Emulsion type modified silicone leather feel agent and preparation method thereof

Abstract

The application belongs to the field of leather auxiliaries, and particularly relates to an emulsion type modified silicone leather hand feel agent and a preparation method thereof. The preparation method is as follows: modified hydroxyl silicone oil is mixed with a silane coupling agent, then an alkaline aqueous solution is added, and after reaction, hydroxyl-terminated amino silicone oil is obtained; the hydroxyl-terminated amino silicone oil is mixed with special polyether and isopropyl alcohol, and after reaction, polyether-modified hydroxyl-terminated silicone oil is obtained; the polyether-modified hydroxyl-terminated silicone oil is mixed with isomeric tridecanol polyoxyethylene ether and glacial acetic acid to obtain a first component; the modified hydroxyl silicone oil is mixed with isomeric tridecanol polyoxyethylene ether to obtain a second component; and the first component and the second component are mixed. The emulsion type modified silicone leather hand feel agent has a comfortable skin-friendly hand feel, is highly versatile, and can be applied to various leather finishing systems. After detection, the emulsion type modified silicone leather hand feel agent has excellent performance in indexes such as moisturizing and delicate feeling, hand feel persistence, leather wear resistance, emulsion stability and the like, and all performances are better than those of similar products on the market.

Description

TECHNICAL FIELD

[0001] The application belongs to the field of leather auxiliaries, and particularly relates to an emulsion type modified silicone leather hand feel agent and a preparation method thereof. BACKGROUND

[0002] Leather hand feel agent is a product used for adjusting the surface touch of leather, and can bring various hand feels such as smoothness, moisturizing, oiliness and softness to the product. The types of hand feel agents are various, and can be classified into silicone hand feel agents, wax hand feel agents and silicone-wax composite hand feel agents according to components.

[0003] The conventional silicone hand feel agent is prepared by using siloxane and various coupling agents, through anionic or cationic polymerization, then hydrophilic modification and emulsification of the hydrophilic silicone oil, but the current silicone hand feel agent has the characteristics of weak combination with the surface of leather; the conventional wax hand feel agent has the defects of difficult emulsification of wax, general emulsion state and few types of hand feel; the conventional silicone-wax composite hand feel agent can obtain special hand feel after combination, but also has defects such as poor physical property, large structural difference between silicone and wax and difficult composite emulsification.

[0004] Therefore, the technical scheme of the present application is proposed. SUMMARY

[0005] In order to solve the problems in the prior art, the present application provides a preparation method of an emulsion type modified silicone leather hand feel agent, which comprises the following steps:

[0006] (1) mixing modified hydroxyl silicone oil and silane coupling agent, then adding an alkaline aqueous solution and reacting under heating to obtain hydroxyl-terminated amino silicone oil;

[0007] (2) mixing the hydroxyl-terminated amino silicone oil with special polyether and isopropyl alcohol and reacting under heating to obtain polyether-modified hydroxyl-terminated silicone oil;

[0008] (3) mixing the polyether-modified hydroxyl-terminated silicone oil with isomeric tridecanol polyoxyethylene ether and glacial acetic acid to obtain a first component;

[0009] (4) mixing the modified hydroxyl silicone oil with isomeric tridecanol polyoxyethylene ether to obtain a second component;

[0010] (5) mixing the first component and the second component to obtain the emulsion type modified silicone leather hand feel agent;

[0011] The modified hydroxyl silicone oil is shown as formula I:

[0012]

[0013] m = 15 ~ 35;

[0014] The special polyether is shown as formula II:

[0015]

[0016] x = 6 ~ 16, y = 0 ~ 10.

[0017] Preferably, the preparation method of the modified hydroxyl silicone oil comprises the following steps:

[0018] (S1) 100 ~ 150 parts by weight of octamethylcyclotetrasiloxane, 1 part by weight of tetramethylammonium hydroxide, 1 part by weight of water are mixed to obtain a mixed raw material;

[0019] (S2) The mixed raw material is heated to 100 ~ 120℃, and reacted for 3 ~ 4h, and then vacuumized at 70℃ to remove methanol, to obtain the modified hydroxyl silicone oil.

[0020] The reaction formula of the preparation process of the modified hydroxyl silicone oil is as follows:

[0021]

[0022] Preferably, in step (1),

[0023] 30 parts by weight of the modified hydroxyl silicone oil is mixed with 1 ~ 3 parts by weight of the 602 type silane coupling agent, then 0.1 parts by weight of 10wt.% KOH alkaline aqueous solution is added, and reacted under heating conditions to obtain the hydroxyl-terminated amino silicone oil;

[0024] And / or, the temperature of the heating is 110 ~ 120℃, and the time of the reaction is 6 ~ 8h.

[0025] The reaction formula of step (1) is as follows:

[0026]

[0027] Preferably, in step (2),

[0028] 80 ~ 100 parts by weight of the hydroxyl-terminated amino silicone oil is mixed with 40 ~ 60 parts by weight of the special polyether, 40 ~ 80 parts by weight of isopropyl alcohol, and reacted under heating conditions to obtain the polyether-modified hydroxyl-terminated silicone oil;

[0029] And / or, the temperature of the heating is 60 ~ 80℃, and the time of the reaction is 6 ~ 12h.

[0030] The reaction formula of step (2) is as follows:

[0031]

[0032] Preferably, in step (3),

[0033] 40-50 parts by weight of polyether-modified hydroxyl-terminated silicone oil is stirred and mixed with 5-10 parts by weight of isomeric tridecanol polyoxyethylene ether of type 1307 for 20-30 min, 3 parts by weight of glacial acetic acid is then added and dispersed for 1-2 h to obtain a first component.

[0034] Preferably, in step (4),

[0035] 5-10 parts by weight of modified hydroxyl silicone oil is stirred and mixed with 5-10 parts by weight of isomeric tridecanol polyoxyethylene ether of type 1303 for 20-30 min to obtain a second component.

[0036] Preferably, in step (5),

[0037] The first component, the second component and 120-140 parts by weight of water are stirred and mixed for 1-2 h to obtain the emulsion type modified silicone leather feel agent.

[0038] Based on the same technical concept, another aspect of the present application provides an emulsion type modified silicone leather feel agent prepared by the above preparation method.

[0039] The present application has the following advantages:

[0040] The emulsion type modified silicone leather feel agent has a comfortable skin-friendly feel and strong versatility, and can be applied to various leather finishing systems. After testing, it performs excellently in terms of moisturizing and delicate feel, hand feel durability, leather wear resistance, emulsion stability and other indicators, and its performance is better than that of similar products on the market.

[0041] The preparation method described in the present application is simple, easy to control, environmentally friendly and can be scaled up. DETAILED DESCRIPTION

[0042] To make the purpose, technical solutions and advantages of the present application clearer, the technical solutions of the present application will be described in detail below. Obviously, the described embodiments are only part of the embodiments of the present application, not all. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor are within the scope of protection of the present application.

[0043] Example 1

[0044] The present embodiment provides a preparation method of an emulsion type modified silicone leather feel agent, which comprises the following steps:

[0045] (I) Preparation of modified hydroxyl silicone oil

[0046] (S1) 100 g octamethylcyclotetrasiloxane, 1 g tetramethylammonium hydroxide, 1 g water were added into a reactor, and after being mixed uniformly, a mixed raw material was obtained;

[0047] (S2) The mixed raw material was warmed to 100°C, and reacted for 4 h. After completion, vacuum was applied at 70°C to -0.1 MPa to remove methanol, to obtain a modified hydroxyl silicone oil.

[0048] (II) Preparation of an emulsion type modified silicone leather feel agent

[0049] (1) 30 g of the modified hydroxyl silicone oil was mixed with 1 g of a 602 type silane coupling agent at 80°C, then 0.1 g of a 10 wt.% KOH alkaline aqueous solution was added, and the temperature was raised to 110°C and kept for 8 h of reaction. After the reaction was completed, an ice acetic acid was added in an amount equivalent to the molar amount of KOH to neutralize the alkalinity of the system. Finally, ethanol and small molecules in the system were removed under high temperature and high pressure to obtain a hydroxyl-terminated amino silicone oil;

[0050] (2) 80 g of the hydroxyl-terminated amino silicone oil, 40 g of a special polyether, and 40 g of isopropyl alcohol were added into a reactor and mixed uniformly, then warmed to 60°C and reacted for 12 h. After the reaction was completed, the solvent isopropyl alcohol was removed under high temperature and high pressure to obtain a polyether-modified hydroxyl-terminated silicone oil;

[0051] (3) 40 g of the polyether-modified hydroxyl-terminated silicone oil was mixed with 5 g of a 1307 type isomeric tridecanol polyoxyethylene ether for 20 min, and then 3 g of ice acetic acid was added and dispersed for 1 h to obtain a first component;

[0052] (4) 5 g of the modified hydroxyl silicone oil was mixed with 5 g of a 1303 type isomeric tridecanol polyoxyethylene ether for 20 min to obtain a second component;

[0053] (5) The first component, the second component, and 120 g of water were mixed for 1 h, and then 80 g of water was added dropwise (25-30 min for dropwise addition) and dispersed for 1 h to obtain the emulsion type modified silicone leather feel agent.

[0054] Example 2

[0055] The present example provides a preparation method of an emulsion type modified silicone leather feel agent, which comprises the following steps:

[0056] (I) Preparation of a modified hydroxyl silicone oil

[0057] (S1) 150 g of octamethylcyclotetrasiloxane, 1 g of tetramethylammonium hydroxide, and 1 g of water were added into a reactor, and after being mixed uniformly, a mixed raw material was obtained;

[0058] (S2) The mixed raw materials are heated to 120°C, reacted for 3h, and then vacuumized to -0.1 MPa at 70°C to remove methanol, to obtain the modified hydroxyl silicone oil.

[0059] (II) Preparation of the emulsion type modified silicone leather feel agent

[0060] (1) 30g of the modified hydroxyl silicone oil is mixed with 3g of the silane coupling agent 602 at 80°C, then 0.1g of 10wt.% KOH alkaline aqueous solution is added, and then the temperature is raised to 120°C and kept for 6h of reaction. After the reaction is completed, an acid of the same molar as KOH, glacial acetic acid, is added to neutralize the alkalinity of the system. Finally, ethanol and small molecules in the system are removed at high temperature and high pressure to obtain an amino silicone oil capped with hydroxyl groups;

[0061] (2) 100g of the amino silicone oil capped with hydroxyl groups, 60g of the special polyether, and 80g of isopropyl alcohol are added to the reactor and mixed uniformly, then the temperature is raised to 80°C and reacted for 6h. After the reaction is completed, the solvent isopropanol is removed at high temperature and high pressure to obtain a polyether modified silicone oil capped with hydroxyl groups;

[0062] (3) 50g of the polyether modified silicone oil capped with hydroxyl groups is mixed with 10g of the isomeric tridecanol polyoxyethylene ether 1307 for 30min, and then 3g of glacial acetic acid is added and dispersed for 2h to obtain the first component;

[0063] (4) 10g of the modified hydroxyl silicone oil is mixed with 10g of the isomeric tridecanol polyoxyethylene ether 1303 for 30min to obtain the second component;

[0064] (5) The first component, the second component, and 140g of water are mixed for 2h, and then 80g of water is added dropwise (25-30min for dropwise addition) and continuously dispersed for 2h to obtain the emulsion type modified silicone leather feel agent.

[0065] Example 3

[0066] The present embodiment provides a preparation method of an emulsion type modified silicone leather feel agent, which comprises the following steps:

[0067] (I) Preparation of the modified hydroxyl silicone oil

[0068] (S1) 125g of octamethylcyclotetrasiloxane, 1g of tetramethylammonium hydroxide, and 1g of water are added to a reactor and mixed uniformly to obtain mixed raw materials;

[0069] (S2) The mixed raw materials are heated to 110°C, reacted for 3.5h, and then vacuumized to -0.1 MPa at 70°C to remove methanol, to obtain the modified hydroxyl silicone oil.

[0070] (II) Preparation of the emulsion type modified silicone leather feel agent

[0071] (1) 30 g modified hydroxyl silicone oil was mixed with 2 g of 602 type silane coupling agent at 80°C, then 0.1 g of 10 wt.% KOH alkaline aqueous solution was added, and then the temperature was raised to 115°C and kept for 7 h. After the reaction was completed, an ice acetic acid was added in an amount equal to the molar amount of KOH to neutralize the alkalinity of the system. Finally, ethanol and small molecules in the system were removed under high temperature and high pressure to obtain a hydroxyl-terminated amino silicone oil;

[0072] (2) 90 g of the hydroxyl-terminated amino silicone oil, 50 g of a special polyether, and 60 g of isopropyl alcohol were added to a reactor and mixed uniformly, then the temperature was raised to 70°C and reacted for 9 h. After the reaction was completed, the solvent isopropyl alcohol was removed under high temperature and high pressure to obtain a polyether-modified hydroxyl-terminated silicone oil;

[0073] (3) 45 g of the polyether-modified hydroxyl-terminated silicone oil was mixed with 7.5 g of 1307 type isomeric tridecanol polyoxyethylene ether for 25 min, and then 3 g of ice acetic acid was added and dispersed for 1.5 h to obtain a first component;

[0074] (4) 7.5 g of modified hydroxyl silicone oil was mixed with 7.5 g of 1303 type isomeric tridecanol polyoxyethylene ether for 25 min to obtain a second component;

[0075] (5) The first component, the second component, and 130 g of water were mixed and dispersed for 1.5 h, and then 80 g of water was added dropwise (added for 25-30 min) and dispersed for another 1.5 h to obtain the emulsion type modified organic silicone leather feel agent.

[0076] Comparative Example 1

[0077] The present comparative example provides a preparation method of a leather feel agent, which comprises the following steps:

[0078] (1) 40 g of polyether-modified hydroxyl-terminated silicone oil was mixed with 5 g of 1307 type isomeric tridecanol polyoxyethylene ether for 20 min, and then 3 g of ice acetic acid was added and dispersed for 1 h to obtain a first mixture;

[0079] (2) 120 g of water was added to the first mixture and dispersed at 3000 r / min for 1 h to obtain a second mixture;

[0080] (3) 80 g of water was added dropwise to the second mixture (added for 25-30 min) and dispersed for 1 h to obtain the leather feel agent.

[0081] Comparative Example 2

[0082] The present comparative example provides a preparation method of a leather feel agent, which comprises the following steps:

[0083] (1) 5 g modified hydroxyl silicone oil was stirred and mixed with 5 g isomeric tridecanol polyoxyethylene ether type 1303 for 20 min to obtain a first mixture;

[0084] (2) 120 g water was added to the first mixture and dispersed at 3000 r / min for 1 h to obtain a second mixture;

[0085] (3) 80 g water was gradually added to the second mixture (25-30 min for complete addition), and dispersed for 1 h to obtain a leather feel agent.

[0086] Comparative test example

[0087] 1. Comparative object:

[0088] The emulsion type modified silicone leather feel agent (feel agent-1) obtained in Example 1, the leather feel agent (feel agent-2) obtained in Comparative Example 1, the leather feel agent (feel agent-3) obtained in Comparative Example 2, and the commercially available classic product Melio 5230.

[0089] 2. Feel style test:

[0090] Four pieces of equal size sheepskin garment leather (having been sprayed with a bottom layer, a middle layer, and a surface layer) were taken, and each group of feel agents was mixed with a bright layer varnish and sprayed on the surface of the leather, and then dried. A subjective score (1-10, 10 being the best and 1 being the worst) was taken to judge the difference in feel style.

[0091] 3. Feel durability test:

[0092] Four pieces of equal size sheepskin garment leather (having been sprayed with a bottom layer, a middle layer, and a surface layer) were taken, and each group of feel agents was mixed with a bright layer varnish and sprayed on the surface of the leather, and then dried. The feel durability of each group was judged by touch after being placed for 72 h.

[0093] 4. Leather blank wear resistance test:

[0094] The wear resistance test referred to QB / T 2726-2005 Leather Physical and Mechanical Test Wear Resistance Determination.

[0095] 5. Emulsion stability test

[0096] 100 mL of each group of feel agents was taken and placed in a 150 mL wide-mouth bottle, and then placed in a 40°C oven for 2 months, and the separation and precipitation were observed.

[0097] The test results are shown in Table 1.

[0098] Table 1

[0099] Test item Result Result Moisture fine feeling Hand feel agent-1 > Hand feel agent-2 > Melio 5230 > Hand feel agent-3 Hand feel durability Hand feel agent-1 > Melio 5230 > Hand feel agent-2 > Hand feel agent-3 Skin embryo abrasion resistance Hand feel agent-1 > Hand feel agent-3 > Melio 5230 > Hand feel agent-2 Emulsion stability Hand feel agent-1 > Hand feel agent-2 > Melio 5230 > Hand feel agent-3 Emulsion stability Hand feel agent-1 > Hand feel agent-2 > Melio 5230 > Hand feel agent-3

[0100] Results: From Table 1, it can be seen that the properties of Hand Feel Agent-2 and Hand Feel Agent-3 cannot completely outperform Melio 5230, while the properties of Hand Feel Agent-1 obtained by mixing and emulsifying the two are completely superior to Melio 5230, which is an excellent solution.

[0101] The above merely provides a specific implementation of the present application, but the protection scope of the present application is not limited thereto, and any person skilled in the art can easily think of changes or replacements within the technical range disclosed by the present application, which should be encompassed in the protection scope of the present application. Therefore, the protection scope of the present application should be subject to the protection scope of the claims.

Claims

1. A method for producing an emulsion-type modified silicone leather feel agent, characterized by, The preparation method comprises the following steps: (1) mixing modified hydroxyl silicone oil with silane coupling agent, then adding alkaline aqueous solution and reacting under heating condition to obtain hydroxyl-terminated amino silicone oil; (2) mixing the hydroxyl-terminated amino silicone oil with special polyether, isopropyl alcohol and reacting under heating condition to obtain polyether-modified hydroxyl-terminated silicone oil; (3) mixing the polyether-modified hydroxyl-terminated silicone oil with 1307 type isomeric tridecanol polyoxyethylene ether and glacial acetic acid to obtain the first component; (4) mixing the modified hydroxyl silicone oil with 1303 type isomeric tridecanol polyoxyethylene ether to obtain the second component; (5) mixing the first component and the second component to obtain the emulsion type modified silicone leather feel agent. The modified hydroxyl silicone oil is shown as formula I: Formula I m=15~35； The special polyether is shown as formula II: Formula II x=6~16, y=0~10.

2. The method for preparing the emulsion-type modified silicone leather feel agent according to claim 1, characterized by, The preparation method of the modified hydroxyl silicone oil comprises the following steps: (S1) mixing 100~150 parts by weight of octamethylcyclotetrasiloxane, 1 part by weight of tetramethylammonium hydroxide and 1 part by weight of water to obtain mixed raw materials; (S2) heating the mixed raw materials to 100~120℃, reacting for 3~4h, and then vacuumizing at 70℃ to remove methanol, thereby obtaining the modified hydroxyl silicone oil.

3. The method for preparing the emulsion-type modified silicone leather feel agent according to claim 1, characterized by, In step (1), mixing 30 parts by weight of modified hydroxyl silicone oil with 1~3 parts by weight of 602 type silane coupling agent, then adding 0.1 part by weight of 10wt.% KOH alkaline aqueous solution and reacting under heating condition to obtain hydroxyl-terminated amino silicone oil; And / or, the heating temperature is 110~120℃, and the reaction time is 6~8h.

4. The method for preparing the emulsion-type modified silicone leather feel agent according to claim 1, characterized by, In step (2), mixing 80~100 parts by weight of hydroxyl-terminated amino silicone oil with 40~60 parts by weight of special polyether and 40~80 parts by weight of isopropyl alcohol and reacting under heating condition to obtain polyether-modified hydroxyl-terminated silicone oil; And / or, the heating temperature is 60~80℃, and the reaction time is 6~12h.

5. The method for preparing the emulsion-type modified silicone leather feel agent according to claim 1, characterized by, In step (3), stirring and mixing 40~50 parts by weight of polyether-modified hydroxyl-terminated silicone oil with 5~10 parts by weight of 1307 type isomeric tridecanol polyoxyethylene ether for 20~30min, then adding 3 parts by weight of glacial acetic acid and dispersing for 1~2h to obtain the first component.

6. The method for preparing the emulsion-type modified silicone leather feel agent according to claim 1, characterized by, In step (4), stirring and mixing 5~10 parts by weight of modified hydroxyl silicone oil with 5~10 parts by weight of 1303 type isomeric tridecanol polyoxyethylene ether for 20~30min to obtain the second component.

7. The method for preparing the emulsion-type modified silicone leather feel agent according to claim 1, characterized by, In step (5), stirring and mixing the first component, the second component and 120~140 parts by weight of water for 1~2h to obtain the emulsion type modified silicone leather feel agent.

8. The emulsion type modified silicone leather feel agent obtained by the preparation method in any one of claims 1~7.

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