JPH0588736B2 - - Google Patents

Description

[Detailed description of the invention]

<Industrial Application Field> The present invention relates to a polyamino acid urethane resin composition with excellent wet film-forming properties. <Conventional techniques and their problems> Conventional methods for producing polyamino acid urethane resins include: (1) A urethane prepolymer or polyurethane resin having terminal isocyanate groups and L-glutamic acid γ-methyl ester N-carboxylic acid anhydride ( (hereinafter referred to as LG-NCA) (Japanese Patent Application Laid-Open No. 58-57420). (2) Polyurethane resin with terminal amino groups and
By copolymerization with LG-NCA (Unexamined Japanese Patent Publication No. 1983-
No. 36132). (3) A method of polymerizing LG-NCA in a polyurethane resin solution (Japanese Patent Publication No. 49-31559). etc. are known. However, although the polyamino acid urethane resins obtained by these manufacturing methods produce porous films by wet methods, they have poor wet film formability compared to wet method polyurethane resins, and have unfavorable productivity. <Means for Solving the Problems> In view of the above, the present invention aims to produce a porous film having a large number of unique fine pores, which has the same film forming performance as a wet polyurethane resin, by a wet method. The present invention was developed as a result of extensive research in order to obtain a polyamino acid urethane resin that can be used. That is, the present invention relates to a polyamino acid urethane resin obtained by polymerizing L-glutamic acid γ-methyl ester N-carboxylic acid anhydride to a polyurethane resin having a terminal isocyanate group or a terminal amino group using an aliphatic isocyanate. A mixture of 10 to 50% by weight of a polyamino acid urethane resin obtained by polymerizing L-glutamic acid γ-methyl ester N-carboxylic acid anhydride to a polyurethane resin having a terminal isocyanate group or a terminal amino group using an aromatic isocyanate group. The present invention provides a polyamino acid urethane resin composition having excellent wet film forming properties. <Function> This invention uses two types of polyurethane resins: a general non-yellowing type polyurethane resin that is difficult to form into a wet film, and a type of polyurethane resin that has good wet film formation properties, but which undergoes copolymerization. This method involves mixing a predetermined amount of polyamino acid urethane resins, and although it is impossible to form a wet film by itself, or even if it is possible, it is quite slow, the wet film formation becomes faster by mixing. It was recognized that it was superior to that of wet polyurethane resin. The purpose of creating a wet film by copolymerizing amino acids in this way is to obtain a film with excellent moisture permeability, hydrolyzability, drapability, etc. In this invention, the polyurethane resins used to obtain two types of polyamino acid urethane resins are not compatible with each other, and it is preferable to use resins that are compatible with each other by copolymerizing amino acids. These two types of polyamino acid urethane resins can be mixed in any ratio to form a semitransparent and uniform dry film, but from the viewpoint of wet film formability, which is the main objective of this invention, A suitable mixing range is 10 to 50% by weight of the polyamino acid urethane resin (B) made of polyurethane using an aromatic isocyanate to the polyamino acid urethane resin (A) made of polyurethane using an isocyanate. When a polyamino acid urethane resin composition having such a mixing ratio is used, the resulting porous film has many fine pores on the surface of the film, forming an uneven surface, unlike polyurethane resins, and the inside of the film is In this case, it is possible to form a structure having small holes that communicate with each other in the cross-sectional direction. <Examples> The present invention will be explained below using examples. All parts are by weight. Example 1 (1) 264 parts of ester diol with a molecular weight of 3000 obtained by ring-opening polymerization of ε-caprolactone using ethylene glycol, 1.36 parts of ethylene glycol, and 57.6 parts of 4,4'-dicyclohexylmethane diisocyanate, which is an aliphatic isocyanate. A portion of the mixture was charged into a reaction vessel and reacted in a nitrogen stream at 100°C for 4 hours to obtain a terminal isocyanate prepolymer. In a separate reaction vessel, 18.7 parts of isophoronediamine and 1366.8 parts of dimethylformamide were mixed and stirred uniformly. The prepolymer having terminal isocyanate groups obtained above was gradually added to this mixed solution while stirring, and the amino value was 150 ppm and the viscosity was
A polyurethane resin solution having a solid content of 20% and a temperature of 30.000 cps/30°C was obtained. Next, 1708.5 parts of this polyurethane resin solution and 600 parts of dimethylformamide were charged into a reaction vessel.
The mixture was stirred uniformly and the solution temperature was brought to 30°C. Then, while stirring, 192 parts of L-glutamic acid γ-methyl ester N-carboxylic anhydride and 10 g of a 10% tributylamine solution were added, and the mixture was reacted at 30°C for 8 hours. As a result, an amino acid urethane copolymer resin solution (A) with a viscosity of 45.000 cps/30°C and a solid content of 20% was obtained.
I got it. (2) 133 parts of butylene adipate with a molecular weight of 4000, 53 parts of ethylene glycol, dimethylformamide
467 parts of 4,4'-diphenylmethane diisocyanate and 55.4 parts of 4,4'-diphenylmethane diisocyanate were charged into a reaction vessel and reacted for 2 hours at 70°C under a nitrogen stream. Next, after cooling to 50℃, 13 parts of ethylene glycol was added in portions while measuring the isocyanate value.
A chain lengthening reaction is performed to increase the terminal isocyanate value.
1500ppm, solid content 30%, viscosity 20.000cps/30℃
A polyurethane resin solution was obtained. 666.9 parts of this polyurethane resin solution and 51.8 parts of dimethylformamide were charged into a reaction vessel, stirred uniformly to bring the solution concentration to 30°C, and while stirring, L-glutamic acid γ-methyl ester N
-29.1 parts of carboxylic acid anhydride, tributylamine
1.5 g of a 10% solution was added and the reaction was carried out at 30°C for 8 hours. As a result, an amino acid urethane copolymer resin solution (B) was obtained at 25,000 cps/30° C. and with a solid content of 30%. (3) Amino acid urethane copolymer resin solution obtained above
A mixed solution in which 10 to 50 parts of (B) was mixed with 100 parts of (A) had better wet film forming properties than each solution (A) or (B) alone. In particular, when a mixed solution of (A)/(B) = 100/30 was applied to a glass plate, immersed in water for 30 minutes, and then dried at 80°C for 10 minutes, a dense porous film was obtained. The porous film obtained in Example 1 can be used as a film made of resin liquid (A) or resin liquid (B), respectively, or a film made of a mixed liquid of resin liquid (A)/(B) = 100/80. When we conducted moisture permeability and other tests, we obtained the results shown in Table 1.

[Table] Measures the immersion time in water.
Example 2 Molecular weight of ring-opening polymerization of tetrahydrofuran
3000 polytetramethylene ether glycol
244, 2 parts, ethylene glycol 3.36 parts, 4,
4'-dicyclohexylmethane diisocyanate
71.1 part was charged into a reaction vessel and heated to 100% in a nitrogen stream.
The mixture was reacted at ℃ for 4 hours to synthesize a terminal isocyanate prepolymer. In a separate container, 23.1 parts of isophorone diamine and 1336.6 parts of dimethylformamide were mixed and stirred uniformly. The terminal isocyanate prepolymer obtained above was gradually added to this mixed solution while stirring to obtain a polyurethane resin solution with an amine value of 1800 ppm, a viscosity of 35000 cps/30°C, and a solid content of 20%. 4 parts of this polyurethane resin solution and 600 parts of dimethylformamide were charged into a reaction vessel, stirred uniformly to bring the solution temperature to 30°C, and then L-glutamic acid γ-methyl ester N-carboxylic anhydride
Add 192 parts and 10 parts of tributylamine 10% solution,
The reaction was carried out at 30°C for 8 hours. As a result, an amino acid urethane copolymer resin solution (A') having a viscosity of 52,000 cps/30°C and a solid content of 20% was obtained. This resin solution (A') and the resin solution (B) obtained in Example 1 were mixed at a ratio of (A')/(B)=100/10.
Then, apply this mixture to a glass plate and submerge it in water for 30 minutes.
After soaking for 1 minute, drying at 80°C for 10 minutes yielded a dense porous film. When this porous film was subjected to the same test as in Example 1, the results shown in Table 2 were obtained. In addition, as a comparative example, a film made of resin solution (A') and (B) each alone, and a film made of resin solution (A') / (B) =
A film made of a 100/70 mixed solution was used.

[Table] <Effects of the Invention> As detailed above, the porous film obtained using the polyamino acid urethane resin composition of the present invention has excellent moisture permeability, weather resistance, etc. It was also observed that the film formation rate when obtained using the method was very good.

Claims (1)

[Claims] 1 L-glutamic acid γ-methyl ester N is added to a polyurethane resin having a terminal isocyanate group or a terminal amino group using an aliphatic isocyanate.
- L-glutamic acid γ-methyl ester N- Polyamino acid urethane resin (B) made by polymerizing carboxylic acid anhydride
A polyamino acid urethane resin composition with excellent wet film formability characterized by containing 10 to 50% by weight.