JPH045789B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for imparting durable antistatic ability, hygroscopicity, and water absorption to a polyester or polyamide fiber structure, as well as improving the bathochromic properties of dyed fabrics. Specifically, the present invention provides a polyester or polyamide fiber structure having the general formula X-Y-R-Y-X [where R is

【formula】

[Formula] or

[Formula] (A is -O-, -NH-, -CH ₂ -, -SO ₂ -,

【formula】

[Formula] or simply a bond connecting benzene nuclei, Y is -(CH ₂ - CH ₂ O-) _4-15 , and X is

【formula】

[Formula] or

[formula] and R ¹ is H or CH ₃ n is 1 to 6]. (which may contain at least one monomer having a monofunctional or polyfunctional unsaturated double bond with a ratio of organic to organic) of 0.55 to 4.0, and then heat-treated. The present invention relates to a method for treating polyester or polyamide fiber structures that imparts durable antistatic properties, hygroscopicity, and water absorption properties, and improves the dyeability of dyed fabrics. Conventionally, it has been known that common drawbacks of polyester or polyamide fiber structures are that they are easily electrostatically charged and have low hygroscopicity and water absorption. At the finishing stage, a method of adhesion treatment to the fiber surface, that is, a post-processing method for antistatic, moisture absorption, and water absorption treatment, has been used, but the effects lacked durability. Recently, however, modified fibers have been considered that impart durable antistatic properties, moisture absorption, and water absorption properties to these fibers during the spinning stage, but these have drawbacks such as reduced spinnability and reduced yarn properties, and are still not fully developed. I haven't reached anything yet. On the other hand, these fibers are given durable antistatic properties, moisture absorption, and water absorption properties through so-called graft polymerization, which is performed by adding and polymerizing hydrophilic monomers having various radically polymerizable functional groups in their molecules. The method is starting to attract attention. However, depending on the monomer used for these, in addition to the performance, changes in texture, decrease in coloring and dyeability, decrease in wrinkle resistance and fastness,
Furthermore, when preparing a monomer solution, it is difficult to dissolve the monomer solution and apply it uniformly to the fiber surface, which causes various problems in terms of quality and workability. Another drawback of polyester and polyamide fibers is that light is easily scattered because the fibers have a large refractive index. In other words, when disperse dyes with poor clarity are used in these fibers, which is important especially in polyester fibers since only disperse dyes can be used, the color of the dyed product will appear pale. In other words, a phenomenon occurs in which deep coloring is lacking. In order to improve these problems, methods have been proposed and attempted in which compounds with low refractive indexes, such as fluorine compounds, silicon compounds, urethane compounds, etc., are applied to the fiber surfaces. However, at present, this method has not achieved sufficient effects. In order to solve these problems, the present inventor has systematically pursued and already proposed several methods, but as a result of further intensive research, he has arrived at the present invention, which has remarkable effects. That is, the present invention applies an aqueous solution, an organic solvent solution, or an emulsion solution containing a monomer having a specific molecular structure as an essential component and optionally containing other monomers to a polyester or polyamide fiber structure. By further applying heat treatment, it has durable antistatic properties, hygroscopicity, and water absorption properties without causing changes in texture, decrease in coloring and dyeability, or decrease in wrinkle resistance and fastness. This further improved deep coloring. In the present invention, as represented by the above general formula, the lipophilic structure R has an aromatic ring, the lipophilic moiety Y has a polyethylene oxide chain, and furthermore, both terminals X
amide bond to

[Formula] Urethane bond

[Formula] or urea bond

Applying an aqueous solution, an organic solvent solution, or an emulsion solution containing a monomer (A) having a monofunctional unsaturated double bond substituent that is polymerizable via [Formula] to a polyester or polyamide fiber structure. The present inventors have discovered a method that can be easily and economically processed over a wide range of conditions, and have arrived at the present invention. Next, the present invention will be explained in more detail. The above monomer (A) is produced by an appropriate method. For example, a compound having the above hydrophilic/oleophilic moiety and having isocyanate groups at both ends can be reacted with an acrylic derivative that can react with the isocyanate group to form a urea bond, urethane bond, or amide bond. It is also possible to use the opposite reaction. Examples of connecting a hydrophilic/oleophilic structure and a structure having monofunctional unsaturated double bonds located at both ends are as follows. (1) Urea bond A compound with an isocyanate group at the end,
Reaction between compounds with an amide group at the end (2) Urethane bond A compound with an isocyanate group at the end,
Reaction between compounds with terminal hydroxy groups (3) Amide bond A compound with an isocyanate group at the end,
Reaction between compounds with terminal carboxylic acid groups In addition, compounds containing an isocyanate group, an amide bond, a urea bond, or a urethane bond in the compound having an unsaturated double bond capable of radical polymerization, such as

【formula】

【formula】

[Formula] etc. can be used to construct a plurality of bonds, and these are also included in the present invention. Examples of compounds having an amide group at the terminal include acrylamide, methacrylamide, N,
N'-methylenebisacrylamide, N,N'-
Examples include methylene methacrylamide and N,N'-methylenebisethylamide. As a compound having a hydroxy group at the end,
Examples include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, N-methylol acrylamide, N-methylol methacrylamide, acrylate or methacrylate of alkylene oxide type compounds, and furthermore, those having a carboxylic acid group at the terminal. Examples of compounds having this include acrylic acid, methacrylic acid, and the like. The monomer (A) used in the present invention can be produced by the method exemplified above, but the monomer (A) produced in this way
Specific examples include the following: In the present invention, in addition to the above monomer (A), if desired,
One or more monomers (B) having a monofunctional or polyfunctional unsaturated double bond having an inorganic to organic ratio of 0.55 to 4.0 are used in combination. Here, a monofunctional unsaturated double bond monomer has one radically polymerizable unsaturated double bond group in the monomer, and a polyfunctional unsaturated double bond monomer is a monomer having one radically polymerizable unsaturated double bond group. A monomer has two or more radically polymerizable unsaturated double bond groups in the monomer. The value of the ratio of inorganic to organic in the present invention is:
It is based on the "organic concept" proposed by Fujita (Chemistry 11, 179, 1957). In other words, it is a concept that indicates that as the value approaches "0", the organicity becomes stronger, that is, it becomes more lipophilic.If the numerical value of the ratio of inorganic to organic is shown with a concrete example, acrylic acid (2.53 ), unsaturated acids such as methacrylic acid (1.90), unsaturated acid esters such as 2-hydroxyethyl methacrylate (1.35), glycidyl methacrylate (0.59), ethylene glycol dimethacrylate (3.94), maleic acid (3.8), Unsaturated acid anhydrides such as itaconic acid (3.0), N-methylolacrylamide (3.8),
There are unsaturated amines such as dimethyl ethyl methacrylate (0.83). Next, the processing method according to the present invention is to apply an aqueous solution, an organic solvent solution, or an emulsion solution containing the above-mentioned monomer to a polyester or holamide fiber structure, and then heat-treat the structure. The concentration of the monomer used in the present invention is 5g/in the form of an aqueous solution, an organic solvent solution, or an emulsion solution.
The range of ~200g/ is preferable, and in order to obtain remarkable durable antistatic properties, water absorbency, and hygroscopicity, the amount of these polymers fixed or adhering to the fiber structure should be 0.5
A range of 15 to 15 weight percent is preferred, especially a range of 2.0 to 8.0 weight percent. As a means for applying the monomer solution, known methods such as an immersion method, a padding method, an ironing method, and a spray method can be used.As for the heat treatment, an immersion heating method, a normal pressure to high pressure steam heating method, and a high frequency heating method can be used. A heating method, an ultraviolet light heating method, a dry heat heating method, an electron beam heating method, or a combination thereof can be used depending on the fiber structure. The processing conditions include a temperature range of 30°C to 200°C and a processing time range of 0.05 to 60 minutes, but preferably a temperature range of 50°C to 180°C and a processing time of 0.5 minutes to 20 minutes. This is the optimal condition. Further, in order to increase the efficiency of heat treatment, it is preferable to use a catalyst, and it is desirable to use organic and inorganic peroxides, persulfates, and the like. Next, the present invention will be explained in detail with reference to Examples. The durability, frictional charging voltage, water absorption, hygroscopicity, wrinkle resistance, and deep color properties shown in Examples were measured using the following methods. Durability: Wash in a domestic washing machine for 10 minutes at a bath ratio of 1:50 using 40°C warm water containing 1 g of synthetic detergent Sub (Kao Soap), then rinse for 5 minutes. Friction. Electrostatic voltage: In an atmosphere of 20℃ and 50% RH, use a Kyoto University Kaken type rotary static tester (manufactured by Koa Shokai) to measure cotton cloth (Kinpu No. 3) as a friction cloth.Water absorption: 20℃ , in an atmosphere of 65% RH, drop a drop of water from the tip of a burette set 5 cm above the horizontal sample onto the sample, and measure the time it takes for the water drop to spread and disappear. Hygroscopicity: Dry. The conditioned sample was heated to 20℃, 65%RH
The sample was left in an atmosphere for 4 hours, and its weight was measured in that atmosphere. This weight increment is calculated as a weight percentage. Wrinkle resistance: Measured using the Monsatu method in an atmosphere of 20°C and 65% RH. Stainability: Measure the L value using a Kollmorgen spectrophotometer. Example 1 The processed polyester yarn fabric (150d) used was refined and dyed in a conventional manner to obtain a black-dyed product. After measuring the weight, the obtained fabric was immersed in a closed container using composition solution (1) at a bath ratio of 1:30, heated from 50°C to 130°C at a rate of 1°C per minute, and left as it was. Treated for 20 minutes. Next, after cooling, the treated cloth taken out is soaked in soaping liquid.
After treatment using (1) at 80°C for 20 minutes, the weight was measured. In order to examine the effects of the present invention, a durability test of 30 washes was conducted. Composition solution (1) 10% owf Ammonium persulfate 0.5% owf Soaping liquid (1) Soda ash 3g/Synthetic detergent 1g/Example 2 The same black-dyed product as in Example (1) was used. After measuring the weight, the fabric was immersed in Composition Solution (2) under the same conditions as in Example 1, heated from 50°C to 100°C at a rate of 1°C per minute, and treated for 60 minutes. Next, after cooling, the treated cloth was taken out and subjected to a soaping treatment under the same conditions as in Example 1, and its weight was measured. In order to examine the effects of the present invention, a durability test was conducted in the same manner as in Example 1. Composition solution (2) 10% owf Methacrylic acid 3% owf Trichlorobenzene 5% owf Emulsifier 1% owf Benzoperoxide 0.5% owf Example 3 The same black-dyed product as in Example 1 was used. After measuring the weight, the fabric was dipped in the composition solution (3) and squeezed uniformly with a mangle under a pick-up condition of 80%. Next, the treated fabric was heat treated in saturated steam at 100°C for 20 minutes, then soaped under the same conditions as in Example 1, and its weight was measured. In order to examine the effects of the present invention, a durability test was conducted in the same manner as in Example 1. Composition solution (3) 50g/2,2'bis(4methacryloxypolyethoxydiphenyl)propane (molecular weight 660) 25g/potassium persulfate 2g/Example 4 The same black-dyed product as in Example 1 was used. After measuring the weight of the fabric, it was dipped in composition solution (4), squeezed with a mangle under the same conditions as in Example 3, and then wound around a glass rod. Next, the treated cloth was placed in a high frequency generator with an output of 7 kW, heated for 10 minutes while rotating, and soaped under the same conditions as in Example 1, followed by weight measurement. In order to examine the effects of the present invention, a durability test was conducted in the same manner as in Example 1. Composition solution (4) 50g/ methacrylic acid 10g/ 2-hydroxyethyl methacrylate
15g/ Potassium Persulfate 2g/ Comparative Example 1 In order to compare the effects of the present invention, the same black-dyed product as in Example 1 was used and a durability test was conducted in the same manner as in Example 1 without any treatment. . The performance measurements of the fabrics obtained above are summarized in Table 1. As a result, high-performance fabrics were obtained in all cases, and their effects were recognized.

[Table] Example 5 A 30D tricot knitted fabric made of polyamide fibers was refined in a conventional manner. After measuring the weight, the fabric was immersed in a closed dyeing machine using composition solution (5) at a bath ratio of 1:42, and was heated from 50°C to 100°C at a rate of 1°C per minute. After processing for 30 minutes, it was washed with water. In order to examine the effects of the present invention, a durability test was conducted under the same conditions as in Example 1. Composition solution (5) 4%owf

[Formula] 0.5% owf Ammonium persulfate 0.5% owf The performance measurements of the fabrics obtained are summarized in Table 2. It was recognized that the results were all improved compared to the comparative examples.

【table】

Claims (1)

[Claims] 1 A polyester or polyamide fiber structure, X-Y-R-Y-X [R is [Formula] [Formula] or [Formula] (A is -O-, -NH-, -CH ₂ −, −SO ₂ −,
[Formula] [Formula] or simply a bond connecting the benzene nuclei, Y is -(CH ₂ - CH ₂ O-) _4-15 , and X is [Formula] [Formula] or [Formula], R ¹ is H or CH ₃ , and n is 1 to 6] is applied with an aqueous solution, an organic solvent solution, or an emulsion solution containing A method for treating a fibrous structure that imparts durable antistatic ability, hygroscopicity, water absorption and bathochromic properties, the method comprising heat-treating it by: 2. The aqueous solution, organic solvent solution, or emulsion solution further contains at least one monomer having a monofunctional or polyfunctional unsaturated double bond with an inorganic to organic ratio of 0.55 to 4.0. A method for treating a fibrous structure according to claim 1, characterized in that: