JPS6334182A - Thermal transfer medium - Google Patents

Abstract

PURPOSE:To obtain a transfer image excellent in heat resistance and improved in abrasion resistance, by constituting the title transfer medium of a thermal transfer sheet provided with a colored thermal transfer layer containing a heat- meltable substance and a cellulosic resin and a receiving sheet having a receiving layer consisting of a resin having a glass transition temp. of specific temp. or higher and an inorg. or org. filler. CONSTITUTION:A thermal transfer medium consists of a thermal transfer sheet wherein a colored thermal transfer layer containing a heat-meltable substance and a cellulosic resin is provided on a support and a receiving sheet having a receiving layer consisting of a resin having a glass transition temp. of 80 deg.C or higher and an inorg. or org. filler. As the support, paper, synthetic paper and, especially, a plastic film are used. As the heat-meltable substance, at least one compound selected from phenols, naphthols, org. acids or salts thereof, esters, amides, alcohols and ethers is used. The use amount of the resin to the filler of the receiving layer of the receiving sheet is about 0.05-5pts.wt. to 1pt.wt. of the filler, and the adhesion amount of the total solid is pref. about 1-15g/m<2>.

Description

DETAILED DESCRIPTION OF THE INVENTION [Technical Field] The present invention relates to a heat-sensitive transfer medium that has excellent heat resistance, is durable, and provides a uniform, high-density transferred image.

[Prior Art] Conventionally, heat-sensitive transfer media include those consisting of a transfer sheet in which a heat-sublimable dye is provided on a support and a receiving sheet that receives a heat-sublimable dye image by thermal printing from the back side of the sheet, and paraffin-based transfer media. A combination of a transfer sheet and a receiving sheet is known, in which a transfer layer of a heat-fusible substance such as wax and a pigment or dye is provided on a support. The dye image on the sheet has poor storage stability, requiring an overcoat to be applied on the transferred image, and in the case of the latter, the transferred image may rub off because the paraffin used as a thermofusible material has low mechanical strength. There was a drawback that the image deteriorated due to friction such as.

It was also disclosed that printing quality could be improved by providing a water-based paint layer or a low-melting point material layer on the receiving paper support (Japanese Patent Publication No. 5)
However, the durability of the transferred image is not necessarily sufficient.

Recently, the scope of use of thermal transfer media has expanded, and their application to recording data input systems, such as bar code systems, has become more prominent. Among these, there is a strong demand for heat resistance and abrasion resistance of transferred images.

In the prior art, when waxes are used in the transfer sheet, the heat resistance temperature is extremely low, and it is almost impossible to use the transfer sheet under environmental conditions of 60 to 70°C or higher.

[Objective] The present invention meets the above-mentioned conventional demands, and provides a transfer image formed on a receiving sheet with significantly excellent heat resistance and improved abrasion resistance due to rough rubbing.

[Groove formation] The present invention provides a thermal transfer sheet in which a colored thermal transfer layer containing a thermofusible substance and a cellulose resin is provided on a support, and a resin having a glass transition temperature (Tg>80°C or higher). A heat-sensitive transfer medium characterized by comprising a receiving sheet having a receiving layer made of an inorganic or organic filler.

Examples of the support in the heat-sensitive transfer sheet include:
Paper, synthetic paper and especially plastic films are used.

The heat-fusible substances in the colored heat-sensitive transfer layer on the support include phenols, naphthols, organic acids or their salts or esters, amides, alcohols, ethers, ketones, and aromatic amines. At least one compound selected from derivatives, biphenyl derivatives, triphenylmethane derivatives, phenanthrene derivatives, fluorene gy 28 derivatives, anthracene derivatives, and carbazole derivatives is used. An example of the arrangement is shown below.

4-1ert-butylphenol 98), 4-hydroxydiphenyl ether (84), 1-naphthol (9
8), 2-naphthol (121), methyl-4-hydroxybenzoate (131), 4-hydroxyacetophenone (109), 2,2°-dihydroxydiphenyl ether (79), 4-phenylphenol (166)
, 4-tert-octylcatechol (109), 2,
2°-dihydroquintuphenyl (103), 4,4゛-
Methylenebisphenol (160), 2,2'--methylenebis(4-chlorophenol) (164), 2,2
゛-Methylenebis(4-methyl-6-tert-butylphenol (125), 4,4゛-isopropylidene diphenol (15B), 4,4゛-isopropylidene bis(2-chlorophenol) (90), 4. 4゛-isopropylidene bis(2,6-didulomphenol), (
172), 4,4"-isopropylidene bis(2-te
rt-butylphenol> (110), 4.4°-
Isopropylidene bis(2-methylphenol) (13
B), 4,4°-isopropylidene bis(2,6-dimethylphenol) (1BB), 4.4'-5eC
-butylidene diphenol (119), 4,4-secondary-butylidene bis(2-methylphenol) (14
2), 4,4゛-cyclohexylidene diphenol (1
80), 4,4"-siloxylidene bis(2-methylphenol) (184), salicylic acid (163)
, salicylic acid methalyl ester (74), salicylic acid phenacyl ester (110), 4-hydroxybenzoic acid methyl ester (131), 4-hydroxybenzoic acid ethyl ester (116), 4-hydroxybenzoic acid propyl ester (98), 4-Hydroxybenzoic acid isopropyl ester (86), 4-hydroxybenzoic acid butyl ester (71), 4-hydroxybenzoic acid isoamyl ester (50), 4-hydroxybenzoic acid phenyl ester (178), 4-didroxybenzoic acid Benzyl ester (111), 4-hydroxybenzoic acid cyclohexyl ester (119), 5-hydroxysalicylic acid (200), 5-chlorosalicylic acid (172), 3
-Chlorsalicyl 1j (17B), thiosalicylic acid (1
64), 2-chloro-5-nitrobenzoic acid (165),
4-methoxyphenol (53), 2-hydroxybenzyl alcohol (87), 2,5-dimethylphenol (75), benzoic acid (122), orthotoluyl 1 (1
07), metatoluic acid 4111), paratoluyl 1l
(181), orthochlorobenzoic acid (142), metaoxybenzoic acid (200), 2,4-dihydroxyacetophenone (97), resorcinol monobenzoate (135), 4-hydroxybenzophenone (133)
), 2,4-dihydroxybenzophenone (144),
2-naphthoic acid (184), 1-hydroxy-2-nano 1-ic acid (195), 3,4-
Dihydroxybenzoic acid ethyl ester (12B), 3,
4-Dihydroxybenzoic acid phenyl ester (189)
, 4-hydroxypropiophenone (150), salicyl salicylate (14B), phthalic acid monobenzyl ester (107), decyl acetamide, decyl propionamide, undecyl acetamide, undecyl propionamide, lauryl acetamide, lauryl propionamide, Tridecyl acetamide, tridecyl propionamide, myristyl acetamide, myristyl propionamide, pentadecyl acetamide, pentadecyl propionamide, balmitylacetamide, palmityl propionamide, palmitic acid amide, heptyl acetamide, heptyl propionamide, stearyl acetamide , stearylpropionamide, stearylbutyramide, stearylvaleramide, stearylcapronamide, stearyllaurinamide, stearylpalmitinamide, stearylstearinamide, nonadecylacetamide, nonadecylpropionamide,
Behenylacetamide, behenylpropionamide, behenylstearinamide, undecanoic acid methylamide,
undecanoic acid ethylamide, lauric acid methylamide,
Lauric acid ethylamide, tridecanoic acid methylamide,
Tridecanoic acid ethylamide, myristic acid ethylamide, myristic acid ethylamide, pentadecanoic acid methylamide, pentadecanoic acid ethylamide, palmitic acid methylamide, palmitic acid dimethylamide, palmitic acid butylamide, stearic acid methylamide, stearic acid ethylamide, stearic acid propylamide, stearic acid butyramide, Stearic acid dimethylamide, stearic acid diethylamide, stearic acid dibutylamide, nonadecanoic acid methylamide, nonadecanoic acid ethylamide, behenic acid methylamide, oleic acid methylamide, oleic acid ethylamide.

N-stearylbenzamide, N-baldityl-2-chloropenzamide, N-stearyl-2-methoxybenzamide, N-stearyl-4-methylbenzamide,
N-palmitic acid 2,4-dimethylbenzamide, N-
Behenylbenzamide, N-behenyl-2-methylbenzamide, N-stearylphenylacetylamide, N
-Behenylphenylacetylamide.

N-cyclohexyl acetamide, N-cyclohexylpropionamide, N-cyclohexylstearamide, N-cyclohexylbenzamide, 'N-cyclohexyl-2-methylbenzamide, N-cyclohexyl-2 -Chlorobenzamide, N-cyclohexyl-
2,4-dimethylbenzamide, N-cyclohexylpalmitic acid amide, N-(2-chlorohexyl) palmitic acid amide, N-(2-methylcyclohexyl)
Stearic acid amide, N-stearylhexahydrobenzamide.

4-hydroxybenzoic acid (2-methoxyphenyl) ester, 4-hydroxybenzoic acid (2-methoxy-4-methylphenyl) ester, 4-hydroxybenzoic acid (3
, 5-dioxyphenyl) ester, 3-hydroxybenzoic acid (4-carboxyphenyl) ester, 4-hydroxybenzoic acid (4-butoxyphenyl) ester, 4
-Citroxybenzoic acid (4-chlorophenyl) ester, salicylic acid (2-chlorophenyl) ester, salicylic acid (4-chlorophenyl) ester, salicylic M (2-chlorophenyl) ester
, 4-dichlorophenyl) ester, salicyl l(2,
6-dichlorophenyl) ester, salicyl 1(2,4
, 6-trichlorophenyl) ester, 1-noritylwi
(2-bromophenyl) ester, salicylic acid (4-bromophenyl) ester, salicylic acid (2,4-dibromophenyl) ester, salicylic acid M (2,6-dibromophenyl) ester, salicylic acid (2,4,6-tribromo phenyl) ester, salicylic acid (3-methylphenyl) ester, salicylic acid l(2,4-dimethylphenyl) ester, 1-noritylic acid (4-tert-aryamylphenyl) nisder, salicylic acid (4-tert-aryamylphenyl) ester, Salicylic! (2-methoxydiphenyl) ester, salicylic acid (2-ethoxyphenyl)
ester, salicylic acid (3-methoxyphenyl) ester, salicylic acid (4-hydroxyphenyl) ester,
Salicylic acid (4-benzylphenyl) ester, salicylic acid (4-benzoylphenyl) ester, salicylic acid (2-methoxy-4-allylphenyl) ester, salicylic acid (alpha naphthyl) ester, salicylic acid (beta naphthyl) ester, salicylic acid (4-chloro) -3
-methylphenyl) ester, salicylic acid (3-hydroxyphenyl) ester, salicylic M (4-propenylphenyl) ester, 5-chlorosalicylic acid (3-methylphenyl) ester, 3,5-dichlorosalicylic acid (
2-methoxyphenyl) ester.

Benzoic acid phenyl ester, benzoic acid-4-methylphenyl ester, benzoic acid-2,4-dichlorophenyl ester, benzoic acid Wl-2,4,6-trichlorophenyl ester, benzoic acid 112-2-methyl-4-chlor Phenyl ester, benzoic acid-3-bromphenyl ester, benzoic acid 1m-2,4-dibromphenyl ester, benzoic acid 1m-3-iodophenyl ester, benzoic acid-3
-21~ phenyl ester, 4-methyl benzoate-
2,6-dichlorophenyl ester, benzoic acid 1-4-isopropylphenyl ester, benzoic acid 4-↑-butylphenyl ester, benzoic acid 4-benzylphenyl ester, benzoic acid fl12-4- (1°-naphthyl)
Phenyl ester, benzoic acid-2-benzoyloxyphenyl ester, benzoic acid-4-(2'-methyl)diphenyl ester, benzoic acid-2-phenylethyloxyphenyl ester, benzoic acid-2-ace1-xyphenyl ester , benzoic M-4-methoxyphenyl ester, benzoic@-4-(4°-methyl)phenoxyphenyl ester, 4-methylbenzoic acid phenyl ester, 4-
Methoxybenzoic acid phenyl ester, 4-phenoxybenzoic acid phenyl ester, 4-acetoxybenzoic acid phenyl ester, 4-methoxybenzoic acid-4°-methoxyphenyl ester, 2-acetoxybenzoic acid phenyl ester, 2-benzoyloxybenzoic acid phenyl ester ester, 2-nitrobenzoic acid-4-methylphenyl ester, 4-nitrobenzoic acid-4-methylphenyl ester,
4-benzoyloxybenzophenone, 2-benzoyloxy-4'-methylbenzophenone.

4-benzoyloxybenzoic acid methyl ester, 4-benzoyloxybenzoic acid ethyl ester, 4-benzoyloxybenzoic acid-n-propyl ester, 4-benzoyloxybenzoic acid benzyl ester, 4-benzoyloxybenzoic acid phenyl ester, 2- Benzoyloxybenzoic acid phenyl ester, 4-(4°-methylbenzoyloxy)benzoic acid ethyl ester, 4-(4°-
methoxybenzoyloxy)benzoic acid ethyl ester,
4-(4'-chlorobenzoyloxy)benzoic acid ethyl ester.

Stearyl alcohol, mericyl alcohol, crotyl alcohol, 1,8-octadiol, 1,14-tetradecanediol, 2,5-dimethyl-3-hexene-
2,5-diol, 2,4-dimethyl-2,3,4-pentatriol, pentamethylglycerin, 1,2,3
．． 4-pentatetrol, polyethylene glycol, monostearate, di-n-hexadecyl phenyl ether, di-n-heptadecylphenyl ether, di-n-
Octadecyl ether, 4-methoxydiphenylamine, 4,4°-dimethoxydiphenylamine, P-benzyl-biphenyltriphenylmethane, alkylated or hydrides of fluorene, phenanthrene or anthracene, and hydrides of alkylphenanthrene or alkylanthracene, N-ethyl Carbazole, N
-benzoylcarbazole, 4,4°-dimethoxydiphenylsulfone, 4,4°-di-n-butoxydiphenylsulfone, 4,4°-di-1SO-pentyloxydiphenylsulfone, 4-iso-n-propoxy-4°
-n-butoxydiphenylsulfone, etc.

Cellulose resins used in combination with these thermofusible substances include, for example, cellulose acetate, ethyl cellulose,
Examples include nitrocellulose, carboxymethylcellulose, cellulose propionate, hydroxypropylcellulose, methylcellulose, ethylhydroxyethylcellulose, cellulose acetate butyrate, and cellulose acetate propionate.

Pigments and/or dyes are dispersed in the heat-sensitive transfer layer.

Pigments or dyes that are thermofusible or thermoinfusible are used, such as carbon black, triiron tetroxide,
Black pigments such as nigrosine base, acetylene black,
In addition to coloring pigments such as lamp black, bone black, graphite, iron black, mineral black, cyanine blue, ultramarine blue, navy blue, cobalt blue, phthalocyanine blue, oil blue, and alkali blue, Iozole red, rose bengal, crystal violet lactone, Examples include brilliant green.

The amount of the pigment or dye and thermofusible substance used is preferably 0.1 to 10 parts by weight per 1 part by weight of the pigment and/or dye. The amount of cellulose resin used is preferably o, oi to 1 part by weight per 1 part by weight of the thermofusible substance. The total solid content is preferably 0.5 to 10 g/l.

The receiving sheet in the present invention is a support such as paper, synthetic paper,
An inorganic or organic filler layer is provided as a receptor layer on the surface of a plastic film. The filler has an oil absorption capacity of 50ml/100g (according to JIS 5101 method)
As mentioned above, it is preferable to contain porous filler in an amount of preferably 150 m1/100 g or more. Specific examples of porous fillers include inorganic and organic fine powders such as silica, aluminum silicate, alumina, aluminum hydroxide, magnesium hydroxide, urea-formalin resin, and styrene resin.

The resin used as a binder has excellent heat resistance and preferably has a glass transition temperature (TO> of 80°C or higher, such as polyisopropyl methacrylate (81°C), polymethyl methacrylate (105°C), polymethacrylic acid Butyl (107℃), polyphenyl methacrylate (110℃)
, polyacrylonitrile (105℃), polyhexyl acrylate (106℃), polystyrene resin (100℃)
, styrene-acrylic resin (103°C), rosin-modified maleic acid resin (120-140°C), epoxy resin (9
Examples include acrylic, styrene, and epoxy resins (7 to 150°C).

The amount of filler and resin used in the receptor layer of the receptor sheet is preferably about 0.05 to 5 parts by weight per 1 part by weight of filler. The total solid content adhesion amount is preferably about 1 to 15 g/m2.

Next, the present invention will be roughly explained in detail with reference to Examples. Note that (parts) shown below is based on weight.

[Example] Creation of transfer sheet (A-1) Carbon black 10 parts P-benzylbiphenyl on a 6 μm thick polyester film
A composition consisting of 27 parts ethyl cellulose, 1 part methyl ethyl ketone, and 100 parts was dispersed for 24 hours using a ball mill and coated using a wire bar.
A transfer sheet (A-1) having a transfer layer of I2 was created.

Preparation of transfer sheet (A-2) Transfer sheet (A-2> was prepared in the same manner as transfer sheet (8-1) except that cellulose acetate was used instead of ethyl cellulose in transfer sheets 1 to (A-1>).

Preparation of transfer sheet (A-3>) Transfer P-benzylbiphenyl from transfer sheet (A-1> to 4-
A transfer sheet (A-3> was prepared in the same manner as the transfer sheet (A-1>) except that hydroxybenzoic acid butyl ester was used.

Preparation of transfer sheet (A-4>) P-penzylbiphenyl of transfer sheet (A-1>) was added to 4,
A transfer sheet (A-4) was prepared in the same manner as the transfer sheet (A-1) except that 4'-dimethoxydiphenyl sulfone was used.

Preparation of receptor sheet (B-1) Styrene-acrylic emulsion (Tg: 105°C, solid content 50%) 10 parts Silica fine powder (oil absorption maximum 200ml/100g> 8 parts water)
A receptor sheet (B-1) having a receptor layer having a thickness of 5.5 g/m' after drying was prepared by uniformly dispersing a composition consisting of 82 parts and coating it on a high-quality paper (52 g/m2).

Preparation of receptor sheets (B-2, B-3, B-4) The styrene-acrylic emulsion of the receptor sheet (B-1) was mixed with polymethyl methacrylate (Tg: 105°C) (B
-2) Polyimpropyl methacrylate (Tg: 81°C) (B-3) [+Zine-modified maleic acid (TCJ: 120'C)
...(B-4>) Receiving sheets (B-2>, (B-3>, and (B-4)) were created in the same manner as the receiving sheet (B-1>) except that the following were prepared.

Preparation of receiving sheet 1" (L3-b, 13-6>
Receptive sheets (B-5) and (B-6> were prepared in the same manner as the receptive sheet (B-1>) except that polyvinyl chloride (Tg near 0° C.) (B-6) was used.

The transfer sheet and receiving sheet 1~ created as above were combined as shown in the table, the transfer sheet and the receiving sheet were stacked, and 1 mJ of heating energy was applied from the back side of the transfer sheet using a thermal head, resulting in a clear black bar. I got the code image.

The following tests were conducted on the images.

(1) Heat resistance environmental temperature 20℃, 50℃, 100℃, 150℃, 200℃
A load of 20 g/c1 at °C was applied, the image was rubbed 10 times with cardboard, and the image after the test was visually evaluated.

The results of the test are shown in the table.

Note: O: Almost no change in bar image [Effect:] According to the thermal transfer medium of the present invention, a uniform, high-density image with excellent heat resistance, abrasion resistance, and durability can be obtained.

Claims (1)

[Claims] A heat-sensitive transfer sheet comprising a colored heat-sensitive transfer layer containing a thermofusible substance and a cellulose resin on a support, and a receptor comprising a resin having a glass transition temperature (Tg) of 80°C or higher and an inorganic or organic filler. A heat-sensitive transfer medium comprising a receiving sheet having layers.