Low-temperature forming, soft-feeling polyurethane fluorine-free fabric waterproof agent and its manufacturing method and application

Abstract

The application relates to the technical field of textile functional finishing agents, and discloses a low-temperature forming, soft-hand polyurethane fluorine-free fabric waterproof agent and a manufacturing method and application thereof, wherein the polyurethane fluorine-free fabric waterproof agent comprises, in mass fraction, 10-20% of polyurethane polymer, 2-10% of polyurethane modified organic silicon, 10-20% of solvent, 2-5% of organic cosolvent, 1-5% of emulsifier, 50-70% of deionized water, and 0.2-1% of pH regulator. The polyurethane fluorine-free waterproof agent is mainly applied to fabric treatment, can be formed at a lower temperature, and has the advantages of good water-repellent performance, low hand-grabbing trace, soft hand feeling, high coating peeling performance and the like.

Description

Technical Field

[0001] This invention relates to the field of functional finishing agents for textiles, specifically to a low-temperature molding, soft-hand-feel polyurethane fluorine-free fabric waterproofing agent, its manufacturing method, and its application as a hydrophobic agent. Background Technology

[0002] To achieve hydrophobicity or oleophobicity in textiles, aqueous or solvent-containing formulations containing silicone oil, paraffin wax, fatty acid-modified melamine resins, fluoropolymers, and other additives are typically used. Textiles finished in this way are waterproof, splash-proof, or moisture-proof.

[0003] Formulas based on fluoropolymers additionally provide stain resistance and oleophobicity (oil repellency), while formulas based on paraffin, fatty acids, fatty acid-modified melamine resins, silicone resins, and octadecyl acrylate polymers only provide hydrophobicity (water repellency). However, fluoropolymer-based formulas are expensive due to their energy-intensive manufacturing process and are suspected of being environmentally and human-toxic, making their use, especially in the clothing industry, increasingly viewed with criticism. Paraffin has poor water-repellent and waterproof properties; melamine resins have a stiff feel and moderate water-repellent effect; silicone resins and octadecyl acrylate have better water-repellent and hydrophobic effects, but silicone resins require a larger quantity, and octadecyl acrylate has a stiff feel. Polyurethane, with its unique structure, has superior overall performance.

[0004] Patent CN103628324A describes a formulation for a fiber finishing waterproofing agent, wherein the formulation comprises a polyisocyanate-functionalized compound and a reaction product, which are then formulated with paraffin. All embodiments contain hydrophilic residues, which significantly affect the waterproofing performance of fabrics. Paraffin also has a significant impact on the feel of the fabric, and the patent describes the waterproofing performance of fabrics treated at a high temperature of 180°C, without explicitly stating its low-temperature performance.

[0005] Patent CN105377935A describes a method for manufacturing a polyurethane fluorine-free waterproofing agent, which has good waterproofing performance, but does not involve silicone modification, nor does it disclose its low-temperature molding waterproofing performance and hand feel.

[0006] Patent CN106632964A describes a method for manufacturing a fluorine-free waterproofing agent modified with amino silicone oil, but it only discloses its waterproofing performance without mentioning its impact on the feel of the fabric or its low-temperature molding performance. Furthermore, the reaction between amino groups and isocyanates is relatively fast, making it difficult to control in industrial production.

[0007] Patent CN114541148A describes a method for manufacturing a blocked isocyanate-modified silicone wax waterproofing synergist, and describes how the product significantly improves the feel of the skin. However, this waterproofing synergist requires blocking the isocyanate before reacting with silicone, making the manufacturing method quite complex, and it is difficult to guarantee the number of blocked ends on each isocyanate molecule. If some molecules are completely blocked while others are not, the reaction with silicone can easily lead to gelation.

[0008] Patent US20240301121A1 describes a fluorine-free polyurethane waterproofing agent composed of esters, isocyanates, and hydroxyl silicone oil. This patent discloses its waterproofing properties but does not disclose low-temperature molding. Furthermore, this hydroxyl silicone oil is not modified with long-chain alkyl isocyanates, which would reduce its waterproofing performance.

[0009] Patent CN112127156A describes a polyurethane waterproofing agent modified with a fluorinated siloxane coupling agent, which has a soft feel and good waterproofing effect, but the fluorine content of this waterproofing agent does not conform to the future trend of environmental protection.

[0010] Patent CN115698221A describes a method for preparing a fluorine-free waterproofing agent using acrylic acid and polyurethane, combined with a crosslinking agent containing blocked isocyanate, which shows good waterproofing properties. However, it does not disclose low-temperature performance and feel, and the polyurethane-based waterproofing agent has not undergone silicone modification, making it difficult to achieve outstanding performance in terms of feel. Summary of the Invention

[0011] (a) Technical problems to be solved

[0012] To address the shortcomings of existing technologies, this invention provides a low-temperature molding, soft-hand-feel polyurethane fluorine-free fabric waterproofing agent. This product offers advantages such as a good hand feel, low-temperature processing, and excellent waterproofing performance, meeting the needs of fabrics requiring high-temperature performance and a comfortable hand feel for waterproofing applications.

[0013] (II) Technical Solution

[0014] To achieve the above objectives, the present invention provides the following technical solution:

[0015] A low-temperature molding, soft-touch polyurethane fluorine-free fabric waterproofing agent, comprising, by mass fraction:

[0016] Polyurethane polymer: 10%-20%

[0017] Polyurethane-modified silicone: 2%-10%

[0018] Solvent: 10%-20%

[0019] Organic cosolvent: 2-5%

[0020] Emulsifier: 1%-5%

[0021] Deionized water: 50%-70%

[0022] pH adjuster: 0.2%-1%.

[0023] Furthermore, the polyurethane polymer has the following general formula:

[0024] ,

[0025] The polyurethane polymer is composed of , and It is prepared by reaction under the action of a catalyst.

[0026] The catalyst is preferably bismuth neodecanoate or dibutyltin dilaurate, and the content of the catalyst is 0.05%-0.2% by mass fraction.

[0027] Furthermore, the polyurethane-modified organosilicon has the following general formula:

[0028] ,

[0029] The polyurethane-modified organosilicon is made from... and It is prepared by reaction under the action of a catalyst.

[0030] The catalyst is preferably bismuth neodecanoate or dibutyltin dilaurate, and the content of the catalyst is 0.05%-0.2% by mass fraction.

[0031] Preferably, the Polyisocyanates include aliphatic diisocyanates, triisocyanates, and higher polyisocyanates, or aromatic diisocyanates, triisocyanates, and higher polyisocyanates, or mixtures thereof. Examples include aromatic or aliphatic diisocyanates, aromatic or aliphatic triisocyanates, aromatic or aliphatic polymeric isocyanates or mixtures thereof, aromatic and aliphatic diisocyanates, aromatic and aliphatic triisocyanates, and aromatic and aliphatic polymeric isocyanates. Specifically, these can be 2,4-toluene diisocyanate copolymers with trimethylolpropane, hexamethylene diisocyanate biuret form, hexamethylene diisocyanate polyisocyanate polyisocyanate, polymethylene polyphenyl isocyanate (PAPI), and other polyisocyanurates.

[0032] Preferably, the It is an octadecyl isocyanate with the following structural formula:

[0033] .

[0034] Preferably, the It is a long-chain alkyl diol, where R3 is a long-chain alkyl group. The long-chain alkyl diol is any one of glyceryl monostearate, glyceryl monostearate, and glyceryl distearate, or a mixture of both, with distilled-grade glyceryl monostearate preferred. It is not limited to esters formed from stearic acid and glycerol, but also includes esters formed from palmitic acid, silicic acid, isostearic acid, etc., with glycerol.

[0035] Preferably, the It is a polyhydroxy polydimethylsiloxane with m numbering from 1 to 100 and n numbering from 1 to 50, wherein R4 is an alkyl group.

[0036] Preferably, the number of n is 20-40, wherein R4 is an alkyl group, such as CH2-; CH2-CH2- or other short-chain alkyl groups with 1-8 carbon atoms.

[0037] Preferably, the solvent is methyl isobutyl ketone.

[0038] Preferably, the organic co-solvent is any one or more of ethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, ethylene glycol butyl ether, diethylene glycol butyl ether, dipropylene glycol butyl ether, and dipropylene glycol methyl ether.

[0039] Preferably, the emulsifier is a mixture of cationic and nonionic emulsifiers. The cationic emulsifier is an ammonium chloride-type cationic emulsifier or an amide-type cationic emulsifier. The nonionic emulsifier is one or a mixture of long-chain isomeric alkyl alcohol polyoxyethylene ether and benzene ring-containing polyoxyethylene ether.

[0040] Preferably, the pH adjuster is glacial acetic acid.

[0041] Preferably, the catalyst used in the polyurethane synthesis process is dibutyltin dilaurate or bismuth neodecanoate.

[0042] This invention also discloses a method for preparing a low-temperature molded, soft-to-the-touch polyurethane fluorine-free fabric waterproofing agent, comprising the following steps:

[0043] Step S1: Polyurethane polymer synthesis

[0044] Add ODI to a three-necked flask equipped with a top stirrer, thermocouple, and reflux condenser. and Add solvent MIBK and heat to 90°C. React for 3 hours with an appropriate catalyst, and continue until the NCO peak disappears using infrared spectroscopy. Then add more polyisocyanate and continue the reaction for another 3 hours. Measure the NCO peak again using infrared spectroscopy until it disappears. Cool to 60°C for later use.

[0045] The obtained polyurethane polymer has the following general formula:

[0046] .

[0047] Preferably, It is distilled glyceryl monostearate or glyceryl monostearate and glyceryl distearate.

[0048] Step S2: Polyurethane-modified organosilicon synthesis of PU-SI

[0049] Add ODI and [other ingredients] to a three-necked flask equipped with a top stirrer, thermocouple, and reflux condenser. ,

[0050] Add solvent MIBK and heat to 90℃. React for 3 hours with an appropriate amount of catalyst. Detect the NCO peak with infrared spectroscopy until it disappears. Then cool to 60℃ for later use.

[0051] Preferably, It is a lateral polyhydroxy polydimethylsiloxane with 20 m and 30 n, and R4 is a short carbon chain alkyl group with 4 carbons.

[0052] Step S3: Emulsion preparation

[0053] Water, emulsifiers (agricultural emulsion 600, OXO-1310 and di-cocoyl dimethyl ammonium chloride), glacial acetic acid, and organic cosolvent (dipropylene glycol) are mixed in a certain proportion, heated to 60°C and stirred evenly.

[0054] Step S4, Emulsification and Homogenization

[0055] The synthesized polyurethane polymer PU, polyurethane-modified silicone PU-SI, and emulsion were mixed at 60°C and homogenized four times under a pressure of 30 MPa in a high-pressure homogenizer.

[0056] Step S5, Desolventizing

[0057] The solvent MIBK is removed from the above homogenized liquid in a vacuum environment to obtain a fluorine-free waterborne polyurethane waterproofing agent with a solid content of 21%.

[0058] This invention also discloses the application of a low-temperature molding, soft-to-the-touch polyurethane fluorine-free fabric waterproofing agent as a hydrophobic agent. It should be specifically noted that the low-temperature molding described in this invention refers to the molding temperature of the polyurethane fluorine-free fabric waterproofing agent during processing and use, which is between 120℃ and 140℃.

[0059] (III) Beneficial Effects

[0060] Compared with existing technologies, this invention provides a fluorine-free polyurethane waterproofing agent obtained by copolymerizing polyurethane with long-chain alkyl esters, while simultaneously modifying the side-side polyhydroxy organosilicon compounds with long-chain alkyl isocyanates, and then emulsifying the mixture in water with an emulsifier. This product has advantages such as good hand feel, low-temperature processing and molding, and excellent waterproofing effect, and can meet the waterproofing requirements of fabrics with high requirements for low temperature and hand feel.

[0061] When the polyurethane polymer of this invention is used as a fabric waterproofing agent, it can be processed and molded at around 120℃-140℃. Compared with the traditional fluorine-free waterproofing agent processing temperature of 150℃-180℃, it has a lower molding temperature and still maintains good waterproof and hydrophobic effects after processing at a lower temperature. Low-temperature molding helps to save energy and also better avoids damage to some fibers caused by high temperatures, thus maintaining the original properties of the fabric. Detailed Implementation

[0062] The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the tables in the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments.

[0063] A low-temperature molding, soft-touch polyurethane fluorine-free fabric waterproofing agent, comprising, by mass fraction:

[0064] Polyurethane polymer: 10%-20%, polyurethane-modified silicone: 2%-10%, solvent: 10%-20%, organic co-solvent: 2-5%, emulsifier: 1%-5%, deionized water: 50%-70%, pH adjuster: 0.2%-1%. Tests can be conducted with polyurethane polymer contents of 10%, 12%, 15%, 18%, and 20%, and with polyurethane-modified silicone contents of 2%, 4%, 6%, 8%, and 10%.

[0065] Specific implementation methods

[0066] Step S1: Preparation of polyurethane-modified silicone (PU-SI) reaction solution

[0067] Following the above preparation method, polyhydroxyl polydimethylsiloxane modified polyurethane PU-SI was first prepared, and specific examples are as follows:

[0068] Add approximately 35 g of ODI, approximately 100 g of side-positioned polyhydroxy polydimethylsiloxane, and approximately 150 g of MIBK solvent to a three-necked flask equipped with a top stirrer, thermocouple, and reflux condenser. Then heat to 90°C and react for 3 hours in the presence of a suitable catalyst, continuing until the NCO peak disappears using infrared spectroscopy. Cool to 60°C for later use. This yields the polyhydroxy polydimethylsiloxane-modified polyurethane (PU-SI) reaction solution.

[0069] Step S2: Preparation of polyurethane polymer (PU) and fluorine-free polyurethane waterproofing agent

[0070] The specific embodiments of the polyurethane polymer-based fluorine-free waterproofing agent, according to the manufacturing method of the fluorine-free waterproofing agent, are as follows:

[0071] Example 1

[0072] In a three-necked flask equipped with a top stirrer, thermocouple, and reflux condenser, add 8 parts ODI, 26 parts distilled glyceryl mono- and glyceryl distearate, and 30.8 parts solvent MIBK. Heat to 90°C and react for 3 hours with 0.1 parts bismuth neodecanoate catalyst, until the NCO peak disappears as detected by infrared spectroscopy. Then add 35 parts toluene diisocyanate adduct and heat to 85°C. Add another 0.1 parts bismuth neodecanoate catalyst and react for 3 hours, again detecting the NCO peak with infrared spectroscopy until it disappears. Cool to 60°C for later use to obtain the polyurethane reaction solution. Add 60 parts PU-SI reaction solution to the above reaction solution and stir at 60°C for half an hour.

[0073] Meanwhile, in another bottle, prepare an emulsion consisting of 400 parts water, emulsifier OXO-1310, agricultural emulsion 600, dimethyl ammonium chloride, acetic acid, and dipropylene glycol as a co-solvent, and heat it to 60°C while stirring until homogeneous. Add the above polyurethane reaction solution and PU-SI reaction solution to the emulsion and stir rapidly. Homogenize four times using a high-pressure homogenizer, and after solvent removal, obtain a polyurethane emulsion with a solid content of 21%.

[0074] Example 2

[0075] The process was the same as above. Using 14 parts ODI, 24 parts distilled glyceryl monostearate, 29.3 parts solvent MIBK, 35 parts toluene diisocyanate adduct, and 1.5 parts 3,5-dimethylpyrazole, a polyurethane reaction solution was obtained after reaction. The catalyst was dibutyltin dilaurate, used in the same amount as in Example 1. 60 parts PU-SI reaction solution were added to the above reaction solution, and the same emulsification and solvent removal methods were used to obtain a polyurethane emulsion with a solid content of 21%.

[0076] Example 3

[0077] The process was the same as above. Using 22 parts ODI, 28 parts distilled glyceryl monostearate, 15.3 parts solvent MIBK, 33 parts toluene diisocyanate adduct, and 1.5 parts 3,5-dimethylpyrazole, a polyurethane reaction solution was obtained after reaction. The type and amount of catalyst were the same as in Example 1. 60 parts PU-SI reaction solution were added to the above reaction solution, and the same emulsification and solvent removal methods were used to obtain a polyurethane emulsion with a solid content of 21%.

[0078] Example 4

[0079] The process was the same as above. Using 14 parts ODI, 28 parts distilled glyceryl monostearate, 34.3 parts solvent MIBK, 22 parts hexamethylene diisocyanate trimer, and 1.5 parts 3,5-dimethylpyrazole, a polyurethane reaction solution was obtained after reaction. The type and amount of catalyst were the same as in Example 1. 60 parts PU-SI reaction solution were added to the above reaction solution, and the same emulsification and solvent removal methods were used to obtain a polyurethane emulsion with a solid content of 21%.

[0080] Comparison Samples

[0081] Comparison Sample 1: Polyurethane fluorine-free waterproofing agent provided by Fuco New Materials (Shanghai) Co., Ltd.

[0082] The product name is ECO-BARRIER@ X-9

[0083] Comparative Sample 2: The polyurethane fluorine-free waterproofing agent described in Example C-8 of Patent CN115698221A.

[0084] The following is a description of the raw materials used in the embodiments of this invention:

[0085]

[0086] The polyurethane emulsion prepared in the embodiments of the present invention was tested together with the comparative example. The test method is as follows:

[0087] 1. Fabric treatment - padding

[0088] Prepare 40 grams per liter of water-based polyurethane waterproofing agent, roll the fabric through the rolling mill at a speed of 6 RPM and a pressure of about 3 kg, then set it in an oven at 130°C for 150 seconds and in an oven at 170°C for about 70 seconds.

[0089] 2. Water repellency test

[0090] To verify the waterproofing effect of textiles treated with the fluorine-free waterproofing agent described in this invention, a standard method can be used for comparison. The standard method is to examine the waterproofing effect according to the national standard GB 4745—1997, which is briefly described below.

[0091] Cut a 22×18cm sample, clamp it firmly, and mount it on a fixed base at a 45° angle to the horizontal. Quickly and steadily pour 250mL (20±2℃) distilled or deionized water into the funnel, and spray it evenly and continuously towards the center of the sample through a nozzle at a distance from the center of the sample for 25–30 seconds. After spraying, quickly remove the clamp, turn the sample face down to a horizontal position, gently tap it twice, observe the degree of wettability of the sample, and then evaluate its grade by describing it in words and comparing it with pictures.

[0092] The rating criteria are as follows:

[0093] Level 1 – The entire surface being sprayed is wetted.

[0094] Level 2 – Half of the surface being wetted, meaning the total area of ​​the small wetted areas is approximately half of the total area.

[0095] Level 3 – The surface being wetted is only a small area and is not continuous.

[0096] Level 4 – The surface being sprayed is not wetted, but small water droplets are present.

[0097] Level 5 – The surface being sprayed is not wetted and there are no small water droplets.

[0098] 3. Referencing the AATCC EP5 feel rating, the following levels are provided:

[0099] Level 1 – Feels stiffer than untreated fabric

[0100] Level 2 – Feels slightly stiffer than untreated fabric

[0101] Level 3 – Feels similar to untreated fabric

[0102] Level 4 – Feels slightly softer than untreated fabric

[0103] Level 5 – Feels softer than untreated fabrics

[0104] 4. Selection of fabrics for testing

[0105] Fabrics selected: Spring spun yarn, 290T polyester taffeta, cotton, memory spun yarn, polyester / cotton blend, nylon spun yarn

[0106] 5. Waterproofing agent stability test

[0107] Use a centrifuge at 3000 RPM for 15 minutes and observe whether there is any sediment at the bottom of the centrifuge dish.

[0108] Test Results

[0109] 1. Low-temperature waterproof test

[0110] The above-described embodiments were prepared with water to form an aqueous solution of 40 g / L. The fabric described in this application and the comparative sample were then impregnated with the aqueous polyurethane solution using a rolling mill, followed by oven treatment at 130°C for approximately 150 seconds. The waterproof performance and hand feel were then tested as follows:

[0111] The low-temperature water-repellent performance test data are as follows:

[0112]

[0113] 2. High-temperature waterproof test

[0114] The above-described embodiments were prepared into a 40 g / L aqueous solution with water. The fabric described in this application and the comparative sample were then impregnated with the aqueous polyurethane solution using a rolling mill, followed by oven treatment at 170°C for approximately 70 seconds. The waterproof performance and hand feel were then tested. The high-temperature water repellency data are as follows:

[0115]

[0116] 3. Hand feel test

[0117]

[0118] As can be seen from the above low-temperature water repellency test, Examples 1, 2, and 3 have good low-temperature molding properties and better low-temperature waterproofing than traditional polyurethane fluorine-free waterproofing agents (Fokco New Materials (Shanghai) Co., Ltd.: brand name ECO-BARRIER@ X-9 and the polyurethane fluorine-free waterproofing agent described in Example C-8 of patent CN115698221A).

[0119] During the high-temperature treatment process, Examples 1, 2, and 3 also exhibited waterproofing performance similar to that of traditional polyurethane fluorine-free waterproofing agents.

[0120] As can be seen from the above fabric hand feel test, Examples 1 and 2 have a relatively soft hand feel compared to traditional fluorine-free waterproofing agents, and are closer to untreated fabrics. This invention successfully developed a fluorine-free waterproofing agent for fabrics by synthesizing a water-based polyurethane polymer and combining it with a polyhydroxy silicone-modified polyurethane polymer. This agent exhibits excellent low-temperature waterproofing performance and a relatively soft hand feel.

[0121] A method for preparing a low-temperature molded, soft-to-the-touch polyurethane fluorine-free fabric waterproofing agent, including the following steps:

[0122] Step S1: Polyurethane polymer synthesis

[0123] Add to a three-necked flask equipped with a top stirrer, thermocouple, and reflux condenser. , , In this embodiment, It is the biuret type of hexamethylene diisocyanate and the polyisocyanurate type of hexamethylene diisocyanate. Distilled glyceryl monostearate or glyceryl monostearate and glyceryl distearate were reacted in MIBK solvent at 90°C for 3 hours with an appropriate catalyst, until the NCO peak disappeared using infrared spectroscopy. Then, additional polyisocyanate was added and the reaction continued for another 3 hours, with infrared spectroscopy again used until the NCO peak disappeared. The mixture was then cooled to 60°C for later use. In this example, the catalyst was bismuth neocaprate, at a mass fraction of 0.08% of the raw material content.

[0124] The obtained polyurethane polymer has the following general formula:

[0125] .

[0126] Step S2: Polyurethane-modified organosilicon synthesis of PU-SI

[0127] Add to a three-necked flask equipped with a top stirrer, thermocouple, and reflux condenser. and , The reaction mixture is a side-positioned polyhydroxy polydimethylsiloxane with 20 m and 30 n atoms, where R4 is a short-chain alkyl group with 4 carbon atoms. The solvent is MIBK. The reaction is carried out at 90°C for 3 hours with a suitable catalyst, and the reaction continues until the NCO peak disappears as detected by infrared spectroscopy. The mixture is then cooled to 60°C for later use. In this example, the catalyst is bismuth neodecanoate, with a mass fraction of 0.1% of the raw material content.

[0128] Step S3: Emulsion preparation

[0129] Water, emulsifiers (agricultural emulsion 600, OXO-1310 and di-cocoyl dimethyl ammonium chloride), glacial acetic acid, and organic cosolvent (dipropylene glycol) are mixed in a certain proportion, heated to 60°C and stirred evenly.

[0130] Step S4, Emulsification and Homogenization

[0131] The synthesized polyurethane polymer PU, polyurethane-modified silicone PU-SI, and emulsion were mixed at 60°C and homogenized four times under a pressure of 30 MPa in a high-pressure homogenizer.

[0132] Step S5, Desolventizing

[0133] The solvent MIBK is removed from the above homogenized liquid in a vacuum environment to obtain a fluorine-free waterborne polyurethane waterproofing agent with a solid content of 21%.

[0134] In other embodiments, the polyisocyanate in step S1 above can also be a copolymer of 2,4-toluene diisocyanate and trimethylolpropane, polymethylene polyphenyl isocyanate (PAPI), or other polyisocyanurates.

[0135] In other embodiments, the long-chain alkyl diol in step S1 above can also be an esterified product formed by palmitic acid, silicic acid, isostearic acid, etc., with glycerol.

[0136] In other embodiments, the Polyisocyanates include aliphatic diisocyanates, triisocyanates, and higher-order polyisocyanates, or aromatic diisocyanates, triisocyanates, and higher-order polyisocyanates, or mixtures of both. Examples include mixtures of aromatic diisocyanates and aliphatic triisocyanates, mixtures of aromatic polymeric isocyanates and aliphatic polymeric isocyanates, and mixtures of aromatic diisocyanates and aliphatic polymeric isocyanates. Specifically, these can be 2,4-toluene diisocyanate copolymers with trimethylolpropane, hexamethylene diisocyanate biuret form, hexamethylene diisocyanate polyisocyanate polyisocyanate, polymethylene polyphenyl isocyanate (PAPI), and other polyisocyanurates.

Claims

1. A low-temperature molded, soft-to-the-touch polyurethane fluorine-free fabric waterproofing agent, characterized in that: According to quality score, including: Polyurethane polymer: 10%-20% Polyurethane-modified silicone: 2%-10% Solvent: 10%-20% Organic cosolvent: 2-5% Emulsifier: 1%-5% Deionized water: 50%-70% pH adjuster: 0.2%-1%; The polyurethane polymer has the following general formula: ， The polyurethane polymer is composed of , and , It is prepared by reaction under the action of a catalyst. The polyurethane-modified organosilicon has the following general formula: ， The polyurethane-modified organosilicon is made from... and It is prepared by reaction under the action of a catalyst. The It is an octadecyl isocyanate with the following structural formula: ， The It is a diol containing long-chain alkyl groups, and R3 is a long-chain alkyl group.

2. The low-temperature molding, soft-to-the-touch polyurethane fluorine-free fabric waterproofing agent according to claim 1, characterized in that: The It is a polyisocyanate, including aliphatic di, tri and higher polyisocyanates, or aromatic di, tri and higher polyisocyanates, or mixtures of both.

3. The low-temperature molding, soft-to-the-touch polyurethane fluorine-free fabric waterproofing agent according to claim 1, characterized in that: The long-chain alkyl diol is any one of glyceryl monostearate, glyceryl monostearate, and glyceryl distearate, or a mixture of both.

4. The low-temperature molding, soft-to-the-touch polyurethane fluorine-free fabric waterproofing agent according to claim 1, characterized in that: The It is a polyhydroxy polydimethylsiloxane with m numbering from 1 to 100 and n numbering from 1 to 50, wherein R4 is an alkyl group.

5. The low-temperature molding, soft-to-the-touch polyurethane fluorine-free fabric waterproofing agent according to claim 1, characterized in that: The solvent is methyl isobutyl ketone.

6. The low-temperature molding, soft-to-the-touch polyurethane fluorine-free fabric waterproofing agent according to claim 1, characterized in that: The organic co-solvent is any one or more of ethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, ethylene glycol butyl ether, diethylene glycol butyl ether, dipropylene glycol butyl ether, and dipropylene glycol methyl ether.

7. The low-temperature molding, soft-to-the-touch polyurethane fluorine-free fabric waterproofing agent according to claim 1, characterized in that: The emulsifier is a mixture of cationic and nonionic emulsifiers.

8. The low-temperature molding, soft-to-the-touch polyurethane fluorine-free fabric waterproofing agent according to claim 1, characterized in that: The pH adjuster is glacial acetic acid.

9. The low-temperature molding, soft-to-the-touch polyurethane fluorine-free fabric waterproofing agent according to claim 1, characterized in that: The catalyst is dibutyltin dilaurate or bismuth neodecanoate.

10. The low-temperature molding, soft-to-the-touch polyurethane fluorine-free fabric waterproofing agent according to claim 1, characterized in that: The processing and molding temperature for polyurethane fluorine-free fabric waterproofing agents is 120℃-140℃.

11. The application of the low-temperature molding, soft-to-the-touch polyurethane fluorine-free fabric waterproofing agent of any one of claims 1-10 as a hydrophobic agent.

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