Fluoride-free water-repellent flame-retardant composite finishing agent as well as preparation method and application thereof

Abstract

The invention relates to a fluoride-free water-repellent flame-retardant composite finishing agent as well as a preparation method and application thereof, and belongs to the technical field of fabric treatment. The composite finishing agent comprises an effective polymer component, the chemical structure of the effective polymer component comprises a first chain segment and a second chain segment, the first chain segment has a water repellent effect, and the second chain segment has a flame retardant effect; a first chain segment with a water-repellent effect and a second chain segment with a flame-retardant effect are linked into a high-molecular long chain to form an effective polymer component, so that the effective polymer component has water-repellent and flame-retardant effects at the same time, and further the composite finishing agent has relatively good water-repellent performance and flame-retardant performance at the same time.

Description

Technical Field

[0001] The present application relates to the technical field of fabric treatment, and in particular to a fluorine-free water-repellent and flame-retardant composite finishing agent and a preparation method and application thereof. Background Art

[0002] With the development of science and technology and the improvement of production and living standards, people have higher and higher functional requirements for textiles. Water-repellent and flame-retardant textiles are two important types. In order to give textiles water-repellent and flame-retardant functions, water-repellent finishing agents and flame retardants are widely used in textile finishing. Fluorinated acrylate polymers contain a unique low-surface-energy CF long-chain structure and are widely used as water-repellent finishing agents in textile water-repellent finishing. They have excellent water-repellent properties, but people have found that fluorinated water-repellents contain PFOA and PFOS, which are extremely difficult to degrade naturally, and accumulate in the human body and the ecological environment and are very harmful.

[0003] As people's environmental awareness increases, fluorine-free water repellents are becoming more and more popular. Flame retardants for textiles mainly include phosphorus- and nitrogen-containing inorganic salts, organic halogens, organic phosphorus, organic nitrogen, and silicones. When both water-repellent and flame-retardant functions are required, flame retardants and fluorine-free water repellents need to be used together. The two have poor compatibility, poor working fluid stability, and negative effects on each other's functions. That is, flame retardants make the water-repellent effect worse, and fluorine-free water repellents cause a significant decrease in flame retardant properties. Summary of the invention

[0004] The present application provides a fluorine-free water-repellent flame-retardant composite finishing agent and a preparation method and application thereof, so that the composite finishing agent has both good water-repellent properties and flame-retardant properties.

[0005] In a first aspect, the present application provides a fluorine-free water-repellent flame-retardant composite finishing agent, the composite finishing agent contains an effective polymer component, the chemical structure of the effective polymer component includes a first segment and a second segment, the first segment has a water-repellent effect, and the second segment has a flame-retardant effect.

[0006] As an optional embodiment, the first segment includes a first connecting base structure, the second segment includes a second connecting base structure, the first connecting base structure is chemically bonded to the second connecting base structure, and the first connecting base structure and the second connecting base structure have the same main structure.

[0007] As an optional embodiment, the main structure includes an acrylate structure.

[0008] As an optional implementation, the first segment includes wherein R1 is hydrogen or methyl, and m is a natural number from 1 to 23; and / or

[0009] The second segment includes Wherein, R2 is hydrogen or methyl, and R3 is hydroxyethyl, hydroxypropyl or blank.

[0010] As an optional embodiment, the chemical structure of the effective polymer component includes:

[0011]

[0012] Wherein, R1 is hydrogen or methyl,

[0013] R2 is hydrogen or methyl,

[0014] R3 is hydroxyethyl, hydroxypropyl or blank,

[0015] R4 is hydrogen or methyl,

[0016] R5 is hydroxyethyl, hydroxypropyl, epoxy, amide, dimethylamino, carboxyl, blocked isocyanate or halogen,

[0017] m is a natural number from 1 to 23,

[0018] x, y, and z are independently selected from any positive integer.

[0019] As an optional implementation, the composite finishing agent comprises, by weight percentage: 10% to 90% of effective polymer components, 1% to 20% of surfactants, 1% to 40% of cosolvents, and the remainder being solvents and unavoidable impurities.

[0020] As an optional embodiment, the surfactant includes at least one of a nonionic surfactant, a cationic surfactant, an anionic surfactant and an amphoteric surfactant; and / or

[0021] The co-solvent comprises at least one of acetone, butanone, ethylene glycol, propylene glycol, 1,2-propylene glycol, dipropylene glycol, hexylene glycol and tripropylene glycol; and / or

[0022] The solvent includes water.

[0023] In a second aspect, the present application provides a method for preparing a fluorine-free water-repellent flame-retardant composite finishing agent, the method comprising:

[0024] The first functional monomer with water repellent function, the second functional monomer with flame retardant function and the cross-linking functional monomer are polymerized under the action of an initiator to obtain an effective polymer component;

[0025] The effective polymer component is prepared into a fluorine-free water-repellent and flame-retardant composite finishing agent.

[0026] As an optional embodiment, the first functional monomer includes at least one of a saturated or unsaturated linear or branched alkyl (meth)acrylate or a cycloalkyl (meth)acrylate having 1 to 24 carbon atoms; and / or

[0027] The first functional monomer comprises at least one of alkyl acrylate or cycloalkyl acrylate with a saturated or unsaturated linear or branched alkyl group having 1 to 24 carbon atoms; and / or

[0028] The second functional monomer comprises at least one of a phosphorus-containing (meth)acrylate functional monomer and a phosphorus-containing acrylate functional monomer; and / or

[0029] The second functional monomer comprises at least one of (meth)acrylate phosphate, 2-hydroxyethyl (meth)acrylate phosphate, 2-hydroxypropyl (meth)acrylate phosphate, acrylate phosphate, 2-hydroxyethyl acrylate phosphate and 2-hydroxypropyl acrylate phosphate; and / or

[0030] The cross-linking functional monomer includes an acrylate or methacrylate containing at least one of a hydroxyl group, an epoxy group, an amide group, a dimethylamino group, a carboxyl group, a blocked isocyanate group and a halogen terminal group; and / or

[0031] The initiator includes at least one of a water-soluble azo initiator, a peroxide initiator and a redox initiator.

[0032] In a third aspect, the present application provides an application of a fluorine-free, water-repellent, flame-retardant composite finishing agent, wherein the composite finishing agent comprises the composite finishing agent described in any one of claims 1 to 7 or the composite finishing agent prepared by the method described in any one of claims 8 to 9, and the application comprises using the composite finishing agent for composite finishing of fabrics.

[0033] The above technical solution provided by the embodiment of the present application has the following advantages compared with the prior art:

[0034] The composite finishing agent provided in the embodiment of the present application forms an effective polymer component by linking a first chain segment with a water-repellent effect and a second chain segment with a flame-retardant effect into a long polymer chain, so that the effective polymer component has both water-repellent and flame-retardant effects, thereby making the composite finishing agent have good water-repellent and flame-retardant properties. BRIEF DESCRIPTION OF THE DRAWINGS

[0035] The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments consistent with the present application and, together with the description, serve to explain the principles of the present application.

[0036] In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. Obviously, for ordinary technicians in this field, other drawings can be obtained based on these drawings without paying any creative labor.

[0037] Figure 1 A flowchart of the method provided in the embodiment of the present application. DETAILED DESCRIPTION

[0038] In order to make the purpose, technical solution and advantages of the embodiments of the present application clearer, the technical solution in the embodiments of the present application will be clearly and completely described below in conjunction with the drawings in the embodiments of the present application. Obviously, the described embodiments are part of the embodiments of the present application, not all of the embodiments. Based on the embodiments in the present application, all other embodiments obtained by ordinary technicians in this field without making creative work are within the scope of protection of this application.

[0039] Unless otherwise specified, various raw materials, reagents, instruments and equipment used in this application can be purchased from the market or prepared by existing methods.

[0040] At present, in order to make fabrics such as pure cotton and polyester have good flame retardant and water repellent effects at the same time, the commonly used operations are: 1) After the fabric is treated with water repellent finishing, it is treated with flame retardant finishing; however, the water repellent effect of the fabric treated in this way will decrease, and the flame retardant effect of the fabric will not be improved, resulting in poor flame retardant effect of the fabric. 2) The water repellent finishing agent and the flame retardant finishing agent are used in the same bath to treat the fabric; however, this method will make the working fluid unstable, which will firstly reduce the factory production efficiency, and secondly, the water repellent and flame retardant effects of the fabric will not be good. At the same time, the applicant found that the washability of the fabric treated by the above two treatment methods is generally poor.

[0041] To this end, the present application intends to provide a composite finishing agent, which has good water repellency and flame retardancy, and enables the fabric treated with the composite finishing agent to have good wash resistance.

[0042] The embodiment of the present application provides a fluorine-free water-repellent flame-retardant composite finishing agent, the composite finishing agent contains an effective polymer component, the chemical structure of the effective polymer component includes a first segment and a second segment, the first segment has a water-repellent effect, and the second segment has a flame-retardant effect.

[0043] The composite finishing agent forms an effective polymer component by linking a first chain segment with a water-repellent effect and a second chain segment with a flame-retardant effect into a long polymer chain, so that the effective polymer component has both water-repellent and flame-retardant effects, thereby making the composite finishing agent have good water-repellent and flame-retardant properties at the same time, and making the fabric treated with the composite finishing agent have good wash resistance.

[0044] In some embodiments, the first segment includes a first connecting base structure, the second segment includes a second connecting base structure, the first connecting base structure is chemically bonded to the second connecting base structure, and the first connecting base structure and the second connecting base structure have the same main structure.

[0045] By making the first chain segment with water repellent effect and the second chain segment with flame retardant effect both segments with the same or similar connecting basic structure and similar main structure, there are similar molecular forces and chemical bond forces between the surface of the fabric and the fiber, and there will be no situation of snatching the combination with the same position of the fiber, thereby improving the firmness of the combination of the composite finishing agent and the fabric fiber. Due to the similarity in the structure of the first chain segment with water repellent effect and the second chain segment with flame retardant effect, the polymer has better stability and better emulsification stability in water. When the fluorine-free water-repellent flame retardant composite finishing agent is used to treat the fabric, the working liquid has better stability and is not easy to precipitate, which is convenient for the printing and dyeing factory to carry out efficient production.

[0046] Further, the main structure includes an acrylate structure. It is understandable that the main structure can be an acrylate structure, a methacrylate structure, etc.

[0047] In some embodiments, the first segment comprises Wherein, R1 is hydrogen or methyl, and m is a natural number from 1 to 23.

[0048] In some embodiments, the second segment comprises Wherein, R2 is hydrogen or methyl, and R3 is hydroxyethyl, hydroxypropyl or blank.

[0049] Typically, the first segment and the second segment are connected via a cross-linking segment. In some embodiments, the cross-linking segment may include Among them, R4 is hydrogen or methyl, and R5 is hydroxyethyl, hydroxypropyl, epoxy, amide, dimethylamino, carboxyl, blocked isocyanate or halogen.

[0050] By controlling the length of the first segment with water repellent effect and the length of the second segment with flame retardant effect, the strength of the water repellent effect and the flame retardant effect can be adjusted to achieve the best water repellent and flame retardant effects.

[0051] In some embodiments, the chemical structure of the effective polymer component comprises:

[0052]

[0053] Wherein, R1 is hydrogen or methyl,

[0054] R2 is hydrogen or methyl,

[0055] R3 is hydroxyethyl, hydroxypropyl or blank,

[0056] R4 is hydrogen or methyl,

[0057] R5 is hydroxyethyl, hydroxypropyl, epoxy, amide, dimethylamino, carboxyl, blocked isocyanate or halogen,

[0058] m is a natural number from 1 to 23,

[0059] x, y, and z are independently selected from any positive integer.

[0060] In some embodiments, the composite finishing agent comprises, by weight percentage: 10% to 90% of effective polymer components, preferably 20-50%, more preferably 25-45%; 1% to 20% of surfactants, preferably 1-15%, more preferably 1-10%; 1% to 40% of cosolvents, preferably 5-25%, more preferably 5-20%; the rest are solvents and unavoidable impurities.

[0061] The composite finishing agent can exist in the form of an aqueous emulsion or an aqueous dispersion.

[0062] Further, the surfactant includes at least one of a nonionic surfactant, a cationic surfactant, an anionic surfactant and an amphoteric surfactant; wherein the nonionic surfactant can be selected from one or a mixture of polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene octadecyl ether, polyoxyethylene oleyl ether, sorbitan laurate, sorbitan stearate, sorbitan palmitate, polyoxyethylene polyoxypropylene block copolymer, etc.; the cationic surfactant can be selected from one or a mixture of octadecyl ammonium acetate, dodecyl trimethyl ammonium chloride (bromide), cetyl trimethyl ammonium chloride (bromide), octadecyl trimethyl ammonium chloride (bromide); the anionic surfactant can be selected from one or a mixture of alkyl sulfonates, alkyl benzene sulfonates and fatty alcohol sulfates; the amphoteric surfactant can be selected from one or a mixture of amino acid type, betaine type, imidazoline type and other amphoteric surfactants. The co-solvent includes at least one of acetone, butanone, ethylene glycol, propylene glycol, 1,2-propylene glycol, dipropylene glycol, hexylene glycol and tripropylene glycol; and the solvent includes water.

[0063] Figure 1 A flow chart of the method provided in the embodiment of the present application is as follows: Figure 1 As shown, based on a general inventive concept, the embodiments of the present application also provide a method for preparing a fluorine-free water-repellent flame-retardant composite finishing agent.

[0064] The method is used for preparing the above-mentioned composite finishing agent. The specific content of the composite finishing agent can refer to the above-mentioned embodiment. Since the method adopts part or all of the technical solutions of the above-mentioned embodiment, it at least has all the beneficial effects brought by the technical solutions of the above-mentioned embodiment, which will not be repeated here one by one.

[0065] In some embodiments, the method comprises:

[0066] S1. The first functional monomer having a water-repellent function, the second functional monomer having a flame-retardant function and the cross-linking functional monomer are polymerized under the action of an initiator to obtain an effective polymer component;

[0067] In some embodiments, the first functional monomer may be a long-chain acrylate or long-chain methacrylate water-repellent functional monomer, which may specifically include at least one of a saturated or unsaturated linear or branched alkyl (meth)acrylate, a cycloalkyl (meth)acrylate, an alkyl acrylate or a cycloalkyl acrylate having a carbon number of 1 to 24. For example, the first functional monomer may be lauryl (meth)acrylate, tetradecyl (meth)acrylate, hexadecyl (meth)acrylate, octadecyl (meth)acrylate, behenyl (meth)acrylate, cyclohexyl (meth)acrylate and isodecyl (meth)acrylate, etc., preferably lauryl (meth)acrylate, tetradecyl (meth)acrylate, hexadecyl (meth)acrylate, octadecyl (meth)acrylate, behenyl (meth)acrylate, more preferably hexadecyl (meth)acrylate, octadecyl (meth)acrylate, behenyl (meth)acrylate. The mass proportion of the first functional monomer in the effective polymer component is about 10%-85%, preferably 25-80%, and further preferably 40-80%.

[0068] In some embodiments, the second functional monomer includes at least one of a phosphorus-containing (meth)acrylate functional monomer and a phosphorus-containing acrylate functional monomer. Further, the second functional monomer includes at least one of (meth)acrylate phosphate, 2-hydroxyethyl (meth)acrylate phosphate, 2-hydroxypropyl (meth)acrylate phosphate, acrylate phosphate, 2-hydroxyethyl acrylate phosphate and 2-hydroxypropyl acrylate phosphate. The mass proportion of the second functional monomer in the effective polymer component is about 1-25%, preferably 5-25%, and more preferably 8-25%.

[0069] In some embodiments, the cross-linking functional monomer includes an acrylate or methacrylate containing at least one of a hydroxyl group, an epoxy group, an amide group, a dimethylamino group, a carboxyl group, a blocked isocyanate group, and a halogen end group. For example, the cross-linking functional monomer can be N-hydroxymethyl acrylamide, glycidyl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, diacetone (meth) acrylic acid, and N, N-dimethyl (meth) acrylic acid, preferably glycidyl (meth) acrylate, hydroxyethyl (meth) acrylate, and hydroxypropyl (meth) acrylate. The mass proportion of the cross-linking functional monomer in the effective polymer component is about 1-15%, preferably 1-12%, and further preferably 1-10%.

[0070] In some embodiments, the initiator includes at least one of a water-soluble azo initiator, a peroxide initiator and a redox initiator, and specifically may be one or more of azobisisobutyramidine hydrochloride, hydrogen peroxide and potassium persulfate.

[0071] It should be noted that, during the polymerization process, dodecyl mercaptan can be used as a regulator in free radical polymerization to control the molecular weight of the polymer.

[0072] S2. The effective polymer component is formulated into a fluorine-free water-repellent and flame-retardant composite finishing agent.

[0073] Specifically, in this embodiment, the entire preparation process of the fluorine-free water-repellent flame-retardant composite finishing agent can be: a pre-emulsion formed by a first functional monomer, a second functional monomer, a cross-linking functional monomer, a surfactant, a cosolvent and softened water is subjected to free radical emulsion polymerization under the action of an initiator to obtain the fluorine-free water-repellent flame-retardant composite finishing agent.

[0074] Based on a general inventive concept, the present application also provides an application of the above-provided fluorine-free water-repellent flame-retardant composite finishing agent in the waterproof and flame-retardant composite finishing of fabrics. Specifically, the fluorine-free water-repellent flame-retardant composite finishing agent is used for water-repellent and flame-retardant composite finishing of natural fiber fabrics, synthetic fiber fabrics or blended fiber fabrics alone or in combination with other treatment agents, through any method of padding or impregnation.

[0075] The present application will be further described below in conjunction with specific embodiments. It should be understood that these embodiments are intended only to illustrate the present application and are not intended to limit the scope of the present application. The experimental methods for which specific conditions are not specified in the following examples are usually measured according to national standards. If there is no corresponding national standard, then the conditions recommended by the manufacturer are followed.

[0076] The specific details of some products used in the following examples are as follows: 2-hydroxyethyl methacrylate phosphate and 2-hydroxypropyl methacrylate phosphate are from Japan Kyoeisha, with trade names P-1M and P-2M respectively; methacrylate phosphate is from Tanextra of the Netherlands, with trade name TANEXTRA MAP.

[0077] Example 1

[0078] A fluorine-free water-repellent flame-retardant composite finishing agent, the preparation of which comprises the following steps:

[0079] 70.0g of octadecyl acrylate, 18.7g of methacrylate phosphate, 7.7g of hydroxyethyl methacrylate, 36.0g of dipropylene glycol, 0.2g of dodecyl mercaptan, 230.0g of softened water, 3.0g of polyoxyethylene lauryl ether, 5.0g of polyoxyethylene oleyl ether and 2.0g of octadecyl trimethyl ammonium chloride are added into a beaker, and a stable oil-in-water emulsion is obtained after emulsification by a homogenizer or ultrasonic wave for 10-15 minutes; then the emulsion is charged into a reaction flask, and then 1.0g of initiator azobisisobutylamidine hydrochloride is added, and the water bath is heated to 70°C at the same time, and the reaction is carried out for 7.5 hours to obtain a uniform and stable polymer aqueous emulsion, i.e., a fluorine-free water-repellent flame-retardant composite finishing agent.

[0080] Example 2

[0081] A fluorine-free water-repellent flame-retardant composite finishing agent, the preparation of which comprises the following steps:

[0082] 72.8g of hexadecyl acrylate, 14.0g of 2-hydroxyethyl methacrylate phosphate, 4.1g of hydroxypropyl methacrylate, 2.25g of glycidyl methacrylate, 34.5g of butanone, 0.2g of dodecyl mercaptan, 225.0g of softened water, 7.9g of polyoxyethylene hexadecyl ether, and 3.1g of hexadecyltrimethylammonium bromide are added into a beaker, and a stable oil-in-water emulsion is obtained after emulsification by a homogenizer or ultrasonic wave for 10-15 minutes; then the emulsion is charged into a reaction flask, and then 1.0g of initiator azobisisobutylamidine hydrochloride is added, and the water bath is heated to 78°C at the same time, and the reaction is carried out for 7 hours to obtain a uniform and stable polymer aqueous emulsion, i.e., a fluorine-free water-repellent flame-retardant composite finishing agent.

[0083] Example 3

[0084] A fluorine-free water-repellent flame-retardant composite finishing agent, the preparation of which comprises the following steps:

[0085] 72.1g of behenyl methacrylate, 18.0g of 2-hydroxypropyl methacrylate phosphate, 2.0g of hydroxyethyl acrylate, 6.3g of N-hydroxymethyl acrylamide, 37.8g of tripropylene glycol, 0.2g of dodecyl mercaptan, 239.0g of softened water, 3.0g of polyoxyethylene octadecyl ether, 6.4g of sorbitan palmitate, and 2.4g of octadecyl trimethyl ammonium chloride are added into a beaker, and a stable oil-in-water emulsion is obtained after emulsification by a homogenizer or ultrasonic wave for 10-15 minutes; then the emulsion is charged into a reaction flask, and then 1.0g of initiator azobisisobutylamidine hydrochloride is added, and the water bath is heated to 83-85°C at the same time, and the reaction is carried out for 6.5 hours to obtain a uniform and stable polymer aqueous emulsion, i.e., a fluorine-free water-repellent flame-retardant composite finishing agent.

[0086] Comparative Example 1

[0087] A fluorine-free water-repellent flame-retardant composite finishing agent, wherein the effective polymer component of the composite finishing agent is a compound of the effective polymer component without the second chain segment in Example 1 and an inorganic salt flame retardant solution with a solid content of 30% (brand name FR-601, manufacturer: Beijing Zhongfang Haitian New Materials Technology Co., Ltd.), and the preparation thereof comprises the following steps:

[0088] 88.7g of octadecyl acrylate, 7.7g of hydroxyethyl methacrylate, 36.0g of dipropylene glycol, 0.2g of dodecyl mercaptan, 230.0g of softened water, 3.0g of polyoxyethylene lauryl ether, 5.0g of polyoxyethylene oleyl ether, and 2.0g of octadecyl trimethyl ammonium chloride are added into a beaker, and a stable oil-in-water emulsion is obtained after emulsification by a homogenizer or ultrasonic wave for 10-15 minutes; then the emulsion is charged into a reaction flask, and then 1.0g of initiator azobisisobutylamidine hydrochloride is added, and the water bath is heated to 70°C at the same time, and the reaction is carried out for 7.5 hours to obtain a uniform and stable polymer aqueous emulsion, and finally compounded with an inorganic salt flame retardant solution FR-601 with a solid content of 30% (the compounding ratio is 1:1), that is, a fluorine-free water-repellent flame retardant composite finishing agent.

[0089] Comparative Example 2

[0090] A fluorine-free water-repellent flame-retardant composite finishing agent, wherein the effective polymer component of the composite finishing agent is a compound of the effective polymer component without the second chain segment in Example 2 and a 30% solid content cotton phosphate flame retardant solution (brand FR-603, manufacturer: Beijing Zhongfang Haitian New Materials Technology Co., Ltd.), and the preparation thereof comprises the following steps:

[0091] 86.8g of hexadecyl acrylate, 4.1g of hydroxypropyl methacrylate, 2.25g of glycidyl methacrylate, 34.5g of butanone, 0.2g of dodecyl mercaptan, 225.0g of softened water, 7.9g of polyoxyethylene hexadecyl ether, and 3.1g of hexadecyltrimethylammonium bromide are added into a beaker, and a stable oil-in-water emulsion is obtained after emulsification by a homogenizer or ultrasonic wave for 10-15 minutes; then the emulsion is charged into a reaction flask, and then 1.0g of initiator azobisisobutylamidine hydrochloride is added, and the water bath is heated to 78°C, and the reaction is carried out for 7 hours to obtain a uniform and stable polymer aqueous emulsion, and finally compounded with 30% solid content of cotton phosphate flame retardant solution FR-603 (compounding ratio is 1:1), that is, a fluorine-free water-repellent flame retardant composite finishing agent.

[0092] Comparative Example 3

[0093] A fluorine-free water-repellent flame-retardant composite finishing agent, wherein the effective polymer component of the composite finishing agent is a compound of the effective polymer component without the second chain segment in Example 3 and a 30% solid content chemical fiber cyclic phosphate flame retardant solution (brand FR-605, manufacturer: Beijing Zhongfang Haitian New Material Technology Co., Ltd.), and the preparation thereof comprises the following steps:

[0094] 90.1g of behenyl methacrylate, 2.0g of hydroxyethyl acrylate, 6.3g of N-hydroxymethyl acrylamide, 37.8g of tripropylene glycol, 0.2g of dodecyl mercaptan, 239.0g of softened water, 3.0g of polyoxyethylene octadecyl ether, 6.4g of sorbitan palmitate, and 2.4g of octadecyl trimethyl ammonium chloride are added into a beaker, and a stable oil-in-water emulsion is obtained after emulsification by a homogenizer or ultrasonic wave for 10-15 minutes; then the emulsion is charged into a reaction flask, and then 1.0g of initiator azobisisobutylamidine hydrochloride is added, and the water bath is heated to 83-85°C at the same time, and the reaction is carried out for 6.5 hours to obtain a uniform and stable polymer aqueous emulsion, and finally compounded with 30% solid content of cyclic phosphate flame retardant solution FR-605 for chemical fiber (compounding ratio is 1:1), that is, a fluorine-free water-repellent flame retardant composite finishing agent.

[0095] Take 240 grams of the fluorine-free water-repellent flame-retardant composite finishing agent provided in each embodiment and comparative example, mix them evenly with 760 ml of water to make a working solution, and use pure cotton and polyester woven fabrics for fluorine-free water-repellent flame-retardant finishing. The pure cotton and polyester fabrics are respectively dipped into the above-mentioned working solution (using two dips and two rolls), and then dried (105°C, 3 minutes) and baked (160°C, 2 minutes) to complete the fluorine-free water-repellent flame-retardant finishing. The liquid carrying rates of each fabric after dipping and rolling are: 84% for pure cotton and 60% for polyester. The fabrics treated with the fluorine-free water-repellent flame-retardant composite finishing agent provided in each embodiment and comparative example are rated for water repellency and flame retardancy.

[0096] Among them, the waterproof test reference standard GB / T 4745-2012 Testing and evaluation of waterproof performance of textiles - water dipping method;

[0097] The flame retardant test reference standard GB / T 5455-2014 Textile combustion performance - Determination of vertical damage length, smoldering and afterflaming time and standard GB / T 17591-2006 Flame retardant fabrics.

[0098] The results are as follows:

[0099]

[0100]

[0101] The fabrics treated with the fluorine-free water-repellent flame-retardant composite finishing agent provided in each embodiment and comparative example were subjected to a fabric washing durability test. Specifically, the fabrics were washed according to the mild washing procedure of the automatic washing machine (type A) in reference to the standard GB / T 17596-1998. Specifically, the fabrics were dried at 105°C for 3 minutes after washing, and the number of washings was 5 times. Then, the water-repellent flame-retardant rating was performed. The results are shown in the following table:

[0102]

[0103] The stability test of the fluorine-free water-repellent flame-retardant composite finishing agent provided in each embodiment and comparative example was conducted, specifically, the stratification of the composite finishing agent was observed after being placed for 3 hours and 30 days. The results are shown in the following table:

[0104] Leave for 3 hours Leave for 30 days Example 1 Stablize Stablize Example 2 Stablize Stablize Example 3 Stablize Stablize Comparative Example 1 Layered precipitation The upper layer is transparent and the layers are precipitated Comparative Example 2 Layered precipitation The upper layer is transparent and the layers are precipitated Comparative Example 3 Layered precipitation The upper layer is transparent and the layers are precipitated

[0105] From the above results, it can be concluded that the fluorine-free water-repellent and flame-retardant composite finishing agent provided in the examples of the present application has excellent water-repellent, flame-retardant and wash-resistant properties, and its storage stability is also good.

[0106] Various embodiments of the present application may be presented in the form of a range; it should be understood that the description in the form of a range is only for convenience and brevity, and should not be understood as a rigid limitation on the scope of the present application; therefore, the range description should be considered to have specifically disclosed all possible sub-ranges and single numerical values ​​within the range. For example, the range description from 1 to 6 should be considered to have specifically disclosed sub-ranges, such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6, etc., as well as single numbers within the range, such as 1, 2, 3, 4, 5 and 6, which apply regardless of the range. In addition, whenever a numerical range is indicated herein, it is meant to include any cited number (fractional or integer) within the indicated range.

[0107] In the present application, in the absence of any contrary description, the directional words used, such as "upper" and "lower", are specifically the directions of the drawings in the accompanying drawings. In addition, in the description of the present specification, the terms "including", "comprising", etc. refer to "including but not limited to". In this article, relational terms such as "first" and "second" are only used to distinguish one entity or operation from another entity or operation, and do not necessarily require or imply that there is any such actual relationship or order between these entities or operations. In this article, "and / or" describes the association relationship of the associated objects, indicating that there may be three relationships, for example, A and / or B, which can represent: A exists alone, A and B exist at the same time, and B exists alone. Wherein A, B can be singular or plural. In this article, "at least one" refers to one or more, and "plural" refers to two or more. "At least one", "at least one of the following" or similar expressions refer to any combination of these items, including any combination of singular or plural items. For example, "at least one of a, b or c", or "at least one of a, b and c", can both mean: a, b, c, ab (i.e. a and b), ac, bc, or abc, where a, b and c can be single or multiple.

[0108] The above description is only a specific implementation of the present application, so that those skilled in the art can understand or implement the present application. Various modifications to these embodiments will be apparent to those skilled in the art, and the general principles defined herein can be implemented in other embodiments without departing from the spirit or scope of the present application. Therefore, the present application will not be limited to the embodiments shown herein, but will conform to the widest range consistent with the principles and novel features applied for herein.

Claims

1. A fluorine-free water-repellent flame-retardant composite finishing agent, characterized in that: The composite finishing agent contains an effective polymer component, the chemical structure of which includes a first segment and a second segment, the first segment has a water-repellent effect, and the second segment has a flame-retardant effect.

2. The fluorine-free water-repellent flame-retardant composite finishing agent according to claim 1, characterized in that: The first segment includes a first connecting base structure, the second segment includes a second connecting base structure, the first connecting base structure is chemically bonded to the second connecting base structure, and the first connecting base structure and the second connecting base structure have the same main structure.

3. The fluorine-free water-repellent flame-retardant composite finishing agent according to claim 2, characterized in that: The main structure includes an acrylate structure.

4. The fluorine-free water-repellent flame-retardant composite finishing agent according to claim 1, characterized in that: The first segment includes wherein R1 is hydrogen or methyl, and m is a natural number from 1 to 23; and / or The second segment includes Wherein, R2 is hydrogen or methyl, and R3 is hydroxyethyl, hydroxypropyl or blank.

5. The fluorine-free water-repellent flame-retardant composite finishing agent according to any one of claims 1 to 4, characterized in that: The chemical structure of the effective polymer component includes: Wherein, R1 is hydrogen or methyl, R2 is hydrogen or methyl, R3 is hydroxyethyl, hydroxypropyl or blank, R4 is hydrogen or methyl, R5 is hydroxyethyl, hydroxypropyl, epoxy, amide, dimethylamino, carboxyl, blocked isocyanate or halogen, m is a natural number from 1 to 23, x, y, and z are independently selected from any positive integer.

6. The fluorine-free water-repellent flame-retardant composite finishing agent according to any one of claims 1 to 5, characterized in that: The composite finishing agent comprises, by weight percentage, 10% to 90% of effective polymer components, 1% to 20% of surfactants, 1% to 40% of cosolvents, and solvents.

7. The fluorine-free water-repellent flame-retardant composite finishing agent according to claim 6, characterized in that: The surfactant comprises at least one of a nonionic surfactant, a cationic surfactant, an anionic surfactant and an amphoteric surfactant; and / or The co-solvent comprises at least one of acetone, butanone, ethylene glycol, propylene glycol, 1,2-propylene glycol, dipropylene glycol, hexylene glycol and tripropylene glycol; and / or The solvent includes water.

8. A method for preparing a fluorine-free water-repellent flame-retardant composite finishing agent, characterized in that: The method comprises: The first functional monomer with water repellent function, the second functional monomer with flame retardant function and the cross-linking functional monomer are polymerized under the action of an initiator to obtain an effective polymer component; The effective polymer component is prepared into a fluorine-free water-repellent and flame-retardant composite finishing agent.

9. The method for preparing the fluorine-free water-repellent flame-retardant composite finishing agent according to claim 8, characterized in that: The first functional monomer comprises at least one of a saturated or unsaturated linear or branched alkyl (meth)acrylate or a cycloalkyl (meth)acrylate having 1 to 24 carbon atoms; and / or The first functional monomer comprises at least one of alkyl acrylate or cycloalkyl acrylate with a saturated or unsaturated linear or branched alkyl group having 1 to 24 carbon atoms; and / or The second functional monomer comprises at least one of a phosphorus-containing (meth)acrylate functional monomer and a phosphorus-containing acrylate functional monomer; and / or The second functional monomer comprises at least one of (meth)acrylate phosphate, 2-hydroxyethyl (meth)acrylate phosphate, 2-hydroxypropyl (meth)acrylate phosphate, acrylate phosphate, 2-hydroxyethyl acrylate phosphate and 2-hydroxypropyl acrylate phosphate; and / or The cross-linking functional monomer includes an acrylate or methacrylate containing at least one of a hydroxyl group, an epoxy group, an amide group, a dimethylamino group, a carboxyl group, a blocked isocyanate group and a halogen terminal group; and / or The initiator includes at least one of a water-soluble azo initiator, a peroxide initiator and a redox initiator.

10. Application of a fluorine-free water-repellent flame-retardant composite finishing agent, characterized in that: The composite finishing agent comprises the composite finishing agent according to any one of claims 1 to 7 or the composite finishing agent prepared by the method according to any one of claims 8 to 9, and the application comprises using the composite finishing agent for composite finishing of fabrics.

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