JP2001329038A - Fluorine-containing diol and its use - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an _Rf which can be produced with high purity by a simple and inexpensive process instead of a conventional diol having one _Rf group when used as a diol component of a polyurethane. Group-containing one-terminal diol, and its production method,
In addition, the present invention provides a novel _Rf group-containing polyurethane which is excellent in water repellency, oil repellency, stain resistance, abrasion resistance, non-adhesiveness and the like without lowering the inherent performance of the polyurethane. SOLUTION: A fluorine-containing diol represented by the following general formula (I) and use thereof.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a novel diol containing a perfluoroalkyl group or a perfluoroalkenyl group (both are abbreviated as R _f groups), and a polyurethane using the diol.

[0002]

2. Description of the Related Art Polyurethane is a polymer which is excellent in abrasion resistance, adhesiveness, flexibility, chemical resistance and the like, and is also excellent in applicability to various processing methods. Therefore, polyurethane is widely used as a binder for various coating agents, paints, inks, and the like, and as a raw material for films, sheets, and other molded articles, and polyurethanes suitable for each use have been proposed. In addition, in this specification, "polyurethane" is a general term for "polyurethane", "polyurea", and "polyurethane-polyurea".

[0003] These polyurethanes are basically obtained by reacting a polyol and / or a polyamine with a polyisocyanate and, if necessary, a chain extender. Provides polyurethanes of various physical properties.

[0004] One of them is to introduce an organic fluorine compound into polyurethane molecules by copolymerization, and to impart the inherent properties of polyurethane to the water repellency, oil repellency, non-adhesion, abrasion resistance and the like of the organic fluorine compound. Methods for imparting performance such as anti-staining properties have been proposed. For example, one end diol having an R _f group (“one end diol”
Fluorine which is used in combination with "a compound having two hydroxyl groups at one end of the molecule") with a conventional diol other than the one-end diol (hereinafter, a diol other than the one-end diol is simply referred to as "diol"). Production method of polyurethane containing polyurethane (JP-B-43-26518, JP-A-61-2)
No. 52220).

[0005]

As a conventional method for producing a diol having a terminal at one end having an R _f group, for example, a method according to the following reaction formula is known.

[0006]

As described above, any of the conventional methods for producing a diol having an R _f group at one terminal requires multiple steps, and the resulting high-purity diol having an R _f group at one end is expensive. There is a problem in practical use on an industrial scale.

In a conventional polyurethane obtained by using a diol having one end at one end having an R _f group in combination with a diol, when the fluorine content in the polyurethane is increased to exert the function of fluorine, rubber elasticity and the like are reduced. Polyurethane inherent performance such as mechanical strength is reduced. This is because, together with the large bulk of the fluorine atoms, the repulsion between the fluorine atoms is strong, and in the fluorine-containing polyurethane molecules, the fluorine atoms are densely packed and the molecular chains are hard to bend, so the molecules are rigid and oriented in a certain direction. This is due to the nature of the R _f group, which makes it easier for polyurethane to reduce the thermal motility of the soft segment in the molecular chain due to the R _f group, lowering the rubber elasticity and inhibiting the aggregation of the hard segment. It is considered that the strength is reduced due to this. That is, the problem in polyurethane one terminal diol is introduced with a conventional _the R _f group points to the main chain of _the R _f group and the polyurethane are close, _the R _f group is a main chain of the polyurethane It was caused by a strong influence.

Accordingly, an object of the present invention is to replace the conventional diol having one end having an R _f group which causes the above-mentioned problems when used as a diol component of polyurethane.
Inexpensive and simple process, _Rf group-containing one-end diol that can be produced with high purity, its production method, and water-repellent / oil-repellent and antifouling properties without lowering the inherent performance of polyurethane. Is to provide a novel _Rf group-containing polyurethane excellent in abrasion resistance, non-adhesion and the like.

[0010]

The above object is achieved by the present invention described below. That is, a first aspect of the present invention provides a fluorine-containing diol represented by the following general formula (I).

A second aspect of the present invention is to react a fluorine-containing compound having an _Rf group and an active hydrogen group with a diisocyanate in NCO / OH ≒ 2, and to obtain one molecule in the molecule obtained by the reaction. Wherein the fluorine-containing compound having a free isocyanate group is reacted with a dialkanolamine at a temperature of 50 ° C. or lower. A method for producing a fluorine-containing diol represented by the above general formula (I).

A third aspect of the present invention is a fluorine-containing diol represented by the above general formula (I), an aliphatic, aromatic or alicyclic diisocyanate, an aliphatic, aromatic or alicyclic diol. A fluorine-containing polyurethane obtained by reacting a diamine and, if necessary, a chain extender, wherein the polyurethane has a general formula (II)
Is bonded to the polyurethane molecule by a urethane bond and / or a urea bond via R ₁ and R ₂ , and the content of the side chain is 3 to 3 as a fluorine content in the polyurethane molecule. Provided is a fluorine-containing polyurethane having an amount of 80% by weight and a weight average molecular weight of 5,000 to 500,000.

[0013]

A fourth aspect of the present invention provides the above-mentioned fluorine-containing polyurethane, which further contains a polysiloxane segment derived from a polysiloxane having at least one active hydrogen group.

A fifth feature of the present invention is that a fluorine-containing diol represented by the above general formula (I) is reacted with a diisocyanate, a diol and / or a diamine, and if necessary, a chain extender. And a method for producing a fluorine-containing polyurethane.

A sixth aspect of the present invention is to produce a fluorine-containing polyurethane by reacting a polysiloxane having at least one active hydrogen group in an amount of 1 to 75% by weight as a polysiloxane segment content in a polyurethane molecule. Provide a way.

[0017]

Next, the present invention will be described in more detail with reference to preferred embodiments. The one-terminal diol having an R _f group represented by the general formula (I) of the present invention can be produced, for example, by the following steps. A) First, a fluorine-containing compound (1) having an active hydrogen group (for example, a hydroxyl group) and a diisocyanate (2) are mixed with N
The reaction is carried out with CO / OH ≒ 2 to obtain a fluorine-containing compound (3) having one free isocyanate group in the molecule. B) Next, the above-mentioned fluorine-containing compound (3) and dialkanolamine (4) are selectively isocyanate at a temperature of 50 ° C. or lower by utilizing the difference in reactivity between amino groups and hydroxyl groups with respect to isocyanate groups. By reacting the group with an amino group, a diol having one end having an R _f group represented by the general formula (A) can be obtained.

[0018]

The fluorine-containing compound used in the present invention includes, for example, the following compounds.

[0020]

[0021]

The above epoxy compound is used by reacting with an active hydrogen-containing compound with a polyol, polyamide, polycarboxylic acid or the like so as to have a terminal hydroxyl group.

[0023]

[0024]

The fluorine-containing compounds having an active hydrogen group listed above are examples of preferred compounds used in the present invention, and the present invention is not limited to these examples. Accordingly, not only the above-exemplified compounds but also other known currently commercially available and commercially available compounds can be used in the present invention. Particularly preferred fluorine-containing compounds in the present invention are the alcohol-type fluorine-containing compounds exemplified above.

As the diisocyanate used in the present invention, any conventionally known diisocyanate can be used and is not particularly limited. For example, toluene-2,4 is preferred.
-Diisocyanate, 4-methoxy-1,3-phenylene diisocyanate, 4-isopropyl-1,3-phenylene diisocyanate, 4-chloro-1,3-phenylene diisocyanate, 4-butoxy-1,3-phenylene diisocyanate, 2,4 -Diisocyanate diphenyl ether, 4,4'-methylenebis (phenyl isocyanate) (MDI), judylene diisocyanate, tolidine diisocyanate, xylylene diisocyanate (XDI), 1,5-naphthalene diisocyanate, benzidine diisocyanate, o-nitrobenzidine diisocyanate, 4, Aromatic diisocyanates such as 4-diisocyanate dibenzyl; methylene diisocyanate, 1,4-tetramethylene diisocyanate;
1,6-hexamethylene diisocyanate, 1,10-
Aliphatic diisocyanates such as decamethylene diisocyanate; 1,4-cyclohexylene diisocyanate;
4,4-methylenebis (cyclohexyl isocyanate), 1,5-tetrahydronaphthalenediisocyanate, isophorone diisocyanate, hydrogenated MDI, hydrogenated X
Naturally, an alicyclic diisocyanate such as DI, or a polyurethane prepolymer obtained by reacting such a diisocyanate with a low molecular weight polyol or polyamine such that the terminal is an isocyanate can also be used.

The dialkanolamine used in the present invention includes compounds represented by the following general formula.

Preferred are, for example, diethanolamine, dipropanolamine, dihexanolamine, 1-aminopropane glycol, diethanolaminomethylamine, diethanolaminoethylamine,
Diethanolaminopropylamine and the like.

The method for producing the R _f group-containing diol represented by the general formula (I) will be described more specifically.
First, a fluorine-containing compound having an active hydrogen group is mixed with a diisocyanate in an equivalent ratio (NCO / OH ≒ 2) in which a reaction product has one free isocyanate group in a molecule, without a solvent or under an organic solvent, usually. In the presence or absence of a polyurethane polymerization catalyst (e.g., an organic metal, a tertiary amine, etc.) at 0 to 150C, preferably 20 to 90C. Next, 50 ° C or less, preferably 40 ° C or less,
More preferably, the fluorine-containing compound having one free isocyanate group is dropped into the dialkanolamine at a temperature of 30 ° C. or lower.

Under these conditions, the isocyanate groups react preferentially with the amino groups before the hydroxyl groups [Ann.
562 , 205 (1949)], and a diol at one end having an R _f group represented by the general formula (I) of the present invention is obtained;
At a low temperature, as the reaction proceeds, the product is partially precipitated as crystals in the organic solvent. After completion of the reaction, the reaction mixture is poured into a poor solvent such as water, toluene, xylene, or n-hexane to precipitate a crystal of a reaction product. The unreacted diisocyanate or dialkanolamine can be removed by washing the precipitated crystals at room temperature with a poor solvent (such as an aromatic or aliphatic hydrocarbon), and the R represented by the general formula (I) can be removed. A high-purity one-terminal diol having an _f group is obtained.

The fluorine-containing polyurethane of the present invention comprises the _Rf group-containing diol represented by the general formula (I) obtained by the above reaction, the diisocyanate and the diol and / or
Alternatively, it can be obtained by reacting with a diamine. As the diol, any of diols conventionally used in the production of polyurethane can be used and is not particularly limited. For example, ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4
-Low molecular weight glycols such as butylene glycol and 1,6-hexamethylene glycol; polyester diols obtained from dibasic acids such as adipic acid, maleic acid and terephthalic acid and glycols; lactones are opened with glycols Polyester diols of polylactones obtained by polymerization; polycarbonate diols; polytetramethylene glycol, polyethylene glycol,
And polyether diols such as polypropylene glycol.

As the diamine, any of those conventionally used in the production of polyurethane can be used and are not particularly limited. For example, aliphatic diamines such as methylenediamine, ethylenediamine, trimethylenediamine, hexamethylenediamine, octamethylenediamine; phenylenediamine, 3,3′-dichloro-4,4′-diaminodiphenylmethane, 4,4′-methylenebis (phenyl) Amines), aromatic diamines such as 4,4'-diaminodiphenyl ether and 4,4'-diaminodiphenylsulfone; and alicyclic diamines such as cyclopentadiamine and cyclohexyldiamine. The chain extender is the above-mentioned low molecular weight diol or diamine, and any of those conventionally used in the production of polyurethane can be used without any particular limitation.

The fluorine-containing polyurethane of the present invention can be obtained by using these components and using a conventionally known polyurethane production method. The method for producing a polyurethane of the present invention comprises reacting the _Rf group-containing diol represented by the general formula (I), a diisocyanate, and a diol and / or a diamine, if necessary, with a chain extender. The production method is not particularly limited. Further, the reaction mode is not particularly limited, and may be any reaction mode such as lump, solution, and dispersion. Further, the diol, diamine, and diisocyanate are not particularly limited as long as a combination suitable for the purpose of use and required performance of the obtained fluorine-containing polyurethane is selected.

In another embodiment of the present invention, the fluorine-containing polyurethane further includes a polysiloxane segment derived from a polysiloxane having at least one active hydrogen group, and a polysiloxane segment content in the polyurethane molecule. And a fluorine-containing polyurethane contained in an amount of 1 to 75% by weight.

The polysiloxane used in the present invention has at least one active hydrogen group in the molecule, for example, an amino group,
It is a polysiloxane having an epoxy group, a hydroxyl group, a mercapto group, a carboxyl group, and the like. Preferred examples thereof include the following compounds.

[0036]

[0037]

[0038]

[0039]

[0040]

The polysiloxanes having active hydrogen groups listed above are preferred compounds used in the present invention, and the present invention is not limited to these exemplified compounds. Therefore, not only the compounds exemplified above, but also other compounds that are currently commercially available and can be easily obtained from the market can be used in the present invention. Particularly preferred compounds according to the invention are polysiloxanes having at least one hydroxyl or amino group. Further, the fluorine-containing polyurethane of the present invention as described above (hereinafter also referred to as further containing a polysiloxane segment) includes a solution dissolved in an organic solvent, a solution dispersed in water, and a solid content of 100% by weight. It can be used in the form of pellets or the like.

In the fluorine-containing polyurethane obtained by using the _Rf group-containing diol of the present invention, the fluorine-containing side chain represented by the general formula (II) has a structure in which R ₁ and R ₂ are interposed in the molecular chain. Bonded by a urethane bond (—NH—CO—O—) and / or a urea bond (—NH—CO—NH—), and polyurethane is used when a diol is used, and polyurea is used when a diamine is used. However, when a diol and a diamine are used in combination, a polyurethane-polyurea can be obtained.

The content of the fluorine-containing side chain in the polyurethane molecule preferably occupies 3 to 80% by weight as the fluorine content based on the _Rf group in the polyurethane molecule. When the content is less than 3% by weight, the function associated with the surface energy based on the _Rf group is insufficiently exhibited. On the other hand, if it exceeds 80% by weight, the inherent properties of polyurethane such as abrasion resistance and mechanical strength become insufficient, which is not preferable. Preferably 5
It is 50% by weight, more preferably 5 to 25% by weight.

The fluorine- and silicon-containing polyurethane of the present invention obtained by using a diol having one terminal at one end having an R _f group, a polysiloxane having at least one active hydrogen group in the molecule, and the above-mentioned other polyurethane component. And fluorine introduced from the fluorine-containing diol represented by the general formula (I) together with a segment introduced into the main chain from the same diisocyanate as in the conventional polyurethane, and a segment introduced from the diol and / or diamine. The containing side chain is bonded to the molecular chain via R ₁ and R ₂ via a urethane bond and / or a urea bond, and the polysiloxane segment introduced from the polysiloxane is bonded to the main chain via a urethane bond and / or a urea bond. Polyurethane bonded.

The content of the polysiloxane segment in the polyurethane molecule is preferably such that the siloxane content in the molecule is 1 to 75% by weight. If the amount is less than 1% by weight, the function associated with the surface energy based on the polysiloxane segment becomes insufficient. On the other hand, if it exceeds 75% by weight, the inherent properties of polyurethane such as abrasion resistance and mechanical strength become insufficient, which is not preferable. Preferably it is 3 to 50% by weight, more preferably 5 to 20% by weight.

Since the preferred fluorine content and polysiloxane content of the fluorine-containing polyurethane of the present invention vary depending on the intended use, it is desirable that the fluorine content and the polysiloxane content be suitable for the intended use. The weight average molecular weight (measured by GPC and in terms of standard polystyrene) of the fluorine-containing polyurethane of the present invention is 5,
000 to 500,000, more preferably 3
It is between 0000 and 150,000.

The fluorine-containing polyurethane (which may contain a polysiloxane segment) obtained from the _Rf group-containing diol represented by the general formula (I) of the present invention has abrasion resistance, mechanical strength, It is an excellent polyurethane having properties such as water repellency, oil repellency, stain resistance and non-adhesion based on _Rf group in addition to properties such as flexibility, recovery elasticity and chemical resistance.

Since the fluorine-containing polyurethane of the present invention has such excellent characteristics, it can be used as a surface coating material for various substrates, a fiber coating material, artificial leather, a paint, a binder for a magnetic recording medium, Thermoplastic molding materials,
It is useful for manufacturing industrial parts, sheets, films, tubes, medical devices and the like. By using a diisocyanate, a diol and a diamine together with a conventionally known trifunctional or higher functional compound, a fluorine-containing polyurethane having a branch or the like can be produced.

[0049]

Next, the present invention will be described more specifically with reference to examples and comparative examples, but the present invention is not limited to these examples. In the following examples, “parts” and “%” are based on weight unless otherwise specified.

Example 1 (Fluorine-containing diol (IA)
A stirrer, a thermometer, a nitrogen gas inlet tube, and a reflux condenser were provided. In a reaction vessel purged with nitrogen, 22.2 parts of isophorone diisocyanate was dissolved in 50 parts of ethyl acetate, and stirred at 60 ° C. 46.4 parts of powdery 2- (perfluorooctyl) ethanol are gradually added, and after completion of the addition, the mixture is reacted at 80 ° C. for 3 hours to obtain a perfluoroalkyl group-containing one-terminal isocyanate (A).

Next, 10.5 parts of diethanolamine is mixed with 10 parts of ethyl acetate while stirring at a temperature of 10 ° C. or less, and the solution of the compound (A) is dropped into this solution.
An exothermic reaction is observed as the solution of the compound (A) is dropped, but the solution is gradually dropped so that the internal temperature does not exceed 20 ° C. The heterogeneous solution becomes homogeneous as the reaction proceeds. After completion of the dropwise addition, the reaction is continued at room temperature (25 ° C.) for 2 hours.

After completion of the reaction, the reaction product was precipitated from the reaction solution by adding toluene, filtered, washed, and dried to obtain a white powder product (yield: 95%). The fluorine content of the powdery reaction product was measured with an ion chromatograph (Yokogawa Hokushin Electric Co., Ltd.). The melting point of the powdery reaction product is 132 ° C.
The hydroxyl value measured according to No. 70 is 138 (mg KOH /
g) (theoretical value is 142).

FIG. 1 shows the infrared absorption spectrum of this reaction product. The characteristic absorption of each atomic group (c
m ^-1 ) is as follows. Urethane (-O-CO-N-): 1,690, tertiary amide (-CO-N <): 1,650, amide (-CO-N
H-): 1,300, 1,530, 1,500, N-
H: 3,351; amide C = O: 1,260; cyclohexane ring 1,3,5-substituted: 670, 705, 76
5 (methyl substituents), - CH ₂ -: 1,470,2,8
50,2,925, -CH _3: 1,460,2,98
0, branching CH _3: 1,380, -OH: 3,41
0, C-F: 1,120,1,210, -CF 2 -:
1,150, -CF _3: 1,346

From the characteristic absorption and the hydroxyl value of the infrared absorption spectrum, it was confirmed that the chemical structure of the reaction product was as follows.

[0055]

Example 2 (Fluorine-containing diol (IB)
Synthesis of white powdery product having the following structure was obtained in the same manner as in Example 1 except that 2,4-tolylene diisocyanate was used in the same equivalent amount instead of isophorone diisocyanate. The melting point of the product is 145 ° C., the hydroxyl value is 148 (theoretical value is 151)
Met. The chemical structure was confirmed in the same manner as in Example 1 except that the characteristic absorption of the infrared absorption spectrum (the characteristic absorption of the above-mentioned 1,3,5-substituted cyclohexane ring was changed to that of 1,2,2 of the benzene ring)
Characteristic absorption of tetrasubstituted compounds (810 to 865, 675 to 73
The reaction product had the following structure from the same as in Example 1 except that the reaction product had a molecular weight of 0,835 cm ^-1 (methyl-substituted product)) and a hydroxyl value.

[0057]

Example 3 (Fluorine-containing diol (IC)
Synthesis of Example 1) The procedure of Example 1 was repeated except that diethanolaminopropylamine was used instead of diethanolamine, and 2- (perfluorodecyl) ethanol was used instead of 2- (perfluoro-7-methyloctyl) ethanol. A white powder of fluorine diol (IC) of the following formula was obtained. The melting point of the product was 153 ° C., and the hydroxyl value was 115 (theoretical value was 118). The chemical structure of the reaction product was confirmed to be the following structure from the characteristic absorption and the hydroxyl value in the same infrared absorption spectrum as in Example 1.

[0059]

Examples 4 to 6 (Synthesis of Polyurethane) In a reaction vessel equipped with a stirrer, a thermometer, a nitrogen gas inlet tube, and a reflux condenser and purged with nitrogen, a fluorine-containing diol (IA) described in Table 1 was placed. IB, IC), a fluorine-free polymer diol and a fluorine-free diol, and dimethylformamide is added so that the solid content becomes 35%, and the mixture is uniformly dissolved. Next, a predetermined equivalent of diisocyanate was added and reacted at a temperature of 80 ° C. until a predetermined solution viscosity was obtained, to obtain a polyurethane of the present invention. FIG. 2 shows an infrared absorption spectrum of the fluorine-containing polyurethane of Example 5.

Comparative Examples 1-4 (Synthesis of Polyurethane) The following three fluorine-containing diols (IA ′, I-
B ′, IC ′) and the polymer diols and diols shown in Table 2 were used to obtain a fluorine-containing polyurethane in the same manner as in the above Examples. In the same manner, a polyurethane containing no fluorine-containing diol (Comparative Example 4) was obtained.

[0062]

Examples 7 to 9 (Synthesis of Polyurethane) In a reaction vessel equipped with a stirrer, a thermometer, a nitrogen gas inlet tube, and a reflux condenser and purged with nitrogen, the fluorine-containing diol obtained in Examples 1 to 3 ( IA, IB, IC), the following polysiloxanes (II-A, II-B, II-C), the fluorine-free polymer diols shown in Table 3, and the fluorine-free diols Dimethylformamide is added at a ratio shown in Table 3 and the mixture is uniformly dissolved so that the solid content becomes 35%. Next, a predetermined equivalent of diisocyanate was added and reacted at a temperature of 80 ° C. until a predetermined solution viscosity was obtained, to obtain a polyurethane of the present invention.

[0064]

Comparative Examples 5 to 8 (Synthesis of Polyurethane) The above two fluorine-containing diols (IA ′, I-
B ′), a polysiloxane and a diol shown in Table 4 were used to obtain a fluorine- and silicon-containing polyurethane in the same manner as in Examples 7 to 9 described above. Similarly, a polyurethane containing no fluorine-containing diol (Comparative Example 7) and a polyurethane containing no fluorine-containing diol and polysiloxane (Comparative Example 8) were produced.

The fluorine content and siloxane content of the polyurethanes of the above Examples and Comparative Examples were measured using an ion chromatograph (Yokogawa Hokushin Electric Co., Ltd.).
The solution viscosity was measured at 25 ° C. using a B-type viscometer.
The weight average molecular weight was determined by using GPC (GPC manufactured by Tosoh Corporation) (column: A-80M manufactured by Shodex) and using THF as a solvent and calculating the weight average molecular weight in terms of standard polystyrene. Physical properties were measured according to JIS K-6301. The surface characteristics were measured by the following method. The above measurement results are shown in Tables 1 to 4.

<Contact Angle> The contact angle was measured using a contact angle meter manufactured by Kyowa Interface Science Co., Ltd. <Abrasion test> According to JIS K-7311, Examples 4 to
9. A film formed by drying each of the polyurethane solutions of Comparative Examples 1 to 8 was adhered to a cardboard substrate, and rotated 100 times with a load of 1 kg using a wear wheel of H-22 with a Taber tester. The weight loss due to abrasion was measured. <Peeling force> A coating was formed by coating each polyurethane solution on a polyester film (PET) so that the thickness after drying was 1 μm.
mm acrylic adhesive tape (Sekisui Chemical)
g of rubber roller, and the peeling force after 1 hour was measured. <Coefficient of static friction> The coefficient of static friction was measured using a surface property tester manufactured by Shinto Kagaku.

[0068]

[0069]

[0070]

[0071]

(Note) (Common to Tables 1 to 4) (* 1) POTMG: polyoxytetramethylene glycol, molecular weight 2000 (* 2) PCDO: polycarbonate diol, molecular weight 2000 (* 3) PCLPO: polycaprolactone polyol,
Molecular weight 2000 (* 4) 1,4-BG: 1,4-butylene glycol (* 5) MDI: 4,4'-methylenebis (phenylisocyanate) PU: polyurethane

In Example 1, the following fluorine-containing alcohols 1 to 8 were used in place of 2- (perfluorooctyl) ethanol, and the corresponding fluorine-containing diols were used in the same manner as in Example 1. I got Using the obtained fluorine-containing diol, corresponding fluorine-containing (polysiloxane-containing) polyurethanes were obtained in the same manner as in Examples 4 and 7. The obtained fluorine-containing (polysiloxane-containing) polyurethane exhibited excellent physical properties similar to those of the fluorine-containing (polysiloxane-containing) polyurethanes of Examples 4 and 7.

[0074]

[0075]

As described above, the novel polyurethane obtained from the _Rf group-containing diol has excellent surface properties such as water repellency, oil repellency, stain resistance, abrasion resistance and non-adhesion. It is a polyurethane having excellent characteristics in which the strength characteristics, rubber elasticity and low-temperature characteristics of the polyurethane are hardly hindered as compared with the conventional polyurethane using the _Rf group-containing diol.

[Brief description of the drawings]

FIG. 1 is an infrared absorption spectrum of the fluorine-containing diol of Example 1.

FIG. 2 is an infrared absorption spectrum of the fluorine-containing polyurethane of Example 5.

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Chiya Kimura 1-7-6 Nibashi Bakucho, Chuo-ku, Tokyo Dainichi Seika Kogyo Co., Ltd. F-term (reference) 4H006 AA01 AA02 AB46 AC56 AC57 BC31 RA28 RA40 RB28 4J034 BA02 CA04 CA12 CA31 CB03 CC06 CC10 CC22 CC23 CC45 CC52 CD01 CD05 CD08 HA01 HA07 QB19 RA07 SA02 SB01 SB04 SB05 SC01 SC03 SC06 SC09

Claims (16)

[Claims] 1. A fluorine-containing diol represented by the following general formula (I). 2. A fluorine-containing compound having an _Rf group and an active hydrogen group is reacted with diisocyanate in NCO / OH ／ 2, and fluorine having one free isocyanate group in a molecule obtained by the reaction. The method for producing a fluorine-containing diol represented by the general formula (I) according to claim 1, wherein the containing compound and the dialkanolamine are reacted at a temperature of 50 ° C or less. 3. The method for producing a fluorine diol according to claim 2, wherein the fluorine-containing compound is at least one selected from the following compound group. 4. The method according to claim 2, wherein the dialkanolamine is represented by the following formula. 5. A fluorine-containing diol represented by the general formula (I), an aliphatic, aromatic or alicyclic diisocyanate, an aliphatic, aromatic or alicyclic diol and / or a diamine, a fluorine-containing polyurethane obtained by reacting a chain extender, the fluorine-containing side chains represented in the polyurethane molecule chain by the following general formula (II) is, via its R ₁ and R ₂ urethane Bond to the polyurethane molecule through a bond and / or a urea bond, and the content of the side chain is 3 to 8 as a fluorine content in the polyurethane molecule.
0% by weight, and the weight average molecular weight is 5,0
A fluorine-containing polyurethane having a molecular weight of from 00 to 500,000. 6. A weight average molecular weight of 50,000 to 15
The fluorine-containing polyurethane according to claim 5, which has a molecular weight of 0.000. 7. The fluorine-containing polyurethane according to claim 5, wherein the fluorine content is 5 to 50% by weight. 8. The fluorine-containing polyurethane according to claim 5, wherein the fluorine content is 5 to 25% by weight. 9. The fluorine-containing polyurethane according to claim 5, further comprising a polysiloxane segment derived from a polysiloxane having at least one active hydrogen group in an amount of 1 to 75% by weight. 10. The polysiloxane segment content is as follows:
The fluorine-containing polyurethane according to claim 9, which is 3 to 50% by weight. 11. The polysiloxane segment content is:
The fluorine-containing polyurethane according to claim 9, which is 3 to 20% by weight. 12. The fluorine-containing polyurethane according to claim 9, wherein the active hydrogen group of the polysiloxane is a hydroxyl group or an amino group. 13. A method comprising reacting a fluorine-containing diol represented by the general formula (I), a diisocyanate, a diol and / or a diamine other than the fluorine-containing diol, and, if necessary, a chain extender. Claim 5
3. The method for producing a fluorine-containing polyurethane according to item 1. 14. The fluorine-containing polyurethane according to claim 13, wherein the fluorine-containing diol represented by the general formula (I) is used in an amount such that the fluorine content in the polyurethane molecule is 3 to 80% by weight. Production method. 15. The fluorine-containing polyurethane according to claim 13, further comprising reacting the polysiloxane having at least one active hydrogen group in an amount of 1 to 75% by weight as a polysiloxane segment content in the polyurethane molecule. Production method. 16. The method for producing a fluorine-containing polyurethane according to claim 15, wherein the active hydrogen group of the polysiloxane is a hydroxyl group or an amino group.