JPH0314942B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for modifying synthetic fibers such as polyester fibers or acrylic fibers. Conventionally, these synthetic fibers and their fiber structures have been treated with a treatment solution containing a vinyl-based hydrophilic modifier made of acrylic acid, acrylamide, polyalkylene glycol diacrylate, or a derivative thereof. It is well known that polymerization of vinyl modifiers such as those used to impart water absorbency, antistatic properties, and antifouling properties to fibers is possible. These conventional treatment methods usually include a padding dry method, padding steam method, or dipping method, but the padding method does not provide a strong adhesion on the fibers, and the dipping method does not require aqueous solution. Because a radicalizing agent is added to the solution, the modifier starts polymerizing in the water layer before it coagulates and deposits on the fiber surface, creating a large amount of homopolymer in the liquid and reducing the rate of adhesion to the fiber surface. However, these methods cannot provide permanent antistatic properties with excellent washing durability.
It is difficult to obtain water absorbency and stain resistance. Recently, a polyalkylene glycol diacrylate has been proposed in which a bisphenol-based aromatic group is introduced into the skeleton to improve its affinity for hydrophobic fibers (Japanese Patent Application Laid-Open No. 150392/1982). By using such modifiers, it has become possible to solve the above problems to some extent, but it is difficult to obtain sufficiently durable treatment effects for polyester fibers and acrylic fibers, and furthermore, it is difficult to obtain a sufficiently durable treatment effect for polyester fibers and acrylic fibers, and furthermore, it is difficult to obtain a sufficiently durable treatment effect for polyester fibers and acrylic fibers. It has the unforeseen drawback of coloring the modifier inside, impairing the whiteness and sharpness of the hue of the processed material, and significantly reducing product quality, so it has hardly been put into practical use. . On the other hand, fiber processing using epoxy compounds is also widely known, and the processing of natural fibers and synthetic fibers using epoxy compounds is widely known. It is introduced in ``Fiber processing (1)''. However, the second and third reports that were published subsequently mainly report on the reaction between cellulose and epoxy compounds, and also mention the reaction between wool and epoxy compounds.
Regarding synthetic fibers, it has been reported that nylon containing amino groups reacts with epoxy compounds. However, even here, there is no mention of treating polyester and acrylic fibers with an epoxy compound to impart antistatic properties, water absorption properties, and antifouling properties to the fibers. The present inventors completed the present invention as a result of intensive research aimed at improving the drawbacks of conventional synthetic fibers. An object of the present invention is to provide synthetic fibers such as polyester fibers and acrylic fibers that have durable antistatic properties, water absorption properties, and antifouling properties. Another object is to provide a new processing method that allows industrially easy production of synthetic fibers that have durable antistatic properties, water absorption properties, and antifouling properties. In the method of the present invention, polyester fibers and/or acrylic fibers have the general formula (1). (In the formula, R is -CH ₂ CH ₂ O-, and n is an integer of 1 to 15.) and the general formula (2) and/or
(3) A modification treatment for synthetic fibers, characterized by applying an emulsion obtained by emulsifying and dispersing a mixture of an epoxy compound represented by the formula and an acidic catalyst in water using a surfactant, drying the mixture, and then heat-treating the mixture. It's in the method. The polyester fiber applied to the present invention is a condensate of an aromatic dicarboxylic acid and an alkylene glycol having 2 to 10 carbon atoms, and is usually polyethylene terephthalate. Of course, a small amount of aliphatic dicarboxylic acid or the like may be copolymerized with this. Acrylic fibers usually contain 85% by weight or more of acrylonitrile, and may be copolymerized with methyl acrylate, methyl methacrylate, sodium allylsulfonate, or the like. These fibers include appropriate shapes such as filaments, staple fibers, tows, threads, knitted fabrics, and nonwoven fabrics. The epoxy compound applied to the present invention has the general formula (1) R represents -CH ₂ CH ₂ O-, and n is 1 to 15, preferably 2 to 8. Here, if n is less than 1, not only the solubility in water will decrease, but also the affinity for water will decrease even when mixed with general formulas (2) and (3), resulting in improved water absorption, antistatic properties, and antistatic properties. It is impossible to sufficiently improve stain resistance. In addition, if n exceeds 15, the affinity for fibers will decrease and the washing durability will decrease, so it must be avoided. General formula (2) used in combination with the above compounds The epoxy compound represented by formula (1) has strong hydrophobicity, shows hydrophobic affinity for synthetic fibers, and exhibits strong adhesion to the fiber surface. By applying and heat-treating, it is possible to impart excellent and durable performance in water absorption, antistatic properties, and antifouling properties. General formula (3) When applying a mixed compound of the epoxy compound represented by the formula (1) and the compound represented by the general formula (1) to synthetic fibers, the compound is hydrophobic as in the case of the general formula (2). It is an excellent compound as a durable fixing agent because it has a hydrophobic affinity to the synthetic fiber, and a mixed compound with a highly hydrophilic compound shown in general formula (1) is applied to the synthetic fiber and heat treated. In particular, it exhibits excellent properties such as durability, water absorption, antistatic properties, and antifouling properties. The mixing ratio of epoxy compounds in the present invention is
In general formulas (1) + (2) and (1) + (3), 15:85-85:
A range of 15 is preferred. However, when n in formula (1) is 8 or more
15:85 to 75:25, preferably 75:25 to 85:15 when it is 7 or less. When general formula (1) is 15:85 or less, formula (2) and
The compound represented by formula (3) has low hydrophilicity, resulting in a decrease in water absorption, which is not preferable. Also, general formula (1) is 85:15
When it exceeds 1, the hydrophilicity of formula (1) increases and performance is improved, but this is not preferable because the epoxy compound will fall off due to repeated washing and the durability of performance will decrease. The amount of the epoxy compound applied to the fiber is usually 1% by weight or more, preferably 2 to 10% by weight, and more preferably 3 to 8% by weight. The acidic catalyst used in the present invention is preferably a metal salt, particularly a borofluoride metal salt, such as zinc borofluoride or magnesium borofluoride. The nonionic surfactants applicable to the present invention include polyoxyalkylene glycol-alkyl ether, polyoxyalkylene glycol-alkylphenyl ether, polyoxyalkylene glycol-alkyl ether, and polyoxyalkylene glycol-alkyl phenyl ether.
Alkyl esters, etc., and the HLB indicated by these
Values range from 10 to 20, depending on the
HLB is 11-16, more preferably 12-15. These HLB values are single or low HLB, high HLB
A mixed compound of two or more HLBs may also be prepared. The emulsifier used in the emulsification of the epoxy compound in the present invention is
It is 80% by weight. The concentration of the epoxy compound in the emulsified aqueous solution containing the epoxy compound is usually 1 to 12% by weight, preferably 2 to 10% by weight. The amount of acidic catalyst in the emulsified aqueous solution is usually 0.3 to 5% by weight, preferably
It is 0.5 to 3% by weight. Although the emulsified aqueous solution used in the method of the present invention contains a catalyst, it has excellent stability and is therefore extremely easy to handle in industrial production. The emulsified aqueous solution is usually applied to the synthetic fibers at room temperature. The application method is not particularly limited, but may be a pad method, a spray method, a coating method, or the like. The synthetic fiber to which the epoxy compound has been applied is then subjected to heat treatment after drying. In this case, heat treatment may be performed immediately after applying the epoxy compound, and drying and heat treatment may be performed in the same step. Drying may be done by air drying, but it is usually carried out at 50 to 120°C for 1 to 30 minutes. Heat treatment is usually dry heat at 80℃ or higher, preferably dry heat at 100℃ or higher.
Perform at 220°C for 1 to 20 minutes. After heat treatment, the synthetic fibers are washed with hot water or water and dried with warm air at 40°C. The synthetic fiber obtained by the method of the present invention usually has an epoxy compound attached in an amount of 1 to 10% by weight, preferably 2 to 8% by weight based on the weight of the fiber. The synthetic fiber obtained in the present invention is
It has excellent antistatic properties, water absorption properties, and antifouling properties.
Moreover, it not only has excellent durability that can withstand repeated washing, but also is of high quality without any discoloration or deterioration in texture as in conventional methods. The present invention will be explained in detail below with reference to Examples. The methods for evaluating durability, antistatic properties, water absorption, and antifouling properties, as well as the washing method for antifouling properties for evaluating durability, shown in the examples are as follows. Γ Charge voltage (V) Measured at 20±2° C. and 40±2% RH using a Kyoto University Kaken type rotary star tickster (manufactured by Koa Shokai) and using cotton gold cloth No. 3 as a friction cloth. Γ Half-life (sec) Static Honest Meter (manufactured by Shishido Shokai)
applied voltage 10KV, 20±2℃, 40±2%
Measured under RH conditions. Γ Water absorption (cm/10min) Measured by JIS L-1079B method (Byreck method). Γ Washing fastness: Measured according to JIS L-0844 method. ΓWashing method: Neutral washing (product name Pinky, Lion Oil
Co., Ltd.) in a cleaning solution at 40℃ containing 0.1% in a household washing machine (fully automatic washing machine FP-578 model, Hitachi, Ltd.).
Washed using. One cycle consisted of washing at 40° C. for 10 minutes, rinsing at room temperature for 3 minutes twice, and dehydration, and this cycle was repeated five times. In addition, in this specification, the adhesion rate (%) refers to the amount of modifier applied (total amount of modifier in the bath in the dipping method, treatment liquid concentration x squeezing rate in the spray method and padding method). The amount of modifier attached to the object to be treated is B
In this case, it is a term represented by B/A×100. Γ Rubbing fastness JIS L-0849 (type) Γ Stain resistance When stains from lipstick, machine oil, and mayonnaise are attached and the above washing method is used, the stain removal status after one wash is 〇 (good removability), × ( Poor removability). The epoxy compounds used in each example are as follows. Example 1 A polyester fabric (75d/36f, taffeta) was immersed in an emulsified dispersion solution having the composition shown below at room temperature, and after squeezing the liquid to a squeezing rate of 100%, it was dried at 100°C for 5 minutes, and then dried at 150°C. After dry heat treatment for 5 minutes at 40℃
After washing with warm water for 1 minute, drying in a hot air dryer at 40°C, and leaving in a constant temperature room at 20°C and 40% RH for 24 hours, the physical properties were evaluated and shown in Table 1. Emulsified dispersion solution composition D compound 2.5 parts by weight I compound 2.5 〃 Catalyst Zn (BF ₄ ) ₂ 1.0 〃 Nonylphenyl polyethylene glycol ether 2.5 〃 Water 89.5 〃

[Table] Example 2 Polyester fabric (75d/36f, taffeta)
Immerse in an emulsified dispersion solution with the composition shown in the table at room temperature, squeeze to a squeezing rate of 100%, dry at 100℃ for 5 minutes, then dry heat at 150℃ for 5 minutes, and then soak in warm water at 40℃ for 1 minute. Wash, rinse with water for 1 minute, dehydrate, and dry in a hot air dryer at 40℃, 20℃, 40% (RH)
After being left in a constant temperature room for 24 hours, the physical properties were evaluated. The results are shown in Table 3.

【table】

【table】

[Table] Example 3 Acrylic fiber knitted fabric (Aqualon: manufactured by Kanebo Co., Ltd.)
was immersed in an emulsified dispersion solution having the composition shown below at room temperature, and then treated in the same manner as in Example 1. Emulsified dispersion solution Compound H 2.5 parts by weight Compound D 2.5 Catalyst Zn (BF ₄ ) ₂ 1 Emulsifier 2.5 Add water to make the total emulsified solution 100 parts by weight. The results are shown in Table 4.

[Table] Example 4 Polyester fabric (decine, basis weight 108g/m ² )
was immersed in an emulsified dispersion solution with the composition shown below at room temperature, dried at 100°C for 3 minutes after squeezing to obtain a squeezing rate of 57%, and then subjected to dry heat treatment at 160°C for 2 minutes.
It was washed with warm water at ℃ for 30 minutes and dried in a hot air dryer at 40℃. This processed cloth was immersed in a dye solution having the composition shown below, heated to 130°C for 45 minutes, and dyed at 130°C for 60 minutes. Emulsified dispersion solution Compound D 1.5 parts by weight Compound I 2.3 Catalyst Zn (BF ₄ ) ₂ 0.4 Nonylphenyl polyethylene glycol ether 3.8 Water 92.0 Dye solution Sumikaron Red SE-RPD (manufactured by Sumitomo Chemical)
0.7 parts by weight Toho Salt UF-350 (manufactured by Toho Chemical)
0.1 〃 Ultra MT #170 (manufactured by Mihejima Chemical)
0.1 〃 Water 99.1 〃 The dyed cloth was subjected to reduction cleaning in a reduction cleaning bath having the composition shown below, washed with hot water and water, and dried in a hot air dryer at 40°C. Next, the fabric (unprocessed fabric) that had been dyed and reduced and washed without any processing was left in a constant temperature room at 20°C and 40% RH for 24 hours, and then the physical properties were evaluated and shown in Table 6. Reduction cleaning bath Sodium carbonate 0.18 parts by weight Sodium hydrosulfite 0.18 Amirazine D (Daiichi Kogyo) 0.18 Water 99.46

[Table] Example 5 Polyester fabric (Calze, basis weight 208g/m ² )
130 in 45 minutes by immersing it in a dye solution with the composition shown below.
The temperature was raised to ℃ and dyed at 130℃ for 60 minutes. Dye solution Sumikaron Blue SE-RPD (manufactured by Sumitomo Chemical)
0.7 parts by weight Toho Salt UF-350 (manufactured by Toho Chemical)
0.1 〃 Ultra MT #170 (manufactured by Mihejima Chemical)
0.1〃Water 99.1 The dyed cloth was reduced and washed according to a conventional method, dried in a hot air dryer at 40°C, and subjected to the next processing. It was immersed in an emulsified dispersion solution with the composition shown below at room temperature, dried at 100℃ for 10 minutes after squeezing the liquid to a squeezing rate of 84%, and then subjected to dry heat treatment at 150℃ for 2 minutes.
It was washed with warm water at ℃ for 30 minutes and dried in a hot air dryer at 40℃. A cloth that had been dyed and reduced-cleaned without any processing (unprocessed cloth) was added and left in a constant temperature room at 20°C and 40% RH for 24 hours, after which physical properties were evaluated. The results are shown in Table 6. Emulsified dispersion liquid Compound D 1.5 parts by weight Compound I 2.3 〃 Catalyst Zn (BF ₄ ) ₂ 0.4 〃 Nonylphenyl polyethylene glycol ether 3.8 〃 Water 92.0 〃

【table】

Claims (1)

[Claims] 1 Polyester fiber and/or acrylic fiber, general formula (1) (In the formula, R is -CH ₂ CH ₂ O-, and n is an integer of 1 to 15.) and the general formula (2) and/or
(3) A method for modifying synthetic fibers, which comprises applying an emulsion obtained by emulsifying and dispersing a mixture of an epoxy compound represented by the above and an acidic catalyst in water using a surfactant, drying the mixture, and then subjecting the emulsion to a heat treatment. 2. The method according to claim 1, wherein the acidic catalyst is a borofluoride metal salt. 3. The method according to claim 1, wherein the surfactant is a nonionic surfactant. 4. The method according to claim 1, wherein drying and heat treatment are performed in the same step. 5. The method according to claim 1, wherein the heat treatment is performed at a dry heat temperature of 80 to 220°C.