CN101157078B - Method for producing organic thin film - Google Patents
Method for producing organic thin film Download PDFInfo
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- CN101157078B CN101157078B CN2007101631665A CN200710163166A CN101157078B CN 101157078 B CN101157078 B CN 101157078B CN 2007101631665 A CN2007101631665 A CN 2007101631665A CN 200710163166 A CN200710163166 A CN 200710163166A CN 101157078 B CN101157078 B CN 101157078B
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Abstract
The purpose of the invention is to provide a method for producing an organic thin film which enables to swiftly form a dense organic thin film which includes little impurities. With this method, such an organic film can be stably formed continuously two or more times. The method for producing an organic thin film on a substrate surface is characterized by comprising a step (A) wherein the substrate is brought into contact with an organic solvent solution containing a metal surfactant having at least one or more hydrolyzable groups and a catalyst which is interactive with the metal surfactant, and by setting or keeping the water content in the organic solvent solution within a certain range.
Description
The application is that application number is 2004800099401, the applying date is that April 14, denomination of invention in 2004 are dividing an application of method for producing organic thin film.
Technical field
The present invention relates to relate to the solution and the resulting organic film of the manufacturing organic film that in the method, uses in the manufacturing approach of substrate surface through metal-organic film that oxygen key etc. forms.
Background technology
As being used for substrate surface is carried out the formation method of filming of modification, the anti-fissility of the manufacturing of having known is excellent and the transparency is high, the method for the chemisorbed film of the transparency of substrate surface gloss and non-wounded substrate has several kinds.(open referring to the spy flat 4-132637 communique, spy are opened flat 4-221630 communique, the spy opens flat 4-367721 communique)
Known be to contact the mixed solution that contains alkoxyl silicone alkanes surfactant at least, do not contain the non-water kind solvent of reactive hydrogen and be selected from least a silanol condensation catalyst in carboxylic metallic salt, carboxylate slaine, carboxylic metallic salt polymer, carboxylic metallic salt chelate, titanate esters and the titanate chelate class with said substrate surface with the manufacturing approach of said substrate surface formation through the covalently bound chemisorbed film of silicon oxygen bond (open put down the 8-337654 communique referring to the spy) containing the method that forms chemisorbed film on the substrate surface of reactive hydrogen.
The known method that is formed with crystalline chemisorbed film at substrate surface is; Dripping on the silicon chip surface of purifying waste water the method launching and form the crystallinity monomolecular film to the organic solvent solution of silanes surfactant (referring to Bull.Chem.Soc.Jpn.; 74,1397-1401 (2001)).
The method of known formation repellency overlay film is; Use the monomer and the polymer of hydrolysis product of the silane compound that contains fluoro-alkyl of acid-catalyzed hydrolysis, the repellency overlay film that utilizes the silanol base to constitute monolayer be fixed on method on the substrate surface (referring to the spy open flat 11-228942 communique, the spy opens flat 11-322368 communique).
The known method containing formation monomolecular film on the substrate surface of reactive hydrogen has the manufacturing approach of chemical adsorption monomolecular film; It is characterized in that, contain on one side following of dry atmosphere with the chemical adsorbing liquid of non-water class organic solvent and the modulation of silanes surfactant be coated on the substrate surface, evaporate, concentrate said organic solvent make in the said adsorption liquid surfactant molecule and substrate surface generation chemical reaction and an end bonding of said surfactant molecule and be fixed on the substrate surface, after falling said organic solvent evaporation, remain in the operation that the unreacted surfactant on the substrate surface cleans, removes (open put down the 11-147074 communique referring to the spy) with the organic solvent handle.
But, thereby all these methods all exist film forming needs the problem of spended time, remain in silanol condensation catalyst in the film hindered chemisorbed can not make the problem of fine and close monomolecular film, since generation acidic materials make problem that base material is restricted and must be in non-aqueous system the problem etc. of film forming.Especially, the fine patternization requirement in the design such as electric device will be stablized the monomolecular film that the least possible densification of impurity is provided.Also have,, still still on noncrystalline substrate, do not form the example of crystallinity chemisorbed film so far even adopt above-mentioned known method.
Summary of the invention
Based on the actual conditions of said prior art, the object of the present invention is to provide a kind of film forming rapidly and can stably repeatedly form the method for producing organic thin film of few, the fine and close organic film of impurity continuously.
The inventor etc. have carried out painstakingly exploring for addressing the above problem; The result finds; If contain metal species surfactant with at least 1 or more a plurality of hydrolization groups and therewith the moisture in the organic solvent solution of the interactional catalyst of metal species surfactant set or remain in the prescribed limit; Perhaps set or remain on the ormal weight scope to the moisture in the organic solvent solution that contains metal species surfactant with at least 1 or more a plurality of hydroxyls; Contact repeatedly 2 times or more times with same solution and substrate, just can stablize and promptly form the organic film of homogeneous.
That is, the present invention relates to
(1) method for producing organic thin film; It is the method for producing organic thin film that on substrate surface, forms organic film; It is characterized in that; Comprise containing metal species surfactant with at least 1 or more a plurality of hydrolization groups and the organic solvent solution of the interactional catalyst of metal species surfactant and the operation (A) of said substrate contacts therewith the moisture setting in its said organic solvent solution or remain on prescribed limit.
(2) method for producing organic thin film described in above-mentioned (1); It is characterized in that, aforementioned organic solvent solution be through use with respect to 1 mole of said metal species surfactant 0.001～1mol's or oxide conversion molal quantity be 0.001～1mol, can obtain with the interactional catalyst adjustment of aforementioned metal class surfactant.
(3) method for producing organic thin film; It is the method for producing organic thin film that on substrate surface, forms organic film; It is characterized in that; Comprise containing metal species surfactant with at least 1 or more a plurality of hydrolization groups and the organic solvent solution of the interactional catalyst of metal species surfactant and the operation (A) of said substrate contacts therewith; Moisture in the aforementioned organic solvent solution is remained on prescribed limit, use same solution to repeat 2 times or more times said operation (A).
(4) method for producing organic thin film described in above-mentioned (3) is characterized in that, aforementioned repetition 2 times or more times said operation (A) are to use same solution, 2 or more a plurality of substrate are carried out said operation (A).
(5) each described method for producing organic thin film in above-mentioned (1)～(4) is characterized in that, has the operation (B) said substrate cleaning afterwards in aforementioned operation (A).
(6) each described method for producing organic thin film in above-mentioned (1)～(5) is characterized in that, has afterwards the operation (C) of said substrate heating in aforementioned operation (A).
(7) method for producing organic thin film described in above-mentioned (6) is characterized in that, aforementioned operation (A) afterwards, aforementioned operation (C) further has the operation (B) said substrate cleaning before.
(8) each described method for producing organic thin film in above-mentioned (1)～(7) is characterized in that, through with aforementioned organic solvent solution the scope that water layer is set the amount of moisture of aforementioned organic solvent solution or remain on ormal weight being set in contact.
(9) each described method for producing organic thin film in above-mentioned (1)～(8); It is characterized in that the scope of setting the amount of moisture of aforementioned organic solvent solution or remain on ormal weight of the water-retaining property material that is in saturation state being arranged through coexistence in aforementioned organic solvent solution.
(10) method for producing organic thin film described in above-mentioned (9) is characterized in that, aforementioned water-retaining property material is a glass fiber filter.
(11) each described method for producing organic thin film in above-mentioned (1)～(10) is characterized in that, through in aforementioned organic solvent solution, being blown into the scope of setting the amount of moisture in the aforementioned organic solvent solution or remain on ormal weight of the gas that contains moisture.
(12) each described method for producing organic thin film in above-mentioned (1)～(11) is characterized in that, sets or remain on 50～1000ppm scope to the amount of moisture in the aforementioned organic solvent solution.
(13) each described method for producing organic thin film in above-mentioned (1)～(12) is characterized in that, the amount of moisture of aforementioned ormal weight scope is a value of measuring this solution of a part of from aforementioned organic solvent solution, taking with Ka Er-Fei Xiefa.
(14) each described method for producing organic thin film in above-mentioned (1)～(13); It is characterized in that at least a in aforementioned hydrolysis product, organic acid, silanol condensation catalyst and the acid catalyst that can be the metallic compound that is selected from metal oxide, metal hydroxides, metal alkoxide class, chelating or coordination, metal alkoxide class partial hydrolysis product with the interactional catalyst of said metal species surfactant, obtain by the said metal alkoxide class of water treatment for 2 times of equivalents of metal alkoxide class or more times of equivalents.
(15) method for producing organic thin film described in above-mentioned (14) is characterized in that, uses the organic acid of pKa value in 1～6 scope.
(16) method for producing organic thin film described in above-mentioned (14) is characterized in that, in organic solvent, does not exist under the situation of acid, alkali and/or dispersion stabilizer aforementioned metal alkoxide partial hydrolysis product to have and does not condense and the character of stable dispersion.
(17) method for producing organic thin film described in above-mentioned (14) or (16); It is characterized in that; Aforementioned metal alkoxide partial hydrolysis product is to use in the organic solvent for the metal alkoxide class to being equal to or greater than 0.5 and less than the water of 2.0 times of moles, the product that obtains being hydrolyzed from-100 ℃ of scopes to the organic solvent reflux temperature.
(18) each described method for producing organic thin film in above-mentioned (14)～(17); It is characterized in that the metal in the metallic compound of aforementioned metal oxide, metal hydroxides, metal alkoxide class, chelating or coordination, metal alkoxide class partial hydrolysis product, the hydrolysis product that obtained by the said metal alkoxide class of water treatment for 2 times of equivalents of metal alkoxide class or more times of equivalents is to be selected from titanium, zirconium, aluminium, silicon, germanium, indium, tin, tantalum, zinc, tungsten, the lead a kind or more kinds of.
Each described method for producing organic thin film is characterized in that in above-mentioned (1)～(18), and aforementioned metal species surfactant with at least 1 or more a plurality of hydrolization groups is the compound with formula (I) expression:
R
1 nMX
m-n (I)
(in the formula, R
1Expression is with or without substituent alkyl, is with or without substituent halo alkyl, contains the alkyl of concatenating group or contains the halo alkyl of concatenating group; M representes to be selected from least a kind of metallic atom in silicon atom, germanium atom, tin atom, titanium atom and the zirconium atom; X representes hydroxyl or hydrolization group; N representes the arbitrary integer in 1～(m-1); M representes the atom rank of M; When n is 2 or more for a long time, R
1For identical or different all can, be 2 or more for a long time and work as (m-n), X identical or differently all can.But in (m-n) individual X, at least 1 X is a hydrolization group.)。
(20) each described method for producing organic thin film in above-mentioned (1)～(18) is characterized in that, aforementioned metal species surfactant with at least 1 or more a plurality of hydrolization groups is the compound with formula (II) expression:
R
2 3C-(CR
3 2)
p-R
4 q-MY
rX
m-r-1 (II)
(in the formula, M representes to be selected from least a metallic atom in silicon atom, germanium atom, tin atom, titanium atom and the zirconium atom; X representes hydroxyl or hydrolization group; R
2And R
3Represent hydrogen atom or fluorine atom respectively independently; R
4The divalent of expression alkylidene, ethenylidene, ethynylene, arlydene or silicon atoms and/or oxygen atom links group; Y representes hydrogen atom, alkyl, alkoxyl, contains fluoroalkyl or fluoroalkoxy; P representes 0 or natural number; Q representes 0 or 1; R representes 0～(m-2) integer; At r is 2 or more for a long time, Y is identical or different all can; At (m-r-1) is 2 or more for a long time, X is identical or different all can.But in (m-r-1) individual X, at least 1 X is a hydrolization group.)。
(21) each described method for producing organic thin film in above-mentioned (1)～(20) is characterized in that, the hydrolization group of aforementioned X is alkoxyl or the acyloxy of halogen atom, C1～C6.
(19) method for producing organic thin film; It is the method for producing organic thin film that on substrate surface, forms organic film; It is characterized in that; Comprise the organic solvent solution and the contacted operation of substrate that make the metal species surfactant that has 1 or more a plurality of hydroxyls at least, set or remain on the ormal weight scope to the amount of moisture in the aforementioned organic solvent solution.
(20) method for producing organic thin film described in above-mentioned (22) is characterized in that, sets or remain on 50～1000ppm scope to the amount of moisture in the aforementioned organic solvent solution.
(21) method for producing organic thin film described in above-mentioned (22) or (23) is characterized in that, the aforementioned metal species surfactant that contains at least 1 or more a plurality of hydroxyls is the compound with formula (III) expression:
R
1 nMX
m-n-1(OH) (III)
(in the formula, R
1Expression is with or without substituent alkyl, is with or without substituent halo alkyl, contains the alkyl of concatenating group or contains the halo alkyl of concatenating group; M representes to be selected from least a kind of metallic atom in silicon atom, germanium atom, tin atom, titanium atom and the zirconium atom; X representes hydroxyl or hydrolization group; N representes any integer of 1～(m-1), and m representes the valence of M; At n is 2 or R more for a long time
1Identical or differently all can; At (m-n-1) is 2 or more for a long time, X is identical or different all can.)。
(22) each described method for producing organic thin film in above-mentioned (1)～(24); It is characterized in that the operation of aforementioned organic solvent solution and substrate contacts is humidity to be remained in 40RH% or the more space said organic solvent solution and the contacted operation of substrate.
(23) each described method for producing organic thin film in above-mentioned (1)～(24); It is characterized in that the operation of aforementioned organic solvent solution and substrate contacts is humidity to be remained in 60RH% or the more space aforementioned organic solvent solution and the contacted operation of substrate.
(24) each described method for producing organic thin film in above-mentioned (1)～(26) is characterized in that, aforementioned organic solvent solution is varsol solution or fluorocarbons kind solvent solution.
(25) each described method for producing organic thin film in above-mentioned (1)～(27) is characterized in that, organic film is the crystallinity organic film.
(26) each described method for producing organic thin film in above-mentioned (1)～(28) is characterized in that organic film is a monomolecular film.
(27) each described method for producing organic thin film in above-mentioned (1)～(29) is characterized in that, what aforesaid base plate used is the substrate that the surface contains reactive hydrogen.
(28) each described method for producing organic thin film in above-mentioned (1)～(30) is characterized in that, aforesaid base plate is to form by at least a kind that is selected from glass, silicon chip, pottery, metal and the plastics.
(29) each described method for producing organic thin film in above-mentioned (1)～(31) is characterized in that organic film is a chemisorbed film.
(30) each described method for producing organic thin film in above-mentioned (1)～(32) is characterized in that, aforementioned organic film is the self aggregation film.
Also have; In above-mentioned organic solvent solution, form the new discovery (34 of claims the) of aggregation based on the metal species surfactant with at least 1 or more a plurality of hydrolization groups or metal species surfactant with at least 1 or more a plurality of hydroxyls, accomplished the invention of (35):
(35) the self aggregation film forms solution, and it is that the self aggregation film that on substrate surface, forms the self aggregation film forms solution, it is characterized in that the molecule that forms the self aggregation film forms aggregation in solution.
Also relate to:
(36) the self aggregation film described in (35) forms solution, it is characterized in that, the molecule that forms aforementioned self aggregation film is the metal species surfactant or derivatives thereof with at least 1 or more a plurality of hydroxyl or hydrolization group.
(37) the self aggregation film described in (35) or (36) forms solution; It is characterized in that aforementioned aggregation is with interactional catalyst of metal species surfactant and water treatment are resulting therewith the metal species surfactant with at least 1 or more a plurality of hydroxyl or hydrolization group.
(38) self aggregation film described in each in (35)～(37) forms solution, it is characterized in that, aforementioned metal species surfactant with at least 1 or more a plurality of hydroxyl or hydrolization group is the compound with formula (IV) expression:
R
11 n1M
1X
1 m1-n1 (IV)
(in the formula, R
11Expression is with or without substituent alkyl, is with or without substituent halo alkyl, contains the alkyl of concatenating group or contains the halo alkyl of concatenating group; M
1Expression is selected from least a kind of metallic atom in silicon atom, germanium atom, tin atom, titanium atom and the zirconium atom; X
1Expression hydroxyl or hydrolization group; n
1Expression 1～(m
1-1) arbitrary integer; m
1Expression M
1Valence; Work as n
1Be 2 or more for a long time, R
11Identical or differently all can; At (m
1-n
1) be 2 or more for a long time, X
1Identical or differently all can.)。
(39) self aggregation film described in each in (35)～(37) forms solution, it is characterized in that, aforementioned metal species surfactant with at least 1 or more hydroxyl or hydrolization group is the compound with formula (V) expression:
R
21 3C-(CR
31 2)
p1-R
41 q1-M
2Y
2 r2X
2 m2-r2-1 (V)
(in the formula, M
2Expression is selected from least a metallic atom in silicon atom, germanium atom, tin atom, titanium atom and the zirconium atom; X
2Expression hydroxyl or hydrolization group; R
21And R
31Represent hydrogen atom or fluorine atom independently of one another; R
41The divalent of expression alkylidene, ethenylidene, ethynylene, arlydene or silicon atoms and/or oxygen atom links group; Y
2Represent hydrogen atom, alkyl, alkoxyl, contain fluoroalkyl or fluoroalkoxy; p
1Expression 0 or natural number; q
1Expression 0 or 1; r
2Expression 0～(m
2-2) integer; At r
2Be 2 or more for a long time, Y
2Identical or differently all can; At (m
2-r
2-1) be 2 or more for a long time, X
2Identical or differently all can.)。
(40) the self aggregation film described in each in (35)～(39) forms solution, it is characterized in that aforementioned hydrolization group is halogen atom, C1～C6 alkoxyl or acyloxy.
(41) the self aggregation film described in each in (35)～(40) forms solution, it is characterized in that the average grain diameter of aforementioned aggregation is in 10～1000nm scope.
(42) the self aggregation film described in each in (35)～(41) forms solution, it is characterized in that the Zeta potential value of aforementioned aggregation is with the Zeta potential value of the said substrate in a kind of solvent or bigger value.
Find that also although employed substrate does not have crystallinity in the method for producing organic thin film, organic film has crystallinity (43 of claims the), has accomplished the invention of (44) in view of the above.That is to say, relate to
(44) chemisorbed film, it is the chemisorbed film that on substrate, forms, and it is characterized in that, aforesaid base plate does not have crystallinity and chemisorbed film has crystallinity.
(45) chemisorbed film described in (44) is characterized in that, it is the chemisorbed film that forms with the metal species surfactant with at least 1 or more a plurality of hydroxyl or hydrolization group.
(46) (44) or the chemisorbed film described in 45 is characterized in that, aforementioned chemisorbed film is a monomolecular film.
(47) each described chemisorbed film is characterized in that in (44)～(46), and aforementioned chemisorbed film is the self aggregation film.
Also find; In substrate in method for producing organic thin film and the contacted operation of said organic solvent solution; Utilize at least a method in infusion process, spin-coating method, rolling method, Meyer rod method, silk screen print method, woodburytype, spread coating and the spraying process; Even the operation of the said organic solvent solution of coating also can be made monomolecular film (48 of claims the) on said substrate, accomplished the invention of (49), (50) in view of the above.
(49) monomolecular film manufacturing approach; It is characterized in that, comprise utilize that at least a method be selected from infusion process, spin-coating method, rolling method, Meyer rod method, silk screen print method, woodburytype, spread coating and the spraying process has hydroxyl containing, the organic solvent solution of the metal species surfactant of oxyl or acyloxy is coated on the operation on the substrate.
(50) the monomolecular film manufacturing approach is characterized in that, drips the organic solvent solution of the metal species surfactant with hydroxyl, oxyl or acyloxy, and the solution that drips is pressurizeed from top, it is spread on substrate come.That is to say, relate to:
(51) manufacturing approach of the monomolecular film described in (50) is characterized in that, said method to the pressurization from top of the solution that drips is film, sheet or dull and stereotyped and method calendering on substrate surface is overlapping.
(52) the described monomolecular film manufacturing approach of each in (49)～(51) is characterized in that, the operation of cleaning aforesaid base plate is set after aforementioned painting process.
(53) the described monomolecular film manufacturing approach of each in (49)～(52) is characterized in that, after aforementioned painting process, is provided with the operation of aforesaid base plate heating.
(54) the described monomolecular film manufacturing approach of each in (49)～(53); It is characterized in that, the aforementioned organic solvent solution that contains the metal species surfactant be further contain can with the organic solvent solution of the interactional catalyst of metal species surfactant.
Specify the present invention below.
1) method for producing organic thin film
Method for producing organic thin film of the present invention is characterised in that; Comprise having the metal species surfactant of at least one or more a plurality of hydrolization groups and the organic solvent solution of the interactional catalyst of metal species surfactant (following be called sometimes " solution (a) ") or (b) have the organic solvent solution (following be called sometimes " solution (b) ") and the contacted operation of substrate of the metal species surfactant of at least one or more a plurality of hydroxyls therewith, the setting of the moisture in the said organic solvent solution or remain on the ormal weight scope containing (a).
As the metal species surfactant in the employed solution (a) among the present invention with at least 1 or more a plurality of hydrolization groups; So long as the material that in same molecule, has at least one or more a plurality of functional group and hydrophobic groups that can hydrolysis just; Have no particular limits, preferably have can with the surfactant of the hydrolization group of reactive with active hydrogen Cheng Jian on substrate surface.Also having, is hydroxyl as what can enumerate with other functional group of reactive with active hydrogen Cheng Jian, also can contain hydroxyl.The such metal species surfactant that specifically can enumerate is being that the compound of above-mentioned formula (I) expression serves as preferred.
In the above-mentioned formula (I), R
1Expression is with or without substituent alkyl, is with or without substituent halo alkyl, contains the alkyl of concatenating group or contains the halo alkyl of concatenating group.
As the said alkyl that is with or without in the substituent alkyl, enumerate: the alkyl of carbon numbers 1～30 such as methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl group, sec-butyl, the tert-butyl group, n-pentyl, isopentyl, neopentyl, tertiary pentyl, n-hexyl, isohesyl, n-heptyl, n-octyl, positive decyl; The thiazolinyl of carbon numbers 2～30 such as vinyl, acrylic, cyclobutenyl, pentenyl; Aryl such as phenyl, naphthyl; Deng.
As the halo alkyl that is with or without in the substituent halogenated hydrocarbons, the haloalkyl of enumerating that carbon number 1～30 is arranged, 2～30 haloalkenyl group, halogenated aryl etc.As halogen atom, enumerated fluorine atom, chlorine atom, bromine atoms etc., be preferred with the fluorine atom.That specifically enumerates has, in the above-mentioned alkyl 1 or more a plurality of hydrogen atom replaced by halogen atoms such as fluorine atom, chlorine atom or bromine atoms and group.
In the middle of these; As said halo alkyl; With 2 in the alkyl of carbon number 1～30 or more a plurality of hydrogen atom replaced by halogen atom and group serve as preferred, with 2 in the alkyl of carbon number 1～30 or more a plurality of hydrogen atom replaced by fluorine atom and must group for more preferably.Also have, when fluoro-alkyl had branched structure, branching partly was preferably the short chain of carbon number 1～4, more preferably the short chain of carbon number 1～2.
As fluoro-alkyl; With bonding on the terminal carbon one or more fluorine atom and group serve as preferred; Have bonding on the terminal carbon group of CF3 group part of 3 fluorine atoms for more preferably, end is not have the substituted alkyl of fluorine atom and the carbochain of inside is that the substituted carbochain of fluorine atom is arranged also is indifferent.Particularly preferably be, all hydrogen atoms that end portion has an alkyl be fluorine atom substituted perfluoroalkyl moieties and and the metallic atom M that says of back between have with-(CH
2)
hThe group of the alkylidene that-(h representes 1～6 integer in the formula, and the integer with 2～4 serves as preferred) is represented.
When % representes the number of fluorine atoms in the fluoro-alkyl, be preferably 60% or more with [(number of fluorine atoms in the fluoro-alkyl)/(fluoro-alkyl is corresponding to contain existing number of hydrogen atoms in the alkyl of same carbon number) * 100], more preferably 80% or more.
As the above-mentioned substituent alkyl or be with or without the substituting group in the substituent halo alkyl of being with or without, that enumerates has: alkoxyl such as carboxyl, amide groups, imide, ester group, methoxyl group, ethyoxyl or hydroxyl etc.These substituent numbers serve as preferred with 0～3.
As the alkyl that contains in the alkyl that links group, what specifically enumerate is same with the above-mentioned alkyl that is with or without in the substituent alkyl.
Also have, as the halo alkyl that contains in the halo alkyl that links group, what specifically enumerate is same with the above-mentioned halo alkyl that is with or without in the substituent halo alkyl.
Said binding group is with between the carbon-carbon bond that is present in alkyl or halo alkyl or serve as preferred between the carbon of alkyl and the metallic atom M that says of back.
The object lesson that links group has been enumerated ,-O-,-S-,-SO
2-,-CO-,-C (=O) O-or-C (=O) NR
51-(in the formula, R
51Alkyl such as expression hydrogen atom, methyl, ethyl, n-pro-pyl, isopropyl) etc.
In the middle of these, consider R from repellency, durability viewpoint
1With the fluoro-alkyl of the alkyl of carbon number 1～30, carbon number 1～30 or to contain the fluoro-alkyl that links group serve as preferred.
R
1Preferred object lesson enumerated CH
3-, CH
3CH
2-, (CH
3)
2CH-, (CH
3)
3C-, CH
3(CH
2)
2-, CH
3(CH
2)
3-, CH
3(CH
2)
4-, CH
3(CH
2)
5-, CH
3(CH
2)
6-, CH
3(CH
2)
7-, CH
3(CH
2)
8-, CH
3(CH
2)
9-, CH
3(CH
2)
10-, CH
3(CH
2)
11-, CH
3(CH
2)
12-, CH
3(CH
2)
13-, CH
3(CH
2)
14-, CH
3(CH
2)
15-, CH
3(CH
2)
16-, CH
3(CH
2)
17-, CH
3(CH
2)
18-, CH
3(CH
2)
19-, CH
3(CH
2)
20-, CH
3(CH
2)
21-, CH
3(CH
2)
22-, CH
3(CH
2)
23-, CH
3(CH
2)
24-, CH
3(CH
2)
25-, CF
3-, CF
3CF
2-, (CF
3)
2CF-, (CF
3)
3C-, CF
3(CH
2)
2-, CF
3(CF
2)
3(CH
2)
2-, CF
3(CF
2)
5(CH
2)
2-, CF
3(CF
2)
7(CH
2)
2-, CF
3(CF
2)
3(CH
2)
3-, CF
3(CF
2)
5(CH
2)
3-, CF
3(CF
2)
7(CH
2)
3-, CF
3(CF
2)
4O (CF
2)
2(CH
2)
2-, CF
3(CF
2)
4O (CF
2)
2(CH
2)
3-, CF
3(CF
2)
7O (CF
2)
2(CH
2)
2-, CF
3(CF
2)
7CONH (CH
2)
2-, CF
3(CF
2)
7CONH (CH
2)
3-, CF
3(CF
2)
3O [CF (CF
3) CF (CF
3) O]
2CF (CF
3) CONH (CH
2)
3-,
CH
3(CF
2)
7(CH
2)
2-, CH
3(CF
2)
8(CH
2)
2-, CH
3(CF
2)
9(CH
2)
2-, CH
3(CF
2)
10(CH
2)
2-, CH
3(CF
2)
11(CH
2)
2-, CH
3(CF
2)
12(CH
2)
2-, CH
3(CF
2)
7(CH
2)
3-, CH
3(CF
2)
9(CH
2)
3-, CH
3(CF
2)
11(CH
2)
3-, CH
3CH
2(CF
2)
6(CH
2)
2-, CH
3CH
2(CF
2)
8(CH
2)
2-, CH
3CH
2(CF
2)
10(CH
2)
2-, CH
3(CF
2)
4O (CF
2)
2(CH
2)
2-, CH
3(CF
2)
7(CH
2)
2O (CH
2)
3-, CH
3(CF
2)
8(CH
2)
2O (CH
2)
3-, CH
3(CF
2)
9(CH
2)
2O (CH
2)
3-, CH
3CH
2(CF
2)
6(CH
2)
2O (CH
2)
3-, CH
3(CF
2)
6CONH (CH
2)
3-, CH
3(CF
2)
8CONH (CH
2)
3-, CH
3(CF
2)
3O [CF (CF
3) CF (CF
3) O]
2CF (CF
3) CONH (CH
2)
3-etc., but be not limited in these.
M representes a kind of atom from silicon atom, germanium atom, tin atom, titanium atom and zirconium atom, selecting, obtains easily considering with viewpoint such as reactivity from raw material, and is wherein preferred for especially with silicon atom.
X representes hydroxyl and hydrolization group.As hydrolization group, so long as with water reaction and the group that decomposes just can, have no particular limits.That can enumerate specifically, has: the alkoxyl that is with or without substituent carbon number 1～6; Be with or without substituent oxyl; Be with or without substituent acyloxy; Halogen atoms such as fluorine atom, chlorine atom, bromine atoms, iodine atom; NCO; Cyanic acid; Amino or amide groups etc.
Particularly preferably be, be with or without the acyloxy such as oxyl, acetoxyl group such as alkoxyl, alicyclic ring, aromatic radical, alkene oxygen base, aralkoxy of substituent carbon number 1～6.
As the alkoxyl of carbon number 1～6, that enumerates has, methoxyl group, ethyoxyl, positive propoxy, isopropoxy, n-butoxy, sec-butoxy, tert-butoxy, n-pentyloxy, just own oxygen base etc.
As acyloxy; Acetoxyl group, propionyloxy, propionyloxy, n-pro-pyl carbonyl oxygen base, isopropyl carbonyl oxygen base, normal-butyl carbonyl oxygen base, propionyloxy, alicyclic ring oxyl, ring propoxyl group, the ring third methyl oxygen base, cyclohexyloxy, norborneol alcoxyl base etc., alkene oxygen base etc. have been enumerated; Vinyl oxygen base, pi-allyl oxygen base etc., alkynyloxy group; Propargyloxy etc., aralkyl oxy; Propargyloxy etc., aralkyl oxy; Aryl radical oxygen such as benzyloxy, benzene ethyoxyl; Phenoxy group, naphthoxy etc., benzoyloxy group or the like.
As their substituting group, carboxyl, amide groups, imide, ester group, hydroxyl etc. have been enumerated.In these, as X, serve as preferred with alkoxyl, acyloxy or the NCO of hydroxyl, halogen atom, carbon number 1～6, the alkoxyl of carbon number 1～4 or acyloxy are for more preferably.
M representes the valence of metallic atom M.
N representes any one integer in 1～(m-1).For making highdensity organic film, be 1 to serve as preferred with n.
When n is 2 or more for a long time, R1 is identical or different all can.
Also have, when (m-n) is 2 or more for a long time, X identical or different all can, but in (m-n) individual X, it is hydrolization group that 1 X will be arranged at least.
In the compound of formula (I) expression, as a preferred form, can use the compound of formula (II) expression is example.
In the formula (II), R
4The divalent functional group of expression alkylidene, ethenylidene, ethynylene, arlydene or silicon atoms and/or oxygen atom.Specifically, can be example with the functional group shown in following.
In above-mentioned formula, a and b represent 1 or bigger any natural number.
Y representes hydrogen atom; Alkyl such as methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl group, sec-butyl, the tert-butyl group, n-pentyl, isopentyl, neopentyl, tertiary pentyl, n-hexyl, isohesyl; Alkoxyls such as methoxyl group, ethyoxyl, positive propoxy, isopropoxy, n-butoxy, sec-butoxy, tert-butoxy, n-pentyloxy, just own oxygen base; Some or all hydrogen atoms of alkyl are that fluorine atom replaces the fluoroalkyl that contains that gets; Or some or all hydrogen atoms of alkoxyl are that fluorine atom replaces the fluoroalkoxy get etc.
R representes 0 or 1～(m-2) integer, in order to make highdensity adsorbed film, with r be 0 o'clock serve as preferred.When r is 2 or more for a long time, Y is identical or different separately all can; (m-r-1) be 2 or more for a long time, X is identical or different separately all can.But, in (m-r-1) individual X, have 1 X at least is hydrolization group.
As compound, except compound, can also enumerate following example etc. and be used as preferred configuration with formula (II) expression with formula (I) expression.
(1)CH
3-(CH
2)
g-MY
rX
m-r-1
(2)CH
3-(CH
2)
s-O-(CH
2)
t-MY
rX
m-r-1
(3)CH
3-(CH
2)
u-Si(CH
3)
2-(CH
2)
v-MY
rX
m-r-1
(4)CF
3COO-(CH
2)
w-MY
rX
m-r-1
In the formula, g, s, t, u, v and w represent integer arbitrarily, as special preferred range can example be, g is 1～25, s is 0～12, t is 1～20, u is 0～12, v is 1～20, w is 1～25.
M, Y, X, r and m represent with formula (III) in identical meaning.
The compound shown in following as having of enumerating with the object lesson of the compound of formula (I) expression.
Be be to be that the compound of metallic atom M is a representative example with the silicon atom below, and the present invention to be not limited to this again.Also have, also be not limited to the functional group of institute's example for hydrolization group, good with other the group of hydrolization group bonding.
CH
3CH
2O(CH
2)
15Si(OCH
3)
3
CF
3CH
2O(CH
2)
15Si(OCH
3)
3，
CH
3(CH
2)
2Si(CH
3)
2(CH
2)
15Si(OCH
3)
3
CH
3(CH
2)
6Si(CH
3)
2(CH
2)
9Si(OCH
3)
3
CH
3COO(CH
2)
15Si(OCH
3)
3
CF
3(CF
2)
5(CH
2)
2Si(OCH
3)
3
CF
3(CF
2)
7-(CH＝CH)
3-Si(OCH
3)
3
CH
3CH
2O(CH
2)
15Si(OC
2H
5)
3
CH
3(CH
2)
2Si(CH
3)
2(CH
2)
15Si(OC
2H
5)
3
CH
3(CH
2)
6Si(CH
3)
2(CH
2)
9Si(OC
2H
5)
3
CF
3(CH
2)
6Si(CH
3)
2(CH
2)
9Si(OC
2H
5)
3
CH
3COO(CH
2)
15Si(OC
2H
5)
3
CF
3COO(CH
2)
15Si(OC
2H
5)
3
CF
3COO(CH
2)
15Si(OCH
3)
3
CF
3(CF
2)
9(CH
2)
2Si(OC
2H
5)
3
CF
3(CF
2)
7(CH
2)
2Si(OC
2H
5)
3
CF
3(CF
2)
5(CH
2)
2Si(OC
2H
5)
3
CF
3(CF
2)
7(CH＝CH)
3Si(OC
2H
5)
3
CF
3(CF
2)
9(CH
2)
2Si(OCH
3)
3
CF
3(CF
2)
5(CH
2)
2Si(OCH
3)
3
CF
3(CF
2)
7(CH
2)
2Si(CH
3)(OC
2H
5)
2
CF
3(CF
2)
7(CH
2)
2Si(CH
3)(OCH
3)
2
CF
3(CF
2)
7(CH
2)
2Si(CH
3)
2(OC
2H
5)
CF
3(CF
2)
7(CH
2)
2Si(CH
3)
2(OCH
3)
CF
3(CH
2)
2Si(OCH
3)
3
CF
3(CF
2)
3(CH
2)
2Si(OCH
3)
3
CF
3(CF
2)
5(CH
2)
2Si(OCH
3)
3
CF
3(CF
2)
7(CH
2)
2Si(OCH
3)
3
CF
3(CF
2)
3(CH
2)
3Si(OCH
3)
3
CF
3(CF
2)
5(CH
2)
3Si(OCH
3)
3
CF
3(CF
2)
7(CH
2)
3Si(OCH
3)
3
CF
3(CF
2)
4O(CF
2)
2(CH
2)
2Si(OCH
3)
3
CF
3(CF
2)
4O(CF
2)
2(CH
2)
3Si(OCH
3)
3
CF
3(CF
2)
7(CH
2)
2O(CH
2)
3Si(OCH
3)
3
CF
3(CF
2)
7CONH(CH
2)
2Si(OCH
3)
3
CF
3(CF
2)
7CONH(CH
2)
3Si(OCH
3)
3
CF
3(CF
2)
3O[CF(CF
3)CF(CF
3)O]
2CF(CF
3)-CONH(CH
2)
3Si(OCH
3)
3
CF
3(CF
2)
3(CH
2)
2Si(CH
3)(OCH
3)
2
CF
3(CF
2)
5(CH
2)
2Si(CH
3)(OCH
3)
2
CF
3(CH
2)
2Si(CH
3)(OCH
3)
2
CF
3(CF
2)
3(CH
2)
3Si(CH
3)(OCH
3)
2
CF
3(CF
2)
5(CH
2)
3Si(CH
3)(OCH
3)
2
CF
3(CF
2)
7(CH
2)
3Si(CH
3)(OCH
3)
2
CF
3(CF
2)
4(CF
2)
2(CH
2)
2Si(CH
3)(OCH
3)
2
CF
3(CF
2)
4(CF
2)
2(CH
2)
3Si(CH
3)(OCH
3)
2
CF
3(CF
2)
4(CH
2)
2O(CH
2)
3Si(CH
3)(OCH
3)
2
CF
3(CF
2)
7CONH(CH
2)
2Si(CH
3)(OCH
3)
2
CF
3(CF
2)
7CONH(CH
2)
3Si(CH
3)(OCH
3)
2
CF
3(CF
2)
3O[CF(CF
3)CF(CF
3)O]
2CF(CF
3)-
CONH(CH
2)
3Si(CH
3)(OCH
3)
2
CH
3(CH
2)
7Si(OCH
3)
3
CH
3(CF
2)
7(CH
2)
2Si(OCH
3)
3
CH
3(CF
2)
7(CH
2)
2Si(CH
3)(OCH
3)
2
CH
3(CF
2)
7(CH
2)
2Si(OCH
3)
3
CH
3(CF
2)
7(CH
2)
2Si(NCO)
3
CH
3(CF
2)
8(CH
2)
2Si(OCH
3)
3
CH
3(CF
2)
8(CH
2)
2Si(NCO)
3
CH
3(CF
2)
9(CH
2)
2Si(OCH
3)
3
CH
3(CF
2)
9(CH
2)
2Si(NCO)
3
CH
3CH
2(CF
2)
6(CH
2)
2Si(OCH
3)
3
CH
3CH
2(CF
2)
6(CH
2)
2Si(NCO)
3
CH
3CH
2(CF
2)
8(CH
2)
2Si(OCH
3)
3
CH
3CH
2(CF
2)
8(CH
2)
2Si(NCO)
3
CH
3CH
2(CF
2)
10(CH
2)
2Si(OCH
3)
3
CH
3(CF
2)
4O(CF
2)
2(CH
2)
2Si(OCH
3)
3
CH
3(CF
2)
7(CH
2)
2O(CH
2)
3Si(OCH
3)
3
CH
3(CF
2)
8(CH
2)
2O(CH
2)
3Si(OCH
3)
3
CH
3(CF
2)
9(CH
2)
2O(CH
2)
3Si(OCH
3)
3
CH
3CH
2(CF
2)
6(CH
2)
2O(CH
2)
3Si(OCH
3)
3
CH
3(CF
2)
6CONH(CH
2)
3Si(OCH
3)
3
CH
3(CF
2)
8CONH(CH
2)
3Si(OCH
3)
3
CH
3(CF
2)
3O[CF(CF
3)CF(CF
3)O]
2CF(CF
3)-
CONH(CH
2)
3Si(OCH
3)
3
To these compounds, can use a kind separately, also can be 2 kinds or more kinds of use that combines.
In solution (a), contained, can with the interactional catalyst of said metal species surfactant; So long as have, have no particular limits through being that intermediary comes partly to wait interaction with the catalyst of the effect of activation hydrolization group or hydroxyl, promotion condensation just with the metal section and part of metal species surfactant or hydrolization group by coordinate bond or hydrogen bond.Wherein, preferably from metal oxide, metal hydroxides, metal alkoxide class, chelating or coordination change metallic compound, metal alkoxide class partial hydrolysis product, the resulting hydrolysis product of water treatment metal alkoxide class, organic acid, silanol condensation catalyst and acid catalyst with 2 times of equivalents or more times of equivalents at least a kind of compound selecting; With metal alkoxide class, metal alkoxide class partial hydrolysis product for more preferably.
For metal oxide, metal hydroxides, metal alkoxide class, chelating or coordination change metallic compound, metal alkoxide class partial hydrolysis product, the metal in the resulting hydrolysis product of water treatment metal alkoxide class, organic acid, silanol condensation catalyst with 2 times of equivalents or more times of equivalents do not have special restriction; With at least a kind of from titanium, zirconium, aluminium, silicon, germanium, indium, tin, tantalum, zinc, tungsten and lead, selecting serves as preferred; Titanium, zirconium, aluminium or silicon are for more preferably, and titanium is preferred for especially.
Metal oxide can be to use with any states such as colloidal sol, gel, solid, shaped.Manufacturing approach for colloidal sol, gel has no particular limits, and for example, is example with the Ludox, can example have, sodium silicate solution carry out the method for cation exchange, method of silane oxide hydrolysis etc.Especially preferred is the colloidal sol of stable dispersion in organic solvent, and then the particle diameter of colloidal sol is preferably in 10～100nm scope, with in 10～20nm scope for more preferably.Shape for colloidal sol has no particular limits, and can use Any shape such as spherical, elongate.
Specifically; Can example have, methyl alcohol Ludox, IPA-ST, IPA-ST-UP, IPA-ST-ZL, NPC-ST-30, DMAC-ST, MEK-ST, MIBK-ST, XBA-ST, PMA-ST (above all expressions are the trade names of the organic silicon sol produced by daily output chemical industry (strain) commercial firm) etc.
The quantity of employed metal oxide is not so long as influence the words of the quantity of formed chemisorbed film; Just have no particular limits; Especially, serve as preferred to use catalytic amount with respect to the metal species surfactant, and then; Its oxide conversion mol number with respect to 1mol metal species surfactant be 0.001～1mol for more preferably, preferred in 0.001～0.2mol scope for further.These metal oxides can independent a kind of use, also can be 2 kinds or more use that combines more.
As metal hydroxides, so long as the hydroxide of metal is resulting all right with which type of manufacturing approach.As the manufacturing approach of metal hydroxides, having of the enumerating method that the back says reacts the method for metal alkoxide class hydrolysis, slaine and metal hydroxides etc.In addition, also can commercially available article be made with extra care by required, to use as metal hydroxides.
Carbon number for the alkoxyl in the metal alkoxide class does not have special restriction, from the difficulty or ease of the concentration of the oxide that contains, organic disengaging, consideration such as whether obtain easily, with carbon number 1～4 for more preferably.What the object lesson of the metal alkoxide class of using among the present invention can be enumerated has,
Si (OCH
3)
4, Si (OC
2H
5)
4, Si (OC
3H
7-i)
4, Si (OC
4H
9-t)
4Deng silane oxide;
Ti (OCH
3)
4, Ti (OC
2H
5)
4, Ti (OC
3H
7-i)
4, Ti (OC
4H
9-t)
4Deng alkyl titanium oxide;
Ti [OSi (CH
3)
3]
4, Ti [OSi (C
2H
5)
3]
4Deng four (trialkylsiloxy) titanium; Zr (OCH
3)
4, Zr (OC
2H
5)
4, Zr (OC
3H
7)
4, Zr (OC
4H
9)
4Deng the zirconium alkoxide; Al (OCH
3)
4, Al (OC
2H
5)
4, Ali (OC
3H
7-i)
4, Al (OC
4H
9-t)
4Deng the aluminium alkoxide; Ge (OC
2H
5)
4Deng the germane oxide;
In (OCH
3)
3, In (OC
2H
5)
3, In (OC
3H
7-i)
3, In (OC
4H
9)
3Deng the indium alkoxide; Sn (OCH
3)
4, Sn (OC
2H
5)
4, Sn (OC
3H
7-i)
4, Sn (OC
4H
9)
4Deng the stannane oxide; Ta (OCH
3)
5, Ta (OC
2H
5)
5, Ta (OC
3H
7-i)
5, Ta (OC
4H
9)
5Deng the tantalum alkoxide; W (OCH
3)
6, W (OC
2H
5)
6, W (OC
3H
7-i)
6, W (OC
4H
9)
4Deng the tungsten alkoxide; Zn (OC
2H
5)
2Deng the zinc alkoxide; Pb (OC
4H
9)
4Deng the plumbane oxide; Deng.These metal alkoxide classes can independent a kind of use, perhaps 2 kinds or more kinds of use that combines.
Also have; In the present invention; As the metal alkoxide class, also can use by 2 kinds or more kinds of metal alkoxide classes and react compound alkoxide that resulting compound alkoxide, a kind or 2 kinds or more kinds of metal alkoxide class and a kind or 2 kinds or more kinds of reacting metal salts obtain and their combination.
The example that is reacted resulting compound alkoxide by 2 kinds or more kinds of metal alkoxide classes has, the compound alkoxide that is obtained by the alkoxide reaction of the alkoxide of alkali metal or alkaline-earth metal and transition metal, the compound alkoxide that obtains with the complex salt form through the combination of 3B family element etc.
Its object lesson has been enumerated, BaTi (OR)
6, SrTi (OR)
6, BaZr (OR)
6, SrZr (OR)
6, LiNb (OR)
6, LiTa (OR)
6And their combination, and LiVO (OR)
4, MgAl
2(OR)
8, (RO)
3SiOAl (OR ')
2, (RO)
3SiOTi (OR ')
3, (RO)
3SiOZr (OR ')
3, (RO)
3SiOB (OR ')
2, (RO)
3SiONb (OR ')
4, (RO)
3SiOTa (OR ')
4Deng the reactant of silane oxide and above-mentioned metal alkoxide class and condensation polymer thereof etc., R wherein and R ' expression alkyl etc.
The compound alkoxide that obtains as a kind or 2 kinds or more kinds of metal alkoxide class and a kind or 2 kinds or more kinds of reacting metal salts can be an example with the resulting compound of reaction by slaine and metal alkoxide class.
As slaine, can example chloride, nitrate, sulfate, acetate, formates, oxalates etc. are arranged; As the metal alkoxide class, can example be and the same material of above-mentioned metal alkoxide class.
The quantity of employed metal alkoxide class is so long as the quantity that formed chemisorbed film is not exerted an influence just has no particular limits; Especially, serve as preferred to use catalytic amount with respect to the metal species surfactant, and then; More preferably it is 0.001～1mol with respect to 1mol metal species surfactant, further is preferably 0.001～0.2mol, perhaps; More preferably oxide conversion mol number is 0.001～1mol, and is preferred for further in 0.001～0.2mol scope.These metal oxides can independent a kind of use, also can be 2 kinds or more kinds of use that combines.
Metal alkoxide class partial hydrolysis product is to instigate resulting material before the metal alkoxide class complete hydrolysis, and the example that can enumerate has, for example, and the precursor of metal oxide sol or the material that exists with the oligomer state etc.
The preferred example that can specifically enumerate has, and having does not have cohesion and the dispersate of the character of stable dispersion under the situation that does not have acid, alkali and/or dispersion stabilizer, in organic solvent.Here, said dispersate is meant the minuteness particle that in dispersion, disperses.Specifically, can example be colloidal particle etc.Here said do not have the cohesion and the state of stable dispersion is meant: under the situation that does not have acid, alkali and/or dispersion stabilizer; In organic solvent; The state of inhomogeneous dispersion is not condensed and do not had to the dispersate of hydrolysis product, preferably representes transparent and uniform state.So-called transparent; Be meant the state that visible light transmissivity is high; Specifically; With dispersate be that the optical path length of 0.5 weight %, quartz cell is that 1cm, organic solvent are that control sample, light wavelength are the spectrophotometric transmittance measured under the condition of 550nm when representing by oxide conversion concentration, serve as preferred with the represented state of 80～100% transmitance.Particle diameter for the dispersate of hydrolysis product does not have special restriction, but in order to obtain high visible light transmissivity, is generally 1～100nm scope, preferred 1～50nm, more preferably 1～10nm.About acid, alkali, dispersion stabilizer, will retell in the back.
The example of the manufacturing approach of preferred metal alkoxide sector of breakdown hydrolysis product is; In organic solvent; In not having acid, alkali and/or dispersion stabilizer to exist down; Use for the metal alkoxide class of above-mentioned example and to be equal to or greater than 0.5 times and less than the water of 2.0 times of moles, in the method that is hydrolyzed to the organic solvent reflow temperature range from-100 ℃.
Specifically, can example have,
(1) in organic solvent, under the situation that does not have acid, alkali and/or dispersion stabilizer, adds for the metal alkoxide class and to be equal to or greater than 0.5 times and less than the method for the water of 2.0 times of moles;
(2) in organic solvent; Under the situation that does not have acid, alkali and/or dispersion stabilizer; The temperature of beginning hydrolysis or more low temperature, or 0 ℃ or more low temperature, preferably-50 ℃～-100 ℃ scopes, add for the metal alkoxide class and to be equal to or greater than 1.0 times and less than the method for the water of 2.0 times of moles;
(3) in organic solvent; Under the situation that does not have acid, alkali and/or dispersion stabilizer; On one side dilute the methods such as concentration that institute adds water and control hydrolysis rate through waiting to the control that adds water speed, with water-soluble solvent, on one side adding is equal to or greater than 0.5 times and less than the method for the water of 2.0 times of moles for the metal alkoxide class; Deng.
In the method for above-mentioned (1), in arbitrary temp down after the water treatment with ormal weight, can the temperature of beginning hydrolysis or more low temperature perhaps at-20 ℃ or more further add water to react under the temperature conditions of low temperature.
The reaction of metal alkoxide class and water is although can carry out without the metal alkoxide class is directly mixed with water, in organic solvent, to carry out to preferably.Specifically; Can adopt as in the organic solvent solution of metal alkoxide class, adding method, suspending or dissolving any method in the method for adding metal alkoxide class in the organic solvent of water or its organic solvent solution, but serve as preferred with the method that adds water after the former with the water of organic solvent diluting.
Used water, so long as neutral, just have no particular limits, serve as preferred with pure water or distilled water, the words that its amount needs only in the scope of afore mentioned rules just have no particular limits, can be by having as the dispersate of destination properties to select arbitrarily.
For the concentration of the metal alkoxide class in the organic solvent, so long as, just have no particular limits, usually in 5～30 weight % scopes suppressing rapid heating, having the scope of the flowability that can stir.
Temperature for the reaction of the metal alkoxide class in the method for above-mentioned (1) and water does not have special restriction, usually-100～+ 100 ℃ of scopes, with from-20 ℃ to the scope by the boiling point of employed organic solvent or the alcohol deviate from by hydrolysis serve as preferred.
Add the stability that coolant-temperature gage depends on the metal alkoxide class in the method for above-mentioned (2); So long as the temperature of beginning hydrolysis or more low temperature or 0 ℃ or the more words of low temperature; Just have no particular limits; But, serve as preferred in-50 ℃～-100 ℃ temperature range, in the metal alkoxide class, to add water according to the kind of metal alkoxide class.Also have, also can adopt: add water at low temperatures and after the slaking certain hour, under the reflux temperature from room temperature to used solvent, be hydrolyzed, the step of going forward side by side is carried out dehydration condensation.
Can be even without the temperature range of using special cooling device also can cool off for example under the scope from 0 ℃ to room temperature; Method with control adds beyond the water speed equitemperature is controlled hydrolysis rate, carries out metal alkoxide class and the reaction of water in the method for above-mentioned (3) thus.Also can under the reflux temperature from room temperature to used solvent, be hydrolyzed after the slaking of certain hour, the step of going forward side by side is carried out dehydration condensation.
As employed organic solvent; So that can be used as dispersate in this organic solvent, the hydrolysis product of metal alkoxide class is separated into preferably; Can consider at low temperature from the reaction of water treatment metal alkoxide class, big with the solubility of water, at the noncondensing solvent of low temperature for more preferably.
As the object lesson of employed organic solvent, alcohols solvents such as methyl alcohol, ethanol, isopropyl alcohol have been enumerated; Halogenated hydrocarbon solvents such as carrene, chloroform, chlorobenzene; Varsols such as hexane, cyclohexane, benzene,toluene,xylene; Ether solvents such as oxolane, ether, dioxane; Ketones solvents such as acetone, MEK, methyl iso-butyl ketone (MIBK); Amide solvents such as dimethyl formamide, N-methyl pyrrolidone; Sulfoxide kind solvents such as dimethyl sulfoxide (DMSO); Polysiloxanes such as methyl polysiloxane, octamethylcy-clotetrasiloxane, decamethylcyclopentaandoxane, methyl phenyl silicone (spy opens flat 9-208438 communique etc.) etc.
These solvents can independent a kind of use or 2 kinds or more kinds of mixing use.
In the occasion of using as mixed solvent, with being combined as preferably of the lower alcohol solvent class of varsols such as toluene, xylenes and methyl alcohol, ethanol, isopropyl alcohol, the tert-butyl alcohol etc.At the lower alcohols solvent of this occasion, with the alcohols solvent that uses 2 grades of isopropyl alcohol, the tert-butyl alcohols etc. or bigger level for more preferably.Mixing ratio for mixed solvent has no particular limits, and serves as preferred with the volume ratio of varsol and lower alcohols solvent in 99/1～50/50 scope.
Also have, when water made the metal alkoxide class be hydrolyzed reaction, adding acid, alkali or dispersion stabilizer were good.For acid and alkali; So long as play degumming agent that coagulable deposition is disperseed again, make the hydrolysis of metal alkoxide class, dehydrating condensation and make catalyst that uses in the dispersate of colloidal particle etc. and the dispersant function that plays the dispersate that is generated, just have no particular limits.
Acid or alkali in this occasion; Make the hydrolysis of metal alkoxide class, dehydrating condensation and make catalyst used in the dispersate of colloidal particle etc. and the dispersant that plays the dispersate that is generated so long as play the degumming agent that coagulable deposition is disperseed again, foregoing conduct, just have no particular limits.
The acid enumerated, for hydrochloric acid, nitric acid, boric acid, boric acid and other mineral acid fluoride, acetic acid, formic acid, oxalic acid, carbonic acid, trifluoroacetic acid, p-toluenesulfonic acid, methanesulfonic acid and the like; diphenyl hexafluorophosphate Iodine
Salt hexafluorophosphate triphenyl
salt, an acid generated by the illumination photoacid generator.
What used alkali was enumerated has, triethanolamine, triethylamine, 1,8-diazabicylo [5,4,0]-7-hendecene, ammoniacal liquor, dimethylformamide, phosphine etc.
Dispersion stabilizer is the reagent with the dispersate of making stable dispersion effect in decentralized medium, has enumerated anticoagulants such as degumming agent, protecting colloid, surfactant etc.The example of specifically enumerating has, polybasic carboxylic acids such as glycolic acid, gluconic acid, lactic acid, tartaric acid, citric acid, malic acid, butanedioic acid; Hydroxycarboxylic acid; Phosphoric acid such as pyrophosphoric acid, tripolyphosphate; Acetylacetone,2,4-pentanedione, methyl acetoacetate, ethyl acetoacetate, acetoacetate n-propyl, isopropyl acetoacetate, the positive butyl ester of acetoacetate, the secondary butyl ester of acetoacetate, tert-butyl acetoacetate, 2; 4-acetyl butyryl, 2; 4-heptadione, 3; 5-heptadione, 2,4-acetyl caproyl, 2,4-diketone in the ninth of the ten Heavenly Stems, 5-methyl-acetyl butyryl etc. have the multidentate ligand compound of strong sequestering power to metallic atom; ス Le パ-ス 3000,9000,17000,20000,24000 (above), Disperbyk-161 ,-162 ,-163 ,-164 fatty amine, hydrogenation stearic acid, polyesteramines such as (above) by PVC Star Network ケ ミ-company's production by the production of ゼ ネ カ company; Dimethyl polysiloxane-methyl (polysiloxanes alkylidene) silicone copolymers, trimethyl silicane ketone acid, carboxy-modified silicone oil, amino modified polysiloxane etc. (spy opens flat 9-208438 communique, the spy opens flat 2000-53421 communique etc.) silicone compounds; Deng.
The quantity of employed metal alkoxide class partial hydrolysis product so long as do not influence the quantity of formed organic film, just has no particular limits; Especially; To use the catalytic amount with respect to the metal species surfactant serves as preferred, and then, for 1mol metal species surfactant; Its oxide conversion mol number is 0.001～1mol, and then is preferred in 0.001～0.2mol scope.These metal oxides can independent a kind of use, also can be 2 kinds or more kinds of use that combines.
The metal alkoxide class hydrolysis product that uses among the present invention is to come the resulting product of hydrolysis with 2 times of metal alkoxide class or the water of more times of equivalents.
This hydrolysis product can be the material that metal alkoxide thing class is obtained with the water hydrolysis of 2 times of equivalents of said metal alkoxide class; Also can be: by carrying out partial hydrolysis to the metal alkoxide class with the water of 2 times of equivalents of less than of said metal alkoxide class; Obtain after the metal alkoxide sector of breakdown hydrolysis product, further use the water (with 2 times of equivalents that add up to said metal alkoxide class of the amount of the employed water of partial hydrolysis of front) of ormal weight to come hydrolysis again and obtain this partial hydrolysis product.
The reaction of metal alkoxide class and water can be directly to be mixed with water by the metal alkoxide class without organic solvent to carry out, and but, preferably in organic solvent, makes the reaction of metal alkoxide class and water in the present invention.
Having no particular limits for employed water, but, consider from the viewpoint that obtains few, the fine and close organic film of impurity, serves as preferred to use pure water, distilled water or ion exchange water.
The use amount of water is 2 times of equivalents or the more times of equivalents with respect to said metal alkoxide class, preferably works as weight range at 2.0～8 times, more preferably works as weight range at 3～5 times.
As the method that metal alkoxide class and water are reacted, enumerated,
(1) in the organic solvent solution of metal alkoxide class, adds entry or by the method for the water of organic solvent diluting;
(2) to the method etc. that suspends or dissolved the organic solvent solution that adds metal alkoxide class or metal alkoxide class in the organic solvent of water.In this occasion, the concentration in the organic solvent of metal alkoxide class, so long as, just have no particular limits suppressing rapid heating, having the scope of the flowability that can stir, but serving as preferred in 5～30 weight % scopes.
Employed organic solvent; Preferably, in this organic solvent, the hydrolysis product of metal alkoxide class can be used as dispersate to be disperseed; As concrete example, preferably with the same organic solvent of foregoing metal alkoxide partial hydrolysis product.
Also have, for the water outside organic solvent, acid, alkali or dispersion stabilizer, this hydrolysis product also can unrestrictedly use in the described in front partial hydrolysis product employed equally.
The hydrolysising reacting temperature of metal alkoxide class depends on reactivity and stability of employed metal alkoxide class etc.; Normally-100 ℃ of temperature ranges that reflux to organic solvent, serving as preferred at-100 ℃～-20 ℃.Also can adopt: add water and through after the slaking of certain hour at low temperature, rise to the reflux temperature of employed solvent to the temperature of reactant liquor from room temperature, further be hydrolyzed, dehydration condensation.
Chelating or coordination metallic compound can modulate through in solution of metal compound, adding chelating agent or the complex that the metal of metallic compound therewith forms complex compound.As chelating agent or complex, if can with the metal-chelating or the coordination of metal hydroxides, metal alkoxide class or the hydrolysis product that obtains with water treatment metal alkoxide class, have no particular limits.
Object lesson as chelating agent or complex has been enumerated, saturated fat acids such as acetate, propionic acid, butyric acid, valeric acid, dodecylic acid, tetradecanoic acid, hexadecanoic acid, octadecanoid acid; Saturated fat two acids such as ethanedioic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, decanedioic acid; Unsaturated carboxylic acids such as acrylic acid, methacrylic acid, butenoic acid, oleic acid, maleic acid; Aromatic carboxylic acid classes such as benzoic acid, phenylacetic acid, phthalic acid; Halogenated carboxylic acid such as monoxone, trifluoroacetic acid class; Beta-diketon classes such as acetylacetone,2,4-pentanedione, BA, hexafluoroacetylacetone; 'beta '-ketoester such as methyl acetoacetate, ethyl acetoacetate class; Heterocycles such as oxolane, furans, furancarboxylic acid, thiophene, thiophenic acid, pyridine, nicotinic acid, iso-nicotinic acid; Deng.They can independent a kind or 2 kinds or more kinds of use that combines.
With respect to metal hydroxides, metal alkoxide class or with the metal 1mol in the resulting hydrolysis product of water treatment metal alkoxide class; The addition of chelating agent or complex is 0.1～10 times of mole; With 0.3～2 times of mole serves as preferred, and 0.5～1.2 times of mole is for more preferably.
After chelating agent or complex adding, fully stir whole system, just can obtain metal complex solution.Whipping temp is generally the temperature range of the boiling point from 0 ℃ to employed solvent.Mixing time was generally a few minutes to several hours.Chelating or coordination metallic compound both can separate use, also can be used as in said solution of metal compound the chelating that adds chelating agent or complex and obtain or coordination solution of metal compound use.Also have, can chelating of being modulated or coordination solution of metal compound preserve.
As silanol condensation catalyst, carboxylic metallic salt, carboxylate slaine, carboxylic metallic salt polymer, carboxylic metallic salt chelate, titanate esters and titanate chelate etc. have been enumerated.Specifically can example have, stannous acetate, dibutyl tin laurate, two sad dibutyl tins, dibutyltin diacetate, two laurate dioctyl tins, two sad dioctyl tins, oxalic acid dioctyl tin, two stannous octoates, lead naphthenate, naphthoic acid cobalt, 2 ethyl hexanoic acid iron, dioctyl THIOGLYCOL acid dioctyl tin, dioctyl tin dimaleate salt, dibutyl tin dimaleate salt polymer, stannous methide mercapto propionate polymer, diacetic acid dibutyl tin, diacetyl dioctyltin laurate, purity titanium tetraethoxide, four titanium butoxide, tetraisopropoxy titanium, two (acetylacetone based) dibutoxy titanium etc.
Employed organic acid has been enumerated among the present invention, saturated fat list acid such as formic acid, acetate, propionic acid, butyric acid, isobutyric acid, valeric acid, isovaleric acid, trimethylace tonitric, caproic acid, sad, capric acid, laurate, myristic acid, palmitic acid, stearic acid; Saturated fat diacid such as oxalic acid, malonic acid, butanedioic acid, glutaric acid, adipic acid; The acid of unsaturated fat lists such as acrylic acid, lactic acid, methacrylic acid, crotonic acid, iso-crotonic acid, oleic acid; Unsaturated fat such as fumaric acid, maleic acid diacid; Aromatic carboxylic acids such as benzoic acid, 4-chloro benzoic acid, naphthoic acid; Chloroacetic acid, trifluoroacetic acid etc. are by the substituted aliphatic carboxylic acid of halogen atom; Hydroxycarboxylic acids such as glycolic acid, lactic acid, malic acid, citric acid; Phenylacetic acid, 3-phenylpropionic acid etc. are by the substituted aliphatic carboxylic acid of aromatic radical; Sulfonic acid such as benzene sulfonic acid, p-methyl benzenesulfonic acid, methanesulfonic acid; Deng.
In these organic acids, from the activity of the hydrolization group of optimizing the metal species surfactant, handle and consider easily, be that 1～6 organic acid serves as preferably with pKa value (logarithm value of the inverse of acid ionization constant), with the pKa value at 2～5 organic acid for more preferably.
Acid ionization constant Ka can use various electrodes such as glass electrode, metal electrode, metallic amalgam electrode, oxidation-reduction electrode, ISE to be come accurately to measure by potentiometer.Among the present invention, acid ionization constant Ka can be tried to achieve by the pH value of measuring in the aqueous solution (undissolved material is then in the mixed solvent of water and suitable organic solvent or suitable organic solvent in water).The pKa value has with condition determination is different ± about 0.3 difference.Be again; Various organic acid acid ionization constant Ka or pKa value are at A.E.Martell; R.M.Smith compiles, 1974,1975,1977 and nineteen eighty-two " Critical Stability Constants (the marginal stability constant) " published by Plenum publishing house 1; On the books in 2,3,5 volumes.
As acid catalyst; Can example have; Organic acids such as the acid of ore deposits such as hydrochloric acid, nitric acid, boric acid, fluoboric acid, acetate, formic acid, oxalic acid, carbonic acid, trifluoroacetic acid, p-methyl benzenesulfonic acid, methanesulfonic acid etc.; And then; Can be by the acidic smooth acid producing agent of illumination, specifically be hexafluorophosphoric acid diphenyl iodine
salt, hexafluorophosphoric acid triphenyl
salt etc.
The metal species surfactant with at least 1 or more a plurality of hydroxyls in the aforementioned solution (b) so long as in same molecule, have hydroxyl and hydrophobic grouping at least, just has no particular limits.Specifically can example be to serve as preferred with the represented compound of aforementioned formula (III).
R in the formula (III)
1, M, X, n and m meaning all the same.At (m-n-1) is 2 or more for a long time, X is identical or different all can.
Also have, in the aforementioned solution (b), except containing metal species surfactant, can also contain the interactional catalyst of metal species surfactant therewith with at least 1 or more a plurality of hydroxyls.As described catalyst, what enumerate is and employed same catalyst in aforementioned solution (a).
With the compound of aforementioned formula (III) expression can example have below the compound that illustrates etc.Again, example is to be the example of the compound of metallic atom M with the silicon atom.
CH
3CH
2O(CH
2)
15Si(OCH
3)(OH)
2
CF
3CH
2O(CH
2)
15Si(OCH
3)
1(OH)
2
CH
3(CH
2)
2Si(CH
3)
2(CH
2)
15Si(OCH
3)(OH)
2
CH
3(CH
2)
6Si(CH
3)
2(CH
2)
9Si(OCH
3)(OH)
2
CH
3COO(CH
2)
15Si(OCH
3)(OH)
2
CF
3(CF
2)
5(CH
2)
2Si(OCH
3)(OH)
2
CF
3(CF
2)
7(CH＝CH)
3Si(OCH
3)(OH)
2
CH
3CH
2O(CH
2)
15Si(OC
2H
5)(OH)
2
CH
3(CH
2)
2Si(CH
3)
2(CH
2)
15Si(OC
2H
5)(OH)
2
CH
3(CH
2)
6Si(CH
3)
2(CH
2)
9Si(OC
2H
5)(OH)
2
CF
3(CH
2)
6Si(CH
3)
2(CH
2)
9Si(OC
2H
5)(OH)
2
CH
3COO(CH
2)
15Si(OC
2H
5)(OH)
2
CF
3COO(CH
2)
15Si(OC
2H
5)(OH)
2
CF
3COO(CH
2)
15Si(OCH
3)(OH)
2
CF
3(CF
2)
9(CH
2)
2Si(OC
2H
5)(OH)
2
CF
3(CF
2)
7(CH
2)
2Si(OC
2H
5)(OH)
2
CF
3(CF
2)
5(CH
2)
2Si(OC
2H
5)(OH)
2
CF
3(CF
2)
7(CH＝CH)
3Si(OC
2H
5)(OH)
2
CF
3(CF
2)
9(CH
2)
2Si(OCH
3)(OH)
2
CF
3(CF
2)
5(CH
2)
2Si(OCH
3)(OH)
2
CF
3(CF
2)
7(CH
2)
2Si(CH
3)(OH)
2
CF
3(CF
2)
9(CH
2)
2Si(CH
3)(OH)
2
CH
3CH
2O(CH
2)
15Si(OCH
3)
2(OH)
CF
3CH
2O(CH
2)
15Si(OCH
3)
2(OH)
CH
3(CH
2)
2Si(CH
3)
2(CH
2)
15Si(OCH
3)
2(OH)
CH
3(CH
2)
6Si(CH
3)
2(CH
2)
9Si(OCH
3)
2(OH)
CH
3COO(CH
2)
15Si(OCH
3)
2(OH)
CF
3(CF
2)
5(CH
2)
2Si(OCH
3)
2(OH)
CH
3CH
2O(CH
2)
15Si(OC
2H
5)
2(OH)
CF
3(CF
2)
7(CH＝CH)
3Si(OCH
3)
2(OH)
CH
3(CH
2)
2Si(CH
3)
2(CH
2)
15Si(OC
2H
5)
2(OH)
CH
3(CH
2)
6Si(CH
3)
2(CH
2)
9Si(OC
2H
5)
2(OH)
CF
3(CH
2)
6Si(CH
3)
2(CH
2)
9Si(OC
2H
5)
2(OH)
CH
3COO(CH
2)
15Si(OC
2H
5)
2(OH)
CF
3COO(CH
2)
15Si(OC
2H
5)
2(OH)
CF
3COO(CH
2)
15Si(OCH
3)
2(OH)
CF
3(CF
2)
9(CH
2)
2Si(OC
2H
5)
2(OH)
CF
3(CF
2)
7(CH
2)
2Si(OC
2H
5)
2(OH)
CF
3(CF
2)
5(CH
2)
2Si(OC
2H
5)
2(OH)
CF
3(CF
2)
7(CH＝CH)
3Si(OC
2H
5)
2(OH)
CF
3(CF
2)
9(CH
2)
2Si(OCH
3)
2(OH)
CF
3(CF
2)
5(CH
2)
2Si(OCH
3)
2(OH)
CF
3(CF
2)
7(CH
2)
2Si(CH
3)(OC
2H
5)(OH)
CF
3(CF
2)
7(CH
2)
2Si(CH
3)(OCH
3)(OH)
CF
3(CH
2)
2Si(OCH
3)(OH)
2
CF
3(CF
2)
3(CH
2)
2Si(OCH
3)(OH)
2
CF
3(CF
2)
5(CH
2)
2Si(OCH
3)(OH)
2
CF
3(CF
2)
7(CH
2)
2Si(OCH
3)(OH)
2
CF
3(CF
2)
3(CH
2)
3Si(OCH
3)(OH)
2
CF
3(CF
2)
5(CH
2)
3Si(OCH
3)(OH)
2
CF
3(CF
2)
7(CH
2)
3Si(OCH
3)(OH)
2
CF
3(CF
2)
4O(CF
2)
2(CH
2)
2Si(OCH
3)(OH)
2
CF
3(CF
2)
4O(CF
2)
2(CH
2)
3Si(OCH
3)(OH)
2
CF
3(CF
2)
7(CH
2)
2O(CH
2)
3Si(OCH
3)(OH)
2
CF
3(CF
2)
7CONH(CH
2)
2Si(OCH
3)(OH)
2
CF
3(CF
2)
7CONH(CH
2)
3Si(OCH
3)(OH)
2
CF
3(CF
2)
3O[CF(CF
3)CF(CF
3)O]
2CF(CF
3)CONH(CH
2)
3Si(OCH
3)(OH)
2
CF
3(CH
2)
2Si(OCH
3)
2(OH)
CF
3(CF
2)
3(CH
2)
2Si(OCH
3)
2(OH)
CF
3(CF
2)
5(CH
2)
2Si(OCH
3)
2(OH)
CF
3(CF
2)
7(CH
2)
2Si(OCH
3)
2(OH)
CF
3(CF
2)
3(CH
2)
3Si(OCH
3)
2(OH)
CF
3(CF
2)
5(CH
2)
3Si(OCH
3)
2(OH)
CF
3(CF
2)
7(CH
2)
3Si(OCH
3)
2(OH)
CF
3(CF
2)
4O(CF
2)
2(CH
2)
2Si(OCH
3)
2(OH)
CF
3(CF
2)
4O(CF
2)
2(CH
2)
3Si(OCH
3)
2(OH)
CF
3(CF
2)
7(CH
2)
2O(CH
2)
3Si(OCH
3)
2(OH)
CF
3(CF
2)
7CONH(CH
2)
2Si(OCH
3)
2(OH)
CF
3(CF
2)
7CONH(CH
2)
3Si(OCH
3)
2(OH)
CF
3(CF
2)
3O[CF(CF
3)CF(CF
3)O]
2CF(CF
3)C
ONH(CH
2)
3Si(OCH
3)
2(OH)
CH
3(CH
2)
7Si(OCH
3)(OH)
2
CH
3(CF
2)
7(CH
2)
2Si(OCH
3)(OH)
2
CH
3(CF
2)
7(CH
2)
2Si(NCO)(OH)
2
CH
3(CF
2)
8(CH
2)
2Si(OCH
3)(OH)
2
CH
3(CF
2)
8(CH
2)
2Si(NCO)(OH)
2
CH
3(CF
2)
9(CH
2)
2Si(OCH
3)(OH)
2
CH
3(CF
2)
9(CH
2)
2Si(NCO)(OH)
2
CH
3CH
2(CF
2)
6(CH
2)
2Si(OCH
3)(OH)
2
CH
3CH
2(CF
2)
6(CH
2)
2Si(OCH
3)(OH)
2
CH
3CH
2(CF
2)
6(CH
2)
2Si(NCO)(OH)
2
CH
3CH
2(CF
2)
8(CH
2)
2Si(OCH
3)(OH)
2
CH
3CH
2(CF
2)
8(CH
2)
2Si(NCO)(OH)
2
CH
3CH
2(CF
2)
10(CH
2)
2Si(OCH
3)(OH)
2
CH
3(CF
2)
4O(CF
2)
2(CH
2)
2Si(OCH
3)(OH)
2
CH
3(CF
2)
7(CH
2)
2O(CH
2)
3Si(OCH
3)(OH)
2
CH
3(CF
2)
8(CH
2)
2O(CH
2)
3Si(OCH
3)(OH)
2
CH
3(CF
2)
9(CH
2)
2O(CH
2)
3Si(OCH
3)(OH)
2
CH
3CH
2(CF
2)
6(CH
2)
2O(CH
2)
3Si(OCH
3)(OH)
2
CH
3(CF
2)
6ONH(CH
2)
3Si(OCH
3)(OH)
2
CH
3(CF
2)
8CONH(CH
2)
3Si(OCH
3)(OH)
2
CH
3(CF
2)
3O[CF(CF
3)CF(CF
3)O]
2CF(CF
3)CONH(CH
2)
3Si(OCH
3)(OH)
2
CF
3(CF
2)
3(CH
2)
2Si(CH
3)(OCH
3)(OH)
CF
3(CF
2)
5(CH
2)
2Si(CH
3)(OCH
3)(OH)
CF
3(CH
2)
2Si(CH
3)(OCH
3)(OH)
CF
3(CF
2)
3(CH
2)
3Si(CH
3)(OCH
3)(OH)
CF
3(CF
2)
5(CH
2)
3Si(CH
3)(OCH
3)(OH)
CF
3(CF
2)
7(CH
2)
3Si(CH
3)(OCH
3)(OH)
CF
3(CF
2)
4(CF
2)
2(CH
2)
2Si(CH
3)(OCH
3)(OH)
CF
3(CF
2)
4(CF
2)
2(CH
2)
3Si(CH
3)(OCH
3)(OH)
CF
3(CF
2)
4(CH
2)
2O(CH
2)
3Si(CH
3)(OCH
3)(OH)
CF
3(CF
2)
7CONH(CH
2)
2Si(CH
3)(OCH
3)(OH)
CF
3(CF
2)
7CONH(CH
2)
3Si(CH
3)(OCH
3)(OH)
CF
3(CF
2)
3O[CF(CF
3)CF(CF
3)O]
2CF(CF
3)CONH(CH
2)
3Si(CH
3)(OCH
3)(OH)
CH
3(CH
2)
7Si(OCH
3)
2(OH)
CH
3(CF
2)
7(CH
2)
2Si(OCH
3)
2(OH)
CH
3(CF
2)
7(CH
2)
2Si(CH
3)(OCH
3)(OH)
CH
3(CF
2)
7(CH
2)
2Si(OCH
3)
2(OH)
CH
3(CF
2)
7(CH
2)
2Si(NCO)
2(OH)
CH
3(CF
2)
8(CH
2)
2Si(OCH
3)
2(OH)
CH
3(CF
2)
8(CH
2)
2Si(NCO)
2(OH)
CH
3(CF
2)
9(CH
2)
2Si(OCH
3)
2(OH)
CH
3(CF
2)
9(CH
2)
2Si(NCO)
2(OH)
CH
3CH
2(CF
2)
6(CH
2)
2Si(OCH
3)
2(OH)
CH
3CH
2(CF
2)
6(CH
2)
2Si(NCO)
2(OH)
CH
3CH
2(CF
2)
8(CH
2)
2Si(OCH
3)
2(OH)
CH
3CH
2(CF
2)
8(CH
2)
2Si(NCO)
2(OH)
CH
3CH
2(CF
2)
10(CH
2)
2Si(OCH
3)
2(OH)
CH
3(CF
2)
40(CF
2)
2(CH
2)
2Si(OCH
3)
2(OH)
CH
3(CF
2)
7(CH
2)
2O(CH
2)
3Si(OCH
3)
2(OH)
CH
3(CF
2)
8(CH
2)
2O(CH
2)
3Si(OCH
3)
2(OH)
CH
3(CF
2)
9(CH
2)
2O(CH
2)
3Si(OCH
3)
2(OH)
CH
3CH
2(CF
2)
6(CH
2)
2O(CH
2)
3Si(OCH
3)
2(OH)
CH
3(CF
2)
6CONH(CH
2)
3Si(OCH
3)
2(OH)
CH
3(CF
2)
8CONH(CH
2)
3Si(OCH
3)
2(OH)
CH
3(CF
2)
3O[CF(CF
3)CF(CF
3)O]
2CF(CF
3)CONH(CH
2)
3Si(OCH
3)
2(OH)
CH
3CH
2O(CH
2)
15Si(OH)
3
CF
3CH
2O(CH
2)
15Si(OH)
3
CH
3(CH
2)
2Si(CH
3)
2(CH
2)
15Si(OH)
3
CH
3(CH
2)
6Si(CH
3)
2(CH
2)
9Si(OH)
3
CH
3COO(CH
2)
15Si(OH)
3
CF
3(CF
2)
5(CH
2)
2Si(OH)
3
CF
3(CF
2)
7(CH＝CH)
3Si(OH)
3
CH
3CH
2O(CH
2)
15Si(OH)
3
CH
3(CH
2)
2Si(CH
3)
2(CH
2)
15Si(OH)
3
CH
3(CH
2)
6Si(CH
3)
2(CH
2)
9Si(OH)
3
CF
3(CH
2)
6Si(CH
3)
2(CH
2)
9Si(OH)
3
CH
3COO(CH
2)
15Si(OH)
3
CF
3COO(CH
2)
15Si(OH)
3
CF
3(CF
2)
9(CH
2)
2Si(OH)
3
CF
3(CF
2)
7(CH
2)
2Si(OH)
3
CF
3(CF
2)
5(CH
2)
2Si(OH)
3
CF
3(CF
2)
7(CH＝CH)
3Si(OH)
3
CF
3(CF
2)
9(CH
2)
2Si(OH)
3
CF
3(CF
2)
5(CH
2)
2Si(OH)
3
CF
3(CF
2)
7(CH
2)
2Si(CH
3)
2(OH)
CF
3(CH
2)
2Si(OH)
3
CF
3(CF
2)
3(CH
2)
2Si(OH)
3
CF
3(CF
2)
5(CH
2)
2Si(OH)
3
CF
3(CF
2)
7(CH
2)
2Si(OH)
3
CF
3(CF
2)
3(CH
2)
3Si(OH)
3
CF
3(CF
2)
5(CH
2)
3Si(OH)
3
CF
3(CF
2)
7(CH
2)
3Si(OH)
3
CF
3(CF
2)
4O(CF
2)
2(CH
2)
2Si(OH)
3
CF
3(CF
2)
4O(CF
2)
2(CH
2)
3Si(OH)
3
CF
3(CF
2)
7(CH
2)
2O(CH
2)
3Si(OH)
3
CF
3(CF
2)
7CONH(CH
2)
2Si(OH)
3
CF
3(CF
2)
7CONH(CH
2)
3Si(OH)
3
CF
3(CF
2)
3O[CF(CF
3)CF(CF
3)O]
2CF(CF
3)CONH(CH
2)
3Si(OH)
3
CH
3(CH
2)
7Si(OH)
3
CH
3(CF
2)
7(CH
2)
2Si(OH)
3
CH
3(CF
2)
7(CH
2)
2Si(OH)
3
CH
3(CF
2)
8(CH
2)
2Si(OH)
3
CH
3(CF
2)
9(CH
2)
2Si(OH)
3
CH
3CH
2(CF
2)
6(CH
2)
2Si(OH)
3
CH
3CH
2(CF
2)
8(CH
2)
2Si(OH)
3
CH
3CH
2(CF
2)
10(CH
2)
2Si(OH)
3
CH
3(CF
2)
40(CF
2)
2(CH
2)
2Si(OH)
3
CH
3(CF
2)
7(CH
2)
2O(CH
2)
3Si(OH)
3
CH
3(CF
2)
8(CH
2)
2O(CH
2)
3Si(OH)
3
CH
3(CF
2)
9(CH
2)
2O(CH
2)
3Si(OH)
3
CH
3CH
2(CF
2)
6(CH
2)
2O(CH
2)
3Si(OH)
3
CH
3(CF
2)
6CONH(CH
2)
3Si(OH)
3
CH
3(CF
2)
8CONH(CH
2)
3Si(OH)
3
CH
3(CF
2)
3O[CF(CF
3)CF(CF
3)O]
2CF(CF
3)CONH(CH
2)
3Si(OH)
3
CF
3(CF
2)
3(CH
2)
2Si(CH
3)(OH)
2
CF
3(CF
2)
5(CH
2)
2Si(CH
3)(OH)
2
CF
3(CH
2)
2Si(CH
3)(OH)
2
CF
3(CF
2)
3(CH
2)
3Si(CH
3)(OH)
2
CF
3(CF
2)
5(CH
2)
3Si(CH
3)(OH)
2
CF
3(CF
2)
7(CH
2)
3Si(CH
3)(OH)
2
CF
3(CF
2)
4(CF
2)
2(CH
2)
2Si(CH
3)(OH)
2
CF
3(CF
2)
4(CF
2)
2(CH
2)
3Si(CH
3)(OH)
2
CF
3(CF
2)
4(CH
2)
2O(CH
2)
3Si(CH
3)(OH)
2
CF
3(CF
2)
7CONH(CH
2)
2Si(CH
3)(OH)
2
CF
3(CF
2)
7CONH(CH
2)
3Si(CH
3)(OH)
2
CF
3(CF
2)
3O[CF(CF
3)CF(CF
3)O]
2CF(CF
3)CONH(CH
2)
3Si(CH
3)(OH)
2
CH
3(CF
2)
7(CH
2)
2Si(CH
3)(OH)
2
These compounds can independent a kind or 2 kinds or more kinds of use that combines.
As the organic solvent that in solution (a) and solution (b), uses, serve as preferably with varsol, fluorinated hydrocarbon solvent and type siloxane solvent, varsol is for more preferably.Wherein, boiling point at 100 ℃～250 ℃ preferred for especially.
That specifically enumerates has, varsols such as n-hexane, cyclohexane, benzene,toluene,xylene, naphtha, solvent naphtha, benzinum, oil light fraction, isoparaffin, positive paraffin hydrocarbon, decahydronaphthalene, industrial gasoline, lam-oil, ligroin; CBr
2ClCF
3, CClF
2CF
2CCl
3, CClF
2CF
2CHFCl, CF
3CF
2CHCl
2, CF
3CBrFCBrF
2, CClF
2CClFCF
2CCl
3, Cl (CF
2CFCl)
2Cl, Cl (CF
2CFCl)
2CF
2CCl
3, Cl (CF
2CFCl)
3Fluon kind solvents such as Cl; Fluorinert (3M Company products), aflude fluorinated hydrocarbon solvents such as (Asahi Glass Company products); Type siloxane solvents such as dimethyl siloxane, phenyl siloxane, alkyl-modified siloxanes, polyether silicone.These solvents can independent a kind or 2 kinds or more kinds of use that combines.
The content of the metal species surfactant in the organic solvent solution has no particular limits, but in order to obtain fine and close monomolecular film, under any situation in solution (a), solution (b), all serving as preferred in 1～30 weight % scope.
Also have; In occasion with solution (a), can with the interactional catalyst consumption of metal species surfactant, so long as do not influence the words of quantity of the rerum natura of formed monomolecular organic film; Just have no particular limits; With respect to 1 mole metal class surfactant, oxide conversion molal quantity is generally 0.001～1mol, serves as preferred with 0.001～0.2mol.
Method for producing organic thin film of the present invention is characterised in that it has comprised the operation of aforementioned solution (a) or solution (b) (following also be referred to as them " organic solvent solution ") and substrate contacts, has set or remain on prescribed limit to the amount of moisture in this solution.Through being controlled in prescribed limit to the amount of moisture in the organic solvent solution, just can on the substrate of all materials, form fine and close organic film rapidly.
Amount of moisture in the organic solvent solution depends on the kind of employed substrate, metal species surfactant, catalyst, organic solvent etc.Specifically; Should be to be less than or equal to cause that obstruction is to the chemisorbed of substrate surface, the quantity that can not make fine and close monomolecular film, make the loss amount of used metal species surfactant big, make problems such as catalysqt deactivation; And, be equal to or greater than the quantity of enough promotions, activation film forming.
The so-called enough quantity of promotion, activation film forming is meant; For example; Make the contacted occasion of this solution and substrate with infusion process, 10min with interior, preferably 5min with interior time of contact under, just can be quickly and on whole base plate, form the fine and close required quantity of organic film uniformly.Specifically be, with 50ppm or mostly serve as preferred, with scope, more specifically say that with 50～1000ppm scope for more preferably, 200～800ppm scope is preferred for especially from 50ppm to the saturation water component organic solvent.When amount of moisture at 50ppm or more for a long time, can form organic film rapidly, and amount of moisture does not have the problem of inactivations such as so-called metal species surfactant at 1000ppm or still less the time.
Be that the amount of moisture shown in here is that the value that the part of organic solvent solution is measured through Ka Er-Fei Xiefa is got in expression again.So long as the value of using the device of the method principle to measure does not have special restriction for determinator.Be again,, get the part of homogeneous solution and measure, and be divided into 2 layers occasion, then get the part of organic solvent layer to measure at organic solvent layer and water layer when organic solvent solution is uniform occasion; Be dispersed in the organic solvent and the situation of indissociable state and be in, then represent the value that former state takes dispersion liquid to measure for water stratification.
For containing metal class surfactant, metal oxide etc. can with the method for adjustment of the organic solvent solution of interactional catalyst of metal species surfactant and water, do not have special restriction, what can specifically enumerate is,
(1) to contain the metal species surfactant, can with the organic solvent solution of the interactional catalyst of metal species surfactant in add the method for water;
(2) in the organic solvent solution of metal species surfactant and water, add can with the method for the interactional catalyst of metal species surfactant, etc.
Also have, in order to suppress rapid reaction, with added catalyst in the method for added water in the method for (1), (2) be use organic solvent diluting serve as preferred.
Occasion for the hydrolysis product that can obtain with the interactional catalyst of the metal species surfactant metallic compound that is metal oxide, metal hydroxides, metal alkoxide class, chelating or coordination, metal alkoxide class partial hydrolysis product, with the said metal alkoxide class of water treatment of 2 times of equivalents that are equivalent to the metal alkoxide class or more times of equivalents; Catalyst consumption is not so long as influence the words of quantity of the rerum natura of formed unimolecule organic film; Just have no particular limits; For 1 mole metal class surfactant; Be generally 0.001～1mol; Be preferably 0.001～0.2mol, perhaps oxide conversion molal quantity is generally 0.001～1mol, serves as preferred with 0.001～0.2mol.
Also have, when said can be the organic acid occasion with the interactional catalyst of metal species surfactant, for 1 mole metal class surfactant, be generally 0.001～100mol, be preferably 0.001～10mol.Use this scope can with the interactional catalyst of metal species surfactant, just can form does not rapidly have impurity and fine and close monomolecular film organic film.
Said metal species surfactant, organic solvent, can stir with the mixture of interactional catalyst of metal species surfactant and water, just can obtain organic film manufacturing of the present invention and use solution.Whipping temp is generally-100 ℃～+ 100 ℃, serves as preferred with-20 ℃～+ 50 ℃.Mixing time was generally a few minutes to several hours.Also have, in this occasion, use solution in order to obtain uniform organic film manufacturing, it also is preferred implementing sonicated.
The manufacturing organic film of being modulated with solution in, produce the precipitate of containing metal oxide etc. sometimes, for the unimolecule organic film of the densification that obtains not having impurity, preferably remove impurity such as these precipitates.Precipitate can be removed by operations such as filtering, topple over very easily.
In the contacted operation of substrate of the present invention and said, preferably remain on the specified quantity scope to the amount of moisture in the aforementioned organic solvent solution, repeat this operation 2 times or more times with same solution.
So-called specified quantity scope representes that the prescribed limit with above-mentioned amount of moisture is same meaning, remains on such scope through making amount of moisture, contacts repeatedly repeatedly even without changing liquid that operation also can form densification and organic film uniformly.Use same solution that 2 or more substrates are carried out the operation of 1 contact operation, just can on whole of being contacted, form fine and close with short time of contact and uniform organic film.
Under this occasion; The same solution of what is called is meant the meaning that changes discarded all or part of solution after having carried out contacting process operations 1 time into the situation eliminating of new solution; As back said, all be included in the category of same solution by the solution in the scope that remains on amount of moisture with any method specified quantity.
The method adjusting amount of moisture and remain in the specified quantity scope specifically has,
(1) with organic solvent solution the method for water layer is set contiguously;
(2) coexistence has the method for the water-retaining property material that is in saturation state in organic solvent solution;
(3) make organic solvent solution and the contacted method of gas that contains moisture;
(4) suitably add the method for water, etc.
These methods no matter be use separately or 2 kinds or more kinds of combine use all right.
Used water preferably uses pure water or distilled water so long as neutrality just has no particular limits.Also have, employed organic solvent is anhydrous or just contain in advance some moisture all it doesn't matter.
In above-mentioned (1) method; The occasion of the organic solvent that use varsol etc. separates with water layer; Can be with the form of separating coexistence water layer with organic solvent layer, also can use organic solvent solution in water layer, to circulate or through separating the organic solvent layer that obtains.
Use that lower alcohol etc. is unseparated with water layer, the occasion of solubility is big in the water organic solvent, can example be to adopt with permeable and film etc. that do not pass through organic solvent is that intermediary makes organic solvent solution and the contacted method of water layer etc.
As the water-retaining property material in the method for above-mentioned (2), its material that in organic solvent solution, does not separate water outlet, in organic solvent solution, do not swim preferably.
That specifically enumerates is organic type of water-keeping material such as absorbent polymer; Mineral-type water-keeping materials such as zeolite, silicic acid carclazyte, vermiculite, porous ceramics; Surfactants etc. can form with water the compound etc. of the little micella molecule that is nuclear in solution, wherein, consider from avoiding reasons such as sneaking into of dust etc., and are preferred for especially with glass fiber filter.
Also have, can example be illustrated in the compound that can form with water the little micella molecule that is nuclear in the solution, particularly like surfactant etc. as the water-retaining property material.
Also have,, consider to adopt the method for hydrophilic solvent in order to improve the solubility of water in organic solvent.In this occasion, hydrophilic solvent is also involved as making things convenient for the material of water conservation.
Amount of moisture for being contained in the water-retaining property material has no particular limits, but preferably amount of moisture will become the state that does not dissociate out from the water-retaining property separating substances until the water in organic solvent solution.Also have, also comprised adding water in good time, but made in its material that is included in water conservation.Be to keep the skin wet to solution through the moisture of drawing ambient atmosphere etc. in interface that also can be through being arranged at the water-retaining property material solution and ambient atmosphere or be set to continuously in the solution from ambient atmosphere again.
In the method for above-mentioned (3), gases used so long as do not have influence for each composition in the solution, just have no particular limits, specifically can example air, nitrogen, argon gas etc. are arranged.
The method that obtains containing the gas of moisture has, and in gas, contains the method for moisture, method of gas humidification etc.
As the method that in gas, contains moisture, can example have: pull the plug gas, the method that water is contacted with gas, the method for the gas of former state use moisture vapor etc. such as contact to gas with water or warm water surface.
The method of gas humidification can example have, steam humidification method, water spray add wet method or gasification heating etc.
Make having that the gas that contains moisture and the contacted method of organic solvent solution can example: be blown into the gas that contains moisture in the organic solvent solution or blow to the method on the surface of organic solvent solution; Stir on one side the method that places the atmosphere that contains moisture on one side to organic solvent solution as required, Yi Bian Yi Bian stir organic solvent solution as required and to place through the method for the atmosphere of humidification etc.Method for being blown into the gas that contains moisture in the organic solvent solution serves as preferred to be provided with device for blowing, cleaning device and filter etc. as required.
Also have; In said method (4); Specifically can example have: observe the minimizing of the amount of moisture in the organic solvent solution; Suitably append according to reduction water or with organic solvent that intermiscibility is arranged or same organic solvent diluting the method for water, method water, that form identical organic solvent solution that contains some etc. is provided.
Do not have special restriction for the substrate that is used for method for producing organic thin film of the present invention; To have from the teeth outwards can serve as preferred with the substrate of the functional group of the interaction of molecules of formation organic film in organic solvent solution, and the surface has the substrate of reactive hydrogen preferred for especially.Use the surface that the substrate of reactive hydrogen is arranged,, just can easily on substrate surface, form chemisorbed film through the reactive hydrogen of substrate surface and the chemical interaction of the molecule in the organic solvent solution.
So-called reactive hydrogen is meant easy hydrogen as proton dissociation.The functional group that contains reactive hydrogen has been enumerated, hydroxyl (OH), carboxyl (COOH), aldehyde radical (CHO), imino group (=NH), amino (NH2), mercapto (wherein, is preferred with the hydroxyl SH) etc..
The surface has the substrate of hydroxyl specifically to enumerate; By formed substrates such as metals such as aluminium, copper, stainless steel, glass, silicon chip, pottery, plastics, paper, natural fiber or synthetic fibers, leather, other hydroaropic substances, wherein serving as preferred by the formed substrate of metal, glass, silicon chip, pottery and plastics.
For by the substrate that material constituted that on the such surface of plastics or synthetic fibers, does not have hydroxyl, can contain oxygen plasma atmosphere and carry out preliminary treatment (for example 20min under 100W) through placing substrate surface, introduce hydrophilic radical by corona treatment.The substrate that constitutes by polyamide or polyurethane resin etc.; Because of having imino group from the teeth outwards; Dealcoholization can take place with the alkoxysilyl of metal species surfactant etc. in the reactive hydrogen of this imino group, and (therefore SiO-) key there is no need to carry out surface treatment to form siloxane bond.
Also have, when using the surface not have the substrate of reactive hydrogen, also can be this substrate surface elder generation and from SiCl
4, SiHCl
3, SiH
2Cl
2, Cl-(SiCl
2O)
b-SiCl
3At least a kind of compound selecting in (b in the formula is a natural number) contacts, and carries out dehydrochlorination reaction then, thereby forms the silicon-dioxide-substrate bottom with reactive hydrogen on the surface.
For having no particular limits the method for organic solvent solution and substrate contacts, can use known method.That specifically enumerates has, and infusion process, spin-coating method, spraying process, rolling method, Meyer rod method, silk screen print method, spread coating etc. wherein are preferred with the infusion process.
The operation of organic solvent solution and substrate contacts can be carried out for 1 time for a long time, also can be coated with by the branch short time several times and carry out.In order to promote the formation of film, also can use ultrasonic.
The temperature of contact is so long as just have no particular limits in the words of the scope of the stability that keeps this solution, but, and normally in scope from room temperature to the reflux temperature of modulating the employed solvent of solution.For contact is carried out in suitable temperature, all right solution heating or substrate heating.
The operation of organic solvent solution and substrate contacts is being to serve as the operation that substrate floods in organic solvent solution preferred.Specifically enumerated the method for substrate dipping when keeping the amount of moisture in the organic solvent solution:
(a) moisture adjustment groove and substrate dipping tank are set, make and adjust groove by moisture adjusted the method that the liquid of moisture circulates in the substrate dipping tank;
(b) a plurality of substrate dipping tanks are set, during with a substrate dipping tank dipping substrate, the method for adjustment moisture in other dipping tanks;
(c) mechanism that above-mentioned amount of moisture is remained on prescribed limit, the method that suitably keeps the skin wet etc. directly are set in the substrate dipping tank.
For after having carried out substrate and operation that organic solvent solution contacts removing attached to unnecessary reagent and the impurity on film surface, the surperficial operation (B) of cleaning base plate also can be set.Owing to be provided with matting, just can control thickness.
The method of cleaning so long as the method that can remove the attachment on surface just have no particular limits.Specifically can example have is immersed in method in can the solvent of dissolution of metals class surfactant, in a vacuum or the method for placing the method for evaporation under the normal pressure in the atmosphere, dispelling with inert gases such as drying nitrogens to matrix, etc.
After having carried out substrate and operation that organic solvent solution contacts, stable in order to make on substrate surface formed film, also can be provided with the operation (C) of substrate heating.Serves as the operation (C) of substrate heating preferred afterwards to be arranged on above-mentioned matting (B).The temperature of heating can be done suitable selection with the stability of substrate, film.
In the present invention, the operation that substrate contacts with organic solvent solution is keeping humidity in the space of 60%RH or bigger humidity, to be embodied as more preferably to keep humidity in the space of 40%RH or bigger humidity, to be embodied as preferably.In such space, the moisture in the organic solvent solution can better be kept, even also can form fine and close monomolecular film with good reappearance with the substrate Continuous Contact.
Method for producing organic thin film of the present invention both can be used to make monomolecular film, also can be used to make 2 layers or the multilayer film of multilayer more, was particularly suitable for the manufacturing of monomolecular film.Also have, also can be used as through physical absorption from the teeth outwards the method for film forming and use.
The store method of the solution that uses in the method for producing organic thin film of the present invention can example have; (α) use water treatment to the organic solvent solution that contains metal species surfactant with at least 1 or more a plurality of hydroxyls the metal species surfactant with at least 1 or more a plurality of hydrolization groups and the interactional catalyst of metal species surfactant therewith or (β); Be set in the ormal weight scope to the amount of moisture in this organic solvent solution; When remaining on prescribed limit to the amount of moisture in the above-mentioned organic solvent solution, place method airtight in the container etc.As being set in the amount of moisture in the organic solvent solution ormal weight scope, remaining on the method for ormal weight scope to the amount of moisture in the above-mentioned organic solvent solution, what enumerate is the method same with preceding method.
Through being enclosed in it in the container, just can prevent greatly to cause amount of moisture to reduce in the atmosphere owing to moisture evaporate into organic solvent.Because organic film manufacturing of the present invention is influential to the formation ability of organic film with the amount of moisture in the solution, therefore, even in preservation, serve as preferred also to remain on the amount of moisture in the solution prescribed limit.
Through adopting above-mentioned method for producing organic thin film, the organic film that can obtain monomolecular film, self aggregation film, chemisorbed film and hold these character.
2) the self aggregation film forms and uses solution
The solution that self aggregation film of the present invention forms usefulness is characterised in that, the molecule that forms autohemagglutination film aggregation in solution.
In the organic solvent solution (to call " organic film manufacturing use solution ") of amount of moisture in prescribed limit; The molecule that forms organic film forms under the situation of aggregation, and resulting organic film becomes self aggregation film (organic film manufacturing in the case is called " the self aggregation film forms and uses solution " with solution).
In above-mentioned formula (IV), except X
1Outside expression hydroxyl or the hydrolization group, R
11, M
1, m
1And n
1With the R in the formula (I) of front
1, M, m and n represent same meaning.
In aforementioned formula (V), except X
2Outside expression hydroxyl and the hydrolization group, R
21, R
31, R
41, M
2, Y
2, p
1, q
1, m
2And r
2With the R in the aforementioned formula (II)
2, R
3, R
4, M, Y, p, q, m and r represent same meaning.
As the compound of aforementioned formula (IV) or aforementioned formula (V) expression, specifically example is the compound with aforementioned formula (I) or aforementioned formula (II) expression.
X
1, X
2Hydrolization group might not be arranged, and specifically also can be the compound with aforementioned listed hydroxyls such as compound with formula (III) expression.
The film of self aggregation described in the present invention is meant the film of formed ordered structure under the situation that does not have external forced power.In the self aggregation film forms with solution, the metal species surfactant molecule no longer through solvent with solvation form individualism, but several molecule is assembled and the formation aggregation.
The metal species surfactant that has at least one or more a plurality of hydrolization groups in use is during as the metal species surfactant, and aggregation is by can be with the interactional catalyst of metal species surfactant and the said metal species surfactant of water treatment and obtain; The metal species surfactant that has at least one or more a plurality of hydroxyls in use is during as the metal species surfactant, and aggregation is obtained by this metal species surfactant of water treatment.
The form of aggregation is: molecule is between the hydrophobic part each other or the form that gathers together with molecular separating force, coordinate bond or hydrogen bond etc. between the hydrophilic segment each other; The form that the molecule of film forming is assembled by covalent bonds; Other media such as water form the form of little micella etc. through nuclear or intermediary; Perhaps these forms of combining etc.
Shape for aggregation has no particular limits, and Any shape such as spherical, chain, band shape is all right.The average grain diameter of aggregation has no particular limits, serving as preferred in 10～1000nm scope.
Also have, the Zeta potential of aggregation (interface electric potential) value is with greatly more preferred than the Zeta potential value of the substrate in same solvent.With the Zeta potential of aggregation be just, the Zeta potential value of substrate is for negative preferred for especially.Use has formed the self aggregation film formation of the aggregation with such Zeta potential value and has used solution, just can make to have crystalline, fine and close monomolecular film.
3) chemisorbed film
Chemisorbed film of the present invention is the chemisorbed film that on substrate, forms, and it is characterized in that said substrate does not have crystallinity and chemisorbed film has crystallinity.That is to say that no matter whether substrate has crystallinity, chemisorbed film all has crystallinity.In this occasion, so-called crystallinity, it is passable to be that polycrystalline or monocrystalline all do not have.
4) manufacturing approach of monomolecular film
The manufacturing approach of monomolecular film of the present invention is characterised in that to have and adopt at least a method that is selected from infusion process, spin-coating method, rolling method, Meyer rod method, silk screen print method, woodburytype, spread coating and the spraying process the operation of solution coat on substrate surface that contains the metal species surfactant.This operation is characterised in that, contain with oxyl or acyloxy be the drips of solution of metal species surfactant of hydrolization group on said substrate, the solution that drips is pressurizeed from top, it is spread on substrate.Have no particular limits for amount of dripping and position etc., can come suitably to select according to the position that forms monomolecular film, area.
To the solution that drips from top pressure method; So long as pressurize so that the method that dripping is spread at substrate from liquid upper; Just have no particular limits, specifically can example have waits method of rolling etc. more above that with roller after laying film, thin slice or flat board on the substrate surface.
The solution that contains said metal species surfactant is being that the organic solvent solution that further contains the catalyst of the hydrolization group activation that makes said metal species surfactant serves as preferred.
Description of drawings
Fig. 1 shows the film X ray crystallogram of organic film SAM-25～SAM-27.
Fig. 2 shows in the forming process of SAM-27, dip time be (a) 1s or still less, the SPM collection of illustrative plates of (b) 15s, (c) 30s, the resulting organic film of (d) 1min.
Fig. 3 shows in the forming process of SAM-31, dip time be (a) 1s or still less, the SPM collection of illustrative plates of (b) 15s, (c) 1min, the resulting organic film of (d) 5min.
The specific embodiment
Come further explain the present invention with embodiment below, still, scope of the present invention is not limited in said embodiment.
Embodiment 1
(1) modulation of catalyst-1
Join 12.4g tetraisopropoxy titanium (A-1: purity 99%, titanium oxide conversion concentration are 28.2 weight %, and Japanese Cao Da (strain) makes) in the four-hole boiling flask,,, in ethanol/liquid nitrogen bath, be cooled to-80 ℃ through after the nitrogen replacement with the dissolving of 45.0g toluene.In addition, 1.26g ion exchange water (H
2O/Ti=1.6 (mol ratio)) mixes with the 11.3g isopropyl alcohol, under-80～-70 ℃ the state of cooling, splash in the above-mentioned four-hole boiling flask under stirring.Splash in the process, the liquid temperature in the flask is maintained at-80～-70 ℃.After dripping off, cool off 30min while stirring, be warming up to room temperature under stirring then, the partial hydrolysis solution (C-1) that to have obtained water white titanium oxide conversion concentration be 5 weight %.
(2) modulation of catalyst-2
In the four-hole boiling flask of nitrogen replacement, be dissolved in 530g tetraisopropoxy titanium (A-1: purity 99%, titanium oxide conversion concentration are 28.2 weight %, and Japanese Cao Da (strain) makes) in the 1960g toluene, in ethanol/the dry ice bath, be cooled to-15 ℃.In addition, 30.4g ion exchange water (H
2O/Ti=0.9 (mol ratio)) mixes with the 274g isopropyl alcohol, splash in the above-mentioned four-hole boiling flask under stirring with 90min.Splash in the process, the liquid temperature in the flask is maintained at-15～-10 ℃.After dripping off, stir 30min, be warming up to the room temperature continued then and stir 1h, obtained colourless transparent liquid at-10 ℃.Be cooled to-80 ℃ to this liquid with ethanol/the dry ice bath, under agitation splash into 20.3g ion exchange water (H with 90min
2O/Ti=0.6 (mol ratio)) with the mixed solution of 183g isopropyl alcohol.Drip off the back and get back to room temperature with 3h, at 90～100 ℃ of backflow 2h, having obtained titanium oxide conversion concentration is the water white transparency partial hydrolysis solution (C-2) of 5 weight % this solution.This solution is that average grain diameter is the sharp-pointed monodispersed colloidal sol of 5.6nm.
(3) modulation of catalyst-3
Under 18 ℃ of liquid temperature, blanket of nitrogen, in flask, mix stirring and dissolving to 17.79g (62.6mmol) tetraisopropoxy titanium (A-1: purity 99.9%, titanium oxide conversion concentration are 28 weight %, and Japanese Cao Da (strain) makes) with the 65.31g dehydrated toluene.Be 18～20 ℃ in the liquid temperature, stir under, with 2h to wherein splashing into 1.69g (93.9mmol, H
2The mixture of the water of O/Ti=1.5 (mol ratio), 30.42g dehydration isopropyl alcohol, 30.42g dehydrated toluene (concentration of water be equivalent to the saturation solubility of water in isopropyl alcohol and toluene mixed solvent 22%) has obtained light yellow transparent solution.Further stir 1.5h down for 18 ℃ in the liquid temperature, yellow is grow slightly, and the 2.5h that refluxes then becomes water white transparency liquid.The oxide concentration of solution is 3.4 weight %.In this solution, add toluene, being diluted to oxide concentration is 1.0 weight %, has obtained catalyst (C-3).
(4) modulation of catalyst-4
Be dispersed in the Ludox (daily output chemical industry (strain) is made for IPA-ST-S, 25 weight %) that is scattered in the isopropyl alcohol (IPA) in the dehydrated toluene, obtain the dispersion liquid (C-4) of silica conversion concentration 1 weight %.
(5) modulation of catalyst-5
In four-hole boiling flask, add 12.4g tetraisopropoxy titanium (A-1: purity 99%, titanium oxide conversion concentration are 28.2 weight %, and Japanese Cao Da (strain) makes), with the dissolving of 45.0g toluene, after nitrogen replacement, in ethanol/the dry ice bath, be cooled to-20 ℃.In addition, 1.26g ion exchange water (H
2O/Ti=1.6 (mol ratio)) mixes with the 11.3g isopropyl alcohol, under-20 ℃ of states of cooling, splash in the above-mentioned four-hole boiling flask while stirring.Splash in the process, the liquid temperature in the flask is maintained at-20 ℃.After dripping off, after stirred on cooling 30min limit, limit, warming while stirring was to room temperature, and having obtained titanium oxide conversion concentration is the water white transparency partial hydrolysis solution (C-5) of 5 weight %.
(6) modulation of catalyst-6
Be dissolved in four (trimethylsiloxy) titanium (Gelest manufactured) in the dehydrated toluene, obtain the catalyst liquid (C-6) of concentration 1 weight %.
(7) modulation of catalyst-7
Except ion exchange water is splashing under-40 ℃, other modulation-1 with catalyst is the same, obtains partial hydrolysis liquid (C-7).
(8) metal species surfactant-1
M-1 conduct with following is used to modulate the metal species surfactant of organic film manufacturing with solution.
M-1: n-octadecane base trimethoxy silane (ODS, Gelest manufactured)
(9) metal species surfactant-2
Use the M-2 that is obtained by following method: n-octadecane base ortho-siliformic acid (ODHS) is used as being used to modulate the metal species surfactant of organic film manufacturing with solution.
At nitrogen replacement four-hole boiling flask in add 82g dewatered ethanol, 0.6g 0.1N hydrochloric acid and 9g water, be cooled to 0 ℃.Then, under agitation in above-mentioned four-hole boiling flask, splash into the 7.8g octadecyltriethoxy silane.After dripping off, reactant liquor at room temperature keeps 3h.Reacting liquid filtering, vacuum drying 2h under room temperature obtains 4.4g white powder (M-2), yield 72%.
(10) the organic film manufacturing is with the modulator approach-1 of solution
Under strong agitation, in dehydrated toluene, add ion exchange water, be modulated into the water-toluene that contains shown in the table 1.Contain adding metal species surfactant M-1 in the water-toluene at this, make final concentration become 0.5 weight %, stir 30min under the room temperature.Then, splash into the catalyst C-1～C-4 of the ormal weight shown in the table 1, after dripping off, at room temperature stir 3h, obtain solution (SA-1～SA-10) to this solution.
(11) the organic film manufacturing is with the modulator approach-2 of solution
Add metal species surfactant M-1 in the water-toluene containing of 350ppm moisture to containing, make ultimate density become 0.5 weight % and at room temperature stir 30min.In this solution, splash into the catalyst C-1～C-4 of ormal weight, at room temperature stir 3h after dripping off.Move into this solution of 100g in the bottle, at the bottom of being sunken to abundant glass fiber filter paper moisture, diameter 3cm (GA-100, Japan's filter paper (strain) manufacturing) bottle, add a cover.After room temperature leaves standstill 2h, obtain solution (SA-11～SA-14).
(12) the organic film manufacturing is with the modulator approach-3 of solution
Add metal species surfactant M-1 in the water-toluene containing of 350ppm moisture to containing, make ultimate density become 0.5 weight %, at room temperature stir 30min.In this solution, splash into the catalyst C-1～C-7 of ormal weight, at room temperature stir 3h after dripping off.Move into this solution of 100g in the bottle, blower and wooden following formula glass marble filter bubbling with 18L/min make the saturated steam bubbling at 25 ℃, have obtained the controlled solution of amount of moisture (SA-15～SA-18, SA-22～SA-25).
(13) the organic film manufacturing is with the modulator approach-4 of solution
In dehydrated toluene, add ion exchange water, strong agitation, modulation water content 100ppm contains water-toluene.In this solution, add metal species surfactant M-1, make ultimate density become 0.5 weight %, at stirring at room 30min.In this solution, splash into the ormal weight catalyst C-3 shown in the table 1, after dripping off, stirring at room 3h.Get this solution of 100g, move in the bottle, add the 10g ion exchange water, add a cover at 25 ℃ and stir 5min gently in order to avoid its emulsification obtains water saturated solution (SA-19, SA-20).After the stirring, lower floor has separated water outlet.
(14) the organic film manufacturing is with the modulator approach-5 of solution
Press the method for organic film manufacturing, obtain the solution (SA-21) of amount of moisture 250ppm with the unclear toluene of amount of moisture through the adjustment bubbling time with the modulator approach-3 (using catalyst C-3) of solution.
(15) the organic film manufacturing is with the modulator approach-6 of solution
In the oxolane (THF) of amount of moisture 400ppm, add metal species surfactant M-2, make ultimate density become 0.5 weight %, at stirring at room 3h.Get this solution 100g and move in the bottle, at the bottom of being sunken to abundant glass fiber filter paper moisture, diameter 3cm (GA-100, Japan's filter paper (strain) manufacturing) bottle, add a cover.After room temperature leaves standstill 2h, obtain solution (SA-26).
(16) the organic film manufacturing is with the modulator approach-7 of solution
The organic film manufacturing that following modulation comparative example is used with solution (R-1～R-6).
R-1: except not adding the ion exchange water other and of the modulator approach-1 the same modulation of manufacturing organic film with solution.
R-2～R-4: in dehydrated toluene, add ion exchange water, strong agitation is modulated into amount of moisture and is 100,210, the toluene of 94ppm.In these solution, add metal species surfactant M-1, make ultimate density become 0.5 weight %, stir 30min under the room temperature.Then, in this solution, splash into the catalyst C-2 of specified quantity, drip off under the room temperature of back and stir 3h, be modulated into the organic film manufacturing and use solution.
R-5: except that not adding the catalyst, other is used and makes the modulator approach-1 of organic film with solution and modulate equally.
R-6: M-1 is dissolved in the dehydrated toluene the metal species surfactant, and after the stirring at room 30min, the catalyst C-5 that drips stirs 3h under the room temperature, is modulated into the organic film manufacturing and uses solution.
(17) the organic film manufacturing is with the evaluation of solution
Measure amount of moisture, average grain diameter, Zeta potential in each solvent or the solution with method described below.
Table 1 is concluded and is shown the mensuration result.
In the table 1, the amount of moisture before handling is expressed as the amount of moisture in the solution that adds in the amount of moisture, SA-19, SA-20 of the solution before the bubbling among amount of moisture in the solution that adds among amount of moisture in the toluene of SA-1～SA-10, R-1～R-6, the SA-11～SA-14 before the glass fiber filter paper, SA-15～SA-18, the SA-22～SA-25 before the water.
< amount of moisture >
Measure by coulometric titration Ka Er-Fischer moisture meter (CA-07, Dia Instruments corporate system).
< average grain diameter >
Measure by dynamic light scattering method particle size determination device (HPPS, Malvern manufactured).
< Zeta potential >
(ELS-8000, big tomb electronics (strain) is made) measures by laser Zeta potential meter.
Table 1
| Solution is used in the organic film manufacturing | Catalyst (C) | The mixed proportion * of M-1 and C | Amount of moisture (PPM) before handling | Amount of moisture in the solution (PPM) | The average grain diameter of the particle in the solution | Zeta potential- |
| SA-1 | C-1 | 95∶5 | 1000 | 520 | - | - |
| SA-2 | C-1 | 90∶10 | 800 | 480 | - | - |
| SA-3 | C-2 | 99∶1 | 700 | 510 | - | - |
| SA-4 | C-2 | 90∶10 | 1000 | 485 | - | - |
| SA-5 | C-2 | 60∶40 | 1000 | 380 | - | - |
| SA-6 | C-3 | 95∶5 | 800 | 450 | - | - |
| SA-7 | C-3 | 90∶10 | 1000 | 480 | - | - |
| SA-8 | C-4 | 90∶10 | 1000 | 390 | - | - |
| SA-9 | C-2 | 90∶10 | 450 | 140 | - | - |
| SA-10 | C-2 | 90∶10 | 320 | 107 | - | - |
| SA-11 | C-1 | 90∶10 | 145 | 550 | - | - |
| SA-12 | C-2 | 90∶10 | 150 | 560 | - | - |
| SA-13 | C-3 | 90∶10 | 132 | 580 | - | - |
| SA-14 | C-4 | 90∶10 | 110 | 560 | - | - |
| SA-15 | C-1 | 90∶10 | 145 | 570 | - | - |
| SA-16 | C-2 | 90∶10 | 150 | 580 | - | - |
| SA-17 | C-3 | 90∶10 | 132 | 580 | - | - |
| SA-18 | C-4 | 90∶10 | 110 | 570 | - | - |
| SA-19 | C-3 | 95∶5 | 110 | 540 | - | - |
| SA-20 | C-3 | 90∶10 | 110 | 530 | - | - |
| SA-21 | C-3 | 90∶10 | - | 250 | - | - |
| SA-22 | C-7 | 90∶10 | 240 | 467 | - | - |
| SA-23 | C-5 | 90∶10 | 250 | 520 | 42nm | +47mV |
| SA-24 | C-5 | 50∶50 | 220 | 490 | 23nm | +53mV |
| SA-25 | C-6 | 98∶2 | 230 | 510 | 150nm | +116mV |
| SA-26 | - | - | - | 410 | - | - |
| R-1 | C-2 | 90∶10 | 7 | 12 | - | - |
| R-2 | C-2 | 90∶10 | 100 | 35 | - | - |
| R-3 | C-2 | 90∶10 | 210 | 82 | - | - |
| R-4 | C-2 | 90∶10 | 94 | 40 | - | - |
| R-5 | - | - | 350 | 510 | Can not measure | 0mV |
| R-6 | C-5 | 90∶10 | 3 | 2 | Can not measure | 0mV |
* (molal quantity of M-1): (the metal oxide conversion molal quantity of C solution metal composition) can be known by table 1; In SA-1～SA-10; When solution is used in the manufacturing of modulation organic film; Amount of moisture in the toluene is reduced to initial half the, although its reason also do not understand so far, think by being caused attached to the volatilization on the wall of a container, in atmosphere etc.
Can know that by SA-11～SA-21 the method that add the method for water after the employing, coexistence has moisture glass fiber filter paper in solution, the method that is blown into steam can the amount of moisturizing.Even solution is used in the organic film manufacturing for caused amount of moisture to reduce by some reason; Through having implemented to keep the means of moisture just can guarantee that it is at specified quantity or more amount of moisture; After preservation, use the occasion of solution, also can readjust the amount of moisture in the solution and use solution as the organic film manufacturing.
Result by the SA-23～SA-25 in the table 1 can know that although its outward appearance of modulated solution is transparent, particle forms.Can know that also this particle forms by adding moisture and catalyst.Inference thus, metal species surfactant M-1, water and catalyst are because some interaction has formed aggregation.
Modulated solution shows positive Zeta potential.In same solution, the Zeta potential of the soda lime glass that becomes substrate that records, alkali-free glass substrate, silicon chip is respectively-42mV ,-69mV and-35mV, littler than the Zeta potential value of solution.In the occasion that does not add water and catalyst, the Zeta potential value of solution is 0mV.
(18) formation of organic film-1
Being immersed in above-mentioned solution (among the SA-1～SA-26, R-1～R-6) through ultrasonic soda lime glass substrate (SLG), alkali-free glass substrate (AN100 that Asahi Glass (strain) is made), silicon chip (Si) and the stainless steel substrate (SUS316, SUS304) cleaned with ozone cleaned; Flooded after the stipulated time shown in the table 2; Put on; After cleaning with toluene is ultrasonic, 60 ℃ of dry 10min form the organic film (organic film (SAM-32) of SAM-1～SAM-31, RL-1～RL-6) and M-2 of M-1.
(19) evaluation of organic film
Through with following method to fine and close adhesion property, thickness, XPS analysis, the SPM of the contact angle of resulting organic film, film analyze, the crystallinity of film measures.Table 2 is concluded and is shown the fine and close adhesion property of contact angle, film, the mensuration result of thickness.
< contact angle >
With micro syringe on the surface of each sample, drip water, toluene or the tetradecane of 5 μ l, measure with contact angle instrument (360S type, エ Le マ manufactured) behind the 60s.
< the fine and close adhesion property of film >
Organic film supersound washing 1h in water, measure contact angle once more, compare with value before the supersound washing, shows same value person with zero expression, the value descender with * represent.
< thickness >
Measure the thickness of resulting organic film with multiple angles of incidence beam split ellipsoid appearance (Woollam manufactured).
< x-ray photoelectron spectrum analysis >
Carry out the elementary analysis in the film with x-ray photoelectron light-dividing device (XPS device, Quntum2000, Ulvac-Phi manufactured).
< SPM analysis >
Whether forming process and the film of measuring resulting organic film with scanning probe microscopy (SPM:SPA400, Seikon Instruments (strain) makes) have defective.
< crystallinity of film >
Measure the crystallinity of resulting organic film with film X-ray diffraction device (ATX-G, RIGAKU manufactured).
Table 2
| Organic film | Solution is used in the organic film manufacturing | Substrate | Dip time | The contact angle of film (°) | The fine and close adhesion property of film | Thickness (nm) | ||
| Water | Toluene or tetradecane * | |||||||
| SAM-1 | SA-1 | ?SLG | 2 minutes | 105 | ?35 | ○ | - | |
| SAM-2 | SA-1 | ?AN100 | 5 minutes | 106 | ?36 | ○ | - | |
| Embodiment | SAM-3 | SA-1 | ?Si | 10 minutes | 102 | ?33 | ○ | - |
| SAM-4 | SA-2 | ?SLG | 2 minutes | 106 | ?36 | ○ | - | |
| SAM-5 | SA-3 | ?AN100 | 5 minutes | 104 | ?34 | ○ | - | |
| SAM-6 | SA-4 | ?Si | 10 minutes | 105 | ?32 | ○ | - | |
| SAM-7 | SA-5 | ?SLG | 2 minutes | 100 | ?30 | ○ | - | |
| SAM-8 | SA-6 | ?AN100 | 2 minutes | 101 | ?32 | ○ | - | |
| SAM-9 | SA-7 | ?Si | 10 minutes | 101 | ?31 | ○ | - | |
| SAM-10 | SA-8 | ?SLG | 5 minutes | 100 | ?30 | ○ | - | |
| SAM-11 | SA-9 | ?SLG | 5 minutes | 101 | ?31 | ○ | - | |
| SAM-12 | SA-10 | ?SLG | 5 minutes | 99 | ?30 | ○ | - | |
| SAM-13 | SA-11 | ?SLG | 1 minute | 102 | ?32 | ○ | - | |
| SAM-14 | SA-12 | ?AN100 | 2 minutes | 106 | ?36 | ○ | - | |
| SAM-15 | SA-13 | ?Si | 5 minutes | 102 | ?32 | ○ | - | |
| SAM-16 | SA-14 | ?SLG | 5 minutes | 100 | ?30 | ○ | - | |
| SAM-17 | SA-15 | ?SLG | 1 minute | 103 | ?34 | ○ | - | |
| SAM-18 | SA-16 | ?Si | 5 minutes | 104 | ?33 | ○ | - | |
| SAM-19 | SA-17 | ?AN100 | 2 minutes | 102 | ?32 | ○ | - | |
| SAM-20 | SA-18 | ?SLG | 5 minutes | 100 | ?31 | ○ | - | |
| SAM-21 | SA-19 | ?Si | 5 minutes | 100 | ?30 | ○ | - | |
| SAM-22 | SA-20 | ?AN100 | 2 minutes | 107 | ?35 | ○ | - | |
| SAM-23 | SA-22 | ?SUS316 | 5 minutes | 109 | ?23 | ○ | - | |
| SAM-24 | SA-22 | ?SUS304 | 5 minutes | 110 | ?27 | ○ | - | |
| SAM-25 | SA-23 | ?SLG | 1 minute | 105 | ?35 | ○ | 2.5 | |
| SAM-26 | SA-23 | ?AN100 | 2 minutes | 105 | ?35 | ○ | 2.5 | |
| SAM-27 | SA-23 | ?Si | 3 minutes | 106 | ?36 | ○ | 2.7 | |
| SAM-28 | SA-24 | ?AN100 | 2 minutes | 102 | ?33 | ○ | 2.5 | |
| SAM-29 | SA-24 | ?Si | 2 minutes | 106 | ?36 | ○ | 2.6 | |
| SAM-30 | SA-25 | ?AN100 | 3 minutes | 104 | ?34 | ○ | 2.5 | |
| SAM-31 | SA-25 | ?Si | 5 minutes | 105 | ?32 | ○ | 2.6 | |
| SAM-32 | SA-26 | ?SLG | 5 minutes | 102 | ?32* | ○ | - | |
| Comparative example | RL-1 | R-1 | ?SLG | 30 minutes | 82 | ?13 | × | - |
| RL-2 | R-2 | ?Si | 60 minutes | 73 | ?9 | × | - | |
| RL-3 | R-3 | ?SLG | 5 minutes | 92 | ?26 | × | - | |
| RL-4 | R-4 | ?SLG | 5 minutes | 88 | ?19 | × | - | |
| RL-5 | R-5 | ?Si | 30 minutes | 65 | ?13 | × | Can not measure | |
| RL-6 | R-6 | ?Si | 60 minutes | 73 | ?9 | × | Can not measure | |
Can know by table 2, when amount of moisture is 50ppm or still less the time, even also do not obtain showing for a long time the organic film of abundant contact angle.Hence one can see that, and in order to obtain fine and close monomolecular film, necessary is: the ormal weight or the amount of moisture of volume more (i) will be arranged; (ii) be the occasion of ormal weight or less amount, come supply moisture, make solution maintain the ormal weight or the amount of moisture of volume more through the means that keep water to amount of moisture.
Secondly, by the XPS analysis of SAM-1～SAM-24 film, observe the strong peak of the elemental carbon beyond the substrate, the while also confirms to have the composition element of substrate, and according to the measuring principle that installs, the indication thickness is 10nm or thinner, and distribution is uniform in the face of carbon.The carbon content of comparative example RL-1～RL-4 embodiment about 1/3 or still less.
Also have, can know by the determining film thickness of SAM-25～SAM-31, the theoretical molecular length of metal species surfactant M-1 (about 2.3nm) no better than, so SAM-25～SAM-31 is a monomolecular film.
The thickness of comparative example R-5 and R-6 can not be measured, and can know not obtain monomolecular film.From the above mentioned; The organic film manufacturing with solution in; Generated the molecule aggregate particle that forms organic film, the Zeta potential value of this particle is bigger than the Zeta potential value of the substrate that forms organic film, and this indicates that it is important for generating good organic film at a high speed.
Also have, use metal species surfactant M-2, can form good organic film SAM-32.This indication has formed the relevant organic film of silanol with the metal species surfactant that contains hydroxyl.
Fig. 1 shows the X-ray diffractogram of SAM-25～SAM-27.Can know by Fig. 1, resulting organic film display surface spacing be about 4.1
well-crystallized property.By on can know that the molecule that constitutes film is that regular high density is filled, even on amorphism substrates such as glass substrate, also can form the crystallinity monomolecular film with very high speed.
Also have, in the film forming procedure of SAM-27 and SAM-31, cut apart dip time, over time by the SPM mensuration film forming procedure of the substrate surface under each time.Fig. 2 and Fig. 3 show the SPM collection of illustrative plates respectively.Fig. 2 be dip time be (a) 1s or still less, the SPM collection of illustrative plates of (b) 15s, (c) 30s, (d) 1min, and Fig. 3 is a dip time be respectively (a) 1s or still less, the SPM collection of illustrative plates of (b) 15s, (c) 1min, (d) 5min.
Can know that by Fig. 2 and 3 organic film on the substrate is film forming slowly along with change of time.Also have, Fig. 2 (a), Fig. 3 (a) indication of etc.ing, film is with the unimolecule growth, but is to grow up in a unit with aggregation.
Measured the particle diameter of this aggregation by Fig. 2 (a) and Fig. 3 (a), Fig. 2 is roughly 50nm, and Fig. 3 is roughly 200nm.The size of this aggregation is amassed with the particle surface that is calculated with the size (SAM-27:42nm, SAM-31:150nm) of the particle in the solution by the organic film manufacturing has good correlation.
By last indication, the organic film manufacturing has become the growth unit of fine and close organic film of growing up at a high speed with the aggregation of the molecule of the formation self aggregation film in the solution.
(18) formation of organic film-2
Under the condition of 25 ℃ of temperature, humidity 35%; 10 rectangle alkali-free glass substrates with the clean 2cm * 5cm of ozone of disposable input in 100g SA-21 solution are put on after the dipping 5min, after cleaning with toluene is ultrasonic; Dry 10min obtains organic film.Repeat this operation 20 times, the amount of moisture in the evaluation solution and the characteristic of resulting chemisorbed film.Also have, through with saturated steam to employed solution bubbling again, adjusting its amount of moisture is 250ppm, obtains organic film with same operation.Table 3 is concluded and is shown the result.
Table 3
| The dipping number of times | The 1st time | The 5th | The 10th time | The 15th time | The 20th time | Bubbling once more |
| Amount of moisture (ppm) | ?250 | 208 | 156 | 112 | 101 | 250 |
| Contact angle: water (°) | ?107 | 95 | 92 | 86 | 83 | 108 |
| Contact angle: toluene (°) | ?35 | 28 | 23 | 16 | 12 | 36 |
Can be known that by table 3 with the increase of substrate dipping number of times, the amount of moisture in the solution reduces, the contact angle of resulting organic film descends.This just indicates the minimizing of amount of moisture, uses the dip time identical with time more than the amount of moisture, does not form fine and close monomolecular film.
(19) formation of organic film-3
(the organic film manufacturing is with the modulation of solution)
In four-hole boiling flask 9.0g tetraisopropoxy titanium (trade name: A-1: purity 99%; Titanium oxide conversion concentration is 28.2 weight %; Japan Cao Da (strain) makes) be dissolved in the 91.0g toluene, through after the nitrogen replacement, in modification alcohol/the dry ice bath, be cooled to-60 ℃.In addition, 2.0g ion exchange water (H
2O/Ti=3.5 (mol ratio)) mixes with the 98.0g isopropyl alcohol, under-60～-50 ℃ the state of cooling, splash into while stirring in the above-mentioned four-hole boiling flask.Splash in the process, the liquid temperature in the flask is maintained at-60～-50 ℃.After dripping off, stir 5min while cooling off, stir 1h at-40 ℃ then, be warming up to room temperature subsequently, obtain colloidal solution.
Then, at room temperature, to 98g contain water-toluene (moisture: add the colloidal solution of 0.65g metal species surfactant M-1 and the above-mentioned manufacturing of 1.0g 460ppm), be immersed in that 30min makes its dissolving in the ultra sonic bath, obtain the organic film manufacturing with solution (SA-101).
Also have, add 20mg metatitanic acid (titanium hydroxide, three Tianjin and chemical reagent (strain) manufacturing) except the colloidal solution that replaces above-mentioned manufacturing and in addition, in ultra sonic bath, soak 1h equally, obtain suspension.Then, remove by filter not solvent components, obtain the organic film manufacturing with solution (SA-102).
In four-hole boiling flask, add 99g water saturation toluene (moisture 460ppm), at room temperature, splash into the toluene solution (H of 10% tetraisopropoxy titanium of 0.45g while stirring
2O/Ti=16 (mol ratio)), obtain colloidal solution.
Then, at room temperature, in this colloidal solution, add 0.65g metal species surfactant M-1, be immersed in that 30min makes it dissolving in the ultra sonic bath, obtain the organic film manufacturing with solution (SA-103).
(formation of organic film, the evaluation of organic film)
With 3 slides separately the organic film manufacturing of modulation here (flood 5min among the SA-101～SA-103) with solution; Take out sheet glass; The surface is cleaned with toluene, and 60 ℃ of dry 10min then obtain having formed on the surface organic film (sheet glass of SAM-101～SAM103) of ODS.Carry out the evaluation test of following < contact angle determination>with resulting 3 organic film sheet glass.
With microsyringe on resulting 3 surfaces, drip the respectively water and the tetradecane of 5 μ L, place 60s with the sheet glass of organic film.Then, be determined at the contact angle that drips the face that the water and the tetradecane are arranged with contact angle instrument (360S type, エ Le マ (strain) makes), the result is illustrated in the table 4, the contact angular unit degree of being in the table 4 (°).
Table 4
| Organic film | Solution is used in the organic film manufacturing | The contact angle of organic film (°) | |
| Water | The tetradecane | ||
| SAM-101 | SA-101 | 106.9 | 35.6 |
| SAM-102 | SA-102 | 99.7 | 28.7 |
| SAM-103 | SA-103 | 104 | 37.2 |
Can know by table 4, slide make organic film with solution in dipping 10min just can be formed with the repellency of excellence rapidly and scold the organic film of oiliness.
(22) formation of organic film-4
Contain the toluene solution 1.3g that adds 0.65g metal species surfactant M-1 and 3.5 weight % tetraisopropoxy titaniums in the water-toluene (moisture 460ppm) at 99g, make it dissolving, slaking 1 day.In this solution, add 2.0g distilled water, placed 1, be modulated into the organic film manufacturing with solution (SA-104).Then, slide resulting organic film manufacturing with solution (SA-104) in after the dipping 5min, take out slide, clean after the surface with toluene, at 60 ℃ of dry 10min, obtain having formed the slide of the organic film (SAM-104) of ODS on the surface.
On the surface of resulting slide with organic film; Drip the water and the tetradecane of last 5 μ L respectively with microsyringe; After placing 60s, use contact angle instrument (360S type, エ Le マ (strain) makes) to be determined at the contact angle that drips the face that the water and the tetradecane are arranged then; The result is that the contact angle of water is 106.3 °, and the contact angle of the tetradecane is 35.8 °
(23) formation of organic film-5
Contain the oleic acid titanium (three Tianjin and chemical reagent (strain) are made) that adds 0.65g metal species surfactant M-1 and 0.3g in the water-toluene (moisture 460ppm) at 99g, make it dissolving, slaking 1 day.At the adding 2.0g of this solution distilled water, placed 1, be modulated into the organic film manufacturing with solution (SA-105).Then, slide resulting organic film manufacturing with solution (SA-105) in after the dipping 5min, take out slide, clean after the surface with toluene, at 60 ℃ of dry 10min, obtain having formed the slide of the organic film (SAM-105) of ODS on the surface.
On the surface of resulting slide with organic film, drip the water and the tetradecane of last 5 μ L, placement 60s respectively with microsyringe.Then, be determined at the contact angle that drips the face that the water and the tetradecane are arranged with contact angle instrument (360S type, エ Le マ (strain) makes), the result is that the contact angle of water is 103.5 °, and the contact angle of the tetradecane is 32.2 °
(24) formation of organic film-6
(modulation of titanium complex solution)
In dehydrated toluene, add the toluene solution 1g of 3.5 weight % tetraisopropoxy titaniums and the complex shown in the table 5, obtain titanium complex solution (T-1～T-5).Table 5 shows the use amount of employed dehydrated toluene, the kind and the use amount of complex.
Table 5
| Titanium complex solution | Solution is used in the organic film manufacturing | Dehydrated toluene | |
| Kind | Addition | ||
| T-1 | Trifluoroacetic acid | 0.40g | 26.9g |
| T-2 | Acetylacetone,2,4-pentanedione | 0.35g | 26.9g |
| T-3 | Ethyl acetoacetate | 0.46g | 26.8g |
| T-4 | Tetrahydrochysene ethane | 0.25g | 27.0g |
| T-5 | Pyridine | 0.28g | 27.0g |
(formation of organic film, the evaluation of organic film)
(T-1～T-5) and 2.0g distilled water placed 1, modulated the organic film manufacturing with solution (SA-106～SA-110) in the water saturated toluene of 99g (moisture 460ppm), to add 0.65g metal species surfactant M-1,1.3g titanium complex solution.Then; (dipping 5min takes out slide then among the SA-106～SA-110), cleans after the surface with toluene with solution in resulting organic film manufacturing slide; At 60 ℃ of dry 10min, obtain having formed the organic film (slide of SAM-106～SAM-110) of ODS on the surface.
On the surface of resulting slide with organic film, drip the water and the tetradecane of last 5 μ L, placement 60s respectively with microsyringe.Then, be determined at a contact angle that drips the face that water and the tetradecane are arranged with contact angle instrument (360S type, エ Le マ (strain) make), mensuration is the result list in table 6, and the contact angular unit of table 6 is °.
Table 6
| Organic film | Titanium complex solution | Solution is used in the organic film manufacturing | The contact angle of organic film (°) | |
| Water | The tetradecane | |||
| ?SAM-106 | T-1 | ?SA-106 | 97.4 | 26.6 |
| ?SAM-107 | T-2 | ?SA-107 | 103.0 | 27.4 |
| ?SAM-108 | T-3 | ?SA-108 | 103.5 | 32.2 |
| ?SAM-109 | T-4 | ?SA-109 | 105.8 | 35.5 |
| ?SAM-110 | T-5 | ?SA-110 | 103.5 | 35.3 |
Can know by table 6,, just can form the repellency organic film excellent rapidly with scolding oiliness through flooding 10min to slide in SA-106～SA-110 organic film manufacturing in solution.
(20) formation of organic film-7
(modulation of titanium complex solution)
In the 19.2g dehydrated toluene, add the hydrolysis product (A-10: Japanese Cao Da (strain) manufacturing) of the alkoxytitanium of 0.51g, add 0.25g acetylacetone,2,4-pentanedione, 0.33g ethyl acetoacetate respectively as complex, obtain titanium complex solution (T-6, T-7).
(formation of organic film, the evaluation of organic film)
99g contain in the water-toluene (moisture 460ppm) add 0.65g metal species surfactant M-1, the above-mentioned titanium complex solution that obtains of 1.3g (T-6 T-7) and 2.0g distilled water, placed 1, modulate the organic film manufacturing with solution (C-11, C-12).Then; (dipping 5min takes out slide then among the SA-111～SA-112), cleans after the surface with toluene with solution in resulting organic film manufacturing slide; At 60 ℃ of dry 10min, obtain having formed the organic film (slide of SAM-111～SAM-112) of ODS on the surface.
On the surface of resulting slide with organic film, drip the water and the tetradecane of last 5 μ L, placement 60s respectively with microsyringe.Use contact angle instrument (360S type, エ Le マ (strain) make) to be determined at a contact angle that drips the face that water and the tetradecane are arranged then, mensuration is the result list in table 7, and the contact angular unit of table 7 is °.
Table 7
| Organic film | Titanium complex solution | Solution is used in the organic film manufacturing | The contact angle of organic film (°) | |
| Water | The tetradecane | |||
| SAM-111 | T-6 | SA-111 | 101.2 | 34.8 |
| SAM-112 | T-7 | SA-112 | 104.9 | 33.1 |
Can know by 7,, just can form the repellency organic film excellent rapidly with scolding oiliness through flooding 10min to slide in the organic film manufacturing of SA-111, SA-112 in solution.
(21) formation of organic film-8
(the organic film manufacturing is with the modulation of solution)
In containing in the water-toluene of moisture component 3 50ppm, add metal species surfactant M-1, the ultimate density that makes ODS is 0.5 weight %, stirring at room 30min.The dehydrated toluene 1 weight % solution (T-8) that in this solution, adds four (trimethyl first siloxy group) titaniums (AZmax manufactured) makes the molal quantity of ODS: the titanium oxide conversion molal quantity (T-8) is 98: 2, stirs 3h under the room temperature.Move into resulting reactant liquor 100g in the bottle of 1000mL,,, obtain organic film manufacturing that amount of moisture is adjusted into 510ppm with solution (SA-113) at 25 ℃ of bubbling saturated steams with blower and the wooden following formula glass marble filter of 18L/min.
(formation of organic film, the evaluation of organic film)
With the ultrasonic alkali-free glass substrate (goods number AN100, Asahi Glass (strain) is made) cleaned with ozone and the silicon chip (Si) cleaned after above-mentioned resulting organic film manufacturing is flooded the time shown in the table 8 in solution, put on next.After substrate surface cleaned with toluene is ultrasonic,, obtain having formed the substrate (SAM-113 (AN100), SAM-114 (Si)) of organic film on the surface at 60 ℃ of dry 10min.
Then, (AN100 is Si) on the organic film on surface at resulting each substrate; Drip the water and the tetradecane of last 5 μ L respectively with microsyringe; Use contact angle instrument (360S type, エ Le マ (strain) makes) to measure the contact angle on organic film surface then, measure the result and list in table 8.
Table 8
| Formed the substrate of organic film | Substrate | Dip time (branch) | The contact angle of organic film (°) | |
| Water | The tetradecane | |||
| SAM-113 | AN-100 | 3 | 104 | 34 |
| SAM-114 | Si | 5 | 105 | 33 |
And then, (AN100, Si) the organic film ultrasonic clean 1h in water that forms is gone up on the surface, measures contact angle once again at each substrate.(AN100 Si) does not see the decline of contact angle to any substrate in ultrasonic clean front and back, can know, any substrate has all been formed the excellent organic film of fine and close adhesion property from the teeth outwards.
(22) formation of organic film-9
(the organic film manufacturing is with the modulation of solution)
In containing in the water-toluene of moisture component 3 50ppm, add metal species surfactant M-1, the ultimate density that makes ODS is 0.5 weight %, stirring at room 30min.The dehydrated toluene 1 weight % solution (T-9) that in this solution, adds benzoic acid; Make the molal quantity of ODS: the benzoic acid molal quantity (T-9) is 10: 1; Stir under the room temperature, move into resulting reactant liquor 100g in the bottle of 1000mL, with blower and the wooden following formula glass marble filter of 18L/min; At 25 ℃ of bubbling saturated steams, obtain organic film manufacturing that amount of moisture is adjusted into 452ppm with solution (SA-114).
Except replacing the benzoic acid with the dehydrated toluene 1 weight % solution (T-10) of n-capric acid or the dehydrated toluene 1 weight % solution (T-11) of acetate; With aforementioned obtained equally organic film manufacturing that amount of moisture is adjusted into 317ppm, 434ppm respectively with solution (SA-115, SA-116).
(formation of organic film, the evaluation of organic film)
(after flooding 30min among the SA-114～SA116), putting on next in above-mentioned resulting organic film manufacturing with solution with the ultrasonic soda lime glass substrate (S-1126, loose unrestrained glass industry (strain) is made) cleaned with ozone cleaned.Behind the ultrasonic clean substrate surface of toluene,, obtain having formed the substrate of organic film on the surface at 60 ℃ of dry 10min.
Then, on the surface of resulting substrate, drip the water and the tetradecane of last 5 μ L respectively, place 60s with microsyringe.Then, be determined at the contact angle that drips the face that the water and the tetradecane are arranged, measure the result and list in table 9 with contact angle instrument (360S type, エ Le マ (strain) makes).PKa in the table 9 representes the acid ionization constant of the used organic acid aqueous solution is measured and the value obtained.The contact angular unit of table 9 is °.
Table 9
| Solution is used in the organic film manufacturing | Organic acid solution | The contact angle of organic film (°) | ||
| Kind | pKa | Water | The tetradecane | |
| SA-114 | Benzoic acid (T-9) | 4.20 | 104.6 | 32.1 |
| SA-115 | N-capric acid (T-10) | 4.89 | 114.4 | 25.3 |
| SA-116 | Acetate (T-11) | 4.56 | 83.8 | 19.6 |
Can know by table 9,, not see the decline of ultrasonic clean front and back contact angle, so, all formed the excellent organic film of fine and close adhesion property on the surface for arbitrary substrate in the organic acid occasion that use pKa is 1～6, preferred 2～5.
(23) formation of organic film-10
In the toilet of 25 ℃ of temperature, relative humidity 30%RH and 80%RH, separately in the SA-2 of 100g solution (amount of moisture 480ppm), with the rectangle alkali-free glass substrate of continuous 7 inputs in the interval of 10min with the clean 2cm * 5cm of ozone.Each puts on after flooding 3min, after cleaning with toluene is ultrasonic, at 60 ℃ of dry 10min, forms organic film, and table 10 shows the result.
Table 10
| The contact angle of organic film: water (°) | ||
| The dipping number of times | Humidity 30%RH | Humidity 80%RH |
| The 1st time | 104 | 105 |
| The 4th | 86 | 104 |
| The 7th time | 77 | 105 |
| Amount of moisture after dipping is over | 180ppm | 600ppm |
Can know that by table 10 under the environment of humidity 80%RH, short time dipping has obtained having the film of 100 ° or bigger high contact angle with good reappearance.On the other hand, under the environment of humidity 30%RH,, see that contact angle descends with the increase of dipping number of times.Hence one can see that, under low-humidity environment, in the dipping operation since the organic film manufacturing descend with the amount of moisture of solution and form the monomolecular film of densification.
(24) formation of monomolecular film
(the monomolecular film manufacturing is with the modulation of solution)
Make monomolecular film with following catalyst solution, the adjustment of metal species surfactant and use solution.
(2) catalyst solution of being modulated in the modulation of catalyst-2 (C-2);
(8) the n-octadecane base trimethoxy silane described in the metal species surfactant (ODS:Gelest manufactured, M-1 representes with the metal species surfactant);
Same with (11) organic film manufacturing with the modulator approach-2 of solution, in the toluene of amount of moisture 350ppm, add metal species surfactant M-1, making its ultimate density is 0.5 weight %, at room temperature stirs 30min.Then, in this solution, splash into the catalyst C-2 of the ormal weight shown in the table 11, after dripping off, stirring at room 3h.Move on to the such solution of 100g in the bottle, at the bottom of being sunken to the abundant glass fiber filter paper (Japan filter paper GA-100) of the diameter 3cm of suction bottle, add a cover then.Room temperature leaves standstill 2h, obtains the monomolecular film manufacturing with solution (SA-201), and its amount of moisture is 550ppm.Table 11 shows the result.In table 11, the amount of moisture before handling is illustrated in the amount of moisture of moisture adjustment monomolecular film manufacturing before with solution.
Also have, amount of moisture is to be measured with Ka Er-Fischer moisture meter (CA-07 of Dia Instruments manufactured) by coulometric titration.
Table 11
| Solution is used in the monomolecular film manufacturing | Catalyst (C) | The mixed proportion * of M-1 and C | Amount of moisture (ppm) | |
| Amount of moisture before handling | The monomolecular film manufacturing is with the amount of moisture of solution | |||
| SA-201 | C-2 | 90∶10 | 350 | 550 |
* (molal quantity of M-1): (the metal oxide conversion molal quantity of C solution metal composition)
(monomolecular film manufacturing approach-1)
Clean on soda lime glass substrate (SLG), alkali-free glass substrate (AN100 that Asahi Glass is made) and the silicon chip of cleaning with ozone (Si) ultrasonic; Be sprayed onto the monomolecular film manufacturing on the substrate with solution (SA-201) with low-pressure spray gun; Make whole surface wettability; After the 10s, on whole, spray SA-201 solution once more.In the moment of having sprayed after the 1st time, SA-1 solution demonstrates good wettability on the whole base plate face; When spraying the 2nd time, substrate surface becomes SA-201 solution is repelled.After having confirmed such repulsion, only spray toluene solution with same spray gun, carry out surface washing.Then, at 60 ℃ of dry 10min, obtained monomolecular film (SAM-201～SAM203).
(manufacturing approach of monomolecular film-2)
Drop in ultrasonic cleaning on soda lime glass substrate (SLG), alkali-free glass substrate (AN100 that Asahi Glass is made) and the silicon chip of cleaning with ozone (Si) to the monomolecular film manufacturing of in the formation-1 of (29) monomolecular film, being adjusted with solution (SA-201); Be covered with polyester film; With rubber rollers roll extrusion on film, make the monomolecular film manufacturing between substrate and film, evenly launch thinly with solution (SA-201).Under this state, leave standstill after the stipulated time, peel off film, substrate ultrasonic clean in toluene, 60 ℃ of dry 10min have obtained monomolecular film (SAM-204～SAM206).
(evaluation of monomolecular film)
Measure contact angle, the fine and close adhesion property of film, the XPS analysis of monomolecular film with evaluation method described in the evaluation of front (19) organic film, table 12 is concluded and is shown evaluation result.
Table 12
| Monomolecular film | The manufacturing of monomolecular film | The rerum natura of film | ||||
| Film manufacturing method | Substrate | Time of repose (branch) | The contact angle of film (°) | Fine and close adhesion property | ||
| Water | Toluene | |||||
| SAM-201 | Manufacturing approach-1 | ?SLG | - | 105 | 35 | ○ |
| SAM-202 | ″ | ?AN100 | - | 106 | 36 | ○ |
| SAM-203 | ″ | ?Si | - | 102 | 30 | ○ |
| SAM-204 | Manufacturing approach-2 | ?SLG | 1 | 106 | 36 | ○ |
| SAM-205 | ″ | ? |
2 | 104 | 34 | ○ |
| SAM-206 | ″ | ?Si | 5 | 105 | 32 | ○ |
Can know the monomolecular film of with manufacturing approach-1 and manufacturing approach-2, just obtained repellency in the short time, scold oiliness, fine and close adhesion property is good by table 12.In the past, be to make monomolecular film with metal species surfactant only, and adopt method of the present invention just can use a spot of solution on large substrate, to make monomolecular film with hydrolization groups such as alkoxyl with infusion process.And, show that by XPS analysis it is exactly a monomolecular film.
The possibility of commercial application
Adopt method for producing organic thin film of the present invention can make few, the fine and close self aggregation monomolecular film of impurity.Also have,, also can carry out the film forming of the chemisorbed film of high crystalline, excellent fine and close adhesion property, unimolecule and homogeneous even on the amorphism substrate.
Chemisorbed film of the present invention is applicable to the formation that forms the layout that appliance device uses etc.; Can also very be applicable to that easily the particularly electrochemical goods of electronic product, automobile, industrial instrumentation, camera lens, lens etc. require the machine of the ultrathin membrane coating of hear resistance, against weather, antifriction consumption, we can say very high industrialization value.
Claims (15)
1. method for producing organic thin film; It is the method for producing organic thin film that on substrate surface, forms organic film; It is characterized in that; Comprise making and contain surfactant, the interactional catalyst of surfactant and the organic solvent solution of organic solvent and the operation A of said substrate contacts therewith; 50～1000ppm scope is set or remained on to moisture in the said organic solvent solution; Wherein said catalyst be selected from ore deposit acid, by the acidic smooth acid producing agent of illumination, the acid of saturated fat list, saturated fat diacid, the acid of unsaturated fat list, unsaturated fat diacid, aromatic carboxylic acids, by the substituted aliphatic carboxylic acid of halogen atom, hydroxycarboxylic acid, by the acid catalyst in substituted aliphatic carboxylic acid of aromatic radical and the sulfonic acid; Organic solvent is the varsol that is selected from cyclohexane, benzene,toluene,xylene, naphtha, benzinum, isoparaffin, positive paraffin hydrocarbon, decahydronaphthalene, industrial gasoline, lam-oil and the ligroin, and said surfactant is the surfactant with formula (I) expression:
R
1 nMX
m-n (I)
In the formula, R
1Expression is with or without substituent alkyl, is with or without substituent halo alkyl, contains the alkyl of concatenating group or contains the halo alkyl of concatenating group, and said substituting group is carboxyl, amide groups, imide, ester group, alkoxyl, hydroxyl; M representes to be selected from least a kind of atom in silicon atom, germanium atom, tin atom, titanium atom and the zirconium atom; X representes hydroxyl or hydrolization group; N representes the arbitrary integer in 1～(m-1); M representes the valence of M; When n is 2 or more for a long time, R
1Identical or different, be 2 or more for a long time, X is identical or different and work as (m-n), still, in (m-n) individual X, at least 1 X is a hydrolization group; Wherein said hydrolization group is the group that decomposes with the water reaction.
2. the described method for producing organic thin film of claim 1 is characterized in that, said organic solvent is replaced by and is selected from n-hexane and solvent naphtha.
3. the described method for producing organic thin film of claim 1 is characterized in that, said organic solvent is replaced by the oil light fraction.
4. the method for producing organic thin film described in one of claim 1～3; It is characterized in that, said organic solvent solution be through use with respect to 1 mole of said surfactant 0.001～1mol's or oxide conversion molal quantity be 0.001～1mol, can obtain with the interactional catalyst adjustment of said surfactant.
5. method for producing organic thin film; It is the method for producing organic thin film that on substrate surface, forms organic film; It is characterized in that; Comprise making and contain surfactant, the interactional catalyst of surfactant and the organic solvent solution of organic solvent and the operation A of said substrate contacts therewith; Moisture in the said organic solvent solution is remained on 50～1000ppm scope; Use same solution to repeat 2 times or more times said operation A; Wherein said catalyst be selected from ore deposit acid, by the acidic smooth acid producing agent of illumination, the acid of saturated fat list, saturated fat diacid, the acid of unsaturated fat list, unsaturated fat diacid, aromatic carboxylic acids, by the substituted aliphatic carboxylic acid of halogen atom, hydroxycarboxylic acid, by the acid catalyst in substituted aliphatic carboxylic acid of aromatic radical and the sulfonic acid; Said organic solvent is the varsol that is selected from cyclohexane, benzene,toluene,xylene, naphtha, benzinum, isoparaffin, positive paraffin hydrocarbon, decahydronaphthalene, industrial gasoline, lam-oil and the ligroin, and said surfactant is the surfactant with formula (I) expression:
R
1 nMX
m-n (I)
In the formula, R
1Expression is with or without substituent alkyl, is with or without substituent halo alkyl, contains the alkyl of concatenating group or contains the halo alkyl of concatenating group, and said substituting group is carboxyl, amide groups, imide, ester group, alkoxyl, hydroxyl; M representes to be selected from least a kind of atom in silicon atom, germanium atom, tin atom, titanium atom and the zirconium atom; X representes hydroxyl or hydrolization group; N representes the arbitrary integer in 1～(m-1); M representes the valence of M; When n is 2 or more for a long time, R
1Identical or different, be 2 or more for a long time, X is identical or different and work as (m-n), still, in (m-n) individual X, at least 1 X is a hydrolization group; Wherein said hydrolization group is the group that decomposes with the water reaction.
6. the described method for producing organic thin film of claim 5 is characterized in that, said organic solvent is replaced by and is selected from n-hexane and solvent naphtha.
7. the described method for producing organic thin film of claim 5 is characterized in that, said organic solvent is replaced by the oil light fraction.
8. the method for producing organic thin film described in one of claim 5～7 is characterized in that, said repetition 2 times or more times said operation A are to use same solution, 2 or more a plurality of substrate are carried out said operation A.
9. method for producing organic thin film; It is the method for producing organic thin film that on substrate surface, forms organic film; It is characterized in that; Comprise make comprise surfactant, can with the organic solvent solution and the contacted operation of substrate of interactional catalyst of this surfactant and organic solvent; Set or remain on 50～1000ppm scope to the amount of moisture in the said organic solvent solution; Wherein said catalyst be selected from ore deposit acid, by the acidic smooth acid producing agent of illumination, the acid of saturated fat list, saturated fat diacid, the acid of unsaturated fat list, unsaturated fat diacid, aromatic carboxylic acids, by the substituted aliphatic carboxylic acid of halogen atom, hydroxycarboxylic acid, by the acid catalyst in substituted aliphatic carboxylic acid of aromatic radical and the sulfonic acid; Said organic solvent is the varsol that is selected from cyclohexane, benzene,toluene,xylene, naphtha, benzinum, isoparaffin, positive paraffin hydrocarbon, decahydronaphthalene, industrial gasoline, lam-oil and the ligroin, and said surfactant is the surfactant with formula (III) expression:
R
1 nMX
m-n-1(OH) (III)
In the formula, R
1Expression is with or without substituent alkyl, is with or without substituent halo alkyl, contains the alkyl of concatenating group or contains the halo alkyl of concatenating group, and said substituting group is carboxyl, amide groups, imide, ester group, alkoxyl, hydroxyl; M representes to be selected from least a kind of atom in silicon atom, germanium atom, tin atom, titanium atom and the zirconium atom; X representes hydroxyl or hydrolization group; N representes any integer of 1～(m-1), and m representes the valence of M; At n is 2 or more for a long time, R
1Identical or different; At (m-n-1) is 2 or more for a long time, X is identical or different; Wherein said hydrolization group is the group that decomposes with the water reaction.
10. the described method for producing organic thin film of claim 9 is characterized in that, said organic solvent is replaced by and is selected from n-hexane and solvent naphtha.
11. the described method for producing organic thin film of claim 9 is characterized in that said organic solvent is replaced by the oil light fraction.
12. the described method for producing organic thin film of each in the claim 1～3,5～7,9～11; It is characterized in that the operation of said organic solvent solution and substrate contacts is humidity to be remained in 40RH% or the more space said organic solvent solution and the contacted operation of substrate.
13. the described method for producing organic thin film of each in the claim 1～3,5～7,9～11; It is characterized in that the operation of said organic solvent solution and substrate contacts is humidity to be remained in 60RH% or the more space said organic solvent solution and the contacted operation of substrate.
14. the described method for producing organic thin film of each in the claim 1～3,5～7,9～11 is characterized in that, organic film is the crystallinity organic film.
15. the described method for producing organic thin film of each in the claim 1～3,5～7,9～11 is characterized in that organic film is a monomolecular film.
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| JP2545642B2 (en) * | 1990-09-26 | 1996-10-23 | 松下電器産業株式会社 | Glass |
| JP2506234B2 (en) * | 1990-12-25 | 1996-06-12 | 松下電器産業株式会社 | Method for manufacturing translucent substrate |
| JP2633747B2 (en) * | 1991-06-14 | 1997-07-23 | 松下電器産業株式会社 | Fluorine-based chemisorbed monomolecular cumulative film and method for producing the same |
| JPH08337654A (en) * | 1995-06-14 | 1996-12-24 | Matsushita Electric Ind Co Ltd | Production of chemisorption film, and chemisorption fluid used therefor |
| JP3599998B2 (en) * | 1998-02-13 | 2004-12-08 | セントラル硝子株式会社 | Method for producing water-repellent liquid and water-repellent coating |
| JP3649585B2 (en) * | 1998-05-15 | 2005-05-18 | セントラル硝子株式会社 | Water repellent coating solution |
| JP5061412B2 (en) * | 2001-07-16 | 2012-10-31 | Ｊｓｒ株式会社 | Film forming composition, film forming method, and silica-based film |
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2004
- 2004-04-14 ES ES04727374T patent/ES2368844T3/en not_active Expired - Lifetime
- 2004-04-14 CN CN2007101631665A patent/CN101157078B/en not_active Expired - Fee Related
- 2004-04-14 CN CNB2004800099401A patent/CN100451054C/en not_active Expired - Fee Related
Non-Patent Citations (1)
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| 王箴主编.《化工辞典》.《化工辞典》.化学工业出版社,2001,(第四版), * |
Also Published As
| Publication number | Publication date |
|---|---|
| ES2368844T3 (en) | 2011-11-22 |
| CN1774305A (en) | 2006-05-17 |
| CN100451054C (en) | 2009-01-14 |
| CN101157078A (en) | 2008-04-09 |
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