TWI780042B - Fluorinated polyether-based polymer modified silanes, surface treatment agents and articles - Google Patents

Abstract

(式中，Rf為1價或2價之含氟氧伸烷基之聚合物殘基，Q為可含有醚鍵之碳數2~6之2價烴基，Y為可具有矽原子、伸矽烷基及/或矽氧烷鍵之2~6價烴基，R獨立為碳數1~4之烷基，X獨立為羥基或水解性基，n為1~3之整數，γ為1~5之整數，m為1~5之整數，R’為碳數1~4之烷基，β為1~3之整數，α為1或2)。 The present invention provides a fluorine-containing polyether-based polymer-modified silane represented by the following general formula (1), which can form a hardened film with excellent water and oil repellency and abrasion resistance, and the silane containing the silane and/or its partial hydrolysis Surface treatment agents for condensates, and articles surface-treated with such surface treatment agents,

(wherein, Rf is the polymer residue of a monovalent or divalent fluorine-containing oxyalkylene group, Q is a divalent hydrocarbon group with 2 to 6 carbon atoms that may contain an ether bond, Y is a silicon atom, a silane 2-6 valent hydrocarbon groups with radicals and/or siloxane bonds, R is independently an alkyl group with 1-4 carbons, X is independently a hydroxyl group or a hydrolyzable group, n is an integer of 1-3, γ is a number of 1-5 Integer, m is an integer of 1 to 5, R' is an alkyl group with 1 to 4 carbons, β is an integer of 1 to 3, and α is 1 or 2).

Description

Fluorine-containing polyether-based polymer modified silane, surface treatment agent and articles

The present invention relates to a fluorine-containing polyether-based polymer-modified silane, specifically, a fluorine-containing polyether-based polymer-modified silane that forms a coating film excellent in water and oil repellency and abrasion resistance, and a silane containing the same A surface treatment agent and/or its partial (hydrolyzed) condensate, and an article that is surface-treated with the surface treatment agent (that is, has a hardened film of the surface treatment agent on the surface).

In recent years, the display of mobile phones has accelerated the use of touch panels for screens. However, the touch panel is in a state where the screen is exposed, and there are many chances of direct contact with fingers or cheeks, and dirt such as sebum is easy to adhere to, which becomes a problem. Therefore, in order to improve the appearance and visibility, there is an increasing demand for technology that prevents fingerprints from adhering to the surface of the display, or technology that makes dirt fall off easily, and it is desired to develop materials that can meet these requirements. In particular, since the surface of the touch panel display is easily stained by fingerprints, it is desirable to provide a water and oil repellent layer. However, although the conventional water- and oil-repellent layer has high water- and oil-repellent properties and excellent stain-removing properties, there is a problem that the antifouling performance deteriorates during use.

Generally, fluorine-containing polyether-based compounds, due to their surface self- Since the energy is very small, it has water and oil repellency, chemical resistance, lubricity, mold release, and antifouling properties. Utilizing its properties, it is widely used in paper industry. Water-repellent, oil-repellent and anti-fouling agents for fibers, slip agents for magnetic recording media, oil-repellent agents for precision machines, mold release agents, cosmetics, protective films, etc. However, this property also means that it is non-adhesive and non-adhesive to other substrates. Even if it can be coated on the surface of the substrate, it is difficult to make the film adhere.

On the other hand, silane coupling agents are well known for bonding organic compounds to the surface of substrates such as glass and cloth, and are widely used as coating agents for the surfaces of various substrates. A silane coupling agent has an organic functional group and a reactive silyl group (generally a hydrolyzable silyl group such as an alkoxy silyl group) in one molecule. The hydrolyzable silyl group forms a film by self-condensation reaction caused by moisture in the air. The coating chemically reacts with the surface of glass or metal through hydrolyzable silane groups. Physically bonded to form a strong coating with durability.

Therefore, it is disclosed that the polymer-modified silane of fluorine-containing polyether group obtained by introducing hydrolyzable silyl group into the compound of fluorine-containing polyether group is easy to adhere to the surface of the substrate, and can form a Water and oil repellency, chemical resistance, lubricity, mold release agent, antifouling properties, etc. (Patent Documents 1~5: JP 2008-534696, JP 2008-537557, JP-A No. 2012-072272, JP-A No. 2012-157856, JP-A No. 2013-136833).

The composition of the polymer-modified silane containing the fluorine-containing polyether group obtained by introducing a hydrolyzable silane group into the compound containing the fluorine-containing polyether group Surface-treated lenses and anti-reflection films, etc., have excellent lubricity and mold release properties. However, in recent years, users have demanded high wear resistance, and cannot fully meet the performance requirements. Moreover, although coating with a thick film is easier to exhibit performance, haze occurs on the glass surface, which impairs visibility.

[Prior Art Literature] [Patent Document]

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

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

[Patent Document 3] Japanese Patent Laid-Open No. 2012-072272

[Patent Document 4] Japanese Unexamined Patent Publication No. 2012-157856

[Patent Document 5] Japanese Patent Laid-Open No. 2013-136833

In view of the above circumstances, the present invention aims to provide a fluorine-containing polyether-based polymer-modified silane capable of forming a hardened film having excellent water and oil repellency and abrasion resistance, and the silane and/or its part (hydrolyzed silane) ) condensate surface treatment agent, and articles treated with the surface treatment agent (having a hardened film of the surface treatment agent on the surface).

As a result of the inventors' active examination to solve the above-mentioned object, it was found that by modifying the silane with the above-mentioned fluorine-containing polyether-based polymer, the Modified silane with fluorine-containing polyether-based polymer represented by the general formula (1) described below, whereby the surface treatment agent containing the silane and/or its partial (hydrolyzed) condensate can form water-repellent, oil-repellent, wear-resistant A cured film excellent in wearability and visibility has been developed, and the present invention has been completed.

Therefore, the present invention provides the following fluorine-containing polyether-based polymer-modified silane, surface treatment agent and articles.

[1]

A fluorine-containing polyether-based polymer-modified silane represented by the following general formula (1),

(wherein, Rf is the polymer residue of a monovalent or divalent fluorine-containing oxyalkylene group, Q is a divalent hydrocarbon group with 2 to 6 carbon atoms that may contain an ether bond, Y is a silicon atom, a silane 2-6 valent hydrocarbon groups with radicals and/or siloxane bonds, R is independently an alkyl group with 1-4 carbons, X is independently a hydroxyl group or a hydrolyzable group, n is an integer of 1-3, γ is a number of 1-5 Integer, m is an integer of 1 to 5, R' is an alkyl group with 1 to 4 carbons, β is an integer of 1 to 3, and α is 1 or 2).

[2]

The fluorine-containing polyether-based polymer-modified silane of the above [1], wherein α in the aforementioned formula (1) is 1, and the Rf group is a monovalent fluorine-containing oxyalkylene group represented by the following general formula (2). polymer residue,

(wherein, p, q, r, and s are integers from 0 to 200, respectively, p+q+r+s=an integer from 3 to 200, and each repeating unit can be linear or branched, and each repeating unit They can be randomly bonded to each other, d is an integer of 1 to 3, and the unit (-C _d F _2d -) can be linear or branched).

[3]

Fluorine-containing polyether-based polymer-modified silane such as [1], wherein α in the aforementioned formula (1) is 2, and the Rf group is a polymerization of a divalent fluorine-containing oxyalkylene group represented by the following general formula (3) substance residues,

(wherein, p, q, r, and s are integers from 0 to 200, respectively, p+q+r+s=an integer from 3 to 200, and each repeating unit can be linear or branched, and each repeating unit They can be randomly bonded to each other, d is an integer of 1 to 3, and the units (-C _d F _2d -) can be independently linear or branched).

[4]

Such as the fluorine-containing polyether-based polymer-modified silane in any one of [1]~[3], wherein in the aforementioned formula (1), Y is selected from an alkylene group with a carbon number of 3~10, a carbon number The alkylene group of the 6-8 arylylene group, the divalent group bonded to each other through the silicon atom, the silylene group, the silylene group structure or the silicon aryl structure, and the number of silicon atoms is 2 to 10 Straight-chain or branched or cyclic 2-4 valent organopolysiloxane residues with 3-10 silicon atoms, or bonded to silicon atoms At least one of the group consisting of 2-4 valent groups of alkylene groups having 2-10 carbon atoms.

[5]

The fluorine-containing polyether-based polymer-modified silane according to any one of [1] to [4], wherein in the aforementioned formula (1), Q is -CH ₂ OCH ₂ -.

[6]

Such as the fluorine-containing polyether-based polymer-modified silane in any one of [1] to [5], wherein in the aforementioned formula (1), X is respectively selected from hydroxyl, alkoxy with 1 to 10 carbons, At least one of the group consisting of alkoxyalkoxy with 2 to 10 carbons, acyloxy with 2 to 10 carbons, alkenyloxy with 2 to 10 carbons, and halo.

[7]

The fluorine-containing polyether-based polymer-modified silane of any one of [1] to [6], wherein the polymer-modified silane represented by formula (1) is represented by any of the following formulas,

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

[8]

A surface treatment agent containing the fluorine-containing polyether-based polymer-modified silane and/or its partial (hydrolyzed) condensate according to any one of [1] to [7].

[9]

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

The fluorine-containing polyether-based polymer-modified silane of the present invention has more reactive functional groups and ether linkage groups, so it improves the adhesion and wettability to the substrate, thereby by containing the silane and/or its Partial (hydrolyzed) condensate surface treatment agent Surface treated articles have excellent water and oil repellency, wear resistance and visibility.

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

(wherein, Rf is a 1- or 2-valent fluorine-containing oxyalkylene polymer residue Q is a divalent hydrocarbon group with 2 to 6 carbons that may contain an ether bond, Y is a 2 to 6 valent hydrocarbon group that may have a silicon atom, a silane group, and/or a siloxane bond, and R is independently a carbon number from 1 to 6. 4 is an alkyl group, X is independently a hydroxyl group or a hydrolyzable group, n is an integer of 1 to 3, γ is an integer of 1 to 5, m is an integer of 1 to 5, R' is an alkyl group with 1 to 4 carbons, β is an integer from 1 to 3, and α is 1 or 2).

The fluorine-containing polyether-based polymer-modified silane of the present invention is characterized in that the polymer residue (Rf) of a monovalent or divalent fluorine-containing oxyalkylene group and a hydrolyzable silyl group such as an alkoxysilyl group or Hydroxyl-containing silyl groups (-Si(R) _3-n (X) _n ) are 2-6 valent through hydrocarbon chains (Q) and ether groups and can have silicon atoms, silane groups and/or siloxane bonds Hydrocarbon group (Y) bonded structure, it is preferable to have more than 3 reactive functional groups (X) in the polymer, and multiple ether linking groups to improve substrate adhesion, wear resistance, and visibility excellent.

As Rf, where α is 1, it is preferably a polymer residue of a monovalent fluorine-containing oxyalkylene group represented by the following general formula (2) (hereinafter sometimes referred to as a monovalent fluorooxyalkylene group).

(wherein, p, q, r, and s are integers from 0 to 200, respectively, p+q+r+s=an integer from 3 to 200, and each repeating unit can be linear or branched, and each repeating unit They can be randomly bonded to each other, d is an integer of 1 to 3, and the unit (-C _d F _2d -) can be linear or branched).

As Rf, when α is 2, it is preferably represented by the following general formula (3): Polymer residues of the indicated divalent fluorooxyalkylene groups (hereinafter sometimes referred to as divalent fluorooxyalkylene groups).

(wherein, p, q, r, and s are integers from 0 to 200, respectively, p+q+r+s=an integer from 3 to 200, and each repeating unit can be linear or branched, and each repeating unit They can be randomly bonded to each other, d is an integer of 1 to 3, and the unit (-C _d F _2d -) can be linear or branched).

In the above formulas (2) and (3), p, q, r, and s are respectively integers of 0 to 200, preferably p is an integer of 5 to 100, q is an integer of 5 to 100, and r is an integer of 0 to 100. Integer, s is an integer from 0 to 100, p+q+r+s=3 to 200, preferably an integer from 10 to 105, each repeating unit can be linear or branched, each repeating unit They may be randomly bonded to each other. More preferably p+q is an integer of 10~105, especially an integer of 15~60, r=s=0. When the value of p+q+r+s is less than the above upper limit, the adhesiveness or curability is good, and when it is greater than the above lower limit, the characteristics of the fluoropolyether group can be fully exhibited, so it is preferable.

In the above formulas (2) and (3), d is an integer of 1 to 3, preferably 1 or 2, and the unit (-C _d F _2d -) may be linear or branched.

As Rf, the following can be specifically illustrated.

(In the formula, p', q', r', and s' are integers of 1 or more, and the upper limit Same as the upper limit of p, q, r, and s mentioned above, u is an integer of 1 to 24, v is an integer of 1 to 24, and each repeating unit can be randomly bonded).

In the above formula (1), Y is preferably 2-6 valence, preferably 2-4 valence, more preferably a divalent hydrocarbon group, and may also have a silicon atom, a silane group and/or a siloxane bond, by There is no linking group with low bonding energy in the molecule, and it can impart a coating film with excellent abrasion resistance.

Specific examples of Y include those having 3 to 10 carbon atoms such as propylene (trimethylene, methylethylene), butyl (tetramethylene, methylpropylene), and hexamethylene. Alkyl, alkylene including arylylene with 6-8 carbons such as phenylene (for example, alkylene with 8-16 carbons, arylylene, etc.), alkylene through silicon atom, silane 2-6 valent groups with 2-10 silicon atoms, preferably 2-5 straight-chain, branched or cyclic An organopolysiloxane residue, or a 2-6 valent group of an alkylene group having 2-10 carbons bonded to a silicon atom, preferably an alkylene group having 3-10 carbons, including The alkylene group of the phenylene group, the divalent group in which the alkylene group is bonded to each other through the structure of the silane group or the structure of the aryl group, and a straight chain with 2 to 10 silicon atoms or 3 to 10 silicon atoms A branched or cyclic 2-4 valent organopolysiloxane residue, or a 2-4 valent group of an alkylene group with 2-10 carbon atoms bonded to the silicon atom, more preferably An alkylene group with 3 to 6 carbon atoms.

Here, the following are exemplified as the silylene group structure and the silylene aryl structure.

(wherein, R ¹ is an alkyl group with 1 to 4 carbons such as methyl, ethyl, propyl, butyl, etc., an aryl group with 6 to 10 carbons such as phenyl, and R ¹ can be the same or different, R2 is an alkylene group with ¹ to 4 carbons such as methylene, ethylidene, propylidene (trimethylene, methylethylidene), and an arylene group with 6 to 10 carbons such as phenylene base).

Furthermore, examples of the linear, branched or cyclic 2- to 6-valent organopolysiloxane residues having 2 to 10 silicon atoms, preferably 2 to 5, can be exemplified below.

(wherein, R1 is the same as above, g is an integer of ¹ to 9, preferably an integer of 1 to 4, h is an integer of 2 to 6, preferably an integer of 2 to 4, j is an integer of 0 to 8 Integer, preferably 0 or 1, h+j is an integer of 3 to 10, preferably an integer of 3 to 5, k is an integer of 1 to 3, preferably 2 or 3).

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

In the above formula (1), Q is a divalent hydrocarbon group having 2 to 6 carbon atoms which may contain an ether bond. As Q, specific examples are ethylenyl, propylenyl (trimethylene C2-6 alkylene group, such as butyl group (tetramethylene group, methyl propylidene group), hexamethylene group, ethylidene group containing ether bond, C2-6 alkylene groups such as propylidene (trimethylene, methylethylidene), butylene (tetramethylene, methylpropylidene), hexamethylene, etc., preferably An alkylene group having 2 or 3 carbon atoms containing an ether bond among them.

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

【Chemical 14】-CH ₂ CH ₂ --CH ₂ CH ₂ CH ₂ --CH ₂ CH ₂ CH ₂ CH ₂ --CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ --CH ₂ -O-CH ₂ --CH ₂ -O-CH ₂ CH ₂ -

In the above formula (1), X is a hydroxyl group or a hydrolyzable group which may be different from each other. Examples of this X include hydroxyl, methoxy, ethoxy, propoxy, isopropoxy, butoxy, and alkoxy groups having 1 to 10 carbon atoms, methoxymethoxy, and methoxyethyl. Alkoxy with 2 to 10 carbons such as oxy, alkoxy with 2 to 10 carbons such as acetyloxy, acyloxy with 2 to 10 carbons such as acetyloxy, alkenyloxy with 2 to 10 carbons such as isopropenyloxy , halogen group of chlorine atom, bromine atom, iodine atom, etc. Among them, methoxy, ethoxy, isopropoxy and chlorine atoms are preferred.

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, or a butyl group, among which methyl and ethyl are preferred. n is an integer of 1 to 3, preferably 2 or 3, based on reactivity and adhesion to the substrate Views, better 3.

In the above formula (1), m is an integer of 1 to 5, preferably 1 or 2 from the viewpoint of raw material acquisition. In addition, γ is an integer of 1 to 5, and is preferably an integer of 1 to 3 from the viewpoint of easiness of synthesis, stability of the product, and the like.

In the above formula (1), R' is an alkyl group having 1 to 4 carbons such as methyl, ethyl, propyl, butyl, etc., among which methyl and ethyl are preferred. β is an integer of 1 to 3, more preferably 2 or 3 from the viewpoint of reactivity and adhesion to the base material.

Examples of the fluorine-containing polyether-based polymer-modified silane represented by the above formula (1) include those represented by the following formula. Also, in each formula, the repeating number (or degree of polymerization) of each repeating unit constituting the fluorooxyalkyl group or fluorooxyalkylene group can be any number satisfying the above 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).

The method for preparing the fluorine-containing polyether-based polymer-modified silane represented by the above formula (1) when α is 1 is, for example, the following method.

Dissolve the polymer containing fluorinated oxyalkyl groups preferably having 2 or more (especially 2 or 3) olefin moieties at the single end of the molecular chain in a solvent such as 1,3-bis(trifluoromethyl)benzene and other fluorine-based polymers In a solvent, an organosilicon compound having a SiH group and a hydrolyzable terminal group (alkoxy group such as methoxy group, etc.) in a molecule such as trimethoxysilane and a hydrosilylation reaction catalyst such as platinum chloride/vinyl group In the presence of a toluene solution of siloxane complex, at a temperature of 40-120°C, preferably 60-100°C, more preferably about 80°C, for 1-48 hours, preferably 2-10 hours, more preferably about 5 hours Under these conditions, the hydrosilylation addition reaction is carried out and matured.

In addition, as another method for preparing the fluorine-containing polyether group polymer-modified silane when α represented by the above formula (1) is 1, the following methods are exemplified.

Dissolve the polymer containing fluorinated oxyalkyl groups preferably having 2 or more (especially 2 or 3) olefin moieties at the single end of the molecular chain in a solvent such as 1,3-bis(trifluoromethyl)benzene and other fluorine-based polymers In the solvent, make trichlorosilane and other organic silicon compounds with SiH groups and hydrolyzable terminal groups in the molecule, in the presence of hydrosilylation reaction catalysts such as chloroplatinic acid/vinylsiloxane complexes in toluene , at a temperature of 40-120°C, preferably 60-100°C, more preferably about 80°C, for 1-48 hours, preferably 2-10 hours, more preferably about 5 hours, carry out the hydrosilylation addition reaction and After ripening, the substituent on the silyl group (A chlorine atom bonded to a silicon atom, etc.) is converted into a hydrolyzable group such as an alkoxy group such as a methoxy group.

Also, instead of the organosilicon compound having a SiH group and a hydrolyzable terminal group in the above molecule, an organosilicon compound containing a SiH group without a hydrolyzable terminal group can be used. In this case, as the organosilicon compound, a molecule Among them, there is no hydrolyzable terminal group, but an organosilicon compound with two or more SiH groups. At this time, it is carried out in the same manner as the above-mentioned method so that the single end of the molecular chain preferably has 2 or more (especially 2 or 3) olefinic moieties. After the hydrosilylation addition reaction of organosilicon compounds containing more than 2 SiH groups, a reactant (intermediate) with preferably 2 or more (especially 2 or 3) residual SiH groups at the single end of the molecular chain is produced, and then used The residual SiH group at the end of the polymer of the reaction product (intermediate) and the organosilicon compound having an olefin moiety and a hydrolyzable terminal group in the molecule of allyltrimethoxysilane, etc., are used in hydrosilylation reaction catalysts such as chlorine In the presence of a toluene solution of platinic acid/vinylsiloxane complex, at a temperature of 40-120°C, preferably 60-100°C, more preferably about 80°C, for 1-48 hours, preferably 2-10 hours , preferably under the condition of about 5 hours, carry out the hydrosilylation addition reaction and mature again.

Here, examples of the fluorinated oxyalkyl group-containing polymer having an olefin moiety at one end of the molecular chain include a fluorinated oxyalkyl group-containing polymer represented by the following formula (4).

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

In the above formula (4), Z is a divalent hydrocarbon group, preferably a divalent hydrocarbon group with a carbon number of 1 to 8, especially a divalent hydrocarbon group with 1 to 4 carbons, specifically, methylene, ethylidene, propylidene (trimethylene) C1-8 alkylene group, including phenylene group, such as methyl ethylidene group), butylene group (tetramethylene group, methyl propylidene group), hexamethylene group, octamethylene group, etc. Such as the alkylene group of the aryl group with 6~8 carbon number (for example, the alkylene group with 7~8 carbon number, the aryl group group, etc.), etc. Z is preferably a straight-chain alkylene group having 1 to 4 carbon atoms.

The fluorinated oxyalkyl group-containing polymer represented by the formula (4) is preferably exemplified below. Also, in each formula, the repeating number (or degree of polymerization) of each repeating unit constituting the fluorooxyalkyl group is 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, and p1+q1 are the same as above).

As a preparation method of the fluorinated oxyalkyl group-containing polymer represented by the above formula (4), for example, a fluorinated oxyalkyl group-containing polymer having a hydroxyl group at one end of the molecular chain and an olefin introducing agent are used in the presence of a base, as required. Using additives or solvents, ripen at 0-90°C, preferably 50-80°C, more preferably about 60°C, for 1-40 hours, preferably 10-30 hours, more preferably about 20 hours.

Examples of the fluorinated oxyalkyl group-containing polymer having a hydroxyl group at one end of the molecular chain used for preparing the fluorooxyalkyl group-containing polymer represented by formula (4) are those shown below.

(In the formula, u1 is an integer from 1 to 24, and r1, p1, q1, p1+q1 are the same as above)

Examples of the olefin-introducing agent used for the preparation of the fluorooxyalkyl group-containing polymer represented by the formula (4) include those shown below, preferably having 2 or more (especially 2 or 3) olefins at one end of the molecular chain The site has a sulfonate residue represented by -S(=O) ₂ O- at the other end, etc.

The olefin introducing agent can be prepared by a known method.

The amount of olefin importing agent, the content of the hydroxyl group at the single end of the molecular chain 1 equivalent of the reactive terminal group (terminal hydroxyl group) of the fluorooxyalkyl polymer is used in an amount of 1 to 5 equivalents, more preferably 1 to 3 equivalents, and more preferably about 1.5 equivalents based on the sulfonate residue.

As the base used for the preparation of the fluorine-containing oxyalkyl group-containing polymer represented by formula (4), for example, amines or alkali metal bases can be used. Specifically, the amines include triethylamine, diisopropylethylamine, and diisopropylethylamine. Amine, pyridine, DBU, imidazole, etc. Examples of alkali metal bases include sodium hydroxide, potassium hydroxide, sodium hydride, potassium hydride, alkyl lithium, potassium tert-butoxide, lithium diisopropylamide, lithium bis(trimethylsilyl)amide, Sodium bis(trimethylsilyl)amide, potassium bis(trimethylsilyl)amide, etc.

The amount of base used is 1 to 20 equivalents, more preferably 5 to 15 equivalents, and more preferably about 9 equivalents to 1 equivalent of the reactive terminal group of the fluorinated oxyalkyl group-containing polymer having a hydroxyl group at one end of the molecular chain.

In the preparation of the fluorinated oxyalkyl group-containing polymer represented by formula (4), tetrabutylammonium halides, alkali metal halides, etc. can also be used as additives for improving reactivity or interphase transfer catalysts. Specific examples of additives include tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium iodide, tetrabutylammonium hydrogensulfate, sodium iodide, potassium iodide, cesium iodide, and crown ether. These additives increase the reactivity by catalytic halogen exchange with the olefin introducing agent in the reaction system, and increase the reactivity by coordinating the crown ether to the metal.

The amount of the additive used is 0.005-0.2 equivalent, more preferably 0.01-0.15 equivalent, and more preferably about 0.1 equivalent to 1 equivalent of the reactive terminal group of the fluorine-oxygen-containing polymer having a hydroxyl group at one end of the molecular chain.

Preparation of the polymer containing fluorooxy group represented by formula (4) In, a solvent can also be used. As the solvent used, examples of fluorinated solvents include fluorinated aromatic hydrocarbon solvents such as 1,3-bis(trifluoromethyl)benzene and trifluoromethylbenzene, 1,1,1,2,3,4 , Hydrofluoroether (HFE)-based solvents such as 4,5,5,5-decafluoro-3-methoxy-2-(trifluoromethyl)benzene (manufactured by 3M Company, trade name: Novec series), and Perfluorinated solvents composed of completely fluorinated compounds (manufactured by 3M Company, trade name: FLUORINERT series), etc. Furthermore, as an organic solvent, dimethylformamide, dimethylacetamide, dimethylsulfoxide, acetonitrile, THF, or the like can be used. And water can also be used.

The amount used when using a solvent is 10-300 parts by mass, more preferably 30-150 parts by mass, and more preferably about 50 parts by mass for 100 parts by mass of a polymer containing a fluorinated oxyalkyl group having a hydroxyl group at one end of the molecular chain. .

Next, the reaction was stopped, and the water layer and the fluorine solvent layer were separated by a liquid separation operation. The obtained fluorinated solvent layer was further washed with an organic solvent, and the solvent was distilled off to obtain a fluorinated oxyalkyl group-containing polymer represented by formula (4).

In the preparation of the fluorine-containing polyether-based polymer-modified silane when α represented by the above formula (1) is 1, the solvent used is preferably a fluorine-based solvent, and the fluorine-based solvent is, for example, 1,3-bis (Trifluoromethyl)benzene, trifluoromethylbenzene, methyl nonafluorobutyl ether, methyl nonafluoroisobutyl ether, ethyl nonafluorobutyl ether, ethyl nonafluoroisobutyl ether, 1,1,1, Hydrofluoroether (HFE)-based solvents such as 2,3,4,4,5,5,5-decafluoro-3-methoxy-2-(trifluoromethyl)benzene (manufactured by 3M Company, trade name: Novec series), perfluorinated solvents composed of fully fluorinated compounds (manufactured by 3M Company, trade name: FLUORINERT series), etc.

The amount of solvent used is 10 to 300 parts by mass for 100 parts by mass of a polymer containing a fluorine-oxygen group having an olefin portion at one end of the molecular chain, and more Preferably, it is 50-150 parts by mass, more preferably about 100 parts by mass.

In the preparation of the fluorine-containing polyether-based polymer-modified silane when α represented by the above formula (1) is 1, the organosilicon compound having a SiH group and a hydrolyzable terminal group in the molecule is preferably represented by the following general formula: Compounds represented by (5)~(8).

(wherein, R, X, n, R ¹ , R ² , g, j are the same as above, R ³ is a divalent hydrocarbon group with 2 to 8 carbons, i is an integer of 1 to 5, preferably 1 to 3 an integer, i+j is an integer of 2 to 9, preferably an integer of 2 to 4).

Here, ^R3 is a divalent hydrocarbon group with 2 to 8 carbon atoms, preferably 2 to 3, such as ethylidene, propylidene (trimethylene, methylethylidene), butylene (tetramethylene Alkylene groups such as methyl, methylpropylene), hexamethylene, octamethylene, etc., arylylene groups such as phenylene, or a combination of two or more of these groups (alkylene. aryl, etc.), among these, ethylidene and trimethylene are preferred.

Such organosilicon compounds with SiH groups and hydrolyzable terminal groups in the molecule are, for example, trimethoxysilane, triethoxysilane, trippropoxysilane, triisopropoxysilane, tributoxysilane, Triisopropenyloxysilane, triacetyloxysilane, trichlorosilane, tribromosilane, triiodosilane, and the following silanes.

In the preparation of the fluorine-containing polyether-based polymer-modified silane when α represented by the above formula (1) is 1, the polymer with a fluorine-containing oxyalkyl group having an olefin moiety at one end of the molecular chain and the SiH group in the molecule When reacting with organosilicon compounds with hydrolyzable end groups, the amount of organosilicon compounds with SiH groups and hydrolyzable end groups in the molecule, and the reactivity to polymers containing fluorooxyalkyl groups with olefin moieties at one end of the molecular chain End group 1 equivalent, can use 1 to 3 equivalents, more preferably 1.5 to 2.5 equivalents, more preferably about 2 equivalents.

In the preparation of the fluorine-containing polyether-based polymer-modified silane when α represented by the above formula (1) is 1, it is preferable as an organosilicon compound that does not have a hydrolyzable terminal group in the molecule but contains two or more SiH groups. It is a compound represented by the following general formula (9)-(11).

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

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

In the preparation of the fluorine-containing polyether-based polymer-modified silane represented by the formula (1) when α is 1, the polymer with a fluorine-containing oxyalkyl group having an olefin moiety at one end of the molecular chain does not have hydrolysis in the molecule. The amount of organosilicon compound containing two or more SiH groups with no hydrolyzable end group in the molecule when reacting with an organosilicon compound with a non-hydrolyzable terminal group and containing more than two SiH groups is the ratio of the content of an alkene moiety at the single end of the molecular chain. Fluorooxyalkyl polymers 1 equivalent of the reactive terminal group can be used in an amount of 7-30 equivalents, more preferably 10-20 equivalents, more preferably about 15 equivalents.

In addition, in the preparation of the fluorine-containing polyether-based polymer-modified silane when α represented by the formula (1) is 1, the organosilicon compound having an olefin moiety and a hydrolyzable end group in the molecule is preferably represented by the following general formula The compound represented by (12).

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

In the above formula (12), U is a single bond or a divalent hydrocarbon group with 1 to 6 carbons, and as a divalent hydrocarbon group with 1 to 6 carbons, for example, methylene, ethylidene, propylidene (trimethylene , methyl ethylene), butyl (tetramethylene, methyl propyl), hexamethylene and other alkylene, phenylene, etc. U is preferably a single bond or a methylene group.

When α represented by formula (1) is 1, in the preparation of fluorine-containing polyether-based polymer-modified silane, the polymer containing fluorine-oxygen group with olefin moiety at one end of the molecular chain is not hydrolyzable in the molecule. The reactant of an organosilicon compound having two or more SiH groups at the end group, and an organosilicon compound having an olefin moiety and a hydrolyzable end group in the molecule when it reacts with an organosilicon compound having an olefin moiety and a hydrolyzable end group in the molecule Usage amount, for polymers containing fluorine oxyalkyl groups with olefin moieties at the single end of the molecular chain and organosilicon compounds with no hydrolyzable terminal groups and more than 2 SiH groups in the molecule 1 equivalent of the reactive terminal group of the reactant can be used in 3-9 equivalents, more preferably in 5-7 equivalents, and more preferably in about 6 equivalents.

In the preparation of fluorine-containing polyether-based polymer-modified silane when α represented by the formula (1) is 1, as a hydrosilylation reaction catalyst, examples include platinum black, chloroplatinic acid, and alcohols of chloroplatinic acid Modifiers, complexes of chloroplatinic acid and olefins, aldehydes, vinyl siloxanes, acetylene alcohols, etc., platinum group metals such as tetrakis (triphenylphosphine) palladium, chloroginseng (triphenylphosphine) rhodium, etc. catalyst. Platinum compounds such as vinylsiloxane complexes are preferred.

The amount of hydrosilylation reaction catalyst used is for the polymer containing fluorooxy group with olefin moiety at one end of the molecular chain, or the polymer and the organic compound containing two or more SiH groups without hydrolyzable terminal group in the molecule. The mass of the reactant of the silicon compound is used in an amount of 0.1 to 100 ppm, more preferably 1 to 50 ppm in conversion metal conversion (mass).

Finally, the target compound can be obtained by distilling off the solvent and unreacted substances under reduced pressure.

For example, a compound represented by the following formula is used as a polymer containing a fluorinated oxyalkyl group having an olefin moiety at one end of the molecular chain,

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.

As a preparation method of the fluorine-containing polyether group polymer-modified silane represented by the above formula (1) when α is 2, the following methods are exemplified.

The two ends of the molecular chain preferably have 2 or more (especially 2 or 3) olefinic moieties. The polymer containing fluorinated oxyalkylene is dissolved in a solvent such as 1,3-bis(trifluoromethyl)benzene, etc. Organosilicon compounds with SiH groups and hydrolyzable terminal groups in the molecules of trimethoxysilane and other fluorine-based solvents, in hydrosilylation reaction catalysts such as toluene of chloroplatinic acid/vinylsiloxane complexes In the presence of the solution, hydrosilylation is carried out at a temperature of 40-120°C, preferably 60-100°C, more preferably about 80°C, for 1-48 hours, preferably 2-10 hours, more preferably about 5 hours. react and mature.

In addition, as another method of preparing the fluorine-containing polyether group polymer-modified silane when α represented by the above formula (1) is 2, the following methods are exemplified.

Dissolve the polymer containing fluorinated oxyalkylene groups preferably having 2 or more (especially 2 or 3) olefin moieties at both ends of the molecular chain in a solvent such as 1,3-bis(trifluoromethyl)benzene, etc. In a fluorine-based solvent, an organosilicon compound having a SiH group and a hydrolyzable terminal group in the molecule of trichlorosilane exists in a toluene solution of a hydrosilylation reaction catalyst such as chloroplatinic acid/vinylsiloxane complex At 40-120°C, preferably 60-100°C, more preferably about 80°C, for 1-48 hours, preferably 2-10 hours, more preferably about 5 hours After hydrosilylation addition reaction and ripening, the substituent on the silyl group is converted to, for example, methoxy group.

Also, instead of the organosilicon compound having a SiH group and a hydrolyzable terminal group in the above molecule, an organosilicon compound containing a SiH group without a hydrolyzable terminal group can be used. In this case, as the organosilicon compound, a molecule Among them, there is no hydrolyzable terminal group, but an organosilicon compound with two or more SiH groups. At this time, the same method as above is carried out so that the two ends of the molecular chain preferably have 2 or more (especially 2 or 3) olefinic moieties. The organosilicon compound containing two or more SiH groups undergoes a hydrosilylation addition reaction to form a reactant (intermediate) that preferably has two or more (especially two or three) residual SiH groups at both ends of the molecular chain After that, it is better to make the polymer terminal of the reactant (intermediate) preferably have more than 2 (especially 2 or 3) SiH groups and allyl trimethoxysilane in the molecule, which has an olefin position and hydrolysis Organosilicon compounds with permanent terminal groups, in the presence of hydrosilylation reaction catalysts such as chloroplatinic acid/vinylsiloxane complexes in toluene, at 40~120°C, preferably 60~100°C, more preferably At a temperature of about 80°C, for 1 to 48 hours, preferably 2 to 10 hours, and more preferably about 5 hours, the hydrosilylation reaction is carried out again and matured.

Here, examples of the fluorinated oxyalkylene group-containing polymer having olefin moieties at both ends of the molecular chain include a fluorinated oxyalkylene group-containing polymer represented by the following formula (13).

(wherein, Rf, R', Q, m, Z, and β are the same as above).

The fluorinated oxyalkylene group-containing polymer represented by the formula (13) is preferably exemplified below. Also, in each formula, the repeating number (or degree of polymerization) of each repeating unit constituting the fluorooxyalkylene group is any number that satisfies the formula (3) in the above Rf.

(wherein, p1, q1, and p1+q1 are the same as above).

As a preparation method of the fluorine oxyalkylene group-containing polymer represented by the above formula (13), for example, a fluorine oxyalkylene group having hydroxyl groups at both ends of the molecular chain Alkyl polymer and olefin introducing agent, in the presence of alkali, use additives or solvents as needed, at 0~90°C, preferably 50~80°C, more preferably about 60°C, for 1~40 hours, preferably 10-30 hours, preferably about 20 hours.

Examples of the fluorinated oxyalkylene-containing polymer having hydroxyl groups at both ends of the molecular chain used for the preparation of the fluorinated oxyalkylene group-containing polymer represented by formula (13) are those represented by the following formulae.

(In the formula, v1 is an integer from 1 to 24, u1, p1, q1, p1+q1 are the same as above)

Examples of the olefin-introducing agent used in the preparation of the fluorinated oxyalkylene group-containing polymer represented by the above formula (13) include those shown below, preferably having two or more (especially two or three) at one end of the molecular chain ) olefin moiety, and those having a sulfonate residue represented by -S(=O) ₂ O- at the other end, etc.

The olefin introducing agent can be prepared by a known method.

The amount of olefin importing agent, the content of hydroxyl groups at both ends of the molecular chain 1 equivalent of the reactive terminal group (terminal hydroxyl group) of the fluorooxyalkylene polymer is used in an amount of 1 to 5 equivalents, more preferably 1 to 3 equivalents, and more preferably about 1.5 equivalents, based on the sulfonate residue.

As the base used for preparing the fluorine oxyalkylene group-containing polymer represented by the formula (13), for example, amines or alkali metal bases can be used. Specifically, the amines include triethylamine, diisopropyl Ethylamine, pyridine, DBU, imidazole, etc. Examples of alkali metal bases include sodium hydroxide, potassium hydroxide, sodium hydride, potassium hydride, alkyl lithium, potassium tert-butoxide, lithium diisopropylamide, lithium bis(trimethylsilyl)amide, Sodium bis(trimethylsilyl)amide, potassium bis(trimethylsilyl)amide, etc.

The amount of base used is 1 equivalent to 1 equivalent of the reactive terminal group of the polymer containing fluorine oxyalkylene groups with hydroxyl groups at both ends of the molecular chain. It can be used in 1~20 equivalents, more preferably 5~15 equivalents, and more preferably about 9 equivalents .

In the preparation of the fluorine oxyalkylene group-containing polymer represented by formula (13), tetrabutylammonium halides, alkali metal halides, etc. can also be used as additives for improving reactivity or interphase transfer catalysts. Specific examples of additives include tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium iodide, tetrabutylammonium hydrogensulfate, sodium iodide, potassium iodide, cesium iodide, and crown ether. These additives increase the reactivity by catalytic halogen exchange with the olefin introducing agent in the reaction system, and increase the reactivity by coordinating the crown ether to the metal.

The amount of the additive used is 0.005-0.2 equivalent, more preferably 0.01-0.15 equivalent, more preferably about 0.1 equivalent to 1 equivalent of the reactive terminal group of the fluorine-oxyalkylene-containing polymer having hydroxyl groups at both ends of the molecular chain.

Preparation of the polymer containing fluorooxy group represented by formula (13) In, a solvent can also be used. The solvent does not necessarily need to be used, but as the solvent used, examples of fluorine-based solvents include fluorine-containing aromatic hydrocarbon solvents such as 1,3-bis(trifluoromethyl)benzene and trifluoromethylbenzene, 1,1, Hydrofluoroether (HFE)-based solvents such as 1,2,3,4,4,5,5,5-decafluoro-3-methoxy-2-(trifluoromethyl)benzene (manufactured by 3M Company, commercial product) name: Novec series), perfluorinated solvents composed of fully fluorinated compounds (manufactured by 3M Company, trade name: FLUORINERT series), etc. Furthermore, as an organic solvent, dimethylformamide, dimethylacetamide, dimethylsulfoxide, acetonitrile, THF, or the like can be used. And water can also be used.

The amount used when using the solvent is 10 to 300 parts by mass, more preferably 30 to 150 parts by mass, and more preferably about 50 parts by mass for 100 parts by mass of the polymer containing fluorine oxyalkylene groups having hydroxyl groups at both ends of the molecular chain. share.

Next, the reaction was stopped, and the water layer and the fluorine solvent layer were separated by a liquid separation operation. The obtained fluorinated solvent layer was further washed with an organic solvent, and the solvent was distilled off to obtain a fluorinated oxyalkylene group-containing polymer represented by formula (13).

In the preparation of the fluorine-containing polyether-based polymer-modified silane when α represented by the above formula (1) is 2, the solvent used is preferably a fluorine-based solvent, and the fluorine-based solvent is, for example, 1,3-bis (Trifluoromethyl)benzene, trifluoromethylbenzene, methyl nonafluorobutyl ether, methyl nonafluoroisobutyl ether, ethyl nonafluorobutyl ether, ethyl nonafluoroisobutyl ether, 1,1,1, Hydrofluoroether (HFE)-based solvents such as 2,3,4,4,5,5,5-decafluoro-3-methoxy-2-(trifluoromethyl)benzene (manufactured by 3M Company, trade name: Novec series), perfluorinated solvents composed of fully fluorinated compounds (manufactured by 3M Company, trade name: FLUORINERT series), etc.

The amount of solvent used is 10-300 parts by mass for 100 parts by mass of polymers containing fluorinated oxyalkylene groups having olefin moieties at both ends of the molecular chain. parts, more preferably 50 to 150 parts by mass, and more preferably about 100 parts by mass.

In addition, when α represented by the formula (1) is 2, in the preparation of the fluorine-containing polyether-based polymer-modified silane, as an organosilicon compound having a SiH group and a hydrolyzable terminal group in the molecule, the following general formula is preferred: Compounds represented by (5)~(8).

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

Such organosilicon compounds with SiH groups and hydrolyzable terminal groups in the molecule are, for example, trimethoxysilane, triethoxysilane, trippropoxysilane, triisopropoxysilane, tributoxysilane, Triisopropyl Alkenyloxysilane, triacetyloxysilane, trichlorosilane, tribromosilane, triiodosilane, and the following silanes.

In the preparation of the fluorine-containing polyether-based polymer-modified silane when α represented by the above formula (1) is 2, the polymer containing fluorinated oxyalkylene groups having olefin moieties at both ends of the molecular chain and the molecule having The amount of organosilicon compounds with SiH groups and hydrolyzable terminal groups used in the molecule when reacting with organosilicon compounds with SiH groups and hydrolyzable terminal groups, for polymers containing fluorinated oxyalkyl groups with olefin moieties at both ends of the molecular chain For 1 equivalent of reactive terminal groups, 1 to 3 equivalents can be used, more preferably 1.5 to 2.5 equivalents, more preferably about 2 equivalents.

And in the preparation of the fluorine-containing polyether-based polymer-modified silane when α represented by formula (1) is 2, as an organosilicon compound that does not have a hydrolyzable terminal group in the molecule and contains more than 2 SiH groups, it is relatively Compounds represented by the following general formulas (9) to (11) are preferred.

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

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

In the preparation of the fluorine-containing polyether-based polymer-modified silane represented by formula (1) when α is 2, the polymer containing fluorinated oxyalkylene groups with olefin moieties at both ends of the molecular chain is combined with no The amount of organosilicon compound containing two or more SiH groups with no hydrolyzable end group in the molecule when reacting with an organosilicon compound having a hydrolyzable end group and containing two or more SiH groups, for the amount of olefins at both ends of the molecular chain Fluoroxane 1 equivalent of the reactive terminal group of the base polymer can be 7-30 equivalents, more preferably 10-20 equivalents, more preferably about 15 equivalents.

In addition, in the preparation of the fluorine-containing polyether-based polymer-modified silane when α represented by formula (1) is 2, the organosilicon compound having an olefin moiety and a hydrolyzable terminal group in the molecule is preferably represented by the following general formula The compound represented by (12).

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

When α represented by the formula (1) is 2, in the preparation of the fluorine-containing polyether-based polymer-modified silane, the polymers with fluorine-containing oxyalkylene groups having olefin moieties at both ends of the molecular chain and the molecules without Reactants of organosilicon compounds with hydrolyzable terminal groups containing two or more SiH groups, organosilicon compounds with olefinic moieties and hydrolyzable terminal groups in the molecule when reacting with organosilicon compounds having olefinic moieties and hydrolyzable terminal groups in the molecule The amount of the compound used is the reactivity of the reactants of a polymer containing fluorine oxyalkylene groups having olefin moieties at both ends of the molecular chain and an organosilicon compound containing two or more SiH groups without hydrolyzable terminal groups in the molecule 1 equivalent of the terminal group can be used in 3-9 equivalents, more preferably 5-7 equivalents, and more preferably about 6 equivalents.

In the preparation of fluorine-containing polyether-based polymer-modified silane when α represented by the formula (1) is 2, as a hydrosilylation reaction catalyst, examples include platinum black, chloroplatinic acid, and alcohols of chloroplatinic acid Modifiers, chloroplatinic acid and olefins, Aldehydes, vinyl siloxanes, complexes of acetylene alcohols, etc., platinum group metal catalysts such as tetrakis (triphenylphosphine) palladium, chloroginseng (triphenylphosphine) rhodium, etc. Platinum compounds such as vinylsiloxane complexes are preferred.

The usage amount of the hydrosilylation reaction catalyst is for the polymer containing fluorinated oxyalkylene groups with olefin moieties at both ends of the molecular chain, or the polymer and the molecule do not have hydrolyzable terminal groups but contain more than 2 SiH groups The mass of the reactant of the organosilicon compound can be used in an amount of 0.1 to 100 ppm, more preferably 1 to 50 ppm, in terms of transition metal conversion (mass).

Finally, the target compound can be obtained by distilling off the solvent and unreacted substances under reduced pressure.

For example, as a polymer containing a fluorinated oxyalkylene group having an olefin moiety at both ends 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 for a polymer-modified silane containing the above-mentioned fluorine-containing polyether group. The surface treatment agent may also include making the The hydroxyl group of the fluoropolyether-based polymer-modified silane or the moiety obtained by condensing the hydroxyl group of the terminal hydrolyzable group of the fluoropolyether-based polymer-modified silane in advance by conventional methods (hydrolysis) Condensate.

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

The amount of hydrolysis and condensation catalyst added is the amount of catalyst, usually 0.01~5 parts by mass, especially 0.1~ 1 part by mass.

The surface treatment agent may also contain a suitable 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-based solvents (methyl perfluorobutyl ether, ethyl perfluorobutyl ether, perfluoro(2-butyltetrahydrofuran), etc.), fluorine-modified alkylamine-based solvents (perfluorotributylamine , perfluorotripentylamine, etc.), hydrocarbon solvents (petroleum benzine, toluene, xylene, etc.), ketone solvents (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.). Among these, fluorine-modified solvents are desired in terms of solubility, wettability, etc., and 1,3-bis(trifluoromethyl)benzene, perfluoro(2-butyltetrahydrofuran), perfluoro(2-butyltetrahydrofuran), and Fluorotributylamine, ethyl perfluorobutyl ether.

The above-mentioned solvents can be mixed with two or more kinds, and it is preferable to make the fluorine-containing poly Ether-based polymer-modified silanes and/or their partial (hydrolyzed) condensates are uniformly dissolved. In addition, the optimum concentration of the fluorine-containing polyether-based polymer-modified silane and/or its partial (hydrolyzed) condensate dissolved in the solvent varies depending on the treatment method, as long as it is an easy-to-scale amount, but in direct coating , preferably 0.01-10 parts by mass, particularly preferably 0.05-5 parts by mass, for a total of 100 parts by mass of the solvent and fluorine-containing polyether-based polymer-modified silane (and its partial (hydrolyzed) condensate), When performing evaporation treatment, it is preferably 1 to 100 parts by mass, particularly preferably 3 parts by mass, based on 100 parts by mass of the total of the solvent and the polymer-modified silane (and its partial (hydrolyzed) condensate) containing fluorine-containing polyether groups. ~30 parts by mass.

The surface treatment agent of the present invention can be applied to the substrate by conventional methods such as brush coating, dipping, spraying, and evaporation treatment. The heating method during the vapor deposition treatment may be either resistance heating or electron beam heating, and is not particularly limited. And the hardening temperature also varies with the hardening method, but for example, in the case of direct coating (brush coating, dipping, spraying, etc.), it is better at 25~200°C, especially at 25~80°C for 30 minutes to 36 hours, especially 1~24 hours. Also, when it is applied by vapor deposition, it is desirable to be in the range of 20 to 200°C. Moreover, it can harden|cure under humidification. The thickness of the cured film is appropriately selected according to the type of base material, but it is usually 0.1 to 100 nm, especially 1 to 20 nm. And, for example, in the case of spray coating, after diluting in advance with a fluorine-based solvent to which water is added, and hydrolyzing, that is, generating Si-OH, when spray coating is performed, the hardening after coating is quick.

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

Examples of articles treated with the surface treatment agent of the present invention are car satellite navigation, mobile phones, digital cameras, digital video cameras, PDAs, portable audio-visual displays, car audio, game machines, eyeglass lenses, camera lenses, lens filters, solar Glasses, gastroscopes and other medical equipment, photocopiers, PCs, liquid crystal displays, organic EL displays, plasma displays, touch panel displays, protective films, anti-reflection films, etc. The surface treatment agent of the present invention can prevent fingerprints and sebum from adhering to the above-mentioned articles, thereby imparting scratch prevention properties, so it can be used especially as a water-repellent and oil-repellent layer for touch panel displays, antireflection films, and the like.

In addition, the surface treatment agent of the present invention can also be used as an antifouling coating film for sanitary products such as bathtubs and washstands, as an antifouling coating film for window glass or tempered glass of automobiles, trams, airplanes, etc., headlight covers, etc., and for outer walls. Water-repellent and oil-repellent coating film for building materials, anti-oil coating film for kitchen building materials, anti-fouling and anti-fouling stickers for telephone booths. Coating film for graffiti, anti-fingerprint coating film for art works, anti-fingerprint coating film for optical discs, DVDs, etc., release agent for molds or coating additives, resin modifier, flow of inorganic fillers It is used as a lubricity enhancer for property modifiers or dispersion modifiers, tapes, films, etc.

[Example]

Reference examples, examples, and comparative examples are illustrated below, and the present invention will be described in more detail, but the present invention is not limited by the following examples.

[Reference example 1]

In the reaction vessel, mix 2.9×10 ^-2 mol of the compound represented by the following formula (A):

4.3×10 ^-2 mol of the compound represented by the following formula (B):

Tetrabutylammonium bisulfate 0.89g (2.6×10 ^-3 mol). Next, after adding 35 g (2.6×10 ^-1 mol) of a 30 mass % sodium hydroxide aqueous solution, it heated at 60 degreeC for 20 hours. After heating, it was cooled to room temperature, and aqueous hydrochloric acid was added dropwise. After recovering the lower fluorine compound layer by a liquid separation operation, it was washed with acetone. The fluorine compound layer, which is the lower layer after washing, was collected again, and the residual solvent was distilled off under reduced pressure. The above operation was performed again to obtain 103 g of a fluorine-containing polyether group polymer represented by the following formula (C).

Also, the results of molecular structure analysis by NMR of the fluorine-containing polyether-based polymer represented by the formula (C) are as follows.

¹ H-NMR

δ3.4-3.5(CC H ₂ -O-CH ₂ CH=CH ₂ )6H

δ3.6-3.7 ( _-CF2 - _CH2 -OCH2 _- C)2H

δ3.7-3.8 ( _-CF2 - CH2 _- OCH2 _- C)2H

δ3.8-3.9(C-CH ₂ -OC H ₂ CH=CH ₂ )6H

δ5.0-5.2(C-CH ₂ -O-CH ₂ CH= CH ₂ )6H

δ5.7-5.9(C- _CH2 -O-CH2CH= _{CH2 )} 3H

In a reaction vessel, mix 1.5×10 ^-2 mol of the compound represented by the following formula (C) obtained above (that is, the terminal allyl ether group; equivalent to 4.5×10 ^-2 mol):

50g of 1,3-bis(trifluoromethyl)benzene, 11g (9.0×10 ^-2 mol) of trimethoxysilane, and 5.0×10 ^-2 toluene solution of chloroplatinic acid/vinylsiloxane complex g (containing 1.5×10 ^-7 mol based on Pt monomer), aged at 80°C for 5 hours. Then, the solvent and unreacted materials were distilled off under reduced pressure to obtain 55 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

δ0.4-0.6 ( _{-CH2CH2CH2 -} Si ₎ 6H

δ1.4-1.6 ( _{-CH2CH2CH2 -} Si ₎ 6H

δ3.1-3.7(-Si(OC H ₃ ) ₃ , -CH ₂ CH ₂ CH ₂ -Si, CCH _{2 -OCH 2 CH 2} CH ₂ -Si, -CF ₂ -CH ₂ -OCH ₂ -C, -CF ₂ -CH ₂ -O- CH ₂ -C)43H

[Example 1]

In the reaction vessel, mix 2.9×10 ^-2 mol of the compound represented by the following formula (A):

4.3×10 ^-2 mol of the compound represented by the following formula (E):

Tetrabutylammonium bisulfate 0.89g (2.6×10 ^-3 mol). Next, after adding 35 g (2.6×10 ^-1 mol) of a 30 mass % sodium hydroxide aqueous solution, it heated at 60 degreeC for 20 hours. After heating, it was cooled to room temperature, and aqueous hydrochloric acid was added dropwise. After recovering the lower fluorine compound layer by a liquid separation operation, it was washed with acetone. The fluorine compound layer, which is the lower layer after washing, was collected again, and the residual solvent was distilled off under reduced pressure. The above operation was performed again to obtain 101 g of a fluorine-containing polyether group polymer represented by the following formula (F).

Also, the results of molecular structure analysis by NMR of the fluorine-containing polyether-based polymer represented by formula (F) are as follows.

¹ H-NMR

_δ0.7-0.9 ( _-CH2CH3 ) 3H

δ1.3-1.5 ( _{-CH2CH3 )} 2H

δ3.2-3.2(CC H ₂ -O-CH ₂ CH=CH ₂ )4H

δ3.4-3.5 ( _-CF2 - _CH2 -OCH2 _- C)2H

δ3.6-3.7 ( _-CF2 - CH2 _- OCH2 _- C)2H

δ3.8-3.9(C-CH ₂ -OC H ₂ CH=CH ₂ )4H

δ4.9-5.2(C-CH ₂ -O-CH ₂ CH= CH ₂ )4H

δ5.7-5.8(C- _CH2 -O-CH2CH= _{CH2 )} 2H

In a reaction vessel, mix 1.5×10 ^-2 mol of the compound represented by the following formula (F) obtained above (ie terminal allyl ether group; equivalent to 3.0×10 ^-2 mol):

50g of 1,3-bis(trifluoromethyl)benzene, 7.3g (6.0×10 ^-2 mol) of trimethoxysilane, and 5.0×10 ^-2 mol of toluene solution of chloroplatinic acid/vinylsiloxane complex ² g (contains 1.5×10 ^-7 mol based on Pt monomer), aged at 80°C for 5 hours. Then, the solvent and unreacted materials were distilled off under reduced pressure to obtain 52 g of a liquid product.

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

¹ H-NMR

_δ0.4-0.6 ( _{-CH2CH2CH2 -} Si) 4H

_δ0.6-0.8 ( _-CH2CH3 ) 3H

δ1.2-1.4 ( _{-CH2CH3 )} 2H

_δ1.5-1.7 ( _{-CH2CH2CH2 -} Si) 4H

δ3.1-3.7(-Si(OC H ₃ ) ₃ , -CH ₂ CH ₂ CH ₂ -Si, CCH _{2 -OCH 2 CH 2} CH ₂ -Si, -CF ₂ -CH ₂ -OCH ₂ -C, -CF ₂ -CH ₂ -O- CH ₂ -C)30H

[Example 2]

In the reaction vessel, mix 2.7×10 ^-2 mol of the compound represented by the following formula (H) (that is, the terminal hydroxyl group; equivalent to 5.4×10 ^-2 mol):

8.1×10 ^-2 mol of the compound represented by the following formula (B):

Tetrabutylammonium bisulfate 1.7g (4.9×10 ^-3 mol). Next, after adding 65 g (4.9×10 ⁻¹ mol) of a 30% by mass sodium hydroxide aqueous solution, it was heated at 60° C. for 20 hours. After heating, it was cooled to room temperature, and aqueous hydrochloric acid was added dropwise. After recovering the lower fluorine compound layer by a liquid separation operation, it was washed with acetone. The fluorine compound layer, which is the lower layer after washing, was collected again, and the residual solvent was distilled off under reduced pressure. The above operation was performed again to obtain 107 g of a fluorine-containing polyether group polymer represented by the following formula (I).

In addition, the molecular structure analysis results of the fluorine-containing polyether-based polymer represented by formula (I) by NMR are as follows.

¹ H-NMR

δ3.4-3.5(CC H ₂ -O-CH ₂ CH=CH ₂ )12H

δ3.6-3.7 ( _-CF2 - _CH2 -OCH2 _- C)4H

δ3.7-3.8(-CF ₂ -CH ₂ -OC H 2 _-C )4H

δ3.8-3.9(C-CH ₂ -OC H ₂ CH=CH ₂ )12H

δ4.9-5.1(C-CH ₂ -O-CH ₂ CH= CH ₂ )12H

δ5.7-5.9( C - _CH2 -O-CH2CH= _{CH2 )} 6H

In a reaction vessel, mix 1.33×10 ^-2 mol of the compound represented by the following formula (I) obtained above (that is, the terminal allyl ether group; equivalent to 8.0×10 ^-2 mol):

50g of 1,3-bis(trifluoromethyl)benzene, 20g of trimethoxysilane (1.6×10 ^-1 mol), and 5.0×10 ^-2 toluene solution of chloroplatinic acid/vinylsiloxane complex g (containing 1.5×10 ^-7 mol based on Pt monomer), aged at 80°C for 5 hours. Then, the solvent and unreacted materials were distilled off under reduced pressure to obtain 60 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

δ0.4-0.7 ( _{-CH2CH2CH2 -} Si ₎ 12H

δ1.4-1.7 ( _{-CH2CH2CH2 -} Si ₎ 12H

δ3.1-3.8(-Si(OC H ₃ ) ₃ , -CH ₂ CH ₂ CH ₂ -Si, CCH _{2 -OCH 2 CH 2} CH ₂ -Si, -CF ₂ -CH ₂ -OCH ₂ -C, -CF ₂ -CH ₂ -O- CH ₂ -C)86H

[Comparative example 1]

As Comparative Example 1, the following polymer was used.

【Chemical 55】CF ₃ O-(CF ₂ O) _p1 -(C ₂ F ₄ O) _q1 -CF ₂ -O-CH ₂ CH ₂ CH ₂ -Si(OCH ₃ ) ₃ (K)

p1:q1=47:53, p1+q1≒43

[Comparative example 2]

As Comparative Example 2, the following polymer was used.

Preparation of surface treatment agent and formation of hardened film

In the fluorine-containing polyether-based polymer-modified silane obtained in Reference Example 1, Example 1, and 2, use the fluorine-containing polyether-based polymer-modified silane obtained in Reference Example 1 and Example 1 as a surface treatment agent Available for evaluation below. That is, the fluorine-containing polyether-based polymer-modified silane obtained in Reference Example 1 and Example 1 and the polymers of Comparative Examples 1 and 2 were dissolved in Novec 7200 (manufactured by 3M Corporation, Ethyl perfluorobutyl ether) prepared surface treatment agent.

[Film Coating]

On the glass (Gorilla manufactured by Corning Incorporated) treated with 10nm SiO ₂ on the outermost surface, 6 mg of each surface treatment agent was vacuum-deposited (processing conditions, pressure: 2.0×10 ^-2 Pa, heating temperature: 700°C), at 25 Cure at 40% humidity for 12 hours to form a cured film with a thickness of 7nm.

[Thick Film Coating]

10 mg of each surface treatment agent was vacuum-deposited on the glass (Gorilla manufactured by Corning Corporation) with a SiO ₂ treatment of 10 nm on the outermost surface (processing conditions, pressure: 2.0×10 ^-2 Pa, heating temperature: 700 ° C), at 25 Cure at 40% humidity for 12 hours to form a cured film with a thickness of 14nm.

Evaluation of water repellency [Evaluation of initial water repellency]

For the above-mentioned glass with a hardened coating formed by thin film coating, the contact angle (water repellency) of the hardened coating to water (droplet: 2 μl, temperature: 25°C, Humidity: 40%). Table 1 shows the results (initial water contact angle).

In the initial stage, all of the Reference Examples, Examples, and Comparative Examples showed good water repellency.

[Evaluation of abrasion resistance]

For the above-mentioned glass (for abrasion resistance evaluation) formed by thin film coating, the cured film was rubbed 10,000 times using a friction tester (manufactured by Shinto Scientific Co., Ltd.) in the same manner as above. The contact angle to water (water repellency) was measured as an evaluation of abrasion resistance. The test environment conditions are 25°C and 40% humidity. The results (water contact angle after abrasion) are shown in Table 1.

Steel wool abrasion resistance

Steel wool: BONSTAR#0000 (manufactured by Japan Steel Wool Co., Ltd.)

Contact area: 10mmΦ

Moving distance (single trip) 30mm

Moving speed 1,800mm/min

Load: 1kg/cm ²

The compound of reference example 1 and embodiment 1 has a plurality of ether linking groups in the molecule, and the adhesion with the substrate is improved, so the hardened film using the surface treatment agent of the compound of reference example 1 and embodiment 1 is comparable to that of the comparative example. Compared with it, it exerts good wear resistance with a contact angle of 100° or more.

[Evaluation of haze value]

For the above-mentioned glass with a hardened film formed by thin film coating and thick film coating (for evaluation of haze value), use a nephelometer (NDH-5000) (manufactured by Nippon Denshoku Industries Co., Ltd.) in accordance with JIS K 7136:2000 Determination of haze value. The results (haze value) are shown in Tables 1 and 2. The haze value was 0.3 or more, and haze was confirmed visually. When the thin film (7nm) is coated, the haze values of the reference example, the example, and the comparative example are all lower than 0.3. On the other hand, when thick film (14nm) is coated, the compound of reference example 1 and embodiment 1 improves the wettability with the substrate due to the ether linking group having multiple polar groups in the molecule, so using reference example 1 and implementing Compared with the comparative example, the cured film of the surface treatment agent of the compound of Example 1 has a haze value of 0.3 or less and improved visibility.

Claims (11)

A fluorine-containing polyether-based polymer-modified silane represented by the following general formula (1),

(wherein, Rf is a polymer residue of a monovalent or divalent fluorine-containing oxyalkylene group, Q is a divalent hydrocarbon group with 2 to 5 carbon atoms that may contain an ether bond, Y is a silicon atom, a silane 2-6 valent hydrocarbon groups with radicals and/or siloxane bonds, R is independently an alkyl group with 1-4 carbons, X is independently a hydroxyl group or a hydrolyzable group, n is an integer of 1-3, γ is a number of 1-5 Integer, m is an integer of 1 to 5, R' is an alkyl group with 1 to 4 carbons, β is 1 or 2, and α is 1 or 2). Such as the fluorine-containing polyether-based polymer-modified silane of claim 1, wherein the α of the aforementioned formula (1) is 1, and the Rf group is the polymerization of a monovalent fluorine-containing oxyalkylene group represented by the following general formula (2) substance residues,

(wherein, p, q, r, and s are integers from 0 to 200, respectively, p+q+r+s=an integer from 3 to 200, and each repeating unit can be linear or branched, and each repeating unit They can be randomly bonded to each other, d is an integer of 1 to 3, and the unit (-C _d F _2d -) can be linear or branched). Such as the fluorine-containing polyether-based polymer-modified silane of claim 1, wherein the α of the aforementioned formula (1) is 2, and the Rf group is the polymerization of a divalent fluorine-containing oxyalkylene group represented by the following general formula (3) substance residues,

(wherein, p, q, r, and s are integers from 0 to 200, respectively, p+q+r+s=an integer from 3 to 200, and each repeating unit can be linear or branched, and each repeating unit They can be randomly bonded to each other, d is an integer of 1 to 3, and the units (-C _d F _2d -) can be independently linear or branched). Such as any one of the fluorine-containing polyether-based polymer-modified silanes in claims 1 to 3, wherein in the aforementioned formula (1), Y is selected from alkylene groups with 3 to 10 carbons (except that α is 1 When β is 1 or 2), the alkylene group of an arylylene group containing 6 to 8 carbons (but when α is 1, β is 1 or 2), the alkylene group passes through the silicon atom, the silylylene group, A divalent group bonded by a siliconyl structure or a siliconyl aryl structure, and a straight chain with 2 to 10 silicon atoms or a branched or cyclic 2 to 4 valent organic group with 3 to 10 silicon atoms Polysiloxane residue, or at least one group of 2-4 valent groups that are bonded to silicon atoms with alkylene groups having 2-10 carbon atoms. As the polymer-modified silane of fluorine-containing polyether group according to any one of claims 1 to 3, wherein Y is a divalent hydrocarbon group that may have a silicon atom, a silane group and/or a siloxane bond (only, Y is A divalent hydrocarbon group not having a silicon atom, a silane group and/or a siloxane bond, and when α is 1, β is 1 or 2). The fluorine-containing polyether-based polymer-modified silane according to any one of claims 1 to 3, wherein in the aforementioned formula (1), Q is -CH ₂ OCH ₂ -. Fluorine-containing polyether-based polymer-modified silane as in claim 6, wherein in the aforementioned formula (1), Q is -CH ₂ OCH ₂ -, and Y does not have a silicon atom, a silane group and/or a siloxane A divalent hydrocarbon group with an alkyl bond (but when α is 1, β is 1 or 2). The fluorine-containing polyether-based polymer-modified silane according to any one of claims 1 to 3, wherein in the aforementioned formula (1), X is respectively selected from hydroxyl group, alkoxy group with carbon number 1 to 10, carbon number At least one of the group consisting of alkoxyalkoxy with 2 to 10 carbons, acyloxy with 2 to 10 carbons, alkenyloxy with 2 to 10 carbons, and halo. A fluorine-containing polyether-based polymer-modified silane according to any one of claims 1 to 3, wherein the polymer-modified silane represented by formula (1) is represented by any of the following formulas,

(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, which contains the fluorine-containing polyether-based polymer-modified silane and/or its partial (hydrolyzed) condensate according to any one of claims 1-9. An article having a hardened film of the surface treatment agent according to claim 10 on the surface.