TWI779101B - Fluorine-containing coating agent composition, surface treatment agent and articles - Google Patents

Abstract

Containing hydroxyl or hydrolyzable groups containing at least 3 siloxane bonds and/or at least 2 siloxane bonds in the molecule and modified by polymers containing fluorooxyalkylene groups in a specific blending ratio A surface treatment agent for the composition of organosilicon compounds and/or their partial (hydrolyzed) condensates and perhydropolysilazane fluorine-containing coating agents, which can form a water-repellent coating with excellent abrasion resistance on resin or metal surfaces Oil-repellent layer.

Description

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

The present invention relates to a fluorine-containing coating agent composition, in detail, to a fluorine-containing coating agent composition that forms a film excellent in water and oil repellency and abrasion resistance, and a surface treatment agent containing the composition, And articles treated with the surface treatment agent.

Most of the surface treatment agents so far have shown good water and oil repellency to glass, but none of them have shown sufficient adhesion, water and oil repellency, or abrasion resistance to surfaces other than glass such as resins or metals. Sex and other superficial characteristics. Also, when a water-repellent and oil-repellent layer is provided on a resin or metal surface, performance is not sufficient when a surface treatment agent is directly applied.

Generally speaking, compounds containing fluoropolyether groups have very small surface free energy, so they have water and oil repellency, chemical resistance, lubricity, mold release, and antifouling properties. Taking advantage of this property, it is widely used in industry as water-repellent, oil-repellent and antifouling agents for paper/fiber, lubricants for magnetic recording media, oil-repellent agents for precision machines, mold release agents, cosmetics, protective films, etc. However, this property also means non-adhesion and non-adhesion to other substrates. Even if it can be coated on the surface of the substrate, it is difficult to make the film adhere.

On the other hand, silane coupling agents are widely known as agents for bonding the surface of substrates such as glass or cloth with organic compounds, and are widely used as coating agents for the surfaces of various substrates. A 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. Hydrolyzable silanes form a film by self-condensation reaction caused by moisture in the air. The film is chemically and physically bonded to the surface of glass or metal through the hydrolyzable silane group to become a durable and strong film.

Therefore, by using a polymer-modified silane containing a fluoropolyether group that introduces a hydrolyzable silyl group into a compound containing a fluoropolyether group, it is easy to adhere to the surface of the substrate, and a water-repellent silane can be formed on the surface of the substrate. The composition of coatings such as oiliness, chemical resistance, lubricity, mold release, and antifouling properties has been disclosed (Patent Documents 1 to 8: Japanese Patent Laid-Open No. 2003-238577, Japanese Patent No. 2860979, Japanese Patent Japanese Patent Application Publication No. 4672095, Japanese Patent Application Publication No. 2008-534696, Japanese Patent Application Publication No. 2008-537557, Japanese Patent Application Publication No. 2012-072272, Japanese Patent Application Publication No. 2012-157856, Japanese Patent Application Publication No. 2013-136833) .

When the surface of the substrate is treated with the above-mentioned polymer-modified silane composition containing a fluoropolyether group, various coating methods are used to form a film on the substrate, but after coating, the hydrolyzable silyl group is hydrolyzed, In the step of hardening the coating, the hydrolysis reaction is accelerated by high temperature conditions such as 80°C or 120°C, or conditions under humidification. Also, at room temperature, a hardened coating can be formed by slowly reacting with moisture in the air. However, this hardening step requires high-temperature humidification conditions, or it takes time to harden at room temperature, which may become a problem in a rate-determining step (delay factor) in production. Furthermore, the film (water and oil repellent layer) hardened under mild conditions such as room temperature hardening for a short time has problems in that abrasion resistance and antifouling performance deteriorate during use.

In Patent Document 9 (Japanese Unexamined Patent Application Publication No. 2008-144144 ), the curing is accelerated by adding fluorine-containing carboxylic acid as a curing catalyst to the coating composition, and the film is formed in a short time under mild conditions. However, when the amount of the catalyst is reduced, the wear resistance is poor, and when the amount of the catalyst is increased, the initial performance decreases. In addition, there is a high possibility that the carboxyl group of the polar group will be exposed on the outermost surface of the film, and in this case, the performance will be lowered.

In order to promote the hydrolysis reaction of the alkoxysilyl group, there is also a method of adding a catalyst. Conventionally known catalysts include organotitanates such as tetrabutyl titanate and tetraisopropyl titanate; organotitanium chelate compounds such as diisopropoxy bis(ethyl acetylacetate)titanium; Organoaluminum compounds of ginseng (acetylacetonate) aluminum, ginseng (ethyl acetylacetonate) aluminum, etc.; organozirconium compounds of tetrakis (acetylacetonate) zirconium, zirconium tetrabutyrate, etc.; dibutyltin dioctoate, dilaurate Organotin compounds such as butyltin, dibutyltin di(2-ethylhexanoate), dioctyltin dilaurate, dioctyltin diacetate, and dioctyltin dioctanoate; tin naphthenate, tin oleate, Metal salts of organic carboxylic acids such as tin butyrate, cobalt naphthenate, and zinc stearate; amine compounds such as hexylamine and dodecylamine phosphate and their salts; quaternary ammonium such as benzyltriethylammonium acetate Salts; lower fatty acid salts of alkali metals such as potassium acetate and lithium nitrate; dialkylhydroxylamines such as dimethylhydroxylamine and diethylhydroxylamine; organic compounds containing guanidine groups such as tetramethylguanidinopropyltrimethoxysilane Silicon compounds; organic acids (acetic acid, methanesulfonic acid, etc.), inorganic acids (hydrochloric acid, sulfuric acid, etc.), etc. However, these catalysts are not soluble in fluorine-based solvents, or even if they are dissolved, only a very small amount is dissolved, so the catalyst efficiency is poor. Moreover, the characteristic deterioration of the cured film may be caused by remaining metal components.

In addition, Patent Document 10 (JP 2004-145283 A) proposes a silane containing a fluoropolyalkylene ether group. The lens treated with the silane containing fluoropolyalkylene ether group has excellent oil repellency and fingerprint wiping property, but insufficient abrasion resistance.

In addition, various coating compositions have been investigated as antifouling surface treatment agents for resins and metals. For example, in Patent Document 11 (Japanese Unexamined Patent Publication No. 2012-017374 ), a surface treatment composition containing polysilazane, polysiloxane, and a curing catalyst is proposed. However, the composition of this document contains a curing catalyst, and when the cured film is formed, there is a possibility of defects caused by the catalyst, or it is not excellent in both water and oil repellency. [Prior Art Literature] [Patent Document]

[Patent Document 1] Japanese Unexamined Patent Publication No. 2003-238577 [Patent Document 2] Japanese Patent No. 2860979 [Patent Document 3] Japanese Patent No. 4672095 [Patent Document 4] Japanese PCT Publication No. 2008-534696 [Patent Document 5] Japanese National Publication No. 2008-537557 [Patent Document 6] Japanese Unexamined Patent Publication No. 2012-072272 [Patent Document 7] Japanese Unexamined Patent Publication No. 2012-157856 [Patent Document 8] Japanese Patent Laid-Open No. 2013-136833 [Patent Document 9] Japanese Unexamined Patent Publication No. 2008-144144 [Patent Document 10] Japanese Unexamined Patent Publication No. 2004-145283 [Patent Document 11] Japanese Patent Laid-Open No. 2012-017374

[Problem to be Solved by the Invention]

The present invention is made in view of the above facts, and its object is to provide a water-repellent and oil-repellent layer with excellent wear resistance, especially on the surface of resin or metal, which contains at least 3 siloxane bonds and/or at least Fluorine-containing coating agent containing hydroxyl or hydrolyzable group-containing organosilicon compounds and/or their partial (hydrolyzed) condensates modified with 2 silphenylene bonds and modified by polymers containing fluorooxyalkylene groups A composition, a surface treatment agent containing the composition, and an article surface-treated with the surface treatment agent. [Means to solve the problem]

As a result of in-depth research by the inventors and others in order to solve the above object, it was found that a polymer containing at least 3 siloxane bonds and/or at least 2 siloxane bonds in the molecule and containing a fluorooxyalkylene group The modified organosilicon compound containing hydroxyl group or hydrolyzable group and/or its partial (hydrolyzed) condensate preferably contains at least 3 siloxane bonds and /or organosilicon compounds containing hydroxyl groups or hydrolyzable groups and/or partial (hydrolyzed) condensates thereof modified by polymers containing fluorooxyalkylene groups, and at least 2 silicon-extended phenylene bonds, and perhydropolysilicon The surface treatment agent of the fluorine-containing coating agent composition in which azane is mixed in a specific blending ratio can form a water-repellent and oil-repellent layer with excellent abrasion resistance on the resin or metal surface, and the present invention has been completed.

(式中，Rf為1價或2價之含有氟氧伸烷基之聚合物殘基，A為具有由矽氧烷鍵、矽伸苯鍵，及與鍵結於A之Si一起形成矽氧烷鍵或矽伸苯鍵之基中選出的1種或2種以上之2~16價有機基，R係獨立地為碳數1~4之烷基或苯基，X係獨立地為羥基或水解性基，n為1~3之整數，m為1~15之整數，α為1或2)。 表示之分子中含有至少3個矽氧烷鍵及/或至少2個矽伸苯鍵，且經含有氟氧伸烷基之聚合物改質之含有羥基或水解性基之有機矽化合物及/或其部分(水解)縮合物，或下述通式(2)

[式中，Rf’為2價之含有氟氧伸烷基之聚合物-含有聚矽氧烷共聚物之基，Q、Q’各自為單鍵，或為可包含醚鍵、亦可經氟取代之2價有機基，Z為由單鍵、-JC=[J為烷基、羥基或K₃ SiO-(K係獨立地為氫原子、烷基、芳基或烷氧基)表示之矽烷基醚基]表示之3價基、-LSi=(L為烷基)表示之3價基、-C≡表示之4價基、-Si≡表示之4價基，及2~8價之矽氧烷殘基中選出之基，m’為1~7之整數，X、R、n係與上述相同)。 表示之分子中含有至少3個矽氧烷鍵及/或至少2個矽伸苯鍵，且經含有氟氧伸烷基之聚合物-聚矽氧烷共聚物改質之含有羥基或水解性基之有機矽化合物及/或其部分(水解)縮合物， (B)成分為下述通式(3)

(式中，x為表示聚合度之數)。 表示之全氫聚矽氮烷。 [3] 如[2]之含氟塗佈劑組成物，其中式(1)表示之分子中含有至少3個矽氧烷鍵及/或至少2個矽伸苯鍵，且經含有氟氧伸烷基之聚合物改質之含有羥基或水解性基之有機矽化合物，為下述通式(4a)或(4b)

[式中，Rf為1價或2價之含有氟氧伸烷基之聚合物殘基，Y係獨立地為可具有由矽原子、矽氧烷鍵、矽伸烷基構造及矽伸芳基構造中選出之1種或2種以上的2~6價有機基，R係獨立地為碳數1~4之烷基或苯基，X係獨立地為羥基或水解性基，n為1~3之整數，a為1~5之整數，W為氫原子，或下述式(4a’)

(式中，Y’為可具有矽原子及/或矽氧烷鍵之2~6價有機基，b為1~5之整數，R、X、n係與上述相同)。 表示之基，Y與Y’之合計中具有至少3個矽氧烷鍵及/或至少2個矽伸苯鍵；α為1或2]；

(式中，U為-(CH₂ )_z1 O-，z1為1~20之整數，A¹ 為 -(CH₂ )_z2 -，z2為1~20之整數，V為具有矽氧烷鍵及/或矽伸苯鍵，且可具有矽伸烷基構造及/或矽伸苯鍵以外之矽伸芳基構造的2~6價烴基，c為1~5之整數；Rf、X、R、n、α係與上述相同)。 表示之分子中含有至少3個矽氧烷鍵及/或至少2個矽伸苯鍵，且經含有氟氧伸烷基之聚合物改質之含有羥基或水解性基之有機矽化合物。 [4] 如[2]或[3]之含氟塗佈劑組成物，其中前述式(1)、(4a)及(4b)中，α各自為1，Rf為下述通式(5)表示之1價之含有氟氧伸烷基之聚合物殘基；

(式中，p、q、r、s各自為0~200之整數，p+q+r+s=3~200，各重複單位可為直鏈狀亦可為分支狀，各重複單位彼此可隨機地鍵結，d為1~3之整數，該單位可為直鏈狀亦可為分支狀)。 [5] 如[2]或[3]之含氟塗佈劑組成物，其中前述式(1)、(4a)及(4b)中，α各自為2，Rf為下述通式(6)表示之2價之含有氟氧伸烷基之聚合物殘基；

(式中，p、q、r、s各自為0~200之整數，p+q+r+s=3~200，各重複單位可為直鏈狀亦可為分支狀，各重複單位彼此可隨機地鍵結，d為1~3之整數，該單位可為直鏈狀亦可為分支狀)。 [6] 如[3]~[5]中任一項之含氟塗佈劑組成物，其中前述式(4a)中，Y為選自由碳數5~10之伸烷基、包含碳數6~8之伸芳基之伸烷基、伸烷基相互透過矽伸烷基構造或矽伸芳基構造而鍵結之2價基，及碳數2~10之伸烷基鍵結於矽原子數2~100個之直鏈狀或分支狀或環狀之2~4價之有機聚矽氧烷殘基的鍵結部位而得的2~4價基所成之群之基。 [7] 如[3]~[6]中任一項之含氟塗佈劑組成物，其中前述式(4a’)中，Y’為選自由碳數2~10之伸烷基、包含碳數6~8之伸芳基之伸烷基、包含二有機亞矽基之碳數2~6之伸烷基、伸烷基相互透過矽伸烷基構造或矽伸芳基構造而鍵結之2價基，及碳數2~10之伸烷基鍵結於矽原子數2~10個之直鏈狀或矽原子數3~10個之分支狀或環狀之2~4價之有機聚矽氧烷殘基的鍵結部位而得的2~4價基所成之群之基。 [8] 如[2]之含氟塗佈劑組成物，其中式(2)中之Rf’，為下述通式(7)或(8)表示之2價之含有氟氧伸烷基之聚合物-含有聚矽氧烷共聚物之基，

(式中，Q為單鍵，或可包含醚鍵，且可經氟取代之2價有機基，Rf¹ 為2價之含有氟氧伸烷基之聚合物殘基，Z’為2價之聚矽氧烷殘基，各自可相同亦可相異；e係獨立地為0或1，f為1~3之整數)。 [9] 如[8]之含氟塗佈劑組成物，其中式(7)及(8)中之Z’為下述通式(9)或(10)表示之聚矽氧烷鏈，Rf¹ 為下述通式(6)表示之2價之含有氟氧伸烷基之聚合物殘基；

(式中，R’係可相同或相異的碳數1~4之烷基、苯基或苯基乙基。t為10~200之整數，y為1~5之整數，w1及w2各自為1~200之整數，可相同或相異)；

(式中，p、q、r、s各自為0~200之整數，p+q+r+s=3~200，各重複單位可為直鏈狀亦可為分支狀，各重複單位彼此可隨機地鍵結，d為1~3之整數，該單位可為直鏈狀亦可為分支狀)。 [10] 如[2]~[9]中任一項之含氟塗佈劑組成物，其中前述式(1)、(2)、(4a)及/或(4b)中，X各自為選自由羥基、碳數1~10之烷氧基、碳數2~10之烷氧基烷氧基、碳數1~10之醯氧基、碳數2~10之烯氧基及鹵基所成之群者。 [11] 如請求項1~10中任一項之含氟塗佈劑組成物，其中(A)成分之分子中含有至少3個矽氧烷鍵及/或至少2個矽伸苯鍵，且經含有氟氧伸烷基之聚合物改質之含有羥基或水解性基之有機矽化合物，為下述式之任一者表示者；

(式中，p1為5~100之整數、q1為5~100之整數，p1+q1為10~105之整數，此等重複單位可隨機地鍵結)；

(式中，p2為5~100之整數、q2為5~100之整數，p2+q2為10~105之整數，t1為4~199之整數，t2為0~99之整數；括弧內所示之各重複單位可隨機地鍵結)。 [12] 如[1]~[11]中任一項之含氟塗佈劑組成物，其中(A)成分之分子中含有至少3個矽氧烷鍵及/或至少2個矽伸苯鍵，且經含有氟氧伸烷基之聚合物改質之含有羥基或水解性基之有機矽化合物及/或其部分(水解)縮合物，為可溶於二丁基醚者。 [13] 一種表面處理劑，其含有如[1]~[12]中任一項之含氟塗佈劑組成物。 [14] 一種硬化被膜，其係由如[13]之表面處理劑之硬化物所構成。 [15] 一種物品，其係於表面具有如[13]之表面處理劑之硬化被膜。 [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 articles surface-treated with the surface treatment agent. [1] A fluorine-containing coating agent composition, characterized in that (A) contains at least 3 siloxane bonds and/or at least 2 siloxane bonds in the molecule, and is polymerized by a fluorooxyalkylene group. Organosilicon compounds containing hydroxyl groups or hydrolyzable groups and/or their partial (hydrolyzed) condensates modified by substances, and (B) perhydropolysilazane, and the mixing mass ratio of (A) component to (B) component 5:95~95:5 (provided that the total mixing mass ratio of (A) component and (B) component is 100). [2] The fluorine-containing coating agent composition according to [1], wherein the component (A) has the following general formula (1)

(In the formula, Rf is a 1- or 2-valent polymer residue containing fluorooxyalkylene groups, and A is a siloxane bond, a siloxane bond, and a siloxane bonded with Si bonded to A. One or two or more 2-16 valent organic groups selected from the bases of alkyl bonds or silicon-extended phenyl bonds, R is independently alkyl or phenyl with 1 to 4 carbons, and X is independently hydroxyl or Hydrolyzable group, n is an integer of 1 to 3, m is an integer of 1 to 15, and α is 1 or 2). Organosilicon compounds containing hydroxyl or hydrolyzable groups and/or containing at least 3 siloxane bonds and/or at least 2 siloxane bonds in the molecule and modified by polymers containing fluorooxyalkylene groups Its partial (hydrolysis) condensate, or the following general formula (2)

[wherein, Rf' is a divalent fluorooxyalkylene-containing polymer-containing polysiloxane copolymer group, Q, Q' are each a single bond, or may contain an ether bond, or may be passed through a fluorine A substituted divalent organic group, Z is a silane represented by a single bond, -JC=[J is an alkyl group, a hydroxyl group or K ₃ SiO- (K is independently a hydrogen atom, an alkyl group, an aryl group or an alkoxy group) 3-valent group represented by base ether group], 3-valent group represented by -LSi=(L is an alkyl group), 4-valent group represented by -C≡, 4-valent group represented by -Si≡, and 2-8 valent silicon A group selected from oxane residues, m' is an integer of 1 to 7, and X, R, and n are the same as above). Indicates that the molecule contains at least 3 siloxane bonds and/or at least 2 siloxane bonds, and is modified by a polymer-polysiloxane copolymer containing a fluorooxyalkylene group, containing a hydroxyl group or a hydrolyzable group The organosilicon compound and/or its partial (hydrolyzed) condensate, (B) component is the following general formula (3)

(In the formula, x is a number indicating the degree of polymerization). Represented perhydropolysilazane. [3] The fluorine-containing coating agent composition as in [2], wherein the molecule represented by formula (1) contains at least 3 siloxane bonds and/or at least 2 siloxane bonds, and contains oxyfluoride An organosilicon compound containing a hydroxyl group or a hydrolyzable group modified by an alkyl polymer is the following general formula (4a) or (4b)

[wherein, Rf is a monovalent or divalent polymer residue containing a fluorooxyalkylene group, and Y is independently a group consisting of a silicon atom, a siloxane bond, a silane group structure, and a silicon aryl group. One or more 2-6 valent organic groups selected in the structure, R is independently an alkyl or phenyl group with 1-4 carbons, X is independently a hydroxyl group or a hydrolyzable group, and n is 1-4 An integer of 3, a is an integer of 1 to 5, W is a hydrogen atom, or the following formula (4a')

(In the formula, Y' is a 2-6 valent organic group that may have a silicon atom and/or a siloxane bond, b is an integer of 1-5, and R, X, and n are the same as above). The base represented by Y and Y' has at least 3 siloxane bonds and/or at least 2 siloxane bonds; α is 1 or 2];

(In the formula, U is -(CH ₂ ) _z1 O-, z1 is an integer from 1 to 20, A ¹ is -(CH ₂ ) _z2 -, z2 is an integer from 1 to 20, V is a siloxane bond and / or a silane phenyl bond, and may have a silane phenylene structure and/or a 2-6 valent hydrocarbon group with a silane aryl structure other than a silane phenyl bond, c is an integer of 1 to 5; Rf, X, R, n and α are the same as above). It refers to organosilicon compounds containing hydroxyl groups or hydrolyzable groups that contain at least 3 siloxane bonds and/or at least 2 siloxane bonds and are modified by polymers containing fluorooxyalkylene groups in the molecule. [4] The fluorine-containing coating agent composition according to [2] or [3], wherein in the aforementioned formulas (1), (4a) and (4b), α is each 1, and Rf is the following general formula (5) The monovalent polymer residue containing fluorooxyalkylene group;

(wherein, p, q, r, and s are each an integer of 0 to 200, p+q+r+s=3 to 200, each repeating unit can be linear or branched, and each repeating unit can be mutually Randomly bonded, d is an integer from 1 to 3, and the unit can be linear or branched). [5] The fluorine-containing coating agent composition according to [2] or [3], wherein in the aforementioned formulas (1), (4a) and (4b), α is each 2, and Rf is the following general formula (6) 2-valent polymer residues containing fluorooxyalkylene groups;

(wherein, p, q, r, and s are each an integer of 0 to 200, p+q+r+s=3 to 200, each repeating unit can be linear or branched, and each repeating unit can be mutually Randomly bonded, d is an integer from 1 to 3, and the unit can be linear or branched). [6] The fluorine-containing coating agent composition according to any one of [3] to [5], wherein in the aforementioned formula (4a), Y is an alkylene group selected from 5 to 10 carbon atoms, including 6 carbon atoms. The alkylene group of the ~8 arylylene group, the divalent group that is bonded to each other through the silicon alkylene structure or the silicon alkylene structure, and the alkylene group with 2 to 10 carbons is bonded to the silicon atom The group of 2-4 valent groups obtained from the bonding sites of 2-100 linear, branched or cyclic 2-4 valent organopolysiloxane residues. [7] The fluorine-containing coating agent composition according to any one of [3] to [6], wherein in the aforementioned formula (4a'), Y' is an alkylene group selected from 2 to 10 carbons, including carbon An alkylene group of an arylylene group with a number of 6 to 8, an alkylene group with a carbon number of 2 to 6 including a diorganosilylene group, and an alkylene group bonded to each other through a siliconyl structure or a silicon aryl structure A divalent group, and an alkylene group with 2 to 10 carbons bonded to a straight chain with 2 to 10 silicon atoms or a branched or cyclic 2 to 4 valent organic polymer with 3 to 10 silicon atoms The base of the group formed by the 2-4 valent groups obtained from the bonding site of the siloxane residue. [8] The fluorine-containing coating agent composition as in [2], wherein Rf' in the formula (2) is a divalent fluorooxyalkylene group-containing compound represented by the following general formula (7) or (8). Polymer-containing polysiloxane copolymer base,

(wherein, Q is a single bond, or may contain an ether bond, and may be fluorine-substituted divalent organic group, Rf ¹ is a divalent polymer residue containing a fluorooxyalkylene group, Z' is a divalent The polysiloxane residues may be the same or different; e is independently 0 or 1, and f is an integer of 1 to 3). [9] The fluorine-containing coating agent composition as in [8], wherein Z' in the formulas (7) and (8) is a polysiloxane chain represented by the following general formula (9) or (10), Rf ¹ is a divalent fluorooxyalkylene group-containing polymer residue represented by the following general formula (6);

(In the formula, R' is an alkyl, phenyl or phenylethyl group with the same or different carbon numbers of 1 to 4. t is an integer of 10 to 200, y is an integer of 1 to 5, and w1 and w2 are respectively Integers from 1 to 200, can be the same or different);

(wherein, p, q, r, and s are each an integer of 0 to 200, p+q+r+s=3 to 200, each repeating unit can be linear or branched, and each repeating unit can be mutually Randomly bonded, d is an integer from 1 to 3, and the unit can be linear or branched). [10] The fluorine-containing coating agent composition according to any one of [2] to [9], wherein in the aforementioned formulas (1), (2), (4a) and/or (4b), X is each selected from Free hydroxyl, alkoxyl with 1~10 carbons, alkoxyalkoxyl with 2~10 carbons, acyloxyl with 1~10 carbons, alkenyloxyl with 2~10 carbons and halogen group of people. [11] The fluorine-containing coating agent composition according to any one of claims 1 to 10, wherein the molecule of component (A) contains at least 3 siloxane bonds and/or at least 2 siloxane bonds, and Organosilicon compounds containing hydroxyl groups or hydrolyzable groups modified by polymers containing fluorooxyalkylene groups are represented by any of the following formulas;

(In the formula, p1 is an integer from 5 to 100, q1 is an integer from 5 to 100, p1+q1 is an integer from 10 to 105, and these repeating units can be randomly bonded);

(In the formula, p2 is an integer from 5 to 100, q2 is an integer from 5 to 100, p2+q2 is an integer from 10 to 105, t1 is an integer from 4 to 199, and t2 is an integer from 0 to 99; shown in brackets Each repeating unit can be randomly bonded). [12] The fluorine-containing coating agent composition according to any one of [1] to [11], wherein the molecule of component (A) contains at least 3 siloxane bonds and/or at least 2 siloxane bonds , and the organosilicon compounds containing hydroxyl or hydrolyzable groups and/or their partial (hydrolyzed) condensates modified by polymers containing fluorooxyalkylene groups are soluble in dibutyl ether. [13] A surface treatment agent containing the fluorine-containing coating composition according to any one of [1] to [12]. [14] A cured film comprising a hardened product of the surface treatment agent described in [13]. [15] An article having a hardened coating of the surface treatment agent described in [13] on its surface. [Effect of Invention]

The fluorine-containing coating agent composition of the present invention preferably contains at least 3 siloxane bonds and/or at least 2 siloxanes in the molecules soluble in dibutyl ether by mixing in a specific blending ratio. Bonds, and containing hydroxyl or hydrolyzable group-containing polymer modified organosilicon compound and/or its partial (hydrolyzed) condensate, and perhydropolysilazane, perhydropolysilazane Adhere to the substrate, and then the hydroxyl group on the perhydropolysilazane layer will react with the hydroxyl group or hydrolyzable group of the polymer-modified organosilicon compound containing fluorooxyalkylene group, so as to make it a surface treatment agent The tightness becomes firm. Thereby, articles surface-treated with a surface treatment agent containing the organosilicon compound and/or its partial (hydrolyzed) condensate and perhydropolysilazane fluorine-containing coating agent composition are water and oil repellent and Excellent abrasion resistance, especially cloth abrasion resistance.

The fluorine-containing coating agent composition of the present invention contains (A) at least 3 siloxane bonds and/or at least 2 siloxane bonds in the molecule, and is modified by a polymer containing a fluorooxyalkylene group Organosilicon compounds containing hydroxyl groups or hydrolyzable groups and/or their partial (hydrolyzed) condensates, and (B) perhydropolysilazane, and the mixing mass ratio of (A) component to (B) component is 5: Composition of 95~95:5, preferably 30:70~95:5, especially preferably 40:60~95:5 (provided that the total mass ratio of (A) component to (B) component is 100) It is characterized in that by mixing these ingredients in the above-mentioned specific blending ratio, it is possible to obtain a cured product with improved adhesion to the base material, water and oil repellency, and abrasion resistance, especially cloth abrasion resistance. Surface treatment agent for film. In the above blending ratio, when the (A) component is too large, the adhesion to the base material is poor, and as a result, a cured coating excellent in abrasion resistance cannot be obtained, and when the (A) component is too small, a coating excellent in abrasion resistance cannot be obtained. Hardened coating.

(A) The molecule of component (A) contains at least 3 siloxane bonds and/or at least 2 siloxane bonds, and is modified by a polymer containing a fluorooxyalkylene group and contains a hydroxyl group or a hydrolyzable group. Organosilicon compounds and/or their partial (hydrolyzed) condensates contain at least 3 siloxane bonds (i.e. Si-O-Si bonds) and/or at least 2 siloxane bonds (i.e. Si-O-Si bonds) in the molecule -C ₆ H ₅ -Si bond), and the molecule contains a hydroxyl group or a hydrolyzable group, and is preferably a dibutyl ether-soluble component.

(式中，Rf為1價或2價之含有氟氧伸烷基之聚合物殘基，A為具有由矽氧烷鍵、矽伸苯鍵，及與鍵結於A之Si一起形成矽氧烷鍵或矽伸苯鍵之基中選出的1種或2種以上之2~16價有機基，R係獨立地為碳數1~4之烷基或苯基，X係獨立地為羥基或水解性基，n為1~3之整數，m為1~15之整數，α為1或2)。 表示之分子中含有至少3個矽氧烷鍵及/或至少2個矽伸苯鍵，且經含有氟氧伸烷基之聚合物改質之含有羥基或水解性基之有機矽化合物及/或其部分(水解)縮合物，或下述通式(2)

[式中，Rf’為2價之含有氟氧伸烷基之聚合物-含有聚矽氧烷共聚物之基，Q、Q’各自為單鍵，或為可包含醚鍵、亦可經氟取代之2價有機基，Z為由單鍵、-JC=[J為烷基、羥基或K₃ SiO-(K係獨立地為氫原子、烷基、芳基或烷氧基)表示之矽烷基醚基]表示之3價基、-LSi=(L為烷基)表示之3價基、-C≡表示之4價基、-Si≡表示之4價基，及2~8價之矽氧烷殘基中選出之基，m’為1~7之整數，X、R、n係與上述相同)。 表示之分子中含有至少3個矽氧烷鍵及/或至少2個矽伸苯鍵，且經含有氟氧伸烷基之聚合物-聚矽氧烷共聚物改質之含有羥基或水解性基之有機矽化合物及/或其部分(水解)縮合物。The molecule of the component (A) contains at least 3, preferably 3 to 100, more preferably 3 to 40, and more preferably 3 to 20 siloxane bonds and/or contains at least 2 siloxane bonds in the molecule , preferably 2 to 10 silicon-extended phenylene bonds, and modified by polymers containing fluorooxyalkylene groups, containing hydroxyl groups or hydrolyzable groups. More suitable ones can include the following general formula (1)

(In the formula, Rf is a 1- or 2-valent polymer residue containing fluorooxyalkylene groups, and A is a siloxane bond, a siloxane bond, and a siloxane bonded with Si bonded to A. One or two or more 2-16 valent organic groups selected from the bases of alkyl bonds or silicon-extended phenyl bonds, R is independently alkyl or phenyl with 1 to 4 carbons, and X is independently hydroxyl or Hydrolyzable group, n is an integer of 1 to 3, m is an integer of 1 to 15, and α is 1 or 2). Organosilicon compounds containing hydroxyl or hydrolyzable groups and/or containing at least 3 siloxane bonds and/or at least 2 siloxane bonds in the molecule and modified by polymers containing fluorooxyalkylene groups Its partial (hydrolysis) condensate, or the following general formula (2)

[wherein, Rf' is a divalent fluorooxyalkylene-containing polymer-containing polysiloxane copolymer group, Q, Q' are each a single bond, or may contain an ether bond, or may be passed through a fluorine A substituted divalent organic group, Z is a silane represented by a single bond, -JC=[J is an alkyl group, a hydroxyl group or K ₃ SiO- (K is independently a hydrogen atom, an alkyl group, an aryl group or an alkoxy group) 3-valent group represented by base ether group], 3-valent group represented by -LSi=(L is an alkyl group), 4-valent group represented by -C≡, 4-valent group represented by -Si≡, and 2-8 valent silicon A group selected from oxane residues, m' is an integer of 1 to 7, and X, R, and n are the same as above). Indicates that the molecule contains at least 3 siloxane bonds and/or at least 2 siloxane bonds, and is modified by a polymer-polysiloxane copolymer containing a fluorooxyalkylene group, containing a hydroxyl group or a hydrolyzable group Organosilicon compounds and/or their partial (hydrolyzed) condensates.

(式中，p、q、r、s各自為0~200之整數，p+q+r+s= 3~200，各重複單位可為直鏈狀亦可為分支狀，各重複單位彼此可隨機地鍵結，d為1~3之整數，該單位可為直鏈狀亦可為分支狀)。In the above formula (1), Rf is a monovalent or divalent polymer residue containing a fluorooxyalkylene group, and when α is 1, it is preferred that Rf is a monovalent fluorooxyalkylene group-containing polymer residue Rf is a monovalent fluorooxyalkylene group-containing polymer residue represented by the following formula (5).

(In the formula, p, q, r, s are respectively the integer of 0～200, p+q+r+s=3～200, each repeating unit can be straight chain shape also can be branched, each repeating unit can mutually Randomly bonded, d is an integer from 1 to 3, and the unit can be linear or branched).

(式中，p、q、r、s各自為0~200之整數，p+q+r+s= 3~200，各重複單位可為直鏈狀亦可為分支狀，各重複單位彼此可隨機地鍵結，d係每單位各自獨立地為1~3之整數，該單位可為直鏈狀亦可為分支狀)。Also, in the above-mentioned formula (1), when α is 2, it is preferable that Rf is a divalent polymer residue containing oxyalkylene fluoride, and Rf is a divalent oxyfluoride-containing polymer residue represented by the following formula (6). Alkylene polymer residue.

(In the formula, p, q, r, s are respectively the integer of 0～200, p+q+r+s=3～200, each repeating unit can be straight chain shape also can be branched, each repeating unit can mutually Randomly bonded, each unit of d is independently an integer of 1 to 3, and the units may be linear or branched).

In the above formulas (5) and (6), p, q, r, and s are each an integer of 0 to 200, preferably, p is an integer of 5 to 100, q is an integer of 5 to 100, and r is an integer of 0 to 100. An integer of 100, s is an integer of 0~100, p+q+r+s=3~200, preferably 10~105, each repeating unit can be linear or branched, and each repeating unit can be mutually Bond randomly. More preferably, p+q is an integer of 10~105, especially 15~60, and r=s=0. If p+q+r+s is less than the above upper limit, the adhesiveness or curability will be good, and if it is greater than the above lower limit, the characteristics of the fluoropolyether group can be fully exhibited, which is preferable.

(式中，p’、q’、r’、s’各自為1以上之整數，其上限係與上述p、q、r、s之上限相同。u為1~24之整數、v為1~24之整數。各重複單位可隨機地鍵結)。As monovalent or divalent Rf, specifically, the following can be exemplified.

(In the formula, p', q', r', and s' are each an integer greater than 1, and the upper limit is the same as the upper limit of the above-mentioned p, q, r, and s. u is an integer from 1 to 24, and v is an integer from 1 to 24. Integer of 24. Each repeating unit can be randomly bonded).

In the above formula (1), A has a siloxane bond, a silicon-extended phenyl bond, and forms a siloxane bond or a silicon-extended phenyl bond with Si bonded to A (that is, the terminal has a -SiO- group or -SiC ₆ H ₅ -group), one or more selected from the group, in the case of siloxane bonds, preferably 3 to 100, and in the case of siloxane bonds, preferably 2 to 100 10 organic groups with a valence of 2 to 16, preferably 2 to 8, more preferably 2 to 7, and are polymer residues containing fluorooxyalkylene groups and polymers containing hydroxyl groups and/or hydrolyzable groups The linking group of the silyl group. As the organic group of A, preferable examples include organosiloxane residues, phenylene residues, etc., which can pass through an oxygen atom (ether bond), amide bond, hydroxyl group, linear, branched or cyclic organosiloxane residues, etc. A siloxane bond and/or a siloxane bond substituted with a heteroatom structure of a silyl aryl residue, etc., or a group that forms a siloxane bond and/or a silyl phenyl bond together with Si bonded to A , in the case of siloxane bonds, it is preferable to have 3 to 100, and in the case of siloxane bonds, it is preferable to have 2 to 10 valences of 2 to 16, especially 2 to 8, and especially 2 to 8. 4-valent hydrocarbon group, etc. As A, specifically, the following groups are mentioned.

Also, in the above formula (1), R is independently an alkyl group such as methyl, ethyl, propyl, butyl, etc. having 1 to 4 carbons, or a phenyl group, preferably a methyl group. X is independently a hydroxyl group or a hydrolyzable group, and the hydrolyzable group can include alkoxy groups with 1 to 10 carbon atoms such as methoxy, ethoxy, propoxy, butoxy; methoxymethoxy, Alkoxyalkoxy with 2 to 10 carbons such as methoxyethoxy; acyloxy with 1 to 10 carbons such as acetyloxy; alkene with 2 to 10 carbons such as isopropenyloxy Oxygen; halogen such as chloro, bromo, iodo, etc. Among them, methoxy and ethoxy are particularly suitable. n is an integer of 1-3, preferably 3, m is an integer of 1-15, preferably an integer of 1-7, more preferably an integer of 1-6, and α is 1 or 2.

[式中，Rf、R、X、n、α係與上述相同，Y係獨立地為可具有由矽原子、矽氧烷鍵、矽伸烷基構造及矽伸芳基構造中選出之1種或2種以上的2~6價有機基，a為1~5之整數，W為氫原子，或下述式(4a’)

(式中，Y’為可具有矽原子及/或矽氧烷鍵之2~6價有機基，b為1~5之整數，R、X、n係與上述相同)。 表示之基，Y與Y’之合計中具有至少3個矽氧烷鍵及/或至少2個矽伸苯鍵]；

(式中，U為-(CH₂ )_z1 O-、z1為1~20之整數，A¹ 為 -(CH₂ )_z2 -，z2為1~20之整數，V為具有矽氧烷鍵及/或矽伸苯鍵，且可具有矽伸烷基構造及/或矽伸苯鍵以外之矽伸芳基構造的2~6價烴基，c為1~5之整數；Rf、X、R、n、α係與上述相同)。Further, the molecule represented by the above general formula (1) contains at least 3 siloxane bonds and/or at least 2 siloxane bonds, and is modified by a polymer containing a fluorooxyalkylene group containing a hydroxyl group or hydrolyzed The organosilicon compound of the sexual group is preferably a molecule represented by the following general formula (4a) or (4b) containing at least 3 siloxane bonds and/or at least 2 siloxane bonds, and containing oxyfluoride An organosilicon compound modified by an alkylene polymer containing a hydroxyl group or a hydrolyzable group.

[In the formula, Rf, R, X, n, and α are the same as above, and Y is independently selected from a silicon atom, a siloxane bond, a siliconyl structure, and a siliconyl structure. or two or more 2-6 valent organic groups, a is an integer of 1-5, W is a hydrogen atom, or the following formula (4a')

(In the formula, Y' is a 2-6 valent organic group that may have a silicon atom and/or a siloxane bond, b is an integer of 1-5, and R, X, and n are the same as above). The group represented, the sum of Y and Y' has at least 3 siloxane bonds and/or at least 2 siloxane bonds];

(In the formula, U is -(CH ₂ ) _z1 O-, z1 is an integer of 1 to 20, A ¹ is -(CH ₂ ) _z2 -, z2 is an integer of 1 to 20, V is a siloxane bond and / or a silane phenyl bond, and may have a silane phenylene structure and/or a 2-6 valent hydrocarbon group with a silane aryl structure other than a silane phenyl bond, c is an integer of 1 to 5; Rf, X, R, n and α are the same as above).

In the above formula (4a), Y can have a valence of 2 to 6 selected from a silicon atom, a siloxane bond, a silane group structure and a silylene aryl structure, preferably 2 ~4-valent, more preferably divalent organic groups, as Y, specifically, butyl (tetramethylene, methylpropyl) and hexamethylene groups having 4 to 10 carbon atoms can be mentioned. Alkylene group; Alkylene group of arylylene group with 6~8 carbon number including phenylene group (such as alkylene group with 8~16 carbon number, arylylene group, etc.); A divalent group bonded by a silicon-extended aryl structure; an alkylene group with 2 to 10 carbon atoms is bonded to silicon atoms with 2 to 100 atoms, preferably 5 to 100 atoms, and more preferably 10 to 50 atoms A 2-6 valent group derived from the bonding site of a straight-chain, branched or cyclic 2-6 valent organopolysiloxane residue, preferably an alkylene group with 5 to 10 carbons; An arylylene group containing 6-8 carbons, especially a phenylene group; a divalent group in which the alkylene groups are bonded to each other through a silylene structure or a silylene aryl structure; carbon numbers 2-10 The alkene group is bonded to the bonding site of a linear 2-100 silicon atom or a branched or cyclic 2-4 valent organopolysiloxane residue with 3-100 silicon atoms. 2-4 valent groups obtained; more preferably alkylene groups with 3-6 carbons.

(式中，R¹ 為甲基、乙基、丙基、丁基等之碳數1~4之烷基；苯基等之碳數6~10之芳基，R¹ 可相同亦可相異；R² 為亞甲基、伸乙基、伸丙基(三亞甲基、甲基伸乙基)等之碳數1~4之伸烷基；伸苯基等之碳數6~10之伸芳基)。Here, the silylene group structure and the silylene aryl structure are exemplified below.

(In the formula, R ¹ is an alkyl group with 1 to 4 carbons such as methyl, ethyl, propyl, butyl, etc.; an aryl group with 6 to 10 carbons such as phenyl, and R ¹ can be the same or different ; R2 is an alkylene group with ¹ to 4 carbons such as methylene, ethylidene, propylidene (trimethylene, methylethylidene); an alkylene group with 6 to 10 carbons such as phenylene Aryl).

(式中，R¹ 係與上述相同。g為1~99、較佳為4~99、較佳為9~49之整數，h為2~6、較佳為2~4之整數，j為0~8之整數、較佳為0或1，h+j為3~100、較佳為5~100、更佳為10~50之整數，k為1~3之整數，較佳為2或3)。In addition, a linear, branched or cyclic 2-6 valent organopolysiloxane residue with 2-100 silicon atoms, preferably 5-100, more preferably 10-50, can be Examples are shown below.

(wherein, R is the same as above. g is ^an integer of 1-99, preferably 4-99, preferably 9-49, h is 2-6, preferably an integer of 2-4, j is An integer of 0~8, preferably 0 or 1, h+j is 3~100, preferably 5~100, more preferably an integer of 10~50, k is an integer of 1~3, preferably 2 or 3).

(式中，g1為2~99之整數、h1為2~10之整數)。 作為Y，較佳為具有矽氧烷鍵及/或矽伸苯鍵之基。Specific examples of Y include, for example, the following groups.

(In the formula, g1 is an integer of 2 to 99, and h1 is an integer of 2 to 10). Y is preferably a group having a siloxane bond and/or a silylphenylene bond.

(式中，Y’為可具有矽原子及/或矽氧烷鍵之2~6價有機基，b為1~5之整數、較佳為1~3之整數，R、X、n係與上述相同)。In the above formula (4a), W is a hydrogen atom or a group represented by the following formula (4a').

(wherein, Y' is a 2-6 valent organic group that may have a silicon atom and/or a siloxane bond, b is an integer of 1-5, preferably an integer of 1-3, R, X, and n are the same as Same as above).

In the above formula (4a'), Y' is an organic group with a valence of 2 to 6, preferably 2 to 4, more preferably divalent, and may have a silicon atom and/or a siloxane bond. Specific examples of Y' include ethylidene, propylidene (trimethylene, methylethylidene), butylene (tetramethylene, methylpropylidene), hexamethylene, etc. Alkylene groups with 2 to 10 carbons, especially 3 to 10 carbons; alkylene groups with 6 to 10 carbons, especially arylylenes with 6 to 8 carbons including phenylene, etc. 8~16 alkylene groups, arylylene groups, etc.); oxyalkylene groups with 2~10 carbon atoms; diorganosilylene groups with 2 carbon atoms including dimethylsilylene or diethylsilylene, etc. An alkylene group of ~6; a divalent group in which the alkylene group is bonded to each other through a silanealkyl structure or a silylene aryl structure; a straight chain containing 2 to 10 silicon atoms, preferably 2 to 5 An alkylene group with 2-6 carbons in a 2-6-valent organopolysiloxane residue in a shape, branched or cyclic shape; an alkylene group with 2-10 carbons is bonded to 2-10 silicon atoms , preferably 2 to 5 valent groups obtained from the bonding sites of 2 to 5 linear, branched or cyclic 2 to 6 valent organopolysiloxane residues, etc., preferably the carbon number 3-10 alkylene groups, phenylene-containing alkylene groups, 2-6-carbon alkylene groups containing dimethylsilylene, and silylene-alkylene groups through a siliconylene structure or siliconylene aryl groups Bivalent groups that are structurally bonded, a straight chain divalent organopolysiloxane residue containing 2 to 10 silicon atoms, an alkene group with 2 to 6 carbons, and an alkene group with 2 to 10 carbons The alkyl group is bonded to the bonding site of a straight chain with 2 to 10 silicon atoms or a branched or cyclic 2 to 4 valent organopolysiloxane residue with 3 to 10 silicon atoms A 2-4 valent group, more preferably an alkylene group with 3-6 carbons.

Here, the siliconyl structure, the silicon aryl structure, and the 2-6 valent organopolysilicon with 2 to 10 silicon atoms, preferably 2 to 5, are linear, branched or cyclic. As the oxane residue, the same ones as those described above can be exemplified.

Specific examples of Y' include, for example, the following groups.

In the above formula (4a), the siloxane bond has at least 3 in the total of Y and Y', preferably 3 to 100; the siloxane bond has at least 3 in the total of Y and Y'. At least 2, preferably 2-10.

In the above formula (4a), a is an integer of 1-5, preferably an integer of 1-3.

In the above formula (4b), U is -(CH ₂ ) _z1 O-, and z1 is an integer of 1-20, preferably an integer of 1-10, more preferably an integer of 1-5. Also, A ¹ is -(CH ₂ ) _z2 -, and z2 is an integer of 1-20, preferably an integer of 1-10, more preferably an integer of 1-5.

In the above formula (4b), V preferably has 3 to 100 siloxane bonds and/or preferably has 2 to 10 siloxane bonds, and may have a silane group structure and/or a silane phenyl bond 2-6 valent hydrocarbon groups other than silicon-extended aryl groups. Specifically, it is a linear, branched or cyclic 2-4 valent organic polymer with 2-10 carbon atoms bonded to 3-100 silicon atoms, preferably 5-100. A 2-4 valent group derived from the bonding site of a siloxane residue; an alkylene group with 2-10 carbon atoms is bonded to a straight-chain organic (poly)silicon phenylene group with 2-10 silicon atoms A divalent group derived from the bonding site of the residue; a group represented by -Si(OSiR ³ ₂ -R ⁴ -) ₃ . Here, ^R3 is independently an alkyl or phenyl group such as methyl, ethyl, propyl, butyl, etc. with 1 to ⁴ carbons, and R4 is independently methylene with 1 to 4 carbons, Alkylene or phenylene such as ethylidene, propylidene (trimethylene, methylethylidene). V is preferably those shown below.

In the above formula (4b), c is an integer of 1-5, preferably an integer of 1-3.

The molecule represented by the above formula (4a) or (4b) contains at least 3 siloxane bonds and/or at least 2 siloxane bonds, and has a hydrolyzable group-containing polymer modified organic fluorooxyalkylene group. The silicon compound specifically includes the following structures. Furthermore, in the following formulae, p1 is an integer of 5~100, q1 is an integer of 5~100, and p1+q1 is an integer of 10~105, but the values of p1 and q1 that are more suitable for each formula are shown in the brackets .

In the above general formula (2), Q and Q' are each a single bond, or a divalent organic group that may contain an ether bond or may be substituted by fluorine, preferably an unsubstituted or fluorine-substituted carbon that may contain an ether bond A divalent organic group with a number of 2 to 12; preferably an unsubstituted or fluorine-substituted divalent hydrocarbon group with a carbon number of 2 to 12 that may contain an ether bond.

Here, unsubstituted or fluorine-substituted divalent hydrocarbon groups with carbon numbers of 2 to 12 can be ethylidene, propylidene (trimethylene, methylethylidene), butylene (tetramethylene, methylidene) propylene), hexamethylene, octamethylene, etc.; arylylene, such as phenylene, or a combination of two or more of these groups (alkylene, arylylene, etc.) Furthermore, some or all of the hydrogen atoms of these groups are substituted by fluorine atoms, among which unsubstituted or substituted C2-C4 alkyl groups and phenyl groups are preferred.

(式中，b1為2~4之整數)。Such Q and Q' include, for example, the following groups.

(In the formula, b1 is an integer of 2 to 4).

(式中，Q係與上述相同，Rf¹ 為2價之含有氟氧伸烷基之聚合物殘基，Z’為2價之聚矽氧烷殘基，各自可相同亦可相異。e係獨立地為0或1，f為1~3之整數、較佳為1或2)。In the above general formula (2), Rf' is a divalent fluorooxyalkylene-containing polymer-containing polysiloxane copolymer group, preferably represented by the following general formula (7) or (8) Divalent fluorooxyalkylene-containing polymer-based polysiloxane copolymer.

(In the formula, Q is the same as above, Rf ¹ is a divalent fluorooxyalkylene-containing polymer residue, Z' is a divalent polysiloxane residue, each of which may be the same or different. e are independently 0 or 1, and f is an integer of 1 to 3, preferably 1 or 2).

In the above (7) and (8), Rf ¹ is a divalent fluorooxyalkylene group-containing polymer residue, and the same ones as in the above formula (6) can be exemplified.

(式中，R’係可相同或相異的碳數1~4之烷基、苯基或苯基乙基。t為10~200之整數，y為1~5之整數，w1及w2各自為1~200之整數，可相同或相異)。In the above (7) and (8), Z' is a divalent polysiloxane residue, preferably a polysiloxane chain represented by the following general formula (9) or (10).

(In the formula, R' is an alkyl, phenyl or phenylethyl group with the same or different carbon numbers of 1 to 4. t is an integer of 10 to 200, y is an integer of 1 to 5, and w1 and w2 are respectively Integers from 1 to 200, can be the same or different).

In the above general formula (2), Z is a single bond, -JC=[J is preferably an alkyl group with 1 to 3 carbons, a hydroxyl group, or K ₃ SiO-(K is independently a hydrogen atom, preferably a carbon Aryl groups such as alkyl groups with a number of 1 to 3, phenyl groups, etc., or preferably alkoxy groups with a carbon number of 1 to 3), trivalent groups represented by silyl ether groups], -LSi=(L is preferably carbon 1-3 alkyl groups), trivalent groups represented by -C≡, 4-valent groups represented by -Si≡, and 2-8-valent, preferably 2-4-valent siloxane residues When the group selected from the group includes a siloxane bond, it is preferably a chain or cyclic organopolysiloxane residue with 2 to 13 silicon atoms, more preferably 2 to 5 silicon atoms . The organopolysiloxane residue may be an alkyl group or phenyl group having 1 to 8 carbon atoms, more preferably 1 to 4 carbon atoms such as methyl, ethyl, propyl, butyl, etc.

(式中，l為1~12之整數、較佳為1~4之整數)。Such Z includes those shown below.

(In the formula, l is an integer of 1 to 12, preferably an integer of 1 to 4).

In the above general formula (2), m' is an integer of 1-7, preferably an integer of 1-3.

(式中，括弧內所示之各單位可隨機地鍵結)。The organosilicon compound containing at least 3 siloxane bonds and/or at least 2 siloxane bonds in the molecule represented by the above formula (2) and modified by a polymer containing a fluorooxyalkylene group includes the following By. Moreover, in the following formula, p2 is an integer of 5-100, q2 is an integer of 5-100, p2+q2 is an integer of 10-105, t1 is an integer of 4-199, preferably an integer of 9-99 , t2 is an integer of 0-99, preferably an integer of 4-49, but the more suitable values of p2, q2, t1, and t2 are shown in the brackets.

(In the formula, each unit shown in parentheses may be randomly bonded).

Component (A) may also include the above-mentioned molecules containing at least 3 siloxane bonds and/or at least 2 siloxane bonds, and modified by polymers containing fluorooxyalkylene groups containing hydroxyl groups or hydrolyzable groups Hydroxyl groups of organosilicon compounds (hereinafter also referred to as polymers containing fluoropolyether groups), or terminal hydrolyzable groups of polymers containing fluoropolyether groups, are partially hydrolyzed in advance by known methods, and the resulting hydroxyl groups The partial (hydrolyzed) condensate obtained by condensation.

(式中，x為表示聚合度之數)。(B) Component The fluorine-containing coating agent composition of the present invention contains at least 3 siloxane bonds and/or at least 2 siloxane bonds and/or at least 2 siloxane bonds in the molecule of the above-mentioned (A) component, and contains oxyfluorine An organosilicon compound containing a hydroxyl group or a hydrolyzable group modified by an alkyl group polymer is blended with perhydropolysilazane as component (B) at the above-mentioned specific ratio. The perhydropolysilazane of the (B) component is preferably a perhydropolysilazane represented by the following general formula (3).

(In the formula, x is a number indicating the degree of polymerization).

The degree of polymerization of the perhydropolysilazane of the component (B) is preferably about 800-8,000, more preferably about 1,000-5,000. In addition, this degree of polymerization can usually be measured as a weight average degree of polymerization in terms of standard polystyrene obtained by gel permeation chromatography (GPC) analysis using toluene as a developing solvent.

As a specific example of the perhydropolysilazane of the component (B), AZ NAX 120-20 (manufactured by Merck Performance Materials Manufacturing Co., Ltd.) and the like are already on the market.

Furthermore, the perhydropolysilazane of the (B) component can also be blended with the (A) component in the form of a perhydropolysilazane solution predissolved in an organic solvent such as dibutyl ether. Mixed mass ratio.

The fluorine-containing coating agent composition of the present invention can be prepared by mixing component (A) and component (B), but it can also be prepared by previously containing component (B) in the raw material used to synthesize component (A). Synthesize (A) component in the state.

Further, the present invention provides a surface treatment agent containing a fluorine-containing coating agent composition. The fluorine-containing coating agent composition contains (A) at least 3 siloxane bonds and/or at least 2 siloxane bonds in the molecule Organosilicon compounds containing hydroxyl groups or hydrolyzable groups and/or their partial (hydrolyzed) condensates modified by polymers containing fluorooxyalkylene groups, and (B) perhydropolysilazane, and ( The mixing mass ratio of A) component to (B) component is 5:95~95:5.

In the surface treatment agent, hydrolysis and condensation catalysts can also be added as needed, such as organic tin compounds (dibutyltin dimethoxide, dibutyltin dilaurate, etc.), organic titanium compounds (tetra-n-butyl titanate, etc.), organic Acids (acetic acid, methanesulfonic acid, fluorine-modified carboxylic acid, etc.), inorganic acids (hydrochloric acid, sulfuric acid, etc.). Among these, acetic acid, tetra-n-butyl titanate, dibutyltin dilaurate, fluorine-modified carboxylic acid, and the like are particularly desirable. The addition amount of the hydrolysis condensation catalyst is a catalytic amount, usually, it is 0.01~5 parts by mass, especially 0.1~ 1 part by mass.

The surface treatment agent may also contain at least 3 siloxane bonds and/or at least 2 siloxane bonds in the molecule used to dissolve the component (A), and is modified by a polymer containing a fluorooxyalkylene group Suitable solvents for organosilicon compounds containing hydroxyl or hydrolyzable groups and/or their partial (hydrolyzed) condensates. Examples of such solvents include fluorine-modified aliphatic hydrocarbon solvents (perfluoroheptane, perfluorooctane, etc.), fluorine-modified aromatic hydrocarbon solvents (1,3-bis(trifluoromethyl)benzene, etc.) , Fluorine-modified ether-based solvents (methyl perfluorobutyl ether, ethyl perfluorobutyl ether, perfluoro(2-butyltetrahydrofuran), etc.), fluorine-modified alkylamine-based solvents (perfluorotributylamine, Perfluorotripentylamine, etc.), hydrocarbon solvents (petroleum, toluene, xylene, etc.), ketone solvents (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.). Among them, from the viewpoints of solubility and wettability, fluorine-modified solvents are more desirable, and 1,3-bis(trifluoromethyl)benzene and perfluoro(2-butyltetrahydrofuran) are particularly preferable. , perfluorotributylamine, ethyl perfluorobutyl ether.

Two or more of the above-mentioned solvents may be mixed, and it is preferable to uniformly dissolve the fluoropolyether group-containing polymer and its partial (hydrolyzed) condensate. Furthermore, the optimal concentration of the fluoropolyether group-containing polymer and its partial (hydrolyzed) condensate dissolved in the solvent varies depending on the treatment method, as long as it is easy to weigh, but in the case of direct coating, 0.01 to 10 parts by mass, preferably 0.05 to 5 parts by mass relative to 100 parts by mass of the solvent and the polymer containing a fluoropolyether group (and its partial (hydrolyzed) condensate) in total, for vapor deposition In the case of handling, it is 1 to 100 parts by mass, especially 3 to 30 parts by mass, relative to a total of 100 parts by mass of the solvent and the polymer containing a fluoropolyether group (and its partial (hydrolyzed) condensate). good.

The surface treatment agent of the present invention can be applied to the substrate by known methods such as brush coating, dipping, and spraying. Also, the curing temperature varies depending on the curing method, but for example, in the case of direct coating (brush coating, dipping, spraying, etc.), it is 25 to 200°C, especially 50 to 150°C for 30 minutes to 36 hours, Especially 1~24 hours is better. In addition, it can also harden under humidification. The film thickness of the cured film is appropriately selected according to the type of substrate, but it is usually 0.1~100nm, especially 1~20nm.

The substrate treated with the surface treatment agent of the present invention is not particularly limited, and can be made of various materials such as paper, cloth, metal and its oxides, glass, plastic, resin, ceramics, and quartz. The surface treatment agent of the present invention can impart water and oil repellency to the aforementioned substrate.

Articles treated with the surface treatment agent of the present invention include car navigation, mobile phones, smart mobile phones, digital cameras, digital video cameras, PDAs, portable audio players, car audio, game machines, eyeglass lenses, Optical articles such as camera lenses, lens filters, sunglasses, gastric cameras, etc., medical equipment, copiers, PCs, liquid crystal displays, organic EL displays, plasma displays, touch panel displays, protective films, and antireflective films. The surface treatment agent of the present invention can prevent fingerprints and sebum from adhering to the above-mentioned articles, and further impart damage prevention properties, so it is particularly useful as a touch panel display, and because it has good adhesion to resin or metal, it is useful as a smart phone. The water-repellent and oil-repellent layer of the shell part of the mobile phone.

In addition, the surface treatment agent of the present invention can also be used for antifouling coating of sanitary products such as bathtubs and washstands; antifouling coating of window glass or tempered glass of automobiles, trams, airplanes, etc., headlight covers, etc.; Water-repellent and oil-repellent coatings for building materials for exterior walls; anti-greasy coatings for kitchen building materials; anti-fouling, anti-sticker and graffiti coatings for telephone booths; anti-fingerprint coatings for art works; optical discs, DVDs Anti-fingerprint coating, etc.; mold release agent or coating additive, resin modifier, fluidity modifier or dispersion modifier of inorganic filler, lubricity improver for adhesive tape, film, etc. [Example]

Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated in detail, this invention is not limited to a following example.

Component (A) contains at least 3 siloxane bonds and/or at least 2 siloxane bonds and is modified with a fluorooxyalkylene group-containing polymer containing hydroxyl or hydrolyzable groups in the molecule As compounds, the following [Compound 1] to [Compound 3] were prepared. Furthermore, [Compound 1] to [Compound 3] are all components soluble in dibutyl ether at room temperature (25° C.). In addition, it is prepared as a polymer containing fluoropolyether groups that does not contain at least 3 siloxane bonds and/or at least 2 siloxane bonds in the molecule, and is not soluble in dibutyl ether at room temperature (25°C). [Compound 4] and [Compound 5] were used for comparison.

[Compound 1]

[Compound 2]

[Compound 3]

[Compound 4]

[compound 5]

As the perhydropolysilazane of the component (B), AZ NAX 120-20 (manufactured by a Merck Performance Materials Manufacturing contract company) was used.

[Examples 1-10, Comparative Examples 1-5] Preparation of surface treatment agent and formation of hardened film In the mixing ratio shown in Table 1, [Compound 1] ~ [Compound 3] of the (A) component and [Compound 4] and [Compound 5] for comparison were modified with a polymer containing a fluorooxyalkylene group. The organosilicon compound containing a hydrolyzable group is mixed with a 10% by mass dibutyl ether solution of perhydropolysilazane as component (B) or dibutyl ether as a solvent to prepare a surface treatment agent. Each surface treatment agent Dip was applied to Duralumin, PMMA (polymethyl methacrylate resin) or PC (polycarbonate resin). Coating conditions were 350 mm/min of extraction speed and 30 seconds of immersion time. Harden the glass immediately after coating at 80°C and 50%RH for 1 hour to form a hardened film with a thickness of about 100nm. In addition, in Comparative Examples 1 to 3, dibutyl ether was dissolved in a solvent to become a 10% by mass solution. In addition, in Comparative Examples 4 and 5, [Compound 4] and [Compound 5] of the (A) component were not dissolved in dibutyl ether in the (B) component, and the coating liquid could not be prepared.

The hardened coatings of Examples 1-10 and Comparative Examples 1-3 were evaluated by the following method. All tests were carried out at 25° C. and a humidity of 40% RH.

[Evaluation of Solubility] (A) component and (B) component are mixed, and if there is no turbidity visually, the evaluation of solubility is "○", and if it is turbid, it is "x". The results (solubility) are shown in Table 2.

Evaluation of water repellency [Assessment of initial water repellency] For the substrate on which the cured film prepared above was formed, the contact angle (water repellency) of the cured film to water was measured using a contact angle meter Drop Master (manufactured by Kyowa Interface Science Co., Ltd.) (droplet: 2 μl, temperature: 25°C, humidity : 40% RH). Furthermore, the water contact angle was measured after 1 second after a 2 μl droplet was dropped on the sample surface. Table 2 shows the results (initial contact angles). Both Examples and Comparative Examples showed good water repellency at the initial stage.

[Evaluation of abrasion resistance] The abrasion resistance against cloth (BEMCOT) was measured for the obtained cured film using TriboGear TYPE: 30S (manufactured by Shinto Scientific Co., Ltd.). The cloth resistance test was carried out under the following conditions, and the contact angle (water repellency) of the cured film after rubbing 4,000 times was measured in the same manner as above to evaluate the abrasion resistance. Table 2 shows the results (contact angles after abrasion). Contact area: 10mm×30mm Load: 1kg Abrasion-resistant cloth: BEMCOT M-3II (manufactured by Asahi Kasei Co., Ltd.) Moving distance (one way) 20mm Moving speed 3,600mm/min Load: 0.5kg/cm ²

The surface treatment agents of Examples 1 to 10 are obtained by mixing the above-mentioned molecules with at least 3 siloxane bonds and/or at least 2 siloxane bonds in a specific blending ratio, and passing through the fluorooxyalkylene group-containing Polymer-modified organosilicon compounds containing hydrolyzable groups and perhydropolysilazane dissolved in dibutyl ether solution improve the adhesion to metal substrates. It can be seen that the hardened coatings of the surface treatment agents of Examples 1-10 contain at least 3 siloxane bonds and/or at least 2 siloxane bonds in the molecules compared to those using only Comparative Examples 1-3, and For the hardened film of the surface treatment agent containing hydrolyzable organosilicon compound modified by the polymer containing fluorooxyalkylene group, the contact angle of the cloth is kept above 100° after 4,000 times of abrasion, and it exhibits excellent durability. Abrasive. In addition, the organosilicon compounds containing hydrolyzable groups ([Compound 4], [Compound 5]) modified by polymers containing fluorooxyalkylene groups used in Comparative Examples 4 and 5 did not satisfy the above-mentioned structure, so they did not dissolve In dibutyl ether solution, the coating solution cannot be prepared.

Claims (15)

A fluorine-containing coating agent composition, characterized in that (A) contains at least 3 siloxane bonds and/or at least 2 siloxane bonds in the molecule, and is modified by a polymer containing a fluorooxyalkylene group Organosilicon compounds containing hydroxyl groups or hydrolyzable groups and/or their partial (hydrolyzed) condensates, and (B) perhydropolysilazane, and the mixing mass ratio of (A) component to (B) component is 5: 95~95:5 (provided that the total of the mixing mass ratio of (A) component and (B) component is 100). Such as the fluorine-containing coating agent composition of claim 1, wherein (A) component is the following general formula (1)

(In the formula, Rf is a 1- or 2-valent polymer residue containing fluorooxyalkylene groups, and A is a siloxane bond, a siloxane bond, and a siloxane bonded with Si bonded to A. One or two or more 2-16 valent organic groups selected from the bases of alkyl bonds or silicon-extended phenyl bonds, R is independently alkyl or phenyl with 1 to 4 carbons, and X is independently hydroxyl or Hydrolyzable group, n is an integer of 1 to 3, m is an integer of 1 to 15, α is 1 or 2) The molecule represented by at least 3 siloxane bonds and/or at least 2 siloxane bonds, and Organosilicon compounds containing hydroxyl groups or hydrolyzable groups and/or their partial (hydrolyzed) condensates modified by polymers containing fluorooxyalkylene groups, or the following general formula (2)

(In the formula, Rf' is a divalent fluorooxyalkylene-containing polymer-containing polysiloxane copolymer group, Q, Q' are each a single bond, or may contain an ether bond, or may be passed through a fluorine A substituted divalent organic group, Z is a silane represented by a single bond, -JC=[J is an alkyl group, a hydroxyl group or K ₃ SiO- (K is independently a hydrogen atom, an alkyl group, an aryl group or an alkoxy group) 3-valent group represented by base ether group], 3-valent group represented by -LSi=(L is an alkyl group), 4-valent group represented by -C≡, 4-valent group represented by -Si≡, and 2-8 valent silicon A group selected from oxane residues, m' is an integer from 1 to 7, and X, R, and n are the same as above) The molecule represented by at least 3 siloxane bonds and/or at least 2 siloxane bonds , and the organosilicon compound containing hydroxyl group or hydrolyzable group and/or its partial (hydrolyzed) condensate modified by polymer-polysiloxane copolymer containing fluorooxyalkylene group, (B) component is as follows Perhydropolysilazane represented by the general formula (3)-(SiH ₂ -NH) _x - (3) (where x is a number indicating the degree of polymerization). The fluorine-containing coating agent composition as in claim 2, wherein the molecule represented by formula (1) contains at least 3 siloxane bonds and/or at least 2 siloxane bonds, and is passed through a fluorooxyalkylene group. Polymer-modified organosilicon compounds containing hydroxyl groups or hydrolyzable groups have the following general formula (4a) or (4b)

[wherein, Rf is a monovalent or divalent polymer residue containing a fluorooxyalkylene group, and Y is independently a group consisting of a silicon atom, a siloxane bond, a silane group structure, and a silicon aryl group. One or more 2-6 valent organic groups selected in the structure, R is independently an alkyl or phenyl group with 1-4 carbons, X is independently a hydroxyl group or a hydrolyzable group, and n is 1-4 An integer of 3, a is an integer of 1 to 5, W is a hydrogen atom, or the following formula (4a')

(wherein, Y' is a 2-6 valent organic group that may have a silicon atom and/or a siloxane bond, b is an integer of 1-5, R, X, and n are the same as above), Y and The sum of Y' has at least 3 siloxane bonds and/or at least 2 siloxane bonds; α is 1 or 2];

(In the formula, U is -(CH ₂ ) _z1 O-, z1 is an integer from 1 to 20, A ¹ is -(CH ₂ ) _z2 -, z2 is an integer from 1 to 20, V is a siloxane bond and / or a silane phenyl bond, and may have a silane phenylene structure and/or a 2-6 valent hydrocarbon group with a silane aryl structure other than a silane phenyl bond, c is an integer of 1 to 5; Rf, X, R, n, α means the same as above) containing at least 3 siloxane bonds and/or at least 2 siloxane bonds, and modified by polymers containing fluorooxyalkylene groups, containing hydroxyl groups or hydrolyzable Based on organosilicon compounds. The fluorine-containing coating agent composition as claimed in item 2 or 3, wherein in the aforementioned formulas (1), (4a) and (4b), α is each 1, and Rf is a monovalent compound represented by the following general formula (5): Polymer residues containing fluorooxyalkylene groups;

(wherein, p, q, r, and s are each an integer of 0 to 200, p+q+r+s=3 to 200, each repeating unit can be linear or branched, and each repeating unit can be mutually Randomly bonded, d is an integer from 1 to 3, and the unit can be linear or branched). The fluorine-containing coating agent composition as claimed in item 2 or 3, wherein in the aforementioned formulas (1), (4a) and (4b), α is 2 each, and Rf is a divalent compound represented by the following general formula (6): Polymer residues containing fluorooxyalkylene groups;

(wherein, p, q, r, and s are each an integer of 0 to 200, p+q+r+s=3 to 200, each repeating unit can be linear or branched, and each repeating unit can be mutually Randomly bonded, d is an integer from 1 to 3, and the unit can be linear or branched). Such as the fluorine-containing coating agent composition of claim 3, wherein in the aforementioned formula (4a), Y is an alkylene group selected from an alkylene group with 5 to 10 carbons, an alkylene group including an arylylene group with 6 to 8 carbons, Alkene groups are bivalent groups bonded to each other through a silane group structure or a sila aryl structure, and a chain alkene group with 2 to 10 carbon atoms is bonded to a straight chain or branched group with 2 to 100 silicon atoms Shaped or cyclic 2-4 valent organopolysiloxane residues The base of the group formed by the 2~4 valent groups obtained from the bonding site. Such as the fluorine-containing coating agent composition of claim 3 or 6, wherein in the aforementioned formula (4a'), Y' is selected from an alkylene group with 2 to 10 carbons and an arylylene group with 6 to 8 carbons. An alkylene group, an alkylene group with 2 to 6 carbon atoms including a diorganosilylene group, a divalent group in which the alkylene group is bonded to each other through a siliconyl structure or a silicon aryl structure, and a carbon number 2 to 6 The alkylene group of 10 is bonded to the bonding site of a straight chain with 2 to 10 silicon atoms or a branched or cyclic 2 to 4 valent organopolysiloxane residue with 3 to 10 silicon atoms The base of the group formed by the obtained 2~4 valence bases. Such as the fluorine-containing coating agent composition of claim 2, wherein Rf' in formula (2) is a divalent fluorooxyalkylene-containing polymer represented by the following general formula (7) or (8)- Contains polysiloxane copolymer base; -(Z'-Q) _e -Rf ¹ -(Q-Z') _e - (7) -Rf ¹ -(Q-Z'-Q-Rf ¹ ) _f - (8) (In the formula, Q is a single bond, or may contain an ether bond, and a divalent organic group that may be substituted by fluorine, Rf is ^a divalent polymer residue containing a fluorooxyalkylene group, and Z' is The divalent polysiloxane residues may be the same or different; e is independently 0 or 1, and f is an integer of 1 to 3). Such as the fluorine-containing coating agent composition of claim 8, wherein Z' in formulas (7) and (8) is a polysiloxane chain represented by the following general formula (9) or (10), and Rf ¹ is as follows The divalent fluorooxyalkylene-containing polymer residue represented by the general formula (6);

(In the formula, R' is an alkyl, phenyl or phenylethyl group with the same or different carbon numbers of 1 to 4; t is an integer of 10 to 200, y is an integer of 1 to 5, and w1 and w2 are each Integers from 1 to 200, can be the same or different);

(wherein, p, q, r, and s are each an integer of 0 to 200, p+q+r+s=3 to 200, each repeating unit can be linear or branched, and each repeating unit can be mutually Randomly bonded, d is an integer from 1 to 3, and the unit can be linear or branched). Such as the fluorine-containing coating agent composition of claim 2 or 3, wherein in the aforementioned formulas (1), (2), (4a) and/or (4b), X is each selected from hydroxyl and carbon number 1-10 A group consisting of alkoxy, alkoxyalkoxy with 2 to 10 carbons, acyloxy with 1 to 10 carbons, alkenyloxy with 2 to 10 carbons, and halogen. The fluorine-containing coating agent composition according to any one of claims 1 to 3, wherein the molecule of component (A) contains at least 3 siloxane bonds and/or at least 2 siloxane bonds, and contains fluorine The organosilicon compound containing hydroxyl group or hydrolyzable group modified by the polymer of oxyalkylene group is represented by any one of the following formulas;

(In the formula, p1 is an integer from 5 to 100, q1 is an integer from 5 to 100, p1+q1 is an integer from 10 to 105, and these repeating units can be randomly bonded);

(In the formula, p2 is an integer from 5 to 100, q2 is an integer from 5 to 100, p2+q2 is an integer from 10 to 105, t1 is an integer from 4 to 199, and t2 is an integer from 0 to 99; shown in brackets Each repeating unit can be randomly bonded). The fluorine-containing coating agent composition according to any one of claims 1 to 3, wherein the molecule of component (A) contains at least 3 siloxane bonds and/or at least 2 siloxane bonds, and contains fluorine Polymer-modified organosilicon compounds containing hydroxyl groups or hydrolyzable groups and/or their partial (hydrolyzed) condensates, which are soluble in Dibutyl ether. A surface treatment agent containing the fluorine-containing coating composition according to any one of claims 1-12. A hardened film, which is composed of the hardened product of the surface treatment agent according to claim 13. An article having a hardened film of the surface treatment agent according to claim 13 on the surface.