CN101151269A - Surface modifier - Google Patents
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- CN101151269A CN101151269A CNA2006800104038A CN200680010403A CN101151269A CN 101151269 A CN101151269 A CN 101151269A CN A2006800104038 A CNA2006800104038 A CN A2006800104038A CN 200680010403 A CN200680010403 A CN 200680010403A CN 101151269 A CN101151269 A CN 101151269A
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Abstract
A surface modifier comprising an organosilicone compound represented by General Formula (A) and/or General Formula(B): F-(CF<SUB>2</SUB>)<SUB>q</SUB>-(OC<SUB>3</SUB>F<SUB>6</SUB>)<SUB>m</SUB>-(OC<SUB>2</SUB>F<SUB>4</SUB>)<SUB>n</SUB>-(OCF<SUB>2</SUB>)<SUB>o</SUB>(CH<SUB>2</SUB>)<SUB>p</SUB>X(CH<SUB>2</SUB>)<SUB>r</SUB> Si(X')<SUB>3-a</SUB>(R<SUP>1</SUP>)<SUB>a</SUB> (A) and F-(CF<SUB>2</SUB>)<SUB>q</SUB>-(OC<SUB>3</SUB>F<SUB>6</SUB>)<SUB>m</SUB>-(OC<SUB>2</SUB>F<SUB>4</SUB>)<SUB>n</SUB>-(OCF<SUB>2</SUB>)<SUB>o</SUB>(CH<SUB>2</SUB>)<SUB>p</SUB>X(CH<SUB>2</SUB>)<SUB>r</SUB> (X')<SUB>2-a</SUB>(R<SUP>1</SUP>)<SUB>a</SUB>SiO(F-(CF<SUB>2</SUB>)<SUB>q</SUB>-(OC<SUB>3</SUB>F<SUB>6</SUB>)<SUB>m</SUB>-(OC<SUB>2</SUB>F<SUB>4</SUB>)<SUB>n</SUB>-(OCF<SUB>2</SUB>)<SUB>o</SUB>(CH<SUB>2</SUB>)<SUB>p</SUB>X(CH<SUB>2</SUB>)<SUB>r</SUB> (X')<SUB>1-a</SUB>(R<SUP>1</SUP>)<SUB>a</SUB>SiO)<SUB>z</SUB>F-(CF<SUB>2</SUB>)<SUB>q</SUB>-(OC<SUB>3</SUB>F<SUB>6</SUB>)<SUB>m</SUB>-(OC<SUB>2</SUB>F<SUB>4</SUB>)<SUB>n</SUB>-(OCF<SUB>2</SUB>)<SUB>o</SUB>(CH<SUB>2</SUB>)<SUB>p</SUB>X(CH<SUB>2</SUB>)<SUB>r</SUB> (X')<SUB>2-a</SUB>(R<SUP>1</SUP>)<SUB>a</SUB>Si (B) wherein q is an integer from 1 to 3; m, n, and o are independently integers from 0 to 200; p is 1 or 2; X is O or a bivalent organic group; r is an integer from 2 to 20; R<SUP>1</SUP> is a C<SUB>1-22</SUB> linear or branched hydrocarbon group; a is an integer from 0 to 2; X' is hydrolysable group; and z is an integer from 0 to 10 when a is 0 or 1.
Description
Technical field
The present invention relates to be used on the surface of various base materials, forming the surface-modifying agent of low surface tension layer or dust layer, and use described surface-modifying agent to form the method for processing layer.In addition, the present invention relates to optical element (for example, anti-reflective film, optical filter, optical lens, glasses lens, spectroscope (beam splitter), prism, mirror etc.), wherein used described surface-modifying agent; Be applied in the antireflective optical member of the screen surface of indicating meter (for example, liquid-crystal display, CRT monitor, projection TV, plasma display, EL indicating meter etc.); The optical functional element; Wherein said optical functional element sticks to the display equipment of display screen surface; Treated eyeglass; Treated pottery etc.
Background technology
Antireflecting coating, optical filter, optical lens, flexible focal length lenses group, spectroscope, prism, mirror and other optical elements and bathroom apparatus are easy to be stained with fingerprint, skin oil (skin oil), sweat, makeup etc. in use.In case be stained with, these dirts are easy-clear not, particularly, be bonded on the optical element with antireflecting coating dirt very obviously and throw into question.In addition, the window of automobile and aircraft requires to have persistent water-repellancy.
Be the solution problem relevant, proposed to use the technology of various stain control agents so far with dirt and water-repellancy.
For example, the Japanese unexamined patent publication compound that proposed to contain by use perfluoroalkyl for 1997-61605 number carries out the antifouling antireflection filter that surface treatment obtains to base material.Japan's unexamined patent communique has proposed a kind of antifouling, low reflection plastic for 1994-29332 number, has in its surface to comprise the single silane that contains poly-fluoroalkyl and the antireflecting coating of disilane compound and halogen silane, alkyl silane or alkoxysilane compound containing trialkylsilyl group in molecular structure.Japanese unexamined patent publication has proposed for 1995-16940 number by forms the optical element that (methyl) perfluoroalkyl acrylate and the monomeric multipolymer that contains alkoxysilane groups obtain on the optical thin film that mainly is made of silicon-dioxide.
Yet the didirtresistance deficiency that the antifouling coating that is formed by hitherto known method has especially, is difficult to remove from it such as dirts such as fingerprint, skin oil, sweat and makeup.In addition, when life-time service, its didirtresistance reduces greatly.Therefore, the antifouling coating that needs exploitation to have excellent stain and excellent wearing quality.
Summary of the invention
The present invention can form surface-modifying agent excellent, long-lived low surface tension processing layer in order to solve the above-mentioned prior art problems of mentioning and to provide, described processing layer can prevent moisture or stick to various base materials such as dirts such as fingerprint, skin oil, sweat and makeup, especially on the surface of optical element such as anti-reflective film and glass, in a single day and when being stained with, can easily wipe dirt or moisture.
Another object of the present invention provides the method that preparation can form the surface-modifying agent of excellent low surface tension layer.
A further object of the present invention provides the method that can easily form excellent low surface tension layer.
Another purpose of the present invention provides the optical element and the various base material of the low surface tension layer that is equipped with described excellence.
Another purpose of the present invention provides the antireflective optical member of the low surface tension layer that is equipped with described excellence.
Another purpose of the present invention provides the optical functional element that is equipped with described antireflection element.
Another purpose of the present invention provides display equipment, and described display equipment has the display screen surface that is equipped with described optical functional element.
Another purpose of the present invention provides compound of the present invention in miniature manufacturing field, for example application in the nano impression (nanoimprinting), and it has significant technical progress in recent years, thereby has realized the accurate demoulding.
Another purpose of the present invention provides the application of compound of the present invention in device is made so that a kind of material and working method to be provided, thereby makes because the excellence of compound of the present invention is repelled the performance lines (line) that easily working width is very little.
Another purpose of the present invention provides compound of the present invention such as the application in the processing of stonewares such as concrete, Wingdale, grouan or marble.
The invention provides a kind of dust-proofing agent, described dust-proofing agent contains the organic silicone compound by general formula (A) and/or partial hydrolysate general formula (B) expression.
F-(CF
2)
q-(OC
3F
6)
m-(OC
2F
4)
n-(OCF
2)
o(CH
2)
pX(CH
2)
rSi(X′)
3-a(R
1)
a (A)
In general formula (A), q is 1～3 integer; M, n and o are 0～200 integer independently; P is 1 or 2; X is O or divalent organic group; R is 2～20 integer; R
1Be C
1-22The alkyl of straight chain or branching; A is 0～2 integer; X ' is a hydrolization group.
F-(CF
2)
q-(OC
3F
6)
m-(OC
2F
4)
n-(OCF
2)
o(CH
2)
pX(CH
2)
r(X′)
2-a(R
1)
aSiO(F-(CF
2)
q-(OC
3F
6)
m-(OC
2F
4)
n-(OCF
2)
o(CH
2)
pX(CH
2)
r(X′)
1-a(R
1)
aSiO)
zF-(CF
2)
q-(OC
3F
6)
m-(OC
2F
4)
n-(OCF
2)
o(CH
2)
pX(CH
2)
r(X′)
2-a(R
1)
aSi (B)
In general formula (B), q is 1～3 integer; M, n and o are 0～200 integer independently; P is 1 or 2; X is O or divalent organic group; R is 2～20 integer; R
1Be C
1-22The alkyl of straight chain or branching; A is 0～2 integer; X ' is a hydrolization group; And when a was 0 or 1, z was 0～10 integer.
In addition, the invention provides the method for the above-mentioned surface-modifying agent of preparation.
The invention provides the method for using described surface-modifying agent to produce low surface tension.
The invention provides by using the surface of the low surface tension that described surface-modifying agent obtains.
The invention provides the optical element that is equipped with the processing layer that contains described surface-modifying agent.
The invention provides the antireflective optical member that is equipped with the processing layer that contains described surface-modifying agent.
The invention provides the optical functional element that contains described antireflective optical member.
The invention provides the display equipment that is equipped with described optical functional element.
The invention provides such as inorganic substrates such as glass, described inorganic substrate has the surface that has been equipped with the processing layer that contains described surface-modifying agent.
The invention provides automobile and aeronautical glasses and bathroom apparatus with the inorganic substrate that has above-mentioned surface.
The invention provides the application of described surface-modifying agent in the accurate demoulding of nano impression.
The invention provides the method for using described surface-modifying agent easily to make device with microtexture.
Embodiment
Because surface-modifying agent of the present invention contains specific organic silicone compound, therefore when going up the described surface-modifying agent formation of use processing layer at for example various optical elements of base material (anti-reflective film, optical filter, optical lens, glasses lens, spectroscope, prism, mirror etc.), can prevent such as the adhesion of dirts such as fingerprint, skin oil, sweat, makeup or moisture and the optical characteristics of the described optical element of non-deterioration, and, even adhere to dirt and moisture, also can easily wipe, make described processing layer have excellent wearing quality thus.
Dust-proofing agent of the present invention contains the organic silicone compound by general formula (A) and/or general formula (B) expression.
F-(CF
2)
q-(OC
3F
6)
m-(OC
2F
4)
n-(OCF
2)
o(CH
2)
pX(CH
2)
rSi(X′)
3-a(R
1)
a (A)
F-(CF
2)
q-(OC
3F
6)
m-(OC
2F
4)
n-(OCF
2)
o(CH
2)
pX(CH
2)
r(X′)
2-a(R
1)
aSiO(F-(CF
2)
q-(OC
3F
6)
m-(OC
2F
4)
n-(OCF
2)
o(CH
2)
pX(CH
2)
r(X′)
1-a(R
1)
aSiO)
zF-(CF
2)
q-(OC
3F
6)
m-(OC
2F
4)
n-(OCF
2)
o(CH
2)
pX(CH
2)
r(X′)
2-a(R
1)
aSi (B)
In general formula (A), q is 1～3 integer; M, n and o are 0～200 integer independently; P is 1 or 2; X is O or divalent organic group; R is 2～20 integer; R
1Be C
1-22The alkyl of straight chain or branching; A is 0～2 integer; X ' is a hydrolization group.
In general formula (B), q is 1～3 integer; M, n and o are 0～200 integer independently; P is 1 or 2; X is O or divalent organic group; R is 2～20 integer; R
1Be C
1-22The alkyl of straight chain or branching; A is 0～2 integer; X ' is a hydrolization group; And when a was 0 or 1, z was 0～10 integer.
Be preferably, at general formula (A) with (B), X is Sauerstoffatom or divalent organic group, as C
1-22The alkylidene group of straight chain or branching;
R
1Be C
1-22Alkyl, more preferably C
1-12Alkyl; And
X ' is a chlorine, alkoxyl group (OR) or-O-N=CR
2, wherein R is C
1-22The alkyl of the alkyl of straight chain or branching, especially straight chain or branching.
Described general formula (A) or hydrolization group X ' (B) can enumerate the group of following formula: alkoxyl group or have the alkoxyl group of alkoxy substituent, as methoxyl group, oxyethyl group, propoxy-and methoxy ethoxy; Acyloxy is as acetoxyl group, propionyloxy and benzoyloxy; Alkene oxygen base is as different propenyloxy group and iso-butylene oxygen base; Inferior aminooxy (iminoxy) is as dimethyl ketone oximido, methyl ethyl ketone oximido, metacetone oximido, hexamethylene oximido; Has substituent amino, as methylamino, ethylamino, dimethylamino and diethylamino; Amido is as N-methyl kharophen and N-buserelin base; Has substituent aminooxy (aminoxy), as dimethyl aminooxy and diethyl aminooxy; Halogen is as chlorine etc.In these hydrolization groups, especially preferably-OCH
3,-OC
2H
5With-O-N=C (CH
3)
2These hydrolization groups can be used as a kind of material or are included in the organic silicone compound of dust-proofing agent of the present invention as the combination of two or more materials.
At general formula (A) with (B), the summation of m, n and o is preferably more than 5, is preferably more than 10 especially.X is preferably oxygen and r is preferably 3.In formula (A), a is preferably 0.
In compound by general formula (A) expression, wherein X be that oxygen, r are 3, a be 0 and X ' be-OCH
3Can be by the particularly preferred compound of general formula (A) expression by trichlorosilane and the hydrosilylation reactions of compound in the presence of transition metal by following general formula (C) expression, and utilize the methyl alcohol dehydrochlorination subsequently and synthesize.Preferably use such as acid acceptors such as sodium methylate or trimethyl orthoformates to promote described dehydrochlorination.
Operable catalytic group VIII transition metal is preferably platinum or rhodium in hydrosilylation.Most preferably be platinum.Preferably as Platinic chloride or as with 1,3-divinyl-1,1,3, the platinum complex of 3-tetramethyl disiloxane provides platinum, perhaps as chlorination three (triphenylphosphinyl) rhodium
IRhodium is provided.
F-(CF
2)
q-(OC
3F
6)
m-(OC
2F
4)
n-(OCF
2)
o(CH
2)
pXCH
2CH＝CH
2 (C)
In general formula (C), q is 1～3 integer; M, n and o are 0～200 integer independently; P is 1 or 2; X is O or divalent organic group.
Specifically be to prepare particularly preferred compound according to following reaction scheme.
F-(CF
2)
q-(OC
3F
6)
m-(OC
2F
4)
n-(OCF
2)
o-(CH
2)
p-X-CH
2CH＝CH
2+HSiCl
3
↓
F-(CF
2)
q-(OC
3F
6)
m-(OC
2F
4)
n-(OCF
2)
o-(CH
2)
p-X-(CH
2)
3-SiCl
3+CH
3OH
↓
F-(CF
2)
q-(OC
3F
6)
m-(OC
2F
4)
n-(OCF
2)
o-(CH
2)
p-X-(CH
2)
3-Si(OCH
3)
3
In above-mentioned reaction scheme, q is 1～3 integer; M, n and o are 0～200 integer independently; P is 1 or 2; X is oxygen or divalent organic group.In above-mentioned reaction scheme, use HSi (OMe)
3Perhaps HSi (OEt)
3Replace HSiCl
3Can make other preferred compound, have the additional advantage that did not need dehydrochlorination to turn into to be second step.
By carrying out hydrosilylation reactions with the appropriate timed interval and thermotonus, finish thereby order about reaction with excessive silicon hydride.As selection, can add suitable solvent to promote mixing.Can use such as various instrumental method monitoring reaction processes such as nucleus magnetic resonance or infrared spectras.For example, preferred condition is at 30 ℃～90 ℃, use conduct with 1,3-divinyl-1,1,3, the platinum complex catalyst of 3-tetramethyl disiloxane, be the platinum of 0.01mmol～10mmol of providing of group VIII transition metal, with the fluorine cpd 1.05mol of every mol～30mol trichlorosilane reaction 1～10 hour.Can easily from reaction product, remove any excessive silicon hydride by vacuum distilling.
If trichlorosilane is used for described hydrosilylation, second reaction is preferably following carrying out, that is, obtain in the compound in every mole first reaction, the trimethyl orthoformate of 0.05 mole～10 molar excess and methanol mixture were reacted 1 hour～10 hours down at 30 ℃～70 ℃.Can use such as various instrumental method monitoring reaction processes such as nucleus magnetic resonance or infrared spectras.Can easily from reaction product, remove any excessive trimethyl orthoformate and methyl alcohol by vacuum distilling.
In the above fluorine cpd that provide by general formula (C) expression, particularly preferably be wherein that q is 3, m is 10～200, and n is 1, and o is 0, and p is 1, X is the fluorine cpd by general formula (C) expression of oxygen.
Other compounds by general formula (A) expression can be synthetic similarly according to above-mentioned reaction scheme.
By can synthesize compound by the partial hydrolysis of the compound of general formula (A) expression and condensation reaction by general formula (B) expression.Can use separately or as the combination of two or more materials use by general formula (A) and/or (B) expression the organic silicone compound to form surface-modifying agent of the present invention.
The surface modification of the organic silicone compound that if desired, can use optional catalyzer to utilize general formula (A) and/or (B) represent with promotion.They can use separately or being used in combination to form surface-modifying agent of the present invention as two or more materials.Suitable catalytic examples for compounds comprises the organic acid metal-salt, as two sad dibutyl tins, iron stearate, lead octoate 36 and other materials; Titanic acid ester is as tetra isopropyl titanate, tetrabutyl titanate ester; Inner complex is as titanium acetylacetone etc.Based on 100 weight parts described by general formula (A) and/or (B) expression the organic silicone compound, preferably use described optional catalyzer, more preferably 0.01 weight part～2 weight parts with the amount of 0 weight part～5 weight parts.
General formula (A) and/or organic silicone compound (B) are the active ingredients of described surface-modifying agent.Described surface-modifying agent is made up of general formula (A) and/or organic silicone compound (B).Described surface-modifying agent can comprise general formula (A) and/or organic silicone compound (B) and such as liquid mediums such as organic solvents.Based on described surface-modifying agent, the organic silicone compound concentrations in the described surface-modifying agent is preferably 0.01 weight %～80 weight %.
Described organic solvent can be an all kinds of SOLVENTS, described organic solvent not with composition of the present invention under the condition that reacts of the component (especially described organic silicone compound) that contained, preferred described solvent can dissolve described organic silicone compound.Described representative examples of organic comprises and contains fluorous solvent, as fluorine-containing alkane, fluorine-containing alkyl halide hydrocarbon, fluorine-containing aromatic hydrocarbon and fluorine-containing ether (for example, hydrogen fluorine ether (HFE)).
The base material of handling to form surface-treated layer with surface-modifying agent of the present invention is not particularly limited.Its example comprises optical element, comprising: inorganic substrate, as sheet glass, the sheet glass that contains inorganic layer and pottery etc.; Organic substrate such as transparent plastic substrate and the transparent plastic substrate that contains inorganic layer; Deng.
The example of inorganic substrate comprises sheet glass.The example that is used to form the mineral compound of the sheet glass that contains inorganic layer comprises metal oxide (silicon oxide (silicon-dioxide, silicon monoxide etc.), aluminum oxide, magnesium oxide, titanium oxide, stannic oxide, zirconium white, sodium oxide, weisspiessglanz, Indium sesquioxide, bismuth oxide, yttrium oxide, cerium oxide, zinc oxide, ITO (tin indium oxide) etc.); And metal halide (magnesium fluoride, Calcium Fluoride (Fluorspan), Sodium Fluoride, lanthanum fluoride, cerium fluoride, lithium fluoride, thorium fluoride etc.).
Described inorganic layer or inorganic substrate (containing this mineral compound) can be single or multiple lifts.Described inorganic layer is used as anti-reflecting layer, and can be by forming such as wet type coating, PVD (physical vapor deposition), CVD currently known methodss such as (chemical vapour depositions).The example of wet type coating method comprises methods such as dip coated, spin coating, flow coat, spraying, roller coat, gravure coating.The example of PVD method comprises methods such as vacuum-evaporation, reactive deposition, ion beam assisted depositing, sputter, ion plating.
In the available organic substrate, the example of transparent plastic substrate comprises the base material that contains various organic polymers.From transparency; specific refractory power; optical properties such as dispersibility; and such as shock resistance; the angle of various other character such as thermotolerance and wearing quality is considered; base material as optical element contains polyolefine (polyethylene usually; polypropylene etc.); polyester (polyethylene terephthalate; Polyethylene Naphthalate etc.); polymeric amide (nylon 6; nylon 66 etc.); polystyrene; polyvinyl chloride; polyimide; polyvinyl alcohol; ethylene-vinyl alcohol (ethylene vinyl alcohol); acrylic resin; Mierocrystalline cellulose (tri acetyl cellulose; diacetyl cellulose; glassine paper etc.), the perhaps multipolymer of these organic polymers.Can mention these base materials conducts example of processed transparent plastic substrate in the present invention.
The available examples of material comprises by add the material for preparing such as additives known such as static inhibitor, UV absorption agent, softening agent, lubricant, tinting material, antioxidant, fire retardants in the organic polymer of these organic substrates.
Also the base material for preparing by formation inorganic layer on organic substrate can be used as base material of the present invention.In this case, described inorganic layer also can be formed on the organic substrate by aforesaid method as anti-reflecting layer.
Pending inorganic substrate or organic substrate are not particularly limited.Be generally the form of film or sheet as the transparent plastic substrate of optical element.The base material of these films or sheet form also can be used as base material of the present invention.The base material of film or sheet form can be the laminate of individual layer organic polymer or multilayer organic polymer.Its thickness is not particularly limited, but is preferably 0.01mm～5mm.
Can between transparent plastic substrate and inorganic layer, form hard coat.Described hard coat can improve the hardness of described substrate surface and substrate surface is flattened with smooth, thereby improves the binding property between described transparent plastic substrate and the inorganic layer.Therefore, can prevent the cut that loads such as pencil cause.In addition, described hard coat can suppress by the breaking of the crooked caused described inorganic layer of described transparent plastic substrate, thereby improves the physical strength of described optical element.
The material of described hard coat is not particularly limited, as long as it has transparency, suitable hardness and physical strength.For example, can use thermosetting resin and by the resin of ionizing radiation or cured with ultraviolet radiation.Preferred especially UV-solidified nature acrylic resin, silicone resin and thermoset polyorganosiloxane resin.It is identical or close with the specific refractory power of described transparent plastic substrate that the specific refractory power of these resins is preferably.
The coating process that forms this hard coat is not particularly limited.Can use any method that can realize the homogeneous coating.During thickness more than described hard coat has 3 μ m, can obtain enough intensity.Yet consider from aspects such as transparency, coating precision and processing eases, be preferably 5 μ m～7 μ m.
In addition, by being the inorganic or organic granular mixing of 0.01 μ m～3 μ m with median size and being scattered in the described hard coat that the light diffusion that can be commonly referred to " antiglare " is handled.Though any transparent grain all can be used as such particle, preferred low-index material.Consider stability, thermotolerance etc., preferred especially silicon oxide and magnesium fluoride.Also can realize the light diffusion processing by the hard coat with hackly surface is provided.
Above-mentioned base material can be used as the transparent substrate of antireflective optical member of the present invention.Particularly, this base material that has anti-reflecting layer from the teeth outwards can be the transparent substrate with anti-reflecting layer.Antireflective optical member of the present invention can obtain by form dust layer on the surface of described base material.
Therefore except that these optical elements, surface-modifying agent of the present invention can be used for the window parts of automobile or aircraft, provides advanced functional.For further improving surface hardness, but also the so-called sol-gel method of the combination of the surface-modifying agent of the application of the invention and TEOS (tetraethoxysilane) is carried out surface modification.
The surface-modifying agent of the application of the invention can easily be realized the accurate demoulding as the releasing agent in the nano impression process.When with surface-modifying agent treat surface of the present invention, described properties-correcting agent almost is diffused as the individual layer state, so the layer of gained only has the thickness of several nanometers.Although be this thickness, also can form water contact angle is more than 110 °, and the water droplet angle is the surface below 5 °, as shown in subsequent embodiment.
Surface-modifying agent of the present invention has excellent liquid-repellency, therefore can be used for lithography and device moulding.
In addition, by handling ceramic material surfaces, also can produce the bathroom apparatus and the outer wall of easy maintenance.
The method of described formation processing layer is not particularly limited.For example, can use wet type coating method and dry type coating method.
The example of wet type coating method comprises methods such as dip coated, spin coating, flow coat, spraying, roller coat and gravure coating.
The example of dry type coating method comprises methods such as vacuum-evaporation, sputter and CVD.The object lesson of vacuum vapor deposition method comprises methods such as resistive heating, electron beam, ratio-frequency heating and ionic fluid.The example of CVD method comprises methods such as plasma body-CVD, optics CVD and hot CVD.
In addition, the coating of being undertaken by the atmospheric pressure plasma method also is fine.
When using the wet type coating method, the available diluting solvent is not particularly limited.From stability and volatile angle of described composition, preferred following compound: have the perfluor aliphatic hydrocarbon of 5～12 carbon atoms, as perflexane, perfluoromethyl cyclohexane and perfluor-1,3-dimethyl cyclohexane; Polyfluoro aromatic hydrocarbon is as two (trifluoromethyl) benzene; The polyfluoro aliphatic hydrocarbon, HFE such as perfluorobutyl methyl ethers etc.These solvents can use separately or use with two or more mixtures.
For base material, preferably use the wet type coating method with complicated shape and/or huge area.
On the other hand, consider the Working environment when forming dust layer, preferably wherein do not need the dry type coating method of diluting solvent.Especially preferred vacuum vapor deposition method.
On described base material, form after the dust layer by dry type or wet type coating method, if desired, can heat, humidification, optical radiation, electron beam irradiation etc.
The thickness of the dust layer that the dust-proofing agent of the application of the invention forms is not particularly limited.Dirt resistance, erasibility and optical property according to described optical element are preferably 1nm～10nm.
Embodiment
Following examples are in order to describing the present invention in detail, but not limit the scope of the invention.
Synthesis example 1
In the 1L three-necked flask of being furnished with magnetic stirring bar, reflux exchanger, temperature control and drying nitrogen headspace cleaner, add 411.2g (F
3CCF
2CF
2(OCF
2CF
2CF
2)
11OCF
2CF
2CH
2OCH
2CH=CH
2), 286.13g 1,3-two (trifluoromethyl) benzene and 110.47g trichlorosilane.Adding 0.045g and 1 with 3.7 hours, 3-divinyl-1,1,3 before the Pt metal of 3-tetramethyl disiloxane complexing, is heated to 60 ℃ with content.Content is kept 30 minutes to make F again at 60 ℃
3CCF
2CF
2(OCF
2CF
2CF
2)
11OCF
2CF
2CH
2OCH
2CH
2CH
2SiCl
3Before adding 156.5g trimethyl orthoformate and 1.8g methyl alcohol, trichlorosilane and the solvent vacuum from reaction mixture of remnants are removed.Content in the described flask is spent the night to promote the methoxylation of chlorosilane 60 ℃ of maintenances.After 14 hours, add other 5.2g methyl alcohol and kept temperature 3 hours.Add the 2.5g activated carbon.Under vacuum, remove excess reagent.By the diatomite on 5 micron membranes (Celite) flocculating aids bed filtration product.With product F
3CCF
2CF
2(OCF
2CF
2CF
2)
11OCF
2CF
2CH
2OCH
2CH
2CH
2Si (OMe)
3Be separated into filtrate.Infrared and nmr analysis shows CH
2=CHCH
2O and the completely dissolve of SiCl functional group.
Synthesis example 2
To the 25mL two neck flasks adding 7.52g (F that is furnished with magnetic stirring bar, reflux exchanger, temperature control and headspace is purified with drying nitrogen
3CCF
2CF
2(OCF
2CF
2CF
2)
11OCF
2CF
2CH
2OCH
2CH=CH
2), 12.02g 1,3-two (trifluoromethyl) benzene and 3.91g Trimethoxy silane.Slowly adding 1.4 * 10 with 16 hours
-3G and 1,3-divinyl-1,1,3 before the Pt metal of 3-tetramethyl disiloxane complexing, is heated to 100 ℃ with content.After two hours, under vacuum, remove excess reagent.Product F
3CCF
2CF
2(OCF
2CF
2CF
2)
11OCF
2CF
2CH
2OCH
2CH
2CH
2Si (OMe)
3Separate as the flask residue, mix with activated carbon and filter.Infrared and nmr analysis shows there is not initial CH
2=CHCH
2O functional group is residual.
Synthesis example 2～8:
According to synthesis example 1 described identical method, synthetic following compound.
Synthetic compound 2;
F
3CCF
2CF
2(OCF
2CF
2CF
2)
21OCF
2CF
2CH
2OCH
2CH
2CH
2Si(OMe)
3
Synthetic compound 3;
F
3CCF
2CF
2(OCF
2CF
2CF
2)
30OCF
2CF
2CH
2OCH
2CH
2CH
2Si(OMe)
3
Synthetic compound 4;
F
3CCF
2CF
2(OCF
2CF
2CF
2)
21OCF
2CF
2CONHCH
2CH
2CH
2Si(OMe)
3
Synthetic compound 5;
F
3CCF
2CF
2O[CF(CF
3)CF
2O]
3CF(CF
3)CH
2OCH
2CH
2CH
2Si(OMe)
3
Synthetic compound 6;
F
3CCF
2CF
2O[CF(CF
3)CF
2O]
3CF(CF
3)CONHCH
2CH
2CH
2Si(OMe)
3
Synthetic compound 7;
F
3CCF
2CF
2O[CF(CF
3)CF
2O]
4CF(CF
3)CH
2OCH
2CH
2CH
2Si(OMe)
3
Synthetic compound 8;
F
3CCF
2CF
2O[CF(CF
3)CF
2O]
5CF(CF
3)CH
2OCH
2CH
2CH
2Si(OMe)
3
Comparative compound a
Buy Optool DSX (producing), be called comparative compound a by Daikin Ind Ltd.
Embodiment 1
The pre-treatment of silicon wafer substrate:
At 25 ℃, (supersound process 10 minutes in acetone of 2cm * 4cm * 0.7mm), and at 100 ℃ was cleaned 1 hour in sulfuric acid/30 quality % superoxol=70/30 (V/V, volume/volume) with silicon wafer.In order wafer is cleaned with methyl alcohol and ethanol subsequently, and dry under the room temperature decompression.In addition, under 70Pa, carried out the UV/ ozonize 10 minutes, confirm that thus water contact angle is 0 °.
Be coated with the surface-modifying agent wet type:
With HFE-7200 (3M manufacturing) each synthetic compound and comparative compound being diluted to concentration is 0.05 quality %, 0.10 quality % and 0.50 quality %.At 25 ℃, will be as above pretreated silicon wafer be immersed in the diluted compounds 30 minutes, then 25 ℃ of dryings 24 hours.Then at 25 ℃, with the ultrasonic cleaning 10 minutes in HFE-7200 of described wafer, and 25 ℃ of drying under reduced pressure 1 hour.
The measurement of contact angle and slide angle (sliding angle):
Use Model CA-X:Kyowa Interface Science Co., Ltd. measures the water contact angle and the water slide angle of described processing sample.Under the condition of 20 ℃ and 65%RH (relative humidity), use the distillation water droplet of 20 μ l to carry out described measurement.
Fingerprint adhesion:
With the finger by on the surface of described processing sample to be stained with fingerprint, the adhesivity of described fingerprint and perceptibility carry out visual assessment according to following standard.
A: only be stained with fingerprint slightly, even and be stained with fingerprint and also be difficult for discovering.
B: the fingerprint that is stained with is easily discovered.
Remove the easiness of fingerprint by wiping:
The fingerprint that uses non-woven fibre cellulose fabric (Bemcot M-3, by Asahi Chemical Co., Ltd. makes) to wipe to be bonded on the sample surfaces is to estimate the removing property of fingerprint according to following standard vision.
A: can wipe fingerprint fully.
B: residual after the wiping have a fingerprint trace.
C: fingerprint can not be wiped.
Erasibility:
Use non-woven fibre cellulose fabric (Bemcot M-3, by Asahi Chemical Co., Ltd. makes) with the load friction sample surfaces of 500gf 100 times, and carry out above test.
Table 1
| Synthetic compound 1 | Comparative example a | |||||
| 0.05 quality % | 0.10 quality % | 0.50 quality % | 0.05 quality % | 0.10 quality % | 0.50 quality % | |
| Contact angle | 115(114) | 116(116) | 120(118) | 114(112) | 115(113) | 120(119) |
| Slide angle | 3(3) | 3(3) | 3(3) | 40(45) | 39(41) | 22(25) |
| Fingerprint adhesion | A(A) | A(A) | A(A) | A(A) | A(A) | A(A) |
| Remove the easiness of fingerprint | A(A) | A(A) | A(A) | A(B) | A(B) | A(A) |
In table 1, the numerical value in the bracket is the value of erasibility test.
Table 1 has shown that the processing layer that uses surface-modifying agent of the present invention to form has the water contact angle similar to the processing layer of comparative example, but has littler water slide angle, therefore is difficult to water-wet and makes fingerprint to wipe easily.Described table has shown that also these excellent properties are persistent.
Embodiment 2
According to the method identical, the various character of synthetic compound 2～8 have been measured with embodiment 1.The result is presented in table 2～5.
Table 2
| Synthetic compound 2 | Synthetic compound 3 | |||||
| 0.05 quality % | 0.10 quality % | 0.50 quality % | 0.05 quality % | 0.10 quality % | 0.50 quality % | |
| Contact angle | 116(115) | 116(116) | 120(118) | 114(114) | 116(115) | 120(119) |
| Slide angle | 3(3) | 3(3) | 3(3) | 4(5) | 3(3) | 3(3) |
| Fingerprint adhesion | A(A) | A(A) | A(A) | A(A) | A(A) | A(A) |
| Remove the easiness of fingerprint | A(A) | A(A) | A(A) | A(A) | A(A) | A(A) |
Table 3
| Synthetic compound 4 | |||
| 0.05 quality % | 0.10 quality % | 0.50 quality % | |
| Contact angle | 115(113) | 115(116) | 119(117) |
| Slide angle | 4(4) | 3(3) | 3(3) |
| Fingerprint adhesion | A(A) | A(A) | A(A) |
| Remove the easiness of fingerprint | A(A) | A(A) | A(A) |
Table 4
| Synthetic compound 5 | Synthetic compound 6 | |||||
| 0.05 quality % | 0.10 quality % | 0.50 quality % | 0.05 quality % | 0.10 quality % | 0.50 quality % | |
| Contact angle | 112(110) | 114(112) | 115(113) | 112(111) | 113(112) | 114(113) |
| Slide angle | 3(3) | 3(3) | 2(3) | 4(5) | 3(3) | 3(3) |
| Fingerprint adhesion | A(A) | A(A) | A(A) | A(A) | A(A) | A(A) |
| Remove the easiness of fingerprint | A(A) | A(A) | A(A) | A(A) | A(A) | A(A) |
Table 5
| Synthetic compound 7 | Synthetic compound 8 | |||||
| 0.05 quality % | 0.10 quality % | 0.50 quality % | 0.05 quality % | 0.10 quality % | 0.50 quality % | |
| Contact angle | 113(112) | 115(114) | 116(115) | 114(113) | 114(113) | 116(115) |
| Slide angle | 3(4) | 3(3) | 2(3) | 3(4) | 3(3) | 2(3) |
| Fingerprint adhesion | A(A) | A(A) | A(A) | A(A) | A(A) | A(A) |
| Remove the easiness of fingerprint | A(A) | A(A) | A(A) | A(A) | A(A) | A(A) |
Table 2, table 3, table 4 and table 5 show and result identical described in the table 1.
Effect of the present invention
Compare with the processing layer that uses hitherto known inorganic agent to form, the processing layer that uses surface modifier of the present invention to form at substrate surface has less slide angle, therefore more anti-dirts such as fingerprint, skin oil, sweat and cosmetics. In addition, even these dirts are bonded on the processing layer of surface modifier of the present invention, they also can be wiped easily. In addition, these character can stably show.
In addition, by the optical functional element that optical element of the present invention or antireflective optical member and optical functional combination of elements are obtained, such as deflecting plates etc., comprise and have above-mentioned excellent functionality and be formed on enduringly its lip-deep processing layer, therefore when when combining with the front panel of the display screen of various displays (liquid crystal display, CRT monitor, the projection display, plasma display, EL display etc.), can provide the display equipment with hi-vision identity of the present invention.
In addition, the processing layer that uses surface modifier of the present invention to be formed on the substrate surface is very thin, therefore has high accuracy processability and excellent micromachining.
Claims (34)
1. surface-modifying agent, described surface-modifying agent contain the organic silicone compound by general formula (A) and/or general formula (B) expression:
F-(CF
2)
q-(OC
3F
6)
m-(OC
2F
4)
n-(OCF
2)
o(CH
2)
pX(CH
2)
rSi(X′)
3-a(R
1)
a (A)
Wherein, q is 1～3 integer; M, n and o are 0～200 integer independently; P is 1 or 2; X is O or divalent organic group; R is 2～20 integer; R
1Be C
1-22The alkyl of straight chain or branching; A is 0～2 integer; X ' is a hydrolization group; With
F-(CF
2)
q-(OC
3F
6)
m-(OC
2F
4)
n-(OCF
2)
o(CH
2)
pX(CH
2)
r(X′)
2-a(R
1)
aSiO(F-(CF
2)
q-(OC
3F
6)
m-(OC
2F
4)
n-(OCF
2)
o(CH
2)
pX(CH
2)
r(X′)
1-a(R
1)
aSiO)
zF-(CF
2)
q-(OC
3F
6)
m-(OC
2F
4)
n-(OCF
2)
o(CH
2)
pX(CH
2)
r(X′)
2-a(R
1)
aSi (B)
Wherein, q is 1～3 integer; M, n and o are 0～200 integer independently; P is 1 or 2; X is O or divalent organic group; R is 2～20 integer; R
1Be C
1-22The alkyl of straight chain or branching; A is 0～2 integer; X ' is a hydrolization group; And when a was 0 or 1, z was 0～10 integer.
2. surface-modifying agent as claimed in claim 1, wherein, in general formula (A) and/or general formula (B), q is 3, m is 10～200 integer, n is 1, o is 0, p is 1, X is O, r be 3 and a be 0 or 1.
3. surface-modifying agent as claimed in claim 1, wherein, unrestricted by the ratio of the compound of general formula (A) and/or general formula (B) expression.
4. as each described surface-modifying agent in the claim 1～3, wherein add catalyzer to promote surface modification, wherein, unrestricted by the ratio of the compound of general formula (A) and/or general formula (B) expression and described catalyzer.
5. as each described surface-modifying agent in the claim 1～3, wherein add catalyzer to promote surface modification, wherein, be 0.001 part～2 parts by general formula (A) and/or the compound of general formula (B) expression and the ratio of described catalyzer.
6. method for preparing by the organic silicone compound of general formula (A) expression, wherein, r is 3, X ' is chlorine or alkoxyl group, and a is 0, described method adopts in the presence of transition metal, the hydrosilylation reactions between trichlorosilane or trialkoxy silane and the compound of being represented by following general formula (C):
F-(CF
2)
q-(OC
3F
6)
m-(OC
2F
4)
n-(OCF
2)
o(CH
2)
pXCH
2CH＝CH
2 (C)
Wherein, q is 1～3 integer; M, n and o are 0～200 integer independently; P is 1 or 2; X is oxygen or divalent organic group.
7. method for preparing by the organic silicone compound of general formula (A) expression, wherein, X ' is that R is C
1-22The alkyl of straight chain or branching-OR, described method adopts in the presence of transition metal, and the hydrosilylation reactions between trichlorosilane and the compound of being represented by general formula (C) adopts in the presence of neutralizing agent and C then
1-22Alkoxylation between the Fatty Alcohol(C12-C14 and C12-C18) of straight chain or branching, thus de-chlorine hydride removed, perhaps adopt alkoxylation with metal alkoxide.
8. method for preparing by the organic silicone compound of general formula (A) expression, wherein, X ' is that R is C
1-22The alkyl of straight chain or branching-O-N=CR
2, described method adopts in the presence of transition metal, trichlorosilane with by the hydrosilylation reactions between the compound of general formula (C) expression, adopt then and be C by R
1-22The HO-N=CR of the alkyl of straight chain or branching
2The dialkyl group ketoxime reaction of expression.
9. as each described method for preparing the organic silicone compound in the claim 6～8, wherein, described transition metal is platinum or rhodium.
10. method for preparing by the organic silicone compound of general formula (B) expression, described method adopt partial hydrolysis and the condensation reaction by the compound of general formula (A) expression that obtains according to each described method in the claim 6～9.
11. a treat surface that obtains by each described surface-modifying agent in the use claim 1～8, described treat surface has at least 110 ° water contact angle and is no more than 5 ° water slide angle.
12. a treat surface that obtains by each described surface-modifying agent in the use claim 1～5, described treat surface contains the PFPE of unimolecular film form.
13. a method of making the surface described in the claim 11, described method are included in the step that forms the film of each described surface-modifying agent in the claim 1～5 on the base material according to the wet type coating method.
14. a method of making the surface described in the claim 11, described method are included in according to the step that forms the film of each described surface-modifying agent in the claim 1～5 on the base material of dry type coating method according to the wet type coating method.
15. method that forms the surface, described method comprises uses each described surface-modifying agent dipping porous article in the claim 1～5, thereby and by heating under vacuum described with the porous article of surface-modifying agent dipping so that the evaporation of described surface-modifying agent forms the step of processing layer on base material.
16. the method that forms the surface as claimed in claim 15, wherein, described porous article contain and are selected from by SiO
2, TiO
2, ZrO
2, MgO, Al
2O
3, CaSO
4, the group formed of Cu, Fe, Al, stainless steel and carbon at least a material.
17. as claim 15 or the 16 described methods that form the surface, wherein, the described surface-modifying agent that is immersed in the described porous article adds at least a heating means of pining for and is evaporated according to being selected from resistive heating, electron beam heating, ionic fluid heating, ratio-frequency heating and optics.
18. a method that forms the described surface of claim 15, thereby described method is included in the existence of plasma body down by the film forming step of each described surface-modifying agent shape on base material in the nozzle ejection claim 1～5.
19. method as claimed in claim 18, wherein, described plasma body is the atmospheric pressure plasma of argon gas or helium.
20. antireflective optical member, described antireflective optical member comprises transparent substrate, be formed on the anti-reflective film at least one side of described transparent substrate, and be formed on the processing layer on the outermost surface, described processing layer contains each described surface-modifying agent in the claim 1～5.
21. antireflective optical member as claimed in claim 20, wherein, described transparent substrate is the organic substrate of for example transparent plastic substrate or the inorganic substrate of glass baseplate for example.
22. an optical functional element, described optical functional element comprise claim 20 or 21 described antireflective optical member and the functional optical element that sticks on the described antireflective optical member.
23. optical functional element as claimed in claim 22, wherein, described functional element is a polaroid.
Stick to coated components on the front panel front side of display screen surface 24. a display equipment, described display equipment comprise with tackiness agent, described coated components is claim 22 or 23 described optical functional elements.
25. display equipment as claimed in claim 24, wherein, described indicating meter is liquid-crystal display, CRT monitor, the projected display, plasma display or EL indicating meter.
26. having, a glass, described glass uses the surface that each described surface-modifying agent obtains in the claim 1～5.
27. being used for automobile, glass as claimed in claim 26, described glass uses or aerospace applications.
28. having, glasses lens or optical mirror slip, described glasses lens or optical mirror slip use the surface that each described surface-modifying agent obtains in the claim 1～5.
29. having, a bathroom apparatus, described bathroom apparatus use the surface that each described surface-modifying agent obtains in the claim 1～5.
30. a release method, each described surface-modifying agent is as release agent in the described release method use claim 1～5.
31. a release method, described release method use, and each described surface-modifying agent is used for nano impression in the claim 1～5.
32. method of using each described surface-modifying agent in the claim 1～5 to set up microtexture.
33. the application of microtexture as claimed in claim 32 in lithography or device manufacturing.
34. having, a stoneware, described stoneware use the surface that each described surface-modifying agent obtains in the claim 1～5.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US66748205P | 2005-04-01 | 2005-04-01 | |
| US60/667,482 | 2005-04-01 | ||
| US60/740,939 | 2005-11-30 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310473055.XA Division CN103551075B (en) | 2005-04-01 | 2006-03-30 | Surface modifier |
| CN201310473099.2A Division CN103551076B (en) | 2005-04-01 | 2006-03-30 | Surface modifier |
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| Publication Number | Publication Date |
|---|---|
| CN101151269A true CN101151269A (en) | 2008-03-26 |
Family
ID=39251236
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|---|---|---|---|
| CNA2006800104038A Pending CN101151269A (en) | 2005-04-01 | 2006-03-30 | Surface modifier |
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Application publication date: 20080326 |