CN108329699B

CN108329699B - Internal addition type antifogging agent composition and application thereof

Info

Publication number: CN108329699B
Application number: CN201810238256.4A
Authority: CN
Inventors: 王文举
Original assignee: Guangzhou Champlane Sports Goods Co ltd
Current assignee: Dongguan changqingshu sporting goods Co.,Ltd.
Priority date: 2018-03-22
Filing date: 2018-03-22
Publication date: 2020-08-25
Anticipated expiration: 2038-03-22
Also published as: CN108329699A

Abstract

The invention provides an internal addition type antifogging agent composition, which at least comprises 50-70 parts by weight of silicon-containing surfactant, 15-30 parts by weight of fluorine-containing surfactant, 1-10 parts by weight of penetrating agent and 0.5-10 parts by weight of modified nano silicon dioxide; wherein the silicon-containing surfactant comprises one or more of a modified silicone surfactant, an aminopolyether silicone surfactant and a siloxane phosphate surfactant; the modified nano-silica is nano-silica modified by dimethyl diphenyl diisocyanate and 4-aminomethyl benzyl alcohol; the anti-fogging coating is well compatible with lenses, does not influence transparency, has a long-acting anti-fogging effect, and has excellent performances of weather resistance, high temperature resistance and low temperature resistance.

Description

Internal addition type antifogging agent composition and application thereof

Technical Field

The invention relates to the technical field of antifogging agents, in particular to an internal addition type antifogging agent composition and application thereof.

Background

People wearing the glasses can realize that when entering a high-temperature environment from a low-temperature environment, a layer of fog is condensed on the glasses, so that the people cannot see clearly, and only need to wipe the glasses; in winter, if the nose is covered by the mask, hot air sprayed out of the nose can be condensed when the nose meets cold glasses, so that the nose mask cannot see the clear road, and the nose mask is very dangerous for people driving vehicles.

Swimming sports are one of the sports items that men, women, old and young all enjoy. Swimming goggles also become the necessity of swimming, and swimming goggles wear in water for a long time, meet cold object because of inside hot air, the vapor in the hot air will condense into water, gathers on cold object surface to form the thin fog of one deck, lead to the definition to descend, obstruct the sight.

According to investigation, the antifogging swimming goggles on the market are expensive, and only one layer of antifogging film is adhered to the inner side of the swimming goggles, so that the antifogging film gradually loses effect after being worn for a long time, and permanent antifogging cannot be achieved. And if violent impact occurs underwater, the lens will break or crack, with the result that the eye is easily injured.

In addition, the antifogging liquid for glasses can prevent the generation of fog to a certain extent after being uniformly coated on the lenses, but many effects are not ideal. Particularly, the sensitive part of the eye is relatively close, and the selection of the raw materials is more careful.

The antifogging agent is divided into an internal addition type and an external spraying type. The external spraying antifogging agent forms an antifogging layer on the surface of the swimming goggles by spraying or dipping. Its advantages are quickly taking its effect, short acting period and easy loss. The inner addition type antifogging agent is added into an extruder together with resin to produce the swimming goggles. The antifogging agent can be separated out on the surface of the swimming goggles, and the antifogging effect is achieved. Because the antifogging agent in the goggles can be continuously precipitated on the surfaces of the goggles, the antifogging agent lost on the surfaces of the goggles is supplemented until the antifogging agent in the goggles is completely transferred to the surfaces of the goggles, so that the antifogging agent added in the goggles can give a long-acting antifogging effect to the goggles.

However, since the temperature of the lens melt is 300 ℃ or higher, the internal addition type antifogging agent is likely to be yellowed at high temperature, and further yellowing of the lens is caused. In order to overcome the problem that the high-temperature internal addition type antifogging agent is yellowed, nano silicon dioxide is added, but the compatibility and the dispersity of the nano silicon dioxide and resin and the transparency of the resin are difficult to achieve.

Therefore, in view of the above problems, the present invention provides an internal addition type antifogging agent composition which has good compatibility with lenses, does not affect transparency, has long-lasting antifogging effect, and has excellent properties of weather resistance, high temperature resistance and low temperature resistance.

Disclosure of Invention

In order to solve the problems, the invention provides an internal addition type antifogging agent composition which at least comprises 50-70 parts of silicon-containing surfactant, 15-30 parts of fluorine-containing surfactant, 1-10 parts of penetrating agent and 0.5-10 parts of modified nano silicon dioxide by weight; wherein the silicon-containing surfactant comprises one or more of a modified silicone surfactant, an aminopolyether silicone surfactant and a siloxane phosphate surfactant; the modified nano silicon dioxide is nano silicon dioxide modified by dimethyl diphenyl diisocyanate and 4-aminomethyl benzyl alcohol.

In one embodiment, the internal addition type antifogging agent composition at least comprises 55-68 parts of silicon-containing surfactant, 15-25 parts of fluorine-containing surfactant, 2-8 parts of penetrating agent and 0.5-6 parts of modified nano silicon dioxide in parts by weight.

In one embodiment, the modified silicone surfactant is prepared from octamethylcyclotetrasiloxane, hydrogen-based POSS, and allyl epoxy polyether.

In one embodiment, the raw materials for preparing the amino polyether silicone surfactant comprise allyl glycidyl ether, (2R) -3- (3, 4-dihydroxyphenyl) -2- [ (E) -3- [2- [ (E) -2- (3, 4-dihydroxyphenyl) vinyl ] -3, 4-dihydroxyphenyl ] prop-2-enoyl ] oxypropionic acid, hydrogen-containing silicone oil and polyether amine.

In one embodiment, the fluorosurfactant comprises one or more of a fluorocarbon surfactant, a fluorosilicone surfactant.

In one embodiment, the fluorosurfactant is a fluorosilicone surfactant.

In one embodiment, the raw materials for preparing the fluorosilicone surfactant comprise allyl polyether, hydrogen-containing silicone oil and N-ethyl perfluorooctyl sulfonamide ethyl acrylate.

In one embodiment, the osmotic agent comprises one or more of isomeric polyoxyethylene lauryl ether, isomeric polyoxyethylene undecyl ether, isomeric polyoxyethylene tridecyl ether, and phosphate ester.

In one embodiment, the internal addition type antifogging agent composition is applied to the field of glasses and swimming goggles.

The invention also provides a preparation method of the internal addition type antifogging agent composition, which comprises the following steps:

adding a silicon surfactant, a fluorine-containing surfactant, a penetrating agent and modified nano silicon dioxide into a reactor according to the parts by weight, stirring at room temperature for 1-3h, and uniformly mixing to obtain the internal addition type antifogging agent composition for the swimming goggles.

The above-described and other features, aspects, and advantages of the present application will become more apparent with reference to the following detailed description.

Detailed Description

The disclosure may be understood more readily by reference to the following detailed description of preferred embodiments of the invention and the examples included therein. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In case of conflict, the present specification, including definitions, will control.

The term "prepared from …" as used herein is synonymous with "comprising". The terms "comprises," "comprising," "includes," "including," "has," "having," "contains," "containing," or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a composition, process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus.

The conjunction "consisting of …" excludes any unspecified elements, steps or components. If used in a claim, the phrase is intended to claim as closed, meaning that it does not contain materials other than those described, except for the conventional impurities associated therewith. When the phrase "consisting of …" appears in a clause of the subject matter of the claims rather than immediately after the subject matter, it defines only the elements described in the clause; other elements are not excluded from the claims as a whole.

When an amount, concentration, or other value or parameter is expressed as a range, preferred range, or as a range of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when a range of "1 to 5" is disclosed, the described range should be interpreted to include the ranges "1 to 4", "1 to 3", "1 to 2 and 4 to 5", "1 to 3 and 5", and the like. When a range of values is described herein, unless otherwise stated, the range is intended to include the endpoints thereof and all integers and fractions within the range.

The singular forms "a", "an" and "the" include plural referents unless the context clearly dictates otherwise. "optional" or "any" means that the subsequently described event or events may or may not occur, and that the description includes instances where the event occurs and instances where it does not.

Approximating language, as used herein throughout the specification and claims, is intended to modify a quantity, such that the invention is not limited to the specific quantity, but includes portions that are literally received for modification without substantial change in the basic function to which the invention is related. Accordingly, the use of "about" to modify a numerical value means that the invention is not limited to the precise value. In some instances, the approximating language may correspond to the precision of an instrument for measuring the value. In the present description and claims, range limitations may be combined and/or interchanged, including all sub-ranges contained therein if not otherwise stated.

In addition, the indefinite articles "a" and "an" preceding an element or component of the invention are not intended to limit the number requirement (i.e., the number of occurrences) of the element or component. Thus, "a" or "an" should be read to include one or at least one, and the singular form of an element or component also includes the plural unless the stated number clearly indicates that the singular form is intended.

The invention provides an internal addition type antifogging agent composition, which at least comprises 50-70 parts by weight of silicon-containing surfactant, 15-30 parts by weight of fluorine-containing surfactant, 1-10 parts by weight of penetrating agent and 0.5-10 parts by weight of modified nano silicon dioxide; wherein the silicon-containing surfactant comprises one or more of a modified silicone surfactant, an aminopolyether silicone surfactant and a siloxane phosphate surfactant; the modified nano silicon dioxide is nano silicon dioxide modified by dimethyl diphenyl diisocyanate and 4-aminomethyl benzyl alcohol.

The silicon-containing surfactant is a surfactant formed from siloxane as lipophilic group and hydrophilic group, and the surfactant for antifogging agent includes silicon-containing block polyether and silicon-containing random polyether, also can use monomer with unsaturated olefinic bond to make emulsion polymerization so as to obtain the invented polymerized antifogging agent containing silicon. When the content of the silicon surfactant is very low, the surface tension of water can be reduced, the interfacial tension of water and greenhouse film can be reduced, and the silicon surfactant has excellent thermal stability and chemical stability. The polysiloxane main chain is composed of-SiO-, has no hydrophilicity, has good compatibility with polyolefin, and introduces polyoxyethylene chain segment on the main chain to enhance the hydrophilicity of siloxane. The polyoxyethylene forms hydrogen bonds when meeting water, enhances the hydrophilicity of the modified polysiloxane, and has binding force with some side groups of the polyolefin, thereby slowly releasing the antifogging agent and improving the durability of the antifogging.

In one embodiment, the silicon-containing surfactant is a modified silicone surfactant, an aminopolyether silicone surfactant.

In one embodiment, the weight ratio of the modified silicone surfactant to the aminopolyether silicone surfactant in the silicon-containing surfactant is 1: (0.2-1.5); preferably, the weight ratio of the modified silicone surfactant to the aminopolyether silicone surfactant is 1: 0.7.

in one embodiment, the modified silicone surfactant is prepared from octamethylcyclotetrasiloxane, hydrogen-based POSS (CAS number 5256-79-1), and allyl epoxy polyether (APEE-550).

In one embodiment, the raw materials for preparing the aminopolyether silicone surfactant include Allyl Glycidyl Ether (AGE), (2R) -3- (3, 4-dihydroxyphenyl) -2- [ (E) -3- [2- [ (E) -2- (3, 4-dihydroxyphenyl) vinyl ] -3, 4-dihydroxyphenyl ] prop-2-enoyl ] oxypropionic acid (CAS: 96574-01-5), hydrogen-containing silicone oil, and polyether amine.

The polyether amine comprises polyether amine M-600, polyether amine M-1000, polyether amine M-2005 and polyether amine M-2070, and is purchased from Guangzhou Heishi chemical products, Inc.

The preparation method of the modified organosilicon surfactant comprises the following steps:

(1) introducing nitrogen into a reactor, adding allyl epoxy polyether (APEE-550), octamethylcyclotetrasiloxane and hydrogen-based POSS, keeping out of the sun, heating to 90 ℃, dropwise adding a chloroplatinic acid catalyst (diluted to 1% by using isopropanol), keeping the temperature for reaction for 5 hours, cooling to room temperature after the reaction is finished, precipitating the liquid in a mixed solution (v/v: 20/1) of n-hexane and tetrahydrofuran for 3 times to remove the catalyst, and removing the n-hexane and the tetrahydrofuran under reduced pressure to obtain the modified organosilicon surfactant; the weight ratio of the allyl epoxy polyether (APEE-550) to the octamethylcyclotetrasiloxane and the hydrogen-based POSS is 1: 0.55: 0.05; the weight ratio of the allyl epoxy polyether to the chloroplatinic acid catalyst is 1: 0.05.

the preparation method of the amino polyether organic silicon surfactant comprises the following steps:

introducing nitrogen into a reactor, adding Allyl Glycidyl Ether (AGE), (2R) -3- (3, 4-dihydroxyphenyl) -2- [ (E) -3- [2- [ (E) -2- (3, 4-dihydroxyphenyl) vinyl ] -3, 4-dihydroxyphenyl ] prop-2-enoyl ] oxypropionic acid and a chloroplatinic acid catalyst (diluted to 1% by using isopropanol), heating to 80 ℃ in the absence of light, dropwise adding a toluene solution of hydrogen-containing silicone oil, carrying out heat preservation reaction for 5 hours, cooling to room temperature after the reaction is finished, precipitating the liquid in a mixed solution (v/v ═ 20/1) of n-hexane and tetrahydrofuran for 3 times to remove the catalyst, removing the n-hexane and tetrahydrofuran in a vacuum drying oven at 80 ℃ for drying for 20 hours, obtaining an epoxy silicone oil intermediate; the weight ratio of the Allyl Glycidyl Ether (AGE) to the (2R) -3- (3, 4-dihydroxyphenyl) -2- [ (E) -3- [2- [ (E) -2- (3, 4-dihydroxyphenyl) vinyl ] -3, 4-dihydroxyphenyl ] prop-2-enoyl ] oxypropionic acid to the hydrogen-containing silicone oil is 1: 0.07: 1.2; the weight ratio of the allyl glycidyl ether to the chloroplatinic acid catalyst is 1: 0.05; the weight ratio of the hydrogen-containing silicone oil to the toluene is 1: 3;

(2) introducing nitrogen into a reactor, adding an epoxy silicone oil intermediate, polyether amine M-1000 and absolute ethyl alcohol, heating to 60 ℃, keeping the temperature for reaction for 3 hours, removing the solvent under reduced pressure, and drying in a vacuum drying oven for 20 hours at 60 ℃ to obtain the amino polyether organic silicon surfactant; the weight ratio of the epoxy silicone oil intermediate to the polyether amine M-1000 to the absolute ethyl alcohol is 1: 0.7: 10.

fluorosurfactants, i.e., fluorosurfactants in which the hydrogen atoms on the lipophilic group (hydrocarbon chain) are completely replaced by fluorine. Due to the particularity of fluorine-carbon bonds, the fluorine-containing antifogging agent is the most effective type at present and has ultrahigh surface activity, heat resistance, chemical resistance and the like. The fluorocarbon bond has an extremely strong hydrophobic and oleophobic ability, and the structure determines that the fluorosurfactant can significantly reduce the surface tension of water, but not the interfacial tension.

In one embodiment, the fluorosurfactant is a fluorosilicone surfactant.

In one embodiment, the allyl polyether has an EO/PO ═ 4: 6.

the allyl polyether is purchased from break Tai chemical Co., Ltd in Nantong city.

The preparation method of the fluorosilicone surfactant comprises the following steps:

introducing nitrogen into a reactor, adding allyl polyether and hydrogen-containing silicone oil, keeping out of the sun, heating to 90 ℃, dropwise adding a chloroplatinic acid catalyst (diluted to 1% by using isopropanol), carrying out heat preservation reaction for 1h, then adding N-ethyl perfluorooctylsulfonamide ethyl acrylate, carrying out heat preservation reaction for 5h, cooling to room temperature after the reaction is finished, precipitating the liquid in a mixed solution (v/v: 20/1) of N-hexane and tetrahydrofuran for 3 times to remove the catalyst, and removing the N-hexane and the tetrahydrofuran under reduced pressure to obtain the fluorosilicone surfactant; the weight ratio of the allyl polyether to the hydrogen-containing silicone oil is 1: 1.3; the weight parts of the allyl polyether and the chloroplatinic acid catalyst are 1: 0.05; the weight ratio of the allyl polyether to the N-ethyl perfluorooctylsulfonamide ethyl acrylate is 1: 0.54.

in one embodiment, the weight ratio of the silicon surfactant to the fluorosurfactant is 1: (0.3-0.6); preferably, the weight ratio of the silicon surfactant to the fluorosurfactant is 1: 0.45.

In one embodiment, the modified nanosilica has a particle size of 10-200 nm; preferably, the particle size of the modified nano silicon dioxide is 50-80 nm.

The preparation method of the modified nano silicon dioxide comprises the following steps:

(1) adding nano-silica, dimethylbenzene and dimethyl diphenyl diisocyanate (CAS: 91-97-4) into a reactor, introducing nitrogen, stirring at room temperature for 0.5h, heating to 50 ℃, dropwise adding a mixed solution of E44 epoxy resin and dimethylbenzene, heating to 130 ℃ after dropwise adding, carrying out heat preservation reaction for 12h, cooling to room temperature, filtering, leaching for 3 times by using absolute ethyl alcohol, and drying at 80 ℃ under reduced pressure to obtain dimethyl diphenyl diisocyanate modified nano-silica; the weight ratio of the nano silicon dioxide to the mixed solution of the xylene, the dimethyl diphenyl diisocyanate and the E44 epoxy resin to the xylene is 1: 10: 0.3: 1; the weight ratio of the E44 epoxy resin to the xylene in the mixed solution of the E44 epoxy resin and xylene is 1: 3;

(2) adding dimethyl diphenyl diisocyanate modified nano silicon dioxide and xylene into a reactor, heating to 50 ℃, adding 4-aminomethyl benzyl alcohol (CAS: 39895-56-2) in 3 batches, heating to 80 ℃, carrying out heat preservation reaction for 3 hours, cooling to room temperature, filtering, leaching for 3 times by using absolute ethyl alcohol, and drying at 80 ℃ under reduced pressure to obtain modified nano silicon dioxide; the weight ratio of the dimethyl biphenyl diisocyanate modified nano silicon dioxide to the dimethylbenzene to the 4-aminomethyl benzyl alcohol is 1: 10: 0.32.

the modified nano silicon dioxide contains both flexible chains and rigid group silicon dioxide, the flexible chains are used as toughening phases, the toughness of the resin can be effectively improved, the modified silicon dioxide rigid inorganic network can compensate modulus loss caused by toughening of the flexible chains, meanwhile, the toughness of the material can be improved, the impact strength of the preparation material of the swimming goggles, namely the resin, can be greatly improved under the synergistic action of the flexible chains and the rigid inorganic network, and meanwhile, the high temperature resistance of the antifogging agent composition in the resin is improved.

When the content of the silicon surfactant is very low, the surface tension of water can be reduced, the interfacial tension of water and resin can be reduced, and the silicon surfactant has excellent thermal stability and chemical stability. The introduction of the hydrogen-based-POSS and phenyl group in the modified organic silicon surfactant reduces the possibility of yellowing of the antifogging agent at high temperature, further causes yellowing of lenses and improves the weather resistance; the amino polyether organic silicon is used as a novel non-toxic, pollution-free and environment-friendly surfactant, combines the advantages of amino silicone oil and polyether silicone oil, has low surface tension and good wetting and spreading performance, amino groups are added in the molecular structure of the amino polyether organic silicon, and the introduction of amino polar groups increases the hydrophilicity of a final product and can improve the dispersibility in a system; the fluorine-containing surfactant has ultrahigh surface activity, heat resistance, chemical resistance and the like. The carbon-fluorine bond has super-strong hydrophobic and oleophobic abilities, and the structure determines that the fluorine-containing surfactant can obviously reduce the surface tension of water but can not reduce the interfacial tension; according to the invention, through the synergistic effect of the modified organic silicon surfactant, the amino polyether organic silicon surfactant and the fluorine-containing surfactant, the surface of the film material prepared by the internal addition method can have a better anti-fog dripping effect; the introduction of amino and fluorine-containing surfactant hydroxyl in the amino polyether organic silicon surfactant can form a cross-linked structure at high temperature, and in the process of anti-fog dripping, the anti-fog agent cannot be separated out and lose effectiveness along with water loss, so that the anti-fog function cannot be lost; the modified nano silicon dioxide contains both flexible chains and rigid group silicon dioxide, the flexible chains are used as toughening phases, the toughness of the resin can be effectively improved, the modified silicon dioxide rigid inorganic network can compensate modulus loss caused by toughening of the flexible chains, and the impact strength of the preparation material of the swimming goggles, namely the resin, can be greatly improved under the synergistic action of the flexible chains and the rigid inorganic network, and meanwhile, the high temperature resistance of the antifogging agent composition in the resin is improved, and the weather resistance, the high temperature resistance, the low temperature resistance and the long-acting antifogging effect of the antifogging agent composition are improved; therefore, the invention provides an internal addition type antifogging agent composition which is well compatible with lenses, does not influence transparency, has long-acting antifogging effect, and has excellent performances of weather resistance, high temperature resistance and low temperature resistance.

In addition, the raw materials used are commercially available from national chemical reagents, unless otherwise specified.

Example 1

The internal addition type antifogging agent composition at least comprises 60 parts of silicon-containing surfactant, 27 parts of fluorine-containing surfactant, 5 parts of penetrating agent and 2 parts of modified nano silicon dioxide by weight; wherein the silicon-containing surfactant is a modified silicone surfactant and an aminopolyether silicone surfactant, and the weight ratio of the modified silicone surfactant to the aminopolyether silicone surfactant is 1: 0.7; the modified organosilicon surfactant is prepared from raw materials including octamethylcyclotetrasiloxane, hydrogen-based POSS and allyl epoxy polyether; the raw materials for preparing the amino polyether organosilicon surfactant comprise Allyl Glycidyl Ether (AGE), (2R) -3- (3, 4-dihydroxyphenyl) -2- [ (E) -3- [2- [ (E) -2- (3, 4-dihydroxyphenyl) vinyl ] -3, 4-dihydroxyphenyl ] prop-2-enoyl ] oxypropionic acid, hydrogen-containing silicone oil and polyether amine M-1000; the fluorine-containing surfactant is a fluorosilicone surfactant, the raw materials for preparing the fluorosilicone surfactant comprise allyl polyether, hydrogen-containing silicone oil and N-ethyl perfluorooctyl sulfonamide ethyl acrylate, and EO/PO (ethylene oxide)/PO (propylene oxide) in the allyl polyether is as follows: 6; the penetrating agent is isomeric tridecanol polyoxyethylene ether; the weight ratio of the silicon surfactant to the fluorine-containing surfactant is 1: 0.45 of; the modified nano-silica is dimethyl diphenyl diisocyanate and 4-aminomethyl benzyl alcohol modified nano-silica, and the particle size of the modified nano-silica is 60 nm;

the preparation method of the internal addition type antifogging agent composition comprises the following steps:

adding a silicon surfactant, a fluorine-containing surfactant, a penetrating agent and modified nano silicon dioxide into a reactor according to the parts by weight, stirring for 3 hours at room temperature, and uniformly mixing to obtain the internal addition type antifogging agent composition for the swimming goggles.

example 2

The internal addition type antifogging agent composition at least comprises 67 parts of a silicon-containing surfactant, 20 parts of a fluorine-containing surfactant, 5 parts of a penetrating agent and 2 parts of modified nano silicon dioxide by weight; wherein the silicon-containing surfactant is a modified silicone surfactant and an aminopolyether silicone surfactant, and the weight ratio of the modified silicone surfactant to the aminopolyether silicone surfactant is 1: 0.7; the modified organosilicon surfactant is prepared from raw materials including octamethylcyclotetrasiloxane, hydrogen-based POSS and allyl epoxy polyether; the raw materials for preparing the amino polyether organosilicon surfactant comprise Allyl Glycidyl Ether (AGE), (2R) -3- (3, 4-dihydroxyphenyl) -2- [ (E) -3- [2- [ (E) -2- (3, 4-dihydroxyphenyl) vinyl ] -3, 4-dihydroxyphenyl ] prop-2-enoyl ] oxypropionic acid, hydrogen-containing silicone oil and polyether amine M-1000; the fluorine-containing surfactant is a fluorosilicone surfactant, the raw materials for preparing the fluorosilicone surfactant comprise allyl polyether, hydrogen-containing silicone oil and N-ethyl perfluorooctyl sulfonamide ethyl acrylate, and EO/PO (ethylene oxide)/PO (propylene oxide) in the allyl polyether is as follows: 6; the penetrating agent is isomeric tridecanol polyoxyethylene ether; the weight ratio of the silicon surfactant to the fluorine-containing surfactant is 1: 0.45 of; the modified nano-silica is dimethyl diphenyl diisocyanate and 4-aminomethyl benzyl alcohol modified nano-silica, and the particle size of the modified nano-silica is 60 nm;

the preparation method of the internal addition type antifogging agent composition, the preparation method of the modified organic silicon surfactant, the preparation method of the amino polyether organic silicon surfactant, the preparation method of the fluorosilicone surfactant and the preparation method of the modified nano silicon dioxide are the same as those of example 1.

Example 3

The internal addition type antifogging agent composition at least comprises 60 parts of silicon-containing surfactant, 27 parts of fluorine-containing surfactant, 5 parts of penetrating agent and 0.5 part of modified nano silicon dioxide by weight; wherein the silicon-containing surfactant is a modified silicone surfactant and an aminopolyether silicone surfactant, and the weight ratio of the modified silicone surfactant to the aminopolyether silicone surfactant is 1: 0.7; the modified organosilicon surfactant is prepared from raw materials including octamethylcyclotetrasiloxane, hydrogen-based POSS and allyl epoxy polyether; the raw materials for preparing the amino polyether organosilicon surfactant comprise Allyl Glycidyl Ether (AGE), (2R) -3- (3, 4-dihydroxyphenyl) -2- [ (E) -3- [2- [ (E) -2- (3, 4-dihydroxyphenyl) vinyl ] -3, 4-dihydroxyphenyl ] prop-2-enoyl ] oxypropionic acid, hydrogen-containing silicone oil and polyether amine M-1000; the fluorine-containing surfactant is a fluorosilicone surfactant, the raw materials for preparing the fluorosilicone surfactant comprise allyl polyether, hydrogen-containing silicone oil and N-ethyl perfluorooctyl sulfonamide ethyl acrylate, and EO/PO (ethylene oxide)/PO (propylene oxide) in the allyl polyether is as follows: 6; the penetrating agent is isomeric tridecanol polyoxyethylene ether; the weight ratio of the silicon surfactant to the fluorine-containing surfactant is 1: 0.45 of; the modified nano-silica is dimethyl diphenyl diisocyanate and 4-aminomethyl benzyl alcohol modified nano-silica, and the particle size of the modified nano-silica is 60 nm;

Example 4

The internal addition type antifogging agent composition at least comprises 60 parts of silicon-containing surfactant, 27 parts of fluorine-containing surfactant, 5 parts of penetrating agent and 6 parts of modified nano silicon dioxide by weight; wherein the silicon-containing surfactant is a modified silicone surfactant and an aminopolyether silicone surfactant, and the weight ratio of the modified silicone surfactant to the aminopolyether silicone surfactant is 1: 0.7; the modified organosilicon surfactant is prepared from raw materials including octamethylcyclotetrasiloxane, hydrogen-based POSS and allyl epoxy polyether; the raw materials for preparing the amino polyether organosilicon surfactant comprise Allyl Glycidyl Ether (AGE), (2R) -3- (3, 4-dihydroxyphenyl) -2- [ (E) -3- [2- [ (E) -2- (3, 4-dihydroxyphenyl) vinyl ] -3, 4-dihydroxyphenyl ] prop-2-enoyl ] oxypropionic acid, hydrogen-containing silicone oil and polyether amine M-1000; the fluorine-containing surfactant is a fluorosilicone surfactant, the raw materials for preparing the fluorosilicone surfactant comprise allyl polyether, hydrogen-containing silicone oil and N-ethyl perfluorooctyl sulfonamide ethyl acrylate, and EO/PO (ethylene oxide)/PO (propylene oxide) in the allyl polyether is as follows: 6; the penetrating agent is isomeric tridecanol polyoxyethylene ether; the weight ratio of the silicon surfactant to the fluorine-containing surfactant is 1: 0.45 of; the modified nano-silica is dimethyl diphenyl diisocyanate and 4-aminomethyl benzyl alcohol modified nano-silica, and the particle size of the modified nano-silica is 60 nm;

Example 5

The internal addition type antifogging agent composition at least comprises 60 parts of silicon-containing surfactant, 27 parts of fluorine-containing surfactant, 5 parts of penetrating agent and 2 parts of modified nano silicon dioxide by weight; wherein the silicon-containing surfactant is a modified silicone surfactant and an aminopolyether silicone surfactant, and the weight ratio of the modified silicone surfactant to the aminopolyether silicone surfactant is 1: 0.2; the modified organosilicon surfactant is prepared from raw materials including octamethylcyclotetrasiloxane, hydrogen-based POSS and allyl epoxy polyether; the raw materials for preparing the amino polyether organosilicon surfactant comprise Allyl Glycidyl Ether (AGE), (2R) -3- (3, 4-dihydroxyphenyl) -2- [ (E) -3- [2- [ (E) -2- (3, 4-dihydroxyphenyl) vinyl ] -3, 4-dihydroxyphenyl ] prop-2-enoyl ] oxypropionic acid, hydrogen-containing silicone oil and polyether amine M-1000; the fluorine-containing surfactant is a fluorosilicone surfactant, the raw materials for preparing the fluorosilicone surfactant comprise allyl polyether, hydrogen-containing silicone oil and N-ethyl perfluorooctyl sulfonamide ethyl acrylate, and EO/PO (ethylene oxide)/PO (propylene oxide) in the allyl polyether is as follows: 6; the penetrating agent is isomeric tridecanol polyoxyethylene ether; the weight ratio of the silicon surfactant to the fluorine-containing surfactant is 1: 0.45 of; the modified nano-silica is dimethyl diphenyl diisocyanate and 4-aminomethyl benzyl alcohol modified nano-silica, and the particle size of the modified nano-silica is 60 nm;

Example 6

The internal addition type antifogging agent composition at least comprises 60 parts of silicon-containing surfactant, 27 parts of fluorine-containing surfactant, 5 parts of penetrating agent and 2 parts of modified nano silicon dioxide by weight; wherein the silicon-containing surfactant is a modified silicone surfactant and an aminopolyether silicone surfactant, and the weight ratio of the modified silicone surfactant to the aminopolyether silicone surfactant is 1: 1.5; the modified organosilicon surfactant is prepared from raw materials including octamethylcyclotetrasiloxane, hydrogen-based POSS and allyl epoxy polyether; the raw materials for preparing the amino polyether organosilicon surfactant comprise Allyl Glycidyl Ether (AGE), (2R) -3- (3, 4-dihydroxyphenyl) -2- [ (E) -3- [2- [ (E) -2- (3, 4-dihydroxyphenyl) vinyl ] -3, 4-dihydroxyphenyl ] prop-2-enoyl ] oxypropionic acid, hydrogen-containing silicone oil and polyether amine M-1000; the fluorine-containing surfactant is a fluorosilicone surfactant, the raw materials for preparing the fluorosilicone surfactant comprise allyl polyether, hydrogen-containing silicone oil and N-ethyl perfluorooctyl sulfonamide ethyl acrylate, and EO/PO (ethylene oxide)/PO (propylene oxide) in the allyl polyether is as follows: 6; the penetrating agent is isomeric tridecanol polyoxyethylene ether; the weight ratio of the silicon surfactant to the fluorine-containing surfactant is 1: 0.45 of; the modified nano-silica is dimethyl diphenyl diisocyanate and 4-aminomethyl benzyl alcohol modified nano-silica, and the particle size of the modified nano-silica is 60 nm;

Comparative example 1

The internal addition type antifogging agent composition at least comprises 60 parts of silicon-containing surfactant, 27 parts of fluorine-containing surfactant, 5 parts of penetrating agent and 2 parts of modified nano silicon dioxide by weight; wherein the silicon-containing surfactant is a modified silicone surfactant; the modified organosilicon surfactant is prepared from raw materials including octamethylcyclotetrasiloxane, hydrogen-based POSS and allyl epoxy polyether; the raw materials for preparing the amino polyether organosilicon surfactant comprise Allyl Glycidyl Ether (AGE), (2R) -3- (3, 4-dihydroxyphenyl) -2- [ (E) -3- [2- [ (E) -2- (3, 4-dihydroxyphenyl) vinyl ] -3, 4-dihydroxyphenyl ] prop-2-enoyl ] oxypropionic acid, hydrogen-containing silicone oil and polyether amine M-1000; the fluorine-containing surfactant is a fluorosilicone surfactant, the raw materials for preparing the fluorosilicone surfactant comprise allyl polyether, hydrogen-containing silicone oil and N-ethyl perfluorooctyl sulfonamide ethyl acrylate, and EO/PO (ethylene oxide)/PO (propylene oxide) in the allyl polyether is as follows: 6; the penetrating agent is isomeric tridecanol polyoxyethylene ether; the weight ratio of the silicon surfactant to the fluorine-containing surfactant is 1: 0.45 of; the modified nano-silica is dimethyl diphenyl diisocyanate and 4-aminomethyl benzyl alcohol modified nano-silica, and the particle size of the modified nano-silica is 60 nm;

the preparation method of the internal addition type antifogging agent composition, the preparation method of the amino polyether organic silicon surfactant, the preparation method of the fluorine-silicon surfactant and the preparation method of the modified nano silicon dioxide are the same as those in example 1.

Comparative example 2

The internal addition type antifogging agent composition at least comprises 60 parts of silicon-containing surfactant, 27 parts of fluorine-containing surfactant, 5 parts of penetrating agent and 2 parts of modified nano silicon dioxide by weight; wherein the silicon-containing surfactant is an amino polyether silicone surfactant; the modified organosilicon surfactant is prepared from raw materials including octamethylcyclotetrasiloxane, hydrogen-based POSS and allyl epoxy polyether; the raw materials for preparing the amino polyether organosilicon surfactant comprise Allyl Glycidyl Ether (AGE), (2R) -3- (3, 4-dihydroxyphenyl) -2- [ (E) -3- [2- [ (E) -2- (3, 4-dihydroxyphenyl) vinyl ] -3, 4-dihydroxyphenyl ] prop-2-enoyl ] oxypropionic acid, hydrogen-containing silicone oil and polyether amine M-1000; the fluorine-containing surfactant is a fluorosilicone surfactant, the raw materials for preparing the fluorosilicone surfactant comprise allyl polyether, hydrogen-containing silicone oil and N-ethyl perfluorooctyl sulfonamide ethyl acrylate, and EO/PO (ethylene oxide)/PO (propylene oxide) in the allyl polyether is as follows: 6; the penetrating agent is isomeric tridecanol polyoxyethylene ether; the weight ratio of the silicon surfactant to the fluorine-containing surfactant is 1: 0.45 of; the modified nano-silica is dimethyl diphenyl diisocyanate and 4-aminomethyl benzyl alcohol modified nano-silica, and the particle size of the modified nano-silica is 60 nm;

Comparative example 3

The internal addition type antifogging agent composition at least comprises 60 parts of silicon-containing surfactant, 27 parts of fluorine-containing surfactant, 5 parts of penetrating agent and 2 parts of modified nano silicon dioxide by weight; wherein the silicon-containing surfactant is a modified silicone surfactant and an aminopolyether silicone surfactant, and the weight ratio of the modified silicone surfactant to the aminopolyether silicone surfactant is 1: 0.7; the modified organosilicon surfactant is prepared from raw materials including octamethylcyclotetrasiloxane and allyl epoxy polyether; the raw materials for preparing the amino polyether organosilicon surfactant comprise Allyl Glycidyl Ether (AGE), (2R) -3- (3, 4-dihydroxyphenyl) -2- [ (E) -3- [2- [ (E) -2- (3, 4-dihydroxyphenyl) vinyl ] -3, 4-dihydroxyphenyl ] prop-2-enoyl ] oxypropionic acid, hydrogen-containing silicone oil and polyether amine M-1000; the fluorine-containing surfactant is a fluorosilicone surfactant, the raw materials for preparing the fluorosilicone surfactant comprise allyl polyether, hydrogen-containing silicone oil and N-ethyl perfluorooctyl sulfonamide ethyl acrylate, and EO/PO (ethylene oxide)/PO (propylene oxide) in the allyl polyether is as follows: 6; the penetrating agent is isomeric tridecanol polyoxyethylene ether; the weight ratio of the silicon surfactant to the fluorine-containing surfactant is 1: 0.45 of; the modified nano-silica is dimethyl diphenyl diisocyanate and 4-aminomethyl benzyl alcohol modified nano-silica, and the particle size of the modified nano-silica is 60 nm;

Comparative example 4

The internal addition type antifogging agent composition at least comprises 60 parts of silicon-containing surfactant, 27 parts of fluorine-containing surfactant, 5 parts of penetrating agent and 2 parts of modified nano silicon dioxide by weight; wherein the silicon-containing surfactant is a modified silicone surfactant and an aminopolyether silicone surfactant, and the weight ratio of the modified silicone surfactant to the aminopolyether silicone surfactant is 1: 0.7; the modified organosilicon surfactant is prepared from raw materials including octamethylcyclotetrasiloxane, hydrogen-based POSS and allyl epoxy polyether; the raw materials for preparing the amino polyether organic silicon surfactant comprise Allyl Glycidyl Ether (AGE), hydrogen-containing silicone oil and polyether amine M-1000; the fluorine-containing surfactant is a fluorosilicone surfactant, the raw materials for preparing the fluorosilicone surfactant comprise allyl polyether, hydrogen-containing silicone oil and N-ethyl perfluorooctyl sulfonamide ethyl acrylate, and EO/PO (ethylene oxide)/PO (propylene oxide) in the allyl polyether is as follows: 6; the penetrating agent is isomeric tridecanol polyoxyethylene ether; the weight ratio of the silicon surfactant to the fluorine-containing surfactant is 1: 0.45 of; the modified nano-silica is dimethyl diphenyl diisocyanate and 4-aminomethyl benzyl alcohol modified nano-silica, and the particle size of the modified nano-silica is 60 nm;

Comparative example 5

The internal addition type antifogging agent composition at least comprises 60 parts of silicon-containing surfactant, 27 parts of fluorine-containing surfactant and 5 parts of penetrating agent by weight; wherein the silicon-containing surfactant is a modified silicone surfactant and an aminopolyether silicone surfactant, and the weight ratio of the modified silicone surfactant to the aminopolyether silicone surfactant is 1: 0.7; the modified organosilicon surfactant is prepared from raw materials including octamethylcyclotetrasiloxane, hydrogen-based POSS and allyl epoxy polyether; the raw materials for preparing the amino polyether organosilicon surfactant comprise Allyl Glycidyl Ether (AGE), (2R) -3- (3, 4-dihydroxyphenyl) -2- [ (E) -3- [2- [ (E) -2- (3, 4-dihydroxyphenyl) vinyl ] -3, 4-dihydroxyphenyl ] prop-2-enoyl ] oxypropionic acid, hydrogen-containing silicone oil and polyether amine M-1000; the fluorine-containing surfactant is a fluorosilicone surfactant, the raw materials for preparing the fluorosilicone surfactant comprise allyl polyether, hydrogen-containing silicone oil and N-ethyl perfluorooctyl sulfonamide ethyl acrylate, and EO/PO (ethylene oxide)/PO (propylene oxide) in the allyl polyether is as follows: 6; the penetrating agent is isomeric tridecanol polyoxyethylene ether; the weight ratio of the silicon surfactant to the fluorine-containing surfactant is 1: 0.45 of;

the preparation method of the internal addition type antifogging agent composition, the preparation method of the modified organic silicon surfactant, the preparation method of the amino polyether organic silicon surfactant and the preparation method of the fluorosilicone surfactant are the same as those of the example 1 (except that the modified nano silicon dioxide is not used).

Comparative example 6

The internal addition type antifogging agent composition at least comprises 60 parts of silicon-containing surfactant, 27 parts of fluorine-containing surfactant and 5 parts of penetrating agent by weight; wherein the silicon-containing surfactant is a modified silicone surfactant and an aminopolyether silicone surfactant, and the weight ratio of the modified silicone surfactant to the aminopolyether silicone surfactant is 1: 0.7; the modified organosilicon surfactant is prepared from raw materials including octamethylcyclotetrasiloxane and allyl epoxy polyether; the raw materials for preparing the amino polyether organic silicon surfactant comprise Allyl Glycidyl Ether (AGE), hydrogen-containing silicone oil and polyether amine M-1000; the fluorine-containing surfactant is a fluorosilicone surfactant, the raw materials for preparing the fluorosilicone surfactant comprise allyl polyether, hydrogen-containing silicone oil and N-ethyl perfluorooctyl sulfonamide ethyl acrylate, and EO/PO (ethylene oxide)/PO (propylene oxide) in the allyl polyether is as follows: 6; the penetrating agent is isomeric tridecanol polyoxyethylene ether; the weight ratio of the silicon surfactant to the fluorine-containing surfactant is 1: 0.45 of; the modified nano-silica is dimethyl diphenyl diisocyanate and 4-aminomethyl benzyl alcohol modified nano-silica, and the particle size of the modified nano-silica is 60 nm;

1. Antifogging effect

Carrying out an antifogging effect comparison experiment on swimming goggles prepared from the antifogging agent composition and swimming goggles prepared from a commercially available spray-type antifogging agent;

the visual acuity of both eyes of a tester wearing the glasses is 1.5, the left side of the glasses is provided with a swimming lens made of the antifogging agent composition, and the right side of the glasses is coated with a swimming lens made of a commercially available antifogging agent. The tester has a visual chart with five meters in front, and the visual chart has fourteen rows from top to bottom, which are marked as 1-14 grades in sequence. The glasses are placed in a refrigerator and taken out after 10min, so that a tester wears the glasses and wears the mask, the mask covers the nose, deep breathing is carried out for 25 times, and then the tester looks at the visual chart to use the clear highest level as the antifogging level of the experiment. The above procedure of putting the glasses into the refrigerator and then taking out the glasses for testing was repeated.

2. Stability: swimming goggles made of the antifogging agent composition are respectively placed for 72 hours at the temperature of 60 ℃ and 72 hours at the temperature of-5 ℃ and tested according to the antifogging effect.

Table 1 results of performance testing

From the data, the internal addition type antifogging agent composition provided by the invention has good compatibility with lenses, does not influence transparency, has long-acting antifogging effect, and has excellent performances of weather resistance, high temperature resistance and low temperature resistance.

The above examples are merely illustrative and serve to explain some of the features of the invention. The appended claims are intended to claim as broad a scope as is contemplated, and the examples presented herein are merely illustrative of selected implementations in accordance with all possible combinations of examples. Accordingly, it is applicants' intention that the appended claims not be limited by the choice of examples illustrating features of the invention, and that technological advances will form possible equivalents or sub-substitutes not presently contemplated for reasons of inaccuracy of the linguistic expressions, and that such variations are to be construed as being covered by the appended claims where possible.

Claims

1. The internal addition type antifogging agent composition is characterized by at least comprising 50-70 parts by weight of silicon-containing surfactant, 15-30 parts by weight of fluorine-containing surfactant, 1-10 parts by weight of penetrating agent and 0.5-10 parts by weight of modified nano silicon dioxide; wherein the silicon-containing surfactant comprises a modified silicone surfactant, an aminopolyether silicone surfactant; the modified nano-silica is nano-silica modified by dimethyl diphenyl diisocyanate and 4-aminomethyl benzyl alcohol;

the modified organosilicon surfactant is prepared from raw materials including octamethylcyclotetrasiloxane, hydrogen-based POSS and allyl epoxy polyether.

2. The internal addition type antifogging agent composition according to claim 1, characterized in that, calculated by weight, the internal addition type antifogging agent composition at least comprises 55-68 parts of silicon-containing surfactant, 15-25 parts of fluorine-containing surfactant, 2-8 parts of penetrating agent and 0.5-6 parts of modified nano silicon dioxide.

3. The internal addition type antifogging agent composition according to claim 1, wherein the raw materials for preparing the amino polyether silicone surfactant comprise allyl glycidyl ether, (2R) -3- (3, 4-dihydroxyphenyl) -2- [ (E) -3- [2- [ (E) -2- (3, 4-dihydroxyphenyl) vinyl ] -3, 4-dihydroxyphenyl ] prop-2-enoyl ] oxypropionic acid, hydrogen-containing silicone oil and polyether amine.

4. The internal addition antifog agent composition according to claim 1, characterized in that, the fluorine-containing surfactant comprises one or more of fluorocarbon surfactant, fluorine silicon surfactant.

5. The internal addition type antifogging agent composition according to claim 4, characterized in that, the fluorine-containing surfactant is a fluorosilicone surfactant.

6. The internal addition type antifogging agent composition according to claim 5, wherein the raw materials for preparing the fluorosilicone surfactant comprise allyl polyether, hydrogen-containing silicone oil and N-ethyl perfluorooctylsulfonamide ethyl acrylate.

7. The internal addition antifog agent composition according to claim 1, wherein the penetrant comprises one or more of isomeric dodecyl alcohol polyoxyethylene ether, isomeric undecyl alcohol polyoxyethylene ether, isomeric tridecyl alcohol polyoxyethylene ether, and phosphate ester.

8. The internal additive antifogging agent composition according to any one of claims 1 to 7, wherein the internal additive antifogging agent composition is applied to the field of glasses and swimming goggles.

9. The process for the preparation of an internal addition antifog agent composition according to any of the claims 1 to 7, characterized in that it comprises the following steps: