TWI504682B - A hardening composition containing a fluorine-containing alcohol compound - Google Patents

Description

Hardenable composition containing a fluorine-containing alcohol compound

The present invention relates to a curable composition containing a fluorine-containing alcohol compound, and more particularly to a curable composition having a coating agent or a coating composition which is cured at room temperature or at room temperature, which is excellent in various antifouling properties and water repellency. .

Furthermore, the present invention imparts excellent water repellency and oil repellency to the surface of parts such as metal, ceramic, quartz glass, glass, polyfluorene, wood, paper, general-purpose resin, electrostatic filter, dust cover, fuel cell, and the like. A curable composition of antifouling, heat resistance, weather resistance and abrasion resistance.

A fluorine-based material is used for the coating material such as polyoxymethylene resin to impart water repellency and antifouling properties.

However, many fluorine-based materials which are known at present are often poor in compatibility with a polyoxyxylene resin of a main component, and if a film is to be formed, twisting or repulsion occurs, and it is difficult to obtain a uniform film.

In addition, when the compatibility of the fluorine-based material is improved and a uniform film is formed, the water repellency and the antifouling property are insufficient.

Further, as a conventional technique related to the present invention, the following documents can be cited.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Publication No. 08-6032

[Patent Document 2] Japanese Patent Publication No. 05-59285

[Patent Document 3] Japanese Patent Laid-Open No. 07-18183

The present invention has been made in view of the above circumstances, and an object thereof is to provide a curable composition which is excellent in water repellency, oil repellency, antifouling property, heat resistance, weather resistance and abrasion resistance, and durability of the properties thereof. Surface treatment agent.

In order to achieve the above object, the inventors of the present invention have repeatedly conducted intensive evaluations, and have found that a fluorine portion for imparting water repellency and antifouling properties, a hydroxyl group for reacting with a curable resin, and a resin for curing and curing are particularly useful. The fluorine-containing alcohol compound represented by the following general formula (1) having a polyoxane-containing siloxane structure is excellent in compatibility with a curable resin such as a polysiloxane resin, and is blended with the above. The curable composition is a surface treatment agent which is excellent in water repellency, antifouling property, heat resistance, weather resistance and abrasion resistance, and durability of the properties, and finally completed the present invention.

Accordingly, the present invention provides a curable composition shown below.

[1] A curable composition characterized by the following: (A) the following general formula (1) (wherein Rf is a one- or divalent group having a molecular weight of 100 to 40,000 containing a fluoropolyether structure; and Q ¹ is a structure of at least (a+b) Si atoms which is unsubstituted or halogen-substituted by a decane. (a+b) valent linking group formed by a combination of an alkylene structure or an arylene structure or a combination of two or more of these, may form a cyclic structure; Q ² is a divalent carbon number of 1 to 20 The hydrocarbon group may also form a cyclic structure, and may also contain an ether bond or an ester bond; when Rf is monovalent, c is 1, and a is an integer from 1 to 6, and when Rf is divalent, a is 1. Further, c is 2; b is a fluorine-containing alcohol compound represented by an integer of 1 to 20: 0.005 to 20 parts by mass, and (B) contains a compound which can react with a hydroxyl group in the fluorine-containing alcohol compound represented by the general formula (1). Hydrolyzable alkylene or stanol-based compound: 100 parts by mass.

[2] The curable composition according to [1], wherein (B) a compound containing a hydrolyzable alkylene group or a stanol group is a polyoxyxylene resin.

[3] The curable composition according to [1] or [2], wherein in the formula (1), Q ¹ is represented by the following formula (2), [wherein, a and b are the same as a and b in the formula (1), and a broken line indicates a bond, a unit having a repeating unit of a and a Rf bond, and a unit having b repeating units and a lower a group bond of the formula -Q ² -OH (wherein Q ² is as defined in the formula (1)); further, the arrangement of the repeating units of the two species is random; and the Rf is as in the formula (1) Defined].

[4] The curable composition according to any one of [1] to [3] wherein, in the formula (1), Q ^{2 is} derived from -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 -

Selected from the group shown.

The curable composition containing a fluorine-containing alcohol compound of the present invention can form a cured layer having a surface excellent in water repellency, oil repellency, fingerprint resistance, and antifouling property by curing without impairing coating film formability and transparency. It is suitable as a forming material of a hardening type antifouling paint which hardens at heat or room temperature.

[Formation of the Invention]

Hereinafter, the present invention will be described in detail.

The curable composition of the present invention contains (A) a fluorine-containing alcohol compound represented by the following formula (1), and (B) contains a fluorine-containing alcohol compound represented by the formula (1). A hydroxy-reactive hydrolyzable decyl or stanol-based compound.

In the curable composition of the present invention, as the component (A), the following general formula (1) is used. (wherein Rf is a one- or divalent group having a molecular weight of 100 to 40,000 containing a fluoropolyether structure; and Q ¹ is a structure of at least (a+b) Si atoms which is unsubstituted or halogen-substituted by a decane. (a+b) valent linking group formed by a combination of an alkylene structure or an arylene structure or a combination of two or more of these, may form a cyclic structure; Q ² is a divalent carbon number of 1 to 20 The hydrocarbon group may also form a cyclic structure, and may also contain an ether bond or an ester bond; when Rf is monovalent, c is 1, and a is an integer from 1 to 6, and when Rf is divalent, a is 1. Further, c is 2; b is a fluorine-containing alcohol compound represented by an integer of 1 to 20. By blending a fluorine-containing alcohol compound, it is possible to impart antifouling property, fingerprint resistance, water repellency, and oil repellency to the surface of the cured product of the curable composition.

In the formula (1), Rf is a fluoropolyether structure having a molecular weight of 100 to 40,000, preferably 500 to 20,000, or a divalent group. Further, in the present invention, the molecular weight is a number average molecular weight calculated from a ratio of a terminal structure to a main chain structure based on ¹ H-NMR and ¹⁹ F-NMR.

As Rf, it contains 1 to 500 repeating units represented by the following formula -C _h F _2h O- (h is an integer of 1 to 6 per unit independently), preferably 2 to 400, more preferably 4~ 200 are suitable.

The particularly preferable structure of Rf can be represented by the following 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 divalent molecular weight of 300 to 30,000, especially a perfluoropolyether group of 500 to 20,000, and may also contain a branch on the way, particularly preferably a divalent perfluoropolyether represented by the following formulas (5) to (7). base.

(In the formula (5), Y is each independently F or a CF ₃ group, r is an integer of 2 to 6, and m and n are each 0 or 1 to 200, preferably 0 or an integer of 1 to 100, but m +n is 2~200, preferably an integer of 3~150; s is an integer of 0 or 1~6, and each repeating unit can also be randomly bonded); [Chemical 6]-C _j F _2j (OCF ₂ CF ₂ CF ₂ ) _k OC _j F _2j - (6) (wherein j is an integer of 1 to 3, and k is an integer of 1 to 200, preferably 1 to 60).

(wherein Y is a F or CF ₃ group, j is an integer from 1 to 3, and t and u are each 0 or 1 to 200, preferably an integer of 2 to 100, but t+u is 2 to 300, Good is an integer from 4 to 200; each repeating unit can also be randomly bonded).

Q ³ is a divalent organic group, preferably a divalent hydrocarbon group having 2 to 20 carbon atoms, particularly preferably 3 to 12, and may also contain an oxygen atom, a nitrogen atom, a fluorine atom or a halogen atom, and may also have a cyclic structure or A group having an unsaturated bond. As such Q ³ , the following is exemplified. Further, in the formula, Ph represents a phenyl group.

Among these, Tejia is

Also, T is the following formula (4) (wherein Q ² , a, and b are as defined above, and Q ⁴ is an anthracene alkyl structure having at least (a+b) Si atoms, a non-substituted or halogen-substituted alkylene structure, and an anthracene aryl group. a (a+b) valent linking group composed of a structure or a combination of two or more of these, wherein the divalent portion is used for the bond with Q ³ among the (a+b) valence of Q ¹ described above A divalent linking group represented by a siloxane structure, an unsubstituted or halogen-substituted fluorene alkyl structure, a fluorene-extended aryl structure, or a combination of two or more of these.

As Q ⁴ , the following are exemplified. However, in the following formula, the bond bond of the divalent moiety shown by the solid line is bonded to Q ^{3 , and the} bond bond of (a+b-2) moiety shown by the dotted line is -Q ² -OH (formula) In the case where Q ² is a base bond as shown in the above). Further, in the case of the following formula (a), the dotted line of the unit at both ends is linked to -Q ² -OH, and the unit of the both ends and the unit of (a+b-4), -Q ² The group represented by -OH is bonded to the bond of (a + b-2) parts. Further, the arrangement of the above-mentioned unit, (a+b-2) unit, and p unit in the divalent portion shown by the solid line is random. a and b are preferably integers of a and b which are 1 to 4, and a+b is 3 to 6, especially an integer of 3 to 5. p is an integer of 0 or more, and the upper limit of p is 12 or less, and particularly preferably 6 or less.

Here, Q ⁵ is a (a+b)-valent linking group, and for example, the following may be exemplified.

When Q _f is Q ³ or V=0, it is a fluorine atom.

Further, v is an integer of 0 or 1 to 5, and particularly preferably 0 or 1, particularly 0. However, 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.

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

In the formula (1), a is 1 to 6, preferably an integer of 1 to 4, b is 1 to 20, preferably an integer of 1 to 4, and c is 1 or 2, except when Rf is monovalent, a is an integer from 1 to 6, and c is 1. When Rf is divalent, a is 1 and c is 2; b is an integer from 1 to 20, particularly preferably an integer from 1 to 6, a+b is Good for 3~6, especially good for 3~5.

In the formula (1), Q ¹ is an alkylene structure having at least (a+b) Si atoms, a non-substituted or halogen-substituted alkylene structure, an anthracene aryl structure, or two or more thereof. The (a+b) valent linking group formed by the combination may form a ring structure, specifically, the following structure.

However, in the following formula, a and b are as defined above, and a and b are preferably integers of 1 to 4, and a+b is an integer of 3 to 6, especially 3 to 5. p is an integer of 0 or more, and the arrangement of each of a and b and p units is random, and the binding bond shown by the dotted line of each of a and b units is Rf- or -Q ² - Any one of the groups represented by OH (wherein Rf and Q ² are as described above) is bonded. Further, the upper limit of p is preferably 12 or less, and particularly preferably 6 or less.

Further, the unit of a+b can be represented separately from the unit of a and the unit of b, the bond of Rf is bonded to the unit of a, and the bond of -Q ² -OH is bonded to the unit of b (Rf Q ² is as described above). In the case of the formula (b), the dotted line of the unit at both ends is connected to Rf or -Q ² -OH, and thus the unit of both ends and the unit of (a+b-2) constitute (a+b). Unit of the unit.

Further, Q ⁵ is as described above, and Q ⁵ can be exemplified as described above.

As Q ¹ , a structure represented by the following formula (2) is more preferable.

[wherein, a and b are the same as described above, and a broken line represents a bond, and a unit having a repeating unit of a is bonded to the above Rf, and a unit having b repeating units and the following formula -Q ² -OH (wherein Q ² is the same as described above); in addition, the arrangement of the two types of repeating units is random].

In the formula (1), the Q ² is a divalent hydrocarbon group having 1 to 20 carbon atoms, preferably 2 to 15 carbon atoms, and may form a cyclic structure or an intermediate ether bond (-O-) or an ester bond (-COO-). ). Specifically, the following constructors are mentioned.

-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 above formula (1) can be synthesized, for example, by the following method.

First, a polyfunctional Si-H compound (for example, a fluorene oxide having two or more, preferably three or more Si-H groups in a molecule, a fluorinated compound (i) having an olefin group at the terminal Alkyl, aryl or such (ii) The hydrofluorination addition reaction is carried out under conditions in which the Si-H group is excessive, and the fluorine-containing polyfunctional Si-H compound (iii) is synthesized.

Among such compounds (i), a general structure is used as an example of generalization, and the following formula (8) can be exhibited.

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 - indicates. In the above formula, Rf', T, Q _f , Q ³ and v are as described above, and the Q ⁶ -based divalent organic group is preferably a divalent hydrocarbon group having 1 to 20 carbon atoms and particularly preferably 1 to 10 carbon atoms, and may contain An oxygen atom, a nitrogen atom, a fluorine atom or a ruthenium atom, and may also be a cyclic structure or a group having an unsaturated bond; x is 1 when Rf ⁰ is monovalent and 2 when it is divalent.

As Q ^6, may be exemplified by the following. Further, in the following examples, Ph represents a phenyl group.

As a particularly preferable compound (i), the following can be exemplified.

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

Further, the compound (ii) may be in the form of the following formula (9) and represented by the formula.

Q ¹ -(H) _a+b (9) (wherein Q ¹ , a, b are as described above, and the H system shown in the parentheses is directly bonded to the hydrogen atom of the Si atom in the Q ¹ structure).

Among the above, as the preferred compound (ii), the following may be exemplified.

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

Any combination of the above compound (i) and the compound (ii) may be carried out in the presence of a platinum group metal addition reaction catalyst at a reaction temperature of 60 to 150 ° C, preferably 70 to 120 ° C, to carry out an addition reaction. A fluorine-containing polyfunctional Si-H compound (iii) was obtained.

For example, when the compound (i) is monofunctional (x=1 in the formula (8)), if the number of the compound (i) added to the compound (ii) is less than (a+b), There is no problem with one or a plurality of compounds. For example, the compound (iii) obtained by adding a is represented by the following formula (10).

(Rf ⁰ -C ₂ H ₄ ) _a -Q ¹ -(H) _b (10) (Rf ⁰ , Q ¹ , a, b are as described above, and the H system shown in parentheses is directly bonded to the Q ¹ structure The hydrogen atom of the Si atom).

On the other hand, when the compound (i) is bifunctional (x = 2 in the formula (8)), it is preferred to use the ratio of the compound (i): compound (ii) = v + 1 : v + 2 (mole ratio) The addition (v is as described above), the obtained compound (iii) can be expressed, for example, by the formula (11), and when v=0, the compound (ii) is introduced at one end of the compound (i). Construction.

(H) _b -Q ¹ -[C ₂ H ₄ -Rf ⁰ -C ₂ H ₄ -T ² ] _v -C ₂ H ₄ -Rf ⁰ -C ₂ H ₄ -Q ¹ -(H) _b (11) (where T ² is The groups shown, Q ¹ , Q ⁴ , Rf ⁰ , a, b, v are as described above, and the H series shown in parentheses is directly bonded to the hydrogen atom of the Si atom in the Q ¹ or Q ⁴ structure).

The above addition reaction can be carried out even in the absence of a solvent, but it may be diluted with a solvent as needed. In this case, the diluent solvent may be a widely used organic solvent such as toluene, xylene or isooctane, but it is preferably at least the reaction temperature of the boiling point and does not hinder the reaction, and the compound (iii) formed after the reaction is The reaction temperature is soluble. For example, it is preferably a fluorine-modified aromatic hydrocarbon solvent such as hexafluoro-m-xylene or trifluoromethylbenzene, or a fluorine-modified solvent such as a fluorine-modified ether solvent such as methyl perfluorobutyl ether. Good is hexafluorom-xylene.

As the addition reaction catalyst, for example, a compound containing platinum, rhodium or palladium can be used. Among them, a platinum-containing compound is preferred, and hexachloroplatinum (IV) acid hexahydrate, platinum carbonyl vinyl methyl complex, platinum-divinyltetramethyldioxane complex, platinum may be used. a cyclovinylmethyl oxime complex, a platinum-octanal/octanol complex, or a platinum supported on activated carbon. The amount of the catalyst to be mixed is preferably from 0.1 to 5,000 ppm by mass, more preferably from 1 to 1,000 ppm by mass, based on the compound (i).

In the addition reaction, the order of addition of the components is not particularly limited. For example, a method of slowly heating a mixture of the compound (i), the compound (ii) and the catalyst from room temperature to the addition reaction temperature may be employed. After heating the mixture of the compound (i), the compound (ii) and the diluent solvent to the intended reaction temperature, a catalyst is added to the mixture of the compound (ii) and the catalyst heated to the intended reaction temperature. In the method of dropping the compound (i), a method of dropping a mixture of the compound (i) and a catalyst in the compound (ii) heated to the intended reaction temperature. In particular, it is particularly preferred to add a catalyst to the mixture of the compound (i), the compound (ii) and the diluent solvent to the desired reaction temperature, or to a compound (ii) which has been heated to the intended reaction temperature. In the method of dropping a mixture of the compound (i) and a catalyst. These methods can be used by diluting the components or mixtures with a solvent as needed. The above reaction is preferably 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 hours.

For the compound (i), the compound (ii) is blended in an amount as long as it is one molecule relative to the compound (ii), and the amount of the compound (i) added is less than (a+b), and the condition that v in the compound (iii) is 0 or an integer of 1 to 5 may be any blending amount, but is preferably relative to the compound (i) in order to prevent cubic cross-linking. The terminal olefin group such as allyl group is subjected to an addition reaction using an excess amount of the compound (ii), and then the unreacted compound (ii) is removed by distillation under reduced pressure or the like, relative to the olefin of the compound (i). The terminal olefin group of the propyl group or the like is preferably one equivalent, and the compound (ii) is preferably reacted in the presence of 1 to 10 equivalents, particularly 2 to 6 equivalents. Further, after the synthesis of the small intermediate of v, the addition reaction may be carried out in stages as needed. For example, after the compound (iii) having v = 0 in the formula (8), the compound (iii) of v=0 in the formula (11) is synthesized, and for the compound (iii) 2 mol, the formula (8) is obtained. Compound (i) in which x = 2 is reacted again with 1 molar to obtain compound (iii) having v = 3. Alternatively, in the compound (iii), a component having a desired v value may be separated by any separation means from a mixture of v. For example, only a component of v = 1 can be taken out from a mixture of v = 0 to 3 in the compound (iii) by means of fractionation chromatography or the like.

The fluorine-containing alcohol compound used in the present invention can be obtained by subjecting an Si-H group of the compound (iii) obtained above to an addition reaction of a compound (iv) having a terminal olefin group and an alcoholic hydroxyl group in one molecule. obtain. As such a compound (iv), the following are particularly preferable. These compounds (iv) may be used alone or in combination of two or more.

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 (iii) with the compound (iv) can be carried out in the same manner as the addition reaction of the compound (i) and the compound (ii). That is, in the presence of the above-mentioned addition reaction catalyst, in a dry environment, in air or an inert gas (N ₂ , Ar, etc.), the reaction temperature is usually 50 to 150 ° C, preferably 60 to 120 ° C. 0.5 to 96 hours, preferably 1 to 48 hours, diluted as needed, and reacted in any order of addition.

For the compound (iii), the compound (iv) may be blended in an arbitrary amount, but is preferably added to the Si-H group of the compound (iii) using an equimolar or excess amount of the compound (iv). After the reaction, the unreacted compound (iv) is removed by distillation under reduced pressure or the like, and particularly preferably 1 to 5.0 equivalents, preferably 1.0 to 2.0 equivalents per equivalent of the Si-H group of the compound (iii). The reaction is carried out in the presence of the compound (iv).

In the present invention, the fluorine-containing alcohol compound (A) can be subjected to the following formula in addition to the above-mentioned method.

(Rf) _a -[Q ¹ -(H) _b ] _c (Q ¹ , b and Rf are as described above) are obtained by an addition reaction of a fluorine-containing organofluorene compound (V) with a compound (iv). In this case, the reaction conditions and the like can be the same as those of the above compound (iii) and the compound (iv).

As the fluorine-containing alcohol compound (A) represented by the formula (1) thus obtained, The particularly preferable structure is exemplified by the following.

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

The curable composition of the present invention is characterized in that the fluorine-containing alcohol compound obtained as described above is blended, and by curing the composition, antifouling properties, fingerprint resistance, water repellency, and oil repellency can be imparted to the surface of the cured product.

The blending amount of the fluorine-containing 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 per 100 parts by mass of the component (B) (component) to be described later. Share. When the above-mentioned upper limit is exceeded, the amount of the fluorine-containing alcohol compound is too large, and the performance of the cured product may be impaired. When the lower limit is not reached, the fluorine component is reduced, and the surface of the hard coat layer may not be sufficiently covered.

In the curable composition of the present invention, as the component (B), a compound containing a hydrolyzable alkylene group or a stanol group capable of reacting with a hydroxyl group in the above fluorine-containing alcohol compound is blended.

Specific examples of the hydrolyzable group include an alkoxy group, a decyl group, an isopropenyloxy group, and a vinyloxy group, and a methoxy group, an ethoxy group, an isopropoxy group or the like is preferable.

The compound containing such a hydrolyzable alkylene group or a stanol group is not particularly limited as long as it contains a hydrolyzable alkylene group or a stanol group which reacts with a hydroxyl group in the above fluorine-containing alcohol compound, and a film can be formed. The following decane compound, or a partially hydrolyzed condensate thereof, and a general-purpose resin such as a polyfluorene oxide resin, an acrylic resin, a polyester resin, or an epoxy resin obtained by the above may be mentioned. These types are used in combination of not only one type but also two or more types. Among them, a polyfluorene oxide resin excellent in compatibility with a fluorine-containing alcohol compound is preferable.

The polyoxyxyl resin may be one or two or more kinds of condensates selected from the group consisting of a hydrolyzable group-containing decane such as alkoxy decane or chlorodecane, and a partial (co)hydrolyzate. The raw material (the hydrolyzable group-containing decane) to be used is one, two or three as long as the type of the hydrolyzable group is a chlorine atom, an alkoxy group, a decyl group, an isopropenyloxy group or a vinyloxy group. Or 4 such hydrolyzable groups, any of the decane compounds satisfying the above conditions may be used.

Specific examples of such a decane compound include tetrachlorodecane, tetramethoxydecane, tetraethoxydecane, tetrabutoxydecane, methyltrichlorodecane, methyltrimethoxydecane, and methyltriethyl. Oxy decane, methyl triisopropoxy decane, methyl tributoxy decane, methyl triisopropoxy decane, dimethyl dichloro decane, dimethyl dimethoxy decane, dimethyl di Ethoxy decane, dimethyl diisopropoxy decane, dimethyl dibutoxy decane, dimethyl diisopropoxy decane, trimethyl chlorodecane, trimethyl methoxy decane, trimethyl Ethoxy decane, trimethyl isopropoxy decane, ethyl trichloro decane, ethyl trimethoxy decane, propyl trichloro decane, butyl trichloro decane, butyl trimethoxy decane, hexyl trichloro Decane, hexyltrimethoxydecane, decyltrichlorodecane, decyltrimethoxydecane, phenyltrichlorodecane, phenyltrimethoxydecane, cyclohexyltrichlorodecane, cyclohexyltrimethoxydecane,propylpropyl Dichlorodecane, propylmethyldimethoxydecane, hexylmethyldichlorodecane, hexylmethyl Methoxydecane, phenylmethyldichlorodecane, phenylmethyldimethoxydecane, diphenyldichlorodecane, diphenyldimethoxydecane, dimethylphenylchlorodecane, and the like Partially hydrolyzed, etc.

In addition, vinyl trichlorodecane, vinyl trimethoxy decane, vinyl triethoxy decane, vinyl methyl dichloro decane, vinyl methyl dimethoxy decane, vinyl methyl diethylene can also be used. Oxydecane, 5-hexenyltrimethoxydecane, 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropyltriethoxydecane, 3-epoxypropoxy Propylmethyldimethoxydecane, 3-glycidoxypropylmethyldiethoxydecane, 3-(A Acryloxypropyltrimethoxydecane, 3-(meth)acryloxypropyltriethoxydecane, 3-(methyl)propenyloxypropylmethyldimethoxydecane , 3-(methyl)propenyloxypropylmethyldiethoxydecane, 4-vinylphenyltrimethoxydecane, 3-(4-vinylphenyl)propyltrimethoxydecane, 4 -vinylphenylmethyltrimethoxydecane, 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 3-aminopropylmethyldimethoxydecane, 3 -Aminopropylmethyldiethoxydecane, 3-(2-aminoethyl)aminopropyltrimethoxydecane, 3-mercaptopropyltrimethoxydecane, 3-mercaptopropyltriethoxylate A decane having a reactive functional group such as decane, 3-mercaptopropylmethyldimethoxydecane or 3-mercaptopropylmethyldiethoxydecane.

From the viewpoints of ease of distillation of the handleability and by-products, it is preferred to use a methoxy group-containing decane or an ethoxy group-containing decane. The decane compound which can be used is not limited to this. Further, one type of these decane compounds or a mixture of two or more types may be used.

Further, in the present invention, a decane compound which forms a siloxane skeleton which is exemplified as the above-mentioned raw material may be used as the component (B) as it is.

The hydrolyzable decane compound is hydrolyzed and condensed to obtain a polyfluorene resin which can be used in the present invention, and can be obtained from aromatic hydrocarbons such as toluene and xylene, hydrocarbons such as hexane and octane. a ketone compound such as methyl ethyl ketone or methyl isobutyl ketone; an ester compound such as ethyl acetate or isobutyl acetate; methanol, ethanol, isopropanol, butanol, isobutanol, and third Hydrolysis and condensation in an organic solvent selected from alcohols such as butanol Further, a polyfluorene oxide resin containing a hydrolyzable alkylene group and/or a stanol group is obtained.

Here, at the time of hydrolysis, the amount of water to be used is less than the amount required for the total hydrolysis of the alkoxy group of the raw material, and the finally obtained polyoxyxene resin after condensation is contained in a large amount. A hydrolyzable decyl methoxy or ethoxylated polyoxyl resin. Further, in order to hydrolyze all of the alkoxy groups of the obtained polyoxynoxy resin, more polyhydric alcohol can be added to the polyfluorene resin by adding more water than necessary. Oxygen resin.

A hydrolysis catalyst can also be used in the case of performing hydrolysis and condensation. As the hydrolysis catalyst, a conventional catalyst can be used, and an acidic solution of pH 2 to 7 can also be used. In particular, an acidic hydrogen halide, a carboxylic acid, a sulfonic acid, an acidic or weakly acidic inorganic salt, a solid acid such as an ion exchange resin, or the like is preferable. As an example, an organic carboxylic acid typified by hydrogen fluoride, hydrochloric acid, nitric acid, sulfuric acid, acetic acid, or maleic acid, methanesulfonic acid, a cation exchange resin having a sulfonic acid group or a carboxylic acid group on the surface, and the like can be given. The amount of the hydrolysis catalyst is preferably in the range of 0.001 to 10 mol% with respect to the hydrolyzable group 1 mol on the ruthenium atom.

The reaction temperature is usually 0 to 120 ° C, and the reaction time may be as long as the reaction is sufficiently carried out, and is usually about 30 minutes to 24 hours.

The polyoxyxylene resin may also be prepared as a solution which is uniformly dissolved in the above solvent. In this case, the concentration of the polyoxyxylene resin in the solution is not particularly limited as long as the range of the homogeneous solution is obtained, but is preferably from 5 to 100% by mass, more preferably from about 20 to 60% by mass.

The polyoxyxylene resin of the component (B) thus obtained has a viscosity at 25 ° C as measured by Cannon-Fenske of usually 1 to 1,000 mm ² /s, preferably 1 to 100 mm ² /s.

Further, the amount of the hydrolyzable alkylene group or stanol group is usually 0.5 to 10% by mass, preferably 1 to 5% by mass.

In the curable composition of the present invention, a curing catalyst for curing the polyoxyxene resin or a leveling agent for the purpose of improving film formation properties may be used. As the curing catalyst, an inorganic or organic acid, an amine compound or an alkali substance, an organometallic compound such as an organotin, a titanium or an aluminum compound, a hydroquinone catalyst such as chloroplatinic acid, or a UV curing agent can be used. material. As the leveling agent, a polyether modified oil, a fluorine-containing surfactant, or the like can be used.

The amount of the catalyst added is usually 0.1 to 15% by mass, preferably 1 to 10% by mass, based on the polyoxymethylene resin.

Further, in the curable composition of the present invention, various additives may be blended as needed. Examples of such an additive include a filler, a dye pigment, a leveling agent, a reactive diluent, a non-reactive polymer resin, a decane coupling agent, an acid-resistant agent, an ultraviolet absorber, a photostabilizer, and an antifoaming agent. A dispersant, an antistatic agent, and a thixotropic imparting agent.

The curable composition of the present invention can also be used by being diluted with any solvent. Examples of the particularly preferable solvent include alcohols such as isopropyl alcohol and butanol, ethers such as tetrahydrofuran and diethylene glycol dimethyl ether, and ketones such as methyl ethyl ketone and methyl isobutyl ketone. An ester such as ethyl acetate or ethyl lactate or a fluorine-based solvent.

The curable composition of the present invention can be coated on the surface of the substrate by hard coating It is hardened by a monomer, and imparts antifouling property, water repellency, oil repellency, fingerprint resistance, and the like to the surface of the cured product. Therefore, it is difficult to be contaminated by human fat such as fingerprints, sebum, sweat, or the like, and the like, and it is possible to give a surface of a cured product which is excellent in wiping property even when stains are adhered. Therefore, the curable composition of the present invention can be used to form a coating film or a protective film, and can be applied to the surface of an article which is likely to be contaminated by human fat or cosmetics due to human contact, and is particularly useful as a hardened film. Coating material.

Examples of such an object treated on the surface of the substrate include optical recording media such as optical disks, CDs, CDs, DVDs, Blu-ray disks, and the like, and holograms, lenses, lenses, and lenses. Optical parts such as sheets, films, polarizers, optical filters, lenticular lenses, Fresnel lenses, anti-reflection films, optical fibers or optical couplers ‧ optical devices; CRT, liquid display, plasma display, electroluminescent display Various screen display devices such as rear projection type display, fluorescent display tube (VFD), electroluminescence display, and toner display, especially PC, mobile phone, portable information terminal, game machine, e-book, digital camera, Digital video camera, automatic cash withdrawal storage device, automatic cash dispenser, vending machine, navigation device for automobile, navigation device, security image system, etc., and touch panel (touch sensing) Device, touch screen) image display input device; mobile phone, portable information terminal, e-book, portable music player, portable game machine, remote controller, controller Input devices such as keyboards, keyboard switches, etc.; mobile phone, portable information terminal, camera, portable music player, portable game machine, etc.; car exterior, piano, high-grade furniture, Painting of marble, etc. And surface; transparent glass made of protective glass, display window, display box, advertising cover, photo seat cover, watch, front glass for automobile, train, aircraft, etc., window glass, automobile headlights, taillights, etc. Or transparent plastic (acrylic, polycarbonate, etc.) components, various mirror components, and so on. In such applications, the curable composition of the present invention is not only applied to the surface of the object but also to a transfer type hard coat which is widely used in in-mold molding.

When the curable composition of the present invention is applied to the surface of a substrate, examples of the coating method include gravure coating, roll coating, rod coating, blade coating, knife coating, and die molding. Coating, impregnation coating, mesh coating, spin coating, curtain coating, spray coating, and the like.

Moreover, the curing conditions of the curable composition of the present invention are usually room temperature to 200 ° C for 30 minutes to 24 hours.

Further, the thickness of the cured film obtained by applying and curing the curable composition of the present invention is preferably 1 μm to 3 mm, more preferably 5 μm to 1 mm.

[Examples]

Hereinafter, the present invention will be specifically described by showing synthesis examples, blending examples, examples and comparative examples, but the present invention is not limited by the following examples.

(A) component

Hereinafter, the compound group of the present invention (F-1 to F-3)

[Rf':-CF ₂ (OCF ₂ CF ₂ ) _y (OCF ₂ ) _z OCF ₂ -(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)]

And a compound not equivalent to the 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 [Synthesis Example 1]

In a 1 liter flask equipped with a stirring device, a Liebig cooler, a dropping funnel and a thermometer, 96.1 parts by mass of a compound having an average composition formula of CH ₃ (OCH ₃ ) ₂ SiOSi(OCH ₃ ) ₂ CH _{3 was added} . 18.0 parts by mass of the compound represented by (CH ₃ ) ₂ Si(OCH ₃ ) ₂ and 76.9 parts by mass of toluene were added while stirring 3.4 g of methanesulfonic acid, and 27.0 parts by mass of water was added dropwise for 1 hour, and the mixture was aged at 30 ° C. 12 hours.

The obtained liquid was neutralized with sodium hydrogencarbonate, and the by-produced alcohol was distilled off, washed with water, dehydrated, filtered, and placed at 105 ° C for 3 hours, and then diluted with toluene so that the measured nonvolatile content was 40% by mass. The decyl alcohol group-containing polyfluorene oxide resin having a viscosity of ² mm ² /s at 25 ° C as measured by a Cannon-Fenske and having a hydroxyl group content of 2.2% by mass as measured by a Grignard method was obtained.

[Admixing Example 1]

Mixed (CH ₃ )(CH ₃ O) ₂ SiOSi(CH ₃ )(OCH ₃ ) ₂ 50 parts by mass, (CH ₃ ) ₂ Si(OCH ₃ ) ₂ 40 parts by mass, (C ₄ H ₉ O)Al(- OC(CH ₃ )=CHCOOC ₂ H ₅ ) ₂ 10 parts by mass to obtain a polyoxyxane mixture containing an alkoxy group.

[Example 1]

(1) part by mass of (A-1) component, 250 parts by mass of the polyfluorene oxide resin obtained in Synthesis Example 1 (100 parts by mass of the active ingredient), and a curing catalyst (C ₄ H ₉ O) _{) Al (-OC (CH 3)} = CHCOOC 2 H 5) ₂₁ parts by mass of methyl and isobutyl ketone solvent of 150 parts by mass, to prepare a composition.

The obtained composition was applied onto a glass plate with a wire rod having a gap of 24 μm, and heated at 150 ° C for 1 hour. After the end of the heating, the temperature was returned to room temperature, and the properties of the cured coated surface were measured by the method shown below. The results are shown in Table 1.

[Exterior]

The transparency and the presence or absence of defects of the coating film were confirmed by visual observation.

[water contact angle]

It was measured using a contact angle meter (A3 type manufactured by Kyowa Interface Science Co., Ltd.).

[oleic acid contact angle]

It was measured using a contact angle meter (A3 type manufactured by Kyowa Interface Science Co., Ltd.).

[Dynamic friction coefficient]

The coefficient of dynamic friction was measured by HEIDON TRIBOGEAR TYPE HSS2000 manufactured by Shinto Scientific Co., Ltd.

[Singular ink repellency]

The singular ink repellency was confirmed by visual inspection using the singular ink No. 500 black manufactured by Sisei Chemical Co., Ltd. by visual inspection to confirm the repulsion when the surface of the hardened film was drawn.

[fingerprint wiping]

After attaching the fingerprint, the appearance after wiping with the toilet paper was visually judged.

[Examples 2, 3, Comparative Examples 1, 2]

The component (A) was changed as shown in Table 1, and evaluated in the same manner as in Example 1. The results are shown together in Table 1.

Regarding Comparative Example 1 (Compound (F-4)), the blend was incompatible, and a smooth surface could not be obtained.

[Example 4]

One part by mass of the component (A-1) (F-1) and 100 parts by mass of the polyfluorene oxide mixture obtained in the blending example 1 of the component (B) were mixed to obtain a composition.

The resulting composition was applied to a glass plate with a wire bar having a gap of 24 μm, and allowed to stand at 25 ° C for 24 hours. The properties of the cured coated surface were measured in the same manner as in Example 1. The results are shown in Table 2.

[Examples 5 and 6, Comparative Examples 3 and 4]

The component (A) was changed as shown in Table 2, and evaluated in the same manner as in Example 4. The results are shown together in Table 2.

Regarding Comparative Example 3 (Compound (F-4)), the blend was incompatible, and a smooth surface could not be obtained.

Claims (4)

A curable composition characterized by the following: (A) the following general formula (1) (wherein Rf is a one- or divalent group having a molecular weight of 100 to 40,000 containing a fluoropolyether structure; and Q ¹ is a structure of at least (a+b) Si atoms which is unsubstituted or halogen-substituted by a decane. (a+b) valent linking group formed by a combination of an alkylene structure or an arylene structure or a combination of two or more of these, may form a cyclic structure; Q ² is a divalent carbon number of 1 to 20 The hydrocarbon group may also form a cyclic structure, and may also contain an ether bond or an ester bond; when Rf is monovalent, c is 1, and a is an integer from 1 to 6, and when Rf is divalent, a is 1. Further, c is 2; b is a fluorine-containing alcohol compound represented by an integer of 1 to 20: 0.005 to 20 parts by mass, and (B) contains a compound which can react with a hydroxyl group in the fluorine-containing alcohol compound represented by the general formula (1). Hydrolyzable alkylene or stanol-based compound: 100 parts by mass. The curable composition of claim 1, wherein (B) the compound containing a hydrolyzable alkylene group or a stanol group is a polyoxyxylene resin. The hardenable composition of claim 1 or 2, wherein in the formula (1), Q ¹ is represented by the following formula (2), [wherein, a and b are the same as a and b in the formula (1), and a broken line indicates a bond, a unit having a repeating unit of a and a Rf bond, and a unit having b repeating units and a lower a group bond of the formula -Q ² -OH (wherein Q ² is as defined in the formula (1)); further, the arrangement of the repeating units of the two species is random; and the Rf is as in the formula (1) Defined]. The sclerosing composition of claim 1 or 2, wherein in the formula (1), Q ^{2 is} derived from -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 - Selected from the group shown.