JP2010024580A - Flame-retarding agent for polyester fiber and method for flame-retarding treatment - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a flame-retarding agent for polyester fibers free from the problem of insufficient flame-retardancy which is inherent in phosphorus-based flame-retarding agents and developing excellent durable flame-retardancy even in a material having high CD blend ratio. <P>SOLUTION: The flame-retarding agent for polyester fibers is produced by dispersing tris(tribromoneopentyl) phosphate expressed by general formula (1) in water with a surfactant or a protective colloid agent. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a flame retardant processing agent capable of imparting flame retardancy to a fiber product such as polyester fiber or 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.

  HBCD that has been used for exhaustion processing has been found to have persistent decomposition and high accumulation, and there is also 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.

There has not yet been obtained a fabric that can solve these various problems and that can impart sufficient durability flame retardance even for fabrics that are more difficult to exhibit flame retardancy, such as blended products of cationic dyeable polyester.
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 exhibits excellent durability flame retardancy even in materials having a high CD mixing ratio. And a flame retardant processing method using the same.

The flame retardant processing agent for polyester fiber according to the present invention is obtained by dispersing tris (tribromoneopentyl) phosphate represented by the following general formula (1) in water with a surfactant and / or a protective colloid agent. Features.

  In the present invention, the surfactant is at least one selected from a nonionic surfactant and an anionic surfactant, the protective colloid agent is a water-soluble polymer, and the surfactant and the protective colloid 1 type (s) or 2 or more types selected from the agent can be used.

In the above, it is preferable that the surfactant is a compound represented by the following general formula (2).

However, X in the general formula (2) represents a hydrogen atom or an anionic group represented by the following general formula (3), Y represents a substituent represented by the following formula (4), and m and n are m = 1 to 5, n = 1 to 200, R ₁ represents an alkylene group having 2 to 4 carbon atoms, and when n is 2 or more, (R ₁ O) may be the same or different, and The form may be block or random. X may be only a hydrogen atom or an anionic group, or may be a mixture. M and M ′ in the general formula (3) represent a hydrogen atom, a metal atom, an ammonium or a hydrocarbon group.

  The method for flame retardant processing of polyester fiber according to the present invention comprises applying the flame retardant processing agent according to 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. It shall be subjected to a heat treatment of at least ° C.

  By dispersing the compound represented by the general formula (1) in water, a flame retardant having a low sedimentation property and a good dispersion state can be obtained as compared with the HBCD dispersion. In particular, by using an anionic surfactant represented by the general formula (2) as a surfactant, a dispersion having a very stable dispersion state can be obtained.

  Effective sorption can be achieved by treating polyester fiber with an aqueous dispersion or O / W emulsion of the compound represented by the general formula (1) by a dye-same bath method, a pad dry thermocuring method, or the like. High sorption rate on processed cloth.

  Therefore, according to the flame retardant processing agent of the present invention, even a composite material having a high CD blending ratio exhibits excellent durability flame resistance equivalent to that of the conventional brominated flame retardant processing agent HBCD.

  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, in order to disperse the flame retardant component in water or form an O / W emulsion, it is particularly preferable to use a nonionic surfactant or an anionic surfactant represented by the general formula (2).

  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 (2) 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 5-50.

  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, polyvinyl alcohol (PVA), gelatin, polyvinyl pyrrolidone, polyethylene oxide , Polyacrylamide, methoxyethylene maleic anhydride copolymer, methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, soluble starch, carboxymethyl starch, cationized starch and the like. 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 is composed of 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.

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

  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.

  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.

  Compounds having the above carrier performance include benzyl benzoate, methyl benzoate, aromatic halogen compounds, N-alkylphthalimides, methylnaphthalene, dibenzyl ether, diphenyl, diphenyl esters, naphthol esters, phenol ethers and hydroxy ethers And diphenyls. 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 subjecting it to a heat treatment of 80 ° C. or more. As an example of such a post-processing treatment, , 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 as to obtain a predetermined adhesion amount, and heat treatment is performed by a steam heat treatment such as a dry heat treatment or a heating 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 [preparation of coarse dispersion solution]
According to the composition (% by weight) shown in Table 1 below, each flame retardant processing agent of Examples and Comparative Examples was prepared. The compounding components used are as follows.

(Compounding ingredients)
-Tristo (ribromoneopentyl) phosphate: Product name CR-900, manufactured by Daihachi Chemical Industry Co., Ltd.-Diphenyl monoorthoxenyl phosphate: manufactured by Daihachi Chemical Industry Co., Ltd.-Surfactant (1): Styrene Phenol (weight ratio mono: di: tri = 15: 50: 35) Phosphate ester / surfactant of 10EO adduct (2): styrenated phenol (weight ratio mono: di: tri = 15: 50: 35) 10EO adduct sulfate ammonium salt / surfactant (3): styrenated phenol (weight ratio mono: di: tri = 15: 50: 35) 10EO adduct / surfactant (4): styrenated phenol (weight) Ratio mono: di: tri = 15: 50: 35) 20EO adduct / surfactant (5): styrenated phenol (weight ratio mono: di: tri = 5: 35: 60) 10E -10PO adduct, block addition / surfactant (6): tribenzylated phenol 10EO adduct / surfactant (7): naphthalenesulfonic acid formalin condensate Na salt: product name Labelin FH-L, Daiichi Kogyo Seiyaku Co., Ltd. Made by Co., Ltd. Antifoam: Product name Anti-Floss M-8, Daiichi Kogyo Seiyaku Co., Ltd. surfactants (1) to (6) are written by Yoshiro Ishii, “Nonionic Surfactant” (Seifumi) Manufactured by the method described in Chapter 2.

[Fine dispersion of coarse dispersion]
Disperser: Batch type bead mill (Imex Co., Ltd .: Sand grinder)
Formulation: Coarse dispersion solution / 2 mm glass beads = 150 g / 225 g
Dispersion time: 2 hours

[Evaluation of dispersion stability]
The stability of the fine dispersion was evaluated. 1st, 7th, 30th, 90th days after fine dispersion, the state of the dispersion after standing at room temperature is “◯” for stable, “△” for surface water separation, and two-layer separation This is shown in Table 2 as “x”.

2. Flame retardant performance evaluation in the dyed bath method Using the flame retardant processing agents listed in Table 1 and comparative products, regular polyester / cation dyeable polyester mixed material fabric (CD blend ratio 50%) by the dyed bath method Flame retardant processing was applied.

[Test conditions]
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 amount of flame retardant processing agent is 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 0.20% 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
・ Tripole TK 1.0 g / L

  In the above, the sorption amount and flame retardancy of the flame retardant finish were evaluated. The results are shown in Table 3. The flame retardant evaluation method is as follows.

[Flame retardance]
For woven fabrics that have been flame-retarded, and those that have been processed and those that have been washed or dry-cleaned under the following conditions, JIS L 1091 A-1 method (microburner method) and JIS L 1091 D method (45 ° coil method) ) To measure flame retardancy. The micro burner method, "both after the heating for 1 minute and Chakuen 3 seconds, with the remaining flame time is 3 seconds or less, or less Zanchiri time 5 seconds, and carbide area as pass those 30 cm ² or less ○ ", And the others were marked with" x ". In the coil method, a case where the number of times of flame contact was 3 times or more was indicated as “O” as a pass, and a case where it was burned out even less than 3 times was determined as “X” as a failure. For comparison, flame resistance was also measured for an untreated fabric (blank).

[Water washing]
According to JIS K 3371, a weak alkaline first-class detergent was used at a rate of 1 g / L, and a bath ratio of 1:40 was washed with water at 60 ° C. ± 2 ° C. for 15 minutes, and then rinsed at 40 ° C. ± 2 ° C. for 5 minutes. Was performed three times, and centrifugal dehydration was performed for 2 minutes. Thereafter, the hot air drying at 60 ° C. ± 5 ° C. was performed once, and this was performed five times.

[Dry cleaning]
Using 12.6 mL of tetrachlorethylene per 1 g of sample and 0.265 g of charge soap (nonionic surfactant / anionic surfactant / water = 10/10/1 (weight ratio)) at 30 ° C. ± 2 ° C. for 15 minutes The treatment was performed once and this was performed 5 times.

[Feel]
The evaluation of the texture was a functional paired comparison using a blank as a control. The case where it was almost the same as the control was “◯”, the case slightly harder than the control was “△”, and the case clearly harder than the control was “X”.

  As can be seen from the results shown in the table, all of the flame retardant processing agents of Examples using tris (tribromoneopentyl) phosphate had excellent durability and flame retardancy.

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

Claims (4)

A flame retardant processing agent for polyester fiber, characterized in that tris (tribromoneopentyl) phosphate represented by the following general formula (1) is dispersed in water with a surfactant and / or a protective colloid agent.

  The surfactant is at least one selected from a nonionic surfactant and an anionic surfactant, the protective colloid agent is a water-soluble polymer, and is selected from the surfactant and the protective colloid agent 1 type or 2 types or more are used, The flame-retardant processing agent of the polyester fiber of Claim 1 characterized by the above-mentioned. The flame retardant processing agent for polyester fiber according to claim 1 or 2, wherein the surfactant is represented by the following general formula (2).

However, X in the general formula (2) represents a hydrogen atom or an anionic group represented by the following general formula (3), Y represents a substituent represented by the following formula (4), and m and n are m = 1 to 5, n = 1 to 200, R ₁ represents an alkylene group having 2 to 4 carbon atoms, and when n is 2 or more, (R ₁ O) may be the same or different, and The form may be block or random. X may be only a hydrogen atom or an anionic group, or may be a mixture. M and M ′ in the general formula (3) represent a hydrogen atom, a metal atom, an ammonium or a hydrocarbon group.

  After applying the flame retardant processing agent for polyester fiber according to any one of claims 1 to 3 to a polyester fiber or a fiber product comprising the same by treatment by a high temperature exhaust method, or by dipping or coating, 80 ° C or higher. A flame retardant processing method for polyester fiber, characterized by subjecting to heat treatment.