CN100451054C - Method for producing organic thin film - Google Patents
Method for producing organic thin film Download PDFInfo
- Publication number
- CN100451054C CN100451054C CNB2004800099401A CN200480009940A CN100451054C CN 100451054 C CN100451054 C CN 100451054C CN B2004800099401 A CNB2004800099401 A CN B2004800099401A CN 200480009940 A CN200480009940 A CN 200480009940A CN 100451054 C CN100451054 C CN 100451054C
- Authority
- CN
- China
- Prior art keywords
- metal
- solution
- film
- group
- active agent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Images
Landscapes
- Application Of Or Painting With Fluid Materials (AREA)
Abstract
A method for producing an organic thin film is disclosed 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
Technical field
The present invention relates to relate to the solution and the resulting organic film of the manufacturing organic film that in this method, uses in the manufacture method of substrate surface by 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-separability 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.(open referring to the spy flat 4-132637 communique, spy are opened flat 4-221630 communique, the spy opens flat 4-367721 communique)
Knownly be that the mixing solutions that contains alkoxyl silicone alkanes tensio-active agent at least, do not contain the non-water kind solvent of active hydrogen and be selected from least a silanol condensation catalyst in carboxylic metallic salt, carboxylicesters metal-salt, carboxylic metallic salt polymkeric substance, carboxylic metallic salt inner complex, titanic acid ester and the titanate chelate class is contacted with described substrate surface with in the manufacture method (referring to spy open flat 8-337654 communique) of described substrate surface formation by the covalently bound chemisorbed film of siloxane bond containing on the substrate surface of active hydrogen the method that forms chemisorbed film.
The known method that is formed with crystalline chemisorbed film at substrate surface is, the organic solvent solution of silicane tensio-active agent is formed the method for crystallinity unimolecular film (referring to Bull.Chem.Soc.Jpn. having dripped expansion on the silicon chip surface of purifying waste water, 74,1397-1401 (2001)).
The method of known formation repellency overlay film is, use the monomer and the polymkeric substance of hydrolysis resultant of the silane compound that contains fluoro-alkyl of acid-catalyzed hydrolysis, the repellency overlay film that utilizes the silanol base that unimolecular layer is constituted 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 manufacture method that chemical adsorption monomolecular film is arranged in the method that contains formation unimolecular film on the substrate surface of active hydrogen, it is characterized in that, contain following of dry atmosphere and be coated on the substrate surface with non-water class organic solvent and the synthetic chemical adsorbing liquid of silicane tensio-active agent, evaporation on one side, concentrate that described organic solvent makes surfactant molecule in the described adsorption liquid and substrate surface generation chemical reaction on one side and an end bonding of described surfactant molecule and be fixed on the substrate surface, after being fallen, described organic solvent evaporation the unreacted tensio-active agent that remains on the substrate surface is cleaned with organic solvent, the operation of removing (opening flat 11-147074 communique) referring to the spy.
But, thereby all these methods all exist film forming needs the problem of spended time, remain in silanol condensation catalyst in the film hindered chemisorption can not make the problem of fine and close unimolecular film, since generation acidic substance make problem that base material is restricted and must be in non-aqueous system film forming problem etc.Especially, the fine patternization requirement in the design such as electric device will be stablized the unimolecular 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 practical situation of described 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, found that, if contain metal species tensio-active agent with at least 1 or more a plurality of hydrolization groups and therewith the moisture content in the organic solvent solution of the interactional catalyzer of metal species tensio-active agent set or remain in the specialized range, perhaps the specified amount scope is set or remained on to the moisture content in the organic solvent solution that contains the metal species tensio-active agent 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 forms organic film on substrate surface, it is characterized in that, comprise containing metal species tensio-active agent with at least 1 or more a plurality of hydrolization groups and the organic solvent solution of the interactional catalyzer of metal species tensio-active agent and the operation (A) of described substrate contacts therewith the moisture content setting in its described organic solvent solution or remain on specialized range.
(2) method for producing organic thin film described in above-mentioned (1), it is characterized in that, aforementioned organic solvent solution be by use with respect to 1 mole of described metal species tensio-active agent 0.001～1mol's or oxide compound conversion mole number be 0.001～1mol, can obtain with the interactional catalyzer adjustment of aforementioned metal class tensio-active agent.
(3) method for producing organic thin film, it is the method for producing organic thin film that forms organic film on substrate surface, it is characterized in that, comprise containing metal species tensio-active agent with at least 1 or more a plurality of hydrolization groups and the organic solvent solution of the interactional catalyzer of metal species tensio-active agent and the operation (A) of described substrate contacts therewith, moisture content in the aforementioned organic solvent solution is remained on specialized range, use same solution to repeat 2 times or more times described 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 described operation (A) are to use same solution, 2 or more a plurality of substrate are carried out described operation (A).
(5) each described method for producing organic thin film in above-mentioned (1)～(4) is characterized in that, has operation (B) described 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 described 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) described substrate cleaning before.
(8) each described method for producing organic thin film in above-mentioned (1)～(7) is characterized in that, by with aforementioned organic solvent solution the scope that water layer is set the amount of moisture of aforementioned organic solvent solution or remain on specified amount being set in contact.
(9) each described method for producing organic thin film in above-mentioned (1)～(8), it is characterized in that the next scope of the amount of moisture of aforementioned organic solvent solution being set or remained on specified amount of the water-retentivity material that is in saturation state being arranged by coexistence in aforementioned organic solvent solution.
(10) method for producing organic thin film described in above-mentioned (9) is characterized in that, aforementioned water-retentivity material is a glass fibre filter.
(11) each described method for producing organic thin film in above-mentioned (1)～(10) is characterized in that, by be blown into the next scope of amount of moisture in the aforementioned organic solvent solution being set or remained on specified amount of the gas that contains moisture in aforementioned organic solvent solution.
(12) each described method for producing organic thin film in above-mentioned (1)～(11) is characterized in that, 50～1000ppm scope is set or remained on 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 specified amount scope is a value of measuring this solution of a part of taking with Ka Er-Fei Xiefa from aforementioned organic solvent solution.
(14) each described method for producing organic thin film in above-mentioned (1)～(13), it is characterized in that aforementioned can be to be selected from metal oxide, metal hydroxides, metal alkoxide class, chelating or coordinate metallic compound, metal alkoxide class partial hydrolysis resultant, at least a by in the hydrolysis resultant, organic acid, silanol condensation catalyst and the acid catalyst that obtain for 2 times of equivalents of metal alkoxide class or more times of described metal alkoxide classes of normal water treatment with the interactional catalyzer of described metal species tensio-active agent.
(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, does not exist under the situation of acid, alkali and/or dispersion stabilizer aforementioned metal alkoxide partial hydrolysis resultant to have in organic solvent 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 resultant 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 resultant 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, aforementioned metal oxide compound, metal hydroxides, metal alkoxide class, chelating or coordinate metallic compound, metal alkoxide class partial hydrolysis resultant, be to be selected from titanium, zirconium, aluminium, silicon, germanium, indium, tin, tantalum, zinc, tungsten, the lead a kind or more kinds of by the metal in the hydrolysis resultant that obtains for 2 times of equivalents of metal alkoxide class or more times of described metal alkoxide classes of normal water treatment.
(19) each described method for producing organic thin film in above-mentioned (1)～(18) is characterized in that, aforementioned metal species tensio-active agent 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 represents to be selected from least a kind of atoms metal in Siliciumatom, germanium atom, tin atom, titanium atom and the zirconium atom; X represents hydroxyl or hydrolization group; N represents the arbitrary integer in 1～(m-1); M represents 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 tensio-active agent 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 represents to be selected from least a atoms metal in Siliciumatom, germanium atom, tin atom, titanium atom and the zirconium atom; X represents hydroxyl or hydrolization group; R
2And R
3Represent hydrogen atom or fluorine atom respectively independently; R
4The divalent of expression alkylidene group, vinylidene, ethynylene, arylidene or silicon atoms and/or Sauerstoffatom links group; Y represents hydrogen atom, alkyl, alkoxyl group, contains fluoroalkyl or fluoroalkoxy; P represents 0 or natural number; Q represents 0 or 1; R represents 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 group or the acyloxy of halogen atom, C1～C6.
(22) method for producing organic thin film, it is the method for producing organic thin film that forms organic film on substrate surface, it is characterized in that, comprise the organic solvent solution and the contacted operation of substrate that make the metal species tensio-active agent that has 1 or more a plurality of hydroxyls at least, the specified amount scope is set or remained on to the amount of moisture in the aforementioned organic solvent solution.
(23) method for producing organic thin film described in above-mentioned (22) is characterized in that, 50～1000ppm scope is set or remained on to the amount of moisture in the aforementioned organic solvent solution.
(24) method for producing organic thin film described in above-mentioned (22) or (23) is characterized in that, the aforementioned metal species tensio-active agent 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 represents to be selected from least a kind of atoms metal in Siliciumatom, germanium atom, tin atom, titanium atom and the zirconium atom; X represents hydroxyl or hydrolization group; N represents any integer of 1～(m-1), and m represents 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.)。
(25) 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 described organic solvent solution and the contacted operation of substrate.
(26) 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.
(27) 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.
(28) each described method for producing organic thin film in above-mentioned (1)～(27) is characterized in that, organic film is the crystallinity organic film.
(29) each described method for producing organic thin film in above-mentioned (1)～(28) is characterized in that organic film is a unimolecular film.
(30) 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 active hydrogen.
(31) 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.
(32) each described method for producing organic thin film in above-mentioned (1)～(31) is characterized in that organic film is a chemisorbed film.
(33) 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 aggregate based on the metal species tensio-active agent with at least 1 or more a plurality of hydrolization groups or metal species tensio-active agent with at least 1 or more a plurality of hydroxyls, finished the invention of (35):
(35) the self aggregation film forms solution, and it is that the self aggregation film that forms the self aggregation film on substrate surface forms solution, it is characterized in that the molecule that forms the self aggregation film forms aggregate 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 tensio-active agent 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 aggregate is with interactional catalyzer of metal species tensio-active agent and water treatment are resulting therewith the metal species tensio-active agent 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 tensio-active agent 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 atoms metal in Siliciumatom, 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 tensio-active agent with at least 1 or more hydroxyl or hydrolization group is the compound of representing with formula V:
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 atoms metal in Siliciumatom, 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 group, vinylidene, ethynylene, arylidene or silicon atoms and/or Sauerstoffatom links group; Y
2Represent hydrogen atom, alkyl, alkoxyl group, 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 group or acyloxy.
(41) the self aggregation film described in each in (35)～(40) forms solution, it is characterized in that the median size of aforementioned aggregate 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 aggregate is with the Zeta potential value of the described 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 finished the invention of (44) in view of the above.That is to say, relate to
(44) chemisorbed film, it is the chemisorbed film that forms on substrate, 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 tensio-active agent 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 unimolecular 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 described organic solvent solution, utilize at least a method in pickling process, spin-coating method, rolling method, Meyer rod method, silk screen print method, woodburytype, spread coating and the spraying method, even the operation of the described organic solvent solution of coating also can be made unimolecular film (48 of claims the) on described substrate, finished the invention of (49), (50) in view of the above.
(49) unimolecular film manufacture method, it is characterized in that, comprise utilize that at least a method be selected from pickling process, spin-coating method, rolling method, Meyer rod method, silk screen print method, woodburytype, spread coating and the spraying method has hydroxyl containing, the organic solvent solution of the metal species tensio-active agent of-oxyl or acyloxy is coated on the operation on the substrate.
(50) the unimolecular film manufacture method is characterized in that, the organic solvent solution of the metal species tensio-active agent with hydroxyl,-oxyl or acyloxy is dripped, and the solution that drips is pressurizeed from top, it is spread on substrate come.That is to say, relate to:
(51) manufacture method of the unimolecular film described in (50) is characterized in that, described is film, sheet or dull and stereotyped and method calendering on substrate surface is overlapping to the solution that drips from the method for top pressurization.
(52) the described unimolecular film manufacture method of each in (49)～(51) is characterized in that, the operation that aforesaid base plate is cleaned is set after aforementioned painting process.
(53) the described unimolecular film manufacture method of each in (49)～(52) is characterized in that, is provided with after aforementioned painting process the operation of aforesaid base plate heating.
(54) the described unimolecular film manufacture method of each in (49)～(53), it is characterized in that, the aforementioned organic solvent solution that contains the metal species tensio-active agent be further contain can with the organic solvent solution of the interactional catalyzer of metal species tensio-active agent.
Describe the present invention below in detail.
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 tensio-active agent of at least one or more a plurality of hydrolization groups and the organic solvent solution of the interactional catalyzer of metal species tensio-active agent (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 tensio-active agent of at least one or more a plurality of hydroxyls therewith, the setting of the moisture content in the described organic solvent solution or remain on the specified amount scope containing (a).
As the metal species tensio-active agent in the employed solution (a) among the present invention with at least 1 or more a plurality of hydrolization groups, so long as same intramolecularly have at least one or more a plurality of can hydrolysis functional group and the material of hydrophobic group just, have no particular limits, preferably have can with the tensio-active agent 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 tensio-active agent 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 described alkyl that is with or without in the substituent alkyl, enumerate: the alkyl of carbon numbers 1～30 such as methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, sec-butyl, the tertiary butyl, n-pentyl, isopentyl, neo-pentyl, tert-pentyl, n-hexyl, isohexyl, n-heptyl, n-octyl, positive decyl; The thiazolinyl of carbon numbers 2～30 such as vinyl, propenyl, butenyl, pentenyl; Aryl such as phenyl, naphthyl; Deng.
As the halo alkyl that is with or without in the substituent halohydrocarbon, 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 described 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 alkyl that fluorine atom replaces and inner carbochain is that the carbochain of fluorine atom replacement is arranged also is indifferent.Particularly preferably be, all hydrogen atoms that terminal portions has an alkyl be perfluoroalkyl moieties that fluorine atom replaced and and the atoms metal M that says later between have with-(CH
2)
hThe group of the alkylidene group that-(h represents 1～6 integer in the formula, and the integer with 2～4 serves as preferred) is represented.
When the number of fluorine atoms of representing 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] % in the fluoro-alkyl, be preferably 60% or more, more preferably 80% or more.
Be with or without substituent alkyl or be with or without substituting group in the substituent halo alkyl as above-mentioned, that enumerates has: alkoxyl group such as carboxyl, amide group, imide, ester group, methoxyl group, oxyethyl group 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.
Described binding group is with between the C-C that is present in alkyl or halo alkyl or serve as preferred between the carbon of alkyl and the atoms metal M that says later.
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-propyl, sec.-propyl) etc.
In the middle of these, consider R from repellency, weather resistance 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)
1 0-, 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)
2CH
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 represents a kind of atom selecting from Siliciumatom, germanium atom, tin atom, titanium atom and zirconium atom, obtain easily considering from raw material with viewpoint such as reactivity, wherein with Siliciumatom for preferred especially.
X represents 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 group 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; Isocyanate group; Cyano group; Amino or amide group etc.
Particularly preferably be, be with or without the acyloxy such as-oxyl, acetoxyl group such as alkoxyl group, alicyclic ring, aromatic base, alkene oxygen base, aralkoxy of substituent carbon number 1～6.
As the alkoxyl group of carbon number 1～6, that enumerates has, methoxyl group, oxyethyl group, positive propoxy, isopropoxy, n-butoxy, sec-butoxy, tert.-butoxy, n-pentyloxy, positive hexyloxy etc.
As acyloxy, acetoxyl group, propionyloxy, propionyloxy, n-propyl carbonyl oxygen base, sec.-propyl carbonyl oxygen base, normal-butyl carbonyl oxygen base, propionyloxy, alicyclic ring-oxyl, ring propoxy-, the ring third methyl oxygen base, cyclohexyloxy, norborneol alcoxyl base etc., alkene oxygen base etc. have been enumerated; Vinyl oxygen base, allyl group oxygen base etc., alkynyloxy group; Propargyloxy etc., aralkyl oxy; Propargyloxy etc., aralkyl oxy; Aryl radical oxygen such as benzyloxy, benzene oxyethyl group; Phenoxy group, naphthyloxy etc., benzoyloxy group or the like.
As their substituting group, carboxyl, amide group, imide, ester group, hydroxyl etc. have been enumerated.In these, as X, serve as preferred with alkoxyl group, acyloxy or the isocyanate group of hydroxyl, halogen atom, carbon number 1～6, the alkoxyl group of carbon number 1～4 or acyloxy are for more preferably.
M represents the valence of atoms metal M.
N represents 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,, can be example with the compound of formula (II) expression as a preferred form.
In the formula (II), R
4The divalent functional group of expression alkylidene group, vinylidene, ethynylene, arylidene or silicon atoms and/or Sauerstoffatom.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 represents hydrogen atom; Alkyl such as methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, sec-butyl, the tertiary butyl, n-pentyl, isopentyl, neo-pentyl, tert-pentyl, n-hexyl, isohexyl; Alkoxyl groups such as methoxyl group, oxyethyl group, positive propoxy, isopropoxy, n-butoxy, sec-butoxy, tert.-butoxy, n-pentyloxy, positive hexyloxy; 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 group are that fluorine atom replaces the fluoroalkoxy get etc.
R represents 0 or 1～(m-2) integer, in order to make highdensity adsorption 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 particularly preferred scope 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 atoms metal M is a representative example with the Siliciumatom 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
3CH2O(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 two or more uses that combines.
In solution (a), contained, can with the interactional catalyzer of described metal species tensio-active agent, so long as have, have no particular limits by being that intermediary comes partly to wait with the metal part of metal species tensio-active agent or hydrolization group and interacts with the catalyzer of the effect that activates hydrolization group or hydroxyl, promotion condensation just 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 resultant, with at least a kind of compound selecting 2 times of equivalents or more times of resulting hydrolysis resultants of normal water treatment metal alkoxide class, organic acid, silanol condensation catalyst and the acid catalysts; With metal alkoxide class, metal alkoxide class partial hydrolysis resultant for more preferably.
For metal oxide, metal hydroxides, metal alkoxide class, chelating or coordination change metallic compound, metal alkoxide class partial hydrolysis resultant, with the not special restriction of metal in 2 times of equivalents or more times of resulting hydrolysis resultants of normal water treatment metal alkoxide class, organic acid, the silanol condensation catalyst, with at least a kind of selecting from titanium, zirconium, aluminium, silicon, germanium, indium, tin, tantalum, zinc, tungsten and lead serves as preferred, titanium, zirconium, aluminium or silicon are for more preferably, and titanium is for preferred especially.
Metal oxide can be to use with any states such as colloidal sol, gel, solid state.Manufacture method for colloidal sol, gel has no particular limits, and for example, is example with the silicon sol, can example have, sodium silicate solution carry out the method for cationic 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 silicon sol, 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, to use the catalytic amount with respect to the metal species tensio-active agent serves as preferred, and then, its oxide compound conversion mol number with respect to 1mol metal species tensio-active agent is 0.001～1mol for more preferably, in 0.001～0.2mol scope for further preferred.These metal oxides can independent a kind of use, also can be 2 kinds or the use that combines more.
As metal hydroxides, so long as the oxyhydroxide of metal is resulting all right with which type of manufacture method.As the manufacture method of metal hydroxides, having of enumerating say later the method for metal alkoxide class hydrolysis, the method for metal-salt and metal hydroxides reaction etc.In addition, also commercially available product can be made with extra care by required, to use as metal hydroxides.
For the not special restriction of the carbon number of the alkoxyl group in the metal alkoxide class, from the difficulty or ease of the concentration of the oxide compound 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 compound; 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 compound; 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 compound; Deng.These metal alkoxide classes can independent a kind of use, perhaps two or more uses that combine.
Also have, in the present invention, as the metal alkoxide class, also can use by the metal alkoxide class of two or more and react compound alkoxide that resulting compound alkoxide, a kind or the metal alkoxide class of two or more and a kind or the reacting metal salt of two or more obtain and their combination.
The example that is reacted resulting compound alkoxide by the metal alkoxide class of two or more has, and reacts the compound alkoxide that obtains, the compound alkoxide that obtains with the complex salt form by the combination of 3B family element etc. by the alkoxide of basic metal or alkaline-earth metal and the alkoxide of transition metal.
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 polycondensate thereof etc., R wherein and R ' expression alkyl etc.
The compound alkoxide that obtains as the metal alkoxide class of a kind or two or more and a kind or the reacting metal salt of two or more can be an example with the resulting compound of reaction by metal-salt and metal alkoxide class.
As metal-salt, can example muriate, nitrate, vitriol, acetate, formate, oxalate 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, so long as the quantity that formed chemisorbed film is exerted an influence not, just having no particular limits, especially, serves as preferred to use the catalytic amount with respect to the metal species tensio-active agent, and then, more preferably it is 0.001～1mol with respect to 1mol metal species tensio-active agent, further is preferably 0.001～0.2mol, perhaps, more preferably oxide compound conversion mol number is 0.001～1mol, in 0.001～0.2mol scope for further preferred.These metal oxides can independent a kind of use, also can be two or more uses that combines.
Metal alkoxide class partial hydrolysis resultant 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 oligopolymer 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, described dispersate is meant dispersive minuteness particle in dispersion system.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 dispersate of hydrolysis resultant is not condensed and is not had inhomogeneous dispersive state, preferably represents transparent and uniform state.So-called transparent, be meant the state that visible light transmissivity is high, specifically, with dispersate be that the 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 compound conversion concentration, serve as preferred with the represented state of 80～100% transmitance.For the not special restriction of the particle diameter of the dispersate of hydrolysis resultant, but in order to obtain high visible light transmissivity, be 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 manufacture method of preferred metal alkoxide sector of breakdown hydrolysis resultant 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 come control hydrolysis speed by 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 with after the water treatment of specified amount, can be at the temperature of beginning hydrolysis or low temperature or at-20 ℃ or more further add water to react under the temperature condition of low temperature more.
The reaction of metal alkoxide class and water is although can carry out without the metal alkoxide class is directly mixed with water, to carry out in organic solvent 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 the neutral words just have no particular limits, serves as preferred with pure water or distilled water, and the words that its amount needs only in the scope of afore mentioned rules just have no particular limits, and can be selected arbitrarily by the dispersate that has as destination properties.
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.
For the not special restriction of the temperature of the metal alkoxide class in the method for above-mentioned (1) and water reaction, 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 water temp 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, be hydrolyzed under the reflux temperature from room temperature to used solvent, the step of going forward side by side is carried out dehydration condensation.
Can be even without using the special refrigerating unit also can the refrigerative temperature range for example under the scope from 0 ℃ to room temperature, come control hydrolysis speed with the method that control adds beyond the water speed equitemperature, carry out the metal alkoxide class in the method for above-mentioned (3) and the reaction of water thus.Also can be hydrolyzed under the reflux temperature from room temperature to used solvent 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 resultant 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 solubleness of water, at the noncondensing solvent of low temperature for more preferably.
As the object lesson of employed organic solvent, alcoholic solvents such as methyl alcohol, ethanol, Virahol have been enumerated; Halogenated hydrocarbon solvents such as methylene dichloride, chloroform, chlorobenzene; Varsols such as hexane, hexanaphthene, benzene,toluene,xylene; Ether solvents such as tetrahydrofuran (THF), ether, dioxane; Ketones solvents such as acetone, methylethylketone, methyl iso-butyl ketone (MIBK); Amide solvent such as dimethyl formamide, N-Methyl pyrrolidone; Sulfoxide kind solvents such as dimethyl sulfoxide (DMSO); Polysiloxane such as methyl polysiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentaandoxane, methyl phenyl silicone (spy opens flat 9-208438 communique etc.) etc.
These solvents can independent a kind of use or two or more mixing uses.
In the occasion of using as mixed solvent, with being combined as preferably of the lower alcohol solvent class of varsols such as toluene, dimethylbenzene and methyl alcohol, ethanol, Virahol, the trimethyl carbinol etc.At the lower alcohols solvent of this occasion, with the alcoholic solvent that uses 2 grades of Virahol, the trimethyl carbinols etc. or bigger level for more preferably.Ratio of mixture 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 make coagulable precipitation again the dispersive dispergator, make the hydrolysis of metal alkoxide class, dehydrating condensation and making catalyzer that uses in the dispersate of colloidal particle etc. and the dispersion agent 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 catalyzer used in the dispersate of colloidal particle etc. and the dispersion agent that plays the dispersate that is generated so long as play the dispergator that makes coagulable precipitation redispersion, foregoing conduct, just have no particular limits.
What used acid was enumerated has, organic acids such as ore deposit acid, acetate, formic acid, oxalic acid, carbonic acid, trifluoroacetic acid, tosic acid, methylsulfonic acid such as hydrochloric acid, nitric acid, boric acid, fluoroboric acid etc.; Phosphofluoric acid diphenyl iodnium, phosphofluoric acid triphenyl phosphonium salt etc. are by the acidic smooth acid producing agent of illumination.
What used alkali was enumerated has, trolamine, 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 dispersion medium, has enumerated antis such as dispergator, protective colloid, tensio-active agent etc.The example of specifically enumerating has, polycarboxylic acids such as oxyacetic acid, glyconic acid, lactic acid, tartrate, citric acid, oxysuccinic acid, succsinic acid; Hydroxycarboxylic acid; Phosphoric acid such as tetra-sodium, tripolyphosphate; Methyl ethyl diketone, methyl acetoacetate, methyl aceto acetate, etheric acid n-propyl, ISOPROPYL ACETOACETATE, the positive butyl ester of etheric acid, the secondary butyl ester of etheric acid, tert-butyl acetoacetate, 2,4-hexanedione, 2,4-heptadione, 3,5-heptadione, 2,4-acetyl caproyl, 2,4-diketone in the ninth of the ten Heavenly Stems, 5-methyl-hexanedione etc. have the polydentate ligand compound of strong sequestering power to atoms metal; 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; (spy opens flat 9-208438 communique, the spy opens flat 2000-53421 communique etc.) silicone compounds such as dimethyl polysiloxane-methyl (polysiloxane alkylidene group) silicone copolymers, trimethyl silicane ketone acid, carboxy-modified silicone oil, amino modified polysiloxane; Deng.
The quantity of employed metal alkoxide class partial hydrolysis resultant, so long as do not influence the quantity of formed organic film, just have no particular limits, especially, to use the catalytic amount with respect to the metal species tensio-active agent serves as preferred, and then, for 1mol metal species tensio-active agent, its oxide compound 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 two or more uses that combines.
The metal alkoxide class hydrolysis resultant that uses among the present invention is to come the resulting resultant of hydrolysis with 2 times of the metal alkoxide class or more times of normal water.
This hydrolysis resultant can be the material that metal alkoxide thing class is obtained with 2 times of normal water hydrolysis of described metal alkoxide class, also can be: by the metal alkoxide class is carried out partial hydrolysis with 2 times of normal water of less than of described metal alkoxide class, obtain after the metal alkoxide sector of breakdown hydrolysis resultant, further use the water (with 2 times of equivalents that add up to described metal alkoxide class of the amount of the employed water of partial hydrolysis of front) of specified amount to come hydrolysis again and obtain this partial hydrolysis resultant.
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 makes the reaction of metal alkoxide class and water in the present invention in organic solvent.
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 exchanged water.
The usage quantity of water is 2 times of equivalents or the more times of equivalents with respect to described 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 resultant 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 resultant.
Also have, for the water outside organic solvent, acid, alkali or dispersion stabilizer, this hydrolysis resultant also can unrestrictedly use in the described in front partial hydrolysis resultant employed equally.
The hydrolysising reacting temperature of metal alkoxide class depends on the reactivity of employed metal alkoxide class and stability 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, the temperature of reaction solution is risen to the reflux temperature of employed solvent from room temperature, further be hydrolyzed, dehydration condensation.
Chelating or coordination metallic compound can modulate by in solution of metal compound, adding sequestrant or the coordination compound that the metal of metallic compound therewith forms complex compound.As sequestrant or coordination compound, if can with the metal-chelating or the coordination of metal hydroxides, metal alkoxide class or the hydrolysis resultant that obtains with water treatment metal alkoxide class, have no particular limits.
Object lesson as sequestrant or coordination compound has been enumerated, saturated fatty acids such as acetate, propionic acid, butyric acid, valeric acid, dodecylic acid, tetradecanoic acid, hexadecanoic acid, octadecanoic acid; Saturated fatty two acids such as oxalic acid, propanedioic acid, Succinic Acid, pentanedioic acid, hexanodioic acid, pimelic acid, suberic acid, nonane diacid, sebacic acid; Unsaturated carboxylic acids such as vinylformic acid, methacrylic acid, butenoic acid, oleic acid, maleic acid; Aromatic carboxylic acid classes such as phenylformic acid, toluylic acid, phthalic acid; Halogenated carboxylic acid such as Mono Chloro Acetic Acid, trifluoroacetic acid class; Beta-diketon classes such as methyl ethyl diketone, BA, hexafluoroacetylacetone; 'beta '-ketoester such as methyl acetoacetate, methyl aceto acetate class; Heterocycles such as tetrahydrofuran (THF), furans, furancarboxylic acid, thiophene, thiophenic acid, pyridine, nicotinic acid, iso-nicotinic acid; Deng.They can independent a kind or two or more uses that combine.
With respect to metal hydroxides, metal alkoxide class or with the metal 1mol in the resulting hydrolysis resultant of water treatment metal alkoxide class, the add-on of sequestrant or coordination compound 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 sequestrant or coordination compound adding, whole system is fully stirred, just can obtain metal complex solution.Whipping temp is generally the temperature range of the boiling point from 0 ℃ to employed solvent.Churning time was generally several minutes to several hours.Chelating or coordination metallic compound both can separate use, also can be used as in described solution of metal compound the chelating that adds sequestrant or coordination compound and obtain or coordination solution of metal compound use.Also have, can synthetic chelating or coordination solution of metal compound preserve.
As silanol condensation catalyst, carboxylic metallic salt, carboxylicesters metal-salt, carboxylic metallic salt polymkeric substance, carboxylic metallic salt inner complex, titanic acid ester and titanate chelate etc. have been enumerated.Specifically can example stannous acetate is arranged, dibutyl tin laurate, two sad dibutyl tins, dibutyltin diacetate, two lauric acid dioctyl tins, two sad dioctyl tins, the 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 polymkeric substance, tin methide mercapto propionate polymkeric substance, the diacetyl acetic acid dibutyl tin, the 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 fatty list acid such as formic acid, acetate, propionic acid, butyric acid, isopropylformic acid, valeric acid, isovaleric acid, trimethylacetic acid, caproic acid, sad, capric acid, lauric acid, tetradecanoic acid, palmitinic acid, stearic acid; Saturated fatty diacid such as oxalic acid, propanedioic acid, succsinic acid, pentanedioic acid, hexanodioic acid; Unsaturated fatty acids list acid such as vinylformic acid, lactic acid, methacrylic acid, Ba Dousuan, iso-crotonic acid, oleic acid; Unsaturated fatty acids such as fumaric acid, toxilic acid diacid; Aromatic carboxylic acid such as M-nitro benzoic acid, 4-chloro M-nitro benzoic acid, naphthoic acid; The aliphatic carboxylic acid that-Mono Chloro Acetic Acid, trifluoroacetic acid etc. are replaced by halogen atom; Hydroxycarboxylic acids such as oxyacetic acid, lactic acid, oxysuccinic acid, citric acid; The aliphatic carboxylic acid that toluylic acid, 3-phenylpropionic acid etc. are replaced by aromatic base; Sulfonic acid such as Phenylsulfonic acid, tosic acid, methylsulfonic acid; Deng.
In these organic acids, from the activity of the hydrolization group of optimizing the metal species tensio-active agent, handle and consider easily, be that 1～6 organic acid serves as preferably with pKa value (logarithmic 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, redox electrode, ion specific electrode accurately to be measured 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 press 1,2, on the books in 3,5 volumes.
As acid catalyst, can example have, organic acids such as ore deposit acid, acetate, formic acid, oxalic acid, carbonic acid, trifluoroacetic acid, tosic acid, methylsulfonic acid such as hydrochloric acid, nitric acid, boric acid, fluoroboric acid etc., and then, can be by the acidic smooth acid producing agent of illumination, specifically be phosphofluoric acid diphenyl iodnium, phosphofluoric acid triphenyl phosphonium salt etc.
The metal species tensio-active agent with at least 1 or more a plurality of hydroxyls in the aforementioned solution (b) so long as have hydroxyl and hydrophobic grouping at least at same intramolecularly, 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 tensio-active agent, can also contain the interactional catalyzer of metal species tensio-active agent therewith with at least 1 or more a plurality of hydroxyls.As described catalyzer, what enumerate is and employed same catalyzer in aforementioned solution (a).
With the compound of aforementioned formula (III) expression can example the compound that illustrates below etc. arranged.Again, example is to be the example of the compound of atoms metal M with the Siliciumatom.
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)C
ONH(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)
6CONH(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)
4O(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)C
ONH(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)C
ONH(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 two or more uses that combine.
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 100 ℃～250 ℃ for preferred especially.
That specifically enumerates has, varsols such as normal hexane, hexanaphthene, benzene,toluene,xylene, petroleum naphtha, solvent naphtha, sherwood oil, oil lighting end, isoparaffin, positive paraffinic hydrocarbon, perhydronaphthalene, non-leaded gasoline, lam-oil, petroleum naphtha; 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 product), 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 two or more uses that combine.
The content of the metal species tensio-active agent in the organic solvent solution has no particular limits, but in order to obtain fine and close unimolecular 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 tensio-active agent, 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 tensio-active agent, oxide compound conversion mole number 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 they are referred to as " organic solvent solution ") and substrate contacts, specialized range has been set or remained on to the amount of moisture in this solution.By the amount of moisture in the organic solvent solution is controlled in specialized range, 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 tensio-active agent, catalyzer, organic solvent etc.Specifically, should be to be less than or equal to cause that obstruction is to the chemisorption of substrate surface, the quantity that can not make fine and close unimolecular film, make the loss amount of used metal species tensio-active agent big, make problems such as catalyst deactivation, and, be equal to or greater than enough promotions, activate film forming quantity.
So-called enough promotions, the film forming quantity of activation are meant, for example, make the contacted occasion of this solution and substrate with pickling process, 10min with interior, preferably 5min with interior duration 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 more mostly be preferred, with scope, more specifically say with 50～1000 and criticize the ppm scopes for more preferably that 200～800ppm scope is for preferred 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 tensio-active agent at 1000ppm or still less the time.
Be that the amount of moisture shown in is that the value of the part of organic solvent solution through Ka Er-Fei Xiefa mensuration got in expression here again.So long as the value of using the device of this method principle to measure, for the not special restriction of 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 tensio-active agent, metal oxide etc. can with the inflation method of the organic solvent solution of interactional catalyzer of metal species tensio-active agent and water, not special restriction, what can specifically enumerate is,
(1) to contain the metal species tensio-active agent, can with the organic solvent solution of the interactional catalyzer of metal species tensio-active agent in add the method for water;
(2) in the organic solvent solution of metal species tensio-active agent and water, add can with the method for the interactional catalyzer of metal species tensio-active agent, etc.
Also have, in order to suppress rapid reaction, with added catalyzer in the method for added water in the method for (1), (2) be with organic solvent diluting serve as preferred.
For can being metal oxide with the interactional catalyzer of metal species tensio-active agent, metal hydroxides, the metal alkoxide class, chelating or coordination metallic compound, metal alkoxide class partial hydrolysis resultant, with 2 times of equivalents that are equivalent to the metal alkoxide class or the more times of described metal alkoxide classes of normal water treatment and the occasion of the hydrolysis resultant that obtains, catalyst consumption is not so long as influence the words of quantity of the rerum natura of formed unit molecule organic film, just have no particular limits, for 1 mole metal class tensio-active agent, be generally 0.001～1mol, be preferably 0.001～0.2mol, perhaps oxide compound conversion mole number is generally 0.001～1mol, serves as preferred with 0.001～0.2mol.
Also have, when described can be the organic acid occasion with the interactional catalyzer of metal species tensio-active agent, for 1 mole metal class tensio-active agent, be generally 0.001～100mol, be preferably 0.001～10mol.Use this scope can with the interactional catalyzer of metal species tensio-active agent, just can form does not rapidly have impurity and fine and close unimolecular film organic film.
Described metal species tensio-active agent, organic solvent, can stir with the mixture of interactional catalyzer of metal species tensio-active agent and water, just can obtain organic film manufacturing solution of the present invention.Whipping temp is generally-100 ℃～+ 100 ℃, serves as preferred with-20 ℃～+ 50 ℃.Churning time was generally several minutes to several hours.Also have, in this occasion, in order to obtain uniform organic film manufacturing solution, it also is preferred implementing supersound process.
With in the solution, produce the precipitate of containing metal oxide compound etc. at the synthetic manufacturing organic film of institute sometimes,, preferably impurity such as these precipitates are removed for the unit molecule organic film of the densification that obtains not having impurity.Precipitate can be removed very easily by operations such as filtering, topple over.
In the contacted operation of substrate of the present invention and described, preferably the amount of moisture in the aforementioned organic solvent solution is remained on the specified quantity scope, repeat this operation 2 times or more times with same solution.
So-called specified quantity scope represents that the specialized range with above-mentioned amount of moisture is same meaning, remains on such scope by 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 duration of contact and uniform organic film.
Under this occasion, the same solution of what is called is meant the meaning that discarded all or part of solution after having carried out contacting process operations 1 time is changed into the situation eliminating of new solution, as described later, all be included in the category of same solution by the solution in the scope that amount of moisture is remained on specified quantity with any method.
Amount of moisture adjustment and the method that remains in the specified quantity scope are specifically had,
(1) with organic solvent solution the method for water layer is set contiguously;
(2) coexistence has the method for the water-retentivity 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.
No matter these methods are that use separately or two or more uses that combines are all right.
Used water preferably uses pure water or distilled water so long as the neutral words just have no particular limits.Also have, employed organic solvent is anhydrous or just contain in advance some amount moisture all it doesn't matter.
In above-mentioned (1) method, use the occasion of varsol etc. and the isolating organic solvent of water layer, can with the isolating form of organic solvent layer coexistence water layer, also can use organic solvent solution in water layer, to circulate or by separating the organic solvent layer that obtains.
Use that lower alcohol etc. is unseparated with water layer, the occasion of solubleness is big in the water organic solvent, can example be that adopting with permeable and film not saturating organic solvent etc. is that intermediary makes organic solvent solution and the contacted method of water layer etc.
As the water-retentivity 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 class water-keeping material such as absorbent polymer; Mineral-type water-keeping materials such as zeolite, silicic acid carclazyte, vermiculite, porous ceramics; Tensio-active agents 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., with glass fibre filter for preferred especially.
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 as tensio-active agent etc. as the water-retentivity material.
Also have,, consider to adopt the method for hydrophilic solvent in order to improve the solubleness of water in organic solvent.In this occasion, hydrophilic solvent is also involved as making things convenient for the material of water conservation.
Have no particular limits for the amount of moisture that is contained in the water-retentivity material, but preferably amount of moisture to become the state that does not dissociate out from the water-retentivity 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 that interface that also can be by the water-retentivity material being arranged at solution and ambient atmosphere or be set to continuously in the solution from ambient atmosphere keeps the skin wet to solution by the moisture of drawing ambient atmosphere etc. 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 contains the method for moisture in gas, method of gas humidification etc.
As the method that in gas, contains moisture, can example have: gas is pulled the plug, gas such as contact at the method that water is contacted with gas, the method for the gas of former state use moisture vapor etc. 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 method etc.
Make having that the gas that contains moisture and the contacted method of organic solvent solution can example: be blown in the organic solvent solution or blow to the method on the surface of organic solvent solution to the gas that contains moisture, organic solvent solution is stirred on one side the method that places the atmosphere that contains moisture on one side as required, Yi Bian Yi Bian organic solvent solution stirred as required place through the method for the atmosphere of humidification etc.Serves as preferred for the method that the gas that contains moisture is blown in the organic solvent solution to be provided with device for blowing, washing unit and filtration unit etc. as required.
Also have, in aforesaid 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 amount etc. is provided.
For the not special restriction of 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 there is the substrate of active hydrogen on the surface for preferred especially.Use the surface that the substrate of active hydrogen is arranged,, just can easily on substrate surface, form chemisorbed film by the active hydrogen of substrate surface and the chemical interaction of the molecule in the organic solvent solution.
So-called active hydrogen is meant easy hydrogen as proton dissociation.The functional group that contains active hydrogen has been enumerated, hydroxyl (OH), carboxyl (COOH), aldehyde radical (CHO), imino-(=NH), amino (NH2), thiol group (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 synthon, 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 synthon, does not have hydroxyl, can contain oxygen plasma atmosphere and carry out pre-treatment (for example 20min under 100W) by substrate surface is placed, introduce hydrophilic radical by corona treatment.The substrate that constitutes by polyamide resin or urethane resin etc., because of having imino-from the teeth outwards, dealcoholization can take place with the alkoxysilyl of metal species tensio-active agent etc. in the active hydrogen of this imino-, 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 active 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 stratum basale with active hydrogen on the surface.
For the method for organic solvent solution and substrate contacts is had no particular limits, can use known method.That specifically enumerates has ， Jin Stains method, spin-coating method, spraying method, rolling method, Meyer rod method, silk screen print method, a spread coating etc., and wherein Yi Jin Stains method serves as preferred.
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 period of 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 of substrate Jin Stains Zhong organic solvent solution preferred.The method of when keeping the amount of moisture in the organic solvent solution basic plate being soaked Stains has specifically been enumerated:
(a) moisture is set and adjusts groove and Ji Ban Jin Stains groove, make by moisture and adjust liquid round-robin method in Ji Ban Jin Stains groove that groove has been adjusted moisture;
(b) a plurality of Ji Ban Jin Stains grooves are set, during with a Ji Ban Jin Stains Cao Jin Stains substrate, in other steeping vats, adjust the method for moisture;
(c) directly in Ji Ban Jin Stains groove, the mechanism that above-mentioned amount of moisture is remained on specialized range is set, the method that suitably keeps the skin wet etc.
For after having carried out substrate and operation that organic solvent solution contacts removing attached to the unnecessary reagent and the impurity on film surface, the operation (B) on cleaning base plate surface 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 dirt settling on surface just have no particular limits.Specifically can example have soaked the method for Stains in can the solvent of dissolution of metals class tensio-active agent, in a vacuum or the method for placing the method for evaporation under the normal pressure in the atmosphere, dispelling with rare gas elementes 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 to be embodied as more preferably in the space of 60%RH or bigger humidity to keep humidity to be embodied as in the space of 40%RH or bigger humidity preferably.In such space, the moisture in the organic solvent solution can better be kept, even also can form fine and close unimolecular film with good circulation ratio with the substrate Continuous Contact.
Method for producing organic thin film of the present invention both can be used to make unimolecular film, also can be used to make 2 layers or more multi-layered multilayer film, was particularly suitable for the manufacturing of unimolecular film.Also have, also can be used as by physical adsorption film forming from the teeth outwards method 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) metal species tensio-active agent with at least 1 or more a plurality of hydrolization groups and the interactional catalyzer of metal species tensio-active agent therewith, or (β) the organic solvent solution water treatment that contains metal species tensio-active agent with at least 1 or more a plurality of hydroxyls, amount of moisture in this organic solvent solution is set in the specified amount scope, when the amount of moisture in the above-mentioned organic solvent solution is remained on specialized range, place method airtight in the container etc.As the amount of moisture in the organic solvent solution being set in the specified amount scope, the amount of moisture in the above-mentioned organic solvent solution being remained on the method for specified amount scope, what enumerate is the method same with preceding method.
By it is enclosed in the container, just can prevent from 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 the amount of moisture in the solution is remained on specialized range.
By adopting above-mentioned method for producing organic thin film, the organic film that can obtain unimolecular 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 aggregate in solution.
In the organic solvent solution (to call " organic film manufacturing solution ") of amount of moisture in specialized range, the molecule that forms organic film forms under the situation of aggregate, 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.
The compound of representing as aforementioned formula (IV) or aforementioned formula V, specifically example is 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.Form with in the solution at the self aggregation film, the metal species surfactant molecule no longer by solvent with solvation form Individual existence, form aggregate but several molecule is assembled.
The metal species tensio-active agent that has at least one or more a plurality of hydrolization groups in use is during as the metal species tensio-active agent, and aggregate is by can be with the interactional catalyzer of metal species tensio-active agent and the described metal species tensio-active agent of water treatment and obtain; The metal species tensio-active agent that has at least one or more a plurality of hydroxyls in use is during as the metal species tensio-active agent, and aggregate is obtained by this metal species tensio-active agent of water treatment.
The form of aggregate is: molecule is between the hydrophobic part each other or the form that gathers together with intermolecular forces, coordinate bond or hydrogen bond etc. between the hydrophilic segment each other; Film forming molecule is the accumulative form by covalent bonds; Other media such as water form the form of little micella etc. by nuclear or intermediary; Perhaps these forms of combining etc.
Shape for aggregate has no particular limits, and Any shape such as spherical, chain, band shape is all right.The median size of aggregate has no particular limits, serving as preferred in 10～1000nm scope.
Also have, the Zeta potential of aggregate (interface electrokinetic potential) value is with greatly more preferred than the Zeta potential value of the substrate in same solvent.With the Zeta potential of aggregate be just, the Zeta potential value of substrate for negative for preferred especially.Use has formed the self aggregation film formation of the aggregate with such Zeta potential value and has used solution, just can make to have crystalline, fine and close unimolecular film.
3) chemisorbed film
Chemisorbed film of the present invention is the chemisorbed film that forms on substrate, it is characterized in that described 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) manufacture method of unimolecular film
The manufacture method of unimolecular film of the present invention is characterised in that to have the operation of solution coat on substrate surface that at least a method handle that adopts in the Jin Stains method that is selected from, spin-coating method, rolling method, Meyer rod method, silk screen print method, woodburytype, spread coating and the spraying method contains the metal species tensio-active agent.This operation is characterised in that, contain with-oxyl or acyloxy be the drips of solution of metal species tensio-active agent of hydrolization group on described 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 suitably select according to the position, the area that form unimolecular film.
To the solution that drips from the 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 thereon with roller after laying film, thin slice or flat board on the substrate surface.
The solution that contains described metal species tensio-active agent is being that the organic solvent solution that further contains the hydrolization group activatory catalyzer that makes described metal species tensio-active agent serves as preferred.
Description of drawings
Fig. 1 shows the film X ray crystallogram of organic film SAM-25～SAM-27.
Fig. 2 show in the forming process of SAM-27 ， Jin Stains time for (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 show in the forming process of SAM-31 ， Jin Stains time for (a) 1s or still less, the SPM collection of illustrative plates of (b) 15s, (c) 1min, the resulting organic film of (d) 5min.
Embodiment
Further describe the present invention with embodiment below, still, scope of the present invention is not limited in described embodiment.
(1) modulation of catalyzer-1
12.4g tetraisopropoxy titanium (A-1: purity 99%, titanium oxide conversion concentration is 28.2 weight %, and Japanese Cao Da (strain) makes) join in the four-hole boiling flask, with the dissolving of 45.0g toluene, through after the nitrogen replacement, in ethanol/liquid nitrogen bath, be cooled to-80 ℃.In addition, 1.26g ion exchanged water (H
2O/Ti=1.6 (mol ratio)) mixes with the 11.3g Virahol, 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 catalyzer-2
In the four-hole boiling flask of nitrogen replacement, 530g tetraisopropoxy titanium (A-1: purity 99%, titanium oxide conversion concentration are 28.2 weight %, and Japanese Cao Da (strain) makes) is dissolved in the 1960g toluene, in ethanol/the dry ice bath, be cooled to-15 ℃.In addition, 30.4g ion exchanged water (H
2O/Ti=0.9 (mol ratio)) mixes with the 274g Virahol, 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, continue to stir 1h after being warming up to room temperature then, obtained colourless transparent liquid at-10 ℃.This liquid is cooled to-80 ℃ with ethanol/the dry ice bath, under agitation splashes into 20.3g ion exchanged water (H with 90min
2O/Ti=0.6 (mol ratio)) with the mixing solutions of 183g Virahol.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 median size is the sharp-pointed monodispersed colloidal sol of 5.6nm.
(3) modulation of catalyzer-3
Under 18 ℃ of liquid temperature, nitrogen atmosphere, 17.79g (62.6mmol) tetraisopropoxy titanium (A-1: purity 99.9%, titanium oxide conversion concentration are 28 weight %, and Japanese Cao Da (strain) makes) is mixed stirring and dissolving with the 65.31g dehydrated toluene in flask.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 Virahol, 30.42g dehydrated toluene (concentration of water be equivalent to the saturation solubility of water in Virahol 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 %.Add toluene in this solution, being diluted to oxide concentration is 1.0 weight %, has obtained catalyzer (C-3).
(4) modulation of catalyzer-4
The silicon sol (daily output chemical industry (strain) is made for IPA-ST-S, 25 weight %) that is scattered in the Virahol (IPA) is dispersed in the dehydrated toluene, obtains the dispersion liquid (C-4) of silicon-dioxide conversion concentration 1 weight %.
(5) modulation of catalyzer-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 exchanged water (H
2O/Ti=1.6 (mol ratio)) mixes with the 11.3g Virahol, 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 catalyzer-6
Four (trimethylsiloxy) titanium (manufacturing of Gelest company) is dissolved in the dehydrated toluene, obtains the catalyzer liquid (C-6) of concentration 1 weight %.
(7) modulation of catalyzer-7
Except ion exchanged water is splashing under-40 ℃, other modulation-1 with catalyzer is the same, obtains partial hydrolysis liquid (C-7).
(8) metal species tensio-active agent-1
Be used to modulate the metal species tensio-active agent of organic film manufacturing with following M-1 conduct with solution.
M-1: Octadecane base Trimethoxy silane (ODS, Gelest company makes)
(9) metal species tensio-active agent-2
Use the M-2 that is obtained by following method: Octadecane base ortho-siliformic acid (ODHS) is used as being used to modulate the metal species tensio-active agent 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, reaction solution 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 modulator approach-1 of solution
Under violent stirring, in dehydrated toluene, add ion exchanged water, be modulated into the water-toluene that contains shown in the table 1.Contain adding metal species tensio-active agent 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 catalyzer C-1～C-4 of the specified amount 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 modulator approach-2 of solution
Add metal species tensio-active agent 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 catalyzer C-1～C-4 of specified amount, at room temperature stir 3h after dripping off.This solution of 100g is moved in the bottle, at the bottom of glass fiber filter paper (GA-100, Japan's filter paper (strain) manufacturing) fully aqueous, diameter 3cm is sunken to bottle, add a cover.After room temperature leaves standstill 2h, obtain solution (SA-11～SA-14).
(12) the organic film manufacturing modulator approach-3 of solution
Add metal species tensio-active agent 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 catalyzer C-1～C-7 of specified amount, at room temperature stir 3h after dripping off.This solution of 100g is moved in the bottle, and blower and wooden following formula glass sphere strainer 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 modulator approach-4 of solution
In dehydrated toluene, add ion exchanged water, violent stirring, modulation water content 100ppm contains water-toluene.In this solution, add metal species tensio-active agent M-1, make ultimate density become 0.5 weight %, at stirring at room 30min.In this solution, splash into the specified amount catalyzer 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 exchanged 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 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 by the adjustment bubbling time with the modulator approach-3 (using catalyzer C-3) of solution.
(15) the organic film manufacturing modulator approach-6 of solution
In the tetrahydrofuran (THF) (THF) of amount of moisture 400ppm, add metal species tensio-active agent 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 glass fiber filter paper (GA-100, Japan's filter paper (strain) manufacturing) fully aqueous, diameter 3cm is sunken to bottle, add a cover.After room temperature leaves standstill 2h, obtain solution (SA-26).
(16) the organic film manufacturing modulator approach-7 of solution
The organic film manufacturing that following modulation comparative example is used solution (R-1～R-6).
R-1: except not adding the ion exchanged water other and of the modulator approach-1 the same modulation of manufacturing organic film with solution.
R-2～R-4: add ion exchanged water in dehydrated toluene, violent stirring is modulated into amount of moisture and is 100,210, the toluene of 94ppm.In these solution, add metal species tensio-active agent M-1, make ultimate density become 0.5 weight %, stir 30min under the room temperature.Then, in this solution, splash into the catalyzer C-2 of specified quantity, drip off under the room temperature of back and stir 3h, be modulated into organic film manufacturing solution.
R-5: except that not adding the catalyzer, 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 tensio-active agent, and after the stirring at room 30min, the catalyzer C-5 that drips stirs 3h under the room temperature, is modulated into organic film manufacturing solution.
(17) the organic film manufacturing evaluation of solution
Measure amount of moisture, median size, Zeta potential in each solvent or the solution with method described below.Table 1 is concluded and is shown measurement 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).
＜median size 〉
(HPPS, Malvern company makes) measures by dynamic light scattering method particle size determination device.
＜Zeta potential 〉
(ELS-8000, big tomb electronics (strain) is made) measures by laser Zeta potential meter.
Table 1
| Organic film manufacturing solution | Catalyzer (C) | The blending ratio * of M-1 and C | Amount of moisture (PPM) before handling | Amount of moisture in the solution (PPM) | The median size 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 |
*(mole number of M-1): (the metal oxide conversion mole number of C solution metal composition)
As shown in Table 1, in SA-1～SA-10, when solution was used in modulation organic film manufacturing, the amount of moisture in the toluene was reduced to initial half, although its reason also do not understand so far, think by being caused attached to volatilization on the wall of a container, in atmosphere etc.
By SA-11～SA-21 as can be known, add after the employing method of water, in solution coexistence have aqueous glass fiber filter paper method, be blown into water vapour method can the amount of moisturizing.Even for the organic film manufacturing solution that causes amount of moisture to reduce by some reason, by 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 in the solution amount of moisture and as organic film manufacturing solution.
By the result of the SA-23～SA-25 in the table 1 as can be known, although its outward appearance of modulated solution is transparent, particle forms.Also as can be known, this particle forms by adding moisture and catalyzer.Inference thus, metal species tensio-active agent M-1, water and catalyzer are because some interaction has formed aggregate.
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 catalyzer, the Zeta potential value of solution is 0mV.
(18) formation of organic film-1
Cleaning and soda-lime glass substrate (SLG), alkali-free glass substrate (AN100 that Asahi Glass (strain) is made), silicon chip (Si) and stainless steel substrate (SUS316, SUS304) that ozone is cleaned are immersed in above-mentioned solution (among SA-1～SA-26, the R-1～R-6) through ultrasonic, flooded after the specified time shown in the table 2, put on, after cleaning with toluene is ultrasonic, 60 ℃ of dry 10min form organic film (SAM-1～SAM-31, RL-1～RL-6) and the organic film (SAM-32) of M-2 of M-1.
(19) evaluation of organic film
By fine and close adhesion property, thickness, XPS analysis, the SPM to the contact angle of resulting organic film, film in the following method analyze, the crystallinity of film measures.Table 2 is concluded and is shown the fine and close adhesion property of contact angle, film, the measurement result of thickness.
＜contact angle 〉
With microsyringe 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 company makes) 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 instrument (manufacturing of Woollam company).
＜x-ray photoelectron spectrum analysis 〉
Carry out the ultimate analysis in the film with x-ray photoelectron light-dividing device (Ulvac-Phi company makes for XPS device, Quntum2000).
＜SPM analyzes 〉
Whether forming process and the film of measuring resulting organic film with Scanning Probe Microscopy (SPM:SPA400, Seikon Instruments (strain) makes) have defective.
The crystallinity of＜film 〉
Measure the crystallinity of resulting organic film with film X-ray diffraction device (ATX-G, RIGAKU company makes).
Table 2
As shown in Table 2, when amount of moisture be 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 unimolecular film, necessary is: the specified amount or the amount of moisture of volume more (i) will be arranged; (ii) be the occasion of specified amount or less amount, come supply moisture, make solution maintain the specified amount or the amount of moisture of volume more by the means that keep water to amount of moisture.
Secondly,, observe the strong peak of substrate elemental carbon in addition, also confirm to have the composition element of substrate simultaneously, and according to the measuring principle that installs, the indication thickness is 10nm or thinner, and interior distribution of the face of carbon is uniform by the XPS analysis of SAM-1～SAM-24 film.The carbon content of comparative example RL-1～RL-4 embodiment about 1/3 or still less.
Also have, by the determining film thickness of SAM-25～SAM-31 as can be known, the theoretical molecular length of metal species tensio-active agent M-1 (about 2.3nm) no better than, so SAM-25～SAM-31 is a unimolecular film.
The thickness of comparative example R-5 and R-6 can not be measured, and does not obtain unimolecular film as can be known.From the above mentioned, use in the solution in the organic film manufacturing, generated the molecule aggregates 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 tensio-active agent M-2, can form good organic film SAM-32.This indication has formed the relevant organic film of silanol with the metal species tensio-active agent that contains hydroxyl.
Fig. 1 shows the X-ray diffractogram of SAM-25～SAM-27.As shown in Figure 1, resulting organic film display surface spacing is for about
Well-crystallized.As from the foregoing, the film forming molecule of structure is that regular high-density is filled, even also can form the crystallinity unimolecular film with very high speed on amorphism substrates such as glass substrate.
Also have, in the film process of SAM-27 and SAM-31, dipping time is cut apart, over time by the SPM mensuration film process of the substrate surface each time under.Fig. 2 and Fig. 3 show the SPM collection of illustrative plates respectively.Fig. 2 be dipping 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 dipping time be respectively (a) 1s or still less, the SPM collection of illustrative plates of (b) 15s, (c) 1min, (d) 5min.
By Fig. 2 and 3 as can be known, the organic film on the substrate is slowly film forming along with the variation of time.Also have, Fig. 2 (a), Fig. 3 (a) indication of etc.ing, film is with the unit molecule growth, but is to grow up in a unit with aggregate.
Measured the particle diameter of this aggregate by Fig. 2 (a) and Fig. 3 (a), Fig. 2 is roughly 50nm, and Fig. 3 is roughly 200nm.The size of this aggregate 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 good dependency.
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 aggregate of the molecule of the formation self aggregation film in the solution.
(20) formation of organic film-2
Under the condition of 25 ℃ of temperature, humidity 35%, the rectangle alkali-free glass substrates of 2cm * 5cm that 10 of disposable inputs are cleaned with ozone 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, by 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 |
As shown in Table 3, with the increase of substrate dipping number of times, the amount of moisture in the solution reduces, and the contact angle of resulting organic film descends.This just indicates the minimizing of amount of moisture, uses the dipping time identical with time more than the amount of moisture, does not form fine and close unimolecular film.
(21) formation of organic film-3
(the organic film manufacturing modulation of solution)
In four-hole boiling flask 9.0g tetraisopropoxy titanium (trade(brand)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 exchanged water (H
2O/Ti=3.5 (mol ratio)) mixes with the 98.0g Virahol, 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 tensio-active agent 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 organic film manufacturing usefulness solution (SA-101).
Also have, add 20mg metatitanic acid (titanium hydroxide, three Tianjin and chemical reagent (strain) are made) 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 organic film manufacturing 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 tensio-active agent 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 the synthetic here separately organic film manufacturing of 3 slide glasss with solution (dipping 5min among the SA-101～SA-103), 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 following＜contact angle determination with resulting 3 organic film sheet glass〉evaluation test.
With micro-syringe 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
As shown in Table 4, slide glass make organic film with solution in dipping 10min just can be formed with the repellency of excellence rapidly and scold the butyrous organic film.
(22) formation of organic film-4
Contain the toluene solution 1.3g that adds 0.65g metal species tensio-active agent 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 organic film manufacturing solution (SA-104).Then, slide glass after the dipping 5min, is taken out slide glass in resulting organic film manufacturing usefulness solution (SA-104), after the clean surface of toluene, at 60 ℃ of dry 10min, obtain having formed the slide glass of the organic film (SAM-104) of ODS on the surface.
On the surface of resulting slide glass with organic film, drip the water and the tetradecane of last 5 μ L respectively with micro-syringe, after placing 60s, use contact angle instrument (360S type then, エ Le マ (strain) manufacturing) is determined at a contact angle that drips the face that the water and the tetradecane are arranged, 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 tensio-active agent 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 organic film manufacturing solution (SA-105).Then, slide glass after the dipping 5min, is taken out slide glass in resulting organic film manufacturing usefulness solution (SA-105), after the clean surface of toluene, at 60 ℃ of dry 10min, obtain having formed the slide glass of the organic film (SAM-105) of ODS on the surface.
On the surface of resulting slide glass with organic film, drip the water and the tetradecane of last 5 μ L, placement 60s respectively with micro-syringe.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 coordination compound shown in the table 5, obtain titanium complex solution (T-1～T-5).Table 5 shows the usage quantity of employed dehydrated toluene, the kind and the usage quantity of coordination compound.
Table 5
(formation of organic film, the evaluation of organic film)
(T-1～T-5) and 2.0g distilled water were placed 1, modulation organic film manufacturing usefulness solution (SA-106～SA-110) to add 0.65g metal species tensio-active agent M-1,1.3g titanium complex solution in the water saturated toluene of 99g (moisture 460ppm).Then, (dipping 5min among the SA-106～SA-110) takes out slide glass, then after the clean surface of toluene with solution in resulting organic film manufacturing slide glass, at 60 ℃ of dry 10min, obtain having formed the organic film (slide glass of SAM-106～SAM-110) of ODS on the surface.
On the surface of resulting slide glass with organic film, drip the water and the tetradecane of last 5 μ L, placement 60s respectively with micro-syringe.Then, be determined at a contact angle that drips the face that the water and the tetradecane are arranged with contact angle instrument (360S type, エ Le マ (strain) make), measurement result is listed in table 6, and the contact angular unit of table 6 is °.
Table 6
As shown in Table 6, by slide glass is flooded 10min in SA-106～SA-110 organic film manufacturing in solution, just can form repellency rapidly and scold the organic film of oiliness excellence.
(25) formation of organic film-7
(modulation of titanium complex solution)
In the 19.2g dehydrated toluene, add the hydrolysis resultant (A-10: Japanese Cao Da (strain) manufacturing) of the titan-alkoxide of 0.51g, add 0.25g methyl ethyl diketone, 0.33g methyl aceto acetate respectively as coordination compound, obtain titanium complex solution (T-6, T-7).
(formation of organic film, the evaluation of organic film)
Contain in the water-toluene (moisture 460ppm) at 99g and to add 0.65g metal species tensio-active agent M-1, the above-mentioned titanium complex solution that obtains of 1.3g (T-6 T-7) and 2.0g distilled water, placed 1, modulation organic film manufacturing usefulness solution (SA-111～SA-112).Then, (dipping 5min among the SA-111～SA-112) takes out slide glass, then after the clean surface of toluene with solution in resulting organic film manufacturing slide glass, at 60 ℃ of dry 10min, obtain having formed the organic film (slide glass of SAM-111～SAM-112) of ODS on the surface.
On the surface of resulting slide glass with organic film, drip the water and the tetradecane of last 5 μ L, placement 60s respectively with micro-syringe.Use contact angle instrument (360S type, エ Le マ (strain) make) to be determined at a contact angle that drips the face that the water and the tetradecane are arranged then, measurement result is listed in table 7, and the contact angular unit of table 7 is °.
Table 7
By 7 as can be known,, just can form repellency rapidly and scold the organic film of oiliness excellence by slide glass is flooded 10min in the organic film manufacturing of SA-111, SA-112 in solution.(26) formation of organic film-8
(the organic film manufacturing modulation of solution)
In containing in the water-toluene of moisture component 3 50ppm, add metal species tensio-active agent 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 adds four (trimethylammonium first siloxanes) titanium (manufacturing of AZmax company) in this solution makes the mole number of ODS: the titanium oxide conversion mole number (T-8) is 98: 2, stirs 3h under the room temperature.Resulting reaction solution 100g is moved in the bottle of 1000mL,,, obtain the organic film manufacturing solution (SA-113) that amount of moisture is adjusted into 510ppm at 25 ℃ of bubbling saturated steams with blower and the wooden following formula glass sphere strainer of 18L/min.
(formation of organic film, the evaluation of organic film)
With ultrasonic clean and alkali-free glass substrate (goods number AN100, Asahi Glass (strain) is made) that ozone is cleaned and silicon chip (Si) after above-mentioned resulting organic film manufacturing is with the time shown in the dipping table 8 in the solution, put on next.After ultrasonic the cleaning of substrate surface usefulness toluene,, 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 Biao Mian the organic film at resulting each substrate, drip the water and the tetradecane of last 5 μ L respectively with micro-syringe, use contact angle instrument (360S type, エ Le マ (strain) makes) to measure the contact angle on organic film surface then, measurement result is listed in table 8.
Table 8
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, as can be known, any substrate has all been formed from the teeth outwards the organic film of fine and close adhesion property excellence.
(29) formation of organic film-9
(the organic film manufacturing modulation of solution)
In containing in the water-toluene of moisture component 3 50ppm, add metal species tensio-active agent 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 M-nitro benzoic acid, make the mole number of ODS: the M-nitro benzoic acid mole number (T-9) is 10: 1, stir under the room temperature, resulting reaction solution 100g is moved in the bottle of 1000mL, blower and wooden following formula glass sphere strainer with 18L/min, at 25 ℃ of bubbling saturated steams, obtain the organic film manufacturing solution (SA-114) that amount of moisture is adjusted into 452ppm.
Except replacing the M-nitro 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)
Cleaning and soda-lime glass substrate (S-1126, loose unrestrained glass industry (strain) is made) that ozone is cleaned (behind the dipping 30min, is put on next among the SA-114～SA116) in above-mentioned resulting organic film manufacturing with solution with ultrasonic.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 micro-syringe.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), measurement result is listed in table 9.PKa in the table 9 represents 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
As shown in Table 9, in the organic acid occasion that use pKa is 1～6, preferred 2～5, do not see the decline of ultrasonic clean front and back contact angle, so, all formed the organic film of fine and close adhesion property excellence on the surface for arbitrary substrate.
(28) formation of organic film-10
In the clean room 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
As shown in Table 10, under the environment of humidity 80%RH, short period of time dipping has obtained having the film of 100 ° or bigger high contact angle with good circulation ratio.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, uses the amount of moisture decline of solution and form fine and close unimolecular film owing to the organic film manufacturing in the dipping operation.
(29) formation of unimolecular film
(the unimolecular film manufacturing modulation of solution)
Make unimolecular film solution with following catalyst solution, the adjustment of metal species tensio-active agent.
(2) synthetic catalyst solution (C-2) in the modulation of catalyzer-2;
(8) the Octadecane base Trimethoxy silane described in the metal species tensio-active agent (ODS:Gelest company makes, and M-1 represents with the metal species tensio-active agent);
Same with (11) organic film manufacturing with the modulator approach-2 of solution, in the toluene of amount of moisture 350ppm, add metal species tensio-active agent M-1, making its ultimate density is 0.5 weight %, at room temperature stirs 30min.Then, in this solution, splash into the catalyzer C-2 of the specified amount shown in the table 11, after dripping off, stirring at room 3h.The such solution of 100g is moved on in the bottle, at the bottom of the abundant glass fiber filter paper (Japan filter paper GA-100) of the diameter 3cm of suction is sunken to bottle, add a cover then.Room temperature leaves standstill 2h, obtains unimolecular film manufacturing 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 unimolecular film manufacturing before with solution.
Also have, amount of moisture is to be measured with Ka Er-Fischer moisture meter (CA-07 that Dia Instruments company makes) by coulometric titration.
Table 11
*(mole number of M-1): (the metal oxide conversion mole number of C solution metal composition) (unimolecular film manufacture method-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, with low-pressure spray gun the unimolecular film manufacturing is sprayed onto on the substrate with solution (SA-201), 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-201 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 unimolecular film (SAM-201～SAM203).
(manufacture method of unimolecular film-2)
The unimolecular film manufacturing of being adjusted in the formation-1 of (29) unimolecular film is dropped 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) with solution (SA-201), be covered with polyester film, with rubber rollers roll extrusion on film, make the unimolecular film manufacturing between substrate and film, evenly launch thinly with solution (SA-201).Under this state, leave standstill after the specified time, film is peeled off, substrate ultrasonic clean in toluene, 60 ℃ of dry 10min have obtained unimolecular film (SAM-204～SAM206).
(evaluation of unimolecular film)
Measure contact angle, the fine and close adhesion property of film, the XPS analysis of unimolecular film with evaluation method described in the evaluation of front (19) organic film, table 12 is concluded and is shown evaluation result.
Table 12
As shown in Table 12, with manufacture method-1 and manufacture method-2, the unimolecular film of just obtained repellency in the short period of time, scold oiliness, fine and close adhesion property is good.In the past, be can not be with metal species tensio-active agent manufacturing unimolecular film only, and adopt method of the present invention just can on large substrate, make unimolecular film with a spot of solution with hydrolization groups such as alkoxyl groups with pickling process.And, show that by XPS analysis it is exactly a unimolecular 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, even on the amorphism substrate, also can carry out the film forming of the chemisorbed film of high crystalline, excellent fine and close adhesion property, unimolecule and homogeneous.
Chemisorbed film of the present invention is applicable to form the formation of the layout that appliance device uses etc., can also very easily be applicable to electronic product particularly electrochemical goods, automobile, industrial instrumentation, camera lens, lens etc. require the machine of the ultrathin membrane coating of heat resistance, against weather, antifriction consumption, very high industrialization value is arranged.
Claims (10)
1. method for producing organic thin film, it is the method for producing organic thin film that forms organic film on substrate surface, it is characterized in that, comprise containing metal species tensio-active agent and the organic solvent solution of the interactional catalyzer of metal species tensio-active agent and the operation (A) of described substrate contacts therewith, 50～1000ppm scope is set or remained on to moisture content in the described organic solvent solution, and wherein said metal species tensio-active agent is the metal species tensio-active agent 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 described substituting group is carboxyl, amide group, imide, ester group, alkoxyl group, hydroxyl; M represents to be selected from least a kind of atoms metal in Siliciumatom, germanium atom, tin atom, titanium atom and the zirconium atom; X represents hydroxyl or hydrolization group; N represents the arbitrary integer in 1～(m-1); M represents 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, described catalyzer is to be selected from metal oxide, metal hydroxides, the metal alkoxide class, chelating or coordinate metallic compound, metal alkoxide class partial hydrolysis resultant, by 2 times of equivalents of metal alkoxide class or the more times of described metal alkoxide classes of normal water treatment and the hydrolysis resultant that obtains, and at least a catalyzer in the silanol condensation catalyst, wherein, described metal oxide, metal hydroxides, the metal alkoxide class, chelating or coordinate metallic compound, metal alkoxide class partial hydrolysis resultant, by 2 times of equivalents of metal alkoxide class or the more times of described metal alkoxide classes of normal water treatment and the hydrolysis resultant that obtains, and the metal in the silanol condensation catalyst, be to be selected from titanium, zirconium, aluminium, silicon, germanium, indium, tin, tantalum, zinc, tungsten, in the lead at least a kind.
2. the method for producing organic thin film described in the claim 1, it is characterized in that, described organic solvent solution be by use with respect to 1 mole of described metal species tensio-active agent 0.001～1mol's or oxide compound conversion mole number be 0.001～1mol, can obtain with the interactional catalyzer adjustment of described metal species tensio-active agent.
3. method for producing organic thin film, it is the method for producing organic thin film that forms organic film on substrate surface, it is characterized in that, comprise containing metal species tensio-active agent and the organic solvent solution of the interactional catalyzer of metal species tensio-active agent and the operation (A) of described substrate contacts therewith, moisture content in the described organic solvent solution is remained on 50～1000ppm scope, use same solution to repeat 2 times or more times described operation (A), wherein said metal species tensio-active agent is the metal species tensio-active agent 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 described substituting group is carboxyl, amide group, imide, ester group, alkoxyl group, hydroxyl; M represents to be selected from least a kind of atoms metal in Siliciumatom, germanium atom, tin atom, titanium atom and the zirconium atom; X represents hydroxyl or hydrolization group; N represents the arbitrary integer in 1～(m-1); M represents 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, described catalyzer is to be selected from metal oxide, metal hydroxides, the metal alkoxide class, chelating or coordinate metallic compound, metal alkoxide class partial hydrolysis resultant, by 2 times of equivalents of metal alkoxide class or the more times of described metal alkoxide classes of normal water treatment and the hydrolysis resultant that obtains, and at least a catalyzer in the silanol condensation catalyst, wherein, described metal oxide, metal hydroxides, the metal alkoxide class, chelating or coordinate metallic compound, metal alkoxide class partial hydrolysis resultant, by 2 times of equivalents of metal alkoxide class or the more times of described metal alkoxide classes of normal water treatment and the hydrolysis resultant that obtains, and the metal in the silanol condensation catalyst, be to be selected from titanium, zirconium, aluminium, silicon, germanium, indium, tin, tantalum, zinc, tungsten, in the lead at least a kind.
4. the method for producing organic thin film described in the claim 3 is characterized in that, described repetition 2 times or more times described operation (A) are to use same solution, 2 or more a plurality of substrate are carried out described operation (A).
5. method for producing organic thin film, it is the method for producing organic thin film that forms organic film on substrate surface, it is characterized in that, comprise and make organic solvent solution and the contacted operation of substrate that comprises metal species tensio-active agent and catalyzer, 50～1000ppm scope is set or remained on to amount of moisture in the described organic solvent solution, and wherein said metal species tensio-active agent is the metal species tensio-active agent 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 described substituting group is carboxyl, amide group, imide, ester group, alkoxyl group, hydroxyl; M represents to be selected from least a kind of atoms metal in Siliciumatom, germanium atom, tin atom, titanium atom and the zirconium atom; X represents hydroxyl or hydrolization group; N represents any integer of 1～(m-1), and m represents 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, described catalyzer is to be selected from metal oxide, metal hydroxides, the metal alkoxide class, chelating or coordinate metallic compound, metal alkoxide class partial hydrolysis resultant, by 2 times of equivalents of metal alkoxide class or the more times of described metal alkoxide classes of normal water treatment and the hydrolysis resultant that obtains, and at least a catalyzer in the silanol condensation catalyst, wherein, described metal oxide, metal hydroxides, the metal alkoxide class, chelating or coordinate metallic compound, metal alkoxide class partial hydrolysis resultant, by 2 times of equivalents of metal alkoxide class or the more times of described metal alkoxide classes of normal water treatment and the hydrolysis resultant that obtains, and the metal in the silanol condensation catalyst, be to be selected from titanium, zirconium, aluminium, silicon, germanium, indium, tin, tantalum, zinc, tungsten, in the lead at least a kind.
6. the method for producing organic thin film described in the claim 1,3 or 5 is characterized in that, the operation of described organic solvent solution and substrate contacts is humidity to be remained in 40RH% or the more space described organic solvent solution and the contacted operation of substrate.
7. the method for producing organic thin film described in the claim 1,3 or 5 is characterized in that, the operation of described organic solvent solution and substrate contacts is humidity to be remained in 60RH% or the more space described organic solvent solution and the contacted operation of substrate.
8. the method for producing organic thin film described in the claim 1,3 or 5 is characterized in that, described organic solvent solution is varsol solution or fluorocarbons kind solvent solution.
9. the method for producing organic thin film described in the claim 1,3 or 5 is characterized in that, organic film is the crystallinity organic film.
Method for producing organic thin film described in 10 claims 1,3 or 5 is characterized in that organic film is a unimolecular film.
Applications Claiming Priority (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP109719/2003 | 2003-04-15 | ||
| JP2003109835 | 2003-04-15 | ||
| JP109835/2003 | 2003-04-15 | ||
| JP321893/2003 | 2003-09-12 | ||
| JP323173/2003 | 2003-09-16 | ||
| JP058778/2004 | 2004-03-03 | ||
| JP108732/2004 | 2004-04-01 |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2007101631665A Division CN101157078B (en) | 2003-04-15 | 2004-04-14 | Method for producing organic thin film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1774305A CN1774305A (en) | 2006-05-17 |
| CN100451054C true CN100451054C (en) | 2009-01-14 |
Family
ID=36760881
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2007101631665A Expired - Fee Related CN101157078B (en) | 2003-04-15 | 2004-04-14 | Method for producing organic thin film |
| CNB2004800099401A Expired - Fee Related CN100451054C (en) | 2003-04-15 | 2004-04-14 | Method for producing organic thin film |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2007101631665A Expired - Fee Related CN101157078B (en) | 2003-04-15 | 2004-04-14 | Method for producing organic thin film |
Country Status (2)
| Country | Link |
|---|---|
| CN (2) | CN101157078B (en) |
| ES (1) | ES2368844T3 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104209258B (en) * | 2006-07-31 | 2017-01-18 | 日本曹达株式会社 | Method for producing organic thin film by using film physical property improving process |
| US7972659B2 (en) * | 2008-03-14 | 2011-07-05 | Ecosil Technologies Llc | Method of applying silanes to metal in an oil bath containing a controlled amount of water |
| JP5793504B2 (en) * | 2010-11-11 | 2015-10-14 | 日本曹達株式会社 | Method for producing organic thin film laminate, and method for producing solid or oily material for forming organic thin film |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04132637A (en) * | 1990-09-26 | 1992-05-06 | Matsushita Electric Ind Co Ltd | Glass and production thereof |
| JPH04221630A (en) * | 1990-12-25 | 1992-08-12 | Matsushita Electric Ind Co Ltd | Translucent substrate and its manufacture |
| JPH04367721A (en) * | 1991-06-14 | 1992-12-21 | Matsushita Electric Ind Co Ltd | Chemically adsorbed fluorine contained laminated monomolecular film and method for preparing the same |
| JPH08337654A (en) * | 1995-06-14 | 1996-12-24 | Matsushita Electric Ind Co Ltd | Production of chemisorption film, and chemisorption fluid used therefor |
| JPH11228942A (en) * | 1998-02-13 | 1999-08-24 | Central Glass Co Ltd | Water-repellent fluid and production of water-repellent film |
| JPH11322368A (en) * | 1998-05-15 | 1999-11-24 | Central Glass Co Ltd | Solution for forming water repellent film |
| JP2003027001A (en) * | 2001-07-16 | 2003-01-29 | Jsr Corp | Composition for film formation, method for film formation, and silica-based film |
-
2004
- 2004-04-14 CN CN2007101631665A patent/CN101157078B/en not_active Expired - Fee Related
- 2004-04-14 ES ES04727374T patent/ES2368844T3/en not_active Expired - Lifetime
- 2004-04-14 CN CNB2004800099401A patent/CN100451054C/en not_active Expired - Fee Related
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04132637A (en) * | 1990-09-26 | 1992-05-06 | Matsushita Electric Ind Co Ltd | Glass and production thereof |
| JPH04221630A (en) * | 1990-12-25 | 1992-08-12 | Matsushita Electric Ind Co Ltd | Translucent substrate and its manufacture |
| JPH04367721A (en) * | 1991-06-14 | 1992-12-21 | Matsushita Electric Ind Co Ltd | Chemically adsorbed fluorine contained laminated monomolecular film and method for preparing the same |
| JPH08337654A (en) * | 1995-06-14 | 1996-12-24 | Matsushita Electric Ind Co Ltd | Production of chemisorption film, and chemisorption fluid used therefor |
| JPH11228942A (en) * | 1998-02-13 | 1999-08-24 | Central Glass Co Ltd | Water-repellent fluid and production of water-repellent film |
| JPH11322368A (en) * | 1998-05-15 | 1999-11-24 | Central Glass Co Ltd | Solution for forming water repellent film |
| JP2003027001A (en) * | 2001-07-16 | 2003-01-29 | Jsr Corp | Composition for film formation, method for film formation, and silica-based film |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101157078A (en) | 2008-04-09 |
| ES2368844T3 (en) | 2011-11-22 |
| CN1774305A (en) | 2006-05-17 |
| CN101157078B (en) | 2012-04-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5411339B2 (en) | Laminated body | |
| CN1988965B (en) | Method for organic thin film formation, assistant for organic thin film formation, and solution for organic thin film formation | |
| KR100902529B1 (en) | Dispersion of titanium oxide particles, titanium oxide thin film, solution for forming organic functional film, substrate having organic functional film formed thereon and method for producing same | |
| JP2010094583A (en) | Method of forming organic thin film | |
| JP5464784B2 (en) | A method for producing an organic thin film, comprising a step of washing a substrate with ozone water or hydrogen peroxide water | |
| JP4602971B2 (en) | Photosensitive substrate and patterning method | |
| CN100451054C (en) | Method for producing organic thin film | |
| JP5275799B2 (en) | Method for producing organic thin film using method for improving physical properties of film | |
| KR100796964B1 (en) | Method for producing organic thin film | |
| KR100748057B1 (en) | Method for producing organic thin film | |
| TW201410692A (en) | Organosilicon compound, thin film forming composition using same, and organic thin film | |
| JP2014100708A (en) | Method of manufacturing organic thin film comprising step of cleaning substrate with ozone water or hydrogen peroxide solution | |
| JP6164448B2 (en) | Manufacturing method of oxide film | |
| JPH06145601A (en) | Coating agent |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20090114 Termination date: 20190414 |