JP6664984B2 - Fluorine-containing siloxane compound, method for producing the same, coating agent containing the same, and surface treatment method for glass substrate - Google Patents

Description

  The present invention relates to a fluorine-containing siloxane compound which 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 same, and a surface treatment method for a glass substrate.

  Compounds having a fluoroalkyl moiety in the molecule exhibit high lubricity and water / oil repellency, and are therefore suitably used as a surface treatment agent. When water- and oil-repellency is imparted to the surface of the base material, dirt can be easily wiped off, thereby improving dirt removal. For this purpose, a reactive silane compound having a fluoroalkyl group or a fluorinated ether compound having a perfluoropolyether as a main chain and having a reactive silyl group at a terminal is used as an antifouling agent, a lubricant, It can be used as a surface treatment agent such as a water repellent agent (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-A-2000-2324071 JP-A-11-092177 JP 2003-238577 A

  However, a surface treatment layer using functional silanes having only a fluoroalkyl main chain as a substituent tends to be inferior in sliding properties for applications such as touch panels. In addition, a fluorinated ether compound having a perfluoropolyether chain as a main chain and having a reactive silyl group at a terminal is a high molecular weight compound having a molecular weight distribution although the sliding property is improved, and its vapor pressure is low. However, there is a problem that high-temperature and high-vacuum are required for vapor deposition, and that it is soluble only in a fluorous solvent such as expensive perfluorohexane.

  The present invention has been made in view of the above circumstances, and it is an object of the present invention to provide a fluorine-containing siloxane compound which can impart good water / oil repellency to a substrate surface, 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 method for treating the surface of a glass substrate using the coating agent.

The present inventors have conducted intensive studies to achieve the above object, and as a result, by reacting a dialkylsiloxane compound having a hydroxyl group at both terminals with a fluoroalkyl-substituted silane compound and then a silane compound having a reactive group. It has been found that a fluorine-containing siloxane compound having desired characteristics can be produced, and the present invention has been completed.
That is, the present invention relates to a fluorine-containing siloxane compound having the following constitutions [1] to [8], a method for producing the same, a coating agent containing the same, and a surface treatment method for a glass substrate.
[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 represent a C ¹ to C 8 optionally substituted by a fluorine atom. And n represents 2 or 3. Z is a hydrogen atom or the general formula (2)

(Wherein, R ⁶ , R ⁷ and R ⁸ each independently represent 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 represents At least one is a halogen atom or an alkoxy group having 1 to 3 carbon atoms). A) a fluorine-containing siloxane compound represented by the formula:
[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 represent a C ¹ to C 8 optionally substituted by a fluorine atom. R ⁶ , R ⁷ and R ⁸ each independently represent 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 ^Wherein at least one of ⁸ is a halogen atom or an alkoxy group having 1 to 3 carbon atoms, and 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 represent a C ¹ to C 8 optionally substituted by a fluorine atom. Wherein n represents 2 or 3.) The fluorine-containing siloxane compound according to item 1, which is represented by the following formula:
[4]
General formula (5)

(Wherein, R ⁴ and R ⁵ each independently represent an alkyl group having 1 to 8 carbon atoms which may be substituted by a fluorine atom, and n represents 2 or 3). A compound represented by 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 represent an alkyl group having 1 to 8 carbon atoms which may be substituted by 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 following 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 represent a C ¹ to C 8 optionally substituted by a fluorine atom. Wherein n represents 2 or 3.) A method for producing a fluorine-containing siloxane compound represented by the formula:
[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 represent a C ¹ to C 8 optionally substituted by a fluorine atom. And n represents 2 or 3.) and a fluorine-containing siloxane compound represented by the general formula (7):

(Wherein, R ⁶ , R ⁷ and R ⁸ each independently represent 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 represents At least one of which 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). , 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 represent a C ¹ to C 8 optionally substituted by a fluorine atom. R ⁶ , R ⁷ and R ⁸ each independently represent 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 ^Wherein at least one of ⁸ is a halogen atom or an alkoxy group having 1 to 3 carbon atoms, and n represents 2 or 3.)
[6]
A coating agent comprising the fluorine-containing siloxane compound according to item 1, 2 or 3, and a liquid medium.
[7]
A method for treating a glass substrate, comprising applying the coating agent according to item 6 to the surface of the substrate and removing the liquid medium.

  According to the method of the present invention, there is provided a low-molecular-weight fluorine-containing siloxane compound having a high fluorine content per unit mass, having one or more fluoroalkyl groups in a molecule, and having a reactive group capable of binding to a substrate. 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 impart good water / oil repellency to the surface of the substrate by preparing a coating agent by dissolving it in a solvent and applying the coating agent.

  Hereinafter, the present invention will be described in detail.

First, the 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, a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a 2-fluoroethyl group, a 1,1,2,2,2-pentafluoroethyl group, a 2,2,2-trifluoroethyl group, , 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- Trifluoro-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 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. In terms of the stability and water repellency of the compound, R ¹ represents 3,3,3-trifluoropropyl, 3,3,4,4,4-pentafluorobutyl, 3,3,4,4,5 , 5,6,6,6-nonafluorohexyl group or 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl group is preferred, 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 any of linear, branched and cyclic, and specifically, a methyl group , Ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, cyclobutyl, n-pentyl, 1-methylbutyl, 2-methylbutyl, isopentyl , 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. Examples can be given. These may be partially or entirely replaced with fluorine atoms. Specifically, a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a 2-fluoroethyl group, a 1,1,2,2,2-pentafluoroethyl group, a 2,2,2-trifluoroethyl group, , 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- Trifluoro-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 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 a 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 a methyl group, an ethyl group, an n-propyl group, a 3,3,3-trifluoropropyl group, a 3,3 , 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, the 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, Examples thereof include a bromine atom, an iodine atom, a methoxy group, an ethoxy group, a (n-propyl) oxy group, and a (1-methylethyl) oxy group. 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, and a methyl group, a chlorine atom, or Methoxy groups are more preferred, and methoxy groups are even more 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, a (1 -Methylethyl) oxy group and the like. In terms of yield, stability, and water repellency, X is preferably a chlorine atom, a bromine atom, a methoxy group, or an ethoxy group, more preferably a chlorine atom or a methoxy group, and particularly preferably a chlorine atom.

  Examples of the fluorine-containing siloxane compound (compound 4) that can be produced by 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-pentane (Fluoroethyl) -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, 1 -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, 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-pentamethyl Tetrasiloxane, 1-hydroxy-7- (3,3,4,4,5,5,6,6,6-nonafluorohexyl) -1,3,5-tris (3,3,3-trifluoropropyl ) To 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. In terms of yield, stability and water repellency, 1-hydroxy-7- (3,3,3-trifluoropropyl) -1,1,3,3,5,5,7,7-octamethyltetra 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, 5,7,9,9-pentamethylpentasiloxane and the like can be exemplified. In terms of yield, stability and water repellency, 1,1,1-trichloro-9- (3,3,3-trifluoropropyl) -3,3,5,5,7,7,9,9 -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) Particularly preferred is -3,5,7,9,9-pentamethylpentasiloxane.

  Next, the manufacturing method of the present invention will be described. The fluorine-containing siloxane compound represented by the compound (4) can be produced by the step 1 of reacting a dihydroxysiloxane compound (compound 5) with a fluoroalkyl-substituted silane compound (compound 6). The fluorine-containing siloxane compound represented by the compound (3) can be produced by the step 2 of reacting the fluorine-containing siloxane compound (4) with the silane compound (7).

(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 represent a C ¹ to C 8 optionally substituted by 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 represent a C ¹ to C 8 optionally substituted by a fluorine atom. R ⁶ , R ⁷ and R ⁸ each independently represent 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 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.)

(Step 1)
Step 1 will be described. Among the dihydroxysiloxane compounds (5) used as a raw material in the step 1, the linear fluorinated trisiloxane compound in which n is 2 or 3 can be obtained by a method described in many patents and non-patent documents by those skilled in the art. It can be easily manufactured (JP-A-2000-113942, Zeitschrift fur 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 the methods described in many patents and non-patent documents (Inorganica Chimica Acta, Vol. 359). , P. 2474, 2006. JP-A-04-059782.).

  It is essential that compound 4 has at least one fluoroalkyl group. Compound 4 can be synthesized by adding compound 6 to a solution of compound 5 in an organic solvent and reacting. The chemical equivalent of compound 6 to compound 5 is preferably prepared in the range of 0.5 to 2 equivalents, and more preferably 0.8 to 1.2 equivalents in terms of a high yield. At the time of this production, it is preferable to add an organic base to accelerate the reaction. As the organic base, an organic amine can be suitably used, 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 6, and more preferably 1 to 2 equivalents.

  Step 1 can be carried out in an atmosphere of air or dry air, but 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 rare gases such as helium, neon, argon, krypton, and xenon, and nitrogen gas, and argon or nitrogen gas is more preferable. The reaction temperature is not particularly limited, and a general temperature condition for a person skilled in the art to produce a siloxane compound having a hydroxyl group can be used. As a specific example, the fluorine-containing siloxane compound of the present invention can be obtained in a high 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 preferred, and more preferably room temperature. The reaction time is appropriately determined by confirming the progress of the reaction by instrumental analysis. Typically, the reaction is preferably performed with a reaction time appropriately selected from the range of 10 minutes to 200 hours.

  Step 1 is preferably performed in an organic solvent in terms of good yield. Usable organic solvents are not limited as long as they do not hinder 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), ethers such as tetrahydrofuran (THF), 1,4-dioxane, 1,2-dimethoxyethane, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, dichloromethane, Halogenated hydrocarbons such as chloroform can be exemplified. One of these organic solvents can be used alone, or a plurality of them can be used as a mixture at an arbitrary ratio. As the organic solvent, ethers are preferred, diethyl ether and THF are preferred, and THF is more preferred, in that the yield is good and the reaction time is short.

  In step 1, the desired product can be purified by appropriately selecting and using a general purification method for purifying a siloxane compound having a hydroxyl group by a person skilled in the art as necessary after the 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.

(Step 2)
It is essential that compound 3 has at least one fluoroalkyl group. The fluorine-containing siloxane compound (4) which can be used as a raw material in the step 2 can be produced by the 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, 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 the methods described in many patents and non-patent documents (Angewante Chemie International Edition, 50, 10708, 2011).

In step 2, it is preferable to add an organic base 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 atmosphere of air or dry air, but is preferably carried out in an atmosphere of an inert gas in terms of good yield. Examples of the inert gas that can be used include rare gases such as helium, neon, argon, krypton, and xenon, and nitrogen gas, and argon or nitrogen gas is more preferable. The reaction temperature is not particularly limited, and a general temperature condition for a person skilled in the art to produce a siloxane compound having a hydroxyl group can be used. As a specific example, the fluorine-containing siloxane compound of the present invention can be obtained in a high 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 preferred, and more preferably room temperature. The reaction time is appropriately determined by confirming the progress of the reaction by instrumental analysis, and is preferably performed with a reaction time appropriately selected from the range of 10 minutes to 200 hours.

  Step 2 is preferably performed in an organic solvent in terms of good yield. Usable organic solvents are not limited as long as they do not inhibit the reaction.Specifically, aliphatic hydrocarbons such as pentane, hexane, cyclohexane and heptane, and aromatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene Ethers such as diethyl ether, diisopropyl ether, cyclopentyl methyl ether (CPME), tetrahydrofuran (THF), 1,4-dioxane and 1,2-dimethoxyethane, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, dichloromethane, Halogenated hydrocarbons such as chloroform can be exemplified. One of these organic solvents can be used alone, or a plurality of them can be used as a mixture at an arbitrary ratio. As the organic solvent, ethers are preferred, diethyl ether and THF are preferred, and THF is more preferred, in that the yield is good and the reaction time is short.

  In step 2, the desired product can be purified by appropriately selecting and using a general purification method for purifying a siloxane compound having a reactive group by a person skilled in the art as necessary after the completion of the reaction. Specific examples of the purification method include washing, filtration, extraction, concentration, distillation, sublimation, recrystallization, and fractionation by normal-phase / reverse-phase liquid chromatography. Purification by distillation under reduced pressure is more preferable in that the purity can be increased by removing high molecular weight impurities.

<Coating agent>
The coating agent of the present invention contains the 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 a liquid, and may be a solution or a dispersion. The coating agent of the present invention only needs to contain the fluorine-containing siloxane compound (1), (2) or (3), and may contain impurities such as by-products generated in the steps 1 and 2. The coating agent of the present invention preferably contains the fluorine-containing siloxane compound (1), (2) or (3) of the present invention in an amount of 0.001 to 10% by mass, more preferably 0.1 to 1% by mass. It is particularly preferable that the coating agent of the present invention contains a fluorine-containing siloxane compound (1), (2) or (3) purified to a purity of 95% by mass or more through Steps 1 and 2, and a liquid medium.

<Liquid medium>
The boiling point of the liquid medium in the present invention is preferably from -10 to 200C, particularly preferably from 40 to 150C. Organic solvents are preferred as the liquid medium. 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-fluorinated 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-based 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 preferred because of its excellent storage stability and high solubility. The coating agent may contain, besides the compound (1), (2) or (3) and the liquid medium, other components as long as the effects of the present invention are not impaired.

The surface treatment of the substrate can be performed by applying a 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. A known method can be appropriately used as a method for applying the coating agent. The coating method is preferably 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-Blodgett method or a gravure coating method, and a spin coating method and a dip coating method. Is more preferred.
The method for removing the liquid medium may be any method capable of evaporating and removing the liquid medium from the coating film of the coating agent, and a known method can be appropriately used. The temperature at which the liquid medium is removed by evaporation may be any temperature as long as it is equal to or higher than the boiling point of the liquid medium, and is appropriately selected depending on the type of the liquid medium. Further, 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 through the surface treatment layer and a method of wiping with a cloth impregnated with the solvent.

<Substrate>
In the present invention, the substrate to be subjected to the surface treatment is not particularly limited as long as it is a glass substrate which is required to be imparted with water / oil repellency.

  By treating the surface of the substrate with the fluorine-containing siloxane compound (compound (1)) of the present invention or a coating agent containing the compound to form a surface-treated layer, good water and oil repellency is imparted. You. Further, since the surface treatment layer is colorless and transparent, it is suitable as a member constituting a touch panel. The touch panel means an input device of an input / display device (touch panel device) in which a device for inputting contact position information by contact with a finger or the like and a display device are combined. The touch panel includes a base material, a transparent conductive film, an electrode, a wiring, an IC, and the like according to an input detection method. By using the surface of the substrate having the surface treatment layer as the input surface of the touch panel, a touch panel having good fingerprint removability can be obtained. The material of the substrate for the touch panel has a light transmitting property. As the material of the substrate for the touch panel, 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 strengthened glass is particularly preferable.

  Further, as a 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. By forming the surface treatment layer by surface treatment using a coating agent, good stain removal properties can be obtained.

  Hereinafter, the present invention will be described specifically with reference to Examples and Reference Examples, but the present invention is not limited to the following Examples.

(Reference Example 1)

A 200 mL two-necked flask equipped with a magnetic stirrer and a Dimroth condenser was replaced with argon, and 0.125 g (0.135 mmol) of chlorotris (triphenylphosphine) rhodium (I), 50 mL of dehydrated toluene, 3, 3, 4, It contained 12.4 g (50.3 mmol) of 4,5,5,6,6,6-nonafluoro-1-hexene and 9.46 g (100 mmol) of chlorodimethylsilane. The mixture was heated under reflux at 120 ° C. for 10 hours, and the completion of the reaction was confirmed by gas chromatography. After distilling off toluene by atmospheric pressure distillation, chloro (3,3,4,4,5,5,6,6,6-nonafluorohexyl) dimethyl is obtained by distillation under reduced pressure (boiling point 67 ° C./2.9 kPa). 6.78 g (yield 39.6%, GC purity 80%) of silane was obtained as a colorless 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)

The 200-mL two-necked flask equipped with a magnetic stirrer and a Dimroth condenser was replaced with argon, and 0.268 g (0.290 mmol) of chlorotris (triphenylphosphine) rhodium (I), 50 mL of dehydrated toluene, (perfluorohexyl) It contained 21.1 g (60.8 mmol) of ethylene and 12.8 g (136 mmol) of chlorodimethylsilane. After heating under reflux at 150 ° C. for 18 hours, 5.48 g (57.9 mmol) of chlorodimethylsilane was added, and the mixture was heated under reflux at 150 ° C. for 3 hours. The completion of the reaction was confirmed by gas chromatography. After toluene was distilled off under reduced pressure, chloro (3,3,4,4,5,5,6,7,6,7,7) was distilled under reduced pressure (distillation temperature 50 ° C / 40Pa) using a Kugelrohr distillation apparatus. (8,8,8-Tridecafluorooctyl) dimethylsilane was obtained as a colorless and 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)

The 200 mL two-necked flask equipped with a magnetic stirrer and a Dimroth condenser was replaced with argon, and 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). The mixture was heated under 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, 7 10.3 g (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. .3; 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 Dimroth was replaced with argon, and charged with t-butylmethyl ether (155 g, 1.77 mol) and bismuth chloride (1.87 g, 5.89 mmol). At room temperature, silicon tetrachloride (99.2 g, 0.589 mol) was added dropwise from the dropping funnel over 2 hours. After stirring at room temperature for 15 hours, it was confirmed by gas chromatography that the reaction was completed. The mixture was distilled under normal pressure (boiling point: 112 ° C.) to obtain 67.4 g (yield: 73.1%) of the target chlorotrimethoxysilane.
_{GC-MS (EI, 70eV)} , m / z (%): 141 ([M-CH 3] +, 9.4), 111 (12), 120 (100). ¹ H NMR (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 7- (3,3,3-trifluoropropyl) -1,1,3,3,5,5,7,7-octamethyltetrasiloxane-1-ol (Compound 2-A) Synthesis

A 200 mL three-necked flask equipped with a magnetic stirrer, 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), 50.0 mL of dehydrated diethyl ether, and 2.24 g (23.2 mmol) of triethylamine were contained. 50.0 mL of dehydrated diethyl ether and 3.94 g (20.7 mmol) of (3,3,3-trifluoropropyl) chlorodimethylsilane were placed in a dropping funnel, and the flask was cooled to 0 ° C. and dropped over 2.5 hours. did. After the dropwise addition, 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 separating funnel, the organic layer is concentrated with a rotary evaporator, and then separated using a recycle-type high performance liquid chromatography (mobile layer: methanol) to obtain the desired 7- (3,3). 5.12 g (3,3-trifluoropropyl) -1,1,3,3,5,5,7,7-octamethyltetrasiloxane-1-ol (compound 2-A) as a colorless and transparent liquid was obtained. 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 ^{.00~2.13 (m, 2H); 13} C-NMR (100MHz, 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 stir 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), 15.0 mL of dehydrated diethyl ether, and 1.65 g (16.3 mmol) of triethylamine were contained. 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 over 30 minutes And dropped. After the dropwise addition, 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 fractionated using a recycle-type high performance liquid chromatography (mobile layer: methanol) to obtain the desired 7- (3,3,4,7). 4,5,5,6,6,6-nonafluorohexyl) -1,1,3,3,5,5,7,7-octamethyltetratrisiloxane-1-ol (compound 2-B) 4.70 g (yield 58.4%, GC purity 82%) was obtained as a transparent liquid.
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 0.02 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, 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. 47 g (6.10 mmol), 5.0 mL of dehydrated diethyl ether and 0.627 g (6.20 mmol) of triethylamine were contained. 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 were placed in a dropping funnel. Over 30 minutes. After the dropwise addition, 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 fractionated using a recycle-type high performance liquid chromatography (mobile layer: methanol) to obtain the desired 7- (3,3,4,7). 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 of (Compound 2-C) was obtained as a colorless transparent liquid (yield: 81.7%, GC purity: 96%).
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 0.02 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, −10.4, ^{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, a Liebig condenser, and a dropping funnel was purged with argon, and the flask was charged with 1,1,3,3,5,5-hexamethyltrisiloxane-1,5-diol. It contained 88 g (12.0 mmol), 10.0 mL of dehydrated diethyl ether and 1.32 g (13.0 mmol) of triethylamine. 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) were added to the dropping funnel. 5.40 g (9.99 mmol) of (decyl) silane was added and added dropwise over 1 hour. After the dropwise addition, 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 separated using a recycle-type high performance liquid chromatography (mobile layer: methanol) to obtain the desired compound (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 and 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 0.07 (s, 6H), 0.09 (s, 6H), 0.14 (s, 6H), 0.15 (s, 6H) 0.76-0.80 (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)

The 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, 30.0 mL of dehydrated diethyl ether, and 2.46 g (31.0 mmol) of pyridine were contained. 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. The desired 9- (3,3,3-trifluoropropyl) -3,3,5,5,7,7,7-distilled by distillation under reduced pressure (distillation temperature 135 ° C./40 Pa) using a Kugelrohr distillation apparatus. 3.26 g (yield: 65.0%, GC purity: 98.8%) of 9,9-octamethyl-1,1,1-trimethoxypentasiloxane (compound 1-A) was obtained as a colorless and 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)

The 50 mL two-necked flask equipped with a magnetic stir bar and a Liebig condenser was replaced with argon, and 7- (3,3,4,4,5,5,6,6,6-nonafluorohexyl) 1,1,1 was added. 3.68 g (6.75 mmol) of 3,3,5,5,7,7-octamethyltrisiloxane-1-ol, 20.0 mL of dehydrated diethyl ether and 1.54 g (19.5 mmol) of pyridine were contained. 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 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 desired 9- (3,3,4,4,5,5,6,6,6-nonafluorohexyl)-was obtained by performing vacuum distillation (a distillation temperature of 135 ° C./40 Pa) using a Kugelrohr distillation apparatus. 2.85 g of 3,3,5,5,7,7,9,9-octamethyl-1,1,1-trimethoxypentasiloxane (compound 1-B) as a colorless and transparent liquid (yield 63.5%) , 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)

The 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 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 desired 9- (3,3,4,4,5,5,6,6,7,7,8,8) was obtained by performing 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 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 (} 79MHz, 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)

The 50 mL two-necked flask equipped with a magnetic stir bar and a Liebig condenser was replaced with argon, and (3,3,4,4,5,5,6,6,7,7,8,8,9,9,9, 4.5.10 g (6.05 mmol) of 10,10,10-heptadecafluorodecyl) -1,1,3,3,5,5,7,7-octamethyltrisiloxane-1-ol, dehydrated diethyl ether It contained 0 mL and 1.44 g (18.2 mmol) of pyridine. 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. The desired 9- (3,3,4,4,5,5,6,6,7,7,8,8) was obtained by performing vacuum distillation (distillation temperature: 145 ° C./40 Pa) using a Kugelrohr distillation apparatus. , 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 (4.09 g, 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 to 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 was replaced with argon. It contained 2.85 g of siloxane-1,5-diol, 8.0 mL of dehydrated diethyl ether and 0.865 g of triethylamine. The dropping funnel contained 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 the dropwise addition, the mixture was stirred at room temperature for 2 hours, and the completion of the reaction was confirmed by gas chromatography (GC). After washing the reaction mixture with water and concentrating the solvent with a rotary evaporator, 7- (3,3,4,4,5,5,6,6,6-nonafluorohexyl) is used by 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 (55.2% yield) 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 to 0.19 (m, 15H), 0.76 to 0.80 (m, 2H), 2.00 to 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)

The 50 mL two-necked flask equipped with a magnetic stir bar and a Liebig condenser was replaced with argon, and 7- (3,3,4,4,5,5,6,6,6-nonafluorohexyl) -1,3 2.32 g (2.93 mmol) of 1,5-tris (3,3,3-trifluoropropyl) -1,3,5,7,7-pentamethyltetrasiloxane-1-ol and 12.0 mL of dehydrated diethyl ether , 1.01 g (12.7 mmol) of pyridine. 1.77 g (11.3 mmol) of trimethoxychlorosilane was added with a syringe over 10 minutes, the mixture was stirred at 25 ° C. for 3 hours, and 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 desired 9- (3,3,4,4,5,5,6,6,6-nonafluorohexyl)-was obtained by performing vacuum distillation (distillation temperature 150 ° C./35 Pa) using a Kugelrohr distillation apparatus. Colorless and transparent 3,5,7-tris (3,3,3-trifluoropropyl) -3,5,7,9,9-pentamethyl-1,1,1-trimethoxypentasiloxane (Compound 1-E) 1.45 g (yield 54.4%) was obtained as a liquid.
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, -0.82, -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, a Liebig condenser, and a dropping funnel was purged 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). Add 7- (3,3,4,4,5,5,6,6,6-nonafluorohexyl) -1,3,5-tris (3,3,3-trifluoropropyl) -1 to the dropping funnel. , 3,5,7,7-Pentamethyltetrasiloxane-1-ol 3.17 g (4.01 mmol) and dehydrated diethyl ether 10.0 mL were added and added dropwise over 1 hour. After the dropwise addition, 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 desired 9- (3,3,4,4,5,5,6,6,6-nonafluorohexyl)-is obtained by distillation under reduced pressure (distillation temperature: 145 ° C./40 Pa) using a Kugelrohr distillation apparatus. 3,5,7-Tris (3,3,3-trifluoropropyl) -3,5,7,9,9-pentamethyl-1,1,1-trichloropentasiloxane (Compound 1-F) 0.457 g (yield 12.3%) was obtained as a liquid.
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 (79MHz, CDCl 3): δ-22.4, -21.7, -17.7,3.38,9 .42; 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 stir bar, a Liebig condenser, and a dropping funnel was purged with argon, and 1.64 g (1,9,3,3-tetramethyldisiloxane-2,4-diol) was added to the flask. 85 mmol), 10.0 mL of dehydrated diethyl ether and 0.953 g (9.42 mmol) of triethylamine. 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 in a dropping funnel, and over 35 minutes And dropped. After the dropwise addition, 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 by a rotary evaporator, and then subjected to reduced pressure distillation (distillation temperature: 100 ° C./40 Pa) using a Kugelrohr distillation apparatus to obtain the desired 5- (3,3,4,4). 4,5,5,6,6,6-nonafluorohexyl) -1,1,3,3,5,5-hexamethyltrisiloxane-1-ol (compound 2-F) as a colorless and transparent liquid 2 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 stir bar, a Liebig condenser, and a dropping funnel was purged 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. 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 were placed in a dropping funnel. Over 25 minutes. After the addition, the mixture was stirred at 25 ° C. for 3 hours. The reaction mixture is washed with water, the organic layer is concentrated on a rotary evaporator, and then subjected to reduced-pressure distillation (distillation temperature: 95 ° C./20 Pa) using a Kugelrohr distillation apparatus to obtain the desired 5- (3,3,4,4). 4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl) -1,1,3,3,5,5-hexamethyltrisiloxane-1-ol (compound 2- G) was obtained as a colorless transparent liquid (6.85 g, yield 74.6%).
GC-MS (EI, 70eV) 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), 0.76-0.80 (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, a Liebig condenser, and a 50 mL dropping funnel was purged with argon, and the flask was charged with 3.30 g of 1,1,3,3-tetramethyldisiloxane-2,4-diol (20 mL). 1.0 mmol), 140 mL of dehydrated diethyl ether and 1.70 g (16.8 mmol) of triethylamine. In a dropping funnel, 10.0 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) 7.01 g (13.0 mmol) of decyl) silane was placed, cooled to 0 ° C. in an ice bath, and added dropwise over 20 minutes. After the dropwise addition, the mixture was stirred at 25 ° C. for 90 minutes. The reaction mixture is washed with water, the organic layer is concentrated by a rotary evaporator, and then subjected to reduced pressure distillation (distillation temperature 110 ° C./20 Pa) using a Kugelrohr distillation apparatus to obtain the desired 5- (3,3,4,4). 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 and 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, a Liebig condenser, and a 25 mL dropping funnel was purged with argon, and 5- (3,3,4,4,5,5,6,6,6-nonafluorohexyl) was added. 1.88 g (3.99 mmol) of -1,1,3,3,5,5-hexamethyltrisiloxane-1-ol, 5.0 mL of dehydrated diethyl ether, and 0.469 g (5.93 mmol) of pyridine were contained. 5.0 mL of dehydrated diethyl ether and 0.981 g (6.26 mmol) of trimethoxychlorosilane were placed in a dropping funnel and added dropwise at 0 ° C. over 10 minutes. 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. The desired 7- (3,3,4,4,5,5,6,6,6-nonafluorohexyl)-was obtained 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 and transparent liquid.
GC-MS (EI, 70 eV) m / z (%): 575 (21), 347 (60), 343 (100), 239 (60), 223 (39), 105 (39); ¹ H-NMR ( _{400MHz, CDCl 3): δ0.08 (} s, 6H), 0.14 (m, 12H), 0.75~0.79 (m, 2H), 1.99~2.13 (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, a Liebig condenser, and a 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 a dropping funnel, and dropped over 5 minutes. Stirred 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. The desired 7- (3,3,4,4,5,5,6,6,7,7,8,8) was obtained by distillation under reduced pressure (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, yield 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. ２．１2.13 (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, a Liebig condenser, and a 25 mL dropping funnel was purged 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 contained. 15.0 mL of dehydrated diethyl ether and 0.787 g (5.24 mmol) of trimethoxychlorosilane were placed in a dropping funnel, 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. The desired 7- (3,3,4,4,5,5,6,6,7,7,8,8) was obtained 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) 1.87 g (yield 71.9%) was obtained as a liquid.
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 to 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 by dip coating on this solution at 50 ° C. went. The contact angles of water and hexadecane (droplet volume: 1 μL) were determined at five locations on the modified surface by the θ / 2 method, and the average was determined. The contact angle with water was 65.5 ° and the contact angle with hexadecane was 18.9. ° 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 by dip coating on this solution at 50 ° C. went. The contact angles of water and hexadecane (droplet volume: 1 μL) were determined at five places on the modified surface by the θ / 2 method, and the average was determined. The contact angle with water was 75.1 °, and the contact angle with hexadecane was 26.1. ° 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 on this solution at 50 ° C. by dip coating. went. The contact angles of water and hexadecane (droplet volume: 1 μL) were determined by the θ / 2 method at the five modified surfaces, and the average was determined. The contact angle with water was 49.8 ° and the contact angle with hexadecane was 22.1. ° 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 on this solution by dip coating at 50 ° C. went. The contact angle of water and hexadecane (droplet volume: 1 μL) was determined by the θ / 2 method at five places on the modified surface, and the average was determined. The contact angle with water was 64.6 °, and the contact angle with hexadecane was 17.8. ° 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 on this solution by dip coating at 50 ° C. went. The contact angle k of water and hexadecane (droplet volume 1 μL) was determined by the θ / 2 method at five places on the modified surface, and the average was determined. 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 by dip coating on this solution at 50 ° C. went. The contact angle k of water and hexadecane (droplet amount: 1 μL) was determined at the five modified surfaces by the θ / 2 method, and the average was determined. 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 on this solution by dip coating at 50 ° C. went. The contact angle k between water and hexadecane (droplet volume: 1 μL) was determined by the θ / 2 method at five places on the modified surface, and the average was determined. 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 glass substrate with compound 2-B A 0.3% by weight chloroform solution of compound 2-B was prepared, and a soda glass substrate was formed by dip coating on this solution at 50 ° C. went. The contact angle k of water and hexadecane (droplet amount: 1 μL) was determined by the θ / 2 method at five places on the modified surface, and the average was determined. 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 on this solution by dip coating at 50 ° C. went. The contact angle k of water and hexadecane (droplet volume: 1 μL) was determined by the θ / 2 method at five places on the modified surface, and the average was determined. The contact angle with water was 53.8 ° and the contact angle with 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 by dip coating on this solution at 50 ° C. went. The contact angle k of water and hexadecane (droplet amount: 1 μL) was determined at the five modified surfaces by the θ / 2 method, and the average was determined. The contact angle with water was 58.2 ° and the contact angle with hexadecane was 20. A value of 8 ° was obtained.

(Example 27) Surface treatment of compound 2-E on glass substrate A 0.3% by weight chloroform solution of compound 2-E was prepared, and a soda glass substrate was formed by dip coating on this solution at 50 ° C. went. The contact angle k between water and hexadecane (droplet volume: 1 μL) was determined by the θ / 2 method at five places on the modified surface, and the average was determined. 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 by dip coating on this solution at 50 ° C. went. The contact angle k of water and hexadecane (droplet amount: 1 μL) was determined at the five modified surfaces by the θ / 2 method, and the average was determined. 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 on this solution by dip coating at 50 ° C. went. The contact angle k of water and hexadecane (drop volume: 1 μL) was determined by the θ / 2 method at five places on the modified surface, and the average was determined. As a result, 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 glass substrate with 1,1,1-trimethoxy-7-phenyl-1,1,3,3,5,5,7,7-octamethylpentasiloxane 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 between water and hexadecane (droplet volume: 1 μL) was determined at the five modified surfaces by the θ / 2 method, and the average was determined. 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 / oil repellency on the surface can be provided. Further, as a fluorine-containing silane coupling agent, the surface of a substrate can be modified and used as an adhesive and dispersant for the substrate.

Claims (3)

General formula (1)

(Wherein, R ¹ represents a fluoroalkyl group having 2 to 8 carbon atoms. R ² , R ³ , R ⁴ and R ⁵ each independently represent a C ¹ to C 8 optionally substituted with a fluorine atom. And n represents 2 or 3. Z represents the general formula (2)

(Wherein, R ⁶ , R ⁷ and R ⁸ each independently represent 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 represents At least two of them are a halogen atom or an alkoxy group having 1 to 3 carbon atoms.). A) a fluorine-containing siloxane compound represented by the formula: A coating agent comprising the fluorine-containing siloxane compound according to claim 1 and a liquid medium. A method for treating a surface of a glass substrate, comprising applying the coating agent of claim 2 to the surface of the substrate and removing the liquid medium.