JPS642710B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for wet-coagulating a polyester solution on a sheet to form a porous resin layer and for wet-processing the sheet to obtain a unique texture and finishing effect. Conventionally, a method of applying a polyurethane solution to a fiber sheet and then immersing it in a non-solvent to coagulate the polyurethane to form a water vapor permeable film is widely known as a method for producing breathable synthetic leather. In these methods, the microporosity of the resin layer varies greatly depending on not only the selection of the type of polymer but also the conditions set during the coagulation step. In general, it is difficult to form a porous resin layer with uniformity and excellent smoothness using polyester, which lacks a good solvent and has a large cohesive force. On the other hand, in resin processing of textile products, water is evaporated by hot air drying after applying an aqueous resin liquid.
Methods of fixing resins onto fibers have been widely used. Although this method is extremely versatile and easy to operate, it has the disadvantage that a uniform and excellent treatment effect cannot be expected because the resin migrates and is fixed on the surface side or surface layer where hot air hits, that is, where water evaporates. have. Particularly in the case of hydrophobic synthetic fibers such as polyester fibers, the amount of water retained inside the fibers is close to zero, so the problem of resin migration is extremely serious. The inventors of the present invention have conducted extensive research into wet processing of sheets that is free from these drawbacks and is highly durable, and have thus arrived at the method of the present invention. That is, the present invention provides a sheet containing a copolymerized polyester containing 0.5 to 10 mol% of a sulfonic acid metal base-containing ester-forming compound based on the total acid component, a softening point of 40 to 200°C, and a substantially water-insoluble copolyester; After applying a solution containing a water-soluble organic solvent, a polyvalent metal salt compound and/or
Alternatively, it is characterized by treatment with an aqueous acid solution. When using the method of the present invention, the adhesion of the resin is uniform, stable and excellent finishing effects can be obtained, and in some cases, a porous resin layer with good microporosity and excellent surface smoothness can be obtained. It has characteristics such as being able to be formed. Another major feature is that it has excellent durability. The method of the present invention will be explained in more detail. Specific water-insoluble copolyesters used in the present invention include terephthalic acid, isophthalic acid, orthophthalic acid, aromatic dicarboxylic acids such as 2,6-naphthalene dicarboxylic acid, succinic acid, adipic acid, azelaic acid, and sebacic acid. , aliphatic or cycloaliphatic dicarboxylic acids such as maleic acid, fumaric acid, dotecanedionic acid, dimer acid, tetrahydrophthalic acid, hexahydrophthalic acid, hexahydroterephthalic acid, oxybenzoic acid, oxyethoxybenzoic acid, oxypivalic acid ,ε−
Oxyacids such as caprolactone or their ester-forming transparent conductors are used as acid components, and aliphatic glycols such as ethylene glycol, propylene glycol, butanediol, diethylene glycol, dipropylene glycol, neopentyl glycol, pentanediol, and hexanediol are used as acid components. , sulfonic acid metal base-containing ester-forming components, such as sulfosuccinic acid, sulfoterephthalic acid, 5-sulfoisophthalic acid, in the production of polyesters containing alicyclic glycols such as cyclohexanedimethanol, or their ester-forming derivatives as glycol components. acid, dicarboxylic acids such as 4-sulfoisophthalic acid, 4-sulfonaphthalene-2,7-dicarboxylic acid, and 5[4-sulfophenoxy]isophthalic acid, as well as oxycarboxylic acids containing sulfonic acid metal groups, and glycols containing sulfonic acid metal groups. The softening point obtained by copolymerizing
~200°C, and 0.5 to 10 mol% of the sulfonic acid metal base-containing ester-forming compound based on the total acid component,
Particularly preferred are copolyesters containing 1 to 7 mol%. If the softening point is less than 40°C, durability will be poor, and if it exceeds 200°C, water dispersibility will be difficult, and the film formed from an aqueous solution will have poor film properties and processability. Furthermore, if the sulfonic acid metal base-containing ester-forming compound is less than 0.5 mol%, the polyester itself will have difficulty dispersing, and the stabilizing effect of the aqueous treatment liquid will not be obtained.
If it exceeds 10 mol %, there will be a drawback that film forming properties, durability, weather resistance, etc. will be reduced. In addition, the molecular weight of copolymerized polyester is about 2,500 to 30,000, especially 5,000.
~25000 is preferred. In the production of the above-mentioned polyester, a crosslinking component such as a trifunctional or higher functional compound such as trimetic acid, pyromellitic acid, trimethylolpropane, trimethylolethane, pentaerythritol, etc. may be copolymerized to the extent that water dispersibility is not impaired. Polyalkylene glycol, such as polytetramethine glycol having a molecular weight of 106 to 10,000, may be used in an amount that does not impair properties and weather resistance, usually 50% by weight or less, preferably 20% by weight or less based on the glycol component. Examples of metal salts include salts of Li, K, Na, etc., and particularly preferred is Na salt. Aromatic dicarboxylic acids account for 40% of the total acid component as the acid component of copolymerized polyester.
-100 mol%, and aromatic carboxylic acid having a sulfonic acid metal base content of 1 to 5 mol% is particularly preferred from the viewpoint of durability and weather resistance. The copolyester may be substantially amorphous or crystalline. Amorphous copolymerized polyester can be easily dispersed in fine particles into a stable aqueous dispersion with a particle size of 1μ or less with the help of water-soluble organic solvents such as lower alcohols, glycols, cellosolves, cyclic ethers, and ketones. Alternatively, the crystalline copolymerized polyester can be mixed with the amorphous copolymerized polyester and the above-mentioned water-soluble organic solvent to disperse fine particles in an aqueous dispersion. As the water-soluble organic solvent, those having a solubility in water 1 at 20°C of 20 g or more and a boiling point of 50 to 200°C are usually used. Particularly preferred are ethyl cellosolve, n-butyl cellosolve, and isoprobanol. The amount of water-soluble organic solvent used is preferably 2 to 50% by weight based on the total amount of water and water-soluble organic solvent. However, water-soluble organic solvent systems with high boiling points other than those mentioned above can also be used. In the present invention, "substantially water-insoluble" means that the solubility in hot water is 70% by weight or less. In addition, hot water solubility is determined by adding 20g of resin powder to 80ml of water at 70°C.
After stirring for 30 minutes, filter through a 1G glass filter,
Concentrate the filtrate to determine the amount of solids dissolved in water. Hot water solubility (%) = Dissolved solid content g/20g x 100 The solution or aqueous dispersion containing the copolymerized polyester and the water-soluble organic solvent may further contain polyalkylene glycols, cellulose derivatives, starches, polyvinyl alcohol, Maleic acid/styrene copolymer, water-soluble polymers that control the fine pores of the film such as sodium algyl acid, fine cellulose powder, organic or inorganic fine powder such as clay, talc, silica, alumina, carbon, acid In addition to water-soluble alkali metal salts or ammonium salts,
Waxes such as fatty acid salts and fatty acid esters,
Other polyesters, polyurethanes, etc. that can be dispersed or dissolved in the softener, crosslinking agent, or processing liquid and coagulated in the same manner as the copolymerized polyester can also be blended. Additionally, a small amount of an activator may be used in combination to adjust the stability of the solution. Sheets to be subjected to the wet treatment of the present invention include fiber sheets, synthetic papers, films, tapes, etc., but it is particularly effective when applied to breathable fiber sheets. Fiber sheets include non-woven sheets, knitted fabrics, and warped sheets made of natural fibers such as cotton, wool, and linen, recycled or semi-synthetic fibers such as rayon and acetate, and synthetic fibers such as polyester, polyamide, and acrylic. , raised sheets, etc., but it is particularly effective when applied to hydrophobic synthetic fiber sheets. In the present invention, the copolyester is applied to the sheet by any means such as impregnation or coating, and then applied with an aqueous solution of polyvalent metal salt and/or acid without substantially drying. The treatment results in wet coagulation of the copolymerized polyester. This wet treatment is usually conveniently carried out by immersion in an aqueous solution of a polyvalent metal salt and/or acid. Examples of polyvalent metal salt compounds include salts of polyvalent metals such as magnesium, calcium, aluminum, iron, manganese, and zinc, such as magnesium chloride and aluminum chloride. The type of polyvalent metal salt depends on the intended use of the treated product, but magnesium chloride and aluminum chloride are usually advantageous when wastewater treatment is also taken into consideration. Further, the acid may be any acid that gives a pH of about 5 or less, preferably 4.0 or less. The concentration of the polyvalent metal salt used is not particularly limited, but it varies depending on the chemical composition of the processing agent used, the amount used, additives, etc., but it is usually 1 to 10% by weight, particularly preferably 5% by weight.
~10% by weight. Further, the temperature of this treatment liquid may normally be room temperature. The immersion time also varies depending on the amount of treatment agent applied to the sheet, but 5 to 30 seconds is usually sufficient. The thus coagulated sheet is washed with hot water, optionally soaped, dehydrated, and then dried. In addition, the treatment with polyvalent metal salt aqueous liquid or acid aqueous liquid in this treatment is not limited to the method of immersion in these water, but also the method of treating the entire surface or part with spray etc. and coagulating only that part. The method is also effective depending on the purpose. Furthermore, it is also possible to perform heat treatment after these treatments (after drying) to harden the resin. Note that the treatment liquid can also be applied to only one side of the sheet or to a portion of the sheet by subjecting it to water-repellent treatment or water- and oil-repellent treatment before the treatment of the present invention. In addition, the sheet obtained by wet coagulation treatment can be further embossed,
It can also be wrinkled to give it a design, or it can be given water-repellent treatment, water- and oil-repellent treatment, etc. to make it breathable and waterproof. The sheets thus obtained have excellent affinity with printing inks and printability, so they can be used as printing cloths, and because they form a breathable film, they can be used as breathable waterproof sheets or synthetic leather-like products. It can be used for many purposes, such as as an adsorption film (when an adsorbent is blended and coagulated), as an adhesion base for marine products and microorganisms, and as an interlining. The present invention will be explained below with reference to Examples. In addition,
In the examples, parts and % simply refer to parts and % by weight unless otherwise specified. Evaluation of various properties was performed according to the following methods. (1) Molecular weight Measured using a molecular weight measuring device (model 115 manufactured by Hitachi, Ltd.). (2) Softening point and crystal melting point Fully automatic melting point measuring device (manufactured by METTLER)
The measurement was carried out using MODEL FP-1). (3) Particle size of aqueous dispersion Measured using a grindmeter and an optical microscope. (4) Viscosity Measured at 25 using a B-type viscometer. Production example of copolymerized polyester 1 95 parts of dimethyl terephthalate, 95 parts of dimethyl isophthalate, 71 parts of ethylene glycol, 110 parts of neopentyl glycol, 0.1 part of zinc acetate and 0.1 part of antimony trioxide were charged in a reaction vessel and the mixture was heated at 140 to
Transesterification reaction was carried out at 220°C for 3 hours.
Then 5-sodium sulfoisophthalic acid 6.0
The esterification reaction was carried out at 220-260°C for 1 hour, and then the
A polycondensation reaction was carried out for 2 hours at 0.2 mmHg) to obtain a copolymerized polyester (A-1) having a molecular weight of 19,500 and a softening point of 160°C. Furthermore, copolymerized polyesters (A-2) to (A-
8) was obtained. Their characteristic values were as shown in Table 1.

[Table] Example of manufacturing an aqueous dispersion of copolymerized polyester 300 parts of copolymerized polyester (A-1) and 140 parts of n-butyl cellosolve are placed in a container,
After stirring at 170℃ for about 3 hours to obtain a homogeneous and viscous melt, 545 parts of water was gradually added while stirring vigorously, and after about 1 hour, a homogeneous pale bluish-white aqueous dispersion (B-1) was obtained. ) was obtained. The obtained aqueous dispersion had good dispersibility and excellent storage stability. Similarly, aqueous dispersions (B-2) to (B-9) were obtained in the proportions shown in Table 2. Their dispersibility and dispersion stability are shown in Table 2.

【table】

[Table] Example 1 A 100% polyester bread fabric (45 x 45/110 x 76) was desized and scoured in a conventional manner, and then padded with a 20% aqueous solution of aqueous dispersion B-1 shown in Table 2. Then, the fabric was immersed in a 5% aqueous solution of magnesium chloride for 5 seconds, washed with hot water, dried, and then heat set at 170°C for 30 seconds, yielding a hard finished fabric with excellent washing durability. The anti-pilling properties were also improved to a level of 2. This finishing cloth is Diacryl Blue KSL-N1%
When the fabric was stained with an aqueous solution at 60°C for 1 minute, there was almost no difference in adhesion between the front and back sides of the fabric. On the other hand, after padding
When the paper was dried in a hot air dryer at 130°C and then set at 170°C for 30 seconds, the same stain test showed that there was a significant difference between the front and back sides. Example 2 After desizing, scouring and dyeing polyester filament taffeta (75d/24f x 75d/24f/128 x 90), it was padded with a 20% aqueous solution of aqueous dispersions B-2 to B-5 in a wet state and immediately washed. After immersing it in an 8% aqueous solution of magnesium chloride for 5 seconds, it was washed with hot water, washed with water, dried, and set to obtain a durable hard finished fabric. On the other hand, in comparative examples using aqueous dispersions B-6 and B-9, wet coagulation was not possible and the expected treatment effect could not be obtained. Moreover, the comparative example using aqueous dispersion B-7 not only had poor treatment effects but also had completely insufficient durability. Production example of copolymerized polyester 2 553 parts of dimethyl terephthalate, 388 parts of dimethyl isophthalate, 45 parts of 5-sodium sulfoisophthalate, 234 parts of butanediol, 266 parts of hexanediol, 150 parts of polytetramethylene glycol (MW=1000), acetic acid A reaction vessel was charged with 0.44 parts of zinc, 0.05 parts of sodium acetate, and 0.43 parts of antimony trioxide, and a transesterification reaction was carried out at 140 to 230°C for 4 hours. Next, while increasing the temperature to 260℃, the pressure inside the reaction system was gradually reduced to 5mmHg after 1 hour.
And so. Finally, a polycondensation reaction was performed at 260℃ for 1 hour under reduced pressure of 0.1 to 0.3 mmHg, resulting in a molecular weight of 16,000,
Melting point 128℃, heat of crystal fusion measured by differential scanning calorimeter
320 cal/unit crystalline copolymer polyester C-1
I got it. On the other hand, 475 parts of dimethyl terephthalate, 466 parts of dimethyl isophthalate, 45 parts of dimethyl 5-sodium sulfoisophthalate, ethylene glycol
443 parts and 400 parts of neopentyl glycol were used, but the molecular weight was 7000 and the softening point was 1.
Amorphous copolymerized polyester D-1 was obtained at 52°C. The heat of crystal fusion of this copolyester was measured using a differential scanning calorimeter, but no endothermic peak was observed. Production example of aqueous dispersion of copolyester 2 120 parts of crystalline copolyester (C-1),
180 parts of amorphous copolymerized polyester (D-1) and 140 parts of n-butyl cellosolve were charged into a container and stirred at 150 to 170°C for about 3 hours to obtain a uniform and viscous melt. While stirring vigorously, 560 parts of water was gradually added, and after about 1 hour, a uniform pale blue aqueous dispersion (E-1) was obtained. The resulting aqueous dispersion had a particle size of 1 μm or less, and no change in appearance was observed even after it was left at −5° C. for one month, indicating excellent storage stability. Example 3 Polyester filament taffeta was desized, scoured and heat set, and then the above aqueous dispersion (E-1) was coated with a bar coater #20 to reduce the film thickness.
Immediately after applying 20μ of magnesium chloride, 10
% water solution for 5 seconds, then rinse with hot water, rinse with water,
After drying, a coated cloth was obtained. Sheets printed on this coated cloth using a label printer have become a display material that is durable against washing. Example 4 Fabric weight made of 0.5d polyester filament
After coating one side of a 60 g/m ² spunbond nonwoven fabric with a water- and oil-repellent agent to make it water- and oil-repellent, the other side was back-coated with the aqueous dispersion (E-1), and then wet coated in the same manner as in Example 3. Coagulated. As a result, a leather-like sheet with a microporous resin layer was obtained.

Claims (1)

[Claims] 1. A copolymer containing 0.5 to 10 mol% of a sulfonic acid metal base-containing ester-forming compound based on the total acid components, a softening point of 40 to 200°C, and a substantially water-insoluble copolymer. A wet processing method for a sheet, which comprises applying a solution containing a polyester and a water-soluble organic solvent, and then treating the sheet with an aqueous solution of a polyvalent metal salt compound and/or an acid. 2. The wet processing method for a sheet according to claim 1, wherein the sheet is a breathable fiber sheet.