JPWO2020148799A1 - Silicone oligomer and coating composition containing it - Google Patents

Abstract

The silicone oligomer represented by the average formula (1) provides a coating film having excellent hardness while maintaining water repellency and oil repellency even when the uncured film is wiped off. [P, q, t, d, m, r are 0 <p ≦ 0.3, 0 ≦ q ≦ 0.5, 0.3 ≦ t <1, 0 ≦ d ≦ 0.5, 0 ≦ m ≦ 0.5, p + q + t + d + m = 1, 0.2 × (3p + 4q + 3t + 2d + m) ≦ r ≦ 0.7 × (3p + 4q + 3t + 2d + m), and R1 to R7 are independent of each other and have 1 to 18 hydrogen atoms or carbon atoms. A monovalent hydrocarbon group, Rf is a divalent poly (perfluoroalkylene ether) group having a number average molecular weight of 500 to 5,000, X is a divalent hydrocarbon group independently of each other, and Q is an independent of each other. Represents an oxygen atom or a linking group of formula (2). (Z represents a divalent hydrocarbon group, and an asterisk (*) represents a binding site with Rf.)]

Description

The present invention relates to a silicone oligomer and a coating composition containing the same, and more particularly to a silicone oligomer linked by a poly (perfluoroalkylene ether) chain and a coating composition containing the same.

Conventionally, a coating agent composition containing a poly (perfluoroalkylene ether) compound has been applied and applied to building materials, painted steel sheets, etc. for the purpose of preventing scratches, imparting water and oil repellency, and improving aesthetics. It is done.

For example, in Patent Document 1, by adding a poly (perfluoroalkylene ether) compound to a silicone composition containing an alkoxy group, a coating film having excellent water repellency, oil repellency, and film hardness can be obtained. It has been disclosed.
Further, Patent Document 2 discloses that water repellency and oil repellency can be imparted to the glass surface by surface-treating the glass with a coating composition obtained by diluting a poly (perfluoroalkylene ether) compound with a fluorine-based solvent. ..

When coating is applied to an automobile body using these coating compositions, it is common to apply a coating agent and then wipe the coating with a cloth to thin the film.
However, when a composition in which a poly (perfluoroalkylene ether) compound is added to silicone is applied as in the technique of Patent Document 1, the poly (perfluoroalkylene ether) compound is formed in the vicinity of the surface of the uncured coating film. It has been clarified by the present inventors that the poly (perfluoroalkylene ether) compound is shed off by wiping because the compounds are unevenly distributed, and the performance such as water repellency and antifouling property of the coating layer is significantly deteriorated. ing.
Further, when the amount of the poly (perfluoroalkylene ether) compound in the composition is increased so that the poly (perfluoroalkylene ether) compound remains in the film even if it is removed to some extent, the poly (perfluoroalkylene ether) compound is precipitated or Since the dissolution is slow, there is a problem that the productivity of the coating composition is significantly reduced.
On the other hand, when a composition obtained by diluting a poly (perfluoroalkylene ether) compound with a fluorine-based solvent is applied as in the technique of Patent Document 2, a film of the poly (perfluoroalkylene ether) compound is formed on the surface of the substrate. However, the film is composed of only a poly (perfluoroalkylene ether) compound, and there is a problem that the hardness of the film is insufficient.

Japanese Patent No. 57512111 Japanese Patent No. 5846466

The present invention has been made in view of the above circumstances, and is a silicone oligomer that provides a coating film having excellent hardness while maintaining water repellency and oil repellency even when a wiping operation is performed on an uncured film. The purpose is to provide.

As a result of diligent studies to achieve the above object, the present inventors have obtained a composition containing a silicone oligomer linked by a poly (perfluoroalkylene ether) chain to give a coating film having excellent hardness, and after wiping. The present invention was completed by finding that water repellency and oil repellency can be maintained.

［式中、ｐ、ｑ、ｔ、ｄ、ｍおよびｒは、０＜ｐ≦０．３、０≦ｑ≦０．５、０．３≦ｔ＜１、０≦ｄ≦０．５、０≦ｍ≦０．５、かつ、ｐ＋ｑ＋ｔ＋ｄ＋ｍ＝１、０．２×（３ｐ＋４ｑ＋３ｔ＋２ｄ＋ｍ）≦ｒ≦０．７×（３ｐ＋４ｑ＋３ｔ＋２ｄ＋ｍ）を満たす数を表し、
Ｒ¹〜Ｒ⁷は、互いに独立して、水素原子、または置換もしくは非置換の炭素原子数１〜１８の１価炭化水素基を表し、Ｒｆは、数平均分子量５００〜５，０００の２価のポリ（パーフルオロアルキレンエーテル）基を表し、Ｘは、互いに独立して２価の炭化水素基を表し、Ｑは、互いに独立して、酸素原子または下記式（２）で表される連結基を表す。

（式中、Ｚは、２価の炭化水素基を表し、アスタリスク（＊）は、前記Ｒｆとの結合部位を表す。）］
２． 前記ｐ、ｑ、ｔ、ｄ、ｍおよびｒが、０＜ｐ≦０．３、ｑ＝０、０．７≦ｔ＜１、ｄ＝０、ｍ＝０、かつ、０．２×（３ｐ＋３ｔ）≦ｒ≦０．７×（３ｐ＋３ｔ）を満たす数を表し、前記Ｘが、炭素原子数１〜１０のアルキレン基を表し、前記Ｚが、炭素原子数１〜６のアルキレン基を表す１のシリコーンオリゴマー、
３． 前記Ｒｆが、数平均分子量１，０００〜３，０００のポリ（パーフルオロアルキレンエーテル）基を表し、当該ポリ（パーフルオロアルキレンエーテル）基におけるパーフルオロアルキレン部位が、パーフルオロメチレンおよびパーフルオロエチレンから構成され、パーフルオロメチレンの数（ａ）とパーフルオロエチレンの数（ｂ）との比（ａ／ｂ）が、１／１０〜１０／１である１または２のシリコーンオリゴマー、
４． １〜３のいずれかのシリコーンオリゴマー１００質量部に対し、加水分解縮合触媒０．０１〜３０質量部を含む組成物、
５． さらに、アルコキシシラン、アルコキシシランの加水分解縮合物および溶剤から選ばれる少なくとも１種を、前記シリコーンオリゴマー１００質量部に対して３００質量部以下の量で含む４の組成物、
６． １〜３のいずれかのシリコーンオリゴマーが加水分解縮合してなる硬化物、
７． ４または５の組成物から得られる硬化物、
８． ４または５の組成物から得られるコーティング膜、
９． ８のコーティング膜を有する物品
を提供する。That is, the present invention
1. 1. A silicone oligomer represented by the following average formula (1),

[In the formula, p, q, t, d, m and r are 0 <p ≦ 0.3, 0 ≦ q ≦ 0.5, 0.3 ≦ t <1, 0 ≦ d ≦ 0.5, 0. Represents a number that satisfies ≦ m ≦ 0.5 and p + q + t + d + m = 1, 0.2 × (3p + 4q + 3t + 2d + m) ≦ r ≦ 0.7 × (3p + 4q + 3t + 2d + m).
R ^{1 to} R ⁷ represent hydrogen atoms or substituted or unsubstituted monovalent hydrocarbon groups having 1 to 18 carbon atoms independently of each other, and Rf is a divalent group having a number average molecular weight of 500 to 5,000. Represents the poly (perfluoroalkylene ether) group of, X represents a divalent hydrocarbon group independently of each other, and Q represents an oxygen atom or a linking group represented by the following formula (2) independently of each other. Represents.

(In the formula, Z represents a divalent hydrocarbon group, and an asterisk (*) represents a binding site with Rf.)]
2. 2. The p, q, t, d, m and r are 0 <p ≦ 0.3, q = 0, 0.7 ≦ t <1, d = 0, m = 0, and 0.2 × (3p + 3t). ) ≤ r ≤ 0.7 × (3p + 3t), where X represents an alkylene group having 1 to 10 carbon atoms and Z represents an alkylene group having 1 to 6 carbon atoms. Silicone oligomer,
3. 3. The Rf represents a poly (perfluoroalkylene ether) group having a number average molecular weight of 1,000 to 3,000, and the perfluoroalkylene moiety in the poly (perfluoroalkylene ether) group is derived from perfluoromethylene and perfluoroethylene. A silicone oligomer of 1 or 2 configured, wherein the ratio (a / b) of the number of perfluoromethylene (a) to the number of perfluoroethylene (b) is 1/10 to 10/1.
4. A composition containing 0.01 to 30 parts by mass of a hydrolysis condensation catalyst with respect to 100 parts by mass of any of 1 to 3 silicone oligomers.
5. Further, the composition of 4 containing at least one selected from alkoxysilane, a hydrolyzed condensate of alkoxysilane, and a solvent in an amount of 300 parts by mass or less with respect to 100 parts by mass of the silicone oligomer.
6. A cured product obtained by hydrolyzing and condensing any of the silicone oligomers 1 to 3.
7. A cured product obtained from the composition of 4 or 5,
8. A coating film obtained from the composition of 4 or 5,
9. An article having the coating film of 8 is provided.

In the cured film obtained by using the silicone oligomer of the present invention, the poly (perfluoroalkylene ether) chain is uniformly incorporated in the film, so that the coating layer is formed by wiping the uncured coating film with a cloth at the time of construction. Even if the film is thinned, a coating layer having a surface having excellent water repellency, oil repellency, and stain resistance can be imparted.
Further, since the silicone oligomer of the present invention contains silicone in its structure, its coating film is excellent in hardness.
The composition containing the silicone oligomer of the present invention is for forming a thin film coating layer that imparts water repellency, oil repellency, durability, and antifouling property to a metal surface, a painted surface, a resin surface, or the like of an automobile body or a train vehicle. It can be suitably used as a coating agent, and can also be suitably used for coating a vehicle body other than an automobile or a train, a building material, a molded body, or the like.

Hereinafter, the present invention will be specifically described.
The silicone oligomer according to the present invention is a silicone oligomer linked by a poly (perfluoroalkylene ether) chain as represented by the following average formula (1).

In the above formula (1), p, q, t, d, m and r are 0 <p ≦ 0.3, 0 ≦ q ≦ 0.5, 0.3 ≦ t <1, 0 ≦ d ≦ 0. 5. Represents a number satisfying 0 ≦ m ≦ 0.5 and p + q + t + d + m = 1, 0.2 × (3p + 4q + 3t + 2d + m) ≦ r ≦ 0.7 × (3p + 4q + 3t + 2d + m).
p is 0 <p ≦ 0.3, but is preferably in the range of 0 <p ≦ 0.1. When p exceeds 0.3, the silicone oligomer becomes cloudy.
q is 0 ≦ q ≦ 0.5, but is preferably in the range of 0 ≦ q ≦ 0.2. When q exceeds 0.5, gelation is likely to occur during polymerization.
t is 0.3 ≦ t <1, but is preferably in the range of 0.5 ≦ t <1. When t is less than 0.3, the crosslink density is lowered and the strength of the coating film is lowered.
d is 0 ≦ d ≦ 0.5, but is preferably in the range of 0 ≦ d ≦ 0.2. When d exceeds 0.5, the crosslink density decreases and the strength of the coating film decreases.
m is 0 ≦ m ≦ 0.5, but is preferably in the range of 0 ≦ m ≦ 0.2. When m exceeds 0.5, the oligomer has a low molecular weight and the strength of the coating film decreases.
r is a number satisfying 0.2 × (3p + 4q + 3t + 2d + m) ≦ r ≦ 0.7 × (3p + 4q + 3t + 2d + m), but preferably 0.2 × (3p + 4q + 3t + 2d + m) ≦ r ≦ 0.6 × (3p + 4q + 3t + 2d + m), more preferably 0. .2 × (3p + 4q + 3t + 2d + m) ≦ r ≦ 0.5 × (3p + 4q + 3t + 2d + m). When r <0.2 × (3p + 4q + 3t + 2d + m), it becomes a highly viscous body and difficult to handle, and when 0.7 × (3p + 4q + 3t + 2d + m) <r, many alkoxy groups remain and cracks due to condensation curing are likely to occur. Become.

In the above formula (1), R ^{1 to} R ⁷ represent a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 18 carbon atoms independently of each other.
The monovalent hydrocarbon group may be linear, branched or cyclic, and specific examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group and a tert-butyl. Linear, branched or cyclic alkyl groups such as groups, n-hexyl groups, cyclohexyl groups, n-octyl groups, 2-ethylhexyl groups, n-decyl groups; vinyl groups, allyl (2-propenyl) groups, 1-propenyl. Examples thereof include an alkenyl group such as a group, an isopropenyl group and a butenyl group; an aryl group such as a phenyl, tolyl, xylyl and naphthyl group; and an aralkyl group such as a benzyl, phenylethyl and phenylpropyl group.

Further, the monovalent hydrocarbon group may have a part or all of its hydrogen atom substituted with another substituent, and specific examples of the other substituent include halogen atoms such as fluorine, chlorine and bromine. ; Reactive groups such as glycidoxy group, acryloyl group, methacryloyl group, acryloyloxy group, metaacryloyloxy group, amino group, mercapto group, hydroxy group and the like can be mentioned.

Among these, R ^{1 to} R ⁷ are preferably a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, and an aryl group having 6 to 12 carbon atoms, and more preferably a hydrogen atom and an alkyl group having 1 to 8 carbon atoms. Preferably, a hydrogen atom, a methyl group and an ethyl group are even more preferable.

In the above formula (1), X represents a divalent hydrocarbon group independently of each other, and Q represents an oxygen atom or a linking group represented by the following formula (2) independently of each other.

（式中、Ｚは、２価の炭化水素基を表し、アスタリスク（＊）は、Ｒｆとの結合部位を表す。）

(In the formula, Z represents a divalent hydrocarbon group, and an asterisk (*) represents a binding site with Rf.)

Examples of the divalent hydrocarbon group of X in the above formula (1) and Z in the above formula (2) include an alkylene group having 1 to 22 carbon atoms and an arylene group having 6 to 22 carbon atoms. Can be mentioned.
The alkylene group may be linear, branched or cyclic, and specific examples thereof include a methylene group, an ethylene group, a trimethylene group, a propylene group, a butylene group, an isobutylene group, a sec-butylene group and a tert-butylene group. 2,2-Dimethylpropylene group, 2-methylbutylene group, 2-methyl-2-butylene group, 3-methylbutylene group, 3-methyl-2-butylene group, pentylene group, 2-pentylene group, 3-pentylene group , 3-Dimethyl-2-butylene group, 3,3-dimethylbutylene group, 3,3-dimethyl-2-butylene group, 2-ethylbutylene group, hexylene group, 2-hexylene group, 3-hexylene group, 1, 2-Cyclohexylene group, 1,3-Cyclohexylene group, 1,4-Cyclohexylene group, 2-Methylpentylene group, 2-Methyl-2-pentylene group, 2-Methyl-3-pentylene group, 3-Methylpentylene group, 3-Methyl-2-pentylene group, 3-Methyl-3-pentylene group, 4-Methylpentylene group, 4-Methyl-2-pentylene group, 2,2-dimethyl-3-pentylene Group, 2,3-dimethyl-3-pentylene group, 2,4-dimethyl-3-pentylene group, 4,4-dimethyl-2-pentylene group, 3-ethyl-3-pentylene group, heptylene group, 2-heptylene Group, 3-heptylene group, 2-methyl-2-hexylene group, 2-methyl-3-hexylene group, 5-methylhexylene group, 5-methyl-2-hexylene group, 2-ethylhexylene group, 6- Methyl-2-heptylene group, 4-methyl-3-heptylene group, octylene group, 2-octylene group, 3-octylene group, 2-propylpentylene group, 2,4,4-trimethylpentylene group, decaoctylene group, etc. Examples of the arylene group include a 1,2-phenylene group, a 1,3-phenylene group, a 1,4-phenylene group and the like.

Among these, as X, an alkylene group having 1 to 10 carbon atoms is preferable, an alkylene group having 1 to 6 carbon atoms is more preferable, and an alkylene group having 1 to 3 carbon atoms is preferable because it is easy to synthesize. Even more preferred, a trimethylene group is particularly preferred.
Further, as the Z, an alkylene group having 1 to 6 carbon atoms is preferable, and an alkylene group having 1 to 6 carbon atoms is preferable, which provides a coating composition having a high fluorine atom content and a film having more excellent antifouling property. The alkylene group is more preferable, the methylene group is more preferable in that it has excellent antifouling property and is easily obtained industrially.

Therefore, a suitable silicone oligomer in the present invention is represented by the following average formula (3).

［式中、ｐ、ｔおよびｒは、０＜ｐ≦０．３、０．７≦ｔ＜１、ｐ＋ｔ＝１、０．２×（３ｐ＋３ｔ）≦ｒ≦０．７×（３ｐ＋３ｔ）を満たす数を表し、Ｒ¹およびＲ⁷は、互いに独立して、水素原子、または置換もしくは非置換の炭素原子数１〜１８の１価炭化水素基を表し、Ｒｆは、数平均分子量５００〜５，０００の２価のポリ（パーフルオロアルキレンエーテル）基を表し、Ｘは、互いに独立して炭素原子数１〜１０の２価の炭化水素基を表し、Ｑは、互いに独立して、酸素原子または下記式（２）で表される連結基を表す。

[In the formula, p, t and r satisfy 0 <p ≦ 0.3, 0.7 ≦ t <1, p + t = 1, 0.2 × (3p + 3t) ≦ r ≦ 0.7 × (3p + 3t). Representing a number, R ¹ and R ⁷ represent hydrogen atoms or substituted or unsubstituted monovalent hydrocarbon groups having 1 to 18 carbon atoms independently of each other, and Rf represents a number average molecular weight of 500 to 5, Represents 000 divalent poly (perfluoroalkylene ether) groups, X represents a divalent hydrocarbon group having 1 to 10 carbon atoms independently of each other, and Q represents an oxygen atom or an oxygen atom independently of each other. It represents a linking group represented by the following formula (2).

（式中、Ｚは、炭素原子数１〜６の２価の炭化水素基を表し、アスタリスク（＊）は、Ｒｆとの結合部位を表す。）］

(In the formula, Z represents a divalent hydrocarbon group having 1 to 6 carbon atoms, and an asterisk (*) represents a binding site with Rf.)]

As the poly (perfluoroalkylene ether) group in Rf of the above formulas (1) and (3), for example, one having a structure in which perfluoroalkylene groups having 1 to 3 carbon atoms and oxygen atoms are alternately linked is preferable. ..
In this case, the perfluoroalkylene group having 1 to 3 carbon atoms in the poly (perfluoroalkylene ether) group may be one kind or a mixture of a plurality of kinds, and is specifically represented by the following structural formula (4). There are things.

In the formula (4), A represents a perfluoroalkylene group having 1 to 3 carbon atoms, all of which may have the same structure, or a plurality of structures may be present in a random or block form.
In addition, n is preferably 6 to 60 in total, more preferably 10 to 35, and even more preferably 12 to 25.
Specific examples of the above A include the structure shown below.

Among these, the poly (perfluoroalkylene ether) chain has a perfluoromethylene group because it has many oxygen atoms that serve as bending points that exhibit slipperiness and has no branched structure that inhibits the bending movement of the chain. And the perfluoroethylene group is preferable, and the structure represented by the general formula (5) in which the perfluoromethylene group and the perfluoroethylene group coexist is particularly preferable in consideration of the fact that it is easily obtained industrially.

In the above general formula (5), the ratio (a / b) of the number of perfluoromethylene groups (a) to the number of perfluoroethylene groups (b) is not particularly limited, but is 1/10 to 10 1/1 is preferable, 3/10 to 10/3 is more preferable, and 3.5 / 10 to 10 / 3.5 is even more preferable.

The number average molecular weight of the poly (perfluoroalkylene ether) group is 500 to 5,000, preferably 1,000 to 3,000, more preferably 1,200 to 1,800 from the viewpoint of compatibility. preferable. If the number average molecular weight of the poly (perfluoroalkylene ether) chain is less than 500, the water repellency is inferior, and if it exceeds 5,000, the compatibility with silicone deteriorates and the silicone oligomer becomes cloudy.

The average molecular weight of the silicone oligomer of the present invention is not particularly limited, but the polystyrene-equivalent weight average molecular weight by gel permeation chromatography (GPC) is preferably 2,000 to 40,000, preferably 5,000 to 20,000. Is more preferable. If the weight average molecular weight is less than 2,000, the condensation does not proceed sufficiently, and the storage stability of the organopolysiloxane compound may be lowered. If the molecular weight is more than 40,000, the workability at the time of coating is deteriorated. there's a possibility that.

The viscosity of the silicone oligomer of the present invention is not particularly limited, but from the viewpoint of workability and workability, the kinematic viscosity at 25 ° C. measured by a Canon Fenceke type viscometer is 1 to 1,000 mm ² / s. Is preferable, and 10 to 300 mm ² / s is more preferable.

The silicone oligomer linked by the poly (perfluoroalkylene ether) chain of the present invention includes, for example, at least a silane compound represented by the following general formula (6) and a trialkoxysilane represented by the following general formula (7). Can be co-hydrolyzed and condensed in the presence of a hydrolysis catalyst such as Bronsted acid or Lewis acid.
Further, if necessary, other alkoxysilane compounds other than the silane compound of the formula (6) and the trialkoxysilane of the formula (7) may be added, and in this case, the trialkoxysilane compound represented by the following general formula (7) may be added. The amount of alkoxysilane is 30 mol% or more and less than 100 mol% with respect to the total amount of alkoxysilane compounds.

（式中、Ｒ⁷、Ｒｆ、ＱおよびＸは、上記と同じ意味を表す。）

(In the formula, R ⁷ , Rf, Q and X have the same meanings as above.)

（式中、Ｒ¹およびＲ⁷は、上記と同じ意味を表す。）

(In the formula, R ¹ and R ⁷ have the same meanings as above.)

Specific examples of the silane compound represented by the above formula (6) include, but are not limited to, the compounds shown below.

（式中、Ｒｆは上記と同じ意味を表し、Ｍｅはメチル基を、Ｅｔはエチル基を意味する。）

(In the formula, Rf has the same meaning as above, Me means a methyl group, and Et means an ethyl group.)

On the other hand, the trialkylsilane represented by the above general formula (7) is not particularly limited, and for example, trimethoxysilane, triethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, and the like. Methyltributoxysilane, methyltriisopropenoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, butyltrimethoxysilane, hexyltrimethoxysilane, decyltrimethoxysilane, phenyltrimethoxysilane, cyclohexyltrimethoxysilane, vinyltrimethoxy Silane, vinyl triethoxysilane, 5-hexenyltrimethoxysilane, 4-vinylphenyltrimethoxysilane, 3- (4-vinylphenyl) propyltrimethoxysilane, 4-vinylphenylmethyltrimethoxysilane, 3-glycidoxypropyl Trimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxipropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyl Examples thereof include triethoxysilane, 3- (2-aminoethyl) aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, and these include two types even when used alone. These combinations may be used, or these hydrolysis condensates may be used.

Further, the silane compound represented by the general formula (6) and other alkoxysilanes other than the trialkoxysilane represented by the general formula (7) have one or more hydrolyzable groups and satisfy the above conditions. Any silane compound having a substituted or unsubstituted monovalent hydrocarbon group can be used, for example, trimethylmethoxysilane, trimethylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, hexamethyldisiloxane, tetramethyldisiloxane. , Didimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldiisopropoxysilane, dimethyldibutoxysilane, dimethyldiisopropenoxysilane, propylmethyldimethoxysilane, hexylmethyldimethoxysilane, phenylmethyldimethoxysilane, diphenyldimethoxysilane, tetramethoxysilane , Tetraethoxysilane and the like.
In addition, vinylmethyldimethoxysilane, vinylmethyldiethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3- (meth) acryloxypropylmethyldimethoxysilane, 3- (meth). ) Has reactive functional groups such as acryloxypropylmethyldiethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropylmethyldiethoxysilane Silane compounds can also be used.
These alkoxysilane compounds may be used alone, in combination of two or more, or further hydrolyzed condensates thereof.

Among these, as the other alkoxysilane compound, methoxysilane and ethoxysilane are preferable because of the ease of volatilization of by-products, methoxysilane is more preferable because of its high reactivity, and methyltrimethoxysilane is even more preferable. preferable.

As the hydrolysis catalyst used when carrying out hydrolysis, a conventionally known catalyst can be used, for example, an acid such as hydrochloric acid, nitrate, sulfuric acid, hydrogen halide, carboxylic acid, sulfonic acid, acidity or weak acidity. Inorganic salts, solid acids such as ion exchange resins, inorganic bases such as ammonia and sodium hydroxide, tributylamine, 1,5-diazabicyclo [4.3.0] nonen-5 (DBN), 1,8-diazabicyclo [5.4.0] Examples thereof include organic basics such as Undecene-7 (DBU), organic tin compounds, organic titanium compounds, organic zirconium compounds, organic metal compounds such as organic aluminum compounds, and these are used alone. May be used in combination with multiple types.

In the present invention, an acid and an organic metal compound selected from an organic tin compound, an organic titanium compound and an organic aluminum-based compound are particularly preferable, and specifically, an acid such as methanesulfonic acid, hydrochloric acid, nitrate and sulfuric acid; dibutyltin. Dilaurate, Dibutyltin Dioctate, Dibutyltin Diacetate, Dioctyltin Dilaurate, Dioctyltin Dioctate, Dioctyltin Diacetate, Dibutyltin Bisacetylacetate, Dioctyltin Bisacetyllaurate, Tetrabutyltitanate, Tetranonyltitanate, Tetrakissethylene Glycolmethyl Ether Titanate, Tetraxethylene Glycolethyl Ether Titanate, Bis (Acetylacetonyl) Dipropyl Titanate, Acetylacetone Aluminum, Aluminum Bis (Ethylacet Acetate) Mononormal Butyrate, Aluminum Ethylacetate Acetate Dinormalal Butyrate, Aluminum Tris (Ethylacet Acetate) Examples thereof include organic metal compounds such as and hydrolysates thereof, and from the viewpoint of reactivity, acids such as methanesulfonic acid, hydrochloric acid and nitrate; tetrabutyl titanate, aluminum ethylacetate acetate dinormal butyrate, aluminum bis (ethyl). Acetacetate) mononormal butyrate and their hydrolyzates are preferred, with methanesulfonic acid being more preferred.
The amount of the hydrolyzable catalyst is not particularly limited, but is preferably in the range of 0.001 to 10 mol% with respect to 1 mol of the hydrolyzable group on the silicon atom, preferably 0.001 to 5 mol%. Especially preferable.

The co-hydrolysis / condensation reaction may be carried out in the presence of an organic solvent.
The organic solvent is not particularly limited as long as it dissolves each of the above compounds as a raw material, and specific examples thereof include aromatic hydrocarbons such as toluene and xylene; hydrocarbons such as hexane and octane; and methyl ethyl ketone. , Ketones such as methyl isobutyl ketone; esters such as ethyl acetate and isobutyl acetate; alcohols such as methanol, ethanol, isopropanol, butanol, isobutanol, t-butanol, fluorine-based solvents and the like.
Examples of the fluorine-based solvent include fluorine-containing aromatic hydrocarbons such as 1,3-bis (trifluoromethyl) benzene and trifluorotoluene; and perfluorohexane, perfluoromethylcyclohexane and the like having 3 to 12 carbon atoms. Perfluorocarbons; 1,1,2,2,3,3,4-heptafluorocyclopentane, 1,1,1,2,2,3,3,4,5,5,6-tri Hydrofluorocarbons such as decafluorooctane; Hydrofluorocarbons such as C ₃ F ₇ OCH ₃ , C ₄ F ₉ OCH ₃ , C ₄ F ₉ OC ₂ H ₅ , C ₂ F ₅ CF (OCH ₃ ) C ₃ F ₇ Classes: Poly (perfluoroalkylene ethers) such as von Bryn, Galden (manufactured by Solbay), Demnum (manufactured by Daikin Industries, Ltd.), and Crytox (manufactured by Chemers).

Here, by reducing the amount of water added during hydrolysis to less than the amount required to hydrolyze all of the alkoxy groups of the raw material, a silicone oligomer containing a large amount of alkoxy groups can be obtained, while water. By increasing the addition amount of the above-mentioned required amount to be larger than the above-mentioned required amount, a silicone oligomer containing a large amount of silanol can be obtained.
Further, since the silicone oligomer linked by the poly (perfluoroalkylene ether) chain of the present invention has a hydrolyzable silyl group and silanol, further hydrolysis condensation is allowed to proceed, and the poly (perfluoroalkylene ether) is obtained. It can be a chained silicone resin.

Since the above-mentioned silicone oligomer of the present invention can be cured by an appropriate hydrolysis-condensation catalyst, it can be suitably used as a composition with a hydrolysis-condensation catalyst.
This hydrolysis-condensation catalyst is a compound for reacting an alkoxysilyl group (Si-OR) contained in a silicone oligomer or a diluent described later with moisture in the air or moisture on a substrate to cause a hydrolysis-condensation reaction. Is.

The hydrolysis condensation catalyst can be appropriately selected from known catalysts and used, for example, organic metal compounds such as organic tin compounds, organic titanium compounds, organic zirconium compounds and organic aluminum compounds; inorganic acids such as hydrochloric acid and sulfuric acid. Organic acids such as p-toluenesulfonic acid, various aliphatic or aromatic carboxylic acids; Ammonia; Inorganic bases such as sodium hydroxide, tributylamine, 1,5-diazabicyclo [4.3.0] Nonen-5 ( Examples thereof include organic bases such as DBN) and 1,8-diazabicyclo [5.4.0] undecene-7 (DBU), which may be used alone or in combination of two or more.
In the composition of the present invention, among these, an organic metal compound selected from an organic tin compound, an organic titanium compound and an organic aluminum compound is preferable, and specifically, dibutyltin dilaurate, dibutyltin dioctate, dibutyltin diacetate and dioctyl are preferable. Tin dilaurate, dioctyl tin dioctate, dioctyl tin diacetate, dibutyl tin bisacetyl acetate, dioctyl tin bisacetyl laurate, tetrabutyl titanate, tetranonyl titanate, tetraxethylene glycol methyl ether titanate, tetraxethylene glycol ethyl ether titanate, bis (acetyl) Acetnyl) dipropyl titanate, acetylacetone aluminum, aluminum bis (ethylacetate acetate) mononormal butyrate, aluminum ethylacetacetate dinormalal butyrate, aluminum tris (ethylacetacetate) and the like are suitable, and are particularly reactive and soluble. From the viewpoint of sex, tetrabutyl titanate, aluminum ethyl acetoacetate dinormal butyrate, aluminum bis (ethyl acetoacetate) mononormal butyrate and their hydrolyzates are preferable.

The blending amount of the hydrolysis condensation catalyst is preferably 0.01 to 30 parts by mass, more preferably 0.5 to 10 parts by mass with respect to 100 parts by mass of the silicone oligomer.
The curing temperature of the composition is not particularly limited, but is preferably 10 ° C to 150 ° C, more preferably 15 ° C to 50 ° C. In addition, it is preferable to carry out under humidification in order to promote the reaction.

In addition to the hydrolysis condensation catalyst, the composition of the present invention may further contain one or more diluents selected from alkoxysilanes, alkoxysilane oligomers and diluent solvents. By adding these diluents, the viscosity, curing time, and hardness of the cured film can be adjusted. Therefore, the composition diluted with such a diluent can be suitably used as a coating agent. ..

The alkoxysilane and the alkoxysilane oligomer to be added for dilution are not particularly limited as long as they have one or more hydrolyzable groups, but in consideration of increasing the degree of polymerization and forming a film having a higher hardness. , A silane compound having two or more hydrolyzable groups is more preferable.
Specific examples thereof include dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldiisopropoxysilane, dimethyldibutoxysilane, dimethyldiisopropenoxysilane, propylmethyldimethoxysilane, hexylmethyldimethoxysilane, phenylmethyldimethoxysilane, and diphenyl. Dimethoxysilane, Methyltrimethoxysilane, Methyltriethoxysilane, Methyltriisopropoxysilane, Methyltributoxysilane, Methyltriisopropenoxysilane, Ethyltrimethoxysilane, Ethyltriethoxysilane, Butyltrimethoxysilane, Hexyltrimethoxysilane , Decyltrimethoxysilane, phenyltrimethoxysilane, cyclohexyltrimethoxysilane, tetramethoxysilane, tetraethoxysilane and partial hydrolyzates thereof.
In addition, vinylmethyldimethoxysilane, vinylmethyldiethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3- (meth) acryloxypropylmethyldimethoxysilane, 3- (meth) ) Acryloxypropylmethyldiethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropylmethyldiethoxysilane, vinyltrimethoxysilane, vinyltri Ethoxysilane, 5-hexenyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxipropyl Triethoxysilane, 4-vinylphenyltrimethoxysilane, 3- (4-vinylphenyl) propyltrimethoxysilane, 4-vinylphenylmethyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, An alkoxysilane compound having a reactive functional group such as 3- (2-aminoethyl) aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, and a partial hydrolyzate thereof are used. You can also do it.
These alkoxysilane compounds may be used alone or in combination of two or more.

Among these, methoxysilane and ethoxysilane are preferable because of the ease of volatilization of by-products, methoxysilane is more preferable because of its high reactivity, and methyltrimethoxysilane, dimethyldimethoxysilane, and its oligomers are even more preferable. preferable.

The diluting solvent is not particularly limited as long as it dissolves or disperses the silicone oligomer, alkoxysilane, or curing catalyst of the present invention.
Specific examples thereof include aromatic hydrocarbons such as toluene and xylene; hydrocarbons such as hexane and octane; ketones such as methyl ethyl ketone and methyl isobutyl ketone; esters such as ethyl acetate and isobutyl acetate; methanol, ethanol, and the like. Alcohols such as isopropanol, butanol, isobutanol, t-butanol; fluorosolvents and the like can be mentioned. Specific examples of the fluorine-based solvent include the same as the fluorine-based solvent in the solvent used in the above-mentioned co-hydrolysis / condensation reaction.

The amount of these diluents used is 300 parts by mass or less with respect to 100 parts by mass of the silicone oligomer of the present invention, that is, the amount of the silicone oligomer of the present invention is 25% by mass or more and less than 100% by mass of the entire composition. It is preferable, 25 to 75% by mass is more preferable.

In addition, any additive can be appropriately added to the composition of the present invention as long as the effect of the present invention is not impaired.
Specific examples of such additives include non-reactive silicone oils, reactive silicone oils, adhesion-imparting agents such as silane coupling agents, antistatic agents, rust inhibitors, colorants, surfactants, and rheology adjusters. , UV absorbers, infrared absorbers, fluorescent agents, abrasives, fragrances, fillers, fillers, dyes, leveling agents, reactive diluents, non-reactive polymer resins, antioxidants, light stabilizers, defoamers Examples thereof include agents, dispersants, antistatic agents, thixotropy-imparting agents and the like.

The composition containing the silicone oligomer of the present invention can be applied as a coating agent to substrates such as various metals, glass, ceramics and resins.
The coating method is not particularly limited, and any method such as hand coating using fibers impregnated with the composition, brush coating, and mechanical coating using an automatic machine can be used.
In the composition of the present invention, in particular, a dry or water-wet fiber such as a sponge or a waste cloth is impregnated with an appropriate amount of the composition of the present invention, spread thinly on the surface of the substrate by hand, and then dried. It is preferable to wipe off the excess composition with a fiber such as a waste cloth and dry it naturally or forcibly dry it using a dryer or the like.
At this time, the alkoxy group contained in the composition is a Lewis acid point such as aluminum, titanium or zirconium incorporated in the silicone resin, or the moisture in the air or the substrate in the presence of the catalyst contained in the composition. The hydrolysis reaction proceeds due to the action of the water contained in the sponge used at the time of construction and crosslinks on the substrate to form a cured coating film.
Here, the coating layer according to the coating agent composition of the present invention is preferably a thin film, and the film thickness thereof is preferably in the range of approximately 0.01 to 100 μm, preferably 0.1 to 50 μm. .. When the coating layer is within the range, good water repellency, water slipperiness, workability at the time of coating, durability and aesthetics can be achieved at the same time.

The mechanism for forming a coating film having excellent properties by the silicone oligomer of the present invention is considered to be as follows.
First, when the silicone oligomer linked with the poly (perfluoroalkylene ether) chain of the present invention is applied to the surface on the substrate, the hydrolyzable group of the oligomer linked with the poly (perfluoroalkylene ether) chain is in the air. It is decomposed by water to become hydroxyl groups, and the hydroxyl groups are dehydrated and condensed to form a siloxane bond and harden.
Further, by adding an alkoxysilane or an oligomer of an alkoxysilane, these alkoxysilyl groups participate in cross-linking by a condensation reaction and are incorporated into the coating film to form a coating film having excellent film strength. In particular, by increasing the proportion of trifunctional and tetrafunctional siloxane bonds, the hardness of the film after curing increases.
At this time, since the poly (perfluoroalkylene ether) chain is uniformly dispersed in the silicone oligomer and is also present near the surface of the substrate, it is poly (perfluoroalkylene ether) even if it is wiped in an uncured state. The chain remains on the film, and a water- and oil-repellent film is obtained.

Since the coating agent composition of the present invention exhibits water and oil repellency even after being applied to the surface of a base material and wiped before curing, it can be applied to a metal steel sheet, a painted metal steel sheet, or a glass surface. It is suitable for application, and is particularly suitable for use in coated steel sheets used for the exterior of automobiles.

Further, in the silicone oligomer of the present invention, the surface of the cured product obtained by coating and curing or curing by itself exhibits properties such as antifouling, water repellency, oil repellency, and fingerprint resistance. Due to these characteristics, it becomes difficult to be soiled by fingerprints, sebum, human oil such as sweat, cosmetics, etc., and even if stains are attached, a cured product surface having excellent wiping property is provided.
Therefore, the silicone oligomer of the present invention and the composition containing the same are used to form a coating film or a protective film on the surface of an article that may be touched by the human body and contaminated by human fat, cosmetics, or the like. It is also useful as a hard coat composition.

Examples of such hard-coated articles include optical recording media such as optical magnetic discs, optical discs such as CDs, LDs, DVDs, and Blu-ray discs, and optical recording media such as hologram recording; glasses lenses, prisms, lens sheets, and pellicle. Optical components and optical devices such as membranes, polarizing plates, optical filters, wrenchular lenses, frennel lenses, antireflection films, optical fibers and optical couplers; CRTs, liquid crystal displays, plasma displays, electroluminescence displays, rear projection displays, fluorescent display tubes Various screen display devices such as (VFD), field emission projection displays, toner-based displays; especially PCs, mobile phones, mobile information terminals, game machines, electronic book readers, digital cameras, digital video cameras, automatic cash withdrawal deposit devices, cash Automatic payment machines, vending machines, navigation devices for automobiles, image display devices such as security system terminals, and touch panel (touch sensor, touch screen) type image display input devices that also operate them; mobile phones, mobile information terminals, Input devices such as electronic book readers, portable music players, portable game machines, remote controllers, controllers, keyboards, panel switches for in-vehicle devices; housings for mobile phones, mobile information terminals, cameras, portable music players, portable game machines, etc. Surfaces; Automotive exteriors, pianos, luxury furniture, marble and other surfaces; Art display protective glass, show windows, showcases, advertising covers, photostand covers, watches, automotive front glass, trains, aircraft, etc. Transparent glass or transparent plastic (acrylic, polycarbonate, etc.) members such as window glasses, automobile headlights, and tail lamps; various mirror members and the like can be mentioned.

In these applications, the coating agent containing the silicone oligomer of the present invention is used not only for coating the surface of an object but also for a transfer method widely used in in-mold molding and the like. can do.

Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples.
In the following, the number average molecular weight and the weight average molecular weight are standard polystyrene-equivalent values measured using tetrahydrofuran using GPC (gel permeation chromatography, product name: HLC-8320GPC EcoSEC, manufactured by Tosoh Corporation) as a developing solvent. be.
The viscosity is a value at 25 ° C. measured using a Canon Fenceke type viscometer.
The values of p, q, t, d, m, and r in the average formula (1) are ^{1 1} H-NMR measurement (device name: ULTRA SHIELD 400 Plus, manufactured by Bruker) and ²⁹ Si-NMR measurement (device name:). Calculated from the results of JNM-ECX5002, manufactured by JEOL).

（式中、ａ１／ｂ１＝０．９であり、ａ１およびｂ１が付された括弧内の繰り返し単位の配列は不定である。）[Synthesis Example 1] Synthesis of poly (perfluoroalkylene ether) chain-containing silane compound (A-1)

(In the formula, a1 / b1 = 0.9, and the arrangement of repeating units in parentheses with a1 and b1 is undefined.)

A compound represented by the following formula (8) (product name: Fomblin D2, manufactured by Solvay Specialty Polymer Co., Ltd., Mn: 1,500) 512 g, 3-in a glass flask equipped with a stirrer, a thermometer, a cooling tube, and a dropping device. 129 g of isocyanatopropyltrimethoxysilane and 0.64 g of tin octylate as a urethanization catalyst were charged, stirring was started under a nitrogen stream, and the mixture was reacted at 60 ° C. for 1 hour. After confirming the disappearance of the isocyanate group in the IR measurement, the reaction was stopped to obtain the compound (A-1) represented by the above formula (9).

（式中、ａ１／ｂ１＝０．３７であり、ａ１およびｂ１が付された括弧内の繰り返し単位の配列は不定である。）

(In the formula, a1 / b1 = 0.37, and the arrangement of the repeating units in parentheses with a1 and b1 is undefined.)

[Example 1] Synthesis of silicone oligomer (A-2) linked by a poly (perfluoroalkylene ether) chain Obtained in Synthesis Example 1 in a glass flask equipped with a stirring device, a thermometer, a cooling tube, and a dropping device. 53.2 g of the silane compound (A-1) and 136.2 g of methyltrimethoxysilane were charged, 1.5 g of methanesulfonic acid was added with stirring, and then 17 g of ion-exchanged water was further added dropwise over 1 hour. After completion of the dropping, the mixture was heated at 67 ° C. for 2 hours, and 61 g of the generated methanol was removed using a Dean-Stark tube. 4.5 g of Kyoward 500SN (manufactured by Kyowa Chemical Industry Co., Ltd.) was added to the obtained liquid, and the mixture was stirred at 25 ° C. for 2 hours to neutralize, and then residual methanol and low molecular weight components were distilled off under reduced pressure to make poly. A silicone oligomer (A-2) linked by a (perfluoroalkylene ether) chain was obtained.
The obtained silicone oligomer has Mw 9,600 and a viscosity of 160 mm ² / s, and the ratios of each structural unit in the average formula (1) calculated from the results of NMR measurement are p = 0.05 and q = 0, respectively. It was t = 0.95, d = 0, m = 0, r = 0.99.

[Example 2] Synthesis of silicone oligomer (A-3) linked by a perfluoropolyether chain The silane compound obtained in Synthesis Example 1 was placed in a glass flask equipped with a stirring device, a thermometer, a cooling tube, and a dropping device. (A-1) 53.2 g, methyltrimethoxysilane 115.8 g, and dimethyldimethoxysilane 18.0 g were charged, 1.5 g of methanesulfonic acid was added with stirring, and then 16.2 g of ion-exchanged water was further added. Dropped over time. After completion of the dropping, the mixture was heated at 67 ° C. for 2 hours, and 57.7 g of the generated methanol was removed using a Dean-Stark tube. 4.5 g of Kyoward 500SN (manufactured by Kyowa Chemical Industry Co., Ltd.) was added to the obtained liquid, and the mixture was stirred at 25 ° C. for 2 hours to neutralize, and then residual methanol and low molecular weight components were distilled off under reduced pressure to make poly. A silicone oligomer (A-3) linked by a (perfluoroalkylene ether) chain was obtained.
The obtained silicone oligomer has Mw10,400 and a viscosity of 200 mm ² / s, and the proportions of each structural unit in the average formula (1) calculated from the results of NMR measurement are p = 0.05 and q = 0, respectively. t = 0.81, d = 0.14, m = 0, r = 1.00.

[Example 3]
In a glass flask equipped with a stirrer, a thermometer, a cooling tube, and a dropping device, 53.2 g of the silane compound (A-1) obtained in Synthesis Example 1, 81.7 g of methyltrimethoxysilane, and 18.0 g of dimethyldimethoxysilane. , 15.2 g of tetramethoxysilane and 8.1 g of hexamethyldisiloxane were charged, 1.3 g of methanesulfonic acid was added with stirring, and then 14.3 g of ion-exchanged water was further added dropwise over 1 hour. After completion of the dropping, the mixture was heated at 67 ° C. for 2 hours, and 50.9 g of the generated methanol was removed using a Dean-Stark tube. 4.2 g of Kyoward 500SN (manufactured by Kyowa Chemical Industry Co., Ltd.) was added to the obtained liquid, and the mixture was stirred at 25 ° C. for 2 hours to neutralize, and then the remaining methanol and low molecular weight components were distilled off under reduced pressure. A silicone oligomer (A-4) linked by a poly (perfluoroalkylene ether) chain was obtained.
The obtained silicone oligomer has Mw11,500 and a viscosity of 250 mm ² / s, and the ratios of each structural unit in the average formula (1) calculated from the results of NMR measurement are p = 0.05 and q = 0, respectively. 10, t = 0.60, d = 0.15, m = 0.10, r = 0.91.

Production of Composition and Cured Product [Examples 4 to 10]
Each composition was prepared by mixing each component at 25 ° C. at the composition ratio shown in Table 1.

組成物（Ｂ）：（ＣＨ₃）（ＣＨ₃Ｏ）₂ＳｉＯＳｉ（ＣＨ₃）（ＯＣＨ₃）₂ ５０質量部と、（ＣＨ₃）₂Ｓｉ（ＯＣＨ₃）₂ ４０質量部との混合物
硬化触媒（Ｃ−１）：（Ｃ₄Ｈ₉Ｏ）Ａｌ（−ＯＣ（ＣＨ₃）＝ＣＨＣＯＯＣ₂Ｈ₅）₂
硬化触媒（Ｃ−２）：Ｔｉ（ＯＣ₄Ｈ₉）₄

Composition (B): Mixture curing catalyst of _{(CH 3} ) (CH ₃ O) ₂ SiOSi (CH ₃ ) (OCH ₃ ) ₂ 50 parts by mass and (CH ₃ ) ₂ Si (OCH ₃ ) _{2 40 parts by mass} (C-1): (C ₄ H ₉ O) Al (-OC (CH ₃ ) = CHCOOC ₂ H ₅ ) ₂
Curing catalyst (C-2): Ti (OC ₄ H ₉ ) ₄

[Example 11]
15.7 g of ion-exchanged water was mixed with 100 parts by mass of the composition prepared in Example 7, and the mixture was hydrolyzed and condensed by stirring at 25 ° C. for 2 hours, and linked with a poly (perfluoroalkylene ether) chain. A composition containing a silicone resin was obtained.

[Comparative Examples 1 to 6]
Each composition was prepared by mixing each component at 25 ° C. at the composition ratio shown in Table 2.

（式中、Ｒｆ¹は−ＣＦ₂（ＯＣＦ₂ＣＦ₂）_a2（ＯＣＦ₂）_b2ＯＣＦ₂−で表され、ａ２／ｂ２＝０．９、Ｒｆ¹部位のＭｎ：４，０００である。）Fluorine solvent (B'): C ₄ F ₉ OC ₂ H ₅
Silicone oligomer (A-6):

(In the formula, Rf ¹ is represented by −CF ₂ (OCF ₂ CF ₂ ) _a2 (OCF ₂ ) _b2 OCF ₂ −, a2 / b2 = 0.9, and Mn: 4,000 at the ^{Rf 1 site.)}

The following evaluations were performed on each of the compositions obtained in Examples 4 to 11 and Comparative Examples 1 to 6. The results are shown in Tables 3 and 4.
(1) Appearance of the composition The appearance of the composition was visually observed.
(2) Appearance of coating film Each of the obtained compositions was coated on a soda lime glass plate with a wire bar having a gap of 20 μm, and allowed to stand at 25 ° C. and 65% RH for 24 hours for moisture curing to cure the surface of the cured film. The appearance was visually observed.
(3) Pencil hardness The test piece used for evaluating the appearance of the coating film was measured under a load of 750 g according to JIS K5600-5-4.
(4) Contact angle Each of the obtained compositions is coated on an electrodeposition coating plate (automotive paint coated black test plate, manufactured by Standard Test Piece Co., Ltd.) with a wire bar with a gap of 20 μm, and at 25 ° C., 65% RH. The water contact angle and hexadecane contact angle (droplet amount: 2 μl) on the surface of the cured film are measured by a contact angle meter (device name: Drop Master DM-701, manufactured by Kyowa Interface Science Co., Ltd.). ).
(5) Contact angle (after wiping)
Each of the obtained compositions was coated on an electrodeposition coating plate (black test plate coated with automobile paint, manufactured by Standard Test Piece Co., Ltd.) with a wire bar with a gap of 20 μm, and after 1 minute, with a microfiber towel wet with water. Wipe 5 times in one direction, then wipe 5 times in one direction with a dry microfiber towel, stand at 25 ° C. at 65% RH for 24 hours, then water contact angle and hexadecane contact angle on the dried surface. (Droplet amount: 2 μl) was measured with a contact angle meter (device name: Drop Master DM-701, manufactured by Kyowa Surface Science Co., Ltd.).

As shown in Table 3, in Examples 4 to 11, it can be seen that the water contact angle and the hexadecane contact angle did not significantly decrease before and after wiping.
As shown in Table 4, in Comparative Examples 1 and 2, it can be seen that the water contact angle and the hexadecane contact angle are lowered by wiping.
It can be seen that in Comparative Example 3, the hardness of the coating film is low, and the water contact angle and the hexadecane contact angle are lowered by wiping.
In Comparative Examples 4 and 5 in which the amount of the poly (perfluoroalkylene ether) chain fluorine component added was increased, it was found that a uniform composition could not be obtained and a smooth surface could not be obtained at the time of film formation.
It can be seen that in Comparative Example 6 having no fluorine component, water repellency and oil repellency cannot be obtained.
From the comparison between Comparative Examples 1 and 2 and Comparative Example 6, it can be seen that in Comparative Examples 1 and 2, the fluorine component was removed by wiping.

Claims (9)

A silicone oligomer represented by the following average formula (1).

[In the formula, p, q, t, d, m and r are 0 <p ≦ 0.3, 0 ≦ q ≦ 0.5, 0.3 ≦ t <1, 0 ≦ d ≦ 0.5, 0. Represents a number that satisfies ≦ m ≦ 0.5 and p + q + t + d + m = 1, 0.2 × (3p + 4q + 3t + 2d + m) ≦ r ≦ 0.7 × (3p + 4q + 3t + 2d + m).
R ^{1 to} R ⁷ represent hydrogen atoms or substituted or unsubstituted monovalent hydrocarbon groups having 1 to 18 carbon atoms independently of each other, and Rf is a divalent group having a number average molecular weight of 500 to 5,000. Represents the poly (perfluoroalkylene ether) group of, X represents a divalent hydrocarbon group independently of each other, and Q represents an oxygen atom or a linking group represented by the following formula (2) independently of each other. Represents.

(In the formula, Z represents a divalent hydrocarbon group, and an asterisk (*) represents a binding site with Rf.)] The p, q, t, d, m and r are 0 <p ≦ 0.3, q = 0, 0.7 ≦ t <1, d = 0, m = 0, and 0.2 × (3p + 3t). ) ≤ r ≤ 0.7 × (3p + 3t), where X represents an alkylene group having 1 to 10 carbon atoms and Z represents an alkylene group having 1 to 6 carbon atoms. 1 The silicone oligomer according to 1. The Rf represents a poly (perfluoroalkylene ether) group having a number average molecular weight of 1,000 to 3,000, and the perfluoroalkylene moiety in the poly (perfluoroalkylene ether) group is derived from perfluoromethylene and perfluoroethylene. The silicone oligomer according to claim 1 or 2, wherein the ratio (a / b) of the number of perfluoromethylene (a) to the number of perfluoroethylene (b) is 1/10 to 10/1. A composition containing 0.01 to 30 parts by mass of a hydrolysis condensation catalyst with respect to 100 parts by mass of the silicone oligomer according to any one of claims 1 to 3. The composition according to claim 4, further comprising at least one selected from alkoxysilane, a hydrolyzed condensate of alkoxysilane, and a solvent in an amount of 300 parts by mass or less with respect to 100 parts by mass of the silicone oligomer. A cured product obtained by hydrolyzing and condensing the silicone oligomer according to any one of claims 1 to 3. A cured product obtained from the composition according to claim 4 or 5. A coating film obtained from the composition according to claim 4 or 5. The article having the coating film according to claim 8.