KR20210002456A - Composition and article - Google Patents

Abstract

Provision of a composition and article capable of forming a surface layer having excellent friction resistance and adhesion to a protective film. R ¹¹ -(OX) _m -YZ(R ¹² ) _q (R ¹³ ) Compound 1 represented by _rq , and a poly(oxyfluoroalkylene) chain including a unit represented by (OX ² ) and -Si(R ²⁾ ) at least one compound selected from the group consisting of compounds 2 having _n2 L ² _3-n2 , (OX ³ ) a poly(oxyperfluoroalkylene) chain comprising a unit represented by _m3 , and two or more -Si(R ³ ) _n3 L ^{3 A} composition containing a compound 3 having _3-n3 and not containing a repeating unit represented by Formula 21. R ¹¹ is a fluoroalkyl group, X is an alkylene group having a fluorine atom, m is 0 to 4, Y is a single bond or a divalent linking group, X ² is a fluoroalkylene group having a hydrogen atom, X ³ is a perfluoroalkyl Ren group, m3 is 5 or more, -Z(R ¹² ) _q (R ¹³ ) _rq , -Si(R ² ) _n2 L ² _3-n2 , -Si(R ³ ) _n3 L ³ _3-n3 has a hydrolyzable group It is.

Description

Composition and article

The present invention relates to a composition and an article capable of forming a surface layer having excellent friction resistance and adhesion.

Since the fluorinated compound exhibits high lubricity, water and oil repellency, etc., it is preferably used as a surface treatment agent. When water and oil repellency is imparted to the surface of the substrate by the surface treatment agent, it becomes easy to wipe off the dirt on the surface of the base material, and the dirt removal property is improved. Among the above fluorinated compounds, fluorinated ether compounds having a poly(oxyperfluoroalkylene) chain in which an ether bond (-O-) is present in the middle of the perfluoroalkylene chain is a compound having excellent flexibility, and in particular It is excellent in removability of such contamination.

The surface treatment agent containing the fluorinated ether compound has a performance that does not degrade water and oil repellency well even if repeatedly rubbed with a finger (friction resistance) and a performance that can easily remove fingerprints attached to the surface by wiping (fingerprints It is used as a surface treatment agent for a member constituting a finger-touched surface of a touch panel, for example, in applications where it is required to maintain the contamination removal property for a long time.

As the fluorinated ether compound, a compound having a poly(oxyperfluoroalkylene) chain and a hydrolyzable silyl group at the terminal is widely used. Among such compounds, Patent Document 1 shows that a fluorinated ether compound having a plurality of hydrolyzable silyl groups is preferable.

Japanese Unexamined Patent Publication No. 2016-037541

After the surface layer is formed on the substrate using the surface treatment agent, a peelable protective film is affixed on the surface layer in order to protect the substrate on which the surface layer is formed until the substrate on which the surface layer is formed is used in the next step. ) In some cases.

Here, the surface treatment agent containing a fluorinated ether compound having a plurality of hydrolyzable silyl groups described in Patent Document 1 can form a surface layer excellent in friction resistance. However, since the adhesion between the surface layer and the protective film is insufficient, there are cases 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, or dust collects in the gap formed between the protective film and the surface layer. .

In view of the above problems, an object of the present invention is to provide a composition and an article capable of forming a surface layer having excellent friction resistance and adhesion to a protective film.

The present invention achieves the above object and has the following aspects.

[1] At least one compound selected from the group consisting of compound 1 represented by formula 1, and compound 2 having a group represented by formula 22 and a poly(oxyfluoroalkylene) chain containing a repeating unit represented by formula 21; ,

A composition comprising a poly(oxyperfluoroalkylene) chain containing a repeating unit represented by formula 31, a compound 3 having two or more groups represented by formula 32, and not containing a repeating unit represented by formula 21.

R ¹¹ -(OX) _m -YZ(R ¹² ) _q (R ¹³ ) _rq Equation 1

However, in Equation 1,

R ¹¹ is a fluoroalkyl group.

X is a C1 or more fluoroalkylene group having 1 or more fluorine atoms.

m is an integer of 0-4.

Y is an alkylene group, a single bond, -O-, -C(O)N(R ¹⁴ )- which may have -O-, -C(O)N(R ¹⁴ )- or -C(O)- Or -C(O)-. The alkylene group which may have -O-, -C(O)N(R ¹⁴ )- or -C(O)- may have a fluorine atom. Note that the Y -OCF ₂ -, if an alkylene group containing, -OCF ₂ in the alkylene group - the number of the first dog.

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 from 0 to 1. When Z is a nitrogen atom, r is 2 and q is 0.

(OX ² ) Equation 21

-Si(R ² ) _n2 L ² _3-n2 Equation 22

However, in Equations 21 and 22,

X ² is a fluoroalkylene group having one or more hydrogen atoms.

R ² is a monovalent hydrocarbon group.

L ² is a hydrolysable group or a hydroxyl group.

n2 is an integer of 0-2.

(OX ³ ) _m3 equation 31

-Si(R ³ ) _n3 L ³ _3-n3 Equation 32

However, in Equations 31 and 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 Formula 2.

R ²¹ -[(OX ² ) _m2 (OX ²¹ ) _m20 ]-Y ² -Z ² (R ²² ) _q2 (R ²³ ) _r2-q2 Equation 2

However, in Equation 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 hydrolysable 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.

When Z ² is a carbon atom or a silicon atom, r2 is 3, and q2 is an integer of 0-2. When Z2 is a nitrogen atom, r2 is 2, and q2 is an integer from 0 to 1.

[4] The composition according to any one of [1] to [3], in which 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 Equation 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 1-10.

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 ) ₀ L ³ _3-n3 ] _k , g + k is an integer of 2 or more. .

[5] The composition according to any one of [1] to [4], wherein the difference between at least one compound selected from the group consisting of the compound 1 and the compound 2 and the number average molecular weight of the compound 3 is 0 to 3,000.

[6] The composition according to any one of [1] to [5], wherein the content of the compound 3 is 0.1 to 4 in terms of mass ratio with respect to the sum of the contents of the compound 1 and the compound 2.

[7] The composition according to any one of [1] to [6], comprising a fluorine-based organic solvent, a non-fluorine-based organic solvent, or a liquid medium containing water.

[8] An article comprising a substrate and a surface layer formed on the substrate from the composition according to any one of [1] to [7].

[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 a metal, resin, glass, sapphire, ceramic, stone, or a composite material thereof.

[11] The article according to any one of [8] to [10], wherein the surface layer has a film thickness of 1 to 100 nm.

[12] The article according to any one of [8] to [11], in which a protective film is adhered to the surface of the surface layer.

Advantageous Effects of Invention According to the present invention, a composition and an article capable of forming a surface layer having friction resistance and excellent in adhesion to a substrate or a protective film can be provided.

The meaning of the terms in this specification and the method of description are as follows.

The "repeating unit represented by Formula 21" is described as the unit 21. Repeating units represented by other formulas are also described accordingly.

The "group represented by formula 22" is described as group 22. Also described in other ways should be written accordingly.

In the case of saying "the alkylene group may have a group A", the alkylene group may have a group A between carbon atoms and a carbon atom in the alkylene group, or may have a group A at the terminal like an alkylene group-a group-.

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. Moreover, g1 is an integer of 1 or more, an integer of 1-9 is preferable, and an integer of 1-4 is especially preferable.

[Formula 1]

The "silphenylene skeleton group" is a group represented by -Si( ^Ry ) ₂ PhSi( ^Ry ) _2- (however, Ph is a phenylene group, and ^Ry is a monovalent organic group.). As R ^y , an alkyl group (preferably 1 to 10 carbon atoms) is preferable.

The "dialkylsilylene group" is a group represented by -Si(R ^z ) _2- (however, R ^Z is an alkyl group (preferably, having 1 to 10 carbon atoms).).

The "surface layer" means a layer formed on a substrate. In addition, the surface layer may be formed directly on the base material, or may be formed on the base material via another layer formed on the surface of the base material.

"Number average molecular weight (hereinafter, also referred to as Mn)" is calculated by calculating the number (average value) of oxyfluoroalkylene groups based on the terminal group by ¹ H-NMR and ¹⁹ F-NMR.

The hydrolyzable silyl group means a group which becomes a silanol group represented by Si-OH by a hydrolysis reaction. The silanol group reacts between the silanol groups to form a Si-O-Si bond. Moreover, it is thought that a silanol group can form a chemical bond (substrate-O-Si) by dehydrating-condensation reaction with the hydroxyl group (substrate -OH) on the surface of a substrate. 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 ``this composition'') is from the group consisting of compound 1 represented by formula 1 and compound 2 having a poly(oxyfluoroalkylene) chain containing unit 21 and group 22 Compound 3 having at least one selected compound, a poly(oxyperfluoroalkylene) chain containing unit 31 and two or more groups 32, and not containing unit 21 are included.

The surface layer formed by using this composition is excellent in friction resistance. This reason is presumed to be because, by using the compound 3 having two or more groups 32, the reaction point between the present composition and the base material increased, and the adhesion between the surface layer and the base material became good.

Moreover, the surface layer formed using this composition is excellent in adhesiveness with a protective film. This reason is thought to be because the number of repeating units (m) of the oxyfluoroalkylene chain represented by (OX) in Compound 1 is as small as 0 to 4, so that the affinity with the pressure-sensitive adhesive of the protective film has improved. do. In addition, since compound 2 has a poly(oxyfluoroalkylene) chain containing a unit 21 having a hydrogen atom, the surface tension is compared to the case where a poly(oxyfluoroalkylene) chain not having a hydrogen atom is used. This is thought to be because of the increase.

As a protective film, a resin film in which an adhesive was formed is mentioned. Examples of the pressure-sensitive adhesive include an acrylic pressure-sensitive adhesive, a urethane-based pressure-sensitive adhesive, or a silicone-based pressure-sensitive adhesive, and from the viewpoint of easy peeling, an acrylic pressure-sensitive adhesive is preferable. As a resin film, a polyvinyl chloride film, a polyethylene film, a polypropylene film, a polycarbonate film, a polyester film, or a polyurethane film is mentioned. From the viewpoint of easy peeling, a polyvinyl chloride film, a polyethylene film, or a polypropylene film is preferable.

(Compound 1)

Compound 1 is represented by Formula 1.

R ¹¹ -(OX) _m -YZ(R ¹² ) _q (R ¹³ ) _rq Equation 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 1 to 20, more preferably 1 to 10, still more preferably 1 to 6, and particularly preferably 1 to 3, from the viewpoint of more excellent weather resistance and corrosion resistance of the surface layer. The fluoroalkyl group may be linear, branched or cyclic.

X is a C1 or more fluoroalkylene group having 1 or more fluorine atoms.

The number of carbon atoms of the fluoroalkylene group is 1 or more, and from the viewpoint of more excellent weather resistance and corrosion resistance of the surface layer, 2 or more are preferable, 2 to 6 are more preferable, and 2 to 3 are particularly preferable.

Although linear or branched chain may be sufficient as a fluoroalkylene group, since the effect of this invention is more excellent, linear is preferable.

The fluoroalkylene group has one or more fluorine atoms. The number of fluorine atoms in the fluoroalkylene group is preferably 2 to 10, particularly preferably 2 to 4, from the viewpoint of more excellent corrosion resistance of the surface layer.

The fluoroalkylene group may be a group (perfluoroalkylene group) in which all hydrogen atoms in the fluoroalkylene group are substituted with fluorine atoms.

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 0 to 3 are preferable, and 0 or 1 is more preferable from the viewpoint of excellent balance of 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.

In addition, when m is 2 or more, a plurality of OX may be the same or different. In short, (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 may be arranged in random, alternating, or block forms.

Y is an alkylene group, a single bond, -O-, -C(O)N(R ¹⁴ )- which may have -O-, -C(O)N(R ¹⁴ )- or -C(O)- Or -C(O)-.

When the alkylene group has -O-, -C(O)N(R ¹⁴ )- or -C(O)-, having these groups between carbon-carbon atoms and at least one of the terminals on the (OX) _m side desirable.

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)-, between carbon-carbon atoms and (OX) _m- side terminal It is preferable to have these groups in both.

The number of carbon atoms of the alkylene group which may have -O-, -C(O)N(R ¹⁴ )- or -C(O)- is preferably 1 to 10, 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 1 to 10 carbon atoms).

Here, Y is -OCF ₂ -, if an alkylene group containing a number of _2- -OCF of the alkylene group is 1 dog. For example, the alkylene group represented by -OCF ₂ -, the alkylene group represented by -OCF ₂ CH ₂ OCH ₂ CH ₂ CH ₂ -, and the alkylene group represented by -OCF ₂ C(O)NHCH ₂ -are all -OCF ₂ -The number of is 1, and the definition of Y is satisfied. On the other hand, an alkylene group having two or more -OCF ₂ -s, 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 satisfy the definition of Y.

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 from 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.

As for the number of carbon atoms of the alkyl group, 1-5 are preferable, 1-3 are more preferable, and 1 is especially preferable.

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.

The number of carbon atoms in L ¹ is preferably 1 to 10, more preferably 1 to 6, and particularly preferably 1 to 4.

When there are more than one R ¹³ in one molecule, the plurality of R ¹³ may be the same or different. It is preferable that they are the same as each other in terms of availability of raw materials and ease of production of compound 1.

R ¹ is a monovalent hydrocarbon group, and a monovalent saturated hydrocarbon group is preferable. The number of carbon atoms 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.

As a specific example of L, an alkoxy group, a halogen atom, an acyl group, and an isocyanate group (-NCO) are mentioned. As the alkoxy group, an alkoxy group having 1 to 4 carbon atoms is preferable. As the halogen atom, a chlorine atom is preferable.

As L, a C1-C4 alkoxy group or a halogen atom is preferable because the preparation of compound 1 is easier. As L, from the viewpoint of less outgassing at the time of application and more excellent storage stability of compound 1, an alkoxy group having 1 to 4 carbon atoms is preferable, and when long-term storage stability of compound 1 is required, an ethoxy group is particularly preferable, When the reaction time after application is shortened, a methoxy group is particularly preferable.

n1 is an integer of 0-2.

As for n1, 0 or 1 is preferable, and 0 is especially preferable. When a plurality of L exist, 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. It is preferable that they are the same as each other from the viewpoints of easiness of obtaining raw materials and the ease of production of compound 1.

As a specific example of compound 1, the following examples 1-48 are mentioned.

[Formula 2]

[Formula 3]

Compound 1 can be produced by a known production method. For example, compound 1 can be produced by reacting a compound represented by formula 1A with a hydrosilylation reaction with HSi(R ¹ ) _n1 L _3-n1 (the definitions of R ¹ , L, n1 are as described above.) have.

R ¹¹ -(OX) _m -YZ(R ¹² ) _q (L ^1A -CH=CH ₂ ) _rq Equation 1A

In the formula, R ¹¹ , The definitions of X, m, Y, Z, R ¹² , q, r are as described above, L ^1A is an alkylene group which may have -O-, a single bond or -O-, and L ^1A -CH=CH _{When 2} is hydrosilylation, it becomes L ¹ of compound 1. When the compound represented by Formula 1A is, for example, when Y is -C(O)NHCH ₂ -, R ¹¹ -OH (the definition of R ¹¹ is as described above) is used as a raw material and is R ¹¹ by a known method. -(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 ) _rq and It can be prepared by reacting.

(Compound 2)

Compound 2 has a poly(oxyfluoroalkylene) chain containing the unit 21.

(OX ² ) Equation 21

X ² is a fluoroalkylene group having one or more hydrogen atoms.

1-6 are preferable and, as for the carbon number of a fluoroalkylene group, 2-4 are especially preferable.

The number of hydrogen atoms possessed by the fluoroalkylene group is one or more, and from the viewpoint of excellent balance of the adhesion of the surface layer to the protective film and the friction resistance of the surface layer, 1 to 3 are preferable, and 1 or 2 are particularly preferable.

The fluoroalkylene group has one or more fluorine atoms. The number of fluorine atoms in the fluoroalkylene group is one or more, and from the viewpoint of excellent balance of the adhesion of the surface layer to the protective film and the friction resistance of the surface layer, 1 to 11 are preferred, and 2 to 7 are particularly preferred.

X ² may be a linear type or a branched chain type, and a linear type is preferable from the viewpoint of more excellent friction resistance of the surface layer.

As for the repeating number m2 of the unit 21 contained in the poly(oxyfluoroalkylene) chain, an integer of 2 or more stages is preferable, an integer of 2 to 200 is more preferable, an integer of 5 to 150 is still more preferable, and 5 to An integer of 100 is particularly preferable, and an integer of 10 to 50 is most preferable.

The poly(oxyfluoroalkylene) chain may contain only one type of unit 21, or may contain two or more types of unit 21.

As two or more types of units 21, for example, two or more units of different carbon number 21, two or more types of units 21 different in the number of hydrogen atoms, and two or more types of units having different side chains or different types of side chains even if the number of carbon atoms is the same. 21 is mentioned.

The order of combining two or more types of units 21 is not limited, and may be arranged in random, alternating, or block forms.

As the (OX ² ) _{m2 of the} poly(oxyfluoroalkylene) chain,

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, and 100 or less are preferable.

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, even more preferably an integer of 5 to 100, and 10 to 50 The integer of is particularly preferred.

Among them, since the solubility of Compound 2 in a non-fluorine-based organic solvent is more excellent, an integer of 1 or more is preferable, and an integer of 2 to 200 is particularly preferable.

In addition, 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 or a linear chain is preferable from the viewpoint of more excellent friction resistance of the surface layer.

In addition, 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.

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, a 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 them, the following (1) to (4) are preferable as the (OX ² ) _m ^{2 of the} poly(oxyfluoroalkylene) chain from the viewpoint of more excellent solubility in the non-fluorine-based organic solvent.

In the above (1), m21, m24, m25 and m26 correspond to an aspect of 0, and m22 + m23 is an integer of 2 or more. In the above (2), m21, m23, m25 and m26 correspond to an aspect of 0, and m22 + m24 is an integer of 2 or more. In the above (3), m21, m23, m24 and m26 correspond to an aspect of 0, and m22 + m25 is an integer of 2 or more. In the above (4), m21, m23, m24 and m25 correspond to an aspect of 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 contain the unit 23.

(OX ²¹ ) Equation 23

X ²¹ is a perfluoroalkylene group. The number of carbon atoms of the perfluoroalkylene group is preferably 1 to 6.

The perfluoroalkylene group may be linear or branched, and a linear type is preferable from the viewpoint of more excellent friction resistance of the surface layer.

The poly(oxyfluoroalkylene) chain may contain only one type of unit 23, or may contain two or more types of unit 23.

As two or more types of units 23, for example, two or more types of units 23 different in number of carbon atoms, and two or more types of units 23 different in the presence or absence of side chains and different types of side chains even if the number of carbon atoms is the same.

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 an integer of 0 to 10 It is more preferable, and an integer of 0-2 is especially preferable.

When the poly(oxyfluoroalkylene) chain contains the unit 21 and the unit 23, the bonding order of the unit 21 and the unit 23 is not limited. For example, the unit 21 and the unit 23 may be arranged in random, alternating, or block forms.

When the poly(oxyfluoroalkylene) chain contains m2 of unit 21 and m20 of unit 23, m2 + m20 is an integer of 5 or more, preferably an integer of 5 to 400, and an integer of 5 to 200 Is more preferable, an integer of 5 to 120 is still more preferable, and an integer of 10 to 52 is particularly preferable.

Compound 2 has group 22.

-Si(R ² ) _n2 L ² _3-n2 Equation 22

The number of groups 22 in compound 2 is 1 or more, and from the viewpoint of more excellent friction resistance of the surface layer, 2 or more are preferable, 2 to 10 are more preferable, 2 to 5 are still more preferable, and 2 or Three are particularly preferred.

When there are more than one group 22 in one molecule, the plurality of groups 22 may be the same or different. In terms of availability of raw materials and ease of production of compound 2, the same ones are preferable.

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

L ² is a hydrolysable 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.

As a specific example of L ² , an alkoxy group, a halogen atom, an acyl group, and an isocyanate group (-NCO) are mentioned. As the alkoxy group, an alkoxy group having 1 to 4 carbon atoms is preferable. As the halogen atom, a chlorine atom is preferable.

As L ² , a C1-C4 alkoxy group or a halogen atom is preferable because the preparation of compound 2 is easier. As L ^{2, from the} viewpoint of less outgassing at the time of application and more excellent storage stability of compound 2, an alkoxy group having 1 to 4 carbon atoms is preferable, and when long-term storage stability of compound 2 is required, an ethoxy group is particularly preferable. When the reaction time after application|coating is made short, a methoxy group is especially preferable.

n2 is an integer of 0-2.

As for n2, 0 or 1 is preferable, and 0 is especially preferable. When a plurality of L ² exist, the adhesion of the surface layer to the substrate becomes stronger.

If n2 is less than or equal to 1, a plurality of L ² present in one molecule it may be the same or different. In terms of availability of raw materials and ease of production of compound 2, the same ones are preferable. If n2 is 2, a plurality of R ² may be the same or different are present in the molecule. In terms of availability of raw materials and ease of production of compound 2, the same ones are preferable.

In addition, the compound corresponding to both of the compound 1 and the compound 2 is handled as if it corresponds to only one of the compound 1 or the compound 2.

As the compound 2, the compound represented by Formula 2 is preferable from the viewpoint of more excellent adhesion of the surface layer to the protective film of 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 Equation 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 . In addition, 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 1 to 20, more preferably 1 to 10, and still more preferably 1 to 6 from the viewpoint of more excellent adhesion of the surface layer to the protective film and the friction resistance of the surface layer. And 1 to 3 are particularly preferable.

The alkyl group which may have a fluorine atom may be linear or branched, and a linear is preferable from the viewpoint of more excellent friction resistance of the surface layer.

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.

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, an integer of 5 to 400 is preferable, an integer of 5 to 200 is more preferable, an integer of 5 to 120 is still more preferable, and an integer of 10 to 52 An integer is particularly preferred.

In [(OX ² ) _m2 (OX ²¹ ) _m20 ], the binding 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.

Moreover, a plurality of (OX ² ) may be the same or different. In short, (OX ² ) _m2 may be composed of two or more types of (OX ² ) different in X ² . The order of combining two or more types of (OX ² ) is not limited, and may be arranged in random, alternating, or block forms.

Moreover, when m20 is 2 or more, a plurality of (OX ²¹ ) may be the same or different. In short, (OX ²¹ ) _m20 may be composed of two or more types of (OX ²¹ ) different in X ²¹ . The order of combining two or more types (OX ²¹ ) is not limited, and may be arranged in random, alternating, or block forms.

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.

The divalent linking group may be, for example, a divalent hydrocarbon group (a divalent saturated hydrocarbon group, a divalent aromatic hydrocarbon group, an alkenylene group, or an alkynylene group. The divalent saturated hydrocarbon group is linear or branched chain type. Or it may be a cyclic type, for example, an alkylene group, as for the number of carbon atoms, preferably 1 to 20, more preferably 1 to 10, particularly preferably 1 to 6. In addition, the divalent aromatic hydrocarbon group is C5-20 are preferable, and a phenylene group is mentioned, for example. In addition, a C2-C20 alkenylene group and a C2-C20 alkynylene group may be sufficient.), a divalent heterocyclic group, -O-, -S-, -SO ₂ -, -N(R ²⁴ )-, -C(O)-, -Si(R ²⁵ ) ₂ -, and groups obtained by combining two or more thereof. R ²⁴ is a hydrogen atom or an alkyl group (preferably 1 to 10 carbon atoms). R ²⁵ is an alkyl group (preferably having 1 to 10 carbon atoms) or a phenyl group.

In addition, as a group in which two or more of these are combined, for example, -C(O)N(R ²⁴ )-, -C(O)N(R ²⁴ )-alkylene group-, -O-alkylene group-, -OC(O)- is mentioned.

Among them, since the synthesis of compound 2 is easier, Y ² is a single bond, -O-, -C(O)-, -C(O)N(R ²⁴ )-, -C(O)N (R ²⁴ )-alkylene group- and -O-alkylene group- are preferable.

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.

As for the number of carbon atoms of the alkyl group, 1-5 are preferable, 1-3 are more preferable, and 1 is especially preferable.

When q2 is 2, two R ²² may be the same or different.

In terms of availability of raw materials and ease of production of the compound represented by Formula 2, the same is preferable.

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.

1-10 are preferable, as for the carbon number of L ²¹ , 1-6 are more preferable, and 1-4 are especially preferable.

When Z ² is a carbon atom or a silicon atom, r2 is 3, and q2 is an integer of 0-2. When Z ² is a nitrogen atom, r2 is 2, and q2 is an integer of 0 to 1.

When there are more than one R ²³ in one molecule, the plurality of R ²³ may be the same or different. In terms of availability of raw materials and ease of production of compound 2, the same ones are preferable.

As the compound 2, the compound represented by Formula 20 is preferable from the viewpoint of more excellent adhesion of the surface layer to the protective film of compound 2 and the friction resistance of the surface layer.

The definition of each group is as described above.

As a specific example of compound 2, the following examples 1-68 are mentioned. In the following table, t represents an integer of 1 or more. t is preferably an integer of 50 or less.

[Formula 4]

[Formula 5]

[Formula 6]

[Formula 7]

[Formula 8]

Compound 2 can be produced by a known production method. For example, in the compound represented by Formula 2 which is an aspect of compound 2, the compound represented by Formula 2A is HSi(R ² ) _n2 L ² _3-n2 (The definition of R ² , L ² , and n2 is as described above.) It can be produced by reacting with hydrosilylation.

R ^21A -[(OX ² ) _m2 (OX ²¹ ) _m20 ]-Y ² -Z ² (R ²² ) _q2 (L ^2A -CH=CH ₂ ) _r2-q2 Equation 2A

In the formula, X ² , X ²¹ , Y ² , Z ² , R ²² , m2, m20, q2, r2 are defined as above, and R ^21A is an alkyl group which may have a fluorine atom, or -Y ^2- Z ² (R ²² ) _q2 (L ^2A -CH=CH ₂ ) _r2-q2 , L ^2A is an alkylene group that may have -O-, a single bond or -O-, and L ^2A -CH=CH ₂ is When hydrosilylation, it becomes L ² of the compound represented by Formula 2. A compound represented by formula 2A, for example, Y ² is -C (O) NHCH ₂ - in the case, in a manner known to the R ^21A -OH as a starting material ^{R 21A - [(OX 2)} m2 (OX 21) m20 ]-C(O)OR ^2B (R ^2B is an alkyl group having 1 to 6 carbon atoms.) and reacted with NH ₂ -CH ₂ -Z ² (R ²² ) _q2 (L ^2A -CH=CH ₂ ) _r2-q2 It can be manufactured.

(Compound 3)

Compound 3 has a poly(oxyperfluoroalkylene) chain containing a repeating unit represented by Formula 31.

(OX ³ ) _m3 equation 31

X ³ is a perfluoroalkylene group.

The number of carbon atoms of the perfluoroalkylene group is preferably 1 to 6 from the viewpoint of more excellent water and oil repellency of the surface layer.

The perfluoroalkylene group may be linear or branched, but a linear is preferable from the viewpoint of more excellent water and oil repellency of the surface layer.

In addition, a plurality of OX ³ may be the same or different. In other words, (OX ³⁾ is _m3, and even if the number of carbon atoms is composed of two or more different OX ^3, or may be composed of a carbon number of side chain in the presence or absence or the side chain of the type with more than two kinds of different OX ³ same.

m3 is an integer of 5 or more, an integer of 5 to 200 is preferable, an integer of 5 to 150 is more preferable, and an integer of 10 to 100 is particularly preferable. When m3 is 5 or more, the water and oil repellency of the surface layer is more excellent. When m3 is less than or equal to 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 are present, 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 in random, alternating, or block forms.

With (OX ³ ) _m3 ,

However, m31 is an integer of 1 or more, m32, m33 and m34 are each an integer of 0 or 1 or more, m31 + m32 + m33 + m34 is an integer of 5 to 200, m31 OCF ₂ , m32 OCF ₂ CF _The order of combining ₂ , m33 OCF ₂ CF ₂ CF ₂ , m34 OCF ₂ CF ₂ CF ₂ CF ₂ is not limited. m36 and m37 are each an integer of 5 to 200, m35, m38 and m39 are an integer of 2 to 99, and m40 is an integer of 3 to 99.

In addition, in {(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 are 0, m32/m31 is , From the viewpoint of further excellent friction resistance of the surface layer, 0.1 to 10 are preferable, 0.2 to 5.0 are more preferable, 0.2 to 2.0 are still more preferable, 0.2 to 1.5 are particularly preferable, and 0.2 to 0.85 are most preferable.

Compound 3 has two or more groups 32.

-Si(R ³ ) _n3 L ³ _3-n3 Equation 32

The number of groups 32 in the compound 3 is 2 or more, and from the viewpoint of excellent friction resistance of the surface layer, 2 to 10 are preferable, 2 to 5 are more preferable, and 2 or 3 are particularly preferable.

When there are more than one group 32 in one molecule, the plurality of groups 32 may be the same or different. It is preferable that they are the same as each other in terms of availability of raw materials and ease of production of compound 3.

R ³ is a monovalent hydrocarbon group, and a monovalent saturated hydrocarbon group is preferable. The number of carbon atoms of R ³ is preferably 1 to 6, 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.

As a specific example of L ³ , an alkoxy group, a halogen atom, an acyl group, and an isocyanate group (-NCO) are mentioned. As the alkoxy group, an alkoxy group having 1 to 4 carbon atoms is preferable. As the halogen atom, a chlorine atom is preferable.

As L ³ , a C 1 to C 4 alkoxy group or a halogen atom is preferable because the preparation of compound 3 is easier. L ³ is preferably an alkoxy group having 1 to 4 carbon atoms from the viewpoint of less outgassing during application and more excellent storage stability of compound 3, and particularly preferably an ethoxy group when long-term storage stability of compound 3 is required. And, when the reaction time after application|coating is made short, a methoxy group is especially preferable.

n3 is an integer of 0-2.

As for n3, 0 or 1 is preferable, and 0 is especially preferable. When a plurality of L ³ exist, the adhesion of the surface layer to the substrate becomes stronger.

when n3 is 1 or less, a plurality of L ³ present in the molecule is may be the same or different. It is preferable that they are the same as each other from the viewpoint of availability of raw materials and ease of production of compound 3. if n3 is 2, plural R ³ may be the same or different are present in the molecule. It is preferable that they are the same as each other from the viewpoint of availability of raw materials and ease of production of compound 3.

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

As the compound 3, the compound represented by Formula 3 is preferable because the surface layer of the compound 3 is more excellent in water and oil repellency and friction resistance.

[A-(OX ³ ) _m3 -] _j Z ³ [-Si(R ³ ) _n3 L ³ _3-n3 ] _g Equation 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 1 to 10, more preferably 1 to 6, and particularly preferably 1 to 3 from the viewpoint of more excellent friction resistance of the surface layer.

The perfluoroalkyl group may be linear or branched.

However, when A is -Q[-Si(R ³ ) _n3 L ³ _3-n3 ] _k , j is 1.

As the perfluoroalkyl group, CF ₃ -, CF ₃ CF ₂ -and CF ₃ CF ₂ CF ₂ -are preferable from the viewpoint of more excellent water and oil repellency of the surface layer.

Q is a (k + 1) valent linking group. As mentioned later, k is an integer of 1-10. Therefore, as Q, a 2-11 valent coupling group is mentioned.

Q may be a group that does not impair the effects of the present invention, for example, an alkylene group, a carbon atom, a nitrogen atom, a silicon atom, or a 2 to 8 valent group which may have an etheric oxygen atom or a divalent organopolysiloxane residue. The organopolysiloxane residue, and the group in which Si(R ³ ) _n3 L ³ _3-n3 was removed from Formulas 3-1A, 3-1B, and 3-1A-1 to 3-1A-6 described later are mentioned.

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 a group that does not impair the effects of the present invention, for example, an alkylene group, a carbon atom, a nitrogen atom, a silicon atom, or 2 to 8 which may have an etheric oxygen atom or a divalent organopolysiloxane residue. A group in which Si(R ³ ) _n3 L ³ _3-n3 was removed from a valent organopolysiloxane residue, and formulas 3-1A, 3-1B, and 3-1A-1 to 3-1A-6 described later.

j is an integer greater than or equal to 1, and since the water and oil repellency of the surface layer is more excellent, an integer of 1 to 5 is preferred, and 1 is particularly preferred from the viewpoint of easy production of 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 since the friction resistance of the surface layer is more excellent, an integer of 2 to 4 is preferable, 2 or 3 is more preferable, and 3 is particularly preferable. Do. When A is -Q[-Si(R ³ ) _n3 L ³ _3-n3 ] _k , g + k is an integer of 2 or more, more preferably 2 or 3, and particularly preferably 3.

Compound 3 is preferably a compound represented by Formula 3-1 from the viewpoint of more excellent water and oil repellency of the surface layer.

A-(OX ³ ) _m3 -Z ³¹ Equation 3-1

In Formula 3-1, the definition of A, X ³ and m3 has the same meaning as the definition of each group in Formula 3.

Z ³¹ is a group 3-1A or a group 3-1B.

Q ^a is a single bond or a divalent linking group.

The divalent linking group may be, for example, a divalent hydrocarbon group (a divalent saturated hydrocarbon group, a divalent aromatic hydrocarbon group, an alkenylene group, or an alkynylene group. The divalent saturated hydrocarbon group is linear or branched chain type. Or it may be a cyclic type, for example, an alkylene group, the number of carbon atoms is preferably 1 to 20. In addition, the divalent aromatic hydrocarbon group is preferably 5 to 20 carbon atoms, for example, a phenylene group. In addition to that, an alkenylene group having 2 to 20 carbon atoms or an alkynylene group having 2 to 20 carbon atoms may be used.), a divalent heterocyclic group, -O-, -S-, -SO ₂ -, -N ( R ^d )-, -C(O)-, -Si(R ^a ) ₂ -, and groups obtained by combining two or more thereof. 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 1 to 10 carbon atoms).

In addition, as a group combining two or more of these, for example, -OC(O)-, -C(O)N(R ^d )-, alkylene group-O-alkylene group, alkylene group-OC(O) -Alkylene group, alkylene group-Si(R ^a ) ₂ -phenylene group-Si(R ^a ) ₂ is mentioned.

X ³¹ is a single bond, an alkylene group, a carbon atom, a nitrogen atom, a silicon atom, or a 2 to octavalent organopolysiloxane residue.

Further, 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 to 20, particularly preferably 1 to 10.

Examples of the 2 to 8 valent organopolysiloxane residues include a divalent organopolysiloxane residue and a (w + 1) valent organopolysiloxane residue described later.

Q ^b is a single bond or a divalent connecting group.

The definition of the divalent linking group has the same meaning as the definition described in Q ^a described above.

R ³¹ is a hydroxyl group or an alkyl group.

As for the number of carbon atoms of the alkyl group, 1-5 are preferable, 1-3 are more preferable, and 1 is especially preferable.

When X ³¹ is a single bond or an alkylene group, h is 1 and 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 h + i = 2 is satisfied,

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 h + i = 3 is satisfied,

When X ³¹ is a 2 to 8 valent 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 .

^{(-Q b -Si (R 3)} n3 L 3 3-n3) is the case where two or more, two or more ^{(-Q b -Si (R 3)} n3 L 3 3-n3) is, may be the same It may be different. When there are two or more R ³¹ , 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 a carbon atom and a carbon atom of an alkylene group having 2 or more carbon atoms, and a single bond is preferable from the viewpoint of easy production of a compound.

1-10 are preferable and, as for the carbon number of an alkylene group, 2-6 are especially preferable.

The number of carbon atoms of the group having an etheric oxygen atom between the carbon atom and the carbon atom of the alkylene group having 2 or more carbon atoms is preferably 2 to 10, particularly preferably 2 to 6.

R ³² is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and a hydrogen atom is preferable 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. 1-10 are preferable and, as for the carbon number of an alkylene group, 1-6 are especially preferable. From the viewpoint of easy production of a compound, Q ^d is preferably a single bond or -CH ₂ -.

R ³³ is a hydrogen atom or a halogen atom, and a hydrogen atom is preferable since it is easy to produce a compound.

y is an integer of 1-10, and an integer of 1-6 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.

As the group 3-1A, groups 3-1A-1 to 3-1A-6 are preferable.

However, when group 3-1A is group 3-1A-1, A in Formula 3-1 is -Q[-Si(R ³ ) _n3 L ³ _3-n3 ] _k .

In addition, in Formulas 3-1A-1 to 3-1A-6, definitions of R ³ , L ³ , and n3 are as described above.

X ³² is -O- or -C(O)N(R ^d )- (however, N in the formula is bonded to Q ^b1 ).

The definition of R ^d is as described above.

s1 is 0 or 1.

Q ^b1 is an alkylene group. Further, 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.

Moreover, 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 a carbon atom and a carbon atom.

1-10 are preferable and, as for the carbon number of the alkylene group represented by Q ^b1 , 2-6 are especially preferable.

For 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 -is preferred. (X ³² ) When _s1 is -O-, -CH ₂ CH ₂ CH ₂ -, -CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ -is preferable. (X ³² ) When _s1 is -C(O)N(R ^d )-, an alkylene group having 2 to 6 carbon atoms is preferable (however, N in the formula is bonded to Q ^b1 ). When Q ^b1 is these groups, it is easy to prepare a compound.

As a specific example of group 3-1A-1, the following groups are mentioned. In the following formula, * represents the bonding position with (OX ³ ) _m3 .

[Formula 9]

X ³³ is -O-, -NH-, or -C(O)N(R ^d )-.

The definition of R ^d is as described above.

Q ^a2 is a single bond, an alkylene group, -C(O)-, or an etheric oxygen atom between a carbon atom-carbon atom of an alkylene group having 2 or more carbon atoms, -C(O)-, -C(O)O-, It is a group having -OC(O)- or -NH-.

1-10 are preferable and, as for the carbon number of the alkylene group represented by Q ^a2 , 2-6 are especially preferable.

Q of a group having an etheric oxygen atom, -C(O)-, -C(O)O-, -OC(O)- or -NH- between carbon atoms and carbon atoms of an alkylene group having 2 or more carbon atoms represented by ^a2 2-10 are preferable and, as for carbon number, 2-6 are especially preferable.

Q ^a2 is -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)- is preferred (however, the right side is bonded to N).

s2 is 0 or 1 (however, when Q ^a2 is a single bond, it is 0.). From the point of easy production of the compound, 0 is preferred.

Q ^b2 is a group having a divalent organopolysiloxane residue, an etheric oxygen atom, or -NH- between carbon atoms and carbon atoms of an alkylene group or an alkylene group having 2 or more carbon atoms.

1-10 are preferable and, as for the carbon number of the alkylene group represented by Q ^b2 , 2-6 are especially preferable.

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 -carbon atoms is preferably 2 to 10, and 2 to 6 is It is particularly preferred.

As Q ^b2 , -CH ₂ CH ₂ CH ₂ -and -CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ -are preferable from the viewpoint of easy preparation of a compound (however, the right side is bonded to Si).

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

As a specific example of group 3-1A-2, the following groups are mentioned. In the following formula, * represents the bonding position with (OX ³ ) _m3 .

[Formula 10]

Q ^a3 is a single bond, an alkylene group, or a group having an etheric oxygen atom between a carbon atom and a carbon atom of an alkylene group having 2 or more carbon atoms, and a single bond is preferable from the viewpoint of easy production of a compound.

1-10 are preferable and, as for the carbon number of the alkylene group represented by Q ^a3 , 2-6 are especially preferable.

The number of carbon atoms of the group having an etheric oxygen atom between the carbon atom and the carbon atom of the alkylene group having 2 or more carbon atoms represented by Q ^a3 is preferably 2 to 10, 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 in the alkyl group represented by R ^g is preferably 1 to 4.

As G(R ^g ), C(OH) or Si(R ^ga ) (However, R ^ga is an alkyl group. The number of carbon atoms of the alkyl group is preferably 1 to 10, and a methyl group is particularly preferable. .) is preferred.

Q ^b3 is a group having an etheric oxygen atom or a divalent organopolysiloxane residue between a carbon atom and a carbon atom of an alkylene group or an alkylene group having 2 or more carbon atoms.

1-10 are preferable and, as for the carbon number of the alkylene group represented by Q ^b3 , 2-6 are especially preferable.

The number of carbon atoms of the group having an etheric oxygen atom or a divalent organopolysiloxane residue between the carbon atom and the carbon atom of the alkylene group having 2 or more carbon atoms represented by Q ^b3 is preferably 2 to 10, and particularly preferably 2 to 6.

As Q ^b3 , -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 -are preferable from the viewpoint of easy preparation of a compound. .

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

As a specific example of group 3-1A-3, the following groups are mentioned. In the following formula, * represents the bonding position with (OX ³ ) _m3 .

[Formula 11]

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 a carbon atom and a carbon atom of an alkylene group having 2 or more carbon atoms.

1-10 are preferable and, as for the carbon number of the alkylene group represented by Q ^a4 , 2-6 are especially preferable.

The number of carbon atoms of the group having an etheric oxygen atom between the carbon atom and the carbon atom of the alkylene group having 2 or more carbon atoms represented by Q ^a4 is preferably 2 to 10, particularly preferably 2 to 6.

t4 is 0 or 1 (however, when Q ^a4 is a single bond, it is 0.).

-Q ^a4 -(O) _t4 -is a single bond, -CH ₂ O-, -CH ₂ OCH ₂ -, -CH ₂ OCH ₂ CH ₂ O when s4 is 0 because it is easy to prepare a compound. -, -CH ₂ OCH ₂ CH ₂ OCH ₂ -, -CH ₂ OCH ₂ CH ₂ CH ₂ CH ₂ OCH ₂ -is preferred (however, the left side is bonded to (R ^f O) _m .), s4 is 1 In the case of, a single bond, -CH ₂ -, and -CH ₂ CH ₂ -are preferable.

Q ^b4 is an alkylene group, and the alkylene group is -O-, -C(O)N(R ^d )- (The definition of R ^d is as described above.), a silphenylene skeleton group, a divalent orthogonal group You may have a ganopolysiloxane residue or a dialkylsilylene group.

Further, when the alkylene group has an -O- or a silphenylene skeleton group, it is preferable to have an -O- or a silphenylene skeleton group between carbon atoms and carbon atoms. In addition, when the alkylene group has -C(O)N(R ^d )-, a dialkylsilylene group or a divalent organopolysiloxane residue, at the end of the side bonded to the carbon atom-carbon atom or (O) _u4 It is preferred to have these groups.

1-10 are preferable and, as for the carbon number of the alkylene group represented by Q ^b4 , 2-6 are especially preferable.

u4 is 0 or 1.

As -(O) _u4 -Q ^b4 -, -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 -is preferred (however, the right side is bonded to Si).

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

As a specific example of group 3-1A-4, the following groups are mentioned. In the following formula, * represents the bonding position with (OX ³ ) _m3 .

[Formula 12]

Q ^a5 is an alkylene group or a group having an ethereal oxygen atom between a carbon atom and a carbon atom of an alkylene group having 2 or more carbon atoms.

1-10 are preferable and, as for the carbon number of the alkylene group represented by Q ^a5 , 2-6 are especially preferable.

The number of carbon atoms of the group having an etheric oxygen atom between the carbon atom and the carbon atom of the alkylene group having 2 or more carbon atoms represented by Q ^a5 is preferably 2 to 10, particularly preferably 2 to 6.

With Q ^a5 , -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 (however, the right side is bonded to Si).

Q ^b5 is a group having an etheric oxygen atom or a divalent organopolysiloxane residue between a carbon atom and a carbon atom of an alkylene group or an alkylene group having 2 or more carbon atoms.

1-10 are preferable and, as for the carbon number of the alkylene group represented by Q ^b5 , 2-6 are especially preferable.

The number of carbon atoms of the group having an etheric oxygen atom or a divalent organopolysiloxane residue between carbon atoms and carbon atoms of the alkylene group having 2 or more carbon atoms represented by Q ^b5 is preferably 2 to 10, particularly preferably 2 to 6.

Q ^b5 is preferably -CH ₂ CH ₂ CH ₂ -, -CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ -from the viewpoint of easy preparation of a compound (however, 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.

As a specific example of group 2-1-5, the following groups are mentioned. In the following formula, * represents the bonding position with (OX ³ ) _m3 .

[Formula 13]

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

v is 0 or 1.

Q ^a6 is a group having an ethereal oxygen atom between a carbon atom and a carbon atom of an alkylene group or an alkylene group having 2 or more carbon atoms.

1-10 are preferable and, as for the carbon number of the alkylene group represented by Q ^a6 , 2-6 are especially preferable.

The number of carbon atoms of the group having an etheric oxygen atom between the carbon atom and the carbon atom of the alkylene group having 2 or more carbon atoms represented by Q ^a6 is preferably from 2 to 10, particularly preferably from 2 to 6.

With Q ^a6 , -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 (however, the right side is bonded to Z ^a ).

Z ^a is a (w + 1) valent organopolysiloxane residue.

w is an integer of 2-7.

The following groups are mentioned as a (w + 1) valent organopolysiloxane residue. However, R ^a in the following formula is as described above.

[Formula 14]

Q ^b6 is a group having an etheric oxygen atom or a divalent organopolysiloxane residue between carbon atoms and carbon atoms of an alkylene group or an alkylene group having 2 or more carbon atoms.

1-10 are preferable and, as for the carbon number of the alkylene group represented by Q ^b6 , 2-6 are especially preferable.

The number of carbon atoms of the group having an etheric oxygen atom or a divalent organopolysiloxane residue between the carbon atom and the carbon atom of the alkylene group having 2 or more carbon atoms represented by Q ^b6 is preferably 2 to 10, particularly preferably 2 to 6.

As Q ^b6 , -CH ₂ CH ₂ -and -CH ₂ CH ₂ CH ₂ -are preferable from the viewpoint of easy production of a compound.

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

(Content ratio of compounds 1 to 3)

Each of the compounds 1 to 3 may be used alone or in combination of two or more.

The content of compound 3 relative to the sum of the contents of compound 1 and compound 2 in the present composition is preferably 0.1 to 10 in terms of mass ratio from the viewpoint of excellent balance of the adhesion of the surface layer to the protective film and the friction resistance of the surface layer, 0.1 to 4 are more preferable, 0.1 to 1.5 are still more preferable, and 0.25 to 0.67 are particularly preferable.

In addition, for the compound corresponding to both of the compound 1 and the compound 2, the mass ratio is calculated assuming that it corresponds to only one of the compound 1 or the compound 2.

(Other ingredients)

This composition may contain a liquid medium.

Water and organic solvents are mentioned as a specific example of a liquid medium. Specific examples of the organic solvent include a fluorine-based organic solvent and a non-fluorine-based organic solvent.

Two or more types of 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, AGC) and C ₂ F ₅ CHFCHFCF ₃ (Battrel: 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 Can be mentioned.

The fluoroalkyl ether is preferably a compound having 4 to 12 carbon atoms, and, 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, 3M company), C ₄ F ₉ OC ₂ H ₅ (Novec 7200: product name, 3M company), C ₂ F ₅ CF(OCH ₃ )C ₃ F ₇ (Novec 7300: product name, 3M Manufactured by Co., Ltd.).

As a specific example of a fluorinated alkylamine, perfluorotripropylamine and perfluorotributylamine are mentioned.

As a specific example of fluoroalcohol, 2,2,3,3-tetrafluoropropanol, 2,2,2-trifluoroethanol, and hexafluoroisopropanol are mentioned.

As the non-fluorine-based organic solvent, a compound consisting of only hydrogen atoms and carbon atoms, and a compound consisting only of hydrogen atoms, carbon atoms and oxygen atoms are preferable, and specifically, a hydrocarbon-based organic solvent, a ketone-based organic solvent, and an ether-based organic solvent , Ester-based organic solvents, and alcohol-based organic solvents.

As a specific example of the hydrocarbon-based organic solvent, hexane, hepta, and cyclohexane are mentioned.

Specific examples of the ketone organic solvent include acetone, methyl ethyl ketone, and methyl isobutyl ketone.

As a specific example of the ether-based organic solvent, diethyl ether, tetrahydrofuran, and tetraethylene glycol dimethyl ether are mentioned.

Ethyl acetate and butyl acetate are mentioned as a specific example of the ester type organic solvent.

As a specific example of an alcoholic organic solvent, isopropyl alcohol is mentioned.

When the present composition contains a liquid medium, the content of the liquid medium is preferably 70 to 99.99 mass%, particularly preferably 80 to 99.9 mass%, based on the total mass of the composition.

When the present composition contains a liquid medium and further contains the compound 1, the content of the compound 1 is preferably 0.002 to 27.3% by mass, and particularly preferably 0.06 to 16.0% by mass, based on the total mass of the composition.

When the present composition contains a liquid medium and further contains the compound 2, the content of the compound 2 is preferably 0.002 to 27.3% by mass, and particularly preferably 0.06 to 16.0% by mass, based on the total mass of the composition.

When the present composition contains a liquid medium, the content of the compound 3 is preferably 0.001 to 24.0 mass%, particularly preferably 0.02 to 8.0 mass% with respect to the total mass of the composition.

This composition may contain components other than the above.

As other components, inevitable compounds in production such as by-products produced in the production process of compounds 1 to 3 and unreacted raw materials can be mentioned.

Moreover, additives, such as an acid catalyst and a basic catalyst, which accelerate 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. As a specific example of a basic catalyst, sodium hydroxide, potassium hydroxide, and ammonia are mentioned.

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 compounds 1 to 3.

[article]

The article of the present invention has a substrate and a surface layer formed of the composition on the substrate. It is preferable that a protective film is adhered to the surface of the surface layer.

The surface layer contains at least one compound selected from the group consisting of compound 1 and compound 2, and a compound obtained through a hydrolysis reaction and a condensation reaction of compound 3.

The film thickness of the surface layer is preferably 1 to 100 nm, particularly preferably 1 to 50 nm. For the film thickness of the surface layer, an X-ray diffractometer for thin film analysis (ATX-G: product name, manufactured by RIGAKU) was used to obtain an interference pattern of reflected X-rays by X-ray reflectance method, and calculated from the vibration period of the interference pattern can do.

The substrate is not particularly limited as long as it is a substrate for which imparting water and oil repellency is required. Specific examples of the material of the substrate include metal, resin, glass, sapphire, ceramic, stone, and composite materials thereof. The glass may be chemically strengthened. The substrate may be subjected to a base treatment with the compound described in paragraphs 0089 to 0095 of International Publication No. 2011/016458, SiO ₂ , or the like.

The article can be produced, for example, by the following method.

-A method of obtaining the article by treating the surface of a substrate by a dry coating method using this composition.

-A method of obtaining the article by applying the present composition to the surface of a substrate by a wet coating method and drying it.

Further, in the wet coating method, a composition comprising a compound obtained by hydrolyzing compounds 1 to 3 in advance using an acid catalyst, a basic catalyst, etc. and a liquid medium may be used.

When the difference between at least one compound selected from the group consisting of compound 1 and compound 2 and compound 3 contained in the present composition is small (preferably the difference between Mn is 0 to 3,000, particularly preferably the difference between Mn is 0 to 2,000), at least one compound selected from the group consisting of compound 1 and compound 2, and a surface layer in which compound 3 is uniformly distributed is obtained, so that the surface layer is preferably formed using a dry coating method.

On the other hand, when the difference between at least one compound selected from the group consisting of compound 1 and compound 2 and compound 3 contained in the present composition is large (preferably, the difference between Mn is 2,000 or more, particularly preferably The difference is 3,000 or more), at least one compound selected from the group consisting of compounds 1 and 2, and a surface layer in which compound 3 is uniformly distributed is obtained, it is preferable to form a surface layer using a wet coating method.

Specific examples of the dry coating method include a vacuum vapor deposition method, a CVD method, and a sputtering method. Among these, the vacuum evaporation method is preferable from the viewpoint of suppressing decomposition of the compounds 1 to 3 and the simplicity of the apparatus. At the time of vacuum vapor deposition, a pellet-like substance obtained by impregnating the present composition in a porous metal body such as iron or steel may be used.

As a specific example of the wet coating method, spin coating method, wipe coating method, spray coating method, squeegee coating method, dip coating method, die coating method, inkjet method, flow coating method, roll coating method, cast method, Langmuir The blowjet method and the gravure coating method are mentioned.

Example

Hereinafter, the present invention will be described in detail with reference to examples. However, the present invention is not limited to these examples. In addition, Examples 6 to 9, 11 to 16, and 18 to 19 are examples, and Examples 5, 10, 17 and 20 are comparative examples. The blending amount of each component represents a mass basis.

[Assessment 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 Corporation). It measured at five different points 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 better than 100 degrees.

(Test method of friction resistance)

For the surface layer, in accordance with JIS L0849:2013 (ISO 105-X12: 2001), a reciprocating traverse tester (manufactured by K&T) was used, and a steel wool Bonstar (#0000) was applied under pressure: 98.07 kPa, speed: 320 It was reciprocated at cm/min. The water contact angle was measured every 1000 reciprocations, and the number of reciprocations at the time when the water contact angle first became 85% or less with respect to the water contact angle before the test was measured. In addition, the upper limit of the number of round trips was 20,000 circuits. The more the number of round trips, the better the friction resistance. The number of round trips is preferably 5000 or more, more preferably 10,000 or more.

(Adhesion test method)

An acrylic adhesive layer of a polyvinyl chloride film having an acrylic adhesive layer (Erep Masking N-380: product name, manufactured by Nitto Electric Co., Ltd., tape width 50 mm) was affixed to the surface layer, and JIS K6854-1: 1999 (ISO 8510 -1: 90 degree peeling when peeling the said polyvinyl chloride film at room temperature (23 degreeC) at a peel rate of 100 mm/min using a 90 degree peeling tester (made by Nisshin Scientific Co., Ltd.) according to -1: 1990) The force was measured. The greater the peeling 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 in the following procedure.

(Example 1-1)

Compound X1 was obtained according to the method described in Example 6-1 of International Publication No. 2013/121984.

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)

To a 50 ml eggplant-shaped flask, 8.0 g of the compound X1 obtained in Example 1-1, 0.34 g of allyl bromide, 0.08 g of tetrabutylammonium bromide, and 0.60 g of a 48% by mass potassium hydroxide aqueous solution were added, and the mixture was 80°C. The mixture was stirred for 5 hours. The mixture was cooled to room temperature (23°C), 10 g of AC-6000 (product name, manufactured by AGC) was added, followed by washing with water twice. The obtained 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;

Compound X2: CH ₃ -(OCF ₂ CFHOCF ₂ CF ₂ CF ₂ CH ₂ ) _n -OCH ₂ CH=CH ₂ , average value of the 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, a xylene solution of platinum/1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum content: 2 mass%) of 0.06 g, HSi(OCH ₃ ) ₂ 1.01 g, aniline 0.02 g, and 1,3-bis(trifluoromethyl)benzene (manufactured by Tokyo Chemical Industry Co., Ltd.) 1.0 g were added, and the mixture was 40 It stirred at °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 (yield: 100%) of compound 2-A.

NMR spectrum of compound 2-A;

Average value of the number of repeating units n: 14, Mn of compound 2-A: 4,420.

[Example 2]

Compound 3-A was synthesized in the following procedure.

(Example 2-1)

Compound Y1 was obtained according to the method described in Examples 11-1 to 11-3 of International Publication No. 2013/121984.

(Example 2-2)

Into a 50 mL three-necked flask, 9.0 g of the compound Y1 and 0.45 g of NH ₂ CH ₂ C (CH ₂ CH = CH ₂ ) ₃ were put, and the mixture was stirred at room temperature (23° C.) for 12 hours. The reaction crude liquid was developed by silica gel column chromatography, and 9.4 g (yield 99%) of compound Y2 was fractionated.

(Example 2-3)

To 100 ml of a tetrafluoroethylene-perfluoro (alkoxy vinyl ether) copolymer made eggplant-shaped flask, 5.0 g of compound Y2, platinum/1,3-divinyl-1,1,3,3-tetramethyldisiloxane 0.03 g of a xylene solution (platinum content: 2% by mass) of the complex, 0.36 g of trimethoxysilane, 0.01 g of aniline and 2.0 g of 1,3-bis(trifluoromethyl)benzene were added, and the mixture was It stirred at room temperature (23 degreeC) for 8 hours. The solvent and the like were distilled off under reduced pressure, and filtered through a membrane filter having a pore diameter of 0.5 µm to obtain 5.2 g (purity of 99% or more, yield 99%) of compound 3-A.

NMR spectrum of compound 3-A;

[Example 3]

Compound 3-B was synthesized in the following procedure.

(Example 3-1)

Into a 50 ml three-neck 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 put, and the mixture was brought 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 by silica gel column chromatography, and 9.5 g (yield 99%) of compound Y3 was fractionated.

NMR spectrum of compound Y3;

(Example 3-2)

To 100 ml of tetrafluoroethylene-perfluoro (alkoxyvinyl ether) copolymer-made eggplant-shaped flask, 5.0 g of compound Y3, platinum/1,3-divinyl-1,1,3,3-tetramethyldisiloxane 0.03 g of a xylene solution (platinum content: 2% by mass) of the complex, 0.36 g of trimethoxysilane, 0.01 g of aniline and 2.0 g of 1,3-bis(trifluoromethyl)benzene were added, and the mixture was It stirred at room temperature (23 degreeC) for 8 hours. The solvent and the like were distilled off under reduced pressure, and filtered through a membrane filter having a pore diameter of 0.5 µm to obtain 5.2 g (purity of 99% or more, yield 99%) of compound 3-B.

NMR spectrum of compound 3-B;

[Example 4]

Compound 1-A is manufactured by Tokyo Chemical Industry Co., Ltd., trimethoxy (1H,1H,2H,2H-tridecafluoro-n-octyl)silane (CF ₃ -(CF ₂ ) ₅ (CH ₂ ) ₂ -Si( OCH ₃ ) ₃ ) was used.

[Examples 5 to 20]

Compositions of Examples 6 to 9, 11 to 16 and 18 to 19 by mixing each compound 1-A, 2-A, 3-A, and 3-B obtained in Examples 1 to 4 in the proportions shown in Tables 1 and 2 Got it.

Using the obtained composition, the substrate was surface-treated by the following dry coating method to obtain an evaluation sample (article) in which a surface layer was formed on the surface of the substrate (chemically strengthened glass).

In addition, about Examples 5, 10, 17 and 20, of the compounds 1-A, 2-A, 3-A, and 3-B, except for using only one type of compound, the above Examples 6 to 9, 11 to Each evaluation sample was produced by carrying out similarly to the case of 16 and 18-19.

Using each obtained evaluation sample, the above-described evaluation test was performed, and the results are shown in Tables 1 and 2.

(Dry coating method)

The composition (0.5 g) shown in Table 1 was disposed as a vapor deposition source in a boat made of molybdenum in a vacuum evaporation apparatus (VTR-350M: product name, manufactured by RBAK). The substrate was placed in a vacuum evaporation apparatus, and the inside of the vacuum evaporation apparatus was evacuated to a pressure of 5×10 ⁻³ Pa or less (absolute pressure). The boat on which the above compositions were placed was heated until it reached 300°C, and each of the compositions described in Table 1 was vacuum-deposited on the substrate to form a vapor deposition film having a thickness of 10 nm. The substrate on which the vapor deposition film was formed was heated (post-treated) at a temperature of 200° C. for 30 minutes to form a surface layer having a thickness of 10 nm to obtain an evaluation sample.

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

Industrial availability

The composition of the present invention can be used for various uses in which imparting water and oil repellency is required. For example, coats of display input devices such as touch panels; Surface protection coats of transparent glass or transparent plastic members, and antifouling coats for kitchens; Water-repellent, moisture-proof coats and antifouling coats such as electronic equipment, heat exchangers, and batteries; Antifouling coat for toiletry; Coat for members that need liquid repellency while conducting; Water-repellent, waterproof, and active water coat of heat exchanger; It can be used for surface low friction coats such as vibrating bodies and cylinder interiors.

More specific examples of use include a front protective plate, an antireflection plate, a polarizing plate, an anti-glare plate, or an anti-reflection film treatment applied to their surfaces, a touch panel sheet or a touch panel display 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 the fingers or palms of a person such as, etc., surface protection coats such as spectacle lenses, coats of decorative building materials for drainage of toilets, baths, washrooms, kitchens, etc. Water-repellent coating for heat exchanger, water-repellent, water-repellent, and active water-repellent coat for solar cells, waterproof and water-repellent coats for printed wiring boards, waterproof and water-repellent coats for electronic equipment casings and electronic parts, insulation improvement coats for transmission lines, and various filters. Waterproof and water-repellent coats, waterproof coats for radio wave absorbers and sound-absorbing materials, anti-soiling coats for bathrooms, kitchen equipment, toiletries, low-friction coats on surfaces such as vibrating bodies and cylinders, mechanical parts, vacuum equipment parts, bearing parts, transportation equipment for automobiles, etc. For example, parts (for example, exterior, glass, mirror, bumper), surface protection coats such as tools, etc. are mentioned.

In addition, the entire contents of the specification, claims, drawings, and abstract of Japanese Patent Application No. 2018-081607 for which it applied on April 20, 2018 are cited here, and taken as an indication of the specification of the present invention.

Claims (12)

At least one compound selected from the group consisting of compound 1 represented by formula 1 and compound 2 having a poly(oxyfluoroalkylene) chain including a repeating unit represented by formula 21 and a group represented by formula 22;
A composition comprising a poly(oxyperfluoroalkylene) chain containing a repeating unit represented by formula 31, a compound 3 having two or more groups represented by formula 32, and not containing a repeating unit represented by formula 21.
R ¹¹ -(OX) _m -YZ(R ¹² ) _q (R ¹³ ) _rq Equation 1
However, in Equation 1,
R ¹¹ is a fluoroalkyl group.
X is a C1 or more fluoroalkylene group having 1 or more fluorine atoms.
m is an integer of 0-4.
Y is an alkylene group, a single bond, -O-, -C(O)N(R ¹⁴ )- which may have -O-, -C(O)N(R ¹⁴ )- or -C(O)- Or -C(O)-. The alkylene group which may have -O-, -C(O)N(R ¹⁴ )- or -C(O)- may have a fluorine atom. Note that the Y -OCF ₂ -, if an alkylene group containing, -OCF ₂ in the alkylene group - the number of the first dog.
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 from 0 to 1. When Z is a nitrogen atom, r is 2 and q is 0.
(OX ² ) Equation 21
-Si(R ² ) _n2 L ² _3-n2 Equation 22
However, in Equations 21 and 22,
X ² is a fluoroalkylene group having one or more hydrogen atoms.
R ² is a monovalent hydrocarbon group.
L ² is a hydrolysable group or a hydroxyl group.
n2 is an integer of 0-2.
(OX ³ ) _m3 equation 31
-Si(R ³ ) _n3 L ³ _3-n3 Equation 32
However, in Equations 31 and 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. The method of claim 1,
The composition in which m in the above formula (1) is 0 or 1. The method according to claim 1 or 2,
The composition, wherein the compound 2 is a compound represented by Formula 2.
R ²¹ -[(OX ² ) _m2 (OX ²¹ ) _m20 ]-Y ² -Z ² (R ²² ) _q2 (R ²³ ) _r2-q2 Equation 2
However, in Equation 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 hydrolysable 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.
When Z ² is a carbon atom or a silicon atom, r2 is 3, and q2 is an integer of 0-2. When Z ² is a nitrogen atom, r2 is 2, and q2 is an integer of 0 to 1. The method according to any one of claims 1 to 3,
The composition, 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 Equation 3
However, in Equation 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 1-10.
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. . The method according to any one of claims 1 to 4,
The composition, wherein the difference between the number average molecular weight of at least one compound selected from the group consisting of compound 1 and compound 2 and compound 3 is 0 to 3,000. The method according to any one of claims 1 to 5,
The composition, wherein the content of the compound 3 is from 0.1 to 10 in terms of mass ratio with respect to the sum of the contents of the compound 1 and the compound 2. The method according to any one of claims 1 to 6,
A composition comprising a fluorine-based organic solvent, a non-fluorine-based organic solvent, or a liquid medium containing water. An article having a substrate and a surface layer formed on the substrate from the composition according to any one of claims 1 to 7. The method of claim 8,
An article formed of the composition by a dry coating method. The method of claim 8 or 9,
The article, wherein the substrate is a metal, resin, glass, sapphire, ceramic, stone, or a composite material thereof. The method according to any one of claims 8 to 10,
The article, wherein the surface layer has a film thickness of 1 to 100 nm. The method according to any one of claims 8 to 11,
An article in which a protective film is adhered to the surface of the surface layer.