CN103451601A - Coating method of dry coating agent containing fluorine - Google Patents
Coating method of dry coating agent containing fluorine Download PDFInfo
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- CN103451601A CN103451601A CN2013101998966A CN201310199896A CN103451601A CN 103451601 A CN103451601 A CN 103451601A CN 2013101998966 A CN2013101998966 A CN 2013101998966A CN 201310199896 A CN201310199896 A CN 201310199896A CN 103451601 A CN103451601 A CN 103451601A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/5406—Silicon-containing compounds containing elements other than oxygen or nitrogen
Abstract
The invention provides a coating method of dry coating agent containing fluorine. According to the invention, the uniform filming on the substrate in a wide range can be realized without being influenced by the organosilane compound containing the fluorine. The coating method is characterized in that the 100 wt% of the organosilane compound containing the fluorine can be diluted by using the 100-99.900 wt% diluents, and the dry coating agent containing the fluorine can be modulated; when the coating agent is coated on the substrate, at least one of the fluorine-series solvents containing (A) having the boiling points in a range from 100 DEG C to 135 DEG C under the normal pressure and at least one of the fluorine-series solvents containing (B) having the boiling points in a range from 80 DEG C to 200 DEG C under the normal pressure can be chosen, and the mass ratio of (A)/(B) is 95/5-5/95.
Description
Technical field
The present invention relates to for wide the coating process of evaporation on base material of fluorine-containing dry type coating (dry coating) agent is even and scope.
Background technology
So far, the optics at lens, polaroid etc. with antireflection film, because the people uses, easily adhere to the dirt that sweat, fingerprint, sebum, makeup etc. produce, especially, because the surface at antireflection film has fine concavo-convexly, therefore be not easy soil release.In addition, the part of only adhering at such dirt becomes high reflection, and dirt is obvious, is therefore the problem place.
As the means that solve such problem, proposed to form on the surface of optics the method for the film of the fluorochemicals with didirtresistance or water-repellancy.For example, patent documentation 1(Unexamined Patent 5-215905 communique) in, the vacuum deposition method of the evaporation source that the sintered filter that makes fluoroalkyl silazane etc. be impregnated in metal-powder forms is disclosed, in addition, patent documentation 2(Unexamined Patent 8-143332 communique), in, the vacuum deposition method that makes the fluoroalkyl silazane be impregnated in the evaporation source that steel wool forms is disclosed.
The fluorochemicals used in such vacuum deposition method, in the impregnation of vapor deposition source, use the product by the fluorochemicals dilution with solvent, but the general molecular weight of the material of didirtresistance excellence is large, does not dissolve in common solvent, therefore the general fluorine series solvent that uses.For this impregnation vapor deposition source, once made the fluorine series solvent evaporation as diluting solvent, then adopt vacuum deposition method to make the stain-proofing layer film forming on processed base material, but the large impact of evapotranspiring property generation when confirming this diluting solvent evaporation and the remaining solvent of a part be not on vacuum evaporation fully.
On the other hand, for adopting step vacuum deposition method to make the method for stain-proofing layer film forming on processed base material, especially, under the situation of the fluorochemicals of high molecular, adhering to of processed base material peripheral part is few etc., evapotranspiring property difference between manufacturing batch sometimes, in this case, implement the disposal such as processings the again necessity that becomes, be large problem aspect productivity.
The prior art document
Patent documentation
Patent documentation 1: Unexamined Patent 5-215905 communique
Patent documentation 2: Unexamined Patent 8-143332 communique
Summary of the invention
The problem that invention will solve
The present invention completes in view of above-mentioned practical situation, its purpose be to provide be not subject to batch the affecting of fluorine-containing organic silicon hydride compounds, can be evenly and wide the coating process of the fluorine-containing dry type coating agent of film forming on base material of scope.
For solving the means of problem
The inventor to achieve these goals, further investigation repeatedly, found that: by use, use the mixed solvent more than 2 kinds of the fluorine series solvent with certain specific boiling spread that the fluorine-containing dry type coating agent of fluorine-containing organic silicon hydride compounds dilution is carried out to vacuum evaporation, can eliminate and result from the evapotranspiring property deficiency of production batch fluctuation (ロ ッ ト Block レ) of fluorine-containing organic silicon hydride compounds, can be evenly and wide the film forming on base material of scope, completed the present invention.
Therefore, the invention provides the coating process of the fluorine-containing dry type coating agent shown in following.
[1] coating process of fluorine-containing dry type coating agent, it is the coating process of fluorine-containing dry type coating agent, it is characterized in that, by fluorine-containing dry type thinner 100～99 for coating agent for fluorine-containing organic silicon hydride compounds 100 mass parts, 900 mass parts dilutions, modulate fluorine-containing dry type coating agent, use the dry type coating on base material of this coating agent, with thinner, to contain (A) boiling point from normal pressure be more than 100 ℃ and be less than at least a kind of selecting in the fluorine series solvent of 135 ℃ and (B) boiling point from normal pressure is different from (A) composition at least a kind that more than 80 ℃, in the fluorine series solvent below 200 ℃, selects in this fluorine-containing dry type coating agent, (A) mass ratio/(B) is 95/5～5/95.
[2] coating process of [1] described fluorine-containing dry type coating agent, wherein, fluorine-containing dry type coating agent is selected from PFTPA and hexafluoro m-xylene with the fluorine series solvent of (A) composition in thinner.
[3] coating process of [1] or [2] described fluorine-containing dry type coating agent, is characterized in that, fluorine-containing dry type coating agent with (A) composition in thinner and (B) boiling-point difference under the normal pressure of composition be more than 10 ℃ below 80 ℃.
The coating process of the described fluorine-containing dry type of any one coating agent of [4] [1]～[3], wherein, the number-average molecular weight of the polystyrene conversion fluorine-containing organic silicon hydride compounds, that the employing gel permeation chromatography is tried to achieve is the scope below 8,000 more than 1,000.
The coating process of the described fluorine-containing dry type of any one coating agent of [5] [1]～[4], wherein, the fluorine-containing organic silicon hydride compounds, adopt
19the amount of the fluorine atom that F-NMR tries to achieve is more than 50 quality % and is less than the scope of 80 quality %.
The coating process of the described fluorine-containing dry type of any one coating agent of [6] [1]～[5], wherein, the fluorine-containing organic silicon hydride compounds is by any expression of following general formula (1)～(3).
(in formula, X is hydrolization group, R
1the monovalence alkyl of carbon number 1～10, R
2be the monovalence alkyl of hydrogen atom or carbon number 1～10, Q is the alkylidene group that can middle have the carbon number 1～10 of NH base.The integer that m is 15～50, n is 2 or 3.）
(in formula, Rf
1mean comprise-(C
tf
2t) the O-(t integer that is 1～6) and shown in unit, there is the divalent group of perfluor polyalkylene ether structure of the straight chain shape of branch, R
3the monovalence alkyl that means carbon number 1～10, X
1mean hydrolization group or halogen atom.P mean independently 0,1 or 2, q mean independently 1～5 integer, r and s mean 2 or 3 separately.）
(in formula, Rf
2for perfluoroalkyl, X
2mean hydrogen atom, bromine atoms or iodine atom, Y is hydrogen atom or low alkyl group, and Z is fluorine atom or trifluoromethyl, R
4for hydroxyl or hydrolyzable group, R
5monovalence alkyl for hydrogen atom or carbon number 1～10.In addition, a, b, c, d, e are the integer more than 0 or 1, and a+b+c+d+e is for more than at least 1, the randomly combination of each repeating unit of a, b, c, d, e.F be 0,1 or 2, g be 1,2 or 3, h be the integer more than 1.）
The effect of invention
The coating process of the application of the invention, be not subject to the impact of fluorine-containing organic silicon hydride compounds batch fluctuation, can be equably and scope extensively on base material, make fluorine-containing dry type coating agent film forming.
The accompanying drawing explanation
Fig. 1 means the evaporation used in the embodiments of the invention sketch chart of base material mounting plate.
Embodiment
Below in more detail to the present invention's explanation.
The coating process of fluorine-containing dry type of the present invention coating agent, it is characterized in that, the fluorine-containing organic silicon hydride compounds is diluted with thinner with fluorine-containing dry type coating agent, modulate fluorine-containing dry type coating agent, use the dry type coating on base material of this coating agent, with thinner, to contain (A) boiling point from normal pressure be more than 100 ℃ and be less than at least a kind of selecting in the fluorine series solvent of 135 ℃ and (B) boiling point from normal pressure is different from (A) composition at least a kind that more than 80 ℃, in the fluorine series solvent below 200 ℃, selects in this fluorine-containing dry type coating agent.
As the fluorine-containing organic silicon hydride compounds used in the present invention, can use various fluorine-containing organic silicon hydride compounds, wishing to use the number-average molecular weight of the polystyrene conversion that preferably the employing gel permeation chromatography is obtained is 1, more than 000 8, below 000, especially 2, the fluorine-containing organic silicon hydride compounds of 000～6,000 scope.If number-average molecular weight is less than 1,000, sometimes can not bring into play fully water and oil-resistant as the feature of perfluor polyalkylene ether structure, didirtresistance etc., if surpass 8,000, sometimes can not the dry type coating.
Said number-average molecular weight in the present invention, refer under the following conditions the number-average molecular weight (lower with) of the polystyrene conversion that the employing gel permeation chromatography (GPC) measured obtains.
[condition determination]
Developing solvent: hydrochlorofluorocarazeotropic (HCFC)-225
Flow: 1mL/ minute
Detector: light scattering detector
Post: Dong Caoshe TSKgel Multipore processed HXL-M
7.8mm φ * 30cm is used 2
Column temperature: 35 ℃
Test portion injection rate: the HCFC-225 solution of 100 μ L(concentration 0.3 quality %)
The fluorine-containing organic silicon hydride compounds used in the present invention, more preferably used and adopt
19the amount of the fluorine atom that F-NMR obtains is more than 50 quality % and is less than the fluorine-containing organic silicon hydride compounds of the scope of 80 quality %, particularly 55～70 quality %.If the amount of fluorine atom is less than 50 quality %, sometimes can't obtain the characteristic such as water and oil-resistant, didirtresistance of target, more than 80 quality %, sometimes can't obtain adaptation, the weather resistance of target if.
As such fluorine-containing organic silicon hydride compounds, particularly, can enumerate the compound shown in following general formula (1)～(3).
(in formula, X is hydrolization group, R
1the monovalence alkyl of carbon number 1～10, R
2be the monovalence alkyl of hydrogen atom or carbon number 1～10, Q is the alkylidene group that can middle have the carbon number 1～10 of NH base.The integer that m is 15～50, n is 2 or 3.）
(in formula, Rf
1mean comprise-(C
tf
2t) the O-(t integer that is 1～6) and shown in unit, there is the divalent group of perfluor polyalkylene ether structure of the straight chain shape of branch, R
3the monovalence alkyl that means carbon number 1～10, X
1mean hydrolization group or halogen atom.P mean independently 0,1 or 2, q mean independently 1～5 integer, r and s mean 2 or 3 separately.）
(in formula, Rf
2for perfluoroalkyl, X
2mean hydrogen atom, bromine atoms or iodine atom, Y is hydrogen atom or low alkyl group, and Z is fluorine atom or trifluoromethyl, R
4for hydroxyl or hydrolyzable group, R
5monovalence alkyl for hydrogen atom or carbon number 1～10.In addition, a, b, c, d, e are the integer more than 0 or 1, and a+b+c+d+e is for more than at least 1, the randomly combination of each repeating unit of a, b, c, d, e.F be 0,1 or 2, g be 1,2 or 3, h be the integer more than 1.）
In above-mentioned formula (1), hydrolization group as X, can enumerate carbon number 1～6, particularly 1～4 alkoxyl groups such as methoxyl group, oxyethyl group, propoxy-, butoxy, the carbon number such as methoxymethoxy, methoxy ethoxy 2～6, particularly 2～4 alkoxyl group alkoxyl group, the acyloxy such as acetoxyl group, the alkene oxygen bases such as different propenyloxy group etc.In these, preferred methoxyl group, oxyethyl group, different propenyloxy group.
In addition, as R
1the monovalence alkyl of carbon number 1～10, can enumerate alkyl, aryl etc., particularly preferably low alkyl group or phenyl, particularly, can enumerate methyl, ethyl, propyl group, butyl, amyl group, hexyl, phenyl etc.In these, preferable methyl.
R
2the monovalence alkyl of hydrogen atom or carbon number 1～10, as R
2the monovalence alkyl, can enumerate alkyl, aryl etc., be preferably hydrogen atom or low alkyl group or phenyl, as concrete example, with R
1equally.In these, preferred hydrogen atom, methyl.
Q is carbon number 1～10,2～8 alkylidene group especially, this alkylidene group can in the middle of have the NH base, be preferably CH
2cH
2cH
2base or CH
2cH
2nHCH
2cH
2cH
2base, in addition, they can mix existence.
The integer that m is 15～50, preferably 20～40, if less than this scope, feature as holo-fluorine polyester is not given full play to, in addition, if larger than this scope, alkoxysilyl shared ratio in molecule is all diminishes terrifically, so the condensation reaction of alkoxysilyl becomes and be difficult to carry out, form aspect tunicle not preferred.N is 2 or 3.
In above-mentioned formula (2), Rf
1to comprise
-（C
tF
2t）O-
(the integer that t is 1～6.）
Shown unit, there is the divalent group of perfluor polyalkylene ether structure of the straight chain shape of branch, be preferably the divalent group shown in following.
-CF
2CF
2O（CF
2CF
2CF
2O）
iCF
2CF
2-
(in formula, i is more than 1, preferred 1～50, more preferably 10～40 integer.）
-CF
2（OC
2F
4）
j-（OCF
2）
k-
(in formula, j and k respectively do for oneself more than 1, preferred 1～50, more preferably 10～40 integer, j+k's and be 10～100, preferably 20～90, more preferably 40～80 integer, the arrangement of above-mentioned repeating unit is random.）
In addition, R
3for the monovalence alkyl of carbon number 1～10, but the R of illustration and above-mentioned formula (1)
1in the identical group of illustrative group.In these, preferable methyl.
X
1for hydrolization group or halogen atom, as hydrolization group, but the identical group of illustrative group in the X of illustration and above-mentioned formula (1).In addition, as halogen atom, can enumerate chlorine atom, bromine atoms, iodine atom etc.In these, preferred chlorine atom.
P is 0,1 or 2 independently, is preferably 1, q and is independently 1～5, preferably 2～4 integer.R and s respectively do for oneself 2 or 3.
In above-mentioned formula (3), Rf
2for perfluoroalkyl, particularly, can enumerate CF
3-, C
2f
5-, C
3f
7-etc.
Y is hydrogen atom or low alkyl group, as low alkyl group, particularly, can enumerate the alkyl of the carbon numbers 1～4 such as methyl, ethyl, propyl group, butyl.
R
4for hydroxyl or hydrolyzable group, as hydrolyzable group, can enumerate carbon number 1～6, particularly 1～4 alkoxyl groups such as methoxyl group, oxyethyl group, propoxy-, butoxy, the carbon number such as methoxymethoxy, methoxy ethoxy 2～6, particularly 2～4 alkoxyl group alkoxyl group, the acyloxy such as acetoxyl group, the alkene oxygen bases such as different propenyloxy group etc.As R
4, preferred methoxyl group, oxyethyl group, different propenyloxy group.
R
5for the monovalence alkyl of hydrogen atom or carbon number 1～10, as the monovalence alkyl of carbon number 1～10, but the R of illustration and above-mentioned formula (1)
1in the identical group of illustrative group.As R
5, preferable methyl.
In addition, a, b, c, d, e are the integer more than 0 or 1, preferably, the integer that a is 0～50, the integer that b is 0～50, the integer that c is 0～50, the integer that d is 0～50, the integer that e is 0～50, a+b+c+d+e is for more than at least 1.The randomly combination of each repeating unit of a, b, c, d, e is arranged again.F be 0,1 or 2, g be 1,2 or 3, h be the integer more than 1.
Next, the fluorine-containing dry type coating agent as for diluting above-mentioned fluorine-containing organic silicon hydride compounds is described with fluorine series solvent (A), (B) of thinner.Said fluorine series solvent in the present invention, refer in molecule that containing under such 25 ℃ of at least one fluorine atom is the organic compound of liquid.
(A) composition is that the boiling point from normal pressure is more than 100 ℃ and is less than at least a kind that selects in the fluorine series solvent of 135 ℃.
As the fluorine series solvent with above-mentioned boiling point, but illustration PFO (bp:104 ℃), Perfluorononane (bp:125 ℃), perfluor-2-butyl tetrahydrofuran (bp:102 ℃), PFTPA (bp:128 ℃) etc. are fluorated solvent fully, and the partially fluorinated solvents such as hexafluoro m-xylene (bp:116 ℃), benzenyl fluoride (bp:102 ℃).
Have again, as (A) composition, can use commercially available product.
As (A) composition, from the easiness of price, solvability and acquisition, preferred PFTPA, hexafluoro m-xylene, benzenyl fluoride, more preferably PFTPA, hexafluoro m-xylene.
(B) composition be the boiling point from normal pressure be more than 80 ℃ below 200 ℃, especially more than 80 ℃ and be less than at least a kind that selects in the fluorine series solvent of 200 ℃.(B) composition can have the boiling point repeated with (A) composition, more than 100 ℃ and be less than the boiling point of 135 ℃, but uses the fluorine series solvent different with the fluorine series solvent as the use of (A) composition.
As the above-mentioned fluorine series solvent with boiling point below 200 ℃ more than 80 ℃, but illustration PF 5070 (bp:82 ℃), PFO (bp:104 ℃), Perfluorononane (bp:125 ℃), perfluor-2-butyl tetrahydrofuran (bp:102 ℃), PFTPA (bp:128 ℃), perfluor tributylamine (bp:174 ℃) etc. are fluorated solvent fully, and the partially fluorinated solvents such as seven fluorine pentamethylene (bp:82.5 ℃), hexafluoro m-xylene (bp:116 ℃), benzenyl fluoride (bp:102 ℃).
Have again, as (B) composition, can use commercially available product, as such fluorine series solvent, can enumerate such as ア サ ヒ Network リ Application AC-6000(Asahi Glass society system, bp:114 ℃), Novec7300(Sumitomo ス リ ー エ system society system, bp:98 ℃) etc.
As (B) composition, from the easiness of price, solvability and acquisition, preferred PFTPA, perfluor tributylamine, perfluor-2-butyl tetrahydrofuran, ア サ ヒ Network リ Application AC-6000, Novec7300.
In the present invention, as above-mentioned (A) composition and (B) composition, (A), (B) compositions different from boiling point evaporate simultaneously, therefore obtain the stable steam output of certain hour, thereby the viewpoint of bringing into play to greatest extent effect of the present invention is set out, preferably use respectively (A) composition and (B) boiling-point difference under the normal pressure of composition be the fluorine series solvent below 80 ℃ more than 10 ℃, particularly preferably use respectively (A) composition and (B) boiling-point difference under the normal pressure of composition be the fluorine series solvent below 60 ℃ more than 10 ℃.If (A), the boiling-point difference of (B) composition is less than 10 ℃, (A), (B) composition evaporates together, the time of stable evaporation capacity shortens, therefore sometimes lose the effect that makes solvent become 2 composition systems, if excessively there is boiling-point difference, for example only (A) composition first evaporates, and becomes (B) composition independent, sometimes loses the effect that makes solvent become 2 composition systems.
For (A), both ratio of mixture of (B) composition (mass ratio), be (A)/(B) 95/5～5/95, be preferably 85/15～15/85.This is than having surpassed in 95/5 situation, or, lower than in 5/95 situation, obtains evenly and the wide difficulty of filming of scope.
Fluorine-containing dry type of the present invention coating agent, so that the fluorine-containing organic silicon hydride compounds is with solid component meter, become 0.1～50 quality %, the preferred mode of 1～30 quality %, with mixing fluorine series solvent (the fluorine-containing dry type coating agent thinner) dilution of above-mentioned (A), (B) composition and use.If the solids component amount of fluorine-containing organic silicon hydride compounds is less than above-mentioned lower value, be difficult to form the coating tunicle of sufficient thickness, if surpass above-mentioned higher limit, in the impregnation of vapor deposition source, become insufficient.
The coating process of fluorine-containing dry type of the present invention coating agent adopts the dry type coating to carry out.
Said dry type coating in the present invention is to instigate the material of gas phase state to be attached to film forming formation face, the method that it is separated out.As the dry type coating, can enumerate PVD methods such as vacuum vapour deposition, sputtering method, ionic fluid method, ionization vapour deposition method and CVD method etc.More specifically, as vacuum vapour deposition, electrical resistance heating, electronic beam method, ratio-frequency heating method, molecular beam epitaxy etc. can be used, as the CVD method, plasma CVD method, optical cvd method, hot CVD method and mocvd method etc. can be used.
The coating of above-mentioned dry type, can adopt known method and condition in the past to carry out.
Wherein, as the base material of coating fluorine-containing dry type of the present invention coating agent, there is no particular restriction, can enumerate the various materials such as paper, cloth, metal and oxide compound thereof, glass, plastics, pottery, quartz.
The fluorine-containing organic silicon hydride compounds that uses fluorine-containing dry type of the present invention coating agent coating on base material by film thickness, preferably 1～50nm, more preferably 5～30nm.
After preferred dry coating, the fluorine-containing organic silicon hydride compounds in the coating agent that makes to separate out solidifies, and as condition of cure, the preferred scope of room temperature to 80 ℃ in addition, is preferably carried out in reaction promoting under humidification.
Embodiment
Referring to embodiment and comparative example, the present invention is illustrated in greater detail, but the present invention is not limited to these embodiment.
[embodiment 1～7, comparative example 1～5]
the modulation of fluorine-containing dry type coating agent
By the fluorine-containing organic silicon hydride compounds shown in following formula (I) (number-average molecular weight: 4,310, fluorine atom amount: 66 quality %), with the solvent composition shown in table 1 dilution, be 20 quality %, make fluorine-containing dry type coating agent.
The solvability of the fluorine-containing dry type coating agent that adopts the method evaluation shown in following to obtain.To the results are shown in table 1.
evaluating characteristics
(a) solvability
Outward appearance by the fluorine-containing dry type of visual investigation coating agent.
Metewand zero: homogeneous transparent
*: muddiness is arranged
the modulation of heating vapor deposition source
After steel wool (Japanese ス チ ー ル ウ ー Le (strain) #0000 processed, wire diameter 0.012mm) 0.005 mass parts is not filled in to the open columnar copper container (internal diameter 6mm * high 1.5mm, capacity 40 μ L) in top with omitting, fill the fluorine-containing dry type coating agent 4 μ L of above-mentioned modulation, make vapor deposition source.
vapor deposition treatment
In small size vacuum evaporation coating device DEPOX VTR-350M/ERH(ア Le バ ッ Network machine work society system) use the base material mounting plate, such as shown in fig. 1, be set to the sliding glass (76mm * 26mm * 1mm) of base material from 4 positions of width between centers 80mm, this base material mounting plate is arranged to the position of the evaporation of evaporation coating device apart from 100mm.Next, in resistive heating, with above-mentioned vapor deposition source is set on the tungsten plate, decompression is to 2.5 * 10
-3after Pa, to the electric current of the logical 67.5A of tungsten plate, heat, by the fluorine-containing organic silicon hydride compounds evaporation in fluorine-containing dry type coating agent in base material and coating has obtained evaporation base material (evaporation thickness: 10nm).Next, under the condition of 40 ℃/80%RH * 16 hour, make it solidify, adopt the method shown in following to carry out evaluating characteristics.
evaluating characteristics
(b) for the static contact angle of water
Use contact angle meter (consonance interface science society system), at room temperature at needle point, make the water droplet of liquid measure 1.2 μ L, it is contacted with the evaporation substrate surface, make drop.Measure the drop of now generation and the angle of face, as static contact angle.To the results are shown in table 1.Have, the A shown in table 1, B, C, D are corresponding to each base material shown in Fig. 1 again.
(c) mensuration of release property
Adopt オ ー ト グ ラ Off AG-IS(Shimadzu Seisakusho Ltd. system), measure under the following conditions.
Pressure sensitive adhesive treated (pressure-sensitive adhesive tape is pasted on to test piece): the wide 19mm of ニ ッ ト ー No.31B(, day eastern electrician (strain) system)
Crimping condition: 20g/cm
2load
Aging: 25 ℃/24 hours
Peeling rate: 300mm/ minute, 180 ° directions
(d) magic ink wiping
At treat surface coating oiliness マ ジ ッ Network (ゼ Block ラ (strain) makes " Ha イ マ ッ キ ー "), with cotton paper (カ ミ business (strain) system " エ Le モ ア "), use following index, by the wiping of visual valuation magic ink.
◎: by 1 wiping operation, wipe fully simply.
Zero: for 1 wiping operation, a small amount of ink residue.
△: for 1 wiping operation, half left and right is residual.
*: do not wipe fully.
[table 1]
(A-1) hexafluoro m-xylene (bp:116 ℃)
(A-2) PFTPA (bp:128 ℃)
(B-1) PFTPA (bp:128 ℃)
(B-2) perfluor tributylamine (bp:174 ℃)
(B-3) perfluor-2-butyl tetrahydrofuran (bp:102 ℃)
(B-4) ア サ ヒ Network リ Application AC-6000(Asahi Glass society system, bp:114 ℃)
(B-5) Novec7300(Sumitomo ス リ ー エ system society system, 1,1,1,2,3,4,4,5,5, the fluoro-3-methoxyl group of 5-ten-2-(trifluoromethyl) pentane, bp:98 ℃)
(B-6) Novec7200(Sumitomo ス リ ー エ system society system, C
4f
9oC
2h
5, bp:78 ℃)
(B-7) perfluor three amylamines (bp:215 ℃)
[embodiment 8～11, comparative example 6～9]
4 batches of the manufactures (all physical property are shown in to table 2) of the fluorine-containing organic silicon hydride compounds that above-mentioned formula (I) is meaned, according to the dilution of the solvent composition shown in table 3, be 20 quality %, make fluorine-containing dry type coating agent, adopt with above-mentioned same method and implement the dry type coating, similarly estimate with above-mentioned.Evaluation result is shown in to table 3 in the lump.
[table 2]
| The manufacture batch of compound | Outward appearance | Number-average molecular weight | Functional group modification rate (%) |
| 1 | Light yellow transparent liquid | 4,310 | 98 |
| 2 | Light yellow transparent liquid | 4,340 | 96 |
| 3 | Colourless transparent liquid | 4,280 | 99 |
| 4 | Yellow transparent liquid | 4,300 | 98 |
Functional group modification rate: with respect to the theoretical amount be modified as containing the methoxyl group of fluorine-based (holo-fluorine polyester), use
1the value that the ratio of the modification amount of the reality that H-NMR obtains is obtained with percentage.
[table 3]
Claims (6)
1. the coating process of fluorine-containing dry type coating agent, it is the coating process of fluorine-containing dry type coating agent, it is characterized in that, by fluorine-containing dry type thinner 100～99 for coating agent for fluorine-containing organic silicon hydride compounds 100 mass parts, 900 mass parts dilutions, modulate fluorine-containing dry type coating agent, use the dry type coating on base material of this coating agent, with thinner, to contain (A) boiling point from normal pressure be more than 100 ℃ and be less than at least a kind of selecting in the fluorine series solvent of 135 ℃ and (B) boiling point from normal pressure is different from (A) composition at least a kind that more than 80 ℃, in the fluorine series solvent below 200 ℃, selects in this fluorine-containing dry type coating agent, (A) mass ratio/(B) is 95/5～5/95.
2. the coating process of fluorine-containing dry type claimed in claim 1 coating agent, wherein, fluorine-containing dry type coating agent is selected from PFTPA and hexafluoro m-xylene with the fluorine series solvent of (A) composition in thinner.
3. the coating process of the described fluorine-containing dry type of claim 1 or 2 coating agent, is characterized in that, fluorine-containing dry type coating agent with (A) composition in thinner and (B) boiling-point difference under the normal pressure of composition be more than 10 ℃ below 80 ℃.
4. the coating process of fluorine-containing dry type claimed in claim 1 coating agent, wherein, the fluorine-containing organic silicon hydride compounds, to adopt the number-average molecular weight of the polystyrene conversion that gel permeation chromatography tries to achieve be the scope below 8,000 more than 1,000.
5. the coating process of fluorine-containing dry type claimed in claim 1 coating agent, wherein, the fluorine-containing organic silicon hydride compounds, adopt
19the fluorine atom amount that F-NMR tries to achieve is more than 50 quality % and is less than the scope of 80 quality %.
6. the coating process of fluorine-containing dry type claimed in claim 1 coating agent, wherein, the fluorine-containing organic silicon hydride compounds is by any expression of following general formula (1)～(3):
In formula, X is hydrolization group, R
1the monovalence alkyl of carbon number 1～10, R
2be the monovalence alkyl of hydrogen atom or carbon number 1～10, Q is the alkylidene group that can middle have the carbon number 1～10 of NH base, the integer that m is 15～50, and n is 2 or 3,
In formula, Rf
1mean comprise-(C
tf
2t) the O-(t integer that is 1-6) and shown in unit, there is the divalent group of perfluor polyalkylene ether structure of the straight chain shape of branch, R
3the monovalence alkyl that means carbon number 1～10, X
1mean hydrolization group or halogen atom, p mean independently 0,1 or 2, q mean independently 1～5 integer, r and s mean 2 or 3 separately,
In formula, Rf
2for perfluoroalkyl, X
2mean hydrogen atom, bromine atoms or iodine atom, Y is hydrogen atom or low alkyl group, and Z is fluorine atom or trifluoromethyl, R
4for hydroxyl or hydrolyzable group, R
5for the monovalence alkyl of hydrogen atom or carbon number 1～10, in addition, a, b, c, d, e are the integer more than 0 or 1, a+b+c+d+e is for more than at least 1, the randomly combination of each repeating unit of a, b, c, d, e, and f is 0,1 or 2, g be 1,2 or 3, h be the integer more than 1.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2012120620A JP2013244470A (en) | 2012-05-28 | 2012-05-28 | Coating method for fluorine-containing dry coating agent |
| JP2012-120620 | 2012-05-28 |
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| CN103451601A true CN103451601A (en) | 2013-12-18 |
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| CN2013101998966A Pending CN103451601A (en) | 2012-05-28 | 2013-05-27 | Coating method of dry coating agent containing fluorine |
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| Country | Link |
|---|---|
| JP (1) | JP2013244470A (en) |
| KR (1) | KR20130133136A (en) |
| CN (1) | CN103451601A (en) |
| TW (1) | TW201406882A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108699394A (en) * | 2016-02-24 | 2018-10-23 | Ａｇｃ株式会社 | Coating fluid composition and used the coating fluid composition the article with film manufacturing method |
| CN110392723A (en) * | 2017-03-14 | 2019-10-29 | 大金工业株式会社 | Surface treating agent containing the silane compound containing perfluor (poly-) ether uses its pellet and article |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR102378656B1 (en) | 2014-10-30 | 2022-03-24 | 에이지씨 가부시키가이샤 | Substrate having antifouling film |
| WO2016136817A1 (en) * | 2015-02-25 | 2016-09-01 | 株式会社ニコン | Fluorine-containing composition, substrate for patterning, photo-degradable coupling agent, method for patterning, and manufacturing method for transistor |
| JP6640593B2 (en) * | 2015-02-25 | 2020-02-05 | 学校法人神奈川大学 | Fluorine-containing composition, pattern forming substrate, photodegradable coupling agent, pattern forming method, and transistor manufacturing method |
| US11681079B2 (en) | 2017-10-31 | 2023-06-20 | Daikin Industries, Ltd. | Surface treatment composition |
| CN111670208A (en) * | 2018-02-02 | 2020-09-15 | 大金工业株式会社 | Silane compound containing fluoro (poly) ether group |
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| JP2009175500A (en) * | 2008-01-25 | 2009-08-06 | Hoya Corp | Method for manufacturing optical member |
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| JP2561395B2 (en) * | 1991-02-27 | 1996-12-04 | ホーヤ株式会社 | Optical member having water-repellent thin film and method for manufacturing the same |
| JPH08143332A (en) * | 1994-11-16 | 1996-06-04 | Oputoron:Kk | Formation of tough water-repellent thin film |
| US8945684B2 (en) * | 2005-11-04 | 2015-02-03 | Essilor International (Compagnie Generale D'optique) | Process for coating an article with an anti-fouling surface coating by vacuum evaporation |
| JP5385146B2 (en) * | 2006-10-20 | 2014-01-08 | スリーエム イノベイティブ プロパティズ カンパニー | Method for easy cleaning substrate and article thereby |
| KR100790426B1 (en) * | 2007-01-30 | 2008-01-03 | 제일모직주식회사 | Coating slurry for manufacturing the cation conductive polymer composite membranes and method for manufacturing the same, membrane-electrode assembly, fuel cell |
-
2012
- 2012-05-28 JP JP2012120620A patent/JP2013244470A/en active Pending
-
2013
- 2013-05-27 TW TW102118640A patent/TW201406882A/en unknown
- 2013-05-27 KR KR1020130059473A patent/KR20130133136A/en not_active Application Discontinuation
- 2013-05-27 CN CN2013101998966A patent/CN103451601A/en active Pending
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| EP0844265A1 (en) * | 1995-08-11 | 1998-05-27 | Daikin Industries, Limited | Silicon-containing organic fluoropolymers and use of the same |
| JP2009139530A (en) * | 2007-12-05 | 2009-06-25 | Seiko Epson Corp | Method for manufacturing optical article |
| JP2009175500A (en) * | 2008-01-25 | 2009-08-06 | Hoya Corp | Method for manufacturing optical member |
| CN102171299A (en) * | 2008-10-01 | 2011-08-31 | 株式会社T&K | Coating composition, method of antifouling treatment and antifouling substrate |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108699394A (en) * | 2016-02-24 | 2018-10-23 | Ａｇｃ株式会社 | Coating fluid composition and used the coating fluid composition the article with film manufacturing method |
| CN108699394B (en) * | 2016-02-24 | 2020-07-31 | Ａｇｃ株式会社 | Coating liquid composition and method for producing article having film using same |
| CN110392723A (en) * | 2017-03-14 | 2019-10-29 | 大金工业株式会社 | Surface treating agent containing the silane compound containing perfluor (poly-) ether uses its pellet and article |
| CN110392723B (en) * | 2017-03-14 | 2022-06-17 | 大金工业株式会社 | Surface treating agent containing silane compound containing perfluoro (poly) ether group, pellet and article using the same |
Also Published As
| Publication number | Publication date |
|---|---|
| TW201406882A (en) | 2014-02-16 |
| KR20130133136A (en) | 2013-12-06 |
| JP2013244470A (en) | 2013-12-09 |
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