JPH02200871A - Fire-proof processing method for synthetic fiber - Google Patents

Abstract

PURPOSE:To raise the adsorbability of a fire-proof agent and improve the fire retardancy of a synthetic fiber in a small amount of the fire-proof agent by treating the synthetic fiber or a composite material thereof with both hexabromocyclododecane and a specific phosphate compound. CONSTITUTION:A synthetic fiber such as polyester fiber or a composite material thereof with a cellulose fiber is treated with an emulsified fire-proof agent comprising hexabromocyclododecane and a phosphate ester of the formula [a, b and c are 0-3, a+b+c=3; A is C6H5, B is C6H4-CH3 or C6H3-(CH3)2; C is C8H17, CH2CH2Cl or CH-(CH2Cl2)2] in a weight ratio of 10:0.5-30 to improve the fire retardancy of the fiber or composite material in a small amount of the agent. The simultaneous treatment of the fiber with both the processing agent and a dye in a dyeing bath permits the improvement of the adsorption of the processing agent at a low temperature of <=120 deg.C and simultaneously permits the dyeing treatment of the fiber.

Description

[Detailed description of the invention] [Industrial application field]

The present invention relates to a flameproofing method for synthetic fiber materials. More specifically, polyester, cationically dyeable polyester,
The present invention relates to a flameproofing method for synthetic fiber materials used for synthetic fibers such as polyamide and films, mixed materials thereof, or composite materials with other cellulose fibers.

[Conventional technology]

Conventional flameproofing methods for synthetic fiber materials using hexabromcyclododecane include 2, for example, Japanese Patent Publication No. 53-88
Examples include those using flame retardant agents disclosed in Japanese Patent Publication No. 40 and Japanese Patent Publication No. 59-36032. These flame retardant finishing methods for synthetic fiber materials basically consist of atomizing and dispersing polybrominated organic compounds 1, such as hexabromocyclododecane, which are solid at room temperature, using dispersants or protective colloids commonly used in the dye and textile industries. are doing.

[Problem to be solved by the invention]

However, in the conventional flameproofing method for water-dispersed synthetic fiber materials using hexabromcyclododecane, the sorption (exhaustion) rate of hexabromcyclododecane to synthetic fibers is low. In order to
For example, when the above-mentioned two hexabromocyclododecane atomized dispersions were treated in the same dyeing bath, it was necessary to carry out flame retardant treatment at 140°C.
After treatment for 1 hour, the sorption rate was 49-57%. Similarly, in the case of Japanese Patent Publication No. 59-36032, 1
After treatment at 30° C. for 30 minutes, the sorption rate was 51.9%. This means that if a micronized aqueous dispersion of hexabromcyclododecane is simply treated in the same dyeing bath to obtain the desired flame retardant effect, 40 to 50% of hexabromcyclododecane will be wasted. This indicates that dyeing treatment at 130°C or higher is necessary. In this way, when hexabromocyclododecane is atomized and dispersed with a conventional dispersant or protective colloid, the adsorption of hexabromocyclododecane to the target fiber is poor, and it is difficult to achieve the desired flame retardancy. To obtain performance, 130
It requires a high temperature of 140°C to 140°C and an excessive amount of the hexabromocyclododecane micronized dispersion. For this reason, residual hexabromcyclododecane turns into a tar-like substance at high temperatures, causing can body contamination, especially synthetic fibers such as ordinary polyester and polyamide, and materials that are sensitive to heat such as CD polyester, acrylic, and wool. In the case of composite materials with fiber materials, high-temperature treatment is not preferred, and there is a problem in that the amount of hexabromocyclododecane adsorbed decreases, thereby making it impossible to obtain the desired flameproofing effect. The present invention improves flame retardancy by increasing adsorption to the fibers to be flame retardant without using excess hexabromocyclododecane. It is also an object of the present invention to provide a flameproofing method for synthetic 1a fiber materials that can be applied to fiber materials that are also sensitive to heat.

[Means to solve the problem]

The present invention has been made by paying attention to such conventional problems. Namely. Hexabromocyclododecane and general formula (I) [wherein a, b, and c are a+b+c+=3, and O≦
It is a natural number such that a≦3.0≦b≦3, and 0≦C≦3. A is -C@H, B is -C6H4-CH8 or -〇6H3(
CHI)2, C is -C8H17, CH2CH2C, or -CH-(CH2cJL)2] is simultaneously used for flameproofing treatment. It is. (Requirements constituting the means) Hexabromocyclododecane used in the present invention is a known compound, and is itself produced by a known method. Compounds represented by the general formula (I) include triphenyl phosphate, tricresyl phosphate, tricylenyl phosphate, cresyl diphenyl phosphate, xylenyl diphenyl phosphate, octyl diphenyl phosphate, tris(chloroethyl ) phosphate and tris(dichloropropyl) phosphate. These compounds are also known compounds and are produced by known methods. The combined ratio of hexabromocyclododecane of the present invention and a phosphoric ester, which is a compound represented by formula (I), is 0.5 to 10 of hexabromocyclododecane (a phosphoric ester, which is a compound of formula I). It is appropriate to use it in a weight ratio of 1 to 30, more preferably in a weight ratio of 1 to 1O. Cyclododecane and the compound of formula (I) may be separately atomized, dispersed and emulsified, and used simultaneously in the above-mentioned blending weight ratio when performing flame retardant treatment, or hexabromocyclo After adjusting the blending ratio of dodecane and phosphoric acid ester which is a compound of formula (I), atomization and emulsification may be carried out simultaneously to obtain the desired product. After atomization and dispersion,
Emulsified in advance using a common surfactant (
The compound of formula I) may be added and prepared in a predetermined weight ratio, that is, if hexabromocyclododecane and the compound of formula (I) are simultaneously treated on the fibers to be treated, then Any blending method may be used, and surfactants, protective colloids, etc. may be used in the flameproofing method of the present invention.Furthermore, in the flameproofing method of the present invention, It showed the same flame retardant effect even when the dyeing temperature was 120°C or lower, making low-temperature treatment possible. Such a flameproofing method of the present invention is applied to synthetic fiber materials and products. In particular, it can be used for flameproofing polyester and polyamide fibers, woven fabrics, knitted fabrics, films, felts, and the like. Furthermore, blends of these with heat-sensitive fiber materials such as CD polyester, acrylic and wool. It is also effective for composite materials such as mixed fibers and knitted and woven materials. The flameproofing method using the flameproofing agent of the present invention can be applied to known methods such as dyeing bath method, thermosol method, and coating method. In particular, its effectiveness is significantly exhibited in the same dyeing bath method at temperatures below 120°C.

[Effect]

An aqueous dispersion of hexabromocyclododecane that has been atomized using a conventional dispersant or protective colloid is difficult to adsorb hexabromocyclododecane to the fibers to be flame retardant. is used in excess and the treatment is carried out at a high temperature of 130° C. to 140° C., which is not only uneconomical but also causes contamination of the fibers to be treated. We investigated various compounds with the aim of improving the adsorption of hexabromocyclododecane and making dyeing treatment possible at lower temperatures. The compound of formula (I) has the effect of promoting the sorption of hexabromocyclododecane to the corresponding treated fiber (carrier effect), the effect of suppressing the nucleation and granulation of hexabromocyclododecane, and also They discovered that it also makes it possible to carry out dyeing treatments. Furthermore, the compound of formula (I) itself is a flame-retardant compound as is well known, and since it is sorbed onto the fibers to be flame-retardant, it exhibits a mutual effect. That is, the advantages of using the processing method of the present invention using a processing agent containing hexabromocyclododecane and the compound of formula (I) are that, first, a small amount of the flame retardant agent can be used to produce excellent flame retardant properties; Second, the contaminating action of unadsorbed hexabromocyclododecane can be suppressed, resulting in lower can cleaning costs, improved operating rates, reduced generation of contaminated cloth, and reduced costs for reworking contaminated cloth. Thirdly, the recent trend is towards the composite of fiber materials, with heat-resistant synthetic fibers such as ordinary polyester and polyamide, and heat-resistant synthetic fibers such as CD polyester, acrylic, and wool. Composite fibers with weak fiber materials are being elongated, and the number of composite fibers with a high composite ratio of the latter is also increasing.6 In these cases, in order to maintain the strength of the latter, low-temperature treatment of 120°C or less is required. However, under such low temperatures, the sorption properties of hexabromocyclododecane would be greatly reduced, and the desired flame retardant performance could not be obtained.However, with the present invention, it is possible to It is now possible to obtain sufficient sorption properties to exhibit flame retardant performance even under low temperatures.

【Example】

EXAMPLES The present invention will be specifically explained below with reference to Examples, but the present invention is not limited thereto in any way. <Production Example 1> A 5% carboxymethyl cellulose aqueous solution 2011 and 90 kg of tap water were placed in a premix mixer equipped with an agitator, and mixed and stirred for a short time. 90 kg of hexabromocyclododecane was gradually added to this aqueous carboxymethylcellulose solution while stirring to prepare a crude dispersion. This coarse dispersion was continuously mixed and pulverized while being fed into a pulverizing dispersion machine (301 volume Viscomil, manufactured by Igarashi Kikai Co., Ltd.) to be pulverized and dispersed. The particle size of the hexabromocyclododecane micronized dispersion thus obtained was measured using a centrifugal particle size distribution analyzer (Model 5A-CP-II manufactured by Itsu Co., Ltd.), and the average particle size was 1.45IL. Met. Next, in a 100 capacity reaction vessel equipped with a mixing stirrer and a reflux condenser, 45 kg of tricylenyl phosphate, 3 kg of a 10 mole adduct of nonylphenol ethylene oxide, and 22 kg of a sodium naphthalene sulfonic acid formalin condensate were placed.
2KKC active ingredient (10 kg) was charged and mixed and stirred at room temperature to make the three components uniform. Then tap water 2
9.8 kg was added over about 1 hour to obtain a tricylenyl phosphate emulsified dispersion. (Usage Example 1) Hexabromcyclodobucuff obtained in Production Example 1 45%
Containing atomized dispersion and tricylenyl phosphate 45
The present invention will be explained using a formulation containing an emulsified dispersion containing %. The dyeing treatment method was dyeing bath treatment.9 per unit area,
A polyester yarn woven fabric weighing 260 g/m2 with regular polyester on both sides and cationic dyeable polyester in the center was prepared using the flame retardant formulation, bath ratio, and dye bath amount as shown in Table 1, and the dye was Kayacry JI Br1l.
liant Yellow 5GL-ED (Nippon Kayaku) 2% ovrf and Kayalon Po1
yester BlueT-50, 3% owf, anionic surfactant 0, 5 g/ as a dyeing dispersant
The dye bath was adjusted to pH 5 with acetic acid. The dyeing machine is a 60-monyo model circular testing machine (Mo
delS Cut-T-5) at 3/min from 60°C.
Raise the temperature to the set dyeing treatment temperature at a heating rate of ℃, and then increase the temperature to 1.
It was kept for 60 hours and stained. After that, the temperature rapidly decreased to 60
When the temperature reached ℃, it was washed with tap water for 10 minutes. Thereafter, a solution of 2 g/fL of sodium hydrosulfide and 2 g/Jl of soda ash was used at a bath ratio of 1/30. The processed cloth was washed with light for 10 minutes at a temperature of 80 to 90° C., washed again with tap water for 10 minutes, and dried. The reason why the above-mentioned Yel 1 ow dye was used as the dye was to make it easier to distinguish between the dyed processed cloth and the adhesion of contaminants. In addition, in order to check the adhesion of contaminants from the flame retardant used on the processed fabric and the dyeing can body, dyeing, waste liquid, washing with water, and dyeing were repeated repeatedly using the same dyeing bath composition. And there is contamination on the dyeing can! Once this was detected, we stopped the dyeing study using that dye bath composition. The amount of sorption after dyeing is measured at constant temperature and humidity (temperature 20°C, humidity 60°C) before and after the above-mentioned dyeing bath treatment of the polyester fabric.
%) was left for 24 hours or more and determined from the difference between the two when the temperature reached a constant temperature. However, as a blank, a polyester cloth to be treated was treated by adding dye, dyeing dispersant, and acetic acid (without adding the flame retardant component), and the amount of sorption of other additive components such as dye and the amount of shedding from the polyester cloth (constant weight) was treated. conditions). The amount of flame retardant sorption was calculated from the two measurements. In addition, the amount of sorption of hexabromcyclododecane itself is determined by the amount of sorbed Br on a dry cloth kept at a constant temperature after the same dyeing bath.
It was quantified by line analysis method. In addition, the evaluation of flame retardancy is based on JIS-L-1091/A-1 method,
It was carried out using the 3 second flame setting method, and the washing fastness was JTS-L-084.
4.A-2 method, and the friction fastness was determined according to JIS-L-0849 method, and the results of 0 or more are shown in Table 1. It can be seen that tricylenyl phosphate has a (carrier) effect that promotes the sorption of hexabromocyclododecane onto polyester fibers. In addition, by simultaneously treating tricylenyl phosphate, the number of repeated dyeing increases, contamination of the dyeing can and the treated fibers is improved, and even if the dyeing temperature is lowered, the flame retardant effect is not so good. It turns out that there isn't. This eliminates the need for flame retardant treatment at a temperature of 130°C or higher, which is normally employed in dyeing bath treatment, and allows the treatment to be performed at a temperature of 110°C or lower, where structural changes in hexabromocyclododecane do not occur much. It can be seen that the desired flame retardancy can also be obtained. Production Example 2> In a premix mixer with a stirrer, 10.0 kg of 5% carboxymethyl cellulose aqueous solution, 27.0 kg of octyl diphenyl phosphate, 3.0 kg of 6 mole adduct of octylphenol ethylene oxide, and 22 kg of naphthalene sulfonic acid soda formalin condensate. .2 kg and 47.8 kg of tap water were charged and mixed and stirred for a while. In this mixed solution, 90.0 kg of hexabromocyclododecane was added.
was gradually added with stirring. This coarse dispersion was continuously mixed and pulverized while being fed into a pulverizing disperser, and pulverization of hexabromocyclododecane and emulsification dispersion of octyl diphenyl phosphate were carried out simultaneously. The average particle size of the micronized emulsified dispersion thus obtained was 1.58μ. Production Examples 3 to 8> In the same manner as Production Example 2, hexabromocyclododecane and various phosphorus compounds were simultaneously atomized and emulsified and dispersed. The blending composition and the average particle diameter of the obtained micronized emulsified dispersion are shown in Tables 2 and 3. The dyeing bath was treated in exactly the same manner as in Use Example 1, and its performance was examined. The results are shown in Tables 2 and 3. Depending on the type of phosphorus compound, the total amount of B and Br sorption sensitivity (
Hexabromocyclododecane) is slightly different, but the amount of Er sorption increases by 50 to 80% when a phosphorus compound is used in combination than when hexabromocyclododecane is treated alone. That is, it can be seen that less flame retardant needs to be added to obtain the same level of flame retardant performance, and at the same time, contamination by residual hexabromcyclododecane is reduced. It can also be seen that the same flame retardant effect can be obtained even if the dyeing treatment temperature is as low as 110°C. (Margin below)

【Effect of the invention】

The flame retardant processing method of the present invention improves the flame retardancy of fibers,
The desired flame retardant performance can be obtained with a small amount of processing agent, the number of repeated dyeing increases, the operation rate is improved, the can body cleaning cost is reduced, the generation of contaminated cloth is reduced, etc.
This makes it possible to dye at the following low temperatures. This can greatly contribute to flame retardant technology for m-fibers. Patent applicant Daiichi Kogyo Seiyaku Co., Ltd.

Claims (1)

[Claims] 1. Hexabromocyclododecane and general formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(I) [In the formula, a, b, and c are a+b+c=3, and 0 ≦
It is a natural number of a≦3, 0≦b≦3, and 0≦c≦3. A is -C_6H_5, B is -C_6H_4-CH_3 or -
C_6H_3-(CH_3)_2, C is -C_8H_1
_7, -CH_2CH_2Cl, or -CH-(CH_
A method for flameproofing synthetic fiber materials, characterized in that flameproofing treatment is performed by simultaneously using a compound represented by 2Cl)_2. 2. The flameproofing method according to claim 1, wherein the dyeing treatment temperature is 120° C. or lower. 3. A synthetic fiber treated by the flameproofing method according to claim 1 or 2.