JPS60126380A - Production of anti-staining fire retardant polyester fiber - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION (Technical Field of the Invention) The present invention provides a method for washing polyester fibers. This invention relates to a method for imparting flame retardance with excellent durability and anti-fouling properties.

(Prior art and its problems) Compounds containing elements such as halogen, nitrogen, phosphorus, and nitrogen are well known as effective flame retardants for making woven fabrics flame retardant. There are methods of producing flame-retardant fibers by applying flame retardants as monomers or additives, and methods of making flame retardant by post-processing the surface of fibers and knitted fabrics thereof with a solution containing a flame retardant. However, in the conventional method, the copolymerization agent or additive is
(In the case of application, the yarn is spun at temperatures of 250°C or higher, so the compound must be able to withstand these conditions. In addition, it may have poor spinnability due to the inclusion of flame retardant components. However, even in yarn spinning, there are many cases in which the quality deteriorates.On the other hand, in the post-processing method mainly used for human-made fibers (Iff), the retardant is applied to the surface of the fiber J3 and its &1 fabric. Because it is applied in a large amount, the adhesion becomes poor and it often gives a sticky hard feeling.Furthermore, for uncolored items, high degree of addition, 1: Moderate drying, heat treatment,
Dye extraction occurs during washing and other processes, resulting in a significant decrease in color fastness.

In order to eliminate this problem, methods are sometimes used to exhaust the flame retardant internally, but conventionally known flame retardant methods (
・Durability of flame retardant performance, i.e., washing resistance, dry cleaning resistance, storage resistance, stable bamboo (no change over time), and washing reverse contamination prevention (1) duality (no darkening due to washing i7J) Nothing has been developed that satisfies all of these requirements. In other words, fibers and fabrics obtained by exhaustion treatment may become flammable after repeated washing, even though the flame retardant itself is generally difficult to remove by washing. This tendency is particularly strong when washing with conventional soaps containing higher fatty acid su-1-lium as a main component, and moreover, this tendency is remarkable for flame retardants containing phosphorus. However, phosphorus compounds, especially compounds containing phosphorus and halogen, are effective in making heat-melting synthetic fibers such as polyester flame retardant and have been widely used (). A decrease in flame retardancy was also observed after washing. In particular, the cause of the decrease in flame retardancy is due to washing with higher fatty acid sodium stones (pour).
Rin Mata lJ.

This is not due to the desorption of the flame retardant containing Cogun, but rather an ion-exchange reaction that causes calcium and magnesium cations from hard water or alkali metal cations from detergents to accumulate on the surface of flame-retardant fibers and their knitted fabrics. It is a powerful tool. In the case of synthetic detergents, this adsorption of stone phosphorus appears in the same way as alkaline stone (though not as noticeable).
, JP 55-122016, JP 53-4459
9 etc. have been proposed. These are made by surface-treating fibers that have been depleted of flame retardant with water-soluble alkylene glycol copolymerized polynisdel to achieve flame retardancy with wash resistance. r sex is i! Although it was washed, there were problems with darkening caused by washing.

(Invention I) The present invention improves the above-mentioned drawbacks.As a result of our own research, we found that when a specific compound is added to silk, the washability is improved without impairing the original properties of the fiber. 5!1 (Flammability and washing (71 Reverse contamination prevention 11 applied to polyester fibers and silk)
If we find that 1q is given, we can make d.

(Structure of the Invention) An antifouling method characterized in that a polynisder-based structure is treated with a flame retardant compound and a polyester copolymer containing 5-(alkali metal)-sulfoisophthalic acid in a separate bath or the same bath. A method for producing flame-retardant polynisdelic cord.

(Mechanism of action of the invention) The flammable compounds of the present invention include halogenated phosphorus (coalkane, halogenated) J, nyl glycidyl ether derivatives, phosphorus halide flQ I sprue derivatives, de Bisphenol Δ derivatives and other halogen compounds, ammonium polyphosphate, guanidine phosphate, phosphorus compounds, ammonium dioxide, etc. In particular, halocogenated cycloalkanes, halogenated cycloalkanes, 3M 4-unit, halogenated phosphate eusdel derivatives are effective. Specific examples of halogenated phosphates [l alkanes include lζ such as 1.2, 3, 4,
5.6-Hekilyb Ill Mosik IJ Heptane, 1.2,
3.4 or 1,2° 4.6 but 1 helazo I comocyclooctane J, or 1,2° 5.6, 9.10-to main rib 1
-1 moshik [1 dodecane, etc. The general formula % formula % (where X, Y, Z are 1-1 or CH3, CI, 1
3+-) and contains 33 to 6 C1 or Br atoms. A typical example is Br 0
Examples include l-I Ct13 (Mi11 point 1371°C) 13 rO1-1 (1Ali point 62°C). In addition, as pigeon 1-glucose phosphoric acid ester, for example, 1-lith 2,3-dibu[lmb]
Copylphosph x, -1~, 1-lith2,3-di[1
Rob (21 biru phosphate, trispromuk 1:10
Examples include propyl small sulfate, tris-dichloro[1-isopropylbosphate, r-1~, tris-dichloro[1-isopropyl phosphate], and the like.

The flame retardant compounds according to the invention are used primarily in aqueous dispersions. The water dispersion method of the flame retardant compound is not particularly limited, but in order for the flame retardant compound to be stably dispersed and absorbed into the binding material 1, particles in the range of 0.1 to 30 microns are required. It is desirable that the diameter is the same. At 0.1 microns or less, the exhausted flame retardant compound is likely to be extracted to the outer surface by a cleaning operation, and at 30 microns or more, the exhaustion efficiency decreases significantly. 1) What is the flame retardant compound listed in a? 11 or two or more types can also be used in combination μ. Methods for exhausting flame retardant compounds into fibers include immersion heat treatment, ¥1
Treatment in a hot water bath is effective. The amount of flame retardant compounds exhausted can be selected as appropriate depending on the desired degree of flame retardancy, but according to research by the present inventors, the amount of flame retardant components exhausted inside the fiber is 2 to 10% owf. A range of is good.

If it is less than 2% OW4, the flame retardance is insufficient, and if it exceeds 10% OWF, the texture and color fastness of the fibers will deteriorate. Incidentally, even if the flame retardant compound is added in advance at the yarn manufacturing stage, the first effect of the present invention can still be obtained.

5-(alkali metal)-sulfoisophthalic acid-containing poly-[Sdelha polymer (hereinafter referred to as
Sulfo polyester polymer) is a polymer containing 10 to 30 mol% of 5-(alkali metal)-sulfoisophthalic acid in the dicarboxylic acid component, and as this component increases, the hydrophilicity increases. The adhesion to polynisder fibers tends to decrease. Further, terephthalic acid or isophthalic acid may be optionally added as other dicarboxylic acid components. Particularly preferred is one in which terephthalic acid is contained in the dicarboxylic acid component in an amount of 30 to 70%. We understand that when terephthalic acid increases, the texture of processed products tends to become rough and hard. As the glycol component added to the d31 small polyester copolymer, ethylene glycol, propylene glycol, tetramethylene glycol, hex→nandi 71-/-, decamethylene glycol, etc. are applicable, as well as the usual alkylene glycol salts. The ratio of the components is arbitrary, and the optimum ratio of the components can be determined depending on the target sulfo-polynisder copolymer.

Specific copolymerization examples of the polyconistyl copolymer include terephthalic acid 15-, alkali metal)-sulfoiphthalic acid/alkylene glycol, prephthalic acid 15- (alkali metal)
-sulfoisophthalic acid/alkylene glycol, j-medyl phthalate 15-(alkali metal)-sullevoisophthalic acid/alkylene glycol] polynisder, etc., but are not limited to these.

In the present invention, the flame retardant sulfo-polyester copolymer is treated with polyester fibers in the same bath or in a separate treatment bath. Pad dry, pad steam, etc. may be applied. In particular, treatment in a bath is preferable in terms of durability and performance.

The amount (11) of the sulfo-polynisder copolymer to the fiber is preferably in the range of 0.01 to 1.00% owl' as the active ingredient (2).

The copolymer, the sulfo-polymer, and the sprue may be added at the yarn production stage, in which case the copolymer becomes rich on the fiber surface, and the effects of the present invention are further improved. Alternatively, after treating one side of Torara in a hot water bath, the other side can be treated with a pad dry method or a pad steam method. You can get some effect by treating it.

According to the present invention, it is possible to carry out treatment in a hot water bath on the dyed surface IS, and in that case, it is possible to avoid adding a nonionic or anisotropic interfacial crystallizing agent, if necessary. .

Polynisder fiber exporter of the present invention 1.1. , high molecular weight polymers produced by the condensation reaction of terephthalic acid and ethylene glycol or bublene glycol, and condensation of sebacic acid, adipic acid, trimelin l-acid, isophthalic acid, paraoxybenzo-12, etc. with ethylene glycol or bublene glycol. It refers to polymers and polyester polymers including other polyesters. Such poly-earth sprue fiber ♀11 may be used alone or in a mixed form with other fibers.
The effects of the present invention are effectively exhibited regardless of the form of the rl antiquities.

When such polynisder fibers are treated with the above-mentioned external combustible compound, the compound is added to the fibers in an amount of 3 to 15% by weight,
Further, the sulfo-poly-1 stellate copolymer is added in a proportion of 0.05 to 5% by weight based on the woven material t and used as a treatment solution.

The treatment liquid is heated to a temperature of 110 to 140°C, and is heated to a temperature of 10 to 9
Process for 0 minutes.

In some cases, it can be processed using the pad dry or pad steam method like normal resin processing. After either the J-flammable compound or the above-mentioned sulbo-polynisder copolymer is immersed and heat-treated in a dye bath, the other can be treated by a pad-1-ly or pad-steam method.

(Effects of the Invention) The feature of the present invention is that by treating with the flame retardant compound and the sulbopolyester copolymer, it has excellent flame retardancy and excellent flame retardancy. Antifouling properties can be added to the fibers.

EXAMPLES Hereinafter, the present invention will be explained in detail with reference to Examples.

Examples 1 to 3 Consisting of polyester fiber shoulder 1 [l i'J' 280
(Addition of J/m2) After relaxing the two-thread fabric - intermediate set 1 - dye flow type dyeing (simultaneous stain-proofing with dyeing method)
It was treated with Il combustion.

The processing conditions are as follows.

Mikawhite ΔN(:
Fluorescent dyeing made by Yobishi Kasei M"I) 1, 8% by weight, to 4=
Solid content of 10,000% solid content of dispersion of 1nozo1'hishiku [1acane], 68 mol% of J-phthalic acid units, 17 mol% of isophthalic acid units, 15 mol% of 5-(sodium)-sulfoisophthalic acid units. Polyester copolymer consisting of and ethylene glycol (resin concentration 20%) 5.
The dye bath was adjusted to contain 0.3 cc/Q of acetic acid and was treated at 13'O<0>C for 45 minutes at a bath ratio of 1:25. Next, Zandet G-29 (nonionic surfactant manufactured by Sanyo Chemical Co., Ltd.) and 1c+/ff were also washed at 60° C. for 10 minutes, dehydrated, and dried. A11 of the flame retardant and the copolymer is 6.
It was 52% (Example 1). As an example of this, 1% by weight of Mikawhite ATN (fluorescent dye made by Mitsubishi Kasei), 10% by weight of a dispersion of Bekizab 1] Moshiku (solid content of a dispersion of Kobukan), and %, acetic acid 0.3cc/ff
The process was carried out at 130° C. for 45 minutes at a bath ratio of 1:25 in a dye bath adjusted to give the desired results. Next, Nandit G
-29 (1 g/(1) r60°C x 10 minutes, dehydrated, and dried.

After that, the same polyester copolymer as in Example 1 (A (resin concentration 20%)) was prepared in an aqueous solution adjusted to IOCI/α to 80%.
Heat treatment at 160°C for 45 seconds using the pad dry method (Example 2) and 110' using the pad steam method.
CX heat treatment for 120 seconds (Example 3) was performed. The adhesion amounts of the flame retardant and the copolymer were 6.60% and 6.55%.

In addition, as a comparative example, using the same polyester processed yarn fabric as in Example 1, Mikawb
A dye bath was prepared by blending 1.8% by weight of ite A T N and 10% by weight of a dispersion of hexabromocyclodecane as a solid content, adding 0.3 cc of acetic acid to this and adjusting the concentration to 10 with water (bath ratio 1:25). ) for 45 minutes at 130°C. Next, it was washed at 60° C. for 10 minutes under Sandwich 1 to G-29 (1 g/α), and dehydrated and dried. The amount of flame retardant is 6.31%
(Comparative Example 1).

In addition, Mikawhite A
1.8% by weight of TN and 5.0% by weight of the same polyester copolymer (resin concentration 20%) as in Example 1 were blended, and 0.0% of acetic acid was added. ．． The dye bath was treated in the same way with 3 cc of water and adjusted to α, and after washing, it was dehydrated and dried.

The amount of the copolymer was 0.15% (Comparative Example 2)
.

These treated fabrics were measured for adsorption of luxury clothing 1j7Ita sodium soap (marcelite), flame retardancy, and anti-laundering back-staining properties, and the results are shown in Table 1.

From Table 1, it can be seen that according to the treatment method of the present invention, excellent durable flame retardance and washing and reverse stain prevention properties can be obtained.

The performance evaluation method is as follows.

[Adsorption properties of Marcel soap] Washing conditions are JIS-
Full cell based on 3301 (Type 1). Add 5E dung to IQ/α and wash at 60℃ x 15 minutes at 4140℃ x 5
Washing was repeated 5 times, with 3 rinses for 3 minutes per cycle, and the adsorption rate of marcelite was determined from the change in weight.

EMti flammability] Evaluated by method D (coil method) of JIS-11091. The passing score is 3 times or more.

[Washing reverse stain prevention property] A staining agent consisting of 15% by weight of stearic acid, 15% by weight of oleic acid, 15% by weight of hydrogenated oil, 15% by weight of olive oil, 23% by weight of solid paraffin, and 91% by weight of carbon bran and viscosity. 58% by weight, Portland cement 15% by weight, silica gel 15% by weight, r]-decane 10% by weight,
A staining agent B consisting of 2% carbon black was mixed in a ratio of 3:1, and the mixed staining agent and an anionic detergent (Super Dib (Hanadama Soap Co., Ltd.)) were mixed in a weight ratio of 7:3. Cover the sample with a scale and mortar so that the amount of the contaminant is 0.2% by adding water to the resulting solution.

A test fabric (5cm x 1Q
cm), and rounder meter one-sided test (4
The treatment is carried out at 0°C for 20 minutes and the blackhead reverse contamination property is determined. If the breath wool test is grade 3 or higher, it will be considered a pass.

Example 4.5 Poly”-sprue textile fiber [;1t318 (J/
After relaxing scouring - intermediate lot of Tn2 knitted fabric (smooth deformation), apply liquid flow Bv + Toiro (color) to the workpiece using 3 umikalon (31ue S - B G
(Disperse dye manufactured by Sumitomo Chemical) 0.05 weight fFi%, dehydrofuric acid 1i position 78E-le%, 5-(sodium)-
511% of a polyester copolymer (resin concentration 20%) consisting of 22 mol% of sulfoisophthalic acid units and ethylene glycol is blended, and 'vinegar lV! Add 20.3CC and add 1'1 of water to KFJ regular dye bath (bath ratio 1:
20) Treated at 130°C for 15 minutes. Then, it was dehydrated and dried.

Thereafter, a treatment bath containing the dispersion of (solid content) adjusted to 40 g/Q (
・160℃ x 4 with bat dryer method at 80% aperture
After heat treatment for 5 seconds, washing with hot water, and drying (Example 4).

J. After being treated with the above treatment bath, the pad dry was replaced with a pad steam method and heat treated at 110° C. for 120 seconds, washed with hot water and dried (Example 5).

The weight ratio of the copolymer and flame retardant is 3.01% and 2.0%.
It was 98%.

In addition, as a comparative example, 5IJIII
ikalon 13 lue S -B G 0.05
% by weight, acetic acid Q, 3 cc and water adjusted to 1 ff in a dye bath (bath ratio 1:20) at 130°C for 455 minutes, dried. Added 400% solid content and squeezed by 80% in a treatment bath adjusted to 1θ, and one was
The other one was heat treated at 110° C. for 120 seconds using a pad steam method (Comparative Example 4), and after washing with hot water, it was dried.

The flame retardant content was 2.90% J5 and 2.81%.

The adsorption properties, flame retardance, and washing back stain prevention properties of Marcel soap were measured in Examples 1 and 2 for these 11 treated sheets, and the results in Example A are shown in Table 1.

From Table 1, it can be seen that according to the treatment method of the present invention, flame retardancy J3 with excellent durability and washing back stain prevention properties can be obtained.

Example 6, eyes made of apolyester fibers (;j1'l 5 (J
The knitted fabric using filaments of /m2 was subjected to relaxing scouring and intermediate cera 1 to 1, and then fluorescent dyeing was carried out using a liquid jet dyeing machine in a conventional manner. Thereafter, a dispersion of hexabromocyclodecane was prepared with a solid content of 45 g/Q and a terephthalic acid unit of 78 mol%.
, a polyester copolymer (resin 1% 20%) consisting of 22 mol% of 5-(sodium>-sulfoisonotalic acid units) and ethylene glycol, 80% squeezed in a treatment bath adjusted to Q/ff, one with a pad・170 in dry method
℃ x 45 seconds (Example 6), and the other one was heated at 110℃ x 120 seconds using a pad steam force method (Example 7)
After washing with hot water, it was dried.

The adhesion amount of the flame retardant and the copolymer is 3.22% and 3.1%.
It was 8%.

In addition, as a comparative example, for a dyed product similar to this example, a dispersion of hexabromocyclodecane was added to the solid content of 4.
．． 5 g/Q, polyethylene glycol (molecule fi
4000), prephthalic acid, and ethylene glycol (resin Ffl e 20%
) 20 Q / Q TeTIJ Wi Shitadokoro BJ
One comparative example was heat-treated at 170°C for 45 seconds using a pad dry method (comparative example 5), and the other was heat-treated at 110°C for 120 seconds using a pad and steam force method, with bath R 80% reduction. 6) Then, after washing with hot water, it was dried.

The f'' coverage of the copolymer was 3.31% and 3.29%.

These treated fabrics were measured for adsorption of marcelite (dirt), flame retardancy, and anti-laundering stain resistance in the same manner as in Example 1, and the results are shown in Table 1.

As can be seen from Table 1, according to the treatment method (b) of the present invention, flame retardancy and washability with durability are achieved. M reverse contamination prevention IJ duality is obtained.

Claims (1)

[Claims] Antifouling M characterized in that polyester fibers are treated with a polynisder copolymer containing a flammable compound and 5-(alkali metal)-sulfoisophthalic acid in a separate bath or in the same bath. Method for producing flammable polyester fiber.