JPS6220307B2 - - 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. In a more special case, when an anionic fabric softener is used in the fabric softening process after fixing, the anionic fabric softener will be adsorbed to the cationized fabric surface caused by the fixing agent, causing complexes. Because the hydrophilic groups act in various ways, an excellent texture can be obtained, but only complete water repellency can be 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, the following general formulas (1), (2) and (3) can be used for the same bath processing with a fixing agent of cellulose-based fibers alone or blended, interwoven, or interwoven fiber materials, or for post-processing after treatment with a fixing agent. We have discovered a softening finishing method with excellent water absorption, which is characterized by using a softening agent containing at least one of the compounds represented by (). (In the above formula, R ₁ , R ₂ , R ₃ , and R ₄ 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 represents an oxyethylene group or an oxypropylene group, n is an integer of 1 to 20,
m represents an integer from 0 to 20. Furthermore, in the structure (-A) _-o or (-B) _-n , there are at least 40
The condition is that it contains oxyethylene groups of at least % by weight. Further, X represents an alkali metal, an ammonium group, or an alkanolamine group, and Y represents a hydrogen atom, an alkali metal, an ammonium group, or an alkanolamine group. ) The present invention is suitable for use in dark colored products, for which it has been considered most difficult to impart water absorption properties, i.e., for fix bath processing or post-fix processing.
By containing oxyethylene chains in a predetermined range, it can be used even as an anionic softener and has both water absorbency and a good texture. This is not just 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. This is the starting material for the softener used in the present invention. Examples of C ₈ to _{C 22} saturated or unsaturated higher alcohols include octyl alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, oleyl alcohol, elaidyl alcohol, linoleyl alcohol, linolenyl alcohol, docosyl alcohol, etc. Examples include synthetic or natural higher alcohols, and higher fatty acid reduced alcohols such as beef tallow fatty acid reduced alcohol and tall fat fatty acid reduced alcohol. 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 40% by weight or less, water absorption and bath compatibility with the fixing agent decrease, which is not preferable. In addition, the chain length of the oxyalkylene group (number of m and n in the above general formula)
If it is 21 or more, the resulting hand feel 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), (2) and (3) used in the present invention can be produced by the following industrially known methods. General formula (1) is obtained by sulfating the alkylene oxide adduct of the above-mentioned higher alcohol with 98% sulfuric acid, chlorosulfonic acid, sulfuric anhydride, sulfamic acid, etc. Obtained by neutralizing with alkanolamines such as triethanolamine. General formulas (2) and (3) are obtained by diesterizing or monoesterifying the alkylene oxide adduct of the above-mentioned higher alcohol and an unsaturated dibasic acid such as maleic anhydride, respectively, and then forming the unsaturated bond. It can be obtained by adding bisulfite or the like. Further, in the case of a monoester, the remaining carboxylic acid terminal can be obtained as is or by appropriately neutralizing it with caustic alkali, ammonia, alkanolamine, etc. 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 cellulose fibers etc. in deep colors. This 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 tallow oil, which have been commonly used as softening ingredients in fabric softeners, is essentially unnecessary. Although necessary, these can be used in combination depending on the situation. Furthermore, emulsions such as paraffins, silicones, polyethylenes, etc. can be mixed and used as necessary for the purpose of preventing thread breakage during sewing of stockinette etc. The present invention will be specifically explained below using examples. (Parts and % are based on weight.) Example 1 Ethylene oxide (hereinafter abbreviated as EO) was added to 1 mole of stearyl alcohol in an autoclave in a conventional manner to 5 moles, 10 moles, 15 moles, 20 moles, respectively.
It was added at a rate of 25 moles. After that, an equivalent amount of chlorosulfonic acid was added dropwise to each of the OH terminals at a temperature of 25 to 30°C in a three-necked flask, and the sulfation reaction was carried out with stirring. After the addition, the mixture was aged for 20 minutes at the same temperature. The mixture was poured into a caustic soda aqueous solution, neutralized at 45°C or lower, adjusted to PH = 9 with a 1% aqueous solution of composition purity, diluted to 25% composition purity, and prepared as Example Sample A ( Sample B (EO 5 mole derivative), Sample B (EO 10 mole derivative), Sample C (EO 15 mole derivative), Sample D (EO 20 mole derivative), and Comparative Sample P (EO 25 mole derivative) were obtained. These were subjected to the performance evaluation test described below. Example 2 First, propylene oxide (hereinafter referred to as
(abbreviated as PO) was added at a ratio of 8 mol, and then EO was added to the end thereof at a ratio of 4 mol, 8 mol, and 12 mol, respectively. After that, an amount of maleic anhydride equivalent to those compounds was put into a three-necked flask equipped with a nitrogen inlet tube and a dehydrator, and 0.3% of the total system was added with P-toluenesulfonic acid as a catalyst, and the mixture was gradually dissolved in a nitrogen stream. The esterification reaction was carried out at 180 to 185° C. while increasing the temperature to 180 to 185° C. until the acid value became 8 or less.
Furthermore, these reaction products are composed of sodium bisulfite in an equimolar amount to the raw material maleic anhydride, water in an amount 3.5 times that amount, isopropyl alcohol that accounts for 15% of the total system, and dilauryl sulfosuccinate sodium salt as a reaction accelerator. After blending to give a purity of 5%, a three-necked flask was equipped with a reflux device and heated to the boiling point of isopropyl alcohol to perform a reflux reaction. After continuing the reaction for about 4 hours under these conditions, free sodium bisulfite was checked in each system, and none was detected, so each system was cooled and the purity of the composition increased to 25%.
Comparative example sample Q (PO
8 mol, EO 4 mol), Example Sample E (PO
8 mol, EO 8 mol), F(PO 8 mol, EO 8 mol)
12 mol) were obtained, and these were also subjected to the performance evaluation test described below. Example 3 To 1 mol of beef tallow reduced alcohol, PO was first added at a ratio of 5 mol in an autoclave using a conventional method, and then EO was added at a ratio of 5 mol, 10 mol, 15 mol, and 20 mol, respectively. . After that, these compounds and the same mole of maleic anhydride were put into a three-necked flask equipped with a nitrogen inlet tube and a reflux device, stirred under a small nitrogen stream, and heated to 110°C to open the maleic anhydride. The ring monoesterification reaction was continued until the respective specified acid values were reached. Then, they were cooled and neutralized by adding an equal amount of diethanolamine to the acid value at 30°C or below, and then 90% sodium bisulfite, which was equivalent to the maleic anhydride charged, was dissolved in 3.5 times the amount of water. The mixture was added to each of the systems and mixed, and the temperature was raised to 75° C. with stirring to cause a reaction. After about 3 hours of reaction, we checked for free sodium bisulfite in each system, but none was detected, so we cooled each system and further diluted with water to a composition purity of 25%. Example Sample G (5 moles of PO, 5 moles of EO), Sample H (5 moles of PO, 10 moles of EO), Sample I
(PO 5 mol, EO 15 mol) and Comparative Example Sample R (PO 5 mol, EO 20 mol) were obtained, and these were also 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) Fixture bath processing test Sample fabric Cotton knitted Smooth fabric Dark blue dyed fabric processing bath disposal (Actex FL ¹⁾ 4% owf (Test softener 4% owf (fixing agent manufactured by Morin Kagaku Kogyo Co., Ltd.) Bath ratio 1:20 Processing conditions Processing bath immersion (40℃ x 15 minutes) → Mangle squeezing (100%) → Hot air drying ( (100℃×30 minutes) (2) Post-fixing processing test Sample fabric Same as above Processing bath prescription Fixing bath: Actex 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) → Mangle drawing (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. case) and Table 2
(In the case of post-processing) Texture Test Five panelists were given a five-point score for handling, as shown below, and the results were averaged and converted into a numerical value. 5: Very soft 4: Fairly soft 3: Fairly 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 gently place it on the fabric and soak 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 rubbing 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 carried out using cotton and silk as target fabrics.

【table】

【table】

[Table] (4) Results As is clear from Tables 1 and 2, according to the present invention, in the use of dark colored products, ie, fixing bath processing or post-fixing processing, where it has been difficult to impart water absorption properties, Good hand feel and water absorption were provided without deterioration in fastness. Furthermore, the wet abrasion fastness was even improved, although it was only 0.5 grade.

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 formula (1), ( 1. A softening finishing method with excellent water absorption, characterized in that treatment is performed using a softening agent containing at least one of the compounds shown in 2) and (3). (In the above formula, R ₁ , R ₂ , R ₃ , and R ₄ 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 represents an oxyethylene group or an oxypropylene group, n is an integer of 1 to 20,
m represents an integer from 0 to 20. Furthermore, in the structure (-A) _-o or (-B) _-n , there are at least 40
The condition is that it contains oxyethylene groups of at least % by weight. Further, X represents an alkali metal, an ammonium group, or an alkanolamine group, and Y represents a hydrogen atom, an alkali metal, an ammonium group, or an alkanolamine group. )