JPWO2019049754A1 - Fluorine-containing compounds, compositions and articles - Google Patents

Abstract

Provided are fluorine-containing compounds, compositions and articles capable of forming a surface layer having excellent weather resistance and corrosion resistance. A fluorine-containing compound represented by R1- (OX) m-Y-Z (R2) q (R3) r-q. R1 is a perfluoroalkyl group. X is an alkylene group having 2 or more carbon atoms and having one or more fluorine atoms. m is an integer from 0 to 6. Y is a single bond or a predetermined linking group. However, when Y is an alkylene group containing -OCF2-, the number of -OCF2- in the alkylene group is one. R4 is a hydrogen atom or an alkyl group. Z is a carbon atom, a silicon atom or a nitrogen atom. R2 is a hydrogen atom, a hydroxyl group or an alkyl group. R3 is −L1-Si (R) nL3-n, R is a monovalent hydrocarbon group, L is a hydrolyzable group or a hydroxyl group, n is an integer of 0 to 2, and L1 has −O−. It is an alkylene group which may be used. r is an integer of 2 or 3, and q is an integer of 0 to 2.

Description

The present invention relates to fluorine-containing compounds, compositions and articles.

Fluorine-containing compounds are preferably used as surface treatment agents because they exhibit water and oil repellency and the like. By imparting water and oil repellency to the surface of the base material with a surface treatment agent, it becomes easier to wipe off the dirt on the surface of the base material, and the dirt removal property is improved. Therefore, a surface layer using a fluorine-containing compound is widely used in transportation equipment such as automobiles where adhesion of dirt is likely to be a problem.
Patent Document 1 describes a fluorine-containing ether compound having a poly (oxyperfluoroalkylene) chain in which an ether bond (-O-) is present in the middle of a perfluoroalkylene chain, and an ether bond (-O-) having a fluoroalkyl group. ), And a composition containing the fluorine-containing compound is disclosed to be applied to transportation equipment.

International Publication No. 2011/016458

In the field of transportation equipment, a surface layer formed by using a fluorine-containing compound is required to have excellent weather resistance and corrosion resistance.
When the present inventor formed a surface layer using a fluorine-containing compound having a fluoroalkyl group and no ether bond (-O-) among the fluorine-containing compounds described in Patent Document 1, weather resistance and corrosion resistance were formed. Was found to be inadequate.

In view of the above problems, an object of the present invention is to provide a fluorine-containing compound, a composition and an article capable of forming a surface layer having excellent weather resistance and corrosion resistance.

The present invention provides fluorine-containing compounds, compositions and articles having the following configurations [1] to [11].
[1] A fluorine-containing compound represented by the formula 1.
R ^1- (OX) _m- Y-Z (R ² ) _q (R ³ ) _r-q Equation 1
However, in the formula,
R ¹ is a perfluoroalkyl group.
X is an alkylene group having 2 or more carbon atoms and having one or more fluorine atoms.
m is an integer from 0 to 6.
Y is a single bond, -O-, -C (O) N (R ⁴ )-, -C (O)-, or -O-, -C (O) N (R ⁴ )-or -C ( O)-is an alkylene group which may have −. The -O -, - C (O) N (R 4) - or -C (O) - alkylene group which may have a may have a fluorine atom. However, the Y is -OCF ₂ - when is an alkylene group containing, -OCF ₂ in the alkylene group - number of is one.
R ⁴ is a hydrogen atom or an alkyl group.
Z is a carbon atom, a silicon atom or a nitrogen atom.
R ² is a hydrogen atom, a hydroxyl group or an alkyl group.
R ³ is −L ¹ −Si (R) _n L _3-n . R is a monovalent hydrocarbon group. L is a hydrolyzable group or a hydroxyl group. n is an integer from 0 to 2. L ¹ is an alkylene group which may have —O−.
When Z is a carbon atom or a silicon atom, r is 3 and q is an integer of 0-2. When Z is a nitrogen atom, r is 2 and q is an integer of 0 to 1.

[2] The fluorine-containing compound according to [1], wherein R ¹ is a perfluoroalkyl group having 1 to 6 carbon atoms.
[3] The fluorine-containing compound of [1] or [2], wherein X is a fluoroalkylene group having 2 or 3 carbon atoms, which has one hydrogen atom or no hydrogen atom.
[4] The fluorine-containing compound according to any one of [1] to [3], wherein m is 0 or 1.
[5] The fluorine-containing compound according to any one of [1] to [4], wherein Z is a carbon atom or a silicon atom, and q is 0 or 1.
[6] The fluorine-containing compound according to any one of [1] to [5] used for forming a surface layer of a base material constituting a transportation device.
[7] A composition comprising the fluorine-containing compound according to any one of the above [1] to [6] and a liquid medium.
[8] It is characterized by having a base material and a surface layer formed on the base material from the fluorine-containing compound of any one of [1] to [6] or the composition of [7]. Goods.
[9] A surface treatment agent containing the fluorine-containing compound according to any one of the above [1] to [6].

[10] A fluorine-containing compound represented by the formula 2.
R ^1- (OX) _m- Y-Z (R ² ) _q (L ² -CH = CH ₂ ) _r-q Equation 2
However, in the formula,
R ¹ is a perfluoroalkyl group.
X is an alkylene group having 2 or more carbon atoms and having one or more fluorine atoms.
m is an integer from 0 to 6.
Y is a single bond, -O-, -C (O) N (R ⁴ )-, -C (O)-, or -O-, -C (O) N (R ⁴ )-or -C ( O)-is an alkylene group which may have −. The -O -, - C (O) N (R 4) - or -C (O) - alkylene group which may have a may have a fluorine atom. However, the Y is -OCF ₂ - when is an alkylene group containing, -OCF ₂ in the alkylene group - number of is one.
R ⁴ is a hydrogen atom or an alkyl group.
Z is a carbon atom, a silicon atom or a nitrogen atom.
R ² is a hydrogen atom, a hydroxyl group or an alkyl group.
L ² is an alkylene group, a single bond or -O- which may have -O-.
When Z is a carbon atom or a silicon atom, r is 3 and q is an integer of 0-2. When Z is a nitrogen atom, r is 2 and q is an integer of 0 to 1.

[11] A method for producing a fluorine-containing compound represented by formula 1, wherein the fluorine-containing compound represented by formula 2 is hydrosilylated with HSi (R) _n L _3-n .
R ^1- (OX) _m- Y-Z (R ² ) _q (R ³ ) _r-q Equation 1
R ^1- (OX) _m- Y-Z (R ² ) _q (L ² -CH = CH ₂ ) _r-q Equation 2
However, in the formula,
R ¹ is a perfluoroalkyl group.
X is an alkylene group having 2 or more carbon atoms and having one or more fluorine atoms.
m is an integer from 0 to 6.
Y is a single bond, -O-, -C (O) N (R ⁴ )-, -C (O)-, or -O-, -C (O) N (R ⁴ )-or -C ( O)-is an alkylene group which may have −. The -O -, - C (O) N (R 4) - or -C (O) - alkylene group which may have a may have a fluorine atom. However, the Y is -OCF ₂ - when is an alkylene group containing, -OCF ₂ in the alkylene group - number of is one.
R ⁴ is a hydrogen atom or an alkyl group.
Z is a carbon atom, a silicon atom or a nitrogen atom.
R ² is a hydrogen atom, a hydroxyl group or an alkyl group.
R ³ is −L ¹ −Si (R) _n L _3-n . R is a monovalent hydrocarbon group. L is a hydrolyzable group or a hydroxyl group. n is an integer from 0 to 2. L ¹ is an alkylene group which may have —O−.
L ² is an alkylene group, a single bond or -O- which may have -O-.
When Z is a carbon atom or a silicon atom, r is 3 and q is an integer of 0-2. When Z is a nitrogen atom, r is 2 and q is an integer of 0 to 1.

According to the present invention, it is possible to provide a fluorine-containing compound, a composition and an article capable of forming a surface layer having excellent weather resistance and corrosion resistance.

In the present specification, the compound represented by the formula 1 is referred to as compound 1. Compounds represented by other formulas are also described in the same manner.
In the present specification, when "the alkylene group may have an A group", the alkylene group may have an A group between carbon atoms in the alkylene group, or the alkylene group-. It may have an A group at the end, such as A group.
The meanings of the terms in the present invention are as follows.
"Surface layer" means a layer formed on a substrate. The surface layer may be formed directly above the base material, or may be formed on the base material via another layer formed on the surface of the base material.

The surface layer formed by using compound 1 has excellent weather resistance. It is presumed that the reason for this is that the number of repeating units (m) of the oxyfluoroalkylene chain represented by (OX), which is easily broken by the action of light, heat, or the like, is as small as 0 to 6.
Further, the surface layer formed by using the compound 1 is also excellent in corrosion resistance. The reason for this is that having a plurality of groups represented by −Si (R) _n L _3-n increases the number of reaction points between compound 1 and the base material or intermediate layer to which the compound 1 is applied, resulting in a dense surface. It is presumed that the layer could be formed.
As described above, since compound 1 has excellent weather resistance and corrosion resistance, it is suitably used for forming a surface layer of equipment used in various environments, particularly transportation equipment (for example, automobiles, trains, ships, aircraft). .. That is, a surface treatment agent containing compound 1 is preferable because a surface layer having excellent weather resistance can be obtained.

[Fluorine-containing compound]
Compound 1 is represented by the formula 1.
R ^1- (OX) _m- Y-Z (R ² ) _q (R ³ ) _r-q Equation 1
R ¹ is a perfluoroalkyl group.
The number of carbon atoms in the perfluoroalkyl group is preferably 1 to 20, more preferably 1 to 10, and particularly preferably 1 to 6 from the viewpoint of more excellent weather resistance and corrosion resistance of the surface layer.
The perfluoroalkyl group may be linear, branched or cyclic, but linear is preferred.

X is an alkylene group having 2 or more carbon atoms and having one or more fluorine atoms.
The alkylene group has 2 or more carbon atoms, and is preferably 2 to 6 and particularly preferably 2 or 3 from the viewpoint of more excellent weather resistance and corrosion resistance of the surface layer.
The alkylene group is preferably linear because the effect of the present invention is more excellent.
The alkylene group preferably has 1 or more fluorine atoms and is more excellent in corrosion resistance of the surface layer, preferably 2 to 10 groups, and particularly preferably 2 to 4 groups. The alkylene group has 0 (perfluoroalkylene group) or 1 hydrogen atom.
The alkylene group may be a group in which all hydrogen atoms in the alkylene group are substituted with fluorine atoms (perfluoroalkylene group).

Specific examples of (OX) include OCHFCF ₂ , OCF ₂ CF ₂ , and OCF (CF ₃ ) CF ₂ .

m is an integer of 0 to 6, and is preferably 0 to 3, more preferably 0 or 1, from the viewpoint of more excellent weather resistance of the surface layer.
When m is 0, (OX) _m is a single bond.

When m is 2 or more, the plurality of OXs may be the same or different. That is, (OX) _m may be composed of two or more different types of (OX). The binding order of two or more types of (OX) is not limited, and may be randomly, alternately, or arranged in blocks.

Y is a single bond, -O-, -C (O) N (R ⁴ )-, -C (O)-, or -O-, -C (O) N (R ⁴ )-or -C ( O)-is an alkylene group which may have −.
Alkylene group -O -, - C (O) N (R 4) - or -C (O) -, then a carbon - between carbon atoms and a _(OX) these groups at at least one end of the _m-side It is preferable to have.
Alkylene group, -O -, - C (O ) N (R 4) - and -C (O) - group may include a plurality of selected from the group consisting of. Alkylene group -O -, - C (O) N (R 4) - and -C (O) - when having a plurality of groups selected from the group consisting of carbon - between carbon atoms and _{(OX) m-side} It is preferable to have these groups at both ends.
-O -, - C (O) N (R 4) - or -C (O) - number of carbon atoms in the alkylene group which may have a is from 1 to 10 are preferred, 1-6 being particularly preferred.
-O -, - C (O) N (R 4) - or -C (O) - alkylene group which may have a may have a fluorine atom. That is, the hydrogen atom in the alkylene group may be substituted with a fluorine atom.
R ⁴ is a hydrogen atom or an alkyl group (preferably having 1 to 10 carbon atoms).
Here, Y is -OCF ₂ - when is an alkylene group containing, -OCF ₂ in the alkylene group - number of is one. For example, any of the alkylene groups represented by −OCF ₂ −, the alkylene group represented by −OCF ₂ CH ₂ OCH ₂ CH ₂ CH ₂ − and the alkylene group represented by −OCF ₂ C (O) NHCH ₂ −. Also, the number of -OCF _2- is one, which satisfies the definition of Y. In contrast, -OCF ₂ OCF ₂ - alkylene group and -OCF ₂ OCF ₂ OCF ₂ represented by - alkylene group represented by like, -OCF ₂ - alkylene group number of two or more of, Y Does not meet the definition of.
-O -, - C (O) N (R 4) - or -C (O) - Examples of alkylene group which may have a _{can, -CH 2 CH 2 -, -} C (O) NHCH _2- , -C (O) N (CH ₃ ) CH _2- , -OCF ₂ C (O) NHCH _2- , -OCH _2- , -OCF _2- , -CH ₂ OCH ₂ CH ₂ CH ₂ -,- OCF ₂ CH ₂ OCH ₂ CH ₂ CH ₂ −, −CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ −.

Z is a carbon atom, a nitrogen atom or a silicon atom.
When Z is a carbon atom or a silicon atom, r is 3, q is an integer of 0-2, preferably 0 or 1, and particularly preferably 0. When Z is a nitrogen atom, r is 2, q is an integer of 0 to 1, and 0 is preferable.

R ² is a hydrogen atom, a hydroxyl group or an alkyl group.
The number of carbon atoms of the alkyl group is preferably 1 to 5, more preferably 1 to 3, and particularly preferably 1.
When q is 2, the two R ^2s may be the same or different. From the viewpoint of easy availability of raw materials and easy production of compound 1, they are preferably the same.

R ³ is −L ¹ −Si (R) _n L _3-n .
L ¹ is an alkylene group which may have —O−.
When the alkylene group has -O-, it is preferable to have -O- between carbon-carbon atoms or at the Z-side terminal.
The number of carbon atoms in L ¹ is preferably 2 to 10, more preferably 2 to 6, and particularly preferably 2 to 4.
When there are a plurality of R ^3s in one molecule, the plurality of R ^3s may be the same or different. From the viewpoint of easy availability of raw materials and easy production of compound 1, they are preferably the same.

R is a monovalent hydrocarbon group, preferably a monovalent saturated hydrocarbon group. The carbon number of R is preferably 1 to 6, more preferably 1 to 3, and particularly preferably 1 or 2.

L is a hydrolyzable group or a hydroxyl group. As L, a hydrolyzable group is preferable.
The hydrolyzable group of L is a group that becomes a hydroxyl group by a hydrolysis reaction. That is, when L is a hydrolyzable group, the hydrolyzable silyl group represented by Si-L becomes a silanol group represented by Si-OH by the hydrolysis reaction. The silanol groups further react between the silanol groups to form a Si—O—Si bond. Further, the silanol group can form a chemical bond (base material-O-Si) by dehydration condensation reaction with a hydroxyl group (base material-OH) on the surface of the base material.

Specific examples of the hydrolyzable group include an alkoxy group, a halogen atom, an acyl group, and an isocyanate group (-NCO). As the alkoxy group, an alkoxy group having 1 to 4 carbon atoms is preferable. As the halogen atom, a chlorine atom is preferable.
As the hydrolyzable group, an alkoxy group having 1 to 4 carbon atoms or a halogen atom is preferable because the compound 1 can be more easily produced. As L, an alkoxy group having 1 to 4 carbon atoms is preferable, and an ethoxy group is required when long-term storage stability of compound 1 is required, because there is little outgassing during coating and the storage stability of compound 1 is more excellent. Is particularly preferable, and a methoxy group is particularly preferable when the reaction time after coating is short.

n is an integer from 0 to 2.
n is preferably 0 or 1, and 0 is particularly preferable. The presence of a plurality of L makes the adhesion of the surface layer to the base material stronger.
When n is 1 or less, the plurality of Ls present in one molecule may be the same or different. From the viewpoint of easy availability of raw materials and easy production of compound 1, they are preferably the same.

Specific examples of Compound 1 include the following.

Compound 1 can be produced by a known production method. For example, compound 1 can be produced by hydrosilylating compound 2 with HSi (R) _n L _3-n .
R ^1- (OX) _m- Y-Z (R ² ) _q (L ² -CH = CH ₂ ) _r-q Equation 2
In the formula, the definitions of R ¹ , X, m, Y, Z, R ² , q, r are as described above, where L ² is an alkylene group, single bond or -O which may have -O-. -, And when L ² -CH = CH ₂ is hydrosilylated, it becomes L ^{1 of} compound 1. For example, when Y is −C (O) NHCH ₂₋ , compound 2 is prepared using R ^{1 −} OH (the definition of R ¹ is as described above) as a raw material by a known method, and R ¹ − (OX) _m −. C (O) OR ⁵ (R ⁵ is an alkyl group having 1 to 6 carbon atoms) is obtained and reacted with NH _2- CH _2- Z (R ² ) _q (L ² -CH = CH ₂ ) _r-q. Can be manufactured.

〔Composition〕
The composition of the present invention (hereinafter, also referred to as "the present composition") contains compound 1 and a liquid medium.

Compound 1 may be used alone or in combination of two or more.
The content of compound 1 is preferably 0.001 to 30% by mass, particularly preferably 0.01 to 20% by mass, based on the total mass of the present composition.

Specific examples of the liquid medium include water and an organic solvent. Specific examples of the organic solvent include a fluorinated organic solvent and a non-fluorinated organic solvent.
The organic solvent may be used alone or in combination of two or more.

Specific examples of the fluorinated organic solvent include fluorinated alkanes, fluorinated aromatic compounds, fluoroalkyl ethers, fluorinated alkylamines, and fluoroalcohols.
The fluorinated alkane is preferably a compound having 4 to 8 carbon atoms, for example, C ₆ F ₁₃ H (AC-2000: product name, manufactured by Asahi Glass Co., Ltd.), C ₆ F ₁₃ C ₂ H ₅ (AC-6000: product name). , Asahi Glass Co., Ltd.), C ₂ F ₅ CHFCHFCF ₃ (Bertrel: product name, manufactured by DuPont).
Specific examples of the fluorinated aromatic compound include hexafluorobenzene, trifluoromethylbenzene, perfluorotoluene, 1,3-bis (trifluoromethyl) benzene, and 1,4-bis (trifluoromethyl) benzene.
The fluoroalkyl ether is preferably a compound having 4 to 12 carbon atoms, for example, CF ₃ CH ₂ OCF ₂ CF ₂ H (AE-3000: product name, manufactured by Asahi Glass Co., Ltd.), C ₄ F ₉ OCH ₃ (Novec-7100:). Product name, C ₄ F ₉ OC ₂ H ₅ (Novec-7200: Product name, manufactured by 3M), C ₂ F ₅ CF (OCH ₃ ) C ₃ F ₇ (Novec-7300: Product name, (Made by 3M).
Specific examples of the fluorinated alkylamine include perfluorotripropylamine and perfluorotributylamine.
Specific examples of the fluoroalcohol include 2,2,3,3-tetrafluoropropanol, 2,2,2-trifluoroethanol, and hexafluoroisopropanol.

As the non-fluorine-based organic solvent, a compound consisting only of a hydrogen atom and a carbon atom and a compound consisting only of a hydrogen atom, a carbon atom and an oxygen atom are preferable, and specifically, a hydrocarbon-based organic solvent and a ketone-based organic solvent are used. , Ether-based organic solvent, ester-based organic solvent, alcohol-based organic solvent can be mentioned.
Specific examples of the hydrocarbon-based organic solvent include hexane, heptane, and cyclohexane.
Specific examples of the ketone-based organic solvent include acetone, methyl ethyl ketone, and methyl isobutyl ketone.
Specific examples of the ether-based organic solvent include diethyl ether, tetrahydrofuran, and tetraethylene glycol dimethyl ether.
Specific examples of the ester-based organic solvent include ethyl acetate and butyl acetate.
Specific examples of the alcohol-based organic solvent include isopropyl alcohol.

The content of the liquid medium is preferably 70 to 99.999% by mass, particularly preferably 80 to 99.99% by mass, based on the total mass of the present composition.

The composition of the present invention may contain components other than compound 1 and a liquid medium.
Examples of other components include by-products produced in the production process of compound 1, unreacted raw materials, and other unavoidable compounds in production.
In addition, additives such as an acid catalyst and a basic catalyst that promote the hydrolysis and condensation reaction of the hydrolyzable silyl group can be mentioned. Specific examples of the acid catalyst include hydrochloric acid, nitric acid, acetic acid, sulfuric acid, phosphoric acid, sulfonic acid, methanesulfonic acid, and p-toluenesulfonic acid. Specific examples of the basic catalyst include sodium hydroxide, potassium hydroxide, and ammonia.
The content of the other components is preferably 0 to 10% by mass, more preferably 0 to 5% by mass, and particularly preferably 0 to 1% by mass with respect to the compound 1.

[Article]
The article of the present invention has a base material and a surface layer formed on the base material from Compound 1 or the present composition.

The surface layer contains a compound obtained through a hydrolysis reaction and a condensation reaction of compound 1.
The film thickness of the surface layer is preferably 1 to 100 nm, particularly preferably 1 to 50 nm. The thickness of the surface layer is determined by obtaining an interference pattern of reflected X-rays by the X-ray reflectivity method using an X-ray diffractometer for thin film analysis (ATX-G: product name, manufactured by RIGAKU). It can be calculated from the vibration cycle.

The base material is not particularly limited as long as it is a base material for which water and oil repellency is required. Specific examples of the material of the base material include metal, resin, glass, sapphire, ceramic, stone, and composite materials thereof. The glass may be chemically strengthened. The base material may be base-treated with the compounds described in paragraphs 0008 to 0995 of International Publication No. 2011/016458, SiO _{2 and the} like.
As the base material, a base material constituting a transportation device is preferable. Specific examples of the base material constituting the transportation equipment include an exterior of the transportation equipment, a window glass (for example, front glass, side glass, rear glass), a mirror, and a bumper.

The article can be manufactured, for example, by the following method.
A method for obtaining the above-mentioned article by treating the surface of a base material by a dry coating method using Compound 1 or the present composition.
-A method in which the present composition is applied to the surface of a base material by a wet coating method and dried to obtain the above-mentioned article.
In the wet coating method, compound 1 may be hydrolyzed in advance using an acid catalyst, a basic catalyst, or the like, and a composition containing the hydrolyzed compound and a liquid medium can also be used.

Specific examples of the dry coating method include a vacuum deposition method, a CVD method, and a sputtering method. Among these, the vacuum vapor deposition method is preferable from the viewpoint of suppressing the decomposition of compound 1 and the simplicity of the apparatus. At the time of vacuum deposition, a pellet-like substance obtained by impregnating a metal porous body such as iron or steel with Compound 1 or the present composition may be used.
Specific examples of the wet coating method include spin coating method, wipe coating method, spray coating method, squeegee coating method, dip coating method, die coating method, inkjet method, flow coating method, roll coating method, casting method, Langmuir Brodget. The method and the gravure coat method can be mentioned.

The article may have a surface layer formed of another compound or a composition containing another compound on a surface different from the surface having the surface layer formed of Compound 1 or the present composition. Good.
Other compounds include poly (oxyperfluoroalkylene) chains and fluorine-containing ether compounds having either or both of a hydrolyzable group bonded to a silicon atom and a hydroxyl group bonded to a silicon atom. Examples of the fluorine-containing ether compound include compound 3.
[A-O-Z ^1- (R ^f O) _r- ] _j Z ² [-SiR _n L _3-n ] _g formula 3
A is a perfluoroalkyl group or −Q [−SiR _n L _3-n ] _k .
Q is a linking group of (k + 1) valence.
k is an integer of 1-10.
The definitions of R, L and n are synonymous with R, L and n in Equation 1, respectively.
Z ¹ is a single bond having an oxyfluoroalkylene group having 1 to 20 carbon atoms in which one or more hydrogen atoms are substituted with fluorine atoms or 1 to 20 carbon atoms in which one or more hydrogen atoms are substituted with fluorine atoms. It is a poly (oxyfluoroalkylene) group.
R ^f is a perfluoroalkylene group.
r is an integer of 5 to ²⁰⁰ and Z ² is a linking group of (j + g) valence.
j and g are independently integers of 1 or more.

As the fluorine-containing ether compound, a commercially available product can also be used. For example, KY-100 series manufactured by Shin-Etsu Chemical Industry Co., Ltd. (KY-178, KY-185, KY-195, etc.), Optool (registered trademark) DSX manufactured by Daikin Industries, Ltd., Optool (registered trademark) AES, Optool (registered trademark). Examples thereof include UF503, Optool (registered trademark) UD509, and Afluid (registered trademark) S550 manufactured by Asahi Glass Co., Ltd.

Hereinafter, the present invention will be described in detail with reference to examples. However, the present invention is not limited to these examples. The blending amount of each component indicates the mass standard. Of Examples 1 to 19, Examples 1 to 8 and 10 to 18 are Examples, and Examples 9 and 19 are Comparative Examples.

〔Evaluation method〕
(Weatherability)
The water contact angle was measured for the evaluation samples before and after the weather resistance test. The smaller the decrease in water contact angle after the weather resistance test, the smaller the decrease in performance due to the weather resistance test, and the better the weather resistance. The decrease in the water contact angle is preferably 25 degrees or less, more preferably 20 degrees or less.
<Measurement method of water contact angle>
The contact angle (water contact angle) of about 2 μL of distilled water placed on the surface of the surface layer was measured using a contact angle measuring device (DM-500: product name, manufactured by Kyowa Interface Science Co., Ltd.). Measurements were made at five different points on the surface of the surface layer, and the average value was calculated. The 2θ method was used to calculate the contact angle.
<Weather resistance test method>
An outdoor exposure test was conducted in accordance with JIS Z2381: 2001. That is, the evaluation sample was installed outdoors for 3 months so that the surface layer of the evaluation sample faced south at an angle of 30 degrees with respect to the horizontal.

(Corrosion resistance)
The water contact angle was measured for the evaluation samples before and after the corrosion resistance test. The smaller the decrease in the water contact angle after the corrosion resistance test, the smaller the decrease in performance due to the corrosion resistance test, and the better the corrosion resistance. The decrease in the water contact angle is preferably 60 degrees or less, more preferably 45 degrees or less, and particularly preferably 35 degrees or less.

<Corrosion resistance test method>
A salt spray test was conducted in accordance with JIS Z2371: 2015. That is, the surface layer of the evaluation sample was placed so as to face upward at an angle of 20 degrees with respect to the horizontal, and a sodium chloride aqueous solution having a concentration of 5% by mass adjusted to a pH range of 6.5 to 7.2 was placed in an atmosphere of 35 ° C. Sprayed for 300 hours.

[Example 1]
Compound 1-1 was synthesized by the following procedure.

(Example 1-1)
10.0 g of compound X1-1 and 5.0 g of compound X2 were placed in a 50 mL eggplant flask, and the mixture in the eggplant flask was stirred for 12 hours. From NMR, it was confirmed that all of compound X1-1 was converted to compound 2-1. In addition, methanol, which is a by-product, was produced. The obtained solution was diluted with 15.0 g of C ₆ F ₁₃ H (Asahiclean® AC-2000, manufactured by Asahi Glass Co., Ltd.), purified by silica gel column chromatography (developing solvent: AC-2000), and compounded. 13.7 g (yield 95%) of 2-1 was obtained.

(Example 1-2)
In a 20 mL glass sample bottle, 10.0 g of compound 2-1 obtained in Example 1-1 and a xylene solution of platinum / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum) Content: 0.52 g of (2% by mass), 10.3 g of HSi (OCH ₃ ) ₃ , 0.17 g of aniline, 1. of 1,3-bis (trifluoromethyl) benzene (manufactured by Tokyo Kasei Kogyo Co., Ltd.). 7 g was added and the mixture was stirred at 40 ° C. for 8 hours. After completion of the reaction, the solvent and the like were distilled off under reduced pressure and filtered through a membrane filter having a pore size of 1.0 μm to obtain 17.7 g (yield 100%) of Compound 1-1.

[Example 2]
Compound 1-2 was synthesized by the following procedure.

(Example 2-1)
In a 50 mL eggplant flask, 8.8 g of a 24% KOH aqueous solution, 13.2 g of tert-butyl alcohol, 6.3 g of compound X3, and 10.0 g of compound X4 were placed. The mixture was stirred at 60 ° C. for 8 hours under a nitrogen atmosphere. After completion of the reaction, the mixture was washed once with a dilute aqueous hydrochloric acid solution, the organic phase was recovered, and the mixture was concentrated with an evaporator. The obtained solution was purified by silica gel column chromatography (developing solvent: AC-2000) to obtain 13.0 g (yield 80%) of compound 2-2.

(Example 2-2)
16.9 g (yield 100%) of compound 1-2 was obtained in the same manner as in Example 1-2 except that compound 2-1 was changed to 9.1 g of compound 2-2 obtained in Example 2-1. It was.

[Example 3]
Compounds 1-3 were synthesized by the following procedure. The reaction formula is also shown in Example 4 described later.

(Example 3-1)
250 g of tetrahydrofuran was placed in a 1 L eggplant flask and cooled to 0 ° C. 260 mL of 0.7 mol / L allylmagnesium bromide was added dropwise thereto, 20.0 g of compound X1-1 was added dropwise, and the mixture was further stirred for 2 hours. 500 mL of a 1 mol / L hydrochloric acid aqueous solution was added to the mixture to stop the reaction, and the lower layer was subjected to silica gel column chromatography (developing solvent: C ₆ F ₁₃ C ₂ H ₅ (Asahiclean® AC-6000, manufactured by Asahi Glass Co., Ltd.)). ) To obtain 17.4 g (yield 75%) of Compound 2-3.

(Example 3-2)
15.8 g (yield 100%) of compound 1-3 was obtained in the same manner as in Example 1-2 except that compound 2-1 was changed to 8.0 g of compound 2-3 obtained in Example 3-1. It was.

[Example 4]
Compounds 1-4 were synthesized by the following procedure. The reaction formula is shown in accordance with Example 3 above.

(Example 4-1)
In a 50 mL eggplant flask, 9.0 g of the compound 2-3 obtained in Example 3-1, 4.3 g of allyl bromide, 0.09 g of tetrabutylammonium iodide and 2.0 g of potassium hydroxide were placed. The mixture was stirred at 80 ° C. for 5 hours. The mixture in the eggplant flask was cooled to 25 ° C., 9 g of CF ₃ CH ₂ OCF ₂ CF ₂ H (Asahi Clean (registered trademark) AE-3000, manufactured by Asahi Glass Co., Ltd.) was added, and the mixture was washed twice. The obtained crude liquid was purified by silica gel column chromatography (developing solvent: AC-6000) to obtain 9.1 g (yield 91%) of compound 2-4.

(Example 4-2)
16.6 g (yield 100%) of compound 1-4 was obtained in the same manner as in Example 1-2 except that compound 2-1 was changed to 8.9 g of compound 2-4 obtained in Example 4-1. It was.

[Example 5]
Compound 1-5 was synthesized by the following procedure.

(Example 5-1)
10.0 g of compound X5 and 0 of xylene solution (platinum content: 2% by mass) of platinum / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex in a 20 mL airtight PTFE container. .47 g, 4.7 g of HSiCl ₃ and 5.0 g of 1,3-bis (trifluoromethyl) benzene were added, and the mixture was stirred at 40 ° C. for 8 hours. After completion of the reaction, the solvent and the like in the mixture were distilled off under reduced pressure to obtain 13.9 g (yield 100%) of compound X6.

(Example 5-2)
10.0 g of the compound X6 obtained in Example 5-1 and 130 g of tetrahydrofuran were placed in a 500 mL eggplant flask and cooled to 0 ° C. 120 mL of 0.7 mol / L allylmagnesium bromide was added dropwise to the eggplant flask, and the mixture was further stirred for 2 hours. The mixture in the eggplant flask was returned to 25 ° C. and stirred for another 8 hours, and 100 mL of a 1 mol / L hydrochloric acid aqueous solution was added to the mixture to stop the reaction. 100 g of AC-6000 was placed in the mixture to extract the lower layer, which was purified by silica gel column chromatography (developing solvent: AC-6000) to obtain 9.5 g (yield 92%) of compound 2-5.

(Example 5-3)
16.6 g (yield 100%) of compound 1-5 was obtained in the same manner as in Example 1-2 except that compound 2-1 was changed to 8.9 g of compound 2-5 obtained in Example 5-2. It was.

[Example 6]
Compound 1-6 was synthesized by the following procedure.

(Example 6-1)
10.0 g of compound X1-2 and 4.6 g of compound X2 were placed in a 50 mL eggplant flask and stirred for 12 hours. From NMR, it was confirmed that all of Compound X1-2 was converted to Compound 2-6. In addition, methanol, which is a by-product, was produced. The obtained solution was diluted with 14.6 g of AC-2000 and purified by silica gel column chromatography (developing solvent: AC-2000) to obtain 13.0 g (yield 95%) of compound 2-6.

(Example 6-2)
18.2 g (yield 100%) of compound 1-6 was obtained in the same manner as in Example 1-2 except that compound 2-1 was changed to 10.4 g of compound 2-6 obtained in Example 6-1. It was.

[Example 7]
Compound 1-7 was synthesized by the following procedure. The reaction formula is also shown in Example 8 described later.

(Example 7-1)
250 g of tetrahydrofuran was placed in a 1 L eggplant flask and cooled to 0 ° C. 300 mL of 0.7 mol / L allylmagnesium bromide was added dropwise to the eggplant flask, 25.0 g of compound X1-2 was added dropwise, and the mixture in the eggplant flask was further stirred for 2 hours. 500 mL of a 1 mol / L hydrochloric acid aqueous solution was added to the mixture to stop the reaction, and the lower layer was purified by silica gel column chromatography (developing solvent: AC-6000)) to obtain 21.5 g (yield 75%) of compound 2-7. Got

(Example 7-2)
16.5 g (yield 100%) of compound 1-7 was obtained in the same manner as in Example 1-2 except that compound 2-1 was changed to 8.7 g of compound 2-7 obtained in Example 7-1. It was.

[Example 8]
Compound 1-8 was synthesized by the following procedure. The reaction formula is shown in accordance with Example 7 above.

(Example 8-1)
In a 50 mL eggplant flask, 10.0 g of the compound 2-7 obtained in Example 7-1, 4.4 g of allyl bromide, 0.09 g of tetrabutylammonium iodide and 2.0 g of potassium hydroxide were placed. The mixture was stirred at 80 ° C. for 5 hours. The mixture in the eggplant flask was cooled to 25 ° C., 10 g of AE-3000 was added, and the mixture was washed twice. The obtained crude liquid was purified by silica gel column chromatography (developing solvent: AC-6000) to obtain 9.1 g (yield 91%) of compound 2-8.

(Example 8-2)
17.3 g (yield 100%) of compound 1-8 was obtained in the same manner as in Example 1-2 except that compound 2-1 was changed to 9.6 g of compound 2-8 obtained in Example 8-1. It was.

[Example 9]
As compound X7, compound A2 described in Examples of International Publication No. 2011/016458 was used.
Compound X7: C ₆ F ₁₃ C ₂ H ₄ Si (OCH ₃ ) ₃

[Preparation of evaluation sample]
Using the compounds obtained in each example, the surface treatment of the base material was performed by the following wet coating method to obtain an evaluation sample in which a surface layer was formed on the base material.
The above-mentioned evaluation test was carried out using the obtained evaluation sample, and the results are shown in Table 3.
Base material A: A clean soda lime glass substrate whose surface is polished and washed with cerium oxide and dried (water contact angle 5 degrees, size 300 mm x 300 mm, thickness 3 mm).
Base material B: The following composition for forming a base layer was applied to the surface of the base material A by a squeegee coating method and naturally dried, and used as the base material B. The surface treatment of the base material B was performed on the surface on which the base layer was formed.
Composition for forming an underlayer: In a glass container in which a stirrer and a thermometer are set, 5 parts by mass of SI-400 (tetraisocyanate silane (Si (NCO) ₄ ), manufactured by Matsumoto Fine Chemical Co., Ltd.), butyl acetate (Junsei Chemical Co., Ltd.) 95 parts by mass of (manufactured by the same company) was added and mixed, and the mixture was obtained by stirring at 25 ° C. for 3 minutes.

[Examples 10 to 19]
1.4 g of the compound obtained in each example, 38.2 g of isopropyl alcohol, and 0.39 g of an aqueous nitric acid solution (concentration: 1% by mass) were mixed and stirred at 25 ° C. for 3 hours to obtain a mixed solution. It was. 40 g of AC-6000 was added to the mixed solution to obtain a composition for wet coating having a compound concentration of 1.75% by mass.
2 g of each of the above compositions was applied onto a substrate by a squeegee coat method and held at 25 ° C. and 60% RH for 1 hour to form a surface layer. Next, the surface layer was wiped with Kimwipe L-100 (product name, manufactured by Nippon Paper Crecia) containing 2 g of isopropyl alcohol to obtain an evaluation sample (article). As the base material, base material A was used in Examples 10 and 12 to 19, and base material B was used in Example 11.

As shown in Table 3, it was confirmed that the surface layer obtained by using Compound 1 was excellent in weather resistance and corrosion resistance (Examples 10 to 18).

The fluorine-containing compound of the present invention can be used in various applications for which water and oil repellency is required. For example, coats for display input devices such as touch panels, surface protective coats for transparent glass or transparent plastic members, antifouling coats for kitchens, water-repellent and moisture-proof coats for electronic devices, heat exchangers, batteries, etc. It can be used as an antifouling coat for toiletries, a coat for members that require liquid repellency while conducting, a water-repellent / waterproof / water-sliding coat for heat exchangers, a vibration sieve, a surface low friction coat for the inside of a cylinder, and the like. More specific examples of use include a display front protective plate, an antireflection plate, a polarizing plate, an antiglare plate, or a surface of which an antireflection film treatment is applied, and a touch panel of a device such as a mobile phone or a mobile information terminal. Coats of various devices that have display input devices such as sheets and touch panel displays that operate on the screen with human fingers or palms, coats of decorative building materials around water such as toilets, baths, washrooms, kitchens, waterproofing for wiring boards Coating, water-repellent / waterproof / sliding coat for heat exchangers, water-repellent coat for solar cells, waterproof / water-repellent coat for printed wiring boards, waterproof / water-repellent coat for electronic device housings and electronic parts, insulation of power transmission lines Performance improvement coat, waterproof / water repellent coat for various filters, waterproof coat for radio wave absorbers and sound absorbing materials, antifouling coat for baths, kitchen equipment, toiletries, surface low friction coat for vibration sieves and cylinder interiors, mechanical parts, etc. Examples include vacuum equipment parts, bearing parts, parts for transportation equipment such as automobiles (for example, exteriors, glass, mirrors, bumpers), surface protective coatings for tools and the like.
The entire contents of the specification, claims and abstract of Japanese Patent Application No. 2017-170240 filed on September 05, 2017 are cited here and incorporated as disclosure of the specification of the present invention. Is.

Claims (11)

A fluorine-containing compound represented by the formula 1.
R ^1- (OX) _m- Y-Z (R ² ) _q (R ³ ) _r-q Equation 1
However, in the formula,
R ¹ is a perfluoroalkyl group.
X is an alkylene group having 2 or more carbon atoms and having one or more fluorine atoms.
m is an integer from 0 to 6.
Y is a single bond, -O-, -C (O) N (R ⁴ )-, -C (O)-, or -O-, -C (O) N (R ⁴ )-or -C ( O)-is an alkylene group which may have −. The -O -, - C (O) N (R 4) - or -C (O) - alkylene group which may have a may have a fluorine atom. However, the Y is -OCF ₂ - when is an alkylene group containing, -OCF ₂ in the alkylene group - number of is one.
R ⁴ is a hydrogen atom or an alkyl group.
Z is a carbon atom, a silicon atom or a nitrogen atom.
R ² is a hydrogen atom, a hydroxyl group or an alkyl group.
R ³ is −L ¹ −Si (R) _n L _3-n . R is a monovalent hydrocarbon group. L is a hydrolyzable group or a hydroxyl group. n is an integer from 0 to 2. L ¹ is an alkylene group which may have —O−.
When Z is a carbon atom or a silicon atom, r is 3 and q is an integer of 0-2. When Z is a nitrogen atom, r is 2 and q is an integer of 0 to 1. The fluorine-containing compound according to claim 1, wherein R ¹ is a perfluoroalkyl group having 1 to 6 carbon atoms. The fluorine-containing compound according to claim 1 or 2, wherein X is a fluoroalkylene group having 2 or 3 carbon atoms, which has one hydrogen atom or no hydrogen atom. The fluorine-containing compound according to any one of claims 1 to 3, wherein m is 0 or 1. The fluorine-containing compound according to any one of claims 1 to 4, wherein Z is a carbon atom or a silicon atom, and q is 0 or 1. The fluorine-containing compound according to any one of claims 1 to 5, which is used for forming a surface layer of a base material constituting a transportation device. A composition comprising the fluorine-containing compound according to any one of claims 1 to 6 and a liquid medium. It is characterized by having a base material and a surface layer formed on the base material from the fluorine-containing compound according to any one of claims 1 to 6 or the composition according to claim 7. Goods to do. A surface treatment agent containing the fluorine-containing compound according to any one of claims 1 to 6. A fluorine-containing compound represented by the formula 2.
R ^1- (OX) _m- Y-Z (R ² ) _q (L ² -CH = CH ₂ ) _r-q Equation 2
However, in the formula,
R ¹ is a perfluoroalkyl group.
X is an alkylene group having 2 or more carbon atoms and having one or more fluorine atoms.
m is an integer from 0 to 6.
Y is a single bond, -O-, -C (O) N (R ⁴ )-, -C (O)-, or -O-, -C (O) N (R ⁴ )-or -C ( O)-is an alkylene group which may have −. The -O -, - C (O) N (R 4) - or -C (O) - alkylene group which may have a may have a fluorine atom. However, the Y is -OCF ₂ - when is an alkylene group containing, -OCF ₂ in the alkylene group - number of is one.
R ⁴ is a hydrogen atom or an alkyl group.
Z is a carbon atom, a silicon atom or a nitrogen atom.
R ² is a hydrogen atom, a hydroxyl group or an alkyl group.
L ² is an alkylene group, a single bond or -O- which may have -O-.
When Z is a carbon atom or a silicon atom, r is 3 and q is an integer of 0-2. When Z is a nitrogen atom, r is 2 and q is an integer of 0 to 1. A method for producing a fluorine-containing compound represented by the formula 1, wherein the fluorine-containing compound represented by the formula 2 is hydrosilylated with HSi (R) _n L _3-n .
R ^1- (OX) _m- Y-Z (R ² ) _q (R ³ ) _r-q Equation 1
R ^1- (OX) _m- Y-Z (R ² ) _q (L ² -CH = CH ₂ ) _r-q Equation 2
However, in the formula,
R ¹ is a perfluoroalkyl group.
X is an alkylene group having 2 or more carbon atoms and having one or more fluorine atoms.
m is an integer from 0 to 6.
Y is a single bond, -O-, -C (O) N (R ⁴ )-, -C (O)-, or -O-, -C (O) N (R ⁴ )-or -C ( O)-is an alkylene group which may have −. The -O -, - C (O) N (R 4) - or -C (O) - alkylene group which may have a may have a fluorine atom. However, the Y is -OCF ₂ - when is an alkylene group containing, -OCF ₂ in the alkylene group - number of is one.
R ⁴ is a hydrogen atom or an alkyl group.
Z is a carbon atom, a silicon atom or a nitrogen atom.
R ² is a hydrogen atom, a hydroxyl group or an alkyl group.
R ³ is −L ¹ −Si (R) _n L _3-n . R is a monovalent hydrocarbon group. L is a hydrolyzable group or a hydroxyl group. n is an integer from 0 to 2. L ¹ is an alkylene group which may have —O−.
L ² is an alkylene group, a single bond or -O- which may have -O-.
When Z is a carbon atom or a silicon atom, r is 3 and q is an integer of 0-2. When Z is a nitrogen atom, r is 2 and q is an integer of 0 to 1.