JPS6223105B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a soft finishing method with excellent water absorption. More specifically, in fiber materials such as cellulose fibers such as cotton, rayon, hemp, etc. alone, blended, interwoven, interwoven, etc., it is particularly difficult to impart water absorbency through deep color dyeing followed by bath processing with a fixing agent, or The present invention provides a soft finishing method with excellent water absorption in post-processing after fixing agent treatment. Until now, with regard to fiber materials such as cellulose fibers such as cotton, rayon, hemp, etc. alone or blended, interwoven, interwoven, etc., there has been a relationship between the dyeing process and the type of softener used. That is, in general, anionic softeners have been mainly used for white goods, and cationic softeners for both shades and colors have been mainly used. On the other hand, there are also non-ionic softeners, which are used in general, especially for colored products, but their amounts are relatively small, except for special uses such as softeners combined with resins. Additionally, in some cases, anionic softeners were used as a post-processing agent for fixing agents for dark colored products. However, recently, there has been a strong demand for both inner and outer garments to be water-absorbent.
Looking at this response individually, when using anionic fabric softeners for white goods, it is relatively easy to impart water absorption properties, but cationic fabric softeners, which are often used for colored goods, do not absorb water. Mechanically, the cationic groups, which are hydrophilic groups, are adsorbed to the fiber side, and the hydrophobic groups are oriented to the outside, so it is extremely difficult to impart water absorption properties, except for a few special types. It was hot. In addition, it is difficult to achieve both water absorption and texture with commonly used nonionic softeners. Furthermore, in special cases, when using an anionic softener for softening after fixing,
The anionic fabric softener is adsorbed where the fabric surface is cationized by the fixing agent, causing the hydrophilic groups to lapse in a way that causes complexes.
Although an excellent texture was obtained, only complete water repellency was obtained. In order to solve these problems, the present inventors have arrived at the present invention as a result of intensive research. In other words, cellulose fiber alone, blended, mixed,
A softener containing at least one of the compounds represented by the following general formulas (1) and (2) can be used for co-bath processing with a fixing agent or for post-processing after the fixing agent treatment of alternating knitted fiber materials. A soft finishing method with excellent water absorption, characterized by the use of (In the above formula, R ₁ , R ₂ , and R ₃ are each the same or different, or represent a single or multiple saturated or unsaturated hydrocarbon group having 8 to 22 carbon atoms, and A and B are oxy Represents an ethylene group or an oxypropylene group, n is an integer of 1 to 20, and m is an integer of 0 to 20.
Represents an integer of 20. Furthermore, the structure of (-A) _-o and (-B) _-n must contain at least 40% by weight of oxyethylene groups. Moreover, X represents an alkali metal, an ammonium group, or an alkanolamine group. ) The present invention can be used for dark colored products, where it has been considered most difficult to impart water absorption properties, that is, by incorporating oxyethylene chains within a predetermined range, as a fix bath processing or a post-fix processing process. This makes it possible to use anionic softeners and provides both water absorbency and a good texture. This is not only because of this, but because the affinity between anionic softeners and cationic fixing agents is high, the adsorption of the softener to the fibers increases significantly, whether in the same bath or in post-processing. This will greatly reduce the amount of softener remaining in the treatment bath, greatly contributing to reducing the wastewater load. The _C8 to _C22 saturated or unsaturated higher alcohols which are the starting materials for the softener used in the present invention include octyl alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol,
Synthetic or natural higher alcohols such as stearyl alcohol, oleyl alcohol, elaidyl alcohol, linoleyl alcohol, linolenyl alcohol, docosyl alcohol, or higher fatty acid reduced alcohols such as tallow fatty acid reduced alcohol and tall oil fatty acid reduced alcohol. can give. In the present invention, the softener used is made by adding ethylene oxide and propylene oxide to such a higher alcohol, and this is done by a conventionally known method. However, in this case, it is essential to contain at least 40% by weight of oxyethylene chains in the oxyalkylene chains obtained from this in order to obtain water absorption and bath compatibility with the fixing agent. That is, if the oxyethylene chain content is less than 40% by weight, water absorption and bath compatibility with the fixing agent will decrease, which is undesirable. Furthermore, if the chain length of the oxyalkylene group (number of m and n in the above general formula) is 21 or more, the resulting texture will be poor, so it is preferably 20 or less.
In order to obtain a particularly excellent hand, it is particularly preferable that the number is 15 or less. Next, the compounds represented by the general formulas (1) and (2) used in the present invention can be produced by the following industrially known methods. That is, general formulas (1) and (2) are prepared by reacting the above-mentioned ethylene oxide adduct of higher alcohol with a phosphorylating agent such as phosphoric anhydride, orthophosphoric acid, or phosphorus oxychloride. Synthesize phosphate esters and combine these compounds with caustic soda, caustic potash,
It can be obtained by neutralizing with ammonia or alkanolamines such as monoethanolamine, diethanolamine, and triethanolamine. In the present invention, the fixing agent that is treated in the same bath as the softener or in advance is a fixing agent for direct dyes or reactive dyes that are commonly used for the purpose of increasing fastness when dyeing deep colors such as cellulose fibers. Refers to types called polycation type or polyamide amine type. According to the present invention, the blending of esters of polyhydric alcohols such as sorbitan or glycerin with higher fatty acids and fats and oils such as hardened beef oil, which have been commonly used as softening ingredients in fabric softeners, is essentially unnecessary. These may be used in combination, if necessary. Furthermore, for the purpose of preventing ground thread breakage when sewing stockinette etc.
Emulsions of paraffins, silicones, polyethylenes, etc. can also be mixed and used as necessary. Next, the present invention will be specifically explained using examples. [Parts and % are based on weight. ] Example 1 5 mol, 10 mol, 15 mol, 20 mol of ethylene oxide (hereinafter abbreviated as EO) were added to 1 mol of stearyl alcohol in an autoclave in a conventional manner.
It was added at a rate of 25 moles. Thereafter, in a three-necked flask, an equal amount of phosphorus oxychloride is added to each of the OH terminals at a temperature of 40°C or lower to carry out a phosphorylation reaction, and after the addition is complete, the mixture is aged at 70 to 80°C for 4 hours. As a result, a phosphoric acid ester was obtained. These phosphoric acid esters have EO addition moles of 5, 10, 15,
AV (acid value) in the order of 20 and 25; 177, 128, 100,
It had 81 and 70. Next, these phosphoric acid esters were adjusted to pH=9 with aqueous caustic soda solution, diluted to a pure composition of 25%, and prepared as Example Sample A.
(EO5 mol derivative), EO B (EO 10 mol derivative), EO C (EO 15 mol derivative), EO D (EO 20 mol derivative) and Comparative Example Sample P (EO 25 mol derivative) were obtained. These were subjected to the performance evaluation test described below. Example 2 First, propylene oxide (hereinafter abbreviated as PO) was added at a ratio of 8 mol to 1 mol of beef tallow reduced alcohol in an autoclave in a conventional manner,
Next, add 4 mol, 8 mol, and 12 mol of EO to the terminal, respectively.
It was added in molar proportions. After that, those
Anhydrous phosphorus, one-third equivalent each, was gradually added to the OH ends in a three-necked flask at a temperature below 40°C. After the addition was completed, the mixture was aged at a temperature of 70 to 80°C for 5 hours to obtain a mixture of phosphoric acid ester and diester. These phosphate esters have AV (acid value) in the order of compounds with EO addition moles of 4, 8, and 12;
It had 66, 55, and 47. Next, an equal amount of diethanolamine was added to the acid value of each of these phosphoric acid ester mixtures at 30°C or below to neutralize the mixture, and the composition purity was 25%.
% to obtain Example Sample E (8 mol of PO derivative), Sample F (8 mol of PO, 12 mol of EO derivative), Comparative Example Sample Q (8 mol of PO, 4 mol of EO),
These were also subjected to the performance evaluation test described below. Example 3 First, 8 moles of PO was added to 1 mole of lauryl alcohol in an autoclave in a conventional manner,
Next, add 5 mol, 10 mol, and 15 mol of EO to the terminal, respectively.
It was added at a rate of 20 mils. After that, 1/3 equivalent amount of phosphoric anhydride was gradually added to the OH end of each of these compounds in a three-necked flask at a temperature below 40°C, and after the addition, the mixture was aged at a temperature of 70 to 80°C for 4 hours. , phosphoric acid mono- and diester compounds were obtained. These phosphoric acid ester mixtures have AV (acid value); 67,
They had 54, 44, and 38. Next, these phosphate ester mixtures were added to a caustic soda aqueous solution and heated to 45°C.
Neutralize as follows, and use a 1% pure aqueous solution of the composition to PH=
9 and diluted to a composition purity of 25%, Example Sample G (8 mol of PO, 10 mol of EO derivative),
Same H (PO8 mol, EO 15 mol derivative), Same I (PO8
mole, EO20 mole derivative), comparative example sample R
(8 mol of PO, 5 mol of EO derivative) were obtained, and these were also subjected to the performance evaluation test described below. Next, these phosphoric acid esters were adjusted to pH=9 with aqueous caustic soda solution, and then diluted to a composition purity of 25% to prepare Example Sample A (EO5 mol derivative),
Sample B (10 mole of EO derivative), C (15 mole of EO derivative), D (20 mole of EO derivative), and comparative sample P (25 mole of EO derivative) were obtained. These were subjected to the performance evaluation test described below. Example 4 (Performance evaluation test) Each example sample (A to I) obtained in Examples 1, 2, and 3 and comparative example samples (P, Q, R)
In addition, the following three types were selected from conventional anionic and cationic soft ingredients, each diluted to a purity of 25%, and used as comparative examples S, T, and U.
Tests were conducted based on the performance evaluation test method described below. The results are shown in Tables 1 and 2. Comparative example S Hexadecyl sulfate Na salt T Di-beef tallow reduced alcohol sulfosuccinate Na salt U Stearyltrimethylammonium chloride (1) Fixtures bath processing test sample fabric Cotton knitted Smooth fabric Red dyed fabric processing bath prescription Aquatex FL*1 4 %owf Test softener 4%owf (*1 Fixing agent manufactured by Morin Chemical Industry Co., Ltd.)
Bath ratio 1:20 Processing conditions Processing bath immersion (40℃ x 15 minutes) → Mangle squeezing (100%) → Hot air drying (100℃ x 30 minutes) (2) Post-fixing processing test sample fabric Same processing bath prescription fixing agent Bath: Aquatex FL
4% owf softener bath: Test softener 4% owf bath ratio 1:20 Processing conditions Fixture bath immersion (40℃ x 15 minutes) → Mangle squeezing (100%) → Softener bath immersion (40℃ x 15 minutes)
minutes) → Mangle squeezing (100%) → Hot air drying (100%)
℃ x 30 minutes) (3) Performance evaluation test The following points were tested using each method, and the results are shown in Table 1 (for same bath processing) and Table 2.
(In the case of post-processing) (3) Performance evaluation test The following points were tested using each method, and the results are shown in Table 1 (for same bath processing) and Table 2.
(In the case of post-processing) Handle Test A panel of five people gave the following five-level scores on handling, and the results were averaged and converted into a numerical value. 5: Very soft 4: Fairly soft 3: Moderately soft 2: Not very soft 1: Hard Water absorption test Attach a needle to a syringe filled with distilled water to create a water droplet, then slowly place it on the fabric and apply it inside the fabric. The time it took for it to disappear was measured. The test was performed five times and the average value was calculated. In addition, when the time was longer than 1 minute, water was not absorbed and was marked with an x mark. Rubbing fastness test Based on JIS L-0849-71, a friction tester type was used to test in dry and wet conditions. Washing fastness test Based on method B-1 of JIS L-0844-70, the test was conducted using cotton and silk as target fabrics.

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[Table] (4) Results As is clear from Tables 1 and 2, according to the present invention, it is possible to apply water absorbency to dark-colored materials, which has been considered difficult up to now, i.e., in the same bath processing of fixes or after fixing. In processing, it was possible to provide good texture and water absorption without reducing fastness.

Claims (1)

[Scope of Claims] 1. For use in bath processing of cellulose-based fiber alone or blended, interwoven, or interwoven fiber materials with a fixing agent, or for post-processing after treatment with a fixing agent, the following general formulas (1) and ( Using a softener containing at least one of the compounds shown in 2),
A flexible finishing method with excellent water absorption that is characterized by (In the above formula, R ₁ , R ₂ , and R ₃ are each the same or different, or represent a single or multiple saturated or unsaturated hydrocarbon group having 8 to 22 carbon atoms, and A and B are oxy Represents an ethylene group or an oxypropylene group, n is an integer of 1 to 20, and m is an integer of 0 to 20.
Represents an integer of 20. Furthermore, the structure of (-A) _-o and (-B) _-n must contain at least 40% by weight of oxyethylene groups. Moreover, X represents an alkali metal, an ammonium group, or an alkanolamine group. )