JPS6254811B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a water-dispersible polyester suitable as a surface modifier or adhesive for polymer molded products and textile products. polyester that can impart improved texture to synthetic fiber products without impairing flame retardancy, or polyester that can be used as an adhesive that does not impair flame retardancy;
Another object of the present invention is to provide a polyester that can impart flame retardancy to combustible textile products. Conventionally, synthetic polymers such as polyester and polyamide have excellent properties not found in natural polymers, so they have been widely used as fibers for clothing and industrial purposes, and as films and other molded products for household use. However, on the other hand, it has drawbacks such as poor adhesion because it is highly hydrophobic and difficult to get wet, and because it is easily charged with static electricity, it attracts dust and clings to it while being worn. It is also thermofusible,
When combustible, it melts and falls and is easily extinguished, so its flammability is lower than that of cellulose fibers, etc., and it is known that it can be made flame retardant relatively easily by adding a small amount of flame retardant; Fiber products also have the disadvantage that they become flammable again if their heat meltability is even slightly impaired by the texture adjustment treatment using a hard finishing agent. Therefore, there is a strong market demand for a treatment agent that imparts a hard texture to flame-retardant textile products without impairing their flame retardancy. The inventors of the present invention have conducted intensive research on a texture modifier that does not impede heat-meltability or flame retardancy even when added to heat-melting flame-retardant fibers, and as a result, they have developed the polyester of the present invention. That is, in the present invention, when producing a polyester from an acid component mainly consisting of at least one aromatic compound selected from terephthalic acid, isophthalic acid, and their ester-forming derivatives, and a glycol component, 5-sodium sulfoisophthalate is used. An acid or its dialkyl ester or 5-potassium isophthalic acid or its dialkyl ester, a polyalkylene glycol with a molecular weight of 400 to 10,000, and a phosphorus-containing carboxylic acid having a phenanthrene skeleton represented by the following general formula [] or its ester-forming derivative. A method for producing a water-dispersible polyester resin characterized by copolymerization. However, R: hydrogen, a hydrocarbon group having 1 to 6 carbon atoms R ₁ , R ₂ : hydrogen, halogen, 1 to 6 carbon atoms
8 alkyl group, aryl group, aralkyl group m: 0 or an integer from 1 to 4 n: 0 or 1 The polyester of the present invention is used as a treatment agent for hydrophobic polymer molded articles to improve the wetting of the surface of the molded article,
It has the characteristics of improving adhesion, reducing adsorption of dust, etc., improving printability, and providing anti-fogging properties. It is also effective as a texture modifier for textile products, and depending on the polymer composition, it can impart a durable hard texture to flame-retardant textile products without sacrificing flame retardancy. Has characteristics. Furthermore, by increasing the copolymerization ratio of the phosphorus-containing carboxylic acid used in the present invention, it becomes useful as a treatment agent for imparting flame retardancy to combustible polymer molded articles and combustible thermoplastic fiber products. Furthermore, it can also be used as a binder for nonwoven fabrics, or as an adhesive between textile products or between textile products and other polymer molded products, or between polymer molded products. To explain the polyester of the present invention in more detail, it mainly contains at least one aromatic carboxylic acid (including ester-forming derivatives) selected from terephthalic acid, oxybenzoic acid, isophthalic acid, and ester-forming derivatives thereof, An acid component optionally combined with an aliphatic carboxylic acid (including ester-forming derivatives) selected from adipic acid, sebacic acid, or their ester-forming derivatives, and ethylene glycol, propylene glycol, butanediol, hexanediol, diethylene glycol, When producing polyester from a glycol component selected from alkylene glycols such as dipropylene glycol, 5-sodium sulfoisophthalic acid or its dialkyl ester or 5-potassium isophthalic acid or its dialkyl ester (hereinafter referred to as metal sulfonate group-containing compound) ), and the molecular weight is 400~
10,000 polyalkylene glycol and (b) a carboxylic acid having a phenanthrene skeleton represented by the above general formula [] or its ester-forming derivative is a method for producing a water-dispersible (including water-soluble) polyester. As the acid component, aromatic carboxylic acid accounts for 50 mol% or more, preferably 70 mol% or more, based on the total acid component, and aromatic carboxylic acids mainly composed of terephthalic acid are particularly preferred. Further, as the alcohol component, diethylene glycol is particularly preferred from the viewpoint of water dispersibility and stability. It is also preferable to substitute a portion of diethylene glycol with another glycol. The bifunctional compound having a metal salt sulfonate group as component (a) to be copolymerized includes dicarboxylic acids, diols, oxycarboxylic acids, or ester-forming derivatives thereof having at least one metal salt sulfonate group in the molecule. Can be mentioned. Specifically, 5-sodium sulfoisophthalic acid, 5-
Examples include potassium sulfoisophthalic acid, 5-sodium sulfoisophthalic acid dimethyl ester, and sodium 2,6-di(carbomethoxy)naphthalenesulfonate. Particularly preferred, however, is 5-sodium sulfoisophthalic acid or its ester-forming derivatives. Examples of polyalkylene glycols include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, random or block copolymers of ethylene oxide and propylene oxide, random or block copolymers of ethylene oxide and butylene oxide, and adducts of glycol and alkylene oxide. The molecular weight is particularly preferably from 600 to 5,000. Specific examples of the compound represented by the formula () of component (b) include compounds represented by the following formulas [] to []. However, particularly preferred are compounds represented by the formulas [] and []. Component (a) is a component that gives water dispersibility or water solubility to polyester, and its copolymerization ratio differs between the metal salt sulfonate group-containing compound and the polyalkylene glycol, but in the case of the metal salt sulfonate group-containing compound alone, compound to total acid components,
It is usually 6 mol% or more, preferably 10 mol% or more, and more preferably 20 to 50 mol%. Further, when polyalkylene glycol is used alone, the copolymerization ratio is such that the polyalkylene glycol accounts for 10 to 80% by weight, preferably 30 to 70% by weight, based on the polymerization of the resulting polyester. A polyester copolymerized solely with a compound containing a metal salt sulfonate group imparts a hard texture, while a polyester copolymerized with a relatively large amount of polyalkylene glycol imparts a soft texture. When the two copolymerization components are copolymerized together, the wide range of proportions in which they are used is determined depending on the desired texture, ranging from a hard texture to a soft texture. However, when durability is also considered, a copolyester containing a metal salt sulfonate group-containing compound as a main component and giving a hard texture is preferred. In addition, component (b) particularly imparts affinity for hydrophobic fibers, and imparts flame retardancy to the polymer itself.
Used as a surface modifier for flame-retardant molding materials to modify surface properties without impairing flame retardancy. The copolymerization molar ratio is usually 1 to 10 mol% based on the total acid component.
is sufficient, preferably 2 to 5 mol%.
When about 5 mol% or more is copolymerized, it becomes useful as a flame retardant agent for combustible thermoplastic fiber products. The method for producing the modifier of the present invention can be carried out in accordance with conventionally known polyester production methods.
For example, it can be produced by transesterifying a predetermined amount of each acid component in the form of dimethyl ester and a glycol component in a known transesterification catalyst, and then polycondensing it in the presence of a polycondensation catalyst. As the transesterification catalyst and polymerization catalyst in this case, titanium-based catalysts are particularly preferred. The reduced viscosity of the polyester determined at a concentration of 0.4 g/dl in a phenol/tetrachloroethane (3/2 weight ratio) solvent at 30°C is 0.1 or more. Although the water-dispersible polyester obtained according to the present invention can be used as an internal additive in polymer molded articles to modify the surface properties, it is usually possible to modify the surface properties by post-treating the molded article. It is particularly useful as a quality agent. When used in post-treatment, it is usually desirable to disperse or dissolve the polyester in water, optionally using a surfactant. Conveniently, the concentration of the modifier is usually 10% by weight or more, especially 20-30% by weight. Treatment methods with modifiers include applying the modifier to the molded product by any means such as spraying or padding, drying and optionally heat-treating, or immersing the molded product in a treatment solution to exhaust the modifier. etc. The amount applied is usually 0.01% by weight or more, preferably 0.1 to 10% by weight. Examples of the polymer molded product include natural, synthetic, and recycled polymers such as cellulose, polyester, polyamide, polyacrylonitrile, etc. The molded product may be in any form such as fiber, film, or plate. However, it is effective for heat-melting fibers such as polyester and polyamide, and is particularly advantageous when applied to flame-retardant polyester fiber products. The present invention will be explained below with reference to Examples. In addition,
Parts and percentages in the examples are parts and percentages by weight. Example 1 1154 parts of dimethyl isophthalate (in total acid components)
56.8 mol%), sodium dimethyl sulfoisophthalate 1243 parts (40 mol% of total acid components), formula []
A mixture consisting of 126 parts of the compound represented by (3.2 mol% in total acid components), 2020 parts of diethylene glycol, 15.0 parts of sodium acetate, and 1.9 parts of potassium titanyl oxalate was subjected to transesterification reaction at a temperature of 160 to 240°C for 2 hours to obtain the ester. 3500 parts of polyethylene glycol with an average molecular weight of 1000 as the exchange reaction product (35 mol% based on the total diol component of the polyester produced)
was added, and then the temperature of the reaction system was raised while gradually reducing the pressure to 265°C and 0.3 mmHg over 80 minutes. Polycondensation was continued under these conditions for an additional 15 minutes. The resulting polymer had a softening point of 140°C, a concentration of 0.4 g/dl in a phenol/tetrachloroethane mixed solvent (3/2), and an intrinsic viscosity of 0.20 as measured at 30°C. The polyester modifier thus obtained was dissolved in water to form a 20% aqueous solution, which was used as a processing agent (A). Heim (Toyobo Co., Ltd. flame-retardant modified polyester fiber) lace curtain was padded with a 5% aqueous solution of processing agent (A), and the squeezing rate was
After squeezing the liquid at 80%, it was dried and heat treated at 150°C for 2 minutes. As a result, a stiff, hard texture was obtained without reducing flame retardancy, and the washing durability was also good. Example 2 A polyester modifier was produced in the same manner as in Example 1 except that the molar ratio of the acid component was changed as shown in Table 1.
It was made into an aqueous solution. With processing agent F, it was difficult to obtain a stable dispersion even when an emulsifier was used.

[Table] Drape curtains made of Heim short fibers (fabric weight
200g/m ² ) and squeezed with a squeezing rate of 80%.
After drying at 120°C, it was heat-treated at 160°C for 1 minute.
The flame retardancy and hardness (cantilever method) of the obtained treated fabric were evaluated, and the results shown in Table 2 were obtained.

【table】

[Table] As is clear from Table 2, the finishing agent E of Comparative Example, in which the compound of formula [] was not co-condensed, has the disadvantage that flame retardancy decreases when used in a large enough amount to obtain a hard texture. In addition, in order to maintain flame retardancy, it is difficult to obtain a hard grain texture when used in small amounts. Example 3 A lace curtain made of polyethylene terephthalate filaments was coated with an aqueous solution consisting of 5 parts of a 30% aqueous dispersion of tris(2,3-dibromopropyl) phosphate, 15 parts of a 20% aqueous solution of processing agent D in Example 2, and 80 parts of water. Pad with liquid, squeeze with 80% squeezing rate, dry and heat treat (150℃, 5 minutes)
As a result, a lace curtain with a firm texture and good flame retardancy was obtained. Example 4 When producing polyethylene terephthalate from dimethyl terephthalate and ethylene glycol by a conventional method, a part of the acid component was replaced with a compound represented by the general formula [] (5 mol % based on the total acid composition) and 5
- Substituted with potassium sulfoisophthalic acid (5 mol% based on the total acid components) and copolymerized with polyethylene glycol having an average molecular weight of about 2000 (15% by weight based on the polyester produced) to obtain a polyester polyether block copolymer (Example 1) A reduced viscosity of 3.25) was produced in the same manner as above. The resulting polyester was dispersed in water, and flame-retardant polyester fibers were treated with a 1% dispersion, then dried and heat-treated (150°C, 3 minutes), resulting in elasticity without impeding flame retardancy. It has a rich texture, improved hydrophilicity, and improved antistatic properties, and also shows excellent durability against repeated washing.

Claims (1)

[Scope of Claims] 1. When producing a polyester from an acid component mainly consisting of at least one aromatic compound selected from terephthalic acid, isophthalic acid, and their ester-forming derivatives, and a glycol component, 5
- sodium sulfoisophthalic acid or its dialkyl ester or 5-potassium isophthalic acid or its dialkyl ester, and the molecular weight is
400 to 10,000 polyalkylene glycol and a phosphorus-containing carboxylic acid having a phenanthrene skeleton represented by the following general formula [ ] or an ester-forming derivative thereof are copolymerized. A method for producing a water-dispersible polyester resin. However, R: hydrogen, a hydrocarbon group having 1 to 6 carbon atoms R ₁ , R ₂ : hydrogen, halogen, 1 to 6 carbon atoms
8 alkyl group, aryl group, aralkyl group m: 0 or an integer from 1 to 4 n: 0 or 1