KR20100035256A - Flame retardant lyocell fibers and process for preparing fabrics using the same - Google Patents

Abstract

The present invention relates to a flame-retardant lyocell fiber and a method for manufacturing a fabric using the same, the surface-treated with a coating composition comprising a polymer resin, a phthalic acid or adipic acid-based plasticizer, and an inorganic or halogen-phosphorous flame retardant in the lyocell fiber It is characterized by.

According to the present invention, by applying a polymer resin coating on the lyocell fibers, it is possible to further improve the flame retardancy with excellent mechanical properties to the fiber itself, it can be effectively used as a fire protection material in a variety of applications such as furniture and interior.

Description

Flame retardant lyocell fiber and fabrication method using the same {FLAME RETARDANT LYOCELL FIBERS AND PROCESS FOR PREPARING FABRICS USING THE SAME}

The present invention relates to a lyocell fiber excellent in flame retardancy and a method for producing a fabric using the same.

Lyocell fiber refers to cellulose fabric yarn spun from a cellulose solution contained in a mixture of organic solvent and water by a method known as solvent spinning.

In particular, methods for making such lyocell fibers are described, for example, in US Pat. Nos. 4,416,698 and 4,246,221. According to the method described above, lyocell fibers dissolve cellulose in a solvent containing tertiary amine N-oxide (hereinafter referred to as amine oxide), for example N-methylmorpholine N-oxide (NMMO), The resulting solution is prepared by extrusion through a suitable spinneret to solidify, wash with water and then dry to produce fibers. In this method the solvent comprises a small amount of cellulose nonsolvent such as water. The method for producing cellulose fibers by dissolving cellulose in a solvent and extruding and solidifying is called "solvent-spinning", and the fibers produced by this method are called "solvent-spun" cellulose fibers or lyocell fibers. It is called.

On the other hand, it is already known that such lyocell fibers can be produced by a method of extruding a solution of a cellulose derivative into a coagulation and regeneration bath. An example of such a method is the Viscose method, in which cellulose xanthate is used as a cellulose derivative. Solvent-spinning methods are known to produce long cellulosic products that have many advantages, such as no pollutant emissions, over the Viscose method.

The lyocell fiber generally has excellent health, wet strength and modulus, and has excellent morphological stability and price competitiveness, but it is a kind of cellulose fiber such as cotton or rayon, which is not highly flame retardant compared to other synthetic fibers. There is this.

In the past, the so-called post-processing disaster prevention method of applying a flame-retardant disaster prevention agent to a textile woven fabric has been applied. However, problems such as uniformity of adhesion of the disaster prevention agent, curing of the woven fabric by adhesion, detachment by washing and stability, etc. there was.

In particular, in order to impart flame retardancy directly to a fiber, a method of adding a flame retardant in a spinning step of fiberizing, or a method of copolymerizing with a monomer containing a component having flame retardancy in a step of preparing a polymer for fiber (mainly a polymerization step), etc. It was also used. However, the method of adding a flame retardant in the spinning step or the polymerization step has a disadvantage in that the physical properties and the spinning properties of the fiber are lowered. In particular, when the flame retardant is added in the spinning step, the flame retardant is decomposed at a high spinning temperature, or in the case of inorganic materials, there is a problem of blocking the spinning nozzle.

In addition, in the case of using synthetic fibers such as polyester instead of lyocell, there is a problem that poisonous gases such as carbon monoxide and carbon dioxide are generated, and there is a problem in that workability is not high due to high shrinkage.

Therefore, to be applicable as various industrial fibers for industrial, architectural, and interior use, it is necessary to study the development of a fiber material provided with excellent flame retardancy while maintaining excellent mechanical properties of the lyocell fiber itself.

The present invention is to provide a lyocell fiber excellent flame retardancy with high mechanical properties.

The present invention also provides a method for producing a flame retardant fabric using the lyocell fibers.

The present invention provides flame retardant lyocell fibers surface-treated with a coating composition comprising a polymeric resin, a phthalic acid or adipic acid based plasticizer, and an inorganic or halogen-phosphorous flame retardant.

The present invention also includes coating a lyocell fiber with a coating composition comprising a polymer resin, a phthalic acid- or adipic acid-based plasticizer and a flame retardant, and weaving and tentering the coated lyocell fiber with warp and weft yarns. It provides a method for producing a flame retardant fabric comprising.

Hereinafter, the present invention will be described in more detail.

In general, a flame retardant fiber material refers to a fiber material that burns when a fiber product is in contact with a flame, but prevents or suppresses combustion by burning a flame by itself when the flame is removed. In other words, it does not prevent the fiber itself from burning, but refers to a fiber that loses the propagation ability of the fire. Instead of flame retardant, terms such as flame retardant, fire retardant, and flame retardant are used. Flame retardant or flame retardant fibrous materials generally refer to a limiting oxygen index (LOI) value of 27 or greater.

Here, the measurement method of the flame retardancy of the fiber material includes the LOI (limiting oxygen index) method, carbonization measurement method, residual flame time test method, combustion test method, etc. Among them, the LOI method is relatively simple and reproducible, etc. It is excellent in number and easy to quantify and is used for comparing the flame retardancy of fibers. The limit oxygen index (LOI) is represented by the minimum oxygen content in the atmosphere necessary to ignite a minimum size of a fiber sample of a constant size. If the LOI value according to the following formula 1 is 27 to 28 or more, it is determined that it is flame retardant.

[Calculation 1]

The lyocell fiber to be developed in the present invention maintains excellent mechanical properties such as strength, elongation and initial elastic modulus, and is characterized by being endowed with excellent flame retardancy to the extent that it can be used as a flame retardant fiber material.

In particular, the lyocell fibers of the present invention are coated with a coating composition comprising a polymeric resin, a phthalic acid or adipic acid plasticizer, and an inorganic or halogen-phosphorous flame retardant directly to the fiber, to provide a high quality yarn of excellent performance.

As the polymer resin, polyvinyl chloride, polyurethane, polyethylene, or a mixture of one or more thereof may be used, and in view of processability and flame retardancy, it is preferable to use polyvinyl chloride.

In addition, the polymer resin is preferably used having a polymerization degree of 800 to 4000. When the degree of polymerization of the polymer resin is more than 4000, heat resistance or aging resistance is increased, but workability is decreased, and as the polyvinyl chloride coating temperature is increased, a problem may occur that the operation becomes difficult. On the other hand, when the degree of polymerization is less than 800, workability and the like are improved, but heat and weather resistance may be poor.

When the polyethylene resin is used as the polymer resin, both linear low density polyethylene (LLDP), low density polyethylene (LDPE), and high density polyethylene (HDPE) can be used.

In the present invention, the plasticizer is a phthalic acid plasticizer or adipic acid plasticizer, and the phthalic acid plasticizer is dioctyl phthalate, dibutyl phthalate, dimethyl phthalate, diethyl phthalate, diheptyl phthalate, dinonyl phthalate, diisodecyl phthalate. , Diundecyl phthalate, ditridecyl phthalate, butylbenzyl phthalate, butyllauryl phthalate or mixtures of one or more thereof may be used. As the adipic acid-based plasticizer, dioctyl adipate, diisononyl adipate, diisodecyl adipate or a mixture of one or more thereof may be used.

The amount of the plasticizer used is preferably 10 to 50 parts by weight, more preferably 20 to 35 parts by weight per 100 parts by weight of the polymer resin. If the amount of the plasticizer exceeds 50 parts by weight per 100 parts by weight of the polymer resin, the flame retardancy is poor, and the migration resistance may not be good. If the amount of the plasticizer is less than 10 parts by weight, the product is too hard and the elongation is not good. Can be.

In the coating composition of the present invention, the flame retardant may be an inorganic flame retardant or a halogen-phosphorus flame retardant, and the inorganic flame retardant may be used by mixing one or more of magnesium hydroxide, aluminum hydroxide, antimony trioxide, or a mixture thereof. In addition, the halogen-phosphorus-based flame retardants include chlorinated organic compounds of tris (2,4-dichloropropyl) phosphate, tris (2-chloropropyl) phosphate, tris (2-chloroethyl) phosphate, chlorinated polyphosphate or mixtures thereof. Polyphosphates may be used. The amount of the flame retardant is preferably 5 to 30 parts by weight, more preferably 10 to 20 parts by weight per 100 parts by weight of the polymer resin. If the amount of the flame retardant is less than 5 parts by weight per 100 parts by weight of the polymer resin, flame retardancy may be lowered. If it exceeds 30 parts by weight, cold resistance may be lowered or processability may be lowered, which is not preferable.

In addition, additives generally used in the preparation of lyocell fibers, for example, azo-based, cyanine-based coloring agents, and imidazole-based antimicrobial agents, may be further added to the coating composition.

The lyocell fibers of the present invention can be prepared by a process comprising a commonly known spinning, coagulation, washing and drying step, wherein the spinning dope is cellulose, pore-forming material, N-methylmorpholine-N -N-methylmorpholine-N-oxide (NMMO) and water.

The cellulose may be conventional in the art to which the present invention pertains, but may be used in an amount of 96% or more of alpha-cellulose to improve physical properties of the fiber. In particular, Southern pine pulp with a content of 96% alpha-cellulose can be used.

The lyocell spinning dope of the present invention may include 5 to 35% by weight of cellulose in consideration of spinning properties, and may also be included to 7 to 18% by weight.

The present invention also includes coating a lyocell fiber with a coating composition comprising a polymer resin, a phthalic acid- or adipic acid-based plasticizer and a flame retardant, and weaving and tentering the coated lyocell fiber with warp and weft yarns. It provides a method for producing a flame retardant fabric comprising.

The coating process may be carried out at 120 to 180 ℃. If the temperature of the coating process is less than 120 ℃ rough surface of the coating yarn, if it exceeds 180 ℃ yellowing phenomenon and concentricity may not be maintained is not preferred.

If necessary, it may further comprise the step of winding and the warp fibers in the coated lyocell fibers. A winding process means the process of preparing an inclination to perform a regular process. The canon process refers to a process of winding an inclined (vertical thread) to a beam to match the length, density, width, etc. of a designed fabric in a fabric manufacturing process, and to wind the work by the desired number of strands and a desired length as needed. it means.

The coated lyocell fibers are woven using warp and weft yarns. In particular, when the warp fibers are normalized, the warp warp fibers and the coated weft fibers can be woven. The weaving process refers to a process of weaving the weft yarns at a right angle to the warp by crossing each other up and down every one or two warps according to a predetermined rule. In this process, a desired pattern can be expressed. That is, in the conventional process, since the fabric is fabricated and then subjected to film lamination, even when weaving according to a desired pattern, there is a disadvantage in that the pattern is hardly shown in the process of performing the laminating process. none.

The woven product is tentered to produce a fabric. The tentering process is one of the finishing steps in manufacturing a fabric, that is, a process of fixing the width of the fabric uniformly using a tenter. In the tenter, the sides of the fabric are held by pins or clips. It refers to a process of raising and fixing the temperature of the tenter at about 150 ° C to 180 ° C, preferably 160 ° C to 170 ° C in a situation of maintaining a constant width in the weft direction. That is, this step is a step of fixing the woven product by applying heat to fix it, and refers to an operation for pasting in order to prevent the thread from being pushed.

After the weaving process, a dough screening process of inspecting and washing the product woven before the tentering process may be further performed.

The flame retardant lyocell fiber of the present invention is free from mechanical property deterioration due to the addition of a flame retardant in the spinning step or the polymerization step, and is directly coated on the yarn, thereby producing excellent flame retardant fiber material with uniform adhesion performance and coating stability, and coated yarn The round strand coating is rounded to produce high quality products. In particular, the fabric produced using the flame retardant lyocell fibers of the present invention can be used for various purposes such as office roll blinds, curtains, shades of open air cafes, mosquito nets, beach chairs.

In addition, when using the flame-retardant lyocell fibers of the present invention there is an advantage that can suppress the generation of carbon monoxide, carbon dioxide poison gas generated when using synthetic fibers such as conventional polyester fibers.

In the present invention, matters other than those described above can be added or subtracted as required, and therefore, the present invention is not particularly limited thereto.

According to the present invention, the polymer resin coating is applied directly to the lyocell fiber itself, thereby maintaining excellent mechanical properties and effectively imparting excellent flame retardance without deteriorating fiber properties and spinning properties due to the addition of a flame retardant.

Hereinafter, the present invention will be described in more detail with reference to the following examples. However, the scope of the present invention is not limited to the following examples.

Example 1

The lyocell fibers were coated at 170 ° C. with the polyvinylchloride resin composition. The coating composition was added to 65% by weight of polyvinyl chloride resin having a polymerization degree of 1200, 20% by weight of diisodecyl phthalate as a phthalic plasticizer and 5% by weight of aluminum hydroxide as an inorganic flame retardant, and an additive of an azo colorant and an imidazole antibacterial agent. It was prepared by adding 10% by weight.

After the coated lyocell fibers were wound and squeezed, weaved and subjected to a dough screening process, a tentering process was applied to heat at 160 ° C. to prepare a flame retardant lyocell fabric.

As a result of evaluating various physical properties of the flame-retardant lyocell fiber yarn and fabric prepared as described above are shown in Table 2.

Examples 2-5

A flame-retardant lyocell fabric was prepared in the same manner as in Example 1 except that the polymerization degree, content and process conditions of the polyvinyl chloride coating composition were changed as shown in Table 1 below.

As a result of evaluating various physical properties of the flame-retardant lyocell fiber yarn and fabric prepared as described above are shown in Table 2.

division Example 1 Example 2 Example 3 Example 4 Example 5 Polyvinylchloride resin polymerization degree 1200 1400 1200 1200 600 Polyvinyl chloride resin content (% by weight) 65 60 65 65 65 Plasticizer ingredients Diisodecyl phthalate Diisodecyl phthalate Diisodecyl phthalate Diisodecyl phthalate Diisodecyl phthalate Plasticizer content (% by weight) 20 25 20 20 20 Flame Retardant Ingredients Aluminum hydroxide Aluminum hydroxide Aluminum hydroxide Aluminum hydroxide Aluminum hydroxide Flame retardant content (% by weight) 5 10 5 5 5 Coating temperature (℃) 170 170 160 170 170 Tentering Temperature (℃) 160 160 160 150 160

Comparative Example 1

A flame-retardant lyocell fabric was prepared in the same process and conditions as in Example 1 except that the polymer resin coating was not performed.

The results of evaluating various physical properties of the lyocell fiber yarn and fabric are shown in Table 2 below.

Comparative Example 2

A flame-retardant lyocell fabric was prepared in the same process and conditions as in Example 1 except that polyester fibers were used instead of lyocell fibers.

The results of evaluating various physical properties of the polyester fiber yarns and fabrics are shown in Table 2 below.

Various physical properties in the present invention were evaluated by the following method.

(1) strong and faithful

A 250 mm sample was measured by tensile testing at a rate of 300 mm / min based on ASTM D885. The strength obtained by dividing the strength of the measured yarn by the weight of 9,000 m of yarn was determined as the strength of the yarn.

(2) shrinkage

In the test light, the length difference was measured after leaving the sample at 190 ° C. for 15 minutes while applying 0.01 g / d load. Measured.

(3) Flame retardant performance

It was determined by the following formula 1 according to the limit oxygen index (Limit Oxygen Index) by the KS M 3032 method.

[Calculation 1]

(4) texture evaluation method

In particular, the sensory evaluation of the dry touch feeling was performed about the texture and the touch of the fabric.

The evaluation method evaluated as being (circle) and what was inferior to that suitable for the surface dough use of the cloth which was cloth | clothed, and ×.

(5) Designability (glossiness, color development) evaluation method

In order to evaluate the designability of the fabric, the sensory evaluation was performed on the glossiness of the sample nonwoven fabric and the color development after dyeing, respectively.

The evaluation method performed the sensory evaluation from a visual viewpoint.

About glossiness, the thing of the level suitable for use in the surface dough use of the cloth | clothed furniture evaluated as (circle) and the unsuitable thing as x.

In the color development property, it was evaluated that (circle) and inadequate ones were levels suitable for use with respect to the color development properties required for the surface stocking use of the cloth.

The dyeing method is cationic dye (Maxilon® Yellow®2RL0.55% omf, Maxilon®Red®GRL0.25% omf, Maxilon®Blue®GRL0.30% omf: manufactured by Ciba-Geigy Co., Ltd.), and as a preparation, acetic acid and acetic acid Using a sodium and anionic dispersant 2% omf (LevenolWX: manufactured by Kao Co., Ltd.) and a catalyst agent 0.4% omf (sodium lauryl sulfate), boil the mixture at a bath ratio of 1: 2.5 at atmospheric pressure for 1 hour and centrifugal dehydrator. After dehydration, the resultant was dried at room temperature to obtain a fabric having a dark brown color.

The results of evaluating various physical properties of the fabrics and fiber yarns prepared according to Examples 1 to 5 and Comparative Examples 1 to 2 are as shown in Table 2 below.

division Example Comparative example One 2 3 4 5 One 2 Elongation (%) 10 11 10 12 10 6 24 Strength (g / d) 8.3 7.9 8.1 7.6 7.6 6.7 7.8 Shrinkage (%) 0.5 0.8 0.4 0.7 0.7 0.6 2.8 LOI 33 30 32 33 32 18 29 Luster O O O O O X O Color development O O O O O X X Texture evaluation O O O O X X X Workability O O O O O X X

As shown in Table 2, the fiber yarns and fabrics of Examples 1 to 5 in which the direct coating on the lyocell fibers with the polymer resin composition according to the present invention maintain excellent mechanical properties such as physical properties, workability, It can be seen that the flame retardancy of LOI of 30 or more can be further improved. On the other hand, Comparative Example 1, which does not perform a separate polymer resin coating is not good in terms of flame retardancy, Comparative Example 2 using the conventional polyester fiber can be seen that the high shrinkage rate is not good in terms of workability. .

In the present invention, in order to impart flame retardance to the lyocell fiber, by performing a polymer resin coating directly on the lyocell fiber itself, it is possible to maintain excellent mechanical properties without further deteriorating the physical properties and the radioactivity of the fiber and further improve the excellent flame retardancy, industrial or construction It can be applied as various industrial fibers for interior use.

Claims (10)

A flame retardant lyocell fiber surface-treated with a coating composition comprising a polymeric resin, a phthalic acid or adipic acid plasticizer, and an inorganic or halogen-phosphorous flame retardant. The method of claim 1, The polymer resin is at least one member selected from the group consisting of polyvinyl chloride, polyurethane, and polyethylene flame retardant lyocell fiber. The method of claim 1, The phthalic acid-based plasticizers include dioctyl phthalate, dibutyl phthalate, dimethyl phthalate, diethyl phthalate, diheptyl phthalate, dinonyl phthalate, diisodecyl phthalate, diundecyl phthalate, ditridecyl phthalate, butylbenzyl phthalate, and butyla. One or more flame retardant lyocell fibers selected from the group consisting of uryl phthalate. The method of claim 1, The adipic acid-based plasticizer is at least one flame retardant lyocell fiber selected from the group consisting of dioctyl adipate, diisononyl adipate, and diisodecyl adipate. The method of claim 1, The amount of the plasticizer is 10 to 50 parts by weight per 100 parts by weight of the polymer resin flame retardant lyocell fiber. The method of claim 1, The inorganic flame retardant is flame retardant lyocell fiber selected from the group consisting of magnesium hydroxide, aluminum hydroxide, and antimony trioxide. The method of claim 1, The halogen-phosphorous flame retardant is at least one selected from the group consisting of tris (2,4-dichloropropyl) phosphate, tris (2-chloropropyl) phosphate, tris (2-chloroethyl) phosphate, and chlorinated organic polyphosphate. Flame retardant lyocell fiber. The method of claim 1, The flame retardant content is 5 to 30 parts by weight per 100 parts by weight of the polymer resin flame retardant lyocell fiber. Coating a lyocell fiber with a coating composition comprising a polymer resin, a phthalic acid or adipic acid plasticizer and a flame retardant, and Weaving and tentering the coated lyocell fibers with warp and weft yarns Method for producing a flame retardant fabric comprising a. 10. The method of claim 9, The coating process is a method of producing a flame retardant fabric is carried out at 120 to 180 ℃.