JPH04175369A - Synthetic resin composition and synthetic sheet prepared therefrom - Google Patents

Abstract

PURPOSE:To improve waterproofness, abrasion resistance, and water vapor permeability by compounding a polyurethane resin with a coupling agent. CONSTITUTION:100 pts.wt. polyurethane resin comprising 0-90wt.% polyamino resin and 100-10wt.% polyurethane resin is compounded with 0.1-30 pts.wt. coupling agent (e.g. isopropyl triisostearoyl titanate) to give a synthetic resin compsn., to which 1-60wt.% water is added to give an emulsion. The emulsion is applied to a substrate, heated to remove a solvent and water, giving a synthetic sheet contg. a porous layer.

Description

[Detailed Description of the Invention] <Industrial Application Field> The present invention relates to a synthetic resin composition and a synthetic sheet using the same. Specifically, the present invention relates to a synthetic resin composition and a synthetic sheet using the same. When manufacturing artificial leather, moisture-permeable waterproof fabric, sheets for building materials, etc. (hereinafter referred to as synthetic sheets), it is possible to obtain excellent waterproof properties (water repellency, water resistance) without sacrificing the favorable properties that are the advantages of these resins.
The present invention relates to a useful synthetic resin composition that provides abrasion resistance and improves moisture permeability, and a synthetic sheet using the same.

<Conventional technology> In recent years, resins for synthetic sheets have been actively developed.
In particular, polyurethane resins and polyamino acid urethane resins are frequently used as materials for porous synthetic sheets.

This porous synthetic sheet can be produced by, for example, dissolving a polyurethane resin or a polyamino acid urethane resin in a water-friendly solvent, applying or impregnating this solution onto a base material, and removing the solvent in water. A porous, highly moisture permeable synthetic sheet is obtained by applying or impregnating a water-in-oil emulsion of polyurethane resin or polyamino acid urethane resin onto a base material, and removing the solvent and dehydrating it by heating and drying. A dry method is known.

In the former wet method, the resulting porous synthetic sheet has a moisture permeability of 8000 g/m for 2 days and a water pressure resistance of 2000 m.
m (Japanese Unexamined Patent Publication No. 6L-284431), it has excellent moisture permeability and waterproofness, but the desolvation process requires a large amount of equipment, takes a long time to perform sufficient desolvation, and generates a large amount of waste liquid. There are problems such as the need for additional treatment, so the dry method is advantageous in terms of productivity and economy. However, although the porous synthetic sheet obtained by the dry method has satisfactory moisture permeability, it has problems with waterproofness, abrasion resistance, etc.

Attempts have been made to solve these problems by selecting raw materials, using them in combination with silicone resins, etc. That is, depending on the type of raw material, the problematic waterproofness and abrasion resistance may be improved, but on the other hand, the moisture permeability, which is one of the characteristics, may be impaired.

Further, when a silicone resin is used in combination, the poor adhesion characteristic of the silane compound appears as a drawback, causing a problem in contact strength with the base material of the porous synthetic sheet. There is a method of using a coupling agent to increase the contact strength (Japanese Patent Laid-Open No. 58-122977), but there is no example of it being used for the purpose of also providing moisture permeability.

Although various studies have been made to solve these problems, the reality is that no resin composition has yet been developed that fully exhibits excellent performance that takes advantage of each of them.

<Problems to be Solved by the Invention> An object of the present invention is to obtain a porous synthetic sheet having a membrane obtained in view of the above-mentioned problems.

Means for Solving the Problems In order to solve the problems, the present inventors conducted intensive research on various synthetic resins, and found that polyurethane resins,
Alternatively, by incorporating a coupling agent into a polyamino acid urethane copolymer resin or a mixed resin of polyamino acid and polyurethane, excellent waterproofness and abrasion resistance can be obtained without sacrificing suitable properties, and at the same time moisture permeability can be achieved. The inventors also discovered that these properties can be further improved by using a silicon-containing compound in combination, leading to the completion of this invention.

That is, the present invention provides (1) a resin composition characterized by containing 0.1 to 30 parts of a coupling agent per 100 parts of a polyurethane resin, and (2) a polyamino acid urethane copolymer. A resin composition containing 0.1 to 30 parts by weight of a coupling agent per 100 parts of a resin or a mixed resin of polyamino acid and polyurethane. J(3)r Claim (1) or (2) 0.1 to 100 parts of the silicon-containing compound to 100 parts of the resin composition described above.
A resin composition characterized in that it contains 50311 parts. J(4)r A porous synthetic sheet obtained by adding water to the resin composition according to claim (1), (2) or (3) to form an emulsion solution, and then coating it on a base material and forming a dry film, j is the gist. The present invention will be explained in detail below.

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

As the polyurethane resin, a reaction product obtained by reacting 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, aromatic diisocyanates, aliphatic diisocyanates, and alicyclic diisocyanates are used alone or in mixtures thereof, for example,
Examples include tolylene 2,4-diisocyanate, 4,4'-diphenylmethane diisocyanate, 1,6-hexamethylene diisocyanate, and 1,4-cyclohexane diisocyanate. As the polyol component, polyether polyols and polyester polyols are used. Polyether polyols include polyethylene glycol, polypropylene glycol, polytetraethylene glycol, etc., and polyester polyols are produced by the reaction of diols such as ethylene glycol and propylene glycol with dibasic acids such as adipic acid and sepatic acid. and ring-opening polymers such as caprolactone and caprolactone.

In addition, as the polyamino acid urethane copolymer resin, terminal OH groups consisting of the above-mentioned isocyanate and polyol components,
A urethane prepolymer having an amino group or an isocyanate group and an amino acid N-carboxylic anhydride (hereinafter referred to as N
It is a copolymer obtained by reaction with carboxylic acid anhydride (NCA). Examples of amino acids include acidic amino acids and their derivatives such as aspartic acid and glutamic acid, and neutral amino acids such as glycine, DL-alanine, cystine, methionine, and leucine. As a method for synthesizing a polyamino acid urethane copolymer, these may be used alone or in combination. Copolymerization with a urethane prepolymer having terminal isocyanate groups involves adding amino acids NCA to a urethane prepolymer solution. It is obtained later by adding hydrazine and amines. As the amines, ethylenediamine, diethylamine, ethanolamine, etc. are used. Furthermore, in copolymerization with a urethane prepolymer having a terminal OH group or amine group, synthesis can be performed by adding the amino acid NCA to the urethane prepolymer solution.

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 hot medium. When polymerizing polyamino acids or copolymerizing amino acids with polyurethane, it is preferable to add a tertiary amine as a catalyst if necessary.

Coupling agents used in the present invention include titanate coupling agents, aluminum coupling agents, and silane coupling agents, and examples of titanate coupling agents include monoalkoxy organic titanates,
Containing at least one aliphatic hydrocarbon group having 8 to 22 carbon atoms as an organic group in the molecule. For example, isopropyl triisostearoyl titanate, isopropylisosteroyl dimethacrylic titanate, isopropylisostearoyl diallyl titanate, isopropyl tri(dioctylphos) phate) titanate, isopropyltri(dioctylpyrophosphate) titanate, and the like. 1 containing at least one aluminum-based cup aliphatic hydrocarbon group or fluorocarbon group in the molecule, such as diisopropoxyaluminum octadecyl acetoacetate, isopropoxy nonadecafluorodecanoyl aluminum ethyl acetoacetate, isopropoxy nonadecafluoro Decanoyl aluminum octadecyl acetoacetate, diisopropoxy aluminum IH, IH
, 2H, 2H-perfluorodecylacetoacetate,
Isopropoxy IH.

IH, 2H, 2H-perfluorodecatoxy aluminum ethyl acetoacetate, isopropoxy IH, IH
, 2H,2H-perfluorodecatoxyaluminum octadecyl acetoacetate, and the like. The silane coupling agent is an alkoxyorganosilane compound containing at least one aliphatic hydrocarbon group having 8 to 22 carbon atoms as an organic group in the molecule. For example, vinyltrimethoxysilane, vinyltriethoxysilane , γ
- such as methacryloxypropyltriethoxysilane, allyltrimethoxysilane, allyltrimethoxysilane, etc. Furthermore, a mixture of these coupling agents may also be used. As for the use of these coupling agents, 0.1 to 30 parts per 100 parts of the raw material resin,
Preferably, it is used in a ratio of 1 to 20 parts.If the amount used is less than 0.1 part, waterproofness and abrasion resistance will be poor, and if it exceeds 30 parts, it will be difficult to synthesize polyurethane resins, polyamino acid urethane resins, etc. This is not preferable because the compatibility with the resin deteriorates and a resin composition cannot be obtained.

Examples of silicon-containing compounds 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, and amines. Organic modified silicone oil such as modified silicone oil, and
It is a silicone-polyoxyalkylene copolymer. Furthermore, a mixture of these silicone-containing compounds may be used. The amount of these silicon-containing compounds to be used is desirably 0.1 to 50 parts, preferably 1 to 30 parts, based on 100 parts of the raw material resin.

If the amount used is less than 0.1 part, waterproofness and abrasion resistance will be poor, and if it exceeds 30 parts, the adhesiveness of the resin to the substrate will be poor, which is not preferable.

In addition, as a solvent for obtaining the resin solution of the above-mentioned polyurethane resin, polyamino acid urethane copolymer resin, or polyamino acid and urethane mixed resin, a solvent that can dissolve these polyamino acid urethane resins and industrially process synthetic sheets can be used. Typical 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, and methyl ethyl ketone. , methyl isobutyl ketone, ketone solvents such as cyclohexanone, N,
N-dimethylformamide, formamide, N,
An amide solvent such as N-dimethylacetamide may be used alone or in a mixture.

Furthermore, in the present invention, in order to improve the peeling resistance between the synthetic sheet film and the base material, a crosslinking agent may be used in combination as necessary. Examples of such crosslinking agents include isocyanate crosslinking agents and epoxy crosslinking agents. agents, etc. The amount of crosslinking agent used is 0.1 to 10%, preferably 0.1 to 10%, based on the raw material resin.
It is desirable to use at a rate of 5-5%, the amount used is 0
．． If it is less than 1%, the adhesive strength of the resin to the base material will be poor, and if it exceeds 10%, the texture will be hard, which is not preferable.

The synthetic resin composition of the present invention is a mixture of the above-mentioned raw material resin, coupling agent, and silicon-containing compound,
The mixing method is mechanical and there are no restrictions on the order or temperature, but it is usually carried out 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 to add 1 part of water to the synthetic resin composition.
~60% by weight is added to make an emulsion solution, then coated on a substrate and the solvent and water removed by heating to form a porous layer on the substrate, resulting in a porous composite with excellent waterproof and abrasion resistance. You can get a seat. Base materials include cotton, linen, bulbs, wood, bamboo, viscose human silk, cellulose and its derivatives such as cellulose acetate, string, wool, hair, natural leather, recycled leather, synthetic leather, artificial leather, Polyamino acids, polyamides, polyurethanes, polyesters, polyesteramides,
Acrylonitrile polymers, vinyl chloride polymers, polystyrene and its copolymers, polyvinyl alcohol and its rust conductors, polyacrylamide, or polymethacrylamide and their rust conductors, natural rubber, and synthetic rubbers such as polyisoprene or polybutadiene; mixtures thereof, polyethylene and copolymers thereof,
Polypropylene and its copolymers, phenolic resins,
Various plastics such as melamine resin and urea resin, quartz,
Examples include one or a mixture of two or more of glass, cement, various metals, and the like.

The present invention has the above-described configuration, but the reason why the porous synthetic sheet of the present invention has excellent abrasion resistance and waterproofness without impairing its favorable properties is not clear. However, when the surface of the film of the obtained porous synthetic sheet was observed, it was found that compared to polyurethane resin or polyamino acid urethane resin alone, the resin composition of the present invention had smaller microcells that were dotted as if they had a surface skin layer. and
This is considered to be a factor that provides excellent abrasion resistance and waterproof properties.

<Example> Hereinafter, this invention will be explained in detail with reference to Examples.

In addition, the evaluation method used below was used for evaluation.

1. Method for measuring surface slipperiness Model: KES-3E (friction tester) KA
TOTECHCO, LTD manufacturing conditions Temperature: 24℃ Humidity: 53% Load: 50g Contact area: 1 cm2 Contact surface Sliding speed between coated surfaces: 1 mm 7 seconds2, abrasion resistance Load: 2 using a Gakushin type friction fastness tester
The film was rubbed 1000 times at 00 g, and the appearance of the film was observed and evaluated on the following three levels.

× Complete wear Δ Partial wear O No abnormality 3, Water repellency Immediately after dropping one drop of water onto the film, the contact angle was measured using an automatic contact angle measuring device.

4. Water pressure resistance JIS L-1092 (water pressure method) 5.
Moisture Permeability JIS L-1099 (calcium chloride method) Synthesis Example 1 Polyurethane resin 900 parts and 200 parts of polytetramethylene glycol and polyethylene glycol with a number average molecular weight of 2000, respectively, 6+ parts of ethylene glycol and 30 parts of methyl ethyl ketone
00 parts were added and dissolved at 50°C, and then 2 parts of a 10% dibutyltin dilaurate solution in methyl ethyl ketone and 400 parts of 4.4'-diphenylmethane diisocyanate were added as solvents. The reaction of this mixed solution was continued under refluxing of methyl ethyl ketone, and the viscosity of the reaction solution was 100,000 CP.
When the temperature reached S/30°C, morpholine was added to stop the reaction. 1600 parts of methyl ethyl ketone was added to this reaction solution to obtain a polyurethane resin solution.

Synthesis Example 2 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 after stirring at 30°C for 10 minutes, 90 parts of methyl isobutyl ketone, 120 parts of toluene, and 80 parts of methyl ethyl ketone were added. 34.5 parts of γ-methyl-L-glutamic acid NCA was dissolved in the mixed solution of 34.5 parts, added to the 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 after stirring at 30°C for 10 minutes, 90 parts of methyl isobutyl ketone, 120 parts of toluene, and 80 parts of methyl ethyl ketone were added. 30 parts of γ-methyl-L-glutamic acid NCA and 30 parts of L-leucine NCAT were dissolved in a mixed solution of 30 parts, added to the above resin solution, and polymerized at 30 to 40 °C for 3 hours to obtain a polyamino acid urethane copolymer resin. Ta.

Synthesis Example 4 Polyamino acid urethane blend resin To a mixed solution of 80 parts of toluene and 20 parts of N,N-dimethylformamide, a mixed NCA of 9 parts of L-leucine NCA and 2 parts of γ-methyl-L-glutamic acid NCAl was added and dissolved, and then 0.2 parts of ethylenediamine was added. After adding 5 parts and stirring at 25°C for 1 hour, polymerization was carried out at 60°C for 5 hours. This polymerization solution 10
To 0 parts, 40 parts of the urethane resin solution obtained in Synthesis Example 1 was added and mixed uniformly to obtain a polyamino acid urethane mixed resin.

Example 1 Preparation of a synthetic resin composition A) To 100 parts of solid content in the resin solution obtained in Synthesis Example 2, 10 parts of an aluminum coupling agent AL-M (Ajinomoto ■1j) was added and mixed uniformly. A synthetic resin composition was obtained.

B) To 100 parts of solid content in the resin solution obtained in Synthesis Example 2, add 10 parts of aluminum coupling agent AL-M (manufactured by Ajinomoto) and 0 parts of TSF451-500 (manufactured by Toshiba Silicone). The mixture was mixed uniformly to obtain a synthetic resin composition.

Example 2 Creation of porous synthetic sheet Synthetic resin composition 100 obtained in A) or B) of Example 1
1 part of water and 1 part of cross-linking agent C-2298 (manufactured by Nippon Polyurethane) were mixed uniformly on a non-woven cotton fabric using a roll coater to coat the nonwoven cotton fabric with a coating of 200 g/m2. °C x 5 minutes, 120°C x 2/5 minutes
A porous synthetic sheet was obtained by performing stage drying to remove the solvent and water. Each N.

, 1. No, set as 2. Table 1 shows the results of evaluating the surface slipperiness and water repellency of this material.

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.

Table 1 Evaluation Results Example 3 Creation of Porous Highly Moisture Permeable Synthetic Sheet 100 parts of the synthetic resin composition obtained in Example 1 A) or B) was mixed with 10 parts of water and the surfactant EMALEX103 (made by Nippon Emulsion Co., Ltd. )0.5 part was added to the emulsion solution and stirred at high speed. Crosslinking agent C-2298 (manufactured by Nippon Polyurethane)
Add 1 part of the resin solution and mix uniformly, coat the nylon taffeta with a roll coater at 50g/m2, and perform two stages of drying at 80℃ x 5 minutes and 120℃ x 5 minutes to remove the solvent and water. A porous high temperature permeable synthetic sheet was obtained. No, 3 respectively. No, set as 4. The results of evaluating the surface slipperiness and water repellency of this material are shown in the table.

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

Table 2 Evaluation Results Example 4 Creation of Porous Synthetic Sheet For 100 parts of solid content in the polyurethane resin of Synthesis Example 1, 3 parts of water and 10 parts of crosslinking agent C-22988 were used. Preparation and evaluation were carried out according to Examples 1 and 2 under the conditions shown in Table 3 regarding the amount, etc. The results are shown in Table 4.

Table 4. Evaluation results In Comparative Examples 4 and 5, it was not possible to form a film.

Example 5 Creation of porous synthetic sheet 3 parts of water, crosslinking agent C-229810 per 100 parts of solid content in the polyamino acid urethane copolymer resin of Synthesis Examples 2 and 3
The following coupling agent, type of polysiloxane,
The cups and the like were prepared and evaluated according to Examples 1 and 2 under the conditions shown in Table 5, and the results are shown in Table 6.

Table 5 Combination prescription table 6. Evaluation Results Example 6 Creation of Porous Synthetic Sheet Solid content in polyamino acid urethane mixed resin of Synthesis Example 4 1
Prepared according to Examples 1 and 2 using 3 parts of water and 10 parts of crosslinking agent C-2298 per 00 parts, and under the conditions shown in Table 7 for the coupling agent, type and amount of polysiloxane, etc., and after coating 80 parts. It was dried at 120° C. for 5 minutes and 120° C. for 30 minutes, and then evaluated. The results are shown in Table 8.

Table 7 Combination prescription table 8. Evaluation Results Example 7 Creation of Porous Highly Moisture Permeable Synthetic Sheet For 100 parts of solid content in the polyurethane resin of the synthetic example, 60 parts of water, 10 parts of C-229810, and the surfactant EMALEX103.
Using 1 part (manufactured by Nippon Emulsion ■), preparation and evaluation were carried out according to Examples 1 and 3 under the conditions shown in Table 9 regarding the coupling agent, type and amount of polysiloxane, etc.

The results are shown in Table 10.

Table 10. Evaluation results In Comparative Examples 9 and 10, it was not possible to form a film.

Example 8 Creation of porous moisture permeable synthetic sheet Solid content in polyamino acid urethane copolymer resin of Synthesis Examples 2 and 3: 10
0 parts, 40 parts of water, 1 part of EMALEX 103, 10 parts of crosslinking agent C-2298 Prepared according to Examples 1 and 3 under the conditions shown in Table 11 regarding the coupling agent, type and amount of polysiloxane, etc. , conducted an evaluation. The results are shown in Table 12.

Table 11 Formulation Table 12 Evaluation Results Example 9 Creation of Porous Highly Moisture Permeable Synthetic Sheet For 100 parts of solid content in the polyamino acid urethane mixed resin of Synthesis Example 4, 40 parts of water and 1031 parts of EMALEX Crosslinking agent C-22
Using 9810 parts, preparation and evaluation were carried out according to Examples 1 and 3 under the conditions shown in Table 13 regarding the coupling agent, type of polysiloxane, (2), etc. The results are shown in Table 14.

Table 13 Formulation Table 14 Evaluation Results Effects of the Invention By using the synthetic resin composition of the present invention, excellent waterproofness and abrasion resistance are imparted to porous synthetic sheets, and moisture permeability is also improved. It can be used not only for synthetic sheets such as leather and moisture-permeable waterproof fabric, but also for industrial applications.

Claims (4)

[Claims] (1) A resin composition containing 0.1 to 30 parts by weight of a coupling agent per 100 parts of polyurethane resin. (2) A resin composition containing 0.1 to 30 parts by weight of a coupling agent per 100 parts of a polyamino acid urethane copolymer resin or a mixed resin of polyamino acid and polyurethane. (3) Resin composition 100 according to claim (1) or (2)
1. A resin composition containing 0.1 to 50 parts by weight of a silicon-containing compound. (4) A porous synthetic sheet obtained by adding water to the resin composition according to claim (1), (2), or (3) to form an emulsion solution, and coating the resulting emulsion solution on a substrate to form a dry film.