KR102124377B1 - Noninflammable and Splittable Microfiber - Google Patents

Abstract

In the present invention, the flame retardant split type microfiber is composed of one component comprising an alkali-soluble polyester polymer resin and two components comprising a polyphenylene sulfide resin, wherein one component is 20 to 60% by weight, and the two The component is 40 to 80% by weight, and the alkali-soluble polyester resin is a copolymer of 0.1 to 5% by weight of polyethylene glycol with a molecular weight of 10,000 to 20,000, and the polyphenylene sulfide resin has a phenolic to phosphorus compound of 4:6. It relates to a flame-retardant split type microfibers, characterized in that an antioxidant composed of a weight ratio of ~6:4 is added.

Description

Flame-retardant split type microfiber {Noninflammable and Splittable Microfiber}

The present invention relates to a split type microfiber having excellent flame retardancy, and more particularly, to a split type microfiber comprising a polyphenylene sulfide (PPS) resin.

The ultrafine fiber in the present invention is a fiber that is developed using a very soft and soft touch, and can make fine fibers up to 0.001 denier by dividing the spun fiber. It is mainly used for high value-added textile products such as artificial leather, artificial suede, automobile interior materials, and case covers, but in this application, it is very important to select the raw material fibers to be used for high-quality products, and the needle is used in the opening process, a post-treatment process. Post-processing conditions ranging from punching and impregnation to brushing are very diverse and complex.

Methods for manufacturing the ultrafine fibers include single component spinning, multicomponent spinning (composite spinning), air jet spinning, and flash spinning. Single-component spinning is a method of directly spinning fibers of a desired fineness, which has the advantage of reducing manufacturing costs by not going through a post-fine process, but there is a limitation in facilities for ultrafine fineness of nano units. Multicomponent spinning can produce island-in-sea, split-type, and multi-layer fibers. Particularly, split-type fibers are spun by spinning two polymers into a splittable conjugate spinning, and post-processing one of them. The advantage is that it has a fineness of about 0.1 denier grade and has a small diameter deviation by reducing or eluting by physical or chemical treatment. Air jet spinning is the most excellent process for extruding polymer melts through custody and then using heated high-speed air to produce fibers and then irregularly stacking them in a collector to form a non-woven fabric structure. Flash spinning melts and extrudes a polymer, such as propylene, and then evaporates the solvent immediately after detention, whereby each fiber is captured on a moving screen in the form of fibrils to form a network structure.

Currently, most split microfibers are mainly made of polyester, nylon, or copolyester. However, in certain fields, such as automotive interior materials, fiber materials with flame retardancy are preferred for stability in case of emergency. In recent years, the application of polyphenylene sulfide (PPS) fibers as a material for flame retardant interior materials is increasing as the limits of the use of flame retardant additives, the national regulations for halogen flame retardants, and the user's expectations increase.

The split-type polyphenylene sulfide microfibers having flame retardancy have a large amount of impurities remaining in the resin, unlike polyester or nylon in which the resin itself is commonly used. Because of the side reaction caused by the resin melt density is partially non-uniform, the flow rate between the spinnerets is unstable, and the cross-section bonding phenomenon in which the divided polyphenylene sulfide components stick together easily occurs, so that the split-type cross-sectional formation of the polyphenylene sulfide resin is generated. The conditions are very demanding. As a result, the process yield is very low, resulting in high process cost, and supply is not smooth compared to market demand.

In order to solve the problems of the prior art, it can be said that it is necessary to develop a polyphenylene sulfide microfiber having flame retardancy and excellent melt spinning processability. Therefore, the present invention is to propose a split-type polyphenylene sulfide microfiber and a method for manufacturing the same to solve the above problems.

In order to solve the above problems, the present invention is to provide a split-type polyphenylene sulfide microfiber having excellent flame retardancy.

It is also an object of the present invention to provide a method for producing a polyphenylene sulfide split type microfiber with improved spinning processability.

In order to solve the above problems, the present invention is an alkali-soluble copolymerized polyester polymer resin and polyphenylene sulfide resin composite spinning by a split-type composite spinning method, wherein the alkali-soluble copolymerized polyester polymer resin is 20 by weight To 50% by weight, the polyphenylene sulfide resin is 50 to 80% by weight, and the alkali-soluble copolymerizable polyester resin is a copolymer of 0.1 to 5% by weight of polyethylene glycol having a molecular weight of 10,000 to 20,000, and the polyphenylene The sulfide resin provides a split-type polyphenylene sulfide microfiber characterized by adding an antioxidant selected from a mixture of a phenolic compound to a phosphorus compound in a weight ratio of 4:6 to 6:4.

In addition, the split-type microfiber provides a split-type polyphenylene sulfide microfiber characterized in that the fineness is 1.0 to 5.0 denier using a 9-split spinneret, and the fineness of one split microfiber is 0.05 to 1.25 denier. .

In addition, the present invention provides a split-type polyphenylene sulfide microfiber characterized in that the antioxidant is 0.05wt% to 2wt% based on the weight of the polyphenylene sulfide resin.

In addition, the present invention is an antioxidant selected from a mixture of an alkali-soluble copolymerizable polyester resin and a phenolic compound to a phosphorus-based compound in a weight ratio of 4:6 to 6:4 with a polyethylene glycol 0.1 to 5 wt% copolymerized in a molecular weight of 10,000 to 20,000. Melting each of the polyphenylene sulfide resins added thereto in a melt extruder; Compound spinning by supplying the molten resin to a spinneret of a split type composite spinning; After the composite spinning step, the solidified fiber aggregate is composed of a step of stretching at a draw ratio of 3.0 to 4.0 and a draw speed of 70 to 120 m/min, wherein the composite spinning speed is 500 to 1,300 m/min, and the alkali availability Provided is a method for producing a split-type polyphenylene sulfide microfiber, characterized in that the copolymerized polyester resin is included in an amount of 20 to 50% by weight, and the polyphenylene sulfide resin is included in an amount of 50 to 80% by weight.

The split polyphenylene sulfide microfibers of the present invention have a flame retardant effect.

In addition, the method of manufacturing the split polyphenylene sulfide microfibers according to the present invention is characterized by improved spinning processability.

1 and 2 are cross-sectional conceptual diagrams and enlarged photographs of a split-type polyphenylene sulfide microfiber, which is an embodiment of the present invention.

Hereinafter, a preferred embodiment of the present invention will be described in detail. First, in describing the present invention, detailed descriptions of related known functions or configurations are omitted so as not to obscure the subject matter of the present invention.

As used herein, the terms'about','substantially', etc. are used in the sense of or close to the numerical values when manufacturing and material tolerances unique to the stated meaning are presented, and to understand the present invention. To aid, accurate or absolute figures are used to prevent unscrupulous use of the disclosed disclosure by unscrupulous infringers.

Split polyphenylene Sulfide Ultrafine fiber

1 and 2 are cross-sectional conceptual diagrams and enlarged photographs of split-type polyphenylene sulfide microfibers according to the present invention, and are composed of one component 100 and two components 200.

The method for producing a split-type polyphenylene sulfide microfiber according to the present invention includes an alkali-soluble polyester as one component (100) and a polyphenylene sulfide resin added with a phenol-based and phosphorus-based antioxidant as two components (200). can do.

In general, in the split type fiber, the one component 100 arranges a material having a lower melting point than the two components 200 and easy to be eluted by alkali.

That is, in the combination of polyester and nylon, nylon is used as two-component (200), in polyester and copolyester combination, polyester is used as two-component (200), and in copolyester and nylon combination, nylon is two-component (200). ).

In the present invention, a polyester resin is used as the one component (100). It is preferable that the polyester resin includes an organic sulfonic acid metal salt and a polyester resin copolymerized with 0.1 to 5% by weight of polyethylene glycol having a molecular weight of 10,000 to 20,000.

In the present invention, a polyphenylene sulfide resin is used as the two-component 200, and the polyphenylene sulfide resin may include a linear, cross-linked, or semi-crosslinked type, but is preferably linear. In addition, the polyphenylene sulfide resin is a resin having an intrinsic viscosity of 0.1 dl/g or more, preferably 0.2 dl/g or more, or a weight average molecular weight (Mw) of 20,000 to 80,000, and a melt viscosity (Mv) of 300°C. It is necessary to use 500 to 2500 poise, so that physical properties including yarn strength are excellent.

The polyphenylene sulfide resin has excellent chemical resistance and heat resistance of 270°C or higher. In addition, the polyphenylene sulfide resin is an environmentally friendly flame retardant resin that is flame retardant without a flame retardant because it has its own flame retardant, and is generally used by adding glass fibers or the like in consideration of mechanical strength, etc., but polyphenylene sulfide according to the present invention It is preferable that the resin is composed of only phenylene sulfide molecular chains for fibers, and more preferably, p-phenylene sulfide units are contained in an amount of 90 mol% or more.

Split polyphenylene Sulfide Microfiber manufacturing method

The method for producing a split-type polyphenylene sulfide microfiber according to the present invention melts an alkali-soluble polyester as a component 100 and a polyphenylene sulfide resin as a component 200 in a melt extruder, respectively. It may include the step of compound spinning by supplying (100) and two components (200) to the spinneret for a split-type composite spinning.

In addition, the two-component polyphenylene sulfide resin is a phenol-based, lactone-based, phosphorus-based, sulfur-based, hydroxyl amine-based, hindered-amine-based, semicarbide-based, benzotriazole-based and mixtures thereof to improve spinning processability. It may include additives selected from the group consisting of.

In general, in the case of a split spinneret, the flow path of the resin is complicated in comparison to the spinneret of a single yarn, and since the weight and flow of the resin discharged per spinneret is small, the probability of side reactions occurring in the molten resin is high, so that the melt spinning of a single yarn During the process, the number of trimmings is large and the flow rate is unstable, resulting in a cross-section bonding phenomenon in which the two components 200 are stuck together.

In the case of the polyphenylene sulfide resin, unlike the polyester-based and polyamide-based resins, the resin itself is generated in a solvent or polymerization process such as N-methyl-pyrrolidone (NMP) introduced in the polymerization process of the resin. Since impurities such as sulfur compounds and phenylene compounds remain in the resin in a large amount, the number of trimming frequently occurs during the process during melt spinning.

In addition, the polyphenylene sulfide is a resin that tends to have a cross-section adhesion between two components 200 due to unstable flow rate between spinnerets due to partially uneven resin melt density due to side reaction by impurities in the molten resin. Therefore, the dividing cross-section-forming spinning conditions of the polyphenylene sulfide resin are very demanding.

Among these processes, trimming and cross-section bonding not only decrease the process yield, but also interfere with the production of products of uniform quality, so an additive that can suppress them is needed.

The additive may be a compound generally selected from the group consisting of phenol, lactone, phosphorus, sulfur, hydroxyl amine, hindered amine, semicarbazide, benzotriazole, and mixtures thereof. Since it has to withstand the development, it is preferably an additive containing a phenolic and phosphorus-based compound.

The additive contained in the two-component 200 is a phenomenon that occurs when the polyphenylene sulfide resin is exposed to high temperature in a molten state for a long time, that is, a chain oxidation reaction by peroxide (ROO-) generated by free radicals and a polymer It suppresses side reactions such as side chain branching reactions by reacting between main chains, and serves to alleviate the trimming and cross-section adhesion during the spinning process of split-type polyphenylene sulfide microfibers.

In addition, phenolic compounds and phosphorus-based compounds have different mechanisms to prevent the oxidation of polymers, such as trapping radicals to prevent the chain reaction of radicals or to remove oxygen from already oxidized polymers.

Therefore, it is preferable to use one or more of each of the phenolic compound antioxidant and the phosphorus compound antioxidant or an antioxidant in which the phenolic compound and the phosphorus compound are blended.

Among the additives included in the two-component 200, a typical example of a phenolic compound is 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl) Benzene) (1,3,5-Trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene), 1,6-bis[3-(3,5-di -tert-butyl-4-hydroxyphenyl)propionamido]hexane (1,6-Bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionamido]hexane), 1,6-bis [3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionamido]propane (1,6-Bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionamido ]propane), tetrakis[methylene(3,5-di-tert-butyl-4-hydroxyhydrocinnamate)]methane (tetrakis[methylene(3,5-di-tert-butyl-4-hydroxyhydrocinnamate)]methane ), Octadecyl3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (Octadecyl3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate), 3,9 -Bis[2-(3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy)-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5.5 ]Undecane (3,9-bis[2-(3-(3-tert-butyl-4-hydroxy-5-methyl phenyl) propionyl oxy)-1,1-dimethyl ethyl]-2,4,8,10 -tetraoxaspiro(5,5)undecane), tetrakis[methylene-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]methane (Tetrakis[methylene-3-(3,5 -di-tert-butyl-4'-hydroxyphenyl)propionate]methane), triethylene glycol-bis(3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate (Triethyleneg and lycol-bis[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate]).

Examples of the phosphorus-based additive compound include tris(2,4-ditert-butylphenyl)phosphate, tris(nonylphenyl)phosphate, and tetrakis. (2,4-di-tert-butylphenyl)4,4-biphenylenediphosphonite (tetrakis(2,4-di-tert-buthylphenyl)-4,4'-biphenylenediphosphonite), tri(2,4- Di-tert-butylphenyl)phosphite, diisodecylpentaerythritolphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol Diphosphite (bis(2,4-di-tert-buthylphenyl)pentaerythritolphosphite), bis(2,6-di-tert-butyl-4-methylphenyl)-pentaerythritol diphosphite (bis(2,6-di-tert -buthyl-4-methylphenyl)pentaerythritolphosphite, diisodecyloxypentaerythritolphosphites, bis(2,4-di-tert-butyl-6-methylphenyl)pentaerythritol diphosphite (bis(2,4 -di-tert-buthyl-6-methylphenyl)pentaerythritolphosphite, bis(2,4,6-tris-(tert-butylphenyl))pentaerythritol diphosphite (bis(2,4,6-tris-(tert- buthylphenyl)pentaerythritolphosphites), tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate (Tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate) And the like.

The additives included in the two-component 200 should have a property that does not easily deteriorate even at a maximum of 320°, and the total weight of the two-component 200 includes 0.05wt% to 2wt% of the total weight of the polyphenylene sulfide resin. Is done.

When it is added at 0.05 wt% or less, it does not sufficiently suppress side reactions in the molten resin, and in the case of over 2 wt%, the lubricating role of the additive component that does not participate in the side reaction suppression function is excessively maximized to reduce the melt viscosity of the resin and uniformity It tends to hinder the formation of one cross section.

In one embodiment of the present invention, the spinneret of the divided composite spinning yarn has four or more spinnerets of the two components 200. Preferably, the number of spinnerets of the two components 200 is 4 or more and 16 or less.

In one embodiment of the present invention, the spinning temperature is 200 to 300°C, and the spinning speed is 600 to 1,300 m/min. If the spinning speed is less than 600 m/min, the cross-section of the fiber is not uniform and is not clean, so the quality is not excellent. If the spinning speed is more than 1,300 m/min, there is a probability that one or more filaments are instantly cut off. This is high, and the cross-sectional formability tends to be poor.

In addition, when the molten one component 100 and two components 200 are radiated at the same spinning speed, the boundary between the one component 100 and the two components 200 becomes clear and the one component 100 is added. Even when used at 20% by weight, uniform quality can be obtained.

In another example of the present invention, after the composite spinning step, the step of stretching the composite-spun 1 component 100 and 2 components 200 at a stretching ratio of 3.0 to 5.0 and a stretching speed of 70 to 120 m/min is further included. It can contain.

In another example of the present invention, after the stretching step may further include the step of manufacturing a non-woven fabric using the stretched one component 100 and two components 200.

In another example of the present invention, after the step of manufacturing the nonwoven fabric, the compound-spun 1 component 100 and 2 components 200 may be further alkali-treated to elute the 1 component 100.

In another example of the present invention, the split-type polyphenylene sulfide microfiber may be made of a non-woven fabric in a post-process, and then composed of two components 200 in which one component 100 is eluted and divided by alkali.

Hereinafter, the present invention will be described in more detail by examples. However, these examples are only presented to understand the contents of the present invention, and the scope of the present invention should not be interpreted as being limited to these examples.

Example One

Intrinsic viscosity 0.2 containing 2 wt% of a polyester resin copolymerized with polyethylene glycol having a molecular weight of 20,000 as one component and 0.1 wt% of phenolic antioxidant and 0.1 wt% of phosphorus antioxidant compared to the total weight of the two components as two components It is composed of 25 parts by weight of 1 component and 75 parts by weight of 2 components melted in each melt extruder using dl/g polyphenylene sulfide resin, and is supplied to a spinneret for a split-type composite spinner with 8 spinnerets of 8 components. After multi-spinning and producing a partially stretched yarn at a spinning speed of 800 m/min, a split-type polyphenylene sulfide having a fineness of 3De' using a conventional drawing equipment at a draw ratio of 3.4 and a draw speed of 100 m/min. Ultrafine fibers were prepared.

Example 2

The same method as in Example 1, except that a polyphenylene sulfide resin having an intrinsic viscosity of 0.2 dl/g, each containing 0.5 wt% of a phenolic antioxidant and 0.5 wt% of a phosphorus antioxidant, respectively, based on the total weight of the two components as two components was used. Was prepared.

Comparative example One

The same method as in Example 1, except that a polyphenylene sulfide resin having an intrinsic viscosity of 0.2 dl/g, each containing 0.02 wt% of a phenolic antioxidant and 0.02wt% of a phosphorus antioxidant, respectively, as a two component total weight by weight, was used. Was prepared.

Comparative Example 2

The same method as in Example 1, except that a polyphenylene sulfide resin having an intrinsic viscosity of 0.2 dl/g, each containing 1.2 wt% of a phenolic antioxidant and 1.2 wt% of a phosphorus antioxidant, respectively, as a two component total weight by weight, was used. Was prepared.

Comparative example 3

It was prepared in the same manner as in Example 1, except that a polyphenylene sulfide resin having an intrinsic viscosity of 0.2 dl/g containing 0.2 wt% of a phenolic antioxidant relative to the total weight of the two components as a two component was used.

Comparative example 4

It was prepared in the same manner as in Example 1, except that a polyphenylene sulfide resin having an intrinsic viscosity of 0.2 dl/g containing 0.2 wt% of a phosphorus-based antioxidant relative to the total weight of the two components as the two components was used.

Comparative example 5

It was prepared in the same manner as in Example 1, except that a polyphenylene sulfide resin having an intrinsic viscosity of 0.2 dl/g containing no antioxidant as a two component was used.

Comparative example 6

It was prepared in the same manner as in Example 1, except that the nylon 6 resin having a relative viscosity of 3.3 as a two-component.

* Property evaluation

(1) Spinning Yield: Spinning Yield (%) = (Amount of Spinned Fiber (g))/(Amount of Initial Polymer (g))*100

(2) Cross-section adhesion rate: The number of yarns attached to the cross-section photograph measured by a microscope was calculated as a frequency.

(3) Alkali loss and reduction rate: The alkali reduction of the fabricated fiber was performed for 30 minutes at 100°C in a 1% NaOH aqueous solution, and the loss rate was the weight between the weight before weight loss (WI) and the weight after loss weight (WF). The difference was calculated using the following equation.

Loss rate (%)=(WI-WF)/(WI)*100

(4) Fiber steel/elongation: Measured by the KS K 0860 method.

(5) Flame retardancy: Flame retardancy for reduced fiber was evaluated by conducting French flame retardant test standard NFP 92-503, 504, 505, which is the most widely used flame retardant certification method in the world.

The additives used are as follows.

(1) Phenolic antioxidant: Octadecyl3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate

(2) Phosphorus antioxidant: tetrakis(2,4-di-tert-butylphenyl)4,4-biphenylenediphosphonite

Emission yield
(%) Section bonding rate
(%) Loss rate
(%) burglar
(g/de) Shinto
(%) Flame retardant Example 1 97.0 0 29.5 3.6 50.2 Pass(M1) Example 2 96.8 0 29.6 3.7 49.2 Pass(M1) Comparative Example 1 90.5 6.5 30.1 3.7 51.4 Pass(M1) Comparative Example 2 92.0 8.9 29.4 3.3 53.5 Pass(M1) Comparative Example 3 95.2 3.2 29.4 3.4 48.7 Pass(M1) Comparative Example 4 94.0 4.1 29.7 3.4 50.0 Pass(M1) Comparative Example 5 86.1 10.2 30.2 3.7 52.7 Pass(M1) Comparative Example 6 98.9 0 30.3 4.8 37.3 Pass(M2)

As can be seen in Examples 1 to 2 of Table 1, the split-type polyphenylene sulfide microfiber containing the antioxidant has no significant change in strength, elongation, loss rate, and flame retardancy compared to Comparative Example 5 without the antioxidant. It can be seen that the emissivity increases and the cross-section adhesion rate decreases.

In addition, in the case of Comparative Examples 1 to 2 in which the total weight of the two antioxidants was 0.05 wt% or less or 2 wt% or more, respectively, based on the total weight of the island components, it was confirmed that the radiation yield and the cross-section adhesion rate were not significantly improved.

In addition, through Comparative Examples 3 to 4, it can be seen that the examples of using one of the phenol-based antioxidants and the phosphorus-based antioxidants are more effective than the ones using one of each.

100: 1 component 200: 2 components

Claims (4)

In the flame retardant split type microfiber,
1 component containing alkali-soluble polyester polymer resin and
It consists of two components containing polyphenylene sulfide resin,
The polyphenylene sulfide resin is linear and has an intrinsic viscosity of 0.2 dl/g or more, a weight average molecular weight (Mw) of 20,000 to 80,000, and a melt viscosity (Mv) of 500 to 2500 poise at 300°C. ,
The first component is 20 to 50% by weight, the second component is 50 to 80% by weight,
The alkali-soluble polyester polymer resin is a copolymer of 0.1 to 5% by weight of polyethylene glycol having a molecular weight of 10,000 to 20,000,
The polyphenylene sulfide resin is a flame-retardant split type ultrafine fiber, characterized in that an antioxidant composed of a phenolic compound to phosphorus compound in a weight ratio of 4:6 to 6:4 is added in an amount of 0.05 wt% to 2 wt% based on the weight of the two components.
According to claim 1,
The number of the two components in the split-type microfiber is 4 to 16, the fineness of the split-type microfiber is 1.0 to 5.0 denier, the fineness of the flame retardant split-type characterized in that the fineness of one of the two components is 0.05 to 1.25 denier. fiber.
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