which a hydroxyl group contained in porous synthetic silica is converted into an organosilicon compound such as silanes.
It is completely hydrophobized by chemical reaction with silazanes, polysiloxanes and the like, and has a di-n-butylamine value of 100 meq / kg or less. The method for producing the porous synthetic silica and the organosilicon compound includes a method performed in an organic solvent, a pressure method, a catalyst heating method, and the like, which are already known.

[0013] Hydrophobic silica is completely hydrophobic due to the small number of hydroxyl groups present on the particle surface, while its adhesion to organic solvents and solvent-based binders is superior to that of porous synthetic silica untreated on the particle surface. . For this reason, it has better compatibility and dispersibility with ultraviolet curable or electron beam curable resins than ordinary porous synthetic silica.

A reversible thermosensitive recording material may be exposed to extremely severe conditions when developing a color.
The hydrophobized silica is used under the condition that the color is pressed against the aggregate of the micro heating elements generating heat at a temperature of 00 ° C. or more with a strong pressure, and at the same time, the color is formed while sliding the assembly of the reversible thermosensitive recording material and the micro heating element. As a result, the contact area with the minute heating element is reduced, so that the protective layer is hardly broken,
In addition, the hydrophobized silica itself does not break or melt due to its heat or pressure, and these effects are maintained even when the color is developed many times. Thus, a stable image can be formed even with a large number of color developments / erasures. Further, the good dispersibility of the hydrophobic silica makes it possible to uniformly disperse the protective layer made of an ultraviolet-curable or electron-beam-curable resin. As a result, the heat resistance of the protective layer is improved, and no yellowing of the decolored portion due to multiple color development / erasing is observed. The effect will be shown in the following example.

The hydrophobic silica particles in the protective layer used in the present invention have an average particle diameter of 1 to 10 μm, preferably 1 to 10 μm.
It is 5 μm, and the compounding amount is 3 to 30% by weight, preferably 5 to 20% by weight. This is kneaded with an electron beam-curable resin or an ultraviolet-curable resin in a mortar, a three-roll mill, or the like, or dispersed in a solvent with hydrophobic silica particles, and further dispersed in an electron beam-curable resin or an ultraviolet-curable resin. For example, particles of hydrophobic silica are contained.

Further, in order to prevent or reduce sticking after the electron beam-curable resin or the ultraviolet-curable resin is cured, a pigment may be contained in the electron beam-curable resin composition together with the hydrophobic silica particles. .
The pigment referred to here may be either an organic pigment or an inorganic pigment. For example, diatomaceous earth, clay, calcined clay, talc, kaolin, calcined kaolin, calcium carbonate, magnesium carbonate, titanium oxide, zinc oxide, aluminum hydroxide, starch granules, urea-formalin resin, synthetic resin particles such as melamine resin and the like. But are not limited to these. These pigments can be used alone or in combination of two or more.

Further, for the purpose of preventing sticking and head abrasion, higher fatty acid metal salts such as zinc stearate and calcium stearate, and waxes such as paraffin, paraffin oxide, polyethylene, polyethylene oxide, stearic amide, and caster wax. Further, one or two or more of a leveling agent, a dispersant, a surfactant, a fluorescent dye and the like can be contained.

The generally colorless or light-colored electron-donating dye precursor used in the present invention is typified by those generally used for pressure-sensitive recording paper, heat-sensitive recording paper and the like, but is not particularly limited. Specific examples include, for example, the following, but the present invention is not limited thereto.

(1) Triarylmethane compound 3,3-bis (p-dimethylaminophenyl) -6-dimethylaminophthalide (crystal violet lactone), 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- (p-dimethylaminophenyl) -3- (2-phenylindole-
3-yl) phthalide, 3,3-bis (1,2-dimethylindol-3-yl) -5-dimethylaminophthalide, 3,3-bis (1,2-dimethylindole-3-
Yl) -6-dimethylaminophthalide, 3,3-bis (9-ethylcarbazol-3-yl) -5-dimethylaminophthalide, 3,3-bis (2-phenylindol-3-yl) -5 -Dimethylaminophthalide, 3-p
-Dimethylaminophenyl-3- (1-methylpyrrol-2-yl) -6-dimethylaminophthalide and the like,

(2) Diphenylmethane compounds 4,4'-bis (dimethylaminophenyl) benzhydryl benzyl ether, N-chlorophenylleuco auramine, N-2,4,5-trichlorophenyl leuco auramine, etc.

(3) Xanthene compounds rhodamine B anilinolactam, rhodamine Bp-chloroanilinolactam, 3-diethylamino-7-dibenzylaminofluoran, 3-diethylamino-7-octylaminofluoran, 3- Diethylamino-7-phenylfluoran, 3-diethylamino-7-chlorofluorane, 3-diethylamino-6-chloro-7-methylfluoran, 3-diethylamino-7- (3,4-dichloroanilino) fluoran, 3 -Diethylamino-7
-(2-chloroanilino) fluoran,

3-diethylamino-6-methyl-7-anilinofluoran, 3- (N-ethyl) tolylamino-
6-methyl-7-anilinofluoran, 3-piperidino-6-methyl-7-anilinofluoran, 3- (N-ethyl) tolylamino-6-methyl-7-phenethylfluoran, 3-diethylamino-7 -(4-nitroanilino) fluoran, 3-dibutylamino-6-methyl-7
-Anilinofluoran, 3- (N-methyl) propylamino-6-methyl-7-anilinofluoran, 3- (N
-Ethyl) isoamylamino-6-methyl-7-anilinofluoran, 3- (N-methyl) cyclohexylamino-6-methyl-7-anilinofluoran, 3- (N-
Ethyl) tetrahydrofurylamino-6-methyl-7-
Anilino fluoran, etc.

(4) Thiazine compounds Benzoyl leucomethylene blue, p-nitrobenzoyl leucomethylene blue, etc.

(5) Spiro compounds 3-methylspirodinaphthopyran, 3-ethylspirodinaphthopyran, 3,3'-dichlorospirodinaphthopyran, 3-benzylspirodinaphthopyran, 3-methylnaphtho- (3 -Methoxybenzo) spiropyran, 3-propylspirobenzopyran and the like.

The above colorless or pale color dye precursors may be used alone or in combination of two or more.

The reversible developer used in the present invention is described below, but is not limited thereto.

The reversible developer used in the present invention is not particularly limited as long as it is a compound capable of causing a reversible color tone change in the dye precursor upon heating. 6-210954
An electron-accepting compound represented by the following formula 1 is preferably used, including a reversible color developing agent comprising a phenolic compound proposed in JP-A No. 6-284.

[0028]

Embedded image

In Formula 1, n represents 1, 2 or 3. m represents 0, 1 or 2. Q represents an aliphatic hydrocarbon group, an alkoxy group, or a halogen atom. The ring represented by A is an aromatic ring. X is a divalent group bonded to the aromatic ring represented by A via a nitrogen atom, a divalent group containing two or more hetero atoms, a nitrogen atom-containing aromatic ring represented by A, It represents a divalent group bonded by the above hydrocarbon group, or a divalent group containing an unsaturated bond or an aromatic ring. R represents an aliphatic hydrocarbon group. The total number of the atoms included in X and R excluding the hydrogen atoms and the atoms constituting the aromatic ring is 8 or more.

[0030] Specific examples of the substituents represented by Q are methyl, ethyl, propyl, isopropyl, n-
Butyl group, t-butyl group, t-pentyl group, 2-ethylhexyl group, cyclohexyl group, aliphatic hydrocarbon group such as allyl group, methoxy group, ethoxy group, n-propyloxy group, i-propyloxy group, n -Butyloxy group, n
An alkoxy group such as an octyloxy group; and a halogen atom such as fluorine, chlorine, bromine and iodine.

[0031] X is, as examples of the divalent group bonding to an aromatic ring represented by A through a nitrogen atom, -NHCO -, -
NH-, -NHCONH-, -NHCONHNH-,-
N = CH -, - N = N -, - NHSO 2 -, - NHCO
_{(P-C 6 H 4)} NHCO -, - NHCO (p-C 6 H 4)
NHCONH -, - NHCO (p- C 6 H 4) NHCOC
ONH -, - NHCO (p- C 6 H 4) CONH -, - N
_{HCO (p-C 6 H 4} ) CONHNHCO -, - NHCO
_{(P-C 6 H 4)} OCONH -, - NHCO (p-C
_{6 H 4) NHCOO -, -} NHCOCH 2 (m-C 6 H 4)
_{NHCO-, -NHCOCH 2 (p-C} 6 H 4) NHCO
_{-, - NHCOCH 2 (p-} C 6 H 4) NHCONH-,
_{-NHCOCH 2 (p-C 6 H} 4) NHCOCONH-,
_{-NHCOCH 2 (p-C 6 H} 4) CONH -, - NHC
_{OCH 2 (p-C 6 H} 4) CONHNHCO -, - NHC
_{OCH 2 (p-C 6 H} 4) CONHNHCONH -, - N
HCOCH ₂ (p-C ₆ H ₄ ) CONNHNHCOO-,-
_{NHCOCH 2 (p-C 6 H} 4) OCONH -, - NHC
_{OCH 2 (p-C 6 H} 4) NHCOO-, -NHCOCH
_{2 CH 2 (p-C 6} H 4) NHCO -, - NHCOCH 2 C
_{H 2 (p-C 6 H} 4) NHCONH -, - NHCOCH 2 C
_{H 2 (m-C 6 H} 4) NHCOO -, - NHCOCH 2 CH
_{2 (p-C 6 H 4} ) NHCOCONH -, - NHCOCH 2
_{CH 2 (p-C 6 H} 4) CONH -, - NHCOCH 2 CH
_{2 (p-C 6 H 4} ) CONHNHCO -, - NHCOCH 2
_{CH 2 (p-C 6 H} 4) CONHNHCONH- the like. When a hydrogen atom is bonded to the nitrogen atom, the hydrogen atom may be substituted with an aliphatic hydrocarbon group such as a methyl group or a cyclohexyl group. Among these, a urea bond is more preferable in terms of decoloring property and image density. Interestingly, when X is -CONH-, -COO-, -S-
Either the decoloring property or the image density becomes unsatisfactory.

[0032] X is, as examples of the divalent group containing a hetero atom two or _{more, -SO 2 NH -, - S} -S -, - CON
_{HNH -, - CONHNHCO-, -CONHCH 2} C
O -, - CONHNHCOO -, - CONHCH 2 CO
_{O-, -CONHNHCONH -, - CONHCH 2} C
ONH-, -CONHNHCONHNH-, -CON
_{HCH 2 CONHNH -, - CH 2} NHCONH -, - C
_{H 2 CH 2 NHCONH -, -} CH 2 CH 2 CH 2 NHCO
_{NH -, - CH 2 CH 2} CH 2 NHCONH -, - SCH 2
_{CONH -, - SCH 2 CH 2} CONH -, - S (C
_{H 2) 5 CONH-, -S (} CH 2) 10 CONH -, - S
_{(P-C 6 H 4)} CONH -, - SCH 2 NHCO -, -
_{SCH 2 CH 2 NHCO -, -} S (CH 2) 6 NHCO-,
_{-S (p-C 6 H 4} ) NHCO -, - SCH 2 NHCON
_{H -, - SCH 2 CH 2} NHCONH-, -S (CH 2)
_{6 NHCONH -, - S (p} -C 6 H 4) NHCONH
_{-, - S (CH 2)} 10 NHCONH -, - SCH 2 CH 2
_{NHCOO-, -S (CH 2) 6} NHCOO -, - S
_{(P-C 6 H 4)} NHCOO -, - S (CH 2) 6 OCON
H -, - S (p- C 6 H 4) OCONH -, - S (C
_{H 2) 11 OCONH-, -SCH 2} CH 2 CONH -, -
_{S (CH 2) 5 CONH -} , - SCH 2 CH 2 NHCO (p
_{-C 6 H 4) -, -} SCH 2 CONHNHCO -, - SC
_{H 2 CH 2 CONHNHCO -, -} S (CH 2) 6 CONH
_{NHCO-, -S (CH 2) 6} CONHNHCO (p-
_{C 6 H 4) -, -} S (CH 2) 10 CONHNHCO-, -
_{S (p-C 6 H 4} ) CONHNHCO -, - SCH 2 (p
—C ₆ H ₄ ) CONHNHCO—, —SCH ₂ CH ₂ NH
_{COCONH -, - SCH 2 CH 2} CH 2 NHCOCON
H—, —S (CH ₂ ) ₁₁ NHCONH—, —S (p
_{-C 6 H 4) NHCOCONH-, -SCH} 2 CONHC
_{ONH -, - SCH 2 CH 2} CONHCONH -, - S
_{(P-C 6 H 4)} CONHCONH -, - SCH 2 CH 2 N
HCONHCO -, - S (p- C 6 H 4) NHCONHC
O—, —SCH ₂ CH ₂ CONHNHCONH—, —S
_{(CH 2) 10 CONHNHCONH -,} - SCH 2 CH 2
NHNHCONH -, - S (p- C 6 H 4) NHNHCO
_{NH -, - SCH 2 CH 2} NHCONHNH -, - S (p
—C ₆ H ₄ ) NHCONHNH—, —SCH ₂ CONHC
ONHNH-, -SCH ₂ CH ₂ CONHCONHNH
_{-, - S (CH 2)} 10 CONHCONHNH-, -S
(P-C ₆ H ₄ ) CONHNHCONH-, -S (p-C
_{6 H 4) CONHCONHNH -, -} SCH 2 CONHC
_{ONHNHCO -, - SCH 2 CH 2} CONHCONHN
_{HCO -, - S (CH 2} ) 10 CONHCONHNHCO
_{-, -S (p-C 6} H 4) CONHNHCONHCO
-, - S (p-C 6 H 4) CONHCONHNHCO-,
_{-SCH 2 CONH (CH 2) NHCO} -, - SCH 2 C
_{H 2 CONH (CH 2) NHCO} -, - S (p-C 6 H 4)
_{CONH (CH 2) NHCO -,} - S (CH 2) 10 CON
_{H (CH 2) NHCO -,} - SCH 2 CON (CH 2) N
_{HCONH -, - SCH 2 CH 2} CON (CH 2) NHC
_{ONH -, - S (CH 2} ) 10 CONHCONH (CH 2)
NHCO -, - S (p- C 6 H 4) CONH (CH 2) N
_{HCO -, - SCH 2 CH 2} NHCONH (CH 2) NH
_{CO -, - SCH 2 CH 2} NHCOCH 2 CONH -, -
_{S (p-C 6 H 4} ) NHCONH (CH 2) NHCO-,
—S (p—C ₆ H ₄ ) NHCOCH ₂ CONH— and the like. Specific examples of the hetero atom include an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, a boron atom, a silicon atom, a selenium atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom,
Tin atom and the like.

[0033] 2 X is, containing an unsaturated bond or aromatic ring
Examples of the valent group include -CH = CH-, -CH = N-,
—SO ₂ —, a phenylene group, a group containing a carbon-carbon triple bond and the like, a group obtained by combining them, and further, on one or both sides thereof, —NHCO
-, -NH-, -NHCONH-, -NHCSNH-,
-N = CH -, - N = N -, - NHSO 2 -, - SO 2 N
A group in which one or two or more linking groups such as H and -S-S- are combined is exemplified. In this case, as a connecting group, other than -CONH-, -O-, -S-, -COO-, -O
Divalent groups such as CO—, —OCOO, —CO—, and —SO ₂ — are also included.

[0034] X comprises a nitrogen atom, examples of the divalent group linked by an aromatic ring and a hydrocarbon group having 1 or more carbon represented by A, -CH ₂ CONH-, -CH ₂ CH ₂ CO
_{NH -, - CH 2 NHCO -} , - CH 2 CH 2 NHCO
_{-, - CH 2 CH 2 CH} 2 NHCO -, - CH 2 CH 2 NH
_{COO -, - (CH 2)} 6 NHCOO -, - (p-C
_{6 H 4) NHCOO -, -} CH 2 CH 2 OCONH-, -
_{(CH 2) 11 OCONH -,} - (p-C 6 H 4) OCON
_{H -, - CH 2 CH 2} CONHCO -, - (CH 2) 5 CO
_{NHCO -, - CH 2 CH 2} CONHCO (p-C 6 H 4)
_{-, -CH 2 CONHNHCO -, -} CH 2 CH 2 CON
_{HNHCO -, - (CH 2)} 5 CONHNHCO -, -
_{(CH 2) 5 CONHNHCO (p} -C 6 H 4) -, -
_{(CH 2) 10 CONHNHCO -,} - (p-C 6 H 4) C
_{ONHNHCO-, -CH 2 (p-C} 6 H 4) CONHN
_{HCO -, - CH 2 CH 2} NHCOCONH-, -CH 2
_{CH 2 CH 2 NHCOCONH -, -} (CH 2) 10 NHC
_{OCONH-, - (p-C 6} H 4) NHCOCONH
_{-, - CH 2 CONHCONH-, -CH} 2 CH 2 CON
HCONH -, - (p-C 6 H 4) CONHCONH-,
_{-CH 2 CH 2 NHCONHCO -, -} (p-C 6 H 4) N
_{HCONHCO -, - CH 2 CH 2} NHCONHNH-,
_{- (p-C 6 H 4} ) NHCONHNH -, - CH 2 CH 2 N
HNHCONH -, - (p-C 6 H 4) NHNHCONH
_{-, -CH 2 CONHNHCONH -, -} CH 2 CH 2 C
_{ONHNHCONH-, - (CH 2) 10} CONHNHC
ONH -, - (p-C 6 H 4) NHNHCO-, -CH 2
_{CONHCH 2 NHCO -, - CH 2} CH 2 CONHCH 2
_{NHCO -, - (CH 2)} 10 CONHCH 2 NHCO-,
_{- (p-C 6 H 4} ) CONHCH 2 NHCO-, -CH 2
_{CONHCH 2 NHCONH -, - CH 2} CH 2 CONH
_{CH 2 NHCONH-, - (CH 2} ) 10 CONHCH 2 N
HCONH -, - (p-C 6 H 4) CONHCH 2 NHC
_{ONH -, - CH 2 CH 2} NHCONHCH 2 NHCO
_{-, - (p-C 6} H 4) NHCONHCH 2 NHCO-,
_{-CH 2 CH 2 NHCOCH 2 CONH -} , - (p-C 6 H
₄ ) NHCOCH ₂ CONH— and the like.

As the aliphatic hydrocarbon group represented by R,
Hexyl, octyl, nonyl, cyclohexyl, decyl, undecyl, dodecyl, cyclododecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, 16-methylheptadecyl, octadecyl, 9-octadecenyl group, nonadecyl group, eicosyl group, henicosyl group,
Examples include a docosyl group, a tricosyl group, a tetracosyl group, a 2-norbornyl group, a 7,7-dimethylnorbornyl group, a 1-adamantyl group, a cholesteryl group, and a 5-phenylpentyl group. These may be branched, may be polycyclic, and may contain an unsaturated bond. However, it is necessary for the decoloring property that the total number of atoms excluding the hydrogen atom and the atoms constituting the aromatic ring among the atoms contained in X and R is 8 or more, especially 14 or more.

Next, specific examples of the reversible developer preferably used in the present invention, the present invention is not limited thereto.

[0037] 4'-hydroxy-heptane anilide, 4 '
-Hydroxy-3-methyloctaneanilide, 4'-hydroxynonadecaneanilide, 3'-hydroxynonadecaneanilide, 4'-hydroxy-10-octadeceneanilide, 15-cyclohexyl-4'-hydroxypentadecaneanilide, 4'- Hydroxy-5-tetradeceneanilide, 3'-cyclohexyl-4'-hydroxyheptadecaneanilide, 3'-allyl-4'-hydroxypentadecaneanilide, 3'-chloro-4'-hydroxyoctadecananilide, 3'-hydroxydodecane Anilide, 2 ', 4'-dihydroxyheptadecane anilide,

[0038] 4'-hydroxy-4-hexyl-benzanilide, 4'-hydroxy-4-octadecyl-benzanilide, 4'-hydroxy-4-pentadecyl aminocarbonyl benzanilide, 4'-hydroxy-4-hexyl-carbonylamino benz Anilide, 4'-hydroxy-4- (heptylthio) benzanilide, 4'-hydroxy-4-octadecyloxybenzanilide, 4 '
-Hydroxy-4-dodecylsulfonylbenzanilide, 4'-hydroxy-4-nonylsulfonyloxybenzanilide, 4'-hydroxy-4-dodecyloxysulfonylbenzanilide, 4'-hydroxy-4-pentadecylaminosulfonylbenzanilide, 4'-hydroxy-4- (N-heptadecylideneamino) benzanilide,

[0039] 4'-hydroxy-3,4-di-octyloxy-benzanilide, 4'-hydroxy-3-octyl-4- (octylthio) benzanilide, 4'-hydroxy-3- (heptadecylthio) -5- pentadecyloxy benz Anilide, 4'-hydroxy-3-heptadecylcarbonylamino-5-dodecylbenzanilide,
4'-hydroxy-3-octadecylaminocarbonyl-5-tetradecylaminocarbonylbenzanilide,
4'-hydroxy-3-octadecylsulfonylamino-5-octadecyloxybenzanilide, 4'-hydroxy-3-heptadecyloxysulfonyl-5-tetradecyloxysulfonylbenzanilide, 4'-hydroxy-3,5-bis ( N-docosylideneamino) benzanilide;

[0040] 4'-hydroxy-4-octadecyl carbonylamino benzanilide, 4'-hydroxy-3-
Octadecylcarbonylamino-5-octadecyloxybenzanilide, 3'-allyl-4'-hydroxy-
4-pentadecylbenzanilide, 4'-hydroxy-
3'-methyl-4-nonyloxybenzanilide, 4 '
-Hydroxy-3'-propyl-4-nonadecylcarbonyloxybenzanilide, 3'-butyl-4'-hydroxy-4-octadecyloxycarbonylbenzanilide, 3'-hydroxy-4-pentadecylcarbonyloxybenzanilide, '-Hydroxy-4-nonadecylsulfonylbenzanilide, 3', 4 ', 5'-trihydroxy-4-tetracosylaminosulfonylbenzanilide, 3', 5'-dihydroxy-4-pentacosylaminocarbonylbenz Anilide, 3'-hydroxy-4- (N-dodecylideneamino) benzanilide,
N- [4- (3-hydroxyphenylaminocarbonyl) benzylidene] pentadecylamine;

[0041] N- cyclohexyl-4-hydroxy benzhydrazide, N- cyclohexylmethyl-4-hydroxybenzamide hydrazide, N- cyclohexyl-4-hydroxybenzamide, N- cyclohexylmethyl 4-
Hydroxybenzamide, N-methyl-N-octadecyl-4-hydroxybenzamide, N- (3-methylhexyl) -4-hydroxybenzamide, N-octadecyl-4-hydroxybenzhydrazide, N- (8-octadecenyl) -4- Hydroxybenzamide,

[0042] 4-hydroxy-4'-dodecyl-benzanilide, N- methyl-4-hydroxy-4'-octadecyl benzanilide, 4-hydroxy-4'-octadecyloxy benzanilide, 4-hydroxy-4'-
(Octadecylthio) benzanilide, 4-hydroxy-4'-hexadecylcarbonylbenzanilide, 4-
Hydroxy-4'-heptadecyloxycarbonyloxybenzanilide, 4-hydroxy-4'-dodecyloxycarbonylbenzanilide, 4-hydroxy-4 '
-Heptadecylcarbonyloxybenzanilide, 4-
Hydroxy-4'-cyclohexylaminobenzanilide, 4-hydroxy-4'-octadecylaminobenzanilide,

[0043] 4-hydroxy-4'-heptadecyl carbonylamino benzanilide, 4-hydroxy-4'-
Octadecylaminocarbonylbenzanilide, 4-hydroxy-4'-dodecylsulfonylbenzanilide, 4-hydroxy-4'-octadecyloxysulfonylbenzanilide, 4-hydroxy-4'-dodecylsulfonyloxybenzanilide, N-4-hydroxybenzoyl -N'-octadecylidene-1,4-phenylenediamine, N-4- (4-hydroxyphenylcarbonylamino) benzylidenedecylamine, 4-
Hydroxy-4'-tetradecyloxycarbonylaminobenzanilide, 4-hydroxy-4'-octadecylureylenebenzanilide,

[0044] 3-hydroxy-4'-dodecyloxy-benzanilide, N- methyl-4-hydroxy-3'-octadecyloxyphenol benzanilide, 3-hydroxy -
4'-tetradecylbenzanilide, N-methyl-3-
Hydroxy-4'-octadecylbenzanilide, N-
Dodecyl-4-hydroxy-3-methylbenzamide,
3-methoxy-4-hydroxy-4'-octadecyloxybenzanilide, 3-chloro-4-hydroxy-
4'-octadecylbenzanilide, N-octadecyl-4-hydroxy-2,5-dimethylbenzamide, 4
-Hydroxy-4'-octadecyloxy-3'-chlorobenzanilide, 4-hydroxy-3 ', 4'-didecyloxybenzanilide, 4-hydroxy-3'-octadecylamino-4'-octadecyloxybenzanilide, 4-hydroxy-2'-chloro-3 ', 5'-
Didecyloxybenzanilide, 4-hydroxy-
3 ', 4'-dioctadecyloxybenzanilide, 4
-Hydroxy-4'-octyl-3'-methylbenzanilide, 3-hydroxy-4-methyl-4'-tetradecylbenzanilide, N-methyl-4-hydroxy-
3'-octadecylbenzanilide,

[0045] 4-(N-octadecylsulfonylamino) phenol, 4-(N-methyl--N- octadecylsulfonylamino) phenol, 4- (N-3- methylhexyl sulfonylamino) phenol, 4'-hydroxy-4- Cyclohexylbenzenesulfonanilide,
4'-hydroxy-4-octadecyloxybenzenesulfonanilide, 4'-hydroxy-4- (dodecylthio) benzenesulfonanilide, 4'-hydroxy-4
-Hexylcarbonylbenzenesulfonanilide, 4 '
-Hydroxy-4- (8-heptadecenyl) carbonylbenzenesulfonanilide, 4'-hydroxy-4-octyloxycarbonyloxybenzenesulfonanilide, 4'-hydroxy-4-dodecylcarbonyloxybenzenesulfonanilide, 4'-hydroxy-4 -Octadecylaminobenzenesulfoneanilide,

[0046] 4'-hydroxy-4-heptadecyl-carbonyl aminobenzenesulfonic anilide, 4'-hydroxy-4-dodecyl-aminocarbonyl benzene sulfonanilide, 4'-hydroxy-4-dodecyl-sulfonyl benzene sulfonanilide, 4'-hydroxy - 4-octadecyloxysulfonylbenzenesulfonanilide, 4'-hydroxy-4-dodecylsulfonyloxybenzenesulfonanilide, N-dodecylidene-4-
(4-hydroxyphenyl) aminosulfonylaniline, N-4- (4-hydroxyphenylaminosulfonyl) benzylideneoctadecylamine, 4'-hydroxy-4-octyloxycarbonylaminobenzenesulfonanilide, 4'-hydroxy-4-octadecyloxy Carbonylaminobenzenesulfonanilide, 4 '
-Hydroxy-4-octadecylureylenebenzenesulfonanilide,

[0047] N- methyl-4'-hydroxy-3-octadecyl oxybenzene sulfonanilide, 3'-hydroxy-4-dodecylbenzenesulfonic anilide, 3-
Methyl-4- (N-dodecylsulfonamino) phenol, 3'-methoxy-4'-hydroxy-4-octadecyloxybenzenesulfonanilide, 3'-chloro-
4'-hydroxy-4-octadecylbenzenesulfonanilide, 4'-hydroxy-2,5-dimethyl-4-
Octadecylbenzenesulfonanilide, 3-methyl-
4- (N-octadecylsulfonamino) phenol,
4'-hydroxy-3,4-dioctadecyloxybenzenesulfoneanilide,

[0048] 1- (4-hydroxyphenyl dithio) octadecane, 1- (4-hydroxyphenyl dithio) -
9-octadecene, 1- (2-fluoro-4-hydroxyphenyldithio) octadecane, 1- (2-ethoxy-4-hydroxyphenyldithio) octadecane, 1-
(3-chloro-4-hydroxyphenyldithio) octadecane,

[0049] 4'-hydroxy-4-tetradecyl diphenyl sulfide, 4'-hydroxy-4-octadecyl sulfide, 4'-hydroxy-4-octadecyl carbonylamino sulfide, 4 '
-Hydroxy-4-octadecyloxydiphenyl sulfide, 4'-hydroxy-4-octadecyloxysulfonyldiphenyl sulfide, 4'-hydroxy-4
-Octadecylsulfonylaminodiphenyl sulfide,

[0050] 4'-hydroxy-3,4-di-decyl oxy diphenyl sulfide, 4'-hydroxy-3,4
Dioctadecyloxydiphenyl sulfide, 4- (1
5-cyclohexylpentadecyl) -4'-hydroxydiphenyl sulfide, 4'-hydroxy-4- (5-
Tetradecenyl) diphenyl sulfide,

[0051] 3'-chloro-4'-hydroxy-4-octadecyl sulfide, 3'-hydroxy -
4-dodecyldiphenyl sulfide, 3'-hydroxy-4-octadecyldiphenyl sulfide, 3'-hydroxy-4-dodecyloxycarbonyldiphenyl sulfide,

[0052] N-(4-hydroxyphenyl)-N'-
Hexylurea, N- (4-hydroxyphenyl) -N '
-Dodecyl urea, N- (4-hydroxyphenyl)-
N'-hexadecyl urea, N- (4-hydroxyphenyl) -N'-octadecyl urea, N- (4-hydroxyphenyl) -N'-icosyl urea, N- (4-hydroxyphenyl) -N'-cyclododecyl Urea, N- (4
-Hydroxyphenyl) -N'-docosylurea, N-
(4-hydroxyphenyl) -N'-cholesteryl urea, N- (4-hydroxyphenyl) -N '-(2-heptyloctyl) urea, N- (4-hydroxyphenyl) -N'-(9-octadecenyl) urea,

[0053] N- (3- allyl-4-hydroxyphenyl)-N'-octadecyl urea, N-(2-hydroxyphenyl)-N'-octyl urea, N- (3- hydroxyphenyl)-N'-octadecyl Urea, N- (3,4
-Dihydroxyphenyl) -N'-octadecylurea,
N- (3,4,5-trihydroxyphenyl) -N'-
Trichosyl urea, N- (4-hydroxyphenyl)-
N '-(4-tetradecylphenyl) urea, N- (4-
(Hydroxyphenyl) -N′-hexadecylthiourea,
N- (4-hydroxyphenyl) -N'-octadecylthiourea;

[0054] 4-undecanoylamino-amino-1- (4-hydroxyphenyl-aminocarbonyl) benzene, 4-octadecanoyl-amino-1- (4-hydroxyphenyl-aminocarbonyl) benzene, 4- (octadecyl amino carbonyl) amino - 1- (4-hydroxyphenylaminocarbonyl) benzene, 4-octadecylamino-1- (4-hydroxyphenylamino) carbonylmethylbenzene, N-octadecyl-N'-p- (4-hydroxyphenylcarbamoyl) phenyl oxamide,
4- (octadecylaminocarbonyl) amino-1-
(4-hydroxyphenylcarbamoyl) methylbenzene, 4- (octadecylamino) carbonyl-1- (4
-Hydroxyphenylcarbamoyl) methylbenzene,
N-octadecanoyl-N'-p- (p-hydroxyphenylcarbamoylmethyl) benzoylhydrazine, N
-Dodecanoyl-N'-p- [2- (p-hydroxyphenylcarbamoyl) ethyl] benzoylhydrazine,

[0055] N-(4-hydroxyphenyl-methyl) -
N'-n-tetradecyl urea, N- (4-hydroxyphenylmethyl) -N'-n-octadecyl urea, N-
[2- (4-hydroxyphenyl) ethyl] -N'-n
-Tetradecyl urea, N- [2- (4-hydroxyphenyl) ethyl] -N'-n-octadecyl urea, N-
[3- (4-hydroxyphenyl) propyl] -N'-
n-dodecyl urea, N- [3- (4-hydroxyphenyl) propyl] -N'-n-octadecyl urea, N-
[6- (4-hydroxyphenyl) hexyl] -N'-
n-dodecyl urea, N- [2- (3-hydroxyphenyl) ethyl] -N'-n-octadecyl urea, N- [2
-(3,4-dihydroxyphenyl) ethyl] -N'-
n-octadecyl urea,

Nn -octadecyl- (4-hydroxyphenyl) acetamide, Nn-dodecyl-3- (4
-Hydroxyphenyl) propanamide, Nn-octadecyl-3- (4-hydroxyphenyl) propanamide, N- (4-hydroxyphenylmethyl) octadecanamide, N- [2- (4-hydroxyphenyl) ethyl] octadecane Amide, N- [3- (4-hydroxyphenyl) propyl] octadecanamide, N- [3
-(3-hydroxyphenyl) propyl] octadecanamide, N- [3- (3,4-dihydroxyphenyl)
Propyl] octadecaneamide,

[0057] N-(4-hydroxybenzoyl) -N '
-N-octanoylhydrazine, N- (4-hydroxybenzoyl) -N'-n-tetradecanoylhydrazine, N- (4-hydroxybenzoyl) -N'-n-octadecanoylhydrazine, N- (2, 4-dihydroxybenzoyl) -N'-n-octanoylhydrazine,
N- (2,4-dihydroxybenzoyl) -N'-n-
Octadecanoylhydrazine, N- (4-hydroxybenzoyl) -N'-n-tetradecylaminocarbonylhydrazine, N- (4-hydroxybenzoyl) -N '
-N-octadecylaminocarbonylhydrazine, N-
(2,4-dihydroxybenzoyl) -N'-n-tetradecylaminocarbonylhydrazine, N- (2,4-
Dihydroxybenzoyl) -N'-n-octadecylaminocarbonylhydrazine, N- (4-hydroxybenzoyl) -N'-n-octyloxycarbonylhydrazine, N- (4-hydroxybenzoyl) -N'-n-
Dodecyloxycarbonylhydrazine, N- (2,4-
Dihydroxybenzoyl) -N'-n-tetradecyloxycarbonylhydrazine, N- (2,4-dihydroxybenzoyl) -N'-n-octadecyloxycarbonylhydrazine, N- (4-hydroxybenzoyl)-
N'-n-tetradecylhydrazinocarbonylhydrazine, N- (4-hydroxybenzoyl) -N'-n-octadecylhydrazinocarbonylhydrazine, N-
(2,4-dihydroxybenzoyl) -N'-n-tetradecylhydrazinocarbonylhydrazine, N- (2
4-dihydroxybenzoyl) -N'-n-octadecylhydrazinocarbonylhydrazine;

[0058] N-(4-hydroxybenzoyl) -N '
-N-octanoylmethylenediamine, N- (4-hydroxybenzoyl) -N'-n-tetradecanoylmethylenediamine, N- (4-hydroxybenzoyl)-
N'-n-octadecanoyl methylenediamine, N-
(2,4-dihydroxybenzoyl) -N'-n-tetradecanoylmethylenediamine, N- (2,4-dihydroxybenzoyl) -N'-n-octadecanoylmethylenediamine, N- (4-hydroxybenzoyl) −
N'-n-octylaminocarbonylmethylenediamine, N- (4-hydroxybenzoyl) -N'-n-dodecylaminocarbonylmethylenediamine, N- (4-
(Hydroxybenzoyl) -N'-n-tetradecylaminocarbonylmethylenediamine, N- (4-hydroxybenzoyl) -N'-n-octadecylaminocarbonylmethylenediamine, N- (2,4-dihydroxybenzoyl) -N'- n-octadecylaminocarbonylmethylenediamine, N- (4-hydroxybenzoyl)-
N'-n-tetradecyloxycarbonylmethylenediamine, N- (4-hydroxybenzoyl) -N'-n-
Octadecyloxycarbonylmethylenediamine, N-
(2,4-dihydroxybenzoyl) -N'-n-tetradecyloxycarbonylmethylenediamine, N-
(2,4-dihydroxybenzoyl) -N'-n-octadecyloxycarbonylmethylenediamine, N- (4
-Hydroxybenzoyl) -N'-n-octylhydrazinocarbonylmethylenediamine, N- (4-hydroxybenzoyl) -N'-n-dodecylhydrazinocarbonylmethylenediamine, N- (2,4-dihydroxybenzoyl) -N '-N-tetradecylhydrazinocarbonylmethylenediamine, N- (2,4-dihydroxybenzoyl) -N'-n-octadecylhydrazinocarbonylmethylenediamine,

Nn -octadecyl-2- (p-hydroxyphenylthio) acetamide, Nn-octadecyl-3- (p-hydroxyphenylthio) propanamide, Nn-decyl-11- (p-hydroxy Phenylthio) undecaneamide, N- (pn-octylphenyl) -6- (p-hydroxyphenylthio) hexanamide, Nn-octadecyl-p- (p-hydroxyphenylthio) benzamide, N- [2 -(P-hydroxyphenylthio) ethyl] -n-octadecanamide, N- [p- (p-hydroxyphenylthio) phenyl] -n-octadecanamide, N- (p-hydroxyphenylthio) methyl-N'- n-octadecyl urea,
N- [2- (p-hydroxyphenylthio) ethyl]-
N'-n-tetradecyl urea, N- [2- (p-hydroxyphenylthio) ethyl] -N'-n-octadecyl urea, N- [2- (3,4-dihydroxyphenylthio) ethyl] -N ' -N-octadecyl urea, N- [p
-(P-hydroxyphenylthio) phenyl] -N'-
n-octadecyl urea, N- [10- (p-hydroxyphenylthio) decyl] -N'-n-decyl urea, N-
[2- (p-hydroxyphenylthio) ethyl] -n-octadecylcarbamate, N- [p- (p-hydroxyphenylthio) phenyl] -n-dodecylcarbamate, Nn-octadecylcarbamic acid- [2 − (P−
Hydroxyphenylthio) ethyl], N- [3- (p-
(Hydroxyphenylthio) propionyl] -NN-octadecanoylamine, N- [2- (p-hydroxyphenylthio) aceto] -N'-n-octadecanohydrazide, N- [3- (p-hydroxy Phenylthio) propiono] -N'-n-octadecanohydrazide, N-
[3- (3,4-dihydroxyphenylthio) propiono] -N'-n-octadecanohydrazide, N- [6-
(P-Hydroxyphenylthio) hexano] -N'-n
-Tetradecanohydrazide, N- [6- (p-hydroxyphenylthio) hexano] -N'-n-octadecanohydrazide, N- [6- (p-hydroxyphenylthio) hexano] -N '-( p-n-octylbenzo) hydrazide, N- [11- (p-hydroxyphenylthio) undecano-N'-n-decanohydrazide, N-
[11- (p-hydroxyphenylthio) undecano-
N'-n-tetradecanohydrazide, N- [11- (p
-Hydroxyphenylthio) undecano-N'-n-octadecanohydrazide, N- [11- (p-hydroxyphenylthio) undecano-N '-(6-phenyl) hexanohydrazide, N- [11- (3 , 4,5-Trihydroxyphenylthio) undecano] -N'-n-octadecanohydrazide, N- [p- (p-hydroxyphenylthio) benzo] -N'-n-octadecanohydrazide, N- [P- (p-hydroxyphenylthiomethyl)
Benzo] -N'-n-octadecanohydrazide, N-
[3- (p-hydroxyphenylthio) propyl]-
N'-n-octadecyl oxamide, N- [3- (3,
4-dihydroxyphenylthio) propyl] -N'-n
-Octadecyloxamide, N- [11- (p-hydroxyphenylthio) undecyl] -N'-n-decyloxamide, N- [p- (p-hydroxyphenylthio)
Phenyl] -N'-n-octadecyloxamide, N-
[2- (p-hydroxyphenylthio) acetyl]-
N'-n-octadecyl urea, N- [3- (p-hydroxyphenylthio) propionyl] -N'-n-octadecyl urea, N- [2- (p-hydroxyphenylthio) ethyl] -N'-n -Octadecanoyl urea, N-
[P- (p-hydroxyphenylthio) phenyl]-
N'-n-octadecanoyl urea, 3- [3- (p-hydroxyphenylthio) propionyl] carbazic acid-
n-octadecyl, 4- [2- (p-hydroxyphenylthio) ethyl] -1-n-octadecyl semicarbazide, 1- [2- (p-hydroxyphenylthio) ethyl] -4-n-octadecyl semicarbazide, 1- [P
-(P-hydroxyphenylthio) phenyl] -4-n
-Tetradecylsemicarbazide, 1- [3- (p-hydroxyphenylthio) propionyl] -4-n-octadecylsemicarbazide, 1- [p- (p-hydroxyphenylthio) benzoyl] -4-n-octadecylsemicarbazide, 4 -[2- (p-hydroxyphenylthio) ethyl] -1-n-tetradecanoyl semicarbazide, 4- [p- (p-hydroxyphenylthio) phenyl] -1-n-octadecanoyl semicarbazide, 1-
[2- (p-hydroxyphenylthio) acetamide]
-1-n-octadecanoylaminomethane, 1- [11
-(P-hydroxyphenylthio) undecaneamide]
-N'-n-decanoylaminomethane, 1- [p- (p
-Hydroxyphenylthio) benzamide] -1-n-
Octadecanoylaminomethane, 1- [3- (p-hydroxyphenylthio) propanamide] -1- (N'-
n-octadecylureido) methane, 1- [11- (p
-Hydroxyphenylthio) undecaneamide] -N '
-(N'-n-decylureido) methane, 1- {N'-
[2- (p-hydroxyphenylthio) ethyl] ureido {-1-n-octadecanoylaminomethane, N-
[2- (p-hydroxyphenylthio) ethyl] -N '
-N-octadecylmalonamide,

[0060] N- [2- (p- hydroxyphenyl) ethyl] carbamate -n- octadecyl, N-n-octadecyl carbamate - [2- (p- hydroxyphenyl) ethyl], N- [3- (p -Hydroxyphenyl)
Propionyl] -Nn-octadecanoylamine, N
-[6- (p-hydroxyphenyl) hexanoyl]-
Nn-octadecanoylamine, N- [3- (p-hydroxyphenyl) propionyl] -N- (pn-octylbenzoyl) amine, N- [2- (p-hydroxyphenyl) aceto] -N '-N-dodecanohydrazide, N- [2- (p-hydroxyphenyl) aceto]-
N'-n-octadecanohydrazide, N- [3- (p-
Hydroxyphenyl) propiono] -N'-n-octadecanohydrazide, N- [3- (p-hydroxyphenyl) propiono] -N'-n-docosanohydrazide, N
-[6- (p-hydroxyphenyl) hexano] -N '
-N-tetradecanohydrazide, N- [6- (p-hydroxyphenyl) hexano] -N'-n-octadecanohydrazide, N- [6- (p-hydroxyphenyl) hexano] -N '-( pn-octylbenzo) hydrazide, N- [11- (p-hydroxyphenyl) undecano-N'-n-decanohydrazide, N- [11- (p-
(Hydroxyphenyl) undecano-N'-n-octadecanohydrazide, N- [p- (p-hydroxyphenyl) benzo] -N'-n-octadecanohydrazide, N
-[P- (p-hydroxyphenylmethyl) benzo]-
N'-n-octadecanohydrazide, N- [3- (p-
Hydroxyphenyl) propyl] -N'-n-octadecyl oxamide, N- [3- (3,4-dihydroxyphenyl) propyl] -N'-n-octadecyl oxamide, N- [p- (p-hydroxyphenyl) ) Phenyl]
-N'-n-octadecyloxamide, N- [2- (p
-Hydroxyphenyl) acetyl] -N'-n-octadecyl urea, N- [3- (p-hydroxyphenyl) propionyl] -N'-n-octadecyl urea, N- [p
-(P-hydroxyphenyl) benzoyl] -N'-n
-Octadecyl urea, N- [2- (p-hydroxyphenyl) ethyl] -N'-n-octadecanoyl urea,
-[2- (p-hydroxyphenyl) ethyl] -1-n
-Octadecylsemicarbazide, 1- [2- (p-hydroxyphenyl) ethyl] -4-n-tetradecylsemicarbazide, 1- [2- (p-hydroxyphenyl) ethyl] -4-n-octadecylsemicarbazide, 1-
[2- (p-hydroxyphenyl) acetyl] -4-n
-Tetradecylsemicarbazide, 1- [3- (p-hydroxyphenyl) propionyl] -4-n-octadecylsemicarbazide, 1- [11- (p-hydroxyphenyl) undecanoyl] -4-n-decylsemicarbazide, 4- [ 2- (p-hydroxyphenyl) ethyl]-
1-n-octadedecanoyl semicarbazide, 4- [p
-(P-hydroxyphenyl) phenyl] -1-n-octadecanoyl semicarbazide, 1- [2- (p-hydroxyphenyl) acetamido] -1-n-octadecanoylaminomethane, 1- [3- (p -Hydroxyphenyl) propanamide] -1-n-octadecanoylaminomethane, 1- [2- (p-hydroxyphenyl) acetamido] -1- (3-n-octadecylureido)
Methane, 1- [3- (p-hydroxyphenyl) propanamide] -1- (3-n-octadecylureido) methane, 1- [11- (p-hydroxyphenyl) undecaneamide] -1- (3-n -Decylureido) methane, 1- {3- [2- (p-hydroxyphenyl) ethyl] ureide} -1-n-octadecanoylaminomethane, N- [2- (p-hydroxyphenyl) ethyl]-
N'-n-octadecylmalonamide,

[0061] 4-n-octadecyl-aminophenol,
4- (1-octadecynyl) phenol, 4- (1,3
-Octadecadinyl) phenol and the like.

[0062] may be used by mixing one or two or more of these, respectively, the normal colorless or pale colored electron-donating dye precursor, 5 to 5000 wt%, preferably from 10 to 3,000% by weight Used.

[0063] The object can also be added to the reversible thermosensitive recording layer in a binder in such to improve the strength of the reversible thermosensitive recording layer. Specific examples of the binder include starches, hydroxyethylcellulose, methylcellulose, carboxymethylcellulose, gelatin, casein, polyvinyl alcohol, modified polyvinyl alcohol, sodium polyacrylate, acrylamide / acrylate copolymer, acrylamide / acryl. Water-soluble polymers such as acid ester / methacrylic acid terpolymer, alkali salt of styrene / maleic anhydride copolymer, alkali salt of ethylene / maleic anhydride copolymer, polyvinyl acetate, polyurethane, polyacrylic acid Latexes such as esters, styrene / butadiene copolymers, acrylonitrile / butadiene copolymers, methyl acrylate / butadiene copolymers, ethylene / vinyl acetate copolymers, and the like, but are not limited thereto. No.

A heat-fusible substance can be contained in the reversible thermosensitive recording layer as an additive for adjusting the color sensitivity and the decoloring temperature of the reversible thermosensitive recording layer. 60 ° C
Those having a melting point of 200 ° C to 200 ° C
Those having a melting point of -180 ° C are preferred. A sensitizer used in general thermosensitive recording paper can also be used. For example, waxes such as N-hydroxymethyl stearamide, stearamide, palmitamide, naphthol derivatives such as 2-benzyloxynaphthalene, biphenyl derivatives such as p-benzylbiphenyl and 4-allyloxybiphenyl, 1,2 -Screw (3-
Polyether compounds such as methylphenoxy) ethane, 2,2'-bis (4-methoxyphenoxy) diethyl ether, bis (4-methoxyphenyl) ether, diphenyl carbonate, dibenzyl oxalate, bis (p-methylbenzyl) oxalate Carbonic acid or oxalic acid diester derivatives such as esters can be added in combination, but are not limited thereto.

[0065] As the electron beam curing resin or an ultraviolet curable resin used in the present invention there may be mentioned compounds having an ethylenically unsaturated bond, and more specifically include the following resins.

[0066] (1) an aliphatic, alicyclic, aromatic, polyhydric alcohols and polyalkylene glycols of poly (meth) acrylates of aromatic aliphatic (2) aliphatic, cycloaliphatic, aromatic, araliphatic Poly (meth) acrylate of polyhydric alcohol obtained by adding alkylene oxide to polyhydric alcohol (3) Polyester poly (meth) acrylate (4) Polyurethane poly (meth) acrylate (5) Epoxy poly (meth) acrylate (6) Polyamide Poly (meth) acrylate (7) Poly (meth) acryloyloxyalkyl phosphate ester (8) Vinyl- or diene-based compound having (meth) acryloyloxy group at the side chain or terminal (9) Monofunctional (meth) acrylate , Vinylpyrrolidone, (meth) acryloyl compound (10) ethylenically unsaturated Cyano compounds having a sum bond (11) Mono- or polycarboxylic acids having an ethylenically unsaturated bond and their alkali metal salts, ammonium salts, amine salts, etc. (12) Ethylenically unsaturated (meth) acrylamide or alkyl-substituted ( (13) Vinyl lactam and polyvinyl lactam compound (14) Polyether having an ethylenically unsaturated bond and its ester (15) Ester of alcohol having an ethylenically unsaturated bond (16) Ethylenic Polyalcohols having saturated bonds and esters thereof (17) Aromatic compounds having one or more ethylenically unsaturated bonds such as styrene and divinylbenzene (18) Polyorgano having a (meth) acryloyloxy group at a side chain or at a terminal Shiroki Emissions-based compound (19) silicone compounds having an ethylenically unsaturated bond (20) above (1) to (19) multimeric or oligoester (meth) acrylate modified compounds of the compounds described

[0067] These resins can be used alone, it can be used as a mixture with other resins. Further, it can be applied without a solvent, can be diluted with a solvent and can be applied, or can be applied in an emulsion state, dried and cured.

[0068] The coating amount of the electron beam curing resin or an ultraviolet curable resin is thinner for the purpose of avoiding thermal shutdown is ^{desired, 0.5g / m 2 ~10.0g / m} 2 is preferred. If less than this range, good repetitive usability is not exhibited,
If the amount is larger than this range, the heat sensitivity is deteriorated.

The method of applying the resin for forming the electron beam or ultraviolet curable resin layer of the present invention includes a gravure roll, a transfer roll coater, a bar coater, and the like.
Roll coater, air knife coater, U comma coater, AKKU coater, smoothing coater, microgravure coater, air knife coater, reverse roll coater, 4 or 5 roll coater, blade coater, dip coater, bar coater, rod coater, kiss coater, gate Any coater such as a roll coater, a squeeze coater, a falling curtain coater, a slide coater, and a die coater may be used.

When the electron beam curing method is used in the present invention, the electron beam irradiation is performed at an accelerating voltage of 100 to 100 from the viewpoint of transmission power and curing power.
1000 kV, more preferably 100-300 k
V electron beam accelerator, the absorbed dose in one pass is 0.5
It is preferable to set to 〜20 Mrad. If the acceleration voltage or the amount of electron beam irradiation is lower than this range, the electron beam transmission power is too low to perform sufficient curing, and if it is higher than this range, not only does the energy efficiency deteriorate, but also the resin, Undesirable effects on quality such as decomposition of additives and reduction in strength of base paper appear.

The electron beam accelerator may be, for example, any of an electron curtain system, a scanning type, a double scanning type, and the like.

When irradiating an electron beam, if the oxygen concentration is high, the curing of the electron beam curable resin is hindered.
Substitution with an inert gas such as helium or carbon dioxide is performed to reduce the oxygen concentration to 600 ppm or less, preferably 400 p.
Irradiation is preferably performed in an atmosphere suppressed to pm or less.

When the resin is cured by the ultraviolet curing method in the present invention, a photoreaction initiator is mixed and used. Examples of photoreaction initiators include acetophenones such as di and trichloroacetophenones, benzophenone, Michler's ketone, benzyl, benzoin, benzoin alkyl ether, benzyldimethyl ketal, tetramethylthiuram monosulfide, thioxanthones, azo compounds, various silver salts, and the like. The use amount of the photoreaction initiator is usually in the range of 0.1 to 10% based on the ultraviolet curable resin. In some cases, a storage stabilizer such as hydroquinone is used as the photoinitiator.

[0074] As the ultraviolet irradiation device, for example, low pressure mercury lamp, medium pressure mercury lamps, high pressure mercury lamp, there is a metal halide lamp or the like, there is also a small ozone-less type ozone generator. Generally, a plurality of lamps having an output of 30 W / cm or more are used in parallel.

[0075] reversible thermosensitive recording material of the present invention other than heating, for example light, in order to prevent deterioration of the reversible thermosensitive recording layer in such a plasticizer, the reversible thermosensitive recording layer and the protective layer if necessary An intermediate layer may be provided therebetween.

[0076] reversible thermosensitive recording layer usually colorless or light-colored dye precursor in, in order to incorporate the reversible color developing agent,
A method of dissolving or dispersing each compound in water or an organic solvent alone, a method of dissolving or dispersing each compound in water or an organic solvent after mixing each compound, cooling each of the compounds after heating and dissolving them to homogeneity, There is a method of mixing each solution or dispersion obtained by a method of dissolving or dispersing in water or an organic solvent, printing on a support, and coating and drying. In this case, for example, each color-forming component may be contained in a single layer to form a multilayer structure, but the present invention is not particularly limited thereto.

The support used in the reversible thermosensitive recording material of the present invention includes paper, coated paper, various nonwoven fabrics, woven fabric, synthetic resin film, synthetic resin laminated paper, synthetic paper, metal foil, glass, etc. A composite sheet combining these can be used arbitrarily according to the purpose, and may be transparent, translucent, or opaque, but is not limited thereto. The thickness of the support is
There is no particular limitation as long as it can withstand repeated use, but 20 to 1300 μm, preferably 40 to 1000 μm
m.

[0078] layer structure of a reversible thermosensitive recording material of the present invention,
An intermediate layer may be provided between the reversible thermosensitive recording layer and the support, and / or between the reversible thermosensitive recording layer and the protective layer. In this case, the intermediate layer may be composed of two or three or more layers. Further, information can be recorded electrically, magnetically and optically in the reversible thermosensitive recording layer and / or on another layer and / or on the surface on which the reversible thermosensitive recording layer is provided and / or on the opposite surface. Materials may be included.
Further, a back coat layer may be provided on the surface opposite to the surface on which the reversible thermosensitive recording layer is provided for the purpose of preventing curling and electrification, and may be further subjected to an adhesive process or the like.

The reversible thermosensitive recording layer and / or the intermediate layer include diatomaceous earth, talc, kaolin, calcined kaolin, calcium carbonate, magnesium carbonate, titanium oxide,
Pigments such as zinc oxide, silicon oxide, aluminum hydroxide, and urea-formalin resin, in addition, zinc stearate,
Higher fatty acid metal salts such as calcium stearate, waxes such as paraffin, paraffin oxide, polyethylene, polyethylene oxide, stearic acid amide, caster wax, etc .; dispersants such as sodium dioctyl sulfosuccinate; further, surfactants, fluorescent dyes, etc. Can also be contained.

The method for forming each layer constituting the reversible thermosensitive recording material of the present invention on a support is not particularly limited, and it can be formed by a conventional method. For example, smearing devices such as air knife coaters, blade coaters, bar coaters, curtain coaters, etc., lithographic, letterpress,
Various printing machines and the like using intaglio, flexo, gravure, screen, hot melt, and the like can be used. Further, each layer can be held by UV irradiation or EB irradiation in addition to the usual drying step. By these methods, smearing and printing can be performed one layer at a time or simultaneously at multiple layers.

In the reversible thermosensitive recording material of the present invention, rapid cooling may be performed after heating in order to form a color-formed image, and the cooling rate after heating is required to decolor the recorded image. Good if it is late. For example, after heating by an appropriate method, by rapidly cooling by pressing a low-temperature metal block or the like, a colored state can be developed. In addition, when heating is performed for a very short time using a thermal head, a laser beam, or the like, cooling is performed immediately after the heating is completed, so that a color-developed state can be maintained. On the other hand, when heated by an appropriate heat source (thermal head, laser light, heat roll, heat stamp, high frequency heating, electric heater, radiant heat from a light source such as a tungsten lamp or a halogen lamp, hot air, etc.) for a relatively long time, recording is performed. Since not only the layer but also the support and the like are heated, even if the heat source is removed, the cooling speed is slow and the color is erased. Therefore, even if the same heating temperature and / or the same heat source is used, the color development state and the decoloration state can be arbitrarily developed by controlling the cooling rate.

[0082]

The present invention will be described in more detail with reference to the following examples.

[0083] Example 1 (A) is a tone made dye precursors reversible thermosensitive coating solution 3- (4-diethylamino-2-ethoxyphenyl) -3- (1-ethyl-2-methylindole-3-yl ) -4-Azaphthalide 40 parts 2.5%
The mixture was ground with a ball mill for 24 hours together with 90 parts of an aqueous polyvinyl alcohol solution to obtain a dye precursor dispersion. Subsequently, N
-[3- (p-hydroxyphenyl) propiono]-
2.5 parts of N'-n-octadecanohydrazide 100 parts
Ball mill and pulverized for 24 hours with 400 parts of polyvinyl alcohol aqueous solution to obtain a dispersion. After mixing the above two dispersions, a 10% aqueous solution of polyvinyl alcohol 200
Parts, 400 parts of water, and mix well to obtain a reversible heat-sensitive coating solution.
Prepared .

[0084] (B) action of the reversible thermosensitive recording layer and the intermediate layer
The reversible heat-sensitive coating solution prepared in (A) was coated on a polyethylene terephthalate (PET) sheet with a solid content of 4 g / m ^2.
After drying, 5% polyvinyl alcohol was further applied and dried so as to have a solid content of 1 g / m ² to obtain an intermediate layer.

[0085] (C) action of the protective layer with ultraviolet curable resin
On the intermediate layer obtained in manufacturing (B), the ultraviolet curable resin (Aronix M8030, Toagosei Chemical Industry Co. product) 5
, N-vinyl-2-pyrrolidone, 5 parts, and a photoreaction initiator (Irgacure 500, a product of Nippon Ciba Geigy Co., Ltd.) were mixed well (a), and hydrophobic silica (Silohobic 100 (average particle size)) was further mixed. SS-70 (average particle size 4.1 μm), product of Fuji Silysia Ltd.
m), Nippon Silica Industrial Co. product, P-363 (average particle diameter 10.5 [mu] m), water Ze Chemical Industry Co., Ltd. Company) were mixed in a ratio shown in Table 1, sufficiently stirred 2.5 g / after m ^{2, and} the coating ultraviolet irradiation device (Ushio Inc.
And rapid cure) to obtain a reversible thermosensitive recording material.

[0086]

[Table 1]

[0087] was made work in the same manner as in Comparative Example 1 Example 1 of Comparative Example which was not added at all hydrophobic silica as Example 1 (C).

[0088]

[Table 2]

[0089] On the intermediate layer obtained in the (B) Example 2 Example 1, an electron beam curable resin (KAYARADR167, Nippon Kayaku Co., Ltd. products) of hydrophobic silica particles in a ratio shown in Table 3 (Silo Hovic 10
0 (average particle size: 1.4 μm), product of Fuji Silysia Ltd., SS-70 (average particle size: 4.1 μm), product of Nippon Silica Industry Co., Ltd., P-363 (average particle size: 10.5 μm)
m), water Ze Chemical Industry Co., Ltd. Company) was added and mixed, was applied so that a sufficiently stirred electron beam-curable resin to 2.5 g / m ^2, nitrogen oxygen concentration of the electron beam irradiation chamber The reversible thermosensitive recording material is guided into an electron beam irradiation device (Curetron, trade name, manufactured by Nissin High Voltage Co., Ltd.) of 200 ppm or less by gas replacement and irradiated with an electron beam so as to have an electron beam acceleration voltage of 200 kV and an absorbed dose of 2 Mrad. I got

[0090]

[Table 3]

[0091] and the one without addition any hydrophobic silica as a comparative example of the Comparative Example 2 Example 2 was created manufactured in the same manner as in Example 2.

[0092]

[Table 4]

[0093] The reversible thermosensitive recording material obtained in Test 1 Examples 1 and 2, Kyocera print head KJT-256-8MGF
1 with Okura Electric Thermal Facsimile Printing Tester TH-P
Using an MD, printing was performed with an applied pulse of 2.0 milliseconds and an applied voltage of 26 volts. Further, the sample was placed in a thermostatic dryer kept at 120 ° C., and the image was erased and printed again. Repeated up to times. Thereafter, L ^* a ^* b ^* of the erased portion was measured with a colorimeter (CR-100, manufactured by Minolta Co., Ltd.).

[0094] yellowing of the degree of the erased portion is represented by L ^* a ^* b ^* of b ^* values. That is, if the b ^* value is positive and takes a larger value than the non-image portion (background portion), it is visually recognized as yellowing. The [Delta] b ^* as the degree of yellowing from this - was defined as the (b ^* of the erased portion b ^* of the non-image portion). Table 5 shows the results.

[0095]

[Table 5]

From Table 5, the values of 1 to 6 and 8 to 9 of Examples 1 and 2 are smaller than those of 7 and 14 of Comparative Examples 1 and 2, that is, hydrophobic silica is effective in suppressing yellowing. Actually, the yellowing of the decolored portion of the example is hardly visible, but in the comparative example, the decolored portion is visually recognized in a yellowed state.

[0097] On the intermediate layer obtained in Comparative Example 3 Example 1 (B), the ultraviolet curable resin (Aronix M8030, Toagosei Chemical Industry Co.,
Product) 5 parts, N-vinyl-2-pyrrolidone 5 parts, photoinitiator (Irgacure 500, Nippon Ciba Geigy Co., Ltd.)
5 parts well mixed (same composition as (C) of Example 1 and Aronix mixture (a))), and further, aluminum hydroxide (H-42, particle size 1 μm, product of Showa Denko KK), Amorphous silica (Mizukasil P-527, particle size 1.
6 μm, Mizusawa Chemical Industry Co., Ltd.), zinc oxide (Zinc Hua No. 1, particle size 0.3-0.6 μm, product of Kasho Co., Ltd.), kaolin (UW-90, particle size 2 μm or less, Ryosan Shoji Co., Ltd.
One of the products was mixed at the following ratio, mixed well, and applied to 2.5 g / m ² , and then cured with an ultraviolet irradiation device (Rapid Cure, manufactured by Ushio Electric Co., Ltd.) A reversible thermosensitive recording material was obtained.

[0098]

[Table 6]

[0099] The reversible thermosensitive recording material obtained in Test 2 Comparative Example 3, an applied pulse 1.1 ms using a Kyocera print head KJT-256-8MGF1 with Ohkura Electric Ltd. thermosensitive facsimile printing tester TH-PMD Printing was performed under the conditions of an applied voltage of 26 volts, and the density of the obtained image portion (colored portion) was measured using a densitometer Macbeth RD9.
18 was used. Further, the operation of placing the sample in a constant temperature dryer kept at 120 ° C., erasing the image and printing again was repeated up to 20 times. Table 7 shows the results.

[0100]

[Table 7]

[0102] The reversible thermosensitive recording material obtained in Test 3 Comparative Example 3, an applied pulse 2.0 ms using a Kyocera print head KJT-256-8MGF1 with Ohkura Electric Ltd. thermosensitive facsimile printing tester TH-PMD Printing was performed under the conditions of an applied voltage of 26 volts, and the operation of placing the sample in a thermostatic dryer kept at 120 ° C., erasing the image, and printing again was repeated up to five times. Thereafter, L ^* a ^* b ^* of the erased portion was measured with a colorimeter (CR-100, manufactured by Minolta Co., Ltd.).

[0102] yellowing of the degree of the erased portion is represented by L ^* a ^* b ^* of b ^* values. That is, if the b ^* value is positive and takes a larger value than the non-image portion (background portion), it is visually recognized as yellowing. The [Delta] b ^* as the degree of yellowing from this - was defined as the (b ^* of the erased portion b ^* of the non-image portion). Table 8 shows the results.

[0103]

[Table 8]

[0104] From Test 2 and Test 3, in addition silicas it it can be seen that there is no effect of suppressing yellowing. Further, in the case of silica which is not hydrophobic silica according to Test 2, although there is some yellowing suppression effect, the density of the image area is reduced during repeated coloring / erasing, and the stable image which is one of the objects of the present invention is obtained. No formation has been achieved.

[0105]

As described in Examples 1 and 2, the blending of hydrophobic silica in the protective layer reduces yellowing,
A reversible thermosensitive recording material capable of forming a stable image even in repeated coloring / erasing was obtained.

────────────────────────────────────────────────── ─── Continued on front page (58) Field surveyed (Int. Cl. ⁷ , DB name) B41M 5/28-5/34

Claims (2)

(57) [Claims] 1. A colorless or light-colored electron-donating dye precursor, and a reversible developer for causing the dye precursor to form a color by heating and decoloring by reheating, on at least one surface of the support. In a reversible thermosensitive recording material provided with a reversible thermosensitive recording layer, the organosilicon compound is hydrophobic on the reversible thermosensitive recording layer or on at least one or more intermediate layers.
Di-n-butylamine value of 100 meq / k
g has the following hydrophobic, average particle size Ri Do a UV-curable or electron beam curable resins comprising hydrophobic silica particles of 1 to 10 [mu] m, characterized in that a protective layer ing and curing it Reversible thermosensitive recording material. Wherein the hydrophobic silica particles 3-30 wt%
Ri Do a UV-curable or electron beam curable resins comprising,
The reversible thermosensitive recording material according to claim 1, wherein a protective layer ing to cure it.