CN101397755B - Flame retardant processing agent for polyester fiber and its processing method - Google Patents

Abstract

The invention provides a flame retardant processing agent for polyester fiber and a processing method using the same, wherein the flame retardant processing agent can obtain excellent durable flame retardance in materials with high mixing ratio of cationic dyeable polyester. The method uses a flame retardant containing a compound represented by the following general formula The component (A) is a flame retardant processing agent prepared by emulsifying or dispersing a surfactant or a water-soluble polymer in water.Wherein, A in the general formula ₁、A₂、A₃Represents a bromoalkyl group, an alkyl group or an alkenyl group in which a hydrogen atom is replaced by a bromine atom, at least one of which is a bromoalkyl group, A₁、A₂、A₃May be the same or different.

Description

Flame retardant processing agent for polyester fiber and its processing method

technical field

The present invention relates to a flame retardant processing agent capable of imparting flame retardancy to fiber products such as polyester fibers or fabrics made thereof, and a flame retardant processing method using the same.

Background technique

At present, as a flame retardant processing agent for imparting flame retardancy to fiber products such as polyester fibers or fabrics made of them, bromine compounds such as hexabromocyclododecane (HBCD) in water are generally used. Dispersed or emulsified products (Patent Document 1).

However, since HBCD has a low adsorption rate to fiber products such as polyester fibers and fabrics made of them, and a large amount is discharged into the environment, there is a problem of a large environmental load.

It is considered that HBCD used for depletion processing is difficult to decompose and highly accumulated, and there is also a demand for HBCD removal.

In this regard, flame retardant processing agents using phosphorus compounds such as organic phosphates are also used, but in condensed phosphoric acid esters, even if surface adhesion is formed, there is less adsorption to the inside of the fiber, and the surface adhesion will be reduced by reduction washing (RC ) and other alkali soaping or water washing, etc. and fall off. Therefore, insufficient durable flame retardancy is easily caused.

On the other hand, when a low-molecular-weight phosphate ester is used as a flame-retardant processing agent, the adhesion after processing is good, but in actual use, due to washing or dry cleaning, the flame-retardant processing agent tends to fall off easily, and the durable flame-retardant Insufficient sex.

In addition, in the durable flame retardancy for curtain applications, even if the durable flame retardancy of conventional polyester (Reg-PET) is obtained, especially for the mixture ratio ( CD compounding ratio) is 50% or more, and it is difficult to express durable flame retardancy.

In order to solve the above-mentioned problems, for example, an aqueous dispersion containing 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (hereinafter referred to as HCA) and an HCA derivative or Flame retardant processing agent for aqueous emulsion (Patent Documents 2 and 3).

However, if phosphorus-based flame retardants satisfy the flame-retardant performance, a large amount of flame retardants must be treated, and due to the large amount of treatment, sometimes the texture will be reduced and the color tone change of the processed fabrics will be reduced.

In addition, since phosphorus is contained in the drainage of phosphorus-based flame retardants, there is a possibility of nurturing seawater, lake water, and the like.

A flame-retardant finishing agent capable of solving the above-mentioned problems, particularly imparting sufficient durable flame retardancy to fabrics that are more difficult to develop flame retardancy, such as blended fabrics of cationic dyeable polyesters, has not yet been obtained.

Patent Document 1: Japanese Unexamined Patent Publication No. 7-70924

Patent Document 2: JP-A-2002-275473

Patent Document 3: JP-A-2003-306679

Contents of the invention

The problem to be solved by the invention

In view of the above, the object of the present invention is to provide a flame retardant processing agent which solves the problem of insufficient flame retardancy peculiar to phosphorus-based flame retardant processing agents and has excellent durable flame retardancy even in materials with a high CD mixing ratio, And a flame-retardant processing method using the same.

method used to solve the problem

In order to solve the above-mentioned problems, the polyester fiber flame retardant processing agent of the present invention emulsifies or disperses a flame retardant component containing a compound represented by the following general formula (I) in water with a surfactant or a water-soluble polymer.

Among them, A ₁ , A ₂ , A ₃ in the general formula (I) represent a bromoalkyl group, an alkyl group or an alkenyl group in which a hydrogen atom is replaced by a bromine atom, and at least one of them is a bromoalkyl group, A ₁ , A ₂ , _A3 can be the same or different.

Among the above, the surfactant is preferably represented by the following general formula (II).

Wherein, X in the general formula (II) represents a hydrogen atom or an anionic group, Y represents a substituent represented by the following formula, m and n represent the numbers of m=1 to 5, n=1 to 200, and _R represents carbon An alkylene group with a number of 2 to 4. X may be only a hydrogen atom or only an anionic group, or may be a mixture.

The flame-retardant processing method of the polyester fiber of the present invention is to process the flame-retardant processing agent of the present invention above in the polyester fiber or the fiber product made of it by high-temperature exhaustion treatment, or by dipping or coating, and then carry out Heat treatment above 80°C.

Invention effect

The aqueous dispersion or O/W type emulsion of the compound represented by the above general formula shows effective adsorption by using dyeing bath method, padding-drying-thermal curing method, etc. in polyester fiber, and it can be absorbed on the processed cloth The adsorption rate is very high.

Therefore, according to the flame retardant processing agent of the present invention, even for a composite material having a high CD mixing ratio, it can exhibit excellent durable flame retardancy over the conventional bromine-based flame retardant processing agent HBCD. In addition, after flame retardant processing, the amount of flame retardant discharged into the environment is less than that of HBCD, and the impact on the environment is very small.

Detailed ways

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-dibromoisocyanurate) Butyl) isocyanurate, 1,3-bis(2,3-dibromopropyl)-5-allyl isocyanurate, 1,3-bis(2,3-dibromoethyl) )-5-ethylisocyanurate, etc. Among them, tris(2,3-dibromopropyl)isocyanurate can be preferably used.

As a flame retardant component, in the flame retardant component represented by the above general formula (1), it is also possible to use a combination of bromine-based flame-retardant compounds, phosphorus-based flame-retardant compounds, nitrogen-based flame-retardant compounds and inorganic flame-retardant compounds. 1 or more than 2 types.

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 ring Alkanes, polybrominated diphenyl ethers, tetrabromobisphenol (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-tribromophenoxy)ethane, 1,2-bis(2,4,6-tribromophenoxy )-1,3,5-triazine, 2,6- or (2,4)-dibromomonophenol, other polyphenyl ring compounds, ethylene bis-tetrabromophthalimide, other phthalimide Dicarboxylic acid compound, tribromophenyl allyl ether, tribromophenyl acrylate, pentabromobenzyl allyl ether, pentabromobenzyl acrylate, and bromoacrylate monomer, brominated polystyrene, Polybromostyrene, hexabromobenzene, methylol compounds of 2,4-diamino-6-(3,3,3-tribromo-1-propyl)-1,3,5-triazine, etc., But it is not limited to this.

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

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

Examples of phosphorus-based flame retardant compounds used together in the present invention include triphenyl phosphate, tricresyl phosphate, tris(xylyl phosphate), cresyl phenyl phosphate, other aromatic phosphates, aromatic condensation Phosphorus compounds such as phosphoric acid esters, and aromatic phosphorus compounds represented by the following chemical formulas (V) and (VI), alkali metal salts, alkaline earth metal salts, aluminum salts, zinc salts, or amine salts of compounds represented by chemical formulas (VI) , or a phosphazene compound represented by the following chemical formula (VIII), but not limited thereto.

In chemical formulas (V) and (VI), R ₃ and R ₄ represent an alkyl group having 1 to 24 carbons, an alkenyl group having 2 to 22 carbons, a hydroxyalkyl group having 1 to 10 carbons, optionally having a substituent Aralkyl group, -OH group, alkoxy group having 1 to 10 carbon atoms, aralkyloxy group optionally having 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 carbons, or an alicyclic alkyl group having 5 to 6 carbons.

In the chemical formula (VIII), R ₆ and R ₇ may be the same or different, respectively representing an alkyl group with 1 to 24 carbons, an alkenyl group with 2 to 22 carbons or an aryl group optionally having substituents, and o represents 3 to Integer of 10.

In particular, triphenyl phosphate, diphenyl mono-ortho-biphenyl phosphate, 2-naphthyl diphenyl phosphate, and 10-benzyl-9,10-dihydro-9 represented by the following chemical formula (IX) can be preferably used. -oxa-10-phosphaphenanthrene-10-oxide.

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

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

A surfactant can be used when dispersing or emulsifying the flame retardant component represented by the general formula (I) and the flame retardant component used together in water. As the surfactant, combinations of known nonionic surfactants and anionic surfactants or any one thereof can be used.

Specific examples of nonionic surfactants include polyoxyalkylene alkylphenyl ethers, polyoxyalkylene alkyl ethers, polyoxyalkylene fatty acid esters, polyol fatty acid ester oxide alkylene ethers, and polyoxyalkylene alkyl ethers. Products, higher alkylamine oxyalkylene adducts, fatty amide oxyalkylene adducts, alkyl glycosides, sucrose fatty acid esters, etc.

Specific examples of anionic surfactants include higher alcohol sulfates, polyoxyalkylene alkyl ether sulfates, alkylbenzenesulfonates, alkylnaphthalenesulfonates, naphthalenesulfonate formaldehyde condensation substances, as well as higher alcohol phosphate ester salts, polyoxyalkylene alkyl ether phosphate ester salts, etc. In addition, polyoxyalkylene alkyl ether carboxylate salt, polycarboxylate, Turkish red oil, petroleum sulfonate, alkyl diphenyl ether sulfonate, etc. are mentioned.

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

Specific examples of amphoteric surfactants include alkyl betaines, fatty amidopropyl betaines, 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaines, alkyl diethylene Ethyltriaminoacetic acid, dialkyldiethylenetriaminoacetic acid, alkylamine oxide, etc.

Specific examples of cationic surfactants include monoalkylamine salts, dialkylamine salts, trialkylamine salts, alkyltrimethylammonium chloride, alkyltrimethylammonium bromide, alkyl Trimethylammonium iodide, dialkyldimethylammonium chloride, dialkyldimethylammonium bromide, dialkyldimethylammonium iodide, alkylbenzalkonium chloride, and the like.

In the present invention, when the flame retardant component is dispersed in water or O/W emulsified, it is particularly preferable to use a nonionic surfactant or an anionic surfactant represented by the general formula (II).

As the nonionic surfactant, specifically, polyoxyalkylene monobenzylated phenyl ether, polyoxyalkylene dibenzylated phenyl ether, polyoxyalkylene tribenzylated phenyl ether, polyoxyalkylene tribenzylated One or more of phenyl ethers, polyoxyalkylene monostyrenated phenyl ethers, polyoxyalkylene distyrenated phenyl ethers and polyoxyalkylene tristyrenated phenyl ethers mixture.

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

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

As the anionic surfactant, specifically, 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 Benzylated phenyl ether phosphate, polyoxyalkylene monostyrenated phenyl ether sulfate, polyoxyalkylene distyrenated phenyl ether sulfate, polyoxyalkylene triphenylene Phenyl ether sulfate, polyoxyalkylene monostyrenated phenyl ether phosphate, polyoxyalkylene distyrenated phenyl ether phosphate and polyoxyalkylene tristyrenated benzene One or more mixtures of base ether phosphate ester salts.

The addition mol number of the polyoxyalkylene group of the said surfactant becomes like this. Preferably it is 1-200, More preferably, it is 10-50.

In the present invention, the usage-amount of the said surfactant is not specifically limited, Usually, it uses in the range of 2-15 weight% with respect to a flame retardant component. If the surfactant is less than this range, it will be difficult to obtain a sufficient dispersion effect, and if it is more than this range, the surfactant which is a flammable substance will remain in the processed cloth, and a sufficient flame retardant effect will not be obtained.

The flame retardant component represented by the said general formula (1), the flame retardant component used together, and surfactant can use a commercially available thing, and can also manufacture by a well-known method. The obtained compound is a mixture, and what is necessary is just to isolate|separate by well-known isolation|separation methods, such as distillation, when it must be a monomer.

In the present invention, a flame retardant component may also be dispersed in a water-soluble polymer (protective colloid). In the case of dispersing the flame retardant component in the water-soluble polymer, the viscosity of the dispersion can be adjusted appropriately, the sedimentation of the slurry can be suppressed, and a uniform fine dispersion can be formed. In addition, there is no need for product separation after productization. Examples of water-soluble polymers that can be used include carboxymethyl cellulose salts, xanthan gum, gum arabic, locust bean gum, sodium alginate, self-emulsifying polyester compounds, polyvinyl alcohol (PVA), Gelatin, polyvinylpyrrolidone, polyethylene oxide, polyacrylamide, methoxyethylene maleic anhydride copolymer, methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, soluble starch, carboxymethyl starch , Cationic starch, etc. Among these, carboxymethylcellulose salt and xanthan gum are preferable from the viewpoint of the physical properties of the resulting solution, its stability, and the like.

The above-mentioned self-emulsifying polyester compound is, specifically, bis(hydroxyalkyl) terephthalate or a mixture of bis(hydroxyalkyl) terephthalate and di(hydroxyalkyl) isophthalate The polycondensate with polyalkylene glycol selected from polyethylene glycol, polypropylene glycol and polytetramethylene glycol has a molecular weight of 300-50,000, preferably 5,000-20,000. Furthermore, the polyalkylene glycol portion is composed of 1 to 150 mol, preferably 50 to 100 mol, of oxyalkylene units.

Furthermore, in order to stabilize the dispersed state, the flame retardant processing agent of the present invention may contain organic solvents such as alcohols, aromatic solvents, glycol ethers, alkylene glycols, and terpenes.

In addition, when processing the flame-retardant processing agent of the present invention, by using a carrier component or a substance containing a carrier component, even conventional polyester/cationically dyeable polyester/recycled polyester hybrid materials, etc., which are generally considered difficult to perform flame-retardant processing, Adsorptivity and flame retardancy can also be improved for materials that are difficult to flame retard.

The so-called carrier component refers to a substance capable of highly adsorbing the flame retardant processing agent uniformly in the polyester fiber and having a strong affinity with both the polyester fiber and the flame retardant processing agent.

Examples of compounds having the above-mentioned carrier components include benzyl benzoate, methyl benzoate, aromatic halogen compounds, N-alkylphthalimides, methylnaphthalene, biphenyl, and biphenyl esters. , naphthol esters, phenol ethers and hydroxybiphenyls, etc. Among them, benzyl benzoate and polyoxyalkylene mononaphthyl ether are preferable.

Various resin additives such as ultraviolet absorbers and antioxidants may be added to the flame-retardant processing agent of the present invention.

As will be described later, the flame retardant processing agent of the present invention can be soaked in a liquid diluted with water by the same-bath dyeing method in which the dye is absorbed into the fiber at the same time, squeezed with a liquid squeezer to a predetermined adhesion amount, and then dried. , heat-setting padding-drying-thermal curing method, mixing resin binder with the product of the present invention and/or flame retardant additives, thickening, coating on fibers and other methods of processing.

The flame-retardant processing method of the present invention includes the steps of post-processing polyester fibers, imparting the above-mentioned flame-retardant processing agent, and performing a heat treatment at 80° C. or higher. Examples of the post-processing include a high-temperature exhaustion method, a pad heat treatment method, and a coating method.

In the high-temperature exhaustion method, the polyester fiber is immersed in a treatment bath with a flame-retardant processing agent, and treated at a high temperature (usually 80°C or higher, preferably 110-140°C) for a predetermined time (for example, 2 to 60 minutes), Make the fiber absorb the flame retardant. It is preferable to use the same-bath dyeing method in which the flame retardant and the dye are simultaneously adsorbed to the fiber. That is, it is effective and preferable to add a flame retardant processing agent to a dyeing bath, immerse polyester fibers in the dyeing bath, and perform an exhaustion treatment at a high temperature.

In addition, in the padding heat treatment method, the polyester fiber is dipped in a liquid containing a flame-retardant processing agent, squeezed to a predetermined adhesion amount with a liquid squeezer, etc., and then subjected to dry heat treatment, or heat treatment is performed by steam heat treatment such as heating steam treatment. , so that the fiber absorbs the flame retardant. The heat treatment temperature is usually in the range of 110 to 210°C. It is preferably treated by a padding-drying-thermal curing method of extrusion with a liquid squeezer after dipping, drying, and heat setting.

In the coating method, the resin binder is mixed with the product of the present invention and/or flame retardant additives, etc., thickened, and coated on the fiber.

In addition, among the polyester fibers to be treated, in addition to polyethylene terephthalate (PET), polybutylene terephthalate (PBT) and polytrimethylene terephthalate (PTT) In addition, copolymers containing a third component such as isophthalic acid, isophthalic acid sulfonate, adipic acid, polyethylene glycol, etc., especially cationic dyeable polyester, etc. In addition, when producing threads, dope dyed threads made of refined mixed pigments can be used. In addition, the fiber products to be treated include various threads, fabrics, non-woven fabrics, ropes, etc., and may also be blended fabrics and composite materials using threads different from the above-mentioned fibers, for example, including polyester fiber dope dyed thread blended cloth etc. Fiber products can also be products made by combining other synthetic fibers, natural fibers or semi-synthetic fibers through blending or the like.

Example

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

1. Preparation of flame retardant processing agent

According to the proportioning (% by weight) shown in the following table 1, mix and stir the prescription liquid of embodiment and comparative example, obtain slurry, then mix and stir the glass beads of diameter 2.0mm with this slurry identical volume, it is filled in The grinding process was carried out for 2 hours in a sand mill manufactured by Aimex Co., Ltd. After the pulverization treatment, the glass beads and the dispersion were separated through a 100-mesh filter cloth.

According to the compounding ratio (weight%) shown in the following Table 1, each flame-retardant processing agent of an Example and a comparative example was prepared. In addition, surfactants (1) to (4) were produced according to the method described in Chapter 2 of "Nonionic Surfactant" by Yoshiro Ishii (Seibundo Shinkosha).

Table 1

Tris(2,3-dibromopropyl)isocyanurate: product name TAIC-6B, manufactured by Nippon Chemicals Co., Ltd.

Surfactant (1): styrenated phenol (weight ratio single: two: three = 15:50:35) 10EO adduct

Surfactant (2): styrenated phenol (weight ratio single: two: three = 5:35:60) 20EO adduct

Surfactant (3): styrenated phenol (weight ratio single: two: three = 5:35:60) sulfate ester ammonium salt of 20EO adduct

Surfactant (4): Phosphate monoethanolamine salt of styrenated phenol (weight ratio single: two: three = 15:50:35) 10EO adduct

Antifoaming agent: ANTIFROS M-8 manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd.

2. Evaluation of the same bath method for dyeing

Using the flame retardant processing agent dispersed in the above examples and comparative examples, the conventional polyester/cation dyeable polyester hybrid material (CD mixing ratio 50%) was subjected to flame retardant processing by the same-bath dyeing method.

Specifically, Mini-Color (manufactured by Texam Giken) was used as a dyeing machine, and the temperature was raised from 60° C. for 30 minutes at 130° C. at a bath ratio of 1:10 for the dyeing bath recipe shown below. The treatment amount of the flame retardant finishing agent was 10% o.w.f (based on the weight of the fiber (ratio to the weight of the fiber)). After treatment, cool down to 80°C, take out the fabric, wash with hot water for 5 minutes, use the following reduction washing bath prescription, wash at 80°C for 10 minutes at a bath ratio of 1:30, and then wash with hot water for 5 minutes. minutes, followed by heat setting 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 1.0g/l

Anhydrous sodium acetate 3.0g/l

Flame retardant X%owf

[Restoration washing bath prescription]

Sodium bisulfite 2.0g/l

Soda lime 1.0g/l

トライポ-ルTK 1.0g/l

In the above, the adsorption amount and flame retardancy of the flame retardant processing agent were investigated. The results are shown in Table 2. In addition, the evaluation method of flame retardancy is as follows.

[flame retardant]

In flame-retardant processed fabrics, the processed fabrics, and the fabrics washed or dry-cleaned under the following conditions, according to JIS L 1091 A-1 method (45° (micro flame lamp) tilt method) and JIS L 1091 D method (45 ° coil method) to determine the flame retardancy. In the 45° tilt method, after heating for 1 minute and burning for 3 seconds, the afterburn time is less than 3 seconds, the afterburn time is less than 5 seconds, and the charring area is less than 30 cm ² is marked as "○", Others were marked with "×". In the 45° coil method, the number of times of ignition is marked as "○" if it is more than 3 times, and it is marked as "×" if it is less than 2 times. In addition, for comparison, the flame retardancy was also measured on untreated fabrics.

(Water washing) According to JIS K 3371, wash with water for 15 minutes at 60°C±2°C with a bath ratio of 1:40 and 60°C±2°C, and then wash at 40°C±2°C The operation of rinsing for 5 minutes was performed 3 times, and the treatment of centrifugal dehydration for 2 minutes, and then drying with hot air at 60°C±5°C was performed 5 times, taking the above operation as 1 time.

(Dry cleaning) For each 1g sample, use 12.6mL tetrachlorethylene, 0.265g filling soap (nonionic surfactant/anionic surfactant/water=10/10/1 (weight ratio)), at 30℃±2 The treatment was carried out at °C for 15 minutes, and the above-mentioned operation was performed 5 times as 1 time.

Table 2

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

3. Flame retardant processing agent using water-soluble polymer

Except for using the combination of the surfactant and the water-soluble polymer shown in Table 3, the flame retardant processing agent was prepared in the same manner as the above-mentioned examples and comparative examples, and its dispersion state was evaluated. The results are shown in Table 3. The evaluation of the dispersion state is as follows: after microdispersion, the dispersion after standing at room temperature for 7 days was marked as "◎", and the dispersion was marked as "○" when the two phases were separated but could be redispersed. The two phases separated and could not be redispersed were marked as "×".

In addition, Table 4 shows examples similar to those of the above-mentioned Examples and Comparative Examples except that only the water-soluble polymer compounding system was compounded. The products of the present invention, as shown in this table, are also dispersible in complex systems containing only water-soluble polymers.

In addition, the adsorption|suction amount and flame retardancy of these flame-retardant processing agents were evaluated similarly to the said Example. The results are shown in Table 5.

Table 4

Tris(2,3-dibromopropyl)isocyanurate: product name TAIC-6B, manufactured by Nippon Chemicals Co., Ltd.

Water-soluble polymer (1): Carboxymethylcellulose sodium salt (manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd.: Serogen BS)

Water-soluble polymer (2): Xanthan gum

Water-soluble polymer (3): methyl cellulose (manufactured by Shin-Etsu Chemical Co., Ltd.: Metro-Z MS)

Water-soluble polymer (4): Hypromellose (manufactured by Shin-Etsu Chemical Co., Ltd.: Metro-Z 60SH)

Water-soluble polymer (5): Self-emulsifying polyester compound (polycondensation product of bis(hydroxyethyl)terephthalate and polyethylene glycol (average molecular weight about 9000))

Surfactant (2): styrenated phenol (weight ratio single: two: three = 5:35:60) 20EO adduct

table 5

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

4. Use other flame retardant raw materials together

Except having used the compounding shown in Table 6, similarly to the said Example, the flame retardant processing agent was prepared, the adsorption|suction amount was examined, and flame retardancy and texture were evaluated. The results are shown in Table 7.

In addition, the evaluation of flame retardancy was carried out in accordance with JIS L 1091 A-1 method (45° tilt method) and JIS L 1091 D method (45° coil method) in the same manner as above. Among them, in the 45° coil method, the number of times of ignition is marked as "◎" for 5 or more times, "○" for 3 to 5 times, and "×" for less than 2 times.

In addition, in the evaluation of the texture, the blank was used as a control, and a one-to-one comparison of the sensory was performed. The case that was basically the same as the control was marked as "◎", the case that was slightly harder than the control was marked as "○", and the case that was significantly harder than the control was marked. The case is recorded as "×".

Table 7

31 ^* "Implementation product I/comparison product G = 7/3" mixed product

32 ^* "implementation product I / phosphorus flame retardant (1) ^* = 8/2" mixed product

33 ^* "Implementation product I/phosphorous flame retardant (2) ^* = 7/3" mixed product

Phosphorous flame retardant (1) ^* "mix and stir 5 parts by weight of styrenated phenol in 40 parts by weight of diphenyl o-biphenyl phosphate (weight ratio: two: three = 15:50:35) 10EO plus into a product, slowly drop into 55 parts by weight of distilled water to obtain an emulsified dispersion."

Phosphorous flame retardant (2) ^* "Same as embodiment 2, mix and stir 5 parts by weight of styrenated phenol in 40 parts by weight of phosphorus compounds (chemical formula (III) ^* (weight ratio single: two: three=5 :35:60) 20EO adduct, using 55 parts by weight of distilled water for wet microdispersion to obtain a dispersion."

Compound of formula (III) ^* "10-benzyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide"

When tris(2,3-dibromopropyl)isocyanurate is used alone, the texture hardness of the processed cloth that is considered to be derived from its structure may sometimes become a problem. It can be confirmed from the results shown in Table 7 that by using other Flame-retardant raw materials can maintain flame-retardant properties and improve texture.

In addition, it was also confirmed that by using tris(2,3-dibromopropyl)isocyanurate and HBCD in combination, due to the synergistic effect, it is possible to obtain Higher flame retardancy when using esters or HBCD alone.

5. Processing of fabrics that are difficult to be flame-retardant processed

Test cloth is conventional polyester/cation dyeable polyester/regenerated polyester hybrid material (50/30/20), except using the proportioning shown in table 8, same as above-mentioned embodiment, prepare flame retardant processing agent, The flame retardant processing was carried out, and the adsorption amount and flame retardancy of the flame retardant processing agent were evaluated. The results are shown in Table 9.

Table 8

[Usage %owf]

Carrier (1): α-naphthol 3EO adduct

Carrier (2): Benzyl Benzoate

^(*) Added for combination of Example 36, 37 and carrier active ingredient

Table 9

As can be seen from the results shown in Table 9, even conventional polyester/cation dyeable polyester/regenerated polyester hybrid materials, which are generally difficult to flame-retardantly process, can be processed by using the flame-retardant processing agent of the present invention. Carrier components or products containing carrier components to improve adsorption and flame retardancy. In addition, it was confirmed that the same effect can be obtained by using a flame retardant processing agent containing a carrier component.

6. Evaluation by pad heat treatment method (pad-dry-heat curing method)

Using the flame-retardant processing agents shown in Table 10, polyester-based fiber fabrics (normal polyester 100% fabric summer fabrics) were subjected to flame-retardant processing by a pad-dry-heat-curing method.

Specifically, the above-mentioned fabric is dipped in a liquid in which the flame retardant processing agent is diluted to 10% with water, squeezed to a squeeze rate of 70% with a liquid manipulator, dried at 110°C for 2 minutes, and then dried at 180°C. Cure for 2 minutes. Then, as a reagent, use 1.0g/L soda lime and 1.0g/L Triple TK (trade name of a surfactant for soaping, manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd.), at a bath ratio of 1:30 , soaped at 80°C for 10 minutes, then washed with hot water for 5 minutes, and then dried.

With regard to the polyester fiber fabric thus flame-retardantly processed, the adsorption capacity and flame retardancy were studied in the same manner as in the above-mentioned examples. In addition, flame retardancy was also determined on the untreated fabric as a blank. The results are shown in Table 10.

Table 10

As can be seen from the results shown in Table 10, the flame retardant processing agents of Examples all showed excellent flame retardancy when subjected to flame retardant processing by the padding-drying-thermal curing method.

7. Evaluation by pad coating method

Polyester-based fiber fabrics (conventional polyester 100% fabrics) were coated according to the coating recipe shown in Table 11 below so that the coating amount in terms of solid content was 70 g/m ² (dry coating amount). Then, it was heated at 150° C. for 90 seconds, dried and adsorbed with a flame retardant compound, and evaluated for flame retardancy. The results are shown in Table 11.

Flame retardancy adopts JIS D-1201 FMVSS (302) flammability testing machine (horizontal method), and is evaluated according to the following criteria;

◎: Self-extinguishing, the flame disappears immediately after the fire source disappears

○: Self-extinguishing, after the fire source disappears, the flame still remains, but the flame disappears within the measurement start point

××: Flammability (full combustion)

Table 11

As can be seen from the results shown in Table 11, the flame retardant finishing agents of Examples all showed excellent flame retardancy in the evaluation by the pad coating method.

Industrial Applicability

The flame retardant processing agent or flame retardant processing method of the present invention can be widely applied to all polyester fiber products, for example, it can be used for various interior decoration purposes such as curtains, fabric shutters, carpets and other articles laid on the ground, wall materials, etc. For example, car interior decoration materials such as surface materials for car covers, surface materials such as sofas, blackout curtains, thick floor curtains, etc.

Claims (3)

1. polyester fiber is used Fire-retardant processed goods, and its fire retardant composition that will contain formula (I) expression compound forms through surfactant and/or water soluble polymer emulsification or dispersion in water,

Wherein, the A in the general formula (I) ₁, A ₂, A ₃Expression is selected from 2,3-dibromopropyl, 2, and 3-dibromo-isobutyl base, 1, at least a bromo alkyl in 2-two bromoethyls, alkyl or alkenyl, at least one in them is the bromo alkyl, A ₁, A ₂, A ₃Can be identical or different,

Above-mentioned surfactant is by formula (II) expression,

Wherein, the X in the general formula (II) representes hydrogen atom or anionic property group, and Y representes the substituting group shown in the following formula, and m and n represent the number of m=1～5, n=1～200, R ₁The alkylidene of expression carbon number 2～4, X can only be hydrogen atom or only be the anionic property group, also can be their mixture,

Above-mentioned water soluble polymer is selected from a kind in the condensation polymer of sanlose, xanthans, methylcellulose, CMC and two (ethoxy) terephthalate and polyethylene glycol.

2. the flame retardant processing method of polyester fiber, it is handled through high temperature exhaustion method or through dipping or coating, give Fire-retardant processed goods as claimed in claim 1 to polyester fiber or by the fibre that it is processed after, implement the heat treatment more than 80 ℃.

3. the flame retardant processing method of polyester fiber as claimed in claim 2 is characterized in that, and uses carrier components.