CN112300348B - Fiber deepening agent and preparation method and application thereof - Google Patents
Fiber deepening agent and preparation method and application thereof Download PDFInfo
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- CN112300348B CN112300348B CN202011253716.4A CN202011253716A CN112300348B CN 112300348 B CN112300348 B CN 112300348B CN 202011253716 A CN202011253716 A CN 202011253716A CN 112300348 B CN112300348 B CN 112300348B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F292/00—Macromolecular compounds obtained by polymerising monomers on to inorganic materials
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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
- 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
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
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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
- 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
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
- D06M15/277—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof containing fluorine
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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
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/16—Synthetic fibres, other than mineral fibres
- D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M2101/32—Polyesters
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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
- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/50—Modified hand or grip properties; Softening compositions
Abstract
The invention provides a fiber deepening agent and a preparation method and application thereof, wherein the fiber deepening agent is of a core-shell structure; the core material of the core-shell structure comprises silicon dioxide; the shell layer material of the core-shell structure comprises fluorine-containing polymer and polyacrylate; through the design of the hard core and soft shell type structure, the fiber deepening agent has a rough surface provided by silicon dioxide particles, and simultaneously has a low-refractive-index film layer brought by a shell polymer, so that the fiber deepening agent has an excellent deepening effect, does not influence the hand feeling and the rubbing fastness of a fiber product, and has a high application value.
Description
Technical Field
The invention belongs to the technical field of polymer materials, and particularly relates to a fiber deepening agent, and a preparation method and application thereof.
Background
The terylene is a synthetic fiber variety with the largest output in the world, wherein the terylene superfine fabric has the characteristics of soft and smooth hand feeling, good drapability, air permeability, moisture absorption, quick drying, fluffy and plump appearance, comfortable wearing and the like, and is deeply loved by people. Some key technologies are not completely broken through when the superfine polyester fiber is rapidly developed, and the key technologies become barriers for the continuous development of the superfine polyester fiber, and the preparation of the deep-color superfine polyester fiber is one of the technologies. This is because the fiber has a small fineness, a high crystallinity, a smooth surface, a high refractive index, a large specific surface area, and almost no reactive groups, and therefore, it is difficult to dye the fiber in a deep color.
At present, the main approaches for deepening and finishing the fabrics at home and abroad have two strategies: the first is a pretreatment method, which comprises the steps of selecting dyes with high affinity and good dyeing performance, and reasonably selecting dyeing auxiliaries and a dyeing process; and the other is post-treatment, which comprises roughening the surface of the polyester fiber, finishing by adopting low-refractive-index resin and the like. The pretreatment method needs to rely on dyes, auxiliaries, processes or equipment with more excellent performance, but related auxiliary products for the superfine terylene are almost not available on the market at present, and corresponding product development is rarely reported, so that the development is rarely advanced. In contrast, the aftertreatment process has been developed more in recent years.
The two strategies of post-treatment are implemented in the same way, i.e. by different methods, the amount of reflected light is reduced, the amount of refracted light entering the fibers is increased, the amount of colored light is increased, and the apparent depth of color of the fabric is increased. The difference between the two methods is that the fiber surface roughening method is to form a layer of uneven surface on the fiber surface by various technologies, light is diffusely reflected on the uneven surface, and most of the light is reflected to other surfaces of the pits and then refracted into the fiber. As a result of repeating the reflection and refraction, the reflected light on the surface of the fiber tends to decrease, the specific gravity of the colored light reflected from the fiber after internal absorption increases, and the apparent dyeing depth of the fiber increases; the low-refractive-index resin finishing utilizes the refraction effect of the low-refractive-index resin, and because the material has a small refractive index, light can easily penetrate through the material, the quantity of reflected light is small, and the obtained color is darker; when the surface of the fiber is treated by the resin with low refractive index, the apparent refractive index of the fiber is reduced, the quantity of reflected light can be reduced, the specific gravity of absorbed light is increased, and the apparent dyeing depth is increased, and the deepening effect is more obvious when the refractive index of the resin is smaller.
CN104074053A discloses an efficient deepening agent and an application method of preparation and after-treatment thereof, which is an acrylate resin deepening agent polymerized by cross-linked polymethacrylate and is matched with an organic silicon emulsion to adopt a two-step treatment application process, namely, the acrylic resin emulsion is used in the first step of padding, is attached to the surface of a fiber through heat setting, and then the second step of padding is carried out, so that an organic silicon film covers the rough surface of the fiber, and the efficient deepening agent has the characteristics of higher deepening rate, small color difference, improved hand feeling, small influence on dry and wet rubbing fastness and the like.
CN106478859A discloses a dyed polyester fabric deepening agent and a preparation method thereof, wherein a semi-continuous seed emulsion polymerization method is used for adding an organic silicon monomer into a back half section of a pre-emulsion for emulsification and dropwise polymerization by using a cationic emulsifier, a non-ionic emulsifier, methyl methacrylate, styrene, acrylonitrile, ethylene glycol methacrylate, a fluorine-containing monomer, an organic silicon monomer, an initiator and deionized water to obtain a deepening agent emulsion with a core-shell structure. CN 11069861A discloses a core-shell type methacrylate copolymer particle emulsion, a preparation method thereof and a fabric deepening agent composition, wherein a similar 'soft core-hard shell' type core-shell structure is also adopted, and the deepening can be increased by 70% at most by constructing an uneven film on a fabric. However, the deepening agent prepared by the two methods has a hard 'shell' structure, so that the treated fiber fabric has the defects of low softness and low rubbing color fastness.
Therefore, it is very important to develop a fiber deepening agent with less dosage, obvious deepening effect and no influence on the hand feeling and the rubbing fastness of the fiber.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a fiber deepening agent, a preparation method and application thereof, wherein the fiber deepening agent is of a core-shell structure; the core material of the core-shell structure comprises silicon dioxide; the shell layer material of the core-shell structure comprises fluorine-containing polymer and polyacrylate, and through the design of the soft-shell hard core, the prepared fiber deepening agent has low dosage, obvious deepening effect, no influence on hand feeling and rubbing fastness of a fiber product, and high application value.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides a fiber deepening agent, wherein the fiber deepening agent is of a core-shell structure;
the core material of the core-shell structure comprises silicon dioxide; the shell layer material of the core-shell structure comprises fluorine-containing polymer and polyacrylate.
Since the refractive index of the fiber material is small, light easily penetrates, the amount of reflected light is small, and the obtained color is dark, the deep dyeing property of the fiber material with the small refractive index is better than that of the fiber material with the large refractive index. The refractive index of the terylene is as high as 1.72, and the terylene has very strong specular reflection performance under the condition of smooth surface, so the terylene is difficult to dye dark color. When the surface of the polyester fiber is covered with the resin layer, the surface reflectivity can be remarkably reduced, so that a larger apparent dyeing depth can be obtained under the same dye using amount.
The core material of the deepening agent with the core-shell structure provided by the invention comprises silicon dioxide, the emulsion with the core-shell structure ensures that silicon dioxide nano particles after film formation can be uniformly distributed in a polymer film, the agglomeration phenomenon of the silicon dioxide nano particles can not occur, the silicon dioxide is equivalent to one physical cross-linking point, the strength of the polymer film and the acting force between the polymer film and a microfiber can be greatly enhanced, and the friction fastness performance can be improved compared with the situation that the silicon dioxide is not added; the shell material comprises a combination of polyacrylate and a fluorine-containing polymer, wherein the polyacrylate has a lower refractive index (1.45-1.50), the fluorine-containing polymer has the lowest refractive index, the higher the fluorine content is, the smaller the refractive index is, and the refractive index of a common fluorine-containing acrylate homopolymer is below 1.40, so that the shell material has a very strong effect of reducing the refractive index of a system; in addition, the fluorine has small surface energy, can spontaneously cover other functional groups and is distributed on the surface of the fiber, so that the aim of greatly reducing the apparent refractive index can be fulfilled by using a small amount. The fiber deepening agent provided by the invention is used by selecting and matching the core material and the shell material to form a 'soft shell and hard core' structure, so that the fiber deepening agent has a good deepening effect and does not influence the hand feeling and the rubbing fastness of a fiber product.
Preferably, the emulsion particle size of the fiber deepening agent is 80-800 nm, such as 325nm, 335nm, 368nm or 405nm, and the specific values therebetween are limited by space and for the sake of brevity, the invention does not exhaust the specific values included in the range, further preferably 180-550 nm, and further preferably 250-450 nm.
Preferably, the content of silica in the fiber deepening agent is 2 to 40% by mass, for example, 11%, 14%, 16% or 17% by mass, and the specific values therebetween are limited by space and for the sake of brevity, the invention does not exhaust the specific values included in the range, and more preferably, the specific values are 5 to 30%, and still more preferably, 10 to 20%.
As a preferred technical scheme, the mass percentage of the silicon dioxide in the fiber deepening agent provided by the invention is 2-40%, so that the fiber deepening agent has a good deepening effect and does not influence the hand feeling of a fiber product. On one hand, if the content of the silicon dioxide is too high, the silicon dioxide can cause great influence on the hand feeling of the fiber product, and in addition, the reaction is easy to lose control, so that a large amount of silicon dioxide accumulation bodies are formed, and the adhesive force between a polymer layer and fibers is weakened; on the other hand, if the content of the silicon dioxide is too low, the deepening effect of the prepared deepening agent is poor, and only when the mass percentage of the silicon dioxide in the fiber deepening agent is 2-40%, the deepening agent with excellent deepening effect and without influencing the hand feeling of the fiber can be obtained.
Preferably, the silica has a particle size of 5 to 120nm, such as 15nm, 20nm or 25nm, and the specific values therebetween are not exhaustive, and for the sake of brevity, the invention is not intended to be exhaustive of the specific values included in the ranges, more preferably 10 to 60nm, and even more preferably 15 to 25nm.
As a preferred technical scheme, when the particle size of the silicon dioxide used as a core material in the fiber deepening agent provided by the invention is 5-120 nm, the deepening agent can have a good deepening effect, and the silicon dioxide is hard and is completely separated from a polymer, so that the prepared fiber deepening agent can form a rugged surface layer structure on the surface of a fiber, and the structure enables incident light to easily form refraction and diffuse reflection on the surface of a microfiber, and reduces reflected light, so that the absorption of the microfiber to the incident light is greatly increased, and the effect of enhancing the color depth is realized. Generally, when the particle size of the particles is less than 1 micron, especially less than 700 nm, the larger the particle size of the particles is, the stronger the refraction and diffuse reflection effects are, and the more obvious the deepening effect is; on the other hand, too large particle size of silica tends to give stiff and rough feeling to the hand of the fiber, and therefore there is a certain demand for the particle size of silica nanoparticles. On the premise of comprehensively considering hand feeling and deepening effect, silicon dioxide with the particle size of 5-120 nm is selected as a core material of the fiber deepening agent provided by the invention.
Preferably, the glass transition temperature of the shell material is-30 to 40 ℃, such as-5 ℃, -1 ℃,3 ℃ or 7 ℃, and the specific values therebetween are not exhaustive, and for brevity, the invention does not include the specific values included in the range, preferably-20 to 25 ℃, and more preferably-5 to 10 ℃.
As a preferred technical scheme, the glass transition temperature of the shell material of the deepening agent provided by the invention is-30-40 ℃, the acrylate polymer has various optional glass transition temperatures, and the acrylate polymer with the glass transition temperature of-30-40 ℃ is selected as the shell material, so that the film forming property and the viscosity of the shell polymer can be ensured, and the strength and the hardness of a polymer film layer can be maintained, therefore, the hand feeling of the microfiber fabric can be adjusted in a wider range by selecting the polymers with different glass transition temperatures, and the treated polyester microfiber still has good hand feeling.
Preferably, the mass percentage of the fluoropolymer in the shell material is 2-40%, for example, 11%, 14%, 15% or 17%, and the specific values therebetween are limited by space and for the sake of brevity, the present invention does not exhaustive list the specific values included in the range, more preferably 5-30%, and still more preferably 10-20%.
Preferably, the shell layer thickness of the core-shell structure is 20 to 350nm, such as 40nm, 60nm, 80nm, 120nm, 140nm, 160nm, 180nm, 220nm, 260nm, 280nm, 300nm, 320nm or 340nm, and the specific values therebetween are limited by the space and the simplicity, and the invention does not exhaustive list of the specific values included in the range, further preferably 80 to 250nm, and further preferably; 120-200 nm.
In a second aspect, the present invention provides a method for preparing the fiber deepening agent according to the first aspect, wherein the method comprises the following steps:
(1) Mixing an acrylate monomer, a first nonionic emulsifier and a first cationic emulsifier to obtain a first pre-emulsion; mixing a fluorine-containing monomer, a second nonionic emulsifier and a second cationic emulsifier to obtain a second pre-emulsion; modifying the silica sol by using a silane coupling agent to obtain modified silica sol;
(2) And (2) mixing the modified silica sol obtained in the step (1) with a cationic initiator, and adding the first pre-emulsion and the second pre-emulsion obtained in the step (1) into the mixture for reaction to obtain the fiber deepening agent.
The method for preparing the fiber deepening agent comprises the steps of firstly preparing a first pre-emulsion, a second pre-emulsion and modified silica sol, modifying silica through a silane coupling agent, increasing the hydrophobicity of particles, enabling polymers on a shell layer to be combined with the silica more easily, then mixing the modified silica sol with a cationic initiator, adding the first pre-emulsion and the second pre-emulsion into the modified silica sol for reaction, selecting the water-soluble cationic initiator as the initiator, mixing the initiator with the silica in advance, anchoring the initiator on the surface of the silica particles by utilizing the electronegativity characteristic of the surface of the silica particles and the interaction between positive charges and negative charges, wherein the whole silica particles play a role of 'seeds' in the polymerization process, and the preparation of the fiber deepening agent with a core-shell silica/polymer structure is realized.
Preferably, the first pre-emulsion in the step (1) comprises 40 to 160 parts by weight of acrylate monomers, 3 to 4 parts by weight of first nonionic emulsifiers and 1.5 to 2 parts by weight of first cationic emulsifiers.
The acrylate monomer may be 70 parts by weight, 75 parts by weight, 80 parts by weight, 90 parts by weight, or the like.
The first nonionic emulsifier can be 3 parts by weight, 3.2 parts by weight, 3.6 parts by weight, or the like.
The first cationic emulsifier can be 1.5 parts by weight, 1.6 parts by weight, 1.8 parts by weight, or the like.
Preferably, the acrylate monomer includes a methacrylate monomer.
Preferably, the methacrylate-based monomer includes any one of methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, or t-butyl methacrylate, or a combination of at least two thereof.
Preferably, the acrylate monomer further comprises any one or a combination of at least two of methyl acrylate, ethyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate or tert-butyl acrylate.
By selecting acrylate monomers with different glass transition temperatures, a polymer is obtained, the hand feeling of the microfiber fabric is adjusted in a wider range, and the treated polyester microfiber still has good hand feeling.
Preferably, the acrylic ester monomer, the first nonionic emulsifier and the first cationic emulsifier of step (1) are mixed for a time ranging from 0.5 to 1.5 hours, for example 1 hour, and the specific values therebetween are not exhaustive for the invention and are included in the range for reasons of brevity and conciseness.
Preferably, the solids content of the first pre-emulsion of step (1) is 30-60%, such as 32%, 34%, 36%, 38%, 42%, 44%, 46%, 48%, 50%, 52%, 54%, 56% or 58%, and the specific values therebetween, for brevity and clarity, are not intended to be exhaustive of the invention to include the specific values within the recited ranges.
Preferably, the second pre-emulsion in the step (1) comprises 5 to 25 parts by weight of fluorine-containing monomer, 0.2 to 1.5 parts by weight of second nonionic emulsifier and 0.1 to 0.75 part by weight of second cationic emulsifier.
The fluorine-containing monomer may be 10 parts by weight, 13 parts by weight, 15 parts by weight, or the like.
The second nonionic emulsifier can be 0.4, 0.52, or 0.6 parts by weight, and the like.
The second cationic emulsifier can be 0.2, 0.26, or 0.3 parts by weight, and the like.
Preferably, the fluorine-containing monomer comprises any one of trifluoroethyl methacrylate, hexafluorobutyl methacrylate or dodecafluoroheptyl methacrylate or a combination of at least two of them.
Preferably, the first nonionic emulsifier and the second nonionic emulsifier in step (1) each independently comprise fatty alcohol-polyoxyethylene ether.
Preferably, the first cationic emulsifier and the second cationic emulsifier of step (1) each independently comprise cetyltrimethylammonium chloride and/or octadecyltrimethylammonium chloride.
Preferably, the mixing time of the fluoromonomer, the second nonionic emulsifier and the second cationic emulsifier in step (1) is 1.5 to 2.5 hours, for example 2 hours, and the specific values therebetween are limited by space and for the sake of brevity, and the invention is not intended to be exhaustive of the specific values included in the ranges.
Preferably, the solids content of the second pre-emulsion of step (1) is 30-60%, such as 32%, 34%, 36%, 38%, 40%, 42%, 44%, 46%, 48%, 50%, 52%, 54%, 56% or 58%, and the specific values therebetween, limited to space and for brevity, the invention is not exhaustive of the specific values included in the ranges.
Preferably, the silica sol of step (1) has a silica content of 10 to 20% by mass, and the specific values between the above values are not exhaustive for the purpose of brevity and conciseness.
Preferably, the mass ratio of the silane coupling agent to the silica sol in the step (1) is 1 (40-600), for example, 1.
Preferably, the silane coupling agent of step (1) includes any one of gamma-aminopropyltriethoxysilane, gamma-glycidoxypropyltrimethoxysilane, gamma-methacryloxypropyltrimethoxysilane, or gamma-mercaptopropyltriethoxysilane, or a combination of at least two thereof.
Preferably, deionized water is also added in the modification process of the step (1).
Preferably, the modification in step (1) is carried out at a pH of 4 to 5.
Preferably, the modification of step (1) is carried out under stirring conditions.
Preferably, the modification time is between 1 and 3 hours, such as 2 hours or 2.8 hours, and the particular points between the above points, limited to space and for the sake of brevity, are not exhaustive of the invention to include the particular points in the stated ranges.
Preferably, the temperature of the modification is between 20 and 40 ℃, for example 30 ℃ or 38 ℃, and the particular values between those stated are not exhaustive for the invention, limited to space and for the sake of brevity.
Preferably, the mass ratio of the cationic initiator and the modified silica sol in the step (2) is 1 (20-50), such as 1.
Preferably, the temperature of the mixing in step (2) is between 60 ℃ and 80 ℃, for example 70 ℃, and the specific values between the above values are not exhaustive for the invention, which is limited by the space and for the sake of brevity.
Preferably, the mixing and the reaction in the step (2) are carried out under the protection of inert gas.
Preferably, the inert gas comprises nitrogen.
Preferably, the method for adding the first pre-emulsion and the second pre-emulsion obtained in the step (1) in the step (2) is dropwise adding.
Preferably, the dropping is simultaneous dropping.
As a preferred technical scheme, the polymer monomer of the shell layer is introduced into the reaction system in a slow dropwise adding mode, so that most of polymerization reaction can be ensured to occur on the surface of the silica particles, the preparation of the core-shell silica/polymer structure is realized, and the reaction can be stably carried out.
Preferably, the time of the dropwise addition is between 1 and 3 hours, for example 2 hours or 2.8 hours, and the specific values therebetween, limited to space and for the sake of brevity, the present invention is not intended to be exhaustive of the specific values included in the ranges.
Preferably, the reaction time of step (2) is between 6 and 9h, for example 8h or 8.8h, and the specific values therebetween, for reasons of space and simplicity, are not exhaustive.
Preferably, the method further comprises a post-treatment step after the reaction in the step (2) is finished.
Preferably, the post-treatment comprises the steps of cooling, filtering and discharging.
As a preferred technical scheme, the preparation method comprises the following steps:
(1) Mixing 40-160 parts by weight of acrylate monomer, 3-4 parts by weight of nonionic emulsifier, 1.5-2 parts by weight of cationic emulsifier and deionized water for 0.5-1.5 h to obtain a first pre-emulsion with a solid content of 30-60%; mixing 5-25 parts by weight of fluorine-containing monomer, 0.2-1.5 parts by weight of non-ionic emulsifier, 0.1-0.75 part by weight of cationic emulsifier and deionized water for 1.5-2.5 h to obtain a second pre-emulsion with the solid content of 30-60%; under the condition that the pH value is 4-5, modifying 40-60 parts by weight of silica sol with the silica mass percentage of 10-20% by 0.1-1 part by weight of silane coupling agent, and stirring for 1-3 h at the temperature of 20-40 ℃ to obtain modified silica sol; the silane coupling agent comprises any one or the combination of at least two of gamma-aminopropyl triethoxysilane, gamma-glycidoxypropyl trimethoxysilane, gamma-methacryloxypropyl trimethoxysilane or gamma-mercaptopropyl triethoxysilane;
(2) Mixing the modified silica sol obtained in the step (1) with a mass ratio of (20-50): 1 with a cationic initiator at 60-80 ℃ under the protection of nitrogen, simultaneously dropwise adding the first pre-emulsion and the second pre-emulsion obtained in the step (1) into the mixture to react for 6-9 h, cooling, filtering and discharging to obtain the fiber deepening agent.
In a third aspect, the present invention provides a use of a fibre depth increasing agent as described in the first aspect in a fibre product.
Compared with the prior art, the invention has the following beneficial effects:
the fiber deepening agent provided by the invention is of a core-shell structure, the core material comprises silicon dioxide, and the shell material comprises fluorine-containing polymer and polyacrylate; through the structural design of the hard core and soft shell, the fiber deepening agent has a rough surface provided by the silicon dioxide particles and a low-refractive-index film layer brought by the polymer, and the interaction of the two substances enables the prepared fiber deepening agent to have an extremely high-efficiency deepening effect on fiber materials. Under the condition that the concentration of the padding liquid is 10g/L, the deepening rate of the deepening agent for the base cloth can reach 43.9 percent, and compared with the deepening effect of the deepening agent provided by the prior art, the deepening rate is improved by 83 percent; under the condition that the concentration of padding liquid is 25g/L, the deepening rate of the deepening base cloth obtained by using the deepening agent provided by the invention is 25.1-28.7%, compared with the deepening base cloth obtained by using the deepening agent provided by the prior art, the deepening rate is improved by 66-158%, the deepening agent provided by the invention has a more efficient deepening effect on the base cloth, and under the condition that the consumption is only 40% of the conventional deepening agent in the prior art, a similar deepening effect can be realized, and the deepening effect is more obvious when the consumption is increased. The characteristic enables the fiber deepening agent provided by the invention to be widely applied to polyester microfiber, and particularly deepening treatment of fiber products with colors of black, dark blue and dark blue which are difficult to be deeply dyed.
On the other hand, the hard core and soft shell type structure of the fiber deepening agent ensures that the film layer has good strength, and meanwhile, the polymer shell layer endows the fiber fabric with more flexible hand feeling, the polyester microfiber can be deepened better under the condition of extremely low using amount due to obvious deepening effect, the attaching amount of the deepening agent on the fiber is reduced, the influence on the hand feeling is further reduced, and the fiber is effectively deepened under the condition of not influencing the performances of the hand feeling, the friction fastness and the like of the fiber.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
A fiber deepening agent, the particle size of emulsion is 368nm, the fiber deepening agent is of a core-shell structure, the core material comprises silicon dioxide, and the shell material comprises fluorine-containing polymer and polyacrylate;
the mass percentage of silicon dioxide in the fiber deepening agent is 17%, the glass transition temperature of the shell material is-1 ℃, and the mass percentage of the fluorine-containing polymer in the shell material is 11%;
the preparation method comprises the following steps:
(1) Emulsifying 50 parts by weight of n-butyl acrylate, 30 parts by weight of methyl methacrylate, 3.2 parts by weight of an emulsifier MOA-5,1.6 parts by weight of hexadecyltrimethylammonium chloride and 84.8 parts by weight of deionized water for 1 hour to obtain a first pre-emulsion; emulsifying 10 parts by weight of dodecafluoroheptyl methacrylate, 0.4 part by weight of an emulsifier MOA-5,0.2 part by weight of hexadecyltrimethylammonium chloride and 10.6 parts by weight of deionized water for 2 hours to obtain a second pre-emulsion; mixing 100 parts by weight of 20% silica sol with a particle size of 20nm, 0.5 part by weight of gamma-glycidoxypropyltrimethoxysilane and 165 parts by weight of water, adding acetic acid to adjust the pH value to 5, and stirring at 30 ℃ for 2 hours to obtain modified silica sol;
(2) And (2) mixing the modified silica sol obtained in the step (1) with 1.8 parts by weight of azodiisobutylaminum dihydrochloride cation initiator under the protection of nitrogen at 70 ℃, stirring for 10 minutes, simultaneously dropwise adding the first pre-emulsion and the second pre-emulsion obtained in the step (1) for reaction, wherein the dropwise adding time is 2 hours, continuously reacting for 8 hours at 70 ℃ after the dropwise adding is finished, cooling, filtering, and discharging to obtain the fiber deepening agent with the solid content of 25%.
Example 2
A fiber deepening agent, the particle size of emulsion is 325nm, the fiber deepening agent is of a core-shell structure, the core material comprises silicon dioxide, and the shell material comprises fluorine-containing polymer and polyacrylate;
the fiber deepening agent comprises 14% of silicon dioxide by mass, 7% of shell material by mass and 17% of fluorine-containing polymer by mass;
the preparation method comprises the following steps:
(1) Emulsifying 45 parts by weight of ethyl acrylate, 25 parts by weight of isobutyl methacrylate, 3 parts by weight of an emulsifier MOA-5,1.5 parts by weight of hexadecyltrimethylammonium chloride and 84.8 parts by weight of deionized water for 1 hour to obtain a first pre-emulsion; emulsifying 15 parts by weight of hexafluorobutyl methacrylate, 0.6 part by weight of emulsifier MOA-5,0.3 part by weight of hexadecyl trimethyl ammonium chloride and 15.9 parts by weight of deionized water for 2 hours to obtain a second pre-emulsion; mixing 75 parts by weight of silica sol with the mass fraction of 20% and the particle size of 15nm, 0.75 part by weight of gamma-glycidoxypropyltrimethoxysilane and 450 parts by weight of water, adding acetic acid to adjust the pH value to 5, and stirring at 30 ℃ for 2 hours to obtain modified silica sol;
(2) And (2) mixing the modified silica sol obtained in the step (1) with 1.8 parts by weight of azodiisobutylaminum dihydrochloride cation initiator under the protection of nitrogen at 70 ℃, stirring for 10 minutes, simultaneously dropwise adding the first pre-emulsion and the second pre-emulsion obtained in the step (1) for reaction, wherein the dropwise adding time is 2 hours, continuously reacting for 8 hours at 70 ℃ after the dropwise adding is finished, cooling, filtering, and discharging to obtain the fiber deepening agent with the solid content of 25%.
Example 3
A fiber deepening agent, the particle size of emulsion is 335nm, the fiber deepening agent is of a core-shell structure, the core material comprises silicon dioxide, and the shell material comprises fluorine-containing polymer and polyacrylate;
the mass percentage of silicon dioxide in the fiber deepening agent is 11%, the glass transition temperature of the shell material is-5 ℃, and the mass percentage of the fluorine-containing polymer in the shell material is 15%;
the preparation method comprises the following steps:
(1) Emulsifying 50 parts by weight of 2-ethylhexyl acrylate, 25 parts by weight of ethyl methacrylate, 3 parts by weight of an emulsifier MOA-5,1.5 parts by weight of hexadecyltrimethylammonium chloride and 79.5 parts by weight of deionized water for 1 hour to obtain a first pre-emulsion; emulsifying 13 parts by weight of hexafluorobutyl methacrylate, 0.52 part by weight of emulsifier MOA-5,0.26 part by weight of hexadecyl trimethyl ammonium chloride and 13.78 parts by weight of deionized water for 2 hours to obtain a second pre-emulsion; mixing 60 parts by weight of 20% silica sol with a particle size of 20nm, 0.6 part by weight of gamma-glycidoxypropyltrimethoxysilane and 159 part by weight of water, adding acetic acid to adjust the pH value to 5, and stirring at 30 ℃ for 2 hours to obtain modified silica sol;
(2) And (2) mixing the modified silica sol obtained in the step (1) with 2.2 parts by weight of azo-diisobutyl imidazoline hydrochloride cation initiator at 70 ℃ in a nitrogen atmosphere, stirring for 10 minutes, simultaneously dropwise adding the first pre-emulsion and the second pre-emulsion obtained in the step (1) for reaction, wherein the dropwise adding time is 2 hours, continuously reacting at 70 ℃ for 8 hours after the dropwise adding is finished, cooling, filtering, and discharging to obtain the fiber deepening agent with the solid content of 25%.
Example 4
A fiber deepening agent, the particle size of emulsion is 405nm, the fiber deepening agent is of a core-shell structure, the core material comprises silicon dioxide, and the shell material comprises fluorine-containing polymer and polyacrylate;
the fiber deepening agent comprises 16 mass percent of silicon dioxide, 3 mass percent of shell material glass transition temperature and 14 mass percent of fluorine-containing polymer;
the preparation method comprises the following steps:
(1) Emulsifying 50 parts by weight of n-butyl acrylate, 40 parts by weight of methyl methacrylate, 3.6 parts by weight of an emulsifier MOA-5,1.8 parts by weight of hexadecyltrimethylammonium chloride and 95.3 parts by weight of deionized water for 1 hour to obtain a first pre-emulsion; emulsifying 15 parts by weight of dodecafluoroheptyl methacrylate, 0.6 part by weight of emulsifier MOA-5,0.3 part by weight of hexadecyltrimethylammonium chloride and 15.9 parts by weight of deionized water for 2 hours to obtain a second pre-emulsion; mixing 100 parts by weight of silica sol with the mass fraction of 20% and the particle size of 25nm, 0.5 part by weight of gamma-glycidoxypropyltrimethoxysilane and 209 parts by weight of water, adding acetic acid to adjust the pH value to 5, and stirring at 30 ℃ for 2 hours to obtain modified silica sol;
(2) And (2) mixing the modified silica sol obtained in the step (1) with 1.8 parts by weight of azodiisobutylaminum dihydrochloride cation initiator under the protection of nitrogen at 70 ℃, stirring for 10 minutes, simultaneously dropwise adding the first pre-emulsion and the second pre-emulsion obtained in the step (1) for reaction, wherein the dropwise adding time is 2 hours, continuously reacting for 8 hours at 70 ℃ after the dropwise adding is finished, cooling, filtering, and discharging to obtain the fiber deepening agent with the solid content of 25%.
Comparative example 1
A fiber deepening agent, the particle size of emulsion is 278nm, and comprises fluorine-containing polymer and polyacrylate;
the preparation method comprises the following steps:
(1) Emulsifying 10 parts by weight of dodecafluoroheptyl methacrylate, 0.4 part by weight of an emulsifier MOA-5,0.2 part by weight of hexadecyltrimethylammonium chloride and 10.6 parts by weight of deionized water for 2 hours to obtain a first pre-emulsion; emulsifying 50 parts by weight of n-butyl acrylate, 30 parts by weight of methyl methacrylate, 3.2 parts by weight of an emulsifier MOA-5,1.6 parts by weight of hexadecyltrimethylammonium chloride and 84.8 parts by weight of deionized water for 1 hour to obtain a second pre-emulsion;
(2) And (2) mixing 190.8 parts by weight of deionized water and 1.8 parts by weight of azodiisobutyl imidazoline hydrochloride cationic initiator at 70 ℃ in a nitrogen atmosphere, stirring for 10 minutes, simultaneously dropwise adding the first pre-emulsion and the second pre-emulsion obtained in the step (1) for reaction, wherein the dropwise adding time is 2 hours, continuing to react for 8 hours at 70 ℃ after the addition is finished, cooling, filtering and discharging to obtain the fiber deepening agent with the solid content of 25%.
Comparative example 2
A fiber deepening agent, the particle size of emulsion is 212nm, and comprises silicon dioxide and polyacrylate;
(1) Emulsifying 50 parts by weight of n-butyl acrylate, 30 parts by weight of methyl methacrylate, 3.2 parts by weight of an emulsifier MOA-5,1.6 parts by weight of hexadecyl trimethyl ammonium chloride and 84.8 parts by weight of deionized water for 1 hour to obtain a pre-emulsion; mixing 50 parts by weight of 20% silica sol with a particle size of 20nm, 0.5 part by weight of gamma-glycidoxypropyltrimethoxysilane and 165 parts by weight of water, adding acetic acid to adjust the pH value to 5, and stirring at 30 ℃ for 2 hours to obtain modified silica sol;
(2) And (2) mixing the modified silica sol obtained in the step (1) with 1.8 parts by weight of azodiisobutylaminum dihydrochloride cation initiator under the protection of nitrogen at 70 ℃, stirring for 10 minutes, dropwise adding the pre-emulsion obtained in the step (1) for reaction, wherein the dropwise adding time is 2 hours, continuously reacting at 70 ℃ for 8 hours after the dropwise adding is finished, cooling, filtering and discharging to obtain the fiber deepening agent with the solid content of 25%.
Comparative example 3
One commercially available deepening agent: the emulsion is milky white in appearance, the particle size of the emulsion is 260nm, the solid content is 28%, the pH =7.0, and the emulsion comprises an aqueous polyurethane emulsion.
Application example 1
A deepening base fabric is obtained by carrying out one-dip-one-roll treatment on a base fabric (Navy polyester microfiber, shanghai Huafeng microfiber science and technology Co., ltd.) by using the fiber deepening agent obtained in the embodiment 1, wherein the concentration of a padding liquid is 25g/L, the rolling residual rate is 80%, and then baking is carried out for 3min at 150 ℃.
Application examples 2 to 5
A piece of deepening base cloth is prepared by respectively carrying out one-dipping-one-rolling treatment on base cloth (Navy polyester microfiber, shanghai Huafeng microfiber science and technology Co., ltd.) by using the fiber deepening agent obtained in the embodiment 1-4, wherein the concentration of a dipping and rolling solution is 10g/L, the rolling rate is 80%, and then, the base cloth is baked for 3min at 150 ℃ to obtain the deepening base cloth.
Comparative application example 1
A darkening base fabric which is different from that of application example 1 in that the fiber-deepening agent obtained in example 1 was replaced with the fiber-deepening agent obtained in comparative example 3, and the other steps and conditions were the same as those of application example 1, to obtain the darkening base fabric.
Comparative application examples 2 to 4
A piece of deepening base cloth is prepared by respectively carrying out one-dipping-one-rolling treatment on base cloth (Navy polyester microfiber, shanghai Huafeng microfiber science and technology Co., ltd.) by using the fiber deepening agents obtained in comparative examples 1-3, wherein the concentration of a padding liquid is 10g/L, the padding rate is 80%, and then, the base cloth is baked for 3min at 150 ℃ to obtain the deepening base cloth.
And (3) performance testing:
(1) K/S value and depth increase rate: testing the base cloth through a Datacolor color measuring instrument, taking the K/S value of the standard dyeing depth as a judgment standard, and calculating the darkening rate according to the formula I:
in the formula I, (K/S) 1 Denotes the K/S value (K/S) of the undensified base fabric 2 Expressing the K/S value of the deepened base cloth;
(2) Flexibility: the hand feeling of the deepened base fabric is evaluated by 6 persons, and the average value is the best 10 points and the worst 1 point.
(3) Dry and wet fastnesses: and (4) detecting the deepening base fabric according to the national standard GB/T3920-2008.
The non-deepened base fabrics, the deepened base fabrics obtained in application examples 1 to 5 and the deepened base fabrics obtained in comparative application examples 1 to 4 were tested according to the test method, and the test results are shown in table 1:
TABLE 1
As can be seen from the data in table 1:
the deepening agent prepared by the invention has very obvious deepening effect on fibers; specifically, under the condition that the concentration of the padding liquid is only 10g/L, the deepening base cloth provided in application example 1 can reach 43.9 percent of deepening rate (compared with the base cloth which is not deepened), and compared with the deepening base cloth provided in application example 1, the deepening rate is improved by 83 percent; the application examples 2-5 are the deepening base cloth obtained under the condition that the concentration of the padding liquid is 25g/L, the deepening rate is 25.1-28.7%, and compared with the deepening base cloth obtained in the comparative application examples 1-4, the deepening rate is improved by 66-158%; the results prove that the deepening agent provided by the invention has obvious deepening effect, and the same deepening effect can be realized only by using 40% of the deepening agent provided by the prior art; when the using amount is increased, the deepening effect can be further improved;
by comparing the application example 1 with the comparative application example 1, and comparing the application examples 2-5 with the comparative application examples 2-4, the deepening agent prepared by the invention has almost no influence on the hand feeling of the fiber and has a certain improvement effect on the color fastness to rubbing; the deepening agent product provided by the prior art has certain negative effects on the rubbing fastness of the fiber and certain influence on the hand feeling of the fiber.
In conclusion, the deepening agent prepared by the invention can realize effective deepening of the fiber under the condition of not influencing the performances of the fiber such as hand feeling, friction fastness and the like, and the deepening effect is very obvious.
The applicant states that the invention is illustrated by the above examples as a fibre depth increasing agent and a method of preparation and application thereof, but the invention is not limited to the above process steps, i.e. it does not mean that the invention must rely on them for implementation. It will be apparent to those skilled in the art that any modification of the present invention, equivalent substitutions of selected materials and additions of auxiliary components, selection of specific modes and the like, which are within the scope and disclosure of the present invention, are contemplated by the present invention.
Claims (47)
1. The fiber deepening agent is characterized in that the fiber deepening agent is of a core-shell structure;
the core material of the core-shell structure comprises silicon dioxide; the shell layer material of the core-shell structure comprises fluorine-containing polymer and polyacrylate;
the mass percentage of the silicon dioxide in the fiber deepening agent is 10-20%;
the particle size of the silicon dioxide is 10-60 nm.
2. The fiber depth enhancer of claim 1, wherein the emulsion particle size of the fiber depth enhancer is 80-800 nm.
3. The fiber depth enhancer of claim 2, wherein the emulsion particle size of the fiber depth enhancer is from 180nm to 550nm.
4. The fiber depth enhancer of claim 3, wherein the emulsion particle size of the fiber depth enhancer is 250-450 nm.
5. The fiber depth increasing agent according to claim 1, wherein the particle size of the silica is 15 to 25nm.
6. The fiber depth increasing agent of claim 1, wherein the glass transition temperature of the shell material is-30 to 40 ℃.
7. The fiber depth increasing agent of claim 6, wherein the glass transition temperature of the shell material is-20 ℃ to 25 ℃.
8. The fiber depth increasing agent of claim 1, wherein the shell material has a glass transition temperature of-5 to 10 ℃.
9. The fiber deepening agent according to claim 1, wherein the mass percentage of the fluoropolymer in the shell material is 2-40%.
10. The fiber deepening agent according to claim 9, wherein the mass percentage of the fluoropolymer in the shell material is 5-30%.
11. The fiber deepening agent of claim 10, wherein the mass percentage of the fluorine-containing polymer in the shell material is 10-20%.
12. The fiber deepening agent according to claim 1, wherein the shell layer thickness of the core-shell structure is 20-350 nm.
13. The fiber deepening agent of claim 12, wherein a shell layer thickness of the core-shell structure is 80 to 250nm.
14. The fiber deepening agent of claim 13, wherein a shell layer thickness of the core-shell structure is 120-200 nm.
15. A method for preparing a fiber depth increasing agent according to any one of claims 1 to 14, wherein the method comprises the following steps:
(1) Mixing an acrylate monomer, a first nonionic emulsifier and a first cationic emulsifier to obtain a first pre-emulsion; mixing a fluorine-containing monomer, a second nonionic emulsifier and a second cationic emulsifier to obtain a second pre-emulsion; modifying the silica sol by using a silane coupling agent to obtain modified silica sol;
(2) And (2) mixing the modified silica sol obtained in the step (1) with a cationic initiator, and adding the first pre-emulsion and the second pre-emulsion obtained in the step (1) into the mixture for reaction to obtain the fiber deepening agent.
16. The method according to claim 15, wherein the first pre-emulsion of step (1) comprises 40 to 160 parts by weight of the acrylate monomer, 3 to 4 parts by weight of the first nonionic emulsifier, and 1.5 to 2 parts by weight of the first cationic emulsifier.
17. The method of claim 16, wherein the acrylate monomer comprises a methacrylate monomer.
18. The method according to claim 17, wherein the methacrylate monomer comprises any one or a combination of at least two of methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, and t-butyl methacrylate.
19. The method of claim 18, wherein the acrylic monomer further comprises any one or a combination of at least two of methyl acrylate, ethyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, or t-butyl acrylate.
20. The method according to claim 15, wherein the acrylic monomer, the first nonionic emulsifier and the first cationic emulsifier in step (1) are mixed for 0.5 to 1.5 hours.
21. The method of claim 15, wherein the first pre-emulsion of step (1) has a solids content of 30-60%.
22. The method of claim 15, wherein the second pre-emulsion of step (1) comprises 5 to 25 parts by weight of the fluoromonomer, 0.2 to 1.5 parts by weight of the second nonionic emulsifier, and 0.1 to 0.75 parts by weight of the second cationic emulsifier.
23. The method of claim 22, wherein the fluorine-containing monomer comprises any one of trifluoroethyl methacrylate, hexafluorobutyl methacrylate or dodecafluoroheptyl methacrylate or a combination of at least two thereof.
24. The method of claim 15, wherein the first nonionic emulsifier and the second nonionic emulsifier of step (1) each independently comprise a fatty alcohol-polyoxyethylene ether.
25. The method of claim 15, wherein the first and second cationic emulsifiers of step (1) each independently comprise cetyltrimethylammonium chloride and/or octadecyltrimethylammonium chloride.
26. The method according to claim 15, wherein the mixing time of the fluorine-containing monomer, the second nonionic emulsifier and the second cationic emulsifier in step (1) is 1.5 to 2.5 hours.
27. The method of claim 15, wherein the second pre-emulsion of step (1) has a solids content of 30-60%.
28. The method according to claim 15, wherein the silica sol of step (1) contains 10 to 20% by mass of silica.
29. The production method according to claim 15, wherein the mass ratio of the silane coupling agent to the silica sol in the step (1) is 1 (40-600).
30. The method of claim 15, wherein the silane coupling agent of step (1) comprises any one of or a combination of at least two of gamma-aminopropyltriethoxysilane, gamma-glycidoxypropyltrimethoxysilane, gamma-methacryloxypropyltrimethoxysilane, and gamma-mercaptopropyltriethoxysilane.
31. The method according to claim 15, wherein deionized water is further added during the modification in step (1).
32. The method according to claim 15, wherein the modification in step (1) is carried out at a pH of 4 to 5.
33. The method according to claim 15, wherein the modification in step (1) is carried out under stirring conditions.
34. The method according to claim 15, wherein the modification time is 1 to 3 hours.
35. The method of claim 15, wherein the temperature of the modification is 20 to 40 ℃.
36. The preparation method according to claim 15, wherein the mass ratio of the cationic initiator to the modified silica sol in the step (2) is 1 (20-50).
37. The method according to claim 15, wherein the mixing temperature in the step (2) is 60 to 80 ℃.
38. The method according to claim 15, wherein the mixing and the reacting in step (2) are carried out under an inert gas atmosphere.
39. The method of claim 38, wherein the inert gas comprises nitrogen.
40. The method according to claim 15, wherein the step (2) of adding the first pre-emulsion and the second pre-emulsion obtained in the step (1) is dropwise.
41. The production method according to claim 40, wherein the dropwise addition is simultaneous dropwise addition.
42. The method of claim 40, wherein the dropping time is 1 to 3 hours.
43. The method according to claim 15, wherein the reaction time in the step (2) is 6 to 9 hours.
44. The method according to claim 15, wherein the reaction of step (2) is completed by a post-treatment step.
45. The method of claim 44, wherein the post-processing comprises the steps of cooling, filtering, and discharging.
46. The method of claim 15, comprising the steps of:
(1) Mixing 40-160 parts by weight of acrylate monomer, 3-4 parts by weight of nonionic emulsifier, 1.5-2 parts by weight of cationic emulsifier and deionized water for 0.5-1.5 h to obtain a first pre-emulsion with a solid content of 30-60%; mixing 5-25 parts by weight of fluorine-containing monomer, 0.2-1.5 parts by weight of non-ionic emulsifier, 0.1-0.75 part by weight of cationic emulsifier and deionized water for 1.5-2.5 h to obtain a second pre-emulsion with the solid content of 30-60%; under the condition that the pH value is 4-5, modifying 40-60 parts by weight of silica sol with the silica mass percentage of 10-20% by 0.1-1 part by weight of silane coupling agent, and stirring for 1-3 h at the temperature of 20-40 ℃ to obtain modified silica sol; the silane coupling agent comprises any one or the combination of at least two of gamma-aminopropyl triethoxysilane, gamma-glycidoxypropyl trimethoxysilane, gamma-methacryloxypropyl trimethoxysilane or gamma-mercaptopropyl triethoxysilane;
(2) Mixing the modified silica sol obtained in the step (1) with a mass ratio of (20-50): 1 with a cationic initiator at 60-80 ℃ under the protection of nitrogen, simultaneously dropwise adding the first pre-emulsion and the second pre-emulsion obtained in the step (1) into the mixture to react for 6-9 h, cooling, filtering and discharging to obtain the fiber deepening agent.
47. Use of a fibre depth increasing agent according to any one of claims 1 to 14 in a fibre product.
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| CN103289010A (en) * | 2013-05-23 | 2013-09-11 | 陕西科技大学 | Method for preparing core-shell nano SiO2/fluorine-containing polyacrylate soap-free emulsion |
| CN104862964A (en) * | 2015-06-09 | 2015-08-26 | 科凯精细化工（上海）有限公司 | Core-shell emulsion deepening agent for polyester fabric and preparation method thereof |
| CN110698614A (en) * | 2019-10-29 | 2020-01-17 | 上海雅运新材料有限公司 | Core-shell (methyl) acrylate copolymer particle emulsion, preparation method thereof and fabric deepening agent composition |
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| CN103289010A (en) * | 2013-05-23 | 2013-09-11 | 陕西科技大学 | Method for preparing core-shell nano SiO2/fluorine-containing polyacrylate soap-free emulsion |
| CN104862964A (en) * | 2015-06-09 | 2015-08-26 | 科凯精细化工（上海）有限公司 | Core-shell emulsion deepening agent for polyester fabric and preparation method thereof |
| CN110698614A (en) * | 2019-10-29 | 2020-01-17 | 上海雅运新材料有限公司 | Core-shell (methyl) acrylate copolymer particle emulsion, preparation method thereof and fabric deepening agent composition |
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