Fluorine-containing boric acid PVB composite

Abstract

A fluorine-containing boric acid PVB composite comprising a condensate of a fluorine-containing alcohol, boric acid and polyvinyl butyral, wherein the fluorine-containing alcohol is represented by the general formula:
Rf(A-OH).sub.k
wherein k is 1 or 2; when k is 1, Rf is a perfluoroalkyl group having 6 or less carbon atoms, a polyfluoroalkyl group in which some of the fluorine atom or atoms of the perfluoroalkyl group are replaced by hydrogen atom or atoms, a polyfluoroalkyl group containing a terminal perfluoroalkyl group having 6 or less carbon atoms and a perfluoroalkylene group having 6 or less carbon atoms, or a linear or branched, perfluoroalkyl group containing a terminal perfluoroalkyl group having 6 or less carbon atoms, a perfluoroalkylene group having 6 or less carbon atoms and ether bonds; when k is 2, Rf is a linear or branched, perfluoroalkylene group or polyfluoroalkylene group, containing a perfluoroalkylene group having 6 or less carbon atoms and ether bonds; and A is an alkylene group having 1 to 6 carbon atoms.

Claims

1. A fluorine-containing boric acid PVB composite comprising a condensate of a fluorine-containing alcohol, boric acid and polyvinyl butyral, wherein the fluorine-containing alcohol is represented by the general formula:
C.sub.nF.sub.2n+1(CH.sub.2CF.sub.2).sub.a(CF.sub.2CF.sub.2).sub.b(CH.sub.2CH.sub.2).sub.cOH[III] wherein n is an integer of 1 to 6, a is an integer of 1 to 4, b is an integer of 0 to 2, and c is an integer of 1 to 3, wherein, based on 100 parts by weight of fluorine-containing alcohol, the boric acid is used at a ratio of 0.1 to 100 parts by weight, and the polyvinyl butyral is used at a ratio of 5 to 600 parts by weight.

2. A fluorine-containing boric acid PVB composite comprising a condensate of a fluorine-containing alcohol, boric acid and polyvinyl butyral, wherein the fluorine-containing alcohol is a hexafluoropropene oxide oligomer alcohol represented by the general formula:
C.sub.mF.sub.2m+1O[CF(CF.sub.3)CF.sub.2O].sub.dCF(CF.sub.3)(CH.sub.2).sub.eOH[IIa] wherein m is an integer of 1 to 3, d is an integer of 0 to 100 and e is an integer of 1 to 3, wherein, based on 100 parts by weight of fluorine-containing alcohol, the boric acid is used at a ratio of 0.1 to 100 parts by weight, and the polyvinyl butyral is used at a ratio of 5 to 600 parts by weight.

3. A fluorine-containing boric acid PVB composite comprising a condensate of a fluorine-containing alcohol, boric acid and polyvinyl butyral, wherein the fluorine-containing alcohol is a perfluoroalkylene ether diol represented by the general formula:
HO(CH.sub.2).sub.fCF(CF.sub.3)[OCF.sub.2CF(CF.sub.3)].sub.gO(CF.sub.2).sub.hO[CF(CF.sub.3)CF.sup.2O].sub.iCF(CF.sub.3)(CH.sub.2).sub.fOH[IIb] wherein f is an integer of 1 to 3, g+i is an integer of 0 to 50, and h is an integer of 1 to 6, wherein, based on 100 parts by weight of fluorine-containing alcohol, the boric acid is used at a ratio of 0.1 to 100 parts by weight, and the polyvinyl butyral is used at a ratio of 5 to 600 parts by weight.

4. A fluorine-containing boric acid PVB composite comprising a condensate of a fluorine-containing alcohol, boric acid and polyvinyl butyral, wherein the fluorine-containing alcohol represented by the general formula [Ib] is a polyfluoroalkylene ether diol represented by the general formula:
HO(CH.sub.2CH.sub.2O).sub.pCH.sub.2CF.sub.2(OCF.sub.2CF.sub.2).sub.q(OCF.sub.2).sub.rOCF.sub.2CH.sub.2(OCH.sub.2CH.sub.2).sub.pOH[IIb] wherein p is an integer of 0 to 6, q+r is an integer of 0 to 50, wherein, based on 100 parts by weight of fluorine-containing alcohol, the boric acid is used at a ratio of 0.1 to 100 parts by weight, and the polyvinyl butyral is used at a ratio of 5 to 600 parts by weight.

5. A surface-treating agent comprising the fluorine-containing boric acid PVB composite according to claim 1, as an active ingredient.

6. A surface-treating agent comprising the fluorine-containing boric acid PVB composite according to claim 2, as an active ingredient.

7. A surface-treating agent comprising the fluorine-containing boric acid PVB composite according to claim 3, as an active ingredient.

8. A surface-treating agent comprising the fluorine-containing boric acid PVB composite according to claim 4, as an active ingredient.

Description

EMBODIMENTS FOR CARRYING OUT THE INVENTION

(1) An example of the fluorine-containing alcohol represented by the general formula [X] is a fluorine-containing alcohol represented by the general formula:
R.sub.F-A-OH[I]
wherein R.sub.F is a perfluoroalkyl group having 6 or less carbon atoms, a polyfluoroalkyl group in which some of the fluorine atom or atoms of the perfluoroalkyl group are replaced by hydrogen atom or atoms, or a polyfluoroalkyl group containing a terminal perfluoroalkyl group having 6 or less carbon atoms and a perfluoroalkylene group having 6 or less carbon atoms; and A is an alkylene group having 1 to 6 carbon atoms. An organic solvent solution comprising a mixture of the fluorine-containing alcohol [I] and polyvinyl butyral is used as a surface-treating agent for various substrates.

(2) Another example of the fluorine-containing alcohol represented by the general formula [X] is a fluorine-containing alcohol represented by the general formula:
R.sub.F-A-OH[Ia]
or the general formula:
HO-A-R.sub.F-A-OH[Ib]
wherein R.sub.F is a linear or branched perfluoroalkyl group containing a terminal perfluoroalkyl group having 6 or less carbon atoms, a perfluoroalkylene group having 6 or less carbon atoms, and ether bonds; R.sub.F is a linear or branched, perfluoroalkylene group or polyfluoroalkylene group, containing a perfluoroalkylene group having 6 or less carbon atoms and ether bonds; and A is an alkylene group having 1 to 6 carbon atoms. An organic solvent solution comprising a mixture of the fluorine-containing alcohol [Ia] or [Ib] and polyvinyl butyral is used as a surface-treating agent for various substrates.

(3) The fluorine-containing alcohol [I] is, for example, a polyfluoroalkyl alcohol represented by the general formula:
C.sub.nF.sub.2n+i(CH.sub.2).sub.jOH[II] n: 1 to 6, preferably 4 to 6 j: 1 to 6, preferably 1 to 3, particularly preferably 2

(4) The alkylene group A is, for example, a CH.sub.2 group, a CH.sub.2CH.sub.2 group, or the like. Examples of the perfluoroalkylalkyl alcohols having such an alkylene group include 2,2,2-trifluoroethanol (CF.sub.3CH.sub.2OH), 3,3,3-trifluoropropanol (CF.sub.3CH.sub.2CH.sub.2OH), 2,2,3,3,3-pentafluoropropanol (CF.sub.3CF.sub.2CH.sub.2OH), 3,3,4,4,4-pentafluorobutanol (CF.sub.3CF.sub.2CH.sub.2CH.sub.2OH), 2,2,3,3,4,4,5,5,5-nonafluoropentanol (CF.sub.3CF.sub.2CF.sub.2CF.sub.2CH.sub.2OH), 3,3,4,4,5,5,6,6,6-nonafluorohexanol (CF.sub.3CF.sub.2CF.sub.2CF.sub.2CH.sub.2CH.sub.2OH), 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctanol (CF.sub.3CF.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.2CH.sub.2CH.sub.2OH), and the like.

(5) Moreover, the polyfluoroalkyl group refers to a group in which a terminal CF.sub.3 group in a terminal perfluoroalkyl group is replaced by, for example, a CF.sub.2H group or a group in which an intermediate CF.sub.2 group is replaced by a CFH group or a CH.sub.2 group. Examples of the fluorine-containing alcohol [I] having such a substituent include 2,2,3,3-tetrafluoropropanol (HCF.sub.2CF.sub.2CH.sub.2OH), 2,2,3,4,4,4-hexafluorobutanol (CF.sub.3CHFCF.sub.2CH.sub.2OH), 2,2,3,3,4,4,5,5-octafluoropentanol (HCF.sub.2CF.sub.2CF.sub.2CF.sub.2CH.sub.2OH), and the like.

(6) The polyfluoroalkyl alcohol represented by the general formula [II] is described, for example, in Patent Document 2, and is synthesized through the following series of steps.

(7) First, a polyfluoroalkyl iodide represented by the general formula:
C.sub.nF.sub.2n+1(CF.sub.2CF.sub.2).sub.b(CH.sub.2CH.sub.2).sub.cI
is reacted with N-methylformamide HCONH(CH.sub.3) to form a mixture of polyfluoroalkyl alcohol and its formate. Then, the mixture is subjected to a hydrolysis reaction in the presence of an acid catalyst to form a polyfluoroalkyl alcohol of the general formula:
C.sub.nF.sub.2+1(CF.sub.2CF.sub.2).sub.b(CH.sub.2CH.sub.2).sub.cOH
However, the value of n+2b is 6 or less.
Examples of the polyfluoroalkyl iodide include the following:

(8) CF.sub.3(CH.sub.2CH.sub.2)I

(9) CF.sub.3(CH.sub.2CH.sub.2).sub.2I

(10) C.sub.2F.sub.5(CH.sub.2CH.sub.2)I

(11) C.sub.2F.sub.5(CH.sub.2CH.sub.2).sub.2I

(12) C.sub.3F.sub.7(CH.sub.2CH.sub.2)I

(13) C.sub.3F.sub.7(CH.sub.2CH.sub.2).sub.2I

(14) C.sub.4F.sub.9(CH.sub.2CH.sub.2)I

(15) C.sub.4F.sub.9(CH.sub.2CH.sub.2).sub.2I

(16) C.sub.2F.sub.5(CF.sub.2CF.sub.2)(CH.sub.2CH.sub.2)I

(17) C.sub.2F.sub.5(CF.sub.2CF.sub.2)(CH.sub.2CH.sub.2).sub.2I

(18) C.sub.2F.sub.5(CF.sub.2CF.sub.2).sub.2(CH.sub.2CH.sub.2)I

(19) C.sub.2F.sub.5(CF.sub.2CF.sub.2).sub.2(CH.sub.2CH.sub.2).sub.2I

(20) C.sub.4F.sub.9(CF.sub.2CF.sub.2)(CH.sub.2CH.sub.2)I

(21) C.sub.4F.sub.9(CF.sub.2CF.sub.2)(CH.sub.2CH.sub.2).sub.2I

(22) The fluorine-containing alcohol [I] may also be a fluorine-containing alcohol wherein the R.sub.F group is a polyfluoroalkyl group which contains a terminal perfluoroalkyl group having 6 or less carbon atoms and a perfluoroalkylene group having 6 or less carbon atoms, specifically, a polyfluoroalkyl group having 3 to 20 carbon atoms, preferably 6 to 10 carbon atoms, and A is an alkylene group having 2 to 6 carbon atoms, preferably 2 carbon atoms. Examples thereof, for example, include a polyfluoroalkyl alcohol represented by the general formula:
C.sub.nF.sub.2n+1(CH.sub.2CF.sub.2).sub.a(CF.sub.2CF.sub.2).sub.b(CH.sub.2CH.sub.2).sub.cOH[III] n: 1 to 6, preferably 2 to 4 a: 1 to 4, preferably 1 b: 0 to 2, preferably 1 or 2 c: 1 to 3, preferably 1

(23) The polyfluoroalkyl alcohol represented by the general formula [III] is disclosed in Patent Document 2, and synthesized through the following series of steps.

(24) First, a polyfluoroalkyl iodide represented by the general formula:
C.sub.nF.sub.2n+1(CH.sub.2CF.sub.2).sub.a(CF.sub.2CF.sub.2).sub.b(CH.sub.2CH.sub.2).sub.cI
is reacted with N-methylformamide HCONH(CH.sub.3) to form a mixture of polyfluoroalkyl alcohol and its formate. The mixture is then subjected to a hydrolysis reaction in the presence of an acid catalyst to form a polyfluoroalkyl alcohol of the general formula:
C.sub.nF.sub.2n+1(CH.sub.2CF.sub.2).sub.a(CF.sub.2CF.sub.2).sub.b(CH.sub.2CH.sub.2).sub.cOH
Examples of the polyfluoroalkyl iodide include the following:

(25) CF.sub.3(CH.sub.2CF.sub.2)(CH.sub.2CH.sub.2)I

(26) C.sub.2F.sub.5(CH.sub.2CF.sub.2)(CH.sub.2CH.sub.2)I

(27) C.sub.2F.sub.5(CH.sub.2CF.sub.2)(CH.sub.2CH.sub.2).sub.2I

(28) C.sub.3F.sub.7(CH.sub.2CF.sub.2)(CH.sub.2CH.sub.2)I

(29) C.sub.3F.sub.7(CH.sub.2CF.sub.2)(CH.sub.2CH.sub.2).sub.2I

(30) C.sub.4F.sub.9(CH.sub.2CF.sub.2)(CH.sub.2CH.sub.2)I

(31) C.sub.4F.sub.9(CH.sub.2CF.sub.2)(CH.sub.2CH.sub.2).sub.2I

(32) C.sub.2F.sub.5(CH.sub.2CF.sub.2)(CF.sub.2CF.sub.2)(CH.sub.2CH.sub.2)I

(33) C.sub.2F.sub.5(CH.sub.2CF.sub.2)(CF.sub.2CF.sub.2)(CH.sub.2CH.sub.2).sub.2I

(34) C.sub.2F.sub.5(CH.sub.2CF.sub.2).sub.2(CF.sub.2CF.sub.2)(CH.sub.2CH.sub.2)I

(35) C.sub.2F.sub.5(CH.sub.2CF.sub.2).sub.2(CF.sub.2CF.sub.2)(CH.sub.2CH.sub.2).sub.2I

(36) C.sub.4F.sub.9(CH.sub.2CF.sub.2)(CF.sub.2CF.sub.2)(CH.sub.2CH.sub.2)I

(37) C.sub.4F.sub.9(CH.sub.2CF.sub.2).sub.2(CF.sub.2CF.sub.2)(CH.sub.2CH.sub.2)I

(38) C.sub.4F.sub.9(CH.sub.2CF.sub.2)(CF.sub.2CF.sub.2)(CH.sub.2CH.sub.2).sub.2I

(39) C.sub.4F.sub.9(CH.sub.2CF.sub.2).sub.2(CF.sub.2CF.sub.2)(CH.sub.2CH.sub.2).sub.2I

(40) The fluorine-containing alcohol [Ia] may be a fluorine-containing alcohol wherein the R.sub.F group is a linear or branched, perfluoroalkyl group containing a terminal perfluoroalkyl group having 6 or less carbon atoms, a perfluoroalkylene group having 6 or less carbon atoms and ether bonds, specifically, an ether bonds-containing perfluoroalkyl group having 3 to 305 carbon atoms, preferably 8 to 35 carbon atoms, and A is an alkylene group having 1 to 3 carbon atoms, preferably 1 carbon atom. Examples thereof, for example, include a hexafluoropropene oxide oligomer alcohol represented by the general formula:
C.sub.mF.sub.2m+1O[CF(CF.sub.3)CF.sub.2O].sub.dCF(CF.sub.3)(CH.sub.2).sub.eOH[IIa] m: 1 to 3, preferably 3 d: 0 to 100, preferably 1 to 10 e: 1 to 3, preferably 1
or polyfluoropolyether alcohol represented by the general formula:
C.sub.mF.sub.2m+1(OCF.sub.2CF.sub.2CF.sub.2).sub.s(OCF.sub.2CF.sub.2).sub.t(OCF.sub.2).sub.u(CH.sub.2).sub.vOH[IIa] m: 1 to 3, preferably 3 s, t, u: integer of 0 to 200, preferably 0 to 80, respectively v: 1 or 2, preferably 1

(41) Moreover, the fluorine-containing alcohol [Ib] may be a fluorine-containing alcohol wherein the R.sub.F group contains a perfluoroalkylene group having 6 or less carbon atoms and ether bonds, specifically, a perfluoroalkylene group or polyfluoroalkylene group having 5 to 160 carbon atoms, and A is an alkylene group having 1 to 3 carbon atoms, preferably 1 carbon atom, for example, a per or polyfluoroalkylene ether diol represented by the general formula:
HO(CH.sub.2).sub.fCF(CF.sub.3)[OCF.sub.2CF(CF.sub.3)].sub.gO(CF.sub.2).sub.hO[CF(CF.sub.3)CF.sub.2O].sub.iCF(CF.sub.3)(CH.sub.2).sub.fOH[IIb] f: 1 to 3, preferably 1 g+i: 0 to 50, preferably 2 to 50 h: 1 to 6, preferably 2
or represented by the general formula:
HO(CH.sub.2CH.sub.2O).sub.pCH.sub.2CF.sub.2(OCF.sub.2CF.sub.2).sub.q(OCF.sub.2).sub.rOCF.sub.2CH.sub.2(OCH.sub.2CH.sub.2).sub.pOH[IIb] p: 0 to 6, preferably 1 to 4 q+r: 0 to 50, preferably 10 to 40

(42) Among the hexafluoropropene oxide oligomer alcohols represented by the general formula [IIa], a compound wherein m is 1 and e is 1 is described in Patent Document 3, and they are synthesized through the following step.

(43) A fluorine-containing ether carboxylic acid alkyl ester represented by the general formula: CF.sub.3O[CF(CF.sub.3)CF.sub.2O].sub.nCF(CF.sub.3)COOR (R: an alkyl group, n: an integer of 0 to 12) is subjected to a reduction reaction using a reducing agent such as sodium boron hydride.

(44) As the polyfluoropolyether alcohol represented by the general formula [IIa], a commercial product, such as DEMNUM SA (produced by Daikin Industries, Ltd.) or the like, can be used.

(45) Moreover, among the perfluoroalkylene ether diols represented by the general formula [IIb], a compound wherein f=1 is disclosed in Patent Documents 4 and 5, and they are synthesized via the following series of steps:
FOCRfCOF.fwdarw.H.sub.3COOCRfCOOCH.sub.3.fwdarw.HOCH.sub.2RfCH.sub.2OH
Rf: CF(CF.sub.3)[OCF.sub.2C(CF.sub.3)].sub.aO(CF.sub.2).sub.cO[CF(CF.sub.3)CF.sub.2O].sub.bCF(CF.sub.3)

(46) As the polyfluoroalkylene ether diol represented by the general formula [IIb], a commercial product, such as Fomblin Z DOL TX (produced by Solvay Solexis) or the like, can be used.

(47) Usable polyvinyl butyral is obtained by saponifying polyvinyl acetate [PVAc], and acetalizing the saponified polyvinyl alcohol [PVA] with butyraldehyde. The degree of saponification of PVAc is generally about 70 to 99.9 mol %, and unsaponified portions remain as acetyl groups. PVB obtained by saponification has an average molecular weight of about 110.sup.4 to 210.sup.5, and a degree of butyralization (according to JIS K6728) of about 50 to 80 mol %

(48) Practically, commercial products, such as S-LEC B series (produced by Sekisui Chemical Co., Ltd.), Denka Butyral (produced by Denka Company Limited), and the like, can be used.

(49) Polyvinyl butyral has the characteristics of being soluble in various solvents, and is mainly used as a glass interlayer or a coating compounding agent (Patent Documents 6 and 7). Patent Document 7 indicates that a compound having a boron atom is uniformly dispersed in polyvinyl butyral resin. This is because, according to Patent Document 7, extrusion molding of each layer in an interlayer for laminated glass is facilitated. Moreover, it is known that a thin film having adhesion, surface hardness and impact resistance can be formed by forming a composite of polyvinyl butyral and inorganic particles, such as silica (Non-Patent Document 1).

(50) For PVA, which is a precursor of PVB, there is fundamental research on the viscosity increase of composite materials in which a boron compound or the like is added (Non-Patent Documents 2 to 4).

(51) The amounts of these components used are as follows: based on 100 parts by weight of the fluorine-containing alcohol, boric acid is used at a ratio of about 0.1 to 100 parts by weight, preferably about 10 to 60 parts by weight, generally in an equimolar amount, and polyvinyl butyral is used at a ratio of about 5 to 600 parts by weight, preferably about 10 to 200 parts by weight. If the ratio of boric acid used is greater than this range, dispersibility in solvents decreases. Moreover, if the ratio of polyvinyl butyral used is greater than this range, water- and oil-repellency decreases. When boric acid is not used, an organic solvent solution of the fluorine-containing alcohol and polyvinyl butyral, such as a methanol or tetrahydrofuran solution having a concentration of about 1.0 to 3.0 g/L, exhibits excellent oil repellency. The reaction between the fluorine-containing alcohol (and boric acid) and polyvinyl butyral is generally performed by mixing them at room temperature using a solvent (e.g., tetrahydrofuran) that can dissolve these components.

(52) The amount of fluorine-containing alcohol in the obtained fluorine-containing boric acid PVB composite is about 25 to 98 mol %, preferably about 40 to 70 mol %. The composite size (measured by a dynamic light scattering method) is about 10 to 600 nm, preferably about 15 to 350 nm.

(53) The use of a mixture of the fluorine-containing alcohol and polyvinyl butyral allows coating having adhesion to inorganic substrates, such as glass, and water- and oil-repellency. Moreover, in the fluorine-containing boric acid PVB composite obtained by reacting these components with boric acid, the fluorine-containing alcohol is considered to be linked to the hydroxyl group of the boric acid particles; therefore, the chemical and thermal stability of boric acid, and the excellent water- and oil-repellency, antifouling properties, etc., of fluorine are effectively exhibited. Actually, a product obtained by treating a glass surface with the fluorine-containing boric acid PVB composite exhibits excellent water- and oil-repellency.

(54) The fluorine-containing boric acid PVB composite can also be formed as a condensation reaction product of the fluorine-containing alcohol, polyvinyl butyral and boric acid particles; however, other components are allowed to be mixed as long as the objects of the present invention are not impaired. Examples of such other components include plasticizers, such as organic ester plasticizers, which are organic mono- or polycarboxylic acid esters, organic phosphate plasticizers, and organic phosphite plasticizers; preferably liquid plasticizers.

EXAMPLES

(55) The following describes the present invention with reference to Examples.

Example 1

(56) In a 30-ml reaction vessel, 100 mg (0.27 mol) of CF.sub.3(CF.sub.2).sub.5(CH.sub.2).sub.2OH [FA-6], 17 mg (0.27 mol) of boric acid, and 5 ml of tetrahydrofuran were charged, and the mixture was stirred at room temperature condition for 5 hours. Thereafter, a polymer solution comprising 500 mg (9.6210.sup.3 mmol; calculated from average molecular weight) of polyvinyl butyral [PVB] (S-LEC B BM-2, produced by Sekisui Chemical Co., Ltd.; average degree of polymerization of PVB: 5.210.sup.4, degree of butyralization: 68 mol %, degree of acetylation: 1 mol %, hydroxyl group content: 31 mol %) dissolved in 15 ml of tetrahydrofuran was added dropwise, and the homogeneity of the reaction solution was visually confirmed. Then, the reaction solution was stirred at room temperature for a whole day and night. After completion of the reaction, the solvent was distilled off at 80 C., and the collected product was dried in a dryer at 70 C., and then in a vacuum dryer at 50 C. Thus, 555.3 mg (yield: 90%) of fluorine-containing boric acid PVB composite was obtained.

(57) The obtained composite was measured for the following items. Particle size and its variation: Table 1

(58) The particle size and its variation were measured using a methanol dispersion having a solid matters content of 1 g/L at 25 C. by a dynamic light scattering (DLS) method

(59) Contact angle of droplets (unit: ): Table 2

(60) Glass slides (micro cover glass, produced by MATSUNAMI Co., Ltd) were dipped in methanol dispersions (particle concentration: 5 g/L), and then dried under room temperature condition. Four l of droplets of n-dodecane or water were gently brought into contact with the obtained thin layer surfaces, and the contact angle of the droplets adhering to the thin layer surfaces was measured by the /2 method using a contact angle meter (Drop Master 300, produced by Kyowa Interface Science Co., Ltd.). The contact angle with water was measured with time.

(61) Adhesion to glass substrate: Adhesion was measured by a tape peeling test

(62) The results indicated that all of the Examples and Comparative Examples did not show a particular decrease in water- and oil-repellency in the contact angle measurement before and after the tape peeling test, and had excellent adhesion.

Examples 2 to 5

(63) In Example 1, the amount of fluorine-containing alcohol (FA-6) and the amount of boric acid were changed in various ways.

(64) TABLE-US-00001 TABLE 1 Product FA-6 Boric acid amount Yield Particle size Example mg mM mg mM (mg) (%) (nm) 1 100 0.27 17 0.27 555.3 90 430.3 44.5 2 200 0.55 43 0.70 594.4 80 24.3 2.4 3 300 0.82 51 0.82 731.9 86 319.6 82.8 4 400 1.10 68 1.10 803.4 83 244.1 61.9 5 500 1.37 85 1.37 889.7 82 482.3 125.4

(65) TABLE-US-00002 TABLE 2 (Glass Substrates) Water (elapsed time: min.) Example n-dodecane 0 5 10 15 20 25 30 1 23 62 63 60 56 51 48 42 2 22 65 64 60 57 52 48 44 3 29 66 66 62 57 54 50 45 4 25 65 62 50 44 39 35 28 5 35 70 50 45 41 34 34 28

Examples 6 to 9

(66) In Example 1, 10 mg (0.03 mmol) of fluorine-containing alcohol (FA-6), 10 ml in total of tetrahydrofuran, and various amounts of polyvinyl butyral (PVB) were used, and boric acid was not used. The obtained mixture solutions were used as coating solutions as they were. Example 6: PVB 10 mg (1.9210.sup.4 mmol) Example 7: PVB 5 mg (9.6210.sup.5 mmol) Example 8: PVB 2 mg (3.8510.sup.5 mmol) Example 9: PVB 1 mg (1.9210.sup.5 mmol)

(67) Table 3 shows the contact angle of the droplet with a glass substrate, and Table 4 shows the contact angle of the droplet with a PET film substrate.

(68) TABLE-US-00003 TABLE 3 (Glass Substrates) Water (elapsed time: min.) Example n-dodecane 0 5 10 15 20 25 30 6 30 59 52 49 42 39 32 30 7 28 52 46 49 36 32 27 22 8 30 51 44 40 36 31 25 20 9 46 79 76 76 64 55 47 44

(69) TABLE-US-00004 TABLE 4 (PET film) Water (elapsed time: min.) Example n-dodecane 0 5 10 15 20 25 30 6 32 81 78 78 74 64 57 50 7 36 77 72 72 65 54 51 44 8 31 81 68 68 65 57 52 46 9 37 90 81 81 74 56 47 46

Examples 10 to 14

(70) In Example 1, 5 mg (0.0024 mmol) of Fomblin Z DOL TX (produced by Solvay Solexis) of the following formula:
HO(CH.sub.2CH.sub.2O).sub.pCH.sub.2CF.sub.2(OCF.sub.2CF.sub.2).sub.q(OCF.sub.2).sub.rOCF.sub.2CH.sub.2(OCH.sub.2CH.sub.2).sub.pOH p: 3 q+r: 20
was used as the fluorine-containing alcohol, and 0.5 mg (9.6210.sup.6 mmol) of polyvinyl butyral, 5 ml in total of tetrahydrofuran, and various amounts of boric acid were used. The obtained reaction solutions were used as coating solutions as they were. Example 10: Boric acid 5.0 mg (0.081 mmol) Example 11: Boric acid 2.5 mg (0.040 mmol) Example 12: Boric acid 1.0 mg (0.016 mmol) Example 13: Boric acid 0.5 mg (0.008 mmol) Example 14: Boric acid
Table 5 shows the contact angle of the droplet with a glass substrate.

(71) TABLE-US-00005 TABLE 5 (Glass Substrates) Water (elapsed time: min.) Example n-dodecane 0 5 10 15 20 25 30 10 57 69 41 39 34 31 28 15 11 60 80 51 48 42 38 34 22 12 57 63 42 38 33 30 21 18 13 56 69 45 43 39 34 32 29 14 57 76 57 53 49 45 41 36

(72) When Examples 10 to 14 described above are each evaluated based on Comparative Example 4 (PVB/boric acid) described below, it is revealed that Examples 10 to 14 are superior in terms of the contact angle with n-dodecane. That is, they are considered to be superior in oil repellency.

Comparative Examples 1 to 5

(73) In the droplet contact angle measurement in Example 1, glass substrates (Table 6) or PET film substrates (Table 7), both of which were coated with a methanol dispersion (5 g/L) of the following sample in place of the fluorine-containing boric acid PVB composite methanol dispersion, were used.

(74) Comparative Example 1: glass substrate alone (no coating)

(75) Comparative Example 2: PET film substrate alone (no coating)

(76) Comparative Example 3: PBV

(77) Comparative Example 4: PBV/boric acid (500 mg, 9.6210.sup.3 mmol/85 mg, 1.37 mmol)

(78) Comparative Example 5: Boric acid

(79) TABLE-US-00006 TABLE 6 (Glass Substrates) Comparative Water (elapsed time: min.) Example n-dodecane 0 5 10 15 20 25 30 1 0 50 41 36 34 31 26 29 2 3 13 85 79 73 70 67 62 52 4 41 93 79 74 71 65 61 50 5 22 66 47 43 39 37 32 27

(80) TABLE-US-00007 TABLE 7 (PET film) Comparative Water (elapsed time: min.) Example n-dodecane 0 5 10 15 20 25 30 1 2 0 76 68 66 61 60 60 58 3 13 85 79 73 70 67 62 52 4 41 93 79 74 71 65 61 50 5 22 66 47 43 39 37 32 27