CN114316570B - Antifogging hydrophilic film and preparation method and application thereof - Google Patents
Antifogging hydrophilic film and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides an anti-fog hydrophilic film, a preparation method and application thereof. The water-absorbing ionic liquid can be well adsorbed in the resin structure, so that the water absorbing capacity of the anti-fog hydrophilic film is greatly improved; the ionic liquid type surfactant provided by the invention has good compatibility with water-absorbing ionic liquid and good compatibility with nonionic surfactant, so that the ionic liquid type surfactant plays roles of hydrophilicity and surface activity in a resin system, and meanwhile, exudation of the nonionic surfactant is reduced.
Description
Technical Field
The invention belongs to the technical field of coatings, relates to an anti-fog hydrophilic film and a preparation method and application thereof, and in particular relates to an anti-fog hydrophilic film added with ionic liquid and a preparation method and application thereof.
Background
When there is a difference in temperature and humidity between the inner surface and the outer surface of a transparent substrate such as glass or plastic, and when one surface is below the dew point or when the temperature and humidity of the substrate surface change greatly due to factors of the external environment, for example, boiling water vapor contacts the substrate and moves from a low-temperature environment to a high-temperature and high-humidity environment, moisture in the air easily adheres to the substrate surface in the form of water drops, so that dew is condensed on the substrate surface, and the condensed water drops cause scattering of light, namely so-called "fog", so that the view is blocked. Such "fog" often significantly impairs the safety and visibility of window glass, showcase glass, front windshield glass of an automobile or aircraft, mirrors, glasses, sunglasses, and the like.
At present, although the common antifogging hydrophilic film materials have a certain antifogging effect, the antifogging films have a microporous structure, are easy to absorb water, and if the water absorption capacity of the films reaches the upper limit or the surface active materials are lost when the antifogging films are used for a long time, the antifogging effect can be lost, so that the water absorption capacity of the antifogging films needs to be improved.
CN109825216a discloses an antistatic antifog film, including antistatic layer a, antifog film, antistatic layer b and basic unit's mucosa, antistatic layer a is located antifog film top, seamless connection between antistatic layer a and the antifog film, antifog film is located between antistatic layer a and antistatic layer b, and heating resistor layer on the antifog film passes through the wire and is connected with the power, antistatic layer b is located antifog film below, with antifog film zonulae occludens, and antistatic layer b another side is connected with basic unit's mucosa, basic unit's mucosa is connected with antistatic layer b, and this invention is through setting up antistatic agent and static eliminator on ordinary antifog film for antifog film when using, can avoid the interference of static, in antifog, can also prevent to adsorb the dust because of producing static, thereby make glass or mirror surface can possess better transparency. However, the antifogging effect and the antifogging period of the antifogging film of the present invention are still further improved.
Accordingly, it is desirable in the art to develop an anti-fog hydrophilic film having better anti-fog hydrophilic properties and longer anti-fog duration.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide an anti-fog hydrophilic film, and a preparation method and application thereof.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
in a first aspect, the present invention provides an anti-fog hydrophilic film, wherein the raw materials for preparing the anti-fog hydrophilic film comprise resin master batches and additives, and the additives comprise a water-absorbing ionic liquid, an ionic liquid type surfactant and a nonionic type surfactant.
When the existing antifogging film is used for a long time, if the water absorption capacity of the film reaches the upper limit, the antifogging effect can be lost, so that the water absorption capacity of the antifogging film needs to be improved. In the invention, the water absorption ionic liquid is added in the membrane system, so that the ionic liquid can be absorbed in the resin structure well, and the water absorption capacity of the anti-fog hydrophilic membrane is improved greatly.
In general, if an excellent antifogging effect is to be obtained, a surfactant material needs to be added, but there is a possibility that the compatibility is poor and the surfactant exudes after the film formation during kneading. The ionic liquid type surfactant provided by the invention has good compatibility with water-absorbing ionic liquid and good compatibility with nonionic surfactant, so that the ionic liquid type surfactant plays roles of hydrophilicity and surface activity in a resin system, and meanwhile, exudation of the nonionic surfactant is reduced.
In the invention, the water-absorbing ionic liquid and the ionic liquid type surfactant act synergistically, so that the prepared anti-fog hydrophilic film has better adhesive force, hydrophilicity and longer service life.
Preferably, the content of the additive is 3% to 40%, for example, 3%, 5%, 8%, 10%, 15%, 20%, 25%, 30%, 35% or 40% based on 100% by mass of the resin master batch.
Preferably, the content of the water-absorbing ionic liquid is 10% to 50%, for example 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45% or 50%, etc., the content of the ionic liquid type surfactant is 5% to 20%, for example 5%, 8%, 10%, 13%, 15%, 18% or 20%, etc., and the content of the nonionic surfactant is 10% to 60%, for example 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55% or 60%, etc., based on 100% by mass of the additive.
If the content of the water-absorbing ionic liquid is too large, the content of the surface active material in the anti-fog hydrophilic film is small, and the anti-fog effect is poor; if the content of the ionic liquid type surfactant is too large, the adhesive force of the surfactant in the resin is poor, the surfactant is easy to exude and run off, and the antifogging is often shortened greatly; if the content of the nonionic surfactant is too large, the antifogging film has poor water absorption capacity and weak continuous antifogging capacity.
Preferably, the resin masterbatch comprises any one of TPU masterbatch, PE masterbatch or PO masterbatch. The resin master batch can be purchased.
Preferably, the water-absorbing ionic liquid comprises [ BMIM ]][Ac]、[BMIM][Cl]、[BMIM][Br]、[BPy][Ac]、[BPy][Br]、[BMIM][TFA]Or [ BMIM ]][NO 3 ]Any one or a combination of at least two of these.
Preferably, the ionic liquid type surfactant comprises a cationic ionic liquid surfactant and/or an anionic ionic liquid surfactant.
Preferably, the cationic ionic liquid surfactant comprises 1-alkyl-3-methylimidazole tetrafluoroborate ([ C) n MIM][BF 4 ]) 1-alkyl-3-methylimidazole hexafluorophosphate ([ C) n MIM][PF 6 ]) Alkyl picoline hydrochloride ([ C) n MPy]Cl), alkyl methyl pyrrole hydrochloride ([ C ] n MPyr]Cl), alkyl triphenyl phosphonium bromide ([ C ] n TP]Br) or N-alkyl-N-methyl-2-pyrrolidone bromide ([ C) n MPn]Br), or a combination of at least two.
Preferably, the anionic ionic liquid surfactant comprises 1-butyl-3-methylimidazole octyl sulfate ([ BMIM)][C 8 AS]) 1- (3-sulfo) propyl-3-methylimidazole dodecylbenzene sulfonate ([ MIMPS)][LAS]) 1-butyl-3-methylimidazole alkyl carboxylate ([ BMIM)][C n H 2n-1 O 2 ]) 1-butyl-3-methylimidazole alkyl sulfate ([ C) 4 MIM][C n AS]) 1-butyl-3-methylimidazole di (2-ethylhexyl) phosphate dioctanoate ([ C) 4 MIM][DEHP]) 1-butyl-3-methylimidazole di (2-ethylhexyl) sulfodibutyrate salt ([ C) 4 MIM][AOT]) 1- (3-sulfonic) propylpiperidyl dodecylbenzenesulfonate ([ PPS)][LAS]) 1- (3-sulfo) propylhexamethyleneimine dodecylbenzene sulfonate ([ HMIPS)][LAS]) Tributyl methylphospholate ([ P) 1444 ][C 12 AS]) Tetrabutyl phosphonium dioctyl sulfosuccinate ([ (C) 4 ) 4 P][AOT]) Tetrabutylammonium chloride dioctyl sulfosuccinate ([ (C) 4 ) 4 N][AOT]) Tetrabutylammonium fluoride fatty alcohol polyoxyethylene ether sulfate ([ (C) 4 ) 4 N][AES]) Tetrabutylammonium lauryl sulfate ([ (C) 4 ) 4 N][C 12 AS]) Or butyl methyl pyrrolidine dodecyl sulfate ([ C) 4 MP][C 12 AS]) Any one or a combination of at least two of these.
Preferably, the nonionic surfactant comprises any one or a combination of at least two of polyether modified polydimethylsiloxane, perfluoroalkyl polyoxyethylene ether, long-chain fatty alcohol polyoxyethylene ether, alkylphenol polyoxyethylene ether, fatty acid polyoxyethylene ester, polyoxyethylene alkylamine, polyoxyethylene alkyl alcohol amide or other polyethers.
In a second aspect, the present invention provides a method for preparing the anti-fog hydrophilic film according to the first aspect, the method comprising the steps of:
mixing the water-absorbing ionic liquid, the ionic liquid type surfactant and the nonionic type surfactant according to the formula amount, then carrying out melt blending with the resin master batch, and carrying out extrusion casting to obtain the anti-fog hydrophilic film.
Preferably, the temperature of the mixing is 30-60 ℃, e.g. 30 ℃, 35 ℃, 40 ℃, 45 ℃, 50 ℃, 55 ℃, 60 ℃, etc.
Preferably, the mixing time is 30-60min, such as 30min, 35min, 40min, 45min, 50min, 55min or 60min, etc.
Preferably, the melt blending is performed in an internal mixer.
Preferably, the temperature of the melt blending is 180-200 ℃, such as 180 ℃, 185 ℃, 190 ℃, 195 ℃, 200 ℃, etc., the rotational speed of the melt blending is 40-60rpm, such as 40rpm, 45rpm, 50rpm, 55rpm, 60rpm, etc., and the time of the melt blending is 5-10min, such as 5min, 6min, 7min, 8min, 9min, 10min, etc.
In a third aspect, the present invention provides the use of an anti-fog hydrophilic film according to the first aspect in an anti-fog film or anti-fog film.
Compared with the prior art, the invention has the following beneficial effects:
(1) The water-absorbing ionic liquid can be well adsorbed in the resin structure, so that the water absorbing capacity of the anti-fog hydrophilic film is greatly improved.
(2) The ionic liquid type surfactant provided by the invention has good compatibility with water-absorbing ionic liquid and good compatibility with nonionic surfactant, so that the ionic liquid type surfactant plays roles of hydrophilicity and surface activity in a resin system, and meanwhile, exudation of the nonionic surfactant is reduced.
(3) In the invention, the water-absorbing ionic liquid and the ionic liquid type surfactant act synergistically, so that the prepared anti-fog hydrophilic film has better adhesive force, hydrophilicity (contact angle of 0 ℃) and longer service life.
Drawings
Fig. 1 is a graph showing the results of antifogging property tests of the antifogging hydrophilic films provided in example 1 (left side graph) and example 6 (right side graph).
Fig. 2 is a graph of the results of anti-fog test of the anti-fog hydrophilic films provided in comparative example 1 (left side graph) and comparative example 2 (right side graph).
Fig. 3 is a graph showing the results of anti-fog property test of the anti-fog hydrophilic film provided in comparative example 3.
Fig. 4 is a graph showing the results of antifogging property test when the antifogging hydrophilic film provided in example 1 (left side graph) and comparative example 1 (right side graph) continuously absorbs water for 5 min.
Fig. 5 is a graph showing the results of antifogging property test when the antifogging hydrophilic film provided in example 6 (left side graph) and comparative example 2 (right side graph) continuously absorbs water for 30 min.
Fig. 6 is a graph showing the results of the antifogging property test of the antifogging hydrophilic film provided in example 1, which continuously absorbs water for 60 minutes.
Fig. 7 is a graph showing the results of an anti-fog property test of the anti-fog hydrophilic film provided in comparative example 2 when the film continuously absorbs water for 60 minutes.
FIG. 8 is a graph showing the test results of comparative example 2 when the 3 rd anti-fog material exudation test was repeated.
Fig. 9 is a graph showing the test result of comparative example 1 when the 4 th anti-fog material exudation test is repeatedly performed.
FIG. 10 is a graph of the test results of example 6 when the 5 th anti-fog material exudation test was repeated.
FIG. 11 is a graph showing the test results of example 1 when the 10 th anti-fog material exudation test was repeated.
Fig. 12 is a graph of test results of example 6 (left panel) and comparative example 1 (right panel) when the 10 th anti-fog material exudation test was repeatedly performed.
Fig. 13 to 17 are graphs showing the results of low-temperature antifogging property tests of the antifogging hydrophilic films provided in example 1, example 6, and comparative examples 1 to 3, respectively.
Fig. 18 to 21 are graphs showing water drop contact angle measurements of the antifogging hydrophilic films provided in example 1, example 6, comparative example 1, and comparative example 3, respectively.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
The sources of the raw materials used in the examples and comparative examples of the present invention are as follows:
TPU master batch: cabot EV1755;
PE master batch: cabot PE6371;
perfluoroalkyl polyoxyethylene ether: a chemical of the family mu;
alkylphenol ethoxylates: shenzhen Jitian chemical Co., ltd;
polyether modified polydimethylsiloxane: pick in Germany.
Example 1
In this embodiment, an antifogging hydrophilic film is provided, and the raw materials for preparing the antifogging hydrophilic film include a resin master batch and an additive, wherein the additive includes a water-absorbing ionic liquid, an ionic liquid type surfactant and a nonionic type surfactant.
Wherein, the content of the additive is 20 percent based on 100 percent of the mass of the resin master batch; the mass of the additive is 100%, the content of the water-absorbing ionic liquid is 30%, the content of the ionic liquid type surfactant is 10%, and the content of the nonionic surfactant is 60%; the resin master batch is TPU master batch; the water-absorbing ionic liquid is [ BMIM ] [ Ac ]; the ionic liquid type surfactant is 1-butyl-3-methylimidazole hexafluorophosphate; the nonionic surfactant is perfluoroalkyl polyoxyethylene ether.
The preparation method comprises the following steps:
mixing the water-absorbing ionic liquid, the ionic liquid surfactant and the nonionic surfactant in the formula amount for 40min at 40 ℃, then carrying out melt blending with the resin master batch in an internal mixer, wherein the melt blending temperature is 190 ℃, the rotating speed is 50rpm, the time is 8min, and then extruding and casting to obtain the antifogging hydrophilic film.
Example 2
In this embodiment, an antifogging hydrophilic film is provided, and the raw materials for preparing the antifogging hydrophilic film include a resin master batch and an additive, wherein the additive includes a water-absorbing ionic liquid, an ionic liquid type surfactant and a nonionic type surfactant.
Wherein, the content of the additive is 3 percent based on 100 percent of the mass of the resin master batch; the mass of the additive is 100%, the content of the water-absorbing ionic liquid is 20%, the content of the ionic liquid type surfactant is 20%, and the content of the nonionic surfactant is 60%; the resin master batch is TPU master batch; the water-absorbing ionic liquid is [ BMIM ] [ Cl ]; the ionic liquid type surfactant is 1-butyl-3-methylimidazole hexafluorophosphate; the nonionic surfactant is alkylphenol polyoxyethylene.
The preparation method comprises the following steps:
mixing the water-absorbing ionic liquid, the ionic liquid surfactant and the nonionic surfactant in the formula amount for 60min at 30 ℃, then carrying out melt blending with the resin master batch in an internal mixer, wherein the melt blending temperature is 180 ℃, the rotating speed is 40rpm, the time is 5min, and then extruding and casting to obtain the antifogging hydrophilic film.
Example 3
In this embodiment, an antifogging hydrophilic film is provided, and the raw materials for preparing the antifogging hydrophilic film include a resin master batch and an additive, wherein the additive includes a water-absorbing ionic liquid, an ionic liquid type surfactant and a nonionic type surfactant.
Wherein, the content of the additive is 40 percent based on 100 percent of the mass of the resin master batch; the mass of the additive is 100%, the content of the water-absorbing ionic liquid is 50%, the content of the ionic liquid type surfactant is 5%, and the content of the nonionic surfactant is 45%; the resin master batch is TPU master batch; the water-absorbing ionic liquid is [ BMIM ] [ Br ]; the ionic liquid type surfactant is 1-butyl-3-methylimidazole tetrafluoroborate; the nonionic surfactant is polyether modified polydimethylsiloxane.
The preparation method comprises the following steps:
mixing the water-absorbing ionic liquid, the ionic liquid surfactant and the nonionic surfactant in the formula amount for 30min at 60 ℃, then carrying out melt blending with the resin master batch in an internal mixer, wherein the melt blending temperature is 200 ℃, the rotating speed is 60rpm, the time is 10min, and then extruding and casting to obtain the antifogging hydrophilic film.
Example 4
In this embodiment, an antifogging hydrophilic film is provided, and the raw materials for preparing the antifogging hydrophilic film include a resin master batch and an additive, wherein the additive includes a water-absorbing ionic liquid, an ionic liquid type surfactant and a nonionic type surfactant.
Wherein, the content of the additive is 10 percent based on 100 percent of the mass of the resin master batch; the mass of the additive is 100%, the content of the water-absorbing ionic liquid is 40%, the content of the ionic liquid type surfactant is 10%, and the content of the nonionic surfactant is 50%; the resin master batch is PE master batch; the water-absorbing ionic liquid is [ BPy ] [ Ac ]; the ionic liquid type surfactant is 1-butyl-3-methylimidazole octyl sulfate; the nonionic surfactant is alkylphenol polyoxyethylene.
The preparation method comprises the following steps:
mixing the water-absorbing ionic liquid, the ionic liquid surfactant and the nonionic surfactant in the formula amount for 40min at 50 ℃, then carrying out melt blending with the resin master batch in an internal mixer, wherein the melt blending temperature is 190 ℃, the rotating speed is 40rpm, the time is 6min, and then extruding and casting to obtain the antifogging hydrophilic film.
Example 5
In this embodiment, an antifogging hydrophilic film is provided, and the raw materials for preparing the antifogging hydrophilic film include a resin master batch and an additive, wherein the additive includes a water-absorbing ionic liquid, an ionic liquid type surfactant and a nonionic type surfactant.
Wherein, the content of the additive is 30 percent based on 100 percent of the mass of the resin master batch; the mass of the additive is 100%, the content of the water-absorbing ionic liquid is 50%, the content of the ionic liquid type surfactant is 20%, and the content of the nonionic surfactant is 30%; the resin master batch is PE master batch; the water-absorbing ionic liquid is [ BPy ] [ Ac ]; the ionic liquid type surfactant is 1-butyl-3-methylimidazole hexafluorophosphate; the nonionic surfactant is perfluoroalkyl polyoxyethylene ether.
The preparation method comprises the following steps:
mixing the water-absorbing ionic liquid, the ionic liquid surfactant and the nonionic surfactant in the formula amount for 50min at 40 ℃, then carrying out melt blending with the resin master batch in an internal mixer, wherein the melt blending temperature is 190 ℃, the rotating speed is 50rpm, the time is 7min, and then extruding and casting to obtain the antifogging hydrophilic film.
Example 6
The present example differs from example 1 only in that the content of the water-absorbent ionic liquid is 60%, the content of the ionic liquid type surfactant is 30%, the content of the nonionic surfactant is 10% based on 100% by mass of the additive, and the other conditions are the same as in example 1.
Comparative example 1
The comparative example differs from example 1 only in that the content of the water-absorbent ionic liquid was 0% (i.e., no water-absorbent ionic liquid was added), the content of the ionic liquid type surfactant was 40%, the content of the nonionic surfactant was 60%, and the other conditions were the same as in example 1, based on 100% of the mass of the additive.
Comparative example 2
The comparative example differs from example 1 only in that the content of the water-absorbent ionic liquid was 40% and the content of the ionic liquid type surfactant was 0% (i.e., no ionic liquid type surfactant was added), the content of the nonionic surfactant was 60%, based on 100% by mass of the additive, and the other conditions were the same as in example 1.
Comparative example 3
The comparative example differs from example 1 only in that the content of the water-absorbent ionic liquid was 50%, the content of the ionic liquid type surfactant was 50%, and the content of the nonionic surfactant was 0% (i.e., no nonionic surfactant was added) based on 100% by mass of the additive, and the other conditions were the same as in example 1.
The anti-fog hydrophilic films of the examples and the comparative examples were subjected to performance tests as follows:
(1) Antifogging test: the sample is stuck on glass, the distance between the sample and the sample is 20cm, high-temperature steam with the temperature of 100 ℃ is used for spraying and steaming, and the sample is immediately transparent, so that the sample is anti-fog.
(2) Antifogging test after water absorption: the sample is stuck on glass, 10cm away from the sample, high-temperature steam at 100 ℃ is used for continuous steam spraying, the anti-fog condition of the sample within 1 hour is observed, and the time for water drops and fog to appear in 30% of the area of the sample is recorded.
(3) Anti-fog material exudation test: adhering the sample on glass, steaming with high temperature steam of 100deg.C for 2min to observe antifogging effect, standing at room temperature for drying, steaming for 2min to observe antifogging effect, and drying at room temperature to obtain water; after the spraying, the number of spraying times when water drops and mist appear in 30% of the area of the sample was recorded.
(4) Low temperature antifogging test: 200mL of 60 ℃ water is added into a beaker with the volume of 250mL, a sample is covered on a cup opening, and the beaker is placed into an ultralow temperature incubator or a refrigerator with the temperature of-18 ℃; after 60 seconds, the samples were visually inspected for hazing.
Haze evaluation criteria:
grade 1 represents a completely transparent, water-free drop;
grade 2 represents better transparency, has a small amount of uneven large water drops, and the area of the water drops is not more than 5%;
grade 3 represents substantially clear with more water droplets, with no more than 30% of the water droplet area;
grade 4 represents translucency, and has a plurality of small water drops, and the water drop area is more than 50%;
grade 5 represents complete opacity.
(5) Drop contact angle test: the contact angle of the water drop is measured by adopting a contact angle measuring instrument (model SDC-200S) device of Cheng Ding precision instruments, dongguan City.
(6) Transmittance: using a light transmittance haze meter, cutting the sample into square sizes of 5cm x 5cm, selecting the center and four vertexes of the sample to test the light transmittance, and taking an average value.
The results of the performance test are shown in Table 1.
TABLE 1
As can be seen from Table 1, the antifogging hydrophilic films prepared in examples 1 to 5 of the present invention all have excellent antifogging property, and the antifogging property after water absorption is also good, and have good hydrophilicity and light transmittance.
The antifogging property of the antifogging hydrophilic film prepared in example 6 was lowered as compared with example 1.
The antifogging property of the antifogging hydrophilic films prepared in comparative examples 1 and 3 was remarkably lowered after water absorption, and the antifogging property of the antifogging hydrophilic film prepared in comparative example 2 was lowered after water absorption, as compared with example 1.
As can be seen from the graphs of the anti-fog test results of fig. 1 to 3, the anti-fog hydrophilic films prepared in example 1 (left side of fig. 1), comparative example 1 and comparative example 2 (fig. 2) have excellent anti-fog properties, while the anti-fog hydrophilic films prepared in example 6 (right side of fig. 1) and comparative example 3 (fig. 3) have slightly inferior anti-fog properties. The black square frames in the figures are encircled by an anti-fog hydrophilic film, and the black square frames in other figures are encircled by the anti-fog hydrophilic film, which is not described one by one.
As can be seen from the graphs of the anti-fog test results after continuous water absorption of fig. 4 to 7, the anti-fog hydrophilic film prepared in example 1 has excellent anti-fog property after continuous water absorption for 60min (as shown in fig. 6), while the anti-fog hydrophilic film prepared in comparative example 1 has significantly reduced anti-fog property after continuous water absorption for 5min (as shown in fig. 4 right side), the anti-fog hydrophilic film prepared in example 6 has 30% of the area after continuous water absorption for 15min, and the sample has a large amount of fog after continuous water absorption for 30min (as shown in fig. 5 left side), and the anti-fog hydrophilic film prepared in comparative example 2 has a large amount of fog after continuous water absorption for 60min (as shown in fig. 7).
As can be seen from the graphs of the exudation test results of the antifogging materials in fig. 8 to 12, the antifogging hydrophilic film prepared in comparative example 2 showed significant fog when the 3 rd test was repeated (as in fig. 8), the antifogging hydrophilic film prepared in comparative example 1 showed significant fog when the 4 th test was repeated (as in fig. 9), the antifogging hydrophilic film prepared in example 6 showed significant fog when the 5 th test was repeated (as in fig. 10), and the antifogging hydrophilic film prepared in example 1 showed no fog when the 10 th test was repeated (as in fig. 11).
As can be seen from the low temperature antifogging property test results of fig. 13 to 17, the antifogging hydrophilic film prepared in example 1 (fig. 13) has excellent low temperature antifogging property, and the antifogging hydrophilic films prepared in example 6 (fig. 14) and comparative examples 1 to 3 (fig. 15 to 17) have slightly inferior low temperature antifogging property.
As can be seen from the contact angle test charts of fig. 18 to 21, the antifogging hydrophilic films prepared in example 1 (fig. 18) and comparative example 1 (fig. 20) have better hydrophilicity, while the antifogging hydrophilic films prepared in example 6 (fig. 19) and comparative example 3 (fig. 21) have slightly worse hydrophilicity.
The applicant states that the present invention is illustrated by the above examples as well as the method of making and using the same, but the present invention is not limited to, i.e., does not mean that the present invention must be practiced in dependence upon the above examples. It should be apparent to those skilled in the art that any modification of the present invention, equivalent substitution of selected raw materials, addition of auxiliary components, selection of specific modes, etc. fall within the scope of the present invention and the scope of disclosure.
Claims (7)
1. The antifogging hydrophilic membrane is characterized in that raw materials for preparing the antifogging hydrophilic membrane comprise resin master batches and additives, wherein the additives comprise water-absorbing ionic liquid, ionic liquid type surfactants and nonionic type surfactants;
the content of the additive is 3% -40% based on 100% of the mass of the resin master batch;
the mass of the additive is 100 percent, the content of the water-absorbing ionic liquid is 10 to 50 percent, the content of the ionic liquid type surfactant is 5 to 20 percent, and the content of the nonionic surfactant is 10 to 60 percent;
the resin master batch comprises any one of TPU master batch, PE master batch or PO master batch;
the water-absorbing ionic liquid comprises [ BMIM ]][Ac]、[BMIM][Cl]、[BMIM][Br]、[BPy][Ac]、[BPy][Br]、[BMIM][TFA]Or [ BMIM ]][NO 3 ]Any one or a combination of at least two of the following;
the ionic liquid type surfactant comprises a cationic ionic liquid surfactant and/or an anionic ionic liquid surfactant;
the cationic ionic liquid surfactant comprises any one or a combination of at least two of 1-alkyl-3-methylimidazole tetrafluoroborate, 1-alkyl-3-methylimidazole hexafluorophosphate, alkyl picoline hydrochloride, alkyl methylpyrrole hydrochloride, alkyl triphenyl phosphate bromide or N-alkyl-N-methyl-2-pyrrolidone bromide;
the anionic ionic liquid surfactant comprises any one or a combination of at least two of 1-butyl-3-methylimidazole octyl sulfate, 1- (3-sulfonic group) propyl-3-methylimidazole dodecyl benzene sulfonate, 1-butyl-3-methylimidazole alkyl carboxylate, 1-butyl-3-methylimidazole alkyl sulfate, 1-butyl-3-methylimidazole di (2-ethylhexyl) phosphate dioctanoate, 1-butyl-3-methylimidazole di (2-ethylhexyl) sulfo dibutyrate, 1- (3-sulfonic group) propyl piperidine dodecyl benzene sulfonate, 1- (3-sulfonic group) propyl hexamethyleneimine dodecyl benzene sulfonate, tributyl methyl phosphorus dodecyl sulfate, tetrabutyl phosphorus dioctyl sulfosuccinate, tetrabutyl ammonium chloride dioctyl sulfosuccinate, tetrabutyl ammonium fluoride fatty alcohol polyoxyethylene ether sulfate, tetrabutyl ammonium oxide dodecyl sulfate or butyl methyl pyrrolidine dodecyl sulfate;
the nonionic surfactant comprises any one or a combination of at least two of polyether modified polydimethylsiloxane, perfluoroalkyl polyoxyethylene ether, long-chain fatty alcohol polyoxyethylene ether, alkylphenol polyoxyethylene ether, fatty acid polyoxyethylene ester, polyoxyethylene alkylamine, polyoxyethylene alkyl alcohol amide or other polyether;
the anti-fog hydrophilic film is prepared by the following method, which comprises the following steps:
mixing the water-absorbing ionic liquid, the ionic liquid type surfactant and the nonionic type surfactant according to the formula amount, then carrying out melt blending with the resin master batch, and carrying out extrusion casting to obtain the anti-fog hydrophilic film.
2. The method for preparing an antifogging hydrophilic membrane according to claim 1, characterized in that the method comprises the steps of:
mixing the water-absorbing ionic liquid, the ionic liquid type surfactant and the nonionic type surfactant according to the formula amount, then carrying out melt blending with the resin master batch, and carrying out extrusion casting to obtain the anti-fog hydrophilic film.
3. The method of claim 2, wherein the temperature of the mixing is 30-60 ℃.
4. The method of claim 2, wherein the mixing is for a period of 30-60 minutes.
5. The method of claim 2, wherein the melt blending is performed in an internal mixer.
6. The method according to claim 2, wherein the melt blending temperature is 180-200 ℃, the melt blending speed is 40-60rpm, and the melt blending time is 5-10min.
7. Use of the anti-fog hydrophilic film according to claim 1 in an anti-fog film.
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| CN202111659369.XA CN114316570B (en) | 2021-12-30 | 2021-12-30 | Antifogging hydrophilic film and preparation method and application thereof |
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| JP2007063298A (en) * | 2005-08-29 | 2007-03-15 | Nippon Carbide Ind Co Inc | Pressure-sensitive adhesive solution composition and surface protective film |
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