CN103319996B - The article that surface treating composition and preparation method thereof is treated with surface - Google Patents
The article that surface treating composition and preparation method thereof is treated with surface Download PDFInfo
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- CN103319996B CN103319996B CN201310202536.7A CN201310202536A CN103319996B CN 103319996 B CN103319996 B CN 103319996B CN 201310202536 A CN201310202536 A CN 201310202536A CN 103319996 B CN103319996 B CN 103319996B
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Abstract
The invention discloses a kind of surface treating composition, it is characterized in that, comprise organic fluorosilicone compound and fluorochemicals.Surface treating composition provided by the invention, can form surface-treated layer on base material, the surface-treated layer surface energy of formation is low, prevents the dirts such as moisture, finger mark, grease, makeup to be attached to substrate surface, and the dirt of attachment can be made easily to wipe, antifouling property is high.
Description
Technical field
The present invention relates to a kind of surface treating composition, be specifically related to the surface treating composition for the formation of low surface energy layer or stain-proofing layer, the invention still further relates to the preparation method of this kind of surface treating composition and the surface article through this kind of surface treating composition process.
Background technology
Antireflecting coating, optical filter, optical mirror slip, glasses lens, beam splitter, prism, speculum and other optical element and sanitary apparatus are in use easily by pollutions such as finger mark, skin oil and fat, sweat, makeup.Such spot is just difficult to be removed once adhere to, and the spot being especially attached to the optics with antireflecting coating is very eye-catching, and causes various problem.
In order to solve and antifouling these relevant problems, propose the technology adopting various surface treating composition so far.
Such as, Japanese Examined Patent discloses No. 1994-29332 and proposes a kind of antifouling low reflection plastic, it has antireflecting coating from the teeth outwards, and this antireflecting coating comprises the silicomethane and disilane compounds and halogen, alkyl or alkoxysilane compound containing trialkylsilyl group in molecular structure that contain poly-fluoroalkyl.
Recently, WO2006/107083 proposes a kind of surface treating composition, and the end that described composition is included in fluoropolymer chains has the silicoorganic compound of alkoxysilyl functional group.This surface treating composition provides low surface energy layer, and this low surface energy layer prevents moisture or dirt to be attached to various material, on the surface of the especially optics such as anti-reflective film and glass.
But, the didirtresistance of the antifouling coating formed by method known is now abundant not, and particularly, their contamination resistance obviously reduces when used over time.Therefore, exploitation is needed to have the antifouling coating of excellent didirtresistance and excellent weather resistance.
Summary of the invention
The object of the invention is, in order to overcome deficiency of the prior art, to provide a kind of surface treating composition of height weather resistance.
For real the above object, the present invention is achieved through the following technical solutions:
A kind of surface treating composition, is characterized in that, comprise organic fluorosilicone compound and fluorochemicals; Described organic fluorinated silicone compound formula (A) is expressed as follows:
F-(CF
2)
q-(OC
3F
6)
m-(OC
2F
4)
n-(CH
2)
o-C(＝O)-NH-(CH
2)
r-C
3H
6-Si(X)
3(A)
Described fluorochemicals general formula (B) is expressed as follows:
F-(CF
2)
q-(OC
3F
6)
m-(OC
2F
4)
n-(CF
2)
o-F (B)
Wherein q is the integer of 1 ~ 3, and m, n are respectively the integer of 0 ~ 200, o be 1 or 2, r be the integer of 0 ~ 17, X is hydrolysable group;
The molar content of described organic fluorinated silicone compound (A) is not less than 75% of described surface treating composition mole total amount; The molar content of described fluorochemicals (B) is not more than 25% of described surface treating composition mole total amount.
Preferably, described X group is alkoxy base or halogen group.Alkoxy base is including, but not limited to methoxyl group, oxyethyl group etc.; Halogen group is including, but not limited to chlorine, bromine, iodine etc.
Preferably, the molar content of described fluorochemicals (B) is less than 15% of described surface treating composition mole total amount.
Preferably, also catalyzer is comprised; The molar content of described catalyzer is less than 5% of described surface treating composition mole total amount; Described catalyzer, for improving the activity of described surface treating composition, promotes that described surface treating composition carries out surface treatment.
Preferably, the molar content of described catalyzer accounts for the 0.01%-2% of described surface treating composition mole total amount.
Preferably, described catalyzer is one in acid, alkali, titanic acid ester, chelate compound or any several mixing.
Available acid includes but not limited to: hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, acetic acid;
Available alkali includes but not limited to: ammonium hydroxide, sodium hydroxide, potassium hydroxide, lithium hydroxide, ammoniacal liquor;
Available metal salts of organic acids includes but not limited to: sodium acetate, potassium acetate, sodium oxalate, potassium oxalate, two sad dibutyl tins;
Available titanic acid ester includes but not limited to: titanium ethanolate, metatitanic acid n-propyl, isopropyl titanate, tetrabutyl titanate;
Available chelate compound includes but not limited to: aluminium acetylacetonate;
Preferably, described organic fluorinated silicone compound (A) and the middle o of described fluorochemicals (B) are 1, and described organic fluorinated silicone compound (A) and described fluorochemicals (B) are converted to following general formula (A-1) and (B-1) represents:
F-(CF
2)
q-(OC
3F
6)
m-(OC
2F
4)
n-CH
2-C(＝O)-NH-(CH
2)
r-C
3H
6-Si(X)
3(A-1)
F-(CF
2)
q-(OC
3F
6)
m-(OC
2F
4)
n-CF
3(B-1)
Wherein q is the integer of 1 ~ 3, and m, n are respectively the integer of 0 ~ 200, and r is the integer of 0 ~ 17, and X is hydrolysable group.
Preferably, also organic solvent is comprised; Described machine solvent is for dissolving described surface treating composition, and in the solution after dissolving, the mole percent concentration of organic fluorinated silicone compound (A) is in 0.01% ~ 80% scope.
Preferably, described organic solvent is for containing fluorous solvent.
Preferably, described organic solvent is any one in fluorine-containing alkane, fluorine-containing aromatic hydrocarbon, fluorine-containing ether.Including, but not limited to ten trifluorohexane, five toluene fluorides, 3M Novec
tM, HFE 7100, HFE 7200 etc.
Another object of the present invention is to provide a kind of method preparing the surface treating composition of height weather resistance.
For real the above object, the present invention is achieved through the following technical solutions:
A preparation method for surface treating composition, is characterized in that, concrete steps are as follows:
A, the compound that represented by following general formula (C) is reacted with the aminosilane represented by following general formula (D);
F-(CF
2)
q-(OC
3F
6)
m-(OC
2F
4)
n-(CH2)
o-C(＝O)OMe (C)
NH
2CH
2CH
2CH
2Si(OCH
3)
3(D)
Wherein q is the integer of 1 ~ 3, and m, n are respectively the integer of 0 ~ 200, and o is 1 or 2;
B, above-mentioned reacted material to be extracted, obtain organic fluorinated silicone compound (A);
F-(CF
2)
q-(OC
3F
6)
m-(OC
2F
4)
n-(CH
2)
o-C(＝O)-NH-(CH
2)
r-C
3H
6-Si(X)
3(A)
Wherein q is the integer of 1 ~ 3, and m, n are respectively the integer of 0 ~ 200, o be 1 or 2, r be the integer of 0 ~ 17, X is hydrolysable group.
Preferably, also comprise step c: mixed with described organic fluoride silicon compound (A) by fluorochemicals (B), the surface treating composition of be uniformly mixed organic fluoride silicon compound (A) and fluorochemicals (B);
F-(CF
2)
q-(OC
3F
6)
m-(OC
2F
4)
n-(CF
2)
o-F (B)
Wherein q is the integer of 1 ~ 3, and m, n are respectively the integer of 0 ~ 200, and o is 1 or 2.
Preferably, described step a also comprises, described fluorochemicals (B) is added in the compound represented by general formula (C) and the mixture of aminosilane represented by general formula (D) and reacts, repeating said steps b, the surface treating composition of be uniformly mixed organic fluoride silicon compound (A) and fluorochemicals (B).
F-(CF
2)
q-(OC
3F
6)
m-(OC
2F
4)
n-(CF
2)
o-F (B)
Wherein q is the integer of 1 ~ 3, and m, n are respectively the integer of 0 ~ 200, and o is 1 or 2.。
Preferably, described compound (C) is 1:1 with the mol ratio of described aminosilane (D).
Preferably, in described surface treating composition, the molar content of described fluorochemicals (B) is less than 15% of described surface treating composition mole total amount.
Preferably, also step c ' is comprised: in described surface treating composition, add catalyzer; The molar content of described catalyzer is less than 5% of described surface treating composition mole total amount; Described catalyzer, for improving the activity of described surface treating composition, promotes that described surface treating composition carries out surface treatment.
Preferably, also comprise steps d: by surface treating composition described in organic solvent dissolution, make organic fluorinated silicone compound (A) mass percentage concentration be 10%.
Another object of the present invention is to provide the article of a kind of surface through the surface treating composition process of height weather resistance.
For real the above object, the present invention is achieved through the following technical solutions:
The article that surface is treated, is characterized in that, comprise base material and surface-treated layer; Described surface-treated layer is arranged at described substrate surface, is formed by surface treating composition.
Preferably, described base material is the transparent material comprising antireflective optical layer.
Preferably, the article that described surface is treated are selected from optics; Described optics is any one in anti-reflective film, optical filter, optical mirror slip, glasses lens, beam splitter, prism, scintilloscope.
Preferably, described surface treatment layer thickness is 0.5nm ~ 30nm.
Preferably, described surface treatment layer thickness is 1nm ~ 10nm.
Surface treating composition provided by the invention, can form surface-treated layer on base material, the surface-treated layer surface energy of formation is low, prevents the dirts such as moisture, finger mark, grease, makeup to be attached to substrate surface, and the dirt of attachment can be made easily to wipe, antifouling property is high.Due to the amido linkage (-CO-NH-) in the component (A) of the surface treating composition in the present invention, there is better chemical stability, compared with conventional surface treatment compositions, product has better enduring quality, there is height weather resistance, add the work-ing life of surface-treated layer, can dirt be prevented for a long time to be attached to substrate surface.The surface-treated layer that surface treating composition is formed has very high transmissivity, is applicable to the optics that transmission requirement is high, applied range simultaneously.The interpolation of component (B) can improve the hydrophobic performance of surface treating composition, but its content needs strict control, the scratch-resistant performance of surface treating composition too much can be made to decline, so the molar content of preferred ingredient (B) is less than 25% of surface treating composition mole total amount.Also added catalyzer in surface treating composition, improve the activity of surface treating composition, improve surface treating composition in the set time of pending article surface, promote to react between surface treating composition and pending article surface.Surface treating composition can also be dissolved by organic solvent, make organic fluorinated silicone compound (A) mass percentage concentration in 0.01% ~ 80% scope, the antifouling property of further raising surface treating composition, work-ing life and transmissivity, reduce its surface energy.
The preparation method of surface treating composition provided by the invention, the surface treating composition that surface energy is low, antifouling property is high, long service life, transmissivity are high is obtained by simple process, reduce production cost, simplify production technique, add the range of application of surface treating composition.
The article that surface provided by the invention is treated, the surface-treated layer comprising substrate and formed at substrate surface by surface treating composition, while not changing himself performance, can add the performances such as high didirtresistance and scratch resistance.Surface treating composition is not high to the selectivity of substrate simultaneously, adds and can carry out surface-treated type of goods.
Embodiment
Embodiment 1
Surface treating composition, comprises organic fluorosilicone compound, fluorochemicals and hydrochloric; Described organic fluorinated silicone compound formula (A) is expressed as follows:
F-(CF
2)
3-(OC
3F
6)
20-(OC
2F
4)
20-CH
2-C(＝O)-NH-C
3H
6-Si(OMe)
3(A)
Described fluorochemicals general formula (B) is expressed as follows:
F-(CF
2)
3-(OC
3F
6)
20-(OC
2F
4)
20-CF
3(B)
The molar content of fluorochemicals (B) is 14% of surface treating composition mole total amount, organic fluorinated silicone compound (A) molar content is 85% of surface treating composition mole total amount, and the molar content of hydrochloric is 1% of surface treating composition mole total amount.Surface treating composition can also be dissolved by organic solvent HFE 7100, to improve the antifouling property of surface treating composition, work-ing life and transmissivity further, reduces its surface energy.
A preparation method for surface treating composition, concrete steps are as follows:
A, under nitrogen flowing, the mixture that fluorochemicals (B) described in the compound represented by the following general formula of 700g (C) and 100g forms is loaded 1.0L be furnished with in the there-necked flask of agitator, dropping funnel, thermometer, then the aminosilane that 300g is represented by following general formula (D) is slowly instilled in there-necked flask; Dropwise rear room temperature reaction 24 hours.
F-(CF
2)
3-(OC
3F
6)
20-(OC
2F
4)
20-CF
3(B)
F-(CF
2)
3-(OC
3F
6)
20-(OC
2F
4)
20-(CH
2)
2-C(＝O)OMe (C)
NH
2CH
2CH
2CH
2Si(OCH
3)
3(D)
B, above-mentioned reacted material dry methane is extracted 3 times, collect lower floor's liquid, and at room temperature use vacuum pump dry 3 hours, obtain the mixture 750g of described organic fluorinated silicone compound (A) and fluorochemicals (B).
F-(CF
2)
3-(OC
3F
6)
20-(OC
2F
4)
20-CH
2-C(＝O)-NH-C
3H
6-Si(OMe)
3(A)
F-(CF
2)
3-(OC
3F
6)
20-(OC
2F
4)
20-CF
3(B)
C, 200g fluorochemicals (B) to be mixed with above-mentioned gained mixture, the composition 950g of be uniformly mixed organic fluoride silicon compound (A) and fluorochemicals (B);
Also comprise step c ': in the composition of step c gained, add hydrochloric, obtain surface treating composition.The molar content of catalyzer is 1% of surface treating composition mole total amount, for improving the activity of surface treating composition, promotes that surface treating composition carries out surface treatment.
Also comprise steps d: dissolve surface treating composition by organic solvent HFE 7100, make organic fluorinated silicone compound (A) mass percentage concentration be 10%.
According to carrying out IR analysis to the surface treating composition by above-mentioned steps gained, in the absorption completely dissolve from-C (=O) OMe of 1890cm-1, newly there is the absorption from-C (=O) NH at 1880cm-1.Therefore, surface treating composition is confirmed to be by chemical formula F-(CF
2)
3-(OC
3f
6)
20-(OC
2f
4)
20-CH
2-CONH-C
3h
6si (OMe)
3represent PFPE ring fourth oxygen alkane silane and by chemical formula F-(CF2)
3-(OC
3f
6)
20-(OC
2f
4)
20-(CF
2) mixture of perfluor polybutylene oxide that represents of-F.Wherein, the content of PFPE ring fourth oxygen alkane silane is 85%, and the content of perfluor polybutylene oxide is 14%.
Surface, through article for described surface treating composition process, comprises base material and surface-treated layer; Surface-treated layer is arranged at substrate surface, is formed by surface treating composition.Base material is the glass baseplate comprising antireflective optical layer.The treated article in surface are selected from optics optical filter.Wherein surface treatment layer thickness is 5nm.
The present invention is comprised with the material of the article forming surface-treated layer by surface treating composition process: inorganic materials is as sheet glass, the glass comprising inorganic layer or pottery etc.; Organic materials is as transparent plastic material, the transparent plastic material etc. comprising inorganic layer.Object origin from optics, as anti-reflective film, optical filter, optical mirror slip, glasses lens, beam splitter, prism, speculum etc.Inorganic materials comprising the glass of inorganic layer can be metal oxide, magnesium oxide, titanium oxide, stannic oxide, zirconium white, sodium oxide, weisspiessglanz, Indium sesquioxide, bismuth oxide, yttrium oxide, cerium oxide, zinc oxide and ITO (indium tin oxide) etc.
Embodiment 2
Surface treating composition, comprises organic fluorosilicone compound, fluorochemicals and catalyzer ammonium hydroxide; Described organic fluorinated silicone compound formula (A) is expressed as follows:
F-(CF
2)
3-(OC
3F
6)
20-(OC
2F
4)
20-CH
2-C(＝O)-NH-C
3H
6-Si(OMe)
3(A)
Described fluorochemicals general formula (B) is expressed as follows:
F-(CF
2)
3-(OC
3F
6)
20-(OC
2F
4)
20-CF
3(B)
The molar content of fluorochemicals (B) is 9% of surface treating composition mole total amount, organic fluorinated silicone compound (A) molar content is 89% of surface treating composition mole total amount, and the molar content of catalyzer ammonium hydroxide is 2% of surface treating composition mole total amount.Surface treating composition can also be dissolved by organic solvent HFE 7100, to improve the antifouling property of surface treating composition, work-ing life and transmissivity further, reduces its surface energy.
A preparation method for surface treating composition, concrete steps are as follows:
A, under nitrogen flowing, the compound represented by the following general formula of 167.5g (C) is loaded 1.0L be furnished with in the there-necked flask of agitator, dropping funnel, thermometer, then the aminosilane that 71.8g is represented by following general formula (D) is slowly instilled in there-necked flask; Dropwise rear room temperature reaction 24 hours.
F-(CF
2)
3-(OC
3F
6)
20-(OC
2F
4)
20-(CH
2)
2-C(＝O)OMe (C)
NH
2CH
2CH
2CH
2Si(OCH
3)
3(D)
B, above-mentioned reacted material dry methane is extracted 3 times, collect lower floor's liquid, and at room temperature use vacuum pump dry 3 hours, obtain described organic fluorinated silicone compound (A).
F-(CF
2)
3-(OC
3F
6)
20-(OC
2F
4)
20-CH
2-C(＝O)-NH-C
3H
6-Si(OMe)
3(A)
C, 43.6g fluorochemicals (B) to be mixed with above-mentioned gained organic fluorinated silicone compound (A), the composition 199.1g of be uniformly mixed organic fluoride silicon compound (A) and fluorochemicals (B).
F-(CF
2)
3-(OC
3F
6)
20-(OC
2F
4)
20-CF
3(B)
Also comprise step c ': in the composition of step c gained, add catalyzer ammonium hydroxide, obtain surface treating composition.The molar content of catalyzer is 2% of surface treating composition mole total amount, for improving the activity of surface treating composition, promotes that surface treating composition carries out surface treatment.
Also comprise steps d: dissolve surface treating composition by organic solvent HFE 7100, make organic fluorinated silicone compound (A) mass percentage concentration be 10%.
According to carrying out IR analysis to the surface treating composition by above-mentioned steps gained, in the absorption completely dissolve from-C (=O) OMe of 1890cm-1, newly there is the absorption from-C (=O) NH at 1880cm-1.Therefore, surface treating composition is confirmed to be by chemical formula F-(CF
2)
3-(OC
3f
6)
20-(OC
2f
4)
20-CH
2-CONH-C
3h
6si (OMe)
3represent PFPE ring fourth oxygen alkane silane and by chemical formula F-(CF2)
3-(OC
3f
6)
20-(OC
2f
4)
20-(CF
2) mixture of perfluor polybutylene oxide that represents of-F.Wherein, the content of PFPE ring fourth oxygen alkane silane is 89%, and the content of perfluor polybutylene oxide is 9%.
Surface, through article for described surface treating composition process, comprises base material and surface-treated layer; Surface-treated layer is arranged at substrate surface, is formed by surface treating composition.Base material is the glass baseplate comprising antireflective optical layer.The treated article in surface are selected from optics optical filter.Wherein surface treatment layer thickness is 5nm.
The present invention is comprised with the material of the article forming surface-treated layer by surface treating composition process: inorganic materials is as sheet glass, the glass comprising inorganic layer or pottery etc.; Organic materials is as transparent plastic material, the transparent plastic material etc. comprising inorganic layer.Object origin from optics, as anti-reflective film, optical filter, optical mirror slip, glasses lens, beam splitter, prism, speculum etc.Inorganic materials comprising the glass of inorganic layer can be metal oxide, magnesium oxide, titanium oxide, stannic oxide, zirconium white, sodium oxide, weisspiessglanz, Indium sesquioxide, bismuth oxide, yttrium oxide, cerium oxide, zinc oxide and ITO (indium tin oxide) etc.
Embodiment 3
Surface treating composition, comprises the sad dibutyl tin of organic fluorosilicone compound, fluorochemicals and catalyzer two; Described organic fluorinated silicone compound formula (A) is expressed as follows:
F-(CF
2)
3-(OC
3F
6)
20-(OC
2F
4)
20-CH
2-C(＝O)-NH-C
3H
6-Si(OMe)
3(A)
Described fluorochemicals general formula (B) is expressed as follows:
F-(CF
2)
3-(OC
3F
6)
20-(OC
2F
4)
20-CF
3(B)
The molar content of fluorochemicals (B) is 4.99% of surface treating composition mole total amount, organic fluorinated silicone compound (A) molar content is 95% of surface treating composition mole total amount, and the molar content of the sad dibutyl tin of catalyzer two is 0.01% of surface treating composition mole total amount.Surface treating composition can also be dissolved by organic solvent HFE 7100, to improve the antifouling property of surface treating composition, work-ing life and transmissivity further, reduces its surface energy.
A preparation method for surface treating composition, concrete steps are as follows:
1. under nitrogen flowing, the mixture that fluorochemicals (B) described in the compound represented by the following general formula of 167.5g (C) and 1.8g forms is loaded 1.0L be furnished with in the there-necked flask of agitator, dropping funnel, thermometer, then the aminosilane that 71.8g is represented by following general formula (D) is slowly instilled in there-necked flask; Dropwise rear room temperature reaction 24 hours.
F-(CF
2)
3-(OC
3F
6)
20-(OC
2F
4)
20-CF
3(B)
F-(CF
2)
3-(OC
3F
6)
20-(OC
2F
4)
20-(CH
2)
2-C(＝O)OMe (C)
NH
2CH
2CH
2CH
2Si(OCH
3)
3(D)
2. above-mentioned reacted material dry methane is extracted 3 times, collect lower floor's liquid, and at room temperature use vacuum pump dry 3 hours, the composition 175.3g of be uniformly mixed organic fluoride silicon compound (A) and fluorochemicals (B).
F-(CF
2)
3-(OC
3F
6)
20-(OC
2F
4)
20-CH
2-C(＝O)-NH-C
3H
6-Si(OMe)
3(A)
F-(CF
2)
3-(OC
3F
6)
20-(OC
2F
4)
20-CF
3(B)
Also comprise step c ': in the composition of step b gained, add the sad dibutyl tin of catalyzer two, obtain surface treating composition.The molar content of catalyzer is 0.01% of surface treating composition mole total amount, for improving the activity of surface treating composition, promotes that surface treating composition carries out surface treatment.
Also comprise steps d: dissolve surface treating composition by organic solvent HFE 7100, make organic fluorinated silicone compound (A) mass percentage concentration be 10%.
According to carrying out IR analysis to the surface treating composition by above-mentioned steps gained, in the absorption completely dissolve from-C (=O) OMe of 1890cm-1, newly there is the absorption from-C (=O) NH at 1880cm-1.Therefore, surface treating composition is confirmed to be by chemical formula F-(CF
2)
3-(OC
3f
6)
20-(OC
2f
4)
20-CH
2-CONH-C
3h
6si (OMe)
3represent PFPE ring fourth oxygen alkane silane and by chemical formula F-(CF2)
3-(OC
3f
6)
20-(OC
2f
4)
20-(CF
2) mixture of perfluor polybutylene oxide that represents of-F.Wherein, the content of PFPE ring fourth oxygen alkane silane is 95%, and the content of perfluor polybutylene oxide is 4.99%.
Surface, through article for described surface treating composition process, comprises base material and surface-treated layer; Surface-treated layer is arranged at substrate surface, is formed by surface treating composition.Base material is the glass baseplate comprising antireflective optical layer.The treated article in surface are selected from optics optical filter.Wherein surface treatment layer thickness is 5nm.
The present invention is comprised with the material of the article forming surface-treated layer by surface treating composition process: inorganic materials is as sheet glass, the glass comprising inorganic layer or pottery etc.; Organic materials is as transparent plastic material, the transparent plastic material etc. comprising inorganic layer.Object origin from optics, as anti-reflective film, optical filter, optical mirror slip, glasses lens, beam splitter, prism, speculum etc.Inorganic materials comprising the glass of inorganic layer can be metal oxide, magnesium oxide, titanium oxide, stannic oxide, zirconium white, sodium oxide, weisspiessglanz, Indium sesquioxide, bismuth oxide, yttrium oxide, cerium oxide, zinc oxide and ITO (indium tin oxide) etc.
Embodiment 4
Surface treating composition, comprises organic fluorosilicone compound, fluorochemicals and catalyzer titanium isopropylate; Described organic fluorinated silicone compound formula (A) is expressed as follows:
F-CF
2-(OC
3F
6)
200-(OC
2F
4)
200-CH
2-C(＝O)-NH-(CH
2)
17-C
3H
6-SiCl
3(A)
Described fluorochemicals general formula (B) is expressed as follows:
F-CF
2-(OC
3F
6)
200-(OC
2F
4)
200-CF
3(B)
The molar content of fluorochemicals (B) is 14% of surface treating composition mole total amount, organic fluorinated silicone compound (A) molar content is 85% of surface treating composition mole total amount, and the molar content of catalyzer titanium isopropylate is 1% of surface treating composition mole total amount.Surface treating composition can also be dissolved by organic solvent ten trifluorohexane, to improve the antifouling property of surface treating composition, work-ing life and transmissivity further, reduces its surface energy.
A preparation method for surface treating composition, concrete steps are as follows:
A, under nitrogen flowing, the mixture that fluorochemicals (B) described in the compound represented by the following general formula of 550g (C) and 90g forms is loaded 1.0L be furnished with in the there-necked flask of agitator, dropping funnel, thermometer, then the aminosilane that 1.8g is represented by following general formula (D) is slowly instilled in there-necked flask; Dropwise rear room temperature reaction 24 hours.
F-CF
2-(OC
3F
6)
200-(OC
2F
4)
200-(CH
2)
2-C(＝O)Cl (C)
NH
2CH
2CH
2CH
2Si(OCH
3)
3(D)
B, above-mentioned reacted material dry methane is extracted 3 times, collect lower floor's liquid, and at room temperature use vacuum pump dry 3 hours, the composition 640g of be uniformly mixed organic fluoride silicon compound (A) and fluorochemicals (B).
F-CF
2-(OC
3F
6)
200-(OC
2F
4)
200-CH
2-C(＝O)-NH-(CH
2)
17-C
3H
6-SiCl
3(A)
F-CF
2-(OC
3F
6)
200-(OC
2F
4)
200-CF
3(B)
Also comprise step c ': in the composition of step b gained, add catalyzer titanium isopropylate, obtain surface treating composition.The molar content of catalyzer is 1% of surface treating composition mole total amount, for improving the activity of surface treating composition, promotes that surface treating composition carries out surface treatment.
Also comprise steps d: dissolve surface treating composition by organic solvent ten trifluorohexane, make organic fluorinated silicone compound (A) mass percentage concentration be 10%.
According to carrying out IR analysis to the surface treating composition by above-mentioned steps gained, in the absorption completely dissolve from-C (=O) Cl of 1890cm-1, newly there is the absorption from-C (=O) NH at 1880cm-1.Therefore, surface treating composition is confirmed to be by chemical formula F-CF
2-(OC
3f
6)
200-(OC
2f
4)
200-CH
2-C (=O)-NH-(CH
2)
17-C
3h
6-SiCl
3represent PFPE ring fourth oxygen alkane silane and by chemical formula F-CF
2-(OC
3f
6)
200-(OC
2f
4)
200-CF
3the mixture of the perfluor polybutylene oxide represented.Wherein, the content of PFPE ring fourth oxygen alkane silane is 85%, and the content of perfluor polybutylene oxide is 14%.
Surface, through article for described surface treating composition process, comprises base material and surface-treated layer; Surface-treated layer is arranged at substrate surface, is formed by surface treating composition.Base material is the glass baseplate comprising antireflective optical layer.The treated article in surface are selected from optics optical filter.Wherein surface treatment layer thickness is 1nm.
The present invention is comprised with the material of the article forming surface-treated layer by surface treating composition process: inorganic materials is as sheet glass, the glass comprising inorganic layer or pottery etc.; Organic materials is as transparent plastic material, the transparent plastic material etc. comprising inorganic layer.Object origin from optics, as anti-reflective film, optical filter, optical mirror slip, glasses lens, beam splitter, prism, speculum etc.Inorganic materials comprising the glass of inorganic layer can be metal oxide, magnesium oxide, titanium oxide, stannic oxide, zirconium white, sodium oxide, weisspiessglanz, Indium sesquioxide, bismuth oxide, yttrium oxide, cerium oxide, zinc oxide and ITO (indium tin oxide) etc.
Embodiment 5
Surface treating composition, comprises organic fluorosilicone compound and fluorochemicals; Described organic fluorinated silicone compound formula (A) is expressed as follows:
F-(CF
2)
2-OC
3F
6-OC
2F
4-CH
2-C(＝O)-NH-(CH
2)
10-C
3H
6-Si(OCH
3)
3(A)
Described fluorochemicals general formula (B) is expressed as follows:
F-(CF
2)
2-OC
3F
6-OC
2F
4-CF
3(B)
The molar content of fluorochemicals (B) is 10% of surface treating composition mole total amount, and organic fluorinated silicone compound (A) molar content is 90% of surface treating composition mole total amount.Surface treating composition can also be dissolved by organic solvent five toluene fluoride, to improve the antifouling property of surface treating composition, work-ing life and transmissivity further, reduces its surface energy
A preparation method for surface treating composition, concrete steps are as follows:
A, under nitrogen flowing, the compound represented by the following general formula of 455g (C) is loaded 1.0L be furnished with in the there-necked flask of agitator, dropping funnel, thermometer, then the aminosilane that 179g is represented by following general formula (D) is slowly instilled in there-necked flask; Dropwise rear room temperature reaction 24 hours.
F-(CF
2)
2-OC
3F
6-OC
2F
4-(CH
2)
2-C(＝O)OCH
3(C)
NH
2CH
2CH
2CH
2Si(OCH
3)
3(D)
B, above-mentioned reacted material dry methane is extracted 3 times, collect lower floor's liquid, and at room temperature use vacuum pump dry 3 hours, obtain described organic fluorinated silicone compound (A).
F-(CF
2)
2-OC
3F
6-OC
2F
4-CH
2-C(＝O)-NH-(CH
2)
10-C
3H
6-Si(OCH
3)
3(A)
C, fluorochemicals described in 51g (B) to be mixed with above-mentioned gained organic fluoride silicon compound (A), the surface treating composition 240g of be uniformly mixed organic fluoride silicon compound (A) and fluorochemicals (B);
F-(CF
2)
2-OC
3F
6-OC
2F
4-CF
3(B)
Also comprise steps d: dissolve surface treating composition by organic solvent five toluene fluoride, make organic fluorinated silicone compound (A) mass percentage concentration be 80%.
According to carrying out IR analysis to the surface treating composition by above-mentioned steps gained, at 1890cm-1 from-C (=O) OCH
3absorption completely dissolve, newly there is the absorption from-C (=O) NH at 1880cm-1.Therefore, surface treating composition is confirmed to be by chemical formula F-(CF
2)
2-OC
3f
6-OC
2f
4-CH
2-C (=O)-NH-(CH
2)
10-C
3h
6-Si (OCH
3)
3represent PFPE ring fourth oxygen alkane silane and by chemical formula F-(CF
2)
2-OC
3f
6-OC
2f
4-CF
3the mixture of the perfluor polybutylene oxide represented.Wherein, the content of PFPE ring fourth oxygen alkane silane is 89%, and the content of perfluor polybutylene oxide is 10%.
Surface, through article for described surface treating composition process, comprises base material and surface-treated layer; Surface-treated layer is arranged at substrate surface, is formed by surface treating composition.Base material is the glass baseplate comprising antireflective optical layer.The treated article in surface are selected from optics optical filter.Wherein surface treatment layer thickness is 10nm.
The present invention is comprised with the material of the article forming surface-treated layer by surface treating composition process: inorganic materials is as sheet glass, the glass comprising inorganic layer or pottery etc.; Organic materials is as transparent plastic material, the transparent plastic material etc. comprising inorganic layer.Object origin from optics, as anti-reflective film, optical filter, optical mirror slip, glasses lens, beam splitter, prism, speculum etc.Inorganic materials comprising the glass of inorganic layer can be metal oxide, magnesium oxide, titanium oxide, stannic oxide, zirconium white, sodium oxide, weisspiessglanz, Indium sesquioxide, bismuth oxide, yttrium oxide, cerium oxide, zinc oxide and ITO (indium tin oxide) etc.
Embodiment 6
Surface treating composition, comprises organic fluorosilicone compound, fluorochemicals and catalyst acetyl acetone aluminium; Described organic fluorinated silicone compound formula (A) is expressed as follows:
F-CF
2-(OC
3F
6)
100-(OC
2F
4)
100-CH
2-C(＝O)-NH-CH
2-C
3H
6-Si(F)
3(A)
Described fluorochemicals general formula (B) is expressed as follows:
F-CF
2-(OC
3F
6)
100-(OC
2F
4)
100-CF
3(B)
The molar content of fluorochemicals (B) is 4.5% of surface treating composition mole total amount, organic fluorinated silicone compound (A) molar content is 94% of surface treating composition mole total amount, and the molar content of catalyst acetyl acetone aluminium is 1.5% of surface treating composition mole total amount.Surface treating composition can also pass through organic solvent 3M Novec
tMdissolve, to improve the antifouling property of surface treating composition, work-ing life and transmissivity further, reduce its surface energy.
A preparation method for surface treating composition, concrete steps are as follows:
A, under nitrogen flowing, the mixture that fluorochemicals (B) described in the compound represented by the following general formula of 274g (C) and 14.5g forms is loaded 1.0L be furnished with in the there-necked flask of agitator, dropping funnel, thermometer, then the aminosilane that 1.8g is represented by following general formula (D) is slowly instilled in there-necked flask; Dropwise rear room temperature reaction 24 hours.
F-CF
2-(OC
3F
6)
100-(OC
2F
4)
100-(CH
2)
2-C(＝O)F (C)
NH
2CH
2CH
2CH
2Si(OCH
3)
3(D)
B, above-mentioned reacted material dry methane is extracted 3 times, collect lower floor's liquid, and at room temperature use vacuum pump dry 3 hours, the composition 289g of obtain being uniformly mixed organic fluoride silicon compound (A) and fluorochemicals (B).
F-CF
2-(OC
3F
6)
100-(OC
2F
4)
100-CH
2-C(＝O)-NH-CH
2-C
3H
6-Si(F)
3(A)
F-CF
2-(OC
3F
6)
100-(OC
2F
4)
100-CF
3(B)
Also comprise step c ': in the composition of step b gained, add catalyst acetyl acetone aluminium, obtain surface treating composition.The molar content of catalyzer is 1.5% of surface treating composition total mass, for improving the activity of surface treating composition, promotes that surface treating composition carries out surface treatment.
Also comprise steps d: by organic solvent 3M Novec
tMdissolve surface treating composition, make organic fluorinated silicone compound (A) mass percentage concentration be 10%.
According to carrying out IR analysis to the surface treating composition by above-mentioned steps gained, in the absorption completely dissolve from-C (=O) F of 1890cm-1, newly there is the absorption from-C (=O) NH at 1880cm-1.Therefore, surface treating composition is confirmed to be by chemical formula F-CF
2-(OC
3f
6)
100-(OC
2f
4)
100-CH
2-C (=O)-NH-CH
2-C
3h
6-Si (F)
3represent PFPE ring fourth oxygen alkane silane and by chemical formula F-CF
2-(OC
3f
6)
100-(OC
2f
4)
100-CF
3the mixture of the perfluor polybutylene oxide represented.Wherein, the content of PFPE ring fourth oxygen alkane silane is 94%, and the content of perfluor polybutylene oxide is 4.5%.
Surface, through article for described surface treating composition process, comprises base material and surface-treated layer; Surface-treated layer is arranged at substrate surface, is formed by surface treating composition.Base material is the glass baseplate comprising antireflective optical layer.The treated article in surface are selected from optics optical filter.Wherein surface treatment layer thickness is 1nm.
In above-described embodiment, after first can also preparing organic fluoride silicon compound (A), then organic fluoride silicon compound (A) and fluorochemicals (B) are mixed to form composition.
The present invention is comprised with the material of the article forming surface-treated layer by surface treating composition process: inorganic materials is as sheet glass, the glass comprising inorganic layer or pottery etc.; Organic materials is as transparent plastic material, the transparent plastic material etc. comprising inorganic layer.Object origin from optics, as anti-reflective film, optical filter, optical mirror slip, glasses lens, beam splitter, prism, speculum etc.Inorganic materials comprising the glass of inorganic layer can be metal oxide, magnesium oxide, titanium oxide, stannic oxide, zirconium white, sodium oxide, weisspiessglanz, Indium sesquioxide, bismuth oxide, yttrium oxide, cerium oxide, zinc oxide and ITO (indium tin oxide) etc.
The following step (i) relates to glass baseplate by the process of the surface treating composition of embodiment 1-6 to (iii) and obtains ophthalmic lens.
The pre-treatment of (i) glass baseplate:
Base material realizes coating, and this base material is the ophthalmic lens based on CR39.RTM., and it includes the wear-resistant coating of the polysiloxane type corresponding to the embodiment 3 in patent documentation EP614957 on both sides.In ultrasonic cleaning tank, wash eyeglass, steam minimum 3 hours the temperature of 100 DEG C.Described eyeglass prepares to process subsequently.The eyeglass of process is circular eyeglass.
(ii) preparation of eyeglass
The vacuum processor used is Syrus 3 machine from Leybold Optics, its evaporation source being configured with electron beam gun, ion gun and having joule effect.Be placed on by eyeglass on the carousel being furnished with the circular open that can hold pending eyeglass, concave side is to evaporation source and ion gun.
Carry out vacuumizing until reach secondary vacuum.
Then, electron beam gun is used to carry out the consecutive evaporation of 4 non-reflective optical layers, high index (IH), low index (B1), HI, BI:ZrO
2, SiO
2, ZrO
2, SiO
2.
Finally, by the surface treating composition that more than hydatogenesis obtains as surface-treated layer.
The surface treating composition of the above acquisition of specified rate being placed on diameter is in the copper chamber of 18mm, then places it in joule effect crucible (tantalum crucible).Be the surface-treated layer of 1nm ~ 5nm by hydatogenesis thickness.
Deposit thickness uses quartz detector to measure.
Subsequently, again heated by enclosure, set handling room makes it return to connect air.
Then eyeglass is inverted, makes convex side towards treatment zone.The process of convex side and similar (the repeating above step (ii)) of recessed side.
(iii) test and measurement
(iii-1) endurance procedures:
Make " Microfiber M840S 30X40 " from FACOL to be immersed in the water of 25 DEG C 1 minute, then take out and be placed in air.(at 25 DEG C while applying 3.5kg load, in the air of the humidity of 40% ~ 60%) carry out mechanical friction with the surface with the glasses lens of surface-treated layer of this Microfiber to step (ii) gained, (namely this mechanical friction carry out 2400 times in reciprocating mode (1 cycle corresponds to and adds forward 1 motion backward for 1 time), 1200 circulations), 4800 times (namely, 2400 circulations), 7200 times (namely, 3600 circulations), 9600 times (namely, 4800 circulations) and 12000 times (namely, 6000 circulations), static contact angle is measured every 1200 rub cycle.Mechanical abrading device is set as in 14 minutes, carry out 1200 circulations.
(iii-2) with the static contact angle of water
Use contact angle measurement (DSA 100 is manufactured by KRUSS Advancing Surface Science), use pin divides in the highest portion of the convex side of eyeglass at the droplet deposition that volume is 4 microlitres by 25 DEG C.Angle between water droplet and surface is defined as " with the static contact angle of water ".Use " drop shape analysis (dripping conformal analysis) " this angle of software measurement of DSA 100.Adopt this technology and this equipment, the uncertainty of measurement is +/-1.3.
Run according to said process.Use above-mentioned durability test program test 3 to be the eyeglass through surface treating composition process of a group, for 3 eyeglasses of different cycle index, repeat above-mentioned steps (i)-(iii), carry out the measurement of static contact angle.Obtain the static contact angle mean value of eyeglass under different cycle index through surface treating composition process.
Comparative example 1: replace surface treating composition with composition (N), repeat above-mentioned steps (i)-(iii), the static contact angle mean value of eyeglass under different cycle index obtaining processing through composition (N) is as shown in table 1.Wherein composition (N) comprises the PFPE F-(CF of the silane functionality of 60 % by mole
2)
3-(OC
3f
6)
20-(OC
2f
4)
20-CH
2-C (=O)-NH-C
3h
6-Si (OMe)
3, the hydrochloric acid of F-(CF2) 3-(OC3F6) 20-(OC2F4) 20-(CF2)-F and 1 % by mole of 39 % by mole.
Comparative example 2: replace surface treating composition with composition (M), repeat above-mentioned steps (i)-(iii), the static contact angle mean value of eyeglass under different cycle index obtaining processing through composition (M) is as shown in table 1.Wherein composition (M) comprises the PFPE F-(CF of the silane functionality of 70 % by mole
2)
3-(OC
3f
6)
20-(OC
2f
4)
20-CH
2-C (=O)-NH-C
3h
6-Si (OMe)
3, the hydrochloric acid of F-(CF2) 3-(OC3F6) 20-(OC2F4) 20-(CF2)-F and 1 % by mole of 29 % by mole.
Each circulation load used is 3.5kg.
As shown in Table 1, eyeglass after the surface treating composition process of embodiment 1-6, carry out static contact angle test, its mean value is 120 °, illustrate that the eyeglass with surface-treated layer has the characteristic that dirts such as preventing moisture, finger mark, grease, makeup is attached to lens surface, and the dirt of attachment can be made easily to wipe, antifouling property is high.And reciprocating machine friction is being carried out to the eyeglass after surface treating composition process, and the static contact angle of lens surface processing layer again after testing friction, its value slightly reduces, but rub after 3000 times and still can reach more than 110 °, illustrate after the mechanical friction of thousands of times, eyeglass after surface treating composition process still has good antifouling capacity, high enduring quality and height weather resistance, namely make extend the work-ing life of surface-treated layer, can dirt be prevented for a long time to be attached to substrate surface.
To the eyeglass processed with comparative example composition (M) and composition (N), namely the eyeglass after composition (M) and the composition (N) of similar surfaces treatment compositions process carries out mechanical friction, and measure its static contact angle mean value, find that its decreasing value is much larger than the eyeglass through surface treating composition process, particularly through eyeglass that composition (M) processes, after 1200 mechanical friction to-and-fro movements, its surface static contact angle mean value is down to less than 100 °, and antifouling property reduces greatly.Illustrate that the surface treating composition within the scope of the component ratio of right expression can make eyeglass have better enduring quality, extend work-ing life.
Claims (14)
1. a surface treating composition, is characterized in that, comprises organic fluorosilicone compound and fluorochemicals; Described organic fluorinated silicone compound formula (A) is expressed as follows:
F-(CF
2)
q-(OC
3F
6)
m-(OC
2F
4)
n-(CH
2)
o-C(＝O)-NH-(CH
2)
r-C
3H
6-Si(X)
3(A)
Described fluorochemicals general formula (B) is expressed as follows:
F-(CF
2)
q-(OC
3F
6)
m-(OC
2F
4)
n-(CF
2)
o-F (B)
Wherein q is the integer of 1 ~ 3, and m, n are respectively the integer of 0 ~ 200, o be 1 or 2, r be the integer of 0 ~ 17, X is hydrolysable group;
The molar content of described organic fluorinated silicone compound (A) is not less than 75% of described surface treating composition mole total amount; The molar content of described fluorochemicals (B) is not more than 25% of described surface treating composition mole total amount.
2. surface treating composition according to claim 1, is characterized in that, described X group is alkoxy base or halogen group.
3. surface treating composition according to claim 1, is characterized in that, the molar content of described fluorochemicals (B) is less than 15% of described surface treating composition mole total amount.
4. surface treating composition according to claim 1, is characterized in that, also comprises catalyzer; The molar content of described catalyzer is less than 5% of described surface treating composition mole total amount; Described catalyzer, for improving the activity of described surface treating composition, promotes that described surface treating composition carries out surface treatment.
5. surface treating composition according to claim 4, is characterized in that, the molar content of described catalyzer accounts for the 0.01%-2% of described surface treating composition mole total amount.
6. surface treating composition according to claim 4, is characterized in that, described catalyzer is one in acid, alkali, organic acid metal-salt, titanic acid ester, chelate compound or any several mixing.
7. the surface treating composition according to any one of right 1 ~ 6, it is characterized in that, described organic fluorinated silicone compound (A) and the middle o of described fluorochemicals (B) are 1, and described organic fluorinated silicone compound (A) and described fluorochemicals (B) are that following general formula (A-1) and (B-1) represent:
F-(CF
2)
q-(OC
3F
6)
m-(OC
2F
4)
n-CH
2-C(＝O)-NH-(CH
2)
r-C
3H
6-Si(X)
3(A-1)
F-(CF
2)
q-(OC
3F
6)
m-(OC
2F
4)
n-CF
3(B-1)
Wherein q is the integer of 1 ~ 3, and m, n are respectively the integer of 0 ~ 200, and r is the integer of 0 ~ 17, and X is hydrolysable group.
8. surface treating composition according to claim 1, is characterized in that, described surface treating composition passes through organic solvent dissolution; In solution after dissolving, the mole percent concentration of organic fluorinated silicone compound (A) is in 0.01% ~ 80% scope.
9. surface treating composition according to claim 8, is characterized in that, described organic solvent is for containing fluorous solvent.
10. surface treating composition according to claim 9, is characterized in that, described organic solvent is any one or a few in fluorine-containing alkane, fluorine-containing aromatic hydrocarbon, fluorine-containing ether.
11. 1 kinds of surfaces, through the article of the surface treating composition process according to any one of claim 1 ~ 10, is characterized in that, comprise base material and surface-treated layer; Described surface-treated layer is arranged at described substrate surface, and the surface treating composition according to any one of claim 1 ~ 10 is formed.
The article that 12. surfaces according to claim 11 are treated, is characterized in that, described base material is the transparent material comprising antireflective optical layer.
The article that 13. surfaces according to claim 11 are treated, is characterized in that, the treated article in described surface are selected from optics; Described optics is any one in anti-reflective film, optical filter, optical mirror slip, glasses lens, beam splitter, prism, scintilloscope.
The article that 14. surfaces according to claim 11 are treated, is characterized in that, described surface treatment layer thickness is 0.5nm ~ 30nm.
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| CN104312397A (en) * | 2014-10-29 | 2015-01-28 | 苏州东杏表面技术有限公司 | Surface treating agent as well as preparation method and use thereof |
| CN105778080B (en) * | 2016-04-12 | 2016-12-14 | 泉州市思康新材料发展有限公司 | A kind of perfluoropolyether-modified silane compound and comprise its surface treating composition and thin film |
| CN107082879B (en) * | 2017-05-04 | 2020-08-28 | 龙岩思康新材料有限公司 | Anti-fingerprint agent and preparation method thereof |
| CN110128941A (en) * | 2018-02-08 | 2019-08-16 | 赛吉材料科技（上海）有限公司 | A kind of surface treating composition |
| CN112851927B (en) * | 2021-01-21 | 2023-09-08 | 广东石油化工学院 | Method for preparing perfluoropolyether and perfluoropolyether thereof |
| CN117062854A (en) * | 2021-03-30 | 2023-11-14 | 大金工业株式会社 | Silane compound containing fluoropolyether group |
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| CN1918326A (en) * | 2004-02-12 | 2007-02-21 | 大金工业株式会社 | Electroplating in presence of co2 |
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| CN102666759A (en) * | 2009-11-11 | 2012-09-12 | 依视路国际集团（光学总公司） | Surface treatment composition, process for producing the same, and surface-treated article |
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| CN1918326A (en) * | 2004-02-12 | 2007-02-21 | 大金工业株式会社 | Electroplating in presence of co2 |
| CN1972759A (en) * | 2004-04-20 | 2007-05-30 | 3M创新有限公司 | Antisoiling coatings for antireflective substrates |
| CN101151269A (en) * | 2005-04-01 | 2008-03-26 | 大金工业株式会社 | Surface modifier |
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