JP5962568B2 - Fluoropolyether compound - Google Patents

Description

  The present invention relates to a novel fluoropolyether compound.

  In recent years, the surface of various articles typified by plastic resins is coated with a hard coat agent and cured to protect the surface and impart a new function in a very wide range.

  These hard coating agents have antifouling properties, weather resistance, slip properties, antistatic properties, antistatic properties in addition to conventionally required hardness, wear resistance, chemical resistance, durability, etc. There has been a demand for further enhancement of functions such as fogging, difficulty in focusing, and antireflection properties. Among them, there is a demand for improvement in antifouling properties, dirt wiping properties, particularly fingerprint resistance and fingerprint wiping properties.

  For example, as a method for imparting antifouling property to an acrylic curable composition, an attempt is made to repel dirt components containing water and oil by creating a fluorine-based compound layer on the surface and improving water and oil repellency. Widely made. As a typical method, there is a wide range of methods in which a polymerizable monomer having a perfluoroalkyl group in the side chain, for example, a polymer obtained from a fluorine-containing alkyl ester of acrylic acid or a fluorine-containing alkyl ester of methacrylic acid is mixed in the composition. As is known, in recent years, blending of an acrylic compound having a fluoropolyether group and the like has been studied in order to obtain more advanced characteristics. These acrylic compounds having a fluoropolyether group are mixed with a curable composition comprising a non-fluorinated acrylic compound, and when coated, the surface-free energy is used to cause the fluorine-containing group to emerge on the surface. The outermost surface layer having a high fluorine content is formed. The present inventor also disclosed a fluoropolyether group in JP 2010-53114 A, JP 2010-138112 A, JP 2010-285501 A, JP 2011-241190 A (Patent Documents 1 to 4), and the like. The invention about the acrylic compound which has and the curable composition using the same is proposed.

  Particularly expected as a useful application field of such a coating agent containing an acrylic compound having a fluoropolyether group is a surface antifouling coating of a touch panel display.

  As the use of touch panel displays expands, in addition to the operation called “tap” in which the finger simply touches one point on the panel, the operation method is “flick” operation, drag “drag” operation, and “pinch”. It has been extended to operations that have a great significance in the dynamic contact between the finger itself and the screen, such as a “pinch” operation. As a result, touch panel display coatings have become extremely important in terms of touch when a finger is slid, in addition to conventional water repellency, oil repellency, antifouling properties, fingerprint resistance, and fingerprint wiping properties. .

  In the case of a coating agent containing an acrylic compound having a fluoropolyether group, the slipping feeling when the finger is slid is fixed to the fluoropolyether structure on the surface of the coating layer by the reaction of the acrylic group. There was a limit to improvement.

  On the other hand, in addition to performance such as antifouling property, fingerprint resistance, and fingerprint wiping property, as a method for obtaining a better tactile sensation, a fluoropolyether compound having no polymerizable group may be disposed on the outermost surface of the coating layer. Conceivable. The simplest method is a method in which a non-functional fluoropolyether compound is further coated on the coating layer once coated. In this case, a double process is required for coating.

  On the other hand, when the non-functional fluoropolyether compound is directly blended into the coating composition, a sufficient slip feeling cannot be obtained in the case of a low molecular fluoropolyether compound soluble in a general non-fluorinated coating agent. Since fluoropolyether having a length sufficient to obtain a slipperiness is not dissolved in the coating composition, precipitation and turbidity are generated, and there is a problem that uniform coating cannot be performed.

  For this reason, it has been desired to develop a fluoropolyether compound that is soluble in a non-fluorinated coating composition, has a sufficient slip feeling, and does not have a polymerizable group.

JP 2010-53114 A JP 2010-138112 A JP 2010-285501 A JP 2011-241190 A

  The present invention has been made in view of the above circumstances, and provides a novel fluoropolyether compound that is soluble in a non-fluorinated coating composition, has a sufficient slip feeling, and does not have a polymerizable group. With the goal.

  As a result of intensive studies to achieve the above object, the inventor has found that the fluoropolyether compound represented by the following general formula (1) is soluble in an existing non-fluorinated coating composition, In addition to the properties such as water repellency, oil repellency, antifouling property, fingerprint resistance and fingerprint wiping property, the inventors have found that a cured product layer having an excellent slip feeling can be formed, and have reached the present invention.

（Ｒは構造中に（メタ）アクリル基、エポキシ基及び水酸基を含まない炭素数２〜３０の１価の炭化水素基であり、環状構造をなしていてもよく、途中エポキシ基以外のエーテル結合又はエステル結合を含んでいてもよく、一部の水素原子がハロゲン原子で置換されていてもよい。）
で表される基である。Ｑはそれぞれ独立に炭素数１〜２０の２価の炭化水素基であり、環状構造をなしていてもよく、途中エーテル結合（−Ｏ−）又はエステル結合（−ＣＯＯ−）を含んでいてもよい。Ｙはそれぞれ（ａ＋１）個のＳｉ原子を有するシロキサン構造、非置換又はハロゲン置換のシルアルキレン構造、シルアリーレン構造又はこれらの２種以上の組み合せからなる（ａ＋１）価の連結基であり、環状構造をなしていてもよい。Ｚは独立に下記式

から選ばれる少なくとも１種の２価の連結基であり、酸素原子、窒素原子、フッ素原子又はケイ素原子を含んでいてもよく、また環状構造及び／又は不飽和結合を有する基であってもよい。〕
で示されるフルオロポリエーテル化合物。
〔２〕
Ｙが、下記式

（式中、ａは式（１）におけるａと同じであり、破線は結合手を示し、ａの繰り返し単位を有するユニットの破線はＱ基と結合し、残る一つの破線はＺと結合する。）
で表される基である〔１〕記載の化合物。
〔３〕
下記一般式（２）
（ＨＯ−Ｑ）_a−Ｙ−Ｚ−Ｒｆ−Ｚ−Ｙ−（Ｑ−ＯＨ）_a （２）
（式中、Ｒｆ、ａ、Ｑ、Ｙ、Ｚは式（１）におけるＲｆ、ａ、Ｑ、Ｙ、Ｚと同じである。）
で示される化合物に、下記一般式（３）
Ｒ−Ｎ＝Ｃ＝Ｏ （３）
（式中、Ｒは式（１）におけるＲと同じである。）
で示される化合物を反応させることにより得られる〔１〕又は〔２〕に記載の化合物。
〔４〕
Ｑが、
−ＣＨ₂ＣＨ₂ＣＨ₂−
−ＣＨ₂ＣＨ₂ＣＨ₂ＣＨ₂−
−ＣＨ₂ＣＨ₂ＣＨ₂ＣＨ₂ＣＨ₂−
−ＣＨ₂ＣＨ₂ＣＨ₂ＯＣＨ₂ＣＨ₂−
−ＣＨ₂ＣＨ₂ＣＨ₂ＯＣＨ₂ＣＨ₂ＯＣＨ₂ＣＨ₂−
−ＣＨ₂ＣＨ₂ＣＨ₂ＯＣＨ₂ＣＨ₂ＯＣＨ₂ＣＨ₂ＯＣＨ₂ＣＨ₂−

で示される群の中より選ばれる基である〔１〕〜〔３〕のいずれかに記載の化合物。
〔５〕
下記式で示される化合物である〔１〕〜〔４〕のいずれかに記載の化合物。

（式中、Ｒは式（１）におけるＲと同じであり、ｊは１又は２であり、ｍ＋ｎは１０〜７０の整数であり、ｍ／ｎは０．５〜１．５であり、各繰り返し単位の配列はランダムである。）

Accordingly, the present invention provides the following fluoropolyether compound.
[1]
The following general formula (1)
(XQ) _a -YZ-Rf-ZY- (QX) _a (1)
[In the formula, Rf is a structural unit having a number average molecular weight of 1,000 to 40,000 as —CF ₂ O—, — (CF ₂ ) ₂ O—, — (CF ₂ ) ₃ O—, — (CF ₂ ) ₄ O-either, or a divalent linear fluoropolyether group having a repeating structure with multiple combinations of these, a is independently an integer from 1 to 20. X is independently

(R is a monovalent hydrocarbon group having 2 to 30 carbon atoms that does not contain a (meth) acryl group, an epoxy group, or a hydroxyl group in the structure, may have a cyclic structure, and is an ether bond other than an epoxy group on the way. Or an ester bond may be included, and a part of hydrogen atoms may be substituted with a halogen atom.)
It is group represented by these. Q is each independently a divalent hydrocarbon group having 1 to 20 carbon atoms, may have a cyclic structure, and may contain an ether bond (—O—) or an ester bond (—COO—). Good. Y is a (a + 1) -valent linking group composed of a siloxane structure having (a + 1) Si atoms, an unsubstituted or halogen-substituted silalkylene structure, a silarylene structure, or a combination of two or more thereof, and a cyclic structure You may have done. Z is independently the following formula

Is a divalent linking group selected from the group consisting of an oxygen atom, a nitrogen atom, a fluorine atom or a silicon atom, or a group having a cyclic structure and / or an unsaturated bond. . ]
In fluoropolyether compound represented.
[2 ]
Y is the following formula

(In the formula, a is the same as a in formula (1), the broken line indicates a bond, the broken line of the unit having the repeating unit of a is bonded to the Q group, and the remaining broken line is bonded to Z. )
[1] The compound according to [1] .
[ 3 ]
The following general formula (2)
(HO-Q) _a -YZ-Rf-ZY- (Q-OH) _a (2)
(In the formula, Rf, a, Q, Y, and Z are the same as Rf, a, Q, Y, and Z in Formula (1).)
In the compound represented by the following general formula (3)
RN = C = O (3)
(In the formula, R is the same as R in formula (1).)
The compound as described in [1] or [2] obtained by making the compound shown by react .
[4 ]
Q is
—CH ₂ CH ₂ CH ₂ —
—CH ₂ CH ₂ CH ₂ CH ₂ —
—CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ —
_{-CH 2 CH 2 CH 2 OCH 2} CH 2 -
_{-CH 2 CH 2 CH 2 OCH 2} CH 2 OCH 2 CH 2 -
_{-CH 2 CH 2 CH 2 OCH 2} CH 2 OCH 2 CH 2 OCH 2 CH 2 -

The compound in any one of [1]-[ 3 ] which is group selected from the group shown by these.
[ 5 ]
The compound according to any one of [1] to [ 4 ], which is a compound represented by the following formula.

(In the formula, R is the same as R in Formula (1), j is 1 or 2, m + n is an integer of 10 to 70, m / n is 0.5 to 1.5, and (The arrangement of repeat units is random.)

  The fluoropolyether compound of the present invention is blended with an existing curable coating composition to give an excellent slip feeling to the surface after curing of the composition in addition to water and oil repellency, fingerprint resistance and antifouling property. The cured product layer can be formed and is extremely useful as an additive for the coating composition.

（Ｒは構造中に（メタ）アクリル基、エポキシ基及び水酸基を含まない炭素数２〜３０の１価の炭化水素基であり、環状構造をなしていてもよく、途中エポキシ基以外のエーテル結合又はエステル結合を含んでいてもよく、一部の水素原子がハロゲン原子で置換されていてもよい。）
で表される基である。Ｑはそれぞれ独立に炭素数１〜２０、好ましくは２〜１５の２価の炭化水素基であり、環状構造をなしていてもよく、途中エーテル結合（−Ｏ−）又はエステル結合（−ＣＯＯ−）を含んでいてもよい。Ｙは独立に（ａ＋１）価の連結基であり、環状構造をなしていてもよい。Ｚは独立に２価の連結基であり、酸素原子、窒素原子、フッ素原子又はケイ素原子を含んでいてもよく、また環状構造あるいは不飽和結合を有する基であってもよい。〕 Hereinafter, the present invention will be described in detail.
The fluoropolyether compound of the present invention is represented by the following general formula (1).
(XQ) _a -YZ-Rf-ZY- (QX) _a (1)
[Wherein, Rf is a divalent linear fluoropolyether group having a number average molecular weight of 1,000 to 40,000, and a is an integer of 1 to 20 independently. X is independently

(R is a monovalent hydrocarbon group having 2 to 30 carbon atoms that does not contain a (meth) acryl group, an epoxy group, or a hydroxyl group in the structure, may have a cyclic structure, and is an ether bond other than an epoxy group on the way. Or an ester bond may be included, and a part of hydrogen atoms may be substituted with a halogen atom.)
It is group represented by these. Each Q is independently a divalent hydrocarbon group having 1 to 20 carbon atoms, preferably 2 to 15 carbon atoms, and may have a cyclic structure, and an ether bond (—O—) or ester bond (—COO—) ) May be included. Y is independently an (a + 1) -valent linking group and may have a cyclic structure. Z is independently a divalent linking group, may contain an oxygen atom, a nitrogen atom, a fluorine atom or a silicon atom, and may be a group having a cyclic structure or an unsaturated bond. ]

In the above formula (1), Rf is a divalent linear fluoropolyether having a number average molecular weight of 1,000 to 40,000, preferably 1,500 to 20,000, particularly preferably 2,000 to 12,000. It is a group. If the number average molecular weight is too small, the sliding effect imparted by the Rf group is lowered, and if the number average molecular weight is too large, the solubility in a non-fluorinated coating composition is lowered. In the present invention, the molecular weight is a number average molecular weight calculated from the ratio between the terminal structure and the main chain structure based on ¹ H-NMR and ¹⁹ F-NMR.

Further, Rf is selected from the group consisting as structural _{units, -CF 2 O -, - CF} 2 CF 2 O -, - CF 2 CF 2 CF 2 O -, - CF 2 CF 2 CF 2 CF 2 O- either, or their It is preferable that it is a linear fluoropolyether group which has a repeating structure by the combination of several of these, Especially preferably, it is a structure represented by the following.
−C _j F _2j (OCF ₂ CF ₂ ) _m (OCF ₂ ) _n OC _j F _2j −
(In the formula, j is 1 or 2, m + n is an integer of 10 to 70, m / n is 0.5 to 1.5, and the arrangement of each repeating unit is random.)

In the formula (1), each Q is independently a divalent hydrocarbon group having 1 to 20 carbon atoms, preferably 2 to 15 carbon atoms, and may have a cyclic structure, and an ether bond (—O—) or An ester bond (—COO—) may be included. Specifically, the following structures are exemplified.
—CH ₂ CH ₂ CH ₂ —
—CH ₂ CH ₂ CH ₂ CH ₂ —
—CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ —
_{-CH 2 CH 2 CH 2 OCH 2} CH 2 -
_{-CH 2 CH 2 CH 2 OCH 2} CH 2 OCH 2 CH 2 -
_{-CH 2 CH 2 CH 2 OCH 2} CH 2 OCH 2 CH 2 OCH 2 CH 2 -

ここで、Ｒは構造中に（メタ）アクリル基、エポキシ基及び水酸基を含まない炭素数２〜３０、特に炭素数４〜２０の１価の炭化水素基であり、環状構造をなしていてもよく、途中エポキシ基以外のエーテル結合又はエステル結合を含んでいてもよく、一部の水素原子がハロゲン原子で置換されていてもよい。 In formula (1), each X is independently a group represented by the following formula.

Here, R is a monovalent hydrocarbon group having 2 to 30 carbon atoms, particularly 4 to 20 carbon atoms, which does not contain a (meth) acryl group, an epoxy group or a hydroxyl group in the structure, and has a cyclic structure. In addition, an ether bond or an ester bond other than an epoxy group may be included on the way, and a part of hydrogen atoms may be substituted with a halogen atom.

上記Ｒ基は、一分子中で１種単独でも、それぞれ独立した２種以上であってもよい。 Particularly preferable examples of such R include an acyclic alkyl group having 2 to 20 carbon atoms, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a phenyl group, a tolyl group, a benzyl group, a toluyl group, a dimethylphenyl group, Examples thereof include a methoxyphenyl group, an ethoxyphenyl group, a phenethyl group, a naphthyl group, or a group having a structure shown below.

The R group may be one kind alone or two or more kinds independently in one molecule.

  In Formula (1), a is an integer of 1-20 independently, Preferably it is an integer of 1-15, More preferably, it is an integer of 1-4.

In the formula (1), Y is independently a (a + 1) -valent linking group and may have a cyclic structure. Preferred examples of such Y include (a + 1) -valent siloxane structures each having (a + 1) Si atoms, an unsubstituted or halogen-substituted silalkylene structure, a silarylene structure, or a combination of two or more thereof. Examples include a linking group. Specifically, the following structures are specifically shown as preferable structures.
However, a is the same as a of the said Formula (1), and is an integer of 1-20 independently, Preferably it is an integer of 1-15, More preferably, it is an integer of 1-4. b is an arbitrary positive integer of 0 or more, and the upper limit of b is preferably 20 or less, particularly preferably 10 or less. The arrangement of each unit is random, and the bond shown by the broken line of each (a + 1) unit is bonded to one of Z and Q groups.

Here, T is a (a + 1) -valent linking group, and examples thereof include the following.

  In the formula (1), Z is independently a divalent linking group, may contain an oxygen atom, a nitrogen atom, a fluorine atom or a silicon atom, or may be a group having a cyclic structure or an unsaturated bond. Good. Examples of such Z include those shown below. In the formula, Ph represents a phenyl group.

が好ましい。 Especially among these

Is preferred.

As a suitable method for obtaining the fluoropolyether compound represented by the general formula (1) as described above, the following general formula (2)
(HO-Q) _a -YZ-Rf-ZY- (Q-OH) _a (2)
(In the formula, Rf, a, Q, Y, and Z are the same as above.)
A fluoropolyether compound (i) having a polyhydric alcohol group at both ends represented by the following general formula (3):
RN = C = O (3)
(In the formula, R is the same as above.)
The method of making it react with the compound (ii) shown by these is mentioned.

The fluoropolyether compound (i) having a polyhydric alcohol group at both ends represented by the general formula (2) can be synthesized, for example, by the following method.
First, with respect to the fluorine-containing compound (a) having an olefin group at the terminal, a polyfunctional Si—H compound (for example, a siloxane having 2 or more, preferably 3 or more Si—H groups in the molecule, An organosilicon compound consisting of silalkylene, silarylene or a combination of two or more thereof (b) is subjected to a hydrosilylation addition reaction under a large excess of Si—H groups to give a fluorine-containing polyfunctional Si—H compound (c ).

As the fluorine-containing compound (a) having an olefin group at the terminal, the following general formula Z′—Rf—Z ′
(In the formula, Rf is the same as described above. Z ′ may independently contain an oxygen atom, a nitrogen atom, a fluorine atom or a silicon atom, or may be a group having a cyclic structure or an unsaturated bond. , A monovalent group having an unsaturated bond at the terminal.)
The compound shown by these is mentioned.

Here, examples of Z ′ include those shown below. In the formula, Ph represents a phenyl group.

（式中、ｊ、ｍ、ｎは上記と同じである。） As such a fluorine-containing compound (a) having an olefin group at the terminal, a structure represented by the following formula is particularly suitable.

(Where j, m and n are the same as above)

Moreover, as a compound (b), what is shown with the following general formula can be illustrated.
Y- (H) _{a + 1}
(In the formula, Y and a are the same as above.)

The following can be illustrated as a preferable compound (b) among such things.

（式中、ａ、ｂは上記と同じである。）

(Wherein a and b are the same as above)

  By performing an addition reaction at a reaction temperature of 50 to 150 ° C., preferably 60 to 120 ° C. in the presence of a platinum group metal-based addition reaction catalyst, in any combination of the compound (a) and the compound (b) as described above. A fluorine-containing polyfunctional Si—H compound (c) can be obtained.

  The above addition reaction can be carried out without a solvent, but may be diluted with a solvent as necessary. At this time, a widely used organic solvent such as toluene, xylene, and isooctane can be used as the diluting solvent. However, the boiling point is higher than the target reaction temperature and does not hinder the reaction, and the compound formed after the reaction ( Those in which c) is soluble at the reaction temperature are preferred. For example, a partially fluorine-modified solvent such as a fluorine-modified aromatic hydrocarbon solvent such as m-xylene hexafluoride or benzotrifluoride or a fluorine-modified ether solvent such as methyl perfluorobutyl ether is desirable. Hexafluoride is preferred.

  As the addition reaction catalyst, for example, a compound containing platinum, rhodium or palladium can be used. Among them, a compound containing platinum is preferable, hexachloroplatinic acid (IV) hexahydrate, platinum carbonyl vinylmethyl complex, platinum-divinyltetramethyldisiloxane complex, platinum-cyclovinylmethylsiloxane complex, platinum-octylaldehyde / octanol complex, Alternatively, platinum supported on activated carbon can be used. The compounding amount of the catalyst is preferably such that the amount of metal contained is 0.1 to 5,000 mass ppm, more preferably 1 to 1,000 mass ppm with respect to the compound (a).

  Compound (a) and compound (b) are preferably added in a ratio (molar ratio) of 1: 2, and for this purpose, compound (b) is added in a large excess to compound (a). Specifically, it is preferable to perform the addition reaction at a ratio of 8 to 20 mol, particularly 10 to 16 mol, of compound (b) with respect to 1 mol of compound (a). If necessary, only components having an addition ratio of 1: 2 may be extracted from a mixture containing different addition ratios of the compound (a) and the compound (b) by means such as preparative chromatography or molecular distillation. .

In the addition reaction, the order in which each component is charged is not particularly limited. For example, the method of gradually heating the mixture of the compound (a), the compound (b) and the addition reaction catalyst from room temperature to the addition reaction temperature, the compound (a) and the compound A method of adding an addition reaction catalyst after heating the mixture of (b) and the diluting solvent to the target reaction temperature, and adding the compound (a) to the mixture of the compound (b) and the addition reaction catalyst heated to the target reaction temperature. Or a method of dropping a mixture of the compound (a) and the addition reaction catalyst into the compound (b) heated to the target reaction temperature. Among these, the method of adding the addition reaction catalyst after heating the mixture of the compound (a), the compound (b) and the diluting solvent to the target reaction temperature, or the compound (b) heated to the target reaction temperature. Particularly preferred is a method in which the mixture of the compound (a) and the addition reaction catalyst is added dropwise. These methods can be used by diluting each component or mixture with a solvent as necessary. The above reaction is carried out in a dry atmosphere in air or an inert gas (N ₂ , Ar, etc.) at a reaction temperature of 50 to 150 ° C., preferably 60 to 120 ° C., and a reaction time of 0.5 to 96 hours, preferably 1 It is desirable to perform for ~ 48 hours.

（式中、ｊ、ｍ、ｎは上記と同じである。） Here, as the obtained fluorine-containing polyfunctional Si—H compound (c), the following general formula (H) _a —YZ—Rf—ZY— (H) _a
(In the formula, Rf, a, Y and Z are the same as above.)
The compound shown by these is mentioned.

(Where j, m and n are the same as above)

  Performing an addition reaction between the Si—H group of the fluorine-containing polyfunctional Si—H compound (c) obtained as described above and the compound (d) having a terminal olefin group and an alcoholic hydroxyl group in one molecule. Thus, a fluoropolyether compound (i) having a polyhydric alcohol group at both ends represented by the general formula (2) can be obtained.

As such a compound (d), the following are particularly preferable. These compounds (d) can be used individually by 1 type or in combination of 2 or more types.
CH ₂ = CHCH ₂ OH
CH ₂ = CHCH ₂ CH ₂ OH
CH ₂ = CHCH ₂ CH ₂ CH ₂ OH
CH ₂ = CHCH ₂ OCH ₂ CH ₂ OH
CH ₂ = CHCH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OH
CH ₂ = CHCH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OH

The addition reaction of the compound (c) and the compound (d) can be performed by the same method as the addition reaction of the compound (a) and the compound (b) described above. That is, in the presence of the above-mentioned addition reaction catalyst, in a dry atmosphere, in air or an inert gas (N ₂ , Ar, etc.), a reaction temperature of 50 to 150 ° C., preferably 60 to 100 ° C., and a reaction time of 0.5 to The reaction can be carried out in any order of addition by performing dilution for 96 hours, preferably 1 to 48 hours, if necessary.

  The compounding amount of the compound (d) with respect to the compound (c) can be any amount, but the terminal olefin group of the compound (d) is equimolar or 1 mol of the Si-H group of the compound (c). Excess amount, specifically, 1.0 to 5.0 mol, preferably 1.0 to 2.0 mol of the terminal olefin group of compound (d) with respect to 1 mol of Si—H group of compound (c). It is desirable to perform an addition reaction using a molar amount, and it is desirable to remove the unreacted compound (d) by distillation under reduced pressure or the like after the reaction.

（式中、ｊ、ｍ、ｎは上記と同じである。） As the particularly preferred structure of the thus obtained fluoropolyether compound (i) having a polyhydric alcohol group at both ends represented by the general formula (2), the following can be exemplified.

(Where j, m and n are the same as above)

The reaction between the compound (i) represented by the general formula (2) and the compound (ii) represented by the general formula (3) is carried out under a dry atmosphere in air or an inert gas (N ₂ , Ar, etc.), at a reaction temperature. It is possible to proceed by mixing both at 0 to 120 ° C., preferably 20 to 100 ° C., under a reaction time of 0.5 to 48 hours, preferably 1 to 4 hours. The reaction of the compound (i) and the compound (ii) can be performed either individually or in combination.

  The reaction ratio of the compound (i) represented by the general formula (2) and the compound (ii) represented by the general formula (3) is to react all the hydroxyl groups of the compound (i) with the isocyanate group of the compound (ii). The compound (ii) is preferably used so that the amount of the isocyanate group is equal to or more than the number of moles of the hydroxyl group of the compound (i). Therefore, the compound (i) contained in the reaction system When the amount of the hydroxyl group is 1 mol, it is preferable to carry out the reaction in such a ratio that the amount of the isocyanate group of the compound (ii) is 1.0 to 3.0 mol, particularly 1.0 to 2.0 mol. When unreacted compound (ii) remains, it may be removed by a known method such as distillation under reduced pressure.

  In the above reaction, an appropriate catalyst may be added to increase the reaction rate. Examples of the catalyst include dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dioctoate, dioctyltin diacetate, dioctyltin dilaurate, dioctyltin dioctate, stannous dioctanoate, tin compounds such as tetraisopropoxytitanium, tetra n-butoxytitanium, tetrakis (2-ethylhexoxy) titanium, dipropoxybis (acetylacetona) titanium, titanium isopropoxyoctylene glycol and other titanates or titanium chelate compounds, zirconium tetraacetylacetonate, zirconium tributoxy Monoacetylacetonate, zirconium monobutoxyacetylacetonate bis (ethylacetoacetate), zirconium dibutoxybis (ethylacetoacetate) Over G), although zirconium tetraacetyl acetonate, zirconium chelate compound and the like, these are not limited to one type thereof may be used as a mixture of two or more kinds. The reaction rate can be increased by adding these catalysts in an amount of 0.01 to 2% by mass, preferably 0.05 to 1% by mass, based on the total mass of the reactants.

  Moreover, you may dilute with a suitable solvent as needed and may react. As such a solvent, any solvent that does not react with isocyanate groups and hydroxyl groups can be used without particular limitation. Specifically, ethers such as tetrahydrofuran, diisopropyl ether, dibutyl ether, acetone, methyl ethyl ketone, methyl butyl, etc. Ketones such as ketone, methyl isobutyl ketone, and cyclohexanone are exemplified.

（式中、Ｒ、ｊ、ｍ、ｎは上記と同じである。） Specific examples of the fluoropolyether compound represented by the general formula (1) thus obtained are shown below.

(In the formula, R, j, m and n are the same as above.)

  The fluoropolyether compound represented by the general formula (1) obtained by the reaction as described above is subjected to purification and isolation operations such as concentration, column purification, distillation, extraction, and the reaction solution is directly represented by the general formula (1). It can also be used as a mixture containing the indicated fluoropolyether compound or further diluted with an organic solvent or the like.

  The fluoropolyether compound of the present invention obtained as described above is formulated on the surface of a substrate by blending it with, for example, an existing coating for surface protection of various substrates and a curable composition for paint. In addition to dirtiness and fingerprint wiping, it can give a smooth feel with high operability. As a result, the surface of the base material becomes difficult to be soiled by human fats such as fingerprints, sebum, sweat, cosmetics, etc., and even if dirt is attached, a surface having excellent wiping properties is provided. For this reason, the fluoropolyether compound of the present invention is used to form a coating film or a protective film applied to the surface of an article that may be touched by the human body and contaminated by human fat, cosmetics, etc. It is particularly useful as an additive for coating compositions.

  Such hard-coated products include various screen display operations such as liquid crystal displays, plasma displays, electroluminescence displays, rear projection displays, fluorescent display tubes (VFD), field emission projection displays, CRTs, and toner-based displays. Equipment; particularly specific applications include information terminals such as PCs, smartphones, tablet terminals, mobile phones, portable media players, portable game machines, game machine controllers, electronic book readers, digital cameras, digital video cameras, digital Photo frames, portable GPS terminals, watches, control terminals for various electronic devices, navigation devices for automobiles, image display devices such as security system terminals, electronic bulletin boards, electronic signage, electronic Guide plates, automatic cash withdrawal deposit device, cash dispenser, various vending machines, electronic registers, a touch panel to display and the operation (touch sensor, a touch screen) image display input device and the like.

  EXAMPLES Hereinafter, although a synthesis example, an Example, and a comparative example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example.

Ｒｆ’：−ＣＦ₂（ＯＣＦ₂ＣＦ₂）_p（ＯＣＦ₂）_qＯＣＦ₂−
（ｐ／ｑ＝０．９、ｐ＋ｑ≒４５） [Synthesis Example 1]
Under a dry nitrogen atmosphere, to a 2,000ml three-necked flask equipped with a reflux device and a stirrer, the following formula _{CH 2 = CH-CH 2 -O} -CH 2 -Rf'-CH 2 -O-CH 2 -CH = CH ₂
Rf ′: —CF ₂ (OCF ₂ CF ₂ ) _p (OCF ₂ ) _q OCF ₂ —
(P / q = 0.9, p + q≈45)
500 g [0.125 mol] of a perfluoropolyether having α-unsaturated bonds at both ends represented by the formula, 700 g of m-xylene hexafluoride and 361 g of tetramethylcyclotetrasiloxane [1.50 mol] And heated to 90 ° C. with stirring. Here, 0.442 g of a toluene solution of platinum / 1,3-divinyl-tetramethyldisiloxane complex (containing 1.1 × 10 ⁻⁶ mol as Pt alone) was added, and the internal temperature was maintained at 90 ° C. or higher. Stirring was continued for 4 hours. After confirming disappearance of the allyl group of the raw material by ¹ H-NMR, the solvent and excess tetramethylcyclotetrasiloxane were distilled off under reduced pressure. Thereafter, activated carbon treatment was performed to obtain 498 g of a colorless and transparent liquid compound (I) represented by the following formula.

Rf ′: —CF ₂ (OCF ₂ CF ₂ ) _p (OCF ₂ ) _q OCF ₂ —
(P / q = 0.9, p + q≈45)

Ｒｆ’：−ＣＦ₂（ＯＣＦ₂ＣＦ₂）_p（ＯＣＦ₂）_qＯＣＦ₂−
（ｐ／ｑ＝０．９、ｐ＋ｑ≒４５） Under a dry air atmosphere, 7.05 g of 2-allyloxyethanol [amount of allyl group: 0.0690 mol] with respect to 50.0 g of compound (I) obtained above [the amount of Si—H group of 0.0669 mol] , 50.0 g of m-xylene hexafluoride, and 0.0442 g of toluene solution of chloroplatinic acid / vinylsiloxane complex (containing 1.1 × 10 ⁻⁷ mol as a simple substance of Pt), and stirred at 100 ° C. for 4 hours. did. After confirming the disappearance of the Si-H group by ¹ H-NMR and IR, the solvent and excess 2-allyloxyethanol were distilled off under reduced pressure, the activated carbon treatment was performed, and a pale yellow transparent liquid represented by the following formula 55.2 g of perfluoropolyether-containing compound (II) was obtained.

Rf ′: —CF ₂ (OCF ₂ CF ₂ ) _p (OCF ₂ ) _q OCF ₂ —
(P / q = 0.9, p + q≈45)

Ｒｆ’：−ＣＦ₂（ＯＣＦ₂ＣＦ₂）_p（ＯＣＦ₂）_qＯＣＦ₂−
（ｐ／ｑ＝０．９、ｐ＋ｑ≒４５）

[Example 1]
Under a dry air atmosphere, 50.0 g of methyl ethyl ketone (MEK) and m-tolyl isocyanate 9.89 g [isocyanate] with respect to 50.0 g of the compound (II) obtained in Synthesis Example 1 [hydroxyl amount 0.0589 mol] Base amount 0.0743 mol] was mixed and heated to 50 ° C. Dioctyltin dilaurate 0.05g was added there, and it stirred at 35 degreeC for 4 hours. After completion of the heating, vacuum distillation was performed at 120 ° C. and 0.27 kPa to obtain 57.1 g of a pale yellow pasty substance. ^From the results of ¹ H-NMR and IR, it was confirmed to be the compound (III) represented by the following formula.

Rf ′: —CF ₂ (OCF ₂ CF ₂ ) _p (OCF ₂ ) _q OCF ₂ —
(P / q = 0.9, p + q≈45)

Ｒｆ’：−ＣＦ₂（ＯＣＦ₂ＣＦ₂）_p（ＯＣＦ₂）_qＯＣＦ₂−
（ｐ／ｑ＝０．９、ｐ＋ｑ≒４５）

[Example 2]
Under a dry air atmosphere, 50.0 g of the compound (II) obtained in Synthesis Example 1 [hydroxyl amount 0.0589 mol], MEK 50.0 g and cyclohexyl isocyanate 9.30 g [isocyanate group amount 0.0743 mol ] And heated to 50 ° C. Dioctyltin dilaurate 0.05g was added there, and it stirred at 35 degreeC for 4 hours. After completion of the heating, vacuum distillation was performed at 120 ° C. and 0.27 kPa to obtain 56.8 g of a pale yellow pasty substance. ^From the results of ¹ H-NMR and IR, it was confirmed to be the compound (IV) represented by the following formula.

Rf ′: —CF ₂ (OCF ₂ CF ₂ ) _p (OCF ₂ ) _q OCF ₂ —
(P / q = 0.9, p + q≈45)

（式中Ｒｆ’は前記と同じ。）
で示される比較化合物（Ｖ）の四種類の化合物を、各々、表３に示す組成で配合した溶液（ハードコート組成物）を調製した。なお、ブランクとして添加剤を含まない溶液（ハードコート組成物）も調製した。 [Examples 3 and 4, Comparative Examples 1 to 3]
Evaluation in Hard Coat Composition Compound (II) obtained in Synthesis Example 1, Compound (III) obtained in Example 1 which is a compound of the present invention, Compound (IV) obtained in Example 2, and further below formula

(Wherein Rf ′ is the same as described above.)
A solution (hard coat composition) was prepared by blending each of the four types of compounds of Comparative Compound (V) represented by the formulas shown in Table 3. In addition, the solution (hard coat composition) which does not contain an additive as a blank was also prepared.

Next, each solution was spin-coated on a glass plate, dried at 80 ° C. for 2 minutes, and then irradiated with 1.6 J / cm ² of ultraviolet rays using a conveyor type ultraviolet irradiation device (manufactured by Panasonic Electric Works Co., Ltd.) in a nitrogen atmosphere. A cured film was formed. The obtained cured film was evaluated by the following method, and the results are shown in Table 4. In addition, about the compound (II), since the cloudiness generate | occur | produced with the said composition and the smooth cured surface was not able to be obtained, the following evaluation was not performed.

Water contact angle:
Measured with a contact angle meter manufactured by Kyowa Interface Science Co., Ltd.

Magic repellency:
The ease of repelling by Zebra Himacky Bold was visually observed.

Magic wipeability:
It was evaluated whether or not the ink written in Himackey Bold by Zebra was removed by wiping with a tissue paper 5 minutes after entry.

Touch:
6 subjects with different age and gender
1. Tap with your fingertips,
2. Pay with your fingertips,
3. Drag with your fingertips,
4. Slide the two fingertips close together,
5. Performs 5 actions of sliding and opening two closed fingertips, giving each sample an evaluation of 2 points, 1 point, and 0 points in the order that the subject felt easy to operate, and comparing the total of 6 points did.

Claims (5)

The following general formula (1)
(XQ) _a -YZ-Rf-ZY- (QX) _a (1)
[In the formula, Rf is a structural unit having a number average molecular weight of 1,000 to 40,000 as —CF ₂ O—, — (CF ₂ ) ₂ O—, — (CF ₂ ) ₃ O—, — (CF ₂ ) ₄ O-either, or a divalent linear fluoropolyether group having a repeating structure with multiple combinations of these, a is independently an integer from 1 to 20. X is independently

(R is a monovalent hydrocarbon group having 2 to 30 carbon atoms that does not contain a (meth) acryl group, an epoxy group, or a hydroxyl group in the structure, may have a cyclic structure, and is an ether bond other than an epoxy group on the way. Or an ester bond may be included, and a part of hydrogen atoms may be substituted with a halogen atom.)
It is group represented by these. Q is each independently a divalent hydrocarbon group having 1 to 20 carbon atoms, may have a cyclic structure, and may contain an ether bond (—O—) or an ester bond (—COO—). Good. Y is a (a + 1) -valent linking group composed of a siloxane structure having (a + 1) Si atoms, an unsubstituted or halogen-substituted silalkylene structure, a silarylene structure, or a combination of two or more thereof, and a cyclic structure You may have done. Z is independently the following formula

Is a divalent linking group selected from the group consisting of an oxygen atom, a nitrogen atom, a fluorine atom or a silicon atom, or a group having a cyclic structure and / or an unsaturated bond. . ]
In fluoropolyether compound represented. Y is the following formula

(In the formula, a is the same as a in formula (1), the broken line indicates a bond, the broken line of the unit having the repeating unit of a is bonded to the Q group, and the remaining broken line is bonded to Z. )
The compound of claim 1 wherein in a group represented by. The following general formula (2)
(HO-Q) _a -YZ-Rf-ZY- (Q-OH) _a (2)
(In the formula, Rf, a, Q, Y, and Z are the same as Rf, a, Q, Y, and Z in Formula (1).)
In the compound represented by the following general formula (3)
RN = C = O (3)
(In the formula, R is the same as R in formula (1).)
The compound of Claim 1 or 2 obtained by making the compound shown by react . Q is
—CH ₂ CH ₂ CH ₂ —
—CH ₂ CH ₂ CH ₂ CH ₂ —
—CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ —
_{-CH 2 CH 2 CH 2 OCH 2} CH 2 -
_{-CH 2 CH 2 CH 2 OCH 2} CH 2 OCH 2 CH 2 -
_{-CH 2 CH 2 CH 2 OCH 2} CH 2 OCH 2 CH 2 OCH 2 CH 2 -

The compound according to any one of claims 1 to 3 , which is a group selected from the group represented by: It is a compound shown by a following formula, The compound of any one of Claims 1-4 .

(In the formula, R is the same as R in Formula (1), j is 1 or 2, m + n is an integer of 10 to 70, m / n is 0.5 to 1.5, and (The arrangement of repeat units is random.)