JPS6186249A - Porous sheet material and manufacture thereof - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a porous polyurethane sheet material and a method for producing the same. The aim is to provide productivity.

(Prior Art) Many porous sheet materials made of polyurethane as natural leather substitutes and methods for producing them have been known, and can be roughly divided into wet methods and dry methods.

(Problem to be solved by the invention) Both methods have their advantages and disadvantages, and the dry method is superior in terms of productivity. As such a dry method, for example, the
There are methods described in Japanese Patent Laid-Open No. 18249 and Japanese Patent Application Laid-Open No. 51-41063, but these conventional methods use a relatively large amount of wood-loving polyurethane to form the polyurethane layer. Mechanical properties, physical and chemical properties are not sufficient, and the cumbersome and time-consuming drying process is a decisive drawback in the production method. In order to solve these drawbacks, it is inevitable to reduce the amount of hydrophilic polyurethane used, but it is clear that this will lead to other drawbacks (for example, instability of the processing solution, etc.). It has become.

As a result of intensive research in order to solve the above-mentioned drawbacks of the prior art, the present inventor has made a hydrophobic polyurethane dispersion or solution based on a specific manufacturing method the main component of the coating material, while A small amount of hydrophilic modified polyurethane obtained by graft polymerizing a specific proportion of at least one type of ionic hydrophilic monomer selected from the group of addition-polymerizable monomers having a tertiary amino group or a quaternary ammonium group is used as an emulsifier. The present invention was completed based on the finding that the above-mentioned drawbacks of the prior art can be solved.

(Means for Solving the Problems) That is, the present invention provides a porous sheet material in which a porous layer comprising a hydrophobic polyurethane (a) and a hydrophilic modified polyurethane (b) is provided on a base material; (a) is a hydrophobic polyurethane obtained by reacting a hydrophobic polyol, an organic diisocyanate, and a chain extender, and the hydrophilic modified polyurethane (
b) is obtained by reacting a hydrophobic polyol and an organic diisocyanate in the presence of a chain extender having an unsaturated double bond.
Next, a polyurethane obtained by graft polymerizing at least one ionic hydrophilic monomer selected from the group of addition polymers having a carboxyl group, a sulfonic acid group, a tertiary amine group, or a quaternary ammonium group. The porous sheet material and its manufacturing method are characterized in that the hydrophilic modified polyurethane (b) contains 10 to 50i1% of a hydrophilic addition-polymerizable monomer polymer.

To explain the present invention in more detail, the hydrophobic polyurethane (a) used in the method of the present invention itself is a conceptually known material, and is obtained by reacting a hydrophobic polyol, an organic diisocyanate, and a chain extender. Examples of the hydrophobic polyol' include polyethylene adipate, polyethylene propylene adipate, polyethylene butylene adipate, polydiethylene adipate, whose terminal group is a hydroxyl group and whose molecular weight is 300 to 4,000.
polybutylene adipate, polyethylene succinate,
polybutylene succinate, polyethylene sebacate,
Polyethylene sebacate, polytetramethylene ether glycol, poly-ε-caprolactone diol, polyhexamethylene adipate, carbonate polyol,
Examples of organic diisocyanates include 4,4'-diphenylmethane diisocyanate (MDI), water-added MDI, inphorone diisocyanate, 1,3-xylylene diisocyanate, 1,
Examples include 4-xylylene diisocyanate, 2,4-)lylene diisocyanate, 2,6-lylene diisocyanate, 1,5-naphthalene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, and chain extenders include ethylene glycol. ,
Propylene glycol, diethylene glycol, 1.4
-Butanediol, 1,6-hexanediol, ethylenediamine, 1,2-propylenediamine, trimethylenediamine, tetramethylenediamine, hexamethylenediamine, decamethylenediamine, inphorondiamine, m-xylylenediamine, hydrazine, water, etc. There is.

The hydrophobic polyurethane dispersion or solution (e) contains polyurethane (a) in an organic solvent (a) which has a limited mutual solubility with water and preferably has a temperature of 120°C or less at normal pressure.
It can be obtained by reacting the three components listed in 1- in e). The reaction conditions, such as temperature and time, may be conventionally known conditions.

Preferred organic solvents (c) include 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 acetone. , cyclohexane, tetrahydrofuran, 'dioxane, methanol, ethanol, isopropyl alcohol, butanol, toluene, xylene, dimethylformamide, dimethyl sulfoxide, perchloroethylene, trichlorethylene, methyl cellosolve, butyl cellosolve, cellosolve acetate, etc. can also be used. Among these organic solvents, organic solvents that have limited mutual solubility with water or those that do not dissolve at all are used as a mixture with other solvents with limited mutual solubility with water. Of course, the above solvents can also be used as a mixed solvent. Polyurethane (a
) to give a dispersion or solution (e), the solids content of which is advantageously in the range from about 5 to 60% by weight by addition or removal of the same or other solvents.

The modified polyurethane (b) used in the present invention has at least one type of ionic hydrophilic polyurethane selected from the group of addition septapolymerized polyurethanes having a carboxyl group, a sulfonic acid group, a tertiary amino group, or a quaternary ammonium group. The graft polymer may contain 10 to 50% by weight of a graft polymer made of a synthetic monomer and be dissolved in the organic solvent (e). Such a modified polyurethane (b) is prepared by reacting the hydrophobic polyol and the organic diisocyanate in the same manner as polyurethane (a) to form a chain extender having an unsaturated double bond, and then adding hydrophilicity to the polyurethane (b). It is obtained by grafting a polymerizable hexamer. The chain extender used in letter L has an average molecular weight of about 140 to 1, in which part or all of the chain extender is obtained by dehydration condensation of an unsaturated dibasic acid and a bifunctional compound having active hydrogen. It is preferable to use an unsaturated compound having active hydrogen at both ends of .000 (hereinafter referred to as a specific chain extender). Unsaturated dibasic acids or their functional derivatives, etc., diamines such as hydrazine, ethylenediamine, piperazine, propylene diamine, xylylene diamine, inphorone diamine, ethylene glycol, 1.4-butanediol, 1.3-butanediol , 2.3-butanediol, propylene glycol, diethylene glycol,
1.5-bentanediol, neopentyl glycol,
Difunctional compounds having active hydrogen such as glycols such as dipropylene glycol, amine alcohols such as monoethanolamine and dimethylethanolamine,
They are obtained by polycondensation at a rate of about 1.2 to 2.0 moles per mole of unsaturated dibasic acid, and particularly preferred are those having an average molecular weight of about 140 to 1,000. This normal condensation reaction itself may be carried out by a conventionally known method, for example, in an inert gas atmosphere at a reaction temperature of 150 to 240°C in the presence of a catalyst such as a sulfonate compound or a titanate compound for about 3 to 15 hours. It's convenient. Such a specific chain extender is used in the method of the present invention in a proportion of 0.001 to 0.5 mol per mol of the hydrophobic polyol.

This particular chain extender is also compatible with other common chain extenders,
For example, it can be used in combination with water or a bifunctional compound containing active hydrogen as described above.

The ionic hydrophilic monomers used in the present invention may be any known ones, such as acrylic acid, methacrylic acid, α-chloroacrylic acid, α-chloromethacrylic acid,
Maleic acid, itaconic acid, vinyl sulfonic acid, sulfonated styrene, 2-acrylamido-2-methylpropanesulfonic acid, dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl acrylate, diethylaminoethyl methacrylate, vinylpyridine, vinylnaphthalene, etc. Preferred are nitrogen-containing vinyl monomers or quaternized products thereof.

In addition, to adjust the balance between wood-philicity and hydrophobicity, it may be used in combination with other addition-polymerizable hexamers. For example, acrylic acid, α-chloroacrylic acid, methacrylic acid, and their methyl, ethyl, and propyl , butyl ester; styrene, methylstyrene, dimethylstyrene, ethylstyrene, methoxystyrene, divinylbenzene, α-methylstyrene, β-methylstyrene, chlorostyrene, 2.
5-dichlorostyrene, α-chlorostyrene or derivatives thereof are preferred.

In addition, in order to increase the stability of the polyurethane emulsion (d),
It is also possible to use the modified polyurethane (b) in combination with a general W2O type emulsifier.

The above-mentioned modified polyurethane (b) can be used as a solution in an organic solvent or alone, as a polyurethane dispersion or solution (b).
Mix with e) and use as is or after neutralization.

In this mixed dispersion or solution, polyurethane (a) is in a dispersed state or solution, and modified polyurethane (b)
is in a dissolved state, and the total solid content is about 5 to 60% by weight.

The polyurethane emulsion (d) used in the present invention is prepared by strongly stirring the mixed dispersion or solution described in L, and adding water of less than saturated φ to the mixed dispersion or solution, for example, the solid content in the mixed dispersion or solution. It is obtained by adding about 5 to 60 parts by weight of water per 100 parts by weight. The emulsion thus obtained is a milky white creamy fluid and remains stable even if left as is for several months. Such an emulsion may optionally contain various additives such as coloring agents, crosslinking agents, stabilizers, fillers and the like, as required.

Examples of the base material used in the present invention include various woven fabrics, knitted fabrics, non-woven fabrics, house paper, plastic films, metal plates,
The emulsion may be applied to any base material such as a glass plate, for example, by a coating method, a dipping method,
Any known method such as a combination method of these may be used, and the amount of application and/or impregnation can be varied within a wide range depending on the purpose, such as about 5 to 2,000 g (compounded liquid)/m''. .

The drying step in the method of the present invention can be completed in a very short time and without the need for complicated processing, and this drying process is the rate-limiting step in productivity in the dry method as in the method of the present invention. Therefore, such a short drying time is extremely advantageous compared to conventional methods. That is, the coated and/or impregnated substrate is
There is no need for any coagulation process as described in Publication No. 3, and approximately 6
0-100℃ for about 1-3 minutes and about 100-150℃
The desired porous sheet material of the present invention can be obtained by only drying for about 1 to 3 minutes. The reason why such a short drying process is achieved is that the hydrophobic polyurethane (a) used as a film forming agent in the present invention accounts for the majority of the total polyurethane, and a small amount of surfactant (polyurethane ( b
)), it is stably dispersed and emulsified with water, and during drying, it quickly and easily comes into contact with water due to evaporation of the organic solvent, resulting in gelation.

(Function/Effect) The porous sheet material obtained by the present invention as described above has a very fine pore structure, has excellent physical properties, and has excellent water vapor permeability, and can be used for various synthetic leathers, etc. Materials include clothing, shoes, waterproof cloth, tents, wallpaper, flooring, 11
1. It is useful for filters, air conditioners, etc.

Next, the present invention will be specifically explained with reference to Examples. In addition,
All numbers in the middle of the text or percentages are based on weight.

Examples 1 to 7 (Production of ili aqueous and woody polyurethane) 1. Polytetramethylene glycol (average molecular weight approx.
, ooo, hydroxyl value 112) 1,000 parts, ethylene glycol 93 parts, diphenylmethane diisocyanate 6
Add 25g to 1.500 parts of methyl ethyl ketone,
After reacting at 0°C for 8 hours, 2,500 parts of methyl ethyl ketone was added and cooled to room temperature with stirring to reduce the solid content to 3.
A 0% milky white polyurethane dispersion (1) was obtained.

2.1.4-Butaneethylene adipate (average molecular weight approximately i, ooo, hydroxyl value 112) 1.000 parts, 1.4
-144 parts of butanediol, 1.1 parts of methyl ethyl ketone
44 parts and 650 parts of diphenylmethane diisocyanate
After reacting at 70° C. for 8 hours, 3.042 parts of methyl ethyl ketone was added to homogenize the mixture, and the mixture was cooled to room temperature while stirring to obtain a milky white polyurethane dispersion (2) with a solid content of 30%.

3.1.6-hexamethylene adipate (average molecular weight 2
,000, hydroxyl value 56) 1,000 parts, 125 parts of 1.4-butanediol, and 472 parts of diphenylmethane diisocyanate were added to 1,200 parts of methyl ethyl ketone, and after reacting at 70°C for 8 hours, an additional 2.526 parts of methyl ethyl ketone was added. The mixture was homogenized and cooled to room temperature while eLff was applied to obtain a milky white polyurethane dispersion (3) with a solid content of 30%.

4.1. After reacting 1,000 parts of 4-butane ethylene adipate (average molecular weight approximately 1,000, hydroxyl value 112) and 408 parts of inphorone diisocyanate at 100°C for 6 hours, 1.230 parts of methyl ethyl ketone and torz 71.23
Add 0 parts of n-butyl, 1.230 flJ of n-butyl, and 148 parts of inphorondiamine, thoroughly homogenize by t't4,
A polyurethane solution (4) with a solid content of 30% was obtained.

5. 100 parts of itaconic acid and 95 parts of ethylene glycol were placed in a reaction vessel equipped with a dehydrator, tuffed by blowing nitrogen gas, and the temperature was raised to 140°C. Thereafter, the temperature was raised to 200°C by increasing the temperature by 30"C every hour. The dehydration polycondensation reaction was continued at that temperature, and the reaction was terminated when the acid value became 1 or less. The unsaturated compound with active hydrogen has an acid value of 0.5 and an average molecular weight of 22.
It was 0.

Next, 100 parts of polytetramethylene glycol ether (V equivalent: about 2,000, hydroxyl value 56), 3 parts of the unsaturated compound having active hydrogen at both ends obtained by the above reaction, 4.4'- 16 parts of diphenylmethane diisocyanate and 7,100 parts of methyl ethyl keto were placed in a reaction vessel and reacted at 75 to 85°C under a nitrogen stream. As the viscosity increased, the mixture was diluted with methyl ethyl ketone to produce a final polyurethane with a resin concentration of 30% and a viscosity of 12.000 cps/20"C. A resin solution was obtained.

Next, to 100 parts of this polyurethane resin solution, 5 parts of n-butyl methacrylate, 15 parts of dimethylaminoethyl methacrylate, 50 parts of methyl ethyl ketone, 30 parts of sec-butyl alcohol, and 0.0 parts of benzoyl peroxide.
2 parts were added and the reaction was carried out for 6 hours at 80-85°C in a nitrogen atmosphere, resulting in a viscosity of 2, 600 cps/25°C,
A modified polyurethane resin solution (5) with a solid content of 25% was obtained.

6. 100 parts of polyethylene glycol adibate glycol (average molecular weight approximately t, ooo, hydroxyl value 112), 4 parts of the unsaturated compound having active hydrogen at both ends obtained in Example 5, 4.4'-diphenylmethane diisocyanate 30 parts of methyl ethyl ketone and 100 parts of hemethyl ethyl ketone were placed in a reaction vessel, reacted at 75 to 85°C under a nitrogen stream, diluted with methyl ethyl ketone as the viscosity increased, and finally obtained polyurethane with a resin concentration of 30% and a viscosity of 8,000 cps/20°C. A resin solution was obtained.

Next, to 100 parts of this polyurethane resin solution, 5 parts of methacrylic acid, 5 parts of 2-acrylamido-2-methylpropanesulfonic acid, 26 parts of methyl ethyl ketone, 24 parts of sec-butyl alcohol, and 0.0 parts of benzoyl peroxide were added.
2 parts and reacted for 6 hours at 80-85°C in a nitrogen atmosphere, resulting in a viscosity of 3.900 cps/25°C and a solid content of 25%.
A modified polyurethane resin solution (6) was obtained.

7. 100 parts of itaconic acid and 1,4-butanediol 13
8 parts were placed in a reaction vessel equipped with a dehydrator, stirred while blowing nitrogen gas, and heated to 140°C. Thereafter, the temperature was raised to 200°C while increasing the temperature by 30°C every hour. The dehydration polycondensation reaction was continued at that temperature, and the reaction was terminated when the acid value became 1 or less.

The resulting unsaturated compound having active hydrogen at both ends had an acid value of 0.4 and an average molecular weight of 280.

Next, 100 parts of polytetramethylene glycol ether (average molecule: about 2,000, hydroxyl value 56), 4 parts of the unsaturated compound having active hydrogen at both ends obtained by the above reaction, hydrogenated 4°4 17 parts of '-diphenylmethane diisocyanate and 100 parts of methyl ethyl ketone were placed in a reaction vessel, and 0.1 part of dibutyltin dilaurate was added while carrying out the reaction at 80 to 85°C in a nitrogen atmosphere.
As the viscosity increases, 26 parts of methyl ethyl ketone is added, and the final resin concentration is 30% and the viscosity is 2,0OOCp s/20.
A polyurethane resin solution at ℃ was obtained.

Next, 10 parts of ethyl methacrylate, 0 parts of methacrylic acid, 65 parts of methyl ethyl ketone, 15 parts of isopropyl alcohol, and 0.4 parts of azobisisobutyronitrile were added to 100 parts of this polyurethane resin solution, and 80 to 80 parts of azobisisobutyronitrile were added in a nitrogen atmosphere. The reaction was carried out at 85°C for 7 hours, and the viscosity was 12
A modified polyurethane resin solution (7) with a solid content of 25% and a temperature of 00 cps/25°C was obtained.

Examples 8 to 13 (Production of polyurethane emulsion) Example 1
The product of ~7, organic solvent and water were adjusted to pH in a homomixer.
Then, the following polyurethane W10 emulsion was prepared.

8. Polyurethane 8 Polyurethane dispersion (1) Too much polyurethane solution (5) 10 parts Methyl ethyl ketone 20 parts Toluene
20 parts water
80 parts 9, polyurethane 7f9 Polyurethane dispersion (2) 100 parts polyurethane solution (5) 12 parts dioxane
10 parts toluene
10 parts xylene 2
0 parts water
60 parts 10, polyurethane, lO Polyurethane dispersion (2) 100 parts Polyurethane solution (6) 7 parts Methyl ethyl ketone 20 parts Kijirole
20 parts water
75 parts 11, polyurethane (1
1 Polyurethane dispersion (3) 100 parts Polyurethane solution (6) 5 parts Tetrahydrofuran 20 parts Xylene
20 parts water
80 parts 12, polyurethane (
12 Polyurethane dispersion (3) ' 100 parts Polyurethane solution (7) 12 parts Methyl ethyl ketone 150 parts Methyl isobutyl ketone 2 (11! Water
70 parts 13, Polyurethane, -13 Polyurethane solution (4) 100 parts Polyurethane solution (5) 10 parts Calcium carbonate 10 parts Toluene
30 parts methyl ethyl ketone
20 parts water
80 parts Polyurethane emulsion (8) - (
The properties of 13) are as shown in Table 1 of F.

La l Knee emulsion Viscosity (25℃) Solid content 8
16.000 (cps) 14.1 (U9
15.000 15.810
28.000 14.311 2
4.000 13.912 18
0 9.413 34.000
17.0 Notes Stability: No change for more than 1 month Example 14~
20 The polyurethane emulsions (8) to (13) shown in Table 1 above were applied to (or impregnated with) various substrates and dried to obtain various porous sheet materials of the present invention.

ノ 2 - - ゛Example 14 1 fork-8L-eyebrow release paper cloth 200 (coating) (180
℃ 2 minutes + 125℃ 2 minutes Example 15 Milk'' 1 scoop-81-M Nylon tack・rn' 600 (coating)
1u" 80℃ 2 minutes + 125℃ 2 minutes Example 16 ML9 □ Cotton cloth・"rn' 400 (coating) LL
SJ 80°C 2 minutes + 125°C 2 minutes Example 17 Breast”E armpit-10 tut T/R brushed fabric °・cloth
IT! '800 (coating) ul' 80℃3
min + 140°C 3 min Example 18 Kuno 1 foot knee 11 Base knee material Cotton Cloth 2
, cloth A11 Go 300 (coating) 41 Ai J
80°C 2 minutes + 125°C 2 minutes Example 19 L color - 121 months Non-woven fabric, cloth (impregnation) early m' 1000 (impregnation) uol
90°C 3 minutes + 140°C 3 minutes Example 20 L color difference -13l Tetron taffeta, -Irj (impregnation) star (m' 100 (coating) (
1 row 180℃ 2 minutes + 125℃ 2 minutes A53-7 (Sheet lamp 11m1V 14 White 0.482 70 8290 Uniform dense 15 // 0.6Q5 1?5 59
70 //18 n O,558109
6250//17 pt nQtsuQ '1llIFi Figwan
〃18 tt O,657755
490ttl g // --3
880/'20 tt O, 8195
85800pt Note ■... Apparent specific gravity (g/crn') ■... Thickness g) ■... Moisture permeability (g/rrr' -24h) (JIS
ZO208B) ■... Internal pore structure As described above, according to the 1!1 method, a porous sheet material with excellent physical properties can be obtained in an extremely short drying process.

Patent applicant: Dainichiseika Kogyo Co., Ltd. (and 1 other person) ・ζ′ρ−・ Agent: Patent attorney Yoshi 1) Katsuhiro 7S>,',,”,
'.

li: ni-1

Claims (3)

[Claims] (1) In a porous sheet material in which a porous layer consisting of a hydrophobic polyurethane (a) and a hydrophilic modified polyurethane (b) is provided on a base material; the above hydrophobic polyurethane (a)
is a hydrophobic polyurethane obtained by reacting a hydrophobic polyol, an organic diisocyanate, and a chain extender. The reaction is carried out in the presence of a chain extender having a carboxyl group, a sulfonic acid group, or a tertiary amino group or a quaternary
A polyurethane obtained by graft polymerizing at least one ionic hydrophilic monomer selected from the group of addition-polymerizable monomers having an ammonium group, the hydrophilic modified polyurethane (b) A porous sheet material containing 10 to 50% by weight of a polymerizable monomer. (2) A water-in-oil polyurethane emulsion (d) consisting of a hydrophobic polyurethane (a), a hydrophilic modified polyurethane (b), an organic solvent (c) and water is impregnated and/or applied to a substrate. In a method for producing a porous sheet material, the hydrophobic polyurethane (a) comprises:
A hydrophobic polyurethane dispersion or solution (e) obtained by reacting a hydrophobic polyol, an organic diisocyanate, and a chain extender in an organic solvent (c) having limited mutual solubility with water; Modified polyurethane (
b) reacts a hydrophobic polyol and an organic diisocyanate in the presence of a chain extender having an unsaturated double bond;
Next, at least one ionic hydrophilic monomer selected from the group of addition-polymerizable monomers having a carboxyl group, a sulfonic acid group, a tertiary amino group, or a quaternary ammonium group is graft-polymerized. A method for producing a porous sheet material, wherein the modified polyurethane (b) contains 10 to 50% by weight of a hydrophilic addition-polymerizable monomer polymer. (3) A chain extender having an unsaturated double bond is attached to both ends with an average molecular weight of approximately 140 to 1,000 obtained by dehydration condensation of an unsaturated dibasic acid and a bifunctional compound having active hydrogen. The manufacturing method according to claim (2), which comprises an unsaturated compound having active hydrogen.