WO2019203320A1 - Composition and article - Google Patents

Abstract

Provided are a composition with which it is possible to form a surface layer having excellent friction resistance and adhesiveness with respect to a protective film, and an article. A composition containing: at least one compound selected from the group consisting of compounds 1 represented by R¹¹-(OX)_m-Y-Z(R¹²)_q(R¹³)_r-q, and compounds 2 that have -Si(R²)_n2L² _3-n2 and a poly(oxyfluoroalkylene) chain including a unit represented by (OX²); and a compound 3 that has a poly(oxyfluoroalkylene) chain including a unit represented by (OX³)_m3, has two or more -Si(R³)_n3L³ _3-n3, and is free of repeating units represented by formula 21. R¹¹ is a fluoroalkyl group, X is an alkylene group having a fluorine atom, m is 0-4, Y is a single bond or a divalent linking group, X² is a fluoroalkylene group having a hydrogen atom, X³ is a perfluoroalkylene group, m3 is 5 or higher, and -Z(R¹²)_q(R¹³)_r-q, -Si(R²)_n2L² _3-n2, and -Si(R³)_n3L³ _3-n3 are groups having a hydrolyzable group.

Description

Compositions and articles

The present invention relates to a composition and an article that can form a surface layer excellent in friction resistance and adhesion.

Since the fluorine-containing compound exhibits high lubricity, water / oil repellency, etc., it is preferably used as a surface treatment agent. When the surface treatment agent imparts water and oil repellency to the surface of the base material, it becomes easy to wipe off the dirt on the surface of the base material, and the removability of the dirt is improved. Among the above-mentioned fluorine-containing compounds, fluorine-containing ether compounds having a poly (oxyperfluoroalkylene) chain in which an ether bond (—O—) is present in the middle of the perfluoroalkylene chain are compounds having excellent flexibility. Excellent dirt removal.

The surface treatment agent containing the above-mentioned fluorine-containing ether compound has the ability to prevent water and oil repellency from being lowered even when repeatedly rubbed with a finger (friction resistance) and the ability to easily remove fingerprints attached to the surface by wiping (fingerprint stains) For example, it is used as a surface treatment agent for a member constituting a surface touched by a finger of a touch panel.
As the fluorine-containing ether compound, compounds having a poly (oxyperfluoroalkylene) chain and having a hydrolyzable silyl group at the terminal are widely used. Among such compounds, Patent Document 1 shows that a fluorine-containing ale compound having a plurality of hydrolyzable silyl groups is preferable.

Japanese Unexamined Patent Publication No. 2016-037541

In order to protect the substrate on which the surface layer is formed, after forming the surface layer on the substrate using the surface treatment agent, until the substrate on which the surface layer is formed is used in the next step, A peelable protective film may be stuck on the surface layer.
Here, the surface treating agent containing a fluorine-containing ether compound having a plurality of hydrolyzable silyl groups described in Patent Document 1 can form a surface layer having excellent friction resistance. However, since the adhesion between the surface layer and the protective film is insufficient, when the protective film is peeled off from the surface layer during storage or transportation of the substrate on which the surface layer is formed, There was a case where trash entered a gap formed between the two.

In view of the above problems, an object of the present invention is to provide a composition and an article that can form a surface layer excellent in friction resistance and adhesion to a protective film.

The present invention achieves the above-mentioned object and has the following aspects.
[1] Selected from the group consisting of Compound 1 represented by Formula 1 and Compound 2 having a poly (oxyfluoroalkylene) chain containing a repeating unit represented by Formula 21 and a group represented by Formula 22 At least one compound
Compound 3 having a poly (oxyperfluoroalkylene) chain containing a repeating unit represented by formula 31 and two or more groups represented by formula 32, and not containing a repeating unit represented by formula 21; A composition comprising:
_{^{R 11 - (OX) m -Y}} -Z (R 12) q (R 13) r-q Formula 1
However, in Formula 1,
R ¹¹ is a fluoroalkyl group.
X is a fluoroalkylene group having 1 or more carbon atoms and having 1 or more fluorine atoms.
m is an integer of 0-4.
Y represents an alkylene group which may have —O—, —C (O) N (R ¹⁴ ) — or —C (O) —, a single bond, —O—, —C (O) N (R ¹⁴ )-or -C (O)-. The alkylene group that may have —O—, —C (O) N (R ¹⁴ ) —, or —C (O) — may have a fluorine atom. However, the Y is -OCF ₂ - when is an alkylene group containing, -OCF ₂ in the alkylene group - number of is one.
R ¹⁴ is a hydrogen atom or an alkyl group.
Z is a carbon atom, a silicon atom or a nitrogen atom.
R ¹² is a hydrogen atom, a hydroxyl group or an alkyl group.
R ¹³ is —L ¹ —Si (R ¹ ) _n1 L _3-n1 . R ¹ is a monovalent hydrocarbon group. L is a hydrolyzable group or a hydroxyl group. n1 is an integer of 0-2. L ¹ is an alkylene group which may have —O—.
When Z is a carbon atom or a silicon atom, r is 3 and q is an integer of 0 to 1. When Z is a nitrogen atom, r is 2 and q is 0.
(OX ² ) Formula 21
—Si (R ² ) _n2 L ² _3-n2 Formula 22
However, in Formula 21 and Formula 22,
X ² is a fluoroalkylene group having one or more hydrogen atoms.
R ² is a monovalent hydrocarbon group.
L ² is a hydrolyzable group or a hydroxyl group.
n2 is an integer of 0-2.
(OX ³ ) _m3 formula 31
—Si (R ³ ) _n3 L ³ _3-n3 Formula 32
However, in Formula 31 and Formula 32,
X ³ is a perfluoroalkylene group.
m3 is an integer of 5 or more.
R ³ is a monovalent hydrocarbon group.
L ³ is a hydrolyzable group or a hydroxyl group. n3 is an integer of 0-2.
[2] The composition according to [1], wherein m in the formula (1) is 0 or 1.
[3] The composition according to [1] or [2], wherein the compound 2 is a compound represented by the formula 2.
_{^{R 21 - [(OX 2)}} m2 (OX 21) m20] -Y 2 -Z 2 (R 22) q2 (R 23) r2-q2 formula 2
However, in Formula 2,
R ²¹ is an alkyl group which may have a fluorine atom, or —Y ² —Z ² (R ²² ) _q2 (R ²³ ) _r2-q2 .
X ² is a fluoroalkylene group having one or more hydrogen atoms.
X ²¹ is a perfluoroalkylene group.
Y ² is a single bond or a divalent linking group.
Z ² is a carbon atom, a silicon atom or a nitrogen atom.
R ²² is a hydrogen atom, a hydroxyl group or an alkyl group.
R ²³ is —L ²¹ —Si (R ² ) _n2 L ² _3-n2 . L ²¹ is an alkylene group which may have —O—. R ² is a monovalent hydrocarbon group. L ² is a hydrolyzable group or a hydroxyl group. n2 is an integer of 0-2.
m2 is an integer of 2 or more, m20 is an integer of 0 or more, and m2 + m20 is an integer of 5 or more.
If Z ² is a carbon atom or a silicon atom, r2 is 3, q2 is an integer of 0-2. If Z ² is a nitrogen atom, r2 is 2, q2 is an integer of 0-1.
[4] The composition according to any one of [1] to [3], wherein the compound 3 is a compound represented by formula 3.
[A- (OX ³ ) _m3 −] _j Z ³ [—Si (R ³ ) _n3 L ³ _3-n3 ] _g Formula 3
However, in the formula:
A is a perfluoroalkyl group or —Q [—Si (R ³ ) _n3 L ³ _3-n3 ] _k .
Q is a (k + 1) -valent linking group.
k is an integer of 1 to 10.
R ³ is a monovalent hydrocarbon group.
L ³ is a hydrolyzable group or a hydroxyl group. n3 is an integer of 0-2.
X ³ is a perfluoroalkylene group.
m3 is an integer of 5 or more.
Z ³ is a (j + g) -valent linking group.
j is an integer of 1 or more.
g is an integer of 1 or more. However, when A is a perfluoroalkyl group, g is an integer of 2 or more, and when A is —Q [—Si (R ³ ) _n3 L ³ _3-n3 ] _k , g + k is an integer of 2 or more. is there.
[5] The difference in number average molecular weight between at least one compound selected from the group consisting of the compound 1 and the compound 2 and the compound 3 is 0 to 3,000, [1] to [4] A composition according to any one of the above.
[6] The composition according to any one of [1] to [5], wherein the content of the compound 3 relative to the total content of the compound 1 and the compound 2 is 0.1 to 4 by mass ratio. object.
[7] The composition according to any one of [1] to [6], comprising a fluorinated organic solvent, a non-fluorinated organic solvent, or a liquid medium containing water.
[8] An article comprising a substrate and a surface layer formed from the composition according to any one of [1] to [7] on the substrate.
[9] The article according to [8], which is formed from the composition by a dry coating method.
[10] The article according to [8] or [9], wherein the substrate is metal, resin, glass, sapphire, ceramic, stone, or a composite material thereof.
[11] The article according to any one of [8] to [10], wherein the film thickness of the surface layer is 1 to 100 nm.
[12] The article according to any one of [8] to [11], wherein a protective film is adhered to the surface of the surface layer.

According to the present invention, it is possible to provide a composition and an article that have a friction resistance and can form a surface layer having excellent adhesion to a substrate and a protective film.

The meanings of terms in this specification and how to describe them are as follows.
“Repeating unit represented by Formula 21” will be referred to as unit 21. Repeating units represented by other formulas are also described accordingly.
The “group represented by the formula 22” is referred to as a group 22. Groups represented by other formulas are also described in the same manner.
When "an alkylene group may have an A group" is mentioned, the alkylene group may have an A group between carbon-carbon atoms in the alkylene group, or an alkylene group-A group- May have an A group at its terminal.

The “divalent organopolysiloxane residue” is a group represented by the following formula. R ^x in the following formula is an alkyl group (preferably having 1 to 10 carbon atoms) or a phenyl group. G1 is an integer of 1 or more, preferably an integer of 1 to 9, and particularly preferably an integer of 1 to 4.

The “silphenylene skeleton group” is a group represented by —Si (R ^y ) ₂ PhSi (R ^y ) ₂ — (where Ph is a phenylene group and R ^y is a monovalent organic group). It is. R ^y is preferably an alkyl group (preferably having 1 to 10 carbon atoms).
The “dialkylsilylene group” is a group represented by —Si (R ^z ) ₂ — (wherein R ^z is an alkyl group (preferably having 1 to 10 carbon atoms)).
“Surface layer” means a layer formed on a substrate. In addition, a surface layer may be directly formed on a base material, and may be formed on a base material through the other layer formed on the surface of the base material.
“Number average molecular weight (hereinafter also referred to as Mn)” is calculated by determining the number (average value) of oxyfluoroalkylene groups based on terminal groups by ¹ H-NMR and ¹⁹ F-NMR.

The hydrolyzable silyl group means a group that becomes a silanol group represented by Si—OH by a hydrolysis reaction. Silanol groups react between the silanol groups to form Si—O—Si bonds. In addition, it is considered that the silanol group can form a chemical bond (base material—O—Si) by a dehydration condensation reaction with a hydroxyl group (base material—OH) on the surface of the base material. The hydrolyzable silyl group is, for example, —Si (R ¹ ) _n1 L _3-n1 in Compound 1.

〔Composition〕
The composition of the present invention (hereinafter also referred to as “the present composition”) is composed of Compound 1 represented by Formula 1 and Compound 2 having a poly (oxyfluoroalkylene) chain containing unit 21 and a group 22. And at least one compound selected from the group, and a compound 3 having a poly (oxyperfluoroalkylene) chain containing the unit 31 and two or more groups 32 and not containing the unit 21.
The surface layer formed using this composition is excellent in friction resistance. The reason for this is presumed that by using Compound 3 having two or more groups 32, the reaction point between the present composition and the substrate increased, and the adhesion between the surface layer and the substrate was improved. Is done.

Moreover, the surface layer formed using this composition is excellent in adhesiveness with a protective film. The reason for this is thought to be that the number of repeating units (m) of the oxyfluoroalkylene chain represented by (OX) in Compound 1 is as small as 0 to 4, thereby improving the affinity with the adhesive of the protective film. It is done. In addition, since the compound 2 has a poly (oxyfluoroalkylene) chain containing the unit 21 having a hydrogen atom, the surface tension is increased as compared with a case where a poly (oxyfluoroalkylene) chain having no hydrogen atom is used. It is thought that it was because.

Examples of the protective film include a resin film with an adhesive. Examples of the pressure-sensitive adhesive include acrylic pressure-sensitive adhesives, urethane pressure-sensitive adhesives, and silicone-based pressure-sensitive adhesives, and acrylic pressure-sensitive adhesives are preferable from the viewpoint of easy peeling. Examples of the resin film include a polyvinyl chloride film, a polyethylene film, a polypropylene film, a polycarbonate film, a polyester film, and a polyurethane film. From the viewpoint of easy peeling, a polyvinyl chloride film, a polyethylene film or a polypropylene film is preferred.

(Compound 1)
Compound 1 is represented by Formula 1.
_{^{R 11 - (OX) m -Y}} -Z (R 12) q (R 13) r-q Formula 1
R ¹¹ is a fluoroalkyl group (an alkyl group having one or more fluorine atoms), and is preferably a perfluoroalkyl group.
The number of carbon atoms in the fluoroalkyl group is preferably from 1 to 20, more preferably from 1 to 10, even more preferably from 1 to 6, and particularly preferably from 1 to 3 from the viewpoint of better weather resistance and corrosion resistance of the surface layer. The fluoroalkyl group may be linear, branched or cyclic.

X is a fluoroalkylene group having 1 or more carbon atoms and having 1 or more fluorine atoms.
The number of carbon atoms of the fluoroalkylene group is 1 or more, preferably 2 or more, more preferably 2 to 6, and particularly preferably 2 to 3 from the viewpoint of better weather resistance and corrosion resistance of the surface layer.
The fluoroalkylene group may be linear or branched, but is preferably linear because the effects of the present invention are more excellent.
The fluoroalkylene group has one or more fluorine atoms. The number of fluorine atoms in the fluoroalkylene group is preferably 2 to 10 and particularly preferably 2 to 4 in view of better corrosion resistance of the surface layer.
The fluoroalkylene group may be a group in which all hydrogen atoms in the fluoroalkylene group are substituted with fluorine atoms (perfluoroalkylene group).

Specific examples of (OX) include OCHF, OCF ₂ , OCHFCF ₂ , OCF ₂ CF ₂ , and OCF (CF ₃ ) CF ₂ .

m is an integer of 0 to 4, and is preferably 0 to 3, more preferably 0 or 1, from the viewpoint of excellent balance between the adhesion of the surface layer to the protective film and the friction resistance of the surface layer.
When m is 0, (OX) _m is a single bond.

When m is 2 or more, the plurality of OXs may be the same or different. That is, (OX) _m may be composed of two or more different types of OX. The order of combining two or more types of (OX) is not limited, and they may be arranged randomly, alternately, or in blocks.

Y represents an alkylene group which may have —O—, —C (O) N (R ¹⁴ ) — or —C (O) —, a single bond, —O—, —C (O) N (R ¹⁴ )-or -C (O)-.
When the alkylene group has —O—, —C (O) N (R ¹⁴ ) —, or —C (O) —, these groups are attached to at least one of the carbon-carbon atom and (OX) _m- side ends. It is preferable to have.
The alkylene group may have a plurality of groups selected from the group consisting of —O—, —C (O) N (R ¹⁴ ) —, and —C (O) —. When the alkylene group has a plurality of groups selected from the group consisting of —O—, —C (O) N (R ¹⁴ ) —, and —C (O) —, the carbon-carbon atom and (OX) _m side It is preferable to have these groups at both ends.
The alkylene group which may have —O—, —C (O) N (R ¹⁴ ) — or —C (O) — preferably has 1 to 10 carbon atoms, particularly preferably 1 to 6.
The alkylene group which may have —O—, —C (O) N (R ¹⁴ ) — or —C (O) — may have a fluorine atom. That is, the hydrogen atom in the alkylene group may be substituted with a fluorine atom.
R ¹⁴ is a hydrogen atom or an alkyl group (preferably having 1 to 10 carbon atoms).
Here, Y is -OCF ₂ - when is an alkylene group containing, -OCF ₂ in the alkylene group - number of is one. For example, an alkylene group represented by —OCF ₂ —, an alkylene group represented by —OCF ₂ CH ₂ OCH ₂ CH ₂ CH ₂ —, and an alkylene group represented by —OCF ₂ C (O) NHCH ₂ — However, the number of —OCF ₂ — is one and satisfies the definition of Y. On the other hand, an alkylene group having two or more —OCF ₂ — such as an alkylene group represented by —OCF ₂ OCF ₂ — and an alkylene group represented by —OCF ₂ OCF ₂ OCF ₂ — Does not meet the definition of
Specific examples of the alkylene group which may have —O—, —C (O) N (R ⁴ ) —, or —C (O) — include —CH ₂ CH ₂ —, —C (O) NHCH. ₂ —, —C (O) N (CH ₃ ) CH ₂ —, —OCF ₂ C (O) NHCH ₂ —, —OCH ₂ —, —OCF ₂ —, —CH ₂ OCH ₂ CH ₂ CH ₂ —, OCF ₂ CH ₂ OCH ₂ CH ₂ CH ₂ —, —CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ —.

Z is a carbon atom, a nitrogen atom or a silicon atom.
When Z is a carbon atom or a silicon atom, r is 3, and q is an integer of 0 to 1 (preferably 0). When Z is a nitrogen atom, r is 2 and q is 0.

R ¹² is a hydrogen atom, a hydroxyl group or an alkyl group.
The alkyl group preferably has 1 to 5 carbon atoms, more preferably 1 to 3 carbon atoms, and particularly preferably 1 carbon atom.

R ¹³ is —L ¹ —Si (R ¹ ) _n1 L _3-n1 .
L ¹ is an alkylene group which may have —O—.
When the alkylene group has —O—, it is preferable to have —O— between carbon-carbon atoms or at the terminal on the Z side.
L ¹ preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and particularly preferably 1 to 4 carbon atoms.
When there are a plurality of R ¹³ in one molecule, the plurality of R ¹³ may be the same or different. From the viewpoint of easy availability of raw materials and ease of production of Compound 1, they are preferably the same.

R ¹ is a monovalent hydrocarbon group, preferably a monovalent saturated hydrocarbon group. The carbon number of R ¹ is preferably 1 to 6, more preferably 1 to 3, and particularly preferably 1 or 2.

L is a hydrolyzable group or a hydroxyl group. That is, when L is a hydrolyzable group, the group represented by Si—L is a hydrolyzable silyl group.

Specific examples of L include an alkoxy group, a halogen atom, an acyl group, and an isocyanate group (—NCO). As the alkoxy group, an alkoxy group having 1 to 4 carbon atoms is preferable. As the halogen atom, a chlorine atom is preferable.
L is preferably an alkoxy group having 1 to 4 carbon atoms or a halogen atom from the viewpoint of easier production of compound 1. L is preferably an alkoxy group having 1 to 4 carbon atoms from the viewpoint of less outgassing at the time of coating and better storage stability of Compound 1, and an ethoxy group when long-term storage stability of Compound 1 is required. Is particularly preferred, and a methoxy group is particularly preferred when the reaction time after coating is short.

n1 is an integer of 0-2.
n1 is preferably 0 or 1, particularly preferably 0. By the presence of a plurality of L, the adhesion of the surface layer to the substrate becomes stronger.
When n1 is 1 or less, a plurality of L present in one molecule may be the same or different. From the viewpoint of easy availability of raw materials and ease of production of Compound 1, they are preferably the same.

Specific examples of compound 1 include the following examples 1 to 48.

Compound 1 can be produced by a known production method. For example, Compound 1 can be produced by subjecting a compound represented by Formula 1A to a hydrosilylation reaction with HSi (R ¹ ) _n1 L _3-n1 (wherein R ¹ , L and n1 are as defined above). .
R ¹¹ — (OX) _m —YZ (R ¹² ) _q (L ^1A —CH═CH ₂ ) _rq Formula 1A
In the formula, the definitions of R ¹¹ , X, m, Y, Z, R ¹² , q, and r are as described above, and L ^1A is an alkylene group that may have —O—, a single bond, or —O When L ^1A —CH═CH ₂ is hydrosilylated, it becomes L ^{1 of} Compound 1. Compounds of the formula 1A, for example Y is -C (O) NHCH ₂ - ^For, R 11 -OH ^(. The definition of ^{R 11} are as described above) ^{R 11} in a known manner as a raw material - (OX) _m —C (O) OR ^1B (R ^1B is an alkyl group having 1 to 6 carbon atoms) was obtained, and NH ₂ —CH ₂ —Z (R ¹² ) _q (L ^1A —CH═CH ₂ ) _It can be produced by reacting with _rq .

(Compound 2)
Compound 2 has a poly (oxyfluoroalkylene) chain containing units 21.
(OX ² ) Formula 21
X ² is a fluoroalkylene group having one or more hydrogen atoms.
The carbon number of the fluoroalkylene group is preferably 1-6, and particularly preferably 2-4.
The fluoroalkylene group has one or more hydrogen atoms, preferably 1 to 3 in terms of excellent balance between the adhesion of the surface layer to the protective film and the friction resistance of the surface layer, and 1 or 2 Particularly preferred.

A fluoroalkylene group has one or more fluorine atoms. The fluoroalkylene group has one or more fluorine atoms, preferably 1 to 11 in terms of excellent balance between the adhesion of the surface layer to the protective film and the friction resistance of the surface layer, preferably 2 to 7 Particularly preferred.
X ² may be linear or branched, and is preferably linear because the surface layer is more excellent in friction resistance.

Specific examples of the unit _{21, OCHF, -OCF 2 CHF -} , - OCHFCF 2 -, - OCF 2 CH 2 -, - OCH 2 CF 2 -, - OCF 2 CF 2 CHF -, - OCHFCF 2 CF 2 -, _{-OCF 2 CF 2 CH 2 -,} - OCH 2 CF 2 CF 2 -, - OCF 2 CF 2 CF 2 CH 2 -, - OCH 2 CF 2 CF 2 CF 2 -, - OCF 2 CF 2 CF 2 CF 2 CH ₂ —, —OCH ₂ CF ₂ CF ₂ CF ₂ CF ₂ —, —OCF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CH ₂ —, and —OCH ₂ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ —.

The number m2 of repeating units 21 contained in the poly (oxyfluoroalkylene) chain is preferably an integer of 2 or more, more preferably an integer of 2 to 200, still more preferably an integer of 5 to 150, and an integer of 5 to 100. Particularly preferred is an integer of 10 to 50.

The poly (oxyfluoroalkylene) chain may contain only one type of unit 21 or may contain two or more types of units 21.
Examples of the two or more types of units 21 include two or more types of units 21 having different carbon numbers, two or more types of units 21 having different numbers of hydrogen atoms, and the presence or absence of side chains or side chains even if the number of carbons is the same. Two or more types of units 21 having different types may be mentioned.
The coupling order of the two or more types of units 21 is not limited, and they may be arranged randomly, alternately, or in blocks.

The (OX ² ) _m2 possessed by the poly (oxyfluoroalkylene) chain is (OCHF) _m21 (OC ₂ H _ma F _(4-ma) ) _m22 (OC ₃ H _mb F _(6-mb) ) _m23 (OC _{4 H mc F (8-mc)} ) m24 (OC 5 H md F (10-md)) m25 (OC 6 H me F (12-me)) m26 is preferred.
ma is an integer of 1 to 3, mb is an integer of 1 to 5, mc is an integer of 1 to 7, md is an integer of 1 to 9, and me is an integer of 1 to 11.
m21, m22, m23, m24, m25 and m26 are each independently an integer of 0 or more, preferably 100 or less.
m21 + m22 + m23 + m24 + m25 + m26 is an integer of 2 or more, more preferably an integer of 2 to 200, more preferably an integer of 5 to 150, still more preferably an integer of 5 to 100, and particularly preferably an integer of 10 to 50.
Among these, m22 is preferably an integer of 1 or more, and particularly preferably an integer of 2 to 200, from the viewpoint that the solubility of Compound 2 in a non-fluorine organic solvent is more excellent.
C ₃ H _mb F _(6-mb) , C ₄ H _mc F _(8-mc) , C ₅ H _md F _(10-md) and C ₆ H _me F _(12-me) are linear It may be a branched chain, and a straight chain is preferable from the viewpoint that the friction resistance of the surface layer is more excellent.

It should be noted that m21 (OCHF), m22 (OC ₂ H _ma F _(4-ma) ), m23 (OC ₃ H _mb F _(6-mb) ), m24 (OC ₄ H _mc F _(8-mc) ), m25 (OC ₅ H _md F _(10-md) ), m26 (OC ₆ H _me F _(12-me) ) are not limited in the joining order.
When m21 is 2 or more, a plurality of (OCHF) may be the same or different.
When m22 is 2 or more, a plurality of (OC ₂ H _ma F _(4-ma) ) may be the same or different.
When m23 is 2 or more, a plurality of (OC ₃ H _mb F _(6-mb) ) may be the same or different.
When m24 is 2 or more, the plurality of (OC ₄ H _mc F _(8-mc) ) may be the same or different.
When m25 is 2 or more, a plurality of (OC ₅ H _md F _(10-md) ) may be the same or different.
When m26 is 2 or more, a plurality of (OC ₆ H _me F _(12-me) ) may be the same or different.

Among these, the following (1) to (4) are preferable as the (OX ² ) _m2 of the poly (oxyfluoroalkylene) chain in that the solubility of the compound 2 in the non-fluorine organic solvent is more excellent.
(1) (OC ₂ H _ma F _(4-ma) ) _m22 (OC ₃ H _mb F _(6-mb) ) _m23
(2) (OC ₂ H _ma F _(4-ma) ) _m22 (OC ₄ H _mc F _(8-mc) ) _m24
(3) (OC ₂ H _ma F _(4-ma) ) _m22 (OC ₅ H _md F _(10-md) ) _m25
(4) (OC ₂ H _ma F _(4-ma) ) _m22 (OC ₆ H _me F _(12-me) ) _m26
The above (1) corresponds to an embodiment in which m21, m24, m25 and m26 are 0, and m22 + m23 is an integer of 2 or more. The above (2) corresponds to an embodiment in which m21, m23, m25 and m26 are 0, and m22 + m24 is an integer of 2 or more. The above (3) corresponds to an embodiment in which m21, m23, m24 and m26 are 0, and m22 + m25 is an integer of 2 or more. The above (4) corresponds to an embodiment in which m21, m23, m24 and m25 are 0, and m22 + m26 is an integer of 2 or more.

In addition to the unit 21, the poly (oxyfluoroalkylene) chain may further contain an oxyperfluoroalkylene unit.
Specifically, the poly (oxyfluoroalkylene) chain may include units 23.
(OX ²¹ ) Formula 23
X ²¹ is a perfluoroalkylene group. The perfluoroalkylene group preferably has 1 to 6 carbon atoms.

The perfluoroalkylene group may be linear or branched, and is preferably linear because the surface layer is more excellent in friction resistance.

The poly (oxyfluoroalkylene) chain may contain only one type of unit 23, or may contain two or more types of unit 23.
Examples of the two or more types of units 23 include two or more types of units 23 having different carbon numbers, and two or more types of units 23 having the same number of carbons but having different side chains and different types of side chains. .

Specific examples of the unit _{23, -OCF 2 -, - OCF} 2 CF 2 -, - OCF 2 CF 2 CF 2 -, - OCF (CF 3) CF 2 -, - OCF 2 CF 2 CF 2 CF 2 -, —OCF (CF ₃ ) CF ₂ CF ₂ —, —OCF ₂ CF ₂ CF ₂ CF ₂ CF ₂ —, —OCF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ — may be mentioned.

The repeating number m20 of the unit 23 contained in the poly (oxyfluoroalkylene) chain is an integer of 0 or more, preferably an integer of 0 to 200, more preferably an integer of 0 to 50, and further an integer of 0 to 10 An integer of 0 to 2 is preferable, and particularly preferable.

When the poly (oxyfluoroalkylene) chain includes the unit 21 and the unit 23, the bonding order of the unit 21 and the unit 23 is not limited. For example, the units 21 and 23 may be arranged randomly, alternately, or in blocks.
When the poly (oxyfluoroalkylene) chain contains m2 units 21 and m20 units 23, m2 + m20 is an integer of 5 or more, preferably an integer of 5 to 400, more preferably an integer of 5 to 200 An integer of 5 to 120 is more preferable, and an integer of 10 to 52 is particularly preferable.

Compound 2 has a group 22.
—Si (R ² ) _n2 L ² _3-n2 Formula 22
The number of the groups 22 contained in the compound 2 is 1 or more, preferably 2 or more, more preferably 2 to 10, more preferably 2 to 5, in terms of more excellent friction resistance of the surface layer. Two or three are particularly preferred.
When there are a plurality of groups 22 in one molecule, the plurality of groups 22 may be the same or different. From the viewpoint of easy availability of raw materials and ease of production of Compound 2, it is preferable that they are the same.

R ² is a monovalent hydrocarbon group, preferably a monovalent saturated hydrocarbon group. R ² preferably has 1 to 6 carbon atoms, more preferably 1 to 3, and particularly preferably 1 or 2.
L ² is a hydrolyzable group or a hydroxyl group. That is, when L ² is a hydrolyzable group, the group represented by Si—L ² is a hydrolyzable silyl group.

Specific examples of L ² include an alkoxy group, a halogen atom, an acyl group, and an isocyanate group (—NCO). As the alkoxy group, an alkoxy group having 1 to 4 carbon atoms is preferable. As the halogen atom, a chlorine atom is preferable.
L ² is preferably an alkoxy group having 1 to 4 carbon atoms or a halogen atom from the viewpoint that the production of compound 2 is easier. L ² is preferably an alkoxy group having 1 to 4 carbon atoms from the viewpoint of less outgassing at the time of coating and better storage stability of compound 2, and ethoxy when long-term storage stability of compound 2 is required. A group is particularly preferred, and a methoxy group is particularly preferred when the reaction time after coating is short.

n2 is an integer of 0-2.
n2 is preferably 0 or 1, particularly preferably 0. The presence of a plurality of L ² makes the adhesion of the surface layer to the substrate stronger.
When n2 is 1 or less, a plurality of L ² present in one molecule may be the same or different. From the viewpoint of easy availability of raw materials and ease of production of Compound 2, it is preferable that they are the same. When n2 is 2, a plurality of R ² present in one molecule may be the same or different. From the viewpoint of easy availability of raw materials and ease of production of Compound 2, it is preferable that they are the same.

Note that a compound corresponding to both compound 1 and compound 2 is treated as corresponding to only one of compound 1 or compound 2.

The compound 2 is preferably a compound represented by the formula 2 in that it is superior in the adhesion of the surface layer to the protective film of the compound 2 and the friction resistance of the surface layer.
_{^{R 21 - [(OX 2)}} m2 (OX 21) m20] -Y 2 -Z 2 (R 22) q2 (R 23) r2-q2 formula 2

R ²¹ is an alkyl group which may have a fluorine atom, or —Y ² —Z ² (R ²² ) _q2 (R ²³ ) _r2-q2 . The definitions of Y ² , Z ² , R ¹ , R ²³ , r2 and q2 are as described later.
The number of carbon atoms in the alkyl group which may have a fluorine atom is preferably from 1 to 20, more preferably from 1 to 10, in terms of excellent adhesion of the surface layer to the protective film and friction resistance of the surface layer. 1 to 6 is more preferable, and 1 to 3 is particularly preferable.
The alkyl group which may have a fluorine atom may be linear or branched, and is preferably linear because the surface layer is more excellent in friction resistance.
The alkyl group which may have a fluorine atom may be a group (perfluoroalkyl group) in which all hydrogen atoms in the alkyl group are substituted with fluorine atoms.

Specific examples of the alkyl group which may have a fluorine atom include CH ₃ —, CF ₃ —, CF ₃ CH ₂ —, CF ₃ CF ₂ —, CF ₃ CF ₂ CF ₂ —, (CF ₃ ) _2. CH—, CF ₃ CF ₂ CF ₂ CF ₂ CH ₂ CH ₂ —, and CF ₃ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CH ₂ CH ₂ —.

The group represented by [(OX ² ) _m2 (OX ²¹ ) _m20 ] is a poly (oxyfluoroalkylene) chain.
The definitions of X ² , X ²¹ , m2 and m20 are as described above. However, m2 + m20 in Formula 2 is an integer of 5 or more, preferably an integer of 5 to 400, more preferably an integer of 5 to 200, still more preferably an integer of 5 to 120, and particularly preferably an integer of 10 to 52.
In [(OX ² ) _m2 (OX ²¹ ) _m20 ], the bonding order of (OX ² ) and (OX ²¹ ) is not limited. For example, (OX ² ) and (OX ²¹ ) may be arranged randomly, alternately, or in blocks.
The plurality of (OX ² ) may be the same or different. That is, (OX ² ) _m2 may be composed of two or more types of (OX ² ) with different X ² . The order of combining two or more types of (OX ² ) is not limited, and they may be arranged randomly, alternately, or in blocks.
Furthermore, when m20 is 2 or more, the plurality of (OX ²¹ ) may be the same or different. That is, (OX ²¹ ) _m20 may be composed of two or more types of (OX ²¹ ) with different X ²¹ . The order of combining two or more types of (OX ²¹ ) is not limited, and they may be arranged randomly, alternately, or in blocks.

As the group represented by [(OX ² ) _m2 (OX ²¹ ) _m20 ], [(OCHF) _m21 (OC ₂ H _ma F _(4-ma) ) _m22 (OC ₃ H _mb F _(6-mb) ) _{m23 (OC 4 H mc F (} 8-mc)) m24 (OC 5 H md F (10-md)) m25 (OC 6 H me F (12-me)) m26 (OX 21) m20] are preferred.
The definitions of m21, m22, m23, m24, m25, m26, ma, mb, mc, md, and me are as described above.

Y ² is a single bond or a divalent linking group.
Examples of the divalent linking group include a divalent hydrocarbon group (a divalent saturated hydrocarbon group, a divalent aromatic hydrocarbon group, an alkenylene group, and an alkynylene group. A divalent saturated carbonization group. The hydrogen group may be linear, branched or cyclic and includes, for example, an alkylene group, preferably 1 to 20, more preferably 1 to 10, and particularly preferably 1 to 6. In addition, the divalent aromatic hydrocarbon group preferably has 5 to 20 carbon atoms, and examples thereof include a phenylene group, other than that, an alkenylene group having 2 to 20 carbon atoms, and an alkynylene group having 2 to 20 carbon atoms. A divalent heterocyclic group, —O—, —S—, —SO ₂ —, —N (R ²⁴ ) —, —C (O) —, —Si (R ²⁵ ) ₂ -And a group obtained by combining two or more of these. R ²⁴ is a hydrogen atom or an alkyl group (preferably having 1 to 10 carbon atoms). R ²⁵ is an alkyl group (preferably having 1 to 10 carbon atoms) or a phenyl group.
Examples of the group in which two or more of these are combined include, for example, —C (O) N (R ²⁴ ) —, —C (O) N (R ²⁴ ) -alkylene group—, —O-alkylene group—, -OC (O)-is mentioned.

Among these, Y ² is a single bond, —O—, —C (O) —, —C (O) N (R ²⁴ ) —, —C (O) because compound 2 is easier to synthesize. N (R ²⁴ ) -alkylene group- and -O-alkylene group- are preferred.

Z ² is a carbon atom, a nitrogen atom or a silicon atom.

R ²² is a hydrogen atom, a hydroxyl group or an alkyl group.
The alkyl group preferably has 1 to 5 carbon atoms, more preferably 1 to 3 carbon atoms, and particularly preferably 1 carbon atom.
If q2 is 2, two is R ²² may be different even in the same. From the viewpoint of easy availability of raw materials and ease of production of the compound represented by Formula 2, they are preferably the same as each other.

R ²³ is —L ²¹ —Si (R ² ) _n2 L ² _3-n2 .
The definitions of R ² , L ² and n2 are as described above.
L ²¹ is an alkylene group which may have —O—.
When the alkylene group has —O—, it is preferable to have —O— between carbon-carbon atoms or at the terminal on the Z ² side.
L ²¹ preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and particularly preferably 1 to 4 carbon atoms.

If Z ² is a carbon atom or a silicon atom, r2 is 3, q2 is an integer of 0-2. If Z ² is a nitrogen atom, r2 is 2, q2 is an integer of 0-1.
When there are a plurality of R ²³ in one molecule, the plurality of R ²³ may be the same or different. From the viewpoint of easy availability of raw materials and ease of production of Compound 2, it is preferable that they are the same.

As the compound 2, a compound represented by the formula 20 is preferable in that it is superior in the adhesion of the surface layer to the protective film of the compound 2 and the friction resistance of the surface layer.
^{_{R 21 - [(OCHF) m21}} (OC 2 H ma F (4-ma)) m22 (OC 3 H mb F (6-mb)) m23 (OC 4 H mc F (8-mc)) m24 (OC 5 _{H md F (10-md)} ) m25 (OC 6 H me F (12-me)) m26 (OX 21) m20] -Y 2 -Z 2 (R 22) q2 (R 23) r2-q2 formula 20
The definition of each group is as described above.

Specific examples of compound 2 include the following examples 1 to 68. In the following table, t represents an integer of 1 or more. t is preferably an integer of 50 or less.

Compound 2 can be produced by a known production method. For example, the compound represented by Formula 2 which is one embodiment of Compound 2 is the same as the compound represented by Formula 2A in which HSi (R ² ) _n2 L ² _3-n2 (R ² , L ² , and n2 are defined above. And the hydrosilylation reaction.
_{^{R 21A - [(OX 2)}} m2 (OX 21) m20] -Y 2 -Z 2 (R 22) q2 (L 2A -CH = CH 2) r2-q2 formula 2A
In the formula, X ² , X ²¹ , Y ² , Z ² , R ²² , m2, m20, q2, and r2 are as defined above, and R ^21A is an alkyl group that may have a fluorine atom, or — Y ² —Z ² (R ²² ) _q2 (L ^2A —CH═CH ₂ ) _r2-q2 and L ^2A is an alkylene group optionally having —O—, a single bond or —O—; When L ^2A —CH═CH ₂ is hydrosilylated, it becomes L ² of the compound represented by Formula 2. For example, when Y ² is —C (O) NHCH ₂ —, the compound represented by Formula 2A is R ^21A — [(OX ² ) _m2 (OX ²¹ ) _m20 ] by a known method using R ^21A —OH as a raw material. —C (O) OR ^2B (R ^2B is an alkyl group having 1 to 6 carbon atoms) was obtained, and NH ₂ —CH ₂ —Z ² (R ²² ) _q2 (L ^2A —CH═CH ₂ ) _r2-q2 It can be produced by reacting with

(Compound 3)
Compound 3 has a poly (oxyperfluoroalkylene) chain containing a repeating unit represented by Formula 31.
(OX ³ ) _m3 formula 31
X ³ is a perfluoroalkylene group.
The number of carbon atoms of the perfluoroalkylene group is preferably 1 to 6 because the water and oil repellency of the surface layer is more excellent.
The perfluoroalkylene group may be linear or branched, but is preferably linear because it is more excellent in water and oil repellency of the surface layer.
The plurality of OXs ³ may be the same or different. That is, (OX ³ ) _m3 is composed of two or more types of OX ³ having different carbon numbers, or two or more types of OX having different side chains or different types of side chains even if the number of carbons is the same. ³ may be comprised.

M3 is an integer of 5 or more, preferably an integer of 5 to 200, more preferably an integer of 5 to 150, and particularly preferably an integer of 10 to 100. When m3 is 5 or more, the water and oil repellency of the surface layer is more excellent. If m3 is not more than the upper limit of the above range, the friction resistance of the surface layer is more excellent.

(OX ³ ) In _m3 , when two or more types of OX ³ having different carbon numbers exist, the bonding order of each OX ³ is not limited. For example, when two types of OX ³ exist, the two types of OX ³ may be arranged randomly, alternately, or in blocks.
^(OX ₃₎ The _m3, from the viewpoint of water and oil repellency of the surface layer is more _{excellent, {(OCF 2) m31 (} OCF 2 CF 2) m32 (OCF 2 CF 2 CF 2) m33 (OCF 2 CF 2 CF 2 _{CF 2) m34}, (OCF} 2 CF 2) m36, (OCF 2 CF 2 CF 2) m37, (OCF 2 CF 2 -OCF 2 CF 2 CF 2 CF 2) m35 (OCF 2 CF 2), (OCF 2 —OCF ₂ CF ₂ CF ₂ CF ₂ CF ₂ ) _m38 (OCF ₂ ), (OCF ₂ CF ₂ —OCF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ ) _m39 (OCF ₂ CF ₂ ), or (OCF ₂₎ CF ₂ —OCF ₂ CF ₂ CF ₂ CF ₂ ) _m40 (OCF ₂ CF ₂ ) (OCF ₂ CF ₂ CF ₂ ) is preferred, and {(OCF _{2 ) M31 (OCF 2 CF 2)} m32 (OCF 2 CF 2 CF 2) m33 (OCF 2 CF 2 CF 2 CF 2) m34}, (OCF 2 CF 2 -OCF 2 CF 2 CF 2 CF 2) m35 (OCF 2 CF ₂ ), (OCF ₂ —OCF ₂ CF ₂ CF ₂ CF ₂ CF ₂ ) _m38 (OCF ₂ ), (OCF ₂ CF ₂ —OCF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ ) _m39 (OCF ₂ CF ₂ ) Or (OCF ₂ CF ₂ -OCF ₂ CF ₂ CF ₂ CF ₂ ) _m40 (OCF ₂ CF ₂ ) (OCF ₂ CF ₂ CF ₂ ) is more preferable, and {(OCF ₂ ) _m31 (OCF ₂ CF ₂ ) _m32 }, {(OCF ₂ ) _m31 (OCF ₂ CF ₂ CF ₂ ) _m33 }, or (OCF ₂ CF ₂ —OCF _{2) CF 2 CF 2 CF 2) m40} (OCF 2 CF 2) (OCF 2 CF 2 CF 2) is particularly preferred.
Here, m31 is an integer of 1 or more, m32, m33 and m34 are each an integer of 0 or 1 and m31 + m32 + m33 + m34 is an integer of 5 to 200, m31 OCF ₂ , m32 OCF ₂ CF _2, m33 amino _OCF 2 _CF 2 _CF 2, m34 pieces of join order _{OCF 2 CF} 2 _CF 2 _CF 2 is not limited. m36 and m37 are each an integer from 5 to 200, m35, m38 and m39 are each an integer from 2 to 99, and m40 is an integer from 3 to 99.
In addition _{{(OCF 2) m31 (OCF} 2 CF 2) m32 (OCF 2 CF 2 CF 2) m33 (OCF 2 CF 2 CF 2 CF 2) m34}, when m33 and m34 is 0, m32 / m31 is From the viewpoint that the friction resistance of the surface layer is further excellent, 0.1 to 10 is preferable, 0.2 to 5.0 is more preferable, 0.2 to 2.0 is more preferable, and 0.2 to 1.5 is preferable Particularly preferred is 0.2 to 0.85.

Compound 3 has two or more groups 32.
—Si (R ³ ) _n3 L ³ _3-n3 Formula 32

The number of the groups 32 included in the compound 3 is 2 or more, preferably 2 to 10, more preferably 2 to 5, and particularly preferably 2 or 3 in view of excellent friction resistance of the surface layer.
When there are a plurality of groups 32 in one molecule, the plurality of groups 32 may be the same or different. From the viewpoint of easy availability of raw materials and ease of production of compound 3, it is preferable that they are the same.

R ³ is a monovalent hydrocarbon group, preferably a monovalent saturated hydrocarbon group. R ³ preferably has 1 to 6 carbon atoms, more preferably 1 to 3, and particularly preferably 1 or 2.

L ³ is a hydrolyzable group or a hydroxyl group. That is, when L ³ is a hydrolyzable group, the group represented by Si—L ³ is a hydrolyzable silyl group.

Specific examples of L ³ include an alkoxy group, a halogen atom, an acyl group, and an isocyanate group (—NCO). As the alkoxy group, an alkoxy group having 1 to 4 carbon atoms is preferable. As the halogen atom, a chlorine atom is preferable.
L ³ is preferably an alkoxy group having 1 to 4 carbon atoms or a halogen atom from the viewpoint that the production of compound 3 is easier. L ³ is preferably an alkoxy group having 1 to 4 carbon atoms from the viewpoint that the outgassing during coating is small and the storage stability of compound 3 is better, and ethoxy is required when long-term storage stability of compound 3 is required. A group is particularly preferred, and a methoxy group is particularly preferred when the reaction time after coating is short.

n3 is an integer of 0-2.
n3 is preferably 0 or 1, particularly preferably 0. By the presence of a plurality of L ³ , the adhesion of the surface layer to the substrate becomes stronger.
When n3 is 1 or less, the plurality of L ³ present in one molecule may be the same or different. From the viewpoint of easy availability of raw materials and ease of production of compound 3, it is preferable that they are the same. When n3 is 2, a plurality of R ³ present in one molecule may be the same or different. From the viewpoint of easy availability of raw materials and ease of production of compound 3, it is preferable that they are the same.

Compound 3 does not contain the unit 21 described above. The phrase “compound 3 does not contain unit 21” means that compound 3 substantially does not contain unit 21. Specifically, ¹ H-NMR (300.4 MHz, solvent: CDCl ₃ , standard: TMS) For the chemical shift value δ obtained by analyzing compound 3 by the above, when all signals observed at δ = 5.0 to 6.5 ppm are converted to the number of H (protons), the above H per molecule It means that the total of the number of is 1.0 or less. It is considered that when the compound 3 does not contain the unit 21 and the compound 2 contains the unit 21, the surface tension of the composition is suitably adjusted and the adhesion of the surface layer is improved.

The compound 3 is preferably a compound represented by the formula 3 in that the surface layer of the compound 3 is more excellent in water / oil repellency and friction resistance.
[A- (OX ³ ) _m3 −] _j Z ³ [—Si (R ³ ) _n3 L ³ _3-n3 ] _g Formula 3

A is a perfluoroalkyl group or —Q [—Si (R ³ ) _n3 L ³ _3-n3 ] _k .
The number of carbon atoms in the perfluoroalkyl group is preferably from 1 to 10, more preferably from 1 to 6, and particularly preferably from 1 to 3 from the viewpoint that the friction resistance of the surface layer is more excellent.
The perfluoroalkyl group may be linear or branched.
However, j is 1 when A is -Q [-Si (R ³ ) _n3 L ³ _3-n3 ] _k .

As perfluoroalkyl groups, CF ₃ —, CF ₃ CF ₂ —, CF ₃ CF ₂ CF ₂ —, CF ₃ CF ₂ CF ₂ CF ₂ —, CF ₃ CF ₂ CF ₂ CF ₂ CF ₂ —, CF ₃ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ —, CF ₃ CF (CF ₃ ) —, and the like can be given.
As the perfluoroalkyl group, CF ₃ —, CF ₃ CF ₂ —, and CF ₃ CF ₂ CF ₂ — are preferable because the water and oil repellency of the surface layer is more excellent.

Q is a (k + 1) -valent linking group. As will be described later, k is an integer of 1 to 10. Accordingly, examples of Q include divalent to eleven valent linking groups.
Q may be any group that does not impair the effects of the present invention. For example, an alkylene group that may have an etheric oxygen atom or a divalent organopolysiloxane residue, a carbon atom, a nitrogen atom, or a silicon atom A divalent to octavalent organopolysiloxane residue, and formulas 3-1A, 3-1B, and 3-1A-1 to 3-1A-6 described below, and Si (R ³ ) _n3 L ³ _3-n3 And a group excluding.

The definitions of R ³ , L ³ , n3, X ³ and m3 are as described above.

Z ³ is a (j + g) -valent linking group.
Z ³ may be any group that does not impair the effects of the present invention. For example, an alkylene group that may have an etheric oxygen atom or a divalent organopolysiloxane residue, a carbon atom, a nitrogen atom, or a silicon atom A divalent to octavalent organopolysiloxane residue, and formulas 3-1A, 3-1B, and 3-1A-1 to 3-1A-6 described below, and Si (R ³ ) _n3 L ³ _3-n3 And a group excluding.

j is an integer of 1 or more, and is preferably an integer of 1 to 5 from the viewpoint of better water and oil repellency of the surface layer, and 1 is particularly preferable from the viewpoint of easy production of the compound 3.
g is an integer of 1 or more. However, when A is a perfluoroalkyl group, g is an integer of 2 or more, and an integer of 2 to 4 is preferable, and 2 or 3 is more preferable, and 3 is particularly preferable from the viewpoint of more excellent friction resistance of the surface layer. preferable. When A is -Q [-Si (R ³ ) _n3 L ³ _3-n3 ] _k , g + k is an integer of 2 or more, 2 or 3 is more preferable, and 3 is particularly preferable.

Compound 3 is preferably a compound represented by Formula 3-1 from the viewpoint that the water and oil repellency of the surface layer is more excellent.
A- (OX ³ ) _m3 -Z ³¹ Formula 3-1
In Formula 3-1, the definitions of A, X ³ and m3 are the same as the definitions of each group in Formula 3.

Z ³¹ is group 3-1A or group 3-1B.
-Q ^a -X ³¹ (-Q ^b -Si (R ³ ) _n3 L ³ _3-n3 ) _h (-R ³¹ ) _i Formula 3-1A
_{^{-Q c - [CH 2 C (}} R 32) (- Q d -Si (R 3) n3 L 3 3-n3)] y -R 33 Formula 3-1B

Q ^a is a single bond or a divalent linking group.
Examples of the divalent linking group include a divalent hydrocarbon group (a divalent saturated hydrocarbon group, a divalent aromatic hydrocarbon group, an alkenylene group, and an alkynylene group. A divalent saturated carbonization group. The hydrogen group may be linear, branched or cyclic and includes, for example, an alkylene group, preferably having 1 to 20 carbon atoms, and a divalent aromatic hydrocarbon group having carbon atoms. 5 to 20 is preferable, and examples thereof include a phenylene group, and may be an alkenylene group having 2 to 20 carbon atoms or an alkynylene group having 2 to 20 carbon atoms. , —O—, —S—, —SO ₂ —, —N (R ^d ) —, —C (O) —, —Si (R ^a ) ₂ —, and groups in which two or more of these are combined. . Here, R ^a is an alkyl group (preferably having 1 to 10 carbon atoms) or a phenyl group. R ^d is a hydrogen atom or an alkyl group (preferably having 1 to 10 carbon atoms).
Examples of the group in which two or more of these are combined include, for example, —OC (O) —, —C (O) N (R ^d ) —, an alkylene group —O-alkylene group, and an alkylene group —OC (O). -Alkylene group, alkylene group-Si (R ^a ) ₂ -phenylene group-Si (R ^a ) ₂

X ³¹ is a single bond, an alkylene group, a carbon atom, a nitrogen atom, a silicon atom, or a divalent to octavalent organopolysiloxane residue.
The alkylene group may have —O—, a silphenylene skeleton group, a divalent organopolysiloxane residue, or a dialkylsilylene group. The alkylene group may have a plurality of groups selected from the group consisting of —O—, a silphenylene skeleton group, a divalent organopolysiloxane residue, and a dialkylsilylene group.
The number of carbon atoms of the alkylene group represented by X ³¹ is preferably 1-20, and particularly preferably 1-10.
Examples of the divalent to octavalent organopolysiloxane residues include divalent organopolysiloxane residues and (w + 1) valent organopolysiloxane residues described below.

Q ^b is a single bond or a divalent linking group.
Definition of the divalent linking group are the same as those defined as described in the above-described Q ^a.

R ³¹ is a hydroxyl group or an alkyl group.
The alkyl group preferably has 1 to 5 carbon atoms, more preferably 1 to 3 carbon atoms, and particularly preferably 1 carbon atom.

When X ³¹ is a single bond or an alkylene group, h is 1, i is 0,
When X ³¹ is a nitrogen atom, h is an integer of 1 or 2, i is an integer of 0 or 1, and satisfies h + i = 2,
When X ³¹ is a carbon atom or a silicon atom, h is an integer of 1 to 3, i is an integer of 0 to 2, and satisfies h + i = 3,
When X ³¹ is a divalent to octavalent organopolysiloxane residue, h is an integer of 1 to 7, i is an integer of 0 to 6, and h + i = 1 to 7 is satisfied.
However, when h is 1, A is -Q [-Si (R ³ ) _n3 L ³ _3-n3 ] _k .
If ^(-Q b ^-Si that _{^{(R 3) n3 L 3 3}} -n3) there are two or more, two or more _{^{(-Q b -Si (R 3)}} n3 L 3 3-n3) are identical It may or may not be. When two or more R ³¹ are present, the two or more (—R ³¹ ) may be the same or different.

Q ^c is a single bond, an alkylene group, or a group having an etheric oxygen atom between carbon atoms of a ^C 2 or more alkylene group, and is preferably a single bond from the viewpoint of easy production of a compound.
The number of carbon atoms of the alkylene group is preferably 1-10, and particularly preferably 2-6.
The number of carbon atoms of the group having an etheric oxygen atom between carbon atoms of the alkylene group having 2 or more carbon atoms is preferably 2 to 10, and particularly preferably 2 to 6.

R ³² is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and is preferably a hydrogen atom from the viewpoint of easy production of a compound.
As the alkyl group, a methyl group is preferable.

Q ^d is a single bond or an alkylene group. The number of carbon atoms of the alkylene group is preferably 1 to 10, and more preferably 1 to 6. Q ^d is preferably a single bond or —CH ₂ — from the viewpoint of easy production of the compound.

R ³³ is a hydrogen atom or a halogen atom, and is preferably a hydrogen atom from the viewpoint of easy production of a compound.

y is an integer of 1 to 10, and an integer of 1 to 6 is preferable. However, when y is 1, A is -Q [-Si (R ³ ) _n3 L ³ _3-n3 ] _k .
Two or more [CH ₂ C (R ³² ) (— Q ^d —Si (R ³ ) _n3 L ³ _3-n3 )] may be the same or different.

The group 3-1A is preferably a group 3-1A-1 to 3-1A-6.
-(X ³² ) _s1 -Q ^b1 -SiR _n L _3-n Formula 3-1A-1
-(X ³³ ) _s2 -Q ^a2 -N [-Q ^b2 -Si (R ³ ) _n3 L ³ _3-n3 ] ₂ Formula 3-1A-2
-Q ^a3 -G (R ^g ) [-Q ^b3 -Si (R ³ ) _n3 L ³ _3-n3 ] Formula ₂ 3-1A-3
-[C (O) N (R ^d )] _s4 -Q ^a4- (O) _t4 -C [-(O) _u4 -Q ^b4 -Si (R ³ ) _n3 L ³ _3-n3 ] ₃ Formula 3-1A -4
-Q ^a5 -Si [-Q ^b5 -Si (R ³ ) _n3 L ³ _3-n3 ] ₃ Formula 3-1A-5
-[C (O) N (R ^d )] _v -Q ^a6 -Z ^a [-Q ^b6 -Si (R ³ ) _n3 L ³ _3-n3 ] _w Formula 3-1A-6
However, when the group 3-1A is the group 3-1A-1, A in the formula 3-1 is —Q [—Si (R ³ ) _n3 L ³ _3-n3 ] _k .
In formulas 3-1A-1 to 3-1A-6, the definitions of R ³ , L ³ , and n3 are as described above.

X ³² is —O— or —C (O) N (R ^d ) — (wherein N binds to Q ^b1 ).
The definition of R ^d is as described above.
s1 is 0 or 1.

Q ^b1 is an alkylene group. The alkylene group may have —O—, a silphenylene skeleton group, a divalent organopolysiloxane residue, or a dialkylsilylene group. The alkylene group may have a plurality of groups selected from the group consisting of —O—, a silphenylene skeleton group, a divalent organopolysiloxane residue, and a dialkylsilylene group.
In addition, when the alkylene group has —O—, a silphenylene skeleton group, a divalent organopolysiloxane residue or a dialkylsilylene group, it is preferable to have these groups between carbon atoms.

The alkylene group represented by Q ^b1 preferably has 1 to 10 carbon atoms, and particularly preferably 2 to 6 carbon atoms.

As Q ^b1 , when s1 is 0, —CH ₂ OCH ₂ CH ₂ CH ₂ —, —CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ —, —CH ₂ CH ₂ —, —CH ₂ CH ₂ CH ₂ —, —CH ₂ OCH ₂ CH ₂ CH ₂ Si (CH ₃ ) ₂ OSi (CH ₃ ) ₂ CH ₂ CH ₂ — are preferred. When (X ³² ) _s1 is —O—, —CH ₂ CH ₂ CH ₂ — and —CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ — are preferred. When (X ³² ) _s1 is —C (O) N (R ^d ) —, an alkylene group having 2 to 6 carbon atoms is preferred (wherein N in the formula binds to Q ^b1 ). A compound is easy to manufacture when ^Qb1 is these groups.

Specific examples of the group 3-1A-1 include the following groups. In the following formula, * represents a bonding position with (OX ³ ) _m3 .

X ³³ is —O—, —NH—, or —C (O) N (R ^d ) —.
The definition of R ^d is as described above.

Q ^a2 represents a single bond, an alkylene group, —C (O) —, or an etheric oxygen atom between carbon atoms of the alkylene group having 2 or more carbon atoms, —C (O) —, —C (O ) A group having O—, —OC (O) — or —NH—.
The alkylene group represented by Q ^a2 preferably has 1 to 10 carbon atoms, and particularly preferably 2 to 6 carbon atoms.
An etheric oxygen atom, —C (O) —, —C (O) O—, —OC (O) — or —NH between carbon atoms of the alkylene group having 2 or more carbon atoms represented by Q ^a2 The number of carbons in the group having — is preferably 2 to 10, and particularly preferably 2 to 6.

The Q ^a2, from the viewpoint of easily producing the _{compound, -CH 2 -, - CH 2} CH 2 -, - CH 2 CH 2 CH 2 -, - CH 2 OCH 2 CH 2 -, - CH 2 NHCH 2 CH 2 —, —CH ₂ CH ₂ OC (O) CH ₂ CH ₂ —, —C (O) — are preferred (where the right side is bonded to N).

s2 is 0 or 1 (provided that 0 when Q ^a2 is a single bond). From the viewpoint of easy production of the compound, 0 is preferable.

Q ^b2 is an alkylene group or a group having a divalent organopolysiloxane residue, an etheric oxygen atom or —NH— between the carbon atoms of the alkylene group having 2 or more carbon atoms.
The alkylene group represented by Q ^b2 preferably has 1 to 10 carbon atoms, and particularly preferably 2 to 6 carbon atoms.
The number of carbon atoms of the group having a divalent organopolysiloxane residue, an etheric oxygen atom or —NH— between the carbon atoms of the alkylene group having 2 or more carbon atoms represented by Q ^b2 is 2 to 10 2 to 6 are particularly preferable.

Q ^b2 is preferably —CH ₂ CH ₂ CH ₂ — or —CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ — (provided that the right side is bonded to Si) from the viewpoint of easy production of the compound.

Two [—Q ^b2 —Si (R ³ ) _n3 L ³ _3-n3 ] may be the same or different.

Specific examples of the group 3-1A-2 include the following groups. In the following formula, * represents a bonding position with (OX ³ ) _m3 .

Q ^a3 is a single bond, an alkylene group, or a group having an etheric oxygen atom between carbon atoms of the alkylene group having 2 or more carbon atoms, and is preferably a single bond from the viewpoint of easy production of a compound.
The alkylene group represented by Q ^a3 preferably has 1 to 10 carbon atoms, and particularly preferably 2 to 6 carbon atoms.
The carbon number of the group having an etheric oxygen atom between carbon atoms of the alkylene group having 2 or more carbon atoms represented by ^Qa3 is preferably 2 to 10, and particularly preferably 2 to 6.

G is a carbon atom or a silicon atom.
R ^g is a hydroxyl group or an alkyl group. The number of carbon atoms of the alkyl group represented by R ^g is preferably 1 to 4.
G (R ^g ) is C (OH) or Si (R ^ga ) (provided that R ^ga is an alkyl group. The alkyl group preferably has 1 to 10 carbon atoms; Group is particularly preferred.).

Q ^b3 is an alkylene group or a group having an etheric oxygen atom or a divalent organopolysiloxane residue between carbon atoms of a C 2 or more alkylene group.
The alkylene group represented by Q ^b3 preferably has 1 to 10 carbon atoms, and particularly preferably 2 to 6 carbon atoms.
The number of carbon atoms of the group having an etheric oxygen atom or a divalent organopolysiloxane residue between carbon atoms of the alkylene group having 2 or more carbon atoms represented by ^Qb3 is preferably 2 to 10. 6 is particularly preferred.
The Q ^b3, from the viewpoint of easily producing the _{compound, -CH 2 CH 2 -, -} CH 2 CH 2 CH 2 -, - CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 - is preferred.

Two [—Q ^b3 —Si (R ³ ) _n3 L ³ _3-n3 ] may be the same or different.

Specific examples of the group 3-1A-3 include the following groups. In the following formula, * represents a bonding position with (OX ³ ) _m3 .

The definition of R ^d in Formula 3-1A-4 is as described above.
s4 is 0 or 1.
Q ^a4 is a single bond, an alkylene group, or a group having an etheric oxygen atom between carbon atoms of the alkylene group having 2 or more carbon atoms.
The alkylene group represented by Q ^a4 preferably has 1 to 10 carbon atoms, and particularly preferably 2 to 6 carbon atoms.
The number of carbon atoms of the group having an etheric oxygen atom between carbon atoms of the alkylene group having 2 or more carbon atoms represented by ^Qa4 is preferably 2 to 6, and particularly preferably 2 to 6.
t4 is 0 or 1 (provided that 0 when Q ^a4 is a single bond).
-Q ^a4- (O) _t4- is a single bond, -CH ₂ O-, -CH ₂ OCH _2- , -CH ₂ OCH ₂ CH ₂ when s4 is 0 because it is easy to produce a compound. O—, —CH ₂ OCH ₂ CH ₂ OCH ₂ —, —CH ₂ OCH ₂ CH ₂ CH ₂ CH ₂ OCH ₂ — are preferred (where the left side is bonded to (R ^f O) _m ), and s4 is 1. In this case, a single bond, —CH ₂ —, —CH ₂ CH ₂ — is preferable.

Q ^b4 is an alkylene group, and the alkylene group is —O—, —C (O) N (R ^d ) — (wherein R ^{d is} as defined above), a silphenylene skeleton group, a divalent group It may have an organopolysiloxane residue or a dialkylsilylene group.
In the case where the alkylene group has —O— or a silphenylene skeleton group, it is preferable to have an —O— or silphenylene skeleton group between carbon atoms. Further, when the alkylene group has —C (O) N (R ^d ) —, a dialkylsilylene group or a divalent organopolysiloxane residue, the terminal on the side bonded to the carbon atom-carbon atom or (O) _u4 side It is preferable to have these groups.
The alkylene group represented by Q ^b4 preferably has 1 to 10 carbon atoms, and particularly preferably 2 to 6 carbon atoms.

u4 is 0 or 1.
As — (O) _u4 —Q ^b4 —, since it is easy to produce a compound, —CH ₂ CH ₂ —, —CH ₂ CH ₂ CH ₂ —, —CH ₂ OCH ₂ CH ₂ CH ₂ —, —CH ₂ OCH ₂ CH ₂ CH ₂ CH ₂ CH ₂ —, —OCH ₂ CH ₂ CH ₂ —, —OSi (CH ₃ ) ₂ CH ₂ CH ₂ CH ₂ —, —OSi (CH ₃ ) ₂ OSi (CH ₃ ) ₂ CH ₂ CH ₂ CH ₂ —, —CH ₂ CH ₂ CH ₂ Si (CH ₃ ) ₂ PhSi (CH ₃ ) ₂ CH ₂ CH ₂ — are preferred (however, the right side is bonded to Si).

Three [— (O) _u4 -Q ^b4 —Si (R ³ ) _n3 L ³ _3-n3 ] may be the same or different.

Specific examples of the group 3-1A-4 include the following groups. In the following formula, * represents a bonding position with (OX ³ ) _m3 .

Q ^a5 is an alkylene group or a group having an etheric oxygen atom between carbon atoms of the alkylene group having 2 or more carbon atoms.
The alkylene group represented by Q ^a5 preferably has 1 to 10 carbon atoms, and particularly preferably 2 to 6 carbon atoms.
The number of carbon atoms of the group having an etheric oxygen atom between carbon atoms of the alkylene group having 2 or more carbon atoms represented by Q ^a5 is preferably 2 to 10, and particularly preferably 2 to 6.
The Q ^a5, from the viewpoint of easily producing the _{compound, -CH 2 OCH 2 CH 2 CH} 2 -, - CH 2 OCH 2 CH 2 OCH 2 CH 2 CH 2 -, - CH 2 CH 2 -, - CH 2 CH ₂ CH ₂ — is preferred (where the right side is bonded to Si).

Q ^b5 is an alkylene group or a group having an etheric oxygen atom or a divalent organopolysiloxane residue between carbon atoms of an alkylene group having 2 or more carbon atoms.
The alkylene group represented by ^Qb5 preferably has 1 to 10 carbon atoms, and particularly preferably 2 to 6 carbon atoms.
The number of carbon atoms of the group having an etheric oxygen atom or a divalent organopolysiloxane residue between carbon atoms of the alkylene group having 2 or more carbon atoms represented by ^Qb5 is preferably 2 to 10. 6 is particularly preferred.
Q ^b5 is preferably —CH ₂ CH ₂ CH ₂ — or —CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ — from the viewpoint of easy production of the compound (where the right side is Si (R ³ ) _n3 L ³ _{3 Bind} to _n3 ).

The three [—Q ^b5 —Si (R ³ ) _n3 L ³ _3-n3 ] may be the same or different.

Specific examples of the group 2-1-5 include the following groups. In the following formula, * represents a bonding position with (OX ³ ) _m3 .

The definition of R ^d in Formula 3-1A-6 is as described above.
v is 0 or 1.

Q ^a6 is an alkylene group or a group having an etheric oxygen atom between carbon atoms of a C 2 or more alkylene group.
The alkylene group represented by Q ^a6 preferably has 1 to 10 carbon atoms, and particularly preferably 2 to 6 carbon atoms.
The carbon number of the group having an etheric oxygen atom between carbon atoms of the alkylene group having 2 or more carbon atoms represented by ^Qa6 is preferably 2 to 10, and particularly preferably 2 to 6.
The Q ^a6, from the viewpoint of easily producing the _{compound, -CH 2 OCH 2 CH 2 CH} 2 -, - CH 2 OCH 2 CH 2 OCH 2 CH 2 CH 2 -, - CH 2 CH 2 -, - CH 2 CH ₂ CH ₂ - is preferred (but the right side is attached to ^{Z a.).}

Z ^a is an organopolysiloxane residue of (w + 1) valence.
w is an integer of 2 to 7.
Examples of the (w + 1) -valent organopolysiloxane residue include the following groups. However, R ^a in the following formula is as described above.

Q ^b6 is an alkylene group or a group having an etheric oxygen atom or a divalent organopolysiloxane residue between carbon atoms of a C 2 or more alkylene group.
The alkylene group represented by ^Qb6 preferably has 1 to 10 carbon atoms, and particularly preferably 2 to 6 carbon atoms.
The number of carbon atoms of the group having an etheric oxygen atom or a divalent organopolysiloxane residue between carbon atoms of the alkylene group having 2 or more carbon atoms represented by ^Qb6 is preferably 2 to 10. 6 is particularly preferred.
The Q ^b6, from the viewpoint of easily producing the _{compound, -CH 2 CH 2 -, -} CH 2 CH 2 CH 2 - is preferred.

The w [—Q ^b6 —Si (R ³ ) _n3 L ³ _3-n3 ] may be the same or different.

(Content ratio of compounds 1 to 3)
Compounds 1 to 3 may be used alone or in combination of two or more.
In the present composition, the content of compound 3 relative to the total content of compound 1 and compound 2 is a mass ratio in that the balance between the adhesion of the surface layer to the protective film and the friction resistance of the surface layer is excellent. 0.1 to 10 is preferable, 0.1 to 4 is more preferable, 0.1 to 1.5 is more preferable, and 0.25 to 0.67 is particularly preferable.
In addition, about the compound applicable to both the compound 1 and the compound 2, the said mass ratio is calculated noting that it corresponds to only one of the compound 1 or the compound 2.

(Other ingredients)
The composition may contain a liquid medium.
Specific examples of the liquid medium include water and organic solvents. Specific examples of the organic solvent include fluorinated organic solvents and non-fluorinated organic solvents.
Two or more organic solvents may be used in combination.

Specific examples of the fluorinated organic solvent include fluorinated alkanes, fluorinated aromatic compounds, fluoroalkyl ethers, fluorinated alkylamines, and fluoroalcohols.
The fluorinated alkane is preferably a compound having 4 to 8 carbon atoms. For example, C ₆ F ₁₃ H (AC-2000: product name, manufactured by AGC), C ₆ F ₁₃ C ₂ H ₅ (AC-6000: product name) , Manufactured by AGC), C ₂ F ₅ CHFCHFCF ₃ (Bertrel: product name, manufactured by DuPont).
Specific examples of the fluorinated aromatic compound include hexafluorobenzene, trifluoromethylbenzene, perfluorotoluene, 1,3-bis (trifluoromethyl) benzene, and 1,4-bis (trifluoromethyl) benzene.
The fluoroalkyl ether is preferably a compound having 4 to 12 carbon atoms. For example, CF ₃ CH ₂ OCF ₂ CF ₂ H (AE-3000: product name, manufactured by AGC), C ₄ F ₉ OCH ₃ (Novec-7100: Product name, manufactured by 3M), C ₄ F ₉ OC ₂ H ₅ (Novec-7200: product name, manufactured by 3M), C ₂ F ₅ CF (OCH ₃ ) C ₃ F ₇ (Novec-7300: product name, 3M).
Specific examples of the fluorinated alkylamine include perfluorotripropylamine and perfluorotributylamine.
Specific examples of the fluoroalcohol include 2,2,3,3-tetrafluoropropanol, 2,2,2-trifluoroethanol, and hexafluoroisopropanol.

As the non-fluorine-based organic solvent, a compound consisting only of a hydrogen atom and a carbon atom and a compound consisting only of a hydrogen atom, a carbon atom and an oxygen atom are preferable. Specifically, a hydrocarbon-based organic solvent, a ketone-based organic solvent , Ether-based organic solvents, ester-based organic solvents, and alcohol-based organic solvents.
Specific examples of the hydrocarbon organic solvent include hexane, heptane, and cyclohexane.
Specific examples of the ketone organic solvent include acetone, methyl ethyl ketone, and methyl isobutyl ketone.
Specific examples of the ether organic solvent include diethyl ether, tetrahydrofuran, and tetraethylene glycol dimethyl ether.
Specific examples of the ester organic solvent include ethyl acetate and butyl acetate.
Specific examples of the alcohol organic solvent include isopropyl alcohol.

When the present composition contains a liquid medium, the content of the liquid medium is preferably 70 to 99.99% by mass, particularly preferably 80 to 99.9% by mass, based on the total mass of the present composition.
When the composition contains a liquid medium and contains Compound 1, the content of Compound 1 is preferably 0.002 to 27.3% by mass, and preferably 0.06 to 16% with respect to the total mass of the composition. 0.0 mass% is particularly preferable.
When the composition contains a liquid medium and contains compound 2, the content of compound 2 is preferably 0.002 to 27.3% by mass, and preferably 0.06 to 16% with respect to the total mass of the composition. 0.0 mass% is particularly preferable.
When the composition contains a liquid medium, the content of the compound 3 is preferably 0.001 to 24.0% by mass, particularly 0.02 to 8.0% by mass, based on the total mass of the composition. preferable.

This composition may contain components other than the above.
Examples of other components include by-products produced in the production steps of Compound 1 to Compound 3, inevitable compounds in production such as unreacted raw materials.
Moreover, additives, such as an acid catalyst and a basic catalyst which accelerate | stimulate the hydrolysis and condensation reaction of a hydrolyzable silyl group, are mentioned. Specific examples of the acid catalyst include hydrochloric acid, nitric acid, acetic acid, sulfuric acid, phosphoric acid, sulfonic acid, methanesulfonic acid, and p-toluenesulfonic acid. Specific examples of the basic catalyst include sodium hydroxide, potassium hydroxide, and ammonia.
The content of the other components is preferably 0 to 10% by mass, more preferably 0 to 5% by mass, and particularly preferably 0 to 1% by mass with respect to the total amount of the compounds 1 to 3.

[Goods]
The article of the present invention has a base material and a surface layer formed from the composition on the base material. It is preferable that the protective film is stuck on the surface of the surface layer.
The surface layer includes at least one compound selected from the group consisting of Compound 1 and Compound 2, and a compound obtained by subjecting Compound 3 to hydrolysis and condensation reactions.
The film thickness of the surface layer is preferably 1 to 100 nm, and particularly preferably 1 to 50 nm. The thickness of the surface layer was determined by obtaining an interference pattern of reflected X-rays by an X-ray reflectivity method using an X-ray diffractometer for thin film analysis (ATX-G: product name, manufactured by Rigaku). It can be calculated from the vibration period.

The substrate is not particularly limited as long as it is required to impart water and oil repellency. Specific examples of the base material include metals, resins, glass, sapphire, ceramics, stones, and composite materials thereof. The glass may be chemically strengthened. The substrate may be ground-treated with the compound described in paragraphs 0089 to 0095 of International Publication No. 2011/016458, SiO ₂ or the like.

The article can be manufactured, for example, by the following method.
-The method of processing the surface of a base material by the dry-coating method using this composition, and obtaining the said article | item.
A method of obtaining the above article by applying the present composition to the surface of a substrate by a wet coating method and drying the composition.
In the wet coating method, compounds 1 to 3 may be hydrolyzed in advance using an acid catalyst, a basic catalyst or the like, and a composition containing the hydrolyzed compound and a liquid medium may be used.

When the difference in Mn between the compound 3 and at least one compound selected from the group consisting of the compound 1 and the compound 2 contained in the composition is small (preferably the difference in Mn is 0 to 3,000, Particularly preferably, a dry layer is obtained in that a surface layer in which at least one compound selected from the group consisting of Compound 1 and Compound 2 and Compound 3 are uniformly distributed with a difference in Mn of 0 to 2,000) is obtained. It is preferable to form the surface layer using a coating method.
On the other hand, when the M difference between the compound 3 and at least one compound selected from the group consisting of the compound 1 and the compound 2 contained in the composition is large (preferably the difference in Mn is 2,000 As described above, wet is particularly preferable in that a surface layer in which at least one compound selected from the group consisting of Compound 1 and Compound 2 and Compound 3 are uniformly distributed can be obtained. It is preferable to form the surface layer using a coating method.

Specific examples of the dry coating method include a vacuum deposition method, a CVD method, and a sputtering method. Among these, vacuum deposition is preferable from the viewpoint of suppressing the decomposition of the compounds 1 to 3 and the simplicity of the apparatus. At the time of vacuum deposition, a pellet-like substance obtained by impregnating the present composition with a porous metal such as iron or steel may be used.
Specific examples of the wet coating method include spin coating method, wipe coating method, spray coating method, squeegee coating method, dip coating method, die coating method, ink jet method, flow coating method, roll coating method, casting method, Langmuir-Blodget Method and gravure coating method.

Hereinafter, the present invention will be described in detail with reference to examples. However, the present invention is not limited to these examples. Examples 6 to 9, 11 to 16, and 18 to 19 are examples, and examples 5, 10, 17, and 20 are comparative examples. The compounding quantity of each component shows a mass reference | standard.

〔Evaluation methods〕
(Measurement method of water contact angle)
The contact angle (water contact angle) of about 2 μL of distilled water placed on the surface of the surface layer was measured using a contact angle measuring device (DM-500: product name, manufactured by Kyowa Interface Science Co., Ltd.). Measurements were made at five different locations on the surface of the surface layer, and the average value was calculated. The 2θ method was used to calculate the contact angle. The contact angle is preferably 100 degrees or more.

(Friction resistance test method)
For the surface layer, using a reciprocating traverse tester (manufactured by KK NTE) in accordance with JIS L0849: 2013 (ISO 105-X12: 2001), a steel wool bonster (# 0000) was pressure: 98.07 kPa, speed: 320 cm It was reciprocated at / min. The water contact angle was measured every 1000 reciprocations, and the number of reciprocations when the water contact angle became 85% or less for the first time with respect to the water contact angle before the test was measured. The upper limit of the number of reciprocations was 20,000. The greater the number of reciprocations, the better the friction resistance. The number of reciprocations is preferably 5000 times or more, and more preferably 10,000 times or more.

(Adhesion test method)
An acrylic adhesive layer of a polyvinyl chloride film having an acrylic adhesive layer (Elep Masking N-380: product name, manufactured by Nitto Denko Corporation, tape width 50 mm) is attached to the surface layer, and JIS K 6854-1: 1999 ( In accordance with ISO 8510-1: 1990), the polyvinyl chloride film was peeled off at a peeling rate of 100 mm / min at room temperature (23 ° C.) using a 90-degree peel tester (manufactured by Nisshin Kagaku). The 90 degree peeling force was measured. The greater the peel force, the better the adhesion. The peeling force is preferably 250 mN / 50 mm or more, and more preferably 370 mN / 50 mm or more.

[Example 1]
Compound 2-A was synthesized by the following procedure.
(Example 1-1)
According to the method described in Example 6-1 of International Publication No. 2013/121984, Compound X1 was obtained.
Compound X1: CH ₃ — (OCF ₂ CFHOCF ₂ CF ₂ CF ₂ CH ₂ ) _n —OH, average value of the number of repeating units n: 14

(Example 1-2)
In a 50 mL eggplant flask, 8.0 g of compound X1 obtained in Example 1-1, 0.34 g of allyl bromide, 0.08 g of tetrabutylammonium bromide, and 0.60 g of 48 mass% aqueous potassium hydroxide solution were placed. The mixture was stirred at 80 ° C. for 5 hours. The mixture was cooled to room temperature (23 ° C.), charged with 10 g of AC-6000 (product name, manufactured by AGC), and washed twice with water. The resulting crude liquid was purified by silica gel column chromatography (developing solvent: AC-6000) to obtain 7.9 g (yield 98%) of compound X2.
NMR spectrum of compound X2;
¹ H-NMR (300.4 MHz, solvent: CDCl ₃ , standard: TMS (tetramethylsilane)) δ (ppm): 2.4 (2H), 4.0 (2H), 4.2 (2H), 4 .5 (2H), 4.8 (26H), 5.2 to 5.4 (2H), 5.8 to 6.0 (1H), 6.7 to 6.9 (14H).
¹⁹ F-NMR (282.7 MHz, solvent: CDCl ₃ , standard: CFCl ₃ ) δ (ppm): -81 (3F), -84 to -85 (28F), -89 to -91 (28F), -114 (2F), -120 (26F), -122 (4F), -123 (2F), -124 (2F), -127 (30F), -145 (14F).
Compound X2: CH ₃ — (OCF ₂ CFHOCF ₂ CF ₂ CF ₂ CH ₂ ) _n —OCH ₂ CH═CH ₂ , average number of repeating units n: 14, Mn of compound X2: 4,300.

(Example 1-3)
In a 10 mL glass sample bottle, 6.0 g of the compound X2 obtained in Example 1-2, xylene solution of platinum / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum content) : 0.02 g of 2 mass%), 1.01 g of HSi (OCH ₃ ) ₃ , 0.02 g of aniline, 1.0 g of 1,3-bis (trifluoromethyl) benzene (manufactured by Tokyo Chemical Industry Co., Ltd.) And the mixture was stirred at 40 ° C. for 8 hours. After completion of the reaction, the solvent and the like were distilled off under reduced pressure and filtered through a membrane filter having a pore size of 1.0 μm to obtain 6.5 g of Compound 2-A (yield 100%).
NMR spectrum of compound 2-A;
¹ H-NMR (300.4 MHz, solvent: CDCl ₃ , standard: TMS) δ (ppm): 0.4 (2H), 1.7 (2H), 3.2 (9H), 3.3 (3H) 3.7 (2H), 4.0 (2H), 4.2 (26H), 5.5 to 5.8 (13H).
¹⁹ F-NMR (282.7 MHz, solvent: CDCl ₃ , standard: CFCl ₃ ) δ (ppm): −84.5 to −87.0 (26F), −90.3 to −92.2 (26F), -120.6 (24F), -124.1 (2F), -128.0 (26F), -143.8 to -145.0 (13F).
Compound 2-A: CH ₃ — (OCF ₂ CFHOCF ₂ CF ₂ CF ₂ CH ₂ ) _n —OCH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃ ,
Average number of repeating units n: 14, Mn of compound 2-A: 4,420.

[Example 2]
Compound 3-A was synthesized by the following procedure.
(Example 2-1)
According to the method described in Examples 11-1 to 11-3 of International Publication No. 2013/121984, Compound Y1 was obtained.
Compound Y1: CF ₃ — (OCF ₂ CF ₂ OCF ₂ CF ₂ CF ₂ CF ₂ ) _n —OCF ₂ CF ₂ —OCF ₂ CF ₂ CF ₂ CF ₂ —OC (O) CF (CF ₃ ) OCF ₂ CF ₂ CF ₃ , Average value of n: 13, Mn: 5,050.

(Example 2-2)
In a 50 mL three-necked flask, 9.0 g of compound Y1 and 0.45 g of NH ₂ CH ₂ C (CH ₂ CH═CH ₂ ) ₃ were placed, and the mixture was stirred at room temperature (23 ° C.) for 12 hours. The reaction crude liquid was developed on silica gel column chromatography to fractionate 9.4 g (yield 99%) of compound Y2.
Compound Y2: CF ₃ — (OCF ₂ CF ₂ OCF ₂ CF ₂ CF ₂ CF ₂ ) _n —OCF ₂ CF ₂ —OCF ₂ CF ₂ CF ₂ —C (O) NHCH ₂ C (CH ₂ CH═CH ₂ ) ₃ ,
Average value of n: 13, Mn: 4,800.

(Example 2-3)
In a 100 mL tetrafluoroethylene-perfluoro (alkoxy vinyl ether) copolymer eggplant flask, 5.0 g of compound Y2 and a xylene solution of platinum / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (Platinum content: 2% by mass) 0.03 g, trimethoxysilane 0.36 g, aniline 0.01 g and 1,3-bis (trifluoromethyl) benzene 2.0 g were added, and the mixture was allowed to cool to room temperature ( At 23 ° C.) for 8 hours. The solvent and the like were distilled off under reduced pressure and filtered through a membrane filter having a pore size of 0.5 μm to obtain 5.2 g of compound 3-A (purity 99% or more, yield 99%).
NMR spectrum of compound 3-A;
¹ H-NMR (300.4 MHz, solvent: CDCl ₃ , standard: TMS) δ (ppm): 0.75 (6H), 1.3 to 1.6 (12H), 3.4 (2H), 3. 7 (27H).
¹⁹ F-NMR (282.7 MHz, solvent: CDCl ₃ , reference: CFCl ₃ ) δ (ppm): −55.2 (3F), −82.1 (54F), −88.1 (54F), −90 .2 (2F), -119.6 (2F), -125.4 (52F), -126.2 (2F).
Compound 3-A: CF ₃ — (OCF ₂ CF ₂ OCF ₂ CF ₂ CF ₂ CF ₂ ) _n —OCF ₂ CF ₂ —OCF ₂ CF ₂ CF ₂ —C (O) NH—CH ₂ —C [CH ₂ CH ₂ CH ₂ —Si (OCH ₃ ) ₃ ] ₃ , n average value: 13, Mn: 5,400.

[Example 3]
Compound 3-B was synthesized by the following procedure.
(Example 3-1)
In a 50 mL three-necked flask, 10.1 g of the compound Y1 obtained in Example 2-1, 0.97 g of diallylamine, and 10 g of 1,3-bis (trifluoromethyl) benzene were placed, and the mixture was cooled to room temperature (23 ) For 8 hours. The reaction crude liquid was concentrated with an evaporator to obtain 9.8 g of a crude product. The crude product was developed on silica gel column chromatography to fractionate 9.5 g (yield 99%) of compound Y3.
NMR spectrum of compound Y3;
¹ H-NMR (300.4 MHz, solvent: CDCl ₃ , standard: TMS) δ (ppm): 4.0 (4H), 5.3 to 5.4 (4H), 5.7 to 6.0 (2H ).
¹⁹ F-NMR (282.7 MHz, solvent: CDCl ₃ , reference: CFCl ₃ ) δ (ppm): −55.1 (3F), −82.6 (54F), −87.9 (54F), −90 0.0 (2F), -110.3 (2F), -124.1 (2F), -125.0 (52F).
Compound Y3: CF ₃ — (OCF ₂ CF ₂ OCF ₂ CF ₂ CF ₂ CF ₂ ) _n —OCF ₂ CF ₂ —OCF ₂ CF ₂ CF ₂ —C (O) N (CH ₂ CH═CH ₂ ) ₂ ,
Average value of n: 13, Mn: 4,790.

(Example 3-2)
In a 100 mL tetrafluoroethylene-perfluoro (alkoxy vinyl ether) copolymer eggplant flask, 5.0 g of compound Y3 and a xylene solution of platinum / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (Platinum content: 2% by mass) 0.03 g, trimethoxysilane 0.36 g, aniline 0.01 g and 1,3-bis (trifluoromethyl) benzene 2.0 g were added, and the mixture was allowed to cool to room temperature ( At 23 ° C.) for 8 hours. The solvent and the like were distilled off under reduced pressure and filtered through a membrane filter having a pore size of 0.5 μm to obtain 5.2 g of compound 3-B (purity 99% or more, yield 99%).
NMR spectrum of compound 3-B;
¹ H-NMR (300.4 MHz, solvent: CDCl ₃ , standard: TMS) δ (ppm): 0.6 (4H), 1.8 (4H), 3.4 (4H), 3.6 (18H) .
¹⁹ F-NMR (282.7 MHz, solvent: CDCl ₃ , reference: CFCl ₃ ) δ (ppm): −55.2 (3F), −82.8 (54F), −88.1 (54F), −90 .2 (2F), -111.4 (2F), -124.2 (2F), -125.2 (52F).
Compound 3-B: CF ₃ — (OCF ₂ CF ₂ OCF ₂ CF ₂ CF ₂ CF ₂ ) _n —OCF ₂ CF ₂ —OCF ₂ CF ₂ CF ₂ —C (O) N [CH ₂ CH ₂ CH ₂ Si ( OCH ₃ ) ₃ ] ₂ ,
Average value of n: 13, Mn: 5,050.

[Example 4]
Compound 1-A is trimethoxy (1H, 1H, 2H, 2H-tridecafluoro-n-octyl) silane (CF _3- (CF ₂ ) ₅ (CH ₂ ) ₂ -Si (OCH ₃ ) manufactured by Tokyo Chemical Industry Co., Ltd. ) ₃ ) was used.
[Examples 5 to 20]
The compounds 1-A, 2-A, 3-A and 3-B obtained in Examples 1 to 4 were mixed in the proportions shown in Tables 1 and 2, and Examples 6 to 9, 11 to 16 and 18 to 19 compositions were obtained.
Using the obtained composition, surface treatment of the base material was performed by the following dry coating method to obtain an evaluation sample (article) in which a surface layer was formed on the surface of the base material (chemically tempered glass).
For Examples 5, 10, 17 and 20, Examples 6 to 9 were used except that only one compound was used among compounds 1-A, 2-A, 3-A and 3-B. , 11 to 16 and 18 to 19, each evaluation sample was produced.
Using the obtained evaluation samples, the above-described evaluation tests were performed, and the results are shown in Tables 1 and 2.

(Dry coating method)
A composition (0.5 g) shown in Table 1 was placed as a vapor deposition source on a molybdenum boat in a vacuum vapor deposition apparatus (VTR-350M: product name, ULVAC Kiko Co., Ltd.). The substrate was placed in a vacuum deposition apparatus, and the inside of the vacuum deposition apparatus was evacuated to a pressure of 5 × 10 ⁻³ Pa or less (absolute pressure). The boat in which each of the above-described compositions was placed was heated to 300 ° C., and each of the compositions shown in Table 1 was vacuum-deposited on a substrate to form a deposited film having a thickness of 10 nm. The base material on which the deposited film was formed was heated (post treatment) at a temperature of 200 ° C. for 30 minutes to form a surface layer having a thickness of 10 nm, and an evaluation sample was obtained.

As shown in Tables 1 and 2, when a composition containing Compound 1 or Compound 2 and Compound 3 was used (Examples 6 to 9, 11 to 16, and 18 to 19), friction resistance and adhesion to a protective film It was confirmed that an excellent surface layer was obtained.

The composition of the present invention can be used for various applications that are required to impart water and oil repellency. For example, coats for display input devices such as touch panels; surface protective coats made of transparent glass or transparent plastic parts, antifouling coats for kitchens; water-repellent moisture-proof coats and antifouling coats for electronic devices, heat exchangers, batteries, etc. Antifouling coating for toiletries; coating on a member that requires liquid repellency while conducting; water-repellent / water-proof / sliding coat for heat exchanger; surface friction coating for vibrating screens and cylinders, etc.

More specific examples of use include a front protective plate of a display, an antireflection plate, a polarizing plate, an antiglare plate, or an antireflection coating on the surface thereof, a touch panel of a device such as a mobile phone or a portable information terminal. Coats for various devices with display input devices that operate on the screen with human fingers or palms such as sheets and touch panel displays, surface protection coats such as eyeglass lenses, decorations around water such as toilets, baths, washrooms, kitchens, etc. Coating for building materials, waterproof coating for wiring boards, water repellent / waterproof / sliding coat for heat exchangers, water repellent coat for solar cells, waterproof / water repellent coat for printed wiring boards, waterproof for electronic equipment casings and electronic components Water repellent coat, insulation improvement coating for power transmission lines, waterproof / water repellent coat for various filters, waterproof coat for radio wave absorber and sound absorbing material, bath, kitchen equipment, toilet Over antifouling coating, the surface a low friction coating of vibrating screen and the cylinder interior and the like, mechanical parts, vacuum equipment parts, bearing parts, parts for transportation equipment such as automobiles (e.g., exterior, glass, mirrors, bumpers),
Examples thereof include a surface protective coat such as a tool.

It should be noted that the entire contents of the specification, claims, drawings, and abstract of Japanese Patent Application No. 2018-081607 filed on April 20, 2018 are cited herein as disclosure of the specification of the present invention. Incorporate.

Claims (12)

1. At least 1 selected from the group consisting of Compound 1 represented by Formula 1 and Compound 2 having a poly (oxyfluoroalkylene) chain containing a repeating unit represented by Formula 21 and a group represented by Formula 22 Species of compounds,
   Compound 3 having a poly (oxyperfluoroalkylene) chain containing a repeating unit represented by formula 31 and two or more groups represented by formula 32, and not containing a repeating unit represented by formula 21; A composition comprising:
   _{^{R 11 - (OX) m -Y}} -Z (R 12) q (R 13) r-q Formula 1
   However, in Formula 1,
   R ¹¹ is a fluoroalkyl group.
   X is a fluoroalkylene group having 1 or more carbon atoms and having 1 or more fluorine atoms.
   m is an integer of 0-4.
   Y represents an alkylene group which may have —O—, —C (O) N (R ¹⁴ ) — or —C (O) —, a single bond, —O—, —C (O) N (R ¹⁴ )-or -C (O)-. The alkylene group which may have —O—, —C (O) N (R ¹⁴ ) — or —C (O) — may have a fluorine atom. However, the Y is -OCF ₂ - when is an alkylene group containing, -OCF ₂ in the alkylene group - number of is one.
   R ¹⁴ is a hydrogen atom or an alkyl group.
   Z is a carbon atom, a silicon atom or a nitrogen atom.
   R ¹² is a hydrogen atom, a hydroxyl group or an alkyl group.
   R ¹³ is —L ¹ —Si (R ¹ ) _n1 L _3-n1 . R ¹ is a monovalent hydrocarbon group. L is a hydrolyzable group or a hydroxyl group. n1 is an integer of 0-2. L ¹ is an alkylene group which may have —O—.
   When Z is a carbon atom or a silicon atom, r is 3 and q is an integer of 0 to 1. When Z is a nitrogen atom, r is 2 and q is 0.
   (OX ² ) Formula 21
   —Si (R ² ) _n2 L ² _3-n2 Formula 22
   However, in Formula 21 and Formula 22,
   X ² is a fluoroalkylene group having one or more hydrogen atoms.
   R ² is a monovalent hydrocarbon group.
   L ² is a hydrolyzable group or a hydroxyl group.
   n2 is an integer of 0-2.
   (OX ³ ) _m3 formula 31
   —Si (R ³ ) _n3 L ³ _3-n3 Formula 32
   However, in Formula 31 and Formula 32,
   X ³ is a perfluoroalkylene group.
   m3 is an integer of 5 or more.
   R ³ is a monovalent hydrocarbon group.
   L ³ is a hydrolyzable group or a hydroxyl group. n3 is an integer of 0-2.
2. The composition according to claim 1, wherein m in the formula (1) is 0 or 1.
3. The composition according to claim 1 or 2, wherein the compound 2 is a compound represented by the formula 2.
   _{^{R 21 - [(OX 2)}} m2 (OX 21) m20] -Y 2 -Z 2 (R 22) q2 (R 23) r2-q2 formula 2
   However, in Formula 2,
   R ²¹ is an alkyl group which may have a fluorine atom, or —Y ² —Z ² (R ²² ) _q2 (R ²³ ) _r2-q2 .
   X ² is a fluoroalkylene group having one or more hydrogen atoms.
   X ²¹ is a perfluoroalkylene group.
   Y ² is a single bond or a divalent linking group.
   Z ² is a carbon atom, a silicon atom or a nitrogen atom.
   R ²² is a hydrogen atom, a hydroxyl group or an alkyl group.
   R ²³ is —L ²¹ —Si (R ² ) _n2 L ² _3-n2 . L ²¹ is an alkylene group which may have —O—. R ² is a monovalent hydrocarbon group. L ² is a hydrolyzable group or a hydroxyl group. n2 is an integer of 0-2.
   m2 is an integer of 2 or more, m20 is an integer of 0 or more, and m2 + m20 is an integer of 5 or more.
   If Z ² is a carbon atom or a silicon atom, r2 is 3, q2 is an integer of 0-2. If Z ² is a nitrogen atom, r2 is 2, q2 is an integer of 0-1.
4. The composition according to any one of claims 1 to 3, wherein the compound 3 is a compound represented by the formula 3.
   [A- (OX ³ ) _m3 −] _j Z ³ [—Si (R ³ ) _n3 L ³ _3-n3 ] _g Formula 3
   However, in Formula 3,
   A is a perfluoroalkyl group or —Q [—Si (R ³ ) _n3 L ³ _3-n3 ] _k .
   Q is a (k + 1) -valent linking group.
   k is an integer of 1 to 10.
   R ³ is a monovalent hydrocarbon group.
   L ³ is a hydrolyzable group or a hydroxyl group. n3 is an integer of 0-2.
   X ³ is a perfluoroalkylene group.
   m3 is an integer of 5 or more.
   Z ³ is a (j + g) -valent linking group.
   j is an integer of 1 or more.
   g is an integer of 1 or more. However, when A is a perfluoroalkyl group, g is an integer of 2 or more, and when A is —Q [—Si (R ³ ) _n3 L ³ _3-n3 ] _k , g + k is an integer of 2 or more. is there.
5. The number average molecular weight difference between at least one compound selected from the group consisting of the compound 1 and the compound 2 and the compound 3 is 0 to 3,000, according to any one of claims 1 to 4. The composition as described.
6. The composition according to any one of claims 1 to 5, wherein the content of the compound 3 with respect to the total content of the compound 1 and the compound 2 is 0.1 to 10 by mass ratio.
7. The composition according to any one of claims 1 to 6, comprising a liquid medium containing a fluorine-based organic solvent, a non-fluorine-based organic solvent, or water.
8. An article having a base material and a surface layer formed on the base material from the composition according to any one of claims 1 to 7.
9. The article according to claim 8, wherein the article is formed from the composition by a dry coating method.
10. The article according to claim 8 or 9, wherein the substrate is metal, resin, glass, sapphire, ceramic, stone, or a composite material thereof.
11. The article according to any one of claims 8 to 10, wherein the film thickness of the surface layer is 1 to 100 nm.
12. The article according to any one of claims 8 to 11, wherein a protective film is attached to the surface of the surface layer.