Fiber treatment composition, fiber treated thereby, and a method of treating fiber thereby

Abstract: A fiber treatment composition containing a synthetic resin such as a silicon resin emulsion, a polyurethane resin emulsion and the like and a pulverized hydrophilic organic group natural material such as collagen. A fiber treated by using the treatment composition. A method of treating the fiber by stirring the fiber treatment composition in a ball mill or the like, soaking a fiber in the composition by the pad method, and drying the fiber under a temperature from 80 to 160 degrees.

Description: BACKGROUND OF THE INVENTION 1. FIELD OF THE INVENTION This invention is broadly concerned with a fibre or cloth treatment composition, a fibre or cloth finished with the composition and a method of treating a fiber or cloth by means of the composition. The composition is intended particularly to be used to cloths like stockings, leather products made of vinyl chloride resin, leather products of synthetic or artificial leather, ground cloth of the leather products, and an upholstery for automobiles. 2. DESCRIPTION OF THE RELATED ART A fiber treatment composition containing silicon resin, polyurethane resin, polyacrylic group resin, or fluorine group resin has previously been know to give flexibility or elasticity in fiber or plain cloth and to prevent wrinkles of plain cloth during processing to achieve handle. In a super-soft processing, the silicon resin and the polyurethane resin are generally employed as the main resins to obtain handle. Giving an example, aminodenatured silicon is commonly used in the art as it is excellent in softening fiber or plain cloth and giving fine soft feeling, draping feeling and stretch-back characteristics. For the purpose of giving a volume, elasticity and dry feeling, polyurethane resin is also utilized. However, it is also noted that an aminodenatured silicon group finisher tends to reduce the hygroscopic property of fiber and cloth. Other treatment compositions containing ethylene oxide or an emulsifying agent are utilized to obtain the desired hygroscopic property, but do not achieve durability or tend to badly influence flexibility. A treatment composition containing methyl groups in order to improve durability is also known well in the art, but is not suitable to be used for treating plain cloth worn next to the skin, as such compositions include formalin. From these viewpoints, a general softening agent for making good the loss of hygroscopic property is used, optionally together with a softening agent for obtaining dry feeling. EP-A2-0413627 discloses the preparation of fine particles of gelatins and amino acids for blending into natural or synthetic resins, in order to prepare paints, coating layers and mouldings. Such particles are alleged to impart excellent moisture absorption and permeation properties to resin coating layers. The gelatin particles used typically have a mean particle size from 3 µm to 5.5 µm, typically with less than 10 wt.% of the particles having a size larger than 9 µm and less than 10 wt.% of the particles having a size smaller than 1.5 µm. According to example 8, a knit fabric is coated with an urethane solution comprising such particles to obtain a moisture permeable fabric with a good feel. JP-A-58-117299 and JP-A-62-263384 disclose cloth treated with emulsions of synthetic resin comprising leather powder to obtain artificial leater products. It is an object of the present invention to provide a treatment composition capable of giving a product selected from fibres, cloths, cloth-like products made of synthetic or artificial leather, and ground cloths of said cloth-like leather products the comfortable, dry, natural feel, fine hygroscopic property and durability, and to provide a fiber or cloth product selected from fibres, cloths, cloth-like products made of synthetic or artificial leather, and ground cloths of said cloth-like leather products finished with the treatment composition and a preferable method of treating a product selected from fibres, cloths, cloth-like products made of synthetic or artificial leather, and ground cloths of said cloth-like leather products by using the treatment composition. The present invention relates to a treatment composition for use with product selected from fibres, cloths, cloth-like products made of synthetic or artificial leather, and ground cloths of said cloth-like leather products, the composition being defined in claim 1. The applicable synthetic resin emulsions are a silicon resin emulsion, a polyurethane resin emulsion, a polyacrylic group resin emulsion or a fluorine group resin emulsion or a mixture thereof. The silicon resin emulsion is preferably aminodenatured. A solid form of the resin will be stable in a film shape. These resins are effective in reducing the quantity of the pulverized hydrophilic organic group containing natural material which falls off the treated fiber or cloth. Generally silicon aminodenatured resins are stable in an oiled state. On changing the aminodenatured emulsion into film shape better handle, adhesion and wash-proofness are achieved than that of the oiled aminodenatured emulsion. The pulverized hydrophilic organic group natural material includes pulverized animal protein like stiff protein such as collagen, elastin, silk powder and sponge powder and wool, and further includes pulverized plant like cellulose such as cotton, hemp, pulp and seaweed. The particles of the pulverized material has a standard deviation 3 micrometers and an average diameter no more than 7 micrometers, preferably less than 4 micrometers so as to improve the adhesive property toward cloth, and the feel of the product. When particle size exceeds 7 micrometers, the adhesion property becomes worse and the product feels rough. A tinge of the pulverized hydrophilic organic group natural material can have a whiteness degree of over 70 %, when the average particle size is 5 micrometers. Whiteness degree is apt to change upon an average particle size. It is naturally noted that if a pulverized material has a color, the produced fiber and cloth do not achieve a preferable tinge. The treatment composition according to this invention comprises 99 -90% of a synthetic resin emulsion and 1 - 10% of a pulverized hydrophilic organic group-containing natural material by weight. The synthetic resin emulsion contains water in an amount of at least 8 times by weight of the pulverized hydrophilic organic group-containing natural material. When the amount of water is less than 8 times by weight of the pulverized hydrophilic organic group-containing natural material, this material absorbs water and then expands, and a desirable emulsion by mixing the two ingredients will not be obtained. The fiber or cloth product selected from fibres, cloths, cloth-like products made of synthetic or artificial leather and ground cloth of said cloth-like leather products according to this invention is characterized by having been finished with the above mentioned treatment composition. The method according to this invention has the steps of stirring the treatment composition and soaking a product selected from fibres, cloths, cloth-like products made of synthetic or artificial leather and ground cloth of said cloth-like leather products in the treatment composition; and drying the soaked product. The stirring step may be carried out in a ball mill, tube mill or by a screw, but preferably, in the ball mill. General stirring of the two ingredients is not usually enough to disperse the pulverized materials sufficiently, so that condensation of the materials occurs, or the tendency of the pulverized material to fall-off the treated fiber or cloth becomes conspicuous. While in the ball mill dispersion of the pulverized material is sufficient and osmotic action to the material and its adhesion property to fiber or cloth can be improved, since pressure is produced in the mill. The ball mill is further effective in crushing the pulverized hydrophilic organic group natural material, which causes an improvement in handle. A pad method or a spray method can be used as the soaking process. A preferable temperature in the drying step is from 80 to 160°C, preferably from 100 to 120°C. The pulverized hydrophilic organic group-containing natural material with water therein has a tendency to be highly hydrolyzed, give off a bad smell and change its color under a high temperature. While under a low heating temperature, rather long time for heating is needed so that a working efficiency becomes bad. BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a diagrammatic view explaining a fiber/cloth processing method according to the present invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT(S) The mentioned objects of the present invention will become more fully apparent with reference to the following experimental examples, control examples and Figure 1 which relate to the preferred embodiment of the present invention. [EXPERIMENTAL EXAMPLE 1] An emulsion solution 1 is prepared by diluting, in 247 grams water in weight, with 100 grams silicon AMZ (13% synthetic resin ingredient, Manufacturer:NIKKA KAGAKU) in weight as an aminodenatured silicon group resin a solid matter of which will be finished in a film shape. Into the prepared solution 1, a 13-gram pulverized collagen 2 having an average particle diameter 5 micrometers is added, and the mixture is stirred for 10 minutes by means of a ball mill 3 (The epicycle ball mill produced by SEISHIN CORPORATION) at 150 revolutions per minute, which is denoted by (A) step in Figure 1. Succeedingly, a 27 grams nylon plain cloth for stocking 5 is first soaked in a fiber/cloth treatment composition 4 which is prepared in the ball mill 3 and second transferred into a mangle 6 with a bite pressure of 1 kilogram per square centimeter between a pair of the accompanied rollers in order to remove an excess treatment, which is so called a pad process for an adhesion of the composition to cloths as denoted by (B) step in the drawing. The mangle 6 is of a machine to wring the wet cloth dry out by using a pair of rollers, one being made from metal and the other from rubber. In this step, the 36 grams treatment 4 (the 2.6 grams solid matter thereof) in weight is used for the cloth 5. The processed cloth for stocking 5 is then transferred into a drying machine 6, which is denoted by (C) step in the drawing. Incidentally, this drying step is taken effect for 5 minutes at a temperature of 120 degrees. [EXPERIMENTAL EXAMPLE 2] This example is carried out in the almost same manner as in the mentioned experimental example 1 except a stirring process by means of a general screw in stead of the ball mill. [EXPERIMENTAL EXAMPLE 3] This example is carried out in the almost same manner as in the mentioned experimental example 1 except an adhesion process, in stead of the soaking process, by spraying the treatment on the cloth so that the sprayed treatment does not drip. [EXPERIMENTAL EXAMPLE 4] This example is carried out in the almost same manner as in the mentioned experimental example 1 except the pulverized collagen 2 having an average particle diameter 7 micrometers. [EXPERIMENTAL EXAMPLE 5] This example is carried out in the almost same manner as in the mentioned experimental example 1 except the pulverized collagen 2 having an average particle diameter 4 micrometers. [EXPERIMENTAL EXAMPLE 6] This example is carried out in the almost same manner as in the mentioned experimental example 1 except an aminodenatured silicon group resin emulsion 1 made by a 100 grams silicon AMZ and a 246.5 grams water and a 38.5 grams pulverized collagen 2. [EXPERIMENTAL EXAMPLE 7] This example is carried out in the almost same manner as in the mentioned experimental example 1 except an aminodenatured silicon group resin emulsion 1 made by a 100 grams silicon AMZ and a 17 grams water and a 13 grams pulverized collagen 2 added into the emulsion 1. [EXPERIMENTAL EXAMPLE 8] This example is carried out in the almost same manner as in the mentioned experimental example 1 except a drying temperature of 100 degrees. [EXPERIMENTAL EXAMPLE 9] This example is carried out in the almost same manner as in the mentioned experimental example 1 except a drying temperature of 80 degrees. [EXPERIMENTAL EXAMPLE 10] This example is carried out in the almost same manner as in the mentioned experimental example 1 except a drying temperature of 160 degrees. [EXPERIMENTAL EXAMPLE 11] In this experimental example, a 34.2 grams oiled aminodenatured silicon group resin (SM8702 silicon produced by TORAI-DAUCAUNING) is employed in stead of the aminodenatured silicon group resin a solid matter of which becomes a film and a 312.8 grams water is used. Except for these differences, this example is carried out in the almost same manner as in the mentioned experimental example 1. [EXPERIMENTAL EXAMPLE 12] In this experimental example, a 34.2 grams silicon resin (SH8710 silicon produced by TORAI-DAUCAUNING) which is not aminodenatured is employed in stead of the aminodenatured silicon group resin and a 312.8 grams water is used. Except for these differences, this example is carried out in the almost same manner as in the mentioned experimental example 1. [EXPERIMENTAL EXAMPLE 13] A 26 grams polyurethane resin (SUPERFLEX E-2000 produced by DAIICHI KOGYO) is used in stead of the silicon resin and a 312.8 grams water is used and further a 13 grams silk powder in stead of the pulverized collagen. Except for these conditions, this example is carried out in the almost same manner as in the mentioned experimental example 1. [EXPERIMENTAL EXAMPLE 14] A 28.9 grams acrylic resin (VINYBRAN 1225 produced by NISSHIN KAGAKU INDUSTRY) is used in stead of the silicon resin and a 318.1 grams water and a 13 grams pulverized wool is used in stead of the pulverized collagen. Except for these conditions, this example is carried out in the almost same manner as in the mentioned experimental example 1. [EXPERIMENTAL EXAMPLE 15] A 100 grams fluorine group resin (NK GUARD FG-270 produced by NIKKA KAGAKU) is used in stead of the silicon resin and a 13 grams sponge powder is used in stead of the collagen powder. Except for these conditions, this example is carried out in the almost same manner as in the mentioned experimental example 1. [EXPERIMENTAL EXAMPLE 16] A mixture resin having a 21 grams silicon resin (SILICON AMZ), a 21 grams polyurethane resin (SUPERFLEX E-2000) and a 305 grams water are used together in stead the emulsion as the silicon group resin and a 13 grams cellulose powder is used in stead of the pulverized collagen. Except for these conditions, this example is carried out in the almost same manner as in the mentioned experimental example 1. [EXPERIMENTAL EXAMPLE 17] A 100 grams mixture resin (EVAPHENOL N-20 produced by NIKKA KAGAKU) containing a polyester resin and polyurethane resin instead of the emulsion as the silicon group resin and a 13 grams hemp powder is used in stead of the pulverized collagen. Except for these conditions, this example is carried out in the almost same manner as in the mentioned experimental example 1. [CONTROL EXAMPLE 1] The hydrophilic organic group natural material is not used and stirring process is omitted. Except for these conditions, this control example is carried out in the almost same manner as in the mentioned experimental example 1. [CONTROL EXAMPLE 2] There is no processing to the nylon plain cloth for stocking 5. [CONTROL EXAMPLE 3] A pulverized collagen 2 having an average particle diameter 8 micrometers is used. Except for this difference, this control example is carried out in the almost same manner as in the mentioned experimental example 1. [CONTROL EXAMPLE 4] A pulverized collagen 2 having an average particle diameter 10 micrometers is used. Except for this difference, this control example is carried out in the almost same manner as in the mentioned experimental example 1. [CONTROL EXAMPLE 5] This example is carried out in the almost same manner as in the mentioned experimental example 1 except an aminodenatured silicon group resin emulsion 1 made by a 100 grams silicon AMZ and a 4 grams water in weight. [CONTROL EXAMPLE 6] This example is carried out in the almost same manner as in the mentioned experimental example 1 except a drying temperature of 75 degrees. [CONTROL EXAMPLE 7] This example is carried out in the almost same manner as in the mentioned experimental example 1 except a drying temperature of 165 degrees. [CONTROL EXAMPLE 8] This example is carried out in the almost same manner as in the mentioned experimental example 1 except a drying temperature of 30 degrees. [CONTROL EXAMPLE 9] This example is carried out in the almost same manner as in the mentioned experimental example 1 except a drying temperature of 200 degrees. The above-mentioned experimental examples 1 to 17 and control examples 1 to 9 have been made Table 1. The obtained plain cloth for stockings from these examples are evaluated and shown the result in Table 2. An item of dispersion of treatment is evaluated upon a quantity of the powder remaining on the 200-mesh filter. The adhesion property is evaluated by flicking a processed sample on a black paper and checking the fallen off powder quantity. The touch feeling is evaluated by 10-person senses base on the dry feeling involved in natural materials or the slimy feeling involved in silicon. The absorption of water property is evaluated under a condition of 40 degrees and 90% RH and the dehumidify of water is done under a condition of 23 degrees and 30% RH. The color change is measured as brightness of color by means of the colorimeter produced by MINOLTA. SYNTHETIC RESIN EMULSION HYDROPHILIC ORGANIC GROUP NATURAL MATERIAL STIR METHOD ADHESION METHOD DRYING METHOD Ex. Exam. 1 AMINODENATURED (SILICON AMZ)100g WATER 247g PULVERIZED COLLAGEN WEIGHT 13g AVERAGE PARTICLE DIAMETER 5µm BALL MILL 150RPM 10min. PAD METHOD 120°C 5 min. Ex. Exam. 2 " " SCREW " " Ex. Exam. 3 " " BALL MILL SPRAY METHOD " Ex. Exam. 4 " PULVERIZED COLLAGEN AVERAGE PARTICLE DIAMETER 7µm " PAD METHOD " Ex. Exam. 5 " PULVERIZED COLLAGEN AVERAGE PARTICLE DIAMETER 4µm " " " Ex. Exam. 6 AMINODENATURED SILICON RESIN EMULSION FINISHED IN FILM SHAPE (SILICON AMZ)100g WATER 246.5g PULVERIZED COLLAGEN WEIGHT 38.5g AVERAGE PARTICLE DIAMETER 5µm " " " Ex. Exam. 7 AMINODENATURED SILICON RESIN EMULSION FINISHED IN FILM SHAPE (SILICON AMZ)100g WATER 17g PULVERIZED COLLAGEN WEIGHT 13g AVERAGE PARTICLE DIAMETER 5µm " " " Ex. Exam. 8 AMINODENATURED SILICON RESIN EMULSION FINISHED IN FILM SHAPE (SILICON AMZ) 100g WATER 247g PULVERIZED COLLAGEN WEIGHT 13g AVERAGE PARTICLE DIAMETER 5µm " " 100°C 5 min. Ex. Exam. 9 " " " " 80°C Ex. Exam.10 " " " " 160°C Ex. Exam.11 OILED AMINODENATURED SILICON RESIN (SM8702) 34.2g WATER 312.8g " " " 120°C 5 min. Ex. Exam.12 DIS-AMINODENATURED SILICON RESIN (SH8710) 34.2g WATER 312.8g " " " " Ex. Exam.13 POLYURETHANE RESIN (SUPERFLEX E-2000) 26g WATER 321g SILK POWDER WEIGHT 13g AVERAGE PARTICLE DIAMETER 5µm " " " Ex. Exam.14 ACRYLIC RESIN (VINYBRAN 1225) 28.9g WATER 318.1g PULVERIZED WOOL WEIGHT 13g AVERAGE PARTICLE DIAMETER 5µm " " " Ex. Exam.15 FLUORINE GROUP RESIN (NK GUARD FG-270) 100g WATER 247g SPONGE POWDER WEIGHT 13g AVERAGE PARTICLE DIAMETER 5µm " " " Ex. Exam.16 SILICON RESIN (SILICON AMZ) 21g + POLYURETHANE RESIN (SUPERFLEX E-2000) 21g WATER 305g CELLULOSE POWDER WEIGHT 13g AVERAGE PARTICLE DIAMETER 5pm " " " Ex. Exam.17 POLYESTER RESIN + POLYURETHANE RESIN (EVAPHENOL N-20) 100g WATER 247g HEMP POWDER WEIGHT 13g AVERAGE PARTICLE DIAMETER 5pm " " " Con. Exam. 1 AMINODENATURATED SILICON RESIN EMULSION FINISHED IN FILM SHAPE (SILICON AMZ) 100g WATER 247g - - " " Con. Exam. 2 - - - - - Con. Exam. 3 AMINODENATURED SILICON RESIN EMULSION FINISHED IN FILM SHAPE (SILICON AMZ) 100g WATER 247g PULVERIZED COLLAGEN WEIGHT 13g AVERAGE PARTICLE DIAMETER 8µm BALL MILL 150RPM 10min. PAD METHOD 120°C 5 min. Con. Exam. 4 " PULVERIZED COLLAGEN AVERAGE PARTICLE DIAMETER 10µm " " " Con. Exam. 5 AMINODENATURED SILICON RESIN EMULSION FINISHED IN FILM SHAPE (SILICON AMZ) 30.8g WATER 4g PULVERIZED COLLAGEN WEIGHT 13g AVERAGE PARTICLE DIAMETER 5µm " " " Con. Exam. 6 AMINODENATURED SILICON RESIN EMULSION FINISHED IN FILM SHAPE (SILICON AMZ) 100g WATER 247g " " 75°C 5 min. Con. Exam. 7 " " " " 165°C Con. Exam. 8 " " " " 30°C Con. Exam. 9 " " " " 200°C Ex. Exam. = Experimental Example Con. Exam. = Control Example DISPERSION OF TREATMENT PROCESSED SAMPLE ADHESION TOUCH HYGROSCOPICITY COLOR CHANGE EX. Exam. 1 5 5 5 5 5 Ex. Exam. 2 3 4 5 5 5 Ex. Exam. 3 5 5 5 5 5 Ex. Exam. 4 5 4 5 5 5 Ex. Exam. 5 5 5 5 5 5 Ex. Exam. 6 5 5 5 5 5 Ex. Exam. 7 5 5 5 5 5 Ex. Exam. 8 5 5 5 5 5 Ex. Exam. 9 5 5 5 5 5 Ex. Exam. 10 5 5 4 5 4 Ex. Exam.11 5 5 5 5 5 EX. Exam.12 5 5 5 5 5 EX. Exam.13 5 5 5 5 5 EX. Exam. 14 5 5 5 5 5 Ex. Exam.15 5 5 5 5 5 Ex. Exam. 16 5 5 5 5 5 Ex. Exam. 17 5 5 5 5 5 Con. Exam. 1 - - 3 3 - Con. Exam. 2 - - 2 3 - Con. Exam. 3 5 2 3 5 5 Con. Exam. 4 5 2 2 5 5 Con Exam. 5 3 3 4 5 5 Con. Exam. 6 5 3 3 4 5 Con. Exam. 7 5 5 4 5 2 Con. Exam. 8 5 3 3 4 5 Con. Exam. 9 5 5 4 5 1 Ex. Exam. = Experimental Example Con. Exam. = Control Example DETERMINATION 1. WORSE 2. BAD 3. AVERAGE 4. GOOD 5. BETTER According to the present fiber/cloth treatment composition, a high adhesion property, natural dry feeling and hygroscopicity in plain cloth can be obtained without the hindrance of aeration in the cloth. The durability of cloth, because of the high adhesion and the hygroscopicity of cloth is therefore improved.

Claims: A composition comprising 90-99 wt.% of a synthetic resin emulsion and 10-1 wt.% of pulverised hydrophilic organic group-containing natural material having an average particle diameter of no more than 7 µ m, with a standard deviation of 3µm, wherein the synthetic resin emulsion is selected from a silicon resin emulsion, a polyurethane resin emulsion, a polyacrylic resin emulsion, a fluorine resin emulsion and mixtures thereof, and contains water in an amount of at least 8 times the weight of the natural material. A composition according to claim 1, wherein the synthetic resin is a silicone resin. A composition according to claim 2, wherein the silicone resin is aminodenatured. A composition according to claim 3, wherein the aminodenatured silicone resin is film-forming. A composition according to claim 1, wherein the synthetic resin is a polyurethane resin. A composition according to any preceding claim, wherein the natural material is selected from collagen, elastin, silk powder, sponge powder, wool, cellulose, cotton, hemp, pulp and seaweed. A composition according to claim 6, wherein the natural material is a collagen. A composition according to claim 6, wherein the natural material is silk powder. A composition according to any preceding claim, wherein the natural material has an average particle diameter of less than 4 µm. A finished product selected from fibres, cloths, cloth-like products made of synthetic or artificial leather, and ground cloth of said cloth-like leather products, the product being obtainable by finishing with a composition as defined in any preceding claim. A method of treating a product selected from fibres, cloths, cloth-like products made of synthetic or artificial leather, and ground cloth of said cloth-like leather products, the method comprising the steps of: stirring an emulsion and a natural material as defined in any of claims 1 to 9 to form a treatment composition; soaking the product in the treatment composition; and drying the soaked product. A method according to claim 11, wherein the stirring is carried out by means of a ball mill. A method according to claim 11 or claim 12, wherein the drying is conducted at 80 - 160°C.

Inventors: FUKATSU FUMIOKI, OHYAMA SHIGERU, SANO MASAHIRO, FUKATSU, FUMIOKI, OHYAMA, SHIGERU, SANO, MASAHIRO
Applicants: IDEMITSU PETROCHEMICAL CO, IDEMITSU PETROCHEMICAL CO., LTD.
Application year: 1993
Main classification: D06N3
IPC codes: D06M15, D06N3, D06M23