JP2014221875A - Curable composition and article having cured coating film of the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a curable composition capable of obtaining a cured coating film having excellent antifouling performance and smooth touch feeling, and to provide an article having a cured coating film of the composition.SOLUTION: There is provided a curable composition containing a curable compound cured by irradiation with active energy rays and/or heating, which contains 0.005 to 20 pts.mass of a fluoropolyether compound represented by the following formula, (X-Q)-Y-Z-Rf-Z-Y-(Q-X)[Rf is a divalent straight chain fluoropolyether group having a number average molecular weight of 1000 to 40000; a is 1 to 20; X is a group represented by the following formula (R is a monovalent hydrocarbon group without containing a (meth)acrylic group, an epoxy group and a hydroxyl group in the structure); Q is a divalent hydrocarbon group; Y is (a+1)valent linking group; and Z is a divalent linking group] in 100 pts.mass of the solid content of the composition.

Description

  The present invention relates to a curable composition containing a novel fluoropolyether compound, and an article formed with a cured film of the composition.

  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 are used in addition to the conventionally required hardness, wear resistance, chemical resistance, durability, etc., according to the spread of their applications, as well as antifouling properties, weather resistance, slip properties, antistatic properties, antistatic properties, 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 blended with 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, development of the cured film which implement | achieves a smooth touch feeling in addition to antifouling performance, and the curable composition for implement | achieving it has been calculated | required.

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 curable composition from which a cured film having excellent antifouling performance and a smooth touch feeling can be obtained, and an article having a cured film of the composition. Objective.

  As a result of intensive studies to achieve the above object, the present inventor is represented by the general formula (1) in a curable composition containing a curable compound that is cured by irradiation with active energy rays and / or heating. The curable composition containing 0.005 to 20 parts by mass of the fluoropolyether compound in 100 parts by mass of the solid content of the composition is found to provide a cured film having excellent antifouling performance and a smooth touch feeling, It came to make this 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を、組成物の固形分１００質量部中に０．００５〜２０質量部含むことを特徴とする硬化性組成物。
〔２〕
硬化性化合物が、（メタ）アクリル基、オキセタン基、ビニルエーテル基、水酸基、カルボキシル基、アミノ基、エポキシ基、メルカプト基、イソシアネート基、加水分解性シリル基、シラノール基、カルボン酸無水物基の中から選ばれる基の少なくとも一つを有し、該基が反応して硬化する化合物であることを特徴とする〔１〕記載の硬化性組成物。
〔３〕
（Ａ）一般式（１）で示されるフルオロポリエーテル化合物、
（Ｂ）１分子中に（メタ）アクリル基を２個以上有する化合物
を含有することを特徴とする〔２〕に記載の硬化性組成物。
〔４〕
（Ａ）一般式（１）で示されるフルオロポリエーテル化合物、
（Ｃ）１分子中にイソシアネート基を２個以上有する化合物、
（Ｄ）１分子中にヒドロキシル基を２個以上有する化合物
を含有することを特徴とする〔２〕に記載の硬化性組成物。
〔５〕
〔１〕〜〔４〕のいずれかに記載の硬化性組成物の硬化皮膜が形成されてなる物品。 Accordingly, the present invention provides the following curable composition and an article having the cured film.
[1]
In the curable composition containing the curable compound which is cured by active energy ray irradiation and / or heating, 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. 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 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 and / or an unsaturated bond. ]
The curable composition characterized by including 0.005-20 mass parts in 100 mass parts of solid content of a composition.
[2]
The curable compound is a (meth) acryl group, oxetane group, vinyl ether group, hydroxyl group, carboxyl group, amino group, epoxy group, mercapto group, isocyanate group, hydrolyzable silyl group, silanol group, or carboxylic anhydride group. [1] The curable composition according to [1], wherein the curable composition has at least one group selected from the group consisting of:
[3]
(A) a fluoropolyether compound represented by the general formula (1),
(B) The curable composition according to [2], which contains a compound having two or more (meth) acrylic groups in one molecule.
[4]
(A) a fluoropolyether compound represented by the general formula (1),
(C) a compound having two or more isocyanate groups in one molecule;
(D) The curable composition according to [2], which contains a compound having two or more hydroxyl groups in one molecule.
[5]
An article formed with a cured film of the curable composition according to any one of [1] to [4].

  The curable composition of the present invention can form a cured product layer having excellent slipperiness in addition to water / oil repellency, fingerprint resistance, and antifouling property on the surface after curing. It is extremely useful as an agent.

（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 curable composition of the present invention contains a fluoropolyether compound represented by the following general formula (1) in a curable composition containing a curable compound that is cured by irradiation with active energy rays and / or heating. It is what.
(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 Of these, a linear fluoropolyether group having a repeating structure of a plurality of combinations is preferable, and a structure represented by the following is particularly preferable.
−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 (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, and is a group having a cyclic structure or an unsaturated bond. Also 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 condition where the Si—H group is in a large excess to obtain 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 an arbitrary 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. Hexachloroplatinum (IV) acid 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.

  In the curable composition of the present invention, the fluoropolyether compound represented by the general formula (1) is contained in an amount of 0.005 to 20 parts by mass in 100 parts by mass of the solid content of the composition. 005 to 10 parts by mass, more preferably 0.05 to 5 parts by mass. If the amount of the fluoropolyether compound represented by the general formula (1) is too small, the fluorine component will be small and it will be difficult to cover the surface of the cured product. If the amount is too large, the amount of the component derived from the fluoropolyether compound will be too large. The physical properties of the product will be impaired.

The curable composition of the present invention is obtained by blending the fluoropolyether compound represented by the general formula (1). The curable compound that is the main component (base polymer) of the curable composition is used as long as the fluoropolyether compound represented by the general formula (1) is mixed and a cured film can be formed. In particular, (meth) acryl group, oxetane group, vinyl ether group, hydroxyl group, carboxyl group, amino group, epoxy group, mercapto group, isocyanate group, hydrolyzable silyl group, silanol group, carboxylic anhydride group It is preferable that the compound has at least one group selected from among the above groups, and the group reacts and cures.
In addition, as a hardening method of a curable composition, arbitrary methods, such as irradiation of active energy rays, such as an ultraviolet-ray and an electron beam, and heat hardening, can be taken. Curing may be performed by a combination of a plurality of methods such as ultraviolet irradiation and heating.

As the curable composition of the present invention,
(A) a fluoropolyether compound represented by the general formula (1),
(B) An ultraviolet curable composition (I) containing a compound having two or more (meth) acrylic groups in one molecule is preferably used.

  In the ultraviolet curable composition (I), (B) the compound having two or more (meth) acrylic groups in one molecule is the main component of the composition, and two (meth) acrylic groups in one molecule. There are no particular restrictions on the structure of the compound having at least one compound, but acrylates are preferred. For example, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, ethylene glycol di (meth) ) Acrylate, isocyanuric acid ethylene oxide modified di (meth) acrylate, isocyanuric acid (poly) ethylene oxide modified tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, glycerol tri (meth) acrylate, Tris (meta) acryloilio Cyethyl phosphate, hydrogen phthalate- (2,2,2-tri- (meth) acryloyloxymethyl) ethyl, glycerol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate 2-6 functional (meth) acrylic compounds such as dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, sorbitol hexa (meth) acrylate, ethylene oxide, propylene oxide, these (meth) acrylic compounds, Epichlorohydrin, modified products modified with fatty acid or alkyl, epoxy acrylates obtained by adding acrylic acid to epoxy resin, (meth) acryloyl group in side chain of acrylic ester copolymer Introduced copolymer, and the like. Further, urethane acrylates, those obtained by reacting polyisocyanate with (meth) acrylate having a hydroxyl group, those obtained by reacting polyisocyanate and terminal diol polyester with (meth) acrylate having a hydroxyl group, excess in polyol Examples include those obtained by reacting a polyisocyanate obtained by reacting a diisocyanate with (meth) acrylate having a hydroxyl group, among which 2-hydroxyethyl (meth) acrylate and 2-hydroxy-3-acryloyloxypropyl. (Meth) acrylate having a hydroxyl group selected from methacrylate, pentaerythritol triacrylate, and poly (ethylene oxide) modified products of these acrylates, hexamethylene diisocyanate, isophorone di Isocyanate, tolylene diisocyanate, and is preferably one containing urethane acrylates of polyisocyanates reacted selected from diphenylmethane diisocyanate. Furthermore, fine particles of hollow or non-hollow inorganic or organic compounds modified with (meth) acrylic groups can also be used. These compounds corresponding to the component (B) may be used alone or in combination of two or more. Moreover, monofunctional acrylates can also be blended for adjusting the physical properties of the uncured and cured composition.

  (B) The compounding quantity of the compound which has 2 or more of (meth) acryl groups in 1 molecule which is a component is 80-99.995 mass parts in 100 mass parts of solid content of ultraviolet curable composition (I), In particular, it is preferably 90 to 99 parts by mass. If the blending amount of the component (B) is too small, curing failure may occur and the cured product layer may not be formed. In the ultraviolet curable composition (I), in order to develop the surface characteristics that are the object of the present invention, in addition to the component (B), the component (A) must be contained within the above-mentioned range. .

  It is preferable to mix a photopolymerization initiator in the ultraviolet curable composition (I). The photopolymerization initiator is not particularly limited as long as the (B) component (meth) acrylic compound can be cured by ultraviolet irradiation, but suitable examples include acetophenone, benzophenone, 2,2-dimethoxy-1, 2-diphenylethane-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1- [4- (2-hydroxyethoxy) -phenyl ] -2-Hydroxy-2-methyl-1-propan-1-one, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino- 1- (4-morpholinophenyl) -butanone-1,2- (dimethylamino) -2-[(4-methylphenyl) methyl -1- [4- (4-morpholinyl) phenyl] -1-butanone, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 1,2-octanedione-1- [4- (phenylthio) phenyl] -2- (O-benzoyloxime), ethanone-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3 -Yl] -1- (O-acetyloxime) and the like. A photoinitiator may be used individually by 1 type, or may use 2 or more types together.

  It is preferable that the usage-amount of a photoinitiator is 0.1-10 mass parts with respect to 100 mass parts of said (B) component, especially 1-5 mass parts. If the blending amount of the photopolymerization initiator is too small, sufficient initiation reaction may not be performed and curing failure may occur. If it is too large, non-uniform portions such as defects are generated in the cured product due to remaining initiator-derived components. There is a case.

As the curable composition of the present invention,
(A) a fluoropolyether compound represented by the general formula (1),
(C) a compound having two or more isocyanate groups in one molecule;
(D) A curable composition (II) containing a compound having two or more hydroxyl groups in one molecule is also preferably used.

  In the curable composition (II), (C) the compound having two or more isocyanate groups in one molecule is not particularly limited in its structure, but a polyfunctional isocyanate compound is preferable, for example, tetramethylene diisocyanate, 1, 6-hexamethylene diisocyanate, dodecamethylene diisocyanate, cyclohexane-1,3-diisocyanate, cyclohexane-1,4-diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, 1,3-bis- (isocyanatomethyl) -cyclohexane, 1,4 -Bis- (isocyanatomethyl) -cyclohexane, 2,4-isocyanatocyclohexyl-2'-isocyanatocyclohexylmethane, 4-isocyanatocyclohexyl-2'-isocyanatocyclohexyl Rumethane, bis- (4-isocyanato-3-methylcyclohexyl) methane, 1,3-tetramethylxylidene diisocyanate, 1,4-tetramethylxylidene diisocyanate, 2,4-diisocyanatotoluene, 2,6-di Isocyanatotoluene, 2,2'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, p-phenylene diisocyanate, m-phenylene diisocyanate, xylylene diisocyanate, diphenyl Examples include -4,4'-diisocyanate and polymethylene polyphenyl polyisocyanate.

Further, in the curable composition (II), (D) the compound having two or more hydroxyl groups in one molecule is not particularly limited in its structure. For example, 1,2-ethanediol, 1,2- Propanediol, 1,3-propanediol, butanediol, pentanediol, hexanediol, heptanediol, octanediol, 1,10-decanediol, 1,2-cyclohexanediol, 1,4-cyclohexanediol, 1,4- Cyclohexanedimethanol, 4,4 ′-(1-methylethylidene) -bis-cyclohexanol, 1,2,3-propanetriol, 1,1,1-trimethinolethane, 1,2,6-hexanetriol, 1,1,1-trimethylolpropane, 2,2-bis (hydroxymethyl) -1,3-propane Diol, bis- (2-hydroxyethyl) hydroquinone, 1,2,4-trihydroxycyclohexane, 1,3,5-trihydroxycyclohexane, 1,3,5-tris (2-hydroxyethyl) isocyanurate, hydroxypivalin Examples include acid neopentyl glycol ester, diethylene glycol, and dipropylene glycol.
In addition, polyfunctional alcohols such as those described above, succinic acid, adipic acid, sebacic acid, phthalic acid, isophthalic acid, trimellitic acid, phthalic anhydride, tetrahydrophthalic acid, maleic acid, maleic anhydride, dimer or trimer Polyester polyols obtained by reacting with acid or acid derivatives such as monomeric fatty acids, dimethyl terephthalate and bisglycol terephthalate can also be used.
Furthermore, in the above polyfunctional alcohol, β-propiolactone, γ-butyrolactone, γ- and δ-valerolactone, ε-caprolactone, 3,5,5- and 3,3,5-trimethylcaprolactone or lactone Polyester polyol in which the mixture is ring-opened, the above polyfunctional alcohol and diphenyl carbonate, dialkyl carbonate (for example, polycarbonate diol that can be produced by reacting with dimethyl carbonate or phosgene), diaryl carbonate (for example, diphenyl carbonate), dialkyl carbonate (For example, dimethyl carbonate) or polycarbonate diol ethylene oxide which can be produced by reacting with phosgene, 2-hydroxyethyl (meth) acrylate, hydroxypropyl ( Acrylic polyols containing tetrahydrofuran as a copolymerization component such as meth) acrylate, 6-hexanolide addition polymer of 2-hydroxyethyl methacrylate, glyceryl (meth) acrylate, glyceryl-1- (meth) acryloyloxyethyl urethane propylene oxide, tetrahydrofuran Polyether glycols obtained from the above polymers can also be used.
These components (D) may be used alone or as a mixture.

  The blending amount of the component (C) and the component (D) is 80 to 99.995 parts by mass in total of the component (C) and the component (D) in 100 parts by mass of the solid content of the curable composition (II). It is preferable that it is 95-99 mass parts. If the blending amount of the components (C) and (D) is too small, a curing failure may occur and the cured product layer may not be formed. In addition, in the curable composition (II), in order to develop the surface characteristics that are the object of the present invention, in addition to the components (C) and (D), the component (A) is added within the above-mentioned amount range. Need to include.

  In the curable composition (II), the compounding ratio of the component (C) and the component (D) is NCO / OH (molar equivalent of isocyanate group contained in the component (C) / hydroxyl group contained in the component (D). Are preferably used in such a manner that the equivalent ratio of 0.5 to 2.0, particularly 0.6 to 1.5. When the equivalent ratio is less than 0.5, the crosslinking density of the coating film is lowered, and the solvent resistance, water resistance, and weather resistance may be poor. On the other hand, if the isocyanate group exceeds 2.0 and the coating film becomes excessive, the coating film becomes brittle and the weather resistance deteriorates, and a satisfactory result may not be obtained in terms of drying properties.

  Furthermore, as curable composition (II), what is called a urethane prepolymer obtained by making the said polyfunctional isocyanate and a polyfunctional hydroxy compound react can also be used.

In these curable compositions (II), an appropriate catalyst can be blended in order to control the curing 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), zirconium tetra acetylacetonate, zirconium chelate compound and the like. These are not limited to one kind, and may be used as a mixture of two or more kinds.
The reaction rate can be increased by adding these catalysts to the total mass of the components (C) and (D), preferably 0.01 to 2% by mass, more preferably 0.05 to 1% by mass. .

  Moreover, the curable composition of this invention can mix | blend various additives in the range which does not impair the objective of this invention as needed. Examples of such additives include curing accelerators, fillers, reactive inorganic fine particles, reactive polymer fine particles, dyes and pigments, leveling agents, reactive diluents, non-reactive polymer resins, silane coupling agents, and oxidation agents. Examples thereof include an inhibitor, an ultraviolet absorber, a light stabilizer, an antifoaming agent, a dispersant, an antistatic agent, and a thixotropic agent.

  The curable composition of the present invention can be used after diluted with an arbitrary solvent. Particularly preferred solvents include alcohols such as isopropanol and butanol, ethers such as tetrahydrofuran and diethylene glycol dimethyl ether, ketones such as methyl ethyl ketone and methyl isobutyl ketone, and esters such as ethyl acetate and ethyl lactate.

  Further, the curable composition of the present invention is a material commercially available as a hard coating agent, a urethane resin, an epoxy resin, a melamine resin, a silicone resin, and a paint comprising these compositions, in which necessary components are already blended. The fluoropolyether compound represented by the general formula (1) may be blended to form a curable composition.

  The curable composition of the present invention obtained as described above is, for example, imparted to the surface of the substrate as a coating agent for protecting the surface of various substrates, in addition to antifouling properties and fingerprint wiping properties, as well as operability. A high smooth feel can be given. 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 curable composition 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 a coating agent.

  As an article formed with such a cured film of the curable composition of the present invention, a liquid crystal display, a plasma display, an electroluminescence display, a rear projection display, a fluorescent display tube (VFD), a field emission projection display, a CRT Various screen display operation devices such as toner-based displays; as specific applications, information terminals such as PCs, smartphones, tablet terminals, mobile phones, portable media players, portable game machines, game machine controllers, electronic books Readers, digital cameras, digital video cameras, digital photo frames, portable GPS terminals, wristwatches, control terminals for various electronic devices, automobile navigation devices, image display devices such as security system terminals, Child bulletin boards, electronic signboards, electronic information boards, automatic cash withdrawal and deposit devices, cash dispensers, various vending machines, electronic registers, touch panels (touch sensors, touch screens) type image display input devices that perform display and operations, etc. Case surface of mobile phones, personal digital assistants, cameras, portable music players, portable game machines, etc .; car exteriors, pianos, luxury furniture, marble coating and surfaces; protective glass for art exhibits, show windows, showcases, A cover for advertisement, a cover for a photo stand, a wristwatch and the like can be mentioned.

  As a method for forming a cured film, any method can be used, but a method of directly applying and curing the curable composition of the present invention to an article, and applying the curable composition to a substrate such as a film. A method of applying a curable composition to a substrate such as a film after curing and curing, a method of curing and molding together with a resin forming the article, a curable composition film Examples thereof include a method of transferring to the surface of the article.

  When the curable composition of the present invention is applied to the surface of an article, examples of the application method include roll coating, gravure coating, dip coating, spray coating, spin coating, bar coating, and screen printing. In addition, when the curable composition of the present invention is transferred to the surface of an article, examples of the transfer method include roll thermal transfer, up-down thermal transfer, vacuum press transfer, in-mold transfer, and hydraulic transfer.

The curing conditions of the curable composition of the present invention are not particularly limited, but in the case of curing by active energy ray irradiation, as a light source of the line irradiation device, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a high power metal halide lamp , UV electrodeless lamp, UV-LED and the like. Irradiation energy can be arbitrarily set according to the type and composition of active energy rays. For example, when a high-pressure mercury lamp is used, the irradiation energy in the UV-A region is 10 to 10,000 mJ / cm ^2. 100 to 5,000 mJ / cm ² is more preferable.
In the case of heat curing, it is preferably from room temperature (25 ° C.) to 200 ° C. for 5 seconds to 240 hours, particularly preferably from 60 to 120 ° C. for 10 minutes to 8 hours.

  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 perfluoropolyether having α-unsaturated bonds at both ends represented by the formula, 700 g of m-xylene hexafluoride and 361 g [1.50 mol] of tetramethylcyclotetrasiloxane are added. 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）

[Synthesis Example 2]
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）

[Synthesis Example 3]
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 9.3 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 1 and 2 and Comparative Examples 1 to 3]
Evaluation in Hard Coat Composition (A) Compound (II) obtained in Synthesis Example 1, Compound (III) obtained in Synthesis Example 2 which is a compound of the present invention, and Compound (IV) obtained in Synthesis Example 3 And the following 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.

[Example 3, Comparative Examples 4 to 6]
Evaluation in Hard Coat Composition (B) Compound (II) obtained in Synthesis Example 1, Compound (IV) obtained in Synthesis Example 3 which is a compound of the present invention, and Compound (V) used in Comparative Example 2 above The solution (hard coat composition) in which the three types of compounds were blended with the compositions shown in Table 5 was prepared. In addition, the solution (hard coat composition) which does not contain an additive as a blank was also prepared.

  Subsequently, each obtained solution was coated on a glass plate with a wire bar having a gap of 24 μm and heated at 120 ° C. for 2 hours. After completion of heating, the temperature was returned to room temperature, and the properties of the cured coating surface were evaluated in the same manner as in Example 1. The results are shown in Table 6.

Claims (5)

In the curable composition containing the curable compound which is cured by active energy ray irradiation and / or heating, 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. 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 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 and / or an unsaturated bond. ]
The curable composition characterized by including 0.005-20 mass parts in 100 mass parts of solid content of a composition.   The curable compound is a (meth) acryl group, oxetane group, vinyl ether group, hydroxyl group, carboxyl group, amino group, epoxy group, mercapto group, isocyanate group, hydrolyzable silyl group, silanol group, or carboxylic anhydride group. The curable composition according to claim 1, wherein the curable composition has at least one group selected from the group consisting of: (A) a fluoropolyether compound represented by the general formula (1),
(B) The curable composition according to claim 2, comprising a compound having two or more (meth) acrylic groups in one molecule. (A) a fluoropolyether compound represented by the general formula (1),
(C) a compound having two or more isocyanate groups in one molecule;
(D) The curable composition according to claim 2, comprising a compound having two or more hydroxyl groups in one molecule.   An article formed with a cured film of the curable composition according to any one of claims 1 to 4.