JPS58219092A - Transfer-type heat-sensitive recording material - Google Patents

Abstract

PURPOSE:To enhance color density and color formation sensitivity, by a method wherein a specified benzyl ether, a specified naphthalene derivative of the like is incorporated as a heat-fusibilizer in a heat-fusible transfer layer of a transfer- type heat-sensitive recording material. CONSTITUTION:At least one heat-fusibilizer of formula I (wherein R1 is an alkyl group or an aralkyl group; Y is an alkyl group, alkoxy group, a halogen atom or the like), formula II (wherein R2 is an alkyl group, an aralkyl group, an alkylcarbonyl group or the like) or formula III (wherein each of R3, R4 is an alkyl group, an aralkyl group or an aryl group) is incorporated into a heat- fusible transfer layer comprising an electron-donating colorless dye such as a triarylmethane compound or a diphenylmethane compound and an electron- accepting compound such as a phenol compound or an organic acid as main constituents. In addition, a binder, an additive or the like may also be incorporated into the layer.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a transfer type heat-sensitive recording material, and more particularly to a transfer type heat-sensitive recording material with improved color development.

In recent years, thermal facsimiles, thermal printers, or thermal recorders that use thermal recording materials have been widely used in various information recording devices because of their many features, such as not making noise during recording and being easy to handle. It's being used. However, the conventional heat-sensitive recording method has the disadvantage that when heat is applied again after recording, parts other than the printed area develop color, and that the printed area can be easily tampered with.

In order to overcome the drawbacks of such conventional single-layer heat-sensitive recording materials, a transfer-type heat-sensitive recording system has been proposed.

For example, Tokko Akira! /-273≠No., JP-A-Sho≠7-. 211
In No. 317, etc., the two heat-sensitive components are printed on separate sheets, and the coating layers are combined to print. l-! In the 1j7rr issue, colored dyes and pigments are added to the heat-sensitive transfer layer, and printing is performed by combining the heat-sensitive transfer layer and plain paper, as disclosed in JP-A-7-4'j.
A heat-sensitive transfer layer is prepared using waxes or low molecular weight resins, and colored dyes are melted or dispersed therein. It is possible to print in close contact with the paper, and JP-A-Kokai Shoj Goo 1oszzz contains a color-forming substance, a 7-enol substance, and a melting point of 0. /! It is described that printing is performed by adhering a heat-sensitive transfer layer containing an OoC thermofusible substance to plain paper.

However, heat-sensitive recording materials produced using these methods are insufficient in color density and color sensitivity.

Therefore, an object of the present invention is to provide a transfer type heat-sensitive recording material having sufficient color density and color development sensitivity.

The object of the present invention is to provide an electron-donating colorless dye, an electron-accepting compound, and a compound of the following general formula (11, (II) or (III)).
This was achieved by a transfer-type heat-sensitive recording material characterized by having a heat-melt transfer layer containing one or more heat-melting agents represented by:

In the above formula, 1 is an alkyl group or an aralkyl group, 2 is an alkyl group, an aralkyl group, an alkylcarbonyl group, or an arylcarbonyl group t=R3 and n(,.

may be the same or different, and an alkyl group,
an aralkyl group or an aryl group, Y is an alkyl group,
Represents an alkoxy group, an aralkyl group, a phenyl group or a halogen atom.

In the above general formula (1), the alkyl group represented by R□ preferably has a carbon number of l-coO, and has a carbon number of /-IO
is more preferable. The aralkyl group represented by 几 preferably has 7 to λ0 carbon atoms, and particularly preferred examples include benzyl group and phenethyl group.

In the above general formula (I), the alkyl group represented by Y preferably has a carbon number of /-/J-, and more preferably has a carbon number of /-1.

The alkoxy group represented by Y preferably has 7 to /j carbon atoms, more preferably fi/-r carbon atoms. The aralkyl group represented by Y preferably has 7 to -0 carbon atoms, and more preferably has 7 to //0 carbon atoms. The halogen atom represented by Y is preferably a chlorine atom.

In general formula (1), the substituent represented by Y is 01
(Although it may be substituted in any of the ortho, meta and para positions relative to the + group, para-substituted ones are particularly preferred.

In the above general formula (II), the naphthalene ring may further have a substituent, and preferred examples of these substituents include an alkyl group, an aralkyl group, a halogen atom, a hydroxy group, an alkoxy group, an aralkyl group, and an aryl group. Examples include oxy group, alkylcarbonyloxy group, arylcarbonyloxy group, alkoxycarbonyl group, aryloki7carbonyl group, -carbamoyl group, and sulfamoyl group.

In the above general formula (n), the substituent represented by 2 may further have a substituent.

Among the substituents represented by 1L2 in the above general formula (II), an alkyl group having from 20 carbon atoms, an aralkyl group having 7 to λ≠ carbon atoms, a 1-alkylcarbonyl group having 7 to 0 carbon atoms, and a 1-alkyl carbonyl group having 7 to 0 carbon atoms. An arylcarbonyl group of coO is preferable,
Particularly preferred are an alkyl group having 7 to t carbon atoms, an aralkyl group having 7 to 3 carbon atoms, a 1-alkylcarbonyl group having 7 to t carbon atoms, and an arylcarbonyl group having 7 to 3 carbon atoms.

In the above general formula (l[), among the substituents on the naphthalene ring, a halogen atom, a hydroxy group, an alkyl group having a carbon number of l to lθ, an alkyloxycarbonyl group having a carbon number of λ to coθ, a carbon number of 7 to . An aryloxycarbonyl group having 20 carbon atoms and a substituted carbamoyl group having 2 to λj carbon atoms are more preferable.

In the above general formula (Ill'), kL3 and 几. Among the substituents represented by, an alkyl group having 1 to 30 carbon atoms,
A 1-ralkyl group having 7 to 20 carbon atoms, a 1-lyl group having t to λO carbon atoms, particularly an alkyl group having 7-0 carbon atoms,
An aralkyl group having 7 to 10 carbon atoms and an aryl group having 6 to 10 carbon atoms are preferred. Further, the substituents represented by kL3 and 几 may further have a substituent, and examples of preferable substituents include an alkyl group, a 1-alkoxy group, and a halogen atom.

Among the heat-fusifying agents represented by the above general formula (1) or (if), those having a melting point of ≠06C-/10°C are preferred, and those having a melting point of zo 0c to /20'C are particularly preferred.

Further, among the heat-fusifying agents represented by the above general formula (Illll), those having a melting point of ≠oc-xoo'c are preferable, and those having a melting point of to''c to 770°C are particularly preferable.

Next, specific examples of the thermofusifying agent according to the present invention will be shown, but the present invention is not limited thereto.

/) Examples of compounds represented by general formula (I) p-t-1-
y-phenylbenzyl ether, p-t-7milphenylbenzyl ether, p-isopropylbenzyl-p
-biphenyl ether, β-phenethyl-p-biphenyl ether, α-7enethyl-p-biphenyl ether, β-n-butoxyethyl-p-biphenyl ether, p-cyclohexylphenylbenzyl ether, p-
Cumylphenylbenzyl ether, p-isozolobylbenzyl-p-7nisyl ether, p-chlorophenyl-
p-isopropylbenzyl ether.

c) Examples of compounds represented by general formula (II)/-benzyloxynaphthalene, copenzyloxynaphthalene,
λ-p-methylbenzyloxynaphthalene, λ-p-chlorobenzyloxynaphthalene, Co1)-isopropylbenzyloxynaphthalene, copenzoyloxynaphthalene, l-hydroxy-111inzoyloxina7
Talene, Cophenoxia, Cetyloxynaphthalene.

3) Examples of compounds represented by general formula (III) Stearoylanilide, stearoyl-9-)leucito, stearoyl-p-chloroanilide, N-p-chlorobenzoylstearylamine, N-p-chlorobenzoylbenzylamine, NI) -chlorobenzoyl-p'-chlorobenzylamine, phenyl7*f rule-chloroanilide, p-chlorophenylacetyl-p'-chloroanilide, p-tolylbucetyl-p'-chloroanilide, and the like.

The transfer type heat-sensitive recording material according to the present invention has the general formula (1)
(II) Contains one or more thermofusible agents represented by (n[).

Examples of the electron-donating colorless dye used in the present invention include triarylmethane compounds, diphenylmethane compounds,
Xanthine compounds, thiazine compounds, spiropidine compounds, etc. are used. To give some examples of these, triarylmethane compounds include 3.3-
Bis(p-dimethylaminophenyl)-4-dimethylaminophthalide (i.e. crystal violet lactone)
, 3.3-bis(p-dimethylaminophenyl) phthalide, J-(p-dimethylaminophenyl)-J-(/,
J-dimethylindol-3-yl]phthalide, J-(
Examples of diphenylmethane compounds include p-dimethylaminophenyl)-j-(cotatylindol-3-yl)phthalide, ≠I-bis-dimethylaminobenzhydrin benzyl ether, N-halophenyl-leuco Auramine, N-2,4', j-trichlorophenylleucoauramine, etc., xanthine compounds include rhodamine-B-anilinolactam, rhodamine (p-nitroanilino)lactam, rhodamine B (
p-chloroanilino)lactam, no-dibenzylamino-t-diethylaminofluorane, λ-anilino-t-
Diethylaminofluorane, co-anilino 3-methyl-4-diethylaminofluorane, λ-anilino 3-
Methyl-6-cyclohexylmethylaminofluorane,
Co〇-chloroanilino-4-diethylaminofluorane 1,2-m-chloroanilino-4-diethylaminofluoran, Co(J, ref.-dichloroanilino)-4-diethylaminofluorane, λ-octylamino-4-diethylaminofluoran Fluorane, -1-dihexylamino-4-
Diethylaminofluoran, Co-m-trifluoromethylanilino-4-diethylaminofluoran, Co-optylamino-3-chloro-6-diethylaminofluoran,
-1ethoxyethylamino-3-chloro-6-diethylaminofluorane, -1anilino-3-chloro-t-diethylaminofluorane, λ-diphenylamino-l-
Diethylaminofluorane, λ-anilino 3-methyl-6-siphenylaminofluorane, cophenylaminofluorane 4
Examples of spiro-based compounds include 3-methyl-spiro-dinaphthopyran, 3-ethyl-spiro- Cina7toviran, 3,3'-cyclolosespiro-dinaphthopyran, 3-benzylspiro-dinaphthopyran, J-methyl-(J-methoxybenzenespiropyran, 3-propyl-spiro-dibenzopyran, etc.) These can be used alone or in combination.

Examples of electron-accepting compounds include phenolic compounds,
Organic acids or their metal salts, ogishibenzoic acid esters,
Phenol compounds are particularly preferred because they require only a small amount. Specifically, daterty butylphenol, μm phenylphenol, ≠
-Hydroxydiphenoxide, α-su7thol, β-naphthol, methyl-≠-hydroxy7penzoate 1.2
゜-'-dihydroxybiphenyl, co, corbis (4
'-Hydroxyphenyl)furopane (bisphenol A
), λ, 2-bis(≠-hydroxyphenyl)butane,
μ, Hiro'-isopropylidene bis(2-methylphenol), lI/-bis-(3-chloro-≠-hydroxyphenyl)cyclohexane, /,/-bis-(3-chloro-Hiro-hydroxyphenyl)-cope thylamino, ≠,
≠'-Secondary isobutyrizo/diphenol, ≠-
Examples include hydroxybenzoic acid benzyl ester.

Next, embodiments of the transfer type heat-sensitive recording material according to the present invention will be described. The most common form is to coat one side of a support with the heat-melt transfer layer according to the present invention to form a transfer sheet, place an image-receiving sheet in close contact with the heat-melt transfer layer of the transfer sheet, and perform thermal printing using a thermal head or the like. , to obtain an image on an image-receiving sheet.

Further, a conventional heat-sensitive layer may be provided on the opposite side of the heat-melting transfer layer of the transfer sheet support.

As the support for the transfer sheet, paper such as plain paper, glassine paper, tracing paper, typewriter paper, condenser paper, synthetic paper, cellulose acetate, Saran, polynystel, etc. can be used. can.

The heat-melting transfer layer according to the present invention contains an electron-donating colorless dye, an electron-accepting compound, and one or more heat-fusifying agents represented by the general formula (1), (If), or (ill), as well as a binder and an additive. It is possible to contain agents such as agents. As a binder, water-soluble resins such as polyvinyl alcohol, methyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose, methyl vinyl ether maleic anhydride copolymer, polyacrylic acid, gelatin, gum arabic, starch, styrene-butadiene latex, xylene resin,
Phenolic resin, coumarin resin, vinyltoluene resin,
Oil-soluble resins such as vinyl acrylic resins and chill-in resins can be used. As additives, in order to improve the adhesion between the transfer layer and the image-receiving sheet, and to improve the transferability to the image-receiving sheet, we use rough-in wax, polyolefin wax, microwax, fatty acid amide wax, celery/, Carnauba wax, monothane wax, polyethylene wax, synthetic wax, polyolefin/,
Waxes such as solid fatty acids and resins such as cellulose resins, acrylic resins, and rosin-modified maleic acid resins can be used.

Further, this additive may be provided alone as an intermediate layer between the hot-melt transfer layer and the image-receiving sheet.

As the image receiving sheet, paper such as plain paper, synthetic paper, laminated paper, etc., or resin film such as polyethylene, polystyrene, polypropylene, etc. is used. Further, a layer containing a receiving agent may be provided on the image receiving sheet in order to further strengthen the fixing of the print transfer portion.

Accepting agents include paraffin, microwax, synthetic wax, waxes such as fatty acid amide, rubbers such as natural rubber, sitadiene rubber, styrene-butadiene rubber, polyolefins, polyvinyl ethers, polyesters, nylon, rosin-modified maleic acid, etc. Various plastics such as resins and rosin-modified phenolic resins, plasticizers, and inorganic pigments such as Kaori, talc, and calcium carbonate can be used.

Next, the most common manufacturing method will be described. The above-mentioned colorless electron-donating dye, electron-accepting compound, and heat-fusifying agent are each separately or appropriately combined and dispersed in a dispersant by means such as a ball mill or a sand mill.

After mixing the champion, binders, additives, brighteners, fillers such as clay, clay, etc. are added as necessary to create a coating liquid.

The coating liquid is applied onto a support sheet and dried. Generally, the amount of coating is 2 to 7 m2 in terms of solid content. The thus obtained transfer sheet is used by bringing the heat-melting transfer layer of the transfer sheet and the image receiving sheet into close contact with each other in advance, or by bringing them into close contact with each other immediately before printing. To achieve close contact, there are methods such as passing through a calender, machine calendar, cross calender, etc., using the nip of a laminator, or simply passing it between a pressurized rubber roller.

Examples will be shown below, but the present invention is not limited only to these examples.

Example 1 Liquids A, D, and C having the following compositions were each separately dispersed in a ball mill for a day and night, and after mixing these three dispersions,
A 30% dispersion of Nomizinoin wax (Middle East Cellosol #4L) toy was added to prepare a coating liquid.

The coating liquid was applied onto typewriter paper having a basis weight of λoy 7m so that the solid content coating amount was ioy, im2, and dried at a relatively low temperature to form a transfer sheet. ≠o
Linear pressure gokgW/ by combining yim2 high quality paper and transfer layer
I applied super calender with α and glued the two pieces together.

This sheet can be heated using Iom by facsimile.
After heating and printing at J/mm2, the two sheets were peeled off.

Measure the density on the image receiving sheet side using a Maquis RDj/Kogata densitometer (
As a result of measurement using a visual filter), the density of the printed area was 0.12, the density of the background area was 0.07, and the recolor density after reheating the background area was 0.

A recording sheet that could be fixed was obtained with almost no color development even after recoloring.

Example 2 Liquid D having the following composition was used instead of liquid C in Example 1, and coating and adhesion were carried out in the same manner as in Example 1. As a result, a fixable recording sheet was obtained.

Example 3 In place of liquid 13 and liquid G in Example 1, Ei and F liquids having the following compositions were used, and dispersion, coating, and adhesion were carried out in the same manner as in Example 3. As a result, fixing was possible in Example 3. 4 Liquids G, H and (2) having the following compositions were each dispersed in the same manner as in Example 1, and then applied onto glassine paper having a basis weight of izy/m2 and dried to obtain a transfer sheet.

After dispersing liquid J with the following composition overnight in a ball mill, ttoy
It was coated on the glossy surface of Yankee finished base paper having a basis weight of 7 m 2 to a solid content coating amount of 3y7 m 2 and dried to form an image-receiving sheet.

The transfer sheet and the image-receiving sheet were combined and glued together using a super calender to obtain a fixable recording sheet.

Next, a comparative example will be shown.

Comparative Example 1 Using liquids A and B of Example 1 and a liquid having the composition shown below, a transfer sheet was formed in the same manner as in Example 1, and was further adhered to an image-receiving sheet.

Table 1 shows the results of Examples and Comparative Examples of the present invention.

Table 1 It can be seen from Table 1 that the recording material according to the invention clearly has a high sensitivity.

Claims (1)

[Scope of Claims] A heat-melting transfer layer containing an electron-donating colorless dye, an electron-accepting compound, and one or more heat-melting agents represented by the following general formula (I), (If), or ([1)] A transfer type heat-sensitive recording material characterized by the following. In the above formula, 几 represents an alkyl group or an aralkyl group, R2 represents an alkyl group, an aralkyl group, an alkylcarbonyl group, or an arylcarbonyl group, and 几 and R4 each may be the same or different and represent an alkyl group, an aralkyl group, or an aralkyl group. Y represents an alkyl group, an alkoxy group, an aralkyl group, a phenyl group, or a halogen atom.