JPS5821933B2 - Polyurethane elastomer solution composition for wet synthetic leather - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a polyurethane elastomer solution composition for wet synthetic leather.

More specifically, it has a fast solidification rate during wet coagulation, a fast solvent removal rate during water washing, excellent moisture permeability and hydrolysis resistance, can form synthetic leather that is flexible, lightweight, and has a uniform microporous structure, and has good storage stability. The present invention relates to a polyurethane elastomer solution composition (mixture).

Conventionally, synthetic leather produced by the wet method involves wet coagulation by coating and impregnating a base fabric or membrane plate with a solution of a polymer such as polyurethane in a water-miscible organic solvent or a mixture thereof, and then immersing it in a coagulating liquid such as water. After that, the solvent remaining in the coagulated product is removed by washing with water and dried.
The solidification rate is fast, the solvent can be removed in a short time when washing with water, the porous sheet after drying has good moisture permeability and hydrolysis resistance, and is flexible and lightweight. It is important that the polyurethane solution or its mixture has good storage stability, that is, it has a uniform and fine porous structure without large pores (cavities) and is stable.

This is because if there is even one giant pore in a porous sheet, stretching stress will be generated there during shoe making and stretch molding during shoe making, and the giant pores will easily burst or break, making it difficult to improve moisture permeability and molding. This is because even though it has good processability, it is treated as a product with low commercial value.

In addition, if the coagulation rate or solvent removal rate during water washing is slow, the ability to produce porous sheets will be reduced, and if solvent remains after washing with water, the heat during drying will cause the polyurethane to swell and soften, crushing micropores and reducing moisture permeability.

Among the above-mentioned problems, methods for producing uniform microporous sheets without large pores include methods such as changing the composition of coagulation rate retarders and coagulants, and methods for speeding up the removal rate of solvents by washing with water include using a special polyurethane elastomer solution. Although methods using such compositions have been proposed, a method that satisfies all of the above-mentioned problems (necessary conditions) has not yet been found.

For example, an opaque solution composition produced by mixing a polyvinyl chloride solution with a polyurethane solution prepared by chain-extending a prepolymer made of polyethylene butylene adipate diphenylmethane diisocyanate with hydrazine and ethylenediamine described in Japanese Patent Publication No. 50-28977 is a solvent-removal agent. Although it has good properties, it has poor storage stability and cannot form a flexible porous film with high moisture permeability.

Furthermore, the composition liquid produced by mixing an emulsion of an elastic polymer with a homogeneous solution of a polyurethane elastomer described in JP-A-52-28906 has poor storage stability, and when coagulated with water, forms a porous film with large pores. is formed, and the rate of removal of the solvent by water washing is also relatively slow.

Also, JP-A-51-111264 and JP-A-51-1
In the polyurethane composition solution described in Japanese Patent Publication No. 11265, which is made by dissolving a blend of two polyurethanes of the same type that have polylactone glycol, polycarbonate, or polyether glycol as soft segments and have different nitrogen content, water When coagulated with water, it forms a sheet with large pores and low moisture permeability, and the rate at which the solvent is removed by water washing is also slow.

As a result of intensive research to solve the above-mentioned problems, the present inventors have found that all of the specific polyurethane elastomer solutions mentioned below have excellent solvent removal properties, moisture permeability, and uniformity of porous structure during wet (water) coagulation. Although it is bad, as described below, the elastomer solution composition (liquid) produced by mixing in a specific combination,
It is stable, quickly solidifies, and the solvent can be easily and quickly removed by washing with water, increasing manufacturing efficiency. It also has excellent moisture permeability and hydrolysis resistance, is flexible, lightweight, and has uniform fine pores without large pores. The inventors have discovered that all of the above-mentioned problems can be easily solved by producing a sheet with a textured structure, and have completed the present invention.

The purpose of the present invention is to be stable even when stored for a long period of time, to solidify quickly when applied to a synthetic leather substrate, impregnated, and wet solidified.
A polyurethane elastomer solution composition that allows the solvent to be removed in a short time when washed with water, has high moisture permeability, hydrolysis resistance, flexibility, and lightness, and can easily produce a leather-like sheet with a uniform fine porous structure without large pores. It's about providing things.

That is, the present invention provides a polyurethane solution composition produced by mixing at least two solutions in which a polyurethane elastomer comprising a polymeric diol, an organic diisocyanate, and a chain extender is dissolved in a water-miscible organic solvent. One of the polyurethane elastomer solutions (support) to be mixed contains polydipropylene glycol adipate diol alone or a diol mixture of polylactone glycol, polyalkylene glycol adipate diol, or polyalkylene ether glycol in a weight ratio of 70 or more and a weight ratio of 30 or less. It is a substantially transparent solution with a turbidity of 0.05 or less in which a polydipropylene glycol adipate-based polyurethane elastomer as a polymeric diol is dissolved.

The other polyurethane elastomer solution (B) contains a single polymeric diol selected from the group consisting of polydiethylene glycol adipate diol, polyε-caprolactone glycol, and polytetramethylene ether glycol, or a polyurethane diol having a weight ratio of 70 to 30% by weight. Polydiethylene glycol adipate-based polyurethane elastomer, polyε, consisting of a diol mixture with lactone glycol, polyalkylene glycol adipate diol, or polyalkylene ether glycol as the polymer diol
- A substantially transparent solution with a turbidity of 0.05 or less in which the caprolactone-based polyurethane elastomer or polytetramethylene ether-based polyurethane elastomer is dissolved, and the composition produced by mixing the polyurethane elastomer solution has a turbidity of This is a polyurethane elastomer solution composition for wet synthetic leather, characterized in that it is a cloudy liquid with a viscosity of 0.2 to 1.5.

Hereinafter, embodiments of the present invention will be explained in detail.

The polyurethane elastomer (
a) has an average molecular weight of 500 to 3000 (preferably 10
00 to 2000) alone or a diol mixture with polylactone glycol, polyalkylene glycol adipate diol, or polyalkylene ether glycol having a weight ratio of 10 or more and a weight ratio of 30 or less, an organic diisocyanate, and chain elongation. agents (e.g. diamines, low molecular weight glycols, etc.)
Polyurethane or polyurethane urea synthesized from polyurethane by one-shot method or prepolymer method, singly or as a mixture.

(This polyurethane elastomer (a) is called a polydipropylene glycol adipate-based polyurethane elastomer for convenience because the soft segment constituting it has polydipropylene glycol adipate diol as a main component.

). In this case, if the amount of polydipropylene glycol adipate diol used as the soft segment is less than 70% by weight, the hydrolysis resistance tends to deteriorate, the coagulation rate of the composition liquid is slow, and the solvent removal, moisture permeability, and flexibility are reduced. This is not preferable because it reduces the

In the synthesis of this polyurethane elastomer (a),
Examples of the polylactone glycol having a weight ratio of 30% or less to be mixed with the 0% weight ratio of polyethylene glycol adibate dilure include polyε-caprolactone glycol, polyγ-butyrolactone glycol, polyvalerolactone glycol, etc. Examples of the alkylene glycol adipate diol include polybutylene glycol adipate diol, polypropylene glycol adipate diol, polyethylene glycol adipate diol, polyhexamethylene glycol adipate diol, polyneopentyl glycol adipate diol, etc. Not included.

Examples of the polyalkylene ether glycol having a weight ratio of 30% or less to be mixed and used include polyethylene ether glycol, polypropylene ether glycol, polytetramethylene ether glycol, polyhexamethylene ether glycol, and the like.

These polymeric diols have an average molecular weight of 500 to 30
00 (preferably 1000 to 2000),
They may be used singly or in combination.

Examples of the organic diisocyanate include tolylene diisocyanate, phenylene diisocyanate, diphenylmethane diisocyanate, naphthylene diisocyanate, xylylene diisocyanate, 4,4'-dodecahydrodiphenylmethane diisocyanate, inphorone diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, and the like. They can be used alone or in combination.

Among these, aromatic diisocyanates are preferred.

- Chain extenders include, for example, ethylene glycol, propylene glycol, phethylene glycol, hexamethylene glycol, diethylene glycol, cyclopylene glycol, 1,4-cyclohexane glycol, 1,4
-Low molecular weight glycols with a molecular weight of 500 or less such as cyclohexane dimetatool, ethylenediamine, hydrazine, 1
,2-propylene diamine hexamethylene diamine
Phenylenediamine, tolylenediamine, 4.4'
-diaminodiphenylmethane, naphthylenediamine, cyclohexylenediamine, isophorodiamine, 4,4'
Examples include diamines such as -diaminododecahydrodiphenylmethane, water, amino alcohols, dihydrazides, and the like.

One or more types of chain extenders are used.

This polyurethane elastomer (a) dissolved in one polyurethane elastomer solution is dissolved in the presence of a water-miscible organic solvent (solution polymerization method) or in the absence of a solvent (bulk polymerization method, etc.).

Therefore, the polyurethane elastomer 7- obtained by polymerization without a solvent is dissolved in an appropriate amount of a water-miscible organic solvent, and the polyurethane elastomer solution (At,
The polyurethane elastomer solutions obtained by preparing each of (B) and solution polymerization are used as they are or after being diluted to an appropriate concentration.

Generally, solution polymerization is preferable because it is easier to obtain a transparent solution and the above-mentioned effects can be sufficiently exhibited.

The polyurethane elastomer solution used in the present invention or (polyurethane elastomer (a) or (b) in BJ)
The content concentration is usually 20 to 40% by weight.

Preferably it is 20 to 35 weight ratio.

If the 20 weight rise is low, the coagulation rate of the mixed composition liquid will be slow, and the moisture permeability and storage stability may be likely to decrease.If the 40 weight rise is high, defoaming will be difficult and the mixed composition liquid will solidify. Solvent removal properties and moisture permeability of the product may decrease.

The polyurethane elastomer solution used in the present invention or (B) is a water-miscible organic solvent solution in which the specific polyurethane elastomer as described above is dissolved, and the turbidity (optical turbidity) is 0.05. Virtually transparent (
It is important that the material be transparent (as observed by naked eye).

When the turbidity is greater than 0.05, it gives a slightly cloudy to white turbid appearance, and the turbidity of the composition liquid produced by mixing both the polyurethane elastomer solution and the former is 0.2 to 1.5.
Even if it is within the range, the storage stability of the composition liquid decreases,
This is not preferred because it tends to form large pores and the solvent removal properties, moisture permeability, etc. of the coagulated product deteriorate.

Next, the polyurethane elastomer (b) dissolved in the other polyurethane elastomer solution (B) used in the present invention is polydiethylene glycol adipate diol having an average molecular weight of 500 to 3000 (preferably 1000 to 2000), A polymeric diol selected from the group consisting of polycaprolactone glycolone ether glycol alone or a diol mixture of polylactone diol, polyalkylene glycol adipate diol, or polyalkylene ether glycol having a weight ratio of 70 or more and a weight ratio of 30 or less; It is a polyurethane or polyurethane urea synthesized from an organic diisocyanate and a chain extender (described above) by a one-shot method or a prepolymer method, either alone or as a mixture.

Among these polyurethane elastomers (b), those whose soft segments are mainly composed of polydiethylene glycol adipate diol are called polydiethylene glycol adipate-based polyurethane elastomers (bl), and those whose soft segments are mainly composed of polycaprolactone glycol are called polyurethane elastomers (b). The caprolactone-based polyurethane elastomer (b21) and the one mainly composed of polytetramethylene ether glycol were called the polytetramethylene ether-based polyurethane elastomer (b3).

These polyurethane elastomers (b,), (b2
) or (b3), if the amount of at least one of polydiethylene glycol adipate diol, polycaprolactone glycol, and polyalkylene glycol adipate diol used as the polymeric glycol is less than 70% by weight, the hydrolysis resistance tends to deteriorate, and the composition This is not preferred because the solidification rate of the liquid is slow and the solvent removal properties, moisture permeability, flexibility, etc. of the solidified product are reduced.

Cholera polyurethane elastomer (BL), (B2)
The organic diisocyanate and chain extender used in the synthesis of (b3) and (b3) are the same as those described above (in the case of one polydipropylene glycol adibate polyurethane elastomer), but the polydiol mixture with a weight coefficient of 30 or less is used as the diol mixture. Examples of the alkylene glycol adipate diol include polybutylene glycol adipate diol, polypropylene glycol adipate diol, polyethylene glycol adipate diol, polyhexamethylene glycol adipate diol, polyneopentyl glycol adipate diol, etc. Not included.

The polylactone glycol with a weight ratio of 30 or less to be used in combination with polydiethylene glycol adipate or polytetramethylene ether glycol flow weight ratio is 30 or less.
(In the case of synthesis of polydipropylene glycol adipate-based polyurethane), the polylactone glycol having a weight ratio of 30% or less to be mixed with polycaprolactone glycol is, for example, polyγ-butyrolactone glycol, polyvalerolactone glycol, etc. does not include polylactone glycol.

Furthermore, polyalkylene ether glycol having a weight ratio of 30 or less and mixed with diethylene glycol adipate diol or polycaprolactone glycol of 70 or more is also used in the same manner as described above (in the case of synthesis of polydipropylene glycol adipate-based polyurethane), but polytetra 30 mixed with methylene ether glycol
Polyalkylene ether glycols below the weight range include, for example, polyethylene ether glycol, polypropylene ether glycol, polyhexamethylene ether glycol, and include polytetramethylene ether glycol.

the above polyethylene elastomer (b) dissolved in the other polyurethane elastomer solution (B);
The polyurethane elastomer (polyurethane elastomer of the above items, b2 or b3) must be obtained without a solvent or by a solvent polymerization method, and the other polyurethane elastomer solution (
B) is obtained by dissolving the polyurethane elastomer (b) obtained by polymerization without a solvent in a water-miscible organic solvent, or by solution polymerization in a water-miscible organic solvent (the solution polymer is dissolved in the solvent). The concentration of the polyurethane elastomer (b) in the solution (B) is usually 20 to 40% by weight (preferably 25 to 35% by weight), and the polyurethane elastomer Solution (b) also has a turbidity (optical turbidity) of 0.05 or less, is substantially transparent (appearance by naked eye observation), and has a turbidity of 0.0.
The reason for limiting the value to 5 or less is the same as in the case of the polyurethane elastomer solution described above.

In addition, the above polyurethane elastomer solution (support) or (
The water-miscible organic solvent in B) (water-miscible organic solvent used for dissolving the polyurethane elastomer obtained by solvent-free polymerization or solvent polymerization) is a water-miscible organic liquid agent for ordinary polyurethane, For example, in addition to amide solvents such as N,N-dimethylformamide, N,N-diethylformamide, and N,N-dimethylacetamide, dimethyl sulfoxide, tetrahydrofuran, tetramethylurea, dioxane, gamma-butyrolactone, cyclohexanone, methyl ethyl ketone, etc. They may be used singly or in combination.

Among the above-mentioned solvents, amide solvents, especially N. N-dimethylformamide is preferred.

The polyurethane elastomer solution composition of the present invention can be prepared by mixing one polyurethane elastomer solution and the other polyurethane elastomer solution (B).
Alternatively, it can be manufactured by adding an appropriate solvent after mixing to adjust the concentration, if necessary.

It is necessary that the turbidity of the polyurethane elastomer solution composition of the present invention to be produced is within the range of 0.2 to 1.5.

If the turbidity is outside the above range, phase separation, polymer precipitation, gelation, etc. will occur during storage, resulting in poor storage stability, low coagulation rate, low solvent removal properties, high density, and low moisture permeability. It is not tricky because it forms a film.

The range of the mixing ratio and amount of (2) and (D) in the polyurethane elastomer solution is relatively wide, and usually the ratio of polyurethane elastomers (a) and (b) in the polyurethane elastomer solution composition is 95:5 by weight. to 5
The contents of the solution are mixed such that the total content of both polyurethane elastomers in the solution composition is 20 to 38% by weight (preferably 25 to 35% by weight). be done.

Outside the above range, storage stability, solvent removal properties, and moisture permeability tend to deteriorate, and large pores tend to occur.

Polydipropylene glycol adipate-based polyurethane elastomer, polytetramethylene ether glycol-based polyurethane elastomer, and polycaprolactone-based polyurethane elastomer have good hydrolysis resistance. Therefore, the polyurethane elastomer solution composition of the present invention containing these polyurethane elastomers , a porous sheet etc. with excellent hydrolysis resistance can be formed.

The polyurethane solution composition of the present invention produced by mixing the aforementioned polyurethane elastomer solution (BA) is a substantially cloudy homogeneous liquid with a turbidity of 0.2 to 1.5 (viscosity is usually 5000 to 100%). ,000cps/
30℃), but it has excellent stability against temperature changes and storage stability, and can be stored stably for a long period of time without quality change, making it convenient and suitable for industrial applications. .

The solution composition of the present invention is used in the production of wet synthetic leather.
After impregnating or applying resin to at least one surface of a fibrous substrate or membrane plate (e.g. glass plate, metal plate), which is woven, knitted or non-woven fabric, or any of these, the resin is first wet-coagulated with a coagulating liquid (bath). In this case, coagulants such as water and alcohol (non-solvent for polyurethane elastomer) may be used alone or as a mixture, or as a water-based solvent for polyurethane elastomer (based on water).
For example, even a mixed solution (DMF) can be solidified relatively quickly and homogeneously to produce a stable leather-like porous sheet-like material with no skin wrinkles on the surface and excellent moisture permeability.

Also, JP-A-52-111264, JP-A-52-111
Another feature of the present invention is that it does not have reduced stability during storage or selectivity of coagulating liquid (agent) unlike the urethane elastomer solution compositions disclosed in Japanese Patent Publication No. 265 and JP-A-52-28905. .

In general, with polyurethane elastomer solutions that have a fast solidification rate and good solvent removal properties when washed with water, the surface of the solution coating film solidifies rapidly to form a skin, and the unsolidified portion inside the coating film is delayed considerably. However, the polyurethane solution composition of the present invention solidifies relatively quickly, and the solvent can be easily and quickly removed during washing with water. Moreover, the uniqueness of the action and effect of forming a leather-like sheet with high moisture permeability and a uniform microporous structure without large pores is remarkable.

The polyurethane elastomer solution composition of the present invention has excellent storage stability, and when wet-coagulated by coating and impregnating a substrate, it coagulates quickly and uniformly with any coagulating liquid, increasing the solvent removal rate during water washing and improving productivity. It is possible to easily form flexible, lightweight leather-like sheets with excellent moisture permeability, hydrolysis resistance, and no large pores, making excellent synthetic leather for shoes, bags, clothing, etc. industrially advantageous. It can be manufactured to

Examples will be described below.

In the Examples, part means part by weight, and part means part by weight.

Furthermore, the measurement or testing methods for turbidity, solvent removal, 100% modulus, density, moisture permeability, and hydrolysis resistance are as follows.

(1) Turbidity Turbidity is defined by the following formula.

Tu-■mtx (I, ・al + I2 ・a2
++++++++++ In0an) where Tu: Turbidity lm1x: Components 1, 2. . . . n is the weight ratio of a3. a2 ,...an Absorbance of the dissolved mixed solution n: Absorbance of a solution of component n as a single solution at the same concentration in the mixed solution an: Weight of component n in the solute in the mixed solution The fraction, therefore, a, +a2+...+an=1.0.

Absorbance was measured using a Double B Hirohito spectrophotometer (e.g. Hitachi 624).
(type digital spectrophotometer), optical path length is 1.0 cIrL.
Measurements are performed using a quartz cell using the following steps.

That is, the quartz cell filled with only a solvent is placed in the control side optical path, and the same quartz cell filled with a sample solution is placed in the sample side optical path, and the absorbance at a wavelength of 400 mm (nanometers) is read.

Note that the room temperature at the time of measurement is 25° C., and the sample solution is left standing under measurement temperature conditions for 24 hours after preparation, and then measured according to the above-mentioned procedure.

Furthermore, when transferring a sample solution to a quartz cell for absorbance measurement, extreme care must be taken to prevent not only foreign matter such as dust but also air bubbles from entering the sample solution.

(2) Solvent removal (residual solvent) A solution of the sample polyurethane in N,N-dimethylformamide was placed on a glass plate to a thickness of 1.0 mm and an area of 100 cy7.
After casting the sample solution into a thin film (10 cm x 10 m), the sample solution is immersed in water (coagulating liquid) IA at 30° C. for 30 minutes to solidify.

After that, the glass plate was taken out, the coagulated film formed on the glass plate was peeled off, and then this coagulated film was left at 60°.
The solvent N contained in the coagulated film was immersed in C water (washing water) for 30 minutes.

Elute N-dimethylformamide (natural washing).

After soaking, take out the film, wipe off the water adhering to its surface with paper, then bend the film from the center and press it firmly with pliers to remove the liquid (N) remaining inside the film. .

If N-dimethylformamide remains, it is an aqueous solution; if not, it is a liquid consisting of water alone.)
Squeeze 1 to 2 drops of the solution onto the sample plate of the Atsube refractometer.

Next, the refractive index of the liquid is measured.

(This operation and measurement are performed in a constant temperature room at 25°C.

) On the other hand, a calibration curve graph showing the relationship between the concentration of N,N-dimethylformamide and the refractive index in an N,N-dimethylformamide aqueous solution is created, and from this graph and the refractive index of the squeeze fluid measured previously, The concentration (by weight) of N,N-dimethylformamide contained in the squeezing fluid is determined.

The lower the concentration, the better the solvent removal property after wet coagulation of the sample polyurethane elastomer solution (the solvent in the wet coagulation product is easily removed by water washing). This means that it has been completely eluted and removed.

(3) 100% modulus (hereinafter abbreviated as 100%M) The coagulated film was immersed in water at 60°C for 120 minutes and then dried with hot air at 80°C, but in the same manner as in the solvent removal test. Create a sample film.

The stress of this sample film at an elongation rate of 100 was measured according to the method of JIS-6650, and the stress was determined to be 10% modulus.

Its unit is U/-1. The smaller the value, the softer the unpleasant feeling the film gives.

(4) Using the same sample film as in the case of density 100% modulus,
The density was determined from its volume and weight.

The lower the density, the lighter the weight.

(5) Moisture Permeability The moisture permeability of the same sample film as in the case of 10% modulus was measured according to the method of JIS-6549.

The unit is m9/cwt/hr, and fabrication humidity with a large value is good.

(6) Presence or absence of giant pores (cavities) formed inside the film10
The cut surface of the same sample film as in the case of 0% modulus and the surface where the film was folded in two were shaved with a razor, and the surfaces were observed under a microscope to determine the presence or absence of large pores (cavities).

(7) Using the same sample film as in the case of V-mouth water decomposition resistance 1oo% modulus,
JIS-6552 in a constant temperature room at 0℃ and relative humidity of 90℃
The strength and elongation was measured according to the method of 2007, and the strength retention rate was expressed as the number of days elapsed when the strength retention rate became smaller than 50% of the initial value.

The longer the number of days, the better the hydrolysis resistance.

Example 1 49.5 parts of polydipropylene glycol adipate diol with a molecular weight of 1960, 30.0 parts of 4,4'-diphenylmethane diisocyanate, 8 parts of 1,4-butanediol
．． 3 parts and N,N-dimethylformamide (hereinafter referred to as DMF
205 parts of the above-mentioned polyurethane elastomer solution (hereinafter referred to as ) was placed in a polymerization machine and the polymerization reaction was carried out at 60°C for 6 hours while stirring under a nitrogen gas atmosphere, and then 0.3 parts of ethanolamine was added as a polymerization terminator to prepare one of the polyurethane elastomer solutions (hereinafter referred to as An elastomer solution A) was obtained.

Its solid content concentration is 30%, and its viscosity is 80,000 cps/
The temperature was 30'C, the turbidity was 0.046, and the appearance was transparent.

Next, the other polyurethane elastomer solution (hereinafter referred to as elastomer solution B) was obtained in the same manner as above except that polydiethylene glycol adipate diol having a molecular weight of 1960 was used instead of polydipropylene glycol adipate diol.

Its solid content concentration is 30%, and the viscosity is 82,000 cps/30℃.
The turbidity was 0.01 and the appearance was transparent.

50 parts each of the thus obtained one elastomer solution and the other elastomer solution (B1) were thoroughly mixed under stirring to form the polyurethane elastomer solution composition of the present invention (hereinafter referred to as a mixed solution of A+B). ) was prepared.

The solid content concentration was 30%, the turbidity was 0.780, and the appearance was a milky white homogeneous liquid.

This composition was left for 6 months in a constant temperature chamber that was cycled back and forth between ±45°C and found to be stable without any abnormalities.

Next, the stability of the elastomer solution A and B, the solvent removal property (residual solvent) in wet coagulation, the 100% M1 density of the resulting film, the moisture permeability, The presence or absence of giant pores was investigated.

The results are shown in Table 1. As is clear from these results, one elastomer solution A (a solution of a polyurethane elastomer in which the polymer diol constituting the soft segment is composed of polydipropylene glycol adipate diol alone) and the other elastomer solution B (a solution of a polyurethane elastomer in which the polymer diol constituting the soft segment is composed of polydipropylene glycol adipate diol alone), The solution composition of the present invention obtained by mixing a solution of a polyurethane elastomer whose molecular diol is polydiethylene glycol adipate diol alone has better solvent removal properties, solution storage stability, etc. of wet coagulation products than each elastomer solution. It is possible to obtain a leather-like sheet-like material which is excellent in weight, has better moisture permeability and flexibility, and has no large internal pores and has a uniform porous structure.

Example 2 A polyurethane elastomer solution (hereinafter referred to as Elasto-7-Solution B2) was prepared in the same manner as in Example 1, except that polyε-caprolactone glycol having a molecular weight of 1960 was used instead of polydipropylene glycol adipate diol.
I got it.

Its solid concentration is 30.1 inches, and its viscosity is 81,000 cps/3.
The temperature was 0°C, the turbidity was 0.035, and the appearance was transparent.

Next, 50 parts each of this elastomer solution (B2) and the elastomer solution (2) used in Example 1 were mixed in the same manner as in Example 1 to prepare a polyurethane elastomer solution composition of the present invention.

Its solid concentration is 30.05% and viscosity is 80,000 cps/3
The temperature was 0°C, the turbidity was 0.854, and it was a milky white homogeneous liquid.

This composition was stored for 6 months in the same manner as in Example 1, and was extremely stable without any abnormalities.

The elastomer solution composition (elastomer solution A+B
2) and the results of wet coagulation using each of the elastomer solutions B2 and elastomer solution A
The results of Example 1 are shown in Table 2.

As is clear from these results, one elastomer solution A (a solution of a polyurethane elastomer in which the polymer diol constituting the soft segment is solely polypropylene glycol adipate diol) and the other elastomer solution B2 (a solution of a polyurethane elastomer in which the polymer diol constituting the soft segment is composed of polypropylene glycol adipate diol alone) The liquid composition of the present invention obtained by mixing a solution of a polyurethane elastomer consisting of polyε-caprolactone glycol alone has a better ability to remove solvent from wet coagulation products than each elastomer solution (A or B2). It is possible to obtain a leather-like sheet-like material that has excellent properties such as elasticity, hydrolysis resistance, etc., is lightweight, has better moisture permeability, and flexibility, and has a uniform porous structure without large pores inside.

Example 3 A polyurethane elastomer solution (hereinafter referred to as elastomer solution B3) was obtained in the same manner as in Example 1, except that polytetramethylene ether glycol having a molecular weight of 1960 was used instead of polydipropylene glycol adipate diol.

Its solid concentration is 30%, and its viscosity is 81,000 cps/30.
℃, turbidity was 0.018, and the appearance was transparent.

Next, 50 parts each of this elastomer solution (B3) and the elastomer solution used in Example 1 were mixed in the same manner as in Example 1 to prepare a polyurethane elastomer solution composition of the present invention.

Its solid content concentration is 30 cm, and its viscosity is 80,000 cps/30
℃, turbidity was 1.150, and it was a milky white homogeneous liquid.

This composition was stored for 6 months in the same manner as in Example 1, and was stable without any abnormalities.

The elastomer solution composition (elastomer solution A+B
Table 3 shows the results of wet coagulation using the elastomer solution A (mixed solution of 3) and the elastomer solution B3 in Example 1.

As is clear from this result, the polyurethane elastomer solution (elastomer solution B3) in which the polymer diol constituting the soft segment is solely polytetramethylene ether glycol was mixed with the elastomer solution A of Example 1.
The solution composition of the present invention obtained by mixing with the elastomer solution A or B3 has superior solvent removal properties and hydrolysis resistance for wet coagulation products, and is lightweight, flexible, and has better moisture permeability. , and a leather-like sheet material with a uniform porous structure without macropores could be obtained.

Example 4 Elastomer solution of Example 1, elastomer solution of Example 1 (B1), and elastomer solution of Example 2 (B2)
(AB1B2 mixed solution) (turbidity 0.740) and (2 parts of the elastomer solution)
), (B2), and 50 parts each of the elastomer solution (B3) of Example 3 (AB2B2 mixed solution)
(turbidity 0.915) and the concentration of the elastomer solution (
A solution composition (-
Table 4 shows the results of wet coagulation using each of AB and B3 (turbidity: 0.889).

*Example 5 Solution polymerization was carried out in the same manner as in Example 1, except that the following diol mixture was used instead of the polydipropylene glycol adipate diol in Example 1, and each of the obtained elastomer solutions was added to one of the elastomer solutions 1 (A ) was used in the same manner as in Example 1.

The results are shown in Table 5. /16. molecular weight 1960
polydipropylene glycol adipate diol 85
A mixture of 15% polybutylene glycol adipate diol with a molecular weight of 42% and 70% of the above polydipropylene glycol adipate diol and 30% of the above butylene gelicol adipate diol 42% and 65% of the above dipropylene glycol adipate diol and the above polybutylene glycol adipate diol Part 35.

44: A mixture of the above polydipropylene glycol adipate diol 85 parts and polypropylene ether glycol 15 parts having a molecular weight of 2000.

As is clear from this result, one elastomer solution was prepared by mixing a polyurethane elastomer solution (with a turbidity of 0.05 or less) prepared as a polymer diol with a diol mixture containing polydipropylene glycol adipate diol of 70 or more. The solution composition also exhibits good properties and effects that are approximately the same as those in Examples 1 to 3.

Example 6 Solution polymerization was carried out in the same manner as in Example 1, except that the following diol mixtures were used instead of the polydipropylene glycol adipate diol in Example 1, and each obtained elastomer solution was added to the other elastomer solution (B, ) was used in the same manner.

The results are shown in Table 6. A mixture of 85% of polydiethylene glycol adipate diol having a molecular weight of 1960 and 15% of polybutylene glycol adipate diol having a molecular weight of 2000 in A2: A mixture of 70% of the above polydiethylene glycol adipate diol and the above polybutylene glycol adipate diol.

A3: A mixture of the above polydiethylene glycol adipate diol 65 and polybutylene glycol adipate diol.

4: A mixture of 85 parts of the above polydiethylene glycol adipate diol and 15 parts of polypropylene ether glycol.

Example 7 Diol mixture of Example 5 (/161 to /164) instead of polydipropylene glycol adipate diol
Table 7 shows the results of polymerization carried out in the same manner as in Example 1, using each of the obtained elastomer solutions in place of elastomer solution (A), and in the same manner as in Example 2.
Table 8 shows the results obtained in the same manner as above.

Example 8 Polydipropylene glycol adipate diol (PD
Instead of PGAD), use the following diol mixture (F1-46).
) was used, and polymerization was carried out in the same manner as in Example 1, except that each of the obtained elastomer solutions was used in place of elastomer solution (5).

The results are shown in Table 9. /161=PD of Example 1
A mixture of PGA 85 and polytetramethylene ether glycol (P, TEG) 15 of Example 3.

, 462: The above PDPGAD 70 and the above PTEG3
A mixture with 0.

A3: A mixture of 65% of the above PDPGAD and 35% of the above PTEG.

Scrap 4: 85% of the above PDPGAD and polyε- of Example 3
Mixture with caprolactone glycol (Pa:CLG) 30%.

Fu 5: The above PDPGAD 70 and the above PεCLG30
A mixture with %.

Scrap 6: 65% of the above PDPGAD and the above PεCLG35
Mixture with attendant.

Example 9 Polydipropylene glycol adipate Instead of the glycol diol, the diol mixture of Example 8 (Scrap 1 to Scrap 6) was used.
) was used in the same manner as in Example 2, except that each obtained elastomer solution was used in place of the elastomer solution. Table 10 shows the results as in Example 3. The results are shown in Table 11.

Example 10 Each elastomer solution (B, Example 1 was carried out in the same manner as in Example 1 except that .

The results are shown in Table 12.

Scrap Diol mixture (1): polyε-caprolactone glycol (PεCLG) 85% with a molecular weight of 1960 and polybutylene glycol adipate diol scrap with a molecular weight of 2000
Mixture with diol mixture (PBGAD) 15 parts.

(2) 2 The above PεCLG 70% and the above PBGAD
A mixture with 30 chi.

(3): The above PεCLG65 and the above PSGAD
A mixture with 35 chi.

(4) 2 A mixture of 85% of the above PεCLG and 15% of the polyethylene diol mixture tramethylene ether cricor (PTEG) of Example 3.

(5): The above PεCLG70 and the above PTEG30
Mixture with attendant.

(6) Two The above PεCLG65 and the above PTEG35
Mixture with attendant.

Example 11 (B) and (B) of the elastomer solution used in Example 1
1) was mixed at the mixing ratio shown in Table 7 to prepare an elastomer solution composition.The results are shown in Table 13.

As described above, the mixing ratio of polyurethane elastomers (a) and (b) in the polyurethane elastomer solution composition is preferably from 95:5 to 5:95.

Example 12 Polylanthanum elastomer concentrations obtained by solution polymerization in the same manner as in Example 1 by varying the amount of DMF were 38% and 35%.
Each elastomer solution of Section 25, Section 20, Section 12 (5
Example 1 was carried out in the same manner as in Example 1, except that each composition obtained by mixing 50 parts of ) and (B, ) was used.

The results are shown in Table 14. Example 13 A prepolymer having a terminal NCO group obtained by reacting 49.5 parts of polydipropylene glycol adipate diol with a molecular weight of 1960 and 30 parts of 4,4-diphenylmendiisocyanate at 80°C for 2 hours was cooled. , DM
After dissolving in 4 parts of F20.

Solution polymerization (60°C, 4 hours) was carried out by adding 8.2 parts of 1,4-butanediol as a chain extender, and 0.3 parts of ethanolamine as a polymerization terminator was added to obtain a polyurethane elastomer solution (A1oλ). .

Its solid content concentration is 30.11%, viscosity 82,000 cps/
It was a transparent liquid with a temperature of 30°C and a turbidity of 0.038.

A polyurethane elastomer solution (Bxo) was obtained by the prepolymer method in the same manner as described above, except that polydiethylene glycol adipate diol having a molecular weight of 1960 was used instead of polydipropylene glycol adipate diol.

The solid content concentration of this solution is 30%, and the viscosity is 82,000 cps.
/30°C, turbidity was 0.015.

Next, 50 parts each of (AlO) and (B10) of the polyurethane elastomer solution obtained by the prepolymer method were used and mixed with thorough stirring to form an elastomer solution composition (A1o+B,
o) was obtained.

This turbidity was 0.830 and it was a milky white homogeneous liquid.

In addition, (A) of the elastomer solution obtained by the prepolymer method
A composition (A
IO+Bl) was a milky white homogeneous liquid with a turbidity of 0.810.

Table 15 shows the results of wet coagulation of these elastomer solutions alone and as a composition.

Example 14 Example 1 and elastomer solution except that the following specific amounts of each chain extender (%1 to /165) were used in place of 8.2 parts of 1,4-butadiol as the chain extender. Table 16 shows the results of each composition (liquid) produced by mixing each elastomer solution obtained in the same manner as above and the other elastomer solution (B1).

Scrap Chain extender Usage amount (parts) /I61 Ethylene glycol 5.6 Comparative example] 35.0 parts of polydipropylene glycol adipate diol with a molecular weight of 980, 30.0 parts of 4.4'-diphenymethane diisocyanate, 1,4- Butanediol 7.5
Polyurethane elastomer solution (All) was polymerized in the same manner as in Example 1 except that 169.1 parts of DMF and 169.1 parts of DMF were used.
I got it.

The polymer concentration (solid content concentration) is 30.0%, the viscosity is 81,000 cps at 730°C, the turbidity is 0.02, the appearance is transparent, and the total nitrogen content in the polymer component is 4. There was a 6% tear.

On the other hand, the total nitrogen content in the polymer components of elastomer solution A in Example 1 was 3.8.

Next, the elastomer solution A7 obtained in step 5. When the elastomer solution A of Example 1 was mixed at a ratio of 50:50, the turbidity of the mixture was 0.03 and was substantially transparent.

In addition, elastomer solution A alone, A3. Single and A+A
Table 17 shows the solvent removal properties and the properties of the formed film during wet coagulation of the liquid mixture.

As is clear from this result, even if two elastomer solutions with the same elastomer components are mixed,
As in the case of each individual elastomer solution, a large amount of residual solvent forms a film with large pores and low moisture permeability, and no mixing effect is observed.

Claims (1)

[Scope of Claims] 1. A polyurethane solution composition produced by mixing at least two solutions in which a polyurethane elastomer comprising a polymeric diol, an organic diisocyanate, and a chain extender is dissolved in a water-miscible organic solvent. , one polyurethane elastomer solution is mixed with polydipropylene glycol adipate diol alone,
Alternatively, a diol mixture of polylactone glycol, polyalkylene glycol adipate diol, or polyalkylene ether glycol having a weight ratio of 70 or more and a weight ratio of 30 or less is dissolved in polydipropylene glycol adipate-based polyurethane elastomer-7- as a polymeric diol. The other polyurethane elastomer solution 1 (B) is selected from the group consisting of polydiethylene glycol adibetodiol, polyε-caprolactone glycol, and polytetramethylene ether glycol. A polydiethylene glycol adipate-based polyurethane elastomer made of a diol mixture of polylactone glycol, polyalkylene glycol adipate diol, or polyalkylene ether glycol having a weight ratio of 70 or less and a weight ratio of 30 or less as the polymer diol. , a substantially transparent solution with a turbidity of 0.05 or less in which polyε-caprolactone-based polyurethane elastomer or polytetramethylene ether-based polyurethane elastomer is dissolved (/), and a composition produced by mixing the polyurethane elastomer solution. A polyurethane elastomer solution composition for wet synthetic leather, which is a cloudy liquid with a turbidity of 0.2 to 1.5.2 The polyurethane elastomer solution to be mixed has a content concentration of each polyurethane elastomer of 20 to 40%. The composition according to claim 1, which is based on weight. 3 One polyurethane elastomer solution (3) and the other polyurethane elastomer solution CB) have a weight ratio of one polyurethane elastomer to the other polyurethane elastomer. The composition according to claim 1, which is mixed in a ratio of 95:5 to 5:95. 4. The composition according to claim 1, wherein the polyurethane elastomer solution on one side and the polyurethane elastomer solution on the other side are mixed such that the concentration of the polyurethane elastomer solution is 20 to 38% by weight of the total amount of polyurethane elastomer. 5. The composition according to claim 1, wherein the chain extender is a diamine, a low molecular weight glycol having a molecular weight of 500 or less, an amino alcohol, water, or a combination thereof. 6. The composition according to claim 1, wherein the water-miscible organic solvent is an amide solvent. 7. The composition according to claim 1, wherein the polyurethane elastomer bath solution to be mixed is a polyurethane elastomer solution obtained by a solution polymerization method.