TWI714662B - Surface-treated resin products - Google Patents

Abstract

The present invention provides a fluorine-containing polyether group-containing polymer modification that can form a water- and oil-repellent layer with excellent abrasion resistance in a short time, especially on the resin surface, even under mild curing conditions such as room temperature curing. Surface treatment agent of silane and/or its partial hydrolysis condensate, resin product for surface treatment.

Use the following formula (1)

[Rf is a polymer residue of a monovalent or divalent fluorine-containing polyether group, Y is a divalent to hexavalent hydrocarbon group with a siloxane bond, a silylene structure or a silylene structure, R is an alkane Group or phenyl group, X is a hydrolyzable group, n is 1~3, m is 1~5, Z is a hydrogen atom or

(R’ is the same as R, X’ is the same as X, W is the same as Y, a is 0~3, b is 1~5, E is a monovalent organic group) The surface treatment agent of the fluorine-containing polyether group polymer modified silane and/or its partial hydrolysis condensate.

Description

Surface-treated resin products

The present invention relates to a resin product that has been surface-treated with a polymer-modified silane containing a fluorine-containing polyether group and a surface treatment agent of the silane and/or its partial hydrolysis condensate.

In recent years, led by mobile phone displays, screen touch panels are accelerating. However, because the touch panel has an open screen, there are many chances of direct contact with fingers or cheeks, which is a problem of easy adhesion of sebum and other dirt. Therefore, in order to make the appearance or recognizability better, there is an increasing demand for fingerprints that are difficult to adhere to the surface of the display or a technology for easy removal of dirt every year, and it is expected to develop materials that can meet these requirements. In particular, fingerprint dirt is easy to adhere to the surface of the touch panel display, so it is desirable to provide a water and oil repellent layer. However, the conventional water and oil repellent layer system has high water and oil repellency and excellent dirt wiping performance, but there is a problem that the anti-fouling performance deteriorates during use. In addition, the performance may vary due to the coating method, or the adhesion of the coated substrate may deteriorate. In addition, most of the surface treatment agents used so far show good surface properties for glass, but for resin surfaces, they do not exhibit sufficient surface properties such as adhesion, water and oil repellency, and abrasion resistance. By.

Generally speaking, fluorine-containing polyether-based compounds have very low surface free energy, so they have water and oil repellency, chemical resistance, lubricity, mold release, antifouling properties, and the like. Utilizing this characteristic, it is widely used in industry as water and oil repellent antifouling agents for paper, fiber, etc., lubricants for magnetic recording media, oil repellents for precision machinery, mold release agents, cosmetics, protective films, etc. However, this characteristic also means non-adhesion and non-adhesion to other substrates. Even if it can be applied to the surface of the substrate, it is difficult to make the film adhere to it.

In addition, the silane coupling agent is well known as a method for bonding the surface of a substrate such as glass or cloth with an organic compound, and is widely used as a coating agent for the surface of various substrates. 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 silyl group forms a film by self-condensation reaction caused by moisture in the air. The film is formed into a durable and strong film by chemically and physically bonding the hydrolyzable silyl group to the surface of glass or metal.

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

When the substrate is surface-treated with a composition containing the above-mentioned fluorine-containing polyether group-modified silane, 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 curing the film, the hydrolysis reaction is promoted by high temperature conditions such as 80°C or 120°C or conditions under humidification. Also, even at room temperature, it slowly reacts with moisture in the air to form a cured film. However, this hardening step requires high-temperature humidification conditions, and it takes more time to harden at room temperature, etc., which has the problem of speed limitation (delay factor) in manufacturing. In addition, under mild conditions such as curing at room temperature, a film (water- and oil-repellent layer) that is cured in a short time has problems with wear resistance and deterioration in antifouling performance during use.

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

In order to promote the hydrolysis reaction of the alkoxysilyl group, there is also a method of adding a catalyst. The previously known catalysts include organic titanates such as tetrabutyl titanate and tetraisopropyl titanate; diisopropoxy bis(ethyl acetate) titanium, diisopropoxy Organic titanium chelate compounds such as bis(ethylacetate) titanium; organoaluminum compounds such as ginseng(ethylacetone) aluminum and ginseng(ethylacetate) aluminum; tetrakis(acetoxyacetone)zirconium , Zirconium tetrabutyrate and other organic zirconium compounds; dibutyltin dicaprylate, dibutyltin dilauric acid Organic tin compounds such as esters, dibutyltin bis(2-ethylhexanoate), dioctyltin dilaurate, dioctyltin diacetate, and dioctyltin dioctanoate; naphthenic acid Metal salts of organic carboxylic acids such as tin, tin oleate, tin butylate, cobalt naphthenate, zinc stearate, etc.; amine compounds such as hexylamine, dodecylamine phosphate and their salts; benzyl triethyl Quaternary ammonium salts such as base ammonium acetate; lower fatty acid salts of alkali metals such as potassium acetate and lithium nitrate; dialkyl hydroxylamine such as dimethyl hydroxylamine and diethyl hydroxylamine; tetramethylguanidine (guanidyl) guanidyl-containing organosilicon compounds such as propyltrimethoxysilane; organic acids (acetic acid, methanesulfonic acid, etc.), inorganic acids (hydrochloric acid, sulfuric acid, etc.), etc. However, these catalysts do not dissolve in fluorine-based solvents or dissolve only a very small amount even if they are dissolved, so the catalyst efficiency is poor. In addition, the characteristics of the cured film may be deteriorated due to the remaining metal content.

In addition, Patent Document 10 (Japanese Patent Application Laid-Open No. 2004-145283) proposes a silane containing a fluoropolyalkylene ether group. Although the lens treated with this fluorine-containing polyalkylene ether group-containing silane has excellent oil repellency and fingerprint wiping properties, it has insufficient wear resistance.

[Prior Technical Literature] [Patent Literature]

[Patent Document 1] JP 2003-238577 A

[Patent Document 2] Japanese Patent No. 2860979

[Patent Document 3] Japanese Patent No. 4672095

[Patent Document 4] JP 2008-534696 Publication

[Patent Document 5] Japanese Special Publication No. 2008-537557

[Patent Document 6] JP 2012-072272 A

[Patent Document 7] JP 2012-157856 A

[Patent Document 8] JP 2013-136833 A

[Patent Document 9] JP 2008-144144 A

[Patent Document 10] JP 2004-145283 A

[Summary of Invention]

The present invention has been completed in view of the above circumstances. The object of the present invention is to provide a water- and oil-repellent layer with excellent abrasion resistance even in a short time under mild curing conditions such as room temperature curing, especially on the resin surface. It is a resin product that contains fluorine-containing polyether group-modified silane and/or its partial hydrolysis condensate surface treatment agent for surface treatment.

In order to solve the above-mentioned object, the inventors of the present invention conducted a careful review and found that the above-mentioned fluorine-containing polyether-based polymer modified silane was modified by a fluorine-containing polyether-based polymer represented by the general formula (1) described later The surface treatment agent of siloxane can form a water- and oil-repellent layer with excellent abrasion resistance even in a short time under mild curing conditions such as curing at room temperature. This completes the present invention.

Therefore, the present invention provides a surface treatment agent for modifying silane and/or its partial hydrolysis condensate with a polymer containing the following fluorine-containing polyether group Surface-treated resin products.

[式中，Rf係一價之含氟氧烷基(fluorooxyalkyl)或二價之含氟氧伸烷基(fluorooxyalkylene)之聚合物殘基，Y獨立為具有矽氧烷鍵、矽伸烷基結構或矽伸芳基結構之二價至六價烴基，R獨立為碳數1~4之烷基或苯基，X獨立為水解性基，n為1~3之整數，m為1~5之整數，Z獨立為氫原子、下述式-SiR’_(3-a)X’_a(式中，R’獨立為碳數1~4之烷基或苯基，X’獨立為水解性基，a為0~3之整數)表示之基、下述式-W-(SiR_(3-n)X_n)_b(式中，R、X、n係與上述相同，W係具有矽氧烷鍵、矽伸烷基結構或矽伸芳基結構之二價至六價烴基，b為1~5之整數)表示之基、或選自下述式

(式中，E為一價有機基)表示之結構之基，α為1或2]。表示之含氟聚醚基之聚合物改質矽烷及/或其部分水解縮合物之表面處理劑，進行表面處理所成。 [1] A resin product, which is the treated surface of a resin product that has been surface-treated with SiO _{2 in} advance, further comprising the following general formula (1)

[In the formula, Rf is a polymer residue of a monovalent fluorooxyalkyl or a divalent fluorooxyalkylene (fluorooxyalkylene), and Y independently has a siloxane bond and a silylene structure Or a divalent to hexavalent hydrocarbon group of the silylene structure, R is independently an alkyl or phenyl group with carbon number of 1 to 4, X is independently a hydrolyzable group, n is an integer from 1 to 3, and m is from 1 to 5 integer, Z is independently a hydrogen atom, by the following formula _{-SiR '(3-a) X} ' a ( wherein, R 'is independently an alkyl group having 1 to 4 carbon atoms or the phenyl group, X' is independently a hydrolyzable group, a is an integer from 0 to 3), the following formula -W-(SiR _(3-n) X _n ) _b (where R, X and n are the same as above, and W has a siloxane bond , Divalent to hexavalent hydrocarbon group of silylene structure or silyl aryl structure, b is an integer from 1 to 5), or selected from the following formulas

(In the formula, E is a monovalent organic group) represents the base of the structure, and α is 1 or 2]. The indicated fluorine-containing polyether-based polymer is modified by the surface treatment agent of silane and/or its partial hydrolysis condensate, and is formed by surface treatment.

(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或分支狀，各重複單位彼此亦可無規地鍵結，d為1~3之整數)。 [2] The resin product according to [1], wherein in the aforementioned formula (1), α is 1, and the Rf group is a group represented by the following general formula (2),

(In the formula, p, q, r, s are each an integer of 0~200, p+q+r+s=3~200, each repeating unit can be linear or branched, and each repeating unit can have no other Regularly bonding, d is an integer of 1~3).

(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或分支狀，各重複單位彼此亦可無規地鍵結，d為1~3之整數)。 [3] The resin product according to [1], wherein in the aforementioned formula (1), α is 2, and the Rf group is a group represented by the following general formula (3),

(In the formula, p, q, r, s are each an integer of 0~200, p+q+r+s=3~200, each repeating unit can be linear or branched, and each repeating unit can have no other Regularly bonding, d is an integer of 1~3).

[4] The resin product according to any one of items [1] to [3], wherein in the aforementioned formula (1), Y is selected from the group consisting of alkylene groups that are bonded to each other via a silylene structure or silylene structure The divalent group and the linear, branched or cyclic organopolysiloxane residues of divalent to tetravalent silicon atoms with 2-10 The group of tetravalent bases.

[5] The resin product of any one of items [1] to [4], wherein the aforementioned formula (1) Where X is selected from the group consisting of alkoxy groups with 1 to 10 carbons, alkoxy groups with 2 to 10 carbons, alkoxy groups with 1 to 10 carbons, alkenyloxy groups with 2 to 10 carbons, and halogens. The foundation is the foundation of the group.

[6] The resin product according to any one of items [1] to [5], wherein in the aforementioned formula (1), Z is a hydrogen atom and a group selected from the groups shown below,

(式中，Z係與上述相同，p1為5~100之整數、q1為5~100之整數、p1+q1為10~105之整數，g1為2~20之整數，w為2~10之整數)。 [7] The resin product of any one of items 1 to 3 of the scope of patent application in any one of items [1] to [6], wherein the fluorine-containing polyether-based polymer represented by the above formula (1) is modified Silane is represented by the following formula,

(In the formula, Z is the same as above, 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, g1 is an integer from 2 to 20, and w is an integer from 2 to 10 Integer).

[8] The resin product according to any one of items [1] to [7], wherein the surface treatment agent further contains the following general formula (4) [Chemical 15] A-Rf'-A (4) (wherein, A series terminal is -CF ₃ group monovalent fluorine-containing group, Rf' is a divalent fluorine-containing oxyalkylene polymer residue) represented by a polymer of fluorine-containing polyether group.

[9] The resin product of any one of items [1] to [8], wherein the resin product is made of thermoplastic resin.

[10] The resin product according to any one of [1] to [9], wherein the aforementioned resin product is a resin product that has been surface-treated with SiO ₂ by a sputtering method.

[11] Resin products such as any one of items [1] to [10], in which resin is made Products are hard film, high hardness resin film or anti-reflection film.

[12] The resin product of any one of items [1] to [10], wherein the resin product is a spectacle lens.

[13] The resin product of any one of items [1] to [10], wherein the resin product is a touch panel display.

[14] The resin product of any one of items [1] to [10], wherein the resin product is a wearable terminal.

On the resin product of the present invention, the coating formed by the surface treatment agent of polymer modified silane containing fluorine-containing polyether group and/or its partial hydrolysis condensate has high water and oil repellency, especially at room temperature. Under mild conditions, the film formed by curing in a short time has excellent abrasion resistance. For the resin product of the present invention, the surface treatment agent containing fluorine-containing polyether group-containing polymer modified silane and/or its partial hydrolysis condensate has special adhesion to the surface of the resin, so by Treatment with this surface treatment agent can easily impart excellent water and oil repellency, low dynamic friction and abrasion resistance to resin products such as resin films or eyeglass lenses in a short time.

[The form of implementing the invention]

The resin product of the present invention is the treated surface of the resin product that has been surface-treated with SiO ₂ in advance, and is further modified by a polymer containing a fluorine-containing polyether group represented by the following general formula (1) to modify silane and/or its partial hydrolysis The surface treatment agent of condensate is formed by surface treatment.

The polymer-modified silane containing fluorine-containing polyether group used in the present invention is represented by the following general formula (1).

[In the formula, Rf is a monovalent fluorine-containing oxyalkylene group or a divalent fluorine-containing oxyalkylene group-containing polymer residue, and Y independently has a siloxane bond, a silylene structure or a silylene aryl structure Is a divalent to hexavalent hydrocarbon group, R is independently an alkyl or phenyl group with carbon number of 1 to 4, X is independently a hydrolyzable group, n is an integer of 1 to 3, m is an integer of 1 to 5, and Z is independently hydrogen atom, the following formula _{-SiR '(3-a) X} ' a

(In the formula, R'is independently an alkyl group or phenyl group having 1 to 4 carbon atoms, X'is independently a hydrolyzable group, and a is an integer of 0 to 3) represented by the following formula -W-(SiR _{(3 -n)} X _n ) _b

(In the formula, R, X, n are the same as above, W is a divalent to hexavalent hydrocarbon group with a siloxane bond, a silylene structure or a silylene aryl structure, b is an integer of 1 to 5) , Or selected from the following formula

(In the formula, E is a monovalent organic group) represents the base of the structure, and α is 1 or 2].

In the above formula (1), when α is 1, Rf is preferably as follows The general formula (2) represents a monovalent fluorooxyalkyl group.

(In the formula, p, q, r, s are each an integer of 0~200, and p+q+r+s=3~200, each repeating unit can be linear or branched, and each repeating unit can also be each other Random bonding. d is an integer from 1 to 3).

In the above formula (1), when α is 2, Rf is preferably a divalent fluorooxyalkyl group represented by the following general formula (3).

(In the formula, p, q, r, s are each an integer of 0~200, and p+q+r+s=3~200, each repeating unit can be linear or branched, and each repeating unit can also be each other Random bonding. d is an integer from 1 to 3).

In the above formulas (2) and (3), p, q, r, and s are each an integer from 0 to 200, preferably p is an integer from 5 to 100, q is an integer from 5 to 100, and r is from 0 to 100 Integer, s is an integer from 0 to 100, p+q+r+s=3 to 200, preferably 10 to 100, each repeating unit can be linear or branched, and each repeating unit can be random to each other To bond. More preferably, p+q is 10~105, especially an integer of 15~60, r=s=0. When p+q+r+s is less than the above upper limit value, the adhesion or hardenability is good, and when it is above the above lower limit value, the characteristics of the fluoropolyether group can be fully exhibited, which is preferable.

In the above formulas (2) and (3), d is an integer of 1 to 3, preferably 1 or 2, and the unit may be linear or branched.

Rf has the main chain structure represented by the above formula (2) or (3), so It can form a hardened film with a low coefficient of dynamic friction.

In addition, the main chain has a fluoropolyether structure and a linear polymer containing a hydrolyzable group at a single end of the molecular chain (α is 1, Rf is the formula (2) representing a monovalent fluorooxyalkyl group), compared to A linear polymer containing hydrolyzable groups at both ends (α is 2, and Rf is a divalent fluorooxyalkylene group represented by formula (3)) can impart more excellent abrasion resistance to the resulting cured film.

Specifically, Rf includes, for example, the following.

(In the formula, p', q', r', and s'are each an integer of 1 or more, and the upper limit is the same as the upper limit of p, q, r, and s. u is 1-24, v is 01-24, And satisfy the number of u+v=r. Each repeating unit can be randomly bonded).

In the above formula (1), Y is a divalent to hexavalent, preferably divalent to tetravalent, and more preferably a divalent hydrocarbon group having a siloxane bond, a silylene structure or a silylene aryl structure. There is no linking group (ether bond, etc.) with low bonding energy, and a coating film with excellent abrasion resistance can be provided.

Specifically, Y includes a divalent group in which alkylene groups are bonded to each other via a silylalkylene structure or a silylalkylene structure, and the number of divalent to hexavalent silicon atoms is 2-40, preferably 2~ 10 linear, branched or cyclic organopolysiloxane residues are bonded with divalent to hexavalent alkylene groups, etc., preferably the alkylene groups pass through the siloxane The linking bond of a divalent group, a divalent to a tetravalent silicon atom number of 2-10, linear, branched or cyclic organopolysiloxane residues The divalent to tetravalent group of alkylene is bonded to it.

Here, the silylalkylene structure and the silylalkylene structure may be those shown below, for example.

(In the formula, R ¹ is an alkyl group such as methyl, ethyl, propyl, butyl, etc. with carbon number of 1 to 4, and an aryl group such as phenyl group. R ¹ may be the same or different. R ² is a carbon number of 1 ~4 Methylene, ethylene, propenyl (trimethylene, methyl ethylene) and other alkylene, phenylene and other aryl group).

Moreover, linear, branched or cyclic organopolysiloxane residues include, for example, those shown below.

(In the formula, R ¹ is the same as above. g is an integer of 1-20, preferably 1-10, h is an integer of 2-6, preferably 2-4, and j is an integer of 0-8. Preferably it is 0 or 1, h+j is an integer of 3 to 10, preferably 3 to 5, and k is an integer of 1 to 3, preferably 2 or 3).

Specific examples of Y include the following groups.

(In the formula, g1 is an integer of 2-20, preferably 2-10, and w is an integer of 2-10, preferably 2-8).

In the above formula (1), X may be different hydrolyzable groups. Such X can include alkoxy, ethoxy, propoxy, isopropoxy, butoxy and other alkoxy groups with 1 to 10 carbon atoms, methoxymethoxy, and methoxyethoxy. Alkoxy groups with 2 to 10 carbon atoms, acetoxy groups with 1 to 10 carbon atoms, isopropenoxy groups, such as alkenyloxy groups with 2 to 10 carbon atoms, chloro groups, etc. Halogen groups such as bromo and iodo. Among them, a methoxy group, an ethoxy group, an isopropenoxy group, and a chloro group are preferred.

In the above formula (1), R is a methyl, ethyl, Among them, an alkyl group such as a propyl group and a butyl group, or a phenyl group, is preferably a methyl group.

n is an integer of 1 to 3, preferably 2 or 3, and more preferably 3 from the viewpoint of reactivity and adhesion to the substrate.

m is an integer from 1 to 5. If it is less than 1, the adhesion to the substrate will decrease. If it is above 6, the terminal alkoxy valence will be too high, which will adversely affect the performance, so it is preferably an integer of 1 to 3 , Especially preferred is 1.

The above-described formula (1), Z is independently a hydrogen atom, by the following formula _{-SiR '(3-a) X} ' a

(In the formula, R'is independently an alkyl group or phenyl group with carbon number of 1 to 4, X'is independently a hydrolyzable group, and a is an integer of 0 to 3)

Representation base, the following formula -W-(SiR _(3-n) X _n ) _b

(In the formula, R, X, and n are the same as above, W is a divalent to hexavalent hydrocarbon group with siloxane bond, silylene structure or silyl aryl structure, b is an integer of 1 to 5)

Represents the base, or is selected from the following formula

(In the formula, E is a monovalent organic group) represents the base of the structure.

_{-SiR '(3-a) X} ' a in, X 'may be different from each other hydrolyzable group. Such X'can include alkoxy, ethoxy, propoxy, isopropoxy, butoxy and other alkoxy groups with 1 to 10 carbon atoms, methoxymethoxy, methoxyethoxy Alkoxy with 2 to 10 carbons such as alkoxy, acetyloxy with 1 to 10 carbons, and alkenyloxy with 2 to 10 carbons such as isopropenoxy, chloro , Bromo, iodo and other halogen groups. Among them, methoxy, ethoxy, isopropenoxy, and chloro are preferred.

R'is an alkyl group such as methyl, ethyl, propyl, butyl, etc. having 1 to 4 carbon atoms, or a phenyl group, of which methyl and ethyl are preferred.

a is an integer of 0 to 3, preferably 0 or 1, and more preferably 0 from the viewpoint of storage stability.

In addition, in -W-(SiR _(3-n) X _n ) _b , R, X, and n are the same as above, and b is an integer of 1 to 5. If it is less than 1, the adhesion to the substrate will decrease , When 6 or more, the terminal alkoxy valence is too high, which will adversely affect the performance, so it is preferably an integer of 1 to 3, particularly preferably 1.

W is a divalent to hexavalent, preferably divalent to tetravalent, and more preferably divalent hydrocarbon group having a siloxane bond, a silylene structure or a silylene structure.

W is a divalent to hexavalent hydrocarbon group having a siloxane bond, a silylene structure or a silylene structure. Specifically, the alkylene groups can be connected to each other via a silylalkylene structure or a silylalkylene structure. On the linking bond of the divalent group, divalent to hexavalent silicon atoms with 2 to 40, preferably 2 to 10, linear, branched or cyclic organopolysiloxane residues Divalent to hexavalent groups bonded with alkylene groups, etc., preferably divalent groups, divalent to tetravalent silicon atoms in which alkylene groups are bonded to each other via a silylalkylene structure or silylalkylene structure A number of 2 to 10 linear, branched or cyclic organopolysiloxane residues have divalent to tetravalent alkylene groups bonded to the linkages.

Here, the silylene structure, the aryl silylene structure, and linear, branched, or cyclic divalent to hexavalent organopolysiloxane residues include, for example, the same ones as described above.

Specific examples of W include the following bases.

In addition, selected from the following formula

表示之結構之基中，E係一價之有機基，以碳數1~10、特別是1~6之非取代或取代之一價烴基、碳數1~6之烷氧 基、或苯氧基為佳。這種E具體而言，可列舉甲基、乙基、丙基、異丙基、丁基、異丁基、sec-丁基、tert-丁基、戊基、異戊基、sec-戊基、tert-戊基、二異戊基(Siamyl)、己基、異己基、sec-己基、tert-己基、2,3-二甲基-2-丁基(THEXYL)等之烷基、乙烯基、烯丙基、丙烯基等之烯基、苯基、甲苯基、二甲苯基等之芳基、苄基、苯基乙基、苯基丙基等之芳烷基等或、此等之基之氫原子之一部分或全部經氟、溴、氯等之鹵素原子、氰基、硝基、碳數1~3之烷氧基等取代者，例如氯甲基、氯丙基、溴乙基、三氟甲基、三氟丙基、九氟丁基、氰基乙基、硝基苯基、甲氧基苯基等，及甲氧基、乙氧基、丙氧基、丁氧基等之烷氧基、苯氧基等，較佳為碳數1~4之烷基、苯基、甲苯基。

In the structure of the group, E is a monovalent organic group, which is an unsubstituted or substituted monovalent hydrocarbon group with 1~10 carbons, especially 1~6, alkoxy with 1~6 carbons, or phenoxy Base is better. Specifically, such E includes methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, and sec-pentyl. , Tert-pentyl, diisopentyl (Siamyl), hexyl, isohexyl, sec-hexyl, tert-hexyl, 2,3-dimethyl-2-butyl (THEXYL) and other alkyl, vinyl, Alkenyl such as allyl, propenyl, aryl such as phenyl, tolyl, xylyl, benzyl, phenylethyl, phenylpropyl, etc. aralkyl, etc. or these groups Part or all of the hydrogen atoms are substituted by halogen atoms such as fluorine, bromine, chlorine, cyano, nitro, and alkoxy with 1 to 3 carbons, such as chloromethyl, chloropropyl, bromoethyl, tri Fluoromethyl, trifluoropropyl, nonafluorobutyl, cyanoethyl, nitrophenyl, methoxyphenyl, etc., and alkanes such as methoxy, ethoxy, propoxy, butoxy, etc. The oxy group, phenoxy group, etc., are preferably alkyl groups having 1 to 4 carbon atoms, phenyl groups, and tolyl groups.

Specifically, Z includes, for example, a hydrogen atom and those shown below.

The fluorine-containing polyether group polymer-modified silane represented by the above formula (1) includes, for example, those represented by the following formula. In addition, in each formula, the number of repetitions (or degree of polymerization) of each repeating unit constituting the fluorooxyalkyl group or the fluorooxyalkylene group can be any number satisfying any of the above-mentioned formulas (2) and (3).

(In the formula, Z, g1, w are the same as above, p1 is an integer from 5 to 100, q1 is an integer from 5 to 100, and p1+q1 is an integer from 10 to 105).

The preparation method of the fluorine-containing polyether group polymer-modified silane represented by the above formula (1) includes, for example, the following methods.

First of all, a fluorinated polyether group polymer having reactive groups such as fluorinated acyl groups, halogenated acyl groups, acid anhydride groups, ester groups, carboxylic acid groups, and amide groups at the end of the molecular chain and a nucleophile are used as Solvents such as 1,3-bis(trifluoromethyl)benzene and tetrahydrofuran are mixed, and aged at 0~80℃, preferably 50~70℃, more preferably about 60℃, for 1~6 hours, preferably It is 3 to 5 hours, more preferably about 4 hours.

Here, specific examples of the polymer having a fluorine-containing polyether group having a reactive group at the end of the molecular chain include those shown below.

(In the formula, Rf and α are the same as above).

In addition, as the nucleophile, allyl magnesium halide, 3-butenyl magnesium halide, 4-pentenyl magnesium halide, 5-hexenyl magnesium halide, and the like can also be used. Furthermore, it is also possible to use the corresponding lithium reagent.

The amount of nucleophile used is 1 equivalent relative to the reactive group of the polymer of the fluorine-containing polyether group with a reactive group at the end of the molecular chain, and it can be used in 2 to 5 equivalents, more preferably 2.5 to 3.5 equivalents, and more It is preferably about 3 equivalents.

Then, the reaction was stopped, and the aqueous layer and the fluorine solvent layer were separated by a liquid separation operation. The obtained fluorine solvent layer is washed with an organic solvent, and the solvent is distilled off to obtain a fluorine-containing polyether group polymer having a hydroxyl group and an olefin moiety at the molecular chain end represented by the following formula (a).

(In the formula, Rf and α are the same as above. U is a divalent hydrocarbon group).

In the above formula (a), U is a divalent hydrocarbon group, specifically, methylene, ethylene, propylene (trimethylene, methylethylene), ethylene (tetramethylene) , Methyl propylene), hexamethylene, octamethylene and other C1-C8 alkylenes, phenylene and other C6-C8 arylalkylenes (e.g. , C7-8 alkyl group, aryl group, etc.) etc. U is preferably a linear alkylene group having 1 to 4 carbon atoms.

Secondly, if necessary, replace the hydrogen atom of the hydroxyl group of the polymer having a hydroxyl group and an olefin moiety at the end of the molecular chain represented by the formula (a) obtained above with another group.

Represents a substituent of the hydrogen atom of a hydroxyl group into the silicon to method A represents -SiR _a sum _{'(3-a) X'} , for example of formula (a) having a hydroxyl group and a molecular chain end portion of the olefin groups of the fluoropolyether Polymers and silylating agents, in the presence of bases such as amines or alkali metal bases, if necessary, use solvents such as fluorine-based solvents, organic solvents, etc., at 0~80℃, preferably 40~60℃ , More preferably, it is aged at a temperature of about 50°C for 1 to 24 hours, preferably 2 to 10 hours, and more preferably about 3 hours.

In addition, another method is to combine a fluorine-containing polyether group polymer with a hydroxyl group and an olefin moiety at the end of the molecular chain represented by the formula (a) and hydrogen silane to a platinum group metal catalyst or a boron catalyst or other dehydrogenation catalyst In the presence of the medium, use solvents such as fluorine-based solvents, organic solvents, etc., at a temperature of 0 to 60°C, preferably 15 to 35°C, more preferably about 25°C, for 10 minutes to 24 hours, preferably The dehydrogenation reaction is carried out in 30 minutes to 2 hours, more preferably about 1 hour.

Here, the silylating agent can be, for example, silyl halide or silyl trifluoromethane sulfonate (triflate). Specifically, trimethylchlorosilane, triethylchlorosilane, tert -Butyldimethyl chloride, triisopropylchlorosilane, triphenylchlorosilane, trimethylsilyl bromide, trimethylsilyl trifluoromethane sulfonate, triethylsilyl three Fluoromethane sulfonate, tert-butyl dimethyl trifluoromethane sulfonate, triisopropylsilyl trifluoromethane sulfonate, etc., and if no alkali is used, hexamethyl bis Silazane, trimethylsilyl dimethyl amine, trimethyl silyl diethyl amine, trimethyl silyl imidazole, the amount used is relative to the molecular chain end represented by formula (a) The hydroxyl group and the olefin part of the fluorine-containing polyether group polymer have 1 equivalent of hydroxyl group, and 1~10 equivalents can be used, more It is preferably 1 to 4 equivalents, and more preferably about 2 equivalents.

In addition, the hydrogen silane can include trimethylsilane, triethylsilane, tert-butyldimethylsilane, triisopropylsilane, triphenylsilane, etc. The amount used is relative to the molecule represented by formula (a) The hydroxyl group of the polymer of the fluorine-containing polyether group having a hydroxyl group and an olefin moiety at the chain end can be used in 1 to 5 equivalents, more preferably 1.5 to 3 equivalents, and more preferably about 2 equivalents.

Then, the reaction was stopped, and the aqueous layer and the fluorine solvent layer were separated by a liquid separation operation. The obtained fluorine solvent layer is washed with an organic solvent, and the solvent is distilled off to obtain a fluorine-containing polyether group polymer having a silyl group and an olefin moiety at the molecular chain end represented by the following formula (b).

(In the formula, Rf, R', X', a, U, and α are the same as above).

The method of substituting the hydrogen atom of the hydroxyl group with the silyl group represented by -W-(SiR _(3-n) X _n ) _b , for example, the fluorine-containing polycarbonate with a hydroxyl group and an olefin site at the end of the molecular chain represented by formula (a) Ether-based polymers and hydrolyzable silyl groups at one end of the hydrogen silane or hydrosiloxane (hydrosiloxane), in the presence of boron catalysts and other dehydrogenation catalysts, use fluorine-based solvents, organic solvents and other solvents , Dehydrogenation is carried out at a temperature of 0~60°C, preferably 15~35°C, more preferably about 25°C, for 10 minutes to 24 hours, preferably 30 minutes to 2 hours, more preferably about 1 hour reaction.

Here, the hydrosilanes or hydrosiloxanes having a hydrolyzable silyl group at one end include, for example, those shown below.

(In the formula, g and w are the same as above).

The usage amount is 1 equivalent to the hydroxyl group of the polymer of the fluorine-containing polyether group having a hydroxyl group and an olefin moiety at the end of the molecular chain represented by formula (a), and 1-10 equivalents can be used, more preferably 1.2-5 equivalents.

Then, the reaction was stopped, and the aqueous layer and the fluorine solvent layer were separated by a liquid separation operation. The obtained fluorine solvent layer is washed with an organic solvent and the solvent is distilled off to obtain a fluorine-containing polyether in which the molecular chain terminal represented by the following formula (c) has an olefin site and the hydroxyl group is substituted with a hydrolyzable silyl group Base polymer.

(In the formula, Rf, W, R, X, n, U, and α are the same as above).

A method of substituting the hydrogen atom of a hydroxyl group with a group containing a carbonyl group, a sulfonyl group or a phosphinyl group, for example, the fluorine-containing polyether group polymer with a hydroxyl group and an olefin moiety at the end of the molecular chain represented by formula (a) is fused with Agent, sulfonating agent or phosphating agent, in the presence of amines or alkali metal bases and other bases, if necessary, use N,N-dimethyl-4-aminopyridine and other catalysts Or solvents such as fluorine-based solvents, organic solvents, etc., at 0-100°C, preferably 50-70°C, More preferably, it is aged at a temperature of about 60°C for 10-25 hours, preferably 15-20 hours, and more preferably about 18 hours.

Here, as the acylating agent, for example, an acyl halide can be used. Specifically, acetic anhydride, propionic anhydride, trifluoroacetic anhydride, benzoic anhydride, acetyl halide, propionyl halide, and trifluoroacetate can be used. Acetyl halide, benzyl halide, methyl benzyl halide, etc. The amount used is relative to the fluorine-containing polyether group with hydroxyl and olefin moiety at the end of the molecular chain represented by formula (a) For 1 equivalent of the hydroxyl group of the polymer, 1-10 equivalents can be used, more preferably 3-6 equivalents, and still more preferably about 5 equivalents.

As the sulfonylating agent, for example, sulfonyl halides, etc. can be used. Specifically, methanesulfonyl chloride, trifluoromethanesulfonic anhydride, nonafluorobutanesulfonyl chloride, p-toluenesulfonyl chloride, o-Nitrobenzenesulfonyl chloride, etc. The amount used is 1 equivalent to the hydroxyl group of the polymer of the fluorine-containing polyether group with a hydroxyl group and an olefin part at the end of the molecular chain represented by formula (a), and 1-10 can be used The equivalent is more preferably 2 to 5 equivalents, and still more preferably about 3 equivalents.

The phosphating agent can be, for example, phosphatidyl halides, etc., specifically, dimethylphosphatidyl chloride, diethylphosphatidyl chloride, diphenylphosphatidyl chloride, etc., and the amount used is 1 to 10 equivalents, more preferably 2 to 5 equivalents, and more preferably about 1 equivalent of the hydroxyl group of the polymer of the fluoropolyether group with a hydroxyl group and an olefin moiety at the end of the molecular chain represented by formula (a) 3 equivalents.

Then, the reaction is stopped, and the organic layer or the water layer and the fluorine solvent layer are separated by a liquid separation operation. The obtained fluorine solvent layer is cleaned with an organic solvent, and the solvent is distilled off. The molecular chain terminal represented by the following formula (d) has a hydroxyl group protected by a carbonyl group, a sulfonyl group, or a phosphinyl group. Fluorine-containing polyether-based polymer.

[In the formula, Rf, U, and α are the same as above. B is selected from the following formula

(In the formula, E is the same as above). The basis of the structure of representation].

In addition, the method of substituting the hydrogen atom of the hydroxyl group with the terminal unsaturated group, for example, the polymer of the fluorine-containing polyether group with the hydroxyl group and the olefin moiety at the end of the molecular chain represented by formula (a) and the olefin introducing agent are used in the amine or In the presence of alkalis such as alkali metal bases, if necessary, use additives such as tetrabutylammonium halide, alkali metal halide, etc. to improve reactivity, or solvents such as fluorine-based solvents, organic solvents, etc., at 0~90℃ , Preferably it is 60~80℃, more preferably about 70℃, aging for 1~25 hours, preferably 3~10 hours, more preferably about 6 hours.

Here, as the olefin introducing agent, for example, allyl halide and the like can be used. Specifically, allyl chloride, allyl bromide, allyl iodide, 4-chloro-1-butene, 4- Bromo-1-butene, 4-iodo-1-butene, 5-chloro-1-pentene, 5-bromo-1-pentene, 5-iodo-1-pentene, etc. The usage amount is relative to Formula (a) represents 1 equivalent of the hydroxyl group of the polymer of the fluoropolyether group with hydroxyl and olefin moiety at the end of the molecular chain. 1-10 equivalents can be used, more preferably 2.5-6 equivalents, and more preferably about 5 equivalents .

Then, the reaction was stopped, and the aqueous layer and the fluorine solvent layer were separated by a liquid separation operation. The obtained fluorine solvent layer is washed with an organic solvent, and the solvent is distilled off to obtain a fluorine-containing polyether group polymer having an olefin moiety at the end of the molecular chain represented by the following formula (e).

(In the formula, Rf, U, and α are the same as above. V is a single bond or a divalent hydrocarbon group).

In the above formula (e), V is a single bond or a divalent hydrocarbon group. Specifically, the divalent hydrocarbon group includes methylene, ethylene, propylene (trimethylene, methylethylene), and ethylene Groups (tetramethylene, methyl propylene), hexamethylene, octamethylene, etc. containing alkylene with carbon number 1-8, phenylene, etc. with carbon number 6-8 The alkylene group (for example, the alkylene group with 7 to 8 carbon atoms, the arylene group, etc.) and the like. V is preferably a single bond or a straight chain alkylene group with 1 to 4 carbon atoms.

Secondly, after reacting any one of the fluorine-containing polyether group polymer having an olefin site at the end of the molecular chain represented by the above-obtained formulas (a) to (e) with an organosilicon compound having two or more SiH groups in the molecule , Make the SiH group at the polymer end of the reactant and the organosilicon compound with olefin site and hydrolyzable end group in the molecule, in the hydrosilation reaction catalyst, such as chloroplatinic acid/vinylsiloxane complex In the presence of a toluene solution, the aging is performed at a temperature of 40 to 120°C, preferably 60 to 100°C, more preferably about 80°C, for 1 to 72 hours, preferably 20 to 36 hours, and more preferably about 24 hours.

Also, another method is to make the molecules represented by the formulas (a)~(e) obtained above Any one of polymers with fluorine-containing polyether groups with olefin moieties at the chain ends and organosilicon compounds with SiH groups and hydrolyzable end groups in the molecule are used in hydrosilation reaction catalysts, such as chloroplatinic acid/vinyl silicone In the presence of a toluene solution of the alkane complex, the temperature is 40 to 120°C, preferably 60 to 100°C, more preferably about 80°C, for 1 to 72 hours, preferably 20 to 60 hours.

Here, the organosilicon compound having two or more SiH groups in the molecule is preferably a compound represented by the following formula.

(In the formula, R ¹ , R ² , g, h, and j are the same as above).

Examples of such organosilicon compounds having two or more SiH groups in the molecule include those shown below.

The amount of the organosilicon compound with more than two SiH groups in the molecule is relative to the terminal unsaturated group of the polymer with olefinic part at the end of the molecular chain represented by the above formula (a)~(e) The equivalent may be 5-20 equivalents, more preferably 7.5-12.5 equivalents, and still more preferably about 10 equivalents.

In addition, the organosilicon compound having an olefin moiety and a hydrolyzable terminal group in the molecule is preferably a compound represented by the following formula.

(In the formula, R, X, and n are the same as above. T is a single bond or a divalent hydrocarbon group).

Here, T is a single bond or a divalent hydrocarbon group. Specifically, the divalent hydrocarbon group includes methylene, ethylene, propylene (trimethylene, methylethylene), ethylene (tetraethylene) Methyl, methacryl), hexamethylene, octaethylene Methyl and other alkylene groups containing 1 to 8 carbon atoms, phenylene and other alkylene groups containing 6 to 8 carbon atoms (e.g., alkylene groups with 7 to 8 carbon atoms. Arylene groups, etc.) )Wait. T is preferably a single bond or a methylene group.

The use amount of the organosilicon compound with olefin moiety and hydrolyzable end group in the molecule is 1 equivalent of the SiH group at the polymer end of the reactant obtained above, and it can be used in 2-6 equivalents, more preferably 2.2-3.5 equivalents. It is more preferably about 3 equivalents.

In addition, the organosilicon compound having a SiH group and a hydrolyzable terminal group in the molecule is preferably a compound represented by the following formula.

(In the formula, g and w are the same as above).

The usage amount of the organosilicon compound with SiH group and hydrolyzable end group in the molecule is relative to the end unsaturation of the polymer with fluorine-containing polyether group with olefin moiety at the end of the molecular chain represented by the above formulas (a)~(e) Based on 1 equivalent, 5-20 equivalents can be used, more preferably 7.5-12.5 equivalents, and still more preferably about 10 equivalents.

Then, the solvent and unreacted materials are removed by vacuum distillation to obtain the polymer-modified silane of the fluorine-containing polyether group represented by the above formula (1). In addition, the above-mentioned reaction may be carried out singly or continuously.

The surface treatment agent of the present invention contains the fluorine-containing polyether group polymer-modified silane represented by the above formula (1). In addition, it is also possible to use a conventional method by modifying the fluorine-containing polyether group-containing polymer to modify the terminal hydrolyzable group of silane in advance. Method, the partial hydrolysis condensation product obtained by partial hydrolysis condensation.

The surface treatment agent of the present invention may further contain the following general formula (4) [formation 52] A-Rf'-A (4)

(In the formula, A is a fluorine atom or a monovalent fluorine-containing group at the terminal -CF ₃ group, and Rf' is a polymer residue of a divalent fluorine-containing oxyalkylene group).

The fluorine-containing polyether group-containing polymer (hereinafter referred to as non-functional polymer).

In the above formula (4), the A-based fluorine atom or a monovalent fluorine-containing group at the terminal -CF ₃ group is preferably a fluorine atom and a linear perfluoroalkyl group having 1 to 6 carbon atoms. Among them, preferred is -F group, -CF ₃ group, -CF ₂ CF ₃ group, -CF ₂ CF ₂ CF ₃ group.

In addition, Rf' is a divalent fluorine-containing oxyalkylene polymer residue, and Rf' is preferably one shown below.

(In the formula, p2 is an integer of 5 to 200, preferably 10 to 100, q2 is an integer of 5 to 200, preferably 10 to 100, r1 is an integer of 10 to 200, preferably 20 to 100, t1 It is an integer of 5~200, preferably 10~100, t2 It is an integer of 10 to 200, preferably 20 to 100, t1+p2 is an integer of 10 to 205, preferably 20 to 110, and q2+p2 is an integer of 10 to 205, preferably 20 to 110).

The non-functional polymer represented by formula (4) includes the following.

(In the formula, p2, q2, r1, t1, and t2 are the same as above).

The amount used when formulating the non-functional polymer represented by formula (4) is not particularly limited, but it is compared with the fluorine-containing polyether-based polymer represented by formula (1) to modify silane and/or its partial hydrolysis condensate The mass is preferably 0.1 to 60% by mass, and particularly preferably in the range of 10 to 40% by mass. If it is too large, adhesion problems may occur.

In addition, if necessary, the surface treatment agent can be added with a hydrolysis condensation catalyst, such as organotin compounds (DIBUTYLTIN DIMETHOXIDE, dibutyltin dilaurate, etc.), organic titanium compounds (tetran titanate -Butyl ester, etc.), organic acid (acetic acid, methanesulfonic acid, fluorine-modified carboxylic acid, etc.), inorganic acid (hydrochloric acid, sulfuric acid, etc.). Among them, acetic acid, tetra-n-butyl titanate, dibutyltin dilaurate, fluorine modification are particularly preferred Carboxylic acid, etc. The addition amount is the amount of the catalyst, usually relative to 100 parts by mass of the fluorine-containing polyether-based polymer-modified silane and/or its partial hydrolysis condensate, preferably 0.01-5 parts by mass, particularly preferably 0.1-1 parts by mass .

The surface treatment agent may also contain an appropriate solvent. Such solvents include, for example, fluorine-modified aliphatic hydrocarbon solvents (perfluoroheptane, perfluorooctane, etc.), fluorine-modified aromatic hydrocarbon solvents (xylenehexafluoride) (1,3 -Bis(trifluoromethyl)benzene), benzotrifluoride, etc.), fluorine-modified ether solvents (methyl perfluorobutyl ether, ethyl perfluorobutyl ether, perfluoro(2-butyltetrahydrofuran) ), etc.), fluorine-modified alkylamine solvents (perfluorotributylamine, perfluorotripentylamine, etc.), hydrocarbon solvents (petroleum ether, mineral spirits, toluene, xylene, etc.) , Ketone solvents (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.). Among these, from the viewpoints of solubility, wettability, etc., fluorine-modified solvents are preferred, and m-xylene hexafluoride, perfluoro(2-butyltetrahydrofuran), and perfluorotributylene are particularly preferred. Base amine, ethyl perfluorobutyl ether.

The above-mentioned solvents can be mixed with two or more kinds, but it is preferable to uniformly dissolve the fluorine-containing polyether group-modified silane and its partial hydrolysis condensate. In addition, the optimal concentration of the fluorine-containing polyether-based polymer modified silane and/or its partial hydrolysis condensate dissolved in the solvent varies depending on the treatment method, but it is preferably 0.01-40% by mass in the surface treatment agent , Particularly preferably 0.05-25% by mass.

The surface treatment agent of the present invention is subjected to surface treatment on the treated surface of a resin product previously treated with SiO ₂ .

Here, the resin product is preferably made of thermoplastic resin. Specifically, it is preferable to use a thermoplastic resin film (hardened (Hard Coat) film), pencil hardness 4H or higher, thermoplastic resin film without hard coating (high hardness resin film) or thermoplastic resin film with anti-reflection layer (anti-reflection film), etc.

In addition, the present invention uses a resin product that has been treated with SiO _{2 in} advance. Here, the processing based SiO ₂ by a sputtering method was treated by SiO _2, from the resin article to improve adhesion with the treatment agent of the viewpoint, preferred.

The surface treatment agent of the present invention can be applied to the above-mentioned substrate by conventional methods such as brushing, dipping, spraying, and evaporation treatment. The heating method at the time of the vapor deposition treatment may be either a resistance heating method or an electron beam heating method, and is not particularly limited. In addition, the curing conditions vary depending on the curing method. For example, in the case of vapor deposition or spray coating, in the case of using a resin film treated with SiO ₂ as the substrate, it can be set at room temperature (25°C) to 200 Within the range of ℃, it can be cured for 5 minutes to 24 hours, especially 10 minutes to 12 hours, and can also be cured under humidification. In particular, even in the present invention, even at room temperature, a short time of about 10 minutes to 24 hours, particularly 30 minutes to 12 hours, especially 30 minutes to 1 hour, is sufficient. In addition, the thickness of the cured film can be appropriately selected according to the type of substrate, but it is usually 0.1 to 100 nm, especially 1 to 25 nm.

In addition, when the surface treatment agent of the present invention is applied to a substrate, the fluorine-containing polyether group polymer in the surface treatment agent can also be modified to partially hydrolyze the silane and/or the fluorine-containing polyether group polymer is modified to partially hydrolyze the silane The hydrolyzable group contained in the condensate is used after being hydrolyzed. For example, during spray coating, it is diluted with a fluorine-based solvent to which water is added in advance, and the hydrolyzable group in the surface treatment agent is hydrolyzed, in other words, it is formed in the solution After Si-OH group, spray When coating, the hardening after coating becomes faster, so it is preferred.

The resin products treated with the above-mentioned surface treatment agent of the present invention can be used as car navigation systems, mobile phones, digital cameras, digital cameras, PDAs, portable audio players, car audio systems, game consoles, glasses lenses, camera lenses , Filters, sunglasses, gastroscopes and other medical equipment, photocopiers, personal computers (PC), liquid crystal displays, organic EL displays, plasma displays, touch panel displays, protective films, hardened films, high hardness resins, Anti-reflective films, wearable terminals, etc. are parts of products or some of the optical items used, touch panels, anti-reflective films, quartz substrates, etc. are preferred.

The surface treatment agent for the surface treatment of the resin product of the present invention shows excellent water and oil repellency or durability even for a short time under mild curing conditions such as room temperature curing for the aforementioned articles, so it is especially useful as eyeglass lenses , Touch panel display, hardened film, high hardness resin, anti-reflective film, wearable terminal, etc. water and oil repellent layer. Here, the high-hardness resin refers to, for example, a product made of resin molded with a pencil hardness of 4H or more, such as the product name SILPLUS manufactured by Nippon Steel Chemical Co., Ltd., or the product name HD film manufactured by Gunze Corporation, which is a film PR that replaces glass, and particularly refers to the resin The molded resin film is not particularly limited to the above products.

[Example]

The following shows synthesis examples, examples, reference examples, and comparative examples to illustrate the present invention in more detail, but the present invention is not limited to the following examples.

The examples and comparative examples used the compounds obtained by the following synthesis examples.

[Synthesis Example 1] Synthesis of Compound 1

In the reaction vessel, 150 g of tetrahydrofuran and 300 g of 1,3-bis(trifluoromethyl)benzene were mixed, and 160 ml of 0.7M allyl magnesium bromide was dropped. Then, slowly drop the following formula (A)

表示之含氟聚醚基之聚合物。 After 200g (4.8×10 ^-2 mol) of the indicated compound, heat at 60°C for 4 hours. After heating, it was cooled to room temperature, and the solution was dropped into 300 g of 1.2 M hydrochloric acid aqueous solution to stop the reaction. After the lower fluorine compound layer was recovered by the liquid separation operation, it was washed with acetone. The fluorine compound layer in the lower layer after washing was recovered again, and the remaining solvent was distilled off under reduced pressure to obtain the following formula (B)

Said fluorine-containing polyether-based polymer.

表示之化合物42.2g(1.0×10^-2mol)，使溶解於1,3-雙(三氟甲基)苯80g中，混合氯化鉑酸/乙烯基矽氧烷錯合物之甲苯溶液8.0×10^-2g(含有Pt單體2.1×10^-6mol)與1，4-雙(二甲基甲矽烷基)苯37g(1.9×10^-1mol)，在80℃下熟成7小時，藉由餾除溶劑及未反應物，得到下述式(C)

表示之含氟聚醚基之聚合物。 In the reaction vessel, add the following formula (B)

The indicated compound 42.2g (1.0×10 ^-2 mol), dissolved in 80g 1,3-bis(trifluoromethyl)benzene, mixed with chloroplatinic acid/vinylsiloxane complex in toluene solution 8.0 ×10 ^-2 g (containing 2.1×10 ^-6 mol of Pt monomer) and 37 g (1.9×10 ^-1 mol) of 1,4-bis(dimethylsilyl)benzene, aged at 80°C for 7 hours, By distilling off the solvent and unreacted substances, the following formula (C) is obtained

Said fluorine-containing polyether-based polymer.

¹ H-NMR δ0-0.2(-Si(C H ₃ ) ₂ )24H δ0.4-0.6(-CH ₂ CH ₂ C H ₂ -Si)4H δ1.3-1.6(-CH ₂ C H ₂ CH ₂ -Si)4H δ1.6-1.9(-C H ₂ CH ₂ CH ₂ -Si)4H δ3.6-4.2(-Si H )2H δ6.6-7.1(-C ₆ H ₄ )8H

表示之化合物23.1g(0.5×10^-2mol)、1,3-雙(三氟甲基)苯100g、烯丙基三甲氧基矽烷3.3g(2.0×10^-2mol)、及氯化鉑酸/乙烯基矽氧烷錯合物之甲苯溶液6.0×10^-2g(含有Pt單體1.6×10^-6mol)，於80℃下使熟成2小時。然後，減壓餾除溶劑及未反應物，得到液狀的產物(化合物1)。 In the reaction vessel, mix the following formula (C)

The indicated compound is 23.1g (0.5×10 ^-2 mol), 1,3-bis(trifluoromethyl)benzene 100g, allyltrimethoxysilane 3.3g (2.0×10 ^-2 mol), and platinum chloride A toluene solution of acid/vinylsiloxane complex compound 6.0×10 ^-2 g (containing 1.6×10 ^-6 mol of Pt monomer), matured at 80°C for 2 hours. Then, the solvent and unreacted materials were distilled off under reduced pressure to obtain a liquid product (Compound 1).

The obtained compound 1 was considered to have a structure represented by the following formula (D) by ¹ H-NMR.

¹ H-NMR δ0-0.2(-Si(C H ₃ ) ₂ )24H δ0.4-0.6(-CH ₂ CH ₂ C H ₂ -Si,-Si-C H ₂ CH ₂ C H ₂ -Si)12H δ0.9-1.3(-CH ₂ C H ₂ CH ₂ -Si,-Si-CH ₂ C H ₂ CH ₂ -Si)12H δ2.8-3.2(-Si(OC H ₃ ) ₃ )18H δ6.3 -7.8(-C ₆ H ₄ )8H

[Synthesis Example 2] Synthesis of Compound 2

表示之化合物114g(2.7×10^-2mol)後，滴下三甲基氯矽烷5.8g(5.4×10^-2mol)。接著，於50℃下加熱3小時。加熱終了後，冷卻至室溫，滴下鹽酸水溶液。藉由分液操作回收下層的氟化合物層後，以甲醇洗淨。再次回收洗淨後之下層的氟化合物層，減壓下，餾除殘存溶劑，得到 下述式(E)

表示之含氟聚醚基之聚合物。 In the reaction vessel, 100 g of 1,3-bis(trifluoromethyl)benzene, 8.2 g (5.4×10 ^-2 mol) of DBU (diazabicycloundecene), and the following formula (B) are mixed

After 114 g (2.7×10 ^-2 mol) of the indicated compound, 5.8 g (5.4×10 ^-2 mol) of trimethylchlorosilane was dropped. Then, it heated at 50 degreeC for 3 hours. After heating, it was cooled to room temperature and an aqueous hydrochloric acid solution was dropped. After the fluorine compound layer in the lower layer was recovered by a liquid separation operation, it was washed with methanol. The fluorine compound layer in the lower layer after washing was recovered again, and the remaining solvent was distilled off under reduced pressure to obtain the following formula (E)

Said fluorine-containing polyether-based polymer.

¹ H-NMR δ0-0.2(-OSi(C H ₃ ) ₃ )9H δ2.4-2.6(-C H ₂ CH=CH ₂ )4H δ5.0-5.2(-CH ₂ CH=C H ₂ )4H δ5.7-5.9(-CH ₂ C H =CH ₂ )2H

表示之化合物60.1g(1.4×10^-2mol)，使溶解於1,3-雙(三氟甲基)苯50g中，混合氯化鉑酸/乙烯基矽氧烷錯合物之甲苯溶液1.5×10^-1g(含有Pt單體4.0×10^-6mol)與1,3,5,7-四甲基環四矽氧烷33g(1.3×10^-1mol)，在80℃下熟成19小時，藉由減壓餾除溶劑及未反應物，得到下述式(F)表示之含氟聚醚基之聚合物。 In the reaction vessel, add the following formula (E)

The indicated compound is 60.1g (1.4×10 ^-2 mol), dissolved in 50g of 1,3-bis(trifluoromethyl)benzene, mixed with chloroplatinic acid/vinylsiloxane complex in toluene solution 1.5 ×10 ^-1 g (containing Pt monomer 4.0×10 ^-6 mol) and 1,3,5,7-tetramethylcyclotetrasiloxane 33g (1.3×10 ^-1 mol), aged 19 at 80℃ After hours, the solvent and unreacted materials were distilled off under reduced pressure to obtain a fluorine-containing polyether group-containing polymer represented by the following formula (F).

¹ H-NMR δ0-0.2(-OSi-C H ₃ 、-OSi(C H ₃ ) ₃ )36H δ0.5-0.8(-CH ₂ CH ₂ C H ₂ -Si)4H δ1.3-2.2(- C H ₂ C H ₂ CH ₂ -Si)8H δ4.3-5.2(-Si H )6H

表示之化合物26.5g(0.6×10^-2mol)、1,3-雙(三氟甲基)苯25g、烯丙基三甲氧基矽烷7.3g(4.5×10^-2mol)、及氯化鉑酸/乙烯基矽氧烷錯合物之甲苯溶液6.5×10^-2g(含有Pt單體1.7×10^-6mol)，於80℃下使熟成12小時。然後，減壓餾除溶劑及未反應物，得到液狀的產物(化合物2)。 In the reaction vessel, mix the following formula (F)

The indicated compound is 26.5g (0.6×10 ^-2 mol), 1,3-bis(trifluoromethyl)benzene 25g, allyltrimethoxysilane 7.3g (4.5×10 ^-2 mol), and platinum chloride The toluene solution of acid/vinylsiloxane complexes is 6.5×10 ^-2 g (containing 1.7×10 ^-6 mol of Pt monomer), and matured at 80°C for 12 hours. Then, the solvent and unreacted materials were distilled off under reduced pressure to obtain a liquid product (compound 2).

The obtained compound 2 was confirmed to have a structure represented by the following formula (G) by ¹ H-NMR.

^{1 H-NMR δ0-0.2 (-OSi-} C H 3, -OSi (C H 3) 3) 33H δ0.4-0.8 (-C H 2 CH 2 C H 2 -Si) 16H δ1.3 - 1.9 ( -CH ₂ C H ₂ CH ₂ -Si,-C H ₂ C H ₂ CH ₂ -Si)12H δ3.3-3.6(-Si(OC H ₃ ) ₃ )54H

[Synthesis Example 3] Synthesis of Compound 3

表示之化合物59g(1.4×10^-2mol)，使溶解於1,3-雙(三氟甲基)苯50g中，混合氯化鉑酸/乙烯基矽氧烷錯合物之甲苯溶液2.5×10^-1g(含有Pt單體6.6×10^-6mol)與下述式(H)

表示之化合物8.7g(3.1×10^-2mol)，於80℃下熟成48小時，藉由減壓餾除溶劑及未反應物，得到下述式(I)

表示之含氟聚醚基之聚合物(化合物3)。 In the reaction vessel, add the following formula (B)

The indicated compound 59g (1.4×10 ^-2 mol), dissolved in 50g 1,3-bis(trifluoromethyl)benzene, mixed with chloroplatinic acid/vinylsiloxane complex toluene solution 2.5× 10 ^-1 g (with Pt monomer 6.6×10 ^-6 mol) and the following formula (H)

8.7 g (3.1×10 ^-2 mol) of the compound indicated, aged at 80°C for 48 hours, and the solvent and unreacted substances were removed by vacuum distillation to obtain the following formula (I)

Fluorine-containing polyether-based polymer (compound 3).

¹ H-NMR δ0-0.2(-OSi(C H ₃ ) ₂ )24H δ0.3-0.6(-C H ₂ C H ₂ -Si,-CH ₂ CH ₂ C H ₂ -Si)12H δ1.3- 1.8(-C H ₂ CH ₂ CH ₂ -Si,-CH ₂ C H ₂ CH ₂ -Si)8H δ3.3-3.6(-Si(OC H ₃ ) ₃ )18H

[Synthesis Example 4] Synthesis of Compound 4

表示之化合物400g(0.95×10^-1mol)，緩慢滴下三乙基矽烷14.1g(1.2×10^-1mol)後，於25℃下攪拌1小時。接著，添加水，藉由分液操作回收下層的氟化合物層後，以丙酮洗淨。再次回收洗淨後之下層的氟化合物層，減壓下，餾除殘存溶劑，得到下述式(J)

表示之含氟聚醚基之聚合物。 In the reaction vessel, mix 200 g of 1,3-bis(trifluoromethyl)benzene, 0.29 g (5.5×10 ^-4 mol) of ginseng(pentafluorophenyl)borane, and the following formula (B)

After 400 g (0.95×10 ^-1 mol) of the compound indicated, 14.1 g (1.2×10 ^-1 mol) of triethylsilane was slowly dropped, and the mixture was stirred at 25°C for 1 hour. Next, water was added, and the lower fluorine compound layer was recovered by a liquid separation operation, and then washed with acetone. The fluorine compound layer in the lower layer after washing was recovered again, and the remaining solvent was distilled off under reduced pressure to obtain the following formula (J)

Said fluorine-containing polyether-based polymer.

¹ H-NMR δ0.5-0.8(-SiC H ₂ CH ₃ )2H δ0.8-1.1(-SiCH ₂ C H ₃ )3H δ2.4-2.6(-C H ₂ CH=CH ₂ )4H δ5. 0-5.1(-CH ₂ CH=C H ₂ )4H δ5.7-5.9(-CH ₂ C H =CH ₂ )2H

表示之化合物60.7g(1.4×10^-2mol)，使溶解於1,3-雙(三氟甲基)苯50g中，混合氯化鉑酸/乙烯基矽氧烷錯合物之甲苯溶液2.5×10^-1g(含有Pt單體6.6×10^-6mol)與下述式(H)

表示之化合物8.7g(3.1×10^-2mol)，於80℃下熟成48小時，藉由減壓餾除溶劑及未反應物，得到下述式(K)

表示之含氟聚醚基之聚合物(化合物4)。 In the reaction vessel, add the following formula (J)

The indicated compound is 60.7g (1.4×10 ^-2 mol), dissolved in 50g of 1,3-bis(trifluoromethyl)benzene, mixed with chloroplatinic acid/vinylsiloxane complex in toluene solution 2.5 ×10 ^-1 g (with Pt monomer 6.6×10 ^-6 mol) and the following formula (H)

8.7g (3.1×10 ^-2 mol) of the compound indicated, aged at 80°C for 48 hours, and the solvent and unreacted substances were removed by vacuum distillation to obtain the following formula (K)

Fluorinated polyether-based polymer (Compound 4).

¹ H-NMR δ0-0.2(-OSi(C H ₃ ) ₂ ,-OSi(C H ₂ C H ₃ ) ₃ )39H δ0.3-0.6(-C H ₂ CH ₂ -Si,-CH ₂ C H ₂ -Si,-CH ₂ CH ₂ C H ₂ -S i)12H δ1.3-1.8(-C H ₂ CH ₂ CH ₂ -Si,-CH ₂ C H ₂ CH ₂ -Si)8H δ3.3- 3.6(-Si(OC H ₃ ) ₃ )18H

[Synthesis Example 5] Synthesis of Compound 5

表示之化合物169g(4.0×10^-2mol)，使溶解於1,3-雙(三氟甲基)苯150g中，混合氯化鉑酸/乙烯基矽氧烷錯合物之甲苯溶液8.0×10^-2g(含有Pt單體4.0×10^-6mol)與1,1,3,3,5,5-六甲基三矽氧烷83g(4.0×10^-1mol)，於80℃下熟成24小時，藉由減壓餾除溶劑及未反應物，得到下述式(L)

表示之含氟聚醚基之聚合物。 In the reaction vessel, add the following formula (B)

The indicated compound 169g (4.0×10 ^-2 mol), dissolved in 150g 1,3-bis(trifluoromethyl)benzene, mixed with chloroplatinic acid/vinylsiloxane complex toluene solution 8.0× 10 ^-2 g (containing 4.0×10 ^-6 mol of Pt monomer) and 83 g (4.0×10 ^-1 mol) of 1,1,3,3,5,5-hexamethyltrisiloxane, at 80℃ After aging for 24 hours, the solvent and unreacted materials were removed by vacuum distillation to obtain the following formula (L)

Said fluorine-containing polyether-based polymer.

^{1 H-NMR δ0-0.2 (-OSi (} C H 3) 2) 36H δ0.3-0.6 (-CH 2 CH 2 C H 2 -Si) 4H δ1.3 - 1.8 (- C H 2 CH 2 CH 2 -Si,-CH ₂ C H ₂ CH ₂ -Si)8H δ3.3-3.6(-SiH)2H

表示之化合物145g(3.1×10^-2mol)、1,3-雙(三氟甲基)苯145g、烯丙基三甲氧基矽烷15.0g(9.3×10^-2mol)、及氯化鉑酸/乙烯基矽氧烷錯合物之甲苯溶液1.4×10^-2g(含有Pt單體3.7×10^-6mol)，於80℃下使熟成3小時。然後，藉由減壓餾除溶劑及未反應物，得到液狀的產物(化合物5)。 In the reaction vessel, mix the following formula (L)

The indicated compound 145g (3.1×10 ^-2 mol), 1,3-bis(trifluoromethyl)benzene 145g, allyl trimethoxysilane 15.0g (9.3×10 ^-2 mol), and chloroplatinic acid /Vinylsiloxane complex toluene solution 1.4×10 ^-2 g (containing Pt monomer 3.7×10 ^-6 mol), matured at 80℃ for 3 hours. Then, the solvent and unreacted materials were distilled off under reduced pressure to obtain a liquid product (compound 5).

The obtained compound 5 was confirmed to have a structure represented by the following formula (M) by ¹ H-NMR.

¹ H-NMR δ0-0.2(-OSi(C H ₃ ) ₂ )36H δ0.3-0.8(-C H ₂ CH ₂ C H ₂ -Si,-CH ₂ CH ₂ C H ₂ -Si)12H δ1. 5-1.9(-C H ₂ C H ₂ CH ₂ -Si,-CH ₂ C H ₂ CH ₂ -Si)12H δ3.3-3.6(-si(OC H ₃ ) ₃ )18H

[Synthesis Example 6] Synthesis of Compound 6

表示之化合物59g(1.4×10^-2mol)，使溶解於1,3-雙(三氟甲基)苯50g中，混合氯化鉑酸/乙烯基矽氧烷錯合物之甲苯溶液8.0×10^-2g(含有Pt單體1.3×10^-6mol)與1,1,3,3,5,5,7,7-八甲基四矽氧烷40g(1.4×10^-1mol)，於80℃下熟成4小時，藉由減壓餾除溶劑及未反應物，得到下述式(N)表示之含氟聚醚基之聚合物。 In the reaction vessel, add the following formula (B)

The indicated compound 59g (1.4×10 ^-2 mol), dissolved in 50g 1,3-bis(trifluoromethyl)benzene, mixed with chloroplatinic acid/vinylsiloxane complex toluene solution 8.0× 10 ^-2 g (containing Pt monomer 1.3×10 ^-6 mol) and 1,1,3,3,5,5,7,7-octamethyltetrasiloxane 40g (1.4×10 ^-1 mol), After aging at 80°C for 4 hours, the solvent and unreacted materials were removed by distillation under reduced pressure to obtain a fluorinated polyether group-containing polymer represented by the following formula (N).

¹ H-NMR δ0-0.2(-OSi(C H ₃ ) ₂ )48H δ0.3-0.6(-CH ₂ CH ₂ C H ₂ -Si)4H δ1.3-1.8(-C H ₂ CH ₂ CH ₂ -Si,-CH ₂ C H ₂ CH ₂ -Si)8H δ3.3-3.6(-SiH)2H

表示之化合物30g(0.63×10^-2mol)、1,3-雙(三氟甲基)苯30g、烯丙基三甲氧基矽烷3.0g(1.8×10^-2mol)、及氯化鉑酸/乙烯基矽氧烷錯合物之甲苯溶液3.0×10^-2g(含有Pt單體0.8×10^-6mol)，於80℃下使熟成6小時。然後，減壓餾除溶劑及未反應物，得到液狀的產物(化合物6)。 In the reaction vessel, mix the following formula (N)

The indicated compound 30g (0.63×10 ^-2 mol), 1,3-bis(trifluoromethyl)benzene 30g, allyl trimethoxysilane 3.0g (1.8×10 ^-2 mol), and chloroplatinic acid /Vinylsiloxane complex toluene solution 3.0×10 ^-2 g (containing 0.8×10 ^-6 mol of Pt monomer), matured at 80°C for 6 hours. Then, the solvent and unreacted materials were distilled off under reduced pressure to obtain a liquid product (compound 6).

The obtained compound 6 was confirmed to have a structure represented by the following formula (O) by ¹ H-NMR.

¹ H-NMR δ0-0.2(-OSi(C H ₃ ) ₂ )48H δ0.3-0.8(-C H ₂ CH ₂ C H ₂ -Si, CH ₂ CH ₂ C H ₂ -Si)12H δ1.5 _{^{- 1.9 (-CH 2 C H 2}} CH 2 -Si, -C H 2 C H 2 CH 2 -Si) 12H δ3.3-3.6 (-Si (OC H 3) 3) 18H

[Synthesis Example 7] Synthesis of Compound 7

表示之化合物4.8g(0.1×10^-2mol)、1,3-雙(三氟甲基)苯5g、5-己烯-1-三甲氧基矽烷0.61g(0.3×10^-2mol)、及氯化 鉑酸/乙烯基矽氧烷錯合物之甲苯溶液0.5×10^-2g(含有Pt單體0.1×10^-6mol)，使於80℃下熟成6小時。然後，減壓餾除溶劑及未反應物，得到液狀的產物(化合物7)。 In the reaction vessel, mix the following formula (N)

The compound represented is 4.8g (0.1×10 ^-2 mol), 1,3-bis(trifluoromethyl)benzene 5g, 5-hexene-1-trimethoxysilane 0.61g (0.3×10 ^-2 mol), And 0.5×10 ^-2 g of toluene solution of chloroplatinic acid/vinylsiloxane complex (containing 0.1×10 ^-6 mol of Pt monomer), and ripen at 80°C for 6 hours. Then, the solvent and unreacted materials were distilled off under reduced pressure to obtain a liquid product (compound 7).

The obtained compound 7 was confirmed to have a structure represented by the following formula (P) by ¹ H-NMR.

¹ H-NMR δ0-0.2(-OSi(C H ₃ ) ₂ )48H δ0.3-0.8(-CH ₂ CH ₂ C H ₂ -Si,-C H ₂ CH ₂ CH ₂ CH ₂ CH ₂ C H ₂ -Si)12H δ1.0-2.2(-C H ₂ C H ₂ CH ₂ -Si,-CH ₂ C H ₂ C H ₂ C H ₂ C H ₂ CH ₂ --Si)24H δ3.3-3.6( -Si(OC H ₃ ) ₃ )18H

[Synthesis Example 8] Synthesis of Compound 8

表示之化合物4.8g(0.1×10^-2mol)、1,3-雙(三氟甲基)苯5g、7-辛烯基三甲氧基矽烷0.7g(0.3×10^-2mol)、及氯化鉑酸/乙烯基矽氧烷錯合物之甲苯溶液0.4×10^-2g(含有Pt單 體0.1×10^-6mol)，使於80℃熟成6小時。然後，減壓餾除溶劑及未反應物，得到液狀的產物(化合物8)。 In the reaction vessel, mix the following formula (N)

The indicated compound is 4.8g (0.1×10 ^-2 mol), 1,3-bis(trifluoromethyl)benzene 5g, 7-octenyl trimethoxysilane 0.7g (0.3×10 ^-2 mol), and chlorine 0.4×10 ^-2 g (containing 0.1×10 ^-6 mol of Pt monomer) in toluene solution of platinic acid/vinylsiloxane complex, and mature at 80°C for 6 hours. Then, the solvent and unreacted materials were distilled off under reduced pressure to obtain a liquid product (compound 8).

The obtained compound 8 was confirmed to have a structure represented by the following formula (Q) by ¹ H-NMR.

^{1 H-NMR δ0-0.2 (-OSi (} C H 3) 2) 48H δ0.3 - 0.8 (-CH 2 CH 2 C H 2 -Si, -C H 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH ₂ C H ₂ -Si)12H δ1.0-2.2(-C H ₂ C H ₂ CH ₂ -Si,-CH ₂ C H ₂ C H ₂ C H ₂ C H ₂ C H ₂ C H ₂ CH _2- Si)28H δ3.3-3.6(-Si(OC H ₃ ) ₃ )18H

[Synthesis Example 9] Synthesis of Compound 9

表示之化合物21g(0.5×10^-2mol)，使溶解於1,3-雙(三氟甲基)苯20g中，混合氯化鉑酸/乙烯基矽氧烷錯合物之甲苯溶液2.0×10^-2g(含有Pt單體0.5×10^-6mol)與下述式(R)

表示之十矽氧烷36.3g(0.5×10^-1mol)，使於80℃熟成7小時，藉由減壓餾除溶劑及未反應物，得到下述式(S)

表示之含氟聚醚基之聚合物。 In the reaction vessel, add the following formula (B)

The indicated compound 21g (0.5×10 ^-2 mol), dissolved in 20g 1,3-bis(trifluoromethyl)benzene, mixed with chloroplatinic acid/vinylsiloxane complex toluene solution 2.0× 10 ^-2 g (containing 0.5×10 ^-6 mol of Pt monomer) and the following formula (R)

The indicated decasiloxane 36.3g (0.5×10 ^-1 mol) was aged at 80°C for 7 hours, and the solvent and unreacted substances were removed by vacuum distillation to obtain the following formula (S)

Said fluorine-containing polyether-based polymer.

¹ H-NMR δ0-0.2(-OSi(C H ₃ ) ₂ )120H δ0.3-0.8(-CH ₂ CH ₂ C H ₂ -Si)4H δ1.3-1.8(-C H ₂ CH ₂ CH ₂ -Si,-CH ₂ C H ₂ CH ₂ -Si)8H δ4.7-5.0(-SiH)2H

表示之化合物11.4g(0.2×10^-2mol)、1,3-雙(三氟甲基)苯10g、烯丙基三甲氧基矽烷1.1g(0.7×10^-2mol)、及氯化鉑酸/乙烯基矽氧烷錯合物之甲苯溶液1.0×10^-2g(含有Pt單體0.3×10^-6mol)，使於80℃下熟成6小時。然後，減壓餾除溶劑及未反應物，得到液狀的產物(化合物9)。 In the reaction vessel, mix the following formula (S)

The indicated compound 11.4g (0.2×10 ^-2 mol), 1,3-bis(trifluoromethyl)benzene 10g, allyltrimethoxysilane 1.1g (0.7×10 ^-2 mol), and platinum chloride The toluene solution of acid/vinylsiloxane complex is 1.0×10 ^-2 g (containing 0.3×10 ^-6 mol of Pt monomer) and matured at 80°C for 6 hours. Then, the solvent and unreacted materials were distilled off under reduced pressure to obtain a liquid product (compound 9).

The obtained compound 9 was confirmed to have a structure represented by the following formula (T) by ¹ H-NMR.

¹ H-NMR δ0-0.2(-OSi(C H ₃ ) ₂ )120H δ0.3-0.8(-CH ₂ CH ₂ C H ₂ -Si,-C H ₂ CH ₂ C H ₂ -Si)12H δ1. 2-2.0(-C H ₂ C H ₂ CH ₂ -Si,-CH ₂ C H ₂ CH ₂ -Si)12H δ3.3-3.6(-Si(OC H ₃ ) ₃ )18H

[Synthesis Example 10] Synthesis of Compound 10

表示之化合物12g(0.21×10^-2mol)、1,3-雙(三氟甲基)苯12g、7-辛烯基三甲氧基矽烷1.9g(0.8×10^-2mol)、及氯化鉑酸/乙烯基矽氧烷錯合物之甲苯溶液1.2×10^-2g(含有Pt單體0.3×10^-6mol)，使於80℃下熟成24小時。然後，減壓餾除溶劑及未反應物，得到液狀的產物(化合物10)。 In the reaction vessel, mix the following formula (S)

The indicated compound 12g (0.21×10 ^-2 mol), 1,3-bis(trifluoromethyl)benzene 12g, 7-octenyl trimethoxysilane 1.9g (0.8×10 ^-2 mol), and chlorinated The toluene solution of platinum acid/vinylsiloxane complex is 1.2×10 ^-2 g (containing 0.3×10 ^-6 mol of Pt monomer), and it is matured at 80°C for 24 hours. Then, the solvent and unreacted materials were distilled off under reduced pressure to obtain a liquid product (Compound 10).

The obtained compound 10 was confirmed to have a structure represented by the following formula (U) by ¹ H-NMR.

¹ H-NMR δ0-0.2(-OSi(C H ₃ ) ₂ )120H δ0.3-0.8(-CH ₂ CH ₂ C H ₂ -Si,-C H ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ C H ₂ -Si)12H δ1.2-2.0(-C H ₂ C H ₂ CH ₂ -Si,-C H ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ C H ₂ -Si)32H δ3 .3-3.6(-Si(OC H ₃ ) ₃ )18H

[Synthesis Example 11] Synthesis of Compound 11

表示之化合物30g(0.7×10^-2mol)，使溶解於1,3-雙(三氟甲基)苯25g中，混合氯化鉑酸/乙烯基矽氧烷錯合物之甲苯溶液2.5×10^-2g(含有Pt單體0.7×10^-6mol)與雙(二甲基甲矽烷基)甲烷9.2g(0.7×10^-1mol)，使於80℃熟成24小時，藉由減壓餾除溶劑及未反應物，得到下述式(V)

表示之含氟聚醚基之聚合物。 In the reaction vessel, add the following formula (B)

The indicated compound 30g (0.7×10 ^-2 mol), dissolved in 25g of 1,3-bis(trifluoromethyl)benzene, mixed with chloroplatinic acid/vinylsiloxane complex toluene solution 2.5× 10 ^-2 g (containing 0.7×10 ^-6 mol of Pt monomer) and 9.2 g (0.7×10 ^-1 mol) of bis(dimethylsilyl)methane, aged at 80°C for 24 hours, by reducing pressure The solvent and unreacted materials are removed by distillation to obtain the following formula (V)

Said fluorine-containing polyether-based polymer.

¹ H-NMR δ0-0.4(-OSi(C H ₃ ) ₂ ,-Si-C H ₂ -Si)28H δ0.4-0.8(-CH ₂ CH ₂ C H ₂ -Si)4H δ1.2-2.0 (-C H ₂ C H ₂ CH ₂ -Si)8H δ3.8-4.2(-SiH)2H

表示之化合物20g(0.45×10^-2mol)、1,3-雙(三氟甲基)苯20g、烯丙基三甲氧基矽烷2.0g(1.2×10^-2mol)、及氯化鉑酸/乙烯基矽氧烷錯合物之甲苯溶液2.0×10^-2g(含有Pt單體0.5×10^-6mol)，使於80℃下熟成6小時。然後，減壓餾除溶劑及未反應物，得到液狀的產物(化合物11)。 In the reaction vessel, mix the following formula (V)

The indicated compound 20g (0.45×10 ^-2 mol), 1,3-bis(trifluoromethyl)benzene 20g, allyltrimethoxysilane 2.0g (1.2×10 ^-2 mol), and chloroplatinic acid /Vinylsiloxane complex toluene solution 2.0×10 ^-2 g (containing 0.5×10 ^-6 mol of Pt monomer), matured at 80°C for 6 hours. Then, the solvent and unreacted materials were distilled off under reduced pressure to obtain a liquid product (Compound 11).

The obtained compound 11 was confirmed to have a structure represented by the following formula (W) by ¹ H-NMR.

¹ H-NMR δ0-0.4(-OSi(C H ₃ ) ₂ ,-Si-C H ₂ -Si)28H δ0.4-1.0(-CH ₂ CH ₂ C H ₂ -Si,-C H ₂ CH ₂ C H ₂ -Si)12H δ1.2-2.0(-C H ₂ C H ₂ CH ₂ -Si,-CH ₂ C H ₂ CH ₂ -Si)12H δ3.2-3.8(-Si(OCH ₃ ) ₃ )18H

[Synthesis Example 12] Synthesis of Compound 12

表示之化合物342g(8.1×10^-2mol)後，以60℃加熱18小時。加熱終了後，冷卻至室溫，將水滴下。藉由分液操作回收下層的氟化合物層後，以甲醇洗淨。再次回收洗淨後之下層的氟化合物層，減壓下，餾除殘存溶劑，得到下述式(X)

表示之含氟聚醚基之聚合物。 In the reaction vessel, mix 300g of 1,3-bis(trifluoromethyl)benzene, 41.9g (0.41mol) of acetic anhydride, 41.5g (4.1×10 ^-1 mol) of triethylamine, N,N-dimethyl -4-aminopyridine 0.49g (4.1×10 ^-3 mol). Then, slowly drop the following formula (B)

After 342g (8.1×10 ^-2 mol) of the indicated compound, it was heated at 60°C for 18 hours. After heating, cool to room temperature and drop water. After the fluorine compound layer in the lower layer was recovered by a liquid separation operation, it was washed with methanol. The fluorine compound layer in the lower layer after washing was recovered again, and the remaining solvent was distilled off under reduced pressure to obtain the following formula (X)

Said fluorine-containing polyether-based polymer.

¹ H-NMR δ1.8-1.9(-OCOC H ₃ )3H δ2.7-2.8,2.9-3.0(-C H ₂ CH=CH ₂ )4H δ5.0-5.1(-CH ₂ CH=C H ₂ )4H δ5.7-5.8(-CH ₂ C H =CH ₂ )2H

表示之化合物171g(4.0×10^-2mol)，使溶解於1,3-雙(三氟甲基)苯150g中，混合氯化鉑酸/乙烯基矽氧烷錯合物之甲苯溶液8.0×10^-2g(含有Pt單體4.0×10^-6mol)與1,1,3,3,5,5-六甲基三矽氧烷83g(4.0×10^-1mol)，使於80℃熟成24小時，藉由減壓餾除溶劑及未反應物，得到下述式(Y)

表示之含氟聚醚基之聚合物。 In the reaction vessel, add the following formula (X)

The indicated compound 171g (4.0×10 ^-2 mol), dissolved in 150g 1,3-bis(trifluoromethyl)benzene, mixed with chloroplatinic acid/vinylsiloxane complex toluene solution 8.0× 10 ^-2 g (containing 4.0×10 ^-6 mol of Pt monomer) and 83 g (4.0×10 ^-1 mol) of 1,1,3,3,5,5-hexamethyltrisiloxane at 80℃ After aging for 24 hours, the solvent and unreacted materials were removed by vacuum distillation to obtain the following formula (Y)

Said fluorine-containing polyether-based polymer.

^{1 H-NMR δ0-0.2 (-OSi (} C H 3) 2) 36H δ0.3-0.6 (-CH 2 CH 2 C H 2 -Si) 4H δ1.3 - 1.8 (-C H 2 CH 2 CH 2 -Si,-CH ₂ C H ₂ CH ₂ -Si)8H δ1.8-1.9(-OCOC H ₃ )3H δ3.3-3.6(-SiH)2H

表示之化合物145g(3.1×10^-2mol)、1,3-雙(三氟甲基)苯145g、烯丙基三甲氧基矽烷15.0g(9.3×10^-2mol)、及氯化鉑酸/乙烯基矽氧烷錯合物之甲苯溶液1.4×10^-2g(含有Pt單體3.7×10^-6mol)，使於80℃下熟成3小時。然後，減壓餾除溶劑及未反應物，得到液狀的產物(化合物12)。 In the reaction vessel, mix the following formula (Y)

The indicated compound 145g (3.1×10 ^-2 mol), 1,3-bis(trifluoromethyl)benzene 145g, allyl trimethoxysilane 15.0g (9.3×10 ^-2 mol), and chloroplatinic acid /Vinylsiloxane complex in toluene solution 1.4×10 ^-2 g (containing 3.7×10 ^-6 mol of Pt monomer), matured at 80°C for 3 hours. Then, the solvent and unreacted materials were distilled off under reduced pressure to obtain a liquid product (Compound 12).

The obtained compound 12 was confirmed to have a structure represented by the following formula (Z) by ¹ H-NMR.

¹ H-NMR δ0-0.2(-OSi(C H ₃ ) ₂ )36H δ0.3-0.8(-C H ₂ CH ₂ C H ₂ -Si,-CH ₂ CH ₂ C H ₂ -Si)12H δ1. 5-1.8(-C H ₂ C H ₂ CH ₂ -Si,-CH ₂ C H ₂ CH ₂ -Si)12H δ1.8-1.9(-OCOC H ₃ )3H δ3.3-3.6(-Si(OC H ₃ ) ₃ )18H

[Synthesis Example 13] Synthesis of Compound 13

表示之化合物30g(0.7×10^-2mol)，使溶解於1,3-雙(三氟甲基)苯50g中，混合三(五氟苯基)硼烷1.3×10^-2g與下述式(H)

表示之化合物8.5g(3.0×10^-2mol)，於80℃下熟成6小時，以甲醇25g(0.8mol)洗淨後，藉由減壓餾除溶劑及未反應物，得到下述式(A’)

表示之含氟聚醚基之聚合物。 In the reaction vessel, add the following formula (B)

30g (0.7×10 ^-2 mol) of the indicated compound, dissolved in 50g of 1,3-bis(trifluoromethyl)benzene, mix 1.3×10 ^-2 g of tris(pentafluorophenyl)borane with the following Formula (H)

8.5g (3.0×10 ^-2 mol) of the compound indicated, aged at 80°C for 6 hours, washed with 25g (0.8mol) of methanol, and the solvent and unreacted substances were removed by vacuum distillation to obtain the following formula ( A')

Said fluorine-containing polyether-based polymer.

¹ H-NMR δ0-0.2(-OSi(C H ₃ ) ₂ )12H δ0.3-0.8(-C H ₂ C H ₂ -Si)4H δ2.4-2.6(-C H ₂ CH=CH ₂ ) 4H δ3.3-3.6(-Si(OC H ₃ ) ₃ )9H δ5.0-5.2(-CH ₂ CH=C H ₂ )4H δ5.7-5.9(-CH ₂ C H =CH ₂ )2H

表示之化合物18.0g(0.4×10^-2mol)，使溶解於1,3-雙(三氟甲基)苯15g中，混合氯化鉑酸/乙烯基矽氧烷錯合物之甲苯溶液1.5×10^-2g(含有Pt單體0.4×10^-6mol)與下述式(H)

表示之化合物11.3g(4.0×10^-2mol)，使於80℃熟成24小時，減壓餾除溶劑及未反應物，得到液狀的產物(化合物13)。 In the reaction vessel, add the following formula (A')

The indicated compound 18.0g (0.4×10 ^-2 mol), dissolved in 15g of 1,3-bis(trifluoromethyl)benzene, mixed with chloroplatinic acid/vinylsiloxane complex in toluene solution 1.5 ×10 ^-2 g (containing 0.4×10 ^-6 mol of Pt monomer) and the following formula (H)

11.3 g (4.0×10 ^-2 mol) of the indicated compound was aged at 80°C for 24 hours, and the solvent and unreacted materials were distilled off under reduced pressure to obtain a liquid product (compound 13).

The obtained compound 13 was confirmed to have a structure represented by the following formula (B') by ¹ H-NMR.

¹ H-NMR δ0-0.2(-OSi(C H ₃ ) ₂ )36H δ0.3-0.8(-Si-C H ₂ C H ₂ -Si,-CH ₂ CH ₂ C H ₂ -Si)16H δ1. 3-1.8(-C H ₂ C H ₂ CH ₂ -Si)8H δ3.3-3.6(-Si(OC H ₃ ) ₃ )27H

[Synthesis Example 14] Synthesis of compound 14 (comparative product)

表示之化合物110g(2.6×10^-2mol)、1,3-雙(三氟甲基)苯200g、三甲氧基矽烷13.4g(1.1×10^-1mol)、及氯化鉑酸/乙烯基矽氧烷錯合物之甲苯溶液6.0×10^-1g(含有Pt單體1.6×10^-5mol)，使於80℃下熟成40小時。然後，減壓餾除溶劑及未反應物。接著，藉由分子蒸餾裝置去除殘存之低沸點成分、高沸點成分，得到液狀的產物(化合物14)201g。 In the reaction vessel, mix the following formula (B)

The indicated compound 110g (2.6×10 ^-2 mol), 1,3-bis(trifluoromethyl)benzene 200g, trimethoxysilane 13.4g (1.1×10 ^-1 mol), and chloroplatinic acid/vinyl The toluene solution of siloxane complex is 6.0×10 ^-1 g (containing 1.6×10 ^-5 mol of Pt monomer) and matured at 80°C for 40 hours. Then, the solvent and unreacted materials were distilled off under reduced pressure. Next, the remaining low boiling point components and high boiling point components were removed by a molecular distillation apparatus to obtain 201 g of a liquid product (compound 14).

The obtained compound 14 was confirmed to have a structure represented by the following formula (C') by ¹ H-NMR.

¹ H-NMR δ0.2-2.2(-C H ₂ C H ₂ C H ₂ -)12H δ3.0-3.5(-Si(OC H ₃ ) ₃ )18H

In addition, the following compounds were used in Comparative Examples.

[Compound 15]

【Chemical 112】(H ₃ CO) ₃ Si-CH ₂ CH ₂ CH ₂ -CH ₂ O-CF ₂ -(CF ₂ O) _p1 -(C ₂ F ₄ O) _q1 -CF ₂ -CH ₂ O-CH ₂ CH ₂ CH ₂ -Si(OCH ₃ ) ₃ p1: q1=47: 53, p1+q1≒45

[Compound 16]

[Examples 1 to 11, Reference Examples 1, 2, and Comparative Examples 1 to 3]

Preparation of surface treatment agent and formation of hardened film

The above-mentioned compounds 1 to 16 were dissolved in Novec 7200 (manufactured by 3M, ethyl perfluorobutyl ether) to a concentration of 20% by mass to prepare a surface treatment agent. After the surface treatment agent is prepared, within 24 hours, the resin film (manufactured by Tigold) after sputtering SiO ₂ on the outermost surface with a thickness of 15 nm is treated with plasma (Ar: 10cc, O ₂ : 80cc, output : 250W, time: 30 seconds) wash, spray the above surface treatment agent using a spray coating device (manufactured by T&K Co., Ltd., NST-51), and cure it at 25°C and humidity 50%RH 24 When it is small, a cured film with a thickness of 15 nm is formed. In addition, the resin film is made of polyethylene terephthalate, and the surface of the film is treated with an acrylic hard film, and then SiO ₂ is sputtered on the outermost surface with a thickness of 15 nm.

In addition, the surface treatment agent of the above compound was prepared with the same prescription, and within 24 hours, the resin film (manufactured by Tigold) after sputtering SiO ₂ with a thickness of 15 nm on the outermost surface was treated with plasma (Ar ：10cc, O ₂ ：80cc, output: 250W, time: 30 seconds) wash, 10mg of surface treatment agent is vacuum evaporated on it (treatment conditions are pressure: 2.0×10 ^-2 Pa, heating temperature: 700℃) Cured for 24 hours in an environment of 25°C and 50%RH to form a cured film with a thickness of 15nm.

The cured films formed from compounds 2 and 4 to 13 were used as Examples 1 to 11, the cured films formed from compounds 1 and 3 were used as Reference Examples 1 and 2, and the cured films formed from compounds 14 to 16 were used as Comparative Examples 1 to 3.

The cured films of Examples 1 to 11, Reference Examples 1, 2, and Comparative Examples 1 to 3 were evaluated by the following methods. Any test was carried out at 25°C and a humidity of 50%RH.

[Evaluation of wear resistance]

In the obtained cured film, Tribogear TYPE: 30S (manufactured by Shinto Scientific Co., Ltd.) was used to measure the abrasion resistance to cloth (BEMCOT).

Under the following conditions, the test is ended when the water contact angle becomes less than 100°. The abrasion resistance was evaluated by the number of times of abrasion with a water contact angle of 100° or more.

Contact area: 10mm×30mm

Load: 1.5kg

Fabric wear resistance

Cloth: BEMCOT M-3II (manufactured by Asahi Kasei Corporation)

Moving distance (one way) 20mm

Moving speed 1,800mm/min

Load: 0.5kg/cm ²

In addition, the water contact angle was measured using a contact angle meter DropMaster (manufactured by Kyowa Interface Science Co., Ltd.) to measure the contact angle of the cured film to water (droplet: 2 μl). In addition, the water contact angle was measured after 1 second after dropping a 2 μl drop onto the sample surface.

The results of Examples 1 to 11, Reference Examples 1, 2, and Comparative Examples 1 to 3 in which the cured film was formed by spray coating are shown in Table 1.

In addition, the results of Examples 3, 4, 7, and 8 in which the cured film was formed by vapor deposition coating are shown in Table 3. For comparison, Examples 3 and 4 in which the cured film was formed by spray coating were selected. The results of 7, 8 are shown in Table 2.

According to the above Table 1, in Comparative Examples 1, 2 and 3, the surface treatment agent was spray-coated on the surface of the substrate, and the abrasion resistance test was performed after hardening. The number of abrasion resistance was 0, and the abrasion durability was not shown. On the other hand, in Examples 1-13, the surface treatment agent was spray-coated on the surface of the base material, and the abrasion resistance test was performed after hardening, and excellent abrasion resistance was exhibited. Examples 1 to 13 are considered to be hydrocarbons with siloxane bonds, silanylene, silanylene structures, etc. on the linking group, so they interact with the SiO ₂ layer on the surface of the substrate. The polymer in the surface treatment agent The alignment becomes easier, so compared to the surface treatment agent of the comparative example, the adhesion to the substrate is improved.

In Tables 2 and 3 above, the same surface treatment agent is used, but the coating method is different. Table 2 shows the results of spray coating, and Table 3 shows the results of vapor deposition coating, but both showed excellent abrasion durability. It can be seen that the surface treatment agents of the examples do not vary depending on the coating method, and all show Excellent abrasion durability.

The resin for forming an antifouling surface layer by the surface treatment agent of the polymer-modified silane containing the fluorine-containing polyether group of the present invention shows excellent abrasion durability regardless of the coating method of the surface treatment agent. The resin for forming an antifouling surface layer with the surface treatment agent of the present invention is particularly suitable for use in spectacle lenses, sunglasses, touch panel displays, anti-reflective films and other applications that require antifouling treatment.

[Industrial availability]

The resin product surface-treated with the surface treatment agent of the polymer-modified silane containing fluorine-containing polyether group and/or its partial hydrolysis condensate of the present invention has excellent abrasion durability on the treated surface. The resin product of the present invention can be particularly used for touch panel displays, anti-reflection films, eyeglass lenses and other resin products that are supposed to adhere to grease.

Claims (15)

A resin product, which is the treated surface of a resin product that has been surface-treated with SiO _{2 in} advance, further by containing the following general formula (1a) or (1b)

[In the formula, Rf is a polymer residue of a monovalent fluorooxyalkyl or a divalent fluorooxyalkylene (fluorooxyalkylene), and Y independently has a siloxane bond and a silylene structure Or the divalent to hexavalent hydrocarbon group of the silyl arylene structure, Y'is independently selected from the following formulae

(In the formula, g1 is an integer from 2 to 20, w is an integer from 2 to 10), R is independently an alkyl group with 1 to 4 carbons or phenyl, X is independently a hydrolyzable group, and n is 1 to 3 the integer, m is an integer of 1 to 5, Z 'is independently represented by the following formula _{-SiR' (3-a) X} 'a ( wherein, R' is independently an alkyl group having 1 to 4 carbon atoms or the phenyl, X 'Independently is a hydrolyzable group, a is an integer from 0 to 3) represented by the following formula -W-(SiR _(3-n) X _n ) _b (where R, X, and n are the same as above, W is a divalent to hexavalent hydrocarbon group having a siloxane bond, a silylene structure or a silyl aryl structure, b is an integer of 1 to 5), or selected from the following formulas

(In the formula, E is a monovalent organic group) represents the structure of the base, α is 1 or 2] represents the fluorine-containing polyether group polymer modified silane and/or its partial hydrolysis condensate surface treatment agent, Made by surface treatment. For example, the resin product of item 1 of the scope of patent application, wherein in the aforementioned formulas (1a) and (1b), α is 1, and the Rf group is the base represented by the following general formula (2),

(In the formula, p, q, r, s are each an integer of 0~200, p+q+r+s=3~200, each repeating unit can be linear or branched, and each repeating unit can have no other Regularly bonding, d is an integer of 1~3). For example, the resin product of item 1 in the scope of the patent application, wherein in the aforementioned formulas (1a) and (1b), α is 2, and the Rf group is the base represented by the following general formula (3),

(In the formula, p, q, r, s are each an integer of 0~200, p+q+r+s=3~200, each repeating unit can be linear or branched, and each repeating unit can have no other Regularly bonding, d is an integer of 1~3). Such as the resin product of any one of items 1 to 3 in the scope of patent application, which In the aforementioned formula (1a), Y is selected from the group consisting of divalent groups in which the alkylene groups are bonded to each other via the silylalkylene structure or silyl aryl structure, and divalent to tetravalent silicon atoms of 2-10. A functional group consisting of a group of divalent to tetravalent alkylene groups is bonded to the linkage of the chain, branched or cyclic organopolysiloxane residue. For example, the resin product of any one of items 1 to 3 in the scope of patent application, wherein in the aforementioned formulas (1a) and (1b), X is selected from the group consisting of alkoxy groups with 1 to 10 carbons, and alkanes with 2 to 10 carbons. A functional group consisting of an oxyalkoxy group, an oxy group with a carbon number of 1-10, an alkenyloxy group with a carbon number of 2-10, and a halogen group. Such as the resin product of any one of items 1 to 3 in the scope of patent application, wherein in the aforementioned formula (1a), Z'is a functional group selected from the following groups, -Si(CH ₃ ) ₃ -Si( CH ₂ CH ₃ ) ₃

For example, the resin product of any one of items 1 to 3 in the scope of the patent application, wherein the polymer-modified silane of the fluorine-containing polyether group represented by the above formulas (1a) and (1b) is selected from the following formulas:

(In the formula, Z is a hydrogen atom or the same as the above Z', 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, g1 is an integer from 2 to 20, w It is an integer from 2 to 10). For example, the resin product of any one of items 1 to 3 in the scope of patent application, wherein the surface treatment agent further contains the following general formula (4) A-Rf'-A (4) (wherein the end of the A series is -CF ₃ A monovalent fluorine-containing group, Rf' is a fluorine-containing polyether group polymer represented by a divalent fluorine-containing oxyalkylene polymer residue). For example, the resin product of any one of items 1 to 3 in the scope of the patent application, wherein the surface treatment agent is surface treated by spray coating or vapor deposition treatment. For example, the resin product of any one of items 1 to 3 in the scope of patent application, wherein the resin product is made of thermoplastic resin. For example, the resin product of any one of items 1 to 3 in the scope of patent application, wherein the aforementioned resin product is a resin product that has been surface-treated with SiO ₂ by a sputtering method, and further the SiO ₂ surface has been treated with plasma. Such as the resin product of any one of items 1 to 3 in the scope of patent application, wherein the resin product is a hard film film, a high hardness resin film or an anti-reflection film. For example, the resin product of any one of items 1 to 3 in the scope of patent application, wherein the resin product is a spectacle lens. For example, the resin product of any one of items 1 to 3 in the scope of patent application, wherein the resin product is a touch panel display. For example, the resin product of any one of items 1 to 3 in the scope of patent application, wherein the resin product is a wearable terminal.