Antibacterial color-fixing polyurethane, preparation method thereof and application of antibacterial color-fixing polyurethane in insole leather

Abstract

The invention discloses antibacterial color-fixing polyurethane, which is prepared from the following raw materials in parts by weight: 100 parts of polyurethane resin, 10 to 20 parts of oregano fiber, 1 to 3 parts of plasticizer, 3 to 8 parts of color paste and 60 to 80 parts of organic solvent 2, wherein the polyurethane resin is prepared from the following raw materials in parts by weight: 3.7 to 8.1 parts of diisocyanate, 14 to 16 parts of polyhydric alcohol, 2 to 6 parts of dihydroxyl organic silicon oligomer, 0.5 to 0.7 part of N-methyldiethanolamine, 0.5 to 0.55 part of capsaicin, 0.03 to 0.06 part of antibacterial agent, 0.55 to 1 part of chain extender, 0.03 to 0.06 part of terminating agent, 0.5 to 0.6 part of organic acid and 61 to 66 parts of organic solvent 1. The invention also discloses a preparation method and application of the antibacterial color-fixing polyurethane. The invention also discloses polyurethane insole leather and a preparation method thereof. The antibacterial color fixing polyurethane disclosed by the invention has good antibacterial property and color fixing property.

Description

Technical Field

[0001] The invention relates to the field of synthetic leather, in particular to an antibacterial color-fixing polyurethane and a preparation method thereof, and application in insole leather. Background Art

[0002] Polyurethane synthetic leather is used in all aspects of people's lives, such as clothes, shoes, footballs, golf clubs, car handles and sofas. The current polyurethane synthetic leather is resistant to viruses, bacteria and fungi because phenol is used as an antibacterial agent and antioxidant in polyurethane synthetic leather, but they are seriously toxic to human health. However, as people pay more and more attention to their own health, it is necessary to provide polyurethane synthetic leather that is non-toxic to human health. In addition, the color fixation performance of existing polyurethane synthetic leather is relatively poor, especially for blue, and it is necessary to provide polyurethane synthetic leather with better color fixation. Summary of the invention

[0003] Based on the technical problems existing in the background technology, the present invention proposes an antibacterial color-fixing polyurethane and a preparation method thereof, and application in insole leather. The antibacterial color-fixing polyurethane of the present invention has good antibacterial and color-fixing properties.

[0004] The invention provides an antibacterial color-fixing polyurethane, the raw materials of which include, by weight: 100 parts of polyurethane resin, 10-20 parts of oregano fiber, 1-3 parts of plasticizer, 3-8 parts of color paste, and 260-80 parts of organic solvent; The raw materials of the polyurethane resin include, by weight: 3.7-8.1 parts of diisocyanate, 14-16 parts of polyol, 2-6 parts of dihydroxy silicone oligomer, 0.5-0.7 parts of N-methyldiethanolamine, 0.5-0.55 parts of caprine, 0.03-0.06 parts of antibacterial agent, 0.55-1 parts of chain extender, 0.03-0.06 parts of terminator, 0.5-0.6 parts of organic acid and 161-66 parts of organic solvent.

[0005] Preferably, the weight average molecular weight of the dihydroxy silicone oligomer is 2000-3000.

[0006] The dihydroxy silicone oligomer may be one or more of 8832F1, 8814, 88158 and 822F2 produced by Silok.

[0007] Preferably, the weight average molecular weight of the polyol is 2000-4000.

[0008] The polyol may be one or more of XCPP-20001, XCPP-20003, XCPP-20008, XCPP-30007, XCPP-30013, XCPP-30001, and XCPP-40013 produced by Asahikawa Chemical (Suzhou) Co., Ltd.

[0009] Preferably, the antimicrobial agent is carvacrol.

[0010] Preferably, the chain extender is one or more of ethylene glycol, 1,4-butanediol, monoethanolamine, and methylpropylene glycol.

[0011] Preferably, the diisocyanate is one or more of 4,4-diphenylmethane diisocyanate and toluene diisocyanate.

[0012] Preferably, the terminator is one or more of ethylene glycol, methanol, 1,4-butanediol, and diethylene glycol.

[0013] Preferably, the organic acid is acetic acid.

[0014] Preferably, organic solvent 1 and organic solvent 2 are one or both of N,N-dimethylformamide and N,N-dimethylacetamide.

[0015] Preferably, the color paste is an anionic color paste.

[0016] Preferably, the oregano fibers have a particle size of 200-500 μm.

[0017] Preferably, in the preparation process of oregano fiber, oregano grass is soaked in a sodium hydroxide aqueous solution, washed with water, dried, sheared, and ball-milled to obtain oregano fiber.

[0018] Preferably, during the preparation of the oregano fiber, the oregano fiber is soaked in an aqueous sodium hydroxide solution with a mass fraction of 8-15 wt % for 1-1.5 h.

[0019] The present invention also provides a method for preparing the antibacterial color-fixing polyurethane, comprising the following steps: S1. In an inert gas atmosphere, a dihydroxy silicone oligomer, a polyol, an antibacterial agent, N-methyldiethanolamine, and an organic solvent 1 are mixed evenly, and then a portion of diisocyanate is added to react; S2. In an inert gas atmosphere, add organic solvent 1, chain extender, caprine and mix well, then add the remaining diisocyanate to react. When the viscosity reaches 25-35cps / 25°C, add terminator, continue the reaction, add organic acid and mix well to obtain polyurethane resin. S3, mixing the polyurethane resin, oregano fiber, plasticizer, color paste and organic solvent 2 to obtain an antibacterial color-fixing polyurethane.

[0020] Preferably, in S1, the reaction temperature is 60-80°C, and the reaction is carried out until the viscosity reaches 10-13 cps / 55°C.

[0021] Preferably, in S1, the weight ratio of diisocyanate to organic solvent 1 is 1.3-2.3:17-21.

[0022] Preferably, in S2, the reaction temperature is 60-80°C.

[0023] Preferably, in S2, a terminator is added and the reaction is continued at 60-80°C for 20-30 minutes.

[0024] Preferably, in S2, an organic acid is added and the reaction is continued at 60-80°C for 20-30 minutes.

[0025] Preferably, in S2, the weight ratio of diisocyanate to organic solvent 1 is 2.4-6:42-49.

[0026] Preferably, the weight ratio of the diisocyanates in S1 and S2 is 1.3-2.3:2.4-6.

[0027] The invention also proposes the application of the antibacterial color-fixing polyurethane in shoe insole leather.

[0028] The present invention also provides a polyurethane insole leather, comprising: an insole base, and antibacterial color-fixing polyurethane filled and distributed inside and on the surface of the insole base; wherein the antibacterial color-fixing polyurethane is the above-mentioned antibacterial color-fixing polyurethane.

[0029] The present invention also provides a method for preparing the polyurethane insole leather, comprising the following steps: A. Squeeze the antibacterial color-fixing polyurethane into the insole base, dry, wash and bake; B. Coating the antibacterial color-fixing polyurethane on the surface of the insole base, drying, washing, and drying to obtain the polyurethane insole leather.

[0030] Preferably, in A, the drying temperature is 100-110° C. and the drying time is 15-45 s.

[0031] Preferably, in A, the number of water washings is 3-8 times.

[0032] Preferably, in B, the coating thickness is 1-2 mm.

[0033] Preferably, in B, washing with water is performed 20-30 times.

[0034] Preferably, in B, the drying temperature is 100-110° C. and the drying time is 20-30 min.

[0035] The invention introduces carvacrol into the polyurethane molecular chain and combines it with oregano fiber to greatly improve the antibacterial property and has no toxic side effects on the human body. In addition, the addition of oregano fiber can also improve the wear resistance, toughness and strength of the polyurethane.

[0036] The invention uses N-methyldiethanolamine and caprine, introduces guanidine groups and tertiary amine groups into polyurethane molecular chains, and after reacting with organic acid, polyurethane is provided with strong cationic groups, anionic color paste can be fixed, and thus color fixing performance is greatly improved; in addition, caprine has carbon-carbon double bonds, and copolymerization can occur during the process of preparing insole leather to improve the cross-linking network, thereby further improving color fixing performance and mechanical properties; and dihydroxy organic silicon oligomer is introduced into the polyurethane molecular chain, thereby further improving the wear resistance of polyurethane and the wear-resistant color fixing performance; in addition, polyurethane resin is prepared in two steps, thereby improving the crystallinity of polyurethane and further improving the wear-resistant color fixing performance; and the quaternary ammonium salt group formed by the tertiary amine group also has antibacterial performance, thereby further improving the antibacterial property of polyurethane. BRIEF DESCRIPTION OF THE DRAWINGS

[0037] Figure 1 The following are photos of the color fading test results of Example 1, Comparative Example 3, and Comparative Example 5. DETAILED DESCRIPTION

[0038] The technical solution of the present invention is described in detail below through specific embodiments. Example 1

[0039] An antibacterial color-fixing polyurethane, the raw materials of which include, by weight: 100 parts of polyurethane resin, 10 parts of oregano fiber, 1 part of plasticizer, 3 parts of anionic blue color paste, and 60 parts of DMF; The raw materials of the polyurethane resin include, by weight: 6.5 parts of 4,4-diphenylmethane diisocyanate, 14 parts of polyol XCPP-20001, 2 parts of dihydroxy silicone oligomer 8832F1, 0.5 parts of N-methyldiethanolamine, 0.55 parts of caprine, 0.03 parts of carvacrol, 0.55 parts of chain extender ethylene glycol, 0.03 parts of terminator ethylene glycol, 0.5 parts of acetic acid and 66 parts of DMF; In the preparation process of oregano fiber, oregano grass is soaked in a sodium hydroxide aqueous solution with a mass fraction of 10wt% for 1 hour, washed with clean water until it does not contain sodium hydroxide, then air-dried to completely dry, and then sheared and ball-milled to obtain oregano fiber with a particle size of 200μm.

[0040] The method for preparing the antibacterial color-fixing polyurethane comprises the following steps: S1. Under nitrogen protection, dihydroxy silicone oligomer 8832F1, polyol XCPP-20001, carvacrol, N-methyldiethanolamine and DMF were mixed, and then part of 4,4-diphenylmethane diisocyanate was added, and the temperature was raised to 60°C for reaction until the viscosity reached 10cps / 55°C, wherein the weight ratio of 4,4-diphenylmethane diisocyanate to DMF was 2.1:17; S2, under nitrogen protection, add DMF, chain extender ethylene glycol, caprine and mix well, then add the remaining 4,4-diphenylmethane diisocyanate, react at 60°C, when the viscosity reaches 25cps / 25°C, add terminator ethylene glycol, continue to react at 60°C for 30min, add acetic acid, continue to stir at 60°C for 30min, and obtain a polyurethane resin, wherein the weight ratio of 4,4-diphenylmethane diisocyanate to DMF in S2 is 4.4:49; the weight ratio of 4,4-diphenylmethane diisocyanate in S1 and S2 is 2.1:4.4; S3, the polyurethane resin, oregano fiber, plasticizer, anionic blue color paste and DMF are mixed to obtain antibacterial color-fixing polyurethane.

[0041] A method for preparing polyurethane insole leather comprises the following steps: A. Extrude the above antibacterial color-fixing polyurethane into the interior of the insole base, dry it, wash it 3 times with regular tap water, and dry it at 110°C for 15 seconds; B. Then, the surface of the insole base is coated with antibacterial color-fixing polyurethane with a coating thickness of 1 mm, dried, washed with conventional tap water for 20 times, and dried at 110° C. for 20 min to obtain a polyurethane insole leather. Example 2

[0042] An antibacterial color-fixing polyurethane, the raw materials of which include, by weight: 100 parts of polyurethane resin, 15 parts of oregano fiber, 2 parts of plasticizer, 5 parts of anionic blue color paste, and 70 parts of DMF; The raw materials of the polyurethane resin include, by weight: 3.84 parts of toluene diisocyanate, 15 parts of polyol XCPP-30007, 4 parts of dihydroxy silicone oligomer 8814, 0.6 parts of N-methyldiethanolamine, 0.55 parts of caprine, 0.04 parts of carvacrol, 0.75 parts of chain extender 1,4-butanediol, 0.04 parts of terminator 1,4-butanediol, 0.55 parts of acetic acid and 61 parts of DMF; In the preparation process of oregano fiber, oregano grass is soaked in a sodium hydroxide aqueous solution with a mass fraction of 10wt% for 1 hour, washed with clean water until it does not contain sodium hydroxide, then air-dried to completely dry, and then sheared and ball-milled to obtain oregano fiber with a particle size of 300μm.

[0043] The method for preparing the antibacterial color-fixing polyurethane comprises the following steps: S1. Under nitrogen protection, dihydroxy silicone oligomer 8814, polyol XCPP-30007, carvacrol, N-methyldiethanolamine and DMF were mixed, and then part of toluene diisocyanate was added, and the temperature was raised to 80°C for reaction until the viscosity reached 11 cps / 55°C, wherein the weight ratio of toluene diisocyanate to DMF was 1.33:19; S2, under nitrogen protection, add DMF, chain extender 1,4-butanediol, caprine and mix well, then add the remaining toluene diisocyanate, react at 80°C, when the viscosity reaches 30cps / 25°C, add terminator 1,4-butanediol, continue to react at 80°C for 20min, add acetic acid, continue to react at 80°C for 20min, obtain polyurethane resin, wherein in S2, the weight ratio of toluene diisocyanate to DMF is 2.51:42; the weight ratio of toluene diisocyanate in S1 and S2 is 1.33:2.51; S3, the polyurethane resin, oregano fiber, plasticizer, anionic blue color paste and DMF are mixed to obtain antibacterial color-fixing polyurethane.

[0044] A method for preparing polyurethane insole leather comprises the following steps: A. Extrude the above antibacterial color-fixing polyurethane into the inside of the insole base, dry, wash with water 6 times, and dry at 100°C for 20 seconds; B. Then, the surface of the insole base is coated with antibacterial color-fixing polyurethane with a coating thickness of 1.5 mm, dried, washed with water 25 times, and dried at 100° C. for 30 min to obtain a polyurethane insole leather. Example 3

[0045] An antibacterial color-fixing polyurethane, the raw materials of which include, by weight: 100 parts of polyurethane resin, 20 parts of oregano fiber, 3 parts of plasticizer, 8 parts of anionic blue color paste, and 80 parts of DMF; The raw materials of the polyurethane resin include, by weight: 6.46 parts of 4,4-diphenylmethane diisocyanate, 16 parts of polyol XCPP-30013, 6 parts of dihydroxy silicone oligomer 822F2, 0.7 parts of N-methyldiethanolamine, 0.5 parts of caprine, 0.06 parts of carvacrol, 1 part of chain extender methylpropylene glycol, 0.06 parts of terminator methanol, 0.59 parts of acetic acid and 66 parts of DMF; In the preparation process of oregano fiber, oregano grass is soaked in a sodium hydroxide aqueous solution with a mass fraction of 10wt% for 1 hour, washed with clean water until it does not contain sodium hydroxide, then air-dried to completely dry, and then sheared and ball-milled to obtain oregano fiber with a particle size of 500μm.

[0046] The method for preparing the antibacterial color-fixing polyurethane comprises the following steps: S1. Under nitrogen protection, dihydroxy silicone oligomer 822F2, polyol XCPP-30013, carvacrol, N-methyldiethanolamine and DMF were mixed, and then part of 4,4-diphenylmethane diisocyanate was added, and the temperature was raised to 70°C for reaction until the viscosity reached 13cps / 55°C, wherein the weight ratio of 4,4-diphenylmethane diisocyanate to DMF was 2.3:21; S2, under nitrogen protection, add DMF, chain extender methyl propanediol, caprine and mix well, then add the remaining 4,4-diphenylmethane diisocyanate, react at 70°C, when the viscosity reaches 35cps / 25°C, add terminator methanol, continue to react at 70°C for 25min, add acetic acid, continue to react at 70°C for 25min, to obtain a polyurethane resin, wherein in S2, the weight ratio of 4,4-diphenylmethane diisocyanate to DMF is 4.16:45; the weight ratio of 4,4-diphenylmethane diisocyanate in S1 and S2 is 2.3:4.16; S3, the polyurethane resin, oregano fiber, plasticizer, anionic blue color paste and DMF are mixed to obtain antibacterial color-fixing polyurethane.

[0047] A method for preparing polyurethane insole leather comprises the following steps: A. Extrude the antibacterial color-fixing polyurethane into the inner part of the insole base, dry, wash with water 8 times, and dry at 110° C. for 45 seconds; B. Then, the surface of the insole base is coated with antibacterial color-fixing polyurethane with a coating thickness of 2 mm, dried, washed with water 30 times, and dried at 110° C. for 30 min to obtain a polyurethane insole leather.

[0048] Comparative Example 1 A polyurethane, the raw material of which does not contain dihydroxy silicone oligomer 8832F1, and the other parts are the same as those in Example 1. The polyurethane and polyurethane insole leather are prepared according to the method in Example 1.

[0049] Comparative Example 2 A polyurethane, whose raw materials do not contain carvacrol, and other parts are the same as those in Example 1. Polyurethane and polyurethane insole leather are prepared according to the method in Example 1.

[0050] Comparative Example 3 A polyurethane, whose formula is the same as that of Example 1.

[0051] The preparation method of the above polyurethane comprises the following steps: Under nitrogen protection, dihydroxy silicone oligomer 8832F1, polyol XCPP-20001, carvacrol, N-methyldiethanolamine, chain extender ethylene glycol, caprine, and DMF were mixed, and then all 4,4-diphenylmethane diisocyanate was added, and the temperature was raised to 60°C for reaction for 2 hours, and terminator ethylene glycol was added, and the reaction was continued at 60°C for 30 minutes, and acetic acid was added, and the reaction was continued at 60°C for 30 minutes to obtain a polyurethane resin, wherein the weight ratio of 4,4-diphenylmethane diisocyanate to DMF was 6.5:66; The polyurethane resin, oregano fiber, plasticizer, anionic blue color paste and DMF are mixed to obtain the antibacterial color-fixing polyurethane.

[0052] And prepare polyurethane insole leather according to the method of Example 1.

[0053] Comparative Example 4 A polyurethane, wherein the oregano fiber in the formula is replaced by wood cellulose, and the other parts are the same as those in Example 1. Polyurethane and polyurethane insole leather are prepared according to the method in Example 1.

[0054] Comparative Example 5 A polyurethane, whose raw materials do not contain caprine, and other parts are the same as those in Example 1. Polyurethane and polyurethane insole leather are prepared according to the method in Example 1.

[0055] The insole leathers prepared in Examples 1-3 and Comparative Examples 1-5 were tested for antibacterial properties according to GB / T 31713-2015; the wear resistance was tested according to GB / T 21196-2007; and the peel strength was tested according to GB / T 3903.3-2011.

[0056] Use a 1kg load to test the alcohol wiping resistance of the insole leather and check whether the insole leather fades after wiping.

[0057] The results are shown in Table 1 and Figure 1 shown.

[0058] Figure 1 The following are photos of the color fading test results of Example 1, Comparative Example 3, and Comparative Example 5.

[0059]

[0060] Examples 1-3 have good antibacterial activity, wear resistance, not easy to fade and high peel strength. However, the above properties of Comparative Examples 1-5 are relatively poor. In Comparative Example 1, no dihydroxy silicone oligomer is added, which makes its wear resistance poor and easy to fade; in Comparative Example 2, no carvacrol is added during the preparation of polyurethane, which reduces its antibacterial performance; in Comparative Example 3, a one-step process for preparing polyurethane resin is used, resulting in poor crystallinity, poor peel strength and wear resistance; in Comparative Example 4, wood cellulose is used to replace oregano fiber with antibacterial properties, which makes its antibacterial activity poor; in Comparative Example 5, caprine is not used, which reduces its wear resistance, color fixation performance and peel strength.

[0061] The above description is only a preferred specific implementation manner of the present invention, but the protection scope of the present invention is not limited thereto. Any technician familiar with the technical field can make equivalent replacements or changes according to the technical scheme and inventive concept of the present invention within the technical scope disclosed by the present invention, which should be covered by the protection scope of the present invention.

Claims

1. An antibacterial color-fixing polyurethane, characterized in that: The raw materials include, by weight: 100 parts of polyurethane resin, 10-20 parts of oregano fiber, 1-3 parts of plasticizer, 3-8 parts of color paste, and 260-80 parts of organic solvent; The raw materials of the polyurethane resin include, by weight: 3.7-8.1 parts of diisocyanate, 14-16 parts of polyol, 2-6 parts of dihydroxy silicone oligomer, 0.5-0.7 parts of N-methyldiethanolamine, 0.5-0.55 parts of caprine, 0.03-0.06 parts of antibacterial agent, 0.55-1 parts of chain extender, 0.03-0.06 parts of terminator, 0.5-0.6 parts of organic acid and 161-66 parts of organic solvent.

2. The antibacterial color-fixing polyurethane according to claim 1, characterized in that: The weight average molecular weight of the dihydroxy silicone oligomer is 2000-3000.

3. The antibacterial color-fixing polyurethane according to claim 1, characterized in that: The antimicrobial agent is carvacrol.

4. The antibacterial color-fixing polyurethane according to claim 1, characterized in that: The color paste is an anionic color paste.

5. A method for preparing the antibacterial color-fixing polyurethane according to any one of claims 1 to 4, characterized in that: The steps include: S1. In an inert gas atmosphere, a dihydroxy silicone oligomer, a polyol, an antibacterial agent, N-methyldiethanolamine, and an organic solvent 1 are mixed evenly, and then a portion of diisocyanate is added to react; S2. In an inert gas atmosphere, add organic solvent 1, chain extender, caprine and mix well, then add the remaining diisocyanate to react. When the viscosity reaches 25-35cps / 25°C, add terminator, continue the reaction, add organic acid and mix well to obtain polyurethane resin. S3, mixing the polyurethane resin, oregano fiber, plasticizer, color paste and organic solvent 2 to obtain an antibacterial color-fixing polyurethane.

6. The method for preparing the antibacterial color-fixing polyurethane according to claim 5, characterized in that: In S1, the reaction temperature is 60-80°C, and the reaction is carried out until the viscosity reaches 10-13 cps / 55°C.

7. Use of the antibacterial color-fixing polyurethane according to any one of claims 1 to 4 in insole leather.

8. A polyurethane insole leather, characterized in that: include: An insole base and an antibacterial color-fixing polyurethane filled and distributed inside and on the surface of the insole base; wherein the antibacterial color-fixing polyurethane is the antibacterial color-fixing polyurethane according to any one of claims 1-4.

9. A method for preparing the polyurethane insole leather as claimed in claim 8, characterized in that: The steps include: A. Squeeze the antibacterial color-fixing polyurethane into the insole base, dry, wash and bake; B. Coating the antibacterial color-fixing polyurethane on the surface of the insole base, drying, washing, and drying to obtain the polyurethane insole leather.

10. The method for preparing the polyurethane insole leather according to claim 9, characterized in that: In B, the coating thickness is 1-2 mm.

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