KR102648009B1 - Polymer-modified silane containing fluoropolyether group, surface treatment agent and article - Google Patents

Abstract

Polymer-modified silane containing a fluoropolyether group capable of forming a water- and oil-repellent layer with excellent slipperiness, a surface treatment agent containing this silane, and a surface treated with this surface treatment agent (i.e., a cured film of this surface treatment agent) provides goods). Equation (1)

(Rf is a polymer residue containing a monovalent or divalent fluoroxyalkylene group, Y is a divalent to hexavalent hydrocarbon group that may have a siloxane bond and/or a silylene group, R is an alkyl group or phenyl group having 1 to 4 carbon atoms, is a hydroxyl group or a hydrolyzable group, Q is a divalent organic group that may have a siloxane bond and/or a silylene group, R' is a monovalent fluoroalkyl group, a polymer residue containing a monovalent fluoroxyalkylene group, and has 1 to 4 carbon atoms. alkyl group or phenyl group, n is an integer of 1 to 3, m is an integer of 1 to 5, and α is 1 or 2.) A polymer-modified silane containing a fluoropolyether group.

Description

Polymer-modified silane containing fluoropolyether group, surface treatment agent and article

The present invention relates to a polymer-modified silane containing a fluoropolyether group, and more specifically, to a polymer-modified silane containing a fluoropolyether group that forms a film with excellent slipperiness, and a surface treatment agent containing this silane; and articles surface-treated with this surface treatment agent (i.e., having a cured film of this surface treatment agent on the surface).

Recently, the conversion of screens into touch panels, including displays of mobile phones, is accelerating. However, the screen of the touch panel is exposed, and there are many opportunities for direct contact with fingers or cheeks, so it is easy for dirt such as sebum to accumulate, which is a problem. Therefore, in order to improve appearance and visibility, the demand for technologies that make it difficult to get fingerprints on the surface of the display or to make it easy to remove dirt is increasing every year, and there is a demand for the development of materials that can meet these demands. . In particular, it is desired to install a water-repellent and oil-repellent layer on the surface of a touch panel display because fingerprints easily adhere thereto. However, although the conventional water and oil repellent layer has high water and oil repellency and is excellent in dirt removal, there is a problem in that the antifouling performance deteriorates during use.

In general, fluoropolyether group-containing compounds have very low surface free energy, so they have water and oil repellency, chemical resistance, lubricity, release properties, antifouling properties, etc. Taking advantage of its properties, it is widely used industrially as a water- and oil- and dirt-repellent agent for paper and textiles, a lubricant for magnetic recording media, an oil-repellent agent for precision equipment, a mold release agent, cosmetics, and a protective film. However, its properties mean that it is non-adhesive and non-adhesive to other substrates, and although it can be applied to the surface of a substrate, it is difficult to make the film adhere to it.

On the other hand, silane coupling agents are well known for bonding organic compounds to the surface of a substrate such as glass or cloth, and are widely used as a coating agent for the surface of various substrates. The silane coupling agent has an organic functional group and a reactive silyl group (generally a hydrolyzable silyl group such as an alkoxysilyl group) in one molecule. Hydrolyzable silyl groups undergo a self-condensation reaction due to moisture in the air, forming a film. This film becomes a strong, durable film by combining hydrolyzable silyl groups chemically and physically with the surface of glass or metal.

Therefore, by using a fluoropolyether group-containing polymer-modified silane in which a hydrolyzable silyl group is introduced into the fluoropolyether group-containing compound, it is easy to adhere to the substrate surface and also has water and oil repellency, chemical resistance, and lubricity on the substrate surface. , compositions capable of forming a film having release properties, antifouling properties, etc. are disclosed (Patent Documents 1 to 5: Japanese Patent Application Publication No. 2008-534696, Japanese Patent Application Publication No. 2008-537557, Japanese Patent Application Laid-open No. 2012-072272, Japan Japanese Patent Application Publication No. 2012-157856, Japanese Patent Application Publication No. 2013-136833).

Lenses or anti-reflective films surface-treated with a composition containing a fluoropolyether group-containing polymer-modified silane in which a hydrolyzable silyl group is introduced into this fluoropolyether group-containing compound have excellent wear resistance and release properties, but are not sufficiently slippery. not.

Japanese Patent Gazette No. 2008-534696 Japanese Patent Gazette No. 2008-537557 Japanese Patent Application Publication No. 2012-072272 Japanese Patent Application Publication No. 2012-157856 Japanese Patent Application Publication No. 2013-136833 Japanese Patent Application Publication No. 2015-199906

The present inventors have developed a fluoropolyether group-containing compound with excellent wear resistance, having the following formula:

(Wherein, Rf is a polymer residue containing a monovalent fluoroxyalkyl group or a divalent fluoroxyalkylene group, Y is a divalent to hexavalent hydrocarbon group that may have a siloxane bond and a silylene group, and R independently has a carbon number is an alkyl group or phenyl group of 1 to 4, X is independently a hydrolyzable group, n is an integer of 1 to 3, m is an integer of 1 to 5, and α is 1 or 2.)

A polymer-modified silane containing a fluoropolyether group, represented by The film formed by the water-containing surface treatment agent exhibits high water and oil repellency and wear resistance. However, the slipperiness was still not improved.

The present invention has been made in consideration of the above circumstances, and includes a polymer-modified silane containing a fluoropolyether group capable of forming a water- and oil-repellent layer with excellent slipperiness, a surface treatment agent containing this silane, and a surface treatment agent using the surface treatment agent. The object is to provide an article that has been treated (i.e., has a cured film of this surface treatment agent on its surface).

The present inventors have conducted intensive studies to solve the above object and have found that, in the polymer-modified silane containing a fluoropolyether group, the hydroxyl group represented by the general formula (1) described later is protected by the -Q-R' group below. It was discovered that polymer-modified silane containing a fluoropolyether group can form a water- and oil-repellent layer with excellent slipperiness and weather resistance and excellent storage stability, leading to the present invention.

Accordingly, the present invention provides the following fluoropolyether group-containing polymer-modified silane, surface treatment agent, and article.

[One]

The following general formula (1)

(Wherein, Rf is a polymer residue containing a monovalent or divalent fluoroxyalkylene group, Y is a 2- to 6-valent hydrocarbon group that may have a siloxane bond and/or a silylene group, and R is a hydrocarbon group having 1 to 4 carbon atoms. is an alkyl group or a phenyl group, It is a polymer residue, an alkyl group or a phenyl group having 1 to 4 carbon atoms, n is an integer of 1 to 3, m is an integer of 1 to 5, and α is 1 or 2.)

A polymer-modified silane containing a fluoropolyether group, represented by .

[2]

The modified polymer containing a fluoropolyether group according to [1], wherein α in the formula (1) is 1 and the Rf group is a monovalent fluoroxyalkylene group-containing polymer residue represented by the general formula (2) below. Silane.

(In the formula, p, q, r, and s are each an integer from 0 to 200, p+q+r+s=an integer from 3 to 200, t is an integer from 1 to 3, and each repeating unit is a linear It may be branched, and each repeating unit may be randomly combined.)

[3]

The modified fluoropolyether group-containing polymer described in [1], wherein α in the formula (1) is 2, and the Rf group is a divalent fluoroxyalkylene group-containing polymer residue represented by the general formula (3) below. Silane.

(In the formula, p, q, r, and s are each an integer from 0 to 200, p+q+r+s=an integer from 3 to 200, t is an integer from 1 to 3, and each repeating unit is a linear It may be branched, and each repeating unit may be randomly combined.)

[4]

In the above formula (1), Y is an alkylene group with 3 to 10 carbon atoms, an alkylene group with 8 to 16 carbon atoms including a phenylene group, or an alkylene group with 2 to 10 carbon atoms each has a silalkylene structure or a silarylene structure. A divalent group bonded through a divalent group, a divalent to tetravalent group bonded to a straight chain organopolysiloxane residue having 2 to 10 silicon atoms, and an alkylene group having 2 to 10 carbon atoms bonded to the bonding hand of a straight-chain organopolysiloxane residue having 2 to 10 silicon atoms. At least one group of [1] to [3] selected from the group consisting of divalent to tetravalent groups in which an alkylene group of 2 to 10 carbon atoms is bonded to the bond of a branched or cyclic organopolysiloxane residue. Polymer-modified silane containing fluoropolyether groups as described in one.

[5]

In the formula (1), each of A polymer-modified silane containing a fluoropolyether group according to any one of [1] to [4], which is selected from the group consisting of a monooxy group and a halogen atom.

[6]

The polymer-modified silane containing a fluoropolyether group according to any one of [1] to [5], wherein in the above formula (1), Q is a divalent organic group represented by the following formula (4).

(Wherein, R'' is an alkylene group or carbonyl group having 1 to 10 carbon atoms which may have any one of ketone, ester, amide, ether, sulfide, amine, and phenylene, and W is an alkylene group having 2 to 40 silicon atoms. straight-chain divalent organo(poly)siloxane residues, a straight-chain silicon alkylene group that may have a siloxane bond with 3 to 40 silicon atoms bonded through an alkylene group with 1 to 4 carbon atoms, and phenylene It is a divalent group selected from a straight-chain siloxane group that may have a siloxane bond of 3 to 40 silicon atoms and may be bonded through an alkylene group of 1 to 4 carbon atoms, and is an organo(poly)siloxane group. The sein residue, silalkylene group, and silarylene group may each be single or mixed, β is 0 or 1, γ is 0 or 1, and β+γ is 1 or 2.)

[7]

The polymer-modified silane containing a fluoropolyether group according to any one of [1] to [6], wherein the polymer-modified silane represented by formula (1) is represented by the following formula.

(In the formula, p1 is an integer from 5 to 100, q1 is an integer from 5 to 100, and p1+q1 is an integer from 10 to 105.)

[8]

A surface treatment agent containing the fluoropolyether group-containing polymer-modified silane according to any one of [1] to [7].

[9]

An article having on its surface a cured film of the surface treatment agent described in [8].

The surface treatment agent of the present invention containing a fluoropolyether group-containing polymer-modified silane in which the hydroxyl group bonded to the carbon atom is sealed with the -Q-R' group can form a water- and oil-repellent layer with excellent slipperiness.

(Form for carrying out the invention)

The polymer-modified silane containing a fluoropolyether group of the present invention is represented by the following general formula (1).

(Wherein, Rf is a polymer residue containing a monovalent or divalent fluoroxyalkylene group, Y is a 2- to 6-valent hydrocarbon group that may have a siloxane bond and/or a silylene group, and R is a hydrocarbon group having 1 to 4 carbon atoms. is an alkyl group or a phenyl group, It is a polymer residue, an alkyl group or a phenyl group having 1 to 4 carbon atoms, n is an integer of 1 to 3, m is an integer of 1 to 5, and α is 1 or 2.)

The polymer-modified silane containing a fluoropolyether group of the present invention contains a polymer residue (Rf) containing a monovalent or divalent fluoroxyalkylene group, and a hydrolyzable silyl group such as an alkoxysilyl group or a hydroxyl group-containing silyl group (-Si( R) _{3-n (} The hydroxyl group may have a divalent organic group (Q) that may have a siloxane bond and/or a silylene group as a linking group, preferably a ketone, ester, amide, ether, sulfide, amine, or phenylene, and may have 1 to 10 carbon atoms. A monovalent fluoroalkyl group, a monovalent fluoroxyalkylene group-containing polymer residue, carbon number 1 to By introducing an alkyl group of 4 or a phenyl group (R'), a water- and oil-repellent layer with excellent slipperiness is formed.

In the above formula (1), when α is 1, Rf is preferably a polymer residue containing a monovalent fluoroxyalkylene group (hereinafter sometimes referred to as a fluoroxyalkyl group) represented by the general formula (2) below. do.

(In the formula, p, q, r, and s are each an integer from 0 to 200, p+q+r+s=an integer from 3 to 200, t is an integer from 1 to 3, and each repeating unit is a linear It may be branched, and each repeating unit may be randomly combined.)

In the above formula (1), when α is 2, Rf is a polymer residue containing a divalent fluoroxyalkylene group (hereinafter sometimes referred to as a fluoroxyalkylene group) represented by the following general formula (3): desirable.

(In the formula, p, q, r, and s are each an integer from 0 to 200, p+q+r+s=an integer from 3 to 200, t is an integer from 1 to 3, and each repeating unit is a linear It may be branched, and each repeating unit may be randomly combined.)

In the above formulas (2) and (3), p, q, r, and s are each an integer from 0 to 200, preferably p is an integer from 5 to 100, q is an integer from 5 to 100, and R is an integer from 0 to 100. An integer of 100, s is an integer of 0 to 100, p+q+r+s=3 to 200, preferably an integer of 10 to 100, each repeating unit may be linear or branched, and each Repeating units may be randomly combined. More preferably, p+q is an integer of 10 to 105, especially 15 to 60, and r=s=0. If p+q+r+s is less than the above upper limit, the adhesion and curability are good, and if it is larger than the above lower limit, the characteristics of the fluoropolyether group can be sufficiently exhibited, so it is preferable.

In addition, t is an integer of 1 to 3, preferably 1 or 2, and C _t F _2t may be linear or branched.

As Rf (polymer residue containing a monovalent or divalent fluoroxyalkylene group), the following can be specifically exemplified.

(In the formula, p', q', r', and s' are each integers of 1 or more, and their upper limits are the same as the upper limits of p, q, r, and s. u is an integer from 1 to 24, and v is an integer from 1 to 24. It is an integer of 24 and is a number that satisfies u+v=r. Each repeating unit may be randomly combined.)

In the above formula (1), Y is a 2-6 valent group that may have a siloxane bond ((di)organosiloxane unit, etc.) and/or a silylene group (diorganosilylene group), preferably 2-4. It is more preferably a divalent hydrocarbon group, and does not contain a linking group (ether bond, etc.) with low binding energy in the molecule, so that a coating film with excellent weather resistance and wear resistance can be provided.

As Y, specifically, alkylene groups with 3 to 10 carbon atoms such as propylene groups (trimethylene group, methylethylene group), butylene groups (tetramethylene group, methylpropylene group), and hexamethylene groups, and 6 carbon atoms such as phenylene groups. Alkylene groups containing arylene groups of ~8 (e.g., alkylene/arylene groups of 8-16 carbon atoms, etc.), alkylene groups of 2-10 carbon atoms have a real-alkylene structure (both ends of the alkylene group are diorganic), A divalent group bonded through a silylene group (structure blocked by a silylene group) or a silylene structure (a structure where both ends of the arylene group are blocked by a diorganosilylene group), 2 to 10 silicon atoms, preferably 2 to 2 A 2-6, preferably 2-4 valent group in which an alkylene group is bonded to the bond of five straight-chain organopolysiloxane residues, and a branched group having 3-10 silicon atoms, preferably 3-5. or a 2- to 6-valent, preferably 2- to 4-valent group in which an alkylene group is bonded to the bond of the cyclic organopolysiloxane residue, and more preferably an alkylene group with 3 to 10 carbon atoms, phenyl. An alkylene group with 8 to 16 carbon atoms including a lene group, a divalent group in which alkylene groups with 2 to 10 carbon atoms are bonded to each other through a silalkylene structure or silarylene structure, and 2 to 10 silicon atoms, preferably A divalent to tetravalent group in which an alkylene group having 2 to 10 carbon atoms is bonded to the bond of 2 to 5 linear organopolysiloxane residues, or a branched group having 3 to 10 silicon atoms, preferably 3 to 5 silicon atoms. Alternatively, it is a divalent to tetravalent group in which an alkylene group having 2 to 10 carbon atoms is bonded to the bond of the cyclic organopolysiloxane residue, and more preferably, it is an alkylene group having 3 to 6 carbon atoms.

Here, examples of the silalkylene structure and silarylene structure include those shown below.

(In the formula, R ¹ is an alkyl group with 1 to 4 carbon atoms, such as a methyl group, ethyl group, propyl group, or butyl group, or an aryl group with 6 to 10 carbon atoms, such as a phenyl group. R ¹ may be the same or different. R ² is an alkylene group with 1 to 4 carbon atoms such as methylene group, ethylene group, propylene group (trimethylene group, methylethylene group), and arylene group with 6 to 10 carbon atoms such as phenylene group.)

In addition, linear organopolysiloxane residues having 2 to 10 silicon atoms, preferably 2 to 5, and branched or cyclic divalent to hexavalent residues having 3 to 10 silicon atoms, preferably 3 to 5, Examples of organopolysiloxane residues include those shown below.

(In the formula, R ¹ is the same as above. g is an integer of 1 to 9, preferably an integer of 1 to 4, h is an integer of 2 to 6, preferably an integer of 2 to 4, and j is an integer of 0 to 4. It is an integer of 8, preferably 0 or 1, h+j is an integer of 3 to 10, preferably an integer of 3 to 5, and k is an integer of 1 to 3, preferably 2 or 3.)

Specific examples of Y include the following groups.

In the above formula (1), X is a hydroxyl group or a hydrolyzable group that may be different from each other. Examples of such Acyloxy groups with 2 to 10 carbon atoms such as substituted alkoxy groups and acetoxy groups, alkenyloxy groups with 2 to 10 carbon atoms such as isopropenoxy groups, halogen atoms such as chloro atoms, bromo atoms, and iodo atoms, etc. I can hear it. Among them, methoxy group, ethoxy group, isopropenoxy group, and chloro atom are suitable.

In the formula (1), R is an alkyl group with 1 to 4 carbon atoms such as methyl, ethyl, propyl, butyl, or a phenyl group, and methyl is particularly suitable.

n is an integer of 1 to 3, preferably 2 or 3, and 3 is more preferable from the viewpoint of reactivity and adhesion to the substrate.

m is an integer of 1 to 5. If it is less than 1, the adhesion to the substrate decreases, and if it is more than 6, the terminal alkoxy value is too high and adversely affects performance. Therefore, it is preferably an integer of 1 to 3, and 1 is especially preferable. do.

In the above formula (1), Q is a divalent organic group that may have a siloxane bond and/or a silylene group, and is particularly preferably a divalent organic group represented by the following formula (4).

(Wherein, R'' is an alkylene group or carbonyl group having 1 to 10 carbon atoms which may have any one of ketone, ester, amide, ether, sulfide, amine, and phenylene, and W is 2 to 40 silicon atoms. straight-chain divalent organo(poly)siloxane residues, a straight-chain silicon alkylene group that may have a siloxane bond with 3 to 40 silicon atoms bonded through an alkylene group with 1 to 4 carbon atoms, and phenylene It is a divalent group selected from a straight-chain siloxane group that may have a siloxane bond of 3 to 40 silicon atoms and may be bonded through an alkylene group of 1 to 4 carbon atoms, and is an organo(poly)siloxane group. The sein residue, silalkylene group, and silarylene group may each be single or mixed, β is 0 or 1, γ is 0 or 1, and β+γ is 1 or 2.)

In the above formula (4), R'' specifically represents the carbon number of methylene group, ethylene group, propylene group (trimethylene group, methylethylene group), butylene group (tetramethylene group, methylpropylene group, hexamethylene group, etc. Alkylene groups with 1 to 10 carbon atoms, divalent groups in which alkylene groups with 1 to 10 carbon atoms are bonded through arylene groups such as ketones, esters, amides, ethers, sulfides, amines, and phenylene groups with 6 to 8 carbon atoms, and carbonyl groups. and is preferably an alkylene group having 1 to 4 carbon atoms, a divalent group where the alkylene groups having 1 to 4 carbon atoms are bonded to each other through an ether, or a carbonyl group.

Specific examples of R'' include the following groups.

In the above formula (4), the linear silarylene group of W, the silarylene structure in the linear silarylene group, and the silarylene structure are specifically shown below.

(In the formula, R ¹ is an alkyl group with 1 to 4 carbon atoms, such as a methyl group, ethyl group, propyl group, or butyl group, or an aryl group with 6 to 10 carbon atoms, such as a phenyl group. R ¹ may be the same or different. R ² is an alkylene group with 1 to 4 carbon atoms such as methylene group, ethylene group, propylene group (trimethylene group, methylethylene group), and arylene group with 6 to 10 carbon atoms such as phenylene group.)

In addition, the linear divalent organopolysiloxane residues having 2 to 40 silicon atoms, preferably 3 to 10 silicon atoms, include those shown below.

(In the formula, R ¹ is the same as above. f is an integer from 1 to 39, preferably an integer from 2 to 9.)

Here, as W, those shown below can be exemplified.

In the formula (1), R' is a monovalent fluoroalkyl group (for example, a fluoroalkyl group with 1 to 6 carbon atoms), a polymer residue containing a monovalent fluoroxyalkylene group, a methyl group with 1 to 4 carbon atoms, or an ethyl group. , an alkyl group such as a propyl group or a butyl group, or a phenyl group, and among these, a polymer residue containing a monovalent fluoroxyalkylene group or an alkyl group having 1 to 4 carbon atoms is preferable, and a polymer residue containing a monovalent fluoroxyalkylene group is particularly suitable. .

In the above formula (1), when R' is a monovalent fluoroxyalkylene group-containing polymer residue, R' is preferably a monovalent fluoroxyalkylene group-containing polymer residue represented by the following general formula (2): do.

(In the formula, p, q, r, and s are each an integer from 0 to 200, p+q+r+s=an integer from 3 to 200, t is an integer from 1 to 3, and each repeating unit is a linear It may be branched, and each repeating unit may be randomly combined.)

Examples of the fluoropolyether group-containing polymer-modified silane represented by the above formula (1) include those represented by the following formula. In addition, in each formula, the number of repetitions (or degree of polymerization) of each repeating unit constituting the fluoroxyalkyl group or fluoroxyalkylene group can be any number that satisfies the above formulas (2) and (3). will be.

(In the formula, p1 is an integer from 5 to 100, q1 is an integer from 5 to 100, and p1+q1 is an integer from 10 to 105.)

Examples of methods for preparing the fluoropolyether group-containing polymer-modified silane expressed by the above formula (1) and where α is 1 include the following methods.

A polymer containing a fluoroxyalkyl group having two olefin moieties at one end of the molecular chain (i.e., a polymer having a polymer residue containing a monovalent fluoroxyalkylene group and two olefin moieties at one end of the molecular chain) is mixed with a solvent, for example. , 1,3-bis (trifluoromethyl) benzene, etc. are dissolved in a fluorine-based solvent, and an organosilicon compound having a SiH group and a hydrolyzable end group in the molecule, such as trimethoxysilane, is used as a hydrosilylation reaction catalyst, For example, in the presence of a toluene solution of the chloroplatinic acid/vinylsiloxane complex, at a temperature of 40 to 120°C, preferably 60 to 100°C, more preferably about 80°C, for 1 to 72 hours, preferably 20°C. The hydrosilylation addition reaction is carried out and aged under conditions of ~36 hours, more preferably about 24 hours.

In addition, as another method for preparing the fluoropolyether group-containing polymer-modified silane expressed by the above formula (1) when α is 1, the following method can be mentioned, for example.

A polymer containing a fluoroxyalkyl group having two olefin moieties at one end of the molecular chain is dissolved in a solvent such as a fluorine-based solvent such as 1,3-bis(trifluoromethyl)benzene, trichlorosilane, etc. An organosilicon compound having a SiH group and a hydrolyzable end group (for example, a halogen atom bonded to a silicon atom such as a chlorine atom) in the molecule is used as a hydrosilylation reaction catalyst, for example, a chloroplatinic acid/vinylsiloxane complex. in the presence of a toluene solution, at a temperature of 40 to 120°C, preferably 60 to 100°C, more preferably about 80°C, for 1 to 72 hours, preferably 20 to 36 hours, more preferably about 24 hours. After performing a hydrosilylation addition reaction and aging under the conditions, the substituents (halogen atoms, etc.) on the silyl group are converted into hydrolyzable groups such as alkoxy groups such as methoxy groups, for example.

Additionally, instead of the organosilicon compound having a SiH group and a hydrolyzable end group in the molecule, an organosilicon compound containing a SiH group without a hydrolyzable end group may be used. In this case, as the organosilicon compound, a hydrolyzable end group is present in the molecule. An organosilicon compound having no terminal group and having two or more SiH groups is used. At that time, in the same manner as above, a polymer containing a fluoroxyalkyl group having two olefin moieties at one end of the molecular chain and an organosilicon compound having two or more SiH groups without a hydrolyzable end group in the molecule were mixed in equal molar amounts. After performing a hydrosilylation addition reaction to produce a reactant (intermediate) having two SiH groups remaining at one end of the molecular chain, the SiH group at the polymer end of this reaction product (intermediate) and the olefin moiety in the molecule such as allyltrimethoxysilane and an organosilicon compound having a hydrolyzable end group in the presence of a hydrosilylation reaction catalyst, for example, a toluene solution of chloroplatinic acid/vinylsiloxane complex, at 40 to 120° C., preferably 60 to 100° C., more preferably. The hydrosilylation addition reaction is further carried out and aged at a temperature of about 80°C for 1 to 72 hours, preferably 20 to 36 hours, more preferably about 24 hours.

Here, examples of the fluoroxyalkyl group-containing polymer having two olefin moieties at one end of the molecular chain include a fluoroxyalkyl group-containing polymer represented by the following general formula (5).

(In the formula, Rf, Q, and R' are the same as above. Z is a divalent hydrocarbon group.)

In the above formula (5), Z is a divalent hydrocarbon group, preferably a divalent hydrocarbon group having 1 to 8 carbon atoms, especially 1 to 4 carbon atoms, and specifically, methylene group, ethylene group, propylene group (trimethylene group, Alkylene groups including alkylene groups with 1 to 8 carbon atoms such as methylethylene group), butylene groups (tetramethylene group, methylpropylene group), hexamethylene group and octamethylene group, and arylene groups with 6 to 8 carbon atoms such as phenylene group. (For example, alkylene/arylene groups having 7 to 8 carbon atoms, etc.). Z is preferably a straight-chain alkylene group having 1 to 4 carbon atoms.

As the fluoroxyalkyl group-containing polymer represented by formula (5), those shown below are preferably exemplified. In addition, in each formula, the repetition number (or degree of polymerization) of each repeating unit constituting the fluoroxyalkyl group can be any number that satisfies formula (2) in Rf above.

(In the formula, r1 is an integer from 1 to 100, and p1, q1, and p1+q1 are the same as above.)

As a method for preparing the fluoroxyalkyl group-containing polymer represented by the above formula (5), for example, a fluoroxyalkyl group-containing polymer (i.e., a monovalent fluoropolymer) having a hydroxyl group at one end of the molecular chain and two olefin moieties is used. (a polymer having a lowoxyalkylene group-containing polymer residue and two olefin moieties and a hydroxyl group at one end of the molecular chain) and hydrosilane in the presence of a dehydrogenation catalyst at 0 to 60°C, preferably 15 to 35°C, using a solvent. More preferably, the dehydrogenation reaction is performed at a temperature of about 25°C for 10 minutes to 24 hours, preferably 30 minutes to 2 hours, and more preferably about 1 hour.

In addition, as another method of preparing the fluoroxyalkyl group-containing polymer represented by the above formula (5), a fluoroxyalkyl group-containing polymer (i.e., a monovalent fluoropolymer) having a hydroxyl group at one end of the molecular chain and two olefin moieties is used. a polymer having a lowoxyalkylene group-containing polymer residue and two olefin moieties and a hydroxyl group at one end of the molecular chain) and, for example, a polymer containing a fluoroxyalkyl group having an acid fluoride at one end of the molecular chain in the presence of a base, Using a solvent, at a temperature of 0 to 100°C, preferably 25 to 80°C, more preferably 60°C, under conditions of 1 to 48 hours, preferably 5 to 36 hours, more preferably about 20 hours. A dehalogenation (dehydrogenation) reaction is performed.

Here, the fluoroxyalkyl group-containing polymer having an acid fluoride at one end of the molecular chain is a group having at one end of the molecular chain, and in addition to the acid fluoride described above, other acid halides (for example, acid chloride) and acid anhydrides. , esters (for example, alkyl esters such as methyl ester), carboxylic acids, etc. can also be used.

Specific examples of perfluoroxyalkyl group-containing polymers having these groups (acid halide, acid anhydride, ester, carboxylic acid, etc.) at one end of the molecular chain include those shown below.

(In the formula, p1, q1, p1+q1 are the same as above.)

The addition amount of the polymer containing a fluoroxyalkyl group having a functional group such as acid fluoride at one end of the molecular chain is 0.5 to 1 equivalent of the reactive end group (hydroxyl group) of the polymer containing a fluoroxyalkyl group having a hydroxyl group at one end of the molecular chain. It can be used in an amount of 1 equivalent, more preferably 0.8 to 1 equivalent, and even more preferably about 0.9 equivalent.

As the base used in preparing the fluoroxyalkyl group-containing polymer represented by formula (5), for example, amines or alkali metal bases can be used. Specifically, amines include triethylamine and diisopropyl. Examples include ethylamine, pyridine, DBU, and imidazole. In alkali metal bases, sodium hydroxide, potassium hydroxide, sodium hydride, potassium hydride, alkyl lithium, t-butoxypotassium, lithium diisopropylamide, lithium bis(trimethylsilyl)amide, sodium bis(trimethylsilyl)amide, Potassium bis(trimethylsilyl)amide, etc. can be mentioned.

The amount of base used is 1 to 10 equivalents, more preferably 1 to 3 equivalents, and even more preferably about 2 equivalents, based on 1 equivalent of the reactive end group of the polymer containing a fluoroxyalkyl group having a hydroxyl group at one end of the molecular chain. You can.

In the preparation of the fluoroxyalkyl group-containing polymer represented by the above formula (5), the solvent used is preferably a fluorine-based solvent, and the fluorine-based solvent is 1,3-bis(trifluoromethyl)benzene or trifluoromethylbenzene. , Methylnonafluorobutylether, Methylnonafluoroisobutylether, Ethylnonafluorobutylether, Ethylnonafluoroisobutylether, 1,1,1,2,3,4,4,5 Hydrofluoroether (HFE)-based solvents such as 5,5-decafluoro-3-methoxy-2-(trifluoromethyl)pentane (manufactured by 3M, brand name: Novec series), fully fluorinated compounds and perfluoro-based solvents (manufactured by 3M, brand name: Fluorinaut series), which are composed of.

The amount of solvent used is 10 to 300 parts by mass, preferably 50 to 150 parts by mass, more preferably about 100 parts by mass, based on 100 parts by mass of the polymer containing a fluoroxyalkylene group having two olefin moieties at one end of the molecular chain. You can use it.

Subsequently, the reaction is stopped, and the water layer and the fluorine solvent layer are 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 fluoroxyalkyl group-containing polymer represented by formula (5).

Here, the raw material used in the preparation of the fluoroxyalkyl group-containing polymer represented by formula (5) is a fluoroxyalkyl group-containing polymer that has a hydroxyl group at one end of the molecular chain and has two olefin moieties, specifically: , the ones shown below can be mentioned.

(In the formula, r1, p1, q1, p1+q1 are the same as above.)

As a method for preparing the polymer containing a fluoroxyalkyl group having a hydroxyl group at one end of the molecular chain and two olefin moieties as the raw material, for example, an acid fluoride group (-C(=O)) is added to one end of the molecular chain. -F), a perfluoroxyalkyl group-containing polymer, a Grignard reagent having an olefin moiety as a nucleating agent, and a solvent such as 1,3-bis(trifluoromethyl)benzene and tetrahydrofuran are mixed. and aging at 0 to 80°C, preferably 50 to 70°C, more preferably about 60°C, for 1 to 6 hours, preferably 3 to 5 hours, more preferably about 4 hours, thereby forming a molecular chain fragment. A hydroxyl group is introduced along with two olefin moieties at the terminal.

Here, the perfluoroxyalkyl group-containing polymer as a raw material used in the preparation of the fluorooxyalkyl group-containing polymer having a hydroxyl group at one end of the molecular chain and two olefin moieties has a group at one end of the molecular chain. , In addition to the above-mentioned acid fluoride, other acid halides (such as acid chloride), acid anhydrides, esters, carboxylic acids, amides, etc. can also be used.

Specific examples of perfluoroxyalkyl group-containing polymers having these groups at one end of the molecular chain include those shown below.

(In the formula, p1, q1, p1+q1 are the same as above.)

Examples of nucleophilic agents used in the preparation of a fluoroxyalkyl group-containing polymer having a hydroxyl group at one end of the molecular chain and two olefin moieties include allyl magnesium halide, 3-butenyl magnesium halide, 4-pentenyl magnesium halide, 5 -Hexenylmagnesium halide, etc. can be used. It is also possible to use the corresponding lithium reagent.

The nucleophilic agent may be used in an amount of 2 to 5 equivalents, more preferably 2.5 to 3.5 equivalents, and still more preferably about 3 equivalents, per 1 equivalent of the reactive end group of the perfluoroxyalkyl group-containing polymer.

In addition, solvents used in the preparation of the fluorooxyalkyl group-containing polymer, which has a hydroxyl group at one end of the molecular chain and two olefin moieties, are fluorine-based solvents such as 1,3-bis(trifluoromethyl)benzene and tri. Fluoromethylbenzene, methylnonafluorobutyl ether, methylnonafluoroisobutyl ether, ethylnonafluorobutyl ether, ethylnonafluoroisobutyl ether, 1,1,1,2,3,4 Hydrofluoroether (HFE)-based solvents such as 4,5,5,5-decafluoro-3-methoxy-2-(trifluoromethyl)pentane (manufactured by 3M, brand name: Novec series), and perfluoro-based solvents (manufactured by 3M, brand name: Fluorinaut series) composed of fully fluorinated compounds. Additionally, organic solvents include tetrahydrofuran, mono-ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, and dioxane. Ether-based solvents such as these can be used.

The amount of solvent used can be 10 to 300 parts by mass, preferably 100 to 200 parts by mass, more preferably about 150 parts by mass, based on 100 parts by mass of the perfluoroxyalkyl group-containing polymer.

Subsequently, the reaction is stopped, and the water layer and the fluorine solvent layer are 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 fluoroxyalkyl group-containing polymer having a hydroxyl group at one end of the molecular chain.

Hydrosilanes used in the preparation of the fluoroxyalkyl group-containing polymer represented by formula (5) include polydimethylsiloxane terminal hydrosilanes having 2 to 40 silicon atoms in which one end group is sealed with an alkyl group; Examples include polydimethylsiloxane-terminated hydrosilanes having 2 to 40 silicon atoms in which one end of the short term is sealed with a fluoroalkyl group or a fluoroxyalkyl group.

Specifically, the hydrosilane used in the preparation of the fluoroxyalkyl group-containing polymer represented by formula (5) includes those shown below.

(In the formula, p1, q1, p1+q1 are the same as above.)

The amount of the hydrosilane used is 1 to 5 equivalents, more preferably 1 to 2 equivalents, based on 1 equivalent of the reactive end group of the fluoroxyalkyl group-containing polymer, which has a hydroxyl group at one end of the molecular chain and two olefin moieties. The equivalent amount can be used, more preferably about 1.2 equivalents.

As a dehydrogenation catalyst used in the preparation of the fluoroxyalkyl group-containing polymer represented by formula (5), for example, platinum group metal catalysts such as rhodium, palladium, and ruthenium, boron catalysts, etc. can be used, and specifically, tetra Platinum group metal catalysts such as kiss(triphenylphosphine)palladium and chlorotris(triphenylphosphine)rhodium, and boron catalysts such as tris(pentafluorophenyl)borane, etc. can be mentioned.

The amount of the dehydrogenation catalyst used is 0.01 to 0.0005 equivalents, more preferably 0.007 to 0.001 equivalents, based on 1 equivalent of the reactive end group of the fluoroxyalkyl group-containing polymer, which has a hydroxyl group at one end of the molecular chain and two olefin moieties. , more preferably about 0.005 equivalent.

The solvent used in the preparation of the fluoroxyalkyl group-containing polymer represented by formula (5) is a fluorine-based solvent, such as fluorinated aromatic hydrocarbons such as 1,3-bis(trifluoromethyl)benzene and trifluoromethylbenzene. Solvent, methylnonafluorobutyl ether, methylnonafluoroisobutyl ether, ethylnonafluorobutyl ether, ethylnonafluoroisobutyl ether, 1,1,1,2,3,4,4, Hydrofluoroether (HFE) solvents such as 5,5,5-decafluoro-3-methoxy-2-(trifluoromethyl)pentane (manufactured by 3M, brand name: Novec series), fully fluorinated and perfluoro-based solvents (manufactured by 3M, brand name: Fluorinaut series) composed of compounds. Also, as an organic solvent, tetrahydrofuran, monoethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, diox. Ether-based solvents such as Cein can be used.

The amount of solvent used is 10 to 300 parts by mass, preferably 50 to 150 parts by mass, more preferably 50 to 150 parts by mass, based on 100 parts by mass of the polymer containing a fluoroxyalkyl group having a hydroxyl group at one end of the molecular chain and two olefin moieties. Approximately 100 parts by mass can be used.

Subsequently, the reaction is stopped, and the water layer and the fluorine solvent layer are 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 fluoroxyalkyl group-containing polymer represented by formula (5).

In the preparation of the fluoropolyether group-containing polymer-modified silane represented by the above formula (1) when α is 1, the solvent used is preferably a fluorine-based solvent, and the fluorine-based solvent is 1,3-bis (tri Fluoromethyl)benzene, trifluoromethylbenzene, methylnonafluorobutyl ether, methylnonafluoroisobutyl ether, ethylnonafluorobutyl ether, ethylnonafluoroisobutyl ether, 1,1, Hydrofluoroether (HFE)-based solvents such as 1,2,3,4,4,5,5,5-decafluoro-3-methoxy-2-(trifluoromethyl)pentane (manufactured by 3M) , brand name: Novec series), and a perfluoro-based solvent consisting of a fully fluorinated compound (manufactured by 3M, brand name: Fluorinaut series).

The amount of solvent used is 10 to 300 parts by mass, preferably 50 to 150 parts by mass, more preferably about 100 parts by mass, based on 100 parts by mass of the polymer containing a fluoroxyalkyl group having two olefin moieties at one end of the molecular chain. You can use it.

In addition, in the preparation of a fluoropolyether group-containing polymer-modified silane represented by formula (1) when α is 1, the organosilicon compound having a SiH group and a hydrolyzable terminal group in the molecule is of the following general formula (6) Compounds represented by ) to (9) are preferable.

( ^Wherein , ^{R ,} It is an integer of ~4, and i+j is an integer of 2~9.)

Here, the divalent hydrocarbon group of R ³ having 2 to 8 carbon atoms, preferably 2 to 3 carbon atoms, includes methylene group, ethylene group, propylene group (trimethylene group, methylethylene group), butylene group (tetramethylene group, methylpropylene) group), alkylene groups such as hexamethylene group and octamethylene group, arylene groups such as phenylene group, or combinations of two or more of these groups (alkylene/arylene group, etc.), and among these, ethylene group, tri A methylene group is preferred.

Among these molecules, organosilicon compounds having a SiH group and a hydrolyzable end group include, for example, trimethoxysilane, triethoxysilane, tripropoxysilane, triisopropoxysilane, and tributoxysilane. Phosphorus, triisopropenoxysilane, triacetoxysilane, trichlorosilane, tribromosilane, triiodosilane, and the following organosilicon compounds can be mentioned.

In the preparation of a fluoropolyether group-containing polymer-modified silane represented by formula (1) when α is 1, a fluorooxyalkyl group-containing polymer having two olefin moieties at one end of the molecular chain and SiH in the molecule When reacting an organosilicon compound having a group and a hydrolyzable end group, the amount of the organosilicon compound having a SiH group and a hydrolyzable end group in the molecule is a fluoroxyalkyl group having two olefin moieties at one end of the molecular chain. Based on 1 equivalent of the reactive end group of the polymer, 2 to 6 equivalents can be used, more preferably 2.2 to 3.5 equivalents, and even more preferably about 3 equivalents.

In addition, in the preparation of the fluoropolyether group-containing polymer-modified silane represented by formula (1) when α is 1, the organosilicon compound having no hydrolyzable terminal group in the molecule and having two or more SiH groups is Compounds represented by the following general formulas (10) to (12) are preferred.

(In the formula, R ¹ , R ² , g, j, and i are the same as above.)

Examples of organosilicon compounds that do not have a hydrolyzable terminal group and have two or more SiH groups in such molecules include those shown below.

In the preparation of a fluoropolyether group-containing polymer-modified silane represented by formula (1) when α is 1, a fluorooxyalkyl group-containing polymer having two olefin moieties at one end of the molecular chain and a hydroxyl group in the molecule are used. When reacting an organosilicon compound that does not have a degradable end group and has two or more SiH groups, the amount of the organosilicon compound that does not have a hydrolyzable end group and has two or more SiH groups in the molecule is determined by adding an olefin at one end of the molecular chain. It can be used in an amount of 5 to 20 equivalents, more preferably 7.5 to 12.5 equivalents, and even more preferably about 10 equivalents, per equivalent of the reactive end group of the fluoroxyalkyl group-containing polymer having two sites.

In addition, in the preparation of a fluoropolyether group-containing polymer-modified silane represented by formula (1) when α is 1, the organosilicon compound having an olefin moiety and a hydrolyzable terminal group in the molecule is the following general formula (13) ) Compounds represented by ) are preferred.

(In the formula, R,

In the formula (13), V is a single bond or a divalent hydrocarbon group having 1 to 6 carbon atoms, and specifically, methylene group, ethylene group, propylene group (trimethylene group, methylethylene group), butylene group (tetramethylene group, methylpropylene group), alkylene group such as hexamethylene group, phenylene group, etc. V is preferably a single bond or a methylene group.

In the preparation of a fluoropolyether group-containing polymer-modified silane represented by formula (1) when α is 1, a fluorooxyalkyl group-containing polymer having two olefin moieties at one end of the molecular chain and a hydroxyl group in the molecule are used. When reacting a reactant with an organosilicon compound that does not have a decomposable end group and has two or more SiH groups, and an organosilicon compound that has an olefin moiety and a hydrolyzable end group in the molecule, an olefin moiety and a hydrolyzable end group in the molecule The amount of the organosilicon compound used depends on the reactivity of the reactant between a polymer containing a fluoroxyalkyl group having two olefin moieties at one end of the molecular chain and an organosilicon compound having two or more SiH groups without a hydrolyzable end group in the molecule. Based on 1 equivalent of the terminal group, 2 to 6 equivalents can be used, more preferably 2.2 to 3.5 equivalents, and even more preferably about 3 equivalents.

In the preparation of a fluoropolyether group-containing polymer-modified silane represented by formula (1) when α is 1, the hydrosilylation reaction catalyst includes platinum black, chloroplatinic acid, an alcohol modification of chloroplatinic acid, chloroplatinic acid, and Complexes with olefins, aldehydes, vinylsiloxanes, acetylene alcohols, etc., and platinum group metal catalysts such as tetrakis(triphenylphosphine)palladium and chlorotris(triphenylphosphine)rhodium. Preferably, it is a platinum-based compound such as a vinylsiloxane coordination compound.

The amount of hydrosilylation reaction catalyst to be used is a polymer containing a fluoroxyalkyl group having two olefin moieties at one end of the molecular chain, or an organosilicon compound having two or more SiH groups without a hydrolyzable end group in the molecule, and this polymer. It is used in an amount of 0.1 to 100 ppm, more preferably 1 to 50 ppm, in terms of transition metal conversion (mass), relative to the mass of the reactant.

Thereafter, the solvent and unreacted substances are distilled off under reduced pressure to obtain the target compound.

For example, a compound represented by the formula below as a fluoroxyalkyl group-containing polymer having two olefin moieties at one end of the molecular chain.

When trimethoxysilane is used as an organosilicon compound having a SiH group and a hydrolyzable end group in the molecule, a compound represented by the following formula is obtained.

Examples of methods for preparing the fluoropolyether group-containing polymer-modified silane expressed by the above formula (1) and where α is 2 include the following methods.

A fluoroxyalkylene group-containing polymer having two olefin moieties at both ends of the molecular chain (i.e., a polymer having a divalent fluoroxyalkylene group-containing polymer residue and two olefin moieties each at both ends of the molecular chain), An organosilicon compound having a SiH group and a hydrolyzable end group in a molecule such as trimethoxysilane is dissolved in a solvent, for example, a fluorine-based solvent such as 1,3-bis(trifluoromethyl)benzene, and hydrolyzed. In the presence of a silylation reaction catalyst, for example, a toluene solution of chloroplatinic acid/vinylsiloxane complex, at a temperature of 40 to 120°C, preferably 60 to 100°C, more preferably about 80°C, for 1 to 72 hours. , preferably aged for 20 to 36 hours, more preferably for about 24 hours.

Additionally, instead of the organosilicon compound having a SiH group and a hydrolyzable end group in the molecule, an organosilicon compound containing a SiH group without a hydrolyzable end group may be used. In this case, as the organosilicon compound, a hydrolyzable end group is present in the molecule. An organosilicon compound having no short period and having two or more SiH groups is used. At that time, in the same manner as above, equimolar amounts of a fluoroxyalkylene group-containing polymer having two olefin moieties at both ends of the molecular chain and an organosilicon compound having two or more SiH groups and no hydrolyzable end groups in the molecule were added. After reacting as above to produce a reactant (intermediate) having two SiH groups remaining at both ends of the molecular chain, the SiH group at the polymer end of this reaction product (intermediate) and the olefin moiety and hydroxide in molecules such as allyltrimethoxysilane are An organosilicon compound having a decomposable end group is reacted in the presence of a hydrosilylation reaction catalyst, for example, a toluene solution of chloroplatinic acid/vinylsiloxane complex, at 40 to 120° C., preferably 60 to 100° C., more preferably about It is aged at a temperature of 80°C for 1 to 72 hours, preferably 20 to 36 hours, and more preferably about 24 hours.

Here, examples of the fluoroxyalkylene group-containing polymer having two olefin moieties at both ends of the molecular chain include a fluoroxyalkylene group-containing polymer represented by the following general formula (14).

(In the formula, Rf, Z, Q, and R' are the same as above.)

As the fluoroxyalkylene group-containing polymer represented by formula (14), those shown below are preferably exemplified. In addition, in each formula, the repetition number (or degree of polymerization) of each repeating unit constituting the fluoroxyalkylene group can be any number that satisfies formula (3) in Rf above.

(In the formula, p1, q1, p1+q1 are the same as above.)

As a method for preparing a fluoroxyalkylene group-containing polymer represented by the above formula (14), for example, a fluoroxyalkylene group having a hydroxyl group at both ends of the molecular chain and two olefin moieties at both ends of the molecular chain is used. A polymer containing a divalent fluoroxyalkylene group (i.e., a polymer having a divalent fluoroxyalkylene group-containing polymer residue and two olefin moieties and a hydroxyl group at each end of the molecular chain) and hydrosilane are reacted at 0 to 60°C using a solvent in the presence of a dehydrogenation catalyst. , the dehydrogenation reaction is performed at a temperature of preferably 15 to 35°C, more preferably about 25°C, for 10 minutes to 24 hours, preferably 30 minutes to 2 hours, and more preferably about 1 hour.

In addition, another method of preparing a fluoroxyalkylene group-containing polymer represented by the above formula (14) is a fluoroxyalkylene group containing hydroxyl groups at both ends of the molecular chain and two olefin moieties at both ends of the molecular chain. Polymers (i.e., polymers containing a divalent fluoroxyalkylene group-containing polymer residue and two olefin moieties and a hydroxyl group at each end of the molecular chain) and, for example, fluorooxyalkyl groups having an acid fluoride at one end of the molecular chain. The containing polymer is reacted using a solvent in the presence of a base at a temperature of 0 to 100°C, preferably 25 to 80°C, more preferably 60°C, for 1 to 48 hours, preferably 5 to 36 hours, more preferably. Specifically, a dehalogenation (dehydrogenation) reaction is performed under conditions of about 20 hours.

Here, the fluoroxyalkyl group-containing polymer having an acid fluoride at one end of the molecular chain can be a group having one end of the molecular chain, and in addition to the acid fluoride described above, acid halides, acid anhydrides, esters, carboxylic acids, etc. can also be used.

Specific examples of perfluoroxyalkyl group-containing polymers having these groups (acid halide, acid anhydride, ester, carboxylic acid, etc.) at one end of the molecular chain include those shown below.

(In the formula, p1, q1, p1+q1 are the same as above.)

The addition amount of the polymer containing a fluoroxyalkylene group having an acid fluoride at one end of the molecular chain is 0.5 to 1 per equivalent of the reactive end group (hydroxyl group) of the polymer containing a fluoroxyalkylene group having a hydroxyl group at both ends of the molecular chain. The equivalent amount can be used, more preferably 0.8 to 1 equivalent, and even more preferably about 0.9 equivalent.

As the base used in preparing the fluoroxyalkylene group-containing polymer represented by formula (14), for example, amines or alkali metal bases can be used. Specifically, amines include triethylamine and diiso. Propylethylamine, pyridine, DBU, imidazole, etc. can be mentioned. In alkali metal bases, sodium hydroxide, potassium hydroxide, sodium hydride, potassium hydride, alkyl lithium, t-butoxypotassium, lithium diisopropylamide, lithium bis(trimethylsilyl)amide, sodium bis(trimethylsilyl)amide, Potassium bis(trimethylsilyl)amide, etc. can be mentioned.

The amount of base used is 1 to 10 equivalents, more preferably 1 to 3 equivalents, and still more preferably about 2 equivalents, based on 1 equivalent of the reactive end group of the fluoroxyalkylene group-containing polymer having hydroxyl groups at both ends of the molecular chain. You can use it.

In the preparation of the fluoroxyalkylene group-containing polymer represented by the above formula (14), the solvent used is preferably a fluorine-based solvent, and examples of the fluorine-based solvent include 1,3-bis(trifluoromethyl)benzene and trifluoromethyl. Benzene, methylnonafluorobutyl ether, methylnonafluoroisobutyl ether, ethylnonafluorobutyl ether, ethylnonafluoroisobutyl ether, 1,1,1,2,3,4,4, Hydrofluoroether (HFE) solvents such as 5,5,5-decafluoro-3-methoxy-2-(trifluoromethyl)pentane (manufactured by 3M, brand name: Novec series), fully fluorinated and perfluoro-based solvents (manufactured by 3M, brand name: Fluorinaut series) composed of compounds.

The amount of solvent used is 10 to 300 parts by mass, preferably 50 to 150 parts by mass, more preferably about 100 parts by mass, based on 100 parts by mass of the polymer containing a fluoroxyalkylene group having hydroxyl groups at both ends of the molecular chain. You can.

Subsequently, the reaction is stopped, and the water layer and the fluorine solvent layer are 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 fluoroxyalkylene group-containing polymer represented by formula (14).

Here, a fluoroxyalkylene group-containing polymer having hydroxyl groups at both ends of the molecular chain and two olefin moieties at both ends of the molecular chain used in the preparation of the fluoroxyalkylene group-containing polymer represented by formula (14). Specifically, those shown below can be mentioned.

(In the formula, p1, q1, p1+q1 are the same as above.)

Here, a method for preparing a fluoroxyalkylene group-containing polymer having a hydroxyl group at both ends of the molecular chain and two olefin moieties at both ends of the molecular chain includes, for example, adding an acid fluoride group to both ends of the molecular chain. A polymer containing a perfluoroxyalkylene group having (-C(=O)-F), a Grignard reagent having an olefin moiety as a nucleating agent, and a solvent such as 1,3-bis(trifluoromethyl ) Benzene and tetrahydrofuran are mixed, and incubated at 0 to 80°C, preferably 50 to 70°C, more preferably about 60°C, for 1 to 6 hours, preferably 3 to 5 hours, more preferably about By aging for 4 hours, hydroxyl groups are introduced along with two olefin moieties at both ends of the molecular chain.

Here, the perfluoroxyalkylene group-containing polymer is a group having groups at both ends of the molecular chain, and in addition to the acid fluoride described above, acid halides, acid anhydrides, esters, carboxylic acids, amides, etc. can be used.

Specific examples of perfluoroxyalkylene group-containing polymers having these groups at both ends of the molecular chain include those shown below.

(In the formula, p1, q1, p1+q1 are the same as above.)

Examples of nucleophilic agents used in the preparation of the fluoroxyalkylene group-containing polymer having hydroxyl groups at both ends of the molecular chain include allyl magnesium halide, 3-butenyl magnesium halide, 4-pentenyl magnesium halide, and 5-hexenyl magnesium halide. You can use it. It is also possible to use the corresponding lithium reagent.

The nucleophilic agent can be used in an amount of 4 to 10 equivalents, more preferably 5 to 7 equivalents, and even more preferably about 6 equivalents, per equivalent of the reactive end group of the perfluoroxyalkylene group-containing polymer.

In addition, solvents used in the preparation of the fluoroxyalkylene group-containing polymer having hydroxyl groups at both ends of the molecular chain include fluorine-based solvents such as 1,3-bis(trifluoromethyl)benzene, trifluoromethylbenzene, and methylnona. Fluorobutyl ether, methylnonafluoroisobutyl ether, ethylnonafluorobutyl ether, ethylnonafluoroisobutyl ether, 1,1,1,2,3,4,4,5,5, It consists of a hydrofluoroether (HFE)-based solvent such as 5-decafluoro-3-methoxy-2-(trifluoromethyl)pentane (manufactured by 3M, brand name: Novec series), and a fully fluorinated compound. and perfluoro-based solvents (manufactured by 3M, brand name: Fluorinaut series). Additionally, organic solvents include tetrahydrofuran, monoethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, and dioxane. Ether-based solvents such as these can be used.

The amount of solvent used can be 10 to 300 parts by mass, preferably 100 to 200 parts by mass, more preferably about 150 parts by mass, based on 100 parts by mass of the perfluoroxyalkylene group-containing polymer.

Subsequently, the reaction is stopped, and the water layer and the fluorine solvent layer are 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 fluoroxyalkylene group-containing polymer having hydroxyl groups at both ends of the molecular chain.

Hydrosilanes used in the preparation of the fluoroxyalkylene group-containing polymer represented by formula (14) include polydimethylsiloxane-terminated hydrosilanes having 2 to 40 silicon atoms in which one end group is sealed with an alkyl group; and polydimethylsiloxane-terminated hydrosilanes having 2 to 40 silicon atoms in which one of the terminal groups is sealed with a fluoroalkyl group or a fluoroxyalkyl group.

The amount of hydrosilane used is 1 to 5 equivalents per equivalent of the reactive end group of the fluoroxyalkylene group-containing polymer, which has a hydroxyl group at one end of the molecular chain and two olefin moieties at both ends of the molecular chain. Typically, 1 to 2 equivalents can be used, and more preferably, about 1.2 equivalents can be used.

As a dehydrogenation catalyst that can be used in the preparation of the fluoroxyalkylene group-containing polymer represented by formula (14), for example, platinum group metal catalysts such as rhodium, palladium, and ruthenium, boron catalysts, etc. can be used, and specifically, , platinum group metal catalysts such as tetrakis(triphenylphosphine)palladium and chlorotris(triphenylphosphine)rhodium, and boron catalysts such as tris(pentafluorophenyl)borane.

The amount of the dehydrogenation catalyst used is 0.01 to 0.0005 equivalents, more preferably 0.01 to 0.0005 equivalents per equivalent of the reactive end group of the fluorooxyalkylene group-containing polymer, which has hydroxyl groups at both ends of the molecular chain and two olefin moieties at both ends of the molecular chain. Can be used in an amount of 0.007 to 0.001 equivalent, more preferably about 0.005 equivalent.

Solvents used in the preparation of the fluoroxyalkylene group-containing polymer represented by formula (14) include fluorine-containing solvents such as 1,3-bis(trifluoromethyl)benzene and trifluoromethylbenzene. , Methylnonafluorobutylether, Methylnonafluoroisobutylether, Ethylnonafluorobutylether, Ethylnonafluoroisobutylether, 1,1,1,2,3,4,4,5 Hydrofluoroether (HFE)-based solvents such as 5,5-decafluoro-3-methoxy-2-(trifluoromethyl)pentane (manufactured by 3M, brand name: Novec series), fully fluorinated compounds and perfluoro-based solvents (manufactured by 3M, brand name: Fluorinaut series), which are composed of. Additionally, organic solvents include tetrahydrofuran, monoethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, and dioxane. Ether-based solvents such as these can be used.

The amount of solvent used is 10 to 300 parts by mass, preferably 50 to 100 parts by mass, based on 100 parts by mass of the fluoroxyalkylene group-containing polymer, which has hydroxyl groups at both ends of the molecular chain and two olefin moieties at both ends of the molecular chain. It can be used in an amount of 150 parts by mass, more preferably about 100 parts by mass.

Subsequently, the reaction is stopped, and the water layer and the fluorine solvent layer are 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 fluoroxyalkylene group-containing polymer represented by formula (14).

In the preparation of the fluoropolyether group-containing polymer-modified silane represented by the above formula (1) when α is 2, the solvent used is preferably a fluorine-based solvent, and the fluorine-based solvent is 1,3-bis(tri Fluoromethyl)benzene, trifluoromethylbenzene, methylnonafluorobutyl ether, methylnonafluoroisobutyl ether, ethylnonafluorobutyl ether, ethylnonafluoroisobutyl ether, 1,1, Hydrofluoroether (HFE)-based solvents such as 1,2,3,4,4,5,5,5-decafluoro-3-methoxy-2-(trifluoromethyl)pentane (manufactured by 3M) , brand name: Novec series), and a perfluoro-based solvent consisting of a fully fluorinated compound (manufactured by 3M, brand name: Fluorinaut series).

The amount of solvent used is 10 to 300 parts by mass, preferably 50 to 150 parts by mass, more preferably about 100 parts by mass, based on 100 parts by mass of the fluoroxyalkylene group-containing polymer having two olefin moieties at both ends of the molecular chain. 100 parts by mass can be used.

In addition, in the preparation of the fluoropolyether group-containing polymer-modified silane represented by formula (1) when α is 2, the organosilicon compound having a SiH group and a hydrolyzable end group in the molecule is of the following general formula (6) Compounds represented by ) to (9) are preferable.

( ^In the formula, ^{R ,}

Among these molecules, organosilicon compounds having a SiH group and a hydrolyzable end group include, for example, trimethoxysilane, triethoxysilane, tripropoxysilane, triisopropoxysilane, and tributoxysilane. Phosphorus, triisopropenoxysilane, triacetoxysilane, trichlorosilane, tribromosilane, triiodosilane, and the following organosilicon compounds can be mentioned.

In the preparation of a fluoropolyether group-containing polymer-modified silane represented by formula (1) when α is 2, a fluorooxyalkylene group-containing polymer and molecule each having two olefin moieties at both ends of the molecular chain are used. When reacting an organosilicon compound having a SiH group and a hydrolyzable end group in the molecule, the amount of the organosilicon compound having a SiH group and a hydrolyzable end group in the molecule is fluorosilicon compound having two olefin moieties at both ends of the molecular chain. It can be used in an amount of 2 to 6 equivalents, more preferably 2.2 to 3.5 equivalents, and even more preferably about 3 equivalents, based on 1 equivalent of the reactive end group of the oxyalkylene group-containing polymer.

In addition, in the preparation of a fluoropolyether group-containing polymer-modified silane represented by formula (1) when α is 2, the organosilicon compound that does not have a hydrolyzable terminal group in the molecule and has two or more SiH groups is Compounds represented by the following general formulas (10) to (12) are preferred.

(In the formula, R ¹ , R ² , g, j, and i are the same as above.)

Examples of organosilicon compounds that do not have a hydrolyzable terminal group and have two or more SiH groups in such molecules include those shown below.

In the preparation of a fluoropolyether group-containing polymer-modified silane represented by formula (1) when α is 2, a fluorooxyalkylene group-containing polymer and molecule each having two olefin moieties at both ends of the molecular chain are used. When reacting an organosilicon compound having two or more SiH groups and not having a hydrolyzable end group in the molecule, the amount of the organosilicon compound having two or more SiH groups and not having a hydrolyzable end group in the molecule must be used at both ends of the molecular chain. It can be used in an amount of 5 to 20 equivalents, more preferably 7.5 to 12.5 equivalents, and even more preferably about 10 equivalents, based on 1 equivalent of the reactive end group of the fluoroxyalkylene group-containing polymer each having two olefin moieties.

In addition, in the preparation of the fluoropolyether group-containing polymer-modified silane represented by formula (1) when α is 2, the organosilicon compound having an olefin moiety and a hydrolyzable terminal group in the molecule is the following general formula (13) ) Compounds represented by ) are preferred.

(Where R, X, V, and n are the same as above.)

In the preparation of a fluoropolyether group-containing polymer-modified silane represented by formula (1) when α is 2, a fluorooxyalkylene group-containing polymer and molecule each having two olefin moieties at both ends of the molecular chain are used. A reaction product (intermediate) with an organosilicon compound that does not have a hydrolyzable end group and has two or more SiH groups, and an olefin moiety in the molecule when reacting an organosilicon compound that has an olefin moiety and a hydrolyzable end group in the molecule. The usage amount of the organosilicon compound having a hydrolyzable end group is a polymer containing a fluoroxyalkylene group, which has two olefin moieties at both ends of the molecular chain, and an organic compound having two or more SiH groups without a hydrolyzable end group in the molecule. It can be used in an amount of 2 to 6 equivalents, more preferably 2.2 to 3.5 equivalents, and even more preferably about 3 equivalents, based on 1 equivalent of the reactive end group of the reactant (intermediate) with the silicon compound.

In the preparation of a fluoropolyether group-containing polymer-modified silane represented by formula (1) when α is 2, the hydrosilylation reaction catalyst includes platinum black, chloroplatinic acid, alcohol modified product of chloroplatinic acid, chloroplatinic acid, and Complexes with olefins, aldehydes, vinyl siloxanes, acetylene alcohols, etc., and platinum group metal catalysts such as tetrakis(triphenylphosphine)palladium and chlorotris(triphenylphosphine)rhodium. Preferably, it is a platinum-based compound such as a vinylsiloxane coordination compound.

The amount of hydrosilylation reaction catalyst to be used is a fluorooxyalkylene group-containing polymer having two olefin moieties at both ends of the molecular chain, or this polymer and an organic silicon having two or more SiH groups without a hydrolyzable end group in the molecule. It is used in an amount of 0.1 to 100 ppm, more preferably 1 to 50 ppm, in terms of transition metal (mass), relative to the mass of the reactant (intermediate) with the compound.

Thereafter, the solvent and unreacted substances are distilled off under reduced pressure to obtain the target compound.

For example, a compound represented by the formula below as a fluoroxyalkylene group-containing polymer having two olefin moieties at both ends of the molecular chain.

When trimethoxysilane is used as an organosilicon compound having a SiH group and a hydrolyzable end group in the molecule, a compound represented by the following formula is obtained.

The present invention further provides a surface treatment agent containing the polymer-modified silane containing the fluoropolyether group. This surface treatment agent is obtained by partially hydrolyzing the terminal hydrolyzable groups of the fluoropolyether group-containing polymer-modified silane into hydroxyl groups by a previously known method, that is, the fluoropolyether group represented by the above formula (1). A silane containing polymer-modified silane in which part of the hydrolyzable group of

Surface treatment agents include, if necessary, hydrolysis condensation catalysts, such as organic tin compounds (dibutyltin dimethoxide, dibutyltin dilaurate, etc.), organic titanium compounds (tetra n-butyl titanate, etc.) ), organic acids (acetic acid, methanesulfonic acid, fluorine-modified carboxylic acid, etc.), and inorganic acids (hydrochloric acid, sulfuric acid, etc.) may be added. Among these, acetic acid, tetran-butyl titanate, dibutyltin dilaurate, fluorine-modified carboxylic acid, etc. are particularly preferable.

The addition amount of the hydrolysis condensation catalyst is a catalytic amount, and is usually 0.01 to 5 parts by mass, especially 0.1 to 1 part by mass, based on 100 parts by mass of the fluoropolyether group-containing polymer-modified silane.

This surface treatment agent may contain an appropriate solvent. Such solvents include fluorine-modified aliphatic hydrocarbon solvents (perfluoroheptane, perfluorooctane, etc.), fluorine-modified aromatic hydrocarbon solvents (1,3-bis(trifluoromethyl)benzene, etc.), and fluorine-modified ether solvents. Solvents (methyl perfluorobutyl ether, ethyl perfluorobutyl ether, perfluoro(2-butyltetrahydrofuran), etc.), fluorine-modified alkylamine-based solvents (perfluorotributylamine, perfluorotributylamine) pentylamine, etc.), hydrocarbon solvents (petroleum benzine, toluene, xylene, etc.), and ketone solvents (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.). Among these, fluorine-modified solvents are preferred in terms of solubility, wettability, etc., especially 1,3-bis(trifluoromethyl)benzene, perfluoro(2-butyltetrahydrofuran), and perfluorine. Lotributylamine and ethylperfluorobutyl ether are preferred.

The solvent may be a mixture of two or more types, and it is preferable to uniformly dissolve the fluoropolyether group-containing polymer-modified silane. In addition, the optimal concentration of the fluoropolyether group-containing polymer-modified silane dissolved in a solvent varies depending on the processing method, and can be any amount that is easy to measure. However, in the case of direct coating, the solvent and the fluoropolyether group-containing polymer-modified silane should be used. It is preferably 0.01 to 10% by mass, especially 0.05 to 5% by mass, relative to the total mass of the silane, and in the case of vapor deposition treatment, 1 to 1% by mass relative to the total mass of the solvent and the polymer-modified silane containing a fluoropolyether group. It is preferably 100% by mass, especially 3 to 30% by mass.

The surface treatment agent of the present invention can be applied to the substrate by known methods such as brush coating, dipping, spraying, and vapor deposition. The heating method during the vapor deposition process may be either a resistance heating method or an electron beam heating method, and is not particularly limited. In addition, the curing temperature varies depending on the curing method, but for example, when applying by vapor deposition, the range is preferably 20 to 200°C. Additionally, it may be cured under humidification. The film thickness of the cured film is appropriately selected depending on the type of substrate, but is usually 0.1 to 100 nm, especially 1 to 20 nm.

The substrate treated with the surface treatment agent of the present invention is not particularly limited, and may be made of various materials such as paper, cloth, metal and its oxides, glass, plastic, ceramic, and quartz. The surface treatment agent of the present invention can impart water and oil repellency to the substrate. In particular, it can be suitably used as a surface treatment agent for SiO ₂ treated glass or film.

Items treated with the surface treatment agent of the present invention include car navigation systems, mobile phones, digital cameras, digital video cameras, PDAs, portable audio players, car audio, game devices, eyeglass lenses, camera lenses, lens filters, sunglasses, eye cameras, etc. Optical products include medical equipment, copiers, PCs, liquid crystal monitors, organic EL displays, plasma displays, touch panel displays, protective films, and anti-reflection films. Since the surface treatment agent of the present invention can prevent fingerprints and sebum from adhering to the article and can also provide scratch prevention, it is particularly useful as a water-repellent and oil-repellent layer for touch panel displays, anti-reflection films, etc.

In addition, the surface treatment agent of the present invention is an antifouling coating for sanitary products such as bathtubs and washbasins, an antifouling coating for window glass or tempered glass of automobiles, trams, and aircraft, and headlamp covers, and a water- and oil-repellent coating for building materials for exterior walls, and for kitchens. Anti-contamination coating for building materials, anti-fouling and anti-paper sticking/graffiti coating for telephone boxes, coating for preventing fingerprint adhesion to artworks, etc., anti-fingerprint coating for compact discs, DVDs, etc., mold release agent or paint additive for molds, resin modifier, inorganic substances. It is also useful as a fluidity modifier or dispersibility modifier for fillers, and a lubricity improver for tapes, films, etc.

Example

Hereinafter, the present invention will be described in more detail by presenting examples and comparative examples, but the present invention is not limited to the following examples.

[Example 1]

In a reaction vessel, 100 g of 1,3-bis (trifluoromethyl) benzene, 0.01 g (2.0 × 10 ^-5 mol) of tris (pentafluorophenyl) borane, and the following formula (A)

Mix 114g (2.7×10 ^-2 mol) of the compound represented by the following formula (B)

13.6 g (3.3 × 10 ^-2 mol) of silane represented by was slowly added dropwise and stirred at 25°C for 1 hour. Subsequently, water was added, and the lower fluorine compound layer was recovered through a liquid separation operation and then washed with acetone. The lower fluorine compound layer after washing is recovered again, and the remaining solvent is distilled off under reduced pressure to obtain the following formula (C)

103 g of a fluoropolyether group-containing polymer represented by was obtained.

The following formula (C) in a reaction vessel:

111 g (2.4 × 10 ^-2 mol) of the compound represented by, 90 g of 1,3-bis (trifluoromethyl) benzene, 9 g (7.4 × 10 ^-2 mol) of trimethoxysilane, and chloroplatinic acid/vinylsiloxane 9.0 x 10 ^-2 g of toluene solution of the complex (containing 2.4 x 10 ^-6 mol as Pt alone) was mixed and aged at 80°C for 24 hours. After that, the solvent and unreacted substances were distilled off under reduced pressure, and 88 g of liquid organism was obtained.

The obtained compound was confirmed to have a structure represented by the following formula (D) by NMR.

[Example 2]

In a reaction vessel, 100 g of 1,3-bis (trifluoromethyl) benzene, 0.01 g (2.0 × 10 ^-5 mol) of tris (pentafluorophenyl) borane, and the following formula (A)

Mix 114g (2.7×10 ^-2 mol) of the compound represented by the formula (E) below:

25.8 g (3.3 × 10 ^-2 mol) of silane represented by was slowly added dropwise and stirred at 25°C for 1 hour. Subsequently, water was added, and the lower fluorine compound layer was recovered through a liquid separation operation and then washed with acetone. The fluorine compound layer, which is the lower layer after washing, is recovered again, and the remaining solvent is distilled off under reduced pressure to obtain the formula (F) below:

125 g of a fluoropolyether group-containing polymer represented by was obtained.

The following formula (F) is added to the reaction vessel:

Compound represented by 120g (2.4×10 ^-2 mol), 90g of 1,3-bis (trifluoromethyl)benzene, 9g (7.4×10 ^-2 mol) of trimethoxysilane, and chloroplatinic acid/vinylsiloxane 9.0 x 10 ^-2 g of toluene solution of the complex (containing 2.4 x 10 ^-6 mol as Pt alone) was mixed and aged at 80°C for 24 hours. After that, the solvent and unreacted substances were distilled off under reduced pressure to obtain 76 g of a liquid product.

The obtained compound was confirmed to have a structure represented by the following formula (G) by NMR.

[Example 3]

In a reaction vessel, 100 g of 1,3-bis (trifluoromethyl) benzene, 0.01 g (2.0 × 10 ^-5 mol) of tris (pentafluorophenyl) borane, and the following formula (H)

Mix 112.2g (2.6×10 ^-2 mol) of the compound represented by the following formula (B)

27.2 g (6.6 × 10 ^-2 mol) of silane represented by was slowly added dropwise and stirred at 25°C for 1 hour. Subsequently, water was added, and the lower fluorine compound layer was recovered through a liquid separation operation and then washed with acetone. The fluorine compound layer, which is the lower layer after washing, is recovered again, and the remaining solvent is distilled off under reduced pressure to obtain the following formula (I)

105 g of a fluoropolyether group-containing polymer represented by was obtained.

The following formula (I) in a reaction vessel:

90 g (1.75 × 10 ^-2 mol) of the compound represented by, 90 g of 1,3-bis (trifluoromethyl) benzene, 12.8 g (10.5 × 10 ^-2 mol) of trimethoxysilane, and chloroplatinic acid/vinyl siloxane. 8.4 x 10 ^-2 g of toluene solution of the cein complex (containing 2.3 x 10 ^-6 mol as Pt alone) was mixed and aged at 80°C for 24 hours. After that, the solvent and unreacted substances were distilled off under reduced pressure to obtain 93 g of a liquid product.

The obtained compound was confirmed to have a structure represented by the following formula (J) by NMR.

[Example 4]

In a reaction vessel, 30 g of 1,3-bis(trifluoromethyl)benzene, 3.0×10 ^-2 g of toluene solution of chloroplatinic acid/vinylsiloxane complex (containing 8.2×10 ^-7 mol as Pt alone), and tetramethyldimethylsiloxane. Mix 6.0g (4.5×10 ^-2 mol) of siloxane, and use the following formula (K)

30 g (7.2 x 10 ^-3 mol) of the compound represented by was slowly added dropwise and stirred at 25°C for 1 hour. After that, the solvent and unreacted substances were distilled off under reduced pressure to obtain 31 g of a liquid product.

The obtained compound was confirmed to have a structure represented by the following formula (L) by NMR.

In a reaction vessel, 10 g of 1,3-bis (trifluoromethyl) benzene, 2.8 × 10 ^-3 g (5.5 × 10 ^-6 mol) of tris (pentafluorophenyl) borane, and the following formula (A)

Mix 11.4 g (2.7 × 10 ^-3 mol) of the compound represented by the formula (L) below:

11.7 g (2.7 x 10 ^-3 mol) of the compound represented by was slowly added dropwise and stirred at 25°C for 1 hour. Subsequently, water was added, and the lower fluorine compound layer was recovered through a liquid separation operation and then washed with acetone. The lower fluorine compound layer after washing is recovered again, and the remaining solvent is distilled off under reduced pressure to obtain the formula (M) below:

20 g of a fluoropolyether group-containing polymer represented by was obtained.

The following formula (M) in a reaction vessel:

17.1 g (2.0 × 10 ^-3 mol) of the compound represented by, 15 g of 1,3-bis (trifluoromethyl) benzene, 0.73 g (6.0 × 10 ^-3 mol) of trimethoxysilane, and chloroplatinic acid/vinyl 2.0 x 10 ^-2 g of a toluene solution of the siloxane complex (containing 5.3 x 10 ^-7 mol as Pt alone) was mixed and aged at 80°C for 24 hours. After that, the solvent and unreacted substances were distilled off under reduced pressure to obtain 14 g of a liquid product.

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

[Example 5]

In a reaction vessel, 10 g of 1,3-bis (trifluoromethyl) benzene, 0.54 g (5.4 × 10 ^-3 mol) of triethylamine, and the following formula (A)

Mix 10.1 g (2.4 × 10 ^-3 mol) of the compound represented by the following formula (O)

10.0 g (2.4 x 10 ^-3 mol) of the compound represented by was slowly added dropwise and stirred at 60°C for 20 hours. Subsequently, hydrochloric acid was added, and the lower fluorine compound layer was recovered through a liquid separation operation and then washed with acetone. The fluorine compound layer, which is the lower layer after washing, is recovered again, and the remaining solvent is distilled off under reduced pressure to obtain the formula (P) below:

17 g of a fluoropolyether group-containing polymer represented by was obtained.

The following formula (P) is placed in the reaction vessel:

Compound represented by 16.7g (2.0×10 ^-3 mol), 15g of 1,3-bis(trifluoromethyl)benzene, 0.73g (6.0× ^10-3 mol) of trimethoxysilane, and chloroplatinic acid/vinyl 2.0 x 10 ^-2 g of a toluene solution of the siloxane complex (containing 5.3 x 10 ^-7 mol as Pt alone) was mixed and aged at 80°C for 24 hours. After that, the solvent and unreacted substances were distilled off under reduced pressure to obtain 13 g of a liquid product.

The obtained compound was confirmed to have a structure represented by the following formula (Q) by NMR.

[Comparative Example 1]

As a comparative example, the following polymers were used.

Preparation of surface treatment agent and formation of hardened film

The fluoropolyether group-containing polymer-modified silane obtained in Examples 1, 2, and 4 and the polymer of Comparative Example 1 were dissolved in Novec 7200 (manufactured by 3M, ethyl perfluorobutyl ether) to a concentration of 20% by mass. A surface treatment agent was prepared. 7 mg of each surface treatment agent was vacuum deposited on glass (Gorilla, manufactured by Corning) whose outermost surface was treated with 10 nm of SiO ₂ (processing conditions were pressure: 2.0×10 ^-2 Pa, heating temperature: 700°C), 25°C, humidity 40%. It was cured for 24 hours in an atmosphere of % to form a cured film with a film thickness of 10 nm.

Evaluation of water repellency

[Evaluation of initial water repellency]

With respect to the glass on which the cured film produced above was formed, the contact angle (water repellency) of the cured film with respect to water was measured using a contact angle meter Drop Master (manufactured by Kyowakaimen Chemical Co., Ltd.). Initially, it showed good water repellency. The results are shown in Table 1.

[Evaluation of dynamic friction coefficient]

For the glass with the cured film produced above, the coefficient of dynamic friction against Bemcoat (manufactured by Asahi Kasei) was measured using a surface tester 14FW (manufactured by Shinto Chemical Company) under the following conditions. The results are shown in Table 1.

Contact area: 10mm×35mm

Load: 100g

[Evaluation of slipperiness]

Ten panelists touched the glass with the cured film produced above with their fingers and evaluated its usability based on the following criteria, and the evaluation by the largest number of people was used as the evaluation of slipperiness. The results are shown in Table 1.

◎: Very good

○+: Good

○: Normal

×: bad

For Examples 1, 2, and 4 in which a siloxane group or a fluoropolyether group was introduced into the fluoropolyether group-containing polymer molecule, the coefficient of dynamic friction was reduced compared to the short chain Comparative Example 1, and the slipperiness was improved. can confirm.

Claims (9)

The following general formula (1)

(In the formula, Rf is CF ₃ O-(CF ₂ O) _p1 -(C ₂ F ₄ O) _q1 -CF ₂ -(In the formula, p1 is an integer of 5 to 100, q1 is an integer of 5 to 100, p1+q1 is an integer of 10 to 105. Each repeating unit may be randomly combined.) A polymer residue containing a monovalent fluorooxyalkylene group represented by or -CF ₂ O-(CF ₂ O) _p1 -( C ₂ F ₄ O) _q1 -CF ₂ -(In the formula, p1 is an integer from 5 to 100, q1 is an integer from 5 to 100, and p1+q1 is an integer from 10 to 105. Each repeating unit is randomly combined. It may be a polymer residue containing a divalent fluoroxyalkylene group, represented by Y, Y is a divalent to hexavalent hydrocarbon group that may have a siloxane bond and/or a silylene group, and R is an alkyl group having 1 to 4 carbon atoms. or a phenyl group, It is a polymer residue, an alkyl group or phenyl group having 1 to 4 carbon atoms, n is an integer of 1 to 3, m is an integer of 1 to 5, and α is 1 or 2.)
A polymer-modified silane containing a fluoropolyether group, represented by . According to claim 1,
In the above formula (1), Y is an alkylene group with 3 to 10 carbon atoms, an alkylene group with 8 to 16 carbon atoms including a phenylene group, or an alkylene group with 2 to 10 carbon atoms each has a silalkylene structure or a silarylene structure. A divalent group bonded through a divalent group, a divalent to tetravalent group bonded to a straight chain organopolysiloxane residue having 2 to 10 silicon atoms, and an alkylene group having 2 to 10 carbon atoms bonded to the bonding hand of a straight-chain organopolysiloxane residue having 2 to 10 silicon atoms. A fluoropolyether group characterized in that it is at least one group selected from the group consisting of divalent to tetravalent groups in which an alkylene group having 2 to 10 carbon atoms is bonded to the bond of a branched or cyclic organopolysiloxane residue. containing polymer-modified silanes. According to claim 1,
In the above formula (1), each of A polymer-modified silane containing a fluoropolyether group, characterized in that it is selected from the group consisting of groups and halogen atoms. The method according to any one of claims 1 to 3,
A polymer-modified silane containing a fluoropolyether group, wherein in the above formula (1), Q is a divalent organic group represented by the following formula (4).

(Wherein, R'' is an alkylene group or carbonyl group having 1 to 10 carbon atoms which may have any one of ketone, ester, amide, ether, sulfide, amine, and phenylene, and W is an alkylene group having 2 to 40 silicon atoms. a straight-chain divalent organo(poly)siloxane residue, a straight-chain silicon alkylene group that may have a siloxane bond with 3 to 40 silicon atoms bonded through an alkylene group with 1 to 4 carbon atoms, and a carbon number It is a divalent group selected from straight-chain siloxane groups that may have siloxane bonds with 3 to 40 silicon atoms bonded through 6 to 10 arylene groups, and organo(poly)siloxane residues, silalkyl The lene group and silarylene group may be single or mixed, β is 0 or 1, γ is 0 or 1, and β+γ is 1 or 2.) The method according to any one of claims 1 to 3,
A polymer-modified silane containing a fluoropolyether group, characterized in that the polymer-modified silane represented by formula (1) is represented by the following formula.

(In the formula, p1 is an integer from 5 to 100, q1 is an integer from 5 to 100, and p1+q1 is an integer from 10 to 105.) A surface treatment agent comprising the fluoropolyether group-containing polymer-modified silane according to any one of claims 1 to 3. An article having a cured film of the surface treatment agent according to claim 6 on its surface. delete delete