KR101306234B1 - Cellulose fiber, preparation method thereof, and celluose fabric comprising the same - Google Patents

Abstract

The present invention relates to a cellulosic fiber having excellent flame retardancy and dyeing property, a manufacturing method thereof, and a cellulose-based fabric comprising the same.

The cellulose-based fiber includes a cellulose polymer in which hydrogen is substituted at 1 to 60% of the hydroxy groups included in the cellulose with a phosphorus-based flame-retardant functional group bonded with a cation of an alkali metal, and the flame retardant functional group is substituted to exhibit excellent flame retardancy. In addition, it can exhibit excellent dyeing property with respect to the cationic dye.

Cellulose Fiber, Flame Retardant, Dyeing, Phosphorus Flame Retardant, Cationic Dye

Description

Cellulose fiber, manufacturing method thereof, and cellulosic fabric comprising the same {CELLULOSE FIBER, PREPARATION METHOD THEREOF, AND CELLUOSE FABRIC COMPRISING THE SAME}

The present invention relates to a cellulosic fiber, a manufacturing method thereof, and a cellulose-based fabric comprising the same.

Cellulose-based fibers such as cotton fibers have a soft touch and a small irritation to the human body as well as excellent chemical resistance and heat resistance, and thus are widely used in various industrial fields as well as paper, clothing or textiles.

By the way, since the cellulose-based fiber exhibits a very burning property, it is necessary to impart flame retardancy to the cellulose-based fiber in order to be used more preferably for clothes or fabrics.

In addition, since the cellulose fibers are used in a dyed state in many cases used in clothing or fabrics, it is necessary to exhibit excellent dyeing properties.

On the other hand, various flame retardants have been developed and used in order to impart better flame retardancy to various plastics or fibers conventionally, and examples of such flame retardants include phosphorus-based flame retardants or halogen-based flame retardants.

However, these flame retardants do not impart excellent flame retardancy even if applied to the cellulose fibers, or even if the degree of flame retardancy has a disadvantage in reducing the dyeability of the cellulose fibers. For this reason, the cellulose fiber which shows the outstanding flame retardance and dyeability is not provided yet, The necessity for this is increasing.

The present invention is to provide a cellulose fiber and a method for producing the same that exhibits excellent flame retardancy and dyeability.

The present invention also provides a cellulose-based fabric showing excellent physical properties using the cellulose-based fibers.

The present invention provides a cellulose-based fiber comprising a cellulose polymer in which hydrogen is substituted at 1 to 60% of the hydroxy groups included in the cellulose of the following formula (1) with a phosphorus-based flame retardant functional group bonded with a cation of an alkali metal.

[Formula 1]

In Formula 1, n represents the degree of polymerization of cellulose.

In the cellulose-based fiber, the phosphorus-based flame retardant functional group may include a flame retardant functional group of Formula 2 or 3 below:

 (2)

(3)

In Formulas 2 and 3, R ₃ is hydrogen, alkyl having 1 to 10 carbon atoms or phenyl, and M is an alkali metal.

The present invention also comprises the steps of reacting the cellulose of formula 1 with a phosphorus flame retardant or anhydride thereof; And reacting the reaction product with an alkali metal hydroxide to provide a method for producing the cellulose fiber of claim 1.

[Formula 1]

In Formula 1, n represents the degree of polymerization of cellulose.

In the manufacturing method of the cellulose-based fiber, the phosphorus-based flame retardant or anhydride thereof may include a flame retardant of the formula (4) or a flame retardant anhydride of the formula (5).

 [Formula 4]

[Chemical Formula 5]

In Formulas 4 and 5, R ₁ and R ₂ are each independently hydrogen, hydroxyethyl or hydroxypropyl, at least one of R ₁ and R ₂ is hydrogen, R ₃ is hydrogen, alkyl having 1 to 10 carbon atoms Or phenyl.

In addition, the present invention provides a cellulose-based fabric comprising the cellulose-based fiber.

Hereinafter, the cellulose fiber according to the present invention, a manufacturing method thereof and a cellulose-based fabric will be described in more detail.

The cellulose fiber of the present invention includes a cellulose polymer in which hydrogen is substituted at 1 to 60% of the hydroxyl group contained in the cellulose of Formula 1 with a phosphorus flame retardant functional group bonded with a cation of an alkali metal. In such a cellulose polymer, the phosphorus-based flame retardant functional group may be one in which a cation of an alkali metal is bonded to a flame-retardant functional group derived from any phosphorus-based flame retardant, and among these, may be a flame-retardant functional group represented by Chemical Formula 2 or 3 above.

Since the cellulose-based fiber has a phosphorous flame retardant functional group (for example, flame retardant functional group of Formula 2 or 3) derived from a phosphorus flame retardant or an anhydride thereof (for example, flame retardant of Formula 4 or flame retardant anhydride of Formula 5) In addition, it can exhibit excellent flame retardancy which does not burn well. In addition, the phosphorus-based flame retardant functional group is ion-bonded with an alkali metal cation (for example, M ⁺ of Formula 2 or 3). When the cellulosic fibers are dyed with a cationic dye, Substituted with the alkali metal cation can be easily ion bonded. Thus, the cellulose fibers may exhibit excellent dyeability for cationic dyes. Therefore, the cellulose-based fiber may exhibit excellent dyeability with excellent flame retardancy.

In contrast, in a cellulose fiber in which an alkali metal cation is not bound and only flame retardant functional groups derived from a conventional phosphorus flame retardant are bound, a large portion of the hydroxy groups included in the cellulose is already bonded to the flame retardant functional group, and the dye is applied to the cellulose itself. It is difficult for ions to bind and dye ions to bond with the flame retardant functional groups. For this reason, such a cellulose fiber shows low dyeability compared with the cellulose fiber of this invention.

On the other hand, in the cellulose fiber of the present invention, 1 to 60% of the hydroxy group contained in the cellulose of the formula (1 part or all of the hydroxy group included in the amorphous region of the cellulose and part of the hydroxy group included on the surface of the crystal region) Hydrogen is substituted with the phosphorus-based flame retardant functional group. If the phosphorus-based flame retardant functional group is introduced only to less than 1% of the hydroxyl group, the flame retardancy of the cellulose fiber may not be sufficient, and it is difficult to introduce the phosphorus-based poorly soluble functional group into the hydroxyl group included in the crystal region of the cellulose. It is not easy to obtain cellulose fibers in which the phosphorus-based poorly water-soluble functional groups are introduced into excess hydroxyl groups.

When the cellulose fibers of the present invention are dyed with a cationic dye, the cation of an alkali metal in a flame retardant functional group substituted with the cellulose polymer has a chemical structure substituted with a dye ion derived from a cationic dye. Cellulose fibers dyed in this way can maintain excellent dyeability and yet exhibit excellent flame retardancy.

In addition, the cellulose fibers of the present invention may have a conventional molecular weight, for example, the cellulose may have a weight average molecular weight of 10,000 ~ 1,000,000.

In addition, the cellulose fiber may be a cotton fiber generally applied to clothing or fabrics, and may be various cellulose fibers.

In addition, any cationic dye applicable to cotton fibers or the like may be applied for dyeing the cellulose fibers of the present invention, and in this case, the cellulose fibers of the present invention may exhibit excellent dyeing properties. Specifically, the cationic dye is C.I. Basic Black 2 or 7; C.I. Basic Blue 1, 3, 6, 7, 9, 11, 12, 16, 17, 24, 26, 40, 41, 57, 66, 80, 123 or 159; C.I. Basic Green 1, 4 or 5; C.I. Basic Orange 2, 14, 21 or 54; C.I. Basic Red 1, 2, 5, 9, 10, 13, 22, 23, 29, 46, or 54, among which C.I. It can be Basic Red 23.

In addition, the cellulose polymer and the cellulose fiber including the same may be substituted with phosphorus-based flame retardant functional groups having various alkyl or phenyl introduced at the R ₃ position in Formula 2 or 3, and among these, dyeability or the like of cellulose fibers. In consideration of physical properties, phosphorus-based flame retardant functional groups into which methyl or phenyl are introduced may be substituted. In addition, a cation of any alkali metal (M) may be introduced into the phosphorus-based flame retardant functional group, and among these, a cation of sodium or potassium may be introduced in consideration of ease of substitution with dye ions derived from cationic dyes and dyeing properties. Can be.

On the other hand, the above-described cellulose fiber is a step of reacting the cellulose of the formula (1) with a phosphorus flame retardant or anhydride thereof; And reacting the reaction product with an alkali metal hydroxide. In this manufacturing method, the phosphorus-based flame retardant or anhydride thereof may be any phosphorus-based flame retardant or anhydride thereof, and among these, may be the flame retardant of Formula 4 or flame retardant anhydride of Formula 5.

In this production method, first, the cellulose of the formula (1) and the phosphorus flame retardant or anhydride thereof (for example, the flame retardant of the formula (4) or the flame retardant anhydride of the formula (5) are reacted. As a result of this reaction, a dehydration condensation reaction is carried out between the hydroxy group of the cellulose and the hydroxy group or carboxylic acid of the phosphorus-based flame retardant or anhydride thereof. At least 1% and at most 60% of the hydroxy groups contained in the cellulose as part of the hydroxyl groups contained on the surface of the hydrogen is replaced with poorly soluble functional groups (for example, functional groups represented by the following formula 6 or 7).

[Formula 6]

[Formula 7]

That is, as a result of this reaction, since the poorly water-soluble work container derived from a phosphorus flame retardant or its anhydride is introduce | transduced into cellulose, the said reaction product can show the outstanding flame retardance. In this state, however, dye ions are difficult to be introduced, and thus the dyeability is insufficient.

On the other hand, before the reaction step, the step of drying the cellulose of Formula 1 at 1 ~ 10 minutes at 70 ~ 100 ℃, this drying step can be performed at about 85 ℃ for about 5 minutes. Through such a drying step, the organic solvent and the like contained in the cellulose may be effectively removed, and then the reaction may proceed preferably.

In the reaction step, phosphorus-based flame retardants or anhydrides thereof in which various alkyls or phenyls are introduced at the R ₃ position in Chemical Formula 4 or 5 may be used, and among them, methyl or Phosphorus-based flame retardants in which a phenyl group is introduced or anhydrides thereof can be used. In addition, R ₁ and R ₂ there of one of the position, the hydrogen for the dehydration condensation reaction is introduced into the other position, the phosphorus-based flame retardant A is hydrogen, hydroxyethyl or hydroxypropyl introduced may be used, for example, the R ₁ A phosphorus flame retardant in which hydrogen is introduced at the position and hydrogen or hydroxyethyl is introduced at the R ₂ position can be used. The anhydride of the phosphorus-based flame retardant may open a ring in the reaction process to cause a dehydration condensation reaction with the cellulose.

In addition, the reaction step may be carried out under water or alcohol or a mixed solvent thereof in consideration of the solubility of each reactant, etc., and in consideration of reactivity, for example, a catalyst such as sodium hypophosphite (NaH ₂ PO ₂ ). It may also proceed in the presence.

And, the reaction step may be carried out at a temperature of 160 ~ 220 ℃. As the reaction step proceeds at such a temperature, a poorly soluble functional group (for example, the functional group represented by Chemical Formula 6 or 7) is introduced at an appropriate ratio among the hydroxyl groups of the cellulose, so that the cellulose fiber may exhibit excellent flame retardancy, but also a side reaction. Etc. can be suppressed.

In addition, the reaction step may be performed by adding the cellulose and the phosphorus-based flame retardant or anhydride thereof in a weight ratio of 9: 1.

On the other hand, after the reaction step, the reaction product is reacted with alkali metal hydroxide, whereby the cellulosic fibers of the present invention described above can be obtained. As already described above, such cellulose fibers can exhibit excellent flame retardancy as the phosphorous flame retardant functional group (for example, the flame retardant functional group of Formula 2 or 3) is introduced, and the cation of the alkali metal can be easily replaced with dye ions. Can exhibit excellent dyeing properties for cationic dyes.

In this reaction step, any alkali metal hydroxide may be used, and among these, sodium hydroxide or potassium hydroxide may be used in consideration of the dyeability of the cellulose fibers.

In addition, the reaction step may be performed by adding the reaction product and the alkali metal hydroxide in an equivalent ratio of 1: 3.

After the reaction with the alkali metal hydroxide, the step of obtaining the cellulose fibers in a dyed state by reacting the cellulose fibers of the present invention with a cationic dye. The dyed cellulosic fibers thus obtained can easily introduce dye ions derived from cationic dyes to maintain excellent dyeability and yet exhibit excellent flame retardancy.

In this dyeing step, any cationic dye applicable to cotton fibers or the like can be used, among which C.I. Basic red 23 can be used.

According to the above-described manufacturing method, cotton fibers and various other cellulose fibers showing excellent dyeability and flame retardancy can be obtained.

On the other hand, the present invention also provides a cellulose-based fabric comprising the cellulosic fibers of the present invention described above. Such a cellulose-based fabric can be obtained by applying a conventional weaving process or the like to the cellulose-based fiber.

In addition, the cellulose-based fabric of the present invention may be any cellulose-based fabric, for example, cotton fabric. Since the cellulose-based fabric of the present invention exhibits excellent flame retardancy and dyeing property, it can be preferably applied to clothes or fabrics.

As described above, the cellulosic fibers of the present invention and cellulose-based fabrics comprising the same may exhibit excellent dyeing property for cationic dyes with excellent flame retardancy.

Hereinafter, the configuration and effects of the present invention will be described in more detail with reference to specific examples and comparative examples in order to help understanding of the present invention. However, the following examples are only intended to more clearly understand the present invention, and are not limited to the following examples of the present invention.

 [Examples and Comparative Examples]

Example 1 Preparation of Cellulose Fibers

First, 21.4 g of a flame retardant of formula 4 wherein R ₁ and R ₂ are each hydrogen and R ₃ is phenyl was dissolved in 100 ml of water or ethanol. This solution was treated with 10 g of cotton fiber, and the cotton fiber was dried at 85 ° C. for 5 minutes. Then, the cotton fibers and the flame retardant were reacted for 3 minutes at 140 ° C, 160 ° C, 180 ° C, 200 ° C and 220 ° C, respectively.

Then, 100 ml of 0.1 M aqueous potassium hydroxide solution was added to the cotton fibers treated with the flame retardant and treated.

Thereafter, the cotton fibers were washed with a mixed solution of ethanol / water (50/50, v / v) for 10 minutes to remove unreacted residues, and rinsed with water to introduce cotton fibers into which a flame retardant functional group of Formula 2 or 3 was introduced. Got it.

Example 2: Preparation of Cellulose Fibers

A cotton fiber was obtained in the same manner as in Example 1, except that 0.4 g of sodium hypophosphite was added in the reaction with the flame retardant and the reaction was carried out in the presence of such a catalyst.

Example 3: Preparation of Cellulose Fibers

In the reaction with the flame retardant, cotton fibers were obtained in the same manner as in Example 1, except that R ₁ and R ₂ were each hydrogen and hydroxyethyl, and R ₃ was methyl.

Example 4: Preparation of Cellulose Fibers

Cotton fiber was obtained in the same manner as in Example 3, except that 0.4 g of sodium hypophosphite was added in the reaction with the flame retardant and the reaction was carried out in the presence of such a catalyst.

Comparative Example 1: Preparation of Cellulose Fibers

A cotton fiber was obtained in the same manner as in Example 1, except that the treatment with potassium hydroxide was not carried out.

Comparative Example 2: Preparation of Cellulose Fibers

Cotton fibers were obtained in the same manner as in Example 2, except that the treatment with potassium hydroxide was not carried out.

Comparative Example 3: Preparation of Cellulose Fibers

A cotton fiber was obtained in the same manner as in Example 3, except that the treatment by adding potassium hydroxide was not carried out.

Comparative Example 4: Preparation of Cellulose Fibers

A cotton fiber was obtained in the same manner as in Example 4, except that the treatment with potassium hydroxide was not carried out.

Test Example 1

The cotton fibers obtained in Comparative Examples 1 to 4 were used as C.I. Stained by reacting with 3 g of Reactive Blue 4. An IR stainer was used for this staining.

The dyeability (dye strength) of the cotton fiber thus dyed was measured by X-Rite Match-Rite spectrometer. The dyeing intensity measurement results are shown in FIG. 1. In Figure 1, the horizontal axis represents the temperature at which the cotton fiber and the flame retardant reacted, and the vertical axis represents the K / S value for the dyeing intensity.

In addition, the flame retardancy of the cotton fibers of 1 to 4 in the comparison was measured by the KS K 0585 method.

As a result of this test, it was found that the flame retardancy of the cotton fiber improved as the temperature at which the cotton fiber reacted with the flame retardant increased. This is because the flame retardant functional group derived from the said flame retardant was introduced in the higher ratio among the hydroxyl groups contained in the cellulose structure of cotton fiber.

1, it was found that as the temperature at which the cotton fiber reacted with the flame retardant increases, the flame retardancy is improved but the dyeing property is lowered. In particular, it was found that when the cotton fiber and the flame retardant were reacted in the vicinity of 200 ° C., the cotton fiber showed very low dyeability (dyeing strength). This is because the flame retardant functional group is already introduced to a substantial portion of the hydroxy group included in the cellulose structure of the cotton fiber, which makes it difficult to bind the dye ions and the dye ion to the flame retardant functional group.

Test Example 2

C.I. Dyeing (dye strength) and flame retardance of the cotton fibers of Comparative Examples 1 to 4 were measured in the same manner as in Test Example 1, except that Reactive Blue 19 was used. The result is as shown in FIG.

According to the measurement result of Test Example 2, as the temperature at which the cotton fiber reacted with the flame retardant increases, the flame retardancy of the cotton fiber is improved, but as shown in FIG. 2, the dyeability (dyeing strength) is deteriorated. Turned out.

Accordingly, it has been found that cotton fibers containing only flame retardant functional groups derived from phosphorus-based flame retardants can exhibit low dyeability.

Test Example 3

C.I., a cationic dye. Dyeing (dye strength) and flame retardance of the cotton fibers of Examples 1 to 4 were measured in the same manner as in Test Example 1, except that Basic Red 23 was used.

As a result, the cotton fibers of Examples 1 to 4 surprisingly exhibited excellent flame retardancy corresponding to Comparative Examples 1 to 4, while the cotton fibers had a minimum K even when the cotton fibers and the flame retardant were reacted at a high temperature of about 200 ° C. It has been found that it can exhibit significantly higher dyeability (dye intensity) of / S value = 12 or more.

This is confirmed because potassium ions are bonded to the flame retardant functional groups bonded to the cotton fiber, because the potassium ions can be easily substituted with the dye ions to help the dye ions bind.

Cellulose-based fibers and cellulose-based fabrics comprising the same according to the present invention exhibits excellent flame retardancy and dyeability, and thus may be preferably applied to clothing or fabrics.

Figure 1a is a C.I. As the degree of reaction of the cotton fiber and the flame retardant in Test Example 1 increases. This is a graph showing the change in the dyeability of cotton fibers for Reactive Blue 4,

Figure 1b is a C.I. As the reaction degree of the cotton fiber and the flame retardant in Test Example 2 increases. This is a graph showing the change in the dyeability of cotton fibers for reactive blue 19.

Claims (19)

In 1 to 60% of the hydroxy group contained in the cellulose of the formula (1) is hydrogen, Cellulose fibers comprising a cellulose polymer substituted with a phosphorus-based flame retardant functional group bonded to the cation of the alkali metal represented by the formula (2) or (3): [Formula 1]

In Formula 1 n represents the degree of polymerization of cellulose,  (2)

(3)

In Formulas 2 and 3, R ₃ is hydrogen, alkyl having 1 to 10 carbon atoms or phenyl, and M is an alkali metal. delete The method of claim 1, The cellulose fibers are dyed with a cationic dye, The cellulose fiber in which the cation of an alkali metal is substituted by the dye ion derived from cationic dye in the flame-retardant functional group substituted by the said cellulose polymer. The method of claim 1, The cellulose is a cellulose fiber having a weight average molecular weight of 10,000 ~ 1,000,000. The method of claim 1, A cellulose fiber in which the cellulose fiber is a cotton fiber. The method of claim 3, wherein The cationic dye is C.I. Cellulose fibers, including Basic Red 23. The method of claim 1, The cellulose-based polymer is a cellulose-based fiber substituted with a flame-retardant functional group in the formula 2 or 3 R ₃ is methyl or phenyl, M is sodium or potassium. Reacting cellulose of Formula 1 with a phosphorus flame retardant of Formula 4 or 5 or an anhydride thereof; And A method for producing the cellulose-based fiber of claim 1 comprising the step of reacting the reaction product with an alkali metal hydroxide: [Formula 1]

In Formula 1 n represents the degree of polymerization of cellulose, [Formula 4]

[Chemical Formula 5]

In Formulas 4 and 5, R ₁ and R ₂ are each independently hydrogen, hydroxyethyl or hydroxypropyl, at least one of R ₁ and R ₂ is hydrogen, R ₃ is hydrogen, alkyl having 1 to 10 carbon atoms Or phenyl. delete 9. The method of claim 8, After the reaction with the alkali metal hydroxide, reacting the reaction product with a cationic dye to obtain a cellulose fiber dyed with the cationic dye. 9. The method of claim 8, The manufacturing method of the cellulose fiber which the said cellulose fiber becomes a cotton fiber. 11. The method of claim 10, The cationic dye is C.I. A method for producing a cellulose-based fiber comprising Basic Red 23. 9. The method of claim 8, A process for producing cellulose fibers using a flame retardant of formula 4 or a flame retardant anhydride of formula 5 wherein R ₃ is methyl or phenyl. 9. The method of claim 8, The alkali metal hydroxide is a method of producing a cellulose-based fiber containing sodium hydroxide or potassium hydroxide. 9. The method of claim 8, Before the reaction with the phosphorus-based flame retardant or anhydride thereof, the method of producing a cellulose fiber further comprising the step of drying the cellulose of the formula (1) at 70 ~ 100 ℃ for 1 to 10 minutes. 9. The method of claim 8, The reaction step with the phosphorus-based flame retardant or anhydride thereof is a method of producing a cellulose-based fiber is carried out under alcohol or water or a mixed solvent thereof. 9. The method of claim 8, Reaction step with the phosphorus-based flame retardant or anhydride thereof, the manufacturing method of the cellulose-based fiber is carried out at 160 ~ 220 ℃. Cellulose-based fabric comprising the cellulosic fibers of claim 1. The method of claim 18, Cellulose-based fabric wherein the cellulose-based fabric is a cotton fabric.

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