TWI720067B - Polymer modified silane, surface treatment agent and articles containing fluoropolyether group - Google Patents

Abstract

The present invention provides a polymer-modified silane containing a fluoropolyether group that can form a water- and oil-repellent layer with excellent sliding properties, a surface treatment agent containing the silane, and a surface treatment agent that has been surface-treated by the surface treatment agent (that is, on the surface The hardened film with the surface treatment agent on it).

A polymer-modified silane containing a fluoropolyether group represented by the following formula (1),

(In the formula, Rf is a monovalent or divalent polymer residue containing fluorooxyalkylene (fluorooxyalkylene), Y is a 2- to 6-valent hydrocarbon group that may have a siloxane bond and/or a silylene group, R It is an alkyl or phenyl group with 1 to 4 carbon atoms, X is a hydroxyl group or 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, Monovalent fluorooxyalkylene-containing polymer residues, C1-C4 alkyl groups or phenyl groups, n is an integer of 1-3, m is an integer of 1-5, and α is 1 or 2).

Description

Polymer modified silane, surface treatment agent and articles containing fluoropolyether group

The present invention relates to polymer-modified silanes containing fluoropolyether groups, and in detail, it relates to polymer-modified silanes containing fluoropolyether groups that form a film with excellent sliding properties, and surface treatment agents containing the silanes, and An article that is surface-treated by the surface treatment agent (that is, has a cured film of the surface treatment agent on the surface).

In recent years, the touch panel system represented by the display of mobile phones is accelerating. However, the touch panel is in a state where the screen is exposed, and there are many opportunities for direct contact with fingers or cheeks, and there is a problem that dirt such as sebum is easy to adhere. Therefore, in order to optimize the appearance or visual recognition, the requirements for technologies that do not easily adhere to fingerprints or easily remove dirt on the surface of the display are increasing year by year, and it is hoped that the development of materials that can respond to these requirements. In particular, since fingerprint dirt is easy to adhere to the surface of the touch panel display, it is advisable to provide a water and oil repellent layer. However, although the conventional water and oil repellent layer has high water and oil repellency and excellent dirt wiping properties, there is a problem that the anti-fouling performance deteriorates during use.

Generally speaking, compounds containing fluoropolyether groups are The surface free energy is very small, and it has water and oil repellency, chemical resistance, lubricity, mold releasability, antifouling properties, etc. Utilizing this property, it is widely used industrially as a water and oil repellent antifouling agent for paper, fiber, etc., a slip agent for magnetic recording media, an oil repellent for precision equipment, mold release agents, cosmetics, protective films, etc. However, this property also means non-adhesiveness and non-adhesion to other substrates. Even if it can be coated on the surface of the substrate, it is difficult to make the film adhere to it.

On the other hand, a silane coupling agent is well known as a compound for bonding the surface of a substrate such as glass or cloth with an organic compound, and it is 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. The hydrolyzable silyl group forms a film by self-condensation reaction of moisture in the air. The film is formed by chemically and physically bonding the hydrolyzable silyl group with the surface of glass or metal to become a durable and strong film.

Therefore, it has been revealed that by using a fluoropolyether group-containing polymer with a hydrolyzable silyl group introduced into the fluoropolyether group-containing compound to modify the silane, it is easy to adhere to the surface of the substrate and on the surface of the substrate. A composition capable of forming a film having water and oil repellency, chemical resistance, lubricity, mold releasability, antifouling properties, etc. (Patent Documents 1 to 5: JP 2008-534696 A, JP 2008-537557 No., Japanese Patent Application Publication No. 2012-072272, Japanese Patent Application Publication No. 2012-157856, Japanese Patent Application Publication No. 2013-136833).

The composition of silane is modified with a fluoropolyether group-containing polymer with hydrolyzable silyl groups introduced into the fluoropolyether group-containing compound Although the lens or anti-reflection film treated on the surface of the object has excellent abrasion resistance and mold release properties, the sliding properties are insufficient.

[Prior Technical Literature]

[Patent Literature]

[Patent Document 1] Japanese Special Publication No. 2008-534696

[Patent Document 2] Japanese Special Publication No. 2008-537557

[Patent Document 3] JP 2012-072272 A

[Patent Document 4] JP 2012-157856 A

[Patent Document 5] JP 2013-136833 A

[Patent Document 6] JP 2015-199906 A

The inventors proposed a polymer-modified silane containing a fluoropolyether group (Patent Document 6: Japanese Patent Application Laid-Open No. 2015-199906), which is a fluoropolyether group-containing compound with excellent abrasion resistance, as follows The formula says,

(In the formula, Rf is a monovalent fluorooxyalkyl group or a divalent fluorooxyalkylene-containing polymer residue, Y is a 2~6 valent hydrocarbon group which may have a siloxane bond and a silylene group, R Independently an alkyl group or phenyl group with 1 to 4 carbon atoms, X is independent Ground hydrolyzable group, n is an integer from 1 to 3, m is an integer from 1 to 5, α is 1 or 2), the silane is modified by the polymer containing the fluoropolyether group and/or its partial hydrolysis condensation The coating formed by the surface treatment agent of the material shows high water and oil repellency and abrasion resistance. However, the sliding properties are still not improved.

The present invention was completed in view of the above matters, and its object is to provide a fluoropolyether group-containing polymer modified silane that can form a water and oil repellent layer with excellent sliding properties, and a surface treatment agent containing the silane, and the surface treatment The article is surface-treated by the agent (that is, having a cured film of the surface treatment agent on the surface).

In order to solve the above-mentioned object, the inventors of the present invention made a intensive review and found that in the polymer-modified silane containing the fluoropolyether group, the hydroxyl group represented by the general formula (1) described later is passed through the following -Q-R'- group The protected polymer-modified silane containing fluoropolyether groups can form a water- and oil-repellent layer with excellent sliding properties, weather resistance, and excellent storage stability. The present invention is finally completed.

Therefore, the present invention provides the following polymer-modified silanes, surface treatment agents and articles containing fluoropolyether groups.

[1] A polymer-modified silane containing a fluoropolyether group, which is represented by the following general formula (1),

(In the formula, Rf is a monovalent or divalent fluorooxyalkylene-containing polymer Residues, Y is a 2--6 valence hydrocarbon group that may have a siloxane bond and/or silylene, R is an alkyl or phenyl group with 1 to 4 carbons, X is a hydroxyl group or a hydrolyzable group, and Q may be A divalent organic group with a siloxane bond and/or a silylene group, R'is a monovalent fluoroalkyl group, a monovalent polymer residue containing a fluorooxyalkylene group, an alkyl group with 1 to 4 carbon atoms, or Phenyl, n is an integer of 1 to 3, m is an integer of 1 to 5, and α is 1 or 2).

[2] The fluoropolyether group-containing polymer-modified silane as described in [1], wherein α of the aforementioned formula (1) is 1, and the Rf group is a monovalent fluorine-containing oxygen-containing compound represented by the following general formula (2) Polymer residues of alkylene;

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

[3] The fluoropolyether group-containing polymer-modified silane as described in [1], wherein α of the aforementioned formula (1) is 2, and the Rf group is a divalent fluorine-containing oxygen-containing compound represented by the following general formula (3) Polymer residues of alkylene;

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

[4] The fluoropolyether group-containing polymer-modified silane as described in any one of [1] to [3], wherein in the aforementioned formula (1), Y is selected from alkylene having 3 to 10 carbon atoms A group, a divalent group in which a phenylene-containing alkylene group with 8 to 16 carbon atoms, and a carbon number 2-10 alkylene group are bonded to each other via a silylalkylene structure or a silylalkylene structure, and a silicon atom The 2~10 linear organopolysiloxane residues have 2~4 valence groups with 2~10 carbon atoms and 3~10 silicon atoms. At least one group consisting of 2 to 4 valent groups of alkylene having 2 to 10 carbon atoms bonded to the bonding bond of the cyclic or cyclic organopolysiloxane residue.

[5] The fluoropolyether group-containing polymer-modified silane as described in any one of [1] to [4], wherein in the aforementioned formula (1), X is each independently selected from a hydroxyl group and a carbon number of 1~ A 10 alkoxy group, a C 2-10 alkoxy-substituted alkoxy group, a C 2-10 acyloxy group, a C 2-10 alkenyloxy group, and a halogen atom.

[6] The fluoropolyether group-containing polymer-modified silane as described in any one of [1] to [5], wherein in the aforementioned formula (1), Q is a divalent formula represented by the following formula (4) Organic base

(In the formula, R" may have any one of ketones, esters, amides, ethers, thioethers, amines, phenylenes, and C1-C10 alkylene or carbonyl groups. W is composed of 2 silicon atoms. ~40 straight-chain divalent organic (poly)siloxane residues, which are bonded via alkylenes with 1 to 4 carbon atoms, and can have 3 to 40 silicon atoms in a straight chain. The silylene group, the phenylene-containing alkylene group can be combined with the alkylene group with 1 to 4 carbon atoms, and the siloxane bond with 3 to 40 silicon atoms The divalent group selected by the linear silyl silylene group, the organic (poly) siloxane residue, the silyl silyl group, and the silyl arylene group may be single or mixed, and β is 0 Or 1, γ is 0 or 1, β+γ is 1 or 2).

[7] The polymer-modified silane containing a fluoropolyether group as described in 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 comprising the fluoropolyether group-containing polymer modified silane as described in any one of [1] to [7].

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

The surface treatment agent of the present invention containing a fluoropolyether group-containing polymer-modified silane whose hydroxyl group bound to a carbon atom is blocked by the -Q-R'- group can form a water- and oil-repellent layer with excellent sliding properties.

[The form of implementing the invention]

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

(In the formula, Rf is a monovalent or divalent polymer residue containing a fluorooxyalkylene 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 carbon number 1~4 alkyl or phenyl group, X is a hydroxyl group or hydrolyzable group, Q is a divalent organic group which may have a siloxane bond and/or a silylene group, R'is a monovalent fluoroalkyl group, a monovalent A polymer residue containing a fluorooxyalkylene group, 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).

The fluoropolyether-containing polymer modified silicon of the present invention contains monovalent or divalent fluorooxyalkylene-containing polymer residues (Rf) and alkoxysilyl groups, such as hydrolyzable silyl groups or hydroxyl groups. The silyl group (-Si(R) _3-n (X) _n ) is a structure in which the 2~6 valence hydrocarbon chain (Y) which may have a siloxane bond and/or a silylene group is combined with a carbon atom, more For the hydroxyl group bonded to the carbon atom in the polymer as the intermediate, the divalent organic group (Q) which may have a siloxane bond and/or a silylene group as a linking group is preferably May have ketones, esters, amides, ethers, thioethers, amines, phenylenes with 1-10 carbon alkylene or carbonyl (R") or organopolysiloxane residues or silylene, silicon Arylene (W), introducing monovalent fluoroalkyl groups, monovalent fluorooxyalkylene-containing polymer residues, C1-C4 alkyl groups or phenyl groups (R'), etc., to form excellent sliding properties The water and oil repellent layer.

In the above formula (1), when α is 1, Rf is preferably a monovalent fluorooxyalkylene-containing polymer residue represented by the following general formula (2) (with Also referred to as fluorooxyalkyl below).

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

In the above formula (1), when α is 2, Rf is preferably a divalent fluorooxyalkylene-containing polymer residue represented by the following general formula (3) (hereinafter, also referred to as fluorooxyalkylene base).

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

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 from 0 to 100 S is an integer from 0 to 100, and p+q+r+s= an integer from 3 to 200, preferably an integer from 10 to 100. Each repeating unit can be linear or branched, each Repeating units can be randomly combined with each other. More preferably, p+q is an integer from 10 to 105, especially an integer from 15 to 60, and r=s=0. If p+q+r+s is less than the above upper limit, the adhesion or curability is good, and if it is more than the above lower limit, the characteristics of the fluoropolyether group can be fully utilized, which 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.

Specific examples of Rf (monovalent or divalent fluorooxyalkylene group-containing polymer residue) include the following.

(In the formula, 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, s. u is an integer from 1 to 24, and v is from 1 to An integer of 24 and a number that satisfies u+v=r. Each repeating unit can be random Land combination).

In the above formula (1), Y is a valence of 2~6, preferably 2~4, which may have a siloxane bond ((two) organosiloxane unit, etc.) and/or an alkylene group (diorganosilylene) Valence, more preferably, a divalent hydrocarbon group does not contain a linking group (ether bond, etc.) with a low bonding energy in the molecule, and can provide a coating film with excellent weather resistance and abrasion resistance.

Specific examples of Y include propylene (trimethylene, methyl ethylene), ethylene (tetramethylene, methyl ethylene), hexamethylene, etc., with carbon numbers ranging from 3 to 3. 10 alkylenes, alkylenes containing phenylenes and other carbon 6-8 arylenes (for example, alkylenes with 8 to 16 carbons, arylalkylenes, etc.), and those with 2 to 10 carbons The alkylene groups are mutually through the silylalkylene structure (the two ends of the alkylene are blocked by the diorganosilylene group) or the silylalkylene structure (the two ends of the arylalkylene are blocked by the diorganosilylene group). Structure) The bonded bivalent group, the 2~6 valence of the alkylene group is bonded to the bonding bond of the linear organopolysiloxane residue with 2 to 10 silicon atoms, preferably 2 to 5 , Preferably 2~4 valent groups, 2~ of alkylene groups are bonded to the bonding bonds of branched or cyclic organopolysiloxane residues with 3~10 silicon atoms, preferably 3~5 6-valent, preferably 2~4 valent groups, etc., preferably alkylene having 3-10 carbons, alkylene having 8-16 carbons containing phenylene, and alkylene having 2-10 carbons Divalent groups bonded to each other via a silylalkylene structure or a silylalkylene structure, on the bonding bond of a linear organopolysiloxane residue with 2 to 10 silicon atoms, preferably 2 to 5 2~4 valence groups with 2~10 carbon alkylene, or 3~10, preferably 3~5 branched or cyclic organopolysiloxane residues The bond has a carbon number of 2~10 The 2- to 4-valent group of the alkylene group is more preferably an alkylene group having 3 to 6 carbon atoms.

Here, as the silylalkylene structure and the silylalkylene structure, those shown below can be exemplified.

(In the formula, R ¹ is a C1-C4 alkyl group such as methyl, ethyl, propyl, butyl, etc., and a C6-C10 aryl group such as phenyl group. R ¹ may be the same or different 。R ² is a C1-C4 alkylene such as methylene, ethylene, propylene (trimethylene, methyl ethylene), and phenylene, such as carbon 6-10. Aryl).

In addition, as a linear organopolysiloxane residue with 2 to 10 silicon atoms, preferably 2 to 5, and branched or cyclic with 3 to 10 silicon atoms, preferably 3 to 5 Examples of the 2- to hexavalent organopolysiloxane residues shown below are examples.

(In the formula, R ¹ is the same as above. g is an integer from 1 to 9, preferably an integer from 1 to 4, h is an integer from 2 to 6, preferably an integer from 2 to 4, and j is from 0 to 8. The integer of is 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).

As a specific example of Y, the following can be mentioned, for example.

In the above formula (1), X is a hydroxyl group or a hydrolyzable group that may be different from each other. Examples of such X include alkoxy groups with 1 to 10 carbon atoms such as hydroxyl, methoxy, ethoxy, propoxy, isopropoxy, butoxy, etc., methoxymethoxy, methyl Alkoxy with 2-10 carbons such as oxyethoxy, etc. substituted alkoxy with 2-10 carbons such as acetoxy, isopropenoxy, etc. Alkenyloxy group with 2 to 10 carbon atoms, chlorine atom, bromine atom, iodine atom and other halogen atoms. Among them, a methoxy group, an ethoxy group, an isopropenoxy group, and a chlorine atom are preferable.

In the above formula (1), R is an alkyl group having 1 to 4 carbon atoms, such as a methyl group, an ethyl group, a propyl group, and a butyl group, or a phenyl group. Among them, a methyl group is preferable.

n is an integer of 1 to 3, preferably 2 or 3, and more preferably 3 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 will decrease. If it is 6 or more, the terminal alkoxy valence will be too high and adversely affect the performance, so it is preferably 1 to 3 An integer, and 1 is particularly preferred.

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

(In the formula, R" may have any one of ketones, esters, amides, ethers, thioethers, amines, phenylenes, and C1-C10 alkylene or carbonyl groups. W is composed of 2 silicon atoms. ~40 straight-chain divalent organic (poly)siloxane residues, which are bonded via alkylenes with 1 to 4 carbon atoms, and can have 3 to 40 silicon atoms in a straight chain. It is selected from the straight-chain silylalkylene group, the phenylene-containing phenylene group which can be combined through the C1-C4 alkylene group, which can have the siloxane bond with the number of silicon atoms of 3-40 Divalent groups, organic (poly)siloxane residues, silylene groups, and silylene groups may be single or mixed, β is 0 or 1, γ is 0 or 1, β+γ Is 1 or 2).

In the above formula (4), as R", specifically methylene, Ethylene, propylene (trimethylene, methyl ethylene), butyl (tetramethylene, methyl propylene, hexamethylene and other alkylene groups with 1 to 10 carbon atoms, A divalent group or a carbonyl group in which alkylene groups having 1 to 10 carbon atoms are bonded to each other via aryl alkylene groups such as ketones, esters, amides, ethers, thioethers, amines, and phenylene groups having 6 to 8 carbon atoms, preferably It is a divalent group in which an alkylene group having 1 to 4 carbon atoms and an alkylene group having 1 to 4 carbon atoms are bonded to each other via an ether, and a carbonyl group.

As specific examples of R", for example, the following groups can be given.

In the above formula (4), as the linear silylene group of W, the silyl group structure in the linear silyl group, and the silyl group structure, there are Specifically, the following can be exemplified.

(In the formula, R ¹ is a C1-C4 alkyl group such as methyl, ethyl, propyl, butyl, etc., and a C6-C10 aryl group such as phenyl group. R ¹ may be the same or different 。R ² is a C1-C4 alkylene such as methylene, ethylene, propylene (trimethylene, methyl ethylene), and phenylene, such as carbon 6-10. Aryl).

In addition, as the linear divalent organopolysiloxane residue having 2 to 40 silicon atoms, preferably 3 to 10, those shown below can be exemplified.

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

Here, as W, the following can be exemplified.

In the above formula (1), R'is a monovalent fluoroalkyl group (for example, a fluoroalkyl group having 1 to 6 carbons), a monovalent polymer residue containing a fluorooxyalkylene group, and a carbon number of 1 to 4 Alkyl groups or phenyl groups such as methyl, ethyl, propyl, butyl, etc., among them, monovalent fluorooxyalkylene-containing polymer residues and alkyl groups having 1 to 4 carbon atoms are preferred, and particularly preferred are Monovalent polymer residues containing fluorooxyalkylene groups.

In the above formula (1), when R'is a monovalent fluorooxyalkylene-containing polymer residue, this R'is preferably a monovalent fluorooxyalkylene-containing polymer represented by the following general formula (2) Alkyl polymer residues.

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

As the fluoropolyether group-containing polymer-modified silane represented by the above formula (1), one represented by the following formula can be exemplified. Furthermore, in each formula, the repeating number (or degree of polymerization) of each repeating unit constituting the fluorooxyalkyl group or the fluorooxyalkylene group may be any number that satisfies the above-mentioned formulas (2) and (3).

(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).

As a method of preparing a fluoropolyether group-containing polymer-modified silane when α represented by the above formula (1) is 1, for example, the following method can be cited.

Make a fluorooxyalkylene-containing polymer having two olefin sites at a single end of the molecular chain (ie, a monovalent fluorooxyalkylene-containing polymer residue with two olefin sites at a single end of the molecular chain) Polymers) are dissolved in solvents such as fluorine-based solvents such as 1,3-bis(trifluoromethyl)benzene to make organosilicon compounds such as trimethoxysilane which have SiH groups and hydrolyzable end groups in the molecule. Hydrosilylation reaction catalyst such as toluene solution of chloroplatinic acid/vinylsiloxane complex at a temperature of 40~120℃, preferably 60~100℃, more preferably about 80℃, at a temperature of 1~72 Under the conditions of hours, preferably 20 to 36 hours, more preferably about 24 hours, the hydrosilylation addition reaction is carried out and the maturation is carried out at the same time.

In addition, as another method of preparing a fluoropolyether group-containing polymer modified silane when α represented by the above formula (1) is 1, for example The following methods can be cited.

Dissolve the fluorooxyalkyl group-containing polymer having two olefin sites at the single end of the molecular chain in a solvent such as a fluorine-based solvent such as 1,3-bis(trifluoromethyl)benzene, and add trichlorosilane, etc. Organosilicon compounds with SiH groups and hydrolyzable end groups (such as chlorine atoms and other halogen atoms bonded with silicon atoms) in the molecule are used as catalysts for the hydrosilylation reaction, such as chloroplatinic acid/vinylsiloxane complexes In the presence of the toluene solution, at a temperature of 40~120℃, preferably at a temperature of 60~100℃, more preferably at a temperature of about 80℃, at a temperature of 1~72 hours, preferably 20~36 hours, more preferably about 24 hours After undergoing a hydrosilylation addition reaction and aging at the same time, the substituent (halogen atom, etc.) on the silyl group is converted into, for example, a hydrolyzable group such as an alkoxy group such as a methoxy group.

Furthermore, instead of the above-mentioned organosilicon compounds having SiH groups and hydrolyzable end groups in the molecule, SiH group-containing organosilicon compounds that do not have hydrolyzable end groups can also be used. In this case, it is used as an organosilicon compound in the molecule An organosilicon compound with two or more SiH groups that does not have a hydrolyzable end group. At that time, in the same way as the above-mentioned method, a fluorooxyalkyl group-containing polymer having two olefin sites at the single end of the molecular chain and an organosilicon having two or more SiH groups without a hydrolyzable end group in the molecule were combined. After the compound undergoes a hydrosilylation addition reaction at a molar level or more to form a reactant (intermediate) with two remaining SiH groups at the single end of the molecular chain, the polymer end of the reaction product (intermediate) SiH groups and allyltrimethoxysilane, such as organosilicon compounds with olefin sites and hydrolyzable end groups in the molecule, are used as catalysts for the hydrosilylation reaction, such as toluene of chloroplatinic acid/vinylsiloxane complexes In the presence of solution, at 40~120℃, Preferably at a temperature of 60~100°C, more preferably at a temperature of about 80°C, in a condition of 1 to 72 hours, preferably 20 to 36 hours, more preferably about 24 hours, further hydrosilylation addition reaction and simultaneous maturation.

Here, as a fluorooxyalkyl group-containing polymer having two olefin moieties at a single end of the molecular chain, a fluorooxyalkyl group-containing polymer represented by the following general formula (5) can be exemplified.

(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, particularly preferably 1 to 4, and specific examples include methylene, ethylene, and propylene ( Trimethylene, methyl ethylene), butyl (tetramethylene, methyl propylene), hexamethylene, octamethylene and other C1-C8 alkylenes, containing ethylene The alkylene group (for example, the alkylene group with 7 to 8 carbon atoms, arylene group, etc.) of aryl group with 6 to 8 carbon atoms such as phenyl group. As Z, a linear alkylene group having 1 to 4 carbon atoms is preferred.

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

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

As a preparation method of the fluorooxyalkyl group-containing polymer represented by the above formula (5), for example, a fluorooxyalkyl group-containing polymer having a hydroxyl group at a single end of the molecular chain and two olefin sites (that is, having 1 Valence polymer residues containing fluorooxyalkylene groups and polymers with two olefin sites and hydroxyl groups at the single end of the molecular chain) and hydrosilanes in the presence of dehydrogenation catalysts, using solvents, at 0~60℃ , Preferably the dehydrogenation reaction is carried out at a temperature of 15~35°C, more preferably about 25°C, for 10 minutes to 24 hours, preferably 30 minutes to 2 hours, more preferably about 1 hour.

In addition, as another method of preparing a fluorooxyalkyl group-containing polymer represented by the above formula (5), a fluorooxyalkyl group-containing polymer having a hydroxyl group at a single end of the molecular chain and two olefin sites (I.e., a polymer having a monovalent fluorooxyalkylene group-containing polymer residue and a polymer having two olefin sites 2 and a hydroxyl group at a single end of the molecular chain), and for example, a fluorine-containing polymer having a fluorine at a single end of the molecular chain Oxyalkyl polymer, in the presence of a base, use a solvent at a temperature of 0~100°C, preferably 25~80°C, more preferably 60°C, for 1~48 hours, preferably 5~36 hours , It is more preferable to carry out dehydrohalogenation (dehydrofluorination) reaction under the conditions of about 20 hours.

Here, the fluorooxyalkyl group-containing polymer having fluorine at a single end of the molecular chain is the group at the single end of the molecular chain. In addition to the above-mentioned fluorine, other halides (for example, Chlorine), acid anhydrides, esters (for example, alkyl esters such as methyl esters), carboxylic acids, and the like.

Specific examples of the perfluorooxyalkyl group-containing polymer having these groups (halogen, acid anhydride, ester, carboxylic acid, etc.) at a single 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 fluorooxyalkyl group-containing polymer having a functional group such as fluorine at one end of the molecular chain is relative to the reactive end group of the fluorooxyalkyl group-containing polymer having a hydroxyl group at the single end of the molecular chain ( Hydroxy) 1 equivalent, which can be 0.5 to 1 equivalent, preferably 0.8 to 1 equivalent, and more preferably about 0.9 equivalent.

As the base used in the preparation of the fluorooxyalkyl group-containing polymer represented by the formula (5), for example, amines or alkali metal bases can be used. Specific examples of amines include triethylamine and diisopropylamine. Propylethylamine, pyridine, DBU, imidazole, etc. Examples of alkali metal bases include sodium hydroxide, potassium hydroxide, sodium hydride, potassium hydride, lithium alkyl, potassium tert-butoxide, lithium diisopropylamide, and bis(trimethylsilyl) Lithium amide, sodium bis(trimethylsilyl) amide, potassium bis(trimethylsilyl) amide, etc.

The amount of the base used can be 1 to 10 equivalents, preferably 1 to 3 equivalents, and more preferably about 1 equivalent to 1 equivalent of the reactive end group of the fluorooxyalkyl group-containing polymer having a hydroxyl group at a single end of the molecular chain. 2 equivalents.

In the preparation of the fluorooxyalkyl group-containing polymer represented by the above formula (5), the solvent used is preferably a fluorine-based solvent. Among the fluorine-based solvents, 1,3-bis(trifluoromethyl) Base) benzene, trifluoromethylbenzene, methyl nonafluorobutyl ether, methyl nonafluoroisobutyl ether, ethyl nonafluorobutyl ether, ethyl nonafluoroisobutyl ether, 1,1,1, Hydrofluoroether (HFE) solvents such as 2,3,4,4,5,5,5-decafluoro-3-methoxy-2-(trifluoromethyl)pentane (manufactured by 3M, trade name : Novec series), perfluorinated solvents composed of fully fluorinated compounds (manufactured by 3M, trade name: Fluorinert series), etc.

Relative to 100 parts by mass of the fluorooxyalkylene-containing polymer having two olefin sites at the single end of the molecular chain, the amount of solvent used can be 10 to 300 parts by mass, preferably 50 to 150 parts by mass, and more preferably Use about 100 parts by mass.

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 fluorooxyalkyl group-containing polymer represented by formula (5).

Here, as a raw material for the preparation of the fluorooxyalkyl group-containing polymer represented by the formula (5), a fluorooxyalkyl group-containing polymer having a hydroxyl group at a single end of the molecular chain and two olefin sites is used, specifically The ground can be as follows.

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

As the raw material, the preparation method of the fluorooxyalkyl group-containing polymer having a hydroxyl group at one end of the molecular chain and two olefin sites at the same time, for example, by mixing the single end of the molecular chain with a fluoro group (-C(=O) )-F) Polymers containing perfluorooxyalkyl groups and Grignard reagents with olefin moieties as nucleophiles, solvents such as 1,3-bis(trifluoromethyl)benzene, tetrahydrofuran, in 0 ~80°C, preferably 50~70°C, more preferably about 60°C, aging for 1~6 hours, preferably 3~5 hours, more preferably about 4 hours, and introduce 2 olefin sites at the single end of the molecular chain together with Hydroxy.

Here, the above-mentioned fluorooxyalkyl group-containing polymer having a hydroxyl group at one end of the molecular chain and two olefin moieties is used in the preparation of As a raw material, a polymer containing a perfluorooxyalkyl group is a group at the single end of the molecular chain. In addition to the above-mentioned fluorine, other halides (chlorine, etc.), acid anhydrides, esters, and carboxylic acids can also be used. , Amide, etc.

Specific examples of the perfluorooxyalkyl group-containing polymer having such a group at a single end of the molecular chain include those shown below.

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

As the nucleophile used in the preparation of the above-mentioned fluorooxyalkyl group-containing polymer having a hydroxyl group at one end of the molecular chain and two olefin moieties, allyl magnesium halide, 3-butenyl magnesium halide, halogenated 4-pentenyl magnesium, 5-hexene magnesium halide, etc. In addition, corresponding lithium reagents can also be used.

The amount of nucleophile used can be 2 to 5 equivalents, preferably 2.5 to 3,5 equivalents, and more preferably about 3 equivalents relative to 1 equivalent of the reactive end groups of the above-mentioned perfluorooxyalkyl group-containing polymer .

烷等之醚系溶劑。 In addition, as the solvent used in the preparation of the fluorooxyalkyl group-containing polymer having a hydroxyl group at a single end of the molecular chain and two olefin moieties, among the fluorine-based solvents, 1,3-bis(trifluoromethyl) Base) benzene, trifluoromethylbenzene, methyl nonafluorobutyl ether, methyl nonafluoroisobutyl ether, ethyl nonafluorobutyl ether, ethyl nonafluoroisobutyl ether, 1,1,1, Hydrofluoroether (HFE) solvents such as 2,3,4,4,5,5,5-decafluoro-3-methoxy-2-(trifluoromethyl)pentane (manufactured by 3M, trade name : Novec series), perfluorinated solvents composed of fully fluorinated compounds (manufactured by 3M, trade name: Fluorinert series), etc. Furthermore, as the organic solvent, tetrahydrofuran, monoethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, and diethylene glycol dimethyl ether can be used.

Ether solvents such as alkanes.

Relative to 100 parts by mass of the aforementioned perfluorooxyalkyl group-containing polymer, the amount of solvent used may be 10 to 300 parts by mass, preferably 100 to 200 parts by mass, and more preferably about 150 parts by mass.

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 the above-mentioned fluorooxyalkyl group-containing polymer having a hydroxyl group at one end of the molecular chain.

As the hydrosilane used in the preparation of the fluorooxyalkyl group-containing polymer represented by the formula (5), a polydimethylsiloxane having 2-40 silicon atoms whose end group is unilaterally blocked by an alkyl group can be mentioned. Alkyl terminal hydrosilane, terminal group The unilateral polydimethylsiloxane with 2-40 silicon atoms blocked by a fluoroalkyl group or a fluorooxyalkyl group is a polydimethylsiloxane terminal hydrogen silane, etc.

Specific examples of the hydrosilane used in the preparation of the fluorooxyalkyl group-containing polymer represented by the formula (5) include those shown below.

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

With respect to 1 equivalent of the reactive end group of the fluorooxyalkyl group-containing polymer having a hydroxyl group at a single end of the molecular chain and two olefin sites, the amount of the hydrosilane used can be 1 to 5 equivalents, preferably 1 to 2 equivalents, more preferably about 1.2 equivalents can be used.

As the dehydrogenation catalyst used in the preparation of the fluorooxyalkyl group-containing polymer represented by the formula (5), for example, platinum group metal catalysts such as rhodium, palladium, ruthenium, or boron catalysts can be used. Specifically Examples include platinum group metal catalysts such as tetrakis(triphenylphosphine)palladium and chlorotris(triphenylphosphine)rhodium, and boron catalysts such as tris(pentafluorophenyl)borane.

Relative to 1 equivalent of the reactive end group of the fluorooxyalkyl group-containing polymer having a hydroxyl group at one end of the molecular chain and two olefin sites, dehydrogenation The usage amount of the catalyst can be 0.01 to 0.0005 equivalents, preferably 0.007 to 0.001 equivalents, more preferably about 0.005 equivalents can be used.

烷等之醚系溶劑。 As the solvent used in the preparation of the fluorooxyalkyl group-containing polymer represented by the formula (5), among the fluorine-based solvents, 1,3-bis(trifluoromethyl)benzene, trifluoromethylbenzene, etc. Fluorinated aromatic hydrocarbon solvents, methyl nonafluorobutyl ether, methyl nonafluoroisobutyl ether, ethyl nonafluorobutyl ether, ethyl nonafluoroisobutyl ether, 1,1,1,2 ,3,4,4,5,5,5-decafluoro-3-methoxy-2-(trifluoromethyl)pentane and other hydrofluoroether (HFE) solvents (manufactured by 3M, trade name: Novec series), perfluorinated solvents composed of fully fluorinated compounds (manufactured by 3M, trade name: Fluorinert series), etc. Furthermore, as the organic solvent, tetrahydrofuran, monoethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, and diethylene glycol dimethyl ether can be used.

Ether solvents such as alkanes.

With respect to 100 parts by mass of a fluorooxyalkyl group-containing polymer having a hydroxyl group at a single end of the molecular chain and two olefin sites, the solvent can be used in an amount of 10 to 300 parts by mass, preferably 50 to 150 parts by mass, and more It is good to use about 100 parts by mass.

Then, 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 fluorooxyalkyl group-containing polymer represented by formula (5).

In the preparation of fluoropolyether group-containing polymer-modified silane when α represented by the above formula (1) is 1, the solvent used is preferably a fluorine-based solvent. Among the fluorine-based solvents, 1,3 -Bis(trifluoromethyl)benzene, trifluoromethyl Benzene, methyl nonafluorobutyl ether, methyl nonafluoroisobutyl ether, ethyl nonafluorobutyl ether, ethyl nonafluoroisobutyl 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, trade name: Novec series) Perfluorinated solvents composed of fluorinated compounds (manufactured by 3M, trade name: Fluorinert series), etc.

Relative to 100 parts by mass of the fluorooxyalkyl group-containing polymer having two olefin sites at the single end of the molecular chain, the amount of solvent used can be 10 to 300 parts by mass, preferably 50 to 150 parts by mass, and more preferably about 100 parts by mass.

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

(In the formula, R, X, n, R ¹ , R ² , g, and j are the same as above. R ³ is a divalent hydrocarbon group having 2 to 8 carbons. i is an integer of 2 to 9, preferably 2 to An integer of 4, i+j is an integer of 2-9).

Here, as the ^{divalent hydrocarbon group of R 3 having} 2 to 8 carbon atoms, preferably 2 to 3, methylene, ethylene, propylene (trimethylene, methylethylene), ethylene Butyl (tetramethylene, methyl propylene), hexamethylene, octamethylene and other alkylene groups, phenylene and other aryl groups, or a combination of two or more of these groups (Alkylene‧Aryl, etc.) etc. Among these, ethylene and trimethylene are preferred.

Examples of organosilicon compounds having SiH groups and hydrolyzable terminal groups in the molecule include trimethoxysilane, triethoxysilane, tripropoxysilane, triisopropoxysilane, and tributoxy Silane, Triisopropenoxysilane, triacetoxysilane, trichlorosilane, tribromosilane, triiodosilane, and the following organosilicon compounds.

In the preparation of fluoropolyether group-containing polymer-modified silane when α represented by formula (1) is 1, the fluorooxyalkyl group-containing polymer having two olefin sites at the single end of the molecular chain is combined with The amount of the organosilicon compound having SiH groups and hydrolyzable end groups in the molecule during the reaction of the organosilicon compound having SiH groups and hydrolyzable end groups in the molecule is relative to the amount of the organosilicon compound having two olefin sites at the single end of the molecular chain The reactive end group of the fluorooxyalkyl polymer is 1 equivalent, which can be 2-6 equivalents, preferably 2.2-3.5 equivalents, and more preferably about 3 equivalents.

In addition, in the preparation of polymer-modified silane containing fluoropolyether group when α represented by formula (1) is 1, it is used as an organic compound with two or more SiH groups that does not have hydrolyzable end groups in the molecule. The silicon compound is preferably a compound represented by the following general formulas (10) to (12).

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

Examples of the organosilicon compound having two or more SiH groups that do not have a hydrolyzable terminal group in the molecule include those shown below.

In the preparation of fluoropolyether-containing polymer modified silane when α represented by formula (1) is 1, the fluorooxyalkyl group-containing polymer having two olefin sites at the single end of the molecular chain and the in-molecular In the reaction of organosilicon compounds with more than 2 SiH groups that do not have hydrolyzable end groups The usage amount of an organosilicon compound with two or more SiH groups that does not have a hydrolyzable end group in the molecule is relative to the reactive end group of a fluorooxyalkyl group-containing polymer having two olefin sites at the single end of the molecular chain One equivalent can be 5-20 equivalents, preferably 7.5-12.5 equivalents, and more preferably about 10 equivalents can be used.

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

(In the formula, R, X, and n are the same as above. V is a single bond or a divalent hydrocarbon group with 1 to 6 carbons).

In the above formula (13), V is a single bond or a divalent hydrocarbon group having 1 to 6 carbons, and specific examples of the divalent hydrocarbon group having 1 to 6 carbon include methylene, ethylene, and propylene ( Trimethylene, methyl ethylene), butylene (tetramethylene, methyl propylene), hexamethylene and other alkylenes, phenylene, etc. V is preferably a single bond or a methylene group.

In the preparation of fluoropolyether group-containing polymer-modified silane when α represented by formula (1) is 1, the fluorooxyalkyl group-containing polymer having two olefin sites at the single end of the molecular chain is combined with When the reactant of an organosilicon compound having two or more SiH groups that does not have a hydrolyzable end group in the molecule reacts with an organosilicon compound having an olefin site and a hydrolyzable end group in the molecule, it has an olefin site in the molecule and hydrolysis Organic silicon The amount of the compound used is relative to the reaction between a fluorooxyalkyl group-containing polymer having two olefin sites at one end of the molecular chain and an organosilicon compound having two or more SiH groups that does not have a hydrolyzable end group in the molecule One equivalent of the reactive end group of the substance can be 2-6 equivalents, preferably 2.2-3.5 equivalents, and more preferably about 3 equivalents can be used.

In the preparation of polymer-modified silane containing fluoropolyether group when α represented by formula (1) is 1, the catalyst for the hydrosilylation reaction includes platinum black, chloroplatinic acid, and chloroplatinic acid. Alcohol modification products, chloroplatinic acid and olefins, aldehydes, vinylsiloxane bonds, acetylenic alcohols, etc., tetrakis (triphenylphosphine) palladium, chlorotris (triphenylphosphine) rhodium, etc. Platinum group metal catalyst. Preferred are platinum compounds such as vinylsiloxane coordination compounds.

Relative to a polymer containing fluorooxyalkyl groups having two olefin sites at a single end of the molecular chain or a reaction material between this polymer and an organosilicon compound having two or more SiH groups that does not have a hydrolyzable end group in the molecule The amount is converted to a transition metal (mass), and the amount of the catalyst used in the hydrosilylation reaction is 0.1-100 ppm, preferably 1-50 ppm.

Then, the solvent and unreacted materials are distilled off under reduced pressure to obtain the desired compound.

For example, as a fluorooxyalkyl group-containing polymer having two olefin moieties at a single end of the molecular chain, a compound represented by the following formula is used:

As an organosilicon compound having a SiH group and a hydrolyzable terminal group in the molecule, when trimethoxysilane is used, a compound represented by the following formula is obtained.

As a method of preparing a polymer-modified silane containing a fluoropolyether group when α represented by the above formula (1) is 2, for example, the following method can be cited.

Make a fluorooxyalkylene-containing polymer having two olefin sites at each end of the molecular chain (that is, a divalent fluorooxyalkylene-containing polymer residue and two at each end of the molecular chain Olefin polymer) is dissolved in a solvent such as 1,3-bis(trifluoromethyl)benzene and other fluorine-based solvents to make trimethoxysilane and other organosilicons having SiH groups and hydrolyzable end groups in the molecule Compound, in the presence of a catalyst for the hydrosilylation reaction, such as a toluene solution of chloroplatinic acid/vinylsiloxane complex, at a temperature of 40~120℃, preferably 60~100℃, more preferably about 80℃ , It is matured for 1 to 72 hours, preferably 20 to 36 hours, more preferably about 24 hours.

In addition, instead of the above-mentioned organosilicon compound having SiH groups and hydrolyzable end groups in the molecule, an organosilicon compound containing SiH groups that does not have a hydrolyzable end group can also be used. An organosilicon compound with more than two SiH groups with hydrolyzable end groups. At that time, using the same method as the above A fluorooxyalkylene-containing polymer having two olefin sites at each end of the chain reacts with an organosilicon compound having two or more SiH groups, which does not have a hydrolyzable end group in the molecule, at a molar ratio or more. After the reactant (intermediate) with two remaining SiH groups at each end of the molecular chain, the reaction product (intermediate) is integrated into the molecule between the SiH group at the end of the polymer and allyltrimethoxysilane. An organosilicon compound with an olefin moiety and a hydrolyzable terminal group in the presence of a hydrosilylation catalyst such as a toluene solution of chloroplatinic acid/vinylsiloxane complex at 40~120℃, preferably at 60 ~100°C, more preferably at a temperature of about 80°C, aging for 1 to 72 hours, preferably 20 to 36 hours, more preferably about 24 hours.

Here, as a fluorooxyalkylene group-containing polymer having two olefin moieties at each end of the molecular chain, a fluorooxyalkylene group-containing polymer represented by the following general formula (14) can be exemplified.

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

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

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

As a preparation method of the fluorooxyalkylene-containing polymer represented by the above formula (14), for example, a fluorooxyalkylene-containing polymer having hydroxyl groups at both ends of the molecular chain and two olefin sites at both ends of the molecular chain Polymers (ie, polymers with divalent fluorooxyalkylene-containing polymer residues and polymers with two olefin sites and hydroxyl groups at each end of the molecular chain) and hydrosilanes in the presence of dehydrogenation catalysts , Use a solvent to perform dehydrogenation at a temperature of 0~60℃, preferably 15~35℃, more preferably about 25℃, for 10 minutes~24 hours, preferably 30 minutes~2 hours, more preferably about 1 hour anti- should.

In addition, as another method of preparing the fluorooxyalkylene-containing polymer represented by the above formula (14), a fluorine-containing polymer having hydroxyl groups at both ends of the molecular chain and two olefin sites at both ends of the molecular chain Oxyalkylene polymers (that is, polymers with divalent fluorooxyalkylene-containing polymer residues and polymers with two olefin sites and hydroxyl groups at each end of the molecular chain) and, for example, at one end of the molecular chain A polymer containing fluorooxyalkyl groups with fluorine, in the presence of a base, use a solvent at a temperature of 0~100°C, preferably 25~80°C, more preferably at a temperature of 60°C, for 1~48 hours, Preferably, the dehydrohalogenation (dehydrofluorination) reaction and the like are carried out under the conditions of 5 to 36 hours, more preferably about 20 hours.

Here, the fluorooxyalkyl group-containing polymer having fluorine at a single end of the molecular chain is used as a group at a single end of the molecular chain. In addition to the above-mentioned fluorine, halides, acid anhydrides, esters, etc. can also be used. Carboxylic acid and so on.

Specific examples of the perfluorooxyalkyl group-containing polymer having these groups (halogen, acid anhydride, ester, carboxylic acid, etc.) at a single 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 fluorooxyalkylene-containing polymer having fluorine at one end of the molecular chain is 1 equivalent to the reactive end group (hydroxyl group) of the fluorooxyalkylene-containing polymer having hydroxyl groups at both ends of the molecular chain , Can be 0.5 to 1 equivalent, preferably 0.8 to 1 equivalent, more preferably about 0.9 equivalent can be used.

As the base used in the preparation of the fluorooxyalkylene-containing polymer represented by the formula (14), for example, amines or alkali metal bases can be used. Specifically, among the amines, triethylamine, two Isopropylethylamine, pyridine, DBU, imidazole, etc. Examples of alkali metal bases include sodium hydroxide, potassium hydroxide, sodium hydride, potassium hydride, lithium alkyl, potassium tert-butoxide, lithium diisopropylamide, and bis(trimethylsilyl) Lithium amide, sodium bis(trimethylsilyl) amide, potassium bis(trimethylsilyl) amide, etc.

The amount of the base used can be 1 to 10 equivalents, preferably 1 to 3 equivalents, and more preferably about 1 equivalent to 1 equivalent of the reactive end groups of the fluorooxyalkyl group-containing polymer having hydroxyl groups at both ends of the molecular chain. 2 equivalents.

In the preparation of the fluorooxyalkylene-containing polymer represented by the above formula (14), the solvent used is preferably a fluorine-based solvent. Among the fluorine-based solvents, 1,3-bis(trifluoromethyl) Base) benzene, trifluoromethylbenzene, methyl nonafluorobutyl ether, methyl nonafluoroisobutyl ether, ethyl nonafluorobutyl ether, ethyl nonafluoroisobutyl ether, 1,1,1, Hydrofluoroether (HFE) solvents such as 2,3,4,4,5,5,5-decafluoro-3-methoxy-2-(trifluoromethyl)pentane (manufactured by 3M, trade name : Novec series), perfluorinated solvents composed of fully fluorinated compounds (manufactured by 3M, trade name: Fluorinert series), etc.

Relative to 100 parts by mass of the fluorooxyalkylene-containing polymer having hydroxyl groups at both ends of the molecular chain, the amount of solvent used can be 10 to 300 parts by mass, preferably 50 to 150 parts by mass, and more preferably about 100 parts by mass. Mass parts.

Then, 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 fluorooxyalkyl group-containing polymer represented by formula (14).

Here, the fluorooxyalkylene-containing polymer used in the preparation of the fluorooxyalkylene-containing polymer represented by the formula (14) has hydroxyl groups at both ends of the molecular chain and two olefin moieties at both ends of the molecular chain. Specific examples of the polymer of the base include those shown below.

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

Here, as the preparation method of the above-mentioned fluorooxyalkylene-containing polymer having hydroxyl groups at both ends of the molecular chain and 2 olefin sites at both ends of the molecular chain, for example, by mixing fluorine at both ends of the molecular chain Group (-C(=O)-F) containing a perfluorooxyalkylene polymer and a Grignard reagent with an olefin site as a nucleophile, as a solvent such as 1,3-bis(trifluoro) (Methyl)benzene, tetrahydrofuran, aged at 0~80℃, preferably at 50~70℃, more preferably at about 60℃, for 1~6 hours, preferably 3~5 hours, more preferably about 4 hours, and in the molecular Two olefin sites and hydroxyl groups are introduced at both ends of the chain.

Here, the perfluorooxyalkylene-containing polymer is a group possessed at both ends of the molecular chain. In addition to the above-mentioned fluorine, halides, acid anhydrides, esters, carboxylic acids, amides, etc. may also be used.

As a group containing perfluorooxane at both ends of the molecular chain Specific examples of the polymer of the base include those shown below.

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

As the nucleophile used in the preparation of the fluorooxyalkylene-containing polymer having hydroxyl groups at both ends of the molecular chain, allyl magnesium halide, 3-butenyl magnesium halide, and 4-pentenyl halide can be used. Magnesium, 5-hexene magnesium halide, etc. In addition, corresponding lithium reagents can also be used.

The amount of the nucleophile used can be 4-10 equivalents, preferably 5-7 equivalents, and more preferably about 6 equivalents, relative to 1 equivalent of the reactive end groups of the above-mentioned perfluorooxyalkylene-containing polymer.

烷等之醚系溶劑。 In addition, as the solvent used in the preparation of the above-mentioned fluorooxyalkylene-containing polymer having hydroxyl groups at both ends of the molecular chain, among the fluorine-based solvents, 1,3-bis(trifluoromethyl)benzene, tris Fluoromethyl benzene, methyl nonafluorobutyl ether, methyl nonafluoroisobutyl ether, ethyl nonafluorobutyl ether, ethyl nonafluoroisobutyl ether, 1,1,1,2,3,4 ,4,5,5,5-Decafluoro-3-methoxy-2-(trifluoromethyl)pentane and other hydrofluoroether (HFE) solvents (manufactured by 3M, trade name: Novec series), Perfluorinated solvents (manufactured by 3M, trade name: Fluorinert series) composed of fully fluorinated compounds. Furthermore, as the organic solvent, tetrahydrofuran, monoethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, and diethylene glycol dimethyl ether can be used.

Ether solvents such as alkanes.

Relative to 100 parts by mass of the above-mentioned perfluorooxyalkylene-containing polymer, the amount of solvent used may be 10 to 300 parts by mass, preferably 100 to 200 parts by mass, and more preferably about 150 parts by mass.

Then, 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 the above-mentioned fluorooxyalkylene-containing polymer having hydroxyl groups at both ends of the molecular chain.

As the hydrosilane used in the preparation of the fluorooxyalkylene-containing polymer represented by the formula (14), there can be exemplified polydimethylsiloxane having a silicon atom number of 2 to 40 whose end group is unilaterally blocked by an alkyl group. The oxane-terminal hydrosilane, the end group unilaterally blocked by a fluoroalkyl group or a polydimethylsiloxane-terminated polydimethylsiloxane with a silicon atom number of 2-40, etc.

Relative to 1 equivalent of reactive end groups of a fluorooxyalkylene-containing polymer having a hydroxyl group at one end of the molecular chain and 2 olefin sites at both ends of the molecular chain, the amount of hydrosilane used can be 1 to 5 equivalents , Preferably 1 to 2 equivalents, more preferably about 1.2 equivalents can be used.

As a polymer containing fluorooxyalkylene represented by formula (14) The dehydrogenation catalyst used in the preparation of the catalyst, for example, platinum group metal catalysts such as rhodium, palladium, ruthenium, or boron catalysts, etc. can be used. Specifically, tetrakis(triphenylphosphine)palladium, chlorotris(tris) Platinum group metal catalysts such as phenylphosphine) rhodium, boron catalysts such as tris(pentafluorophenyl)borane, etc.

The amount of dehydrogenation catalyst can be 0.01~0.0005 relative to 1 equivalent of reactive end group of fluorooxyalkylene-containing polymer with hydroxyl groups at both ends of the molecular chain and 2 olefin sites at both ends of the molecular chain. The equivalent is preferably 0.007 to 0.001 equivalent, more preferably about 0.005 equivalent can be used.

烷等之醚系溶劑。 As the solvent used in the preparation of the fluorooxyalkylene-containing polymer represented by the formula (14), among the fluorine-based solvents, 1,3-bis(trifluoromethyl)benzene and trifluoromethylbenzene Fluorine-containing aromatic hydrocarbon solvents, methyl nonafluorobutyl ether, methyl nonafluoroisobutyl ether, ethyl nonafluorobutyl ether, ethyl nonafluoroisobutyl ether, 1,1,1, Hydrofluoroether (HFE) solvents such as 2,3,4,4,5,5,5-decafluoro-3-methoxy-2-(trifluoromethyl)pentane (manufactured by 3M, trade name : Novec series), perfluorinated solvents composed of fully fluorinated compounds (manufactured by 3M, trade name: Fluorinert series), etc. Furthermore, as the organic solvent, tetrahydrofuran, monoethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, and diethylene glycol dimethyl ether can be used.

Ether solvents such as alkanes.

With respect to 100 parts by mass of a fluorooxyalkylene-containing polymer having hydroxyl groups at both ends of the molecular chain and 2 olefin sites at both ends of the molecular chain, the amount of solvent used may be 10 to 300 parts by mass, preferably 50 to 150 parts by mass, more preferably about 100 parts by mass can be used.

Then, the reaction is stopped, and the water layer is separated by liquid separation operation With fluorine solvent layer. The obtained fluorine solvent layer is further washed with an organic solvent, and the solvent is distilled off to obtain a fluorooxyalkylene-containing polymer represented by formula (14).

In the preparation of fluoropolyether group-containing polymer-modified silane when α represented by the above formula (1) is 2, the solvent used is preferably a fluorine-based solvent. Among the fluorine-based solvents, 1, 3-bis(trifluoromethyl)benzene, trifluoromethylbenzene, methyl nonafluorobutyl ether, methyl nonafluoroisobutyl ether, ethyl nonafluorobutyl ether, ethyl nonafluoroisobutyl ether , 1,1,1,2,3,4,4,5,5,5-decafluoro-3-methoxy-2-(trifluoromethyl)pentane and other hydrofluoroether (HFE) solvents (Manufactured by 3M Company, trade name: Novec series), perfluorinated solvents composed of fully fluorinated compounds (manufactured by 3M Company, trade name: Fluorinert series), etc.

Relative to 100 parts by mass of the fluorooxyalkylene-containing polymer having two olefin sites at both ends of the molecular chain, the amount of solvent used can be 10 to 300 parts by mass, preferably 50 to 150 parts by mass, and more preferably Use about 100 parts by mass.

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

(In the formula, R, X, n, R ¹ , R ² , R ³ , g, i, and j are the same as above).

Examples of organosilicon compounds having SiH groups and hydrolyzable terminal groups in the molecule include trimethoxysilane, triethoxysilane, tripropoxysilane, triisopropoxysilane, and tributoxy Silane, triisopropenoxysilane, triacetoxysilane, trichlorosilane, tribromosilane, triiodosilane, and the following organosilicon compounds.

In the preparation of fluoropolyether group-containing polymer modified silane when α represented by formula (1) is 2, a fluorooxyalkylene-containing polymer having two olefin sites at each end of the molecular chain When reacting with 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 used relative to each having 2 olefins at both ends of the molecular chain One equivalent of the reactive end group of the polymer containing the fluorooxyalkylene group at the site may be 2-6 equivalents, preferably 2.2-3.5 equivalents, and more preferably about 3 equivalents may be used.

In addition, in the preparation of polymer-modified silane containing fluoropolyether group when α represented by formula (1) is 2, it is used as an organic compound with two or more SiH groups that does not have hydrolyzable end groups in the molecule. The silicon compound is preferably a compound represented by the following general formulas (10) to (12).

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

Examples of the organosilicon compound having two or more SiH groups that do not have a hydrolyzable terminal group in the molecule include those shown below.

In the preparation of a fluoropolyether group-containing polymer modified silane when α represented by formula (1) is 2, a fluorooxyalkylene-containing polymer having two olefin sites at both ends of the molecular chain and Reaction of organosilicon compounds with more than 2 SiH groups that do not have hydrolyzable end groups in the molecule The amount of the organosilicon compound with two or more SiH groups that does not have a hydrolyzable end group in the molecule at that time is relative to the fluorooxyalkylene-containing polymer having two olefin sites at each end of the molecular chain The reactive end group of 1 equivalent can be 5-20 equivalents, preferably 7.5-12.5 equivalents, and more preferably about 10 equivalents can be used.

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

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

In the preparation of fluoropolyether group-containing polymer modified silane when α represented by formula (1) is 2, a fluorooxyalkylene-containing polymer having two olefin sites at each end of the molecular chain When reacting with the reactant (intermediate) of an organosilicon compound having two or more SiH groups that does not have a hydrolyzable end group in the molecule, and an organosilicon compound having an olefin site and a hydrolyzable end group in the molecule, it is in the molecule The usage amount of the organosilicon compound with olefin moiety and hydrolyzable end group is relative to the fluorooxyalkylene-containing polymer having 2 olefin moieties at each end of the molecular chain and the molecule that does not have hydrolyzable end group. The reactant (intermediate) of an organosilicon compound having two or more SiH groups has 1 equivalent of reactive end groups, which can be 2-6 equivalents, preferably 2.2-3.5 equivalents, and preferably about 3 equivalents can be used.

When α expressed by formula (1) is 2, the fluoropolyether group-containing In the preparation of polymer-modified silanes, as catalysts for the hydrosilylation reaction, platinum black, chloroplatinic acid, alcohol-modified products of chloroplatinic acid, chloroplatinic acid and olefins, aldehydes, vinyl siloxanes, and alkynes can be mentioned. It is a platinum group metal catalyst such as complex compounds such as alcohols, tetrakis(triphenylphosphine) palladium, and chlorotris(triphenylphosphine) rhodium. Preferred are platinum compounds such as vinylsiloxane coordination compounds.

The amount of the catalyst used in the hydrosilylation reaction is relative to the fluorooxyalkylene-containing polymer having two olefin sites at each end of the molecular chain, or the polymer having no hydrolyzable end groups in the polymer and the molecule. The mass of the reactant (intermediate) of more than one SiH-based organosilicon compound is converted to transition metal (mass). The amount of the catalyst used in the hydrosilylation reaction is 0.1-100 ppm, preferably 1-50 ppm. use.

Then, the solvent and unreacted materials are distilled off under reduced pressure to obtain the desired compound.

For example, as a fluorooxyalkylene-containing polymer having two olefin sites at each end of the molecular chain, a compound represented by the following formula is used,

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

The present invention further provides a surface treatment agent containing the above-mentioned fluoropolyether group-containing polymer modified silane. The surface treatment agent can also be used to partially hydrolyze the terminal hydrolyzable groups of the above-mentioned fluoropolyether group-containing polymer modified silane to become hydroxyl groups by a well-known method. The fluoropolyether-based polymer modifies a part of the hydrolyzable group of X in the silane to be hydrolyzed to become a hydroxyl group.

In the surface treatment agent, hydrolysis and condensation catalysts can also be added as needed, such as organic tin compounds (dibutyl tin dimethoxide, dibutyl tin dilaurate, etc.), organic titanium compounds (tetra-n-butyl titanate, etc.), Organic acids (acetic acid, methanesulfonic acid, fluorine-modified carboxylic acid, etc.), inorganic acids (hydrochloric acid, sulfuric acid, etc.), etc. Among these, particularly preferred are acetic acid, tetra-n-butyl titanate, dibutyl tin dilaurate, and fluorine-modified carboxylic acid.

The addition amount of the hydrolysis condensation catalyst is the amount of the catalyst, usually 0.01 to 5 parts by mass, especially 0.1 to 1 part by mass relative to 100 parts by mass of the polymer-modified silane containing fluoropolyether groups.

The surface treatment agent may also contain an appropriate solvent. Examples of such solvents include fluorine-modified aliphatic hydrocarbon solvents (perfluoroheptane, perfluorooctane, etc.), fluorine-modified aromatic hydrocarbon solvents (1,3-bis(trifluoromethyl)benzene, etc.) ), fluorine-modified ether solvents (methyl perfluorobutyl ether, ethyl perfluorobutyl ether, perfluoro(2-butyltetrahydrofuran), etc.), fluorine-modified alkylamine solvents (all Fluorotributylamine, perfluorotripentylamine, etc.), hydrocarbon solvents (petroleum ether, toluene, xylene, etc.), ketone solvents (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.). Among these, in terms of solubility, wettability, etc., a fluorine-modified solvent is preferred, especially 1,3-bis(trifluoromethyl)benzene, perfluoro(2-butyltetrahydrofuran) ), perfluorotributylamine, ethyl perfluorobutyl ether.

The above-mentioned solvent system may be a mixture of two or more kinds thereof, and it is preferably one that uniformly dissolves the fluoropolyether group-containing polymer-modified silane. Furthermore, the most suitable concentration of fluoropolyether-containing polymer-modified silane dissolved in the solvent varies with the processing method, as long as it is an amount that is easy to weigh, but when it is directly coated, it is relative to the solvent The total mass of silane and the polymer-modified silane containing fluoropolyether group is preferably 0.01-10% by mass, particularly preferably 0.05-5% by mass. When the vapor deposition process is performed, it is relative to the solvent and fluoropolyether-containing polymer. The total mass of the polymer-modified silane is preferably 1-100% by mass, particularly preferably 3-30% by mass.

The surface treatment agent of the present invention can be applied to the substrate by well-known coating methods such as brush coating, dipping, spraying, and vapor deposition treatment. The heating method at the time of the vapor deposition treatment 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 applied by vapor deposition treatment, it is preferably in the range of 20 to 200°C. In addition, it can be hardened under humidification. The thickness of the cured film is appropriately selected according to the type of substrate, but it 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 can be made of various materials such as paper, cloth, metal and its oxide, glass, plastic, ceramic, and quartz. In particular, it can be suitably used as a surface treatment agent for glass or thin film treated _{with SiO 2.}

Examples of articles treated with the surface treatment agent of the present invention include car navigation devices, mobile phones, digital cameras, digital cameras, PDAs, portable audio players, car audios, game consoles, spectacle lenses, camera lenses, filters Optical objects such as medical equipment such as optical mirrors, sunglasses, gastroscopes, photocopiers, PCs, liquid crystal displays, organic EL displays, plasma displays, touch panel displays, protective films, anti-reflection films, etc. Since the surface treatment agent of the present invention can prevent fingerprints and sebum from adhering to the aforementioned articles, and can impart damage resistance, it is particularly useful as a water and oil repellent layer for touch panel displays, anti-reflection films, and the like.

In addition, the surface treatment agent of the present invention is also useful as antifouling coating for sanitary products such as baths and washstands, antifouling coatings for window glass or tempered glass, headlight covers, etc. of automobiles, trams, aircrafts, etc., and building materials for outer walls. Water-repellent and oil-repellent coating, anti-oil coating for kitchen building materials, anti-fouling and anti-sticker for telephone booths, graffiti coating, anti-fingerprint coating for art, etc., anti-fingerprints for CD, DVD, etc. Adhesive coatings, mold release agents or paint additives, resin modifiers, fluidity modifiers or dispersibility modifiers for inorganic fillers, lubricity improvers for tapes, films, etc.

[Example]

Hereinafter, examples and comparative examples are shown to explain the present invention in more detail, but the present invention is not limited by the following examples.

[Example 1]

In the reaction vessel, 100 g of 1,3-bis(trifluoromethyl)benzene, 0.01 g (2.0×10 ^-5 mol) of tris(pentafluorophenyl)borane, and 114 g of a compound represented by the following formula (A) were mixed ( 2.7×10 ^-2 mol),

^{After slowly dropping 13.6 g (3.3×10 -2} mol) of silane represented by the following formula (B),

Stir at 25°C for 1 hour. Next, water was added, the lower fluorine compound layer was recovered by a liquid separation operation, and then washed with acetone. The fluorine compound layer in the lower layer after washing was recovered again, and the remaining solvent was distilled off under reduced pressure to obtain 103 g of a fluoropolyether group-containing polymer represented by the following formula (C).

¹ H-NMR

δ 0-0.2(-OSi(C H ₃ ) ₃ )24H

δ 0.5-0.7(-SiC H ₂ CH ₂ CH ₂ CH ₃ )2H

δ 0.8-1.0(-SiCH ₂ CH ₂ CH ₂ C H ₃ )3H

δ 1.2-1.4(-SiCH ₂ C H ₂ C H ₂ CH ₃ )4H

δ 2.4-2.6(-C H ₂ CH=CH ₂ )4H

δ 4.9-5.1(-CH ₂ CH=C H ₂ )4H

δ 5.7-5.9(-CH ₂ C H =CH ₂ )2H

Mix in the reaction vessel with the following formula (C)

The indicated compound 111g (2.4×10 ^-2 mol), 1,3-bis(trifluoromethyl)benzene 90g, trimethoxysilane 9g (7.4×10 ^-2 mol) and chloroplatinic acid/vinylsiloxane The toluene solution of the complex is 9.0×10 ^-2 g (containing 2.4×10 ^-6 mol of Pt element) and matured at 80°C for 24 hours. Then, the solvent and unreacted materials were distilled off under reduced pressure to obtain 88 g of a liquid product.

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

¹ H-NMR

δ 0-0.2(-OSi(C H ₃ ) ₃ )24H

δ 0.5-0.7(-SiC H ₂ CH ₂ CH ₂ CH ₃ ,-CH ₂ CH ₂ C H ₂ -Si(OCH ₃ ) ₃ )6H

δ 0.8-1.0(-SiCH ₂ CH ₂ CH ₂ C H ₃ )3H

δ 1.3-1.4(-SiCH ₂ C H ₂ C H ₂ CH ₃ )4H

δ 1.5-1.9(-CH ₂ C H ₂ CH ₂ -Si(OCH ₃ ) ₃ ,-C H ₂ CH ₂ CH ₂ -Si(OCH ₃ ) ₃ )8H

δ 3.4-3.7(-Si(OC H ₃ ) ₃ )18H

[Example 2]

In the reaction vessel, 100 g of 1,3-bis(trifluoromethyl)benzene, 0.01 g (2.0×10 ^-5 mol) of tris(pentafluorophenyl)borane, and 114 g of a compound represented by the following formula (A) were mixed ( 2.7×10 ^-2 mol),

^{After slowly dropping 25.8 g (3.3×10 -2} mol) of silane represented by the following formula (E),

Stir at 25°C for 1 hour. Next, water was added, the lower fluorine compound layer was recovered by a liquid separation operation, and then washed with acetone. The fluorine compound layer in the lower layer after washing was recovered again, and the remaining solvent was distilled off under reduced pressure to obtain 125 g of a fluoropolyether group-containing polymer represented by the following formula (F).

¹ H-NMR

δ 0-0.2(-OSi(C H ₃ ) ₃ )60H

δ 0.5-0.7(-SiC H ₂ CH ₂ CH ₂ CH ₃ )2H

δ 0.8-1.0(-SiCH ₂ CH ₂ CH ₂ C H ₃ )3H

δ 1.2-1.4(-SiCH ₂ C H ₂ C H ₂ CH ₃ )4H

δ 2.4-2.6(-C H ₂ CH=CH ₂ )4H

δ 4.9-5.1(-CH ₂ CH=C H ₂ )4H

δ 5.7-5.9(-CH ₂ C H =CH ₂ )2H

Mix in the reaction vessel with the following formula (F)

The indicated compound 120g (2.4×10 ^-2 mol), 1,3-bis(trifluoromethyl)benzene 90g, trimethoxysilane 9g (7.4×10 ^-2 mol), and chloroplatinic acid/vinylsiloxane The toluene solution of the complex is 9.0×10 ^-2 g (containing 2.4×10 ^-6 mol of Pt element) and matured at 80°C for 24 hours. Then, the solvent and unreacted materials were distilled off under reduced pressure to obtain 76 g of a liquid product.

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

¹ H-NMR

δ 0-0.2(-OSi(C H ₃ ) ₃ )60H

δ 0.5-0.7(-SiC H ₂ CH ₂ CH ₂ CH ₃ ,-CH ₂ CH ₂ C H ₂ -Si(OCH ₃ ) ₃ )6H

δ 0.8-1.0(-SiCH ₂ CH ₂ CH ₂ C H ₃ )3H

δ 1.3-1.4(-SiCH ₂ C H ₂ C H ₂ CH ₃ )4H

δ 1.5-1.9(-CH ₂ C H ₂ CH ₂ -Si(OCH ₃ ) ₃ ,-C H ₂ CH ₂ CH ₂ -Si(OCH ₃ ) ₃ )8H

δ 3.4-3.7(-Si(OC H ₃ ) ₃ )18H

[Example 3]

Mix 100 g of 1,3-bis(trifluoromethyl)benzene, 0.01 g (2.0×10 ^-5 mol) of tris(pentafluorophenyl)borane, and 112.2 g of the compound represented by the following formula (H) in the reaction vessel (2.6×10 ^-2 mol),

^{After slowly dropping 27.2 g (6.6×10 -2} mol) of silane represented by the following formula (B),

Stir at 25°C for 1 hour. Next, water was added, the lower fluorine compound layer was recovered by a liquid separation operation, and then washed with acetone. After recycling and washing again In the lower fluorine compound layer, the remaining solvent was distilled off under reduced pressure to obtain 105 g of a fluoropolyether group-containing polymer represented by the following formula (I).

¹ H-NMR

δ 0-0.2(-OSi(C H ₃ ) ₃ )48H

δ 0.5-0.7(-SiC H ₂ CH ₂ CH ₂ CH ₃ )4H

δ 0.8-1.0(-SiCH ₂ CH ₂ CH ₂ C H ₃ )6H

δ 1.2-1.4(-SiCH ₂ C H ₂ C H ₂ CH ₃ ) 8H

δ 2.4-2.6(-C H ₂ CH=CH ₂ )8H

δ 4.9-5.1(-CH ₂ CH=C H ₂ )8H

δ 5.7-5.9(-CH ₂ C H =CH ₂ )4H

Mix in the reaction vessel with the following formula (I)

The indicated compound 90g (1.75×10 ^-2 mol), 1,3-bis(trifluoromethyl)benzene 90g, trimethoxysilane 12.8g (10.5×10 ^-2 mol) and chloroplatinic acid/vinyl silicone The toluene solution of the alkane complex is 8.4×10 ^-2 g (contains 2.3×10 ^-6 mol of Pt element) and matured at 80°C for 24 hours. Then, the solvent and unreacted materials 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.

¹ H-NMR

δ 0-0.2(-OSi(C H ₃ ) ₃ )48H

δ 0.5-0.7(-SiC H ₂ CH ₂ CH ₂ CH ₃ ,-CH ₂ CH ₂ C H ₂ -Si(OCH ₃ ) ₃ )12H

δ 0.8-1.0(-SiCH ₂ CH ₂ CH ₂ C H ₃ )6H

δ 1.3-1.4(-SiCH ₂ C H ₂ C H ₂ CH ₃ ) 8H

δ 1.5-1.9(-CH ₂ C H ₂ CH ₂ -Si(OCH ₃ ) ₃ ,-C H ₂ CH ₂ CH ₂ -Si(OCH ₃ ) ₃ )16H

δ 3.4-3.7(-Si(OC H ₃ ) ₃ )36H

[Example 4]

Mix 30 g of 1,3-bis(trifluoromethyl)benzene, 3.0×10 ^-2 g of toluene solution of chloroplatinic acid/vinylsiloxane complex in the reaction vessel (containing 8.2×10 ^-7 mol of Pt Simple substance), 6.0g (4.5×10 ^{-2 mol) of tetramethyldisiloxane, slowly drop 30g (7.2×10 -3} mol) of the compound represented by the following formula (K),

Stir at 25°C for 1 hour. Then, the solvent and unreacted materials 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.

¹ H-NMR

δ 0-0.2(-OSi(C H ₃ ) ₃ )12H

δ 0.5-0.7(-OCH ₂ CH ₂ C H ₂ -Si)2H

δ 1.6-1.8(-OCH ₂ C H ₂ CH ₂ -Si)2H

δ 3.5-3.6(-OC H ₂ CH ₂ CH ₂ -Si)2H

δ 3.7-3.8(-C ₂ F ₂ C H ₂ O-) 2H

δ 4.7-4.8(-Si- H )1H

Mix 10g of 1,3-bis(trifluoromethyl)benzene and 2.8×10 ^-3 g (5.5×10 ^-6 mol) of tris(pentafluorophenyl)borane in the reaction vessel, expressed by the following formula (A) 11.4g (2.7×10 ^-3 mol) of the compound,

^{After slowly dropping 11.7 g (2.7×10 -3} mol) of the compound represented by the following formula (L),

Stir at 25°C for 1 hour. Next, water was added, the lower fluorine compound layer was recovered by a liquid separation operation, and then washed with acetone. The fluorine compound layer in the lower layer after washing was recovered again, and the remaining solvent was distilled off under reduced pressure to obtain 20 g of a fluoropolyether group-containing polymer represented by the following formula (M).

¹ H-NMR

δ 0-0.2(-OSi(C H ₃ ) ₂ )12H

δ 0.5-0.7(-OCH ₂ CH ₂ C H ₂ -Si)2H

δ 1.6-1.8(-OCH ₂ C H ₂ CH ₂ -Si)2H

δ 2.5-2.7(-C H ₂ CH=CH ₂ )4H

δ 3.4-3.6(-OC H ₂ CH ₂ CH ₂ -Si)2H

δ 3.6-3.8(-C ₂ F ₂ C H ₂ O-) 2H

δ 5.0-5.2(-CH ₂ CH=C H ₂ )4H

δ 5.7-5.9(-CH ₂ C H =CH ₂ )2H

Mix in the reaction vessel with the following formula (M)

The indicated compound 17.1g (2.0×10 ^-3 mol), 1,3-bis(trifluoromethyl)benzene 15g, trimethoxysilane 0.73g (6.0×10 ^-3 mol) and chloroplatinic acid/vinyl silicon The toluene solution of the oxane complex is 2.0×10 ^-2 g (containing 5.3×10 ^-7 mol of Pt element) and matured at 80°C for 24 hours. Then, the solvent and unreacted materials were distilled off under reduced pressure to obtain 14 g of a liquid product.

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

¹ H-NMR

δ 0-0.2(-OSi(C H ₃ ) ₂ )12H

δ 0.5-0.7(-OCH ₂ CH ₂ C H ₂ -Si,-CH ₂ CH ₂ C H ₂ -Si(OCH ₃ ) ₃ )6H

δ 1.4-2.0(-OCH ₂ C H ₂ CH ₂ -Si,-C H ₂ C H ₂ CH ₂ -Si(OCH ₃ ) ₃ )10H

δ 3.3-3.8(-C ₂ F ₂ C H ₂ O-,-OC H ₂ CH ₂ CH ₂ -Si,-Si(OC H ₃ ) ₃ )22H

[Example 5]

In the reaction vessel, mix 10 g of 1,3-bis(trifluoromethyl)benzene, 0.54 g (5.4×10 ^{-3 mol) of triethylamine, and 10.1 g (2.4×10 -3} ) of the compound represented by the following formula (A) mol),

^{After slowly dropping 10.0 g (2.4×10 -3} mol) of the compound represented by the following formula (O),

Stir at 60°C for 20 hours. Next, water was added, the lower fluorine compound layer was recovered by a liquid separation operation, and then washed with acetone. The fluorine compound layer in the lower layer after washing was recovered again, and the remaining solvent was distilled off under reduced pressure to obtain 17 g of a fluoropolyether group-containing polymer represented by the following formula (P).

¹ H-NMR

δ 2.7-3.0(-C H ₂ CH=CH ₂ )4H

δ 4.9-5.1(-CH ₂ CH=C H ₂ )4H

δ 5.6-5.8(-CH ₂ C H =CH ₂ )2H

Mix in the reaction vessel with the following formula (P)

The indicated compound is 16.7g (2.0×10 ^-3 mol), 1,3-bis(trifluoromethyl)benzene 15g, trimethoxysilane 0.73g (6.0×10 ^-3 mol) and chloroplatinic acid/vinyl silicon The toluene solution of the oxane complex is 2.0×10 ^-2 g (containing 5.3×10 ^-7 mol of Pt element) and matured at 80°C for 24 hours. Then, the solvent and unreacted materials were distilled off under reduced pressure to obtain 13 g of a liquid product.

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

¹ H-NMR

δ 0.5-0.7(-OCH ₂ CH ₂ C H ₂ -Si)4H

δ 1.7-2.1(-OCH ₂ C H ₂ CH ₂ -Si,-OC H ₂ CH ₂ CH ₂ -Si).8H

δ 3.4-3.7(-Si(OC H ₃ ) ₃ )18H

[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 perfluoro) at a concentration of 20% by mass. Butyl ether), and prepare a surface treatment agent. The outermost surface was _{treated with SiO 2} for 10nm (Gorilla manufactured by Corning Corporation), and vacuum evaporation (treatment conditions: pressure: 2.0×10 ^-2 Pa, heating temperature: 700°C) each surface treatment agent 7mg, at 25 Cured for 24 hours in an environment of ℃ and 40% humidity to form a cured film with a thickness of 10nm.

Evaluation of water repellency

[Evaluation of initial water repellency]

For the glass with the cured film formed above, a contact angle meter Drop Master (manufactured by Kyowa Interface Science Co., Ltd.) was used to measure the contact angle (water repellency) of the cured film with respect to water. Shows good water repellency in the initial stage. table The result is shown in 1.

[Evaluation of Dynamic Friction Coefficient]

With respect to the glass with the cured film formed above, the surface property tester 14FW (manufactured by Shinto Scientific Co., Ltd.) was used to measure the dynamic friction coefficient with respect to Bemcot (manufactured by Asahi Kasei Co., Ltd.) under the following conditions. The results are shown in Table 1.

Contact area: 10mm×35mm

Load: 100g

[Sliding evaluation]

Ten panelists touched the glass with the cured film formed above with their fingers, and evaluated the feeling of use according to the following criteria, and the evaluation with the largest number of people was regarded as the evaluation of the sliding property. The results are shown in Table 1.

◎: Very good

○+: Good

○: Normal

×: Poor

Regarding Examples 1, 2, and 4 in which a siloxane group or a fluoropolyether group was further introduced into the molecule of the polymer containing a fluoropolyether group, the dynamic friction coefficient was lower than that of the single-stranded comparative example 1, and the sliding properties were confirmed improve.

Claims (7)

A polymer-modified silane containing fluoropolyether group, which is represented by the following general formula (1),

In formula (1), Rf is a monovalent or divalent polymer residue containing a fluorooxyalkylene group, Y is a 2- to 6-valent hydrocarbon group that may have a siloxane bond and/or a silylene group, and R is C1-C4 alkyl or phenyl group, X is a hydroxyl group or hydrolyzable group, Q is a divalent organic group which may have a siloxane bond and/or a silylene group, R'is a monovalent fluoroalkyl group, 1 Valence polymer residues containing fluorooxyalkylene groups, alkyl groups with 1 to 4 carbons or phenyl groups, n is an integer of 1 to 3, m is an integer of 1 to 5, and α is 1 or 2; the aforementioned α When it is 1, the Rf group is a monovalent fluorooxyalkylene-containing polymer residue represented by the following general formula (2); when the aforementioned α is 2, the Rf group is represented by the following general formula (3) 2 Valence of polymer residues containing fluorooxyalkylene groups;

In formula (2), p, q, r, and s are each an integer from 0 to 200, and p+q+r+s= an integer from 3 to 200, t is an integer from 1 to 3, and each repeating unit can be a straight The chain shape can also be branched, and the repeating units can be randomly combined with each other;

In formula (3), p, q, r, and s are each an integer from 0 to 200, and p+q+r+s= an integer from 3 to 200, t is an integer from 1 to 3, and each repeating unit can be a straight The chain shape may also be branched, and each repeating unit may be randomly combined with each other. For example, the fluoropolyether-containing polymer-modified silane of claim 1, wherein in the aforementioned formula (1), Y is selected from the group consisting of alkylene groups having 3 to 10 carbon atoms, and phenylene-containing carbon numbers of 8-16 A divalent group in which the alkylene group, the alkylene group with 2 to 10 carbon atoms are bonded to each other via the silylalkylene structure or the silyl aryl structure, and the linear organopolysilicon with 2 to 10 silicon atoms One of the 2--4 valent groups of alkylene groups with 2-10 carbon atoms and the branched or cyclic organopolysiloxane residues with 3-10 silicon atoms are bonded to the bonding bonds of the oxane residues. At least one group of a group consisting of a 2- to 4-valent group of an alkylene group having 2 to 10 carbon atoms is bonded to the bonding bond. For example, the fluoropolyether-containing polymer-modified silane of claim 1, wherein in the aforementioned formula (1), X is each independently selected from the group consisting of hydroxyl, alkoxy with 1 to 10 carbons, and 2 to 10 carbons. Alkoxy substituted alkoxy, C 2-10 acyloxy group, C 2-10 alkenyloxy group, and halogen atom. For example, the fluoropolyether-containing polymer-modified silane of claim 1, wherein in the aforementioned formula (1), Q is a divalent organic group represented by the following formula (4);

In the formula, R" may have any one of ketones, esters, amides, ethers, thioethers, amines, and phenylene groups with 1-10 carbon atoms or carbonyl groups, and W is composed of silicon atoms with 2~ 40 straight-chain divalent organic (poly)siloxane residues, which are combined through alkylenes with 1 to 4 carbon atoms, which can have 3 to 40 siloxane bonds with silicon atoms. Silylidene, phenylene-containing, straight-chain silylylene that can be combined with alkylene having 1 to 4 carbon atoms, and siloxane bond with 3-40 silicon atoms, selected from 2 Valence groups, organic (poly)siloxane residues, silylene groups, and silylene groups may be single or mixed, β is 0 or 1, γ is 0 or 1, β+γ is 1 or 2. For example, the polymer-modified silane containing a fluoropolyether group in any one of claims 1 to 4, 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. A surface treatment agent comprising the polymer-modified silane containing a fluoropolyether group according to any one of claims 1 to 5. An article formed with a hardened film, which has a hardened film of the surface treatment agent of claim 6 on the surface.