JP6993894B2 - Composition - Google Patents

Description

The present invention relates to a composition.

Compositions containing compounds having a perfluoropolyether structure are used as antifouling coating agents, adhesives, water- and oil-repellent coating agents, and the like.

For example, Patent Document 1 describes a method for producing an antifouling base material by applying a photocurable hard coat agent composition to the surface of a base material made of a resin, curing it, and then treating it with an antifouling coating agent. As an antifouling coating agent, perfluoropolyether-modified silane is disclosed. Further, Patent Document 2 discloses an adhesive composition containing a linear polyfluoro compound having two or more alkenyl groups in one molecule and having a perfluoropolyether structure in the main chain. .. Further, Patent Document 3 discloses a coating agent composition containing a fluorosilicon compound containing a perfluoropolyether residue, and the film obtained from this coating agent composition is resistant to water-based and oily stains. Is described.

Japanese Unexamined Patent Publication No. 2011-93964 Japanese Unexamined Patent Publication No. 2011-168768 Japanese Unexamined Patent Publication No. 2009-30039

When a composition containing a compound having a perfluoropolyether structure is used for the above-mentioned applications, the adhesion between the base material and the film is good so that the obtained film can exhibit its performance for a long period of time. Is required. When the film is used in applications where water and oil repellency is required, it is also important that the film has good sliding properties such as water droplets on the film.

Therefore, the present invention is a composition containing a compound having a perfluoropolyether structure, and forms a film having excellent adhesion between the film obtained from this composition and a substrate and having good slipperiness such as water droplets. It is an object of the present invention to provide a possible composition.

In the present invention, a monovalent group having a perfluoropolyether structure, a first organic silicon compound (A) in which a hydrolyzable group is bonded to a silicon atom, and a hydrolyzable group bonded to a silicon atom. It is a composition containing a second organic silicon compound (B) having a perfluoropolyether structure and having a metal element of Group 13 of the periodic table.

The compound having a metal element of Group 13 of the periodic table is preferably a complex having a metal element of Group 13 of the periodic table.

The first organosilicon compound (A) is preferably represented by the following formula (a1).

In the above formula (a1),
Rf ^a1 has a divalent perfluoropolyether structure in which both ends are oxygen atoms.
R ¹¹ , R ¹² , and R ¹³ are independently alkyl groups having 1 to 20 carbon atoms, and when a plurality of R ^11s are present, a plurality of R ^11s may be different from each other, and a plurality of R ^12s are present. If multiple R 12s are present, the plurality of R ^12s may be different, and if multiple R ^13s are present, the plurality of R ^13s may be different from each other.
E ¹ , E ² , E ³ , E ⁴ , and E ⁵ are independent hydrogen atoms or fluorine atoms, and when multiple E ^1s are present, the plurality of E ^1s may be different from each other. When there are a plurality of ² 's, a plurality of E ² 's may be different, when there are a plurality of E ³ 's, a plurality of E ³ 's may be different, and when there are a plurality of E ⁴ 's, a plurality of E's are used. ⁴ may be different,
G ¹ and G ² are 2- to 10-valent organosiloxane groups each independently having a siloxane bond.
J ¹ , J ² , and J ³ are independently hydrolyzable groups or-(CH ₂ ) _e6 -Si (OR ¹⁴ ) ₃ , e 6 is 1-5, and R ¹⁴ is a methyl group. Alternatively, it is an ethyl group, and when a plurality of J ^1s are present, a plurality of J ^1s may be different from each other, and when a plurality of J ^2s are present, a plurality of J ^2s may be different from each other, and a plurality of J ^3s are present. If present, multiple J ^3s may be different,
L ¹ and L ² are divalent linking groups having 1 to 12 carbon atoms which may independently contain an oxygen atom, a nitrogen atom, and a fluorine atom, and when a plurality of L ^1s are present, a plurality of L 1 and L 2 are divalent linking groups. L ¹ may be different from each other, and when a plurality of L ² are present, a plurality of L ² may be different from each other.
d11 is 1 to 9,
d12 is 0-9,
a10 and a14 are 0 to 10 independently, respectively, and are 0 to 10.
a11 and a15 are independently 0 or 1, respectively, and are 0 or 1.
a12 and a16 are independently 0 to 9, respectively, and are 0 to 9.
a13 is 0 or 1 and is
a21, a22, and a23 are 0 to 2 independently, respectively.
e1, e2, and e3 are 1 to 3 independently of each other.

Further, it is preferable that the second organosilicon compound (B) contains a compound represented by the following formula (b1).

In the above formula (b1),
Rf ^b10 is an alkyl group or a fluorine atom having 1 to 20 carbon atoms in which one or more hydrogen atoms are substituted with a fluorine atom.
R ^b11 , R ^b12 , R ^b13 , and R ^b14 are each independently an alkyl group having a hydrogen atom or 1 to 4 carbon atoms, and when a plurality of R ^b11s are present, the plurality of R ^b11s are different from each other. If there are a plurality of R ^b12s , the plurality of R ^b12s may be different, if there are a plurality of R ^b13s , the plurality of R ^b13s may be different, and if there are a plurality of R ^b14s . May have different R ^b14s ,
Rf ^b11 , Rf ^b12 , Rf ^b13 , and Rf ^b14 are independently alkyl groups or fluorine atoms having 1 to 20 carbon atoms in which one or more hydrogen atoms are substituted with fluorine atoms, and a plurality of Rf ^b11 are present. In this case, a plurality of Rf ^b11s may be different from each other, a plurality of Rf ^b12s may be different from each other when a plurality of Rf ^b12s are present, and a plurality of Rf ^b13s may be different from each other when a plurality of Rf ^b13s are present. If there are a plurality of Rf ^b14s , the plurality of Rf ^b14s may be different from each other.
R ^b15 is an alkyl group having 1 to 20 carbon atoms, and when a plurality of R ^b15s are present, the plurality of R ^b15s may be different from each other.
A ¹ is -O-, -C (= O) -O-, -OC (= O)-, -NR-, -NRC (= O)-, or -C (= O) NR-. Yes, the 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, and when a plurality of A ^1s are present, the plurality of A ^1s may be different from each other.
A ² is a hydrolyzable group, and when a plurality of A ^2s are present, the plurality of A ^2s may be different from each other.
b11, b12, b13, b14, and b15 are independently integers of 0 or more and 100 or less, respectively.
c is an integer of 1 or more and 3 or less,
Rf ^b10 -,-Si (A ² ) _c (R ^b15 ) _3-c , b11-{C (R ^b11 ) (R ^b12 )}-, b12- {C (Rf ^b11 ) (Rf ^b12 ) }-, B13-{Si (R ^b13 ) (R ^b14 )}-, b14-{Si (Rf ^b13 ) (Rf ^b14 )}-, b15 -A ^1- are Rf ^b10- , -Si (A ² ) _c (R ^b15 ) _3-c is the terminal, does not form a polysiloxane structure, does not form a perfluoropolyether structure, and -O- does not connect with -O- to -F. As long as they are combined side by side in any order.

The metal compound is preferably an Al compound, more preferably an Al complex.

The ratio of the compound of the metal to the total of the first organosilicon compound (A) and the second organosilicon compound (B) is preferably 0.6 to 5.0 mol% in terms of mass ratio. In terms of mass ratio, it is preferably 0.1 to 2.0% by mass.

The present invention also includes a covering having a film obtained by curing the above-mentioned composition of the present invention. The present invention also includes a method for producing the coating, which comprises curing the composition at room temperature.

The composition of the present invention comprises a monovalent group having a perfluoropolyether structure and a first organic silicon compound (A) in which a hydrolyzable group is bonded to a silicon atom, and water bonded to the silicon atom. Since the second organic silicon compound (B) having a degradable group and no perfluoropolyether structure and the compound having a metal element of Group 13 of the periodic table are contained, the obtained film is a base material. It has the effect of excellent adhesion to (especially iron-based base materials) and excellent sliding property.

The composition of the present invention contains a specific organosilicon compound (A), (B) and a compound having a specific metal (hereinafter, may be referred to as a "metal compound"). Some metal compounds are known as catalysts for accelerating the reaction rate of the condensation reaction, but the present inventors, together with the specific organic silicon compounds (A) and (B), are metal elements of Group 13 of the periodic table. It was clarified that the adhesion between the film obtained from this composition and the substrate is improved by using the composition containing the compound having the above. Further, when the composition contains the organosilicon compound (B) together with the organosilicon compound (A), the sliding property of the obtained film is improved. Hereinafter, the organosilicon compounds (A), (B) and the metal compounds in the present invention will be described in order.

1. 1. First organosilicon compound (A)
The first organic silicon compound (A) (hereinafter, may be simply referred to as “compound (A)”) contains fluorine and polymerizes with each other or with other monomers (particularly heavy). It is a compound that can be a matrix of a film by being bonded through a condensation reaction), specifically, a compound in which a monovalent group having a perfluoropolyether structure and a hydrolyzable group are bonded to a silicon atom. ..

The perfluoropolyether structure is a structure in which all hydrogen atoms of the polyoxyalkylene group are replaced with fluorine atoms, and can be said to be a perfluoropolyoxyalkylene group. The perfluoropolyether structure can impart water repellency to the obtained film. The number of carbon atoms contained in the longest linear portion of the perfluoropolyether structure is, for example, preferably 5 or more, more preferably 10 or more, still more preferably 20 or more. The upper limit of the number of carbon atoms is not particularly limited, and may be, for example, about 200.

In compound (A), the monovalent group having the perfluoropolyether structure is bonded to the silicon atom. A suitable linking group may be present on the side where the perfluoropolyether structure is bonded to the silicon atom, or the perfluoropolyether structure may be directly bonded to the silicon atom without the linking group. As the linking group, for example, a hydrocarbon group such as an alkylene group or an aromatic hydrocarbon group, a (poly) alkylene glycol group, a group in which at least a part of these hydrogen atoms is substituted with a fluorine atom, and these are suitable. Examples include groups linked to. The carbon number of the linking group is, for example, 1 or more and 20 or less, preferably 2 or more and 15 or less, and more preferably 2 or more and 10 or less.

A plurality of silicon atoms may be bonded to one linking group, or a plurality of perfluoropolyether structures may be bonded to one linking group. The number of monovalent groups having the perfluoropolyether structure bonded to the silicon atom may be 1 or more, may be 2 or 3, but is preferably 1 or 2. It is particularly preferable to have it.

Further, in the compound (A), a hydrolyzable group is bonded to the silicon atom, and the hydrolyzable group is a group of the compounds (A) with each other or with the compound (A) through a hydrolysis / dehydration condensation reaction. It has the function of binding to active hydrogen derived from hydroxy groups on the surface of the material. Examples of such a hydrolyzable group include an alkoxy group (particularly an alkoxy group having 1 to 4 carbon atoms), an acetoxy group, and a halogen atom (particularly a chlorine atom). Preferred hydrolyzable groups are an alkoxy group and a halogen atom, and a methoxy group, an ethoxy group and a chlorine atom are particularly preferable.

The number of hydrolyzable groups bonded to the silicon atom may be 1 or more, may be 2 or 3, but is preferably 2 or 3, and particularly preferably 3. When two or more hydrolyzable groups are bonded to a silicon atom, different hydrolyzable groups may be bonded to the silicon atom, but the same hydrolyzable group is bonded to the silicon atom. preferable. The total number of monovalent groups having a perfluoropolyether structure and hydrolyzable groups bonded to a silicon atom is usually 4, but may be 2 or 3 (particularly 3). In the case of 3 or less, for example, an alkyl group (particularly an alkyl group having 1 to 4 carbon atoms), a hydrogen atom, an isocyanate group, or the like can be bonded to the remaining bonding hands.

The monovalent group having a perfluoropolyether structure of compound (A) may be linear or may have a side chain. Further, a monovalent group having a perfluoropolyether structure may further have a silicon atom and a hydrolyzable group bonded to the silicon atom.

The number average molecular weight of compound (A) is not particularly limited, but is preferably 2,000 or more and 50,000 or less, for example. The lower limit of the number average molecular weight of compound (A) is preferably 4,000 or more, more preferably 6,000 or more, still more preferably 7,000 or more, and the upper limit is preferably 40,000 or less, more preferably 20. It is 000 or less, more preferably 15,000 or less.

The compound (A) can be represented by, for example, the following formula (a1).

In the above formula (a1),
Rf ^a1 has a divalent perfluoropolyether structure in which both ends are oxygen atoms.
R ¹¹ , R ¹² , and R ¹³ are independent alkyl groups having 1 to 20 carbon atoms (that is, R ¹¹ and R ¹² and R ¹³ may be the same or different from each other). When there are a plurality of R ^11s , the plurality of R ^11s may be different from each other, when there are a plurality of R ^12s , a plurality of R ^12s may be different from each other, and when there are a plurality of R ^13s . May have different R ^13s ,
E ¹ , E ² , E ³ , E ⁴ and E ⁵ are independently hydrogen or fluorine atoms, respectively.
When there are multiple E ^1s , multiple E ^1s may be different, when there are multiple E ^2s , multiple E ^2s may be different, and when there are multiple E ^3s , there are multiple E 3s. E ³ may be different, and if there are multiple E ^4s , multiple E ^4s may be different.
G ¹ and G ² are 2- to 10-valent organosiloxane groups each independently having a siloxane bond.
J ¹ , J ² , and J ³ are independently hydrolyzable groups or-(CH ₂ ) _e6 -Si (OR ¹⁴ ) ₃ , e 6 is 1-5, and R ¹⁴ is a methyl group. Alternatively, it is an ethyl group, and when a plurality of J ^1s are present, a plurality of J ^1s may be different from each other, and when a plurality of J ^2s are present, a plurality of J ^2s may be different from each other, and a plurality of J ^3s are present. If present, multiple J ^3s may be different,
L ¹ and L ² are divalent linking groups having 1 to 12 carbon atoms which may independently contain an oxygen atom, a nitrogen atom, and a fluorine atom, and when a plurality of L ^1s are present, a plurality of L 1 and L 2 are divalent linking groups. L ¹ may be different from each other, and when a plurality of L ² are present, a plurality of L ² may be different from each other.
d11 is 1 to 9,
d12 is 0-9,
a10 and a14 are 0 to 10 independently, respectively, and are 0 to 10.
a11 and a15 are independently 0 or 1, respectively, and are 0 or 1.
a12 and a16 are independently 0 to 9, respectively, and are 0 to 9.
a13 is 0 or 1 and is
a21, a22, and a23 are 0 to 2 independently, respectively.
e1, e2, and e3 are 1 to 3 independently of each other.

In the above formula (a1)
Rf ^a1 is preferably -O- (CF ₂ CF ₂ O) _e4- or -O- (CF ₂ CF ₂ CF ₂ O) _e5- (e4 is preferably 1 to 85, and e5 is 25 to. It is preferably 70, more preferably 35 to 50),.
R ¹¹ , R ¹² , and R ¹³ are each independently preferably an alkyl group having 1 to 10 carbon atoms.
It is preferable that L ¹ and L ² are independently divalent linking groups having 1 to 5 carbon atoms containing a fluorine atom.
G ¹ and G ² are preferably 2- to 5-valent organosiloxane groups each independently having a siloxane bond.
J ¹ , J ² , and J ³ are each independently preferably a methoxy group, an ethoxy group, or-(CH ₂ ) _e6 -Si (OR ¹⁴ ) ₃ .
a10 is preferably 0 to 5 (more preferably 0 to 3), a11 is preferably 0, a12 is preferably 0 to 7 (more preferably 0 to 5), and a14 is preferably 1 to 6 (more preferably 1). ~ 3), a15 is preferably 0, a16 is preferably 0 to 6, a21 to a23 are all preferably 0 or 1 (more preferably all 0), and d11 is preferably 1 to 5 (more preferably 1). ~ 3), d12 is preferably 0 to 3 (more preferably 0 or 1), and e1 to e3 are all preferably 3.

As the compound (A), Rf ^a1 of the above formula (a1) is −O— (CF ₂ CF ₂ CF ₂ O) _e5- , e5 is 35 to 50, and L ¹ and L ² are both carbons. It is a perfluoroalkylene group of the number 1 to 3, where E ¹ , E ² , and E ³ are all hydrogen atoms, and E ⁴ and E ⁵ are hydrogen atoms or fluorine atoms, and J ¹ , J ² , and J ³ are used. Are all methoxy groups or ethoxy groups (particularly methoxy groups), a10 is 1 to 3, a11 is 0, a12 is 0 to 5, a13 is 1, and a14 is 2 to 5. Yes, a15 is 0, a16 is 0-6, a21-a23 are independently 0 or 1 (more preferably a21-a23 are all 0), d11 is 1 and d12. Is 0 or 1, and it is preferable to use a compound in which e1 to e3 are all 3.

When the compound a used as the compound (A) in the examples described later is represented by the above formula (a1), Rf ^a1 is −O— (CF ₂ CF ₂ CF ₂ O) ₄₃ −, and L ¹ and L ² is- (CF ₂ )-, E ¹ , E ² , and E ³ are all hydrogen atoms, E ⁵ is a fluorine atom, and J ¹ and J ² are all methoxy groups. a10 is 2, a11 is 0, a12 is 0-5, a13 is 1, a14 is 3, a15 is 0, a16 is 0, a21, a22 are all 0, d11 is 1, d12 is 0, e1, e2 is 3 in each case.

As the compound (A), Rf ^a1 of the above formula (a1) is −O— (CF ₂ CF ₂ CF ₂ O) _e5- , e5 is 25 to 40, and L ¹ is a fluorine atom and an oxygen atom. It is a divalent linking group containing 3 to 6 carbon atoms, L ² is a perfluoroalkylene group having 1 to 3 carbon atoms, E ² and E ³ are both hydrogen atoms, and E ⁵ is a fluorine atom. Yes, J ² is-(CH ₂ ) _e6 -Si (OCH ₃ ) ₃ , e6 is 2-4, a10 is 1-3, a11 is 0, a12 is 0, a13. Is 0, a14 is 2 to 5, a15 is 0, a16 is 0, and a21 to a23 are independently 0 or 1 (more preferably, all a21 to a23 are 0). ), It is also preferable to use a compound in which d11 is 1, d12 is 0, and e2 is 3.

Further, the compound (A) can also be represented by the following formula (a2-1).

In the above formula (a2-1),
Rf ^a21 is an alkyl group or a fluorine atom having 1 to 20 carbon atoms in which one or more hydrogen atoms are substituted with a fluorine atom.
Rf ^a22 , Rf ^a23 , Rf ^a24 , and Rf ^a25 are independently alkyl groups or fluorine atoms having 1 to 20 carbon atoms in which one or more hydrogen atoms are substituted with fluorine atoms, and a plurality of Rf ^a22s are present. In this case, a plurality of Rf ^a22s may be different from each other, a plurality of Rf ^{a23s may be different from each other when a plurality of Rf a23s are present, and a plurality of Rf a24s may be different from each other when a plurality of Rf a24s are present .} If there are a plurality of Rf ^a25s , the plurality of Rf ^a25s may be different from each other.
R ²⁰ , R ²¹ , R ²² and R ²³ are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and when multiple R ^20s are present, even if the plurality of R ^20s are different from each other. Often, when there are a plurality of R ^21s , the plurality of R ^21s may be different, when there are a plurality of R ^22s , the plurality of R ^22s may be different, and when there are a plurality of R ^23s , the plurality of R 23s may be different. Multiple R ^23s may be different,
R ²⁴ is an alkyl group having 1 to 20 carbon atoms, and when a plurality of R ^24s are present, the plurality of R ^24s may be different from each other.
M ¹ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and when a plurality of M ^1s are present, the plurality of M ^1s may be different from each other.
M ² is a hydrogen atom or a halogen atom,
M ³ is -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), and when a plurality of M ^3s are present, the plurality of M ^3s may be different from each other.
M ⁴ is a hydrolyzable group, and when a plurality of M ^4s are present, the plurality of M ^4s may be different from each other.
f11, f12, f13, f14, and f15 are independently integers of 0 or more and 600 or less, and the total value of f11, f12, f13, f14, and f15 is 13 or more.
f16 is an integer of 1 or more and 20 or less.
f17 is an integer of 0 or more and 2 or less.
g1 is an integer of 1 or more and 3 or less.
Rf ^a21- , M ^2- , f11-{C (R ²⁰ ) (R ²¹ )}-, f12- {C (Rf ^a22 ) (Rf ^a23 )}-, f13-{Si (R) ²² ) (R ²³ )}-, f14-{Si (Rf ^a24 ) (Rf ^a25 )}-, f15 -M ^3- , f 16- [CH ₂ C (M ¹ ) {(CH ₂ ) ) _F17 -Si (M ⁴ ) _g1 (R ²⁴ ) _3-g1 }]-is arranged in the order of Rf ^a21- and M ^2- at the end, forming a perfluoropolyether structure at least in part, and- Unless O- is connected to -O- to -F, they are combined side by side in any order. That is, in the equation (a2-1), f11-{C (R ²⁰ ) (R ²¹ )}-are always continuous, and f12-{C (Rf ^a22 ) (Rf ^a23 )}-are continuous. , F13-{Si (R ²² ) (R ²³ )}-is continuous, f14-{Si (Rf ^a24 ) (Rf ^a25 )}-is continuous, and f15-M ³ -is continuous. However, it does not mean that f16- [CH ₂ C (M ¹ ) {(CH ₂ ) _f17 -Si (M ⁴ ) _g1 (R ²⁴ ) _3-g1 }]-are arranged in this order in succession. , -C (R ²⁰ ) (R ²¹ ) -Si (Rf ^a24 ) (Rf ^a25 ) -CH ₂ C (M ¹ ) {(CH ₂ ) _f17 -Si (M ⁴ ) _g1 (R ²⁴ ) _3-g1 } -C (Rf ^a22 ) (Rf ^a23 ) -M ³ -Si (R ²² ) (R ²³ ) -C (Rf ^a22 ) (Rf ^a23 ) -and so on, each can be arranged in any order. be.

Rf ^a21 is preferably an alkyl group having 1 to 10 carbon atoms substituted with one or more fluorine atoms, more preferably a perfluoroalkyl group having 1 to 10 carbon atoms, and further preferably 1 to 10 carbon atoms. It is a perfluoroalkyl group of 5.

Rf ^a22 , Rf ^a23 , Rf ^a24 , and Rf ^a25 are preferably independent alkyl groups having 1 to 2 carbon atoms in which a fluorine atom or one or more hydrogen atoms are substituted with a fluorine atom, and more preferably. Are all fluorine atoms.

R ²⁰ , R ²¹ , R ²² and R ²³ are preferably independent hydrogen atoms or alkyl groups having 1 to 2 carbon atoms, and more preferably all hydrogen atoms.

R ²⁴ is preferably an alkyl group having 1 to 5 carbon atoms.

M ¹ is preferably a hydrogen atom or an alkyl group having 1 to 2 carbon atoms independently of each other, and more preferably all hydrogen atoms.

M ² is preferably a hydrogen atom.

M ³ is preferably —C (= O) —O—, —O—, —OC (= O) −, and more preferably all —O—.

M ⁴ is preferably an alkoxy group or a halogen atom, and particularly preferably a methoxy group, an ethoxy group or a chlorine atom.

Preferably, f11, f13, and f14 are each 1/2 or less of f12, more preferably 1/4 or less, further preferably f13 or f14 is 0, and particularly preferably f13 and f14 are 0.

f15 is preferably 1/5 or more of the total value of f11, f12, f13, and f14, and is not more than or equal to the total value of f11, f12, f13, and f14.

The f12 is preferably 20 or more and 600 or less, more preferably 20 or more and 200 or less, still more preferably 50 or more and 200 or less (more preferably 30 to 150, particularly 50 to 150, and most preferably 80 to 80 to). 140). f15 is preferably 4 or more and 600 or less, more preferably 4 or more and 200 or less, still more preferably 10 or more and 200 or less (more preferably 30 to 60). The total value of f11, f12, f13, f14, and f15 is preferably 20 or more and 600 or less, more preferably 20 or more and 200 or less, and further preferably 50 or more and 200 or less.

f16 is preferably 1 or more and 18 or less. It is more preferably 1 or more and 15 or less, and further preferably 1 or more and 10 or less.

f17 is preferably 0 or more and 1 or less.

g1 is preferably 2 or more and 3 or less, and more preferably 3.

f11-{C (R ²⁰ ) (R ²¹ )}-, f12-{C (Rf ^a22 ) (Rf ^a23 )}-, f13-{Si (R ²² ) (R ²³ )}- , F14 − {Si (Rf ^a24 ) (Rf ^a25 )} −, f15 −M ³ − are arbitrary in the formula as long as they are arranged in the order of forming a perfluoropolyether structure at least in part. However, preferably, the repeating unit (that is,-{C (Rf ^a22 ) (Rf ^a23 )}-) enclosed in parentheses with f12 on the most fixed end side (the side bonded to the silicon atom) is It is located on the free end side of the repeating unit (that is,-{C (R ²⁰ ) (R ²¹ )}-) enclosed in parentheses with f11 on the most free end side, and more preferably on the fixed end side. Repeat units with f12 and f14 in parentheses (ie,-{C (Rf ^a22 ) (Rf ^a23 )}-and-{Si (Rf ^a24 ) (Rf ^a25 )}-) are the most. Repeat units with f11 and f13 on the free end side and enclosed in parentheses (ie-{C (R ²⁰ ) (R ²¹ )}-and-{Si (R ²² ) (R ²³ )}-) Located on the free end side.

In the above formula (a2-1), Rf ^a21 is a perfluoroalkyl group having 1 to 5 carbon atoms, Rf ^a22 , Rf ^a23 , Rf ^a24 , and Rf ^a25 are all fluorine atoms, and M ³ is all -O-. M ⁴ is all a methoxy group, an ethoxy group or a chlorine atom (particularly a methoxy group or an ethoxy group), M ¹ and M ² are both hydrogen atoms, f11 is 0, and f12 is 30 to 150 (from). It is preferable that 80 to 140), f15 is 30 to 60, f13 and f14 are 0, f17 is 0 or more and 1 or less (particularly 0), g1 is 3, and f16 is 1 to 10.

In the compound a used as the compound (A) in the examples described later, when expressed by the above formula (a2-1), Rf ^a1 is C ₃ F ₇ −, and both Rf ^a22 and Rf ^a23 are fluorine atoms. Yes, f11 = f13 = f14 = 0, f12 is 131, f15 is 44, f16 is 1 to 6, f17 is 0, M ¹ and M ² are hydrogen atoms, M ³ is -O-, and M ⁴ Is a methoxy group and g1 is 3.

Further, the compound (A) can also be represented by the following formula (a2-2).

In the above formula (a2-2),
Rf ^a26 , Rf ^a27 , Rf ^a28 , and Rf ^a29 are independently alkyl groups or fluorine atoms having 1 to 20 carbon atoms in which one or more hydrogen atoms are substituted with fluorine atoms, and there are a plurality of Rf ^a26 . In this case, a plurality of Rf ^a26s may be different from each other, a plurality of Rf ^{a27s may be different from each other when a plurality of Rf a27s are present, and a plurality of Rf a28s may be different from each other when a plurality of Rf a28s are present .} If there are a plurality of Rf ^a29s , the plurality of Rf ^a29s may be different from each other.
R ²⁵ , R ²⁶ , R ²⁷ , and R ²⁸ are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and when multiple R ^25s are present, even if the plurality of R ^25s are different from each other. Often, when there are a plurality of R ^26s , the plurality of R ^26s may be different, when there are a plurality of R ^27s , the plurality of R ^27s may be different, and when there are a plurality of R ^28s , the plurality of R 28s may be different. Multiple R ^28s may be different,
R ²⁹ and R ³⁰ are independently alkyl groups having 1 to 20 carbon atoms, and when a plurality of R ^29s are present, the plurality of R ^29s may be different from each other, and when a plurality of R ^30s are present. May have different R ^30s ,
M ⁷ is -O-, -C (= O) -O-, -OC (= O)-, -NR-, -NRC (= O)-, or -C (= O) NR-. Yes, the 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, and when a plurality of M ^7s are present, the plurality of M ^7s may be different from each other.
M ⁵ and M ⁹ are independently hydrogen atoms or alkyl groups having 1 to 4 carbon atoms, and when a plurality of M ^5s are present, a plurality of M ^5s may be different from each other, and a plurality of M ^9s are present. If present, multiple ^M9s may be different, respectively.
M ⁶ and M ¹⁰ are independently hydrogen atoms or halogen atoms, respectively.
M ⁸ and M ¹¹ are independently hydrolyzable groups, and when a plurality of M ^8s are present, a plurality of M ^8s may be different from each other, and when a plurality of M ^11s are present, a plurality of Ms are present. ¹¹ may be different,
f21, f22, f23, f24, and f25 are independently integers of 0 or more and 600 or less, and the total value of f21, f22, f23, f24, and f25 is 13 or more.
f26 and f28 are independently integers of 1 or more and 20 or less, respectively.
f27 and f29 are independently integers of 0 or more and 2 or less, respectively.
g2 and g3 are independently integers of 1 or more and 3 or less, respectively.
M ^10- , M ^6- , f21-{C (R ²⁵ ) (R ²⁶ )}-, f22-{C (Rf ^a26 ) (Rf ^a27 )}-, f23- {Si (R) ²⁷ ) (R ²⁸ )}-, f24-{Si (Rf ^a28 ) (Rf ^a29 )}-, f25 -M ^7- , f26- [CH ₂ C (M ⁵ ) {(CH ₂ ) ) _F27 -Si (M ⁸ ) _g2 (R ²⁹ ) _3-g2 }], f28- [CH ₂ C (M ⁹ ) {(CH ₂ ) _f29 -Si (M ¹¹ ) _g3 (R ³⁰ ) _{3- g3} }] are arranged in the order of forming a perfluoropolyether structure at least in part, with M ^10- and M ^6- at the ends, and are arranged in any order unless -O- is continuous with -O-. Join. The joining in any order is the same as described in the above formula (a2-1), and each repeating unit is continuously arranged in the order as described in the above formula (a2-2). Not limited to meaning.

In the above formula (a2-2), Rf ^a26 , Rf ^a27 , Rf ^a28 , and Rf ^a29 are all fluorine atoms, M ⁷ is all -O-, and M ⁸ and M ¹¹ are all methoxy groups, ethoxy groups, or A chlorine atom (particularly a methoxy group or an ethoxy group), where M ⁵ , M ⁶ , M ⁹ and M ¹⁰ are all hydrogen atoms, f21 is 0 and f22 is 30 to 150 (more preferably 80 to 140). It is preferable that f25 is 30 to 60, f23 and f24 are 0, f27 and f29 are 0 or more and 1 or less (particularly 0), g2 and g3 are 3, and f26 and f28 are 1 to 10.

More specifically, the compound (A) includes a compound of the following formula (a3).

In the above formula (a3), R ³⁰ is a perfluoroalkyl group having 2 to 6 carbon atoms, and R ³¹ and R ³² are independently perfluoroalkylene groups having 2 to 6 carbon atoms. R ³³ is a trivalent saturated hydrocarbon group having 2 to 6 carbon atoms, and R ³⁴ is an alkyl group having 1 to 3 carbon atoms. The carbon atoms of R ³⁰ , R ³¹ , R ³² , and R ³³ are preferably 2 to 4 independently, and more preferably 2 to 3. h1 is 5 to 70, h2 is 1 to 5, and h3 is 1 to 10. h1 is preferably 10 to 60, more preferably 20 to 50, h2 is preferably 1 to 4, 1 to 3 is more preferable, h3 is preferably 1 to 8 and 1 to 6 is more preferable.

As the compound (A), a compound represented by the following formula (a4) can also be mentioned.

In the above formula (a4), R ⁴⁰ is a perfluoroalkyl group having 2 to 5 carbon atoms, R ⁴¹ is a perfluoroalkylene group having 2 to 5 carbon atoms, and R ⁴² is a perfluoroalkylene group having 2 to 5 carbon atoms. A fluoroalkylene group in which a part of the hydrogen atom of the alkylene group is substituted with fluorine, R ⁴³ and R ⁴⁴ are independently alkylene groups having 2 to 5 carbon atoms, and R ⁴⁵ is a methyl group or an ethyl group. be. k1, k2, and k3 are independently integers of 1 to 5.

2. 2. Second organosilicon compound (B)
The second organosilicon compound (B) is a compound having a hydrolyzable group bonded to a silicon atom and having no perfluoropolyether structure. Since the second organosilicon compound has a hydrolyzable group, it can undergo a condensation reaction with the hydrolyzable group of the first organosilicon compound (A) or with active hydrogen such as a hydroxyl group on the surface of the substrate. Examples of the hydrolyzable group include an alkoxy group (particularly an alkoxy group having 1 to 4 carbon atoms) or a halogen atom. Further, it is preferable that the second organosilicon compound (B) does not have a polyether structure.

Examples of the compound (B) include a compound represented by the following formula (b1).

In the above formula (b1),
Rf ^b10 is an alkyl group or a fluorine atom having 1 to 20 carbon atoms in which one or more hydrogen atoms are substituted with a fluorine atom.
R ^b11 , R ^b12 , R ^b13 , and R ^b14 are each independently an alkyl group having a hydrogen atom or 1 to 4 carbon atoms, and when a plurality of R ^b11s are present, the plurality of R ^b11s are different from each other. If there are a plurality of R ^b12s , the plurality of R ^b12s may be different, if there are a plurality of R ^b13s , the plurality of R ^b13s may be different, and if there are a plurality of R ^b14s . May have different R ^b14s ,
Rf ^b11 , Rf ^b12 , Rf ^b13 , and Rf ^b14 are independently alkyl groups or fluorine atoms having 1 to 20 carbon atoms in which one or more hydrogen atoms are substituted with fluorine atoms, and a plurality of Rf ^b11 are present. In this case, a plurality of Rf ^b11s may be different from each other, a plurality of Rf ^b12s may be different from each other when a plurality of Rf ^b12s are present, and a plurality of Rf ^b13s may be different from each other when a plurality of Rf ^b13s are present. If there are a plurality of Rf ^b14s , the plurality of Rf ^b14s may be different from each other.
R ^b15 is an alkyl group having 1 to 20 carbon atoms, and when a plurality of R ^b15s are present, the plurality of R ^b15s may be different from each other.
A ¹ is -O-, -C (= O) -O-, -OC (= O)-, -NR-, -NRC (= O)-, or -C (= O) NR-. Yes, the 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, and when a plurality of A ^1s are present, the plurality of A ^1s may be different from each other.
A ² is a hydrolyzable group, and when a plurality of A ^2s are present, the plurality of A ^2s may be different from each other.
b11, b12, b13, b14, and b15 are independently integers of 0 or more and 100 or less, respectively.
c is an integer of 1 or more and 3 or less,
Rf ^b10 -,-Si (A ² ) _c (R ^b15 ) _3-c , b11-{C (R ^b11 ) (R ^b12 )}-, b12- {C (Rf ^b11 ) (Rf ^b12 ) }-, B13-{Si (R ^b13 ) (R ^b14 )}-, b14-{Si (Rf ^b13 ) (Rf ^b14 )}-, b15 -A ^1- are Rf ^b10- , -Si (A ² ) _c (R ^b15 ) _3-c is the terminal, does not form a polysiloxane structure, does not form a perfluoropolyether structure, and -O- does not connect with -O- to -F. As long as they are combined side by side in any order.

Rf ^b10 is preferably a fluorine atom or a perfluoroalkyl group having 1 to 10 carbon atoms (more preferably 1 to 5 carbon atoms) independently of each other.
Hydrogen atoms are preferable for R ^b11 , R ^b12 , R ^b13 , and R ^b14 .
R ^b15 is preferably an alkyl group having 1 to 5 carbon atoms.
A ¹ is preferably —O—, —C (= O) —O—, or —OC (= O) −.
A ² is preferably an alkoxy group or a halogen atom having 1 to 4 carbon atoms, and more preferably a methoxy group, an ethoxy group or a chlorine atom.
b11 is preferably 1 to 30, more preferably 1 to 25, further preferably 1 to 10, particularly preferably 1 to 5, and most preferably 1 to 2.
b12 is preferably 0 to 15, more preferably 0 to 10.
b13 is preferably 0 to 5, more preferably 0 to 2.
b14 is preferably 0 to 4, more preferably 0 to 2.
b15 is preferably 0 to 4, more preferably 0 to 2.
c is preferably 2 to 3, more preferably 3.
The total value of b11, b12, b13, b14, and b15 is preferably 3 or more, preferably 5 or more, preferably 80 or less, more preferably 50 or less, and further preferably 20 or less.

In particular, Rf ^b10 is a fluorine atom or a perfluoroalkyl group having 1 to 5 carbon atoms, R ^b11 and R ^b12 are both hydrogen atoms, A ² is a methoxy group or an ethoxy group, and b11 is 1 to 1. 5, b12 is 0 to 5, b13, b14, and b15 are all 0, and c is preferably 3, and it is more preferable that both Rf ^b11 and Rf ^b12 are fluorine atoms.

In the examples described later, when FAS13E used as the compound (B) is represented by the above formula (b1), R ^b11 and R ^b12 are all hydrogen atoms, b11 is 2, b13, b14 and b15 are all 0. c is 3, A ² is an ethoxy group, Rf ^b10- {C (Rf ^b11 ) (Rf ^b12 )} _b12 -is the terminal, and C ₆ F ₁₃ -is defined (that is, Rf ^b11 and Rf ^b12 ). All are hydrogen atoms).

Specific examples of the compound represented by the above formula (b1) include CF ₃ -Si- (OCH ₃ ) ₃ , C _j F _{2j + 1} -Si- (OC ₂ H ₅ ) ₃ (j is 1 to 12). Integer), among which C ₄ F ₉ -Si- (OC ₂ H ₅ ) ₃ , C ₆ F ₁₃ -Si- (OC ₂ H ₅ ) ₃ , C ₇ F ₁₅ -Si- (OC) ₂ H ₅ ) ₃ and C ₈ F ₁₇ -Si- (OC ₂ H ₅ ) ₃ are preferable. Also, CF ₃ CH ₂ O (CH ₂ ) _k SiCl ₃ , CF ₃ CH ₂ O (CH ₂ ) _k Si (OCH ₃ ) ₃ , CF ₃ CH ₂ O (CH ₂ ) _k Si (OC ₂ H ₅ ) ₃ , CF ₃ (CH ₂ ) ₂ Si (CH ₃ ) ₂ (CH ₂ ) _k SiCl ₃ , CF ₃ (CH ₂ ) ₂ Si (CH ₃ ) ₂ (CH ₂ ) _k Si (OCH ₃ ) ₃ , CF ₃ ( CH ₂ ) ₂ Si (CH ₃ ) ₂ (CH ₂ ) _k Si (OC ₂ H ₅ ) ₃ , CF ₃ (CH ₂ ) ₆ Si (CH ₃ ) ₂ (CH ₂ ) _k SiCl ₃ , CF ₃ (CH ₂ ) ) ₆ Si (CH ₃ ) ₂ (CH ₂ ) _k Si (OCH ₃ ) ₃ , CF ₃ (CH ₂ ) ₆ Si (CH ₃ ) ₂ (CH ₂ ) _k Si (OC ₂ H ₅ ) ₃ , CF ₃ COO (CH ₂ ) _k SiCl ₃ , CF ₃ COO (CH ₂ ) _k Si (OCH ₃ ) ₃ , CF ₃ COO (CH ₂ ) _k Si (OC ₂ H ₅ ) ₃ (k is 5 to 20 in each case). It is preferably 8 to 15). In addition, CF ₃ (CF ₂ ) _m- (CH ₂ ) _n SiCl ₃ , CF ₃ (CF ₂ ) _m- (CH ₂ ) _n Si (OCH ₃ ) ₃ , CF ₃ (CF ₂ ) _m- (CH ₂ ) _n Si (OC ₂ H ₅ ) ₃ can also be mentioned (m is 1 to 10, preferably 3 to 7, and n is 1 to 5, preferably 2 to 4). ). CF ₃ (CF ₂ ) _p- (CH ₂ ) _q -Si- (CH ₂ CH = CH ₂ ) ₃ can also be mentioned (p is 2 to 10, preferably 2 to 8, q). Is 1 to 5, preferably 2 to 4). Furthermore, CF ₃ (CF ₂ ) _p- (CH ₂ ) _q SiCH ₃ Cl ₂ , CF ₃ (CF ₂ ) _p- (CH ₂ ) _q SiCH ₃ (OCH ₃ ) ₂ , CF ₃ (CF ₂ ) _p- ( CH ₂ ) _q SiCH ₃ (OC ₂ H ₅ ) ₂ (p is 2 to 10, preferably 3 to 7, and q is 1 to 5, preferably 2 to 4). be).

Among the compounds represented by the above formula (b1), the compound represented by the following formula (b1-2) is preferable.

In the above formula (b1-2), R ⁶⁰ is a perfluoroalkyl group having 3 to 8 carbon atoms, R ⁶¹ is an alkylene group having 1 to 5 carbon atoms, and R ⁶² is an alkyl group having 1 to 3 carbon atoms. Is. As the compound represented by the above formula (b1-2), it is also preferable to use a compound having a boiling point of 100 ° C. or higher (preferably 300 ° C. or lower).

Further, as the compound (B), a compound represented by the following formula (b2) can also be mentioned.

In the above formula (b2), X ¹ , X ² , X ³ , and X ⁴ are independently hydrolyzable groups, alkyl groups having 1 to 4 carbon atoms, or one or more hydrogen atoms are replaced with fluorine. Alkyl groups having 1 to 4 carbon atoms are used, and the three X ^1s may be different from each other, and the three X ^2s may be different from each other. When there are a plurality of X ^3s , each of them may be different. It may be different, and when there are multiple ^X4s , they may be different.
At least one of X ¹ , X ² , X ³ , and X ⁴ is a hydrolyzable group.
b21 is an integer of 0 or more and 100 or less.

Examples of the hydrolyzable group of X ¹ , X ² , X ³ and X ⁴ include an alkoxy group such as a methoxy group, an ethoxy group, a propoxy group and a butoxy group. It is preferable that all of X ¹ , X ² , X ³ , and X ⁴ are alkoxy groups, or at least one of X ¹ , X ² , X ³ , and X ⁴ has one or more hydrogen atoms substituted with fluorine. It is also preferable that the alkyl group has 1 to 4 carbon atoms.

Examples of the compound represented by the above formula (b2) include (H ₅ C ₂ O) ₃ -Si- (OSI (OC ₂ H ₅ ) ₂ ) ₄ OC ₂ H ₅ , (H ₃ CO) ₂ Si ( CH ₂ CH ₂ CF ₃ )-(OSI CH ₃ (CH ₂ CH ₂ CF ₃ )) ₄ -OCH ₃ and the like can be mentioned.

3. 3. Metallic compound As the metal compound, a compound of a metal element belonging to Group 13 of the periodic table is used. Examples of the metal element belonging to Group 13 of the periodic table include aluminum (Al), gallium (Ga), indium (In), thallium (Tl) and the like, and aluminum is preferable. The metal compound is preferably a complex of a metal element belonging to Group 13 of the periodic table, and more preferably a metal complex having a chelate ligand. As the metal compound belonging to Group 13 of the periodic table, an Al compound is preferable, and an Al complex is more preferable.

As an Al compound,
Aluminum inorganic compounds such as aluminum hydroxide and aluminum oxide;
Aluminum alcoholate such as aluminum secondary butoxide, aluminum trisacetylacetonate, aluminum bisethylacetate monoacetylacetonate, aluminumtrisethylacetate, aluminum diisopropyrate monosecondary butyrate, aluminum isopropylate, aluminum ethylate, aluminum ethyl Al complexes such as acetoacetate diisopropyrate, aluminum alkyl acetoacetate diisopropyrate, aluminum monoacetylacetonate bis (ethylacetacetate), aluminumtris (acetylacetonate), and cyclic aluminum oxide isopropylate are mentioned, among which aluminumtris. (Ethylacetacetate) is the most preferable.

Examples of the gallium compound include gallium inorganic compounds such as gallium hydroxide and gallium oxide; and Ga complexes such as tris (2,4-pentandionato) gallium (III).

Examples of the indium compound include indium inorganic compounds such as indium tin oxide; and In complexes such as tris (2,4-pentanedionato) indium (III).

The composition of the present invention may contain a first organosilicon compound (A), a second organosilicon compound (B), and a metal compound of Group 13 of the periodic table, and may also contain a fluorine-based solvent (C). preferable. As the fluorinated solvent (C), for example, a fluorinated ether solvent, a fluorinated amine solvent, a fluorinated hydrocarbon solvent (particularly a fluorinated aromatic solvent) and the like can be used, especially at a boiling point of 100 ° C. or higher. It is preferable to have. As the fluorinated ether solvent, a hydrofluoro ether such as a fluoroalkyl (particularly a perfluoroalkyl group having 2 to 6 carbon atoms) -alkyl (particularly a methyl group or an ethyl group) ether is preferable, and for example, ethyl nonafluorobutyl ether or ethyl nona. Fluoroisobutyl ether can be mentioned. Examples of the ethyl nonafluorobutyl ether or ethyl nonafluoroisobutyl ether include Novec® 7200 (manufactured by 3M, molecular weight of about 264, boiling point 76 ° C.). As the fluorinated amine-based solvent, an amine in which at least one hydrogen atom of ammonia is substituted with a fluoroalkyl group is preferable, and a third in which all hydrogen atoms of ammonia are substituted with a fluoroalkyl group (particularly a perfluoroalkyl group). Primary amines are preferred, and specific examples thereof include tris (heptafluoropropyl) amines, such as Florinate (registered trademark) FC-3283 (molecular weight: about 521, boiling point: 128 ° C.). Examples of the fluorinated hydrocarbon solvent include 1,3-bis (trifluoromethylbenzene) (boiling point: about 116 ° C.).

In addition to the above, the fluorocarbon solvent (C) includes hydrochlorofluorocarbons such as Asahiclean (registered trademark) AK225 (manufactured by Asahi Glass Co., Ltd.) and hydrofluorocarbons such as Asahiclean (registered trademark) AC2000 (manufactured by Asahi Glass Co., Ltd.). Can be used.

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

The total content of the first organosilicon compound (A) and the second organosilicon compound (B) in 100% by mass of the composition of the present invention is preferably 0.05% by mass or more, more preferably 0.08. It is 0% by mass or more, more preferably 0.10% by mass or more, preferably 10% by mass or less, more preferably 5% by mass or less, still more preferably 1% by mass or less. The mass ratio of the first organosilicon compound (A) to the second organosilicon compound (B) in the composition of the present invention is preferably 0.5 or more, more preferably 1.0 or more, and 4 It is preferably 0.0 or less, and more preferably 3.5 or less.

The ratio of the metal compound of the present invention is preferably 0.3 mol% or more, more preferably 0.5 mol% or more, still more preferably 0. It is 6 mol% or more, particularly preferably 1.0 mol% or more, most preferably 1.5 mol% or more, and preferably 6.0 mol% or less, more preferably 5.0 mol% or less. It is more preferably 4.5 mol% or less, further preferably 3.5 mol% or less, particularly preferably 3.0 mol% or less, and most preferably 2.5 mol% or less. The ratio of the above metal compound is determined from the amount of each substance of the metal compound, the compound (A) and the compound (B), and the formula "ratio of the metal compound (mol%) = metal compound / (compound (A) + compound". (B)) × 100 ”.

When the ratio of the metal compound is expressed by mass ratio, the ratio to the total of the compound (A) and the compound (B) is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, and further. It is preferably 0.4% by mass or more, particularly 0.5% by mass or more, preferably 2.0% by mass or less, more preferably 1.7% by mass or less, and further preferably 1.3% by mass. % Or less, particularly 1.2% by mass or less, most preferably 0.9% by mass or less. The mass ratio of the above metal compound is calculated from the mass of each of the metal compound, the compound (A) and the compound (B) by the formula “mass ratio of the metal compound (mass%) = metal compound / (compound (A) +). It can be calculated by "Compound (B)) x 100".

The metal compound is an Al complex, and the ratio of the metal complex to the total of the compound (A) and the compound (B) is preferably 0.6 to 5.0 mol% (preferably 0.2 to 1.8% by mass in terms of mass ratio). ), In particular, the ratio is preferably 1.4 mol% to 2.5 mol% (that is, 0.5 to 0.9% by mass).

The composition of the present invention contains a silanol condensation catalyst, an antioxidant, a rust inhibitor, an ultraviolet absorber, a light stabilizer, an antifungal agent, an antibacterial agent, an antistatic agent, and an antistatic agent, as long as the effects of the present invention are not impaired. It may contain various additives such as odorants, pigments, flame retardants, and antistatic agents.

The base material to which the composition of the present invention is applied is not particularly limited, and may be either an organic material or an inorganic material, but the surface is preferably a metal or an alloy. More preferably, a metal such as iron, silicon, copper, zinc, aluminum or an alloy containing these metals can be mentioned, and in particular, a base material which is iron or an iron alloy (particularly stainless steel represented by "SUS" in the JIS standard). In the case of a chrome-containing steel such as (preferably), the effect of excellent adhesion between the composition of the present invention and the base material can be maximized. Therefore, the present invention also includes a coating material provided with a film obtained by curing the composition of the present invention on the surface of iron or an iron alloy.

When the composition of the present invention is applied to a substrate, it is preferable to wash the substrate with an alkaline cleaning solution. As the alkaline cleaning solution, an aqueous sodium hydroxide solution may be used, and commercially available products such as Escreen W-3000L (manufactured by Sasaki Chemicals Co., Ltd.) and Escreen AL-13 (manufactured by Sasaki Chemicals Co., Ltd.) may be used. A detergent or a liquid containing thioglycolic acid may be used.

The base material may be subjected to an easy-adhesion treatment, and the easy-adhesion treatment may be applied after the first-stage cleaning. Examples of the easy-adhesion treatment include hydrophilization treatments such as corona treatment, plasma treatment, and ultraviolet treatment. Further, a primer treatment with a resin, a silane coupling agent, tetraalkoxysilane or the like may be performed, or a glass film such as polysilazane may be applied to the base material in advance.

Preferably, after washing the substrate, the composition of the present invention is applied and dried to form a film on the substrate. Examples of the method for applying the composition of the present invention include a dip coating method, a roll coating method, a bar coating method, a spin coating method, a spray coating method, a die coating method, a gravure coating method, and hand coating (soaking a cloth with a liquid). (Method of applying to the object), flushing (method of applying the liquid to the object as it is using a dropper, etc.), spraying (method of applying to the object using a sprayer), and the like. In particular, from the viewpoint of workability, the hand-painting, flushing, spraying, and spray-coating methods are preferable.

The conditions after the composition of the present invention is applied to the substrate are not particularly limited, and may be allowed to stand at room temperature in the air, for example, for 1 hour or more. In the present invention, the normal temperature is 5 ° C. or higher and 60 ° C. or lower. The production of the covering body of the present invention can be carried out particularly in the temperature range of 15 to 40 ° C. Then, it may be further heated and dried at a temperature of 50 to 300 ° C., preferably 100 to 200 ° C. for about 10 to 60 minutes.

The thickness of the film obtained from the composition of the present invention can be, for example, about 1 nm to 100 nm. It is preferably 5 nm or more and 100 nm or less. Further, the film obtained from the composition of the present invention has water repellency, and the contact angle measured at a liquid volume of 3 μL by the sessile drop method (analysis method: θ / 2 method) is, for example, 110 to 125 °. Degree. The sliding angle measured by the sliding method (analysis method: contact method) with a liquid volume of 6.0 μL and a sliding determination distance of 0.25 mm can be 50 ° or less, preferably 48 ° or less (although the lower limit is not limited). , About 30 °).

Hereinafter, the present invention will be described in more detail with reference to examples. The present invention is not limited by the following examples, and it is of course possible to carry out the present invention with appropriate modifications within a range that can be adapted to the above-mentioned purpose, and all of them are technical of the present invention. Included in the range.

Cleaning of Substrate Prior to preparing the composition for forming the film, the SUS substrate (stainless steel substrate) to which the composition was applied was washed as follows. First, the cloth was impregnated with an alkaline detergent and modified by wiping the surface of the SUS substrate, and then the substrate was allowed to stand for 30 minutes while the surface of the substrate was moistened with the alkaline detergent. Subsequently, the alkaline cleaning agent on the surface was washed away with running water and dried with air.

Example 1
The first organic silicon compound (A) is a compound represented by the following formula (1) (hereinafter, compound a), and the second organic silicon compound (B) is FAS13E (C ₆ F _{13 -} C ₂ H 4--. Si (OC ₂ H ₅ ) ₃ , boiling point 220 ° C., manufactured by Tokyo Kasei Kogyo Co., Ltd.) and FC-3283 (C ₉ F ₂₁ N, Florinate, manufactured by 3M) were mixed and stirred at room temperature for a predetermined time. After that, ALCH-TR-20 (manufactured by Kawaken Fine Chemical Co., Ltd., aluminum tris (ethylacetacetate)), which is an Al complex, is adjusted to 0.6 mol% with respect to the total amount of the compounds (A) and (B). The mixture was added dropwise, stirred for 10 seconds, and then allowed to stand for 15 minutes to obtain a film-forming solution. In the solution, the ratio of the compound (A) is 0.08% by mass, the ratio of the compound (B) is 0.05% by mass, and the ratio of the Al complex is the total of the compounds (A) and (B). It is 0.2% by mass. The obtained solution was applied onto SUS304 manufactured by Shiraimatsu Kikai Co., Ltd. treated by the above-mentioned base material cleaning method using a spray coater manufactured by Apiros Co., Ltd. Then, it was allowed to stand at room temperature for 3 hours to obtain a transparent film on a SUS substrate.

The compound a represented by the above formula (1) is synthesized by the method described in Synthesis Examples 1 and 2 of JP-A-2014-15609, where r is 43 and s is an integer of 1 to 6. The number average molecular weight is about 8000.

Example 2
The same as in Example 1 except that the ratio of the added Al complex was 1.4 mol% (that is, the mass ratio of the Al complex to the total of the compounds (A) and (B) was 0.5% by mass). A transparent film was obtained on the SUS substrate.

Example 3
The same as in Example 1 except that the ratio of the added Al complex was 2.5 mol% (that is, the mass ratio of the Al complex to the total of the compounds (A) and (B) was 0.9% by mass). A transparent film was obtained on the SUS substrate.

Example 4
The same as in Example 1 except that the ratio of the added Al complex was 4.2 mol% (that is, the mass ratio of the Al complex to the total of the compounds (A) and (B) was 1.4% by mass). A transparent film was obtained on the SUS substrate.

Example 5
The same as in Example 1 except that the ratio of the added Al complex was 5.0 mol% (that is, the mass ratio of the Al complex to the total of the compounds (A) and (B) was 1.8% by mass). A transparent film was obtained on the SUS substrate.

Comparative Example 1
A transparent film was obtained on the SUS substrate in the same manner as in Example 1 except that the metal complex was not added.

Comparative Example 2
Examples except that the ratio of the added Al complex was 2.5 mol% with respect to the compound (A) (that is, 0.9% by mass with respect to the compound (A)) without using the compound (B). In the same manner as in No. 1, a transparent film was obtained on the SUS substrate.

The following measurements were performed on the films obtained in the above Examples and Comparative Examples.

(1) Measurement of water contact angle Using a contact angle measuring device (DM700 manufactured by Kyowa Interface Science Co., Ltd.), the water contact angle was measured with a liquid volume of 3 μL by the sessile drop method (analysis method: θ / 2 method). ..

(2) Evaluation of adhesion between the film and the base material Using a scratch device equipped with an HB pencil with an eraser manufactured by Mitsubishi Pencil, a load of 500 g is applied with the eraser in contact with the film, and the sample is moved at 40 r / min for adhesion. A sex evaluation test was conducted. The contact angle was measured every time the eraser reciprocated 10 times in the film, and the number of times when the contact angle after the test fell below 100 ° was measured.

(3) Measurement of sliding angle Using DM700 manufactured by Kyowa Interface Science Co., Ltd., sliding method (analysis method: contact method, water droplet amount: 6.0 μm, tilt method: continuous tilt, slip detection: after slip, movement judgment: forward angle , Sliding judgment distance: 0.25 mm), the sliding angle of the film was measured.

The results are shown in Table 1.

From Table 1, in the film of Comparative Example 1 obtained by using the composition containing no compound (complex) of the metal of Group 13 of the periodic table, the number of adhesion tests was less than 10 times, and the compound (B). In the film of Comparative Example 2 obtained by using the composition not containing), the sliding angle was large. On the other hand, in Examples 1 to 5 in which the compound (B) was contained together with the compound (A) and the Al complex was further contained, the number of adhesion tests was 10 or more, and the adhesion between the film and the substrate was achieved. In addition to being excellent, the sliding angle was small and the sliding property was excellent.

The composition of the present invention can be applied to various members such as metal members, plastic members, ceramic members, and glass members, and in particular, members having a metal surface used for automobiles, cooking utensils, shelves, workbenches, tools, and the like. It is industrially useful because it can form a water-repellent film with high adhesion.

Claims (9)

A monovalent group having a perfluoropolyether structure, a first organosilicon compound (A) in which a hydrolyzable group is bonded to a silicon atom, and the like.
A second organosilicon compound (B) having a hydrolyzable group bonded to a silicon atom and having no perfluoropolyether structure,
A mixed composition of compounds having a metal element of Group 13 of the Periodic Table .
A mixed composition in which the first organosilicon compound (A) is a compound represented by the following formula (a3) or (a4) .

In the above formula (a3), R ³⁰ is a perfluoroalkyl group having 2 to 6 carbon atoms, and R ³¹ and R ³² are independently perfluoroalkylene groups having 2 to 6 carbon atoms. R ³³ is a trivalent saturated hydrocarbon group having 2 to 6 carbon atoms, R ³⁴ is an alkyl group having 1 to 3 carbon atoms, h1 is 5 to 70, and h2 is 1 to 5. , H3 is 1-10.

In the above formula (a4), R ⁴⁰ is a perfluoroalkyl group having 2 to 5 carbon atoms, R ⁴¹ is a perfluoroalkylene group having 2 to 5 carbon atoms, and R ⁴² is a perfluoroalkylene group having 2 to 5 carbon atoms. Part of the hydrogen atom of the alkylene group is a fluoroalkylene group substituted with fluorine, R ⁴³ and R ⁴⁴ are independently alkylene groups having 2 to 5 carbon atoms, and R ⁴⁵ is a methyl group or an ethyl group. Yes, k1, k2, and k3 are independently integers of 1 to 5. The mixed composition according to claim 1, wherein the compound having a metal element of Group 13 of the periodic table is a complex having a metal element of Group 13 of the periodic table. The mixed composition according to claim 1 or 2 , wherein the second organosilicon compound (B) contains a compound represented by the following formula (b1).

In the above formula (b1),
Rf ^b10 is an alkyl group or a fluorine atom having 1 to 20 carbon atoms in which one or more hydrogen atoms are substituted with a fluorine atom.
R ^b11 , R ^b12 , R ^b13 , and R ^b14 are each independently an alkyl group having a hydrogen atom or 1 to 4 carbon atoms, and when a plurality of R ^b11s are present, the plurality of R ^b11s are different from each other. If there are a plurality of R ^b12s , the plurality of R ^b12s may be different, if there are a plurality of R ^b13s , the plurality of R ^b13s may be different, and if there are a plurality of R ^b14s . May have different R ^b14s ,
Rf ^b11 , Rf ^b12 , Rf ^b13 , and Rf ^b14 are independently alkyl groups or fluorine atoms having 1 to 20 carbon atoms in which one or more hydrogen atoms are substituted with fluorine atoms, and a plurality of Rf ^b11 are present. In this case, a plurality of Rf ^b11s may be different from each other, a plurality of Rf ^b12s may be different from each other when a plurality of Rf ^b12s are present, and a plurality of Rf ^b13s may be different from each other when a plurality of Rf ^b13s are present. If there are a plurality of Rf ^b14s , the plurality of Rf ^b14s may be different from each other.
R ^b15 is an alkyl group having 1 to 20 carbon atoms, and when a plurality of R ^b15s are present, the plurality of R ^b15s may be different from each other.
A ¹ is -O-, -C (= O) -O-, -OC (= O)-, -NR-, -NRC (= O)-, or -C (= O) NR-. Yes, the 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, and when a plurality of A ^1s are present, the plurality of A ^1s may be different from each other.
A ² is a hydrolyzable group, and when a plurality of A ^2s are present, the plurality of A ^2s may be different from each other.
b11, b12, b13, b14, and b15 are independently integers of 0 or more and 100 or less, respectively.
c is an integer of 1 or more and 3 or less,
Rf ^b10 -,-Si (A ² ) _c (R ^b15 ) _3-c , b11-{C (R ^b11 ) (R ^b12 )}-, b12- {C (Rf ^b11 ) (Rf ^b12 ) }-, B13-{Si (R ^b13 ) (R ^b14 )}-, b14-{Si (Rf ^b13 ) (Rf ^b14 )}-, b15 -A ^1- are Rf ^b10- , -Si (A ² ) _c (R ^b15 ) _3-c is the terminal, does not form a polysiloxane structure, does not form a perfluoropolyether structure, and -O- does not connect with -O- to -F. As long as they are combined side by side in any order. The mixed composition according to any one of claims 1 to 3 , wherein the metal compound is an Al compound. The mixed composition according to claim 4 , wherein the metal compound is an Al complex. One of claims 1 to 5 , wherein the ratio of the compound of the metal to the total of the first organosilicon compound (A) and the second organosilicon compound (B) is 0.6 to 5.0 mol%. The mixed composition described. According to any one of claims 1 to 6 , wherein the ratio of the compound of the metal to the total of the first organosilicon compound (A) and the second organosilicon compound (B) is 0.1 to 2.0% by mass. The mixed composition described. A coating body comprising a film obtained by curing the mixed composition according to any one of claims 1 to 7 . The method for producing a coating body according to claim 8 , wherein the mixed composition is cured at room temperature.