JPS61173929A - Porous composite material - 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 <Industrial Application Field> The present invention relates to a porous composite material made of a polyamino acid urethane copolymer resin. A polyamino acid urethane copolymer resin composition consisting of glutamic acid-γ-methyl ester N-carboxylic acid anhydride is coated on a fabric, and it has excellent moisture permeability, chemical resistance, and resistance to hydrolysis in the groin provided by a wet method. It is intended to provide a porous composite material.

<Conventional technology and its problems> Conventionally, polyamino acid resin (poly L-glutamic acid-γ-
It is known that methyl ester) has excellent hydrolysis resistance, chemical resistance, and moisture permeability, but on the other hand, it is brittle and is not suitable for applications that require flexibility, so it is not suitable for polyurethane resins. It is used as a polyamino acid urethane copolymer resin by copolymerizing with.

However, conventional polyurethane resins consisting of polyol components (e.g., polyether glycol, polyester glycol, polycaprolactone, etc.) and diisocyanate are combined with L-glutamic acid-γ-methyl ester N-carboxylic acid anhydride (hereinafter abbreviated as L-GNCA). ) was copolymerized with polyamino acid urethane resin, which had poor hydrolysis resistance and chemical resistance (acid resistance, alkali resistance), and was unable to fully demonstrate the characteristics of polyamino acid resin.

<Means for Solving the Problems> The present invention was obtained as a result of studies to eliminate the above-mentioned drawbacks of conventional products.

That is, this invention uses 1,6-hexane polycarbonate diol in place of the polyol component conventionally used in polyurethane resins, and copolymerizes L-GNCA with a polyurethane resin consisting of 1,6-hexane polycarbonate diol and an organic diisocyanate. The obtained polyamino acid urethane resin has significantly improved hydrolysis resistance and chemical resistance compared to conventional resins.

In addition, conventional wet methods in which woven fabrics are coated, immersed in water to coagulate, and the solvent is removed have been used to form porous layers such as polyurethane resins, polyamino acid resins, and copolymerized resins with other resins. A product or blend is introduced or put into practical use.
~ However, all of these have a common drawback of poor hydrolysis resistance and chemical resistance.

<Function> The polyamino acid urethane resin used in this invention, which is composed of a polyurethane resin containing 1.6-hexane polycarbonate diol and L-GNCA, has excellent hydrolysis resistance and chemical resistance, and can be made porous by a wet method. When a thin film is formed, it exhibits extremely high moisture permeability.

This performance can be used for processing various fabric materials such as wet processing, impregnation processing, and dry processing, and resin-treated clothing fabrics with excellent wash resistance, especially high moisture permeability.
It is also ideal as a durable sports clothing fabric and footwear base material, and can also exhibit excellent performance in industrial material applications such as abrasive cloths that require chemical resistance.

Next, the polyurethane resin containing 1,6-hexane polycarbonate diol and L-GNCA used in this invention will be explained in detail.

11. 6-Hexane polycarbonate diol alone or other diols are added as needed depending on the application, and an organic diisocyanate is added thereto to obtain a prepolymer having isocyanate at the terminal.

Examples of organic diisocyanates include 1,6-hexamethylene diisocyanate, 4.,4' diphenylmethane diisocyanate (MDI), isophorone diisocyanate, toluene-2,4-diisocyanate, and 4.4-hexamethylene diisocyanate. '-dicyclohexylmethane diisocyanate (H12MD
I), etc.

Other diols used in combination with 1,6-hexane polycarbonate diol include ethylene glycol, 1.
4-butanediol and the like can be used.

Next, chain extension is carried out while gradually adding the above prepolymer to a separately prepared solution of diamine in dimethylformamide.

Diamines include 4,4'-diphenylmethane diamine, isophorone diamine, anhydrous piperazine, hydrated hydrazine,
Examples include 4.4'-dicyclohexylmethanediamine.

At the end of the reaction, the terminal amino group is quantified, and the terminal amino group is regarded as -NH2 group, and the weight fraction is 200 to 300.
An appropriate point within the range of 0 ppm is set.

Next, the production of the polyamino acid urethane resin copolymer may be carried out according to JP-A-59-36132. For example, in a solution containing 100 parts by weight of a polyurethane resin having terminal amino groups, 7 to 85 parts by weight of L-GNCA and Add tertiary amine catalyst if necessary and stir for 3-5 hours, then
The temperature is raised to 0-70°C and stirred for 1-2 hours.

The polyamino acid urethane resin solution thus obtained is coated on a woven fabric (e.g. nylon, polyester fabric) or non-woven fabric, immersed in water or hot water, DMF removed, wet film formed, and then dried. It was recognized that the material had excellent hydrolysis resistance, chemical resistance, and moisture permeability.

That is, regarding hydrolysis resistance, the number of days for the wet porous film to maintain the breaking strength of 80% in the jungle test at 70°C and 95% humidity was 10 days in the comparative example (conventional product), but in the case of the present invention In the example, it was maintained for more than 200 days and a significant improvement was observed.

Furthermore, regarding alkali resistance and acid resistance, when immersed for 7 days in 40% sodium hydroxide and 35% hydrochloric acid, respectively, the comparative example decomposed, but no abnormality was observed in the example, and the chemical resistance was excellent.

<Example> This invention will be explained below with reference to Examples.

Example 1 (A) Production of polyamino acid urethane resin 1. 128 parts of 6-hexane polycarbonate, 1 part of ethylene glycol,
0 parts, 4.4'-diphenylmethane diisocyanate 4
0 parts and 170 parts of dimethylformamide were charged into a polymerization vessel, and maintained at 70 to 80°C for 1 hour while stirring to obtain a prepolymer having an average molecular weight of 2000.

While stirring a separately prepared solution consisting of 13.6 parts of isophoronediamine and 562 parts of dimethylformamide, the prepolymer obtained above was added little by little at room temperature, and the terminal amino groups were measured, and when the terminal amino group reached 1120 ppm. The addition of the prepolymer was stopped at , and the reaction was terminated.

The obtained polyurethane resin solution has a concentration of 20% and a viscosity of 25
．． 300 parts of dimethylformamide and 1 part of 10% tributylamine were added to 600 parts of this polyurethane resin solution, which was heated at ooocps/atao°C, and 50 parts of L-GNCA was added at 30°C with stirring and maintained for 3 hours.

Next, the temperature was raised to 60°C and stirred for 1 hour to obtain a polyamino acid urethane resin solution.

This solution has a concentration of 20% and a viscosity of 20000CDS/at3.
It was 0°C.

(B) Manufacture of porous composite material The polyamino acid urethane resin solution obtained in (A) was applied to nylon taffeta with 1009/metal coating, immersed in water at 20°C for 30 minutes, and thoroughly dried. A nylon taffeta with a white film was obtained.

In addition, resin films were prepared using conventional polyurethane resins and polyamino acid urethane resins in the same manner, and the results were as shown in Table 1 for comparison.

In addition, the polyamino acid urethane obtained in (A>) was coated on a glass plate, immersed in water at 20°C for 60 minutes, and then dried to form a porous film with a thickness of 450μ.
The physical properties of the film were also measured and are shown in Table 1.

Example 2 (A> Production of polyamino acid urethane resin 140 parts of 1,6-hexane polycarbonate diol used in Example 1 and 36.7 parts of H12M DI were charged into a polymerization container.
After keeping it at 100℃ for 4 hours while stirring, DMF
177 parts were added to obtain a prepolymer.

11.9 parts of isophoronediamine and DMF5 prepared separately
While stirring the solution consisting of 78 parts, the prepolymer was added little by little at room temperature, and the reaction was stopped at 4 ppm of terminal amino group 9B.

As a result, the concentration was 20%, the viscosity was 18000 cps/at3
A polyurethane resin solution at 0°C was obtained.

This polyurethane resin solution and L-GNCA were reacted in the same manner as in Example 1 (A) to a concentration of 20% and a viscosity of 1500.
A polyamino acid urethane resin solution of 0 cps/at 30°C was obtained.

(B) Production of porous composite material A microporous white membrane was obtained in the same manner as in Example 1 (B).

When this was compared with polyurethane resin and polyamino acid urethane in the same manner as in Example 1, the results shown in Table 1 were obtained.

Comparative Example 1 140 parts of 1.4-butanediol-adipate polyester with an average molecular weight of 2000 and 31.1 parts of isophorone diisocyanate were charged into a polymerization container, and 100 parts of
After keeping at ℃ for 4 hours, 171 parts of DMF was added to obtain a prepolymer.

11.9 parts of inphorondiamine and DMF5 prepared separately
While stirring a solution consisting of 61 parts, 1250 ppm of terminal amine groups were added while adding the prepolymer little by little at room temperature.
When the reaction is stopped, the concentration is 20% and the viscosity is 16,000 cp.
A polyurethane resin solution of s/at 30'c was obtained.

When this polyurethane resin solution and L-GNCA were reacted in the same manner as in Example 1 (A), the concentration was 20% and the viscosity was 1.
A polyamino acid urethane resin solution of 9000 cps/at30'c was obtained.

This polyamino acid urethane resin solution was prepared as (B) in Example 1.
When processed into nylon taffeta in the same manner as above, nylon taffeta with a microporous white film was obtained.

When this was compared with Examples 1 and 2, the results shown in Table 1 were obtained.

Comparative Example 2 Average molecule consisting of ethylene glycol, 1,4-butanediol and adipic acid! 2000 polyester 120
1 part, 8.7 parts of ethylene glycol, and 400 parts of DMF were placed in a polymerization vessel, and 50 parts of MDI was added while stirring and maintained at 80°C for 2 hours. Then, 315 parts of DMF was added, resulting in a polymer with a concentration of 20% and a viscosity of 10,000 cps/at 30°C. A Boliu L/Tan resin solution was obtained.

When this polyurethane resin solution was processed into nylon taffeta in the same manner as in Example 1 (B), nylon taffeta having a microporous white film was obtained. Its performance is shown in Table 1.

Notes to Table 1 *Hydrolysis resistance is the number of days in which the retention rate of breaking strength is 80%.

<Effects of the Invention> As described above, the porous composite material of this invention has hydrolysis resistance,
It was found to have excellent chemical resistance and high moisture permeability.

Claims (1)

[Claims] 1 in a water-soluble solvent mainly composed of dimethylformamide.
, 6-hexane polycarbonate diol-containing polyurethane resin and L-glutamic acid-γ-methyl ester N
- A porous composite material obtained by coating a fabric with a composition obtained by polymerizing a carboxylic acid anhydride and then immersing it in water.