JPH0543792A - Polyamino acid urethane resin and product using the same - Google Patents

Abstract

PURPOSE:To provide the title composition reduced in discoloration and deterioration due to sunlight, ultraviolet light, heat, or nitrogen oxides, and also obtain moisture-permeable waterproof fabrics excellent in wear resistance and waterproofness, etc., by processing the above composition. CONSTITUTION:The objective resin can be obtained by incorporating (A) a copolymer resin from an amino acid and urethane or a polyamino acid urethane resin, a blended resin of polyamino acid resin and polyurethane resin with (B) 0.05-30 (pref. 1-10) pts.wt., per 100 pts.wt. on a resin solid basis of the resin A, of a hydrazine compound (e.g. oxalic dihydrazide). The present composition is applied on a fibrous base material (e.g. cellulosic material such as cotton or linen) to obtain the other objective product (moisture-permeable waterproof fabric).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyamino acid urethane resin composition and a cloth foil using the same, and in manufacturing a breathable waterproof cloth or the like using a polyamino acid urethane resin as a raw material, the resin A polyamino acid urethane resin composition that provides excellent weather resistance, abrasion resistance, waterproofness (water resistance, washing resistance), and softness without impairing favorable characteristics such as moisture permeability, which is an advantage, and the use thereof Related to the product obtained.

[0002]

2. Description of the Related Art In recent years, resins for moisture-permeable waterproof cloth have been actively developed. In particular, polyamino acid urethane resin is
It is widely used as a material for synthetic leather, artificial leather, and breathable waterproof cloth. However, there is a problem that it gradually turns yellow due to sunlight, ultraviolet rays, heat, nitrogen oxides and the like. Also,
There are also problems with abrasion resistance, waterproofness, flexibility, etc.

As a method for improving the weather resistance, a semicarbazide compound (JP-A-52-15548, 15549), a phosphite polymer and a semicarbazide compound (JP-A-62-25155),
A method of adding a triazine derivative (JP-A-53-144957) or the like has been proposed, but these additives have poor compatibility with a polyamino acid urethane resin, or
There were problems such as exudation and volatilization after addition. In addition, these additives have a problem that the synthesis process is long and complicated.

[0004]

SUMMARY OF THE INVENTION The object of the present invention is to solve the problems of compatibility and to cause discoloration and deterioration due to sunlight, ultraviolet rays, heat, nitrogen oxides, etc. It is an object of the present invention to obtain a polyamino acid urethane resin composition which is reduced in the amount thereof, and a product such as a moisture-permeable waterproof cloth satisfying abrasion resistance, waterproofness and flexibility by processing the composition.

[0005]

Means for Solving the Problems As a result of intensive studies on polyamino acid urethane resin in order to solve such a problem, the present inventors have made it possible to include a hydrazide compound which is easily available at the time of preparing the polyamino acid urethane resin. As a result, the hydrazide compound has sunlight, ultraviolet rays,
It was found that compatibility with polyamino acid urethane resin can be solved while maintaining durability against discoloration and deterioration due to heat, nitrogen oxides, etc., and surprisingly, this polyamino acid urethane resin composition was processed. The inventors have found that the moisture-permeable waterproof cloth and the like obtained as described above have excellent wear resistance and waterproofness, and completed the present invention.

That is, the present invention relates to a polyamino acid urethane resin containing a hydrazide compound, and
The gist is a cloth foil obtained by applying a resin composition comprising a polyamino acid urethane resin containing a hydrazide compound to a fiber base material. The present invention will be described in detail below.

The polyamino acid urethane resin in the present invention is a copolymer resin composed of amino acid and urethane, or a mixed resin of polyamino acid resin and polyurethane resin.

The copolymer resin is a urethane prepolymer having a terminal amino group obtained by extending the chain length of a urethane prepolymer having a terminal OH group, a terminal isocyanate group, or a terminal isocyanate group composed of an isocyanate and a polyol component with a diamine. It is a copolymer obtained by the reaction of an amino acid N-carboxylic acid anhydride (hereinafter, N-carboxylic acid anhydride is referred to as NCA). Examples of the amino acid include acidic amino acids such as aspartic acid and glutamic acid and derivatives thereof, and neutral amino acids such as glycine, DL-alanine, cystine, methionine, and leucine, and any of these optically active forms and racemic forms may be used. Well, these may be used alone or in combination. The copolymerization with the urethane prepolymer having a terminal isocyanate group can be obtained by adding the amino acid NCA to the urethane prepolymer solution and then adding hydrazine, amines and alcohols. Ethylenediamine, diethylamine, ethanolamine and the like are used as the amines. Further, in the case of copolymerization with a urethane prepolymer having a terminal OH group and an amino group, it can be synthesized by adding the amino acid NCA to the urethane prepolymer solution. The weight ratio of urethane prepolymer to amino acid NCA is 90:10 to 10:90. This ratio is determined according to the desired physical properties of the product. For example, in the case of giving an artificial leather silver surface excellent in texture and moisture permeability, the amino acid NC
It is preferable that the content of A is large, and if the elasticity and adhesiveness of the artificial leather and the nonwoven fabric binder are important, the content of urethane prepolymer is large.

As the isocyanate component, aromatic diisocyanate, aliphatic diisocyanate, and alicyclic diisocyanate may be used alone or in a mixture thereof. For example, tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 1,6-hexa Examples thereof include methylene diisocyanate and 1,4-cyclohexane diisocyanate. As the polyol component, polyether polyol or polyester polyol is used. Polyether polyols include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, and the like, and polyester polyols include the reaction formation of diols such as ethylene glycol and propylene glycol with dibasic acids such as adipic acid and sebacic acid. And ring-opening polymers such as caprolactone.

The mixed resin of polyamino acid resin and polyurethane resin is a mixture of polyamino acid resin and polyurethane resin mechanically in a weight ratio of 99: 1 to 10:90.

The polyamino acid resin referred to herein is obtained by polycondensing the above amino acid NCA with a compound having active hydrogen in a solvent in a usual manner. Amino acid N
In the case of polycondensation of CA or copolymerization of the above amino acid NCA and urethane prepolymer, 3 is used as a catalyst if necessary.
It is advisable to add a primary amine.

As the polyurethane resin, a reaction product of a reaction product of the above organic diisocyanate and diol in a solvent and, if necessary, a product whose chain length is extended with a diamine are used.

As a method of incorporating the hydrazide compound, the hydrazide compound is simultaneously added at the time of synthesizing the above polyamino acid resin or polyurethane resin, or at the time of copolymerizing the amino acid NCA and urethane prepolymer at the time of synthesizing the polyamino acid urethane resin. All you have to do is react.

The hydrazide compound used in the present invention may be any compound having a hydrazide in the molecule,
For example, oxalic acid dihydrazide, adipic acid dihydrazide, sebacic acid dihydrazide, succinic acid dihydrazide,
Dodecanedioic acid dihydrazide, eicosanedioic acid dihydrazide, hexadecanedioic acid dihydrazide, isophthalic acid dihydrazide, 7,11-octadecadiene-1,18-dicarbohydrazide, 1,3-bis (hydrazinocarboethyl) -5-isopropyl Examples thereof include dibasic acid dihydrazides such as hydantoin, acetohydrazide, propionic acid hydrazide, butyric acid hydrazide, fatty acid hydrazides such as lauric acid hydrazide, N, N-dimethylglycine hydrazide, nicotinic acid hydrazide, isonicotinic acid hydrazide, and salicylic acid hydrazide. Also, a mixture of these may be used.

The amount of these hydrazide compounds used is 0.05 to 3 with respect to 100 parts of the resin solid content obtained.
It is desirable to use 0 part, preferably 1 to 10 parts. If the amount used is less than 0.05 parts, the effect of preventing yellowing and deterioration of mechanical properties due to sunlight and ultraviolet rays is poor, and 3
If the amount exceeds 0 part, the characteristics of the polyamino acid urethane resin are affected, which is not preferable.

As a solvent that can be used for the resin composition of the above-mentioned polyamino acid urethane copolymer resin or polyamino acid and polyurethane mixed resin, these polyamino acid urethane resins are dissolved or suspended to prepare a synthetic sheet or cloth foil. There is no limitation as long as it is a solvent that can be industrially processed, and representative examples thereof include ether solvents such as dioxane, tetrahydrofuran and isopropyl ether, aromatic solvents such as benzene, toluene and xylene, ethyl acetate and butyl acetate. Etc., ester solvents such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc., amide solvents such as N, N-dimethylformamide, formamide, N, N-dimethylacetamide, etc., alcohols such as ethanol, isopropyl alcohol, butanol, etc. Solvent It may be a German or a mixture.

Further, in the present invention, a crosslinking agent may be used in combination, if necessary, for the purpose of improving the adhesion between the coating of the polyamino acid urethane resin and the substrate. Examples of the cross-linking agent include isocyanate cross-linking agents and epoxy cross-linking agents. The amount of the crosslinking agent used is 0.0 with respect to the resin solid content.
It is desirable to use 5 to 10%, preferably 0.1 to 5%. If the amount used is less than 0.05%, the adhesive force of the resin to the base fabric will be poor, and if it exceeds 10%, the texture will be hardened, which is not preferable.

In order to improve the texture, if necessary, a moisturizing agent such as glycerin, propylene glycol, sorbitol, polyethylene glycol, sodium pyrrolidonecarboxylate, sodium lactate, water-soluble chitin, a coupling agent, a silicone resin, Fluorine-based resin and liquid rubber may be added as appropriate.

A waterproof highly moisture-permeable cloth foil can be produced by dissolving the polyamino acid urethane resin of the present invention in a water-soluble solvent, coating or impregnating the fiber base material, and removing the solvent in water. Alternatively, a water-in-oil emulsion of a polyamino acid urethane resin may be applied to or impregnated in a fiber base material, and the solvent may be dried by heating to remove the solvent, followed by dehydration.

The fibrous base material includes fibrin such as cotton, hemp, wood and human silk and derivatives thereof, silk, wool, natural leather, synthetic leather,
Artificial leather, polyamides, polyurethanes, polyesters and their derivatives, natural rubber, synthetic rubber or mixtures thereof, and various plastics, which are used according to the application. Examples of the obtained molded article using the waterproof highly breathable cloth foil include gloves, windbreakers, raincoats, shoes, handle covers, sheets, furniture covers and the like.

The present invention has the above-mentioned constitution. Needless to say, the reason why the compatibility problem is solved in the present invention is that the hydrazide compound is incorporated into the polyamino acid urethane molecule. This is because the problem of compatibility itself is eliminated by reacting with. Further, whether the cloth foil obtained by using the polyamino acid resin containing the hydrazide compound of the present invention is excellent in abrasion resistance, waterproofness, and flexibility, the reason is not critical, but it has a hydrazide skeleton in the molecule. As a result, the strength increases,
It is considered that abrasion resistance and heat resistance are improved, and accordingly, waterproofness is also improved.

[0022]

The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples.
Moreover, the evaluation used the evaluation method shown below. The number of parts means parts by weight.

1. Light resistance test: A carbon arc meter "manufactured by Suga Test Instruments Co., Ltd." is irradiated with light for 50 and 100 hours, and the discoloration of the sample is visually evaluated. 2. Heat resistance test: The sample is left in a gear oven at 120 ° C for 100 hours, and the discoloration of the sample is visually evaluated. 3. Nitrogen oxide resistance test: 3 units are exposed to a nitrogen dioxide gas atmosphere based on JIS-L-0855, and the discoloration of the sample is visually evaluated. The visual evaluation criteria for each of the above tests are as follows. ⊚: Very good (no discoloration) ○: Good (pale yellow) Δ: Slightly bad (yellow) ×: Poor (brown) 4. Abrasion resistance test: Gakushin-type friction fastness tester (JIS
L 0823) was rubbed 1000 times with a load of 200 g according to JIS L 1084 (friction tester method), and the appearance state of the film was observed to perform the following three-stage evaluation. ×: Complete wear Δ: Partial wear ○: No abnormality 5. Water pressure resistance According to JIS L 1092 (low water pressure method). The washing condition is 40. 82.5g of cloth including sample cloth.
After soaking in 30 liters of water of ° C and adding 44 ml of liquid top (manufactured by Lion Corporation) as a detergent, it was washed in a washing machine for 100 minutes. Rinsing was performed 3 times for 20 minutes with 30 liters of water at room temperature. Dehydration 3 minutes, rinse rinse 6 minutes, dehydration 3
After minutes, the sample was air dried. 6. Water vapor transmission rate According to JIS L 1099 (calcium chloride method).

Example 1 Polyurethane resin 900 parts and 200 parts of polytetramethylene glycol and polyethylene glycol, respectively, having a number average molecular weight of 2000
Parts, ethylene glycol 58.3 parts, and adipic acid hydrazide 15.6 parts were added with 3000 parts of methyl ethyl ketone, dissolved at 50 ° C., and added with 2 parts of 10% dibutyltin dilaurate solution in methyl ethyl ketone as a catalyst.
40,4,4'-diphenylmethane diisocyanate
0 part was added. The reaction is continued under reflux of this mixed solution of methyl ethyl ketone, and the viscosity of the reaction solution is 100,000 cPs / 30 ° C.
The reaction was stopped by adding morpholine. 1600 parts of methyl ethyl ketone was added to this reaction liquid to obtain a polyurethane resin solution (a).

Example 2 Polyamino Acid Urethane Copolymer Resin 900 parts and 200 parts of polytetramethylene glycol and polyethylene glycol having a number average molecular weight of 2,000, respectively.
Part, ethylene glycol 63.86 parts, and methyl ethyl ketone 3000 parts were dissolved at 50 ° C. and 10% dibutyltin dilaurate methyl ethyl ketone solution 2 parts was added as a catalyst, followed by addition of 4,4′-diphenylmethane diisocyanate 400 parts. .. The reaction is continued under reflux of this mixed solution of methyl ethyl ketone, and the viscosity of the reaction solution becomes 1
Morpholine was added to stop the reaction at a time point of 0,000 cPs / 30 ° C. Methyl ethyl ketone 160 was added to this reaction solution.
0 part was added to obtain a polyurethane resin solution. To 500 parts of the polyurethane resin solution thus obtained, 2.5 parts of adipic dihydrazide was added and stirred at 30 ° C. for 10 minutes, then 90 parts of methyl isobutyl ketone and 120 parts of toluene.
34.5 parts of γ-methyl-L-glutamic acid NCA was dissolved in a mixed solution of 80 parts of methyl ethyl ketone and 80 parts of methyl ethyl ketone, and the resulting solution was added to the resin solution and polymerized at 30 to 40 ° C. for 3 hours to obtain a polyamino acid urethane copolymer resin (roth). ).

Example 3 Mixed Resin of Polyamino Acid and Polyurethane A mixed solution of 80 parts of toluene and 20 parts of N, N-dimethylformamide was added to 9 parts of L-leucine NCA and γ-methyl-L.
-A mixed NCA of 12 parts of glutamic acid NCA was added and dissolved, then 0.5 part of ethylenediamine was added, and the mixture was stirred at 25 ° C for 1 hour and then polymerized at 60 ° C for 5 hours. This polymerization solution 1
To 00 parts, 40 parts of the urethane resin solution (a) obtained in Example 1 was added and uniformly mixed to obtain a mixed resin (c) of polyamino acid and polyurethane.

Example 4 A resin solution (d) was obtained by using sebacic acid dihydrazide instead of adipic acid dihydrazide in Example 2.

Example 5 A resin solution (e) was obtained by using oxalic acid dihydrazide instead of adipic acid dihydrazide in Example 2.

Example 6 A resin solution (f) was obtained by using eicosane diacid dihydrazide instead of adipic acid dihydrazide in Example 2.

Example 7 (A) The resin solution (b) obtained in Example 2 was coated on a release paper and dried at 80 ° C. for 3 minutes and then at 120 ° C. for 3 minutes to prepare by a dry method. A transparent film having a thickness of 0.06 mm was obtained.

(B) Resin solution (d) obtained in Example 4
A film was obtained in the same manner as in (A).

(C) Resin solution (e) obtained in Example 5
A film was obtained in the same manner as in (A).

(D) Resin solution (f) obtained in Example 6
A film was obtained in the same manner as in (A).

(E) Resin solution (C) obtained in Example 3
On release paper, apply at 80 ° C for 3 minutes, then 120
0.06m thickness prepared by dry method after drying at ° C for 3 minutes
m transparent film was obtained.

The results of the light resistance, heat resistance and nitrogen oxide resistance tests of the films (A) to (E) are shown in Table 1.

[0036]

[Table 1]

Comparative Example 1 (F) In Example 2, the reaction was carried out without adding adipic acid dihydrazide to obtain a resin solution (g). A film was obtained from this resin solution in the same manner as in Example 7 (A).
The results of the light resistance, heat resistance and nitrogen oxide resistance test of this film are shown in Table 1.

Example 8 Using the resin solutions obtained in Examples 2, 4, 5 and 6, Table 2
A resin composition was obtained with the additive composition shown in FIG. 30 parts of water, surfactant E to 100 parts of solid content of this resin composition
1 part of MALEX103 (manufactured by Nippon Emulsion Co., Ltd.),
C-2298 10 parts was added and the emulsion solution stirred at high speed was added to nylon taffeta (flexibility 48 mm) at 10 g /
Roll coater to make m2, 8
The solvent and water were removed by two-stage drying at 0 ° C × 5 minutes and 120 ° C × 5 minutes to obtain a porous highly permeable cloth foil. Table 3 shows the results of evaluating the abrasion resistance, washing resistance, and water vapor transmission rate of these cloth foils.

[0039]

[Table 2]

[0040]

[Table 3]

Comparative Example 2 (D) In Example 2, the reaction was carried out without adding adipic acid dihydrazide to obtain a resin solution. A cloth foil was obtained in the same manner as in Example 8 except that this resin solution was used. The results of evaluation of abrasion resistance, washing resistance, and water vapor transmission rate of this cloth foil are shown in Table 3.

[0042]

[Effects of the Invention] At the time of preparing a polyamino acid urethane resin, by reacting a hydrazide compound that is easily available, while maintaining the durability of the hydrazide compound against discoloration due to sunlight, ultraviolet rays, heat, nitrogen oxides, etc., Moreover, the compatibility with the resin can be solved, and the polyamino acid urethane resin composition can be processed to obtain a moisture-permeable waterproof cloth having excellent abrasion resistance and waterproofness.

─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] October 28, 1991

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] 0002

[Correction method] Change

[Correction content]

[0002]

2. Description of the Related Art In recent years, active development of resins for breathable waterproof cloths has been made. In particular, polyamino acid urethane resin has a polyamino acid structure similar to that of natural protein.
Since it has a texture and a texture similar to that of natural leather, it is often used as a material for synthetic leather, artificial leather, breathable waterproof cloth and the like. However, the urethane bond of polyamino acid urethane resin
Deterioration of joint area due to sunlight, ultraviolet rays, heat, nitrogen oxides
Then, gradually there is a problem of yellowing. Further, there are problems in abrasion resistance, waterproofness, flexibility and the like.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0017

[Correction method] Change

[Correction content]

Further, in the present invention, a crosslinking agent may be used in combination, if necessary, for the purpose of improving the adhesion between the coating of the polyamino acid urethane resin and the substrate. Examples of the cross-linking agent include isocyanate cross-linking agents and epoxy cross-linking agents. The amount of the crosslinking agent for the tree fat 0.05
It is desirable to use 0%, preferably 0.1 to 5%. If the amount used is less than 0.05%, the adhesive force of the resin to the base fabric will be poor, and if it exceeds 10%, the texture will be poor.
It becomes hard, which is not preferable.

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0024

[Correction method] Change

[Correction content]

Example 1 Polyurethane resin 900 parts and 200 parts of polytetramethylene glycol and polyethylene glycol, respectively, having a number average molecular weight of 2000
Parts, ethylene glycol 58.3 parts, and adipic acid hydrazide 15.6 parts were added with 3000 parts of methyl ethyl ketone, dissolved at 50 ° C., and added with 2 parts of 10% dibutyltin dilaurate solution in methyl ethyl ketone as a catalyst.
400 4,4'-diphenylmethane diisocyanate
Added parts. The reaction is continued under reflux of this mixed solution with methyl ethyl ketone, and the viscosity of the reaction solution is 100,000 cps / 30 ° C.
The reaction was stopped by adding morpholine. 1600 parts of methyl ethyl ketone was added to this reaction liquid to obtain a polyurethane resin solution (a).

[Procedure amendment 4]

[Document name to be amended] Statement

[Name of item to be corrected] 0025

[Correction method] Change

[Correction content]

Example 2 Polyamino Acid Urethane Copolymer Resin 900 parts and 200 parts of polytetramethylene glycol and polyethylene glycol having a number average molecular weight of 2,000, respectively.
Parts, 3000 parts of methyl ethyl ketone to 63.86 parts of ethylene glycol, and dissolved at 50 ° C., 2 parts of a solution of 10% dibutyltin dilaurate in methyl ethyl ketone was added as a catalyst, and then 400 parts of 4,4′-diphenylmethane diisocyanate was added. .. The reaction is continued under refluxing of this mixed solution with methyl ethyl ketone, and the viscosity of the reaction solution becomes 10
When the temperature reached 10,000 cps / 30 ° C, morpholine was added to stop the reaction. Methyl ethyl ketone 1600 was added to this reaction solution.
Parts were added to obtain a polyurethane resin solution. To 500 parts of the polyurethane resin solution thus obtained, 2.5 parts of adipic dihydrazide was added and stirred at 30 ° C. for 10 minutes, then 90 parts of methyl isobutyl ketone and 120 parts of toluene.
34.5 parts of γ-methyl-L-glutamic acid NCA was dissolved in a mixed solution of 80 parts of methyl ethyl ketone and 80 parts of methyl ethyl ketone, and the resulting solution was added to the resin solution and polymerized at 30 to 40 ° C. for 3 hours to obtain a polyamino acid urethane copolymer resin (roth). ) Got.

[Procedure Amendment 5]

[Document name to be amended] Statement

[Correction target item name] 0038

[Correction method] Change

[Correction content]

Example 8 Using the resin solutions obtained in Examples 2, 4, 5 and 6, Table 2
A resin composition was obtained with the additive composition shown in FIG. 30 parts of water, surfactant E to 100 parts of solid content of this resin composition
1 part of MALEX103 (manufactured by Nippon Emulsion Co., Ltd.),
The emulsion solution obtained by adding C-229810 parts and stirring at high speed was dried on nylon taffeta (flexibility 48 mm) .
Coat with a roll coater to a coating amount of 10 g / m ² and perform two-step drying at 80 ° C. × 5 minutes, 120 ° C. × 5 minutes to remove the solvent and water to form a porous highly moisture-permeable cloth foil. Obtained. Table 3 shows the results of evaluating the abrasion resistance, washing resistance, and water vapor transmission rate of these cloth foils.

[Procedure Amendment 6]

[Document name to be amended] Statement

[Item name to be corrected] 0040

[Correction method] Change

[Correction content]

[0040]

[Table 3]

[Procedure Amendment 7]

[Document name to be amended] Statement

[Correction target item name] 0042

[Correction method] Change

[Correction content]

[0042]

When polyamino acid urethane resin prepared according to the present invention, Ri by <br/> to reacting readily available hydrazide compounds, discoloration due to day light, ultraviolet light, heat, nitrogen oxides, etc., holds the durability against deterioration In addition, the compatibility with the resin can be solved, and the polyamino acid urethane resin composition can be processed to obtain a breathable waterproof cloth having excellent wear resistance and waterproofness.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Masaho Enomoto 1109 Junwa, Iwatani, Ikawadani, Nishi-ku, Kobe-shi, Hyogo Seiko-Kasei Co., Ltd.

Claims (2)

[Claims] 1. A polyamino acid urethane resin containing a hydrazide compound. 2. A cloth foil obtained by applying a resin composition comprising a polyamino acid urethane resin containing a hydrazide compound to a fiber base material.