JPH05271432A - Production of hygroscopic polyurethane - Google Patents

Abstract

PURPOSE:To produce a polyurethane molding, such as an elastic polyurethane fiber or a polyurethane film, which has washing-resistant hygroscopicity, can prevent dew condensation resulting from insensible perspiration and perspiration caused by a sport and dew condensation occurring indoors in winter and can give a noncurling coated cloth. CONSTITUTION:The title polyurethane is prepared by dissolving 0.1-10wt.%, based on the polyurethane, magnesium salt (used as such when soluble in the solvent, (for polyrethane and dissolved in an acid when insoluble in the solvent) in a polyurethane composition and molding the resulting composition.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for producing hygroscopic polyurethane. More specifically, polyurethane elastic fibers, polyurethane sheets, and films that can suppress dew condensation caused by perspiration caused by dead steam or sweat caused by exercise and dew condensation that occurs indoors in winter, and can prevent curling, which is a problem with coated cloth, The present invention relates to a representative method for producing a hygroscopic polyurethane molded article.

[0002]

2. Description of the Related Art Conventionally, a composite sheet in which a knitted fabric or a woven fabric is coated or laminated with a polyurethane molding is used for sports clothing. Since polyurethane has moisture permeability, even a non-porous molded article does not retain water in the space between the clothing and the body against water with a small particle size such as sweat due to insensitive vaporization. However, with respect to water with a large particle size such as sweat due to exercise, the moisture permeability of polyurethane itself does not allow the moisture to be released from the clothing in time, causing condensation on the surface of the polyurethane molded product, which is extremely uncomfortable to wear. Becomes In order to avoid this, it was essential to use a composite sheet coated or laminated with a porous type polyurethane molding. However, since improvement in moisture permeability brings about a decrease in waterproofness, it has been desired to develop one having both moisture permeability and waterproofness.

For example, it has been attempted to knead a water-absorbing substance into polyurethane so that the water-absorbing substance absorbs vapor (Japanese Patent Laid-Open No. 3-76871). However, these coated composite sheets have a problem that they are easily curled especially in a high humidity environment and are difficult to sew in the summer. Curling is said to occur because the base fabric set by dry heat during resin coating absorbs moisture and expands at room temperature, whereas the urethane resin layer does not absorb moisture and does not expand. Even if a water-absorbing substance is added, the polyurethane resin itself absorbs moisture and does not expand, so the problem of curling cannot be solved.

Further, it is known as a chlorine resistant yarn made of polyurethane elastic fiber to which magnesium oxide or magnesium hydroxide is added (Japanese Patent Laid-Open No. 59-1332).
No. 48), in which a water-soluble and acid-soluble magnesium salt, which is insoluble in a polyurethane solvent such as magnesium oxide or magnesium hydroxide, is not dissolved in the polyurethane composition, was thus obtained. The fibers are not hygroscopic.

As described above, a polyurethane molded product (fiber, sheet, film, etc.) which itself has high hygroscopicity and has no curling problem under normal temperature environment when laminated (coating, laminating) with a cloth made of another material. Appearance was desired.

[0006]

SUMMARY OF THE INVENTION It is an object of the present invention to solve the above-mentioned problems of the prior art and to provide a method for producing a hygroscopic polyurethane molded article having hygroscopicity which is durable to washing.

[0007]

The present invention provides a polyurethane polymer composition containing 0.1 to 0.1 parts by weight of polyurethane polymer.
A method for producing a hygroscopic polyurethane molded product, which comprises dissolving 10% by weight of a magnesium salt and molding. The polyurethane polymer used in the present invention is a substantially linear polymer having hydroxyl groups at both ends and a molecular weight of 600 to 5000, such as polyester diol,
Copolyester diol consisting of dicarboxylic acid and two or more kinds of diol, polylactone diol, polyether diol, polyester amide diol, JP-A-63-1
One or more of copolycarbonate diols, polycarbonate diols, polysiloxane diols, polyurethane diols described in No. 90656, an organic diisocyanate and a chain extender having a polyfunctional active hydrogen atom, for example, hydrazine, polyhydrazide, polysemicarbazide, polyol, Polyurethane, hydroxylamine, water, and an end-capping agent having a monofunctional active hydrogen atom, for example, a dialkylamine, which is obtained by reacting in a single step or in a multi-step manner, to obtain an elastic high molecular polymer having a urethane group in the molecule, is a polyurethane polymer. Examples of the polyurethane polymer composition include a solvent which is dissolved in dimethylformamide, dimethylacetamide or the like.

In addition, if desired, the polyurethane polymer composition contains a compounding agent of an organic or inorganic substance having a specific chemical structure which is useful for known polyurethane polymer compositions, for example, a gas yellowing inhibitor, UV absorbers, antioxidants, antifungal agents, barium sulfate, aluminum silicate, magnesium silicate, calcium silicate, inorganic fine particles such as zinc oxide, calcium stearate, magnesium stearate, polytetrafluoroethylene, organopolysiloxane, etc. It is also possible to appropriately add an inhibitor.

The magnesium salt used in the present invention is a magnesium salt having solubility in dimethylformamide or dimethylacetamide, which is a solvent for the polyurethane polymer, such as magnesium chloride or magnesium acetate. Used by adding 10 to 10% by weight. The magnesium salt used in the present invention is
In the case of dimethylformamide and dimethylacetamide which are the solvents of the polyurethane polymer, magnesium salts which have no solubility, for example, in the case of magnesium oxide or magnesium hydroxide, magnesium ions can be added to the polyurethane polymer to add magnesium ions to the polyurethane molecular chain. Cannot coordinate to the oxygen atom in the soft segment of. Therefore, it is necessary to dissolve the magnesium salt in an acid and add it to the polyurethane polymer composition. Examples of the acid in this case include acetic acid, citric acid, hydrochloric acid and sulfuric acid. The amount of the acid added is preferably equimolar to the magnesium salt. It is not preferable because excessive addition of the acid adversely affects the physical properties of the resulting polyurethane molded product.

After adding a magnesium salt to the polyurethane polymer composition, it is formed into a fiber, sheet, film or the like. When forming into fibers, conventionally known dry spinning and wet spinning are applied. When forming into a film, it is as follows. The film structure applicable to the present invention may be either a microporous film or a non-porous film.
To create a polymer film, a solvent that dissolves the polymer,
There is a wet coagulation method in which a polymer is not dissolved and a solvent in which a polymer is dissolved is freely mixed with a solvent which is freely mixed, and a dry coagulation method in which a polymer is dried at a high temperature to prepare, and the like. Good. However, when water is used in the wet coagulation method, a part of the added magnesium salt moves to water, and thus dry coagulation is preferable.

When the hygroscopic polyurethane molding of the present invention is used as a film to form a composite sheet with a fiber base cloth or the like, it may be laminated by any of a coating method and a laminating method. When laminating by a laminating method, the adhesive may be a polyurethane polymer, a polyacrylic polymer, a polyamide polymer, a polyester polymer, a polyvinyl acetate polymer, etc., but preferably a polyurethane polymer,
Examples thereof include polyamide polymers and polyester polymers.

There are two methods of applying the adhesive agent: a total adhesion method of applying the adhesive agent on the entire surface and a partial adhesion method of partially applying the adhesive agent in a dotted or linear manner. The partial adhesion method of applying is preferably used. The coating method for coating the polymer and the adhesive is not particularly limited, but generally, a floating knife coater, a knife over roll coater, a reverse roll coater, a roll doctor coater, a gravure roll coater, a kiss roll coater, a nip roll. Coating is possible using a coater or the like.

The thickness of the film is 5 to 50 microns. If it is less than 5 microns, the water pressure resistance is low, and if it exceeds 50 microns, the texture becomes coarse and hard. A decorative paper or a cloth provided with a non-porous film layer or a microporous film of the hygroscopic polyurethane of the present invention on one surface is useful as a wallpaper.
In this case, it is possible to print a pattern on the microporous film layer in order to enhance the design of the wallpaper.

The hygroscopic polyurethane molded product obtained in the present invention is used for sports clothes such as windbreakers, rain gear such as rainwear, dust-proof gloves, wallpaper, sponge-like shoulder pads used for keeping the shape of clothes, etc. can do.

[0015]

The present invention will be described in more detail with reference to the following examples. The method of measuring the characteristics shown in the examples is as follows. (Evaluation of film) 1. Moisture content: The formed film was absolutely dried at 105 ° C. for 2 hours and conditioned under an atmosphere of 20 ° C. × 65% RH for 24 hours to determine the moisture content.

Moisture content (%) = {moisture content (g) / weight of film at absolute dryness (g)} × 100 2. Swelling rate: The film prepared was dried at 105 ° C. for 2 hours, marked at 10 cm intervals, and kept at 20 ° C. × 65.
After controlling the humidity for 24 hours in a% RH atmosphere, the length of the marked portion was measured to determine the expansion coefficient. Expansion rate (%) = {(length after humidity control (cm-10) / 1
0} × 100 3. Washing conditions: New beads from Kao Co., Ltd. 2 g / L
It was washed in a household washing machine at a water temperature of 40 ° C. Washing for 5 minutes and rinsing for 10 minutes were set as 1 time, and the washing was repeated 10 times. (Evaluation of coated cloth) 1. Moisture permeability: JIS L-1099 A-1 method 2. Water resistance: JIS L-1092 Water resistance test 3. Dew condensation prevention: Keep water bath at 40 ℃, 10
A 15 cm square sample, whose weight (W ₀ ) was measured, was attached to a plastic plate cut out in a cm square, with the coating surface facing downward, and after 10 minutes, the weight (W ₁ ) of the sample was measured. Immediately thereafter, water droplets attached to the coated surface of the sample were wiped off with a filter paper, and the weight (W ₂ ) of the sample was measured.

Dew Condensation (g / m ² ) = (W ₁ ) − (W ₂ ) Water Absorption (g / m ² ) = (W ₂ ) − (W ₀ ). 4. Curling: Warp 25 cm The fabric cut to a width of 20 cm was allowed to stand for 24 hours in a 20 ° C. × 65% RH atmosphere, and the curling angle was measured. (Evaluation of wallpaper) 1. Condensation test: indoor temperature 25 ° C, indoor humidity 70% RH,
It was attached to the wall surface of a closed chamber having a wall temperature of 10 ° C., and the occurrence of dew condensation was observed after 12 hours.

[0018]

Example 1 1000 g of polytetramethylene glycol having an average molecular weight of 1200 (parts by weight, the same applies hereinafter) and 4,
312 g of 4'-diphenylmethane diisocyanate,
The reaction was carried out in a nitrogen gas stream at 95 ° C. for 90 minutes while stirring to obtain a prepolymer having an isocyanate group remaining.
Then, this was cooled to room temperature, and 2360 g of dry dimethylformamide was added and dissolved to obtain a prepolymer solution. On the other hand, 23.4 g of ethylenediamine and 3.7 g of diethylamine were dissolved in 765 g of dry dimethylformamide, and the prepolymer solution was added thereto at room temperature to obtain a polyurethane solution having a viscosity of 1200 poise (30 ° C.). In the viscous polymer solution thus obtained, 4,
4'-Butylidene-bis (3-methyl-6-t-butylphenol) 2% (wt%, the same applies hereinafter) 2- (2'-
Hydroxy-3'-t-butyl-5'-methylphenyl) -5-chloro-benzotriazole 0.7% was added. 10 g of this polymer solution was added to 10 g of dimethylacetamide, and various magnesium salts as shown in Table 1 were added.
Add 15g dissolved or dispersed and coat it on release paper with a clearance of 0.5mm.
A film was prepared by drying at 0 ° C. The moisture content of the prepared film was determined, and the results are shown in Table 1. Further, magnesium oxide and magnesium hydroxide were dissolved in 0.8 g of acetic acid and then added to the mixed resin of 10 g of the polymer solution to form a film in the same manner. The moisture content of the prepared film was determined, and the results are shown in Table 1.

[0019]

Example 2 Copolymerization polyester diol of 1,4-butanediol, ethylene glycol 6: 4 and adipic acid having an average molecular weight of 2000: 1667 g (parts by weight; hereinafter the same).
And 4,4'-diphenylmethane diisocyanate 3
12 g was reacted with stirring in a nitrogen gas stream at 95 ° C. for 90 minutes to obtain a prepolymer having an isocyanate group remaining. Then, after cooling this to room temperature, 3111 g of dry dimethylformamide was added and dissolved to obtain a prepolymer solution. On the other hand, 23.4 g of ethylenediamine and 3.7 g of diethylamine were dissolved in 1570 g of dry dimethylformamide, and the prepolymer solution was added thereto at room temperature to obtain a polyester polyurethane solution having a viscosity of 3000 poise (30 ° C.). In the viscous polymer solution thus obtained, 4,4'-butylidene-bis (3-methyl-6-t-butylphenol) 2% (wt%, the same applies hereinafter) 2- (2'-hydroxy-3 ' 0.7% of -t-butyl-5'-methylphenyl) -5-chloro-benzotriazole and 1% of 2- (4-thiazolyl) benzimidazole were added.

To 10 g of this polymer solution, 10 g of dimethylacetamide dissolved in 0.15 g of magnesium chloride was added, coated on release paper with a clearance of 0.5 mm, and dried at 80 ° C. to form a film. did. The moisture content of the prepared film was determined, and the results are shown in Table 1.

[0021]

Comparative Example 1 10 g of the polymer solution used in Example 1 was added.
Add 10 g of dimethylacetamide, stir it, and coat it on release paper with a clearance of 0.5 mm.
A film was prepared by drying. The moisture content of the prepared film was determined, and the results are shown in Table 1.

[0022]

Comparative Example 2 10 g of the polymer solution used in Example 2 was added.
Add 10 g of dimethylacetamide, stir it, and coat it on release paper with a clearance of 0.5 mm.
A film was prepared by drying. The moisture content of the prepared film was determined, and the results are shown in Table 1.

[0023]

Example 3 To 10 g of the polymer solution used in Example 1,
2 g of dimethylacetamide was added with magnesium chloride in Table 2
0.1 (0.003g) to 10% by weight
(0.3 g) was added and coated on a release paper with a clearance of 0.5 mm and dried at 80 ° C. to form a film. The moisture content of the prepared film was determined, and the results are shown in Table 2.

Further, the water content after 10 times of washing was also measured for the films containing magnesium chloride of 3% by weight and 5% by weight. As a result, it was found that the water content after washing was almost the same as that before washing.

[0025]

Example 4 70 denier nylon 66 (with a density of 13
Fluorine-based water repellent (Asahi Guard LS3 manufactured by Meisei Chemical Co., Ltd.) with 6 fibers / inch and lateral density of 104 fibers / inch
17) Dip in 0.8% and squeeze at 80% drawing ratio, then 1
It was dried at 50 ° C. for 2 minutes. Next, ether polyurethane resin (Heimlen X303 manufactured by Dainichi Seika Co., Ltd.)
8) 100 parts, methyl ethyl ketone 23 parts, toluene 1
3 parts, cross-linking agent (Resamine X-10 manufactured by Dainichiseika Co., Ltd.)
0) 2 parts and 50 parts of water were mixed. Magnesium chloride (5% by weight (0.15 g)) was added to 40 g of this coating solution, and one side of the fiber base cloth was coated with a knife coater, dried at 80 ° C. for 2 minutes, and then heat-treated at 100 ° C. for 1 minute to form a composite sheet. Was manufactured. The coating amount was 25 g / m ² .

Using this composite sheet, moisture permeability, waterproofness, dew condensation prevention and curling were evaluated. The results are shown in Table 3.

[0027]

Comparative Example 3 The coating solution prepared in Example 5 was coated on one side of a fiber base cloth with a knife coater,
After being dried at 0 ° C for 2 minutes, it was heat-treated at 100 ° C for 1 minute to manufacture a composite sheet. The coating amount was 25 g / m ² . Using this composite sheet, moisture permeability, waterproofness, dew condensation prevention and curling were evaluated.

[0028]

Example 5 100 parts of the polymer solution used in Example 1 was dry-spun with a polymer solution containing 3% by weight (0.1 part) of magnesium chloride to obtain a 280 denier polyurethane elastic yarn. A body suit was made and worn with a 6-course satin knitted fabric knitted using this yarn and a nylon yarn of 50d. As a result, the sample of Example 6 had little stuffiness or stickiness and was comfortable to wear.

[0029]

Comparative Example 4 The polymer solution prepared in Example 1 was dry-spun to obtain a 280 denier polyurethane elastic yarn. A body suit was created and worn with a 6-course satin knitted fabric knitted using this yarn and nylon yarn. The sample of Comparative Example 4 had a feeling of stuffiness and stickiness and was uncomfortable to wear.

[0030]

Example 6 A polymer solution prepared by adding 5% by weight of magnesium chloride (0.15 part) to 100 parts of the polymer solution used in Example 1 was dry-spun to obtain a 20 denier polyether polyurethane elastic yarn. Obtained. Draft 3.3 with this denier thread 30 denier 24 filament nylon 66
FTY covering the yarn at 1100 times / m is used for weft and 30
A denier 10 filament nylon 66 yarn was used as a warp to produce a warp density of 160 yarns / inch and a weft yarn density of 140 yarns / inch (woven fabric A).

In 100 parts of the polymer solution used in Example 1, 0.4 part of acetic acid and 5% by weight of magnesium oxide (0.1%) were added.
5 parts of the polymer solution was dry-spun to obtain a 20 denier polyether polyurethane elastic yarn. Using this elastic yarn, a woven fabric having a warp density of 160 yarns / inch and a weft yarn density of 140 yarns / inch was obtained as a woven fabric (woven fabric B) in the same manner as the woven fabric A.

Woven fabrics A and B were scoured under the following conditions. Anhydrous calcium carbonate 0.5 g / L core roll FC-12 (manufactured by Kao Corporation) 2 g / L Treatment temperature 60 ° C x 20 minutes A dew condensation test was conducted using this as a wallpaper, and the results are shown in Table 4.

[0033]

Comparative Example 5 The polymer solution used in Example 1 was dry-spun to obtain a 20-denier polyether polyurethane elastic yarn. Using this elastic yarn, an FTY was formed in the same manner as the woven fabric A of Example 7, and a nylon 66 yarn having 30 denier 10 filaments was used as a warp to have a warp density of 160 / inch and a weft density of 140 / inch. C). This woven fabric was dyed in the same manner as in Example 6, and a dew condensation test was conducted using this as a wallpaper. The results are shown in Table 4.

[0034]

[Table 1]

[0035]

[Table 2]

[0036]

[Table 3]

[0037]

[Table 4]

[0038]

According to the present invention, hygroscopicity can be imparted to a polyurethane elastic yarn and a molded article, dew condensation on a fabric containing this hygroscopic polyurethane can be suppressed, and curling of the coating fabric can be prevented. .. In addition, the stickiness of clothes such as foundations using polyurethane elastic yarn interwoven fabric can be improved.

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Claims (1)

[Claims] 1. A method for producing a hygroscopic polyurethane molded article, which comprises dissolving 0.1 to 10% by weight of a magnesium salt in a polyurethane polymer composition with respect to the polyurethane polymer, and molding.