JPH0132250B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a polyester film treatment agent, and more specifically, it is used as a surface treatment agent for molded products, especially polyester molded products, and for textile products, especially polyester fiber products, with excellent washing resistance and dry cleaning resistance. Another object of the present invention is to provide a polyester-based processing agent suitable as a processing agent that provides a soft texture with color fastness. In recent years, polyester molded products have been used in large quantities for various purposes. In particular, polyester fibers occupy a very advantageous position compared to other fibers due to their excellent performance. These polyester molded products also have drawbacks, and in order to solve these drawbacks, they can be treated with various processing agents (e.g., softening agents, hard finishing agents, antistatic agents, adhesion improvers, etc.) depending on the purpose. However, polyester-based processing agents are generally preferred due to their compatibility with molded articles. In addition, various processing agents that are water-soluble or water-dispersible have been studied for ease of processing. For example, as a water-soluble or water-dispersible polyester treatment agent, a polyester consisting of dicarboxylic acids, polyethylene glycol with a degree of polymerization of 2 to 10, and a bifunctional compound containing sulfonic acid or a sulfonic acid metal base (Japanese Patent Publication No. 47-40873 ),
Block copolymerized poly(ester ether) consisting of an aromatic dicarboxylic acid, glycol, an ester-forming sulfonic acid alkali metal salt compound, and polyethylene glycol (Japanese Patent Application Laid-open No. 12336/1982),
Aromatic dicarboxylic acids, aliphatic dicarboxylic acids,
Polyesters made of ester-forming alkali metal sulfonic acid salt compounds, glycol and diethylene glycol (Japanese Patent Application Laid-Open No. 54-3848) are known. These polyesters are useful as adhesives, sizing agents, etc. that do not require washing durability, but they do not provide flexibility, and on the contrary, not only do they harden the texture, but they also have poor color fastness (especially light resistance). There are drawbacks such as poor performance. On the other hand, block copolymer poly(ester ether) consisting of terephthalic acid component, ethylene glycol component and polytetramethylene glycol component
It is known that a treatment agent that is eutectic with a nonionic surfactant and dispersed in water imparts a flexible texture to polyester fibers and has good washing durability (Japanese Patent Publication No. 48-6619). , Special Publication No. 49-16774).
However, this treatment agent has the major drawbacks of being limited in its use for dyed products, as it significantly reduces the color fastness (particularly abrasion fastness) of molded products, and that its dry cleaning resistance is somewhat insufficient. have. The present inventors have arrived at the present invention as a result of intensive research to improve the above-mentioned drawbacks while maintaining the excellent performance of the processing agent. That is, the present invention uses as acid components (A) terephthalic acid or its ester-forming derivative, (B) isophthalic acid or its ester-forming derivative, and (C) 3,5-dicarboxybenzenesulfonic acid alkali metal salt or its ester. Formation derivatives, and as glycol components (D) diethylene glycol and (E) molecular weight 400
A block copolymerized poly(ether ester) obtained using polytetramethylene glycol of ~6000, the composition ratio of (A), (B) and (C) being 10~
50:50-90:2-5 moles, and the content of (E) is the block copolymerized poly(ether ester)
This is a polyester film processing agent characterized by an amount of 50 to 80% by weight. The polyester-based treatment agent according to the present invention exhibits an excellent softening effect particularly on textile products, especially polyester-based textile products, and the resulting products have excellent color fastness, washing resistance, dry cleaning resistance, etc. It is characterized by excellent durability.
It is also effective in improving the printability, antifogging properties, etc. of molded products, especially polyester molded products. Furthermore, the polyester treatment agent may contain small amounts of nonionic surfactants, particularly ethylene oxide or ethylene oxide/propylene oxide adducts of higher alcohols and/or higher fatty acids, polyether organopolysiloxane copolymers, Pluronic type surfactants, and perpendicular surfactants. Another major advantage in industrialization is that by containing ethylene oxide or ethylene oxide/propylene oxide adducts of fluoroalcohols and/or perfluorocarboxylic acids, they can be easily dispersed in water. The treatment agent of the present invention is a block copolymerized poly(ester ether) having a specific composition. Specifically, it contains (A) a terephthalic acid component, (B) an isophthalic acid component, and (C) a 3,5-dicarboxybenzenesulfonic acid alkali metal salt component as acid components. Particularly preferred alkali metals are sodium and potassium. The composition ratio is molar ratio (A):
(B):(C)=25-50:50-75:2-5. Particularly preferred is (A):(B):(C)=25-50:50-75:2-4. The composition ratio of the acid component is important because it affects the dispersibility of the treatment agent in water and the durability of the treated product. A part of component (B) can also be substituted with adipic acid, pimelic acid, azelaic acid, sebacic acid, etc., which are aliphatic dicarboxylic acids having 2 to 8 methylene groups. Further, the glycol component includes a diethylene glycol component and a polytetramethylene glycol component. The molecular weight of polytetramethylene glycol is usually 400 to 6000, preferably 700 to 4000
It is. The content of the polytetramethylene glycol component is 50 to 80% by weight based on the produced polymer.
The texture of treated products is greatly influenced by the content of polytetramethylene glycol components.
Therefore, its content is determined depending on the target product texture, the amount of treatment agent applied, etc. The production of the block copolymerized poly(ester ether) in the present invention is carried out in accordance with a conventional method for producing a conventional block copolymerized poly(ester ether). For example, lower alkyl esters of each acid component and diethylene glycol in an amount of about 1.5 times or more moles relative to the acid component are transesterified in the presence of a suitable catalyst (eg, a titanium compound, etc.). After completion of the reaction, a predetermined amount of polytetramethylene glycol is added and the polycondensation reaction is carried out under reduced pressure. A polymer with good color tone can be obtained by using a small amount of an oxidative decomposition inhibitor before or at the same time as adding polytetramethylene glycol. The block copolymerized poly(ester ether) has a reduced specific viscosity (solvent phenol/1,1,2,2-
Tetrachloroethane 6/4 weight ratio, polymer concentration
0.2g/100c.c., temperature 30°C) is usually preferably 0.8 or more, particularly preferably 1.0 or more. The block copolymerized poly(ester ether) is usually conveniently used as an aqueous dispersion. The characteristic feature is that it can be easily dispersed in water with the help of a small amount of nonionic surfactant. In particular, when the composition ratio of the acid component is less than 2 moles of 3,5-dicarboxybenzenesulfonic acid alkali metal salt (hereinafter referred to as DSN), water dispersibility deteriorates, so a large amount of dispersion aid is required, or dispersion is difficult. It is necessary to melt and depolymerize the prepolymer in the presence of water, which not only reduces the color fastness of the treated product but also reduces its dry cleaning resistance. Moreover, if DSN exceeds 5 moles, the washing durability of the effect decreases, making it unsuitable. Examples of nonionic surfactants include ethylene oxide or ethylene oxide/propylene oxide adducts of higher alcohols and/or higher fatty acids, ethylene oxide or ethylene oxide/propylene oxide adducts of perfluoroalcohols and/or perfluorocarboxylic acids, etc. It is preferable because it has less negative effect on various fastnesses of treated products. Higher alcohols and/or higher fatty acids include saturated or unsaturated alcohols with 8 to 40 carbon atoms, polyols, monocarboxylic acids, polycarboxylic acids, or each having one or more hydroxyl groups and carboxyl groups in one molecule. It is a compound. Specifically, alcohols or polyols such as octanol, octadecyl alcohol, cetyl alcohol, decanol, oleyl alcohol, lauryl alcohol, decamethylene diol, octadecane diol, lauric acid, myristic acid, palmitic acid, stearic acid, linoleic acid, linolenic acid. , mono- or polycarboxylic acids such as oleic acid, dodecanedicarboxylic acid, dimer acid, or ω-
Oxycarboxylic acids such as oxystearic acid. Perfluoroalcohols and perfluorocarboxylic acids have a structure in which part or all of the hydrophobic groups in the above-mentioned higher alcohols and higher fatty acids are substituted with fluorine atoms. Usually, ethylene oxide or ethylene oxide and propylene oxide are added randomly or in blocks to these compounds or a mixture thereof in the presence of a suitable catalyst.
The number of moles of these added is about 6 to 100, but it is usually preferable to add them so that the HLB is about 10 to 20. Different surfactants may be mixed and used to achieve the above HLB value. The amount of nonionic surfactant added is usually 15% by weight.
If more than this amount is added, it not only does not contribute to improving the dispersibility, but also causes a decrease in the performance of the treated product, such as a decrease in color fastness and washing resistance, which is undesirable. The lower limit of the blending amount is preferably about 3% by weight. A melt mixing method is usually employed to mix the block copolymerized poly(ester ether) and the nonionic surfactant. Examples include a method in which a predetermined amount of both are placed in a reactor equipped with a suitable stirrer and heated and melt-mixed, or a method in which a predetermined amount of a surfactant is added and mixed at the end of polycondensation of the block copolymerized poly(ester ether). In this case, favorable results can be obtained by taking care to remove moisture from both or mixing in an inert gas.
As the treatment agent, the above mixture is usually used by dispersing it in water. The above mixture can be easily dispersed in water by any method. The concentration of the dispersed polymer is determined by the purpose of the treatment or the treatment method,
Although not particularly limited, it is usually appropriate for the stock solution to contain about 5 to 30% by weight. Also, organic solvents that are miscible with water, such as alcohols such as methanol, ethanol, and propanol, ketones such as acetone and methyl ethyl ketone, ethers such as dioxane and ethylene glycol ethyl ether, and esters such as ethyl acetate, are used as polymers. An aqueous dispersion can also be produced by dissolving and dispersing by mixing with surfactant-containing water and optionally removing the organic solvent. By using an organic solvent in combination, water dispersion can be achieved with a smaller amount of surfactant than when using only a surfactant. As described above, the polyester treatment agent according to the present invention can be easily used as an aqueous dispersion, has good processing workability, and improves the texture, color fastness, washing resistance, dry cleaning resistance, etc. of treated products. Demonstrates excellent effects. The treatment agent according to the present invention can be used as a treatment agent for textile products, especially polyester fiber products such as woven and knitted fabrics, yarns, batting, non-woven fabrics, synthetic papers, rugs, cords, etc., and also for other molded products, especially polyester molded products such as films, tapes, etc. It is particularly useful as a surface treatment agent for plate-shaped objects, etc. These effects will be explained in detail in Examples below, but the present invention is not limited by the Examples. In addition, parts and percentages in the examples are based on weight unless otherwise specified. Example 1 54.6 parts of dimethyl terephthalate (DMT), 77.9 parts of dimethyl isophthalate (DMI), 6.3 parts of dimethyl 5-sodium sulfoisophthalate (DSN), and diethylene glycol (DEG) were placed in a reactor equipped with a stirrer, a thermometer, and a methanol outflow tube. ) 93 parts, and 0.5 part of titanium tetrabutoxide (5% butanol solution)
and gradually raise the temperature while stirring. After a predetermined amount of methanol has flowed out (internal temperature is 220°C), 352.1 parts of polytetramethylene glycol (PTG) with a number average molecular weight of 2000 and 1,3,5-trimethyl-2,4,6-tri(4-hydroxy- 3,5-
Add 1.5 parts of di-t-butylbenzyl)benzene,
While stirring, bring the internal temperature to 230°C. Transfer the resulting reaction mixture to an autoclave at 230°C. Then, while stirring, gradually reduce the pressure to 60
0.5 mmHg per minute. During this time, the temperature is increased to 245°C. After reacting for 60 minutes, the pressure is returned to normal using nitrogen gas, and the polymer is extruded onto a Teflon plate through the pores provided at the bottom of the autoclave using nitrogen gas pressure. The reduced specific viscosity of the obtained polymer was 2.36. Add 0.8 parts of polyoxyethylene lauryl ether (HLB 20) to 10 parts of the obtained polymer, melt it at 250°C under a nitrogen stream, and stir it into 90 parts of a 0.3% aqueous solution of monoethanolamine prepared in advance. The mixture was added to obtain an aqueous dispersion. Example 2 A 25 μm thick polyethylene terephthalate film was prepared using a 10% solution of the 10% dispersion obtained in Example 1 using A: Coating method B: Padding method, and the film was held horizontally for 120 minutes. ℃
After drying for 2 minutes, it was heat treated for fixation at 170°C for 30 seconds. Table 1 shows the antifogging properties and printing properties of the treated film.

【table】

【table】

[Table] Example 3 Polymers with various composition ratios were produced in the same manner as in Example 1, and their performance as film processing agents was evaluated in the same manner as in Example 2. The results are shown in Table 2.

【table】

Claims (1)

[Scope of Claims] 1. As acid components, (A) terephthalic acid or its ester-forming derivative, (B) isophthalic acid or its ester-forming derivative, and (C) 3,5-dicarboxybenzenesulfonic acid alkali metal salt. or its ester-forming derivatives, and as glycol components
(D) diethylene glycol and (E) molecular weight 400~
Block copolymerized poly(ester ether) obtained using 6000 polytetramethylene glycol
and the composition ratio of (A), (B) and (C) is 10 to 50:50
~90: 2 to 5 mol, and the content of (E) is relative to the produced block copolymerized poly(ether ester).
A polyester film processing agent characterized by having a content of 50 to 80% by weight. 2. The polyester film processing agent according to claim 1, which contains 15% by weight or less of a nonionic surfactant based on the block copolymerized poly(ester ether). 3. A polyester film processing agent according to claim 1 or 2, which is obtained by dispersing a polyester processing agent in water.