CN109790443A - Surface treating agent - Google Patents
Surface treating agent Download PDFInfo
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- CN109790443A CN109790443A CN201780061386.9A CN201780061386A CN109790443A CN 109790443 A CN109790443 A CN 109790443A CN 201780061386 A CN201780061386 A CN 201780061386A CN 109790443 A CN109790443 A CN 109790443A
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- base
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/10—Block or graft copolymers containing polysiloxane sequences
- C09D183/12—Block or graft copolymers containing polysiloxane sequences containing polyether sequences
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/60—Deposition of organic layers from vapour phase
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
- B05D5/08—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain an anti-friction or anti-adhesive surface
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/63—Additives non-macromolecular organic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/18—Materials not provided for elsewhere for application to surfaces to minimize adherence of ice, mist or water thereto; Thawing or antifreeze materials for application to surfaces
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
- G02B1/11—Anti-reflection coatings
- G02B1/111—Anti-reflection coatings using layers comprising organic materials
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- Chemical Kinetics & Catalysis (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)
- Paints Or Removers (AREA)
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- Laminated Bodies (AREA)
- Treatments Of Macromolecular Shaped Articles (AREA)
Abstract
Hardening envelope and the excellent surface treating agent of keeping quality can be rapidly formed using simple step the purpose of the present invention is to provide a kind of.The present invention provides the article of following surface treating agent and the hardening thing with the surface treating agent, wherein the surface treating agent contains: (A) is in a molecule with the fluorine-containing organic silicon compound of at least one water-disintegrable base；And (B) is 0.001 mass parts~15 mass parts amount relative to total 100 mass parts of (A) ingredient and (B) ingredient in the molecule with the compound of phosphonate group.
Description
Technical field
The present invention relates to a kind of surface treating agents containing fluorine-containing organic silicon compound.Specifically it is related to a kind of save surely
It is qualitative excellent and can between low-temperature short-time under hardened and the surface of envelope that water and oil-resistant and excellent wear resistance are provided
Inorganic agent and the article handled using the surface treating agent.
Background technique
In recent years, using the display of mobile phone as representative, the touch screenization of picture is accelerating.But touch screen is big
Mostly picture is completely exposed, and the chance that finger or cheek etc. directly contact is more, therefore easy to attach become of dirt of sebum etc. is asked
Topic.Therefore, it in order to improve appearance or visibility, is not easy to adhere to the technology of fingerprint on the surface of display or is easy to make dirt
The requirement of the technology to fall off improves year by year.
The compound of commonly known fluorine-containing oxyalkylene has waterproof and oilproof since its surface free energy is very small
Property, chemical-resistant, lubricity, release property and soil resistance etc..Using its property, and industrially in the waterproof of paper, fiber etc.
In grease proofing anti-fouling agent, the lubricant of magnetic recording media, the oil-proofing agent of precision equipment, release agent, cosmetic preparation, protective film etc. widely
It utilizes.But the compound of the fluorine-containing oxyalkylene is poor for the adherence and adhesion of other substrates, therefore, it is difficult to make to wrap
The envelope and substrate of hardening thing containing the composition containing the compound touch.
In addition, silane coupling agent is public as the additive for being bonded the substrate surfaces such as glass or cloth and organic compound
Know, additive contained in the smears as various substrate surfaces and widely utilize.Silane coupling agent is in a molecule
Compound with organic functional base Yu reactive silicon alkyl (usually alkoxysilane group).Alkoxysilane group utilizes air
In moisture etc. and self-condensation reaction occurs.In the envelope made of hardening smears, the alkoxysilane group or conduct
The silanol group of its hydrolysate and the surface of glass or metal etc. are chemically physically bonded, and are thus become with durable
The firm envelope of property.
In patent document 1 (Japanese Patent Laid-Open 2003-238577 bulletin), describe with represented by following formula
The polymer modification silane containing perfluorooxyalkylene groups of straight-chain perfluorooxyalkylene groups is as with fluorine oxyalkylene and alcoxyl
The compound of base silane base.Utilize the hardening of the surface treating agent comprising the polymer modification silane containing perfluorooxyalkylene groups
Object handles glass surface, and excellent lubricity, release property and abrasion performance thus can be assigned to glass surface.
[changing 1]
(in formula, Rf is the straight chain type perfluorooxyalkylene groups of divalent, and R is the alkyl or phenyl of carbon number 1~4, and X is water-disintegrable
Base, n are the integer that 0~2, m is 1~5, and a is 2 or 3)
But the firm time that the surface treating agent recorded in the patent document 1 needs 1 day or so at room temperature,
1 hour or so firm time is needed under 100 DEG C or so of heating, therefore there is a problem of productivity difference.In this way, existing anti-
The anti-oil-treatment agent of water (surface treating agent) though can be formed with good water and oil-resistant and dirt erasing property film, hardenability
Difference.It is therefore desirable to the exploitation between the Waterproof, grease proof treating compound (surface treating agent) that can be hardened down low-temperature short-time.
As promote hardening catalyst, it is known to organic titanate, organic titanium chelate compound, organo-aluminum compound,
Organic zirconate, organo-tin compound, the metal salt of organic carboxyl acid, amine compounds and its salt, quarternary ammonium salt, alkali metal it is low
Grade fatty acid salt, dialkylhydroxylamine, the organo-silicon compound containing guanidine radicals, organic acid and inorganic acid etc..However, these catalyst
Be not dissolved in fluorine series solvent, even if dissolution also few dissolution, therefore catalyst efficiency is poor.In addition, sometimes because of metal component
It remains and leads to the deterioration for hardening the characteristic of envelope.
In order to solve described problem, packet is described in patent document 2 (Japanese Patent Laid-Open 2008-144144 bulletin)
The coating agent composition of perfluoro-polyether carboxylic acid is as the hardening catalyst for dissolving in fluorine series solvent.
Existing technical literature
Patent document
Patent document 1: Japanese Patent Laid-Open 2003-238577 bulletin
Patent document 2: Japanese Patent Laid-Open 2008-144144 bulletin
Summary of the invention
Problem to be solved by the invention
The composition recorded in patent document 2 is hardened under the short time and provides waterproofness, grease proofness and prevent
The hardening envelope of dirty physical properties excellent, but keeping quality becomes problem.
Therefore, hardening envelope and preservation can be rapidly formed using simple step the purpose of the present invention is to provide a kind of
The excellent surface treating agent of property.
Technical means to solve problem
It has carried out making great efforts research in order to solve the problem, as a result the inventors discovered that by using with phosphonate group
Compound as with water-disintegrable base fluorine-containing organic silicon compound hardening catalyst, can to solve the problem.
That is, the present invention provides the article of following surface treating agent and the hardening thing with the surface treating agent, wherein
The surface treating agent contains:
(A) with the fluorine-containing organic silicon compound of at least one water-disintegrable base in a molecule；And
(B) total 100 mass parts in the molecule with the compound of phosphonate group, relative to (A) ingredient and (B) ingredient
And it is 0.001 mass parts~15 mass parts amount.
The effect of invention
The surface treating agent of the invention quick-hardening and is close contact on substrate securely on substrate, and it is anti-to form waterproof
The excellent envelope such as oiliness, lubricity and release property.
In addition, the compound contained in surface treating agent of the invention with phosphonate group with the moisture in air because connecing
Touching and phosphonate group fast hydrolyzing and become phosphonic acids.The phosphonic acids promotes the water with the fluorine-containing organic silicon compound of water-disintegrable base
Solution, quickly hardens surface treating agent.The phosphonate ester can steadily exist in the state of not with contact with moisture.Therefore, may be used
The surface treating agent of excellent storage stability is provided.
Specific embodiment
[(A) fluorine-containing organic silicon compound]
(A) ingredient is the fluorine-containing organic silicon compound in a molecule at least one water-disintegrable base.The ingredient exists
There is the water-disintegrable bases such as hydroxyl, the alkoxy of carbon number 1~12 and alkyloxy-alkoxy, as long as and for fluorine atom in one molecule
Organo-silicon compound.So-called fluorine-containing organic silicon compound, it is however preferred to have the compound of fluorine oxyalkylene.It is so-called to have
The compound of fluorine oxyalkylene is with multiple by-CjF2j(poly-) fluorine oxyalkylene that repetitive unit represented by O- is bonded
The compound of structure (in the structure, j is 1 or more, is preferably the integer of 1~6, more preferably 1~4).In particular, can have 10
A~500, preferably 15~200 and then preferably 20~100, more preferably 25~80 repetitions
Unit.
Repetitive unit-the CjF2jO- can be any one of straight chain type and branching type.Such as following units can be enumerated,
Bond person can be carried out for the two or more of these repetitive units.
-CF2O-
-CF2CF2O-
-CF2CF2CF2O-
-CF(CF3)CF2O-
-CF2CF2CF2CF2O-
-CF2CF2CF2CF2CF2O-
-C(CF3)2O-
The fluorine oxyalkylene structure is especially by-(CF2)d-(OCF2)p(OCF2CF2)q(OCF2CF2CF2)r
(OCF2CF2CF2CF2)s(OCF(CF3)CF2)tO(CF2)dIt indicates.It can are as follows: the integer that d is 0~5 in the formula, p, q, r, s, t
It is separately 0~200 integer, and p+q+r+s+t=10~200.Furthermore represented each unit can be random in bracket
Bond.It can especially be indicated with following structural formula.
In the formula, the integer that d' is 0~5, p', q', r', s', t' are separately 0~200 integer, and p'
+ q'+r'+s'+t'=10~200.
(A) represented by the fluorine-containing organic silicon compound of ingredient is more preferably by any one of following formula (1)~formula (4)
Fluorine-containing organic silicon compound.These one kind that can be used alone, can also and with two or more.
(A-Rf)α-ZWβ (1)
Rf-(ZWβ)2 (2)
A-Rf-Q-(Y)γB (3)
Rf-(Q-(Y)γB)2 (4)
In formula (1) and formula (2), Rf base is-(CF2)d-(OCF2)p(OCF2CF2)q(OCF2CF2CF2)r
(OCF2CF2CF2CF2)s(OCF(CF3)CF2)t-O(CF2)d, p, q, r, s, t are as described above.Represented each unit in bracket
It can randomly be bonded.A is that fluorine atom, hydrogen atom or end are-CF3Base ,-CF2H base or-CH2The fluorine-containing base of the monovalence of F base,
Z is singly-bound, carbon atom, silicon atom, nitrogen-atoms or the divalent~octavalence organic group that can replace through fluorine atom, in formula (1)
The valence mumber of Z is (β+α), and the valence mumber of the Z in formula (2) is (β+1), and W is the organic group for the monovalence for having water-disintegrable base in end.α
For 1~7 integer, preferably 1~3 integer.The integer that β is 1~7, preferably 1~3 integer.
In formula (3) and formula (4), Rf and A are as described above, Q is the organic group of singly-bound or divalent, and γ is separately
1~10 integer, Y are the organic group of the divalent with water-disintegrable base, and B is the alkyl or halogen atom of hydrogen atom, carbon number 1~4.
In the formula (1) and formula (3), A is fluorine atom, hydrogen atom or has-CF in end3Base ,-CF2H base or-
CH2The fluorine-containing base of the monovalence of F base.Wherein, preferably-CF3Base ,-CF2CF3Base ,-CF2CF2CF3Base.
In the formula (1) and formula (2), Z be singly-bound, carbon atom, silicon atom, nitrogen-atoms or can be fluorine-substituted two
Valence~octavalence organic group.The valence mumber of Z in formula (1) is (β+α), and the valence mumber of the Z in formula (2) is (β+1).The organic group can
It is indicated by-Q-M-.
Q is the organic group of singly-bound or divalent, and is the concatenating group of Rf base and M base.Preferably may include selected from by amido bond,
One or both of group composed by the organic silylene of ehter bond, ester bond, ethylenic linkage or dimethylsilylene etc. two with
On, the divalent organic base of carbon number 2~12 that is unsubstituted or is substituted.Can more preferably have the bivalent hydrocarbon radical of the key.
As the bivalent hydrocarbon radical of the carbon number 2~12 for being unsubstituted or being substituted represented by by the Q, such as can enumerate:
Methylene, ethylidene, propylidene (trimethylene, methyl ethylidene), butylidene (tetramethylene, methyl propylene), six methylenes
Two or more combination (the alkylenearylenes of the arlydene such as alkylidenes, the phenylenes such as base, eight methylene or these bases
Deng).In turn, can also replace for part or all for the hydrogen atom being bonded with the carbon atom of these bases through halogen atoms such as fluorine
Base.Wherein, the alkylidene or phenylene for the carbon number 2~4 for being preferably unsubstituted or being substituted.
Base as Q, such as represented by can enumerating by following structural formula.
[changing 2]
-(CH2)a-O-(CH2)b-
[changing 3]
(in formula, the integer that f is 2~4, the integer that a, b, g are 1~4, the integer that h is 1~50, Me is methyl)
M is singly-bound, selected from-R independently of one another1 2The base ,-R of divalent represented by C-3 2The base of divalent represented by Si- ,-
R1The base ,-R of trivalent represented by C=3The base and-Si ≡ institute table of tetravalence represented by the base of trivalent represented by Si=,-C ≡
Base or divalent~octavalence silicone residual in the base for the tetravalence shown.In described, R1It is independently of one another preferably carbon number 1
~3 alkyl, hydroxyl or R2 3Silylation ether, R represented by SiO-2It is independently of one another hydrogen atom, is preferably carbon number 1~3
The aryl such as alkyl, phenyl or carbon number 1~3 alkoxy.R3It is independently of one another preferably alkyl, the carbon number 2 or 3 of carbon number 1~3
Alkenyl, carbon number 1~3 alkoxy or chloro.In the case where M is silicone residual, it is however preferred to have silicon atom number is 2
~13, preferably silicon atom number be 2~5 chain, branch-like or cyclic annular organopolysiloxane structure.It is described organic poly-
Siloxanes can have the alkyl or phenyls such as methyl, ethyl, propyl and the butyl that carbon number is 1~8, more preferably 1~4.In addition,
It may include the sila alkylen structures or silicon phenylene structure, i.e. Si- that two silicon atoms are bonded through alkylidene or phenylene
(CH2)n- Si or Si- (C6H4)-Si.In the formula, the integer that n is 2~6, preferably 2~4 integer.
As the M, person represented by following structural formula can be enumerated.
[changing 4]
(in formula, i be 1~20 integer)
[changing 5]
[changing 6]
[changing 7]
(in formula, Me is methyl)
[changing 8]
(in formula, the integer that f is 2~4, the integer that h is 1~50, Me is methyl)
In the formula (1) and formula (2), W is the organic group for the monovalence for having water-disintegrable base in end, preferably by following
Base represented by formula.
[changing 9]
(in formula, R is the alkyl or phenyl of carbon number 1~4, and X is water-disintegrable base, and a is 2 or 3, the integer that m is 0 or 1~10)
It as X, can enumerate: alkoxy, the methoxy methyl of the carbon numbers such as methoxyl group, ethyoxyl, propoxyl group, butoxy 1~10
Acyloxy, the isopropyl alkene oxygen of the carbon numbers 1~10 such as the oxygroup alkoxies of the carbon numbers such as oxygroup, methoxy ethoxy 2~10, acetoxyl group
Halogen radicals such as alkenyloxy group, chloro, bromo, the iodo of the carbon numbers such as base 2~10 etc..It is wherein preferably methoxyl group and ethyoxyl.Institute
It states in formula, R is the alkyl or phenyl of carbon number 1~4, wherein preferably methyl.A is 2 or 3, with regard to reactivity, for the contiguity of substrate
For the viewpoint of property, preferably 3.B is the integer of 1~7, preferably 1~3, and c is the integer of 1~5, preferably 1~3.
In formula (1) and formula (2), as-ZWβRepresented structure can enumerate person represented by following structural formula.
[changing 10]
[changing 11]
In formula (7a)~formula (7e), Q, R, X and a are as described above, m1For 0~10 integer, preferably 2~8 it is whole
Number, m2For 1~10 integer, preferably 2~8 integer.The integer that b is 2~6, preferably 2~4 integer, c are 1~50
Integer, preferably 1~10 integer, Me are methyl.
In the formula (3) and formula (4), Q is the organic group of divalent, and is the concatenating group of Rf base and Y base.The Q's is detailed
Feelings are such as explained above.
In the formula (3) and formula (4), Y is the organic group of the divalent with water-disintegrable base independently of one another.Preferably by
Base represented by following formula.
[changing 12]
In formula, R, X, a and m are as described above.The integer that p is 1~6, preferably 1~3 integer, more preferably 1 or 2.
M' is the alkyl for being substituted or being unsubstituted of trivalent~octavalence, preferably trivalent~pentavalent, more preferably trivalent or tetravalence, institute
Part or all for stating the carbon atom in alkyl can be replaced silicon atom, in addition, with the hydrogen atom of carbon atom bond
Part or all can be replaced the halogen atoms such as fluorine atom.Furthermore the valence mumber of M' is p+2.M' is preferably by following structural formula
Represented base.
[changing 13]
(in described, M1For bivalent hydrocarbon radical or organosilicon alkyl, M2For trivalent hydrocarbon radical or organosilicon alkyl, R is carbon number 1~6
Monovalent hydrocarbon)
As the Y, such as base represented by following structural formula can be enumerated.
[changing 14]
[changing 15]
(in formula, X with it is described identical, j be 0~10 integer, preferably 1~8 integer, k be 2~10 integer, preferably
For 3~8 integer.Me is methyl)
In the formula (3) and formula (4), the integer that γ is 1~10, preferably 1~4 integer.In addition, B is independent of one another
Ground is alkyl or fluorine atom, chlorine atom, bromine atom and the iodine such as hydrogen atom, the methyl of carbon number 1~4, ethyl, propyl and butyl
The halogen atoms such as atom.
As fluorine-containing organic silicon compound represented by the formula (1)~formula (4), such as following structural formula institute table can be enumerated
The compound shown.
[changing 16]
[changing 17]
[changing 18]
[changing 19]
[changing 20]
[changing 21]
[changing 22]
[changing 23]
[changing 24]
[changing 25]
[changing 26]
[changing 27]
[changing 28]
[changing 29]
[changing 30]
[changing 31]
[changing 32]
[changing 33]
(in formula, Me is methyl, and represented each unit can be randomly bonded in bracket)
Surface treating agent of the invention may include the water-disintegrable base (X) in (A) ingredient part or all through water
The compound (compound that X is OH base) of solution, also may include part or all of compound being condensed of these OH bases.
[(B) ingredient]
(B) ingredient is compound in the molecule with phosphonate group.Phosphonate group in the so-called present invention is-P (O)
(OX')2Represented base.As long as X' is-P (O) (OX')2Base possessed by represented general phosphonate ester.Preferably
The alkyl or aryl or-SiR for the carbon number 1~5 for being unsubstituted or being substituted3Represented base.R is carbon number 1 independently of one another
~5 alkyl or aryl.More preferably X' is phenyl or trimethylsilyl.
For the viewpoint of the compatibility with (A) ingredient, (B) ingredient is preferably the compound with fluorine atom.Especially
It preferably has the compound of fluorine oxyalkylene.In the case where (B) ingredient is the compound without fluorine atom, surface treatment
Agent be preferably include aftermentioned fluorine series solvent and non-fluorine series solvent mixture as solvent.Can be improved as a result, (A) ingredient with
(B) compatibility of ingredient.
So-called fluorine oxyalkylene refers to multiple by-C as illustrated in described (A) ingredientjF2jWeight represented by O-
(poly-) fluorine oxyalkylene structure that multiple unit is bonded.Details are such as the fluorine oxyalkylene documented by (A) ingredient
Explanation it is such.Wherein, the structure of described (A) ingredient and fluorine oxyalkylene possessed by (B) ingredient is independent of one another.(B) ingredient
In fluorine oxyalkylene Rf' preferably-(CF2)d'-(OCF2)p'(OCF2CF2)q'(OCF2CF2CF2)r'(OCF2CF2CF2CF2)s'
(OCF(CF3)CF2)t'-O(CF2)d'Represented base.Can are as follows: the middle d' be 0~5 integer, p', q', r', s' and t' that
This independently is 0~200 integer, and p'+q'+r'+s'+t'=10~200.Furthermore represented each unit can in bracket
Random bond.
(B) ingredient is preferably compound represented by following formula (5) or formula (6).
A'-Rf'-Z'W'α' (5)
Rf'-(Z'W'α')2 (6)
In formula, Rf' base is as described above, the integer that α ' is 1~7, A' are that fluorine atom, hydrogen atom or end are-CF3
Base ,-CF2H base or-CH2The fluorine-containing base of the monovalence of F base, Z' are singly-bound, carbon atom, silicon atom, nitrogen-atoms or can take through fluorine
Divalent~octavalence organic group in generation, W' are the organic group for the monovalence for having phosphonate group in end.
In the formula (5), A' is that fluorine atom, hydrogen atom or end are-CF3Base ,-CF2H base or-CH2The one of F base
The fluorine-containing base of valence, wherein preferably-CF3Base ,-CF2CF3Base ,-CF2CF2CF3Base.
In the formula (5), formula (6), Z' be singly-bound, carbon atom, silicon atom, nitrogen-atoms or can be fluorine-substituted two
Valence~octavalence organic group.Furthermore the valence mumber of Z' is α '+1.The details of Z' are as represented by the Z recorded in described (A) ingredient
The explanation of base is such, and so-called organic group is base represented by the-Q-M-.Details are as recorded in described (A) ingredient.
Wherein, (A) ingredient and (B) ingredient have independent structure.
In the formula (5) and formula (6), W' be end have phosphonate group monovalence organic group, such as can by-
Q'-P(O)(OX')2It indicates.Q' is the organic group of singly-bound or divalent.As the organic group of divalent, preferably carbon number 1~20, more
Preferably carbon number 2~10 may include two organic silylenes alkyl.In addition, can also have in the options selected from the Q
Divalent organic group.
Base as W', represented by can preferably enumerating by following formula.
[changing 34]
In formula, X' is as described above, the integer that l' is 0~20.
[changing 35]
In formula, X' is as described above, l', m', n' are 1~20 integer independently of one another preferably respectively 2 or 3.
In addition, can also be person represented by following formula as W'.
[changing 36]
In formula, X' and Q are as described above, m' and n' are 0~20 integer independently of one another preferably respectively 2 or 3.
As compound represented by the formula (5) or formula (6), such as compound represented by following formula can be enumerated.
[changing 37]
[changing 38]
[changing 39]
[changing 40]
[changing 41]
[changing 42]
[changing 43]
[changing 44]
In surface treating agent of the invention, the blending amount of (B) ingredient because required firm time, its molecular weight without
Together, total 100 mass parts relative to (A) ingredient and (B) ingredient, preferably become 0.001 mass parts~15 mass parts amount,
And then preferably become 0.05 mass parts~10 mass parts amount, more preferably become 0.1 mass parts~8 mass parts amount, especially
It is to become 0.5 mass parts~5 mass parts amount.If the less than lower limit value of the amount of (B) ingredient, is difficult to show catalyst
Effect.In addition, there is waterproofness decline of hardening envelope etc. if being more than the upper limit value and cause adverse effect to surface characteristic
Tendency.Ingredient (A) and ingredient (B) if mixing carried out using well known mixed method, can also be molten by each ingredient
It is mixed after in the following solvents of Xie Yu.
[solvent]
Preferably coating agent composition of the invention first passes through solvent in advance and is diluted, as the solvent, as long as being
It is then not particularly limited containing fluorine-based modified silane (A) with compound (B) uniform dissolution person of phosphonate group described in making.
For example, can enumerate: fluorine richness aliphatic hydrocarbon series solvent (PF 5070, perfluorooctane etc.), fluorine richness aromatic hydrocarbon series solvent (1,
3- trifluoromethylbenzene etc.), fluorine richness ether series solvent (methyl perfluoro butyl ether, ethylperfluoro butyl ether, perfluor (2- butyl tetrahydrofuran)
Deng), fluorine richness alkyl amine series solvent (perfluorotributylamine, three amylamine of perfluor etc.), hydrocarbon system solvent (benzin, toluene, diformazan
Benzene etc.), ketone series solvent (acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK) etc.).In these, with regard to the side of dissolubility and stability etc.
For face, it is generally desirable to the solvent through fluorine richness, especially preferably fluorine richness ether series solvent, fluorine richness aromatic hydrocarbon series solvent.
The solvent can be used alone one kind, can also be used in mixed way two or more.Solvent be preferably in composition (A) ingredient with
(B) mode that total quality of ingredient becomes 0.01%~50%, preferably 0.03%~25% contains.
Surface treating agent of the invention is by becoming phosphonic acids for the phosphonate group hydrolysis of (B) ingredient and promoting (A) ingredient
Hydrolysis and hardened.In general, about phosphonic acid base (- P (O) (OH)2), if not adding for a long time in 100 DEG C or more progress
Heat not will do it with reacting for OH base present in substrate then, thus under the heating between room temperature low-temperature short-time substrate and (B) at
The reaction divided not will do it.On the other hand, described (A) even if ingredient hydrolyze at room temperature also gently with the-OH of substrate base key
Knot.Therefore, under room temperature or low temperature, carried out using the catalyst function of (B) ingredient (A) ingredient hydrolysis it is preferential and
It carries out rapidly.Even if under the heating as a result, between low-temperature short-time, also can provide the hardening envelope excellent with the adhesion of substrate.
[coating method]
Surface treating agent can be using known in wet coating method (hairbrush coating, dipping, spraying, injection), vapor deposition etc.
Method be applied to substrate.As long as coating condition etc. is according to conventionally known method.Surface treating agent of the invention is applying
Cloth after-hardening is fast, can harden at room temperature.And then in order to be hardened under the short time, can also be carried out at 30 DEG C~200 DEG C
Heating.Hardening is carried out under humidification can improve catalyst action, therefore preferred in terms of promoting hydrolysis.As long as firm time is suitable
Preferably select, for example, can at 25 DEG C with 40 minutes~80 minutes, especially 60 minute or so are hardened.In addition, can be
It was hardened at 80 DEG C with 30 minutes or so.As long as humidity is suitable for adjustment, preferably relative humidity is 40%~50% left
It is right.Furthermore in the case where carrying out wet coating method, the influence of molecular weight is small, therefore there is no restriction for molecular weight, but is utilizing steaming
When gas sedimentation applies surface treating agent of the invention, preferably (A) ingredient and the number average molecular weight of (B) ingredient are phase
Number average molecular weight with degree or (B) ingredient is big.
Particularly preferably number average molecular weight possessed by (B) ingredient is quantity mean molecule possessed by (A) ingredient
0.5 times~5 times of amount.If the number average molecular weight of (B) ingredient is significantly less than the number average molecular weight of (A) ingredient,
It is difficult to (B) ingredient reacted with substrate at room temperature mostly in the initial stage of vacuum evapn deposition step by vapor deposition.Such as
This, is easy (A) ingredient reacted with substrate in the later period of vapor deposition step by vapor deposition, there is the adhesion with substrate
The case where variation.By the way that the difference of number average molecular weight to be set as in the range, effect of the invention can without drawback be played,
Therefore preferably.
It is hardened after surface treating agent of the invention is applied on substrate and forms envelope.The hardening envelope
The film thickness of (fluorine layer) is preferably 50nm hereinafter, especially preferably 0.5nm~20nm, and then preferably 2nm~15nm.
Surface treating agent of the invention assigns water and oil-resistant to substrate surface.The compound with phosphonate ester has
The hardening facilitation effect same with existing hardening accelerator, especially acid catalyst, and the preservation of surface treating agent can be improved
Property.In general, acid catalyst it is rigid mixed with main reagent after play the effect that hardening promotes, but carry out during preservation hardening anti-
It answers, therefore the service life for the treatment of fluid becomes problem often.On the other hand, phosphonate group with reaction of moisture and become phosphonic acid base after send out
The effect of hardening catalyst is waved, therefore the service life bring of surface treating agent is influenced small.
To the substrate handled using surface treating agent of the invention, there is no particular restriction, can for paper, cloth, metal and its
The various materials such as oxide, glass, plastics, ceramics, quartz.It is anti-that surface treating agent of the invention can assign waterproof to the substrate
Oiliness.Especially preferably it is used as through SiO2The glass of processing, film, sapphire substrate surface treating agent.
As the article handled using surface treating agent of the invention, can enumerate: auto navigation, tablet computer,
Smart phone, mobile phone, digital camera, digital camera, personal digital assistant (Personal Digital
Assistant, PDA), portable audio player (portable audio player), car audio, game machine, glasses
The medical instruments such as piece, camera lens, filter, sunglasses, gastroscope, duplicator, personal computer (Personal Computer,
PC), liquid crystal display, organic electroluminescent (electroluminescence, EL) display, plasma scope, touch
The optical articles such as panel type display, protective film, antireflection film.Vapor deposition fluorine system surface treating agent of the invention can prevent fingerprint
And sebum is attached to the article, and assigns antisitic defect in turn, therefore can especially act effectively as touch-screen display, antireflection
The waterproof and oilproofs layer such as film.
[embodiment]
Hereinafter, showing Examples and Comparative Examples, the present invention will be described in more detail, but the present invention is not restricted to
Following embodiments.
Hereinafter, each ingredient used in Examples and Comparative Examples is as described below.Furthermore following number average molecular weight
To pass through1H- nuclear magnetic resonance (Nuclear Magnetic Resonance, NMR) and calculate value.
(A) fluorine-containing organic silicon compound:
(A-1)
[changing 45]
Number average molecular weight: 3,891
(B) containing the compound of phosphonate group:
(B-1)
[changing 46]
Number average molecular weight: 3,943
(B-2)
[changing 47]
Number average molecular weight: 4,369
(B-3)
[changing 48]
Number average molecular weight: 2,999
Compare with hardening catalyst:
(C-1)
[changing 49]
Number average molecular weight: 3,802
(C-2)
[changing 50]
Number average molecular weight: 4,347
(C-3) trifluoroacetic acid
[1~embodiment of embodiment 5 and 1~comparative example of comparative example 4]
The preparation of surface treating agent
In 1~embodiment of embodiment 5, respectively with it is following it is recorded in table 1 form will described in (A-1) ingredient, with (B-1)
Any one of~(B-3) ingredient is mixed (1~mixture of mixture 5), with the mixture (total 100 mass parts)
Concentration is dissolved in as the mode of 20 mass % exerts in hectogram (Novec) 7200 (manufacture of 3M company) 400 mass parts and prepares table
Surface treatment agent.In 1~comparative example of comparative example 4, (A-1) ingredient by described in is formed, compared with what is recorded in following table 2 respectively
Example is mixed (6~mixture of mixture 9) with any one of hardening catalyst (C-1)~(C-3), with the mixture
The concentration of (total 100 mass parts) is dissolved in as the mode of 20 mass % exerts hectogram (Novec) 7200 (manufacture of 3M company) 400
Surface treating agent is prepared in mass parts.
[table 1]
[table 2]
Utilize the formation of the hardening envelope of vacuum evapn deposition
Following object is set as the test body in following evaluations, the object is by following conditions by each of the preparation
5 μ L vacuum evapn of surface treating agent is deposited to the SiO for utilizing 15nm in most surface2The glass handled is (healthy and free from worry
(Corning) company's manufacture, gorilla (Gorilla) 3), it carries out hardening and shape for 1 hour in the environment of 25 DEG C, humidity 50%
At envelope (film thickness: about 10nm).
[utilizing the coating condition and device of vacuum evapn deposition]
Measurement device: small size vacuum vapor deposition apparatus VPC-250F
Pressure: 2.0 × 10-3Pa~3.0 × 10-2Pa
Vapor deposition temperature (the arrival temperature of combustion boat): 500 DEG C
Vapor deposition distance: 20mm
The charge weight of inorganic agent: 5mg
Vapor deposition amount: 5mg
The hardening envelope of the test body is evaluated by following methods.
[waterproofness]
Use contact angle meter Depew Maas special (DropMaster) (consonance interface science company manufactures), measurement hardening envelope
Contact angle relative to water.It records the result in following Table 3.
[abrasion performance]
Abrasion performance relative to steel wool (#0000):
Use Te Bujie (TRIBOGEAR) model (TYPE): 30S (new east scientific company manufacture) utilizes following conditions pair
It hardens envelope to carry out 10,000 time after wearing away back and forth, uses contact angle meter Depew Maas special (DropMaster) (consonance interface section
Company manufacture) contact angle of the measurement hardening envelope relative to water.It records the result in following Table 3.
Contact area: 1cm2
Load: 1kg
[evaluation of keeping quality]
It is saved one month at 50 DEG C, in closed container by the test body.For the test body after saving, contact is used
Count contact angle of Depew Maas special (DropMaster) (manufacture of consonance interface science company) the measurement hardening envelope relative to water in angle.
In turn, it is measured relative to the contact angle of water to implementing the hardening envelope after abrasion performance test.It records the result in
In following Table 3.
[table 3]
As indicated shown in 3, the surface treating agent of comparative example 1 is due to being free of catalyst, and hardening is slow, between low-temperature short-time
Curing condition under will not be sufficiently hardened, therefore it is resulting hardening envelope abrasion performance it is poor.The table of comparative example 2 and comparative example 3
Surface treatment agent contains the fluorochemical with phosphonic acids as hardening catalyst.The surface treating agent between low-temperature short-time under into
Row hardening and the hardening envelope with abrasion performance is provided, but envelope obtained by being hardened after being saved one month at 50 DEG C
Waterproofness is poor, and then abrasion performance is also poor.Speculate that its reason is that surface treating agent includes phosphonic acids, therefore during preservation
(A) ingredient is condensed each other.Comparative example 4 is the surface treating agent comprising existing hardening catalyst.Resulting hardening envelope is prevented
Aqueous difference, and then abrasion performance is also poor.The low boiling point due to trifluoroacetic acid is speculated, in vacuum evapn deposition, on surface
Inorganic agent is sucked into pump before being attached to substrate, and is unable to fully obtain the effect as catalyst.In addition, comparative example 4
The storage stability of surface treating agent is also poor.Think the reason is that the surface treating agent during preservation also because of trifluoroacetic acid
Influence and (A) ingredient is condensed.
In contrast, as shown in 1~embodiment of embodiment 5 of table 3, even if surface treating agent of the invention is in room temperature (25
DEG C, humidity 50%) hardening in 1 hour low-temperature short-time between curing condition under also can provide the hardening with excellent abrasion performance
Envelope.In turn, it even if excellent abrasion performance will not decline after the hardening envelope is saved one month at 50 DEG C, protects
It is also excellent to deposit stability.
[6~embodiment of embodiment 10 and 5~comparative example of comparative example 8]
Utilize the formation of the hardening envelope of spraying coating
Make the 1~mixture of mixture 9 prepared in the 1~embodiment of embodiment 5 and 1~comparative example of comparative example 4 with solid
Body constituent concentration is dissolved in 1,1,1,3,3-pentafluorobutane [Su Kaen (Solkane) 365mfc as the mode of 0.1 mass %
(manufacture of Su Weite (Solvay) company)] in and prepare surface treating agent.
Surface treatment after being prepared 1 hour using spraying applying device (manufacture of T&K limited liability company, NST-51)
It is spraying coated on having carried out corona treatment using following conditions respectively that surface treating agent after a week is saved at agent and 50 DEG C
The surface of the chemically reinforced glass (healthy and free from worry (Corning) company manufacture, gorilla (Gorilla) II) of cleaning.Thereafter, 80
DEG C, carry out hardening in 30 minutes under 40%RH and form hardening envelope, and obtain test body.
[condition of corona treatment]
Device: plasma dry cleaning device PDC210
Gas: O2Gas 80cc, Ar gas 10cc
Output: 250W
Time: 30 seconds
About resulting hardening envelope, waterproofness, abrasion performance and keeping quality are evaluated by following methods.Result is recorded
In table 4.
The evaluation method of waterproofness: it is evaluated by method identical with the waterproof test.
The evaluation of abrasion performance: in addition to round-trip abrasion number to be set as other than 3,000 time, by being tried with the abrasion performance
Identical method is tested to be evaluated.
The evaluation of keeping quality: each test body is saved after a week at 50 DEG C, in closed container, carry out the waterproofness and
The evaluation of abrasion performance.
[table 4]
As shown in table 4, the surface treating agent of comparative example 1 is free of hardening catalyst, therefore short in the low temperature of 80 DEG C, 30 minutes
Envelope with sufficient abrasion performance can not be provided under the curing condition of time.The surface treating agent of 2~comparative example of comparative example 4
Storage stability it is poor.Think that its reason is as described above during preservation, (A) ingredient is condensed each other.
In contrast, as shown in 6~embodiment of embodiment 10 of table 4, even if surface treating agent of the invention is in 80 DEG C, 30
It also can provide the hardening envelope with excellent abrasion performance under curing condition between the low-temperature short-time of minute.It in turn, even if will
After the hardening envelope saves one month at 50 DEG C, excellent abrasion performance will not decline, and storage stability is also excellent.
Industrial availability
It is excellent, with substrate that surface treating agent of the invention can provide water and oil-resistant using the hardening between low-temperature short-time
The excellent hardening envelope of adhesion, and keeping quality is excellent.Therefore, it can be expected that surface treating agent of the invention industrially widely
It is utilized.Especially it can be expected that having the attachment of grease but the important purposes of visibility in hypothesis such as touch-screen display, antireflection films
In, the surface treating agent to form waterproof and oilproof film is acted effectively as, and the productivity for facilitating these products improves.
Claims (12)
1. a kind of surface treating agent, comprising:
(A) with the fluorine-containing organic silicon compound of at least one water-disintegrable base in a molecule；And
(B) in the molecule with the compound of phosphonate group, it is relative to the adding up to 100 mass parts of (A) ingredient and (B) ingredient
0.001 mass parts~15 mass parts amount.
2. surface treating agent according to claim 1, wherein (B) ingredient is the compound with fluorine atom.
3. surface treating agent according to claim 2, wherein (B) ingredient is the compound with fluorine oxyalkylene.
4. surface treating agent according to any one of claim 1 to 3, wherein (A) ingredient is with fluorine oxyalkylene
Fluorine-containing organic silicon compound.
5. surface treating agent according to claim 4, wherein (A) ingredient be selected from the following general formula (1), general formula (2),
At least one of fluorine-containing organic silicon compound represented by general formula (3) or general formula (4):
(A-Rf)α-ZWβ (1)
Rf-(ZWβ)2 (2)
A-Rf-Q-(Y)γB (3)
Rf-(Q-(Y)γB)2 (4)
[in each general formula, Rf base is-(CF independently of one another2)d-(OCF2)p(OCF2CF2)q(OCF2CF2CF2)r
(OCF2CF2CF2CF2)s(OCF(CF3)CF2)t-O(CF2)d-；The integer that d is 0~5；P, q, r, s, t be separately 0~
200 integer, and p+q+r+s+t=10~200；Represented each unit can be randomly bonded in bracket；A is fluorine independently of one another
Atom, hydrogen atom or end are-CF3Base ,-CF2H base or-CH2The fluorine-containing base of the monovalence of F base；Z is single independently of one another
Key, carbon atom, silicon atom, nitrogen-atoms or can be fluorine-substituted divalent~octavalence organic group；W is at end independently of one another
Hold the organic group with the monovalence of water-disintegrable base；The integer that α is 1~7；β is 1~7 integer independently of one another；Z in formula (1)
Valence mumber be (β+α)；The valence mumber of Z in formula (2) is (β+1)；Q is the organic group of singly-bound or divalent independently of one another；γ is each other
It independently is 1~10 integer, Y is the organic group of the divalent with water-disintegrable base independently of one another；And B is independently of one another
The alkyl or halogen atom of hydrogen atom, carbon number 1~4].
6. surface treating agent according to claim 4 or 5, wherein (B) ingredient is by the following general formula (5) or general formula (6) institute
The compound of expression:
A'-Rf'-Z'W'α' (5)
Rf'-(Z'W'α')2 (6)
[in formula, Rf' base is-(CF independently of one another2)d'-(OCF2)p'(OCF2CF2)q'(OCF2CF2CF2)r'
(OCF2CF2CF2CF2)s'(OCF(CF3)CF2)t'-O(CF2)d'-；The integer that d' is 0~5；P', q', r', s', t' are 0~200
Integer, and p'+q'+r'+s'+t'=10~200；Represented each unit can be randomly bonded in bracket；α ' is independently of one another
For 1~7 integer；A' is that fluorine atom, hydrogen atom or end are-CF independently of one another3Base ,-CF2H base or-CH2The one of F base
The fluorine-containing base of valence；Z' be independently of one another singly-bound, carbon atom, silicon atom, nitrogen-atoms or can be fluorine-substituted divalent~eight
The organic group of valence；And W' is the organic group for the monovalence for having phosphonate group in end independently of one another].
7. surface treating agent according to any one of claim 1 to 6, wherein the phosphonate group in described (B) ingredient is
By-P (O) (OX')2It indicates, X' is the alkyl or aryl or-SiR for the carbon number 1~5 for being unsubstituted or being substituted3Represented
Base (alkyl or aryl that the R is carbon number 1~5 independently of one another).
8. surface treating agent according to claim 7, wherein the X' is phenyl or-Si (CH3)3Represented base.
9. surface treating agent according to any one of claim 1 to 7, wherein quantity possessed by described (B) ingredient is flat
Average molecular weight is 0.5 times~5 times of the number average molecular weight of (A) ingredient.
10. a kind of article of the hardening thing with surface treating agent, wherein the surface treating agent is such as claim 1 to the 9
Any one of described in surface treating agent.
11. the article of the hardening thing according to claim 10 with surface treating agent, wherein the article is selected from optics
Article, touch screen, antireflection film, through SiO2The glass and pottery of processing.
12. a kind of method that the surface in article forms hardening envelope, being will be as in claim 1 to 9 by vapor deposition
Described in any item surface treating agents are applied to the surface of article, are hardened and form hardening envelope on the surface of article.
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| JP2016198339 | 2016-10-06 | ||
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| PCT/JP2017/035573 WO2018066479A1 (en) | 2016-10-06 | 2017-09-29 | Surface-treating agent |
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| CN111630123B (en) * | 2018-01-22 | 2023-02-17 | 信越化学工业株式会社 | Coating agent composition, surface treatment agent comprising the same, and article surface-treated with the surface treatment agent |
| WO2023132276A1 (en) * | 2022-01-05 | 2023-07-13 | Ａｇｃ株式会社 | Composition, method for producing composition, coating liquid, article, and method for producing article |
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| JP6683823B2 (en) | 2020-04-22 |
| JPWO2018066479A1 (en) | 2019-08-29 |
| CN109790443B (en) | 2022-03-29 |
| KR20190060768A (en) | 2019-06-03 |
| TWI766887B (en) | 2022-06-11 |
| WO2018066479A1 (en) | 2018-04-12 |
| KR102489200B1 (en) | 2023-01-16 |
| TW201829719A (en) | 2018-08-16 |
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