TWI693261B - Fluorine-containing coating agent and articles treated with the coating agent - Google Patents

Abstract

The object of the present invention is to provide a fluorine-containing coating agent that can stably form a water-repellent and oil-repellent film that does not impair the visibility of the substrate even if the film thickness becomes thicker, and to provide a coating agent coated with the coating agent article.

The fluorine-containing coating agent of the present invention as a means for solving the problem, which contains: (A) a silane having a hydrolyzable group at one terminal modified from a polymer containing a fluorooxyalkylene group and/or a portion thereof Hydrolyzed condensates; and (B) Silanes having hydrolyzable groups at both ends and/or partially hydrolyzed condensates thereof modified with a polymer containing a fluorooxyalkylene group, (A) component and (B) component The mixing mass ratio is 20:80~60:40, which is characterized in that when the thickness of the cured coating of the coating agent is 20 nm, the haze measured according to the method described in JIS K7136 is 0.5 or less, with 2,000 reciprocations The water contact angle after abrasion is at least 100° of abrasion durability.

Description

Fluorine-containing coating agent and articles treated with the coating agent

The present invention relates to a coating agent, which contains a silane having a hydrolyzable group modified by a polymer containing a fluorooxyalkylene group, and an article treated with the coating agent.

In recent years, led by the display of mobile phones, is accelerating the touch panel of the screen. However, the touch panel is mostly exposed to the screen, and there are many opportunities for direct contact with fingers or cheeks, and it has the problem of easy adhesion of dirt such as sebum. Here, in order to improve the appearance and visibility, the requirements for the technology that makes it difficult to attach fingerprints to the surface of the display or the technology that can easily remove dirt are increasing year by year. Although the conventional water- and oil-repellent agent can form a film with high water-repellent and oil-repellent properties and excellent dirt-erasing properties, it has a disadvantage that the difference in durability performance every time the film is formed is large. In addition, the treatment agents aggregate with each other, making it difficult to obtain a smooth film. Therefore, the development of treatment agents or treatment methods that can form stable, high-performance films is expected.

Generally speaking, the compound containing perfluorooxyalkylene group (perfluorooxyalkylene group), because the surface free energy is very small, and has water and oil repellency, chemical resistance, lubricity, mold release Sex, anti-fouling, etc. Using this property, it has been widely used in industry for water and oil repellent antifouling agents such as paper and fiber, lubricants for magnetic recording media, oil repellents for precision machines, mold release agents, cosmetics, protective films, etc. However, this property also means that it is non-adhesive and non-adhesive for other substrates, and even if it can be applied to the surface of the substrate, it is difficult to make the coating adhere.

On the other hand, silane coupling agents are commonly known as materials that bond substrate surfaces such as glass or cloth to organic compounds, and have been widely used as coating agents on various substrate surfaces. The silane coupling agent has an organic functional group and a reactive silane group (generally, an alkoxysilane group) in one molecule. Alkoxy silane groups form a coating by self-condensation reaction caused by moisture in the air. The coating is an alkoxysilane group that is hydrolyzed by moisture in the air and is chemically and physically bonded to the surface of glass, metal, or the like to form a durable and durable coating.

As the alkoxysilyl group is bonded to the end of the fluorooxyalkylene group, for example, Patent Document 1 (Japanese Patent Laid-Open No. 2003-238577) proposes a fluorooxyalkylene group-containing silane represented by the following formula. The silane-treated glass or anti-reflection film containing a fluorooxyalkylene group has excellent dirt-erasing properties, but because the terminal groups are bonded to the substrate, the surface lubricity is insufficient, and the sliding properties or scratch resistance are not full.

(In the formula, Rf is a divalent linear perfluorooxyalkylene group, R is carbon Number 1~4 alkyl or phenyl, X is a hydrolyzable group, n is 0~2, m is an integer of 1~5, a is 2 or 3).

In addition, Patent Document 2 (Japanese Patent Laid-Open No. 2013-136833) discloses that by mixing "fluorooxyalkylene-containing silanes", "the average molecular weight is larger than fluorooxyalkylene-containing silanes and has no functional groups. The fluorooxyalkylene group-containing polymer", when applied by vacuum evaporation, can suppress the unevenness of the coated surface to a few nm. The vapor deposition coating system is vapor-deposited starting from a low-boiling component. Therefore, a layer containing a large amount of polymer-modified silane containing a fluorooxyalkylene group is formed on the substrate side, and a non-functional group with a larger molecular weight is formed on the surface side. Of polymer layers containing fluorooxyalkylene groups. Even if agglomeration occurs in the fluorooxyalkylene group-containing polymer layer, the non-functional fluorooxyalkylene group-containing polymer layer on the outermost layer fills the unevenness, so the haze is unlikely to increase. However, when this composition is diluted with a fluorine-based solvent and subjected to surface treatment by spray coating or Dip coating, "fluoroalkoxyalkylene-containing silane" and "non-functional fluorooxyalkylene-containing alkylene The compatibility of the "polymer" will become a problem, and the haze may increase. In this way, it can be seen that even the same composition has a difference in the degree of haze increase due to the coating method.

Patent Document 3 (Japanese Patent Laid-Open No. 2014-015609) discloses that one or more types of perfluoropolyether group-containing silane compounds having hydrolyzable silane groups defined as a specific molecular weight range can be used for substrates Gives water repellency, oil repellency, antifouling properties, and friction durability. However, the above haze problem cannot be solved.

Therefore, it is expected that even if the processing conditions are different Development of treatment agents or treatment methods that stably form a rise in haze to a suppressed, high-performance film.

[Prior Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2003-238577

[Patent Document 2] Japanese Unexamined Patent Publication No. 2013-136833

[Patent Document 3] Japanese Patent Laid-Open No. 2014-015609

The present invention is in view of the above circumstances, and the object of the present invention is to provide a fluorine-containing coating agent, which can stably form a water-repellent oil-repellent film, even if the water-repellent oil-repellent film is about 10 nm thicker than a general film Thick films, especially when the film thickness is thickened to 15 nm or more, can also provide articles coated with the coating agent without impairing the visibility of the substrate.

In order to solve the above-mentioned problems, the present inventors have conducted intensive studies and found that a specific amount is added to the fluorine-containing coating agent containing a polymer having a hydrolyzable group at one terminal and a fluorooxyalkylene structure in the main chain. The polymer with a hydrolyzable group at both ends and a fluorooxyalkylene structure in the main chain, the treatment agent obtained by applying this to the substrate can reduce the haze and at the same time wear durability Excellent.

That is, a fluorine-containing coating agent was found to contain: (A) a silane having a hydrolyzable group at one terminal modified from a polymer containing a fluorooxyalkylene group and/or a partially hydrolyzed condensate thereof; Mixture mass ratio of (B) component and (B) silane and/or its partially hydrolyzed condensate modified with fluorooxyalkylene-containing polymer modified at both ends 20:80~60:40, when the thickness of the cured coating of the coating agent is 20 nm, the haze measured according to the method described in JIS K7136 is 0.5 or less, and the water contact angle after 2,000 reciprocating abrasions is 100 The wear durability of ° or more, such a fluorine-containing coating agent can stably form a water- and oil-repellent film that does not impair the visibility of the substrate even if the film thickness becomes thick, and the wear durability is excellent, and the present invention has been completed.

Furthermore, the present invention provides a fluorine-containing coating agent and articles treated with the coating agent.

[1]. A fluorine-containing coating agent containing: (A) a polymer modified with a fluorooxyalkylene group represented by the following general formula (4) and having a hydrolyzable group at one terminal Silane and/or its partially hydrolyzed condensate; modified with (B) a polymer containing a fluorooxyalkylene group represented by the following general formula (6), a silane having a hydrolyzable group at both ends and /Or its partial hydrolysis condensate, the mixing mass ratio of (A) component with a weight average molecular weight of 1,000 to 20,000 and (B) component with a weight average molecular weight of 1,000 to 20,000 is 20:80 to 60:40, which is characterized by the coating When the film thickness of the hardened coating of the cloth agent is 20 nm, the haze measured according to the method described in JIS K7136 is 0.5 or less, and it has abrasion durability after a water contact angle of 2,000 reciprocating abrasions of 100° or more.

[上述式(4)及(6)中，R¹為碳數1~6之烷基或苯基，X為水解性基，a為2或3，Rf係具有-C_gF_2gO-(式中，g在每單位中獨立為1~6之整數)所表示的重複單位10~200個的2價的(聚)氟氧基伸烷基，A為氟原子、氫原子、或末端為-CF₃基、-CF₂H基或-CFH₂基的1價的含氟基，Q為單鍵、或可具有氧原子、氮原子或矽原子的取代或非取代的碳數2~12之2價的有機基，Q’為碳原子，B為氫原子、碳數1~4之烷基、羥基、或鹵素原子，n為2，m為1，f’為0~10之整數]。

[In the above formulas (4) and (6), R ¹ is an alkyl group having 1 to 6 carbon atoms or a phenyl group, X is a hydrolyzable group, a is 2 or 3, and Rf has -C _g F _2g O-( In the formula, g is independently an integer of 1 to 6 per unit) a repeating unit of 10 to 200 divalent (poly)fluorooxyalkylene groups represented by A, a fluorine atom, a hydrogen atom, or a terminal of- Monovalent fluorine-containing group of CF ₃ group, -CF ₂ H group or -CFH ₂ group, Q is a single bond, or a substituted or unsubstituted carbon number of 2 to 12 which may have an oxygen atom, a nitrogen atom or a silicon atom A divalent organic group, Q'is a carbon atom, B is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a hydroxyl group, or a halogen atom, n is 2, m is 1, and f'is an integer of 0 to 10].

[2]. The fluorine-containing coating agent of [1], wherein Rf is -(CF ₂ ) _d -(OCF ₂ ) _p (OCF ₂ CF ₂ ) _q (OCF ₂ CF ₂ CF ₂ ) _r (OCF ₂ CF ₂ CF ₂ CF ₂ ) _s (OCF(CF ₃ )CF ₂ ) _t -O-(CF ₂ ) _d -(d is an integer independently of 0~5, p, q, r, s and t are mutually Independently is an integer of 0~200, and p+q+r+s+t is an integer of 10~200, and the units shown in parentheses can also be randomly bonded).

[3]. The fluorine-containing coating agent according to [2], which further contains a (poly)fluorooxyalkylene-containing polymer represented by the following general formula (7), A-Rf-A (7)

(In the formula, Rf is a divalent (poly)fluorooxy group having 10 to 200 repeating units represented by -C _g F _2g O- (wherein g is independently an integer of 1 to 6 in each unit)) Alkyl group, A is a fluorine atom, a hydrogen atom, or a monovalent fluorine-containing group having a terminal -CF ₃ group, -CF ₂ H group or -CFH ₂ group).

[4]. The fluorine-containing coating agent according to [2] or [3], which further contains a solvent.

[5]. A cured film obtained by curing the fluorine-containing coating agent of any one of [1] to [4].

[6]. An article with a hardened coating of [5].

[7]. A touch panel covered with the hardened film of [5].

[8]. An anti-reflective article covered with the hardened coating of [5].

[9]. A strengthened glass, which is covered with the cured film of [5].

The hardened film formed by applying the fluorine-containing coating agent of the present invention on a substrate by wet coating can maintain a low-haze surface even when the film thickness is increased, and also has excellent abrasion durability. Therefore, the fluorine-containing coating agent of the present invention can impart low haze and wear durability to various articles by wet processing.

[Figure 1] Example 1 of the present invention, Reference Example 1, and Comparative Example The relationship between the film thickness and the haze of the hardened coatings of 1, 2, 5, and 6.

[Fig. 2] A graph showing the relationship between the film thickness and the haze of the cured film of Reference Example 2 and Comparative Examples 3 and 4 of the present invention.

[Fig. 3] A graph showing the relationship between the content of the (A) component in the cured films of Example 1, Reference Example 1, and Comparative Examples 1, 2, 5, and 6 of the present invention and the haze at a film thickness of 20 nm.

[Fig. 4] A graph showing the relationship between the content of the component (A) in the cured films of Reference Example 2 and Comparative Examples 3 and 4 of the present invention and the haze at a film thickness of 20 nm.

[Best form for carrying out the invention]

The fluorine-containing coating agent of the present invention contains: a silane having a hydrolyzable group at one terminal modified from a polymer containing a fluorooxyalkylene group and/or its partially hydrolyzed condensate (A), and Silanes having hydrolyzable groups at both ends and/or their partially hydrolyzed condensates (B), modified by a polymer containing a fluorooxyalkylene group, the mixing mass ratio of the components (A) and (B) is 20:80~60:40, preferably 25:75~55:45, particularly preferably 30:70~50:50. As long as it is within this range, it is possible to suppress the haze value of the cured film to be a low value and to have excellent abrasion durability.

In addition, it is preferable that the component (B) has the same structure as the silane of the component (A) except for the portion having hydrolyzable groups at both ends.

(A) Ingredients

The component (A) is a silane having a hydrolyzable group at one terminal modified from a polymer containing a fluorooxyalkylene group and/or a partially hydrolyzed condensate thereof. As the silane, the following formula (1)-C _g F _2g O- (1)

(In the formula, g is independently an integer of 1~6 in each unit)

The repeating units represented by 10 to 200 fluorooxyalkylene groups have the following formula (2) at one end

(In the formula, R ¹ is an alkyl group having 1 to 6 carbon atoms or a phenyl group, X is a hydrolyzable group, and a is 2 or 3) The hydrolyzable group represented by is preferably.

Examples of the repeating unit represented by the above formula (1) include the following structures. The fluorooxyalkylene group may be composed of a single type of the structure shown below, or a combination of two or more types. Moreover, these units can also be randomly bonded.

-CF ₂ O-

-CF ₂ CF ₂ O-

-CF ₂ CF ₂ CF ₂ O-

-CF(CF ₃ )CF ₂ O-

-CF ₂ CF ₂ CF ₂ CF ₂ O-

-CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ O-

-CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ O-

-C(CF ₃ ) ₂ O-

Among the groups represented by the above formula (2), X series may be mutually different hydrolyzable groups. Examples of the hydrolyzable group include an alkoxy group having 1 to 10 carbon atoms Group, an alkoxy alkoxy group having 2 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkoxy group having 2 to 10 carbon atoms and a halogen atom. Examples of alkoxy groups include methoxy, ethoxy, propoxy, and butoxy. Examples of alkoxyalkoxy groups include methoxymethoxy and methoxyethoxy. Examples of the acetyloxy group include acetoxy group. Examples of alkenyloxy groups include isopropenyloxy and the like. Examples of the halogen atom include chlorine atom, bromine atom, and iodine atom. Among them, methoxy, ethoxy, isopropenyloxy, and chlorine atoms are preferred.

In the group represented by the above formula (2), R ¹ is C 1-6, especially C 1-4 alkyl, such as methyl, ethyl, propyl, butyl, or phenyl, wherein Methyl is preferred.

a is 2 or 3, and in terms of reactivity and adhesion to the substrate, 3 is preferred.

As the silane having a hydrolyzable group at one terminal modified from the polymer containing a fluorooxyalkylene group, at least one selected from the compounds represented by the following general formulas (3) and (4) is Better.

[In the above formula (3), R ¹ , X, and a are as described above, and Rf is a divalent (poly)fluorine having 10 to 200 repeating units represented by -C _g F _2g O- (g is as described above) Extended alkyl group, A is a fluorine atom, a hydrogen atom, or a monovalent fluorine-containing group with a terminal -CF ₃ group, -CF ₂ H group or -CFH ₂ group, Q is a single bond, or may have an oxygen atom, nitrogen A substituted or unsubstituted C 2-12 valence organic group of atoms or silicon atoms, Z is a 2-8 valence organic siloxane residue which may have a silylalkyl structure or a silylphenyl structure, Or a divalent organosilicon alkylidene residue or organosilicon phenylene residue, e is 0 or 1, b is an integer from 1 to 7, α is 0 or 1, and c is an integer from 1 to 3, where, When e is 0, b is 1, α is 0, and c is 1, when e is 1, b is an integer from 1 to 7, α is 0 or 1, c is 1 when α is 0, and c is 1 when α is 1. Integer of 1~3, W is -C _j H _2j -R ⁵ _(3-c) Si- or -C _j H _2j -R ⁵ _(3-c) C-(wherein, j is an integer of 0~10 , C is as described above, R ⁵ is an alkyl group having 1 to 12 carbons, but W is -C _j H _2j -R ⁵ _(3-c) Si- and the end of Q or Z connected to W is a silicon atom, j is an integer from 1 to 10) (c+1) valence, f is an integer from 1 to 10]

[In the above formula (4), R ¹ , X, a, Rf, A, and Q are as described above, Q′ is a carbon atom, or a trivalent hydrocarbon group having 2 to 12 carbon atoms, and B is a hydrogen atom, and 1 to 4 carbon atoms. Alkyl group, hydroxyl group, or halogen atom, m is an integer from 1 to 10, k is 0 or 1, n is an integer from 1 to 3, wherein, when Q'is a carbon atom, k is 0, n is 2, m Is 1, when Q'is a trivalent hydrocarbon group, k is 0 or 1, n is 1, m is an integer from 2 to 10 when k is 0, n is an integer from 1 to 3 when k is 1, and m is 1 to 10 Integer, and when B is a hydrogen atom, m is an integer from 2 to 10, Y is phenylene, or (n+1)-valent R ⁸ _(3-n) Si or R ⁶ _(3-n) C [In the formula, n is as described above, R ⁸ is an alkyl group having 1 to 12 carbons, R ⁶ is an alkyl group having 1 to 12 carbons, a hydroxyl group or R ⁷ ₃ SiO- (wherein R ⁷ is independently hydrogen Atom, alkyl group having 1 to 12 carbons, aryl group having 6 to 12 carbons or alkoxy group having 1 to 12 carbons)], f'is an integer of 0 to 10].

In the above formulas (3) and (4), R ¹ , X, and a are as described in the above formula (2).

In the above formulas (3) and (4), Rf is a divalent (poly)fluorooxyalkylene group having 10 to 200 repeating units represented by -C _g F _2g O- (g is as described above) as Rf , With -(CF ₂ ) _d -(OCF ₂ ) _p (OCF ₂ CF ₂ ) _q (OCF ₂ CF ₂ CF ₂ ) _r (OCF ₂ CF ₂ CF ₂ CF ₂ ) _s (OCF(CF ₃ )CF ₂ ) _t -O-(CF ₂ ) _d -is preferred.

In the above formula, d is independently an integer of 0~5, preferably an integer of 0~2, and p, q, r, s, and t are independently an integer of 0~200, preferably: p is 5 Integer of ~100; q is an integer of 5-100; r is an integer of 0-100; s is an integer of 0-50; t is an integer of 0-100. p+q+r+s+t is an integer from 10 to 200, preferably an integer from 20 to 100. The units shown in parentheses can also be randomly bonded.

Examples of Rf include the following structures.

(In the formula, d'is the same as d above, p', q', r', s', t'are integers of 1 or more, and the upper limit is the same as the upper limit of p, q, r, s, t) .

In the above formulas (3) and (4), A is a fluorine atom, a hydrogen atom, or a monovalent fluorine-containing group whose terminal is a -CF ₃ group, -CF ₂ H group, or -CFH ₂ group.

As A, for example: -CF ₃

-CF ₂ CF ₃

-CF ₂ CF ₂ CF ₃

-CF ₂ H

-CH ₂ F.

In the above formulas (3) and (4), Q is a single bond, or a substituted or unsubstituted divalent organic group having 2 to 12 carbon atoms that may have an oxygen atom, a nitrogen atom, or a silicon atom. The divalent organic group becomes a linking group between Rf group and Z group, a linking group between Rf group and W group, a linking group between Rf group and -C _f H _2f -group, or a linking group between Rf group and Q'group .

Here, as the divalent organic group, for example, a diamine selected from the group consisting of an amide bond, an ether bond, an ester bond, a dimethylsilylene group, a diethylsilylene group, and a diphenylsilylene group can be included. Structure of one or more groups of groups represented by organic silyl groups and groups represented by -Si[OH][(CH ₂ ) _w Si(CH ₃ ) ₃ ]-(w is an integer of 2 to 4) Substituted or unsubstituted C 2-12 (preferably C 2-8) divalent hydrocarbon group.

Examples of the divalent hydrocarbon group include methylene, ethylidene, propylidene (trimethylene, methylethylidene), butylidene (tetramethylene, methylpropylidene), hexamethylene , Extend alkyl groups such as octamethylene, extend aryl groups such as phenyl. These may be a combination of two or more types, and may also be a combination of alkylene groups and aryl groups. Furthermore, some or all of the hydrogen atoms bonded to carbon atoms in these groups may be replaced by halogen atoms such as fluorine atoms.

As Q, a substituted or unsubstituted alkylene group having 2 to 4 carbon atoms or a phenylene group is preferred. More preferably, it has a diorganosilylene group selected from the group consisting of an amide bond, an ether bond, an ester bond, a dimethylsilylene group, and -Si[OH][(CH ₂ ) _w Si(CH ₃ ) ₃ ] -(w is an integer of 2 to 4) one or more structures of groups represented by groups, and having substituted or unsubstituted C 1-4 alkylene and/or phenylene Constructor.

Examples of such Q include the following.

(In the formula, u is an integer from 0 to 4, v is an integer from 0 to 4, w is an integer from 2 to 4, and Me is a methyl group).

In the above formula (3), Z is a 2- to 8-valent organosilicon residue or a divalent organosilicon residue or organosilicon that may have a silylalkyl structure or a silylphenyl structure Phenyl residues. As a 2-8 valence organosiloxane residue, it is preferable that it can have a silylalkyl structure or a silylphenyl structure having 2 to 13 silicon atoms (preferably 2 to 5 silicon atoms) Chain or cyclic organic polysiloxane residues. Here, the silylidene structure can be represented by Si-(CH ₂ ) _h -Si. In the above formula, h is preferably an integer of 2 to 6, more preferably an integer of 2 to 4.

Among the organic polysiloxane residues, the monovalent hydrocarbon group bonded to the silicon atom is preferably an alkyl group having 1 to 8 carbon atoms (particularly preferably 1 to 4 carbon atoms). Or phenyl. Examples of the alkyl group include methyl, ethyl, propyl, and butyl.

Examples of Z include the following.

(In the formula, h is an integer of 2 to 6, preferably an integer of 2 to 4, and Me is a methyl group).

In the above formula (3), e is 0 or 1, b is an integer from 1 to 7, α is 0 or 1, c is an integer from 1 to 3, where when e is 0, b is 1, α is 0, and c is 1. In addition, when e is 1, b is an integer of 1 to 7, α is 0 or 1, c is 1 when α is 0, and c is an integer of 1 to 3 when α is 1.

Moreover, f is an integer of 1-10, Preferably it is an integer of 2-6.

In the above formula (3), W is the (c+1) valence represented by -C _j H _2j -R ⁵ _(3-c) Si- or -C _j H _2j -R ⁵ _(3-c) C- In the foregoing formula, j is an integer of 0-10, preferably an integer of 2-6, c is as described above, and R ⁵ is an alkyl group having 1 to 12 carbon atoms, preferably an alkyl group having 1 to 6 carbon atoms. However, when W is -C _j H _2j -R ⁵ _(3-c) Si- and the end of Q or Z connected to W is a silicon atom, j is an integer of 1-10.

Here, examples of the alkyl group for R ⁵ include methyl, ethyl, propyl, butyl, pentyl, hexyl, and octyl groups, and methyl, ethyl, and propyl groups are preferred.

Examples of W include 2-4 valent groups shown below.

(In the formula, j is as described above, and Me is methyl).

As W, particularly preferred is a group represented by the following structure.

Examples of the compound represented by the above formula (3) include the following.

(In the formula, p1 and q1 are the numbers that satisfy p1/q1=0.9 and p1+q1≒45).

The compound represented by the above formula (3) is also preferably a compound shown below.

[Chem 23] HF ₂ C(OC ₂ F ₄ ) _q1 (OCF ₂ ) _p1 -OCF ₂ CH ₂ OC ₃ H ₆ Si(OCH ₃ ) ₃

(In the formula, p1 and q1 are the numbers that satisfy p1/q1=1.1 and p1+q1≒45).

[Chem 24] F ₃ C(OC ₂ F ₄ ) _q1 (OCF ₂ ) _p1 -OCF ₂ CH ₂ OC ₃ H ₆ Si(OCH ₃ ) ₃

(In the formula, p1 and q1 are the numbers that satisfy p1/q1=1.1 and p1+q1≒45).

(In the formula, p1 and q1 are the numbers that satisfy p1/q1=0.9 and p1+q1≒45).

(In the formula, p1 and q1 are the numbers that satisfy p1/q1=1.1 and p1+q1≒45).

In the above formula (4), Q'is a carbon atom or a trivalent hydrocarbon group having 2 to 12 carbon atoms. As the trivalent hydrocarbon group of Q', for example, it is bonded to methylene, ethylidene, propylidene (trimethylene, methylethylidene), butylidene (tetramethylene, methylpropylidene) ), a trivalent structure obtained by removing one hydrogen atom from a carbon atom of an alkylene group such as hexamethylene and octamethylene. Furthermore, it may have a structure in which a part or all of hydrogen atoms bonded to carbon atoms are replaced with halogen atoms such as fluorine atoms.

As Q', a carbon atom or a trivalent hydrocarbon group having 2 to 8 carbon atoms is particularly preferable, and a carbon atom or a group having the following structure is more preferable.

In the above formula (4), B is a hydrogen atom, an alkyl group such as a methyl group having 1 to 4 carbon atoms, an ethyl group, a propyl group, a butyl group, a hydroxyl group, or a halogen atom such as a chlorine atom, a bromine atom, or an iodine atom. B is preferably a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, and a hydroxyl group.

In the above formula (4), m is an integer from 1 to 10, k is 0 or 1, n is an integer from 1 to 3, preferably 2 or 3, wherein when Q′ is a carbon atom, k is 0 or n Is 2, and m is 1. When Q'is a trivalent hydrocarbon group, k is 0 or 1. At this time, when k is 0, n is 1, and m is an integer of 2-10, preferably m is an integer of 2-5, and particularly preferably m is 2. In addition, when k is 1, n is an integer of 1 to 3, and m is an integer of 1 to 10, preferably m is 1 to 5. Integer, especially m is 1 or 2.

Moreover, when B is a hydrogen atom, m is an integer of 2-10.

In the above formula (4), f'is an integer of 0-10, preferably an integer of 2-6.

In the above formula (4), Y is phenylene, or (n+1)-valent R ⁸ _(3-n) Si or R ⁶ _(3-n) C. In the above formula, n is as described above and R ⁸ is C 1-12 (preferably C 1-6) alkyl, R ⁶ is C 1-12 (preferably C 1-6) alkyl, hydroxyl, or R ⁷ ₃ SiO-, R ⁷ is independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms.

Here, examples of the alkyl group for R ⁶ and R ⁸ include methyl, ethyl, propyl, butyl, pentyl, hexyl, and octyl groups, preferably methyl, ethyl, and butyl.

In addition, as the alkyl group of R ⁷ , the same as the above R ⁶ and R ⁸ can be exemplified. As the aryl group, phenyl, tolyl, etc. can be exemplified. As the alkoxy group, methoxy, ethoxy can be exemplified. Group, propoxy, butoxy, etc. R ^{7 is} preferably methoxy or ethoxy.

Examples of (n+1)-valent R ⁸ _(3-n) Si or R ⁶ _(3-n) C include the following 2-4 valent groups.

(In the formula, Me is methyl).

In addition, when Y is R ⁸ _(3-n) Si-, Q′ is a trivalent hydrocarbon group having 2 to 12 carbon atoms, and a group represented by the following structure is particularly preferable.

Y is preferably a group represented by phenylene or the following structure.

(In the formula, Me is methyl).

Examples of the compound represented by the above formula (4) include the following.

(In the formula, p1 and q1 are the numbers that satisfy p1/q1=0.9 and p1+q1≒45).

(In the formula, p1 and q1 are the numbers that satisfy p1/q1=1.1 and p1+q1≒45).

(In the formula, p1 and q1 are the numbers that satisfy p1/q1=1.1 and p1+q1≒45).

(In the formula, p1 and q1 are the numbers that satisfy p1/q1=1.1 and p1+q1≒45).

(In the formula, p1 and q1 are the numbers that satisfy p1/q1=1.1 and p1+q1≒45).

(In the formula, p1 and q1 are the numbers that satisfy p1/q1=1.1 and p1+q1≒45).

As the compound represented by the above formula (4), it is more preferable that n is 2 or 3.

In the fluorine-containing coating agent of the present invention, as the component (A), a terminal hydrolyzable group of a silane having a hydrolyzable group at one terminal modified from the polymer containing a fluorooxyalkylene group may be contained The partially hydrolyzed condensate obtained by partial hydrolysis and condensation in advance by a conventional method.

Still, the weight average molecular weight of the component (A) is preferably 1,000 to 20,000, more preferably 2,000 to 10,000. If the weight average molecular weight is too small, the water and oil repellency and wear durability of the fluoropolyether group may not be exhibited. If the weight average molecular weight is too large, the adhesion to the substrate may be deteriorated. In the present invention, the weight average molecular weight can be measured as the standard polystyrene conversion value of gel permeation chromatography (GPC) using AK-225 (manufactured by Asahi Glass) as the developing solvent (the same applies hereinafter).

(B) Ingredients

The component (B) is a silane having a hydrolyzable group at both ends modified from a polymer containing a fluorooxyalkylene group and/or a partially hydrolyzed condensate thereof. As the silane, the following formula (1)-C _g F _2g O- (1) containing

(Where g is the same as above)

The repeating units represented by 10 to 200 fluorooxyalkylene groups have the following formula (2) described above at both ends

(In the formula, R ¹ , X, and a are the same as described above) The hydrolyzable group represented by is preferred.

As the silane having a hydrolyzable group at both ends modified by the polymer containing a fluorooxyalkylene group, at least one kind selected from the compounds represented by the following general formulas (5) and (6) is Better.

[In the above formula (5), R ¹ , X, a, Rf, Q, Z, e, b, α, c, W and f are as described above].

[In the above formula (6), R ¹ , X, a, Rf, Q, Q′, B, m, k, n, Y and f′ are as described above].

In the above formulas (5) and (6), R ¹ , X, a, Rf, Q, Z, e, b, α, c, W, f, Q′, B, m, k, n, Y and f 'Is as described in the above formulas (2) to (4), and the examples can be the same as those shown above, and can be the same as or different from the component (A), respectively.

Examples of the compound represented by the above formula (5) include the following.

所表示的基，p2、q2為滿足p2/q2=0.9、p2+q2≒45之數)。 (In the formula, Rf ² is the following formula

The basis represented, p2 and q2 are the numbers that satisfy p2/q2=0.9 and p2+q2≒45).

(In the formula, Rf ² is the same as described above, and p2 and q2 are numbers satisfying p2/q2=0.9 and p2+q2=23).

(In the formula, Rf ² is the same as described above, and p2 and q2 are numbers satisfying p2/q2=0.9 and p2+q2=45).

(In the formula, Rf ² is the same as described above, and p2 and q2 are numbers satisfying p2/q2=0.9 and p2+q2=60).

(In the formula, p2 and q2 are the numbers that satisfy p2/q2=1.1 and p2+q2≒23).

(In the formula, p2 and q2 are the numbers that satisfy p2/q2=1.1 and p2+q2≒45).

(In the formula, p2 and q2 are the numbers that satisfy p2/q2=1.1 and p2+q2≒60).

The compound represented by the above formula (5) is also preferably a compound shown below.

[Chem 49] (CH ₃ O) ₃ SiC ₃ H ₆ OCH ₂ -CF ₂ (OC ₂ F ₄ ) _q2 (OCF ₂ ) _p2 OCF ₂ -CH ₂ OC ₃ H ₆ Si(OCH ₃ ) ₃

(In the formula, p2 and q2 are the numbers that satisfy p2/q2=1.1 and p2+q2≒45).

【Chem 50】(CH ₃ O) ₃ SiC ₃ H ₆ OCH ₂ -CF ₂ (OC ₂ F ₄ ) _q2 (OCF ₂ ) _p2 OCF ₂ -CH ₂ OC ₃ H ₆ Si(OCH ₃ ) ₃

(In the formula, p2 and q2 are the numbers that satisfy p2/q2=1.1 and p2+q2≒23).

(In the formula, Rf ² is the same as described above, and p2 and q2 are numbers satisfying p2/q2=0.9 and p2+q2≒45).

Furthermore, the compounds represented by the above formula (6) include the following.

(In the formula, Rf ² is the same as described above, and p2 and q2 are numbers satisfying p2/q2=0.9 and p2+q2≒45).

(In the formula, Rf ² is the same as described above, and p2 and q2 are numbers satisfying p2/q2=1.1 and p2+q2≒45).

(In the formula, Rf ² is the same as described above, and p2 and q2 are numbers satisfying p2/q2=1.1 and p2+q2≒45).

(In the formula, Rf ² is the same as described above, and p2 and q2 are numbers satisfying p2/q2=1.1 and p2+q2≒45).

(In the formula, Rf ² is the same as described above, and p2 and q2 are numbers satisfying p2/q2=1.1 and p2+q2≒45).

(In the formula, Rf ² is the same as described above, and p2 and q2 are numbers satisfying p2/q2=1.1 and p2+q2≒45).

(In the formula, p2 and q2 are the numbers that satisfy p2/q2=1.1 and p2+q2≒45).

As the compound represented by the above formula (6), it is more preferable that n is 2 or 3.

In the fluorine-containing coating agent of the present invention, as the component (B), a terminal hydrolyzable group of a silane having hydrolyzable groups at both ends modified from the polymer containing a fluorooxyalkylene group may be contained The partially hydrolyzed condensate obtained by partial hydrolysis and condensation in advance by a conventional method.

Still, the weight average molecular weight of the component (B) is preferably 1,000 to 20,000, and more preferably 2,000 to 10,000. If the weight average molecular weight is too small, the water and oil repellency and wear durability of the fluoropolyether group may not be exhibited. If the weight average molecular weight is too large, the adhesion to the substrate may be deteriorated.

(Poly)fluorooxyalkylene-containing polymer

The fluorine-containing coating agent of the present invention may further contain the following general formula (7) A-Rf-A (7) as long as the characteristics of the present invention are not impaired

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

The represented (poly)fluorooxyalkylene group-containing polymer having no hydrolyzable group at any terminal (hereinafter referred to as "non-functional polymer").

In the above formula (7), Rf and A are as described above, and can be exemplified by the same as Rf and A shown in the above example, Rf can be the same or the same as Rf in the above components (A), (B) Differently, in addition, A may be the same as or different from A in the component (A).

Examples of the non-functional polymer represented by formula (7) include the following.

(In the formula, p3, q3, r3, t3 are based on the fluoropolyether group-containing polymer The weight-average molecular weight of the compound becomes a number between 1,000 and 50,000, and the units shown in parentheses can also be randomly bonded).

The weight average molecular weight of the non-functional polymer will vary depending on the length of the fluoropolyether chain and the combination with the non-fluorinated portion, but the weight average molecular weight of the functional polymer with the components (A) and (B) above 0.25~4 times is better. When the difference between the weight average molecular weight of the non-functional polymer and the weight average molecular weight of the components (A) and (B) is within the above range, the components (A) and (B) are easily compatible with each other, so Better.

The non-functional polymer may be a commercially available product. For example, FOMBLIN (manufactured by Solvay Solexis), DEMNUM (manufactured by Daikin Industries), and KRYTOX (manufactured by DuPont) are preferred because they are easy to obtain.

More detailed examples include the products shown below.

FOMBLIN Y (trade name manufactured by Solvay Solexis, compound represented by the following formula (8), FOMBLIN Y25 (weight average molecular weight: 3,200), FOMBLIN Y45 (weight average molecular weight: 4,100))

(In the formula, p3 and t3 are the numbers satisfying the above-mentioned weight average molecular weight, and the units shown in parentheses may also be randomly bonded).

FOMBLIN Z (Solvay Solexis trade name, compound represented by the following formula (9), FOMBLIN Z03 (weight average molecule Quantity: 4,000), FOMBLIN Z15 (weight average molecular weight: 8,000), FOMBLIN Z25 (weight average molecular weight: 9,500))

(In the formula, p3 and q3 are the numbers satisfying the above-mentioned weight average molecular weight, and each unit shown in parentheses may also be randomly bonded).

DEMNUM (trade name manufactured by Daikin Industries, Ltd., compound represented by the following formula (10), DEMNUM S20 (weight average molecular weight: 2,700), DEMNUM S65 (weight average molecular weight: 4,500), DEMNUM S100 (weight average molecular weight: 5,600))

(In the formula, r3 is a number satisfying the above-mentioned weight average molecular weight).

KRYTOX (trade name manufactured by DuPont, compound represented by the following formula (11), KRYTOX 143AB (weight average molecular weight: 3,500), KRYTOX 143AX (weight average molecular weight: 4,700), KRYTOX 143AC (weight average molecular weight: 5,500), KRYTOX 143AD (weight average molecular weight: 7,000))

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

The amount of the non-functional polymer is preferably 0.001 to 10 parts by mass, and more preferably 0.05 to 2 parts by mass with respect to the total of 100 parts by mass of the component (A) and the component (B).

In addition, the fluorine-containing coating agent can be blended with other additives according to the needs without impairing the scope of the present invention. Specifically, the hydrolytic condensation catalyst includes, for example, organic tin compounds (dibutyltin dimethoxide, dibutyltin dilaurate, etc.), organic titanium compounds (tetra-n-butyl titanate, etc.), and organic acids (fluorine Carboxylic acid, acetic acid, methanesulfonic acid, etc.), inorganic acids (hydrochloric acid, sulfuric acid, etc.), etc. Among these, fluorine-based carboxylic acid, acetic acid, tetra-n-butyl titanate, and dibutyltin dilaurate are preferred. Although the amount of addition is the amount of catalyst, it is usually 0.01 to 5 parts by mass, and particularly 0.1 to 1 part by mass relative to 100 parts by mass of the total of the components (A) and (B).

The fluorine-containing coating agent is preferably applied after being dissolved in an appropriate solvent. Examples of such solvents include fluorine-modified aliphatic hydrocarbon solvents (pentafluorobutane, decafluoropentane, perfluorohexane, perfluoroheptane, perfluorooctane, perfluorocyclohexane, and perfluorohexane). Fluorine-1,3-dimethylcyclohexane, etc.), fluorine-modified aromatic hydrocarbon solvents (m-xylene hexafluoride, trifluoromethylbenzene, 1,3-trifluoromethylbenzene, etc.), fluorine Modified ether solvents (methyl perfluoropropyl ether, methyl perfluorobutyl ether, ethyl perfluorobutyl ether, perfluoro (2-butyltetrahydrofuran), etc.), fluorine-modified alkylamine solvents (Perfluorotributylamine, perfluorotripentylamine, etc.), hydrocarbon solvents (petroleum benzene, mineral spirits, toluene, stubble, etc.), Ketone solvents (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.), ether solvents (tetrahydrofuran, diethyl ether, etc.), ester solvents (ethyl acetate, etc.), alcohol solvents (isopropyl) Base alcohol, etc.). Among these, from the viewpoint of solubility, wettability, etc., it is more preferably a fluorine-modified solvent, especially ethyl perfluorobutyl ether, or decafluoropentane, pentafluorobutane, perfluorohexyl Alkanes are better. The above-mentioned solvent system may be used alone or in combination of two or more.

The optimal concentration of the (A) and (B) components dissolved in the solvent will vary depending on the treatment method, but the content of the (A) and (B) components in the fluorine-containing coating agent becomes 0.01 to 50 mass %, particularly preferably an amount of 0.03 to 20% by mass.

The fluorine-containing coating agent of the present invention can be applied to the substrate by conventional methods such as wet coating method (brush coating, dipping, spraying, inkjet), and vapor deposition method, but the wet coating method is particularly used. The cloth method is more effective when coating.

In addition, the curing conditions of the fluorine-containing coating agent will vary depending on the coating method, but within the range of room temperature (20°C) to 200°C (especially 25°C to 150°C), 30 minutes to 24 Hours (especially 30 minutes to 1 hour) are ideal. As a curing humidity system, it is preferable to promote the reaction by proceeding under humidification.

Although the thickness of the cured film is appropriately selected according to the type of the substrate, it is usually 0.1 to 100 nm, especially 3 to 30 nm.

The substrate treated with the above-mentioned fluorine-containing coating agent is not particularly limited, and can be of various materials such as paper, cloth, metal and its oxide, glass, plastic, ceramic, quartz, sapphire, etc., which can impart such water and oil repellency , Chemical resistance, mold release, wear durability, antifouling. The surface of the substrate can be hard-coated or anti-reflective. When the adhesion is poor, it can also be provided as an undercoat layer by providing a SiO ₂ layer, or a silane coupling agent layer having a hydrolyzable group or a SiH group, or by vacuum plasma treatment, atmospheric pressure plasma treatment, alkali treatment Or acid treatment to improve adhesion.

Since the fluorine-containing coating agent of the present invention has a hydrolyzable group, it is preferable to provide an SiO ₂ layer on the substrate as an undercoat layer, and apply the fluorine-containing coating agent on the undercoat layer. In addition, when a hydrolyzable group such as a glass substrate can directly adhere to the base material, it is not necessary to provide an SiO ₂ layer. In this case, the coating method is preferably spray coating, inkjet coating, or Dip coating.

Examples of the articles treated with the fluorine-containing coating agent of the present invention include car navigation, car audio, tablet PCs, smartphones, wearable devices, mobile phones, digital cameras, digital video recorders, PDAs, portable audio and video Medical devices such as liquid crystal displays, organic EL displays, plasma displays, touch panel displays, or eyeglass lenses, camera lenses, lens filters, sunglasses, and gastroscopes used in players, game consoles, various operation panels, and electronic bulletins Use equipment, photocopiers, protective films, anti-reflection films and other optical items. The fluorine-containing coating agent of the present invention can prevent fingerprints and sebum from adhering to the aforementioned articles, and further impart scratch resistance, so it is particularly useful as a water and oil repellent layer for touch panel displays, anti-reflection treated articles, and strengthened glass .

The fluorine-containing coating agent of the present invention contains the above-mentioned components (A) and (B) in a specific ratio, and the fluorine-containing coating agent of the present invention is applied to a glass or a substrate treated with SiO ₂ (previously deposited or sputtered by SiO ₂ substrate) and other anti-fouling treatment substrates obtained by spray coating, inkjet coating, spin coating, dip coating, or vacuum evaporation coating, as compared to those obtained by coating only component (A) For anti-fouling articles, the increase in haze is small.

In the fluorine-containing coating agent of the present invention, when the thickness of the cured coating of the coating agent is 20 nm, the haze measured according to the method described in JIS K7136 is 0.5 or less, preferably 0.45 or less, and more preferably 0.4 or less. If the haze value exceeds 0.5, the appearance of white turbidity on the surface of the substrate will be confirmed.

Here, the cured film of the fluorine-containing coating agent can be obtained by, for example, the following method.

[Method of making hard coating]

(1). The components (A) and (B) are dissolved in ethyl perfluorobutyl ether [Novec 7200 (manufactured by 3M)] so as to become a solid content concentration of 20% by mass, and then further become a solid content concentration It is dissolved in 1,1,1,3,3-pentafluorobutane [Solkane 365mfc (manufactured by Solvay)] by 0.1 mass% to prepare a fluorine-containing coating agent.

(2). The fluorine-containing coating agent prepared in (1) above is used within 24 hours of preparation using a spray coating device ((Co., Ltd. T&K, NST-51), spray-coated on plasma-treated (Ar : 10cc, O _2: 100cc, output: 250W, time: 20 seconds) of the chemically strengthened glass (Corning Incorporated, GorillaII) on.

(3). A cured film was formed by curing at a temperature of 80° C. and a humidity of 80% RH for 1 hour to produce a test body.

The film thickness of the obtained cured film can be measured by the following method.

[Measurement method of film thickness of hardened coating]

Using the test body prepared as described above, the amount of fluorescent X-rays of fluorine atoms was quantified using a wavelength-dispersed small fluorescent X-ray analyzer (manufactured by Rigaku, ZSX-mini), and the coating was calculated using the detection line The thickness of the hardened coating on the glass plate.

The haze value of the resulting cured film having a thickness of 20 nm can be measured by the following method.

[Method of measuring haze value]

A haze meter (manufactured by Nippon Denshoku Industries Co., Ltd., NDH-5000) was used to obtain a haze value according to the measurement method described in JIS K7136:2000. It should be noted that the so-called haze value in the present invention is expressed by the total value of the glass substrate and the cured film.

In order to adjust the haze value to the above range, the fluorinated coating agent of the present invention contains (A) a silane having a hydrolyzable group at one terminal modified by a polymer containing a fluorooxyalkylene group And/or its partially hydrolyzed condensate, and (B) modified with a fluorooxyalkylene-containing polymer modified silanes having hydrolyzable groups at both ends and/or its partially hydrolyzed condensate, and (A ) Component and (B) component can be achieved by mixing 20:80~60:40.

In addition, the fluorine-containing coating agent of the present invention is one having abrasion durability, and the water contact angle of the cured film after 2,000 reciprocating abrasions is 100° or more, particularly 101° or more. If the above water contact angle is less than 100°, As the water repellency of the coating film is insufficient, it cannot be said that the film has excellent abrasion durability.

The so-called abrasion durability in the present invention means that the hardened film of the fluorine-containing coating agent is subjected to 2,000 reciprocal abrasion using a steel wool (No. #0000) by a friction measuring machine, and the water resistance before and after the abrasion is measured. The contact angle can be evaluated. A film having a small change in contact angle before and after abrasion and a high contact angle after abrasion (that is, a water contact angle of 100° or more) can be said to be a film having excellent abrasion durability.

Here, the cured film of the fluorine-containing coating agent can be produced by the same method as the above-mentioned cured film production method.

As a specific measurement method of the wear durability, the method shown below can be used.

[Measurement method of wear durability] ‧Measurement method of water contact angle

Using a contact angle meter (DropMaster manufactured by Kyowa Interface Science Co., Ltd.), the water contact angle of the hardened film was measured at 25° C. and a humidity of 50% RH. In the water contact angle system, 2 μl of droplets were attached to the surface of the sample, and the measurement was performed after 1 second.

‧Abrasion of hardened coating and measuring method

Using the above-mentioned hardened film with steel wool (BONSTAR business steel wool, No. #0000, manufactured by Japan Steel Wool Co., Ltd.), abrasion tester (TriboGear TYPE: 30S (manufactured by Shinto Science Co., Ltd.)) was used for 2,000 reciprocations Abrasion, the contact angle to water after abrasion was measured in the same manner as above.

Contact area: 10mm×10mm

Load: 1kg

In addition, in order to make the water contact angle of the above-mentioned cured film to the above-mentioned value, by modifying the polymer containing (A) with a fluorooxyalkylene group in the fluorine-containing coating agent of the present invention, it is Silanes having hydrolyzable groups at the ends and/or their partially hydrolyzed condensates, and (B) silanes having hydrolyzable groups at both ends modified from polymers containing fluorooxyalkylene groups and/or their partial hydrolysis The condensate can be achieved by mixing the (A) component and (B) component with a fluorine-containing coating agent in a ratio of 20:80 to 60:40.

[Example]

The following examples and comparative examples illustrate the present invention in more detail, but the present invention is not limited to the following examples. In this embodiment, the component (A) and the component (B) are mixed, but the component (A) may be synthesized in a state in which the component (B) is previously contained in the raw material used to synthesize the component (A).

[Example 1, Reference Examples 1, 2, Comparative Examples 1 to 6]

As the component (A), the fluorooxyalkylene group-containing polymer-modified silane, the following compounds 1, 3 are prepared; as the (B) component, the fluorooxyalkylene group-containing polymer-modified silane, the following compounds are prepared 2. 4.

(In the formula, p1 and q1 are p1/q1=0.9, p1+q1≒45, and the weight average molecular weight is 4,000).

(In the formula, p2 and q2 are p2/q2=0.9, p2+q2≒45, and the weight average molecular weight is 4,000).

(In the formula, p1 and q1 are p1/q1=0.9, p1+q1≒45, and the weight average molecular weight is 4,000).

(In the formula, p2 and q2 are p2/q2=0.9, p2+q2≒45, and the weight average molecular weight is 4,000).

Preparation of fluorine-containing coating agent and formation of cured coating

The above compounds 1 to 4 were dissolved in ethyl perfluorobutyl ether [Novec 7200 (manufactured by 3M)] at a mixing ratio as shown in Table 1 so as to become a solid concentration of 20% by mass, and then further became The fluorine-containing coating agent was prepared by dissolving in 1,1,1,3,3-pentafluorobutane [Solkane 365mfc (manufactured by Solvay)] at a solid concentration of 0.1% by mass. After the fluorine-containing coating agent is prepared, use a spray coating device (manufactured by T&K, NST-51) within 24 hours to spray-coat the fluorine-containing coating agent with plasma treatment (Ar: 10cc, O ₂ : 100cc, output: 250W, time: 20 seconds) on washed chemically strengthened glass (Gorilla II manufactured by Corning Incorporated). After that, a cured film was formed by curing at a temperature of 80° C. and a humidity of 80% RH for 1 hour to produce a test body.

The cured films obtained in Example 1, Reference Examples 1, 2 and Comparative Examples 1 to 6 were evaluated by the following methods. The tests were conducted at 25°C and 50% RH. The results of Example 1 and Reference Examples 1 and 2 are described in Tables 2 to 4, respectively, and the results of Comparative Examples 1 to 6 are described in Tables 5 to 10.

[Evaluation of film thickness]

The film thickness of the cured film produced above was measured using the following apparatus.

Device name: Wavelength dispersion compact fluorescent X-ray analyzer (ZSX-mini (manufactured by Rigaku))

[Evaluation of Haze]

The haze of the test body produced above is based on JIS K7136: In 2000, the following equipment was used for measurement.

Device name: Haze meter (NDH-5000 (made by Nippon Denshoku Industries Co., Ltd.))

[Evaluation of water and oil repellency]

Using the test body prepared as described above, the contact angle of the hardened film with respect to water (droplets: 2 μl) was measured using a contact angle meter DropMaster (manufactured by Kyowa Interface Science Co., Ltd.). In the water contact angle system, 2 μl of droplets were attached to the surface of the sample, and the measurement was performed after 1 second.

[Evaluation of wear resistance]

The wear resistance of the hardened film to steel wool (BONSTAR business steel wool, No. 0000, manufactured by Japan Steel Wool Corporation) was measured by TriboGear TYPE: 30S (manufactured by Shinto Science Corporation) after 2,000 reciprocating wears The contact angle with respect to water (droplet: 2 μl).

Contact area: 10mm×10mm

Load: 1kg

The relationship between the film thickness and the haze of the cured films of Example 1, Reference Example 1, and Comparative Examples 1, 2, 5, and 6 is shown in FIG. 1, and the films of the cured films of Reference Example 2 and Comparative Examples 3, 4 are shown. The relationship between thickness and haze is shown in Figure 2.

In addition, the relationship between the content of the (A) component in the cured films of Example 1, Reference Example 1 and Comparative Examples 1, 2, 5, and 6 and the haze at a film thickness of 20 nm is shown in FIG. 3, and the reference example The relationship between the content of the (A) component in the cured coatings of 2 and Comparative Examples 3 and 4 and the haze at a film thickness of 20 nm is shown in FIG. 4.

The results of Tables 2 to 10 and FIGS. 1 to 4 above are remarkable. Since Comparative Examples 1 and 3 do not contain the (B) component, it can be observed that the haze increases as the film thickness increases. In addition, since Comparative Examples 2 and 4 also do not contain the component (A), it can be observed that the haze increases as the film thickness increases, and the wear durability is also poor. In the mixing mass ratio of (A) component and (B) component of Comparative Example 5, the amount of (A) component is more than the range of the present invention, so it can be observed that the haze increases as the film thickness increases; In the mixing mass ratio of (A) component and (B) component in Example 6, the amount of (B) component is more than the range of the present invention, so it can be observed that the haze increases as the film thickness increases, in addition, The wear durability is the worst. On the other hand, the mixing mass ratio of the component (A) and the component (B) is the fluorine-containing coating agent contained in 20:80 to 60:40, and the test bodies of Examples 1 to 3 obtained by coating this may be The one that suppresses the increase in haze and wear durability is also excellent. Especially, even if the coating is thicker than the general film thickness (about 10 nm), the film thickness is 15 nm or more At that time, it was found that in the examples, the increase in haze was suppressed, and the wear durability was also excellent.

[Industry availability]

The present invention contains (A) a silane modified with a fluorooxyalkylene-containing polymer modified at a specific ratio and has a hydrolyzable group at one terminal and/or its partially hydrolyzed condensate, and (B) contains fluorine Fluorine-containing coating agent modified by oxyalkylene polymer modified silane with hydrolyzable groups at both ends and/or its partially hydrolyzed condensate without compromising the optical properties or texture of the substrate, and Shows wear durability and low haze value. The fluorine-containing coating agent of the present invention is very effective particularly in applications such as touch panel displays and anti-reflection films that assume adhesion of grease and visibility is important. Since the fluorine-containing coating agent of the present invention can suppress the increase in haze, there is no need for washing or wiping operations for reducing the haze after coating.

Claims (9)

A fluorine-containing coating agent comprising: (A) a silane having a hydrolyzable group at one terminal modified by a polymer containing a fluorooxyalkylene group represented by the following general formula (4) and/ Or a partially hydrolyzed condensate thereof; and (B) a silane having a hydrolyzable group at both ends modified from a polymer containing a fluorooxyalkylene group represented by the following general formula (6) and/or a portion Hydrolyzed condensate, the mixing mass ratio of (A) component with a weight average molecular weight of 1,000 to 20,000 and (B) component with a weight average molecular weight of 1,000 to 20,000 is 20:80 to 60:40, which is characterized by the hardening of the coating agent When the thickness of the coating is 20 nm, the haze measured according to the method described in JIS K7136 is 0.5 or less, and has a wear durability of 2,000 reciprocating abrasions with a water contact angle of 100° or more.

[In the above formulas (4) and (6), R ¹ is an alkyl group having 1 to 6 carbon atoms or a phenyl group, X is a hydrolyzable group, a is 2 or 3, and Rf has -C _g F _2g O-( In the formula, g is independently an integer of 1 to 6 per unit) a repeating unit of 10 to 200 divalent (poly)fluorooxyalkylene groups represented by A, a fluorine atom, a hydrogen atom, or a terminal of- Monovalent fluorine-containing group of CF ₃ group, -CF ₂ H group or -CFH ₂ group, Q is a single bond, or a substituted or unsubstituted carbon number of 2 to 12 which may have an oxygen atom, a nitrogen atom or a silicon atom A divalent organic group, Q'is a carbon atom, B is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a hydroxyl group, or a halogen atom, n is 2, m is 1, and f'is an integer of 0 to 10]. The fluorine-containing coating agent according to claim 1, wherein Rf is -(CF ₂ ) _d -(OCF ₂ ) _p (OCF ₂ CF ₂ ) _q (OCF ₂ CF ₂ CF ₂ ) _r (OCF ₂ CF ₂ CF ₂ CF ₂ ) _s (OCF(CF ₃ )CF ₂ ) _t -O-(CF ₂ ) _d -(d is an integer independently of 0~5, p, q, r, s and t are independently 0~ Integer of 200, and p+q+r+s+t is an integer of 10~200, the units shown in parentheses can also be randomly bonded). The fluorine-containing coating agent according to claim 2, which further contains a (poly)fluorooxyalkylene group-containing polymer represented by the following general formula (7), A-Rf-A (7) (where, Rf is a divalent (poly)fluorooxyalkylene group having 10 to 200 repeating units represented by -C _g F _2g O- (wherein g is independently an integer of 1 to 6 in each unit), A It is a fluorine atom, a hydrogen atom, or a monovalent fluorine-containing group whose terminal is -CF ₃ group, -CF ₂ H group, or -CFH ₂ group). The fluorine-containing coating agent according to claim 2 or 3, which further contains a solvent. A cured coating of a fluorine-containing coating agent according to any one of claims 1 to 4. An article treated with a fluorine-containing coating agent, which has the cured film of claim 5. A touch panel which is covered by the hardened film of claim 5 cover. An anti-reflection treated article covered with the hardened film of claim 5. A strengthened glass which is covered with the hardened film of claim 5.

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