CN109563338A - Composition - Google Patents
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- CN109563338A CN109563338A CN201780050159.6A CN201780050159A CN109563338A CN 109563338 A CN109563338 A CN 109563338A CN 201780050159 A CN201780050159 A CN 201780050159A CN 109563338 A CN109563338 A CN 109563338A
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/28—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material
- C03C17/30—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material with silicon-containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/02—Polyalkylene oxides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/321—Polymers modified by chemical after-treatment with inorganic compounds
- C08G65/323—Polymers modified by chemical after-treatment with inorganic compounds containing halogens
- C08G65/3233—Molecular halogen
- C08G65/3236—Fluorine
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/336—Polymers modified by chemical after-treatment with organic compounds containing silicon
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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
Abstract
The purpose of the present invention is to provide the application compositions with good wear resistance.The present invention is a kind of composition, characterized by comprising: compound (A), is bonded with either one in (a1) 1 valence group and (a2) hydrolization group with perfluoropolyether structures and hydroxyl on the silicon atoms；With compound (B), with hydroxyl and oxygroup alkylidene unit, at least part in the hydrogen atom of oxygroup alkylidene unit is replaced by fluorine atoms, and number-average molecular weight is less than 10000.
Description
Technical field
The present invention relates to compositions.
Background technique
For by the composition comprising the compound containing fluorine oxygroup alkylidene (fluoro oxyalkylene group)
For the envelope of formation, since its surface free energy is very small, thus there is hydro-oleophobicity, chemical resistance, release property
Deng.Using its property, a kind of fluorine-containing coating agent is disclosed in patent document 1, it includes (A) through poly- containing fluorine oxygroup alkylidene
The polymer modified mean molecule containing the silane of hydrolization group and/or its partial hydrolysis condensate and with (A) ingredient
(B) of average molecular weight below is measured containing the polymer of fluorine oxygroup alkylidene.It records and (B) of patent document 1 is claimed to contain fluorine oxygen
The polymer of base alkylidene is containing whether there is or not the fluorine oxygroup alkylidenes of function.
In addition, disclosing a kind of vapor deposition fluorine system surface treating agent in patent document 2, it includes (A) through containing fluorine oxygroup
The polymer modification of alkylidene contains the silane of hydrolization group and/or its partial hydrolysis condensate and weight average molecular weight ratio
It is somebody's turn to do the big polymer of (B) containing fluorine oxygroup alkylidene of (A) ingredient, and the mixing mass ratio of (A) ingredient and (B) ingredient is 6:
4~9:1.It records and (B) of patent document 2 is claimed also to be similarly no function with patent document 1 containing the polymer of fluorine oxygroup alkylidene.
Existing technical literature
Patent document
Patent document 1: Japanese Unexamined Patent Publication 2015-199915 bulletin
Patent document 2: Japanese Unexamined Patent Publication 2013-136833 bulletin
Summary of the invention
Problems to be solved by the invention
It is described in patent document 1 containing whether there is or not the excellent in wear resistance of the polymer of the fluorine oxygroup alkylidene of function, in addition,
It is described in patent document 2 when being vaporized on fluorine system surface treating agent on substrate using vacuum vapour deposition, forms excellent in te pins of durability
Envelope.However, remaining in terms of the raising of wear resistance improves space.
The present invention be in view of the above subject and make, and it is an object of the present invention to provide the quilt with good wear resistance can be formed
The composition of film.
Means for solving the problems
The present invention is a kind of composition, it includes: it is poly- with perfluor to be bonded with (a1) on the silicon atoms for compound (A)
Either one in the 1 valence group and (a2) hydrolization group and hydroxyl of ether structure；With compound (B), with hydroxyl and
Oxygroup alkylidene unit, at least part in the hydrogen atom of oxygroup alkylidene unit are replaced by fluorine atoms, and number-average molecular weight is small
In 10000.
Aforesaid compound (A) is preferably following formula (1a) or the compound that (2a) is indicated.
[chemical formula 1]
In formula (1a),
Rf1The alkyl or fluorine atom that the carbon atom number being replaced by fluorine atoms for 1 or more hydrogen atom is 1~20,
Rf2It is former for 1~20 alkyl or fluorine to be each independently the carbon atom number that 1 or more hydrogen atom is replaced by fluorine atoms
Son,
R1It is each independently the alkyl that hydrogen atom or carbon atom number are 1~4,
R2It is each independently the alkyl that carbon atom number is 1~20,
D is each independently-O- ,-C (=O)-O- ,-O-C (=O)-,-NR- ,-NRC (=O)-or-C (=O) NR-, R
For hydrogen atom, carbon atom number be 1~4 alkyl or carbon atom number be 1~4 containing fluoroalkyl,
E is each independently hydrolization group or hydroxyl,
A1, b1, c1, d1 and e1 are each independently 0 or more and 600 integers below, and a1, b1, c1, d1 and e1's is total
Value is 9 or more,
N is 1 or more and 3 integers below,
For each repetitive unit for indicating a1, b1, c1, d1 and e1 and being bracketed with bracket, as long as with by least one
Part forms the sequence arrangement of perfluoropolyether structures, can respectively arrange in any order.
[chemical formula 2]
In formula (2a),
Rf3The alkyl or fluorine atom that the carbon atom number being replaced by fluorine atoms for 1 or more hydrogen atom is 1~20,
Rf4It is former for 1~20 alkyl or fluorine to be each independently the carbon atom number that 1 or more hydrogen atom is replaced by fluorine atoms
Son,
R3It is each independently the alkyl that hydrogen atom or carbon atom number are 1~4,
R4It is each independently the alkyl that carbon atom number is 1~20,
M is each independently-O- ,-C (=O)-O- ,-O-C (=O)-,-NR- ,-NRC (=O)-or-C (=O) NR-, R
For hydrogen atom, carbon atom number be 1~4 alkyl or carbon atom number be 1~4 containing fluoroalkyl,
G is each independently hydrolization group or hydroxyl,
The alkyl that Y is each independently hydrogen atom or carbon atom number is 1~4,
Z be hydrogen atom or halogen atom,
A2, b2, c2, d2 and e2 are each independently 0 or more and 600 integers below, and a2, b2, c2, d2 and e2's is total
Value is 9 or more,
F2 is 1 or more and 20 integers below,
G2 is 0 or more and 2 integers below,
P is 1 or more and 3 integers below,
For each repetitive unit for indicating a2, b2, c2, d2 and e2 and being bracketed with bracket, as long as with by least one
Part forms the sequence arrangement of perfluoropolyether structures, can respectively arrange in any order.
Aforesaid compound (A) is preferably the chemical combination that the aggregate value of a1, b1, c1, d1 and e1 of above-mentioned formula (1a) are 13 or more
The compound that the aggregate value of object or a2, b2, c2, d2 and e2 of above-mentioned formula (2a) are 13 or more.
Aforesaid compound (B) is preferably the compound that following formula (1b) is indicated.
[chemical formula 3]
In above-mentioned formula (1b), X is each independently hydrogen atom or fluorine atom, Rf5It is former to be each independently hydrogen atom, fluorine
Son or-CF3, J be-O- ,-C (=O)-O- or-O-C (=O)-O-, a3 be 1 or more and 5 hereinafter, b3 be 20 or more and 200 with
Under, c3 is 5 or more and 200 hereinafter, for each repetitive unit for indicating a3~c3 and being bracketed with bracket, as long as with by extremely
Few a part forms the sequence arrangement of oxygroup alkylidene unit, can respectively arrange in any order, the oxygroup alkylene
At least part hydrogen atom in base unit is replaced by fluorine atoms.
The number for the hydroxyl for including in aforesaid compound (B) is preferably 1~2.In addition, in aforesaid compound (B), relatively
The ratio of number of fluorine atoms for the summation of the number of hydrogen atoms other than hydrogen atom in hydroxyl-removal and number of fluorine atoms be 40% with
Upper is also preferred.
It is preferred that aforesaid compound (A) is 1 or more relative to the mass ratio of aforesaid compound (B).
The effect of invention
Composition through the invention, due to making while using compound (A) for being characterized in that perfluoropolyether structures
It is taken at least part in the hydrogen atom with hydroxyl and oxygroup alkylidene unit and oxygroup alkylidene unit by fluorine atom
The compound (B) in generation, thus it is able to achieve the hydrophobicity envelope of excellent in wear resistance.
Specific embodiment
Composition of the invention is comprising the compound (A) with perfluoropolyether structures and has hydroxyl and oxygroup alkylidene
The compound (B) of unit.By in hydrogen atom possessed by perfluoropolyether structures possessed by compound (A) and compound (B)
The oxygroup alkylidene unit that is replaced by fluorine atoms of at least part, envelope can be made to play good hydrophobicity.In addition, by making
Compound (B) has hydroxyl, can ensure that the wear resistance of envelope.
Compound (A) as long as not only containing fluorine and also can by via polymerization reaction (especially polycondensation reaction) will change
Close object (A) each other or its compound for being bonded and being formed the matrix of envelope together with other monomers.Preferably, compound
It (A) is preferably the compound containing at least one party and fluoro-containing group in hydrolization group and hydroxyl, wherein in the present invention, make
For compound (A), the 1 valence group and (a2) water-disintegrable base for being bonded with (a1) on the silicon atoms there are perfluoropolyether structures are used
The compound of either one in group and hydroxyl.
Aforementioned perfluoropolyether structures refer to that whole hydrogen of polyalkylene ether or polyalkyleneglycol dialkylether residue are former
Structure obtained from son is replaced by fluorine atoms, alternatively referred to as perfluor polyalkylene ether or perfluor polyalkylene glycol dialkyl group
Ether residue.In addition, perfluoropolyether structures can also be known as perfluorooxyalkylene.Perfluoropolyether structures are assigned to obtained envelope
Hydrophobicity.The carbon atom number for including in the longest linear fraction of perfluoropolyether structures is for example preferably 5 or more, more preferably 10
More than, further preferably 20 or more.The upper limit of aforementioned carbon atom number is not particularly limited, such as can be 200 or so.
In compound (A), above-mentioned 1 valence group and silicon atom bonding with perfluoropolyether structures.In perfluoropolyether structures
With the side of silicon atom bonding, may exist linking group appropriate, the linking group also may not be present but above-mentioned perfluor is poly-
Ether structure is bonded directly to silicon atom.As linking group, the alkyl such as alkylidene, aromatic hydrocarbyl, (poly-) Asia can be enumerated
Group obtained from least part in alkyl diol base and their hydrogen atom is replaced by fluorine atoms and they are appropriate
The group etc. that ground is formed by connecting.The carbon atom number of linking group be, for example, 1 or more and 20 hereinafter, preferably 2 or more and 10 with
Under.
It should be noted that multiple silicon atoms can be bonded on a linking group, it can also be on a linking group
It is bonded multiple perfluoropolyether structures.Be bonded to the above-mentioned 1 valence group with perfluoropolyether structures of silicon atom number be 1 with
It is upper, it can be 2 or 3, but preferably 1 or 2, particularly preferably 1.
In addition, in compound (A), it is bonded with either one in hydrolization group and hydroxyl, the water on the silicon atoms
Solution property group and hydroxyl be respectively provided with via hydrolysis and/or dehydration condensation and each other or compound (A) by compound (A)
The effect being bonded with the reactive hydrogen of hydroxyl from substrate surface etc..As such hydrolization group, such as alcoxyl can be enumerated
Base (especially carbon atom number be 1~4 alkoxy), acetoxyl group, halogen atom (especially chlorine atom) etc..Preferred hydrolysis
Property group be alkoxy and halogen atom, particularly preferably methoxyl group, ethyoxyl, chlorine atom.
The number for being bonded to the hydrolization group of silicon atom is 1 or more, can be 2 or 3, but preferably 2 or 3,
Particularly preferably 3.When being bonded with 2 or more hydrolization groups on the silicon atoms, it can be bonded with different water on the silicon atoms
Solution property group, but it is preferably bonded with identical hydrolization group on the silicon atoms.It is bonded to fluoro-containing group and the hydrolysis of silicon atom
Property group sum be usually 4, but may be 2 or 3 (especially 3).It, can be in remaining chemistry in 3 situations below
It is bonded on key such as alkyl (especially carbon atom number be 1~4 alkyl), hydrogen atom, isocyanate group.
The 1 valence group with perfluoropolyether structures of compound (A) can be straight-chain, it is possible to have side chain.
The number-average molecular weight of compound (A) is not particularly limited, and for example, 6000 or more, preferably 7000 or more, in addition,
For 15000 hereinafter, preferably 12000 or less.
As compound (A), the compound of such as following formula (1a) can be enumerated.
[chemical formula 4]
In formula (1a),
Rf1The alkyl or fluorine atom that the carbon atom number being replaced by fluorine atoms for 1 or more hydrogen atom is 1~20,
Rf2It is former for 1~20 alkyl or fluorine to be each independently the carbon atom number that 1 or more hydrogen atom is replaced by fluorine atoms
Son,
R1It is each independently the alkyl that hydrogen atom or carbon atom number are 1~4,
R2It is each independently the alkyl that carbon atom number is 1~20,
D is each independently-O- ,-C (=O)-O- ,-O-C (=O)-,-NR- ,-NRC (=O)-or-C (=O) NR-, R
For hydrogen atom, carbon atom number be 1~4 alkyl or carbon atom number be 1~4 containing fluoroalkyl,
E is each independently hydrolization group or hydroxyl,
A1, b1, c1, d1 and e1 are each independently 0 or more and 600 integers below, and a1, b1, c1, d1 and e1's is total
Value is 9 or more, preferably 13 or more,
N is 1 or more and 3 integers below,
For each repetitive unit for indicating a1, b1, c1, d1 and e1 and being bracketed with bracket, as long as with by least one
Part forms the sequence arrangement of perfluoropolyether structures, can respectively arrange in any order.In addition, each repetitive unit can
With there are multiple in the molecule.In this specification, there are multiple situations in the molecule for so-called repetitive unit, also include weight
The case where multiple unit discontinuously exists, for example a certain repetitive unit have 2, respectively by 2 different repetitions in the molecule
The case where unit clamps.
Rf1The alkyl that the carbon atom number preferably replaced by 1 or more fluorine atom is 1~10, more preferably carbon atom number
For 1~10 perfluoroalkyl, further preferably carbon atom number be 1~5 perfluoroalkyl.
Rf2It is preferred that being each independently fluorine atom or carbon atom number as 1~2 containing fluoroalkyl, more preferably all fluorine are former
Son.
R1Preferably hydrogen atom or carbon atom number are 1 or 2 alkyl, more preferably all hydrogen atoms each independently.
R2It is each independently preferably the alkyl that carbon atom number is 1~5.
D is preferably each independently-C (=O)-O- ,-O- ,-O-C (=O)-, more preferable all-O-.
E is preferably the alkoxy that carbon atom number is 1~4, halogen atom, particularly preferably methoxyl group, second each independently
Oxygroup, chlorine atom.
About the sequence for each repetitive unit for indicating a1, b1, c1, d1 and e1 and being bracketed with bracket, preferably near fixation
The repetitive unit for indicating b1 and being bracketed with bracket of end side (side with silicon atom bonding) is located at than near free end side
Indicate a1 and the repetitive unit that is bracketed with bracket more lean on the position of free end side, more preferably near fixed end side indicate b1 and
D1 and the repetitive unit bracketed with bracket are located at than the repetition for indicating a1 and c1 and bracketed with bracket near free end side
Unit more leans on the position of free end side.It indicates e1 and preferably at least has 2 with each repetitive unit that bracket brackets.
N is preferably 2 or more and 3 hereinafter, more preferably 3.
In above-mentioned formula (1a), it is therefore particularly preferred that Rf1The perfluoroalkyl for being 1~5 for carbon atom number, Rf2All fluorine are former
Son, R1All hydrogen atoms, D all-O-, E are methoxy or ethoxy, the integer that a1 is 1~3, c1=d1=0, b1 and
E1 is the value set in such a way that the compound of formula (1a) can maintain liquid under normal pressure, n=3.It can make the aggregate value of b1 and e1
It is 8 or more.
As the compound that above-mentioned formula (1a) is indicated, the compound of such as following formula (1a-1) can be enumerated.
[chemical formula 5]
In above-mentioned formula (1a-1), R10The perfluoroalkyl for being 1~5 for carbon atom number, R11The perfluor for being 1~5 for carbon atom number
Alkylidene, R12The perfluorinated alkylidene for being 1~3 for carbon atom number, R13The alkylidene for being 1~3 for carbon atom number, R14For carbon atom
The alkyl that number is 1~3, z2 and z3 are 1~3 integer, and z1 is can be under normal pressure with the compound that above-mentioned formula (1a-1) indicates
The value for maintaining the mode of liquid to set, such as may be set to 3 or more.
In addition, other than the compound of above-mentioned formula (1a), the chemical combination of following formula (2a) can be enumerated as compound (A)
The compound of object, preferably following formula (2a).
[chemical formula 6]
In above-mentioned formula (2a),
Rf3The alkyl or fluorine atom that the carbon atom number being replaced by fluorine atoms for 1 or more hydrogen atom is 1~20,
Rf4It is former for 1~20 alkyl or fluorine to be each independently the carbon atom number that 1 or more hydrogen atom is replaced by fluorine atoms
Son,
R3It is each independently the alkyl that hydrogen atom or carbon atom number are 1~4,
R4It is each independently the alkyl that carbon atom number is 1~20,
M is each independently-O- ,-C (=O)-O- ,-O-C (=O)-,-NR- ,-NRC (=O)-or-C (=O) NR-, R
For hydrogen atom, carbon atom number be 1~4 alkyl or carbon atom number be 1~4 containing fluoroalkyl,
G is each independently hydrolization group or hydroxyl,
The alkyl that Y is each independently hydrogen atom or carbon atom number is 1~4,
Z be hydrogen atom or halogen atom,
A2, b2, c2, d2 and e2 are each independently 0 or more and 600 integers below, and a2, b2, c2, d2 and e2's is total
Value is 9 or more, preferably 13 or more,
F2 is 1 or more and 20 integers below,
G2 is 0 or more and 2 integers below,
P is 1 or more and 3 integers below,
For each repetitive unit for indicating a2, b2, c2, d2 and e2 and being bracketed with bracket, as long as with by least one
Part forms the sequence arrangement of perfluoropolyether structures, can respectively arrange in any order.In addition, each repetitive unit can
With there are multiple in the molecule.
Rf3The alkyl that the carbon atom number preferably replaced by 1 or more fluorine atom is 1~10, more preferably carbon atom number
For 1~10 perfluoroalkyl, further preferably carbon atom number be 1~5 perfluoroalkyl.
Rf4It is preferred that being each independently fluorine atom or carbon atom number as 1~2 containing fluoroalkyl, more preferably all fluorine are former
Son.
R3It is preferred that it is each independently the alkyl that hydrogen atom or carbon atom number are 1 or 2, more preferable all hydrogen atoms.
R4It is each independently preferably the alkyl that carbon atom number is 1~5.
M is preferably each independently-C (=O)-O- ,-O- ,-O-C (=O)-, more preferable all-O-.
G is preferably alkoxy, halogen atom, particularly preferably methoxyl group, ethyoxyl, chlorine atom each independently.
The alkyl that Y is preferably each independently hydrogen atom or carbon atom number is 1 or 2, more preferable all hydrogen atoms.
Z is preferably hydrogen atom.
It is preferred that a2, c2 and d2 are respectively the 1/2 of b2 hereinafter, more preferably 1/4 hereinafter, further preferably c2 or d2 is 0, it is special
Not preferred c2 and d2 is 0.
E2 is preferably 1/5 or more of the aggregate value of a2, b2, c2 and d2, and for a2, b2, c2 and d2 aggregate value below.
B2 be preferably 20 or more and 600 hereinafter, more preferably 20 or more and 200 hereinafter, further preferably 50 or more,
And 200 or less.E2 be preferably 4 or more and 600 hereinafter, more preferably 4 or more and 200 hereinafter, further preferably 10 or more,
And 200 or less.The aggregate value of a2, b2, c2, d2 and e2 are preferably 20 or more and 600 hereinafter, more preferably 20 or more and 200
Hereinafter, further preferably 50 or more and 200 or less.
F2 is preferably 1 or more and 18 or less.Further preferably 1 or more and 15 or less.
G2 is preferably 0 or more and 1 or less.
P is preferably 2 or more and 3 hereinafter, more preferably 3.
About the sequence for each repetitive unit for indicating a2, b2, c2, d2 and e2 and being bracketed with bracket, preferably near fixation
The repetitive unit for indicating b2 and being bracketed with bracket of end side (side with silicon atom bonding) is located at than near free end side
Indicate a2 and the repetitive unit that is bracketed with bracket more lean on the position of free end side, more preferably near fixed end side indicate b2 and
D2 and the repetitive unit bracketed with bracket are located at than the repetition for indicating a2 and c2 and bracketed with bracket near free end side
Unit more leans on the position of free end side.In addition, indicating e2 and preferably at least having 2 with each repetitive unit that bracket brackets.
In formula (2a), it is therefore particularly preferred that Rf3The perfluoroalkyl for being 1~5 for carbon atom number, Rf4All fluorine atoms, M
All-O-, G are methoxyl group, ethyoxyl or chlorine atom (especially methoxy or ethoxy), and Y and Z are hydrogen atom, and a2 is
(more preferable 80~140), it be 0, g2 is 0 or more and 1 or less (especially 0), p that e2, which is 30~60, c2 and d2,0, b2 for 30~150
It is 1~10 for 3, f2.
As the compound that above-mentioned formula (2a) is indicated, the compound of such as following formula (2a-1) can be enumerated.
[chemical formula 7]
In above-mentioned formula (2a-1), R20The perfluoroalkyl for being 2~6 for carbon atom number, R21And R22Be carbon atom number be 2~6
Perfluorinated alkylidene, R23The trivalent saturated hydrocarbyl for being 2~6 for carbon atom number, R24The alkyl for being 1~3 for carbon atom number.R20、R21、
R22And R23Carbon atom number each independently be preferably 2~4, more preferably 2~3.X1 be 5~70, x2 be 1~5, x3 be 1~
10.X1 is preferably 10~60, and more preferably 20~50, x2 is preferably 1~4, and more preferably 1~3, x3 is preferably 1~8, more excellent
It is selected as 1~6.
Compound (B) has hydroxyl and an oxygroup alkylidene unit, and at least one in the hydrogen atom of oxygroup alkylidene unit
Divide and be replaced by fluorine atoms, number-average molecular weight is less than 10000.The substrates such as the hydroxyl and glass of compound (B) or compound (A) formation
Interaction, becomes to be not easily stripped, it is therefore contemplated that replacing compound with the compound of the similar structures without hydroxyl is used
(B) the case where, is compared, and the wear resistance of envelope improves.
In addition, substantially ensuring the viewpoint of the ingredient from compound (B) from the envelope as obtained from vacuum evaporation
Consider, the number-average molecular weight of compound (B) is important less than 10000, and lower limit is for example preferably 1000 or so.Compound (B)
Number-average molecular weight be preferably 8000 hereinafter, more preferably 6000 or less.
Hydroxyl in compound (B) is there are at least one, preferably 5 hereinafter, more preferably 2 or less.In addition,
Fluorine atom in compound (B), for the summation of number of hydrogen atoms and number of fluorine atoms other than the hydrogen atom in hydroxyl-removal
Several ratios is preferably 40% or more, can play good hydrophobicity as a result,.The ratio of number of fluorine atoms above-mentioned is more preferably
50% or more, further preferably 55% or more, the upper limit is not particularly limited, and can be 100%, such as can be left for 80%
It is right.
As compound (B), the compound that for example following formula (1b) indicates can be enumerated.
[chemical formula 8]
In formula (1b), X is each independently hydrogen atom or fluorine atom, Rf5Be each independently hydrogen atom, fluorine atom or-
CF3, J is that-O- ,-C (=O)-O- or-O-C (=O)-O-, a3 are 1 or more and 5 hereinafter, b3 is 20 or more and 200 hereinafter, c3
For 5 or more and 200 hereinafter, for each repetitive unit for indicating a3~c3 and being bracketed with bracket, as long as with by least one
Part forms the sequence arrangement of oxygroup alkylidene unit, can respectively arrange in any order, the oxygroup alkylidene list
At least part hydrogen atom in member is replaced by fluorine atoms.In addition, each repetitive unit for indicating a3~c3 and being bracketed with bracket
There may be multiple in the molecule.
Rf5It is each independently preferably hydrogen atom or fluorine atom, X is preferably hydrogen atom, and J is preferably-O-, and a3 is preferably 1
Above and 3 hereinafter, more preferably 1 or 2 (most preferably 2).B3 be preferably 30 or more and 100 hereinafter, c3 be preferably 10 or more and
80 or less.The number-average molecular weight for the compound that b3, c3 are indicated with above-mentioned formula (1b) becomes 2000~4500, it is more preferable 2500~
It is also preferred that 4500 mode, which determines,.Most desirably, preferably Rf5It is each independently hydrogen atom or fluorine atom, X is that hydrogen is former
Son, J are-O-, and a3 is 1 or 2, and b3, c3 are that the number-average molecular weight of the compound indicated with above-mentioned formula (1b) becomes 2000~4500
(the value that the mode of more preferable 2500~4500) determines.
As compound (B), the hydrogen that can enumerate an OH base in the polyalkylene glycol that such as two ends are OH base is former
The polyalkylene glycol that son can be substituted and at least part in the hydrogen atom of alkylidene is replaced by fluorine atoms.As change
It closes object (B), the polyalkylene glycol that at least part in the hydrogen atom of particularly preferred alkylidene is replaced by fluorine atoms is such
Polyalkylene glycol can for example be indicated by following formula (1b-1) and (1b-2).
[chemical formula 9]
In formula (1b-1), R30、R31、R32、R34And R35It is each independently the alkylidene that carbon atom number is 2~6, R33For carbon
The alkylidene that atomicity is 1~5, R30~R35In whole alkylidenes in, at least one alkylidene, in hydrogen atom at least 1
It is a to be replaced by fluorine atoms.Y1 is that 2~10, y2 is the number-average molecular weight that 1~4, y3~y5 is the compound indicated with formula (1b-1)
The value determining as 2000~2400 mode, y6 is that 1~4, y7 is 2~10.
R30、R31、R32、R34And R35It is each independently preferably the alkylidene that carbon atom number is 2~4, more preferably carbon is former
The alkylidene that subnumber is 2~3.In addition, R33Preferably carbon atom number is 1~3 alkylidene, and more preferably carbon atom number is 1~2
Alkylidene.Y1 is preferably 3~9, and more preferably 4~8, y2 is preferably 1~3, and more preferably 1~2, y6 is preferably 1~3, more
Preferably 1~2, y7 is preferably 3~9, and more preferably 4~8.
[chemical formula 10]
In formula (1b-2), R40And R43It is each independently the alkylidene that carbon atom number is 1~3, R41For in hydrogen atom extremely
The alkylidene that few 1 carbon atom number being replaced by fluorine atoms is 1~5, R42It is replaced by fluorine atoms at least one in hydrogen atom
The alkylidene that carbon atom number is 1~3, w1 and w4 is each independently 1~3, w2 and w3 is the compound indicated with formula (1b-2)
Number-average molecular weight as 3800~4200 mode determine value.
R40And R43It is each independently preferably the alkylidene that carbon atom number is 1~2, R41At least 1 preferably in hydrogen atom
The alkylidene that a carbon atom number being replaced by fluorine atoms is 1~3, R42At least one preferably in hydrogen atom is replaced by fluorine atoms
Carbon atom number be 1~2 alkylidene, w1 and w4 are preferably 1~2 each independently, more preferably meet these important documents simultaneously.
Compound (A) in composition is preferably 1 or more relative to the mass ratio of compound (B).It can improve to obtain as a result,
Envelope hydrophobicity and wear resistance harmony.Compound (A) in composition relative to compound (B) mass ratio more
Preferably 2.0 or more, further preferably 3.5 or more, further preferably 5 or more (especially 7 or more).Furthermore, it is contemplated that
The hydrophobicity of obtained envelope and the harmony of wear resistance, the upper limit of the mass ratio be preferably 13 hereinafter, more preferably 11 with
Under.
For the gross mass of composition, total mass ratio of compound (A) and compound (B) in composition
Example is preferably 10 mass % or more, more preferably 12 mass % or more, further preferably 14 mass % or more.The upper limit is without spy
It does not limit, for example, 30 mass % are hereinafter, can be 27 mass % hereinafter, be 25 mass % or less being also preferred.
Composition of the invention preferably includes not only above-mentioned compound (A) and (B), but also includes fluorine series solvent (C).It closes
In fluorine series solvent (C), such as fluoro ether series solvent, fluoro amine series solvent, fluoro hydrocarbon system solvent (especially fluoro fragrance can be used
Race's solvent) etc., particularly preferred boiling point is 100 DEG C or more.As fluoro ether series solvent, preferably fluoroalkyl (especially carbon atom number
Perfluoroalkyl for 2~6) hydrofluoroethers such as-alkyl (especially methyl or ethyl) ether, can enumerate such as ethyl no nafluoro butyl ether or
Nine fluorine isobutyl ether of ethyl.As nine fluorine isobutyl ether of ethyl no nafluoro butyl ether or ethyl, such as Novec (registrar can be enumerated
Mark) 7200 (3M corporation, molecular weight are about 264, and boiling point is 76 DEG C).As fluoro amine series solvent, preferably in the hydrogen atom of ammonia
The amine that is replaced by fluoroalkyl of at least one, the preferred uncle that is replaced by fluoroalkyl (especially perfluoroalkyl) of whole hydrogen atoms of ammonia
Amine, specifically, three (heptafluoropropyl) amine can be enumerated, (molecular weight is about 471 to Fluorinert (registered trademark) FC-3283, boiling
Point is 128 DEG C) belong to the compound.As fluoro hydrocarbon system solvent, 1,3- bis- (trifluoromethylbenzenes) (boiling point: about 116 can be enumerated
℃)。
As fluorine series solvent (C), in addition to that mentioned above, ASAHIKLIN (registered trademark) AK225 can be used, and (Asahi Glass is public
Department's system) etc. hydrofluorocarbon such as hydrochlorofluorocarbons, ASAHIKLIN (registered trademark) AC2000 (Asahi Glass corporation) etc..
The molecular weight of fluorine series solvent (C) is preferably 900 hereinafter, more preferably 800 hereinafter, lower limit is not particularly limited, example
For example 300 or so.
For the gross mass of composition, the content of the fluorine series solvent (C) in composition of the invention is, for example, 20
Quality % or more, more preferably 50 mass % or more, further preferably 70 mass % or more, preferably 90 mass % hereinafter,
More preferably 88 mass % are hereinafter, further preferably 86 mass % or less.
Composition of the invention can also include silanol condensation catalyst.As silanol condensation catalyst, can enumerate
The organic acids such as the inorganic acids such as hydrochloric acid, nitric acid, acetic acid, titanium complex are (for example, Matsumoto Fine Chemical Co.Ltd.
System, Orgatics TC-750 etc.), metal complexes, the metal alkoxide such as tin complex etc..Relative to composition gross mass and
Speech, the amount of silanol condensation catalyst is, for example, 0.00001~0.1 mass %, preferably 0.00002~0.01 mass %, into
One step is preferably 0.0005~0.001 mass %.
Composition of the invention can contain antioxidant, antirust agent, purple in the range of not interfering effect of the invention
Ultraviolet absorbers, light stabilizer, mould inhibitor, antibacterial agent, anti-halobios adhersion agent, deodorant, pigment, fire retardant, antistatic agent etc.
Various additives.
When composition of the invention includes various additives, as the content of various additives, for example, relative to the present invention
Composition component of polymer for, be 0.01~70 mass %, preferably 0.05~50 mass %, more preferably 0.1~
30 mass %, further preferably 0.5~5 mass %.
Composition of the invention can be suitably used for forming envelope on substrate by vacuum evaporation.It is steamed as vacuum
Known condition can be used in the condition of plating.Vacuum degree is, for example, 10-2The left and right Pa or less.In addition, heating when as vapor deposition treatment
Resistance heating manner, any in electron beam heating method can be used in method, and heating temperature is, for example, 100~400 DEG C.Film forming
Time is, for example, 1~60 second or so.
After vacuum evaporation, in air, stand at room temperature, or heated (such as in 50~150 DEG C keep 5~
30 minutes), the moisture in air is absorbed, the hydrolization group for being bonded to silicon atom of compound (A) is hydrolyzed, siloxanes is formed
Key can obtain cured envelope.The film thickness of obtained envelope for example can be 2~10nm.
The material that the substrate of composition of the invention is deposited is not particularly limited, and can be organic based material, inorganic system's material
It is any in material, the shape of substrate can be it is any in plane, curved surface, be also possible to three-dimensional made of combining multiple faces and tie
Structure.As aforementioned organic based material, acrylic resin, polycarbonate resin, polyester resin, styrene resin, propylene can be enumerated
The thermoplastic resins such as acid-styrene copolymerized resin, celluosic resin, polyolefin resin, polyvinyl alcohol；Phenolic resin, urea tree
Thermosetting resins such as rouge, melamine resin, epoxy resin, unsaturated polyester (UP), organic siliconresin, polyurethane resin etc..As
Aforementioned inorganic based material can enumerate the metals such as iron, silicon, copper, zinc, aluminium, the alloy comprising these metals, ceramics, glass etc..Its
In, composition of the invention is particularly preferably deposited on the substrate of the inorganic material such as glass, metal, ceramics and forms envelope.
After forming envelope on substrate, the state after being deposited can be kept, defined post-processing can also be carried out, pass through progress
Post-processing, can be further improved the wear resistance of envelope.As post-processing, it can enumerate and carry out heating holding, in the case where humidifying atmosphere
Stand, carry out ultrasonic washing, with solvent wiping surface etc., these post-processings can be carried out individually, can also combine two or more and
It carries out.Wherein, it particularly preferably carries out heating holding, carry out ultrasonic washing, kept about heating, such as protected in 100~200 DEG C
It holds 10~60 minutes, in addition, about ultrasonic washing, such as uses water, fluorine series solvent or alcohol etc. as cleaning solution, into
Row 1~5 minute or so.From the viewpoint of further increasing wear resistance, preferred ultrasonic washing.Combination of the invention
Object is due to comprising the compound (B) with hydroxyl, thus the case where with composition include the previous compound without hydroxyl
It compares, by being post-processed, it can be expected that compound (B) and the interaction of substrate (such as glass) or compound (A) become
State with higher endurance.
Easy bonding can be implemented to substrate in advance to handle.As the processing of easy bonding, sided corona treatment can be enumerated, at plasma
The hydrophilicity-imparting treatments such as reason, UV treatment.In addition, using the primary coat based on resin, silane coupling agent, tetraalkoxysilane etc.
Processing.In addition, vapor deposition can also be used and be film-made and form silicon dioxide layer.
As priming coat, it is preferable to use comprising being condensed by following formula (p1) compound indicated and/or its partial hydrolysis
The layer that the priming coat formation of (E) ingredient that object is formed is formed with composition.
Si(X2)4 ···(p1)
(wherein, in formula (p1), there are multiple X2Each independently represent halogen atom, alkoxy or isocyanates
Base.)
In above-mentioned formula (p1), X2It is each independently preferably chlorine atom, alkoxy or isocyanic acid that carbon atom number is 1~4
Ester group, in turn, preferably 4 X2It is identical.
As the compound that such formula (p1) is indicated, specifically, preferably using Si (NCO)4、Si(OCH3)4、Si
(OC2H5)4Deng.(E) ingredient can be used alone, and can also be used in combination of two or more.
(E) ingredient for including in priming coat formation composition can be the part water of above-mentioned formula (p1) compound indicated
Solve condensation product.The partial hydrolysis condensate for the compound that above-mentioned formula (p1) indicates can be by using acidand basecatalysts
Routine hydrolysis method of condensing and obtain.But the condensation degree of partial hydrolysis condensate (multimerization degree) needs to can dissolve for product
Degree in solvent.As (E) ingredient, it can be the compound of above-mentioned formula (p1) expression, be also possible to above-mentioned formula (p1) table
The partial hydrolysis condensate of the compound shown is also possible to the compound and its partial hydrolysis condensate of above-mentioned formula (p1) expression
The partial hydrolysis condensate of the compound including mixture, the compound for example indicated comprising unreacted above-mentioned formula (p1).
It should be noted that as above-mentioned formula (p1) indicate compound, its partial hydrolysis condensate, commercially available product, the present invention in can
Use such commercially available product.
In addition, priming coat formation can be with composition comprising above-mentioned (E) ingredient and the chemical combination indicated by following formula (p2)
The composition of (F) ingredient that object (sometimes referred to as compound (p2)) and/or its partial hydrolysis condensate are formed or comprising above-mentioned
(E) partial hydrolysis condensate of ingredient and above-mentioned (F) ingredient (wherein, may include above-mentioned (E) ingredient and/or above compound
(p2)) composition.
(X3)3Si-(CH2)p-Si(X3)3 ···(p2)
(wherein, in formula (p2), there are multiple X3Hydrolization group or hydroxyl are each independently represented, p is 1~8
Integer.)
The compound that formula (p2) indicates is that have hydrolyzable silyl group in two ends in a manner of clipping divalent organic group
Or the compound of silanol group.
In formula (p2), as X3The hydrolization group of expression can be enumerated and above-mentioned X2Same group or atom.From above-mentioned
From the aspect of the harmony of the easiness of the stability and hydrolysis for the compound that formula (p2) indicates, as X3, preferably alkoxy
And isocyanate group, particularly preferably alkoxy.As alkoxy, preferably carbon atom number be 1~4 alkoxy, more preferable first
Oxygroup or ethyoxyl.They can suitably select according to purpose, the purposes etc. in manufacture and be used.There are multiple in formula (p2)
X3It can be identical group, be also possible to different groups, from the aspect of accessibility, preferably identical base
Group.
As the compound that formula (p2) is indicated, specifically, (CH can be enumerated3O)3SiCH2CH2Si(OCH3)3、(OCN)3SiCH2CH2Si(NCO)3、Cl3SiCH2CH2SiCl3、(C2H5O)3SiCH2CH2Si(OC2H5)3、(CH3O)3SiCH2CH2CH2CH2CH2CH2Si(OCH3)3Deng.(F) ingredient can be used alone, and can also be used in combination of two or more.
The ingredient for including in priming coat formation composition can be the partial hydrolysis condensation of formula (p2) compound indicated
Object.The partial hydrolysis condensate for the compound that formula (p2) indicates contracts using the partial hydrolysis with the compound indicated in formula (p1)
The same method of method illustrated in the manufacture of object is closed to obtain.The condensation degree (multimerization degree) of partial hydrolysis condensate needs to produce
Object is dissolvable in water the degree in solvent.As (F) ingredient, the compound that can be indicated for formula (p2), or formula (p2) table
The partial hydrolysis condensate of the compound shown, or the mixing of compound and its partial hydrolysis condensate that formula (p2) indicates
The partial hydrolysis condensate of the compound including object, the compound for example indicated comprising unreacted formula (p2).It needs to illustrate
, as above-mentioned formula (p2) indicate compound, its partial hydrolysis condensate, commercially available product, the present invention in can be used in this way
Commercially available product.
In addition, in priming coat, it is usable to obtain with above-mentioned formula (p1) similarly using silicon as each of the oxidation film of principal component
Kind polysilazane.
For priming coat formation composition, in general, going back base other than as the solid state component of layer constituent
Include organic solvent in the consideration to economy, workability, the easiness of thickness control of obtained priming coat etc..It is organic molten
Agent is not particularly limited, as long as by the solvent of the solid state component dissolution contained by priming coat formation composition.As
Organic solvent can enumerate compound same as the solvent of composition for use in the present invention.Organic solvent is not limited to a kind, can
Two or more different solvent such as polarity, evaporation rate is used in mixed way.Priming coat formation composition contains partial hydrolysis condensation
It also may include the solvent used to manufacture them when object, partial hydrolysis cocondensation.
It is used in composition in addition, priming coat is formed, even if not including partial hydrolysis condensate, partial hydrolysis cocondensation
When, in order to promote to hydrolyze cocondensation reaction, cooperation is urged with same acid usually used in partial hydrolysis condensation reaction in advance
The catalyst such as agent are also preferred.Even if when comprising partial hydrolysis condensate, partial hydrolysis cocondensation, in their system
In the case that catalyst used in making does not remain in composition, it is also preferred that cooperation catalyst.Composition is used in priming coat formation
It may include for making the above-mentioned water that condensation reaction, hydrolysis cocondensation reaction are hydrolyzed containing ingredient.
As the method for using priming coat formation composition to form priming coat, using the table of organic silane compound system
Known method in surface treatment agent.For example, using brushing, flow coat, rotary coating, dip coated, blade coating, spraying painting
Priming coat formation, is coated on the surface of matrix by the methods of cloth, hand painting with composition, in an atmosphere or in nitrogen atmosphere, according to
It needs to be dried, then makes its solidification, priming coat is consequently formed.Cured condition can according to the type of the composition used,
The suitable controls such as concentration.It should be noted that solidifying for priming coat formation composition can be with hydrophobic membrane formation composition
Solidify while carrying out.
The thickness of priming coat is not particularly limited, as long as moisture-proof can not only be assigned to the transparent coating being formed on
It property and can assign and the adaptation of substrate, the thickness that substrate and alkali etc. can also be isolated.
The static hydrophobic property and dynamic hydrophobic property of the envelope obtained by composition of the invention are excellent.Static hydrophobic spy
Property for example can by using sessile drop method through θ/the 2 methods initial contact angles analyzed evaluates, in addition, dynamic hydrophobic property can lead to
It crosses the contact angle hysteresis (contact angle hysteresis) measured using landing method or slides angle to evaluate.For example, can
Making the initial contact angle measured with the water droplet of 3 μ L is, for example, 110 ° or more, preferably 113 ° or more, more preferably 115 ° with
On, the upper limit is not particularly limited, and for example, 125 ° or so.In addition, the contact angle hysteresis example measured with the water droplet of 6.0 μ L can be made
For example 12 ° hereinafter, preferably 10 ° hereinafter, more preferably 9 ° hereinafter, lower limit is not particularly limited, for example, 3 ° or so.In addition,
With the landing angle that the water droplet of 6 μ L measures be, for example, 30 ° hereinafter, preferably 25 ° hereinafter, more preferably 23 ° hereinafter, lower limit does not have
Especially limitation, for example, 5 ° or so.
Embodiment
Hereinafter, enumerating embodiment further specifically describes the present invention.The present invention is not limited by embodiment below,
It can meet and suitably change and implement to be certainly possible in the range of aforementioned, aftermentioned purport, they are comprised in
In technical scope of the invention.
For envelope obtained in the embodiment of the present invention and comparative example, it is measured using following methods.
(1) measurement of film thickness
Rigaku Corporation X ray reflection rate measurement device (SmartLab) has been used in measurement.It is penetrated as X
Line source uses the X-ray generator of 45kW, the Alpha-ray wavelength X of the CuK based on Cu target=1 ray of 0.15418nm or CuK α
Wavelength X=0.15406nm, in addition, be not used monochromator.As setting condition, sampling width is set as 0.01 °, will be swept
It retouches range and is set as 0.0~2.5 °.Then, it is measured by above-mentioned setting condition, obtains reflectance measurements.Use the public affairs
Obtained measured value is analyzed in department's analysis software (GlobalFit).
(2) measurement of initial contact angle
Using contact angle determination device (consonance interface science corporation DM700), sessile drop method (analysis method: θ/2 is utilized
Method) with the contact angle of the water of the liquid measure measurement envelope surface of 3 μ L.
(3) measurement at contact angle hysteresis and landing angle
Using consonance interface science corporation DM700, using slide method (analysis method: contact method, water droplet amount: 6.0 μ L,
Method of tilting: continuous tilt slides detection: mobile to determine after landing: advancing angle slides and determines distance: 0.125mm), measurement
The dynamic hydrophobic property of envelope surface (contact angle hysteresis slides angle).
(4) evaluation of wear resistance
Using the scratch device for having HB pencil of Mitsubishi's pencil corporation with erasing rubber, contacted in erasing rubber with sample
In the state of, apply 500g load, keeps sample mobile with 40r/min, thus carry out wear test.Every 1000 abrasions time
Number i.e. measurement contact angle, measures the number until becoming -15 degree or less from initial contact angle.
Embodiment 1
Using the method recorded in the synthesis example 1,2 of Japanese Unexamined Patent Publication 2014-15609 bulletin, synthesizing following formula (a) is indicated
Compound (number-average molecular weight about 8000).
[chemical formula 11]
In above-mentioned formula (a), n 43, m be 1~6 integer.
As compound (A), the compound (a) for having used above-mentioned formula (a) to indicate has used following as compound (B)
The compound (b1) that formula (b1) indicates (number-average molecular weight is about 2240).
[chemical formula 12]
In above-mentioned formula (b1), r and s are the integer of the range as aforementioned average molecular weight.In addition, in above-mentioned formula (b1),
The ratio of number of fluorine atoms for the summation of number of hydrogen atoms and number of fluorine atoms other than the hydrogen atom in hydroxyl-removal is
40% or more.
As fluorine series solvent (C), using Novec7200 (registered trademark), preparing mass ratio is compound (A): compound
(B): the composition of fluorine series solvent (C)=89:11:400 ratio.1mL is added dropwise into the Ta boat of vapor deposition, is then made molten
Agent evaporation, sample of the preparation for vapor deposition.Using ULVAC KIKO, Inc. VPC-410A, using vacuum vapour deposition, (resistance adds
Thermal method, pressure are 8 × 10-3Pa, application electric current are 20A, and the vapor deposition treatment time is 15 seconds), in alkali-free glass EAGLE-XG (registration
Trade mark, Corning corporation) on film is made in sample above-mentioned, so that film properties sample for evaluation be made.
By the wear resistance of obtained envelope evaluation result is shown in table 1.It should be noted that initial in embodiment 1
Contact angle is 115.8 °, and sliding angle is 27.7 °, and contact angle hysteresis is 10.6 °.
Embodiment 2
After film is made, further carries out heating for 30 minutes in 150 DEG C, in addition to this, carry out similarly to Example 1
Operation.The sample for evaluation of film properties is made.
By the wear resistance of obtained envelope evaluation result is shown in table 1.It should be noted that initial in embodiment 2
Contact angle is 115.8 °, and sliding angle is 17.3 °, and contact angle hysteresis is 7.1 °.
Embodiment 3
After film is made, ultrasonic washing processing in 3 minutes is further carried out in water and is in addition to this carried out and embodiment 1
Same operation, is made the sample for evaluation of film properties.
By the wear resistance of obtained envelope evaluation result is shown in table 1.It should be noted that initial in embodiment 3
Contact angle is 117.9 °, and sliding angle is 22.3 °, and contact angle hysteresis is 8.3 °.
Embodiment 4
Instead of compound (b1), having used Fluorolink (registered trademark) D4000 shown in following formula (b2), (number is divided equally
Son amount is about 4000), in addition to this, to carry out operation similarly to Example 2, the sample for evaluation of film properties is made.
Fluorolink (registered trademark) D4000 not only has hydroxyl in end, but also has oxygroup alkylidene unit, oxygroup alkylidene
A part of the hydrogen atom of unit is replaced by fluorine atoms.In addition, in FluorolinkD4000, it is former relative to the hydrogen in hydroxyl-removal
The ratio of number of hydrogen atoms other than son and the number of fluorine atoms for the summation of number of fluorine atoms is 40% or more.
[chemical formula 13]
By the wear resistance of obtained envelope evaluation result is shown in table 1.It should be noted that initial in embodiment 4
Contact angle is 111.1 °, and sliding angle is 7.3 °, and contact angle hysteresis is 4.8 °.
Embodiment 5
The mass ratio of composition is changed to compound (A): compound (B): fluorine series solvent (C)=80:20:400 ratio
Example, in addition to this, carries out operation similarly to Example 2, film properties sample for evaluation is made.
By the wear resistance of obtained envelope evaluation result is shown in table 1.It should be noted that initial in embodiment 5
Contact angle is 114.9 °, and sliding angle is 26.3 °, and contact angle hysteresis is 14.5 °.
Embodiment 6
The mass ratio of composition is changed to compound (A): compound (B): fluorine series solvent (C)=80:20:400 ratio
Example, in addition to this, carries out operation similarly to Example 4, film properties sample for evaluation is made.
By the wear resistance of obtained envelope evaluation result is shown in table 1.It should be noted that initial in embodiment 6
Contact angle is 117.1 °, and sliding angle is 26.7 °, and contact angle hysteresis is 16.3 °.
Embodiment 7
The mass ratio of composition is changed to compound (A): compound (B): fluorine series solvent (C)=67:33:400 ratio
Example, in addition to this, carries out operation similarly to Example 4, film properties sample for evaluation is made.
By the wear resistance of obtained envelope evaluation result is shown in table 1.It should be noted that initial in embodiment 7
Contact angle is 115.6 °, and sliding angle is 22.7 °, and contact angle hysteresis is 9.5 °.
Comparative example 1
Instead of compound (b1), (number-average molecular weight is by Fomblin (registered trademark) M03 for having used following formula (c) to indicate
About 4000), in addition to this, operation similarly to Example 1 is carried out, the sample for evaluation of film properties is made.Fomblin (registration
Trade mark) M03 has oxygroup alkylidene unit, and whole hydrogen atoms of oxygroup alkylidene unit are replaced by fluorine atoms, but in its point
Do not have hydroxyl in sub.
[chemical formula 14]
By the wear resistance of obtained envelope evaluation result is shown in table 1.It should be noted that initial in comparative example 1
Contact angle is 115.7 °, slides angle and is greater than 50 °, even if substrate is tilted to 50 °, water droplet is not also slid.
Comparative example 2
Instead of compound (b1), Fomblin (registered trademark) M03 has been used, in addition to this, has been carried out similarly to Example 2
Operation, the sample for evaluation of film properties is made.
By the wear resistance of obtained envelope evaluation result is shown in table 1.It should be noted that initial in comparative example 2
Contact angle is 116.5 °, and sliding angle is 13.7 °, and contact angle hysteresis is 4.2 °.
Comparative example 3
Instead of compound (b1), Fomblin (registered trademark) M03 has been used, in addition to this, has been carried out similarly to Example 3
Operation, the sample for evaluation of film properties is made.
By the wear resistance of obtained envelope evaluation result is shown in table 1.It should be noted that initial in comparative example 3
Contact angle is 118.3 °, and sliding angle is 13.3 °, and contact angle hysteresis is 6.5 °.
[table 1]
※ post-treatment condition are as follows: 1. without, 2. 150 DEG C × 30 minutes, 3. water ultrasonic washing 3 minutes
As shown in Table 1, used the Examples 1 to 7 of the compound (B) with hydroxyl compared with comparative example 1~3, it is wear-resisting
Damage property improves.In addition, for the envelope for using composition of the invention to obtain, after being carried out after forming envelope
Reason, can be further improved wear resistance, especially, carry out to the identical Examples 1 to 3 of condition other than post-treatment condition
Compare it is found that the wear resistance carried out in the embodiment 3 of ultrasonic washing is best.
Industrial availability
Composition of the invention can be formed suitable for the display devices such as touch panel display, optical element, semiconductor element,
The pottery such as metal products, the tablewares such as construction material, nanometer embossing, solar battery, automobile, the glass pane of building, kitchen tools
The film of ceramic products, plastic automobile component etc., it is industrially useful.In addition, it also may be preferable for for kitchen, bathroom, washstand,
Mirror, article, goggles, the glasses of each component on toilet periphery etc..
Claims (7)
1. composition, characterized by comprising:
Compound (A), the compound (A) be bonded on the silicon atoms (a1) with perfluoropolyether structures 1 valence group and
(a2) either one in hydrolization group and hydroxyl；With
Compound (B), the compound (B) has hydroxyl and oxygroup alkylidene unit, in the hydrogen atom of oxygroup alkylidene unit
At least part be replaced by fluorine atoms, number-average molecular weight is less than 10000.
2. composition as described in claim 1, wherein compound (A) indicates by following formula (1a) or (2a),
[chemical formula 1]
In formula (1a),
Rf1The alkyl or fluorine atom that the carbon atom number being replaced by fluorine atoms for 1 or more hydrogen atom is 1~20,
Rf2It is each independently alkyl or fluorine atom that carbon atom number that 1 or more hydrogen atom is replaced by fluorine atoms is 1~20,
R1It is each independently the alkyl that hydrogen atom or carbon atom number are 1~4,
R2It is each independently the alkyl that carbon atom number is 1~20,
It is hydrogen that D, which is each independently-O- ,-C (=O)-O- ,-O-C (=O)-,-NR- ,-NRC (=O)-or-C (=O) NR-, R,
The alkyl or carbon atom number that atom, carbon atom number are 1~4 are 1~4 containing fluoroalkyl,
E is each independently hydrolization group or hydroxyl,
A1, b1, c1, d1 and e1 are each independently 0 or more and 600 integers below, and the aggregate value of a1, b1, c1, d1 and e1 are
9 or more,
N is 1 or more and 3 integers below,
For each repetitive unit for indicating a1, b1, c1, d1 and e1 and being bracketed with bracket, as long as with by least part
The sequence arrangement for forming perfluoropolyether structures, can respectively arrange in any order,
[chemical formula 2]
In formula (2a),
Rf3The alkyl or fluorine atom that the carbon atom number being replaced by fluorine atoms for 1 or more hydrogen atom is 1~20,
Rf4It is each independently alkyl or fluorine atom that carbon atom number that 1 or more hydrogen atom is replaced by fluorine atoms is 1~20,
R3It is each independently the alkyl that hydrogen atom or carbon atom number are 1~4,
R4It is each independently the alkyl that carbon atom number is 1~20,
It is hydrogen that M, which is each independently-O- ,-C (=O)-O- ,-O-C (=O)-,-NR- ,-NRC (=O)-or-C (=O) NR-, R,
The alkyl or carbon atom number that atom, carbon atom number are 1~4 are 1~4 containing fluoroalkyl,
G is each independently hydrolization group or hydroxyl,
The alkyl that Y is each independently hydrogen atom or carbon atom number is 1~4,
Z be hydrogen atom or halogen atom,
A2, b2, c2, d2 and e2 are each independently 0 or more and 600 integers below, and the aggregate value of a2, b2, c2, d2 and e2 are
9 or more,
F2 is 1 or more and 20 integers below,
G2 is 0 or more and 2 integers below,
P is 1 or more and 3 integers below,
For each repetitive unit for indicating a2, b2, c2, d2 and e2 and being bracketed with bracket, as long as with by least part
The sequence arrangement for forming perfluoropolyether structures, can respectively arrange in any order.
3. composition as claimed in claim 2, wherein the compound (A) is a1, b1, c1, d1 and e1 of above-mentioned formula (1a)
The aggregate value compound for being 13 or more or above-mentioned formula (2a) a2, b2, c2, d2 and e2 aggregate value be 13 or more change
Close object.
4. composition according to any one of claims 1 to 3, wherein compound (B) by following formula (1b) indicate,
[chemical formula 3]
In above-mentioned formula (1b), X is each independently hydrogen atom or fluorine atom, Rf5Be each independently hydrogen atom, fluorine atom or-
CF3, J is that-O- ,-C (=O)-O- or-O-C (=O)-O-, a3 are 1 or more and 5 hereinafter, b3 is 20 or more and 200 hereinafter, c3
For 5 or more and 200 hereinafter, for each repetitive unit for indicating a3~c3 and being bracketed with bracket, as long as with by least one
Part forms the sequence arrangement of oxygroup alkylidene unit, can respectively arrange in any order, the oxygroup alkylidene list
At least part hydrogen atom in member is replaced by fluorine atoms.
5. composition as described in any one of claims 1 to 4, wherein the number for the hydroxyl for including in compound (B) is 1
~2.
6. such as composition according to any one of claims 1 to 5, wherein in compound (B), relative to the hydrogen in hydroxyl-removal
The ratio of number of hydrogen atoms other than atom and the number of fluorine atoms for the summation of number of fluorine atoms is 40% or more.
7. such as composition according to any one of claims 1 to 6, wherein quality of the compound (A) relative to compound (B)
Than being 1 or more.
Applications Claiming Priority (3)
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| JP2016-161470 | 2016-08-19 | ||
| JP2016161470 | 2016-08-19 | ||
| PCT/JP2017/028728 WO2018034202A1 (en) | 2016-08-19 | 2017-08-08 | Composition |
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| CN109563338A true CN109563338A (en) | 2019-04-02 |
| CN109563338B CN109563338B (en) | 2021-11-26 |
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| CN201780050159.6A Active CN109563338B (en) | 2016-08-19 | 2017-08-08 | Composition comprising a metal oxide and a metal oxide |
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| JP (1) | JP6996898B2 (en) |
| KR (1) | KR102338219B1 (en) |
| CN (1) | CN109563338B (en) |
| TW (1) | TWI725219B (en) |
| WO (1) | WO2018034202A1 (en) |
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| EP3540026B1 (en) * | 2017-03-07 | 2024-04-24 | AGC Inc. | Water repellent oil repellent article, method for producing same, and water repellent oil repellent agent composition |
| TW202041371A (en) * | 2019-04-26 | 2020-11-16 | 日商尼康依視路股份有限公司 | Stacked body and production method therefor |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4849305A (en) * | 1985-09-26 | 1989-07-18 | Nec Corporation | Magnetic recording medium |
| TW200922969A (en) * | 2007-07-06 | 2009-06-01 | Asahi Glass Co Ltd | Surface treating agent, article, and novel fluorine-containing ether compound |
| JP2016132719A (en) * | 2015-01-19 | 2016-07-25 | ダイキン工業株式会社 | Surface-treating agent containing perfluoro(poly)ether group-containing silane compound |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5857942B2 (en) | 2011-11-30 | 2016-02-10 | 信越化学工業株式会社 | Fluorine surface treatment agent for vapor deposition and article vapor-deposited with the surface treatment agent |
| CN105814139B (en) * | 2013-12-13 | 2017-10-17 | 旭硝子株式会社 | Fluorine-containing ether composition, its manufacture method, coating fluid, the base material with surface-treated layer and its manufacture method |
| JP6319143B2 (en) | 2014-03-31 | 2018-05-09 | 信越化学工業株式会社 | Fluorine-containing coating agent and article treated with the coating agent |
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2017
- 2017-08-04 JP JP2017151823A patent/JP6996898B2/en active Active
- 2017-08-08 KR KR1020197007641A patent/KR102338219B1/en active IP Right Grant
- 2017-08-08 WO PCT/JP2017/028728 patent/WO2018034202A1/en active Application Filing
- 2017-08-08 CN CN201780050159.6A patent/CN109563338B/en active Active
- 2017-08-11 TW TW106127297A patent/TWI725219B/en not_active IP Right Cessation
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4849305A (en) * | 1985-09-26 | 1989-07-18 | Nec Corporation | Magnetic recording medium |
| TW200922969A (en) * | 2007-07-06 | 2009-06-01 | Asahi Glass Co Ltd | Surface treating agent, article, and novel fluorine-containing ether compound |
| JP2016132719A (en) * | 2015-01-19 | 2016-07-25 | ダイキン工業株式会社 | Surface-treating agent containing perfluoro(poly)ether group-containing silane compound |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2018034202A1 (en) | 2018-02-22 |
| KR20190042033A (en) | 2019-04-23 |
| KR102338219B1 (en) | 2021-12-10 |
| JP6996898B2 (en) | 2022-01-17 |
| TWI725219B (en) | 2021-04-21 |
| CN109563338B (en) | 2021-11-26 |
| TW201816009A (en) | 2018-05-01 |
| JP2018031000A (en) | 2018-03-01 |
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