JP4527797B2 - Flame-retardant finishing agent for polyester fiber and its processing method - Google Patents

Description

  The present invention relates to a flame retardant processing agent capable of imparting flame retardancy to a polyester fiber or a textile product such as a fabric made of the same, and a flame retardant processing method using the same.

  Conventionally, brominated compounds such as hexabromocyclododecane (HBCD) are dispersed in water as a flame retardant processing agent for imparting flame retardancy to post-processing fiber products such as polyester fibers or fabrics made thereof. Or what was emulsified has been generally used (patent document 1).

  However, HBCD has a low sorption rate with respect to polyester fiber or a textile product such as a fabric, and a large amount of HBCD is discharged into the environment.

  In addition, HBCD that has been used for exhaustion processing has been found to have persistent decomposition and high accumulation, and there is a demand for de-HBCD.

  In contrast, flame retardants that use phosphorus compounds such as organophosphates are also used, but condensed phosphates have little sorption inside the fibers, even if they are attached to the surface, and are attached to the surface. Drops off by alkaline soaping such as reduction cleaning (RC) or water washing. For this reason, it tends to be insufficient in durability and flame retardancy.

  On the other hand, when a low molecular weight phosphate ester is used as a flame retardant, the sorption after processing is good, but in practice, the flame retardant tends to drop off by water washing or dry cleaning. There was insufficient durability and flame retardancy.

  Moreover, in the durable flame retardance of curtain use, even if the durable flame retardance of regular polyester (Reg-PET) is obtained, it is mixed with cationic dyeable polyester (CD-PET), especially its mixing ratio ( When the CD mixing ratio was 50% or more, it was difficult to develop durable flame retardancy.

  In order to solve the above problems, for example, an aqueous dispersion or an emulsion containing 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (hereinafter referred to as HCA) and an HCA derivative. The flame retardant processing agent which is is proposed (patent documents 2 and 3).

  However, it is necessary to process a large amount of the flame retardant in order to satisfy the flame retardant performance with the phosphorus-based flame retardant, and due to the large amount of processing, the texture and the hue change of the processed fabric may decrease. is there.

  Moreover, since phosphorus flame retardant contains phosphorus in waste water, there is concern about eutrophication of seawater, lake water, and the like.

There has not yet been obtained a flame retardant processing agent that solves these problems and can impart sufficient durability flame resistance even to fabrics that are more difficult to express flame retardancy, such as blends of cationic dyeable polyesters.
JP-A-7-70924 JP 2002-275473 A JP 2003-306679 A

  In view of the above, the present invention solves the problem of lack of flame retardance peculiar to phosphorus-based flame retardants, and presents a flame retardant finish that exhibits excellent durability flame retardancy even in a material having a high CD mixing ratio, and An object of the present invention is to provide a flame retardant processing method using the above.

In order to solve the above problems, the flame retardant processing agent for polyester fiber of the present invention is an interface in which a flame retardant component containing a compound represented by the following general formula (I) is represented by the following general formula (II): The aqueous dispersion is dispersed in water with an activator.
Provided that A ₁ , A ₂ and A ₃ in the general formula (I) are at least one brominated alkyl group selected from 2,3-dibromopropyl, 2,3-dibromoisobutyl and 1,2-dibromoethyl. Represents an alkyl group or an alkenyl group, at least one of which is a brominated alkyl group, and these A ₁ , A ₂ , and A ₃ may be the same or different.
However, X in the general formula (II) represents an anionic group capable of forming a hydrogen atom or a sulfate and / or phosphate ester salts,, Y represents a substituent represented by the following formula, m and n are , M = 1 to 3 and n = 1 to 200, and R ₁ represents an alkylene group having 2 to 4 carbon atoms. X may be only a hydrogen atom or an anionic group, or may be a mixture.

The flame retardant processing agent for polyester fibers of the present invention may further comprise a water-soluble polymer as a dispersant.

  The flame retardant processing method of the polyester fiber of the present invention, after applying the flame retardant processing agent of the present invention to a polyester fiber or a fiber product comprising the same by treatment by a high temperature exhaust method, or by dipping or coating, Heat treatment at 80 ° C. or higher shall be performed.

The aqueous dispersion of the compound represented by the above general formula shows effective sorption when the polyester fiber is treated by the same dyeing bath method, pad dry thermocuring method, etc., and the sorption rate to the processed fabric. Is very expensive.

  Therefore, according to the flame retardant processing agent of the present invention, even a composite material having a high CD mixing ratio exhibits superior durability flame retardancy that is superior to that of the conventional brominated flame retardant processing agent HBCD. In addition, after the flame retardant processing, the amount of the flame retardant discharged into the environment is small compared to HBCD, and the environmental impact is very small.

The flame retardant component used in the present invention is a compound represented by the above general formula (I). Specific examples include tris (1,2-dibromoethyl) isocyanurate, tris (2,3-dibromopropyl) isocyanurate, tris (2,3-dibromoisobutyl) isocyanurate, 1,3-bis (2 , 3-dibromopropyl) -5-allyl isocyanurate, 1,3-bis ( 1,2 -dibromoethyl) -5-ethyl isocyanurate, and the like. Among these, tris (2,3-dibromopropyl) isocyanurate can be preferably used.

  As a flame retardant component, the flame retardant component represented by the general formula (1) is selected from a brominated flame retardant compound, a phosphorus flame retardant compound, a nitrogen flame retardant compound, and an inorganic flame retardant compound. Or 2 or more types can also be used together.

Specific examples of brominated flame retardant compounds that can be used in combination include hexabromocycloheptane, tetrabromocycloheptane, tetrabromocyclooctane, hexabromocyclododecane (hereinafter referred to as HBCD), other brominated cycloalkanes, and polybromo. diphenyl ether, tetrabromobisphenol a (hereinafter referred to as TBBA), TBBA · epoxy oligomers, TBBA · carbonate oligomers, TBBA · bis (dibromopropyl ether), other TBBA derivatives, bis (pentabromophenyl) ethane, 1,2 Bis (2,4,6-trisbromophenoxy) ethane, 1,2-bis (2,4,6-trisbromophenoxy) -1,3,5-triazine, 2,6-or (2,4) dibromo Monophenol, other polybenzene cyclization Compound, ethylenebistetrabromophthalimide, other phthalic acid compounds, tribromophenyl allyl ether, tribromophenyl acrylate, pentabromobenzyl allyl ether, pentabromobenzyl acrylate, other, bromoacrylate monomer, brominated polystyrene, polybrominated styrene , Hexabromobenzene, 2,4-diamino-6- (3,3,3-tribromo-1-propyl) -1,3,5-triazine methylol compound, and the like.

In particular, HBCD, tetrabromocyclooctane, tris (tribromoneopentyl) phosphate represented by the following chemical formula (III), TBBA · bis (2,3-dibromopropyl ether) represented by the chemical formula (IV), TBBA -Bis (2,3-dibromomethyl propyl ether) etc. can be used conveniently.

However, in the formula (IV), R ₂ is H or CH ₃ .

Specific examples of the phosphorus-based flame retardant compound used in the present invention include triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl phenyl phosphate, other aromatic phosphate esters, aromatic condensed phosphate esters, etc. Phosphorus compounds, aromatic phosphorus compounds represented by the following chemical formulas (V) and (VI), alkali metal salts, alkaline earth metal salts, aluminum salts, zinc salts, or amines of the compounds represented by the chemical formula (VI) Examples thereof include, but are not limited to, a salt or a phosphazene compound represented by the following chemical formula (VIII).

In the chemical formulas (V) and (VI), R ₃ and R ₄ have an alkyl group having 1 to 24 carbon atoms, an alkenyl group having 2 to 22 carbon atoms, a hydroxyalkyl group having 1 to 10 carbon atoms, and a substituent. An aralkyl group which may be substituted, an -OH group, an alkoxy group having 1 to 10 carbon atoms, an aralkyloxy group which may have a substituent, or a group represented by the following chemical formula (VII);

In the chemical formula (VII), R ₅ represents a hydrogen atom, an alkyl group having 1 to 24 carbon atoms, or an alicyclic alkyl group having 5 to 6 carbon atoms.

In the chemical formula (VIII), R ₆ and R ₇ may be the same or different and each is an alkyl group having 1 to 24 carbon atoms, an alkenyl group having 2 to 22 carbon atoms, or an aryl group optionally having a substituent. And o represents an integer of 3 to 10.

In particular, triphenyl phosphate, diphenyl monoorthoxenyl phosphate, 2-naphthyl diphenyl phosphate, 10-benzyl-9,10-dihydroxy-9-oxa-10-phosphaphenanthrene-10- represented by the following chemical formula (IX) Oxides can be preferably used.

  Specific examples of the nitrogen-based flame retardant compound used in the present invention include, but are not limited to, guanidine-based compounds, guanylurea-based compounds, melamine-based compounds, and ammonium polyphosphates. In particular, polymellated melamine phosphate, melamine sulfate, melamine cyanurate, and guanylurea phosphate can be suitably used.

  Specific examples of the inorganic flame retardant compound used in the present invention include antimony trioxide, antimony pentoxide, magnesium hydroxide, and aluminum hydroxide, but are not limited thereto.

  In dispersing or emulsifying the flame retardant component and the combined flame retardant component represented by the general formula (1) in water, a surfactant can be used. As the surfactant, a combination of known nonionic surfactants and anionic surfactants, or any one of them can be used.

  Specific examples of the nonionic surfactant include polyoxyalkylene alkyl phenyl ether, polyoxyalkylene alkyl ether, polyoxyalkylene fatty acid ester, polyhydric alcohol fatty acid ester alkylene oxide adduct, higher alkylamine alkylene oxide adduct, Examples thereof include fatty acid amide alkylene oxide adducts, alkyl glycosides, and sucrose fatty acid esters.

  Specific examples of anionic surfactants include higher alcohol sulfates, polyoxyalkylene alkyl ether sulfates, alkylbenzene sulfonates, alkyl naphthalene sulfonates, naphthalene sulfonate formalin condensates, Higher alcohol phosphate ester salts, polyoxyalkylene alkyl ether phosphate ester salts and the like can be mentioned. Moreover, polyoxyalkylene alkyl ether carboxylate salt, polycarboxylate, funnel oil, petroleum sulfonate, alkyl diphenyl ether sulfonate salt, etc. are mentioned.

  In the present invention, amphoteric surfactants and cationic surfactants can also be used.

  Specific examples of amphoteric surfactants include alkylbetaines, fatty acid amidopropylbetaines, 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaines, alkyldiethylenetriaminoacetic acids, dialkyldiethylenetriaminoacetic acids, alkylamines. And oxides.

  Specific examples of the cationic surfactant include monoalkylamine salt, dialkylamine salt, trialkylamine salt, alkyltrimethylammonium chloride, alkyltrimethylammonium bromide, alkyltrimethylammonium iodide, dialkyldimethylammonium chloride, bromide. Examples include dialkyldimethylammonium, dialkyldimethylammonium iodide, and alkylbenzalkonium chloride.

In the present invention, the flame retardant component to moisture diversification is to use a non-ionic surfactant or anionic surfactant represented by the general formula (II) is particularly preferred.

  Specific nonionic surfactants include polyoxyalkylene monobenzylated phenyl ether, polyoxyalkylene dibenzylated phenyl ether, polyoxyalkylene tribenzylated phenyl ether, polyoxyalkylene monostyrenated phenyl ether, polyoxyalkylene One or a mixture of two or more of alkylene distyrenated phenyl ether and polyoxyalkylene tristyrenated phenyl ether can be used particularly preferably.

Examples of the anionic group of the anionic surfactant represented by the general formula (II) include the following.

  M and M ′ in the above formulas each represent a hydrogen atom, a metal atom, ammonium or a hydrocarbon group.

  Specific examples of anionic surfactants include polyoxyalkylene monobenzylated phenyl ether sulfate, polyoxyalkylene dibenzylated phenyl ether sulfate, polyoxyalkylene tribenzylated phenyl ether sulfate, polyoxyalkylene Monobenzylated phenyl ether phosphate, polyoxyalkylene dibenzylated phenyl ether phosphate, polyoxyalkylene tribenzylated phenyl ether phosphate, polyoxyalkylene monostyrenated phenyl ether sulfate, polyoxy Alkylene distyrenated phenyl ether sulfate and polyoxyalkylene tristyrenated phenyl ether sulfate, polyoxyalkylene monostyrene Phenyl ether phosphate salts, polyoxyalkylene styrenated phenyl ether phosphate salts, and one or a mixture of two or more polyoxyalkylene Rent Li styrenated phenyl ether phosphate can be used particularly suitably.

  As for the addition mole number of the polyoxyalkylene of the said surfactant, 1-200 are preferable, More preferably, it is 10-50.

  In the present invention, the amount of the surfactant as described above is not particularly limited, but it is usually used in the range of 2 to 15% by weight with respect to the flame retardant component. If the amount of the surfactant is less than this, it is difficult to obtain a sufficient dispersion effect, and if it is more than this, a surfactant which is a flammable substance remains on the work cloth and a sufficient flame retardant effect cannot be obtained.

  Commercially available products can be used as the flame retardant component represented by the general formula (1), the flame retardant component used together with the surfactant, and can also be produced by a known method. When the obtained compound is a mixture and a simple substance is required, it may be separated by a known separation means such as distillation.

  In the present invention, the flame retardant component can be dispersed with a water-soluble polymer (protective colloid agent). When the flame retardant component is dispersed with a water-soluble polymer, the viscosity of the dispersion can be suitably adjusted, the sedimentation of the slurry can be suppressed, and the fine dispersion can be uniformly performed. In addition, product separation does not occur after commercialization. Examples of water-soluble polymers that can be used include carboxymethyl cellulose salt, xanthan gum (xanthan gum), gum arabic, locust bean gum, sodium alginate, self-emulsifying polyester compound, water-soluble polyester, polyvinyl alcohol (PVA), gelatin, polyvinyl Examples include pyrrolidone, polyethylene oxide, polyacrylamide, methoxyethylene maleic anhydride copolymer, methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, soluble starch, carboxymethyl starch, and cationized starch. Among these, carboxymethylcellulose salt and xanthan gum are preferable from the viewpoints of the properties of the resulting solution and its stability.

  Specifically, the self-emulsifying polyester compound comprises bishydroxyalkyl terephthalate or a mixture of bishydroxyalkyl terephthalate and bishydroxyalkyl isophthalate, and a polyalkylene glycol selected from polyethylene glycol, polypropylene glycol, and polybutylene glycol. It is a condensation polymer and has a molecular weight of 300 to 50,000, preferably 5,000 to 20,000. The polyalkylene glycol moiety consists of 1 to 150 moles, preferably 50 to 100 moles of alkylene oxide units.

  The water-soluble polyester is specifically a terminal sulfonate Na-modified product of polyethylene terephthalate-polyethylene glycol copolymer, and has a molecular weight of 3000 to 60000.

  In order to stabilize the dispersion state, the flame retardant processing agent of the present invention may contain an organic solvent such as a water-soluble polymer, alcohols, aromatic solvents, glycol ethers, alkylene glycols, and terpenes. Good.

  In addition, by using a carrier component or a carrier component-containing product at the time of processing the flame retardant processing agent of the present invention, a flame retardant such as a regular polyester / cationic dyed polyester / recycled polyester mixed material, which is generally difficult to flame retardant. It is possible to improve the sorption property and flame retardancy even for materials that are difficult to make.

  Here, the carrier component is an agent having a strong affinity for both the polyester fiber and the flame retardant finishing agent, which can uniformly sorb the flame retardant finishing agent to the polyester fiber.

  Examples of the compounds having the above carrier component include benzyl benzoate, methyl benzoate, aromatic halogen compounds, N-alkylphthalimides, methylnaphthalene, diphenyl, diphenyl esters, naphthol esters, phenol ethers, and hydroxydiphenyls. Can be mentioned. Of these, benzyl benzoate and polyoxyalkylene mononaphthyl ether are preferred.

  The flame retardant processing agent of the present invention may further contain various resin additives such as an ultraviolet absorber and an antioxidant.

  As will be described later, the flame retardant processing agent of the present invention can be dyed in the fiber at the same time as the dye, or in a mangle so that the fiber is immersed in a solution diluted with water so that a predetermined adhesion amount is obtained. It can be processed by a method such as a pad-drying thermo-cure method for drawing, drying, and heat setting, a coating method for coating a fiber by mixing and thickening a resin binder and this product and / or a flame retardant aid.

  The flame-retardant processing method of the present invention comprises a step of applying the above-mentioned flame-retardant processing agent to a polyester fiber by a post-processing treatment, and performing a heat treatment at 80 ° C. or higher. , High temperature exhaustion method, pad thermo method, coating method and the like.

  In the high temperature exhaustion method, the polyester fiber is immersed in a treatment bath to which a flame retardant is added, and is treated at a high temperature (usually 80 ° C. or more, preferably 110 to 140 ° C.) for a predetermined time (for example, 2 to 60 minutes). To sorb the flame retardant to the fiber. Preferably, a dyeing and bathing method in which the flame retardant is sorbed onto the fiber simultaneously with the dye is used. That is, it is efficient and preferable to add a flame retardant processing agent to the dyeing bath, immerse the polyester fiber in the dyeing bath, and perform exhaustion treatment at a high temperature.

  In the pad thermo method, the polyester fiber is immersed in a liquid containing a flame retardant processing agent, and is squeezed with a mangle or the like so that a predetermined adhesion amount is obtained, and heat treatment is performed by dry heat treatment or steam heat treatment such as heat steam treatment. To sorb the flame retardant to the fiber. The heat treatment temperature is usually in the range of 110 to 210 ° C. Preferably, after dipping, treatment is performed by a pad-dry thermo-curing method in which squeezing is performed with a mangle, followed by drying and heat setting.

  In the coating method, a resin binder and this product and / or a flame retardant aid are mixed and thickened to coat the fiber.

  The polyester fibers to be treated include polyethylene terephthalate (PET), polybutylene terephthalate (PBT), and polytrimethylene terephthalate (PTT), as well as isophthalic acid, isophthalic acid sulfonate, adipic acid, polyethylene glycol, etc. Copolymerized third component, particularly cationic dyeable polyester and the like are included. In addition, an original yarn formed by kneading a pigment when producing a yarn can be used. The textile products to be treated include various yarns, woven and knitted fabrics, non-woven fabrics, ropes, etc., and may be woven fabrics or composite materials using different yarns of the above-mentioned fibers. Includes union cloth. The fiber product may be a combination of other synthetic fibers, natural fibers, or semi-synthetic fibers by blending or the like.

  Examples of the present invention will be described below, but the present invention is not limited to the following examples.

1. Preparation of Flame Retardant Finishing Agent According to the formulation (% by weight) shown in Table 1 below, the formulation solutions of Examples and Comparative Examples were mixed and stirred to obtain a slurry, and then glass beads having a diameter of 2.0 mm and the same volume as the slurry. Were mixed and stirred, and this was filled in a sand grinder manufactured by IMEX Co., Ltd. and pulverized for 2 hours. After the grinding treatment, the glass beads and the dispersion were separated with a 100 mesh filter cloth.

  According to the composition (% by weight) shown in Table 1 below, each flame retardant processing agent of Examples and Comparative Examples was prepared. The surfactants (1) to (4) were produced by the method described in Chapter 2 of “Nonionic Surfactant” (Seikodo Shinko Co., Ltd.) by Yoshiro Ishii.

2. Evaluation in the same dye bath method Using the flame retardant processing agent immediately after dispersion in the above examples and comparative examples, flame retardant processing is performed by the dye same bath method on a regular polyester / cationic dyeable polyester mixed material (CD mixing ratio 50%). gave.

  Specifically, using Mini-Color (manufactured by Teksam Giken) as a dyeing machine, the following dyeing bath formulation was heated from 60 ° C. at a bath ratio of 1:10 and treated at 130 ° C. for 30 minutes. The treatment amount of the flame retardant finish was 10% o.w.f (on the weight of fiber). After the treatment, the temperature is lowered to 80 ° C., and then the fabric is taken out. After 5 minutes of washing with hot water, the following reduction washing bath formulation, bath ratio 1:30, reduction washing at 80 ° C. for 10 minutes, and further washing with hot water for 5 minutes. After that, heat setting was performed at 180 ° C. for 30 seconds.

[Dye bath prescription]
Dianix Red AC-E 0.20% owf
Dianix Yellow AC-E 0.12% owf
Dianix Blue AC-E 0.02% owf
Kayacryl Black BS-ED 0.30% owf
Acetic acid 1.0 g / l
Anhydrous sodium acetate 3.0 g / l
Flame retardant x% owf

[Reduction cleaning bath prescription]
Hydrosulfite sodium 2.0 g / L
Soda ash 1.0 g / L
TRIPOL TK 1.0 g / L

  In the above, the sorption amount and flame retardancy of the flame retardant finish were examined. The results are shown in Table 2. In addition, the evaluation method of a flame retardance is as follows.

[Flame retardance]
For woven fabrics that have been flame-retarded, those that have been processed, and those that have been subjected to water washing or dry cleaning under the following conditions, JIS L 1091 A-1 method (45 ° micro burner method) and JIS L 1091 D method (45 ° The flame retardancy was measured by the coil method. In the 45 ° micro burner method, “○” indicates that after 1 minute heating and after 3 seconds of flame, the after flame is 3 seconds or less, the residual dust is 5 seconds or less, and the carbonized area is 30 cm ² or less Other than that, “x” was given. In the 45 ° coil method, the case where the number of flame contact was 3 times or more was “◯”, and the case where it was 2 times or less was “x”. For comparison, flame resistance was also measured for untreated fabrics.

(Washing) According to JIS K 3371, a weak alkaline first-class detergent is used at a rate of 1 g / L, and a bath ratio of 1:40 is washed at 60 ° C. ± 2 ° C. for 15 minutes, and then at 40 ° C. ± 2 ° C. This was performed 5 times, with a 5-minute rinse 3 times, a centrifugal dehydration for 2 minutes, and then a hot air drying at 60 ° C. ± 5 ° C. once.

(Dry cleaning) Using 12.6 mL of tetrachloroethylene and 0.265 g of charge soap (nonionic surfactant / anionic surfactant / water = 10/10/1 (weight ratio)) per 1 g of sample, 30 ° C. ± 2 ° C. The treatment for 15 minutes was defined as one time, and this was performed five times.

  As can be seen from the results shown in Table 2, all of the flame retardant processing agents of Examples using tris (2,3-dibromopropyl) isocyanurate had excellent durability and flame retardancy.

3. Flame retardant processing agent using water-soluble polymer A flame retardant processing agent was used in the same manner as in the above Examples and Comparative Examples, except that a formulation containing a surfactant and a water-soluble polymer shown in Tables 3 and 4 was used. It was prepared and its dispersion state was evaluated. The results are shown in Tables 3 and 4 . The evaluation of the dispersion state is “◎” when the dispersion after standing at room temperature for 7 days after fine dispersion is not precipitated or two-phase separated, “◎” when the dispersion is two-phase separated but redispersible. “O” means that the two-phase separation was impossible and redispersion was impossible.

  Further, the sorption amount and flame retardancy of these flame retardant finishing agents were evaluated in the same manner as in the above examples. The results are shown in Table 5.

  As can be seen from the results shown in Table 5, good flame retardancy was obtained in any of the examples.

4). Combined use of other flame retardant bases A flame retardant processing agent was prepared in the same manner as in the above example except that the formulation shown in Table 6 was used, the amount of sorption was examined, and flame retardance and texture were evaluated. The results are shown in Table 7.

  The flame retardancy was evaluated by the JIS L 1091 A-1 method (45 ° micro burner method) and the JIS L 1091 D method (45 ° coil method) in the same manner as described above. However, in the 45 ° coil method, “◎” indicates that the number of flame contacts is 5 or more, “◯” indicates 3 to 5 times, and “x” indicates 2 or less.

  In addition, the evaluation of the texture is a paired sensory comparison with a blank as a control, “◎” when almost the same as the control, “○” when slightly harder than the control, and “X” when clearly harder than the control. .

  When tris (2,3-dibromopropyl) isocyanurate is used alone, the texture hardness of the work cloth, which is considered to be derived from the structure, may be a problem, but it can be seen from the results shown in Table 7. Thus, it was confirmed that the texture can be improved while maintaining the flame retardancy by using other flame retardant raw materials together.

  In addition, the combined use of tris (2,3-dibromopropyl) isocyanurate and HBCD makes it difficult to exceed the case of using tris (2,3-dibromopropyl) isocyanurate alone or HBCD alone due to a synergistic effect. It was also confirmed that flammability was obtained.

5). Fabrication of fabrics that are difficult to flame retardant The test cloth was a regular polyester / cationic dyeable polyester / regenerated polyester mixed material (50/30/20), and the same composition as in the above example was used except that the composition shown in Table 8 was used. The flame retardant was prepared and subjected to flame retardant processing, and the sorption amount and flame retardancy of the flame retardant were evaluated. The results are shown in Table 9.

  From the results shown in Table 9, even for a regular polyester / cationic dyeable polyester / regenerated polyester mixed material, which is generally difficult to be flame retardant processed, a carrier component or carrier component during processing of the flame retardant processing agent of the present invention. It was found that by using the contained product, it is possible to improve sorption and flame retardancy. It was also confirmed that the same effect can be obtained with a flame retardant processing agent containing a carrier component.

6). Formulation for improving processability According to the formulation (% by weight) shown in Table 10, each flame retardant processing agent is prepared in the same manner as in the above Examples and Comparative Examples, and a regular polyester / cationic dyeable polyester mixed material (CD mixing ratio 50%). Flame retardant processing was performed.

  The dough (dirt) state and the flame retardance after heat setting were evaluated for the case of only soaping using an activator without reducing cleaning and the case of reducing cleaning. In addition, when the reduction cleaning was performed, the light fastness was also evaluated.

  For the evaluation of the fabric state, the ratio of soiling to the entire fabric after heat setting was evaluated by area measurement. Items with 0% contamination are indicated by “◯”, and those with 1% or more contamination are indicated by percentage.

  The evaluation of flame retardancy was carried out in the same manner as in the above example, and after processing, after 5 times of water washing and after 5 times of dry cleaning, all of those with “◯” in the 45 ° micro burner method and 45 ° coil method were evaluated as “○”. And “×” means that there is at least one “×”.

  The light fastness was evaluated in accordance with JIS L 7751 (Test method for fastness to dyeing with respect to ultraviolet carbon arc lamp light) and after irradiating at a black panel temperature of 63 ° C. for 24 hours, it was evaluated using JIS L 0804 (gray scale for fading). .

  As shown in Table 10, by using TBBA derivative, polypropylene glycol, or water-soluble polyester in combination, reduction cleaning is not performed, and even with soaping alone, a good finish is achieved, and the processing process is simplified while maintaining flame retardancy. I was able to confirm that it was possible.

  In addition, when tris (2,3-dibromopropyl) isocyanurate is used alone, it has a high sorption property that is considered to be derived from its structure, so that it adheres to the surface of the fabric more, and the light fastness is lowered. The problem is that only light fastness comparable to that of HBCD, which has low properties, can be obtained, but by using a water-soluble polyester together as shown in Examples 45 to 48 of Table 10, excessive adhesion to the surface is prevented. It was confirmed that the light fastness can be further improved.

7). Evaluation by the Pad Thermo Method (Pad Dry Thermo Cure Method) Using the flame retardant processing agent shown in Table 11, the polyester fiber fabric (regular polyester 100% woven tropical) was subjected to the pad dry thermo cure method. Flame retardant processing was applied.

  Specifically, after immersing the fabric in a solution obtained by diluting the flame retardant to 10% by weight with water, the fabric is squeezed to 70% with a mangle, dried at 110 ° C. for 2 minutes, and cured at 180 ° C. for 2 minutes. did. Then, using soda ash 1.0 g / L and Tripol TK (Daiichi Kogyo Seiyaku Co., Ltd.) 1.0 g / L as chemicals, soaping was performed at a bath ratio of 1:30 at 80 ° C. for 10 minutes. After 5 minutes of hot water washing, it was dried.

  The sorption amount and flame retardancy of the polyester-based fiber fabric thus flame-treated were examined in the same manner as in the above examples. Moreover, the flame retardance was measured also about the untreated textile as a blank. The results are shown in Table 11.

  As can be seen from the results shown in Table 11, the flame retardant processing agents of the examples all exhibited excellent flame retardancy even in the flame retardant processing by the pad dry thermocuring method.

8). Evaluation by Back Coating Method The coating formulation shown in Table 12 below was applied to a polyester fiber fabric (regular polyester 100% fabric) so that the coating amount in terms of solids was 70 g / m ² (Dry). Then, drying and sorption of the flame retardant compound were performed by heating at 150 ° C. for 90 seconds, and the flame retardancy was evaluated. The results are shown in Table 12.

Flame retardancy was evaluated according to the following criteria using a JIS D-1201 FMVSS (302) flammability tester (horizontal method);
◎: Self-extinguishing, flame disappears immediately after digestion of fire source ○: Self-extinguishing, residual flame after digestion of fire source, extinguishes within measurement start point XX: Flammability (burnt)

  As can be seen from the results shown in Table 12, the flame retardant processing agents of the examples all exhibited excellent flame retardancy even in the evaluation by the back coat method.

  The flame retardant processing agent or flame retardant processing method of the present invention is a general polyester fiber product, for example, various interior uses such as curtains, cloth blinds, carpets and other rugs, wall coverings, automobile interior materials such as car seat skin materials, Widely used for sofas and other skin materials, black curtains, notebooks, etc.

Claims (6)

Flame retardant for polyester fiber, which is an aqueous dispersion in which a flame retardant component containing a compound represented by the following general formula (I) is dispersed in water by a surfactant represented by the following general formula (II) Processing agent.
Provided that A ₁ , A ₂ and A ₃ in the general formula (I) are at least one brominated alkyl group selected from 2,3-dibromopropyl, 2,3-dibromoisobutyl and 1,2-dibromoethyl. Represents an alkyl group or an alkenyl group, at least one of which is a brominated alkyl group, and these A ₁ , A ₂ , and A ₃ may be the same or different.
However, X in the general formula (II) represents an anionic group capable of forming a hydrogen atom or a sulfate and / or phosphate ester salts,, Y represents a substituent represented by the following formula, m and n are , M = 1 to 3 and n = 1 to 200, and R ₁ represents an alkylene group having 2 to 4 carbon atoms. X may be only a hydrogen atom or an anionic group, or may be a mixture.
  The flame retardant processing agent for polyester fibers according to claim 1, further comprising a water-soluble polymer as a dispersant.   After applying the flame retardant processing agent according to claim 1 or 2 to a polyester fiber or a fiber product made of this by treatment by a high temperature exhaustion method, or by dipping or coating, heat treatment at 80 ° C. or more is performed. A flame-retardant processing method for polyester fiber, characterized by   The flame-retardant processing method for a polyester fiber according to claim 3, wherein a carrier component is used in combination. The flame retardant processing agent for polyester fibers according to claim 1 or 2, wherein the amount of the surfactant used is in the range of 2 to 15% by weight based on the flame retardant component. The flame retardant processing agent for polyester fibers according to claim 1, 2 or 5, further comprising at least one selected from a tetrabromobisphenol A derivative, polypropylene glycol and a water-soluble polyester.