JPH0541745B2 - - Google Patents

Description

[Detailed description of the invention]

(Industrial Application Field) The present invention mainly relates to polyester fiber products,
Excellent SR (SOIL RELEASE) properties, especially for knitted fabrics,
This invention relates to a polyester-based finishing agent for imparting hydrophilicity, elasticity, etc. (Prior art) Polyester processing agents obtained by block copolymerizing polyester segments consisting of a terephthalic acid component and/or isophthalic acid component and alkylene glycol with polyethylene glycol blocked at one end have traditionally been used in polyester fiber products. It is already known that it can impart excellent SR properties and hydrophilicity to. (See Special Publication 13197, 1977). However, this processing agent cannot impart excellent stretching performance to textile products. This is especially inconvenient as a processing agent for textile products such as knitted fabrics, which have a major feature of stretchability. (Problems to be Solved by the Invention) The present invention provides a processing agent capable of imparting stretchability in addition to excellent SR properties and hydrophilicity to polyester fiber products, particularly knitted fabrics. (Means for Solving the Problems) In order to solve the above problems, the present invention uses the following processing agent. That is, it is a polyester polyether copolymer obtained by block copolymerizing a polyethylene glycol segment whose one end is blocked with a polyester segment consisting of tetrahydrophthalic acid or its ester-forming derivative and an aliphatic glycol component, and whose composition is ( a) 5 to 50 mol% of tetrahydrophthalic acid or its ester-forming derivative based on the total acid component (b) 95 to 50 mol% of aromatic dicarboxylic acid or oxycarboxylic acid component based on the total acid component (c ) 50 mol% or more of the aliphatic glycol component is ethylene glycol and/or 1,4-butanediol; (d) 50 to 80% by weight of polyethylene glycol with one end blocked based on the resulting polymer It is characterized by having a molecular weight of 800 to 4000. Along with tetrahydrophthalic acid or its ester-forming derivative, an aliphatic or alicyclic dicarboxylic acid or oxycarboxylic acid component having or not having an unsaturated group can be used within a range that does not impair the effects of the present invention. . Specific examples of the above aliphatic or alicyclic dicarboxylic or oxycarboxylic acid components with or without unsaturated groups include itaconic acid, octadeca-7,11-diene-1,18- Dicarboxylic acid, 6-vinyl-dodecane-1,12-dicarboxylic acid, 7-vinyl-hexadec-9-ene-
Dicarboxylic acids such as 1,16-dicarboxylic acid, 7,12-dimethyl-octadeca-7,11-diene-1,18-dicarboxylic acid, dodecanedicarboxylic acid, polybutadiene dicarboxylic acid, octadecanedicarboxylic acid, and dimer acid, or lower versions thereof Examples include ester-forming derivatives such as alkyl esters and ethylene glycol esters, oxycarboxylic acids such as hydroxytetrahydrophthalic acid, glycolic acid, and β-hydroxyacetic acid, and their ester-forming derivatives, including tetrahydrophthalic acid or its ester-forming derivatives. The total amount used including the sexual derivatives is 5 to 50 mol% based on the total acid components. If it is less than 5 mol%, good stretchability cannot be imparted. If 50 mol% or more is copolymerized, the melting point or softening point of the processing agent will decrease, resulting in poor handling and poor hand feel. preferably 10
~40 mol%. Specific examples of aromatic dicarboxylic acid or oxycarboxylic acid components (component (b) above) include:
Terephthalic acid, isophthalic acid, phenoxybenzenedicarboxylic acid, diphenylmethanedicarboxylic acid, naphthalenedicarboxylic acid or their lower alkyl esters, ester-forming derivatives such as ethylene glycol ester, hydroxybenzoic acid, hydroxyethoxybenzoic acid, etc. Ester-forming derivatives thereof may be mentioned, and terephthalic acid or isophthalic acid, their ester-forming derivatives, or mixtures thereof are particularly preferred. The amount used is 95 to 50 mol%, preferably 90 to 60 mol%, based on the total acid components. Examples of the glycol component include ethylene glycol, propylene glycol, 1,4-butanediol, diethylene glycol, dipropylene glycol, neopentyl glycol, etc. Ethylene glycol and 1,4-butanediol are particularly preferred, and 50 mol of the glycol component At least % must be ethylene glycol or 1,4-butanediol or mixtures thereof. Polyethylene glycol with one end blocked has a molecular weight of 800 to 4000, preferably 1000.
-3500 is used, and the group used for blocking is not particularly limited, but a hydrocarbon group having 1 to 20 carbon atoms is preferred. Examples include alkyl groups having 1 to 15 carbon atoms, phenyl groups, naphthyl groups, alkylphenyl groups, and benzyl groups. The amount of polyethylene glycol used above is 50% of the produced polymer.
~80% by weight, and if the amount used is less than 50% by weight, sufficient performance such as SR properties cannot be obtained, and if it is more than 80% by weight, block copolymerized polyester/ether cannot be obtained. Furthermore, if the molecular weight of the one-end-blocked polyethylene glycol used is less than 800, it will easily volatilize during polymerization, and if it is more than 4000, it will be difficult to handle due to insufficient solubility in the system. The number of polyester units contained in the polymer of the present invention is preferably about 6 to 20, and furthermore, at least one aliphatic or alicyclic dicarboxylic acid or oxycarboxylic acid component of the above (a) is always present therein. There is a need to. Therefore, it is necessary to determine the molecular weight that satisfies the above conditions based on the amount of polyethylene glycol used. The method for creating the above polymer is not particularly limited, but for example, a dicarboxylic acid component and a glycol component are heated to react in the presence of an appropriate esterification catalyst or transesterification catalyst to create a glycol ester, and then a predetermined amount of polyethylene glycol is Examples include a method of adding and mixing and then performing polycondensation under reduced pressure. Note that if an antioxidant is added when adding polyethylene glycol, a polymer with less coloring can be obtained. The above polymer is applied to textile products as an aqueous dispersion using a surfactant or as a solution in an appropriate solvent. Furthermore, this does not preclude the use of coloring agents, antioxidants, light-fastening agents, and other various processing agents together with this processing agent. (Effects of the invention) Polyester fiber products, especially knitted fabrics, treated with the polyester processing agent of the present invention have improved elasticity and elasticity in addition to excellent SR properties and hydrophilicity.
A product with good texture can be obtained. (Example) Hereinafter, the effects of the present invention will be explained in more detail with reference to Examples. The obtained polyester-based processing agent and textile products processed using the same were evaluated using the following test method. (1) Reduced specific viscosity of polymer (ηsp/c) Solvent Phenol/1,1,2,2-tetrachloroethane 3/2 (volume ratio) Concentration 0.2g/100ml Temperature 30℃ (2) Performance test of processed fabric Fabric: Polyester jersey Processing method (exhaustion method) Processing agent (10% aqueous dispersion) 3% OWF, acetic acid (90%) 0.3g/, bath ratio 1:20, 130℃, 30
After treatment for 1 minute, washing with water, drying, heat setting at 80℃ for 1 minute SR property (B heavy oil method) Drop 1 drop of B heavy oil on the sample, leave it for 24 hours, wash (JIS-L-1042G method) B after washing Examine the removability of heavy oil. Judgment is 1-5
There are five grades, with grade 5 indicating complete removal. Water absorption: According to JIS-1096-1979 6.26, 1.A method (dropping method). Elongation rate and recovery rate
Mark the cm intervals. This sample is hung, a charge of 1 kg is applied to the lower end, and the length between the marks is measured after 1 minute. Next, the load was removed, and the length between the marks was measured again after 30 seconds, and the elongation rate and recovery rate were calculated using the following formula. Elongation rate = L ₁ - L ₀ /L ₀ ×100 Recovery rate = L ₁ -L ₂ /L ₁ -L ₀ ×100 However, L is the original length (15 cm), L ₁ is after applying the load, The length between marks after 1 minute, L ₂ indicates the length after 30 seconds after removing the load. Example 1 In a reactor equipped with a stirrer, a thermometer, and a methanol distillation tube, 108.9 g (0.561 mol) of dimethyl terephthalate, 9.5 g (0.063 mol) of tetrahydrophthalic anhydride, 85.1 g (1.373 mol) of ethylene glycol, and 0.18 g of zinc acetate were added. g
Collect 0.18 g of antimony trioxide and gradually raise the temperature while stirring. After a predetermined amount of methanol has been distilled out (inner temperature 220°C), 380g of monophenoxy polyethylene glycol with a molecular weight of 3300 and 1,3,5
-Trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene (1 g) was added, and the mixture was stirred and heated for 20 minutes. The resulting reaction mixture was placed in an autoclave with an internal temperature of 230°C, and the pressure was gradually reduced while stirring, and the pressure was reduced to 1 in 30 minutes.
The temperature is raised to 250°C during this time, keeping the temperature below mmHg. After reacting at this temperature for 180 minutes, the pressure is returned to normal using nitrogen gas, and the polymer is taken out from the pores at the bottom of the autoclave. The reduced specific viscosity of the obtained polymer was 0.203. The polymer is called Polymer A
shall be. Example 2, Comparative Example Polymers having different compositions as shown in Table 1 were prepared in the same manner as in Example 1. Table 1 shows the composition and reduced specific viscosity of the obtained polymer. These polymers will be referred to as Polymers B and C. Polymers a and b were also prepared as a comparative example. Example 3 Using the polymers obtained in Examples 1 and 2,
The performance of the processing agent was evaluated using the processing method described above. The results obtained are shown in Table 2.

【table】

[Table] *2: Value when the above elasticity test is performed once
*3: Value when the above elasticity test was repeated three times In Table 2, when polymers A, B, or C are compared with a, the elasticity is the former A, B, or C for both elongation rate and recovery rate. It can be seen that the latter is better than the latter a.

Claims (1)

[Scope of Claims] 1. A polyester ether copolymer obtained by block copolymerizing polyethylene glycol whose one end is blocked with a polyester segment consisting of tetrahydrophthalic acid or its ester-forming derivative and an aliphatic glycol component, the composition of which is: However, (a) Tetrahydrophthalic acid or its ester-forming derivative is 5 to 50 mol % of the total acid component (b) Aromatic dicarboxylic acid or oxycarboxylic acid component is 95 to 50 mol % of the total acid component % (c) 50 mol % or more of the aliphatic glycol component is ethylene glycol and/or 1,4-butanediol; (d) polyethylene glycol with one end blocked has a mol ratio of 50 to 80 mol % of the resulting polymer; A polyester fiber processing agent characterized by containing % by weight and having a molecular weight of 800 to 4000. 2. The polyester fiber processing agent according to claim 1, wherein the aromatic dicarboxylic acid or oxycarboxylic acid component is terephthalic acid and/or isophthalic acid or an ester-forming derivative thereof. 3. The polyester fiber processing agent according to claim 1 or 2, wherein the aliphatic glycol is ethylene glycol and/or 1,4-butanediol.