JPH04279635A - Polyamino acid urethane resin and product using the same - Google Patents

Abstract

PURPOSE:To provide the subject resin solution which is a polyamino acid urethane resin solution, used for obtaining fabrics simultaneously having both functions of moisture permeability and waterproofness and excellent in preservation stability of the solution and uniform coating properties. CONSTITUTION:A polyamino acid urethane resin solution is obtained by reacting a polyurethane resin having amino groups of 1-130ppm amine value at both terminals with an amino acid N-carbonic acid anhydride. The resultant resin solution has 5-95wt.% content of amino acid residue. The preservation stability and uniform coating properties of the resin solution are excellent and moisture permeable waterproof fabrics obtained by using the aforementioned resin solution according to a wet process have performance of >=1500mm water-resistant pressure and >=7000g/m<2>.24hr moisture permeability. When the abovementioned resin solution is used in a dry process, the fabrics have characteristics of hand and touch close to those of natural leather, sweat absorptivity and heat resistance.

Description

[Detailed description of the invention]

0001

[Industrial Application Field] The present invention relates to polyamino acid urethane resins and products using the same, and more specifically to polyurethane resins having amino groups at both ends with an amine value of 1 to 130 ppm and acidic amino acid ω-alkyl N-carbonic anhydrides. A polyamino acid urethane resin containing 5 to 95% by weight of amino acid residues obtained by reacting amino acid N-carbonic anhydride, which is mainly composed of amino acids, or a polymer compound further mixed with the resin. The present invention relates to a composition and a product using the same.

0002

[Prior art and its problems] Conventionally, polyamino acid urethane resin (hereinafter referred to as PAU) maintains the characteristics of polyamino acids such as high moisture permeability and abrasion resistance, and improves shortcomings such as elasticity and adhesion. When used in the production of synthetic leather, artificial leather, moisture-permeable waterproof fabric, etc., products with excellent moisture permeability, texture, and strength can be obtained. Because it uses halogen-based hydrocarbons, wet processing is difficult, and it can only be produced by dry methods.

[0003] When PAU produced by a dry process is made into a film and used as a skin material for synthetic leather, or
When AU is used as a surface treatment agent for synthetic leather, artificial leather, etc. using a gravure printer (Japanese Patent Publication No. 52-278
No. 61), or when the PAU is used as a spray treatment agent to modify the surface of molded products, etc., the characteristics of PAU include the texture and feel of the surface, which is extremely similar to natural leather, sweat absorption, heat resistance, etc. However, because it uses conventional halogen-based hydrocarbon solvents, it is difficult to use industrially due to environmental hygiene problems and corrosion problems of equipment. Ta.

Furthermore, the neutral amino acid N-
It is also known that carbonic anhydride (hereinafter N-carbonic anhydride is abbreviated as NCA) and acidic amino acid ω-alkyl NCA are used together to react with a polyurethane resin to obtain PAU without using a halogenated hydrocarbon solvent. (Unexamined Japanese Patent Publication No. 1983
-54020), from an industrial standpoint, the neutral amino acid NCA is expensive, making it difficult to use in large quantities.

[0005] Next, as a method for producing PAU using DMF as a water-miscible organic solvent in PAU used to obtain synthetic leather or fabric by a wet method, (1) a urethane prepolymer having an isocyanate group at the end; A method for obtaining a random copolymer by reacting γ-methylglutamic acid NCA with water, hydrazine, or an organic amine having active hydrogen (JP-A-60-154054, JP-A-60-1
62872, JP-A No. 61-40315), or (2) a polyurethane resin having terminal amino groups with an amine value controlled within the range of 150 to 3000 ppm, γ-methylglutamic acid NCA, and a tertiary amine catalyst. Method for obtaining PAU (Unexamined Japanese Patent Publication No. 61-17
No. 3929, JP-A No. 62-25156), etc. are known.

However, when these conventional methods are carried out industrially, problems have been pointed out during reaction, storage and operation.

That is, PAU obtained by method (1) requires frozen storage for long-term storage, and if it is not frozen, the viscosity of the solution increases sharply over time, making coating processing impossible.

In addition, in method (2), the viscosity during the reaction becomes rubber elastic, making it difficult to achieve a uniform reaction.Furthermore, even if a uniform reaction occurs, the resulting resin is coated with a highly viscous resin. Therefore, uniform coating is difficult.

[0009] Furthermore, in the case of a moisture-permeable waterproof fabric using PAU, the water pressure resistance was determined by JI in Japanese Patent Application Laid-Open No. 162872/1983.
Water pressure resistance measured according to SL-1079 is 1500mm
In addition, it is known that the moisture permeability is 7000 g/m 2 ·24 hrs or more when measured in accordance with JIS Z-0208.

[0010] However, even with such a moisture-permeable waterproof fabric using PAU, the above-mentioned storage and viscosity problems have not been solved.

[0011] In addition, the so-called wet coagulation method (Japanese Patent Publication Publication No. 1983-1983) involves coating a fiber base material with a water-miscible solvent solution of polyurethane resin and then immersing it in a water bath to form a microporous film made of polyurethane resin. No.-47955, JP-A-5
No. 9-145139), for coated fabrics with a water pressure resistance of 1500 mm or more, the moisture permeability is 5000 g/m2.
・I can only get about 24 hours.

[0012] In addition, a moisture-permeable waterproof fabric is manufactured by using polyvinylidene fluoride/polyurethane that does not have uniform mixing, and by applying shear to the resin during coating, particularly long cells are formed in a direction parallel to the fabric surface. A method (Japanese Patent Publication No. 63-60156) is also known, but the liquid separation of the liquid mixture is severe and there is a problem in putting it to practical use.

[0013]

[Means for Solving the Problems] In view of the problems of the conventional method described above, the present inventors have made extensive studies and have developed a polyurethane resin having amino groups at both ends with an amine value of 1 to 130 ppm and an acidic amino acid. When a polyamino acid urethane resin obtained by reacting amino acid NCAs mainly composed of ω-alkylNCA is used as a resin for moisture permeable waterproof fabric by a wet method, it has a water vapor permeability of 700 at a water pressure resistance of 1500 mm or more.
It has a performance of 0g/m2・24hrs or more, and has excellent liquid storage stability and uniform coating properties, and when used in the dry method, it has a texture, feel, sweat absorption, and heat resistance similar to that of natural leather. The inventors have discovered that this invention has the following characteristics and can solve the problems caused by the reaction solvent.

That is, this invention has an amine value of 1 to 130 pp.
The content of amino acid residues obtained by reacting a polyurethane resin having m amino groups at both ends with an amino acid N-carbonic anhydride mainly composed of acidic amino acid ω-alkyl N-carbonic anhydride is 5 to 95% by weight. % of polyamino acid urethane resin, or even 0.0% per part by weight of the resin.
A resin composition characterized by being obtained by mixing 01 to 20 parts by weight of a polymer compound, and synthetic leather, artificial leather, fabric or molding obtained by coating the resin and the composition as a treatment agent. The purpose is to provide products.

[0015]

[Operation] This invention will be explained in detail below.

First, the polyurethane resin used to obtain the PAU of the present invention will be described.
000 polyalkylene ether glycol, polyester polyol having hydroxyl groups at both ends, polyε-caprolactone polyol or polycarbonate diol alone or as a mixture, and if necessary, diol etc. 2
An organic diisocyanate is added to a mixture containing a compound having active hydrogens to obtain a prepolymer having terminal isocyanate groups.

Next, the prepolymer obtained above is added to a separately prepared solution of a diamine in an organic solvent mainly composed of DMF to effect chain extension. The end point of the reaction is determined by measuring the amine value, and the weight fraction is 1 to 130 ppm, preferably 2 to 130 ppm.
50 ppm, thus obtaining the polyurethane resin used for PAU preparation.

The end point of the reaction of this resin was determined to be 1 by measuring the amine value.
~130ppm means that the amine value is 130ppm
If it exceeds, the viscosity during the reaction with the amino acid NCA to obtain PAU becomes rubber elastic, making it difficult to carry out a uniform reaction.
Furthermore, even if a uniform reaction occurs, uniform coating becomes difficult when performing wet coating using the obtained PAU due to the high viscosity of the resin.

The polyalkylene ether glycol used above includes polytetramethylene ether glycol, polypropylene glycol, polyethylene glycol, glycerin propylene oxide adduct, polyether polyol with ethylene oxide added to the terminal,
Examples include vinyl monomer-grafted polyether polyols.

[0020] Polyester polyols include ethylene glycol, butylene glycol, hexylene glycol, diethylene glycol, dipropylene glycol,
Alkylene glycols such as neopentyl glycol are reacted with carboxylic acids such as succinic acid, glutaric acid, adipic acid, sebacic acid, maleic acid, fumaric acid, phthalic acid, and trimellitic acid so that the terminal becomes a hydroxyl group. What is given is good.

Compounds having two active hydrogens such as diols include ethylene glycol, butylene glycol, hexylene glycol, diethylene glycol, dipropylene glycol, neopentyl glycol, 4,4'-
Diphenylmethanediamine, 4,4'-dicyclohexylmethanediamine, hydrazine, ethylenediamine, tetramethylenediamine, water, piperazine, isophoronediamine, etc. are used alone or in combination.

As the organic diisocyanate, 2,4-
and 2,6-toluylene diisocyanate, 4,4'
- Aromatic isocyanates such as diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, xylylene diisocyanate, 1,6-hexamethylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, isophorone diisocyanate, 2,
There are aliphatic isocyanates such as 6-diisocyanate methyl caproate, which can be used alone or in combination.

As the diamine, 4,4'-diphenylmethanediamine, 4,4'-dicyclohexylmethanediamine, hydrazine, ethylenediamine, tetramethylenediamine, piperazine, isophoronediamine, etc. are used alone or in combination.

[0024] When using the obtained resin in a wet method, any water-miscible organic solvent may be used as the organic solvent solution containing DMF as a main component. When used in a dry method, conventionally known organic solvents such as toluene and methyl ethyl ketone can be used.

Next, amino acid NCAs mainly composed of acidic amino acid ω-alkyl NCAs and optionally a tertiary amine catalyst are added to the above polyurethane resin solution having terminal amino groups, and the mixture is stirred for 3 to 10 hours. PAU
A solution is obtained.

The acidic amino acid ω-alkylNCA includes γ-methyl-glutamate NCA, γ-ethyl-glutamate NCA, γ-benzyl-glutamate NCA,
Examples include β-methyl-aspartate NCA, which may be used in either an optically active form or a racemic form, and these may be used alone or in combination.

Furthermore, the above acidic amino acid ω-alkyl N
It is also possible to use CA in combination with the neutral amino acid NCA. In this case, the amount of neutral amino acid NCA used is 5% by weight.
A range not exceeding 0% is preferable.

Examples of the neutral amino acid NCA include valine, norvaline, leucine, isoleucine, norleucine, phenylalanine, and methionine, and these may be used in either an optically active form or a racemic form, and these may be used alone or as a mixture. and can be used.

[0029] The content of amino acid residues in the PAU of this invention is 5 to 95%. If it is less than 5%, high moisture permeability and natural leather-like texture cannot be obtained, and if it is less than 95%
This is because if it is contained in a larger amount, the texture becomes hard, the coating film has no strength, and the adhesion to base materials such as synthetic leather and fabric is unfavorable.

[0030] If necessary, a polymer compound can be added to the PAU of the present invention.

Examples of polymeric compounds that can be added include urethane resins such as polyurethane resins, polyurethane urea resins, and polyurea resins, fluororesin copolymers, acrylic resins, acrylic rubbers, silicone resins, vinyl chloride resins, and epoxy resins. Copolymers of urethane resins and other resins may be used alone or in mixtures.

The amount of the polymer compound to be used is preferably 0.01 to 20 parts by weight per 1 part by weight of PAU of the present invention. If this is less than 0.01 part by weight, it is preferable to add a surfactant, which is a conventionally known film-forming aid, for high moisture permeability and wet film-forming properties when the obtained PAU is used in a wet method. This is because if the amount exceeds 20 parts by weight, the natural leather feel, heat resistance, sweat absorption, etc. will be poor.

[0033] Next, a conventionally known organic solvent is added to the PAU or resin composition of the present invention as necessary to obtain a treatment agent, and molded products, synthetic leather, and artificial leather obtained by coating the treatment agent will be explained. do.

[0034] When a spray treatment agent was prepared using the PAU of the present invention and an organic solvent and applied to the surface of an ABS molded product, it had a texture and feel very similar to natural leather, sweat absorption,
Scratch resistance, jet blackness, and matteness were improved, and the surface could be modified without leaving any fingerprint marks.

[0035] Furthermore, a treatment agent consisting of PAU of the present invention and an organic solvent is coated onto a release paper by a dry method to form a film.
Similar effects and even higher moisture permeability are observed when used for surface materials such as synthetic leather, and when applied to the surface of synthetic leather, artificial leather, etc. using a gravure printer. It was suitable as a treatment agent for synthetic leather and artificial leather.

[0036] Furthermore, when the PAU of the present invention or a resin composition comprising PAU and a polymer compound is used for wet processing of wet synthetic leather or artificial leather used for shoes, furniture, vehicles, sporting goods, etc., Due to the difference in solidification rate between the amino acid segment and the urethane segment in the PAU resin, or the difference in the solidification rate between the PAU resin and the polymer compound, the cell forming ability is better than that of commonly used wet urethane resins. As a result, fine cells are formed even in areas close to the coating substrate, making it possible to finish wet synthetic leather or artificial leather with a soft texture with excellent drapability, as well as moisture permeability and
It also has an effect on air permeability.

[0037] Furthermore, the PAU of the present invention or the resin composition comprising PAU and a polymer compound can be coated on a base material such as a textile and subjected to a wet treatment to provide moisture permeability with excellent moisture permeability and water pressure resistance. A waterproof fabric can be obtained.

That is, when PAU or a resin composition consisting of PAU and a polymer compound is coated on a substrate and immersed in water, the solidification rate difference between the amino acid segment and the urethane segment in PAU causes Spaces are created between each resin due to the difference in solidification rate and solidification rate of the polymer compound, forming micropores. If the diameter of these micropores is small, the moisture permeability will decrease, and if the diameter is large, the water pressure resistance will be poor.

Therefore, the adjustment of the pore size, which is an important element in the present invention, is determined by the amino acid content in PAU and the content or composition of the polymer compound mixed with PAU.

[0040] This PAU or a resin composition composed of PAU and a polymer compound may be applied to a fiber base material such as nylon taffeta to obtain a highly moisture permeable waterproof fabric by a conventional coating method, and the coating thickness may be determined as follows: 10~300μ
m is appropriate.

[0041] The suitable water temperature when immersing the coated substrate in water is 0 to 30°C; if it is higher than 30°C, the pores of the resin film become large and the water pressure resistance performance decreases.

[0042] The dipping time must be 30 seconds or more. This is because if the time is less than 30 seconds, the solidification of the resin will be insufficient.

[0043] In order to completely remove the remaining water-miscible organic solvent, hot water washing at 30 to 80°C for 3 to 10 minutes may be performed. Water pressure resistance can also be improved by further applying a water repellent to the coated fabric obtained after washing with hot water and drying.

[0044] There are various types of water repellent such as paraffin type, silicone type, and fluorine type, and the appropriate one may be selected depending on the purpose. The water repellent may be applied by a conventional patting method, coating method, spraying method, or the like.

In addition, when using the PAU or resin composition of the present invention in a wet method, polyfunctional polyisocyanates (for example, Coronate, manufactured by Nippon Polyurethane Industries, Ltd.) may be used as additives to improve the adhesion to the coating substrate. It is also effective to add EH, Coronate HL) or a blocked polyfunctional polyisocyanate (manufactured by Huls, B-1370).

A nonionic surfactant may also be added as a speed regulator for solvent removal during wet coagulation.

[0047] The coated fabric thus obtained under the optimum conditions does not cause uneven coating, exhibits moisture permeability of 10,000 to 12,000 g/m2/24 hrs over the entire surface, and water pressure resistance of 1500 mm or more, and is suitable for golf wear, ski wear, etc. It can be used for a wide range of purposes, including sportswear, winter clothing, raincoats, and workwear.

[0048]

EXAMPLES Next, the present invention will be explained in detail with reference to Examples, but the present invention is not limited to these Examples. Note that all parts in the examples are parts by weight.

Example 1 (Preparation of polyamino acid urethane resin) (1-1) 62 parts of poly-ε-caprolactone polyol having an average molecular weight of 3000 and having hydroxyl groups at both ends, an average molecular weight of 3
000 polytetramethylene ether glycol, 0.6 part of ethylene glycol, and 27 parts of 4,4'-dicyclohexylmethane diisocyanate were uniformly mixed under a nitrogen stream and then heated to obtain a urethane prepolymer.

Next, the urethane prepolymer obtained above was gradually added to a solution prepared by adding and dissolving 8 parts of isophorone diamine in 904 parts of DMF, and the mixture was homogeneously mixed. After heating, the amine value was measured. )2ppm, (2
Three types of polyurethane resin solutions with a viscosity of 60,000 cps/30° C. and an amine value of (3) 50 ppm and (3) 200 ppm were obtained.

Next, 363 parts of the polyurethane resin solution with an amine value of 2 ppm from the above (1), 50 parts of γ-methyl-L-glutamate NCA, and 20 parts of leucine NCA were mixed in DMF.
Dissolve 158 parts of tributylamine in 1 part of tributylamine while stirring.
．． 14 parts and heated at 30°C for 5 hours until the solid content concentration was 1.
A polyamino acid urethane resin (PAU-1) having a viscosity of 9% and a viscosity of 80,000 cps/30°C was obtained.

Further, 363 parts each of the two types of polyurethane resin solutions having the amine values (2) and (3) above and 76 parts of γ-methyl-L-glutamate NCA were mixed in DMF.
Dissolve 158 parts of tributylamine in 1 part of tributylamine while stirring.
．． Add 14 parts and heat at 30°C for 5 hours to prepare 5 of (2).
A polyamino acid urethane resin (PAU-2) with a solid content concentration of 19% and a viscosity of 80,000 cps/30°C was obtained from a polyurethane resin solution with an amine value of 0 ppm, and 2 of (3)
A polyamino acid urethane resin (PAU-3) having a solid content concentration of 19% and a viscosity of 750,000 cps/30°C was obtained from a polyurethane resin solution having an amine value of 00 ppm.

(1-2) 53 parts of poly-ε-caprolactone polyol having an average molecular weight of 3000 and having hydroxyl groups at both ends, 0.3 part of ethylene glycol, 4,
4'-dicyclohexylmethane diisocyanate 12
．． After uniformly mixing and heating 1 part under a nitrogen stream, DMF
291 parts of isophorone diamine was added thereto, and further 35 parts of isophoronediamine were added to obtain a urethane prepolymer having isocyanate groups at the terminals.

Next, this urethane prepolymer 360
part and 36 parts of γ-methyl-L-glutamate NCA to 4 parts
Dissolved in 4 parts of DMF, added 0.2 parts of hydrazine hydrate dissolved in 10 parts of DMF with stirring, and heated at 30°C for 5 hours to obtain a solid concentration of 18% and a viscosity of 100,000 cp.
s/30℃ polyamino acid urethane resin (PAU-4)
I got it.

(1-3) 1000 parts of poly-ε-caprolactone polyol having an average molecular weight of 1000 and having hydroxyl groups at both ends and 500 parts of 4,4'-diphenylmethane diisocyanate were mixed uniformly under a nitrogen stream, and then heated. A urethane prepolymer was obtained.

Next, 54 parts of hydrazine hydrate was added to 8 parts of DMF.
The urethane prepolymer obtained above was gradually added to the dissolved solution in addition to 520 parts, mixed uniformly, and the amine value was measured after heating. A polyurethane resin solution at ℃ was obtained.

[0057] 968 parts of γ-methyl-L-glutamate NCA was dissolved in 10,070 parts of this polyurethane resin solution, and 14.5 parts of tributylamine was added with stirring, and the mixture was heated at 30°C for 5 hours until the solid content concentration was 20% and the viscosity was 20%. 60
,000cps/30℃ polyamino acid urethane resin (
PAU-5) was obtained.

Example 2 (Preparation of polymer compound) (2-1) 89 parts of poly-ε-caprolactone polyol having an average molecular weight of 3000 and having hydroxyl groups at both ends, and butylene having an average molecular weight of 3000 and having hydroxyl groups at both ends. 89 parts of adipate and 15 parts of ethylene glycol were uniformly mixed under a nitrogen stream, 75 parts of 4,4'-diphenylmethane diisocyanate was added thereto, and the mixture was heated in DMF until the solid content concentration was 3.
A polyurethane resin solution (U-1) with a viscosity of 0% and a viscosity of 80,000 cps/30°C was obtained.

(2-2) 20 parts of a 20% DMF solution of vinyl chloride-polyurethane resin copolymer (manufactured by Nippon Polyurethane Industries Co., Ltd., trade name Dominus K-650F) was added to (2-2)
1) was mixed with 80 parts of the polyurethane resin solution (U-1) obtained in step 1) to obtain a mixed solution (U-2) of vinyl chloride-polyurethane resin and polyurethane resin.

(2-3) 199 parts of ethylene butylene adipate having an average molecular weight of 4000 and having hydroxyl groups at both ends and 18 parts of ethylene glycol were stirred under a nitrogen stream to form a homogeneous mixture, and 4,4'-diphenylmethane diisocyanate was added to this mixture. Add 80 parts and heat in DMF to obtain a solid concentration of 30% and a viscosity of 60,000 cps/30.
A polyurethane resin solution (U-3) at ℃ was obtained.

Example 3 Polyamino acid urethane resin PAU-21 obtained in Example 1
A surface treatment agent (PAU-2C) was prepared by adding 25 parts of toluene and 25 parts of methyl ethyl ketone to 0.0 parts of the sample.

[0062] Using this treatment agent (PAU-2C), 50 g/m2 wet was applied onto synthetic leather for furniture and artificial leather for sports shoes using a gravure printer.
The surface was finished by drying at ℃ for 5 minutes.

The obtained leather was tested for physical properties such as texture, sweat absorption, and scratch resistance, and the results shown in Table 1 were obtained.

Comparative Example 1 Using a commercially available surface treatment agent made of a polyurethane resin solution (manufactured by Seiko Kasei Co., Ltd., trade name Luxkin U-97), 50g was applied to synthetic leather for furniture and artificial leather for sports shoes using a gravure printer. /m2wet coated, 1
The surface was finished by drying at 20° C. for 5 minutes.

Physical property tests such as texture, moisture absorption, and scratch resistance were conducted on the obtained leather, and the results were as shown in Table 1.
The results shown are obtained.

Example 4 Surface treatment agent (PAU-2C) prepared in Example 3 100
35 parts of methyl isobutyl ketone, 35 parts of cyclohexanone, 35 parts of ethylene glycol monomethyl ether
A spray treatment agent PAU-2S was prepared.

[0067] A molded product obtained by heat-molding an ABS sheet using this treatment agent was spray-painted at 100 g/m2 wet and dried at 120°C for 5 minutes.

The obtained product was subjected to the same physical property tests as in Example 3. The results are shown in Table 1.

Comparative Example 2 Commercially available polyurethane resin solution (Luxkin U-97)
A spray treatment agent (U-97S) was prepared by adding 35 parts of methyl isobutyl ketone, 35 parts of cyclohexanone, and 35 parts of ethylene glycol monomethyl ether to 100 parts.

This treatment agent was sprayed at 100 g/m2 onto a molded product obtained by heating and molding an ABS sheet.
It was dried at 20°C for 5 minutes. When the obtained product was subjected to physical property tests similar to those in Example 3, the results shown in Table 1 were obtained.

The evaluation criteria in the physical property test items in Table 1 are as follows. (1) Texture of coating ○: The texture is very similar to natural leather. ×: Cold feel peculiar to urethane. (2) Sweat absorption ○: The surface feels dry to the touch. ×: When touched with the hand, the surface feels sticky due to the sweat of the hand. (3) Scott abrasion Scott abrasion tester (manufactured by Uejima Seisakusho, UF-rubbe
r Tester) 1kg x 1000 times/25
This is a series evaluation in °C.

[0072]

[Table 1]

From the above table, it can be seen that the products using the processing agents PAU-2C and PAU-2S made of the resin of the present invention are more natural than those using the processing agents U-97 and U-97S made of commercially available polyurethane resin It has a leather-like texture, excellent sweat absorption, and is also scratch resistant and has no fingerprint marks.
In terms of Scott abrasion resistance, the surface strength was high and the required coating film properties were met.

Example 5 Polyamino acid urethane resin PAU-26 obtained in Example 1
To 0 parts, 100 parts of the polyurethane resin solution U-3 obtained in Example 2 (2-3) was added and mixed uniformly. A resin solution and a commercially available moisture permeable polyurethane resin solution (manufactured by Seiko Kasei Co., Ltd., trade name Luxkin U-3) were uniformly mixed. 360) were each made into a 10μ thick film on release paper using a dry method,
Further, a two-component urethane adhesive was applied thereon using a dot printer and laminated with a base material of nylon taffeta (wool fabric made of 6-nylon fibers) to obtain dry synthetic leather for clothing.

The moisture permeability and water pressure resistance of each of the synthetic leathers obtained were measured, and the results shown in Table 2 were obtained.

[0076] The water vapor permeability was measured according to JIS Z-0208, and the water pressure resistance was measured according to JIS L-1079.

[0077]

[Table 2]

From the above table, it can be seen that products using the resin of the present invention have higher moisture permeability and a dry feel when compared to products made of commercially available moisture permeable polyurethane resin solutions, and are suitable for dry synthetic leather for clothing. It met the physical properties required as

Example 6 Polyamino acid urethane resin PAU- obtained in Example 1
To 2100 parts, add 1 part of nonionic surfactant (manufactured by Dainippon Ink & Chemicals Co., Ltd., SD-7) and 30 parts of DMF,
A coating liquid was prepared by uniformly mixing. On the other hand, as a base material, a water-repellent base material was prepared by patting nylon taffeta (wool fabric made of 6-nylon fibers) with a 1% aqueous solution of a fluorine-based water repellent emulsion and heat-treating it at 160° C. for 1 minute.

[0080] The coating liquid prepared above was applied onto this substrate using a floating knife coater at a rate of 100 g/m.
After 2 wet coatings, the resin was immersed in a 20°C water bath for 8 minutes to solidify the resin. Then, in warm water at 50°C for 10
After soaking for a minute to fully extract DMF, drying was performed.

[0081] After that, 5 of the fluorine-based water repellent emulsion
% aqueous solution and heated at 160℃ x 3
A coated fabric was obtained by heat treatment for 1 minute.

Comparative Example 3 Polyamino acid urethane resin PAU- obtained in Example 1
3 and PAU-4, 1 nonionic surfactant (manufactured by Dainippon Ink & Chemicals Co., Ltd., SD-7) was added to 100 parts each of PAU-4.
and 30 parts of DMF were added and mixed uniformly to prepare a coating liquid.

Example 6 Using the obtained coating liquid
A coated fabric was obtained in the same manner as above.

[0084] Furthermore, due to the poor viscosity of the coating liquid,
It is difficult to obtain a fabric with a uniform coating film, so the physical properties of the fabric obtained in this comparative example were evaluated by selecting the best parts of the fabric.

Example 7 Polyamino acid urethane resin PAU-5 obtained in Example 1
30 parts of DMF was added to 100 parts and mixed uniformly to prepare a coating liquid.

[0086] The obtained coating liquid was applied to nylon taffeta using a floating knife coater at 100 g/m.
After 2 wet coatings, the resin was immersed in a 15° C. water bath for 1 minute to solidify the resin.

[0087] Thereafter, the sample was immersed in warm water at 50°C for 10 minutes to fully extract DMF. Subsequently, drying was performed to obtain a coated fabric.

Example 8 Polyamino acid urethane resin PAU-21 obtained in Example 1
00 parts of polyurethane resin solution U-1 obtained in Example 2
, add 100 parts each of U-2 and 20 parts of DMF,
A coating liquid was prepared by uniformly mixing.

[0089] Further, 100 parts of the polyurethane resin solution U-1 obtained in Example 2 and 20 parts of DMF were added to 1100 parts of the polyamino acid urethane resin PAU-1 obtained in Example 1 and mixed uniformly to prepare a coating liquid. did.

[0090] The obtained coating liquid was applied to nylon taffeta using a floating knife coater at 100 g/m.
After 2 wet coatings, the resin was immersed in a 15° C. water bath for 1 minute to solidify the resin.

[0091] Thereafter, the sample was immersed in warm water at 50°C for 10 minutes to fully extract DMF. Subsequently, drying was performed to obtain a coated fabric.

Example 9 To 220 parts of PAU obtained in Example 1, (2-3
) 100 parts of the polyurethane resin solution U-3 obtained in
70 parts of DMF and 2 parts of a nonionic surfactant (manufactured by Dainippon Ink & Chemicals, Inc., SD-7) were added and mixed uniformly to obtain a coating liquid.

[0093] The obtained coating liquid was applied onto a raised cloth made of Tetron/rayon at 800 g/m2 wet using a floating knife coater, and then immersed for 5 minutes in a 15% concentration aqueous solution of DMF kept at 30°C to remove the resin content. was solidified.

[0094] Thereafter, it was immersed in warm water at 50°C for 10 minutes to sufficiently extract DMF, and then dried at 120°C for 10 minutes to obtain a synthetic leather substrate (wet base).

Comparative Example 4 Polyurethane resin solution U obtained in (2-1) of Example 2
A coating liquid was prepared by mixing 100 parts of this solution with 20 parts of DMF using only -1. A coated fabric was obtained in the same manner as in Example 7 using this coating liquid.

Comparative Example 5 Polyurethane resin solution U obtained in (2-3) of Example 2
-3 alone, 100 parts of this solution was mixed with 70 parts of DMF, a nonionic surfactant (manufactured by Dainippon Ink & Chemicals, SD
-7) Two parts were uniformly mixed to obtain a coating liquid.

[0097] Using this coating liquid, a synthetic leather substrate (wet base) was obtained in the same manner as in Example 8.

Physical properties such as moisture permeability and water pressure resistance were measured for the coated fabrics and synthetic leather substrates (wet base) obtained in Examples 6 to 9 and Comparative Examples 3, 4, and 5, and the results are shown in Table 3. The results were obtained.

0099

[Table 3]

[0100] From Table 3 above, the coated fabric obtained using the resin composition of the present invention has higher values in moisture permeability and water pressure resistance than the coated fabric using a general wet processing urethane resin. It was recognized that it has both outstanding moisture permeability and waterproof performance.

[0101] Also, the amine value of the terminal amino group is 130 pp
Comparing PAU-4, which is a random copolymer of urethane prepolymer with terminal isocyanate group, amino acid, and hydrazine, and PAU-2, PAU-3 has an amine value of 130 p at the terminal amino group.
pm or higher, not only the viscosity at the end of the reaction was high, but also the coating uniformity was unfavorable.

[0102] In PAU-4, the reaction solution was heated to 25°C.
The viscosity after storage for 60 days was about 8 times thicker than that during reaction, and uniform coating was not favorable.

[0103]

Effects of the Invention As explained above, when the resin or resin composition obtained by the present invention is used as a treatment agent for the purpose of surface modification, it has a texture that is very similar to that of natural leather.
Sweat absorbency and strength can be imparted to it, and when it is made into dry-processed synthetic leather for clothing using the dry process, it can provide high moisture permeability and a dry feel. When used, the resulting coated fabric and artificial leather have high moisture permeability and water pressure resistance, as well as a soft texture similar to natural leather and good surface smoothness, making them suitable for use in sportswear, raincoats, sports shoes, etc. It was recognized that it is suitable for

Claims (5)

[Claims] Claim 1: A polyurethane resin having amino groups at both ends with an amine value of 1 to 130 ppm and an acidic amino acid ω-
The content of amino acid residues obtained by reacting with amino acid N-carbonic anhydride mainly composed of alkyl N-carbonic anhydride is 5
-95% by weight polyamino acid urethane resin. Claim 2: A polyurethane resin having amino groups at both ends with an amine value of 1 to 130 ppm and an acidic amino acid ω-
The content of amino acid residues obtained by reacting with amino acid N-carbonic anhydride mainly composed of alkyl N-carbonic anhydride is 5.
A resin composition characterized in that 0.01 to 20 parts by weight of a polymer compound is mixed with 1 part by weight of a polyamino acid urethane resin having a content of 95% by weight. 3. Synthetic leather or artificial leather obtained by coating a synthetic sheet with a treatment agent comprising the polyamino acid urethane resin or resin composition obtained according to claim 1 or 2 and a solvent. 4. A fabric obtained by coating a fabric with a treatment agent comprising the polyamino acid urethane resin or resin composition obtained according to claim 1 or 2 and a solvent. 5. A molded article obtained by applying a treatment agent comprising the polyamino acid urethane resin or resin composition obtained according to claim 1 or 2 and a solvent to a synthetic resin molded article.