JP2023170334A - Perfluoropolyether-organopolysiloxane block copolymer - Google Patents

Abstract

To provide a perfluoropolyether-organopolysiloxane block copolymer that includes a perfluoropolyether group, enables the control of the number of siloxane units in the molecule, and exhibits superior affinity for a fluorine-free organic compound.SOLUTION: A perfluoropolyether-organopolysiloxane block copolymer includes a perfluoropolyether block and an organopolysiloxane block. The organopolysiloxane block includes, on its side chain, at least one organic group including a reactive functional group selected from an oxyalkylene group, a hydroxyalkyl group, a hydroxyaryl group, an epoxy group and a carboxylic acid anhydride group.SELECTED DRAWING: None

Description

The present invention relates to perfluoropolyether-organopolysiloxane block copolymers.

In general, perfluoropolyether group-containing compounds have very low surface free energy and therefore have chemical resistance, lubricity, mold releasability, water and oil repellency, and the like. Utilizing its properties, it is used industrially as a lubricant for magnetic recording media, an oil-proofing agent for precision equipment, a mold release agent, a water-repellent, oil-repellent and stain-proofing agent for paper, fiber, glass, resin, etc., cosmetics, and protective films. It is widely used as such.

However, because the surface free energy of perfluoropolyether group-containing compounds is low, their compatibility and affinity with other substances are extremely low, and perfluoropolyether group-containing compounds are added to various industrial materials. Attempts to impart properties to the perfluoropolyether group caused problems in dispersion stability, reactivity, etc., and it was difficult to incorporate perfluoropolyether group-containing compounds into various industrial materials.

On the other hand, polysiloxane compounds also have properties such as water repellency, lubricity, and mold releasability due to their low surface free energy. Polysiloxane compounds have a better affinity for other substances than perfluoropolyether compounds, and it is possible to further improve dispersion stability by various modifications. Therefore, polysiloxane compounds can be easily added to various industrial materials to impart the properties of silicone, and are used as additives for improving performance in a wide range of fields. As a compound having a perfluoropolyether group and a polysiloxane chain, there is a perfluoropolyether-modified polysiloxane compound (Patent Document 1).
However, in this polysiloxane compound, if the fluorine modification rate is increased in an attempt to improve the properties of the perfluoropolyether group, the affinity for other industrial materials will be significantly reduced. Therefore, problems may occur in dispersion stability, reactivity, etc.

In view of this, perfluoropolyether-organopolysiloxane block copolymers have been developed that have the properties of both perfluoropolyether and polysiloxane and have excellent affinity with non-fluorinated organic compounds ( Patent Documents 2, 3).
Additionally, perfluoropolyether-modified organopolysiloxanes having reactive functional groups such as carbinol groups and epoxy groups in the siloxane moiety have also been developed (Patent Documents 4 and 5).

Japanese Patent Application Publication No. 2006-321764 JP2008-88412A Japanese Patent Application Publication No. 2011-21158 Japanese Patent Application Publication No. 10-330487 Japanese Patent Application Publication No. 5-43587

The perfluoropolyether-organopolysiloxane block copolymers disclosed in Patent Document 2 and Patent Document 3 have good affinity with non-fluorine organic compounds, but because they do not have reactive functional groups, they can be used in various ways. It cannot react with organic compounds, and even if it is blended into a curable composition, it cannot impart lasting water and oil repellency.
In addition, the perfluoropolyether-modified organopolysiloxanes having reactive functional groups disclosed in Patent Documents 4 and 5 have a limited number of organosiloxane units and reactive functional groups that can be introduced, and the curable composition It is difficult to control the compatibility with materials and the crosslink density of the resulting cured product.
Therefore, the present invention has a perfluoropolyether group, and it is possible to control the molecular structure such as the number of each unit constituting the block copolymer and the modification rate of the group introduced into the side chain of the organopolysiloxane block. A perfluoropolyether-organopolysiloxane block copolymer (hereinafter simply abbreviated as block copolymer) that has a functional group that can react with various organic compounds in the organopolysiloxane block and has excellent affinity with non-fluorinated organic compounds. The purpose is to provide

As a result of intensive research to solve the above-mentioned problems, the present inventors have discovered that the following perfluoropolyether-organopolysiloxane block copolymer can achieve the above-mentioned objects, and have completed the present invention.
That is, the present invention is as follows.

［式（１）中、
Ｒｆは下記式（２）

（式（２）中、ｚは１～４の数であり、ｖ、ｗ、ｘ及びｙはそれぞれ独立に０～２００の数であり、ｖ＋ｗ＋ｘ＋ｙ＝３～２００である。また、各繰り返し単位は直鎖状でも分岐状であってもよい。各繰り返し単位の配列順序は限定されず、ランダムであってもブロックであってもよい。）
で表されるパーフルオロポリエーテルブロックであり、
Ｗ１は下記式（Ａ）

（式（Ａ）中、Ｒ¹は独立して炭素数１～１８のアルキル基及びフェニル基から選ばれる基である。Ｒ²は下記式（３）で表されるオキシアルキレン基、炭素数３～１２のω－ヒドロキシアルキル基、ヒドロキシアリール基を有する炭素数９～１８の有機基、エポキシ基を有する炭素数６～１５の有機基及びカルボン酸無水物基を有する炭素数４～３２の有機基から選ばれる１種以上の反応性官能基である。Ｒ³は炭素数７～１８のアラルキル基、炭素数３～１２のアルコキシアルキル基、及び下記式（４）で表されるオキシアルキレン基から選ばれる１種以上の基である。

（式（３）中、Ｒ⁴は炭素数２～４のアルキレン基であり、ｊは３～１２の数であり、ｋは１～６０の数である。なお、上記ｋで括られたオキシアルキレン単位は１種または２種以上で構成されたものであり、２種以上で構成される場合の各単位の配列順序は限定されず、ランダムであってもブロックであってもよい。）

（式（４）中、Ｒ⁴は炭素数２～４のアルキレン基であり、Ｒ⁵は炭素数１～４のアルキル基であり、ｍは３～１２の数であり、ｎは１～６０の数である。なお、上記ｎで括られたオキシアルキレン単位は１種または２種以上で構成されたものであり、２種以上で構成される場合の各単位の配列順序は限定されず、ランダムであってもブロックであってもよい。）
ｐ１、ｑ１、及びｒ１はそれぞれ０～１，０００の数である。各繰り返し単位の配列順序は限定されず、ランダムであってもブロックであってもよい。）
で表される２価のオルガノポリシロキサンブロックであり、
Ｗ２はそれぞれ独立に下記式（Ｂ）

（式（Ｂ）中、Ｒ¹は独立して炭素数１～１８のアルキル基及びフェニル基から選ばれる基である。Ｒ²は上記式（３）で表されるオキシアルキレン基、炭素数３～１２のω－ヒドロキシアルキル基、ヒドロキシアリール基を有する炭素数９～１８の有機基、エポキシ基を有する炭素数６～１５の有機基及びカルボン酸無水物基を有する炭素数４～３２の有機基から選ばれる１種以上の反応性官能基である。Ｒ³は炭素数７～１８のアラルキル基、炭素数３～１２のアルコキシアルキル基、及び上記式（４）で表されるオキシアルキレン基から選ばれる１種以上の基である。Ｒ¹’は独立して炭素数１～１８のアルキル基及びフェニル基から選ばれる基である。ｐ２、ｑ２及びｒ２はそれぞれ０～１，０００の数である。各繰り返し単位の配列順序は限定されず、ランダムであってもブロックであってもよい。）
で表される１価のオルガノポリシロキサンブロックであり、
但し、上記式（Ａ）のｑ１及び上記式（Ｂ）のｑ２は同時に０とならない。
Ｑは炭素数２～１２の２価の有機基であり、また、上記式（１）中、ＱはＲｆの末端の炭素原子、Ｗ１の末端のケイ素原子又はＷ２の末端のケイ素原子のいずれかと結合しており、
ｇは０～５０の数であるが、ｇが０のときＷ２の式（Ｂ）中のｑ２は０とならない。］

［２］
重量平均分子量が４，０００～５００，０００であり、１分子中のオルガノポリシロキサンブロック含有量が５０％以上である、［１］に記載のパーフルオロポリエーテル－オルガノポリシロキサンブロックコポリマー。

［３］
Ｒｆで表されるパーフルオロポリエーテルブロックが、下記式（５）で表される基である、［１］又は［２］に記載のパーフルオロポリエーテル－オルガノポリシロキサンブロックコポリマー。

（式（５）中、ｖ及びｗはそれぞれ０～２００の数で、但しｖ＋ｗ＝３～２００である。また、（ＯＣ₂Ｆ₄）の繰り返し単位は直鎖状でも分岐状であってもよい。各繰り返し単位の配列順序は限定されず、ランダムであってもブロックであってもよい。）

［４］
式（Ａ）又は式（Ｂ）中のＲ²が上記式（３）で表されるオキシアルキレン基であり、式（３）中のＲ⁴が炭素数２または３のアルキレン基である、［１］～［３］のいずれかに記載のパーフルオロポリエーテル－オルガノポリシロキサンブロックコポリマー。

［５］
式（Ａ）又は式（Ｂ）中のＲ²が炭素数３～１２のω－ヒドロキシアルキル基である、［１］～［３］のいずれかに記載のパーフルオロポリエーテル－オルガノポリシロキサンブロックコポリマー。

［６］
式（Ａ）又は式（Ｂ）中のＲ²が下記式（６）で表されるヒドロキシアリール基を有する有機基である、［１］～［３］のいずれかに記載のパーフルオロポリエーテル－オルガノポリシロキサンブロックコポリマー。

（式（６）中、ａは３～４の数であり、Ｒ⁶は水素原子、メトキシ基及びヒドロキシ基から選ばれる基である。）

［７］
式（６）において、Ｒ⁶が水素原子又はメトキシ基である、［６］に記載のパーフルオロポリエーテル－オルガノポリシロキサンブロックコポリマー。

［８］
式（Ａ）又は式（Ｂ）中のＲ²が下記式（７）で表されるエポキシ基を有する有機基である、［１］～［３］のいずれかに記載のパーフルオロポリエーテル－オルガノポリシロキサンブロックコポリマー。

（式（７）中、ｊは３～１２の数である。）

［９］
式（Ａ）又は式（Ｂ）中のＲ²が下記式（８）で表されるエポキシ基を有する有機基である、［１］～［３］のいずれかに記載のパーフルオロポリエーテル－オルガノポリシロキサンブロックコポリマー。

［１０］
式（Ａ）又は式（Ｂ）中のＲ²が下記式（９）または（１０）で表されるカルボン酸無水物基を有する有機基である、［１］～［３］のいずれかに記載のパーフルオロポリエーテル－オルガノポリシロキサンブロックコポリマー。

（式（９）中、Ｒ⁷は独立して、水素原子、または炭素数１～８のアルキル基、及びフェニル基から選ばれる基である。ｂは０～４である。）

［１１］
式（Ａ）及び式（Ｂ）において、ｒ１＋ｒ２＞１である、［１］～［１０］のいずれかに記載のパーフルオロポリエーテル－オルガノポリシロキサンブロックコポリマー。

［１２］
式（Ａ）又は式（Ｂ）中のＲ³が式（４）で表されるオキシアルキレン基である、［１１］に記載のパーフルオロポリエーテル－オルガノポリシロキサンブロックコポリマー。 [1]
A perfluoropolyether-organopolysiloxane block copolymer having a perfluoropolyether block and an organopolysiloxane block represented by the following formula (1), wherein the side chain of the organopolysiloxane block has an oxyalkylene group, A perfluoropolyether-organopolysiloxane block copolymer having one or more organic groups containing a reactive functional group selected from a hydroxyalkyl group, a hydroxyaryl group, an epoxy group, and a carboxylic acid anhydride group.

[In formula (1),
Rf is the following formula (2)

(In formula (2), z is a number from 1 to 4, v, w, x and y are each independently a number from 0 to 200, and v+w+x+y=3 to 200. Also, each repeating unit is It may be linear or branched. The arrangement order of each repeating unit is not limited and may be random or block.)
It is a perfluoropolyether block represented by
W1 is the following formula (A)

(In formula (A), R ¹ is a group independently selected from an alkyl group having 1 to 18 carbon atoms and a phenyl group. R ² is an oxyalkylene group represented by the following formula (3), and 3 carbon atoms. ~12 ω-hydroxyalkyl group, an organic group having 9 to 18 carbon atoms having a hydroxyaryl group, an organic group having 6 to 15 carbon atoms having an epoxy group, and an organic group having 4 to 32 carbon atoms having a carboxylic acid anhydride group R ³ is an aralkyl group having 7 to 18 carbon atoms, an alkoxyalkyl group having 3 to 12 carbon atoms, and an oxyalkylene group represented by the following formula (4). One or more groups selected from

(In formula (3), R ⁴ is an alkylene group having 2 to 4 carbon atoms, j is a number from 3 to 12, and k is a number from 1 to 60. The alkylene unit is composed of one type or two or more types, and when composed of two or more types, the arrangement order of each unit is not limited and may be random or block.)

(In formula (4), R ⁴ is an alkylene group having 2 to 4 carbon atoms, R ⁵ is an alkyl group having 1 to 4 carbon atoms, m is a number from 3 to 12, and n is 1 to 60 In addition, the oxyalkylene units bracketed by n above are composed of one type or two or more types, and when composed of two or more types, the arrangement order of each unit is not limited, (Can be random or block.)
p1, q1, and r1 are each a number from 0 to 1,000. The arrangement order of each repeating unit is not limited, and may be random or block. )
It is a divalent organopolysiloxane block represented by
W2 is each independently expressed by the following formula (B)

(In formula (B), R ¹ is a group independently selected from an alkyl group having 1 to 18 carbon atoms and a phenyl group. R ² is an oxyalkylene group represented by the above formula (3), and 3 carbon atoms. ~12 ω-hydroxyalkyl group, an organic group having 9 to 18 carbon atoms having a hydroxyaryl group, an organic group having 6 to 15 carbon atoms having an epoxy group, and an organic group having 4 to 32 carbon atoms having a carboxylic acid anhydride group R ³ is an aralkyl group having 7 to 18 carbon atoms, an alkoxyalkyl group having 3 to 12 carbon atoms, and an oxyalkylene group represented by the above formula (4). R ¹ ' is a group independently selected from an alkyl group having 1 to 18 carbon atoms and a phenyl group. p2, q2 and r2 are each a number from 0 to 1,000. (The arrangement order of each repeating unit is not limited and may be random or block.)
A monovalent organopolysiloxane block represented by
However, q1 in the above formula (A) and q2 in the above formula (B) do not become 0 at the same time.
Q is a divalent organic group having 2 to 12 carbon atoms, and in the above formula (1), Q is either the terminal carbon atom of Rf, the terminal silicon atom of W1, or the terminal silicon atom of W2. are combined,
g is a number from 0 to 50, but when g is 0, q2 in formula (B) of W2 does not become 0. ]

[2]
The perfluoropolyether-organopolysiloxane block copolymer according to [1], which has a weight average molecular weight of 4,000 to 500,000 and an organopolysiloxane block content in one molecule of 50% or more.

[3]
The perfluoropolyether-organopolysiloxane block copolymer according to [1] or [2], wherein the perfluoropolyether block represented by Rf is a group represented by the following formula (5).

(In formula (5), v and w are each a number from 0 to 200, provided that v+w = 3 to 200. Also, the repeating unit of (OC ₂ F ₄ ) may be linear or branched. (The arrangement order of each repeating unit is not limited, and may be random or block.)

[4]
^R2 in formula (A) or formula (B) is an oxyalkylene group represented by the above formula (3), and ^R4 in formula (3) is an alkylene group having 2 or 3 carbon atoms, [ The perfluoropolyether-organopolysiloxane block copolymer according to any one of [1] to [3].

[5]
The perfluoropolyether-organopolysiloxane block according to any one of [1] to [3], wherein R ² in formula (A) or formula (B) is an ω-hydroxyalkyl group having 3 to 12 carbon atoms. copolymer.

[6]
The perfluoropolyether according to any one of [1] to [3], wherein R ² in formula (A) or formula (B) is an organic group having a hydroxyaryl group represented by the following formula (6) -Organopolysiloxane block copolymer.

(In formula (6), a is a number from 3 to 4, and R ⁶ is a group selected from a hydrogen atom, a methoxy group, and a hydroxy group.)

[7]
The perfluoropolyether-organopolysiloxane block copolymer according to [6], wherein in formula (6), R ⁶ is a hydrogen atom or a methoxy group.

[8]
The perfluoropolyether according to any one of [1] to [3], wherein R ² in formula (A) or formula (B) is an organic group having an epoxy group represented by the following formula (7). Organopolysiloxane block copolymer.

(In formula (7), j is a number from 3 to 12.)

[9]
The perfluoropolyether according to any one of [1] to [3], wherein R ² in formula (A) or formula (B) is an organic group having an epoxy group represented by the following formula (8). Organopolysiloxane block copolymer.

[10]
Any one of [1] to [3], wherein R ² in formula (A) or formula (B) is an organic group having a carboxylic acid anhydride group represented by the following formula (9) or (10). Perfluoropolyether-organopolysiloxane block copolymers as described.

(In formula (9), R ⁷ is independently a group selected from a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, and a phenyl group. b is 0 to 4.)

[11]
The perfluoropolyether-organopolysiloxane block copolymer according to any one of [1] to [10], wherein in formula (A) and formula (B), r1+r2>1.

[12]
The perfluoropolyether-organopolysiloxane block copolymer according to [11], wherein R ³ in formula (A) or formula (B) is an oxyalkylene group represented by formula (4).

The block copolymer of the present invention has perfluoropolyether blocks, has a high siloxane content, and has organopolysiloxane blocks at both ends of the molecular chain. Furthermore, the side chain of the organopolysiloxane block has one or more groups selected from oxyalkylene groups, hydroxyalkyl groups, hydroxyaryl groups, epoxy groups, and carboxylic acid anhydride groups. Therefore, even though it has a perfluoropolyether block, it is easily compatible with non-fluorine organic compounds and can react with various organic compounds. Further, in the block copolymer of the present invention, the number of organopolysiloxane units and the modification rate of the groups possessed by the side chains of the organopolysiloxane blocks can be easily controlled. Furthermore, it is also easy to introduce one or more groups selected from groups having an aralkyl group and an oxyalkylene unit, which have excellent affinity with non-fluorine organic compounds.
Therefore, the block copolymer of the present invention is useful for applications such as a surface modifier for non-fluorine organic resins.

式（１）中の各符号の定義は前記と同じである。 The present invention will be explained in more detail below.
The perfluoropolyether-organopolysiloxane block copolymer of the present invention is represented by the following formula (1). In the block copolymer, perfluoropolyether blocks (Rf) and organopolysiloxane blocks (W1 or W2) are present alternately.

The definition of each symbol in formula (1) is the same as above.

The above-mentioned organopolysiloxane block has one or more types of organic groups including a reactive functional group selected from an oxyalkylene group, a hydroxyalkyl group, a hydroxyaryl group, an epoxy group, and a carboxylic acid anhydride group in its side chain. Can react with organic compounds.

In the block copolymer of formula (1) above, the organopolysiloxane block content in one molecule is preferably 50% or more and 99% or less, more preferably 60% or more and 90% or less. When the organopolysiloxane block content is at least the above lower limit, it has excellent compatibility with non-fluorine organic compounds, and when it is at most the above upper limit, the properties of perfluoropolyether groups are easily expressed. The organopolysiloxane block content is determined by the ¹ H-NMR spectrum of the block copolymer of formula (1), the peak derived from alkylene of Q in formula (1), and the organic group on the silicon atom in W1 and W2. The molar ratio of the perfluoropolyether block Rf with a known molecular weight and the organosiloxy unit is determined from the integral ratio with the derived peak, and this molar ratio is calculated by converting it into a molecular weight ratio. Note that since the block copolymer of formula (1) usually has a distribution in its structure, the above organopolysiloxane block content is an average value per molecule.

It is preferable that one or more of the organopolysiloxane blocks W1 and W2 has a siloxane unit represented by the following formula (11).

In the above formula (11), R ² is an oxyalkylene group represented by the following formula (3), an ω-hydroxyalkyl group having 3 to 12 carbon atoms, an organic group having 9 to 18 carbon atoms having a hydroxyaryl group, or an epoxy It is one or more reactive functional groups selected from an organic group having 6 to 15 carbon atoms and an organic group having 4 to 32 carbon atoms having a carboxylic acid anhydride group.

式（３）中、Ｒ⁴は炭素数２～４のアルキレン基であり、好ましくは炭素数２～３のアルキレン基である。ｊは３～１２の数であり、好ましくは３～８の数である。ｋは１～６０の数であり、好ましくは１～１２の数である。上記ｋで括られたオキシアルキレン単位は１種または２種以上で構成されたものであり、２種以上で構成される場合の各単位の配列順序は限定されず、ランダムであってもブロックであってもよい。

In formula (3), R ⁴ is an alkylene group having 2 to 4 carbon atoms, preferably an alkylene group having 2 to 3 carbon atoms. j is a number from 3 to 12, preferably from 3 to 8. k is a number from 1 to 60, preferably from 1 to 12. The oxyalkylene units bracketed by k above are composed of one type or two or more types, and when composed of two or more types, the arrangement order of each unit is not limited, and even if it is random, it can be a block. There may be.

The C3-C12 ω-hydroxyalkyl group of R ² is preferably a C3-C8 ω-hydroxyalkyl group.

（式（６）中、ａは３～４の数であり、好ましくは３である。Ｒ⁶は水素原子、メトキシ基及びヒドロキシ基から選ばれる基であり、好ましくは水素原子又はメトキシ基である。 The organic group having 9 to 18 carbon atoms and having a hydroxyaryl group as R ² is preferably exemplified by a group represented by the following formula (6).

(In formula (6), a is a number from 3 to 4, preferably 3. R ⁶ is a group selected from a hydrogen atom, a methoxy group, and a hydroxy group, and is preferably a hydrogen atom or a methoxy group. .

式（７）中、ｊは３～１２の数であり、好ましくは３～８の数である。 The organic group having 6 to 15 carbon atoms and having an epoxy group as R ² is preferably exemplified by a group represented by the following formula (7) or the following formula (8).

In formula (7), j is a number from 3 to 12, preferably from 3 to 8.

式（９）中、ｂは０～４であり、好ましくはｂ＝０（単結合）、ｂ＝３（トリメチレン基）又はｂ＝４（テトラメチレン基）である。Ｒ⁷は独立して、水素原子、または炭素数１～８のアルキル基及びフェニル基から選ばれる基であり、好ましくは水素原子である。

Preferred examples of the organic group having 4 to 32 carbon atoms and having a carboxylic acid anhydride group for R ² are groups represented by the following formula (9) or (10).

In formula (9), b is 0 to 4, preferably b = 0 (single bond), b = 3 (trimethylene group) or b = 4 (tetramethylene group). R ⁷ is independently a hydrogen atom or a group selected from an alkyl group having 1 to 8 carbon atoms and a phenyl group, preferably a hydrogen atom.

From an oxyalkylene group represented by the above formula (3), an ω-hydroxyalkyl group having 3 to 12 carbon atoms, an organic group having a hydroxyaryl group, an organic group having an epoxy group, and an organic group having a carboxylic acid anhydride group. One or more siloxane units represented by the above formula (11) having a selected group are present in the above formula (1), and preferably two or more siloxane units are present from the viewpoint of reactivity with organic compounds. Note that the siloxane units of formula (11) in the organopolysiloxane blocks W1 and W2 may be the same or different, but are preferably the same.

上記式（１２）中、Ｒ³は炭素数７～１８のアラルキル基、炭素数３～１２のアルコキシアルキル基、及び下記式（４）で表されるオキシアルキレン基から選ばれる１種以上の基である。 The above formula (1) may have a siloxane unit represented by the following formula (12) in one or more of the organopolysiloxane blocks W1 and W2.

In the above formula (12), R ³ is one or more groups selected from an aralkyl group having 7 to 18 carbon atoms, an alkoxyalkyl group having 3 to 12 carbon atoms, and an oxyalkylene group represented by the following formula (4). It is.

式（４）中、Ｒ⁴は炭素数２～４のアルキレン基であり、好ましくは炭素数２～３のアルキレン基である。Ｒ⁵は炭素数１～４のアルキル基であり、好ましくはメチル基である。ｍは３～１２の数であり、好ましくは３である。ｎは１～６０の数であり、好ましくは２～１２の数である。上記ｎで括られたオキシアルキレン基の繰り返し単位は１種または２種以上で構成されたものであり、２種以上で構成される場合の各単位の配列順序は限定されず、ランダムであってもブロックであってもよい。

In formula (4), R ⁴ is an alkylene group having 2 to 4 carbon atoms, preferably an alkylene group having 2 to 3 carbon atoms. R ⁵ is an alkyl group having 1 to 4 carbon atoms, preferably a methyl group. m is a number from 3 to 12, preferably 3. n is a number from 1 to 60, preferably from 2 to 12. The repeating unit of the oxyalkylene group enclosed by n above is composed of one type or two or more types, and when composed of two or more types, the arrangement order of each unit is not limited and is random. may also be a block.

式（１３）中、Ｒ⁸は水素原子、メチル基又はフェニル基であり、好ましくはメチル基である。 Further, the aralkyl group having 7 to 18 carbon atoms for R ³ is preferably a group represented by the following formula (13).

In formula (13), R ⁸ is a hydrogen atom, a methyl group or a phenyl group, preferably a methyl group.

A siloxane unit represented by the above formula (12) having one or more groups selected from a group having an aralkyl group, an alkoxyalkyl group, and an oxyalkylene unit may optionally be present in the above formula (1), When having a siloxane unit represented by formula (12), the block copolymer of formula (1) becomes easily compatible with a non-fluorine organic compound. Note that the siloxane units of formula (12) in the organopolysiloxane blocks W1 and W2 may be the same or different.

In the above formula (1), the organopolysiloxane block W1 is a divalent group represented by the following formula (A).

In the above formula (A), R ¹ is a group independently selected from an alkyl group having 1 to 18 carbon atoms and a phenyl group. Here, examples of the alkyl group having 1 to 18 carbon atoms include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, octyl group, dodecyl group, octadecyl group, and the like. Preferred examples of R ¹ include a methyl group, an ethyl group, and a phenyl group, with a methyl group being particularly preferred.

Examples of R ² and R ³ in the above formula (A) include those exemplified for R ² in formula (11) and R ³ in formula (12).

In the above formula (A), p1, q1, and r1 are each a number from 0 to 1,000, preferably a number from 0 to 500, and more preferably a number from 0 to 200. The arrangement order of each repeating unit is not limited, and may be random or block.

Examples of the group represented by the above formula (A) include groups represented by the following formulas (14) to (26), but are not limited to the following formulas.

In the above formula (1), the organopolysiloxane block W2 is a monovalent group represented by the following formula (B).

In the above formula (B), R ¹ , R ² and R ³ are the same as those listed in the above formula (A). R ¹ ' is a group independently selected from an alkyl group having 1 to 18 carbon atoms and a phenyl group, specifically a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group, a dodecyl group, Examples include octadecyl group. Preferred are methyl group, butyl group, hexyl group, octyl group, and dodecyl group.

In the above formula (B), p2, q2 and r2 are each a number from 0 to 1,000, preferably a number from 0 to 500, and more preferably a number from 0 to 200. Note that the arrangement order of each repeating unit is not limited, and may be random or block. However, q1 in the above formula (A) and q2 in the above formula (B) do not become 0 at the same time.

Examples of the group represented by formula (B) include groups represented by the following formulas (27) to (37), but are not limited to the following formulas.

The perfluoropolyether block Rf in the above formula (1) is represented by the following formula (2).

In formula (2), z is a number from 1 to 4, and v, w, x and y are each independently a number from 0 to 200, preferably each from 0 to 50, provided that v+w+x+y= 3 to 200, preferably 10 to 50, each repeating unit may be linear or branched, the arrangement order of each repeating unit is not limited, and may be random or block. Good too.

Examples of each repeating unit of the above formula (2) include the following repeating units.

Among these, a perfluoropolyether block of the following formula (5) in which z=1 and x and y are 0 in the above formula (2) is preferable because it has excellent compatibility with non-fluorine organic compounds.

In formula (5), v and w are each a number from 0 to 200, preferably each from 0 to 50, provided that v+w=3 to 200, preferably 10 to 50, and (OC The repeating unit of ₂ F ₄ ) may be linear or branched, and the arrangement order of each repeating unit is not limited and may be random or block.

The perfluoropolyether blocks represented by the above formulas usually have a distributed structure, and v, w, x, and y are each average values per molecule.

（式中、＊はＲｆに結合する遊離基、＊＊はＷ１またはＷ２に結合する遊離基を示す。） In the above formula (1), Q is a divalent organic group having 2 to 12 carbon atoms, preferably 3 to 6 carbon atoms. In the above formula (1), Q is bonded to either the terminal carbon atom of Rf, the terminal silicon atom of W1, or the terminal silicon atom of W2. Note that Q may contain an oxygen atom or a nitrogen atom. Specific examples include ether bonds, ester bonds, amide bonds, and secondary amino groups. Specific examples of Q include the following groups.

(In the formula, * represents a free group that binds to Rf, and ** represents a free group that binds to W1 or W2.)

Among the specific examples of Q above, ^* -CH ₂ OCH ₂ CH ₂ CH ₂ - ^** is preferred in that it is easy to connect the organopolysiloxane block and the perfluoropolyether block.

The weight average molecular weight of the block copolymer of formula (1) is preferably 4,000 to 500,000. When the weight average molecular weight is within this range, it tends to have excellent solubility in non-fluorine organic compounds and is easy to handle. In addition, in this specification, the weight average molecular weight is a polystyrene equivalent value determined by GPC (gel permeation chromatography) measurement under the following conditions (the same applies hereinafter).

[Measurement condition]
Developing solvent: toluene Flow rate: 0.6 mL/min
Detector: Differential refractive index detector (RI)
Column:TSK Guardcolumn SuperH-H
TSKgel SuperH5000 (6.0mm I.D. x 15cm x 1)
TSKgel SuperH4000 (6.0mm I.D. x 15cm x 1)
TSKgel SuperH3000 (6.0mm I.D. x 15cm x 1)
TSKgel SuperH2000 (6.0mm I.D. x 15cm x 1)
(Both manufactured by Tosoh Corporation)
Column temperature: 40℃
Sample injection amount: 50 μL (toluene solution with a concentration of 0.3% by mass)

In the above formula (1), g is a number from 0 to 50, but it is preferably a number that satisfies the weight average molecular weight of the block copolymer of formula (1) from 4,000 to 500,000. Specifically, g is preferably a number from 0 to 20, more preferably from 0 to 10. However, when g is 0, q2 in equation (B) of W2 does not become 0.

[Method for producing perfluoropolyether-organopolysiloxane block copolymer]
The block copolymer of the present invention can be produced by the method described below.
Component (a): an organohydrogenpolysiloxane having a perfluoropolyether block represented by the following formula (38),
(b) Component: Compound having an oxyalkylene group having a terminal carbon-carbon double bond represented by the following formula (39), ω-hydroxy-1-alkene having 3 to 12 carbon atoms, terminal carbon-carbon double bond Phenolic compounds with 9 to 18 carbon atoms having a bond, epoxy compounds with 6 to 15 carbon atoms having a terminal carbon-carbon double bond, and carbon having a terminal carbon-carbon double bond or alicyclic carbon-carbon double bond and one or more selected from the number 4 to 32 carboxylic acid anhydride compounds,
Component (c): A block copolymer represented by the above formula (1) can be obtained by carrying out a hydrosilylation reaction of components (a) and (b) in the presence of a hydrosilylation reaction catalyst.

（式（３９）中、Ｒ⁴、ｊ及びｋはそれぞれ上記式（３）に示すものと同じである。なお、上記ｋで括られた繰り返し単位の配列順序は限定されず、ランダムであってもブロックであってもよい。また、上記オキシアルキレン単位は１種または２種以上で構成されたものである。）

(In formula (39), R ⁴ , j and k are each the same as shown in formula (3) above. The arrangement order of the repeating units enclosed by k above is not limited and may be random. (Also, the above oxyalkylene units may be composed of one type or two or more types.)

In the above formula (38), Rf is a perfluoropolyether block represented by the above formula (2), and g' is a number from 0 to 50.

上記式（Ａ’）中、Ｒ¹は上記式（Ａ）中のものと同じである。ｐ１’及びｓ１’はそれぞれ０～１，０００の数であり、好ましくは０～２００の数である。なお、各繰り返し単位の配列順序は限定されず、ランダムであってもブロックであってもよい。 In formula (38), the organopolysiloxane blocks W3 are each independently a divalent group represented by the following formula (A').

In the above formula (A'), R ¹ is the same as in the above formula (A). p1' and s1' are each a number from 0 to 1,000, preferably from 0 to 200. Note that the arrangement order of each repeating unit is not limited, and may be random or block.

上記式（Ｂ’）中、Ｒ¹及びＲ¹’は上記式（Ｂ）中のものと同じである。ｐ２’及びｓ２’はそれぞれ０～１，０００の数であり、好ましくは０～２００の数である。なお、各繰り返し単位の配列順序は限定されず、ランダムであってもブロックであってもよい。
但し、上記式（Ａ’）のハイドロジェンシロキサン単位の数ｓ１’と上記式（Ｂ’）のハイドロジェンシロキサン単位の数ｓ２’は同時に０とならないものである。 In formula (38), the organopolysiloxane blocks W4 are each independently a monovalent group represented by the following formula (B').

In the above formula (B'), R ¹ and R ¹ ' are the same as those in the above formula (B). p2' and s2' are each a number from 0 to 1,000, preferably from 0 to 200. Note that the arrangement order of each repeating unit is not limited, and may be random or block.
However, the number s1' of hydrogen siloxane units in the above formula (A') and the number s2' of hydrogen siloxane units in the above formula (B') do not become 0 at the same time.

In the above formula (38), Q is a divalent organic group having 2 to 12 carbon atoms. Further, Q is bonded to either the terminal carbon atom of Rf, the terminal silicon atom of W3, or the terminal silicon atom of W4.

（式（４０）中、Ｒ⁶及びａは上記式（６）中のものと同じである。） Component (b): The phenol compound having 9 to 18 carbon atoms and having a terminal carbon-carbon double bond is preferably a compound represented by the following formula (40).

(In formula (40), R ⁶ and a are the same as in formula (6) above.)

（式（４１）中、ｊは上記式（７）中のものと同じである。） Component (b): The epoxy compound having 6 to 15 carbon atoms and having a terminal carbon-carbon double bond is preferably a compound represented by the following formula (41) or the following formula (42).

(In formula (41), j is the same as in formula (7) above.)

（式（４３）中、Ｒ⁷は独立して上記式（９）中のものと同じであり、ｂは２～４の数である。）

（式（４４）中、Ｒ⁷は独立して上記式（９）中のものと同じである。）

Component (b): The carboxylic acid anhydride compound having 4 to 32 carbon atoms and having a terminal carbon-carbon double bond or an alicyclic carbon-carbon double bond is preferably represented by the following formulas (43) to (45). It is a compound that is

(In formula (43), R ⁷ is independently the same as in formula (9) above, and b is a number from 2 to 4.)

(In formula (44), R ⁷ is independently the same as in formula (9) above.)

Component (c): The hydrosilylation reaction catalyst is, for example, a platinum, palladium, rhodium or ruthenium catalyst, preferably a platinum catalyst. Examples of platinum catalysts include chloroplatinic acid, alcoholic or aldehyde solutions of chloroplatinic acid, complexes of chloroplatinic acid with various olefins or vinyl siloxanes, and complexes of platinum with various olefins or vinyl siloxanes.

The above component (c): hydrosilylation reaction catalyst may be used in a so-called catalytic amount, and is preferably 0.1 to 200 ppm in terms of metal atomic weight based on the total of the above components (a) and (b).

In the method for producing a block copolymer of the above formula (1) by the hydrosilylation reaction of the above components (a) and (b), optionally the component (d) has a carbon number of 7 to 18 and has a terminal carbon-carbon double bond. aralkyl compounds, ether compounds having 3 to 12 carbon atoms having a terminal carbon-carbon double bond, and oxyalkylene units having 6 to 248 carbon atoms having a terminal carbon-carbon double bond represented by the following formula (46). The hydrosilylation reaction may be performed by adding one or more selected from the compounds having. A siloxane unit represented by the above formula (12) is introduced into the block copolymer of the above formula (1), making it easily compatible with a non-fluorine organic compound.

（式（４６）中、Ｒ⁴、Ｒ⁵、ｍ及びｎはそれぞれ上記式（４）に示すものと同じである。なお、上記ｎで括られた繰り返し単位の配列順序は限定されず、ランダムであってもブロックであってもよい。また、上記オキシアルキレン単位は１種または２種以上で構成されたものである。）

(In formula (46), R ⁴ , R ⁵ , m and n are each the same as shown in formula (4) above. Note that the arrangement order of the repeating units enclosed by n above is not limited and is random. (The oxyalkylene unit may be one type or a block type.)

（式（４７）中、Ｒ⁸は上記式（１３）中のものと同じである。） Component (d): The aralkyl compound having 7 to 18 carbon atoms and having a terminal carbon-carbon double bond is preferably a compound represented by the above formula (47).

(In formula (47), R ⁸ is the same as in formula (13) above.)

Component (d): Examples of the ether compound having 3 to 12 carbon atoms and having a terminal carbon-carbon double bond include compounds represented by the following formula, but are not limited to the following formula.

Component (d): Examples of compounds having an oxyalkylene unit having 6 to 248 carbon atoms and a terminal carbon-carbon double bond include compounds represented by the following formula, but are limited to the following formula: isn't it.

In the method for producing the block copolymer of formula (1) above, component (e): an organic solvent may optionally be added to carry out the hydrosilylation reaction. This reaction can be carried out without a solvent, but by adding an organic solvent, components (a), (b), and (d) become more compatible and the hydrosilylation reaction can proceed efficiently. be.

Component (e) above: Organic solvents include, for example, aromatic hydrocarbons such as toluene and xylene; alcohols such as 1-propanol, 2-propanol, and 1-butanol; (trifluoromethyl)benzene, 1,3-bis Examples include fluorinated aromatic hydrocarbons such as (trifluoromethyl)benzene, and toluene is preferred because it has good compatibility with the components (a), (b), and (d).

Component (e) above: The amount of organic solvent to be used is not particularly limited as long as the above components (a), (b) and (d) are compatible with each other. The amount is preferably 10 to 300% by mass based on the total of components () and (d).

Component (a): The organohydrogenpolysiloxane having a perfluoropolyether block represented by the above formula (38) can be produced using the following method.

In detail, component (f): perfluoropolyether-organopolysiloxane block copolymer represented by the following formula (48), component (g): organohydrogenpolysiloxane, and component (h): acid catalyst. , if necessary, component (i): one or more selected from polysiloxanes represented by the following formula (49) and the following formula (50) are mixed, and component (f), component (g), and ( i) Carry out an exchange reaction between the siloxane and the component.

（式（４９）中、Ｒ¹は上記式（Ａ’）中のものと同じである。ｔ１は３～１０の数であり、好ましくは３～８の数である。）

(In formula (49), R ¹ is the same as in formula (A') above. t1 is a number from 3 to 10, preferably from 3 to 8.)

（式（５０）中、Ｒ¹は上記式（Ｂ’）中のものと同じである。Ｒ⁹は独立してヒドロキシ基、炭素数１～４のアルキル基、又は炭素数１～４のアルコキシ基であり、好ましくはヒドロキシ基、メチル基又はメトキシ基である。ｔ２は０～５，０００の数であり、好ましくは２～１，０００の数である。）

(In formula (50), R ¹ is the same as in formula (B') above. R ⁹ is independently a hydroxy group, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms. (t2 is a number from 0 to 5,000, preferably from 2 to 1,000.)

上記式（Ａ”）中、Ｒ¹は上記式（Ａ’）中のものと同じである。ｐ”は０～１，０００の数であり、好ましくは０～５００の数であり、より好ましくは０～２００の数である。 In the above formula (48), Rf is a perfluoropolyether block represented by the above formula (2), and g'' is a number from 0 to 50.
In the above formula (48), the organopolysiloxane blocks W5 are each independently a divalent group represented by the following formula (A'').

In the above formula (A"), R ¹ is the same as in the above formula (A'). p" is a number from 0 to 1,000, preferably a number from 0 to 500, and more preferably is a number from 0 to 200.

上記式（Ｂ”）中、Ｒ¹及びＲ¹’は上記式（Ｂ’）中のものと同じである。ｑ”は０～１，０００の数であり、好ましくは０～５００の数であり、より好ましくは０～２００の数である。 In the above formula (48), the organopolysiloxane block W6 is a monovalent group represented by the following formula (B'').

In the above formula (B''), R ¹ and R ¹ ' are the same as in the above formula (B'). q'' is a number from 0 to 1,000, preferably a number from 0 to 500. More preferably, the number is from 0 to 200.

In the above formula (42), Q is a divalent organic group having 2 to 12 carbon atoms. Further, Q is bonded to either the terminal carbon atom of Rf, the terminal silicon atom of W5, or the terminal silicon atom of W6.

The above component (g): organohydrogenpolysiloxane may be linear, branched or cyclic, and examples thereof include the following siloxanes.

Component (h) above: The acid catalyst is not particularly limited as long as it can hydrolyze the siloxane bonds of component (f) and (g) above, but sulfuric acid, methanesulfonic acid, trifluoromethanesulfonic acid, etc. preferable.

Component (i): Examples of the polysiloxane represented by the above formula (49) and the above formula (50) include the following siloxanes.

In the method for producing the organohydrogenpolysiloxane of formula (38) using the exchange reaction between siloxanes, optionally component (j): an organic solvent may be added to carry out the exchange reaction between siloxanes. Although this reaction is possible without a solvent, by adding an organic solvent, component (f): perfluoropolyether-organopolysiloxane block copolymer, and the polysiloxanes of components (g) and (i) can be made to interact with each other. It becomes easier to dissolve, and the exchange reaction between siloxanes can proceed efficiently.

(j) Component: The amount of organic solvent used is not particularly limited as long as the above (f) component, (g) component, and (i) component are compatible; It is preferably 10 to 300% by mass based on the total of component (i).

EXAMPLES Hereinafter, the present invention will be specifically explained with reference to Examples and Comparative Examples, but the present invention is not limited to the Examples below. In addition, in the following examples, the weight average molecular weight is a polystyrene equivalent value determined by GPC measurement based on the measurement conditions described above. In addition, in the following example, the number of repeating units g is determined by the integral value M derived from Si of the Si(R ^1' ) ₃ -O- structure based on the above formula (1) in the ²⁹ Si-NMR spectrum, and the above formula (1). ) based on the -Q-Si(R ¹ ) ₂ -O- structure and the integral value M' derived from Si, and g=(M'/M)-1.

[Example 1] Synthesis of block copolymer (1-1) 2.2 g of organohydrogenpolysiloxane having a perfluoropolyether block represented by the following formula (38-1) and ethylene glycol monoallyl ether were placed in a reaction vessel. 0.39 g and 2.5 g of toluene as a solvent were added and stirred at 80° C. for 5 minutes. Next, 0.01 g of a toluene solution of a platinum vinylsiloxane complex was added, and the mixture was stirred at 110° C. for 4 hours. Next, excess ethylene glycol monoallyl ether and toluene as a solvent were distilled off under reduced pressure to obtain 2.3 g of a liquid product.

The measurement results of each NMR spectrum of the obtained product are shown in Tables 1 to 3.

From the above results, it was found that the product had a structure represented by the following formula (1-1) and was a block copolymer with an organopolysiloxane block content of 77% in the molecule. Moreover, the weight average molecular weight of the block copolymer measured by GPC was 12,440 in terms of polystyrene.

[Example 2] Synthesis of block copolymer (1-2) In a reaction vessel, 2.0 g of an organohydrogenpolysiloxane having a perfluoropolyether block represented by the above formula (38-1) and the following formula (46- 0.89 g of a compound having a hydroxyl group having a terminal carbon-carbon double bond represented by 2) and 2.9 g of toluene as a solvent were added, and the mixture was stirred at 85° C. for 5 minutes. Next, 0.02 g of a toluene solution of a platinum vinylsiloxane complex was added, and the mixture was stirred at 100° C. for 3 hours. Next, the solvent toluene was distilled off under reduced pressure to obtain 2.5 g of a liquid product.

The measurement results of each NMR spectrum of the obtained product are shown in Tables 4 to 6.

From the above results, it was found that the product had a structure represented by the following formula (1-2) and was a block copolymer with an organopolysiloxane block content of 83% in the molecule. Moreover, the weight average molecular weight of the block copolymer measured by GPC was 16,600 in terms of polystyrene.

[Example 3] Synthesis of block copolymer (1-3) In a reaction vessel, 3.5 g of organohydrogenpolysiloxane having a perfluoropolyether block represented by the following formula (38-2) and 2-allylphenol 0 .58 g and 3.5 g of toluene as a solvent were added and stirred at 100° C. for 5 minutes. Next, 0.01 g of a toluene solution of a platinum vinylsiloxane complex was added, and the mixture was stirred at 100° C. for 4 hours. Next, excess 2-allylphenol and toluene as a solvent were distilled off under reduced pressure to obtain 3.7 g of a liquid product.

The measurement results of each NMR spectrum of the obtained products are shown in Tables 7 to 9.

From the above results, it was found that the product had a structure represented by the following formula (1-3) and was a block copolymer with an organopolysiloxane block content of 62% in the molecule. Moreover, the weight average molecular weight of the block copolymer measured by GPC was 8,850 in terms of polystyrene.

[Example 4] Synthesis of block copolymer (1-4) 3.0 g of organohydrogenpolysiloxane having a perfluoropolyether block represented by the above formula (38-1) and 0.0 g of allyl glycidyl ether were placed in a reaction vessel. 51 g and 3.0 g of toluene as a solvent were added and stirred at 100° C. for 5 minutes. Next, 0.02 g of a toluene solution of a platinum vinylsiloxane complex was added, and the mixture was stirred at 100° C. for 7 hours. Next, excess allyl glycidyl ether and toluene as a solvent were distilled off under reduced pressure to obtain 2.8 g of a liquid product.

The measurement results of each NMR spectrum of the obtained product are shown in Tables 10 to 12.

From the above results, it was found that the product had a structure represented by the following formula (1-4) and was a block copolymer with an organopolysiloxane block content of 78% in the molecule. Moreover, the weight average molecular weight of the block copolymer measured by GPC was 8,680 in terms of polystyrene.

[Example 5] Synthesis of block copolymer (1-5) In a reaction vessel, 3.0 g of organohydrogenpolysiloxane having a perfluoropolyether block represented by the above formula (38-1) and 0 g of allylsuccinic anhydride were added. .52g and 3.0g of toluene as a solvent were added and stirred at 105°C for 5 minutes. Next, 0.02 g of a toluene solution of a platinum vinylsiloxane complex was added, and the mixture was stirred at 105° C. for 8 hours. Next, excess allylsuccinic anhydride and toluene as a solvent were distilled off under reduced pressure to obtain 3.1 g of a liquid product.

The measurement results of each NMR spectrum of the obtained product were as follows.

From the above results, it was found that the product had a structure represented by the following formula (1-5) and was a block copolymer with an organopolysiloxane block content of 78% in the molecule. Moreover, the weight average molecular weight of the block copolymer measured by GPC was 9,220 in terms of polystyrene.

[Example 6] Synthesis of block copolymer (1-6) In a reaction vessel, 3.0 g of organohydrogenpolysiloxane having a perfluoropolyether block represented by the above formula (38-1) and 0.0 g of isopropenylbenzene were added. 15 g and 3.0 g of toluene as a solvent were added and stirred at 100° C. for 5 minutes. Next, 0.02 g of a toluene solution of a platinum vinylsiloxane complex was added, and the mixture was stirred at 100° C. for 3 hours. Next, 0.30 g of allyl glycidyl ether was added and stirred at 100° C. for 7 hours. Next, excess allyl glycidyl ether and toluene as a solvent were distilled off under reduced pressure to obtain 3.1 g of a liquid product.

The measurement results of each NMR spectrum of the obtained product were as follows.

From the above results, it was found that the product had a structure represented by the following formula (1-6) and was a block copolymer with an organopolysiloxane block content of 76% in the molecule. Moreover, the weight average molecular weight of the block copolymer measured by GPC was 8,950 in terms of polystyrene.

[Example 7] Synthesis of block copolymer (1-7) In a reaction vessel, 3.0 g of organohydrogenpolysiloxane having a perfluoropolyether block represented by the above formula (38-1) and the following formula (46- 0.77 g of a compound having an oxyalkylene unit having a terminal carbon-carbon double bond represented by 7) and 3.5 g of toluene as a solvent were added, and the mixture was stirred at 100° C. for 5 minutes. Next, 0.02 g of a toluene solution of a platinum vinylsiloxane complex was added, and the mixture was stirred at 100° C. for 1 hour. Next, 0.30 g of allyl glycidyl ether was added and stirred at 100° C. for 7 hours. Next, excess allyl glycidyl ether and toluene as a solvent were distilled off under reduced pressure to obtain 3.7 g of a liquid product.

The measurement results of each NMR spectrum of the obtained product were as follows.

From the above results, it was found that the product was a block copolymer having a structure represented by the following formula (1-7), and the organopolysiloxane block content in the molecule was 81%. Moreover, the weight average molecular weight of the block copolymer measured by GPC was 11,170 in terms of polystyrene.

[Comparative example 1 (organopolysiloxane block content in molecule: 0%)]
Perfluoropolyether diol (manufactured by Solvay Specialty Polymers, trade name, Fomblin D2).

[Comparative example 2 (organopolysiloxane block content in molecule: 25%)]
0.59 g of 2-allylphenol and 0.59 g of 1,3-bis(trifluoromethyl)benzene were placed in a reaction vessel, stirred for 5 minutes at 100°C, and 0.01 g of a toluene solution of platinum vinylsiloxane complex was added. added. Next, a mixed solution of 4.4 g of organohydrogenpolysiloxane having a perfluoropolyether block represented by the following formula (51) and 4.4 g of 1,3-bis(trifluoromethyl)benzene was heated at 100°C. The mixture was added dropwise over 15 minutes and further stirred at 100°C for 2 hours. Next, excess 2-allylphenol and 1,3-bis(trifluoromethyl)benzene as a solvent were distilled off under reduced pressure to obtain 4.6 g of a block copolymer represented by the following formula (52).

[Comparative example 3 (organopolysiloxane block content in molecule: 24%)]
Put 0.59 g of allyl glycidyl ether and 0.59 g of 1,3-bis(trifluoromethyl)benzene into a reaction container, stir at 100°C for 5 minutes, and add 0.01 g of a toluene solution of platinum vinyl siloxane complex. added. Next, a mixed solution of 4.4 g of organohydrogenpolysiloxane having a perfluoropolyether block represented by the above formula (51) and 4.4 g of 1,3-bis(trifluoromethyl)benzene was heated at 100°C. The mixture was added dropwise over 15 minutes and further stirred at 100°C for 3 hours. Next, excess allyl glycidyl ether and 1,3-bis(trifluoromethyl)benzene as a solvent were distilled off under reduced pressure to obtain 4.6 g of a block copolymer represented by the following formula (53).

[Comparative example 4 (organopolysiloxane block content in molecule: 26%)]
0.60 g of allylsuccinic anhydride and 0.60 g of 1,3-bis(trifluoromethyl)benzene were placed in a reaction vessel, stirred for 5 minutes at 100°C, and 0.01 g of a toluene solution of platinum vinylsiloxane complex was added. added. Next, a mixed solution of 4.4 g of organohydrogenpolysiloxane having a perfluoropolyether block represented by the above formula (51) and 4.4 g of 1,3-bis(trifluoromethyl)benzene was heated at 105°C. The mixture was added dropwise over 15 minutes and further stirred at 105°C for 4 hours. Next, excess allyl glycidyl ether and the solvent 1,3-bis(trifluoromethyl)benzene were distilled off under reduced pressure to obtain 4.6 g of a block copolymer represented by the following formula (54).

[Evaluation of solubility in non-fluorine organic compounds]
1 g of the block copolymers of the above Examples and Comparative Examples were mixed with 9 g of the non-fluorine organic compound below, and the mixture was visually observed to evaluate solubility according to the following criteria.

Evaluation criteria ○: The mixed liquid is transparent.
△: The mixed liquid is cloudy.
×: The mixed liquid is separated into two phases.

From the results in Table 22, the perfluoropolyether-organopolysiloxane block copolymer of the present invention is more effective than the perfluoropolyether compound without organopolysiloxane or the comparative example block copolymer with a low siloxane content. It was found that it has excellent solubility in organic compounds.
In addition, the perfluoropolyether-organopolysiloxane block copolymer of the present invention has a number of organosiloxane units and a number of siloxane units having one or more groups selected from a hydroxy group, a phenol group, an epoxy group, and a carboxylic acid anhydride group. Since it is easy to control the number of siloxane units having one or more groups selected from , and groups having an aralkyl group and an oxyalkylene unit, it is also possible to control the compatibility and the crosslinking density of the cured product. It is useful as a surface modifier for organic resins, etc.

Claims (12)

A perfluoropolyether-organopolysiloxane block copolymer having a perfluoropolyether block and an organopolysiloxane block represented by the following formula (1), wherein the side chain of the organopolysiloxane block has an oxyalkylene group, A perfluoropolyether-organopolysiloxane block copolymer having one or more organic groups containing a reactive functional group selected from a hydroxyalkyl group, a hydroxyaryl group, an epoxy group, and a carboxylic acid anhydride group.

[In formula (1),
Rf is the following formula (2)

(In formula (2), z is a number from 1 to 4, v, w, x and y are each independently a number from 0 to 200, and v+w+x+y=3 to 200. Also, each repeating unit is It may be linear or branched. The arrangement order of each repeating unit is not limited and may be random or block.)
It is a perfluoropolyether block represented by
W1 is the following formula (A)

(In formula (A), R ¹ is a group independently selected from an alkyl group having 1 to 18 carbon atoms and a phenyl group. R ² is an oxyalkylene group represented by the following formula (3), and 3 carbon atoms. ~12 ω-hydroxyalkyl group, an organic group having 9 to 18 carbon atoms having a hydroxyaryl group, an organic group having 6 to 15 carbon atoms having an epoxy group, and an organic group having 4 to 32 carbon atoms having a carboxylic acid anhydride group R ³ is an aralkyl group having 7 to 18 carbon atoms, an alkoxyalkyl group having 3 to 12 carbon atoms, and an oxyalkylene group represented by the following formula (4). One or more groups selected from

(In formula (3), R ⁴ is an alkylene group having 2 to 4 carbon atoms, j is a number from 3 to 12, and k is a number from 1 to 60. The alkylene unit is composed of one type or two or more types, and when composed of two or more types, the arrangement order of each unit is not limited and may be random or block.)

(In formula (4), R ⁴ is an alkylene group having 2 to 4 carbon atoms, R ⁵ is an alkyl group having 1 to 4 carbon atoms, m is a number from 3 to 12, and n is 1 to 60 In addition, the oxyalkylene units bracketed by n above are composed of one type or two or more types, and when composed of two or more types, the arrangement order of each unit is not limited, (Can be random or block.)
p1, q1, and r1 are each a number from 0 to 1,000. The arrangement order of each repeating unit is not limited, and may be random or block. )
It is a divalent organopolysiloxane block represented by
W2 is each independently expressed by the following formula (B)

(In formula (B), R ¹ is a group independently selected from an alkyl group having 1 to 18 carbon atoms and a phenyl group. R ² is an oxyalkylene group represented by the above formula (3), and 3 carbon atoms. ~12 ω-hydroxyalkyl group, an organic group having 9 to 18 carbon atoms having a hydroxyaryl group, an organic group having 6 to 15 carbon atoms having an epoxy group, and an organic group having 4 to 32 carbon atoms having a carboxylic acid anhydride group R ³ is an aralkyl group having 7 to 18 carbon atoms, an alkoxyalkyl group having 3 to 12 carbon atoms, and an oxyalkylene group represented by the above formula (4). R ¹ ' is a group independently selected from an alkyl group having 1 to 18 carbon atoms and a phenyl group. p2, q2 and r2 are each a number from 0 to 1,000. (The arrangement order of each repeating unit is not limited and may be random or block.)
A monovalent organopolysiloxane block represented by
However, q1 in the above formula (A) and q2 in the above formula (B) do not become 0 at the same time.
Q is a divalent organic group having 2 to 12 carbon atoms, and in the above formula (1), Q is either the terminal carbon atom of Rf, the terminal silicon atom of W1, or the terminal silicon atom of W2. are combined,
g is a number from 0 to 50, but when g is 0, q2 in formula (B) of W2 does not become 0. ]
The perfluoropolyether-organopolysiloxane block copolymer according to claim 1, which has a weight average molecular weight of 4,000 to 500,000 and an organopolysiloxane block content in one molecule of 50% or more.
The perfluoropolyether-organopolysiloxane block copolymer according to claim 1 or 2, wherein the perfluoropolyether block represented by Rf is a group represented by the following formula (5).

(In formula (5), v and w are each a number from 0 to 200, provided that v+w = 3 to 200. Also, the repeating unit of (OC ₂ F ₄ ) may be linear or branched. (The arrangement order of each repeating unit is not limited, and may be random or block.)
A claim in which R ² in formula (A) or formula (B) is an oxyalkylene group represented by formula (3), and R ⁴ in formula (3) is an alkylene group having 2 or 3 carbon atoms. 1. The perfluoropolyether-organopolysiloxane block copolymer according to 1.
The perfluoropolyether-organopolysiloxane block copolymer according to claim 1, wherein R ² in formula (A) or formula (B) is an ω-hydroxyalkyl group having 3 to 12 carbon atoms.
The perfluoropolyether-organopolysiloxane block copolymer according to claim 1, wherein R ² in formula (A) or formula (B) is an organic group having a hydroxyaryl group represented by the following formula (6).

(In formula (6), a is a number from 3 to 4, and R ⁶ is a group selected from a hydrogen atom, a methoxy group, and a hydroxy group.)
The perfluoropolyether-organopolysiloxane block copolymer according to claim 6, wherein in formula (6), R ⁶ is a hydrogen atom or a methoxy group.
The perfluoropolyether-organopolysiloxane block copolymer according to claim 1, wherein R ² in formula (A) or formula (B) is an organic group having an epoxy group represented by the following formula (7).

(In formula (7), j is a number from 3 to 12.)
The perfluoropolyether-organopolysiloxane block copolymer according to claim 1, wherein R ² in formula (A) or formula (B) is an organic group having an epoxy group represented by the following formula (8).

The perfluoropolyether according to claim 1, wherein R ² in formula (A) or formula (B) is an organic group having a carboxylic acid anhydride group represented by the following formula (9) or (10). Organopolysiloxane block copolymer.

(In formula (9), R ⁷ is independently a group selected from a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, and a phenyl group. b is 0 to 4.)

The perfluoropolyether-organopolysiloxane block copolymer according to claim 1, wherein in formula (A) and formula (B), r1+r2>1.
The perfluoropolyether-organopolysiloxane block copolymer according to claim 11, wherein R ³ in formula (A) or formula (B) is an oxyalkylene group represented by formula (4).