JP2017145199A - Fluorine-containing siloxane compound, method for producing the same, coating agent comprising the same, and surface treatment method for glass base material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a fluorine-containing siloxane compound that can impart water repellent and antifouling properties to the surface of a base material, and allows distillation purification and can be produced conveniently, and provide a coating agent comprising the same.SOLUTION: The present invention provides a fluorine-containing siloxane compound produced by making a dihydroxy siloxane compound react with a fluoroalkyl-substituted silane compound, then a silane compound having a reactive group, and a coating agent comprising the fluorine-containing siloxane compound and a liquid medium.SELECTED DRAWING: None

Description

  The present invention relates to a fluorine-containing siloxane compound that can be suitably used for surface treatment for imparting water / oil repellency to a substrate surface, a method for producing the same, a coating agent containing the compound, and a surface treatment method for a glass substrate.

  A compound having a fluoroalkyl moiety in the molecule exhibits high lubricity and water / oil repellency, and is therefore suitably used as a surface treatment agent. When water and oil repellency is imparted to the surface of the base material, it is easy to wipe off the dirt, and the dirt removal property is improved. For such purposes, a reactive silane compound having a fluoroalkyl group or a fluorinated ether compound having a perfluoropolyether as a main chain and a reactive silyl group at the terminal is used as an antifouling agent, lubricant, repellent. It can be used as a surface treatment agent such as a water / oil repellent (Patent Documents 1 to 3). A compound having a reactive silyl group is likely to have good durability because the reactive silyl group is strongly chemically bonded to the surface of the substrate.

JP 2000-234071 A Japanese Patent Application Laid-Open No. 11-092177 JP 2003-238777 A

  However, a surface treatment layer using functional silanes having only a fluoroalkyl main chain as a substituent has a tendency to be inferior in sliding properties for applications such as touch panels. In addition, fluorine-containing ether compounds having a perfluoropolyether chain as the main chain and having a reactive silyl group at the end are high molecular weight compounds having a molecular weight distribution, although the slip characteristics are improved. However, there is a problem that high-temperature and high-vacuum is required for vapor deposition, and that it is soluble only in an expensive fluorous solvent such as perfluorohexane.

  The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a fluorine-containing siloxane compound that can impart good water and oil repellency to a substrate surface and can be purified by distillation and can be easily produced. Another object of the present invention is to provide a coating agent containing the fluorine-containing siloxane compound and a medium, and a surface treatment method for a glass substrate using the coating agent.

As a result of intensive studies to achieve the above object, the present inventors have reacted a dihydroxysiloxane compound having hydroxyl groups at both ends with a fluoroalkyl-substituted silane compound and then a silane compound having a reactive group. The inventors have found that a fluorine-containing siloxane compound having desired characteristics can be produced, and have completed the present invention.
That is, this invention relates to the fluorine-containing siloxane compound which has the structure of following [1]-[8], its manufacturing method, the coating agent containing it, and the surface treatment method of a glass base material.
[1]
General formula (1)

(In the formula, R ¹ represents a fluoroalkyl group having 1 to 8 carbon atoms. R ² , R ³ , R ⁴ and R ⁵ each independently represents 1 to 8 carbon atoms which may be substituted with a fluorine atom. N represents 2 or 3. Z represents a hydrogen atom, or General Formula (2)

(In the formula, R ⁶ , R ⁷ and R ⁸ each independently represents an alkyl group having 1 to 2 carbon atoms, a halogen atom or an alkoxy group having 1 to 3 carbon atoms, and R ⁶ , R ⁷ or R ⁸ At least one is a halogen atom or an alkoxy group having 1 to 3 carbon atoms). The fluorine-containing siloxane compound represented by this.
[2]
General formula (3)

(In the formula, R ¹ represents a fluoroalkyl group having 1 to 8 carbon atoms. R ² , R ³ , R ⁴ and R ⁵ each independently represents 1 to 8 carbon atoms which may be substituted with a fluorine atom. R ⁶ , R ⁷ and R ⁸ each independently represents an alkyl group having 1 to 2 carbon atoms, a halogen atom or an alkoxy group having 1 to 3 carbon atoms, and R ⁶ , R ⁷ or R ^8. The fluorine-containing siloxane compound according to item 1, wherein at least one of ⁸ is a halogen atom or an alkoxy group having 1 to 3 carbon atoms, n represents 2 or 3.
[3]
General formula (4)

(In the formula, R ¹ represents a fluoroalkyl group having 1 to 8 carbon atoms. R ² , R ³ , R ⁴ and R ⁵ each independently represents 1 to 8 carbon atoms which may be substituted with a fluorine atom. The fluorine-containing siloxane compound according to Item 1, wherein n represents 2 or 3.
[4]
General formula (5)

(Wherein R ⁴ and R ⁵ each independently represents an alkyl group having 1 to 8 carbon atoms which may be substituted with a fluorine atom. N represents 2 or 3). Compound and the following general formula (6)

(In the formula, R ¹ represents a fluoroalkyl group having 1 to 8 carbon atoms. R ² and R ³ each independently represents an alkyl group having 1 to 8 carbon atoms which may be substituted with a fluorine atom. X represents a halogen atom or an alkoxy group having 1 to 3 carbon atoms.), And is reacted with a fluoroalkyl-substituted silane compound represented by the general formula (4)

(In the formula, R ¹ represents a fluoroalkyl group having 1 to 8 carbon atoms. R ² , R ³ , R ⁴ and R ⁵ each independently represents 1 to 8 carbon atoms which may be substituted with a fluorine atom. Wherein n represents 2 or 3.) A method for producing a fluorine-containing siloxane compound represented by:
[5]
General formula (4)

(In the formula, R ¹ represents a fluoroalkyl group having 1 to 8 carbon atoms. R ² , R ³ , R ⁴ and R ⁵ each independently represents 1 to 8 carbon atoms which may be substituted with a fluorine atom. And n represents 2 or 3.) and a fluorine-containing siloxane compound represented by the general formula (7):

(In the formula, R ⁶ , R ⁷ and R ⁸ each independently represents an alkyl group having 1 to 2 carbon atoms, a halogen atom or an alkoxy group having 1 to 3 carbon atoms, and R ⁶ , R ⁷ or R ⁸ At least one is a halogen atom or an alkoxy group having 1 to 3 carbon atoms, and X represents a halogen atom or an alkoxy group having 1 to 3 carbon atoms). And general formula (3)

(In the formula, R ¹ represents a fluoroalkyl group having 1 to 8 carbon atoms. R ² , R ³ , R ⁴ and R ⁵ each independently represents 1 to 8 carbon atoms which may be substituted with a fluorine atom. R ⁶ , R ⁷ and R ⁸ each independently represents an alkyl group having 1 to 2 carbon atoms, a halogen atom or an alkoxy group having 1 to 3 carbon atoms, and R ⁶ , R ⁷ or R ^And at least one of ⁸ is a halogen atom or an alkoxy group having 1 to 3 carbon atoms, n is 2 or 3.).
[6]
Item 4. A coating agent comprising the fluorine-containing siloxane compound according to item 1, 2 or 3, and a liquid medium.
[7]
The surface treatment method of the glass base material which removes a liquid medium after apply | coating the coating agent of the item 6 to the surface of a base material.

  According to the method of the present invention, a low molecular weight fluorine-containing siloxane compound having a high fluorine content per unit mass, having one or more fluoroalkyl groups in the molecule, and having a reactive group capable of binding to a substrate is provided. can do. This is a compound having a single composition with no molecular weight distribution, can be purified by distillation, and is easily soluble in general-purpose organic solvents.

  The fluorine-containing siloxane compound of the present invention can give good water and oil repellency to the substrate surface by dissolving in a solvent to prepare a coating agent and coating it.

  Hereinafter, the present invention will be described in detail.

First, definitions of R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and X in the general formulas (1) to (8) will be described. In the formula, the fluoroalkyl group having 1 to 8 carbon atoms represented by R ¹ may be linear, branched or cyclic. Specifically, fluoromethyl group, difluoromethyl group, trifluoromethyl group, 2-fluoroethyl group, 1,1,2,2,2-pentafluoroethyl group, 2,2,2-trifluoroethyl group, 1 , 1,2,2-tetrafluoroethyl group, 1,1,2,2,3,3,3-heptafluoropropyl group, 3,3,3-trifluoropropyl group, 2,2,2-trifluoro -1- (trifluoromethyl) ethyl group, 1,2,2,2-tetrafluoro-1- (trifluoromethyl) ethyl group, 3,3,4,4,4-pentafluorobutyl group, 2,2 , 3,3,4,4,4-heptafluorobutyl group, 3,3,3-trifluoro- (2-trifluoromethyl) propyl group, 3,3,3-trifluoro- (1-trifluoromethyl) ) Propyl group, 2,2,2- Lifluoro-1,1-bis (trifluoromethyl) ethyl group, 3,3,4,4,5,5,5-heptafluoropentyl group, 2,2,3,3,4,4,5,5 5-nonafluoropentyl group, 3,3,4,4,5,5,6,6,6-nonafluorohexyl group, 2,2,3,3,4,4,5,5,6,6 6-undecafluorohexyl group, 3,3,4,4,5,5,6,6,7,7,7-undecafluoroheptyl group, 2,2,3,3,4,4,5, 5,6,6,7,7,7-tridecafluoroheptyl group, 2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-pentadeca Examples thereof include a fluorooctyl group, 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl group and the like. R ¹ is 3,3,3-trifluoropropyl group, 3,3,4,4,4-pentafluorobutyl group, 3,3,4,4,5 in terms of stability and water repellency of the compound. , 5,6,6,6-nonafluorohexyl group or 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl group, 3,4,4,5,5,6,6,6-nonafluorohexyl group or 3,3,4,4,5,5,6,6,7,7,8,8,8-trideca A fluorooctyl group is more preferred, and a 3,3,4,4,5,5,6,6,6-nonafluorohexyl group is particularly preferred.

In the formula, the alkyl group having 1 to 8 carbon atoms represented by R ² , R ³ , R ⁴ and R ⁵ may be linear, branched or cyclic, specifically a methyl group. , Ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, cyclobutyl group, n-pentyl group, 1-methylbutyl group, 2-methylbutyl group, isopentyl group , Neopentyl group, cyclopentyl group, n-hexyl group, 1-methylpentyl group, 2,3-dimethylbutyl group, cyclohexyl group, cyclopentylmethyl group, n-heptyl group, 2-norbornyl group, n-octyl group, etc. It can be illustrated. Further, in these, some or all of hydrogen atoms may be substituted with fluorine atoms. Specifically, fluoromethyl group, difluoromethyl group, trifluoromethyl group, 2-fluoroethyl group, 1,1,2,2,2-pentafluoroethyl group, 2,2,2-trifluoroethyl group, 1 , 1,2,2-tetrafluoroethyl group, 1,1,2,2,3,3,3-heptafluoropropyl group, 3,3,3-trifluoropropyl group, 2,2,2-trifluoro -1- (trifluoromethyl) ethyl group, 1,2,2,2-tetrafluoro-1- (trifluoromethyl) ethyl group, 3,3,4,4,4-pentafluorobutyl group, 2,2 , 3,3,4,4,4-heptafluorobutyl group, 3,3,3-trifluoro- (2-trifluoromethyl) propyl group, 3,3,3-trifluoro- (1-trifluoromethyl) ) Propyl group, 2,2,2- Lifluoro-1,1-bis (trifluoromethyl) ethyl group, 3,3,4,4,5,5,5-heptafluoropentyl group, 2,2,3,3,4,4,5,5 5-nonafluoropentyl group, 3,3,4,4,5,5,6,6,6-nonafluorohexyl group, 2,2,3,3,4,4,5,5,6,6 6-undecafluorohexyl group, 3,3,4,4,5,5,6,6,7,7,7-undecafluoroheptyl group, 2,2,3,3,4,4,5, 5,6,6,7,7,7-tridecafluoroheptyl group, 2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-pentadeca Examples thereof include a fluorooctyl group and 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl group. R ² , R ³ , R ⁴ and R ⁵ are each a methyl group, an ethyl group, an n-propyl group, a 3,3,3-trifluoropropyl group, 3, 3 in terms of stability and water repellency of the compound. , 4,4,4-pentafluorobutyl group, 3,3,4,4,5,5,6,6,6-nonafluorohexyl group, or 3,3,4,4,5,5,6, A 6,7,7,8,8,8-tridecafluorooctyl group is preferred, a methyl group or a 3,3,3-trifluoropropyl group is more preferred, and a methyl group is particularly preferred.

In the formula, an alkyl group having 1 to 2 carbon atoms, a halogen atom or an alkoxy group having 1 to 3 carbon atoms represented by R ⁶ , R ⁷ and R ⁸ includes a methyl group, an ethyl group, a fluorine atom, a chlorine atom, A bromine atom, an iodine atom, a methoxy group, an ethoxy group, a (n-propyl) oxy group, a (1-methylethyl) oxy group and the like can be exemplified. In terms of yield, stability and water repellency, R ⁶ , R ⁷ and R ⁸ are preferably a methyl group, an ethyl group, a chlorine atom, a bromine atom, a methoxy group, an ethoxy group, a methyl group, a chlorine atom, or A methoxy group is more preferred, and a methoxy group is particularly preferred.

  In the formula, the halogen atom represented by X or the alkoxy group having 1 to 3 carbon atoms includes a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a methoxy group, an ethoxy group, an (n-propyl) oxy group, (1 -Methylethyl) oxy group etc. can be illustrated. From the viewpoint of yield, stability and water repellency, X is preferably a chlorine atom, bromine atom, methoxy group or ethoxy group, more preferably a chlorine atom or methoxy group, and particularly preferably a chlorine atom.

  Examples of the fluorine-containing siloxane compound (compound 4) that can be produced according to the present invention include 1-hydroxy-7- (trifluoromethyl) -1,1,3,3,5,5,7,7-octamethyltetrasiloxane, 1-hydroxy-7- (difluoromethyl) -1,1,3,3,5,5,7,7-octamethyltetrasiloxane, 1-hydroxy-7- (fluoromethyl) -1,1,3,3 , 5,5,7,7-octamethyltetrasiloxane, 1-hydroxy-7- (3,3,3-trifluoropropyl) -1,1,3,3,5,5,7,7-octamethyl Tetrasiloxane, 1-hydroxy-7- (2,2,2-trifluoroethyl) -1,1,3,3,5,5,7,7-octamethyltetrasiloxane, 1-hydroxy-7- (1 , 1,2,2,2-penta (Luoroethyl) -1,1,3,3,5,5,7,7-octamethyltetrasiloxane, 1-hydroxy-7- (3,3,3-trifluoropropyl) -1,1,3,3 5,5,7,7-octamethyltetrasiloxane, 1-hydroxy-7- (2,2,3,3,3-pentafluoropropyl) -1,1,3,3,5,5,7,7 -Octamethyltetrasiloxane, 1-hydroxy-7- (3,3,4,4,4-pentafluorobutyl) -1,1,3,3,5,5,7,7-octamethyltetrasiloxane, -Hydroxy-7- (3,3,4,4,5,5,5-heptafluoropentyl) -1,1,3,3,5,5,7,7-octamethyltetrasiloxane, 1-hydroxy- 7- (3,3,4,4,5,5,6,6,6-nonafluoro Xyl) -1,1,3,3,5,5,7,7-octamethyltetrasiloxane, 1-hydroxy-7- (3,3,4,4,5,5,6,6,7,7) , 7-Undecafluoroheptyl) -1,1,3,3,5,5,7,7-octamethyltetrasiloxane, 1-hydroxy-7- (3,3,4,4,5,5,5) 6,6,7,7,8,8,8-tridecafluorooctyl) -1,1,3,3,5,5,7,7-octamethyltetrasiloxane, 1-hydroxy-7- (trifluoro Methyl) -1,3,5-tris (3,3,3-trifluoropropyl) -1,3,5,7,7-pentamethyltetrasiloxane, 1-hydroxy-7- (3,3,3- Trifluoropropyl) -1,3,5-tris (3,3,3-trifluoropropyl) -1,3,5 , 7,7-pentamethyltetrasiloxane, 1-hydroxy-7- (2,2,2-trifluoroethyl) -1,3,5-tris (3,3,3-trifluoropropyl) -1,3 , 5,7,7-pentamethyltetrasiloxane, 1-hydroxy-1,3,5,7-tetrakis (3,3,3-trifluoropropyl) -1,3,5,7,7-pentamethyltetra Siloxane, 1-hydroxy-7- (3,3,4,4,4-pentafluorobutyl) -1,3,5-tris (3,3,3-trifluoropropyl) -1,3,5,7 , 7-pentamethyltetrasiloxane, 1-hydroxy-7- (3,3,4,4,5,5,5-heptafluoropentyl) -1,3,5-tris (3,3,3-trifluoro Propyl) -1,3,5,7,7-pentamethy Tetrasiloxane, 1-hydroxy-7- (3,3,4,4,5,5,6,6,6-nonafluorohexyl) -1,3,5-tris (3,3,3-trifluoropropyl) ) -1,3,5,7,7-pentamethyltetrasiloxane, 1-hydroxy-7- (3,3,4,4,5,5,6,6,7,7,7-undecafluoro Butyl) -1,3,5-tris (3,3,3-trifluoropropyl) -1,3,5,7,7-pentamethyltetrasiloxane, 1-hydroxy-7- (3,3,4, 4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl) -1,3,5-tris (3,3,3-trifluoropropyl) -1,3,5 , 7,7-pentamethyltetrasiloxane and the like. 1-hydroxy-7- (3,3,3-trifluoropropyl) -1,1,3,3,5,5,7,7-octamethyltetra in terms of yield, stability and water repellency Siloxane, 1-hydroxy-7- (3,3,4,4,4-pentafluorobutyl) -1,1,3,3,5,5,7,7-octamethyltetrasiloxane, 1-hydroxy-7 -(3,3,4,4,5,5,6,6,6-nonafluorohexyl) -1,3,5-tris (3,3,3-trifluoropropyl) -1,3,5 7,7-pentamethyltetrasiloxane is preferred, and 1-hydroxy-7- (3,3,4,4,5,5,6,6,6-nonafluorohexyl) -1,3,5-tris (3 , 3,3-trifluoropropyl) -1,3,5,7,7-pentamethyltetrasiloxane A further preferred.

  Examples of the fluorine-containing siloxane compound (compound 3) that can be produced by the present invention include 1,1,1-trichloro-9- (trifluoromethyl) -3,3,5,5,7,7,9,9-octa. Methylpentasiloxane, 1,1,1-trichloro-9- (difluoromethyl) -3,3,5,5,7,7,9,9-octamethylpentasiloxane, 1,1,1-trichloro-9- (Fluoromethyl) -3,3,5,5,7,7,9,9-octamethylpentasiloxane, 1,1,1-trichloro-9- (3,3,3-trifluoropropyl) -3, 3,5,5,7,7,9,9-octamethylpentasiloxane, 1,1,1-trichloro-9- (2,2,2-trifluoroethyl) -3,3,5,5,7 , 7,9,9-octamethylpentasiloxane, 1,1, -Trichloro-9- (1,1,2,2,2-pentafluoroethyl) -3,3,5,5,7,7,9,9-octamethylpentasiloxane, 1,1,1-trichloro- 9- (2,2,3,3,3-pentafluoropropyl) -3,3,5,5,7,7,9,9-octamethylpentasiloxane, 1,1,1-trichloro-9- ( 3,3,4,4,4-pentafluorobutyl) -3,3,5,5,7,7,9,9-octamethylpentasiloxane, 1,1,1-trichloro-9- (3,3 , 4,4,5,5,5-heptafluoropentyl) -3,3,5,5,7,7,9,9-octamethylpentasiloxane, 1,1,1-trichloro-9- (3 3,4,4,5,5,6,6,6-nonafluorohexyl) -3,3,5,5,7,7,9, -Octamethylpentasiloxane, 1,1,1-trichloro-9- (3,3,4,4,5,5,6,6,7,7,7-undecafluoroheptyl) -3,3 5,5,7,7,9,9-octamethylpentasiloxane, 1,1,1-trichloro-9- (3,3,4,4,5,5,6,6,7,7,8, 8,8-tridecafluorooctyl) -3,3,5,5,7,7,9,9-octamethylpentasiloxane, 1,1,1-trichloro-9- (trifluoromethyl) -3,5 , 7-Tris (3,3,3-trifluoropropyl) -3,5,7,9,9-pentamethylpentasiloxane, 1,1,1-trichloro-9- (3,3,3-trifluoro Propyl) -3,5,7-tris (3,3,3-trifluoropropyl) -3,5,7,9,9 -Pentamethylpentasiloxane, 1,1,1-trichloro-9- (2,2,2-trifluoroethyl) -3,5,7-tris (3,3,3-trifluoropropyl) -3,5 , 7,9,9-pentamethylpentasiloxane, 1,1,1-trichloro-3,5,7,9-tetrakis (3,3,3-trifluoropropyl) -3,5,7,9,9 -Pentamethylpentasiloxane, 1,1,1-trichloro-9- (3,3,4,4,4-pentafluorobutyl) -3,5,7-tris (3,3,3-trifluoropropyl) -3,5,7,9,9-pentamethylpentasiloxane, 1,1,1-trichloro-9- (3,3,4,4,5,5,5-heptafluoropentyl) -3,5 7-Tris (3,3,3-trifluoropropyl) -3,5 7,9,9-pentamethylpentasiloxane, 1,1,1-trichloro-9- (3,3,4,4,5,5,6,6,6-nonafluorohexyl) -3,5,7 -Tris (3,3,3-trifluoropropyl) -3,5,7,9,9-pentamethylpentasiloxane, 1,1,1-trichloro-9- (3,3,4,4,5, 5,6,6,7,7,7-undecafluoroheptyl) -3,5,7-tris (3,3,3-trifluoropropyl) -3,5,7,9,9-pentamethyl Pentasiloxane, 1,1,1-trichloro-9- (3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl) -3,5, 7-tris (3,3,3-trifluoropropyl) -3,5,7,9,9-pentamethylpentasiloxane, 1 1,1-trichloro-9- (trifluoromethyl) -3,3,5,5,7,7,9,9-octamethylpentasiloxane, 1,1,1-trichloro-9- (difluoromethyl)- 3,3,5,5,7,7,9,9-octamethylpentasiloxane, 1,1,1-trichloro-9- (fluoromethyl) -3,3,5,5,7,7,9, 9-octamethylpentasiloxane, 1,1,1-trichloro-9- (3,3,3-trifluoropropyl) -3,3,5,5,7,7,9,9-octamethylpentasiloxane, 1,1,1-trichloro-9- (2,2,2-trifluoroethyl) -3,3,5,5,7,7,9,9-octamethylpentasiloxane, 1,1,1-trichloro -9- (1,1,2,2,2-pentafluoroethyl) -3,3 , 5,5,7,7,9,9-octamethylpentasiloxane, 1,1,1-trichloro-9- (2,2,3,3,3-pentafluoropropyl) -3,3,5, 5,7,7,9,9-octamethylpentasiloxane, 1,1,1-trichloro-9- (3,3,4,4,4-pentafluorobutyl) -3,3,5,5,7 , 7,9,9-octamethylpentasiloxane, 1,1,1-trichloro-9- (3,3,4,4,5,5,5-heptafluoropentyl) -3,3,5,5 7,7,9,9-octamethylpentasiloxane, 1,1,1-trichloro-9- (3,3,4,4,5,5,6,6,6-nonafluorohexyl) -3,3 , 5,5,7,7,9,9-octamethylpentasiloxane, 1,1,1-trichloro-9- (3,3, , 4,5,5,6,6,7,7,7-undecafluoroheptyl) -3,3,5,5,7,7,9,9-octamethylpentasiloxane, 1,1,1 -Trichloro-9- (3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl) -3,3,5,5,7,7, 9,9-octamethylpentasiloxane, 1,1,1-trimethoxy-9- (trifluoromethyl) -3,5,7-tris (3,3,3-trifluoropropyl) -3,5,7, 9,9-pentamethylpentasiloxane, 1,1,1-trimethoxy-9- (3,3,3-trifluoropropyl) -3,5,7-tris (3,3,3-trifluoropropyl)- 3,5,7,9,9-pentamethylpentasiloxane, 1,1,1-trimethoxy-9- (2 2,2-trifluoroethyl) -3,5,7-tris (3,3,3-trifluoropropyl) -3,5,7,9,9-pentamethylpentasiloxane, 1,1,1-trimethoxy -3,5,7,9-tetrakis (3,3,3-trifluoropropyl) -3,5,7,9,9-pentamethylpentasiloxane, 1,1,1-trimethoxy-9- (3 3,4,4,4-pentafluorobutyl) -3,5,7-tris (3,3,3-trifluoropropyl) -3,5,7,9,9-pentamethylpentasiloxane, 1,1 , 1-Trimethoxy-9- (3,3,4,4,5,5,5-heptafluoropentyl) -3,5,7-tris (3,3,3-trifluoropropyl) -3,5 7,9,9-pentamethylpentasiloxane, 1,1,1-tri Methoxy-9- (3,3,4,4,5,5,6,6,6-nonafluorohexyl) -3,5,7-tris (3,3,3-trifluoropropyl) -3,5 , 7,9,9-pentamethylpentasiloxane, 1,1,1-trimethoxy-9- (3,3,4,4,5,5,6,6,7,7,7-undecafluoroheptyl ) -3,5,7-tris (3,3,3-trifluoropropyl) -3,5,7,9,9-pentamethylpentasiloxane, 1,1,1-trimethoxy-9- (3,3 , 4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl) -3,5,7-tris (3,3,3-trifluoropropyl) -3, Examples thereof include 5,7,9,9-pentamethylpentasiloxane. 1,1,1-trichloro-9- (3,3,3-trifluoropropyl) -3,3,5,5,7,7,9,9 in terms of yield, stability and water repellency -Octamethylpentasiloxane, 1,1,1-trimethoxy-9- (3,3,3-trifluoropropyl) -3,3,5,5,7,7,9,9-octamethylpentasiloxane, , 1,1-trichloro-9- (3,3,4,4,4-pentafluorobutyl) -3,3,5,5,7,7,9,9-octamethylpentasiloxane, 1,1, 1-trimethoxy-9- (3,3,4,4,4-pentafluorobutyl) -3,3,5,5,7,7,9,9-octamethylpentasiloxane, 1,1,1-trichloro -9- (3,3,4,4,5,5,6,6,6-nonafluorohexyl) -3,5,7- Lis (3,3,3-trifluoropropyl) -3,5,7,9,9-pentamethylpentasiloxane, 1,1,1-trimethoxy-9- (3,3,4,4,5,5 , 6,6,6-nonafluorohexyl) -3,5,7-tris (3,3,3-trifluoropropyl) -3,5,7,9,9-pentamethylpentasiloxane, 1,1-trimethoxy-9- (3,3,4,4,5,5,6,6,6-nonafluorohexyl) -3,5,7-tris (3,3,3-trifluoropropyl) -3,5,7,9,9-pentamethylpentasiloxane is particularly preferred.

  Next, the manufacturing method of this invention is demonstrated. The fluorine-containing siloxane compound represented by the compound (4) can be produced by Step 1 in which a dihydroxysiloxane compound (Compound 5) and a fluoroalkyl-substituted silane compound (Compound 6) are reacted. The fluorine-containing siloxane compound represented by the compound (3) can be produced by the step 2 in which the fluorine-containing siloxane compound (4) and the silane compound (7) are reacted.

(In the formula, R ¹ represents a fluoroalkyl group having 1 to 8 carbon atoms. R ² , R ³ , R ⁴ and R ⁵ each independently represents 1 to 8 carbon atoms which may be substituted with a fluorine atom. X represents a halogen atom or an alkoxy group having 1 to 3 carbon atoms, and n represents 2 or 3.)

(In the formula, R ¹ represents a fluoroalkyl group having 1 to 8 carbon atoms. R ² , R ³ , R ⁴ and R ⁵ each independently represents 1 to 8 carbon atoms which may be substituted with a fluorine atom. R ⁶ , R ⁷ and R ⁸ each independently represents an alkyl having 1 to 2 carbon atoms, a halogen atom or an alkoxy group having 1 to 3 carbon atoms, and R ⁶ , R ⁷ or R ^8. At least one is a halogen atom or an alkoxy group having 1 to 3 carbon atoms, X represents a halogen atom or an alkoxy group having 1 to 3 carbon atoms, and n represents 2 or 3.)

(Process 1)
Step 1 will be described. Of the dihydroxysiloxane compound (5) used as the raw material in step 1, the linear fluorine-containing trisiloxane compound in which n is 2 or 3 is a method described in many patents and non-patent documents. It can be easily produced (Japanese Patent Laid-Open No. 2000-113942, Zeitschrift for Anorganische und Allgemeine Chemie, 536, 197, 1986). Further, the fluoroalkyl-substituted silane compound represented by the general formula (6) can be easily produced by those skilled in the art by methods described in many patents and non-patent literature (Inorganica Chimica Acta, Vol. 359). 2674, 2006. Japanese Patent Laid-Open No. 04-059782.).

  In the compound 4, it is essential to have at least one fluoroalkyl group. The synthesis of compound 4 can be produced by adding compound 6 to the organic solvent solution of compound 5 and reacting it. The chemical equivalent of compound 6 with respect to compound 5 is preferably produced in the range of 0.5 to 2 equivalents, and more preferably 0.8 to 1.2 equivalents in terms of high yield. In this production, it is preferable to add an organic base in order to accelerate the reaction. As the organic base, an organic amine can be suitably used. Examples of the organic amine include trimethylamine, diethylamine, triethylamine, propylamine, isopropylamine, diisopropylamine, pyridine, aniline, and quinoline. The chemical equivalent of the organic amine is preferably in the range of 1 to 10 equivalents relative to compound 6, and more preferably 1 to 2 equivalents.

  Step 1 can be carried out in an air or dry air atmosphere, but it is preferably carried out in an inert gas atmosphere in terms of a good yield. Examples of the inert gas that can be used include noble gases such as helium, neon, argon, krypton, and xenon, and nitrogen gas, and argon or nitrogen gas is more preferable. There is no particular limitation on the reaction temperature, and those skilled in the art can use general temperature conditions for producing a siloxane compound having a hydroxyl group. As a specific example, the fluorine-containing siloxane compound of the present invention can be obtained with good yield at a reaction temperature appropriately selected from a temperature range of -80 ° C to 80 ° C. From the viewpoints of yield, safety and operability, an operating temperature selected from the range of −30 to 30 ° C. is preferable, and room temperature is more preferable. The reaction time is appropriately determined by confirming the progress of the reaction by instrumental analysis. Typically, the reaction time is preferably selected from the range of 10 minutes to 200 hours.

  Step 1 is preferably carried out in an organic solvent in terms of good yield. The usable organic solvent is not limited as long as it does not inhibit the reaction. Specifically, it is an aliphatic hydrocarbon such as pentane, hexane, cyclohexane or heptane, or an aromatic hydrocarbon such as benzene, toluene, xylene or ethylbenzene. , Ethers such as diethyl ether, diisopropyl ether, cyclopentyl methyl ether (CPME), tetrahydrofuran (THF), 1,4-dioxane, 1,2-dimethoxyethane, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, dichloromethane, A halogenated hydrocarbon such as chloroform can be exemplified. These organic solvents can be used singly or as a mixture of plural kinds at an arbitrary ratio. In terms of good yield and short reaction time, the organic solvent is preferably an ether, diethyl ether and THF are preferred, and THF is more preferred.

  In Step 1, the desired product can be purified by appropriately selecting and using a general purification method when a person skilled in the art purifies a siloxane compound having a hydroxyl group as necessary after completion of the reaction. Specific examples of the purification method include washing, filtration, concentration, extraction, distillation, sublimation, recrystallization, fractionation by normal phase / reverse phase liquid chromatography, and the like.

(Process 2)
In compound 3, it is essential to have at least one fluoroalkyl group. The fluorine-containing siloxane compound (4) that can be used as a raw material in Step 2 can be produced by Step 1 described above. The chemical equivalent of compound 7 with respect to compound 4 is preferably in the range of 0.5 to 100 equivalents and more preferably 1 to 10 equivalents in terms of good yield. The silane compound (7) can be easily produced by those skilled in the art by methods described in many patents and non-patent documents (Angewandte Chemie International Edition, 50, 10708, 2011).

In step 2, it is preferable to add an organic base in order to accelerate the reaction. An organic amine can be used as the organic base, and examples of the organic amine include trimethylamine, diethylamine, triethylamine, propylamine, isopropylamine, diisopropylamine, pyridine, aniline, and quinoline. The chemical equivalent of the organic amine is preferably in the range of 1 to 10 equivalents relative to compound 7, and more preferably 1 to 2 equivalents.
Step 2 can be carried out in an air or dry air atmosphere, but it is preferably carried out in an inert gas atmosphere in terms of a good yield. Examples of the inert gas that can be used include noble gases such as helium, neon, argon, krypton, and xenon, and nitrogen gas, and argon or nitrogen gas is more preferable. There is no particular limitation on the reaction temperature, and those skilled in the art can use general temperature conditions for producing a siloxane compound having a hydroxyl group. As a specific example, the fluorine-containing siloxane compound of the present invention can be obtained with good yield at a reaction temperature appropriately selected from a temperature range of -80 ° C to 80 ° C. From the viewpoints of yield, safety and operability, an operating temperature selected from the range of −30 to 30 ° C. is preferable, and room temperature is more preferable. The reaction time is appropriately determined by confirming the progress of the reaction by instrumental analysis, but it is preferable to carry out the reaction time appropriately selected from the range of 10 minutes to 200 hours.

  It is preferable to implement the process 2 in an organic solvent at a point with a sufficient yield. The usable organic solvent is not limited as long as it does not inhibit the reaction, specifically, aliphatic hydrocarbons such as pentane, hexane, cyclohexane and heptane, and aromatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene. , Diethyl ether, diisopropyl ether, cyclopentyl methyl ether (CPME), tetrahydrofuran (THF), ethers such as 1,4-dioxane, 1,2-dimethoxyethane, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, dichloromethane, A halogenated hydrocarbon such as chloroform can be exemplified. These organic solvents can be used singly or as a mixture of plural kinds at an arbitrary ratio. In terms of good yield and short reaction time, the organic solvent is preferably an ether, diethyl ether and THF are preferred, and THF is more preferred.

  In Step 2, the desired product can be purified by appropriately selecting and using a general purification method when a siloxane compound having a reactive group is purified by a person skilled in the art as necessary after completion of the reaction. Specific examples of the purification method include washing, filtration, extraction, concentration, distillation, sublimation, recrystallization, fractionation by normal phase / reverse phase liquid chromatography, and the like. Purification by vacuum distillation is more preferable from the viewpoint that the purity can be further improved by removing high molecular weight impurities.

<Coating agent>
The coating agent of the present invention contains a fluorine-containing siloxane compound (1), (2) or (3) and a liquid medium, and can be produced by mixing them. The coating agent of the present invention may be liquid, and may be a solution or a dispersion. The coating agent of this invention should just contain the fluorine-containing siloxane compound (1), (2) or (3), and may also contain impurities, such as a by-product produced | generated at the process 1 or the process 2. It is preferable that the coating agent of this invention contains 0.001-10 mass% of fluorine-containing siloxane compounds (1), (2) or (3) of this invention, and 0.1-1 mass% is still more preferable. The coating agent of the present invention particularly preferably contains the fluorinated siloxane compound (1), (2) or (3) purified to 95% by mass or more through Step 1 and Step 2 and a liquid medium.

<Liquid medium>
The boiling point of the liquid medium in the present invention is preferably −10 to 200 ° C., particularly preferably 40 to 150 ° C. As the liquid medium, an organic solvent is preferable. The organic solvent may be a fluorinated organic solvent or a non-fluorinated organic solvent. Preferred examples of the fluorinated organic solvent include perfluorohexane, perfluorooctane, and perfluorokerosene. Preferred examples of the non-fluorine organic solvent include hydrocarbon organic solvents, alcohol organic solvents, ketone organic solvents, ether organic solvents, ester organic solvents, and haloalkanes. As the hydrocarbon organic solvent, hexane, heptane, cyclohexane and the like are preferable. As the ketone organic solvent, acetone, methyl ethyl ketone, methyl isobutyl ketone and the like are preferable. As the ether organic solvent, diethyl ether, tetrahydrofuran, tetraethylene glycol dimethyl ether and the like are preferable. As the ester organic solvent, ethyl acetate, butyl acetate and the like are preferable. As the haloalkane, dichloromethane, chloroform, carbon tetrachloride and the like are preferable. Chloroform is more preferable in terms of excellent storage stability and high solubility. The coating agent may contain other components in addition to the compound (1), (2) or (3) and the liquid medium as long as the effects of the present invention are not impaired.

By applying the coating agent containing the fluorine-containing siloxane compound of the present invention to the surface of the substrate to form a coating film, and removing the liquid medium from the coating film, the surface treatment of the substrate can be performed. As a method for applying the coating agent, a known method can be appropriately used. As the coating method, a spin coating method, a wipe coating method, a spray coating method, a dip coating method, an ink jet method, a roll coating method, a casting method, a Langmuir-Blodget method or a gravure coating method is preferable, and a spin coating method and a dip coating method are used. Is more preferable.
The method for removing the liquid medium may be any method that can evaporate and remove the liquid medium from the coating film of the coating agent, and known methods can be used as appropriate. The temperature at which the liquid medium is removed by evaporation may be at least the boiling point of the liquid medium, and is appropriately selected depending on the type of the liquid medium. In some cases, the liquid medium can be removed under reduced pressure, so that the liquid medium can be removed by evaporation at a temperature lower than the boiling point of the liquid medium.

  After the surface treatment, the surface treatment layer may be washed as necessary. Specific examples of the cleaning method include a method of pouring a solvent over the surface treatment layer and a method of wiping with a cloth soaked with a solvent.

<Base material>
In the present invention, the substrate to be surface-treated is not particularly limited as long as it is a glass substrate that is required to be imparted with water and oil repellency.

  By treating the surface of the substrate with the fluorine-containing siloxane compound (compound (1)) or the coating agent containing the compound of the present invention to form a surface treatment layer, good water and oil repellency is imparted. The Moreover, since this surface treatment layer is colorless and transparent, it is suitable as a member constituting the touch panel. The touch panel means an input device of an input / display device (touch panel device) that combines a display device and a device that inputs contact position information by contact with a finger or the like. The touch panel is composed of a base material and a transparent conductive film, an electrode, a wiring, an IC, and the like depending on the input detection method. By making the surface having the surface treatment layer of the base material the input surface of the touch panel, a touch panel having good fingerprint removability can be obtained. The material of the base material for touch panels has translucency. As the material for the touch panel substrate, a glass substrate is preferable. As the glass, soda lime glass, borosilicate glass, alkali-free glass, crystal glass, and quartz glass are preferable, and chemically tempered glass is particularly preferable.

  Further, as the substrate in the present invention, a display substrate constituting the outermost surface of various displays such as a liquid crystal display, a CRT display, a projection display, a plasma display, and an EL display is also suitable, and the fluorine-containing siloxane compound of the present invention or By forming the surface treatment layer by surface treatment using a coating agent, good dirt removal property can be obtained.

  EXAMPLES Hereinafter, although an Example and a reference example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example.

(Reference Example 1)

A 200 mL two-necked flask equipped with a magnetic stir bar and a Dimroth condenser was replaced with argon, 0.125 g (0.135 mmol) of chlorotris (triphenylphosphine) rhodium (I), 50 mL of dehydrated toluene, 3,3,4, 4,5,5,6,6,6-Nonafluoro-1-hexene (12.4 g, 50.3 mmol) and chlorodimethylsilane (9.46 g, 100 mmol) were contained. The mixture was heated to reflux at 120 ° C. for 10 hours, and the completion of the reaction was confirmed by gas chromatography. Toluene was distilled off by atmospheric distillation, followed by distillation under reduced pressure (boiling point 67 ° C./2.9 kPa) to obtain chloro (3,3,4,4,5,5,6,6,6-nonafluorohexyl) dimethyl. 6.78 g (yield 39.6%, GC purity 80%) of silane was obtained as a colorless and transparent liquid.
GC-MS (EI, 70 eV) m / z (%): 228 (2), 189 (21), 145 (24), 119 (8), 109 (100); ¹ H-NMR (400 MHz, CDCl ₃ ) : Δ 0.48 (s, 6H), 1.04 to 1.08 (m, 2H), 2.10 to 2.23 (m, 2H); ¹³ C-NMR (100 MHz, CDCl ₃ ): δ 1.36 , 8.95, 25.6, 116.3, 118.9, 121.6; ²⁹ Si-NMR (79 MHz, CDCl ₃ ): δ-22.9; ¹⁹ F-NMR (376 MHz, CDCl ₃ ): δ -123.1, -124.2, -116.0, -81.0; IR (neat, cm- ¹ ): 2970, 2908, 1442, 1350, 1211, 879, 849, 802, 702.

(Reference Example 2)

A 200 mL two-necked flask equipped with a magnetic stir bar and a Dimroth condenser was replaced with argon, 0.268 g (0.290 mmol) of chlorotris (triphenylphosphine) rhodium (I), 50 mL of dehydrated toluene, (perfluorohexyl) 21.1 g (60.8 mmol) of ethylene and 12.8 g (136 mmol) of chlorodimethylsilane were stored. After heating to reflux at 150 ° C. for 18 hours, 5.48 g (57.9 mmol) of chlorodimethylsilane was added, and the mixture was heated to reflux at 150 ° C. for 3 hours. The completion of the reaction was confirmed by gas chromatography. After distilling off toluene under reduced pressure, chloro (3,3,4,4,5,5,6,6,7,7) was distilled under reduced pressure using a Kugelrohr distillation apparatus (distillation temperature 50 ° C / 40 Pa). , 8,8,8-tridecafluorooctyl) dimethylsilane was obtained as a colorless transparent liquid, 14.7 g (yield 55.0%, GC purity 91%).
GC-MS (EI, 70 eV) m / z (%): 309 (3), 269 (2), 245 (13), 239 (14), 219 (3), 119 (8), 109 (100); ¹ H-NMR (400 MHz, CDCl ₃ ): δ 0.48 (s, 6H), 1.04 to 1.09 (m, 2H), 2.10 to 2.23 (m, 2H); ¹³ C-NMR (100 MHz, CDCl ₃ ): δ 1.27, 9.36, 26.17, 109.64, 122.26, 114.48, 116.80, 119.48, 122.18; ²⁹ Si-NMR (79 MHz, CDCl ₃ ): δ-31.7; ¹⁹ F-NMR (376 MHz, CDCl ₃ ): δ-126.2, -123.3, -122.9, -122.0, -81.0; IR (neat , ^cm -1): 2968,291 , 1442,1362,1234,1066,844,810,802,634.

(Reference Example 3)

A 200 mL two-necked flask equipped with a magnetic stir bar and a Dimroth condenser was replaced with argon, 0.110 g (0.119 mmol) of chlorotris (triphenylphosphine) rhodium (I), 25 mL of dehydrated toluene, 3,3,4, 4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluoro-1-decene 11.2 g (25.1 mmol) and chlorodimethylsilane 4.78 g (50.5 mmol) was stored. The mixture was heated to reflux at 150 ° C. for 17 hours, and the completion of the reaction was confirmed by gas chromatography. After distilling off toluene under reduced pressure, chloro (3,3,4,4,5,5,6,6,7, Thus, 10.3 g (yield 75.5%, GC purity 94%) of 7,8,8,9,9,10,10,10-heptadecafluorodecyl) dimethylsilane was obtained as a colorless transparent liquid.
GC-MS (EI, 70 eV) m / z (%): 409 (2), 339 (10), 119 (112), 109 (100); ¹ H-NMR (400 MHz, CDCl ₃ ): δ 0.48 ( s, 6H), 1.04 to 1.08 (m, 2H), 2.10 to 2.23 (m, 2H); ¹³ C-NMR (100 MHz, CDCl ₃ ): δ 0.97, 8.97, 25.73, 106.39, 109.08, 111.51, 111.57, 114.56, 116.30, 118.99, 121.69; ²⁹ Si-NMR (79 MHz, CDCl ₃ ): δ-31 ¹⁹ F-NMR (376 MHz, CDCl ₃ ): δ-126.2, -123.3, -122.3, -122.7, -122.0, -121.8, -115.9, −80.9; IR (neat, m ^-1): 2962,2908,1442,1357,1203,1149,848,802,656.

(Reference Example 4)

A 500 mL three-necked flask equipped with a magnetic stir bar, a 100 mL dropping funnel and a Dim funnel was replaced with argon, and t-butyl methyl ether (155 g, 1.77 mol) and bismuth chloride (1.87 g, 5.89 mmol) were placed. Silicon tetrachloride (99.2 g, 0.589 mol) was added dropwise from the dropping funnel at room temperature over 2 hours. After stirring for 15 hours at room temperature, it was confirmed by gas chromatography that the reaction was complete. This mixture was distilled at normal pressure (boiling point 112 ° C.) to obtain 67.4 g (yield 73.1%) of the desired chlorotrimethoxysilane.
_{GC-MS (EI, 70eV)} , m / z (%): 141 ([M-CH 3] +, 9.4), 111 (12), 120 (100). ¹ HNMR (400 MHz, CDCl ₃ ), a (ppm): 3.60 (s, 9H, OMe). ¹³ C NMR (100 MHz, CDCl ₃ ), a (ppm): 51.8. ²⁹ Si NMR (79 MHz, CDCl ₃ ), a (ppm): −66.6.

Example 1 of 7- (3,3,3-trifluoropropyl) -1,1,3,3,5,5,7,7-octamethyltetrasiloxane-1-ol (Compound 2-A) Composition

A 200 mL three-necked flask equipped with a magnetic stirring bar, a Liebig condenser and a dropping funnel was replaced with argon, and 1,1,3,3,5,5-hexamethyltrisiloxane-1,5-diol was added to the flask. 56 g (23.1 mmol), dehydrated diethyl ether 50.0 mL, and triethylamine 2.24 g (23.2 mmol) were stored. A dropping funnel was charged with 50.0 mL of dehydrated diethyl ether and 3.94 g (20.7 mmol) of (3,3,3-trifluoropropyl) chlorodimethylsilane, and the flask was cooled to 0 ° C. and added dropwise over 2.5 hours. did. After dropping, the mixture was stirred at 25 ° C. for 1 hour, and the completion of the reaction was confirmed by gas chromatography (GC). The reaction mixture is washed with water in a separatory funnel, the organic layer is concentrated with a rotary evaporator, and then collected using a recycle type high performance liquid chromatography (moving layer: methanol) to obtain the intended 7- (3, 3,3-trifluoropropyl) -1,1,3,3,5,5,7,7-octamethyltetrasiloxane-1-ol (Compound 2-A) as a colorless transparent liquid (5.12 g) Rate 62.7%, GC purity 99%).
GC-MS (EI, 70 eV) m / z (%): 379 (1), 281 (100), 227 (35), 207 (71), 133 (49); ¹ H-NMR (400 MHz, CDCl ₃ ) : Δ 0.07 (s, 6H), 0.09 (s, 6H), 0.13 (s, 6H), 0.14 (s, 6H) 0.74 to 0.79 (m, 2H), 2 0.00 to 2.13 (m, 2H); ¹³ C-NMR (100 MHz, CDCl ₃ ): δ-0.14, 0.32, 1.00, 1.10, 9.87, 28.3, 128 ²⁹ Si-NMR (79 MHz, CDCl ₃ ): δ-20.9, -20.3, -10.6, 7.09; ¹⁹ F-NMR (376 MHz, CDCl ₃ ): δ-68.7; IR ^(neat, cm -1): 3322,2962,2906,1446,136 , 1259,1065,1028,791,685.

(Example 2) 7- (3,3,4,4,5,5,6,6,6-nonafluorohexyl) -1,1,3,3,5,5,7,7-octamethyltetra Synthesis of siloxane-1-ol (compound 2-B)

A 100 mL three-necked flask equipped with a magnetic stirring bar, a Liebig condenser and a dropping funnel was replaced with argon, and 1,1,3,3,5,5-hexamethyltrisiloxane-1,5-diol was added to the flask. 89 g (16.2 mmol), dehydrated diethyl ether 15.0 mL, and triethylamine 1.65 g (16.3 mmol) were stored. In a dropping funnel, 15.0 mL of dehydrated diethyl ether and 5.04 g (14.8 mmol) of chlorodimethyl (3,3,4,4,5,5,6,6,6-nonafluorohexyl) silane were placed and taken over 30 minutes And dripped. After dropping, the mixture was stirred at 25 ° C. for 1 hour, and the completion of the reaction was confirmed by gas chromatography (GC). The reaction mixture is washed with water, the organic layer is concentrated with a rotary evaporator, and then collected using recycle type high performance liquid chromatography (moving layer: methanol) to obtain the intended 7- (3, 3, 4, 4,5,5,6,6,6-nonafluorohexyl) -1,1,3,3,5,5,7,7-octamethyltetratrisiloxane-1-ol (compound 2-B) colorless As a transparent liquid, 4.70 g (yield 58.4%, GC purity 82%) was obtained.
GC-MS (EI, 70 eV) m / z (%): 529 (2), 285 (100), 281 (85), 207 (40), 133 (9); ¹ H-NMR (400 MHz, CDCl ₃ ) : Δ 0.07 (s, 6H), 0.09 (s, 6H), 0.14 (s, 6H), 0.15 (s, 6H) 0.76 to 0.80 (m, 2H), 2 0.00 to 2.13 (m, 2H); ¹³ C-NMR (100 MHz, CDCl ₃ ): δ-0.11, 0.35, 1.00, 1.10, 7.53, 25.4, 111 .01, 116.13, 118.81, 121.50; ²⁹ Si-NMR (79 MHz, CDCl ₃ ): δ-20.9, -20.3, -10.7, 7.38; ¹⁹ F-NMR _{(376MHz, CDCl 3): δ} -126.1, -124.3, -122.3, ^{81.05; IR (neat, cm -1} ): 3323,2962,2908,1442,1352,1259,1066,1032,795,702.

(Example 3) 7- (3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl) -1,1,3,3,5 Synthesis of 5,7,7-octamethyltetrasiloxane-1-ol (Compound 2-C)

A 50 mL three-necked flask equipped with a magnetic stir bar, Liebig condenser and dropping funnel was replaced with argon, and 1,1,3,3,5,5-hexamethyltrisiloxane-1,5-diol was added to the flask. 47 g (6.10 mmol), dehydrated diethyl ether 5.0 mL and triethylamine 0.627 g (6.20 mmol) were stored. The dropping funnel contains 5.0 mL of dehydrated diethyl ether and 2.43 g of chlorodimethyl (3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl) silane. For 30 minutes. After dropping, the mixture was stirred at 25 ° C. for 1 hour, and the completion of the reaction was confirmed by gas chromatography (GC). The reaction mixture is washed with water, the organic layer is concentrated with a rotary evaporator, and then collected using recycle type high performance liquid chromatography (moving layer: methanol) to obtain the intended 7- (3, 3, 4, 4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl) -1,1,3,3,5,5,7,7-octamethyltetrasiloxane-1-ol 2.91 g (yield 81.7%, GC purity 96%) of (Compound 2-C) was obtained as a colorless transparent liquid.
GC-MS (EI, 70 eV) m / z (%): 629 (2), 285 (100), 281 (87), 207 (39), 133 (8); ¹ H-NMR (400 MHz, CDCl ₃ ) : Δ 0.07 (s, 6H), 0.09 (s, 6H), 0.14 (s, 6H), 0.15 (s, 6H) 0.76 to 0.80 (m, 2H), 2 0.00 to 2.13 (m, 2H); ¹³ C-NMR (100 MHz, CDCl ₃ ): δ-0.17, 0.29, 0.94, 1.04, 7.55, 25.5, 108 7, 111.3, 114.0, 116.2, 118.8, 121.0; ²⁹ Si-NMR (79 MHz, CDCl ₃ ): δ-20.8, -20.3, -10. ^{7.38; 19 F-NMR (376MHz} , CDCl 3): δ-126.2, -123.3 ^{-122.9, -122.0, -116.1, -80.87;} IR (neat, cm -1): 3303,2962,2908,1442,1350,1259,1066,1033,795,705.

(Example 4) 7- (3, 3, 4, 4, 5, 5, 6, 6, 7, 7, 8, 8, 9, 9, 10, 10, 10-heptadecafluorodecyl) -1, Synthesis of 1,3,3,5,5,7,7-octamethyltetrasiloxane-1-ol (compound 2-D)

A 100 mL three-necked flask equipped with a magnetic stir bar, Liebig condenser and dropping funnel was replaced with argon, and 1,1,3,3,5,5-hexamethyltrisiloxane-1,5-diol was added to the flask. 88 g (12.0 mmol), dehydrated diethyl ether 10.0 mL, and triethylamine 1.32 g (13.0 mmol) were stored. Add 15.0 mL of dehydrated diethyl ether and chlorodimethyl (3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluoro to the dropping funnel. Decyl) silane (5.40 g, 9.99 mmol) was placed and added dropwise over 1 hour. After dropping, the mixture was stirred at 25 ° C. for 3 hours, and the completion of the reaction was confirmed by gas chromatography (GC). The reaction mixture is washed with water, the organic layer is concentrated with a rotary evaporator, and then collected by using a high performance liquid chromatography (moving layer: methanol) to obtain the target (3, 3, 4, 4, 5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluorodecyl) -1,1,3,3,5,5,7,7-octamethyl 5.64 g (yield 72.9%, GC purity 73%) of trisiloxane-1-ol (compound 2-D) was obtained as a colorless transparent liquid.
EI-MS (70 eV) m / z (%): 729 (3), 285 (100), 281 (91), 207 (40), 133 (8); ¹ H-NMR (400 MHz, CDCl ₃ ): δ0 .07 (s, 6H), 0.09 (s, 6H), 0.14 (s, 6H), 0.15 (s, 6H) 0.76 to 0.80 (m, 2H), 2.00 -2.14 (m, 2H); ¹³ C-NMR (100 MHz, CDCl ₃ ): δ-1.93, -0.48, 0.59, 0.77, 7.49, 25.4, 106. 2, 108.7, 110.5, 111.1, 111.5, 111.6, 117.4, 118.6; ²⁹ Si-NMR (79 MHz, CDCl ₃ ): δ-20.8, −20. ^{3, -10.3,7.40; 19 F-NMR} (376MHz, CDCl 3): δ-12 ^{.1, -123.3, -122.6, -81.1;} IR (neat, cm -1): 3286,2962,2908,1442,1357,1234,1033,795,705.

Example 5 9- (3,3,3-trifluoropropyl) -3,3,5,5,7,7,9,9-octamethyl-1,1,1-trimethoxypentasiloxane (Compound 1) Synthesis of -A)

A 100 mL two-necked flask equipped with a magnetic stir bar and a Liebig condenser was replaced with argon, and 7- (3,3,3-trifluoropropyl) -1,1,3,3,5,5,7,7 -3.85 g (9.75 mmol) of octamethyltetrasiloxane-1-ol, dehydrated diethyl ether 30.0 mL, and 2.46 g (31.0 mmol) of pyridine were stored. 4.65 g (29.7 mmol) of trimethoxychlorosilane was added with a syringe over 10 minutes, the mixture was stirred at 25 ° C. for 2 hours, and the completion of the reaction was confirmed by gas chromatography (GC). After filtration through a Schlenk tube equipped with a sintered glass filter, the solvent was distilled off under reduced pressure. 9- (3,3,3-trifluoropropyl) -3,3,5,5,7,7, the target, by distillation under reduced pressure (distillation temperature 135 ° C./40 Pa) using a Kugelrohr distillation apparatus. 9.26 g (yield 65.0%, GC purity 98.8%) of 9,9-octamethyl-1,1,1-trimethoxypentasiloxane (Compound 1-A) was obtained as a colorless transparent liquid.
GC-MS (EI, 70 eV) m / z (%): 499 (14), 347 (100), 313 (84), 297 (47), 273 (65), 269 (63), 195 (32); ¹ H-NMR (400 MHz, CDCl ₃ ): δ 0.06 (s, 6H), 0.09 (s, 6H), 0.12 (s, 6H), 0.15 (s, 6H), 0.73 −0.78 (m, 2H), 1.99-2.12 (m, 2H), 3.56 (s, 9H); ¹³ C-NMR (100 MHz, CDCl ₃ ): δ-0.15, 0 .64, 0.92, 1.04, 9.85, 28.2, 51.0, 25.2, 128; ²⁹ Si-NMR (79 MHz, CDCl ₃ ): δ-85.3, -21.3 , −20.5, −19.7, 6.84; ¹⁹ F-NMR (376 MHz, CDCl ₃ ): δ-68.7; IR (neat, cm ⁻¹ ) 2960, 2908, 2844, 1446, 1365, 1259, 1201, 1065, 1026, 796, 687.

Example 6 9- (3,3,4,4,5,5,6,6,6-nonafluorohexyl) -3,3,5,5,7,7,9,9-octamethyl-1 Of 1,1,1-trimethoxypentasiloxane (Compound 1-B)

A 50 mL two-necked flask equipped with a magnetic stir bar and Liebig condenser was replaced with argon, and 7- (3,3,4,4,5,5,6,6,6-nonafluorohexyl) 1,1, 3,3,5,5,7,7-octamethyltrisiloxane-1-ol 3.68 g (6.75 mmol), dehydrated diethyl ether 20.0 mL and pyridine 1.54 g (19.5 mmol) were stored. 3.19 g (20.4 mmol) of trimethoxychlorosilane was added with a syringe over 10 minutes, the mixture was stirred at 25 ° C. for 2 hours, and the completion of the reaction was confirmed by gas chromatography (GC). After filtration through a Schlenk tube equipped with a sintered glass filter, the solvent was distilled off under reduced pressure. The target 9- (3,3,4,4,5,5,6,6,6-nonafluorohexyl)-by distillation under reduced pressure using a Kugelrohr distillation apparatus (distillation temperature 135 ° C./40 Pa) 2.85 g (yield 63.5%) of 3,3,5,5,7,7,9,9-octamethyl-1,1,1-trimethoxypentasiloxane (compound 1-B) as a colorless transparent liquid , GC purity 94%).
GC-MS (EI, 70 eV) m / z (%): 649 (25), 417 (9), 313 (100), 297 (42), 269 (22), 195 (27), 163 (31); ¹ H-NMR (400 MHz, CDCl ₃ ): δ 0.07 (s, 6H), 0.09 (s, 6H), 0.14 (s, 6H), 0.15 (s, 6H) 0.75- 0.79 (m, 2H), 1.99-2.13 (m, 2H); ¹³ C-NMR (100 MHz, CDCl ₃ ): δ-0.10, 0.68, 0.94, 1.06 , 7.58, 25.4, 51.1, 111.1, 116.1, 118.9, 121.6; ²⁹ Si-NMR (79 MHz, CDCl ₃ ): δ-85.3, -21.2 , −20.4, 19.63, 7.16; ¹⁹ F-NMR (376 MHz, CDCl ₃ ): Δ-126.1, -124.3, -116.3, -81.06; IR (neat, cm ⁻¹ ) 2962, 2844, 1442, 1352, 1259, 1066, 1029, 796, 702.

(Example 7) 9- (3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl) -3,3,5,5,7, Synthesis of 7,9,9-octamethyl-1,1,1-trimethoxypentasiloxane (Compound 1-C)

A 50 mL two-necked flask equipped with a magnetic stir bar and a Liebig condenser was replaced with argon, and 7- (3, 3, 4, 4, 5, 5, 6, 6, 7, 7, 8, 8, 8- Tridecafluorooctyl) -1,1,3,3,5,5,7,7-octamethyltrisiloxane-1-ol 2.46 g (3.82 mmol), dehydrated diethyl ether 10.0 mL and pyridine 0.620 g (7.84 mmol). 1.23 g (7.85 mmol) of trimethoxychlorosilane was added with a syringe over 10 minutes, the mixture was stirred at 25 ° C. for 2 hours, and the completion of the reaction was confirmed by gas chromatography (GC). After filtration through a Schlenk tube equipped with a sintered glass filter, the solvent was distilled off under reduced pressure. 9- (3,3,4,4,5,5,6,6,7,7,8,8) by subjecting it to vacuum distillation (distillation temperature 120 ° C / 40 Pa) using a Kugelrohr distillation apparatus. , 8-tridecafluorooctyl) -3,3,5,5,7,7,9,9-octamethyl-1,1,1-trimethoxypentasiloxane (compound 1-C) as a colorless transparent liquid 1 0.83 g (yield 61.6%, GC purity 91%) was obtained.
GC-MS (EI, 70 eV) m / z (%): 749 (22), 417 (10), 313 (100), 297 (42), 268 (22), 195 (27), 163 (30); ¹ H-NMR (400 MHz, CDCl ₃ ): δ 0.07 (s, 6H), 0.09 (s, 6H), 0.14 (s, 6H), 0.15 (s, 6H) 0.75- 0.79 (m, 2H), 1.99-2.13 (m, 2H); ¹³ C-NMR (100 MHz, CDCl ₃ ): δ-0.11, 0.64, 0.90, 1.03 , 7.54, 25.4, 51.06, 108.9, 111.4, 113.5, 116.0, 118.7, 121.4; ²⁹ Si-NMR (79 MHz, CDCl ₃ ): δ- ^{85.4, -21.4, -20.5, -19.7,7.13;} 19 F-NM _{(376MHz, CDCl 3): δ} -126.1, -123.3, -122.9, -122.0, -116.0, -80.81; IR (neat, cm -1): 2962,2844 1442, 1356, 1259, 1068, 1027, 796, 706.

(Example 8) 9- (3, 3, 4, 4, 5, 5, 6, 6, 7, 7, 8, 8, 9, 9, 10, 10, 10-heptadecafluorodecyl) -3, Synthesis of 3,5,5,7,7,9,9-octamethyl-1,1,1-trimethoxypentasiloxane (Compound 1-D)

A 50 mL two-necked flask equipped with a magnetic stir bar and a Liebig condenser was replaced with argon, and (3, 3, 4, 4, 5, 5, 6, 6, 7, 7, 8, 8, 9, 9, 10,10,10-heptadecafluorodecyl) -1,1,3,3,5,5,7,7-octamethyltrisiloxane-1-ol 4.51 g (6.05 mmol), dehydrated diethyl ether 0 mL and 1.44 g (18.2 mmol) of pyridine were stored. 2.90 g (18.5 mmol) of trimethoxychlorosilane was added with a syringe over 10 minutes, the mixture was stirred at 25 ° C. for 2 hours, and the completion of the reaction was confirmed by gas chromatography (GC). After filtration through a Schlenk tube equipped with a sintered glass filter, the solvent was distilled off under reduced pressure. 9- (3,3,4,4,5,5,6,6,7,7,8,8) is obtained by performing distillation under reduced pressure using a Kugelrohr distillation apparatus (distillation temperature 145 ° C./40 Pa). , 9,9,10,10,10-heptadecafluorodecyl) -3,3,5,5,7,7,9,9-octamethyl-1,1,1-trimethoxypentasiloxane (Compound 1-D) ) Was obtained as a colorless transparent liquid (yield 78.2%, GC purity 97%).
GC-MS (EI, 70 eV) m / z (%): 417 (10), 371 (13), 313 (100), 297 (43), 269 (23), 195 (25), 163 (29); ¹ H-NMR (400 MHz, CDCl ₃ ): δ 0.07 (s, 6H), 0.09 (s, 6H), 0.14 (s, 6H), 0.15 (s, 6H) 0.75 0.79 (m, 2H), 1.99-2.13 (m, 2H); ¹³ C-NMR (100 MHz, CDCl ₃ ): δ-0.10, 0.68, 0.96, 1.06 , 7.62, 25.4, 51.1, 105.73, 108.2, 110.1, 110.6, 111.0, 111.2, 116.9, 118.3; ²⁹ Si-NMR ( _{79MHz, CDCl 3): δ-} 85.3, -21.2, -20.4, -19.6, ^{.17; 19 F-NMR (376MHz} , CDCl 3): δ-126.1, -123.3, -122.7, -121.9, -121.7, -116.0, -80.84; IR (neat, cm ⁻¹ ): 2962, 2846, 1442, 1357, 1242, 1034, 802, 702.

(Example 9) 7- (3,3,4,4,5,5,6,6,6-nonafluorohexyl) -1,3,5-tris (3,3,3-trifluoropropyl) Synthesis of -1,3,5,7,7-pentamethyltetrasiloxane-1-ol (Compound 2-E)

A 50 mL three-necked flask equipped with a stirrer, a Dimroth condenser and a dropping funnel was replaced with argon, and 1,3,5-tris (3,3,3-trifluoropropyl) -1,3,5-trimethyl 2.85 g of siloxane-1,5-diol, 8.0 mL of dehydrated diethyl ether and 0.865 g of triethylamine were stored. The dropping funnel was filled with 8.0 mL of dehydrated diethyl ether and 4.21 g of chlorodimethyl (3,3,4,4,5,5,6,6,6-nonafluorohexyl) silane. After dropping, the mixture was stirred at room temperature for 2 hours, and the completion of the reaction was confirmed by gas chromatography (GC). The reaction mixture was washed with water, the solvent was concentrated with a rotary evaporator, and then 7- (3,3,4,4,5,5,6,6,6-nonafluorohexyl) using liquid chromatography (methanol). -1,3,5-tris (3,3,3-trifluoropropyl) -1,3,5,7,7-pentamethyltetrasiloxane-1-ol (compound 2-E) as a colorless transparent liquid 3.65 g (yield 55.2%) was obtained.
GC-MS (EI, 70 eV) m / z (%): 293 (4), 237 (33), 233 (40), 215 (81), 159 (26), 137 (100), 109 (29); ¹ H-NMR (400 MHz, CDCl ₃ ): δ 0.13-0.19 (m, 15H), 0.76-0.80 (m, 2H), 2.00-2.13 (m, 2H); ¹³ C-NMR (100 MHz, CDCl ₃ ): δ-1.50, -0.89, -0.77, -0.22, 7.45, 9.00, 25.2, 27.96, 111. 01, 116.13, 118.81, 121.50; ²⁹ Si-NMR (79 MHz, CDCl ₃ ): δ-22.8, -22.5, -22.2, -13.0, -12.8 , 9.13, 9.36; ¹⁹ F-NMR (376 MHz, CDCl ₃ ): δ -126.1, -124.3, -116.3, -81.07, -68.73; IR (neat, cm- ¹ ): 3410, 2964, 2908, 1446, 1369, 1263, 1207, 1065 898, 701.

Example 10 9- (3,3,4,4,5,5,6,6,6-nonafluorohexyl) -3,5,7-tris (3,3,3-trifluoropropyl)- Synthesis of 3,5,7,9,9-pentamethyl-1,1,1-trimethoxypentasiloxane (compound 1-E)

A 50 mL two-necked flask equipped with a magnetic stir bar and Liebig condenser was replaced with argon and 7- (3,3,4,4,5,5,6,6,6-nonafluorohexyl) -1,3 , 5-tris (3,3,3-trifluoropropyl) -1,3,5,7,7-pentamethyltetrasiloxane-1-ol 2.32 g (2.93 mmol) and dehydrated diethyl ether 12.0 mL And 1.01 g (12.7 mmol) of pyridine. 1.77 g (11.3 mmol) of trimethoxychlorosilane was added with a syringe over 10 minutes, stirred at 25 ° C. for 3 hours, and the completion of the reaction was confirmed by gas chromatography (GC). After filtration through a Schlenk tube equipped with a sintered glass filter, the solvent was distilled off under reduced pressure. The target 9- (3,3,4,4,5,5,6,6,6-nonafluorohexyl)-by distillation under reduced pressure (distillation temperature 150 ° C./35 Pa) using a Kugelrohr distillation apparatus 3,5,7-tris (3,3,3-trifluoropropyl) -3,5,7,9,9-pentamethyl-1,1,1-trimethoxypentasiloxane (compound 1-E) is colorless and transparent As a liquid, 1.45 g (yield 54.4%) was obtained.
GC-MS (EI, 70 eV) m / z (%): 491 (5), 335 (54), 277 (34), 253 (38), 199 (100), 137 (96), 105 (47); ¹ H-NMR (400 MHz, CDCl ₃ ): δ 0.13 to 0.19 (m, 15H), 0.71 to 0.82 (m, 8H), 2.00 to 2.13 (m, 8H), 3.56 (s, 9H); ¹³ C-NMR (100 MHz, CDCl ₃ ): δ-1.29, -0.98, -0.82, -0.22, 7.39, 9.03, 25 2, 27.8, 51.1, 126.2, 128.9, 131.7; ²⁹ Si-NMR (79 MHz, CDCl ₃ ): δ-85.6, −22.4, −21.3, ^{9.17; 19 F-NMR (376MHz} , CDCl 3): δ-126.1, -124 ^{4, -116.2, -81.1, -68.9;} IR (neat, cm -1) 2951,2848,1446,1369,1263,1207,1089,1024,837,769,702.

Example 11 9- (3,3,4,4,5,5,6,6,6-nonafluorohexyl) -3,5,7-tris (3,3,3-trifluoropropyl)- Synthesis of 3,5,7,9,9-pentamethyl-1,1,1-trichloropentasiloxane (Compound 1-F)

A 100 mL three-necked flask equipped with a magnetic stir bar, Liebig condenser and dropping funnel was replaced with argon, and 10.0 mL of dehydrated diethyl ether, 3.41 g (20.3 mmol) of tetrachlorosilane and 1.99 g of triethylamine (19) were added to the flask. 7 mmol). 7- (3,3,4,4,5,5,6,6,6-nonafluorohexyl) -1,3,5-tris (3,3,3-trifluoropropyl) -1 in the dropping funnel 3,5,7,7-pentamethyltetrasiloxane-1-ol 3.17 g (4.01 mmol) and 10.0 mL of dehydrated diethyl ether were added dropwise over 1 hour. After dropping, the mixture was stirred at 25 ° C. for 60 hours, and the completion of the reaction was confirmed by GC-MS. After filtration through a Schlenk tube equipped with a sintered glass filter, the solvent was distilled off under reduced pressure. The target 9- (3,3,4,4,5,5,6,6-nonafluorohexyl)-by distillation under reduced pressure using a Kugelrohr distillation apparatus (distillation temperature 145 ° C./40 Pa) 3,5,7-tris (3,3,3-trifluoropropyl) -3,5,7,9,9-pentamethyl-1,1,1-trichloropentasiloxane (compound 1-F) is colorless and transparent As a liquid, 0.457 g (yield 12.3%) was obtained.
GC-MS (EI, 70 eV) m / z (%): 293 (5), 233 (47), 215 (53), 155 (44), 137 (100), 109 (23); ¹ H-NMR ( 400 MHz, CDCl ₃ ): δ 0.14 (s, 3H), 0.17 (s, 6H), 0.19 (s, 3H), 0.31 (s, 3H), 0.72 to 0.82 ( m, 8H), 1.97-2.14 (m, 8H); ²⁹ Si-NMR (79 MHz, CDCl ₃ ): δ-22.4, -21.7, -17.7, 3.38, 9 ¹⁹ F-NMR (376 MHz, CDCl ₃ ): δ-126.1, -124.4, -116.3, -81.1, -68.7; IR (neat, cm ⁻¹ ): 2960 2910, 1446, 1369, 1263, 1207, 1066, 1024, 8 1,771,600.

Example 12 5- (3,3,4,4,5,5,6,6,6-nonafluorohexyl) -1,1,3,3,5,5-hexamethyltrisiloxane-1- Synthesis of all (compound 2-F)

A 50 mL three-necked flask equipped with a magnetic stirrer, a Liebig condenser and a dropping funnel was replaced with argon, and 1.64 g of 1,1,3,3-tetramethyldisiloxane-2,4-diol (9. 85 mmol), 10.0 mL of dehydrated diethyl ether and 0.953 g (9.42 mmol) of triethylamine. In a dropping funnel, 5.0 mL of dehydrated diethyl ether and 2.51 g (7.36 mmol) of chlorodimethyl (3,3,4,4,5,5,6,6,6-nonafluorohexyl) silane were placed over 35 minutes. And dripped. After dropping, the mixture was stirred at 25 ° C. for 3 hours, and the completion of the reaction was confirmed by gas chromatography (GC). The reaction mixture is washed with water, the organic layer is concentrated with a rotary evaporator, and then subjected to distillation under reduced pressure (distillation temperature 100 ° C./40 Pa) using a Kugelrohr distillation apparatus to obtain the intended 5- (3, 3, 4, 4,5,5,6,6,6-nonafluorohexyl) -1,1,3,3,5,5-hexamethyltrisiloxane-1-ol (compound 2-F) as a colorless transparent liquid 0.08 g (yield 60.0%) was obtained.
GC-MS (EI, 70 eV) m / z (%): 455 (1), 227 (19), 211 (100), 207 (94), 191 (14); ¹ H-NMR (400 MHz, CDCl ₃ ) : Δ 0.08 (s, 6H), 0.13 (s, 6H), 0.15 (s, 6H), 0.76 to 0.80 (m, 2H), 2.00 to 2.14 (m , 2H); ¹³ C-NMR (100 MHz, CDCl ₃ ): δ-0.11, 0.28, 1.06, 7.48, 25.3, 116, 118, 119, 121; ²⁹ Si-NMR ( 79 MHz, CDCl ₃ ): δ-19.9, −10.8, 7.37; ¹⁹ F-NMR (376 MHz, CDCl ₃ ): δ-126, −124, −116, −81.1; IR (neat) , ^cm -1): 3305,2962,2906,12 9,1218,1041,796.

Example 13 5- (3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl) -1,1,3,3,5 Synthesis of 5-hexamethyltrisiloxane-1-ol (Compound 2-G)

A 500 mL three-necked flask equipped with a magnetic stirrer, a Liebig condenser and a dropping funnel was replaced with argon, and 3.15 g of 1,1,3,3-tetramethyldisiloxane-2,4-diol (18. 9 mmol), 130 mL of dehydrated diethyl ether and 1.92 g (19.0 mmol) of triethylamine. The dropping funnel contains 20.0 mL of dehydrated diethyl ether and 7.10 g of chlorodimethyl (3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl) silane. For 25 minutes. After dropping, the mixture was stirred at 25 ° C. for 3 hours. The reaction mixture is washed with water, the organic layer is concentrated with a rotary evaporator, and then subjected to distillation under reduced pressure (distillation temperature 95 ° C./20 Pa) using a Kugelrohr distillation apparatus to obtain the target 5- (3, 3, 4, 4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl) -1,1,3,3,5,5-hexamethyltrisiloxane-1-ol (compound 2- 6.85 g (yield 74.6%) of G) was obtained as a colorless and transparent liquid.
GC-MS (EI, 70 eV) m / z (%): 555 (0.4), 227 (23), 223 (35), 211 (100), 207 (99), 191 (16); ¹ H- NMR (400 MHz, CDCl ₃ ): δ 0.08 (s, 6H), 0.13 (s, 6H), 0.15 (s, 6H), 0.76 to 0.80 (m, 2H), 2. 00-2.14 (m, 2H); ¹³ C-NMR (100 MHz, CDCl ₃ ): δ-0.11, 0.27, 1.05, 7.47, 25.1-25.6; ²⁹ Si -NMR (79 MHz, CDCl ₃ ): δ-19.9, -10.6, 7.39; ¹⁹ F-NMR (376 MHz, CDCl ₃ ): δ-126.1, -123.3, -122.9 ^{, -121.9, -80.8; IR (neat} , cm -1): 3338, 964,1442,1236,1045,796,702.

Example 14 5- (3, 3, 4, 4, 5, 5, 6, 6, 7, 7, 8, 8, 9, 9, 10, 10, 10-heptadecafluorodecyl) -1, Synthesis of 1,3,3,5,5-hexamethyltrisiloxane-1-ol (Compound 2-H)

A 300 mL three-necked flask equipped with a magnetic stir bar, Liebig condenser and 50 mL dropping funnel was replaced with argon, and 3.30 g of 1,1,3,3-tetramethyldisiloxane-2,4-diol was added to the flask (20 0.0 mmol), 140 mL of dehydrated diethyl ether and 1.70 g (16.8 mmol) of triethylamine. To the dropping funnel 10.0 mL dehydrated diethyl ether and chlorodimethyl (3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluoro Decyl) silane (7.01 g, 13.0 mmol) was placed, cooled to 0 ° C. in an ice bath, and added dropwise over 20 minutes. After dropping, the mixture was stirred at 25 ° C. for 90 minutes. The reaction mixture is washed with water, the organic layer is concentrated with a rotary evaporator, and then subjected to distillation under reduced pressure (distillation temperature 110 ° C./20 Pa) using a Kugelrohr distillation apparatus to obtain the target 5- (3, 3, 4, 4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl) -1,1,3,3,5,5-hexamethyltrisiloxane-1-ol (compound 2- 6.52 g (yield 75.0%) of H) was obtained as a colorless transparent liquid.
GC-MS (EI, 70 eV) m / z (%): 655 (0.4), 227 (27), 223 (38), 211 (100), 207 (99.5); ¹ H-NMR (400 MHz , CDCl ₃ ): δ 0.08 (s, 6H), 0.14 (s, 6H), 0.15 (s, 6H), 0.76 to 0.80 (m, 2H), 2.01 to 2 ^{.14 (m, 2H); 13} C-NMR (100MHz, CDCl 3): δ-1.10,0.26,1.04,7.48,25.5; 29 Si-NMR (79MHz, CDCl 3 ): Δ-19.9, −10.6, 7.35; ¹⁹ F-NMR (376 MHz, CDCl ₃ ): δ-126.1, -123.3, -122.7, -122.0, − 121.7, -116.0, -80.74; IR ( neat, cm -1): 3 86,2962,1201,1145,1043,796,795,704.

Example 15 7- (3,3,4,4,5,5,6,6,6-nonafluorohexyl) -3,3,5,5,7,7-hexamethyl-1,1,1 -Synthesis of trimethoxypentasiloxane (compound 1-G)

A 50 mL three-necked flask equipped with a magnetic stir bar, Liebig condenser and 25 mL dropping funnel was replaced with argon and 5- (3,3,4,4,5,5,6,6,6-nonafluorohexyl) -1,1,3,3,5,5-hexamethyltrisiloxane-1-ol 1.88 g (3.99 mmol), dehydrated diethyl ether 5.0 mL, and pyridine 0.469 g (5.93 mmol) were stored. In a dropping funnel, 5.0 mL of dehydrated diethyl ether and 0.981 g (6.26 mmol) of trimethoxychlorosilane were placed and added dropwise at 0 ° C. over 10 minutes. Stir at 25 ° C. for 3 hours. After filtration through a Schlenk tube equipped with a sintered glass filter, the solvent was distilled off under reduced pressure. The target 7- (3,3,4,4,5,5,6,6,6-nonafluorohexyl)-by distillation under reduced pressure (distillation temperature 80 ° C./25 Pa) using a Kugelrohr distillation apparatus 1.40 g (yield 59.4%) of 3,3,5,5,7,7-hexamethyl-1,1,1-trimethoxypentasiloxane (Compound 1-G) was obtained as a colorless transparent liquid.
GC-MS (EI, 70 eV) m / z (%): 575 (21), 347 (60), 343 (100), 239 (60), 223 (39), 105 (39); ¹ H-NMR ( 400 MHz, CDCl ₃ ): δ 0.08 (s, 6H), 0.14 (m, 12H), 0.75 to 0.79 (m, 2H), 1.99 to 2.13 (m, 2H); ¹³ C-NMR (100 MHz, CDCl ₃ ): δ-0.15, 0.60, 0.98, 7.49, 25.3, 51.1; ²⁹ Si-NMR (79 MHz, CDCl ₃ ): δ- 85.3, -20.0, 19.5, 7.31; ¹⁹ F-NMR (376 MHz, CDCl ₃ ): δ-126.1, -124.3, -116.3, -81.1; IR ^(neat, cm -1) 2962,2844,1442,1352 1261,1087,1035,829,798,746.

Example 16 7- (3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl) -3,3,5,5,7, Synthesis of 7-hexamethyl-1,1,1-trimethoxypentasiloxane (Compound 1-H)

A 100 mL three-necked flask equipped with a magnetic stir bar, Liebig condenser and 50 mL dropping funnel was replaced with argon, and 5- (3, 3, 4, 4, 5, 5, 6, 6, 7, 7, 8, 8,8-tridecafluorooctyl) -1,1,3,3,5,5-hexamethyltrisiloxane-1-ol 1.92 g (3.37 mmol), dehydrated diethyl ether 30.0 mL and pyridine 0.48 g (6.12 mmol). 10.0 mL of dehydrated diethyl ether and 1.67 g (10.6 mmol) of trimethoxychlorosilane were placed in the dropping funnel and dropped over 5 minutes. Stir at 25 ° C. for 2 hours. After filtration through a Schlenk tube equipped with a sintered glass filter, the solvent was distilled off under reduced pressure. 7- (3,3,4,4,5,5,6,6,7,7,8,8) by subjecting it to vacuum distillation (distillation temperature 120 ° C / 45 Pa) using a Kugelrohr distillation apparatus. , 8-tridecafluorooctyl) -3,3,5,5,7,7-hexamethyl-1,1,1-trimethoxypentasiloxane (Compound 1-H) as a colorless transparent liquid (1.56 g) Rate 75.2%).
GC-MS (EI, 70 eV) m / z (%): 675 (17), 347 (66), 343 (100), 273 (29), 268 (24), 239 (58), 223 (37), 105 (32); ¹ H-NMR (400 MHz, CDCl ₃ ): δ 0.08 (s, 6H), 0.14 (s, 12H), 0.75 to 0.80 (m, 2H), 1.99 To 2.13 (m, 2H) 3.56 (s, 12H); ¹³ C-NMR (100 MHz, CDCl ₃ ): δ-0.16, 0.57, 0.96, 7.43, 25.3 , 51.0; ²⁹ Si-NMR (79 MHz, CDCl ₃ ): δ-85.4, -20.1, -19.6, 7.30; ¹⁹ F-NMR (376 MHz, CDCl ₃ ): δ-126 .1, -123.4, -122.9, -122.0, -116 ^{1, -80.8; IR (neat,} cm -1): 2962,2846,1442,1362,1238,1194,1088,1036,827,798,706.

(Example 17) 7- (3, 3, 4, 4, 5, 5, 6, 6, 7, 7, 8, 8, 9, 9, 10, 10, 10-heptadecafluorodecyl) -3, Synthesis of 3,5,5,7,7-hexamethyl-1,1,1-trimethoxypentasiloxane (Compound 1-I)

A 100 mL three-necked flask equipped with a magnetic stir bar, Liebig condenser and 25 mL dropping funnel was replaced with argon, and 5- (3, 3, 4, 4, 5, 5, 6, 6, 7, 7, 8, 8,9,9,10,10,10-heptadecafluorodecyl) -1,1,3,3,5,5-hexamethyltrisiloxane-1-ol 2.21 g (3.29 mmol) and dehydrated diethyl ether 25.0 mL and 0.323 g (4.08 mmol) of pyridine were stored. The dropping funnel was charged with 15.0 mL of dehydrated diethyl ether and 0.787 g (5.24 mmol) of trimethoxychlorosilane, added dropwise over 20 minutes, and then stirred at 25 ° C. for 3 hours. After filtration through a Schlenk tube equipped with a sintered glass filter, the solvent was distilled off under reduced pressure. 7- (3,3,4,4,5,5,6,6,7,7,8,8) by distillation under reduced pressure (distillation temperature 110 ° C / 40 Pa) using a Kugelrohr distillation apparatus , 9,9,10,10,10-heptadecafluorodecyl) -3,3,5,5,7,7-hexamethyl-1,1,1-trimethoxypentasiloxane (Compound 1-I) is colorless and transparent As a liquid, 1.87 g (yield 71.9%) was obtained.
GC-MS (EI, 70 eV) m / z (%): 775 (9), 347 (60), 343 (100), 273 (27), 239 (43), 223 (26), 105 (24); ¹ H-NMR (400 MHz, CDCl ₃ ): δ 0.08 (s, 6H), 0.14 (s, 12H), 0.15 (s, 6H) 0.75 to 0.80 (m, 2H), 1.99-2.13 (m, 2H); ¹³ C-NMR (100 MHz, CDCl ₃ ): δ-0.16, 0.58, 0.96, 7.47, 25.4, 51.0; ²⁹ Si-NMR (79 MHz, CDCl ₃ ): δ-85.4, -20.1, -19.6, 7.30; ¹⁹ F-NMR (376 MHz, CDCl ₃ ): δ-126.1, -123 .3, -122.7, -122.0, -121.8, -116.1, ^{80.76; IR (neat, cm -1} ): 2962,2846,1201,1090,1035,1034,829,798,704.

(Example 18) Surface treatment of compound 1-A on glass substrate A 0.3 wt% chloroform solution of compound 1-A was prepared, and a soda glass substrate was formed into a film by dip coating at 50 ° C in this solution. went. When the contact angles of water and hexadecane (droplet volume 1 μL) were obtained by the θ / 2 method at five modified surfaces and the average was obtained, the contact angle with water was 65.5 ° and the contact angle with hexadecane was 18.9. A value of ° was obtained.

(Example 19) Surface treatment of compound 1-B on glass substrate A 0.3 wt% chloroform solution of compound 1-B was prepared, and a soda glass substrate was formed into a film by dip coating at 50 ° C in this solution. went. When the contact angles of water and hexadecane (droplet volume 1 μL) were obtained by the θ / 2 method at five modified surfaces and the average was obtained, the contact angle with water was 75.1 ° and the contact angle with hexadecane was 26.1. A value of ° was obtained.

(Example 20) Surface treatment of compound 1-C on glass substrate A 0.3 wt% chloroform solution of compound 1-C was prepared, and a soda glass substrate was formed into a film by dip coating at 50 ° C in this solution. went. When the contact angles of water and hexadecane (droplet volume 1 μL) were obtained by the θ / 2 method at five modified surfaces and the average was obtained, the contact angle for water was 49.8 ° and the contact angle for hexadecane was 22.1. A value of ° was obtained.

(Example 21) Surface treatment of compound 1-D on glass substrate A 0.3 wt% chloroform solution of compound 1-D was prepared, and a soda glass substrate was formed into a film by dip coating at 50 ° C in this solution. went. When the contact angles of water and hexadecane (droplet volume: 1 μL) were obtained by the θ / 2 method at five modified surfaces and the average was obtained, the contact angle for water was 64.6 ° and the contact angle for hexadecane was 17.8. A value of ° was obtained.

(Example 22) Surface treatment of compound 1-E on glass substrate A 0.3 wt% chloroform solution of compound 1-E was prepared, and a soda glass substrate was formed into a film by dip coating at 50 ° C in this solution. went. The contact angle k of water and hexadecane (droplet volume 1 μL) was determined at the five modified surfaces by the θ / 2 method, and the average was obtained. The contact angle with water was 73.8 °, and the contact angle with hexadecane was 24. A value of 7 ° was obtained.

Example 23 Surface Treatment of Compound 1-F on Glass Substrate A 0.3 wt% chloroform solution of Compound 1-F was prepared, and a soda glass substrate was formed into a film by dip coating at 50 ° C. in this solution. went. The contact angle k of water and hexadecane (droplet volume 1 μL) was determined at the five modified surfaces by the θ / 2 method, and the average was obtained. The contact angle with water was 92.2 °, and the contact angle with hexadecane was 44. A value of 0 ° was obtained.

(Example 24) Surface treatment of compound 2-A on glass substrate A 0.3 wt% chloroform solution of compound 2-A was prepared, and a soda glass substrate was formed into a film by dip coating at 50 ° C in this solution. went. The contact angle k of water and hexadecane (droplet volume 1 μL) was obtained at the five modified surfaces by the θ / 2 method, and the average was obtained. The contact angle with water was 54.8 °, and the contact angle with hexadecane was 15. A value of 4 ° was obtained.

(Example 25) Surface treatment of compound 2-B on glass substrate A 0.3 wt% chloroform solution of compound 2-B was prepared, and a soda glass substrate was formed into a film by dip coating at 50 ° C in this solution. went. When the contact angle k of water and hexadecane (droplet volume 1 μL) was obtained by the θ / 2 method at five modified surfaces, and the average was obtained, the contact angle with water was 63.4 °, and the contact angle with hexadecane was 20. A value of 5 ° was obtained.

(Example 26) Surface treatment of compound 2-C on glass substrate A 0.3 wt% chloroform solution of compound 2-C was prepared, and a soda glass substrate was formed into a film by dip coating at 50 ° C in this solution. went. When the contact angle k of water and hexadecane (droplet volume 1 μL) was obtained by the θ / 2 method at five modified surfaces, and the average was obtained, the contact angle for water was 53.8 ° and the contact angle for hexadecane was 16. A value of 7 ° was obtained.

Example 27 Surface Treatment of Compound 2-D on Glass Substrate A 0.3 wt% chloroform solution of Compound 2-D was prepared, and a soda glass substrate was formed into a film by dip coating at 50 ° C. in this solution. went. When the contact angle k of water and hexadecane (droplet volume 1 μL) was obtained at the five modified surfaces by the θ / 2 method and the average was obtained, the contact angle for water was 58.2 ° and the contact angle for hexadecane was 20. A value of 8 ° was obtained.

Example 27 Surface Treatment of Compound 2-E on Glass Substrate A 0.3 wt% chloroform solution of compound 2-E was prepared, and a soda glass substrate was formed into a film by dip coating at 50 ° C. in this solution. went. When the contact angle k of water and hexadecane (droplet volume 1 μL) was determined by the θ / 2 method at five modified surfaces and the average was obtained, the contact angle with water was 47.6 ° and the contact angle with hexadecane was 16. A value of 3 ° was obtained.

Example 28 Surface Treatment of Compound 1-G on Glass Substrate A 0.3 wt% chloroform solution of compound 1-G was prepared, and a soda glass substrate was formed into a film by dip coating at 50 ° C. in this solution. went. The contact angle k of water and hexadecane (droplet volume 1 μL) was determined at the five modified surfaces by the θ / 2 method, and the average was obtained. The contact angle with water was 66.5 °, and the contact angle with hexadecane was 34. A value of 1 ° was obtained.

(Example 29) Surface treatment of compound 1-H on glass substrate A 0.3 wt% chloroform solution of compound 1-H was prepared, and a soda glass substrate was formed into a film by dip coating at 50 ° C in this solution. went. The contact angle k of water and hexadecane (droplet volume 1 μL) was determined at the five modified surfaces by the θ / 2 method, and the average was obtained. The contact angle with water was 91.6 °, and the contact angle with hexadecane was 37. A value of 1 ° was obtained.

(Comparative Example 1) Surface treatment of 1,1,1-trimethoxy-7-phenyl-1,1,3,3,5,5,7,7-octamethylpentasiloxane on a glass substrate 1,1,1 -A 0.3 wt% chloroform solution of trimethoxy-7-phenyl-1,1,3,3,5,5,7,7-octamethylpentasiloxane was prepared, and a soda glass substrate was added to this solution at 50 ° C. Film formation was performed by dip coating. The contact angle k of water and hexadecane (droplet volume 1 μL) was determined at the five modified surfaces by the θ / 2 method, and the average was obtained. The contact angle with water was 63.7 °, and the contact angle with hexadecane was 10. A value of 0 ° was obtained.

By using the fluorine-containing siloxane compound produced according to the present invention, a glass substrate having water and oil repellency on its surface can be provided. Moreover, the surface of a base material can be modified as a fluorine-containing silane coupling agent, and can be used as a base material adhesion and dispersing agent.

Claims (7)

General formula (1)

(In the formula, R ¹ represents a fluoroalkyl group having 1 to 8 carbon atoms. R ² , R ³ , R ⁴ and R ⁵ each independently represents 1 to 8 carbon atoms which may be substituted with a fluorine atom. N represents 2 or 3. Z represents a hydrogen atom, or General Formula (2)

(In the formula, R ⁶ , R ⁷ and R ⁸ each independently represents an alkyl group having 1 to 2 carbon atoms, a halogen atom or an alkoxy group having 1 to 3 carbon atoms, and R ⁶ , R ⁷ or R ⁸ At least one is a halogen atom or an alkoxy group having 1 to 3 carbon atoms). The fluorine-containing siloxane compound represented by this. General formula (3)

(In the formula, R ¹ represents a fluoroalkyl group having 1 to 8 carbon atoms. R ² , R ³ , R ⁴ and R ⁵ each independently represents 1 to 8 carbon atoms which may be substituted with a fluorine atom. R ⁶ , R ⁷ and R ⁸ each independently represents an alkyl group having 1 to 2 carbon atoms, a halogen atom or an alkoxy group having 1 to 3 carbon atoms, and R ⁶ , R ⁷ or R ^The fluorine-containing siloxane compound according to claim 1, wherein at least one of ⁸ is a halogen atom or an alkoxy group having 1 to 3 carbon atoms, n represents 2 or 3. General formula (4)

(In the formula, R ¹ represents a fluoroalkyl group having 1 to 8 carbon atoms. R ² , R ³ , R ⁴ and R ⁵ each independently represents 1 to 8 carbon atoms which may be substituted with a fluorine atom. The fluorine-containing siloxane compound according to claim 1, wherein n represents 2 or 3. General formula (5)

(Wherein R ⁴ and R ⁵ each independently represents an alkyl group having 1 to 8 carbon atoms which may be substituted with a fluorine atom. N represents 2 or 3). The compound and the general formula (6)

(In the formula, R ¹ represents a fluoroalkyl group having 1 to 8 carbon atoms. R ² and R ³ each independently represents an alkyl group having 1 to 8 carbon atoms which may be substituted with a fluorine atom. X represents a halogen atom or an alkoxy group having 1 to 3 carbon atoms.)
And a fluoroalkyl-substituted silane compound represented by the general formula (4):

(In the formula, R ¹ represents a fluoroalkyl group having 1 to 8 carbon atoms. R ² , R ³ , R ⁴ and R ⁵ each independently represents 1 to 8 carbon atoms which may be substituted with a fluorine atom. Wherein n represents 2 or 3.) A method for producing a fluorine-containing siloxane compound represented by: General formula (4)

(In the formula, R ¹ represents a fluoroalkyl group having 1 to 8 carbon atoms. R ² , R ³ , R ⁴ and R ⁵ each independently represents 1 to 8 carbon atoms which may be substituted with a fluorine atom. And n represents 2 or 3.) and a fluorine-containing siloxane compound represented by the general formula (7):

(In the formula, R ⁶ , R ⁷ and R ⁸ each independently represents an alkyl group having 1 to 2 carbon atoms, a halogen atom or an alkoxy group having 1 to 3 carbon atoms, and R ⁶ , R ⁷ or R ⁸ At least one is a halogen atom or an alkoxy group having 1 to 3 carbon atoms, and X represents a halogen atom or an alkoxy group having 1 to 3 carbon atoms). And general formula (3)

(In the formula, R ¹ represents a fluoroalkyl group having 1 to 8 carbon atoms. R ² , R ³ , R ⁴ and R ⁵ each independently represents 1 to 8 carbon atoms which may be substituted with a fluorine atom. R ⁶ , R ⁷ and R ⁸ each independently represents an alkyl group having 1 to 2 carbon atoms, a halogen atom or an alkoxy group having 1 to 3 carbon atoms, and R ⁶ , R ⁷ or R ^And at least one of ⁸ is a halogen atom or an alkoxy group having 1 to 3 carbon atoms, n is 2 or 3.).   A coating agent comprising the fluorinated siloxane compound according to claim 1, 2 or 3 and a liquid medium. A surface treatment method for a glass substrate, wherein the liquid medium is removed after the coating agent according to claim 6 is applied to the surface of the substrate.