JPH0791354B2 - Polyurethane emulsion - Google Patents

Description

TECHNICAL FIELD The present invention relates to a polyurethane emulsion, and has various properties such as surface lubricity, water repellency (water pressure resistance), washing durability, mechanical properties, and water vapor permeability. An object of the present invention is to provide a polyurethane emulsion capable of providing a porous sheet material excellent in texture and good in texture.

(Prior Art) Conventionally, a large number of porous sheet materials made of polyurethane resins and methods for producing them have been known as natural leather substitutes and the like, and can be 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. Examples of such a dry method include JP-B-48-4380, JP-B-48-8742 and JP-A-51.
-41063, JP-A-54-66961 and JP-A-54-
The method described in Japanese Patent No. 68498 is known.

According to these known methods, a porous sheet material having excellent moisture permeability is provided. However, since these porous sheet materials are porous, it is natural that the surface smoothness is improved. Is inferior and is easily soiled. In addition, the texture is insufficient.

In addition, since the fine pores of these porous sheets are communicating holes for the purpose of moisture permeability, it is easy for water to enter from the outside, so when used in rainy weather, water penetrates into the inside. There is a problem that the inside gets wet.

As a method for solving such a problem, a method of incorporating a so-called softening agent such as a silicone compound or a fluorine-containing compound or a water repellent in the porous layer is also widely used. Since the agent is a relatively low molecular weight compound and has poor compatibility with polyurethane resins, it bleeds out over time on the surface of the porous layer, making the surface sticky or dusty. The problem of pollution arises.

Repeated washing further removes softeners and water repellents, resulting in loss of washing durability due to loss of surface lubricity, texture, and water repellency (water pressure resistance) imparted by the softeners and water repellents. Is occurring.

Therefore, there is a demand for the development of a porous sheet material which is porous but has excellent surface slipperiness, good feeling, water pressure resistance and washing durability.

As a result of earnest research to meet the above-mentioned demands, the present inventor has solved the above-mentioned drawbacks of the prior art when using a specific polyurethane emulsion, and is a porous sheet material that can sufficiently meet the above-mentioned demands of the industry. The present invention has been completed by finding that it can be provided.

(Means for Solving Problems) That is, in the present invention, when reacting a polyol, a polyisocyanate, an extender or the like which does not contain a fluorine atom, the reactivity of the polyol, the polyisocyanate or the chain extender as a whole or a part thereof is increased. A polyurethane emulsion obtained by using a silicone compound having a group, which is obtained by emulsifying water in an organic solvent solution of a polyurethane resin having a silicone segment in a main chain and / or a side chain. .

(Function) Next, the present invention will be described in more detail. The present inventor has found that the above-mentioned problems with the prior art include polyurethane specific to the formation of the porous layer, that is, a silicone segment in the main chain and / or side chain. It was discovered that this can be solved by using a polyurethane resin having

That is, in the present invention, since the silicone compound as the softening agent or the water repellent is included in the polyurethane by the covalent bond, the softening agent or the water repellent bleeds on the surface with time even after the formation of the porous layer. Out or
It is not permanently removed by washing, and can almost permanently retain excellent surface slipperiness, high flexibility, water pressure resistance and washing resistance.

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

The polyurethane-based resin having a silicone segment, which is used in the present invention and mainly characterizes the present invention,
When a polyurethane resin is obtained by reacting a polyol, a polyisocyanate, a chain extender, etc., a polyol,
All or part of the polyisocyanate or chain extender, amino group, epoxy group, hydroxyl group, carboxyl group,
It is obtained by using a silicone compound having a reactive functional machine such as a thioalcohol group. None of the above compounds contain a fluorine atom.

Preferred examples of such a silicone compound having a reactive organic functional group include the following compounds.

(1) Amino-modified silicone oil (M = 1 to 10, n = 2 to 10, R = CH ₃ or OCH ₃ ) (M = 1 to 10, n = 2 to 10, R = CH ₃ or OCH ₃ ) (M = 0 to 200) (N = 2 to 10) (Branch point = 2 to 3, R = lower alkyl group, l = 2 to
200, m = 2 to 200, n = 2 to 200) (N = 1 to 200, R = lower alkyl group) (2) Epoxy-modified silicone oil (N = 1 to 200) (M = 1 to 10, n = 2 to 10) (N = 1 to 200) (Branch point = 2 to 3, R = lower alkyl group, l = 2 to
200, m = 2 to 200, n = 2 to 200) (N = 1 to 10) (M = 1 to 10, n = 2 to 10) (3) Alcohol-modified silicone oil (N = 1 to 200) (M = 1 to 10, n = 2 to 10) (N = 0 to 200) (L = 1 to 10, m = 10 to 200, n = 1 to 5) (L = 1 to 200, R = lower alkyl) (4) Mercapto-modified silicone oil (M = 1 to 10, n = 2 to 10) (N = 2 to 10) (Branch point = 2 to 3, R = lower alkyl group, l = 2 to
200, m = 2 to 200, n = 2 to 200) (N = 1 to 200, R = lower alkyl group) (5) Carboxyl-modified silicone oil (M = 1 to 10, n = 2 to 10) (N = 1 to 200) (Branch point = 2 to 3, R = lower alkyl group, l = 2 to
200, m = 2 to 200, n = 2 to 200) (N = 1 to 200, R = lower alkyl group) The silicone compound having a reactive organic functional group as described above is an example of a preferred silicone compound in the present invention, and the present invention is limited to these examples. However, the above-exemplified compounds and other silicone compounds are commercially available at present, and are easily available from the market, and any of them can be used in the present invention.

Further, an intermediate obtained by reacting a silicone compound as described above and a polyisocyanate as described below so that at least one of the reactive group of the silicone compound or the isocyanate group of the polyisocyanate group remains, for example,
It is also possible to use a product obtained by reacting a bifunctional silicone compound with a polyfunctional polyisocyanate in a rich isocyanate group, or conversely, an intermediate obtained by reacting a silicone compound with a rich reactive group.

Further, the reactive group of the silicone compound is a hydroxyl group, an amino group,
When it is a carboxyl group, an epoxy group, etc., a polyol to be described later, a polyester polyol obtained by reacting with a chain extender or a polyvalent carboxylic acid or a polyvalent amine, a polyamide polyamine, a polyether polyol, etc. may be similarly used. You can

As the polyol, any conventionally known polyol for polyurethane can be used.For example, as a preferred one, polyethylene adipate having a hydroxyl group as a terminal group and a molecular weight of 300 to 4,000, polyethylene propylene adipate, polyethylene butylene adipate, polydiethylene adipate, poly 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 those containing an appropriate amount of polyoxyethylene chains.

As the organic polyisocyanate, any conventionally known one can be used, but preferred examples include 4,4′-diphenylmethane diisocyanate (MDI), water-added MDI, isophorone diisocyanate, 1,3-xylylene diisocyanate, 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 Urethane prepolymers obtained by reacting low molecular weight polyols and polyamines to form terminal isocyanates can of course be used.

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

Any of the silicone segment-containing polyurethane-based resins obtained from the materials as described above can be used in the present invention, but preferred are those in which the silicone segment accounts for about 0.2 to 50% by weight in the molecule, and the silicone segment is about If it is less than 0.2% by weight, the intended purpose of the present invention will not be achieved sufficiently, and if it exceeds about 50% by weight, problems such as deterioration of adhesiveness will occur, which is not preferable.

The preferred ones have a molecular weight of 20,000 to 500,000, and the most preferred ones have a molecular weight of 20,000 to 250,000.

The silicone segment-containing polyurethane resin as described above can be easily obtained by a conventionally known production method. These polyurethane-based resins may be prepared without a solvent or may be prepared in an organic solvent, but in the process, an organic solvent for preparing a polyurethane emulsion,
That is, it is advantageous that it can be used as it is for the preparation of a polyurethane emulsion by preparing it in an organic solvent having a certain degree of mutual solubility with water.

Preferred as such an organic solvent 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, dimethylsulfoxide, perchlorethylene, trichloroethylene, methylcellosolve, butylcellosolve, cellosolve acetate and the like can also be used. Those which have no limit in mutual solubility with water in these organic solvents or those which do not dissolve at all are used as a mixture with other organic solvents, with a limit in mutual solubility with water. Of course, the above organic solvents can be used as a mixed organic solvent.

A polyurethane resin solution can be obtained by preparing a polyurethane resin in such an organic solvent, and it is convenient that the solid content is in the range of about 5 to 60% by weight by adding or removing the same or another solvent. Is. In the present invention, the polyurethane resin may be a solution which is sufficiently dissolved in an organic solvent, or may be a dispersion which 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 polyurethane solution, if necessary, while stirring it vigorously. It can be obtained by adding a subsaturated amount of water, for example, about 50 to 500 parts by weight of water per 100 parts by weight of the solid content in the solution.

As the emulsifier, any conventionally known water-in-oil type emulsifier can be used, but a particularly preferable one is a polyurethane-based interfacial lubricant having an appropriate amount of polyoxyethylene chains in the molecule. The emulsifier is preferably used in a proportion 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-white cream-like fluid, and maintains a stable state even when left as it is for several months. Such a polyurethane emulsion may optionally contain various additives such as colorants,
Known additives such as a cross-linking agent, a stabilizer and a filler can be optionally added.

Examples of the substrate used for producing the porous sheet from the polyurethane emulsion as described above include various woven fabrics,
Any substrate such as knitted cloth, non-woven cloth, release paper, plastic film, metal plate, glass plate may be used.

The method of applying the polyurethane emulsion to the substrate is
For example, any known method such as a coating method, a dipping method, or a combination method thereof may be used, and the impregnation and / or coating amount is about 5 to 2,000 g (blended liquid) / m ² according to the purpose. It can be varied over a wide range.

The gelation and drying of the substrate impregnated and / or coated with the above polyurethane emulsion may be the same as in the prior art, for example, at a temperature of about 40 to 200 ° C for several minutes to several hours. Upon drying, a polyurethane porous sheet material having excellent properties is 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, It is useful as a material for synthetic leather, etc., for clothing, shoes, waterproof cloth, tents, wallpaper, flooring materials, filter 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 in the main chain and / or side chain of its molecule, and as a result, even if a porous layer is formed from the emulsion, The silicone segment in the layer does not bleed out to the surface of the porous layer over time, and thus it is possible to maintain semipermanently excellent surface slipperiness, feeling, water pressure resistance and washing durability.

Next, the present invention will be specifically described with reference to Reference Examples, Examples, Use Examples and Comparative Examples. In addition, in the text, "%" and "%" are based on weight.

Reference Example 1 (Production Example of Intermediate) 175 parts of an adduct of 1 mol of trimethylolpropane and 3 mol of tolylene diisocyanate (TDI) (Coronate L, made by Nippon Polyurethane, NCO% 12.5, solid content 75%) at 50 ° C. While stirring well, the terminal aminopropylpolydimethylsiloxane (molecular weight 2,20
0) Gradually add 880 parts to react.

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

According to the infrared absorption spectrum of this intermediate, the absorption due to the free isocyanate group of 2270 / cm remains, and 10
An absorption band due to the Si-OC group was shown at 90 / cm.

Moreover, when the free isocyanate group in this intermediate was quantified, the theoretical value was 0.83%, whereas the measured value was 0.78.
%Met.

Therefore, the main structure of the above intermediate is estimated 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 well at 60 ° C. and reacted to give a transparent liquid reaction product. (A) 213 parts were obtained.

(N is the value at which the molecular weight is 980) Next, 52 parts of the adduct of hexamethylene diisocyanate and water (Duranate 24A-100, manufactured by Asahi Kasei, NCO% 23.5) is thoroughly stirred at 60 ° C. into the above. (220 parts) of the reaction product (A) was gradually added and reacted to obtain 263 parts of a colorless and transparent liquid intermediate.

According to the infrared absorption spectrum of this intermediate, the absorption due to the free isocyanate group of 2270 / cm remains, and 10
An absorption band due to the Si-OC group was shown at 90 / cm.

Also, when the free isocyanate group in this intermediate was quantified, the theoretical value was 1.54%, while the measured value was 1.37.
%Met.

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

Reference Example 3 (Production Example of Intermediate) To 230 parts of terminal aminopropylpolydimethylsiloxane (molecular weight 1,150) having the following structure, 15 parts of n-butyraldehyde was added, and the mixture was stirred well at 80 ° C. and reacted to produce water. Was removed from the system under reduced pressure and reacted for 3 hours,
238 parts of a transparent liquid reaction product (B) was obtained.

(N is a value at which the molecular weight is 1,150) Next, 186 parts of an adduct of 1 mol of trimethylolpropane and 3 mol of xylylenediisocyanate (Takenate D110N, Takeda Yakuhin, NCO% 11.5, solid content 75%) is added. While stirring well at room temperature, 490 parts of the above reaction product (B) was gradually added dropwise thereto, and the reaction was carried out at 60 ° C.

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

According to the infrared absorption spectrum of this intermediate, the absorption due to the free isocyanate group of 2270 / cm remains, and 10
An absorption band due to the Si-OC group was shown at 90 / cm.

Moreover, when the free isocyanate group in this intermediate was quantified, the theoretical value was 1.34%, whereas the measured value was 1.25.
%Met.

Therefore, the main structure of the above intermediate is estimated 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 were thoroughly stirred at 60 ° C., and a terminal mercaptopropyl polydimethylsiloxane (molecular weight 1,580) having the following structure was added thereto. 316 parts are gradually dropped to react.

(L, m, and n are values at which the molecular weight becomes 1,580) After the reaction was completed, ethyl acetate was evaporated to obtain 340 parts of a transparent liquid intermediate.

According to the infrared absorption spectrum of this intermediate, the absorption due to the free isocyanate group of 2270 / cm remains, and 10
An absorption band due to the Si-OC group was shown at 90 / cm.

In addition, when the free isocyanate group in this intermediate was quantified, the theoretical value was 2.39%, whereas the measured value was 2.12.
%Met.

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

(L, m, n are the values at which the molecular weight is 1,580) Reference Example 5 (Production Example of Intermediate) Hexamethylene diisocyanate 52 parts and ethyl acetate 160
While thoroughly stirring the mixture at 60 ° C., 450 parts of terminal hydroxypropylpolydimethylsiloxane (molecular weight 2,250) having the following structure is gradually added dropwise to the reaction.

(N is the value at which the molecular weight is 1,580) After completion of the reaction, 488 parts of a transparent liquid intermediate was obtained by evaporating ethyl acetate.

According to the infrared absorption spectrum of this intermediate, the absorption due to the free isocyanate group of 2270 / cm remains, and 10
An absorption band due to the Si-OC group was shown at 90 / cm.

Also, when the free isocyanate group in this intermediate was quantified, the theoretical value was 1.67%, while the measured value was 1.52.
%Met.

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

Reference Example 6 (Modification of Resin ... Side 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 at 70 ° C. for 8 hours. After the reaction, 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%.

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

The resin obtained above had no isocyanate group by infrared absorption spectrum. It is presumed that this is an intermediate grafted to the resin.

Reference Example 7 (Modification of resin ... Side chain) 1,4-butane ethylene adipate (average molecular weight about 1,000,
Hydroxyl value 112) 1,000 parts, 1,4-butanediol 144 parts, methyl ethyl ketone 1,144 parts and diphenylmethane diisocyanate 650 parts are reacted at 70 ° C. for 8 hours, and then methyl ethyl ketone 3,042 parts are further added to homogenize and cooled to room temperature with stirring. A milky white polyurethane dispersion having a solid content of 30% was obtained.

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

The resin obtained above had no isocyanate group by infrared absorption spectrum. It is presumed that this is an intermediate grafted to the resin.

Reference Example 8 (Modification of resin ... Side chain) 1,000 parts of 1,6-hexamethylene adipate (average molecular weight 2,000, hydroxyl value 56), 125 parts of 1,4-butanediol and 472 parts of diphenylmethane diisocyanate were added to 1,200 parts of methyl ethyl ketone. After reacting at 70 ° C. for 8 hours, 2,526 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%.

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

The resin obtained above had no isocyanate group by infrared absorption spectrum. It is presumed that this is an intermediate grafted to the resin.

Reference Example 9 (Modification of resin ... Side chain) Polytetramethylene glycol (average molecular weight about 1,000,
Hydroxyl value 112) 1,000 parts, ethylene glycol 93 parts and diphenylmethane diisocyanate 652 parts are added into 1,500 parts of methyl ethyl ketone, reacted at 60 ° C for 8 hours, further added with 2,500 parts of methyl ethyl ketone and cooled to room temperature with stirring to obtain a solid content of 30 % White milky polyurethane dispersion (4) was obtained.

To 100 parts of this polyurethane dispersion, 5 parts of the intermediate of Reference Example 4 was added and reacted at 60 ° C. for 4 hours to obtain a milky white polyurethane dispersion (4) in which the intermediate and the polyurethane resin were bonded.

The resin obtained above had no isocyanate group by infrared absorption spectrum. It is presumed that this is an intermediate grafted to the resin.

Reference Example 10 (Modification of resin ... Side chain) 1,000 parts of polycarbonate polyol (average molecular weight 2,000, hydroxyl value 56), 86 parts of ethylene glycol and 509 parts of diphenylmethane diisocyanate were added to 1,200 parts of methyl ethyl ketone, and after reacting at 70 ° C. for 8 hours, Further, 2,522 parts of methyl ethyl ketone was 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%.

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

The resin obtained above had no isocyanate group by infrared absorption spectrum. It is presumed that this is an intermediate grafted to the resin.

Reference Example 11 (Modification of resin: main chain) 1,4-butane ethylene adipate (average molecular weight about 1,000,
Hydroxyl value 112) 1,000 parts, silicone compound of the following structure 10
0 parts, 31 parts of 1,4-butanediol and 338 parts of diphenylmethane diisocyanate were added to 3,435 parts of methyl ethyl ketone and reacted at 70 ° C. for 8 hours to give a polyurethane dispersion liquid having a solid content of 30% and an average molecular weight of 65,000 ( A) was obtained.

Then, 130 parts of ethylene glycol and 524 parts of diphenylmethane diisocyanate were added to the above dispersion liquid, and the mixture was mixed at 60 ° C. for 10 hours.
After the reaction for 1 hour, 1,526 parts of methyl ethyl ketone was added to homogenize, and the mixture was cooled at room temperature with stirring. The average molecular weight of polyurethane was 126,000, and the precipitated particles had a particle diameter of 1 μm or less. A polyurethane dispersion (6) of was obtained.

(M in the formula is a value at which the molecular weight becomes 5,000) Reference Example 12 (Modification of Resin: Main Chain) Polytetramethylene glycol (average molecular weight of about 1,000,
Hydroxyl value 112) 1,000 parts, silicone compound of the following structure 10
0 part, 25 parts of ethylene glycol and 348 parts of diphenylmethane diisocyanate were added to 3,435 parts of methyl ethyl ketone and reacted at 70 ° C. for 9 hours to obtain a polyurethane dispersion liquid (B) having an average molecular weight of 52,000 and a solid content of 30%. It was

Then, 116 parts of ethylene glycol and 465 parts of diphenylmethane diisocyanate were added to the above resin solution, and the mixture was mixed at 60 ° C. for 1 hour.
After reacting for 0 hours, 1,356 parts of methyl ethyl ketone was further added to homogenize, and the mixture was cooled to room temperature while stirring. The average molecular weight of polyurethane was 103,000, and the precipitated particles had a particle size of 1 μm or less and a solid content of 30%. A milky white polyurethane dispersion (7) was obtained.

(N in the formula is a value at which the molecular weight becomes 5,000) Reference Example 13 (Modification of resin: main chain) 1,6-hexamethylene adipate (average molecular weight of about 2,000,
Hydroxyl value 56) 2,000 parts, silicone compound 200 with the following structure
Parts, 20 parts of 1,4-butanediol and 310 parts of diphenylmethane diisocyanate were added to 5,903 parts of methyl ethyl ketone and reacted at 70 ° C. for 9 hours to give a polyurethane resin solution having an average molecular weight of 73,000 and a solid content of 30% (C ) Got.

Next, 390 parts of trimethylolpropane and 1,091 parts of diphenylmethane diisocyanate were added to the above resin solution,
After reacting at 0 ° C for 10 hours, add 3,456 parts of methyl ethyl ketone to homogenize it, cool to room temperature with stirring, and have an average molecular weight of polyurethane of 178,000 and a milky white polyurethane dispersion with a solid content of 30% (8). Got

(In the formula, n is a value at which the molecular weight becomes 5,000.) Reference Example 14 (Modification of resin: main chain) 1,4-butane ethylene adipate (average molecular weight about 1,000,
Hydroxyl value 112) 1,000 parts, silicone compound of the following structure 10
0 parts, 31 parts of 1,4-butanediol and 338 parts of diphenylmethane diisocyanate were added to 3,435 parts of methyl ethyl ketone and reacted at 70 ° C. for 8 hours to give a polyurethane resin solution having a solid content of 30% and an average molecular weight of 55,000 ( D) was obtained.

Next, 130 parts of ethylene glycol and 542 parts of diphenylmethane diisocyanate were added to the above resin solution, and the mixture was stirred at 60 ° C for 1 hour.
After reacting for 0 hours, 1,526 parts of methyl ethyl ketone was further added to homogenize, and the mixture was cooled to room temperature while stirring. The average molecular weight of polyurethane was 112,000, and the precipitated particles had a particle size of 1 μm or less and a solid content of 30%. A milky white polyurethane dispersion (9) was obtained.

(N in the formula is a value at which the molecular weight becomes 5,000) Examples 1 to 9 The products of Reference Examples 6 to 14, the emulsifier, the organic solvent and the water are stirred with a homomixer to prepare the polyurethane emulsion of the present invention described below. A liquid was prepared.

Example 1; Polyurethane emulsion (1) Polyurethane dispersion (1) 100 parts Urethane emulsifier 2 parts Methyl ethyl ketone 20 parts Xylene 20 parts Water 85 parts Example 2; Polyurethane emulsion (2) Polyurethane dispersion (2) 100 parts Urethane emulsifier 2 parts Methyl ethyl ketone 20 parts Toluene 20 parts Water 80 parts Example 3; Polyurethane emulsion (3) Polyurethane dispersion (3) 100 parts Urethane emulsifier 2 parts Methyl ethyl ketone 150 parts Toluene 20 parts Water 80 parts Example 4; Polyurethane emulsion (4) Polyurethane dispersion (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 dispersion (5) 100 parts Urethane emulsifier 1 part Methyl isobutyl ketone 20 parts Toluene 20 parts Water 75 parts Example 6; Polyurethane Suspension (6) Polyurethane dispersion (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 dispersion (7) 100 parts Urethane emulsifier 2 parts Methyl ethyl ketone 20 parts Xylene 20 parts Water 85 parts Example 8; Polyurethane emulsion (8) Polyurethane dispersion (8) 100 parts Urethane emulsifier 2 parts Methyl ethyl ketone 20 parts Toluene 20 parts Water 80 parts Example 9 Polyurethane emulsion (9) Polyurethane dispersion (9) 100 parts Urethane emulsifier 2 parts Methyl ethyl ketone 150 parts Toluene 20 parts Water 80 parts Comparative Examples 1 to 9 Instead of the silicone segment-containing polyurethane resin in Examples 1 to 9 , A silicone prepared in the same manner as in Reference Examples 6 to 14 except that no silicone compound was used. Using no polyurethane resin dispersion segments, others in the same manner as in Example 1-9 to prepare a polyurethane emulsion of Comparative Example 1-9.

The properties of the polyurethane emulsions of Examples 1 to 9 and Comparative Examples 1 to 9 are shown in Table 1 below.

Use Examples 1 to 9 Various polyurethanes having the properties shown in Table 3 below were obtained by impregnating and / or coating various substrates with the polyurethane emulsion shown in Table 1 under the conditions shown in Table 2 below. To obtain a porous sheet material. The comparative use examples 1 to 9 are also the use examples 1 to 9, respectively.
The same conditions were used.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Katsumi Kuriyama 1135-1, Shimonoma Kuriya, Koshigaya City, Saitama (56) References JP-A-52-12246 (JP, A) JP-A-62-218471 (JP, A) ) JP-A-60-144318 (JP, A)

Claims (2)

[Claims] 1. When reacting a polyol, a polyisocyanate, a chain extender or the like which does not contain a fluorine atom, a silicone compound having a reactive group is used as all or part of the polyol, polyisocyanate or the chain extender. A polyurethane emulsion obtained by emulsifying water in an organic solvent of a polyurethane resin having a silicone segment in a main chain and / or a side chain, which is obtained as described above. 2. The polyurethane emulsion according to claim 1, wherein the amount of the silicone segment is 0.2 to 50% by weight based on the total amount of the polyurethane resin.