JPH0253476B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to flame retardants that provide excellent flame retardancy, texture and light resistance. Conventionally, flame retardants for fibers and textile products, etc.
Inorganic compounds such as ammonium phosphate, ammonium bromide, borax, boric acid, ammonium sulfamate, ammonium hydroxide, hexabromobenzene,
Organic halogen compounds such as decabromodiphenyl oxide, chlorinated paraffin, and tetrabromobisphenol A, and organic phosphoric acid esters such as tris-dichloropropyl phosphate, tris-chloroethyl phosphate, and tricresyl phosphate are known. There is. However, when these flame retardants are attached to the surface of fibers and textile products, the surface becomes white, sticky, rough and stiff, and the texture is extremely deteriorated. In addition, halogen compounds,
In particular, bromine compounds have poor light resistance and have the disadvantage of causing discoloration. The present invention is based on the following formula 2,2-bisbromomethyl-1,3 represented by
- For post-processing containing acidic phosphoric acid ester and/or its salt of dibromoneopentyl glycol obtained by reacting propanediol (hereinafter referred to as dibromoneopentyl glycol) and phosphoric anhydride in a ratio of 3:0.5 to 4 moles It is a flame retardant. The flame retardant of the present invention can eliminate the drawbacks of conventional products and provide excellent flame retardant performance. In addition, conventional water-soluble flame retardants have poor compatibility with various synthetic resin emulsions (latexes) and are difficult to use together with latexes, whereas the flame retardant of the present invention is compatible with various synthetic resin emulsions. It has an excellent feature of good compatibility. When producing acidic phosphoric acid ester of dibromoneopentyl glycol, 0.5 to 4 mol of phosphoric anhydride is added to 3 mol of dibromoneopentyl glycol.
Both are reacted in a molar ratio, preferably 1 to 3 molar. If the amount of phosphoric anhydride used is less than 0.5 mol, unreacted dibromoneopentyl glycol will increase, resulting in poor flame retardant effect and texture. If the amount is more than 4 moles, there will be a large amount of unreacted phosphoric anhydride, and when water is added, phosphoric acid will be produced, resulting in poor texture and poor compatibility of the obtained flame retardant with the synthetic resin emulsion. Reaction temperature is 50-220℃, preferably 100-150℃
Add phosphoric anhydride little by little to dibromoneopentyl glycol and let it react. At first, the reaction is weakly exothermic, but in the latter half of the reaction, the heat disappears and heating is required. However, heating above 220°C is undesirable because it causes coloration and decomposition of the reaction product. This reaction can also be carried out in the presence of a solvent. Preferred solvents include those without active hydrogen, such as xylene, toluene, perchloroethylene, and the like. When a solvent is used, the reaction conditions are milder and stirring becomes easier, but it is economically disadvantageous to use a large amount of solvent because the solvent needs to be removed after the reaction is completed. After the reaction is completed, the reaction mixture can be used as it is to prepare a flame retardant, usually without isolating and purifying the reaction product. The acidic phosphoric acid ester of dibromoneopentyl glycol produced by the reaction of dibromoneopentyl glycol and phosphoric anhydride is used after being dissolved or dispersed in water or the like. Since the aqueous solution of this compound is acidic, it is preferable to neutralize it with a basic substance and use it in the form of a salt, but it does not have to be in a complete salt form, and some acidic phosphate ester may be present. . Basic substances used for neutralization include, for example, inorganic compounds such as sodium hydroxide, potassium hydroxide, ammonia, magnesium hydroxide, calcium hydroxide, monoethanolamine, diethanolamine, ethylenediamine, guanidine, guanidine-formaldehyde condensate, Examples include organic bases such as guanylurea and melamine. The flame retardant of the present invention can be applied to fibers and textile products, as well as papers, urethane foams, plastic foams, etc., by a post-processing method in which it is deposited on the surface. Fibers include natural fibers such as cotton, wool,
Silk, linen, etc., regenerated cellulose fibers such as rayon,
acetate, synthetic fibers such as polypropylene,
Examples of fiber products include polymers and copolymers of polyester, polyamide, polyacrylonitrile, vinylon, etc., olefins, and vinyl compounds, and textiles, knits, nonwovens, blends, and blends of these fibers. Specific examples include curtains, carpets, carpets, mats, sheets (chairs, benches, seats, etc.), blankets, wall coverings, air filters, heat insulating materials, etc. When used in fibers and textile products, the amount of flame retardant used in the present invention is 0.5 to 0.5 to
50% by weight, preferably 3-30% by weight. If the amount used is less than 0.5%, the flame retardant performance is insufficient.
If the amount is more than 50%, not only will there be no particular improvement in flame retardant effect, but the texture may deteriorate. Conventional methods can be used to perform flame retardant processing using the flame retardant of the present invention. In other words, a flame retardant is dissolved or dispersed in water, etc., additives are added as necessary to prepare a flame retardant processing liquid, and this is applied to fibers, etc. by spraying, coating, dipping, etc., and then dried. do it. This flame-retardant processing liquid may be used as necessary for activators, dispersants, penetrants, colorants such as dyes, water repellents, softeners, finishing agents, latexes, resin processing agents, thickeners, adhesives, etc. may contain flame retardants, etc. Examples of acidic phosphoric acid esters produced by the reaction of dibromoneopentyl glycol and phosphoric anhydride are shown below. A in the formula is a group

[Formula] is shown. (7) Pyrophosphate ester combined with A The reaction ratio and composition of the product are shown in the following table.

[Table] Production example 1 786 g (3 mol) of dibromoneopentyl glycol was heated to 120°C, and 142 g (1 mol) of phosphoric anhydride was added.
Add in small portions at 120-150°C while stirring. Subsequent reaction at 140-160°C for 90 minutes yields 928 g of transparent acidic phosphoric acid ester of dibromoneopentyl glycol. Appearance: white solid, melting point:
Melts transparent at 138℃.

[Table] Production example 2 786 g (3 moles) of dibromoneopentyl glycol was heated to 120°C, and 284 g (2 moles) of phosphoric anhydride was added.
Add in small portions at 120-150°C while stirring. Subsequent reaction at 140-160°C for 90 minutes yields 1070 g of transparent acidic phosphoric acid ester of dibromoneopentyl glycol. Appearance: white solid, melting point:
Melts transparent at 140℃.

[Table] Production example 3 786 g (3 mol) of dibromoneopentyl glycol was heated to 120°C, and 426 g (3 mol) of phosphoric anhydride was added.
Add 120 to 160℃ little by little while stirring. Subsequent reaction at 150-170°C for 90 minutes yields 1212 g of transparent acidic phosphoric acid ester of dibromoneopentyl glycol. Appearance: white solid, melting point:
Melts transparent at 145℃.

TABLE Parts and percentages in the examples below relate to weight. Example 1 After adding 300 g of water to 320 g of the reaction product of Production Example 2, 120 g of 25% aqueous ammonia was added to neutralize the mixture.
Each aqueous solution prepared in this way contains 2760 ml of water.
g and 426 g to prepare processing liquids with concentrations of 10% and 30%. Various base fabrics are dipped in this processing liquid,
After squeezing with a mangle and drying at 80℃, flame retardancy was examined. The test is based on JISL1091A-4 Law and Ministry of Home Affairs Ordinance No. 3
Test method (Fire Service Act) was used. The results are shown in Table 1. All unprocessed products were completely burnt down.

[Table] Example 2 260 g of water was added to 320 g of the reaction product of Production Example 2, and then 120 g of 25% ammonia water was added to neutralize it.
Prepare an aqueous solution with a concentration of 50%. Add 15 parts of the above aqueous solution (7.5 parts solids) to 100 parts of ethylene-vinyl acetate-vinyl chloride latex (Sumicaflex CY-830, manufactured by Sumitomo Chemical Co., Ltd., solids content 50%) to prepare a processing liquid. A processing liquid ^{of 240 g/m 2 (} solid content: 120 g/m 2 ) was applied to the back side of a polypropylene needle punch (fabric weight 260 g/m ² ), and after drying at 85° C. for 30 minutes, flame retardancy was examined. The test was conducted using the FMVSS302 method. For comparison, tests were conducted after processing in the same manner using latex alone or a processing fluid consisting of 7.5 parts of aluminum hydroxide and 100 parts of latex. The results are shown in Table 2. The numerical values in the table are the average values of five measurements, and the values in parentheses indicate the minimum and maximum values.

[Table] Example 3 After adding 748 g of water to 300 g of the reaction product of Production Example 1, 80 g of guanidine carbonate-formalin (1:2 mol) initial condensate and 32 g of 25% aqueous ammonia were added to neutralize the mixture. Prepare a 30% processing solution. Using this processing fluid, polyester/rayon (28:
72) Mixed woven drape curtain (weighing 265g/cm ² )
Processed with 2 days and 2 nips at room temperature and squeezing rate 80
%, and after pre-drying at 80°C, heat-treating at 140°C for 3 minutes, a flexible flame-retardant curtain with a good texture can be obtained. Using this curtain, a test was conducted according to Test Method No. 3 of the Ministry of Home Affairs Ordinance Notification. The results are shown below. The numerical value is the average value of three measurements. The unprocessed products were completely burnt down. 1 minute heating test Afterflame: 0 seconds Residual dust: 0 seconds Carbonized area: 19.5 cm ² 3 seconds after flame application Heating test Afterflame: 0 seconds Residual dust: 0 seconds Carbonized area: 8.2 cm ² Example 4 Production example 2 After adding 251 g of water to 250 g of the reaction product and 100 g of the reaction product of Production Example 3, the mixture was neutralized with 50 g of a 10% aqueous sodium hydroxide solution and 115 g of 25% aqueous ammonia to prepare an aqueous solution with a concentration of 50%. Acrylic ester latex (manufactured by Nippon Acrylic Chemical Co., Ltd.)
60 parts of the above aqueous solution (solid content 30 parts) and a sodium polyacrylate thickener are added to 100 parts of Brimar HA-24 (solid content 50%) to make a processing fluid with a viscosity of 8000 cps. Polyester car seat (basis weight)
300g/m ² ) was coated with this processing liquid at a rate of 200g/m ² (solid content: 100g/m ² ).
After drying at 150°C for 15 minutes and curing for 1 minute at 150°C, flame retardancy was examined. The test was conducted using the FMVSS302 method. As comparative examples, tests were conducted in the same manner in the case of latex alone and in the case of adding 30 parts of aluminum hydroxide.
The results are shown in Table 3. The numerical values in the table are the average values of five measurements, and the values in parentheses indicate the minimum and maximum values.

[Table] Example 5 100 parts of an aqueous solution with a concentration of 50% prepared in the same manner as in Example 2, 30 parts of the same acrylic ester latex as in Example 4, and 700 parts of water were mixed to prepare a processing liquid. Soft urethane foam (density
0.020, thickness 10mm), squeezed to 200% with a mangle, and dried at 80℃. The solid content of this urethane foam was 15.5%. Using this urethane foam, tests were conducted using the FMVSS302 method. As a comparative example, an emulsion of tris dichloropropyl phosphate (concentration 50%)
A similar test was conducted using urethane foam. The results are shown in Table 4. The numerical values in the table are the average values of five measurements, and the values in parentheses indicate the minimum and maximum values.

[Table] Example 6 A 30% concentration processing fluid used in Examples 1 and 3 and a 30% concentration aqueous solution of a conventionally used flame retardant processing agent as a comparative example were prepared, and polyester/
A rayon (20:80) interwoven drape curtain (basis weight: 280 g/m ² ) was subjected to flame retardant treatment in the same manner as in Example 3, and its flame retardance, texture and light resistance were examined. Flame retardancy is determined by the Ministry of Home Affairs Ordinance Notification No. 3 test method, texture is determined by texture, and light resistance is determined by JIS L-
Tested according to the method of 0820 (fademeter, irradiation at 63°C for 40 hours). The results are shown in Table 5.

【table】

[Table] Example 7 600 parts of a 50% aqueous solution prepared in the same manner as in Example 2 was added to an ethylene-vinyl acetate-vinyl chloride latex (manufactured by Sumitomo Chemical Co., Ltd.: Sumikaflex).
Add to 1000 parts of CY-850 (solid content approx. 50%) and use it as a processing liquid. After immersing a polyester air filter nonwoven fabric (fabric weight 280 g/m ² ) in the processing liquid, it was squeezed to 150% with a mangle, and heated at 80°C for 15 minutes and at 150°C for 5 minutes.
After heat treatment for a minute, flame retardancy was examined. The test was conducted according to Test Method No. 3 of the Ministry of Home Affairs Ordinance. The results are shown below. The numerical value is the average value of three measurements. The unprocessed nonwoven fabric was completely burnt down. 1 minute heating test Afterflame: 0 seconds Residual dust: 0 seconds Carbonized area: 19.1 cm ² 3 seconds after flame application Heating test Afterflame: 0 seconds Residual dust: 0 seconds Carbonized area: 8.4 cm ² Example 8 Various synthetic resin emulsions (latex) and the flame retardant of the present invention were tested. The test method was to add 50 parts of the following processing liquid with a concentration of 20% to 100 parts of latex, and observe compatibility and stability over 48 hours. In addition, as a comparative example, 20 of the flame retardants shown in Table 6
% solution was added to the latex. Processing liquid 1 Prepared by adding 120 parts of 25% aqueous ammonia and 1310 parts of water to 320 parts of the reaction product of Production Example 2. Processing liquid 2 250 parts of the reaction product of Production Example 2 and 100 parts of the reaction product of Production Example 3, 50 parts of 10% caustic soda aqueous solution, 25
% ammonia water and 1403 parts of water. Processing liquid 3 Prepared by adding 71 parts of 25% ammonia water and 1257 parts of water to 310 parts of the reaction product of Production Example 1. As latex, acrylic ester type (manufactured by Nippon Acrylic Chemical Co., Ltd., Primal HA-
24), ethylene-vinyl acetate-vinyl chloride type (manufactured by Sumitomo Chemical Co., Ltd., CY-830), vinyl chloride type (manufactured by Nippon Zeon Co., Ltd., GE-576), vinylidene chloride-acrylic acid ester type (manufactured by Kureha Chemical Co., Ltd., VAT -S-
312), an acrylic acid ester-vinylidene chloride system (manufactured by Kureha Chemical Co., Ltd., VAT-R-305), and a styrene-butadiene system (manufactured by Nippon Zeon Co., Ltd., LX-426) were used.

【table】

[Table] △ Thickening, slightly unstable × No compatibility, gum up immediately

Claims (1)

[Claims] 1 After containing acidic phosphoric acid ester of dibromoneopentyl glycol and/or its salt obtained by reacting 2,2-bisbromomethyl-1,3-propanediol and phosphoric anhydride in a ratio of 3:0.5 to 4 moles Flame retardant for processing.