CN107974826B - Fluoride-free waterproof finishing emulsion for fabric and application thereof - Google Patents

Fluoride-free waterproof finishing emulsion for fabric and application thereof Download PDF

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CN107974826B
CN107974826B CN201711292001.8A CN201711292001A CN107974826B CN 107974826 B CN107974826 B CN 107974826B CN 201711292001 A CN201711292001 A CN 201711292001A CN 107974826 B CN107974826 B CN 107974826B
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CN107974826A (en
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鲁琴
王新
付洪娥
王玉灿
刘博�
吴井龙
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Shenyang Research Institute of Chemical Industry Co Ltd
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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
    • D06M13/372—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen containing etherified or esterified hydroxy groups ; Polyethers of low molecular weight
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    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/02—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with hydrocarbons
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
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    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
    • D06M13/184—Carboxylic acids; Anhydrides, halides or salts thereof
    • D06M13/188—Monocarboxylic acids; Anhydrides, halides or salts thereof
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    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
    • D06M13/46—Compounds containing quaternary nitrogen atoms
    • D06M13/463—Compounds containing quaternary nitrogen atoms derived from monoamines
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    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/39—Aldehyde resins; Ketone resins; Polyacetals
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    • D06M2200/10—Repellency against liquids
    • D06M2200/12—Hydrophobic properties

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Abstract

The invention relates to a fabric waterproof agent, in particular to a fluorine-free waterproof finishing emulsion for fabric and application thereof. The components of the fluorine-free waterproof finishing emulsion are calculated according to the parts by weight (dry matter components): a)80-40 parts of long carbon chain modified amino resin, b)1-8 parts of cation modified long carbon chain amino resin, c)1-10 parts of metal complex of long carbon chain carboxylic acid, d)10-55 parts of wax, e)0.05-3 parts of cation emulsifier, f)0.01-2 parts of nonionic emulsifier and g)0.001-1.5 parts of organic acid or inorganic acid. The waterproof agent is suitable for waterproof finishing of terylene, cotton, ester, artificial boards or papermaking and various blended fabrics, and has excellent waterproof performance.

Description

Fluoride-free waterproof finishing emulsion for fabric and application thereof
Technical Field
The invention relates to a fabric waterproof agent, in particular to a fluorine-free waterproof finishing emulsion for fabric and application thereof.
Background
The fabric water repellent is generally an organic fluoride, silicone, melamine resin, wax, polyurethane, pyridinium salt, or the like. Among them, the organofluorine compounds have the best effect and are water-repellent, oil-repellent and stain-repellent. But the PFOS and PFOA are very stable in properties, difficult to degrade and high in bioaccumulation and are harmful to organisms. The European Union has already established legislation to gradually forbid PFOA and salts thereof, and starting from 7 months in 2020, PFOA and substances containing PFOA in degradation products are completely forbidden. Other types of water repellent agents have not the same water repellent performance as organic fluorides, but they have advantages in that they are safe and environmentally friendly. For example, silicone based water repellents are often harsh to the process conditions under which the fabric is treated, otherwise it tends to cause spotting of the fabric surface. Polyurethane can cover the surface of the fabric to form a waterproof film, but the air permeability of the fabric is hindered, and the comfort is poor. And the polyurethane is not very hydrophobic and has poor water resistance. Similar problems exist with other types of waterproofing agents, and therefore, it is desirable to try to achieve the waterproofing level of organofluoro compounds to reduce or replace the use of organofluoro compounds by modifying these types of waterproofing agents to improve their waterproofing, air permeability, hand feel, and wash resistance.
For example, japanese patent No. EP0632157a1 discloses a copolymer of acrylic acid ester and methacrylic acid ester copolymerized with silicone, which is used with ethanol or the like as a solvent and gives water resistance and soft hand to fabrics after use.
US patent US3374100A discloses an emulsion of a combination of a tertiary amine, a wax and a polyvalent metal salt. The fabric treated by the emulsion has water resistance.
US3432319A discloses a paraffin emulsion with methyl cellulose as emulsifier, which is mainly used for water and moisture proofing of fiber board.
US7354458B2 discloses a composition emulsion of wax, polyurethane and emulsifier. The emulsion can endow the fabric with waterproof performance.
U.S. patent No. WO2013057303A discloses a crosslinker resin prepared from melamine, formaldehyde and an alkanol which is capable of reacting with a heat sensitive substrate to impart a certain water repellency to the substrate.
For environmental protection and convenience of operation, the fabric waterproofing agent is generally processed into an aqueous emulsion, which requires introduction of a hydrophilic group in the structure of the waterproofing agent or use of an external emulsifier having hydrophilicity, resulting in a decrease in the water resistance of the final product. Therefore, a plurality of emulsifiers suitable for main waterproof substances are often required to be screened out, and are reasonably matched to play a synergistic effect, so that the stability of the emulsion is ensured and the waterproof performance is ensured. The invention adopts a cation modified long carbon chain amino resin, and the stability of the emulsion can be obviously improved by matching the resin with other cation and nonionic emulsifiers.
Disclosure of Invention
The invention aims to provide a fluoride-free waterproof finishing emulsion for fabrics and application thereof.
In order to achieve the purpose, the invention adopts the technical scheme that:
a fluorine-free waterproof finishing emulsion for fabrics comprises the following components in parts by weight (dry matter components): a)80-40 parts of long carbon chain modified amino resin, b)1-8 parts of cation modified long carbon chain amino resin, c)1-10 parts of metal complex of long carbon chain carboxylic acid, d)10-55 parts of wax, e)0.05-3 parts of cation emulsifier, f)0.01-2 parts of nonionic emulsifier and g)0.001-1.5 parts of organic acid or inorganic acid.
The solid content of the fluorine-free waterproof finishing emulsion is 20-40wt%, preferably 30-40 wt%, and more preferably 40 wt%.
The long carbon chain modified amino resin of the component a) is obtained by reacting hexamethylol melamine or short carbon chain alcohol ether compound of hexamethylol melamine with aliphatic long carbon chain alcohol, aliphatic long carbon chain carboxylic acid or aliphatic long carbon chain N-methylolamide.
Further, the product is obtained by reacting 1mol of hexamethylol melamine or short carbon chain alcohol ether compound thereof with 6mol of long carbon chain alcohol or carboxylic acid and hydroxymethyl amide, and the obtained product can be long carbon chain ether, ester or amide. The substance has good water resistance due to a large number of hydrophobic groups distributed on the periphery of the structure.
Taking hexamethylol melamine or its short carbon chain alcohol ether compound and long carbon chain alcohol to prepare component a) as an example, the reaction formula is as follows:
Figure BDA0001499561840000021
radical R1Is H or C1-C8 alkyl, preferably C1-C4 alkyl, R2Is C12-C40 alkyl, C12-C40 alkenyl or C12-C40 alkynyl, preferably C12-C22 alkyl, C12-C22 alkenyl or C12-C22 alkynyl.
The component a long carbon chain modified amino resin is obtained by reacting 1mol of hexamethylol melamine or short carbon chain alcohol ether compound thereof with 6mol of long carbon chain alcohol or carboxylic acid and hydroxymethyl amide, and the obtained product can be long carbon chain ether, ester or amide. On the upper partThe short carbon chain alcohol generally refers to an aliphatic alcohol having less than 4 carbon atoms, and most used is methanol. Due to the presence of melamine on>N(CH2OH)2The group activity is high, the methylol melamine monomers are easy to crosslink, so the reaction is preferably performed by using methylol melamine with short carbon chain etherification. The preparation process comprises the following steps: mixing short carbon chain etherified methylol melamine with long carbon chain ether or carboxylic acid, methylol amide, heating to melt, adding 0.1-0.5% hydrochloric acid or sulfuric acid as catalyst, heating to 90 deg.c to react for 1.5 hr, heating to 140 deg.c to react for 2 hr, and vacuum eliminating low-boiling-point matter during the reaction. The product obtained is component a. It is worth noting that when hydroxymethyl amide is used to react with hydroxymethyl melamine with short carbon chain etherified, the reaction is more vigorous, and the system is easy to flush when the vacuum is reduced due to the viscous material, and the vacuum degree should be carefully controlled.
The component b) cation modified long carbon chain amino resin is prepared by reacting hexamethylol melamine or hexamethylol melamine short carbon chain alcohol ether compound with quaternary ammonium salt or tertiary amine and then reacting with aliphatic long carbon chain alcohol or aliphatic long carbon chain carboxylic acid or aliphatic long carbon chain N-hydroxymethyl amide.
Furthermore, the compound is prepared by reacting 1mol of hexamethylol melamine or short carbon chain alcohol ether compound thereof with 5mol of long carbon chain alcohol (or carboxylic acid, hydroxymethyl amide and the like) and 1mol of quaternary ammonium salt or tertiary amine with one hydroxyl group. The main structure of the compound is similar to that of the component a, the hydrophobic part of the compound can be well embedded into the component a, and the hydrophilic group extends into the water phase, so that the compound has a certain surface activity effect.
Taking hexamethylol melamine or its short carbon chain alcohol ether compound to react with long carbon chain alcohol and quaternary ammonium salt with hydroxyethyl group to prepare component b) as an example, the reaction formula is as follows:
Figure BDA0001499561840000031
the preparation process comprises the following steps: mixing 1mol of short carbon chain etherified methylol melamine with 1mol of quaternary ammonium salt or tertiary amine with hydroxyl, heating to melt, adding 0.1-0.5% hydrochloric acid or sulfuric acid and the like as a catalyst, heating to 90 ℃ to react for 1.5h, adding 5mol of long carbon chain ether or carboxylic acid and methylol amide, continuing to react at 90 ℃ for 2h, and always performing vacuum removal on low-boiling-point substances in the reaction process. The product obtained is component b.
In the reaction formula, the negative ion of the quaternary ammonium salt is Cl-The anion of the quaternary ammonium salt can be bromide ion, methyl sulfate group and the like besides chloride ion.
The examples listed in the above reaction formula are the reaction of hexamethylol melamine or its short carbon chain alcohol ether compound with long carbon chain alcohol and quaternary ammonium salt with hydroxyethyl group to prepare component b, and the procedure and principle for preparing component b by using hexamethylol melamine or its short carbon chain alcohol ether compound with long carbon chain alcohol and tertiary amine with hydroxyethyl group are the same as those when using quaternary ammonium salt, and will not be described repeatedly.
The short-carbon-chain alcohol etherate of the hexamethylol melamine is obtained by the reaction of hexamethylol melamine and fatty alcohol of C1-C8;
the carbon number of the aliphatic long carbon chain alcohol, the aliphatic long carbon chain carboxylic acid or the aliphatic long carbon chain N-hydroxymethyl amide is C12-C20, preferably C12-C18. Such as lauryl alcohol, stearyl alcohol, palmitic acid, oleic acid, N-methylol octadecanamide, and the like.
The structure of the quaternary ammonium salt or the tertiary amine respectively contains a hydroxyl group and a rosin group; or a hydroxyl group and an aliphatic long carbon chain of C12-C20.
Wherein the rosin group comprises abietic acid group and dehydroabietic amine group
Wherein the typical structure of the abietic acid group is:
Figure BDA0001499561840000041
since rosin is a mixture of various resin acids, the structure is only that of the main component rosin acid in rosin, and the rosin-based surfactant actually used also includes other components in rosin resin, such as levopimaric acid, palustric acid, dehydroabietic acid, neoabietic acid, dihydroabietic acid, tetrahydroabietic acid, and the like.
The typical structure of dehydroabietylamine is:
Figure BDA0001499561840000042
likewise, dehydroabietylamine includes dehydroabietylamine prepared from other components of the rosin resin.
The quaternary ammonium salt containing rosin groups is quaternary ammonium salt shown as formula I or quaternary ammonium salt shown as formula II
Formula I
Figure BDA0001499561840000051
In the formula, R8,R9Alkyl of ═ C1-C20, R6Is a rosin acid group;
formula II
Figure BDA0001499561840000052
In the formula, R8,R9Alkyl of ═ C1-C20, R7Is a dehydroabietylamine group;
the tertiary amine containing the rosin group is tertiary amine shown as III or tertiary amine shown as IV,
formula III
Figure BDA0001499561840000053
In the formula, R8Alkyl of ═ C1-C20, R6Is a rosin acid group;
formula IV
Figure BDA0001499561840000054
In the formula, R8Alkyl of ═ C1-C20, R7Is dehydroabietylamine group.
Examples of suitable linear aliphatic hydrocarbyl quaternary or tertiary amines containing one hydroxyl group in the above reaction processes are N, N-dimethyl-N-hydroxyethyl-N-octadecyl ammonium methylsulfate, N-methyl-N-hydroxyethyl-N, N-dioctadecyl ammonium methylsulfate, N-methyl-N-hydroxyethyl-N-octadecyl amine, N-methyl-N-hydroxyethyl-N-tetradecyl amine, N, N-dioctadecyl-N-hydroxyethyl amine, N, N-didodecyl-N-hydroxyethyl amine.
Examples of suitable quaternary ammonium salts containing one hydroxyl group and a rosin-based group in the above reaction process are N, N-dimethyl-N-hydroxyethyl-N-abietic acid carboxymethoxymethylammonium chloride, N, N-dimethyl-N-hydroxyethyl-N-dehydroabietic ammonium chloride. Examples of suitable tertiary amines containing one hydroxyl group and a rosin group are N-methyl-N-hydroxyethyl-N-abietic acid carboxymethoxymethylamine, N-methyl-N-hydroxyethyl-N-dehydroabietylamine.
The component c) long carbon chain carboxylic acid metal complex is (RCOO)nM, wherein R is C12-C20 straight-chain aliphatic carboxylic acid or C12-C20 carboxylic acid containing 1-3 unsaturated double bonds or triple bonds, n is 1-4, and M is metal ions.
Further, the long carbon chain carboxylic acid metal complex of component C is C12-C20 linear aliphatic carboxylic acid or carboxylic acid containing 1-3 unsaturated double or triple bonds, preferably C12-C18 linear aliphatic carboxylic acid or carboxylic acid containing 1-3 unsaturated double or triple bonds, the above carboxylic acid and Ca2+、Mg2+、Al3+、Zr4+、Ba2+The complex formed by water-soluble salt of metal ion can be selected from calcium chloride, magnesium chloride, aluminum chloride, barium chloride, zirconium acetate, magnesium sulfate, aluminum sulfate, etc., preferably calcium chloride, aluminum sulfate and zirconium acetate, more preferably aluminum sulfate and zirconium acetate. Examples of the carboxylic acid metal complex which can be used are calcium stearate, aluminum stearate, magnesium stearate, zirconium stearate, magnesium oleate, aluminum oleate, zirconium oleate and the like, with aluminum stearate and zirconium stearate being preferred.
The wax in the component d) is one or a mixture of several of waxes with the melting point of 40-85 ℃.
Further, component d is a wax having a melting point of 40-85 deg.C, preferably 50-75 deg.C, more preferably 50-65 deg.C. Natural animal and vegetable waxes that may be selected include, but are not limited to, candelilla wax, carnauba wax, white insect wax, spermaceti wax, beeswax, and the like. The paraffin can be refined or semi-refined paraffin. Suitable wax components also include synthetic waxes such as microcrystalline waxes, polyethylene waxes, and the like. Preferred waxes are refined paraffin waxes and microcrystalline waxes, more preferably refined paraffin waxes.
The emulsifier used in the emulsion preparation process includes cationic emulsifier (e) and nonionic emulsifier (f), which can be mixed with component b to stabilize the emulsion well.
The cationic emulsifier in the component e) is a C8-C20 quaternary ammonium salt type cationic emulsifier, preferably a long carbon chain with carbon number of C16-C18, wherein the negative ion of the quaternary ammonium salt is chloride ion or methyl sulfate; the non-ionic emulsifier in the component f) is C8-C20 polyoxyethylene ether, Tween and span.
The cationic emulsifier can be selected from coco trimethyl ammonium chloride, tetradecyl trimethyl ammonium chloride, hexadecyl trimethyl ammonium chloride, octadecyl trimethyl ammonium chloride, tetradecyl benzyl dimethyl ammonium chloride, dioctadecyl dimethyl ammonium chloride, palm carboxyethyl hydroxyethyl methyl ammonium sulfate, lauroyl propyl trimethyl methyl ammonium sulfate, distearoyl ethyl dimethyl ammonium chloride, propylene-bis (octadecyl dimethyl) diammonium, tricetyl methyl ammonium chloride, dioctadecyl polyoxyethylene diquaternary ammonium salt, etc.
The non-ionic emulsifier is long carbon chain initial polyoxyethylene ether, tween, span and the like. The carbon number of the long carbon chain end of the polyoxyethylene ether is C8-C20, preferably C12-C18; the number of polymerized ethoxy groups is from 3 to 20, preferably from 3 to 15, more preferably from 5 to 12. Examples of alternative polyoxyethylene ethers are AEO-10, polyoxyethylene (15) stearate, polyoxyethylene (20) ricinoleate, polyoxyethylene (10) isomerate, and the like.
The pH range of the waterproof agent emulsion prepared by the method is 4-6, and inorganic acid or organic acid can be used for adjusting the pH. The inorganic acid can be selected from hydrochloric acid, sulfuric acid, phosphoric acid, phosphorous acid, etc. The organic acid can be selected from formic acid, acetic acid, citric acid, etc. Weak organic acids, such as acetic acid, are preferred.
During emulsification, all materials are mixed, heated to about 95 ℃, then water with the temperature of about 95 ℃ is added, the mixture is uniformly dispersed by a high-speed dispersion machine, the particle size is smaller than 1 mu, and then the mixture is treated by a high-pressure homogenizer at the temperature of 75-85 ℃, so that stable emulsion with the particle size of about 400nm is obtained. In order to ensure that the emulsion particles are small enough, the circumferential linear speed of the high-speed dispersion machine is not less than 15m/s when the high-speed dispersion machine works, and the working pressure of the high-pressure homogenizer is not less than 800 bar.
The application of the fluorine-free waterproof finishing emulsion for the fabric is characterized in that: the emulsion is applied as a water-proofing agent in the preparation process of blended fabrics, artificial boards or papermaking. The water-proof finishing agent is suitable for water-proof finishing of terylene, cotton, ester and various blended fabrics, artificial boards or papermaking, and has excellent water-proof performance. The invention has the advantages that:
the emulsion of the invention introduces long carbon chain hydrophobic group into melamine molecule, which plays a role of water resistance. Meanwhile, a small amount of cationic structures are introduced into melamine molecules, so that the waterproof agent can be successfully emulsified while the water resistance is ensured, and the emulsion is stable in storage.
The fluorine-free waterproof emulsion comprises a waterproof component which takes wax and long carbon chain modified amino resin as main components, amino resin which has a structure similar to that of the long carbon chain modified amino resin and has a cationic hydrophilic group, quaternary ammonium salt, a nonionic surfactant, other auxiliary components and the like. The waterproof emulsion comprises a long carbon chain modified cationic amino resin, and the main structure of the resin is similar to that of the long carbon chain modified amino resin with waterproof performance, except that a cationic hydrophilic group is introduced. The amino resin introduced with the cationic hydrophilic group can be well blended with the original amino resin, and is greatly helpful for the stability of the emulsion. The invention adopts cation modified long carbon chain amino resin, and the stability of the emulsion can be obviously improved by matching the resin with other cation and nonionic emulsifiers. Furthermore, the composition is suitable for the waterproof finishing of terylene, cotton, ester, various blended fabrics, artificial boards or papermaking, and has excellent initial waterproof performance. The emulsion prepared by the invention can be matched with polyurethane emulsion for use, and can provide water resistance after multiple times of washing.
Detailed Description
The invention is further illustrated by the following examples.
Example 1.
Synthesis of component a 1: a500 mL four-necked flask was charged with 39g of hexamethoxymethylenemelamine, 0.1mol of hexamethoxymethylenemelamine, 162g of octadecanol, and heated to melt the mixture, and then 0.4g of concentrated hydrochloric acid was added to continue the temperature rise to 90 ℃. When the system started to reflux, methanol was distilled off under vacuum. After the reaction is carried out for 1.5h at the temperature of 90 ℃, the temperature is raised to 140 ℃ for reaction for 2h, the product is colorless and transparent viscous substance, and the waxy solid is obtained after cooling.
Example 2.
Synthesis of component a 2: a500 mL four-necked flask was charged with 39g of hexamethoxymethylenemelamine (0.1 mol) and 170g of octadecanoic acid (0.6 mol), heated to melt the contents, and then 0.4g of concentrated hydrochloric acid was added to continue the temperature rise to 90 ℃. When the system started to reflux, methanol was distilled off under vacuum. After the reaction is carried out for 1.5h at the temperature of 90 ℃, the temperature is raised to 140 ℃ for reaction for 2h, the product is colorless and transparent viscous substance, and the waxy solid is obtained after cooling.
Example 3.
Synthesis of component a 3: a500 mL four-necked flask was charged with 39g of hexamethoxymethylenemelamine, 0.1mol of hexamethoxymethylenemelamine, 188g of octadecanol, 0.6mol of octadecanol, heated to melt the mixture, and then 0.4g of concentrated hydrochloric acid was added to continue the temperature rise to 90 ℃. When the system begins to have reflux, adding vacuum to distill off methanol, and controlling the vacuum degree to prevent flushing. The reaction is carried out at 90 ℃ for 1.5h, then the temperature is raised to 140 ℃ for 2h, the product is light yellow transparent viscous substance, and the waxy solid is obtained after cooling.
Example 4.
Synthesis of component b 1: 18g of hexamethoxy methylene melamine, 0.05mol of hexamethoxy methylene melamine, 22.5g of N, N-dimethyl-N-hydroxyethyl-N-abietic acid carboxymethoxy methyl ammonium chloride and 0.05mol of N, N-dimethyl-N-hydroxyethyl-N-abietic acid are put into a 250mL four-neck flask, the materials are heated to melt, 0.4g of concentrated hydrochloric acid is added, the temperature is continuously raised to 90 ℃ for reaction for 1.5h, 67.5g of octadecanol and 0.25mol of octadecanol are added, and the reaction is continuously carried out for 2h at 90 ℃. After the reaction is started to have reflux, vacuum is added to remove low-boiling substances. The product was a colorless, clear, viscous mass which cooled to a waxy solid.
Example 5.
Synthesis of component b 2: a250 mL four-neck flask was charged with 18g, 0.05mol of hexamethoxymethylenemelamine and 22.6g, 0.05mol of N, N-dimethyl-N-hydroxyethyl-N-octadecylammonium methylsulfate, heated to melt the materials, and then added with 0.4g of concentrated hydrochloric acid, further heated to 90 ℃ to react for 1.5h, then added with 67.5g, 0.25mol of octadecanol, and further reacted at 90 ℃ for 2 h. After the reaction is started to have reflux, vacuum is added to remove low-boiling substances. The product was a colorless, clear, viscous mass which cooled to a waxy solid.
Example 6.
Synthesis of component b 3: a250 mL four-necked flask was charged with 18g, 0.05mol of hexamethoxymethylenemelamine and 13.5g, 0.05mol of N-methyl-N-hydroxyethyl-N-tetradecylamine, heated to melt the materials, and then added with 0.4g of concentrated hydrochloric acid, heated to 90 ℃ to react for 1.5 hours, and then added with 67.5g, 0.25mol of octadecanol, and reacted at 90 ℃ for 2 hours. After the reaction is started to have reflux, vacuum is added to remove low-boiling substances. The product was a colorless, clear, viscous mass which cooled to a waxy solid.
Examples 7 to 17.
Various examples of emulsion preparations are provided, some of which are listed in Table 1.
TABLE 1 examples 7 to 17
Figure BDA0001499561840000081
Figure BDA0001499561840000091
1631: cetyltrimethylammonium chloride, D1821: dioctadecyldimethylammonium chloride, TC-90: tricetyl methyl ammonium chloride, E1310: isomeric tridecanol polyoxyethylene (10) ethers
*: solid separation rate of emulsion after centrifugation at 2300G for 15min
The fabric waterproof finishing process comprises the following steps: and (3) diluting the emulsion to 1% by using deionized water, soaking the fabric in the working solution, and rolling off the excess solution, wherein the solution feeding rate is about 60%. The rolled cloth is dried at the temperature of 100-120 ℃ for 60-120s and then dried at the temperature of 160 ℃ for 60-120 s. The waterproof performance of the fabric after being treated by the waterproof emulsion is evaluated according to the GB/T4745-.
TABLE 2 Primary waterproofness of treated fabrics
Figure BDA0001499561840000092
From the above experimental data, it can be seen that the emulsion with the cationic modified melamine added is more stable than the emulsion without the cationic modified melamine added, and the solid separation rate of the emulsion after centrifugation for 15min at 2300G is obviously reduced. And through reasonable matching of different substances, the water resistance of the emulsion is not influenced.
Examples 18 to 19
The waterproof emulsion provided by the invention can provide good primary waterproof performance for fabrics, and can meet the waterproof application without being washed by a chemical cleaning agent. However, the cloth treated by the waterproof emulsion prepared by the invention has poor washing waterproofness, and in order to improve the washing waterproofness, the emulsion and the cationic or nonionic polyurethane emulsion can be compounded for use, so that the washing waterproofness of the fabric can be obviously improved. Typically, the polyurethane emulsion is used in an amount of 5-20% of the composite finish. The polyurethane emulsion used in the following examples was FP-BA available from Shanghai Yayun textile auxiliaries Co., Ltd in an amount of 10%. Table 3 shows the comparison of the water-proof performance of the fabric before and after adding the polyurethane.
TABLE 3 comparison of the Water resistance of the fabrics before and after addition of polyurethane
Figure BDA0001499561840000093
IN SR: primary water-proofing, 5HL IR SR: domestic washing and ironing for 5 times
As can be seen from the data in Table 3, the waterproof emulsion provided by the invention can be used together with polyurethane emulsion to remarkably improve the washing waterproofness of fabrics, and particularly has more obvious effect on polyester fabrics.

Claims (7)

1. A fluoride-free waterproof finishing emulsion for fabrics is characterized in that: the fluorine-free waterproof finishing emulsion comprises the following components in parts by weight: a)80-40 parts of long carbon chain modified amino resin, b)1-8 parts of cation modified long carbon chain amino resin, c)1-10 parts of metal complex of long carbon chain carboxylic acid, d)10-55 parts of wax, e)0.05-3 parts of cation emulsifier, f)0.01-2 parts of nonionic emulsifier and g)0.001-1.5 parts of organic acid or inorganic acid;
the long carbon chain modified amino resin of the component a) is obtained by reacting hexamethylol melamine or short carbon chain alcohol ether of hexamethylol melamine with aliphatic long carbon chain alcohol, aliphatic long carbon chain carboxylic acid or aliphatic long carbon chain N-methylolamide;
the component b) cation modified long carbon chain amino resin is prepared by reacting hexamethylol melamine or hexamethylol melamine short carbon chain alcohol ether compound with quaternary ammonium salt or tertiary amine and then reacting with aliphatic long carbon chain alcohol or aliphatic long carbon chain carboxylic acid or aliphatic long carbon chain N-methylolamide;
the short-carbon-chain alcohol etherate of the hexamethylol melamine is obtained by the reaction of hexamethylol melamine and fatty alcohol of C1-C8;
the carbon number of the aliphatic long carbon chain alcohol, the aliphatic long carbon chain carboxylic acid or the aliphatic long carbon chain N-hydroxymethyl amide is C12-C20.
2. The fluorine-free water repellent finish emulsion for fabrics according to claim 1, characterized in that: the solid content of the fluorine-free waterproof finishing emulsion is 20-40 wt%.
3. The fluorine-free water repellent finish emulsion for fabrics according to claim 1, characterized in that: the structure of the quaternary ammonium salt or the tertiary amine respectively contains a hydroxyl group and a rosin group; or a hydroxyl group and an aliphatic long carbon chain of C12-C20.
4. The fluorine-free water repellent finish emulsion for fabrics according to claim 3, characterized in that: the quaternary ammonium salt containing rosin groups is quaternary ammonium salt shown as formula I or quaternary ammonium salt shown as formula II
Formula I
Figure 465781DEST_PATH_IMAGE001
Ⅰ
In the formula, R8, R9= C1-C20 alkyl, R6Is a rosin acid group;
formula II
Figure 662407DEST_PATH_IMAGE002
Ⅱ
In the formula, R8, R9= C1-C20 alkyl, R7Is a dehydroabietylamine group;
the tertiary amine containing the rosin group is tertiary amine shown as III or tertiary amine shown as IV,
formula III
Figure 885578DEST_PATH_IMAGE003
Ⅲ
In the formula, R8= C1-C20 alkyl, R6Is a rosin acid group;
formula IV
Figure 825852DEST_PATH_IMAGE004
Ⅳ
In the formula, R8= C1-C20 alkyl, R7Is dehydroabietylamine group.
5. The fluorine-free water repellent finish emulsion for fabrics according to claim 1, characterized in that:
the component c) long carbon chain carboxylic acid metal complex is (RCOO)nM, wherein R is C12-C20 straight-chain aliphatic carboxylic acid or C12-C20 carboxylic acid containing 1-3 unsaturated double bonds or triple bonds, n is 1-4, and M is metal ions.
6. The fluorine-free water repellent finish emulsion for fabrics according to claim 1, characterized in that: the cationic emulsifier in the component e) is a quaternary ammonium salt type cationic emulsifier C8-C20, wherein the negative ions of the quaternary ammonium salt are chloride ions or methyl sulfate; the non-ionic emulsifier in the component f) is C8-C20 polyoxyethylene ether, Tween and span.
7. Use of a fluorine-free water repellent finishing emulsion for fabric according to claim 1, characterized in that: the emulsion is applied as a water-proofing agent in the preparation process of blended fabrics, artificial boards or papermaking.
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