Source: https://patents.justia.com/patent/4027345
Timestamp: 2019-10-19 04:13:48
Document Index: 174706819

Matched Legal Cases: ['arts 12', 'arts 11', 'arts 12', 'arts 12', 'arts 11', 'arts 12', 'arts 11']

US Patent for Transfer printing Patent (Patent # 4,027,345 issued June 7, 1977) - Justia Patents Search
Justia Patents US Patent for Transfer printing Patent (Patent # 4,027,345)
Jun 12, 1975 - Toyo Boseki Kabushiki Kaisha
A method of transfer printing, wherein a release layer is formed on a temporary support; printing a pattern on said release layer with an ink containing coloring matter therein to obtain a transfer sheet; superposing an article to be transfer-printed on the printed surface of said transfer sheet; heating the superposed aggregate under pressure to transfer the release layer with the pattern onto said article to be transfer-printed; fixing the coloring matter to said article, and then soaping said article to remove the release layer, characterized in that the release layer consists of (1) 10-90 wt. percent of one or more thermoplastic polymers having excellent film-forming properties and water-solubility or alkaline water solubility as well as organic solvent solubility and (2) 90 to 10 wt. percent of one or more plasticizers having a melting point between 30.degree. and 120.degree. C selected from oxycarboxylic acids or their derivatives having water solubility or alkaline water solubility as well as organic solvent solubility.
We made an intensive study to remedy the above-mentioned defects of the conventional methods. As a result, we achieved the transfer printing method of the present invention which uses an entirely new release layer. The present invention is a transfer printing method which comprises forming a release layer on a temporary support; printing a pattern on said release layer with an ink containing a coloring matter to obtain a transfer sheet; superposing an article to be transfer-printed on the printed surface of said transfer sheet; heating the superposed aggregate under pressure to transfer the pattern on the transfer sheet onto said article to be transfer-printed; fixing the coloring matter to said article and then washing the article. The release layer consists of 10 to 90 weight percent of one or more water-soluble or alkaline-water-soluble and organic-solvent-soluble thermoplastic polymers having excellent film-forming properties and 90 to 10 weight percent of one or more plasticizers having a melting point between 30.degree. and 120.degree. C. selected from water-soluble or alkaline-water-soluble and organic-solvent-soluble oxycarboxylic acids or their derivatives.
Thus, the most important feature of the method of the present invention is to use, as the release layer, a mixture of at least one thermoplastic polymer (A) having excellent film-forming properties which is water-soluble or alkaline-water-soluble and organic-solvent-soluble, and at least one plasticizer (B) having a melting point between 30.degree. and 120.degree. C., selected from oxycarboxylic acids or their derivatives which are water-soluble or alkaline-water-soluble and organic-solvent-soluble. Because the thermoplastic polymer (A) has excellent film-forming properties, such defects as the penetration of ink into the release layer during pattern printing, the bleeding and deformation of printed patterns, the cracking and blocking during storage of the printed transfer sheets, the soiling of guide rollers in the printing machine, etc. are eliminated. Also, good smoothness of the release layer surface enables delicate, fine printing at highlighted portions which is, a characteristic feature of transfer printing. Because of the excellent film-forming properties of the thermoplastic polymer, there is no fear that the pattern may be deformed in the fixing treatment of the coloring matter after transferring. Further, because the release layer of the present invention is a combination of the thermoplastic polymer (A) and the plasticizer (B) having a plasticizing effect on the former, it is possible to stably transfer the pattern on the transfer sheet onto the article to be transfer-printed under comparatively low temperature and pressure conditions in a uniform manner and at a high transfer efficiency. In addition, because both the release layer composed of components (A) and (B) are water-soluble or alkaline-water-soluble, the release layer composition moved by transferring to the article to be transfer-printed can be easily and completely eliminated by the usual water-washing or soaping or alkaline soaping. Further, the fact that the release layer components (A) and (B) are organic-solvent-soluble, besides being water-soluble or alkaline-water-soluble, is quite advantageous. That is, because a coating liquid dissolved in an organic solvent medium can be prepared, even if the temporary support is paper, there will be no lowering of smoothness by swelling or deformation of the design by contraction, as may occur when using an aqueous medium. It is possible, therefore, to produce a transfer sheet which is excellent in printing properties and good in pattern fitting. Further, the use of an organic solvent as the medium enables short time drying and high speed production of transfer sheets.
Among the thermoplastic polymers having excellent film-forming properties which are water-soluble or alkaline-water-soluble and organic-solvent soluble, used as a component of the release layer composition formed on the temporary support, there may be mentioned; cellulose derivatives, e.g. hydroxy lower alkyl ethers of cellulose such as hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxyethyl-hydroxypropyl cellulose; hydroxy lower alkyl-lower alkyl mixed ethers of cellulose such as hydroxyethyl-methyl cellulose, hydroxypropyl-methyl cellulose, hydroxyethyl-hydroxypropylmethyl cellulose, hydroxyethyl-ethyl cellulose, hydroxypropyl-ethyl cellulose; derivatives of cyanoethyl cellulose such as cyanoethyl-hydroxyethyl cellulose, cyanoethyl-hydroxypropyl cellulose, cyanoethyl-methyl cellulose, partially hydrolyzed products of cyanoethyl cellulose; cellulose ether-esters such as methyl cellulose acetate, methyl cellulose phthalate, hydroxyethyl cellulose acetate, hydroxyethyl cellulose phthalate, hydroxypropyl cellulose acetate, hydroxypropyl cellulose phthalate, hydroxyethyl-methyl cellulose phthalate; various vinyl copolymers consisting of an ethylenically unsaturated mono- or dicarboxylic acid (such as acrylic acid, methacrylic acid, maleic acid, fumaric acid) and another ethylenically unsaturated monomer copolymerizable therewith (such as acrylic acid ester, methacrylic acid ester, acrylonitrile, vinyl acetate, vinyl propionate, vinyl chloride, acrylamide). The copolymerization ratio of the ethylenically unsaturated mono- or dicarboxylic acid and the other monomer copolymerizable therewith varies depending on the type of the unsaturated carboxylic acid to be used and the other component to be copolymerized. Generally, the unsaturated carboxylic acid is 5-20 mol percent and the copolymerizable component is 95-80 mol percent. Most of the copolymers thus obtained are water-insoluble but are alkaline-water-soluble polymers which, when the free acid groups are neutralized with alkali, becomes water-soluble. Among the above-mentioned cellulose derivatives and vinyl copolymers, particularly preferred are hydroxypropyl cellulose, hydroxypropyl-hydroxyethyl cellulose, hydroxypropyl cellulose phthalate, hydroxypropylmethyl cellulose phthalate, and copolymers composed of 10-15 mol percent of acrylic acid and/or methacrylic acid and 90-85 mol percent of a copolymerizable ethylenically unsaturated monomer consisting mainly of acrylic acid ester and/or methacrylic acid ester. Preferably, the above-mentioned thermoplastic polymers generally have a softening point between 60.degree. and 200.degree. C. Polymers having a softening point below 60.degree. C. are sticky and therefore transfer sheets containing such polymers in the form of rolls are liable to cause blocking during storage. On the other hand, polymers having a softening point above 200.degree. C. require higher temperature because such polymers have low power of transfer.
As the plasticizers having a melting point between 30.degree. and 120.degree. C. which are water-soluble or alkaline-water-soluble and organic-solvent-soluble, selected from oxycarboxylic acids or their derivatives, there are exemplified compounds represented by the general formula:
(HO).sub.n --R.sub.1 --COOR.sub.2
wherein R.sub.1 is a straight-chained or branched aliphatic hydrocarbon residue having 3 or more carbon atoms, preferably 5 to 21 carbon atoms, or aromatic hydrocarbon residue; R.sub.2 is hydrogen or an alkyl group having 1 to 4 carbon atoms; and n is a positive integer from 1 to 3. More concrete examples of preferred plasticizers are: monoxy fatty acids such as hydroxystearic acid, hydroxytetradecanoic acid, hydroxycaproic acid, hydroxydocosanoic acid; dioxy fatty acids such as 2,10-dioxy-tridecanoic acid, 3,11-dioxy-tetradecanoic acid, 2,15-dioxy-pentadecanoic acid, 15,16-dioxy-hexadecanoic acid; trioxy fatty acids such as 8,9,10-trioxy-hexadecanoic acid, 9,10,16-trioxy-hexadecanoic acid; oxybenzoic acid esters such as oxybenzoic acid-n-ethyl, -n-propyl, -n-butyl esters, etc. Oxycarboxylic acids or their derivatives having a melting point below 30.degree. C. are tacky and liable to block although they have a large plasticizing effect. On the other hand, oxycarboxylic acids or their derivatives having a melting point above 120.degree. C. are small in plasticizing effect and poor in transfer efficiency and have low solubility in organic solvents. Thus both are unsuitable. It is desirable that the R.sub.1 of the oxy fatty acids or their derivatives in the above-mentioned general formula be above 5 in the number of carbon atoms. Where paper is used as the temporary support, because a plasticizer having a small number of carbon atoms has a high affinity for paper, it penetrates deeply into the paper during the storage of transfer sheets and seriously lowers the power of transfer. Among the above-mentioned plasticizers, particularly preferred are oxy fatty acids having a melting point between 50.degree. and 100.degree. C. and having R.sub.1 above 5 in the number of carbon atoms. Such oxy fatty acids include 12-hydroxystearic acid (m.p. 78.degree. C.), 2-hydroxypalmitic acid (m.p. 93.5.degree. C.), 11-hydroxypalmitic acid (m.p. 65.5.degree. C.), 14-hydroxypalmitic acid (m.p. 72.8.degree. C.), 16-hydroxypalmitic acid (m.p. 95.degree. C.), .omega.-hydroxylauric acid (m.p. 84.degree.C.), 2-hydroxydodecanoic acid (m.p. 78.5.degree. C.), 2-hydroxytetradecanoic acid (m.p. 88.5.degree. C.), 11-hydroxytetradecanoic acid (m.p. 51.degree.-2.degree. C.), 3,11-dihydroxytetradecanoic acid (m.p. 68.degree. C.), 9,10-dihydroxyundecanoic acid (m.p. 82.degree.-3.degree. C.), etc. Among these, 12-hydroxystearic acid, 11-hydroxypalmitic acid and .omega.-hydroxylauric acid are particularly preferable.
The release layer composition in the present invention consists essentially of a mixture of 10-90 weight percent of the above-mentioned thermoplastic polymer and 90-10 weight percent of the above-mentioned plasticizer. A small amount of a certain kind of additive such as a filler, siccative or other resins may be properly added within the range in which the objects of the present invention are not obstructed. With the amount of addition of the plasticizer less than 10 weight percent, the plasticizing effect is low and the power of transfer is poor. Inversely, where the amount of addition is above 90 weight percent, the design bleeds into the release layer and hinders sharp printing at pattern edges. In addition, contamination of the ink bath, lowering of smoothness of the coated surface, etc. are caused. A more preferable ratio of compounding of the release layer composition is 30-90 weight percent of the above-mentioned thermoplastic polymer and 70-10 weight percent of the above-mentioned plasticizer. Additionally, it is preferable that the release layer of the present invention have a melting point normally between 50.degree. and 150.degree. C., particularly between 70.degree. and 120.degree. C.
In the present invention, one or more kinds of the above-mentioned plasticizers and one or more kinds of the above-mentioned thermoplastic polymers, dissolved in an organic solvent, are coated on the temporary support by means of a gravure coater or roll coater and then dried to form the release layer. Where the temporary support to be used is paper having a comparatively rough surface, a resin such as polyvinyl alcohol, sodium alginate, carboxymethyl cellulose, styrene-butadiene copolymer, etc. may be coated on the surface before the formation of the release layer to fill the roughness or to give smoothness so that the coating efficiency of the release layer composition can be increased and the printing and transferring efficiencies can be promoted. The amount of coating of the release layer composition depends on the kind of temporary support and the composition of the release layer composition to be used, though it is normally 0.5-15 g/m.sup.2, preferably 2-5 g/m.sup.2 in dry amount of coating.
The transfer sheet thus obtained is normally rolled up, and then introduced to the transfer printing process or stored. In the transfer printing process, the printed surface of the transfer sheet and the article to be transfer-printed are placed on each other so that the printed surface of the transfer sheet contacts the surface of the article. The superposed assembly is then heated under pressure by means of calender rolls or hot plates normally at a temperature between 80.degree. and 180.degree. C., preferably between 100.degree. and 150.degree. C., instantaneously or for a short time. The design on the transfer sheet, together with the release layer, is transferred onto the article to be transfer-printed. Where the transfer sheet of the present invention is used, the transference is accomplished instantaneously under heat and pressure by hot calender rolls at a temperature between 80.degree. C. and 180.degree. C., preferably between 100.degree. C. and 150.degree. C. at a pressure between 1 and 100 kg/cm.sup.2, preferably between 10 and 50 kg/cm, with the transfer efficiency attaining above 90 %. Therefore, this enables continuous transference and provides great industrial and economical advantages. In the case of heat and pressure by means of a hot plate press at a temperature between 100.degree. and 150.degree. C. at a pressure between 0.2 and 5 kg/cm.sup.2, the transfer efficiency of the printing layer attains above 90%.
The following release layer composition (a) was coated uniformly on a glassine paper by a gravure coater so that the dry amount of coating was 2.5 g/m.sup.2, and was then dried.
______________________________________ (a) Release layer composition ______________________________________ Hydroxypropyl cellulose (HPC-SL, Nippon Soda Co., Ltd.) 13 parts 12-Hydroxystearic acid 7 parts Methanol 40 parts Toluene 40 parts ______________________________________
______________________________________ (b) Printing ink ______________________________________ Sumikaron Red E-FBL Conc. (Sumitomo Chemical Co., Ltd.; C.I. Disperse Red 60) 7 parts Copolymer of ethyl acrylate/methyl acrylate/acrylic acid (50/30/12 mol %) 15 parts Toluene 30 parts Methyl ethyl ketone 30 parts Isopropanol 18 parts ______________________________________
A polyester fabric suede was placed on the printed surface and was passed between calender rolls heated to 130.degree. C. under a pressure of 30 kg/cm at the rate of 5 m/min. Upon leaving the calender, the glassine paper of the support had been already separated. The transfer efficiency of the ink (dye) was about 90 %. The transfer-printed fabric was then steamed at 130.degree. C. for 30 minutes for dye fixation and color development. Thereafter, the fabric was subjected to reducing washing at 70.degree. C. for 20 minutes with an aqueous solution composed of 2 g/l sodium hydroxide, 2 g/l sodium hydrosulfite and 2 g/l Amylasin (a detergent; Dai-ichi Kogyo Seiyaku Co., Ltd.) to dissolve and remove unfixed dye, the release layer and ink binder and then washed with water and dried. As a result, there was obtained a printed product having a photograph-like design and an excellent touch and which was sharp at pattern edges. Additionally, in a comparative example by a transfer sheet using only hydroxypropyl cellulose as the release layer, the transfer efficiency was below 30 %. In another comparative example using 12-hydroxystearic acid singly, in addition to a difficulty in the pattern printing in preparing the transfer sheet, deformation of the pattern occurred upon transferring, so that no practicable one was obtained.
The following release layer composition (c) was coated uniformly on a cellophane film with a gravure coater so that the dry amount of coating was 3 g/m.sup.2, and was then dried.
______________________________________ (c) Release layer composition ______________________________________ Copolymer of ethyl acrylate/methyl methacrylate/acrylic acid (50/38/12 mol %) 10 parts 11-Hydroxypalmitic acid 10 parts Toluene 20 parts Isopropanol 20 parts Methyl ethyl ketone 40 parts ______________________________________
______________________________________ (d) Printing ink ______________________________________ Sumiacryl Brilliant Red N-4G Conc. (Sumitomo Chemical Co., Ltd.; C.I. Basic Red 14) 5 parts Rosin modified alkyd resin (Malkyd 30 A; Arakawa Rinsan Co.) 20 parts Methanol 20 parts Isopropanol 55 parts ______________________________________
On the printed surface of the transfer sheet thus obtained, a knitted fabric composed of an acrylic fiber (Exlan.sup.R ; Japan Exlan Co. Ltd.) was placed and was heat-pressed at a pressure of 5 kg/cm.sup.2 with a plate press heated to 105.degree. C. for 10 seconds. Thereafter, the cellophane film was removed and the pattern was transferred onto the knitted fabric. The transfer efficiency of the ink (dye) was about 90 %. Subsequently, the transfer-printed fabric was steamed at 110.degree. C. for 20 minutes for dye fixation and color development. Thereafter, the fabric was soaped with an aqueous solution composed of 2 g/l chip soap and 2 g/l sodium carbonate at 60.degree. C. for 10 minutes to dissolve and remove unfixed dye, the release layer and ink binder. The fabric was then washed and dried. There was obtained a printed product on which the pattern with sharp edges was reproduced and which had an excellent hand.
The following release layer composition (e) was coated on a polyethylene terephthalate film (polyester film produced by Toyo Boseki Kabushiki Kaisha, 25 .mu. in thickness) with a gravure coater so that the dry amount of coating was 3 g/m.sup.2, and was then dried.
______________________________________ (e) Release layer composition ______________________________________ Hydroxypropyl-methyl cellulose phthalate (HP-50; Shin-etsu Chemical Co., Ltd.) 10 parts .omega.-Hydroxylauric acid 10 parts Methanol 60 parts Isopropanol 20 parts ______________________________________
______________________________________ (f) Printing ink ______________________________________ Suminol Fast Blue-PR Conc. (Sumitomo Chemical Company Limited; C.I. Acid Blue 129) 10 parts Copolymer of ethyl acrylate/methyl methacrylate/acrylic acid (50/38/12 mol %) 15 parts Isopropanol 30 parts Methyl ethyl ketone 30 parts Toluene 15 parts ______________________________________
A nylon crepon produced by Toyo Boseki Kabushiki Kaisha was placed on the printed surface of the thus obtained transfer sheet and was passed between calender rolls heated to 100.degree. C. at a pressure of 30 kg/cm.sup.2 at the rate of 5 m/min. Thereafter, the polyester film was separated and removed. The transfer efficiency of the ink (dye) was about 100 %. The transfer-printed fabric was then steamed at 105.degree. C. for 30 minutes to fix the dye and to develop color. The fabric was then soaped with an aqueous solution composed of 2 g/l sodium carbonate and 5 g/l Marseilles soap at 70.degree. C. for 10 minutes to dissolve and remove unfixed dye, the release layer and ink binder. The fabric was then washed with water and dried. A printed cloth which was sharp at pattern edges and had a good hand was obtained.
A 5 % aqueous solution of polyvinyl alcohol (Gosenol NH-20; Nippon Synthetic Chemical Industry Co., Ltd.) was coated with a gravure coater on a copy paper so that the dry amount of coating was 0.5 g/m.sup.2, and then dried and passed between heated calender rolls to obtain a sized paper of excellent smoothness. On this paper, the same release layer composition (a) as in Example 1 was coated so that the dry amount of coating was 2.5 g/m.sup.2 and was dried. A pattern was offset-printed on this release layer using the following printing ink (g) and the printed ink was dried.
______________________________________ (g) Printing ink ______________________________________ Sumifix Brilliant Red BS Conc. (Sumitomo Chemical Company Limited; C.I. Reactive Red 111) 10 parts Hydroxypropyl cellulose 5 parts Rosin-modified maleic acid resin (Malkyd 30 A; Arakawa Rinsan Co.) 10 parts Isopropanol 30 parts Toluene 30 parts Ethyl acetate 15 parts ______________________________________
A cotton poplin which had been impregnated with the following treating liquid (h) (squeezed to a wet pick-up of 70 %) and dried, was placed on the printed surface of thus obtained transfer sheet, and was passed between calender rolls heated to 150.degree. C. at a pressure of 30 kg/cm.sup.2 at the rate of 5 m/min. At the outlet of the calender rolls, the temporary support (copy paper) had been already separated. The transference was performed extremely uniformly and smoothly. The transfer efficiency of the ink (dye) reached as high as 95 %.
______________________________________ (h) Treating liquid ______________________________________ Sodium alginate 5 parts Sodium bicarbonate 3 parts Urea 5 parts Water 87 parts ______________________________________
This transfer-printed cloth was then steamed at 100.degree. C. for 10 minutes to fix the dye and to develop color. Thereafter, the cloth was soaped with an aqueous solution composed of 2 g/l sodium carbonate and 5 g/l Marseilles soap at 80.degree. C. for 10 minutes to dissolve and remove unfixed dye, the ink binder and the release layer, and was then washed with water and dried. There was obtained a clear deep-colored printed cloth having sharp pattern edges.
______________________________________ (i) Release layer composition (present invention) ______________________________________ Hydroxypropyl cellulose 12 parts 12-Hydroxystearic acid 12 parts Metanol 40 parts Isopropanol 16 parts Toluene 20 parts (j) Printing ink composition ______________________________________ Disperse dye (Sumitomo Chemical Company Limited) 7 parts Yellow ink: Sumikaron Yellow SE:5G conc. (C.I. Disperse Yellow 5) Red ink: Sumikaron Red S-BL Conc. (C.I. Disperse Red 88) Blue ink: Sumikaron Blue S-BG Conc. (C.I. Diserse Blue 73) Hydroxypropyl cellulose 5 parts Rosin-modified maleic acid resin (Malkyd 32; Arakawa Rinsan Co.) 10 parts Isopropanol 50 parts Toluene 15 parts Ethyl acetate 13 parts ______________________________________
On a copy paper which had been surface-sized with polyvinyl alcohol (Gosenol NH-20.RTM.; Japan Synthetic Chemical Industry Co.) and hot calender-finished, release layer formation and three-color printing were performed continuously by a four-color gravure printing machine, using the above-mentioned release layer composition (i) and the three-color printing inks shown in (j) to prepare a transfer sheet. During the printing process, pollution of the guide rolls of the printing machine, deformation of the pattern and picking did not occur to allow excellent printing which was sharp at pattern edges and had a good printing effect at highlight portions. The transfer sheets, after storage for 6 months at room temperatures in the form of rolls, did no show any blocking phenomenon. A polyester texturized yarn fabric was placed on the printed surface of this transfer sheet and was passed between calender rolls heated to 130.degree. C. under the conditions of 30 kg/cm.sup.2 and 5 m/min. Upon leaving the calender, the copy paper and the polyester cloth had been already separated from each other. The transfer efficiency of the ink was about 90 %. After the transfer-printed cloth was then steamed at 130.degree. C. for 30 minutes for dye fixation and color development, it was subjected to reducing washing treatment as in Example 1 to dissolved and remove unfixed dyes and the release layer and ink binder, and then washed with water and dried. There was obtained a printed product which was sharp at pattern edges and splendid in tones and which was not impaired in hand.
______________________________________ Release layer compositions (comparative examples) ______________________________________ (k) Rosin ester (Ester Gum A; Arakawa Rinsan Co.) 40 parts Calcium bicarbonate 20 parts Toluene 40 parts (1) Polyethylene (AC Polyethylene 629; Allied Chemical Co., Ltd.) 10 parts Paraffin wax 10 parts Nonylphenol ethylene oxide 5 parts Water 75 parts (m) Polyamide resin 30 parts Polyethylene glycol No. 6000 5 parts Ethyl cellulose 3 parts Toluene 40 parts Ethanol 22 parts (n) Picotex 120 (Esso Standard Petroleum Co., Ltd.) 30 parts Stearic acid 5 parts Ethyl cellulose 3 parts Toluene 62 parts (o) Polyvinyl alcohol (Gosenol CH-17; Japan Synthetic Chemical Industry Co.) 5 parts Resorcine 20 parts Ethanol 15 parts Water 60 parts ______________________________________
______________________________________ (p) Release layer composition ______________________________________ Hydroxypropyl-methyl cellulose phthalate (HP-50; The Shin-etsu Chemical Industry Co.) 10 parts 12-Hydroxystearic acid 15 parts Toluene 25 parts Methanol 30 parts Isopropanol 20 parts (q) Printing ink composition ______________________________________ Acid dye (Sumitomo Chemical Company Limited) Yellow ink: Aminyl Yellow F-5GL (C.I. Acid Yellow 127) Red ink: Aminyl Brilliant Red F-4B (C.I. Acid Red 247) Blue ink: Aminyl Sky Blue F-R (C.I. Acid Blue 112) Hydroxypropyl cellulose 5 parts Rosin-modified maleic acid resin (Malkyd -32; Arakawa Rinsan Co.) 10 parts Isopropanol 35 parts Methanol 35 parts ______________________________________
On a fine quality paper which had been surface-sized with polyvinyl alcohol and hot calender-finished as in Example 5, release layer formation and three color printing were performed continuously by a four color gravure printing machine, using the above-mentioned release layer composition (p) and three color inks (q), to prepare a transfer sheet. During the printing process, pollution of the guide rolls of the printing machine, deformation of the pattern and picking did not occur to allow excellent printing which was sharp at pattern edges and had a good printing effect at highlight portions. The transfer sheets, after storage for 6 months at room temperatures in the form of rolls, did not show any blocking phenomenon. A wool muslin was placed on the printed surface of this transfer sheet, and was passed between calender rolls heated to 140.degree. C. under the conditions of 50 kg/cm.sup.2 and 5 m/min. Upon leaving the calender, the fine quality paper and the wool fabric had been already separated from each other. The transfer efficiency of the ink was 92 %. After the transfer-printed fabric was steamed at 100.degree. C. for 60 minutes for dye fixation and color development, it was soaped with an aqueous solution composed of 1 g/l polyphosphoric acid and 2 g/l Amylasin at 60.degree. C. for 10 minutes to dissolve and remove unfixed dyes and the release layer and ink binder, and then washed and dried. There was obtained a printed product which was sharp at pattern edges and splendid in tones and which was not impaired in hand.
______________________________________ (r) Release layer composition ______________________________________ Hydroxypropyl cellulose 10 parts 11-Hydroxypalmitic acid 20 parts Toluene 20 parts Methanol 30 parts Isopropanol 20 parts (s) Printing ink composition ______________________________________ Basic dye (Hodogaya Chemical Co.) 15 parts Yellow ink: Aizen Catilon Brilliant Yellow (C.I. Basic Yellow 13) Red ink: Aizen Catilon Brilliant Pink BH (C.I. Basic Red 36) Blue ink: Aizen Catilon Pure Blue 5GH (C.I. Basic Blue 3) Hydroxypropyl cellulose 5 parts Rosin-modified maleic acid resin (Malkyd-32) 10 parts Isopropanol 70 parts ______________________________________
On a fine quality paper which had been surface-sized with polyvinyl alcohol and hot calender-finished, continuous (on-line printing) as in Example 5 was performed, using the above-mentioned release layer composition (r) and the three color inks (s), to prepare a transfer sheet. During the printing process, pollution of the guide rolls of the printing machine, deformation of the pattern and picking did not occur, to allow excellent printing which was sharp at pattern edges and had good printing effect at highlight portions. The transfer sheets, after storage for 6 months at room temperatures in the form of rolls, did not show any blocking phenomenon. A basic dyeable polyester texturized yarn woven fabric was placed on the printed surface of this transfer sheet and was passed between calender rolls heated to 130.degree. C. at a pressure of 30 kg/cm.sup.2 and at the rate of 5 m/min. Upon leaving the calender, the fine quality paper and the fabric had been already separated from each other. The transfer efficiency of the inks was 95 %. After the transfer-printed fabric was steamed at 120.degree. C. for 30 minutes to fix the dyes and to develop color, it was subjected to reducing washing with a solution of the same recipe as in Example 1 and washed with water and dried. There was obtained a printed product which was sharp at pattern edges and splendid in tones and which was not impaired in hand.
______________________________________ (t) Release layer composition ______________________________________ Copolymer of n-butyl acrylate/methyl methacrylate/methacrylic acid (20/65/15 mol %) 10 parts 12-Hydroxystearic acid 15 parts Toluene 15 parts Isopropanol 20 parts Methanol 40 parts ______________________________________
On a copy paper, a styrene-butadiene copolymer emulsion (Hycar LX 204.RTM.; The Japan Geon Co.) was coated with a gravure coater so that the dry amount of coating was 0.5 g/m.sup.2, and was then dried and passed between hot calender rolls to obtain a sized paper of excellent smoothness. On this sized paper, the above-mentioned release layer composition (t) was coated with a gravure coater so that the dry amount of coating was 3 g/m.sup.2, and then dried. On this release layer, the following printing ink composition (u) was coated uniformly by the roll coating method so that the dry amount of coating was 10 g/m.sup.2.
______________________________________ (u) Printing ink composition ______________________________________ Sumikaron Blue S-BG Conc. Cake (Sumitomo Chemical Company Limited; C.I. Disperse Blue 73) 10 parts Hydroxypropyl cellulose 20 parts Rosin-modified maleic acid resin (malkyd-32) 10 parts Isopropanol 60 parts ______________________________________
______________________________________ (v) Release layer composition ______________________________________ Copolymer of acrylonitrile/ethyl acry- late/methacrylic acid (60/30/10 mol %) 10 parts 11-Hydroxypalmitic acid 15 parts Toluene 20 parts Methyl ethyl ketone 15 parts Isopropanol 20 parts Methanol 20 parts ______________________________________
In the same way as in Example 4, a polyvinyl alcohol-sized paper was prepared, on which the release layer composition (v) was coated by the gravure coat method so that the dry amount of coating was 3.5 g/m.sup.2, and was then dried. A pattern was gravure-printed on this release layer with the following printing ink composition (w).
______________________________________ (w) Printing ink composition ______________________________________ Sumikaron Blue S-BG Conc. Cake (Sumitomo Chemical Company Limited; C.I. Disperse Blue 73) 10 parts Hydroxypropyl cellulose 5 parts Rosin-modified maleic acid resin (Malkyd-32.sup.R) 10 parts ______________________________________
______________________________________ (x) Release layer composition ______________________________________ Hydroxypropyl cellulose 13 parts Hydroxybenzoic acid-n-propyl ester 13 parts Isopropanol 37 parts Methanol 37 parts ______________________________________
The above-mentioned release layer composition (x) was coated uniformly on a glassine paper by the gravure coat method so that the dry amount of coating was 2.5 g/m.sup.2. A pattern was gravure-printed on this release layer, using the printing ink (b) shown in Example 1. An acetate woven fabric was placed on this printed surface and was passed between calender rolls heated to 120.degree. C. at a pressure of 10 kg/cm and at the rate of 5 m/min. to transfer the pattern. The transfer-printed cloth, after being steamed at 110.degree. C. for 30 minutes, was soaped with an aqueous solution composed of 1 g/l sodium tripolyphosphate and 2 g/l Amylasin at 60.degree. C. for 10 minutes, and was then washed with water and dried. There was obtained an acetate print which was sharp at pattern edges and not impaired in hand.
1. In a method of transfer printing which comprises forming a release layer on a temporary support; printing a pattern on said release layer with an ink containing coloring matter therein to obtain a transfer sheet; superposing an article to be transfer-printed on the printed surface of said transfer sheet; heating the superposed aggregate under pressure to transfer the release layer with the pattern onto said article to be transfer-printed; fixing the coloring matter to said article, and then soaping said article to remove the release layer; the improvement wherein the release layer consists essentially of
1. 10 to 90 weight percent of one or more thermoplastic polymers having excellent film-forming properties, water-solubility or alkaline water-solubility and organic solvent-solubility and having a softening point of between 60.degree. and 200.degree. C, said polymers being selected from the group consisting of hydroxypropyl cellulose, hydroxypropyl-hydroxyethyl cellulose, hydroxypropyl-methyl cellulose phthalate, hydroxypropyl-hydroxyethyl cellulose phthalate and vinyl copolymers consisting of an ethylenically unsaturated mono- or dicarboxylic acid and another ethylenically unsaturated monomer copolymerizable therewith and,
2 90 to 10 weight percent of one or more water-soluble or alkaline water-soluble and organic solvent-soluble oxycarboxylic acids and derivatives as plasticizers having a melting point between 30.degree. and 120.degree. C, said plasticizer being selected from the group consisting of 12-hydroxystearic acid, 2-hydroxypalmitic acid, 11-hydroxypalmitic acid, 14-hydroxypalmitic acid, 16-hydroxypalmitic acid, 2-hydroxytetradecanoic acid, 11-hydroxytetradecanoic acid, 2-hydroxydodecanoic acid,.omega.-hydroxylauric acid, 3,11-dihydroxytetradecanoic acid and 9,10-dihydroxyundecanoic acid.
2. The method as claimed in claim 1 wherein said thermoplastic polymers used in the release layer composition, are vinyl copolymers consisting of 5-20 mol %, of acrylic acid or methacrylic acid and 95-80 mol % of a copolymerizable ethylenically unsaturated monomer composed of an acrylic acid ester, methacrylic acid ester or mixtures thereof.
5. The method as claimed in claim 4 wherein the release layer composition has a softening point between 50.degree. and 150.degree. C.
6. The method as claimed in claim 4, wherein the release layer composition has a softening point between 70.degree. and 120.degree. C.
11. The method as claimed in claim 1 wherein the article to be transfer-printed placed on the printed surface of the transfer sheet is heated under pressure between calender rolls at a temperature between 80.degree. and 180.degree. C., at a pressure between 1 and 100 kg/cm.sup.2, for a period of time from an instant to several seconds, to transfer the pattern onto the article to be transfer-printed.
12. A method according to claim 11 wherein the transfer sheet is heated between the calender rolls at a temperature between 100.degree. and 150.degree. C at a pressure of 50 kg/cm.sup.2.
2469059 May 1949 Turk
2685549 August 1954 Wooldrik
3897469 July 1975 Stein et al.
3918895 November 1975 Mizuno
Patent number: 4027345
Inventors: Michio Fujisawa (Otsu), Hatsuo Matsumoto (Otsu), Shuzo Sawada (Otsu), Kiyoshi Yamane (Otsu), Hideo Kato (Kashiwara), Takayuki Shimizu (Habikino), Shigeo Kato (Kashiwara)
Application Number: 5/586,281
Current U.S. Class: 8/25R; 8/25A; Utilizing Radiant Energy Or Heat (101/470); 106/26; 106/30; 106/178; Of Portion Only Of Lamina From Carrier (156/234); Transfer Of Printing Or Design (156/240); With Printing (156/277); 260/23R; 260/406; 260/407; Heat Sensitive (427/148); Coating Opposite Sides Or Forming Plural Or Nonuniform Coats (427/152); Removable Protective Coating Applied (427/154); Material Designed To Be Responsive To Temperature, Light, Moisture, Etc. (428/913); Transfer Or Decalcomania (428/914)
International Classification: D06P 500; C08L 132; C08L 9100;