Super-soft hand feeling agent and application thereof

Abstract

The invention provides a super-soft hand feeling agent and application thereof, and belongs to the field of PU synthetic leather. The invention provides a super-soft hand feeling agent. The super-soft hand feeling agent comprises a silicone oil emulsion and a paraffin emulsion, the silicone oil emulsion comprises the following raw materials in percentage by mass: 12-40% of block silicone oil; 1.5-4% of a reactive emulsifier; 0.2%-6% of a non-ionic surface active agent; 0.01 to 0.5 percent of organic acid; and the balance of water. Two ends of a molecule of the reactive emulsifier contain hydroxyl groups; the paraffin emulsion is prepared from the following raw materials in percentage by mass: paraffin, an emulsifier, an alkaline pH regulator and water, the mass ratio of the paraffin to the emulsifier is (3-4): 1; the mass ratio of the paraffin to the water is 1: (1-3); the pH value of the paraffin emulsion is 5-9. After the super-soft hand feeling agent with the raw materials of silicone oil emulsion and paraffin emulsion is mixed with the water-based surface treatment agent, the surface of the synthetic leather can be soft and moist in touch.

Description

Technical Field

[0001] The present invention relates to the field of PU synthetic leather, and particularly relates to a super soft and delicate hand feeling agent and its application. Background Art

[0002] With the development of the economy and the improvement of living standards, people's demand for leather is increasing, and the quality requirements for it are also getting higher and higher. Traditional natural leather has limited resources, and the production process will cause relatively large pollution, which can no longer meet the market demand. Synthetic leather is a composite material that simulates the organizational structure and service performance of natural leather and can be used as a substitute for natural leather.

[0003] Synthetic leather usually uses non-woven fabric to simulate the reticular layer and microporous polyurethane coating to simulate the granular layer. The obtained synthetic leather is very similar to leather on both the front and back sides, and has certain air permeability, being closer to natural leather than ordinary artificial leather, and is widely used in the production of products such as shoes, boots, luggage, and balls.

[0004] However, the surface of synthetic leather is shiny and has a strong plastic feeling. In order to make the appearance and hand feeling of synthetic leather closer to natural leather and achieve a more ideal use effect, during the production process of synthetic leather, the surface of synthetic leather must be treated to endow the surface of synthetic leather with a smooth and soft hand feeling as well as water-proof, stain-proof, and wear-resistant service performance. Existing water-based surface treatment agents generally add micron-level emulsions such as macromolecular hydroxyl and methyl silicone oil to achieve the surface touch of synthetic leather, but the existing water-based surface treatment agents generally have the problem of too hard hand feeling, which affects the overall quality of PU leather. Summary of the Invention

[0005] The present invention provides a super soft and delicate hand feeling agent and its application. The super soft and delicate hand feeling agent of the present invention can be evenly dispersed when added to the PU water-based surface treatment agent, endowing a super soft and delicate touch feeling.

[0006] The present invention provides a super soft and delicate hand feeling agent, which includes silicone oil emulsion and paraffin emulsion;

[0007] In terms of mass fraction, the silicone oil emulsion includes the following raw materials:

[0008]

[0009] The molecular two ends of the reactive emulsifier contain hydroxyl groups;

[0010] In terms of mass fraction, the paraffin emulsion includes the following raw materials:

[0011] Paraffin, emulsifier, alkaline pH regulator, and water;

[0012] The mass ratio of the paraffin to the emulsifier is 3 - 4:1;

[0013] The mass ratio of the paraffin to the water is 1:1 - 3;

[0014] The pH value of the paraffin emulsion is 5-9.

[0015] Preferably, the mass fraction of the silicone oil emulsion in the super soft and delicate feel agent is 40-70%.

[0016] Preferably, the preparation method of the block silicone oil includes the following steps:

[0017] Mix the terminal epoxy silicone oil, aliphatic diamine and polar organic solvent, and carry out a ring-opening reaction to obtain the block silicone oil.

[0018] Preferably, the molar ratio of the terminal epoxy silicone oil to the aliphatic diamine is 1:0.5-2;

[0019] The relative molecular mass of the terminal epoxy silicone oil is 4000-20000; the relative molecular mass of the aliphatic diamine is 200-2000.

[0020] Preferably, the preparation method of the reactive emulsifier includes the following steps:

[0021] Mix the terminal hydrogen-containing silicone oil, allyl polyether and inorganic catalyst to carry out a hydrosilylation reaction to obtain the reactive emulsifier.

[0022] Preferably, the molar ratio of the terminal hydrogen-containing silicone oil to the allyl polyether is 1.0:1.0-2.2;

[0023] The relative molecular mass of the terminal hydrogen-containing silicone oil is 2000-6000;

[0024] The relative molecular mass of the allyl polyether is 200-5000.

[0025] Preferably, the emulsifier includes one or more of OP-10, Span emulsifier, Tween emulsifier, fatty alcohol polyoxyethylene ether and glyceryl stearate.

[0026] Preferably, the Span emulsifier is Span 80, the Tween emulsifier is Tween 80, and the fatty alcohol polyoxyethylene ether is fatty alcohol polyoxyethylene ether O-3, fatty alcohol polyoxyethylene ether O-9 and fatty alcohol polyoxyethylene ether O-20.

[0027] Preferably, when the emulsifier is Span 80 and Tween 80, the mass ratio of Span 80 to Tween 80 is 1:2;

[0028] When the emulsifier is fatty alcohol polyoxyethylene ether O-3, fatty alcohol polyoxyethylene ether O-9 and fatty alcohol polyoxyethylene ether O-20, the mass ratio of fatty alcohol polyoxyethylene ether O-3, fatty alcohol polyoxyethylene ether O-9 and fatty alcohol polyoxyethylene ether O-20 is 2:2:1.

[0029] The present invention also provides an application of the above-described super soft and tender feel agent in the aqueous surface treatment of PU synthetic leather.

[0030] The present invention uses a reactive emulsifier with active hydroxyl groups at both ends and strictly controls the content of each material to prepare After the hydroxyl groups in the stable silicone oil emulsion are mixed with the aqueous surface treatment agent, they can crosslink into a homogeneous system, endowing the PU leather with a lasting soft and tender touch; paraffin can prevent water and adhesion and has a soft feel. Therefore, the super soft and tender feel agent with silicone oil emulsion and paraffin emulsion as raw materials can endow the surface of the synthetic leather with a soft and moist touch after being mixed with the aqueous surface treatment agent. Specific Embodiments

[0031] The present invention provides a super soft and tender feel agent, comprising a silicone oil emulsion and a paraffin emulsion;

[0032] In terms of mass fraction, the silicone oil emulsion comprises the following raw materials:

[0033]

[0034] The molecular ends of the reactive emulsifier contain hydroxyl groups;

[0035] In terms of mass fraction, the paraffin emulsion comprises the following raw materials:

[0036] Paraffin, emulsifier, alkaline pH regulator and water;

[0037] The mass ratio of the paraffin to the emulsifier is 3 - 4:1;

[0038] The mass ratio of the paraffin to the water is 1:1 - 3;

[0039] The pH value of the paraffin emulsion is 5 - 9.

[0040] In the present invention, the mass fraction of the silicone oil emulsion in the super soft and tender feel agent is preferably 40 - 70%. In specific embodiments of the present invention, the mass fraction of the silicone oil emulsion in the super soft and tender feel agent can be 40%, 50%, 60% or 70%.

[0041] In the present invention, unless otherwise specified, the raw materials are all commercially available products well-known to those skilled in the art.

[0042] The following is an introduction to the silicone oil emulsion:

[0043] In terms of mass fraction, the raw materials of the silicone oil emulsion provided by the present invention include 12 - 40% of block silicone oil. In specific embodiments of the present invention, the mass fraction of the block silicone oil can be 12%, 15%, 20%, 25%, 30%, 35% or 40%.

[0044] In the present invention, the preparation method of the block silicone oil preferably comprises the following steps:

[0045] The terminal epoxy silicone oil, aliphatic diamine and polar organic solvent are mixed and then subjected to a ring-opening reaction to obtain the block silicone oil.

[0046] In the present invention, the molar ratio of the terminal epoxy silicone oil to the aliphatic diamine is preferably 1:0.5 to 2. Among them, In specific embodiments of the present invention, the molar ratio of the terminal epoxy silicone oil to the aliphatic diamine can be 1:0.5, 1:1, 1:1.5 or 1:2; the relative molecular mass of the terminal epoxy silicone oil is preferably 4000 - 20000, and in specific embodiments of the present invention, the relative molecular mass of the terminal epoxy silicone oil can be 4000, 6000, 8000, 10000, 12000, 14000, 16000, 18000 or 20000; the relative molecular mass of the aliphatic diamine is preferably 200 - 2000, and in specific embodiments of the present invention, the relative molecular mass of the aliphatic diamine can be 200, 400, 600, 800, 1000, 1200, 1400, 1600, 1800 or 2000; the aliphatic diamine is preferably one or more of D400, ED600 and ED900 produced by Huntsman Corporation, Yangzhou Chenhua New Materials Co., Ltd. or Zhejiang Huangma Science & Technology Co., Ltd., and more preferably ED600 and / or ED900 of Huntsman Corporation.

[0047] In the present invention, the mass of the polar organic solvent preferably accounts for 20 - 40% of the total mass of the terminal epoxy silicone oil and the aliphatic diamine. In specific embodiments of the present invention, the addition amount of the polar organic solvent preferably accounts for 20%, 25%, 30%, 35% or 40% of the total amount of the reactants; the polar organic solvent preferably includes one or more of isopropanol, ethylene glycol monobutyl ether and diethylene glycol monobutyl ether, and more preferably isopropanol.

[0048] In the present invention, the temperature of the ring-opening reaction is 80 - 120 °C and the time is 6 - 10 h. In specific embodiments of the present invention, the temperature of the ring-opening reaction can be 80 °C, 90 °C, 100 °C, 110 °C or 120 °C, and the time can be 6 h, 7 h, 8 h, 9 h or 10 h.

[0049] In the present invention, the ring-opening reaction is preferably carried out under stirring conditions, and the stirring speed is preferably 200 - 600 r / min. In specific embodiments of the present invention, the stirring speed can be 200 r / min, 300 r / min, 400 r / min, 500 r / min or 600 r / min.

[0050] In the present invention, after the ring-opening reaction is completed, the present invention preferably cools the obtained product to room temperature to obtain the block silicone oil.

[0051] In terms of mass fraction, the raw materials of the silicone oil emulsion provided by the present invention include 2-4% of a reactive emulsifier. In specific embodiments of the present invention, the mass fraction of the reactive emulsifier can be 2%, 2.5%, 3%, 3.5% or 4%.

[0052] In the present invention, the preparation method of the reactive emulsifier preferably includes the following steps:

[0053] Mix a hydrogen-terminated silicone oil, an allyl polyether and an inorganic catalyst to carry out a hydrosilylation reaction to obtain the reactive emulsifier.

[0054] In the present invention, the mixing preferably includes first mixing the hydrogen-terminated silicone oil and the allyl polyether. Then The obtained mixture is secondarily mixed with an inorganic catalyst.

[0055] In the present invention, the first mixing is preferably carried out under stirring, and the stirring speed is preferably 200-600 r / min. In specific embodiments of the present invention, the stirring speed can be 200 r / min, 300 r / min, 400 r / min, 500 r / min or 600 r / min.

[0056] The temperature of the first mixing is 40-60 °C. In specific embodiments of the present invention, the temperature of the first mixing can be 40 °C, 45 °C, 50 °C, 55 °C or 60 °C.

[0057] In the present invention, the reaction molar ratio of the hydrogen-terminated silicone oil and the allyl polyether is preferably 1:1-2.2. In specific embodiments of the present invention, the reaction molar ratio of the hydrogen-terminated silicone oil and the allyl polyether can be 1:1, 1:1.2, 1:1.5, 1:1.8, 1:2 or 1:2.2; the relative molecular mass of the hydrogen-terminated silicone oil is preferably 2000-6000. In specific embodiments of the present invention, the relative molecular mass of the hydrogen-terminated silicone oil can be 1000, 2500, 3000, 3500, 4000, 4500, 5000, 5500 or 6000; the relative molecular mass of the allyl polyether is preferably 200-5000. In specific embodiments of the present invention, the relative molecular mass of the allyl polyether can be 200, 1000, 2000, 3000, 4000 or 5000; the allyl polyether preferably includes polyether F6 or polyether F10 produced by Jiangsu Zhongshan Chemical Co., Ltd., Yangzhou Chenhua New Materials Co., Ltd. or Liaoning Kelong Fine Chemical Co., Ltd., and more preferably polyether F6 or polyether F10 of Jiangsu Zhongshan Chemical Co., Ltd.

[0058] In the present invention, the mass ratio of the hydrogen-terminated silicone oil to the inorganic catalyst is preferably 1:0.005; the inorganic catalyst includes chloroplatinic acid.

[0059] In the present invention, the temperature of the hydrosilylation reaction is preferably 100-140°C, and the time is preferably 2-6 h. In specific embodiments of the present invention, the temperature of the hydrosilylation reaction can be 100°C, 110°C, 120°C, 130°C or 140°C, and the time can be 2 h, 3 h, 4 h, 5 h or 6 h.

[0060] In the present invention, after the hydrosilylation reaction is completed, the product obtained is preferably cooled to room temperature to obtain the reactive emulsifier. Let the emulsion cool naturally to room temperature to make the structure of the emulsion more stable.

[0061] By mass fraction, the raw materials of the silicone oil emulsion provided by the present invention include 0.2-6% of non-ionic surfactant. In specific embodiments of the present invention, the mass fraction of the non-ionic surfactant can be 0.2%, 0.5%, 1%, 2%, 3%, 4%, 5% or 6%; the non-ionic surfactant preferably includes isomeric alcohol polyoxyethylene ether and / or fatty alcohol polyoxyethylene ether; the fatty alcohol polyoxyethylene ether preferably includes AEO series products, and the AEO series products preferably come from BASF SE, Shell Group or Sanjiang Chemical Co., Ltd. In specific embodiments of the present invention, the linear alkyl alcohol polyoxyethylene ether is preferably BASF AEO-9; the isomeric alcohol polyoxyethylene ether preferably includes isomeric tridecyl alcohol polyoxyethylene Ether; the isomeric tridecyl alcohol polyoxyethylene ether is preferably from BASF SE or Sasol Chemicals ether. In specific embodiments of the present invention, the isomeric tridecyl alcohol polyoxyethylene ether is specifically Sasol 1370 isomeric tridecyl alcohol polyoxyethylene ether

[0062] By mass fraction, the raw materials of the silicone oil emulsion provided by the present invention include 0.01-0.5% of organic acid. In specific embodiments of the present invention, the mass fraction of the organic acid can be 0.1%, 0.2%, 0.3%, 0.4% or 0.5%; the organic acid preferably includes one or more of glacial acetic acid, citric acid and lactic acid, preferably glacial acetic acid; the function of the organic acid is to promote the conversion of the oil phase to the water phase and adjust the pH value of the emulsion.

[0063] By mass fraction, the raw materials of the silicone oil emulsion provided by the present invention include the balance of water.

[0064] In the present invention, the preparation method of the silicone oil emulsion preferably includes the following steps:

[0065] Mix the block silicone oil, reactive emulsifier, non-ionic surfactant and glacial acetic acid (the third mixing), and then mix with water (the fourth mixing) to obtain the silicone oil emulsion.

[0066] In the present invention, the third mixing is preferably carried out under stirring, and the stirring speed is preferably 600 - 2000 r / min. In specific embodiments of the present invention, the stirring speed can be 600 r / min, 1000 r / min, 1500 r / min, 1800 r / min or 2000 r / min.

[0067] In the present invention, the third mixing preferably includes: carrying out a third' mixing of the block silicone oil and the reactive emulsifier and then carrying out a third'' mixing with the nonionic surfactant and glacial acetic acid.

[0068] In the present invention, the time for the third' mixing and the third'' mixing is independently preferably 30 - 60 min. In specific embodiments of the present invention, the time for the third' mixing and the third'' mixing can independently be 30 min, 40 min, 50 min or 60 min.

[0069] In the present invention, the fourth mixing preferably includes adding water droplets to the mixture obtained in the third step.

[0070] In the present invention, the dropping time is preferably 2.5 - 3 h.

[0071] The paraffin emulsion is introduced below:

[0072] In terms of mass fraction, the raw materials of the paraffin emulsion include paraffin, emulsifier, alkaline pH regulator and water.

[0073] In the present invention, the mass ratio of the paraffin to the emulsifier is 3 - 4:1; the melting point of the paraffin is preferably 58 - 60 °C; the emulsifier preferably includes one or more of OP-10, Span emulsifier, Tween emulsifier, fatty alcohol polyoxyethylene ether and glyceryl stearate; the Span emulsifier is Span 80, the Tween emulsifier is Tween 80, and the fatty alcohol polyoxyethylene ether is fatty alcohol polyoxyethylene ether O-3, fatty alcohol polyoxyethylene ether O-9 and fatty alcohol polyoxyethylene ether O-20; when the emulsifier is Span 80 and Tween 80, the mass ratio of Span 80 to Tween 80 is preferably 1:2; when the emulsifier is fatty alcohol polyoxyethylene ether When it is O-3, fatty alcohol polyoxyethylene ether O-9 and fatty alcohol polyoxyethylene ether O-20, the fatty alcohol poly Oxyethyl The mass ratio of fatty alcohol polyoxyethylene ether O-3, fatty alcohol polyoxyethylene ether O-9 and fatty alcohol polyoxyethylene ether O-20 is preferably 2:2:1. The composite emulsifier can convert the paraffin from the oil phase to the water phase.

[0074] In the present invention, the mass ratio of the paraffin to the water is 1:1 - 3.

[0075] In the present invention, the pH value of the paraffin emulsion is 5 - 9.

[0076] In the present invention, the alkaline pH regulator preferably comprises sodium hydroxide solution and / or AMP-95 pH regulator (Dow Chemical) with a concentration of 0.9%.

[0077] In the present invention, the preparation method of the paraffin emulsion preferably comprises the following steps:

[0078] The emulsifier is added dropwise to the melted paraffin, and then the obtained mixture is successively mixed with the alkaline pH regulator and water to obtain the paraffin emulsion.

[0079] The emulsifier is slowly added dropwise to the melted paraffin, and the dropping speed should not be too fast. At the same time, stirring is maintained to fully mix the paraffin and the emulsifier.

[0080] In the present invention, the temperature of the dropping is preferably 80-90 °C, the dropping is preferably carried out under stirring conditions, and the stirring speed is preferably 300-500 r / min. In specific embodiments of the present invention, the stirring speed can be 300 r / min, 350 r / min, 400 r / min, 450 r / min or 500 r / min.

[0081] In the present invention, the temperature when successively mixing with the alkaline pH regulator and water is preferably 80-90 °C.

[0082] After mixing with water, the present invention preferably cools the obtained emulsion to room temperature naturally. Allowing the emulsion to cool to room temperature naturally makes the structure of the emulsion more stable.

[0083] In the present invention, the preparation method of the super soft and delicate hand feel agent preferably comprises the following steps:

[0084] Mix the silicone oil emulsion and the paraffin emulsion.

[0085] The present invention also provides the application of the super soft and delicate hand feel agent described in the above technical solution in the water-based surface treatment of PU synthetic leather.

[0086] The present invention has no special requirements for the specific implementation manner of the application, and the common methods of those skilled in the art can be adopted.

[0087] In specific embodiments of the present invention, the method of the application preferably comprises the following steps:

[0088] After mixing the water-based surface treatment agent and the super soft and delicate hand feel agent, it is coated on the surface of the PU synthetic leather and then dried.

[0089] In the present invention, by mass, the first raw material of the water-based surface treatment agent preferably comprises:

[0090]

[0091]

[0092] 4 parts of low-shear associative polyurethane thickener.

[0093] The solid content of the aqueous polyurethane resin is preferably 25%.

[0094] In the present invention, when the raw material of the aqueous surface treatment agent is the first raw material, the mass ratio of the aqueous surface treatment agent to the super soft and delicate hand feeling agent is preferably 20-50:1.

[0095] When the raw material of the aqueous surface treatment agent is the first raw material, the aqueous surface treatment of the PU synthetic leather preferably includes: coating the slurry after mixing the aqueous surface treatment agent and the super soft and delicate hand feeling agent on the surface of the synthetic leather.

[0096] The present invention has no special limitation on the coating. In the specific embodiments of the present invention, the slurry is scraped and coated on the surface of the synthetic leather by a 100-mesh roller of a three-color printing press.

[0097] In the present invention, in terms of parts by mass, the second raw material of the aqueous surface treatment agent preferably includes:

[0098]

[0099] In the present invention, when the raw material of the aqueous surface treatment agent is the second raw material, the mass ratio of the aqueous surface treatment agent to the super soft and delicate hand feeling agent is preferably 30-100:1.

[0100] When the raw material of the aqueous surface treatment agent is the second raw material, the aqueous surface treatment of the PU synthetic leather preferably includes: mixing and coating the aqueous surface treatment agent and the super soft and delicate hand feeling agent on the release paper and then transferring it to the wet BASE after baking.

[0101] The following is a detailed description of the super soft and delicate hand feeling agent and its application provided by the present invention in combination with examples, but they should not be construed as limiting the protection scope of the present invention.

[0102] Example 1

[0103] Preparation of silicone oil emulsion:

[0104] Preparation of block silicone oil:

[0105] Add the terminal epoxy silicone oil YK-276-6000 (Zhejiang Yingke New Materials Co., Ltd.), aliphatic diamine ED600 (Huntsman Corporation), and isopropyl alcohol (the amount used is 30% of the total mass of the terminal epoxy silicone oil and the aliphatic diamine) into a four-necked flask, start stirring, and raise the temperature to 80-82 °C at a rotation speed of 400 r / min, react for 8 h, and cool to room temperature to obtain a light yellow to golden yellow transparent liquid, which is the block silicone oil.

[0106] Among them, the molar ratio of the terminal epoxy silicone oil to the aliphatic diamine is 1.0:1.2.

[0107] Preparation of reactive emulsifier:

[0108] Add 3000 molecular weight hydrogen-terminated silicone oil YK-616-3000 (Zhejiang Yingke Chemical Co., Ltd.) and allyl polyether (polyether F6 from Jiangsu Zhongshan Chemical Co., Ltd.) into a four-necked flask, start stirring, heat up to 45 °C at a stirring speed of 600 r / min, add the catalyst chloroplatinic acid, continue to heat up to 120 °C. After the reaction solution turns transparent, continue the heat preservation reaction for 4 h, and cool to room temperature to obtain a colorless to light yellow transparent liquid, which is the reactive emulsifier.

[0109] The molar ratio of the hydrogen-terminated silicone oil to the allyl polyether is 1.0:2.2;

[0110] The catalyst is 0.5% of the mass of the hydrogen-terminated silicone oil.

[0111] Add 20 g of the reactive emulsifier and 200 g of block silicone oil into the emulsifier, turn on the power of the emulsifier, stir at a speed of 800 r / min for 0.5 h, then add 40 g of non-ionic surfactant AE0-9 and 1 g of glacial acetic acid while stirring, continue to stir for 0.5 h, and slowly drop 1000 g of non-ionic water within 2 h to obtain a silicone oil emulsion.

[0112] ② Preparation of paraffin emulsion:

[0113] Mix and compound 2:2:1 by mass of fatty alcohol polyoxyethylene ether O-3, fatty alcohol polyoxyethylene ether O-9 and fatty alcohol polyoxyethylene ether O-20 evenly to prepare a composite emulsifier.

[0114] Heat and stir solid paraffin to gradually melt it, and control the temperature between 80 - 90 °C. Under stirring conditions, slowly drop the composite emulsifier solution into the melted paraffin (the mass ratio of paraffin to the composite emulsifier is 3:1), the dropping speed should not be too fast, and at the same time keep the stirring speed at 300 - 500 r / min to make the paraffin and the emulsifier fully mixed.

[0115] After dropping the composite emulsifier, continue to stir for a period of time, and then adjust the pH value of the emulsion to 8 with 0.9% AMP-95 PH regulator (Dow Chemical).

[0116] Under stirring, slowly add deionized water (the mass ratio of paraffin to deionized water is 1:2) to the emulsion to dilute the emulsion to the required concentration. Then cool down and continue stirring to let the emulsion cool naturally to room temperature to make the structure of the emulsion more stable.

[0117] Preparation of water-based delicate hand feel agent:

[0118] Mix the prepared ① silicone oil emulsion and ② paraffin emulsion evenly according to the mass ratio of 7:3.

[0119] Example 2

[0120] ① Preparation of silicone oil emulsion:

[0121] Preparation of block silicone oil:

[0122] Add the terminal epoxy silicone oil YK-276-8000 with a relative molecular mass of 8000 (Zhejiang Yingke Chemical Co., Ltd., 30% of the total mass of diamine) to a four-necked flask, start stirring, and raise the temperature to 80-82 °C at a rotation speed of 500 r / min. React for 10 h, and cool to room temperature to obtain a light yellow to golden yellow transparent liquid, which is the block silicone oil. Company), fatty Aliphatic diamine ED900 (Huntsman Corporation), isopropyl alcohol (the amount used is based on the terminal epoxy silicone oil and the aliphatic The molar ratio of the terminal epoxy silicone oil to the aliphatic diamine is 1.0:1.2.

[0123] The molar ratio of the terminal epoxy silicone oil to the aliphatic diamine is 1.0:1.2.

[0124] Preparation of reactive emulsifier:

[0125] Add the terminal hydrogen-containing silicone oil YK-616-4000 with a relative molecular mass of 4000 (Zhejiang Yingke New Materials Co., Ltd.) and allyl polyether (polyether F10 of Jiangsu Zhongshan Chemical Co., Ltd.) to a four-necked flask, start stirring, and raise the temperature to 50 °C at a rotation speed of 600 r / min. Add the catalyst chloroplatinic acid, continue to raise the temperature to 120 °C, and after the reaction solution turns transparent, continue to keep the temperature for reaction for 3 h. Cool to room temperature to obtain a colorless to light yellow transparent liquid, which is the reactive emulsifier.

[0126] The molar ratio of the terminal hydrogen-containing silicone oil to the allyl polyether is 1.0:2.2;

[0127] The catalyst is 0.5% of the mass of the terminal hydrogen-containing silicone oil.

[0128] Preparation of super-smooth handfeel agent:

[0129] Add 30 g of reactive emulsifier and 200 g of block silicone oil to the emulsifier, turn on the power of the emulsifier, rotate at 800 r / min, stir mechanically for 0.5 h, then add 40 g of non-ionic surfactant AE0-9 and 1 g of glacial acetic acid while stirring, continue to stir for 0.5 h, and slowly add 800 g of non-ionic water within 2.5 h to obtain the silicone oil emulsion.

[0130] ② Preparation of paraffin emulsion:

[0131] Mix and disperse the Span 80 emulsifier and Tween 80 emulsifier according to the mass ratio of 1:2 to obtain a composite emulsifier

[0132] Heat and stir solid paraffin to gradually melt it, and control the temperature at 80 - 90 °C. Under stirring conditions, slowly add the composite emulsifier to the melted paraffin (the mass ratio of the paraffin to the composite emulsifier is 3:1). The dropping speed should not be too fast, and at the same time, keep the stirring speed at 300 - 500 r / min to fully mix the paraffin and the emulsifier.

[0133] After adding the emulsifier solution, continue stirring for a period of time, and then adjust the pH value of the emulsion to 8 with 0.9% AMP - 95 (Dow Chemical).

[0134] Under stirring conditions, slowly add deionized water (the mass ratio of paraffin to deionized water is 1:2) to the emulsion to dilute the emulsion to the required concentration. Then cool down and continue stirring to let the emulsion cool naturally to room temperature to make the structure of the emulsion more stable.

[0135] ③ Preparation of water - based delicate hand feel agent:

[0136] The prepared silicone oil emulsion ① and paraffin emulsion ② are mixed and dispersed evenly according to a mass ratio of 7:3.

[0137] Example 3

[0138] Preparation of block silicone oil:

[0139] Add epoxy - terminated silicone oil YK - 276 - 9000 with a relative molecular mass of 9000 (Zhejiang Yingke Chemical Co., Ltd.), aliphatic diamine ED900 (Huntsman Corporation), and isopropanol (the amount is 40% of the total mass of the epoxy - terminated silicone oil and the aliphatic diamine) into a four - necked flask, start stirring, and under a rotation speed of 500 r / min, heat up to 80 - 82 °C and react for 10 h. Then cool down to room temperature to obtain a light yellow to golden - yellow transparent liquid, which is the block silicone oil.

[0140] The molar ratio of the epoxy - terminated silicone oil to the aliphatic diamine is 1.0:1.2.

[0141] Preparation of reactive emulsifier:

[0142] Add hydrogen - terminated silicone oil YK - 616 - 4000 with a relative molecular mass of 4000 (Zhejiang Yingke Chemical Co., Ltd.) and allyl polyether (polyether F6 from Jiangsu Zhongshan Chemical Co., Ltd.) into a four - necked flask, start stirring, and under a rotation speed of 400 r / min, heat up to 40 °C, add the catalyst chloroplatinic acid, continue to heat up to 110 °C. After the reaction solution turns transparent, continue to hold the reaction for 2 h, and then cool down to room temperature to obtain a colorless to light yellow transparent liquid, which is the reactive emulsifier.

[0143] The molar ratio of the hydrogen - terminated silicone oil to the allyl polyether is 1.0:2.2;

[0144] The catalyst is 0.5% of the mass of the hydrogen - terminated silicone oil;

[0145] Preparation of super-smooth handfeel agent:

[0146] Add 40 g of reactive emulsifier and 200 g of block silicone oil into the emulsifier, turn on the power of the emulsifier, with a rotation speed of 800 r / min, mechanically stir for 0.5 h, then add 4 g of non-ionic surfactant Sasol 1370 (isotridecyl alcohol polyoxyethylene ether) and 0.2 g of glacial acetic acid while stirring, continue to stir for 0.5 h, and slowly drop 1200 g of deionized water within 3 h to obtain a silicone oil emulsion;

[0147] ② Preparation of paraffin emulsion:

[0148] Disperse fatty alcohol polyoxyethylene ether O-3, fatty alcohol polyoxyethylene ether O-9 and fatty alcohol polyoxyethylene ether O-20 in a mass ratio of 2:2:1 to prepare a composite emulsifier.

[0149] Heat and stir solid paraffin to gradually melt it, with the temperature controlled at 80 - 90 °C. Under stirring conditions, slowly drop the emulsifier solution into the melted paraffin (the mass ratio of paraffin to the composite emulsifier is 3:1), the dropping speed should not be too fast, and at the same time keep the stirring speed at 300 - 500 r / min to fully mix paraffin and the emulsifier.

[0150] After dropping the emulsifier solution, continue to stir for a period of time, and then use AMP - 95 with a concentration of 0.9% (Dow Chemical Adjust the pH value of the emulsion to 8

[0151] Under stirring, slowly add deionized water (the mass ratio of paraffin to deionized water is 1:2) to the emulsion to dilute the emulsion to the required concentration. Then cool down and continue to stir, allowing the emulsion to cool naturally to room temperature to make the structure of the emulsion more stable.

[0152] ③ Preparation of water-based delicate handfeel agent:

[0153] Mix and disperse the prepared ① silicone oil emulsion and ② paraffin emulsion evenly according to a mass ratio of 4:6.

[0154] Example 4

[0155] ① Preparation of silicone oil emulsion:

[0156] Preparation of block silicone oil:

[0157] Add the epoxy-terminated silicone oil YK-276-8000 with a relative molecular mass of 8000 (Zhejiang Yingke Chemical Co., Ltd.), aliphatic diamine ED900 (Huntsman Corporation), and isopropyl alcohol (with a dosage of 30% of the total mass of the epoxy-terminated silicone oil and aliphatic diamine) into a four-necked flask, start stirring, and while stirring at a speed of 500 r / min, heat up to 80 - 82 °C and react for 10 h. Then cool to room temperature to obtain a light yellow to golden transparent liquid, which is the block silicone oil.

[0158] The molar ratio of the epoxy-terminated silicone oil to the aliphatic diamine is 1.0:1.2.

[0159] Preparation of the reactive emulsifier:

[0160] Add the hydrogen-terminated silicone oil YK-616-4000 with a relative molecular mass of 4000 (Zhejiang Yingke New Materials Co., Ltd.) and allyl polyether (polyether F10 from Jiangsu Zhongshan Chemical Co., Ltd.) into a four-necked flask, start stirring, and while stirring at a speed of 600 r / min, heat up to 50 °C, add the catalyst chloroplatinic acid, continue to heat up to 120 °C, and after the reaction solution turns transparent, continue to keep the temperature for reaction for 3 h. Then cool to room temperature to obtain a colorless to light yellow transparent liquid, which is the reactive emulsifier.

[0161] The molar ratio of the hydrogen-terminated silicone oil to the allyl polyether is 1.0:2.2;

[0162] The catalyst is 0.5% of the mass of the hydrogen-terminated silicone oil.

[0163] Preparation of the super-smooth handfeel agent:

[0164] Add 30 g of the reactive emulsifier and 200 g of the block silicone oil into an emulsifying machine, turn on the power of the emulsifying machine, stir at a speed of 800 r / min for 0.5 h, then while stirring, add 40 g of non-ionic surfactant AE0-9 and 1 g of glacial acetic acid, continue to stir for 0.5 h, and slowly add 800 g of non-ionic water dropwise within 2.5 h to obtain a silicone oil emulsion.

[0165] ② Preparation of the paraffin emulsion:

[0166] Disperse the Span 80 emulsifier and Tween 80 emulsifier in a mass ratio of 1:2 to prepare a composite emulsifier.

[0167] Heat and stir the solid paraffin to gradually melt it, and control the temperature at 80 - 90 °C. Under the stirring condition Under the conditions of The emulsifier solution is slowly added dropwise to the melted paraffin (the mass of the paraffin and the composite emulsifier (with a ratio of 3:1), the dropping speed should not be too fast, and at the same time, keep the stirring speed at 300 - 500 r / min to fully mix the paraffin and the emulsifier.

[0168] After adding the emulsifier solution dropwise, continue stirring for a period of time, and then adjust the pH value of the emulsion to 8 with 0.9% AMP-95 (Dow Chemical).

[0169] Under stirring, slowly add deionized water (the mass ratio of paraffin to deionized water is 1:2) to the emulsion to dilute the emulsion to the desired concentration. Then cool down and continue stirring to allow the emulsion to cool naturally to room temperature to make the structure of the emulsion more stable.

[0170] ③ Preparation of water-based delicate hand feel agent:

[0171] Mix the prepared ① silicone oil emulsion and ② paraffin emulsion evenly according to the mass ratio of 4:6

[0172] Application Example 1

[0173] Mix 50 parts of water-based treatment agent chemical synthetic material (25% solid content, Zhejiang Xinnuo Polymer Materials Co., Ltd.), 140 parts of water, 2 parts of emulsion-type defoaming agent SY-2130W (Jiangxi Sanyue Polymer Materials Co., Ltd.), 4 parts of polyether-modified polysiloxane wetting and leveling agent SY-8029 (Jiangxi Sanyue Polymer Materials Co., Ltd.), 4 parts of dimethylformamide and 2 parts of low-shear associative polyurethane thickener Anke A50 to obtain a water-based treatment agent;

[0174] Mix again according to 100 parts of the water-based treatment agent and 1 part of the water-based delicate auxiliary agent prepared in Example 1 to obtain a water-based delicate treatment agent slurry.

[0175] Apply the water-based delicate hand feel treatment agent slurry on the surface of the water-based dry synthetic leather by scraping with a 100-mesh roller of a three-plate printing machine.

[0176] Application Example 2

[0177] Prepare the water-based treatment agent slurry according to the preparation method of Application Example 1, the difference is:

[0178] Replace the water-based delicate auxiliary agent prepared in Example 2 with the water-based delicate auxiliary agent prepared in Example 1.

[0179] Application Example 3

[0180] Prepare the water-based treatment agent slurry according to the preparation method of Application Example 1, the difference is:

[0181] Replace the water-based delicate auxiliary agent prepared in Example 1 with the water-based delicate auxiliary agent prepared in Example 3.

[0182] Application Example 4

[0183] Prepare the water-based treatment agent slurry according to the preparation method of Application Example 1, the difference is:

[0184] Replace the aqueous soft and delicate hand feeling agent prepared in Example 1 with the aqueous soft Softening aid

[0185] Comparative Application Example 1

[0186] Prepare the aqueous treatment agent leather according to the preparation method of Application Example 1, with the difference that:

[0187] Do not add the softening aid for cotton

[0188] Application Example 5

[0189] Mix 100 parts of Huafeng aqueous resin (35% solid content) JF-PDY-1821H, 1 part of defoamer SY-2130W (Jiangxi Sanyue High Molecular Materials Co., Ltd.), 0.5 part of wetting and leveling agent SY-8029 (Jiangxi Sanyue High Molecular Materials Co., Ltd.), 3 parts of aqueous black paste PH-930A (Jiangxi Sanyue High Molecular Materials Co., Ltd.) and 2 parts of associative polyurethane thickener SY-1052 (Jiangxi Sanyue High Molecular Materials Co., Ltd.) to obtain an aqueous dry masterbatch; mix again according to 100 parts of the aqueous dry masterbatch and 1 part of the aqueous softening aid for cotton obtained in Example 1 to obtain an aqueous dry slurry.

[0190] Scrape the aqueous dry slurry on the release paper, transfer it to the wet BASE after baking in an oven at 100 °C to obtain an aqueous synthetic leather.

[0191] Application Example 6

[0192] Prepare the aqueous dry slurry according to the preparation method of Application Example 5, with the difference that:

[0193] Replace the aqueous softening aid for cotton prepared in Example 1 with the aqueous softening aid prepared in Example 2.

[0194] Application Example 7

[0195] Prepare the aqueous dry agent slurry according to the preparation method of Application Example 5, with the difference that:

[0196] Replace the aqueous softening aid for cotton prepared in Example 1 with the aqueous softening aid prepared in Example 3.

[0197] Application Example 8

[0198] Prepare the aqueous dry agent slurry according to the preparation method of Application Example 5, with the difference that:

[0199] Replace the aqueous softening aid for cotton prepared in Example 1 with the aqueous softening aid prepared in Example 4.

[0200] Comparative Application Example 2

[0201] Prepare the aqueous dry agent slurry according to the preparation method of Application Example 5, with the difference that:

[0202] Do not add soft touch additives.

[0203] Performance test

[0204] Observe whether the slurries prepared in Application Examples 1 to 3 and Comparative Application Example 1 have a layering phenomenon, and The surface of the synthetic leather was subjected to a tactile comparison, and the records are shown in Table 1 below:

[0205] Table 1 Tactile test results of the synthetic leather in Application Examples 1-3 and Comparative Application Example 1

[0206]

[0207] As can be seen from Table 1, the soft touch of the treating agents prepared in Application Examples 1-3 is better than that of Comparative Application Example 1. However, after the slurry was placed for 24 hours, there was a slight surface wax floating phenomenon in both Application Example 3 and Application Example 4, and there was an obvious wax feeling when touching the surface of the leather sample.

[0208] The surface of the synthetic leather prepared in Application Examples 4-6 and Comparative Application Example 2 was observed and subjected to a tactile comparison, and the records are shown in Table 2 below:

[0209] Table 2 Tactile test results of the synthetic leather in Application Examples 5-8 and Comparative Application Example 2

[0210]

[0211] As can be seen from Table 2, the soft touch and softness of the treating agents prepared in Application Examples 5-8 are better than those of Comparative Application Example 2.

[0212] The above are only the preferred embodiments of the present invention. It should be noted that for those of ordinary skill in the art, without departing from the principle of the present invention, several improvements and refinements can be made, and these improvements and refinements should also be regarded as the protection scope of the present invention.

Claims

1. A super soft and tender feel agent, characterized in that: Including silicone oil emulsion and paraffin emulsion; The silicone oil emulsion comprises the following raw materials by mass fraction: The reactive emulsifier has hydroxyl groups at both ends of the molecule; The paraffin wax emulsion comprises the following raw materials by mass fraction: Paraffin, emulsifier, alkaline pH adjuster and water; The mass ratio of the paraffin wax to the emulsifier is 3 to 4:1; The mass ratio of paraffin wax to water is 1:1-3; The pH value of the paraffin emulsion is 5-9.

2. The super soft and tender feel agent according to claim 1, characterized in that: The mass fraction of the silicone oil emulsion in the super soft and tender feel agent is 40-70%.

3. The super soft and tender feel agent according to claim 1, characterized in that: The preparation method of the block silicone oil comprises the following steps: The block silicone oil is obtained by mixing epoxy-terminated silicone oil, aliphatic diamine and polar organic solvent and performing a ring-opening reaction.

4. The super soft and tender feel agent according to claim 3, characterized in that: The molar ratio of the terminal epoxy silicone oil to the aliphatic diamine is 1:0.5-2; The relative molecular mass of the epoxy-terminated silicone oil is 4000-20000; the relative molecular mass of the aliphatic diamine is 200-2000.

5. The super soft and tender feel agent according to claim 1, characterized in that: The preparation method of the reactive emulsifier comprises the following steps: The reactive emulsifier is obtained by mixing hydrogen-terminated silicone oil, allyl polyether and an inorganic catalyst to carry out a silylation reaction.

6. The super soft and tender feel agent according to claim 5, characterized in that: The molar ratio of the terminal hydrogen silicone oil to the allyl polyether is 1.0:1.0-2.2; The relative molecular mass of the terminal hydrogen-containing silicone oil is 2000-6000; The relative molecular mass of the allyl polyether is 200-5000.

7. The super soft and tender feel agent according to claim 1, characterized in that: The emulsifier includes one or more of OP-10, Span emulsifier, Tween emulsifier, fatty alcohol polyoxyethylene ether and stearic acid glyceryl ester.

8. The super soft and tender feeling agent according to claim 7, characterized in that: The Span emulsifier is Span 80, the Tween emulsifier is Tween 80, and the fatty alcohol polyoxyethylene ethers are fatty alcohol polyoxyethylene ether O-3, fatty alcohol polyoxyethylene ether O-9 and fatty alcohol polyoxyethylene ether O-20.

9. The super soft and tender feeling agent according to claim 8, characterized in that: When the emulsifier is Span 80 and Tween 80, the mass ratio of Span 80 to Tween 80 is 1:2; When the emulsifier is fatty alcohol polyoxyethylene ether O-3, fatty alcohol polyoxyethylene ether O-9 and fatty alcohol polyoxyethylene ether O-20, the mass ratio of fatty alcohol polyoxyethylene ether O-3, fatty alcohol polyoxyethylene ether O-9 and fatty alcohol polyoxyethylene ether O-20 is 2:2:

1.

10. Use of the super soft and tender feel agent according to any one of claims 1 to 9 in water-based surface treatment of PU synthetic leather.

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