KR101992446B1 - Noninflammable Sea-island Type Microfiber Having Good Touch - Google Patents

Abstract

The present invention relates to fire retardant sea-island type ultrafine fiber with excellent tactile sensation, which comprises a sea component containing alkali-soluble polyester polymer resin and an island component including polyphenylene sulfide resin. The sea component is 20 to 60 wt%, the island component is 40 to 80 wt%, and the alkali-soluble polyester resin is a copolymer of 0.1 to 5 wt% of polyethylene glycol having a molecular weight of 10,000 to 20,000. An inorganic additive is added to the polyphenylene sulfide resin to have soft tactile sensation; and an antioxidant composed of a phenol compound and a phosphorus compound in a weight ratio of 4:6 to 6:4 is added to the polyphenylene sulfide resin.

Description

[0001] The present invention relates to a non-flammable sea-island type microfiber Having Good Touch,

The present invention relates to a flame-retardant sea-island microfine fiber, and more particularly, to a sea-island microfine fiber comprising polyphenylene sulfide (PPS) resin as an ingredient and having excellent feel.

The microfine fiber in the present invention is a fiber developed so as to have a very smooth and soft touch. By dividing the spinning fiber, fine fibers of up to 0.001 denier can be produced. Although it is mainly used for high value-added fiber products such as artificial leather, artificial suede, automobile interior material and case cover, it is very important to select the raw material fiber to be used as the higher quality product in this application. In the post- Punching, impregnation, brushed and the like are very various and complicated.

Methods for producing microfine fibers include single component spinning, multicomponent spinning (composite spinning), air jet spinning, flash spinning, and the like. The single component spinning has the advantage of directly spinning the fibers of the desired fineness, which is advantageous in that the production cost is reduced because the process is not performed after the fineness. However, there is a limitation in the ultrafine fineness of the nano unit. Multi-component spinning can produce sea-island type, split type, multi-layer type fibers. The sea-island type fiber is called extraction type, and two or more polymers having different solvent extraction properties are spin- It is possible to produce 0.01 denier fiber by the extraction method, and there is a merit that the diameter deviation is small. Air jet spinning is the most superior process for producing fine fibers by extruding a polymer melt through a spinneret, then using the heated high-speed air to make the fibers, and then to accumulate irregularly in the collector to form a nonwoven structure. The flash radiation is produced by extruding a polymer such as propylene, and then evaporating the solvent immediately after detachment, whereby each fiber is collected on a moving screen in a fibril form to form a network structure.

Currently, the composition of most sea-island microfiber is 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. Recently, polyphenylene sulfide (PPS) fibers have been increasingly used as an interior material for flame retardant materials due to limitations in the use of flame retardant additives and national regulations and users' expectations for halogen flame retardants.

Such a sea-island polyphenylene sulfide superfine fiber having such flame retardancy has a problem in that since a large amount of impurities remain in the resin, unlike the polyester or nylon in which the resin itself is usually used, the number of times of refolding during the melt- , The resin melt density is partially uneven and the flow velocity between the spinning nozzles is unstable. As a result, the cross-linking phenomenon in which the components are stuck together easily occurs. Therefore, the conditions of the sea-island cross-sectional spinning of the polyphenylene sulfide resin are very difficult . As a result, the process yield is very low, resulting in high process costs and the supply is not smooth compared to the market demand.

Particularly, when sea-island microfibers are applied to synthetic leather, titanium oxide or calcium carbonate is added to the metallic components to enhance the softness of the tactile feel. Such minerals also have an adverse effect on the sea-island cross-section spinning process of the polyphenylene sulfide resin.

In order to solve the problems of the prior art, it is necessary to develop polyphenylene sulfide microfine fibers having flame retardancy and excellent melt spinning processability and softness for synthetic leather. Therefore, in the present invention, sea water-type polyphenylene sulfide microfine fibers and a manufacturing method thereof are proposed to solve the above problems.

In order to solve the above problems, it is an object of the present invention to provide a sea-island polyphenylene sulfide microfine fiber having excellent flame retardancy and feel.

It is another object of the present invention to provide a method for producing polyphenylene sulfide isothermal ultrafine fibers with improved spinnability.

In order to solve the above-mentioned problems, the present invention is a flame-retarded sea-island microfine fiber comprising a sea component containing an alkali-soluble polyester polymer resin and a component containing a polyphenylene sulfide resin, wherein the sea component comprises 20 Wherein the alkali-soluble polyester resin is a copolymer of 0.1 to 5 wt% of polyethylene glycol having a molecular weight of 10,000 to 20,000, and the polyphenylene sulfide resin is soft An inorganic additive exhibiting tactile feel; Wherein the polyphenylene sulfide resin is a polyphenylene sulfide microfine fiber having excellent tactile feel and characterized by addition of an antioxidant comprising a phenol compound and a phosphorus compound in a weight ratio of 4: 6 to 6: 4.

Further, the present invention is characterized in that the number of islands in the sea-island microfine fiber is 10 to 100, the fineness of the sea-island microfine fiber is 1.0 to 5.0 denier, and the fineness of the island component is 0.07 to 0.28 denier To provide sea-island polyphenylene sulfide microfine fibers.

In addition, the inorganic additive of the present invention is characterized by being composed of titanium oxide or calcium carbonate, and is characterized in that it is 0.1 wt% to 5 wt%, based on the weight of the conductive component, to provide the sea-island polyphenylene sulfide microfine fiber having excellent tactile feel.

Also, the present invention provides a sea-island polyphenylene sulfide microfine fiber characterized in that the antioxidant is 0.05 wt% to 2 wt%, based on the weight of the component.

In addition, the present invention relates to a method for producing a polyester resin composition, which comprises a step of blending a polyester resin copolymerized with 0.1-5 wt% of polyethylene glycol having a molecular weight of 10,000-20,000 as a marine component and an inorganic additive, 6: 4 by weight in a melt extruder, respectively; Supplying the molten sea component and the molten salt to the sea salt-type complex spinning spinneret and spinning the combined spinneret; The composite spinning step may include stretching the composite spinning halide and the component with a stretching ratio of 3.0 to 4.0 and a stretching speed of 70 to 120 m / min, wherein the composite spinning speed is 800 to 1,300 m / min And the sea component is contained in an amount of 20 to 60% by weight and the island component is contained in an amount of 40 to 80% by weight. The present invention also provides a method for manufacturing sea-island polyphenylene sulfide microfine fibers.

The sea-island polyphenylene sulfide microfine fiber of the present invention has a flame retarding effect.

The method of producing polyphenylene sulfide sea-island microfine fibers according to the present invention is characterized in that the spinning processability is improved.

1 is a conceptual diagram of sea-island polyphenylene sulfide microfine fibers according to an embodiment of the present invention.

Hereinafter, preferred embodiments of the present invention will be described in detail. In the following description of the present invention, a detailed description of known functions and configurations incorporated herein will be omitted so as to avoid obscuring the subject matter of the present invention.

As used herein, the terms " about, " " substantially, " " etc. ", when used to refer to a manufacturing or material tolerance inherent in the stated sense, Accurate or absolute numbers are used to help prevent unauthorized exploitation by unauthorized intruders of the referenced disclosure.

Sea-island polyphenylene Sulfide  Microfiber

Fig. 1 is a cross-sectional view of sea-island polyphenylene sulfide microfine fibers according to the present invention, which is composed of a sea component 100 and a component component 110. Fig.

The method for producing sea-island polyphenylene sulfide microfine fibers according to the present invention is characterized in that an alkali-soluble polyester as a sea component (100) and an inorganic additive composed of titanium oxide or calcium carbonate as a component (110), a phenol- And a polyphenylene sulfide resin added thereto.

Generally, in sea-island type fibers, the sea component (100) arranges a material having a melting point lower than that of the island component (110) and being liable to be eluted by alkali.

That is, in the combination of polyester and nylon, nylon is used as the component 110. In the combination of polyester and copolyester, polyester is used as component 110. In the combination of copolyester and nylon, nylon is used as component 110 ).

In the present invention, a polyester resin is used as the sea component (100). The polyester resin preferably includes a polyester resin in which an organic sulfonic acid metal salt is copolymerized with 0.1 to 5 wt% of polyethylene glycol having a molecular weight in the range of 10,000 to 20,000.

In the present invention, polyphenylene sulfide resin is used as the filler (110), and the polyphenylene sulfide resin may include linear, cross-linked, and semi-cross-linked, but preferably linear. 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 has a melt viscosity (Mv) 500 ~ 2500 poise should be used for excellent physical properties including yarn strength.

The polyphenylene sulfide resin has excellent chemical resistance and excellent heat distortion temperature of 270 DEG C or more. The polyphenylene sulfide resin is an environmentally friendly flame retardant resin which can be flame retarded even without a flame retardant because it has its own flame retardant property. Generally, glass fiber or the like is added in consideration of mechanical strength and the like, but polyphenylene sulfide The resin is preferably composed of only the molecular chain of phenylene sulfide for the fiber, and more preferably 90 mol% or more of the p-phenylene sulfide unit.

Sea-island polyphenylene Sulfide  Method for manufacturing microfine fibers

The method for producing sea-island polyphenylene sulfide microfine fibers according to the present invention comprises melting alkali-soluble polyester as a sea component (100) and polyphenylene sulfide resin as a component (110) in a melt extruder, (100) and the island component (110) to the sea-island complex spinning spinneret and radiating composite radiation.

At this time, the metallic polyphenylene sulfide resin may include an inorganic material selected from the group consisting of titanium oxide, calcium carbonate, and mixtures thereof to soften the feel of microfine fibers.

In addition, the above-mentioned isocyanate polyphenylene sulfide resin is preferably used in the form of a phenol-based, lactone-based, phosphorus-based, sulfur-based, hydroxylamine-based, hindered amine-based, semicarbazide-based, benzotriazole- And an additive selected from the group consisting of

Generally, in comparison with the single yarn spinneret, since the flow path of the resin is complicated in the case of the sea-island spinneret, the weight and flow of the resin discharged per spinneret are low and the probability of occurrence of the side reaction in the resin is high. There is a phenomenon of cross-sectional adhesion, in which the number of energizing times is large and the flow velocity is unstable, so that the metal particles 110 stick together.

In the case of the polyphenylene sulfide resin, the resin itself is different from a commonly used polyester-based or polyamide-based resin, and occurs in a solvent such as N-methyl-pyrrolidone (NMP) And a large amount of impurities such as sulfur compounds and phenylene compounds remain in the resin, so that the number of times of refolding during the melt spinning frequently occurs.

In addition, the polyphenylene sulfide has a problem that the resin melt density is partially uneven due to a side reaction caused by impurities in the molten resin, so that the flow rate between the spinning nozzles is unstable and the resin particles 110 stick together, Therefore, the conditions for the sea-island cross-sectional spinning of the polyphenylene sulfide resin are very difficult.

In order to produce microfine fibers for synthetic leather, an inorganic material such as titanium oxide or calcium carbonate should be added in an amount of 0.1 wt% to 5 wt% with respect to the total weight of the conductive particles to form a soft touch. The polyphenylene sulfide- When calcium carbonate is added, it acts as an impurity and tends to cause the phenomenon of reflux and cross-section adhesion in the spinning process.

Among these processes, embedding phenomenon and cross-linking phenomenon not only deteriorate the process yield but also hinder the production of uniform quality products, so that an additive that can be suppressed is required.

The additive may generally be a compound selected from the group consisting of phenol, lactone, phosphorus, sulfur, hydroxylamine, hindered amine, semicarbazide, benzotriazole and mixtures thereof, It is preferably an additive containing a phenolic compound and a phosphorus compound.

The additive included in the filler 110 is a phenomenon that occurs when the polyphenylene sulfide resin is exposed to a high temperature in a molten state for a long time, that is, a chain oxidation reaction by peroxide (ROO-) generated by a free radical, It suppresses side reactions such as Side Chain Branch phenomenon which reacts with main chains and plays a role of mitigating embossing and cross-sticking phenomenon during the spinning process of sea-island polyphenylene sulfide microfine fibers.

In addition, the phenolic compound and the phosphorous compound have different mechanisms for preventing the oxidation of the polymer, such as capturing radicals to block the chain reaction of radicals or removing the oxygen of the already oxidized polymer.

Therefore, it is preferable to use at least one phenolic compound antioxidant and at least one phosphorus compound antioxidant, respectively, or to use an antioxidant in which a phenolic compound and a phosphorus compound are blended.

Representative examples of the phenol compound among the additives contained in the metallic component 110 include 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) Benzene), 1,6-bis [3- (3,5-di (tert-butyldimethylsilyl) butyl-4-hydroxyphenyl) propionamido] hexane), 1,6-bis [3- (3,5- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionamido] propane ] propane, tetrakis [methylene (3,5-di-tert-butyl-4-hydroxyhydrocinnamate)] methane (tetrakis [ Octadecyl 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate), 3,9 -Bis [2- (3- (tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy) -1,1- dimethylethyl] -2,4,8,10-tetraoxa 3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy) -1,1-dimethyl ethyl] -2,4- Tetraoxaspiro (5,5) undecane, tetrakis [methylene-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane (Tetrakis [methylene- 3-tert-butyl-4-hydroxyphenyl) propionate] methane, triethyleneglycol- bis [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate].

 Phosphorus additive compounds include tris (2,4-ditert-butylphenyl) phosphate, tris (nonylphenyl) phosphate, tetrakis (2,4-di-tert-butylphenyl) -4,4'-biphenylenediphosphonite, tetrakis (2,4- Di- tert-butylphenyl) phosphite, diisodecylpentaerythritolphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol Bis (2,4-di-tert-buthylphenyl) pentaerythritolphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) -pentaerythritol diphosphite -buthyl-4-methylphenyl) pentaerythritolphosphite, diisodecyloxypentaerythritolphosphites, bis (2,4-di-tert-butyl-6-methylphenyl) pentaerythritol diphosphite bis -di (2,4,6-tris- (tert-buthylphenyl) pentaerythritolphosphite), bis (2,4,6-tris- pentaerythritolphosphites and 4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl isocyanurate. And the like.

The additive included in the filler 110 must have a property of not easily deteriorating even at a maximum of 320 ° and a weight sum of 0.05 to 2 wt% based on the total weight of the polyphenylene sulfide resin as the filler 110 .

When the amount of the additive is less than 0.05wt%, the side reaction can not be sufficiently suppressed in the molten resin. If the amount of the additive is over 2wt%, the additive ingredient which does not participate in the side reaction inhibition function is maximized, There is a tendency to interfere with formation of one cross section rather.

In one embodiment of the present invention, the radial detachable spinneret for use in the sea-island type combined spinnerette has 10 or more spinnerets of the filler 110. Preferably, the number of discharge ports of the conductive component 110 is 10 or more and 100 or less.

In one embodiment of the present invention, the spinning temperature is 200 to 300 占 폚, 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 not clean, and the quality is not excellent. If the spinning speed is more than 1,300 m / min, there is a possibility that one or more filaments are instantly broken Is high and the cross-sectional formability is also poor, so that only one component other than the two components is radiated.

The boundary between the sea component 100 and the island component 110 becomes clear when the molten sea component 100 and the island component 110 are radiated at the above-mentioned spinning speed to form the sea component 100 Even when used in an amount of 20% by weight, a uniform quality can be obtained.

In another example of the present invention, after the composite spinning step, the step of stretching the composite spinning solution 100 and the island component 110 at a stretching ratio of 3.0 to 5.0 and a stretching speed of 70 to 120 m / min .

In yet another embodiment of the present invention, the method may further include the step of fabricating the nonwoven fabric using the elongated marine component (100) and the island component (110) after the stretching step.

In still another embodiment of the present invention, the step of preparing the nonwoven fabric may further include a step of alkali-treating the composite spinneret 100 and the component 110 to remove the component 100.

In still another aspect of the present invention, the sea-island polyphenylene sulfide microfine fiber may be composed of a remaining component 110 that is produced as a nonwoven fabric in a later process, and then the marine component 100 is eluted by alkali.

Hereinafter, the present invention will be described in more detail with reference to examples. It is to be understood, however, that these examples are provided so as to understand the scope of the present invention, and are not to be construed as limiting the scope of the present invention.

Example  One

A polyester resin having a molecular weight of 20,000 and having a molecular weight of 20,000 and having a molecular weight of 20,000 was used. As a flame retardant, 2 wt% of an inorganic titanium oxide was contained as a glass component and 0.1 wt% of a phenolic antioxidant and 0.1 wt% By weight of a polyphenylene sulfide resin having an intrinsic viscosity of 0.5 dl / g, each containing 30% by weight of a molten salt dissolved in each of the melt extruders and 70% The composite yarn was supplied to the composite spinning spinneret to perform composite spinning, and a partially drawn yarn was produced at a spinning speed of 700 m / min. The spinning spinning ratio was set to 3.7 and a drawing speed of 100 m / min to 4.0 denier / 37 filaments were prepared.

Example  2

Except that a polyphenylene sulfide resin having an intrinsic viscosity of 0.5 dl / g containing 2 wt% of inorganic calcium carbonate as a filler was used as a filler.

Example  3

Except that a polyphenylene sulfide resin having an intrinsic viscosity of 0.5 dl / g containing 0.5 wt% of a phenol-based antioxidant and 0.5 wt% of a phosphorus-based antioxidant was used as a filler in the same manner as in Example 1 .

Comparative Example  One

Except that a polyphenylene sulfide resin having an intrinsic viscosity of 0.5 dl / g containing 0.05 wt% of an inorganic titanium oxide as a filler was used as a filler.

Comparative Example  2

Except that a polyphenylene sulfide resin having an intrinsic viscosity of 0.5 dl / g containing 8 wt% of an inorganic titanium oxide as a filler was used as the filler.

Comparative Example  3

Except that a polyphenylene sulfide resin having an intrinsic viscosity of 0.5 dl / g containing 0.2 wt% of a phenolic antioxidant alone was used without containing a phosphorus antioxidant as a flame retardant. .

Comparative Example  4

Except that a polyphenylene sulfide resin having an intrinsic viscosity of 0.5 dl / g containing 0.2 wt% of phosphorus-based antioxidant alone was used as a flame retardant, Respectively.

Comparative Example  5

Except that polyphenylene sulfide resin having an intrinsic viscosity of 0.2 dl / g, which does not contain an inorganic substance and an antioxidant, was used as a filler.

Comparative Example  6

Except that a polyphenylene sulfide resin containing 0.1 wt% of a phenolic antioxidant and 0.1 wt% of a phosphorus-based antioxidant and having an intrinsic viscosity of 0.2 dl / g, which does not contain an inorganic substance, is used as a starting material Was prepared in the same manner as in Example 1.

Comparative Example  7

Except for using a polyphenylene sulfide resin having an intrinsic viscosity of 0.2 dl / g, which contains 2 wt% of inorganic titanium oxide as a filler and does not contain an antioxidant.

Comparative Example  8

Except that a polyester resin having an intrinsic viscosity of 0.64 dl / g containing 2 wt% of an inorganic titanium oxide as a filler was added to the total weight of the glass beads.

* Property evaluation

(1) Radial yield: Radial yield (%) = (amount of radiated fiber (g)) / (amount of initial polymer (g)) * 100

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

(3) Alkali reduction and weight loss: The alkali loss of the prepared fibers was carried out in a 1% aqueous solution of NaOH at 100 ° C for 30 minutes. The weight loss rate was calculated by subtracting the weight between the weight before weight loss (WI) The difference was calculated using the following equation.

Weight loss rate (%) = (WI-WF) / (WI) * 100

(4) Fiber steel / elongation: measured by KS K 0860 method

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

The additives used are as follows.

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

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

Radiation yield
(%) Cross-section adhesion rate
(%) Weight loss rate
(%) burglar
(g / de) Shindo
(%) touch Flammability Example 1 95.4 0 30.1 3.7 52.0 ○ Pass (M1) Example 2 95.1 0 29.8 3.7 54.7 ○ Pass (M1) Comparative Example 1 96.2 0 30.8 3.8 53.2 △ Pass (M1) Comparative Example 2 85.2 12.3 29.9 2.9 67.2 ○ Pass (M1) Comparative Example 3 91.8 5.2 30.1 3.7 50.0 ○ Pass (M1) Comparative Example 4 92.0 4.4 30.5 3.7 53.9 ○ Pass (M1) Comparative Example 5 90.3 7.2 30.2 3.8 49.2 X Pass (M1) Comparative Example 6 95.4 0 30.4 3.8 51.5 X Pass (M1) Comparative Example 7 88.6 9.7 30.5 3.3 60.7 ○ Pass (M1) Comparative Example 8 97.4 0 29.7 5.0 37.5 ○ Pass (M2)

As can be seen from Examples 1 and 2 of Table 1, the sea-island polyphenylene sulfide microfine fibers containing an antioxidant had a higher strength compared to Comparative Example 5 containing no antioxidant even though an inorganic material adversely affecting the spinning process was added, Although there is no significant change in elongation, weight loss, and flame retardancy, the radiation yield increases and the cross-section adhesion rate decreases.

In the case of Comparative Examples 1 and 2 in which the total weight of the inorganic materials is not more than 0.1 wt% or not less than 5 wt% with respect to the total weight of the components, the touch feeling is not good.

In Comparative Examples 3 to 4 using only one of the phenolic antioxidants and the phosphorus-based antioxidants, the radiation yield and the cross-sectional densification were slightly improved, but the effects of the same additives were greater than those of Examples 1 and 2, You can see that there is no.

In addition, it was confirmed that Comparative Example 5 in which the inorganic component and the antioxidant were not contained and the Comparative Example 7 in which only the inorganic component was used did not improve the radiation yield and the cross-sectional adhesion rate.

100: sea component 110: city component

Claims (5)

In the flame-retardant sea-island microfine fibers,
A sea component containing an alkali-soluble polyester polymer resin and
And a polyphenylene sulfide resin,
The sea component is 20 to 60% by weight, the content of the component is 40 to 80% by weight,
The alkali-soluble 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,
Wherein the polyphenylene sulfide resin is an inorganic additive that exhibits soft touch;
The polyphenylene sulfide resin is prepared by adding an antioxidant composed of a phenol compound and a phosphorus compound in a weight ratio of 4: 6 to 6: 4,
The sea-island polyphenylene sulfide microfine fiber is characterized by a cross-sectional adhesion rate of 1% or less.
The method according to claim 1,
Characterized in that the number of islands in the sea-island microfine fiber is 10 to 100, the fineness of the sea-island microfine fibers is 1.0 to 5.0 denier, and the fineness of one fineness is 0.07 to 0.28 denier. Type polyphenylene sulfide microfine fibers.

The method according to claim 1,
The inorganic additive is characterized by being composed of titanium oxide or calcium carbonate, and is 0.1 wt% to 5 wt%, based on the weight of the metallic component, of the sea-island polyphenylene sulfide microfine fiber.
The method according to claim 1,
Wherein the antioxidant is 0.05 wt% to 2 wt%, based on the weight of the catalyst component.
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