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Publication numberUS3769060 A
Publication typeGrant
Publication date30 Oct 1973
Filing date1 Feb 1971
Priority date3 Feb 1970
Also published asCA941692A1, DE2105019A1, DE2105019B2, DE2105019C3
Publication numberUS 3769060 A, US 3769060A, US-A-3769060, US3769060 A, US3769060A
InventorsH Hasegawa, S Nakanishi, S Ida, K Hosokawa, K Kajino, K Ueda
Original AssigneeKanegafuchi Spinning Co Ltd
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Specific processed cloths and a method of producing the same
US 3769060 A
Abstract
Specific processed fabric or sheet material which has been finished with a plurality of finishing agents differing in their chemical and/or physical function. The fabric or sheet material has a finishing agent fixed uniformly on its one part and another finishing agent on its different part. Those parts which respectively provide the fabric or sheet material with different chemical or physical properties may consist of a large number of small zones substantially uniformly distributed on the surface of the fabric or sheet material, or may be two surfaces, i.e., one surface and the reverse surface. The proposed processes enable a fabric or sheet material to be finished with a plurality of finishing agents which are incompatible with one another.
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Description  (OCR text may contain errors)

v o r I 1. Ute States atent 11 1 [111 3,769,

Eda et a1. Get. 30, 11973 [54] SPECIFIC PROCESSED CLOTHS AND A 3,336,153 8/1967 Juda l17/68.5

METHOD OF PRODUCING THE S 2,911,756 1l/1959 Geary 117/68.5 3,620,797 11/1971 Feitlowitz 117/68 X [75] Inventors; Shunya Ida, Nara City; Kenjil'o 3,521,638 7/1970 Parrish 117/44 Hosokawa, Osaka; Hiroyoshi 3,617,188 11/1971 Snyder 117/138.5 X Hasegawa, Osaka; Seinosuke 3,615,745 10/1971 Crovetti... 117/138.5 X Nakanishi, Osaka; Katsura Kajino, 3,127,281 3/1964 Meyer 117144 Osaka; Keizo Ueda Ashiya City all 3,437,508 4/1969 Gorski 117/54 3,553,005 1/1971 Moragne 117/119 of Japan Kanegafuchi Boseki Kabushiki Kaisha, Tokyo, Japan Filed: Feb. 1, 1971 Appl. No.: 111,252

Assignee:

Foreign Application Priority Data Feb. 3, 1970 Japan 45/10179 Sept. 29, 1970 Japan 45/85682 References Cited UNITED STATES PATENTS 12/1967 Meulenbeld 117/37 R 10/1967 Rabuse et a1. 117/44 12/1966 Haines 117/68 Primary Examiner-Alfred L. Leavitt Assistant Examiner-M. F. Esposito Attorney-Woodhams, Blanchard & Flynn [57] ABSTRACT Specific processed fabric or sheet material which has been finished with a plurality of finishing agents differing in their chemical and/or physical function. The fabric or sheet material has a finishing agent fixed unifonnly on its one part and another finishing agent on its different part. Those parts which respectively provide the fabric or sheet material with different chemical or physical properties may consist of a large number of small zones substantially uniformly distributed on the surface of the fabric or sheet material, or may be two surfaces, i.e., one surface and the reverse surface. The proposed processes enable a fabric or sheet material to be finished with a plurality of finishing agents which are incompatible with one another.

45 Claims, 5 Drawing Figures SPECIFIC PROCESSED CLOTHS AND A METHOD OF PRODUCING THE SAME The present invention relates to cloths whose physical and chemical properties are modified by a plurality of processing agents and a method of producing the same.

The term cloths used herein means various materials for clothings and industry and the like, for example, woven fabrics, knitted goods, unwoven fabrics, sheets, felts, bats, carpets, films, laminated cloths, etc.

Heretofore, the means for applying a plurality of processing agents on a cloth include treating the cloth with a bath containing a mixture of a plurality of processing agents or treating the cloth serially with separate baths containing different processing agents but in both cases, both the surfaces of the cloth are throughout processed uniformly with a bath, because the treating bath has a permeability into the cloth. Accordingly, for example, if an antistatic processing and a processing for providing elasticity are applied simultaneously on a cloth, such as knitted goods or woven fabrics composed of a synthetic fiber, any one of the antistatic-agents provided with a hygroscopic function and the elastic agents provided with a water repellent function covers the other agent and hence both effects are mutually eliminated or reduced and it is impossible to develop both the properties simultaneously and efficiently.

Recently, the technic for processing cloths has been highly developed'and various processing agents for supplementing the defects of cloths and modifying the properties thereof have been proposed and used practically, but the processing agents other than the above embodiment, in many cases, can not be used together, because of functions of these processing agents are opposite and are in contention with each other or one of the processing agents is covered with the other agent or a chemical reaction occurs between the processing agents, whereby the functions decrease mutually or there is no common solvent for both the processing agents. Accordingly an effective process by which various processing agents are used together simultaneously according to the desired application to provide the plural effect thereof on cloths, has not been discovered.

The inventors have made various investigations to solve such previous problems and accomplished the present invention.

The object of the present invention is to provide novel processed cloths developing each of the effects of different processing agents plurally and efficiently, which cloths have been treated with a plurality of processing agents having different functions.

Namely, the specific processed cloth of the present invention is characterized in that a large number of small zones distributed substantially uniformly on the cloth surface or the whole of one surface of the cloth is treated with a processing agent and at least one part of a portion other than said treated zones or the whole of the other surface of the cloth is treated with a second processing agent having a function different from the first processing agent.

In general it has been considered in the processing of a cloth that it is conventional to coat a processing agent over all of both the surfaces and that such a means is absolutely necessary in order to develop the effect of the processing agent. However, the inventors have found that most processing agents, although they depend upon the degree of function and the deposited amount, need not always necessarily be deposited uniformly over all of both the surfaces of a cloth and that if a processing agent of one plurality of processing agents is deposited on a large number of small zones uniformly distributed on a surface of the cloth or over all of one surface of the cloth and the other processing agents are deposited on a large number of small zones other than the above described small zones, which are also uniformly distributed on the cloth surface, or when the other processing agent is one kind, if said processing agent is deposited over all of the surface opposite to the surface treated with the first processing agent, the desired properties can be satisfactorily developed on the whole of the cloth and that in some cases, undesirable actions provided by the processing agents are restrained. For example, if the antistatic processing is effected locally, the object can be fully attained and in an extreme case, even when only the periphery of the cloth is processed, a desired antistatic cloth can be obtained. Furthermore, if a silicone processing is made throughout the surface of the cloth in order to improve the elastic property of the cloth and to provide crease proofness, the cloth loses its hygroscopicity, while if such a processing agent is applied so as to be deposited on a large number of distributed small zones, the cloth can be provided with the crease resistance while maintaining the hygroscopicity or vapor permeability.

If a crease proofing agent, such as tetraoxane and an antistatic agent and an antiflaming agent are applied according to the present invention, the effects of the treatments owing to each processing agent, that is, the crease resistance and wash wear property due to tetraoxane, the antistatic property due to the antistatic agent and the flame resisting property due to the antiflaming agent can be provided on knitted goods and woven fabrics.

The present invention has been accomplished by utilizing these facts skillfully. The method of producing the above described specific processed cloth comprises:

l. applying one processing agent for a cloth on a large number of small zones substantially uniformly distributed on the surface of cloth or over all of one surface of the cloth,

2. applying at least one processing agents other than the above described processing agent on at least a part of the cloth surface including the portion other than the above described zones or over all of another surface of the cloth and 3. fixing the above described applied agents on the cloth.

The method of the present invention will be explained practically hereinafter.

Firstly, a processing agent for a cloth is deposited on a large number of small zones substantially uniformly distributed on a surface of a cloth or over all of one surface of the cloth. In the case of depositing the processing agent on a large number of small zones, the processing agent is deposited on a proper pattern uniformly distributed on the cloth surface, for example, pointlike, spot-like, parallel line-like, stripe-like, mosaiclike, mesh-like pattern and the like. In this case, one processing agent is usually used alone but if the processing agents have no interference and hindrance between one another, two or more processing agents may be used together.

Then, if necessary, a treatment for fixing the applied agent to the cloth, for example drying, heating and the like is effected or such a treatment is not effected, after which another processing agent having a function different from the above described processing agent is applied on the spaces between the above described patterns or over all of another surface of the cloth. Then, the cloth, in which these processing agents are applied on the small zones, such as mosaic-like, alternating stripe-like pattern and the like or in which each of both the whole surfaces is coated with different processing agents respectively, is subjected to a treatment for fixing the processing agent.

The deposited state of two processing agents in the small zone type may be any of the following. Namely both the boundaries in the deposited zones may be in contact with each other or be spaced somewhat or be overlapped to some extent but non-overlapped portions of at least one of the processing agents must be distributed uniformly. Furthermore, when using processing agents not interferring with each other, one of the agents may be arranged in the small zones and the other agent may be applied on the whole surface. The order of the step for applying one of the processing agent on the small zones and the step for applying the other processing agent on the whole surface is not limited. The processing agents to be applied are not limited to two kinds and may be used optionally in a number of more than two depending upon the object.

The embodiments of patterns when the processing agents are deposited on the cloth in the small zones will be explained with respect to the drawings.

FIG. 1 shows the state where different processing agents are deposited on a stripe-like small zone 1 and the remaining zone 2 respectively. In this embodiment, both the zones are arranged so that the edges of both the zones are in contact with each other. The stripes may be longitudinal stripes, transverse stripes or inclined stripes along the longitudinal direction of the cloth but in order to distribute these small zones uniformly throughout the cloth surface, it is desirable that the width and distance of every stripes are substantially equal respectively;

FIG. 2 shows the state wherein both the small zones 1 and 2 are spot-like and the zones are spaced from each other and arranged uniformly. The shapes of the spots may be selected optionally in square, circular and the other forms;

FIG. 3 shows an embodiment wherein the small zone 1 is arranged in a spot-like or dot-like form and in the remainder 2 another processing agent is distributed in point-like form;

FIG. 4 shows the state wherein small zones 1, 2 and 3 deposited different processing agents respectively are distributed uniformly and regularly; and

FIG. 5 shows an embodiment wherein the small zone 1 and the small zone 2 are partially overlapped at the zone 3. Even in this case, each processing agent has non-overlapped portions uniformly distributed.

The means for distributing and depositing the processing agents on the cloth in these patterns may be effected by printing or spraying the processing agent liquid or a solution of a processing agent or a dispersion of the agent in a proper solvent or a paste of a processin g agent mixed with a sizing agent is printed or sprayed in a given pattern and then evaporating, removing or extracting the solvent or the sizing agent.

When one of the processing agents is applied throughout the surface as mentioned above, the conventional immersing process, the process for coating the whole surface or a vapor phase treating process and the like may be naturally adopted. Furthermore, the object can be attained by dispersing and depositing microcapsules containing sealed therein a processing agent on the cloth surface uniformly and breaking the capsules by the action of pressure, heating and the like.

Such operations for applying the processing agents are generally carried out by repeating the operations for each of the processing agents employed. When repeating the printings, it is desirable to arrange the succeeding patterns in the spaces of the preceding patterns but when the permeability of the cloth is high, the processing agent may penetrate and extend from the succeedingly applied zones and overlap with the preceding zones. Accordingly, when the overlapped zones where the effects are reduced by the action of contention and hindrance of mutual processing agents, are formed, it is desired that each area of the applied zones is made small as much as possible to reduce the overlapped portions, or that a processing for restraining the permeability is previously applied to the cloth or a process for printing a paste is adopted. In order to carry out the removal of solvent rapidly, it is effective to apply the processing agent on a heated cloth.

Moreover, for promoting the rapid penetration or depositing of the processing agent into the interior of the cloth, the following means are carried out optionally, if necessary. Namely, an assistant, such as a surface active agent is used together with the processing agent or the cloth to be treated is subjected to a preliminary treatment by means of such an assistant. Alternatively, when the cloth is a film composed of an organic synthetic thermoplastic polymer, the film is previously subjected to a surface active treatment, such as corona discharge treatment and the like.

When combining the treatment'with the spray treatment, the printing treatment with the immersing treatment or the printing treatment with the vapor phase treatment, that is when overlapping of both the processing agents are is carried out, it is essential to select both the processing agents so as not to reduce the effect of the processing agents to be printed by the processing agent to be sprayed, immersed or vapor phase treated; In addition, the object of the present invention can be accomplished by combining two spraying treatments.

When using the micro-capsule process, several processing agents can be applied on the cloth surface in small zones where these agents are distributed alternately and substantially uniformly by contacting the cloth with a system containing a mixture of different microcapsules a one step operation, therefore such a process is very convenient.

The above described small zones in which the processing agents are deposited should be distributed substantially uniformly over the whole surface of the cloth and a preferred result can be obtained. The smaller the areas of the small zones and the larger the number of such zones, the better is the result. In the line-like or the stripe'like pattern, the width is at most about 2 cm, preferably at most about 1 cm and in the case of the spot-like pattern, the area of one small zone is not more than about 4 cm preferably not more than about l cm. When the area is too large, it is difficult to develop the plural effects harmonized uniformly over the whole cloth and local unevenness of texture and appearance and the like is noticeable and this can not attain the object of the present invention.

Then, the processing agents applied on the cloth are subjected to an appropriate fixing treatment. The setting treatment includes generally drying at room temperature or at an elevated temperature, aging, baking, steaming, extraction with a solvent, fixing by a reaction with another chemical and the like, but it is selected properly depending upon the properties of the processing agents deposited on the cloth. If it is possible to carry out the fixing treatment commonly for various deposited processing agents, it is preferred to effect the fixing step at the same time after finished the steps for applying the processing agents.

In addition, it is effective to effect the fixing treatment each time a processing agent is applied, particularly in the case when the manners of the fixing treatment are different or there is a risk that a plurality of processing agents may cause undesirable interferences by carrying out continuously the steps for applying said processing agents.

As the apparatus for carrying out the above described processes, well known textile printing machines, such as roller printing machine, screen printing machine and the like, printing machines, such as relief printing, intaglio printing, and the like, a well known spraying device, saturation bath, ager type vapor phase treating device and the like may be used depending upon the object.

The processing agents applicable to the present invention are treating agents, which can be deposited or adsorbed on the cloths to give or modify the particular chemical or physical properties and, for example, shrink proofing agent, antipilling agent, water repelling agent, elastic agent, hygroscopic agent, antistatic agent, stain proofing agent, antiflaming agent, antifusing agent, softening agent, ultraviolet absorbing agent, crease proofing agent, water absorbing agent, heat resisting agent, soil releasing (SR) agent oil repelling agent, moth proofing agent, dust proofing agent, mildew proofing agent, delustering agent and the like may be mentioned.

In the present invention, when these processing agents are applied only on one surface of the cloth, there is no problem in the permeability into the cloth, while when both the surfaces of the cloth are applied with the processing agent, it is preferable to select the processing agent having a very low permeability or no permeability into the cloth.

The above described various processing agents can provide the inherent effect to the cloth alone respectively but when these processing agents are used together and applied on knitted goods and woven fabrics, the applied processing agents interfere with one another in the conventional processes as described above and it is difficult to develop the inherent treating effects brought about by the respective processing agents together, while according to the present invention when ,such a plurality of processing agents are used, the effects of these agents can be developed most efficiently.

The shrink proofing agents include the reaction products of phosphorus pentachloride with carboxyl group of ethylene/acrylic acid copolymer, ethylene/methacrylic acid copolymer, ethylene/itaconic acid copolymer, ethylene/methylhydrogen maleate copolymer,

ethylene/maleic acid copolymer, ethylene/acrylic acid/methyl methacrylate copolymer, ethylene/methacrylic acid/ethyl acrylate copolymer, ethylene/itaconic acid/methyl methacrylate copolymer, ethylene/methylhydrogen maleate/ethyl acrylate copolymer, ethylene/- methacrylic acid/vinyl acetate copolymer, ethylene/acrylic acid/vinyl formate copolymer, ethylene/- propylene/acrylic acid copolymer, ethylene/styrene/acrylic acid copolymer, ethylene/methacrylic acid/acrylonitrile copolymer, ethylene/fumaric acid/vinyl methyl ether copolymer, ethylene/vinyl chloride/acrylic acid copolymer, ethylene/vinylidene chloride/acrylic acid copolymer, ethylene/vinyl fluoride/methacrylic acid copolymer, ethylene/chlorotrifluoroethylene/methacrylic acid copolymer, polyethylene/acrylic acid graft copolymer, polyethylene/methacrylic acid graft copolymer, polyethylene/propylene acrylate graft copolymer, polyethylene/butene-llmethacrylic acid graft copolymer, polyethylene/vinyl acetate/methacrylic acid graft copolymer, polypropylene/acrylic acid graft copolymer, polypropylene/methacrylic acid graft copolymer, polybutene/acrylic acid graft copolymer, poly-3-methylbutene/acrylic acid graft copolymer, and polyethylene/acrylic acid/methyl acrylate graft copolymer and particularly the reaction products containing at least 0.1 mol% of acid chloride group are preferable.

As the ultraviolet absorbing agents, 2-hydroxy-4- octoxybenzophenone, 2,2,4,4'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, sodium salt of 2,2-dihydroxy-4,4'-dimethoxy-5- sulfobenzophenone, 2,4-dihydroxybenzophenone, 2- hydroxy-4-methoxybenzophenone, 2,2'-dihydroxy- 4,4-dimethoxybenzophenone and di-p-n-nonylphenol isophthalate are frequently used.

As the water repellent agents, use may be made of dialkyl-polysiloxanediol, alkylhydrogen polysiloxane, alkylpyridium halide, Werner type metal complex, the other long chain aliphatic derivatives and the like and particularly alkylhydrogen polysiloxane is used in many cases. The most preferable one is methylhydrogen polysiloxane having a viscosity of less than centistokes.

As the antistatic agents, use may be made of, for example anionic, cationic, amphoteric or non-ionic compounds. The antistatic agents having a durability, as the anionic antistatic agents are, for example, ammonium polyacrylate, alkali metal salts of copolymer of styrene/vinylacetate/methy] methacrylate with maleic anhydride (or ethylene oxide addition product), carboxylic acid compounds, such as Werner type complex prepared from chromium chloride and l,2,3,4-butanetetracarboxylic acid, polyester derivatives, such as esters of styrene/maleic anhydride copolymer with polyethylene glycol or polyhydric alcohol, copolymer of higher fatty acid bis (hydroxyalkyl) amide with maleic anhydride and the like, sulfonic acid derivatives, such as polyvinylsulfonic acid, polystyrenesulfonic acid, polyvinyltoluenesulfonic acid or copolymer of methyl methacrylate with ethylenesulfonic acid, copolymer of acrylic amide with ethylenesulfonic acid and the like, phosphorus compounds, such as polymer of diallyl-2- cyanoethylphosphonate, polymer of dimethylvinylphosphonate, etc.

As the above described cationic antistatic agents, use may be made of quaternary ammonium salt obtained by reacting diethylaminoethylmethacrylate with dimethyl sulfate, acrylate derivatives, such as triacryloylhexahydrotriazine derivative, acrylic amide derivatives, such as a polymer of acrylic amide, methy lene urea, a polymer of melaminemonomethyleneacrylic amide, a polymer of acrylic amide-propylbutyloxymethyl morpholinium chloride, vinyl ether derivatives, such as polyvinyl-Z-chloroethyl ether pyridinium salt, a polymer of unsaturated ureide ether from aminoethyl vinyl ether and isocyanate, a quaternary ammonium salt of copolymer of vinyl cyclohexyl ether and diethylaminovinyl ether, vinyl nitrogen derivatives, such as a quaternary salt of polymer or copolymer of vinylpyridine, a quaternary salt of poly-2- vinylpyridine and p-toluenesulfonic acid, polyamine resins, such as polyethyleneglycol polyamine and the like.

As the non-ionic antistatic agents, use may be made of acrylates, such as a copolymer of polyethylene glycol ester and acrylic amide, ethylene oxide derivatives, such as a reaction product of melamine, formaldehyde and ethylene oxide, an addition product of phenol resin and ethylene oxide, an addition product of cellulose and ethylene oxide, a reaction product of polyethylene glycol and chlorohydrin, a copolymer of dimethyl terephthalate with ethylene glycol and polyethylene glycol, use of combination of tolylene-diisocyanate and polyethylene glycol, use of combination of polyacetal from polyethylene glycol and dimethylol urea, polyester of polyethylene glycol with maleic acid and itaconic acid, use of combination of polyethylene glycol and 1,3,5- triacryloyl-hexahydro-S-triazine, amide compounds, such as N-methoxymethylated polyamide, N,N'- dimethyl-N,N '-bishydroxymethyladipic amide.

The amphoteric antistatic agents include alanine type, imidazoline type, carboxylic acid type, dicarboxylic acid type, diamine type, betaine type and sulfobetaine type.

The cationic antistatic agents are preferable in view of the effect and antiwashing property.

As the softening agents, mention may be made of anionic agents, such as long chain alkyl sulphates, cationic agents, such as long chain alkyl quaternary ammonium salts, betaine type of amphoteric agents and the like.

The stain proofing agents applicable to the present invention include polymers having the general formula tcnnmooca' wherein RF represents a linear or branched perfluoroalkyl group having three to 2! carbon atoms, R represents an alkyl group having one to 17 carbon atoms, R represents hydrogen or methyl group and m and n represents 1 to I Oj polymershaving the general formula RF'Cl-l Cl-l(CH ),,,'OOCCR=CI-lg wherein RF represents a linear or branched perfluoroalkyl group. m represents 2 to and R" represents hydrogen or methyl group; polymers having the general formula wherein RF represents a linear or branched perfluoroalkyl group having one to 20 carbon atoms and R represents hydrogen or methyl group; polymers having the general formula wherein RF represents a linear or branched perfluoroalkyl group having three to 21 carbon atoms, R represents an alkyl group having one to 17 carbon atoms, R represents hydrogen or methyl group and m and n represents 1 to 10;

polymers having the general formula wherein RF represents a linear or branched perfluoroalkyl group having three to l8 carbon atoms, m represents 0 to 16 and R represents hydrogen or methyl group;

polymers having the general formula RF CON OOCC=CH2 wherein RF represents a linear or branched perfluoroalkyl group having, one to 18 carbon atoms, R and R" represent alkyl group having one to six carbon atoms and R represents hydrogen or methyl group and A represents (CH in which a represents 0 to 4;

polymers having the general formula wherein RF represents a linear or branched perfluoroalkyl group having three to 18 carbon atoms, n represents an alkyl group having zero to 16 carbon atoms and R represents hydrogen or methyl group; and

polymers having the general formula wherein RF represents a linear or branched perfluoroalkyl group having three to 21 carbon atoms, m represents an alkyl group having zero to five carbon atoms, R and R represent alkyl groups having one to 19 carbon atoms, B represents or [RF ]A'Z, wherein [RF"] is a linear or branched perfluoroalkyl group having three to 20 carbon atoms, A is O- or -S- and Z is a triazine or pyridine ring.

The soil releasing agents include, for example a reaction product of poly-(N-methylperfluorooctane-sulfon amide-ethyl) acetate-ethylperfluorooctanoate and polyethyleneimine, a copolymer having polyoxyethylene group, which is obtained by copolymerizing dimethyl terephthalate, ethylene glycol and polyethylene glycol, a copolymer having polyoxyethylene group, which is obtained by copolymerizing dimethyl terephthalate, l,4-bis-hydroxymethylcyclohexane and poly (oxyethylene) glycol.

As the other stain proofing agents, there are inorganic processing agents, such as alumina sol, silica sol and the like and they are used in an amount of 0.1 to 10 percent by weight based on the fibers, preferably 0.4 to 3 percent by weight.

As the oil repelling agents, use may be made of mainly low molecular substances or polymers containing fluorine atom and further the substances having soil releasing property may be used.

As the fluorine-containing compounds, for example mention may be made of the above described stain proofing agents.

The soil releasing agents include, for example a reaction product of poly-(N-methyl-perfluorooctanesulfonamide-ethyl) acetate, ethyl-perfluorooctanoate and polyethyleneimine, and a copolymer having polyoxyethylene group, which is obtained by copolymerizing dimethyl terephthalate, ethylene glycol and polyethylene glycol.

The dust proofing agents include, for example in organic agents, such as alumina sol, silica sol and the like.

As the antiflaming agents, use may be made of mainly compounds containing phosphorus or halogen, for example 2,3-dibromopropyl phosphate, trisdichloropropyl phosphate, l,2,3,4-tetrabromoethane, tetrakishydroxy-dimethyl phosphonium chloride, tris-2- chloroethyl phosphate, tris-aziridinyl-phosphin oxide, bis-B-chloroethyl phosphate, dialkyl phosphate carboxymethylolamide, dimethylol phosphono-propylene monomethylol amide, chloroparaffin, diammonium hydrogen phosphate, ammonium sulfamate, ammonium phosphate, borax and boric acid.

As the antifusing agents, organopolysiloxane is effective and the above described dialkyl-polysiloxanediol and alkyl hydrogen polysiloxane are mainly used.

As the crease proofing agents, use may be made of urea derivatives, triazine derivatives, triazone derivatives, dihydrazide derivatives, hydrazine derivatives, alkylcarbamate derivatives, acetal derivatives, organic silicone series prepolymers, and polyurethane prepolymers. As the urea derivatives, dimethylol compounds are used in many cases, for example dimethylol urea, dimethylol-ethylene urea, dimethylolpropylene urea, and dimethylol-dihydroxyethylene urea. The triazine derivatives include trimethylolmelamine and hexamethylolmelamine. The triazone derivatives include dimethyloltriazone. The hydrazide derivatives include methylolated product of dihydrazide. The hydrazine derivatives include dimethylolated product of symmetric hydrazine. The alkyl carbamate derivatives include dimethylolmethylcarbamate, dimethylolethylcarbamate, dimethylolpropylcarbamate, and dimethylolbutylcarbamate. As the organic silicone prepolymer,

dialkylpolysiloxane diols are used in many cases, for example dimethylpolysiloxane diol and diethylpolysiloxane diol having a viscosity of at least centistokes, preferably at least 2,000 centistrokes. As the polyurethane prepolymers, the prepolymers having a high polymerization degree of a viscosity of at least 1,000 centistokes, preferably at least 3,000 centistokes are used.

Furthermore, as the crease proofing agents, tetraoxane of methylol derivatives can be preferably used. Tetraoxane is a tetramer of aldehyde and even if it is fixed on knitted goods or woven fabrics alone, the crease proofing property or the wash wear property can be provided on the cloths.

The water absorbing agents or moisture absorbing agents are mainly polyester compounds and polyamide compounds containing a hydrating group and include relatively low molecular weight carboxylic acid and sulfonic acid derivatives. The polyester compounds are mainly a copolymer containing hydrating polyoxyalkylene group, which is a copolymer of polyoxyalkylene glycol having an avarage molecular weight of 300 to 6,000, particularly poly (oxyethylene) glycol or alkoxypoly (oxyalkylene) glycol, particularly methoxyl poly (oxyethylene) glycol with dimethyl terephthalate and ethylene glycol, for example a copolymer of dimethyl terephthalate, ethylene glycol, and polyoxyethylene glycol and a copolymer of dimethyl terephthalate, ethylene glycol and methoxy-poly (oxyethylene) glycol. As the polyamide compounds, use may be made of mainly N-methoxymethyl-polyhexamethylene adipamide and the addition product of a lactam or a derivative thereof with polyalkylene glycol is particularly preferable and an addition product of caprolactam oligomer having a polymerization degree of at most 5 with 2 to 50 mole of alkylene oxide having at most four carbon atoms is the most excellent in the treating effect and durability.

The elastic agents include polyorganosiloxane prepolymers or urethane prepolymers. As the polyorganosiloxane prepolymers, use may be made of polyorganosiloxane diols and alkyl hydrogen polysiloxanes.

The polyorganosiloxane diols are shown by the general formula HO (SiRR'O),, H

and have a viscosity of 1,000 to 100,000 centistokes of 15 percent trichlene solution at 25C and have OH group at the end and R and R may be the same or different and show alkyl, aryl, CH=CH CH --CH- -CF NCO, OH, OCH;,, etc. and the alkyl group has one to four carbon atoms. Dialkyl polysiloxane diol, diphenyl polysiloxane diol and alkyl phenyl polysiloxane diol are most frequently used and particularly dimethyl polysiloxane diol is the most preferable. The viscosity of polyorganosiloxane diol is 1,000 to 100,000 centistokes, preferably 5,000 to 50,000 centistokes. The alkyl hydrogen polysiloxane is somewhat poor in view of the elasticity of the formed film as compared with polyorganosiloxane diol but is advantageous in view of the water repellent property. The alkyl groups in alkyl hydrogen polysiloxane include methyl, ethyl, propyl and butyl groups but methyl hydrogen polysiloxane is the most preferable. The viscosity is preferred to be at most 1,000 centistokes, preferably 5 to 50 centistokes.

The polyurethane prepolymers to be used in the present invention have urethane bonds or urea bonds in the molecular chain and have isocyanate group in the end and such prepolymers can be produced by reacting a compound having active hydrogen with a compound having isocyanate group.

The organic diisocyanates to be used for the production of the prepolymers include 1,5-naphthalene diisocyanate, 4,4-diphenyl methane diisocyanate, 2,6- tolylene diisocyanate, 2,4-tolylene diisocyanate, methylene bis (4-phenyl isocyanate), m-phenylene diisocyanate, p-phenylene diisocyanate, diphenylmethane-3,3'- dimentyl-4,4'-diisocyanate, xylene diisocyanate, cyclohexylene diisocyanate, 1,6-hexamethylene diisocyanate, dimethyl diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, methylcyclohexylene diisocyanate and the like. The active hydrogen compounds to be used for the formation of long chain segments are mainly diols and triols having a linear structure and also include polyols. As the triols, for example glycerin-propylene oxide adduct is used. As the diols, polyalkylene oxide glycols, such as poly-1,2propyle'ne oxide glycol, polyethylene oxide glycol, ethylene oxide/propylene oxide copolymer glycol are preferable. The molecular weight of the diols is preferred to be at most 5,000. The prepolymers are preferred to be high molecular weight and 3,000 to 50,000, more preferably 10,000 to 25,000 and the isocyanate group is 1 to 3 percent, preferably 1.5 to 2.5 percent.

According to the present invention, it is possible to use polyorganosiloxane prepolymer and urethane prepolymer together. In this case, the isocyanate group in the polyurethane prepolymer and the hydroxyl group in the polyorganosiloxane diol form a block copolymer through the polyaddition reaction and the thus. treated cloth is low in the waxy touch and has a feeling enriched in weight feeling and thickness as compared with the case when the urethane polymer of silicone polymer is used alone. The above described conditions concerning the urethane prepolymer are preferable for the formation of the block copolymer and the ratio of the mixture is preferred to be from :2 to 2:10.

in the present invention, an addition of a catalyst is preferable in order to carry out the hardening of the prepolymer under a practical industrial condition and in the case of polyorganosiloxane prepolymer, the use of catalyst is necessary. Dibutyltin dilaurate, dibutyltin octanoate, dibutyltin diethyl hexonate, chelate tin and the like are preferable but the catalyst is not limited thereto. They are used within the range of l to 30 percent by weight, preferably 3 to 10 percent by weight based on polyorganosiloxane prepolymer alone or in admixture. According to the present invention, a primer may be used together with the above catalyst in order to deposit the formed polymer on the fibers. The primers are, for example silane isocyanate, alkoxysilane, silane acetate, vinylthrichlorosilane, vinyl-tris (B-methoxyethoxy) silane. B-(3.4-epoxycycl0hexyl) ethyltrimethoxysilane, 'y-glycidoxypropyltrimethoxysilane, -y'-methacrylo-propyl-methoxysilane and the like. They are used in an amount of not'more than percent by weight based on polyorganosiloxane prepolymer.

The amount of polyorganosiloxane prepolymer and urethane prepolymer to be used in the present invention is 0.1 to 10 percent by weight, preferably 0.2 to 3 percent by weight based on the fibers. The amount of less than 0.1 percent by weight can not attain the satisfactory effect and the amount of more than 10 percent by weight is not preferable in the texture of the finished base cloth.

As the soil releasing agents, use may be made of carboxymethyl cellulose, hydroxyethyl cellulose, starch, water soluble polyvinyl alcohol, a block copolymer of polyethylene glycol and polyethylene terephthalate, a reaction product of an amino resin and polyethylene glycol, a reaction product of polyamide and polyethylene glycol, an acrylate/acrylic acid copolymer, an acrylate/methylol acrylic amide copolymer and acrylic acid/acrylic amide copolymer.

As the antipilling agents, use may be made of polyurethane compounds having a high polymerization degree, for example the above described elastic processing urethane prepolymer, reactive acrylate resins, butadiene latex and the like.

As the moth proofing agents and mildew proofing agents, use may be made of pentachlorophenol, sodium salt of pentachlorophenol, metal salts of naphthenic acid, cetyl pyridium bromide, dimethylbenzyl ammonium phosphate, trimethylcetyl ammonium pentachlorophosphate, tributyltin phthalate mercuric chloride, phenyl mercuric chloride, phenyl mercuric acetate, phenyl mercuric oleate, phenyl mercuric urea, phenyl mercuric p-toluene-sulfonanilide, phenyl mercuric triethanol ammonium acetate, ethyl mercuric chloride, ethyl mercuric oleate, ethyl mercuric ptoluene sulfonanilide, bistributyltin oxide, tributyltin acetate, tributyltin propionate, tributyltin butyrate, butyl p-oxybenzoate, sodium 3,5,3',5-tetrachloro- 2,2'-dioxytriphenyl methane-2-sulfonate, disulfobenzoate of pentachlorodioxytriphenyl methane, dichlorodiphenyl, dichlorodiphenyl trichloroethane, sodium 3,5,3,5, 4"-pentachloro-2,2-dioxytriphenyl methane-2"-sulfonate, 3,4-dichlorobenzene sulfomethylamide, sodium chloro-o-cresolate, 3,3',4- trichloro-6-(2"-sulfo-4-chloro) phenoxydichloro urea and the like.

It has been usually carried out in dyeing, textile printing, printing and the like to disperse, distribute and fix a dye stuff, pigment and the like on a cloth. However, these procedures intend to obtain multi-color effect or design effect relying upon vision by the agents having different color tones and are fundamentally different from the present invention, in which a plurality of physical and chemical properties are given; Accordingly, the dye stuffs and pigments, which aim only the provision of color and do not bring about the modification of the physical and chemical properties, are not included in the processing agents of the present invention.

An embodiment wherein tetraoxane is used as a crease proofing agent of an example of treating of a cloth in the process of the present invention will be explained hereinafter.

In the process of the present invention, tetraoxane is usually applied on knitted goods or woven fabrics as an aqueous solution. In this case, the concentration of tetraoxane in the aqueous solution is selected variously depending upon the kind of knitted goods or woven fabrics to be treated, the means depositing it on them, the kind of the processing agents other than tetraoxane or with or without the drying treatment after the applying treatment and it is difficult to determine the concentration generally and the concentration is preferred to be 0.05 to 25 percent by weight, more particularly 0.5 to 20 percent by weight, most preferably 2 to 15 percent by weight.

Tetraoxane can be easily dissolved in water at room temperature but the solubility of tetraoxane at room temperature is about 5 to 8 per cent and in hot water, for example at 80C, it reaches more than 13 percent, so that it is desirable to dissolve tetraoxane in water at a high temperature.

Furthermore, in order to promote the dispersion of tetraoxane in water, it is possible to use a dispersing agent (for example, anionic, cationic or nonionic various surfactants).

If the dispersing agent is used together it is possible to obtain a dispersion having a stable high concentration, for example more than 15 percent by weight of tetraoxane even at room temperature.

When tetraoxane is fixed on knitted goods or woven fabrics according to the present invention, a desirable result can be obtained by existing various catalysts to be used generally in theprocessing for crease proofing or wash wear, for example ammonium salts, organic amine salts or metal salts (for example, magnesium chloride, zinc nitrate or zinc fluoride etc.) together. The amount of the catalyst used is generally l/l0 to 1/2, preferably 1/4 to l/ (weight ratio) based on tetraoxane.

Moreover, according to the present invention, the most effective result can be obtained by applying tetraoxane on knitted goods or woven fabrics together with a sizing agent.

As the above described sizing agents, mention may be made of, for example starch, carboxylmethyl cellulose, polyvinyl alcohol and propylene glycol ester of alginic acid. Propylene glycol ester of alginic acid gives the best result.

However, some of the sizing agents can react with tetraoxane to fix tetraoxane on knitted goods or woven fabrics, but it is difficult to remove the sizing agent by washing and the knitted goods and woven fabrics become rigid, so that it is necessary to take account of the selection of the sizing agent deeply. Among the above described sizing agents, particularly propylene glycol ester of alginic acid, after it is deposited on knitted goods or woven fabrics together with tetraoxane, can be easily removed by washing with water and give an excellent effect resulting from tetraoxane to the cloth without hardening the cloth, so that it is the best sizing agent.

According to the present invention, tetraoxane and the other processing agents are deposited on the respective separate positions of the surface of knitted goods or woven fabrics. The order of the depositing treatment is not particularly defined and after the deposition of tetraoxane, the other processing agents may be deposited or the deposition treatments may be effected in the reverse order. Alternatively, if it is possible to deposit the processing agents in different positions, a plurality of processing agents may be deposited simultaneously in one step.

Tetraoxane can be deposited on knitted goods or woven fabrics in an aqeuous solution but if tetraoxane can be deposited on the given portion of the cloth surface in a desired state, the process is not particularly limited and various depositing processes or printing processes are applicable in relation to the depositing condition or means of the processing agents other than tetraoxane.

When tetraoxane is applied over all of one surface of the cloth, the printing process is convenient in many cases.

The processing agents other than tetraoxane are applied directly or in the solution state suitable for each processing agent on knitted goods or woven fabrics.

Particularly, when tetraoxane and the other processing agents are applied on the same surface of the cloth, unless a fairly broad portion on the surface of the cloth is coated or fixed with the respective processing agent in the conventional processing treatment, the effect can not be attained, while according to the present invention, the same treating effect as brought about by the conventional process can be attained by a small area partially deposited with the processing agent.

For example, when tetraoxane and the other processing agents are fixed so that the processing agents are separated independently in spot-like uniformly on the same surface of the cloth without doubling with each other, the above described treating effect is noticeably shown.

Tetraoxane and the other processing agents in the process of the present invention are fixed so that they occupy at least 20%, preferably at least 40 percent of the surface area of the cloth (the sum of the upper surface and the under surface).

When the deposited surface is less than 20 percent, it is impossible to obtain the treating effect owing to each of the processing agents on the cloth and such an amount is not preferable.

When tetraoxane is deposited on the cloth according to the present invention, it is desirable to select the concentration, viscosity or depositing condition of the solution so as not to penetrate to tetraoxane from the applied surface into the opposite surface. Because when a processing agent other than tetraoxane is applied on the opposite surface to the surface applied with tetraoxane, it is difficult to provide the effect of the processing agent satisfactorily on the cloth.

Tetraoxane may be applied on the upper surface or the under surface of the cloth or on both the surfaces and the processing agents other than tetraoxane also may be applied on the upper surface or the under surface of the cloth or on both the surfaces and such application is variously determined depending upon the kind of processing agent, the depositing state or the depositing means.

Furthermore, when tetraoxane is applied over all of one surface of the cloth, tetraoxane or the other processing agents are partially applied on the other surface.

The amount of tetraoxane deposited is 0.05 to 25 percent by weight, preferably 0.5 to 15 percent by weight based on the cloth. Particularly when tetraoxane is partially deposited, even if the amount is small, the effect can be fully developed.

The apparatuses for applying tetraoxane and the other processing agent on the cloth include, for example rollers textile printing machines, such as relief printing or intaglio printing machine, textile printing machines, such as manual or automatic screen printing machine or paper printing machines, such as relief printing or intaglio printing machine or a mangle.

When tetraoxane solution is printed on the cloth by means of these apparatuses, it is desirable to restrain and penetration of the solution into the under surface of the cloth as far as possible. Accordingly, a better result can be obtained, when the depth of the engraved portion of roll on the roller printing machine is small as far as possible. The permeability of tetraoxane solution into the cloth varies depending upon the fineness of yarns, density, knitted or woven structure and the like and therefore it is impossible to make a general statement but, for example when the cloth to be treated is a thin base cloth, such as a broad, the roullete number in a roller printing machine is at least 30, a gravure printing machine is at least 100 meshes and a screen printing machine is at least 200 meshes. The processing agents other than tetraoxane have no such a limitation. The amount of tetraoxane deposited on the cloth by these printing machines is considerablyv smaller than the total deposited amount by means of the immersing padding process, and for example is less than half.

However, when the area deposited with the printed processing agent on the cloth is very small or the depth of the roll is extremely small, the amount of the processing agent deposited is considerably small, so that in such a case it is desirable to make the concentration of the processing agent sufficiently high. On the other hand, when the printing is effected by means of various printing machines, a plurality of solutions of processing agents to be deposited on the cloth must beadjusted to a proper viscosity by the content of processing agent, sizing agent and the like in order not to flowout the processing agent from the engraved portion or in order to make the pattern edge of the engraved portion clear.

Thus, according to the present invention, the property of the cloth material can be optionally modified by means of different processing agents without causing interference and hindrance of processing agents with one another and the cloth providing each effect of the processing agent together can be produced. The cloth can be variously processed by a plurality of processing agents, which have never been heretofore used together because of the mutually opposing and contending function or shielding function and further by using a much smaller amount of processing agent as compared with the conventional means for processing the cloth, substantially the same effect can be attained. Accordingly, the present invention is very excellent as the means for processing cloth. In addition, the cloth obtained by the present invention is provided with a plurality of effects of various processing agents, which have never been previously provided together and the cloth has a novel combined plural properties and feeling and the demand field can be widely broadened.

The invention will be explained by the following examples but is not limited thereto.

In the examples, the crease resistance is determined by JlSLlO79-22B process, the tear strength is determined by Pendulum process, the tensile strength is determined by strip process, the bending resistance is determined by Clerk process and the water repellent property is determined by JISL-l079-5,24,2 spray process. I

The soil releasing property is determined by measuring the reflection factor of 550 muby a spectrophotometer (made by HITACHI LTD., EPU-2A type), after treated with the test process for oil stain of Japan Oil Chemical Society.

The water absorbing property is determined by expressing the time necessary until 0.02 cc of potassium permanganate solution dropped on a center portion of a circle having a diameter of 3 cm made in a sample spread and reaches the periphery, by second.

The frictional electrostatic voltage is measured by Rotary static tester (made by KOA SHOKAI) by using a cotton broad cloth of 60 count yarn as a friction member.

The compression elasticity is determined as follows:

The thickness after the piled four sheets of cloths are subjected to a load of 10 g/cm for one minute is t, the thickness after the cloths are further subjected to a load of 300 g/cm for one minute is and the thickness after the said cloths are left to stand under no load for one minute is t Compression degree [(t t,)/: 1 X

Elasticity [(t n)/(: t,)] x 100 Pilling test: JIS-L-l076 (l967)-A Method (using [CI type tester).

Oil repellent property: AATCC Test Method Iii-i966 T.

Light resistance: Irradiation by a fadometer for 20 hours. I

Wash and wear property: The determination was made from 5th class (best) to lst class (worst) according to small crease grade standard photograph of AATCC TEST METHOD 88A. The washing condition is as follows: A sample of 30 cm X 30 cm was washed with 45 times amount of solution containing l g of Zabu (made by KAO SEKKEN I(.K.', anionic detergent, Trade Mark) in l lof waterb y means of an automatic reversing washing machine at 40C for 15 minutes and then washed with water for 15 minutes and taken out from the washing machine and two points in one end were suspended without squeezing and dried at room temperature. This procedure was repeated five times.

Antiflaming property: Test method of the Autonomy Agency of Japan, Law, Article 4, Item 3, No. 5 (practiced on April, 1969).

Mildew proofing property: JIS-L-l006 (I956).

Shrink proofing property: Treated with AATCC type launder-o-meter at 60 C for 20 minutes? I I Antifusing property: Time (second) until a bore is made on a sample cloth by the fusion of the fiber, when an ignited incense having a diameter of 1 mm is put on the cloth.

Bending resistance JlS-L-1079 C Method (Clerk method).

Test method for oil stain: One drop of colored paraffin is fallen on a sample cloth and this cloth is immersed in water and the behavior of the oil drop is observed.

Test method for aqueous stain: One drop of red ink is fallen on a smaple cloth and this is washed and the removal is observed.

Test method for redeposition of wet stain: A sample cloth having 3 inch and a flannel having the same area, which has been stained in the following manner are washed together in a launder-o-meter and the redeposition of the stain on the sample is observed.

A process for making the stained cloth:

40 g cars black 20 g tallow 20 g paraffin 4 l trichloroethylene A flannel is padded with a liquid having the above composition and dried.

whiteness: The opposite reflection factor against a standard white sheet (magnesium oxide) at 440 mp. by means of a spectrophotometer.

Tear strength Pendulum process.

Tensile strength JIS-L-l004, 511-(1) strip method.

Dust proofing property Natural dust collected through a screen having 250 meshes is added to a cloth of cm X 5 cm in an amount of percent by weight based on the cloth and charged in a glass bottle of 500 cc having a cap together with 10 steel balls having a diameter of 10 mm. The glass bottle is rotated at a rate of 45 raolutions per minute and the sample is taken out after 10 minutes and is treated with a tumbler of 45 revolutions per minute for 5 minutes and the excess dust deposited on the sample is removed and then the sample cloth is compared with the standard white sheet (magne sium oxide) with respect to the whiteness.

Washing condition: 50 times amount of solution containing l g of the above described detergent of Zabu is used and the washing is effected by means of an automatic reversing washing machine at 40C for minutes and then water washing is performed at 40C for 15 minutes. This procedure is repeated several times.

Example 1 A crease proofing agent solution having the following composition was applied to a nylon tricot cloth to form longitudinal stripes, each having a width of 2 mm and arranged at 2 mm intervals, as shown in FIG. 1 by means of a gravure roll, and the solvent was removed by means of a drier attached to the gravure roll. Then, a hygroscopic agent solution having the following composition was applied to the cloth to form another stripes as not to double on the two kinds of stripes by means of a roll, and dried, after which the cloth was heat treated at 150C for 3 minutes. The thus obtained cloth had an excellent crease resistance and hygroscopicity as shown in the following Table l.

(l) Crease proofing agent solution:

Organopolysiloxane diol having a Note: Twmbath method: After a crease proofing agent was applied to the cloth by a padding method and dried, a hygroscopic agent was applied to the cloth by the same method and dried, after which the cloth was heat treated at 150C for 3 minutes. The amounts of the crease proofing agent and hygroscopic agent adhered were the same as those in the present invention.

Example 2 An elastic processing agent solution having the following composition was applied to a woven fabric prepared from polyester finished yarns in the form of a spot composed of squares having a dimension of 5 X 5 mm arranged at 3 mm intervals as shown in FIG. 5, and dried in the same manner as described in Example 1. Then, an antistatic agent solution having the following composition was applied to the fabric in the space between the spots after which the cloth was dried and cure d aTl60C for 2 minutes. i

The thus obtained cloth had an excellent elastic property and antistatic property as shown in the following Table 2.

(l) Antistatic agent solution:

AMS-3l3 (made by Lion Yushi K.K.) 2 parts Perchlene parts (2) Elastic processing agent solution:

Organosiloxane diol having a polymerization degree of 800 2 parts Catalyst PC (made by Shinetsu Kagaku K.K.) 0.02 part Catalyst PD (made by Shinetsu Kagaku K.K.) 0.02 part Perchlene 100 parts TABLE 2 Compression Frictional elasticity charge Compression Elasti- (V) degree city Not treated l0,000 21.9 85.2 Present invention 1,000 23.5 94.0 Conventional method 4,100 22.9 89.8

Note: Conventional method: After a solution containing the antistatic agent and elastic processing agent was applied to the woven fabric, the fabric was dried and heat treated at C for 2 minutes. The amounts of the antistatic agent and the elastic processing agent were the same as those in the present invention.

Example 3 A stain proofing agent solution having the following composition was applied to a cotton/polyester blended yarn fabric in the form of a spot as shown in FIG. 3, and dried. Then a soil releasing agent (SR agent) having the following composition was further applied to the fabric in the form of a spot composed of circles, each having a diameter of 1 mm, by means of a printing roll, and dried at 100C for 45 seconds, after which the fabric was heat treated at 160C for 2 minutes.

The thus obtained cloth had an excellent resistance against both oily stain and aqueous stain as shown in the following Table 3.

(I) Stain proofing agent solution: Scotch guard FC-3 l0 A softener solution having the following composition was applied to a polyethylene film so as to form longitudinal stripes, each having a width of 2 mm and arranged at 1 mm intervals as shown in FIG. 1 by means of a gravure roll, and dried. Then-an antistatic agent solution having the following composition was further applied to spaces between the above obtained stripes of the softener by means of the same roll, and dried at 160C for 2 minutes. A

The thus obtained film had an excellent softness and antistatic property as shown in the following Table 4.

A crease proofing agent solution having the following composition was applied to the portion 1 of the surface of a scoured and dyed tricot knitted from polyester f n ished yarns as shown in FIG. 5 by means a gravure roll, and dried by means of a drier attached to the roll. Then, an antistatic agent solution having the following composition was further applied to the portion 2 of the tricot surface so as not to double on the two port-ions l and 2, and dried by the drier. Then, a stain proofing agent solution having the following composition was further applied to the portion 3 of the tricot surface, and dried by the drier. The treated tricot cloth was heat treated at lC for 2 minutes.

The thus obtained cloth contained the above described crease proofing agent, antistatic agent and stain proofing agent in amounts of 0.4 percent, 2.0 percent and 3.2 percent as a solid component respectively, and had an excellent crease resistance, antistatic property and stain proofing property as shown in the following Table 5.

(l) Creasing proofing agent solution:

Dimethyl-polyoxysiloxane diol (polymerization degree: 1500) 70 parts Starinous octoate 0.7 part Trichloroethylene 30 parts (2) Antistatic agent solution: 1

Copolymer of polyethylene glycol ester and acrylamide 10 parts Water I00 parts (3) Stain proofing agent solution: Scotch guard FC-2l8 (made by Sumitomo-3M K.l(.) 10 parts Acetone 100 parts TABLE 5 Crease Frictional Oil repellresistance charge ing property (g wale course Not treated 57.l 95 .7 7.500 0 Present 77.4 94.7 150 6 invention Control 1 77.5 96.0 5,500 0 Control 2 78.5 96.1 9,000 0 Note: Control 1: Only above described the crease proofing agent was applied and adhered to the tricot in an amount of 0.6 percent as a solid component.

Control 2: The above described crease proofing agent was diluted with trichlene and adhered to the tricot in an amount of 0.4 percent by padding. I

Example 6 A printing bath was made from parts of an emulsion composed of 47 percent of Kerosene, 51 percent of water and 2 percent of polyethylene glycol oleyl ether (H.L.B: 14), 20 parts of ethylene glycol diglycidyl ether and 5 parts of 25 percent aqueous solution of magnesium borofluoride. This printing bath was printed only on one surface of a scoured and bleached broad cloth composed of cotton yarns of 40 counts by means of a gravure roll engraved a pattern of 150 meshes on its entire surface. After the printed cloth was dried by a drier attached to the gravure roll, a dispersion having the following composition was printed on the other surface of the cloth by means of the above described gravure roll. This dispersion was composed of 92.5 parts of the above described emulsion, 5 parts of 50 percent emulsion of an emulsion copolymer (polymerization degree: 300) prepared from vinyl acetate and maleic acid anhydride in a mixing ratio of 1:1 2 parts of ethylene glycol diglycidyl ether and 05 part of 50 percent aqueous solution of zinc borofluoride. The thus treated broad cloth, both surfaces of which were printed, was dried and then heat treated in a dry state at 150C for 3 minutes. This procedure is the present invention. I

As a control, a conventional padding method is shown. The above described broad cloth was immersed in an aqueous solution composed of 3 parts of the above described vinyl acetate/maleic acid anhydride copolymer, [.2 parts of ethylene glycol diglycidyl ether, 0.3 part of 50 percent aqueous solution of zinc borofluoride and 95.5 parts of water, and the solution was squeezed to 60 percent based on the weight of the cloth by means of a padder.'After dried, the cloth was further immersed in an aqueous solution composed of 12 parts of ethylene glycol diglycidyl ether, 3 parts of 50 percent aqueous solution of magnesium borofluoride and parts of water, and the solution was squeezed to 60 percent based on the weight of the Cloth. The resulting cloth was dried and heat treated in a dry state at C for 3 minutes.

The obtained result is shown in the following Table TABLE 6 Crease resistance Soil re- (average of warp Bending Tear leasing and weft) (71) resisstrength property dry wet tance (g) treflec state state (mm) tance)(%) Not 50 46 62 W23 24 treated Control 76 76 I02 604 39 Present 80 80 75 831 48 invention As seen from Table 6, the cloth treated with the method of the present invention is excellent in all the properties, and the present invention is suitable for improving both of crease resistance and soil releasing property of cloth.

Example 7 A printing bath was prepared from 77 parts of the emulsion described in Example 6, 18 parts of 1,4- butane diol diglycidyl ether and 5 parts of 25 percent aqueous solution of magnesium borofluoride. This printing bath was printed only on upper surface of a scoured and bleached gaberdine cloth composed of polyester/cotton blended yarns (mix spinning ratio: 65:35) of 45 counts by means of a gravure roll engraved a pattern of 150 meshes on its entire surface. After the printed cloth was dried by means by a drier attached to the gravure roll, a dispersion having the following composition was printed to the under surface of the cloth by means of a gravure roll engraved a pattern of 180 meshes on its entire surface. This dispersion was composed of 88 parts of the above described emulsion, 10 parts of stearoylmethylamide-methylenepyridinium chloride and 2 parts of sodium acetate. The treated cloth, both surfaces of which were effected with different printings, was dried and heat treated in a dry state at 150C for 3 minutes. The above procedure is the present invention.

As a control, a conventional padding method is shown. A treating bath was produced from 10 parts of 1,4-butane diol diglycidyl ether, 3 parts of 50 percent aqueous solution of magnesium borofluoride and 82 parts of water. The above'described gaberdine cloth was immersed in the bath and the liquid was squeezed to 60 percent based on the weight of the cloth.

Then. the cloth was immersed in a treating solution composed of 6 parts of stearoylmethylamidemethylenepyridinium chloride, 1.5 parts of sodium acetate and 92.5 parts of water, and the solution was squeezed to 60 percent based on the weight of the cloth. Then, the cloth was dried and heat treated in a dry state at 150C for 3 minutes;

The obtained result is shown in the following Table 7.

TABLE 7 Wash and Water Water absorb- Bendwear pro repelling property ing perty ing (sec.) resis- (grade) property upper under tance surface surface (mm) Not 2.5 26 27- 68 treated Control 5.0 70 w w 105 Present 5.0 70 34 72 invention Note: Water absorbing property is designated by the time required until one drop of water of cc dropped on a cloth is dispersed and disappeared.

As seen from Table 7 in the treated cloth according to the present invention, the under surface has water absorbing property, but the upper surface has water repelling property. Further, the cloth has an excellent wash wear resistance and a unique cloth.

Example 8' A printing bath was prepared from 75 parts of the emulsion described in Example 6, 20 parts of diglycerol dibutyl ether and 5 parts of 50 percent aqueous so1ution of zinc borofluoride. This printing bath was printed on the same gabardine cloth as used in Example 7 to form a longitudinal stripe by means of a gravure roll having engraved portions of 1 mm width (150 meshes) and non-engraved portions of 1 mm width, and dried by means of a drier attached to gravure roll. Further, another longitudinal stripe composed of engraved portions of 0.8 mm width (200 meshes) and non-engraved portions of 1.2 mm width was applied to the cloth so as not to double on the two stripes-by using 1 percent aqueous solution of distearyl-dimethylammonium chlo- 22 ride. The treated cloth was dried and treated with steam at 120C for 5 minutes to obtain a result as shown in the following Table 8.

TABLE 8 Crease resistance (average of warp Frictional and weft) charge dry wet (V) state state Not treated 40 50 1650 Present 84 83 50 invention As seen fromTable 8, the cloth treated with the method of the present invention is excellent in the crease resistance and antistatic property.

Example 9 A printing bath was prepared from parts the emulsion as described in Example 6, 20 parts of propylene glycol diglycidyl ether and 5 parts of 25 percent aqueous solution of zinc borofluoride. This printing bath was printed on the upper surface of a broad cloth composed of 40 count yarns by means of a gravure roll hav ing a spotted pattern wherein 100 circles having a diameter of 1 mm were spotted per 400 cm". After the printed cloth was dried by means of a roller attached to the gravure roll, a solution composed of 85 parts of the above described emulsion, and 15 parts of aniline salt of hydroxymethanephosphonic acid was printed on the under surface of the printed cloth by means of a gravure roll engraved a pattern of meshes on the entire surface. Then the cloth was dried and heat treated in a dry state at C for 2 minutes. This procedure is the present invention.

As a control, a conventional padding method is shown. The above described broad cloth was immersed in an aqueous solution composed of 12 parts of propylene glycol diglycidyl ether, 3.5 parts of 25 percent aqueous solution of zinc borofluoride and 84.5 parts of water, and the solution was squeezed to 60 percent based on the weight of the cloth by means of a padder. The cloth was dried and heat treated in a dry state at 150C for 2 minutes. Then, the cloth was further immersed in 9 percent aqueous solution of aniline salt of hydroxymethanephosphonic acid, and the solution was squeezed to 60 percent based on the weight of the cloth by means of a padder and dried.

The obtained result is shown in the following Table 9.

TABLE 9 Crease resistance (average of warp The broad cloth not treated has no flame resistance, but both of the broad cloths treated with the method of the present invention and with the controlled method have an excellent flame resistance. However, the cloth treated with the controlled method has a rigid texture, while the cloth treated with the method of the present invention has a favourable texture.

Example 10 A first printing bath was prepared from 2 parts of [3-(acryloxyethyl)-diethylmethylammonium metasulfate (polymerization degree: 200), 10 parts of water, 1.5 parts of lauryl sulfate and 86.5 parts of the emulsion described in Example6. This printing bath was printed on one surface of a scoured and bleached polyester/- cotton mix spun tasah cloth (mix spinning ratio: 65:35) by means of a first gravure roll having a transverse stripe composed of engraved portions of 0.5 mm Width and non-engraved portions of 0.7 mm width and dried by means of an attached drier. Then, a second printing bath composed of 20 parts of diethylene glycol, 5 parts of 2.5 percent aqueous solution of magnesium borofluoride and 75 parts of the above described emulsion was printed on the same surface as described above of the cloth by means of a second gravure roll having a transverse stripe composed of engraved portions of 0.5 mm width and non-engraved portions of 0.7 mm width so as not to double on the two stripes, and dried by means of an attached roll. Further, a third printing bath composed of parts of stearoylmethylamidemethylenepyridiniurn chloride, 2 parts of sodium acetate and 88 parts of the above described emulsion was printed on the other surface of the above treated cloth, on which the first and second printing baths were not printed, by means of a third printing gravure roll engraved a pattern of 150 meshes on the entire surface, and dried by means of an attached drier. Then, the thus treated cloth was heat treated in a dry state at 150C for 3 minutes. The thus obtained cloth, which was treated with three processing agents of the antistatic agent, the crease proofing agent and the water repelling agent simultaneously, developed no static electricity, and had a crease resistance. Further, one surface of the cloth had water absorbing property, but the other surface had water repelling property. Consequently, this cloth was a unique finished cloth.

Example 1 1 An antistatic agent solution having the following composition was applied to the upper surface of a scoured and dyed tricot composed of 40 denier nylon yarns to form longitudinal stripes, each stripe having a width of 1 mm and arranged at 1' mm intervals, as shown in P10. 1 by means of a gravure roll, and dried by means of an attached drier. Then, a crease proofing agent solution having the following composition was applied to the same surface in the form of a stripe so as not to double on the former and latter stripes and not to penetrate to the under surface, and dried by an attached drier. Further, a water absorbing agent solution having the following composition was applied to the entire under surface of the cloth, and dried. The thus treated cloth was heat treated at 130C for 3 minutes.

The thus obtained cloth contained the above described antistatic agent, crease proofing and water absorbing agent in amounts of 0.8 percent, 0.4 percent and 0.5 percent as a solid component respectively, and had an excellent antistatic property, crease resistance and water absorbing property as shown in the following Table 10.

parts 80 parts Dimethylpolysiloxane (polymeri- Note: Control 1 z The above described antistatic agent was diluted with water and adhered to the cloth in an amount of 0.8 percent as a solid component by padding. Control 2: The above described crease proofing agent was diluted with water and adhered to the cloth in an amount of 0.4 percent as a solid component by padding. Control 3: The above described water absorbing agent was diluted with water and adhered to the cloth in an amount of 0.5 percent as a solid component by padding.

Example 12 An antistatic agent solution having the following composition was applied to the upper surface of a scoured polyester tricot in the form of longitudinal stripes, each having a width of 10 mm arranged at 1 mm intervals as shown in FIG. 1, by means a gravure roll, and dried by means of an attached drier. A stain proofing agent solution having the following composition was applied to the entire under surface of the treated cloth and dried by means of an attached drier. Then the treated tricot was heat treated at 150C for 1 minutes. The thus obtained cloth contained the antistatic agent and the stain proofing agent in amounts of 1.0 percent and 4.2 percent as a solid component, respectively, and had an excellent antistatic property and stain proofing property as shown in the following Table 11.

(l) Antistatic agent solution:

Quaternary ammonium salt of vinyl cyclohexyl ether and diethylamino vinyl ether 5 parts Water 100 parts (2) Stain proofing agent solution:

Scotch guard FC-2l8 (made by Surnitomo-3M K.K.) 25 parts Acetone 100 parts TABLE 1 l Frictional Oil repelling charge property (g Not treated 8500 0 Present 100 6 invention Control 1 0 Control 2 1000 7 Note: Control 1: The above described antistatic agent was diluted with water and adhered to the cloth in an amount of 1.0 percent as a solid component by padding. 7

Control 2: The above described stain proofing agent was diluted with water and adhered to the cloth in an amount of 4.0 percent as a solid component by padding.

Example 13 An antiflaming agent solution (A) having the following composition was applied to the upper surface of a lace stitched certain cloth prepared from a fluorescently whitened ground weave of polyethylene terephthalate filaments and a pattern of rayon filaments in the form of spots as shown in FIG. 2 by means of a gravure roll, and dried by means of an attached drier. Then, an ultraviolet absorbing agent solution having the following composition was further applied to the upper surface so as not to double on the two agents, and dried by means of an attached drier. Further, antiflaming agent solution (B) having the following composition was applied to the entire under surface of the cloth, and dried by means of an attached drier. The resulting cloth was heat treated at 120C for 5 minutes. The thus obtained cloth contained the above described antiflaming agent (A), antiflaming agent (B) and ultraviolet absorbing agent in amounts of 4.1 percent, 2.1 percent and 0.1 percent as a solid component respectively, and had an excellent flame resistance and light resistance as shown in the following Table 12.

(1) Antiflaming agent solution (A): Tris-2,3-dibrornopropyl Note: Control 1: The above described antiflaming agent (A) was diluted with perchlene and adhered to the cloth in an amount of 4.2 percent as a solid component by padding.

Control 2: The above described ultraviolet absorbing agent was diluted with acetone and adhered to the cloth in an amount of 0.1 percent as a solid component by padding.

Example 14 An antifusing agent solution having the following composition was applied to the entire upper surface of a broad cloth composed of blended yarns of 65 percent of polyester and 35 percent of cotton in the form of spots by means of an gravure roll, and dried by means of an attached drier. Then, a softening agent solution having the following composition was applied to the surface in the form of spots so as not to double on the two agents, and dried by an attached drier. The resulting cloth was heat treated at 150C for 2 minutes.

The thus obtained cloth contained the above described antifusing agent and softening agent in amounts of 7.0 percent and 3.2 percent as a solid component respectively, and had an excellent fuse resistance and softness as shown in the following Table 13.

(l) Antiflaming agent solution:

Dimethylpolysiloxsne diol (2) Softening agent solution:

Cetylpyrimidium bromide 20 parts Water parts TABLE 13 Fuse Texture resistance (sec.) Not treated poor Present 30 excellent invention Control 25 poor (rigid, stiff) Note: Control: The above described antifusing agent was printed and adhered to the cloth in an amount of 7.0 percent as a solid component.

Example 15 An antipilling agent solution having the following composition was applied to the upper surface of a scoured and dyed ester/rayon staple mix spun serge in the form of stripes having a 1.5 mm width at 1.5 mm intervals as shown in FIG. 1 by means of a gravure roll, and dried by means of an attached drier. Then, a softening agent solution having the following composition was applied to the surface so as not to double on the two agents, and dried by means of an attached drier. The resulting cloth was heat treated at C for 5 minutes.

The thus obtained cloth contained the above described antipilling agent and softening agent in amounts of 2.5 percent and 2.0 percent as a solid component respectively, and had an excellent anitpilling property and softening as shown in the following Table 14.

( l) Antipilling agent solution:

Polyurethane prepolymer (average molecular weight 18,000; NCO content 1.8%) prepared from 6 moles of polypropylene ether glycol (M.W. 2,000), 12 moles of tolylene diisocyanate, and

' 1 mole of polypropylene triol 30 parts Trichloroethylene 100 parts (2) Softening agent solution:

DKS Taflon Perma A sol (made by Daiichi Kogyo K.K.; 10 parts polyamine series compound) Water 100 parts TABLE 14 Antipilling property Texture (g Not treated 1 poor Present 4 soft and invention excellent Control 1 5 highly stiff Control 2 2 soft and excellent Note: Control 1: The above described antipilling agent was diluted with water and adhered to the cloth in an amount of 2.5 percent as a solid component by padding.

Control 2: The above described softening agent was diluted with water and adhered to the cloth in an amount of 2.0 percent as a solid component by padding.

Example 16 A moth proofing agent solution having the following composition was applied to the entire upper surface of a scoured and dyed serge made of worsted yarns in the form of spots by means of a gravure roll, and dried by means of an attached drier. Then, a shrinkproofing agent having the following composition was applied to the entire under surface, and dried by means of an at- (1) Moth proofing agent solution:

Pentachlorophenol 0.1 part Methanol 100 parts (2) Shrink proofing agent solution:

Zeset T (made by Du Pont Co., 100 parts reactive polyethylene) Perchloroethylene 900 parts TABLE 15 Shrink proofing Moth proofing property (areal property shrinkage) (moth proofing effect) 12 20 Not treated Present invention 6 80 Example 17 An antipilling agent solution having the following composition was applied to the upper surface of a scoured and dyed jersey knitted from polyacrylonitrile spun yarn in the form of spots as shown in FIG. 3 by means of a gravure roll, and dried by means of an'attached drier. A stain proofing agent solution having the following composition was further applied to the jersey in the form of spots so as not to double on the spots of the above two processing agents, and dried by means of an attached drier. The resulting cloth was heat treated at 150C for 1 minute.

The thus obtained cloth contained the above described antipilling agent and stain proofing agent in amounts of 2.5 percent and 4.0 percent as a solid component respectively, and had an excellent antipilling property and stain proofing property as shown in the following Table 16.

(I) Antipilling agent solution:

Polyurethane prepolymer (average molecular weight 20,000; NCO content 1.7. 96) prepared from 6 moles of polypropylene ether 3 PHMM- 892 l molea of hexamethylbne diisocyanate, and

1 mole of polypropylene triol 10 parts Trichloroethylene. 100 parts (2) Staln proofing agent solution:

Scotch guard FC-SlO 20 parts Perchloroethylene 80 parts TABLE 16 Antipilling Oil repelling property property (grade) (grade) Not treated 1.5 0 Present 4.5 6 invention Control 1 5.0 4 Control 2 2.0 7

Note: Control I: The above described antipilling agent was diluted with trichloroethylene and adhered to the cloth in an amount of 2.5 percent as a solid component by padding.

Control 2: The above described stain proofing agent was diluted with perchloroethylene and adhered to the cloth in an amount of 4.0 percent as a solid component by padding.

Example 18 A stain proofing agent solution having the following composition was applied to the entire upper surface of a scoured and dyed denier nylon taffeta so as not to penetrate to the under surface by means of a gravure roll, and dried by means of an attached drier. An antiflaming agent solution having the following composition was further applied to the entire under surface of the tafieta, and dried by means of an attached drier. Then, the treated taffeta was heat treatedat l50C for 1 minute.

The thus obtained cloth contained the above described stain proofing agent and antiflaming agent in amounts of 3.0 percent and 4.0 percent as a solid component respectively, and had an excellent stain proofing property and flame resistance as shown in the following Table 17.

(l) Stain proofing agent solution:

Scotch guard FC-2l8 22 parts Water parts lsobutanol 2 parts (2) Antiflaming agent solution:

Tris-(chloroethyl) phosphate 340 parts Trichloroethylene 660 parts TABLE 17 Oil repelling Flame resis' property lance (number (grade) of times conupper under tacted with surface surface tire) Not treated 0 l Present invention 6 4 4 Control 1 6 4 2 Control 2 0 4 4 Note: Control 1: Only the above described stain proofing agent was printed and adhered to the cloth in an amount of 3.0 percent as a solid component.

Control 2: Only the above described anti-flaming agent was printed and adhered to the cloth in an amount of 4.0 percent as a solid component.

Example 19 An antiflaming agent solution having the following composition was applied to the entire under surface of a scoured and dyed twill curtain fabric composed lOO percent nylon by means of a gravure roll, and dried by means of an attached drier. An ultraviolet absorbing agent solution having the following composition was further applied to the entire upper surface of the fabric, and dried by means of an attached drier. The thus treated curtain fabric was heat treated at C for 7 m u es The thus obtained cloth contained the above described antiflaming agent and ultraviolet absorbing agent in amounts of 5.2 percent and 0.1 percent as a solid component respectively, and had an excellent flame resistance and light resistance as shown in the following Table 18.

(l) Antiflaming agent solution:

Tetraquis-hydroxydimethylphosphonium chloride 25 parts Ethanol 100 parts (2) Ultraviolet absorbing agent solution: 2,2,4,4'-tetrahydroxybenzophenone 0.5 part Methanol 100 parts TABLE 18 Flame resistance Light (vertical test) resistance remained carbonized grade fire(sec.) length (in.) Not treated completely I burned Present 0 4.2 3 invention Control 1 0 3.6 l

completely 3 burned Control 2 Example 20 A water repelling agent solution having the following composition was applied to. the entire under surface of a scoured and dyed woven fabric composed of polyester finished yarns by means of an gravure roll, and dried by means of an attached drier. Then an antifusing agent solution having the following composition was applied to the entire upper surface of the woven fabric, and dried by means of an attached drier. The thus treated fabric was heat treated at 150C for 2 minutes.

The thus obtained cloth contained the above described water repelling agent and antifusing agent in amounts of 3.0 percent and 5.8 percent as a solid component respectively, and had an excellent water repelling property and fuse resistance as shown in the following Table 19. (1) Water repelling agent solution:

Methyl-hydrogempolysiloxane (viscosity 100 centistokes) 10 parts Perchloroethylene 90 parts (2) Antifusing agent solution:

Methyl-hydrogen-polysiloxane diol (polymerization degree 1,500) 90 parts Dibutyltin dioctoate 0.9 part Perchloroethylene 30 parts Butylated melamine 10 parts TABLE 19 Water repell- Fuse ing property resistance (sec.) Not treated Present invention 100 32 Control 1 100 Control 2 80 27 Note: Control 1: The above described water repelling agent was diluted with perchlene and adheredto the cloth in an amount of 3.0 percent as a solid component by padding.

Control 2: The above described antifusing agent was diluted with perchlene and adhered to the cloth in an amount of 5.8 percent as a solid component by padding.

Example 21 In 60 parts of water was dissolved 4.5 parts of tetraoxane at 40C, and 1.5 parts of Scourol 400 (made by Kao Sekken K.l(.,non-ionic surfactant) was added to the solution. Then, 34 parts of kerosene was gradually added to the solution while stirring vigorously to prepare an emulsion having a viscosity of 430 cps. This emulsion was printed on one surface of a scoured and bleached polyester/cotton mixed spun broad (mix spinning ratio: polyester/cotton=65/35) by means of a gravure roll engraved a pattern of 150 meshes on its entire surface, and dried. Then, an soil releasing agent solution composed of 3 parts of Serogen 7 (made by Daiichi Kogyo K.K.) 1 part of polyethylene glycol diglycidyl ether (polymerization degree of polyethylene glycol: 400), 0.2 part of zinc borofluoride and 96 parts of water was further printed on the other surface of the broad by means of the same roll, and dried. The printed broad was heat treated in a dry state at 150C for 3 minutes.

The thus treated cloth had a crease resistance and a soil releasing property, and further a soft texture as shown in the following Table 20.

As a control, a conventional one-bath method was effected. The same starting broad cloth was immersed in a solution composed of 4 parts of tetraoxane, 1 part of polyethylene glycol diglycidyl ether, 3 parts of Serogen 7A, 1 part of zinc borofluoride and 91 parts of water, and the solution was squeezed to 60 percent based on the weight of the cloth by means of a padder. After dried, the resulting cloth was heat treated in a dry state. The result is also shown in Table 20.

TABLE 20 Crease Wash and Soil reresistance wear leasing Bending property property resist- (average of (grade) (reflecance warp and weft) lance) (mm) Not treated 76 3.0 42 62 One-bath method 84 4.0 57 1 18 Present invention 85 4.5 63 77 Example 22 A dispersion composed of 12 parts of tetraoxane, 77 parts of water and 1 part of Noigen ET 120 (made by Daiichi Kogyo K.K.) was heated to C. After the tetraoxane was dissolved, 7 parts of 5 percent aqueous solution of Dacloid HF (made by Kamogawa Kako K.K.) was added to the solution, and the resulting mixture was cooled to room temperature from outside, and added with 3 parts of 50 percent aqueous solution of zinc chloride to obtain an opaque dispersion having a viscosity of 280 cps. The resulting dispersion was printed on a scoured and bleached polyester/cotton mix spun broad (mix spinning ratio of polyester/cotton= 65/35) by the use of a stripe pattern having engraved portions of 2 mm width, each portion being patterned to 160 meshes, and nonengraved portions of 1 mm width by means a gravure roll, and dried. Then, 2 percent aqueous solution of cetyl-trimethylpyridinium chloride was printed on the above printed broad by the use of a stripe pattern having engraved portions of 1 mm width, each portion being patterned to meshes, and non-engraved portions of 2 mm width by means of a gravure roll so as not to double on the two kinds of stripes. After dried, the printed borad was heat treated in a dry stateat C for 3 minutes. I

The thus obtained cloth had a crease resistance and an antistatic property as shown in the following Table 21.

TABLE 21 Treating Crease resis- Frictional method tance (average charge of warp and weft) Not treated 75 330 Present 90 0 invention Example 23 A solution of 15 parts of tetraoxane and 4 parts of 50 percent aqueous solution of zinc borofluoride dissolved in dimethylformamide was printed on a woolen tropical suiting by means of a gravure roll engraved a pattern of 200 meshes on its entire surface. After dried, the

printed tropical suiting was treated with steam at 130C for 20 minutes.

The thus treated wool was excellent in the wash and wear property as shown in the following Table 22.

TABLE 22 Crease resist- Wash and Wash and tance (areal wear wear shrinkage) property property (grade) after 5 times washing (g Not treated 23 2 1 Present invention 6 5 5 Example 24 A scoured and bleached polyester/cotton mix spun broad was printed by using the following three printing baths and patterns on both surfaces by means of a three color gravure roll. 3

i. Composition of the first bath and pattern of the first roll:

The first bath is the same as the tetraoxane dispersion in Example 22. The first roll has a transverse linear stripe pattern having engraved portions of v 0.5 mm without mesh and non-engraved portions of 0.5 mm width.

ii. Composition of the second bath and pattern of the second roll:

The second bath is a emulsion having the following composition, wherein Permalose T is used as a water absorbing agent.

Permalose T 7 parts Kerosene/water emulsion (viscosity: 3,500 cps) 75 parts Water 18 parts The second roll has a longitudinal stripe pattern having engraved portions of 1 mm width, each engraved portion being patterned to 120 meshes, and non-engraved portions of 1 mm width.

iii. Composition of the third bath and the pattern of the third roll:

The third bath is a dispersion having the following composition, wherein vinyl acetate/maleic acid anhydride copolymer is used as a soil releasing Namely, the above described polyester/cotton mix spun broad was printed on its upper surface by using the first bath and roll and the second bath and roll, and was printed on its under surface by using the third bath and roll, after which the printed broad was heat treated in a dry state at 150C for 3 minutes. The obtained result is shown in the following Table 23.

As seen from Table 23, the thus obtained cloth had an excellent crease resistance, water absorbing property and soil releasing property.

A crease proofing agent solution having the following composition was applied to the entire upper surface of a cotton twill fabric cloth (count: warp 36/2 weft 24/2 density: warp l 1 1.5/inch, weft 57/inch; 264.4g/m so as not to penetrate to the under surface by means of an intaglio roll, and dried at 80C. Then,

a catalyst solution having the following composition was further applied to the under surface of the cloth by means of the above described roll, and dried. The cloth was heat treated at 150C for 3 minutes, washed with a bath composed 1 g of Scourol 400 (made by Kao Sci:-

ken K.K.; non-ionic surfactant), 1 g of soda ash and 1 l of water at 70C for 30 seconds, and dried. The thus obtained cloth contained the creasing proofing agent resin in an amount of 3.2 as a solid component, which was set only in the middle layer of the cloth, and had an excellent crease resistance, wash and wear property,

abrasion resistance, tensile strength and tear strength. Even when this cloth was washed repreatedly, there was no difference between the both surfaces in the whiteness.

agent (1) Crease proofing agent solution:

Dimethyl-dihydroxyethylene urea 15 parts vinyl emu/mam; i Kerosene viscosity increasing anhydride copolymer (polymeriage"! Paris zation degree: 150) 12 parts Bicron K 43 (Softener) Glycerin diglycidyl ether 2 parts (made y 1171305113 YuShi 2 Parts Zinc borofluoride 0.5 parts 50 Water 23 parts water 85.5 pang (2) Catalyst solution:

Zinc nitrate 8 parts The third roll in engraved to 150 meshes on its en- 22:? Emmy 3O pans tire surface. Water 62 parts Crease Crease resistance Tensile Tear whiteness resistance (percent) Wash strength strength after water (percent) (after washing) and (K8) (9 Washing absorbwear ing prop- Upper Under prop- Dry Wet Dry Wet erty Warp Weft Warp Weft surface surface erty Not treated 51 45 52 45 1 101 42 2,400 2,950 115 115 7 Present invention. 76 73 73 4.3 92 37 2,230 2,710 108 107 7 Control l 75 71 75 71 3.9 53 24 1,946 2,310 84 84 28 Control 2 75 72 74 73 4.1 74 31 2,150 2,560 86 91 24 Note Control l-A cloth was treated with a processing soiution containing both of the above described crease proofing agent and catalyst so as to obtain pick up by padding method. dried and heat treated, whereby 3.2% of solid resin was applied to the cloth.

Control 2 A processing solution containing both of the above described crease proofing agent and catalyst was applied to the upper surface of a cloth, and 3.2% of solid resin was set to the upper surface layer and the middle layer of the cloth.

33 Example 26 A crease proofing agent solution having the following composition was applied to the entire upper surface of a mix spun broad cloth (count: warp 45 weft 45 density: warp l41/inch, weft 73/inch; 122.9 g/m composed of 65 percent of polyethylene terephthalate and 35 percent of cotton so as to penetrate as far as the middle layer of the cloth by means of an intaglio roll, and dried at 80C for 7 minutes. A catalyst solution having the following composition was applied to the under surface of the cloth by means of the same roll, and dried. The cloth was further heat treated at 140C for minutes, washed with a bath composed of 1 g of Emal NC (made by Kao Sekken K.l(.; anionic surfactant), 1 g of soda ash and 1 l of water at 50C for l minute, and dried. l

The thus obtained cloth contained the crease proofing agent resin in an amount of 3.0 percent as a solid component, which was set only in the middle layer, and had an excellent crease resistance, wash and wear property, abrasion resistance, tensile strength and tear strength, and further had substantially the same water absorbing property as that of the untreated cloth. Even when the cloth was washed repeatedly, there was no difference between the both surfaces in the whiteness.

34 Example 27 10 having the following composition was further applied to the under surface of the cloth so as to penetrate as far as the middle layer by means of a roll having a pattern of longitudinal lines, and dried. The cloth was heat treated at 160C for 2 minutes, washed with a bath composed of 2 g of Scourol 100 (made by Kao Sekken K.l(.; non-ionic surfactant) and 1 lot water at 70C for 15 seconds, and dried.

The thus obtained cloth contained the crease proofing agent resin in an amount of 3.2 percent as a solid 2 component, which was set in a pattern of lines in the middle layer of the cloth, and had an excellent crease resistance, wash and wear property, abrasion resistance, tensile strength and tear strength, and further had substantially the same excellent water absorbing property as that of untreated cloth. Even when the cloth was washed repeatedly, there was no difference between the both surfaces of the cloth in the whiteness. The obtained result is shown in Table 26.

(1) Catalyst solution: (1) Crease proofing agent solution: Magnesium chloride 1.2 parts lmidazolidone resin Kerosene viscosity increasing (trade mark: Permafresh D.C.) 30 parts agent 30 parts 1% aqueous solution of hydroxy- Water 69 parts ethyl-cellulose (trade mark: (2) Crease proofing agent solution: cellosize QP 15.000) 90 pans Dimethylolethyl carbamate 20 parts (2) Catalyst solution: Kerosene viscosity increasing Zinc nitrate catalyst (trade mark: Catalyst F) 2 parts agent parts 0.3% aqueous solution of Bicron K 43 (softener 2 parts hydroxyethyl-cellulose 98 parts V W ater i W W WV 20 parts TABLE 25 Crease resistance Crease (percent) Wash Abrasion at Abrasion at Tensile Tear Water Whiteness after resistance (after and plane fold strength strength absorbwashing (percent) washing) wear (kg) (8} ing prop- Upper Under Upper Under prop- Upper Under Dry Wet Dry Wet erty surface surface surface surface Warp Weft Warp Weft erty surface surface Not treated 76 76 75 3 101 97 173 167 36 17 1,035 651 7 116 116 Present invention 89 88 89 88 4.4 82 83 157 152 35 17 1.010 623 7 107 108 Control 1 87 86 87 87 3.8 68 66 133 137 33 15 980 &Q 34 82 31 Control 2 89 87 88 88 4.3 65 79 129 143 33 16 992 605 28 81 97 Note:

Control l-A cloth was treated with a processing solution containing both of the above described crease proofing agent and catalyst so as to obtain 60% pick up by padding method, dried and heat treated, whereby 3.0% of solid resin was applied to the cloth.

Control 2-A processing solution containing both of the above crease proofing agent and catalyst was applied to the upper surface of a cloth, and 3.0% of solid resin was set to the upper surface layer and the middle layer of thecloth. V V

TABLE 26 Crease resistance Crease (percent) Wash Abrasion at Abrasion at Tensile Tear Water whiteness after resistance (after and plane fold strength strength absorbwashing (per ent) washing) wear (kg) (g) ing prop- Upper Under Upper Under prop- Upper Under Dry Wet Dry Wet erty surface surface surface surface Warp Weft Warp Weft erty surface surface Nottreated..... 77 7s 77 76 '3 103 104 178 171 36 17 1,042 660 6 114 114 Present invention..... 89 88 88 87 4.3 84 159 157 35 17 1,010 618 6 106 107 Controll 86 85 84 83 3.8 '67 65 .129 131 34 15 972 557 35 83 83 Contro12 88 88 87 86 43 72 81 128 148 35 16 986 615 32 82 96 Note: 4

Control 1- A cloth was treated with a processing solution containing both of the above described catalyst and crease proofing agent so as to obtain 60% pick up by padding method, dried and heat treated, whereby 3.2% of solid resin was applied to the cloth.

Control 2 A processing solution containing both of the above described crease proofing agent and catalyst was applied to the upper surface of a cloth. and 3.2% of solidresin wa s set tothe uppersurface layg and the mfldlt layer of the clotl Example 28 scribed antistatic agent and water absorbing agentin A crease proofing agent solution having the following both the surfzfces m amounts of 1 Rercem and 04 P composition was applied to the upper surface of a mix cent as a solid component respectively, and both the spun broad cloth (density: warp Em/inch weft agents did penetrate from the applied surface to the 72/inch) made of mix spun monofilaments composed 5 other f g and consequently the cloth i an excelof 65 percent of polyethylene terephthalate and 35 pera t i g z g n P g gl cent of rayon by means of a roll having a pattern of pare o tame t is 5 Own m t e O Owmg a e 28. allel fine lines, the direction of which are parallel to the direction of the warp of the cloth. Then, the catalyst 50- TABLE 28 lution was further applied to the under surface of the o Frictional Water absorbing cloth at an angle 80 against the direction of the warp. chargqm H propgurgsem 7 M by means of a roll having a pattern of parallel fine lines. I before after before after The cloth was dried at 100C for seconds, heat Washmg Washing Washmg Washing treated at 170C for 1 minute, washed with perchloro- 5 gigs? 9200 65 38 ethylene at 20C for 5 minutes and dried. invention 150 350 s 7 Control 1 I40 420 60 I The thus obtained cloth contained the crease proof Comm! 2 230 5500 5 6 ing agent in an amount of 2.8 percent as a solid compocomm] 3 45 440 65 58 nent, which formed a spotted pattern in the middle COMO 4 5 5 layer of the cloth, and had an excellent crease resis- 20 N T r I rf tance ra o resistance tensile strength, tear otogelggntrol l. he antistatic agent was app ted to on y one su ace Strength, and water absorbing p p ywhen the Control 2: The water absorbing agent was applied to only one surface cloth was washed repeatedly, there was no difference Control 3; The antistatic agent was applied by padding method. between the both Surfaces of the cloth In the whlteness' Control 4: The water absorbing agent was applied by padding method.

The obtained result is shown in Table 27. 25

(l) Crease proofing agent solution: E l 30 Dimethyl-polysiloxane diol 2.5 parts d' th th is! l l ZJ IZLZdQZEZ g -$25 0, 3 pm An antistatic agent solution composed of 20 g of a Trichlene P 30 cationic antistatic agent prepared by copolymeri'zation I y of 3 parts of 2-methacryloyloxyethyl-trimethyiammoni- Viscosity of this solution is 110 centistokes. ummwthy] lf t and 1 part f z,3 dibromopropyl methacrylate, 60 g of a viscosity increasing agent pre- (2) Candy mum: pared from kerosene and 20 g of water was applied to Dibutyltin dilaurate 0.03 part Trichlene 100 parts the under surface of a twill fabric cloth having 2/2 twill TAB LE 27 Crease re- Abrasion sistance resistance Abrasion whiteness Crease re (percent) at plane at fold Tensile Tear Water after washing sistance (after strength strength absorb- (percent) washing) Upper Under Upper Under (kg) (g) ing Upper Under sursursursurpropsursur- Dry Wet Dry Wet face face face face Warp Weft Warp Weft erty face face Texture Not treated 77 75 77 76 90 88 125 I24 35 i5 980 450 7 116 116 l.

Present invention.. 90 89 89 88 82 84 H5 H7 38 18 l 100 560 [2 H38 107 Good hand.

Control 1... 83 87 87 86 62 102 101 37 18 1:080 540 65 88 87 Waxy. Control 2.. 90 89 S9 87 58 56 98 96 36 17 1.070 530 83 102 Waxy.

Note:

Control 1 -A cloth was treated with a processing solution containing both of the above described crease proofing agent and catalyst so as to obtain 130% pick up by padding method, dried and heat treated, whereby 2.8% of solid resin was applied to the cloth.

Control 2-A processing solution containing both of the above described crease proofing agent and catalyst was applied to the upper surface of a cloth. and 2.8% of solid resin was set to the upper surface layer and the middle layer of the cloth.

Example 29 50 texture which was prepared from polyester false twist I R 0 yarns of l00d/32f/2p, and dried at 100C. Then, an an- An antistatic agent solution prepared from 15 parts tipilling agent composed of 10 parts of a prepolymer of a cationic antistatic agent of a polymer, which was prepared from 1 mole of polypropylene ether glycol a polymerization product of quaternary ammonium salt (molecular weight: 2,000), 2 moles of tolylene diisocyof diethylarninoethyl methacrylate with dimethyl sul- 55 anate and 1.6 mole of polypropylene ether triol (mofate, and parts of 45 percent aqueous solution of lecular weight 4,000) and parts of xylene as a solhydroxyethyl-cellulose was applied to one surface of a vent was further applied to the upper surface of thescoured and dyed cloth of nylon jersey knitted from nycloth, and the cloth was heat treated at C for 5 lon-6 twist yarns of 70d/18f/2p by means of a gravure minutes. roll, and dried at 80C. Then, water absorbing agent so- 60 The thus obtained cloth contained the above deiution composed of 2 g of a reaction product, which scribed antistatic agent and antipilling agent in was obtained by reacting 31 g of ethylene oxide with 60 amounts of 1 percent and 1 .2 percent as a solid compog of dimer or trimer of caprolactam, and l g of water nent respectively, and both the processing agents did was further applied to the other surface of the cloth, not penetrate from the applied surface to the other surafter'which the cloth was heat treated at 130C for 5 65 face of the cloth. minutes. The cloth had an excellent antipilling property and The thus obtained cloth contained the above deantistatic property as shown in Table 29.

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Classifications
U.S. Classification428/196, 427/210, 428/922, 428/907, 427/170, 427/160, 428/920, 428/921
International ClassificationD06M23/00, D06M23/16
Cooperative ClassificationY10S428/922, Y10S428/92, D06M23/16, Y10S428/921, D06M23/00, Y10S428/907
European ClassificationD06M23/00, D06M23/16