TW202208720A - Method for manufacturing synthetic fiber treatment agent, synthetic fiber treatment agent, synthetic fiber, and method for manufacturing synthetic fiber - Google Patents

Abstract

The present invention addresses the problem of suitably suppressing fluffing during a spinning process. This method for producing a treatment agent for synthetic fibers, wherein the boron content in the nonvolatile content of the treatment agent for synthetic fibers as detected by ICP emission spectrometry is 200 ppm or less, comprises: an addition step wherein a (poly)oxyalkylene derivative is produced by adding an alkylene oxide to an alcohol in the presence of a catalyst that has a boron atom in each molecule; and a removal step wherein the catalyst is removed so that the boron content in the nonvolatile content of the treatment agent for synthetic fibers as detected by ICP emission spectrometry becomes 200 ppm or less.

Description

Manufacturing method of processing agent for synthetic fibers, processing agent for synthetic fibers, synthetic fiber, and manufacturing method of synthetic fiber

The present invention relates to a method for producing a treatment agent for synthetic fibers, a treatment agent for synthetic fibers, synthetic fibers, and a method for producing synthetic fibers.

For example, carbon fibers are produced by performing the following steps: a spinning step in which acrylic resin or the like is spun to produce a carbon fiber precursor of synthetic fibers; and a firing step in which the synthetic fibers are fired.

Patent Document 1 discloses an acrylic fiber treatment agent containing an amine group-modified polysiloxane and a polyoxyalkylene alkyl ether.

prior art literature Patent Literature Patent Document 1: International Publication No. 2017/169632

The problem to be solved by the invention However, in the spinning step, the fibers sometimes generate fluff, and therefore, suppressing the fluff in the spinning step is a current problem.

The present invention is made in view of the above-mentioned circumstances, and an object thereof is to provide a method for producing a treatment agent for synthetic fibers which can preferably suppress fluff in the spinning step. Further, the present invention provides a treatment agent for synthetic fibers capable of preferably suppressing fluff in the spinning step, a synthetic fiber to which the treatment agent for synthetic fibers adheres, and a method for producing synthetic fibers using the treatment agent for synthetic fibers.

means of solving problems The method for producing a treatment agent for synthetic fibers for solving the above-mentioned problems is characterized in that the content of boron detected from the nonvolatile portion of the treatment agent for synthetic fibers by ICP emission analysis is 200 ppm or less. Removal step; the above-mentioned addition step is to add alkylene oxide to alcohols in the presence of a catalyst having a boron atom in the molecule to make a (poly)oxyalkylene derivative; the above-mentioned removal step is to remove the above-mentioned catalyst. , so that the content of boron detected from the non-volatile part of the above-mentioned processing agent for synthetic fibers by ICP emission analysis method is 200 ppm or less.

In the method for producing the above-mentioned treatment agent for synthetic fibers, preferably, in the above-mentioned removing step, the above-mentioned catalyst is removed so that the content of boron detected from the non-volatile portion of the above-mentioned treatment agent for synthetic fibers by ICP emission analysis becomes 40ppm or less.

In the method for producing the above-mentioned treatment agent for synthetic fibers, preferably, the (poly)oxyalkylene derivative contains a ring having 2 to 4 carbon atoms added to 1 mol of alcohols at a ratio of 1 to 30 mol in total. A compound made of oxane.

As for the manufacturing method of the said processing agent for synthetic fibers, it is preferable that the said alcohol has a C10-C18 alkyl chain in a molecule|numerator.

As for the manufacturing method of the said processing agent for synthetic fibers, it is preferable that the said alcohol has a C12-C16 alkyl chain in a molecule|numerator.

In the manufacturing method of the said processing agent for synthetic fibers, it is preferable that the said alcohol is a monovalent aliphatic alcohol which has a hydroxyl group in the β-position of an alkyl chain.

It is preferable that the manufacturing method of the said processing agent for synthetic fibers further has a mixing step of mixing a smoothing agent.

As for the manufacturing method of the said processing agent for synthetic fibers, it is preferable that the said smoothing agent contains polysiloxane.

As for the manufacturing method of the said processing agent for synthetic fibers, it is preferable that the said smoothing agent contains amine group-modified polysiloxane.

In the method for producing the above-mentioned treatment agent for synthetic fibers, preferably, in the above-mentioned mixing step, the above-mentioned smoothing agent is mixed so that the total content ratio of the above-mentioned (poly)oxyalkylene derivative and the above-mentioned smoothing agent is 100 In the case of parts by mass, the ratio of 10 to 70 parts by mass of the (poly)oxyalkylene derivative and 90 to 30 parts by mass of the above-described smoothing agent is included.

In the method for producing the above-mentioned treatment agent for synthetic fibers, it is preferable that the above-mentioned synthetic fibers are carbon fiber precursors.

A treatment agent for synthetic fibers for solving the above-mentioned problems, which contains a smoothing agent and a (poly)oxyalkylene derivative, and focuses on the content of boron detected from the non-volatile part of the treatment agent by ICP emission analysis 200ppm or less.

It is preferable that the content of the said boron is 40 ppm or less in the said processing agent for synthetic fibers.

In the above-mentioned treatment agent for synthetic fibers, it is preferable that the above-mentioned (poly)oxyalkylene derivative contains an alkylene oxide having 2 to 4 carbon atoms added to 1 mol of alcohols at a ratio of 1 to 30 mol in total. formed compounds.

As for the said processing agent for synthetic fibers, it is preferable that the said alcohol has a C10-C18 alkyl chain in a molecule|numerator.

It is preferable that the said alcohol has an alkyl chain of C12-C16 in a molecule|numerator in the said processing agent for synthetic fibers.

In the above-mentioned treatment agent for synthetic fibers, it is preferable that the above-mentioned alcohols are monovalent aliphatic alcohols having a hydroxyl group at the β-position of the alkyl chain.

As for the above-mentioned treatment agent for synthetic fibers, it is preferable that the above-mentioned smoothing agent contains amine group-modified polysiloxane.

It is preferable that the said processing agent for synthetic fibers contains the said (poly)oxyalkylene derivative 10 when the sum total of the content ratio of the said (poly)oxyalkylene derivative and the said smoothing agent is made into 100 mass parts to 70 parts by mass, and the ratio of 90 to 30 parts by mass of the above-mentioned smoothing agent.

In the above-mentioned treatment agent for synthetic fibers, it is preferable that the above-mentioned synthetic fibers are carbon fiber precursors.

The synthetic fiber for solving the above-mentioned problem is characterized in that the above-mentioned processing agent for synthetic fibers is adhered.

The manufacturing method of the synthetic fiber for solving the above-mentioned subject is characterized by the step of adhering the above-mentioned processing agent for synthetic fibers to the fiber.

Invention effect According to the present invention, fluff in the spinning step can be preferably suppressed.

(first embodiment)

The first embodiment of the present invention, that is, a treatment agent for synthetic fibers (hereinafter referred to as a treatment agent) will be described.

The treatment agent of the present embodiment contains a smoothing agent and a (poly)oxyalkylene derivative. The content of boron detected from the nonvolatile portion of the treatment agent by the ICP emission analysis method in the treatment agent was 200 ppm or less. The content of boron in the treatment agent is 200 ppm or less, which can preferably suppress fluff in the spinning step.

Further, the content of boron detected from the nonvolatile portion of the treatment agent by ICP emission analysis is preferably 40 ppm or less, more preferably 15 ppm or less. When the content of boron is 40 ppm or less, fluff in the spinning step can be suppressed more preferably.

In addition, the content of boron detected from the nonvolatile portion of the processing agent by ICP emission analysis is, for example, 0.1 ppm or more, 0.6 ppm or more, 0.9 ppm or more, or 2 ppm or more.

Examples of the (poly)oxyalkylene derivatives include compounds obtained by adding alkylene oxide to alcohols or carboxylic acids, ether and ester compounds obtained by adding alkylene oxide to ester compounds of carboxylic acids and polyols, and the like. . The alcohols or carboxylic acids may be linear or branched aliphatic alcohols or carboxylic acids, or may be aromatic alcohols or carboxylic acids. Moreover, saturated alcohol or carboxylic acid may be sufficient, and unsaturated alcohol or carboxylic acid may be sufficient. In addition, monohydric or dihydric alcohols or carboxylic acids may also be used.

Specific examples of the above-mentioned (poly)oxyalkylene derivatives include, for example, compounds obtained by adding 1 mol of 2-dodecanol to 12 mols of ethylene oxide, and 1 mol of 2-tetradecanol. A compound obtained by adding 9 moles of oxyethane, a compound obtained by adding 1 mole of 2-dodecanol to 5 moles of ethylene oxide, and a compound formed by adding 1 mole of 2-dodecanol to 9 moles of ethylene oxide The compound formed by adding 1 mole of 2-dodecanol to 30 moles of ethylene oxide, the compound formed by adding 1 mole of 2-tridecanol to 9 moles of ethylene oxide, 2 - A compound obtained by adding 1 mol of tridecanol to 12 mol of ethylene oxide, a compound obtained by adding 1 mol of 2-decanol to 9 mol of ethylene oxide, and 1 mol of 2-octadecanol A compound obtained by adding 9 mol of ethylene oxide, a compound obtained by adding 1 mol of 2-nonanol to 5 mol of ethylene oxide, and a compound obtained by adding 1 mol of 4-dodecanol to ethylene oxide A compound formed by adding 1 mole of 1-tetradecanol to 25 moles of ethylene oxide, and a compound formed by adding 1 mole of 2-pentadecanol to 5 moles of ethylene oxide , 1-octanol 1 mol added ethylene oxide 7 mol compound, 1-nonanol 1 mol added ethylene oxide 20 mol compound, 1-dodecanol 1 mol A compound obtained by adding 9 mol of ethylene oxide to the ear, a compound obtained by adding 1 mol of 2-dodecanol to 5 mol of ethylene oxide, and the like.

The above-mentioned (poly)oxyalkylene derivatives may be used alone or in combination of two or more.

In the above-mentioned (poly)oxyalkylene derivatives, the number of added moles of alkylene oxides having 2 to 4 carbon atoms to 1 mole of alcohols is not particularly limited, but it is preferable to contain more than 1 mole of alcohols to alcohols. A compound obtained by adding an alkylene oxide having 2 to 4 carbon atoms in a total ratio of 1 to 30 moles.

The aforementioned alcohols are preferably those having an alkyl chain having 10 to 18 carbon atoms in the molecule, and more preferably those having an alkyl chain having 12 to 16 carbon atoms in the molecule.

In addition, the above-mentioned alcohols are preferably monovalent aliphatic alcohols having a hydroxyl group at the β-position of the alkyl chain. The monovalent aliphatic alcohols may be saturated aliphatic alcohols or unsaturated aliphatic alcohols. In addition, the monovalent aliphatic alcohol may be a linear aliphatic alcohol or a branched aliphatic alcohol.

By using the monohydric aliphatic alcohol having a hydroxyl group at the β-position of the alkyl chain, the wettability of the treatment agent to synthetic fibers can be improved as will be described later.

Specific examples of the above-mentioned alkylene oxide having 2 to 4 carbon atoms include, for example, ethylene oxide, propylene oxide, butylene oxide, and the like. Among these, ethylene oxide is more preferable. The polymerization arrangement is not particularly limited, and may be a random adduct or a block adduct.

As the smoothing agent contained in the processing agent of this embodiment, polysiloxane, ester, etc. are mentioned, for example.

The polysiloxane used as the smoothing agent is not particularly limited, and examples thereof include dimethyl polysiloxane, phenyl-modified polysiloxane, amine group-modified polysiloxane, amide group-modified polysiloxane, polysiloxane Ether-modified polysiloxane, amine-based polyether-modified polysiloxane, alkyl-modified polysiloxane, alkyl aralkyl-modified polysiloxane, alkyl polyether-modified polysiloxane, ester-modified polysiloxane Silicone, epoxy modified polysiloxane, methanol modified polysiloxane, mercapto modified polysiloxane, etc.

Among these, those containing amine group-modified polysiloxane are preferred.

The smoothing agent is one containing amine-modified polysiloxane, which can improve the smoothness of the treatment agent as described later.

The esters used as the smoothing agent are not particularly limited, and examples thereof include (1) octyl palmitate, oleyl laurate, oleyl oleate, isotetracosyl oleate, and the like, Ester compound formed by aliphatic monohydric alcohol and aliphatic monohydric carboxylic acid; (2) 1,6-hexanediol dicaprate, glyceryl trioleate, trimethylolpropane trilaurate, neopentyltetrakis Alcohol tetracaprylate, etc., ester compounds formed by aliphatic polyhydric alcohol and aliphatic monocarboxylic acid; (3) Dioleyl rhodochroic acid ester, dioleyl alcohol base mercaptan dipropionate, diisocetyl Thiol dipropionate, diisostearyl thiol dipropionate, etc., ester compounds formed by aliphatic monohydric alcohol and aliphatic polybasic acid; (4) benzyl oleate, benzyl laurate etc., ester compound formed by aromatic monohydric alcohol and aliphatic monocarboxylic acid; (5) bisphenol A dilaurate, dilaurate of bisphenol A alkylene oxide adduct, etc., aromatic polyol Complete ester compounds formed with aliphatic monocarboxylic acids; (6) bis-2-ethylhexyl phthalate, diisostearyl isophthalate, trioctyl trimellitic acid ester, etc., Complete ester compound formed by aliphatic monohydric alcohol and aromatic polybasic acid; (7) Natural oils such as coconut oil, rapeseed oil, sunflower oil, soybean oil, castor oil, sesame oil, fish oil and tallow. In addition to this, a well-known smoothing agent etc. which are used for the processing agent for synthetic fibers can also be used.

Specific examples of the smoothing agent include, for example, amine group-modified polysiloxane having a kinematic viscosity at 25°C of 650 mm ² /s and an amine group equivalent of 1800 g/mol; a kinematic viscosity at 25° C. of 90 mm ² /s, amine Amino-modified polysiloxane with a base equivalent of 5000 g/mol; an amine-modified polysiloxane with a kinematic viscosity of 4500 mm ² /s and an amine equivalent of 1200 g/mol at 25°C; the kinematic viscosity at 25°C of 40mm ² /s, amine group modified polysiloxane with amine group equivalent of 1800g/mol; amine group modified polysiloxane with dynamic viscosity of 8000mm ² /s and amine group equivalent of 1000g/mol at 25℃; Polyether-modified polysiloxane whose kinematic viscosity at 25°C is 500mm ² /s, ethylene oxide/propylene oxide=100/0, and the mass ratio of polysiloxane/polyether=50/50; Polyether-modified polysiloxane with a kinematic viscosity of 1700mm ² /s, ethylene oxide/propylene oxide=40/60, and polysiloxane/polyether mass ratio=20/80; the kinematic viscosity at 25°C is 10000mm ² /s dimethyl polysiloxane; di(n-dodecyl) thiol dipropionate; dilauryl ester of ethylene oxide 2 molar adduct of bisphenol A, etc.

The said smooth agent may be used individually by 1 type, and may be used in combination of 2 or more types.

The content ratio of the above-mentioned (poly)oxyalkylene derivative and smoothing agent is not limited. When the total of the content ratio of the (poly)oxyalkylene derivative and the smoothing agent is 100 parts by mass, the treatment agent preferably contains 10 to 70 parts by mass of the (poly)oxyalkylene derivative and 90 parts by mass of the smoothing agent ~30 parts by mass ratio. Moreover, it is more preferable that a processing agent is a ratio containing 20-60 mass parts of (poly)oxyalkylene derivatives, and 80-40 mass parts of smoothing agents.

(Second Embodiment)

The second embodiment of the present invention, that is, a method for producing a treatment agent will be described. The difference from the first embodiment will be mainly described.

The manufacturing method of a processing agent has an addition process and a removal process. The addition step is to add the above-mentioned alkylene oxide to the above-mentioned alcohols in the presence of a catalyst having a boron atom in the molecule to prepare a (poly)oxyalkylene derivative; the removal step is to remove the catalyst, so that the treatment agent The content of boron detected by the ICP emission analysis method in the non-volatile part of 200 ppm or less.

The catalyst having a boron atom in the molecule is not particularly limited, and an acidic catalyst composed of, for example, boron trifluoride, a complex thereof, or the like can be used.

As an example of the addition step, an acidic catalyst composed of boron trifluoride or a complex thereof is used to react alcohols with low molar, for example, 1 to 5 molar ethylene oxide, and then remove catalyst to obtain low molar ethoxide. Next, in the presence of an alkaline catalyst composed of sodium hydroxide, potassium hydroxide, sodium alkoxide, etc., the obtained low-molar ethoxide is further reacted with ethylene oxide, and then the catalyst media removal.

The method of removing the catalyst from the liquid that has passed through the addition step is not particularly limited, and a known method can be used. The method of removing the catalyst includes, for example, a method of filtering a liquid using diatomaceous earth to isolate the catalyst, or a method of removing the catalyst by adsorption from the liquid using an inorganic synthetic adsorbent.

The ICP emission analysis method can be performed in the following manner, for example. First, solutions with known boron concentrations (eg, 0, 5 ppm, and 1 ppm solutions) are prepared in advance, and the ICP emission analyzer is used to create a calibration curve. Next, the treatment agent that has passed the removal step is transferred to an ICP emission analyzer, and the content of boron contained in the nonvolatile portion of the treatment agent is measured using the calibration curve prepared above.

It is preferable that the manufacturing method of the processing agent of this embodiment has a mixing process of mixing the said smoothing agent. In the mixing step, the smoothing agent and the (poly)oxyalkylene derivative are preferably mixed in such a manner that the content ratios of the (poly)oxyalkylene derivative and the smoothing agent are defined in the first embodiment.

(third embodiment)

A third embodiment of the present invention, that is, synthetic fibers will be described. The synthetic fiber of this embodiment has the processing agent of 1st Embodiment adhered. Specific examples of the synthetic fibers are not particularly limited, and examples thereof include (1) polyester fibers such as polyethylene terephthalate, polytrimethylene terephthalate, and polylactate; (2) nylon 6 , nylon 66 and other polyamide fibers; (3) polyacrylic acid, modified acrylic acid and other polyacrylic fibers; (4) polyethylene, polypropylene and other polyolefin fibers; (5) celluloid fibers; (6) Lignin-based fibers, etc. The synthetic fiber is preferably a resin-made carbon fiber precursor that becomes carbon fiber through a carbonization treatment step described later. The resin constituting the carbon fiber precursor is not particularly limited, and examples thereof include acrylic resin, polyethylene resin, phenol resin, celluloid resin, lignin resin, pitch, and the like.

The amount of adhering the treating agent of the first embodiment to the synthetic fibers is not particularly limited, but it is preferable to adhere the treating agent (excluding the solvent) in an amount of 0.1 to 2 mass % with respect to the synthetic fibers, more preferably The agent adheres so as to be 0.3 to 1.2 mass % with respect to the synthetic fiber.

(4th embodiment)

A fourth embodiment of the present invention, that is, a method for producing synthetic fibers will be described. The manufacturing method of the synthetic fiber of this embodiment consists of the process of making the processing agent of 1st Embodiment adhere to a fiber.

As the form of the treatment agent when the treatment agent of the first embodiment is adhered to fibers, for example, an organic solvent solution, an aqueous liquid, and the like can be mentioned.

As a method of adhering the treatment agent to the synthetic fibers, for example, the following method can be applied: using an aqueous solution containing the treatment agent of the first embodiment and water, or a further diluted aqueous solution, by a known method such as a dipping method, a spray method, The roller method, the pilot oil method using a metering pump, etc. make it adhere.

The manufacturing method of the carbon fiber using the synthetic fiber of this embodiment is demonstrated.

The manufacturing method of carbon fiber is preferably carried out through the following steps 1 to 3.

Step 1: A spinning step in which the synthetic fiber is spun and the treatment agent of the first embodiment is attached.

Step 2: In the flame retardant treatment step, the synthetic fibers obtained in the above step 1 are converted into flame retardant fibers in an oxidative atmosphere of 200-300°C, preferably 230-270°C.

Step 3: carbonization treatment step, the flame retardant fiber obtained in the above step 2 is further carbonized in an inert atmosphere of 300-2000°C, preferably 300-1300°C.

Among them, the above-mentioned steps 2 and 3 constitute a firing step.

The spinning step preferably further includes the following steps: a wet spinning step, in which the resin is dissolved in a solvent for spinning; a drying and densification step, in which the wet spinning synthetic fibers are dried and densified; and an extension step , extending the dried and densified synthetic fibers.

The temperature of the drying and densification step is not particularly limited, but it is preferable to heat the synthetic fiber passed through the wet spinning step at, for example, 70 to 200°C. The timing of attaching the treatment agent to the synthetic fibers is not particularly limited, but is preferably between the wet spinning step and the dry densification step.

The oxidative atmosphere in the flame-retardant treatment step is not particularly limited, and, for example, an air atmosphere can be used.

The inert atmosphere in the carbonization treatment step is not particularly limited, and for example, a nitrogen atmosphere, an argon atmosphere, a vacuum atmosphere, or the like can be used.

According to the processing agent of this embodiment, its manufacturing method, a synthetic fiber, and its manufacturing method, the following effects can be acquired.

(1) The processing agent of the present embodiment contains a smoothing agent and a (poly)oxyalkylene derivative, and the content of boron detected from the nonvolatile portion of the processing agent by ICP emission analysis is a predetermined value. Therefore, the fluff of the fibers passing through the spinning step can be preferably suppressed. In addition, the smoothness of the fibers passing through the spinning step can be improved. In addition, the bundling properties of the flame-retardant fibers that have passed through the flame-retardant treatment step can be improved.

(2) According to the treating agent of the present embodiment, since the wettability to synthetic fibers is improved, the treating agent can be more uniformly adhered to the synthetic fibers.

(3) Between the wet spinning step and the dry densification step, the treatment agent is attached to the synthetic fibers. Therefore, in the spinning step, it is particularly preferable to suppress the fluff in the drying and densification step.

The above-described embodiment can be modified and implemented as follows. The above-described embodiment and the following modified examples can be implemented in combination with each other within the scope of not being technically inconsistent.

- In this embodiment, the step of removing the catalyst having a boron atom may be performed after the addition step is completed, or may be performed in the middle of the addition step, or the removal treatment may be performed after mixing other components.

・In the present embodiment, for example, synthetic fibers may be fibers that have not undergone a sintering step.

・As long as the effects of the present invention are not impaired, the treatment agent or aqueous solution of the present embodiment may further contain a stabilizer, antistatic agent, charge inhibitor, and adhesive for maintaining the quality of the treatment agent or aqueous solution , antioxidants, ultraviolet absorbers, etc. are usually used in treatment agents or components of aqueous liquids.

Example

Hereinafter, in order to demonstrate the structure and effect of this invention more concretely, although an Example etc. are given, this invention is not limited to these Examples. In addition, in the following description of an Example and a comparative example, a part shows a mass part, and % shows a mass %.

Test Category 1 (Preparation of Treatment Agents for Synthetic Fibers)

(Example 1) First, in terms of the addition step, 186 parts of 2-dodecanol and 0.5 part of boron trifluoride were added to the autoclave, and the atmosphere was replaced with nitrogen, and then 132 parts of ethylene oxide was slowly added at 150° C. for etherification. reaction.

Next, in the catalyst removal step, 5 parts of an anion exchange resin was added to the liquid subjected to the etherification reaction, and the mixture was stirred at room temperature for 30 minutes. Then, it was transferred to a filter pre-coated with diatomaceous earth, the anion exchange resin adsorbed with boron trifluoride catalyst was removed, and the ethylene oxide 3-molar adduct of 2-dodecanol was prepared. .

Furthermore, 318 parts of the obtained ethylene oxide 3-molar adduct of 2-dodecanol and 0.5 part of sodium hydroxide were added to the autoclave, the atmosphere was replaced with nitrogen, and then cyclohexane was slowly added at 150° C. 396 parts of oxyethanes were subjected to etherification reaction.

Furthermore, 10 parts of inorganic synthetic adsorbents were added to the liquid subjected to the etherification reaction, and the mixture was stirred at 80° C. for 30 minutes. Then, it was transferred to a filter pre-coated with diatomaceous earth, the inorganic synthetic adsorbent adsorbed with the sodium hydroxide catalyst was removed, and the (poly)oxyalkylene derivatives shown in Table 1 were prepared (poly)oxyalkylene derivatives ( A-1).

Each component shown in Table 1 was used, and it added to the beaker so that it might become a compounding ratio of 30 parts of (poly)oxyalkylene derivatives (A-1), and 70 parts of smoothing agents (B-1). These are stirred well to mix. The 25% aqueous liquid of the processing agent for synthetic fibers of Example 1 was prepared by slowly adding ion-exchanged water so that the density|concentration of solid content might become 25% while continuing stirring.

(Examples 2 to 23 and Comparative Examples 1 to 3) The treatment agents for synthetic fibers of Examples 2 to 23 and Comparative Examples 1 to 3 were prepared in the same manner as in Example 1 using the components shown in Table 1.

Among them, the type and content of the (poly)oxyalkylene derivative, the type and content of the smoothing agent, and the content of boron in the treatment agent in each example are shown in Table 1 "(A) (poly)oxyalkylene derivative, respectively. "Alkyl derivatives" column, "(B) Smoothing agent" column, and "Treatment agent boron content (ppm)" column.

Table 1

Details of each component of A-1 to A-14, a-1 to a-3, and B-1 to B-10 described in the symbol column of Table 1 are as follows.

((poly)oxyalkylene derivatives) A-1: A compound obtained by adding 1 mol of 2-dodecanol to 12 mol of ethylene oxide A-2: A compound obtained by adding 1 mol of 2-tetradecanol to 9 mol of ethylene oxide A-3: A compound obtained by adding 1 mol of 2-dodecanol to 5 mol of ethylene oxide A-4: A compound obtained by adding 1 mol of 2-dodecanol to 9 mol of ethylene oxide A-5: A compound obtained by adding 1 mol of 2-dodecanol to 30 mol of ethylene oxide A-6: A compound obtained by adding 1 mol of 2-tridecanol to 9 mol of ethylene oxide A-7: A compound obtained by adding 1 mol of 2-tridecanol to 12 mol of ethylene oxide A-8: A compound obtained by adding 1 mol of 2-decanol to 9 mol of ethylene oxide A-9: A compound obtained by adding 1 mol of 2-octadecanol to 9 mol of ethylene oxide A-10: A compound obtained by adding 1 mol of 2-nonanol to 5 mol of ethylene oxide A-11: A compound obtained by adding 1 mol of 4-dodecanol to 7 mol of ethylene oxide A-12: A compound obtained by adding 1 mol of 1-tetradecanol to 25 mol of ethylene oxide A-13: Compound obtained by adding 1 mol of 2-pentadecanol to 5 mol of ethylene oxide A-14: A compound obtained by adding 1 mol of 1-octanol to 7 mol of ethylene oxide a-1: A compound obtained by adding 1 mol of 1-nonanol to 20 mol of ethylene oxide a-2: A compound obtained by adding 1 mol of 1-dodecanol to 9 mol of ethylene oxide a-3: A compound obtained by adding 1 mol of 2-dodecanol to 5 mol of ethylene oxide

The type of the (poly)oxyalkylene derivative used in the above (poly)oxyalkylene derivative, the carbon number of the alcohol, the position of the hydroxyl group in the alkyl chain, and the boron of the (poly)oxyalkylene derivative The contents are shown in the column of "(A) (poly)oxyalkylene derivatives", the column of "carbon number of monovalent aliphatic alcohols", the column of "position of hydroxyl group", and the column of "boron content (ppm)" in Table 2, respectively .

Table 2 symbol (A) (Poly)oxyalkylene derivatives Carbon number of monohydric aliphatic alcohols The position of the hydroxyl group Boron content (ppm) A-1 A compound obtained by adding 1 mol of 2-dodecanol to 12 mol of ethylene oxide 12 beta 3 A-2 A compound obtained by adding 1 mole of 2-tetradecanol to 9 moles of ethylene oxide 14 beta 4 A-3 A compound obtained by adding 1 mol of 2-dodecanol to 5 mol of ethylene oxide 12 beta 3 A-4 A compound obtained by adding 1 mol of 2-dodecanol to 9 mol of ethylene oxide 12 beta 9 A-5 A compound obtained by adding 1 mol of 2-dodecanol to 30 mol of ethylene oxide 12 beta 9 A-6 A compound obtained by adding 1 mole of 2-tridecanol to 9 moles of ethylene oxide 13 beta twenty one A-7 A compound obtained by adding 1 mol of 2-tridecanol to 12 mol of ethylene oxide 13 beta 1 A-8 A compound obtained by adding 1 mole of 2-decanol to 9 moles of ethylene oxide 10 beta 9 A-9 A compound obtained by adding 1 mole of 2-octadecanol to 9 moles of ethylene oxide 18 beta 8 A-10 A compound obtained by adding 1 mole of 2-nonanol to 5 moles of ethylene oxide 9 beta 9 A-11 A compound obtained by adding 1 mol of 4-dodecanol to 7 mol of ethylene oxide 12 delta bit 12 A-12 A compound obtained by adding 1 mole of 1-tetradecanol to 25 moles of ethylene oxide 14 alpha position 9 A-13 A compound obtained by adding 1 mole of 2-pentadecanol to 5 moles of ethylene oxide 15 beta 216 A-14 1-Octanol 1 mol added to 7 mol of ethylene oxide 8 alpha position 194 a-1 1-Nonanol 1 mol added to 20 mol of ethylene oxide 9 alpha position 1320 a-2 1-Dodecanol 1 mol added to 9 mol of ethylene oxide 12 alpha position 1547 a-3 A compound obtained by adding 1 mol of 2-dodecanol to 5 mol of ethylene oxide 12 beta 1432

Among them, the difference in boron content of each (poly)oxyalkylene derivative in Table 2 is based on the removal of the catalyst by using a filter pre-coated with diatomaceous earth to adsorb the anion of boron trifluoride catalyst. Differences in the time of exchange resin removal. That is, the longer the anion exchange resin adsorbed with boron trifluoride catalyst is removed by a filter pre-coated with diatomaceous earth, the lower the boron content in the (poly)oxyalkylene derivative.

(Smoothing agent) B-1: Amine group-modified polysiloxane with a kinematic viscosity of 650 mm ² /s and an amine group equivalent of 1800 g/mol at 25°C B-2: A kinematic viscosity of 90 mm ² /s at 25°C , Amino group-modified polysiloxane B-3 with an amine group equivalent of 5000 g/mol: Amine group-modified polysiloxane B-4 with a kinematic viscosity of 4500 mm ² /s and an amine group equivalent of 1200 g/mol at 25°C : Amino group-modified polysiloxane B-5 with a kinematic viscosity of 40 mm ² /s and an amine group equivalent of 1800 g/mol at 25°C: a kinematic viscosity of 8000 mm ² /s at 25°C and an amine group equivalent of 1000 g/mol mol of amine modified polysiloxane B-6: kinematic viscosity at 25°C is 500mm ² /s, ethylene oxide/propylene oxide=100/0, mass ratio of polysiloxane/polyether=50/ 50 polyether-modified polysiloxane B-7: kinematic viscosity at 25℃ is 1700mm ² /s, ethylene oxide/propylene oxide=40/60, mass ratio of polysiloxane/polyether=20/ 80 polyether-modified polysiloxane B-8: dimethyl polysiloxane B-9 with a kinematic viscosity of 10,000 mm ² /s at 25°C: di(n-dodecyl) thiol dipropionate B-10: Dilauryl ester of ethylene oxide 2-molar adduct of bisphenol A

Test Category 2 (Manufacture of Synthetic Fibers and Carbon Fibers)

Synthetic fibers and carbon fibers were produced using the aqueous liquid of the synthetic fiber treatment agent prepared in Test Category 1.

First, as step 1, acrylic resin is wet-spun as synthetic fibers. Specifically, a copolymer having an intrinsic viscosity of 1.80 consisting of 95% by mass of acrylonitrile, 3.5% by mass of methacrylate, and 1.5% by mass of methacrylic acid was dissolved in dimethylacetamide (DMAC) to prepare a polymer A spinning dope with a concentration of 21.0 mass % and a viscosity of 500 poise at 60°C. The spinning dope was ejected from a spinning nozzle having a hole diameter (inner diameter) of 0.075 mm and a number of holes of 12,000 at a draft ratio of 0.8 in a coagulation tank of a DMAC 70 mass % aqueous solution maintained at a spinning bath temperature of 35°C.

The agglomerated yarn was removed from the solvent in a water washing tank, and was stretched 5 times to prepare an acrylic fiber strand (raw material) in a water-swelled state. This acrylic fiber strand was oiled with the treatment agent for synthetic fibers prepared in Test Category 1 so that the solid content adhesion amount was 1 mass % (solvent not included). The oiling of the treatment agent for synthetic fibers was carried out by a dipping method using a 4% ion-exchange aqueous solution of the treatment agent for synthetic fibers. Then, the acrylic fiber strands were dried and densified with a heating roll at 130°C, and then stretched by 1.7 times between the heating rolls at 170°C, and then wound up by a winding device (hereinafter referred to as a reel). on the wire tube.

Next, as step 2, the yarn is unwound from the wound synthetic fiber, and is subjected to flame retardant treatment in an air atmosphere using a flame retardant furnace with a temperature gradient of 230 to 270° C. for 1 hour, and then it is wound up. The flame retardant yarn (flame retardant fiber) is obtained on the silk tube.

Next, as step 3, the yarns are loosened from the coiled flame-retardant yarns, fired in a carbonization furnace with a temperature gradient of 300 to 1300° C. under a nitrogen atmosphere, and converted into carbon fibers, which are then wound into carbon fibers. Carbon fiber is obtained on the wire tube.

Test Category 3 (Evaluation)

The treatment agents of Examples 1 to 23 and Comparative Examples 1 to 3 were evaluated for fluff in the spinning step of synthetic fibers, bundling properties of flame-retardant fibers, smoothness of synthetic fibers, and wettability to synthetic fibers. The sequence of each test is as follows. In addition, the test results are shown in the columns of "spinning fluff", "flame retarding bundling", "smoothness", and "wetting properties" in Table 1.

(spinning fluff) In step 1 of test category 2, a fluff counting device was installed in front of the winding device for winding the synthetic fiber, the number of fluff per hour was measured, and the evaluation was performed according to the following criteria.

・Evaluation criteria for fluff ◎◎ (excellent): The number of fluffs is 0 to 2 ◎ (good): The number of fluffs is 3 to 5 〇 (acceptable): The number of fluffs is 6 to 10 × (defective): The number of fluffs is 11 or more

(Flame-retardant bundle) In step 2 of the test category 2, the flame-retardant fiber was subjected to the flame-retardant treatment by visually observing the bundled state of the flame-retardant yarn before winding, and the flame-retardant bundled property was evaluated according to the following criteria.

・Evaluation criteria for flame retardancy clustering ◎ (good): clustering, fixed width 〇 (Fair): Bundles are presented, but the width is not fixed × (defective): There are voids in the fiber bundles, and no bundles appear

(smoothness) An apparatus for measuring smoothness was AUTOGRAPH ABS-1kNX (tensile measuring apparatus) manufactured by Shimadzu Corporation.

As shown in FIG. 1 , one end of the synthetic fiber (hereinafter referred to as the test wire 1 ) to which the treatment agent is attached is fixed on the holding jig 2 of AUTOGRAPH, and then passes through the movable roller 3 , the chrome-plated rough body 4 , and the movable roller 5 in this order. , and a 50g weight 6 is fixed on the other end of the test wire 1 . In the chrome-plated rough body 4, the diameter of the drive shaft 4a in contact with the test wire 1 was 1 cm, and the surface roughness was 2S. It is arranged so that the extending direction of the test wire 1 between the chrome-plated rough body 4 and the movable roller 5 forms an angle of 90° with respect to the extending direction of the test wire 1 between the movable roller 3 and the chrome-plated asperity 4 . In this state, under the conditions of 25°C and 60% RH, the drive shaft 4a of the chrome-plated rough body 4 is rotated at a peripheral speed of 100 m/min in the direction of causing tension to the AUTOGRAPH, and the tension of the AUTOGRAPH in this state is measured every 0.1 second. 30 seconds. The average value (N) of the tension at this time was calculated|required, and it evaluated by the following reference|standard.

◎◎ (excellent): The average value of tension is less than 2N ◎ (good): The average value of the tension is 2N or more and less than 3N 〇 (acceptable): The average value of tension is more than 3N, less than 4N × (defective): The average value of the tension is 4N or more

(wetting) An ion-exchanged aqueous solution containing 4% of the active ingredient in the treatment agent for synthetic fibers (other than ion-exchanged water is regarded as an active ingredient) was prepared, 0.1 g of it was dropped on an acrylic plate, and the maximum diameter (mm) was measured 1 minute later. , and evaluated using the following criteria.

◎(Good): Maximum diameter of 12mm or more 〇 (acceptable): the maximum diameter is more than 10mm, less than 12mm × (defective): The maximum diameter is less than 10mm

From the results in Table 1, it can be seen that according to the present invention, fuzzing in the spinning step of synthetic fibers can be preferably suppressed. In addition, the bundling properties of the flame-retardant fibers and the smoothness of the synthetic fibers can be improved. In addition, the treatment agent according to the present invention can improve the wettability to synthetic fibers.

FIG. 1 is a schematic diagram of an apparatus for measuring smoothness.

Claims (22)

A method for producing a treatment agent for synthetic fibers, wherein the content of boron detected from the non-volatile portion of the treatment agent for synthetic fibers by ICP emission analysis is 200 ppm or less, characterized in that: There are addition steps and removal steps; The above-mentioned addition step is to add an alkylene oxide to alcohols in the presence of a catalyst having a boron atom in the molecule to make a (poly)oxyalkylene derivative; The said removal process removes the said catalyst so that the content of boron detected from the non-volatile part of the said processing agent for synthetic fibers by ICP emission analysis method may become 200 ppm or less. The method for producing a treatment agent for synthetic fibers according to claim 1, wherein In the said removal process, the said catalyst was removed so that the content of boron detected from the non-volatile part of the said processing agent for synthetic fibers by ICP emission analysis method might become 40 ppm or less. The method for producing a treatment agent for synthetic fibers according to claim 1 or 2, wherein The above-mentioned (poly)oxyalkylene derivative is a compound containing an alkylene oxide having 2 to 4 carbon atoms added to 1 mol of alcohols at a ratio of 1 to 30 mol in total. The method for producing a treatment agent for synthetic fibers according to any one of claims 1 to 3, wherein The above-mentioned alcohols are those having an alkyl chain having 10 to 18 carbon atoms in the molecule. The method for producing a treatment agent for synthetic fibers according to any one of claims 1 to 4, wherein The above-mentioned alcohols are those having an alkyl chain having 12 to 16 carbon atoms in the molecule. The method for producing a treatment agent for synthetic fibers according to claim 4 or 5, wherein The above-mentioned alcohols are monovalent aliphatic alcohols having a hydroxyl group at the β-position of the alkyl chain. The method for producing a treatment agent for synthetic fibers according to any one of claims 1 to 6, wherein Furthermore, there is a mixing step of mixing a smoothing agent. The method for producing a treatment agent for synthetic fibers according to claim 7, wherein The above-mentioned smoothing agent contains polysiloxane. The method for producing a treatment agent for synthetic fibers according to claim 7 or 8, wherein The above-mentioned smoothing agent contains amine-modified polysiloxane. The method for producing a treatment agent for synthetic fibers according to any one of claims 7 to 9, wherein In the above-mentioned mixing step, the above-mentioned smoothing agent is mixed so that the above-mentioned (poly)oxyalkylene derivative is included when the total content ratio of the above-mentioned (poly)oxyalkylene derivative and the above-mentioned smoothing agent is 100 parts by mass. 10 to 70 parts by mass of the material and 90 to 30 parts by mass of the above-mentioned smoothing agent. The method for producing a treatment agent for synthetic fibers according to any one of claims 1 to 10, wherein The above-mentioned synthetic fibers are carbon fiber precursors. A treatment agent for synthetic fibers, comprising a smoothing agent and a (poly)oxyalkylene derivative, characterized in that: The content of boron detected from the nonvolatile portion of the treatment agent by ICP emission analysis was 0.1 ppm or more and 200 ppm or less. The treatment agent for synthetic fibers according to claim 12, wherein The content of the above-mentioned boron is 40 ppm or less. The treatment agent for synthetic fibers according to claim 12 or 13, wherein The above-mentioned (poly)oxyalkylene derivative is a compound containing an alkylene oxide having 2 to 4 carbon atoms added to 1 mol of alcohols at a ratio of 1 to 30 mol in total. The treatment agent for synthetic fibers according to claim 14, wherein The above-mentioned alcohols are those having an alkyl chain having 10 to 18 carbon atoms in the molecule. The treatment agent for synthetic fibers according to claim 14 or 15, wherein The above-mentioned alcohols are those having an alkyl chain having 12 to 16 carbon atoms in the molecule. The treatment agent for synthetic fibers according to claim 15 or 16, wherein The above-mentioned alcohols are monovalent aliphatic alcohols having a hydroxyl group at the β-position of the alkyl chain. The treatment agent for synthetic fibers according to any one of claims 12 to 17, wherein The above-mentioned smoothing agent contains amine-modified polysiloxane. The treatment agent for synthetic fibers according to any one of claims 12 to 18, wherein When the total content of the (poly)oxyalkylene derivative and the smoothing agent is 100 parts by mass, the (poly)oxyalkylene derivative and 90 to 70 parts by mass of the above-mentioned smoothing agent are contained. 30 parts by mass. The treatment agent for synthetic fibers according to any one of claims 12 to 19, wherein The above-mentioned synthetic fibers are carbon fiber precursors. A synthetic fiber, characterized in that: The processing agent for synthetic fibers in any one of Claims 12-19 adheres. A method for producing synthetic fibers, characterized in that: By the step of attaching the treatment agent for synthetic fibers according to any one of claims 12 to 19 to fibers.

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