KR20190060768A - Surface treatment agent - Google Patents

Abstract

An object of the present invention is to provide a surface treatment agent capable of rapidly forming a cured film by a simple process and having excellent storage stability. The present invention provides a surface treatment agent comprising (A) a fluorinated organosilicon compound having at least one hydrolyzable group And (B) a compound having an amount of 0.001 to 15 parts by mass per 100 parts by mass of the total of the component (A) and the component (B) having a phosphonic acid ester group in the molecule, and a cured product of the surface treatment agent And to provide an article having the same.

Description

Surface treatment agent

The present invention relates to a surface treatment agent containing a fluorinated organosilicon compound. More particularly, the present invention relates to a surface treatment agent which is excellent in storage stability and can be cured at a low temperature in a short time to provide a film excellent in water and oil repellency and abrasion resistance and an article treated with the surface treatment agent.

Recently, a touch panel of a screen has been accelerated including a display of a cellular phone. However, since many touch panels are exposed to the screen, there are many opportunities for the finger or cheek to come into direct contact with the touch panel, so that contamination of sebum or the like is liable to occur. Therefore, a technique for making fingerprints hard to get on the display surface and a technique for making it easier to remove the fouling are getting higher every year in order to improve appearance and visibility.

Generally, fluorooxyalkylene group-containing compounds are known to have water- and oil-repellency, chemical resistance, lubricity, releasability and antifouling property because their surface free energy is very small. Industrially, it is industrially widely used as a water-repellent oil-repellent antifouling agent for paper and fiber, a lubricant for magnetic recording medium, an oil repellent for precision instruments, a release agent, a cosmetic, a protective film and the like. However, since the fluoroxyalkylene group-containing compound has poor adhesiveness and adhesiveness to other substrates, it is difficult to adhere the coating comprising the cured product of the composition containing the compound to the substrate.

The silane coupling agent is known as an additive for bonding an organic compound to the surface of a base material such as glass or cloth, and is widely used as an additive contained in coating materials on various substrate surfaces. The silane coupling agent is a compound having an organic functional group and a reactive silyl group (generally an alkoxysilyl group) in one molecule. The alkoxysilyl group causes self-condensation reaction by moisture in air or the like. In the film formed by curing the coating agent, the alkoxysilyl group or the silanol group as the hydrolyzate thereof is chemically and physically bonded to the surface of glass, metal, or the like to provide a durable film having durability.

Patent Document 1 (Japanese Unexamined Patent Publication (Kokai) No. 2003-238577) discloses a compound having a fluoroxyalkylene group and an alkoxysilyl group and a perfluorooxyalkylene group-containing polymer having a straight chain perfluorooxyalkylene group represented by the following formula Silane. By treating the glass surface with the cured product of the surface treatment agent containing the perfluorooxyalkylene group-containing polymer modified silane, it is possible to provide excellent sliding property, releasability and abrasion resistance on the glass surface.

(Wherein R is a divalent straight-chain perfluorooxyalkylene group, R is an alkyl group having 1 to 4 carbon atoms or a phenyl group, 2 or 3)

However, the surface treatment agent described in Patent Document 1 requires a curing time of about one day at room temperature and about one hour at about 100 占 폚 of heating, resulting in a problem of low productivity. As described above, the conventional water- and oil-repellent agent (surface-treating agent) can form a film having good water- and oil-repellency and decontamination properties, but has poor curability. For this reason, development of a water-repellent oil repellent agent (surface treatment agent) that can be cured at a low temperature and in a short time is required.

Catalysts for promoting curing include organic titanic acid esters, organic titanium chelate compounds, organoaluminum compounds, organic zirconium compounds, organic tin compounds, metal salts of organic carboxylic acids, amine compounds and salts thereof, quaternary ammonium salts, Acid salts, dialkylhydroxylamines, guanidyl group-containing organic silicon compounds, organic acids and inorganic acids. However, these catalysts do not dissolve in the fluorine-based solvent or dissolve only in a very small amount even if they are dissolved, resulting in poor catalyst efficiency. Further, the metal powder may remain, resulting in deterioration of the properties of the cured coating.

In order to solve the above problem, Patent Document 2 (Japanese Patent Laid-Open Publication No. 2008-144144) discloses a coating composition comprising a perfluoropolyether carboxylic acid as a curing catalyst soluble in a fluorine-based solvent.

Japanese Patent Application Laid-Open No. 2003-238577 Japanese Patent Application Laid-Open No. 2008-144144

The composition disclosed in Patent Document 2 is cured in a short time to provide a cured coating excellent in water repellency, oil repellency and anti-contamination property, but has a problem of preservability.

It is therefore an object of the present invention to provide a surface treatment agent capable of forming a cured film quickly with a simple process and having excellent storage stability.

As a result of intensive investigations to solve the above problems, the present inventors have found that the above problems can be solved by using a compound having a phosphonic acid ester group as a curing catalyst for a fluorinated organic silicon compound having a hydrolysable group.

That is,

(A) a fluorinated organosilicon compound having at least one hydrolyzable group in one molecule, and

(B) a compound having a phosphonic acid ester group in a molecule and having an amount of 0.001 to 15 parts by mass per 100 parts by mass of the total of the component (A) and the component (B), and an article having a cured product of the surface- to provide.

The surface treatment agent of the present invention is rapidly cured on the base material, firmly adhered to the base material, and forms a film excellent in water and oil repellency, slipperiness and releasability.

Further, the compound having a phosphonic acid ester group contained in the surface treatment agent of the present invention is brought into contact with moisture in the air, whereby the phosphonic acid ester group is hydrolyzed quickly to be a phosphonic acid. The phosphonic acid accelerates the hydrolysis of the fluorinated organosilicon compound having a hydrolyzable group to rapidly cure the surface treatment agent. The phosphonic acid ester can stably exist in a state where it is not in contact with water. Therefore, a surface treatment agent having excellent storage stability can be provided.

[(A) Fluorine Organosilicon Compound]

(A) is a fluorinated organosilicon compound having at least one hydrolyzable group in one molecule. The above component may be any organic silicon compound having a hydrolyzable group such as a hydroxyl group, an alkoxy group having 1 to 12 carbon atoms and an alkoxy alkoxy group in one molecule and having a fluorine atom. The fluorinated organic silicon compound is preferably a compound having a fluorooxyalkylene group. The compound having a fluoroxyalkylene group is a compound having a (poly) fluorooxyalkylene structure in which a plurality of repeating units represented by -C _j F2 _j O- is bonded (in the above structure, j is 1 or more, preferably 1 to 6, more preferably an integer of 1 to 4). In particular, it is preferable that the repeating unit has 10 to 500, preferably 15 to 200, more preferably 20 to 100, and more preferably 25 to 80 repeating units.

The repeating unit -C _j F _2j O- may be either straight chain or branched. For example, the following units may be mentioned, and two or more of these repeating units may be 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-

-C (CF _{3) 2} O-

The fluoroxyalkylene structure is particularly preferably selected from - (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 - represented by. P, q, r, s, and t are each independently an integer of 0 to 200, and p + q + r + s + t = 10 to 200. In the above formula, d is an integer of 0 to 5; In addition, each unit shown in parentheses may be combined at random. In particular, it can be represented by the following structural formula.

P ', q', r ', s' and t' are each independently an integer of 0 to 200, and p '+ q' + r '+ s' + t '= 10-200.

The fluorinated organic silicon compound of component (A) is more preferably a fluorinated organic silicon compound represented by any of the following formulas (1) to (4). These may be used singly or in combination of two or more.

(A-Rf) _? -ZW _? (1)

Rf- (ZW _? ) ₂ (2)

A-Rf-Q- (Y) _? B (3)

Rf- (Q- (Y) _? B) ₂ (4)

Rf group in the formula (1) and _{(2) - (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 - a, p, q, r, s , t are as above. The units indicated in parentheses may be combined at random. 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 -CH ₂ F group, and Z is a single bond, a carbon atom, a silicon atom, a nitrogen atom, Wherein the atomic valence of Z in the formula (1) is (? +?), The valence of Z in the formula (2) is (? + 1) and the valence of W in the formula Monovalent organic group. ? is an integer of 1 to 7, preferably an integer of 1 to 3. beta is an integer of 1 to 7, preferably an integer of 1 to 3.

In the formulas (3) and (4), Rf and A are as defined above, Q is a single bond or a divalent organic group, y is independently an integer of 1 to 10, Y is a divalent organic group having a hydrolysable group And B is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a halogen atom.

In the formulas (1) and (3), A is a fluorine atom, a hydrogen atom, or a monovalent fluorine-containing group having a -CF ₃ group, -CF ₂ H group or -CH ₂ F group at a terminal. Among them, -CF ₃ group, -CF ₂ CF ₃ group and -CF ₂ CF ₂ CF ₃ group are preferable.

In the above formulas (1) and (2), Z represents a single bond, a carbon atom, a silicon atom, a nitrogen atom or a fluorine-substituted 2- to 8-membered organic group. The valence of Z in (1) is (β + α), and the valence of Z in (2) is (β + 1). The organic group may be represented by -Q-M-.

Q is a single bond or a divalent organic group and is a linking group of Rf group and M group. Preferably an unsubstituted or substituted alkylene group having 2 to 20 carbon atoms, which may contain one or more kinds selected from the group consisting of amide bond, ether bond, ester bond, vinyl bond, and diorganosilylene group such as dimethylsilylene group, 12 < / RTI > More preferably a divalent hydrocarbon group which may have the above bond.

Examples of the unsubstituted or substituted divalent hydrocarbon group having 2 to 12 carbon atoms represented by Q include methylene, ethylene, propylene (trimethylene, methylethylene), butylene (tetramethylene, methyl Propylene group), an alkylene group such as a hexamethylene group and an octamethylene group, an arylene group such as a phenylene group, or a combination of two or more of these groups (alkylene, arylene group and the like). Further, a part of or all of the hydrogen atoms bonded to the carbon atoms of these groups may be substituted with a halogen atom such as fluorine. Among them, an unsubstituted or substituted alkylene group having 2 to 4 carbon atoms or a phenylene group is preferable.

Examples of Q include groups represented by the following structural formulas.

(Wherein f is an integer of 2 to 4, a, b and g are integers of 1 to 4, h is an integer of 1 to 50, and Me is a methyl group)

M is independently a single bond, a bivalent group represented by -R ¹ ₂ C-, a bivalent group represented by -R ³ ₂ Si-, a trivalent group represented by -R ¹ C═, or -R ³ Si═ A trivalent group, a tetravalent group represented by -C≡, and a tetravalent group represented by -Si≡, or a siloxane residue having 2 to 8 carbon atoms. R ¹ is independently an alkyl group having 1 to 3 carbon atoms, a hydroxyl group or a silyl ether group represented by R ² ₃ SiO-, R ² is independently a hydrogen atom, An aryl group such as a phenyl group, or an alkoxy group having 1 to 3 carbon atoms. R ³ is independently of each other preferably an alkyl group having 1 to 3 carbon atoms, an alkenyl group having 2 or 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, or a chlorine group. When M is a siloxane residue, it is preferable that it has a chain-like, branched or cyclic organopolysiloxane structure having 2 to 13 silicon atoms, preferably 2 to 5 silicon atoms. The organopolysiloxane preferably has an alkyl group of 1 to 8 carbon atoms, more preferably 1 to 4, such as a methyl group, an ethyl group, a propyl group and a butyl group, or a phenyl group. Further, it may contain a silylene structure or a silphenylene structure in which two silicon atoms are bonded to an alkylene group or a phenylene group, that is, Si- (CH ₂ ) _n -Si or Si- (C ₆ H ₄ ) -Si . In the above formula, n is an integer of 2 to 6, preferably an integer of 2 to 4.

Examples of such M include those shown in the following structural formulas.

(Wherein i is an integer of 1 to 20)

(Wherein Me is a methyl group)

(Wherein f is an integer of 2 to 4, h is an integer of 1 to 50, and Me is a methyl group)

In the above formulas (1) and (2), W is a monovalent organic group having a hydrolyzable group at the terminal, and is preferably a group represented by the following formula.

(Wherein R is an alkyl group having 1 to 4 carbon atoms or a phenyl group, X is a hydrolyzable group, a is 2 or 3, and m is 0 or an integer of 1 to 10)

Examples of X include alkoxy groups of 1 to 10 carbon atoms such as methoxy, ethoxy, propoxy and butoxy, oxyalkoxy groups of 2 to 10 carbon atoms such as methoxymethoxy and methoxyethoxy, An alkenyloxy group having 2 to 10 carbon atoms such as an isopropenoyl group, an acyloxy group having 1 to 10 carbon atoms, and a halogen group such as a chlorine group, a bromo group and an iodine group. Among them, a methoxy group and an ethoxy group are preferable. In the above formula, R is an alkyl group having 1 to 4 carbon atoms or a phenyl group, and among these, a methyl group is preferable. a is 2 or 3, and 3 is preferred from the viewpoints of reactivity and adhesion to a substrate. b is an integer of 1 to 7, preferably 1 to 3, and c is an integer of 1 to 5, preferably 1 to 3.

Structures represented by -ZW _{? In the} formulas (1) and (2) include those represented by the following structural formulas.

In the formulas (7a) to (7e), Q, R, X and a are as defined above, m ¹ is an integer of 0 to 10, preferably an integer of 2 to 8, and m ² is an integer of 1 to 10 And preferably an integer of 2 to 8. b is an integer of 2 to 6, preferably an integer of 2 to 4, c is an integer of 1 to 50, preferably an integer of 1 to 10, and Me is a methyl group.

In the formulas (3) and (4), Q is a divalent organic group and is a linking group of Rf group and Y group. The details of Q are as described above.

In the formulas (3) and (4), Y is a divalent organic group having a hydrolyzable group independently of each other. Preferably a group represented by the following formula.

Wherein R, X, a and m are as defined above. p is an integer of 1 to 6, preferably an integer of 1 to 3, more preferably 1 or 2. M 'is a hydrocarbon group of 3 to 8 carbon atoms, preferably 3 to 5 carbon atoms, more preferably a trivalent or tetravalent hydrocarbon group, and a part or all of carbon atoms in the hydrocarbon group is substituted with a silicon atom And some or all of the hydrogen atoms bonded to the carbon atoms may be substituted with a halogen atom such as a fluorine atom. Also, the valence of M 'is p + 2. M 'is preferably a group represented by the following structural formula.

(Wherein M ¹ is a divalent hydrocarbon group or an organosilyl group, M ² is a trivalent hydrocarbon group or an organosilyl group, and R is a monovalent hydrocarbon group having 1 to 6 carbon atoms)

Examples of such Y include a group represented by the following structural formula.

(Wherein X is as defined above, j is an integer of 0 to 10, preferably an integer of 1 to 8, k is an integer of 2 to 10, preferably an integer of 3 to 8. Me is a methyl group )

In the formulas (3) and (4),? Is an integer of 1 to 10, preferably an integer of 1 to 4. B is independently a hydrogen atom, an alkyl group such as a methyl group, an ethyl group, a propyl group or a butyl group having 1 to 4 carbon atoms, or a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

Examples of the fluorine-containing organosilicon compound represented by the above formulas (1) to (4) include compounds represented by the following structural formulas.

(Wherein Me is a methyl group, and each unit in parentheses may be bonded at random)

The surface treatment agent of the present invention may contain a compound in which part or all of the hydrolyzable group (X) in the component (A) is hydrolyzed (X is an OH group), and some or all of these OH groups Or a condensed compound.

[Component (B)] [

(B) is a compound having a phosphonic acid ester group in its molecule. The phosphonic acid ester group in the present invention is a group represented by -P (O) (OX ') ₂ . X 'may be a group having a general phosphonic acid ester represented by -P (O) (OX') ₂ . Preferably an unsubstituted or substituted alkyl group or aryl group having 1 to 5 carbon atoms, or a group represented by -SiR ₃ . R is independently an alkyl group having 1 to 5 carbon atoms or an aryl group. More preferably, X 'is a phenyl group or a trimethylsilyl group.

From the viewpoint of compatibility with the component (A), the component (B) is preferably a compound having a fluorine atom. Particularly preferred are compounds having a fluorooxyalkylene group. When the component (B) is a compound having no fluorine atom, it is preferable that the surface treating agent includes a mixture of a fluorine-containing solvent and a non-fluorine-containing solvent, which will be described later, as a solvent. This makes it possible to improve the compatibility of the components (A) and (B).

The fluorooxyalkylene group refers to a (poly) fluorooxyalkylene structure having a plurality of repeating units represented by -C _j F _2j O- bonded thereto, as described in the component (A). Specifically, it is the same as the description of the fluoroxyalkylene group described for the component (A). However, the structures of the fluoroxyalkylene groups of the components (A) and (B) are independent of each other. Fluoro in the component (B), the oxyalkylene group, Rf 'is preferably _{- (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' -. P ', q', r ', s' and t 'are independently an integer of 0 to 200, and p' + q '+ r' + s '+ t' Preferably from 10 to 200. In addition, each unit shown in parentheses may be combined at random.

(B) is preferably a compound represented by the following formula (5) or (6).

A'-Rf'-Z'W '_{α '} (5)

Rf '- (Z'W'_{α '})₂ (6)

Wherein A 'represents a fluorine atom, a hydrogen atom, or a monovalent group represented by a -CF ₃ group, a -CF ₂ H group or a -CH ₂ F group, wherein Rf' is as defined above, α 'is an integer of 1 to 7, And Z 'is a monovalent organic group having a phosphonic acid ester group at the terminal thereof, and Z' is an organic group having a single bond, a carbon atom, a silicon atom, a nitrogen atom or a fluorine-

The formula (5) A 'is a fluorine atom, a hydrogen atom, or a terminal -CF ₃ group, -CF ₂ H group or a fluorine-containing monovalent -CH ₂ F group, particularly groups -CF _3, -CF ₂ CF ₃ group, and -CF ₂ CF ₂ CF ₃ group are preferable.

In the formulas (5) and (6), Z 'represents an organic group having a single bond, a carbon atom, a silicon atom, a nitrogen atom or a fluorine- Also, the valence of Z 'is?' + 1. The details of Z 'are the same as those of the group represented by Z described in the above component (A), and the organic group is a group represented by -QM-. The details are as described in the component (A) above. However, the components (A) and (B) have independent structures.

In the formulas (5) and (6), W 'is a monovalent organic group having a phosphonic acid ester group at the terminal, and can be represented, for example, as -Q'-P (O) (OX') ₂ . Q 'is a single bond or a divalent organic group. The divalent organic group is preferably a hydrocarbon group having 1 to 20 carbon atoms, more preferably 2 to 10 carbon atoms, which may contain a diorganosilylene group. Further, it may have a divalent organic group selected from the above-mentioned Q.

W 'is preferably a group represented by the following formula.

Wherein X 'is as defined above, and l' is an integer of 0 to 20.

In the formulas, X 'is as defined above, and l', m 'and n' are independently integers of 1 to 20, preferably 2 or 3, respectively.

Further, W 'may be represented by the following formula.

In the formulas, X 'and Q are as defined above, and m' and n 'are independently an integer of 0 to 20, preferably 2 or 3, respectively.

Examples of the compound represented by the formula (5) or (6) include compounds represented by the following formulas.

The blending amount of the component (B) in the surface treatment agent of the present invention varies depending on the desired curing time and the molecular weight, but is preferably 0.001 to 15 parts by mass per 100 parts by mass of the total of the components (A) and (B) More preferably 0.05 to 10 parts by mass, more preferably 0.1 to 8 parts by mass, particularly preferably 0.5 to 5 parts by mass. When the amount of the component (B) is less than the above lower limit value, the effect of the catalyst is difficult to manifest. On the other hand, if the upper limit is exceeded, the water repellency of the cured coating tends to deteriorate, which tends to adversely affect the surface characteristics. The component (A) and the component (B) may be mixed by a known mixing means, and they may be mixed after they are dissolved in the following solvents.

[menstruum]

The coating composition of the present invention is preferably diluted beforehand with a solvent. Such a solvent is not particularly limited as long as it uniformly dissolves the fluorine group-containing modified silane (A) and the phosphonic acid ester group-containing compound (B) Do not. Examples of the solvent include fluorine-modified aliphatic hydrocarbon solvents such as perfluoroheptane and perfluorooctane, fluorine-modified aromatic hydrocarbon solvents such as 1,3-trifluoromethylbenzene, fluorine-modified ether solvents such as methylpurple Fluorine-modified alkylamine-based solvents (perfluorotributylamine, perfluorotripentylamine, etc.), hydrocarbon-based solvents (such as perfluorohexylamine, perfluorohexylamine, (Petroleum benzene, toluene, xylene and the like) and ketone solvents (acetone, methyl ethyl ketone, methyl isobutyl ketone and the like). Of these, fluorine-modified solvents are preferable from the viewpoints of solubility and stability, and fluorine-modified ether solvents and fluorine-modified aromatic hydrocarbon solvents are particularly preferable. These solvents may be used singly or in combination of two or more kinds. The solvent is preferably contained so that the total mass% of the components (A) and (B) in the composition is 0.01 to 50%, preferably 0.03 to 25%.

In the surface treatment agent of the present invention, the phosphonic acid ester group of the component (B) is hydrolyzed to be a phosphonic acid, which is cured by accelerating the hydrolysis reaction of the component (A). In general, since the reaction with the OH group in the substrate does not proceed unless the phosphonic acid group (-P (O) (OH) ₂ ) is heated for a long time at 100 ° C or higher, The reaction of the components does not proceed. On the other hand, the component (A) is hydrolyzed even at room temperature and gradually bonds with the -OH group of the substrate. Therefore, at room temperature or at low temperature, the hydrolysis reaction of the component (A) by the catalytic function of the component (B) proceeds preferentially and rapidly. As a result, it is possible to provide a cured coating excellent in adhesion to a substrate even in a short-time heating at a low temperature.

[Coating method]

The surface treatment agent can be deposited on a substrate by a known method such as a wet coating method (brush coating, dipping, spraying, ink jet), or vapor deposition. The coating conditions and the like can be obtained by conventionally known methods. The surface treatment agent of the present invention can be cured at room temperature because of its rapid curing after application. Further, it may be heated at 30 to 200 DEG C for curing in a short time. The curing is preferably carried out under humidification in order to accelerate the hydrolysis because it enhances the catalytic action. The curing time may be appropriately selected, but can be set at, for example, 25 占 폚 for 40 minutes to 80 minutes, particularly about 60 minutes. Further, it can be cured at 80 DEG C for about 30 minutes. The humidity should be appropriately adjusted, and the relative humidity is preferably about 40 to 50%. When the wet coating method is used, the molecular weight is not limited because the effect of the molecular weight is small. However, when the surface treatment agent of the present invention is coated by the vapor deposition method, the number average molecular weight of the component (A) And the component (B) is preferably larger.

Particularly preferably, the component (B) has a number average molecular weight of 0.5 to 5 times the number average molecular weight of the component (A). When the number average molecular weight of the component (B) is significantly smaller than the number average molecular weight of the component (A), the component (B), which is difficult to react with the substrate at room temperature, is much deposited in the initial stage of the vacuum deposition process. Then, the component (A), which is liable to react with the substrate, is deposited at the latter stage of the vapor deposition process, resulting in poor adhesion to the substrate. By setting the difference in the number average molecular weight within the above-mentioned range, the effect of the present invention can be exerted without any adverse effect.

The surface treatment agent of the present invention is deposited on a substrate and then cured to form a film. The film thickness of the cured coating (fluorine layer) is preferably 50 nm or less, more preferably 0.5 to 20 nm, further preferably 2 to 15 nm.

The surface treatment agent of the present invention imparts water and oil repellency to the substrate surface. The compound having a phosphonic acid ester can increase the preservability of a surface treatment agent while having a curing accelerating effect equivalent to that of a conventional curing accelerator, particularly an acid catalyst. Generally, the acid catalyst exerts hardening accelerating effect immediately after mixing with the subject, but since the hardening reaction proceeds during storage, the lifetime of the treatment liquid often becomes a problem. On the other hand, since the phosphonate group reacts with moisture to become a phosphonic acid group and exerts a curing catalyst effect, the effect on the lifetime of the surface treatment agent is small.

The substrate treated with the surface treatment agent of the present invention is not particularly limited and may be of various materials such as paper, cloth, metal and its oxide, glass, plastic, ceramic, quartz and the like. The surface treatment agent of the present invention may impart water and / or oil repellency to the substrate. In particular, it can be suitably used as a surface treatment agent for SiO ₂ -treated glass, film or sapphire substrate.

The article to be treated with the surface treatment agent of the present invention includes at least one member selected from the group consisting of a car navigation system, a tablet PC, a smart phone, a mobile phone, a digital camera, a digital video camera, a PDA, a portable audio player, , A medical device such as a sunglass and an endoscope camera, a copying machine, a PC, a liquid crystal display, an organic EL display, a plasma display, a touch panel display, a protective film, and an antireflection film. The fluorine-containing surface treatment agent of the present invention is useful as a water-repellent and oil-repellent layer of a touch panel display, an antireflection film, and the like, because it can prevent the fingerprint and sebum from adhering to the article and further provide damage prevention property .

Example

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples.

Hereinafter, the respective components used in Examples and Comparative Examples are as follows. The number average molecular weight in the following is a value calculated by ¹ H-NMR.

(A) Fluorine organosilicon compound:

(A-1)

(B) a phosphonic acid ester group-containing compound:

(B-1)

(B-2)

(B-3)

Comparative curing catalyst:

(C-1)

(C-2)

(C-3) Trifluoroacetic acid

[Examples 1 to 5 and Comparative Examples 1 to 4]

Preparation of surface treatment agent

In Examples 1 to 5, the above-mentioned components (A-1) and (B-1) to (B-3) were mixed in the compositions shown in Table 1 below (Mixtures 1 to 5) (100 parts by mass in total) was dissolved in 400 parts by mass of Novec 7200 (manufactured by 3M Company) so as to have a concentration of 20% by mass. In Comparative Examples 1 to 4, the above-mentioned component (A-1) and the curing catalysts (C-1) to (C-3) for Comparative Examples were mixed in the compositions shown in Table 2 below (Mixtures 6 to 9) , And 400 parts by mass of Novec 7200 (manufactured by 3M Co.) so that the concentration of the mixture (100 parts by mass in total) was 20% by mass.

Formation of Cured Coating by Vacuum Deposition

By curing each of the surface treatment agent for a 5㎕ 15㎚ handle SiO ₂ on the outermost surface of glass 1 hour under an atmosphere of 25 ℃, humidity of 50% evaporation, and vacuum by means of the following conditions (manufactured by Corning Gorilla3) prepared in coating ( Film thickness: about 10 nm) was formed as a specimen in the evaluation described below.

[Coating conditions and apparatus by vacuum deposition]

· Measuring device: Small vacuum deposition device VPC-250F

Pressure: 2.0 x 10 ^-3 Pa to 3.0 x 10 ^-2 Pa

· Deposition temperature (arrival temperature of boat): 500 ℃

· Deposition distance: 20 mm

· Amount of treatment agent injected: 5 mg

Deposition amount: 5 mg

The cured coatings on the test specimens were evaluated by the following methods.

[Water repellency]

Using a contact angle meter DropMaster (manufactured by Kyoei Interface Science Co., Ltd.), the contact angle of the cured coating to water was measured. The results are shown in Table 3 below.

[Abrasion resistance]

Wear resistance for steel wool (# 0000):

The contact angle of the cured coating to water was measured using a contact angle meter DropMaster (manufactured by Kyowa Interface Science Co., Ltd.) after the cured coating was subjected to reciprocating wear 10,000 times under the following conditions using a Tribo Gear TYPE: 30S (manufactured by Shinto Scientific Co., Ltd.). The results are shown in Table 3 below.

Contact area: 1 cm 2

Load: 1 kg

[Evaluation of preservability]

The test piece was stored at 50 DEG C in a sealed container for one month. The contact angle of the cured coating to water was measured using a DropMaster (manufactured by Kyowa Interface Science Co., Ltd.) with respect to the test sample after storage. Further, the contact angle of the cured coating film against water after the above abrasion resistance test was measured. The results are shown in Table 3 below.

As shown in Table 3, the surface treatment agent of Comparative Example 1 does not contain a catalyst and is therefore hard to cure under a curing condition of a low temperature for a short time because of a slow curing, so that the cured coating obtained is poor in abrasion resistance. The surface treating agents of Comparative Examples 2 and 3 contain a fluorine compound having a phosphonic acid as a curing catalyst. The surface treatment agent cured in a short time at a low temperature to provide a cured coating having abrasion resistance. However, the coating obtained by curing after storage at 50 캜 for one month has poor water repellency and abrasion resistance. It is presumed that the components (A) are condensed during storage because the surface treatment agent contains phosphonic acid. Comparative Example 4 is a surface treatment agent containing a conventional curing catalyst. The resulting cured coating was poor in water repellency and also in abrasion resistance. Since trifluoroacetic acid has a low boiling point, it is presumed that the effect of the catalyst as a catalyst is not obtained when the surface treatment agent is absorbed in the pump before the surface treatment agent is attached to the substrate during vacuum deposition. In addition, the storage stability of the surface treatment system of Comparative Example 4 is poor. It is considered that the component (A) is condensed due to the influence of trifluoroacetic acid during the preservation of the surface treatment system.

On the other hand, as shown in Examples 1 to 5 of Table 3, the surface treatment agent of the present invention provides a cured coating having excellent abrasion resistance even at a low temperature short time curing condition of 1 hour of curing at room temperature (25 DEG C, 50% . In addition, excellent abrasion resistance is not lowered even after the cured coating is stored at 50 캜 for one month, and storage stability is also excellent.

[Examples 6 to 10 and Comparative Examples 5 to 8]

Formation of cured coating by spray coating

The mixtures 1 to 9 prepared in Examples 1 to 5 and Comparative Examples 1 to 4 were mixed with 1,1,1,3,3-pentafluorobutane (Solkane 365mfc, manufactured by Solvay Co., Ltd.) so as to have a solid content concentration of 0.1% ] To prepare a surface treating agent.

(Surface of Gorilla II manufactured by Corning Incorporated, Corning Inc.) subjected to a plasma treatment under the following conditions were each coated with a spray coating device (NST- 51) was used for spray coating. Thereafter, the resultant was cured at 80 DEG C and 40% RH for 30 minutes to form a cured film, thereby obtaining a specimen.

[Plasma treatment conditions]

· Apparatus: Plasma dry cleaning device PDC210

Gas: O ₂ gas 80 cc, Ar gas 10 cc

· Output: 250W

· Time: 30 seconds

Water repellency, abrasion resistance and storage stability of the obtained cured film were evaluated by the following methods. The results are shown in Table 4.

Evaluation method of water repellency: Evaluated by the same method as the above water repellency test.

Evaluation of abrasion resistance: The abrasion resistance test was carried out in the same manner as in the abrasion resistance test except that the number of times of reciprocating abrasion was changed to 3,000.

Evaluation of preservability: Each of the test specimens was stored at 50 캜 in a hermetically sealed container for 1 week, and then the water repellency and abrasion resistance were evaluated.

As shown in Table 4, since the surface treatment agent of Comparative Example 1 did not contain a curing catalyst, it was impossible to provide a coating having sufficient abrasion resistance at a low temperature short time curing condition of 80 占 폚 for 30 minutes. The surface treatment agents of Comparative Examples 2 to 4 are inferior in storage stability. This is presumably because the components (A) are condensed during storage as described above.

On the other hand, as shown in Examples 6 to 10 of Table 4, the surface treatment agent of the present invention can provide a cured coating having excellent abrasion resistance even at a low temperature short time curing condition of 80 占 폚 for 30 minutes. In addition, excellent abrasion resistance is not lowered even after the cured coating is stored at 50 캜 for one month, and storage stability is also excellent.

The surface treatment agent of the present invention is excellent in water-repellent and oil-repellency due to low-temperature short-time curing, can provide a cured film having excellent adhesion with a substrate, and is also excellent in preservability. Therefore, the surface treatment agent of the present invention can be expected to be widely used industrially. In particular, it is useful as a surface treatment agent for forming a water-repellent and oil-repellent film in applications where adhesion of the oil is anticipated, such as a touch panel display and an antireflection film, and in which visibility becomes important, and it is expected that this product contributes to improvement of productivity.

Claims (12)

(A) which is a fluorinated organosilicon compound having at least one hydrolyzable group in one molecule and
(B) which is a compound having a phosphonic acid ester group in its molecule,
Wherein the blending amount of the component (B) is 0.001 to 15 parts by mass per 100 parts by mass of the total of the component (A) and the component (B). The method according to claim 1,
(B) is a compound having a fluorine atom. 3. The method of claim 2,
(B) is a compound having a fluoroxyalkylene group. 4. The method according to any one of claims 1 to 3,
Wherein the component (A) is a fluorinated organosilicon compound having a fluoroxyalkylene group. 5. The method of claim 4,
Wherein the component (A) is at least one selected from the group consisting of fluorinated organic silicon compounds represented by the following general formula (1), (2), (3) or (4)
(A-Rf)_alpha-ZW_beta  (One)
Rf- (ZW_beta)₂  (2)
A-Rf-Q- (Y)_gammaB  (3)
Rf- (Q- (Y)_gammaB)₂ (4)
[In the above formulas, the Rf groups independently of one another are - (CF₂)_d- (OCF₂)_p(OCF₂CF₂)_q(OCF₂CF₂CF₂)_r(OCF₂CF₂CF₂CF₂)_s(OCF (CF₃) CF₂)_t-O (CF₂)_dP + q + r + s + t = 10 to 200, wherein each unit represented by parentheses is a random combination of And A is independently a fluorine atom, a hydrogen atom, or a -CF₃Group, -CF₂H group or -CH₂And Z is independently a monovalent bond, a carbon atom, a silicon atom, a nitrogen atom, or a fluorine-substituted 2- to 8-membered organic group, and W is independently an alkylene group having 1 to 1 (1) wherein the valence of Z in the formula (1) is (? +?) And the valence of Z in the formula (2) is an integer of 1 to 7; and? Is an integer of 1 to 7;? Is independently an integer of 1 to 7; Is a bivalent organic group having a hydrolyzable group independently of each other, and B is a divalent organic group having a hydrolyzable group independently of each other, and Q is a single bond or a divalent organic group independently of each other, y is independently an integer of 1 to 10, Independently of each other, a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a halogen atom] 5. The method of claim 4,
(B) is a compound represented by the following general formula (5) or (6).
A'-Rf'-Z'W 'a _' (5)
Rf ' - (Z'W ' a _' ) ₂ (6)
[Wherein, Rf 'groups are independently from each other _{- (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' - and, d 'is an integer of 0~5, p', q ', r', s', t ' Is an integer of 0 to 200 and p '+ q' + r '+ s' + t' = 10 to 200, each unit represented by parentheses may be bonded at random, A 'is independently a fluorine atom, a hydrogen atom, or a monovalent fluorine-containing group whose terminal is -CF ₃ group, -CF ₂ H group or -CH ₂ F group, and Z' is independently a single bond, a carbon And W 'each independently represent a monovalent organic group having a phosphonic acid ester group at the end thereof, and R < 2 > 4. The method according to any one of claims 1 to 3,
Wherein the phosphonic acid ester group in the component (B) is represented by -P (O) (OX ') ₂ , X' is an unsubstituted or substituted alkyl group or aryl group having 1 to 5 carbon atoms, or -SiR ₃ (Wherein R is independently an alkyl group having 1 to 5 carbon atoms or an aryl group). 8. The method of claim 7,
Wherein X 'is a group represented by a phenyl group or a -Si (CH _{3) 3,} a surface treatment agent. 4. The method according to any one of claims 1 to 3,
Wherein the component (B) has a number average molecular weight of 0.5 to 5 times the number average molecular weight of the component (A). An article having a cured product of the surface treatment agent according to any one of claims 1 to 3. 11. The method of claim 10,
Wherein the article is selected from an optical article, a touch panel, an antireflection film, a SiO ₂ treated glass and a ceramic article. A surface treatment agent according to any one of claims 1 to 3, which is deposited on the surface of an article by vapor deposition and cured to form a cured coating on the surface of the article.