TW202342409A - Article and method for producing the same, and surface treatment agent - Google Patents

Abstract

Provided are an article having a surface treatment layer with excellent weather resistance and wear resistance, a method for producing the same, and a surface treatment agent. The article includes, an organic substrate, a primer layer positioned on the organic substrate and formed of a primer containing a coupling agent having an organic reactive group and a hydrolyzable silyl group in one molecule, and a surface treatment layer formed from a surface treatment agent containing a fluoropolyether group-containing silane compound, located immediately above the primer layer, wherein the he fluoropolyether group-containing silane compound represented by the following formula (α1) or formula (α2):

In the formulae, each note has the same meaning as defined in the specification.

Description

Articles, manufacturing methods thereof, and surface treatment agents

The present disclosure relates to an antifouling article, a manufacturing method thereof, and a surface treatment agent.

In order to impart antifouling properties to an organic base material, Patent Documents 1 and 2 provide a primer layer and an antifouling layer on the base material.

[Prior technical literature]

[Patent Document]

[Patent Document 1] Japanese Patent Application Publication No. 2005-186576

[Patent Document 2] Japanese International Publication No. 2018/207811

However, the antifouling layers of Patent Documents 1 and 2 are insufficient in wear resistance and weather resistance. The purpose of this disclosure is to provide an article having a surface treatment layer with excellent weather resistance and abrasion resistance, a manufacturing method thereof, and a surface treatment agent.

This disclosure includes the following aspects.

[1]

An item that has:

organic substrate;

The primer layer is located on the aforementioned organic substrate and is formed of a primer. The primer contains a coupling agent, and the coupling agent has an organic reactive group and a hydrolyzable silicon group in one molecule; and

A surface treatment layer, which is located directly above the aforementioned primer layer and is formed of a surface treatment agent, which includes a silane compound α containing a fluoropolyether group;

The aforementioned silane compound α containing a fluoropolyether group is represented by the following formula ( α 1) or formula ( α 2),

In the formula,

R ¹ is a univalent organic group containing a polyether chain,

R ^1' is a divalent organic group containing a polyether chain,

X ¹ are each independently a reactive cross-linking group containing silane,

X ² are independently monovalent bases;

The aforementioned polyether chains are independently represented by the following formula each time they appear,

Formula: -(OC ₆ F ₁₂ ) _a -(OC ₅ F ₁₀ ) _b -(OC ₄ F ₈ ) _c -(OC ₃ X ¹⁰ ₆ ) _d -(OC ₂ F ₄ ) _e -(OCF ₂ ) _f -

In the formula,

a, b, c, d, e and f are each independently an integer of 0 or 1 or above,

The sum of a, b, c, d, e and f is 1 or more,

X ¹⁰ are independently H, F or Cl,

The order of existence of each repeating unit marked with the subscript a, b, c, d, e or f and enclosed in parentheses is arbitrary in the formula.

[2]

The article as described in the above [1], wherein the aforementioned polyether chain is independently represented by any one of the following formulas (f1) to formula (f6) each time it appears,

-(OC ₃ F ₆ ) _d -(OC ₂ F ₄ ) _e - (f1)

In the formula,

d is an integer from 1 to 200, e is 0 or 1;

-(OC ₄ F ₈ ) _c -(OC ₃ F ₆ ) _d -(OC ₂ F ₄ ) _e -(OCF ₂ ) _f - (f2)

In the formula,

c and d are each independently an integer from 0 to 30,

e and f are each independently an integer from 1 to 200,

The sum of c, d, e and f is 2 or more,

The order of existence of each repeating unit marked with the subscript c, d, e or f and enclosed in parentheses is arbitrary in the formula;

-(R ²¹ -R ²² ) _g - (f3)

In the formula,

R ²¹ is OCF ₂ or OC ₂ F ₄ ,

R ²² is a group selected from OC ₂ F ₄ , OC ₃ F ₆ , OC ₄ F ₈ , OC ₅ F ₁₀ and OC ₆ F ₁₂ , or 2 or 3 groups independently selected from these groups. combination,

g is an integer from 2 to 100;

-(R ²¹ -R ²² ) _g -R ^r -(R ^22' -R ^21' ) _g' - (f4)

In the formula, R ²¹ is OCF ₂ or OC ₂ F ₄ ,

R ²² is a group selected from OC ₂ F ₄ , OC ₃ F ₆ , OC ₄ F ₈ , OC ₅ F ₁₀ and OC ₆ F ₁₂ , or 2 or 3 groups independently selected from these groups. combination,

R ^21' is OCF ₂ or OC ₂ F ₄ ,

R ^22' is a group selected from OC ₂ F ₄ , OC ₃ F ₆ , OC ₄ F ₈ , OC ₅ F ₁₀ and OC ₆ F ₁₂ , or 2 or 3 groups independently selected from these groups. combination,

g is an integer from 2 to 100,

g' is an integer from 2 to 100,

R ^r is the following formula:

In the formula, * represents the bonding position;

-(OC ₆ F ₁₂ ) _a -(OC ₅ F ₁₀ ) _b -(OC ₄ F ₈ ) _c -(OC ₃ F ₆ ) _d -(OC ₂ F ₄ ) _e -(OCF ₂ ) _f - (f5)

In the formula,

e is an integer from 1 to 200,

a, b, c, d and f are each independently an integer from 0 to 200,

The order of existence of each repeating unit marked a, b, c, d, e or f and enclosed in parentheses is arbitrary in the formula;

-(OC ₆ F ₁₂ ) _a -(OC ₅ F ₁₀ ) _b -(OC ₄ F ₈ ) _c -(OC ₃ F ₆ ) _d -(OC ₂ F ₄ ) _e -(OCF ₂ ) _f - (f6)

In the formula,

f is an integer from 1 to 200,

a, b, c, d and e are each independently an integer from 0 to 200,

The order of existence of each repeating unit marked a, b, c, d, e or f and enclosed in parentheses is arbitrary in the formula.

[3]

Articles as described in the above [1] or [2], wherein X ¹ is represented by the following formula,

-L ¹ -{Si(R ^a ) _s (R ^b ) _t (R ^c ) _u (R ^d ) _v } _n

In the formula,

L ¹ is a single bond or a divalent linking group,

R ^a , R ^b and R ^c are each independently halogen, an alkoxy group having 1 to 10 carbon atoms, an amine group having 1 to 10 carbon atoms, an acetyloxy group having 1 to 10 carbon atoms, or an acetyloxy group having 3 to 10 carbon atoms. Allyl, or glycidyl with 3 to 10 carbon atoms,

R ^d are independently -O-, -NH-, -C≡C- or silane bond,

s, t and u are independently 0 or 1,

v is an integer from 0 to 3,

n is an integer from 1 to 20,

When n is 1, s+t+u is 3 and v is 0;

When n is 2 to 20, s+t+u is 0 to 2 independently, v is 0 to 2 independently,

When v is an integer of 1 or more, at least two Si are bonded via R ^d in a straight chain, ladder type, cyclic or polycyclic form.

[4]

The article as described in any one of the above [1] to [3], wherein the aforementioned surface treatment agent further contains: the aforementioned fluoropolyether group-containing agent represented by the aforementioned formula ( α 1) and the aforementioned formula ( α 2) Silane compound β containing fluoropolyether groups other than silane compound α .

[5]

The article according to any one of [1] to [4] above, wherein the number average molecular weight of the fluoropolyether group-containing silane compound α is 500 or more and 10,000 or less.

[6]

The article according to any one of the above [1] to [5], wherein the organic reactive group of the coupling agent contains an amine group, a glycidyl group, an epoxy group, a vinyl group, and a methacrylic group. At least one kind from the group consisting of acyl group, acryl group, styryl group, phenyl group, isocyanate group and mercapto group.

[7]

The article according to any one of [1] to [6] above, wherein the hydrolyzable silicon group of the coupling agent has two or more alkoxy groups having 1 to 5 carbon atoms.

[8]

The article according to any one of the above [1] to [7], wherein the hydrolyzable silicon group of the coupling agent contains at least one of a trimethoxysilyl group and a triethoxysilyl group.

[9]

The article according to any one of the above [1] to [8], wherein the aforementioned surface treatment agent further contains a cross-linking compound,

The cross-linked compound contains at least one of a compound represented by the following formula (Q1) and a compound represented by the following formula (Q2),

A[Z ^q1 -M ^q (OR ^q1 ) _wn1 (R ^q2 ) _wn2-wn1 ] _wa1 [Z ^q2 -R ^q3 ] _wa2 (Q1)

In the formula,

A is an organic radical with 1 to 10 valence,

Z ^q1 are independently single bonds or divalent organic groups,

M ^q is Al, Ca, Fe, Ge, Hf, In, Si, Ta, Ti, Sn, Zr or Zn;

R ^q1 are each independently a hydrogen atom or a C _1-6 alkyl group,

R ^q2 are each independently a hydrogen atom or a hydrocarbon group,

wn1 is independently 1 or more and (valence of M ^q -1) or less,

wn2 are independently (valence of M ^q -1),

Z ^q2 are independently single bonds or divalent organic groups,

R ^q3 are independently reactive groups,

wa1 is an integer from 1 to 10,

wa2 is an integer from 0 to 10,

The sum of wa1 and wa2 is the valence of A;

In the formula,

M is Al, Ca, Fe, Ge, Hf, In, Si, Ta, Ti, Sn, Zr or Zn;

R ^q are independently a hydrogen atom, C _1-6 alkyl group or R ^q1 -CO-;

R ^q1 is a 1-valent hydrocarbon group;

R ^q' are independently C _1-3 alkyl or C _1-3 alkoxy;

mq is the valence of the aforementioned M;

nq is 0 or more and less than the valence of M mentioned above.

[10]

The article described in [9] above, wherein wn1 is 2 or more.

[11]

The article according to the above [9] or [10], wherein the aforementioned R ^q1 groups are each independently a C _1-6 alkyl group.

[12]

The article according to any one of the above [9] to [11], wherein A is an alkylene group.

[13]

The article according to any one of the above [9] to [11], wherein A is a base represented by the following formula,

In the formula,

X ^a is each independently a single bond or a divalent organic group.

[14]

The article according to any one of the above [9] to [13], wherein the aforementioned R ^q3 groups are each independently an isocyanate group, an epoxy group or a vinyl group.

[15]

The article according to any one of the above [1] to [14], wherein the primer further contains at least one of an ultraviolet absorber and a radical scavenger.

[16]

The article according to any one of the above [1] to [15], wherein the surface treatment agent further contains at least one of an ultraviolet absorber and a radical scavenger.

[17]

A method of manufacturing an article, including:

Use a primer to form a primer layer on an organic substrate, where the primer contains a coupling agent that has an organic reactive group and a hydrolyzable silicone group in one molecule; and

Use a surface treatment agent to form a surface treatment layer directly above the above-mentioned primer layer. Here, the surface treatment agent includes a silane compound α containing a fluoropolyether group;

Among them, the aforementioned silane compound α containing a fluoropolyether group is represented by the following formula ( α 1) or formula ( α 2),

In the formula,

R ¹ is a univalent organic group containing a polyether chain,

R ^1' is a divalent organic group containing a polyether chain,

X ¹ are each independently a reactive cross-linking group containing silane,

X ² are independently monovalent bases;

The aforementioned polyether chains are independently represented by the following formula each time they appear,

Formula: -(OC ₆ F ₁₂ ) _a -(OC ₅ F ₁₀ ) _b -(OC ₄ F ₈ ) _c -(OC ₃ X ¹⁰ ₆ ) _d -(OC ₂ F ₄ ) _e -(OCF ₂ ) _f -

In the formula,

a, b, c, d, e and f are each independently an integer of 0 or 1 or above,

The sum of a, b, c, d, e and f is 1 or more,

X ¹⁰ are independently H, F or Cl,

The order of existence of each repeating unit marked with the subscript a, b, c, d, e or f and enclosed in parentheses is arbitrary in the formula.

[18]

A surface treatment agent used to manufacture the article described in any one of the above [1] to [16].

According to the present disclosure, an article having a surface treatment layer with excellent weather resistance and abrasion resistance, a manufacturing method thereof, and a surface treatment agent are provided.

FIG. 1 is a graph showing the results of the weather resistance test of the articles produced in Examples and Comparative Examples.

[thing]

An article according to one embodiment of the present disclosure includes: an organic substrate, a primer layer located on the organic substrate, and a surface treatment layer located directly above the primer layer. The primer layer is formed of a primer, and the primer contains a coupling agent that has an organic reactive group and a hydrolyzable silicon group in one molecule. The surface treatment layer is formed of a surface treatment agent containing a fluoropolyether group-containing silane compound α represented by the above formula (formula ( α 1) or formula α 2)) (hereinafter sometimes also referred to as PFPE Silane compound α ).

(organic substrate)

The organic base material is not particularly limited as long as at least part of the region where the primer layer is formed is formed of an organic material. Examples of organic materials include natural resins, synthetic resins, elastomers, rubber, and fibers (such as natural fibers, synthetic fibers, and regenerated fibers). Specifically, examples of organic substrates include hard-coated inorganic/organic substrates, coated inorganic/organic substrates, and fiber cloths (eg, woven fabrics, nonwoven fabrics).

Examples of synthetic resins include polycarbonate resin, poly(meth)acrylate resin, polyethylene terephthalate resin, cellulose triacetate resin, polyimide resin, and modified (transparent) polyimide. Amine resin, polycycloolefin resin, polyethylene naphthalate resin. The organic material can also be polycarbonate resin. Examples of the rubber include nitrile rubber, hydrogenated nitrile rubber, ethylene-propylene rubber, chloroprene rubber, acrylic rubber, urethane rubber, butyl rubber, natural rubber, fluorine rubber, and silicone rubber.

The shape of the organic substrate is not particularly limited, and may be, for example, plate-shaped, film-shaped, or other forms. In addition, the surface area of the base material on which the surface treatment layer is to be formed only needs to be at least a part of the surface of the base material, and can be appropriately determined according to the use of the article, specific specifications, etc.

The surface of the organic substrate may have hydroxyl groups. Hydroxyl groups can be introduced onto the surface of the organic substrate by plasma treatment (eg, corona discharge) or ion beam irradiation. The surface of the organic substrate may have silicone groups. When the hydrolyzable silicon group of the coupling agent contained in the primer is hydrolyzed, a silicon alcohol group is generated. When “organic substrate surface When the hydroxyl group or silanol group of the coupling agent reacts with the silanol group of the coupling agent, dehydration and condensation will occur to form a strong chemical bond.

(primer layer)

The primer layer sits on the organic substrate. The primer layer improves the adhesion between the organic substrate and the surface treatment layer.

The thickness of the primer layer is not particularly limited. From the viewpoint of adhesion, the thickness of the primer layer may be, for example, 1 nm or more or 5 nm or more. The thickness of the primer layer may be, for example, 50 nm or less, or 30 nm or less. In one aspect, the thickness of the primer layer is 1 nm or more and 50 nm or less.

〈Primer〉

The primer layer is formed from primer. The primer contains a coupling agent that has an organic reactive group and a hydrolyzable silicone group in one molecule.

The concentration of the coupling agent may be, for example, 0.05 mass% or more, 0.1 mass% or more, or 0.5 mass% or more based on 100 mass% of the primer. The concentration of the coupling agent may be, for example, 20 mass% or less, 10 mass% or less, or 5 mass% or less. In one aspect, the concentration of the coupling agent is, for example, 0.05 mass% or more and 20 mass% or less based on 100 mass% of the primer.

"Coupling Agent"

The coupling agent has an organic reactive group and a hydrolyzable silicon group in one molecule. These functional groups react with the PFPE silane compound α and/or the functional groups located on the surface of the organic substrate respectively, thereby improving the adhesion between the surface treatment layer and the organic substrate.

There may be only one organic reactive group (for example, at least one group "A" in the general formula of the coupling agent described below) in one molecule of the coupling agent, or two or more. The organic reactive group is not particularly limited. Examples of organic reactive groups include: amine group, glycidyl group, epoxy group, vinyl group, At least one kind from the group consisting of methacrylyl group, acrylyl group, styryl group, phenyl group, isocyanate group and mercapto group. The plurality of organic reactive groups may be of the same type or different types. The organic reactive group may be an amine group.

The hydrolyzable group (for example, at least one of the groups "B" in the general formula of the coupling agent described below, and together with the adjacent Si atoms constitute a hydrolyzable silicon group) only needs to be one in one molecule of the coupling agent. Yes, it can be more than 2, it can also be 3. The hydrolyzable group is not particularly limited as long as it is hydrolyzed to generate a siliconol group together with an adjacent Si atom. Examples of the hydrolyzable group include an alkoxy group, an acetyloxy group, and a chlorine atom. The hydrolyzable group may be an alkoxy group. The number of carbon atoms in the alkoxy group may be 1 to 5, or may be 1 to 3, or may be 1 or 2. The coupling agent may have two or more alkoxy groups having 1 to 5 carbon atoms bonded to Si. The plurality of hydrolyzable groups may be of the same type or different types. The carbon chain of the alkoxy group may be linear or branched.

Specific examples of the hydrolyzable silicon group include: trimethoxysilyl group, triethoxysilyl group, tripropoxysilyl group, tris(2-methoxyethoxy)silyl group, and dimethoxysilyl group Alkylsilyl, diethoxyalkylsilyl, dipropoxyalkylsilyl, bis(2-methoxyethoxy)alkylsilyl. The hydrolyzable silicon group may be at least either a trimethoxysilyl group or a triethoxysilyl group.

The coupling agent is represented by the following general formula, for example:

(AR ^CP ) _4-ns -Si-B _ns

In the formula, at least one of A is the above-mentioned organic reactive group, at least one of B is the above-mentioned hydrolyzable group, R ^CP is each independently a single bond or a divalent organic group, and ns is an integer from 1 to 3.

"-Si-B _ns " constitutes a hydrolyzable silicon group. In the above general formula, A other than the organic reactive group may be a hydrogen atom, for example. In the above general formula, B other than the hydrolyzable group may be, for example, a hydrocarbon group. ns can be 2 or more, or 3.

In the above general formula, R ^CP is a single bond or a divalent organic group, and may be a divalent organic group. Examples of R ^CP include: C _1-6 alkylene group, -(CH ₂ ) _cp1 -O-(CH ₂ ) _cp2 - (cp1 is an integer from 1 to 6, cp2 is an integer from 1 to 6), or - Phenylene-(CH ₂ ) _cp3 - (cp3 is an integer from 0 to 6). R ^CP may be C _1-3 alkylene group, C _2-3 alkylene group, or -CH ₂ CH ₂ CH ₂ -. These groups may be substituted by, for example, one or more substituents selected from the group consisting of fluorine atom, C _1-6 alkyl group, C _2-6 alkenyl group and C _2-6 alkynyl group.

Examples of the coupling agent include vinyltriethoxysilane, vinyltrimethoxysilane, vinyltris(2-methoxyethoxy)silane, vinylmethyldimethoxysilane, and p-styrylethoxysilane. Trimethoxysilane, p-styryltriethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methyl Acryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxysilane Propyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane Ethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-Mercaptopropyltrimethoxysilane, 3-Mercaptopropyltriethoxysilane, 3-octylthio-1-propyltriethoxysilane, 3-aminopropyltriethoxysilane, 3- Aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyl Dimethoxysilane, 3-(N-phenyl)aminopropyltrimethoxysilane, 3-triethoxysilyl-N-(1,3-dimethylbutylene)propylamine, N-( Vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-isocyanatepropyltriethoxysilane, 3-isocyanate Propyltrimethoxysilane, tris-(trimethoxysilylpropyl)isocyanurate. A coupling agent can be used individually by 1 type or in combination of 2 or more types.

"other"

Primers may also contain other additives. Examples of other additives include: tackifiers, leveling agents, defoaming agents, antistatic agents, antiturbidity agents, ultraviolet absorbers, free radical scavengers, pigments, dyes and fillers. Among them, from the viewpoint of weather resistance, the primer may contain at least one of an ultraviolet absorber and a radical scavenger.

(Triazine)系化合物、自由基聚合性化合物、無機系化合物。紫外線吸收劑可為三

系化合物。 Examples of ultraviolet absorbers include benzophenone compounds, benzotriazole compounds, and triazole compounds.

(Triazine) compounds, radically polymerizable compounds, and inorganic compounds. UV absorbers can be three

system compound.

Examples of benzophenone-based ultraviolet absorbers include 2,4-dihydroxydiphenylketone, 2-hydroxy-4-methoxydiphenylketone, and 2-hydroxy-4-methoxydiphenyl Ketone-5-sulfonic acid, 2-hydroxy-4-n-octyloxydiphenyl ketone, 2-hydroxy-4-n-dodeoxydiphenyl ketone, 2-hydroxy-4-benzyloxydiphenyl ketone Ketone, bis(5-benzyl-4-hydroxy-2-methoxyphenyl)methane, 2,2'-dihydroxy-4-methoxydiphenyl ketone, 2,2'-dihydroxy- 4,4'dimethoxydiphenylketone, 2,2',4,4'-tetrahydroxydiphenylketone, 4-dodeoxy-2-hydroxydiphenylketone, 5-benzyl ketone -2,4-Dihydroxydiphenylketone, 2-hydroxy-4-methoxy-2'-carboxydiphenylketone, 2-hydroxy-4-octadecyloxydiphenylketone, 4, 6-Dibenzylresorcinol.

Examples of benzotriazole-based ultraviolet absorbers include: 2-(2'-hydroxy-5'-methylphenyl) benzotriazole, 2-(2'-hydroxy-5'-tert-butylphenyl) )benzotriazole, 2-(2'-hydroxy-3',5'-di(tert-butyl)phenyl)benzotriazole, 2-(2-hydroxy-5-tert-octylphenyl )benzotriazole, 2-(2-hydroxy-3,5-di-tertiary octylphenyl)benzotriazole, 2-[2'-hydroxy-3',5'-bis(α,α '-Dimethylbenzyl)phenyl]benzotriazole), 2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3',5'-di-tert-pentylphenyl) benzotriazole, 2-(2'-hydroxy-4'-octyloxyphenyl) benzotriazole, 2-[2'-hydroxy-3'-(3",4",5",6"-tetrahydrophthalimidemethyl)-5'-methylphenyl]benzotriazole, 2,2-Methylenebis[4-(1,1,3,3-tetramethylbutyl)-6-(2H-benzotriazol-2-yl)phenol].

系紫外線吸收劑可列舉例如：2-[4-[(2-羥基-3-十二氧基丙基)氧基]-2-羥基苯基]-4,6-雙(2,4-二甲基苯基)-1,3,5-三

、2-[4-[(2-羥基-3-十三氧基丙基)氧基]-2-羥基苯基]-4,6-雙(2,4-二甲基苯基)-1,3,5-三

。 three

Examples of UV absorbers include: 2-[4-[(2-hydroxy-3-dodeoxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-di Methylphenyl)-1,3,5-tri

, 2-[4-[(2-hydroxy-3-tridecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1 ,3,5-three

.

Examples of radically polymerizable ultraviolet absorbers include 2-hydroxy-4-acryloxydiphenylketone, 2-hydroxy-4-methacryloxydiphenylketone, and 2-hydroxy-5-propene. Diphenyloxydiphenyl ketone, 2-hydroxy-5-methacryloxydiphenylketone, 2-hydroxy-4-(acrylyloxy-ethoxy)diphenylketone, 2-hydroxy- 4-(methacryloxy-ethoxy)diphenylketone, 2-hydroxy-4-(methacryloxy-diethoxy)diphenylketone, 2-hydroxy-4-( Acryloxy-triethoxy)diphenylketone, 2-(2'-hydroxy-5'-methacryloxyethyl-3-tert-butylphenyl)-2H-benzotri Azole, 2-(2'-hydroxy-5'-methacryloxypropyl-3-tert-butylphenyl)-5-chloro-2H-benzotriazole.

Examples of the inorganic ultraviolet absorber include cerium oxide, zinc oxide, aluminum oxide, zirconium oxide, bismuth oxide, cobalt oxide, copper oxide, tin oxide, and titanium oxide.

Examples of radical scavengers include hindered amine compounds.

Examples of hindered amine-based light stabilizers include bis(2,2,6,6-tetramethyl-4-piperidyl)succinate and bis(2,2,6,6-tetramethylpiperidyl). ) sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)2-(3,5-di(tert-butyl)-4-hydroxybenzyl)- 2-Butylmalonate, 1-[2-[3-(3,5-di(tert-butyl)-4-hydroxyphenyl)propynyloxy]ethyl]-4-[3- (3,5-Di(tert-butyl)-4-hydroxyphenyl)propynyloxy]-2,2,6,6-tetramethylpiperidine, bis(1-octyloxy-2,2 ,6,6-tetramethyl-4-piperidinyl) sebacate.

The (total) concentration of the ultraviolet absorber and/or radical scavenger may be, for example, 1 mass% or more, 2 mass% or more, or 3 mass% or more based on 100 mass% of the primer. The (total) concentration of the ultraviolet absorber and/or radical scavenger may be, for example, 10 mass% or less, 8 mass% or less, or 6 mass% or less based on 100 mass% of the primer. In one form, relative to primer 100 % by mass, the (total) concentration of the ultraviolet absorber and/or radical scavenger is 1 mass % or more and 10 mass % or less.

"Organic Solvent"

Primers can also be diluted with organic solvents. The organic solvent is not particularly limited. Examples of organic solvents include: lower alcohols such as ethanol, butanol, and isopropyl alcohol; ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; and cellosolve agents such as methyl cellosolve and ethyl cellosolve. ; Aromatic hydrocarbons such as xylene and toluene; aliphatic hydrocarbons such as n-hexane and n-heptane; esters such as ethyl acetate and butyl acetate.

(surface treatment layer)

The surface treatment layer is located directly above the primer layer. The surface treatment layer imparts antifouling properties to the organic substrate. The surface treatment layer used in this disclosure has excellent wear resistance and weather resistance, so it can maintain antifouling properties even when used under harsh outdoor environmental conditions for a long period of time.

The thickness of the surface treatment layer is not particularly limited. From the viewpoint of wear resistance and weather resistance, the thickness of the surface treatment layer may be 1 nm or more or 100 nm or more. The thickness of the surface treatment layer may be 2000 nm or less, 500 nm or less, or 200 nm or less. In one aspect, the thickness of the surface treatment layer is 1 nm or more and 2000 nm or less.

〈Surface treatment agent〉

The surface treatment layer is formed from a surface treatment agent. The surface treatment agent contains PFPE silane compound α . The concentration of the PFPE silane compound α relative to 100 mass% of the surface treatment agent is, for example, 0.001 mass% or more, 0.005 mass% or more, or 0.01 mass% or more. The concentration of the PFPE silane compound α is, for example, 1 mass% or less, 0.5 mass% or less, or 0.2 mass% or less. In one aspect, the concentration of the PFPE silane compound α is 0.001 mass% or more and 1 mass% or less.

"Silane Compounds Containing Fluoropolyether Groups"

The fluoropolyether group-containing silane compound α (PFPE silane compound α ) has a polyether chain and a reactive cross-linking group containing silane. PFPE silane compound α further has an isocycyanuric acid skeleton (hereinafter also referred to as an isocycyanuric acid ring). Through the isocycyanuric acid skeleton, the wear resistance and weather resistance of the obtained surface treatment layer are improved.

When used in this specification, the term "hydrocarbon group" means a group containing carbon and hydrogen, and is a group obtained by removing one hydrogen atom from a hydrocarbon. The hydrocarbon group is not particularly limited, and examples thereof include hydrocarbon groups having 1 to 20 carbon atoms that may be substituted by one or more substituents, such as aliphatic hydrocarbon groups, aromatic hydrocarbon groups, and the like. The above-mentioned "aliphatic hydrocarbon group" may be any one of linear chain, branched chain and cyclic, and may be any one of saturated and unsaturated. In addition, the hydrocarbon group may also contain one or more ring structures. The hydrocarbon may also have one or more N, O, S, Si, amide, sulfonyl, siloxane, carbonyl, carbonyloxy, etc. groups at the end or in the molecular chain.

When used in this specification, the substituent of "hydrocarbyl" is not particularly limited. Examples include: halogen atoms; those that may be substituted by one or more halogen atoms are selected from C _1-6 alkyl, C _{2- 6} alkenyl, C _2-6 alkynyl, C _3-10 cycloalkyl, C _3-10 unsaturated cycloalkyl, 5 to 10 membered heterocyclic group, 5 to 10 membered unsaturated heterocyclic group, C One or more of _6-10 aryl groups and 5 to 10-membered heteroaryl groups.

As used in this specification, "organic group" means a group containing carbon. The organic group is not particularly limited and may be a hydrocarbon group. In addition, the "2- to 10-valent organic group" means a 2- to 10-valent group containing carbon. The 2- to 10-valent organic group is not particularly limited, and may be a 2- to 10-valent group obtained by further detaching 1 to 9 hydrogen atoms from the hydrocarbon group. For example, the divalent organic group is not particularly limited, and examples include divalent groups obtained by detaching one hydrogen atom from a hydrocarbon group.

As used in this specification, "hydrolyzable group" means a group that can be separated from the main skeleton of the compound through a hydrolysis reaction. Examples of hydrolyzable groups include: -OR, -OCOR, -ON=CR ₂ , -NR ₂ , -NHR, halogen (in this equation, R represents a substituted or unsubstituted carbon number of 1 to 4 Alkyl), etc., can be -OR (that is, alkoxy). Examples of R include: unsubstituted alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, etc.; substituted alkyl groups such as chloromethyl. The hydroxyl group is not particularly limited and may be one capable of hydrolyzing a hydrolyzable group.

PFPE silane compound α is represented by the following formula ( α 1) or formula ( α 2).

[In the formula,

R ¹ is a univalent organic group containing a polyether chain,

R ^1' is a divalent organic group containing a polyether chain,

X ¹ are each independently a reactive cross-linking group containing silane,

X ² are independently monovalent bases;

The aforementioned polyether chains are independently represented by the following formula each time they appear,

Formula: -(OC ₆ F ₁₂ ) _a -(OC ₅ F ₁₀ ) _b -(OC ₄ F ₈ ) _c -(OC ₃ X ¹⁰ ₆ ) _d -(OC ₂ F ₄ ) _e -(OCF ₂ ) _f -

In the formula,

a, b, c, d, e and f are each independently an integer of 0 or 1 or above,

The sum of a, b, c, d, e and f is 1 or more,

X ¹⁰ are independently H, F or Cl,

The order of existence of each repeating unit marked with the subscript a, b, c, d, e or f and enclosed in parentheses is arbitrary in the formula].

As for R ¹ , it can be a monovalent organic group containing a polyether chain (but excluding those containing urethane bonds).

As for R ^1' , it can be a divalent organic group containing a polyether chain (but excluding those containing urethane bonds).

X ¹⁰ can be F.

a, b, c, d, e and f can each independently be an integer from 0 to 100.

The sum of a, b, c, d, e and f can be more than 5, more than 10, more than 15 or more than 20. The sum of a, b, c, d, e and f can be less than 200, less than 100, less than 60, less than 50 or less than 30.

The repeating units in the polyether chain can be linear or branched, and can also contain ring structures. The repeating units in the polyether chain can especially be linear.

-(OC ₆ F ₁₂ )-, for example, can be -(OCF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ )-, -(OCF(CF ₃ )CF ₂ CF ₂ CF ₂ CF ₂ )-, -(OCF ₂ CF(CF ₃ )CF ₂ CF ₂ CF ₂ )-, -(OCF ₂ CF ₂ CF(CF ₃ )CF ₂ CF ₂ )-, -(OCF ₂ CF ₂ CF ₂ CF(CF ₃ )CF ₂ )- or -(OCF ₂ CF ₂ CF ₂ CF ₂ CF(CF ₃ ))-, or -(OCF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ )-.

-(OC ₅ F ₁₀ )-, for example, can be -(OCF ₂ CF ₂ CF ₂ CF ₂ CF ₂ )-, -(OCF(CF ₃ )CF ₂ CF ₂ CF ₂ )-, -(OCF ₂ CF(CF ₃ )CF ₂ CF ₂ )-, -(OCF ₂ CF ₂ CF(CF ₃ )CF ₂ )- or -(OCF ₂ CF ₂ CF ₂ CF(CF ₃ ))-. It can also be -(OCF ₂ CF ₂ CF ₂ CF ₂ CF ₂ )-.

-(OC ₄ F ₈ )-, for example, can be -(OCF ₂ CF ₂ CF ₂ CF ₂ )-, -(OCF(CF ₃ )CF ₂ CF ₂ )-, -(OCF ₂ CF(CF ₃ )CF ₂ ) -, -(OCF ₂ CF ₂ CF(CF ₃ ))-, -(OC(CF ₃ ) ₂ CF ₂ )-, -(OCF ₂ C(CF ₃ ) ₂ )-, -(OCF(CF ₃ )CF (CF ₃ ))-, -(OCF(C ₂ F ₅ )CF ₂ )- or -(OCF ₂ CF(C ₂ F ₅ ))-. It can also be -(OCF ₂ CF ₂ CF ₂ CF ₂ )-.

-(OC ₃ F ₆ )- may be, for example, -(OCF ₂ CF ₂ CF ₂ )-, -(OCF(CF ₃ )CF ₂ )- or -(OCF ₂ CF(CF ₃ ))-. It can also be -(OCF ₂ CF ₂ CF ₂ )-.

-(OC ₂ F ₄ )- is -(OCF ₂ CF ₂ )- or -(OCF(CF ₃ ))-. Which can be -(OCF ₂ CF ₂ )-.

In one aspect, the repeating units are linear. By configuring the above repeating units into a linear chain, the surface smoothness of the surface treatment layer can be improved.

In one aspect, the repeating units are in the form of branched chains. By configuring the above repeating units in a branched chain shape, the dynamic friction coefficient of the surface treatment layer can be increased.

The above-mentioned ring structure may be the following three-member ring, four-member ring, five-member ring or six-member ring.

[In the formula, * represents the bonding position].

The above-mentioned ring structure can preferably be a four-member ring, a five-member ring or a six-member ring, and particularly preferably it can be a four-member ring or a six-member ring.

The repeating unit having a ring structure is preferably the following unit.

[In the formula, * represents the bonding position].

In one aspect, the polyether chain is independently a group represented by any one of the following formulas (f1) to formula (f6) each time it appears.

-(OC ₃ F ₆ ) _d -(OC ₂ F ₄ ) _e - (f1)

[In the formula,

d is an integer from 1 to 200,

e is 0 or 1];

-(OC ₄ F ₈ ) _c -(OC ₃ F ₆ ) _d -(OC ₂ F ₄ ) _e -(OCF ₂ ) _f - (f2)

[In the formula,

c and d are each independently an integer from 0 to 30,

e and f are each independently an integer from 1 to 200,

The sum of c, d, e and f is 2 or more,

The order of existence of each repeating unit marked with the subscript c, d, e or f and enclosed in parentheses is arbitrary in the formula];

-(R ²¹ -R ²² ) _g - (f3)

[In the formula,

R ²¹ is OCF ₂ or OC ₂ F ₄ ,

R ²² is a group selected from OC ₂ F ₄ , OC ₃ F ₆ , OC ₄ F ₈ , OC ₅ F ₁₀ and OC ₆ F ₁₂ , or 2 or 3 groups independently selected from these groups. combination,

g is an integer from 2 to 100];

-(R ²¹ -R ²² ) _g -R ^r -(R ^22' -R ^21' ) _g' - (f4)

[In the formula, R ²¹ is OCF ₂ or OC ₂ F ₄ ,

R ²² is a group selected from OC ₂ F ₄ , OC ₃ F ₆ , OC ₄ F ₈ , OC ₅ F ₁₀ and OC ₆ F ₁₂ , or 2 or 3 groups independently selected from these groups. combination,

R ^21' is OCF ₂ or OC ₂ F ₄ ,

R ^22' is a group selected from OC ₂ F ₄ , OC ₃ F ₆ , OC ₄ F ₈ , OC ₅ F ₁₀ and OC ₆ F ₁₂ , or 2 or 3 groups independently selected from these groups. combination,

g is an integer from 2 to 100,

g' is an integer from 2 to 100,

R ^r is the following formula:

In the formula, * represents the bonding position];

-(OC ₆ F ₁₂ ) _a -(OC ₅ F ₁₀ ) _b -(OC ₄ F ₈ ) _c -(OC ₃ F ₆ ) _d -(OC ₂ F ₄ ) _e -(OCF ₂ ) _f - (f5)

[In the formula,

e is an integer above 1 and below 200,

a, b, c, d and f are each independently an integer from 0 to 200,

The order of existence of each repeating unit marked a, b, c, d, e or f and enclosed in parentheses is arbitrary in the formula];

-(OC ₆ F ₁₂ ) _a -(OC ₅ F ₁₀ ) _b -(OC ₄ F ₈ ) _c -(OC ₃ F ₆ ) _d -(OC ₂ F ₄ ) _e -(OCF ₂ ) _f - (f6)

[In the formula,

f is an integer from 1 to 200,

a, b, c, d and e are each independently an integer from 0 to 200,

The order of existence of each repeating unit marked a, b, c, d, e or f and enclosed in parentheses is arbitrary in the formula].

In the above formula (f1), d is an integer from 5 to 200, 10 to 100, 15 to 50 or 25 to 35. OC ₃ F ₆ can be (OCF ₂ CF ₂ CF ₂ ) or (OCF (CF ₃ )CF ₂ ) or (OCF ₂ CF (CF ₃ )), or (OCF ₂ CF ₂ CF ₂ ). (OC ₂ F ₄ ) can be (OCF ₂ CF ₂ ) or (OCF (CF ₃ )), or (OCF ₂ CF ₂ ). In one state, e is 0. In other modalities, e is 1.

In the above formula (f2), e and f can be independently from 5 to 200, or can be an integer from 10 to 200. The sum of c, d, e and f may be 5 or more, 10 or more, 15 or more or 20 or more. In one form, the above formula (f2) is -(OCF ₂ CF ₂ CF ₂ CF ₂ ) _c -(OCF ₂ CF ₂ CF ₂ ) _d -(OCF ₂ CF ₂ ) _e -(OCF ₂ ) _f - express. In other aspects, formula (f2) is represented by -(OC ₂ F ₄ ) _e -(OCF ₂ ) _f -.

In the above formula (f3), R ²¹ may be OC ₂ F ₄ . R ²² can be a group selected from OC ₂ F ₄ , OC ₃ F ₆ and OC ₄ F ₈ or a combination of 2 or 3 groups independently selected from these groups, or it can also be selected from OC ₃ F ₆ and the base in OC ₄ F ₈ . The combination of the above two or three groups is not particularly limited, and examples include: -OC ₂ F ₄ OC ₃ F ₆ -, -OC ₂ F ₄ OC ₄ F ₈ -, -OC ₃ F ₆ OC ₂ F ₄ -, -OC ₃ F ₆ OC ₃ F ₆ -, -OC ₃ F ₆ OC ₄ F ₈ -, -OC ₄ F ₈ OC ₄ F ₈ -, -OC ₄ F ₈ OC ₃ F ₆ -, -OC ₄ F ₈ OC ₂ F ₄ -, -OC ₂ F ₄ OC ₂ F ₄ OC ₃ F ₆ -, - OC ₂ F ₄ OC ₂ F ₄ OC ₄ F ₈ -, -OC ₂ F ₄ OC ₃ F ₆ OC ₂ F ₄ -, -OC ₂ F ₄ OC ₃ F ₆ OC ₃ F ₆ -, -OC ₂ F ₄ OC ₄ F ₈ OC ₂ F ₄ -, -OC ₃ F ₆ OC ₂ F ₄ OC ₂ F ₄ -, -OC ₃ F ₆ OC ₂ F ₄ OC ₃ F ₆ -, -OC ₃ F ₆ OC ₃ F ₆ OC ₂ F ₄ - and OC ₄ F ₈ OC ₂ F ₄ OC ₂ F ₄ -, etc. g may be 3 or more, or an integer of 5 or more. g can be an integer below 50. OC ₂ F ₄ , OC ₃ F ₆ , OC ₄ F ₈ , OC ₅ F ₁₀ and OC ₆ F ₁₂ may be either linear or branched chains, and may also be linear chains. In one aspect, the above formula (f3) is -(OC ₂ F ₄ -OC ₃ F ₆ ) _g - or (OC ₂ F ₄ -OC ₄ F ₈ ) _g -.

In the above-mentioned formula (f4), R ²¹ , R ²² and g have the same meaning and the same aspect as those described in the above-mentioned formula (f3). R ^21' , R ^22' and g' respectively have the same meaning and form as R ²¹ , R ²² and g described in the above formula (f3). R ^r is preferably the following formula:

[In the formula, * represents the bonding position],

Particularly preferred is the following formula:

[In the formula, * represents the bonding position].

In the above formula (f5), e may be 1 or more and 100 or less, or may be an integer of 5 or more and 100 or less. The sum of a, b, c, d, e and f may be 5 or more, 10 or more, or 10 or more and 100 or less.

In the above formula (f6), f may be 1 or more and 100 or less, or may be an integer of 5 or more and 100 or less. The sum of a, b, c, d, e and f may be 5 or more, 10 or more, or 10 or more and 100 or less.

In one aspect, the polyether chain is represented by formula (f1).

In one aspect, the polyether chain is represented by formula (f2).

In one aspect, the polyether chain is represented by formula (f3).

In one aspect, the polyether chain is represented by formula (f4).

In one aspect, the polyether chain is represented by formula (f5).

In one aspect, the polyether chain is represented by formula (f6).

In the polyether chain, the larger the ratio of e to f (hereinafter referred to as the "e/f ratio"), the greater the stability of the PFPE silane compound α can be improved. The smaller the e/f ratio is, the better the surface smoothness of the surface treatment layer can be improved. The e/f ratio is, for example, 0.1 or more. When the e/f ratio is above 0.1, the stability of PFPE silane compound α will be further improved. The e/f ratio is, for example, 10 or less. When the e/f ratio is below 10, the smoothness of the surface treatment layer can be easily further improved, which can improve abrasion resistance and chemical resistance (such as durability against artificial sweat). The e/f ratio can be above 0.2. The e/f ratio may be 5 or less, 2 or less, 1.5 or less, or 0.85 or less. In one aspect, the e/f ratio is, for example, 0.1 or more and 10 or less.

The average molecular weight of the polyether chain is not particularly limited. The average molecular weight of the polyether chain is, for example, 500 or more, 1,500 or more, or 2,000 or more. The average molecular weight of the polyether chain is, for example, 30,000 or less, and may be 10,000 or less. In one aspect, the average molecular weight of the polyether chain is above 500 and below 30,000. In this specification, the average molecular weight means the number average molecular weight, which is measured by ¹⁹ F-NMR.

In other aspects, the average molecular weight of the polyether chain is, for example, 500 or more, 1,000 or more, 2,000 or more, or 3,000 or more. The average molecular weight of the polyether chain is, for example, 30,000 or less, 20,000 or less, 15,000 or less, 10,000 or less, or 6,000 or less. In one aspect, the average molecular weight of the polyether chain is above 500 and below 30,000.

In other aspects, the average molecular weight of the polyether chain is, for example, more than 4,000, may be more than 5,000, or may be more than 6,000. The average molecular weight of the polyether chain is, for example, 30,000 or less, and may be 10,000 or less. In one form, the average molecular weight of the polyether chain is between 4,000 and 30,000.

R ¹ is, for example, a monovalent organic group represented by the following formula,

R ³ -(PAO)-L ^α2 -

[In the formula, PAO is the above-mentioned polyether chain,

R ³ is alkyl or fluorinated alkyl,

L ^α2 is a single bond or a divalent linking group].

R ^1' is, for example, a monovalent organic group represented by the following formula,

-L ^α3 -(PAO)-L ^α2 -

[In the formula, PAO is the above-mentioned polyether chain,

L ^α2 is a single bond or a divalent linking group,

L ^α3 is a single bond or a divalent linking group,

L ^α2 is bonded to the isocyanuric acid ring on the right side of formula ( α 2), and L ^α3 is bonded to the isocyanuric acid ring on the left side].

The carbon number of R ³ is, for example, 1 to 16, 1 to 8, 1 to 6, or 1 to 3. ^R3 can be a straight chain or a branched chain.

R ³ is, for example, a linear or branched chain alkyl group having 1 to 16 carbon atoms or a fluorinated alkyl group. The number of carbon atoms in the alkyl group may be 1 to 8, or may be 1 to 6, or may be 1 to 3. R ³ may be a linear alkyl group having 1 to 3 carbon atoms or a fluorinated alkyl group.

R ³ may be a fluorinated alkyl group having 1 to 16 carbon atoms, a CF ₂ HC _1-15 fluoroalkylene group, or a perfluoroalkyl group having 1 to 16 carbon atoms.

R ³ may be a linear or branched perfluoroalkyl group having 1 to 16 carbon atoms. The number of carbon atoms in the perfluoroalkyl group may be 1 to 6, or may be 1 to 3. R ³ may be a linear perfluoroalkyl group having 1 to 3 carbon atoms. R ³ is, for example, -CF ₃ , -CF ₂ CF ₃ or CF ₂ CF ₂ CF ₃ .

L ^α2 is a single bond or a divalent linking group directly bonded to the "isocyanuric acid ring of formula ( α 1) or formula ( α 2)". L ^α2 may be a single bond, an alkylene group, or a divalent group containing at least one of an ether bond and an ester bond. L ^α2 may be a single bond, an alkylene group having 1 to 10 carbon atoms, or a divalent hydrocarbon group having 1 to 10 carbon atoms containing at least one of an ether bond and an ester bond.

L ^α2 can be the base represented by the following formula,

-(CX ¹²¹ X ¹²² ) _o -(L') _p -(CX ¹²³ X ¹²⁴ ) _q -

_[ ^In the ^{formula ,} X ¹²¹ to

L' is -C(=O)NH-, -NHC(=O)-, -O-, -C(=O)O-, -OC(=O)-, -OC(=O)O- or -NHC(=O)NH-(the left side of each bond is bonded to CX ¹²¹ X ¹²² ),

o is an integer from 0 to 10,

p is 0 or 1,

q is an integer from 1 to 10].

L ^α2 can be a base represented by the following formula,

-(CF ₂ ) _m11 -(CH ₂ ) _m12 -O-(CH ₂ ) _m13 -

[In the formula, m11 is an integer from 1 to 3, m12 is an integer from 1 to 3, and m13 is an integer from 1 to 3];

Or the basis represented by the following formula,

-(CF ₂ ) _m14 -(CH ₂ ) _m15 -O-CH ₂ CH(OH)-(CH ₂ ) _m16 -

[In the formula, m14 is an integer from 1 to 3, m15 is an integer from 1 to 3, and m16 is an integer from 1 to 3];

Or the basis represented by the following formula,

-(CF ₂ ) _m17 -(CH ₂ ) _m18 -

[In the formula, m17 is an integer from 1 to 3, m18 is an integer from 1 to 3];

Or the basis represented by the following formula:

-(CF ₂ ) _m19 -(CH ₂ ) _m20 -O-CH ₂ CH(OSi(OCH ₃ ) ₃ )-(CH ₂ ) _m21 -

[In the formula, m19 is an integer from 1 to 3, m20 is an integer from 1 to 3, and m21 is an integer from 1 to 3].

Examples of L ^α2 include: -C ₂ H ₄ -, -C ₃ H ₆ -, -C ₄ H ₈ -O-CH ₂ -, -CO-O-CH ₂ -CH(OH)-CH ₂ -, - (CF ₂ ) _n1 -(n1 is an integer from 0 to 4), -CH ₂ -, -C ₄ H ₈ -, -(CF ₂ ) _n2 -(CH ₂ ) _n3 -(n2, n3 are both 0 independently to 4), -CF ₂ CF ₂ CH ₂ OCH ₂ CH(OH)CH ₂ - and -CF ₂ CF ₂ CH ₂ OCH ₂ CH(OSi(OCH ₃ ) ₃ )CH ₂ -.

L ^α3 can be the base represented by the following formula,

-(CX ¹²⁶ X ¹²⁷ ) _r -( ^{CX 121} X ¹²² ) _o - ₍ L') _p -(CX ¹²³

[In the formula, X ¹²¹ to X ¹²⁴ , L', o, p and q have the same meaning as those specified in L ^α2 above,

X ¹²⁶ and X ¹²⁷ are independently H, F or Cl, and can be F,

R is an integer from 1 to 6,

^- ( _CX ¹²⁶ X ¹²⁷ ) _r - is bonded to (PAO), (CX ¹²³

L' can be -O- or C(=O)O.

X ¹ is a monovalent reactive cross-linking group containing silane. X ¹ system is beneficial to the adhesion with the substrate. X ¹ can also react chemically with the material of the above substrate.

In one state, X ¹ is represented by the following formula,

-L ^α1 -{Si(R ^a ) _s (R ^b ) _t (R ^c ) _u (R ^d ) _v } _n

[In the formula,

L ^α1 is a single bond or a divalent linking group,

R ^a , R ^b and R ^c are each independently halogen, an alkoxy group having 1 to 10 carbon atoms, an amine group having 1 to 10 carbon atoms, an acetyloxy group having 1 to 10 carbon atoms, or an acetyloxy group having 3 to 10 carbon atoms. Allyl or glycidyl group having 3 to 10 carbon atoms,

R ^d are independently -O-, -NH-, -C≡C- or silane bond,

s, t and u are independently 0 or 1,

v is an integer from 0 to 3,

n is an integer from 1 to 20,

When n is 1, s+t+u is 3 and v is 0;

When n is 2 to 20, s+t+u is 0 to 2 independently, v is 0 to 2 independently,

When v is an integer of 1 or more, at least two Si are bonded via R ^d in a straight chain, ladder type, cyclic or polycyclic form].

L ^α1 is a single bond or a bivalent linking group directly bonded to the "isocyanuric acid ring of formula ( α 1) or formula ( α 2)". L ^α1 may be a single bond, an alkylene group, or a divalent group containing at least one of an ether bond and an ester bond. L ^α1 may be a single bond, an alkylene group having 1 to 10 carbon atoms, or a divalent hydrocarbon group having 1 to 10 carbon atoms containing at least one of an ether bond and an ester bond.

Examples of L ^α1 include: -C ₂ H ₄ -, -C ₃ H ₆ -, -C ₄ H ₈ -O-CH ₂ -, -CO-O-CH ₂ -CH(OH)-CH ₂ -, - CH ₂ -, -C ₄ H ₈ -.

R ^a , R ^b and R ^c are univalent groups bonded to Si. At least one of R ^a , R ^b and R ^c may be a halogen, an alkoxy group having 1 to 10 carbon atoms, or an amine group having 1 to 10 carbon atoms. In addition, R ^a , R ^b and R ^c may be an acetyloxy group having 1 to 10 carbon atoms, an allyl group having 3 to 10 carbon atoms, or a glycidyl group having 3 to 10 carbon atoms. R ^a , R ^b and R ^c may each be an alkoxy group having 1 to 5 carbon atoms, or may be an alkoxy group having 1 to 4 carbon atoms.

In R ^a , R ^b and R ^c , the halogen may be Cl, Br or I, and may also be Cl.

In R ^a , R ^b and R ^c , the carbon number of the alkoxy group may be 1 to 5. Alkoxy groups can be chain, cyclic or branched. The hydrogen atom of the alkoxy group may be replaced by a fluorine atom or the like. The alkoxy group may be methoxy, ethoxy, propoxy, or butoxy, and may also be methoxy or ethoxy.

R ^d is a divalent group bonded to two Si. R ^d are independently -O-, -NH-, -C≡C- or silane bond. R ^d can be -O-, -NH- or -C≡C-. By R ^d , two or more silicon atoms can be bonded through R ^d into a straight chain, ladder type, ring or polycyclic form. When n is an integer of 2 or more, silicon atoms can be bonded to each other.

In one state, X ¹ is represented by the following formula,

-L ^α1 -{Si(R ^a ) _s (R ^b ) _t (R ^c ) _u (R ^d' ) _v } _n

[In the formula,

L ^α1 is a single bond or a divalent linking group,

R ^a , R ^b and R ^c are each independently halogen, an alkoxy group having 1 to 10 carbon atoms, an amine group having 1 to 10 carbon atoms, an acetyloxy group having 1 to 10 carbon atoms, or an acetyloxy group having 3 to 10 carbon atoms. Allyl or glycidyl group having 3 to 10 carbon atoms,

R ^d' are independently the basis represented by -Z-SiR ^d1 _p' R ^d2 _q' R ^d3 _r' :

(In the formula, Z is independently a single bond or a divalent linking group,

R ^d1 are independently R ^d" ,

R ^d" and R ^d' have the same meaning,

In R ^d' , there are up to 5 Si bonded in a linear chain across the Z group.

R ^d2 are each independently a hydroxyl group or a hydrolyzable group,

R ^d3 are each independently a hydrogen atom or lower alkyl group,

p' is independently an integer from 0 to 3,

q' are independently integers from 0 to 3,

r' are independently integers from 0 to 3,

However, the sum of p', q' and r' is 3);

s, t and u are independently 0 or 1,

v is an integer from 0 to 3,

n is an integer from 1 to 20].

Examples of Z include -C ₂ H ₄ -, -C ₃ H ₆ -, -CO-O-CH ₂ -CH(OH)-CH ₂ -, -CH ₂ -, and -C ₄ H ₈ -.

In the above-mentioned R ^d' , when there is at least one R ^d1 , it means that there are two or more "Si atoms connected in a straight chain through the Z group" in R ^d' , which are directly connected through the Z group. The number of Si atoms connected in a chain is at most 5. In addition, "the number of Si atoms linearly connected via Z groups in R ^d' " is equal to "the repeating number of -Z-Si- linearly connected in R ^d' ".

For example, the following shows an example of connecting Si atoms via Z groups in R ^d' .

In the above formula, * means the position of Si bonded to the main chain,... means bonded with a predetermined group other than ZSi, that is, when the three bonds of the Si atom are all... In the case of ., it indicates where the repetition of ZSi ends. In addition, the number in the upper right corner of Si means "the number of occurrences of Si connected in a linear chain across the Z group" counted from *. That is, in a chain in which ZSi is repeatedly terminated by Si ² , "the number of Si atoms connected in a straight chain across the Z group in R ^d' " is 2. Similarly, Si ³ , Si ⁴ and Si ⁵ are used to make ZSi repeat terminated chains, and the "number of Si atoms connected in a straight chain across the Z group in R ^d' " are 3, 4 and 5 respectively. In addition, from the above formula, it can be known that there are a plurality of ZSi chains in R ^d' , but they do not all have to be of the same length and can be of any length.

In one form, as shown below, "the number of Si atoms connected in a linear chain across the Z group in R ^d' " is 1 (left formula) or 2 (right formula) in all chains. Mode).

In one state, the number of Si atoms connected in a straight chain across the Z group ^{in R d'} is 1 or 2, and may be 1.

R ^d2 each independently represents a hydroxyl group or a hydrolyzable group. The hydroxyl group is not particularly limited, and may be one generated by hydrolysis of a hydrolyzable group.

R ^d2 can be -OR ⁴ (R ⁴ is a substituted or unsubstituted C _1-3 alkyl group, for example, it can be methyl).

R ^d3 each independently represents a hydrogen atom or a lower alkyl group. The lower alkyl group is an alkyl group having 1 to 20 carbon atoms, and may be an alkyl group having 1 to 6 carbon atoms, or may be a methyl group.

In the same state, in the terminal R ^d1 of R ^d' (R ^d ' when R ^d1 does not exist), q' can be 2 or more, 2 or 3, or 3.

In one aspect, R ^d may have at least 1 -Si(-Z-SiR ^d2 _q' R ^d3 _r' ) ₂ or Si(-Z-SiR ^d2 _q' R ^d3 _r' ) ₃ at the terminal portion, and With -Si(-Z-SiR ^d2 _q' R ^d3 _r' ) ₃ . (-Z-SiR ^d2 _q' R ^d3 _r' ) can also be (-Z-SiR ^d2 ₃ ). In other forms, the terminal portion of R ^d is -Si(-Z-SiR ^d2 _q' R ^d3 _r' ) ₃ , and may also be -Si(-Z-SiR ^d2 ₃ ) ₃ . The more R ^d2 bonded to each Si at the terminal portion, the easier it is to increase the adhesion to the base material, and the wear resistance can be further improved.

In one state, X ¹ is represented by the following formula,

-L ^α1 -{C(R ^a6 ) _s6 (R ^b6 ) _t6 (R ^c6 ) _u6 (R ^d6 ) _v6 } _n6

[In the formula,

L ^α1 is a single bond or a divalent linking group,

R ^a6 , R ^b6 and R ^c6 are independently hydrogen, halogen, alkoxy group having 1 to 10 carbon atoms, amine group having 1 to 10 carbon atoms, acetyloxy group having 1 to 10 carbon atoms, and acetyloxy group having 3 to 10 carbon atoms. Allyl group of 10, glycidyl group with 3 to 10 carbon atoms, OCOR ⁶⁷ (in the formula, R ⁶⁷ is an alkyl group with 1 to 6 carbon atoms), OH or Y ⁶ -SiR ⁶⁵ _j6 R ⁶⁶ _3-j6 ,

R ^d6 are independently -O-, -NH-, -C≡C- or -Z ⁶ -CR ⁶¹ _p6 R ⁶² _q6 R ⁶³ _r6 ,

Z ⁶ is independently an oxygen atom or a divalent organic group,

R ⁶¹ independently represents R ^d6' ,

R ^d6' and R ^d6 have the same meaning,

In R ^d6 , the maximum number of Cs connected in a straight chain through the Z ⁶ group is 5.

R ⁶² are independently -Y ⁶ -SiR ⁶⁵ _j6 R ⁶⁶ _3-j6 ,

Y ⁶ are independently divalent organic groups,

R ⁶⁵ are each independently a hydroxyl group or a hydrolyzable group,

R ⁶⁶ are each independently a hydrogen atom or lower alkyl group,

j6 is independently an integer from 1 to 3 in each (-Y ⁶ -SiR ⁶⁵ _j6 R ⁶⁶ _3-j6 ) unit,

R ⁶³ are each independently a hydrogen atom or lower alkyl group,

p6 are independently integers from 0 to 3,

q6 are independently integers from 0 to 3,

r6 are independently integers from 0 to 3,

s6, t6 and u6 are independently 0 or 1,

v6 is an integer from 0 to 3,

n6 is an integer from 1 to 20,

There are at least 2 (-Y ⁶ -SiR ⁶⁵ _j6 R ⁶⁶ _3-j6 )] in the formula.

In R ^a , R ^b , R ^c , R ^a6 , R ^b6 and R ^c6 , the halogen may be Cl, Br or I, or Cl.

In R ^a , R ^b , R ^c , R ^a6 , R ^b6 and R ^c6 , the carbon number of the alkoxy group may be 1 to 5. Alkoxy groups can be chain, cyclic or branched. The hydrogen atom of the alkoxy group may be replaced by a fluorine atom or the like. The alkoxy group can be methoxy, ethoxy, propoxy or butoxy, and can also be methoxy or ethoxy.

Z ⁶ is, for example, C _1-6 alkylene group, -(CH ₂ ) _g -O-(CH ₂ ) _h - (g can be an integer from 0 to 6, or an integer from 1 to 6; h can be 0 to 6, and may be an integer from 1 to 6) or -phenylene-(CH ₂ ) _i -(i may be an integer from 0 to 6). Z ⁶ may be C _1-3 alkylene group. These groups may be substituted by, for example, one or more substituents selected from the group consisting of fluorine atom, C _1-6 alkyl group, C _2-6 alkenyl group and C _2-6 alkynyl group.

R ⁶¹ independently represents R ^d6' on each occurrence. R ^d6' and R ^d6 have the same meaning.

In R ^d6 , the maximum number of Cs connected in a linear chain via the Z ⁶ group is 5. That is, in R ^d6 , when at least one R ⁶¹ is present, it means that there are two or more "C atoms connected in a linear chain through the Z ⁶ group" in R ^d6 , which are separated through the Z ⁶ group The maximum number of C atoms connected in a straight chain is 5. "The number of linearly connected C atoms in R ^d6 via the Z ⁶ group" is equal to "the number of repeating -Z ⁶ -C- linearly connected in R ^d6 ".

In one form, as shown below, "the number of C atoms in R ^d6 connected in a straight chain through the Z ⁶ group" is 1 (left formula) or 2 (right formula) in all chains Mode).

In one state, "the number of C atoms connected in a linear chain via the Z ⁶ group in R ^d6 " is 1 or 2, and may be 1.

R ⁶² means -Y ⁶ -SiR ⁶⁵ _j6 R ⁶⁶ _3-j6 .

Y ⁶ independently represents a divalent organic group each time it appears.

In one form, Y ⁶ is a C _1-6 alkylene group, -(CH ₂ ) _g' -O-(CH ₂ ) _h' -(g' can be an integer from 0 to 6, or 1 to 6 an integer; h' can be an integer from 0 to 6, or an integer from 1 to 6) or -phenylene-(CH ₂ ) _i' - (i' can be an integer from 0 to 6). These groups may be substituted by, for example, one or more substituents selected from the group consisting of fluorine atom, C _1-6 alkyl group, C _2-6 alkenyl group and C _2-6 alkynyl group.

In one aspect, Y ⁶ can be C _1-6 alkylene or phenylene-(CH ₂ ) _i' -. In this case, the light resistance, especially the ultraviolet resistance, can be improved.

Each occurrence of R ⁶⁵ independently represents a hydroxyl group or a hydrolyzable group. Examples of the "hydrolyzable group" include the same ones as mentioned above.

In one aspect, R ⁶⁵ is -OR (R is a substituted or unsubstituted C _1-3 alkyl group, which can be methyl or ethyl, or methyl).

Each occurrence of R ⁶⁶ independently represents a hydrogen atom or a lower alkyl group. The carbon number of the lower alkyl group may be 1 to 20, or may be 1 to 6. R ⁶⁶ can be methyl.

j6 in each (-Y-SiR ⁶⁵ _j6 R ⁶⁶ _3-j6 ) unit is independently an integer from 1 to 3, which can be 2 or 3, or 3.

Each occurrence of R ⁶³ independently represents a hydrogen atom or a lower alkyl group. The carbon number of the lower alkyl group may be 1 to 20, or may be 1 to 6. R ⁶³ can be methyl.

p6 is independently an integer from 0 to 3 each time it appears. q6 is independently an integer from 0 to 3 each time it appears. r6 is independently an integer from 0 to 3 on each occurrence. However, the sum of p6, q6 and r6 is 3.

In one form, in the terminal R ^d6' of R ^d6 (or R ^d6 itself when R ^d6' does not exist), q6 is 2 or more, it can be 2 or 3, or it can be 3.

In one aspect, the number of Si atoms having hydroxyl groups or hydrolyzable groups in formula (α1) may be 1 to 6, may be 2 to 4, or may be 3. The number of Si atoms having hydroxyl groups or hydrolyzable groups in formula (α2) may be 2 to 12, 4 to 8, or 6.

In the same state, v in X ¹ is 3, and R ^d' are independently -Z-SiR ^d2 _q' R ^d3 _r' .

X ¹ can be, for example, -L ^α1 -SiR ⁵ ₃ , -L ^α1 -Si(OR ⁶ ) ₃ , -L ^α1 -Si(NR ⁶ ₂ ) ₃ or -L ^α1 -Si(OCOR ⁶ ) ₃ (in each formula , L ^α1 is as described above, R ⁵ is a halogen atom, and R ⁶ is independently an alkyl group having 1 to 4 carbon atoms).

In one state, X ¹ is represented by the following formula:

-L ^α1 -{Si(R ^a ) _s (R ^b ) _t (R ^c ) _u (R ^d ) _v } _n , or

-L ^α1 -{C(R ^a6 ) _s6 (R ^b6 ) _t6 (R ^c6 ) _u6 (R ^d6 ) _v6 } _n6

[In the formula, each symbol has the same meaning as above].

In one aspect, X ² can each independently be a valent organic group containing the above-mentioned polyether chain. Suitable groups for the above-mentioned organic groups are the same as for ^R1 .

In other aspects, X ² can each independently be the above-mentioned reactive cross-linking group containing silane.

In other aspects, X ² can be the same as X ¹ .

In other aspects, X ² may be independently at least one group selected from the group consisting of a polysiloxy residue, a sesquioxane residue and a silazane group.

Examples of the polysiloxy residue include the following groups.

In each formula, L ² is a single bond or a bivalent linking group, n30 is an integer from 1 to 20, m30 is an integer from 0 to 10, R ³¹ is independently a monovalent group, and one of the R ³¹ possessed by each group is At least one is a reactive group.

The reactive group is, for example, selected from H, a halogen atom, OR ³¹⁰ (R ³¹⁰ is an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 20 carbon atoms), -L ³ -SiR ³¹¹ ₃ (L ³ is a single bond or an alkylene group having 1 to 10 carbon atoms, R ³¹¹ is a halogen atom), -L ³ -Si(OR ³¹² ) ₃ (L ³ is as described above, R ³¹² is independently a carbon number 1 to 4 alkyl group), -L ³ -Si(NR ³¹² ₂ ) ₃ (L ³ and R ³¹² are as described above), -L ³ -Si(OCOR ³¹² ) ₃ (L ³ and R ³¹² are as described above), and At least one of the group consisting of a group containing any one of these groups.

Groups other than the above-mentioned reactive groups are, for example, selected from the group consisting of alkyl groups, halogenated alkyl groups, alkyl ester groups, halogenated alkyl ester groups, alkyl ether groups, halogenated alkyl ether groups, alkyl amide groups, halogenated alkyl amide groups, and glyceryl groups. Urea (uril) group, halogenated glycoluril group, urea group, halogenated urea group, -CONR ³¹³ COR ³¹⁴ (R ³¹³ and R ³¹⁴ are independently H, alkyl or halogenated alkyl), sugar chain-containing group, extension At least one kind from the group consisting of an alkyl polyether group, an aromatic hydrocarbon group, a halogenated aromatic hydrocarbon group, a heterocyclic ring-containing group, an aryl group and a halogenated aryl group.

L ² is a single bond or a bivalent linking group directly bonded to the "isocyanuric acid ring of formula ( α 1) or formula ( α 2)". L ² may be a single bond, an alkylene group, or a divalent group containing at least one of an ether bond and an ester bond. L ² may be a single bond, an alkylene group having 1 to 10 carbon atoms, or a divalent hydrocarbon group having 1 to 10 carbon atoms containing at least one of an ether bond and an ester bond.

Examples of L ² include: -C ₂ H ₄ -, -C ₃ H ₆ -, -C ₄ H ₈ -O-CH ₂ -, -CO-O-CH ₂ -CH(OH)-CH ₂ -, - CH ₂ -, -C ₄ H ₈ -.

The above-mentioned polysiloxy residue may be the following groups.

In each formula, L ² is a single bond or a bivalent linking group, R ³⁴ is each independently a monovalent group, and at least one of the R ³⁴ in each group is a reactive group.

The reactive group is, for example, selected from -H, -OR ³⁴⁰ (R ³⁴⁰ is an alkyl group with 1 to 4 carbon atoms), a halogen atom, -OH, -O-CR ³⁴⁰ =CH ₂ (R ³⁴⁰ is as described above (as described above), -OCOR ³⁴⁰ (R ³⁴⁰ is as described above), -OCOOR ³⁴¹ (R ³⁴¹ is an alkyl group or a halogenated alkyl group), -NR ³⁴⁰ ₂ (R ³⁴⁰ is as described above) and any of these groups. At least one of the groups consisting of a person's base.

Examples of groups other than the above reactive groups include alkyl groups, halogenated alkyl groups, alkyl ester groups, halogenated alkyl ester groups, alkyl ether groups, halogenated alkyl ether groups, alkyl amide groups, and halogenated alkyl amide groups. , glycoluril (uril) group, halogenated glycoluril group, urea (urea) group, halogenated urea group, -CONR ³⁴² COR ³⁴³ (R ³⁴² and R ³⁴³ are independently H, alkyl or halogenated alkyl), groups containing sugar chains At least one of the group consisting of an alkylene polyether group, an aromatic hydrocarbon group, a halogenated aromatic hydrocarbon group, a heterocyclic-containing group, an aryl group and a halogenated aryl group.

L ² is a single bond or a bivalent linking group directly bonded to the "isocyanuric acid ring of formula (α1) or formula (α2)". Suitable ones as ^L2 are as described above.

Examples of the sesquioxane residue include the following groups.

In each formula, L ² is a single bond or a bivalent linking group, R ³⁷ is independently a monovalent group, at least one of the R ³⁷ in each group is a reactive group, and p30 is independently from 0 to 5000. integer.

The above-mentioned reactive group is, for example, selected from -H, -OR ³⁷⁰ (R ³⁷⁰ is an alkyl group with 1 to 4 carbon atoms), a halogen atom, -OH, -O-CR ³⁷⁰ =CH ₂ (R ³⁷⁰ is an alkyl group with 1 to 4 carbon atoms) as described above), -OCOR ³⁷⁰ (R ³⁷⁰ is as described above), -OCOOR ³⁷¹ (R ³⁷¹ is an alkyl group or alkyl halide), -NR ³⁷⁰ ₂ (R ³⁷⁰ is as described above) and those containing these groups At least one of the groups consisting of any base.

Examples of groups other than the above reactive groups include alkyl groups, halogenated alkyl groups, alkyl ester groups, halogenated alkyl ester groups, alkyl ether groups, halogenated alkyl ether groups, alkyl amide groups, and halogenated alkyl amide groups. , glycoluril (uril) group, halogenated glycoluril group, urea (urea) group, halogenated urea group, -CONR ³⁷² COR ³⁷³ (R ³⁷² and R ³⁷³ are independently H, alkyl or halogenated alkyl), groups containing sugar chains At least one of the group consisting of an alkylene polyether group, an aromatic hydrocarbon group, a halogenated aromatic hydrocarbon group, a heterocyclic-containing group, an aryl group and a halogenated aryl group.

L ² is a single bond or a bivalent linking group directly bonded to the "isocyanuric acid ring of formula ( α 1) or formula ( α 2)". Suitable ones as ^L2 are as described above.

X ² may also be a group different from "the above-mentioned monovalent organic group containing polyether chain, reactive cross-linking group containing silane, polysiloxy residue, sesquisiloxane residue and silazane group".

That ^is , Glycyluril (uril) group, halogenated glycoluril group, urea group, halogenated urea group, -OCOOR ^j (R ^j is an alkyl group or a halogenated alkyl group), -CONR ^k COR ^l (R ^k and R ^l are independently H , alkyl or halogenated alkyl), sugar chain-containing groups, alkylene polyether groups, aromatic hydrocarbon groups, halogenated aromatic hydrocarbon groups, heterocyclic groups, aryl groups, halogenated aryl groups, polysiloxane residues (but exclude At least one of the group consisting of those with reactive groups) and sesquioxane residues (but excluding those with reactive groups).

The above-mentioned polysiloxy residues (excluding those having reactive groups) include the following groups. In addition, examples of the above-mentioned reactive group include reactive groups capable of constituting R ³⁷ .

In each formula, L ⁴ is a single bond or a bivalent linking group, and R ⁴¹ is each independently a group other than a monovalent reactive group.

Groups other than the reactive group may be selected from alkyl groups, halogenated alkyl groups, alkyl ester groups, halogenated alkyl ester groups, alkyl ether groups, halogenated alkyl ether groups, alkyl amide groups, and halogenated alkyl amide groups. , glycoluril (uril) group, halogenated glycoluril group, urea (urea) group, halogenated urea group, -CONR ^k COR ^l (R ^k and R ^l are independently H, alkyl or halogenated alkyl), groups containing sugar chains At least one of the group consisting of an alkylene polyether group, an aromatic hydrocarbon group, a halogenated aromatic hydrocarbon group, a heterocyclic-containing group, an aryl group and a halogenated aryl group.

L ⁴ is a single bond or a bivalent linking group directly bonded to the "isocyanuric acid ring of formula ( α 1) or formula ( α 2)". L ⁴ may be a single bond, an alkylene group, or a divalent group containing at least one bond selected from the group consisting of an ether bond and an ester bond, or a single bond, an extension group having 1 to 10 carbon atoms. an alkyl group, or a divalent hydrocarbon group having 1 to 10 carbon atoms containing at least one bond selected from the group consisting of an ether bond and an ester bond.

Specific examples of L ⁴ include -C ₂ H ₄ -, -C ₃ H ₆ -, -C ₄ H ₈ -O-CH ₂ -, -CO-O-CH ₂ -CH(OH)-CH. ₂ - Wait.

Examples of the above-mentioned sesquisiloxane residues (excluding those having reactive groups) include the following groups. In addition, examples of the above-mentioned reactive group include reactive groups capable of constituting R ³⁷ .

In each formula, L ⁴ is a single bond or a bivalent linking group, R ⁴¹ is each independently a group other than a monovalent reactive group, and p30 is independently an integer from 0 to 5000.

Examples of groups other than the above reactive groups include alkyl groups, halogenated alkyl groups, alkyl ester groups, halogenated alkyl ester groups, alkyl ether groups, halogenated alkyl ether groups, alkyl amide groups, and halogenated alkyl amide groups. , glycoluril (uril) group, halogenated glycoluril group, urea (urea) group, halogenated urea group, -CONR ^k COR ^l (R ^k and R ^l are independently H, alkyl or halogenated alkyl), groups containing sugar chains At least one of the group consisting of an alkylene polyether group, an aromatic hydrocarbon group, a halogenated aromatic hydrocarbon group, a heterocyclic-containing group, an aryl group and a halogenated aryl group.

L ⁴ is a single bond or a bivalent linking group directly bonded to the "isocyanuric acid ring of formula ( α 1) or formula ( α 2)". Suitable ones as ^L4 are as described above.

Examples of the silazane group include the following groups.

In each formula, L ⁵ is a single bond or a divalent linking group, m31 is an integer from 2 to 100, n31 is an integer below 100, and R ⁴² is independently H, an alkyl group with 1 to 10 carbon atoms, an alkenyl group, Cycloalkyl group having 5 to 12 carbon atoms, aryl group having 6 to 10 carbon atoms, alkylsilyl group, alkylcyano group, and alkoxy group having 1 to 4 carbon atoms.

L ⁵ is a single bond or a bivalent linking group directly bonded to the "isocyanuric acid ring of formula ( α 1) or formula ( α 2)". L ⁵ may be a single bond, an alkylene group, or a divalent group containing at least one of an ether bond and an ester bond. L ⁵ may be a single bond, an alkylene group having 1 to 10 carbon atoms, or a divalent hydrocarbon group having 1 to 10 carbon atoms containing at least one of an ether bond and an ester bond.

Examples of L ⁵ include -C ₂ H ₄ -, -C ₃ H ₆ -, -C ₄ H ₈ -O-CH ₂ -, -CO-O-CH ₂ -CH(OH)-CH ₂ -.

Specific examples of the silazane group include the following groups.

In the compound represented by formula (α1) or formula (α2), the average molecular weight of R ¹ is not particularly limited. The average molecular weight of R ¹ is, for example, 500 or more, 1,500 or more, or 2,000 or more. The average molecular weight of R ¹ is, for example, 30,000 or less, and may be 10,000 or less. In one form, the average molecular weight of R ¹ is 500 or more and 30,000 or less.

The average molecular weight of the PFPE silane compound α is not particularly limited. From the viewpoint of ultraviolet resistance and abrasion resistance, the average molecular weight of the PFPE silane compound α is, for example, 500 or more, 1,000 or more, or 2,000 or more. The average molecular weight of the PFPE silane compound may be 10,000 or less, or 6,000 or less. In one aspect, the average molecular weight of the PFPE silane compound α is, for example, 500 or more and 10,000 or less.

In one aspect, the PFPE silane compound α is represented by the above formula ( α 1).

In other aspects, the PFPE silane compound α is a mixture of the compound represented by the above formula ( α1 ) and the compound represented by the formula ( α2 ). The content ratio of the compound represented by formula ( α1 ) in the mixture may be 1 mol% or more, or 10 mol% or more, 50 mol% or more, 80 mol% or more, 90 mol% or more, 95 mol% or more, or 99 mol% or more. The above-mentioned content ratio of the compound represented by formula ( α1 ) only needs to be less than 100 mol%, and may be 99 mol% or less, 95 mol% or less, 90 mol% or less, 85 mol% or less, or 80 mol% or less.

The content of the PFPE silane compound α in the surface treatment agent is, for example, 0.01% by mass or more, 0.1% by mass or more, 1% by mass or more, or 5% by mass or more. The content of the PFPE silane compound α in the surface treatment agent is, for example, 99.9% by mass or less, 50% by mass or less, 30% by mass or less, or 20% by mass or less. In one aspect, the content of the PFPE silane compound α in the surface treatment agent is 0.01 mass % or more and 99.9 mass % or less.

In the composition obtained after excluding the solvent from the surface treatment agent, the content of PFPE silane compound α can be 100 mol% (that is, the surface treatment agent only contains compound α as a non-volatile component), or it can be less than 99.9 mol%. , it can also be less than 99 mol%, it can be less than 98 mol%, it can also be less than 95 mol%. In the composition obtained by excluding the solvent from the surface treatment agent, the content of the PFPE silane compound α may be 1 mol% or more, or 10 mol% or more, or 30 mol% or more, or even 50 mol%. It can be more than 60 mol%, it can be more than 60 mol%, it can be more than 70 mol%, it can be more than 80 mol%.

The PFPE silane compound α can be produced by, for example, the method described in Japanese International Publication No. 2018/056410.

"Silane Compound β Containing Fluoropolyether Group"

The surface treatment agent may further contain "a fluoropolyether group-containing silane compound β other than the PFPE silane compound α (hereinafter also referred to as the PFPE silane compound β )." The PFPE silane compound β has a perfluoropolyether group and Si having a hydroxyl group or a hydrolyzable group. PFPE silane compound β does not have an isocycyanuric acid skeleton.

The perfluoropolyether group of PFPE silane compound β contains a polyether chain represented by the following formula,

-(OC ₆ F ₁₂ ) _a1 -(OC ₅ F ₁₀ ) _b1 -(OC ₄ F ₈ ) _c1 -(OC ₃ F ₆ ) _d1 -(OC ₂ F ₄ ) _e1 -(OCF ₂ ) _f1 -

[In the formula, a1, b1, c1, d1, e1 and f1 are each independently an integer above 0 and below 200. Label a1, b1, c1, d1, e1 or f1 and the order of existence of each repeating unit enclosed in brackets is arbitrary in the formula].

In a state, a1, b1, c1, d1 and e1 are each independently an integer from 0 to 100, and f1 is an integer from 1 to 200. The sum of a1, b1, c1, d1, e1 and f1 may be 5 or more, 10 or more, or 10 or more and 100 or less.

The repeating units in the polyether chain of the PFPE silane compound β can be linear or branched, especially linear. Specific examples of the repeating units in the polyether chain of the PFPE silane compound β are the same as those of the PFPE silane compound α .

In one aspect, the polyether chains of the PFPE silane compound β can each independently be "a group represented by any one of the formulas (f1) to (f6) listed as the polyether chain in the PFPE silane compound α ", It may also be a base represented by formula (f2) or (f3).

In one aspect, the polyether chain system of the PFPE silane compound β has at least 1 (or more than 5, or further more than 10) OCF ₂ units.

In one aspect, the PFPE silane compound β can be represented by the following formula (A1), (A2), (B1), (B2), (C1), (C2), (D1), (D2) or (E1) represents the compound.

(Rf-PFPE) _β' -X ¹⁰⁵ -(SiR ¹⁴ _n R ¹⁵ _3-n ) _β …(B1)

(R ¹⁵ _3-n R ¹⁴ _n Si) _β -X ¹⁰⁵ -PFPE-X ¹⁰⁵ -(SiR ¹⁴ _n R ¹⁵ _3-n ) _β …(B2)

(Rf-PFPE) _γ' -X ¹⁰⁷ -(SiR ^a3 _k R ^b3 _l R ^c3 _m ) _γ …(C1)

(R ^c3 _m R ^b3 _l R ^a3 _k' Si) _γ -X ¹⁰⁷ -PFPE-X ¹⁰⁷ -(SiR ^a3 _k R ^b3 _l R ^c3 _m ) _γ …(C2)

(Rf-PFPE) _δ' -X ¹⁰⁹ -(CR ^d3 _k' R ^e3 _l' R ^f3 _m' ) _δ ...(D1)

(R ^f3 _m' R ^e3 _l' R ^d3 _k' C) _δ -X ¹⁰⁹ -PFPE-X ¹⁰⁹ -(CR ^d3 _k' R ^e3 _l' R ^f3 _m' ) _δ …(D2)

(Rf-PFPE-G ⁵ ) _a5 -Z ⁵ -((OR ¹⁶ ) _c5 -SiR ¹⁴ _n R ¹⁵ _3-n ) _b5 …(E1)

In each formula, Rf is independently an alkyl group having 1 to 16 carbon atoms that may be substituted by one or more fluorine atoms, and PFPE represents a perfluoropolyether group.

The alkyl group having 1 to 16 carbon atoms may be a straight chain or a branched chain. The carbon number may be 1 to 6 or 1 to 3. Rf can especially be a straight-chain alkyl group having 1 to 3 carbon atoms.

Rf may be a CF ₂ HC _1-15 fluoroalkyl group or a perfluoroalkyl group having 1 to 16 carbon atoms, or a perfluoroalkyl group having 1 to 16 carbon atoms.

Rf can be a linear or branched perfluoroalkyl group having 1 to 16 carbon atoms. The number of carbon atoms in the perfluoroalkyl group may be 1 to 6, or may be 1 to 3. Rf may be a linear perfluoroalkyl group having 1 to 3 carbon atoms. Rf is, for example, -CF ₃ , -CF ₂ CF ₃ or CF ₂ CF ₂ CF ₃ .

The perfluoropolyether group is as described above.

In formulas (A1) and (A2), R ¹² independently represents a hydrogen atom or a lower alkyl group each time it appears. The carbon number of the lower alkyl group may be 1 to 20, or may be 1 to 6. R ¹² can be methyl, ethyl or propyl.

In formulas (A1) and (A2), R ¹³ independently represents a hydrogen atom or a halogen atom each time it appears. The halogen atom can be an iodine atom, a chlorine atom or a fluorine atom, and can also be a fluorine atom.

In formulas (A1) to (B2), each occurrence of R ¹⁴ is independently a hydrogen atom or an alkyl group having 1 to 22 carbon atoms, and may be an alkyl group having 1 to 4 carbon atoms.

In formulas (A1) to (B2), R ¹⁵ independently represents a hydroxyl group or a hydrolyzable group each time it appears.

In formulas (A1) to (B2), n in each (-SiR ¹⁴ _n R ¹⁵ _3-n ) unit is independently an integer from 0 to 3, and may be an integer from 0 to 2, or may be 0. However, all n in the formula will not be 3 at the same time. In other words, at least one R ¹⁵ exists in the formula.

In formulas (A1) and (A2), t is each independently an integer from 1 to 10, and may be an integer from 1 to 6, or may be an integer from 2 to 10, or may be an integer from 2 to 6.

In formulas (A1) and (A2), X ¹⁰¹ each independently represents a single bond or an organic group with 2 to 10 valence. X ¹⁰¹ is understood to be the combination of “the perfluoropolyether part (that is, the Rf-PFPE part or PFPE-part) that mainly provides water repellency and surface smoothness, etc.” That is, the connecting base marked α and enclosed in parentheses)" is used to connect. Therefore, if the compounds represented by formulas (A1) and (A2) can exist stably, X ¹⁰¹ may be a single bond or any organic group.

In formulas (A1) and (A2), X ¹⁰² independently represents a single bond or a divalent organic group each time it appears. X ¹⁰² is, for example, an alkylene group having 1 to 20 carbon atoms, and may be -(CH ₂ ) _u - (in the formula, u is an integer from 0 to 2).

In formulas (A1) and (A2), α is an integer from 1 to 9, and α ' is an integer from 1 to 9. These α and α ' may change depending on the valence of X ¹⁰¹ . In formula (A1), the sum of α and α ' is the same as the valence of X ¹⁰¹ . When X ¹⁰¹ is a 10-valent organic group, the sum of α and α ′ is 10. In this case, α is 9 and α ' is 1, for example. Or α is 5, α ' is 5. Furthermore, α may be 1 and α ' may be 9. When X ¹⁰¹ is a single bond or a divalent organic group, α and α ′ are 1. In formula (A2), α is the value obtained by subtracting 1 from the valence of X ¹⁰¹ .

X ¹⁰¹ is an organic radical with 2 to 7 valence, 2 to 4 valence or 2 valence.

In one form, X ¹⁰¹ is a 2- to 4-valent organic group, α is from 1 to 3, and α ′ is 1.

In other forms, X ¹⁰¹ is a divalent organic group, α is 1, and α ′ is 1. In this case, formulas (A1) and (A2) are represented by the following formulas (A1') and (A2').

In formulas (B1) and (B2), X ¹⁰⁵ each independently represents a single bond or an organic group with 2 to 10 valence. X ¹⁰⁵ is understood to be the combination of “the perfluoropolyether part (that is, the Rf-PFPE part or PFPE-part) that mainly provides water repellency and surface smoothness, etc.” That is, the connecting base marked β and enclosed in parentheses)" is used to connect. Therefore, if the compounds represented by formulas (B1) and (B2) can exist stably, X ¹⁰⁵ may be a single bond or any organic group.

In formulas (B1) and (B2), β is an integer from 1 to 9, and β ′ is an integer from 1 to 9. These β and β ' can be determined according to the valence of X ¹⁰⁵ . In formula (B1), the sum of β and β ′ is the same as the valence of X ¹⁰⁵ . When X ¹⁰⁵ is a 10-valent organic group, the sum of β and β ′ is 10. In this case, β is 9 and β ′ is 1, for example. Or β is 5, β ' is 5. Furthermore, β may be 1 and β ′ may be 9. When X ¹⁰⁵ is a single bond or a divalent organic group, β and β ′ are 1. In formula (B2), β is the value obtained by subtracting 1 from the valence value of X ¹⁰⁵ .

X ¹⁰⁵ is an organic radical with 2 to 7 valence, 2 to 4 valence or 2 valence.

In one form, X ¹⁰⁵ is a 2- to 4-valent organic group, β is 1 to 3, and β ′ is 1.

In other forms, X ¹⁰⁵ is a divalent organic group, β is 1, and β ′ is 1. In this case, formulas (B1) and (B2) are represented by the following formulas (B1') and (B2').

_Rf -PFPE-X ¹⁰⁵ -SiR ¹⁴ⁿ R ¹⁵ _3-n …(B1')

R ¹⁵ _3-n R ¹⁴ _n Si-X ¹⁰⁵ -PFPE-X ¹⁰⁵ -SiR ¹⁴ _n R ¹⁵ _3-n …(B2')

In formulas (C1) and (C2), X ¹⁰⁷ each independently represents a single bond or an organic group with 2 to 10 valence. X ¹⁰⁷ is understood to be a combination of "the perfluoropolyether part (that is, the Rf-PFPE part or PFPE-part) that mainly provides water repellency and surface smoothness, etc." and "the silane part that provides the ability to bond with the base material ( That is, the connecting base marked with γ and enclosed in parentheses)" is used to connect. Therefore, if the compounds represented by formulas (C1) and (C2) can exist stably, X ¹⁰⁷ may be a single bond or any organic group.

In formulas (C1) and (C2), γ is an integer from 1 to 9, and γ ' is an integer from 1 to 9. These γ and γ ' can be determined according to the valence of X ¹⁰⁷ . In formula (C1), the sum of γ and γ ' is the same as the valence of X ¹⁰⁷ . When X ¹⁰⁷ is a 10-valent organic group, the sum of γ and γ ' is 10. In this case, for example, γ is 9 and γ ' is 1. Or γ is 5, γ ' is 5. Furthermore, γ can also be 1 and γ ' can be 9. When X ¹⁰⁷ is a single bond or a divalent organic group, γ and γ ' are 1. In the formula (C2), γ is the value obtained by subtracting 1 from the valence value of X ¹⁰⁷ .

In formulas (C1) and (C2), k is an integer from 0 to 3 independently every time it appears, l is an integer from 0 to 3 independently every time it appears, and m is an integer from 0 to 3 each time it appears. Independently an integer from 0 to 3. However, the sum of k, l and m is 3.

X ¹⁰⁷ is an organic radical with 2 to 7 valence, 2 to 4 valence or 2 valence.

In one form, X ¹⁰⁷ is a 2- to 4-valent organic group, γ is 1 to 3, and γ ' is 1.

In other forms, X ¹⁰⁷ is a divalent organic group, γ is 1, and γ ' is 1. In this case, formulas (C1) and (C2) are represented by the following formulas (C1') and (C2').

Rf-PFPE-X ¹⁰⁷ -SiR ^a3 _k R ^b3 _l R ^c3 _m …(C1')

R ^c3 _m R ^b3 _l R ^a3 _k Si-X ¹⁰⁷ -PFPE-X ¹⁰⁷ -SiR ^a3 _k R ^b3 _l R ^c3 _m …(C2')

In formulas (C1) and (C2), R ^a3 independently represents -Z ³ -SiR ⁷¹ _p1 R ⁷² _q1 R ⁷³ _r1 each time it appears.

Z ³ is, for example, a divalent organic group. ^Z3 preferably does not include those that form siloxane bonds with Si atoms (Si atoms to which R ^a3 is bonded) at the end of the main chain of the molecule in formula (C1) or formula (C2). Z ³ is, for example, C _1-6 alkylene group, -(CH ₂ ) _g3 -O-(CH ₂ ) _h3 - (g3 is an integer from 1 to 6, h3 is an integer from 1 to 6) or -phenylene group -(CH ₂ ) _i3 -(i3 is an integer from 0 to 6). Z ³ may be a C _1-3 alkylene group, a C _2-3 alkylene group, or -CH ₂ CH ₂ -. These groups may be substituted with one or more substituents selected from, for example, a fluorine atom, a C _1-6 alkyl group, a C _2-6 alkenyl group, and a C _2-6 alkynyl group.

R ⁷¹ represents R ^a' independently on each occurrence. R ^a' and R ^a3 have the same meaning.

In R ^a3 , the number of Si connected linearly via the Z ³ group is at most 5. That is, when at least one R ⁷¹ is present in the above-mentioned R ^a3 , there are two or more "Si atoms connected in a linear chain across the Z ³ group" in R ^a3 , and "the Si atoms are connected in a straight chain across the Z ³ group" The maximum number of Si atoms connected in a linear chain is 5. "The number of Si atoms connected linearly via the Z ³ group in R ^a3 " is equal to "the number of repeating -Z ³ -Si- connected linearly in R ^a3 ".

In one form, "the number of Si atoms connected in a linear chain via the Z ³ group in R ^a3 " is 1 (left-hand formula) or 2 (right-hand formula) in all chains. In other words, in the -Si-R ^a3 portion containing Si bonded to X ¹⁰⁷ in formulas (C1) and (C2), the left formula has two Si bonded, and the right formula has three Si bonded.

In one form, "the number of Si atoms connected in a linear chain via the Z ³ group in R ^a3 " is 1 or 2 in all chains, and may be 1.

In one state, k is 3, and "the number of Si atoms connected in a linear chain via the Z ³ group in R ^a3 " is 1 in all chains.

Each occurrence of R ⁷² independently represents a hydroxyl group or a hydrolyzable group. R ⁷² may be -OR (R is substituted or unsubstituted C _1-3 alkyl, which may be methyl). Each occurrence of R ⁷³ independently represents a hydrogen atom or a lower alkyl group. The carbon number of the lower alkyl group may be 1 to 20, or may be 1 to 6. R ⁷³ can be methyl.

p1 is an integer from 0 to 3 independently every time it appears, q1 is an integer from 0 to 3 independently every time it appears, and r1 is an integer from 0 to 3 independently every time it appears. However, the sum of p1, q1 and r1 is 3.

In one aspect, in the terminal R ^a3' of R ^a3 (or R ^a3 itself when R ^a3' does not exist), the above-mentioned q1 is 2 or more, and may be 2 or 3, or may be 3.

In one aspect, R ^a3 may have at least one -Si(-Z ³ -SiR ⁷² _q1 R ⁷³ _R1 ) ₂ or Si(-Z ³ -SiR ⁷² _q1 R ⁷³ _R1 ) ₃ at the terminal part, or may have - Si(-Z ³ -SiR ⁷² _q1 R ⁷³ _R1 ) ₃ . The unit of (-Z ³ -SiR ⁷² _q1 R ⁷³ _R1 ) may be (-Z ³ -SiR ⁷² ₃ ). In one form, the terminal portion of R ^a may be -Si(-Z ³ -SiR ⁷² _q1 R ⁷³ _R1 ) ₃ or -Si(-Z ³ -SiR ⁷² ₃ ) ₃ .

In the above formulas (C1) and (C2), at least one R ⁷² exists.

In formulas (C1) and (C2), R ^b3 independently represents a hydroxyl group or a hydrolyzable group each time it appears. R ^b3 can be -OR (R is a substituted or unsubstituted C _1-3 alkyl group, which can be methyl).

In formulas (C1) and (C2), R ^c3 independently represents a hydrogen atom or a lower alkyl group each time it appears. The carbon number of the lower alkyl group may be 1 to 20, or may be 1 to 6. R ^c3 can be methyl.

In formulas (D1) and (D2), X ¹⁰⁹ each independently represents a single bond or an organic group with 2 to 10 valence. X ¹⁰⁹ is understood to be the combination of “the perfluoropolyether part (that is, the Rf-PFPE part or PFPE-part) that mainly provides water repellency and surface smoothness, etc.” That is, the connecting base marked with δ and enclosed in parentheses)" is used to connect. Therefore, if the compounds represented by formulas (D1) and (D2) can exist stably, X ¹⁰⁹ may be a single bond or any organic group.

In formulas (D1) and (D2), δ is an integer from 1 to 9, and δ' is an integer from 1 to 9. δ and δ ' can change depending on the valence of X ¹⁰⁹ . In formula (D1), the sum of δ and δ ' is the same as the valence of X ¹⁰⁹ . For example, when X ¹⁰⁹ is a 10-valent organic group, the sum of δ and δ ' is 10. In this case, for example, δ is 9 and δ ' is 1. Or δ is 5 and δ ' is 5. Furthermore, δ may be 1 and δ ' may be 9. When X ¹⁰⁹ is a divalent organic group, δ and δ ' are 1. In the formula (D2), δ is the value obtained by subtracting 1 from the valence value of X ¹⁰⁹ .

X ¹⁰⁹ is an organic radical with 2 to 7 valence, 2 to 4 valence or 2 valence.

In one form, X ¹⁰⁹ is a 2- to 4-valent organic group, δ is from 1 to 3, and δ ' is 1.

In other forms, X ¹⁰⁹ is a divalent organic group, δ is 1, and δ ' is 1. In this case, the formulas (D1) and (D2) are represented by the following formulas (D1') and (D2').

Rf-PFPE-X ¹⁰⁹ -CR ^d3 _k' R ^e3 _l' R ^f3 _m' ...(D1')

R ^f3 _m' R ^e3 _l' R ^d3 _k' CX ¹⁰⁹ -PFPE-X ¹⁰⁹ -CR ^d3 _k' R ^e3 _l' R ^f3 _m' ...(D2')

In formulas (D1) and (D2), R ^d3 independently represents -Z ^3' -CR ⁸¹ _p4 R ⁸² _q4 R ⁸³ _r4 each time it appears.

Z ^3' independently represents an oxygen atom or a divalent organic group each time it appears.

Z ^3' is, for example, C _1-6 alkylene group, -(CH ₂ ) _g4 -O-(CH ₂ ) _h4 - (g4 is an integer from 0 to 6, and may be an integer from 1 to 6; h4 is 0 to 6 can be an integer from 1 to 6) or -phenylene-(CH ₂ ) _i4 - (i4 can be an integer from 0 to 6). Z ^3' may be a C _1-3 alkylene group, a C _2-3 alkylene group, or -CH ₂ CH ₂ -. These groups may be substituted with one or more substituents selected from, for example, a fluorine atom, a C _1-6 alkyl group, a C _2-6 alkenyl group, and a C _2-6 alkynyl group.

R ⁸¹ independently represents R ^d3" each time it appears. R ^d3" and R ^d3 have the same meaning.

In R ^d3 , the maximum number of Cs connected in a linear chain via the Z ^3' group is 5. That is, when there is at least one R ⁸¹ in the above-mentioned R ^d3 , there are two or more "C atoms connected in a linear chain through the Z ^3' group" in R ^d3 , and "through Z The maximum number of C atoms connected in a linear chain to the ^3' group is 5. In addition, "the number of C atoms connected linearly via the Z ^3' group in R d3" is equal to "the number of repeating -Z ^{3 '} -C- connected linearly in R ^d3 ".

In one form, as shown below, "the number of C atoms connected in a straight chain through the Z ^3' group in R ^d3 " is 1 (left-hand formula) or 2 ( Right type).

In one form, "the number of C atoms connected in a linear chain via the Z ^3' group in R ^d3 " is 1 or 2 in all chains, and may be 1.

R ⁸² represents -Y ³ -SiR ⁸⁵ _j R ⁸⁶ _3-j .

Each occurrence of Y ³ independently represents a divalent organic group.

In one form, Y ³ is a C _1-6 alkylene group, -(CH ₂ ) _g5 -O-(CH ₂ ) _h5 - (g5 is an integer from 0 to 6, and can be an integer from 1 to 6; h5 is (i5 is an integer from 0 to 6) or -phenylene-(CH ₂ ) _5' - (i5 is an integer from 0 to 6). These groups may be substituted by, for example, one or more substituents selected from the group consisting of fluorine atom, C _1-6 alkyl group, C _2-6 alkenyl group and C _2-6 alkynyl group.

In one aspect, Y ³ can be C _1-6 alkylene or phenyl-(CH ₂ ) _j5 -. In this case, the light resistance, especially the ultraviolet resistance, can be improved.

Each occurrence of R ⁸⁵ independently represents a hydroxyl group or a hydrolyzable group. R ⁸⁵ can be -OR (R is a substituted or unsubstituted C _1-3 alkyl group, which can be methyl or ethyl, or methyl).

R ⁸⁶ independently represents a hydrogen atom or a lower alkyl group each time it appears. The carbon number of the lower alkyl group may be 1 to 20, or may be 1 to 6. R ⁸⁶ can be methyl.

j in each (-Y ³ -SiR ⁸⁵ _j R ⁸⁶ _3-j ) unit is independently an integer from 1 to 3, and may be 2 or 3, or 3.

Each occurrence of R ⁸³ independently represents a hydrogen atom, a hydroxyl group or a lower alkyl group. R ⁸³ may also be independently a hydrogen atom or lower alkyl group in each occurrence. The carbon number of the lower alkyl group may be 1 to 20, or may be 1 to 6. R ⁸³ can be methyl.

p4 is an integer from 0 to 3 independently every time it appears, q4 is an integer from 0 to 3 independently every time it appears, and r4 is an integer from 0 to 3 independently every time it appears. However, the sum of p4, q4 and r4 is 3.

In one state, in the terminal R ^d3' of R ^d3 (or R ^d3 itself when R ^d3' does not exist), q4 is 2 or more, it can be 2 or 3, or it can be 3.

In formulas (D1) and (D2), R ^e3 independently represents -Y ³ -SiR ⁸⁵ _j R ⁸⁶ _3-j each time it appears. Y ³ , R ⁸⁵ , R ⁸⁶ and j have the same meanings as described in R ⁸² above.

In formulas (D1) and (D2), R ^f3 independently represents a hydrogen atom, a hydroxyl group or a lower alkyl group each time it appears. Each occurrence of R ^f3 may be independently a hydrogen atom or a lower alkyl group. The carbon number of the lower alkyl group may be 1 to 20, or may be 1 to 6. R ^f3 may be methyl.

In formulas (D1) and (D2), k' is an integer from 0 to 3 independently every time it appears, l is an integer from 0 to 3 independently every time it appears, and m' is an integer from 0 to 3 every time it appears. are independently integers from 0 to 3. However, the sum of k', l' and m' is 3.

In a modality, at least one k' is 2 or 3, and may be 3.

In one state, k' is 2 or 3, and can be 3.

In one state, l' is 2 or 3, and can be 3.

At least one q4 is 2 or 3, or at least one l' is 2 or 3. That is, there are at least two -Y ³ -SiR ⁸⁵ _j R ⁸⁶ _3-j groups in the formula.

In formula (E1), G ⁵ is -R ¹⁷ -O-, -R ¹⁷ -CONH-, -CONH- or a single bond. From the viewpoint of light resistance, G ⁵ may be -R ¹⁷ -CONH- or CONH-. From the viewpoint of chemical resistance, G ⁵ may be -R ¹⁷ -O-.

R ¹⁷ is an alkylene group. From the viewpoint of ease of production, R ¹⁷ may be an alkylene group having 1 to 4 carbon atoms, or -CH ₂ -.

In the formula (E1), Z ⁵ is a (a5+b5)-valent hydrocarbon group, or a carbon number of 2 or more (a5+b5) with one or more etheric oxygen atoms between the carbon atoms of the hydrocarbon group. base. When G ⁵ is -R ¹⁷ -O- and c5 is 1, Z ⁵ is a residue obtained by excluding hydroxyl groups from a polyol having (a5+b5) hydroxyl groups.

In one state, Z ⁵ can be the following bases.

From the viewpoint of excellent reactivity of the hydroxyl group, Z ⁵ may be a residue obtained by excluding the hydroxyl group from the polyol having a primary hydroxyl group. From the viewpoint of the ease of acquisition of raw materials, Z ⁵ may be a group represented by the following formula (Z-1), a group represented by the following formula (Z-2), a group represented by the following formula (Z-3) The represented group is a group represented by the following formula (Z-4) or a group represented by the following formula (Z-5). In the formula, R ^e is an alkyl group, which can be a methyl group or an ethyl group.

In formula (E1), R ¹⁶ is an alkylene group. From the viewpoint of ease of production, R ¹⁶ may be an alkylene group having 4 to 14 carbon atoms. During hydrosilylation in manufacturing, it is difficult to produce by-products in which part or all of the allyl group (-CH ₂ CH=CH ₂ ) isomerized into internal olefins (-CH=CHCH ₃ ). That is, R ¹⁶ may be an alkylene group having 4 to 10 carbon atoms.

In formula (E1), a5 is an integer greater than or equal to 1. b5 is an integer above 1. (a5+b5) is 3 or more. When a5 is 1, b5 is 4 or more. When a5 is 2 or more, b5 is 1 or more. When a5 is 2 or more, a5 [Rf-PFPE-G ⁵ ] may be the same or different. When b5 is 2 or more, b5 [(OR ¹⁶ ) _c5 -SiR ¹⁴ _h R ¹⁵ _3-h ] may be the same or different. c5 is 0 or 1.

a5 can be from 1 to 10 or from 1 to 4. When a5 is 1 or more, the water and oil repellency, abrasion resistance, fingerprint dirt removal performance, and lubricity of the surface treatment layer can be further improved easily. When a5 is 10 or less, the surface treatment layer has a good appearance. (a5+b5) can be 3 to 15, or 3 to 12.

When a5 is 1, b5 is 4 or more, it can be 4 to 10, or it can be 4 to 5. When a5 is 1 and b5 is 4 or more, the wear resistance of the surface treatment layer can be easily improved. When b5 is 10 or less, the appearance of the surface treatment layer and the stability of the compound can be easily improved.

When a5 is an integer of 2 or more, b5 is an integer of 1 or more, and may be an integer from 1 to 10, or an integer from 1 to 4. When a5 is an integer of 2 or more, since the lubricity of the surface treatment layer is improved, frictional force is less likely to be applied to the surface treatment layer. Therefore, even if b5 is 1, the wear resistance of the surface treatment layer can be easily improved. When b5 is 10 or less, the appearance of the surface treatment layer and the stability of the compound can be easily improved.

In formula (E1), c5 is 0 or 1. From the viewpoint of excellent light resistance of the compound, c5 may be 0. From the viewpoint of ease of manufacture of the compound, c5 may be 1.

In one aspect, X ¹⁰¹ , X ¹⁰⁵ , X ¹⁰⁷ and X ¹⁰⁹ may each independently be a divalent base represented by the following formula,

-(R ²⁰ ) _p2 -(X ²⁰ ) _q2 -

[In the formula,

R ²⁰ is a single bond, -(CH ₂ ) _s' -, or ortho, m or p-phenylene group, which can be -(CH ₂ ) _s' -,

s' is an integer from 1 to 20, 1 to 6, 1 to 3, or 1 or 2,

X ²⁰ means -(X ²¹ ) _l' -,

^Each _occurrence ^of (R ³³⁰ ) ₂ O) _m" -Si(R ³³⁰ ) ₂ -, -CONR ³³¹ -, -O-CONR ³³¹ -, -NR ³³¹ - and (CH ₂ ) _n' - in the group consisting of ,

R ³³⁰ independently represents phenyl, C _1-6 alkyl or C _1-6 alkoxy each time it appears, and can be phenyl or C _1-6 alkyl, or methyl,

R ³³¹ independently represents a hydrogen atom, phenyl or C _1-6 alkyl group (typically methyl) each time it appears,

m" is independently an integer from 1 to 100 or 1 to 20 on each occurrence,

n' is independently an integer from 1 to 20, 1 to 6 or 1 to 3 on each occurrence,

l' is an integer from 1 to 10, 1 to 5 or 1 to 3,

p2 is 0 or 1,

q2 is 0 or 1,

Here, at least one of p2 and q2 is 1, and the order in which the repeating units enclosed in parentheses marked with p2 or q2 is arbitrary].

R ²⁰ and X ²⁰ ₍ typically ^, the hydrogen atoms _{of R 20} ^and .

In one state, X ¹⁰¹ , X ¹⁰⁵ , X ¹⁰⁷ and X ¹⁰⁹ can each independently be a divalent base represented by the following formula,

-(R ²⁰ ) _p2 -(X ²⁰ ) _q2 -

[In the formula,

R ²⁰ represents -(CH ₂ ) _s' -,

s' is an integer from 1 to 20,

X ²⁰ means -(X ²¹ ) _l' -,

^{Each occurrence of} _{_ _}

R ³³¹ independently represents a hydrogen atom, phenyl or C _1-6 alkyl group each time it appears,

Each occurrence of n' is independently an integer from 1 to 20,

l' is an integer from 1 to 10,

p2 is 0 or 1,

q2 is 0 or 1,

Here, at least one of p2 and q2 is 1, and the order in which the repeating units enclosed in parentheses marked with p2 or q2 is arbitrary].

R ²⁰ _and X ^{20 (} typically the hydrogen _atoms of R ²⁰ and .

In one state, X ¹⁰¹ , X ¹⁰⁵ , X ¹⁰⁷ and X ¹⁰⁹ are independently -(R ²⁰ ) _p2 -(X ²⁰ ) _q2 -R ³² -. R ³² represents a single bond, -(CH ₂ ) _t' -, or ortho, m or p-phenylene group, and may be -(CH ₂ ) _t' -. t' is an integer from 1 to 20, 2 to 6, or 2 to 3.

R ³² (typically the hydrogen atom of R ³² ) may be substituted with one or more substituents selected from a fluorine atom, a C _1-3 alkyl group and a C _1-3 fluoroalkyl group.

In one state, X ¹⁰¹ , X ¹⁰⁵ , X ¹⁰⁷ and X ¹⁰⁹ can be independently:

single key,

-X ^f -C _1-20 alkylene group,

-X ^f -R ²⁰ -X ^c -R ³² -, or

-X ^f -X ^d -R ³² -

[In the formula,

R ²⁰ and R ³² have the same meaning as above,

X ^f is a single bond or a perfluoroalkylene group having 1 to 6 carbon atoms, 1 to 4 carbon atoms, or 1 to 2 carbon atoms, and may be difluoromethylene].

In one state, X ¹⁰¹ , X ¹⁰⁵ , X ¹⁰⁷ and X ¹⁰⁹ are independently:

single key,

-X ^f -C _1-20 alkylene group,

-X ^f -(CH ₂ ) _s' -X ^c -,

-X ^f -(CH ₂ ) _s' -X ^c -(CH ₂ ) _t' -

-X ^f -X ^d -, or

-X ^f -X ^d -(CH ₂ ) _t' -

[In the formula, X ^f , s' and t' have the same meaning as above].

In the above formula, X ^c represents:

-O-、

-S-、

-C(O)O-、

-CONR ³³¹ -,

-O-CONR ³³¹ -,

-Si(R ³³⁰ ) ₂ -,

-(Si(R ³³⁰ ) ₂ O) _m" -Si(R ³³⁰ ) ₂ -,

-O-(CH ₂ ) _u' -(Si(R ³³⁰ ) ₂ O) _m" -Si(R ³³⁰ ) ₂ -,

-O-(CH ₂ ) _u' -Si(R ³³⁰ ) ₂ -O-Si(R ³³⁰ ) ₂ -CH ₂ CH ₂ -Si(R ³³⁰ ) ₂ -O-Si(R ³³⁰ ) ₂ -,

-O-(CH ₂ ) _u' -Si(OCH ₃ ) ₂ OSi(OCH ₃ ) ₂ -,

-CONR ³³¹ -(CH ₂ ) _u' -(Si(R ³³⁰ ) ₂ O) _m" -Si(R ³³⁰ ) ₂ -,

-CONR ³³¹ -(CH ₂ ) _u' -N(R ³³¹ )-, or

-CONR ³³¹ -(o-, m- or p-phenyl)-Si(R ³³⁰ ) ₂ -

[In the formula, R ³³⁰ , R ³³¹ and m" have the same meaning as above,

u' is an integer from 1 to 20, can be an integer from 2 to 6, or can be an integer from 2 to 3;

X ^c can be -O-].

In the above formula, X ^d represents:

-S-、

-C(O)O-、

-CONR ³³¹ -,

-O-CONR ³³¹ -,

-CONR ³³¹ -(CH ₂ ) _u' -(Si(R ³³⁰ ) ₂ O) _m" -Si(R ³³⁰ ) ₂ -,

-CONR ³³¹ -(CH ₂ ) _u' -N(R ³³¹ )-, or

-CONR ³³¹ -(o-, m- or p-phenyl)-Si(R ³³⁰ ) ₂ -

[In the formula, each symbol has the same meaning as above].

In one state, X ¹⁰¹ , X ¹⁰⁵ , X ¹⁰⁷ and X ¹⁰⁹ can be independently:

single key,

-X ^f -C _1-20 alkylene group,

-X ^f -(CH ₂ ) _s' -X ^c -(CH ₂ ) _t' -, or

-X ^f -X ^d -(CH ₂ ) _t' -

[In the formula, each symbol has the same meaning as above].

In one state, X ¹⁰¹ , X ¹⁰⁵ , X ¹⁰⁷ and X ¹⁰⁹ can be independently:

single key,

-X ^f -C _1-20 alkylene group,

-X ^f -(CH ₂ ) _s' -X ^c -, or

-X ^f -(CH ₂ ) _s' -X ^c -(CH ₂ ) _t' -

[In the formula,

X ^c is -O-, -CONR ³³¹ - or O-CONR ³³¹ -,

R ³³¹ independently represents a hydrogen atom, phenyl or C _1-6 alkyl group each time it appears,

s' is an integer from 1 to 20,

t' is an integer from 1 to 20].

In one state, X ¹⁰¹ , X ¹⁰⁵ , X ¹⁰⁷ and X ¹⁰⁹ are independently:

single key,

-X ^f -C _1-20 alkylene group,

-X ^f -(CH ₂ ) _s' -O-(CH ₂ ) _t' -,

-X ^f -(CH ₂ ) _s' -(Si(R ³³⁰ ) ₂ O) _m" -Si(R ³³⁰ ) ₂ -(CH ₂ ) _t' -,

-X ^f -(CH ₂ ) _s' -O-(CH ₂ ) _u' -(Si(R ³³⁰ ) ₂ O) _m" -Si(R ³³⁰ ) ₂ -(CH ₂ ) _t' -, or

-X ^f -(CH ₂ ) _s' -O-(CH ₂ ) _t' -Si(R ³³⁰ ) ₂ -(CH ₂ ) _u' -Si(R ³³⁰ ) ₂ -(C _v H _2v )-

[In the formula, X ^f , R ³³⁰ , m", s', t' and u' have the same meaning as above,

v is an integer from 1 to 20, 2 to 6, or 2 to 3].

In the above formula, -(C _v H _2v )- can be a straight chain or a branched chain. -(C _v H _2v )- can be, for example, -CH ₂ CH ₂ -, -CH ₂ CH ₂ CH ₂ -, -CH(CH ₃ )-, -CH(CH ₃ )CH ₂ -.

^{The X 101 ,} _{_ _ _} Substituted by more than one substituent.

The left sides of X ¹⁰¹ , X ¹⁰⁵ , X ¹⁰⁷ and X ¹⁰⁹ are bonded to the PFPE base.

X ^f can be a single bond in formulas (A1), (B1), (C1) and (D1). X ^f in formulas (A2), (B2), (C2) and (D2) may be a perfluoroalkylene group having 1 to 6 carbon atoms, 1 to 4 carbon atoms or 1 to 2 carbon atoms, or may be a difluoromethylene group.

In the same aspect, the X ¹⁰¹ , X ¹⁰⁵ , X ¹⁰⁷ and X ¹⁰⁹ groups may each independently be a group other than -OC _1-6 alkylene group.

In other aspects, X ¹⁰¹ , X ¹⁰⁵ , X ¹⁰⁷ and X ¹⁰⁹ are represented by the following formulas:

In the formula,

R ⁴¹ is independently a hydrogen atom, a phenyl group, an alkyl group with 1 to 6 carbon atoms or a C _1-6 alkoxy group, and may be a methyl group;

D is a basis selected from the following:

-CH ₂ O(CH ₂ ) ₂ -,

-CH ₂ O(CH ₂ ) ₃ -,

-CF ₂ O(CH ₂ ) ₃ -,

-(CH ₂ ) ₂ -,

-(CH ₂ ) ₃ -,

-(CH ₂ ) ₄ -,

-CONH-(CH ₂ ) ₃ -,

-CON(CH ₃ )-(CH ₂ ) ₃ -,

-CON(Ph)-(CH ₂ ) ₃ -(where Ph means phenyl), and the following formula:

In the formula, R ⁴² is independently a hydrogen atom, a C _1-6 alkyl group or a C _1-6 alkoxy group, which can be a methyl group or a methoxy group, or a methyl group;

E is -(CH ₂ ) _n -(n is an integer from 2 to 6),

D is bonded to PFPE in the main chain of the molecule, and E is bonded to the opposite group to PFPE.

Specific examples of X ¹⁰¹ , X ¹⁰⁵ , X ¹⁰⁷ and X ¹⁰⁹ can be listed:

single key,

-CH ₂ OCH ₂ -,

-CH ₂ O(CH ₂ ) ₂ -,

-CH ₂ O(CH ₂ ) ₃ -,

-CH ₂ O(CH ₂ ) ₆ -,

-CF ₂ -CH ₂ -O-CH ₂ -,

-CF ₂ -CH ₂ -O-(CH ₂ ) ₂ -,

-CF ₂ -CH ₂ -O-(CH ₂ ) ₃ -,

-CF ₂ -CH ₂ -O-(CH ₂ ) ₆ -,

-CH ₂ O(CH ₂ ) ₃ Si(CH ₃ ) ₂ OSi(CH ₃ ) ₂ (CH ₂ ) ₂ -,

-CH ₂ O(CH ₂ ) ₃ Si(CH ₃ ) ₂ OSi(CH ₃ ) ₂ OSi(CH ₃ ) ₂ (CH ₂ ) ₂ -,

-CH ₂ O(CH ₂ ) ₃ Si(CH ₃ ) ₂ O(Si(CH ₃ ) ₂ O) ₂ Si(CH ₃ ) ₂ (CH ₂ ) ₂ -,

-CH ₂ O(CH ₂ ) ₃ Si(CH ₃ ) ₂ O(Si(CH ₃ ) ₂ O) ₃ Si(CH ₃ ) ₂ (CH ₂ ) ₂ -,

-CH ₂ O(CH ₂ ) ₃ Si(CH ₃ ) ₂ O(Si(CH ₃ ) ₂ O) ₁₀ Si(CH ₃ ) ₂ (CH ₂ ) ₂ -,

-CH ₂ O(CH ₂ ) ₃ Si(CH ₃ ) ₂ O(Si(CH ₃ ) ₂ O) ₂₀ Si(CH ₃ ) ₂ (CH ₂ ) ₂ -,

-CH ₂ OCF ₂ CHFOCF ₂ -,

-CH ₂ OCF ₂ CHFOCF ₂ CF ₂ -,

-CH ₂ OCF ₂ CHFOCF ₂ CF ₂ CF ₂ -,

-CH ₂ OCH ₂ CF ₂ CF ₂ OCF ₂ -,

-CH ₂ OCH ₂ CF 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 OCF (CF ₃ )CF ₂ OCF ₂ -,

-CH ₂ OCH ₂ CF ₂ CF ₂ OCF (CF ₃ )CF ₂ OCF ₂ CF ₂ -,

-CH ₂ OCH ₂ CF ₂ CF ₂ OCF (CF ₃ )CF ₂ OCF ₂ CF ₂ CF ₂ -,

-CH ₂ OCH ₂ CHFCF ₂ OCF ₂ -,

-CH ₂ OCH ₂ CHFCF ₂ OCF ₂ CF ₂ -,

-CH ₂ OCH ₂ CHFCF ₂ OCF ₂ CF ₂ CF ₂ -,

-CH ₂ OCH ₂ CHFCF ₂ OCF(CF ₃ )CF ₂ OCF ₂ -,

-CH ₂ OCH ₂ CHFCF ₂ OCF(CF ₃ )CF ₂ OCF ₂ CF ₂ -,

-CH ₂ OCH ₂ CHFCF ₂ OCF(CF ₃ )CF ₂ OCF ₂ CF ₂ CF ₂ -,

-CH ₂ OCF ₂ CHFOCF ₂ CF ₂ CF ₂ -C(O)NH-CH ₂ -,

-CH ₂ OCH ₂ (CH ₂ ) ₇ CH ₂ Si(OCH ₃ ) ₂ OSi(OCH ₃ ) ₂ (CH ₂ ) ₂ Si(OCH ₃ ) ₂ OSi(OCH ₃ ) ₂ (CH ₂ ) ₂ -,

-CH ₂ OCH ₂ CH ₂ CH ₂ Si(OCH ₃ ) ₂ OSi(OCH ₃ ) ₂ (CH ₂ ) ₃ -,

-CH ₂ OCH ₂ CH ₂ CH ₂ Si(OCH ₂ CH ₃ ) ₂ OSi(OCH ₂ CH ₃ ) ₂ (CH ₂ ) ₃ -,

-CH ₂ OCH ₂ CH ₂ CH ₂ Si(OCH ₃ ) ₂ OSi(OCH ₃ ) ₂ (CH ₂ ) ₂ -,

-CH ₂ OCH ₂ CH ₂ CH ₂ Si(OCH ₂ CH ₃ ) ₂ OSi(OCH ₂ CH ₃ ) ₂ (CH ₂ ) ₂ -,

-(CH ₂ ) ₂ -Si(CH ₃ ) ₂ -(CH ₂ ) ₂ -,

-CH ₂ -,

-(CH ₂ ) ₂ -、

-(CH ₂ ) ₃ -,

-(CH ₂ ) ₄ -,

-(CH ₂ ) ₅ -、

-(CH ₂ ) ₆ -,

-CF ₂ -CH ₂ -,

-CF ₂ -(CH ₂ ) ₂ -,

-CF ₂ -(CH ₂ ) ₃ -,

-CF ₂ -(CH ₂ ) ₄ -,

-CF ₂ -(CH ₂ ) ₅ -,

-CF ₂ -(CH ₂ ) ₆ -,

-CO-、

-CONH-、

-CONH-CH ₂ -,

-CONH-(CH ₂ ) ₂ -,

-CONH-(CH ₂ ) ₃ -,

-CONH-(CH ₂ ) ₆ -,

-CF ₂ CONHCH ₂ -,

-CF ₂ CONH(CH ₂ ) ₂ -,

-CF ₂ CONH(CH ₂ ) ₃ -,

-CF ₂ CONH(CH ₂ ) ₆ -,

-CON(CH ₃ )-(CH ₂ ) ₃ -,

-CON(Ph)-(CH ₂ ) ₃ -(where Ph means phenyl),

-CON(CH ₃ )-(CH ₂ ) ₆ -,

-CON(Ph)-(CH ₂ ) ₆ -(where Ph means phenyl),

-CF ₂ -CON(CH ₃ )-(CH ₂ ) ₃ -,

-CF ₂ -CON(Ph)-(CH ₂ ) ₃ -(where Ph means phenyl),

-CF ₂ -CON(CH ₃ )-(CH ₂ ) ₆ -,

-CF ₂ -CON(Ph)-(CH ₂ ) ₆ -(where Ph means phenyl),

-CONH-(CH ₂ ) ₂ NH(CH ₂ ) ₃ -,

-CONH-(CH ₂ ) ₆ NH(CH ₂ ) ₃ -,

-CH ₂ O-CONH-(CH ₂ ) ₃ -,

-CH ₂ O-CONH-(CH ₂ ) ₆ -,

-S-(CH ₂ ) ₃ -,

-(CH ₂ ) ₂ S(CH ₂ ) ₃ -,

-CONH-(CH ₂ ) ₃ Si(CH ₃ ) ₂ OSi(CH ₃ ) ₂ (CH ₂ ) ₂ -,

-CONH-(CH ₂ ) ₃ Si(CH ₃ ) ₂ OSi(CH ₃ ) ₂ OSi(CH ₃ ) ₂ (CH ₂ ) ₂ -,

-CONH-(CH ₂ ) ₃ Si(CH ₃ ) ₂ O(Si(CH ₃ ) ₂ O) ₂ Si(CH ₃ ) ₂ (CH ₂ ) ₂ -,

-CONH-(CH ₂ ) ₃ Si(CH ₃ ) ₂ O(Si(CH ₃ ) ₂ O) ₃ Si(CH ₃ ) ₂ (CH ₂ ) ₂ -,

-CONH-(CH ₂ ) ₃ Si(CH ₃ ) ₂ O(Si(CH ₃ ) ₂ O) ₁₀ Si(CH ₃ ) ₂ (CH ₂ ) ₂ -,

-CONH-(CH ₂ ) ₃ Si(CH ₃ ) ₂ O(Si(CH ₃ ) ₂ O) ₂₀ Si(CH ₃ ) ₂ (CH ₂ ) ₂ -,

-C(O)O-(CH ₂ ) ₃ -,

-C(O)O-(CH ₂ ) ₆ -,

-CH ₂ -O-(CH ₂ ) ₃ -Si(CH ₃ ) ₂ -(CH ₂ ) ₂ -Si(CH ₃ ) ₂ -(CH ₂ ) ₂ -,

-CH ₂ -O-(CH ₂ ) ₃ -Si(CH ₃ ) ₂ -(CH ₂ ) ₂ -Si(CH ₃ ) ₂ -CH(CH ₃ )-,

-CH ₂ -O-(CH ₂ ) ₃ -Si(CH ₃ ) ₂ -(CH ₂ ) ₂ -Si(CH ₃ ) ₂ -(CH ₂ ) ₃ -,

-CH ₂ -O-(CH ₂ ) ₃ -Si(CH ₃ ) ₂ -(CH ₂ ) ₂ -Si(CH ₃ ) ₂ -CH(CH ₃ )-CH ₂ -,

-OCH ₂ -,

-O(CH ₂ ) ₃ -,

-OCFHCF ₂ -,

In one state, X ¹⁰¹ , X ¹⁰⁵ , X ¹⁰⁷ and X ¹⁰⁹ are independently represented by the following formula,

-(R ³⁵ ) _x1 -(CFR ³⁶ ) _y1 -(CH ₂ ) _z1 -

[In the formula,

x1, y1 and z1 are independently integers from 0 to 10,

The sum of x1, y1 and z1 is more than 1,

The order of existence of the repeating units enclosed in parentheses is arbitrary in the formula].

Each time R ³⁵ appears, it is independently an oxygen atom, a phenyl group, a carbazolyl group (Carbazolylene), -NR ³⁵⁰ - (in the formula, R ³⁵⁰ represents a hydrogen atom or an organic group) or a divalent organic group. It is an oxygen atom or a divalent polar group.

The "divalent polar group" is not particularly limited, and examples thereof include -C(O)-, -C(=NR ³⁵¹ )-, and C(O)NR ³⁵¹ - (in this equation, R ³⁵¹ represents a hydrogen atom or a lower alkane base). Here, the lower alkyl group is, for example, an alkyl group having 1 to 6 carbon atoms (for example, methyl, ethyl, n-propyl). The lower alkyl group may be substituted by more than 1 fluorine atom.

Each time R ³⁶ appears, it is independently a hydrogen atom, a fluorine atom or a lower fluoroalkyl group, and may be a fluorine atom. Here, the lower fluoroalkyl group may be, for example, a fluoroalkyl group having 1 to 6 carbon atoms or 1 to 3 carbon atoms, a perfluoroalkyl group having 1 to 3 carbon atoms, or a trifluoromethyl or pentafluoroethyl group. Can be trifluoromethyl.

In one form, X ¹⁰¹ , X ¹⁰⁵ , X ¹⁰⁷ and X ¹⁰⁹ are represented by the following formula,

In the formula,

R ⁵¹ is each independently a hydrogen atom, a phenyl group, an alkyl group with 1 to 6 carbon atoms or a C _1-6 alkoxy group, and may be a methyl group,

Among each X ¹⁰¹ group, any number of T are the following groups bonded to "PFPE in the main chain of the molecule":

-CH ₂ O(CH ₂ ) ₂ -,

-CH ₂ O(CH ₂ ) ₃ -,

-CF ₂ O(CH ₂ ) ₃ -,

-(CH ₂ ) ₂ -,

-(CH ₂ ) ₃ -,

-(CH ₂ ) ₄ -,

-CONH-(CH ₂ ) ₃ -,

-CON(CH ₃ )-(CH ₂ ) ₃ -,

-CON(Ph)-(CH ₂ ) ₃ -(where Ph means phenyl), or the following formula:

[In the formula, R ⁵² is independently a hydrogen atom, a C _1-6 alkyl group or a C _1-6 alkoxy group, which can be a methyl group or a methoxy group, which can be a methyl group];

Among the other T's, there is a group opposite to the PFPE in the main chain of the molecule (that is, a carbon atom in the formulas (A1), (A2), (D1) and (D2). In addition, in the following formula ( When B1), (B2), (C1) and (C2) are Si atoms), the remaining T is independently a methyl group, a phenyl group, a C _1-6 alkoxy group or a radical capturing group or ultraviolet light Absorbent base.

類的殘基。 The radical capturing group is not particularly limited as long as it can capture radicals generated by light irradiation. Examples of free radical trapping groups include benzophenones, benzotriazoles, benzoates, phenyl salicates, crotonic acids, malonates, organic acrylates, hindered amines, hindered Phenols or tri

class residues.

酮(Benzoxazinone)類、苯并

唑(Benzoxazole)類的殘基。 The ultraviolet absorbing group is not particularly limited as long as it can absorb ultraviolet rays. Examples of ultraviolet absorbing groups include benzotriazoles, hydroxybenzophenones, substituted and unsubstituted esters of benzoic acid or salicylic acid compounds, acrylates or alkoxycinnamates (Cinnamate). , Oxamides, Oxanilides, Benzo

Ketones (Benzoxazinone), benzo

Benzoxazole residues.

In one aspect, the radical trapping group or the ultraviolet absorbing group is represented by the following formula,

In this aspect, X ¹⁰¹ , X ¹⁰⁵ , X ¹⁰⁷ and X ¹⁰⁹ can each independently be a 3 to 10 valent organic group.

In one aspect, the PFPE silane compound β is a compound represented by the above formula (A1), (B1), (C1), (D1) or (E1).

In one aspect, the PFPE silane compound β is a compound represented by the above formula (A2), (B2), (C2) or (D2).

In one aspect, the PFPE silane compound β is a compound represented by the above formula (A1), (A2), (C1), (C2), (D1), (D2) or (E1). Since these compounds can have a plurality of Si having hydroxyl groups or hydrolyzable groups at the terminal, the wear resistance can be further improved.

In one aspect, the PFPE silane compound β is the compound represented by (C1), (C2), (D1), (D2) or (E1) above.

In one aspect, the PFPE silane compound β is the compound represented by (C1), (C2), (D1) or (D2) above.

In one aspect, the PFPE silane compound β is a compound represented by the above formulas (A1) and (A2).

In one aspect, the PFPE silane compound β is a compound represented by the above formulas (B1) and (B2).

In one aspect, the PFPE silane compound β is a compound represented by the above formulas (C1) and (C2). In this way, the wear resistance and surface smoothness can be further improved. In addition, the compounds represented by the above-mentioned formulas (C1) and (C2) have high miscibility with compounds containing an isocyanuric acid skeleton such as the PFPE silane compound α .

In one aspect, the PFPE silane compound β is a compound represented by the above formulas (D1) and (D2).

In one aspect, the PFPE silane compound β is a compound represented by the above formula (E1).

The average molecular weight of the PFPE silane compound β may be 1,000 or more, 1,500 or more, or 2,000 or more. The average molecular weight of the PFPE silane compound β may be 30,000 or less, or 10,000 or less. In one aspect, the average molecular weight of the PFPE silane compound β is 1,000 or more and 10,000 or less.

In the surface treatment agent of the present disclosure, the weight ratio of PFPE silane compound α to PFPE silane compound β can be 1:99 to 99:1, 5:95 to 90:10, 30:70 to 90:10 or 30:70 to 70:30.

The compounds represented by the above formulas (A1), (A2), (B1), (B2), (C1), (C2), (D1), (D2) and (E1) can be prepared by commonly known methods. manufacturing.

"Other Compounds"

The surface treatment agent of the present disclosure may further contain compounds other than PFPE silane compounds α and β . Typical examples of other compounds include compounds obtained by ring-opening the isocyanuric acid ring of PFPE silane compound α (other silane compounds) and compounds derived from the synthesis of PFPE silane compound α .

Examples of other silane compounds include compounds represented by the following formula ( α 1') and formula ( α 2'),

[In the formula, each symbol has the same meaning as formula ( α 1) and formula ( α 2)]; and

Except that the perfluoropolyether group does not have OCF ₂ units, the rest have the same formulas (A1), (A2), (B1), (B2), (C1), (C2), (D1), (D2) and (E1) Silane compound with the same structure.

The above-mentioned perfluoropolyether group without OCF ₂ unit is represented by the following formula,

-(OC ₆ F ₁₂ ) _a -(OC ₅ F ₁₀ ) _b -(OC ₄ F ₈ ) _c -(OC ₃ X ¹⁰ ₆ ) _d -(OC ₂ F ₄ ) _e -

[In the formula, each symbol has the same meaning as the above-mentioned polyether chain].

The above-mentioned perfluoropolyether group without OCF ₂ unit can also be: a group represented by the following formula,

-(OC ₃ X ¹⁰ ₆ ) _d -

[In the formula, d and X ¹⁰ have the same meaning as above, X ¹⁰ can be F]; and

The basis represented by the following formula,

-(OC ₂ F ₄ -R ^2" ) _g" -

[In the formula, R ^2" is a group selected from OC ₂ F ₄ , OC ₃ F ₆ and OC ₄ F ₈ , and g" is an integer from 2 to 100].

^- _{( OC 3 _ _ _ _ _ _ _ _ _ _} It can be -(OCF ₂ CF ₂ CF ₂ ) _d -.

The content of other silane compounds may be 0.01 to 20 mol parts, 0.1 to 15 mol parts, 1 to 10 mol parts, or 3 to 5 mol parts per 100 mol parts of PFPE silane compound α, for example.

Examples of compounds derived from the synthesis of PFPE silane compound α include: R ¹ -OSO ₂ CF ₃ or CF ₃ SO ₂ OR ^1' -OSO ₂ CF ₃ .

"Cross-linking Compounds"

The surface treatment agent may further contain a cross-linking compound. The cross-linking compound causes the PFPE silane compound α to undergo a sol-gel reaction. The surface treatment layer is formed through a sol-gel reaction, thereby promoting the surface segregation of the PFPE silane compound α , thereby further improving the antifouling property.

The crosslinking compound contains at least one of a compound represented by the following formula (Q1) and a compound represented by the following formula (Q2),

A[Z ^q1 -M ^q (OR ^q1 ) _wn1 (R ^q2 ) _wn2-wn1 ] _wa1 [Z ^q2 -R ^q3 ] _wa2 (Q1)

[In the formula,

A is an organic radical with 1 to 10 valence,

Z ^q1 are independently single bonds or divalent organic groups,

M ^q is Al, Ca, Fe, Ge, Hf, In, Si, Ta, Ti, Sn, Zr or Zn;

R ^q1 are each independently a hydrogen atom or a C _1-6 alkyl group,

R ^q2 are each independently a hydrogen atom or a hydrocarbon group,

wn1 is independently 1 or more and (valence of M ^q -1) or less,

wn2 are independently (valence of M ^q -1),

Z ^q2 are independently single bonds or divalent organic groups,

R ^q3 are independently reactive groups,

wa1 is an integer from 1 to 10,

wa2 is an integer from 0 to 10,

The sum of wa1 and wa2 is the valence of A];

[In the formula,

M is Al, Ca, Fe, Ge, Hf, In, Si, Ta, Ti, Sn, Zr or Zn;

R ^q are independently a hydrogen atom, C _1-6 alkyl group or R ^q1 -CO-;

R ^q1 is a 1-valent hydrocarbon group;

R ^q' are independently C _1-3 alkyl or C _1-3 alkoxy;

mq is the valence of the aforementioned M;

nq is 0 or more and less than the valence of the aforementioned M].

(Compound represented by formula (Q1))

A[Z ^q1 -M ^q (OR ^q1 ) _wn1 (R ^q2 ) _wn2-wn1 ] _wa1 [Z ^q2 -R ^q3 ] _wa2 (Q1)

A is an organic base with 1 to 10 valences, preferably 1 to 8 valences, particularly preferably 1 to 6 valences, more preferably 1 to 4 valences, still more preferably 1 to 3 valences, particularly preferably 2 or 3 valences. base.

In one form, A is a divalent organic radical.

The above-mentioned divalent organic group is preferably a group represented by the following formula:

-[(R ^A1 ) _a11 -(R ^A2 ) _a12 -(R ^A3 ) _a13 ]-

[In the formula,

R ^A1 are each independently an alkylene group, preferably a C _1-20 alkylene group, especially a C _1-10 alkylene group, more preferably a C _1-6 alkylene group, and even more preferably a C _{1- 4} alkylene;

R ^A2 are each independently a cycloalkyl group, preferably a C _3-20 cycloalkyl group, especially a C _3-10 cycloalkyl group, more preferably a C _5-8 cycloalkyl group, and still more preferably It is C _5-7 cycloalkylene group;

R ^A3 are each independently an aryl group, preferably a C _6-20 aryl group, especially a C _6-10 aryl group, more preferably a C _6-8 aryl group, particularly preferably a phenyl group;

a11 is an integer from 0 to 5, preferably an integer from 0 to 3, especially an integer from 0 to 2, and more preferably 1 or 2;

a12 is an integer from 0 to 5, preferably an integer from 0 to 3, especially 0 or 1;

a13 is an integer from 0 to 5, preferably an integer from 0 to 3, especially 0 or 1;

The total of a11, a12 and a13 is 1 or more, preferably an integer from 1 to 5, particularly preferably an integer from 1 to 3;

The order of existence of the repeating units marked a11, a12 and a13 and enclosed in parentheses is arbitrary].

In one aspect, A is R ^A1 (alkylene group above).

The alkylene group in the above R ^A1 may be a straight chain or a branched chain, preferably a straight chain.

In other forms, A is a trivalent organic group.

The above-mentioned trivalent organic group is preferably represented by the following formula:

[In the formula,

X ^a is each independently a single bond or a divalent organic group].

In one state, X ^a is a single bond.

In other forms, X ^a is a divalent organic group.

_The divalent organic group ⁱⁿ ₁₀ Alkylene group, or a divalent hydrocarbon group having 1 to 10 carbon atoms containing at least one bond selected from the group consisting of ether bond and ester bond.

In a preferred aspect, the divalent organic group in X ^a is a group represented by the following formula,

-(CX ²²¹ X ²²² ) _x11 -(X ^a1 ) _y11 -(CX ²²³ X ²²⁴ ) _z11 -

[ ^{In the} _formula ^, X ²²¹ to

The above X ^a1 is -C(=O)NH-, -NHC(=O)-, -O-, -C(=O)O-, -OC(=O)-, -OC(=O)O- Or -NHC(=O)NH-(the left side of each bond is bonded to CX ²²¹ X ²²² ),

x11 is an integer from 0 to 10, y11 is 0 or 1, z11 is an integer from 1 to 10].

In addition, the left side of the above-mentioned group is bonded to the isocyanuric acid ring.

X ^a1 is preferably -O- or C(=O)O-.

The divalent organic group in X ^a is particularly preferably a group represented by the following formula

-(CF ₂ ) _m111 -(CH ₂ ) _m112 -O-(CH ₂ ) _m113 -

[In the formula, m111 is an integer from 1 to 3, m112 is an integer from 1 to 3, and m113 is an integer from 1 to 3]; or

The basis represented by the following formula

-(CF ₂ ) _m114 -(CH ₂ ) _m115 -O-CH ₂ CH(OH)-(CH ₂ ) _m116 -

[In the formula, m114 is an integer from 1 to 3, m115 is an integer from 1 to 3, and m116 is an integer from 1 to 3]; or

The basis represented by the following formula

-(CF ₂ ) _m117 -(CH ₂ ) _m118 -

[In the formula, m117 is an integer from 1 to 3, m118 is an integer from 1 to 3]; or

The basis represented by the following formula

-(CF ₂ ) _m119 -(CH ₂ ) _m120 -O-CH ₂ CH(OSi(OCH ₃ ) ₃ )-(CH ₂ ) _m121 -

[In the formula, m119 is an integer from 1 to 3, m120 is an integer from 1 to 3, m121 is an integer from 1 to 3]; or

The basis represented by the following formula

-(CH ₂ ) _m122 -

[In the formula, m122 is an integer from 1 to 3].

The divalent organic group in X ^a is not particularly limited, and specific examples include:

-CH ₂ -, -C ₂ H ₄ -, -C ₃ H ₆ -, -C ₄ H ₈ -, -C ₄ H ₈ -O-CH ₂ -, -CO-O-CH ₂ -CH(OH) -CH ₂ -, -(CF ₂ ) _n15 -(n15 is an integer from 0 to 4), -(CF ₂ ) _n25 -(CH ₂ ) _m25 -(n25 and m25 are independently an integer from 0 to 4), -CF ₂ CF ₂ CH ₂ OCH ₂ CH(OH)CH ₂ -, - CF ₂ CF ₂ CH ₂ OCH ₂ CH(OSi(OCH ₃ ) ₃ )CH ₂ -etc.

Z ^q1 are each independently a single bond or a divalent organic group.

In one state, Z ^q1 is a single bond.

In other forms, Z ^q1 are independently divalent organic groups.

The divalent organic groups in the above Z ^q1 are each independently an alkylene group, preferably a C _1-20 alkylene group, especially a C _1-10 alkylene group, and more preferably a C _1-6 alkylene group, Still more preferably, it is C _1-4 alkylene group.

M ^q is Al, Ca, Fe, Ge, Hf, In, Si, Ta, Ti, Sn, Zr or Zn.

M ^q is preferably Si, Ti or Zr, particularly Si.

R ^q1 are each independently a hydrogen atom or a C _1-6 alkyl group.

In a preferred embodiment, R ^q1 are each independently a C _1-6 alkyl group, preferably a C _1-3 alkyl group, especially a C _1-2 alkyl group.

R ^q2 are each independently a hydrogen atom or a hydrocarbon group.

R ^q2 are each independently a hydrocarbon group.

The hydrocarbon group in R ^q2 is preferably a C _1-6 alkyl group, preferably a C _1-3 alkyl group, and particularly preferably a C _1-2 alkyl group.

wn1 is independently 1 or more and (valence of M ^q -1) or less, and wn2 is (valence of M ^q -1).

wn1 is preferably 2 or more and (valence number of M ^q -1) or less, particularly preferably 3 or more and (valence number of M ^q -1) or less, more preferably (valence number of M ^q -1).

Z ^q2 are each independently a single bond or a divalent organic group.

In one state, Z ^q2 is a single bond.

In other forms, Z ^q2 are independently divalent organic groups.

The divalent organic group in the above Z ^q2 is preferably a C _1-6 alkylene group, -(CH ₂ ) _z21 -O-(CH ₂ ) _z22 -(in the formula, z21 is an integer from 0 to 6, for example, 1 to an integer of 6, z22 is an integer of 0 to 6, for example, an integer of 1 to 6) or -(CH ₂ ) _z23 -phenylene-(CH ₂ ) _z24 -(wherein, z23 is an integer of 0 to 6 an integer, for example, an integer from 1 to 6, z24 is an integer from 0 to 6, for example, an integer from 1 to 6). The C _1-6 alkylene group can be a straight chain or a branched chain, preferably a straight chain. These groups may be substituted by one or more substituents selected from, for example, a fluorine atom, C _1-6 alkyl group, C _2-6 alkenyl group and C _2-6 alkynyl group, and are preferably unsubstituted.

In a preferred embodiment, Z ¹ is a C _1-6 alkylene group or -(CH ₂ ) _z21 -O-(CH ₂ ) _z22 -(in the formula, z21 is an integer from 0 to 6, for example, 1 to 6 an integer, z22 is an integer from 0 to 6, for example, an integer from 1 to 6).

R ^q3 are each independently a reactive group.

The above-mentioned R ^q3 groups are each independently an isocyanate group, an epoxy group or a vinyl group.

In one aspect, the reactive group is an isocyanate group.

In other aspects, the reactive group is an epoxy group.

In other aspects, the reactive group is vinyl.

wa1 is an integer from 1 to 10, wa2 is an integer from 0 to 10, and the sum of wa1 and wa2 is the valence of A.

In one state, wa1 is an integer from 1 to 10, and wa2 is 0.

In other modes, wa1 is an integer from 1 to 10, and wa2 is an integer from 1 to 10.

In a preferred pattern, wa1 is 1 or 2, and wa2 is 0 or 1. Preferably, wa1 is 1, and wa2 is 1.

(Compound represented by formula (Q2))

M is Al, Ca, Fe, Ge, Hf, In, Si, Ta, Ti, Sn, Zr or Zn.

M is preferably Si, Ti or Zr, particularly preferably Si.

R ^q is each independently a hydrogen atom, a C _1-6 alkyl group or R ^q1 -CO-.

R ^q are each independently preferably a C _1-6 alkyl group, particularly preferably a C _1-3 alkyl group, and even more preferably a C _1-2 alkyl group.

R ^q' are each independently C _1-3 alkyl or C _1-3 alkoxy.

The alkyl group in R ^q' is preferably a methyl group or an ethyl group, and is particularly preferably a methyl group.

The alkoxy group in the above R ^q' is preferably a methoxy group or an ethoxy group, particularly preferably an ethoxy group.

mq is the valence of the above-mentioned M, and nq is 0 or more and less than the valence of the above-mentioned M.

In one state, nq is the valence of M.

In other modalities, (mq-nq) is 1.

The concentration of the crosslinking compound may be, for example, 3 parts by mass or more, and may be 10 parts by mass or more relative to 100 parts by mass of the surface treatment agent. The concentration of the crosslinkable compound is, for example, 30 parts by mass or less, and may be 20 parts by mass or less. In one aspect, the concentration of the cross-linkable compound is 3 parts by mass or more and 30 parts by mass or less.

"Acid Catalyst"

The surface treatment agent containing the cross-linking compound may further contain an acid catalyst. The content of the acid catalyst may be 0.1 parts by mass or more or more than 0.5 parts by mass relative to 100 parts by mass of the surface treatment agent. acid catalyst The content may be 5 parts by mass or less, or 3 parts by mass or less. In one aspect, the content of the acid catalyst is 0.1 parts by mass or more and 5 parts by mass or less.

Examples of acid catalysts include inorganic acids such as nitric acid, hydrochloric acid, and sulfuric acid; dicarboxylic acids such as oxalic acid and hexafluoroglutaric acid; and organic acids such as p-toluenesulfonic acid and trifluoroacetic acid. Acid catalysts can be hydrochloric acid, oxalic acid and nitric acid.

"Organic Solvent"

Surface treatment agents can be diluted with organic solvents. The organic solvent is not particularly limited as long as it can uniformly disperse and dissolve the PFPE silane compound α and the like. From the viewpoint of the stability of the surface treatment agent and the volatility of the organic solvent, examples of the organic solvent include perfluoroaliphatic hydrocarbons having 5 to 12 carbon atoms (such as perfluorohexane, perfluoromethylcyclohexane, and Perfluoro-1,3-dimethylcyclohexane); polyfluoroaromatic hydrocarbons (such as bis(trifluoromethyl)benzene); polyfluoroaliphatic hydrocarbons; hydrofluoroethers (HFE). These organic solvents can be used alone or in a mixture of two or more types.

When the surface treatment agent contains a cross-linking compound, examples of the organic solvent include lower alcohols such as ethanol, butanol, and isopropyl alcohol; ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; methyl cellosolve, Cellosolves such as ethyl cellosolve; aromatic hydrocarbons such as xylene and toluene; aliphatic hydrocarbons such as n-hexane and n-heptane; esters such as ethyl acetate and butyl acetate. These organic solvents may be used alone or in the form of a mixture of two or more fluorine-containing solvents.

Examples of polyfluoroaliphatic hydrocarbons include: C ₆ F ₁₃ CH ₂ CH ₃ (for example, ASAHIKLIN (registered trademark) AC-6000 manufactured by Asahi Glass Co., Ltd.), 1,1,2,2,3,3,4-7 Fluorocyclopentane (for example, ZEORORA (registered trademark) H manufactured by Zeon Japan Co., Ltd.). Examples of hydrofluoroethers (HFE) include perfluoropropyl methyl ether (C ₃ F ₇ OCH ₃ ) (for example, Novec (trademark) 7000 manufactured by Sumitomo 3M Co., Ltd.), perfluorobutyl methyl ether (C ₄ F ₉ OCH ₃ ) (such as Novec (trademark) 7100 manufactured by Sumitomo 3M Co., Ltd.), perfluorobutyl ether (C ₄ F ₉ OC ₂ H ₅ ) (such as Novec (trademark) 7200 manufactured by Sumitomo 3M Co., Ltd.), all Alkyl perfluoroalkyl ethers such as fluorohexyl methyl ether (C ₂ F ₅ CF (OCH ₃ ) C ₃ H ₇ ) (for example, Novec (trademark) 7300 manufactured by Sumitomo 3M Co., Ltd.) (perfluoroalkyl and alkyl can linear or branched); or CF ₃ CH ₂ OCF ₂ CHF ₂ (for example, ASAHIKLIN (registered trademark) AE-3000 manufactured by Asahi Glass Co., Ltd.). The organic solvent can be hydrofluoroether, perfluorobutyl methyl ether (C ₄ F ₉ OCH ₃ ) and/or perfluorobutyl ethyl ether (C ₄ F ₉ OC ₂ H ₅ ).

"Fluorinated oil"

The surface treatment agent may also contain a (non-reactive) fluoropolyether compound (typically a perfluoro(poly)ether compound) that can be understood as a fluorine-containing oil (hereinafter referred to as "fluorinated oil"). Fluorine-containing oil can improve the surface smoothness of the surface treatment layer.

The fluorine-containing oil is not particularly limited. Examples include perfluoropolyether compounds represented by the following general formula (3).

Rf ¹¹ -(OC ₄ F ₈ ) _a1 -(OC ₃ F ₆ ) _b1 -(OC ₂ F ₄ ) _c1 -(OCF ₂ ) _d1 -Rf ²¹ ． ． ． (3)

In the formula, Rf ¹¹ represents a C _1-16 alkyl group that may be substituted by one or more fluorine atoms (typically a C _1-16 perfluoroalkyl group);

Rf ²¹ represents a C _1-16 alkyl group (typically a C _1-16 perfluoroalkyl group) that may be substituted by one or more fluorine atoms, a fluorine atom or a hydrogen atom;

Rf ¹¹ and Rf ²¹ can each independently be a C _1-3 perfluoroalkyl group;

a1, b1, c1 and d1 respectively represent the number of four repeating units of perfluoropolyether constituting the main skeleton of the polymer, and are independently integers between 0 and 300;

The sum of a1, b1, c1 and d1 is at least 1, can be 1 to 300, or can be 20 to 300.

The order of existence of each repeating unit marked with the subscript a1, b1, c1 or d1 and enclosed in parentheses is arbitrary in the formula.

-(OC ₄ F ₈ )- can be -(OCF ₂ CF ₂ CF ₂ CF ₂ )-, -(OCF(CF ₃ )CF ₂ CF ₂ )-, -(OCF ₂ CF(CF ₃ )CF ₂ )- ,-(OCF ₂ CF ₂ CF(CF ₃ ))-,-(OC(CF ₃ ) ₂ CF ₂ )-,-(OCF ₂ C(CF ₃ ) ₂ )-,-(OCF(CF ₃ )CF( CF ₃ ))-, -(OCF(C ₂ F ₅ )CF ₂ )- or -(OCF ₂ CF(C ₂ F ₅ ))-, or -(OCF ₂ CF ₂ CF ₂ CF ₂ )-.

-(OC ₃ F ₆ )- can be -(OCF ₂ CF ₂ CF ₂ )-, -(OCF(CF ₃ )CF ₂ )- or -(OCF ₂ CF(CF ₃ ))-, or -( OCF ₂ CF ₂ CF ₂ )-.

-(OC ₂ F ₄ )- can be -(OCF ₂ CF ₂ )- or -(OCF(CF ₃ ))-, or -(OCF ₂ CF ₂ )-.

In one aspect, the perfluoropolyether compound is represented by any one of the following general formulas (3a) and (3b). These can be used individually by 1 type or in mixture of 2 or more types.

Rf ¹¹ -(OCF ₂ CF ₂ CF ₂ ) _b1" -Rf ²¹ ...(3a)

Rf ¹¹ -(OCF ₂ CF ₂ CF ₂ CF ₂ ) _a1" -(OCF ₂ CF ₂ CF ₂ ) _b1" -(OCF ₂ CF ₂ ) _c1" -(OCF ₂ ) _d1" -Rf ²¹ ． ． ． (3b)

In the formula, Rf ¹¹ and Rf ²¹ are as explained above;

In formula (3a), b1" is an integer from 1 to 100;

In formula (3b), a1" and b1" are independently from 0 to 30, and can be an integer from 1 to 30; c1" and d1" are independently from 1 to 300; mark The subscripts a1", b1", c1", d1" and the order of existence of each repeating unit enclosed in parentheses is arbitrary in the formula.

The average molecular weight of fluorinated oil can range from 1,000 to 30,000. This can further improve surface smoothness.

The content of the fluorine-containing oil may be, for example, 0.1 to 500 parts by mass, 1 to 400 parts by mass, or 5 to 300 parts by mass relative to a total of 100 parts by mass of the PFPE silane compound α and the PFPE silane compound β .

Fluorine-containing oil can be a compound represented by the following general formula:

Rf ³¹ -F

[In the formula, Rf ³¹ is C _5-16 perfluoroalkyl];

Or chlorotrifluoroethylene oligomer.

"Polysilicone Oil"

The surface treatment agent may also contain a (non-reactive) polysilicone compound understood as polysilicone oil (hereinafter referred to as "polysilicone oil"). Thereby, the surface smoothness of the surface treatment layer can be improved.

Examples of the polysiloxane oil include linear or cyclic ones with a siloxane bond number of 2,000 or less. Linear polysilicone oil can be so-called pure polysilicone oil and modified polysilicone oil. Examples of pure polysilicone oil include dimethyl polysilicone oil, methylphenyl polysilicone oil, and methyl hydrogen polysilicone oil. Examples of modified polysilicone oil include those that modify pure polysilicone oil through alkyl groups, aralkyl groups, polyethers, higher fatty acid esters, fluoroalkyl groups, amine groups, epoxy groups, carboxyl groups, alcohols, etc. . Examples of the cyclic polysiloxane oil include cyclic dimethylsiloxane oil.

The content of the polysiloxane oil may be, for example, 0 to 300 parts by mass, or 0 to 200 parts by mass relative to the total of 100 parts by mass of the PFPE silane compound α and the PFPE silane compound β .

"other"

The surface treatment agent may further contain other additives. Examples of other additives include: tackifiers, leveling agents, defoaming agents, antistatic agents, antiturbid agents, ultraviolet absorbers, free radical scavengers, pigments, dyes, fillers, catalysts, alcohols, transition metals, Halide ions are compounds containing atoms with lone pairs of electrons in their molecular structure.

Among them, from the viewpoint of weather resistance, the surface treatment agent may contain at least one of an ultraviolet absorber and a radical scavenger. Examples of ultraviolet absorbers and radical scavengers include those exemplified as "things that may be contained in the primer." The (total) concentration of the ultraviolet absorber and/or radical scavenger is, for example, 0.5 mass% or more, 1.0 mass% or more, or 2.0 mass% or more, based on 100 mass% of the surface treatment agent. The concentration of the ultraviolet absorber and/or radical scavenger is, for example, 3.0 mass% or less, and may be 2.5 mass% or less. In one aspect, the concentration of the ultraviolet absorber and/or radical scavenger is 0.5 mass% or more and 3.0 mass% or less.

Examples of the catalyst include acids (eg, acetic acid, formic acid, trifluoroacetic acid), bases (eg, ammonia, triethylamine, diethylamine), and transition metals (eg, Ti, Ni, Sn). Regarding the catalyst, it is preferable to add it to the solution containing the PFPE silane compound α just before applying the surface treatment agent.

Examples of the alcohol include alcohol compounds having 1 to 6 carbon atoms.

Examples of transition metals include platinum, ruthenium, and rhodium.

Examples of halide ions include chloride ions.

A compound containing an atom with a lone pair of electrons in its molecular structure contains at least one atom selected from the group consisting of a nitrogen atom, an oxygen atom, a phosphorus atom and a sulfur atom, and may contain a sulfur atom or nitrogen atoms.

Compounds containing atoms with lone pairs of electrons in the molecular structure may contain amine groups, amide groups, sulfenyl groups, P=O groups, S=O groups and sulfonyl groups in the molecular structure. At least one functional group in the group may also contain at least one functional group selected from the group consisting of P=O group and S=O group.

Compounds containing atoms with lone pairs of electrons in the molecular structure are selected from, for example, aliphatic amine compounds, aromatic amine compounds, phosphorus amide compounds, amide compounds, urea compounds, and At least one kind from the group consisting of trisine compounds. The above-mentioned compound may be at least one selected from the group consisting of aliphatic amine compounds, aromatic amines, phosphate amide, urea compounds and sulfonylene compounds, or may be selected from the group consisting of styrene compounds, At least one kind from the group consisting of an aliphatic amine compound and an aromatic amine compound may also be a styrene compound.

Examples of aliphatic amine compounds include diethylamine and triethylamine. Examples of aromatic amine compounds include aniline and pyridine. Examples of the phosphatidamide compound include hexamethylphosphatidamide. Examples of amide compounds include: N,N-diethylformamide, N,N-diethylformamide, N,N-dimethylacetamide, N-methylformamide, N, N-Dimethylformamide, N-methyl Pyrrolidone. Examples of urea compounds include tetramethylurea. Examples of the sericene compound include dimethylsulfoxide (DMSO: Dimethyl Sulfoxide), tetramethylene sulfoxide, methylphenyl sulfoxide, and diphenyl sulfoxide. Compounds containing atoms with lone pairs of electrons in their molecular structure may be dimethylstyrene or tetramethylenesityrene.

[How to make items]

The manufacturing method of the article disclosed herein includes the following steps: using a primer to form a primer layer on an organic substrate, where the primer contains a coupling agent, and the coupling agent has an organic reactive group in one molecule and hydrolyzable silicone base; and using a surface treatment agent to form a surface treatment layer directly above the primer layer, where the surface treatment agent contains PFPE silane compound α . The primer and surface treatment agent are as described above respectively.

(1) Formation of primer layer

The method of applying the primer is not particularly limited. Examples of the coating method include a wet coating method. Examples of wet coating methods include dip coating, spin coating, flow coating, spray coating, roll coating, and gravure coating. The primer can be applied by spin coating.

The amount of primer applied is not particularly limited. The primer is applied, for example, so that the thickness of the primer layer becomes 1 nm or more and 50 nm or less.

After the primer is applied, it can be heat treated to remove the organic solvent contained in the primer. The heat treatment conditions are appropriately set according to the type and amount of the organic solvent, the thickness of the primer layer, etc.

(2) Formation of surface treatment layer

The method of applying the surface treatment agent is not particularly limited. Examples of the coating method include the above-mentioned wet coating method. The surface treatment agent can be applied by spray coating.

The coating amount of the surface treatment agent is not particularly limited. The surface treatment agent is applied so that the thickness of the surface treatment layer becomes 1 nm or more and 50 nm or less, for example.

After the surface treatment agent is applied, it can be post-processed. Through post-treatment, the durability of the surface treatment layer can be improved.

Post-processing can be heating. The heating conditions are not particularly limited. The heating temperature may be, for example, 60 to 250°C, or 100°C to 180°C. The heating time is, for example, 30 minutes to 5 hours, or 1 to 3 hours.

Post-processing may also be performed by sequentially supplying water and heating. By supplying water, the water system acts on the hydrolyzable group of the PFPE silane compound α in the surface treatment agent that is bonded to Si, so that the compound can be rapidly hydrolyzed. By heating, the dehydration condensation reaction between the hydrolyzed groups bonded to Si becomes easy to proceed between the PFPE silane compounds α . In addition, by heating, "the hydrolyzed group bonded to Si of the PFPE silane compound α " and "the reactive group existing on the surface of the organic base material" are reacted. When the reactive group present on the surface of the organic substrate is a hydroxyl group, a dehydration condensation reaction can occur. As a result, a bond is formed between the PFPE silane compound α and further between the PFPE silane compound α and the organic base material.

The method of supplying moisture is not particularly limited. Moisture can be supplied by, for example, "condensation caused by the temperature difference between the film formed of the surface treatment agent (the precursor of the surface treatment layer, also referred to as the "precursor layer" below) and the surrounding gas environment" or "for "Steam blowing of the precursor layer" is performed.

The ambient environment when supplying water or the temperature of the water are not particularly limited. The temperature is, for example, 0 to 250°C, may be 60°C or higher, or may be 100°C or higher. The temperature may be 180°C or lower, or 150°C or lower. By supplying water in this gas environment, hydrolysis can be rapidly performed. Moisture supply can also be performed under normal pressure.

Heating is performed, for example, in a dry gas environment exceeding 60°C. The heating method is not particularly limited. For example, it is only necessary to place the organic substrate with the precursor layer in a gas environment exceeding 60°C and having an unsaturated water vapor pressure. The heating temperature may exceed 100°C, may be below 250°C, or may be below 180°C. Heating can also be performed under normal pressure.

Regarding post-processing, water supply and drying and heating can be performed continuously. Continuous post-treatment can be carried out by, for example, superheated steam.

For superheated steam, it is obtained by heating saturated steam to a temperature higher than the boiling point. Superheated steam is high-temperature water vapor obtained by heating water to a temperature exceeding the boiling point (more than 100°C under normal pressure, generally 250°C or lower, for example, 180°C or lower). When the precursor layer is exposed to superheated vapor, first, condensation is generated on the surface of the precursor layer due to the temperature difference between the superheated vapor and the precursor layer, thereby supplying moisture to the precursor layer. As the temperature difference between the superheated vapor and the precursor layer decreases, the moisture on the surface of the precursor layer will vaporize in the dry gas environment formed by the superheated vapor, and the amount of moisture on the surface of the precursor layer gradually decreases. . During the period when the moisture content on the surface of the precursor layer decreases, that is, during the period when the precursor layer is in a dry gas environment, the precursor layer is The superheated steam comes into contact and is heated to the temperature of the superheated steam (a temperature exceeding 100°C under normal pressure). That is, moisture supply and drying and heating can be continuously performed simply by exposing the precursor layer to superheated vapor.

After the surface treatment agent is coated, the above-mentioned post-treatment may not be performed. In this case, after the precursor layer is formed on the organic substrate, the organic substrate can be left to stand for more than 8 hours, preferably for more than 12 hours, and especially for more than 15 hours. The temperature during standing may be room temperature, or may be, for example, 20 to 35°C.

[Surface treatment agent]

The present disclosure includes surface treatment agents used in the manufacture of the above-mentioned articles.

The surface treatment agent contains the above-mentioned PFPE silane compound α . Details of the concentration of the PFPE silane compound α and other components that may be contained in the surface treatment agent are as described above.

The articles disclosed herein maintain antifouling properties even after long-term use under severe outdoor environmental conditions such as wind, rain or adhesion of pollutants. The surface treatment agent of the present disclosure can form an antifouling layer with excellent wear resistance and weather resistance.

[Example]

Next, examples are given to illustrate the disclosure, but the disclosure is not limited only to the examples. In addition, in this embodiment, the chemical formulas shown below all represent the average composition of the repeating units ((CF ₂ CF ₂ CF ₂ O), (CF ₂ CF ₂ O), (CF ₂ O) constituting the perfluoropolyether. etc.) exist in any order.

[Synthesis example 1]

The following PFPE-containing silane compound (A) was synthesized according to the method described in the publication WO2010/125964.

[Synthesis example 2]

Next, the following PFPE-containing silane compound (B) was synthesized according to the method described in the publication WO2018/056410.

[Synthesis example 3]

The following PFPE-containing silane compound (C) was synthesized according to the method described in the publication WO2010/125964.

． Target base material: Resin

[Example 1]

(1) Preparation of organic substrate

A polycarbonate base material (thickness 2 mm, planar size 100 mm×100 mm) was washed with water and alcohol to obtain an organic base material.

(2) Preparation of primer

3-Aminopropyltrimethoxysilane (APTMS) was added to ethanol to obtain a primer with an APTMS concentration of 1.0 mass%.

(3) Preparation of surface treatment agent

The PFPE-containing silane compound (A) was dissolved in hydrofluoroether (Novec HFE7200, manufactured by 3M Company) so that the concentration would be 0.1 wt%, thereby obtaining a surface treatment agent.

(4) Formation of primer layer

The primer is coated on the surface of the organic substrate by spin coating. Then, drying was performed at 130° C. for 5 minutes to form a primer layer with a thickness of 5 nm.

(5) Formation of surface treatment layer

Use a commercially available spray coating device equipped with a 2-fluid nozzle to uniformly spray the surface treatment agent onto the primer layer at a nozzle speed of 70 mm/sec. Then, it was left to stand at room temperature in the air for 24 hours to form a surface treatment layer with a thickness of 5 nm. Through this operation, an article having an organic base material, a primer layer and a surface treatment layer is obtained.

[Example 2]

An article was obtained in the same manner as in Example 1 except that the PFPE-containing silane compound (B) was used instead of the PFPE-containing silane compound (A).

[Example 3]

In addition to using the PFPE-containing silane compound (C) to replace the PFPE-containing silane compound (A), tetraethoxysilane (crosslinking compound, TEOS) was further added to the surface treatment agent so that the concentration would be 4.5%. ), and an article was obtained in the same manner as in Example 1, except that 0.01N hydrochloric acid was further added so as to obtain a concentration of 0.03%.

[Example 4]

Except that 3-glycidoxypropyltrimethoxysilane (GPTMS) was added in place of APTMS, the same operation as in Example 1 was performed to obtain an article.

[Comparative example 1]

Except that the primer layer was not formed, the same operation as in Example 1 was performed to obtain an article.

[Comparative example 2]

An article was obtained in the same manner as in Example 1 except that the following PFPE-containing silane compound (a) was used instead of the PFPE-containing silane compound (A).

CF ₃ O-(CF ₂ CF ₂ O) _m (CF ₂ O) _n CF ₂ CH ₂ OSi(OCH ₃ ) ₃ (a)

(m=22,n=19)

[Evaluation (Substrate: Resin)]

Make the following evaluation of the items obtained. The results are shown in Table 1 or Figure 1.

(1) Appearance

Assess the appearance of the item visually. The evaluation criteria are explained below.

G: Transparent.

NG: Whitening or foreign matter such as slight unevenness on the surface.

(2) Adhesion

The adhesion of the surface treatment layer is evaluated by cross-cut test. Specifically, a cutting knife was used to cut 11 cuts that reached the base material texture on the test surface to create 100 checkerboard squares with 2 mm intervals between cuts, and Sellotape (registered trademark) was strongly pressed against the parts. , and then peel off the end of the tape in one breath at an angle of 45°. A black oil-based pen (manufactured by Zebra Co., Ltd., trade name: Mackee) was used to paint the checkerboard squares after the tape was peeled off, and the portion where the ink was not removed was used as the defective portion of the surface treatment layer. The evaluation criteria are explained below.

10 points: No peeling on any grid

8 points: There is some slight peeling at the intersection of the cuts, and the area of the defect is within 5% of the area of the entire square.

6 points: There is peeling on both sides of the cut and at the intersection, and the area of the defect is more than 5% and less than 15% of the area of the entire square.

4 points: Partial or complete peeling along the line of the incision, the area of the defective part is more than 15% and less than 35% of the area of the entire square.

2 points: Partial or complete peeling along the line of the incision, the area of the defective part is more than 35% and less than 65% of the area of the entire square.

0 points: The area of the defective part of the cut is more than 65% of the entire square.

(3) Antifouling property A (repellency of oily ink)

On the surface treatment layer, use a black oil-based pen (manufactured by Zebra Co., Ltd., trade name: Mackee) to draw a straight line of about 3cm in a single direction with a certain load, and evaluate the repellency of the oil-based ink at this time. The evaluation criteria are explained below.

G: The oily ink is pushed aside and a continuous straight line cannot be drawn.

NG: The oil-based ink has not been removed and a continuous straight line can be drawn.

(4) Antifouling property B (removability of oil-based ink)

On the surface treatment layer, use a black oil-based pen (manufactured by Zebra Co., Ltd., trade name: Mackee) to draw a straight line of about 3 cm in a single direction with a certain load. After leaving it for 10 minutes, it was wiped off three times with a cellulose nonwoven fabric to evaluate the removability. The evaluation criteria are explained below.

G: Oil-based ink is completely wiped off within 3 times

NG: Unable to completely remove oily ink

(5)Alcohol resistance

The surface treatment layer was wiped back and forth 5 times with a cellulose non-woven fabric fully dyed with ethanol (manufactured by Jujo Kimberly, trade name: KimWipe), and then wiped back and forth 5 times with another dried cellulose non-woven fabric. Then, on the surface treatment layer, use a black oil-based pen (manufactured by Zebra Co., Ltd., trade name: McKee) to draw a straight line of approximately 3 cm in one direction with a constant load, and perform (3) prevention in the same manner as above. Evaluation of antifouling property A and (4) antifouling property B.

G: Antifouling properties A and B are both the evaluation results of G

NG: Either one of antifouling properties A and B is NG.

(6)Wear resistance

Conduct durability evaluation by rubbing with cotton cloth. Specifically, the obtained article was arranged horizontally so that cotton cloth (manufactured by Asahi Kasei Co., Ltd., trade name: BEMCOT (registered trademark) M3-II) came into contact with the surface treatment layer. Then, while applying a load of 1 kg/ ^cm2 , the cotton cloth was slid back and forth at a speed of 60 times/min. Every 1,000 times, the static contact angle of water (contact angle with water) is measured.

The static contact angle of water was measured by the following method using a fully automatic contact angle meter DropMaster R700 (manufactured by Kyowa Interface Science Co., Ltd.). Add 2 μL of water dropwise from a microsyringe onto an object placed horizontally, and take a still image of the droplet for 1 second using a microscope camera. The water contact angle was measured at five different points, and the average value was set as the water contact angle of the article.

(7) Weather resistance

Implementation of accelerated weather resistance test using Super Xenon Weather Meter. Detailed conditions are described below. Measure the water contact angle of the sample after the accelerated weather resistance test.

Light source: xenon carbon arc lamp (illuminance 180W/m ² )

Illumination panel temperature: 63℃

Irradiation time: continuous irradiation

Wetting cycle (120 minutes/cycle): Wetting time (water spray at about 20°) 18 minutes, drying time 102 minutes

The irradiation is carried out continuously, except when the static contact angle of water is measured, the object is removed from the device. Wipe the surface treatment layer of the removed article back and forth 5 times with a cellulose non-woven fabric (manufactured by Jujo Kimberly Co., Ltd., trade name: KimWipe) that is fully dyed with pure water, and then use another fiber that is fully dyed with ethanol. After the plain non-woven fabric was wiped back and forth 5 times and dried, the water-resistant contact angle was measured. Figure 1 shows the relationship between cumulative exposure (total exposure) and water contact angle.

[Table 1]

． Target base material: rubber

[Example 5]

(1) Preparation of organic substrate

A nitrile rubber base material (thickness 5 mm, planar size 50 mm×100 mm) was washed with water and alcohol to obtain an organic base material.

(2) Preparation of primer

An appropriate amount of 3-aminopropyltrimethoxysilane (APTMS) was added to ethanol to obtain a primer with an APTMS concentration of 1.0% by mass.

(3) Preparation of surface treatment agent

The PFPE-containing silane compound (A) was dissolved in hydrofluoroether (Novec HFE7200, manufactured by 3M Company) so that the concentration became 0.1 wt%, thereby obtaining a surface treatment agent.

(4) Formation of primer layer

The primer is coated on the surface of the organic substrate by spin coating. Then, drying was performed at 120°C for 5 minutes to form a primer layer with a thickness of 5 nm.

(5) Formation of surface treatment layer

The surface treatment agent is applied by spin coating. Then, heat drying was performed at 120°C for 30 minutes in the air to form a surface treatment layer. In this way, an article having a rubber organic base material, a primer layer and a surface treatment layer is obtained.

[Comparative example 3]

Except that the primer layer was not formed, the other operations were carried out in the same manner as in Example 5 to obtain an article.

[Comparative example 4]

The untreated product in which the primer layer and the surface treatment layer were not formed was set as Comparative Example 4.

[Evaluation (base material: rubber)]

Make the following evaluation of the items obtained. The results are shown in Table 2.

(a) Appearance

Assess the appearance of the item visually. The evaluation criteria are explained below.

G: There is no processing unevenness of the coating film, but it is uniform.

NG: There is uneven processing, and the coating film is not uniformly formed.

(b)Alcohol resistance

Wipe back and forth 10 times with KimWipe containing ethanol, and evaluate the static contact angles of water and n-hexadecane before and after wiping. The smaller the change in static contact angle before and after erasure, the better the alcohol resistance. The static contact angle is measured by the same method as (6) abrasion resistance evaluation performed on the above-mentioned resin base material (the same is true below).

(c)Abrasion resistance

Conduct durability evaluation by rubbing with cotton cloth. Specifically, the obtained article was arranged horizontally so that cotton cloth (manufactured by Asahi Kasei Co., Ltd., trade name: BEMCOT (registered trademark) M3-II) came into contact with the surface treatment layer. Then, while applying a load of 1 kg/ ^cm2 , the cotton cloth was slid back and forth at a speed of 60 times/min. Measure the static contact angle of water (contact angle with water) after 50 times of back and forth.

(d) Weather resistance

Carry out the accelerated weather resistance test by the same method as (7) weather resistance evaluation for the above resin base material, and measure the exposure to water when the cumulative exposure dose (total exposure dose) is 300MJ/ ^m2 horn.

[Table 2]

It can be understood from the results in Table 1 and Figure 1 that the resin-made articles produced in Examples 1 to 4 were excellent in initial antifouling performance, and were also excellent in abrasion resistance and weather resistance.

From the results in Table 1 and Figure 1, it can be understood that the rubber articles produced in Examples 5 and 6 have excellent initial antifouling performance, and are also excellent in abrasion resistance and weather resistance.

[Industrial applicability]

The articles of the present disclosure are particularly suitable for outdoor use because of their excellent wear resistance and weather resistance.

This application claims priority based on Japanese Patent Application No. 2022-031218 filed in Japan on March 1, 2022, and all the contents described in it are incorporated into this specification by reference.

Claims (18)

An item that has: organic substrate; The primer layer is located on the aforementioned organic substrate and is formed of a primer. The primer contains a coupling agent, and the coupling agent has an organic reactive group and a hydrolyzable silicon group in one molecule; and A surface treatment layer, which is located directly above the aforementioned primer layer and is formed of a surface treatment agent, which includes a silane compound α containing a fluoropolyether group; Among them, the aforementioned silane compound α containing a fluoropolyether group is represented by the following formula ( α 1) or formula ( α 2),

In the formula, R ¹ is a univalent organic group containing a polyether chain, R ^1' is a divalent organic group containing a polyether chain, X ¹ are each independently a reactive cross-linking group containing silane, X ² are independently monovalent bases; The aforementioned polyether chains are independently represented by the following formula each time they appear, Formula: -(OC ₆ F ₁₂ ) _a -(OC ₅ F ₁₀ ) _b -(OC ₄ F ₈ ) _c -(OC ₃ X ¹⁰ ₆ ) _d -(OC ₂ F ₄ ) _e -(OCF ₂ ) _f - In the formula, a, b, c, d, e and f are each independently an integer of 0 or 1 or above, The sum of a, b, c, d, e and f is 1 or more, X ¹⁰ are independently H, F or Cl, The order of existence of each repeating unit marked with the subscript a, b, c, d, e or f and enclosed in parentheses is arbitrary in the formula. The article as described in claim 1, wherein the aforementioned polyether chain is independently represented by any one of the following formulas (f1) to formula (f6) each time it appears, -(OC ₃ F ₆ ) _d -(OC ₂ F ₄ ) _e - (f1) In the formula, d is an integer from 1 to 200, e is 0 or 1; -(OC ₄ F ₈ ) _c -(OC ₃ F ₆ ) _d -(OC ₂ F ₄ ) _e -(OCF ₂ ) _f - (f2) In the formula, c and d are each independently an integer from 0 to 30, e and f are each independently an integer from 1 to 200, The sum of c, d, e and f is 2 or more, The order of existence of each repeating unit marked with the subscript c, d, e or f and enclosed in parentheses is arbitrary in the formula; -(R ²¹ -R ²² ) _g - (f3) In the formula, R ²¹ is OCF ₂ or OC ₂ F ₄ , R ²² is a group selected from OC ₂ F ₄ , OC ₃ F ₆ , OC ₄ F ₈ , OC ₅ F ₁₀ and OC ₆ F ₁₂ , or 2 or 3 groups independently selected from these groups. combination, g is an integer from 2 to 100; -(R ²¹ -R ²² ) _g -R ^r -(R ^22' -R ^21' ) _g' - (f4) In the formula, R ²¹ is OCF ₂ or OC ₂ F ₄ , R ²² is a group selected from OC ₂ F ₄ , OC ₃ F ₆ , OC ₄ F ₈ , OC ₅ F ₁₀ and OC ₆ F ₁₂ , or 2 or 3 groups independently selected from these groups. combination, R ^21' is OCF ₂ or OC ₂ F ₄ , R ^22' is a group selected from OC ₂ F ₄ , OC ₃ F ₆ , OC ₄ F ₈ , OC ₅ F ₁₀ and OC ₆ F ₁₂ , or 2 or 3 groups independently selected from these groups. combination, g is an integer from 2 to 100, g' is an integer from 2 to 100, R ^r is the following formula:

In the formula, * represents the bonding position; -(OC ₆ F ₁₂ ) _a -(OC ₅ F ₁₀ ) _b -(OC ₄ F ₈ ) _c -(OC ₃ F ₆ ) _d -(OC ₂ F ₄ ) _e -(OCF ₂ ) _f - (f5) In the formula, e is an integer from 1 to 200, a, b, c, d and f are each independently an integer from 0 to 200, The order of existence of each repeating unit marked a, b, c, d, e or f and enclosed in parentheses is arbitrary in the formula; -(OC ₆ F ₁₂ ) _a -(OC ₅ F ₁₀ ) _b -(OC ₄ F ₈ ) _c -(OC ₃ F ₆ ) _d -(OC ₂ F ₄ ) _e -(OCF ₂ ) _f - (f6) In the formula, f is an integer from 1 to 200, a, b, c, d and e are each independently an integer from 0 to 200, The order of existence of each repeating unit marked a, b, c, d, e or f and enclosed in parentheses is arbitrary in the formula. The article as described in claim 1 or 2, wherein X ¹ is represented by the following formula, -L ¹ -{Si(R ^a ) _s (R ^b ) _t (R ^c ) _u (R ^d ) _v } _n In the formula, L ¹ is a single bond or a divalent linking group, R ^a , R ^b and R ^c are each independently halogen, an alkoxy group having 1 to 10 carbon atoms, an amine group having 1 to 10 carbon atoms, an acetyloxy group having 1 to 10 carbon atoms, or an acetyloxy group having 3 to 10 carbon atoms. Allyl, or glycidyl with 3 to 10 carbon atoms, R ^d are independently -O-, -NH-, -C≡C- or silane bond, s, t and u are independently 0 or 1, v is an integer from 0 to 3, n is an integer from 1 to 20; When n is 1, s+t+u is 3 and v is 0; When n is 2 to 20, s+t+u are 0 to 2 independently, and v is 0 to 2 independently; When v is an integer of 1 or more, at least two Si are bonded via R ^d in a straight chain, ladder type, cyclic or polycyclic form. The article according to any one of claims 1 to 3, wherein the surface treatment agent further contains: the aforementioned fluoropolyether group-containing silane compound α represented by the aforementioned formula ( α1 ) and the aforementioned formula ( α2 ) Silane compounds containing fluoropolyether groups other than β . The article according to any one of claims 1 to 4, wherein the number average molecular weight of the silane compound α containing a fluoropolyether group is 500 or more and 10,000 or less. The article according to any one of claims 1 to 5, wherein the organic reactive group of the coupling agent contains an amine group, a glycidyl group, an epoxy group, a vinyl group, a methacrylyl group, At least one kind from the group consisting of acryl group, styrene group, phenyl group, isocyanate group and mercapto group. The article according to any one of claims 1 to 6, wherein the hydrolyzable silicon group of the coupling agent has two or more alkoxy groups having 1 to 5 carbon atoms. The article according to any one of claims 1 to 7, wherein the hydrolyzable silicon group of the coupling agent contains at least one of a trimethoxysilyl group and a triethoxysilyl group. The article according to any one of claims 1 to 8, wherein the aforementioned surface treatment agent further contains a cross-linking compound, The cross-linked compound contains at least one of a compound represented by the following formula (Q1) and a compound represented by the following formula (Q2), A[Z ^q1 -M ^q (OR ^q1 ) _wn1 (R ^q2 ) _wn2-wn1 ] _wa1 [Z ^q2 -R ^q3 ] _wa2 (Q1) In the formula, A is an organic radical with 1 to 10 valence, Z ^q1 are independently single bonds or divalent organic groups, M ^q is Al, Ca, Fe, Ge, Hf, In, Si, Ta, Ti, Sn, Zr or Zn; R ^q1 are each independently a hydrogen atom or a C _1-6 alkyl group, R ^q2 are each independently a hydrogen atom or a hydrocarbon group, wn1 is independently 1 or more and (valence of M ^q -1) or less, wn2 are independently (valence of M ^q -1), Z ^q2 are independently single bonds or divalent organic groups, R ^q3 are independently reactive groups, wa1 is an integer from 1 to 10, wa2 is an integer from 0 to 10, The sum of wa1 and wa2 is the valence of A;

In the formula, M is Al, Ca, Fe, Ge, Hf, In, Si, Ta, Ti, Sn, Zr or Zn, R ^q are each independently a hydrogen atom, C _1-6 alkyl group or R ^q1 -CO-, R ^q1 is a univalent hydrocarbon group, R ^q' are independently C _1-3 alkyl or C _1-3 alkoxy, mq is the valence of the aforementioned M, nq is 0 or more and less than the valence of M mentioned above. The item described in claim 9, wherein wn1 is 2 or more. The article according to claim 9 or 10, wherein the aforementioned R ^q1 groups are each independently a C _1-6 alkyl group. The article according to any one of claims 9 to 11, wherein A is an alkylene group. The article according to any one of claims 9 to 11, wherein A is a base represented by the following formula,

In the formula, X ^a is each independently a single bond or a divalent organic group. The article according to any one of claims 9 to 13, wherein the aforementioned R ^q3 groups are each independently an isocyanate group, an epoxy group or a vinyl group. The article according to any one of claims 1 to 14, wherein the primer further contains at least one of an ultraviolet absorber and a radical scavenger. The article according to any one of claims 1 to 15, wherein the surface treatment agent further contains at least one of an ultraviolet absorber and a radical scavenger. A method of manufacturing an article, including: Use a primer to form a primer layer on an organic substrate, where the primer contains a coupling agent that has an organic reactive group and a hydrolyzable silicone group in one molecule; and Use a surface treatment agent to form a surface treatment layer directly above the above-mentioned primer layer. Here, the surface treatment agent includes a silane compound α containing a fluoropolyether group; Among them, the aforementioned silane compound α containing a fluoropolyether group is represented by the following formula ( α 1) or formula ( α 2),

In the formula, R ¹ is a univalent organic group containing a polyether chain, R ^1' is a divalent organic group containing a polyether chain, X ¹ are each independently a reactive cross-linking group containing silane, X ² are independently monovalent bases; The aforementioned polyether chains are independently represented by the following formula each time they appear, Formula: -(OC ₆ F ₁₂ ) _a -(OC ₅ F ₁₀ ) _b -(OC ₄ F ₈ ) _c -(OC ₃ X ¹⁰ ₆ ) _d -(OC ₂ F ₄ ) _e -(OCF ₂ ) _f - In the formula, a, b, c, d, e and f are each independently an integer of 0 or 1 or above, The sum of a, b, c, d, e and f is 1 or more, X ¹⁰ are independently H, F or Cl, The order of existence of each repeating unit marked with the subscript a, b, c, d, e or f and enclosed in parentheses is arbitrary in the formula. A surface treatment agent used to manufacture the article described in any one of claims 1 to 16.