TWI776970B - Fluorine-containing coating agent composition, surface treatment agent and articles - Google Patents

Abstract

(A) Silane and/or partially hydrolyzed condensate having an alkoxysilyl group and/or aryloxysilyl group modified by a polymer containing a fluorine-containing polyether group, and (B) having a fluorine-containing polyether group Silane and/or its partially hydrolyzed condensate of polymer-modified acyloxysilyl and/or aryloxysilyl group, by setting the mass ratio as (A)/(B)=99.9/ In the range of 0.1 to 80/20 (total 100), a fluorine-containing coating agent composition can be obtained that can form a stable and uniform film in a short time, especially in vacuum deposition coating, the curing speed after coating is improved.

Description

Fluorine-containing coating agent composition, surface treatment agent and articles

The present invention relates to a coating agent containing a hydrolyzable alkoxy group or aryloxy group-containing silane modified by a polymer containing a fluorine polyether group and/or a partially hydrolyzed condensate thereof, especially for vacuum evaporation coating. Fluorine-containing coating agent composition that can form a stable film in a short time, and the surface treatment agent containing the coating agent composition, and the surface treatment agent treated thing.

In recent years, including the display of mobile phones, the touch panel of the screen has been accelerated. However, the touch panel is often exposed to the screen, and there are many opportunities for direct contact with fingers or cheeks, and there is a problem that dirt such as sebum easily adheres. Therefore, in order to improve the appearance and visibility, a technology that makes it difficult for fingerprints to adhere to the surface of a display, or a technology that makes it easy to remove contamination is increasingly required.

Generally, the surface free energy of the fluoropolyether group-containing compound is very small, so it has water and oil repellency, chemical resistance, lubricity, mold release, and antifouling. Utilizing its properties, it is widely used in industry as a water-repellent, oil-repellent and antifouling agent for paper and fibers, a slip agent for magnetic recording media, an oil-repellent agent for precision machines, a mold release agent, cosmetics, and protective films. However, its properties also mean that it is non-adhesive and non-adhesive to other substrates, and even if it can be applied to the surface of the substrate, it is difficult to adhere the film to the substrate.

On the other hand, a silane coupling agent is known widely as a coating agent on the surface of various substrates, as a bonding agent to an organic compound on the surface of a substrate such as glass or cloth. The silane coupling agent has an organic functional group and a reactive silyl group (generally a hydrolyzable silyl group such as an alkoxysilyl group) in one molecule. The hydrolyzable silane group forms a film by self-condensation reaction caused by moisture in the air or the like. The coating is chemically and physically bonded to the surface of glass, metal, etc. by the hydrolyzable silane group, and becomes a durable and strong coating.

Therefore, it is disclosed that by introducing a hydrolyzable silane group into a compound containing a fluorine polyether group, it is easy to adhere to the surface of the substrate, and the surface of the substrate can be formed with water and oil repellency, chemical resistance, lubricity, and mold release. The composition of the coating film with properties, antifouling properties, etc. (Patent Documents 1 to 8: Japanese Patent Laid-Open No. 2003-238577, Japanese Patent No. 2860979, Japanese Patent No. 4672095, Japanese Patent Publication No. 2008-534696, JP 2008-537557 A, JP 2012-072272 A, JP 2012-157856 A, JP 2013-136833 A).

These compositions can generally be used by diluting a solvent capable of dissolving the fluoropolyether group-containing silane compound. The dilution concentration varies depending on the coating method, but in the case of vapor deposition coating, the range of 10 to 50 mass % is often used, and in the case of spray coating or dip coating, the range of 0.03 to 5 mass % is often used. The fluorinated polyether group-containing polymer used in these compositions is mainly a compound containing an alkoxysilyl group such as a methoxy group or an ethoxy group as a hydrolyzable silyl group. When it is coated on the surface of substrates such as glass, it will be hydrolyzed due to moisture in the air or adsorbed water on the substrate, and cross-linking reaction with the active groups on the surface of the polymer or the substrate will form chemical bonds. The faster the crosslinking reaction is, the faster the coating film is formed, and the longer the film can be formed, but the alkoxysilyl group does not have a sufficient reaction speed from the viewpoint of hydrolyzability, and requires faster curing.

Therefore, the aforementioned prior art documents describe a method of adding basic compounds such as various inorganic acids, organic acids, or amines as catalysts for the purpose of increasing the curing rate. However, after coating, the remaining catalyst components may lead to re-decomposition of the cross-linked portion, which may adversely affect surface properties such as contact angle and friction coefficient. In addition, in the case of use on the surface of a touch panel of a smartphone or the like, since direct contact with a finger is required, it is preferable to use a compound that gradually volatilizes over time without remaining on the surface. On the other hand, in vapor deposition coating, the polymer component is heated and evaporated in a vacuum, and then adheres to the substrate. However, if the additive is volatile, it may evaporate before the polymer, and it is easy to be sucked into the vacuum line. On the other hand, it is difficult to fix to the base material, and sufficient effect cannot be obtained. [Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2003-238577 [Patent Document 2] Japanese Patent No. 2860979 [Patent Document 3] Japanese Patent No. 4672095 [Patent Document 4] Japanese Patent Publication No. 2008-534696 [Patent Document 5] Japanese Patent Publication No. 2008-537557 [Patent Document 6] Japanese Patent Laid-Open No. 2012-072272 [Patent Document 7] Japanese Patent Laid-Open No. 2012-157856 [Patent Document 8] Japanese Patent Laid-Open No. 2013-136833

[The problem to be solved by the invention]

The present invention is made in view of the above-mentioned circumstances, and an object of the present invention is to provide a stable coating that can be formed in a short period of time by improving the curing speed after coating, and exhibiting properties such as abrasion durability at an early stage in vacuum deposition coating. A fluorine-containing coating agent composition, a surface treatment agent containing the coating agent composition, and articles treated with the surface treatment agent. [means to solve the problem]

In order to achieve the above-mentioned object, the inventors of the present invention have made efforts to review and found that by using (A) a silane having a hydrolyzable silane group modified by a polymer containing a fluorine polyether group and/or a partial hydrolysis condensate thereof, and the hydrolyzable silyl group is a compound of an alkoxysilyl group and/or an aryloxysilyl group, and (B) a silane having a hydrolyzable silyl group modified by a polymer containing a fluorine polyether group and/or a part thereof In the coating agent composition of the hydrolyzed condensate, and the hydrolyzable silyl group is a compound of an aldoloxysilyl group and/or an aryloxysilyl group, the mass ratio of the (A) component to the (B) component is (A) )/(B)=99.9/0.1~ 80/20 (the total mass of (A) component and (B) component is 100), specifically, by adding a small amount of molecular weight distribution to the same extent as the main agent and hydrolyzed Compounds with hydrolyzable silane groups separated from catalytically active compounds, especially in vacuum evaporation coating, can increase the curing speed after coating, and can obtain fluorine-containing coating that can form a stable film in a short time. The present invention has been completed by using an agent composition.

(式中，g為每單位獨立地1~6的整數。) 所表示之重複單位，且含氟聚醚基之聚合物的至少1個的末端，至少具有1個下述一般式(2a)

(式中，R¹ 為碳數1~4的烷基、碳數2~4的烷氧基取代烷基、或苯基，R為氫原子之一部份可被鹵素原子取代的碳數1~6的1價烴基，a為2或3。) 所示之水解性烷氧基矽烷基及/或芳氧基矽烷基者。 [3]如[2]記載之含氟塗佈劑組成物，其中， 前述式(2a)中，R¹ 為甲基或乙基。 [4]如[1]~[3]之任一記載之含氟塗佈劑組成物，其中， (B)成分的具有經含氟聚醚基之聚合物改性的水解性矽烷基之矽烷為分子中含有10~200個下述一般式(1)

(式中，g為每單位獨立地1~6的整數。) 所表示之重複單位，且含氟聚醚基之聚合物的至少1個的末端具有至少1個下述一般式(2b)

(式中，R² 為碳數1~4的烷基、碳數2~4的烷氧基取代烷基、或苯基，R為氫原子之一部份可被鹵素原子取代的碳數1~6的1價烴基，a’為1、2或3。) 所示之水解性醯氧基矽烷基及/或芳醯基氧基矽烷基者。 [5]如[4]記載之含氟塗佈劑組成物，其中， 前述式(2b)中，R² 為甲基或乙基，a’為1或2。 [6]如[1]~[5]之任一記載之含氟塗佈劑組成物，其中， (A)成分及(B)成分的具有經含氟聚醚基之聚合物改性的水解性矽烷基之矽烷為選自下述一般式(3)、(4)、(5)及(6)所表示之含氟聚醚基之聚合物改性水解性矽烷的至少1種。

[式中，Rf為-(CF₂ )_d -O-(CF₂ O)_p (CF₂ CF₂ O)_q (CF₂ CF₂ CF₂ O)_r (CF₂ CF₂ CF₂ CF₂ O)_s (CF(CF₃ )CF₂ O)_t -(CF₂ )_d -，p、q、r、s、t各自獨立為0~200的整數，且p+q+r+s+t=10~200的整數，此等之括弧內所表示的各單位可隨機鍵結，d獨立地為0~5的整數。A為氟原子、氫原子、或末端為-CF₃ 基、-CF₂ H基或者-CFH₂ 基之1價含氟之基，Q為單鍵、或可被氟取代的2價有機基，Z為單鍵、二有機亞矽烷基、-JC=[J為烷基、羥基或者K₃ SiO-(K獨立地為氫原子、烷基、芳基或烷氧基)所表示之矽烷基醚基]所示之3價基、-LSi=(L為烷基)所表示之3價基、-C≡所示之4價基、-Si≡所示之4價基、及2~8價矽氧烷殘基所選出的基，W為下述一般式(7a)~(7d)

[式中，X為下述一般式(2a)或一般式(2b)

(式中，R¹ 及R² 各自獨立地為碳數1~4的烷基、碳數2~4的烷氧基取代烷基、或苯基，R為氫原子之一部份可被鹵素原子取代的碳數1~6的1價烴基，a為2或3，a’為1、2或3。) 所表示之基，f為1~10的整數，D為單鍵或碳數1~20的可被氟取代的2價有機基，m為2~6的整數，Me為甲基。] 所表示之具有水解性矽烷基的基所選出的基，α為1~7的整數。Y為具有烷氧基矽烷基、芳氧基矽烷基、醯氧基矽烷基或芳醯基氧基矽烷基之2價基，β為1~10的整數，B為氫原子、碳數1~4的烷基、或鹵素原子。] [7]如[6]記載之含氟塗佈劑組成物，其中 Y選自下述一般式(8)~(10)所表示之基的至少1種。

(式中，X為上述一般式(2a)或一般式(2b)所表示之基，D為單鍵或碳數1~20的可被氟取代的2價有機基，D’為碳數1~10的可被氟取代的2價有機基，R³ 為碳數1~20的1價烴基，e為1或2。) [8]如[6]或[7]記載之含氟塗佈劑組成物，其中 Q為由單鍵或下述式所示之2價基選出者。

(式中，b為2~4的整數，c為2~4的整數，Me為甲基。) [9]如[6]~[8]之任一記載之含氟塗佈劑組成物，其中 Z為單鍵或由下述式所表示之基選出者。

(式中，h為2~4的整數，Me為甲基。) [10]如[1]~[9]之任一記載之含氟塗佈劑組成物，其中 再含有下述一般式(11)所表示之含氟聚醚基之聚合物(C)。

(式中，Rf’為2價含有氟氧化烯基之聚合物殘基。A為氟原子、氫原子、或末端為-CF₃ 基、-CF₂ H基或者-CFH₂ 基之1價含氟之基。) [11]一種表面處理劑，其特徵係含有如[1]~[10]之任一記載之含氟塗佈劑組成物。 [12]如[11]記載之表面處理劑，其中 再含有經含有氟原子之溶劑稀釋者。 [13]一種物品，其特徵係經如[11]或[12]記載之表面處理劑處理。 [14]一種觸控面板，其特徵係經如[11]或[12]記載之表面處理劑處理。 [15]一種防反射處理物品，其特徵係經如[11]或[12]記載之表面處理劑處理。 [16]一種以如[11]或[12]記載之表面處理劑處理的玻璃、強化玻璃、藍寶石玻璃、石英玻璃或SiO₂ 處理基板。 [發明之效果]Therefore, the present invention provides the following fluorine-containing coating agent composition, a surface treatment agent containing the coating agent composition, and an article treated with the surface treatment agent. [1] A fluorine-containing coating agent composition comprising the following (A) components and (B) components, and the mass ratio of (A) components to (B) components is (A)/(B)=99.9 /0.1 to 80/20 (the sum of the mass of (A) component and (B) component is 100). (A) Silane having a hydrolyzable silane group modified by a polymer containing a fluoropolyether group and/or a partial hydrolysis condensate thereof, and the hydrolyzable silane group is an alkoxysilyl group and/or an aryloxysilane (B) a silane having a hydrolyzable silane group modified by a polymer containing a fluoropolyether group and/or a partial hydrolysis condensate thereof, and the hydrolyzable silane group is an oxysilyl group and/or Aryloxysilyl compounds. [2] The fluorine-containing coating agent composition according to [1], wherein the silane of the component (A) having a hydrolyzable silane group modified by a polymer containing a fluorine polyether group contains 10 to 200 silanes in the molecule The following general formula (1)

(In the formula, g is an integer of 1 to 6 per unit independently.) The repeating unit represented by the fluoropolyether group-containing polymer has at least one terminal of at least one of the following general formula (2a)

(in the formula, R ¹ is an alkyl group having 1 to 4 carbon atoms, an alkoxy-substituted alkyl group having 2 to 4 carbon atoms, or a phenyl group, and R is a carbon number 1 in which a part of the hydrogen atom can be substituted by a halogen atom. A monovalent hydrocarbon group of ~6, a is 2 or 3.) The hydrolyzable alkoxysilyl group and/or aryloxysilyl group indicated. [3] The fluorine-containing coating agent composition according to [2], wherein in the aforementioned formula (2a), R ¹ is a methyl group or an ethyl group. [4] The fluorine-containing coating agent composition according to any one of [1] to [3], wherein the silane of the component (B) having a hydrolyzable silane group modified by a polymer containing a fluorine polyether group It contains 10 to 200 of the following general formula (1) in the molecule

(In the formula, g is an integer of 1 to 6 per unit independently.) The repeating unit represented by the fluoropolyether group-containing polymer has at least one terminal at least one of the following general formula (2b)

(in the formula, R ² is an alkyl group having 1 to 4 carbon atoms, an alkoxy-substituted alkyl group having 2 to 4 carbon atoms, or a phenyl group, and R is a carbon number 1 in which a part of the hydrogen atom can be substituted by a halogen atom. The monovalent hydrocarbon group of ~6, a' is 1, 2 or 3.) The hydrolyzable aryloxysilyl group and/or the aryloxysilyl group indicated. [5] The fluorine-containing coating agent composition according to [4], wherein, in the above formula (2b), R ² is a methyl group or an ethyl group, and a' is 1 or 2. [6] The fluorine-containing coating agent composition according to any one of [1] to [5], wherein the components (A) and (B) have a hydrolyzed polymer modified with a fluorinated polyether group The silane of the silane group is at least one kind selected from the polymer-modified hydrolyzable silanes of the fluorine polyether group represented by the following general formulae (3), (4), (5) and (6).

[Wherein, Rf is -(CF ₂ ) _d -O-(CF ₂ O) _p (CF ₂ CF ₂ O) _q (CF ₂ CF ₂ CF ₂ O) _r (CF ₂ CF ₂ CF ₂ CF ₂ O) _s (CF(CF ₃ )CF ₂ O) _t -(CF ₂ ) _d -, p, q, r, s, and t are each independently an integer from 0 to 200, and p+q+r+s+t=10 An integer of ~200, the units represented in these parentheses can be randomly bonded, and d is independently an integer of 0 to 5. A is a fluorine atom, a hydrogen atom, or a monovalent fluorine-containing group whose terminal is -CF ₃ group, -CF ₂ H group or -CFH ₂ group, Q is a single bond, or a divalent organic group that can be substituted by fluorine, Z is a single bond, a diorganosilylene group, -JC=[J is an alkyl group, a hydroxyl group or a silyl ether represented by K ₃ SiO- (K is independently a hydrogen atom, an alkyl group, an aryl group or an alkoxy group) group], the trivalent group represented by -LSi= (L is an alkyl group), the tetravalent group represented by -C≡, the tetravalent group represented by -Si≡, and the 2~8 valent group The group selected by the siloxane residue, W is the following general formula (7a)~(7d)

[wherein, X is the following general formula (2a) or general formula (2b)

(in the formula, R ¹ and R ² are each independently an alkyl group having 1 to 4 carbon atoms, an alkoxy-substituted alkyl group having 2 to 4 carbon atoms, or a phenyl group, and R is a part of the hydrogen atom that can be replaced by halogen Atom-substituted monovalent hydrocarbon group with 1 to 6 carbon atoms, a is 2 or 3, and a' is 1, 2 or 3.) In the group represented, f is an integer of 1 to 10, and D is a single bond or carbon number 1 ~20 divalent organic groups that can be substituted by fluorine, m is an integer from 2 to 6, and Me is a methyl group. ] is a group selected from a group having a hydrolyzable silyl group, and α is an integer of 1 to 7. Y is a divalent group having an alkoxysilyl group, an aryloxysilyl group, an acyloxysilyl group or an aryloxysilyl group, β is an integer from 1 to 10, B is a hydrogen atom, and the number of carbon atoms is from 1 to 10. 4 alkyl group, or halogen atom. ] [7] The fluorine-containing coating agent composition according to [6], wherein Y is selected from at least one of groups represented by the following general formulae (8) to (10).

(in the formula, X is a group represented by the above general formula (2a) or general formula (2b), D is a single bond or a divalent organic group having 1 to 20 carbon atoms that can be substituted by fluorine, and D' is a carbon number 1 ~10 divalent organic groups that may be substituted by fluorine, R ³ is a monovalent hydrocarbon group having 1 to 20 carbon atoms, and e is 1 or 2.) [8] The fluorine-containing coating described in [6] or [7] agent composition, wherein Q is selected from a single bond or a divalent group represented by the following formula.

(In the formula, b is an integer of 2 to 4, c is an integer of 2 to 4, and Me is a methyl group.) [9] The fluorine-containing coating agent composition according to any one of [6] to [8], wherein Z is a single bond or one selected from a group represented by the following formula.

(In the formula, h is an integer of 2 to 4, and Me is a methyl group.) [10] The fluorine-containing coating agent composition according to any one of [1] to [9], further comprising the following general formula ( 11) The fluoropolyether group-containing polymer (C) represented.

(In the formula, Rf' is a divalent polymer residue containing a fluorooxyalkylene group. A is a fluorine atom, a hydrogen atom, or a monovalent compound containing a -CF ₃ group, -CF ₂ H group or -CFH ₂ group at the end. Fluorine base.) [11] A surface treatment agent characterized by containing the fluorine-containing coating agent composition according to any one of [1] to [10]. [12] The surface-treating agent according to [11], further comprising one diluted with a fluorine atom-containing solvent. [13] An article characterized by being treated with the surface treatment agent described in [11] or [12]. [14] A touch panel characterized by being treated with the surface treatment agent described in [11] or [12]. [15] An antireflection treated article characterized by being treated with the surface treatment agent described in [11] or [12]. [16] A glass, tempered glass, sapphire glass, quartz glass or SiO ₂ treated substrate treated with the surface treating agent as described in [11] or [12]. [Effect of invention]

The fluorine-containing coating agent composition of the present invention is prepared by adding a hydrolyzable alkoxysilyl group and/or an aryloxysilyl group modified by a polymer containing a fluorine-containing polyether group to a silane and/or a part thereof. Coating agent composition of hydrolyzed condensate, added in a small amount, it basically has the same degree of molecular weight distribution as the aforementioned polymer, and has hydrolyzable oxosilyl group and/or arylidene group detached from acetic acid compound with catalytic activity after hydrolysis For the compound of the oxysilyl group, the two kinds of polymers evaporate at the same time during the vacuum evaporation coating, and the coating is uniformly dispersed on the substrate, and then the catalyst compound is uniformly generated by hydrolysis, so that the curing speed after coating is improved, A stable and uniform film is formed in a short time. Moreover, not only vacuum vapor deposition coating, but also wet coating (spray coating, dip coating) can exhibit the effect of accelerating curing. [The best form of implementing the invention]

The fluorine-containing coating agent composition of the present invention is characterized in that (A) a silane having a hydrolyzable silane group modified with a fluorine-containing polyether group-containing polymer and/or a partial hydrolysis condensate thereof, and the hydrolyzable The silyl group is a compound of an alkoxysilyl group and/or an aryloxysilyl group and (B) a silane having a hydrolyzable silyl group modified by a polymer containing a fluoropolyether group and/or a partial hydrolysis condensate thereof, And in the coating agent composition in which the hydrolyzable silyl group is a compound of an aldoloxysilyl group and/or an aryloxysilyl group, the mass ratio of the (A) component to the (B) component is (A)/( B) = 99.9/0.1 ~ 80/20 (the sum of the mass of (A) component and (B) component is 100).

The mass ratio of (A) component to (B) component is (A)/(B)=99.9/0.1~80/20, preferably 99.8/0.2~85/15, more preferably 99.5/0.5~90/10 (The total of the mass of (A) component and (B) component is 100). If the component (B) is less than the above ratio, it may be difficult to exhibit the effect of promoting curing, and if it is more than the above ratio, the storage stability of the polymer when it is not cured may decrease.

In addition, the components (A) and (B) are hydrolyzable silyl groups bonded to silicon atoms that are different (component (A) is an alkoxysilyl group and/or an aryloxysilyl group, and component (B) is sulfonyloxysilyl group and/or arylyloxysilyl group.), and the structure of the silane modified by the polymer containing fluorine polyether group may have the same degree of molecular weight distribution, and the same The constructor of , can also use a different constructor.

(式中，g為每單位獨立地1~6的整數。) 所表示之重複單位，且含氟聚醚基之聚合物的至少1個末端、較佳為1個或2個末端、更佳為1個的末端具有至少1個下述一般式(2a)

(式中，R¹ 為碳數1~4的烷基、碳數2~4的烷氧基取代烷基、或苯基，R為氫原子之一部份可被鹵素原子取代的碳數1~6的1價烴基，a為2或3。) 所示之水解性烷氧基矽烷基及/或芳氧基矽烷基者。In the case of the silane of the component (A) having a hydrolyzable silane group modified by a polymer containing a fluoropolyether group, the fluoropolyether group of the component (A) is preferably used in a molecule containing 10 to 200, preferably 20 ~100 of the following general formula (1)

(In the formula, g is an integer of 1 to 6 per unit independently.) The repeating unit represented by the fluoropolyether group-containing polymer has at least one terminal, preferably one or two terminals, more preferably One terminal has at least one of the following general formula (2a)

(in the formula, R ¹ is an alkyl group having 1 to 4 carbon atoms, an alkoxy-substituted alkyl group having 2 to 4 carbon atoms, or a phenyl group, and R is a carbon number 1 in which a part of the hydrogen atom can be substituted by a halogen atom. A monovalent hydrocarbon group of ~6, a is 2 or 3.) The hydrolyzable alkoxysilyl group and/or aryloxysilyl group indicated.

Further, the component (A) is one having at least one, preferably 1 to 12, hydrolyzable alkoxysilyl groups and/or aryloxysilyl groups represented by the above formula (2a) in the molecule, more preferably There are 1 to 6 persons.

(式中，g為每單位獨立地1~6的整數。) 所表示之重複單位，且含氟聚醚基之聚合物的至少1個末端、較佳為1個或2個末端、更佳為1個的末端具有至少1個下述一般式(2b)

(式中，R² 為碳數1~4的烷基、碳數2~4的烷氧基取代烷基、或苯基，R為氫原子之一部份可被鹵素原子取代的碳數1~6的1價烴基，a’為1、2或3。) 所示之水解性醯氧基矽烷基及/或芳醯基氧基矽烷基者。In the case of the silane of the component (B) having a hydrolyzable silane group modified by a polymer containing a fluoropolyether group, the fluoropolyether group of the component (B) is preferably used in a molecule containing 10 to 200, preferably 20 ~100 of the following general formula (1)

(In the formula, g is an integer of 1 to 6 per unit independently.) The repeating unit represented by the fluoropolyether group-containing polymer has at least one terminal, preferably one or two terminals, more preferably One terminal has at least one of the following general formula (2b)

(in the formula, R ² is an alkyl group having 1 to 4 carbon atoms, an alkoxy-substituted alkyl group having 2 to 4 carbon atoms, or a phenyl group, and R is a carbon number 1 in which a part of the hydrogen atom can be substituted by a halogen atom. The monovalent hydrocarbon group of ~6, a' is 1, 2 or 3.) The hydrolyzable aryloxysilyl group and/or the aryloxysilyl group indicated.

Further, the component (B) has at least one, preferably 1 to 12 hydrolyzable aldoloxysilyl groups and/or aryloxysilyl groups represented by the above formula (2b), more preferably There are 1 to 6 persons.

The repeating unit represented by the general formula (1) of the fluoropolyether group includes, for example, the following units. In addition, the fluoropolyether group may be constituted by one of these repeating units alone, or may be a combination of two or more, or each repeating unit may be randomly bonded.

In the above formula (2a), R ¹ is an alkyl group such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, etc. having 1 to 4 carbon atoms, Alkoxy-substituted alkyl groups such as methoxymethyl, methoxyethyl, ethoxymethyl, ethoxyethyl, etc. of carbon number 2 to 4, or phenyl, wherein methyl and ethyl are should. R is a monovalent hydrocarbon group having 1 to 6 carbon atoms in which a part of the hydrogen atom may be substituted by a halogen atom, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl unsubstituted or halogen-substituted alkyl groups such as tert-butyl, tert-butyl, trifluoroethyl, trichloroethyl, etc., unsubstituted or halogen-substituted aryl groups such as phenyl, and the like. Among them, methyl and ethyl are suitable.

In the above formula (2b), R ² is an alkyl group such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl and the like having 1 to 4 carbon atoms, Alkoxy-substituted alkyl groups such as methoxymethyl, methoxyethyl, ethoxymethyl, ethoxyethyl, etc. of carbon number 2 to 4, or phenyl, wherein methyl and ethyl are should. R is a monovalent hydrocarbon group having 1 to 6 carbon atoms in which a part of the hydrogen atom may be substituted by a halogen atom, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl unsubstituted or halogen-substituted alkyl groups such as tert-butyl, tert-butyl, trifluoroethyl, trichloroethyl, etc., unsubstituted or halogen-substituted aryl groups such as phenyl, and the like. Among them, methyl and ethyl are suitable.

[式中，Rf為-(CF₂ )_d -O-(CF₂ O)_p (CF₂ CF₂ O)_q (CF₂ CF₂ CF₂ O)_r (CF₂ CF₂ CF₂ CF₂ O)_s (CF(CF₃ )CF₂ O)_t -(CF₂ )_d -，p、q、r、s、t各自獨立為0~200的整數，且p+q+r+s+t=10~200的整數，此等之括弧內所表示的各單位可隨機鍵結，d獨立地為0~5的整數。A為氟原子、氫原子、或末端為-CF₃ 基、-CF₂ H基或者-CFH₂ 基之1價含氟之基，Q為單鍵、或可被氟取代的2價有機基，Z為單鍵、二有機亞矽烷基、-JC=[J為烷基、羥基或者K₃ SiO-(K獨立地為氫原子、烷基、芳基或烷氧基)所表示之矽烷基醚基]所示之3價基、-LSi=(L為烷基)所表示之3價基、-C≡所示之4價基、-Si≡所示之4價基、及2~8價矽氧烷殘基所選出的基，W為下述一般式(7a)~(7d)

(式中，X為上述一般式(2a)或(2b)所表示之基，f為1~10的整數，D為單鍵或碳數1~20的可被氟取代的2價有機基，m為2~6的整數，Me為甲基。) 所表示之具有水解性矽烷基的基所選出的基，α為1~7的整數。Y為烷氧基矽烷基、芳氧基矽烷基、醯氧基矽烷基及芳醯基氧基矽烷基所選出的具有水解性矽烷基的2價基，β為1~10的整數，B為氫原子、碳數1~4的烷基、或鹵素原子。](A) Fluoropolyether group-containing polymer-modified hydrolyzable alkoxysilyl group and/or aryloxysilyl group-containing silane of component (A) and fluorinated polyether group-containing polymer of (B) component As for the modified silane containing hydrolyzable aldoloxysilyl group and/or aryloxysilyl group, those represented by the following general formulae (3), (4), (5) and (6) are preferably used At least one selected from the fluoropolyether group-containing polymer-modified hydrolyzable silane.

[Wherein, Rf is -(CF ₂ ) _d -O-(CF ₂ O) _p (CF ₂ CF ₂ O) _q (CF ₂ CF ₂ CF ₂ O) _r (CF ₂ CF ₂ CF ₂ CF ₂ O) _s (CF(CF ₃ )CF ₂ O) _t -(CF ₂ ) _d -, p, q, r, s, and t are each independently an integer from 0 to 200, and p+q+r+s+t=10 An integer of ~200, the units represented in these parentheses can be randomly bonded, and d is independently an integer of 0 to 5. A is a fluorine atom, a hydrogen atom, or a monovalent fluorine-containing group whose terminal is -CF ₃ group, -CF ₂ H group or -CFH ₂ group, Q is a single bond, or a divalent organic group that can be substituted by fluorine, Z is a single bond, a diorganosilylene group, -JC=[J is an alkyl group, a hydroxyl group or a silyl ether represented by K ₃ SiO- (K is independently a hydrogen atom, an alkyl group, an aryl group or an alkoxy group) group], the trivalent group represented by -LSi= (L is an alkyl group), the tetravalent group represented by -C≡, the tetravalent group represented by -Si≡, and the 2~8 valent group The group selected by the siloxane residue, W is the following general formula (7a)~(7d)

(wherein, X is a group represented by the above general formula (2a) or (2b), f is an integer of 1 to 10, D is a single bond or a divalent organic group having 1 to 20 carbon atoms that can be substituted by fluorine, m is an integer of 2 to 6, and Me is a methyl group.) In the group selected from the group having a hydrolyzable silyl group, α is an integer of 1 to 7. Y is a divalent group with hydrolyzable silyl group selected from alkoxysilyl group, aryloxysilyl group, aryloxysilyl group and aryloxysilyl group, β is an integer from 1 to 10, B is A hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a halogen atom. ]

In the above formulas (3) to (6), Rf is -(CF ₂ ) _d -O-(CF ₂ O) _p (CF ₂ CF ₂ O) _q (CF ₂ CF ₂ CF ₂ O) _r (CF ₂ CF ₂ CF ₂ CF ₂ O) _s (CF(CF ₃ )CF ₂ O) _t -(CF ₂ ) _d -. Here, p, q, r, s, and t are each independently an integer of 0 to 200, preferably p is an integer of 5 to 100, q is an integer of 5 to 100, r is an integer of 0 to 100, and s is an integer from 0 to 50, t is an integer from 0 to 100, and p+q+r+s+t is an integer from 10 to 200, preferably an integer from 20 to 100. Units can be randomly bonded. d is independently an integer of 0 to 5, preferably an integer of 0 to 2, and more preferably 1 or 2.

(式中，d’同上述d，p’、q’、r’、s’、t’各自為1以上之整數，其上限同上述p、q、r、s、t之上限，且p’、q’、r’、s’、t’的合計為1~200。u為1以上之整數、v為1以上之整數，且u+v=2~100的整數。各重複單位可隨機鍵結。)Specifically, Rf can be exemplified by those shown below.

(in the formula, d' is the same as the above d, p', q', r', s', t' are each an integer of 1 or more, the upper limit is the same as the upper limit of the above p, q, r, s, t, and p' The total of , q', r', s', and t' is 1~200. u is an integer of 1 or more, v is an integer of 1 or more, and u+v=2~100. Each repeating unit can be randomly keyed Knot.)

In the above formulas (3) and (5), A is a fluorine atom, a hydrogen atom, or a monovalent fluorine-containing group whose terminal is -CF ₃ group, -CF ₂ H group or -CFH ₂ group, and a monovalent fluorine-containing group. Specifically, those shown below can be exemplified as the base.

In the above formulae (3) to (6), Q is a single bond or a divalent organic group which may be substituted by fluorine, and is a linking group between the Rf group and the terminal group. Q may preferably contain diorganosilylene groups such as amide bonds, ether bonds, ester bonds or dimethylsilylene groups, -Si[OH][(CH ₂ ) _b Si(CH ₃ ) ₃ ]- (b is an integer of 2 to 4) an unsubstituted or substituted divalent organic group with 2 to 12 carbon atoms selected from the group consisting of one or more groups of structures, more preferably containing The unsubstituted or substituted divalent hydrocarbon group having 2 to 12 carbon atoms of the aforementioned structure.

Here, the unsubstituted or substituted divalent hydrocarbon group having 2 to 12 carbon atoms may be ethylidene, propylidene (trimethylene, methylethylidene), butylene (tetramethylene, methylidene) propylidene), alkylidene such as hexamethylene, octamethylene, arylidene such as phenylene, or a combination of two or more of these groups (alkylidene, arylidene, etc. ), and further, for example, a part or all of the hydrogen atoms of these bases can be substituted with halogen atoms such as fluorine, iodine, etc., wherein unsubstituted or substituted alkyl with 2 to 4 carbon atoms, benzene Base is better.

As such Q, the following groups are exemplified.

(式中，b為2~4的整數，c為2~4的整數，Me為甲基。)

(In the formula, b is an integer of 2 to 4, c is an integer of 2 to 4, and Me is a methyl group.)

In the above formulas (3) and (4), Z is a single bond, preferably two organic silylene groups such as a dialkylsilylene group having 1 to 3 carbon atoms, -JC=[J is preferably a carbon number 1 to 3 alkyl groups, hydroxyl groups or K ₃ SiO—(K is independently a hydrogen atom, preferably an aryl group such as an alkyl group with 1 to 3 carbon atoms, a phenyl group, or the like, or preferably an alkane with 1 to 3 carbon atoms. trivalent group represented by oxy), silyl ether group], trivalent group represented by -LSi= (L preferably an alkyl group having 1 to 3 carbon atoms), tetravalent group represented by -C≡ group, a tetravalent group represented by -Si≡, and a group selected from a 2-8-valent, preferably a 2-4-valent siloxane residue, when a siloxane bond is included, the number of silicon atoms is 2-13 , preferably a chain, branched or cyclic organopolysiloxane residue with 2 to 5 silicon atoms. In addition, it may contain a silylene group structure in which two silicon atoms are bonded by an alkyl group, that is, Si-(CH ₂ ) _n -Si (in the above formula, n is an integer of 2 to 6). The organopolysiloxane residue is preferably one having an alkyl group or a phenyl group such as methyl, ethyl, propyl, butyl and the like having 1 to 8 carbon atoms, more preferably 1 to 4 carbon atoms. In addition, the alkylene group in the silylidene bond has 2 to 6 carbon atoms, preferably 2 to 4 carbon atoms.

As such a Z aspect, the following are exemplified.

(式中，h為2~4的整數、Me為甲基。)

(In the formula, h is an integer of 2 to 4, and Me is a methyl group.)

(式中，X同上述，f為1~10、較佳為2~8的整數，D為單鍵或碳數1~20的可被氟取代的2價有機基，m為2~6、較佳為2~4的整數，Me為甲基。)In the above formulae (3) and (4), W is a group selected from the group having a hydrolyzable silyl group represented by the following general formulae (7a) to (7d).

(in the formula, X is the same as above, f is an integer of 1~10, preferably 2~8, D is a single bond or a divalent organic group having 1~20 carbon atoms that can be substituted by fluorine, m is 2~6, It is preferably an integer of 2 to 4, and Me is a methyl group.)

Here, X is the same as above. D is a single bond, or a divalent organic group having 1 to 20 carbon atoms, preferably a divalent organic group having 2 to 8 carbon atoms that can be substituted by fluorine, preferably a divalent hydrocarbon group. Examples of the divalent hydrocarbon group include methylene, ethylidene , Propylene (trimethylene, methyl ethylidene), butylene (tetramethylene, methyl propylidene), hexamethylene, octamethylene and other alkylene, phenylene An aryl group such as a group, or a combination of two or more of these groups (alkylene group, an aryl group, etc.), etc., or a part or all of the hydrogen atoms of these groups are substituted with fluorine atoms, etc. In aspect D, ethylidene, propylidene and phenylene are preferred.

(式中，f同上述。)In the aspect, the following can be specifically exemplified.

(In the formula, f is the same as above.)

In the above formulae (3) and (4), α is an integer of 1 to 7, preferably an integer of 1 to 3.

(式中，X、D同上述，D’為碳數1~10的可被氟取代的2價有機基，R³ 為碳數1~20的1價烴基，e為1或2。)In the above formulas (5) and (6), Y is a divalent hydrolyzable silyl group selected from an alkoxysilyl group, an aryloxysilyl group, an aryloxysilyl group and an aryloxysilyl group The group is preferably a group represented by the following general formula (8), (9) or (10).

(In the formula, X and D are the same as above, D' is a divalent organic group having 1 to 10 carbon atoms that can be substituted by fluorine, R ³ is a monovalent hydrocarbon group having 1 to 20 carbon atoms, and e is 1 or 2.)

Here, X and D are the same as above. D' is a divalent organic group having 1 to 10 carbon atoms, preferably a fluorine-substituted organic group having 2 to 8 carbon atoms, preferably a divalent hydrocarbon group. For the divalent hydrocarbon group, for example, a methylene group, an ethylidene group can be mentioned. , Propylene (trimethylene, methyl ethylidene), butylene (tetramethylene, methyl propylidene), hexamethylene, octamethylene and other alkylene, phenylene An aryl group such as a group, or a combination of two or more of these groups (alkylene group, an aryl group, etc.), etc., or a part or all of the hydrogen atoms of these groups are substituted with fluorine atoms, etc. For D', ethylidene and propylidene are preferred.

In addition, R ³ is a monovalent hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, and the monovalent hydrocarbon group includes, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and an isobutyl group. Alkyl, tert-butyl, pentyl, neopentyl, hexyl, octyl, etc. alkyl, cyclohexyl, etc., cycloalkyl, vinyl, allyl, propenyl, etc. alkenyl, phenyl, tolyl Aryl such as aryl, benzyl, phenylethyl, phenylpropyl, etc., etc. Among these, a methyl group is preferable.

In terms of Y, specifically, the following groups may be mentioned.

(式中，X同上述，Me為甲基。)

(In the formula, X is the same as above, and Me is a methyl group.)

In the above formulas (5) and (6), β is an integer of 1 to 10, preferably an integer of 1 to 4. In addition, in the above formulae (5) and (6), B is a hydrogen atom, an alkyl group such as a methyl group having 1 to 4 carbon atoms, an ethyl group, a propyl group, a butyl group, etc., or a fluorine atom, a chlorine atom, a bromine atom, Halogen atoms such as iodine atoms.

，Z基為

，含有水解性矽烷基的W基為

而表示者例示如下述。此等Q、Z、W的組合不限於此等者，藉由單純將Q、Z、W變更，可得到同數之含氟聚醚基之聚合物改性水解性矽烷。任一含氟聚醚基之聚合物改性水解性矽烷皆可發揮本發明之效果。Regarding the polymer-modified hydrolyzable silanes containing fluorine polyether groups represented by the above formulas (3) and (4), let the linking group Q be

, the Z base is

, the W group containing a hydrolyzable silyl group is

The representations are exemplified as follows. The combination of these Q, Z, and W is not limited to these, and by simply changing Q, Z, and W, the same number of fluoropolyether group-containing polymer-modified hydrolyzable silanes can be obtained. Any polymer-modified hydrolyzable silane containing a fluoropolyether group can exert the effect of the present invention.

(式中，t1、r1各自同t’、r’。)

(In the formula, t1 and r1 are the same as t' and r', respectively.)

(式中，p1、q1各自同p’、q’。)

(In the formula, p1 and q1 are the same as p' and q', respectively.)

(式中，p1、q1各自同p’、q’。)

(In the formula, p1 and q1 are the same as p' and q', respectively.)

(式中，u1、v1為1以上之整數，且u1+v1=t1，t1同t’。)

(In the formula, u1 and v1 are integers of 1 or more, and u1+v1=t1, t1 is the same as t'.)

(式中，t1同t’。)In addition, in terms of the fluoropolyether group-containing polymer-modified hydrolyzable silane represented by the above-mentioned formulas (3) and (4) using those other than the above-mentioned Q, Z, and W, and combining these, the following structures can be further exemplified. By. In addition, Xa is the same as above.

(In the formula, t1 is the same as t'.)

(式中，p1、q1各自同p’、q’。)

(式中，p1、q1各自同p’、q’。)

(式中，p1、q1各自同p’、q’。)

(In the formula, p1 and q1 are the same as p' and q', respectively.)

(In the formula, p1 and q1 are the same as p' and q', respectively.)

(In the formula, p1 and q1 are the same as p' and q', respectively.)

(式中，Rfa=-CF₂ O-(C₂ F₄ O)_q1 (CF₂ O)_p1 -CF₂ -，p1、q1各自同p’、q’。f1為1~10的整數。)

(In the formula, Rfa=-CF ₂ O-(C ₂ F ₄ O) _q1 (CF ₂ O) _p1 -CF ₂ -, and p1 and q1 are respectively the same as p' and q'. f1 is an integer of 1 to 10.)

(式中，p1、q1各自同p’、q’。f1為1~10的整數。)

(In the formula, p1 and q1 are respectively the same as p' and q'. f1 is an integer of 1 to 10.)

(式中，p1、q1各自同p’、q’。)

(In the formula, p1 and q1 are the same as p' and q', respectively.)

(式中，Rfb為-CF₂ O-(C₂ F₄ O)_q1 (CF₂ O)_p1 -CF₂ -，p1、q1各自同p’、q’。R⁴ 為-CH₂ CH₂ -及/或-CH(CH₃ )-。)

(式中，Rfb為-CF₂ O-(C₂ F₄ O)_q1 (CF₂ O)_p1 -CF₂ -，p1、q1各自同p’、q’。)

(wherein, Rfb is -CF ₂ O-(C ₂ F ₄ O) _q1 (CF ₂ O) _p1 -CF ₂ -, and p1 and q1 are respectively the same as p' and q'. R ⁴ is -CH ₂ CH ₂ - and/or -CH(CH ₃ )-.)

(In the formula, Rfb is -CF ₂ O-(C ₂ F ₄ O) _q1 (CF ₂ O) _p1 -CF ₂ -, and p1 and q1 are the same as p' and q', respectively.)

(式中，p1、q1、t1各自同p’、q’、t’。)

(In the formula, p1, q1, and t1 are the same as p', q', and t', respectively.)

(式中，p1、q1、t1各自同p’、q’、t’。)As the fluorinated polyether group-containing polymer-modified hydrolyzable silane represented by the above formulae (5) and (6), the following structures may be mentioned, for example. In addition, Xa is the same as above.

(In the formula, p1, q1, and t1 are the same as p', q', and t', respectively.)

(式中，p1、q1、t1各自同p’、q’、t’。)

(In the formula, p1, q1, and t1 are the same as p', q', and t', respectively.)

(式中，p1、q1、t1各自同p’、q’、t’。)

(In the formula, p1, q1, and t1 are the same as p', q', and t', respectively.)

(式中，p1、q1、t1各自同p’、q’、t’。)

(In the formula, p1, q1, and t1 are the same as p', q', and t', respectively.)

(式中，p1、q1、t1各自同p’、q’、t’。)

(In the formula, p1, q1, and t1 are the same as p', q', and t', respectively.)

The fluorine-containing coating agent composition of the present invention may contain, as component (A) or component (B), a terminal hydrolyzability of a silane having a hydrolyzable silane group modified by a polymer modified with a fluorine-containing polyether group. A partially hydrolyzed condensate obtained by partially hydrolyzing and condensing the group in advance by a known method.

Moreover, the molecular weight of (A) component and (B) component may be the same degree (for example, the weight average molecular weight of (B) component is 0.6 to 1.3 times the weight average molecular weight of (A) component, especially 0.7 to 1.2 times, especially 0.74~1.1 times the range), the weight average molecular weights of these are preferably 1,000~20,000, more preferably 2,000~10,000. If the weight average molecular weight is too small, the water and oil repellency and low dynamic friction properties of the fluoropolyether group may not be exhibited, and if the weight average molecular weight is too large, the adhesion to the substrate may be deteriorated. In addition, in this invention, the weight average molecular weight can be measured by the standard polystyrene conversion value of colloid permeation chromatography (GPC) using AK-225 (made by Asahi Glass Co., Ltd.) as a developing solvent (the same applies hereinafter).

(式中，A同前述，Rf’為2價含有氟氧化烯基之聚合物殘基。) 所表示之含氟聚醚基之聚合物(以下，亦稱無官能性聚合物)。The fluorine-containing coating agent composition of the present invention may further contain the following general formula (11) as the component (C)

(In the formula, A is the same as above, and Rf' is a divalent fluorooxyalkylene group-containing polymer residue.) The represented fluoropolyether group-containing polymer (hereinafter, also referred to as a non-functional polymer).

為佳。In the above formula (11), A can be exemplified as the same as the above exemplified A, and as A,

better.

(式中，p2為5~200、較佳為10~100的整數、q2為5~ 200、較佳為10~100的整數、r2為10~200、較佳為20~100的整數、t2為5~200、較佳為10~100的整數、t3為10~ 200、較佳為20~100的整數、t2+p2為10~200、較佳為20~ 100的整數、q2+p2為10~200、較佳為20~100的整數。)Rf' is a divalent fluorooxyalkylene group-containing polymer residue, and may be the same as or different from the Rf exemplified above, but Rf' is preferably the one shown below.

(in the formula, p2 is 5~200, preferably an integer of 10~100, q2 is 5~200, preferably an integer of 10~100, r2 is 10~200, preferably an integer of 20~100, t2 is 5~200, preferably 10~100 integer, t3 is 10~200, preferably 20~100 integer, t2+p2 is 10~200, preferably 20~100 integer, q2+p2 is 10 to 200, preferably an integer of 20 to 100.)

(式中，p2、q2、r2、t2、t3同上述。)The non-functional polymer represented by formula (11) includes, for example, the following.

(In the formula, p2, q2, r2, t2, and t3 are the same as above.)

The weight average molecular weight of the fluoropolyether group-containing polymer of the component (C) is preferably 1,000 to 50,000, more preferably 1,000 to 10,000, and furthermore, the weight in the range of 0.5 to 1.5 times the weight average molecular weight of the (A) component The average molecular weight is preferred. If the weight average molecular weight is too small, the excellent smoothness of the component (A) may be impaired, and if the weight average molecular weight is too large, the transparency of the coating film may be lowered.

Moreover, since the non-functional polymer of (C)component can use a commercial item, for example, it is sold under the brand name of FOMBLIN, DEMNUM, KRYTOX, and it can acquire easily. As such a polymer, the following structure is mentioned, for example.

(式中，t2’、p2’為滿足上述重量平均分子量的數。)FOMBLIN Y (trade name manufactured by Solvay Solexis, FOMBLIN Y25 (weight average molecular weight: 3,200), FOMBLIN Y45 (weight average molecular weight: 4,100))

(In the formula, t2' and p2' are numbers satisfying the above-mentioned weight average molecular weight.)

(式中，q2’、p2’為滿足上述重量平均分子量的數。)FOMBLIN Z (trade name manufactured by Solvay Solexis, FOMBLIN Z03 (weight average molecular weight: 4,000), FOMBLIN Z15 (weight average molecular weight: 8,000), FOMBLIN Z25 (weight average molecular weight: 9,500)

(In the formula, q2' and p2' are numbers satisfying the above-mentioned weight average molecular weight.)

(式中，r2’為滿足上述重量平均分子量的數。)DEMNUM (trade name manufactured by Daikin Industries, Ltd., DEMNUM S20 (weight average molecular weight: 2,700), DEMNUM S65 (weight average molecular weight: 4,500), DEMNUM S100 (weight average molecular weight: 5,600))

(In the formula, r2' is a number satisfying the above-mentioned weight average molecular weight.)

(式中，t3’為滿足上述重量平均分子量的數。)KRYTOX (trade name, manufactured by DuPont, KRYTOX 143AB (weight average molecular weight: 3,500), KRYTOX 143AX (weight average molecular weight: 4,700), KRYTOX 143AC (weight average molecular weight: 5,500), KRYTOX 143AD (weight average molecular weight: 7,000)

(In the formula, t3' is a number satisfying the above-mentioned weight average molecular weight.)

Although the usage-amount when combining (C) component is not specifically limited, the range of 0-50 mass % is preferable with respect to the mass of (A) component, and the range of 5-50 mass % is more preferable.

In addition, the fluorine-containing coating agent composition of the present invention may be combined with other additives as necessary without impairing the scope of the present invention. Specifically, it is a hydrolysis condensation catalyst, such as organotin compounds (dibutyldimethoxytin, dibutyltin dilaurate, etc.), organotitanium compounds (tetra-n-butyl titanate, etc.), organic acids ( Fluorine-based carboxylic acids, acetic acid, methanesulfonic acid, etc.), inorganic acids (hydrochloric acid, sulfuric acid, etc.), compounds with primary amine groups, compounds with secondary amino groups, compounds with tertiary amino groups, and guanidine groups Basic organic compounds such as compounds, compounds containing alkali metals such as lithium, sodium, potassium, etc., compounds containing alkaline earth metals such as magnesium, calcium, etc. Among these, fluorine-based carboxylic acid, acetic acid, tetra-n-butyl titanate, and dibutyltin dilaurate are particularly preferable. The addition amount of the hydrolysis-condensation catalyst is the catalyst amount, but is usually 0.01 to 5 parts by mass, particularly 0.1 to 1 part by mass, with respect to 100 parts by mass of the component (A).

The fluorine-containing coating agent composition of the present invention can be prepared by uniformly mixing the above components by a conventional method.

The surface treatment agent of this invention contains the said fluorine-containing coating agent composition. The surface treatment agent of the present invention, which contains a fluorine-containing coating agent composition containing (A) components and (B) components, generally dissolves these polymers ((A) components and (B) components). Use after dissolving and diluting in solvent. The dilution solvent is not particularly limited if it can dissolve uniformly. Examples of such a solvent include fluorine-modified aliphatic hydrocarbon-based solvents (perfluorohexane, perfluoroheptane, perfluorooctane, etc.), fluorine-modified aromatic hydrocarbon-based solvents (m-xylene hexafluoride, etc.) , benzotrifluoride, 1,3-trifluoromethylbenzene, etc.), fluorine-modified ether solvents (methyl perfluoropropyl ether, methyl perfluorobutyl ether, ethyl perfluorobutyl ether, perfluoro(2-butyltetrahydrofuran, etc.), fluorine-modified alkylamine-based solvents (perfluorotributylamine, perfluorotripentylamine, etc.), partially fluorine-modified solvents (1,1,1,2 ,2,3,3,4,4-Nonafluorohexane, 1,1,1,2,2,3,4,5,5,5-Decafluoropentane, 1,1,1,2,2 ,3,3,4,4,5,5, 6,6-tridecafluorohexane, 1,1,1,2,2,3,3,4,4,5,5,6,6-ten Trifluorooctane, 1,1,1,3,3-pentafluorobutane, etc.), hydrocarbon-based solvents (petroleum, mineral spirits, toluene, xylene, etc.), ketone-based solvents (acetone, methyl ethyl acetate, etc.) ketone, methyl isobutyl ketone, etc.) and other solvents. Among them, fluorine-modified fluorine-containing solvents are preferred in terms of solubility and wettability, especially ethyl perfluorobutyl ether, decafluoropentane and 1,1,1,3, 3-Pentafluorobutane is more preferred. The above-mentioned solvents may be used alone or in combination of two or more.

The optimum concentration of the components (A) and (B) dissolved in the solvent varies depending on the method of coating treatment, but in the entire surface treatment agent containing the fluorine-containing coating agent composition and the solvent, (A) The content of the components is preferably in the range of 0.01 to 50 mass %, particularly in the range of 0.03 to 25 mass %. When the concentration of the component (A) is too low, sufficient antifouling properties or water and oil repellency cannot be obtained after the coating treatment, and when the concentration is too high, the coating film becomes uneven, the transparency decreases, and the surface becomes sticky.

The surface treatment agent containing the fluorine-containing coating agent composition of the present invention can be applied to the substrate by conventional methods such as brush coating, dipping, spraying, and vapor deposition. In addition, although the curing temperature varies depending on the curing method, for example, when it is carried out by the spray method, the ink jet method, the dipping method, the brush coating, and the vacuum vapor deposition method, it is room temperature (20°C) to 200°C, especially 50°C. The range of ~150°C is preferred. In terms of curing humidity, it is desirable to perform under humidification to accelerate the reaction. Moreover, although the film thickness of a cured film is suitably selected according to the kind of base material, it is 0.1-100 nm normally, and 3-30 nm is especially preferable. In addition, when the adhesiveness is poor, the adhesiveness can be improved by providing a SiO ₂ layer as an undercoat layer, or by performing vacuum plasma treatment, atmospheric pressure plasma treatment, or alkali treatment.

The substrate treated with the surface treatment agent containing the fluorine-containing coating agent composition of the present invention is not particularly limited, and may be various materials such as paper, cloth, metal and its oxide, glass, plastic, ceramic, and quartz. The surface treatment agent containing the fluorine-containing coating agent composition of the present invention can impart water and oil repellency, chemical resistance, mold release properties, low dynamic friction properties, and antifouling properties to these substrates. In particular, it can impart excellent antifouling performance without impairing the transparency or texture of various articles, and can prevent the penetration of drugs, etc. into the protective substrate, and maintain long-term antifouling performance. Articles treated with the surface treatment agent containing the fluorine-containing coating agent composition of the present invention include, for example, optical articles, films, glass, quartz substrates, and antireflection films, and are especially used for touch panels and antireflection treated articles. , glass, tempered glass, sapphire glass, quartz glass, SiO ₂ treated substrate.

[Example]

Hereinafter, the present invention will be described in more detail by way of Examples and Comparative Examples, but the present invention is not limited to the following Examples.

As the hydrolyzable alkoxysilyl group and/or aryloxysilyl group-containing silane (A) modified by the fluoropolyether group-containing polymer, the following compounds A1 to A4 were prepared as the fluorinated polyether group-containing silane (A) The following compounds B1 and B2 were prepared for the polymer-modified silane (B) containing a hydrolyzable aldoloxysilyl group and/or an aryloxysilyl group.

(重量平均分子量：4,600)Compound A1

(weight average molecular weight: 4,600)

(Rfa：-CF₂ O-(C₂ F₄ O)_q1 (CF₂ O)_p1 -CF₂ -、q1/p1=0.9、p1 +q1≒45、f=3) (重量平均分子量：5,500)Compound A2

(Rfa: -CF ₂ O-(C ₂ F ₄ O) _q1 (CF ₂ O) _p1 -CF ₂ -, q1/p1=0.9, p1 +q1≒45, f=3) (weight average molecular weight: 5,500)

(Rfb：-CF₂ O-(C₂ F₄ O)_q1 (CF₂ O)_p1 -CF₂ -、q1/p1=1.1、p1 +q1≒50、f=3) (重量平均分子量：4,800)Compound A3

(Rfb: -CF ₂ O-(C ₂ F ₄ O) _q1 (CF ₂ O) _p1 -CF ₂ -, q1/p1=1.1, p1 +q1≒50, f=3) (weight average molecular weight: 4,800)

(Rfb：-CF₂ O-(C₂ F₄ O)_q1 (CF₂ O)_p1 -CF₂ -、q1/p1=1.1、p1+q1≒40) (重量平均分子量：4,100)Compound A4

(Rfb: -CF ₂ O-(C ₂ F ₄ O) _q1 (CF ₂ O) _p1 -CF ₂ -, q1/p1=1.1, p1+q1≒40) (weight average molecular weight: 4,100)

(Rfb：-CF₂ O-(C₂ F₄ O)_q1 (CF₂ O)_p1 -CF₂ -、q1/p1=1.1、p1 +q1≒50、f=3) (重量平均分子量：4,800)Compound B1

(Rfb: -CF ₂ O-(C ₂ F ₄ O) _q1 (CF ₂ O) _p1 -CF ₂ -, q1/p1=1.1, p1 +q1≒50, f=3) (weight average molecular weight: 4,800)

(Rfb：-CF₂ O-(C₂ F₄ O)_q1 (CF₂ O)_p1 -CF₂ -、q1/p1=1.1、p1 +q1≒40) (重量平均分子量：4,100)Compound B2

(Rfb: -CF ₂ O-(C ₂ F ₄ O) _q1 (CF ₂ O) _p1 -CF ₂ -, q1/p1=1.1, p1 +q1≒40) (weight average molecular weight: 4,100)

The following C1 and C2 were prepared as the curing catalyst for the comparative example. C1: trifluoroacetic acid C2: Acetic acid

[Examples 1 to 6 and Comparative Examples 1 to 6] Preparation of surface treatment agent In Examples 1 to 6, any of the above-mentioned components A1 to A4 and any of components B1 and B2 were mixed with the compositions described in Table 1 below (mixtures 1 to 6), and dissolved in Novec 7200 (manufactured by 3M). ) 400 mass parts so that the density|concentration of this mixture (100 mass parts in total) becomes 20 mass %, and prepares a surface treatment agent. In Comparative Examples 1 to 6, any one of the above-mentioned components A1 to A4, or any of the hardening catalysts C1 and C2 for the comparative example were mixed with the compositions described in the following Table 2 (mixtures 7 to 12), A surface treatment agent was prepared by dissolving 400 parts by mass of Novec 7200 (manufactured by 3M) so that the concentration of the mixture (100 parts by mass in total) would be 20% by mass.

Forming a cured film by vacuum deposition Each surface treatment agent prepared above was vacuum-deposited on glass (Gorilla 3 manufactured by Corning Incorporated) whose outermost surface was treated with SiO ₂ 15 nm under the following conditions, and was carried out at 25° C. and a humidity of 50% for 1 A film (film thickness: about 10 nm) formed after curing for 1 hour was used as a sample in the following evaluation. [Coating conditions and apparatus for vacuum deposition] Measuring device: small vacuum deposition device VPC-250F Pressure: 2.0×10 ^-3 Pa~3.0×10 ^-2 Pa Evaporation temperature (reaching temperature of the deposition boat): 500 ℃ Evaporation distance: 20mm Additive amount of treatment agent: 5mg Evaporation amount: 5mg

The cured coatings in the above-mentioned samples were evaluated by the following method. [Water repellency] Using a contact angle meter DropMaster (manufactured by Kyowa Interface Science Co., Ltd.), the contact angle with respect to water of the cured film was measured. The results are shown in Table 3 below.

[Abrasion resistance] Abrasion resistance to steel wool (#0000): Using Tribo-gearTYPE: 30S (manufactured by Shinto Science Co., Ltd.), the cured coating was subjected to 5,000 and 10,000 reciprocating abrasions under the following conditions, and the contact angle was used The contact angle with respect to water of the cured film was measured with a DropMaster (manufactured by Kyowa Interface Science Co., Ltd.). The results are shown in Table 3 below. In addition, in the case where the water contact angle did not reach 100° at the time of 5,000 abrasions, the subsequent test was not performed. Contact area: 1cm ² load: 1kg Moving distance (one way): 30mm Moving speed: 3,600mm/min

Description of Table 3 Comparison of Examples 1 to 6 with Comparative Examples 1 to 4 Examples 1 to 6 are cases in which a polymer (A) having an alkoxysilyl group at a terminal is added and matched with a polymer (B) having an alkoxysilyl group at a terminal having the same degree of molecular weight distribution. On the other hand, Comparative Examples 1 to 4 are the cases in which only the polymer (A) is used without the compounding polymer (B). In Examples 1 to 6, the polymer (A) and the polymer (B) were vapor-deposited and coated on the substrate, and the acid (acetic acid) generated by the hydrolysis of the polymer (B) accelerated the curing. On the other hand, Comparative Examples 1 to 4 are polymers of only terminal alkoxysilanes (methoxysilanes), so hydrolysis is slow, and film hardening on the substrate is slow, and abrasion durability is inferior to Examples.

Comparison of Example 6 with Comparative Examples 5 and 6 Comparative Examples 5 and 6 are examples in which an organic acidic compound was added as a catalyst instead of (B) component. During the vacuum deposition, the additives such as these have a low boiling point, are easily attracted to the side of the vacuum exhaust line, and are hardly fixed to the surface of the substrate, and the effect of promoting hardening cannot be seen. to the same extent.

Claims (15)

A fluorine-containing coating agent composition is characterized by containing the following (A) components and (B) components, and the mass ratio of (A) components and (B) components is (A)/(B)=99.9/0.1~ 80/20 (the total mass of components (A) and (B) is 100), (A) a silane having a hydrolyzable silane group modified by a polymer containing a fluoropolyether group and/or its partial hydrolysis condensation and the hydrolyzable silyl group is a compound of an alkoxysilyl group and/or an aryloxysilyl group, (B) a silane having a hydrolyzable silyl group modified by a polymer containing a fluorine polyether group and/or It is a partially hydrolyzed condensate, and the hydrolyzable silyl group is a compound of an acyloxysilyl group and/or an aryloxysilyl group. The fluorine-containing coating agent composition according to claim 1, wherein the silane of the component (A) having a hydrolyzable silane group modified by a polymer containing a fluorine polyether group contains 10 to 200 silanes in the molecule of the following A repeating unit represented by the general formula (1)-C _g F _2g O- (1) (in the formula, g is an integer of 1 to 6 per unit independently), and at least one of the fluoropolyether group-containing polymer , with at least one of the following general formula (2a)

(in the formula, R ¹ is an alkyl group having 1 to 4 carbon atoms, an alkoxy-substituted alkyl group having 2 to 4 carbon atoms, or a phenyl group, and R is a carbon number 1 in which a part of the hydrogen atom can be substituted by a halogen atom. A monovalent hydrocarbon group of ~6, a is a hydrolyzable alkoxysilyl group and/or an aryloxysilyl group represented by 2 or 3). The fluorine-containing coating agent composition according to claim 2, wherein, in the aforementioned formula (2a), R ¹ is a methyl group or an ethyl group. The fluorine-containing coating agent composition according to any one of Claims 1 to 3, wherein the silane of the component (B) having a hydrolyzable silane group modified by a polymer containing a fluorine-containing polyether group is a molecule containing 10 to 200 repeating units represented by the following general formula (1)-C _g F _2g O- (1) (in the formula, g is an integer of 1 to 6 per unit independently), and the fluorine-containing polyether group At least one terminal of the polymer has at least one with the following general formula (2b)

(in the formula, R ² is an alkyl group having 1 to 4 carbon atoms, an alkoxy-substituted alkyl group having 2 to 4 carbon atoms, or a phenyl group, and R is a carbon number 1 in which a part of the hydrogen atom can be substituted by a halogen atom. The monovalent hydrocarbon group of ~6, a' is a hydrolyzable aryloxysilyl group and/or an aryloxysilyl group represented by 1, 2 or 3). The fluorine-containing coating agent composition according to claim 4, wherein, in the above formula (2b), R ² is a methyl group or an ethyl group, and a' is 1 or 2. The fluorine-containing coating agent composition according to any one of Claims 1 to 3, wherein the components (A) and (B) having a hydrolyzable silane group modified with a fluorinated polyether group-containing polymer The silane is at least one selected from the polymer-modified hydrolyzable silanes containing fluorine polyether groups represented by the following general formulae (3), (4), (5) and (6), A-Rf-QZ ( W) _α (3) Rf-(QZ(W) _α ) ₂ (4) A-Rf-Q-(Y) _β B (5) Rf-(Q-(Y) _β B) ₂ (6) [Eq. where Rf is -(CF ₂ ) _d -O-(CF ₂ O) _p (CF ₂ CF ₂ O) _q (CF ₂ CF ₂ CF ₂ O) _r (CF ₂ CF ₂ CF ₂ CF ₂ O) _s ( CF(CF ₃ )CF ₂ O) _t -(CF ₂ ) _d -, p, q, r, s, and t are each independently an integer from 0 to 200, and p+q+r+s+t=10 to 200 The integers of , the units represented in these brackets can be randomly bonded, d is independently an integer from 0 to 5, A is a fluorine atom, a hydrogen atom, or a terminal -CF ₃ group, -CF ₂ H group or -CFH is a monovalent fluorine-containing group of ₂ groups, Q is a single bond or a divalent organic group that can be substituted by fluorine, Z is a single bond, a diorganosilylene group, -JC=[J is an alkyl group, a hydroxyl group or A trivalent group represented by K ₃ SiO-(K is independently a hydrogen atom, an alkyl group, an aryl group, or an alkoxy group) represented by a silyl ether group], -LSi= (L is an alkyl group) represented by 3 A valence group, a tetravalent group represented by -C≡, a tetravalent group represented by -Si≡, and a group selected from 2 to 8 valent siloxane residues, W is a group having the following general formula (7a)~ (7d)

[wherein, X is the following general formula (2a) or general formula (2b)

(in the formula, R ¹ and R ² are each independently an alkyl group having 1 to 4 carbon atoms, an alkoxy-substituted alkyl group having 2 to 4 carbon atoms, or a phenyl group, and R is a part of the hydrogen atom that can be replaced by halogen Atom-substituted monovalent hydrocarbon group with 1 to 6 carbon atoms, a is 2 or 3, a' is a group represented by 1, 2 or 3), f is an integer of 1 to 10, and D is a single bond or a carbon number of 1 to 1 20 divalent organic groups that can be substituted by fluorine, m is an integer of 2 to 6, Me is a group selected from the hydrolyzable silyl group represented by methyl], α is an integer of 1 to 7, and Y is a group with Divalent group of alkoxysilyl group, aryloxysilyl group, aryloxysilyl group or aryloxysilyl group, β is an integer of 1~10, B is hydrogen atom, alkane having 1~4 carbon atoms group, or halogen atom]. The fluorine-containing coating agent composition according to claim 6, wherein Y is at least one selected from the groups represented by the following general formulas (8) to (10),

(in the formula, X is a group represented by the above general formula (2a) or general formula (2b), D is a single bond or a divalent organic group having 1 to 20 carbon atoms that can be substituted by fluorine, and D' is a carbon number 1 ~10 divalent organic groups that can be substituted by fluorine, R ³ is a monovalent hydrocarbon group with 1 to 20 carbon atoms, and e is 1 or 2). The fluorine-containing coating agent composition according to claim 6, wherein Q is a single bond or one selected from a divalent group represented by the following formula,

(In the formula, b is an integer of 2 to 4, c is an integer of 2 to 4, and Me is a methyl group). The fluorine-containing coating agent composition according to claim 6, wherein Z is a single bond or one selected from a group represented by the following formula,

(in the formula, h is an integer of 2 to 4, and Me is a methyl group). The fluorine-containing coating agent composition according to any one of Claims 1 to 3, which further contains a fluorine-containing polyether group-containing polymer (C) represented by the following general formula (11), A-Rf '-A (11) (wherein, Rf' is a divalent polymer residue containing a fluorooxyalkylene group, A is a fluorine atom, a hydrogen atom, or a terminal -CF ₃ group, -CF ₂ H group or -CFH ₂ groups of monovalent fluorine-containing groups). A surface treatment agent characterized by containing the fluorine-containing coating agent composition according to any one of Claims 1 to 10. The surface treatment agent of Claim 11 which is further diluted with the solvent containing a fluorine atom. A touch panel characterized by being treated with the surface treatment agent described in claim 11 or 12. An anti-reflection treated article characterized by being treated with the surface treatment agent described in claim 11 or 12. A glass, tempered glass, sapphire glass, quartz glass or SiO ₂ treated substrate treated with the surface treatment agent according to claim 11 or 12.