CN108350168A - Polymer modification organo-silicon compound, surface conditioning agent and article containing perfluoroalkyl polyether base - Google Patents

Polymer modification organo-silicon compound, surface conditioning agent and article containing perfluoroalkyl polyether base Download PDF

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CN108350168A
CN108350168A CN201680064424.1A CN201680064424A CN108350168A CN 108350168 A CN108350168 A CN 108350168A CN 201680064424 A CN201680064424 A CN 201680064424A CN 108350168 A CN108350168 A CN 108350168A
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changing
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integer
perfluoroalkyl polyether
silicon
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CN108350168B (en
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片山理佐
松田高至
山根祐治
酒匈隆介
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Shin Etsu Chemical Co Ltd
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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
    • 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
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/42—Block-or graft-polymers containing polysiloxane sequences
    • C08G77/46—Block-or graft-polymers containing polysiloxane sequences containing polyether sequences
    • 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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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of 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; Compositions of derivatives of such polymers
    • C08L83/10—Block- or graft-copolymers containing polysiloxane sequences
    • C08L83/12—Block- or graft-copolymers containing polysiloxane sequences containing polyether sequences
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    • 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
    • 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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  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Polymers & Plastics (AREA)
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  • Wood Science & Technology (AREA)
  • Combustion & Propulsion (AREA)
  • Polyethers (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Silicon Polymers (AREA)
  • Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)

Abstract

The present invention provide under mild conditions, can also be formed with the short time excellent in wear resistance waterproof and oilproof layer the polymer modification organo-silicon compound containing perfluoroalkyl polyether base and the surface conditioning agent comprising the compound and the article that is surface-treated with the inorganic agent.With the following general formula (1)[Rf is the polymer residue containing fluoro oxyalkyl or fluoro oxyalkylene, and Y is divalent alkyl, and Q is divalent organosiloxane residue, silicon alkylidene or silicon arlydene, and X is hydrogen atom, alkyl or phenyl, and Z is hydrogen atom, by following formula SiR3(R is alkyl or phenyl.) indicate group or by following formula W Q'X (W be singly-bound or divalent alkyl, Q' be the divalent with the structure in siloxanes key, silicon alkylen structures and silicon arlydene structure group.) indicate group, α be 1 or 2.] indicate the polymer modification organo-silicon compound containing perfluoroalkyl polyether base.

Description

Polymer modification organo-silicon compound, surface conditioning agent containing perfluoroalkyl polyether base and Article
Technical field
The present invention relates to the polymer modification organo-silicon compound containing perfluoroalkyl polyether base and include the organo-silicon compound Surface conditioning agent and the article being surface-treated with the surface conditioning agent.
Background technology
In recent years, headed by the display of mobile phone, the touch panel of picture is accelerating.But touch panel is The bare state of picture, the chance that finger, cheek etc. directly adhere to is more, and the dirts such as sebum, which are easily adhered, becomes problem.Therefore, In order to improve appearance, visuality, the surface of display is made to be difficult to the technology for carrying fingerprint, the need for the technology for making dirt be easy to fall off It is surging on many years ground, it is desirable to which that exploitation disclosure satisfy that the material of these requirements.Particularly, the surface of touch panel display by It is easy attachment in fingerprint dirt, therefore, it is desirable to waterproof and oilproof layer is arranged.But the water and oil-resistant of existing waterproof and oilproof layer Height, dirt erasing property is excellent, but there is use middle antifouling property to deteriorate.In addition, according to the method being coated, have When in performance generate fluctuation, according to the base material being coated, adaptation is poor sometimes.In turn, surface conditioning agent so far Good surface characteristic mostly is shown for glass, but for resin surface, does not show adaptation, waterproof and oilproof fully The surfaces characteristic such as property, wear resistance.
Usually, compound containing perfluoroalkyl polyether base since its surface free energy is very small, have water and oil-resistant, Chemical-resistant, lubricity, release property, soil resistance etc..Using its property, the industrially waterproof and oilproof as paper-fiber etc. Anti-fouling agent, the lubricant of magnetic recording media, the oil-proofing agent of precision equipment, releasing agent, cosmetic preparation, protective film etc. widely utilize. But property means to allow in substrate surface for the non-sensitive adhesiveness for other base materials, non-adaptation simultaneously Coating keeps its envelope closely sealed also difficult.
On the other hand, as the coupling agent for making the substrate surface of glass, cloth etc. be combined with organic compound, known silane is even Join agent, the smears as various substrate surfaces widely utilizes.Silane coupling agent in 1 molecule have organo-functional group and Reactive silicyl (the generally hydrolyzable silyl groups such as alkoxysilyl).Hydrolyzable silyl group utilizes in air Moisture etc. cause self-condensation reaction and form envelope.The surface that the envelope passes through hydrolyzable silyl group and glass, metal etc. Chemically-physically combine, to as the firm envelope with durability.
Therefore, following composition is disclosed, it is water-disintegrable by using being introduced in the compound containing perfluoroalkyl polyether base The polymer modification silane containing perfluoroalkyl polyether base of silicyl, to be easy with substrate surface it is closely sealed and substrate surface can Being formed has the envelope (Patent Documents 1 to 8 of water and oil-resistant, chemical-resistant, lubricity, release property, soil resistance etc.：Japan Special open 2003-238577 bulletins, No. 2860979 bulletins of Japanese Patent No., No. 4672095 bulletins of Japanese Patent No., Japan are special Table 2008-534696 bulletins, Japanese Unexamined Patent Application Publication 2008-537557 bulletins, Japanese Unexamined Patent Publication 2012-072272 bulletins, Japan Special open 2012-157856 bulletins, Japanese Unexamined Patent Publication 2013-136833 bulletins).
When being surface-treated to base material with the composition containing the above-mentioned polymer modification silane containing perfluoroalkyl polyether base, make Envelope is carried out to base material to be formed, make hydrolyzable silyl group hydrolysis after coating, make the cured work of envelope with various coating methods In sequence, hydrolysis is promoted using the condition under 80 DEG C, the hot conditions such as 120 DEG C, humidification.In addition, can at room temperature Enough by being reacted at leisure with the moisture in air, to form solidification envelope.But the curing process needs high-temperature humidifying item Part, carry out at room temperature it is cured in the case of spend time etc., there is the rule that can become in manufacture speed (delay principal elements) The problem of.In turn, with short time cured envelope (waterproof and oilproof layer), there is wear-resisting under conditions of room temperature curing etc. is mild Antifouling property deteriorates this problem in damage property, use.
In patent document 9 (Japanese Unexamined Patent Publication 2008-144144 bulletins), by adding fluorine-containing carboxylic in coating composition Acid is used as curing catalysts, promotes solidification, to be formed a film under mild conditions, with the short time.But it if reduces Catalytic amount, then wear resistance is poor, if increasing catalytic amount, initial performance reduces.In addition, the carboxyl as polar group It is also a high possibility of exposing in envelope most surface, reduced performance at this time.
In addition, in patent document 10 (Japanese Unexamined Patent Publication 2004-145283 bulletins), it is proposed that contain fluoro polyalkylene The silane of ether.It is excellent with the grease proofness of the lens of the silane treatment for containing fluoro polyalkylene ether, fingerprint erasing property, but Wear resistance is insufficient.
Existing technical literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 2003-238577 bulletins
Patent document 2：No. 2860979 bulletins of Japanese Patent No.
Patent document 3：No. 4672095 bulletins of Japanese Patent No.
Patent document 4：Japanese Unexamined Patent Application Publication 2008-534696 bulletins
Patent document 5：Japanese Unexamined Patent Application Publication 2008-537557 bulletins
Patent document 6：Japanese Unexamined Patent Publication 2012-072272 bulletins
Patent document 7：Japanese Unexamined Patent Publication 2012-157856 bulletins
Patent document 8：Japanese Unexamined Patent Publication 2013-136833 bulletins
Patent document 9：Japanese Unexamined Patent Publication 2008-144144 bulletins
Patent document 10：Japanese Unexamined Patent Publication 2004-145283 bulletins
Invention content
The subject that the invention solves
The present invention is completed in view of above-mentioned actual conditions, and it is an object of the present invention to provide especially mild in room temperature etc. in resin surface Under conditions of, can also be formed with the short time excellent in wear resistance waterproof and oilproof layer the polymer modification containing perfluoroalkyl polyether base Organo-silicon compound and surface conditioning agent comprising the organo-silicon compound and with the processed object of the surface treatment agent Product.
Means for solving the problems
The present inventor in order to solve above-mentioned purpose sharp study, as a result, it has been found that：It has used and has been indicated by aftermentioned general formula (1) Even if even if the surface conditioning agent of the polymer modification organo-silicon compound containing perfluoroalkyl polyether base does not have functional end-group, in room The resins such as resin film, plastic lens formation excellent in wear resistance can also be prevented under conditions of temperature etc. is mild, with the short time The anti-oil reservoir of water, completes the present invention.
Therefore, the present invention provide following polymer modification organo-silicon compound containing perfluoroalkyl polyether base, surface conditioning agent and Article.
[1] the polymer modification organo-silicon compound containing perfluoroalkyl polyether base indicated by the following general formula (1).
[changing 1]
[in formula, Rf is the polymer residue containing fluoro oxyalkyl of 1 valence or the gathering containing fluoro oxyalkylene of divalent Object residue is closed, Y independently is the alkyl of divalent, and Q independently is the straight-chain or cyclic organic siloxane residue, silicon alkylidene of divalent Or silicon arlydene, X independently are the alkyl or phenyl of hydrogen atom, carbon number 1~4, Z independently is hydrogen atom, by following formula
-SiR3
(in formula, R independently is the alkyl or phenyl of carbon number 1~4.)
The group of expression or by following formula
-W-Q’-X
(in formula, X is same as described above, and W is the alkyl of singly-bound or divalent, and Q ' is with selected from siloxanes key, silicon alkylene base junction The group of structure and the divalent of the structure in silicon arlydene structure.)
The group of expression, α are 1 or 2.].
[2] the polymer modification organo-silicon compound containing perfluoroalkyl polyether base described in [1], which is characterized in that above-mentioned formula (1) In, α 1, Rf bases are the group indicated by the following general formula (2).
[changing 2]
(in formula, p, q, r, s are respectively 0~200 integer, are p+q+r+s=3~200, each repetitive unit can be straight Chain, or branch-like can be combined randomly between each repetitive unit, and the integer that d is 1~3, which can be straight chain Shape can also be branch-like.)
[3] the polymer modification organo-silicon compound containing perfluoroalkyl polyether base described in [1], which is characterized in that above-mentioned formula (1) In, α 2, Rf bases are the group indicated by the following general formula (3).
[changing 3]
(in formula, p, q, r, s are respectively 0~200 integer, are p+q+r+s=3~200, each repetitive unit can be straight Chain may be branch-like, can randomly be combined between each repetitive unit, and the integer that d is 1~3, which can be straight chain Shape may be branch-like.)
[4] the polymer modification organo-silicon compound containing perfluoroalkyl polyether base described in any one of [1]~[3], wherein In above-mentioned formula (1), Y is the alkylidene of carbon number 3~10.
[5] the polymer modification organo-silicon compound containing perfluoroalkyl polyether base described in any one of [1]~[4], wherein on It states in formula (1), Q is the group in the group indicated by following formula.
[changing 4]
(in formula, X is same as described above, R1It independently is the alkyl or phenyl of carbon number 1~4, R2For the alkylidene of carbon number 1~4 Or the arlydene of carbon number 6~12.The integer that g is 1~20, the integer that j is 1~8.)
[6] the polymer modification organo-silicon compound containing perfluoroalkyl polyether base described in any one of [1]~[5], wherein In above-mentioned formula (1), Z be selected from hydrogen atom and it is following shown in group in group.
[changing 5]
[changing 6]
[changing 7]
[changing 8]
(in formula, the integer that g1 is 2~20, the integer that e is 0~3.)
[7] the polymer modification organo-silicon compound containing perfluoroalkyl polyether base described in any one of [1]~[6], wherein by The polymer modification organo-silicon compound containing perfluoroalkyl polyether base that above-mentioned formula (1) indicates are indicated by either one or two of following formula.
[changing 9]
[changing 10]
[changing 11]
[changing 12]
[changing 13]
[changing 14]
[changing 15]
[changing 16]
[changing 17]
[changing 18]
[changing 19]
(in formula, Z is same as described above, the integer that p1 is 5~100, the integer that q1 is 5~100, and p1+q1 is 10~105 Integer.The integer that g1 is 2~20, the integer that e is 0~3.)
[8] surface conditioning agent, it includes the polymer modifications containing perfluoroalkyl polyether base described in any one of [1]~[7] to have Organic silicon compound.
[9] surface conditioning agent described in [8], which is characterized in that surface conditioning agent also contains by the following general formula (4)
[changing 20]
A-Rf′-A (4)
(in formula, A is that end is-CF3The fluoro-containing group of 1 valence of base, Rf ' are the polymerization containing fluoro oxyalkylene of divalent Object residue.)
The polymer containing perfluoroalkyl polyether base indicated.
[10] article being surface-treated with the surface conditioning agent described in [9].
The effect of invention
It is formed by the surface conditioning agent of the polymer modification organo-silicon compound containing perfluoroalkyl polyether base containing the present invention The water and oil-resistant of envelope is high, and the wear resistance of the envelope especially formed under conditions of room temperature etc. is mild, with the short time is excellent It is different.The surface conditioning agent of the polymer modification organo-silicon compound containing perfluoroalkyl polyether base containing the present invention is especially for resin Surface has special adaptation, therefore by being handled with the surface conditioning agent, so as to easily right with the short time Resin as resin film, spectacle lens assigns excellent water and oil-resistant, low dynamic, wear resistance.
Specific implementation mode
The polymer modification organo-silicon compound containing perfluoroalkyl polyether base of the present invention are indicated by the following general formula (1).
[changing 21]
[in formula, Rf is the polymer residue containing fluoro oxyalkyl of 1 valence or the gathering containing fluoro oxyalkylene of divalent Object residue is closed, Y independently is the alkyl of divalent, and Q independently is the straight-chain or cyclic organic siloxane residue, silicon alkylidene of divalent Or silicon arlydene, X independently are the alkyl or phenyl of hydrogen atom, carbon number 1~4, Z independently is hydrogen atom, by following formula
-SiR3
(in formula, R independently is the alkyl or phenyl of carbon number 1~4.)
The group of expression or by following formula
-W-Q’-X
(in formula, X is same as described above, and W is the alkyl of singly-bound or divalent, and Q ' is with selected from siloxanes key, silicon alkylene base junction The group of structure and the divalent of the structure in silicon arlydene structure.) indicate group, α be 1 or 2.]
In above-mentioned formula (1), in the case that α is 1, as Rf, the fluoro oxyalkyl of 1 valence preferably indicated by the following general formula (2).
[changing 22]
(in formula, p, q, r, s are respectively 0~200 integer, are the integer of p+q+r+s=3~200, each repetitive unit can Think that straight-chain may be branch-like, can randomly be combined between each repetitive unit, the integer that d is 1~3, which can be with For straight-chain or branch-like.)
In above-mentioned formula (1), in the case that α is 2, as Rf, the Replacement of Oxygen by Fluorine of the divalent preferably indicated by the following general formula (3) is sub- Alkyl.
[changing 23]
(in formula, p, q, r, s are respectively 0~200 integer, are p+q+r+s=3~200, each repetitive unit can be straight Chain may be branch-like, can randomly be combined between each repetitive unit, and the integer that d is 1~3, which can be straight chain Shape may be branch-like.)
In above-mentioned formula (2), (3), p, q, r, s are respectively 0~200 integer, it is preferable that the integer that p is 5~100, q 5 ~100 integer, r be 0~100 integer, s be 0~100 integer, be p+q+r+s=3~200, preferably 10~100, Each repetitive unit can be that straight-chain may be branch-like, can randomly be combined between each repetitive unit.It is highly preferred that p+q For 10~105 integer, particularly 15~60 integer, be r=s=0.If p+q+r+s is smaller than above-mentioned upper limit value, closely sealed Property, envelope formative it is good, if bigger than above-mentioned lower limiting value, can fully play the feature of perfluoroalkyl polyether base, therefore preferably.
In above-mentioned formula (2), (3), the integer that d is 1~3, preferably 1 or 2, which can be straight-chain, or Branch-like.
As Rf, by having the backbone structure by above-mentioned formula (2) or (3) expression, so as to form the coefficient of kinetic friction Low envelope.
In addition, containing siloxanes key, silicon phenylene key or silicon with perfluoroalkyl polyether structure, in single end of strand in main chain The straight chain polymer (the fluoro oxyalkyl for 1 valence that α 1, Rf are indicated by formula (2)) of alkylene bond in two ends contain silica Straight chain polymer (the Replacement of Oxygen by Fluorine alkylene for the divalent that α 2, Rf are indicated by formula (3) of alkane key, silicon phenylene key or silicon alkylene bond Base) compare, excellent wear resistance can be assigned to obtained envelope.
As Rf, following groups can be specifically illustrated.
[changing 24]
(in formula, p ', q ', r ', s ' are respectively 1 or more integer, and the upper limit is identical as the upper limit of above-mentioned p, q, r, s.U is 1 ~24, v is 1~24 and meets the number of u+v=r.Each repetitive unit can be combined randomly.)
In above-mentioned formula (1), Y independently is the alkyl of divalent, the preferably alkylene of carbon number 3~10, particularly carbon number 3~8 Base, such as propylidene (trimethylene, methyl ethylidene), butylidene (tetramethylene, methyl propylene), hexa-methylene, eight methylenes Base etc., particularly preferably trimethylene.
In above-mentioned formula (1), X independently is alkyl such as methyl, ethyl, propyl, butyl of hydrogen atom, carbon number 1~4 etc. or benzene Base, preferably hydrogen atom, methyl.
In above-mentioned formula (1), Q independently is the straight-chain or cyclic organic siloxane residue of divalent, the sub- virtue of silicon alkylidene or silicon Base, the group being preferably selected from the group indicated by following formula.
[changing 25]
(in formula, X is same as described above, R1It independently is alkyl or the benzene such as methyl, ethyl, propyl, the butyl of carbon number 1~4 Base, R2The Asias such as the phenylene of alkylidene such as methylene, ethylidene, propylidene, butylidene for carbon number 1~4 etc. or carbon number 6~12 Aryl.The integer that g is 1~20, preferably 1~10, the integer that j is 1~8, preferably 1~3.)
As the concrete example of Q, such as following groups can be enumerated.
[changing 26]
(in formula, g1 be 2~20, preferably 2~10 integer.)
In above-mentioned formula (1), Z independently is hydrogen atom, by following formula
-SiR3
(in formula, R independently is the alkyl or phenyl of carbon number 1~4.)
The group of expression or by following formula
-W-Q’-X
(in formula, X is same as described above, and W is the alkyl of singly-bound or divalent, and Q ' is with selected from siloxanes key, silicon alkylene base junction The group of structure and the divalent of the structure in silicon arlydene structure.)
The group of expression.
-SiR3In, R is alkyl or the phenyl such as methyl, ethyl, propyl, the butyl of carbon number 1~4, wherein it is preferred that methyl, second Base.
In addition, in-W-Q '-X, W is the alkyl of singly-bound or divalent, as the alkyl of divalent, can enumerate carbon number 2~10, The particularly alkylidene of carbon number 2~8 such as ethylidene, propylidene (trimethylene, methyl ethylidene), butylidene (tetramethylene, first Base propylidene), hexa-methylene, eight methylene etc., as W, preferably singly-bound or trimethylene.
X is same as described above, preferably hydrogen atom, methyl.
In addition, Q ' is the base of the divalent with the structure in siloxanes key, silicon alkylen structures and silicon arlydene structure Group, preferably straight-chain or cyclic organic siloxane residue, silicon alkylen structures, silicon arlydene with the divalent illustrated in above-mentioned Q Structure.
As the concrete example of Q ', such as following groups can be enumerated.
[changing 27]
(in formula, g1 is same as described above.)
As Z, can specifically illustrate hydrogen atom and it is following shown in group.
[changing 28]
[changing 29]
[changing 30]
[changing 31]
(in formula, g1 is same as described above, the integer that e is 0~3.)
As the polymer modification organo-silicon compound containing perfluoroalkyl polyether base indicated by above-mentioned formula (1), can illustrate by The compound that following formula indicates.It should be noted that in various, each repetitive unit of fluoro oxyalkyl or fluoro oxyalkylene is constituted Repeat number (or degree of polymerization) is desirable meet above-mentioned formula (2), (3) arbitrary number.
[changing 32]
[changing 33]
[changing 34]
[changing 35]
[changing 36]
[changing 37]
[changing 38]
[changing 39]
[changing 40]
[changing 41]
[changing 42]
[changing 43]
[changing 44]
(in formula, Z, g1, e are same as described above, p1 be 5~100 integer, q1 be 5~100 integer, p1+q1 be 10~ 105 integer.)
As the preparation method of the polymer modification organo-silicon compound containing perfluoroalkyl polyether base indicated by above-mentioned formula (1), Such as following such methods can be enumerated.
First, there will be the reactions such as acyl fluorides base, acid halide group, anhydride group, ester group, carboxylic acid group, acylamino- in molecule chain end The polymer containing perfluoroalkyl polyether base of property group, nucleophilic reagent and bis- (trifluoromethyl) benzene of such as 1,3-, tetrahydrochysene furan as solvent Mutter mixing, cured at 0~80 DEG C, preferably 50~70 DEG C, more preferably from about 60 DEG C 1~6 hour, preferably 3~5 hours, more preferably About 4 hours.
Wherein, it as the polymer containing perfluoroalkyl polyether base in molecule chain end with reactive group, can specifically arrange Enumerate it is following shown in polymer.
[changing 45]
(in formula, Rf, α are same as described above.)
In addition, as nucleophilic reagent, allylic halogenated magnesium, 3- cyclobutenyls magnesium halide, 4- pentenyls magnesium halide, 5- can be used Hexenyl magnesium halide etc..In addition, it is possible to use corresponding lithium reagent.
For the usage amount of nucleophilic reagent, contain perfluoroalkyl polyether with reactive group in molecule chain end relative to above-mentioned 1 equivalent of reactive group of the polymer of base can use 2~5 equivalents, more preferable 2.5~3.5 equivalent, further preferably about 3 Equivalent.
Then, stop reaction, operated water layer and fluorous solvent layer separation by liquid separation.Obtained fluorous solvent layer is further Cleaned with organic solvent, by by solvent distillation, to obtain by following formula (a) indicates molecule chain end have hydroxyl with The polymer containing perfluoroalkyl polyether base of olefinic sites.
[changing 46]
(in formula, Rf, α are same as described above.U is the alkyl of divalent.)
In above-mentioned formula (a), U, which is the alkyl of divalent, specifically can enumerate methylene, ethylidene, propylidene (three methylenes Base, methyl ethylidene), the alkylene of butylidene (tetramethylene, methyl propylene), hexa-methylene, the carbon numbers 1~8 such as eight methylene Base, the alkylidene (such as alkylene-arylene etc. of carbon number 7~8) of arlydene etc. comprising the carbon numbers such as phenylene 6~8.As U, the preferably straight-chain alkyl-sub of carbon number 1~4.
Next, as needed, there is hydroxyl and alkene portion in molecule chain end by what formula (a) indicated by obtained above The hydrogen atom of the hydroxyl of the polymer containing perfluoroalkyl polyether base of position is substituted by other groups.
It is substituted by by-SiR as by the hydrogen atom of hydroxyl3The method of the silicyl of expression, for example, in amine, alkali gold In the presence of the alkali such as category system alkali, as needed use fluorine series solvent, organic solvent equal solvent 0~80 DEG C, preferably 40~60 DEG C, Make to contain perfluoroalkyl polyether what molecule chain end had hydroxyl and an olefinic sites by what formula (a) indicated at a temperature of more preferably from about 50 DEG C The polymer of base cures 1~24 hour, preferably 2~10 hours, more preferably from about 3 hours with silanizing agent.
In addition, as other method, in the presence of the dehydrogenations such as platinum group metal catalyst, B catalyst, Using fluorine series solvent, organic solvent equal solvent to by formula at a temperature of 0~60 DEG C, preferably 15~35 DEG C, more preferably from about 25 DEG C (a) what is indicated in molecule chain end there is the polymer containing perfluoroalkyl polyether base and hydrogen silane of hydroxyl and olefinic sites to carry out 10 points Clock~24 hour, preferably 30 minutes~2 hours, more preferably from about 1 hour dehydrogenation reactions.
Wherein, as silanizing agent, such as halogen silyl, trifluoromethanesulfonic acid silyl ester etc. can be used, specifically Ground can enumerate chlorotrimethylsilane, triethyl group silyl chloride, tert-butyldimethylsilyl chloride monosilane, triisopropyl chloromethane silicon Alkane, triphenyl silyl chloride, trimethyl silyl bromide, trifluoromethanesulfonic acid trimethyl silyl ester, trifluoromethanesulfonic acid triethyl group Silyl ester, trifluoromethanesulfonic acid t-butyldimethylsilyl ester, trifluoromethanesulfonic acid triisopropylsilyl ester etc., separately Outside, without using alkali, hexamethyldisilazane, trimethyl silyl dimethyl amine, trimethyl first silicon can be used Alkyl diethyl amine, trimethyl-silyl-imidazole, for its usage amount, relative to by formula (a) indicate in molecule last-in-chain(LIC) 1 equivalent of hydroxyl of the polymer containing perfluoroalkyl polyether base with hydroxyl and olefinic sites is held, 1~10 equivalent can be used, it is more excellent Select 1~4 equivalent, further preferably about 2 equivalents.
In addition, as hydrogen silane, trimethyl silane, triethylsilane, t-butyldimethyl silane, three isopropyls can be enumerated Base silane, tri-phenyl-silane etc., for its usage amount, relative to by formula (a) indicate molecule chain end have hydroxyl and 1 equivalent of hydroxyl of the polymer containing perfluoroalkyl polyether base of olefinic sites, can use 1~5 equivalent, more preferable 1.5~3 equivalent, Further preferred about 2 equivalents.
Then, stop reaction, operated water layer and fluorous solvent layer separation by liquid separation.Obtained fluorous solvent layer is further Cleaned with organic solvent, by by solvent distillation, to obtain by following formula (b) indicates in molecule chain end with monosilane The polymer containing fluoro oxyalkyl of base and olefinic sites.
[changing 47]
(in formula, Rf, R, U, α are same as described above.)
In addition, being substituted by by-W-Q as by the hydrogen atom of hydroxyl '-X indicate group method, for example, boron be catalyzed In the presence of the dehydrogenations such as agent, using fluorine series solvent, organic solvent equal solvent 0~60 DEG C, preferably 15~35 DEG C, it is more excellent At a temperature of about 25 DEG C of choosing to by formula (a) indicates molecule chain end with hydroxyl and olefinic sites containing perfluoroalkyl polyether base Polymer and organo-silicon compound with SiH bases carry out 10 minutes~24 hours, preferably 30 minutes~2 hours, more preferably from about 1 Hour dehydrogenation reaction.
Wherein, as the organo-silicon compound with SiH bases, can illustrate it is for example following shown in organo-silicon compound.
[changing 48]
(in formula, g, e are same as described above, the integer that c is 1~4.)
For its usage amount, there is containing for hydroxyl and olefinic sites in molecule chain end relative to what is indicated by formula (a) There is 1 equivalent of hydroxyl of the polymer of perfluoroalkyl polyether base, 1~10 equivalent, more preferable 1.2~5 equivalent can be used.
Then, so that reaction is stopped, being operated water layer and fluorous solvent layer separation by liquid separation.By obtained fluorous solvent layer into one Step is cleaned with organic solvent, by by solvent distillation, to obtain it is being indicated by following formula (c), in molecule chain end with alkene Hydrocarbon position and the part of hydroxyl are replaced into the polymer containing fluoro oxyalkyl of organo-silicon compound group.
[changing 49]
(in formula, Rf, Q ', X, U, α it is same as described above, W ' be singly-bound.)
In turn, be substituted by by-W-Q as by the hydrogen atom of hydroxyl '-X indicate group method other methods, can arrange Enumerate following method：First, the hydrogen atom of hydroxyl is substituted by terminal unsaturation group, then, makes the terminal unsaturation group (olefinic sites) together with other olefinic sites with the reactive organic silicon compound with SiH bases.
As the method that the hydrogen atom of hydroxyl is substituted by terminal unsaturation group, for example, in amine, alkali metal system alkali etc. It is molten that reactive additive, fluorine system are improved in the presence of alkali, as needed using tetrabutyl ammonium halide, alkali metal series halide etc. Agent, organic solvent equal solvent will be existed at a temperature of 0~90 DEG C, preferably 60~80 DEG C, more preferably from about 70 DEG C by formula (a) expression Molecule chain end have the polymer containing perfluoroalkyl polyether base and alkene of hydroxyl and olefinic sites introduce agent cure 1~25 hour, It is preferred that 3~10 hours, more preferably from about 6 hours.
Wherein, agent is introduced as alkene, such as allyl halide etc. can be used, specifically, allyl chloride, alkene can be enumerated The chloro- 1- butylene of propyl bromide, allyl iodide, 4-, the bromo- 1- butylene of 4-, the iodo- 1- butylene of 4-, the chloro- 1- amylenes of 5-, the bromo- 1- amylenes of 5-, Iodo- 1- amylenes of 5- etc. have hydroxyl and alkene portion relative to what is indicated by formula (a) for its usage amount in molecule chain end 1 equivalent of hydroxyl of the polymer containing perfluoroalkyl polyether base of position, can be using 1~10 equivalent, more preferable 2.5~6 equivalent, further Preferably from about 5 equivalents.
Then, stop reaction, operated water layer and fluorous solvent layer separation by liquid separation.Obtained fluorous solvent layer is further Cleaned with organic solvent, by by solvent distillation, to obtain by following formula (d) indicates in molecule chain end with alkene portion The polymer containing fluoro oxyalkyl of position.
[changing 50]
(in formula, Rf, U, α are same as described above.V is the alkyl of singly-bound or divalent.)
In above-mentioned formula (d), V specifically, can enumerate methylene, Asia for the alkyl of singly-bound or divalent as the alkyl of divalent Ethyl, propylidene (trimethylene, methyl ethylidene), butylidene (tetramethylene, methyl propylene), hexa-methylene, eight methylenes Alkylidene (such as the alkylene of carbon number 7~8 of the alkylidene of the carbon numbers such as base 1~8, arlydene comprising the carbon numbers such as phenylene 6~8 Base-arlydene etc.) etc..As V, preferably methylene.
Next, in the toluene solution of hydrosilylation reaction catalyst such as chloroplatinic acid/vinylsiloxane complex compound In the presence of, make at a temperature of 40~120 DEG C, preferably 60~100 DEG C, more preferably from about 80 DEG C it is obtained above by formula (a)~(d) Either one or two of the polymer containing perfluoroalkyl polyether base in molecule chain end with olefinic sites indicated in the molecule with SiH The organo-silicon compound of base cure 1~72 hour, preferably 20~36 hours, more preferably from about 24 hours.
Wherein, as the organo-silicon compound in the molecule with SiH bases, preferably by the compound of following formula expression.
[changing 51]
(in formula, R1、R2, X, g, j it is same as described above, i be 1~6, preferably 1~4 integer, i+j be 3~10, preferably 3~5 Integer.)
As it is such in the molecule with SiH bases organo-silicon compound, such as can enumerate it is following shown in it is organic Silicon compound etc..
[changing 52]
[changing 53]
(in formula, g, g1, e are same as described above.)
For the usage amount of the organo-silicon compound in the molecule with SiH bases, relative to by above-mentioned formula (a)~(d) What is indicated has 1 equivalent of terminal unsaturation base of the polymer containing perfluoroalkyl polyether base of olefinic sites in molecule chain end, can Use 5~20 equivalents, more preferable 7.5~12.5 equivalent, further preferably about 10 equivalents.
Then, by the way that solvent and unreacted reactant are depressurized distillation, so as to obtain containing fluorine by what above-mentioned formula (1) indicated The polymer modification organo-silicon compound of polyether-based.Further more, above-mentioned reaction can be carried out individually, also can be performed continuously.
The surface conditioning agent of the present invention contains the polymer modification organosilicon containing perfluoroalkyl polyether base indicated by above-mentioned formula (1) Compound.
In the surface conditioning agent of the present invention, can also it contain by the following general formula (4)
[changing 54]
A-Rf′-A (4)
(in formula, A is fluorine atom or end is-CF3The fluoro-containing group of 1 valence of base, Rf ' contain Replacement of Oxygen by Fluorine alkylene for divalent The polymer residue of base.)
The polymer containing perfluoroalkyl polyether base indicated (hereinafter referred to as without functional initiator).
In above-mentioned formula (4), A is fluorine atom or end is-CF3The fluoro-containing group of 1 valence of base, preferably fluorine atom, carbon number 1 ~6 straight-chain perfluoroalkyl, wherein it is preferred that-F bases ,-CF3Base ,-CF2CF3Base ,-CF2CF2CF3Base.
In addition, Rf ' is the polymer residue containing fluoro oxyalkylene of divalent, as Rf ', it is preferably following shown in gather Close object residue.
[changing 55]
(in formula, p2 be 5~200 integer, preferably 10~100 integer, q2 be 5~200 integer, preferably 10~100 Integer, r1 be 10~200 integer, preferably 20~100 integer, t1 be 5~200 integer, preferably 10~100 it is whole Number, t2 be 10~200 integer, preferably 20~100 integer, t1+p2 be 10~205 integer, preferably 20~110 it is whole Number, q2+p2 are 10~205 integer, preferably 20~110 integer.)
As by formula (4) indicate without functional initiator, following polymer can be enumerated.
[changing 56]
(in formula, p2, q2, r1, t1, t2 are same as described above.)
To coordinate by formula (4) indicate without functional initiator when usage amount be not particularly limited, relative to by formula (1) The quality of the polymer modification organo-silicon compound containing perfluoroalkyl polyether base indicated, preferably 0.1~60 mass %, particularly preferred 10 The range of~40 mass %, if excessively, leading to the problem of adaptation sometimes.
The surface conditioning agent may include solvent appropriate.As such solvent, fluorine richness aliphatic hydrocarbon system can be illustrated Solvent (PF 5070, perfluorooctane etc.), fluorine richness aromatic hydrocarbon series solvent (hexafluoro meta-xylene (1,3- bis- (trifluoromethyls) Benzene), benzenyl fluoride etc.), fluorine richness ether series solvent (methyl perfluorobutyl ether, ethyl perfluorobutyl ether, perfluor (2- butyl four Hydrogen furans) etc.), fluorine richness alkyl amine series solvent (perfluorotributylamine, perfluor triamylamine etc.), hydrocarbon system solvent (benzin, dormant oil Essence, toluene, dimethylbenzene etc.), ketone series solvent (acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK) etc.).In these, from dissolubility, wetability Etc. set out, the preferred solvent of fluorine richness, particularly preferred hexafluoro meta-xylene, perfluor (2- butyl tetrahydrofurans), perfluor three Butylamine, ethyl perfluorobutyl ether.
For above-mentioned solvent, it can be mixed two or more, preferably make the polymer modification organosilicon containing perfluoroalkyl polyether base Compound equably dissolves.Further more, the optium concentration of the polymer containing fluoro oxyalkylene dissolved in a solvent is because of processing Method and different, 0.01~40 mass % preferably in surface conditioning agent, particularly preferably 0.05~25 mass %.
The surface conditioning agent of the present invention is surface-treated resin as resin film, spectacle lens.Wherein, as Resin, the preferably resin made of thermoplastic resin, and specifically, it is preferable to use the thermoplastic resin through hard conating process Adipose membrane (hard coat film), pencil hardness are 4H or more and do not impose the thermoplastic resin film (high hardness resin film) or tool of hard conating There is the thermoplastic resin film (antireflective coating) etc. of antireflection layer.
In addition, it is preferable to use having carried out SiO to above-mentioned resin in advance in the present invention2The product of processing.Wherein, SiO2For processing, SiO has been carried out using sputtering method2The product of processing makes the adaptation of above-mentioned resin and inorganic agent improve, It is preferred from this respect.
The surface conditioning agent of the present invention can use method well known to hairbrush coating, dipping, spraying, vapor deposition treatment etc. in base It is granted on material.For heating means when vapor deposition treatment, resistance heating manner, electron beam mode of heating have no especially It limits.In addition, post-treatment condition is different because of post-processing approach, for example, in the case where being granted by vapor deposition treatment, spraying, make With through SiO2In the case that the resin film of processing is as base material, 5 can be defined as in the range of room temperature (25 DEG C) is to 200 DEG C Minute~24 hours, particularly 10 minutes~12 hours, it can also be post-processed under humidification.Especially in the present invention, i.e., Make at room temperature, it is just enough with 10 minutes~24 hours, particularly 30 minutes~12 hours.In addition, for the film thickness of envelope, It is properly selected according to the type of base material, usually 0.1~100nm, especially 1~25nm.
As the resin handled by the above-mentioned surface conditioning agent with the present invention, preferably as auto navigation, mobile electricity Words, digital camera, DV, PDA, portable audio player, vehicle audio, game station, spectacle lens, camera mirror The medical instruments such as head, filter, sunglasses, gastroscope, duplicator, PC, liquid crystal display, organic el display, plasma The portion of the products such as display, touch panel display, protective film, hard coat film, high hardness resin, antireflective coating, wearable terminal That part or a part use, optical article, touch panel, antireflective coating, quartz base plate etc..
Even if to the surface conditioning agent that is surface-treated of resin of the present invention under conditions of room temperature etc. is mild, use Short time also can form envelope in above-mentioned article, and the envelope is special due to showing excellent water and oil-resistant, durability It not can be used as the waterproof of spectacle lens, touch panel display, hard coat film, high hardness resin, antireflective coating, wearable terminal etc. Anti- oil reservoir.Wherein, so-called high hardness resin, such as refer to as glass alternative membrane through PR, Nippon Steel Chemical Co., Ltd's system Made of the resin forming by pencil hardness 4H or more such as trade name シ Le プ ラ ス, GUNZE LIMITED. trade name HD films Product particularly relates to, by resin film made of the resin forming, not limited by above-mentioned product especially.
Embodiment
Synthesis example, embodiment and comparative example described below, are described in more detail the present invention, but the present invention is not by following Embodiment limits.
Embodiment and comparative example have used the compound obtained by following synthesis examples.
The synthesis of [synthesis example 1] compound 1
Bis- (trifluoromethyl) the benzene 300g of tetrahydrofuran 150g, 1,3- are mixed in the reaction vessel, instill the allyl of 0.7M Base magnesium bromide 160ml.Then, it instills at leisure by following formula (A)
[changing 57]
The compound 300g (4.8 × 10 of expression-2Mol it after), is heated 4 hours at 60 DEG C.After heating, it is cooled to room Solution is instilled in 1.2M aqueous hydrochloric acid solutions 300g, reaction is made to stop by temperature.It is operated, will be closed as the fluorination of lower layer by liquid separation After nitride layer recycling, cleaned with acetone.The fluorine compound layer as lower layer after cleaning recycles again, by under reduced pressure will be residual Solvent distillation is deposited, to obtain the polymer 292g containing perfluoroalkyl polyether base indicated by following formula (B).
[changing 58]
It is put into the reaction vessel by following formula (B)
[changing 59]
The compound 80g (1.0 × 10 of expression-2Mol), bis- (trifluoromethyl) the benzene 80g of 1,3- are dissolved in, by chloroplatinic acid/second The toluene solution 8.0 × 10 of alkenyl siloxane complex compound-2G (in terms of Pt simple substance, contains 2.1 × 10-6) and the bis- (diformazans of 1,4- mol Base silicyl) benzene 37g (1.9 × 10-1Mol it) mixes, is cured 7 hours at 80 DEG C, by depressurizing solvent and unreacted reactant Distillation, to obtain polymer (compound 1) 70g containing perfluoroalkyl polyether base indicated by following formula (C).
[changing 60]
1H-NMR
δ0-0.2(-Si(CH 3)2)24H
δ0.4-0.6(-CH2CH2CH 2-Si)4H
δ1.3-1.6(-CH2CH 2CH2-Si)4H
δ1.6-1.9(-CH 2CH 2 CH2-Si)4H
δ3.6-4.2(-SiH)2H
δ6.6-7.1(-C6 H 4)8H
The synthesis of [synthesis example 2] compound 2
In the reaction vessel by 1,3- bis- (trifluoromethyl) benzene 100g, DBU (diazabicyclo endecatylene) 8.2g (5.4 ×10-2Mol), by following formula (B)
[changing 61]
The compound 100g (2.7 × 10 of expression-2Mol after) mixing, trim,ethylchlorosilane 5.8g (5.4 × 10 is instilled- 2mol).Then, it is heated 3 hours at 50 DEG C.After heating, it is cooled to room temperature, instills aqueous hydrochloric acid solution.It is grasped by liquid separation Make, after being recycled as the fluorine compound layer of lower layer, uses methanol cleaning.Again by the fluorine compound layer as lower layer after cleaning Recycling, by under reduced pressure by residual solvents distillation, to obtain the polymerization containing perfluoroalkyl polyether base indicated by following formula (D) Object 90g.
[changing 62]
1H-NMR
δ0-0.2(-OSi(CH 3)3)9H
δ2.4-2.6(-CH 2CH=CH2)4H
δ5.0-5.2(-CH2CH=CH 2)4H
δ5.7-5.9(-CH2CH=CH2)2H
It is put into the reaction vessel by following formula (D)
[changing 63]
The compound 50g (1.4 × 10 of expression-2Mol), bis- (trifluoromethyl) the benzene 50g of 1,3- are dissolved in, by chloroplatinic acid/second The toluene solution 1.5 × 10 of alkenyl siloxane complex compound-1G (in terms of Pt simple substance, contains 4.0 × 10-6Mol) and 1,3,5,7- tetra- Methyl cyclotetrasiloxane 33g (1.3 × 10-1Mol it) mixes, is cured 19 hours at 80 DEG C, by subtracting solvent and unreacted reactant Distillation is pressed, to obtain polymer (compound 2) 56g containing perfluoroalkyl polyether base indicated by following formula (E).
[changing 64]
1H-NMR
δ0-0.2(-OSi-CH 3、-OSi(CH 3)3)36H
δ0.5-0.8(-CH2CH2CH 2-Si)4H
δ1.3-2.2(-CH 2CH 2CH2-Si)8H
δ4.3-5.2(-SiH)6H
The synthesis of [synthesis example 3] compound 3
It is put into the reaction vessel by following formula (B)
[changing 65]
The compound 150g (4.0 × 10 of expression-2Mol), be dissolved in bis- (trifluoromethyl) the benzene 150g of 1,3-, by chloroplatinic acid/ The toluene solution 8.0 × 10 of vinylsiloxane complex compound-2G (in terms of Pt simple substance, contains 4.0 × 10-6Mol) and 1,1,3,3, 5,5- hexam ethylcyclotrisiloxane 83g (4.0 × 10-1Mol it) mixes, is cured 24 hours at 80 DEG C, by by solvent and unreacted Object depressurizes distillation, to obtain polymer (compound 3) 150g containing perfluoroalkyl polyether base indicated by following formula (F).
[changing 66]
1H-NMR
δ0-0.2(-OSi(CH 3)2)36H
δ0.3-0.6(-CH2CH2CH 2-Si)4H
δ1.3-1.8(-CH 2CH2CH2- Si ,-CH2CH 2CH2-Si)8H
δ3.3-3.6(-SiH)2H
The synthesis of [synthesis example 4] compound 4
It is put into the reaction vessel by following formula (B)
[changing 67]
The compound 50g (1.4 × 10 of expression-2Mol), bis- (trifluoromethyl) the benzene 50g of 1,3- are dissolved in, by chloroplatinic acid/second The toluene solution 8.0 × 10 of alkenyl siloxane complex compound-2G (in terms of Pt simple substance, contains 1.3 × 10-6Mol) and 1,1,3,3,5, 5,7,7- octamethylcyclotetrasiloxane 40g (1.4 × 10-1Mol it) mixes, is cured 4 hours at 80 DEG C, by by solvent and unreacted Object depressurizes distillation, to obtain polymer (compound 4) 41g containing perfluoroalkyl polyether base indicated by following formula (G).
[changing 68]
1H-NMR
δ0-0.2(-OSi(CH 3)2)48H
δ0.3-0.6(-CH2CH2CH 2-Si)4H
δ1.3-1.8(-CH 2CH2CH2- Si ,-CH2CH 2CH2-Si)8H
δ3.3-3.6(-SiH)2H
The synthesis of [synthesis example 5] compound 5
It is put into the reaction vessel by following formula (B)
[changing 69]
The compound 20g (0.5 × 10 of expression-2Mol), bis- (trifluoromethyl) the benzene 20g of 1,3- are dissolved in, by chloroplatinic acid/second The toluene solution 2.0 × 10 of alkenyl siloxane complex compound-2G (in terms of Pt simple substance, contains 0.5 × 10-6Mol) and by following formula (H)
[changing 70]
The ten siloxanes 40g (0.5 × 10 indicated-1Mol it) mixes, is cured 7 hours at 80 DEG C, by by solvent and not anti- Object is answered to depressurize distillation, to obtain polymer (compound 5) 10g containing perfluoroalkyl polyether base indicated by following formula (I)s.
[changing 71]
1H-NMR
δ0-0.2(-OSi(CH 3)2)120H
δ0.3-0.8(-CH2CH2CH 2-Si)4H
δ1.3-1.8(-CH 2CH2CH2- Si ,-CH2CH 2CH2-Si)8H
δ4.7-5.0(-SiH)2H
The synthesis of [synthesis example 6] compound 6
It is put into the reaction vessel by following formula (B)
[changing 72]
The compound 50g (1.3 × 10 of expression-2Mol), bis- (trifluoromethyl) the benzene 50g of 1,3- are dissolved in, by chloroplatinic acid/second The toluene solution 5.0 × 10 of alkenyl siloxane complex compound-2G (in terms of Pt simple substance, contains 1.4 × 10-6) and two silicon of pentamethyl mol Oxygen alkane 20g (1.4 × 10-1Mol it) mixes, is cured 8 hours at 80 DEG C, by the way that solvent and unreacted reactant are depressurized distillation, to Polymer (compound 6) 54g containing perfluoroalkyl polyether base indicated by following formula (J) is obtained.
[changing 73]
1H-NMR
δ0-0.2(-Si-CH 3)30H
δ0.2-0.4(-CH2CH2CH 2-Si)4H
δ1.0-1.6(-CH 2CH2CH2- Si ,-CH2CH 2CH2-Si)8H
The synthesis of [synthesis example 7] compound 7
It is put into the reaction vessel by following formula (B)
[changing 74]
The compound 50g (1.3 × 10 of expression-2Mol), bis- (trifluoromethyl) the benzene 50g of 1,3- are dissolved in, by chloroplatinic acid/second The toluene solution 1.0 × 10 of alkenyl siloxane complex compound-1G (in terms of Pt simple substance, contains 2.8 × 10-6) and-ten first of 1- butane mol Five siloxanes 13g (3.2 × 10 of base-2Mol it) mixes, is cured 20 hours at 80 DEG C, by evaporating solvent and unreacted reactant decompression It removes, to obtain polymer (compound 7) 54g containing perfluoroalkyl polyether base indicated by following formula (K).
[changing 75]
1H-NMR
δ0-0.2(-Si-CH 3)60H
δ0.3-0.6(-CH2CH2CH 2-Si)8H
δ0.6-0.8(-CH2CH2CH2-CH 3)6H
δ1.1-1.3(-CH2CH 2CH 2-CH 3)8H
δ1.4-1.8(-CH 2CH 2CH2-Si)8H
The synthesis of [synthesis example 8] compound 8
It is put into the reaction vessel by following formula (B)
[changing 76]
The compound 25g (0.7 × 10 of expression-2Mol), bis- (trifluoromethyl) the benzene 25g of 1,3- are dissolved in, by chloroplatinic acid/second The toluene solution 2.5 × 10 of alkenyl siloxane complex compound-2G (in terms of Pt simple substance, contains 0.7 × 10-6) and bis- (dimethyl methyls mol Silylation) methane 8.9g (0.7 × 10-1Mol it) mixes, is cured 24 hours at 80 DEG C, by depressurizing solvent and unreacted reactant Distillation, to obtain polymer (compound 8) 10g containing perfluoroalkyl polyether base indicated by following formula (L).
[changing 77]
1H-NMR
δ0-0.4(-OSi(CH 3)2,-Si-CH 2-Si)28H
δ0.4-0.8(-CH2CH2CH 2-Si)4H
δ1.2-2.0(-CH 2CH 2CH2-Si)8H
δ3.8-4.2(-SiH)2H
The synthesis of [synthesis example 9] compound 9
It is put into the reaction vessel by following formula (M)
[changing 78]
The compound 200g (2.6 × 10 of expression-2Mol), bis- (trifluoromethyl) the benzene 200g of 1,3-, 1,1,3,3,5,5- pregnancy Base trisiloxanes 108g (5.2 × 10-3) and the toluene solution 6.0 × 10 of chloroplatinic acid/vinylsiloxane complex compound mol-1G (with Pt simple substance meters contain 1.6 × 10-5Mol it) mixes, is cured 40 hours at 80 DEG C.Then, solvent and unreacted reactant decompression are evaporated It removes.Then, the low boiling point component of remaining, higher boiling ingredient are removed using molecular distillation apparatus, has as a result obtained the life of liquid At object (compound 9) 200g.
Using1The compound 9 that H-NMR confirmed is the structure indicated by following formula (N).
[changing 79]
1H-NMR
δ0-0.4(-OSi(CH 3)2)72H
δ0.4-0.8(-CH2CH2CH 2-Si)8H
δ1.2-2.0(-CH 2CH 2CH2-Si)16H
δ3.8-4.2(-SiH)4H
The synthesis of [synthesis example 10] compound 10 (comparing product)
It in the reaction vessel will be by following formula (B)
[changing 80]
The compound 200g (2.6 × 10 of expression-2Mol), bis- (trifluoromethyl) the benzene 200g of 1,3-, trimethoxy silane 12.7g(1.1×10-1) and the toluene solution 6.0 × 10 of chloroplatinic acid/vinylsiloxane complex compound mol-1G (in terms of Pt simple substance, Contain 1.6 × 10-5Mol it) mixes, is cured 40 hours at 80 DEG C.Then, solvent and unreacted reactant are depressurized into distillation.Then, it adopts The low boiling point component of remaining, higher boiling ingredient are removed with molecular distillation apparatus, as a result obtained the product (compound of liquid 10)201g。
Using1The compound 10 that H-NMR confirmed is the structure indicated by following formula (O).
[changing 81]
1H-NMR
δ0.2-2.2(-CH 2CH 2CH 2-)12H
δ3.0-3.5(-Si(OCH 3)3)18H
In turn, compound below has been used in a comparative example.
[compound 11]
[changing 82]
[compound 12]
[changing 83]
[Examples 1 to 9, comparative example 1~3]
The preparation of surface conditioning agent and the formation of envelope
Above compound 1~12 is set to be dissolved in Novec 7200 (manufacture of 3M companies, ethyl perfluorobutyl ether) so that concentration As 20 mass %, surface conditioning agent is prepared.After prepared by surface conditioning agent, resin film (manufacture of タ イ go ー ルド societies) is passed through Corona treatment (Ar：10cc、O2：80cc, output power：250W, time：30 seconds) it cleans, vacuum evaporation (processing on it Condition is pressure：2.0×10-2Pa, heating temperature：700 DEG C) above-mentioned surface conditioning agent 10mg, in 25 DEG C, the gas of humidity 50%RH Atmosphere forms the envelope of film thickness 15nm after lower 24 hours.It should be noted that resin film has been used by polyethylene terephthalate System implements film surface after acrylic acid series hard conating process in most surface with the thickness SiO of 100nm2What sputter process was crossed Resin film.
The envelope that compound 1~9 is formed will be used as Examples 1 to 9, the envelope that compound 10~12 will be used to be formed As comparative example 1~3.
The envelope of Examples 1 to 9 and comparative example 1~3 is evaluated using following methods.All experiments all exist 25 DEG C, implement under humidity 50%RH.
[evaluation of wear resistance]
For obtained envelope, Tribogear TYPE are used：30S (manufacture of Xin Dong science Co., Ltd.) determine for The wear resistance of cloth (non-dust cloth).
Using following conditions, terminate to test at the time of water contact angle becomes less than 100 °.It is contacted using water is kept The abrasion number at 100 ° of angle or more has carried out the evaluation of wear resistance.
Contact area：10mm×30mm
Load：1.5kg
Resistance to cloth abrasiveness
Cloth：BEMCOT M-3II (Asahi Kasei Corporation's manufacture)
Displacement distance (one way) 20mm
1800mm/ points of movement speed
Load：0.5kg/cm2
In addition, for water contact angle, use contact angle meter DropMaster (consonance interface science Co., Ltd. manufactures) Determine envelope for water (drop：2 μ l) contact angle.Further more, water contact angle be make the drips of 2 μ l in sample table It is measured after 1 second behind face.
[table 1]
Compound Wear resistance (secondary)
Embodiment 1 1 1,000
Embodiment 2 2 2,300
Embodiment 3 3 8,500
Embodiment 4 4 8,700
Embodiment 5 5 10,000
Embodiment 6 6 5,300
Embodiment 7 7 9,300
Embodiment 8 8 6,000
Embodiment 9 9 2,`00
Comparative example 1 10 0
Comparative example 2 11 0
Comparative example 3 12 0
According to above-mentioned table 1, in Comparative Examples 1 and 2 and 3, surface conditioning agent vapor deposition is coated on substrate surface, post-processing is laggard Row Abrasion resistance test, then wear-resistant number is 0 time, does not show wear durability.And in Examples 1 to 9, by surface conditioning agent Vapor deposition is coated on substrate surface, carries out Abrasion resistance test after post-processing, then shows excellent wear resistance.Examples 1 to 9 by In there are siloxanes key, silicon phenylene structure or silicon alkylen structures in molecule chain end (the concatenating group part of molecule), therefore The especially SiCH of these concatenating group parts3The SiO of part and substrate surface2Layer comes from SiO2OH base portions point pass through molecule Between power interact, the polymer in surface conditioning agent becomes easy orientations, therefore, it is considered that being hydrolyzed even if not having in terminal groups Property group also improves compared with the surface conditioning agent of comparative example with the adaptation of base material.
It is formed using the surface conditioning agent of the polymer modification organo-silicon compound containing perfluoroalkyl polyether base comprising the present invention The resin of the superficial layer of soil resistance can show that excellent wear durability.Surface conditioning agent using the present invention forms The resin of the superficial layer of soil resistance can be particularly suitable for needing in spectacle lens, sunglasses, touch panel display, antireflective coating etc. Want the antifouling process on surface with using on the way.
Industrial availability
It is carried out using the surface conditioning agent of the polymer modification organo-silicon compound containing perfluoroalkyl polyether base containing the present invention The article of surface treatment shows excellent wear durability.The tree that surface conditioning agent using the present invention is surface-treated The resin that grease article adheres to grease especially as estimations such as touch panel display, antireflective coating, spectacle lens is effective 's.

Claims (10)

1. the polymer modification organo-silicon compound containing perfluoroalkyl polyether base are indicated by the following general formula (1)：
[changing 1]
In formula, Rf is residual for the polymer residue containing fluoro oxyalkyl of 1 valence or the polymer containing fluoro oxyalkylene of divalent Base, Y independently are the alkyl of divalent, and Q independently is the straight-chain or cyclic organic siloxane residue of divalent, silicon alkylidene or silicon Asia Aryl, X independently are the alkyl or phenyl of hydrogen atom, carbon number 1~4, and Z independently is hydrogen atom, by following formula-SiR3It indicates Group or the group indicated by following formula-W-Q '-X, α are 1 or 2,
-SiR3
In formula, R independently is the alkyl or phenyl of carbon number 1~4,
-W-Q’-X
In formula, X is same as described above, and W is the alkyl of singly-bound or divalent, and Q ' is with selected from siloxanes key, silicon alkylen structures and silicon The group of the divalent of structure in arlydene structure.
2. the polymer modification organo-silicon compound according to claim 1 containing perfluoroalkyl polyether base, which is characterized in that above-mentioned In formula (1), α 1, Rf bases are the group indicated by the following general formula (2),
[changing 2]
In formula, p, q, r, s are respectively 0~200 integer, are p+q+r+s=3~200, each repetitive unit can be straight-chain It can be branch-like, can randomly be combined between each repetitive unit, the integer that d is 1~3, which can be that straight-chain also may be used To be branch-like.
3. the polymer modification organo-silicon compound according to claim 1 containing perfluoroalkyl polyether base, which is characterized in that above-mentioned In formula (1), α 2, Rf bases are the group indicated by the following general formula (3),
[changing 3]
In formula, p, q, r, s are respectively 0~200 integer, are p+q+r+s=3~200, each repetitive unit can be straight-chain It can be branch-like, can randomly be combined between each repetitive unit, the integer that d is 1~3, the unit can be that straight-chain also may be used Think branch-like.
4. the polymer modification organo-silicon compound described in any one of claim 1 to 3 containing perfluoroalkyl polyether base, In, in above-mentioned formula (1), Y is the alkylidene of carbon number 3~10.
5. the polymer modification organo-silicon compound according to any one of claims 1 to 4 containing perfluoroalkyl polyether base, In, in above-mentioned formula (1), Q is the group in the group indicated by following formula,
[changing 4]
In formula, X is same as described above, R1It independently is the alkyl or phenyl of carbon number 1~4, R2For the alkylidene or carbon number of carbon number 1~4 6~12 arlydene, the integer that g is 1~20, the integer that j is 1~8.
6. the polymer modification organo-silicon compound according to any one of claims 1 to 5 containing perfluoroalkyl polyether base, In, in above-mentioned formula (1), Z be selected from hydrogen atom and it is following shown in group in group,
[changing 5]
-Si(CH3)3
-Si(CH2CH3)3
[changing 6]
[changing 7]
[changing 8]
In formula, the integer that g1 is 2~20, the integer that e is 0~3.
7. according to the polymer modification organo-silicon compound according to any one of claims 1 to 6 containing perfluoroalkyl polyether base, In, the polymer modification organo-silicon compound containing perfluoroalkyl polyether base indicated by above-mentioned formula (1) are by any one table in following formula Show：
[changing 9]
[changing 10]
[changing 11]
[changing 12]
[changing 13]
[changing 14]
[changing 15]
[changing 16]
[changing 17]
[changing 18]
[changing 19]
In formula, Z is same as described above, the integer that p1 is 5~100, the integer that q1 is 5~100, the integer that p1+q1 is 10~105, The integer that g1 is 2~20, the integer that e is 0~3.
8. surface conditioning agent, it includes the polymer modifications according to any one of claims 1 to 7 containing perfluoroalkyl polyether base Organo-silicon compound.
9. surface conditioning agent according to claim 8, which is characterized in that surface conditioning agent also contains by the following general formula (4) The polymer containing perfluoroalkyl polyether base indicated：
[changing 20]
A-Rf′-A (4)
In formula, A is that end is-CF3The fluoro-containing group of 1 valence of base, Rf ' are that the polymer containing fluoro oxyalkylene of divalent is residual Base.
10. the article being surface-treated with surface conditioning agent according to claim 9.
CN201680064424.1A 2015-11-06 2016-10-13 Polymer-modified organosilicon compound containing fluoropolyether group, surface treatment agent, and article Active CN108350168B (en)

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