TW201734086A - Fluoropolyether group-containing polymer-modified organic silicon compound, surface treatment agent, and product - Google Patents

Abstract

Provided are: a fluoropolyether group-containing polymer-modified organic silicon compound capable of forming a water- and oil-repellent layer exhibiting excellent wear resistance in a short time under mild conditions; a surface treatment agent containing said compound; and a product, the surface of which is treated using the treatment agent. Thus, a fluoropolyether group-containing polymer-modified organic silicon compound represented by general formula (1) [Rf represents a fluorooxyalkyl group- or fluorooxyalkylene group-containing polymer residue; Y represents a divalent hydrocarbon group; Q represents a divalent organosiloxane residue, a silalkylene group, or a silarylene group; X is a hydrogen atom, an alkyl group or a phenyl group; Z represents a hydrogen atom, a group represented by the formula -SiR3 (R is an alkyl group or a phenyl group), or a group represented by the formula -W-Q'-X (W is a single bond or a divalent hydrocarbon group; and Q' is a divalent group having a structure selected from a siloxane bond, a silalkylene structure, and a silarylene structure); and [alpha] is 1 or 2].

Description

Fluoropolyether-based polymer modified organic bismuth compound, surface treatment agent and articles

The present invention relates to a fluoropolyether group-containing polymer-modified organic ruthenium compound, a surface treatment agent containing the organic ruthenium compound, and an article surface-treated with the surface treatment agent.

In recent years, with the display of mobile phones, the touch panel of the screen is accelerating. However, since the touch panel is in an open state, there are many opportunities for direct attachment of fingers or cheeks, and it is a problem that sebum and the like are easily attached. Therefore, in order to make the appearance or the recognizability better, a technique in which fingerprints are less likely to adhere to the surface of the display or a technique in which dirt is easily removed is increasingly required each year, and therefore, it is desired to develop a material that meets such requirements. In particular, fingerprint dirt is likely to adhere to the surface of the touch panel display, so it is desirable to provide a water-repellent layer. However, the conventional water-repellent oil-repellent layer has high water-repellent property and excellent dirt-wiping property, but has problems in that the anti-fouling performance is deteriorated during use. Further, there is a case where the performance is deviated due to the method of coating, or the adhesion is deteriorated due to the applied substrate. In addition, the surface treatment agent so far has a good surface property for glass, but for the resin surface, The surface characteristics such as adhesion, water repellency, and abrasion resistance are not sufficiently exhibited.

In general, a fluorine-containing polyether group-containing compound has water repellency, chemical resistance, lubricity, mold release property, antifouling property, and the like because of its extremely small surface free energy. By utilizing this property, it is widely used in the industry for water-repellent oil-repellent and antifouling agents such as paper and fibers, slip agents for magnetic recording media, oil repellents for precision machines, mold release agents, cosmetics, protective films, and the like. However, this characteristic also means non-adhesiveness and non-adhesion to other substrates, and it is difficult to adhere the film even if it can be applied to the surface of the substrate.

Further, a decane coupling agent is known as a substrate for bonding a substrate such as glass or cloth to an organic compound, and is widely used as a coating agent for various substrate surfaces. The decane coupling agent is a hydrolyzable formyl group having an organic functional group and a reactive onarmany alkyl group (generally, an alkoxycarbenyl group or the like) in one molecule. The hydrolyzable formyl group forms a film by a self-condensation reaction by moisture or the like in the air. This film is chemically and physically bonded to the surface of glass or metal by a hydrolyzable formyl group to form a film having durability.

Therefore, it has been revealed that a polymer modified decane having a fluorine-containing polyether group in which a hydrolyzable formyl group is introduced into a fluorine-containing polyether group-containing compound is easily adhered to the surface of the substrate, and can be formed on the surface of the substrate. A composition of a film such as a water-repellent property, a chemical-resistance, a lubricity, a mold release property, and an anti-staining property (Patent Documents 1 to 8: Japanese Patent Laid-Open Publication No. 2003-238577, Japanese Patent No. 2860979, Japanese Patent Japanese Patent No. 4672095, Japanese Patent Publication No. 2008-534696, and Japanese Special Publication No. 2008-537557 Japanese Laid-Open Patent Publication No. 2012-072272, Japanese Laid-Open Patent Publication No. 2012-157856, and JP-A-2013-136833.

When the substrate is surface-treated with a composition containing the fluoropolyether group-containing polymer modified decane, the substrate is formed into a film by various coating methods, but after the application, the hydrolyzable formyl group is hydrolyzed. In the step of hardening the film, the hydrolysis reaction is promoted by high temperature conditions such as 80 ° C or 120 ° C or conditions under humidification. Further, even at room temperature, it reacts slowly with moisture in the air to form a hardened film. However, this hardening step requires high-temperature humidification conditions, and hardening at room temperature, which takes time and the like, and has a problem of control in production (delay factor). Further, under mild conditions such as room temperature hardening, the film which has been hardened for a short time (water-repellent oil-repellent layer) has a problem of abrasion resistance and deterioration of antifouling performance during use.

In the patent document 9 (JP-A-2008-144144), a fluorine-containing carboxylic acid as a curing catalyst is added to a coating composition to promote curing, and a film is formed in a short time under mild conditions. However, when the amount of the catalyst is reduced, the wear resistance is poor, and when the amount of the catalyst is increased, the initial performance is lowered. Further, the carboxyl group of the polar group is highly likely to appear on the outermost surface of the film, and the performance is lowered at this time.

Further, in the patent document 10 (JP-A-2004-145283), a fluorene-containing alkyl ether group-containing decane is proposed. The lens treated with the fluorine-containing polyalkylene ether-based decane is excellent in oil repellency and fingerprint wiping property, but has insufficient abrasion resistance.

[Previous Technical Literature] [Patent Literature] [Patent Document 1] Japanese Patent Laid-Open Publication No. 2003-238577 [Patent Document 2] Japanese Patent No. 2860979 [Patent Document 3] Japanese Patent No. 4672095 [Patent Document 4] Japanese Patent Publication No. 2008-534696 [Patent Document 5] Japanese Patent Publication No. 2008-537557 [Patent Document 6] Japanese Patent Laid-Open Publication No. 2012-072272 [Patent Document 7] Japanese Patent Laid-Open Publication No. 2012-157856 [Patent Document 8] Japanese Laid-Open Patent Publication No. 2013-136833 [Patent Document 9] Japanese Patent Laid-Open Publication No. 2008-144144 [Patent Document 10] Japanese Patent Laid-Open Publication No. 2004-145283

[Summary of the Invention]

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a fluorine-containing oil-repellent layer which is excellent in abrasion resistance even in a short period of time, particularly under mild conditions such as room temperature. A polyether-based polymer-modified organic ruthenium compound, a surface treatment agent containing the organic ruthenium compound, and an article surface-treated with the surface treatment agent.

The inventors of the present invention have found that the surface treatment agent of the polymer-modified organic ruthenium compound having a fluorine-containing polyether group represented by the following formula (1), even if it does not have a terminal functional group, is obtained by careful examination of the above object. Under mild conditions such as room temperature, even in a short period of time, a water-repellent oil-repellent layer excellent in abrasion resistance can be formed for a resin product such as a resin film or a plastic lens, and the present invention has been completed.

Accordingly, the present invention provides a fluorine-containing polyether-based polymer-modified organic hydrazine compound, a surface treatment agent, and an article.

[1] A fluorine-containing polyether-based polymer-modified organic ruthenium compound represented by the following formula (1),

Wherein Rf is a monovalent fluorooxyalkyl group or a divalent fluorooxyalkylene polymer residue, Y is independently a divalent hydrocarbon group, and Q is independently a divalent linear or cyclic organic a hydrazine residue, an alkylene group or an arylene group, X is independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a phenyl group, and Z is independently a hydrogen atom, and the following formula is -SiR ₃

(wherein R is independently an alkyl group having 1 to 4 carbon atoms or a phenyl group.)

The base of the expression, or the following formula -W-Q’-X

(wherein X is the same as the above, W is a single bond or a divalent hydrocarbon group, and Q' is a divalent group having a structure selected from the group consisting of a decane bond, an alkyl group structure, and an arylene structure)

The base of the representation, α is 1 or 2].

[2] The fluoropolyether-based polymer-modified organic hydrazine compound according to [1], wherein α is 1 in the above formula (1), and the Rf group is a group represented by the following formula (2),

(wherein, p, q, r, and s are each an integer from 0 to 200, and p+q+r+s=3 to 200, and each repeating unit may be linear or branched, and each repeating unit may be free from each other. Regularly bonded, d is an integer from 1 to 3, and the unit can be linear or branched).

[3] The fluoropolyether-based polymer-modified organic ruthenium compound according to [1], wherein α is 2 in the above formula (1), and the Rf group is a base represented by the following formula (3),

(wherein, p, q, r, and s are each an integer from 0 to 200, and p+q+r+s=3 to 200, and each repeating unit may be linear or branched, and each repeating unit may be free from each other. Regularly bonded, d is an integer from 1 to 3, and the unit can be linear or branched).

[4] The fluoropolyether-based polymer-modified organic ruthenium compound according to any one of [1] to [3] wherein, in the above formula (1), Y is an alkylene group having a carbon number of 3 to 10 .

[5] The fluoropolyether-based polymer-modified organic ruthenium compound according to any one of [1] to [4] wherein, in the above formula (1), Q is a group selected from the group represented by the following formula: base,

(wherein X is the same as above, R ^{1 is} independently an alkyl group having 1 to 4 carbon atoms or a phenyl group, and R ² is an alkylene group having 1 to 4 carbon atoms or an exoaryl group having 6 to 12 carbon atoms, g It is an integer from 1 to 20, and j is an integer from 1 to 8.)

[6] The fluoropolyether-based polymer-modified organic ruthenium compound according to any one of [1] to [5] wherein, in the above formula (1), Z is a hydrogen atom, and is selected from the group consisting of Base of the foundation,

(wherein g1 is an integer from 2 to 20, and e is an integer from 0 to 3).

[7] The fluoropolyether-based polymer-modified organic ruthenium compound according to any one of [1] to [6], wherein the fluoropolyether-based polymer represented by the above formula (1) is modified organic The hydrazine compound is represented by any of the following formulae,

(In the formula, Z is the same as above, p1 is an integer from 5 to 100, q1 is an integer from 5 to 100, p1+q1 is an integer from 10 to 105, g1 is an integer from 2 to 20, and e is from 0 to 3. Integer).

[8] A surface treatment agent comprising the fluoropolyether group-containing polymer-modified organic ruthenium compound according to any one of [1] to [7].

[9] The surface treatment agent according to [8], wherein the surface treatment agent further contains the following general formula (4) [Chemical 20] A-Rf'-A (4)

(wherein the end of the A system is a monovalent fluorine-containing group of -CF ₃ group, and Rf' is a polymer residue of a divalent fluorine-containing oxygen alkyl group)

A fluorine-containing polyether-based polymer.

[10] An article which is surface-treated with a surface treating agent as in [9].

Modified by a polymer containing the fluorine-containing polyether group of the present invention The film formed of the surface treatment agent of the organic compound has high water repellency, and particularly under mild conditions such as room temperature, the film formed in a short period of time is excellent in abrasion resistance. The surface treatment agent containing the fluoropolyether group-containing polymer-modified organic ruthenium compound of the present invention has a special adhesion to the surface of the resin, and is treated by the surface treatment agent, such as a resin film or The resin product of the spectacle lens can easily impart excellent water repellency, low dynamic friction, and abrasion resistance in a short period of time.

[Formation of the Invention]

The fluorine-containing polyether-based polymer-modified organic ruthenium compound of the present invention is represented by the following formula (1).

Wherein Rf is a monovalent fluorooxyalkyl group or a divalent fluorooxyalkylene polymer residue, Y is independently a divalent hydrocarbon group, and Q is independently a divalent linear or cyclic organic a hydrazine residue, an alkylene group or an arylene group, X is independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a phenyl group, and Z is independently a hydrogen atom, and the following formula is -SiR ₃

(wherein R is independently an alkyl group having 1 to 4 carbon atoms or a phenyl group.)

The base of the expression, or the following formula -W-Q’-X

(wherein the X system is the same as the above, W is a single bond or a divalent hydrocarbon group, and Q' is a structure having a structure selected from the group consisting of a decane bond, a fluorene chain structure, and an arylene group structure. Divalent base)

The base of the representation, α is 1 or 2].

In the above formula (1), when α is 1, Rf is preferably a one-valent fluorooxyalkyl group represented by the following formula (2).

(wherein, p, q, r, and s are each an integer from 0 to 200, and p+q+r+s=3 to 200, and each repeating unit may be linear or branched, and each repeating unit may be free from each other. Regularly bonded, d is an integer from 1 to 3, and the unit can be linear or branched).

In the above formula (1), when α is 2, Rf is preferably a divalent fluorooxyalkylene group represented by the following formula (3).

(wherein, p, q, r, and s are each an integer from 0 to 200, and p+q+r+s=3 to 200, and each repeating unit may be linear or branched, and each repeating unit may be free from each other. Regularly bonded, d is an integer from 1 to 3, and the unit can be linear or branched).

In the above formulas (2) and (3), p, q, r, and s are each an integer of 0 to 200, preferably p is an integer of 5 to 100, q is an integer of 5 to 100, and r is 0 to 100. The integer, s is an integer from 0 to 100, p+q+r+s=3~200, preferably 10~100, each repeating unit may be linear or branched, and each repeating unit may be randomly linked to each other. Knot. More preferably, p+q is 10 to 105, especially an integer of 15 to 60, and r = s = 0. When p+q+r+s is less than the above upper limit, the adhesion or film formation property is good, and when it is larger than the above lower limit, the fluorine can be sufficiently exhibited. The characteristics of the polyether group are preferred.

In the above formulae (2) and (3), d is an integer of 1 to 3, preferably 1 or 2, and the unit may be linear or branched.

Since Rf has a main chain structure represented by the above formula (2) or (3), a film having a low dynamic friction coefficient can be formed.

Further, the main chain has a fluoropolyether structure, and a linear polymer having a siloxane chain, a phenylene bond or a hydrazone bond at a single terminal of the molecular chain (α is 1, and Rf is a formula ( 2) represents a monovalent fluorooxyalkyl group, compared to a linear polymer having a siloxane linkage, a phenylene bond or a hydrazine linkage at both ends (α is 2, Rf is a formula) (3) a divalent fluorooxyalkylene group), which imparts excellent abrasion resistance to the obtained film

Specific examples of Rf include the following.

(wherein p', q', r', and s' are each an integer of 1 or more, and the upper limit is the same as the upper limit of the above p, q, r, and s. u is 1 to 24, and v is 1 to 24, And satisfy the number of u + v = r. Each repeating unit can be randomly bonded.)

In the above formula (1), Y is independently a divalent hydrocarbon group, a carbon number of 3 to 10, particularly a propylene group having a carbon number of 3 to 8 (trimethylene group, methyl group ethyl group), and a butyl group (fourth armor) The alkyl group, the methyl propyl group, the hexamethylene group, the octamethyl group and the like are preferably an alkyl group, and particularly preferably a trimethylene group.

In the above formula (1), X is independently a hydrogen atom and has a carbon number of 1 to 4. An alkyl group or a phenyl group such as a methyl group, an ethyl group, a propyl group or a butyl group is preferably a hydrogen atom or a methyl group.

In the above formula (1), Q is independently a divalent linear or cyclic organodecane residue, an alkylene group or an anthracene group, and is preferably a group selected from the group represented by the following formula.

(In the formula, X is the same as above, and R ^{1 is} independently an alkyl group or a phenyl group such as a methyl group, an ethyl group, a propyl group or a butyl group having a carbon number of 1 to 4, and R ² is a methylene group having a carbon number of 1 to 4; a aryl group such as an alkyl group, an extended propyl group, a butyl group or the like, or a phenyl group having a carbon number of 6 to 12, and a g of 1 to 20, preferably an integer of 1 to 10, j. It is 1~8, preferably an integer of 1~3.)

Specific examples of Q include, for example, the following groups.

(wherein g1 is an integer of 2 to 20, preferably 2 to 10.)

In the above formula (1), Z is independently a hydrogen atom, and the following formula -SiR ₃

(wherein R is independently an alkyl group having 1 to 4 carbon atoms or a phenyl group.)

The base of the expression, or the following formula -W-Q’-X

(In the formula, X is the same as described above, W is a single bond or a divalent hydrocarbon group, and Q' is a divalent group having a structure selected from the group consisting of a decane chain, an alkyl group structure, and an arylene structure.)

The base of expression.

In -SiR ₃ , R is an alkyl group such as a methyl group, an ethyl group, a propyl group or a butyl group having a carbon number of 1 to 4, or a phenyl group, and among them, a methyl group or an ethyl group is preferred.

Further, in -W-Q'-X, W is a single bond or a divalent hydrocarbon group, and the divalent hydrocarbon group may, for example, be an ethyl group having a carbon number of 2 to 10, particularly a carbon number of 2 to 8, and a stretching propyl group (trimethylene group). , methyl extended ethyl), butyl (tetramethylene, methyl propyl), hexamethylene, octamethyl, etc. alkyl, W is preferably a single bond Or trimethylene.

X is the same as above, and is preferably a hydrogen atom or a methyl group.

Further, Q' is a divalent group having a structure selected from the group consisting of a decane olefin bond, a fluorene alkyl group structure, and a fluorene arylene structure, and has a bivalent linear or cyclic organoxanthene exemplified in the above Q. Residues, alkylene structures, and aryl structures are preferred.

Specific examples of Q' include, for example, the following groups.

(wherein g1 is the same as above.)

Specific examples of Z include a hydrogen atom and those described below.

(In the formula, g1 is the same as above, and e is an integer of 0 to 3.)

The polymer-modified organic ruthenium compound of the fluorine-containing polyether group represented by the above formula (1) is represented by the following formula. Further, in each of the formulas, the number of repetitions (or polymerization degree) of each repeating unit constituting the fluorooxyalkyl group or the fluorooxyalkylene group can be any one of the above formulas (2) and (3).

(In the formula, Z, g1, and e are the same as above, p1 is an integer of 5 to 100, q1 is an integer of 5 to 100, and p1+q1 is an integer of 10 to 105.)

The method for preparing the fluoropolyether group-containing polymer-modified organic quinone compound represented by the above formula (1) includes, for example, the following method.

First, a fluorine-containing polyether group-containing polymer having a reactive group such as a fluorinated fluorenyl group, a halogenated fluorenyl group, an acid anhydride group, an ester group, a carboxylic acid group or a guanamine group at the end of the molecular chain, and a nucleophilic agent The solvent is mixed, for example, 1,3-bis(trifluoromethyl)benzene or tetrahydrofuran, and is aged at 1 to 6 hours, preferably at 0 to 80 ° C, preferably 50 to 70 ° C, more preferably at about 60 ° C. It is 3 to 5 hours, more preferably about 4 hours.

Here, the polymer of the fluorine-containing polyether group having a reactive group at the end of the molecular chain may, for example, be as described below.

(In the formula, Rf and α are the same as described above.)

Further, as the nucleophilic agent, allyl magnesium halide, 3-butenyl magnesium halide, 4-pentenyl magnesium halide, 5-hexenyl magnesium halide, or the like can be used. Also, it is also possible to use a corresponding lithium reagent.

The amount of the nucleophilic agent used is 1 equivalent of the reactive group of the fluorine-containing polyether group-containing polymer having a reactive group at the end of the above molecular chain, and 2 to 5 can be used. The equivalent weight is more preferably 2.5 to 3.5 equivalents, still more preferably about 3 equivalents.

Next, the reaction was stopped, and the aqueous layer and the fluorine solvent layer were separated by a liquid separation operation. The obtained fluorine solvent layer is further washed with an organic solvent, and the solvent is distilled off to obtain a polymer having a fluorine-containing polyether group having a hydroxyl group and an olefin moiety at the molecular chain terminal represented by the following formula (a).

(In the formula, Rf and α are the same as described above. U is a divalent hydrocarbon group.)

In the above formula (a), U is a divalent hydrocarbon group, and specific examples thereof include a methylene group, an exoethyl group, a propyl group (trimethylene group, a methyl group ethyl group), and a butyl group (tetramethylene group). a methyl group having a carbon number of from 1 to 8 such as a methyl propyl group, a hexamethylene group or an octamethyl group; and an alkyl group having a carbon number of from 6 to 8 such as a stretching phenyl group (for example, , a carbon number of 7 to 8 alkyl, an aryl group, etc.). U is preferably a linear alkyl group having 1 to 4 carbon atoms.

Next, if necessary, the hydrogen atom of the hydroxyl group of the polymer of the fluorine-containing polyether group having a hydroxyl group and an olefin moiety represented by the above formula (a) is substituted with another group.

A method of substituting a hydrogen atom of a hydroxyl group with a carboxyalkyl group represented by -SiR ₃ , for example, a polymer having a fluorine-containing polyether group having a hydroxyl group and an olefin moiety at a terminal of the molecular chain represented by the formula (a) and a formylating agent In the presence of a base such as an amine or an alkali metal base, a solvent such as a fluorine-based solvent or an organic solvent is used, preferably at 0 to 80 ° C, preferably 40 to 60 ° C, more preferably about 50 ° C. At a temperature, it is aged for 1 to 24 hours, preferably 2 to 10 hours, more preferably about 3 hours.

Further, another method is a dehydrogenation contact between a polymer having a fluorine-containing polyether group having a hydroxyl group and an olefin moiety at the end of the molecular chain represented by the formula (a) and a hydrohalane, and a platinum group-based catalyst or a boron catalyst. In the presence of a medium, a solvent such as a fluorine-based solvent or an organic solvent is used at a temperature of 0 to 60 ° C, preferably 15 to 35 ° C, more preferably about 25 ° C, for 10 minutes to 24 hours, preferably The dehydrogenation reaction is carried out for 30 minutes to 2 hours, more preferably for about 1 hour.

Here, as the methyl hydrazine alkylating agent, for example, a methyl hydrazine halide or a mercapto trifluoromethane sulfonate or the like can be used, and specific examples thereof include trimethylchloro decane, triethyl chloro decane, and tert. -butyldimethyl chloride, triisopropylchlorodecane, triphenylchlorodecane, trimethylformamidine bromide, trimethylformamidine trifluoromethanesulfonate, triethylformamidine Fluoromethanesulfonate, tert-butyldimethyltrifluoromethanesulfonate, triisopropylformamyltrifluoromethanesulfonate, etc. Further, in the case where no base is used, hexamethyldiene may also be used. Indoxazane, trimethylmethanyl dimethylamine, trimethylformamidinyldiethylamine, trimethylcarbamimidazole, used in an amount relative to the end of the molecular chain represented by formula (a) The hydroxyl group of the fluorine-containing polyether group-containing polymer of the hydroxy group and the olefin moiety may be used in an amount of from 1 to 10 equivalents, more preferably from 1 to 4 equivalents, still more preferably about 2 equivalents.

Further, examples of the hydrohalane include trimethyldecane, triethyldecane, tert-butyldimethylsilane, triisopropyldecane, and triphenyldecane. The amount used is relative to the molecule represented by the formula (a). The hydroxyl group of the fluorine-containing polyether group-containing polymer having a hydroxyl group and an olefin moiety at the end of the chain may be used in an amount of 1 to 5 equivalents, more preferably 1.5 to 3 equivalents, still more preferably about 2 equivalents.

Then, the reaction is stopped, and the water layer is separated by a liquid separation operation. Fluorine solvent layer. The obtained fluorine solvent layer is further washed with an organic solvent, and the solvent is distilled off to obtain a polymer having a fluorinated oxyalkyl group having a germyl group and an olefin moiety at the molecular chain terminal represented by the following formula (b).

(wherein Rf, R, U, and α are the same as described above.)

a method of substituting a hydrogen atom of a hydroxyl group with a carboxyalkyl group represented by -W-Q'-X, for example, a polymer having a fluorine-containing polyether group having a hydroxyl group and an olefin moiety at a terminal of the molecular chain represented by the formula (a) The organic ruthenium compound of the SiH group is used in the presence of a dehydrogenation catalyst such as a boron catalyst, and a solvent such as a fluorine-based solvent or an organic solvent is used at 0 to 60 ° C, preferably 15 to 35 ° C, more preferably about The dehydrogenation reaction is carried out at a temperature of 25 ° C for 10 minutes to 24 hours, preferably 30 minutes to 2 hours, more preferably about 1 hour.

Here, examples of the organic ruthenium compound having a SiH group include those shown below.

(In the formula, g and e are the same as above, and c is an integer of 1 to 4.)

The amount used is 1 equivalent of the hydroxyl group of the polymer having a fluorine-containing polyether group having a hydroxyl group and an olefin moiety at the terminal of the molecular chain represented by the formula (a). It can be used in an amount of 1 to 10 equivalents, more preferably 1.2 to 5 equivalents.

Next, the reaction was stopped, and the aqueous layer and the fluorine solvent layer were separated by a liquid separation operation. The obtained fluorine solvent layer is further washed with an organic solvent, and the solvent is distilled off to obtain a fluorine-containing oxyalkyl group having an olefin moiety at the molecular chain terminal represented by the following formula (c) and a hydroxyl group portion substituted with an organic sulfonium compound group. The polymer.

(wherein, Rf, Q', X, U, and α are the same as described above, and W' is a single bond.)

Further, a method of substituting a hydrogen atom of a hydroxyl group into a group represented by -W-Q'-X may, for example, first, after replacing a hydrogen atom of a hydroxyl group with a terminal unsaturated group, the terminal unsaturated group (olefin moiety) A method of reacting with an organic ruthenium compound having a SiH group together with other olefin sites.

The method of substituting a hydrogen atom of a hydroxy group into a terminal unsaturated group, the polymer of the fluorine-containing polyether group which has a hydroxyl group and an olefin part in the molecular chain terminal of the formula (a), and an olefin-introducing agent, in an amine or alkali In the presence of a base such as a metal base, if necessary, an additive such as a tetrabutylammonium halide or an alkali metal halide or a solvent such as a fluorine-based solvent or an organic solvent is used, and the solvent is at 0 to 90 ° C. It is preferably 60 to 80 ° C, more preferably about 70 ° C, and is aged for 1 to 25 hours, preferably 3 to 10 hours, more preferably about 6 hours.

Here, as the olefin introducing agent, for example, an allyl halide can be used. Etc., specifically, allyl chloride, allyl bromide, allyl iodide, 4-chloro-1-butene, 4-bromo-1-butene, 4-iodo-1-butene Alkene, 5-chloro-1-pentene, 5-bromo-1-pentene, 5-iodo-1-pentene, etc., which are used in the presence of a hydroxyl group and an olefin moiety relative to the terminal of the molecular chain represented by the formula (a) The hydroxyl group of the fluorine-containing polyether group-containing polymer may be used in an amount of from 1 to 10 equivalents, more preferably from 2.5 to 6 equivalents, still more preferably about 5 equivalents.

Next, the reaction was stopped, and the aqueous layer and the fluorine solvent layer were separated by a liquid separation operation. The obtained fluorine solvent layer is further washed with an organic solvent, and the solvent is distilled off to obtain a polymer of a fluorine-containing oxyalkyl group having an olefin moiety at a molecular chain terminal represented by the following formula (d).

(wherein Rf, U, and α are the same as described above. V is a single bond or a divalent hydrocarbon group.)

In the above formula (d), V is a single bond or a divalent hydrocarbon group, and specific examples of the divalent hydrocarbon group include a methylene group, an exoethyl group, a propyl group (trimethylene group, a methyl group ethyl group), and a dibutyl group. a alkyl group having a carbon number of 1 to 8 such as a tetramethylene group, a methyl propyl group, a hexamethylene group or an octamethyl group, and a aryl group having a carbon number of 6 to 8 such as a phenyl group. An alkyl group (for example, a C 7-8 alkyl group, an aryl group, etc.). V is preferably a methylene group.

Next, any one of the polymers of the fluorinated polyether group having an olefin moiety at the end of the molecular chain represented by the above formula (a) to (d) and an organic ruthenium compound having a SiH group in the molecule are obtained in the hydrogenation reaction of ruthenium Medium, such as chlorine In the presence of a toluene solution of a platinum acid/vinyl oxane complex, it is aged at 1 to 72 hours, preferably at a temperature of 40 to 120 ° C, preferably 60 to 100 ° C, more preferably about 80 ° C. It is 20 to 36 hours, more preferably about 24 hours.

Here, the organic ruthenium compound having a SiH group in the molecule is preferably a compound represented by the following formula.

(wherein R ¹ , R ² , X, g, and j are the same as above, i is an integer of 1 to 6, preferably 1 to 4, and i + j is 3 to 10, preferably 3 to 5 Integer.)

Examples of the organic ruthenium compound having a SiH group in the molecule include, for example, those described below.

(In the formula, g, g1, and e are the same as described above.)

The amount of the organic ruthenium compound having a SiH group in the molecule is 1 equivalent of the terminal unsaturated group of the polymer having a fluoropolyether group having an olefin moiety at the terminal of the molecular chain represented by the above formulas (a) to (d). It is used in an amount of 5 to 20 equivalents, more preferably 7.5 to 12.5 equivalents, still more preferably about 10 equivalents.

Then, by distilling off the solvent and the unreacted product under reduced pressure, the fluoropolyether-based polymer-modified organic ruthenium compound represented by the above formula (1) can be obtained. Further, the above reaction may be carried out singly or continuously.

The surface treatment agent of the present invention contains the polymer-modified organic ruthenium compound of the fluorine-containing polyether group represented by the above formula (1).

The surface treatment agent of the present invention may further contain the following general formula (4) [ Chem . 54] A-Rf'-A (4)

(wherein the A-based fluorine atom or the terminal is a -CF ₃ -based one-valent fluorine-containing group, and the Rf' is a divalent fluorine-containing oxygen-extended alkyl group polymer residue.)

A fluorine-containing polyether-based polymer (hereinafter referred to as a non-functional polymer).

In the above formula (4), the fluorine atom of the A atom or the one-valent fluorine-containing group of the -CF ₃ group is preferably a fluorine atom or a linear perfluoroalkyl group having 1 to 6 carbon atoms, and among them, preferably -F group, -CF ₃ group, -CF ₂ CF ₃ group, -CF ₂ CF ₂ CF ₃ group.

Further, Rf' is a polymer residue of a divalent fluorine-containing oxygen alkyl group, and Rf' is preferably as described below.

(wherein p2 is an integer from 5 to 200, preferably from 10 to 100, q2 is from 5 to 200, preferably from 10 to 100, and r1 is from 10 to 200, preferably from 20 to 100, t1 It is an integer of 5~200, preferably 10~100, t2 is 10~200, preferably an integer of 20~100, t1+p2 is 10~205, preferably an integer of 20~110, q2+p2 10~205, preferably an integer of 20~110.)

The non-functional polymer represented by the formula (4) includes the following ones.

(In the formula, p2, q2, r1, t1, and t2 are the same as described above.)

The amount of the non-functional polymer represented by the formula (4) is not particularly limited, but is preferably 0.1 with respect to the mass of the fluoropolyether-based polymer-modified organic quinone compound represented by the formula (1). ~60% by mass, particularly preferably in the range of 10 to 40% by mass, when there is too much, there is a problem that adhesion is caused.

The surface treatment agent may contain a suitable solvent. Examples of such a solvent include a fluorine-modified aliphatic hydrocarbon solvent (perfluoroheptane, perfluorooctane, etc.) and a fluorine-modified aromatic hydrocarbon solvent (xylenehexafluoride (1, 3). - bis(trifluoromethyl)benzene), benzotrifluoride, etc., fluorine modified ether solvent (methyl perfluorobutyl ether, ethyl perfluorobutyl ether, perfluoro(2-butyltetrahydrofuran) )), a fluorine-modified alkylamine solvent (perfluorotributylamine, perfluorotributylamine, etc.), a hydrocarbon solvent (petroleum ether, mineral spirit, toluene, xylene, etc.) A ketone solvent (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.). Among these, a solvent modified with fluorine is preferred from the viewpoints of solubility, wettability, and the like. Particularly preferred are hexafluoro-m-xylene, perfluoro(2-butyltetrahydrofuran), perfluorotributylamine, and ethyl perfluorobutyl ether.

The above solvent may be used in combination of two or more kinds, but it is preferred to uniformly dissolve the fluoropolyether-based polymer-modified organic hydrazine compound. Further, the optimum concentration of the polymer having a fluorine-containing oxyalkylene group dissolved in a solvent varies depending on the treatment method, but the surface treatment agent is preferably from 0.01 to 40% by mass, particularly preferably from 0.05 to 25% by mass.

The surface treating agent of the present invention is subjected to surface treatment of a resin article such as a resin film or a spectacle lens. Here, the resin product is preferably made of a thermoplastic resin, and specifically, a hard-coated thermoplastic resin film (hardened Coat film) is preferably used, and the pencil hardness is 4H or more, which is not administered. A cured thermoplastic resin film (high hardness resin film) or a thermoplastic resin film (antireflection film) having an antireflection layer.

Further, in the present invention, the above resin product is treated with SiO _{2 in} advance. Here, the SiO ₂ treatment is preferably treated by SiO ₂ by a sputtering method from the viewpoint of improving the adhesion between the resin product and the treatment agent.

The surface treatment agent of the present invention can be applied to a substrate by a conventional method such as brushing, dipping, spraying, or vapor deposition. The heating method in the vapor deposition treatment may be either a resistance heating method or an electron beam heating method, and is not particularly limited. Further, the post-treatment conditions vary depending on the post-treatment method, for example, in the case of vapor deposition treatment or spray coating, and the use of the SiO ₂ -treated resin film as a substrate, at room temperature (25 ° C) to In the range of 200 ° C, it can be 5 minutes to 24 hours, especially 10 minutes to 12 hours, or can be post-treated under humidification. In particular, the present invention can be used for 10 minutes to 24 hours, particularly 30 minutes to 12 hours, even at room temperature. Further, the film thickness of the film can be appropriately selected depending on the type of the substrate, but is usually 0.1 to 100 nm, particularly 1 to 25 nm.

The resin product treated by the above surface treatment agent of the present invention can be used as a car navigation system, a mobile phone, a digital camera, a digital camera, a PDA, a portable audio player, a car audio system, a game machine, an eyeglass lens, a camera lens Medical equipment such as filters, sunglasses, gastroscopes, photocopiers, personal computers (PCs), liquid crystal displays, organic EL displays, plasma displays, touch panel displays, protective films, hardened films, high hardness resins, An optical article, a touch panel, an antireflection film, a quartz substrate, or the like which is used for a part or a part of a product such as an antireflection film or a wearable terminal is preferable.

The surface treatment agent for surface-treating the resin product of the present invention can form a film for a short period of time even under mild conditions such as curing at room temperature, and the film exhibits excellent water repellency or durability, so it is particularly It can be used as a water-repellent layer for eyeglass lenses, touch panel displays, hardened films, high-hardness resins, anti-reflective films, and wearable terminals. Here, the high-hardness resin is, for example, a resin molded product having a pencil hardness of 4H or more, such as the product name SILPLUS manufactured by Nippon Steel Chemical Co., Ltd., or the HD film manufactured by Gunze Co., Ltd., which is a film PR instead of glass. The resin film of the resin is not particularly limited to those described above.

[Examples]

The present invention will be described in more detail with reference to Synthesis Examples, Examples and Comparative Examples, but the present invention is not limited to the following examples.

In the examples and comparative examples, the compounds obtained by the following synthesis examples were used.

[Synthesis Example 1]

Synthesis of Compound 1

150 g of tetrahydrofuran and 300 g of 1,3-bis(trifluoromethyl)benzene were mixed in a reaction container, and 160 ml of 0.7 M allyl magnesium bromide was added dropwise. Then, slowly add the following formula (A)

After 300 g of the compound (4.8 × 10 ^-2 mol), it was heated at 60 ° C for 4 hours. After the completion of the heating, the mixture was cooled to room temperature, and the solution was dropped into 300 g of a 1.2 M aqueous hydrochloric acid solution to terminate the reaction. The lower layer of the fluorine compound layer was recovered by a liquid separation operation, and then washed with acetone. The fluorine compound layer of the lower layer after washing was collected again, and the residual solvent was distilled off under reduced pressure to obtain 292 g of a polymer of the fluorine-containing polyether group represented by the following formula (B).

In the reaction vessel, add the following formula (B)

80 g (1.0 × 10 ^-2 mol) of the compound was dissolved in 80 g of 1,3-bis(trifluoromethyl)benzene, and a toluene solution of chloroplatinic acid/vinyloxirane complex was mixed 8.0×. 10 ^-2 g (containing 2.1 × 10 ^-6 mol of Pt monomer) and 37 g (1.9 × 10 ^-1 mol) of 1,4-bis(dimethylformamido)benzene, aged at 80 ° C for 7 hours, borrowed The solvent and the unreacted product were distilled off under reduced pressure to obtain 70 g of a fluorine-containing polyether group-containing polymer (Compound 1) represented by the following formula (C).

¹ H-NMR δ0-0.2 (-Si(C H ₃ ) ₂ )24H δ0.4-0.6(-CH ₂ CH ₂ C H ₂ -Si)4H δ1.3-1.6 (-CH ₂ C H ₂ CH ₂ -Si)4H δ1.6-1.9(-C H ₂ CH ₂ CH ₂ -Si)4H δ3.6-4.2(-Si H )2H δ6.6-7.1(-C ₅ H ₄ )8H

[Synthesis Example 2]

Synthesis of Compound 2

In the reaction vessel, 100 g of 1,3-bis(trifluoromethyl)benzene and 8.2 g (5.4×10 ^-2 mol) of DBU (diazabicycloundecene) were mixed, and the following formula (B)

After 100 g of the compound (2.7 × 10 ^-2 mol), 5.8 g (5.4 × 10 ^-2 mol) of trimethylchloromethane was added dropwise. Then, it was heated at 50 ° C for 3 hours. After the end of the heating, the mixture was cooled to room temperature, and an aqueous hydrochloric acid solution was dropped. The lower layer of the fluorine compound layer was recovered by a liquid separation operation, and then washed with methanol. The fluorine compound layer of the lower layer after washing was collected again, and the residual solvent was distilled off under reduced pressure to obtain 90 g of a polymer of the fluorine-containing polyether group represented by the following formula (D).

¹ H-NMR δ0-0.2 (-OSi(C H ₃ ) ₃ )9H δ2.4-2.6(-C H ₂ CH=CH ₂ )4H δ5.0-5.2(-CH ₂ CH=C H ₂ )4H Δ5.7-5.9(-CH ₂ C H =CH ₂ )2H

Add the following formula (D) to the reaction vessel

50 g (1.4 × 10 ^-2 mol) of the compound was dissolved in 50 g of 1,3-bis(trifluoromethyl)benzene, and a toluene solution of a platinum chloride acid/vinyl alkane complex was mixed 1.5 × 10 ^-1 g (containing Pt monomer 4.0 × 10 ^-6 mol) and 1,3,5,7-tetramethylcyclotetraoxane 33 g (1.3 × 10 ^-1 mol), cooked at 80 ° C for 19 hours The solvent and the unreacted product were distilled off under reduced pressure to obtain 56 g of a fluorine-containing polyether group-containing polymer (compound 2) represented by the following formula (E).

¹ H-NMR δ0-0.2 (-OSi-C H ₃ , -OSi(C H ₃ ) ₃ )36H δ0.5-0.8(-CH ₂ CH ₂ C H ₂ -Si)4H δ1.3-2.2(- C H ₂ C H ₂ CH ₂ -Si)8H δ4.3-5.2(-Si H )6H

[Synthesis Example 3]

Synthesis of Compound 3

In the reaction vessel, add the following formula (B)

150 g (4.0 × 10 ^-2 mol) of the compound was dissolved in 150 g of 1,3-bis(trifluoromethyl)benzene, and a toluene solution of chloroplatinic acid/vinyloxirane complex was mixed 8.0×. 10 ^-2 g (containing Pt monomer 4.0 × 10 ^-6 mol) and 1,1,3,3,5,5-hexamethyltrioxane 83 g (4.0 × 10 ^-1 mol) at 80 ° C After aging for 24 hours, the solvent and the unreacted product were distilled off under reduced pressure to obtain 150 g of a fluoropolyether group-containing polymer (compound 3) represented by the following formula (F).

¹ H-NMR δ0-0.2 (-OSi(C H ₃ ) ₂ )36H δ0.3-0.6(-CH ₂ CH ₂ C H ₂ -Si)4H δ1.3-1.8(-C H ₂ CH ₂ CH ₂ -Si,-CH ₂ C H ₂ CH ₂ -Si)8H δ3.3-3.6(-SiH)2H

[Synthesis Example 4]

Synthesis of Compound 4

In the reaction vessel, add the following formula (B)

50 g (1.4 × 10 ^-2 mol) of the compound is dissolved in 50 g of 1,3-bis(trifluoromethyl)benzene, and a toluene solution of chloroplatinic acid/vinyloxirane complex is mixed 8.0×. 10 ^-2 g (containing 1.3 × 10 ^-6 mol of Pt monomer) and 40 g (1.4 × 10 ^-1 mol) of 1,1,3,3,5,5,7,7-octamethyltetraoxane, After aging at 80 ° C for 4 hours, the solvent and the unreacted product were distilled off under reduced pressure to obtain 41 g of a fluoropolyether group-containing polymer (compound 4) represented by the following formula (G).

¹ H-NMR δ0-0.2 (-OSi(C H ₃ ) ₂ )48H δ0.3-0.6(-CH ₂ CH ₂ C H ₂ -Si)4H δ1.3-1.8 (-C H ₂ CH ₂ CH ₂ -Si,-CH ₂ C H ₂ CH ₂ -Si)8H δ3.3-3.6(-SiH)2H

[Synthesis Example 5]

Synthesis of Compound 5

In the reaction vessel, the following formula (B) is added

20g (0.5×10 ^-2 mol) of the compound, dissolved in 1,3-bis(trifluoromethyl)benzene 20g, mixed with chloroplatinic acid/vinyl oxime complex toluene solution 2.0× 10 ^-2 g (containing Pt monomer 0.5 × 10 ^-6 mol) and the following formula (H)

40 g (0.5 × 10 ^-1 mol) of decahydroaloxane, which was aged at 80 ° C for 7 hours, and the solvent and the unreacted product were distilled off under reduced pressure to obtain a polymerization of a fluorine-containing polyether group represented by the following formula (I). (Compound 5) 10 g.

¹ H-NMR δ0-0.2 (-OSi(C H ₃ ) ₂ ) 120H δ 0.3-0.8 (-CH ₂ CH ₂ C H ₂ -Si) 4H δ 1.3-1.8 (-C H ₂ CH ₂ CH ₂ -Si,-CH ₂ C H ₂ CH ₂ -Si)8H δ4.7-5.0(-SiH)2H

[Synthesis Example 6]

Synthesis of Compound 6

In the reaction vessel, add the following formula (B)

50g (1.3×10 ^-2 mol) of the compound, dissolved in 50g of 1,3-bis(trifluoromethyl)benzene, mixed with chloroplatinic acid/vinyl oxime complex toluene solution 5.0× 10 ^-2 g (containing Pt monomer 1.4 × 10 ^-6 mol) and pentamethyldioxane 20 g (1.4 × 10 ^-1 mol), aging at 80 ° C for 8 hours, distilling off the solvent by vacuum distillation As the unreacted product, 54 g of a fluorine-containing polyether group-containing polymer (compound 6) represented by the following formula (J) was obtained.

¹ H-NMR δ0-0.2(-Si-C H ₃ )30H δ0.2-0.4(-CH ₂ CH ₂ C H ₂ -Si)4H δ1.0-1.6(-C H ₂ CH ₂ CH ₂ -Si ,-CH ₂ C H ₂ CH ₂ -Si)8H

[Synthesis Example 7]

Synthesis of Compound 7

In the reaction vessel, add the following formula (B)

50 g (1.3 × 10 ^-2 mol) of the compound, dissolved in 50 g of 1,3-bis(trifluoromethyl)benzene, mixed with a toluene solution of a platinum chloride acid/vinyl alkane complex 1.0 × 10 ^-1 g (containing 2.8 × 10 ^-6 mol of Pt monomer) and 13 g (3.2 × 10 ^-2 mol) of 1-butane-decamethylpentaoxane, cooked at 80 ° C for 20 hours, by subtraction The solvent and the unreacted product were distilled off to obtain 54 g of a fluorine-containing polyether group-containing polymer (compound 7) represented by the following formula (K).

¹ H-NMR δ0-0.2(-Si-C H ₃ )60H δ0.3-0.6(-CH ₂ CH ₂ C H ₂ -Si)8H δ0.6-0.8(-CH ₂ CH ₂ CH ₂ -C H ₃ )6H δ1.1-1.3(-CH ₂ C H ₂ C H ₂ -C H ₃ )8H δ1.4-1.8(-C H ₂ C H ₂ CH ₂ -Si)8H

[Synthesis Example 8]

Synthesis of Compound 8

In the reaction vessel, the following formula (B) is added

25 g (0.7 × 10 ^-2 mol) of the compound was dissolved in 25 g of 1,3-bis(trifluoromethyl)benzene, and mixed with a platinum chloride acid/vinyl alkane complex toluene solution 2.5 × 10 ^-2 g (containing 0.7 × 10 ^-6 mol of Pt monomer) and 8.9 g (0.7 × 10 ^-1 mol) of bis(dimethylformanyl)methane, which were aged at 80 ° C for 24 hours by decompression The solvent and the unreacted product were distilled off to obtain 10 g of a fluorine-containing polyether group-containing polymer (compound 8) represented by the following formula (L).

¹ H-NMR δ0-0.4 (-OSi(C H ₃ ) ₂ ,-Si-C H ₂ -Si)28H δ0.4-0.8(-CH ₂ CH ₂ C H ₂ -Si)4H δ1.2-2.0 (-C H ₂ C H ₂ CH ₂ -Si) 8H δ3.8-4.2(-SiH)2H

[Synthesis Example 9]

Synthesis of Compound 9

In the reaction vessel, mix the following formula (M)

200g (2.6×10 ^-2 mol), 1,3-bis(trifluoromethyl)benzene 200g, 1,1,3,3,5,5-hexamethyltrioxane 108g (5.2×) 10 ^-3 mol), and a toluene solution of chloroplatinic acid/vinyl fluorene complex complex 6.0 × 10 ^-1 g (containing Pt monomer 1.6 × 10 ^-5 mol), and aging at 80 ° C for 40 hours . Then, the solvent and the unreacted product were distilled off under reduced pressure. Then, the remaining low-boiling component and high-boiling component were removed by a molecular distillation apparatus to obtain 200 g of a liquid product (Compound 9).

The obtained compound 9 was confirmed to have a structure represented by the following formula (N) by ¹ H-NMR.

¹ H-NMR δ0-0.4 (-OSi(C H ₃ ) ₂ )72H δ0.4-0.8(-CH ₂ CH ₂ C H ₂ -Si)8H δ1.2-2.0(-C H ₂ C H ₂ CH ₂ -Si)16H δ3.8-4.2(-SiH)4H

[Synthesis Example 10]

Synthesis of Compound 10 (Comparative)

In the reaction vessel, mix the following formula (B)

200g (2.6×10 ^-2 mol), 1,3-bis(trifluoromethyl)benzene 200g, trimethoxydecane 12.7g (1.1×10 ^-1 mol), and chloroplatinic acid/vinyl The toluene solution of the oxime complex was 6.0 × 10 ^-1 g (containing 1.6 × 10 ^-5 mol of Pt monomer), and it was aged at 80 ° C for 40 hours. Then, the solvent and the unreacted product were distilled off under reduced pressure. Next, the remaining low-boiling component and high-boiling component were removed by a molecular distillation apparatus to obtain 201 g of a liquid product (Compound 10).

The obtained compound 10 was confirmed to have a structure represented by the following formula (O) by ¹ H-NMR.

¹ H-NMR δ 0.2-2.2 (-C H ₂ C H ₂ C H ₂ -) 12H δ 3.0-3.5 (-Si(OC H ₃ ) ₃ ) 18H

Further, the following compounds were used in the comparative examples.

[Compound 11] (H ₃ CO) ₃ Si-CH ₂ CH ₂ CH ₂ -CH ₂ O-CF ₂ -(CF ₂ O) _p1 -(C ₂ F ₄ O) _q1 -CF ₂ -CH ₂ O-CH ₂ CH ₂ CH ₂ -Si(OCH ₃ ) ₃ p1:q1=47:53, p1+q1≒45

[Compound 12]

[Examples 1 to 9 and Comparative Examples 1 to 3]

Modification of surface treatment agent and formation of hardened film

The above compounds 1 to 12 were dissolved in Novec 7200 (ethyl perfluorobutyl ether, manufactured by 3M Company) to have a concentration of 20% by mass to prepare a surface treatment agent. After the preparation of the surface treatment agent, the resin film (Ar: 10 cc, O ₂ : 80 cc, output: 250 W, time: 30 seconds) was used to wash the resin film (manufactured by Tigold Co., Ltd.), and the surface treatment agent was vacuumed at 10 mg. After vapor deposition (treatment conditions: pressure: 2.0 × 10 ^-2 Pa, heating temperature: 700 ° C), a film having a film thickness of 15 nm was formed after 24 hours in an environment of 25 ° C and a humidity of 50% RH. Further, the resin film was made of polyethylene terephthalate, and after the surface of the film was subjected to an acrylic hardening treatment, SiO ₂ was sputter-coated at a thickness of 100 nm on the outermost surface.

The film formed using the compounds 1 to 9 was used as the examples 1 to 9, and the film formed using the compounds 10 to 12 was used as the comparative examples 1 to 3.

The films of Examples 1 to 9 and Comparative Examples 1 to 3 were evaluated by the following methods. Either test was carried out at 25 ° C and a humidity of 50% RH.

[Evaluation of wear resistance]

In the obtained film, the abrasion resistance of the cloth (BEMCOT) was measured using Tribogear TYPE: 30S (manufactured by Shinto Scientific Co., Ltd.).

The test was completed when the water contact angle was less than 100° under the following conditions. The abrasion resistance was evaluated by maintaining the number of wear of the water contact angle of 100 or more.

Contact area: 10mm × 30mm

Load: 1.5kg

Resistance to cloth

Cloth: BEMCOT M-3II (made by Asahi Kasei Corporation)

Moving distance (one way) 20mm

Movement speed 1,800mm/min

Load: 0.5kg/cm ²

Further, the contact angle of the water contact angle was measured using a contact angle meter DropMaster (manufactured by Kyowa Interface Science Co., Ltd.), and the contact angle of the film to water (droplet: 2 μl) was measured. Further, the water contact angle was measured by dropping 2 μl of the droplet onto the surface of the sample after 1 second.

According to the above Table 1, in Comparative Examples 1, 2 and 3, the surface treatment agent was vapor-deposited on the surface of the substrate, and after the post-treatment, the abrasion resistance was 0 times, and the abrasion resistance was not exhibited. . On the other hand, in Examples 1 to 9, the surface treatment agent was vapor-deposited on the surface of the substrate, and after the post-treatment, the abrasion resistance test was performed to exhibit excellent abrasion resistance. Examples 1 to 9 have a siloxane chain, a phenylene structure, or a fluorene alkyl structure at the end of the molecular chain (the linking moiety of the molecule), so in particular, the SiCH ₃ moiety and the group of the linking moiety the surface of the SiO ₂ layer of material from the interaction forces between the SiO ₂ OH moiety of the molecule, the polymer of the surface treatment agent can be easily aligned, so even if the terminal group having no hydrolyzable groups, compared to the surface of the Comparative Example The treatment agent improves the adhesion to the substrate.

The resin which forms the antifouling surface layer by the surface treatment agent containing the fluoropolyether group-containing polymer-modified organic ruthenium compound of the present invention exhibits excellent wear durability. The resin which forms the antifouling surface layer with the surface treatment agent of the present invention is particularly suitable for use in the surface of an eyeglass lens, a sunglass lens, a touch panel display, an antireflection film or the like which requires an antifouling treatment.

[Industrial availability]

The article subjected to surface treatment with a surface treatment agent containing the polymer-modified organic ruthenium compound of the fluorine-containing polyether group of the present invention exhibits excellent abrasion durability. The resin article surface-treated by the surface treatment agent of the present invention is particularly useful for a resin product such as a touch panel display, an antireflection film, an eyeglass lens, or the like which is assumed to adhere to grease.

Claims (10)

A fluoropolyether-based polymer-modified organic ruthenium compound represented by the following formula (1), Wherein Rf is a monovalent fluorooxyalkyl group or a divalent fluorooxyalkylene polymer residue, Y is independently a divalent hydrocarbon group, and Q is independently a divalent linear or cyclic organic a hydrazine residue, an alkylene group or an arylene group, X is independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a phenyl group, and Z is independently a hydrogen atom, and the following formula is -SiR ₃ (wherein R is independently a group represented by an alkyl group having 1 to 4 carbon atoms or a phenyl group, or a formula -W-Q'-X (wherein the X system is the same as the above, and W is a single bond or a divalent hydrocarbon group, Q 'is a group represented by a divalent group having a structure selected from the group consisting of a siloxane chain, an alkylene structure, and an arylene structure, and α is 1 or 2]. The fluoropolyether-based polymer-modified organic ruthenium compound according to the first aspect of the invention, wherein in the formula (1), α is 1, and the Rf group is a base represented by the following formula (2). (wherein, p, q, r, and s are each an integer from 0 to 200, and p+q+r+s=3 to 200, and each repeating unit may be linear or branched, and each repeating unit may be free from each other. Regularly bonded, d is an integer from 1 to 3, and the unit can be linear or branched). The fluoropolyether-based polymer-modified organic ruthenium compound according to the first aspect of the invention, wherein in the formula (1), α is 2, and the Rf group is a base represented by the following formula (3). (wherein, p, q, r, and s are each an integer from 0 to 200, and p+q+r+s=3 to 200, and each repeating unit may be linear or branched, and each repeating unit may be free from each other. Regularly bonded, d is an integer from 1 to 3, and the unit can be linear or branched). The fluoropolyether-based polymer-modified organic ruthenium compound according to any one of claims 1 to 3, wherein, in the above formula (1), Y is an alkylene group having 3 to 10 carbon atoms. The fluoropolyether-based polymer-modified organic ruthenium compound according to any one of the above-mentioned formulas (1), wherein Q is a group selected from the group represented by the following formula, (wherein X is the same as above, R ^{1 is} independently an alkyl group having 1 to 4 carbon atoms or a phenyl group, and R ² is an alkylene group having 1 to 4 carbon atoms or an exoaryl group having 6 to 12 carbon atoms, g It is an integer from 1 to 20, and j is an integer from 1 to 8.) The fluoropolyether-based polymer-modified organic ruthenium compound according to any one of claims 1 to 3, wherein in the above formula (1), Z is a hydrogen atom and a group selected from the group consisting of Base, (wherein g1 is an integer from 2 to 20, and e is an integer from 0 to 3). The fluoropolyether-based polymer-modified organic ruthenium compound according to any one of claims 1 to 3, wherein the fluoropolyether-based polymer-modified organic ruthenium compound represented by the above formula (1) is Any of the following expressions, (In the formula, Z is the same as above, p1 is an integer from 5 to 100, q1 is an integer from 5 to 100, p1+q1 is an integer from 10 to 105, g1 is an integer from 2 to 20, and e is from 0 to 3. Integer). A surface treatment agent comprising a fluoropolyether-based polymer-modified organic ruthenium compound according to any one of claims 1 to 3. The surface treatment agent of claim 8, wherein the surface treatment agent further comprises the following general formula (4) [Chemical 20] A-Rf'-A (4) (wherein the end of the A system is -CF ₃ group) A fluorine-containing polyether-based polymer represented by a one-valent fluorine-containing group, Rf' is a polymer residue of a divalent fluorine-containing oxygen-extended alkyl group. An article which is surface-treated with a surface treating agent as in claim 9 of the patent application.