Fluorine-containing boric acid composite capsule particles

Abstract

Fluorine-containing boric acid composite capsule particles comprising a condensate of a fluorine-containing alcohol, a guest compound, and boric acid particles, wherein the fluorine-containing alcohol is represented by the general formula:
R.sub.F-A-OH
wherein R.sub.F is: a perfluoroalkyl group having 6 or less carbon atoms, a linear or branched perfluoroalkyl group containing a terminal perfluoroalkyl group having 6 or less carbon atoms and a perfluoroalkylene group having 6 or less carbon atoms, and containing an O, S, or N atom, or a polyfluoroalkyl group in which some of the fluorine atom or atoms of the perfluoroalkyl group are replaced by hydrogen atom or atoms, and which contains a terminal perfluoroalkyl group having 6 or less carbon atoms and a perfluoroalkylene group having 6 or less carbon atoms, wherein the perfluoroalkylene group may contain an O, S, or N atom, and one fluorine atom of the terminal perfluoroalkyl group may be replaced by (CH.sub.2).sub.fOH (wherein f is an integer of 1 to 3); and A is an alkylene group having 1 to 6 carbon atoms.

Claims

1. Boric acid composite capsule particles containing fluorine comprising a condensate of a fluorinated alcohol, a guest compound, and boric acid particles, wherein the fluorinated alcohol is 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 linear or branched perfluoroalkyl group containing a terminal perfluoroalkyl group having 6 or less carbon atoms and a perfluoroalkylene group having 6 or less carbon atoms, and containing an O, S, or N atom, or a polyfluoroalkyl group in which some of the fluorine atom or atoms of the perfluoroalkyl group are replaced by hydrogen atom or atoms, and which contains a terminal perfluoroalkyl group having 6 or less carbon atoms and a perfluoroalkylene group having 6 or less carbon atoms, wherein the perfluoroalkylene group may contain an O, S, or N atom, and one fluorine atom of the terminal perfluoroalkyl group may be replaced by (CH.sub.2).sub.fOH (wherein f is an integer of 1 to 3); and A is an alkylene group having 1 to 6 carbon atoms.

2. The boric acid composite capsule particles containing fluorine according to claim 1, wherein the fluorinated alcohol represented by the general formula [I] is a polyfluoroalkyl alcohol represented by the general formula:
CnF.sub.2n+1(CH.sub.2).sub.jOH[II] wherein n is an integer of 1 to 6, and j is an integer of 1 to 6.

3. The boric acid composite capsule particles containing fluorine according to claim 1, wherein the boric acid is used at a ratio of 0.01 to 10 parts by weight based on 100 parts by weight of the fluorinated alcohol, and the guest compound is used in an amount equimolar to the boric acid.

4. The boric acid composite capsule particles containing fluorine according to claim 1, wherein the amount of the guest compound in the fluorine-containing boric acid composite capsule particles is 0.1 to 70wt. %.

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

6. The boric acid composite capsule particles containing fluorine according to claim 1, wherein the guest compound is a fluorescent compound.

7. The boric acid composite capsule particles containing fluorine according to claim 6, wherein the boric acid is used at a ratio of 0.01 to 10 parts by weight based on 100 parts by weight of the fluorinated alcohol, and the guest compound is used in an amount equimolar to the boric acid.

8. A method for producing boric acid composite capsule particles containing fluorine, the method comprising subjecting a fluorinated alcohol, a guest compound, and boric acid particles to a condensation reaction under acidic or alkaline conditions, wherein the fluorinated alcohol is represented by the general formula:
R.sub.F-A-OH[I] wherein RF is: a perfluoroalkyl group having 6 or less carbon atoms, a linear or branched perfluoroalkyl group containing a terminal perfluoroalkyl group having 6 or less carbon atoms and a perfluoroalkylene group having 6 or less carbon atoms, and containing an O, S, or N atom, or a polyfluoroalkyl group in which some of the fluorine atom or atoms of the perfluoroalkyl group are replaced by hydrogen atom or atoms, and which contains a terminal perfluoroalkyl group having 6 or less carbon atoms and a perfluoroalkylene group having 6 or less carbon atoms, wherein the perfluoroalkylene group may contain an O, S, or N atom, and one fluorine atom of the terminal perfluoroalkyl group may be replaced by (CH.sub.2).sub.fOH (wherein f is an integer of 1 to 3); and A is an alkylene group having 1 to 6 carbon atoms.

Description

BRIEF DESCRIPTION OF DRAWINGS

(1) FIG. 1: FT-IR of the reaction product obtained in Example 1.

(2) FIG. 2: UV spectrum absorption curve of the reaction product obtained in Example 1.

(3) FIG. 3: FT-IR of the reaction product obtained in Example 2.

(4) FIG. 4: FT-IR of the reaction product obtained in Example 3.

(5) FIG. 5: UV spectrum absorption curve of the reaction product obtained in Example 3.

(6) FIG. 6: FT-IR of the reaction product obtained in Example 5.

(7) FIG. 7: FT-IR of the reaction product obtained in Example 6.

(8) FIG. 8: FT-IR of the reaction product obtained in Example 7.

EMBODIMENTS FOR CARRYING OUT THE INVENTION

(9) The fluorine-containing alcohol [I] can be a fluorine-containing alcohol wherein the R.sub.F group is a perfluoroalkyl group having 6 or less carbon atoms, for example, a polyfluoroalkyl alcohol represented by the general formula:
C.sub.nF.sub.2n+1(CH.sub.2).sub.j OH [II] n: 1 to 6, preferably 4 to 6 j: 1 to 6, preferably 1 to 3, particularly preferably 2

(10) 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.

(11) Moreover, a polyfluoroalkyl group refers to a group in which the terminal CF.sub.3 group of a perfluoroalkyl group is replaced by, for example, a CF.sub.2H group or a group in which the 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.

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

(13) 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 formula:
C.sub.nF.sub.2n+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.

(14) Examples of the polyfluoroalkyl iodide include the following: CF.sub.3(CH.sub.2CH.sub.2)I CF.sub.3(CH.sub.2CH.sub.2).sub.2I C.sub.2F.sub.5(CH.sub.2CH.sub.2)I C.sub.2F.sub.5(CH.sub.2CH.sub.2).sub.2I C.sub.3F.sub.7(CH.sub.2CH.sub.2)I C.sub.3F.sub.7(CH.sub.2CH.sub.2).sub.2I C.sub.4F.sub.9(CH.sub.2CH.sub.2)I C.sub.4F.sub.9(CH.sub.2CH.sub.2).sub.2I C.sub.2F.sub.5(CF.sub.2CF.sub.2)(CH.sub.2CH.sub.2)I C.sub.2F.sub.5(CF.sub.2CF.sub.2)(CH.sub.2CH.sub.2).sub.2I C.sub.2F.sub.5(CF.sub.2CF.sub.2).sub.2(CH.sub.2CH.sub.2)I C.sub.2F.sub.5(CF.sub.2CF.sub.2).sub.2(CH.sub.2CH.sub.2).sub.2I C.sub.4F.sub.9(CF.sub.2CF.sub.2)(CH.sub.2CH.sub.2)I C.sub.4F.sub.9(CF.sub.2CF.sub.2)(CH.sub.2CH.sub.2).sub.2I

(15) The fluorine-containing alcohol [I] may also be a fluorine-containing alcohol wherein the R.sub.F group is a polyfluoroalkyl group in which some of the fluorine atom or atoms of the perfluoroalkyl group are replaced by hydrogen atom or atoms, and 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

(16) The polyfluoroalkyl alcohol represented by the general formula [III] is disclosed in Patent Document 6, and synthesized through the following series of steps.

(17) 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 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

(18) Examples of the polyfluoroalkyl iodide include the following: CF.sub.3(CH.sub.2CF.sub.2)(CH.sub.2CH.sub.2)I C.sub.2F.sub.5(CH.sub.2CF.sub.2)(CH.sub.2CH.sub.2)I C.sub.2F.sub.5(CH.sub.2CF.sub.2)(CH.sub.2CH.sub.2).sub.2I C.sub.3F.sub.7(CH.sub.2CF.sub.2)(CH.sub.2CH.sub.2)I C.sub.3F.sub.7(CH.sub.2CF.sub.2)(CH.sub.2CH.sub.2).sub.2I C.sub.4F.sub.9(CH.sub.2CF.sub.2)(CH.sub.2CH.sub.2)I C.sub.4C.sub.9(CH.sub.2CF.sub.2)(CH.sub.2CH.sub.2).sub.2I C.sub.2F.sub.5(CH.sub.2CF.sub.2)(CF.sub.2CF.sub.2)(CH.sub.2CH.sub.2)I C.sub.2F.sub.5(CH.sub.2CF.sub.2)(CF.sub.2CF.sub.2)(CH.sub.2CH.sub.2).sub.2I C.sub.2F.sub.5(CH.sub.2CF.sub.2).sub.2(CF.sub.2CF.sub.2)(CH.sub.2CH.sub.2)I C.sub.2F.sub.5(CH.sub.2CF.sub.2).sub.2(CF.sub.2CF.sub.2)(CH.sub.2CH.sub.2).sub.2I C.sub.4F.sub.9(CH.sub.2CF.sub.2)(CF.sub.2CF.sub.2)(CH.sub.2CH.sub.2)I C.sub.4C.sub.9(CH.sub.2CF.sub.2).sub.2(CF.sub.2CF.sub.2)(CH.sub.2CH.sub.2)I C.sub.4F.sub.9(CH.sub.2CF.sub.2)(CF.sub.2CF.sub.2)(CH.sub.2CH.sub.2).sub.2I C.sub.4F.sub.9(CH.sub.2CF.sub.2).sub.2(CF.sub.2CF.sub.2)(CH.sub.2CH.sub.2).sub.2I

(19) The fluorine-containing alcohol [I] is a fluorine-containing alcohol wherein the R.sub.F group is a linear or branched perfluoroalkyl group containing an O, S, or N atom, specifically, a perfluoroalkyl group having 3 to 305 carbon atoms, preferably 8 to 35 carbon atoms, and containing O, S, or N atom, 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 [IV] m: 1 to 3, preferably 3 d: 0 to 100, preferably 1 to 10 e: 1 to 3, preferably 1

(20) Moreover, the R.sub.F group of the fluorine-containing alcohol [I] can also contain a terminal alcohol group. Such a divalent fluorine-containing alcohol is one wherein the R.sub.F group is a linear or branched polyfluoroalkylene group containing an O, S, or N atom; specifically, a divalent fluorine-containing alcohol wherein the R.sub.F group is a polyfluoroalkylene group containing an O, S, or N atom and a terminal alcohol group, and having 5 to 160 carbon atoms, and A is an alkylene group having 1 to 3 carbon atoms, preferably 1 carbon atom. Examples thereof, for example, include 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.sub.2O].sub.iCF(CF.sub.3)(CH.sub.2).sub.fOH [V] f: 1 to 3, preferably 1 g+i: 0 to 50, preferably 2 to 50 h: 1 to 6, preferably 2

(21) Among the hexafluoropropene oxide oligomer alcohols represented by the general formula [IV], a compound wherein m=1 and e=1 is described in Patent Document 7, and they are synthesized through the following step.

(22) 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.

(23) Moreover, among the perfluoroalkylene ether diols represented by the general formula [V], a compound wherein f=1 is disclosed in Patent Documents 8 and 9, 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)

(24) The guest compound is generally a fluorescent compound, such as alizarin, alizarin red S, 2,3-dihydroxynaphthalene, diethoxydiphenylsilane, or diphenylsilanediol. In addition, the quest compounds include aliphatic alcohols, such as pentaerythritol, -CD (cyclodextrin), -CD (cyclodextrin), and -CD (cyclodextrin).

(25) The proportion of these components is such that the boric acid is used at a ratio of about 0.01 to 10 parts by weight, preferably about 0.1 to 5 parts by weight, based on 100 parts by weight of the fluorine-containing alcohol, and such that the guest compound is generally used in an amount equimolar to the boric acid. When the amount of boric acid used is less than this range, water- and oil-repellency decreases. In contrast, when the amount of boric acid used is greater than this range, dispersibility in a solvent decreases. Moreover, when the amount of guest compound used is less than this range, dispersibility in a solvent decreases. In contrast, when the amount of guest compound used is greater than this range, water- and oil-repellency decreases.

(26) The reaction between these components is performed under acidic or basic conditions. In the present Examples, the pH of the reaction solution becomes acidic by adding boric acid to a fluorine-containing alcohol. When they are reacted under basic conditions, an alkali metal hydroxide, such as KOH or NaOH, or an N-containing compound, such as NH.sub.3, NH.sub.4OH, triethylamine, or choline acid, is used.

(27) The amount of the guest compound in the obtained fluorine-containing boric acid composite capsule particles is about 0.1 to 70 wt. %, preferably about 1 to 50 wt. %. The composite capsule particle size (measured by a dynamic light scattering method) is about 10 to 600 nm, preferably about 15 to 350 nm.

(28) The FT-IR and UV absorption spectra of the fluorine-containing boric acid composite capsule particles, which are the reaction product, show the same peaks as those of the guest compound; therefore, it is considered that the guest molecule is clathrated or adsorbed, and encapsulated. The fluorine-containing boric acid composite capsule particles are formed as a reaction product of boric acid particles and both a fluorine-containing alcohol and a guest compound; however, other components may be mixed therein unless the object of the present invention is hindered.

EXAMPLES

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

Example 1

(30) 1,100 mg (3.02 mmol) of CF.sub.3(CF.sub.2).sub.5(CH.sub.2).sub.2OH [FA-6], 50 mg (0.81 mmol) of boric acid, 200 mg (0.81 mmol) of alizarin, and 2.0 ml of tetrahydrofuran were changed in a 20-ml reaction vessel, and the mixture was stirred at room temperature for a day. Thereafter, the precipitate was removed by centrifugation, the solvent was distilled off, and drying was conducted, thereby obtaining 0.19 g of the target fluorine-containing boric acid composite capsule particles. The resulting fluorine-containing boric acid composite capsule particles were measured for particle size (by a dynamic light scattering method), FT-IR, and UV. The FT-IR and UV absorption spectra showed the same peaks as those of the guest compound; therefore, it was considered that the guest molecule was clathrated or adsorbed, and encapsulated.

Examples 2 to 10

(31) In Example 1, various guest compounds were used in place of alizarin.

(32) The following table shows the results obtained in the above Examples.

(33) TABLE-US-00001 TABLE Guest Composite compound Guest compound Amount Yield content Example Name mg mmol (mg) (%) (wt. %) 1 Alizarin 194 0.81 188 14 14 2 Alizarin red S 277 0.81 29 2 19 3 2,3- 130 0.81 95 7.4 10 Dihydroxy- naphthalene 4 Phenyl- 160 0.81 212 16 12 trimethoxysilane 5 Diethoxy- 220 0.81 192 14 16 diphenylsilane 6 Diphenylsilane- 176 0.81 358 27 13 diol 7 Pentaerythritol 110 0.81 139 11 9 8 -CD 50 0.05 18 1.5 4 9 -CD 50 0.04 23 1.9 4 10 -CD 50 0.04 23 1.9 4

(34) The reaction products of Examples 1 to 7 were measured for FT-IR and UV-vis. FT-IR: A dry powder was measured by the KBr method using FT/IR-480 Plus (produced by JASCO Corporation) UV-vis: A dispersion of composite particles adjusting a concentration of 0.02 g/L with a 1,2-dichloroethane solution was measured in the visible light range using V-570 (produced by JASCO Corporation)