JPH09310272A - Flame retardant fiber and flame retardant fibrous product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a flame retardant fiber or a flame retardant fibrous product, excellent in washing endurance and having a highly fire retarding property by imparting a treating liquid obtained by dispersing an insoluble polyphosphoric acid ammonium into a synthetic resin emulsion, to the fiber. SOLUTION: This fire retardant fiber is obtained by preparing a flame retarding treating liquid by dispersing 10-100 pt.wt. insoluble polyphosphoric acid ammonium obtained by treating melamine-covered polyphosphoric acid ammonium particles with a compound such as a formalin capable of treating with an active hydrogen belonging to an amino group of the melamine molecule on surface of the particle, into 100 pts.wt. acrylic emulsion, imparting the above treating liquid to a fibrous substrate containing at least >=30wt.% natural organic fiber or cellulose-based man-made fiber and then drying and/or curing.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a flame-retardant fiber and a flame-retardant fiber product which are excellent in texture and exhibit high flame retardancy. Specifically, flame-retardant fibers containing insoluble ammonium polyphosphate, flame-retardant fiber products and synthetic resin emulsions coated with or impregnated with a treatment liquid in which ammonium insoluble polyphosphate is dispersed. Regarding textile products.

[0002]

2. Description of the Related Art Conventionally, clothing, bedding, wallpaper, automobiles,
Many textile products are used as interior materials for aircraft, railways and ships. With the expansion and diversification of these applications,
Fireproof, flameproof, fireproof or flame retardant is required for applications using fibers, and the performance is becoming severer year by year. In particular, recently, products using halogen compounds and halogenated organophosphorus compounds, which are the mainstream of conventional flame retardant technology, generate halogen-based gas at the time of combustion, and flame retarding treatment using these halogen compounds. The above-mentioned fiber product is dissolved or swelled in the organic solvent used during the dry cleaning, and the fiber product becomes sticky, the texture is impaired, and the flame retardancy is lowered.

There are known examples of using a water-soluble inorganic salt such as ammonium phosphate monomer, borate and ammonium sulfamate as a flameproofing agent which does not generate halogen gas. The flameproofing agent is water-soluble. It has a drawback that it is inferior in water washing resistance of the textile product due to its property.

In order to meet these demands, studies have been carried out using a poorly soluble salt such as ammonium polyphosphate. For example, JP-B-51-46200 discloses a reaction of a fiber or a textile product with a phosphorus compound such as ammonium polyphosphate and a formaldehyde condensation polymer of a guanidine salt or a guanylurea salt, or a cocondensation polymer thereof with another compound. A flame-retardant processing method of a product-attached fiber or textile is disclosed. However, the flame-retardant processed fiber product obtained by the method disclosed in the publication is not only poor in water resistance because ammonium polyphosphate used in the product is water-soluble, but also from a formaldehyde polycondensation product of a guanidine salt or a guanylurea salt. It has a problem in environmental hygiene that a large amount of free formalin is generated.

Further, Japanese Patent Laid-Open Nos. 4-214471 and 4-228676 disclose a woven fabric containing a partially water-soluble ammonium polyphosphate, a surfactant, a heat-curable resin and water. Compositions for flame retarding are disclosed. However, ammonium polyphosphate, which is one component of the composition disclosed in this publication, has a problem that it has poor wash resistance in water, especially at relatively high temperatures, due to its partial solubility in water. ing.

The present inventors have conducted extensive studies to solve the above problems. As a result, the melamine present on the surface of the melamine-coated ammonium polyphosphate having melamine added and / or attached to the surface of the powdery ammonium polyphosphate particles is reacted with a functional group capable of reacting with the active hydrogen of the amino group in the melamine molecule. Insoluble ammonium polyphosphate particles obtained by cross-linking the surface of the melamine-coated ammonium polyphosphate particles with a crosslinking agent having a fiber or fiber product containing a specific amount has an excellent texture and is excellent in solvent resistance and water resistance. Based on this finding, the present invention was completed.

As is clear from the above description, the object of the present invention is to have an excellent texture and to exhibit excellent flame retardancy even after washing with water and dry cleaning.
A flame-retardant fiber and a flame-retardant fiber product are provided.

The present invention consists of the following: (1) Dry weight of insoluble ammonium polyphosphate obtained by treating melamine on the surface of melamine-coated ammonium polyphosphate particles with a compound having a functional group capable of reacting with active hydrogen belonging to an amino group in the melamine molecule A flame-retardant fiber or a flame-retardant fiber product contained in a fiber or a fiber product in an amount of 3 to 50% by weight based on the total weight. (2) Melamine-coated ammonium polyphosphate particles, in which 0.5 to 20% by weight of the total weight of melamine is added and / or attached to the surface of the powdery ammonium polyphosphate particles by sublimation. The flame-retardant fiber or flame-retardant fiber product according to the above-mentioned item 1, which is (3) A compound having a functional group capable of reacting with active hydrogen belonging to an amino group in a melamine molecule is an isocyanate group,
The flame-retardant fiber or flame-retardant fiber product according to the above item 1, which is a compound having an epoxy group, a carboxyl group, a methylol group or a formyl group. (4) The fiber or textile product is a natural organic fiber, a cellulosic artificial fiber or at least 30% by weight of them.
The first to third items which are fibers or fiber products to be contained.
The flame-retardant fiber or flame-retardant product according to any one of items. (5) A flame-retardant fiber or a flame-retardant fiber product obtained by coating or impregnating a fiber or a fiber product with a treatment liquid in which 10 to 100 parts by weight of insoluble ammonium polyphosphate is dispersed in 100 parts by weight of a synthetic resin emulsion. (6) The insoluble ammonium polyphosphate is 10% of the insoluble ammonium polyphosphate particles after 2 hours at 25 ° C.
The flame-retardant fiber or the flame-retardant fiber product according to any one of the above items 1 to 5, which has an elution rate of 1% by weight or less from an aqueous suspension slurry of 1% by weight. (7) Insoluble ammonium polyphosphate was added at 75 ° C, 24
Of insoluble ammonium polyphosphate particles after 1 hour
The flame-retardant fiber or the flame-retardant fiber product according to any one of the above items 1 to 5, which has an elution rate of 30 wt% or less from a 0 wt% aqueous suspension slurry. (8) The synthetic resin emulsion is selected from the group consisting of acrylic ester emulsion, urethane emulsion, epoxy emulsion, vinyl acetate emulsion, vinyl chloride emulsion, vinylidene chloride emulsion, polyvinyl alcohol emulsion 1
The flame-retardant fiber or the flame-retardant fiber product according to the above-mentioned item 5, which is a mixture of two or more kinds.

The insoluble ammonium polyphosphate according to the present invention is the active hydrogen of the amino group in the melamine molecule present in the coating layer of the melamine-coated ammonium polyphosphate.
By reacting a crosslinking agent having a functional group capable of reacting with the active hydrogen such as an isocyanate group, a methylol group, a formyl group, or an epoxy group, a crosslinked structure is formed between the melamine molecule on the same particle. It is ammonium polyphosphate, and such insoluble ammonium polyphosphate can be obtained by the following method.

That is, a melamine-coated ammonium polyphosphate and a crosslinking agent having a functional group capable of reacting with active hydrogen belonging to an amino group in a melamine molecule, for example, an aqueous formaldehyde solution, are placed in a reactor equipped with a heating stirring or kneading mechanism. Add and mix. Then, the temperature is raised to 50 to 200 ° C., preferably 70 to 130 ° C., more preferably 80 to 110 ° C., at which the crosslinked structure is easily formed between the active hydrogens of the amino groups in the melamine molecule, and the reaction is sufficient. When the reaction is completed for 0.5 to 2 hours or 1 to 4 hours, a crosslinked structure is formed in the melamine coating layer of the melamine-coated ammonium polyphosphate, and insoluble ammonium polyphosphate particles according to the present invention are obtained. To be

The reaction may be carried out in either a solvent system or a non-solvent system, and in the solvent system, a single solvent or a mixed solvent comprising water and / or an organic solvent can be used. The cross-linking agent used is a compound having one or more functional groups capable of reacting with the active hydrogen of the amino group in the melamine molecule, and the amount used is the amount of melamine contained in the melamine-coated ammonium polyphosphate. The amount of the functional group is 0.5 to 6 times, and preferably 1 to 3 times the molar equivalent of one molecule.

The functional group capable of reacting with the active hydrogen of the amino group in the melamine molecule includes an isocyanate group, a methylol group, a formyl group or an epoxy group. As a compound containing one or more of the functional groups, For example, as a compound having an isocyanate group, 1,6-diisocyanate hexane, 1,1'-methylenebis (4-
Isocyanatobenzene), 3,3′-dimethyldiphenyl-4,4′-diisocyanate, 1,5-diisocyanonaphthalate, and the like, and as a compound having a methylol group, a methylol (thio) having 2 to 5 carbon atoms.
Urea, methylolmelamine having 4 to 9 carbon atoms, trimethylolethane, trimethylolpropane, neopentyl glycol, pentaerythritol and the like, and formyl group-containing compounds such as formaldehyde, malonaldehyde and glyoxal, epoxy group and the like. Examples of the compound having a can include ethylene glycol diglycidyl ether, glycerol polyglycidyl ether and various epoxy resins represented by bisphenol A type epoxy resin, phenol novolac type epoxy resin, cycloaliphatic epoxy resin, and the like. Any commercially available product can be used.

The melamine-coated ammonium polyphosphate used for the production of the insoluble ammonium polyphosphate of the present invention is ammonium polyphosphate obtained by sublimating melamine and adding and / or adhering melamine on the surface of ammonium polyphosphate particles, The melamine-coated ammonium polyphosphate can be obtained, for example, by the following method.

Ammonium polyphosphate is charged into a heating kneader such as a heated kneader so that the ammonium polyphosphate is not melted and the ammonia added to the ammonium polyphosphate is easily desorbed, and melamine is also added. Melamine is added and / or attached to the surface of the ammonium polyphosphate particles by adding melamine and heating at 350 ° C or lower, preferably 200 to 300 ° C, which is the temperature at which the sublimation can be sublimated. The proportion of melamine added at this time is 0.5 to 20% by weight, preferably 2 to 15% by weight, based on the ammonium polyphosphate. When produced by the above method, most of the added melamine is ammonium polyphosphate. A melamine-coated ammonium polyphosphate in the state of being added to and / or attached to is obtained.

Here, the addition means a state in which melamine is chemically bonded to a hydroxyl group on the surface in a state where ammonia is desorbed from ammonium polyphosphate, the added melamine is stable even when heated, and is removed again. Never let go.
Further, the adhesion means a state in which melamine is adsorbed on the surface of ammonium polyphosphate particles, and melamine is repeatedly sublimated and adsorbed on the surface of ammonium polyphosphate particles by continuing heating.

As the raw material of the melamine-coated ammonium polyphosphate, ammonium polyphosphate may be a commercially available product or one obtained by a known method, and as the commercially available product, Exolit-422 (trade name, Hoechst Manufactured by Monsanto), Phos-chek P / 40 (trade name, manufactured by Monsanto), and the like. As a known method, for example, it can be obtained by heating approximately equimolar amounts of ammonium orthophosphate and phosphorus pentoxide to a temperature of 170 to 350 ° C. in the presence of gaseous ammonia and simultaneous movement of reactants. However, atomized ammonium polyphosphate can also be obtained by spraying urea water when the raw material is melted.

The insoluble ammonium polyphosphate obtained by the above-mentioned method is insoluble in commonly known organic solvents. The elution rate in water is calculated by the following method. That is, a 10% by weight aqueous suspension slurry at each measurement temperature, for example, an accurately weighed 5 g sample, and 45 g
Pure water is mixed and suspended to form a slurry, which is shaken at a constant temperature for a certain period of time, and then the slurry is subjected to solid-liquid separation with a centrifuge or the like. Next, a part of the supernatant liquid, for example, about 5 g is taken out, precisely weighed, evaporated to dryness, and the dry matter weight is measured, and the elution rate is determined by the following formula. The insoluble ammonium polyphosphate used in the present invention has an elution rate of 1% by weight or less after shaking at 25 ° C. for 2 hours,
It is 30% by weight or less, preferably 15% by weight or less after shaking at 75 ° C for 24 hours. As the elution rate of ammonium polyphosphate becomes worse, the washing resistance becomes worse.

As the raw material fibers of the flame-retardant fiber of the present invention,
Natural organic fibers such as cotton, cotton, kapok, flax, ramie, jute, jute, hemp, wool and silk, cellulosic artificial fibers such as viscose, rayon and acetate, and those natural fibers or cellulosic artificial fibers As the raw material fiber product of the flame-retardant fiber product of the present invention, various knitted or woven fabrics obtained by using the above-mentioned various fibers can be used. , Various processed fiber products using the knitted / woven fabric.

As a method for obtaining the flame-retardant fiber or the flame-retardant fiber product according to the present invention, a base fiber or fiber product is coated with a flame-retardant treatment agent in which insoluble ammonium polyphosphate is dispersed in a synthetic resin emulsion, It can be obtained by incorporating a conventionally known fiber treatment agent such as spraying and impregnation by a method for treating, and drying and / or curing.

As the synthetic resin used in the synthetic resin emulsion, for example, as an acrylic resin, 2-ethylhexyl acrylate, butyl acrylate, methyl acrylate and methyl methacrylate are mainly used, and acrylic acid, acrylonitrile, styrene and the like are copolymerized,
Further, acrylic acid ester-based resins having a cross-linking group such as methylol acrylamide, glycidyl methacrylate, allylaminodichlorotriazine, and monochlorovinyl acetate can be mentioned.

As the urethane resin, a mixture of polyols such as polyether polyol, polyester polyol and polymer polyol and / or a polyamine is used as a first component, and an average of two or more terminal isocyanate groups is contained in one molecule. Second polyisocyanate
As a component, a urethane-based resin obtained by reaction curing may be mentioned.

Examples of the vinyl acetate resin include polyvinyl acetate, vinyl acetate-ethylene copolymer, vinyl acetate-vinyl propionate copolymer, vinyl acetate-acrylate copolymer and the like. As the epoxy resin, any of the commonly used ones such as aliphatic, aromatic, cyclic, acyclic, alicyclic or heterocyclic can be used. Besides, vinyl chloride resin, vinylidene chloride resin, polyvinyl alcohol resin can be preferably used.

The synthetic resin emulsion contains the synthetic resin in an amount of 5 to 60% by weight, preferably 10 to 50, in terms of solid content.
% By weight and 0.1 to 5% by weight of emulsifier, preferably 1 to
3% by weight, in which any amount of cationic, anionic or nonionic surfactants, softening agents, antistatic agents, polishes, antibacterial agents, water / oil repellents, defoamers, It is prepared by appropriately mixing a dye, a pigment and the like. 10 to 100 parts by weight, preferably 20 to 80 parts by weight, of insoluble ammonium polyphosphate is mixed and dispersed with 100 parts by weight of the synthetic resin emulsion to obtain a flame retardant treatment agent.

[0024]

The present invention will be described in more detail with reference to the following Examples and Comparative Examples, which by no means limit the scope of the present invention. The evaluation in Examples and Comparative Examples was performed by the following method. (1) Flame-retardant test According to JIS-L-1091A-1 method. (2) Measurement of Adhesion Amount of Flame Retardant The adhesion amount of each insoluble ammonium polyphosphate in each of the Examples and Comparative Examples was calculated by measuring the dry weight of the flame-retarded fabrics produced in each of the Examples and Comparative Examples. The value obtained by dividing the weight difference between the chemical fabrics and the dry weight of the original fabrics was taken as the adhesion amount (%). (3) Washing resistance test (3-1) Water washing test According to JIS-L-1042 6.6.2 (2) F-2 method, the test was continuously performed 5 times. (3-2) Dry cleaning test E-2 of 6.30 (2) (e) of JIS-L-1018
Was washed for 15 minutes, rinsed twice with a sufficient amount of perchlorethylene, drained, and naturally dried, and this operation was repeated 5 times in succession.

The insoluble ammonium polyphosphate used in each of the examples of the present invention and the comparative examples was manufactured as follows. In a flask having an internal volume of 5 liters equipped with a heating and stirring function and a reflux function, 1000 g of melamine-coated ammonium polyphosphate and water with a methanol concentration of 12% by weight-
2000 g of a methanol solution and 122 g of formalin aqueous solution having a concentration of 35% by weight are added, heated and reacted at a reflux temperature for 1 hour. Then it is rapidly cooled to 30-40 ° C, filtered, concentration 1
Repeatedly wash with 2% by weight methanol aqueous solution,
It was dried in an oven set at 0 ° C. to obtain 990 g of insoluble ammonium polyphosphate. The dissolution rate of the insoluble ammonium polyphosphate after 2 hours at 25 ° C was 0.1%, and the dissolution rate after 24 hours at 75 ° C was 3.5%. Here, the melamine-coated ammonium polyphosphate was treated using the following procedure.

To a kneader preheated to 280 to 320 ° C., 2000 parts by weight of powdery ammonium polyphosphate was charged, and the mixture was heated and mixed for 3 hours in a nitrogen gas or inert gas atmosphere to desorb ammonia. 110 parts by weight of melamine is added to the ammonia-deficient ammonium polyphosphate. At this point, close the top of the kneader, and
The mixture was heated and stirred at 0 ° C. for 5 hours to obtain a melamine-coated ammonium polyphosphate.

Example 1 As a synthetic resin emulsion, 100 parts by weight of an acrylic emulsion AA-80 (trade name, manufactured by Kanebo NSC Co., Ltd.) containing an anionic surfactant and having a solid content concentration of 47% by weight and a viscosity of 3000 cps. On the other hand, insoluble ammonium polyphosphate was mixed well at a ratio of 50 parts by weight to obtain a flame retardant treatment agent. As a base textile, cotton 1
00% woven fabric was used, the flame retardant treatment agent was applied with a spatula, and then a roll linear pressure of 25 kg /
It was squeezed in cm ² and dried at 80 ° C. for 3 hours to obtain a flame-retardant woven fabric. The woven fabric was cut into a predetermined size, and the amount of adhesion was measured before and after water washing and dry cleaning, and the flame retardancy test was performed. The results are shown in Table 1.

Example 2 As a synthetic resin emulsion, 100 parts by weight of a urethane emulsion GC-52 (trade name, manufactured by Kanebo NSC Co., Ltd.) containing an anionic surfactant and having a solid content of 33% by weight and a viscosity of 500 cps was used. On the other hand, 33 parts by weight of insoluble ammonium polyphosphate and 1 part by weight of a sodium acrylate-based thickener were well mixed to obtain a flame retardant treatment agent. A woven cloth made of 100% cotton is used as a base fiber product, which is sufficiently dipped in the flame retardant treatment agent placed in an appropriate container, and then rolled with a roll squeezing machine to obtain a roll linear pressure of 2
It was squeezed at 5 kg / cm ² and dried at 80 ° C. for 3 hours to obtain a flame-retardant woven fabric. The woven fabric was cut into a predetermined size, and the amount of adhesion before and after water washing and dry cleaning was measured and the flame retardancy test was performed. The results are shown in Table 1.

Example 3 A flame-retardant woven fabric was obtained in the same manner as in Example 1 except that a 100% rayon woven fabric was used as the base fiber product. The woven fabric was cut into a predetermined size, and the amount of adhesion before and after water washing and dry cleaning was measured and the flame retardancy test was performed. The results are shown in Table 1.

Example 4 Example 2 was repeated except that as the base fiber product, a mixed woven fabric in which the warp yarn was 100% cotton, the weft yarn was 40% acrylic, 25% polyester, 20% cotton, and 15% nylon was used. A flame-retardant woven fabric was obtained in conformity with the standards. The woven fabric was cut into a predetermined size, and the amount of adhesion before and after water washing and dry cleaning was measured and the flame retardancy test was performed. The results are shown in Table 1.

Comparative Example 1 In place of insoluble ammonium polyphosphate, Sumisafe-P (trade name, manufactured by Sumitomo Chemical Co., Ltd., which is uncoated ammonium polyphosphate;
The elution rate of P after 2 hours at 25 ° C. was 38.1%.
The elution rate after 24 hours at 5 ° C is 100%. A flame-retardant woven fabric was obtained in the same manner as in Example 1 except that The woven fabric was cut into a predetermined size, and the amount of adhesion before and after water washing and dry cleaning was measured and the flame retardancy test was performed. Table 1 shows the results.

Comparative Example 2 A flame-retardant woven fabric was obtained in the same manner as in Example 1 except that melamine-modified ammonium polyphosphate was used instead of insoluble ammonium polyphosphate. The woven fabric was cut into a predetermined size, and the amount of adhesion before and after water washing and dry cleaning was measured and the flame retardancy test was performed. The results are shown in Table 1. The melamine-modified ammonium polyphosphate used here was prepared by the following method. A raw material prepared by mixing 1-ammonium phosphate, urea, and melamine in a molar ratio of 2: 2: 1 was supplied to a kneader held at 260 to 270 ° C., and a temperature of 270 ° C. was applied in an ammonia gas atmosphere at a temperature of 1.5. Heated for ~ 2 hours to obtain melamine modified ammonium polyphosphate. This was crushed and used. The resulting melamine-modified ammonium polyphosphate is
The elution rate after 2 hours at 25 ° C. was 11.1%,
The elution rate after 24 hours at ℃ was 95%.

Comparative Example 3 A flame-retardant woven fabric was obtained in the same manner as in Example 2 except that 20 parts by weight of trisdichloropropyl phosphate was used instead of insoluble ammonium polyphosphate. The woven fabric was cut into a predetermined size, and the amount of adhesion before and after water washing and dry cleaning was measured and the flame retardancy test was performed.
The results are shown in Table 1.

[0034]

[Table 1]

[0035]

INDUSTRIAL APPLICABILITY The flame-retardant fiber product containing the insoluble ammonium polyphosphate according to the present invention has high flame retardancy and is capable of releasing the flame retardant upon washing with water or an organic solvent.
Suitable for various clothing, bedding, wallpaper, and various interior materials such as automobiles, airplanes, railroads and ships, etc. without dissolution and without deterioration of texture and flame retardancy after washing. Can be used.

Claims (8)

[Claims] 1. An insoluble ammonium polyphosphate obtained by treating melamine on the surface of melamine-coated ammonium polyphosphate particles with a compound having a functional group capable of reacting with active hydrogen belonging to an amino group in the melamine molecule is dried. A flame-retardant fiber or a flame-retardant fiber product, which is contained in a fiber or a fiber product in an amount of 3 to 50% by weight based on the total weight. 2. Melamine-coated polyphosphoric acid, wherein the melamine-coated ammonium polyphosphate particles are added and / or attached by sublimation of 0.5 to 20% by weight of the total weight of melamine to the surface of the powdery ammonium polyphosphate particles. The flame-retardant fiber or flame-retardant fiber product according to claim 1, which is an ammonium particle. 3. A compound having a functional group capable of reacting with active hydrogen belonging to an amino group in a melamine molecule is a compound having an isocyanate group, an epoxy group, a carboxyl group, a methylol group or a formyl group. Flame-retardant fiber or flame-retardant fiber product. 4. The fiber or textile product is a natural organic fiber,
Cellulosic artificial fibers or at least 30 of them
It is a fiber or a fiber product containing wt%.
The flame-retardant fiber or flame-retardant fiber product according to claim 3. 5. A flame-retardant fiber or a flame-retardant fiber product obtained by coating or impregnating a fiber or a fiber product with a treatment liquid in which 10 to 100 parts by weight of insoluble ammonium polyphosphate is dispersed in 100 parts by weight of a synthetic resin emulsion. 6. The insoluble ammonium polyphosphate is 25
6. The flame retardancy according to claim 1, wherein the insoluble ammonium polyphosphate particles have an elution rate of 1% by weight or less from a 10% by weight aqueous suspension slurry after 2 hours at [deg.] C. Textiles or flame retardant textiles. 7. The insoluble ammonium polyphosphate is 75
The insoluble ammonium polyphosphate particles after 24 hours at 30 ° C. have an elution rate of 30% from an aqueous suspension slurry of 10% by weight.
The flame-retardant fiber or the flame-retardant fiber product according to any one of claims 1 to 5, wherein the content of the flame-retardant fiber is not more than wt%. 8. A synthetic resin emulsion selected from the group consisting of acrylic ester emulsions, urethane emulsions, epoxy emulsions, vinyl acetate emulsions, vinyl chloride emulsions, vinylidene chloride emulsions, and polyvinyl alcohol emulsions. Alternatively, the flame-retardant fiber or the flame-retardant fiber product according to claim 5, which is a mixture of two or more kinds.