JPH06157901A - Synthetic resin composition and synthetic sheet using the same - Google Patents

Abstract

PURPOSE:To obtain a resin composition providing a synthetic sheet having excellent waterproofness, wear resistance, water vapor transmission, etc., comprising a polyurethane resin, liquid rubber, etc., and a coupling agent. CONSTITUTION:(A) 100 pts.wt. polyurethane resin alone or mixed by blending a polyamino resin with a polyurethane resin in a weight ratio of 0:100 to 90:10 is mixed with (B) 0.1-50 pts.wt. (preferably 1-30 pts.wt) liquid rubber or its derivative, (C) 0.1-30 pts.wt. (preferably 1-20 pts.wt.) coupling agent such as isopropyltriisostearoyl titanate or vinyltrimethoxysilane and (D) 0.1-50 pts.wt. (preferably 1-30 pts.wt.) silicon-containing composition such as dimethylsilicone oil to give the objective composition.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a synthetic resin composition and a synthetic sheet using the synthetic resin composition. More specifically, it is made of polyurethane resin and polyamino acid urethane resin, and synthetic leather, artificial leather, and moisture-permeable waterproof cloth. Etc. (hereinafter referred to as a synthetic sheet), while imparting excellent waterproofness (water repellency, water resistance) abrasion resistance and softness without impairing the favorable characteristics of these resins, The present invention relates to a useful synthetic resin composition that improves moisture permeability and a synthetic sheet using the same.

[0002]

2. Description of the Related Art In recent years, development of resins for synthetic sheets has been actively carried out, and in particular, polyurethane resins and polyamino acid urethane resins are widely used as materials for porous synthetic sheets.

As a method for producing the porous synthetic sheet, for example, a polyurethane resin or a polyamino acid urethane resin is dissolved in a water-affinitive solvent, the solution is applied to or impregnated into a base material, and the solvent is removed in water to obtain the porous material. Method for forming a high quality synthetic sheet, and by applying or impregnating a base material with a water-in-oil emulsion of polyurethane resin, polyamino acid urethane resin, etc. A dry method using a sheet is known.

In the former wet method, the porous synthetic sheet obtained has a moisture permeability of 8000 g / m ² days and a water pressure resistance of 2000.
mm (Japanese Patent Laid-Open No. 61-284431), which has excellent moisture permeability and waterproofness, but requires a large amount of equipment in the solvent removal step, and it takes a long time to perform sufficient solvent removal, and a large amount of waste liquid. However, the dry method is advantageous from the viewpoints of productivity and economic efficiency. However,
Although the porous synthetic sheet obtained by the dry method is satisfactory in moisture permeability, it has problems in waterproofness, abrasion resistance, flexibility and the like.

[0005] Attempts have been made to solve these problems by selecting raw materials and using them in combination with a silicone resin, a coupling agent and the like. That is, depending on the type of raw material, the water resistance, abrasion resistance, and flexibility of the problem are improved, but the moisture permeability, which is one of the characteristics, is impaired. In addition, when a silicone resin is used in combination, poor adhesiveness, which is a characteristic of silane compounds, is manifested as a defect, and a problem arises in the adhesive strength with the material that is the base of the porous synthetic sheet. In addition, the combined use of a coupling agent improves the waterproof property and wear resistance, which are problems, but
There is no significant improvement in flexibility.

As described above, although various investigations have been made for solving the problems, the actual situation is that a resin composition which makes good use of each of them and still sufficiently exhibits excellent performance has not been obtained.

[0007]

SUMMARY OF THE INVENTION The object of the present invention was made in view of the above problems, and is a synthetic resin having excellent waterproofness, abrasion resistance, flexibility, and improved moisture permeability. It is intended to obtain a porous synthetic sheet having a composition and a film obtained by processing the composition.

[0008]

Means for Solving the Problems As a result of intensive studies on various synthetic resins in order to solve the above problems, the present inventors have found that polyurethane resins, polyamino acid urethane copolymer resins, polyamino acids and polyurethane By including liquid rubber or its derivative and a coupling agent in the mixed resin, excellent waterproofness, abrasion resistance, flexibility can be obtained without impairing the suitable characteristics, and at the same time moisture permeability can be improved. Further, they have found that these properties are further improved by using a silicon-containing compound in combination, and have completed the present invention.

That is, the present invention relates to (1) "0.1 parts of liquid rubber or its derivative is added to 100 parts of polyurethane resin.
50 parts by weight and 0.1 to 30 parts by weight of a coupling agent are contained in the resin composition. (2) "0.1 to 30 parts by weight of a liquid rubber or a derivative thereof and a coupling agent is added to 100 parts of a polyamino acid urethane copolymer resin or a mixed resin of polyamino acid and polyurethane. Resin composition. (3) "A resin composition containing 0.1 to 50 parts by weight of a silicon-containing compound with respect to 100 parts of the resin composition according to claim 1 or 2. (4) "A porous synthetic sheet obtained by adding water to the resin composition according to claim 1 or claim 2 or claim 3 to form an emulsion solution, coating the base material and performing dry film formation." It is a summary. The present invention will be described in detail below.

The resin used in the present invention is a polyurethane resin alone or a mixed resin in which a polyamino acid resin and a polyurethane resin are mechanically blended at a weight ratio of 0: 100 to 90:10, or a copolymer of amino acid and urethane. It is a resin (hereinafter referred to as a raw material resin).

As the polyurethane resin, a reaction product of a reaction product of an organic diisocyanate and a diol in a solvent and, if necessary, a product whose chain length is extended with a diamine are used. As the isocyanate component, an aromatic diisocyanate, an aliphatic diisocyanate, and an alicyclic diisocyanate may be used alone or in a mixture thereof. For example, tolylene 2,4-diisocyanate, 4 ,.
4'-diphenylmethane diisocyanate, 1,6-hexamethylene diisocyanate, 1,4-cyclohexane diisocyanate and the like can be mentioned. As the polyol component, polyether polyol or polyester polyol is used. Polyether polyols include polyethylene glycol, polypropylene glycol, polytetraethylene glycol and the like, and polyester polyols include reaction formation between diols such as ethylene glycol and propylene glycol and dibasic acids such as adipic acid and sebacic acid. And ring-opening polymers such as caprolactone.

The polyamino acid urethane copolymer resin has a terminal OH group composed of the above-mentioned isocyanate and polyol components, an isocyanate group, or a terminal amino group obtained by chain-extending a urethane prepolymer having the above-mentioned isocyanate group with a diamine. It is a copolymer obtained by a reaction between a urethane prepolymer and 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 compounds and racemic compounds may be used. Well, these may be used alone or in combination. As a method of synthesizing a polyamino acid urethane copolymer, copolymerization with a urethane prepolymer having a terminal isocyanate group is obtained by adding amino acid NCA to the urethane prepolymer solution and then adding hydrazine, amines, and alcohols. To be As the amines, ethylenediamine, diethylamine, ethanolamine and the like are used. Also, terminal OH
In copolymerization with a urethane prepolymer having an amino group and an amino group, the amino acid NC is added to the urethane prepolymer solution.
It can be synthesized by adding A.

The mixed resin of polyamino acid and polyurethane is a mechanical mixture of the above-mentioned polyurethane resin and polyamino acid resin. The polyamino acid can be synthesized by polycondensing the above amino acid NCA with a compound having active hydrogen in a solvent. When polymerizing a polyamino acid or copolymerizing an amino acid and polyurethane, a tertiary amine may be added as a catalyst, if necessary.

Examples of the liquid rubber used in the present invention include liquid butadiene rubber, liquid styrene-butadiene rubber, liquid acrylonitrile-butadiene copolymer rubber, liquid polychloroprene, liquid polysulfide, and other functional rubbers having terminal functional groups, and derivatives thereof. Non-functional liquid rubbers such as rubber, liquid polyisoprene, liquid butyl rubber, and liquid polyisobutylene. Further, a mixture of these liquid rubbers may be used. The amount of the liquid rubber used is 0.1 to 50 parts with respect to 100 parts of the raw material resin.
It is desirable to use it in a ratio of preferably 1 to 30 parts. If the amount used is less than 0.1 part, flexibility is poor, and 5
If it exceeds 0 part, the compatibility with synthetic resins such as polyamino acid urethane resin deteriorates and a resin composition cannot be obtained, which is not preferable.

Examples of the coupling agent used in the present invention include titanate coupling agents, aluminum coupling agents and silane coupling agents. The titanate coupling agent is a monoalkoxy organic titanate. At least one aliphatic hydrocarbon group having 8 to 22 carbon atoms is contained in the molecule as an organic group. For example, isopropyl triisostearoyl titanate, isopropyl isosteroyl dimethacryl titanate, isopropyl isostearoyl diallyl titanate, isopropyl tri (dioctyl phosphate) titanate, isopropyl tri (dioctyl pyrophosphate) titanate and the like. The aluminum-based coupling agent is an alkoxyorganoaluminum compound, and contains at least one aliphatic hydrocarbon group having 8 to 22 carbon atoms or fluorocarbon group as an organic group in the molecule. For example, diisopropoxy aluminum octadecyl acetoacetate, isopropoxy nonadecafluorodecanoyl aluminum ethyl acetoacetate, isopropoxy nonadecafluorodecanoyl aluminum octadecyl acetoacetate, diisopropoxy aluminum 1H, 1
H, 2H, 2H-perfluorodecyl acetoacetate, isopropoxy 1H, 1H, 2H, 2H-perfluorodecanoxyaluminum ethylacetoacetate,
Such as isopropoxy 1H, 1H, 2H, 2H-perfluorodecanoxyaluminum octadecyl acetoacetate, and the like. The silane coupling agent is an alkoxyorganosilane compound, and contains at least one aliphatic hydrocarbon group having 8 to 22 carbon atoms in the molecule as an organic group. For example, vinyltrimethoxysilane,
Examples thereof include vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, allyltrimethoxysilane, and allyltrimethoxysilane. Further, a mixture of these coupling agents may be used. The amount of these coupling agents used is 0.1 to 30 parts, preferably 1 to 20 parts, relative to 100 parts of the raw material resin. If the amount used is less than 0.1 part, the waterproofness and abrasion resistance are poor, and if it exceeds 30 parts, the compatibility with synthetic resins such as polyurethane resin and polyamino acid urethane resin deteriorates, and a resin composition cannot be obtained. Not preferable.

Examples of the silicon-containing compound used in the present invention include silicone oils such as dimethyl silicone oil, methylphenyl silicone oil, methylhydrogen silicone oil, and chlorophenyl silicone oil, alcohol-modified silicone oil, mercapto-modified silicone oil, alkyl-modified silicone. oil,
Organic modified silicone oils such as amino modified silicone oils and silicone-polyoxyalkylene copolymers. Further, it may be a mixture of these silicone-containing compounds. The amount of these silicon-containing compounds used is 0.1 with respect to 100 parts of the resin composition.
It is desirable to use at a ratio of -50 parts, preferably 1-30 parts. If the amount used is less than 0.1 part, the waterproofness and abrasion resistance will be poor, and if it exceeds 50 parts, the adhesiveness of the resin to the substrate will be poor, such being undesirable.

Further, as a solvent for obtaining a resin solution of the above-mentioned polyurethane resin, polyamino acid urethane copolymer resin, or polyamino acid / polyurethane mixed resin, these polyamino acid urethane resins are dissolved and a synthetic sheet is industrially used. There is no limitation as long as it is a processable solvent, and representative examples include ether solvents such as dioxane, tetrahydrofuran and isopropyl ether, aromatic solvents such as benzene, toluene and xylene, ester solvents such as ethyl acetate and butyl acetate. Solvents, ketone-based solvents such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, amide-based solvents such as N, N-dimethylformamide, formamide and N, N-dimethylacetamide, alcohol-based solvents such as ethanol, isopropyl alcohol and butanol It may be a single or a mixture.

Further, in the present invention, a crosslinking agent may be used in combination, if necessary, for the purpose of improving the peel resistance between the film of the synthetic sheet and the substrate. Examples of the cross-linking agent include isocyanate cross-linking agents and epoxy cross-linking agents. The cross-linking agent is used in an amount of 0.1 to 10%, preferably 0.5 to 5%, based on the raw material resin. If the amount used is less than 0.1%, the adhesive force of the resin to the substrate will be poor, and if it exceeds 10%, the texture will be hardened, which is not preferable.

The synthetic resin composition of the present invention is a mixture of the above-mentioned raw material resin, liquid rubber or a derivative thereof, a coupling agent and a silicon-containing compound, and the mixing method is mechanical and the sequence and temperature are There are no restrictions, etc.,
It is usually performed at room temperature.

A method for obtaining a porous synthetic sheet by dry film formation using the synthetic resin composition of the present invention is as follows. A porous synthetic sheet can be obtained on a base material by coating on a substrate and removing the solvent and water by heating. As the base material, cotton, hemp, pulp, wood, bamboo, viscose silk, Bemberg silk, cellulose acetate and other fibrin and its derivatives, silk, wool, hair, natural leather, regenerated leather, synthetic leather, artificial Leather, polyamino acids,
Polyamides, polyurethanes, polyesters, polyesteramides, acrylonitrile polymers, polystyrene and its derivatives, polyacrylamide or polymethacrylamide and its derivatives, natural rubber and synthetic rubbers such as polyisobrene or polybutadiene, or mixtures thereof, polyethylene. Examples thereof include copolymers thereof, polypropylene and copolymers thereof, various plastics such as phenol resin, melamine resin and urea resin, and one or a mixture of two or more of quartz, glass, cements and various metals.

The present invention has the above-mentioned constitution. The reason why it has excellent flexibility is that liquid rubber or its derivative is added to the raw material resin in an appropriate amount.
It is considered that the rubber elasticity, which is the characteristic of the rubber, is imparted without impairing other properties. Further, the reason why the porous synthetic sheet of the present invention has excellent wear resistance and waterproofness without impairing the suitable properties, and the reason is not critical, but the surface of the film of the obtained porous synthetic sheet. Observing, compared to polyurethane resin, polyamino acid urethane resin alone, the resin composition of the present invention, the microcells are scattered as if it has a small surface skin layer, excellent wear resistance from this, It is considered to be a factor that gives waterproofness.

Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to these examples.
Moreover, the evaluation used the following evaluation method.

[0023]

【Example】

1. Abrasion resistance Gakushin-type friction fastness tester (JIS L
0823) and rubbed 1000 times according to JIS L 1084 (friction tester method) with a load of 200 g,
The appearance state of the film was observed and the following three-stage evaluation was performed. × Complete wear △ Partial wear ○ No abnormality

2. Water pressure resistance According to JIS L 1092 (low water pressure method).

3. Water vapor transmission rate According to JIS L 1099 (calcium chloride method).

4. Rigidity JIS L 1084 (45
° Cantilever method).

Synthesis Example 1 Polyurethane Resin 900 parts and 200 parts of polytetramethylene glycol and polyethylene glycol having a number average molecular weight of 2000, respectively.
Parts, and 3000 parts of methyl ethyl ketone to 63.86 parts of ethylene glycol and dissolved at 50 ° C., 2 parts of a methyl ethyl ketone solution of 10% dibutyltin dilaurate and 400 parts of 4,4′-diphenylmethane diisocyanate were added as a solvent. The reaction was continued under the reflux of this mixed solution of methyl ethyl ketone, and morpholine was added to stop the reaction when the viscosity of the reaction solution reached 100,000 cPs / 30 ° C. To this reaction solution, 1600 parts of methyl ethyl ketone was added to obtain a polyurethane resin solution.

Synthetic Example 2 Polyamino Acid Urethane Copolymer Resin To 500 parts of the polyurethane resin solution obtained in Synthetic Example 1 was added 0.25 parts of triethylamine, and the mixture was stirred at 30 ° C. for 10 minutes, then 90 parts of methyl isobutyl ketone and 12 parts of toluene.
34.5 parts of γ-methyl-L-glutamic acid NCA was dissolved in a mixed solution of 0 parts and 80 parts of methyl ethyl ketone,
It was added to the above resin solution and polymerized at 30 to 40 ° C. for 3 hours to obtain a polyamino acid urethane copolymer resin.

Synthesis Example 3 Polyamino Acid Urethane Copolymer Resin 0.25 parts of triethylamine was added to 500 parts of the polyurethane resin solution obtained in Synthesis Example 1 and stirred at 30 ° C. for 10 minutes, and then 90 parts of methyl isobutyl ketone and 120 parts of toluene.
30 parts of γ-methyl-L-glutamic acid NCA and L-leucine NCA in a mixed solution of 80 parts of methyl ethyl ketone.
Dissolve 7 parts, add to the above resin solution, and add 30-4
Polymerization was performed at 0 ° C. for 3 hours to obtain a polyamino acid urethane copolymer resin.

Synthesis Example 4 Polyamino acid urethane mixed resin 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 7-methyl-L.
-A mixed NCA of 12 parts of glutamic acid NCA was added and dissolved, and then 0.5 part of ethylenediamine was added and stirred at 25 ° C for 1 hour, and then polymerized at 60 ° C for 5 hours. This polymerization solution 1
40 parts of the urethane resin solution obtained in Synthetic Example 1 was added to 00 parts and mixed uniformly to obtain a polyamino acid urethane mixed resin.

Example 1 Preparation of Synthetic Resin Composition A) Liquid polybutadiene rubber Poly bd R- was added to 100 parts of solid content in the resin solution obtained in Synthesis Example 2.
45HT (manufactured by Idemitsu Petrochemical Co., Ltd.) and 25 parts of aluminum coupling agent AL-M (manufactured by Ajinomoto Co., Inc.) were added and mixed uniformly to obtain a synthetic resin composition.

B) Liquid polybutadiene rubber Pory was added to 100 parts of the solid content in the resin solution obtained in Synthesis Example 2.
bd R-45HT (manufactured by Idemitsu Petrochemical Co., Ltd.) 25
Parts, aluminum-based coupling agent AL-M (manufactured by Ajinomoto Co., Inc.), and 10 parts TSF451-500 (manufactured by Toshiba Silicone Co., Ltd.) were added and mixed uniformly to obtain a synthetic resin composition.

Example 2 Preparation of Porous High Moisture Permeability Synthetic Sheet 40 parts of water to 100 parts of solid content of the synthetic resin composition obtained in A) or B) of Example 1, and surfactant EMALEX
103 (manufactured by Nippon Emulsion Co., Ltd.) 1 part, C-229
The emulsion solution obtained by adding 8 10 and stirring at high speed was coated on a nylon taffeta (flexibility 48 mm) with a roll coater so as to have a weight of 50 g / m ² , and then at 80 ° C. for 5 minutes.
The solvent and water were removed by two-step drying at 120 ° C. for 5 minutes to obtain a porous highly moisture-permeable synthetic sheet. No. 1, No.
2, Abrasion resistance table of this material, water pressure resistance, moisture permeability,
The results of evaluation of bending resistance are shown in Table 1.

Comparative Example 1 As Comparative Example 1, the resin solution of Synthesis Example 2 was evaluated in the same manner, and the results are shown in Table 1.

[0035]

[Table 1]

Example 3 Preparation of Porous High Moisture Permeability Synthetic Sheet 60 parts of water, 10 parts of C-2298, 10 parts of EMALEX1 based on 100 parts of solid content in the polyurethane resin of Synthesis Example 1.
Preparation and evaluation were carried out according to Examples 1 and 2 under the conditions shown in Table 2 for the coupling agent, polysiloxane, type and amount of liquid rubber, etc. The results are shown in Table 3.

[0037]

[Table 2]

[0038]

[Table 3]

Example 4 Preparation of Porous High Moisture Permeability Synthetic Sheet With respect to 100 parts of solid content in the polyamino acid urethane copolymer resin of Synthesis Examples 2 and 3, 40 parts of water and C-2298 10
And 1 part of EMALEX 103 were used and prepared and evaluated according to Examples 1 and 2 under the conditions shown in Table 4 for the coupling agent, polysiloxane, type and amount of liquid rubber. The results are shown in Table 5.

[0040]

[Table 4]

[0041]

[Table 5]

Example 5 Preparation of Porous High Moisture Permeability Synthetic Sheet Solid content 1 in the polyamino acid urethane mixed resin of Synthesis Example 4
To 00 parts, 40 parts of water, 10 parts of C-2298, EM
Using 1 part of ALEX103, preparation and evaluation were performed according to Examples 1 and 2 under the conditions shown in Table 6 for the coupling agent, polysiloxane, type and amount of liquid rubber.
The results are shown in Table 7.

[0043]

[Table 6]

[0044]

[Table 7]

[0045]

EFFECT OF THE INVENTION By using the synthetic resin composition of the present invention, excellent waterproofness, abrasion resistance and flexibility are imparted to the porous synthetic sheet, and at the same time moisture permeability is improved.
It can be used for a wide range of purposes such as artificial leather and synthetic sheets such as breathable waterproof cloth.

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[Procedure amendment]

[Submission date] May 30, 1991

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0013

[Correction method] Change

[Correction content]

The mixed resin of polyamino acid and polyurethane is a mechanical mixture of the above-mentioned polyurethane resin and polyamino acid resin. The polyamino acid can be synthesized by polycondensing the above amino acid NCA with a compound having active hydrogen in a solvent. Compounds having active hydrogen that can be used in the present invention
As substances, ammonia, monomethylamine, dimethylamine
Min, diethylamine, ethylenediamine, propylene
Diamine, hexamethylenediamine, 1,4-cyclohexyl
Xanthiamine, o-phenylenediamine, p-phenyl
Diamine, toluene-2,4-diamine, 4,4 '
-Diphenylmethanediamine, polyoxypropylene di
Amine, N, N-dimethylethylenediamine, N, N-
Dimethyl-1,3-propanediamine, isophoronedia
Min, 1,2-cyclohexanediamine, primary or secondary
Polysiloxane with primary amino group, polybutadiene
Amino compounds such as compounds, ethylene glycol, 1,3-
Butanediol, Hexamethylene glycol, Poly
Has terglycol, polyester glycol, hydroxyl group
Alcohols such as polysiloxanes and polybutadiene compounds
Compounds. When polymerizing a polyamino acid or copolymerizing an amino acid and polyurethane, a tertiary amine may be added as a catalyst, if necessary.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0014

[Correction method] Change

[Correction content]

Examples of the liquid rubber used in the present invention include liquid butadiene rubber, liquid styrene-butadiene rubber, liquid acrylonitrile-butadiene copolymer rubber, liquid polychloroprene, liquid polychlorosulfide, and other terminal functional group-type liquid rubbers and their derivatives, and liquid silicones. And non-functional liquid rubbers such as liquid rubber , liquid natural rubber, liquid polyisoprene, liquid butyl rubber, and liquid polyisobutylene. Further, a mixture of these liquid rubbers may be used. Also,
Chain length of these liquid rubbers using diisocyanate compounds
Extending, or even a part of the double bond in liquid rubber or
The whole can be hydrogenated and used. The amount of these liquid rubbers used is 0.1 to 50 parts, preferably 1 to 30 parts, relative to 100 parts of the raw material resin. If the amount used is less than 0.1 part, flexibility is poor, and if it exceeds 50 parts, compatibility with synthetic resins such as polyamino acid urethane resin deteriorates and a resin composition cannot be obtained, which is not preferable.

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0019

[Correction method] Change

[Correction content]

The synthetic resin composition of the present invention is a mixture of the above-mentioned raw material resin, liquid rubber or its derivative, and a coupling agent and a silicon-containing compound. The mixing method is mechanical and the order is There are no restrictions on the temperature,
It is usually performed at room temperature. The synthetic resin composition of the present invention contains various stabilizers, if necessary, such as hindered amine light stabilizers, phenolic antioxidants, thioether antioxidants, phosphite antioxidants, and inorganic or organic fillers. It can also be used by kneading. As a method for obtaining the porous synthetic sheet, either a dry film formation or a wet film formation can be used, but the dry film formation is preferable in view of the processing steps. Also, a molded product made of the synthetic resin composition of the present invention can be used.

[Procedure amendment 4]

[Document name to be amended] Statement

[Name of item to be corrected] 0030

[Correction method] Change

[Correction content]

Synthesis Example 4 Polyamino acid urethane mixed resin In a mixed solution of 80 parts of toluene and 20 parts of N, N-dimethylformamide, 9 parts of L-leucine NCA and γ-methyl-L.
-A mixed NCA of 12 parts of glutamic acid NCA was added and dissolved, and then 0.5 part of ethylenediamine was added and stirred at 25 ° C for 1 hour, and then polymerized at 60 ° C for 5 hours. This polymerization solution 1
40 parts of the urethane resin solution obtained in Synthetic Example 1 was added to 00 parts and mixed uniformly to obtain a polyamino acid urethane mixed resin. Synthesis Example 5 Synthesis of liquid butadiene rubber derivative Liquid polyolefin polyol (Epol, manufactured by Idemitsu Petrochemical Co., Ltd.) 952.4 parts, isophorone diisocyanate 4
7.6 parts and 1000 parts of toluene were mixed and stirred at 65 ° C. for 3 hours to obtain a liquid butadiene rubber derivative.

[Procedure Amendment 5]

[Document name to be amended] Statement

[Name of item to be corrected] 0032

[Correction method] Change

[Correction content]

B) Liquid polybutadiene rubber Pory was added to 100 parts of the solid content in the resin solution obtained in Synthesis Example 2.
bd R-45HT (manufactured by Idemitsu Petrochemical Co., Ltd.) 25
Parts, 10 parts of aluminum-based coupling agent AL-M (manufactured by Ajinomoto Co., Inc.), and 10 parts of TSF451-500 (manufactured by Toshiba Silicone Co., Ltd.) were uniformly mixed to obtain a synthetic resin composition. c) 25 parts of the liquid butadiene rubber derivative obtained in Synthesis Example 5 and the aluminum-based coupling agent A based on 100 parts of the solid content in the resin solution obtained in Synthesis Example 2.
10 parts of LM (manufactured by Ajinomoto Co., Inc.) were uniformly mixed to obtain a synthetic resin composition. D) Liquid silicone rubber (TS) was added to 100 parts of the solid content in the resin solution obtained in Synthesis Example 2.
E-399, 25 parts by Toshiba Silicone Co., Ltd., aluminum-based coupling agent AL-M (manufactured by Ainomoto Co., Ltd.) 1
0 parts were uniformly mixed to obtain a synthetic resin composition.

[Procedure correction 6]

[Document name to be amended] Statement

[Correction target item name] 0040

[Correction method] Change

[Correction content]

[0040]

[Table 4] Combination recipe

[Procedure Amendment 7]

[Document name to be amended] Statement

[Correction target item name] 0041

[Correction method] Change

[Correction content]

[0041]

[Table 5] Evaluation results

[Procedure Amendment 8]

[Document name to be amended] Statement

[Correction target item name] 0043

[Correction method] Change

[Correction content]

[0043]

[Table 6] Formulation

[Procedure Amendment 9]

[Document name to be amended] Statement

[Correction target item name] 0044

[Correction method] Change

[Correction content]

[0044]

[Table 7] Evaluation results

Claims (4)

[Claims] 1. A resin composition comprising 0.1 to 50 parts by weight of a liquid rubber or a derivative thereof and 0.1 to 30 parts by weight of a coupling agent with respect to 100 parts of a polyurethane resin. 2. 0.1 to 50 parts by weight of liquid rubber or its derivative with respect to 100 parts of polyamino acid urethane copolymer resin or mixed resin of polyamino acid and polyurethane,
And 0.1 to 30 parts by weight of a coupling agent, a resin composition. 3. A resin composition comprising 0.1 to 50 parts by weight of a silicon-containing compound with respect to 100 parts of the resin composition according to claim 1 or 2. 4. A porous synthetic sheet obtained by adding water to the resin composition according to claim 1, 2 or 3 to make an emulsion solution, coating the base material and performing dry film formation.