JPH08199432A - Synthetic fiber treating agent and synthetic fiber provided with the treating agent - Google Patents

Abstract

(57) [Summary] (Modified) [Purpose] Synthetic fiber treatment agent with excellent heat resistance that does not impair the stretchability of synthetic fiber, and flexibility and productivity obtained by applying this treatment agent. We also provide synthetic fibers with excellent post-processability such as adhesive treatment. [Structure] Diester compound (A) of thiodipropionic acid and monohydric alcohol (A) 75 to 90% by weight From ethylene oxide adduct of polyhydric alcohol fatty acid ester having two or more hydroxyl groups, monocarboxylic acid and dicarboxylic acid Nonionic activator (B) of 10 to 25% by weight, formula RO (AO) m H (wherein R is an alkyl group having 8 to 20 carbon atoms, AO is an alkylene oxide group having 2 to 4 carbon atoms, and m is An integer of 0 to 10), a mixture of an alcoholic phosphorus oxide represented by 0.3 to 5% by weight with an amine compound, and 0.5 to 5% by weight of a sulfonate anionic surfactant (D). It accounts for 95% by weight or more of the entire treating agent.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a synthetic fiber treating agent which is mainly used in the process of producing industrial synthetic fibers. More specifically, a treatment agent for synthetic fibers having excellent heat resistance that does not impair the stretchability of synthetic fibers, and the flexibility, productivity and post-processability such as adhesive treatment obtained by applying this treatment agent. Relates to excellent synthetic fibers.

[0002]

2. Description of the Related Art Conventionally, various treating agents have been used as needed in the spinning and drawing processes of synthetic fibers, but in recent years, the spinning and drawing speeds have become faster and faster to improve productivity and quality. However, since the temperature of the heating body such as the drawing roller is also increased, it is strongly desired to improve the performance such as heat resistance, extreme pressure property and lubricity of the synthetic fiber treating agent.

In addition, synthetic fiber treating agents are strongly required to have properties that allow synthetic fibers treated with the treating agents to exhibit sufficient practical performance.

The conventional treating agent for synthetic fibers comprises a composition in which thiodipropionic acid ester and a monocarboxylic acid and dicarboxylic acid reaction product of ethylene oxide adduct of polyhydric alcohol fatty acid ester are mixed. However, it is known, for example, from Japanese Patent Laid-Open No. 4-34074.

The synthetic fiber treating agent described in the above-mentioned JP-A-4-34074 specifically comprises 75 to 95% by weight of a diester compound of thiodipropionic acid and a monohydric alcohol having 12 to 18 carbon atoms. , A monocarboxylic acid and dicarboxylic acid reaction product of an ethylene oxide adduct of a polyhydric alcohol fatty acid ester and 25 to 10% by weight, which eliminates fumes during hot drawing and / or heat treatment of synthetic fibers, It has the property of ensuring heat resistance.

However, with the recent development of technology, the spinning and drawing speeds of fibers have become higher in order to improve the productivity and quality of synthetic fibers. For example, it is described in JP-A-4-34074. Even if the treated synthetic fiber treating agent is applied, heat resistance and lubricity are not sufficient, and as the running speed of the yarn increases,
Frequent yarn breakage during stretching, tar remains on the heat roller, and the yarn touches the tar, causing more fluff and yarn breakage, and shortening the cleaning period for the heat roller to which the tar adheres. However, there has been a problem that the cleaning takes a long time and the productivity is lowered.

[0007] Further, the synthetic fibers treated with the treatment agent,
It is required to sufficiently exhibit high-performance fiber functions at the stage of its use, but synthetic fibers treated with the above-mentioned conventional synthetic fiber treating agents have poor flexibility, and therefore, for example, adhesion to rubber. When used for applications, it was not possible to exhibit sufficient productivity and adhesiveness.

[0008]

The present invention has been achieved as a result of studying to solve the above-mentioned problems in the prior art.

Therefore, an object of the present invention is to provide a synthetic fiber treating agent having excellent heat resistance which does not impair the stretchability of synthetic fibers, and the flexibility, productivity and adhesion obtained by applying this treating agent. It is intended to provide synthetic fibers having excellent post-processability such as treatment with agents.

[0010]

In order to achieve the above object, the synthetic fiber treating agent of the present invention spins synthetic fibers.
A treating agent for synthetic fibers used in production by a stretching method, which is a diester compound (A) of thiodipropionic acid and a monohydric alcohol (A) 75 to 90% by weight, and a polyhydric alcohol fatty acid having two or more hydroxyl groups. Nonionic activator (B) consisting of ethylene oxide adduct of ester, monocarboxylic acid and dicarboxylic acid 10 to 25% by weight,
Formula RO (AO) m H (where R in the formula is 8 to 18 carbon atoms)
Alkyl group, AO is an alkylene oxide group having 2 to 4 carbon atoms, m is an integer of 0 to 10), and a phosphorus oxide of an alcohol, and an alkylamine having 8 to 20 carbon atoms or an alkylamine ethylene oxide 1 A mixture obtained by mixing 0.3 to 5% by weight of a salt with an adduct and 0.5 to 5% by weight of a sulfonate anionic surfactant (D) is 95% by weight or more of the entire treating agent. The synthetic fiber of the present invention comprises a thermoplastic synthetic fiber spun-
In the production by the drawing method, the above-mentioned synthetic fiber treating agent is added at a stage after spinning and before drawing.

[0011]

[Embodiment] Regarding the synthetic fiber treating agent according to the present invention,
A detailed description will be given below.

According to the synthetic fiber treating agent of the present invention,
By containing the above-mentioned components (A), (B) and the modified polyorganosiloxane (C) in a specific ratio, the heat resistance is excellent, and thus the smoke generation on the heating roller during the heat treatment of the synthetic fiber is reduced. In addition, since the adhesion of tar to the heating element is reduced and the lubricity is excellent, the smoothness between the running yarn and the metal roller is good,
It becomes possible to obtain a high-quality synthetic fiber having improved adhesiveness to rubber without improving the spinnability and causing single yarn breakage or yarn cracking.

The treatment agent for synthetic fibers of the present invention contains the above compounds (A), (B), (C) and (D) in an amount of 75 to 75%, respectively.
90% by weight, 10 to 25% by weight, 0.3 to 5% by weight and a mixture obtained by mixing in the range of 0.5 to 5% by weight, containing 95% by weight or more as a main component. is there.

The above component (A) is composed of thiodipropionic acid and 12 carbon atoms having two or more hydroxyl groups.
It can be obtained by reacting with a monohydric branched alcohol of 20 to 20. However, when an unsaturated alcohol such as oleyl alcohol is used in place of the monohydric branched alcohol, stains on the stretching roller are significantly increased, and stretching operability is increased. Is decreased, which is not preferable.

When a straight chain saturated alcohol such as lauryl alcohol or stearyl alcohol is used instead of the monohydric branched alcohol, the treating agent is solidified and is applied to the yarn splicing portion in the spinning process or the post-processing process. It is not preferable because the amount of kimono is increased, the drawability is lowered, and the performance is lowered when the fiber is used.

The monohydric branched alcohol in the compound (A) preferably has a carbon number in the range of 12 to 20, particularly 12 to 18. When the carbon number is less than 12, the yarn is exposed to high heat such as hot drawing. It is not preferable because it sometimes causes thermal decomposition to generate tar on the heated stretching roller or the like, or increase smoke.

When the carbon number of the monohydric branched alcohol in the compound (A) exceeds 20, the spreading property of the treating agent is lowered and the friction between the heated drawing roller and the yarn is increased, It is not preferable because it tends to cause yarn breakage or fluff during drawing.

Among the monohydric branched alcohols having 12 to 20 carbon atoms, dioleyl alcohol and distearyl alcohol are particularly preferably used from the viewpoint of stretchability.

The compounding amount of the compound (A) in the fiber treating agent of the present invention is 75 to 90% by weight, particularly 80 to 8% by weight.
5% by weight. If it is less than 75% by weight, the spreading property of the treatment agent is lowered, and the friction between the synthetic fiber and the drawing roller is increased, which causes yarn breakage and fluffing, and exceeds 90% by weight. If so, the sizing property of the synthetic fibers is lowered, yarn cracks are caused by the stretching roller, and the operability is deteriorated, which is not preferable.

The above component (B) comprises an ethylene oxide adduct of a polyhydric alcohol fatty acid ester having two or more hydroxyl groups, a monocarboxylic acid and a dicarboxylic acid, and preferably has an ethylene oxide content of 20 to 60% by weight. Is a non-ionic activator.

Specific examples of the ethylene oxide adduct of the polyhydric alcohol fatty acid ester having two or more hydroxyl groups constituting the compound (B) include ethylene oxide adduct of glycerin monostearate and ethylene of hydrogenated castor oil. Examples include oxide adducts, ethylene oxide adducts of castor oil, pentaerythritol diisostearate ethylene oxide adducts, sorbitol trilaurate ethylene oxide adducts, and trimethylolpropane ethylene oxide adducts. Preferably, an ethylene oxide adduct of hydrogenated castor oil is used.

The amount of ethylene oxide added to the ethylene oxide adduct component is 20 to 60% by weight, preferably 25 to 55% by weight in the nonionic activator. Addition amount of ethylene oxide is 20% by weight
If it is less than 60% by weight, the yarn tends to break frequently on the drawing roller due to insufficient sizing property, and if it exceeds 60% by weight, the compatibility with the thiodipropionate ester component deteriorates and the function as a treating agent deteriorates. It is not preferable because

Examples of the monocarboxylic acid in the above compound (B) include capric acid, lauric acid, stearic acid, oleic acid, erucic acid and isostearic acid. Among them, stearic acid and oleic acid are preferably used. preferable.

Further, examples of the dicarboxylic acid in the above compound (B) include maleic acid, adipic acid, sebacic acid, dodecanoic acid and the like. Among them, maleic acid and adipic acid are preferably used.

The above-mentioned compound (B), that is, the ratio of the nonionic activator component to the total treating agent is 10 to 25% by weight,
Particularly, it is 15 to 20% by weight.

If the proportion of the compound (B) in the total treating agent is less than 10% by weight, yarn cracks may occur on the stretching roller to deteriorate the operability, and if it exceeds 25% by weight, the treating agent content may increase. Not only is the heat resistance and wettability lowered, the cleaning cycle of the stretching roller becomes shorter, and moreover, yarn breakage and fluffing frequently occur, leading to deterioration in operability and yarn quality, which is not preferable.

The above component (C) component has the formula RO (AO)
m H (wherein R is an alkyl group having 8 to 20 carbon atoms,
AO is an alkylene oxide group having 2 to 4 carbon atoms, and m is 0.
An integer of 10 to 10) and a salt of an alcohol phosphoric acid represented by the formula 8 and an alkylamine having 8 to 20 carbon atoms or an alkylamine ethylene oxide 1 to 10 adduct,
When used in combination with the above-mentioned compounds (A) and (B), it functions to facilitate cleaning of dirt on the fibers and the stretching roller.

8 to 20 carbon atoms in the above compound (B)
Examples of the alcohol include octyl alcohol, 2-ethylhexyl alcohol, lauryl alcohol, cetyl alcohol, isocetyl alcohol, oleyl alcohol and isoeicosanol.

Here, when the carbon number of the alcohol is less than 8, the compatibility of the treating agent is lowered to increase the deposits on the stretching roller, and when it is more than 20, the extreme pressure property is lowered and the stretching roller is increased. If this is the case, the friction of the yarn will increase, and fluff and yarn breakage will tend to occur, which is not preferable.

In the compound (C), the amine compound which forms a salt with the phosphorus oxide of the alcohol is an alkylamine or alkylamine alkylene oxide adduct represented by the following formula (I).

Embedded image (However, R in the formula is an alkyl group having 8 to 18 carbon atoms, A
O is an alkylene oxide group having 2 to 4 carbon atoms, and m and n are each an integer such that m + n is 0 to 10).

More specifically, alkylamines having 8 to 20 carbon atoms or alkylamine ethylene oxide 1 to
The 10-adduct, and the alkylamine as used herein includes octylamine, dodecylamine, laurylamine, laurylmonomethylamine, oleylamine and dimethylstearylamine.

When the alkylamine has less than 8 carbon atoms, the odor generated from the treating agent becomes remarkable and the spinning environment is deteriorated, and when it exceeds 20, extreme pressure and lubricity are deteriorated, resulting in poor operability. Is worse, which is not preferable.

In the above compound (C), when an ethylene oxide adduct of alkylamine is used, the number of moles of ethylene oxide added is preferably 1 to 10 moles.

When the number of moles of ethylene oxide added exceeds 10 moles, the basicity of the amine becomes weak,
Since the amount of amine used increases, the amount of phosphorus compound of alcohol relatively decreases, the extreme pressure property and the lubricity decrease, and the operability tends to deteriorate, which is not preferable.

The use of metal salts of phosphorus compounds, such as sodium salts and potassium salts, is poor in compatibility with other treating agent components, so that they are deposited on the stretching roller to clean the stretching roller. This is not preferable because it shortens the cycle and lowers the operability.

The proportion of the compound (C) in the total treating agent is preferably 0.3 to 5% by weight, particularly preferably 0.5 to 3% by weight. Lubricity is reduced and static electricity is often generated, making it difficult to clean the stretching roller. If the amount exceeds 5% by weight, stains on the stretching roller tend to increase, which is not preferable.

Further, the compound (D), that is, the sulfonate type anionic surfactant includes a dialkyl sulfosuccinate salt, an alkylbenzene sulfonate salt and an alkane sulfonate salt. Among them, the compound is represented by the following formula (II). Secondary alkane sulfonate salts are preferably used.

[Chemical 4] (However, in the formula, R1 and R2 are alkyl groups having a sum of carbon numbers of 10 to 19, and M is an alkali metal).

The secondary alkane sulfonate salt represented by the above formula (II) preferably contains potassium or sodium as an alkali metal, and its specific example is trade name: "Cactus" (manufactured by Nikko Oil Co., Ltd.). , Trade name: "Mersorat H" (manufactured by Bayer) and trade name: "Hoster SUS" (manufactured by Hoechst).

The proportion of the compound (D) in the total treating agent is preferably 0.5 to 5% by weight, particularly preferably 1 to 3% by weight. If the improvement effect is small, and if it exceeds 5% by weight, the friction between the fiber and the metal is increased, the drawability is lowered, and the yarn breakage and the fluff tend to increase, which is not preferable.

In order to apply the synthetic fiber treating agent of the present invention to synthetic fibers, a mixed composition comprising the compounds (A) to (D) is dispersed in a non-hydrated system diluted with mineral oil and / or water. It is effective either as an emulsion system or as an undiluted solution, but especially when used as a non-hydrate system.

Therefore, the synthetic fiber treating agent of the present invention is
Compared with conventional synthetic fiber treatment agents, it has superior heat resistance when drawing and / or heat-treating synthetic fibers, and has excellent extensibility with no yarn breakage or fluffing, and high performance. Synthetic fibers can be provided.

When the synthetic fiber treating agent according to the present invention is applied to fibers, the mixed composition comprising the compounds (A) to (D) is diluted or emulsified with, for example, a non-aqueous oil agent or water. It is used as an emulsion treatment agent and is applied to synthetic fibers by a roller or a guide oil supply device in a step after the spinning step and before the drawing.

The amount of the above treatment agent attached to the synthetic fiber is
A range of 0.3 to 2.0% by weight, particularly 0.5 to 1.5% by weight is preferable.

The synthetic fiber of the present invention obtained by applying the treating agent in this manner, particularly the polyamide fiber or the polyester fiber is excellent in heat resistance, flexibility, lubricity and extreme pressure, and is treated with an adhesive. It is possible to give a treatment code that is stably treated with an adhesive in the post-processing step,
The product obtained in this post-processing step has significantly improved adhesion between the cord and rubber.

Therefore, the synthetic fiber to which the treating agent of the present invention has been applied takes advantage of the characteristics of excellent flexibility, heat resistance and post-processability, thereby making it possible to use tire cords, seat belts,
It can be suitably applied to various industrial applications such as heavy cloth, fishing nets, ropes, and V-belts.

The constitution and effects of the present invention will be described in more detail below with reference to examples.

[0047]

EXAMPLES The evaluation in each example and each comparative example was performed and displayed by the following method.

The stretchability: viewed in yarn breakage number that occurred during the stretching one tons of nylon 66 filaments by weight of the polymer.

Smoke emission : Smoke emission on the hot roller during stretching was visually observed. ◯: No smoke generated △: Almost no smoke generated ×: A large amount of smoke generated

Contamination of hot roller : The state of contamination on the hot roller during stretching was observed. ◯: No stains Δ: Almost no stains ×: A lot of stains

Odor : The odor generated around the hot roller during stretching was actually judged. ◯: Acceptable odor ×: Unpleasant odor

Thread splitting: The state of thread splitting during stretching was visually observed. A: Almost no yarn cracks X: Many yarn cracks

Washability of hot roller: When the dirt of the hot roller is wiped off with a cleaning cloth after stretching is continued for 24 hours, it is evaluated by the number of times of wiping until the dirt is completely removed. ◯: The stain was wiped off by 10 times. Δ: The stain was wiped off by 10 times to 30 times. ×: The stain was not removed even after 30 times.

Flexibility: A fiber yarn bundle was prepared and judged by a tactile test by hand. ○: Large flexibility (soft) △: Medium flexibility ×: Small flexibility (slightly hard)

[Examples 1 to 3, Comparative Examples 1 to 6] 1260
Denier, 204 filaments of nylon 66 filaments were melt-spun by a usual method, and 1% by weight of a treating agent having the composition shown in Table 1 was applied to a yarn obtained at a spinning speed of 500 m / min by a roller lubrication method. Without being wound up, the film was hot-stretched at a total draw ratio of 5.3 times by a two-stage drawing method using a 240 ° C. hot roller.

[0056]

[Table 1] The details of each symbol of the treatment agent component in Table 1 are as shown below.

A1 ... Diisostearyl thiodipropionate (C18) A2 ... Diisolauryl thiodipropionate (C12) A3 ... Isooctylthiodipropionate (C8) A4. Isotetracosanate (24 carbon atoms) A5 ... Diisostearyl adipate A6 ... Dioleyl thiodipropionate B1 ... Hardened castor oil EO adduct oleic acid ester (EO: 42% by weight) B2 ... Hardened castor oil EO25 mol adduct C1 ... Oleyl phosphate amine EO25 mol adduct D1 ... Secondary alkane sulfonate sodium.

Table 2 shows the evaluation results of stretchability, heat resistance, and flexibility of the obtained fibers when each treating agent was used.

[0059]

[Table 2] As is clear from the results of Table 2, Example 1 according to the present invention
The synthetic fiber treating agents of ~ 3 are compared with Comparative Examples 1 to 4,
The stretchability and heat resistance are excellent, and the flexibility of the fiber obtained by the treatment is also very good.

[Examples 4 and 5, Comparative Examples 7 to 13] 126
Nylon 66 filaments of 0 denier and 204 filaments were melt-spun by a usual method, and the spinning speed was 500 m.
1% by weight of the treating agent having the composition shown in Table 3 is applied to the yarn obtained at 1 / min by a roller lubrication method, and then the entire drawing is performed by two-step drawing using a hot roller at 240 ° C. without winding. Multi-stage hot drawing was performed at a magnification of 5.3 times.

[0061]

[Table 3] The details of each symbol of the treatment agent component in Table 3 are as shown below. A1 ... Diisostearyl thiodipropionate (18 carbon atoms) B3 ... Trimethylolpropane EO adduct monooleate fumarate lauric acid ester (EO: 50% by weight) B4 ... Hardened castor oil EO adduct Adipic acid olein Acid ester (EO: 67% by weight) B5 ... hydrogenated castor oil EO adduct adipic acid oleic acid ester (EO: 10% by weight) C2 ... oleyl phosphate stearyl monomethylamine C3 ... oleyl phosphate dimethylamine D1 ... second Grade alkane sulfonate sodium.

Table 4 shows the evaluation results of the stretchability, heat resistance and flexibility of the obtained fibers when each treating agent was used.

[0063]

[Table 4] As is clear from Table 4, the synthetic fiber treating agents of Examples 4 to 5 according to the present invention have excellent heat resistance, stretchability, smoke generation, and hot roller contamination in a balanced manner as compared with Comparative Examples 7 to 13. And the flexibility of the fibers obtained by the treatment is also very good.

[0064]

The treatment agent for synthetic fibers according to the present invention has excellent heat resistance when the synthetic fibers are stretched and / or heat-treated, and has excellent extensibility without causing yarn breakage or fuzz. , Can give high performance synthetic fibers.

Further, the synthetic fiber of the present invention, especially the polyamide fiber or the polyester fiber is excellent in heat resistance, flexibility, lubricity and extreme pressure property, and is stably treated with an adhesive in a post-processing step such as an adhesive treatment. It is possible to provide a treated cord, and the product obtained in this post-processing step has a significantly improved adhesion between the cord and rubber.

Therefore, the synthetic fiber to which the treating agent of the present invention has been applied makes good use of the characteristics of excellent flexibility, heat resistance and post-processability, and is utilized for tire cords, seat belts,
It can be suitably applied to various industrial applications such as heavy cloth, fishing nets, ropes, and V-belts.

Claims (9)

[Claims] 1. A treating agent for synthetic fibers used when producing synthetic fibers by a spinning-drawing method, comprising 75 to 90% by weight of diester compound (A) of thiodipropionic acid and monohydric alcohol, 2 Nonionic activator (B) 1 comprising ethylene oxide adduct of polyhydric alcohol fatty acid ester having the above hydroxyl group, monocarboxylic acid and dicarboxylic acid
0 to 25% by weight, the formula RO (AO) m H (where R in the formula is 8 to 20 carbon atoms)
An alkyl group, AO is an alkylene oxide group having 2 to 4 carbon atoms, m is an integer of 0 to 10), and a salt of an amine compound with a phosphorus oxide of 0.3 to 5% by weight, and Sulfonate anionic surfactant (D)
A treatment agent for synthetic fibers, wherein the mixture obtained by mixing 0.5 to 5% by weight accounts for 95% by weight or more of the entire treatment agent. 2. The treating agent for synthetic fibers according to claim 1, wherein the monovalent branched alcohol in the compound (A) has a carbon number in the range of 12 to 18. 3. The synthetic fiber treating agent according to claim 1 or 2, wherein the polyhydric alcohol fatty acid ester in the compound (B) is hydrogenated castor oil. 4. The treating agent for synthetic fibers according to claim 1, 2 or 3, wherein the ethylene oxide content of the ethylene oxide adduct in the compound (B) is in the range of 20 to 60% by weight. 5. The amine compound in the compound (C) is an alkylamine or an alkylamine alkylene oxide adduct represented by the following formula (I), wherein the amine compound is 1, 2, 3 or 4. Treatment agent for synthetic fibers. Embedded image (However, R in the formula is an alkyl group having 8 to 18 carbon atoms, A
O is an alkylene oxide group having 2 to 4 carbon atoms, and m and n are each an integer such that m + n is 0 to 10). 6. The synthetic fiber treatment according to claim 1, wherein the compound (D) is a secondary alkane sulfonate salt represented by the following formula (II). Agent. Embedded image (However, in the formula, R1 and R2 are alkyl groups having a sum of carbon numbers of 10 to 19, and M is an alkali metal). 7. The synthetic fiber treating agent according to claim 1, 2, 3, 4, 5 or 6 is applied in the step of producing a thermoplastic synthetic fiber by a spinning-drawing method, after the spinning and before the drawing. Synthetic fiber characterized by being. 8. The synthetic fiber treated with the synthetic fiber treating agent according to claim 1, 2, 3, 4, 5 or 6, is a polyamide fiber or a polyester fiber. The synthetic fiber described. 9. The synthetic fiber according to claim 7, wherein the treatment agent for synthetic fiber is attached to the synthetic fiber in an amount of 0.3 to 2.0% by weight.