TW201816009A - Composition - Google Patents

Abstract

The object of the present invention is to provide a coating composition having good abrasion resistance. The composition of the present invention contains: a compound (A) in which (a1) a monovalent group having a perfluoropolyether structure and (a2) at least one of a hydrolyzable group and a hydroxy group are bonded to a silicon atom, and a compound (B) having a hydroxy group and an oxyalkylene unit, at least a part of hydrogen atoms of the oxyalkylene unit being substituted with fluorine atoms, the compound (B) having a number average molecular weight of less than 10,000.

Description

 Composition  

The present invention is related to compositions.

Since the film formed of the composition containing a fluorooxyalkylene group compound has a very small surface free energy, it has water repellency, chemical resistance, release property and the like. According to this property, Patent Document 1 discloses that (A) a hydrolyzable group-containing decane and/or a partially hydrolyzed condensate thereof modified with a fluorooxyalkylene group-containing polymer, and having the (A) (B) A fluorine-containing coating agent containing a polymer of a fluorooxyalkylene group having an average molecular weight of less than or equal to the average molecular weight of the component. (B) A polymer containing a fluorooxyalkylene group in Patent Document 1 mainly describes a non-functional fluorooxyalkylene group.

Further, Patent Document 2 discloses that a hydrolyzable group-containing decane and/or a partially hydrolyzed condensate thereof containing (A) a polymer containing a fluorooxyalkylene group is modified, and the component (A) is more The (B) fluorooxyalkylene group-containing polymer having a large weight average molecular weight and a fluorine-based surface treatment agent for vapor deposition of a mass ratio of the component (A) to the component (B) of 6:4 to 9:1. In the case of (B) a polymer containing a fluorooxyalkylene group in Patent Document 2, as in Patent Document 1, it is described as having no functional group.

 [Previous Technical Literature]    [Patent Literature]  

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2015-199915

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

Patent Document 1 describes a polymer containing a non-functional fluorooxyalkylene group and has excellent abrasion resistance. In Patent Document 2, a fluorine-based surface treatment agent is deposited on a substrate by a vacuum deposition method. Then, it becomes a film excellent in durability. However, there is room for improvement in the improvement of wear resistance.

The present invention has been made in view of the above problems, and an object thereof is to provide a composition which can form a film having good abrasion resistance.

The composition of the present invention comprises: (a1) a compound (A) having a monovalent group having a perfluoropolyether structure and at least one of (a2) a hydrolyzable group and a hydroxyl group bonded to a halogen atom; and having a hydroxyl group and The oxygen is extended to the alkyl unit, and at least a part of the hydrogen atom of the oxygen alkyl unit is substituted by a fluorine atom, and the number average molecular weight is less than 10,000 (B).

The compound (A) is preferably a compound represented by the following formula (1a) or (2a).

In the formula (1a), Rf ¹ is an alkyl group having 1 to 20 carbon atoms or a fluorine atom in which one or more hydrogen atoms are substituted by a fluorine atom, and Rf ^{2 is} independently substituted by one or more hydrogen atoms by a fluorine atom. The alkyl group having 1 to 20 carbon atoms or the fluorine atom, and each of R ^{1 is} independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and each of R ^{2 is} independently an alkyl group having 1 to 20 carbon atoms, and D each independently Is -O-, -C(=O)-O-, -OC(=O)-, -NR-, -NRC(=O)-, or -C(=O)NR-, R is a hydrogen atom, The alkyl group having 1 to 4 carbon atoms or the fluorine-containing alkyl group having 1 to 4 carbon atoms, each of E is independently a hydrolyzable group or a hydroxyl group, and each of a1, b1, c1, d1 and e1 is independently an integer of 0 or more and 600 or less. The total value of a1, b1, c1, d1, and e1 is 9 or more, n is an integer of 1 or more and 3 or less, and each of the overlapping units enclosed by a1, b1, c1, d1, and e1 is enclosed in parentheses, as long as at least A part is arranged in the order of forming a perfluoropolyether structure, and each of them may be arranged in an arbitrary order.

In the formula (2a), Rf ³ is an alkyl group having 1 to 20 carbon atoms or a fluorine atom in which one or more hydrogen atoms are substituted by a fluorine atom, and Rf ^{4 is} independently one or more hydrogen atoms by a fluorine atom. The substituted alkyl group having 1 to 20 carbon atoms or a fluorine atom, each of R ^{3 is} independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and each of R ^{4 is} independently an alkyl group having 1 to 20 carbon atoms, and M each Independently -O-, -C(=O)-O-, -OC(=O)-, -NR-, -NRC(=O)-, or -C(=O)NR-, R is hydrogen An atom, an alkyl group having 1 to 4 carbon atoms or a fluorine-containing alkyl group having 1 to 4 carbon atoms, each independently being a hydrolyzable group or a hydroxyl group, and each Y is independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Z is a hydrogen atom or a halogen atom, and a2, b2, c2, d2, and e2 are each independently an integer of 0 or more and 600 or less, and a total of a2, b2, c2, d2, and e2 is 9 or more, and f2 is 1 or more and 20 or less. An integer of g2 is an integer of 0 or more and 2 or less, p is an integer of 1 or more and 3 or less, and each of the overlapping units enclosed by a2, b2, c2, d2, and e2 is formed by at least one portion. The perfluoropolyether structures are arranged in order, and each can be arranged in any order.

The compound (A) is preferably a compound having a total value of a1, b1, c1, d1 and e1 of the above formula (1a) of 13 or more, or a2, b2, c2, d2 and e2 of the above formula (2a). A compound having a total value of 13 or more.

The compound (B) is preferably a compound represented by the following formula (1b).

In the above formula (1b), X is each independently a hydrogen atom or a fluorine atom, and Rf ^{5 is} each independently a hydrogen atom, a fluorine atom or -CF ₃ , and J is -O-, -C(=O)-O. - or -OC(=O)-O-, a3 is 1 or more and 5 or less, b3 is 20 or more and 200 or less, and c3 is 5 or more and 200 or less, and each of the overlapping units enclosed by a3 to c3 is enclosed in parentheses. As long as at least a portion is arranged in the order of forming an oxygen-extended alkyl unit, they may each be arranged in any order, and at least a part of the hydrogen atoms of the oxygen-extended alkyl unit are replaced by fluorine atoms.

The number of hydroxyl groups contained in the above compound (B) is preferably from 1 to 2. In the compound (B), the total number of hydrogen atoms other than the hydrogen atom in the hydroxyl group and the number of fluorine atoms are counted, and the ratio of the number of fluorine atoms is preferably 40% or more.

The mass ratio of the compound (A) to the compound (B) is preferably 1 or more.

According to the composition of the present invention, at least a part of a hydrogen atom having an oxygen-extended alkyl unit and a fluorine atom having a hydroxyl group and an oxygen-extended alkyl unit is used as a fluorine atom by using a perfluoropolyether structure as a characteristic compound (A). By substituting the compound (B), a water-repellent film excellent in abrasion resistance can be obtained.

The composition of the present invention contains a compound (A) having a perfluoropolyether structure, and a compound (B) having a hydroxyl group and an oxygen alkyl group. The film exhibits good water repellency by the perfluoropolyether structure of the compound (A) and the oxygen-extended alkyl unit in which at least a part of the hydrogen atom of the compound (B) is substituted by a fluorine atom. Further, since the compound (B) has a hydroxyl group, the abrasion resistance of the film can be ensured.

The compound (A) may be a substrate containing fluorine and the compound (A) may be bonded to each other via a polymerization reaction (particularly, a polycondensation reaction) to form a film. The compound (A) is preferably a compound containing a fluorine group and at least one containing a hydrolyzable group and a hydroxyl group, wherein the compound (A) used in the present invention has a monovalent structure of a perfluoropolyether structure (a1). a compound obtained by combining at least one of (a2) a hydrolyzable group and a hydroxyl group with a ruthenium atom.

The perfluoropolyether structure refers to a structure in which all hydrogen atoms of a polyalkylene ether group or a polyalkylene glycol dialkyl ether group are substituted by a fluorine atom, and may also be referred to as a perfluoropolyalkylene ether group. Or a perfluoropolyalkylene glycol dialkyl ether residue. Further, the perfluoropolyether structure may also be referred to as a perfluorooxyalkylene group. The perfluoropolyether structure imparts water repellency to the obtained film. The number of carbon atoms contained in the longest linear portion of the perfluoropolyether structure is preferably 5 or more, more preferably 10 or more, still more preferably 20 or more. The upper limit of the carbon number is not particularly limited, and may be, for example, about 200.

In the compound (A), the above monovalent group having a perfluoropolyether structure is bonded to a ruthenium atom. The perfluoropolyether structure may be bonded to the ruthenium atom, or a suitable linking group may be present. If the linking group is absent, the perfluoropolyether structure may be directly bonded to the ruthenium atom. Examples of the linking group include a hydrocarbon group such as an alkylene group or an aromatic hydrocarbon group, a (poly)alkylene glycol group, and a group in which at least a part of the hydrogen atoms are replaced by a fluorine atom, and the like. It is a base that is properly linked. The carbon number of the linking group is, for example, 1 or more and 20 or less, preferably 2 or more and 10 or less.

Further, in one of the linking groups, a plurality of germanium atoms may be combined, and one of the linking groups may be combined with a plurality of perfluoropolyether structures. The number of the monovalent groups having the above-mentioned perfluoropolyether structure in combination with the ruthenium atom may be one or more, and may be 2 or 3, preferably 1 or 2, more preferably 1 or more.

Further, in the compound (A), at least one of the hydrolyzable group and the hydroxyl group is bonded to a ruthenium atom, and the water-decomposable group and the hydroxyl group have a hydrolysis reaction and/or a dehydrogenation condensation reaction, respectively, so that the compound (A) is mutually Or the action of the compound (A) in combination with active hydrogen derived from a hydroxyl group or the like on the surface of the substrate. Examples of such a hydrolyzable group include an alkoxy group (particularly an alkoxy group having 1 to 4 carbon atoms), an ethoxylated group, a halogen atom (particularly a chlorine atom), and the like. The preferred hydrolyzable group is an alkoxy group and a halogen atom, and particularly preferably a methoxy group, an ethoxy group or a chlorine atom.

The number of hydrolyzable groups bonded to the ruthenium atom is as long as 1. More than one can be, or 2 or 3, but 2 or 3 is better, and 3 is particularly good. When two or more hydrolyzable groups are bonded to a ruthenium atom, different hydrolyzable groups may be bonded to the ruthenium atom, but it is preferred to bond the ruthenium atom with the same hydrolyzable group. The total number of fluorine-containing groups and hydrolyzable groups bonded to the ruthenium atom is usually 4, but may be 2 or 3 (particularly 3). In the case of 3 or less, the residual bonding bond may be, for example, combined with an alkyl group (particularly an alkyl group having 1 to 4 carbon atoms), a hydrogen atom, an isocyanate group or the like.

The compound (A) is a monovalent group having a perfluoropolyether structure, and may be a linear one or a side chain.

The number average molecular weight of the compound (A) is not particularly limited, and may be, for example, 6,000 or more, preferably 7,000 or more, or 15,000 or less, and more preferably 12,000 or less.

The compound (A) is, for example, a compound of the following formula (1a).

In the formula (1a), Rf ¹ is an alkyl group having 1 to 20 carbon atoms or a fluorine atom in which one or more hydrogen atoms are substituted by a fluorine atom, and Rf ^{2 is} independently one or more hydrogen atoms by a fluorine atom. The substituted alkyl group having 1 to 20 carbon atoms or a fluorine atom, each of R ^{1 is} independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and each of R ^{2 is} independently an alkyl group having 1 to 20 carbon atoms, and each of D Independently -O-, -C(=O)-O-, -OC(=O)-, -NR-, -NRC(=O)-, or -C(=O)NR-, R is hydrogen An atom, an alkyl group having 1 to 4 carbon atoms or a fluorine-containing alkyl group having 1 to 4 carbon atoms, each of E is independently a hydrolyzable group or a hydroxyl group, and each of a1, b1, c1, d1 and e1 is independently 0 or more and 600 or less. The total value of a1, b1, c1, d1, and e1 is 9 or more, preferably 13 or more, and n is an integer of 1 or more and 3 or less, and is enclosed in parentheses with a1, b1, c1, d1, and e1. Each of the overlapping units may be arranged in any order as long as at least a portion is arranged in the order of forming a perfluoropolyether structure. Further, each of the overlapping units may be plural in the molecule. In the present specification, the case where the repeating unit has a complex number in the molecule means that the repeating unit does not continuously exist. For example, there are two overlapping units in the molecule, and two different ones are included. Repeat the situation of the unit.

Rf ^{1 is} preferably an alkyl group having 1 to 10 carbon atoms substituted by one or more fluorine atoms, more preferably a perfluoroalkyl group having 1 to 10 carbon atoms, and still more preferably 1 to 5 carbon atoms. Fluoroalkyl.

Rf ^{2 is} preferably each independently a fluorine atom or a fluorine-containing alkyl group having 1 to 2 carbon atoms, more preferably all fluorine atoms.

R ^{1 is} preferably an alkyl group each independently a hydrogen atom or a carbon number of 1 or 2, and more preferably all hydrogen atoms.

R ^{2 is} preferably an alkyl group each independently having a carbon number of 1 to 5.

D is preferably each independently -C(=O)-O-, -O-, -O-C(=O)-, and more preferably all -O-.

E is preferably an alkoxy group or a halogen atom each independently having 1 to 4 carbon atoms, and particularly preferably each independently a methoxy group, an ethoxy group or a chlorine atom.

In the order of the respective overlapping units enclosed by a1, b1, c1, d1, and e1 in parentheses, it is preferable that the most fixed end side (the side joined to the helium atom) is enclosed by b1 and enclosed in brackets. The repeating unit is located at the free end side of the repetitive unit enclosed in abbreviated with the a1 on the most free end side, and more preferably, the b1 and d1 are attached to the most fixed end side in parentheses. The repetitive unit that is enclosed is located on the free end side of the repetitive unit enclosed in parentheses with a1 and c1 on the most free end side. It is preferable that at least two of the overlapping units are enclosed in e1 and enclosed in brackets.

n is preferably 2 or more and 3 or less, more preferably 3.

In the above formula (1a), it is particularly preferred that Rf ¹ is a perfluoroalkyl group having 1 to 5 carbon atoms, Rf ² is a fluorine atom, R ¹ is a hydrogen atom, D is all -O-, and E is a The oxy group or the ethoxy group, a1 is an integer of 1 to 3, and c1 = d1 = 0, and b1 and e1 are values set by the formula (1a) in which the compound can maintain a liquid under normal pressure, n = 3. The total value of b1 and e1 may be 8 or more.

The compound represented by the above formula (1a) includes, for example, a compound of the following formula (1a-1).

In the above formula (1a-1), R ¹⁰ is a perfluoroalkyl group having a carbon number of 1 to 5, R ¹¹ is a perfluoroalkylene group having a carbon number of 1 to 5, and R ¹² is a carbon number of 1 to 3. a perfluoroalkylene group, R ¹³ is an alkylene group having 1 to 3 carbon atoms, R ¹⁴ is an alkyl group having 1 to 3 carbon atoms, and any of z2 and z3 is an integer of 1 to 3, and z1 is The compound represented by the above formula (1a-1) may be set to a value such that the liquid can be maintained at a normal pressure, and may be, for example, 3 or more.

Further, the compound (A) may, in addition to the compound of the above formula (1a), be a compound of the following formula (2a), and is preferably a compound of the following formula (2a).

In the above formula (2a), Rf ³ is an alkyl group having 1 to 20 carbon atoms or a fluorine atom in which one or more hydrogen atoms are substituted by a fluorine atom, and each of Rf ^{4 is} independently one or more hydrogen atoms. The alkyl group having 1 to 20 carbon atoms or the fluorine atom substituted by an atom, each of R ^{3 is} independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and each of R ^{4 is} independently an alkyl group having 1 to 20 carbon atoms. M is each independently -O-, -C(=O)-O-, -OC(=O)-, -NR-, -NRC(=O)-, or -C(=O)NR-,R Is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a fluorine-containing alkyl group having 1 to 4 carbon atoms, each of which is independently a hydrolyzable group or a hydroxyl group, and each of Y is independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Further, Z is a hydrogen atom or a halogen atom, and a2, b2, c2, d2 and e2 are each independently an integer of 0 or more and 600 or less, and a total of a2, b2, c2, d2 and e2 is 9 or more, preferably 13 or more, f2 is an integer of 1 or more and 20 or less, g2 is an integer of 0 or more and 2 or less, p is an integer of 1 or more and 3 or less, and each repetition is enclosed by a2, b2, c2, d2, and e2. The units may be arranged in any order as long as at least a portion is arranged in the order of forming a perfluoropolyether structure. . Further, each of the overlapping units may be plural in the molecule.

Rf ^{3 is} preferably an alkyl group having 1 to 10 carbon atoms substituted by one or more fluorine atoms, more preferably a perfluoroalkyl group having 1 to 10 carbon atoms, and still more preferably 1 to 5 carbon atoms. Perfluoroalkyl.

Rf ^{4 is} preferably each independently a fluorine atom or a fluorine-containing alkyl group having 1 to 2 carbon atoms, more preferably all fluorine atoms.

R ^{3 is} preferably each independently a hydrogen atom or an alkyl group having 1 or 2 carbon atoms, more preferably all hydrogen atoms.

R ^{4 is} preferably an alkyl group each independently having a carbon number of 1 to 5.

M is preferably each independently -C(=O)-O-, -O-, -O-C(=O)-, more preferably all -O-.

G is preferably each independently an alkoxy group or a halogen atom, and particularly preferably each independently a methoxy group, an ethoxy group or a chlorine atom.

Y is preferably each independently a hydrogen atom or an alkyl group having 1 or 2 carbon atoms, more preferably all hydrogen atoms.

Z is preferably a hydrogen atom.

Preferably, a2, c2 and d2 are respectively 1/2 or less of b2, more preferably 1/4 or less, still more preferably c2 or d2 is 0, and particularly preferably c2 and d2 are 0.

E2 is preferably 1/5 or more of the total value of a2, b2, c2, and d2, and is equal to or less than the total value of a2, b2, c2, and d2.

B2 is preferably 20 or more, 600 or less, more preferably 20 or more, 200 or less, and still more preferably 50 or more and 200 or less. The e2 is preferably 4 or more, 600 or less, more preferably 4 or more, 200 or less, and still more preferably 10 or more and 200 or less. The total value of a2, b2, c2, d2, and e2 is preferably 20 or more, 600 or less, 20 or more, 200 or less, more preferably 50 or more, and still more preferably 200 or less.

F2 is preferably 1 or more and 18 or less. More preferably, it is 1 or more and 15 or less.

G2 is preferably 0 or more and 1 or less.

p is preferably 2 or more and 3 or less, and 3 is more preferable.

In the order of the respective overlapping units enclosed by a2, b2, c2, d2, and e2 in parentheses, it is preferable that the most fixed end side (the side joined to the helium atom) is enclosed by b2 and enclosed in brackets. The repetitive unit is located at the free end side of the repetitive unit enclosed in abbreviated with the a2 on the most free end side, and more preferably, the b2 and d2 are attached to the most fixed end side in parentheses. The repetitive unit is surrounded by a repetitive unit surrounded by a2 and c2 on the free-most end side and located at the free end side. Further, it is preferable that at least two of the overlapping units enclosed in parentheses are provided with e2.

In the formula (2a), particularly preferably, Rf ³ is a perfluoroalkyl group having 1 to 5 carbon atoms, Rf ⁴ is a fluorine atom, M is all -O-, and G is a methoxy group, an ethoxy group or a chlorine atom. (especially methoxy or ethoxy), any of Y and Z are hydrogen atoms, a2 is 0, b2 is 30 to 150 (more preferably 80 to 140), and e2 is 30 to 60, c2 and D2 is 0, g2 is 0 or more and 1 or less (particularly 0), p is 3, and f2 is 1 to 10.

The compound represented by the above formula (2a) is, for example, a compound of the following formula (2a-1).

In the above formula (2a-1), R ²⁰ is a perfluoroalkyl group having a carbon number of 2 to 6, and any of R ²¹ and R ^{22 is} a perfluoroalkylene group having a carbon number of 2 to 6, and R ²³ is A trivalent saturated hydrocarbon group having 2 to 6 carbon atoms, and R ²⁴ is an alkyl group having 1 to 3 carbon atoms. The carbon numbers of R ²⁰ , R ²¹ , R ²² and R ²³ are preferably independently from 2 to 4, more preferably from 2 to 3. X1 is 5 to 70, x2 is 1 to 5, and x3 is 1 to 10. X1 is preferably from 10 to 60, more preferably from 20 to 50, x2 is preferably from 1 to 4, more preferably from 1 to 3, and x3 is preferably from 1 to 8, more preferably from 1 to 6.

The compound (B) is a compound having a hydroxyl group and an oxygen-extended alkyl unit, and at least a part of a hydrogen atom of the oxygen-extended alkyl unit is substituted by a fluorine atom, and the number average molecular weight is less than 10,000. The hydroxy group of the compound (B) interacts with a substrate such as glass or the compound (A), so that it is difficult to peel off, and the resistance of the salt-like film is compared with the case where the compound (B) is substituted with a compound having a similar structure without a hydroxyl group. Increased wear resistance.

In addition, from the viewpoint of sufficiently securing the component derived from the compound (B) in the film obtained by vacuum vapor deposition, the number average molecular weight of the compound (B) is less than 10,000, and the lower limit is, for example, about 1,000. It is better. The number average molecular weight of the compound (B) is preferably 8,000 or less, more preferably 6,000 or less.

The number of the hydroxyl groups in the compound (B) may be at least one, preferably 5 or less, more preferably 2 or less. In addition, the ratio of the number of hydrogen atoms other than the hydrogen atom in the hydroxyl group to the number of fluorine atoms is preferably 40% or more in the ratio of the number of fluorine atoms in the compound (B), and the water repellency can be exhibited by setting it. The ratio of the number of fluorine atoms is preferably 50% or more, more preferably 55% or more, and the upper limit is not particularly limited, and may be 100%, for example, about 80%.

The compound (B) is, for example, a compound represented by the following formula (1b).

In the formula (1b), X is each independently a hydrogen atom or a fluorine atom, and Rf ^{5 is} each independently a hydrogen atom, a fluorine atom, or -CF ₃ , and J is -O-, -C(=O)-O-, Or -OC(=O)-O-, a3 is 1 or more and 5 or less, b3 is 20 or more and 200 or less, c3 is 5 or more and 200 or less, and each of the overlapping units enclosed by a3 to c3 and enclosed in parentheses is required to be at least A portion is arranged in the order of forming an oxygen-extended alkyl unit, that is, each of them may be arranged in an arbitrary order, and at least a part of the hydrogen atoms of the oxygen-extended alkyl unit are replaced by a fluorine atom. Further, each of the overlapping units enclosed by a3 to c3 and enclosed in parentheses may be plural in the molecule.

Rf ^{5 is} preferably independently a hydrogen atom or a fluorine atom, X is preferably a hydrogen atom, J is preferably -O-, a3 is preferably 1 or more, more preferably 1 or 2. Is 2). B3 is preferably 30 or more and 100 or less, and c3 is preferably 10 or more and 80 or less. B3 and c3 are preferably set such that the number average molecular weight of the compound represented by the above formula (1b) is from 2,000 to 4,500, more preferably from 2,500 to 4,500. Most preferably, Rf ^{5 is} each independently a hydrogen atom or a fluorine atom, X is a hydrogen atom, J is -O-, a3 is 1 or 2, and b3 and c3 are the number of compounds represented by the above formula (1b). The average molecular weight is set to a value of from 2,000 to 4,500 (more preferably from 2,500 to 4,500).

The compound (B) may, for example, be a polyalkylene glycol in which a hydrogen atom of one OH group of a polyalkylene glycol having an OH group at both ends may be substituted, and at least a part of a hydrogen atom of an alkyl group may be substituted by a fluorine atom. Polyalkylene glycol. The compound (B) is particularly preferably a polyalkylene glycol in which at least a part of a hydrogen atom of an alkylene group is substituted by a fluorine atom, and such a polyalkylene glycol can be, for example, the following formulas (1b-1) and (1b-2). ) said.

In the formula (1b-1), R ³⁰ , R ³¹ , R ³² , R ³⁴ and R ³⁵ are each independently an alkylene group having 2 to 6 carbon atoms, and R ³³ is an alkylene group having 1 to 5 carbon atoms, R Among all of the alkyl groups of ³⁰ to R ³⁵ , at least one of the hydrogen atoms is substituted with a fluorine atom in at least one alkyl group. Y1 is 2 to 10, y2 is 1 to 4, and y3 to y5 are values set such that the number average molecular weight of the compound represented by the formula (1b-1) is 2,000 to 2,400, and y6 is 1 to 4, y7. It is 2 to 10.

R ³⁰ , R ³¹ , R ³² , R ³⁴ and R ³⁵ are preferably an alkylene group each independently having 2 to 4 carbon atoms, more preferably an alkylene group having 2 to 3 carbon atoms. Further, R ³³ is preferably an alkylene group having 1 to 3 carbon atoms, more preferably an alkylene group having 1 to 2 carbon atoms. Y1 is preferably from 3 to 9, more preferably from 4 to 8, y2 is preferably from 1 to 3, more preferably from 1 to 2, and y6 is preferably from 1 to 3, more preferably from 1 to 2. , y7 is preferably 3 to 9, and more preferably 4 to 8.

In the formula (1b-2), R ⁴⁰ and R ⁴³ are each independently an alkylene group having 1 to 3 carbon atoms, and R ⁴¹ is at least one alkyl group having 1 to 5 carbon atoms substituted by a fluorine atom. R ⁴² is at least one alkyl group having 1 to 3 carbon atoms substituted by a fluorine atom, and w1 and w4 are each independently 1 to 3, and w2 and w3 are represented by the formula (1b-2). The number average molecular weight of the compound is set to a value of 3,800 to 4,200.

R ⁴⁰ and R ⁴³ each independently take a C 1 to 2 alkyl group, and R ⁴¹ preferably has at least one alkyl group having 1 to 3 carbon atoms substituted by a fluorine atom, and R ⁴² is It is preferred that at least one of the hydrogen atoms is substituted with a fluorine atom and the alkyl group having 1 to 2 carbon atoms, and w1 and w4 are each independently preferably from 1 to 2, and it is more preferable to satisfy such requirements at the same time.

The mass ratio of the compound (A) to the compound (B) in the composition is preferably 1 or more. With such a setting, the balance between the water repellency and the abrasion resistance of the obtained film can be improved. The mass ratio of the compound (A) to the compound (B) in the composition is preferably 2.0 or more, more preferably 3.5 or more, and still more preferably 5 or more (particularly 7 or more). Further, in consideration of the balance between the water repellency and the abrasion resistance of the obtained film, the upper limit of the mass ratio is preferably 13 or less, more preferably 11 or less.

The total mass ratio of the compound (A) and the compound (B) in the composition is preferably 10% by mass or more, more preferably 12% by mass or more, and still more preferably 14% by mass based on the total mass of the composition. the above. The upper limit is not particularly limited, and may be, for example, 30% by mass or less, or 27% by mass or less, and preferably 25% by mass or less.

The composition of the present invention preferably contains the above-mentioned compounds (A) and (B) and a fluorine-based solvent (C). For the fluorine-based solvent (C), for example, a fluorinated ether solvent, a fluorinated amine solvent, a fluorinated hydrocarbon solvent (particularly a fluorinated aromatic solvent), or the like can be used, and particularly preferably a boiling point of 100 ° C or higher. The fluorinated ether solvent is preferably a hydrofluoroether such as a fluoroalkyl group (particularly a perfluoroalkyl group having 2 to 6 carbon atoms)-alkyl group (particularly methyl or ethyl) ether, and examples thereof include: Hexafluorobutyl ether or ethyl nonafluoroisobutyl ether. Ethyl nonafluorobutyl ether or ethyl nonafluoroisobutyl ether is, for example, Novec (registered trademark) 7200 (manufactured by 3M Company, having a molecular weight of about 264 and a boiling point of 76 ° C). The fluorinated amine solvent is preferably an amine in which at least one hydrogen atom of ammonia is substituted with a fluoroalkyl group, and a third stage in which all hydrogen atoms of ammonia are replaced by a fluoroalkyl group (particularly a perfluoroalkyl group). The amine is preferred, and specific examples thereof include ginseng (heptafluoropropyl)amine and Fluorinert (registered trademark) FC-3283 (having a molecular weight of about 471 and a boiling point of 128 ° C). The fluorinated hydrocarbon-based solvent may, for example, be 1,3-bis(trifluoromethylbenzene) (boiling point: about 116 ° C).

In addition to the above, a fluorine-based solvent (C) can be used, such as hydrochlorofluorocarbon such as ASAHIKLIN (registered trademark) AK 225 (manufactured by Asahi Glass Co., Ltd.), and ASAHIKLIN (registered trademark) AC 2000 (manufactured by Asahi Glass Co., Ltd.). Fluorocarbon, etc.

The molecular weight of the fluorine-based solvent (C) is preferably 900 or less, more preferably 800 or less, and the lower limit is not particularly limited, but may be, for example, about 300.

In the composition of the present invention, the content of the fluorine-based solvent (C) is, for example, 20% by mass or more, more preferably 50% by mass or more, and still more preferably 70% by mass or more, based on the total mass of the composition. It is preferably 90% by mass or less, more preferably 88% by mass or less, still more preferably 86% by mass or less.

The composition of the present invention may further contain a stanol condensation catalyst. Examples of the stanol-condensation catalyst include inorganic acids such as hydrochloric acid and nitric acid, organic acids such as acetic acid, titanium complexes (for example, manufactured by Matsumoto Seika Co., Ltd., Orgatix TC-750, etc.), or metal complexes such as tin complexes. a compound or a metal alkoxide or the like. The amount of the stanol condensation catalyst is, for example, 0.00001 to 0.1% by mass, preferably 0.00002 to 0.01% by mass, more preferably 0.0005 to 0.001% by mass, based on the total mass of the composition.

The composition of the present invention may contain an antioxidant, a rust preventive, an ultraviolet absorber, a light stabilizer, an antifungal agent, an antibacterial agent, a bioadhesive preventing agent, a deodorant, or the like, within a range not inhibiting the effects of the present invention. Various additives such as pigments, flame retardants, and antistatic agents.

The composition of the present invention is a case containing various additives, and the content of each additive is, for example, 0.01 to 70% by mass, preferably 0.05 to 50% by mass, more preferably 0.1, based on the polymer component of the composition of the present invention. It is 30% by mass, and more preferably 0.5 to 5% by mass.

The composition of the present invention is suitable for forming a film on a substrate by vacuum evaporation. The conditions of the vacuum evaporation can be carried out under known conditions. The degree of vacuum is, for example, about 10 ^-2 Pa or less. Further, in the heating method at the time of vapor deposition treatment, any one of a resistance heating method and an electron beam heating method may be used, and the heating temperature is, for example, 100 to 400 °C. The film formation time is, for example, about 1 to 60 seconds.

After vacuum evaporation, in the air at room temperature or at room temperature (for example, 5 to 30 minutes at 50 to 150 ° C), the moisture in the air is absorbed, and the hydrolyzable group in the compound (A) is bonded to the ruthenium atom. It will hydrolyze and form a combination of oxane to obtain a hardened film. The film thickness of the obtained film may be, for example, 2 to 10 nm.

The material of the substrate to which the composition of the present invention is to be deposited is not particularly limited, and may be any of an organic material and an inorganic material. The shape of the substrate may be either a flat surface or a curved surface, or a combination of a plurality of The three-dimensional structure of the surface. Examples of the organic material include thermoplastic resins such as acrylic resin, polycarbonate resin, polyester resin, styrene resin, acrylic-styrene copolymer resin, cellulose resin, polyolefin resin, and polyvinyl alcohol; phenol resin and urea; A thermosetting resin such as a resin, a melamine resin, an epoxy resin, an unsaturated polyester, a polyoxyxylene resin, or an amine ester resin. Examples of the inorganic material include metals such as iron, barium, copper, zinc, and aluminum, alloys containing such metals, ceramics, and glass. Among them, it is preferable to deposit a composition of the present invention on a substrate of an inorganic material such as glass, metal or ceramic to form a film.

After the substrate is formed into a film, a predetermined post-treatment can be performed by vapor deposition, and the abrasion resistance of the film can be further improved by post-treatment. Examples of the post-treatment include heat retention, standing in a humidified environment, ultrasonic cleaning, and wiping the surface with a solvent. These post-treatments may be carried out singly or in combination of two or more. In particular, it is preferable to wash by heating and ultrasonic cleaning, and the heating is maintained, for example, at 100 to 200 ° C for 10 to 60 minutes, and ultrasonic cleaning, for example, washing with water, a fluorine-based solvent, or an alcohol. The liquid can be carried out for about 1 to 5 minutes. Ultrasonic cleaning is preferred from the viewpoint of improving wear resistance. Since the composition of the present invention contains the compound (B) having a hydroxyl group, the compound (B) and the substrate (for example, glass) can be expected by post-treatment as compared with the case where the composition contains a compound having no hydroxyl group in the past. Or the interaction of the compound (A) changes to a state in which a higher durability is maintained.

The substrate can also be pre-implemented for easy subsequent processing. The subsequent treatment may be a hydrophilization treatment such as corona treatment, plasma treatment, or ultraviolet treatment. Further, it may be treated with a primer such as a resin, a decane coupling agent or a tetraalkoxy decane. Further, a film of a ceria layer may be formed by vapor deposition.

The primer layer is preferably a layer formed using a composition for forming a primer layer containing the component (E) composed of the compound represented by the following formula (p1) and/or a partial hydrolysis-condensation product thereof.

Si(X ² ) ₄ ‧‧‧(p1) (However, in the formula (p1), the plural X ² each independently represents a halogen atom, an alkoxy group or an isocyanate group).

In the above formula (p1), X ^{2 is} preferably each independently a chlorine atom or an alkoxy group having 1 to 4 carbon atoms or an isocyanate group, and further preferably 4 X ² is the same.

Specifically, the compound represented by the formula (p1) is preferably Si(NGO) ₄ , Si(OCH ₃ ) ₄ or Si(OC ₂ H ₅ ) ₄ or the like. The component (E) may be used alone or in combination of two or more.

The component (E) contained in the composition for forming a primer layer may be a partial hydrolysis condensate of the compound represented by the above formula (p1). The partial hydrolysis condensate of the compound represented by the above formula (p1) can be suitably obtained by a general hydrolysis condensation method using an acid or a base catalyst. However, the degree of condensation (degree of polymerization) of the partially hydrolyzed condensate must be such that it is soluble in the solvent. The component (E) may be a compound represented by the above formula (p1), a partial hydrolysis condensate of the compound represented by the above formula (p1), a compound represented by the above formula (p1), and a partially hydrolyzed condensate thereof. The mixture may, for example, be a partial hydrolysis condensate of the compound containing an unreacted compound represented by the above formula (p1). Further, the compound represented by the above formula (p1) or a partially hydrolyzed condensate thereof is commercially available, and such a commercially available product may be used in the present invention.

Further, the composition for forming a primer layer contains the component (E), and is a compound represented by the following formula (p2) (also referred to as a compound (p2)) and/or a partial hydrolysis condensate thereof. The composition of the component (F) may be a partial hydrolysis condensate containing the component (E) and the component (F) (however, the component (E) and/or the compound (p2) may be contained. )) The composition.

(X ³ ) ₃ Si-(CH ₂ ) _p -Si(X ³ ) ₃ ‧‧‧(p2) (However, in the formula (p2), the plural X ³ each independently represents a hydrolyzable group or a hydroxyl group, and p is An integer from 1 to 8.)

The compound represented by the formula (p2) is a compound having a hydrolyzable mercapto group or a stanol group at both terminals via a divalent organic group.

The hydrolyzable group represented by X ³ in the formula (p2) may, for example, be the same group or atom as the above X ² . From the viewpoint of the balance between the stability of the compound represented by the above formula (p2) and the ease of hydrolysis, X ³ is preferably an alkoxy group or an isocyanate group, and particularly preferably an alkoxy group. The alkoxy group is preferably an alkoxy group having 1 to 4 carbon atoms, more preferably a methoxy group or an ethoxy group. These may be appropriately selected and used depending on the purpose, use, and the like of the manufacturing. The plurality of X ³ present in the formula (p2) may be the same group or different groups, and from the viewpoint of easy availability, the same group is preferred.

Specific examples of the compound represented by the formula (p2) include: (CH ₃ O) ₃ SiCH ₂ CH ₂ Si(OCH ₃ ) ₃ , (OCN) ₃ SiCH ₂ CH ₂ Si(NCO) ₃ , Cl ₃ SiCH ₂ CH ₂ SiCl ₃ , (C ₂ H ₅ O) ₃ SiCH ₂ CH ₂ Si(OC ₂ H ₅ ) ₃ , (CH ₃ O) ₃ SiCH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ Si(OCH ₃ ) ₃ or the like. The component (F) may be used alone or in combination of two or more.

The component contained in the composition for forming a primer layer may be a partial hydrolysis condensate of the compound represented by the formula (p2). The partial hydrolysis condensate of the compound represented by the formula (p2) can be obtained by the same method as described in the production of the partial hydrolysis condensate of the compound represented by the formula (p1). The degree of condensation (degree of polymerization) of the partially hydrolyzed condensate must be such that the product can be dissolved in the solvent. The component (F) may be a compound represented by the formula (p2) or a partial hydrolysis condensate of the compound represented by the formula (p2), a mixture of the compound represented by the formula (p2) and a partial hydrolysis condensate thereof, for example, It may also be a partial hydrolysis condensate of the compound containing an unreacted compound represented by the formula (p2). Further, the compound represented by the above formula (p2) or a partially hydrolyzed condensate thereof is commercially available, and in the present invention, it is possible to use such a commercially available product.

Further, in the primer layer, various polyazoxides which can obtain an oxide film containing ruthenium as a main component similarly to the above formula (p1) can be used.

In addition to the solid content which is a layer constituent component, the composition for forming a primer layer usually contains an organic solvent in consideration of economy, workability, ease of controlling the thickness of the obtained primer layer, and the like. The organic solvent is not particularly limited as long as it can dissolve the solid content contained in the primer layer-forming composition. The organic solvent may, for example, be the same compound as the solvent used in the composition of the present invention. The organic solvent is not limited to one type, and two or more solvents having different polarities and evaporation rates may be used in combination. When the primer layer-forming composition contains a partial hydrolysis condensate or a partial hydrolysis co-condensate, a solvent used for the production of the solvent may be contained.

Further, even if the primer layer forming composition does not contain a partial hydrolysis condensate or a partial hydrolysis cocondensate, in order to promote the hydrolysis co-condensation reaction, the same acid contact generally used in the partial hydrolysis hydrolysis reaction is also formulated. Catalysts such as media are preferred. In the case where a partially hydrolyzed condensate or a partially hydrolyzed co-condensate is contained, it is preferred to use a catalyst when the catalyst used in the production does not remain in the composition. The primer layer-forming composition may contain water for the above-described component-containing hydrolysis condensation reaction or hydrolysis co-condensation reaction.

A method of forming a primer layer using a composition for forming a primer layer can be carried out by a conventional method in a surface treatment agent of an organic decane compound. For example, a method of brushing, flow coating, spin coating, dip coating, blade coating, spray coating, hand coating, etc., coating the primer layer forming composition on the surface of the substrate, in the atmosphere or in a nitrogen atmosphere, as needed After drying, it is hardened to form a primer layer. The conditions of hardening are appropriately controlled depending on the kind, concentration, and the like of the composition to be used. Further, the curing of the composition for forming the primer layer may be performed simultaneously with the curing of the composition for forming a water-repellent film.

The thickness of the primer layer can impart adhesion to the substrate in addition to the transparent film formed on the surface of the primer layer, and it is possible to impart adhesion to the substrate as long as it can block the thickness of the alkali or the like from the substrate. Special restrictions.

The film obtained from the composition of the present invention has excellent static water repellency characteristics and dynamic water repellency characteristics. The static water-repellent property can be evaluated, for example, in the initial contact angle of the droplet method by the θ/2 method, and the dynamic water-repellent property is the contact angle hysteresis (hysteresis) or the slip angle measured by the sliding method. And can be assessed. For example, the initial contact angle measured at a water droplet amount of 3 μL may be, for example, 110° or more, preferably 113° or more, more preferably 115° or more, and the upper limit is not particularly limited, and may be, for example, about 125°. Further, the contact angle hysteresis measured in the amount of water droplets of 6.0 μL may be, for example, 12° or less, preferably 10° or less, more preferably 9° or less, and the lower limit is not particularly limited, and may be, for example, about 3°. Further, the slip angle measured at a water droplet amount of 6 μL is, for example, 30° or less, preferably 25° or less, more preferably 23° or less, and the lower limit is not particularly limited, and may be, for example, about 5°.

 [Examples]  

Hereinafter, the present invention will be more specifically described by way of examples. The present invention is not limited to the following embodiments, and may be appropriately modified and implemented within the scope of the above-described gist of the present invention, and any of these are included in the technical scope of the present invention.

The film obtained by the examples and the comparative examples of the present invention was measured by the following method.

(1) Determination of film thickness

For the measurement, an X-ray reflectance measuring device (Smart Lab) manufactured by Rigaku Corporation was used. The 45 kW X-ray generating device of the X-ray source uses a wavelength of λ = 0.141618 nm of Cu Kα line by Cu label or a wavelength λ = 0.15406 nm of Cu Kα1 line, and a monochromator is not used. The conditions set are a sample width of 0.01° and a scan range of 0.0 to 2.5°. Then, the reflectance measurement value can be obtained by the above-described setting conditions. The obtained measured values were analyzed using the analysis software (Global Fit) of the same company.

(2) Determination of initial contact angle

The contact angle measuring device (DM 700 manufactured by Kyowa Interface Science Co., Ltd.) was used, and the liquid contact angle of the surface of the film was measured by a liquid drop method (analytical method: θ/2 method): 3 μL.

(3) Determination of contact angle hysteresis and slip angle

Using DM 700 manufactured by Concord Interface Science Co., Ltd. by sliding method (analytical method: contact method, water drop amount: 6.0 μL, tilt method: continuous tilt, slip detection: slip backward, movement judgment: advancing angle, slip determination distance: 0.125 Mm), the dynamic water-repellent characteristics (contact angle hysteresis, slip angle) of the surface of the film were measured.

(4) Evaluation of wear resistance

An abrasion test was carried out by moving the sample at a speed of 40 r/min with a load of 500 g in a state where the eraser was in contact with the sample, using a gripper equipped with an HB eraser equipped with an eraser. The contact angle of the number of abrasions per 1000 times was measured, and the number of times from the initial contact angle to -15 degrees or less was measured.

Example 1

The compound represented by the following formula (a) (number average molecular weight: about 8,000) was synthesized by the method described in Synthesis Examples 1 and 2 of JP-A-2014-15609.

In the above formula (a), n is 43, and m is an integer of 1 to 6.

In the compound (A), the compound (b) and the compound (B) represented by the above formula (a) are a compound (b1) represented by the following formula (b1) (the number average molecular weight is about 2,240).

In the above formula (b1), r and s are integers which are in the range of the above average molecular weight. In the above formula (b1), the ratio of the number of hydrogen atoms and the number of fluorine atoms excluding the hydrogen atom in the hydroxyl group is 40% or more.

Using a Novec 7200 (registered trademark) as a fluorine-based solvent (C), a composition having a mass ratio of compound (A): compound (B): fluorine-based solvent (C) = 89:11:400 was prepared. This 1 mL was dropped on the Ta boat for vapor deposition, and the solvent was evaporated to prepare a sample for vapor deposition. Using the VPC-410A manufactured by ULVAC Machine Co., Ltd., the above sample was in the absence of vacuum evaporation method (resistance heating method, pressure 8×10 ^-3 Pa, applied current 20 A, vapor deposition treatment time 15 seconds). A film was formed on an alkali glass EAGLE-XG (registered trademark, manufactured by Corning Incorporated), and used as a sample for evaluating film properties.

The evaluation results of the abrasion resistance of the obtained film are shown in Table 1. Further, in Example 1, the initial contact angle was 115.8°, the slip angle was 27.7°, and the contact angle hysteresis was 10.6°.

Example 2

After the film formation, a sample for evaluating the film properties was prepared in the same manner as in Example 1 except that the heat treatment was further carried out at 150 ° C for 30 minutes.

The results of the evaluation of the abrasion resistance of the obtained film are shown in Table 1. Further, in Example 2, the initial contact angle was 115.8°, the slip angle was 17.3°, and the contact angle hysteresis was 7.1°.

Example 3

After the film formation, a sample for evaluating the film properties was prepared in the same manner as in Example 1 except that the ultrasonic cleaning treatment was further performed in water for 3 minutes.

The evaluation results of the abrasion resistance of the obtained film are shown in Table 1. Further, in Example 3, the initial contact angle was 117.9°, the slip angle was 22.3°, and the contact angle hysteresis was 8.3°.

Example 4

A sample for evaluating film properties was prepared in the same manner as in Example 2 except that Fluorolink (registered trademark) D4000 (number average molecular weight: about 4000) represented by the following formula (b2) was used instead of the compound (b1). . Fluorolink (registered trademark) D4000 has a hydroxyl group at the terminal and an oxygen-extended alkyl unit, and a part of the hydrogen atom of the oxygen-extended alkyl unit is substituted by a fluorine atom. Further, in the Fluorolink D4000, the ratio of the number of hydrogen atoms to the number of fluorine atoms in the total number of fluorine atoms in the hydroxyl group is 40% or more.

The evaluation results of the abrasion resistance of the obtained film are shown in Table 1. Further, in Example 4, the initial contact angle was 111.1°, the slip angle was 7.3°, and the contact angle hysteresis was 4.8°.

Example 5

The film was evaluated in the same manner as in Example 2 except that the mass ratio of the composition was changed to the ratio of the compound (A): the compound (B): the fluorine-based solvent (C) = 80:20:400. Sample.

The results of evaluation of the abrasion resistance of the obtained film are shown in Table 1. Further, in Example 5, the initial contact angle was 114.9°, the slip angle was 26.3°, and the contact angle hysteresis was 14.5°.

Example 6

The film was evaluated in the same manner as in Example 4 except that the mass ratio of the composition was changed to the ratio of the compound (A): the compound (B): the fluorine-based solvent (C) = 80:20:400. Sample.

The evaluation results of the abrasion resistance of the obtained film are shown in Table 1. Further, in Example 6, the initial contact angle was 117.1°, the slip angle was 26.7°, and the contact angle hysteresis was 16.3°.

Example 7

The film was evaluated in the same manner as in Example 4 except that the mass ratio of the composition was changed to the ratio of the compound (A): the compound (B): the fluorine-based solvent (C) = 67:33:400. Sample.

The evaluation results of the abrasion resistance of the obtained film are shown in Table 1. Further, in Example 7, the initial contact angle was 115.6°, the slip angle was 22.7°, and the contact angle hysteresis was 9.5°.

Comparative example 1

A sample for evaluating the film properties was prepared in the same manner as in Example 1 except that Fomblin (registered trademark) M03 (number average molecular weight: about 4000) represented by the following formula (c) was used instead of the compound (b1). . Fomblin (registered trademark) M03 has an oxygen alkyl unit, and the hydrogen atom of the oxygen alkyl unit is entirely substituted by a fluorine atom, but has no hydroxyl group in its molecule.

The evaluation results of the abrasion resistance of the obtained film are shown in Table 1. Further, in Comparative Example 1, the initial contact angle was 115.7° and the slip angle was more than 50°, but even if the substrate was tilted to 50°, the water droplets did not slip.

Comparative example 2

A sample for evaluating the film properties was prepared in the same manner as in Example 2 except that the compound (b1) was replaced with Fomblin (registered trademark) M03.

The evaluation results of the abrasion resistance of the obtained film are shown in Table 1. Further, in Comparative Example 2, the initial contact angle was 116.5°, the slip angle was 13.7°, and the contact angle hysteresis was 4.2°.

Comparative example 3

A sample for evaluating the film properties was prepared in the same manner as in Example 3 except that the compound (b1) was replaced with Fomblin (registered trademark) M03.

The evaluation results of the abrasion resistance of the obtained film are shown in Table 1. Further, in Comparative Example 3, the initial contact angle was 118.3°, the slip angle was 13.3°, and the contact angle hysteresis was 6.5°.

As is apparent from Table 1, in Examples 1 to 7 using the compound (B) having a hydroxyl group, the abrasion resistance was improved as compared with Comparative Examples 1 to 3. Further, the film obtained by using the composition of the present invention can further improve the abrasion resistance by post-treatment after the formation of the film, and particularly in Examples 1 to 3 in which conditions other than the subsequent processing conditions are all the same. In the comparison, the third example in which ultrasonic cleaning was performed was the most excellent in abrasion resistance.

 [Industry use possibility]  

The composition of the present invention is a display device such as a touch panel display, an optical element, a semiconductor element, a building material, a nanoimprint technique, a solar cell, a window glass for an automobile or a building, a metal product such as a conditioning device, a food container, and the like. Among ceramics and plastic automobile parts, it is suitable for film formation and is industrially useful. Moreover, it is also suitable for use in kitchens, bathrooms, washstands, mirrors, toilet articles, goggles, glasses, and the like.

Claims (7)

 A composition comprising: (a1) a monovalent group having a perfluoropolyether structure and (a2) a compound (A) in which at least one of a hydrolyzable group and a hydroxyl group is bonded to a halogen atom, and having a hydroxyl group and an oxygen extension An alkyl unit, wherein at least a portion of the hydrogen atom of the oxygen alkyl unit is replaced by a fluorine atom, and the number average molecular weight is less than 10,000 (B).   The composition according to claim 1, wherein the compound (A) is represented by the following formula (1a) or (2a): In the formula (1a), Rf ¹ is an alkyl group having 1 to 20 carbon atoms or a fluorine atom in which one or more hydrogen atoms are replaced by a fluorine atom, and Rf ^{2 is} independently substituted by one or more hydrogen atoms by a fluorine atom. The alkyl group having 1 to 20 carbon atoms or a fluorine atom, and each of R ^{1 is} independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and each of R ^{2 is} independently an alkyl group having 1 to 20 carbon atoms, and each of D Independently -O-, -C(=O)-O-, -OC(=O)-, -NR-, -NRC(=O)-, or -C(=O)NR-, R is hydrogen An atom, an alkyl group having 1 to 4 carbon atoms or a fluorine-containing alkyl group having 1 to 4 carbon atoms, each of E is independently a hydrolyzable group or a hydroxyl group, and a1, b1, c1, d1 and e1 are each independently 0 or more and 600 or less. The integer value of a1, b1, c1, d1, and e1 is 9 or more, and n is an integer of 1 or more and 3 or less, and each of the overlapping units enclosed by a1, b1, c1, d1, and e1 is enclosed in parentheses. As long as at least a portion is arranged in the order of forming a perfluoropolyether structure, each can be arranged in any order. In the formula (2a), Rf ³ is an alkyl group having 1 to 20 carbon atoms or a fluorine atom in which one or more hydrogen atoms are replaced by a fluorine atom, and each of Rf ⁴ is independently one or more hydrogen atoms by a fluorine atom. The substituted alkyl group having 1 to 20 carbon atoms or a fluorine atom, each of R ^{3 is} independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and each of R ^{4 is} independently an alkyl group having 1 to 20 carbon atoms, M Each is independently -O-, -C(=O)-O-, -OC(=O)-, -NR-, -NRC(=O)-, or -C(=O)NR-, R is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a fluorine-containing alkyl group having 1 to 4 carbon atoms, each of which is independently a hydrolyzable group or a hydroxyl group, and each of Y is independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. a Z-based hydrogen atom or a halogen atom, and a2, b2, c2, d2, and e2 are each independently an integer of 0 or more and 600 or less, and a total of a2, b2, c2, d2, and e2 is 9 or more, and f2 is 1 or more. The following integer, g2 is an integer of 0 or more and 2 or less, p is an integer of 1 or more and 3 or less, and each of the overlapping units enclosed by a2, b2, c2, d2, and e2 is enclosed by at least a part. The sequential arrangement of the perfluoropolyether structures can be arranged in any order.  The composition according to the second aspect of the invention, wherein the compound (A) is a compound having a total value of a1, b1, c1, d1 and e1 of the above formula (1a) of 13 or more, or the above formula (2a) The total value of a2, b2, c2, d2, and e2 is 13 or more.   The composition according to any one of claims 1 to 3, wherein the compound (B) is represented by the following formula (1b), In the above formula (1b), X is each independently a hydrogen atom or a fluorine atom, and Rf ^{5 is} each independently a hydrogen atom, a fluorine atom, or -CF ₃ , and J is -O-, -C(=O)-O-. Or -OC(=O)-O-, a3 is 1 or more and 5 or less, b3 is 20 or more and 200 or less, c3 is 5 or more and 200 or less, and each of the overlapping units enclosed by a3 to c3 is enclosed in parentheses, as long as At least a portion of the alkylene units are arranged in the order in which they are formed, that is, they are each arranged in any order, and at least a portion of the hydrogen atoms of the oxygen-extended alkyl unit are replaced by fluorine atoms.  The composition according to any one of claims 1 to 4, wherein the number of hydroxyl groups contained in the compound (B) is 1 to 2.    In the compound (B), the total number of hydrogen atoms other than the hydrogen atom in the hydroxyl group and the number of fluorine atoms, and the number of fluorine atoms in the compound (B). The ratio is 40% or more.    The composition according to any one of claims 1 to 6, wherein the mass ratio of the compound (A) to the compound (B) is 1 or more.