WO2016052906A1 - 방오성을 가지는 스웨이드형 인공피혁 및 이의 제조방법 - Google Patents
방오성을 가지는 스웨이드형 인공피혁 및 이의 제조방법 Download PDFInfo
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- WO2016052906A1 WO2016052906A1 PCT/KR2015/009995 KR2015009995W WO2016052906A1 WO 2016052906 A1 WO2016052906 A1 WO 2016052906A1 KR 2015009995 W KR2015009995 W KR 2015009995W WO 2016052906 A1 WO2016052906 A1 WO 2016052906A1
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- fluorine
- artificial leather
- modified polyurethane
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
- D06N3/14—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes
- D06N3/146—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes characterised by the macromolecular diols used
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/0002—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate
- D06N3/0004—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate using ultra-fine two-component fibres, e.g. island/sea, or ultra-fine one component fibres (< 1 denier)
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/0002—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate
- D06N3/0011—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate using non-woven fabrics
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/0002—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate
- D06N3/004—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate using flocked webs or pile fabrics upon which a resin is applied; Teasing, raising web before resin application
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/007—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by mechanical or physical treatments
- D06N3/0075—Napping, teasing, raising or abrading of the resin coating
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
- D06N3/14—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
- D06N3/14—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes
- D06N3/147—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes characterised by the isocyanates used
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N2209/00—Properties of the materials
- D06N2209/12—Permeability or impermeability properties
- D06N2209/126—Permeability to liquids, absorption
- D06N2209/128—Non-permeable
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N2209/00—Properties of the materials
- D06N2209/14—Properties of the materials having chemical properties
- D06N2209/142—Hydrophobic
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N2209/00—Properties of the materials
- D06N2209/14—Properties of the materials having chemical properties
- D06N2209/146—Soilproof, soil repellent
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N2209/00—Properties of the materials
- D06N2209/14—Properties of the materials having chemical properties
- D06N2209/147—Stainproof, stain repellent
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N2211/00—Specially adapted uses
- D06N2211/12—Decorative or sun protection articles
- D06N2211/28—Artificial leather
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S428/00—Stock material or miscellaneous articles
- Y10S428/904—Artificial leather
Definitions
- the present invention relates to a suede-type artificial leather having antifouling properties, and more particularly, to an artificial leather impregnated with a modified polyurethane having an antifouling function, and to a simple manufacturing method without additional addition of an antifouling function. .
- Artificial leather is made of polymer elastomer impregnated with a nonwoven fabric formed by interweaving microfibers three-dimensionally, and has a soft texture and unique appearance similar to natural leather, such as shoes, clothing, gloves, sundries, furniture, and automobile interior materials. It is widely used in various fields.
- Such artificial leather has different characteristics to be provided according to its use.
- the characteristics required for artificial leather for clothes include high durability, high sensitivity, excellent dyeability and high fastness that can be dyed in various colors and concentrations.
- fluorine- or silicon-based surfactants are mixed with polyurethane, a polymer elastomer, and impregnated into a nonwoven fabric to incubate fluorine or silicon chains on the surface of artificial leather to suppress contamination from the outside. There is a way.
- fluorine-based or silicon-based surfactants are generally inert additives and do not form chemical bonds when mixed with polyurethane, resulting in free behavior in the urethane molecular structure, which leads to the transition of artificial leather to the surface of artificial leather. There is a problem causing change over time.
- a modified polyurethane in which fluorine is bonded without adding a fluorine-based compound and a method of manufacturing a leather-like sheet-like article using the modified polyurethane are described in Korean Patent No. 0969839.
- 3-12 fluorine-containing side chains of the molecular weight 200-1,000 are couple
- the use of the fluorine-containing side chain-modified urethane compound containing 6 to 36 sugar urethane bonds and the urethane compound has been described to be excellent in water repellency and water resistance in the cut section of the leather-like sheet-like product.
- the modified polyurethane according to the above patent is used as an additive added together with polyurethane, which is an elastic body, as a treatment liquid of a leather-like sheet form, and shows an effect as a water repellent.
- an object of the present invention is to provide an artificial leather impregnated with a new modified polyurethane which will have an antifouling function without the addition of an antifouling function.
- the polymer elastic body is a fluorine-containing modified polyurethane
- a fluorine-containing modified polyurethane is a polymerization product by reaction of the urethane prepolymer in which the isocyanate group is located in the terminal obtained by making diol and diisocyanate react, and the fluorinated carbon compound provided with the hydroxy functional group at both terminals, and has a weight average molecular weight (Mw). It provides a suede-type artificial leather having antifouling properties characterized in that 50) ⁇ 800,000.
- the present invention is a method of manufacturing artificial leather in which the nonwoven fabric formed by interweaving microfibers three-dimensionally immersed in the impregnation solution containing a polymer elastomer, the polymer elastic body is impregnated and brushed, the polymer elastic body is fluorine-containing Modified polyurethane, wherein the fluorine-containing modified polyurethane reacts with diol and diisocyanate to prepare a urethane prepolymer having a weight average molecular weight (Mw) of 400,000 ⁇ 700,000, and the prepared prepolymer and hydroxy functional groups at both ends It provides a method for producing suede artificial leather having antifouling properties characterized in that the weight average molecular weight (Mw) is made of a polymer of 500,000 ⁇ 800,000 by reacting the fluorinated carbon compound.
- Mw weight average molecular weight
- Artificial leather impregnated with a fluorine-containing modified polyurethane elastic body imparted with antifouling function according to the present invention exhibits excellent water repellency in addition to antifouling properties, and artificial leather prepared by adding a fluorine-based surfactant separately changes surface surface upon implementation of the surfactant. Compared to the large occurrence of the artificial leather of the present invention can make the surface aging change small.
- the manufacturing method can be simplified.
- 3 is a rating criteria of the water repellency evaluation.
- the present invention relates to an artificial leather, wherein the polymer elastic body is a fluorine-containing modified polyurethane in an artificial leather in which a polymer elastic body is impregnated and raised to a nonwoven fabric formed by interweaving microfibers three-dimensionally.
- the fluorine-containing modified polyurethane is a urethane prepolymer having a weight average molecular weight (Mw) of 400,000 to 700,000 having an isocyanate group at the terminal obtained by addition reaction of a diol and a diisocyanate, and a fluorinated carbon to which hydroxy functional groups are provided at both terminals.
- Mw weight average molecular weight
- Diols such as 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, ethylene glycol, diethylene glycol, polyethylene glycol, polypropylene glycol and polytetramethylene glycol may be used alone or in combination. Can be used.
- the diisocyanate is 1,4-tetramethylene diisocyanate, 1,6 hexamethylene diisocyanate, 1,12-dodecamethylene diisocyanate, cyclohexane-1,3- to 1,4-diisocyanate, 1-isocyanate 3-isocyanatemethyl-3,5,5-trimethylcyclohexane (isophorone diisocyanate), bis- (4-isocyanate cyclohexyl) methane (hydrogenated MDI), 2- to 4-isocyanate cyclohexyl-2-isocyanate cyclo Hexylmethane, 1,3- to 1,4-tetramethylxylene diisocyanate, 2,4- to 2,6-diisocyanate toluene, 2,2-2,4- to 4,4'-diphenylmethane diisocyanate , 1,5-naphthalene diisocyanate, xylene diisocyanate, diphenyl-4,
- the urethane prepolymer obtained can have an isocyanate group terminal in a side chain.
- the molar ratio of diol and diisocyanate is preferably in the range of 1: 1.2 to 1: 1.4, since it is possible to produce a fluorine-containing modified polyurethane having a weight average molecular weight range of the present invention.
- the molar ratio When the molar ratio is less than 1: 1.2, side reactions occur due to moisture in the air, active hydrogen, or the like, or isocyanates react to form a trimer to form a trimer, thereby increasing the inert NCO, thereby decreasing polymerization efficiency.
- the molar ratio is greater than 1: 1.4, the shortage of the OH group becomes severe due to the excess NCO group, making it difficult to increase the degree of polymerization, which is not preferable.
- a urethane prepolymer may be prepared first.
- the weight average molecular weight (Mw) of the urethane prepolymer is less than 400,000, the molecular weight of the finally obtained fluorine-containing modified polyurethane is lowered, thereby lowering mechanical properties such as tear strength, and chemical properties such as thermal stability and hydrolysis resistance. If it exceeds 700,000, gelation may occur in the production of the fluorine-containing modified polyurethane, and when the mixture is prepared with an elastomeric impregnating solution, the viscosity of the fluorine-containing modified polyurethane may be high, resulting in deterioration of workability. The resulting fluorine-containing modified polyurethane can be hardened, and the quality of sensibility can be degraded in artificial leather, which is undesirable.
- the fluorinated carbon compound provided with hydroxy functional groups at both ends thereof is represented by the following Chemical Formula 1, wherein 8 to 14 fluorine groups are bonded to one side chain, and the fluorine content is 50 to 70 mol% at one structural end. And ether diols having hydroxy functional groups at both ends.
- the fluorine-containing modified polyurethane of the present invention can suppress the deposition of the external pollution source and can be easily removed the contamination rate of the coating surface.
- Solvay's FLUOROLINK ® is a commercialized product of fluorinated carbon compounds with hydroxy functional groups at both ends.
- the urethane prepolymer is a fluorinated carbon compound having a hydroxy functional group at both ends by the molar excess of isocyanate (mol) of the urethane prepolymer isocyanate is bonded to both ends
- the addition polymerization can be carried out while adding dropwise to until it reaches the appropriate molecular weight.
- the fluorine-containing modified polyurethane of the present invention is polymerized by the above method, characterized in that the weight average molecular weight (Mw) is 500,000 ⁇ 800,000, if the weight average molecular weight (Mw) is less than 500,000 mechanical strength such as tear strength in artificial leather It may cause the deterioration of chemical properties such as strength, thermal stability and hydrolysis resistance. If it exceeds 800,000, the viscosity of the fluorine-containing modified polyurethane is high when the elastomeric impregnating solution is formulated. The resulting fluorine-containing modified polyurethane may be hardened, and thus the quality of the sensitization in artificial leather may be degraded, which is not preferable.
- the fluorine-containing modified polyurethane of the present invention has a fluorine content of 5 to 20 mol%, but if it is 5 mol% or less, the expression of antifouling performance is insufficient, and if the content exceeds 20 mol%, the water repellent performance is too strongly expressed to prepare artificial leather. Substituted solidification of the fluorine-containing modified polyurethane may not be achieved in the process, which is not preferable.
- R and R ' are each independently an alkyl group.
- artificial leather is immersed in the impregnating solution containing a polymer elastic body such as polyurethane to immerse the non-woven fabric formed by three-dimensional intertwined fibers, impregnated and solidified the polymer elasticity, imparts an elastic body to the non-woven fabric, then grinding and brushed It can be prepared by dyeing.
- a polymer elastic body such as polyurethane
- the fluorine-containing modified polyurethane of the present invention can be used as the polymer elastic body of the impregnation liquid, impregnated by diluting the fluorine-containing modified polyurethane in dimethylformamide of 100 to 200% by weight of the fluorine-containing modified polyurethane.
- NCO-terminated polyurethane prepolymer having a weight average molecular weight (Mw) of 700,000 was prepared by diluting and dissolving in dimethylformamide so that the total solid content was 40% by weight.
- the prepared prepolymer was added with 0.2 mol of fluorinated carbon compound (trade name FLUOROLINK D10-H, Solvay Co., Mw: 1,400) having a hydroxyl group at both ends, and after addition polymerization, dimethylform was added so that the total solid of the polymerized polymer was 30% by weight.
- fluorinated carbon compound trade name FLUOROLINK D10-H, Solvay Co., Mw: 1,400
- NCO-terminated polyurethane prepolymer having a weight average molecular weight (Mw) of 600,000 was prepared by diluting and dissolving in dimethylformamide so that the total solid content was 40% by weight.
- the prepared prepolymer was added with 0.3 mol of fluorinated carbon compound (trade name FLUOROLINK D10-H, Solvay, Mw: 1,400) having a hydroxyl group at both ends, and after addition polymerization, dimethylform was added so that the total solid of the polymerized polymer was 30% by weight.
- fluorinated carbon compound trade name FLUOROLINK D10-H, Solvay, Mw: 1,400
- NCO-terminated polyurethane prepolymer having a weight average molecular weight (Mw) of 400,000 was prepared by diluting and dissolving in dimethylformamide so that the total solid content was 40% by weight.
- NCO-terminated polyurethane prepolymer having a weight average molecular weight (Mw) of 350,000 was prepared by diluting and dissolving in dimethylformamide so that the total solid content was 40% by weight.
- the prepolymer was diluted and dissolved in dimethylformamide so that the total solid content of the polymerized polymer was 30% by weight (Mw).
- a fluorine-containing modified polyurethane compound having 450,000) was prepared.
- An impregnation solution was prepared by diluting the fluorine-containing modified polyurethane compound of Preparation Example 1 in 150% of dimethylformamide relative to the weight of the compound.
- a polyester fiber (0.3 denier, 51 mm long fiber) was immersed in the impregnation solution, and the solid nonwoven fabric was immersed in the impregnation solution, and coagulated in an aqueous solution in which 20 wt% of dimethylformamide was diluted to impregnate the fluorine-containing modified polyurethane compound elastomer.
- An elastic-impregnated nonwoven fabric was prepared in which a fine porous layer was formed in the fiber structure.
- Example 1 suede artificial leather was manufactured in the same manner as in Example 1, except that the impregnation solution was prepared using the fluorine-containing modified polyurethane compound of Preparation Example 2.
- Example 1 suede artificial leather was manufactured in the same manner as in Example 1 except that the impregnation solution was prepared using the fluorine-containing modified polyurethane compound of Preparation Example 3.
- Example 1 suede artificial leather was manufactured in the same manner as in Example 1 except that the impregnation solution was prepared using the fluorine-containing modified polyurethane compound of Preparation Example 4.
- Example 1 suede artificial leather was manufactured in the same manner as in Example 1 except that the impregnation solution was prepared using the fluorine-containing modified polyurethane compound of Preparation Example 5.
- Example 1 the impregnation solution was prepared by diluting the reaction-terminated polyurethane compound of Preparation Example 6 to a mixture of 150% dimethylformamide and 0.5% fluorine-based surfactant (trade name FC-4430, 3M company) by weight. Except that, suede-type artificial leather was manufactured in the same manner as in Example 1.
- the weight average molecular weight (Mw) of the polymers prepared in Examples and Comparative Examples is a mobile phase using tetrahydrofuran (flow rate 1 mL / min) using gel permeation chromatography (GPC) (RI-8000, Tosoh).
- GPC gel permeation chromatography
- the TSKgel super HM-L, TSKgel super HM-M, and TSKgel super HM-N were passed through a column connected in series, and the temperature of the column oven was measured at 40 ° C.
- Table 1 shows the polymerization raw material composition ratio and the weight average molecular weight of the polymerized polymer for the above Preparation Example.
- the artificial leather prepared in Examples and Comparative Examples was evaluated according to the following pollution resistance evaluation method, and the results are shown in Table 2 below.
- the artificial leather measurement sample is cut into a size of 5 x 15 cm, placed in a friction fastness tester (model DL-2007), and a contaminated cloth (Test fabric, namely IEC carbon black / mineral oil, EMPA) is placed on the surface of the contaminated sample.
- a friction fastness tester model DL-2007
- EMPA contaminated cloth
- 10 reciprocating frictions are performed and the contamination level is compared by visual comparison of the contaminated sample.
- the artificial leather measurement sample is fixed as shown in FIG. 2 (diameter 10 cm), and then tilted at an angle of 45 ° to be mounted. Thereafter, 100 ml of water is sprayed into the spray funnel located at the top, and after completion of spraying, the degree of distribution of water droplets formed on the surface of the sample is observed, and grades are given based on the criteria of FIG. 3.
- Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Pollution Degree 3.5 3.5 3.5 2.0 2.5 3.5 Water repellency grade 3.5 4.0 4.5 2.5 3.0 2.5
- the artificial leather of the Example which impregnated the fluorine-containing modified polyurethane of this invention as an elastic body in the state which does not add a fluorine-type surfactant separately from Table 2 is equivalent to the artificial leather (Comparative Example 3) which added the fluorine-type surfactant separately. It can be seen that it exhibits antifouling performance and at the same time has improved water repellency.
- Artificial leather of the present invention is an artificial leather impregnated with a fluorine-containing modified polyurethane imparted with antifouling function, it is not necessary to use a fluorine-based surfactant for the antifouling property in the production of artificial leather to improve productivity, fluorine-based surfactant It improves the appearance quality of artificial leather by showing excellent antifouling performance that suppresses the change of surface of artificial leather over time.
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- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Dispersion Chemistry (AREA)
- Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
Description
구분 | 제조예 1 | 제조예 2 | 제조예 3 | 제조예 4 | 제조예 5 | 제조예 6 |
디올 | 1 mol | 1 mol | 1 mol | 1 mol | 1 mol | 1 mol |
디이소시아네이트 | 1.2 mol | 1.3 mol | 1.4 mol | 1 mol | 1.7 mol | 1 mol |
프리폴리머 | 700,000 | 600,000 | 400,000 | 700,000 | 350,000 | 700,000 |
FLUOROLINK D10-H | 0.2 mol | 0.3 mol | 0.4 mol | - | 0.7 mol | - |
불소 함유 변성 폴리우레탄 | 800,000 | 700,000 | 500,000 | - | 450,000 | - |
계면활성제(FC-4430) | - | - | - | - | - | 0.5% |
계면활성제의 수치는 탄성체 함침액에서의 함량임. |
실시예 1 | 실시예 2 | 실시예 3 | 비교예 1 | 비교예 2 | 비교예 3 | |
오염등급 | 3.5 | 3.5 | 3.5 | 2.0 | 2.5 | 3.5 |
발수등급 | 3.5 | 4.0 | 4.5 | 2.5 | 3.0 | 2.5 |
Claims (6)
- 극세섬유가 3차원적으로 교락되어 형성된 부직포에 고분자 탄성체가 함침되고 기모가 형성되어 이루어진 인공피혁에 있어서,상기 고분자 탄성체가 불소 함유 변성 폴리우레탄이되,상기 불소 함유 변성 폴리우레탄은, 디올과 디이소시아네이트를 반응시켜 얻어진 말단에 이소시아네이트기가 위치한 우레탄 예비중합체와, 양 말단에 히드록시 관능기가 부여된 불소화 탄소화합물의 반응에 의한 중합 생성물로서, 중량평균분자량(Mw)이 500,000~800,000인 것을 특징으로 하는 방오성을 가지는 스웨이드형 인공피혁.
- 제 1항에 있어서,상기 우레탄 예비중합체는 중량평균분자량(Mw)이 400,000~700,000인 것을 특징으로 하는 방오성을 가지는 스웨이드형 인공피혁.
- 제 1항에 있어서,상기 양 말단에 히드록시 관능기가 부여된 불소화 탄소화합물은 1개의 측쇄 사슬에 불소기 8~14개가 결합하고 있고, 1개의 구조단에 불소 함량이 50~70 mol%이며, 양 말단에 히드록시 관능기가 부여된 에테르 디올인 것을 특징으로 하는 방오성을 가지는 스웨이드형 인공피혁.
- 극세섬유가 3차원적으로 교락되어 형성된 부직포를 고분자 탄성체를 포함한 함침액에 침지하여 상기 고분자 탄성체를 함침시키고 기모 가공하여 이루어지는 인공피혁의 제조방법에 있어서,상기 고분자 탄성체가 불소 함유 변성 폴리우레탄이되,상기 불소 함유 변성 폴리우레탄은 디올과 디이소시아네이트를 반응시켜 중량평균분자량(Mw)이 400,000~700,000인 우레탄 예비중합체를 제조하고, 상기 제조된 예비중합체와 양 말단에 히드록시 관능기가 부여된 불소화 탄소화합물을 반응시켜 중량평균분자량(Mw)이 500,000~800,000의 중합물로 제조되는 것을 특징으로 하는 방오성을 가지는 스웨이드형 인공피혁의 제조방법.
- 제 4항에 있어서,상기 우레탄 예비중합체를 제조할 때에 상기 디올과 디이소시아네이트의 몰비를 1:1.2 ~ 1:1.4의 범위로 반응시키는 것을 특징으로 하는 방오성을 가지는 스웨이드형 인공피혁의 제조방법.
- 제 4항에 있어서,상기 양 말단에 히드록시 관능기가 부여된 불소화 탄소화합물은 1개의 측쇄 사슬에 불소기 8~14개가 결합하고 있고, 1개의 구조단에 불소 함량이 50~70 mol%이며, 양 말단에 히드록시 관능기가 부여된 에테르 디올인 것을 특징으로 하는 방오성을 가지는 스웨이드형 인공피혁의 제조방법.
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JP2017516349A JP6530810B2 (ja) | 2014-09-29 | 2015-09-23 | 防汚性を有するスエードタイプ人工皮革及びその製造方法 |
EP15846907.2A EP3202976B1 (en) | 2014-09-29 | 2015-09-23 | Suede type artificial leather with soiling protection property and preparation therefor |
CN201580052246.6A CN107075792A (zh) | 2014-09-29 | 2015-09-23 | 具有防污性能的绒面型人造革及其制备方法 |
US15/512,235 US20170284018A1 (en) | 2014-09-29 | 2015-09-23 | Suede type artificial leather with antifouling property and preparation method therefor |
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KR1020140130226A KR101963127B1 (ko) | 2014-09-29 | 2014-09-29 | 방오성을 가지는 스웨이드형 인공피혁의 제조방법 |
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EP (1) | EP3202976B1 (ko) |
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WO2018215386A1 (en) * | 2017-05-24 | 2018-11-29 | Solvay Specialty Polymers Italy S.P.A. | Monolithic breathable membrane |
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- 2015-09-23 WO PCT/KR2015/009995 patent/WO2016052906A1/ko active Application Filing
- 2015-09-23 CN CN201580052246.6A patent/CN107075792A/zh active Pending
- 2015-09-23 EP EP15846907.2A patent/EP3202976B1/en active Active
- 2015-09-23 JP JP2017516349A patent/JP6530810B2/ja active Active
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KR101963127B1 (ko) | 2019-03-28 |
JP2017534773A (ja) | 2017-11-24 |
US20170284018A1 (en) | 2017-10-05 |
KR20160037538A (ko) | 2016-04-06 |
CN107075792A (zh) | 2017-08-18 |
EP3202976A1 (en) | 2017-08-09 |
EP3202976B1 (en) | 2019-06-12 |
EP3202976A4 (en) | 2018-05-30 |
JP6530810B2 (ja) | 2019-06-12 |
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