CN105400423B - Fluorine-containing smears and with the processed article in the smears - Google Patents
Fluorine-containing smears and with the processed article in the smears Download PDFInfo
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Abstract
The present invention provides the fluorine-containing smears and the article surface-treated with the smears that can be stably formed uniform coated film while raising using the storage stability under preceding solution state on substrate.Fluorine-containing smears, it is characterized in that, in the smears containing following (A)~(C) ingredient, (A) content of ingredient is relative to smears entirety, for 0.01~50 mass %, and the content of (C) ingredient is relative to smears entirety, for 0.01~5 mass %, (A) contain the silane of hydrolization group and/or its partial hydrolysis condensate with the polymer modification containing perfluoroalkyl polyether base, (B) solvent that above-mentioned (A) ingredient can be made equably to dissolve, (C) molecular weight is 250 silane compounds below with hydrolization group.
Description
Technical field
The present invention relates to containing the useful polymer modification containing perfluoroalkyl polyether base containing the silane of hydrolization group and/or its
The smears of partial hydrolysis condensate, in detail, energy while being related to improving using the storage stability under preceding solution state
The excellent envelope of uniform coated film, formation water resistant grease resistance, low dynamic is enough stably formed on substrate includes to use
Polymer modification containing perfluoroalkyl polyether base contains fluorine coating containing the silane of hydrolization group and/or its partial hydrolysis condensate
Agent and with the processed article in the smears.
Background technique
In recent years, headed by the display of mobile phone, the touch panel of picture is accelerating.But touch panel is more
It is that picture exposes, the chance that finger, cheek etc. directly contact is more, and the spots such as sebum are easy to attach to become problem.Therefore, in order to
Improve appearance, visibility, fingerprint is made to be difficult to the requirement of the technology adhered to, the technology for being easy to fall off spot on the surface of display
It is surging on many years ground.
Generally, the compound containing perfluoroalkyl polyether base has water resistant oil resistant since its surface free energy is very small
Property, chemical-resistant, lubricity, release property, soil resistance etc..Using its property, the water resistant industrially as paper, fiber etc. is anti-
The extensive land productivity such as oily anti-fouling agent, the lubricant of magnetic recording media, the oil-proofing agent of precision equipment, release agent, cosmetic preparation, protective film
With.But property means it is non-sensitive adhesiveness for other substrates, non-adaptation simultaneously, that is, enables in substrate table
Face coating, it is also difficult to keep the envelope and substrate closely sealed.
On the other hand, known silane coupled as making substance of the substrate surface of glass, cloth etc. in conjunction with organic compound
Agent is widely utilized as the smears of various substrate surfaces.Silane coupling agent has organo-functional group and anti-in 1 molecule
Answering property silicyl (being generally, the hydrolyzable silyl groups such as alkoxysilyl).Hydrolyzable silyl group utilizes air
In moisture etc. self-condensation reaction occurs and forms envelope.The table that the envelope passes through hydrolyzable silyl group and glass, metal etc.
Face chemically, is physically combined into as the firm envelope with durability.
Therefore, it discloses by importing hydrolyzable silyl group in the compound containing perfluoroalkyl polyether base, easy and substrate
Surface is closely sealed and can be formed in substrate surface with water resistant grease resistance, chemical-resistant, lubricity, release property, soil resistance
Deng envelope composition (Patent Documents 1 to 8: special open 2003-238577 bulletin, patent No. 2860979 bulletin, patent
No. 4672095 bulletin, spy table 2008-534696 bulletin, spy table 2008-537557 bulletin, special open 2012-072272
Bulletin, special open 2012-157856 bulletin, special open 2013-136833 bulletin).
These compositions are usually to be used with that can dilute the solvent dissolved containing the silane compound of perfluoroalkyl polyether base.
Diluted concentration is different because of coating method, in the case where injection coating, dip coated etc., is mostly made with the range of 0.03~5 mass %
With.These solvents are generally bought from solvent manufacturer and are used, and a small amount of moisture is usually contained.For these moisture, it is believed that molten
The moisture in atmosphere is absorbed after being mixed into or manufacture in agent manufacture, where moisture of wall of a container face attachment etc. is reason.It is molten
Moisture in agent is reacted with hydrolyzable silyl group, and the 2 polymerizations~poly incurred between polymer closes, and is caused gelation sometimes, is gathered
The precipitating for closing object, leads to the problem of on storage stability.
In addition, if the molecular weight of polymer increases, being applied in injection even if there is no gelations, the precipitating of polymer
Cloth, ink-jet application in dip coated, generate the unfavorable situation of nozzle blockage sometimes, are easy to produce in the film thickness of substrate surface sometimes
It is raw uneven, uniform film cannot be formed, sufficient performance, the damage transparency, optical characteristics can not be obtained.
Existing technical literature
Patent document
Patent document 1: special open 2003-238577 bulletin
Patent document 2: No. 2860979 bulletin of patent
Patent document 3: No. 4672095 bulletin of patent
Patent document 4: special table 2008-534696 bulletin
Patent document 5: special table 2008-537557 bulletin
Patent document 6: special open 2012-072272 bulletin
Patent document 7: special open 2012-157856 bulletin
Patent document 8: special open 2013-136833 bulletin
Summary of the invention
Subject to be solved by the invention
The present invention is completed in view of above-mentioned actual conditions, and it is an object of the present invention to provide storage stability under solution state before use
The fluorine-containing smears of uniform coated film can be stably formed while raising on substrate and is surface-treated with the smears
The article crossed.
Means for solving the problems
The present inventor furthers investigate to achieve the goals above and repeatedly, as a result, it has been found that: by containing (A) with containing fluorine
Capable of making containing the silane of hydrolization group and/or its partial hydrolysis condensate, (B) for the polymer modification of polyether-based is above-mentioned
(A) ingredient equably dissolves solvent, the coating that (C) molecular weight is 250 silane compounds below with hydrolization group
In agent, make the content of (A) ingredient relative to 0.01~50 mass % of smears entirety, and keeps the content of (C) ingredient opposite
It is 0.01~5 mass % in smears entirety, the storage stability so as to become under the solution state before use improves
While the fluorine-containing smears of uniform coated film can be stably formed on substrate, complete the present invention.
Therefore, the present invention provides following fluorine-containing smears and with the processed article in the smears.
[1] fluorine-containing smears, which is characterized in that in the smears containing following (A)~(C) ingredient, (A) ingredient contains
Amount is 0.01~50 mass % relative to smears entirety, and the content of (C) ingredient is relative to smears entirety, is 0.01
~5 mass %,
(A) contracting containing the silane of hydrolization group and/or its partial hydrolysis with the polymer modification containing perfluoroalkyl polyether base
Object is closed,
(B) solvent that above-mentioned (A) ingredient can be made equably to dissolve,
(C) molecular weight is 250 silane compounds below with hydrolization group.
[2] fluorine-containing smears described in [1], which is characterized in that (C) ingredient is the silane chemical combination indicated by the following general formula
Object.
R2 (4-k)-Si-Xk
(in formula, R2For 1 valency alkyl that hydrogen atom or the unsubstituted or halogen atom of carbon atom number 1~6 replace, X is
Hydrolization group, the integer that k is 2~4.)
[3] fluorine-containing smears described in [1] or [2], which is characterized in that (A) ingredient with the polymerization containing perfluoroalkyl polyether base
The modified silane containing hydrolization group of object includes 10~200 by the following general formula (1)
-CgF2gO- (1)
(in formula, g independently is 1~6 integer in each unit.)
The repetitive unit of expression, and have at least one by the following general formula (2) at least one end
(in formula, R is the alkyl or phenyl of carbon atom number 1~4, and X is hydrolization group, and a is 2 or 3.)
Shown in hydrolyzable silyl group.
[4] fluorine-containing smears described in [3], which is characterized in that the hydrolization group X of formula (2) is methoxy or ethoxy.
[5] described in any item fluorine-containing smears of [1]~[4], which is characterized in that (A) ingredient with containing perfluoroalkyl polyether
The silane containing hydrolization group of the polymer modification of base is to contain shown in the following general formula (3), (4), (5) and (6)
It is at least one kind of in the polymer modification silane of perfluoroalkyl polyether base.
A-Rf-QZ(W)α (3)
Rf-(QZ(W)α)2 (4)
A-Rf-Q-(Y)βB (5)
Rf-(Q-(Y)βB)2 (6)
[in formula, Rf is-(CF2)d-O-(CF2O)p(CF2CF2O)q(CF2CF2CF2O)r(CF2CF2CF2CF2O)s(CF(CF3)
CF2O)t-(CF2)d, d independently is 0~5 integer, and p, q, r, s, t are each independently 0~200 integer, and are p+q
The integer of+r+s+t=10~200, each unit shown in bracket can be combined randomly.A is fluorine atom, hydrogen atom or end
End is-CF3Base ,-CF2H base or-CFH2The fluoro-containing group of 1 valence of base, Q are singly-bound or can be by the organic groups of fluorine-substituted divalent
Group, Z are that [J is alkyl, hydroxyl or K selected from singly-bound, two organic silicylenes ,-JC=3SiO- (K independently be hydrogen atom,
Alkyl, aryl or alkoxy) shown in silicyl ether] shown in the group of trivalent, trivalent shown in-LSi=(L is alkyl)
Group, the groups of 4 valences shown in-C ≡, the group in the group of 4 valences and the silicone residual of 2~8 valences shown in-Si ≡,
W is the following general formula (7a)~(7d)
(in formula, R is the alkyl or phenyl of carbon atom number 1~4, and X is hydrolization group, and a is 2 or 3, f be 1~10 it is whole
Number, D be singly-bound or carbon atom number 1~20 can be by the organic group of fluorine-substituted divalent, the integer that m is 2~6, Me is first
Base.)
Shown in hydrolization group group, α be 1~7 integer.Y is the base of the divalent with hydrolization group
Group, the integer that β is 1~10, B are the alkyl or halogen atom of hydrogen atom, carbon atom number 1~4.]
[6] fluorine-containing smears described in [5], wherein Y is indicated by following formula (8)~(10).
(in formula, R is the alkyl or phenyl of carbon atom number 1~4, and X is hydrolization group, and a is 2 or 3, D be singly-bound or
Carbon atom number 1~20 can by the organic group of fluorine-substituted divalent, D ' be carbon atom number 1~10 can be by fluorine-substituted divalent
Organic group, R1For 1 valency alkyl of carbon atom number 1~20, e is 1 or 2.)
[7] fluorine-containing smears described in [5] or [6], wherein Q is selected from the group of divalent shown in singly-bound or following formula.
(in formula, the integer that b is 2~4, the integer that c is 1~4, the integer that j is 1~50, Me is methyl.)
[8] described in any item fluorine-containing smears of [5]~[7], wherein Z is selected from group shown in singly-bound or following formula.
(in formula, the integer that h is 2~4, Me is methyl.)
[9] described in any item fluorine-containing smears of [1]~[8], which is characterized in that also containing shown in the following general formula (11)
The polymer (D) containing perfluoroalkyl polyether base.
A-Rf-A (11)
(in formula, Rf is-(CF2)d-O-(CF2O)p(CF2CF2O)q(CF2CF2CF2O)r(CF2CF2CF2CF2O)s(CF(CF3)
CF2O)t-(CF2)d, d independently is 0~5 integer, and p, q, r, s, t are each independently 0~200 integer, and are p+q
The integer of+r+s+t=10~200, each unit shown in bracket can be combined randomly.A is fluorine atom, hydrogen atom or end
End is-CF3Base ,-CF2H base or-CFH2The fluoro-containing group of 1 valence of base.)
[10] described in any item fluorine-containing smears of [1]~[9], wherein the solvent of (B) ingredient is fluoride solvent.
[11] with described in any item fluorine-containing processed articles in smears of [1]~[10].
[12] with described in any item fluorine-containing processed touch panels in smears of [1]~[10].
[13] with described in any item fluorine-containing processed antireflection process articles in smears of [1]~[10].
[14] with the processed glass in described in any item fluorine-containing smears, the tempered glass, sapphire glass of [1]~[10]
Glass, quartz glass or SiO2Handle substrate.
In addition, the present invention also provides following fluorine-containing smears and the processed articles in fluorine-containing smears.
[1] the fluorine-containing smears, which is characterized in that in the smears containing following (A)~(C) ingredient, (A) ingredient
Content is 0.01~50 mass % relative to smears entirety, and the content of (C) ingredient is relative to smears entirety
0.01~5 mass %,
(A) in the polymer modification silane containing perfluoroalkyl polyether base as shown in the following general formula (3), (4), (5) and (6)
At least one kind of contracted with the contain silane of hydrolization group and/or its partial hydrolysis of the polymer modification containing perfluoroalkyl polyether base
Object is closed,
A-Rf-QZ(W)α’ (3)
Rf-(QZ(W)α)2 (4)
A-Rf-Q-(Y)β’B (5)
Rf-(Q-(Y)βB)2 (6)
In formula, Rf is-(CF2)d-O-(CF2O)p(CF2CF2O)q(CF2CF2CF2O)r(CF2CF2CF2CF2O)s(CF(CF3)
CF2O)t-(CF2)d, d independently is 0~5 integer, and p, q, r, s, t are each independently 0~200 integer, and are p+q
The integer of+r+s+t=10~200, each unit shown in bracket can be combined randomly；
A is that fluorine atom, hydrogen atom or end are-CF3Base ,-CF2H base or-CFH2The fluoro-containing group of 1 valence of base,
Q be singly-bound or can by the organic group of fluorine-substituted divalent,
Z be selected from
Singly-bound,
Two organic silicylenes,
The group of the trivalent as shown in-JC=,
Wherein J is for alkyl, hydroxyl or by K3Silicyl ether shown in SiO-,
Wherein K independently is hydrogen atom, alkyl, aryl or alkoxy,
The group of trivalent shown in-LSi=,
Wherein L is alkyl,
The group of 4 valences shown in-C ≡,
Group in the silicone residual of the group of 4 valences and 2~8 valences shown in-Si ≡,
W is the group as shown in the following general formula (7a)~(7d) with hydrolization group,
In formula, R is the alkyl or phenyl of carbon atom number 1~4, and X is hydrolization group, and a is 2 or 3, f be 1~10 it is whole
Number, D be singly-bound or carbon atom number 1~20 can be by the organic group of fluorine-substituted divalent, the integer that m is 2~6, Me is methyl；
The integer that α is 1~7；
α ' is 2~7 integer in the case of W is formula (7a), (7c), (7d), is 1~7 in the case of W is formula (7b)
Integer；
Y is the group of the divalent as shown in following formula (9) or (10) with hydrolization group,
In formula, R is the alkyl or phenyl of carbon atom number 1~4, and X is hydrolization group, and a is 2 or 3, and D is that singly-bound or carbon are former
Subnumber 1~20 can by the organic group of fluorine-substituted divalent, D ' be carbon atom number 1~10 can be by the organic of fluorine-substituted divalent
Group, R1For 1 valency alkyl of carbon atom number 1~20, e is 1 or 2；
The integer that β is 1~10,
The integer that β ' is 2~10,
B is the alkyl or halogen atom of hydrogen atom, carbon atom number 1~4；
(B) solvent that above-mentioned (A) ingredient can be equably dissolved, and
It (C) is 250 silane compounds below with hydrolization group by the molecular weight that the following general formula indicates
R2 (4-k)-Si-Xk
In formula, R2For 1 valency alkyl that hydrogen atom or the unsubstituted or halogen atom of carbon atom number 1~6 replace, X is water
Solution property group, the integer that k is 2~4.
[2] .[1] described in fluorine-containing smears, which is characterized in that X is methoxy or ethoxy.
[3] .[1] described in fluorine-containing smears, wherein Q is selected from the group of divalent shown in singly-bound or following formula,
In formula, the integer that b is 2~4, the integer that c is 1~4, the integer that j is 1~50, Me is methyl.
[4] .[1] described in fluorine-containing smears, wherein Z is selected from group shown in singly-bound or following formula,
In formula, the integer that h is 2~4, Me is methyl.
[5] .[1] described in fluorine-containing smears, which is characterized in that also containing containing perfluoroalkyl polyether shown in the following general formula (11)
The polymer (D) of base,
A-Rf-A (11)
In formula, Rf is-(CF2)d-O-(CF2O)p(CF2CF2O)q(CF2CF2CF2O)r(CF2CF2CF2CF2O)s(CF(CF3)
CF2O)t-(CF2)d, d independently is 0~5 integer, and p, q, r, s, t are each independently 0~200 integer, and are p+q
The integer of+r+s+t=10~200, each unit shown in bracket can be combined randomly；A is fluorine atom, hydrogen atom or end
End is-CF3Base ,-CF2H base or-CFH2The fluoro-containing group of 1 valence of base.
[6] .[1] described in fluorine-containing smears, wherein the solvent of (B) ingredient be fluoride solvent.
[7] described in any item fluorine-containing processed articles in smears of [1]~[6].
[8] described in any item fluorine-containing processed touch panels in smears of [1]~[6].
[9] described in any item fluorine-containing processed antireflection process articles in smears of [1]~[6].
[10] the processed glass in described in any item fluorine-containing smears, the tempered glass, sapphire glass of [1]~[6]
Glass, quartz glass or SiO2Handle substrate.
The effect of invention
Fluorine-containing smears of the invention, if containing water-disintegrable base containing the useful polymer modification containing perfluoroalkyl polyether base
Addition cooperation molecular weight is 250 below with hydrolization group in the silane of group and/or the solution of its partial hydrolysis condensate
Silane compound, in the solution moisture exist in the case of, the silane compound of low molecular weight preferentially with reaction of moisture.By
This, is able to suppress the hydrolysis of principal component polymer end, therefore storage stability improves, while can prevent fiber crops when coating
It is tired, uniform coated film can be stably formed on substrate.It therefore, can be in the transparency, the texture for not damaging various articles
In the case of assign excellent anti-pollution, intrusion of the substrate not by chemicals etc. can be protected, chronically keep anti-pollution.
In addition, the excellent in wear resistance of the coated film.The fluorine-containing smears of the invention especially weak solution used in injection coating
In excellent storage stability.
Specific embodiment
Fluorine-containing smears of the invention, which is characterized in that containing (A) containing with the polymer modification containing perfluoroalkyl polyether base
Have the silane of hydrolization group and/or solvent that its partial hydrolysis condensate, (B) can be such that above-mentioned (A) ingredient equably dissolves,
(C) molecular weight is in the smears of 250 silane compounds below with hydrolization group, the content of (A) ingredient relative to
Smears is all, is 0.01~50 mass %, and the content of (C) ingredient is relative to smears entirety, is 0.01~5 matter
Measure %.
As the silane containing hydrolization group with the polymer modification containing perfluoroalkyl polyether base of (A) ingredient, preferably make
It include 10~200, preferably 20~100 by the following general formula (1) with the perfluoroalkyl polyether base of (A) ingredient
-CgF2gO- (1)
(in formula, g independently is 1~6 integer in each unit.)
The repetitive unit of expression and at least one end, preferably 1 end have at least one by the following general formula (2)
(in formula, R is the alkyl or phenyl of carbon atom number 1~4, and X is hydrolization group, and a is 2 or 3.)
The silane of the hydrolyzable silyl group of expression.
In turn, (A) ingredient preferably has at least one, preferably 1~12 water-disintegrable first silicon indicated by above-mentioned formula (2)
Alkyl more preferably has multiple, preferably 2~36, more preferably 2~18 hydrolization groups represented by X.
As the repetitive unit of perfluoroalkyl polyether base indicated by above-mentioned general formula (1), it can be mentioned, for example following units etc..Again
Have, perfluoroalkyl polyether base can be separately formed by a kind of these repetitive units, be also possible to combination of more than two kinds, each repetitive unit can
Randomly combine.
-CF2O-
-CF2CF2O-
-CF2CF2CF2O-
-CF(CF3)CF2O-
-CF2CF2CF2CF2O-
-CF2CF2CF2CF2CF2O-
-CF2CF2CF2CF2CF2CF2O-
-C(CF3)2O-
In above-mentioned formula (2), R is alkyl or the phenyl such as methyl, ethyl, propyl, the butyl of carbon atom number 1~4.
X is hydrolization group, as hydrolization group, can enumerate the carbon such as methoxyl group, ethyoxyl, propoxyl group, butoxy original
The halogenated alkoxies of carbon atom numbers 1~6 such as alkoxy, trifluoromethoxy, trifluoro ethoxy, the tri-chloroethoxy base of subnumber 1~10,
The carbon atom numbers such as alkyloxy-alkoxy, the acetoxyl group of the carbon atom numbers such as methoxymethoxy, methoxy ethoxy 2~10 1~
Halogen radicals such as alkenyloxy group, chloro, bromo, the iodos of carbon atom numbers 2~10 such as 10 acyloxy, isopropyl alkenyloxy group etc..Wherein, excellent
Select methoxyl group, ethyoxyl, isopropyl alkenyloxy group, chloro.
As the silane containing hydrolization group with the polymer modification containing perfluoroalkyl polyether base of (A) ingredient, more preferably
It is at least one kind of in the polymer modification silane containing perfluoroalkyl polyether base indicated by the following general formula (3), (4), (5) and (6).
A-Rf-QZ(W)α (3)
Rf-(QZ(W)α)2 (4)
A-Rf-Q-(Y)βB (5)
Rf-(Q-(Y)βB)2 (6)
[in formula, Rf is-(CF2)d-O-(CF2O)p(CF2CF2O)q(CF2CF2CF2O)r(CF2CF2CF2CF2O)s(CF(CF3)
CF2O)t-(CF2)d, d independently is 0~5 integer, and p, q, r, s, t are each independently 0~200 integer, and are p+q
The integer of+r+s+t=10~200, each unit shown in bracket can be combined randomly.A is fluorine atom, hydrogen atom or end
End is-CF3Base ,-CF2H base or-CFH2The fluoro-containing group of 1 valence of base, Q are singly-bound or can be by the organic groups of fluorine-substituted divalent
Group, Z are that [J is alkyl, hydroxyl or K selected from singly-bound, two organic silicylenes ,-JC=3SiO- (K independently be hydrogen atom,
Alkyl, aryl or alkoxy) shown in silicyl ether] shown in the group of trivalent, trivalent shown in-LSi=(L is alkyl)
Group, the groups of 4 valences shown in-C ≡, the group in the group of 4 valences and the silicone residual of 2~8 valences shown in-Si ≡,
W is the following general formula (7a)~(7d)
(in formula, R, X, a are as described above, the integer that f is 1~10, D are being taken by fluorine for singly-bound or carbon atom number 1~20
The organic group of the divalent in generation, the integer that m is 2~6, Me is methyl.)
Shown in hydrolization group group, α be 1~7 integer.Y is the base of the divalent with hydrolization group
Group, the integer that β is 1~10, B are the alkyl or halogen atom of hydrogen atom, carbon atom number 1~4.]
In above-mentioned formula (3)~(6), Rf is-(CF2)d-O-(CF2O)p(CF2CF2O)q(CF2CF2CF2O)r
(CF2CF2CF2CF2O)s(CF(CF3)CF2O)t-(CF2)d-。
Wherein, d independently is 0~5 integer, preferably 0~2 integer, more preferably 1 or 2, and p, q, r, s, t are respectively
It independently is 0~200 integer, it is preferable that the integer that p is 5~100, the integer that q is 5~100, the integer that r is 0~100, s
For 0~50 integer, the integer that t is 0~100, and p+q+r+s+t be 10~200 integer, preferably 20~100 it is whole
It counts, each unit shown in bracket can be combined randomly.
As Rf, specifically, can illustrate it is following shown in group.
-(CF2)d′-O-(CF2O)p′-(CF2)d′-
-(CF2)d′-O-(CF2CF2O)q′-(CF2)d′-
-(CF2)d′-O-(CF2CF2CF2O)r′-(CF2)d′-
-(CF2)d′-O-(CF2O)p′(CF2CF2O)q′-(CF2)d′-
-(CF2)d′-O-(CF2O)p′(CF2CF2O)q′(CF2CF2CF2O)r′(CF2CF2CF2CF2O)s′-(CF2)d′-
(in formula, d ' is identical as above-mentioned d, and p ', q ', r ', s ', t ' are respectively 1 or more integer, the upper limit and above-mentioned p, q,
R, the upper limit of s, t are identical.)
In above-mentioned formula (3), (5), A is that fluorine atom, hydrogen atom or end are-CF3Base ,-CF2H base or-CFH2The 1 of base
The fluoro-containing group of valence, as the fluoro-containing group of 1 valence, specifically, can illustrate it is following shown in group.
-CF3
-CF2CF3
-CF2CF2CF3
-CF2H
-CFH2
In above-mentioned formula (3)~(6), Q is singly-bound or can be Rf base and terminal groups by the organic group of fluorine-substituted divalent
Linker.As Q, it is preferable that may include organic selected from amido bond, ehter bond, ester bond or dimethylated methylene silylation etc. two
The organic group of the divalent of the unsubstituted or substituted carbon atom number 2~12 of one kind or two or more structure in silicylene,
It preferably may include the alkyl of the divalent of the unsubstituted or substituted carbon atom number 2~12 of above structure.
Wherein, the alkyl as the divalent of unsubstituted or substituted carbon atom number 2~12, can be ethylidene, propylidene
The alkylidenes such as (trimethylene, methyl ethylidene), butylidene (tetramethylene, methyl propylene), hexa-methylene, eight methylene,
The combination of more than two kinds (alkylenearylene etc.) of the arlydene such as phenylene or these groups, in addition, these can be enumerated
The group etc. that the halogen atoms such as part or all of the hydrogen atom of group fluorine, iodine replace, wherein preferably unsubstituted or substituted
Carbon atom number 2~4 alkyl, phenyl.
As such Q, it can be mentioned, for example following groups.
(in formula, the integer that b is 2~4, the integer that c is 1~4, the integer that j is 1~50, Me is methyl.)
In above-mentioned various (3), (4), Z is selected from singly-bound, dialkyl group silicylene of preferably carbon atom number 1~3 etc.
[J is preferably the alkyl, hydroxyl or K of carbon atom number 1~3 by two organic silicylenes ,-JC=3(K independently is hydrogen original to SiO-
The alkoxy of the aryl such as son, the alkyl of preferably carbon atom number 1~3, phenyl or preferably carbon atom number 1~3) shown in first
Silylation ether] shown in the group of trivalent, trivalent shown in-LSi=(alkyl that L is preferably carbon atom number 1~3) group ,-
In the group and 2~8 valences of 4 valences shown in the group of 4 valences ,-Si ≡ shown in C ≡, the silicone residual of preferably 2~4 valences
Group, comprising in the case where siloxanes key, preferably silicon atom number 2~13, preferably silicon atom number 2~5 chains or
Cyclic annular organopolysiloxane residue.In addition, may include silicon alkylen structures, the i.e. Si- that 2 silicon atom alkylidenes combine
(CH2)n- Si (in above-mentioned formula, n be 2~6 integer).
The organopolysiloxane residue has carbon atom number 1~8, more preferably 1~4 methyl, ethyl, propyl, butyl
Equal alkyl or phenyls are advisable.In addition, the alkylidene that the alkylidene in silicon alkylene bond is carbon atom number 2~6, preferably 2~4 is
Preferably.
As such Z, can enumerate it is following shown in group.
(in formula, the integer that h is 2~4, Me is methyl.)
In above-mentioned formula (3), (4), W is the group shown in the following general formula (7a)~(7d) with hydrolization group.
(in formula, R, X, a are same as described above, the integer that f is 1~10, preferably 2~8, and D is singly-bound or carbon atom number 1
~20 can be by the organic group of fluorine-substituted divalent, the integer that m is 2~6, preferably 2~4, Me is methyl.)
Wherein, R, X, a are same as described above, can illustrate R, X, a similar to the above.
D be singly-bound or carbon atom number 1~20, preferably carbon atom number 2~8 can be by the organic group of fluorine-substituted divalent
Group, preferably divalent alkyl, as divalent alkyl, can enumerate methylene, ethylidene, propylidene (trimethylene, methyl ethylidene),
The arlydene such as alkylidenes, the phenylenes such as butylidene (tetramethylene, methyl propylene), hexa-methylene, eight methylene or these
Combination of more than two kinds (alkylene-arylene etc.) of group etc., these groups hydrogen atom part or all by fluorine atom
Substituted group etc..As D, preferably ethylidene, propylidene, phenylene.
As W, specifically, can illustrate it is following shown in group.
-(CH2)f-Si-(OCH3)3
(in formula, f is same as described above.)
In above-mentioned formula (3), (4), α is 1~7 integer, preferably 1~3 integer.
In above-mentioned formula (5), (6), Y is the group of the divalent with hydrolization group, preferably by the following general formula (8), (9)
Or the group that (10) indicate.
(in formula, R, X, a, D are same as described above, D ' be carbon atom number 1~10 can by the organic group of fluorine-substituted divalent,
R1For 1 valency alkyl of carbon atom number 1~20, e is 1 or 2.)
Wherein, R, X, a, D are same as described above, can illustrate R, X, a, D similar to the above.
D ' be carbon atom number 1~10, preferably carbon atom number 2~8 can by the organic group of fluorine-substituted divalent, preferably
Ground divalent alkyl can enumerate methylene, ethylidene, propylidene (trimethylene, methyl ethylidene), butylidene as divalent alkyl
The arlydene such as alkylidenes, the phenylene such as (tetramethylene, methyl propylene), hexa-methylene, eight methylene or these groups
Combination (alkylene-arylene etc.) etc. of more than two kinds, these groups part or all of hydrogen atom be replaced by fluorine atoms
Group etc..As D ', preferably ethylidene, propylidene.
In addition, R1It can be arranged for carbon atom number 1~20,1 valency alkyl of preferably carbon atom number 1~10 as 1 valency alkyl
Citing such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl group, tert-butyl, amyl, neopentyl, hexyl, octyl alkyl, ring
The aryl such as the alkenyls such as the naphthenic base such as hexyl, vinyl, allyl, acrylic, phenyl, tolyl, benzyl, phenylethyl, phenyl
Aralkyl such as propyl etc..In these, preferred methyl.
As Y, specifically, following groups can be enumerated.
(in formula, X is same as described above, and Me is methyl.)
In above-mentioned formula (5), (6), β is 1~10 integer, preferably 1~4 integer.
In addition, B is the alkane such as hydrogen atom, the methyl of carbon atom number 1~4, ethyl, propyl, butyl in above-mentioned formula (5), (6)
The halogen atoms such as base or fluorine atom, chlorine atom, bromine atom, iodine atom.
As the polymer modification silane shown in above-mentioned formula (3), (4) containing perfluoroalkyl polyether base, following illustrations make linker Q
It is expressed as
, it is shown as Z base table
, it is shown as the W base table comprising hydrolization group
In addition, as shown in the group used other than above-mentioned Q, Z, W, the above-mentioned formula (3) that they are composed, (4)
Polymer modification silane containing perfluoroalkyl polyether base can also enumerate the polymer modification silane containing perfluoroalkyl polyether base of following structures.
HF2CO(C2F4O)q1(CF2O)p1CF2-CH2OC3H6Si(OCH3)3
(q1/p1=0.9, p1+q1 ≒ 45)
F3CO(C2F4O)q1(CF2O)p1CF2-CH2OC3H6Si(OCH3)3
(q1/p1=0.9, p1+q1 ≒ 45)
(CH3O)3SiC3H6OCH2-CF2O(C2F4O)q1(CF2O)p1CF2-CH2OC3H6Si(OCH3)3
(q1/p1=0.9, p1+q1 ≒ 45)
(CH3O)3SiC3H6OCH2-CF2O(C2F4O)q1(CF2O)p1CF2-CH2OC3H6Si(OCH3)3
(q1/p1=0.9, p1+q1 ≒ 23)
(Rfa=-CF2O-(C2F4O)q1(CF2O)p1-CF2, q1/p1=0.9, p1+q1 ≒ 45, f=3)
(q1/p1=1.1, p1+q1 ≒ 45)
(q1/p1=0.9, p1+q1 ≒ 45)
(Rfb:-CF2O-(C2F4O)q1(CF2O)p1-CF2, q1/p1=1.1, p1+q1 ≒ 50, R=-CH2CH2-、-CH
(CH3)-)
(q1/p1=0.9, p1+q1 ≒ 45)
As the polymer modification silane shown in above-mentioned formula (5), (6) containing perfluoroalkyl polyether base, following structures can be enumerated
Polymer modification silane containing perfluoroalkyl polyether base.
(q1/p1=0.9, p1+q1 ≒ 45)
(q1/p1=0.9, p1+q1 ≒ 45)
(q1/p1=0.9, p1+q1 ≒ 45)
(q1/p1=0.9, p1+q1 ≒ 45)
(q1/p1=1.0, p1+q1 ≒ 40)
It may include making to contain using above-mentioned using well known method in advance as (A) ingredient in fluorine-containing smears of the invention
There is the terminal hydrolysis group of the silane containing hydrolization group of the polymer modification of perfluoroalkyl polyether base partly to hydrolyze, be condensed and
Obtained partial hydrolysis condensate.
Further more, the weight average molecular weight of (A) ingredient is preferably 1,000~20,000, more preferably 2,000~10,000.Such as
Fruit weight average molecular weight is too small, cannot play the water resistant grease resistance of perfluoroalkyl polyether base, low dynamic sometimes, if excessive, sometimes with
The adaptation of substrate is deteriorated.Further more, weight average molecular weight can be as using AK-225 (manufacture of Asahi Glass society) as exhibition in the present invention
Open the standard polystyren scaled value measurement (similarly hereinafter) of the gel permeation chromatography (GPC) of solvent.
(B) solvent of ingredient is not particularly limited as long as can equably dissolve (A) ingredient.As such molten
Agent can illustrate fluorine richness aliphatic hydrocarbon series solvent (perflexane, PF 5070, perfluorooctane etc.), fluorine richness aromatic hydrocarbon
Series solvent (hexafluoro meta-xylene, trifluoromethylbenzene, 1,3- trifluoromethylbenzene etc.), fluorine richness ether series solvent (methyl perfluoro propyl
Ether, methyl perfluorobutyl ether, ethyl perfluorobutyl ether, perfluor (2- butyl tetrahydrofuran) etc.), fluorine richness alkyl amine series solvent
(perfluorotributylamine, three amylamine of perfluor etc.), part fluorine richness solvent (1,1,1,2,2,3,3,4,4- nine fluorine hexane, 1,1,
1,2,2,3,4,5,5,5- Decafluoropentane, 1,1,1,2,2,3,3,4,4,5,5,6,6- ten trifluorohexane, 1,1,1,2,2,3,3,
4,4,5,5,6,6- ten three fluoro-octanes, 1,1,1,3,3- 3-pentafluorobutane etc.), hydrocarbon system solvent (petroleum ether, mineral spirits, toluene, two
Toluene etc.), ketone series solvent (acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK) etc.) equal solvent.In these, in dissolubility, wetability
Etc., the preferred fluoride solvent of fluorine richness, particularly, more preferable ethyl perfluorobutyl ether, Decafluoropentane and 1,1,1,3,3-
3-pentafluorobutane.Above-mentioned solvent can be used alone a kind, can also be used in mixed way two or more.
The optium concentration of (A) ingredient dissolved in a solvent different, preferably fluorine-containing smears due to the method for coating process
In (A) ingredient content as 0.01~50 mass % range amount, particularly preferably become 0.03~25 mass % model
The amount enclosed.If the concentration of (A) ingredient is too low, sufficient soil resistance, water resistant grease resistance can not be obtained after coating process, if mistake
Height, coated film become unevenly, and the transparency reduces, and the tacky of surface occurs.
(C) it is 250 silane compounds below with hydrolization group that ingredient, which is molecular weight,.(C) ingredient due to (A)
Ingredient is small compared to molecular weight, is easy movement (in solution) in the composition, so if moisture exists in the composition, then preferentially
The probability of reaction is high.Even if the hydrolization group of (A) ingredient hydrolyzes and becomes silanol due to mixed hydrone,
Since (C) ingredient is promptly reacted with the silanol group of (A) ingredient, it can prevent the 2 of (A) ingredient from polymerizeing.
(C) molecular weight of the silane compound of ingredient is 250 hereinafter, preferably 100~250, more preferably 120~220.
If molecular weight is more than 250, water-disintegrable reduction cannot play sufficient keeping quality, if extra alkyl exists, damage this
The anti-pollution come.
(C) ingredient is preferably the silane compound indicated by the following general formula.
R2 (4-k)-Si-Xk
(in formula, R2For 1 valency alkyl that hydrogen atom or the unsubstituted or halogen atom of carbon atom number 1~6 replace, X is water
Solution property group, the integer that k is 2~4.)
In above-mentioned formula, R2For hydrogen atom or carbon atom number 1~6, the unsubstituted or halogen of particularly carbon atom number 1~4
1 valency alkyl that atom replaces, as 1 valency alkyl, it can be mentioned, for example methyl, ethyl, propyl, isopropyl, butyl, isobutyl group, uncles
The alkenyls such as the naphthenic base such as the alkyl such as butyl, amyl, neopentyl, hexyl, cyclohexyl, vinyl, allyl, acrylic, phenyl etc.,
The group that part or all of the hydrogen atom of these groups is replaced by halogen atoms such as fluorine, bromine, chlorine, such as chloromethyl, chlorine third
Base, bromoethyl, trifluoro propyl etc..As R2, preferably methyl, ethyl, vinyl, trifluoro propyl.
X is hydrolization group, can illustrate group same as above-mentioned X.Wherein, preferably methoxyl group, ethyoxyl, the third oxygen
Base, acetoxyl group.
Integer, preferably 3 or 4 that k is 2~4.
As the example of (C) ingredient, dimethyldimethoxysil,ne, diethyldimethoxysilane, trimethoxy can be enumerated
Base silane, methyltrimethoxysilane, vinyltrimethoxysilane, ethyl trimethoxy silane, n-propyl trimethoxy silicon
Alkane, allyltrimethoxysilanis, 3,3,3- trifluoro propyl trimethoxy silanes, tetramethoxy-silicane, tetraethoxysilane, first
Ethyl triethoxy silicane alkane, vinyltriethoxysilane, three isopropenoxysilane of vinyl, methyl triacetoxysilane etc..
If it is considered that water-disintegrable excellent person's storage stability effect raising, preferably methyltrimethoxysilane, vinyl trimethoxy silicon
Alkane, tetramethoxy-silicane, tetraethoxysilane, three isopropenoxysilane of vinyl, methyl triacetoxysilane.
(C) content of ingredient, relative to smears entirety, be 0.01~5 mass %, preferably 0.05~3 mass %, more
Preferably 0.05~2 mass %.If the content of (C) ingredient is very few, the sufficient preservation that can not be obtained under solution state is stablized
Property effect, if excessively, being easy to happen the bad orders such as crawling.
Fluorine-containing smears of the invention can also contain as (D) ingredient by the following general formula (11)
A-Rf-A (11)
(in formula, Rf and A are same as described above.)
The polymer containing perfluoroalkyl polyether base indicated (below also sometimes referred to as without functional initiator).
In above-mentioned formula (11), Rf and A can illustrate group same as foregoing illustrative Rf and A, Rf and above-mentioned (A) at
Rf in point can it is identical can also be different, as Rf, preferably
(in formula, the integer that p2 is 5~200, preferably 10~100, the integer that q2 is 5~200, preferably 10~100,
R2 be 10~200, preferably 20~100 integer, t2 be 5~200, preferably 10~100 integer, t3 be 10~200, it is excellent
The integer of selection of land 20~100, the integer that t2+p2 is 10~200, preferably 20~100, q2+p2 are 10~200, preferably 20
~100 integer.), in addition, as A, preferably
-F
-CF3
-CF2CF3
-CF2CF2CF3。
As without functional initiator, following polymer can be enumerated shown in formula (11).
(in formula, p2, q2, r2, t2, t3 are same as described above.)
(D) weight average molecular weight of the polymer containing perfluoroalkyl polyether base of ingredient is preferably 1,000~50,000, more preferably
1,000~10,000, the further preferably weight average molecular weight of 0.5~1.5 times of range of the weight average molecular weight of (A) ingredient.
If weight average molecular weight is too small, the excellent sliding property of (A) ingredient, if excessive, the transparency of coated film sometimes are damaged sometimes
It reduces.
Further more, (D) ingredient is able to use commercially available product without functional initiator, for example, due to FOMBLIN,
The sale of trade (brand) name as DEMNUM, KRYTOX, therefore can be readily derived.As such polymer, it can be mentioned, for example
The polymer of following structures.
FOMBLIN Y (Solvay Solexis society trade name, FOMBLIN Y25 (weight average molecular weight: 3,200),
FOMBLIN Y45 (weight average molecular weight: 4,100))
(in formula, t2, p2 are the number for meeting above-mentioned weight average molecular weight.)
FOMBLIN Z (Solvay Solexis society trade name, FOMBLIN Z03 (weight average molecular weight: 4,000),
FOMBLIN Z15 (weight average molecular weight: 8,000), FOMBLIN Z25 (weight average molecular weight: 9,500))
(in formula, q2, p2 are the number for meeting above-mentioned weight average molecular weight.)
DEMNUM (ダ イ キ Application industry society trade name, DEMNUM S20 (weight average molecular weight: 2,700), DEMNUM S65
(weight average molecular weight: 4,500), DEMNUM S100 (weight average molecular weight: 5,600))
(in formula, r2 is the number for meeting above-mentioned weight average molecular weight.)
KRYTOX (DuPont society trade name, KRYTOX 143AB (weight average molecular weight: 3,500), KRYTOX 143AX
(weight average molecular weight: 4,700), KRYTOX 143AC (weight average molecular weight: 5,500), KRYTOX 143AD (weight average molecular weight: 7,
000))
(in formula, t3 is the number for meeting above-mentioned weight average molecular weight.)
Usage amount when to cooperation (D) ingredient is not particularly limited, relative to the quality of (A) ingredient, preferably 0~50 matter
The range for measuring %, if excessively, leading to the problem of adaptation sometimes.Further more, cooperation when lower limit, from effectively play (D) at
It sets out in terms of the effect divided, preferably 5 mass % or more.
In addition, in fluorine-containing smears of the invention as needed, it can be cooperated not damaging in the scope of the present invention
His additive.Specifically, hydrolytic condensation catalyst, such as organo-tin compound (dimethoxide base tin, February can be enumerated
Dilaurylate etc.), organic titanic compound (tetra-n-butyl titanate etc.), organic acid (fluorine system carboxylic acid, acetic acid, methanesulfonic acid etc.),
Inorganic acid (hydrochloric acid, sulfuric acid etc.) etc..In these, particularly preferred fluorine system carboxylic acid, acetic acid, tetra-n-butyl titanate, two fourth of tin dilaurate
Ji Xi.The additive amount of hydrolytic condensation catalyst is catalytic amount, in general, being 0.01 relative to above-mentioned 100 mass parts of (A) ingredient
~5 mass parts, particularly 0.1~1 mass parts.
Fluorine-containing smears of the invention, due to the polymer ends in the preservation that is able to suppress under the solution state before use
Hydrolysis, therefore storage stability provide, while can prevent coating when trouble, can be stably formed on substrate uniformly
Coated film.
Fluorine-containing smears of the invention can be applied using method well known to hairbrush coating, dipping, spraying, vapor deposition treatment etc.
With substrate.In addition, solidification temperature is different because of curing method, for example, being coated with using spray coating method, ink-jet method, infusion process, hairbrush, being true
In the case that empty vapour deposition method is granted, the preferred range of room temperature (20 DEG C)~200 DEG C, particularly 50~150 DEG C.It is wet as solidifying
Degree, under humidification carry out due to promote reaction and it is preferred that.In addition, the film thickness for solidifying envelope is suitably selected according to the type of substrate
It selects, but usually 0.1~100nm, particularly 3~30nm.
Further more, in the case where adaptation difference, it can be by the way that SiO be arranged2Layer is used as prime coat, or carries out vacuum plasma
Body processing, atmospheric plasma treatment, alkali process, to improve adaptation.
To the substrate handled with fluorine-containing smears of the invention, there is no particular restriction, can be paper, cloth, metal and its oxidation
The substrate of the various materials such as object, glass, plastics, ceramics, quartz.Fluorine-containing smears of the invention can assign these substrates anti-
Water grease resistance, chemical-resistant, release property, low dynamic, soil resistance.Particularly, the saturating of various articles can not damaged
In the case where bright property, texture, excellent anti-pollution is assigned, intrusion of the substrate not by chemicals etc. can be protected, chronically protected
Hold anti-pollution.As the article handled with fluorine-containing smears of the invention, optical article, film, glass, quartzy base can be enumerated
Article as plate, antireflection film particularly can be used for touch panel, antireflection process article, tempered glass.
Embodiment
Embodiment, reference example and comparative example described below, are described in more detail the present invention, but the present invention is not by following
Embodiment limits.
As the silane containing hydrolization group with the polymer modification containing perfluoroalkyl polyether base, prepare following compounds
1~4.
Compound 1
(weight average molecular weight: 4,600)
Compound 2
(Rfa:-CF2O-(C2F4O)q1(CF2O)p1-CF2, q1/p1=0.9, p1+q1 ≒ 45, f=3)
(weight average molecular weight: 5,500)
Compound 3
(Rfb:-CF2O-(C2F4O)q1(CF2O)p1-CF2, q1/p1=1.1, p1+q1 ≒ 50, f=3)
(weight average molecular weight: 4,800)
Compound 4
(Rfb:-CF2O-(C2F4O)q1(CF2O)p1-CF2, q1/p1=1.1, p1+q1 ≒ 50, R:-CH2CH2Or-CH
(CH3)-、-CH2CH2-/-CH(CH3)-≒0.65/0.35)
(weight average molecular weight: 4,000)
It is quasi- as the solvent for making the silane dissolution containing hydrolization group using the polymer modification containing perfluoroalkyl polyether base
Standby following solvent.
Solvent A: Novec7200 (ethyl perfluorobutyl ether, the manufacture of 3M society)
Solvent B:Solkane365mfc (1,1,1,3,3- 3-pentafluorobutane, the manufacture of ソ Le ベ イ society)
Solvent C: ア サ ヒ Network リ Application AC-2000 (1,1,1,2,2,3,3,4,4,5,5,6,6- ten trifluorohexane, Asahi Glass
Society's manufacture)
With AQUACOUNTER AQ-2100 (カ ー Le Off ィ ッ シ ャ ー type determination of trace water device；Ping Zhao industry society system
Make) amount of moisture in the above-mentioned solvent of measurement, result is the result of table 1.
[table 1]
| The type of solvent | Amount of moisture (ppm) |
| Solvent A | 45 |
| Solvent B | 87 |
| Solvent C | 36 |
It is 250 silane compounds below with hydrolization group as molecular weight, prepares 2 kinds of following compounds.
Silane α: vinyltrimethoxysilane (molecular weight 148)
Silane β: tetraethoxysilane (molecular weight 208)
In addition, being more than 250 silane compound with hydrolization group as molecular weight, prepare following compounds.
Silane γ: n- ruthenium trimethoxysilane (molecular weight 262)
The modulation of smears
Inorganic agent A~G:
To be combined shown in table 2, with what is become with the polymer modification containing perfluoroalkyl polyether base containing hydrolization group
0.1 mass parts of silane, molecular weight are 250 silane compound 0.2 mass parts below with hydrolization group, 99.7 matter of solvent
The mode of amount part modulates 100 mass parts of smears, is fitted into embolism in the brown bottle of 100mL and seals.
Inorganic agent H, I:
To be combined shown in table 2, with what is become with the polymer modification containing perfluoroalkyl polyether base containing hydrolization group
0.1 mass parts of silane, the mode of 99.9 mass parts of solvent modulate 100 mass parts of smears, are fitted into embolism in the brown bottle of 100mL
Sealing.
Inorganic agent J:
To be combined shown in table 2, with what is become with the polymer modification containing perfluoroalkyl polyether base containing hydrolization group
0.1 mass parts of silane, molecular weight are more than 250 0.2 mass parts of silane compound with hydrolization group, 99.7 mass of solvent
The mode of part modulates 100 mass parts of smears, is fitted into embolism in the brown bottle of 100mL and seals.
These inorganic agents A~J was fitted into 50 DEG C of baking oven after 72 hours, various tests are implemented.
[table 2]
[Examples 1 to 6, reference example 1, comparative example 1~3]
The confirmation of keeping quality
Using gel permeation chromatography (GPC), above-mentioned inorganic agent A~J as smears is measured, calculates 2 polymerizations
The generation ratio of above high molecular weight body.Determination condition is as described below.Show the result in table 3.
[determination condition]
Developing solvent: hydrochlorofluorocarazeotropic (HCFC) -225
Flow: 1mL/min.
Detector: evaporative light scattering detector
Column: Dong ソ ー society manufactures TSKgel Multipore HXL-M
Use 2
Column temperature: 35 DEG C
Sample injection rate: 100 μ L (solution of 0.1 mass % of concentration)
[table 3]
[embodiment 7~12, reference example 2, comparative example 4~6]
Solidify the formation of envelope and the evaluation of the transparency, wear resistance
Glass (コ ー ニ Application グ society manufacture GorillaII) on use jet foundation applicator (NST-51；ティーアン
The manufacture of De ケ イ society) the above-mentioned modulation of coating inorganic agent A~J as smears, make it under 80 DEG C, the atmosphere of humidity 80%
Solidification 1 hour forms solidification envelope (film thickness: about 15nm), makes test body.
Mist degree (transparency) measurement and abrasion test of the test body are carried out using condition shown in following.By result
It is shown in table 4.
[mist degree determination condition]
The mist degree of the test body of above-mentioned production is measured according to JIS K 7136, using following apparatus.
Device name: NDH-5000 (Japanese electricity Se society manufacture)
[abrasion test condition]
The wear test for carrying out 10,000 time under the following conditions, by the contact in the surface after wear test relative to water
Angle is 100 ° or more and is evaluated as qualification.
Device name: reciprocating wear testing machine TRIBOGEAR 30S (the new scientific society's manufacture in east) lost material: ベ Application U ッ ト
(manufacture of society, Asahi Chemical Industry)
Moving distance (single track): 30mm
Movement speed: 1,600mm/ point
Load: 1kg/cm2
Contact angle meter device name: Drop Master (manufacture of consonance interface science society)
[table 4]
By above-mentioned result it is found that not adding molecular weight is 250 silane compounds below with hydrolization group
Inorganic agent H, I, due to save in hydrolyze, 2 polymerization more than molecular weight polymer ratio increase (comparative example
1,2).It is added to the inorganic agent J that molecular weight is more than 250 silane compound with hydrolization group, although molecular weight
The generation of polymer be inhibited, but be compared to the examples, big value (comparative example 3).In addition, if using these processing
Agent H, I, J form envelope in glass surface, then the uniformity on surface is poor, finds the rising of haze value, while wear durability
It reduces (comparative example 4~6).
On the other hand, be added to molecular weight be 250 silane compounds below with hydrolization group inorganic agent A~
G is difficult to happen the molecular weight (Examples 1 to 6) of polymer in preservation, and the uniformity of the envelope after being as a result coated with is good,
The transparency and wear durability are excellent (embodiment 7~12).
Claims (11)
1. fluorine-containing smears, which is characterized in that in the smears containing following (A)~(C) ingredient, the content phase of (A) ingredient
It is 0.01~50 mass % for smears entirety, and the content of (C) ingredient is relative to smears entirety, is 0.01~5 matter
% is measured,
(A) in the polymer modification silane containing perfluoroalkyl polyether base as shown in the following general formula (3), (4), (5) and (6) extremely
Few a kind with the polymer modification containing perfluoroalkyl polyether base containing the silane of hydrolization group and/or its partial hydrolysis condensate,
A-Rf-QZ(W)α’ (3)
Rf-(QZ(W)α)2 (4)
A-Rf-Q-(Y)β’B (5)
Rf-(Q-(Y)βB)2 (6)
In formula, Rf is-(CF2)d-O-(CF2O)p(CF2CF2O)q(CF2CF2CF2O)r(CF2CF2CF2CF2O)s(CF(CF3)CF2O)t-
(CF2)d, d independently is 0~5 integer, and p, q, r, s, t are each independently 0~200 integer, and are p+q+r+s+t
=10~200 integer, each unit shown in bracket can be combined randomly；
A is that fluorine atom, hydrogen atom or end are-CF3Base ,-CF2H base or-CFH2The fluoro-containing group of 1 valence of base,
Q be singly-bound or can by the organic group of fluorine-substituted divalent,
Z be selected from
Singly-bound,
Two organic silicylenes,
The group of the trivalent as shown in-JC=,
Wherein J is for alkyl, hydroxyl or by K3Silicyl ether shown in SiO-,
Wherein K independently is hydrogen atom, alkyl, aryl or alkoxy,
The group of trivalent shown in-LSi=,
Wherein L is alkyl,
The group of 4 valences shown in-C ≡,
Group in the silicone residual of the group of 4 valences and 2~8 valences shown in-Si ≡, W are by the following general formula (7a)~(7d)
Shown in hydrolization group group,
In formula, R is the alkyl or phenyl of carbon atom number 1~4, and X is hydrolization group, and a is 2 or 3, the integer that f is 1~10, D
For singly-bound or carbon atom number 1~20 can be by the organic group of fluorine-substituted divalent, the integer that m is 2~6, Me is methyl；
The integer that α is 1~7；
α ' in the case of W is formula (7a), (7c), (7d) be 2~7 integer, in the case of W be formula (7b) be 1~7 it is whole
Number；
Y is the group of the divalent as shown in following formula (9) or (10) with hydrolization group,
In formula, R is the alkyl or phenyl of carbon atom number 1~4, and X is hydrolization group, and a is 2 or 3, and D is singly-bound or carbon atom number
1~20 can by the organic group of fluorine-substituted divalent, D ' be carbon atom number 1~10 can be by the organic group of fluorine-substituted divalent
Group, R1For 1 valency alkyl of carbon atom number 1~20, e is 1 or 2；
The integer that β is 1~10,
The integer that β ' is 2~10,
B is the alkyl or halogen atom of hydrogen atom, carbon atom number 1~4；
(B) solvent that above-mentioned (A) ingredient can be equably dissolved, and
It (C) is 250 silane compounds below with hydrolization group by the molecular weight that the following general formula indicates
R2 (4-k)-Si-Xk
In formula, R2For 1 valency alkyl that hydrogen atom or the unsubstituted or halogen atom of carbon atom number 1~6 replace, X is water-disintegrable base
Group, the integer that k is 2~4.
2. fluorine-containing smears described in claim 1, which is characterized in that X is methoxy or ethoxy.
3. fluorine-containing smears described in claim 1, wherein Q is selected from the group of divalent shown in singly-bound or following formula,
In formula, the integer that b is 2~4, the integer that c is 1~4, the integer that j is 1~50, Me is methyl.
4. fluorine-containing smears described in claim 1, wherein Z is selected from group shown in singly-bound or following formula,
In formula, the integer that h is 2~4, Me is methyl.
5. fluorine-containing smears described in claim 1, which is characterized in that also contain shown in the following general formula (11) and contain perfluoroalkyl polyether
The polymer (D) of base,
A-Rf-A (11)
In formula, Rf is-(CF2)d-O-(CF2O)p(CF2CF2O)q(CF2CF2CF2O)r(CF2CF2CF2CF2O)s(CF(CF3)CF2O)t-
(CF2)d, d independently is 0~5 integer, and p, q, r, s, t are each independently 0~200 integer, and are p+q+r+s+t
=10~200 integer, each unit shown in bracket can be combined randomly；A be fluorine atom, hydrogen atom or end be-
CF3Base ,-CF2H base or-CFH2The fluoro-containing group of 1 valence of base.
6. fluorine-containing smears described in claim 1, wherein the solvent of (B) ingredient is fluoride solvent.
7. with described in any item fluorine-containing processed articles in smears of claim 1~6.
8. with described in any item fluorine-containing processed touch panels in smears of claim 1~6.
9. with described in any item fluorine-containing processed antireflection process articles in smears of claim 1~6.
10. with the processed glass in described in any item fluorine-containing smears or SiO of claim 1~62Handle substrate.
11. with the processed tempered glass in described in any item fluorine-containing smears, sapphire glass or the stone of claim 1~6
English glass.
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| JP2014184099A JP6398500B2 (en) | 2014-09-10 | 2014-09-10 | Fluorine-containing coating agent and article treated with the coating agent |
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| JP6582652B2 (en) * | 2015-07-13 | 2019-10-02 | ダイキン工業株式会社 | Surface treatment agent |
| JP2017193666A (en) * | 2016-04-21 | 2017-10-26 | 大日本印刷株式会社 | Member for low temperature environment having anti-frost, anti-condensation, and anti-icing properties |
| JP2019035077A (en) * | 2017-08-14 | 2019-03-07 | 住友化学株式会社 | Composition |
| JP6922996B2 (en) | 2017-10-31 | 2021-08-18 | ダイキン工業株式会社 | Surface treatment composition |
| CN109486371A (en) * | 2018-10-29 | 2019-03-19 | 深圳市派恩新材料技术有限公司 | A kind of fluorochemicals coatings and preparation method thereof, application method |
| CN114502661A (en) * | 2019-09-30 | 2022-05-13 | 信越化学工业株式会社 | Fluorine-containing curable composition and article |
| KR20220031931A (en) * | 2019-12-27 | 2022-03-14 | 네오스 컴파니 리미티드 | Coating compositions and articles having coatings |
| JP7330883B2 (en) * | 2019-12-27 | 2023-08-22 | 株式会社ネオス | Coating compositions and articles with coatings |
| JP7252500B2 (en) * | 2021-01-19 | 2023-04-05 | ダイキン工業株式会社 | Surface treatment agent |
| WO2022186269A1 (en) * | 2021-03-05 | 2022-09-09 | Ａｇｃ株式会社 | Fluorine-containing ether compound, surface treatment agent, fluorine-containing ether composition, coating liquid, article, method for producing article, and compound |
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| TW201619170A (en) | 2016-06-01 |
| CN105400423A (en) | 2016-03-16 |
| KR102457676B1 (en) | 2022-10-24 |
| TWI669306B (en) | 2019-08-21 |
| JP2016056293A (en) | 2016-04-21 |
| KR20160030445A (en) | 2016-03-18 |
| JP6398500B2 (en) | 2018-10-03 |
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