JPH0127195B2 - - Google Patents

Description

[Detailed description of the invention]

<Industrial Application Field> The present invention relates to an oil agent for treating polyester fibers dyeable with cationic dyes (hereinafter abbreviated as dyeable polyester) and a method for treating dyeable polyester using the oil agent. General polyester fiber (hereinafter abbreviated as general polyester), which mainly consists of ethylene terephthalate units, has various excellent properties.
For example, it is widely used as a textile for clothing. However, since this general polyester does not have a reactive group, it has problems in dyeing properties, such as not being able to obtain a clear hue like wool or acrylic fibers, and also not having sufficient color fastness. Therefore, in recent years, in order to solve the above-mentioned problem of dyeability, for example, metal salt sulfonate groups have been introduced into the main chain or terminals of polyesters mainly composed of ethylene terephthalate units, so that they can be dyed with cationic dyes at high pressure or normal pressure. Various dyeable polyesters have been developed. However, when these dyeable polyesters are subjected to a false twisting process, unpredictable crimp spots and fuzz frequently occur, degrading quality, and yarn breakage also frequently occurs. There is a particular problem in that it reduces workability. The present invention relates to a treatment oil that addresses the above-mentioned unique problems in dyeable polyester, and a method for treating dyeable polyester using the oil. <Prior art and its problems> Conventionally, even if a commonly used oil agent for general polyester is applied to dyeable polyester, the commonly used oil agent hardly exhibits the desired effect. Oil agents have been proposed (JP-A-51-55496, JP-A-52-74021).
etc). However, although this type of conventional oil agent is somewhat effective in improving the uniformity of dyeable polyester and preventing a decrease in strength and elongation, it is difficult to solve a particular problem in the processing of dyeable polyester, namely in the false twisting process of dyeable polyester. It is impossible to solve the problem that unpredictable crimp spots, fuzz, and even thread breakage frequently occur when subjected to water, which significantly reduces quality and workability. <Problems to be Solved by the Invention and Means for Solving the Problems> The present invention provides a processing oil that solves the problems specific to the processing of dyeable polyester as described above, and a method for processing dyeable polyester using the oil. It is something. However, as a result of careful observation of the above-mentioned unique problems that occur in the processing of dyeable polyester, the inventors of the present invention have determined that the cause is friction between fibers and between fibers and between fibers and metal. It has been found that this is particularly affected by the phenomenon of the running yarn jumping out from the heater track (hereinafter abbreviated as "jumping"). Therefore, the present inventors further conducted intensive research to develop an oil agent that resists the above-mentioned friction and suppresses the above-mentioned jumping. As a result, the present inventors found that a specific high molecular weight polyether compound has excellent wear resistance between fibers and between fibers and between fibers and metals. In addition, specific quaternary ammonium salts reduce jumping, and specific smoothing agent components reduce the coefficient of friction between fibers and metals. Therefore, an oil agent containing these in a predetermined proportion is appropriate. The inventors have discovered that, by appropriately applying the oil agent to dyeable polyester, the problems peculiar to the processing of dyeable polyester can be better solved comprehensively. That is, the present invention provides a compound with a molecular weight of 7000, which is obtained by adding ethylene oxide and propylene oxide in a random or block manner.
10 to 40% by weight of the above high molecular weight polyether compound, 5 to 30% by weight of a quaternary ammonium salt represented by the following general formula (), and one or more types selected from the following group A. 30-80% by weight of smoothing agent component
A cationic dye further comprising 0.5 to 3% by weight of a mono- to divalent aliphatic carboxylic acid soap. A second invention relating to a treatment oil agent for dyeable polyester fibers; A treatment oil agent of the first invention is applied to cationic dye dyeable polyester fibers after melt spinning and before false twisting. The third invention relates to a method for treating polyester fibers dyeable with cationic dyes, characterized in that the amount of dyed polyester fibers is 1.2% by weight. General formula ()

[Formula] [However, R ¹ is both an alkyl group or an alkenyl group having 6 to 18 carbon atoms, or

N-acylaminoalkyl group represented by [Formula] (here, R ⁵ both have 5 carbon atoms)
~17 alkyl or alkenyl groups. ^R6 is hydrogen,
Methyl group, hydroxyethyl group or hydroxypropyl group. p is an integer of 2 or 3). ^R2 , ^R3 , ^R4
each independently represents a methyl group, an ethyl group, a hydroxyethyl group or a hydroxypropyl group. A ^-n is carboxylic acid, phosphoric acid, phosphoric ester,
An n-valent anion residue obtained by removing a hydrogen ion from each group of a sulfuric acid ester or a sulfonic acid ester. H ⁺ is a hydrogen ion. m and n are 0≦m≦2, 1≦n≦3, and n
- m = 0 or an integer from 1 to 3 that satisfies 1 to 3. ] Group A: (1) polyether compound with a molecular weight of 700 to 3,500 to which ethylene oxide and propylene oxide are added randomly or in blocks, (2) mono- or poly(2-10 mol) oxyalkylene aliphatic alcohol and monohydric fatty acid. monoester with,
(3) Diester of mono- or poly(2-10 mol) oxyalkylene aliphatic alcohol and divalent fatty acid In the present invention, the dyeable polyester to be treated is modified to be dyeable with a cationic dye. Polyester fibers include polyester fibers mainly composed of ethylene terephthalate units with metal salt sulfonate groups introduced into the main chain or ends, but other fibers may be used to enable non-carrier atmospheric boiling dyeing. It also includes those using copolymerized components. Further, in the present invention, the high molecular weight polyether compound contains ethylene oxide and propylene oxide as the active hydrogen compound, preferably ethylene oxide/propylene oxide = 50 to 90/50.
-10 (weight ratio), and has a molecular weight of 7,000 or more obtained by adding randomly or in blocks, and is contained in the oil agent in an amount of 10 to 40% by weight. Molecular weight is 7000
If the content is less than 10% by weight, the fiber-to-fiber and fiber-to-metal abrasion resistance will be poor in the processing of dyeable polyester, and the cohesiveness and lubricity will be insufficient. become. On the other hand, if the content exceeds 40% by weight, problems will occur with the winding shape.
The twill may fall off and other problems may occur. Usually, the high molecular weight polyether compound having a molecular weight of 7,000 to 15,000 can be conveniently used. Specific examples of high molecular weight polyether compounds include alcohols (saturated alcohols with 1 to 18 carbon atoms, oleyl alcohol, synthetic alcohols and reduced alcohols with 10 to 15 carbon atoms, diols with 2 to 12 carbon atoms, glycerin and Polyhydric alcohols such as methylolpropane, alkylphenols, etc.), carboxylic acids (capric acid, adipic acid, trimellitic acid, etc.), amine compounds (laurylamine, ethylenediamine, triethanolamine, etc.), thioether compounds, or mercaptan compounds ( There are compounds in which ethylene oxide and propylene oxide are randomly or block-addition polymerized to active hydrogen compounds such as thioglycol, triethylene glycol dimercaptan, etc.). In this case, the addition polymer may be one in which the terminal hydroxy group is etherified or silylated, or further, the two molecules of the terminal hydroxy group may be condensed by formalization or silylation. Furthermore, in the present invention, the quaternary ammonium salt is represented by the general formula (), and is contained in the oil agent in an amount of 5 to 30% by weight. General formula ()
If the above conditions are not met or the content exceeds 5 to 30% by weight, the jumping suppressing effect will be poor, and the adhesion of the oil to the dyeable polyester may become unstable or fuzz may occur. It also begins to cause harm. In order to better demonstrate the effect of the quaternary ammonium salt, R ¹ to R ⁴ of the general formula () and H ⁺ _n A ^-n
etc. are selected as appropriate depending on the composition of the dyeable polyester to be treated and the processing conditions of the dyeable polyester (number of twists, denier, filament count, etc.), but usually as H ⁺ _n A ^-n ,

It is preferable to use a phosphoric acid ester ion represented by the formula or a sulfuric acid ester ion represented by R ⁹ OSO ₃ ^- (here, R ⁷ to ^{R 9} are each independently a methyl group or an ethyl group). Specific examples of the quaternary ammonium salt represented by the general formula () include the following (a) to (k). These quaternary ammonium salts can be easily synthesized by conventional methods. For example, (a) above
- (c), (j) and (k) are obtained by reacting the corresponding tertiary amine with ethylene oxide in the presence of water to obtain quaternary ammonium hydroxide, and then adding phosphoric acid and stirring. can be obtained by
Moreover, the above (d) to (f) can be obtained by stirring and reacting the corresponding tertiary amine with triethyl phosphate or trimethyl phosphate, and the above (g) to (i) can be obtained by stirring and reacting the corresponding tertiary amine with triethyl phosphate or trimethyl phosphate. can be obtained by stirring and reacting the corresponding tertiary amine with dimethyl sulfuric acid or dimethyl sulfuric acid. In the present invention, the smoothing agent component is the above-mentioned A
One or more components selected from the group consisting of 30 to 80% by weight of the oil. In Group A, polyether compounds with a molecular weight of 700 to 3500 are similar to the high molecular weight polyether compounds,
It is obtained by adding ethylene oxide and propylene oxide to an active hydrogen compound, preferably at a ratio of ethylene oxide/propylene oxide of 10 to 50/90 to 50 (weight ratio), either randomly or in blocks. In Group A, the oxyalkylene aliphatic alcohol used for the synthesis of monoester or diester has an oxyethylene group and/or oxypropylene group as its oxyalkylene group, and the aliphatic group has 4 to 12 carbon atoms. is preferred. The carboxylic acid used to esterify the oxyalkylene aliphatic alcohol is preferably a monovalent fatty acid having 8 to 18 carbon atoms or a divalent fatty acid having 6 to 10 carbon atoms. Specific examples of monoesters in Group A include:
POE (3 moles) octyl ether octanoate, POE (5 moles) POP (5 moles) butyl ether oleate, POE (7 moles) octyl ether octanoate, etc. Specific examples of diesters in group A are listed below. , bisPOE (2 mol) decyl ether sebacate, bisPOE (6 mol) octyl ether adipate, etc. Here,
POE stands for polyoxyethylene and POP stands for polyoxypropylene. The oil agent according to the present invention comprises the high molecular weight polyether compound having a molecular weight of 7000 or more and the general formula ()
It will be more effective if 0.5 to 3% by weight of mono- to divalent aliphatic carboxylic acid soap is further added to the quaternary ammonium salt shown by and the smoothing agent component of Group A. This is dyeable polyester,
If the material is subjected to extremely harsh conditions during its various processing steps (twisting, knitting, diameter adjusting step, fabric preparation step, etc.), metal abrasion and metal corrosion are likely to occur, and this is to prevent such inconveniences. The aliphatic carboxylic soaps include alkali metal salts, amine salts, and alkanolamine salts of aliphatic mono- or dicarboxylic acids having 8 to 20 carbon atoms, and more specifically, isostearic acid triethanolamine salts and dodecenyl succinic acid. There are acid sodium salts, etc. In addition to the above-mentioned components, the oil according to the present invention may appropriately contain an emulsifier, an emulsification regulator, a wetting agent, an antistatic agent, a rust preventive, a preservative, etc. within a range that does not impair the effects of the present invention. obtain. Next, a method for treating dyeable polyester with the oil agent according to the present invention explained above will be explained. The oil agent is applied to dyeable polyester as a spinning oil agent and exhibits its effect better. For its use, it can be applied to the dyeable polyester as an aqueous emulsion, as a solution in an organic solvent or as an oil. The amount of adhesion to the dyeable polyester is preferably 0.2 to 1.5% by weight (effective oil component). In particular, 0.3 to 1.2% by weight of the oil agent is added to the dyeable polyester at a stage after melt spinning and before stretching or false twisting.
(Oil agent effective ingredient) When applied, the desired effect is extremely pronounced. <Actions, Effects of the Invention, etc.> Very common polyether compounds themselves, quaternary ammonium salts themselves, and smoothing agent components themselves are already well known as textile oil components. However, in the processing, problems specific to dyeable polyester, such as friction and abrasion between fibers and metals, as well as jumping, can be solved by using a specific three-component or four-component oil agent as in the present invention. I have yet to see a clear solution to this problem. The reason why the present invention can solve such unique problems is that the specific three or four components in the present invention
It is presumed that this is because the components together effectively mask the anionic groups such as sulfone groups present on the surface of the dyeable polyester and change the properties of the surface. Therefore, the present invention solves urgent problems in the art in the processing of dyeable polyester, namely, fiber-to-fiber and fiber-to-metal friction, abrasion, and jumping, and thereby solves crimping spots, fuzz, and threads. This has the effect of preventing the occurrence of cuts, etc., and ultimately significantly improving product quality and workability. <Examples, etc.> Hereinafter, examples and comparative examples will be given to clarify the structure and effects of the present invention, but the present invention is not limited to these examples. Examples 1 to 4, Comparative Examples 1 to 9 Each oil agent listed in Table 1 was blended and prepared. Then, using these oil agents, dyeable polyester yarns are produced by the following methods, and the dyeable polyester yarns are further subjected to false twisting, and the resulting false-twisted yarns are jumped and fluffed. , and heater contamination was measured or evaluated. The results are shown in Table 1. ...Production of dyeable polyester yarn 3 mol% of sodium 5-sulfoisophthalate
The copolymerized polyethylene terephthalate polymer was melt-spun at 283°C, and after air cooling, 10% of each oil was spun.
% emulsion using the roller touch method,
0.8% by weight (active ingredient of the oil) of each oil agent was deposited.
Subsequently, the yarn was wound at a speed of 1200 m/min and stretched 3.2 times to produce a dyeable polyester yarn of 75 denier x 36 filaments. ...False twisting The above dyeable polyester yarn was subjected to one stage of false twisting under the following conditions. Twisting method: Spindle method (Sapphire Yapin) Yarn running speed: 130 m/min Overfeed rate: +4% Number of false twists: 3100 T/m False twisting temperature: 190°C ...Jumping measurement and evaluation: Possible during false twisting A peculiar phenomenon occurs in which the dyed polyester yarn deviates from the normal yarn path to an abnormal location in the torque direction, that is, jumping. This jump returns to normal after a certain period of time,
Furthermore, if the false twisting process is continued, the problem may occur again. Therefore, the false twisting time was set to A minutes (target 60 minutes).
The jumping value was calculated using the following formula, with the cumulative jumping time being B seconds, and evaluated based on the following criteria. Jumping value = (B/A) × 10 〇: Jumping value 0 △: Jumping value 1 to 10 ×: Jumping value 11 or more When jumping occurs, crimp spots, fuzz, thread breakage, etc. occur accordingly. . ...Evaluation of fluff on false-twisted yarn The presence or absence of fluff on the end face of false-twisted yarn cheese (rolled at 2 kg) was visually observed and evaluated according to the following criteria. ○: No fuzz generation ×: 1 to 2 fuzzes present XX: 3 or more fuzzes present...Evaluation of heater contamination Continuous operation was performed for 6 days under the above false twisting conditions. During this time,
If the thread breaks due to jumping, etc.,
The yarn was re-set and false-twisted. Then, the presence or absence of tar compounds in the thread path of the heater was observed using a magnifying glass, and then evaluated using a standard. ○: Almost no heater contamination is observed ×: Heater contamination is observed If the heater is contaminated, the thread will be damaged accordingly.

【table】

[Table] From the results in Table 1, the excellent effects of the present invention are clear. In addition, regarding each oil agent of Comparative Examples 1 to 9,
Measurements and evaluations were carried out in the same manner except that general polyester was used instead of dyeable polyester. In this case, for example, all the jumping values were 0. Therefore, it can be seen that although each of the oils in the comparative examples can be applied to the processing of general polyester, it cannot be applied to the processing of dyeable polyester, which has its own problems such as jumping. Examples 5 to 7, Comparative Examples 10 to 14 Each oil agent listed in Table 2 was blended and prepared. Then, using these oils, use the following method.
Manufacture dyeable polyester POY, and
was stretched and false-twisted, and measured and evaluated in the same manner as in the above case. The results are shown in Table 2. ...Manufacture of POY 5-sulfoisophthalic acid sodium salt and 1,
A polymer of polyethylene terephthalate copolymerized with 2 mol% of each 4-butanediol was heated at 285°C.
After melt spinning and air cooling, a 10% emulsion of each oil was applied using the roller touch method, and each oil was added to a concentration of 0.6
% by weight (oil agent effective ingredient) was attached. continuation
Winding at a speed of 3300m/min, 115 denier x 36
Filament POY was manufactured. ...Stretching and false-twisting The above POY was subjected to one-stage stretching and false-twisting under the following conditions. Twisting method: Spindle method (Sapphire Yapin) Yarn running speed: 180m/min Stretching ratio: 1.518 Number of false twists: 3200T/m False twisting temperature: 200℃

【table】

[Table] From the results in Table 2, the effects of the present invention are clear.

Claims (1)

[Claims] 1. Molecular weight of ethylene oxide and propylene oxide added randomly or in blocks
10-40 high molecular weight polyether compounds over 7000
Contains 5-30% by weight of a quaternary ammonium salt represented by the following general formula () and 30-80% by weight of one or more smoothing agent components selected from Group A below. An oil agent for treating polyester fibers dyeable with cationic dyes. General formula () [Formula] [However, R ¹ is both an alkyl group or alkenyl group having 6 to 18 carbon atoms, or an N-acylaminoalkyl group represented by [Formula] (wherein R ⁵ is both an alkyl group or alkenyl group having 5 carbon atoms)
~17 alkyl or alkenyl groups. ^R6 is hydrogen,
Methyl group, hydroxyethyl group or hydroxypropyl group. p is an integer of 2 or 3). ^R2 , ^R3 , ^R4
each independently represents a methyl group, an ethyl group, a hydroxyethyl group or a hydroxypropyl group. A ^-n is carboxylic acid, phosphoric acid, phosphoric ester,
An n-valent anion residue obtained by removing a hydrogen ion from each group of a sulfuric acid ester or a sulfonic acid ester. H ⁺ is a hydrogen ion. m and n are 0≦m≦2, 1≦n≦3, and n
−m=0 or an integer from 1 to 3 that satisfies 1 to 3. ] Group A: (1) polyether compound with a molecular weight of 700 to 3,500 to which ethylene oxide and propylene oxide are added randomly or in blocks, (2) mono- or poly(2-10 mol) oxyalkylene aliphatic alcohol and monohydric fatty acid. monoester with,
(3) Diester of mono- or poly(2-10 mol) oxyalkylene aliphatic alcohol and divalent fatty acid 2 In the general formula (), H ⁺ _n A ^-n is [formula] (where R ⁷ , R ⁸ The oil agent for treating polyester fibers dyeable with cationic dyes according to claim 1, wherein each of the phosphoric acid esters is a phosphate ion represented by the following (methyl group or ethyl group). 3 In the general formula (), H ⁺ _n A ^-n is R ⁹ OSO ₃ ^-
(herein, R ⁹ is a methyl group or an ethyl group)
An oil agent for treating polyester fibers dyeable with cationic dyes as described in 2. 4 Molecular weight of ethylene oxide and propylene oxide added randomly or in blocks
10-40 high molecular weight polyether compounds over 7000
5 to 30% by weight of a quaternary ammonium salt represented by the following general formula (), 30 to 80% by weight of one or more smoothing agent components selected from the following Group A, and 1 ～Divalent aliphatic carboxylic acid soap
An oil agent for treating polyester fibers dyeable with cationic dyes containing 0.5 to 3% by weight. General formula () [Formula] [However, R ¹ is both an alkyl group or alkenyl group having 6 to 18 carbon atoms, or an N-acylaminoalkyl group represented by [Formula] (wherein R ⁵ is both an alkyl group or alkenyl group having 5 carbon atoms)
~17 alkyl or alkenyl groups. ^R6 is hydrogen,
Methyl group, hydroxyethyl group or hydroxypropyl group. p is an integer of 2 or 3). ^R2 , ^R3 , ^R4
each independently represents a methyl group, an ethyl group, a hydroxyethyl group or a hydroxypropyl group. A ^-n is carboxylic acid, phosphoric acid, phosphoric ester,
An n-valent anion residue obtained by removing a hydrogen ion from each group of a sulfuric acid ester or a sulfonic acid ester. H ⁺ is a hydrogen ion. m and n are 0≦m≦2, 1≦n≦3, and n
−m=0 or an integer from 1 to 3 that satisfies 1 to 3. ] Group A: (1) polyether compound with a molecular weight of 700 to 3,500 to which ethylene oxide and propylene oxide are added randomly or in blocks, (2) mono- or poly(2-10 mol) oxyalkylene aliphatic alcohol and monohydric fatty acid. monoester with,
(3) Diester of mono- or poly(2-10 mol) oxyalkylene aliphatic alcohol and divalent fatty acid 5 In the general formula (), H ⁺ _n A ^-n is [formula] (where R ⁷ , R ⁸ The oil agent for treating cationic dye-dyeable polyester fibers according to claim 4, wherein each of the cationic dyes is a phosphate ester ion represented by the following (methyl group or ethyl group). 6 In the general formula (), H ⁺ _n A ^-n is R ⁹ OSO ₃ ^-
(herein, R ⁹ is a methyl group or an ethyl group)
An oil agent for treating polyester fibers dyeable with cationic dyes as described in 2. 7. After melt spinning the cationic dye-dyeable polyester fiber and before false twisting,
10 to 40% by weight of a high molecular weight polyether compound with a molecular weight of 7,000 or more to which ethylene oxide and propylene oxide are added randomly or in blocks; 5 to 30% by weight of a quaternary ammonium salt represented by the following general formula (); and 30 to 80% by weight of one or more smoothing agent components selected from the following Group A:
1. A method for treating polyester fibers dyeable with cationic dyes, the method comprising applying 0.3 to 1.2% by weight of an oil containing the same. General formula () [Formula] [However, R ¹ is both an alkyl group or alkenyl group having 6 to 18 carbon atoms, or an N-acylaminoalkyl group represented by [Formula] (wherein R ⁵ is both an alkyl group or alkenyl group having 5 carbon atoms)
~17 alkyl or alkenyl groups. ^R6 is hydrogen,
Methyl group, hydroxyethyl group or hydroxypropyl group. p is an integer of 2 or 3). ^R2 , ^R3 , ^R4
each independently represents a methyl group, an ethyl group, a hydroxyethyl group or a hydroxypropyl group. A ^-n is carboxylic acid, phosphoric acid, phosphoric ester,
An n-valent anion residue obtained by removing a hydrogen ion from each group of a sulfuric acid ester or a sulfonic acid ester. H ⁺ is a hydrogen ion. m and n are 0≦m≦2, 1≦n≦3, and n
−m=0 or an integer from 1 to 3 that satisfies 1 to 3. ] Group A: (1) polyether compound with a molecular weight of 700 to 3,500 to which ethylene oxide and propylene oxide are added randomly or in blocks, (2) mono- or poly(2-10 mol) oxyalkylene aliphatic alcohol and monohydric fatty acid. monoester with,
(3) Diester of mono- or poly(2-10 mol) oxyalkylene aliphatic alcohol and divalent fatty acid 8 In the general formula (), H ⁺ _n A ^-n is [formula] (where R ⁷ , R ⁸ 8. The method for treating polyester fibers dyeable with cationic dyes according to claim 7, wherein each is independently a phosphate ester ion represented by a methyl group or an ethyl group. 9 In the general formula (), H ⁺ _n A ^-n is R ⁹ OSO ₃ ^-
(herein, R ⁹ is a methyl group or an ethyl group) Claim 7 is a sulfate ester ion.
A method for treating polyester fibers dyeable with cationic dyes as described in 1.