CN111471331A

CN111471331A - Antibacterial, antiviral and antifogging coating sol, goggles and preparation method

Info

Publication number: CN111471331A
Application number: CN202010212379.8A
Authority: CN
Inventors: 陈广川; 于红光; 李梦婷
Original assignee: Tongxi Group Co ltd
Current assignee: Tongxi Group Co ltd
Priority date: 2020-03-24
Filing date: 2020-03-24
Publication date: 2020-07-31

Abstract

The invention relates to an antibacterial, antiviral and antifogging coating sol, goggles and a preparation method, wherein the sol comprises an inorganic photocatalyst sol, a flatting agent, a binder and a thickening agent; the inorganic photocatalyst sol is prepared from the following raw materials: the antibacterial and antifogging goggles prepared by the method have excellent antibacterial and antiviral functions, the antibacterial rate to escherichia coli and staphylococcus aureus can be up to more than 99% through tests, the antiviral activity rate to H1N1 and H3N2 is up to more than 99%, the antifogging effect is excellent, the antibacterial and antifogging film layer coated on the prepared lens substrate is mainly made of inorganic photocatalyst materials and can play an antibacterial role under the action of light and no light, meanwhile, the prepared goggles have high light transmission, the light transmittance is up to more than 95%, and the use requirements of medical goggles are met.

Description

Antibacterial, antiviral and antifogging coating sol, goggles and preparation method

Technical Field

The invention belongs to the field of goggles, and particularly relates to an antibacterial, antiviral and antifogging coating sol, goggles and a preparation method.

Background

Fogging of goggles is a very common and troublesome problem for people who wear goggles on a regular or extended basis, especially in winter or when there are large temperature differences between the inside and outside of the room and when warmer temperatures from perspiration and breathing enter the goggle housing. The fogging of the goggles causes a wearer to see objects or expected targets in front clearly, easily causes traffic accidents in the driving process of the driver wearing the goggles, causes medical accidents in the operation process of medical workers wearing the goggles, and causes various accidents in the use process of the workers wearing the goggles, such as swimming and mountaineering. Therefore, how to perform an anti-fog treatment on the goggles is an urgent problem to be solved. In addition, because the goggles are in contact with the most fragile organs and eyes of the human body, bacteria are easy to breed due to the existence of water vapor in the using process of the goggles, once the bacteria are settled in the eyes of the human body, the bacteria are always kept in a stable and unchangeable state within six weeks, and therefore serious harm is caused to the eyes and the health of the human body, and therefore the antibacterial effect is also a problem to be solved urgently. In addition, when the medical staff uses the goggles, viruses easily enter the inside of the goggles to cause cross infection of the medical staff, and therefore, the viruses are also an important problem to be solved by the goggles.

At present, in order to solve the problems, the lenses are mostly treated by coating a plurality of functional film layers on the surfaces of the lenses, and the process for carrying out anti-fog treatment on the lenses mainly comprises the step of adding a hydrophilic high polymer material into a coating material of the anti-fog film layers so as to form a hydrophilic organic anti-fog film layer on the surfaces of the lenses, wherein the problem is that the durability is poor; the antibacterial and antiviral agent is added into the antibacterial film layer material at present for the treatment of the antibacterial and antiviral film layer, but the organic antibacterial agent added by the common treatment method has poor durability and poor durability of the antibacterial effect, and the added inorganic antibacterial agent can cause the reduction of the transparency of the goggles due to the uneven dispersion of the inorganic particles, thereby seriously affecting the use of the goggles; in addition, at present, a film material which has excellent transparency and can integrate the functions of antibiosis, antivirus and antifogging is not available for being used as a lens coating of the goggles.

Disclosure of Invention

The invention aims to overcome the defects of the prior art and provides an antibacterial, antiviral and antifogging coating sol, goggles and a preparation method.

In order to achieve the purpose, the technical scheme adopted by the invention is as follows:

the first technical scheme is as follows:

the utility model provides an antibiotic antiviral antifog coating sol coats the surface of goggles lens, includes inorganic photocatalyst sol, inorganic photocatalyst sol is prepared by each raw materials and antibacterial ion including following mole fraction:

1-5 parts by mole of a precursor; 1-3 parts by mole of a complexing agent; 1-5 parts by mole of an acidic catalyst; 2-5 parts by mole of water; 15-50 parts by mole of an organic solvent, wherein the addition amount of the antibacterial ions is 1-9wt% of the precursor.

Further, the antibacterial antiviral antifogging coating sol is characterized by further comprising a flatting agent, a binder and a thickening agent, wherein the antibacterial antiviral antifogging coating sol comprises the following raw materials in parts by weight: 2-10 parts of inorganic photocatalyst sol; 2-10 parts of a leveling agent; 1-5 parts of a binder; 1-5 parts of thickening agent.

Further, the leveling agent is selected from one or two of acrylate homopolymer, organic silicon modified acrylate polymer, polysiloxane/silicone oil and silicon dioxide adsorbed polyacrylate;

the binder is selected from one or two of acrylic acid, sodium polyacrylate, vinyl acetate, epoxy resin and polyurethane;

the thickening agent is one or two selected from carboxymethyl cellulose, propylene glycol alginate, methyl cellulose, sodium starch phosphate, sodium carboxymethyl cellulose, sodium alginate, casein, sodium polyacrylate, polyoxyethylene and polyvinylpyrrolidone.

Further, the molar ratio of water to the organic solvent in the inorganic photocatalyst sol is as follows: 1: 6-13.

Further, the preparation method of the inorganic photocatalyst sol specifically comprises the following steps:

step 1, weighing the raw materials, and dividing the organic solvent into 2 parts, wherein the molar ratio of the first part of organic solvent to the second part of organic solvent is 1: 0.5-3;

step 2, mixing the precursor, the complexing agent and the first part of organic solvent, and stirring until the mixture is dissolved to obtain a solution A;

step 3, mixing water, an acidic catalyst and a second part of organic solvent, adding antibacterial ions, and stirring until the antibacterial ions are completely dissolved to obtain a solution B;

and 4, slowly dripping the solution A into the solution B, and after dripping is finished, magnetically stirring for 60-120min until the solution is uniformly dispersed to obtain the inorganic photocatalyst antibacterial agent sol.

Furthermore, magnetic stirring is adopted for stirring in the step 2, and the stirring time is 30-90 min;

magnetic stirring is adopted for stirring in the step 3, and the stirring time is 30-60 min;

magnetic stirring is adopted for stirring in the step 4, and the stirring time is 60-120 min;

the dropping speed of the slow dropping in the step 4 is that the corresponding dropping speed of the prepared 1L antibacterial, antiviral and antifogging coating sol is 15-40 drops/min.

Furthermore, the precursor is selected from one or more of a titanium dioxide precursor, a zinc oxide precursor, a tungsten oxide precursor, an iron oxide precursor, a tin oxide precursor, a silicon oxide precursor, a bismuth tungstate precursor, a bismuth molybdate precursor and a strontium titanate precursor;

the complexing agent is selected from one or more of diethanolamine, triethanolamine, acetylacetone and methyl tetramine;

the organic solvent is selected from one or more of ethanol, propanol, isopropanol, glycol methyl ether and glycol ethyl ether;

the acidic catalyst is selected from one or more of nitric acid, sulfuric acid, sulfurous acid, hydrochloric acid, phosphoric acid, acetic acid and formic acid;

the antibacterial ions are one or more of silver ions, copper ions, zinc ions and rare earth ions.

Furthermore, the precursor of the titanium dioxide is tetrabutyl titanate, the precursor of the zinc oxide is zinc nitrate hexahydrate, the precursor of the tungsten oxide is ammonium tungstate, the precursor of the iron oxide is ferric nitrate, the precursor of the tin oxide is stannic chloride, the precursor of the silicon oxide is ethyl orthosilicate, the precursor of the bismuth tungstate is a composition of ammonium tungstate and bismuth nitrate, the precursor of the bismuth molybdate is a composition of ammonium molybdate and bismuth nitrate, and the precursor of the strontium titanate is one or more of a composition of butyl titanate and strontium nitrate.

The second technical scheme is as follows:

a preparation method of an antibacterial antiviral antifogging coating sol specifically comprises the following steps:

weighing the inorganic photocatalyst sol, the flatting agent, the binder and the thickening agent according to the weight parts, mixing and stirring until the inorganic photocatalyst sol, the flatting agent, the binder and the thickening agent are uniformly dispersed to obtain the antibacterial, antiviral and antifogging coating sol.

The third technical scheme is as follows:

the utility model provides a goggles, includes picture frame, lens base member, and coat in antibiotic antiviral antifog coating layer on the lens base member, antibiotic antiviral antifog coating layer specifically coats the step as follows:

dropping the antibacterial, antiviral and antifogging coating sol on a lens substrate at 10-30 drops/min, and rotating the lens substrate at the rotation speed of 1200-1500rpm/min for 20-30s while dropping the antibacterial, antiviral and antifogging coating sol;

and (2) after the rotation is finished, placing the lens substrate in an oven for low-temperature drying at 40-70 ℃ for 1-8 h.

Compared with the prior art, the invention has the following beneficial effects:

1. according to the invention, the precursor of the photocatalyst is used as a raw material, the inorganic photocatalyst sol containing the photocatalyst is formed by an acid catalyst, antibacterial ions are added in the preparation process of the inorganic photocatalyst sol, and the antibacterial and antiviral effects of the lens coating are greatly improved by the composite use of the antibacterial ions and the photocatalyst, so that the lens coating can play an antibacterial role under the action of light and no light; tests show that after the inorganic photocatalyst sol prepared by the method is coated on lenses, the antibacterial rate to escherichia coli and staphylococcus aureus can reach more than 99%, and the antiviral activity rate to H1N1 and H3N2 influenza viruses can reach more than 99%.

2. According to the invention, the precursor of the photocatalyst is used as a raw material, and the inorganic photocatalyst sol containing the photocatalyst is formed by the acid catalyst, so that the antifogging principle of the traditional lens is broken through, the lens coating has an antifogging effect on the premise of not additionally adding a hydrophilic polymer, and the luminous flux before and after fogging is almost unchanged through detection; the antifogging principle is as follows: photocatalyst that forms in the coating is through the light irradiation back, can take place the photocatalytic reaction on the surface of goggles rete, form electron-hole pair, form microcosmic hydrophilic region near the oxygen hole, when the water droplet is on its surface, the contact angle can reduce, the water droplet can be because capillary action spreads out on the surface of goggles, forms continuous water film, when the light shines the goggles on, no longer has strong diffuse reflection and refraction to make it have antifog function.

3. The photocatalyst is added in the form of a precursor of the photocatalyst instead of directly, and the antibacterial ions are added in the preparation process of the inorganic photocatalyst sol, so that the antibacterial ions are directly doped into crystal lattices of the photocatalyst, the photocatalytic activity of the photocatalyst is further enhanced, the compatibility problem of the antibacterial ions and the photocatalyst is avoided, and the uniformity of a film coating is not influenced, so that the antibacterial, antiviral and antifogging effects of the coating sol prepared by the method are better after the coating sol is coated on a lens to form a film.

4. According to the invention, researches show that the ratio of the organic solvent to the water has a crucial influence on the transparency of the lens coating in the preparation process of the inorganic photocatalyst sol, and the high-transparency goggles lens is obtained by strictly controlling the ratio of the organic solvent to the water in the inorganic photocatalyst sol system, so that the light transmittance of the goggles lens is detected to be more than 95%, and the problems of poor light transmittance and influence on visual properties of goggles caused by poor transparency of the lens coating prepared by the traditional method are solved.

5. The complexing agent is added in the preparation process of the inorganic photocatalyst sol, so that the problem of poor solubility of an intermediate (organic metal salt) in a solvent in the process of preparing the photocatalyst by reacting a precursor is solved, the solubility of the intermediate in the organic solvent is improved, and the problem of poor film material uniformity caused by high reaction activity of an acidic catalyst and excessively high hydrolysis speed of the precursor is solved, so that the antibacterial, antiviral and antifogging effects of the coating are improved.

6. The invention promotes the coating sol to form a film on the surface of the lens by adding the leveling agent into the coating sol, enhances the adhesive force of the lens coating by adding the binder, and adjusts the thickness of the lens coating by adding the thickening agent.

7. The antibacterial and antiviral antifogging film layer of the lens has higher light transmittance and adhesive force, and is non-toxic and non-irritant to skin by comprehensively acting all the raw materials and controlling all the parameters in the preparation process; in addition, the raw materials adopted by the invention are environment-friendly, low in cost, simple in preparation method and mild in condition, and are beneficial to industrial popularization.

Detailed Description

The present invention will be described in further detail with reference to examples.

Example 1

A first part:

an antibacterial antiviral antifogging coating sol comprises the following raw materials in parts by weight:

wherein, the inorganic photocatalyst sol comprises the following raw materials:

antibacterial ion (antibacterial silver ion): is 6 wt% of the tetrabutyl titanate;

the molar ratio of water to the organic solvent in the inorganic photocatalyst sol system is as follows: 1:10.5.

A second part:

step one, preparation of inorganic photocatalyst sol

Step 1, weighing the raw materials according to the proportion, and dividing the organic solvent into 2 parts, namely a first part of organic solvent and a second part of organic solvent;

step 2, mixing the precursor, the complexing agent and the first part of organic solvent, and magnetically stirring for 60min until the mixture is dissolved to obtain a solution A;

step 3, mixing water, an acidic catalyst and a second part of organic solvent, adding antibacterial ions, and then magnetically stirring for 50min until the antibacterial ions are completely dissolved to obtain a solution B;

step 4, slowly dripping the solution A into the solution B, preparing 1L antibacterial, antiviral and antifogging coating sol with the corresponding dripping speed of 30 drops/min, preparing 2L antibacterial, antiviral and antifogging coating sol with the corresponding dripping speed of 2 × 30 drops/min, and repeating the steps in the same way, preparing n L antibacterial, antiviral and antifogging coating sol with the corresponding dripping speed of n × 30 antibacterial, antiviral and antifogging coating sol with the corresponding dripping speed of n × drops/min, and after finishing dripping, magnetically stirring for 90min until the inorganic photocatalyst sol is uniformly dispersed, thus obtaining the inorganic photocatalyst sol;

step two: adding an auxiliary agent

Third part

dripping the antibacterial and antiviral antifogging coating sol on a lens substrate at 20 drops/min, and rotating the lens substrate at a rotating speed of 1400rpm/min for 30s while dripping the antibacterial and antiviral antifogging coating sol;

and (2) after the rotation is finished, placing the lens substrate in an oven for low-temperature drying at the drying temperature of 60 ℃ for 6 hours.

Example 2

A first part:

wherein, the inorganic photocatalyst sol comprises the following raw materials:

antibacterial ion (antibacterial copper ion): 4 wt% of the zinc nitrate hexahydrate;

the molar ratio of water to the organic solvent in the inorganic photocatalyst sol system is as follows: 1:6.67.

A second part:

a preparation method of an antibacterial antiviral antifogging coating sol specifically comprises the following steps: the same as in example 1.

Third part

Goggles as in example 1.

Example 3

A first part:

wherein, the inorganic photocatalyst sol comprises the following raw materials:

antibacterial ion (antibacterial zinc ion): is 3 wt% of the ammonium tungstate;

the molar ratio of water to the organic solvent in the inorganic photocatalyst sol system is as follows: 1:8.5.

A second part:

Third part

Goggles as in example 1.

Example 4

A first part:

wherein, the inorganic photocatalyst sol comprises the following raw materials:

antibacterial ion (antibacterial silver ion): 7 wt% of the ferric nitrate;

the molar ratio of water to the organic solvent in the inorganic photocatalyst sol system is as follows: 1:7.33.

A second part:

Third part

Goggles as in example 1.

Example 5

A first part:

wherein, the inorganic photocatalyst sol comprises the following raw materials:

antibacterial ion (antibacterial copper ion): 9wt% of the tin chloride;

the molar ratio of water to the organic solvent in the inorganic photocatalyst sol system is as follows: 1:9.2.

A second part:

Third part

Goggles as in example 1.

Example 6

A first part:

wherein, the inorganic photocatalyst sol comprises the following raw materials:

antibacterial ion (antibacterial zinc ion): 2 wt% of the ethyl orthosilicate;

the molar ratio of water to the organic solvent in the inorganic photocatalyst sol system is as follows: 1:9.33.

A second part:

Third part

Goggles as in example 1.

Example 7

A first part:

wherein, the inorganic photocatalyst sol comprises the following raw materials:

antibacterial ion (antibacterial silver ion): 5 wt% of the mixture of ammonium tungstate and bismuth nitrate;

the molar ratio of water to the organic solvent in the inorganic photocatalyst sol system is as follows: 1:13.

A second part:

Third part

Goggles as in example 1.

Example 8

A first part:

wherein, the inorganic photocatalyst sol comprises the following raw materials:

antibacterial ion (antibacterial zinc ion): is 7 wt% of the mixture of ammonium molybdate and bismuth nitrate;

A second part:

Third part

Goggles as in example 1.

Example 9

A first part:

wherein, the inorganic photocatalyst sol comprises the following raw materials:

antibacterial ion (antibacterial zinc ion): is 4 wt% of the mixture of ammonium molybdate and bismuth nitrate;

the molar ratio of water to the organic solvent in the inorganic photocatalyst sol system is as follows: 1:7.

A second part:

Third part

Goggles as in example 1.

Comparative example 1

A first part:

the same as in example 6, except for the difference from example 6:

the organic solvent ethanol is increased from 28 mol parts to 51 mol parts (wherein, the first part of organic solvent is 31 mol parts, the second part of organic solvent is 20 mol parts, and the mol ratio of the first part of organic solvent to the second part of organic solvent is 1: 0.65);

the molar ratio of water to the organic solvent in the inorganic photocatalyst sol system is as follows: 1:17.

A second part:

a preparation method of an antibacterial antiviral antifogging coating sol specifically comprises the following steps: the same as in example 6.

Third part

Goggles as in example 6.

Comparative example 2

A first part:

the same as in example 6, except for the difference from example 6:

the organic solvent ethanol is reduced from 28 molar parts to 14 molar parts (wherein, the first part of the organic solvent is 8.5 molar parts, the second part of the organic solvent is 5.5 molar parts, and the molar ratio of the first part of the organic solvent to the second part of the organic solvent is 1: 0.65);

the molar ratio of water to the organic solvent in the inorganic photocatalyst sol system is as follows: 1:4.67.

A second part:

Third part

Goggles as in example 6.

Comparative example 3

wherein, the inorganic photocatalyst sol comprises the following raw materials:

antibacterial ion (antibacterial zinc ion): 2 wt% of the ethyl orthosilicate;

A second part:

step one, preparation of inorganic photocatalyst sol

Step 1, same as example 1;

step 2, mixing the precursor with the first part of organic solvent, and magnetically stirring for 30-90min until the precursor is dissolved to obtain a solution A;

step 3, the same as example 1;

step 4, the same as example 1;

step two: adding an auxiliary agent

The same as in example 1.

Third part

Goggles as in example 1.

Comparative example 4

antibacterial ion (antibacterial zinc ion): is 0.6 wt% of the silica;

the molar ratio of water to organic solvent in the antibacterial, antiviral and antifogging coating sol system is as follows: 1:9.33.

A second part:

dispersing antibacterial ions and silicon dioxide by using water, adding the dispersed antibacterial ions and silicon dioxide into an organic solvent, uniformly stirring, adding a flatting agent, a binder and a thickening agent, and uniformly stirring.

Third part

Goggles as in example 1.

Effect test

The lenses prepared in the examples 1 to 9 and the comparative examples 1 to 4 are detected, and the main indexes comprise key indexes of antibiosis, antivirus, light transmission and antifogging, and the method comprises the following steps:

according to the determination method disclosed by the national standard GB/T31402-2015 method for testing the antibacterial performance of the plastic surface, escherichia coli and staphylococcus aureus are used as test strains for testing the antibacterial performance;

antiviral performance tests were performed according to the test method disclosed in ISO 21702:2019 "determination of antiviral activity on plastics and other non-porous surfaces", using H1N1 and H3N2 as test viruses;

according to a test method disclosed in GB/T24128-2009 plastic mildew resistance test method, carrying out a mildew resistance test by taking Aspergillus niger, Aureobasidium pullulans, Penicillium funiculosum, Chaetomium globosum and Gliocladium virens as test strains;

carrying out antifogging performance and light transmittance detection according to the national standard GB/T32166.2-2016 eye and face protection instrument for individual protection equipment, eye and face protection occupational eye and face protection instrument, wherein the antifogging performance calculation formula

The detection data of examples 1-9 and comparative examples 1-4 are shown in the following table:

from the comparison of the data of the example 6 and the comparative example 4, it can be seen that the lens film prepared by adopting the preparation process of using the raw material of the precursor, controlling the reaction speed by acid catalysis and the complexing agent, and adding the antibacterial ions in the reaction process of the precursor has better light transmittance, antibacterial, antiviral, mildew-proof and antifogging properties than the comparative example 4 in which the antibacterial ions and the photocatalyst are directly added into the film sol; in the preparation process of the inorganic photocatalyst sol, the embodiment 6 with the complexing agent and the comparative embodiment 3 without the complexing agent are better in all aspects; in addition, as can be seen from the comparison of the data in example 6 and comparative examples 1 to 2, the ratio of water to the organic solvent in the inorganic photocatalyst sol reaction system is a key index affecting the antifogging property and the light transmittance, and the ratio of water to the organic solvent is too high or too low, which both affects the antifogging property and the light transmittance of the lens.

The embodiments described above are only preferred embodiments of the invention and are not exhaustive of the possible implementations of the invention. Any obvious modifications to the above would be obvious to those of ordinary skill in the art, but would not bring the invention so modified beyond the spirit and scope of the present invention.

Claims

1. The utility model provides an antibiotic antiviral antifog coating sol coats the surface of goggles lens, its characterized in that, including inorganic photocatalyst sol, inorganic photocatalyst sol is prepared by each raw materials and antibacterial ion including following mole fraction:

2. The antibacterial antiviral antifogging coating sol according to claim 1, further comprising a leveling agent, a binder and a thickening agent, wherein the antibacterial antiviral antifogging coating sol comprises the following raw materials in parts by weight: 2-10 parts of inorganic photocatalyst sol; 2-10 parts of a leveling agent; 1-5 parts of a binder; 1-5 parts of thickening agent.

3. The antibacterial antiviral antifog coating sol according to claim 2,

the leveling agent is selected from one or two of acrylate homopolymer, organic silicon modified acrylate polymer, polysiloxane/silicone oil and silicon dioxide adsorbed polyacrylate;

4. The antibacterial, antiviral and antifogging coating sol according to claim 1, wherein the molar ratio of water to organic solvent in the inorganic photocatalyst sol is: 1: 6-13.

5. The antibacterial antiviral antifog coating sol according to claim 1,

the preparation method of the inorganic photocatalyst sol specifically comprises the following steps:

6. The antibacterial antiviral antifog coating sol according to claim 5,

magnetic stirring is adopted for stirring in the step 2, and the stirring time is 30-90 min;

7. The antibacterial antiviral antifog coating sol according to claim 1,

the precursor is selected from one or more of a titanium dioxide precursor, a zinc oxide precursor, a tungsten oxide precursor, an iron oxide precursor, a tin oxide precursor, a silicon oxide precursor, a bismuth tungstate precursor, a bismuth molybdate precursor and a strontium titanate precursor;

8. The antibacterial antiviral antifog coating sol according to claim 7,

the precursor of the titanium dioxide is tetrabutyl titanate, the precursor of the zinc oxide is zinc nitrate hexahydrate, the precursor of the tungsten oxide is ammonium tungstate, the precursor of the iron oxide is ferric nitrate, the precursor of the tin oxide is tin chloride, the precursor of the silicon oxide is ethyl orthosilicate, the precursor of the bismuth tungstate is a composition of ammonium tungstate and bismuth nitrate, the precursor of the bismuth molybdate is a composition of ammonium molybdate and bismuth nitrate, and the precursor of the strontium titanate is one or more of a composition of butyl titanate and strontium nitrate.

9. The preparation method of the antibacterial antiviral antifogging coating sol is characterized by comprising the following steps of:

10. The utility model provides a goggles, includes picture frame, lens base member, and coat in antibiotic antiviral antifog coating layer on the lens base member, antibiotic antiviral antifog coating layer specifically coats the step as follows: