JP5893398B2 - Silicon-containing treatment agent and water repellent film - Google Patents

Description

  The present invention relates to a silicon-containing treatment agent having optical transparency and capable of easily forming a water-repellent film having excellent light resistance, heat resistance, and chemical stability, and a method for producing the same. Furthermore, the present invention relates to a water repellent film using a silicon-containing treatment agent.

  Conventionally, as a water and oil repellency imparting agent applied to various substrate surfaces, a substrate is immersed in a solution of a fluoroalkylalkoxysilane compound or an alkylalkoxysilane compound and subjected to a heat treatment to obtain a fluoroalkylsilane group or an alkylsilane. Patent Document 1 discloses a method for forming a film having a group. The water / oil repellency imparting agent shown in Patent Document 1 is a heat treatment using a fluoroalkylalkoxysilane compound or an alkylalkoxysilane compound alone, and the silane compound is a polyoxygen than a heat treatment using a monomer. This is what makes silane.

  Patent Document 2 discloses that cosmetic pigments having water repellency and oil repellency can be formed by subjecting a perfluoroalkylalkoxysilane and a polysiloxane derivative to a surface coating treatment. Also in Example 2, a monomer is used for the fluoroalkylalkoxysilane used.

  As described above, the treatment agent using the fluoroalkylalkoxysilane monomer has a problem that the side chain containing the perfluoroalkyl group is not uniform and sufficient water repellency cannot be obtained.

  Further, Patent Document 3 is a mixture of a fluorocarbon group-containing alkoxysilane, an alkylalkoxysilane, and an alkylsilicate, and the formed product is sufficient because the side chain containing a perfluoroalkyl group is not uniform. There was a problem similar to the above in that water repellency was not achieved.

JP2002-105661 JP2007-91638 JP2008-38086

  The present invention solves the above-mentioned problem, and without using a fluoroalkylalkoxysilane as a monomer, it has optical transparency, and a water repellent film excellent in light resistance, heat resistance, and chemical stability can be easily obtained. An object is to provide a silicon-containing treatment agent that can be formed. It is another object of the present invention to provide a water-repellent film excellent in optical transparency, light resistance, heat resistance, and chemical stability.

In order to solve the above-mentioned problems, the present inventors have conducted intensive research, and as a result, have completed the present invention characterized in that it contains a polysiloxane comprising a side chain containing an alkoxy group and a perfluoroalkyl group as a side chain. It came.
That is, the silicon-containing treatment agent of the present invention is characterized by the following.

［４］前記ポリシロキサンに加えて、主鎖のケイ素に側鎖としてアルコキシ基及び反応性官能基を含むアルキルシロキシル基（アルキルシロキシル基の一部がアルキル基であるものを含む）が結合したポリシロキサンを含むことを特徴とする前記［１］〜［３］のいずれかに記載のケイ素含有処理剤
［５］前記主鎖のケイ素に側鎖としてアルコキシ基及び反応性官能基を含むアルキルシロキシル基が結合したポリシロキサンが、化学式３又は４（Ｒ^rは反応性官能基を含むアルキルシロキシル基（アルキルシロキシル基の一部がアルキル基であるものを含む）、Ｒはアルキル基、Ｒ^１はアルキル基又はアルコキシシロキシル基、ｍは１以上の整数、ｎは０又は１以上の整数で、１≦ｍ＋ｎ≦２０）で表されるポリシロキサンであることを特徴とする前記［４］に記載のケイ素含有処理剤

［６］前記［１］から［５］のいずれかに記載のケイ素含有処理剤を基材表面に塗布してなる撥水膜 [1] A silicon-containing treatment agent comprising a polysiloxane formed by bonding a side chain containing an alkoxy group and a perfluoroalkyl group as a side chain to silicon of a main chain.
[2] An alkylsiloxyl group in which the side chain containing the perfluoroalkyl group includes a perfluoroalkyl group represented by the structural formula C _X F _{2X + 1} (1 ≦ x ≦ 6) (a part of the alkylsiloxyl group is an alkyl group) The silicon-containing treatment agent according to [1], wherein the silicon-containing treatment agent is.
[3] The polysiloxane is represented by chemical formula 1 or 2 (R ^f is an alkylsiloxyl group containing a perfluoroalkyl group having 1 to 6 carbon atoms (including a part of the alkylsiloxyl group is an alkyl group), R Is an alkyl group, R ¹ is an alkyl group or an alkoxysiloxyl group, m and n are integers of 1 or more, and is a polysiloxane represented by m ≦ n, 4 ≦ m + n ≦ 20) The silicon-containing treatment agent according to [1] or [2]

[4] In addition to the polysiloxane, an alkylsiloxyl group containing an alkoxy group and a reactive functional group as a side chain (including those in which a part of the alkylsiloxyl group is an alkyl group) is bonded to silicon of the main chain. [5] The silicon-containing treating agent according to any one of [1] to [3], wherein the main chain silicon includes an alkoxy group and a reactive functional group as a side chain. A polysiloxane to which a siloxyl group is bonded is represented by chemical formula 3 or 4 (R ^r is an alkylsiloxyl group containing a reactive functional group (including a part of the alkylsiloxyl group is an alkyl group), and R is an alkyl group. , characterized in that R ¹ is an alkyl group or an alkoxyalkyl siloxyl group, m is an integer of 1 or more, n represents 0 or an integer of 1 or more, a polysiloxane represented by 1 ≦ m + n ≦ 20) Silicon-containing treatment agent according to [4] to

[6] A water-repellent film formed by applying the silicon-containing treatment agent according to any one of [1] to [5] to a substrate surface

  The silicon-based treatment agent of the present invention can easily form a homogeneous water-repellent film due to its chemical structure. That is, when the silicon-based treatment agent of the present invention is applied to the substrate surface, the alkoxy groups are organized on the substrate side by self-organization, and the perfluoroalkyl groups are arranged on the surface side of the film, so that the water repellent performance is good. It is possible to form a water repellent film having Since the main component is a silicon compound, it is possible to form a water-repellent film having optical transparency and excellent light resistance, heat resistance, and chemical stability.

  In addition, the coexistence of the compounds of Chemical Formulas 3 and 4 containing a polymerizable functional group makes it possible to impart affinity to the base material and the silicon composition, and it is easy to obtain uniform water repellency even on organic base materials. The film can be formed in a single step. That is, also in this case, the self-organization of the silicon-based treatment agent of the present invention occurs, and a perfluoroalkyl group is arranged on the surface of the film to be formed, and the silicon-based treatment agent of the present invention is applied to the substrate surface. It is possible to form a tilted film simply by simply.

  Furthermore, when a perfluoroalkyl group-containing fluoropolymer having 6 or less carbon atoms is used, perfluorooctanoic acid (PFOA) is not generated by decomposition of the fluoropolymer having a perfluoroalkyl group, and the PFOA biological There is also an effect that the influence on the environment such as the possibility of accumulation in the environment can be improved.

²⁹ Si-NMR spectrum of polysiloxane as the product of Example 1 ²⁹ Si-NMR spectrum of nonafluorohexyltrimethoxysilane ²⁹ Si-NMR spectrum of polysiloxane as product of Example 3 ²⁹ Si-NMR spectrum of methacryloxypropyltrimethoxysilane

  Next, specific embodiments of the silicon-containing treatment agent of the present invention and a water-repellent film using the same will be described.

  The silicon-containing treatment agent of the present invention is not particularly limited as long as it contains a polysiloxane formed by bonding a side chain containing a perfluoroalkyl group as a side chain to the main chain silicon, but in terms of environmental considerations. The side chain containing the perfluoroalkyl group is preferably an alkylsiloxyl group containing a perfluoroalkyl group having 6 or less carbon atoms (including a part of the alkylsiloxyl group being an alkyl group).

  The silicon-containing treatment agent of the present invention contains the above polysiloxane, but may be the above polysiloxane itself, or may contain an alkoxysilane polymer and the compound represented by Formula 3 or 4 in addition to the above polysiloxane. It may contain compounds such as various alkoxysilane polymers such as alkoxysilane polymers substituted with functional groups and various alcosilane polymers. And the solution in which these things were melt | dissolved in the solvent may be sufficient.

  The main chain of the polysiloxane into which the alkylsiloxyl group containing a perfluoroalkyl group having 6 or less carbon atoms is introduced may be linear, branched or cyclic, and is not particularly limited.

  More specifically, the silicon-containing treatment agent of the present invention is a silicon-containing treatment agent containing the chemical formula (1) or (2).

In the chemical formula (1) or (2), R ^f is an alkylsiloxyl group containing a perfluoroalkyl group having 1 to 6 carbon atoms (including a part of the alkylsiloxyl group is an alkyl group), and R is An alkyl group, R ¹ is an alkyl group or an alkoxysiloxyl group, m ≦ n, 4 ≦ m + n ≦ 20.

In the alkylsiloxyl group containing a perfluoroalkyl group having 6 or less carbon atoms and R ^f , the alkylsiloxyl group is an alkylsiloxyl group including a part of the alkylsiloxyl group being an alkyl group. This is because, in the process of producing the polysiloxane of the present invention, there is a possibility that an alkyl group may be bonded to the main chain silicon instead of an alkylsiloxyl group as a side reaction.
Even if an alkyl group is introduced into a part of the alkylsiloxyl group, a perfluoroalkyl group is bonded to the terminal, and the effect as the silicon-containing treatment agent of the present invention is not changed at all.

R ^f is an alkylsiloxyl group (Chemical Formula 6) having a perfluoroalkyl group represented by Chemical Formula 5 at its end, and x in Chemical Formula 5 and Chemical Formula 6 is preferably 1-6. If it exceeds 7, perfluoroalkyl acid is formed as a decomposition product of the final product, which is not preferable. Further, y in Chemical Formula 5 and Chemical Formula 6 is not particularly limited because it is determined by the relationship with x, but 0 to 5 is preferable.

In Chemical Formula 6, R ² and R ³ are any of an alkyl group, an alkoxyl group, and a fluoroalkylsiloxyl group, and R ² and R ³ may be the same or different.

  The degree of polymerization (m + n) in Chemical Formulas 1 and 2 is not particularly limited as long as it is soluble in the solvent used as the coating solution, but is preferably 4 to 20. When it is smaller than 4, it becomes difficult to constitute the polymerizable silicon compound of the present invention. If it exceeds 20, problems in handling such as a decrease in solubility may occur, so 20 is sufficient.

The amount ratio (m / n ratio of the chemical formulas 1 and 2) of the siloxane part into which the R ^f group is introduced and the non-introduced siloxane part is not particularly limited, but preferably m ≦ n. The siloxane unit ^the R ^f group has been introduced and not installed siloxane unit is may be present as a block be present continuously each alternately, as much as possible, R ^f with respect to non-introducing siloxane unit It is preferable that the siloxane part into which the group is introduced is present uniformly.

  The polysiloxane contained in the silicon-based treatment agent of the present invention is synthesized by a reaction between an alkoxysilane or an alkoxysilane polymer and a fluoroalkylalkoxysilane. Specifically, after partially hydrolyzing an alkoxyl group by adding water to a fluoroalkylalkoxysilane solution, a silicon-based treatment agent is formed by mixing with an alkoxysilane or an alkoxysilane polymer or a solution thereof. To obtain a polysiloxane having a side chain containing a perfluoroalkyl group bonded thereto.

  The reaction solvent is not particularly limited as long as the raw materials and products are possible or dispersible, but the following solvents are preferably used.

  That is, preferable solvents include aromatic solvents such as benzene, toluene, ethylbenzene and xylene, hydrocarbon solvents such as hexane, pentane, octane and cyclohexane, ketones such as acetone and methyl ethyl ketone, ethyl acetate and acetic acid. Ester solvents such as propyl, cyclic ether solvents such as tetrahydrofuran and dioxane, alcohol solvents such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol and t-butanol, glycol, glycerol, Glycols such as diethylene glycol and triethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl Ether, ethylene glycol monoacetate, ethylene glycol diacetate, ethylene glycol monomethyl ether acetate, propylene glycol-α-monomethyl ether, propylene glycol-α-monoethyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol-α-acetate Glycol derivatives such as are used.

  The partial hydrolysis of the fluoroalkylalkoxysilane is preferably performed by adding 1 to 2 moles of water to a solution obtained by dissolving the fluoroalkylalkoxysilane in the above solvent at a ratio of 1 to 60% by weight. A more preferable amount of water added is 1.1 to 1.5 mole times. If the amount of water added is small, sufficient hydrolysis will not proceed, and a polysiloxane composed of a side chain containing an alkoxy group and a perfluoroalkyl group as the target side chain cannot be efficiently formed. When the amount of water added is large, polycondensation between fluoroalkylalkoxysilanes proceeds, and polysiloxanes composed of side chains containing alkoxy groups and perfluoroalkyl groups as side chains cannot be efficiently formed.

The hydrolysis proceeds only by adding water, but it is preferable to use a catalyst in combination. As the catalyst, mineral acids such as hydrochloric acid, nitric acid, sulfuric acid and phosphoric acid, organic acids such as formic acid and acetic acid, bases such as ammonia, amine, sodium hydroxide and potassium hydroxide are used.
The catalyst is preferably used in an aqueous solution with a concentration of about 0.005 to 5M.

  The reaction time for the hydrolysis of the fluoroalkylalkoxysilane is not particularly limited as long as the hydrolysis of the fluoroalkylalkoxysilane proceeds and the formed hydroxyl group can exist stably, but it is preferably 10 minutes to 2 hours. More preferably, it is 15 minutes to 1 hour.

  The reaction temperature is not particularly limited as long as hydrolysis of the fluoroalkylalkoxysilane proceeds and the formed hydroxyl group can exist stably, but a range of 0 to 50 ° C. is preferable.

  The fluoroalkylalkoxysilane used in the present invention includes fluoroalkyltrialkoxysilane in which one perfluoroalkyl group and three alkoxyl groups are bonded to silicon, one perfluoroalkyl group, one alkyl group and two A fluoroalkylalkyldialkoxysilane having an alkoxyl group bonded thereto and a fluoroalkyldialkylalkoxysilane having one perfluoroalkyl group, two alkyl groups and one alkoxyl group bonded to silicon, wherein the perfluoroalkyl group is a carbon atom. Fluoroalkyl groups of formulas 1 to 8, such as trifluoromethyl group, pentafluoroethyl group, heptafluoropropyl group, heptafluoroisopropyl group, nonafluorobutyl group, nonafluoroisobutyl group, It is one of linear or branched perfluoroalkyl groups such as ndecafluoropentyl group, tridecafluorohexyl group, pentadecafluoroheptyl group, heptadecafluorooctyl group, and the alkyl group is methyl Fluoroalkyl, which is any one of a group, an ethyl group, and a propyl group, and the alkoxy group is any one of an alkoxy group having 1 to 6 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group, and a butoxy group An alkoxysilane etc. are mentioned.

  Preferably, trifluoropropyltrimethoxysilane, pentafluorobutyltrimethoxysilane, heptafluoropentyltrimethoxysilane, nonafluorohexyltrimethoxysilane, undecafluoroheptyltrimethoxysilane, tridecafluorooctyltrimethoxysilane, pentadecafluoro Fluoroalkyltrimethoxysilanes such as nonyltrimethoxysilane, heptadecafluorodecyltrimethoxysilane, nonadecafluoroundecyltrimethoxysilane, trifluoropropyltriethoxysilane, pentafluorobutyltriethoxysilane, heptafluoropentyltriethoxysilane , Nonafluorohexyltriethoxysilane, undecafluoroheptyltriethoxylane, tridecafluorooctyltri Fluoroalkyltriethoxysilanes such as toxisilane, pentadecafluorononyltriethoxysilane, hepadecafluorodecyltriethoxysilane, nonadecafluoroundecyltriethoxysilane, trifluoropropylmethyldimethoxysilane, pentafluorobutylmethyldimethoxysilane, hepta Fluoropentylmethyldimethoxysilane, nonafluorohexylmethyldimethoxysilane, undecafluoroheptylmethyldimethoxysilane, tridecafluorooctylmethyldimethoxysilane, pentadecafluorononylmethyldimethoxysilane, heptadecafluorodecylmethyldimethoxysilane, nonadecafluoroundecyl And fluoroalkylmethyldimethoxysilanes such as methyldimethoxysilane.

  More preferably, trifluoropropyltrimethoxysilane, pentafluorobutyltrimethoxysilane, heptafluoropentyltrimethoxysilane, nonafluorohexyltrimethoxysilane, trifluoropropyltriethoxysilane having a fluoroalkyl group having 3 to 6 carbon atoms , Pentafluorobutyltriethoxysilane, heptafluoropentyltriethoxysilane, nonafluorohexyltriethoxysilane, trifluoropropylmethyldimethoxysilane, pentafluorobutylmethyldimethoxysilane, heptafluoropentylmethyldimethoxysilane, nonafluorohexylmethyldimethoxysilane, etc. And alkoxysilanes.

  The polysiloxane contained in the intended silicon-containing treatment agent is obtained by mixing and reacting the obtained partial hydrolyzate of fluoroalkylalkoxysilane and alkoxysilane or alkoxysilane polymer in a solution in the above solvent. .

  When alkoxysilane is used, the alkoxysilane is not particularly limited, but an alkoxysilane having an alkoxyl group having 1 to 4 carbon atoms is preferable. Particularly preferred alkoxysilanes include tetramethoxysilane, tetratoxylsilane, tetrapropoxysilane, tetrabutoxysilane and the like.

  When using alkoxysilane, first, the resulting hydroalkylalkoxysilane partial hydrolyzate and alkoxysilane are mixed and reacted in a solution of the above solvent, and then additional alkoxysilane is added for hydrolysis and polymerization. By doing so, the polysiloxane contained in the target silicon-containing treatment agent is obtained.

  The reaction in the solution of the partial hydrolyzate of fluoroalkylalkoxysilane and alkoxysilane in the previous stage is carried out at a solution concentration of 1 to 60% by weight. The molar ratio of fluoroalkylalkoxysilane / alkoxysilane is preferably 1/2 to 3/2.

  The reaction time is not particularly limited as long as the reaction between the fluoroalkylalkoxysilane and the alkoxysilane can proceed, but is preferably 1 minute to 24 hours. More preferably, it is 15 minutes to 6 hours.

  The reaction temperature is not particularly limited as long as the reaction proceeds and the formed siloxane can stably exist. The reaction temperature is 0 to the boiling point of the solvent. A range of 0 to 50 ° C is preferred.

The reaction of hydrolysis and polymerization by adding an alkoxysilane in the latter stage is added to the reactant solution obtained in the former stage as needed, and then 1 to 2 moles of water is added to the added alkoxysilane. By adding. A preferable amount of water added is 1.1 to 1.5 mole times. If the amount of water added is small, sufficient hydrolysis does not proceed and the desired polysiloxane of the present invention cannot be obtained.
Although the process proceeds only by adding water, it is preferable to use a catalyst similar to the hydrolysis of fluoroalkylsilane.

  As for the additional amount of alkoxysilane, the molar ratio of fluoroalkylalkoxysilane / alkoxysilane is preferably 1/4 to 1/20 as the total amount including the added alkoxysilane.

  The reaction time is not particularly limited as long as the polymerization of the reaction product of the fluoroalkylalkoxysilane generated in the previous stage and the additional alkoxysilane can proceed, but it is preferably 1 minute to 24 hours. More preferably, it is 15 minutes to 6 hours.

  The reaction temperature is not particularly limited as long as the polymerization proceeds and the formed polysiloxane can stably exist. The reaction temperature is 0 ° C. to the boiling point of the solvent. A range of 0 to 50 ° C is preferred.

  By the above reaction, a polysiloxane solution contained in the silicon-containing treatment agent of the present invention is obtained. The resulting polysiloxane solution can be used to obtain the silicon-containing treatment agent of the present invention as a polysiloxane by removing the solvent, or as a polysiloxane solution adjusted to a desired concentration by removing or adding the solvent.

  Furthermore, an alkoxysilane polymer can be used to obtain the polysiloxane of the present invention. When an alkoxysilane polymer is used, the alkoxysilane polymer is preferably a 3 to 20 mer of alkoxysilane. More preferably, it is an 8- to 15-mer. When the degree of polymerization is less than 3, the homogeneity of the target compound of Formula 1 or 2 is lowered. If it exceeds 20, the desired water-repellent property cannot be obtained.

  The alkoxysilane polymer can be synthesized by a tetraalkoxysilane hydrolysis polymerization reaction known to those skilled in the art, but methyl silicate 51 (manufactured by Colcoat), ethyl silicate 40 (manufactured by Colcoat), HAS-1 Commercial products such as (manufactured by Colcoat), HAS-6 (manufactured by Colcoat), HAS-10 (manufactured by Colcoat), and atron (manufactured by Nippon Soda Co., Ltd.) can also be used.

  When using an alkoxysilane polymer, it is included in the target silicon-containing treatment agent by mixing and reacting in the solution obtained by dissolving the obtained partial hydrolyzed fluoroalkylalkoxysilane and alkoxysilane polymer in the above solvent. Polysiloxane is obtained.

  The reaction in the fluoroalkylalkoxysilane partial hydrolyzate and alkoxysilane polymer solution is carried out at a solution concentration of 1 to 60% by weight.

  The reaction time is not particularly limited as long as the reaction between the fluoroalkylalkoxysilane and the alkoxysilane or the alkoxysilane polymer can proceed, but it is preferably 1 minute to 24 hours. More preferably, it is 15 minutes to 6 hours.

  The reaction temperature is not particularly limited as long as the reaction proceeds and the formed polysiloxane can stably exist. The reaction temperature is 0 to the boiling point of the solvent. A range of 0 to 50 ° C is preferred.

  By the above reaction, a polysiloxane solution contained in the silicon-containing treatment agent of the present invention is obtained. The resulting polysiloxane solution can be used to obtain the silicon-containing treatment agent of the present invention as a polysiloxane by removing the solvent, or as a polysiloxane solution adjusted to a desired concentration by removing or adding the solvent.

The amount ratio (m / n ratio of the chemical formulas 1 and 2) of the siloxane part into which the ^Rf group of the polysiloxane contained in the silicon-containing treatment agent of the present invention is introduced and the non-introduced siloxane part is in the range of 4 ≦ m + n ≦ 20. If it is, it will not specifically limit, Preferably it is m <= n, It can change with the amount ratio of fluoroalkyl alkoxysilane and alkoxysilane. For example, when an alkoxysilane polymer is used, if 1 mole of fluoroalkylalkoxysilane is used per mole of 15-mer of alkoxysilane polymer, a polysiloxane of m + n = 15 and m / n = 1/15 is formed.

  Furthermore, the silicon-containing treatment agent of the present invention can be added with various alkoxysilane polymers and polysiloxane having a reactive functional group in order to ensure affinity and reactivity with different substrates to be applied. Preferably, the compounds represented by Formulas 3 and 4 may be mixed.

In the case of a highly hydrophilic substrate, only a polysiloxane formed by bonding a side chain containing an alkoxy group and a perfluoroalkyl group as a side chain to silicon of the main chain (preferably a polysiloxane represented by the above-described chemical formulas 1 and 2). However, for an organic base material, a polysiloxane having a reactive functional group (a preferable polysiloxane is a functional group according to the chemical structure of the base material introduced into the R ^r group of the above chemical formulas 3 and 4). It is preferable to mix polysiloxane).

  Polysiloxane having a reactive functional group with a polysiloxane formed by bonding a side chain containing an alkoxy group and a perfluoroalkyl group as a side chain to silicon of the main chain (preferably, the polysiloxane of the above formulas 1 and 2). (The preferred polysiloxane is not particularly limited as the mixing ratio of the above-mentioned polysiloxanes of formulas 3 and 4), and is selected according to the desired film physical properties.

  By increasing the mixing ratio of the polysiloxane having a reactive functional group in the silicon-containing treatment agent of the present invention, between the substrate and the polysiloxane film having fluoroalkyl end groups that self-assemble on the film surface. The film thickness can be increased. If the film thickness may be large, polysiloxane having 1000 times the amount of reactive functional groups can be mixed with polysiloxane having fluoroalkyl end groups.

The functional group (R ^r group) introduced into the compounds of Chemical Formulas 3 and 4 is not particularly limited because it is selected depending on the substrate to be coated. Examples of the reactive functional group introduced into the R ^r group include a (meth) acryl group, an epoxy group, a vinyl group, a cyano group, an isocyanate group, a styryl group, an amino group, a ureido group, and a mercapto group. When introducing a reactive functional group, it is also possible to add a polymerization initiator, a catalyst, etc. as needed.

  The compounds described in the chemical formulas 3 and 4 can be obtained by changing the fluoroalkoxysilane of the chemical formulas 1 and 2 to the alkylalkoxysilane having the reactive end.

  The silicon-based treatment agent of the present invention can be used for forming a water-repellent film. That is, a water-repellent film can be obtained by applying the obtained silicon-based treatment agent to a target substrate.

  The silicon-containing treatment agent of the present invention is preferably used in the form of a solution dissolved or dispersed in a solvent, but is not particularly limited as long as it can be dissolved or dispersed. When the water-repellent film is formed using the silicon-containing treatment agent of the present invention, the silicon-containing treatment agent of the present invention is selected in consideration of the affinity and solubility for the substrate to be applied.

  The water-repellent film of the present invention is formed by coating and forming on a target substrate. The film forming method is not particularly limited, and is selected according to the type and shape of the base material on which the water repellent film is formed. For example, generally used spin coating, dip coating, flow coating, bar coating, spray coating, ultrasonic spray coating, and the like are used.

  Since the polymerization is promoted by moisture in the air, the coating film is preferably left in the range of 10 to 90% relative humidity. More preferably, it is 30 to 60%. Moreover, it is possible to accelerate | stimulate drying and the said polymerization reaction by heating in the range from room temperature after application | coating to the temperature according to the heat-resistant temperature of a board | substrate.

In order to adjust the affinity with the substrate, the compounds represented by the chemical formulas 3 and 4 can be mixed and then applied to the equipment. In this case, it is also possible to add a catalyst or a polymerization initiator in advance and promote the reaction by heat treatment, light irradiation treatment, etc. after coating.
Heat treatment, light irradiation treatment, etc. promotes bond formation by polymerization between the polymerizable terminals contained in the film and reaction with the substrate surface, resulting in a film with strong adhesion to the substrate and a film with excellent mechanical properties. It can be formed.

  The resulting film is a film having water repellency with a contact angle with water exceeding 90 °. It also has oil repellency to oil components.

[Example 1]
After dissolving 1.32 g of nonafluorohexyltrimethoxysilane in 11.9 g of ethanol, 80 mg of 0.1 M hydrochloric acid was added and stirred at room temperature for 30 minutes. The obtained reaction solution was added to 12 g of an ethanol solution of ethoxysilane polymer (manufactured by Colcoat, HAS-6, average 10-mer, silica oxide equivalent concentration 18% by weight). After stirring at room temperature for 16 hours, the mixture was heated and stirred at 60 ° C. for 1 hour to obtain an ethanol solution of polysiloxane having fluoroalkylsiloxane ends, which is a constituent of the silicon-containing treatment agent of the present invention.
The obtained polysiloxane ethanol solution was concentrated and a ²⁹ Si-NMR spectrum was measured. In the obtained siloxane (FIG. 1), the −53.4 ppm peak observed in the starting material nonafluorohexyltrimethoxysilane (FIG. 2) disappears, and −54.4, −61.5, −63 A reactant peak was observed at .7 ppm. Moreover, the peak attributed to the alkoxysiloxane which is a principal chain was observed in the range of -100 to -115 ppm. From the above, it was confirmed that polysiloxane having the target fluoroalkylsiloxyl group was introduced. As described above, according to this example, in Chemical Formula 1, R ^f is C ₄ F ₉ (CH ₂ ) ₂ Si (OCH ₃ ) ₂ O—, R and R ¹ are C ₂ H ₅ −, m + n is 10 on average, m = 1 and n = 9 were obtained.
The ethanol solution obtained by this reaction is used as a silicon-containing treatment agent.

[Example 2]
The molar ratio of the fluoroalkylsilane: ethoxysilane polymer (as an average 10-mer) in the ethanol solution of the polysiloxane having fluoroalkylsiloxane ends obtained in Example 1 and HAS-6 is 1/20. Thus, a silicon-containing treatment agent was obtained.

[Example 3]
After 0.9 g of methacryloxypropyltrimethoxysilane was dissolved in 8.1 g of ethanol, 80 mg of 0.1 M hydrochloric acid was added, and the mixture was stirred at room temperature for 30 minutes. The obtained reaction solution was added to 12 g of an ethanol solution of ethoxysilane polymer (manufactured by Colcoat, HAS-6, average 10-mer, silica oxide equivalent concentration 18% by weight). After stirring at room temperature for 16 hours, the mixture was heated and stirred at 60 ° C. for 1 hour to obtain an ethanol solution of polysiloxane having a reactive terminal, which is a constituent of the silicon-containing treatment agent of the present invention.
The obtained polysiloxane ethanol solution was concentrated and a ²⁹ Si-NMR spectrum was measured. In the obtained siloxane (FIG. 3), the −50.9 ppm peak observed in the starting material methacryloxypropyltrimethoxysilane (FIG. 4) disappears, and −59.9, −61.5, −64 A peak of the reactant was observed at ˜−70 ppm. Moreover, the peak attributed to the alkoxysiloxane which is a principal chain was observed in the range of -100 to -115 ppm. From the above, formation of a polysiloxane having an alkylsiloxyl group having a methacryloxy group as a target reactive functional group was confirmed.
The polysiloxane ethanol solution obtained here was added to the polysiloxane ethanol solution of Example 1 and HAS-6 to form a mole of fluoroalkylsilane: methacryloxypropyltrimethoxysilane: ethoxysilane polymer (as an average 10-mer). Mixing was performed so that the ratio was 1/1/30 to obtain a silicon-containing treatment agent.

[Example 4]
Using the silicon-based treatment agent obtained in Example 1, a film was formed on a silica glass substrate by a casting method. After film formation, the film was dried at 120 ° C. for 30 minutes to obtain a transparent film.
The contact angles of water and hexane of the obtained film were measured, which were 97 ° and 29 °, respectively, and it was confirmed that a water / oil repellent film was formed.

[Example 5]
Using the silicon-based treatment agent obtained in Example 2, a film was formed on a silica glass substrate by a casting method. After film formation, the film was dried at 80 ° C. for 30 minutes to obtain a transparent film.
The contact angles of water and hexane of the obtained film were measured, which were 97 ° and 29 °, respectively, and it was confirmed that a water / oil repellent film was formed.

[Example 6]
Using the silicon-based treatment agent obtained in Example 3, a film was formed on a PET substrate by a casting method. After film formation, the film was dried at 80 ° C. for 30 minutes to obtain a transparent film.
The contact angles of water and hexane of the obtained film were measured, which were 100 ° and 33 °, respectively, and it was confirmed that a water / oil repellent film was formed.
The obtained film was peeled from the PET substrate, and IR spectra were measured from the surface and the substrate side. In the measurement from the surface side, an absorption peak characteristic of the fluoroalkyl group was observed, but no absorption peak attributed to the methacryloxy group was observed. On the contrary, in the measurement from the substrate side, the absorption peak attributed to the methacryloxy group was clearly observed, but the absorption peak of the fluoroalkyl group was not observed.
From the above, it was confirmed that a film in which the composition of the fluoroalkyl group and the methacryloxy group changed in a gradient from the surface toward the substrate side was formed.

  As described above in detail, according to the present invention, a coating film having excellent water repellency and oil repellency can be easily formed. Further, the water-repellent film according to the present invention is a transparent film excellent in durability such as antifouling property, abrasion resistance, chemical resistance, heat resistance, etc., and plastic materials, glass materials, etc. are spectacle lenses, camera lenses, As a light beam condensing lens or a light diffusing lens, it can be widely applied to consumer use or industrial use as an antifouling metal material, ceramic material, or the like.

Claims (5)

The polysiloxane side chains containing silicon alkoxy group and a perfluoroalkyl group as a side chain of a main chain formed by bonding a free towards Lee-containing treatment agent, is the side chain containing the perfluoroalkyl group, the structural formula Silicon-containing, characterized by being an alkylsiloxyl group containing a perfluoroalkyl group represented by C _X F _{2X + 1} (1 ≦ x ≦ 6) (including a part of the alkylsiloxyl group being an alkyl group) Processing agent. The polysiloxane is represented by chemical formula 1 or 2 (R ^f is an alkylsiloxyl group containing a perfluoroalkyl group having 1 to 6 carbon atoms (including a part of the alkylsiloxyl group is an alkyl group), and R is an alkyl group. , R ¹ represents an alkyl group or an alkoxyalkyl siloxyl group, m and n represent an integer of 1 or more, according to claim 1, characterized in that a polysiloxane represented by m ≦ n, 4 ≦ m + n ≦ 20) Silicon-containing treatment agent .

In addition to the polysiloxane, a polysiloxane in which an alkylsiloxyl group containing an alkoxy group and a reactive functional group as a side chain (including those in which a part of the alkylsiloxyl group is an alkyl group) is bonded to silicon of the main chain silicon-containing treatment agent according to claim 1 or claim 2, characterized in that it comprises a. Polysiloxanes alkyl siloxyl group is bonded to a silicon containing alkoxy group and a reactive functional group as a side chain of the main chain, alkyl siloxyl group (alkyl siloxy containing chemical formula 3 or 4 (R ^r is a reactive functional group R is an alkyl group, R ¹ is an alkyl group or an alkoxysiloxyl group, m is an integer of 1 or more, n is an integer of 0 or 1 and 1 ≦ 4. The silicon-containing treatment agent according to claim 3, which is a polysiloxane represented by m + n ≦ 20) .

A water repellent film obtained by applying the silicon-containing treatment agent according to any one of claims 1 to 4 to a substrate surface .

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