A kind of acrylate fluorine-free waterproof agent and its application

Abstract

The present invention relates to the technical field of functional finishing agents for textiles, and discloses an acrylic ester fluorine-free waterproofing agent, comprising the following components in mass percentage: 25-35% of fluorine-free copolymer, 1-5% of surfactant, 0.2-0.5% of acid regulator, 5-10% of organic solvent, and the rest being water. Aiming at the defects of insufficient water resistance and washability of existing acrylic ester fluorine-free waterproofing agents on textiles, as well as poor hand feel and serious hand scratches, a fluorine-free waterproofing agent is prepared, which has more excellent water resistance, and does not need to be combined with a cross-linking agent or copolymerized vinyl chloride / vinylidene chloride to give textiles a durable waterproof effect. At the same time, a better hand feel can be obtained without compounding silicone oil or silicone resin, and the hand scratch phenomenon is significantly improved, avoiding the negative impact of the compounding of fluorine-free waterproofing agents, cross-linking agents and other additives on emulsion stability and other properties, and also avoiding the potential threats and process uncertainties brought by the use of vinyl chloride, making the polymerization process simpler and safer.

Description

Technical Field

[0001] The invention relates to the technical field of functional finishing agents for textiles, in particular to an acrylic ester fluorine-free waterproofing agent and application thereof. Background Art

[0002] Waterproof finishing involves many application areas of textiles, such as jackets, tents, luggage fabrics and umbrellas. Waterproof finishing agents can be divided into two categories: fluorine-containing and fluorine-free. Among them, fluorocarbon finishing agents can give textiles excellent water and oil resistance, especially C8 waterproofing agents, but due to the harmfulness of PFOA / PFOS, European and American countries have explicitly banned the use of C8 waterproofing agents. After C8, PFAS has also received attention from the international community, so the use of C6 waterproofing agents has also been gradually restricted. Compared with fluorine-containing waterproofing agents, fluorine-free waterproofing agents are more environmentally friendly and safer, so they will definitely become the mainstream in the field of waterproof finishing.

[0003] Fluorine-free waterproofing agents mainly include three categories: acrylates, polyurethanes and silicones. Silicone waterproofing agents have excellent hand feel, but their waterproof performance is far from meeting actual needs; polyurethanes have relatively balanced performance, but their process is complicated and the cost is high, making them a "luxury" among fluorine-free waterproofing agents; acrylate waterproofing agents have simple processes, low costs, and acceptable waterproof performance, so they are widely used. Unfortunately, the waterproofness and washability of acrylate fluorine-free waterproofing agents are not outstanding, and there is still a lot of room for improvement. The hand feel of the finished fabric is significantly reduced, and the hand scratch phenomenon is also very serious. At present, the waterproof performance of acrylate fluorine-free waterproofing agents is mostly improved by compounding paraffin-like substances on the market. For example, patent CN106661303A discloses a fluorine-free waterproofing composition, which improves the waterproof performance by adding paraffin with a higher melting point. However, the addition of paraffin is not conducive to the stability of the emulsion and will aggravate the decline in the hand feel of the fabric. In order to improve the feel and hand scratch problems of acrylic fluorine-free waterproofing agents, a common method is to compound silicone oil or silicone resin. For example, patents CN106661303A and CN112955519A both obtain fluorine-free waterproofing compositions with good feel by adding silicone resin. However, this requires full consideration of the compatibility between different components, and the waterproofing performance of the waterproofing agent is usually reduced after compounding with silicone oil or silicone resin. Furthermore, acrylic fluorine-free waterproofing agents currently mainly improve durable waterproofing through the following two ways: (1) adding a cross-linking agent to use in the same bath, such as polyurethane or melamine cross-linking agents; (2) adding vinyl chloride or vinylidene chloride copolymerization, which can further improve the washability of the waterproofing agent. For example, the fluorine-free waterproofing compositions disclosed in patents CN112673128A and CN112955519A both require copolymerization of vinyl chloride or vinylidene chloride and combine with a cross-linking agent to improve washability.

[0004] However, adding crosslinking agents to fluorine-free waterproofing agents may not only affect the stability of the finishing solution, but also aggravate the decline in the feel of textiles and affect basic properties such as strength and color change. Substances such as vinyl chloride are dangerous goods, have the potential to cause cancer, and require high-pressure polymerization, which has more stringent process conditions. Summary of the invention

[0005] 1. Technical issues to be resolved

[0006] In view of the deficiencies of the prior art, the present invention provides an acrylic fluorine-free waterproofing agent and its application. In view of the shortcomings of the existing acrylic fluorine-free waterproofing agents on textiles, such as insufficient water resistance and washability, poor hand feel, and severe hand scratches, a fluorine-free waterproofing agent is prepared, which has more excellent water resistance and can give textiles a durable waterproof effect without the need for the use of a cross-linking agent or copolymerization of vinyl chloride / vinylidene chloride. At the same time, a better hand feel can be obtained without compounding with silicone oil or silicone resin, and the hand scratch phenomenon is significantly improved, avoiding the negative impact of the compounding of fluorine-free waterproofing agents, cross-linking agents, and other additives on the stability of the emulsion and other properties, and also avoiding the potential threats and process uncertainties brought by the use of vinyl chloride, making the polymerization process simpler and safer.

[0007] (II) Technical solution

[0008] To achieve the above purpose, the present invention provides the following technical solution: an acrylic fluorine-free waterproofing agent, comprising the following components in mass percentage: 25-35% fluorine-free copolymer, 1-5% surfactant, 0.2-0.5% acid regulator, 5-10% organic solvent, and the rest water.

[0009] Preferably, the fluorine-free copolymer is obtained by polymerizing the following monomers under the action of an initiator and a chain transfer agent, specifically including:

[0010] (meth)acrylate monomer (a),

[0011] (meth)acrylate monomer (b),

[0012] Modified silicone containing reactive groups (c),

[0013] Modified silicone containing reactive groups (d)

[0014] a blocked isocyanate monomer (e) containing a reactive group,

[0015] The (meth)acrylate monomer (a) has the following general formula:

[0016]

[0017] Wherein, R1 is H or CH3, R2 is a straight-chain alkyl group having 12 or more carbon atoms, preferably 16-22, more preferably 18,

[0018] The (meth)acrylate monomer (b) has the following general formula:

[0019]

[0020] Wherein, R3 is H or CH3, R4 is a straight chain hydrocarbon group with a carbon number of less than 8, and X is an active group such as hydroxyl, amino, or epoxy.

[0021] The modified silicone containing reactive groups (c) has the following general formula:

[0022]

[0023] or

[0024]

[0025] Wherein, Z1 and Z2 are reactive groups that can be copolymerized with acrylate monomers, specifically, (meth)acryloyloxy, (meth)acrylamide and vinyl groups; R5 and R9 are hydrocarbon groups that can contain O, S and N; R8 is an alkyl group that can contain O, S and N; R6, R7, R 10 is methyl or other alkyl or phenyl, m is an integer greater than 0,

[0026] The modified silicone containing reactive groups (d) has the following general formula:

[0027]

[0028] Wherein, Z3 is a reactive group that can be copolymerized with an acrylate monomer, specifically, one of (meth)acryloyloxy, (meth)acrylamide and vinyl, R11 is a hydrocarbon group that can contain O, S, or N, and R 12 , R 13 is methyl or other alkyl or phenyl, n is an integer greater than 0,

[0029] The reactive group-containing blocked isocyanate monomer (e) is obtained by blocking a compound having the following general formula:

[0030] Z4-R 14 -NCO,

[0031] Wherein, Z4 is a reactive group that can be copolymerized with an acrylate monomer, and specifically can be one of (meth)acryloyloxy, (meth)acrylamide and vinyl. 14 A hydrocarbon group may contain O, S, or N.

[0032] Preferably, the end-capping agent used for the monomer e is selected from phenols, caprolactam, acetylacetone, methyl ethyl ketone oxime, imidazoles and pyrazoles, preferably methyl ethyl ketone oxime and pyrazoles.

[0033] Preferably, the mass composition ratio of each monomer in the fluorine-free copolymer is 50-85% of monomer (a), 2-10% of monomer (b), 5-15% of monomer (c), 5-15% of monomer (d), and 2-10% of monomer (e).

[0034] Preferably, the surfactant is one or more of a nonionic surfactant or a cationic surfactant. The nonionic surfactant includes but is not limited to: one or more of Span 40, Span 60, Span 80, polyoxyethylene monostearate, sorbitan monostearate, sorbitan monooleate, polyoxyethylene octadecyl ether, etc.; the cationic surfactant includes but is not limited to: one or more of hexadecyltrimethylammonium bromide, octadecyltrimethylammonium chloride, docosyltrimethylammonium chloride, alkylbenzyldimethylammonium chloride, etc.

[0035] Preferably, the acid regulator is glacial acetic acid, the water is deionized water, and the organic solvent is selected from methyl ethyl ketone, ethylene glycol, propylene glycol and tripropylene glycol.

[0036] Preferably, the preparation method of the acrylic fluorine-free waterproofing agent comprises the following steps:

[0037] S1: Mix the above components in proportion at 60°C and shear homogenize;

[0038] S2: react at 60-80°C for more than 3 hours under the action of an initiator and a chain transfer agent to obtain a fluorine-free waterproofing agent.

[0039] An application of an acrylic ester fluorine-free waterproofing agent, wherein the textiles processed by the fluorine-free waterproofing agent are diluted with water in a certain proportion to form a finishing liquid, and the textiles are subjected to immersion-padding-baking finishing, the baking temperature is 130°C-180°C, preferably 150°C-170°C, and the baking time is 0.5-2 minutes, preferably 1-1.5 minutes.

[0040] (III) Beneficial effects

[0041] Compared with the prior art, the present invention provides an acrylic ester fluorine-free waterproofing agent and its application, which has the following beneficial effects:

[0042] 1. An acrylic ester fluorine-free waterproofing agent and its application. The modified silicone structure is introduced into both the side chain and the main chain of the waterproofing agent molecular structure by copolymerizing an acrylic ester monomer with a modified silicone containing a carbon-carbon double bond. The silicone structure of the side chain can greatly improve the waterproofing performance of the acrylic ester waterproofing agent, while the silicone structure of the main chain can enhance the flexibility of the molecular structure and significantly improve the hand feel and hand scratch phenomenon. By copolymerizing with a blocked isocyanate monomer containing a carbon-carbon double bond, the self-crosslinking of the waterproofing agent and the crosslinking effect on the fiber are enhanced, and the water washing resistance is significantly improved. Even if it is not used in combination with a crosslinking agent and does not copolymerize with a chlorine-containing monomer, a durable waterproofing effect can be obtained.

[0043] 2. This acrylic fluorine-free waterproofing agent and its application avoid the defects of poor emulsion stability and processing stability caused by the use of fluorine-free waterproofing agent and cross-linking agent or silicone softener, and also avoid the potential threats and process uncertainties brought by the use of vinyl chloride, making the polymerization process simpler and safer. BRIEF DESCRIPTION OF THE DRAWINGS

[0044] The accompanying drawings are used to provide a further understanding of the present invention and constitute a part of the specification. Together with the embodiments of the present invention, they are used to explain the present invention and do not constitute a limitation of the present invention. In the accompanying drawings:

[0045] Figure 1 It is a structural schematic diagram of the fluorine-free waterproofing agent of the present invention;

[0046] In the figure: including but not limited to Figure 1 In the structure, R1, R2, R3, R9, R 13 is H or CH3, R4, R 10 , R8 is a hydrocarbon group or an alkyl group which may contain O, S, or N, R6, R7, R 11 , R 12 is methyl or other alkyl or phenyl, X is one of active groups such as hydroxyl, amino and epoxy, Y1, Y2, Y3 are blank or acyloxy or acylamino, Q is an isocyanate-terminated compound, and m and n are integers greater than 0. DETAILED DESCRIPTION

[0047] The technical solutions in the embodiments of the present invention will be described clearly and completely below in conjunction with the drawings in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, rather than all the embodiments.

[0048] Example 1

[0049] 200g of octadecyl acrylate, 10g of hydroxyethyl methacrylate, 20g of single-end acrylate modified silicone, 20g of double-end acrylate modified silicone oil, 10g of 2-[(3,5-dimethyl-1-H-pyrazolyl)carboxyamino]ethyl acrylate, 12g of Span 80, 8g of octadecyltrimethylammonium chloride, 2.5g of glacial acetic acid, 60g of tripropylene glycol, and 480g of deionized water were mixed in a 60°C constant temperature water bath for 30 minutes, and sheared and homogenized at high speed to obtain a pre-emulsion. The pre-emulsion was added to a 1L reactor, and the chain transfer agent n-dodecyl mercaptan and initiator V50 were added. Under continuous stirring and nitrogen protection, the reaction was kept at 60°C for more than 3 hours to obtain a fluorine-free waterproofing agent. The above-mentioned fluorine-free waterproofing agent was diluted with water to 40 g / L, and nylon spunbond 400T, 55 / 45 polyester-cotton and pure cotton fabrics were subjected to dip-padding-drying treatments respectively. The drying conditions were a temperature of 170° C. and a time of 90 s.

[0050] Comparative Example 1

[0051] 220g octadecyl acrylate, 10g hydroxyethyl methacrylate, 20g single-end acrylate modified silicone, 10g 2-[(3,5-dimethyl-1-H-pyrazolyl) carboxylamino] ethyl acrylate, 12g Span 80, 8g octadecyl trimethyl ammonium chloride, 2.5g glacial acetic acid, 60g tripropylene glycol, 480g deionized water, in a 60°C constant temperature water bath for 30 minutes, high-speed shearing and homogenization to obtain a pre-emulsion. The pre-emulsion was added to a 1L reactor, and the chain transfer agent n-dodecyl mercaptan and initiator V50 were added. Under continuous stirring and nitrogen protection, the reaction was kept at 60°C for more than 3 hours to obtain a fluorine-free waterproofing agent. The above-mentioned fluorine-free waterproofing agent was diluted with water to 40g / L, and nylon spinning 400T, 55 / 45 polyester-cotton and pure cotton fabrics were dip-padding-drying treatment, and the drying conditions were temperature 170°C and time 90s.

[0052] Comparative Example 2

[0053] 220g octadecyl acrylate, 10g hydroxyethyl methacrylate, 20g double-end acrylate modified silicone, 10g 2-[(3,5-dimethyl-1-H-pyrazolyl) carboxylamino] ethyl acrylate, 12g Span 80, 8g octadecyl trimethyl ammonium chloride, 2.5g glacial acetic acid, 60g tripropylene glycol, 480g deionized water, in a 60°C constant temperature water bath for 30 minutes, high-speed shearing and homogenization to obtain a pre-emulsion. The pre-emulsion was added to a 1L reactor, and the chain transfer agent n-dodecyl mercaptan and initiator V50 were added. Under continuous stirring and nitrogen protection, the reaction was kept at 60°C for more than 3 hours to obtain a fluorine-free waterproofing agent. The above-mentioned fluorine-free waterproofing agent was diluted with water to 40g / L, and nylon spinning 400T, 55 / 45 polyester-cotton and pure cotton fabrics were dip-padding-drying treatment, and the drying conditions were temperature 170°C and time 90s.

[0054] Comparative Example 3

[0055] 210g octadecyl acrylate, 10g hydroxyethyl methacrylate, 20g single-end acrylate modified silicone, 20g double-end acrylate modified silicone oil, 12g Span 80, 8g octadecyl trimethyl ammonium chloride, 2.5g glacial acetic acid, 60g tripropylene glycol, 480g deionized water, in a 60°C constant temperature water bath for 30 minutes, high-speed shearing, homogenization, to obtain a pre-emulsion. The pre-emulsion was added to a 1L reactor, and the chain transfer agent n-dodecyl mercaptan and initiator V50 were added. Under continuous stirring and nitrogen protection, the reaction was kept at 60°C for more than 3 hours to obtain a fluorine-free waterproofing agent. The above-mentioned fluorine-free waterproofing agent was diluted with water to 40g / L, and nylon spinning 400T, 55 / 45 polyester-cotton and pure cotton fabrics were dip-padding-drying treatment, and the drying conditions were temperature 170°C and time 90s.

[0056] Comparative Example 4

[0057] 250g octadecyl acrylate, 10g hydroxyethyl methacrylate, 12g Span 80, 8g octadecyl trimethyl ammonium chloride, 2.5g glacial acetic acid, 60g tripropylene glycol, 480g deionized water, in a 60°C constant temperature water bath for 30 minutes, high-speed shearing and homogenization to obtain a pre-emulsion. The pre-emulsion was added to a 1L reactor, and the chain transfer agent n-dodecyl mercaptan and initiator V50 were added. Under continuous stirring and nitrogen protection, the reaction was kept at 60°C for more than 3 hours to obtain a fluorine-free waterproofing agent. The above-mentioned fluorine-free waterproofing agent was diluted with water to 40g / L, and nylon spinning 400T, 55 / 45 polyester-cotton and pure cotton fabrics were dip-padding-drying treatment, and the drying conditions were temperature 170°C and time 90s.

[0058] Comparative Example 5

[0059] The commercially available fluorine-free waterproofing agent XF-5007 (copolyvinyl chloride type fluorine-free waterproofing agent) was diluted with water to 40 g / L, and nylon spunbond 400T, 55 / 45 polyester-cotton and pure cotton fabrics were subjected to dip-padding-drying treatments, respectively. The drying conditions were a temperature of 170°C and a time of 90 seconds.

[0060] Comparative Example 6

[0061] The commercially available fluorine-free waterproofing agent RUCO-DRY ECO PLUS was diluted with water to 40 g / L, and 10 g / L of a cross-linking agent was added. Nylon 400T, 55 / 45 polyester-cotton and pure cotton fabrics were subjected to dip-padding-drying treatments, respectively. The drying conditions were a temperature of 170 °C and a time of 90 s.

[0062] The fabrics treated with the fluorine-free waterproofing agent in the above examples and comparative examples were subjected to performance evaluation according to the following test standards. The results are shown in Tables 1 and 2.

[0063] (1) Waterproof performance test, carried out according to AATCC-22 spray test;

[0064] (2) Washability test: The washing method was carried out according to AATCC 135 standard, washing at 40°C for 15 min and tumble drying.

[0065] (3) Stability test: Pour the fluorine-free waterproofing agent into a 10 mL centrifuge tube and centrifuge it at a speed of 5000 r / min for 15 min to observe the sedimentation.

[0066] (4) Hand feel test: refer to AATCC EP5 fabric hand feel evaluation procedure for evaluation, with level 1 being the softest and level 5 being the stiffest.

[0067] (5) Hand scratch test: Use your fingers to scratch the surface of the fabric with uniform force, observe the surface marks and evaluate according to the following standards:

[0068] ○: Slight scratches

[0069] △: There are obvious scratches

[0070] ×: There are particularly obvious scratches

[0071] Table 1 Evaluation of water resistance and washability of fabrics treated with fluorine-free water repellent

[0072]

[0073]

[0074] Table 2 Stability of fluorine-free waterproofing agent and evaluation of hand scratches on treated fabrics

[0075] Example stability Feel Hand scratches Example 1 No settlement 2 ○ Comparative Example 1 No settlement 3 △ Comparative Example 2 No settlement 1.5 ○ Comparative Example 3 No settlement 2 ○ Comparative Example 4 No settlement 3.5 × Comparative Example 5 - 3 △ Comparative Example 6 - 3 △

[0076] From the test results of Table 1 and Table 2, it can be seen that compared with Comparative Example 1, Example 1 shows better hand feel and hand scratches due to the introduction of a flexible organosilicon structure in the main chain of the waterproofing agent molecule; compared with Comparative Example 2, Example 1 has better water resistance due to the introduction of an organosilicon structure in the side chain of the waterproofing agent molecule; compared with Comparative Example 3, Example 1 has better wash resistance due to the copolymerization of blocked isocyanate monomers; and compared with Comparative Example 4, Example 1 has significantly improved water resistance, wash resistance, hand feel and hand scratches due to the organosilicon modification of the main chain and side chain of the waterproofing agent and the copolymerization of blocked isocyanate monomers. In addition, compared with the commercially available chlorinated waterproofing agent (Comparative Example 5) and the waterproofing agent combined with a cross-linking agent (Comparative Example 6), Example 1 still has better wash resistance.

Claims

1. An acrylic fluorine-free waterproofing agent, characterized in that: The composition comprises the following components in mass percentage: 25-35% of fluorine-free copolymer, 1-5% of surfactant, 0.2-0.5% of acid regulator, 5-10% of organic solvent, and the rest of water; The fluorine-free copolymer is obtained by polymerizing the following monomers under the action of an initiator and a chain transfer agent, specifically comprising: (Meth)acrylate monomer (a), (Meth)acrylate monomer (b), Modified silicone containing reactive groups (c), Modified silicone containing reactive groups (d) a blocked isocyanate monomer containing a reactive group (e), The (meth)acrylate monomer (a) has the following general formula: ， Wherein, R1 is H or CH3, R2 is a straight chain alkyl group having more than 12 carbon atoms, The (meth)acrylate monomer (b) has the following general formula: ， Wherein, R3 is H or CH3, R4 is a straight chain hydrocarbon group with a carbon number of less than 8, X is an active group hydroxyl, amino or epoxy, The modified silicone containing reactive groups (c) has the following general formula: ， or ， Wherein, Z1 and Z2 are reactive groups that can be optionally copolymerized with acrylate monomers, and the reactive group is one of (meth)acryloyloxy, (meth)acrylamide and vinyl; R5 and R9 are hydrocarbon groups containing O, S, and N, or hydrocarbon groups not containing O, S, and N; R8 is an alkyl group containing O, S, and N, or an alkyl group not containing O, S, and N; R6, R7, R 10 is a methyl group or a phenyl group, m is an integer greater than or equal to 0, The modified silicone containing reactive groups (d) has the following general formula: ， Wherein, Z3 is a reactive group optionally copolymerizable with an acrylate monomer, the reactive group is one of (meth)acryloyloxy, (meth)acrylamide and vinyl, R11 is a hydrocarbon group containing O, S, N, or a hydrocarbon group not containing O, S, N; R 12 , R 13 is a methyl group or a phenyl group, and n is an integer greater than or equal to 0, The reactive group-containing blocked isocyanate monomer (e) is obtained by blocking a compound having the following general formula: ， Wherein, Z4 is a reactive group that can be optionally copolymerized with an acrylate monomer, and the reactive group is one of (meth)acryloyloxy, (meth)acrylamide and vinyl. 14 is a hydrocarbon group containing O, S, or N, or a hydrocarbon group not containing O, S, or N, The end-capping agent used for the monomer e is selected from phenols, caprolactam, acetylacetone, methyl ethyl ketone oxime, imidazoles or pyrazoles.

2. The acrylate fluorine-free waterproofing agent according to claim 1, characterized in that: The mass composition ratio of each monomer in the fluorine-free copolymer is (meth)acrylate monomer (a) 50-85%, (meth)acrylate monomer (b) 2-10%, modified silicone containing reactive groups (c) 5-15%, modified silicone containing reactive groups (d) 5-15%, and blocked isocyanate monomer containing reactive groups (e) 2-10%.

3. The acrylic ester fluorine-free waterproofing agent according to claim 1, characterized in that: The surfactant is one or more of a nonionic surfactant or a cationic surfactant. The nonionic surfactant is one or more of Span 40, Span 60, Span 80, polyoxyethylene monostearate, sorbitan monostearate, sorbitan monooleate, and polyoxyethylene octadecyl ether; the cationic surfactant is one or more of hexadecyltrimethylammonium bromide, octadecyltrimethylammonium chloride, docosyltrimethylammonium chloride, and alkylbenzyldimethylammonium chloride.

4. The acrylic ester fluorine-free waterproofing agent according to claim 1, characterized in that: The acid regulator is glacial acetic acid, the water is deionized water, and the organic solvent is selected from methyl ethyl ketone, ethylene glycol, propylene glycol and tripropylene glycol.

5. The acrylic ester fluorine-free waterproofing agent according to claim 1, characterized in that: The (meth)acrylate monomer (a) has the general formula: ， Wherein R2 is a straight chain alkyl group having 16 to 22 carbon atoms.

6. A method for preparing an acrylic fluorine-free waterproofing agent according to any one of claims 1 to 5, characterized in that: The following steps are involved: S1: Mix the components according to the proportion at 60°C and shear homogenize; S2: react at 60-80°C for more than 3 hours under the action of an initiator and a chain transfer agent to obtain a fluorine-free waterproofing agent.

7. The use of an acrylic ester fluorine-free waterproofing agent according to claim 1, characterized in that: The textiles processed by the fluorine-free waterproofing agent are diluted with water in a certain proportion to form a finishing liquid, and the textiles are subjected to immersion-padding-baking finishing, the baking temperature is 130° C.-180° C., and the baking time is 0.5-2 minutes.

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