CN1331260A - Process for preparing anti-pollution film - Google Patents
Process for preparing anti-pollution film Download PDFInfo
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- CN1331260A CN1331260A CN 00109709 CN00109709A CN1331260A CN 1331260 A CN1331260 A CN 1331260A CN 00109709 CN00109709 CN 00109709 CN 00109709 A CN00109709 A CN 00109709A CN 1331260 A CN1331260 A CN 1331260A
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- film
- add
- siloxane
- organo
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Abstract
A process for preparing the anti-polluting film includes adding deionized water and hydrolyzing catalyst to the precursor (organic siloxane or alcohol, adding metallic alkoxide and alcohol solution, heating to 80-120 deg.C, refluxing for 1-3 hrs, cooling, adding fluoric surfactant to obtain sol, coating on substrate, solidifciation at 120-350 deg.C for 1 hr, and natural cooling. Its advantages include easy control of process, high transparency and antiwear nature of film, high adhesion, and high anti-polluting effect.
Description
The invention belongs to the thin-film material field, particularly the preparation method of anti-pollution film.
Glass or plastic or other material are during as the decoration of buildings and skeleton construction, owing to be subjected to Effect of Environmental such as variation of temperature, humidity, dust, in use its surface tends to occur phenomenons such as some knot mists or adhesion dust, thereby influenced the outward appearance of decorated thing, also lost its functions of use simultaneously as finishing material.In order to address these problems, antifouling paint and film have appearred in recent years.
Because the critical surface tension of fluoro-containing group compound is lower, so be commonly used for hydrophobic surface promoting agent or surface treatment raw material.At " Japanese Applied Physics periodical ", 1993,32 roll up people such as having reported Ogawa in the L614 pages or leaves (Jpn.J.Appl.Phys., 1993,32 volume L614 pages or leaves) when preparation " super-hydrophobic " glass, at first glass surface are carried out etching (etching) to handle, then at CF
3(CF
2)
7(CH
2)
2SiCl
3Dipping system film in the solution.People such as Yuasa adopt sol-gel process, prepare one deck porous SiO at glass surface earlier
2, utilize the CF of partial hydrolysis then
3(CF
2)
7(CH
2)
2Si (OCH
3)
3Processing obtains hydrophobic layer (Gong Fangtian compiles, the 17 world's glass conference collection of thesis, Beijing: ten thousand state academic presses, 1995, the 445th page of Volume Four).The shortcoming of aforesaid method is a complex process, and raw materials cost is too high, and the film transparency is relatively poor.
Recently to utilizing organopolysiloxane to prepare antifouling paint or the anti-research that adheres to film is more, having adopted a kind of organopolysiloxane mixture among the CN1102841A is raw material, is used for the anti-film that adheres to of coating various substrates preparation.Selecting polysiloxane hydroxyl, that have water-disintegrable or specific volatile among the JP8-283662 for use is raw material, is used to prepare antifouling paint.This method is mainly used in the coating preparation, with direct preparation film on base material very big difference is arranged, and its weak point is that the bonding strength of coating and base material is lower, does not possess the scuff resistance energy, and work-ing life is short.
The objective of the invention is to overcome preparation anti-pollution film method complexity, the film transparency of making is relatively poor, film short defective in work-ing life; A kind of material surface free energy that reduces is provided, makes material surfaces such as glass, pottery, plastics possess the method for manufacturing thin film that oil rub resistance, anti-dust etc. pollute function.
The preparation method of anti-pollution film provided by the invention comprises the following steps: successively
1. in container, add organo-siloxane, deionized water, alcohol, the add-on of deionized water is for making the stoichiometry of organo-siloxane hydrolysis at least fully, the add-on of alcohol is the volume sum of organo-siloxane and deionized water, adding an amount of hydrolyst again is hydrolyzed, the add-on of catalyzer is as the criterion with the pH value aequum between 1～5 that keeps system, hydrolysis temperature is controlled between 25 ℃～60 ℃, 1～3 hour time.
The general formula of the organo-siloxane of selecting for use is: R ' (CH
2)
nSi (OR)
3
Wherein:
R′＝-CH
3，-NH
2，-SH，-NH(CH
2)
2NH
2，-CH＝CH
2，
R＝-CH
3，-CH
2CH
3，n＝1，2，3，...，16
Required hydrolyst is: hydrochloric acid, nitric acid, sulfuric acid, acetic acid or hydrofluoric acid.
2. add the mixture of metal alkoxide and alcoholic solvent in said vesse, the mol ratio of alcohol and alkoxide is between 1: 11～1: 9, and the molar ratio of alkoxide and organo-siloxane is 1: 12-1: between 2.Allow system between 80 ℃～120 ℃, reflux 1～3 hour then, make single aggressiveness raw material produce polyreaction.The purpose that adds metal alkoxide is in order to promote the polymerization of hydrolysate, to improve the compactness of film on the one hand; Be in order to improve the antifriction performance of film on the other hand.Its add-on is very big to the film forming influence, the metal alkoxide too high levels, and the system hydrolytic polymerization is difficult to control, generates precipitation easily; Content is low excessively, and the compactness of film will be affected.
The metal alkoxide general formula is: Me (OR)
4Or Me ' (OR)
3,
Wherein:
Me=Ti or Zr, Me '=Al
R＝-CH
2CH
3、-CH
2CH
2CH
3、-CH(CH
3)
2、-(CH
2)
3CH
3、-CH(CH
3)CH
2CH
3
Or-CH
2CH (CH
3)
2
The structural models of above-mentioned steps products therefrom when relating to metal titanium salt raw material is:
Wherein:
R′＝-CH
3，-NH
2，-SH，-NH(CH
2)
2NH
2，-CH＝CH
2，
3. system is cooled between 40 ℃～80 ℃, adds fluorine surfactant, its add-on be and the mol ratio of organo-siloxane between 0.0001-0.05, keep system constant temperature, stirred 1～3 hour, under continuous condition of stirring, be cooled to room temperature then.Described fluorine surfactant refers to contain-CF
3Or-CF
2The tensio-active agent of group.The adding of fluorine surfactant is very big to the influence of film antifouling property, and its adding is in order to reduce the free energy of film surface.
4. after above-mentioned products therefrom being left standstill for some time, promptly can be used to make film.Make the sophisticated pickling process of film adopting process, hang and cover method (drawing formulation) or brushing, can prepare the film of different thickness at different substrate surfaces according to different requirements.As substrate surfaces such as glass, plastics and potteries.
5. the above-mentioned film for preparing is placed on drying in the baking oven, it is placed on drying in the baking oven, temperature is controlled at constant temperature for some time between 40 ℃～80 ℃.The exsiccant purpose is in order to remove a small amount of solvent of film surface remnants.
6. the film that drying is good places electric furnace to be cured, and slowly is warming up to 120 ℃-350 ℃, and constant temperature naturally cools to room temperature after for some time, promptly obtains anti-pollution film.Solidification process is a densification process, and it is too fast in order to prevent intensification slowly heating up, and causes film to chap in temperature-rise period.
Advantage of the present invention and positively effect are as follows:
(1) the present invention is applied to the preparation of anti-pollution film with a kind of principle advanced person's method, and precursor material adopts industrialized organo-siloxane, and the hydrolytic polymerization process temperature is low, and technical process simply is easy to control.
(2) anti-pollution film of the present invention's preparation combines closely with the substrate material, film densification, transparent, scuff resistance can be good, can be applicable to as glass, pottery, the opposing of plastic or other material surface or the minimizing adhesion to greasy dirt, dust, its antipollution effect is good, and duration of service is long.
The present invention will be described in detail below in conjunction with specific embodiment:
Embodiment 1:
1. get ne-butyltriethoxysilaneand 46ml and 62ml dehydrated alcohol, the adding of 16ml deionized water is equipped with in the clean Erlenmeyer flask of reflux condensing tube, adds 1N hydrochloric acid 6ml, hydrolysis under hydrochloric acid catalysis, and temperature is controlled at 50 ℃, and pH is about 1.5, continues to stir 1 hour;
2. add tetrabutyl titanate 34 gram and propyl carbinol 96ml in hydrolysate, be warming up to 120 ℃ of backflows, constant temperature stirred 1.5 hours;
3. be cooled to 60 ℃, add 2ml 3,3,3-trifluoro propyl triethoxyl silane, constant temperature keeps system, stirs 2 hours, constantly is being cooled to room temperature under the condition of stirring then;
4. after above-mentioned products therefrom being left standstill 2 hours, be used for making film.Employing is revolved the method for covering make film on the synthetic glass substrate, and system film parameter is controlled to be: 10 seconds membranae praeformativa time, even 40 seconds glue time, membranae praeformativa revolution 650r/min, film forming revolution 3200r/min;
5. after making film with aforesaid method, film is placed on drying in the baking oven, temperature was controlled at 60 ℃ of constant temperature 1 hour;
6. the sample that drying is good places the time variable control electric furnace, and the heat-up rate with 2 ℃/min in air atmosphere is warming up to 120 ℃, and constant temperature naturally cooled to room temperature after 1 hour, promptly obtained anti-pollution film.
Embodiment 2;
1. get γ-(2, the 3-glycidoxy) propyl trimethoxy silicane 50ml, propyl carbinol 65ml and deionized water 15ml adding are equipped with in the clean Erlenmeyer flask of reflux condensing tube, the hydrochloric acid 5ml that adds 0.1N, hydrolysis under hydrochloric acid catalysis, temperature is controlled at 30 ℃, pH is about 3, continues to stir 2 hours;
2. add normal-butyl zirconium 8.5 gram and dehydrated alcohol 13ml in hydrolysate, be warming up to 95 ℃ of backflows, constant temperature stirred 1.5 hours;
3. be cooled to 80 ℃, add 0.2ml CF
3-CF
2-CH
2COOH, constant temperature keeps system, stirs 1 hour, constantly is being cooled to room temperature under the condition of stirring then;
4. after above-mentioned products therefrom being left standstill 2 hours, promptly can be used to make film.Employing is revolved the method for covering make film on glass substrate, and system film parameter is controlled to be: 10 seconds membranae praeformativa time, even 30 seconds glue time, membranae praeformativa revolution 600r/min, film forming revolution 3200r/min;
5. after making film with aforesaid method, it is placed on drying in the baking oven, temperature was controlled at 40 ℃ of constant temperature 1 hour;
6. the sample that drying is good places the time variable control electric furnace, and the heat-up rate with 3 ℃/min in air atmosphere is warming up to 350 ℃, and constant temperature naturally cooled to room temperature after 1 hour, promptly obtained anti-pollution film.
Embodiment 3:
1. get vinyl ethyl triethoxysilane 70ml and 92ml dehydrated alcohol, the adding of 22ml deionized water is equipped with in the clean Erlenmeyer flask of reflux condensing tube, adds 0.01N hydrochloric acid 2ml, hydrolysis under hydrochloric acid catalysis, temperature is controlled at 60 ℃, and pH is about 4, continues to stir 3 hours;
2. add tetrabutyl titanate 17 gram and propyl carbinol 46ml in the said hydrolyzed product, be heated to 100 ℃ of backflows, constant temperature stirred 3 hours;
3. be cooled to 60 ℃, add 0.6ml CF
3-CF
2-CF
2-(CH
2)
3-Si (OCH
2CH
3)
3, constant temperature keeps system, stirs 1 hour, constantly is being cooled to room temperature under the condition of stirring then;
4. after above-mentioned products therefrom being left standstill 2 hours, promptly can be used to make film.Adopt pickling process (crystal pulling method) on glass substrate, to make film;
5. after making film with aforesaid method, it is placed on drying in the baking oven, temperature was controlled at 50 ℃ of constant temperature 1 hour;
6. the sample that drying is good places the time variable control electric furnace, and the heat-up rate with 2 ℃/min in air atmosphere is warming up to 180 ℃, and constant temperature naturally cooled to room temperature after 1 hour, promptly obtained anti-pollution film.
The antifouling property experiment:
The antifouling property check does not still have the ideal method.Among the JP8-283662, adopt hairbrush that sesame oil is brushed on test film as pollutent, place after 1 hour, use cloth to wipe with and get, the anti-fouling effect of coating is estimated according to the complexity of wiping.Adopted a kind of more direct method in this experiment: in the 250ml beaker, add each 10 gram of vacuum pump oil and kerosene, add water to 2/3 scale of beaker then, be made into the greasy dirt sample.Insertion was coated with the slide glass of film, leave standstill 2 hours after, how much take out to observe the existence of greasy dirt on slide glass and stain, and compared with the sample of not filming.The results are shown in the table one.
Table one
| Sample | The anti-soil effect |
| Example 1 sample | A small amount of stain is wiped easily |
| Example 2 samples | The minute quantity stain is wiped easily |
| Example 3 samples | A small amount of stain is more easily wiped |
| Be not coated with the filth-resisting thin film slide glass | Stick greasy dirt, be not easy to wipe |
Claims (5)
1. the preparation method of an anti-pollution film is characterized in that step is:
(1). in container, add organo-siloxane, deionized water, alcohol; Wherein, the add-on of deionized water is for making the stoichiometry of organo-siloxane hydrolysis at least fully, the add-on of alcohol is the volume sum of organo-siloxane and deionized water, adding hydrolyst again is hydrolyzed, the add-on of catalyzer with the pH value that keeps system between 1～5, hydrolysis temperature is controlled between 25 ℃～60 ℃, 1～3 hour time;
(2). add the mixture of metal alkoxide and alcoholic solvent in said vesse, the mol ratio of alcohol and alkoxide is between 1: 11～1: 9, and the molar ratio of alkoxide and organo-siloxane is 1: 12-1: between 2; Allow system between 80 ℃～120 ℃, reflux 1～3 hour then, make single aggressiveness raw material produce polyreaction;
(3). system is cooled between 40 ℃～80 ℃, adds fluorine surfactant, its add-on be and the mol ratio of organo-siloxane between 0.0001-0.05, keep system constant temperature, stirred 1～3 hour, under continuous condition of stirring, be cooled to room temperature then;
(4). after above-mentioned products therefrom left standstill for some time, adopt pickling process, outstandingly cover method or brushing prepares film at substrate surface;
(5). the above-mentioned film for preparing is placed on drying in the baking oven, and temperature is controlled at constant temperature between 40 ℃～80 ℃;
(6). the film that drying is good places electric furnace to be cured, and slowly is warming up to 120 ℃-350 ℃, and constant temperature naturally cools to room temperature after for some time, promptly obtains anti-pollution film.
2. the preparation method of anti-pollution film as claimed in claim 1, it is characterized in that: the general formula of described organo-siloxane is: R ' (CH
2)
nSi (OR)
3, wherein:
R′＝-CH
3，-NH
2，-SH，-NH(CH
2)
2NH
2，-CH＝CH
2，
R＝-CH
3，-CH
2CH
3，n＝1，2，3，...，16
3. the preparation method of anti-pollution film as claimed in claim 1, it is characterized in that: described metal alkoxide general formula is: Me (OR)
4Or Me ' (OR)
3,
Wherein:
Me=Ti or Zr, Me '=Al
R＝-CH
2CH
3、-CH
2CH
2CH
3、-CH(CH
3)
2、-(CH
2)
3CH
3、-CH(CH
3)CH
2CH
3
Or-CH
2CH (CH
3)
2
4. the preparation method of anti-pollution film as claimed in claim 1, it is characterized in that: described hydrolyst is hydrochloric acid, nitric acid, sulfuric acid, acetic acid or hydrofluoric acid.
5. the preparation method of anti-pollution film as claimed in claim 1, it is characterized in that: described fluorine surfactant refers to contain-CF
3Or-CF
2The tensio-active agent of group.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 00109709 CN1331260A (en) | 2000-06-30 | 2000-06-30 | Process for preparing anti-pollution film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 00109709 CN1331260A (en) | 2000-06-30 | 2000-06-30 | Process for preparing anti-pollution film |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1331260A true CN1331260A (en) | 2002-01-16 |
Family
ID=4579810
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 00109709 Pending CN1331260A (en) | 2000-06-30 | 2000-06-30 | Process for preparing anti-pollution film |
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|---|---|
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100462223C (en) * | 2001-09-28 | 2009-02-18 | 松下电工株式会社 | Soil-resisting film formed article |
| CN102079947A (en) * | 2010-12-01 | 2011-06-01 | 北京航空航天大学 | Preparation method of titanium alloy surface sol-gel conversion film |
| CN102198374A (en) * | 2011-05-16 | 2011-09-28 | 杭州费尔过滤技术有限公司 | Asymmetric polyvinylidene fluoride microporous membrane with high intensity and preparation method thereof |
| CN102500241A (en) * | 2011-11-22 | 2012-06-20 | 南京工业大学 | Preparation method for anti-pollution permeable vaporization film |
-
2000
- 2000-06-30 CN CN 00109709 patent/CN1331260A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100462223C (en) * | 2001-09-28 | 2009-02-18 | 松下电工株式会社 | Soil-resisting film formed article |
| CN102079947A (en) * | 2010-12-01 | 2011-06-01 | 北京航空航天大学 | Preparation method of titanium alloy surface sol-gel conversion film |
| CN102079947B (en) * | 2010-12-01 | 2012-11-21 | 北京航空航天大学 | Preparation method of titanium alloy surface sol-gel conversion film |
| CN102198374A (en) * | 2011-05-16 | 2011-09-28 | 杭州费尔过滤技术有限公司 | Asymmetric polyvinylidene fluoride microporous membrane with high intensity and preparation method thereof |
| CN102198374B (en) * | 2011-05-16 | 2013-07-17 | 杭州费尔过滤技术有限公司 | Asymmetric polyvinylidene fluoride microporous membrane with high intensity and preparation method thereof |
| CN102500241A (en) * | 2011-11-22 | 2012-06-20 | 南京工业大学 | Preparation method for anti-pollution permeable vaporization film |
| CN102500241B (en) * | 2011-11-22 | 2014-02-26 | 南京工业大学 | Preparation method for anti-pollution permeable vaporization film |
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