KR102489200B1 - surface treatment agent - Google Patents

Abstract

An object of the present invention is to provide a surface treatment agent capable of quickly forming a cured film through a simple process and having excellent preservation properties. A compound and (B) a compound having a phosphonic acid ester group in the molecule, a surface treatment agent containing an amount of 0.001 to 15 parts by mass based on 100 parts by mass of the total of component (A) and component (B), and a cured product of the surface treatment agent It is to provide goods with

Description

surface treatment agent

The present invention relates to a surface treatment agent containing a fluorine-containing organosilicon compound. Specifically, it relates to a surface treatment agent capable of providing a coating having excellent storage stability and curing at a low temperature in a short time, and having excellent water and oil repellency and abrasion resistance, and an article treated with the surface treatment agent.

BACKGROUND OF THE INVENTION [0002] In recent years, touch panelization of screens, including displays of mobile phones, is accelerating. However, since touch panels often have exposed screens and there are many opportunities for direct contact with fingers, cheeks, etc., contamination with sebum or the like has become a problem. Therefore, in order to improve the appearance and visibility, the demand for a technology that makes it difficult to get fingerprints on the display surface or a technology that makes it easy to erase stains is increasing year by year.

In general, fluorooxyalkylene group-containing compounds are known to have water and oil repellency, chemical resistance, lubricity, releasability and antifouling properties because their surface free energy is very small. Due to its properties, it is widely used industrially as a water and oil repellent antifouling agent for paper and textiles, a lubricant for magnetic recording media, an oil repellent for precision equipment, a mold release agent, cosmetics, and protective films. However, since the fluorooxyalkylene group-containing compound has poor adhesiveness and adhesion to other substrates, it has been difficult to adhere a film formed of a cured product of a composition containing the compound to a substrate.

In addition, a silane coupling agent is known as an additive that bonds organic compounds to the surface of substrates such as glass or cloth, and is widely used as an additive included in coating agents for various substrate surfaces. A silane coupling agent is a compound which has an organic functional group and a reactive silyl group (usually an alkoxysilyl group) in one molecule. The alkoxysilyl group causes a self-condensation reaction with moisture in the air or the like. In the film formed by curing the coating agent, the alkoxysilyl group or the silanol group, which is a hydrolyzate thereof, is chemically and physically bonded to the surface of glass or metal to form a durable film.

Patent Document 1 (Japanese Unexamined Patent Publication No. 2003-238577) is a compound having a fluorooxyalkylene group and an alkoxysilyl group, and a perfluorooxyalkylene group-containing polymer having a linear perfluorooxyalkylene group represented by the following formula: Silanes are described. By treating the glass surface with the cured surface treatment agent containing the perfluorooxyalkylene group-containing polymer-modified silane, the glass surface can be provided with excellent slipperiness, releasability and wear resistance.

(Wherein, Rf is a divalent straight-chain perfluorooxyalkylene group, R is an alkyl group or phenyl group having 1 to 4 carbon atoms, X is a hydrolyzable group, n is 0 to 2, m is an integer of 1 to 5, and a is 2 or 3)

However, the surface treatment agent described in Patent Literature 1 requires a curing time of about 1 day at room temperature and about 1 hour when heated at 100°C, resulting in poor productivity. In this way, the conventional water/oil repellent treatment agent (surface treatment agent) can form a film having good water/oil repellency and soil repellency, but has poor curing properties. For this reason, development of a water and oil repellent treatment agent (surface treatment agent) that can be cured at a low temperature and in a short time has been demanded.

Catalysts that promote curing include organic titanate esters, organic titanium chelate compounds, organic aluminum compounds, organic zirconium compounds, organic tin compounds, metal salts of organic carboxylic acids, amine compounds and salts thereof, quaternary ammonium salts, alkali metal lower fats Acid salts, dialkylhydroxylamines, organosilicon compounds containing a guanidyl group, organic acids and inorganic acids, and the like are known. However, since these catalysts do not dissolve in fluorine-based solvents or dissolve only in very small amounts even when dissolved, their catalytic efficiency is poor. In addition, deterioration of the characteristics of the cured film may be caused by remaining metal powder.

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

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

The composition described in Patent Literature 2 cures in a short time to provide a cured film having excellent water repellency, oil repellency and antifouling properties, but storage is a problem.

Therefore, an object of the present invention is to provide a surface treatment agent capable of quickly forming a cured film through a simple process and having excellent storage properties.

As a result of intensive studies 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 organosilicon compound having a hydrolyzable group.

That is, the present invention

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

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

The surface treatment agent of the present invention rapidly cures on a substrate, firmly adheres to the substrate, and forms a film excellent in water and oil repellency, slipperiness and releasability.

Further, when the compound having a phosphonic acid ester group contained in the surface treatment agent of the present invention comes into contact with moisture in the air, the phosphonic acid ester group is rapidly hydrolyzed to form phosphonic acid. The phosphonic acid accelerates the hydrolysis of the fluorinated organosilicon compound having a hydrolysable group, so that the surface treatment agent is rapidly cured. The phosphonic acid ester may stably exist in a state not in contact with moisture. Therefore, a surface treatment agent excellent in storage stability can be provided.

[(A) Fluorinated Organosilicon Compound]

Component (A) is a fluorine-containing organosilicon compound having at least one hydrolysable group in one molecule. The said component should just be an organosilicon compound which has hydrolysable groups, such as a hydroxyl group, a C1-C12 alkoxy group, and an alkoxy alkoxy group, in 1 molecule, and also has a fluorine atom. The fluorine-containing organosilicon compound is preferably a compound having a fluorooxyalkylene group. A compound having a fluorooxyalkylene group is a compound having a (poly)fluorooxyalkylene structure in which a plurality of repeating units represented by -C _j F2 _j O- are 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 to have 10 to 500, preferably 15 to 200, more preferably 20 to 100, and still more preferably 25 to 80 repeating units.

The repeating unit -C _j F _2j O- may be either linear or branched. For example, the following units are mentioned, and two or more types of these repeating units may be bonded together.

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

In the above formula, d' is an integer of 0 to 5, p', q', r', s', t' are each independently an integer of 0 to 200, and p' + q' + r' + s' + t '= 10 to 200.

The fluorine-containing organosilicon compound of component (A) is more preferably a fluorine-containing organosilicon compound represented by any one of the following formulas (1) to (4). These may be used individually by 1 type, and may use 2 or more types together.

(A-Rf) _α -ZW _β (1)

Rf-(ZW _β ) ₂ (2)

A-Rf-Q-(Y) _γ B (3)

Rf-(Q-(Y) _γ B) ₂ (4)

In equations (1) and (2), 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 -, and p, q, r, s, and t are the same as above. Each unit shown in parentheses may be combined randomly. 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 -CH ₂ F group, and Z is a single bond, a carbon atom, a silicon atom, a nitrogen atom, or fluorine. It is a divalent to octavalent organic group which may be substituted by an atom, the valence of Z in formula (1) is (β + α), the valence of Z in formula (2) is (β + 1), and W has a hydrolysable group at the terminal. It is a monovalent organic group. α is an integer of 1 to 7, preferably an integer of 1 to 3. β is an integer of 1 to 7, preferably an integer of 1 to 3.

In formulas (3) and (4), Rf and A are the same as above, Q is a single bond or a divalent organic group, γ is independently an integer of 1 to 10, and 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 above 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 the terminal. Among them, -CF ₃ group, -CF ₂ CF ₃ group, and -CF ₂ CF ₂ CF ₃ group are preferable.

In the formulas (1) and (2), Z is a single bond, a carbon atom, a silicon atom, a nitrogen atom, or a di- to octavalent organic group which may be substituted with fluorine. The valence of Z in Formula (1) is (β + α), and the valence of Z in Formula (2) is (β + 1). The organic group can be represented by -Q-M-.

Q is a single bond or a divalent organic group, and is a linking group between the Rf group and the M group. Preferably, an amide bond, an ether bond, an ester bond, a vinyl bond or a diorganosilylene group such as a dimethylsilylene group may contain one or two or more unsubstituted or substituted carbon atoms of 2 to 100 12 is an organic group. More preferably, it is a divalent hydrocarbon group which may have the said bond.

Examples of the unsubstituted or substituted divalent hydrocarbon group having 2 to 12 carbon atoms represented by Q include a methylene group, an ethylene group, a propylene group (trimethylene group, methylethylene group), a butylene group (tetramethylene group, 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, etc.). In addition, a part or all of the hydrogen atoms bonded to the carbon atoms of these groups may be substituted with halogen atoms such as fluorine. Among them, an unsubstituted or substituted alkylene group or phenylene group having 2 to 4 carbon atoms is preferable.

As Q, group represented by the following structural formula is mentioned, for example.

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

M is independently of each other a single bond, a divalent group represented by -R ¹ ₂ C-, a divalent group represented by -R ³ ₂ Si-, a trivalent group represented by -R ¹ C =, and -R ³ Si = represented by It is a group selected from a trivalent group, a tetravalent group represented by -C≡, and a tetravalent group represented by -Si≡, or a 2 to 8 valent siloxane residue. In the above, R ¹ is independently of each other, preferably an alkyl group having 1 to 3 carbon atoms, a hydroxyl group or a silyl ether group represented by R ² ₃ SiO-, and R ² is independently of each other a hydrogen atom, preferably having 1 to 1 carbon atoms. An aryl group such as an alkyl group of 3 or 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 chlor group. When M is a siloxane residue, it preferably has a chain, branched or cyclic organopolysiloxane structure of 2 to 13 silicon atoms, preferably 2 to 5 silicon atoms. The organopolysiloxane preferably has an alkyl group having 1 to 8 carbon atoms, more preferably 1 to 4 carbon atoms, such as a methyl group, an ethyl group, a propyl group and a butyl group, or a phenyl group. It may also contain a silalkylene 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.

As such M, what is shown to the following structural formula is mentioned.

(In the formula, i is an integer from 1 to 20)

(In the formula, Me is a methyl group)

(In the formula, 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, preferably a group represented by the following formula.

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

X is a methoxy group, an ethoxy group, an alkoxy group having 1 to 10 carbon atoms such as a propoxy group and a butoxy group, an oxyalkoxy group having 2 to 10 carbon atoms such as a methoxymethoxy group and a methoxyethoxy group, an acetoxy group, etc. C1-C10 acyloxy group, C2-C10 alkenyloxy groups, such as an isopropenoxy group, halogen groups, such as a chlor group, a bromo group, and an iodine group, etc. are mentioned. Especially, 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 preferable from the viewpoint of reactivity and adhesion to the base material. 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.

Examples of structures represented by -ZW _β in formulas (1) and (2) include those represented by the following structural formula.

In formulas (7a) to (7e), Q, R, X, and a are the same as 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 is 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 above formulas (3) and (4), Q is a divalent organic group and is a linking group between the Rf group and the Y group. Details of the Q are as described above.

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

In the formula, R, X, a and m are as described above. p is an integer of 1 to 6, preferably an integer of 1 to 3, more preferably 1 or 2. M' is a trivalent to octavalent, preferably trivalent to pentavalent, more preferably trivalent or tetravalent, substituted or unsubstituted hydrocarbon group, in which some or all of the carbon atoms in the hydrocarbon group are substituted with silicon atoms, It may be present, and some or all of the hydrogen atoms bonded to the carbon atoms may be substituted with halogen atoms such as fluorine atoms. In addition, 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 organosilyl group, M ² is a trivalent hydrocarbon group or organosilyl group, and R is a monovalent hydrocarbon group having 1 to 6 carbon atoms)

As such Y, the group represented by the following structural formula is mentioned, for example.

(In the formula, X is the same as 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 above formulas (3) and (4), γ is an integer of 1 to 10, preferably an integer of 1 to 4. Further, B is each independently a hydrogen atom, an alkyl group such as a methyl group having 1 to 4 carbon atoms, an ethyl group, a propyl group, and a butyl group, 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 formulas (1) to (4) include compounds represented by the following structural formula.

(In the formula, Me is a methyl group, and each unit shown in parentheses may be randomly bonded)

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

[(B) component]

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

From the viewpoint of compatibility with the component (A) described above, the component (B) is preferably a compound containing a fluorine atom. Compounds having a fluorooxyalkylene group are particularly preferred. When component (B) is a compound having no fluorine atom, it is preferable that the surface treatment agent contains a mixture of a fluorine-based solvent and a non-fluorine-based solvent described later as a solvent. Thereby, the compatibility of (A) component and (B) component can be improved.

A fluorooxyalkylene group refers to a (poly)fluorooxyalkylene structure in which a plurality of repeating units represented by -C _j F _2j O- are bonded together as described above for the component (A). In detail, it is the same as the description of the fluorooxyalkylene group described about the said (A) component. However, the structure of the fluorooxyalkylene group which said (A) component and (B) component have is mutually independent. (B) The fluorooxyalkylene group in the component, 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' is a group represented by -O(CF ₂ ) _d' -. In the above, d' is an integer from 0 to 5, p', q', r', s' and t' are independently integers from 0 to 200, and p' + q' + r' + s' + t' = It is good that it is 10-200. In addition, each unit shown in parentheses may be combined randomly.

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

A'-Rf'-Z'W'_α' (5)

Rf'-(Z'W'_α')₂ (6)

In the formula, the Rf' group is the same as above, α' is an integer of 1 to 7, A' is a fluorine atom, a hydrogen atom, or a monovalent group having a terminal -CF ₃ group, -CF ₂ H group, or -CH ₂ F group. A fluorine-containing group, Z' is a single bond, a carbon atom, a silicon atom, a nitrogen atom, or a divalent to octavalent organic group which may be substituted with fluorine, and W' is a monovalent organic group having a phosphonic acid ester group at the terminal.

In the above formula (5), A' is a fluorine atom, a hydrogen atom, or a monovalent fluorine-containing group whose terminal is -CF ₃ group, -CF ₂ H group, or -CH ₂ F group, among which -CF ₃ group, -CF ₂ CF ₃ groups and -CF ₂ CF ₂ CF ₃ groups are preferred.

In the formulas (5) and (6), Z' is a single bond, a carbon atom, a silicon atom, a nitrogen atom, or a divalent to octavalent organic group which may be substituted with fluorine. In addition, the valence of Z' is α'+1. The details of Z' are the same as the description of the group represented by Z described in the component (A) above, and the organic group is a group represented by -Q-M- described above. The details are as described in the above (A) component. However, component (A) and component (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 by, for example, -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. Moreover, you may have a divalent organic group selected from the above-mentioned Q option.

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

In formula, X' is the same as the above, and l' is an integer of 0-20.

In the formula, X' is as described above, and l', m', and n' are each independently an integer of 1 to 20, preferably 2 or 3, respectively.

In addition, what is represented by the following formula may be sufficient as W'.

In the formula, X' and Q are as described above, and m' and n' are independently integers of 0 to 20, preferably 2 or 3, respectively.

As a compound represented by the said formula (5) or (6), the compound represented by the following formula is mentioned, for example.

In the surface treatment agent of the present invention, the blending amount of component (B) varies depending on the desired curing time and molecular weight, but the amount is preferably 0.001 to 15 parts by mass with respect to 100 parts by mass of the total of component (A) and component (B). It is an amount that is more preferably 0.05 to 10 parts by mass, more preferably 0.1 to 8 parts by mass, and particularly 0.5 to 5 parts by mass. (B) If the amount of the component is less than the lower limit, the effect of the catalyst is difficult to express. In addition, when the above upper limit is exceeded, there is a tendency to adversely affect the surface properties, such as lowering the water repellency of the cured film. Mixing of component (A) and component (B) may be performed by a known mixing means, and may be mixed after dissolving each in the following solvent.

[menstruum]

The coating agent composition of the present invention is preferably diluted in advance with a solvent, and such a solvent is not particularly limited as long as it uniformly dissolves the fluorine-containing modified silane (A) and the compound (B) having a phosphonic acid ester group. don't For example, fluorine-modified aliphatic hydrocarbon-based solvents (perfluoroheptane, perfluorooctane, etc.), fluorine-modified aromatic hydrocarbon-based solvents (1,3-trifluoromethylbenzene, etc.), fluorine-modified ether-based solvents (methyl purple Fluorobutyl ether, ethyl perfluorobutyl ether, perfluoro (2-butyltetrahydrofuran, etc.), fluorine-modified alkylamine solvents (perfluorotributylamine, perfluorotripentylamine, etc.), hydrocarbon solvents (petroleum benzene, toluene, xylene, etc.), and ketone solvents (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.). Among these, from the viewpoint of solubility and stability, fluorine-modified solvents are preferred, and fluorine-modified ether-based solvents and fluorine-modified aromatic hydrocarbon-based solvents are particularly preferred. The said solvent may be used individually by 1 type, and may mix and use 2 or more types. It is preferable to contain a solvent so that the total mass % of component (A) and component (B) in the composition may be 0.01 to 50%, preferably 0.03 to 25%.

The surface treatment agent of the present invention is cured by hydrolyzing the phosphonic acid ester group of component (B) to form phosphonic acid and accelerating the hydrolysis reaction of component (A). In general, phosphonic acid groups (-P(O)(OH) ₂ ) do not react with OH groups in the base material unless heated at 100 ° C. or higher for a long time, so heating at room temperature and low temperature for a short time can cause 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. For this reason, at room temperature or low temperature, the hydrolysis reaction of component (A) by the catalytic function of component (B) proceeds preferentially and rapidly. This makes it possible to provide a cured film with excellent adhesion to the substrate even when heated at a low temperature and for a short time.

[Coating method]

The surface treatment agent can be deposited on the substrate by a known method such as a wet coating method (brush application, dipping, spraying, inkjet) or a vapor deposition method. Coating conditions etc. may follow a conventionally well-known method. The surface treatment agent of the present invention cures quickly after application and can be cured at room temperature. Moreover, you may heat at 30-200 degreeC in order to harden in a short time. Since curing is carried out under humidification to enhance the catalytic action, it is preferable for accelerating hydrolysis. The curing time may be appropriately selected, but, for example, at 25°C, it can be cured from 40 minutes to 80 minutes, particularly about 60 minutes. Moreover, it can harden in about 30 minutes at 80 degreeC. The humidity may be appropriately adjusted, and a relative humidity of about 40 to 50% is preferable. In the case of wet coating, the influence of molecular weight is small, so the molecular weight is not limited. (B) The one where the component is larger is preferable.

Particularly preferably, it is good for component (B) to have a number average molecular weight of 0.5 to 5 times the number average molecular weight of component (A). If the number average molecular weight of component (B) is significantly smaller than the number average molecular weight of component (A), a large amount of component (B), which is difficult to react with the substrate at room temperature, is deposited at the initial stage of the vacuum deposition process. Then, the component (A) that reacts easily with the substrate is deposited at a later stage of the deposition process, and adhesion to the substrate may deteriorate. It is preferable to set the difference in number average molecular weight within the above range because the effects of the present invention can be exhibited without adverse effects.

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

The surface treatment agent of the present invention imparts water and oil repellency to the surface of the substrate. The compound having the phosphonic acid ester can improve the preservation of the surface treatment agent while having a curing accelerating effect equivalent to that of conventional curing accelerators, particularly acid catalysts. In general, an acid catalyst exhibits a curing accelerating effect immediately after mixing with the main agent, but since the curing reaction proceeds during storage, the life of the treatment liquid is often a problem. On the other hand, since the phosphonic acid ester group reacts with moisture to become a phosphonic acid group and exhibits a curing catalyst effect, the effect on the life 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 made of various materials such as paper, cloth, metal and its oxide, glass, plastic, ceramic, and quartz. The surface treatment agent of the present invention can impart water and oil repellency to the substrate. In particular, it can be preferably used as a surface treatment agent for SiO ₂ -treated glass, film, and sapphire substrates.

Articles treated with the surface treatment agent of the present invention include car navigation devices, tablet PCs, smart phones, mobile phones, digital cameras, digital video cameras, PDAs, portable audio players, car audio players, game devices, spectacle lenses, camera lenses, and lens filters. , sunglasses, medical devices such as gastroscopic cameras, photocopiers, PCs, liquid crystal displays, organic EL displays, plasma displays, touch panel displays, protective films, and optical articles such as antireflection films. The fluorine-based surface treatment agent for vapor deposition of the present invention prevents fingerprints and sebum from adhering to the article and can additionally impart damage prevention properties, so it is particularly useful as a water- and oil-repellent layer for touch panel displays and anti-reflection films. .

Example

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

Hereinafter, each component used in Examples and Comparative Examples is as follows. In addition, the number average molecular weight in the following is a value calculated by ¹ H-NMR.

(A) a fluorinated organosilicon compound:

(A-1)

(B) Compound containing a phosphonic acid ester group:

(B-1)

(B-2)

(B-3)

Comparative Curing Catalysts:

(C-1)

(C-2)

(C-3) trifluoroacetic acid

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

Manufacture of surface treatment agent

In Examples 1 to 5, the above-described component (A-1) and any of the components (B-1) to (B-3) were mixed in the composition shown in Table 1 below (mixtures 1 to 5), and the mixtures A surface treatment agent was prepared by dissolving 400 parts by mass of Novec 7200 (manufactured by 3M) so that the concentration of (100 parts by mass in total) was 20% by mass. In Comparative Examples 1 to 4, the above-described component (A-1) and any of the curing catalysts (C-1) to (C-3) for comparative examples were mixed in the composition shown in Table 2 below (Mixtures 6 to 9) , 400 parts by mass of Novec 7200 (manufactured by 3M) was dissolved so that the concentration of the mixture (100 parts by mass in total) was 20% by mass, and a surface treatment agent was prepared.

Formation of cured film by vacuum deposition

5 μl of each surface treatment agent prepared above was vacuum-deposited on glass (Gorilla3 manufactured by Corning Co., Ltd.) treated with 15 nm of SiO ₂ on the outermost surface under the following conditions, and cured for 1 hour at 25 ° C. in an atmosphere of 50% humidity to form a film ( Film thickness: about 10 nm) was used as a test body in the following evaluation.

[Coating conditions and apparatus by vacuum deposition]

・Measuring Device: Small Vacuum Evaporator VPC-250F

· Pressure: 2.0×10 ^-3 Pa∼3.0×10 ^-2 Pa

Deposition temperature (attainment temperature of the boat): 500°C

Deposition distance: 20 mm

· Injection amount of treatment agent: 5 mg

Deposition amount: 5 mg

The cured coating on the test body was evaluated by the following method.

[Water repellency]

The contact angle of the cured film to water was measured using a contact angle meter DropMaster (manufactured by Kyowa Interface Science Co., Ltd.). Results are shown in Table 3 below.

[wear resistance]

Abrasion resistance against steel wool (#0000):

Tribo Gear TYPE: 30S (manufactured by Shinto Scientific Co., Ltd.) was used to abrade the hardened film 10,000 times under the following conditions, and then the contact angle of the hardened film to water was measured using a contact angle meter DropMaster (manufactured by Kyowa Interface Science Co., Ltd.). Results are shown in Table 3 below.

Contact area: 1 cm2

Load: 1kg

[Storability evaluation]

The test body was stored at 50°C in an airtight container for one month. About the test body after preservation, the contact angle of the hardened film with respect to water was measured using the contact angle meter DropMaster (made by Kyowa Interface Science Co., Ltd.). In addition, the contact angle with respect to water of the cured film after carrying out the abrasion resistance test was measured. Results are shown in Table 3 below.

As shown in Table 3, since the surface treatment agent of Comparative Example 1 does not contain a catalyst, curing is slow and does not sufficiently cure under low-temperature and short-time curing conditions, so the resulting cured coating has poor wear resistance. The surface treatment agents of Comparative Examples 2 and 3 contain a fluorine-containing compound having phosphonic acid as a curing catalyst. The surface treatment agent was cured at a low temperature in a short time to provide a cured coating having wear resistance, but the coating obtained by curing after storage at 50° C. for one month had poor water repellency and poor wear resistance. Since this surface treatment agent contains phosphonic acid, it is estimated that (A) component condensed with each other during storage. Comparative Example 4 is a surface treatment agent containing a conventional curing catalyst. The obtained cured film had poor water repellency and also poor abrasion resistance. Since trifluoroacetic acid has a low boiling point, it is presumed that during vacuum deposition, the surface treatment agent is absorbed by the pump before adhering to the substrate, so that the effect as a catalyst is not sufficiently obtained. In addition, the storage stability of the surface treatment agent of Comparative Example 4 is poor. It is considered that component (A) was condensed under the influence of trifluoroacetic acid during storage of the surface treatment agent.

In contrast, as shown in Examples 1 to 5 in Table 3, the surface treatment agent of the present invention can provide a cured film having excellent wear resistance even under low-temperature and short-time curing conditions such as room temperature (25° C., 50% humidity) curing for 1 hour. can In addition, even after storing the cured film at 50°C for one month, the excellent abrasion resistance does not decrease and the storage stability is also excellent.

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

Formation of cured film by spray coating

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)] to a solid content concentration of 0.1% by mass. ] to prepare a surface treatment agent.

Spray coating device (manufactured by T&K Co., Ltd., NST- 51) was used for spray coating. After that, it was cured at 80°C and 40% RH for 30 minutes to form a cured film, and a test body was obtained.

[Plasma treatment conditions]

Device: Plasma dry cleaning device PDC210

Gas: O ₂ gas 80cc, Ar gas 10cc

·Output: 250W

· Time: 30 seconds

The resulting cured coating was evaluated for water repellency, abrasion resistance and storage properties by the following methods. Results are shown in Table 4.

Evaluation method of water repellency: Evaluation was conducted by the same method as the above-described water repellency test.

Evaluation of abrasion resistance: Evaluation was performed by the same method as in the abrasion resistance test described above except that the number of reciprocating abrasion was set to 3,000.

Evaluation of preservability: After each test piece was stored at 50°C in an airtight container for 1 week, the above 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 not possible to provide a film having sufficient abrasion resistance under the low-temperature and short-time curing conditions of 80°C and 30 minutes. The surface treatment agents of Comparative Examples 2 to 4 are inferior in storage stability. This is considered that (A) components condensed with each other during storage as mentioned above.

On the other hand, as shown in Examples 6 to 10 in Table 4, the surface treatment agent of the present invention can provide a cured coating having excellent wear resistance even under a low-temperature and short-time curing condition of 80°C for 30 minutes. In addition, even after storing the cured film at 50°C for one month, the excellent abrasion resistance does not decrease and the storage stability is also excellent.

The surface treatment agent of the present invention can provide a cured film having excellent water and oil repellency and excellent adhesion to a substrate by curing at a low temperature and in a short time, and also has excellent storage properties. 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 and oil repellent film in applications where adhesion of fats and oils is assumed and visibility is important, such as touch panel displays and antireflection films, and it can be expected to contribute to improving productivity of these products.

Claims (12)

As component (A), which is a fluorinated organosilicon compound having at least one hydrolyzable group in one molecule,
Component (A) is at least one selected from fluorine-containing organosilicon compounds represented by the following general formula (1), (2), (3) or (4);
(A-Rf) _α -ZW _β (1)
Rf-(ZW _β ) ₂ (2)
A-Rf-Q-(Y) _γ B (3)
Rf-(Q-(Y) _γ B) ₂ (4)
[In each of the above formulas, the Rf groups are independently of 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 -, d is a number from 0 to 5, p, q, r, s, and t are each independently an integer from 0 to 200, and p + q + r + s + t = 10 to 200, each unit shown in parentheses may be randomly bonded, and A is independently a fluorine atom, a hydrogen atom, or a terminal -CF ₃ group, -CF ₂ H group or -CH ₂ F group A monovalent fluorine-containing group, Z is a single bond or a divalent to octavalent organic group which may be substituted with a carbon atom, a silicon atom, a nitrogen atom or a fluorine atom independently of each other, and W is independently of each other a hydrolyzable group at the terminal. is a monovalent organic group having, α is an integer of 1 to 7, β is an integer of 1 to 7 independently of each other, and when Z is the organic group, the valence of Z in formula (1) is (β + α) , The valence of Z in formula (2) is (β + 1), Q is a single bond or a divalent organic group independently of each other, γ is an integer from 1 to 10 independently of each other, and Y is a hydrolyzable group independently of each other. is a divalent organic group having, and B is independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a halogen atom], and
Including component (B), which is a compound having a phosphonic acid ester group in the molecule,
A surface treatment agent having an amount of 0.001 to 15 parts by mass of the component (B) with respect to 100 parts by mass in total of the component (A) and the component (B). According to claim 1,
(B) The surface treatment agent whose component is a compound which has a fluorine atom. According to claim 2,
(B) The surface treatment agent whose component is a compound which has a fluorooxyalkylene group. delete delete According to claim 1,
(B) The surface treatment agent whose component is a compound represented by the following general formula (5) or (6).
A'-Rf'-Z'W'_α' (5)
Rf'-(Z'W'_α' ) ₂ (6)
[In the formula, Rf' groups are independently of 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' -, d' is an integer from 0 to 5, p', q', r', s', t' is an integer of 0 to 200, and p' + q' + r' + s' + t' = 10 to 200, and each unit shown in parentheses may be randomly combined, and α' is an integer of 1 to 7 independently of each other And, 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 -CH ₂ F group independently of each other, and Z' are independently of each other, a single bond, Alternatively, it is a divalent to octavalent organic group which may be substituted with a carbon atom, a silicon atom, a nitrogen atom, or a fluorine atom, and W' is a monovalent organic group having a phosphonic acid ester group at the terminal independently of each other.] According to any one of claims 1 to 3,
The phosphonic acid ester group in the component (B) is represented by -P(O)(OX') ₂ , and X' is an unsubstituted or substituted alkyl group or aryl group having 1 to 5 carbon atoms or a group represented by -SiR ₃ . (The R is independently of each other an alkyl group or an aryl group having 1 to 5 carbon atoms), a surface treatment agent. According to claim 7,
A surface treatment agent in which X' is a phenyl group or a group represented by -Si(CH ₃ ) ₃ . According to any one of claims 1 to 3,
The surface treatment agent in which the said (B) component has a number average molecular weight 0.5 to 5 times with respect to the number average molecular weight of (A) component. An article comprising a cured product of the surface treatment agent according to any one of claims 1 to 3. According to claim 10,
wherein the article is selected from optical articles, touch panels, anti-reflection films, SiO ₂ treated glass and pottery. A method in which the surface treatment agent according to any one of claims 1 to 3 is deposited on the surface of an article by vapor deposition and cured to form a cured film on the surface of the article.