JP2012188776A - Method for manufacturing synthetic fiber, fiber treating agent and method for preventing fusion of synthetic fiber - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for manufacturing high-strength synthetic fiber, which prevents fusion between single filaments during hot drawing and/or a heat treatment of raw material synthetic fiber and has excellent fiber productivity, processability and productivity, to provide a fiber treating agent used in manufacturing the synthetic fiber, and to provide a method for preventing fusion of synthetic fiber by using the treating agent.SOLUTION: A method for manufacturing synthetic fiber with strength of 18 cN/dtex or more, comprises: a step (A) of providing raw material synthetic fiber with a fiber treating agent essentially including at least one kind of organic phosphorus compound selected from a compound represented by a general formula (1), a compound represented by a general formula (2) and a compound represented by a general formula (3); and a step (B) of subjecting the raw material synthetic fiber having been provided with the fiber treating agent to hot drawing and/or a heat treatment.

Description

  The present invention relates to a synthetic fiber production method, a fiber treatment agent, and a synthetic fiber fusion prevention method. More specifically, a method for producing a synthetic fiber capable of preventing fusion between single fibers, which is likely to occur when producing a high-strength synthetic fiber, a fiber treatment agent used in producing the synthetic fiber, and the treatment agent The present invention relates to a method for preventing fusion of synthetic fibers used.

  In recent years, the demand for synthetic fibers has been advanced, and in particular, the demand for fibers exhibiting high strength and high elastic modulus has increased. In order to satisfy this requirement, high-strength synthetic fibers (so-called super fibers) are produced by heat-stretching raw synthetic fibers at high temperatures or by performing heat treatment for a long time.

  In order to obtain high strength and high elastic modulus, when heat-stretching and heat-treating raw material synthetic fibers that become high-strength synthetic fibers, the fibers soften and stick between single fibers, and are called fusion or glue. Will occur. When fusion occurs between single fibers, not only the fiber spinning property is deteriorated, but also fibers having high strength and high elastic modulus cannot be obtained, which cannot meet the recent market demand.

  In order to solve these problems, methods using various inorganic fine particles have been proposed. For example, a method for imparting a hydrated gel-forming inorganic compound to a fusible fiber (Patent Document 1), a method for surface-treating inert inorganic particles such as talc, alumina, graphite, etc. (Patent Document 2), an inorganic material for synthetic fibers, etc. There has been proposed a method in which particles are applied to perform heat stretching and heat treatment. However, in the method using these inorganic fine particles, a large amount of the inorganic fine particles applied to the fibers remain after the hot drawing or heat treatment, so that the yarn making process is fouled. Further, the fiber is easily damaged due to the lack of smoothness of the inorganic fine particles, and the obtained raw yarn has a lot of fluff and the quality is lowered. Further, in post-processing steps such as a yarn-making step, a twisting step, and a weaving step, guide wear and scum are generated due to the dropping of inorganic fine particles, and the workability is remarkably lowered.

  In order to solve these problems of workability, a method of removing inorganic fine powder by applying water and air jet treatment (Patent Document 3), a method of removing after heat treatment using hydrophilic inorganic fine powder (Patent Document 4) ), A method of limiting the remaining amount of non-fusible fine powder (Patent Document 5), and the like. However, although these methods can improve post-processability, there is a problem that a step of removing inorganic fine particles is required, and not only productivity is lowered, but also the yarn damage is increased due to an increase in the number of steps.

JP 58-54021 A JP-A-50-157619 JP-A-62-149934 JP 2005-23500 A JP 2005-15931 A

  An object of the present invention is a method for producing a high-strength synthetic fiber that can prevent fusion between single fibers at the time of heat-stretching and / or heat-treating a raw synthetic fiber, and has excellent yarn-making properties, workability, and productivity, An object of the present invention is to provide a fiber treatment agent used for producing the synthetic fiber, and a method for preventing fusion of the synthetic fiber using the treatment agent.

  As a result of intensive studies to solve the above-described problems, the present inventors have found that when a fiber treatment agent containing a specific organophosphorus compound is used, a single synthetic fiber is subjected to thermal drawing and / or heat treatment. It has been found that fusion can be prevented and excellent spinning properties are obtained. Further, the present inventors have found that there is no scum generation in the post-process, excellent workability, and further, it is not necessary to remove the organophosphorus compound, so that the productivity is excellent and the raw yarn is not damaged.

  That is, the production method of the present invention is a method for producing a synthetic fiber having a strength of 18 cN / dtex or more, and includes a compound represented by the following general formula (1), a compound represented by the following general formula (2), and the following general formula: A step (A) of applying to the raw synthetic fiber a fiber treating agent that essentially contains at least one organic phosphorus compound selected from the compounds represented by (3), and a raw synthetic fiber to which the fiber treating agent is applied And a step (B) of heat stretching and / or heat treatment.

(In the formulas (1), (2) and (3), R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are each independently a hydrocarbon group having 2 to 18 carbon atoms. X ¹ , X ² and X ³ are each independently represented by a hydrocarbon group having 2 to 18 carbon atoms, a hydrogen atom, an alkali metal, an alkaline earth metal and NR ^a R ^b R ^c R ^d And at least one selected from a group, R ^a , R ^b , R ^c and R ^d each independently represent a hydrogen atom, an alkyl group, an alkanol group or a polyoxyalkylene group.)

  In the step (B), the temperature for the heat stretching and / or heat treatment is preferably 260 ° C. or higher.

  The production method of the present invention is suitable when the synthetic fiber is at least one selected from wholly aromatic polyester fibers, wholly aromatic polyamide fibers, and wholly aromatic copolyamide fibers.

  The amount of the organic phosphorus compound attached to the synthetic fiber is preferably 0.05 to 10% by weight.

  The fiber treatment agent of the present invention is a fiber treatment agent used when producing a synthetic fiber having a strength of 18 cN / dtex or more, and is represented by the compound represented by the general formula (1) and the general formula (2). And at least one organic phosphorus compound selected from the compounds represented by the above general formula (3).

In the fiber treatment agent of the present invention, it is preferable that the weight ratio of the organophosphorus compound in the nonvolatile content of the treatment agent is 50 to 100% by weight.
The fiber treatment agent of the present invention preferably contains a solvent and the organic phosphorus compound is dissolved in the solvent.

  The fiber treatment agent of the present invention is suitable when the synthetic fiber is at least one selected from wholly aromatic polyester fibers, wholly aromatic polyamide fibers, and wholly aromatic copolyamides.

  The method for preventing fusion of synthetic fibers according to the present invention is a method for preventing fusion between single fibers when producing a synthetic fiber having a strength of 18 cN / dtex or more. After applying the above, the fiber is subjected to hot drawing and / or heat treatment.

The method for producing a synthetic fiber of the present invention can prevent fusion between single fibers when the raw synthetic fiber is hot-drawn and / or heat-treated, and is excellent in yarn production. In addition, there is no scum generation in the subsequent process, and the processability is excellent. Furthermore, since it is not necessary to remove the organophosphorus compound, the productivity is excellent and the raw yarn is not damaged.
The fiber treatment agent of the present invention can prevent fusion between single fibers when the raw synthetic fiber is hot-drawn and / or heat-treated, and can impart excellent yarn-making properties, workability, and productivity.
The method for preventing fusion of synthetic fibers of the present invention can prevent fusion between single fibers when the raw synthetic fiber is subjected to hot drawing and / or heat treatment.

  The fiber treatment agent of the present invention is a fiber treatment agent used when producing a high-strength synthetic fiber, and essentially contains a specific organophosphorus compound. Moreover, the manufacturing method of this invention is a manufacturing method of a high intensity | strength synthetic fiber using the fiber processing agent which contains a specific organophosphorus compound essential. Details will be described below.

[Organic phosphorus compounds]
The organophosphorus compound used in the present invention has at least one bond between a phosphorus atom and a hydrocarbon group. The compound represented by the general formula (1), the compound represented by the general formula (2), and It is at least one selected from the compounds represented by the general formula (3). By pre-applying such an organic phosphorus compound to the raw material synthetic fiber before hot drawing and / or heat treatment, it is possible to prevent fusion between single fibers that occurs during heat drawing and / or heat treatment. It can give the yarn-making property. Further, there is no occurrence of scum in the subsequent process, and excellent workability can be imparted. Furthermore, since it is not necessary to remove the organophosphorus compound, excellent productivity can be imparted and there is no damage to the raw yarn.

The organophosphorus compound represented by the general formula (1) has one bond between a phosphorus atom and a hydrocarbon group, and is composed of an organic phosphonic acid, an organic phosphonic acid salt, an organic phosphonic acid monoester, and an organic phosphonic acid monoester. It is at least one selected from ester salts and organic phosphonic acid diesters.
In the general formula (1), R ¹ represents a hydrocarbon group having 2 to 18 carbon atoms. When the number of carbon atoms of the hydrocarbon group is less than 2, the friction of the fiber to which the organophosphorus compound has been added becomes high, causing fluff. On the other hand, when the number of carbon atoms exceeds 18, the effect of preventing fusion is low, and it is necessary to increase the amount applied to the fiber, which is not preferable. Examples of the hydrocarbon group include an alkyl group, an alkenyl group, an aryl group, and an aralkyl group. Among these, as the hydrocarbon group, an alkyl group, an alkenyl group, and an aryl group are preferable from the viewpoint of easy preparation of a solution and easy availability.

2-18 are preferable, as for carbon number of an alkyl group, 4-18 are more preferable, and 4-12 are more preferable. Such alkyl groups include ethyl, butyl, isobutyl, tertiary butyl, hexyl, octyl, nonyl, decyl, lauryl, tridecyl, isotridecyl, cetyl, isocetyl, stearyl. Groups and the like.
Moreover, 2-18 are preferable, as for carbon number of an alkenyl group, 4-18 are more preferable, and 8-18 are more preferable. Examples of such alkenyl groups include octenyl, decenyl, dodecenyl, tetradecenyl, palmitoleyl, oleyl, linoleyl and the like.
Moreover, 6-18 are preferable, as for carbon number of an aryl group, 6-12 are more preferable, and 6 is more preferable. Examples of such an aryl group include a phenyl group, a biphenyl group, and a naphthyl group.
Moreover, 7-18 are preferable, as for carbon number of an aralkyl group, 7-15 are more preferable, and 7-13 are more preferable. Examples of such an aralkyl group include a benzyl group, a phenylethyl group, a phenylbutyl group, a methylbenzyl group, and a naphthylmethyl group.

In the general formula (1), X ¹ and X ² are each independently a hydrocarbon group having 2 to 18 carbon atoms, a hydrogen atom, an alkali metal, an alkaline earth metal, and NR ^a R ^b R ^c R ^d At least one selected from the groups shown is shown.
When the carbon number of the hydrocarbon group is less than 2, the friction of the fiber to which the organophosphorus compound has been added becomes high, which may cause fluff. On the other hand, when the number of carbon atoms exceeds 18, the effect of preventing fusion is low, and a large amount of fiber may be required. Examples of the hydrocarbon group having 2 to 18 carbon atoms include the same ones as the hydrocarbon group having 2 to 18 carbon atoms described for R ¹ .
Examples of the alkali metal include lithium, sodium, and potassium. The alkaline earth metal as used in the field of this invention means the alkaline earth metal of the broad sense which shows the whole group 2 element. Examples of the alkaline earth metal include magnesium, calcium, barium and the like.

R ^a , R ^b , R ^c and R ^d in the group represented by NR ^a R ^b R ^c R ^d each independently represent a hydrogen atom, an alkyl group, an alkanol group or a polyoxyalkylene group.
1-18 are preferable, as for carbon number of an alkyl group, 4-18 are more preferable, and 4-12 are more preferable. Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an octyl group, a lauryl group, and a stearyl group.
As for carbon number of an alkanol group, 1-8 are preferable normally, 2-4 are more preferable, and 2-3 are more preferable. Examples of the alkanol group include methanol group, ethanol group, n-propanol group, isopropanol group, normal butanol group, octanol group, and the like.
2-6 are preferable, as for carbon number of a polyoxyalkylene group, 2-4 are more preferable, and 2-3 are more preferable. Examples of the polyoxyalkylene group include a polyoxyethylene group, a polyoxypropylene group, and a polyoxybutylene group.

X ¹ and X ² are preferably a hydrogen atom, sodium, potassium, and magnesium, and more preferably hydrogen, sodium, and potassium from the viewpoint that contamination of the apparatus due to thermal deterioration during heat treatment can be suppressed and fluff of fibers can be suppressed.

  Examples of the organic phosphorus compound represented by the general formula (1) include monobutylphosphonic acid, monohexylphosphonic acid, monooctylphosphonic acid, monolaurylphosphonic acid, monostearylphosphonic acid, monooleylphosphonic acid, monophenylphosphonic acid, Organic phosphonic acids such as monobenzylphosphonic acid; organic phosphonates such as potassium, sodium, magnesium, ammonium, diethanolamine, and laurylaminoether salts of these organic phosphonic acids; monobutylphosphonic acid monobutyl ester, mono Butylphosphonic acid monohexyl ester, monobutylphosphonic acid monooctyl ester, monobutylphosphonic acid monolauryl ester, monobutylphosphonic acid monooleyl ester, monooctylphosphonic acid monobutyl ester, monooctyl ester Phosphonic acid monohexyl ester, monooctylphosphonic acid monooctyl ester, monooctylphosphonic acid monolauryl ester, monooctylphosphonic acid monooleyl ester, phenylphosphonic acid monobutyl ester, phenylphosphonic acid monohexyl ester, phenylphosphonic acid monooctyl ester Organic phosphonic acid monoesters such as phenylphosphonic acid monolauryl ester; organic phosphonic acid monoester salts such as potassium salt, sodium salt, magnesium salt, ammonium salt, diethanolamine salt, and lauryl amino ether salt of these organic phosphonic acid monoesters; Monobutylphosphonic acid dibutyl ester, monobutylphosphonic acid dioctyl ester, monobutylphosphonic acid dilauryl ester, monooctylphosphone Dibutyl ester, monooctylphosphonic acid dihexyl ester, monooctylphosphonic acid dioctyl ester, monooctylphosphonic acid dilauryl ester, phenylphosphonic acid dibutyl ester, phenylphosphonic acid dihexyl ester, phenylphosphonic acid dioctyl ester, phenylphosphonic acid dilauryl ester, And organic phosphonic acid diesters such as phenylphosphonic acid diphenyl ester.

Among these organophosphorus compounds represented by the above general formula (1), from the viewpoint of solubility of the organophosphorus compound, monobutylphosphonic acid, monohexylphosphonic acid, monooctylphosphonic acid, monolaurylphosphonic acid, monostearyl Organic phosphonic acids such as phosphonic acid, monooleylphosphonic acid, monophenylphosphonic acid, monobenzylphosphonic acid; organic phosphonic acid salts such as potassium, sodium, ammonium, diethanolamine and laurylaminoether salts of these organic phosphonic acids Monobutylphosphonic acid monobutyl ester, monobutylphosphonic acid monohexyl ester, monobutylphosphonic acid monooctyl ester, monobutylphosphonic acid monolauryl ester, monobutylphosphonic acid monooleyl ester, monooctylphosphonic acid Nobutyl ester, monooctylphosphonic acid monohexyl ester, monooctylphosphonic acid monooctyl ester, monooctylphosphonic acid monolauryl ester, monooctylphosphonic acid monooleyl ester, phenylphosphonic acid monobutyl ester, phenylphosphonic acid monohexyl ester, Organic phosphonic acid monoesters such as phenylphosphonic acid monooctyl ester and phenylphosphonic acid monolauryl ester; organic phosphonic acid monoesters such as potassium salt, sodium salt, ammonium salt, diethanolamine salt and laurylamino ether salt of these organic phosphonic acid monoesters Ester salts are preferred.
Furthermore, organic phosphonic acids such as monobutylphosphonic acid, monohexylphosphonic acid, monooctylphosphonic acid, monolaurylphosphonic acid, monostearylphosphonic acid, monooleylphosphonic acid, monophenylphosphonic acid, monobenzylphosphonic acid; Organic phosphonates such as potassium salt, sodium salt, ammonium salt of phosphonic acid; monobutylphosphonic acid monobutyl ester, monobutylphosphonic acid monohexyl ester, monobutylphosphonic acid monooctyl ester, monobutylphosphonic acid monolauryl ester, Monobutylphosphonic acid monooleyl ester, monooctylphosphonic acid monobutyl ester, monooctylphosphonic acid monohexyl ester, monooctylphosphonic acid monooctyl ester, monooctylphosphonic acid model Organic phosphonic acid monoesters such as lauryl ester, monooctylphosphonic acid monooleyl ester, phenylphosphonic acid monobutyl ester, phenylphosphonic acid monohexyl ester, phenylphosphonic acid monooctyl ester, phenylphosphonic acid monolauryl ester; Organic phosphonic acid monoester salts such as potassium, sodium and ammonium salts of monoesters are preferred.

The organic phosphorus compound represented by the general formula (2) has two bonds between a phosphorus atom and a hydrocarbon group, and is at least one selected from organic phosphinic acid, organic phosphinic acid salt, and organic phosphinic acid monoester. It is a seed.
In the general formula (2), R ² and R ³ each independently represent a hydrocarbon group having 2 to 18 carbon atoms. When the number of carbon atoms of the hydrocarbon group is less than 2, the friction of the fiber to which the organophosphorus compound has been added becomes high, causing fluff. On the other hand, when the number of carbon atoms exceeds 18, the effect of preventing fusion is low, and it is necessary to increase the amount applied to the fiber, which is not preferable. Examples of R ² and R ³ are the same as those of the hydrocarbon group having 2 to 18 carbon atoms described in R ¹ .

In the general formula (2), X ³ is at least 1 selected from a hydrocarbon group having 2 to 18 carbon atoms, a hydrogen atom, an alkali metal, an alkaline earth metal, and ^a group represented by NR ^a R ^b R ^c R ^d Indicates the species. R ^a , R ^b , R ^c and R ^d each independently represent a hydrogen atom, an alkyl group, an alkanol group or a polyoxyalkylene group. The X ^3, may include the same as those described in X ¹ and X ^2.

  Examples of the organic phosphorus compound represented by the general formula (2) include dibutylphosphinic acid, dihexylphosphinic acid, dioctylphosphinic acid, dilaurylphosphinic acid, distearylphosphinic acid, dioleylphosphinic acid, diphenylphosphinic acid, dibenzylphosphinic acid. Organic phosphinic acids such as potassium phosphates, sodium salts, magnesium salts, ammonium salts, diethanolamine salts, laurylamino ether salts, etc .; dibutyl phosphinic acid monobutyl esters, dibutyl phosphinic acid monooctyl esters , Dioctylphosphinic acid monobutyl ester, dioctylphosphinic acid monooctyl ester, dilaurylphosphinic acid monobutyl ester, dilaurylphosphinic acid monooctyl ester And the like organic phosphinic acid monoester.

Among these organophosphorus compounds represented by the above general formula (2), from the viewpoint of solubility of the organophosphorus compound, dibutylphosphinic acid, dihexylphosphinic acid, dioctylphosphinic acid, dilaurylphosphinic acid, distearylphosphinic acid, Organic phosphinic acids such as dioleyl phosphinic acid, diphenyl phosphinic acid, dibenzyl phosphinic acid; organic phosphinic acid salts such as potassium salt, sodium salt, magnesium salt, ammonium salt, diethanolamine salt, lauryl amino ether salt of these organic phosphinic acids preferable.
Furthermore, organic phosphinic acids such as dibutylphosphinic acid, dihexylphosphinic acid, dioctylphosphinic acid, dilaurylphosphinic acid, distearylphosphinic acid, dioleylphosphinic acid, diphenylphosphinic acid, dibenzylphosphinic acid; potassium of these organic phosphinic acids Organic phosphinic acid salts such as salts, sodium salts and ammonium salts are preferred.

The organophosphorus compound represented by the general formula (3) is a tertiary phosphine oxide having three bonds between a phosphorus atom and a hydrocarbon group.
In the general formula ^{(3), R 4, R} 5 and ^{R 6} each independently represent a hydrocarbon group having 2 to 18 carbon atoms. When the number of carbon atoms of the hydrocarbon group is less than 2, the friction of the fiber to which the organophosphorus compound has been added becomes high, causing fluff. On the other hand, when the number of carbon atoms exceeds 18, the effect of preventing fusion is low, and it is necessary to increase the amount applied to the fiber, which is not preferable. Examples of R ⁴ , R ⁵ and R ⁶ are the same as those of the hydrocarbon group having 2 to 18 carbon atoms described in R ¹ .

  Examples of the organophosphorus compound represented by the general formula (3) include tributylphosphine oxide, trioctylphosphine oxide, trilaurylphosphine oxide, tristearylphosphine oxide, triphenylphosphine oxide, and the like. Among these, trioctyl phosphine oxide and trilauryl phosphine oxide are more preferable.

  The organophosphorus compound used in the present invention is diluted with water, an organic solvent or the like and applied to the raw synthetic fiber, but it is preferably used in an aqueous solution from the viewpoint of handleability. From these points, among the compound represented by the general formula (1), the compound represented by the general formula (2), and the compound represented by the general formula (3), the compound represented by the general formula (1) is used. The compound, the compound represented by the general formula (2) is preferable, and the compound represented by the general formula (1) is more preferable.

  The method for producing the compound represented by the general formula (1), the compound represented by the general formula (2), and the compound represented by the general formula (3) is not particularly limited, and a known method can be employed. Many of these organophosphorus compounds are commercially available, and they can be used in the present invention.

[Fiber treatment agent]
The fiber treatment agent of the present invention is a treatment agent used when producing a synthetic fiber (hereinafter sometimes referred to as high-strength fiber) having a strength of 18 cN / dtex or more. In order to produce such a high-strength fiber, it is usually necessary to carry out heat drawing and / or heat treatment. In order to prevent fusion between single fibers, which is likely to occur at that time, the fiber treatment agent of the present invention is used. Can be used. The high-strength fiber will be described later in the synthetic fiber manufacturing method.
The fiber treatment agent of this invention contains said organic phosphorus compound essential. The weight ratio of the organophosphorus compound in the entire nonvolatile content of the treating agent is preferably 40% by weight or more, more preferably 60% by weight or more, and further preferably 80% by weight or more. When the weight ratio is less than 40% by weight, the anti-fusing property is lowered. In addition, due to thermal deterioration of components other than the organophosphorus compound used at the same time, the apparatus may become dirty and productivity may be reduced. The non-volatile content in the present invention refers to an absolutely dry component when the treatment agent is heat treated at 105 ° C. to remove the solvent and the like and reach a constant weight.

  Examples of the solvent contained in the treatment agent include water, low-viscosity mineral oil, and organic solvents such as ethanol, isopropyl alcohol, pentanol, and toluene. In order to obtain an excellent anti-fusing property, it is necessary to sufficiently infiltrate the treating agent between the single fibers and uniformly adhere to the fiber surface. The treatment agent is preferably water-based from the viewpoint of imparting it uniformly and convenience. That is, it is preferable to contain water as a solvent essential.

  As described above, the fiber treatment agent of the present invention is preferably in a state in which the above organic phosphorus compound is dissolved in a solvent, and more preferably in a state in which the organic phosphorus compound is dissolved in water from the viewpoint that it is uniformly applied to the raw synthetic fibers. The dissolved state refers to a state in which the organophosphorus compound is uniformly mixed in a liquid (solvent), and is a state where the solution is allowed to stand at room temperature for 24 hours and no separation or sediment is generated.

  In the fiber treatment agent of the present invention, the organic phosphorus compound may be dissolved alone in water, but an emulsifier or the like may be used in combination for the purpose of assisting water solubility. When the emulsifier is used, the weight ratio of the emulsifier to the entire nonvolatile content of the treatment agent is preferably 2 to 60% by weight, more preferably 5 to 55% by weight, and further preferably 10 to 50% by weight. When the weight ratio is less than 2% by weight, a stable solution may not be obtained. On the other hand, when it exceeds 60% by weight, in the step (B), contamination of the apparatus due to thermal deterioration of the emulsifier may occur, and productivity may decrease. In addition, 40 to 98 weight% is preferable, as for the weight ratio of the organophosphorus compound to the whole non volatile matter of a processing agent when using an emulsifier, 50 to 95 weight% is more preferable, and 60 to 90 weight% is further more preferable.

  The emulsifier is not particularly limited. For example, POE (5 mol addition) octyl ether, POE (5 mol addition) lauryl ether, POE (9 mol addition) lauryl ether, POE (8 mol addition) oleyl ether, POE ( 10 mol addition) Polyoxyethylene alkyl ethers such as stearyl ether, POE (9 mol addition) nonylphenyl ether; POE (10 mol addition) castor oil ether, POE (10 mol addition) hydrogenated castor oil ether, POE (20 mol addition) Castor oil derivatives such as hydrogenated castor oil ether, POE (20 mol addition) hydrogenated castor oil ether trioleate, POE (20 mol addition) hydrogenated castor oil ether monolaurate; POE (20 mol addition) sorbitan ether monolaurate, POE ( 20 mole addition) sorbita Sorbitan derivatives such as ether trilaurate, POE (20 mole addition) sorbitan ether monooleate, POE (20 mole addition) sorbitan ether trioleate; POE (15 mole addition) ether, polyethylene glycol monooleate, polyethylene glycol dilaurate, etc. And polyhydric alcohol derivatives thereof.

  Further, the fiber treatment agent of the present invention may contain other components such as an antistatic agent, a bundling agent, a preservative, and a rust preventive agent within a range that does not hinder the effects of the present invention in order to wait for other characteristics. Good.

  The fiber treatment agent of the present invention may be composed of the above-described components consisting only of non-volatile content, or may be diluted with water or low-viscosity mineral oil, and emulsifies the non-volatile content in water using an emulsifier. It may be a water-based emulsion. When the fiber treatment agent is transferred to a factory or the like, the weight ratio of the non-volatile content in the fiber treatment agent is preferably 30 to 100% by weight from the viewpoint of transportation cost and stability of the treatment agent. The weight ratio of the non-volatile content in the fiber treatment agent when applied to the raw synthetic fiber is preferably 0.01 to 20% by weight, and more preferably 0.1 to 15% by weight.

  There is no limitation in particular as a manufacturing method of the fiber treatment agent of this invention, A well-known method is employable. For example, in the case of an aqueous solution obtained by neutralizing the unneutralized organic phosphorus compound, the aqueous solution can be prepared by gradually adding the organic phosphorus compound to an aqueous solution in which a predetermined amount of alkali is dissolved to neutralize the aqueous solution. In the case of an aqueous solution (emulsion) obtained by emulsifying the organophosphorus compound, the organophosphorus compound mixed in advance with the emulsifier can be gradually added to the soft water under stirring to prepare an emulsion. In this case, soft water may be heated as necessary. When diluted with an organic solvent, the organic phosphorus compound can be gradually added to the organic solvent.

[Method for producing synthetic fiber]
The production method of the present invention is a production method for synthetic fibers (high-strength fibers) having a strength of 18 cN / dtex or more, and the step (A) of applying the fiber treatment agent of the present invention to the raw synthetic fibers; And (B) heat-drawing and / or heat-treating the raw synthetic fiber to which the fiber treatment agent has been applied. As described above, in order to produce a high-strength fiber, it is usually necessary to perform hot drawing and / or heat treatment. However, the present invention prevents fusion between single fibers that is likely to occur at that time, Strength fibers can be produced.
The fiber treatment agent and the production method of the present invention are suitable for the case of high-strength fibers having the following strength and elastic modulus from the viewpoint that the effects of the present invention can be further exhibited. About the measuring method of intensity | strength and an elasticity modulus, the method described in the Example can be used.
The strength of the high strength fiber is 18 cN / dtex or more, more preferably 18 to 60 cN / dtex, and still more preferably 19 to 40 cN / dtex. The elastic modulus of the high-strength fiber is preferably 450 cN / dtex or more, more preferably 450 to 2000 cN / dtex, and even more preferably 500 to 1000 cN / dtex.

  The (raw material) synthetic fiber is a synthetic fiber that exhibits high strength when heat-treated and / or heat-drawn, and in which fusion occurs. Examples of such (raw material) synthetic fibers include wholly aromatic polyester fibers such as parahydroxybenzoic acid / 2,6-hydroxynaphthoic acid copolymer fibers, wholly aromatic polyamide fibers such as polyparaphenylene terephthalamide fibers, Examples include wholly aromatic copolyamide fibers such as copolyparaphenylene and 3,4-oxydiphenyleneamide fibers, polyparaphenylene benzbisoxazole fibers, polyethylene fibers, and polyolefin ketone fibers. Among these, wholly aromatic polyester fibers, wholly aromatic copolyamide fibers, and polyolefin ketone fibers that are heat-treated and / or heat-stretched at 260 ° C. or higher are preferred, and wholly aromatic polyester fibers and wholly aromatic copolyamide fibers are preferred. Further preferred.

  The raw material synthetic fiber itself is known. For example, it is mentioned in Unexamined-Japanese-Patent No. 2004-107826. In addition, the raw material synthetic fiber here means the filament which can be heat-processed and / or heat-stretched. The method for producing the raw material synthetic fiber (spinning method) is not particularly limited, and known techniques and methods can be employed. For example, methods such as liquid crystal spinning, dry spinning, wet spinning, semi-dry semi-wet spinning, melt spinning, gel spinning and the like can be mentioned. Usually, fully aromatic polyester raw fiber and fully aromatic polyamide raw fiber are obtained by liquid crystal spinning, fully aromatic copolyamide raw fiber is obtained by semi-dry semi-wet spinning, and polyethylene raw fiber is gel-spun semi-dry semi-wet. Obtained by spinning.

  Step (A) is a step of applying the fiber treatment agent of the present invention to the raw synthetic fiber, and the above-mentioned organophosphorus compound is added before the step (B) of heat stretching and / or heat treatment for high strength expression. It is given to raw synthetic fibers. That is, in order to impart the effect of preventing fusion, the above-described organophosphorus compound is imparted before passing through the step (B) in which fusion occurs.

  There is no limitation in particular as a method of providing an organic phosphorus compound to raw material synthetic fiber, and a publicly known method can be adopted. For example, a method of dipping a raw synthetic fiber in a treatment liquid (fiber treatment agent) containing the above organic phosphorus compound and then drying, a method of quantitatively applying the treatment liquid to the raw synthetic fiber with a guide, and the treatment liquid using a roller Examples thereof include a method of applying to the raw material synthetic fiber, a method of applying the treatment liquid to the raw material synthetic fiber by spraying, and the like. Among these, from the viewpoint that the organophosphorus compound can be uniformly applied, a method of drying after the synthetic fiber is dipped in the treatment liquid, a method of quantitatively applying the raw material synthetic fiber with a guide, and a raw material synthesis of the treatment liquid using a roller A method of imparting to fibers is preferred. Further, in order to uniformly apply the organic phosphorus compound by the raw material synthetic fiber, the treatment liquid may be diluted and applied. In this case, the weight ratio of the nonvolatile content is as described above.

  The amount of the organic phosphorus compound attached to the synthetic fiber is preferably 0.05 to 10% by weight, more preferably 0.1 to 5% by weight, and still more preferably 0.1 to 3% by weight. When the application amount is less than 0.05%, it may be difficult to sufficiently suppress the fusion between the single fibers at the time of heat stretching and / or heat treatment at a high temperature. On the other hand, when the applied amount exceeds 10.0% by weight, thread breakage, fluff and yarn path stains may be caused.

  Step (B) is a step (B) in which the raw synthetic fiber to which the fiber treatment agent of the present invention is applied is subjected to hot drawing and / or heat treatment. In general, high-strength fibers are obtained by improving the strength and elastic modulus of raw fiber synthetic fibers by hot drawing and / or heat treatment at high temperatures. Step (B) is a step for improving the strength and elastic modulus of such fibers. As in step (B), by performing heat drawing and / or heat treatment in a state where the organic phosphorus compound is applied to the raw synthetic fiber, fusion between single fibers during heat drawing and / or heat treatment can be prevented. Excellent in yarn production. In addition, although the organophosphorus compound remains on the fiber that has been heat-drawn and / or heat-treated, it does not cause scum generation in the subsequent process, and therefore has excellent workability. Furthermore, since it is not necessary to remove the organophosphorus compound, the yarn is not damaged.

There is no limitation in particular as a method of carrying out heat | fever drawing and / or heat processing of raw material synthetic fiber, A well-known method is employable. In the case of wholly aromatic polyester fibers, a heat treatment method is generally used. For example, there can be mentioned a method in which the wholly aromatic polyester raw fiber that has been spun and wound up is allowed to stand at a predetermined temperature for a predetermined time and heat-treated.
For the wholly aromatic copolyamide fiber and polyethylene fiber, a method of hot drawing is generally used. For example, after spinning or after being wound and once wound, using a plurality of rollers at a predetermined temperature or heated, the fibers are gripped by contacting or winding the rollers, and the speed difference between the rollers is reduced. A method for gradually and continuously stretching the film can be used.

The temperature for heat stretching and / or heat treatment is preferably 260 ° C. or higher, more preferably 270 to 700 ° C., and even more preferably 280 to 700 ° C. for the reason of obtaining higher strength fibers. When the temperature is less than 260 ° C., the intended strength may not be obtained or fusion may not occur.
The time for heat drawing and / or heat treatment varies depending on the raw fiber, and is not particularly limited. For example, in the case of wholly aromatic polyester fiber, the heat treatment is performed at 280 ° C. or more for 10 hours or more, and in the case of wholly aromatic copolyamide fiber, heat stretching is performed at 350 ° C. or more for several seconds.

  The use of the high-strength fiber obtained by the production method of the present invention is not particularly limited, but is used for reinforcement of tire cords, cement reinforcements, resin reinforcements, etc., because the sticking between filaments is prevented. It is particularly suitable for composite materials and clothing materials.

[Method of preventing fusion of synthetic fibers]
The present invention is a method for preventing fusion between single fibers when producing a synthetic fiber having a strength of 18 cN / dtex or more, and after applying the fiber treatment agent of the present invention to a raw synthetic fiber in advance, the fiber It can also be referred to as a method for preventing fusion of synthetic fibers by subjecting the fiber to hot drawing and / or heat treatment. (Raw material) Synthetic fiber, fiber treatment agent, application of the treatment agent, heat stretching and / or heat treatment are as described above.

  Hereinafter, the contents and effects of the present invention will be described in detail based on Examples and Comparative Examples, but the present invention is not limited thereto. Unless otherwise specified, “%” and “ratio” in the text and table mean “% by weight” and “weight ratio”. In addition, each physical-property value in an Example was measured with the following method.

[Amount of fiber treatment agent attached]
20 g of a synthetic fiber to which a fiber treating agent was applied was collected, and the mass (S) after being left in a hot air drier at 105 ° C. for 60 minutes was measured with an electronic balance and placed in a Soxhlet extractor. Next, about 100 g of methanol was added and heated to reflux for about 4 hours, after which methanol was recovered, the absolute dry weight (M) of the extract was measured, and the amount of residual oil was determined from the following equation to obtain the amount of adhesion.
Residual oil content (% by weight) = M / S × 100

[Strength of synthetic fiber]
The strength (cN / dtex) of the synthetic fiber was measured according to JIS-L-1013.
Grasp interval: 20cm
Tensile speed: 100% of gripping interval per minute
Tensile testing machine:

[Elastic modulus of synthetic fiber]
The elastic modulus (cN / dtex) of the synthetic fiber was measured according to JIS-L-1013.

[Fused prevention]
Of the total number of filaments (A) of the sample fiber, the number of filaments (n) that can be separated one by one without fusion is counted, and the degree of fusion is determined by the following equation.
Degree of fusion (%) = {(A−n) / A} × 100
A case where the degree of fusion was 10% or less was evaluated as good ◯, and a case where the degree of fusion exceeded 10% was evaluated as poor.

[Thread path dirt]
After the fiber treatment agent was applied, the scum accumulated in the guides in contact with the fibers (stained state of the guides after the guides were washed and then spun for 24 hours) was visually confirmed. When other amount of scum or sticky material was observed, it was evaluated as “Poor”, when the scum and the sticky material were not observed or slight, and when no fluff was generated, it was evaluated as “Good”.

[Fuzz]
The surface and the side surface of 5 kg of the synthetic fiber after hot drawing and / or heat treatment wound in a cheese shape in a winder were visually observed, and the number of fluff was measured. The case where it was 5 or less was evaluated as “good”, and the case where it exceeded 5 was evaluated as “bad”.

[Stability of treatment agent]
The fiber treatment agent was allowed to stand at room temperature for 24 hours, and the case where separation or sediment did not occur was good. The case where some or all of the treatment agent was settled, floated, or both was judged as poor x.

Example 1
As shown in Table 1, treating agent components consisting of monooctylphosphonic acid potassium salt / pentanol = 90/10 (weight ratio), the total weight ratio of these components in the entire treating agent (in Table 1, the concentration applied and The fiber treatment agent, which is an aqueous solution, was prepared by gradually throwing it into a predetermined amount of soft water so as to be 10% by weight, and stirring and homogenizing for 60 minutes.
Next, a polymer obtained by copolymerizing parahydroxybenzoic acid and 2,6-hydroxynaphthoic acid was subjected to liquid crystal spinning, and the fiber treatment agent prepared above was applied to the obtained raw synthetic fiber by guide lubrication. Then, it was wound up into a cheese shape by a winder. At this time, the non-volatile matter adhered to the fiber was 0.7% by weight.
Subsequently, the synthetic fiber wound up in the shape of cheese was heat-treated in an oven at 280 to 330 ° C. for 24 hours to obtain a high-strength synthetic fiber. The adhesion amount of the treating agent, the strength of the synthetic fiber, the elastic modulus, the anti-fusing property, the yarn path dirt, the fluff, and the stability of the treating agent were evaluated by the methods described above. The results are shown in Table 1.

(Examples 2 to 11)
In Example 1, evaluation was performed in the same manner as in Example 1 except that the treatment agent composition and treatment agent application conditions (application concentration, oil supply method, application amount) shown in Table 1 were changed. The results are shown in Table 1.

(Example 12)
As shown in Table 1, tribenzylphosphine oxide was dissolved in a solvent isopropanol so that the total weight ratio of these components in the entire treatment agent (denoted as application concentration in Table 1) was 10% by weight. A treating agent was prepared.
Evaluation was performed in the same manner as in Example 1 except that the obtained fiber treatment agent and treatment agent application conditions (application concentration, oil supply method, application amount) shown in Table 1 were changed. The results are shown in Table 1.

(Example 13)
As shown in Table 1, the treatment agent component consisting of monooctylphosphonic acid potassium salt / ethanol = 90/10 (weight ratio) is the total weight ratio of these components in the entire treatment agent (in Table 1, described as the applied concentration) ) Was gradually poured into a predetermined amount of soft water so as to be 1% by weight, and stirred and homogenized for 60 minutes to prepare a fiber treatment agent as an aqueous solution.
Next, a copolyparaphenylene / 3,4-oxydiphenyleneamide copolymer obtained by copolymerizing paraphenylenediamine, 3,4-diaminodiphenyl ether and terephthalic acid chloride was obtained by semi-dry and semi-wet spinning. The fiber treatment agent prepared above was applied to the raw synthetic fiber by dipping. At this time, the non-volatile matter adhered to the fiber was 0.7% by weight.
Subsequently, the synthetic fiber provided with the fiber treating agent was stretched 10 times at 530 ° C. to obtain a high-strength synthetic fiber. The adhesion amount of the treating agent, the strength of the synthetic fiber, the elastic modulus, the anti-fusing property, the yarn path dirt, the fluff, and the stability of the treating agent were evaluated by the methods described above. The results are shown in Table 1.

(Comparative Examples 1-11)
In Example 1, evaluation was performed in the same manner as in Example 1 except that the treatment agent composition and treatment agent application conditions (application concentration, oil supply method, application amount) shown in Table 1 were changed. The results are shown in Table 2. In addition, the comparative example 1 is a case where a processing agent is not used. Comparative Example 3 is a case where an aqueous dispersion of 5% by weight of magnesium silicate was used as a treating agent. The comparative example 5 is a case where 100 weight% of mineral oil (viscosity 100 mm < ² > / sec) is used as a processing agent.

The synthetic fibers obtained in Examples 1 to 13 had a strength of 18 cN / dtex or higher and high strength. Moreover, compared with the synthetic fiber obtained by the comparative example, fusion was prevented, it was very flexible, fluff was not observed, and a very high quality product was obtained. Furthermore, no occurrence of scum was observed in the guide or the like after the treatment agent was applied, and yarn path soiling did not occur.
On the other hand, in Comparative Examples 1 to 11 (excluding Comparative Example 4), very much fusion occurred in the obtained synthetic fiber, and the raw yarn was rigid. In Comparative Examples 1-4, in the obtained synthetic fiber, many fluff was observed and it was inferior in quality. In Comparative Examples 2 to 5 and 9, a large amount of scum adhered to a guide or the like that comes into contact with the fiber after the treatment agent was applied, and frequent cleaning was required, resulting in a decrease in productivity. In Comparative Example 3, the stability of the treatment agent was poor, and precipitation of magnesium silicate was observed.

Claims (9)

A method for producing a synthetic fiber having a strength of 18 cN / dtex or more,
A fiber treating agent that essentially contains at least one organic phosphorus compound selected from a compound represented by the following general formula (1), a compound represented by the following general formula (2), and a compound represented by the following general formula (3): A method for producing a synthetic fiber, comprising: a step (A) for imparting a raw material synthetic fiber to a raw material synthetic fiber; and a step (B) for thermally stretching and / or heat-treating the raw material synthetic fiber to which the fiber treatment agent is imparted.

(In the formulas (1), (2) and (3), R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are each independently a hydrocarbon group having 2 to 18 carbon atoms. X ¹ , X ² and X ³ are each independently represented by a hydrocarbon group having 2 to 18 carbon atoms, a hydrogen atom, an alkali metal, an alkaline earth metal and NR ^a R ^b R ^c R ^d And at least one selected from a group, R ^a , R ^b , R ^c and R ^d each independently represent a hydrogen atom, an alkyl group, an alkanol group or a polyoxyalkylene group.)   The method for producing a synthetic fiber according to claim 1, wherein in the step (B), the temperature for heat drawing and / or heat treatment is 260 ° C or higher.   The method for producing a synthetic fiber according to claim 1 or 2, wherein the synthetic fiber is at least one selected from wholly aromatic polyester fiber, wholly aromatic polyamide fiber, and wholly aromatic copolyamide.   The manufacturing method of the synthetic fiber in any one of Claims 1-3 whose adhesion amount of the said organophosphorus compound with respect to the said synthetic fiber is 0.05-10 weight%. A fiber treatment agent used for producing a synthetic fiber having a strength of 18 cN / dtex or more,
A fiber treatment essentially containing at least one organic phosphorus compound selected from a compound represented by the following general formula (1), a compound represented by the following general formula (2) and a compound represented by the following general formula (3) Agent.

(In the formulas (1), (2) and (3), R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are each independently a hydrocarbon group having 2 to 18 carbon atoms. X ¹ , X ² and X ³ are each independently represented by a hydrocarbon group having 2 to 18 carbon atoms, a hydrogen atom, an alkali metal, an alkaline earth metal and NR ^a R ^b R ^c R ^d And at least one selected from a group, R ^a , R ^b , R ^c and R ^d each independently represent a hydrogen atom, an alkyl group, an alkanol group or a polyoxyalkylene group.)   The fiber treatment agent of Claim 5 whose weight ratio of the said organophosphorus compound which occupies for the whole non volatile matter of a treatment agent is 50 to 100 weight%.   The fiber treatment agent according to claim 5 or 6, wherein the synthetic fiber is at least one selected from wholly aromatic polyester fibers, wholly aromatic polyamide fibers, and wholly aromatic copolyamides.   The fiber treatment agent in any one of Claims 5-7 which is a state which contains the solvent and the said organic phosphorus compound melt | dissolved in this solvent. A method for preventing fusion between single fibers when producing a synthetic fiber having a strength of 18 cN / dtex or more,
A method for preventing fusion of synthetic fibers, wherein the fiber treatment agent according to any one of claims 5 to 8 is applied in advance to the raw synthetic fibers, and then the fibers are hot-drawn and / or heat-treated.