JP2626765B2 - Polyurethane emulsion - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a polyurethane emulsion, which has surface lubricity, water repellency (water resistance), stain resistance, washing durability, mechanical properties,
An object of the present invention is to provide a polyurethane emulsion which is capable of providing a porous sheet material having excellent properties such as water vapor permeability and a good feeling.

(Prior Art) Conventionally, a large number of porous sheet materials made of polyurethane resin and methods for producing the same have been known as substitutes for natural leather and the like, and they are roughly classified into a wet method and a dry method.

(Problems to be Solved by the Invention) Both methods have advantages and disadvantages, and the dry method is superior in terms of productivity. As such a dry method,
JP-B-48-4380, JP-B-48-8742, JP-A-Showa
JP-A-51-41063, JP-A-54-66961 and JP-A-54-66961
A method described in -68498 or the like is known.

According to these known methods, respectively, excellent porous sheet materials having excellent moisture permeability are provided. However, since these porous sheet materials are porous, it is a matter of course that the surface lubricity is high. In addition, there is a problem that the feeling is inferior and the soil is more likely to be soiled.

In addition, since the micropores of these porous sheets are formed as communication holes for the purpose of moisture permeability, water can easily enter from the outside. There is a problem that the inside gets wet.

As a method of solving such a problem, a method of including a so-called softener or water repellent such as a silicone compound or a fluorine compound in the porous layer has been widely performed. Since the liquid agent is a compound having a relatively low molecular weight and poor compatibility with the polyurethane resin, the liquid agent bleeds out to the surface of the porous layer over time, and the surface becomes sticky or dust easily adheres. Contamination problem.

Further, by repeating the washing, the softener and the water repellent are removed, and the performance of the surface smoothness, hand, water repellency (water pressure resistance), and stain resistance imparted by the softener and the water repellent is lost. There is a problem of durability.

Also, U.S. Pat.No. 4,987,742 discloses an O / O of a polyurethane resin having a fluorine-containing segment having a perfluoroalkyl group in a side chain and a siloxane-containing segment in a molecular chain.
W-type aqueous dispersions are disclosed. The sheet produced using this aqueous dispersion is a transparent sheet having no pores and having flexibility and water repellency, and does not transmit water or water vapor.

Therefore, development of a porous sheet material that is porous and has excellent surface lubricity, good feeling, water pressure resistance, stain resistance and washing durability is demanded.

The inventor of the present invention has conducted intensive studies to meet the above-mentioned demands. As a result, when a specific polyurethane emulsion is used, the above-mentioned drawbacks of the prior art are solved, and a porous sheet material which can sufficiently meet the needs of the above-mentioned industry. The inventors have found that the present invention can be provided and completed the present invention.

(Means for Solving the Problems) That is, the present invention relates to a polyurethane resin having a silicone segment and a fluorocarbon segment in a main chain and / or a side chain, provided that at least two polyfluoroalkyl group-containing terminal structures are used. And an intermediate component linking the terminal components, wherein the terminal components are:
The intermediate component is an oligomer containing an organosiloxane molecular chain containing at least one polyfluoroalkyl group bonded via a urethane bond or a urea bond, and the terminal component and the intermediate component are connected by a urethane bond. Or a polyurethane emulsion characterized by emulsifying water in an organic solvent solution excluding a compound bound by a urea bond.

(Operation) Next, the present invention will be described in more detail. The inventor of the present invention has found that the problem of the prior art as described above is that a polyurethane specific to the formation of the porous layer, that is, a silicone in the main chain and / or the side chain, It has been found that the problem is solved by using a polyurethane resin having a segment and a fluorocarbon segment.

That is, in the present invention, the silicone compound and the fluorine compound as the softening agent or the water repellent are covalently included in the polyurethane. It does not bleed out to the surface or is not removed by washing, and can maintain excellent surface lubricity, high flexibility, water pressure resistance, stain resistance and washing resistance almost permanently. is there.

(Preferred Embodiment) The present invention will be described in more detail with reference to preferred embodiments of the present invention.

The polyurethane resin having a silicone segment and a fluorocarbon segment used in the present invention and which mainly characterizes the present invention is a polyol, a polyisocyanate, a polyol, a polyisocyanate, when a polyurethane resin is obtained by reacting a polyol, a polyisocyanate, a chain extender, or the like. Alternatively, it can be obtained by using a silicone compound having a reactive functional group such as an amino group, an epoxy group, a hydroxyl group, a carboxyl group, a thioalcohol group, or a fluorine compound as all or a part of the chain extender.

Further, when synthesizing a polyurethane resin as described above, a polyurethane resin having a silicone segment is synthesized using a silicone compound having a reactive functional group, while a polyurethane resin having a carbon fluoride segment is similarly formed. May be synthesized, and these may be mixed and used at an appropriate ratio.

Preferred examples of the silicone compound having a reactive organic functional group as described above include, for example, the following compounds.

(1) Amino-modified silicone oil (M = 1 to 10, n = 2 to 10, R = CH ₃ or OCH ₃ ) (2) Epoxy-modified silicone oil (3) Alcohol-modified silicone oil (4) Mercapto-modified silicone oil (5) Carboxyl-modified silicone oil Examples of the carbon fluoride compound having a reactive functional group as described above include the following compounds.

(1) H (CF ₂ CF ₂ ) _n CH ₂ OH (n = 1 to 7) (2) CF ₃ (CF ₂ CF ₂ ) _n CH ₂ CH ₂ OH (n = 1 to 10) (3) CF ₃ (CF ₂ CF ₂ ) _n COOH (n = 1 to 10) (4) CF ₃ (CF ₂ CF ₂ ) _n CH ₂ CH ₂ SH (n = 1 to 10) (5) H (CF ₂ CF ₂ ) ₁ (CH ₂ ) _m (OCH ₂ CH ₂ (OH) CH ₂ ) _n
OH (1 = 1 to 10, m = 1 to 10, n = 1 to 3) (6) F (CF ₂ CF ₂ ) ₁ (CH ₂ ) _m (OCH ₂ CH ₂ (OH) CH ₂ ) _n
OH (1 = 1 to 10, m = 1 to 10, n = 1 to 3) The silicone compound and the fluorocarbon compound having a reactive organic functional group as described above are examples of preferable compounds in the present invention. The present invention is not limited to these exemplifications, and the above-exemplified compounds and other compounds are currently commercially available and can be easily obtained from the market, and all of them can be used in the present invention. It is.

Furthermore, at least one of the reactive group of the silicone compound and / or the fluorocarbon compound or the isocyanate group of the polyisocyanate group remains by the silicone compound and / or the carbon fluoride compound and the polyisocyanate as described below. Intermediate obtained by the reaction, for example,
A compound obtained by reacting a bifunctional silicone compound and / or a fluorocarbon compound with a polyfunctional polyisocyanate in an isocyanate group-rich manner, or conversely, a silicone compound and / or
Alternatively, an intermediate obtained by enriching a reactive group of a carbon fluoride compound and reacting the same can also be used.

Further, when the reactive group of the silicone compound and / or the fluorocarbon compound is a hydroxyl group, an amino group, a carboxyl group, an epoxy group, or the like, it is reacted with a polyol, a chain extender, a polycarboxylic acid, or a polyamine described below. Polyester polyols, polyamide polyamines, polyether polyols and the like obtained by the above method can be used in the same manner.

As the polyol, any of the conventionally known polyols for polyurethane can be used.For example, polyethylene glycol adipate having a terminal group of hydroxyl group and a molecular weight of 300 to 4,000, polyethylene propylene adipate, polyethylene butyl adipate, polyethylene butylene adipate, polydiethylene adipate, poly is preferable. Butylene adipate, polyethylene succinate, polybutylene succinate, polyethylene sebacate, polybutylene sebacate, polytetramethylene ether glycol, poly-ε-caprolactone diol, polyhexamethylene adipate, carbonate polyol, polypropylene glycol, etc., and in the above polyols Containing an appropriate amount of a polyoxyethylene chain.

As the organic polyisocyanate, any known organic polyisocyanate can be used. For example, preferred are 4,4'-diphenylmethane diisocyanate (MDI), water-added MDI, isophorone diisocyanate, 1,3-xylylene diisocyanate, and 1 , 4-xylylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,5-naphthalene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, etc., or these organic polyisocyanates A urethane prepolymer obtained by reacting a low molecular weight polyol or polyamine with a terminal isocyanate can also be used.

As the chain extender, any of those conventionally known can be used. For example, preferred are ethylene glycol, propylene glycol, diethylene glycol, 1,4-butanediol, 1,6-hexanediol, ethylenediamine, 2-propylenediamine, trimethylenediamine, tetramethylenediamine, hexamethylenediamine, decamethylenediamine, isophoronediamine, m-xylylenediamine, hydrazine, water and the like.

The polyurethane resin containing the silicone segment and the fluorocarbon segment obtained from the above-mentioned materials together or the blend of the polyurethane resin having the silicone segment and the polyurethane resin having the fluorocarbon segment can be used in the present invention. You can,
Preferred are those in which the sum of the silicone segment and the carbon fluoride segment accounts for about 0.2 to 50% by weight of the resin, and the present invention is used when the total amount of the silicone segment and the carbon fluoride segment is less than about 0.2% by weight. If the amount exceeds about 50% by weight, problems such as a decrease in adhesiveness to the substrate occur, which is not preferable.

The weight ratio of the silicone segment to the fluorocarbon segment in the resin is preferably in the range of the former: the latter = 95 to 5: 5 to 95. The flexibility and surface lubrication are insufficient, and too small a number of the carbon fluoride segments are not preferred because the water pressure resistance and the washing durability become insufficient.

Preferred are those having a molecular weight of 20,000 to 500,000, and most preferred are those having a molecular weight of 20,000 to 250,000.

The polyurethane resin containing the silicone segment and the fluorocarbon segment as described above can be easily obtained by a conventionally known production method. These polyurethane-based resins may be prepared without solvent or may be prepared in an organic solvent, but in a process, an organic solvent to prepare a polyurethane emulsion, i.e., water and a certain amount of water. The preparation in a mutually soluble organic solvent is advantageous because it can be used for preparing a polyurethane emulsion as it is.

Preferred as such organic solvents are methyl ethyl ketone, methyl-n-propyl ketone, methyl isobutyl ketone, diethyl ketone, methyl formate, ethyl formate, propyl formate, methyl acetate, ethyl acetate, butyl acetate and the like, and acetone , Cyclohexane, tetrahydrofuran, dioxane, methanol, ethanol, isopropyl alcohol, butanol, toluene, xylene, dimethylformamide, dimethyl sulfoxide, perchlorethylene, trichloroethylene, methyl cellosolve, butyl cellosolve, cellosolve acetate, and the like. Those having no or no solubility in water in these organic solvents are used as a mixture with other organic solvents with a limit in the mutual solubility with water. The above organic solvents can of course be used as mixed organic solvents.

By preparing a polyurethane-based resin in such an organic solvent, a polyurethane-based resin solution can be obtained, and its solid content is about 5% by adding or removing the same or another solvent.
Conveniently it is in the range of from 60 to 60% by weight. In the present invention, the polyurethane resin may be a solution sufficiently dissolved in an organic solvent, or a dispersion in which the resin is partially or entirely precipitated (hereinafter simply referred to as a solution).

In order to prepare a polyurethane emulsion from the above polyurethane solution, an appropriate amount of a water-in-oil emulsifier is added to the above-mentioned polyurethane solution, if necessary, and, while being vigorously stirred, the emulsifier is added thereto. It is obtained by adding water below the saturation amount, for example, about 50 to 500 parts by weight of water per 100 parts by weight of solids in the solution.

As the emulsifier, any of the conventionally known water-in-oil emulsifiers can be used, but a particularly suitable emulsifier is a polyurethane-based interfacial lubricant having an appropriate amount of polyoxyethylene chain in the molecule. The emulsifier is preferably used in an amount of about 1 to 10 parts by weight per 100 parts by weight of the solid content of the polyurethane resin solution.

The polyurethane emulsion thus obtained is a milky creamy fluid, and maintains a stable state even when left as it is for several months. Such a polyurethane emulsion may optionally contain various additives, for example, known additives such as a coloring agent, a crosslinking agent, a stabilizer, and a filler.

As the base material used for producing a porous sheet from the above-mentioned polyurethane emulsion, for example, various types of woven fabric, knitted fabric, nonwoven fabric, release paper, plastic film, metal plate, glass plate, etc. It may be a material.

The method of applying the polyurethane emulsion to the substrate may be any known method such as, for example, a coating method, a dipping method, or a combination thereof, and the impregnation and / or application amount is about 5 to 2,000 g ( It can be changed in a wide range depending on the purpose, such as (mixed solution) / m ² .

The gelation and drying of the substrate impregnated and / or coated with the polyurethane emulsion may be the same as those in the related art, for example, at a temperature of about 40 to 200 ° C. for several minutes to several hours. By drying, a porous polyurethane sheet material having excellent properties can be obtained.

(Effect) The porous sheet material obtained by using the polyurethane emulsion of the present invention as described above has a very fine pore structure,
Has excellent physical properties and excellent water vapor permeability,
As a material of various synthetic leathers and the like, it is useful for clothing, shoes, waterproof cloth, tents, wallpaper, flooring materials, filtration materials, filters for air conditioners and the like.

In particular, the polyurethane resin in the polyurethane emulsion of the present invention contains a silicone segment and a carbon fluoride segment in the main chain and / or side chain of the molecule, so that a porous layer is formed from the emulsion. However, the silicone segment and the carbon fluoride segment in the porous layer do not bleed out to the surface of the porous layer with the passage of time, and therefore, have a semipermanently excellent surface lubricity, feeling, water pressure resistance, and stain resistance. And can maintain the washing durability.

Next, the present invention will be specifically described with reference to Reference Examples, Examples, Usage Examples, and Comparative Examples. The term “parts by mass” or “%” is based on weight unless otherwise specified.

Reference Example 1 (Production Example of Intermediate) An adduct of 1 mol of trimethylolpropane and 3 mol of tolylene diisocyanate (TDI) (Coronate L, Nippon Polyurethane, 12.5% NCO, 75% solids) 175 parts at 50 ° C.
While stirring well, a terminal aminopropyl polydimethylsiloxane having the following structure (molecular weight 2,20)
0) Slowly add 880 parts to react.

(N is a value at which the molecular weight becomes 2,200) After completion of the reaction, ethyl acetate was evaporated to obtain 976 parts of a transparent liquid intermediate.

According to the infrared absorption spectrum of this intermediate, 2270 / cm
Absorption by free isocyanate groups of
The absorption band due to the Si-OC group was shown at 1090 / cm.

When the free isocyanate group in this intermediate was quantified, the theoretical value was 0.83%, whereas the actual measured value was 0.1%.
78%.

Therefore, the main structure of the above intermediate is presumed to be the following formula.

Reference Example 2 (Production Example of Intermediate) 24 parts of phenylisocyanate was added to 196 parts of terminal hydroxypropylpolydimethylsiloxane (molecular weight: 980) having the following structure, and the mixture was stirred at 60 ° C. and reacted to form a transparent liquid. 213 parts were obtained.

Next, 52 parts of an adduct of hexamethylene diisocyanate and water (duranate 24A-100, manufactured by Asahi Kasei Corporation, NCO% 23.5) was stirred well at 60 ° C., and the above reaction product was added thereto.
220 parts were gradually added dropwise and reacted to obtain 263 parts of a colorless and transparent liquid intermediate.

According to the infrared absorption spectrum of this intermediate, 2270 / cm
Absorption by free isocyanate groups of
The absorption band due to the Si-OC group was shown at 1090 / cm.

When the free isocyanate group in this intermediate was quantified, the theoretical value was 1.54%, whereas the measured value was 1.
37%.

Therefore, the main structure of the above intermediate is presumed to be the following formula.

Reference Example 3 (Production Example of Intermediate) To 230 parts of terminal aminopropyl polydimethylsiloxane (molecular weight 1,150) having the following structure, 15 parts of n-butyraldehyde was added, and the mixture was reacted at 80 ° C. with good stirring to produce. Reaction was carried out for 3 hours while removing water out of the system under reduced pressure.
238 parts of a transparent liquid reaction product were obtained.

Next, an adduct of 1 mol of trimethylolpropane and 3 mol of xylylene diisocyanate (takenate D110N,
While 186 parts of Takeda Pharmaceutical, NCO% 11.5, solid content 75%) were stirred well at room temperature, 490 parts of the above reaction product was gradually dropped therein and reacted at 60 ° C.

After completion of the reaction, the ethyl acetate was evaporated to obtain 610 parts of a transparent liquid intermediate.

According to the infrared absorption spectrum of this intermediate, 2270 / cm
Absorption by free isocyanate groups of
The absorption band due to the Si-OC group was shown at 1090 / cm.

When the free isocyanate group in this intermediate was quantified, the theoretical value was 1.34%, whereas the actual value was 1.
25%.

Therefore, the main structure of the above intermediate is presumed to be the following formula.

Reference Example 4 (Production example of intermediate) 35 parts of 2,6-tolylene diisocyanate and 110 parts of ethyl acetate
While thoroughly stirring the mixture at 60 ° C., 316 parts of mercaptopropyl-terminated polydimethylsiloxane (molecular weight: 1,580) having the following structure and having the following structure are gradually reacted dropwise.

After completion of the reaction, the ethyl acetate was evaporated to obtain 340 parts of a transparent liquid intermediate.

According to the infrared absorption spectrum of this intermediate, 2270 / cm
Absorption by free isocyanate groups of
The absorption band due to the Si-OC group was shown at 1090 / cm.

When the free isocyanate groups in this intermediate were quantified, the theoretical value was 2.39%, whereas the measured value was 2.
It was 12%.

Therefore, the main structure of the above intermediate is presumed to be the following formula.

Reference Example 5 (Production example of intermediate) 52 parts of hexamethylene diisocyanate and 16 parts of ethyl acetate
While stirring 0 parts at 60 ° C., 450 parts of terminal hydroxypropyl polydimethylsiloxane (molecular weight 2,250) having the following structure is gradually dropped therein and reacted.

After the reaction was completed, the ethyl acetate was evaporated to obtain 488 parts of a transparent liquid intermediate.

According to the infrared absorption spectrum of this intermediate, 2270 / cm
Absorption by free isocyanate groups of
The absorption band due to the Si-OC group was shown at 1090 / cm.

When the free isocyanate group in this intermediate was quantified, the theoretical value was 1.67%, whereas the measured value was 1.67%.
52%.

Therefore, the main structure of the above intermediate is presumed to be the following formula.

Reference Example 6 (Production Example of Intermediate) 52 parts of an adduct of hexamethylene diisocyanate and water (Duranate 24A-100, manufactured by Asahi Kasei Corporation, NCO% 23.5) was heated at 60 ° C.
While stirring well, 53 parts of a fluorinated alcohol having the following structure was slowly added dropwise thereto, and reacted to obtain 103 parts of a colorless and transparent liquid intermediate.

H (CF ₂ CF ₂ ) ₅ CH ₂ OH According to the infrared absorption spectrum of this intermediate, 2270 / cm
Absorption by free isocyanate groups of
/ -CF ₂ to cm - it showed an absorption band by the group. Further, when the free isocyanate groups in this intermediate were quantified, the theoretical value was 2.65%, whereas the measured value was 2.51%.

Therefore, the main structure of the above intermediate is presumed to be the following formula.

Reference Example 7 (Production Example of Intermediate) An adduct of 1 mol of trimethylolpropane and 3 mol of tolylene diisocyanate (TDI) (Coronate L, Nippon Polyurethane, NCO% 12.5, solid content 75%) 120 parts at 50 ° C.
While stirring well, 114 parts of a fluorinated alcohol having the following structure is gradually dropped therein to react.

After the completion of the CF ₃ (CF ₂ CF ₂ ) ₃ CH ₂ CH ₂ OH reaction, 198 parts of a transparent liquid intermediate was obtained.

According to the infrared absorption spectrum of this intermediate, 2270 / cm
Absorption by free isocyanate groups of
/ -CF ₂ to cm - it showed an absorption band by the group. Further, when the free isocyanate group in this intermediate was quantified, the theoretical value was 2.83%, whereas the measured value was 2.68%.

Therefore, the main structure of the above intermediate is presumed to be the following formula.

Reference Example 8 (Production Example of Intermediate) 186 parts of an adduct (takenate D110N, manufactured by Takeda Pharmaceutical Co., Ltd., NCO% 11.5, solid content 75%) of 1 mol of trimethylolpropane and 3 mol of xylylene diisocyanate were thoroughly stirred at room temperature. Meanwhile, 172 parts of a fluorinated thioalcohol having the following structure was gradually added dropwise and reacted.

After completion of the reaction of CF ₃ (CF ₂ CF ₂ ) ₃ CH ₂ CH ₂ SH, 320 parts of a transparent liquid intermediate was obtained.

According to the infrared absorption spectrum of this intermediate, 2270 / cm
Absorption by free isocyanate groups of
/ -CF ₂ to cm - it showed an absorption band by the group. When the free isocyanate group in this intermediate was quantified, the theoretical value was 2.69%, whereas the measured value was 2.51%.

Therefore, the main structure of the above intermediate is presumed to be the following formula.

Reference Example 9 (Modification of resin: terminal of main chain) 1,000 parts of polyethylene adipate (average molecular weight: about 1,000, hydroxyl value: 112), 144 parts of 1,4-butanediol, 1,144 parts of methyl ethyl ketone, and 650 parts of diphenylmethane diisocyanate were added at 70 ° C for 8 hours. After the reaction for a period of time, 3,042 parts of methyl ethyl ketone was further added to homogenize, and the mixture was cooled to room temperature with stirring to obtain a milky white polyurethane dispersion having a solid content of 30%.

The intermediate 5 of Reference Example 1 was added to 100 parts of this polyurethane dispersion.
And 5 parts of the intermediate of Reference Example 6 were added and reacted at 70 ° C. for 4 hours to obtain a milky white modified resin liquid (1) in which the intermediate and the polyurethane resin were bonded.

The modified resin obtained above did not show any isocyanate group by infrared absorption spectrum. This is presumed that the intermediate was grafted to the resin.

Reference Example 10 (Modification of resin: terminal of main chain) 1,4-butaneethylene adipate (average molecular weight: about 1,00
0, hydroxyl value 112) 1,000 parts, 1,4-butanediol 144
Part, 1,144 parts of methyl ethyl ketone and 650 parts of diphenylmethane diisocyanate were reacted at 70 ° C. for 8 hours.
42 parts of methyl ethyl ketone was added to homogenize, and the mixture was cooled to room temperature with stirring to obtain a milky white polyurethane dispersion having a solid content of 30%.

The intermediate 5 of Reference Example 2 was added to 100 parts of this polyurethane dispersion.
And 5 parts of the intermediate of Reference Example 7 were added and reacted at 70 ° C. for 4 hours to obtain a milky white modified resin liquid (2) in which the intermediate and the polyurethane resin were bonded.

The modified resin obtained above did not show any isocyanate group by infrared absorption spectrum. This is presumed that the intermediate was grafted to the resin.

Reference Example 11 (Modification of resin: terminal of main chain) 1,6-hexamethylene adipate (average molecular weight: about 2,000
0, hydroxyl value 56) 1,000 parts, 1,4-butanediol 125 parts,
After 1,200 parts of methyl ethyl ketone and 472 parts of diphenylmethane diisocyanate were reacted at 70 ° C. for 8 hours, 2,526 parts of ethyl ethyl ketone was further added and homogenized, and the mixture was cooled to room temperature with stirring to obtain a milky white polyurethane dispersion having a solid content of 30%. .

The intermediate 5 of Reference Example 3 was added to 100 parts of this polyurethane dispersion.
And 5 parts of the intermediate of Reference Example 8, and reacted at 70 ° C. for 4 hours to obtain a milky white modified resin liquid (3) in which the intermediate and the polyurethane resin were bonded.

The modified resin obtained above did not show any isocyanate group by infrared absorption spectrum. This is presumed that the intermediate was grafted to the resin.

Reference Example 12 (Modification of resin: terminal of main chain) Polytetramethylene glycol (average molecular weight: about 1,00
0, hydroxyl value 112) 1,000 parts, ethylene glycol 93 parts,
After 1,500 parts of methyl ethyl ketone and 625 parts of diphenylmethane diisocyanate were reacted at 70 ° C. for 8 hours, 2,500 parts of methyl ethyl ketone was further added and homogenized, and the mixture was cooled to room temperature with stirring to obtain a milky white polyurethane dispersion having a solid content of 30%. .

The intermediate 5 of Reference Example 4 was added to 100 parts of this polyurethane dispersion.
Then, 5 parts of the intermediate of Reference Example 7 was added and reacted at 70 ° C. for 4 hours to obtain a milky white modified resin liquid (4) in which the intermediate and the polyurethane resin were bonded.

The modified resin obtained above did not show any isocyanate group by infrared absorption spectrum. This is presumed that the intermediate was grafted to the resin.

Reference Example 13 (Modification of resin: terminal of main chain) Polycarbonate polyol (average molecular weight: about 2,000,
Hydroxyl value 56) 1,000 parts, 86 parts of ethylene glycol, 1,200 parts of methyl ethyl ketone and 509 parts of diphenylmethane diisocyanate were reacted at 70 ° C. for 8 hours, and further, 2,522 parts of methyl ethyl ketone was added to homogenize, cooled to room temperature with stirring, and solid content was 30 % Milky polyurethane dispersion was obtained.

The intermediate 5 of Reference Example 5 was added to 100 parts of this polyurethane dispersion.
And 5 parts of the intermediate of Reference Example 8 were added and reacted at 70 ° C. for 4 hours to obtain a milky white modified resin liquid (5) in which the intermediate and the polyurethane resin were bonded.

The modified resin obtained above did not show any isocyanate group by infrared absorption spectrum. This is presumed that the intermediate was grafted to the resin.

Reference Example 14 (Modification of resin: main chain) 1,4-butaneethylene adipate (average molecular weight: about 1,00
0, hydroxyl value 112) 1,000 parts, 100 parts of a silicone compound having the following structure (A), and 50 parts of a carbon fluoride compound having the following structure (B):
, 31 parts of 1,4-butanediol and 362 parts of diphenylmethane diisocyanate were added to 3,600 parts of methyl ethyl ketone and reacted at 70 ° C for 8 hours to obtain a polyurethane resin solution having an average molecular weight of 64,000 and a solid content of 30%. Was.

Next, 130 parts of ethylene glycol and 503 parts of diphenylmethane diisocyanate were added to the resin solution,
After further reacting for 10 hours, the mixture was further homogenized by adding 1,477 parts of methyl ethyl ketone, and cooled to room temperature with stirring. The solid content of polyurethane having an average molecular weight of 133,000 and a particle diameter of precipitated particles of 1 μm or less was 30 μm. % Milky polyurethane dispersion (6) was obtained.

Reference Example 15 (Modification of resin: main chain) Polytetramethylene glycol (average molecular weight: about 1,00
0, hydroxyl value 112) 1,000 parts, 100 parts of a silicone compound having the following structure (C), and 50 parts of a carbon fluoride compound having the following structure (D)
Parts, ethylene glycol 24 parts and diphenylmethane diisocyanate 360 parts were added to methyl ethyl ketone 3,580 parts and reacted at 70 ° C. for 9 hours to obtain a polyurethane resin solution having an average molecular weight of 53,000 and a solid content of 30%.

Subsequently, 116 parts of ethylene glycol and 465 parts of diphenylmethane diisocyanate were added to the resin solution,
After further reacting for 10 hours, the mixture was further homogenized by adding 1,356 parts of methyl ethyl ketone, cooled to room temperature with stirring, and solid content of polyurethane having an average molecular weight of 107,000 and a particle diameter of precipitated particles of 1 μm or less was 30 μm. % Milky polyurethane dispersion (7) was obtained.

Reference Example 16 (Modification of resin: main chain) 1,6-hexamethylene adipate (average molecular weight: about 2,000
0, hydroxyl value 56) 2,000 parts, 200 parts of a silicone compound having the following structure (E), 50 parts of a carbon fluoride compound having the following structure (F),
31 parts of 1,4-butanediol and 346 parts of diphenylmethane diisocyanate were added to 6,135 parts of methyl ethyl ketone and reacted at 70 ° C. for 9 hours to obtain a polyurethane resin solution having an average molecular weight of 72,000 and a solid content of 30%.

Next, 390 parts of trimethylolpropane and 1,047 parts of diphenylmethane diisocyanate were added to the resin solution, and the mixture was reacted at 60 ° C. for 10 hours.
Add 3 parts, homogenize, cool to room temperature with stirring,
Polyurethane has an average molecular weight of 178,000 and a solid content of 30
% Milky polyurethane dispersion (8) was obtained.

Examples 1 to 8 The products of Reference Examples 9 to 16, the emulsifier, the organic solvent and water were stirred with a homomixer to prepare the following polyurethane emulsion of the present invention.

Example 1: Polyurethane emulsion (1) Polyurethane liquid (1) 100 parts Urethane emulsifier 2 parts Methyl ethyl ketone 20 parts Xylene 20 parts Water 85 parts Example 2: Polyurethane emulsion (2) 100 parts polyurethane liquid (2) Urethane emulsifier 2 parts Methyl ethyl ketone 20 parts Toluene 20 parts Water 80 parts Example 3; polyurethane emulsion (3) Polyurethane liquid (3) 100 parts Urethane emulsifier 2 parts Methyl ethyl ketone 150 parts Toluene 20 parts Water 80 parts Example 4; Polyurethane emulsion (4) Polyurethane emulsion (4) 100 parts PO / EO block copolymer type emulsifier 4 parts Dioxane 10 parts Toluene 10 parts Xylene 20 parts Water 70 parts Example 5; Polyurethane emulsion (5) Polyurethane liquid (5) 100 parts Urethane emulsifier 1 part Methyl isobutyl ketone 20 parts Toluene 20 parts Water 75 parts Example 6; polyurethane emulsion (6) polyurethane (6) 100 parts PO / EO block copolymer type emulsifier 1 part Tetrahydrofuran 20 parts Toluene 20 parts Water 60 parts Example 7; polyurethane emulsion (7) Polyurethane liquid (7) 100 parts Urethane emulsifier 2 parts Methyl ethyl ketone 20 parts Xylene 20 parts Water 85 parts Example 8; Polyurethane emulsion (8) Polyurethane liquid (8) 100 parts Urethane emulsifier 2 parts Methyl ethyl ketone 20 parts Toluene 20 parts Water 80 parts Comparative Examples 1 to 8 Silicones in Examples 1 to 8 As the polyurethane resin containing a segment and a carbon fluoride segment, a polyurethane resin liquid having no silicone segment and no carbon fluoride segment prepared in the same manner as in Reference Examples 9 to 16 was used, and the other conditions were the same as in Examples 1 to 8. Thus, polyurethane emulsions of Comparative Examples 1 to 8 were prepared.

The properties of the polyurethane emulsions of Examples 1 to 8 and Comparative Examples 1 to 8 are as shown in Table 1 below.

Use Examples 1 to 8 The polyurethane emulsions shown in Table 1 were impregnated and / or coated on various substrates under the conditions shown in Table 2 below, and dried to obtain various types having the properties shown in Table 3 below. Was obtained. Note that Comparative Use Examples 1 to 8 were performed under the same conditions as Use Examples 1 to 8, respectively.

Continued on the front page (72) Inventor Iwao Mihozu 2-5-2 Fujimi, Ageo City, Saitama Prefecture (72) Inventor Masashi Kashimura 4-18-13 Ukima, Kita-ku, Tokyo (72) Inventor Tomoko Goto Kawaguchi-shi, Saitama 4-4-33 Nishi Aoki (72) Inventor Katsumi Kuriyama 1135-1 Shimokuma Kuri, Koshigaya City, Saitama Prefecture (56) References JP-A-62-218471 (JP, A) U.S. Pat.

Claims (3)

(57) [Claims] 1. A polyurethane resin having a silicone segment and a fluorocarbon segment in a main chain and / or a side chain (provided that at least two polyfluoroalkyl group-containing terminal members are connected to an intermediate member connecting the terminal members). Wherein the terminal structure has at least one polyfluoroalkyl group bonded through a urethane bond or a urea bond, and the intermediate structure has an organosiloxane molecular chain. A polyurethane emulsion, which is obtained by emulsifying water in an organic solvent solution of an oligomer, excluding a compound in which the above-mentioned terminal structure and intermediate structure are bonded by a urethane bond or a urea bond). 2. The total amount of the silicone segment and the carbon fluoride segment is 0.2 to 5 in the total amount of the polyurethane resin.
The polyurethane emulsion according to claim 1, which is in an amount occupying 0% by weight. 3. The polyurethane emulsion according to claim 1, wherein the weight ratio of the silicone segment to the fluorocarbon segment is 95 to 5: 5 to 95.