JP2001164463A - Flameproof processing agent for polylactic acid fiber and method for flameproof processing of polylactic acid fiber structure - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a flameproof processing agent for polylactic acid fibers capable of carrying out flameproof processing of the biodegradable polylactic acid fibers while retaining the strength of the fibers. SOLUTION: This flameproof processing agent for the polylactic acid fibers comprises both an alicyclic bromine compound and a phosphoric ester-based compound.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a flameproofing agent for polylactic acid fibers and a method for flameproofing polylactic acid fiber structures.

[0002]

2. Description of the Related Art Conventionally, curtains, beddings (futons,
Flameproof products such as blankets) have been used in which polyester fibers represented by polyethylene terephthalate (PET) or the like are subjected to flameproof processing. However, in recent years, from the viewpoint of global environmental protection, biodegradable polylactic acid fibers have attracted attention instead of the above polyester fibers such as PET, and a technology for applying the polylactic acid fibers to flameproofing products has been expected.

[0003]

However, the above-mentioned polylactic acid fiber is subjected to the same flameproofing treatment as that of polyester fiber such as PET due to physical properties such as lower melting point than polyester fiber such as PET. In such a case, there is a problem that the strength of the fiber is reduced. As described above, it is a fact that an appropriate flameproofing technique has not been established for the polylactic acid fiber.

[0004] The present invention has been made in view of such circumstances, and a flame retardant for polylactic acid fibers that can perform flameproofing on biodegradable polylactic acid fibers while maintaining fiber strength. It is an object of the present invention to provide a processing agent and a flameproofing method for a polylactic acid fiber structure.

[0005]

In order to achieve the above-mentioned object, the present invention provides a flame retardant for polylactic acid fibers containing both an alicyclic bromine compound and a phosphate ester-based compound as the first invention. Make a summary.

Further, the present invention provides a treatment liquid containing the flame retardant for polylactic acid fibers, and the polylactic acid fiber structure is immersed in the treatment liquid at 110 to 130 ° C.
The second gist is a method for flameproofing a polylactic acid fibrous structure that is heat-treated at a temperature of.

That is, the present inventors have conducted intensive studies to obtain a flameproofing agent capable of performing flameproofing on biodegradable polylactic acid fibers while maintaining the strength of the fibers. . As a result, they have found that when both an alicyclic bromine compound and a phosphate ester compound are used in combination, the flame retardancy is improved as compared with the case where these are used alone, and the present invention has been achieved.

[0008]

Next, embodiments of the present invention will be described in detail.

The flame retardant for polylactic acid fibers of the present invention can be obtained by using both an alicyclic bromine compound and a phosphate compound.

In the present invention, the polylactic acid fiber to be subjected to the flameproofing treatment preferably has an optical purity of 90% or more, more preferably 95% or more. In particular, 9
If it is 7% or more, it is most suitable for fiberization.

The alicyclic bromine compound is not particularly limited. For example, hexabromocyclododecane (HBC
D), tetrabromocyclohexane, tetrabromocyclododecane (TBCD) and the like. These may be used alone or in combination of two or more.

The alicyclic bromine compound may be a single compound or a mixture as described above, but in any case, it is preferable to set the melting point to be lower than 200 ° C. Preferably it is the range of 150 to less than 200 ° C. That is, when the melting point of the alicyclic bromine compound is 200 ° C. or higher, the internal permeation into the polylactic acid fiber tends to decrease, and when it is lower than 150 ° C., the flame resistance of the polylactic acid fiber tends to decrease. Because. In addition, since several kinds of stereoisomers exist in the alicyclic bromine compound, for example, HBCD and the like, even if the same compound, the melting point may be different depending on the kind of the stereoisomer.

When the alicyclic bromine compound is a mixture, the alicyclic bromine compound (X) having a melting point of not less than 200 ° C.
And an alicyclic bromine compound (Y) having a melting point of less than 200 ° C. are preferably used as a mixture. In this case, the weight mixing ratio of the two is preferably set in the range of X: Y = 1: 0.1 to 1: 1 and particularly preferably X: Y = 1: 0.3 to
1: 0.6. That is, when the weight mixing ratio of the alicyclic bromine compound (Y) having a melting point of less than 200 ° C. is less than 0.1, the internal permeation into the polylactic acid fiber tends to decrease, and conversely, the melting point is less than 200 ° C. Alicyclic bromine compound (Y)
If the weight mixing ratio exceeds 1, the flame retardancy of the polylactic acid fibers tends to be reduced.

The phosphate compound used together with the alicyclic bromine compound is not particularly limited. For example, tricresyl phosphate, triethyl phosphate, tributyl phosphate, triphenyl phosphate (TPP), cresyl diphenyl phosphate, Phosphates such as xylenyl diphenyl phosphate, tris (tribromoneopentyl) phosphate,
Halogen-containing phosphates such as tris (bromoethyl) phosphate and tris (dibromopropyl) phosphate, and condensed phosphates such as 1,3-phenylenebis (2,6-dimethylphenylphosphate). These may be used alone or in combination of two or more.

In the flame retardant for polylactic acid fibers of the present invention, the weight mixing ratio of the alicyclic bromine compound and the phosphate compound is such that alicyclic bromine compound: phosphate compound = 1: 0. It is preferably set in the range of 0.05 to 1: 1 and particularly preferably alicyclic bromine compound: phosphate compound = 1: 0.1 to 1: 0.7. That is, when the weight mixing ratio of the phosphate compound is 0.05
When the weight ratio is less than 1, the internal permeation into the polylactic acid fiber tends to decrease. Conversely, when the weight mixing ratio of the phosphate compound exceeds 1, the flame retardancy of the polylactic acid fiber tends to decrease. Because it can be seen.

In the flame retardant for polylactic acid fibers of the present invention, the alicyclic bromine compound is preferably used as a dispersion, and the phosphate compound is preferably used as an emulsion or a dispersion. . The dispersant or emulsifier for dispersing or emulsifying these compounds is not particularly limited. For example, higher alcohol alkylene oxide adducts, alkylphenol alkylene oxide adducts, styrenated alkylphenol alkylene oxide adducts, styrenated phenol alkylene oxide adducts Products, fatty acid alkylene oxide adducts, polyhydric alcohol fatty acid ester alkylene oxide adducts, higher alkylamine alkylene oxide adducts, fatty acid amide alkylene oxide adducts, alkylene oxide adducts of fats and oils, polyalkylenes such as polypropylene glycol ethylene oxide adducts Glycol-type nonionic surfactants, fatty acid esters of glycerol, fatty acid esters of pentaerythritol, sorby Fatty acid esters of Lumpur and sorbitan,
Fatty acid esters of sucrose, alkyl ethers of polyhydric alcohols, polyhydric alcohol type nonionic surfactants such as fatty acid amides of alkanolamines, and carboxylic acid salts such as fatty acid soaps, higher alcohol sulfate salts,
Higher alkyl polyalkylene glycol ether sulfates, sulfated oils, sulfated fatty acid esters, sulfated fatty acids, sulfated esters such as sulfated olefins, formalin condensation of alkylbenzenesulfonates, alkylnaphthalenesulfonates, naphthalenesulfonates, etc. Object, α-
Anionic surfactants such as sulfonates such as olefin sulfonates, paraffin sulfonates, Igepon T type, sulfosuccinic acid diester salts, and phosphoric ester salts such as higher alcohol phosphate ester salts, and the like. These may be used alone or in combination of two or more. further,
In the case of a dispersion, a stabilizer such as carboxymethylcellulose or hydroxyethylcellulose can be used.

The method for dispersing or emulsifying the alicyclic bromine compound or the phosphoric ester compound is not particularly limited. For example, a disperser or an emulsifier such as a homogenizer, a colloid mill, a ball mill, and a sand grinder may be used. Can be done. In this case, the average particle size of the compound is preferably set to 1 μm or less.

The flameproofing agent for polylactic acid fibers of the present invention comprises, for example, a mixture of both an alicyclic bromine compound and a phosphate compound at a predetermined ratio, a dispersant,
It can be produced by appropriately mixing additives such as an emulsifier and a stabilizer as needed.

Next, a particularly preferred method for flameproofing the polylactic acid fiber structure of the present invention will be described. That is, first, a treatment liquid (water diluent) containing the flameproofing agent of the present invention is prepared. Next, using a package dyeing machine such as a liquid jet dyeing machine, a beam dyeing machine, a cheese dyeing machine, etc., in a state where the polylactic acid fiber structure is immersed in a treatment liquid (water dilution liquid) containing the above flame retardant, By performing the heat treatment under the conditions described above, the above-mentioned polylactic acid fiber structure can be subjected to flameproofing.

By immersing the polylactic acid fiber structure in the treatment liquid (water diluent) containing the flame retardant, the flame retardant of the present invention adheres to the surface of the polylactic acid fiber. Flame retardancy can be imparted to the polylactic acid fiber structure. Further, by performing a heat treatment in a state of being immersed in the treatment liquid, the flameproofing agent of the present invention penetrates into and adheres to the inside of the polylactic acid fiber, and thus has a laundry durability against the polylactic acid fiber structure. Can also be given. As a result, the polylactic acid fiber structure treated by the flameproofing method of the present invention has excellent washing resistance as well as flame retardancy.

In applying the flameproofing agent to the polylactic acid fiber by the immersion heat treatment as described above, it may be performed before, simultaneously with, or after dyeing the polylactic acid fiber. However, by performing it at the same time as dyeing, the number of work steps is reduced, and work efficiency is improved.

The temperature conditions for the above heat treatment are 110-110.
The temperature is preferably set in the range of 130 ° C, particularly preferably 115 to 120 ° C. That is, the higher the temperature of the heat treatment, the stronger the adhesion of the flameproofing agent to the polylactic acid fiber. However, if the temperature exceeds 130 ° C, the polylactic acid fiber has an adverse effect such as a decrease in strength and the properties of the polylactic acid fiber. This is because there is a risk of damaging it. Conversely, heat treatment temperature is 110 ° C
If the amount is less than the above, the flameproofing agent may not be well attached to the polylactic acid fiber.

The time of the heat treatment is 15 to
90 minutes is preferable, and particularly preferably 30 to 60 minutes. That is, if the heat treatment time is less than 15 minutes, the flame retardant may not adhere well to the polylactic acid fiber. If the heat treatment time is more than 90 minutes, the polylactic acid fiber has an adverse effect such as a decrease in strength, and This is because the properties of the lactic acid fiber may be impaired.

In the flameproofing method of the present invention, the adsorption amount of the flameproofing agent to the polylactic acid fiber is 0.5% o. w. f
It is preferable to set the above, particularly preferably 2.0
% O. w. f or more. In addition,% o. w. f is a weight ratio with respect to the untreated polylactic acid fiber (in this case, it means an absolute dry weight increase ratio).

When the above-mentioned polylactic acid fiber structure is required to have light fastness or the like, a benzotriazole-based or benzophenone-based ultraviolet ray is added to the treatment solution containing the flameproofing agent of the present invention. Absorbents and other conventionally used agents may be blended.

The polylactic acid fiber structure in the present invention is not particularly limited as long as it is a product using polylactic acid fibers. For example, it is determined that the material has flame resistance according to the fire service law for curtains, blackout curtains, carpets and the like. Flame retardant articles,
Bedding (futons, blankets), tents, curtains, sheets, emergency carry-out bags, disaster prevention hoods, clothing, upholstered furniture, etc., which are desirable to have flameproofing performance according to the fire department's administrative guidance And automotive materials for which flame retardant standards have been set by manufacturers of automotive seats and the like.

The flameproofing method using the flameproofing agent of the present invention can be performed by a pad-dry-steam method, a pad-steam method, a pad-dry-cure method, or the like. Specifically, the polylactic acid fiber structure is subjected to a pad treatment with a treatment liquid (water diluent) containing the flameproofing agent of the present invention, and then subjected to a heat treatment at a temperature of 110 to 130 ° C. The lactic acid fiber structure may be subjected to flameproofing.

Next, examples will be described together with comparative examples.

[Preparation of flameproofing agent]

[0030]

EXAMPLE A 21 g of HBCD (melting point: 205 ° C.) and HB
9 g mixture of CD (melting point: 170 ° C.)
C), 10 g of tricresyl phosphate and 5 g of an adduct of 20 mol of ethylene oxide of tristyrenated phenol as a dispersant were added, and 53 g of water was added thereto with stirring. Thereafter, 2 g of a 10% aqueous solution of carboxymethyl cellulose was added as a stabilizer to prepare a white-dispersed liquid flame retardant.

[0031]

Example B As alicyclic bromine compounds, 26.6 g of HBCD (melting point: 205 ° C.) and HBCD (melting point: 170 ° C.)
C.) 11.4 g of a mixture (melting point: 195 ° C.) was used, and the amount of tricresyl phosphate was changed to 2 g. Otherwise, the procedure of Example A was repeated to prepare a flameproofing agent.

[0032]

Example C As alicyclic bromine compounds, 14 g of HBCD (melting point: 205 ° C.) and HBCD (melting point: 170 ° C.) 6
g of the mixture (melting point: 195 ° C.) and the amount of tricresyl phosphate was changed to 20 g. Otherwise, the procedure of Example A was repeated to prepare a flameproofing agent.

[0033]

EXAMPLE D As an alicyclic bromine compound, 11.2 g of HBCD (melting point: 205 ° C.) and HBCD (melting point: 170 ° C.)
C.) 4.8 g of a mixture (melting point: 195 ° C.), and the amount of tricresyl phosphate was changed to 24 g. Otherwise, the procedure of Example A was repeated to prepare a flameproofing agent.

[0034]

Example E As an alicyclic bromine compound, 27.3 g of HBCD (melting point: 205 ° C.) and HBCD (melting point: 170 ° C.)
C.) 2.73 g of a mixture (mp: 199.degree. C.) were used.
Otherwise, the procedure of Example A was repeated to prepare a flameproofing agent.

[0035]

Example F As alicyclic bromine compounds, 15 g of HBCD (melting point: 205 ° C.) and 1 HBCD (melting point: 170 ° C.)
5 g of the mixture (mp: 185 ° C.) were used. Otherwise, the procedure of Example A was repeated to prepare a flameproofing agent.

[0036]

Comparative Example A As alicyclic bromine compounds, 28 g of HBCD (melting point: 205 ° C.) and 1 HBCD (melting point: 170 ° C.)
2 g of the mixture (mp: 195 ° C.) were used without tricresyl phosphate. Otherwise, the procedure of Example A was repeated to prepare a flameproofing agent.

[0037]

Comparative Example B As an alicyclic bromine compound, 30 g of HBCD (melting point: 205 ° C.) was used, and tricresyl phosphate was not used. Otherwise, the procedure of Example A was repeated to prepare a flameproofing agent.

[0038]

Comparative Example C In place of 10 g of tricresyl phosphate, 40 g of triphenyl phosphate (TPP) was used, and no alicyclic bromine compound was used. Otherwise, the procedure of Example A was repeated to prepare a flameproofing agent.

[Flameproofing method]

[0040]

Examples 1 to 6 and Comparative Examples 1 to 3 Polylactic acid fiber woven fabrics were subjected to a flameproofing treatment using the flameproofing agents shown in Tables 1 and 2 below by the following method. . The structure of the polylactic acid fiber woven fabric was warp: 83.3 dtexf2.
4. Density: 280 lines / 5cm, weft: 111.1 dtex
f24, density 160 lines / 5cm, structure: 2/2 twill weave,
The mass was 88 g / m ² , and as pretreatment, washing was performed at 80 ° C. × 10 minutes in an aqueous solution containing a small amount of a nonionic surfactant.

[Flame-proof treatment a] Using a mini color dyeing machine (manufactured by Texam Giken Co., Ltd.), disperse dye (CI Di
sperse Blue 56) 1% o. w. f, dispersing and leveling agent (Nikka Chemical Co., Nikka Sun Salt SN-130)
0.5 g / l, flameproofing agent 20% o. w. The polylactic acid fiber fabric was immersed in a treatment liquid containing f at a bath ratio of 1:15, and was heat-treated at 120 ° C. for 30 minutes. afterwards,
Soaping agent (Nichika Chemical Co., Ltd., Escudo FR) 2g /
1 in an aqueous solution to which 80 ° C. × 20 minutes have been added,
After washing with hot water and water, it was air-dried. In addition,% o. w.
f is the weight ratio to the untreated polylactic acid fiber fabric.

The flame retardancy test was performed on the thus-treated flame-resistant polylactic acid fiber fabric according to the following criteria. The results are shown in Tables 1 and 2 below.

[Flame Retardancy Test] The afterflame time and carbonized area were measured according to the JIS L-1091 A-1 method. The number of times of flame contact was measured according to JIS L-1091 D method. The tear strength was measured according to JIS L-1096 D method (Pendulum method). In addition, washing
The measurement was performed according to JIS L-1042.

[0044]

[Table 1]

[0045]

[Table 2]

From the results shown in Tables 1 and 2, all of the examples were treated with a flameproofing agent containing both an alicyclic bromine compound and a phosphoric ester compound. It can be seen that both the properties and the washing durability are excellent.

On the other hand, in Comparative Example 1, only the alicyclic bromine compound was used and a flameproofing agent (comparative example A) not used in combination with the phosphate compound was used. It turns out that the property is insufficient. Comparative Example 2 has a high melting point H
Since only BCD (melting point: 205 ° C.) was used and a flameproofing agent (comparative example B product) not used in combination with the phosphate compound was used, it was found that no flameproofness was imparted at all. Comparative Example 3 uses only a phosphoric ester compound and uses a flameproofing agent (Comparative Example C product) that is not used in combination with an alicyclic bromine compound, so that no flameproofness is imparted at all. I understand. In addition, it turns out that the conventional example which did not perform a flameproofing process does not have flame retardancy and washing durability naturally.

[0048]

Examples 7 to 12 and Comparative Examples 4 to 6 Flameproofing was carried out on the same polylactic acid fiber fabric as described above, using the flameproofing agents shown in Tables 3 and 4 below. Processing was performed.

[Flameproofing treatment b] The above-mentioned polylactic acid fiber woven fabric is subjected to padding treatment (drawing ratio: 70%) in a treatment bath containing 20% by weight of a flameproofing agent, and then dried (110 ° C × 1 minute).
Then, a heat set treatment (120 ° C. × 30 seconds) was performed.

The flame retardancy test was carried out in the same manner as described above, using the polylactic acid fiber woven fabric subjected to the flameproofing treatment as described above. These results are shown in Tables 3 and 4 below.

[0051]

[Table 3]

[0052]

[Table 4]

From the results shown in Tables 3 and 4, it can be seen that the excellent results obtained in Examples 7 to 12 having the flameproofing treatment b were substantially the same as those of Examples 1 to 6 having the flameproofing treatment a. I understand. Further, in Comparative Examples 4 to 6 having the flameproofing treatment b, as in Comparative Examples 1 to 3 having the flameproofing treatment a, the flameproofness was insufficient or no flameproofness was imparted. Understand.

[0054]

As described above, since the flame retardant for polylactic acid fibers of the present invention contains both an alicyclic bromine compound and a phosphate ester compound, these may be used alone. Compared to the case, it has excellent flame retardancy and also has excellent washing durability. In addition, the flameproofing method of the present invention comprises the steps of: adding a polylactic acid fiber structure to a treatment liquid containing the flameproofing agent of the present invention;
The heat treatment is performed at a temperature of 0 ° C. That is, by immersing the polylactic acid fiber structure in the treatment liquid containing the flame retardant of the present invention, the flame retardant of the present invention adheres to the surface of the polylactic acid fiber. On the other hand, flame retardancy can be imparted. Further, by performing a heat treatment in a state of being immersed in the treatment liquid, the flameproofing agent of the present invention penetrates into and adheres to the inside of the polylactic acid fiber, and thus has a laundry durability against the polylactic acid fiber structure. Can also be given. As a result, the polylactic acid fiber structure treated by the flameproofing method of the present invention has excellent washing resistance as well as flame retardancy. As described above, according to the present invention, flame-retardant articles such as curtains that are required to have flame-retardant performance based on the Fire Service Law, which has been performed with conventional polyester fibers, and automotive materials for which flame-retardant standards have been set by manufacturers, etc. In addition, a biodegradable polylactic acid fiber can be used, which is preferable from the viewpoint of global environment conservation.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Shigeji Uchida 4-231-1, Bunkyo, Fukui City, Fukui Prefecture Within Nikka Kagaku Co., Ltd. (72) Inventor Tadaatsu Nozu 1-2-2 Umeda, Kita-ku, Osaka-shi, Osaka No. 2 Kanebo Textile Co., Ltd. (72) Inventor Toyoichi Nonaka 1-2-2 Umeda, Kita-ku, Osaka City, Osaka Prefecture Kanebo Textile Co., Ltd. F-term (reference) 4H028 AA28 AA35 BA04 4L033 AB01 AB09 AC05 BA05 BA39 4L048 AA20 BA01 BA02 CA06 CA15 DA13 DA19 EB00

Claims (7)

[Claims] 1. A flameproofing agent for polylactic acid fibers comprising both an alicyclic bromine compound and a phosphate compound. 2. The weight mixing ratio of the alicyclic bromine compound and the phosphate compound is set in the range of alicyclic bromine compound: phosphate compound = 1: 0.05 to 1: 1. The flameproofing agent for polylactic acid fibers according to claim 1, wherein 3. The alicyclic bromine compound has a melting point of 200 ° C.
A mixture of the above alicyclic bromine compound and an alicyclic bromine compound having a melting point of less than 200 ° C., and the mixture has a melting point of 2
The flame retardant for polylactic acid fibers according to claim 1 or 2, which is lower than 00 ° C. 4. The alicyclic bromine compound (X) having a melting point of 200 ° C. or more and the alicyclic bromine compound (Y) having a melting point of less than 200 ° C.
The flameproofing agent for polylactic acid fibers according to claim 3, wherein the weight mixing ratio of X and Y is set in the range of 1: 0.1 to 1: 1. 5. The flameproofing agent for polylactic acid fibers according to claim 1, wherein the phosphate compound is an emulsion or a dispersion. 6. A treatment liquid containing the flameproofing agent for polylactic acid fibers according to any one of claims 1 to 5 is prepared, and the polylactic acid fiber structure is immersed in the treatment liquid. A flameproofing method for a polylactic acid fibrous structure, wherein the method is heat-treated at a temperature of from 130 to 130C. 7. The flameproofing method according to claim 6, wherein the heat treatment time is 15 to 90 minutes.