JP5737221B2 - Curable composition containing fluorine-containing alcohol compound - Google Patents

Description

  The present invention relates to a curable composition containing a fluorinated alcohol compound, and particularly to a curable composition useful as a thermosetting coating agent or coating composition for various substrates having excellent water repellency.

Resin materials such as alkyd resins, epoxy resins, unsaturated polyester resins, phenol resins, melamine resins, urea resins and urethane resins are used not only as structural materials but also as paints.
For example, urethane-based paints containing polyisocyanate as an essential component can provide coatings with excellent weather resistance and abrasion resistance, coating outdoor equipment such as building materials and civil engineering structures, automobile repairs, plastic coating, etc. Used in a wide range of fields. In recent years, with the expansion of the application range of such paints, there has been a demand for higher functionality of the paints themselves. In particular, various attempts have been made to introduce fluorine-based compounds into resin coatings in order to obtain more excellent properties such as water repellency, oil repellency, and antifouling properties.

For example, a urethane-based paint is obtained by modifying perfluoropolyether with diisocyanate and blending with a polyol (Non-Patent Document 1: C. Tonelelli, et al., Journal of Applied polymer science, Vol. 57 1031). -1042 (1995)) and as a curing agent for a two-component fluorine-based coating composition, an allophanate group-containing polyisocyanate obtained by reaction of a monoalcohol having 1 to 10 carbon atoms with an aliphatic organic polyisocyanate is used. A technique to be used (Patent Document 1: Japanese Patent Laid-Open No. 5-287240) is disclosed.
However, in such a method, since the fluorine-containing component in the composition is a main component constituting the polyurethane paint film, the handling properties and mechanical properties are greatly affected as compared with the conventional urethane paint. .

  On the other hand, paying particular attention to antifouling properties and fingerprint resistance on the surface of the paint film, the performance of fluorine compounds such as water repellency and oil repellency is maintained on the surface while maintaining the handleability of existing paint and the mechanical properties of the paint film. There is a growing demand for methods of granting.

Japanese Patent Laid-Open No. 5-287240

C. Toneelli,. et. al. , Journal of Applied polymer science, Vol. 57 1031-1042 (1995)

  The present invention has been made in view of the above circumstances, and a cured product layer having a surface excellent in water repellency, oil repellency, fingerprint resistance, and antifouling property can be formed by curing, and a thermosetting antifouling coating. It aims at providing the curable composition useful as a forming material of an agent.

  As a result of intensive studies in order to achieve the above object, the inventors have obtained 0.005 to 20 parts by mass of the fluorinated alcohol compound represented by the following general formula (1) in 100 parts by mass of the whole composition. When the curable composition containing it was used as a coating agent, it discovered that the characteristic of the fluorine-type compound could be provided on the surface, maintaining the property of the existing coating materials as mentioned above, and came to make this invention.

［式中、Ｒｆはフルオロポリエーテル構造を含む ¹ Ｈ−ＮＭＲ及び ¹⁹ Ｆ−ＮＭＲに基づく末端構造と主鎖構造との比率から算出される数平均分子量１００〜４０，０００の一価又は二価の基である。Ｑ¹は下記式（２）

（式中、ａ、ｂは式（１）におけるａ、ｂ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はＲｆと結合し、ｂの繰り返し単位を有するユニットは下記式
−Ｑ ² −ＯＨ
で示される基と結合する。また、２種類の繰り返し単位の並びはランダムである。Ｒｆは上記の通りである。）
で表される連結基であり、Ｑ ² は炭素数１〜２０の二価の炭化水素基であり、環状構造をなしていてもよく、途中エーテル結合又はエステル結合を含んでいてもよい。Ｒｆが一価のときにはｃは１であり、かつａは１〜６の整数であり、Ｒｆが二価のときにはａは１であり、かつｃは２である。ｂは１〜２０の整数である。］
で表される含フッ素アルコール化合物、
（Ｂ）１分子中にイソシアネート基を２個以上有する化合物、
（Ｃ）１分子中にヒドロキシル基を２個以上有し、フッ素原子を含まない多官能ヒドロキシル基含有化合物
を含有し、（Ａ）成分を（Ａ）、（Ｂ）、（Ｃ）成分の合計量１００質量部中０．００５〜２０質量部含み、かつＮＣＯ／ＯＨ（組成物中の全成分のヒドロキシル基の総量）の当量比が０．５〜２．０であることを特徴とする硬化性組成物。
〔２〕
更に、触媒を含有する〔１〕記載の硬化性組成物。
〔３〕
一般式（１）において、Ｑ²が
−ＣＨ₂ＣＨ₂ＣＨ₂−
−ＣＨ₂ＣＨ₂ＣＨ₂ＣＨ₂−
−ＣＨ₂ＣＨ₂ＣＨ₂ＣＨ₂ＣＨ₂−
−ＣＨ₂ＣＨ₂ＣＨ₂ＯＣＨ₂ＣＨ₂−
−ＣＨ₂ＣＨ₂ＣＨ₂ＯＣＨ₂ＣＨ₂ＯＣＨ₂ＣＨ₂−
−ＣＨ₂ＣＨ₂ＣＨ₂ＯＣＨ₂ＣＨ₂ＯＣＨ₂ＣＨ₂ＯＣＨ₂ＣＨ₂−

で示される群の中より選ばれる〔１〕又は〔２〕記載の硬化性組成物。 Therefore, this invention provides the curable composition shown below.
[1]
(A) The following general formula (1)

[ Wherein, Rf is a monovalent or divalent number average molecular weight of 100 to 40,000 calculated from the ratio of the terminal structure and the main chain structure based on ¹ H-NMR and ¹⁹ F-NMR including a fluoropolyether structure. It is the basis of. Q ¹ is the following formula (2)

(Wherein, a and b are the same as a and b in formula (1), the broken line indicates a bond, a unit having a repeating unit of a is bonded to Rf, and a unit having a repeating unit of b is formula
-Q ² -OH
It bonds with the group shown by. Also, the arrangement of the two types of repeating units is random. Rf is as described above. )
In a linking group represented, Q ² is a divalent hydrocarbon group having 1 to 20 carbon atoms which may form a cyclic structure may include a middle ether bond or an ester bond. When Rf is monovalent, c is 1 and a is an integer of 1 to 6. When Rf is divalent, a is 1 and c is 2. b is an integer of 1-20. ]
A fluorine-containing alcohol compound represented by :
(B) a compound having two or more isocyanate groups in one molecule;
(C) Polyfunctional hydroxyl group-containing compound having two or more hydroxyl groups in one molecule and containing no fluorine atom
The component (A) is contained in an amount of 0.005 to 20 parts by mass in 100 parts by mass of the total amount of the components (A), (B) and (C), and NCO / OH (hydroxyl of all components in the composition) A curable composition having an equivalent ratio of (total amount of groups) of 0.5 to 2.0 .
[2]
Furthermore, the curable composition of [1] containing a catalyst.
[ 3 ]
In the general formula (1), Q ² 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 curable composition according to [1] or [2] , which is selected from the group represented by:

  The curable composition containing the fluorinated alcohol compound of the present invention can form a cured product layer having a surface excellent in water repellency, oil repellency, fingerprint resistance, and antifouling property by curing, and is capable of forming a thermosetting type It is useful as a material for forming a dirt coating agent.

Hereinafter, the present invention will be described in detail.
The curable composition of the present invention comprises:
(A) characterized in that it contains a fluorine-containing alcohol compound represented by the following general formula (1), preferably
(B) a compound having two or more isocyanate groups in one molecule;
More preferably,
(C) The polyfunctional hydroxyl group containing compound which has two or more hydroxyl groups in 1 molecule, and does not contain a fluorine atom is contained.

（式中、Ｒｆはフルオロポリエーテル構造を含む分子量１００〜４０，０００の一価又は二価の基である。Ｑ¹は少なくとも（ａ＋ｂ）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＋ｂ）価の連結基であり、環状構造をなしていてもよい。Ｑ²は炭素数１〜２０の二価の炭化水素基であり、環状構造をなしていてもよく、途中エーテル結合又はエステル結合を含んでいてもよい。Ｒｆが一価のときにはｃは１であり、かつａは１〜６の整数であり、Ｒｆが二価のときにはａは１であり、かつｃは２である。ｂは１〜２０の整数である。）
で表される含フッ素アルコール化合物を用いる。含フッ素アルコール化合物を配合することにより、硬化性組成物の硬化物表面に防汚性、耐指紋性、撥水性、撥油性を付与することができる。 In the curable composition of the present invention, as the component (A), the following general formula (1)

(Wherein, Rf is .Q ¹ is a monovalent or divalent group having a molecular weight 100～40,000 containing fluoropolyether structure having at least (a + b) number of Si atoms, a siloxane structure, unsubstituted or halogen A substituted (a + b) -valent linking group comprising a substituted silalkylene structure, a silarylene structure, or a combination of two or more thereof, and may have a cyclic structure, and Q ² is a divalent group having 1 to 20 carbon atoms. It is a hydrocarbon group, may have a cyclic structure, and may contain an ether bond or an ester bond, and when Rf is monovalent, c is 1 and a is an integer of 1 to 6. When Rf is divalent, a is 1 and c is 2. b is an integer of 1 to 20.)
The fluorine-containing alcohol compound represented by these is used. By mix | blending a fluorine-containing alcohol compound, antifouling property, fingerprint resistance, water repellency, and oil repellency can be provided to the hardened | cured material surface of a curable composition.

In the formula (1), Rf is a monovalent or divalent group having a molecular weight of 100 to 40,000, preferably 500 to 20,000, containing a fluoropolyether structure. 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.

As Rf, the following formula -C _h F _2h O-
(H is an integer of 1 to 6 independently for each unit.)
Those containing 1 to 500, preferably 2 to 400, more preferably 4 to 200 repeating units represented by formula (1) are suitable.

A particularly preferable structure as Rf can be represented by the following general formula (3) or (3 ′).
− [Q ³ −Rf′−Q ³ −T] _v −Q _f −Rf′−Q ³ − (3)
F-Rf′-Q ³ − (3 ′)

  Rf ′ is a perfluoropolyether group having a divalent molecular weight of 300 to 30,000, particularly 500 to 20,000, and may contain a branch, and is particularly represented by the following formulas (5) to (7). Divalent perfluoropolyether groups are preferred.

（式（５）中、Ｙはそれぞれ独立にＦ又はＣＦ₃基、ｒは２〜６の整数、ｍ、ｎはそれぞれ０又は１〜２００、好ましくは０又は１〜１００の整数、但し、ｍ＋ｎは２〜２００、好ましくは３〜１５０の整数である。ｓは０又は１〜６の整数であり、各繰り返し単位はランダムに結合されていてよい。）

(In Formula (5), Y is each independently F or CF ₃ group, r is an integer of 2 to 6, m and n are each 0 or 1 to 200, preferably 0 or an integer of 1 to 100, provided that m + n Is an integer of 2 to 200, preferably 3 to 150. s is an integer of 0 or 1 to 6, and each repeating unit may be bonded at random.)

（式中、ｊは１〜３の整数、ｋは１〜２００、好ましくは１〜６０の整数である。）

(In the formula, j is an integer of 1 to 3, and k is an integer of 1 to 200, preferably 1 to 60.)

（式中、ＹはＦ又はＣＦ₃基、ｊは１〜３の整数、ｔ、ｕはそれぞれ０又は１〜２００、好ましくは２〜１００の整数、但し、ｔ＋ｕは２〜３００、好ましくは４〜２００の整数である。各繰り返し単位はランダムに結合されていてもよい。）

Wherein Y is an F or CF ₃ group, j is an integer of 1 to 3, t and u are each 0 or 1 to 200, preferably 2 to 100, provided that t + u is 2 to 300, preferably 4 It is an integer of -200. Each repeating unit may be couple | bonded at random.)

Q ³ is a divalent organic group, preferably a divalent hydrocarbon group having 2 to 20 carbon atoms, particularly 3 to 12 carbon atoms, and may contain an oxygen atom, a nitrogen atom, a fluorine atom or a silicon atom, Further, it may be a group having a cyclic structure or an unsaturated bond. Examples of such Q ³ include the following. In the formula, Ph represents a phenyl group.

が好ましい。 Especially among these

Is preferred.

（式中、Ｑ²、ａ、ｂは前述の通りであり、Ｑ⁴は少なくとも（ａ＋ｂ）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＋ｂ）価の連結基であり、上記Ｑ¹の（ａ＋ｂ）価のうち、二価分がＱ³との結合に使用されたシロキサン構造、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構造である。）
で表される二価の連結基である。 T is the following formula (4)

(Wherein Q ² , a, and b are as defined above, and Q ⁴ has at least (a + b) Si atoms, a siloxane structure, an unsubstituted or halogen-substituted silalkylene structure, a silarylene structure, or a combination thereof. It is a (a + b) -valent linking group comprising a combination of two or more types. Among the (a + b) valences of Q ¹ , the divalent component is a siloxane structure used for bonding with Q ³ , unsubstituted or halogen-substituted It is a silalkylene structure, a silarylene structure, or a structure comprising a combination of two or more of these.)
It is a bivalent coupling group represented by these.

Examples of Q ⁴ include the following. However, in the following formula, the divalent bond indicated by the solid line is bonded to Q ^3, and the (a + b−2) bond indicated by the broken line is −Q ² —OH. (Wherein Q ² is as described above). In addition, in the case of the following formula (a), -Q ² -OH is connected to the broken lines of the units at both ends, and (a + b-2) units are formed by these units at both ends and the unit (a + b-4). min bond to bind a group represented by -Q ² -OH. In addition, the arrangement of the above-described units for two valences indicated by the solid line, (a + b−2) units, and p units are random. a and b are each preferably an integer of 1 to 4 and a + b is an integer of 3 to 6, particularly 3 to 5. p is 0 or an integer of 1 or more, and the upper limit of p is preferably 12 or less, particularly 6 or less.

Here, Q ⁵ is an (a + b) -valent linking group, and examples thereof include the following.

Q _f is Q ³ , or a fluorine atom when v = 0.
Further, v is 0 or an integer of 1 to 5, particularly 0 or 1, and particularly 0. When Q _f is a fluorine atom, v is 0 and Rf has the following structure (3 ′).
F-Rf′-Q ³ − (3 ′)

Specific examples of Rf include the following.

（上記式中、ｊ、ｋ、ｍ、ｎ、ｒ、ｓ、ｔ、ｕは上述した通りである。）

(In the above formula, j, k, m, n, r, s, t, and u are as described above.)

  In the formula (1), a is an integer of 1-6, preferably 1-4, b is an integer of 1-20, preferably 1-4, c is 1 or 2, but Rf is one. In the case of valence, a is an integer of 1 to 6, and c is 1, and when Rf is divalent, a is 1 and c is 2. b is an integer of 1 to 20, particularly preferably an integer of 1 to 6, and a + b is preferably an integer of 3 to 6, particularly 3 to 5.

In the formula (1), Q ¹ is an (a + b) -valent compound comprising a siloxane structure having at least (a + b) Si atoms, an unsubstituted or halogen-substituted silalkylene structure, a silarylene structure, or a combination of two or more thereof. The linking group may have a cyclic structure, and specifically, the following structures are shown.
However, in the following formula, a and b are as defined above, preferably both a and b are integers of 1 to 4, and a + b is an integer of 3 to 6, particularly 3 to 5. p is an integer of 0 or 1 or more, the arrangement of each of a units, b units, and p units is random, and a bond indicated by a broken line of each of the a units and b units is Rf− or -Q (wherein, Rf, Q ² are as defined above.) ² -OH is bonded to any one of the radicals represented by. The upper limit of p is preferably 12 or less, particularly 6 or less.

The a + b unit can be represented separately as a unit and b unit, Rf is connected to the bond of the unit a, and -Q ² —OH is connected to the bond of the unit b. Are linked (Rf and Q ² are as described above). In the case of formula (b), Rf or -Q ² -OH is connected to the broken lines of the units at both ends, and (a + b) units are constituted by these units at both ends and the unit (a + b-2). To do.

Q ⁵ is as described above, and examples of Q ⁵ are the same as those described above.

［式中、ａ、ｂは上記と同じであり、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は上記Ｒｆと結合し、ｂの繰り返し単位を有するユニットは下記式
−Ｑ²−ＯＨ
（式中、Ｑ²は上記と同じである。）
で示される基と結合する。また、２種類の繰り返し単位の並びはランダムである。］ Q ¹ is more preferably a structure represented by the following formula (2).

[Wherein, a and b are the same as above, the broken line indicates a bond, a unit having a repeating unit of a is bonded to the above Rf, and a unit having a repeating unit of b is represented by the following formula -Q ² -OH
(Wherein Q ² is the same as above)
It bonds with the group shown by. Also, the arrangement of the two types of repeating units is random. ]

In Formula (1), Q ² is 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 on the way (-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 -

The fluorine-containing alcohol compound represented by the general formula (1) as described above can be synthesized, for example, by the following method.
First, with respect to the fluorine-containing compound (i) 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) (ii) is subjected to a hydrosilylation addition reaction under an excessive Si-H group condition to give a fluorine-containing polyfunctional Si-H compound (iii) Is synthesized.

Among such compounds (i), the following formula (8) can be shown as an example of generalizing a particularly desirable structure.
Rf ⁰ − (CH═CH ₂ ) _x (8)

Here, Rf ⁰ is represented by the following formula:-[Q ⁶ -Rf′-Q ³ -T] _v -Q _f -Rf′-Q ^6-
F-Rf′-Q ⁶ −
It is represented by In the above formula, Rf ′, T, Q _f , Q ³ and v are as described above, Q ⁶ is a divalent organic group, preferably a divalent carbonization having 1 to 20 carbon atoms, particularly 1 to 10 carbon atoms. It is a hydrogen group and 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. x is 1 when Rf ⁰ is monovalent and 2 when Rf ⁰ is divalent.

Examples of Q ⁶ include the following. In the following examples, Ph represents a phenyl group.

The following can be illustrated as a particularly preferable compound (i).

（上記式中、ｊ、ｋ、ｍ、ｎ、ｒ、ｓは上述した通りである。）

(In the above formula, j, k, m, n, r, and s are as described above.)

Compound (ii) can be expressed as a general formula in the form of the following formula (9).
Q ¹ − (H) _{a + b} (9)
(In the formula, Q ¹ , a and b are as described above, and H shown in parentheses is a hydrogen atom directly bonded to an Si atom in the Q ¹ structure.)

Among these, the following can be illustrated as a preferable compound (ii).

（上記式中、ａ、ｂは前述の通りであり、ｐは０又は１以上の整数である。）

(In the above formula, a and b are as described above, and p is 0 or an integer of 1 or more.)

  By performing an addition reaction at a reaction temperature of 60 to 150 ° C., preferably 70 to 120 ° C. in the presence of a platinum group metal-based addition reaction catalyst, in any combination of the above compound (i) and compound (ii). A fluorine-containing polyfunctional Si—H compound (iii) can be obtained.

For example, when compound (i) is monofunctional (x = 1 in formula (8)), compound (ii) is added if the number of compounds (i) added to one molecule is less than (a + b). The compound (iii) obtained when, for example, a is added can be represented by the following general formula (10).
(Rf ⁰ -C ₂ H ₄ ) _a -Q ^1- (H) _b (10)
(Rf ⁰ , Q ¹ , a, and b are as described above, and H shown in parentheses is a hydrogen atom directly bonded to a Si atom in the Q ¹ structure.)

（式中、Ｔ²は

で示される基であり、Ｑ¹、Ｑ⁴、Ｒｆ⁰、ａ、ｂ、ｖは上記の通りであり、かっこ内に示されたＨはＱ¹又はＱ⁴構造中のＳｉ原子に直接結合する水素原子である。） On the other hand, when the compound (i) is bifunctional (x = 2 in the formula (8)), it is desirable to add at a ratio (molar ratio) of the compound (i): the compound (ii) = v + 1: v + 2. (V is as described above), and the resulting compound (iii) can be expressed, for example, as in formula (11). When v = 0, the compound (i) has one molecule at both ends. (Ii) is introduced.

(Where T ² is

Q ¹ , Q ⁴ , Rf ⁰ , a, b, v are as described above, and H shown in parentheses is directly bonded to the Si atom in the Q ¹ or Q ⁴ structure. It is a hydrogen atom. )

  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 ( It is preferred that iii) is soluble at the reaction temperature. 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 compound (i).

In the addition reaction, the order in which the components are charged is not particularly limited. For example, the method of gradually heating the mixture of compound (i), compound (ii) and catalyst from room temperature to the addition reaction temperature, compound (i), compound (ii ) And a dilute solvent mixture after heating to the target reaction temperature, adding the catalyst, dropping the compound (i) to the mixture of the compound (ii) and catalyst heated to the target reaction temperature, The method of dripping the mixture of a compound (i) and a catalyst etc. to the compound (ii) heated to reaction temperature to make can be taken. Among them, a method of adding a catalyst after heating a mixture of the compound (i), the compound (ii) and the diluting solvent to a target reaction temperature, or a compound (ii) heated to the target reaction temperature. A method in which a mixture of (i) and a catalyst is dropped is particularly preferable. 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., for 0.5 to 96 hours, preferably 1 to 48. It is desirable to do time.

  The amount of compound (ii) to compound (i) is such that the number of compounds (i) to be added is less than (a + b) per molecule of compound (ii), and v in compound (iii) is 0. Alternatively, any compounding amount may be used as long as it is an integer of 1 to 5, but in order to prevent three-dimensional crosslinking, the compound (ii) with respect to a terminal olefin group such as an allyl group of the compound (i) It is desirable to remove the unreacted compound (ii) by distillation under reduced pressure or the like after the addition reaction using an excess amount of the compound (i) with respect to 1 equivalent of the terminal olefin group such as the allyl group of the compound (i). It is preferable to react ii) in the presence of 1 to 10 equivalents, particularly 2 to 6 equivalents. If necessary, an addition reaction may be carried out stepwise after synthesizing an intermediate having a small v. For example, after synthesizing the compound (iii) with v = 0 in the formula (11) using the compound (i) with x = 2 in the formula (8), the formula (iii) Compound (iii) of v = 3 can be obtained by reacting again 1 mol of compound (i) of x = 2 in 8). Alternatively, in the compound (iii), a component having a target value of v can be separated from a mixture having a different v by any separation means. For example, you may take out only the component of v = 1 from a mixture of v = 0-3 in compound (iii) by means, such as a preparative chromatograph.

  The fluorine-containing alcohol compound used in the present invention is an addition reaction between the Si—H group of the compound (iii) obtained as described above and the compound (iv) having a terminal olefin group and an alcoholic hydroxyl group in one molecule. Can be obtained by performing As such compound (iv), the following are particularly preferable. These compounds (iv) 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 compound (iii) and compound (iv) can be carried out in the same manner as the addition reaction of compound (i) and compound (ii) 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 120 ° C., for 0.5 to 96 hours, Preferably, the reaction can be carried out in any order of addition by performing dilution as necessary for 1 to 48 hours.

  The compounding amount of compound (iv) with respect to compound (iii) can be any amount, but compound (iv) is added in an equimolar or excess amount relative to the Si-H group of compound (iii). After the reaction, it is desirable to remove the unreacted compound (iv) by distillation under reduced pressure or the like. In particular, the compound (iv) is added in an amount of 1.0 to 1.0 to 1 equivalent of the Si—H group of the compound (iii). It is desirable to carry out the reaction in the presence of 5.0 equivalents, preferably 1.0 to 2.0 equivalents.

In the present invention, the fluorinated alcohol compound (A) is a compound represented by the following formula (Rf) _a- [Q ^1- (H) _b ] _{c in} addition to the above method.
(Q ¹ , b and Rf are as described above.)
It can also be obtained by performing an addition reaction between the fluorine-containing organosilicon compound (v) and the compound (iv). In this case, the reaction conditions and the like can be the same as the reaction conditions for the compound (iii) and the compound (iv) described above.

As the fluorine-containing alcohol compound (A) represented by the formula (1) thus obtained, examples of particularly preferred structures include the following.

（上記式中、ｎ、ｊ、ｔ、ｕは上記と同じである。）

(In the above formula, n, j, t and u are the same as above.)

The curable composition of the present invention is characterized by blending the fluorinated alcohol compound obtained as described above. By curing the composition, the surface of the cured product is antifouling, fingerprint-proof, and repellent. Water and oil repellency can be imparted.
The compounding amount of the fluorinated alcohol compound is 0.005 to 20 parts by mass, preferably 0.01 to 10 parts by mass, more preferably 0.05 to 5 parts by mass in 100 parts by mass of the whole composition. It is. If the value exceeds the above upper limit value, the amount of the fluorinated alcohol compound is excessively increased, which may impair the performance as a cured product, and if it is less than the lower limit value, the fluorine component is reduced and the hard coat layer surface is sufficiently covered. May not be possible.

  In the composition of the present invention, as the component (B), a compound having 2 or more, preferably 2 to 20, isocyanate groups in one molecule can be blended. The component (B) is not particularly limited as long as it is a polyfunctional isocyanate compound. 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′-isocyanatocyclohexylmethane, bis- (4-isocyanato-3-methylcyclohexyl) methane, 1,3-te Lamethylxylidene diisocyanate, 1,4-tetramethylxylidene diisocyanate, 2,4-diisocyanatotoluene, 2,6-diisocyanatotoluene, 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-4,4'-diisocyanate, polymethylene polyphenyl polyisocyanate and the like.

  (B) Although the compounding quantity of a component can be arbitrarily set with the physical property of the target hardened layer, and the property of each component, when the sum total of (A) component and (C) component is 100 mass parts normally 5 to 100 parts by mass, particularly 10 to 50 parts by mass. If the amount of the component (B) is too small, the distribution of isocyanate groups in the composition may be biased, and the component (A) and the component (B) may not be sufficiently reacted. Ingredients become difficult to move, and there is a case where the target surface cannot be cured.

  Further, as one embodiment of the present invention, a polyfunctional hydroxyl group-containing compound having 2 or more, preferably 2 to 20 hydroxyl groups in one molecule and not containing a fluorine atom, that is, a non-fluorinated polyfunctional hydroxyl group. A group containing compound can be mix | blended as (C) component.

  Examples of such component (C) include non-fluorinated polyfunctional alcohols such as 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, butanediol, pentanediol, hexanediol, and heptane. Diol, 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-trimethylolethane, 1,2,6-hexanetriol, 1,1,1-trimethylolpropane, 2,2-bis (hydroxymethyl)- 1,3-propanediol, bis- (2-hydroxyethyl) hydroquinone, 1,2,4 Trihydroxy cyclohexane, 1,3,5-trihydroxy-cyclohexane, 1,3,5-tris (2-hydroxyethyl) isocyanurate, hydroxypivalic acid neopentyl glycol ester, diethylene glycol, 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.

In addition, in the above polyfunctional alcohols, β-propiolactone, γ-butyrolactone, γ- and δ-valerolactone, ε-caprolactone, 3,5,5- and 3,3,5-trimethylcaprolactone or lactones thereof Polyester polyol obtained by ring opening of the mixture, polycarbonate diol, diaryl carbonate (eg, diphenyl carbonate), dialkyl carbonate that can be produced by reacting the above polyfunctional alcohol with diphenyl carbonate, dialkyl carbonate (eg, dimethyl carbonate) or phosgene. (For example, dimethyl carbonate) or polycarbonate diol ethylene oxide which can be produced by reacting with phosgene, 2-hydroxyethyl (meth) acrylate, hydroxypropyl ( Acrylic polyols and tetrahydrofuran polymers containing, as copolymerization components, meth) acrylate, 6-hexanolide addition polymer of 2-hydroxyethyl methacrylate, glyceryl (meth) acrylate, glyceryl-1-methacryloyloxyethylurethane propylene oxide and the like Polyether glycols obtained by the above can also be used.
These may be used alone or as a mixture.

  Component (C) is preferably blended in an amount of 1 to 1,000 parts by mass, particularly 50 to 500 parts by mass, with 1 part by mass of component (A). If the amount of the component (C) is too small, the effect of the component (A) on the physical properties of the cured product layer will be too great, and the properties of the hard coat layer may be impaired. It may become difficult to move, and the target surface may not be cured.

  Moreover, in this invention, what is called a urethane prepolymer obtained by making it react with the said polyfunctional isocyanate and a non-fluorinated polyfunctional hydroxyl group containing compound can also be used as (B) component.

Moreover, the curable composition of this invention can also mix | blend alcohols containing the fluorine atom which does not correspond to (A) component for dilution, compatibility, and leveling improvement.
In this case, the blending amount of the alcohol containing a fluorine atom not corresponding to the component (A) is preferably 0.01 to 0.2 parts by mass when the component (A) is 1 part by mass.

  In the curable composition of the present invention, as described above, the above component (A) is 0 with respect to all the components in the composition, particularly 100 parts by mass in total of the above components (A), (B) and (C). 0.005 to 20 parts by mass, but preferably, the equivalent ratio of isocyanate groups to hydroxyl groups in the composition, that is, NCO / OH (total amount of hydroxyl groups of all components in the composition) is 0.00. It is desirable to mix and use so that it may become a ratio of 5-2.0, especially 0.8-1.2. 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 exceeds 2.0 and the coating film becomes excessive, the coating film becomes brittle and the weather resistance decreases, and a satisfactory result may not be obtained in terms of drying properties.

In the thermosetting composition of the present invention, an appropriate catalyst can be blended in order to control the curing rate. For example, tertiary amines such as triethylamine, pyridine, methylpyridine, benzyldimethylamine, N, N-endoethylenepiperazine, N-methylpiperidine, pentamethyldiethylenetriamine, N, N-dimethylaminocyclohexane, N, N′-dimethylpiperazine , Iron (III) chloride, zinc chloride, zinc-2-ethylcaproate, tin (II) octoate, tin (II) ethylcaproate, dibutyltin (IV) dilaurate, bismuth (III) -2-ethylhexa Examples thereof include metal salts such as noate, bismuth (III) octoate and molybdenum glycolate.
The addition amount of the catalyst is desirably 0.01 to 5 parts by mass, particularly 0.05 to 1 part by mass when the total mass of the curable composition is 100 parts by mass.

  Various additives can be blended with the curable composition of the present invention as necessary. Examples of such additives include fillers, dyes and pigments, leveling agents, reactive diluents, non-reactive polymer resins, silane coupling agents, antioxidants, ultraviolet absorbers, light stabilizers, and antifoaming agents. , Dispersants, antistatic agents, and thixotropic agents.

  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, esters such as ethyl acetate and ethyl lactate, and fluorinated solvents. .

  The curable composition of the present invention can impart antifouling property, water repellency, oil repellency, fingerprint resistance and the like to the surface of the cured product by coating and curing on the surface of the substrate or by curing alone. As a result, it becomes difficult to be soiled by human fats such as fingerprints, sebum, sweat, cosmetics, and the like, and a cured product surface excellent in wiping property is provided even when the soil adheres. 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 material.

  Examples of articles on which the surface of the base material is treated include optical magnetic media such as magneto-optical discs, optical discs such as CD / LD / DVD / Blu-ray discs, optical recording media represented by hologram recording, etc .; eyeglass lenses, prisms, lens sheets , Pellicle film, polarizing plate, optical filter, lenticular lens, Fresnel lens, antireflection film, optical components and optical devices such as optical fiber and optical coupler; CRT, liquid crystal display, plasma display, electroluminescence display, rear projection display, fluorescence Various screen display devices such as display tubes (VFD), field emission projection displays, toner-based displays; especially PCs, mobile phones, personal digital assistants, game machines, electronic book readers, digital cameras, digital video cameras, Cash withdrawal and deposit device, cash dispenser, vending machine, navigation device for automobiles, image display device such as security system terminal, and touch panel (touch sensor, touch screen) type image display input device for operation thereof; Input devices such as telephones, portable information terminals, electronic book readers, portable music players, portable game machines, remote controllers, controllers, keyboards, panel switches for in-vehicle devices; cellular phones, portable information terminals, cameras, portable music players, mobile phones Case surface of game machines, etc .; Painting and surfaces of automobile exteriors, pianos, luxury furniture, marble, etc .; Protective glass for art exhibits, show windows, showcases, advertising covers, photo stand covers, watches, automobiles Windshields for windshields, trains, aircraft, etc. Scan, automobile headlights, made of transparent glass of the tail lamp and the like or a transparent plastic (acrylic, polycarbonate, etc.) member; various mirror member, and the like. In these applications, the curable composition of the present invention can be used not only for coating on the surface of the object, but also for transfer type hard coats widely used in in-mold molding and the like. .

When the curable composition of the present invention is applied to the surface of a substrate, examples of the application method include roll coating, gravure coating, dip coating, spray coating, spin coating, bar coating, and screen printing.
Further, the curing conditions of the curable composition of the present invention are not particularly limited, but are preferably 15 to 150 ° C. for several minutes to several tens of hours, particularly preferably 50 to 100 ° C. for 10 minutes to About 2 hours is desirable. Moreover, in order to suppress the reaction between the moisture in the air and the isocyanate group of the component (B), it is desirable that the humidity is an environment of 70% or less.
In addition, the thickness of the cured film obtained by applying and curing the curable composition of the present invention is usually about several nm to 100 μm, preferably several nm to 10 μm. When the obtained film thickness is less than the lower limit, sufficient surface hardness cannot be obtained, and when it is 100 μm or more, the mechanical strength of the coating film is lowered and cracks are likely to occur.

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

[Examples 1 to 3, Comparative Examples 1 and 2]
(A) Component: The following compound groups of the present invention (F-1 to F-3)

［Ｒｆ’：−ＣＦ₂（ＯＣＦ₂ＣＦ₂）_y（ＯＣＦ₂）_zＯＣＦ₂−
（ｙ／ｚ＝０．９、ｙ＋ｚ≒４５）］

[Rf ′: —CF ₂ (OCF ₂ CF ₂ ) _y (OCF ₂ ) _z OCF ₂ —
(Y / z = 0.9, y + z≈45)]

［Ｒｆ’：−ＣＦ₂（ＯＣＦ₂ＣＦ₂）_y（ＯＣＦ₂）_zＯＣＦ₂−
（ｙ／ｚ＝０．９、ｙ＋ｚ≒４５）］
及び、
本発明（Ａ）成分に相当しない化合物
ＨＯＣＨ₂Ｒｆ’ＣＨ₂ＯＨ （Ｆ−４）
［Ｒｆ’：−ＣＦ₂（ＯＣＦ₂ＣＦ₂）_y（ＯＣＦ₂）_zＯＣＦ₂−
（ｙ／ｚ＝０．９、ｙ＋ｚ≒４５）］
（Ｂ）成分：イソホロンジイソシアネート
（Ｃ）成分：メタクリル酸メチル（ＭＭＡ）と２−ヒドロキシ−エチルメタクリレート（ＨＥＭＡ）のランダム共重合体（ｍｏｌ比：ＭＭＡ／ＨＥＭＡ＝８８／１２、数平均分子量８，４００、ＯＨ基０．００１１ｍｏｌ／ｇ）

[Rf ′: —CF ₂ (OCF ₂ CF ₂ ) _y (OCF ₂ ) _z OCF ₂ —
(Y / z = 0.9, y + z≈45)]
as well as,
Compound not corresponding to component (A) of the present invention HOCH ₂ Rf′CH ₂ OH (F-4)
[Rf ′: —CF ₂ (OCF ₂ CF ₂ ) _y (OCF ₂ ) _z OCF ₂ —
(Y / z = 0.9, y + z≈45)]
(B) component: isophorone diisocyanate (C) component: random copolymer of methyl methacrylate (MMA) and 2-hydroxy-ethyl methacrylate (HEMA) (mol ratio: MMA / HEMA = 88/12, number average molecular weight 8, 400, OH group 0.0011 mol / g)

The above components (A), (B), and (C) were blended with a catalyst and a solvent in the following proportions to prepare a composition.
(Mixing ratio)
(A) Component 1 part by mass (not blended in the comparative example)
(B) Component 10 parts by mass (C) Component 89 parts by mass Dibutyltin (IV) dilaurate 0.1 parts by mass Tetrahydrofuran 100 parts by mass Methyl isobutyl ketone 100 parts by mass

The obtained composition 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 the heating, the temperature was returned to room temperature, and the properties of the cured coating surface were measured by the following method. The results are shown in Table 1.
In addition, about the comparative example 1 (compound (F-4)), the formulation was not compatible and the smooth surface was not obtained.

〔appearance〕
The transparency of the coating film and the presence or absence of defects were confirmed visually.
[Water contact angle / oleic acid contact angle]
Using a contact angle meter (A3 type, manufactured by Kyowa Interface Science Co., Ltd.), the water contact angle of the cured film and the contact angle with respect to oleic acid were measured.
(Dynamic friction coefficient)
Using a surface property tester (manufactured by Shinto Kagaku Co., Ltd.), the dynamic friction coefficient for Bencott M-3II (manufactured by Asahi Kasei Co., Ltd.) was measured.
[Magic repellency]
Using Hi-Maky Bold (manufactured by Zebra), the repelling condition when a line was drawn on the surface of the cured film was visually confirmed.
[Fingerprint wiping properties]
The fingerprint wiping property was evaluated by visually wiping with a tissue paper after the finger was pressed against it and wiped with tissue paper.

Claims (3)

(A) The following general formula (1)

[ Wherein, Rf is a monovalent or divalent number average molecular weight of 100 to 40,000 calculated from the ratio of the terminal structure and the main chain structure based on ¹ H-NMR and ¹⁹ F-NMR including a fluoropolyether structure. It is the basis of. Q ¹ is the following formula (2)

(Wherein, a and b are the same as a and b in formula (1), the broken line indicates a bond, a unit having a repeating unit of a is bonded to Rf, and a unit having a repeating unit of b is formula
-Q ² -OH
It bonds with the group shown by. Also, the arrangement of the two types of repeating units is random. Rf is as described above. )
In a linking group represented, Q ² is a divalent hydrocarbon group having 1 to 20 carbon atoms which may form a cyclic structure may include a middle ether bond or an ester bond. When Rf is monovalent, c is 1 and a is an integer of 1 to 6. When Rf is divalent, a is 1 and c is 2. b is an integer of 1-20. ]
A fluorine-containing alcohol compound represented by :
(B) a compound having two or more isocyanate groups in one molecule;
(C) Polyfunctional hydroxyl group-containing compound having two or more hydroxyl groups in one molecule and containing no fluorine atom
The component (A) is contained in an amount of 0.005 to 20 parts by mass in 100 parts by mass of the total amount of the components (A), (B) and (C), and NCO / OH (hydroxyl of all components in the composition) A curable composition having an equivalent ratio of (total amount of groups) of 0.5 to 2.0 . Furthermore, the curable composition of Claim 1 containing a catalyst. In the general formula (1), Q ² 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 curable composition of Claim 1 or 2 chosen from the group shown by these.