WO2007058247A1 - Clathrate compound of fluoropolyether molecule - Google Patents

Abstract

It is intended to realize dissolution or dispersion of a fluoropolyether in a solvent having no affinity with the fluoropolyether, for example, a polar solvent and also realize uniform loading to a resin with poor compatibility with the fluoropolyether. There is provided a clathrate compound comprising a molecule of host compound, such as cyclodextrin, having a cyclic structure or spiral structure and having inside the structure a hydrophobic group and, enclosed therein, a fluoropolyether molecule as a guest compound.

Description

 Specification

 Inclusion compounds of fluoropolyether molecules

 Technical field

 [0001] In the present invention, a fluoropolyether molecule is included as a guest compound in a host compound molecule having a ring structure or a helical structure and having a hydrophobic group inside the structure. It is related to the inclusion compound.

 Background art

 [0002] Cyclodextrin, one of the polysaccharide compounds, is a cyclic oligomer of glucose and has a hydrophilic group on the outside of the ring and a hydrophobic pore on the inside. Therefore, the hydrophobic compound on the inside of the ring It is known to contain. The main ones are a-cyclodextrin, j8-cyclodextrin, and y-cyclodextrin in which 6, 7, and 8 darcoviranose residues are linked by α-1, 4 glycosidic bonds.

 [0003] The inner diameter of the ring varies depending on the type of cyclodextrin, and thus the size of the guest compound that is easily included is also different. As a typical guest molecule (hydrophobic polymer) that can be included in β-cyclodextrin and y-cyclodextrin, polydimethylsiloxane; ^ known (Okumura, H., Kawaguchi, Y., Harada , A., Macromolecules, 2003, 36, 6422-6429.), Mixed with a saturated aqueous solution of cyclodextrin and a hydrophobic polymer.

 [0004] In addition, a method for separating ι8-cyclodextrin utilizing the specific inclusion of poly (buryl ether) molecules by / 3-cyclodextrin is also known (Patent No. 2798514).

[0005] In addition, a polyortaxene molecule in which polyethylene glycol molecules are clasped into the openings of α-cyclodextrin molecules is a compound or gel rich in high water absorption, uniform expansion, elasticity, viscoelasticity, etc. It is also known to give a product (Patent No. 3475252) ο In the case of this invention, a specific example of a fluoropolymer, in particular a perfluoropolyether, can be obtained. However, there are still problems such as the heat resistance of compounds and gels rich in elasticity and viscoelasticity, chemical resistance, and compatibility with fluoropolymers. [0006] Furthermore, the inclusion phenomenon between water-soluble polyethylene glycol modified with perfluorohydrocarbon and β-cyclodextrin has also been investigated (H. Zhang, et al., Langmuir 1998, 14, pp4972- 4977).

 [0007] In addition, Hiroto Tatsuno et al., “Analysis of structure and dynamics of perfluoroalkane Z cyclodextrin inclusion complex using solid-state 19F— and 13C—NMR”, 23rd cyclodextrin The symposium abstract, 162-163 (2005), reports the inclusion phenomenon of 13-cyclodextrin with 9 and 20 perfluoroalkanes.

 [0008] However, these guest compounds are structural units having a relatively small volume, and there has been no report on a large volume of fluoroether! /.

 Disclosure of the invention

 [0009] Fluoropolyether is particularly excellent in water and oil repellency, antifouling, and lubricity. However, it does not dissolve in some fluorinated solvents such as perfluorinated hexane, either alone or in particular. It is only used as a fluorinated solution. However, the above characteristics are difficult to dispose of as an additive. Because it dissolves only certain fluorinated solvents and has poor compatibility with hydrocarbon resins, it can be used as an additive. Is limited.

 [0010] Therefore, the present inventors focused on clathrate compounds that have been studied for some fluorine-based compounds, and as a result of intensive studies on molecules having a fluoroether unit, the fluoroether unit is a cyclodextrin. In particular, it was found that a good inclusion complex with γ-cyclodextrin was formed, and further studies were made to complete the present invention.

 That is, in the present invention, a fluoropolyether molecule is included as a guest compound in a host compound molecule having a ring structure or a helical structure and having a hydrophobic group inside the structure. Related to the inclusion.

[0012] The hydrophobicity of fluoropolyether compounds and the low solubility in hydrocarbon solvents are caused by fluorine atoms surrounding the surface. Therefore, a fluoropolyether compound is encapsulated in a host compound molecule having a ring structure or a helical structure characterized by inclusion of a hydrophobic compound and having a hydrophobic group inside the structure. By contacting, fluorine atoms are taken into the inside of the host compound ring, while carbon atoms, hydrogen atoms, By exposing the group to the surface of the host compound molecule, the poor solubility and poor compatibility of the fluoropolyether compound can be overcome.

 [0013] As the host compound, a polysaccharide compound is exemplified, and examples thereof include cyclodextrin which is a polysaccharide having a ring structure, amylose having a helical structure, and the like. Among these, γ-cyclodextrin forms a good inclusion complex.

 [0014] As the fluoropolyether, the formula (1):

Υ ¹ -R ^1- (RfO)-R ² -Y ²

[In the formula, R ¹ and R ² are the same force or different, and each has a bond, a functional group Z ¹ and may be substituted with a fluorine atom; a divalent hydrocarbon group; Y ¹ and Y ² is the same or different, and all are H, a halogen atom or a functional group Z ² ; n is 2 to: an integer of LOO; — (RfO) 1 is a formula (2):

 [0015] [Chemical 1]

~ cx ^ cx cx o) _nl (cx ⁷ x ^s cx ⁹ x ^{1 Q} o) _ng (cx ^ll x ^{1 2} o-^-

(Wherein xi to X ¹² are the same or different and all are H, CH, F or CF, ^ to X

 3 3

Any one of ⁶ is F or CF, any one of X ⁷ to X ^1Q is F or CF

 3 3

, X ^{U to} X ¹² is F or CF, and nl, n2 and n3 are the same or different

 Three

 Preferred examples include fluoropolyethers represented by a fluoropolyether unit represented by the following formula: 0 or an integer of 1 or more and nl + n2 + n3 = n.

[0016] The inclusion compound is sometimes called an inclusion complex or an inclusion body.

 BEST MODE FOR CARRYING OUT THE INVENTION

First, the fluoropolyether that is a guest compound will be described.

In the present invention, the fluoropolyether that is a guest compound may have a fluoropolyether unit in its molecule. The inclusion structure occurs in this fluoropolyester unit! /.

[0019] Fluoropolyether as a preferable good guest compound is represented by the formula (1):

Y ¹ -R ^1- (RfO)-R ² -Y ²

It is represented by In the formula (1), one (RfO) — is the formula (2):

[0021] [Chemical 2] cx ^^ x ^^ x-'x ^) _nl (cx ⁷ x ^s cx ⁹ x ^{1 Q} o) _a2 (cx "x ^{1 2} o ~ ^

(Wherein xi to X ¹² are the same or different and all are H, CH, F or CF, ^ to X

 3 3

Any force one ⁶ is F or CF, any force one of X ⁷ to X ^1Q is F or CF

 3 3

, X ^{U to} X ¹² is F or CF, and nl, n2 and n3 are the same or different

 Three

 Fluoropolyether represented by a fluoropolyether unit represented by 0 or an integer of 1 or more and nl + n2 + n3 = n (n = integer of 2 to 100)] .

[0022] In this fluoropolyether unit RfO! /, Xi to X ¹² !, deviation is F, or F and CF

 When γ-cyclodextrin is used as a combination of the three compounds, especially as a host compound molecule, it is necessary to have a perfluoroether unit, which is F, in terms of size compatibility with the pores of γ-cyclodextrin. I also like power.

[0023] In equation (2), nl + n2 + n3 is η (= 2 to 100 integer), but one (ΟΧ ^ Χ ^ ΟΧ ^ ⁴ CX ⁵ X ⁶ 0) —unit (hereinafter “1 ^ 0 unit ") (single (n2 = n3 = 0)) or — (CX ⁷ X ⁸ CX ⁹ X ¹⁰ O) —unit (hereinafter also referred to as“ Rf ² 0 unit ”) alone (nl = (N3 = 0) or — (CX ^u X ¹² 0) — (hereinafter sometimes referred to as “Rf ³ 0 unit”) alone (nl = n2 = 0) or Rf ^ unit and Rf ²⁰ unit And Rf ³ 0 unit! /, Displacement force 2 units or all units may be combined. Especially when Ύ-cyclodextrin is used as the host compound molecule, the RfO unit must contain the Rf ^ unit alone or in combination with Rf ² 0 and / or Rf ³ 0. Compared with γ-cyclodextrin, it is easier to be included in γ-cyclodextrin, and it is desirable to have a strong spot power.

 [0024] Further, it can be said that those having a linear fluoroether unit having different forces depending on the pore size of the host compound are easier to include than those having a branched fluoroether unit.

[0025] Preferable η is 2 to 50, more preferably 11 to 30, from the viewpoint of the viscosity of the fluoropolyether. nl is 0-50, more preferably 11-30, n2 is 0-50, more preferably 7-36, and n3 is preferably 0-50, more preferably 0-20. [0026] Also, for example — (Ι ^ Ο)-(Rf ² 0)-(Rf ^)-(Rf ² 0)-(v, x, y and z are positive vxyz

 It is also possible that a plurality of chain portions having the same structure are present in the RfO unit of one fluoropolyether molecule as in (integer).

[0027] Y ¹ and Y ² are the same or different and all are H, a halogen atom or a functional group Z ² .

[0028] Roh, fluorine atom heat resistance as androgenic atom, the preferred tool officers functional group Z ² from chemical viewpoint of good, a carboxyl group, a hydroxyl group, an amino group, an amide group, a nitro group, Shiano group An acyl group, a halogen acyl group, a sulfonic acid group, an ester group, and the like, and a carboxyl group and a hydroxyl group are particularly preferable.

In the formula (1), R ¹ and R ² are the same or different and both have a bond, a functional group Z ^1, and may be substituted with a fluorine atom. It is a hydrocarbon group.

[0030] R ¹ and R ² may be a divalent hydrocarbon group having a relatively small number of carbon atoms (for example, 1 to 10 carbon atoms, or even 1 to 2 carbon atoms), and V, one or both of them are polymers. Chain (number average molecular weight 100

0 ~: L00000, even this [1000 ~ 20000)! / ヽ.

[0031] Examples of the functional group Zeta ^1, carboxyl group, a hydroxyl group, an amino group, an amide group, a nitro group, Shiano group

, Acyl groups, halogen acyl groups, sulfonic acid groups, ester groups and the like.

[0032] Preferred examples of R ¹ and R ² include the following types.

[0033] (I) Fluorine-containing alkylene group

 Equation (3):

 One (CF) — (CH) —

 2 ρ 2 q

 (Wherein p is an integer of 1 to 5 and q is an integer of 0 to 5). Preferred examples include CF—, —CF CF—, and —CF CF CH—.

 2 2 2 2 2 2

 [0034] As such a type (I) fluoropolyether,

 F- CRf'O)-(CF) F,

 nl 2 p

 F- CRf'O)-(CF) —OH,

 nl 2 p

 F- CRf'O)-(CF) One (CH) — COOH,

 nl 2 p 2 q

F- CRf'O)-(Rf ² 0)-(CF) F, F- (Rf ^) (Rf ² 0) (CF) COOH ゝ

 nl n: 2 2 E

F- (Rf ^) (Rf ² 0)-(CF)-(CH)-OH,

 nl n: 2 2 E> 2 q

F- (Rf ^) (Rf ³ 0)-(CF) F,

 nl n: 3 2 E

F- (Rf ^) (Rf ³ 0)-(CF) COOH ゝ

 nl n: 3 2 E

F- (Rf ^) (Rf ³ 0)-(CF)-(CH)-OH,

 nl n: 3 2 E i 2 q

(Where 1 ^ 0, Rf ² 0, Rf ³ 0, nl, n2, n3 and p, q are the same as above)

 Etc.

 [0035] Examples of commercially available products include the demnum series manufactured by Daikin Industries, Ltd., the NORELTA series manufactured by NOK CRUBA, the Fomblin series manufactured by Solvay, and the Crite Tux series manufactured by DuPont.

 [0036] (II) Polymer chain

Examples of polymer chains include chains containing acrylic units, styrene units, butyl ether units, _a -olefin units, and non-fluorinated polyether units.

 [0037] As an acrylic unit, for example, the formula (4):

 [0038] [Chemical 3]

R ³ H ₂ C —

COOR ⁴

(Wherein r is an integer of 2 to: L000; R ³ is H or an organic group which may contain halogen, for example, F, CF, H or CH; R ⁴ is H or an organic group) can give.

 3 3

[0039] R ⁴ may have a fluorine atom! /, But may be a hydrocarbon group, a non-fluorinated polyether chain (polyoxyethylene chain, polyoxypropylene chain, etc.) and the like.

 [0040] As another type of polymer chain, for example, a fluoropolyether bonded to a side chain of a non-fluorinated polymer:

[0041] [Chemical 4] R ³ CH ₂ ― C)

COO— R ⁵ — (R f 0) _n -R ⁶ -Y ³

nおよび rは前記と同じ; R⁵および R⁶は同じかまたは異なりフッ素原 子で置換されていてもよいアルキレン基; Y³は前記 Y¹または Y²)で示されるものが例 示できる。 (Where RfO,

n and r are the same as described above; R ⁵ and R ⁶ are the same or different and may be substituted with a fluorine atom; Y ³ is exemplified by those represented by Y ¹ or Y ² ).

 [0042] The host ich compound may be a compound having a ring structure or a helical structure and having a hydrophobic group inside the structure and capable of including a fluoropolyether molecule.

 [0043] Specific examples include polysaccharide compounds having a ring structure or a helical structure and a hydrophobic group inside the structure, and synthetic compounds such as calixarene and crown ether. .

 [0044] Examples of polysaccharide compounds having a ring structure and having a hydrophobic group inside the structure include α-cyclodextrin, j8-cyclodextrin, γ cyclodextrin, oral amylose, and these Derivatives (modified products) of γ-cyclodextrin or derivatives thereof are preferred because they form a particularly stable inclusion compound with a fluoropolyether molecule.

 [0045] Derivatives of polysaccharide compounds having a ring structure include, for example, those in which all or part of the hydroxyl groups of the polysaccharide compounds are acetylated, methyl etherified, 2-hydroxyethylated, etc. And a polymer compound having a polysaccharide compound having a cyclic structure as a side chain (pendant) of the polymer.

 [0046] Examples of the polysaccharide compound having a helical structure and having a hydrophobic group inside the structure include amyloses.

[0047] Amylose is a linear molecule contained in starch, and has a structure in which a glucose is linked by a 1,4 daricoside bond. There are two known amylose crystal structures: double helix (A, B type) and single helix (V type). The oil and fat component contained in the granule is included in the helical structure and exists as an inclusion compound. Bociek et al. Have studied the structure of amylose by inclusion of palmitate, hexanoic acid, etc. (Gidley. MJ, Bociek. SMJAm. Chem. Soc, 1988, 110, 3820-382 9). In the present invention, V-amylose is preferred because it has a structure similar to cyclodextrin and can include a wide range of guest compound molecules.

[0048] As synthetic host compounds, for example, host compounds described in JP-A-09-241248, such as calixarene and crown ether, are known and can include a fluoropolyether molecule. Can be used in the present invention.

 [0049] The ratio of the host compound molecule to the fluoropolyether molecule in the clathrate compound varies depending on the type, structure, number, molecular weight, etc. of the fluoroether unit (RfO). It is usually in the range of iZi to iZiooo, and further iZi to iZioo, in terms of the molar ratio of host compound molecules (hereinafter sometimes referred to as “inclusion ratio” t).

 [0050] When シ ク ロ -cyclodextrin is used as the host compound, the inclusion ratio of the fluoropolyether molecule Ζ Ύ-cyclodextrin molecule molar ratio (inclusion ratio) is 1 to 1 to 20 The point of stability is also preferable.

 [0051] The clathrate compound of the present invention is obtained by adding a guest compound molecule in a saturated aqueous solution of a water-soluble compound molecule and leaving it alone after being irradiated with ultrasonic waves, or host compound molecules and guest compound molecules. It can manufacture by the method of kneading, adding water little by little to this mixture.

 [0052] The inclusion complex of the present invention is usually obtained in a solid form (powder form). Therefore, the clathrate compound of the present invention can be used as a modifier for various materials using the properties of fluoropolyether in the powder state as it is.

 Therefore, the present invention also relates to a powder of the clathrate compound of the present invention alone or a powder (composition) containing the clathrate compound.

 [0054] The particle size of the powder may be appropriately selected depending on the material to be blended, the production method, etc. Usually, it is in the range of 0.001 to 100 / ζ πι.

[0055] In the case of a powder composition containing other additives, the additives may be those usually used in powder compositions, for example, flame retardants, antistatic agents, thickeners, surface active agents. And preservatives. The amount of inclusion compound in the powder composition is the type, degree, A wide range of 0.01-99.99% by mass based on fluoropolyether can be adopted as appropriate depending on the type of material to be modified.

 [0056] The present invention also relates to a liquid composition containing the inclusion compound of the present invention and a solvent.

 [0057] The solvent may be any solvent that can dissolve or disperse the host compound. Therefore, the solvent that can be used depends on the host compound.

 [0058] Particularly when the host compound is a polysaccharide compound, the inclusion of a fluoropolyether as a guest compound makes it extremely difficult for the fluoropolyether to dissolve or disperse. Since it can be uniformly dissolved or dispersed in an ionic solvent, it can be easily blended into a material having an affinity only for a powerful polar solvent that could not be uniformly mixed in the prior art.

 [0059] Preferably, the polar solvent includes hydrocarbon alcohols such as methanol and ethanol; fluorine-containing alcohols such as hexafluoroisopropanol and pentafluoropropanol; hydrocarbons such as acetic acid. Fluoric carboxylic acids such as trifluoroacetic acid; dimethylformamide, dimethylacetamide, dimethyl sulfoxide, pyridine, acetone, and water depending on the host compound.

 [0060] Examples of the nonpolar solvent include hexane and benzene.

 [0061] To the liquid composition of the present invention, usual additives such as a flame retardant, an antistatic agent, a thickener, a surfactant and a preservative may be added.

 [0062] The concentration of the inclusion complex in the liquid composition of the present invention may be selected as appropriate depending on the type and degree of properties to be modified, the type of solvent, and the type of material to be modified. A wide range of 0.01 to 99.99% by mass on the basis of olopolyether can be adopted.

 [0063] Dissolution or dispersion in a solvent can be easily carried out by a method such as stirring, heating, and ultrasonic waves, and a liquid group in which an inclusion compound and further a fluoropolyether are uniformly dispersed in the solvent. A composition is obtained.

 [0064] The powder (or powder composition) and liquid composition of the present invention may be directly applied to the surface of various articles as a surface modifier, or may be blended with various polymers to form a fluoropolymer. You can show the characteristics of Tell.

That is, the present invention also relates to a polymer composition containing the inclusion complex of the present invention and a polymer. [0066] The polymer to be modified by adding the clathrate compound of the present invention is not particularly limited, and the clathrate compound is not limited.

In particular, uniform blending is possible if it has an affinity with the host compound.

[0067] In particular, when the host compound is a polysaccharide compound, a polymer having a polar group that could not be uniformly blended conventionally, such as acrylic resin, epoxy resin, polyester resin, etc.

It can also be easily blended with synthetic resins such as polyurethane resin; natural polymers such as cellulose and natural polymer derivatives.

[0068] Of course, various additives usually blended according to the application, purpose, use form, environment in which the polymer composition is used, for example, flame retardants, antistatic agents, thickeners, surfactants, antiseptics You can also add other agents.

[0069] The concentration of the clathrate compound in the polymer composition of the present invention is 0 on the basis of fluoropolyether, which may be appropriately selected depending on the type and degree of properties to be modified, the type of polymer to be modified, etc. 01-99. A wide range of 99% by mass can be used.

 [0070] The compound can be easily blended into the polymer solution by adding a liquid composition or a powder composition containing the inclusion complex to the polymer solution and stirring the mixture. As a result, a polymer composition in which fluoropolyether is uniformly dispersed in the polymer can be obtained.

 [0071] The powerful polymer composition may be used as a molding material as it is, or may be used as various modifiers by pulverizing a powder frame or pellets.

[0072] By using the clathrate compound of the present invention, excellent properties of fluoropolyether, such as water and oil repellency and antifouling effects, lubrication effect, electrical insulation effect, chemical resistance effect, The range of use of heat resistance can be greatly expanded.

Therefore, the clathrate compound of the present invention is useful as an antifouling agent, lubricant, etc. in the form of a powder (or a powder composition), a liquid composition, a polymer composition, etc. In addition, it is possible to provide a molded product in which fluoropolyether is uniformly dispersed.

[0074] Further, the compound of the present invention is used in the same manner as the compound and the gel-like substance having high absorbency, uniform expansibility, and elasticity or viscoelasticity as described in Japanese Patent No. 3475252. It can also be used as a material. However, the compound and gel-like substance comprising the fluoropolyether of the present invention can be a material having excellent heat resistance, chemical resistance and compatibility with fluoropolymers. Example

 [0075] Hereinafter, the present invention will be described in detail according to examples. The present invention is not limited to only these examples.

[0076] The materials used in the examples are as follows.

[0077] (Hosty compound)

 J8-cyclodextrin and 0-cyclodextrin manufactured by Tokyo Chemical Industry Co., Ltd.

[0078] (Guest mix)

 PFPE-1:

 [Chemical 5]

— ^ CF ₂ CF ₂ CF ₂ Q) _{Fluoropolyether} with a basic skeleton of _nl (nl = 22-26) and a carboxyl group at one end (number average molecular weight 4000)

[0079] PFPE-2:

 [Chemical 6]

— (-CF ₂ CF ₂ CF ₂ Q) _{Fluoropolyether} with a basic skeleton of _nl (nl = 22-26) and a methylol group at one end (number average molecular weight 4000)

[0080] PFPE-3:

 [Chemical 7]

— ^ CFCF ₂ O) _n2

 | (n 2 = 1 9-23)

Fluoropolyether with CF ₃ as the basic skeleton and a perfluoroalkyl group at the end (number average molecular weight 3500)

[0081] Further, it was confirmed by the following method that it was an inclusion complex.

[0082] (1) Solid ¹⁹ F— MAS NMR analysis

Equipment: AVANCE300 and 2.5mmMAS probe made by BRUKER BIOSPIN Measurement conditions: MAS speed 34kHz. room temperature.

[0083] (2) ¹ H → ¹³ C-CP / MAS NMR¾

 Equipment: AVANCE300 and 4mmMAS probe made by BRUKER BIOSPIN

 Measurement conditions: MAS rotation speed 7kHz. room temperature.

[0084] (3) Powder X-ray diffraction

 Equipment: Ultima III from Rigaku

 Measurement conditions: CuKa, X-Ray 40kV / 40mA, 2θ = 2-60 °

[0085] (4) Thermal analysis (differential heat / thermogravimetry (TGZDTA))

 Apparatus: Perkin-Elmer RTG220

 Measurement conditions: Temperature increase from 20 ° C to 605 ° C at a temperature increase rate of 10 ° CZmin

[0086] (5) State change

 Equipment: Nikon Corporation Polarizing Microscope and METTLER TOLEDO FP900 Thermo System Measurement conditions: Temperature rise from 30 ° C to 280 ° C at 20 ° CZmin

Example 1 (Synthesis of inclusion compound of PFPE 1 and γ-cyclodextrin)

 PFPE-1 (7 mg, 0.0019 mmol) was added dropwise as a fluoropolyether to a saturated aqueous solution of γ-cyclodextrin (γ cyclodextrin 0.5 g, 0.386 mmol / 2 ml). After applying ultrasonic waves for about 15 minutes, it was left overnight. Thereafter, the precipitate was collected by suction filtration, and the precipitate was dried overnight at 60 ° C. under reduced pressure to obtain 28 mg of a powdery white solid.

[0088] The obtained solid was analyzed by the above-mentioned method, and confirmed to be an inclusion complex of PFPE-1 and γ-cyclodextrin.

[0089] That is, in the solid ¹⁹ F- MAS NMR analysis, when PFPE-1 alone is used, (CF CF

 2

(CF CF) unit (CF CF CF O) is -129ppm, (CF CF CF O) is -83ppm

2 2 2 2 2 2 2 2

 Force at which characteristic peaks are observed In the white solid of Example 1, it was observed that some of these peaks (about 2Z3) were shifted to high frequencies of 126.5 ppm and 81.5 ppm, respectively. These results suggest that the white solid contains (CF CF CF Ο) units included in γ-cyclodextrin.

 2 2 2

[0090] In the CP / MAS NMR method, in the case of γ-cyclodextrin, the range is 58-66 ppm [5, 69-87 ppm [21, 97-106 ppm [9] In the white solid of Example 1, the observed peaks were simplified in comparison with the spectrum of 1, 8, and 2 γ-cyclodextrin alone in each range. This suggests an improvement in cyclodextrin symmetry and the formation of a cylindrical crystal structure (formation of an inclusion structure).

 [0091] In powder X-ray diffraction, the powder X-ray diffraction pattern of the white solid of Example 1 is different from the spectrum of γ-cyclodextrin alone, and the diffraction pattern (Li, J., Toh. KC, Ni, X "Zhou, Z" Leong, KW Macromolecules, 2001, 34, 8829-8831.), And it was confirmed that an inclusion complex was formed.

 [0092] In thermal analysis (differential heat / thermogravimetry (TGZDTA)), the melting point of γ-cyclodextrin alone is not observed, and the force at which decomposition begins gradually from above 250 ° C. At 230 ° C, an endothermic change that was not observed in the measurement data of γ-cyclodextrin and PFPE-1 was observed. As a result, it is suggested that the white solid of force Example 1 may have some state change near 230 ° C.

 [0093] Thus, when the state change was observed with a microscope at 30 to 280 ° C, the white solid of Example 1 was observed to have a phenomenon estimated to be melted at around 230 ° C. This phenomenon can be ruled out by the fact that PFPE-1, which was included by the start of the decomposition of γ-cyclodextrin, precipitates.

 [0094] The number average molecular weight of PFPE-1 (4000), γ, from the fluorine content (% by mass) measured by elemental analysis of the number of γ-cyclodextrins enclosing one molecule of PFPE-1 -The number average molecular weight (1297) of cyclodextrin was used to calculate the inclusion ratio of PFPE-1 and γ-cyclodextrin (PFPE / Ύ-cyclodextrin, molar ratio) was 1Z12.6.

 [0095] (6) Elemental analysis

 Equipment: Orion F ion meter model 901

 Measurement conditions: 25 ° C

[0096] In Example 1, the amount of PFPE-1 mixed was changed as shown in Table 1, and the inclusion state was examined. The results are shown in Table 1. In the table, γ-CD is γ-cyclodextrin. [0097] [Table 1]

 table 1

 [0098] Example 2 (Synthesis of inclusion compound of PFPE-2 and γ-cyclodextrin)

 The same procedure as in Example 1 was conducted except that PFPE-2 was used as a fluoropolyether in the amount shown in Table 2 against a saturated aqueous solution of γ-cyclodextrin (γ-cyclodextrin 0.5 g, 0.386 mmol / 2 ml). A powdery white solid was obtained, confirmed to be an inclusion complex of PFPE-2 and γ-cyclodextrin by the same analysis method as in Example 1, and the inclusion ratio was calculated. The results are shown in Table 2.

 [0099] [Table 2]

 Table 2

 Inclusion compound P FP Ε-2 er CD Inclusion compound Fluorine content Inclusion ratio

 ¾ (mg (g) ^ mg) (mass%) (PFPE 2 / y CD)

2- 1 7 0.5 26 15.0 1 / 11.5

2— 2 15 0.5 56 15.1 1 / Π..4

2— 3 41 0,5 153 16.7 1/10

2-4 78 0.5 276 18.0 1/9

2 -5 161 0.5 414 21.0 1 / 7.3 [0100] From Tables 1 and 2, it can be seen that the number of γ-cyclodextrin enclosing one molecule of PFPE-1 and PFPE 2 is in the range of 2 to 13. It can also be seen that there is no difference in the formation of the inclusion complex between the force carboxyl group and the methylol group as the terminal functional group.

 [0101] Example 3 (Synthesis of inclusion complex of PFPE 3 and γ-cyclodextrin)

 270 mg of PFPE-3, which has a different structure from PFPE-1 and PFPE-2, as a fluoropolyether against a saturated aqueous solution of γ-cyclodextrin (γ cyclodextrin 0.5 g, 0.386 mmol / 2 ml). 077 mmol) A powdery white solid was obtained in the same manner as in Example 1, except that it was used. The precipitate was much less than in Examples 1 and 2 with the same molar amounts of PFPE-1 and PFPE-2. Subsequently, it was confirmed by the same analysis method as in Example 1 that it was an inclusion complex of PFP E-3 and γ-cyclodextrin.

 [0102] From the results of Examples 1-3, when cyclocyclodextrin is used as the host compound molecule, linear fluoropolyether is more branched than fluoropolyether depending on the size of the pores. It is easy to include.

 [0103] Example 4 (Synthesis of inclusion compound of PFPE-1 and | 8-cyclodextrin)

 The same procedure as in Example 1 was performed except that 309 mg (0.077 mmol) of PFPE-1 was used as a fluoropolyether with respect to a saturated aqueous solution of β-cyclodextrin (j8-cyclodextrin 438 mg, 0.386 mmo 1/24 ml). Thus, a powdery white solid was obtained. The precipitate was much smaller than when the same molar amount of γ-cyclodextrin was used. Subsequently, it was confirmed by the same analysis method as in Example 1 that it was an inclusion complex of PFPE-1 and β-cyclodextrin.

 [0104] Example 5 (Preparation of liquid composition)

 For the inclusion compound number 1 of Example 1, the inclusion compound number 2-3 of Example 2, and the inclusion compounds of Example 3 and Example 4, hexafluoroisopropanol (HFIP), dimethylformamide Liquid compositions using (DMF) and dimethyl sulfoxide (DMSO) as solvents were prepared, and their solubility (dispersibility) was investigated. In addition, the solubility (dispersibility) of each of y-cyclodextrin, β-cyclodextrin, and PFPE-1 to PFPE-3 was also investigated. The results are shown in Table 3.

[0105] (7) Solubility (dispersibility) test Add a sample (20mg) to lg of each solvent (about 25 ° C), stir for 20 minutes, let stand for 1 hour, and visually observe the liquid state. Evaluation is based on the following criteria.

 1: Does not dissolve or disperse but precipitates immediately.

 2: Some dissolve, but most precipitate.

 3: Dispersed partly but mostly precipitated.

 4: Dispersed (slightly clouded).

 5: All are dissolved and become a transparent liquid.

[0106] [Table 3]

 [0107] As shown in Table 3, when a simple substance becomes a fluoropolyether force inclusion compound that does not dissolve or disperse alone, it can be dissolved or dispersed.

 Industrial applicability

[0108] By including a fluoropolyether molecule in a host compound molecule such as cyclodextrin, it can be dissolved in a conventional solvent having no affinity with fluoropolyether, such as a polar solvent, or Can be dispersed. In addition, it is possible to uniformly add a resin having a poor compatibility with the fluoropolyether compound. Furthermore, the phenomenon that the fluoropolyether compound encapsulated inside the host compound gradually precipitates on the surface (sustained release) is used for a long time. Antifouling and lubricating effects can be achieved.

Claims

The scope of the claims  [1] Inclusion formed by inclusion of a fluoropolyether molecule as a guest compound in a host compound molecule having a ring structure or a helical structure and having a hydrophobic group inside the structure.匕 Compound.  [2] The inclusion compound according to claim 1, wherein the host compound is a polysaccharide compound.  [3] Fluoropolyether force Formula (1): Y ¹ -R ^1- (RfO)-R ² -Y ² [In the formula, R ¹ and R ² are the same force or different, and each has a bond, a functional group Z ¹ and may be substituted with a fluorine atom; a divalent hydrocarbon group; Y ¹ and Y ² is the same or different, and all are H, a halogen atom or a functional group Z ² ; n is 2 to: an integer of LOO; — (RfO) 1 is a formula (2):  [Chemical 1] ~ c

(Wherein xi to X ¹² are the same or different and all are H, CH, F or CF, ^ to X  3 3 Any force one ⁶ is F or CF, any force one of X ⁷ to X ^1Q is F or CF  3 3 , X ^{U to} X ¹² is one of F or CF and nl  3, n2 and n3 are the same or different and are an integer of 0 or 1 and nl + n2 + n3 = n). The inclusion compound according to the first or second range. [4] The fluoropolyether unit RfO! /, Xi to X ¹² is !, the deviation is F, or F and CF  The inclusion compound according to claim 3, which is a combination of 3. [5] The full O b Te Contact! /, The polyether unit RfO, xi~X ¹² is!, Clathrate range囲第3 claim of claim displacement also F. [6] The functional group Z ² is a carboxyl group, a hydroxyl group, an amino group, an amide group, a nitro group, Shiano group, § sill group, Harogeni spoon Ashiru group, claim 3 is a sulfonic acid group or an ester group; 6. The clathrate compound according to item 5 above. 7. The method according to any one of claims 2 to 6, wherein the polysaccharide compound is γ-cyclodextrin. An inclusion compound as described above. [8] Full O b polyether molecule and _Ί over cyclodextrin molecule force full O b polyether content child Zeta Y- inclusion compound in the range 7 claim of claim is 1Ζ1~1Ζ20 molar ratio of the cyclodextrin molecule.  [9] A powder comprising the inclusion compound alone or the inclusion compound according to any one of claims 1 to 8.  [10] A liquid composition comprising the inclusion compound according to any one of claims 1 to 8 and a solvent.  [11] The liquid composition according to claim 10, wherein the solvent is a polar solvent. [12] A polymer composition comprising the inclusion complex according to any one of claims 1 to 8 and a polymer.