JP2001254268A - Flameproof finishing agent for synthetic fiber structure - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a flameproof finishing agent capable of imparting flameproof properties excellent in durability to a synthetic fiber structure without using a halogen-based compound. SOLUTION: This flameproof finishing agent for the synthetic fiber structure is characterized in that an aromatic diphosphate powder represented by general formula (I) (wherein, R1 and R2 are each a same or different lower alkyl group; R3 and R4 are each a same or different hydrogen atom or lower alkyl group; Y is a bond between carbons,-CH2-,-C(CH3)2-,-S-,-SO2-,-O-,-CO- or -N=N-; (m) is an integer of 0-4; (n)is 0 or 1) is dispersed in water as fine particles having <=2 μm average particle diameter by a nonionic surfactant selected from a polyoxyalkylene alkyl ether and a polyoxyalkylene alkylphenyl ether.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a flameproofing agent capable of imparting excellent durability to flameproofing without using a halogen compound in a synthetic fiber structure.

[0002]

2. Description of the Related Art Hitherto, as a method for imparting flameproofing properties to a synthetic fiber structure by post-processing, a halogen compound, typically, for example, 1,2,5,6,9,10-hexabromo A method is known in which a brominated cycloalkane such as cyclododecane is used as a flameproofing agent and dispersed in water with a dispersing agent, and a flameproofing agent is attached to a synthetic fiber structure (Japanese Patent Publication No. Sho 5).
No. 3-8840). However, according to the method of imparting flameproofing performance by attaching a halogen-based compound to a synthetic fiber structure as described above, when such a synthetic fiber structure burns, a harmful halogenated gas is generated, There is a problem that this adversely affects the natural environment. Accordingly, in recent years, the use of such a halogen-based compound as a flame retardant has been regulated.

[0003] Therefore, it has heretofore been attempted to provide a synthetic fiber structure with flame retardancy by using a phosphorus compound such as an organic phosphate as a flame retardant instead of such a halogen compound. Have been done. However, conventionally, phosphorus-based compounds generally used as flame retardants have a low phosphorus content in the compound and, because of their low molecular weight, for example, below the flash point of polyester-based synthetic fiber structures. In order to decompose and volatilize, it was difficult to impart sufficient flameproofing performance to the synthetic fiber structure. Therefore,
In order to impart sufficient flame resistance to a polyester-based synthetic fiber structure with such a phosphorus-based compound, it was necessary to use a large amount of the phosphorus-based compound.

However, when a large amount of the phosphorus-based compound is used, the texture of the synthetic fiber structure is impaired, and the phosphorus-based compound migrates to the surface of the synthetic fiber structure with the passage of time. Dyes and the like used for dyeing the fibrous structure also cause so-called surface bleeding which migrates to the surface of the synthetic fibrous structure, and there is a problem that the color fastness is reduced.

Therefore, in order to solve such a problem, a flame-retardant performance has been conventionally imparted to a synthetic resin molded article or a synthetic fiber structure by using a high molecular weight, crystalline phosphorus compound as a flame retardant. It has been proposed to apply the method (Japanese Patent Laid-Open No.
-1079 publication). However, in order to impart flameproofing properties to the synthetic fiber structure by post-processing, such a phosphorus-based compound is formulated, that is, a dispersion liquid is prepared which is stably dispersed in water at a high concentration as fine particles. However, conventionally, it has been difficult to stably disperse the crystalline phosphorus compound as such fine particles in water at a high concentration.

Under these circumstances, the present inventors have developed a crystalline powder of a certain aromatic diphosphate into a synthetic fiber structure,
In particular, as a result of intensive studies on the use as a flameproofing agent for polyester-based synthetic fiber structures, by selecting and using a certain nonionic surfactant, the aromatic diphosphate as fine particles, stably in water, Moreover, it can be dispersed in a high concentration, and thus the flameproofing agent composed of such a dispersion is adhered to the synthetic fiber structure by a post-processing treatment, so that the synthetic fiber has excellent flameproofing performance. The present invention has been found that it can be applied to a structure, and has led to the present invention.

Accordingly, the present invention has been made to solve the above-mentioned problem in the flameproofing treatment of a conventional synthetic fiber structure, particularly a polyester-based synthetic fiber structure, and has excellent durability. An object of the present invention is to provide a flameproofing agent capable of imparting flameproof performance to a synthetic fiber structure.

[0008]

According to the present invention, a synthetic fiber structure has the general formula (I)

[0009]

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(Wherein, R ₁ and R ₂ represent a lower alkyl group and may be the same or different. R ₃ and R ₄ represent a hydrogen atom or a lower alkyl group and may be the same or different. Y is a carbon-carbon _{bond, -CH 2 -, - C (} C
H ₃ ) ₂ —, —S—, —SO ₂ —, —O—, —CO— or —N ＝ N—, m represents an integer of 0 to 4, and n represents 0
Or 1 is shown. Wherein the aromatic diphosphate powder is dispersed in water as fine particles having an average particle size of 2 μm or less by a nonionic surfactant selected from polyoxyalkylene alkyl ethers and polyoxyalkylene alkyl phenyl ethers. A flame retardant for a fibrous structure is provided.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION In the flameproofing agent for a synthetic fiber structure according to the present invention, the flameproofing agent is represented by the general formula (I):

[0012]

Embedded image

(Wherein, R ₁ and R ₂ represent a lower alkyl group and may be the same or different. R ₃ and R ₄ represent a hydrogen atom or a lower alkyl group and may be the same or different. Y is a carbon-carbon _{bond, -CH 2 -, - C (} C
H ₃ ) ₂ —, —S—, —SO ₂ —, —O—, —CO— or —N ＝ N—, m represents an integer of 0 to 4, and n represents 0
Or 1 is shown. The aromatic diphosphate powder represented by ()) is used.

In the aromatic diphosphate represented by the general formula (I), R ₁ and R ₂ represent a lower alkyl group, which may be the same or different. Also, R ₃ and R
₄ represents a hydrogen atom or a lower alkyl group, which may be the same or different. Here, each of the lower alkyl groups is a linear or branched alkyl group having 1 to 5 carbon atoms, and is a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, t-butyl group, n-
It is a pentyl group, an isopentyl group, a t-pentyl group or neopentyl. In the present invention, in particular, R ₁ and R
Preferably, ₂ is a methyl group, and R ₃ and R ₄ are hydrogen atoms.

In the aromatic diphosphate represented by the above general formula (I), Y is a carbon-carbon bond, -CH _{2
-, - C (CH 3)} 2 -, - S -, - SO 2 -, - O
-Represents -CO- or -N = N-, m represents an integer of 0 to 4, and n represents 0 or 1. Of these, Y is a carbon-carbon _{bond, -CH 2 -, - C (} CH 3) 2 - or -O
Is preferred, and particularly preferred is a carbon-carbon bond. Further, m is preferably 0.

Therefore, according to the present invention, as the aromatic diphosphate represented by the general formula (I), for example, tetra (2,6-dimethylphenyl) -m-phenylene phosphate, tetra (2,6-dimethyl) Phenyl)-
p-phenylene phosphate, bisphenol A bis [di (2,6-dimethylphenyl)] phosphate, bisphenol S bis [di (2,6-dimethylphenyl)] phosphate, biphenylbis [di (2,6-dimethylphenyl)] Phosphate, diphenyl ether bis [di (2,6-dimethylphenyl)] phosphate and the like can be mentioned. Among these, especially tetra (2,6
-Dimethylphenyl) -m-phenylene phosphate,
Tetra (2,6-dimethylphenyl) -p-phenylene phosphate or bisphenol A bis [di (2,6-dimethylphenyl)] phosphate is preferably used.
Such an aromatic diphosphate is a crystalline powder, and is described in, for example, JP-A-5-1079, and can be obtained as a commercial product.

In general, when a fiber structure is subjected to post-processing, the particle size of the flameproofing agent used is a very important factor for the flameproofing performance imparted to the fiber structure by the processing. The smaller the particle size, the higher the flame resistance performance can be given to the fibrous structure. In particular, when durability is required for the flameproofing performance of the flameproofing agent, the particle size of the flameproofing agent should be small so that the flameproofing agent can sufficiently diffuse inside the fiber structure. Is essential. According to the present invention, by using the nonionic surfactant as a dispersant, the aromatic diphosphate has an average particle size of 2 μm.
The following fine particles can be stably dispersed in water at a high concentration.

According to the present invention, by using a nonionic surfactant selected from polyoxyalkylene alkyl ethers and polyoxyalkylene alkyl phenyl ethers as a dispersant, the above-mentioned aromatic diphosphate powder can be converted to an average particle size of 2 μm. The following fine particles can be stably dispersed in water at a high concentration. Even if a surfactant other than the above is used as a dispersant, the aromatic diphosphate powder cannot be stably dispersed in water as fine particles. That is, with the pulverizing treatment of the dispersion in which the aromatic diphosphate powder is dispersed, the dispersion becomes a paste, and the aromatic diphosphate cannot be finely divided.

In particular, according to the present invention, the polyoxyalkylene alkyl ether has 10 to 2
Polyoxyethylene alkyl ethers having 0 oxyalkylene units and polyoxyethylene polyoxypropylene alkyl ethers are preferred, and those having an alkyl group molecular weight of 150 or more are particularly preferred. The polyoxyalkylene alkyl phenyl ether is preferably a polyoxyethylene alkyl phenyl ether having 10 to 20 oxyethylene units in the molecule.

Such a nonionic surfactant is used in an amount of usually 1 to 60% by weight, preferably 1 to 10% by weight, based on the aromatic diphosphate. In the flameproofing agent according to the present invention, the content of the aromatic diphosphate as a flameproofing agent is usually 10%.
It is in the range of 70 to 70% by weight, preferably in the range of 20 to 50% by weight.

The flameproofing agent according to the present invention may contain, if necessary, a surfactant other than the above as a dispersant within a range that does not impair the performance or the handleability during processing. Furthermore, according to the present invention, if necessary, to increase storage stability, polyvinyl alcohol, methyl cellulose, carboxymethyl cellulose,
It may contain a protective colloid agent such as starch paste, a flameproofing aid for enhancing flameproofness, an ultraviolet absorber for improving lightfastness, an antioxidant, and the like. In addition, if necessary,
It may contain a conventionally known flame retardant.

The flameproofing agent according to the present invention is effective for imparting flameproofing properties to various synthetic fiber structures by post-processing, and is particularly effective in preventing post-processing of polyester-based synthetic fiber structures. Useful for flame processing. Here, polyester-based synthetic fibers are, for example, polyesters such as polyethylene terephthalate, polybutylene terephthalate, polyoxyethoxybenzoate, polyethylene naphthalate, and cyclohexane dimethylene terephthalate, and as additional components, isophthalic acid, adipic acid, Examples thereof include, but are not limited to, those obtained by copolymerizing a dicarboxylic acid component such as an acid and a diol component such as propylene glycol, butylene glycol, cyclohexanedimethanol, and diethylene glycol. In addition, as a fiber structure,
Any form such as a thread, a woven fabric, a knitted fabric, and a non-woven fabric may be used.

The flameproofing of the synthetic fiber structure by the flameproofing agent according to the present invention can be carried out by a bath treatment method or a padding method. For example, in order to perform flameproofing by a bath treatment method, the synthetic fiber structure is immersed in a flameproofing agent at a temperature in the range of 110 to 150 ° C, preferably 120 to 140 ° C for about 10 to 60 minutes. Then, it may be exhausted. In particular, in the case where the polyester-based synthetic fiber structure is subjected to flameproofing by the in-bath treatment method, it is preferable to perform the dyeing simultaneously with ordinary dyeing. That is, in dyeing a polyester-based synthetic fiber structure in a bath, the flameproofing agent according to the present invention can be subjected to an exhaustion treatment using the disperse dye and the fluorescent dye in the same bath.

When the polyester-based synthetic fiber structure is treated by the padding method, the polyester-based synthetic fiber structure is padded and then subjected to a dry heat treatment, a saturated atmospheric pressure steam treatment, a superheated steam treatment, a high-pressure steam treatment, or the like. Heat treatment by steaming heat treatment. In both the dry heat treatment and the steam heat treatment, the heat treatment temperature is usually in the range of 110 to 210 ° C, and preferably in the range of 170 to 210 ° C.
When the heat treatment temperature exceeds 210 ° C., the polyester synthetic fiber may be yellowed or embrittled.

According to the present invention, in order to impart effective flameproofing properties, the aromatic diphosphate is added to the synthetic fiber structure.
0.5 to 10% by weight, particularly preferably 1 to 5% by weight, is preferred. If necessary, before applying this padding method, the polyester-based synthetic fiber structure can be subjected to flameproofing treatment by the above-mentioned in-bath treatment method to further impart high flameproofing performance.

[0026]

EXAMPLES The present invention will be described below with reference to examples.
The present invention is not limited by these examples.

(Average Particle Size of Flame Retardant (Aromatic Diphosphate)) The particle size distribution of the flame retardant in the flame retardant was measured using a laser diffraction particle size distribution analyzer SALD-20 manufactured by Shimadzu Corporation.
It measured at 00J and made the median diameter the average particle diameter. (Flameproofing performance) JIS for flameproofed fabric and water-washed or dry-cleaned fabric under the following conditions
L 1091 A-1 method (micro burner method) and J
The flameproof performance was measured by ISL 1091 D method (coil method). In the micro burner method, heating for 1 minute
In both cases of heating for 2 seconds, those with a residual flame within 3 seconds, residual dust within 5 seconds, and carbonized area within 30 cm ² were rated as ○. In the coil method, a sample having the number of times of flame contact of 3 or more was evaluated as ○.

(Washing) In accordance with JIS K 3371, a weak alkaline type 1 detergent is used at a rate of 1 g / L.
After washing with water at 60 ° C. ± 2 ° C. for 15 minutes at a bath ratio of 1:40, rinsing three times at 40 ° C. ± 2 ° C. for 5 minutes, centrifugal dehydration for 2 minutes, and then at 60 ° C. ± 5 ° C. One cycle of hot air drying was performed for 5 cycles. (Dry cleaning) Per gram of sample, 12.6 mL of tetrachloroethylene and 0.265 g of charge soap (weight composition of charge soap is nonionic surfactant / anionic surfactant / water = 10/10/1) at 30 ° C. ±
One cycle of the treatment at 2 ° C. for 15 minutes was repeated 5 times.

Example 1 40 parts by weight of crystalline powder of tetra (2,6-dimethylphenyl) -m-phenylene phosphate, 3.5 parts by weight of a 10 mol ethylene oxide adduct of octylphenol, and a silicone-based antifoaming agent 0.1 Parts by weight were mixed with 25 parts by weight of water and pulverized at 6000 rpm for 3 hours or more using a homomixer to obtain a treatment liquid having the above phosphate having an average particle diameter of 50 μm or less. Next, this treatment liquid was charged into a mill filled with glass beads having the same volume of 0.8 mm in diameter and pulverized at a peripheral speed of 2.6 m / sec, and the average particle diameter of the phosphate and the treatment liquid were changed every hour. Was observed. After 3 hours from the start of the pulverization, a processing agent A according to the present invention containing the fine particles of the above phosphate having an average particle diameter of 0.996 μm was obtained.

Example 2 40 parts by weight of crystalline powder of tetra (2,6-dimethylphenyl) -p-phenylene phosphate, 5 mol of ethylene oxide of dodecyl ether and 9 parts of propylene oxide
3.5 parts by weight of the molar adduct and 0.1 part by weight of a silicone-based antifoaming agent were mixed with 25 parts by weight of water, and mixed with a homomixer.
Pulverization treatment was performed at 00 rpm for 3 hours or more to obtain a treatment liquid in which the phosphate had an average particle diameter of 50 μm or less. Thereafter, this treatment liquid was charged into a mill filled with glass beads, and pulverized in the same manner as in Example 1. After 3 hours from the start of the pulverization, a processing agent B according to the present invention containing the above phosphate fine particles having an average particle diameter of 0.764 μm was obtained.

Example 3 40 parts by weight of crystalline powder of bisphenol A bis [di (2,6-dimethylphenyl)] phosphate, 3.5 parts by weight of an adduct of 5 mol of dodecyl ether with ethylene oxide and 9 mol of propylene oxide, and silicone System defoamer
0.1 part by weight was mixed with 25 parts by weight of water, and pulverized at 6000 rpm for 3 hours or more using a homomixer to obtain a treatment liquid having an average particle size of the above phosphate of 50 μm or less. Thereafter, this treatment liquid was charged into a mill filled with glass beads, and pulverized in the same manner as in Example 1. After 3 hours from the start of the pulverization, a processing agent C according to the present invention containing the above phosphate having an average particle diameter of 0.964 μm was obtained.

Comparative Example 1 40 parts by weight of crystalline powder of tetra (2,6-dimethylphenyl) -p-phenylene phosphate, 3.5 parts by weight of sodium dodecyldiphenylethersulfonate and 0.1 part by weight of a silicone antifoaming agent The resulting mixture was mixed with 25 parts by weight of water and pulverized at 6000 rpm for 3 hours or more using a homomixer to obtain a treatment liquid having the above phosphate having an average particle diameter of 50 μm or less. Thereafter, this treatment liquid was charged into a mill filled with glass beads, and pulverized in the same manner as in Example 1. After commencement of grinding, one hour later, the average particle size is 2.232μ.
Thus, a processing agent D according to a comparative example containing m particles of the above phosphate was obtained. However, when the treatment liquid was continuously pulverized, the pulverization was started, and the treatment liquid turned into a paste two hours later.

Comparative Example 2 40 parts by weight of crystalline powder of tetra (2,6-dimethylphenyl) -p-phenylene phosphate, 3.5 parts by weight of sodium dioctylsulfosuccinate and 0.1 part of a silicone antifoaming agent.
One part by weight was mixed with 25 parts by weight of water and pulverized at 6000 rpm for 3 hours or more using a homomixer to obtain a treatment liquid having an average particle size of the phosphate of 50 μm or less.
Thereafter, this treatment liquid was charged into a mill filled with glass beads, and pulverized in the same manner as in Example 1. One hour after the start of the pulverization, a processing agent E according to a comparative example containing the above phosphate having an average particle size of 2.437 μm was obtained. However, when the treatment liquid was continuously pulverized, pulverization was started, and a paste was formed 2 hours later.

Comparative Example 3 Ethylene oxide 20 of sorbitan monostearate
Using 3.5 parts by weight of a molar adduct as an emulsifier, 40 parts by weight of a liquid substance of tetraphenyl-m-phenylene phosphate were emulsified and dispersed in 50 parts by weight of water together with 0.1 part by weight of a silicone-based antifoaming agent. To prepare a processing agent F. The average particle size of the liquid flame retardant in this processing agent is 1.523.
μm.

Example 4 Using the flameproofing agents prepared in the above Examples 1 to 3 and Comparative Examples 1 to 3, a polyester synthetic fiber cloth was exhausted by the same dyeing and bathing method. That is, as a dye bath, 0.3% owf of a disperse dye and a dye dispersant (anionic dispersant 0.3.
5 g / L), adjusted to pH 4.6-4.8 with acetic acid,
130 ° C at a rate of 2 ° C / min from 50 ° C at a bath ratio of 1:15.
C., and kept at this temperature for 60 minutes for treatment in a bath. Thereafter, the dyeing bath was cooled to 60 ° C., washed and dehydrated, and sodium carbonate 1 g / L and anionic surfactant 1 g.
/ L aqueous solution at a bath ratio of 1:30 at 80 ° C. for 10 minutes, followed by drying.

The non-volatile matter when dried at 105 ° C., the average particle size of the flame retardant (aromatic diphosphate), and the flame retardant in the flame retardant used for flame retardant treatment of such a polyester synthetic fiber cloth. The content of the flame retardant, the processing ability of the flame retardant, the amount of the flame retardant added, the amount of the flame retardant adhered to the flame retarded fabric, the feeling and the flame retardant performance of the flame retarded fabric. Examined. Table 1 shows the results.

[0037]

[Table 1]

All of the flameproofing agents according to the present invention are excellent in fluidity and processing handleability, and synthetic fiber structures subjected to flameproofing by post-processing using such flameproofing agents are high. It has flameproofing properties and is also excellent in durability such as washing resistance. Further, no bleeding was observed in which the flame retardant did not migrate to the surface of the cloth to be treated over time, and the disperse dye used for dyeing migrated to the surface of the cloth to be treated together with the flame retardant.

[0039]

As described above, the flameproofing agent for a synthetic fiber structure according to the present invention is obtained by dispersing the crystalline powder of the aromatic diphosphate represented by the general formula (I) as fine particles in water. By attaching such a processing agent to a synthetic fiber structure in a post-processing treatment, it is possible to impart flame resistance performance with excellent durability.

Claims (3)

[Claims] 1. A synthetic fiber structure having the general formula (I): (Wherein, R ₁ and R ₂ represent a lower alkyl group and may be the same or different. R ₃ and R ₄ represent a hydrogen atom or a lower alkyl group and may be the same or different.
The carbon-carbon _{bond, -CH 2 -, - C (} CH 3) 2 -, - S
_{-, - SO 2 -, -} O -, - CO- or -N = N-a shows, m represents an integer of 0 to 4, n is 0 or 1. )
Wherein the aromatic diphosphate powder represented by the formula (1) is dispersed in water as fine particles having an average particle size of 2 μm or less by a nonionic surfactant selected from polyoxyalkylene alkyl ethers and polyoxyalkylene alkyl phenyl ethers. Flameproofing agent for structures. 2. A nonionic surfactant having a molecular weight of 10 to 20 per molecule.
The flameproofing agent according to claim 1, which is selected from a polyoxyalkylene alkyl ether having an oxyalkylene unit and a polyoxyalkylene alkyl phenyl ether. 3. The flameproofing agent according to claim 1, wherein the synthetic fiber structure is a polyester-based synthetic fiber structure.